Síntesis II resumen, Resúmenes de Economía

¡Descarga Síntesis II resumen y más Resúmenes en PDF de Economía solo en Docsity! de E A  TABLE - OF CONTENTS DISCLAIMER | WARNING! This books intended for informational dy is currently ilegal to attempt almost any procedure depicted ii pi pr dure listed herein be used by the reader or anyone else tor that WHERE TO BUY matter. Even if the chemistry were legal Strike would not advise so y Hnoce procedures unleosthoy have ahorough MHAT TO BUY. . derstanding of chemistry, chemical reactions and methodology. 18 METHodology, 24 Even tha most basic chemical or reaction has the potential to do A 7 great harm. ii METHOD ¿41 Copyright 21999 by Strike. All rights reserved: METHOD +2... METHOD AS... METHOD $4. Panda Ink METHOD +5. 2211 NW Military Hwy, Ste. 115 METHOD 5 PMB4-+15. METHOD 4: San Antonio, TX 78213 Al PHENYLACETONES METHOD +1 METHOD $2 METHOD +3. METHOD METHOD ¿5 METHOD +6. METHOD *7 METHOD ¿8, METHOD +t9. METHODH10- f-NITROPROPENES METHOD ¿HH METHOD +:  Fhe-scst laculo-taclfja just phetamine-with-a-coupl WHERE TO BUY of extra things attached to it. The chemical structures of the major ecstasy class drugs and speed class drugs can be seen m the preceding schematic: So how does one go about beginning an Underground | laboratory? volve the least watched chemicals and are the strongest_ MDMA inetically though, one woul need 3 rings. a combination Heat. and speed, alfñouzh less strong and shorerTasing, are perceived ing-magnetíe sliming plate, Chemicals and giassWare. — The are very oubjecive. Trey, are "equaly 'ine in their efe! except with crude, makeshift equipment,_But believe Strike, the most ef- that MDA ls better The sooner the chemist accopts this, Ms fectiva chemistry possible is achioved wi a good hentro strpiato MDMA (mostiy MDA),_Strke wil lel you know hen a specife ing Scion stuf difierenos is required, Anyway, ifone were to look al tal nitrogen more carbon groups are added on, the weaker the drug becomes. These kinds of stores cany hobby/craft supplies, gimmicky sat 7 am are even Wesker am pee, DU Pp , i they do retain some pretty fair activity. And a few pages away you scienceware products such as beakers, thermometers, scales are going to actually learn every excruciating detail of how under- rubber stoppers and most of hs basic chemicals such as acids, del d-solvents-These-pl listed in the-ch e al dor any big citys yellow pages and are relatively safe Sacos to get most of the basic lab necessiies. The drawback is that they are teally expensive and dont sell very large quantities of any chemical, li is possible to have these places special order a ded chemieatas ds noto controlled chemicar 9 12) Loca midalemen companies These places are also local businesses that can be found in the chemicals section of or big city yellow pages excepl Ihat these placesh snatth y are licensed distributors for some of the bigges! chemical and scienceware companies and manufacturers. Those big compar nies would never sell a thing to a punk like you or Strike. Even if a punk like you or Strike was to present a fake business frant or -9>  veould si proafs of clientele eto., eto. Its needless to say thai this is too much to ask of a street punk. That is where Thess distributors can help. They have the license What the chemist is looking for are product companies that sell sveryiting but glassware and cnemicals. —1n6 feason for this is that if they know they don't sell anything that is watched then the: have no reason to care who buys their stuff. In fact, they want to ) that the chemíst needs and are not subject to the same policies that the-companies-they-selkHor-employ—This-is-trotmeantzas-a put Featalogues to look for are those that accept credit cards and money orders as down but these distributors are like car salesmen. The only wa; they make money g ihrough the commission on sales. This companies: products to. They Just vent to sel stuff. A chemist payment These companies obviously sell to Individuals. All of the chemist needs, especially low piced magnetis srplate, vas- electronic scales and, in some insiances, chemicals and alas: tiermomeler or water and then pays for it prompliy. Having then establsied an account (a fot in the door) the chemist will have ware. These companies are just like local distributors only bigger. (8) Big name science houses and chemical manufacturers p e a ; ame, good custamer_ Then, next time, a lite catayst ether or, per. Alech, Aldrich and Sigma. ls very hard lo qut a fedaling ae. y estantishes count with these giants, bul if one can then the skys the limit that the chemis is 2 good customer they terd not to ask for the Most-chemists should bo-happy gotting-l panies-produet required permit to Buy glassware or as to the purpose (hat some through the distributors. L And-sotho-charad a to get that specialty chemical or piece of glaseware. There are thousands of such places around the nation, Canada and Mexico, (3) National distributors go-down to her local university or graduate research school she could find science compar library and in the divisional labs and offices of Je resaaroh cents. tatives-oF br menutactures [ko lo crop off tons Of their catalegues in the "hope marsomeons will order some or her products. fine Morary has none, then the chemist goes u somepne if she could take a look at some of their catalogues blem-bs me Fi et futt-obgraduate-stu= pr dents, who are dying for attention. Some have so many cata- Togues they dontuse hal, asked, Iney would probably give the chem'St some. 10 . No matter what type of company the chemist chooses to pul Cese types of businesses are the prime choice a chsmistwiluse from its a good idea to have some of he actual catalogues from big gta: rers—Fhit is because it wil help to have the companys actual produc cata- 190 number nr one is ardering from 8 dato ortrom catalogues are down at the university or the horitas request books and are just plain interesting to read and daydream of the day when one can order such-and-such an apparatus as ls de- picted on page whatever chemist to order. The following is an example of how a typical call will proceed and how it will bs handled by a chemist no matter hat busine: he call =RingiRingi= 1  Evil chemist: "Uh, yes, this is Fake Name calling for Fake Com. pany possibly open ar account.” Rep: "Does your company currently have an existing account with ey always asks whether ornotthey were justtola hata customer is a new one ] dto hi latwith-Rival Seientif pany but they couldn't seem to get our orders on time.” Rep: "And Whatis your company's name and address [ They ask this first because they want to bag the chemist as cus- the chemist later to buy more of their stuff ] few companies that will deliver science products to a P.O. box] Rep:"O.K Mr Fake Name, what. can we.do for you today?" she wants and the quantity of each. After the order is confirmed the chemist asks that the enfire order be shipped by overnight ex- for the purchase order number of ihe purchase she just made so í Tí chemist uses a reputable money order and sends this money or- der to fhe company via priority overnight mail. All this rushing ac- professional, goal- criented company, and it also gives no one any ery site. At times it may seem that Strike is implying that buying from these companies is a cat-and-mouse affalr that leaves suspicions high and traces put on one's phone line. This cannot be further from the truth. These companies want to sel their products. If they had to file notice to he DEA or demand documentation every time someone called then they would be broke in a week. This does not mean that a chemist should be careless. fs just that if a chemist is polite, friendly and smart then almost anything can be had. And since, as this book will point out, most everything the chemist needs will be unwatched, there will not be a great deal of suspicion no matter what the chemist orders. Just remember one thing: the chemist never orders anything to the same place she cooks at, Science dealerships aren't the only places to get the stuff one needs, At those mega hardware stores one can find pure acetone, methano!, ethanol, toluene, methyl ethyl ketone, DCMías a con- stituent of some stripping agents), sodium hydroxide in the form of lye, and some acids such as sulfuric and hydrochlorio. These precious tools can be bought there cheaply and in great quantity. Then there are other places such as chemical waste exchanges, pool supply companies, electroplating companies, photography supply shops, agriculture companies, specialty gas canister com panies and just about any place where a chemical can be sold. Finally, if one simply cannot find the thing one needs then it's time to hit the bibles of industrial and commercial sources: "Chemical Buyers Weekly", "Chemsource U-S.A." and the massive "Thomas Register". These three source books can be found at most librar- ies and contain the listings and services of just about every busi- ness in the country. No matter what the chemist needs, it can be found in these books. Even ¡f it takes going one-by-one through the listings, Strike can assure you that ihe chemist will find what she needs and someone that wil! sell to her. The one source Strike does not condone ¡is theft. If you steal then you are a weasel and a coward. -13- Strike is sure that an imaginative person can look around her eve- fay Surrou 5 something can act as a re- other gízmos, As it so happens Strike has thought about this too. made, The best replacement for borosilicate glassware is stainless steel. is about as resistant to chemical degradation as the chemist can tems wow sul rect ure 3 is shown how flasks of any size can be made with two vacuum adaptor and condenser._For the condenser only the inner pipe e steel. The outside pipe can be copper or something made just as they look In figure 4 is shown how a separatory funnel and a Ll equalized addition funnel are made, The funnel part ís just a PP less steel ball valve, See how the addition funnel is made by us- the funnel?_Well, that's how nel out of the ordinary glass separatory funnel that one gets with a  ured hi 10! j each other and “ats going to cause all sorts of leaks. The an- ike-toves-tefion-tape!—This-Inexpensive product ís found in the plumbing department of any hardware store and ls iñe duet tape of the next centuy, Teflon tapo is ha around any piece af pipe or joint, said part then jammed nto lo Hell can mummify a whole jo complex to make It absolute! impregnabla, So what's the downside of using a stainless steel distillation kit? it There is a definite advantage of being able to see a reaction as it takes place and to see when some- thing starts to dístill over. Al) Strike can say ís that the chemist bos h ha the-readi fherth Y Y S , and have a greater faith in the chemistry she is doing. By this trke means that since there. is probably going to be no more than 2-3 diff s in action flask, then all the chemist need be aare of is what thing comes aver first, second He —Strike-knows Ps-aditie-more-complex than that,_Butif a chemist gets he hang of distlation e realy can be as simple as that. PIPE BOMBS A pipe bomb is not a bomb, H is just a device to ha ili D or high-pressure reactions in an enclosed cell. The bomb should be ! HI | madefromrar staintess stest pipe thactas as vigo O mary Erie ter as possible (width, bubba!), There are two good con which can be seen in figure 5. One end is permanently sealed by - . used should have as much and as fine a threading as possible. Also, when scaling up the pipe bomb, it is a great idea to wrap a lot of form an absolutely air tight seal. lt js also possible to substitute a stuinless steel pressure cookcr for some scaled, pressured reactions. [Figs] Some of the feactions that the chemist may use will just naturally retning smells bad then 18 probably ba for the chemist to smell IL Some feactions are. by desien. sup posed to vent bad tings that , when unchanneled, have nowhere lo-go-butinto-ihe+ a no guarantes that a method e go as onned There may be a mistake or unforseen side reaction and some of the most desaly shit imaginable can be evolved. That is why the chemist will con- struct the one thing that may end up saving her life: a fume hood. -2l-  In professional laboratories fume hoods are big metal ing on counter tops and are comected by ducts to blower motors A fume hood is constructed in the manner shown in figure 6. the air from the hoods to the outside so that chemists will not be of rebar cr, preferably, from PVC asseml [sassem And joints so that £ase. The frame is enclosed the hood. The same precautions are taken by no: ground chemists. front face of the hood is halfway covered with plastic while the a to mal le thl on of the chamber is al s dryer duct or some such crap which ¡s led to a leaf blower outside. Although a leaf blower adequate at its lowest setting. To insure that a correct aírflow is the hood's opening aleda 50: d looks to see ¡f the smoke trail is bei: so, Then wo! ne. an Many houses have outside-venting blowers over their stoves. around their stovetop to make a ever, dl ect; in apartmen adequate hood. How- never, ever attempt any stoves lack an outside vent; but to vent a constructed hood about is just way. Mv impo: lain ad id. It is also in another fucks up and blows herself up or to put a lot of her neighbors out on the street, In the hospital or in ers ín this manner. That is why drug making is always done ¡in a house, bam, mobile home (watch out for tornados), submarine or  WASHING o Haking-an-organie-soh layer (ros! lkely the one that was obtained from the extraction of some previous aqueous solulon) which usually contains product Terres, bubba!) for some of íhe recipes in This book that call for uch things Bryingiisnitabsotutely necessary butitis-argoodbetihatifarao" ipe stresses its use then an evil underground chemist will do so, water. A solvent layer is often washed with a dilute acid or base from previous extractions. These salt solution washings are then followed by clean water washings. Since were on the subject of clean water, this is as good a time as any - clean water Strike means distiled water (dH20)._All reactions are to use distilled water (H¿0) only. All solutions and dlutions are to This procedure is ussd to separate crystallizad product from sor vent or to remove crap and solids from a liguid. Figure 8 shows the proper apparalus to use, The ¿lecirs asks called a side uum source, The mino that is shoved through the rubber stopper 15 called a Buchner funnel and ls usually made of while porcelain lo rid. the solvent of any water that it absorbed. All solvents a mitsesit—itis-a-goodidearto id the solventíproduct of any water, especially before distillation,. be- be made wihrdhigo as well Disllled water colls for about $1 ar, preferahiy, PP._The Buchner funnel,wten viewed trar above, llon down at the supermarket__Tap water is an absolute no-no Can be seen to have lots of pin holes in the bottom surface ofits lassware. z Ín chemistry except for deaning lhe glassware rose a face is ayerectar single siect-ofreunded DRYING To filter a ask leaving what is called a er cake in the funnel. The liquid that has collected in the € - pecially bel ilaion. a llad-tho-filrate—Usually,_th Cause fs one less fhing to wory aboul and because there s an past O mon che ln a Ile O Or we 5 4 hi clean Wwhat- heated with product oil under distillation conditions. er iind-ot-solventitwasjustiitercd fam. E All one has to do to dry something is to take a sheet of filter paper or paper towel, fold ít into a cone and place it into a funne!. Abour hatal: full of sodium sulfate (Ma¿S0D,) or magnesium suifate is dumped into the filter and the solvent poured through it. It is also-a good ides to follow-up by rising tie Na SO withatitie extra, clean solvent to insure that everything gets washed out of the diying agent. The Na,SOs is a white crystaline salt tha! fastes without readily dissolving and leaves the solvent water free. This way of drying is also an That extra washing is then combined with the É is going to see in a mardesine om mo ¿£ Ts atihe very end oFthe drug-making process É where ihe chemísi will have crystallizea her É- treebase oil into a final, marketable torm and then-need: parate—thi rystals+ the solvent they are in. [Fig 8] -29-  SAFROLE Where to-begin! Where-to-begintWell starting -withthis-chapter+ a good ideal Every amphetamine is a chemical. And sinos your government doesnt allow one to own or buy the chemical Rself, sometimes legal) Chemicals that: are as close to he final drug ES frole, Jafrole is the 441 starting material for making tod: p chemical itis a schedule | controlled substance and, obviously, ls iisgalto-own-orbay without-a permi Bul, safrole is the major componeni ot / O the essential oll of sassafas which ls St bl S quite legalto obt Hs strong licorice smell which is imparted tol] _[ Uirom tie safrole molecule. Commer- SS Cially, there are two kinds of sassafra 2) bemg sold today American sasafras (Sassars alum and ld American sas” safras contains about 80% safrole but the Brazllan sassafras olla almost 9U-95% safrole and can prefly much be Used as ls, So where does one go lo get sassalras oil? Mb if one Were to cense shops there, on the shelves, vil be small bolles ol 90-90% ecstasy starting material Tabeled as sassatras oll. Larger quanti- comparies that one can find in any big iy yellow pages. Now he idea of what some of their essential ols can be used for so, they might ask. But they still have no legal reason not to sell tnese things to the chemist._After all, the same stuff is-b: del the counter to hippies just down the street. Just to make every- 2307 h S vee OMS NOrS Me company al the fake name of her business and that she make: cense, polpoumi or is an aromatherapisl (no kdcing). "mer is would-be—home—care products houos, tolletry base companies, soap companies, flavoring com- panies, aromatherapy stores and organic foodstuff companies. As of the year 1998, small quantities of sassafras oil are stil being He Ht t OZ SIZeS. Anything larger is usually sold only through distributors a manul aclurers. nd as of 1998, the DEA has informed most of ported of most, Y mot all, Sassafras oil rurchases. 'Mina you lt is notittegabto-boythe ot ¡ts just that you Wi be put on a Tist if you do. The operativo term here is Watched Substance'_ Solution: have someone else buy il for you. Strike has also been poking around the DEA and is getting the distinet Impresion hal tisy Will Very soon reschedule sassafras oil as schedule |, Then one won! be able to gat it at all without a permit or some serious deception. Al of the above safrolelsassafras oil sources are the more stan- dard avenues to gsHihese commodities. There are some ralher exotic sources of safrole for the desperate y po: tally-challenged citizens of the future, Certain kinds of Asian cam- p! —esperi . = safrole (another term to look for is "Camphor 1070), Sources selling “artificial sassaftas ol are actually selling a mix of 50% pr ciable amount of safrole can be four in star anise ol 08, leaf and nutmeg (ots of fun íhinge in nutmes). Alo, there ls a sp bush That grows in India called Betel Batal leaf cl can Bs on he region ¡twas culivated in. The sassafras tree itself grows like a weed in the wilds and along disturbed fence lines throughout the south, southeasl, eastern -31-  Usual Components of Sassafras Oil aboard—and—Appatachian—mountainregions—ofthe—United States. The trunk and root bark of older, mature sassafras trees Component range of content — bollingponiiamtoS can be steam distiled to afford the safrole-containing oil. Another leaf oilofa liíle shrub that pinen 10% 154 grows down in the low woods and swamps throughout the coastal phellandrene 2-10% 175 ñ -— 5 a C Fsamphor 05% 204 [61], The plant is known as Illicium parvifiorurn michx_and Strike alrole 80-209 34 has no idea what the hell t looks like. eugenol 0-10% 252 A new source of safrole that Strike has just stumbled upon is in [Table 1] mike's back yara. Momma comes home from the local nursery culents and grow like crazy, Strike: "What ya got there Momma write, you sick little monkey!” Strike: “Aw cmon, Mom. Let's not get into Mis AN Se doesnt...” Momma: vel T peoded twisted licorice thing..so | bought these wecds That are called “ticorice Plants”" Strike breaks otr a piece of He plant, sand smells 1. > Yeah! mame ¡s Hojo a Strike loves Strike" Ss mother. Suffice to say thal anyihing that remotely smells like sassafras oil or carios or any of those strong rusllc spices is going lo have cy but definitely oi There is just no nr uba in nature tor the aroma ese Imique tOMpoumds give. The sassafras oil that one gets these days is nat only going to efrole br 7 e mps seenin o 1 E with two plants that have these enormous leaves, They are suc- No matter what the satrole content is, even-that-efihe Brazilian sassatras oil itis always a good dea to try to get rd ofaas much of is to throw all of the crude Solas oil into a PP container and stir with an equal amount of 3-5% sodium hydroxide (NaOH) terlayer, The water layer ls poured al and saved. That eugenol ts valuable. Eugenolis usually the main contaminant In safrole in more ways than one, ltis the only molecule in sassafras oil that ¡il mac (he same way as safole so ft hangs argund with the (Also, eugonol ls about the dlosest to safrole In both Siructure and SOÍmg points hatlying to gstrd oy fractional distilation wi be ver ofi the oil that remains is stirred with 3 washings of clean water. know why. But it never seems to hurt anyiting. Añer the third Wwashing is poured away from the al, the oil is transferved to an off all the water. What would you think of french fries cooked in mike wrote to above paragraph relying on The Tew acecunts of assafras oil content that Strike had at the tim: ince then, Strike has come across more substantial data showing that Brazilian assafras-has-NO-eugenotin-t—This-agrees witttre-ttaims-of many bees who have stated that no appreciable recovery of -33-  lo form lo own top layer. There was no separation using 99.8% acetic acid Added 112 grams sassafras ol, Shake for a couple of minutes. ences for it ín the Ieratur. and a co 7 ñ uple of Very convincing exam. pl the iPHHKAL—by Alexander and Ann Shulgin. PlonecrS the research of amphelamines they are Sounas good engugh for Strike so someone other than Strike gave ¡ta few shots, get dsion_Clears withio_15 minute iwo layers, boltom (a ol, top layer acetic acia, proa + ie 5 55 SEparated 18 O TOM UE OIES, WASISA 16 O layer 2x with fresh dH,O. Weight after acetic acid E water washes: 101.5 (-10.5 grams). athappens when Isomerizafion 15 performed is that the doubie bond of the allylbenzene safrole migrat rgeti= cally favorable position between the alpha an ea carbons of the Added 100 grams denaturad alcohol, no layer formed as the oíly prep; hainFhus isosafrole, a propenyibenzene, is bom. E sr F pulled the ethanol and other product into the top laysr, boltom layer containing some elfanal and sale. Separaled layers, right o 234 C. The ethanol and water came 107 100 S. tained (2 234 C. Product was yellow orange in color, suitable for whalaver purpose one has in mina! BTW, añar the safrola cocled, To isomerize safrole to isosafral dd io-to have pure ya frole to start with. This, usually, is not the case. Quasi-pure safrole Os o SiO sassalas al iS prosably ok too, though not recommended. The safrole under a condenser) in a saturated KOHithanal solution for about a day and that's ¡t_The t 7 bout-t26=140*C- oming to e fact that tho eiñanol (usually boíling around 65-70*C) ul TOK-Bean Strike suspecte from this gifted chemist later on in the book. ISOSAFROLE has ho water. The cosest one can get commerdaly to anhydrous ethanol is Everciear whish 15 95% ethanol and 5% water (190 proof). A lot of chemical supply stores will nat carry 100% (200 proof) ethanol because tisa Ba (drinkable) product, This means that th h Al AE this point the chemist has what can be Joosely considered as State perrnt 10 ssl Me So and Mata hassle that many dont mA to isosafrole for others, Isosalrole ls the runner-up precursor for making Ebefouncinmaturo-butrathoris-made+rom-af= most exclusively safrole Tho-95% otto ot Evora trated KOH (Potassium Hydroxide) in ethanol. This was actually the only -38- istotanarbitrary concentration har ne producer decided to stop at, mind you. lt so happens that 95% Stand 5% waleris a constant boiling mix that no more etña- purified from, That 5% is there to ways to remove that water uc as s producing a temary azcotope by-the-addit bubtirey aretóndohahassie-and mar 9 not be necessary. Why? Because an alternative reaction for iso- merization would bo to use a salurated agueous (water, Zak) KOH solution instead of an alcoholic one. This will raise the tempera- ture of reflux to over 200"C but is not too bad an can be used if desired. So, if ít is ok to isomerizo in pure water, then the litle bit of water (say 5%) in Everclear shouldn't effect ihings too greatly except raise the reflux temperature a tad. What are some of the alternatives for is procedure? Well, one can use NaOH (ye) in place of KOH but the yields will go down Also, what about using denatured alcohol instead of pure ethano!? Denatured alcohol is ethanol contaminated with 5-10% methanol The methanol is there because it is poisonous and prevents peo- ple from using ihe ethanol for drinking. This means that places like the giant hardware stores can carry gallons of cheap contami- nated ethanol as many of you have discovered. This product CAN be used, So now that we have all the reagents out of the way let's see how the reaction proceeds. There's the clear- yellow "safrole" sitting in ihe bottom if ihe flask and the clear saturated KOH solution is dumped in. The solution is heated to reflux etc. and yes, some brown byproducts and destruction artifacts will appear. Especially if the safrole ¡s not pure. These byproducts should be expected to some extent because concentrated basic (OH) solutions can be as nasty as concentrated acidic solutions. One is mindful that KOH is less intrusive towards the dellcate methylenedioxy ring structure of the safrolefisosafrole moleculs. After 12-24 hours of reflux the reaction is, for the most part, com- plete. The reaction mix will be a dark brown. So what does one da about all those brown particles and junk, Well, usually there arert any. The solution should be uniformiy dark. If any sollds can be seen it means thal they are insoluble in ethanol and can be re- moved from solution by gravity or vacuum filtration through a cof- feo filter or some paper towels. Ifit takes a day to drip through the filter then so-bewit. The ethanol with its payload of isosafrola will -40- t o with water atihis point cannot be done because water is infinitely soluble in ethanol (and visa versa) so two layers will not form. Eltered_or-nol, tho-othanolisasafrolel relieved of ts elanal by openly boiling lton the on or by atan Any moved by distilation 15 saved because Tis clean and ertecty reusable (remember. 4 should not remove al! of the solvent this way because things can the flask which is perfectly normal. Any solvent that remains will > ing To overwhelm it by adding a buttload of water. If there is about 100- 200mL af dark oily layer then a Iter or more of water is pored in layer of clear isosafrole form at the bottom, a murky brown lyikes! sor fi ñ water Tayer on top, The oil is separated and the emulsion is dealt with in any way that ls best from tho below mentioned strategies for emulsion fighting. This particul: a yt + pi isosafrole in it. lf one is pas then one can add solvent (DCM is good) to the remaining wateremulsion layer, shake Men vacuum filter. The crud remaining in the filter is the junk that was causing all the trouble. Witn it gone one can now extract the remaining tor: rent ade-thi mit the isosafrole oil Mon remove the solvent by boiling or distillation to gat pure tsosatrole (70-80% trans, Z0-30% cis). caused by introducing the water is to slowly acidify the water layer with HCL. As The waler layor acidifies one will see the emulsión and stuff start lo exit the water layer and go into the DCM layer. Y AL  oa . . , Gee, that all sounds fine and dandy. But Strike blethe < last. Without a doubt, the cleanest, fastest and the whole mess into a distillation set up and fractionally distil._ Sol isomeriziag_salrole_and_olhor allbereenes ie ia o tor vent comes first, water second and (eventually) isosafrole will Someone who is 'Not Tim" (Strike's name tor her) emailed Strike come as well the Chemical Abstracts entry forte procedure; Sound sasy? Well, Procedurally itis. But the ye can really < suck A 5 9360. pnosatrole From safrole. Yoshiharu Ogata (Regen- a . , Saul 18 Sofa been pleased win e Sifke was But wal con you do) O O 15 ana ron ed Jr Well, someone named Osmium sent Strike a journal reference 243.59, the CaO and KOH filtered off and the titrate dista, ta at- about doing the exact procedure above but carrying it out in a mi- lain 95% isosafrote, b.240-80. K. Kitsuta” microwave heating. They had strangely high yields (all above , , , a El incentratio! Al a- ol ns Were nolKOH recipe and you wanna know what? He was kind: ing 24 KC long vai he KOH hood pgs, Tr "el coa al, ihose Brazilian improvements above aren't here Just to take had lo apply 1Smin of bollng to get a yield af 99%! SU he otner onetoes istolow that CATECpEtOme Aaa T os 0+%. A small fat- resoliors in precanal and elhanal any needed 23h Tor 90s boom Mask placa pri e 158 er a na source, a shallow oll bath can he, melo: to get even heat. USAS TES misavaye Jus desressad Me reaion Une 3 TT NY ME MOS ABOUT meno e proofpasiive heat gradations thal sil occur, e y Sugn tna e we oven, They then killed Inemselves mos! lKkely. But nal before lo Sara enough, aer cy 1Smin ol is the temperalre read were able to scratch down this procedure as they slowly burned to ng pat a sosafrole (-243-280"C), And that, as they death: say, is onolic alKalme Solution TS pre o ma dark. De ace pared hy Eroinaed sÚrring of a 2 (or 4.49) of KOH pelteis in viicnia alos ray “one cen then ade some var to take up the unreacted salis and separate the oil from this. If an emulsión 30m al alcohol. The alkaine sotuion js placed in a soundabotlom a sacied salte and separate Ie OÍ fiom th, Tan omulsio systemg). Then 4.09 of Safrole (or eugenol) is acidad and no So. clean enough to proceed with but it can of course be distilled for - - de + tatiorrheaten. . z -47> -3-  IN LL) > PHENYLACETIC ACID: Very important fragran: hemical_Only recently was. e banned by the DEA. Fragrance companies tl ya mine oÍl (very expensive). No Up to 60% in various parts of the basil plant. mMoumts IM calamas, cas sie, myrile, “pimento, pistacia, pleronia and some forms of tarra- gon. Icom 2, 3,4,5- -TETRAMETHOXYALLYLBENZENE: ln varying amounts li justthrow parsiey oli potto-geta OCHa grab bag of psychedetio amphetamines)) HO AS OCH, 1] MYRISTICIN: ln moderate amounts in dill, carrot, celery, fennel, mace and nutmeg (no more than 10% tops). Makes up about 40% > parsley leaves and seeds, Give nutmeg a rest folks! It just don't NS 3 havebwhen-comparedto parstey and-parsnip: H,CO 'OSMORHIZOLE: Makes up 25% of the essential oil of chervil. VANILLIN: In vanilla beans of course. But never more than 2%. This stuff js bought thotic and is-chi qe HOLAS LA "CHO et a ery hard to find This al Though. The standard way that scientists get these allylbenzenes and ts e ot ils-fe-bn hi stilati A e y d + You can see from above that some of the more desirable allylben- [ zenes do not occur in high concentrations ln the olís they are found in. Sa that m to isolate the goods. This ¡s not as big of a concern as one might Ebinke 48  sulfate intermediate with the elemicin causing it to migrate out of Essential oils from plants are technically Aron as “volatile' olls. the oil layer and go into the sulfuric acid layer. And since elemicin them will eventually evaporate í (ettto stand. So there is a definite alkene, itis going lo be aboul the only thing that ques into the acid boling range for these oí which, compared to other things in na- tayer. almost e cñemist riko means_lo say that when these_oll dies next ls scparale the acid layer ¡stl cold mina you) place 1 were sntacted dan the plants they come from. they were taken in some vessel and pour in a big old excess of water, The tem- Ah compounde that have relative low boiling points with 300%C drolyzed hy the water lo forman OH, One can also heal lor 8 being close to the max, And Strike can tell you right now that in minutes to nsure conversion. ls that , always going to > the oie boiling conca al the What happens during hydrolysis is that the OH forms and the om Pelo W mico alcoh s nebforms-its-oweroi the alyibanzenes layer. Of course one won't see this because the solution Ís a big SIE BONA PRESS, TOI8Y sa emulsión particles. Emuisions suck b 4 h A acid or ha of this fact. Just boll or distil off most of the OI up to the tempera. filtration mame le Anyway, atera lo or up one gets some Ture of your preferred allylbenzene and stop. There 15 a very good yipropyi compound: And if Strike had Strikee's way; n : an Strike would have that OH stuci right on the middle (beta) carbon e species. Work could then progress on jusing that OH to get would prefer a more e pecto Solution. Unfortunately Strike has Strike was prepared to put in this book). ane. For over half a year preceding this second edillon Stiks was But that is not the case. What the Korean lab found out was that iiermediato out of safroe using sultuio acid (plesse dom asi) when this procedure is performed, ¡he OH stabilizes on ihe al ana Wel, things didn't work “outfor the "Sopropyi intermediate, but it did any use for it as is then that is fine. But wat: is most preferable is confirm the following procedure as a nifiy way of isolating allyl- S p . , benzenes (sort of) chemical our example). Using the simple potassium hisulfate reduction recípe, one can get rid of the OH with no problems at all. Ttreiteraturesstates thatifuone- uses icecotd toncentratedsuifurio acid_on a terminal alene (a.k.a. allylbenzene) an alcohol (OH) Hey! That really wasn't a lot of work. Just a to oral an Strike's intermediate will form “Markovnikovly' an the secondary carbon ñ rar idor't asko What does this mean? Let's take an example Say one isolated. One gets some pure propenyibenzene wiihout eisiilaon has some elemi ol and wants that etemicin that is in lt What one Done en a massive scale, this is a cheap method for getting lots of for about 100-: 200 of concentrated sulfuric acid (at least 20% mixes. And since Strike blew so much cough on this Sion ex eN conc.). Next, one jus! mixes the two together for about 5 min. y dam use ji (mamadas What will happen is that the cold HaSO, will make a hydrogen demic lab of course) 9 =51-  A much more forgiving yet limited extraction method can be used PRENYLACE PONES to Isolate phenol species such as eugenol and chavico!. You see ¡er b: it is chapter whe: Ni 1e- move eugenal from sassafras oli? Well, why not use to isolate me . opposite of what this book Says. and went ahead and got some There ars probably other methods for purfylng the products one *, remicals-and-some-safrale, isasafrnies wants. But as this hook makes clear Strike ls no chemisf in tha andior the precursor of thelr choice: They may very well decido to. real sense of e word Ste has no reales of he ue avpica do something to io ge farher along the Path 16 final product you isa. But on the Hive. Strike gave La few otabo. Things (10d precursor for X and amphetamino production is the phenylace- recrystallization (dor't ask), partial solubilities like what our friend Eleusis proposed ahove, treezing, heating, freezing-and-heating in ylacetone (aka. phenyi-24 -propanone, aka. P2P). For X the a two solvent system, solld phase extraction and altemative forms precursor would be called 3,43 pMethylenodioxyphenyiacetone bination. AI of these are ways that an industrigus chemist ma Strike knows it should tecmioaly bo writen as MOP-2.P, Dil wish to further study and apply. So hit the library, Bra" : ll Ss MD-P2P and thats Jus how stupid-ass Strike is always gonna refer to it. And now for the hardcore chemistry you've been waiting for.. [po ? MD-P2P P2P That double bonded oxygen (a.k.a. ketone) is very amenable to attack and replacement and ¡s the ideal stepping stone to final product There are a variety of methods t mplish-this inte mediate. Many of which Strike is now gonna lay on you! METHOD 41: Strike's sentimental favorite. The one Strike has dream about so very often, This method involves taking hydrogen peroxide-and-t dto termediate which is subsequently hydrolyzed with e aio give the ever- tovely ketore-  pliest). ln the methods to come, Strike wil) let you know when it can be done. Anyway, one has the P2Pfcrap oil, right? Right. Next one makes a saturaled sogtam bis $ much sodial bisulfite as will dissolve in a given amount of water (say, 1000mL). hemistteltthatitmay have been due to the Solv rent solvatin the isosafrole which gave the P2P a chance y Ea crystat sti ¡cal Organic Chemistry" (3% ed,137], Int, viga Crstalizes his Ketonas a usa e sodium bisuinte solution that aíso'contains a ltle ear. Now one adds the MD-P2P oil into some of the saturated solution vent. This is in contrast to the straight up tonty-watery dotiretor-30-minutes, The temporaturo th sl Solution that Strike described above. Here is what Vogel said en and a big old mass of F2P orystals wil form. People often say that page 542- he crystals Tool like chicken tar Those crystals tormet because De but from the sodium bisulfite latched onto the ketone of the P2P to form a a precipitate. And since the o par 5 probably the any consequence that crystallizes. addition compound are then separated by vacuum fitration, dred_mls_of_ether, DCM or benzene, The filter cake of MD-F2P iu ls prosessed By seraping the crysis Into a 10% ACI solution are “added a works best). The solution is is ZP will ren MD-P2P-bisulfite complex will be busted up and the P2F í form, The P2P ls then taken up with ether, PENAS apo de Eine solventlo-glve-pure MDLPZR. Yinadaya think of that?! This procedure can be applied to most P2P mixes but is especially effective on the methods to follow. However, ín super clean met duced, the iso byoreduel can interfere with crystal formation. amount of isosafrole was formed to the detriment of MD-P2P, the wants lo know Ral they made is P2P all one has 10 do le Jue trata solalion af sodum bis al tha faboratory temperature from 409 o, Oi. of water are roquirad. Measure (he volumo. o. "ho resul solution and te lina prat 08 UE O reci spint (or methylated spirit) lethanol or methanol a water bout 45mL.) o just dissolve the precinitata mien Separates ' Eltb SOT AQUEDUS/SONVenT solUlons work, is en tírely up to the preference of ho Chera a a which one the UStTo make one Teel more secure, there ¡s a little test one can do with the bisulfi E itright-3ust puta Mile of that ketone known as acetone into the saturated solution and kchthe-erystals grow. tstrbitmice How chemistry works?! e METE are some chemists that rely on bisulfte as a tool to physical) parate all of tha fromrarrottmix Butsome Chemists, Using some methods, are rightfuly sure enough that ¿hoi kotones were produced in such high yields, and so cleaniy, that separation isn't necessary at all But even they 1% Y Es8 modi SI le to know for sure that sia hey made was Pap. lle pro well TFone sointo the-saturated bisulfite solution and see what oli screwed up the crystal matrix disallowing it to form, Confused, ocn H crystals form, One has ketone 1f nor has fucked: iho-chemistiriadt sallizod-oiLf w_. solution by extracting out ne sito ty other things But when the solution, 7 One can even use this test as a quantitative measure, The chem- igh5gorso oMherP2P product, crystallize it and weigh -58- 39 -  the-subsequent-P2R ojHthatresults-to getan-idea-of how much of their product is honey, and how much ís nat. Get it?! As Strike hopes yau can see, this simple sodium bisuifits tool has amrenor / mous amount af potential for helping the evil chemist out. a] mf trought- Ste owner jet oLoompaní A that do not sell sodium bisulfite (NaHSOy). In fact, a lot of compa- ¿ ROO nies ist sodium Bisuifts' in their catalogs Buttel ns readerTo 598 “hatis the only form o! this YA] PACA MD-P2P compound they carry. In ner words, a lot of companies sell so- eg > han le-altemati other, The Merck Index even says about sodium bisulfite that "the Satrole El [sodiury bisulite of commeres consists chieiy ol sadium metab < toral prostical_nurposes possesses. fhs 7 same ros as lhe true bisulfile”. What this meant to Strike was that metabisuifite would work justas well So -some-was pur= isasatrolo ant A al os nin CS EEES A E E aboY: 0D , o see In the above schematic, the major side prod can making P2PS. This method is known as the Wacker oxidation and is not tar or junk but is the very uscable isosafrole. This is Just us miing sarcle. for any oler alslbenzane), Dalladium Poor ilustrafion of ho desire of the sarole double bond ta mb lid, cuaras sblorde ae dmolayformamide in an exigen gate to he Rosarcle posllon uhen gen the chance, Tnegu= atmosphere to get MD-P2P very quickly and in a totally ciean loride 1CUCI and Oxygen are there to promote and keep manmertH+2] There's ak y otH43. the PCI in a +2 state (don't ask) There are two different appa-—————— ralus setups that a chemist can use to complete this recipe de- L——Gike ranked 43 in the Top Ten from he first editon because Pending-onthe-equipmentavaitable—Figure10-SNOWS A S8Up O PL st tl o ar Elec EFEC ADOS a Mp RO Bo ne nt O expensive catalyst as pacta Street chemists are often ghtassed a fem can be altalned using a single neck flask. Also, one can duction. But this has rot been the case with this procedure as ones distan set into the Mask's neck Strike has happlly found out, ALE7 00-59.00/9, PCI 1S SH pretty - e not been a deterrent as many chemísts have No matter which flask is used, an addition tunnel is required. An foam, dor nod ft be This procedure works so well that itwould, saco Funnel ls Just ke a separatory furnol except there 1s an mm dotstoo a a credilga licensed research lab. The tolowng |s what Strke first sure > Cuhich this one is s going to have). Strike knows! Strike wrote about it. Pm ure-sounds complicated but this one st You see, The addition funnel can be bought, made from a separatary Tunnel as explained in the How to Make section of this book, or =50= =61>  s an 3 eng used then the Openings € on top ofthe additon famel and. “he Une tion. the fasicare piogged Wim stoppers and the stoppers seguro Is going to come from oxygen t lla to the e ms ts > balsos Al osygen, pnehes 4 ses sul system using a balloon. Pure oxygenis easy to get. The chemist Sa bal . an cargar e nsenboconó ascity ges cdo compe and releases. This setup can noo pres, qn dependa na and gel a small. personal use Bote Mes Ts gen Ts Men ellipical kind or one vih a O pinte an be bought at any toy store. Anyway, all that infitrated-every parto tas en ya he a, closed system and the solution in the reaction flask is allowed to. : y tir-expusea-to all that oxygen fort hour. Át first the solution is ] brownish black, but as it absorba the axygen Ls Evilltura an olive green, Añer 1hr ¡ts time for the pi to add Le the safrol period As t1e safrols 15 Being - added it will Sn to take up all that oxygen causing the Sama Sos That things are woring) but after tho addition is complete and the safrole h; ted—to- MD-F2P the palladium will again start to saak up ths remaining rice agair-The-solutorremains stiing at room rra for 18-24 hours, If the balloon lo: es significant volume during the reaction, one just Fils K up again. Nothing bad will happen. Eh + day the-chemisttaes a PP container of T500mL cold 3N HCL out of the fridge and pours the contents ol Ina read ol Ina 1 TRE MIX is stirad a te and oxtracied 3 times wn 10m! p Mo 7 Airmet to be added here 1 that ne DOM extrac meedn iodo Mata a ith-water.—Many—bees have reported af His re . (Fig 100] duces/prevents an emulsion from happening in the next step_ The. [Fig 103] Selventis then mashed wi 200m! saturated sodium biartonate na stiminc Tezmnialy he washings can be opa, but elther way the sol plied So, 1009 of safrole 2 he sal on fumel an 9 caly ho ve A e sol 62. srl the sodium sulfate washed with a little extra solvent just as is de- qa 7 E nal ts Seed in the methodology section o his fine book,_The Solvont el a a  F A Buchner funnel Whatnan Tier paper lite (Heauy Walled) Support stands and clamps Phase Two - Chems 3N HICT Book calís for 1500 mis, on [he 5x scale up she used Fhe-extraete Westronce wittra seturated solulan of socium bicarbonato. _ This washing is absolutoly necescare lea took says 1 can bo Skipped - DONT. The problem with Ít [and ihis is the ot j 4 emuision develop from the wash neutralizing the acidic naturs of th Fhe-sastest-way to dentWwitir is 10 vac-Mter Ihe Mess. Your na Yourself of the scum and breakup the emuision Into a rey easy io separato fquia. Ono washing wi soci be Methyiene Chloride E A iny lo fiter this solution before_acidifi catión. First, setup your vac-fíter flask with vac-rap, Buchner mel 8 VAS SOUIGS and Start UTE 7 wil take about 6-8 hours to fiter. The cuprous chloride ls in sus- pension and it almost completely clogs the filter paper. mas ho s p> land reduces tho fiter time to about an poa So cup your vaciiferng as usual, moistenthe Wer paperwrttr a ie 1420, Her washed white sitica san on the fiter paper. Moistan he sand with a small amount af HO. Apply the vacuutrtothe-set-t1p-andtia th ahi into the sand. The sand wil keep the cuprous chloride from totally clogging the paper up. Celta can be used Im place of Me and _Celite is a filter ajd' is aunilable wherever fine chemicals are sold lfs a slandard and unwatched laboratory ter._Calito works able wihoul having to deal wih a chemfab supplisr, Place the fitered liquid into a PP container and add the appropriate amount E INHCI She stimed itwitha wooden padole far a few minutes had a 2er separalry fune), Sinos DOM goes ta tha Dortora, a lo! jorr. DCM and broke if into 4 extractions of about 1500 mis each (she 3000 ml carbonate is sufficiont then wash op th te Silica sana (white, sterlized and washed) or sodium ahloride, then once with fresh H20. Now o oiraal a Celis ttsoctny sutfate-—YOurare ready vor Vacuum distilalion. The DCM extraction should be golden to dark brown in color Phase Three - Equipment (Vac distillation) Vacuum pump Heat Mantle with heat controller Or hot plate with ol bath 1 3-tter boling Aeste Lorfatbelt 3-way adapter (stil head) 24/40 +Westrondenser Vacuum adapter; condenser fo receivin 1 T-fiter round or fiat lask (used for recelving ketone) 1 herm: le daplor (24/40) 1 thormometer -10 to 400 € TObiTg POT Water TvDar Misc filtings to hook water fines ua Aluminum foi (to wrap ask 8 still head-insulation) Washed € dried DCM extractions  vacuum. Her vac-pump would ont pull 100min Ha, so the temp at colar of the reaction aller 72 hours was mn which product frs started coming over was 198-200 C fawprox 60 the final yield was 362 grams ketone 72.4%, 51 grams isosafrole td S 204 6H :—Not-tad for very little work was 308 grams 61.6% +)... The plas being residue that could not this «p! Once ho Sao ls good vol aan ing o Be disiled as there was no a Small enough Fask To Imish Te dis- time lo check the balloon” fillation. DO NOT run the larger flask close to dry If you do, upon cooling the reside wil carbonize and push black crap thou the Note TDK's appalling pronoun use. Actually, nisther TDK nor conde Stnke van be held accountable because this was witen by expand so rapidly hal e carbonized mass will cause the flask lo someone else who addresses tha audience ina normal Way Thee push away from the condenser sad possidly break 3 valuadio asida, look what happened in Lal account. Seems lko the tradi me to stop. El ol with her similar mate ay have b tilea, 1f's time to st pOr sae 1o po with other similar mat overkil. Given enough time to react, very Small amounta ol PáG, do the job Justine. Tha? vertalnly makes a difference ii separele and purify. This was explained from experience; she ran wallet! y in one's ñ close to dry and had the worse happen: Black pas Shooting e e 0 e ane ampl pos ive by a bee named TaRa (Coula be an las of TOK, Strike ant sure.) It is essentially the ame old song except tl gl proved that CuCl, (oupric *Yield: isosafrole, 60 grams (12%) TOTAL-MDP2P, 338 grams can indeed be used in place of CuCI a aan Morida) (67.8%) The smaller porton was dise ía a 500 o Mask and Ques you more examples of tecmnigue The more of this one has tlations dd completely nd of te aiscaloratan or smell 1 12% ISOSAFROLO. method. . The above dream was scaled up in exact portions, as tt was her m i de d meas- for-sonetiaing tral Was INOUGAT o be a lost first, Her next dream had some variations to weights ar cause ¡Lost Cause?], Dreamt about using CUE lo reia da > as TONoWS; Noted are the changes to fe above dream. Ta ihis dream the book writers Shapter began tike this - It took 800 Phase One - Chems yg saf_ 44 y PoCt, 240 0-mis-H8 Safrole: 500 grams (same) e es, stitred in O, atmosphere with Soon me 96 hours in a 3-neck 12 rflasis-yietdwas-69-71%, (distiied, dia bisulfte and then re- Cuprous Chloride: 300 grams (ost have cut this to 200 9) distiled the oll from the bisutfite procede 7 AMET AROMEmidEJ” TeaUction) miques would got better yieid. Materials lost in wasting and filtra Distilod HO: 300 mts tion, purification distil wet the-book li ep 1 cylinder of pure Oz (TS) outline, bid a few simple. Pia Were appiiea. To elimj- rate tie nasty emuistorr tom the sodum bicarbonate Wash they Do everything else the same except, let the solution stir in the Oz washed the initia) sovent extracis a atmosphere lor 77 HOUrS. YOU ME9d 10 CNEGK MS DSNODM eVEy HO. Used DCM as extrad solvent Remowed a good deal of 12 ha o y  much a pressure as tha Ballaan would hold as they leed the Mask direct from the Os cyiinders putting ho balloon on the Top apen- hase tom to roguiator la feed Os into Mhe stem Was casi able To KeBp ESK STO as posi hurst when flted beyond capaciy and ll wil give you e rush tha! not forgotten easily. (makes you think yow blew you 1xn up)" mn 8, Str Tate. 15 min el and another mé Enzo. added Extemal heat íf needed ís used. AL4:90 another mi was added, na temp held at 700. at 2: 30 tho final a was added, and thera sho at 70 e tor 30 more minutes, alos! to: cad lo room temp, odo starting fuidínod Q)....BODOOOM! yietd; over 70%" * Interesting note, Using uc for the first time. NO OLIVE GREEN rough the xn, Never cama close to Green ffght, dark or olive) When xn finished solution was very dark reddish-brown, even hours maybe excessive, | bolovo they were hoping : would turn green ara te Tongert ttroag! lost cause. Fortunately it worked out on the +++ side) o read more about the Use Of UUCITeadTe! Jhatooks great Spiosboy Thanks, Bra And to show yos tha Spiceboy isn't making this up, ihe following_exps prove R. This was taken tom the revisw [13] written by the same y dactor that auths nitor- PASE articie ti STMRE drew from to formulate ee reaipe. And just as Spiceboy says pray compe" compound or baligon, Also, tre reaction time is seríon a needed is drastically reduced: * in a 100mL round-bottomed fask filted with a magnetic stirrar is placed a miture of palladium (11) chioride (B9mg, 0.5mmol), benzoquino: 4d í (20mb), To the solution, T-decene [substitute satrole for this com- Now here ís a post from a very infuential chemist named Erico of course). She decided to go ahead and apply the ¡dea of using benzoquinone as Iho oxygen source: IF works (Usocia mean tro entre <pparatus "much more simpler and causing an increase mster-byth mot) isatted TO Mi and the mixtura is sttred at room temperature for 7h. The Sa bon is paured into pora fiydrochlona acid (100m) and extracted wth 5 portons of ether. The extracts are hed-mitirifras por tions of 10 aqusous Sodium hydroxide solution and a portion of. e solveni, the residue is ited to give 2 decanone [P2PF yiejd 6 tg (78%) “Holy Ketonel What a dream... 100 ml of DMF stiring in a Mask equieped w a rate was upped. Finally, 7 y of pdcl2 was added. A dry addifion Mixed intima, Next 11tg of pbenzaquinono was added, Stir lets see what Spleeboy dreamt might happen if this Were actually The last variati houle_di is-aboutihe-use-orsoluent applied: Ever-bitching got the rarity and price of chemicals, the bees tr ratthe used in this method. TDK sent Strike an article that gives some credence to this [16] In it the al cohols methanol. ethanol, 1- chrapanol, Araneda! and others were sample Sxpermental from the article (ust picture using Salrole or attyibenzeneimplace o the Thexene):  thon-Esmoll_Eheres smell bet fro tone in my fingers. 1 dorrt know fr probelms are if temp is not used, ¡'s necessary more solent, may muctHtait-complicat extraction, although in my test o are 70 cc and lí seems to work, but itis not an fomogeneus solution. In JOC they say the reaction can be done in dual phase, this will he my next try, ¡6 jt uns, lt wil be the best, just stir safrol with H¿02 and solvent (HI try , , 3 ” separate layers, distil. Perfect simplicity, will it work ? ¡t seems best temp wifi be 40-50 C, it will increase reaction speed.” A few days later: *P m workáng now. Best results were obtained with dual phase with toluene at 50-60 C 24 hours stiring. The isolated ot Smelled a fot lo kt Evita elote ; yield —Fhe-pa is needed a good Stirer, and | was working with a motor cassette mi 18 magra, seasea ani 300-400 ora Then Thought a must run 24 hours, . The recipe will be something like 300 grams of salrol 150 ec of toluene 100 cc H¿0, 30 % added dropwise cc H0730-% added dropwiseatS tro 100 cc at 12 hours 10066 af 18 hours.. 2.5 00 0f acetic acid 0.5 - 1 gram of PA(ACO): stir about 24 hours.... thats all 87 TheraddabitorNaHCO; (TF grams ) and saltfo saturate solution, more volatile than ketone, after 5 minutes (or more depending ra- Stir a bit more. Sepa, o Sator ketone) star Ie kelors SMBl. Y can now smell lie Ko- Time depends on reaction speed. Reosetion speed depends on the a S8ms o De good, more catalyst, dess time, More temperature ? May be more hy. products, this 18 whaf happen when acefic acid is the solvent Probably a 900 way wii he also acetio-acig Phase is Easy to extract ans uses less omic > bútiva f hope my reaction success and | can run the 'omorow. Another ici is nom water ap is at about 29 C (to distil), may be Jl Hinata enough to desd ketone at abost 180 0 Couple of questions for me: 2>Acd tha toluene + satrotint ¡then add acatic acid >PA(AcO)a, then start stiming, then start dripping in 40,2 of sodium metabisulphite ma stired, practically all meaciod forming Well, l thiniciés better to ad A ST RYO VERBO YO US DOMO: TÚNDREAS EDU als lo prevent ostelal aecomposii lora RO O [89 % yield. but fs oniy an impression, may be less, Now fmre- ccofsatol 1000.01 4.0, and then add tire rest dopise. peating the experiment to determine conditions and then, lll da a ISO 150 BPAGUATOT acaTs acid Pas, Tor example wo1id 5 00 ut >the ran or helo Ein pour opinion)... 10m think more 0re Dy-producisT 7 ws 1 ¡Oda prENiOSY 4 Bi of acelí acid cen help reaction to prevent decomposition vf catalyst_ Ne OC article 1425 limes, acetio acid 5 not eacad af al, because ll tatyst-degrades to-Pd-metal-1S 710T MOTE OiSSolvaT, So WAy add gcetis acid ? My last test with 10 00 of salrol had 0% cc of acetío acid, but FI omit A in next xa. + thatuntortanately tere 15 a Hyper oxyaaton or oleoTin as side reaction, and gives organic acids, probably MDPhenylace- 16 acid and may be a bit of piperonylic acid. ¡Es easy to realise ll 79 -  e lng-ph-att ti eh tion: 00 y safrol +1 y POACOJ, + 500 mis fent buy alcohol + 400 mis more important when rar is high My last try was dual 35% Hz0, Added evervíhing but HO to a phase, 1000 Sama 07 PACO, 20 of foluens and aboul 46 co ap, with a refux Condensos amore, ana dropping O, in fhre pan, w added over a 30 minute time Tramo As this was HO: concentration decrease, so reaciily decrease also a Dl ( 7 added they rotioed an evalullo ol Poo mo / BesT sofuljon wi be inorease a biF catalyst BTW, in my (O; from the hos. Monitorad ¿Siri and temp With no unusal ee e y SOtutiorT was a Tght orange ld also ketone. So IM do a sample vt exact conditions do brown, after 4 hours in started to turn a very deep ora, Is polos Also ia small of sofol was completely gone and PCI, Now, when | come back lo home, 1 extract my last 10 00 was replaced with a unique aroma_ot ete tribu resclíon, and ff sos fho lose of material n carboxytic acids, bo- able to this rn as it differs from the smell of the wacker oxidation ause they wil Faralmaic ny lastyiola ec rxrfora total of 6 RoUs, mamtained temp af about 50-60 % only, es from Good 30%, but not bad havid the E to 820. Color at tho end of ren was deep oran, matara Or rmemicals HOenE and ¿05 OTC T 850 16 M6 emOT O ASA O a A that supposes. But 1 would prefer 70 + So try ta sena me the in- formation of your ¿end's triend, may be there is some 10 key in it im- To Eeporate, pe ol Ea an equal volume of fresh coof water e or 0 tetore addí: 4 ta y ol started ta. drop >ul perfect used DOM to extract all traces of *legant, chesp, OTC, High yielding procedure. 1 have only a bil OTE ET TOO EN SO] O 0 ro TAS OTE 0d hen tro oil This work up is By Tar tho cleanes! pasiest ana simplest Hi process tha a o stone be 1H have your post tomorrow > SiS)... Doe Me ol Wes extracted, (Ne Oxtacts Mero pooled weshed-wtisodium bicartonefe TX, saturated solution of NaCT : 1x, and two washes with fresh dH:O... Same time was required. Ss Mos Tings happen Aena compeient snergzed anemist Tor fho work up as there was a lío emuision from the use of tha geting a a little rio e the results (as | was communi- gested Using a an alumna coma to remove the Catalyst (008 yA use of tert-butyl alcohol and other solvents as was discussed in me French joumal articles, But just days Bofore this. book went to So po we have this solvent ¿containing tone, aried jon Vlacetones forever. TOK, bolstered ey Me reassurances fo a solveniíetone and placed in beaker on sti plate and boited olfihe usiMg E suling ol Was a nice reddish-orange color. Had a recipe for years but forgot to tell everyone else, came NOugA very unique smell too. —Took about 2 grams worth of this ol agaín. The following is the proof positive definitive application of added to a test tubo containing a saturated solution of sodium br. Mis recipe- dto tere tive-oi+precipitatecnto a witistr yellow mass e simitar to what acetone would do if added to a hisaifite-SOfuton). Never had His quick of a crystalizalion. Not 807 31  ss E out say the e pul ol tnis ketone is >90% and the 9 yiald will be minimum 78% and probably as high as 86%. No isosafral el- E is highly selectivo. hadto go to press, the ball was Stl up In the air on his one. Con- icting, oud results from many different-groups- i has a lot of advarates and proot of its efficacy. But it seems to be a little fickle at times; the causes of wnich are still A dto this-de Y 100%.of. the reactante consumed. Example-5t-Add—t-mole 01373 4m8MyIeedoypheny) propyl ene, .25 mole of methyi niítrite, .5L NE Í .00025 mole of lrimethylemine, and .0006 mole of paltadium chlo- de date” > tidea: Eslysti ly tor +5 tours at 250. The conversion of the Storing material was 92%, the yield of P was 83% and Me Pd Turnover Number was 166, ene, 25 mola ofmetiy! hitrite, .SL or methanol, 36g of water, .006 ke paltadiora (tj vttoride as a tataiystio a fask, Si magnetically for 1.5 hours et 25C, The conversion of the about And ere seems to be a lot of poste regarding 1s high success rates. Most people gel started from them iure where they were first published. The following are some representative examples from the U.S. Patent MEN =ThS is a P2PT80pe - stanting matenal was 100%, the yield oFMDP-2-P was 88%. trike never even knew about it until Strike saw everybody talking atout it on the net Butt seems lo be extremely popular. Shulgin sama 86. o a hydroxypheny) dorpyiena, 0.25 mole of metnyl nine, 0.3 Her of nds catalyS were charged into a reaction vessel. Thenthe reaction was gar: red out at a temperature of 20.degres, O. for 1.5hours.” +h,838,094 Process for Producing mo Those propylene' species that the authors were using are no dif- pe 7 Terent than safrole or allylbenzene, In fact, sarrolo isa perfect | ol ubstífute —Yowzal Those recipes look N Y MENOJELN o Understand ít, there has already been a di s it AA 'eNO ¿EL NS y o ly been a detailed writeup of the Satrole MD-P2P A ISAZA "Example 24: Add 1 mals ol 53 LME pro. je o£methyl nitrite, 008 male palladiumn bromide as 2 pe SL of metanol and 36g af water to a flask, Stir mag- iy a methylenedioxyphenylacetone (also known as 34 bythe=mumbers-eppticationr ufne-above patent as witen—TAIS, Strike believes, can be found in Undle Festers “Secrets of LSD Manufaciure” andíor “Secrets of Methamphetamine Manufac- sure! and submitted a new, hybrid form of this method which she seems to-have-tommutated afterarioruf-mought-on he matter, So here again is Sunlight: > PSTÍCMEA E TTSW TESTI [she's just kidding folks!] with the nev experience, with ís much boHerihan the other, Derkness part is extraction (yes, a lot of dark 827  METHOD +85: Could something this easy really work? Actually, yes! Well, ya wanna know something? Actually Strke doesnt know if this really works or not (Well discuss this ín a bit. But first read the following which was what Strike wrote in the first edition of TS). Safrole is converted to MD-P-2-P in about 8 hours with no watched chemicals and a yield of 70%-80% [19]. The reaction is shown in the accompanying diagram. COLE OA o > o "CH HIDAC COn sosa This will work for conversion of allylbenzene to P2P. And the bo- nus is that Ye major side producl is isosafrole- The mercury (II) ñ be made quantitatively (100% bubba) from mercuric oxide (HgO) and aceño acid (why anyone would do that is beyond Strike since HO and propionie acid, The oxidation of the intermediate aleohol ís achieved by using Jones reagent [153]. An 8M solution of Jones reagent is made mixing 267g of cold chromic acid (CrOy) 230mL cold H¿SO. and 400mL cold dH¿O then the solution is brought up to a final volume of 1L witk dHO (or can be pur- chased). The working concentration that one wants is 2M, so the chemist mixes 125mL. 8M stock with 375mL dH20. The chemist now gives her knuckles a crack and begins. An ap" propriate sized fiask or PP container is placed in a tray of water on the stirplate. Into the flask is dumped 800mL acetone, 25mL -88- dH2O and 329 HgOAc. This is stirred a little, then 829 of safrole is slowly poured in. The solution should be bright yellow. Now, 375mL of 2M Jones reagent is added drop by excruciating drop over a period of dhrs, The chemist will keep chunking pieces of ice im the tray to keep te temperature al 250 +/- 5", and the solutión will turn dark greenish brown. After addition is complete the solution stirs for 4hrs more. When completed, the solution is merely dumped into 1L of dH20 and extracted 3 x 100mL Et¿O or DCM or benzene. BUT when that solution hits the solvent, the biggest, ugliest emulsion Strike has ever hypothesized occurs. it is wicked! The chemists can try all the usual tricks to get rid of that biteh, but when ¡t comes down to it, there is only ons way that works. The chemist is going to have to extract with hundreds upon hundreds of mLs of solvent. The idea here ís to saturale bath the aquecus and emulsion lay with so much solvent that a separate solvent layer can form. Once saturated, the entire mix can then be properly extracted. The solvent ís then washed 3 x 50m1 dH,O and, if desired, can be washed once with 100mL saturated NaC! solution. Finally, the solvent is dried through NazSO,, removed by vacuum distillation, and the first 5 to 10mL of oil that distills over is saved because it ís isomerized safrole (iososafrole), which is suitable for reuse,_The Tes] e ol that comes over will be the ever lovely MD-P2P, which is perfectly suítable for amination by any method given in this book What you have just read is what Strike wrote in the first edition. Stike laid down one day just before publishing and had this bad ass premonition regarding the recipe. But most people since then have not. Let's see what the problem ¡s. Sirike got the journal article for this recipe as literature citation used in the original Wacker oxidation Strike used for Method 42. ln ít both _mercuric acetate, and to an extent, lead acetate pro- duced ketones as described. Someone-Who-Is-Not-Strike also got a certain ketone. But maybe they were lucky or just plain virong. Most people on Strike's site say this mercuric acetate thing -89-  just ain't happening. But some say that it does. Funny how Strike oxidetion requires NO excess to be present during the oxidation. sitive posts... That's why one has to drip in over a four hour period. Also, after only happened to save those positive p the drip, ihe full 4 hours following of stiring IS required but tho “Posted by Dr. Queck on March 08, 1998 at 16:53:53: temp should remain stable... QuasaaaacK, B. Big secret...QuackilMI, Use approximately a total of 800 ml NADIA E . "y Quack, Quack (twice the amount prescribed) for the tree extractions. Dont 's this fítle duck and round and round she struggled with queck at me... starting fai. ls cirsapti Quackl Hors 15: Let 2 od, 3 here la o report for all to benefit from, Quack, the fist extraction st for several hours (or ovemighl) and the Quack.. seperation wil be VERY clean. However, there wil stil be an emulsion present in the ether layer. Now, the Quackload of prod- uct will be in the first extraction, so the emutsion and settling of the book owners out there, boy did you get following two will be much quacker (faster). Combine ALÍ. three paa vorth, Check this ou (btw, Dr. Quack has NO idea ether extracts and note that there wil be a little water that wil how this came about, but Quackl, Quack itwhat the pigeons told separate out from them. Dr Quect- promise): C. Big secret $$2...Quackill!...One MUST filter this 600+ mi of Mercurio Acetate method) use ihe fofowing in etiar,.but a duok cant do íhis all at once...so one must filter in ac Dl roagort rudo moral. ! vacuum fíter in 200 ml portions...ohanging the duck paper every p ” timo and wash tha flter cake with sther..Dr. Quack thinks a vac 1. Ethier- Starting fud (works great - Quasacack) 2. Home made uum fiter (apirator) at this stage is a must... QuacktM2) te (Now this stuff can bs special ordered from ones ! o em spot, 0 aros a delay, may look funny - Quaaaaaci, 0, Now e ito de o deep recstyolom: Dist! af tro h h hat is the solution to this? Make ll e and teke the temp up to 170 C to drive off am and is more expensive. So wha , and fare 100 Co dio al e J0ok and points ducks to a referenos. Follow the EXACT Now add 500 mi of saturaied bisulfite and stir for 1.5 RS procedure Eo nero Propionete except use glacial acetio hours... QuackMII! Vacuum Filter, the duck fet orystalsil! Wash acid, ki) You'll need t 20 to 25% £thsta vuith ak y , stable : nato uso Zo , , bisufite action product..cen be stored forever... Quackll Yield brew mercurio acetete since it ís a fitle Conteminated wi aoetis : (ducks cart get lt totally dry without a vacuum oven). 3. NaOH -50 10 80% depending on a ducks techniquelill itian is fine!! Queckt'! No need lo purity further for OO pu Dr. Quack thought ola Strike had e screw loose af first. but after y a continual quacking and persistence, Dr. Quack is convincod. this ; (S): thod ís great as wellil! Quaaacasaaasaraaaciimnii Hope Now hero ¡is the secratís): , methods a A, Ducke/Boes/ Whatever MUST koep the temperature in the ího pigeons cleered some flíngs up for somo range of 20 to 30 C during the dripping of the Jones Reagent Et of you bees and ducks. Quack_Quack Y ice to the water balh to keep ll in This EEES largo drop Sue 4 lo 5 500. Now as you can see, Dr. Quack is half nuts! And his description of ends... Quecklll This is imperativo since the mecanism of chromic things and outcomes are right in line with what Someone-Who-s- -90- ole  Not-Strike may have seen. But what Dr. Quack did that SWINS did not was use the bisulfite test with positive results, What does ——— that mean? It means that some doublebonded oxygen was formed, unless Dr. Quack was fibbing to us. It cannot have been a propi the_bisulíite addition product. Could an aldehyde have formed (don't ask)? Maybe. But highly untikely considering the mecha- nisma of the reaction. Later on Strike noticed a few posts from Dr. Quack grumbling about how things did not, in the end, work out with the products of this procedure. ls Dr. Quack cwazy? Yes! Is she a bad chemist? NOI So what gives? Well, the following is a personal communique from Merlin: a chemist that all of you will thank when you see thie ———atutshe wrote later on in this book... “42 without water - proceed as follows. After the 4 hours stirring is ——— tompiete extract direct with Ether. A normal amount of Ether will de nothing so add more till a layer forms. This is due to the need to drag the acetone out from the water. Water and Acetone mix, the Ether needs a helf of a pulí to drag it out. The layer will be huge as it includes the Acetone. This will leave the mush which wants to form an emulsion in the water tayer which can now be discarded. The etherfacelone layer is Now washed with water which will extract the acetone from the ether, leaving a small ether ——ayerwhich contains the product. This layer will be deep red in colour. After three weshings (leaving the boogers ín the lower water h hi 8 MOTA of isosaffy will come over beforehand (a couple of mils) which wil foat on top of the product (which 1 hope is MDP2P as this method is so fucking quick and easy compared to Isosafiy bastards and inat palladium chloride method). This extraction method would teke 3 hours in total including purtfication, no need to fuck about with_nasty emulsions, and the yield seemed to be nearer 60% (rather than 50%) giving just less Ihan 60g product from 829 of salfy." —— And atater email said this. -92- “Well the gospel according to Sooium Bi: ñ isultete Ketono. Whether that's a is ll know tomorroma ni IS a See?! There it is agaín! But even when this person sat down and contemplated the use of the P2P nothing but misery followee his use Is potential is massive. But it needs further study! Yeeshil! METHOD K6: This one ís for methi cooks only as it í j ! ly as ltis only practical for making P2P, not MD-P2P because Sinke dont knay mero ene san get 'piperonylic acid”. lt has been around awhile and works really well [20]. Therefore the cnemicals needed have been restricted for quite some time. But if resisto ut if one can get them then what O Os S coom —— ll fl Phenylacetic Acid P2P This is a way to do thís procedure without havi ¡aving to use one of Mose crazy tube fumaces stufied with thorium oxide or manga» hous oxide catalyst [21]. The key here is to use an excess of ace. lic annydride. Using even more than the amount specified wil insure that the reaction proceeds in the right direction «y ion aT dibenzylketone will be mínimalized (dont ask). 189 piperonyiic acia or 13.69 phenylacetia acid, 50m acetic anhydride and 50mL pyridine are refluxed fór 6 hi 'Ours and the solvent removed by vacuum distillation. The remaining resi- due is taken up in benzene or ether, washed with 10% NaOH so- lution (discard the sti Pe a le water layer), and vacuum distilled to get - 8y METH z i 4 - ur parusal [22, 23). 709 piperonylic acid or 659 phenylacetio acid in 250mL. DOM is stirred in a fiask and 64g SOCL le added dropwise. The solution is heated to reflux until na e Fotutión. The shemíst should have a tube leading from the top of the reflux condenser to a glass of water to catch all that HC! -93-  , 0 looking for! Solve any polymerized mass (No, Strike stil ain't gonna tell you So without further ado, here's the recipes you've been a how to calculate '3N'. You really need to learn.to calculate Nor- o favorite. Guaran- mality 8 Molariy. Sigh! But in this case 3N = 3M which is ap- METHOD 41: Strike's extra o Ts led cleanest, highes! Proximately a 10% HC! solution), “The entire solution can, teed to put the starch in your sos S Here is where the chem- ist comes to a slight variation in what ls normaly considered washing and extracting, Ths MDA is, at this point, an acid loving ielding procedure Tor malingMDA Aer kicwn. Itis absolutely impossible to fuck up. o species and is actually going to stay ín al that HC! Solution even Y me fr that solution is mixed with an organic soent. This gives the chemist an excellent ohanse to recover all of the valuable, unre. o == o NABH,CN/CH,COONH, NHo acted MD-P2P which is not acid loving and will go into the solvent, Í —— So the chemist extracts the HCI/MDA solution with a few hundred 2 ms of DCM (aka. methylene chloride, or dichloromethane) and MDA saves the DCM to recover the MD-P2P for later use. Technically, MD-P2P tha concentrate is supposed to be dissalved in DCM and then “ex. talyst needed is called sodium oyanoborohydride tracted ' three times with about 500mL_of 3N HCI each. Strike" ECN Iris nol very common but tere ae a Way works justas well. e ut of El a A e piro sitting out al night. After the DCM ís separated from the HCYMDA, it's time to release chemist makes sure that E the MDA from the water, To do this the chemnist has to make The method ¡s simplicity itsel some saturated sodium hydroxide solution. A saturated solution is uo 100g MD-P2P (or made by dissolving as much sodium hydroxide as possible in an Into a large flask or glass ala. 200 methanol amount of water (say, 500mL).. This NaOH solution should be aa ten 739 ef powdery sodum cyancborohydrids chiled in the freezer. So, the chemist is going to place her e it n from a MD. eHtati: P tine : e PP containeramd amics balh tray baby nitrogen tank ¡s blawn into the airspace of the flask to dispel with stirring. Next she starts adding the cota NaOH solution in aby it and the ask is immediately covered with foil, The clear, small increments so that bubbling wont get out of hand. The solu- sc irs at room temperature tor 24hrs. tion will start t — beautiful, clear-amber beads of MDA fresbase oil will appear all . ade. The sotution is com- about the solution (most of it settling at the bottom) and the e a lola el lor produosd, ana all el is chemist adds a fitle more base to insure an excess so that al paty e Temperature with no pressure needed. Strike MDA will separate out, This is one of the more pleasant events of al . fala you tés was good. The solution ls now cleaned up a lle and dmug chemistry. the MDA isolated, Now tha chemist need only extract tie MDA oil from the water istilled from the flaskc (his accurs be- with some DCM. Yes, this time the MDA will go into the DCM. The a rmeraarEra! o - merely pours about ADOmLs of DCM into the con. Rvesn Tis . a izo 1 l lrs 4 | for a few minutes while she walches Í ted mixture will polymerize into a tainer and stirs it really well for a fe e a ass. 1h "il go away in the nexi step. TO TV. As much of the water as possible is poured off or separated ia, the concentrate is added o 3N HCI solution which will dis- a.  in a separatory funnel and then the DCM layer ¡s dried through aluminum foil to reduce ketones, Strike thought that it was proba» 100g of sodium sulfate ( see methodology chapter). The DOM is bly a bunch of baloney because thi then removed by simple or vacuum distillation to afford a clear, dimped in the backwash of pS o o lightzamber MDA freebase. This oil is so clean as is that it can be as if merited much consideration, in fact, this proceriye wo, + - SIper 885 jeld ís a li to get rid of the color impurities, but there is so little: contamination But since the catalyst is plain le mo pcs eli and, besides, what little there is will separate out ín the process of prove to be the perfect 'foll' (ha ha!) for those who can't get th erystallizing the product for consumer usage (see Crystallization hands on other high-powered catalysts. Strike did say da ms chapter). method will produce methamphetamines, but the trade-off for - . . o those spolled babies that just have to have this kind of drug is that The yield here is 80-90%, No, that is not bulishit! This method they are going to have to use a watched chemical: the dreaded has not been given the proper credit it deserves and sometimes melhylamine, Its pretty groowy that this book has gone Ia fe has been dismissed without due process. Does Strike sound de- without having to rely on any controlled substances except sor fensive? You bet! Strike has been in the science game for a long Precursors, As one of the most watched chemicals of all mottul. time and knows that bilterness, doubt and contempt abound. But amine is going to have lo be made. In the Chemicals secta ms that's ok, because those who do not use this method simply get this book is an easy methad for makina theta or met hammered by those who do! that is required for this method which is methylamine hyarochlo: ride (CHaNHa.HCI). For those chemists that prefer MDMA or meth, this method can work for them too [27]. Everything about the catalytic reduction remains the same except that instead of using ammonium acetate To as the amine source, one is golng ta use 10009 methylamine hy- drachloride (see the Chemicals section on how to make). The o screwier thing about this procedure is thal someone ¡s going to ñ have-to-babysit-that-stispid-faskfor-24-26-hours-checkingthe-pH every now and then. The reaction has to remain neutral (pH 6-8, MD-P2P MDMA bubba!) the entire time, but that aín't going to happen because the dissociatian products from the methylamine j tum things basic. So someone has lo keep it neLitral by checking the pH with pH paper and adding a couple of drops of straight-from-the-bottle concentrated HCL Aside of the two changes, the reaction, cleanup and yield remain exactly the same. Here's how the chemist proceeds, Next to ettally unemptied ashtray full of cigarette and joint butt: rave fllers and the decomposing cat cronos the budang pi may find her roll of aluminum fol. 50 of the foil is cut Up into tin x in squares and chunked into a big flask or glass sun tea jug. Older methods suggest that those pieces of aluminum foil be washed with some dilute aqueous NaOH, draíned, then washed Ihree more times with fresh dHyO. This is meant to 'clean' the surface of the aluminum before itis amalgamated. This really ist METHOD 42: By far the most popular method currently available. This is a really convenient way to convert P2P or MD-P2P into meth and MDMA (ecstacy'). It is a very clean procedure, akin to laBH¿CN=metnod, USING amalgarmated- aluminum catalyst made from ordinary household foil [26, 28]. When Strike was reading all the underground literature on the Lise of household Elher way, the happy little foil pieces end up lying at the bottom of the flask ready to be turned into a catalyst. To do this the chemist -100- -101-  i Cl) dissolved in jours a solution of 1,3g mercuric chloride (HOCI») d e A o0mL dhs0 and stirring is started. The Hg starts to immediately react wi y y lor wi lowed to continue the solution will start to get really hol. This is al ——— 01-45-30 mil i Jutión will get -30 minutes during which time the stirring sol > cloudy grey with metal particles from the degradation of the alumj- num. t about all of that There are a couple of notes to consider here. Jus pomor dust o amalgamated catalyst, which ís great except that almost all of it will be lost in the next cleanup step. One can make up for the loss of catalyst by increasing the aluminum batch size, but care is necessary in doing this. There is a danger point in making too big a batch of AlHa. Beyond the size of a 1509 otAL, the reacti > le ky! Also, the amount anic steam cloud may erupt. !t can get freal Also St HgCt2 shouid not be increased beyond the ratio given here be- cause ¡tl + ing but dust. -30 minutes the water is decanted from the catalyst leav- Pi anouoh to cover the metal chunks. 1f the catalyst is ax. posed to air it quickly degrades. The aluminum is then washe: times with fresh dHzO decanting each washing so that a little vaz ———— ter remains to cover. In the clean water the catalyst looks to be frosted with grey dust and is now ready for the big reaction. After the last decanting the chemist, in rapid fire succession, dumps * ———_Sollowing ingredients into the flask holding the catalyst in the exact order as follows: (1) 769 methylamine-HIC! in 76mL. dHz0 (2) 230mL isopropyl alcohol o (3) 183 mL 25% aqueous NaOH solution (4) 679 MD-P2P or 50g P2P (5) 440mtisopropyratcohl __—— —Q—————— The flask is placed in a plastic tray because an ¡ce bath may be a e a o that the temperature stays below 50"C and the solution stirs -102- this way for 3 hours. Usually, over 300 no matter what one does, Some folks say necessary. Strike does not think it is. The solution looks very het. erogenous. By this Strike junk is swirling arena in Wo Mook Amber Esad ol PER Ho A by as do Chunks of foil, grey dust, and frosted beads of oil, the temperature never seems to rise Aíter 3 hours the stirrin settle. By this time just which is going to make $ Cult because it will plug chemist lets it settls, thex fitration setup (see met with 100mL methanol, ta cake and the filter cake 9 is stopped and the solution allowed to about all the foil will have tumed to dust, he next step of vacuum fitration very dif Up the filter paper in a second. So the mn pours off the liquid through the vacuum hodology section). The flask is rinsed e methanol poured through tha discarded. All of the filtrate is placed in a 5 melanol, isopropyl alcohol and water which will leave the chemist with ail and ¡ the bottom of the flask The cleanup of this oil ¡s exa Method 1. The oil is dissolve: solution extracted with 100; that in this particular case the HClíwater but th; ing to be ín that DCM so it, of course, is saved. The HCUMDMA. Solution is then basifted with concentrated NaOH so thatat around | pH 9 the happy little beads of final, freebase ll appear in —— fre sotoionAS Usual, Me Ol E envases dr EC dried through Na»SO, and the DCM removed by distillation. The final product here is Usually a little darkes in cotor than ths product Echieved in Method 44, but it is stil remarkably clean and may be Srystallized as is with the crystallization process removing most of the colar impurities. Of course the chemist may wish to vacuum distill to afford clear product. The average yield with this-method——] is 60-70%, clly like that which was done in d in about 800mL of 3N HCI and the mL of DCM. The chemist remembers the MDMA or meth is going to stay in P2P is go- METHOD +3: This ¡s a sim, cept that ammonia is use: ine.HC[ so one can make ¡ple one pot version of Method 43 ex- | d instead of the watched methylam- MDA instead of MDMA [28]. This is - 103 -  A : to do but can be is merely an aluminum sauce pan with enough com oil in it to METHOD 45: This method ls e say A ihie section to equal the height of the liquid in the flask. A thermometer is placed messy. One needs to re: El le nal a a in the flask and another one placed in the oil so that the wirola—— htih A setup looks like figure 11. action and ¡t converts P2Ps into amphetamines or methamphet- —ámines as shown below. This method is very simple to do but has ' . ; icablity to. X Stirring is started and heat is applied so that the oil and reaction—— been grosely misrapored, aspecialy waste O od mix achieve a temperature of about 120*C in about an hours timo. e Sn Cronica Abstracta [8]. This Its at this point that CO, bubbles will begin to emerge signaling the longest for is e one mess) and de yiekdo suck (about that the reaction has begun. Some amount of ammonia will start method Jrs Join lo detal how this mood works, DULa few lo be given off at this point so the apparatus, if not already in a 20%). Strike is A is going to lay down lots of ways that this hood, should be placed in one. Itis from this point that the solu- paragraphs away Strike is going ñ y a production tion will start to turn from its clear yellow color to that of a more method can be better for bath X and speed pr : orangy hue. The temperature of the solution is allowed to slowly o dlimb until it reaches the blistering temperature of 190%. ltig > Í held at this temperature for 5 hours then allowed to cool. What a romano A mo Sm the chemist will have af thi: i jack Fomanido < — l ——————_H£ chemist will have at this point js a thick, goney mass-af bl XX) o SNA tar that has probably gotten so thick from polymerization and o aa sos evaporation that even the magnetic stirbar has been hatted. 239 of MD-P2P or 179 of P2P that was made by any method and When cool, 100mL ether is added to the flask to dissolve al! the 859 formamide (HCONH2) is poured int a small Pyrex flask (sorry, tar and then the black tar/ether is poured into a separatory funnel loss is a no-nD The ethor is washed once with 10ÓmL. dH¿O, the upper ether layer hero) )f one wanted Separated away and the water extracted once with 100mL fresh to make meth or ether. The two baches of etñer are combined and the solvent ——— MDMA then one removed by simple distilation leaving the chemist with a black would use 60g of a mass of oil in the bottom of the flask. Next, the chemist pours——| chemical —— called Bm. of methianal into the ftask, suits to mix the tar wit the MeoH ii y jar three O ora haurs during which time the whole solution becomes black. The ide. However, ino e chemist is using HC] to hydrolyze the formyl intermediate. The chemical. ls ex soluñon is allowed to cool then is basifed wi concentrated tremely watched NacH salution until pH 9 is reached. The chemist won't really because of lts use nesd to check the pH with iitmus paper because, as Usual, dark in this recipe so it is drops af MDA oi! will appear all about the surface of the solution not something as a pleasant indlcation._All that js left is for the chemist to extract il ————__H2 MDA mt etter or DOM and distil away the soluent—How- PA error ever, separating the solvent layer from the water layer is a bit chemist would use, ricky in this case because the two layers are so equally blacktrat———] This flask is placed [Figure 11] it may require a lot of squinting and a flashlight to spot the inter- in an oil bath which 108 -109- face between the two. Neadiess to say, the oil obtained is way to flthy to use and must be vacuum distiled to afford clean yellow (Sy mmm o. A ——_MDA freebase. The distilled freebase is really pure, but to Strike, 0 > == ¡9 o the effort to get this sorry yield is not worth it, especially if this is e HOGONH, Co ae tried in large batch amounts. By largs Strike means an altemplat more naa medico Mormts0A ——— conversion of at least 200g MD-P2P or P2P. II O o, lf one is using formamide or N-methylformamide then one is not If ever there was a reaction that was batch size independent then going to have the advantage of creating formie acid as a break- it has to be this one. A chemist can try to process 200, 500 or down product, so the Idea is to have formis acid already in the re- even 10009 of P2P using this version of Leuckart and never re- action mix. To do this one takes the 659 of formamide and mixes it cover more than 100g no matter how careful she is. This proce- with 309 of 88% fommic acid, places this flask in the oil bath and dure is more in line with those who wish to make steady altaches a simple distillation set up to it as shown in figure 12 /easonable supplies of X and should not be used to process mora Since the formic acid has somo water in itthe chemist is going to than 100g of P2P at a time. In fact, it shoulan't be used to make remove that water by heating the oil b; 17000 and al- Any aru at all. You see that would be ilegal. lowig Me water to distil over with no vacuum. When no more water distills over the chemist allows the reaction flasicto- cool] Strike's mission with this book is to provide as many methods for a adds the 23g of MD-P2P, reattaches that distilation setup and al. ———— Conversion as possible. Slight corrections to a recipe can make a h ise ature to 160-1700. The re- great difference; and to become a truly great chemist one should action stays at this temperature for 5 hours, any longer makes be aware of both the good ways and the bad ways and what it little difference. Also, if the temperature rises above 170% then was that made one recipe a poor one and another a good one, destruction, not production, will occur, The distiliation setup is Then, when a chemist comes across other or future experiments, there to condense any product that happens to exit the reaction she can make a more educated assessment as to its worthiness. flask. This distilate is returned to reaction while things are still This whole Leuckart business is a good example. The Chemical hot. Using formic acid effectively doubles the yield. Abstracts article Nas been around so long and (Is Meris so TeW when there have been so many blatantiy better recipes staring illegal chemists in the face. Not until very recently has some cor- rection bes E hi - interested ín speed manufacture should read this closely. It all relates in every way to the betterment of methamphetamine syn- thesis, The Leuckart reaction was originally conceived using a chemical called ammonium formate (HCOONH¿) which ¡s very Similar to ——— Tormamide (HCONH,) [S0]. lt is pretty much believed that this molecule donates ¡ts ammonium part to the P2P and then the for- mate part turns into formic acid (HCOOH) which then acts to re- intermediate into its stable formy! derivative (don't ask). - 110- 112  are more amenable to production. Whichever way was used, the chemist is going to have a cooled solution of formyl intermediate, and formamide etc. There are a couple of ways to process this stuff from here that are better and more convenient than the origi- [Fig 12] e hat the dudes did in the old days: ammonium formate (25). This way uses 609 of ammeonium formate, no formic acid, and a distillation setup. An- other combination that works equally well is 1:1 formic acid and ammonia in place of formamide. It is also perfectly fine to remove the water under the distillation setup, then replace it with a reflux condenser and conduct the reaction under refiix for the 5 hours [10]. In fact, reñiux is a good way to do any of these Leuckart re- actions. These strategies reduce the amount of tar immensely and keeps the reactants together a lot longer under reaction conditions that -112- matway 122,31]. Instead of washing the reactants with water, extracting the product with ether, removing the ether then hydrolyzing, why couldn't one just hydrolyze right off the bat in the original reaction pot? As itso happens this can be done. The chemist can put 200mL of 30% aqueous NaOH or 200mL 30% HCI right into the flask and reflux for 5 hours. Using NaOH to hydrolyze has two advantages: it is gentler on the methylenedioxy ring structure of the X molecule and itis faster to process. After hydrolysis is over and the solution has cooled all one needs to do is extract with ether to obtain the MDA oil because Using NaOH means that the MDA stays as an cil throughout. A really frugal chemist can do one extra thing to help herself out. She can take that ether/MDA layer and mix it with a few hundred mLs of 3N HCL This, as usual, will cause the MDA to go into the water layer but what ¡s going to be left behind in the ether besides tar is going to be-a lot of unreacted, valuable P2P. The chemist saves that layer to deal with ¡ts P2P payload at an- other time. Meanwhile, all that remains is for the chemist to re- lease the MDA from the water/HC! by basifying and extracting with einer, Of course, there are a couple advantages to using HCI as the hy- MDA or amphetamine ¡s ín the water solution, the chemist can vacuum filter the solution to get rid of all the tar and crap which will give a remarkably clean water solution. The X is released by ba- sifying and extracting with solvent. Since the formamide reaction solution is going to be a lot cleaner than the tarry mess of the original recipe, the chemist has yet an- other option to explore._Instead of hydrolyzing in the reaction pot, the chemist can add 500mL of clean dHz0 and stir just like in the crappy original method except that this time the chemist is going to lock for a heavy oil layer that wil saltle at the bottom. The up- -113-  give much higher yields than the finer powdered magnesium. The bined extracts were dried (K¿COy), filtered and evaporated on 2 purity of the particular Mg used was 99.5%. The last note is that rotatory evaporator." an excess of amine produces max yields. Strike is stopping the quotation here because the chemist is a monium acetate to make MDA or amphetamine, or methylamine has left after evaporation (or distillationj is freebase residue with in methanol for MDMA. But methylamine is optimal because it some contaminants. The chemist can work this up as usual which gives higher yield and less byproducts. Also, if ammonium acetate Would be to do a little more acid/base clean up like has been done is used, one must use either ammonia (NH) or a primary amine with all freebase recipes, Or crystallize the final product for rec- (any of one's choosing, Strike supposes) in place of the triethyla- reational use. The authors contínue by making an oxalate salt out mine in the reaction. of their freebase. One can make whatever salt they want out of an amine freebase. Making an HCI, like what naughty chemists nor- la articles like this one, the scientists don't have the time nor the Mally do, is just one way of doing things. Here ¡s the rest of the space to write out the details and amounts of reactants used for experimental. We're continuing right where the last sentence every single substrate they tried things on. So they pick just a few above ends. af the precursors they tried and use their numbers as an example of how the reaction typically goes. All one does is just substitute The residue was dissolved in MeOn (20 cra") and added slowhy, an equal amount of their favorite phenylacetone for the one in the with stiring, to a solution of anh. Oxalic acid (5.409, S0mmo) ín example while keeping everything else the same. This will not be MeOH. Complete precipilation was effected by adding Et,0 (50 too big of a stretch of the old imagination with the first example con”) to the mixture and cooling it to -20C." below. The example ketone is just phenylbutanone. One little car- bon more than phenylacetone, but a methyl ketone nonetheless They are actually using crystallization to purify the amine from any (don't ask) They react exactly the same. As it so happens this first non-amine contaminants. They later freebased the crystals and example is also the one using ammonium acetate to make MDA. fractional distilled to get pure amphetamine with a yield of 50%. Sweet Wow! That looked pretty good, huh?! The following example is *“1-Melhy!-3-phenyipropylamine-—In a 250 crf, single-necked one of the papers experimental examples of using Methylamine m as the amine source. This allows one to get MDMA or Meth. Th: ACONH, [ammonium acetate] (38.549, 500mmoN), Mg (6.089, authors used methylamine in methanol. That means they are us- 250mmol) and 70% aqueous MeOH (100 cm). The flesk was ing the MeNH, freebase, not MeNHZFHCI. The authors explain capped with a mercury filled bubbjer [feel free to substitute this that they made their methylamine/MeOH solution by dripping one], to reduce escape of NH, and the mixture was stimed at 20- (Strike thinks) aq. 40% methylamine onto solid KOH and bubbling 29C, for 12h, If the reaction was not complete (TLC), additional the liberated MeNH) ¡nto ¡ce cold methanol. One can do this, or ACOH (6.0g, 5.7onP, 100mmol) and Mg (2.439, 100mmol) were buy a gas eyllnder of MeNH, gas which can be bubbled into the added and the stiring continued for an additional 12h. The mix methanol or whatever. ture was poured into water (600 cm) to which NaHCO, (509) was then added: the whole was then internally steam distilled' uni + 1, 9-1 + — . en” of the distillate collected. lt was made alkaline (pH > 12) with glenecked fíask, were combined 1,5-diphenyipentan-3-one (7.159, 50% aq. NaOH and extracted with CH¿Ct? (3 x 50 cm”). The com- 30mmo!) [<-insert said P2P here!], a sofution of MeNH, in MeOH -118- -119- (5.4mol dnf”, 44.5 or, 240mmo1), and Mg (3.289, 1358mmo1). As you are about to see, the standard methods for using the AcOH (14,49, 13.75 ca, 240mmo)) was added with a pipette be- NaBH(OAo)s cataiyst cali for it to be in a dried, powder form. Strike low the surface of the liguid and ihe Mask capped with a mercury- ———Supposes the berzene ln the above reaction can be distilled off to filed bubbler, to reduce escape of MeNH, The mixture was stirred leave dry catalyst. But don't quote Stri " i —— vigorousiy, at 20-28%C, for 12h. a be made ín situ in the DCE solvent of the reaction to come (don't (TLC), additional Mg (0.739, 30mmo), MeNH, sofution (11.1 cn?, the shit! — mol) and AGOR (3-69, 3-4 cm, 60mmol) were added and the stirring continued until completion (3-6h). Work-up afíorded ihe Anyway, with catalyst in hand it is time to proceed with the reduc- moncoxalate salt (6.72g, 65%)," » tive amination [56]. As far as Strike can see, this method will not work well in making MDA. 1£will not use ammonium acetate in the same way as NaBH.CN. So one is stuck with making MDMA or meth using this method. And without further ado, here's your rec- ipe: METHOD X9: This method ¡is not 49" because it is bad. l''s just that it, and 8 above, are still in the experimental stage as far as Underground chemists are concemed. So Strike placed the less tested methods down here $0 as not to confuse people too much “General Notes: (a) The emine [methyiamine] mixed in 1,2-dichloroethane and treated with NABH(OAc), THF, Ct, Or GHSCN may also 56 used as solvents [but a longer re- action time wil be necessary] (b) Acetio acid (1 - 2 mol equiv) may ba used in reactions of ke- tones [the paper says that AcOH acts as an accelerator to Speed up the reaction with the P2P. But without it, the reaction will still go to completion. It will just take longer to do.] (c) Reactions are normaliy cart i But this method has been generating more rabid attention than any other in the underground. Feck sent Strike some articles on il. in il e same references [56, 57]. Everyone ¡s talking about it. And for good reason. lt is essentially the second generation of reductive amination using superclean, gentls catalysts, Just think of it as Method +4 - except that the NaBHsCN has been replaced by a more workable catalyst: So- dium Triacetoxyborohydride [NaBH(OAc)a]. ——— Thís catalyst works in a similar manr 3 methylamine freebase. One can saturate the reaction solvent with does not suffer from the same potential toxicity that NaBH.CN Y il L r to achieve this]: however, the does. Tfis also diferentin That one can synthesize the damn stuff amino salt [ MeNH¿HOI ] may be used. /n this case. 1d equi ar —— rather easily in one's own garage, as appasad to NaBH,CN which — EtN [triethylamine] ¡s added (0 Tha reaction madero TRE EN will require a very complicated and dangerous cyanide generation must be removed from besified product prior to salt formation." apparatus as is shown in the Chemicals section af this book. The following ís about all Strike has on the making of the catalyst NaBH(OAc), [55] And here's the two representative methods one would use. Just imagine the carbonyi precursor as a P2P and the amine as meth- . . famine. Visualize....man! *Treating a benzene suspension of sodium borohydrida (4 equiv.) y . iva And reftuxing the mixtura for “Method | This procedure is used for most ketone reactions. A 15 min under nitrogen, afler ihe intial rapid gas evolution sub- Method !. This p or most ke! » representative example is tha FE sided (oa. 3 mojof Fiz liberatec) [No Smokingi] gave a ciear sol pone [2P] with hexamethyleneimino [MONH,]:. Hexamothyr tion ofNaBHÍOA* ), TOMO) and cyiclopentanone (0.849, 10mimol) were Mixed in 1,2-dichloroethane (35mL) and then treated with -120- -121- sodium trlacetoxyborohydride (3.09, 14mmol) and AcOH (0.89, 10mmol). The mixtura was stired a room temperature for under a horofor24h until th lante were consumed as de. termined by GC analysis. The reaction mixture was quenched by adding TN NaOH and the product was extracted with efher. The ether extracl was washed with brine [NaCI solution]_and dried (MGSO). The solvent was evaporated to give Ihe crude freebase (1.69, 96%). Method ll. The above procedure is followed without the addition of glacial acetic acid. The reaction mixfure remains cloudy throughout the reaction. This procedure is more appropriate with most aldehydes and unhindered aliohatic ketones [which P2Ps happen to be], A representative example is the reductive amina- nor yriaina piperidinecarboxytate [MeNH]: * Ethy!_ 2-piperidinecarboxylate (1-579, 10mmo) and 4 pyridinecarboxaldenyde (1.079, T0mma) 1,2 dichiorelhane_(35mL) and then_treated_with sodium oo Doraivid (3.09, 14mmal). The mixture was stirred at room temperature under Na atmosphere for 24-30 h. The reaction mixture was quenched by adding aqueous saturated Na- HCO», and the product was extracted with EtOAc [ethyl acetate] The EtOAc extract was dried (MGSO,), and the solvent was evaporated to give the crude freebase (2.49, 96.7%)" Both those methods look pretty equal to Strike. Still, Strike tends to think that the Method | looks like ¡l's 1he best of the two. There are some definite advantages that this method has over the NaBH3CN one. But all in all, they look about even to Strike. If's great to have options though. sn't it?! METHOD +10: You girls need to know that Strike is not just listing every method that produces a precursor or makes a final product. There are hundreds out there. Many make the product bul are too both. There are special criteria that makes a melhod worthy of in- clusion in this book. Often, a method has been reviewed by many person that has actually tried a particular method on our special -122- precursors, then that method had better have a lot of merit and unique potential. This really crazy looking method is one of them. There are a lot of the article: Rajender S. Varma. You will see ín the Nitropropene section of this book (and in references from many other parts of the book) that this guy has been making a lot of strangely applica- ble advances in catalysis, amination, and reduction of ampheta- mines and related compounds. lt is uncanny how often Strike has come across this person's work. lts like he ís the Shulgin of basic precursor and amphetamine progress. Go figure! The other attraction is the method itself: clay, a Sears microwave oven and the most lightning-quick results ever imagined! Some- one sent Strike this method vía fax, but dumbass Strike did not get Anyway, there have been two very hot topics in chemistry lately: clay € microwaves. Both have been shown to do remarkable things ín preparative organic chemistry. And this article Strike has [58], has combined both to produce some stunning reductive ami- nations of ketones to final amine products. The procedure in- volves mixing naked ketone, the amine, some clay and some ple of minutes. That's it. The general procedure is as follows: “Iypical Procedure The synthesis of Nphenyp- chlorobenzylamine is representalve of the general procedure em- ployed. A midure of p-chlorobenzaldehyde (0.7, Smmol), antine (0.4559, Smmo)) and montmorilonite K10 clay (0.19) contained in a 25mL beaker was placed in an alumina bath inside the micro- wave oven and irradiated for two min, The in situ generated Schiff's base was mixed thoroughly with freshiy prepared NaBHy- clay (5.0mo! of NaBHs on 1.72g of reagent) and water (1mL). The reaction mixture was again irradiated for 30 sec (65"C). Upon extracted into melhylene chloride (3x18mL), The removal of sol- vent under reduced pressure provided pure N-phenypr -123-  a e E SA, CANO JH LION Ls NO, ! LAA “Az e Ao Piperonal MD-Pheenyi-beta-Nitropropene OL CHNOZOMLQOONA, NO, 2 CHO Benzaldehyde Phenyl-beta-Nitropropene Both piperonal and benzaldehyde are List | controlled substances just as safrole and isosafrole are, but the speed maker has the advantage here because benzaldehyde makes up over 95% of the quasi-legal bitter almond oíl whereas there ís no natural source of piperonal. Piperonal, also knawn as Heliotropin, can be made from sassafras oil. lt is also a very important chemical in the fra- grance industry. But there are so many ways ta make both it and benzaldehyde in the Build from Scratch section of this book that the Knoevenagel synihesis has a potential for resurection from s pu av strike means that et only are the precursors controlled bat so Ís the main processing chemical: nitroethane. This. substance does across some ¡n daily life (yeah, right) or Y aho stuf can bo made as described in the Chemicals section. In fact, we have quite a few more recipes for making nitroethane than before! This procedure has been performed in a variety of ways [28 p714, 38-42] with variations in Solvent, base and time of reaction. For piperanal conversion, the consensus is toward the use of acetic acid as the solvent, ammonium acetate as the base and 4 hours of reflux time. Dr. Alexander Shulgin, a giant in this field, prefers the use of cyclonexylamine as the base. Strike would not tend to doubt this man's choice, especially since Strike is also getting the - 128 - feeling that ammonium acetate ¡s heading towards the schedule | graveyard. In a Hlask the chemist mixes 50g piperonal into 200mL glacial ace- tic-acid, then -adds-45mi_nitrocthane-and-17g) dot The solution is then rosas 4 hours and takes on the color of yellow to yellow-orange. After 4 hours and cooling, yellowish crystals of f-nitropropene will spontaneously form. If not, the so- Iution can be diluted with S0m! of dH¿O and chilled in an ice bath for an hour to form the crystals with some slushy glacial acetic acid and water intermixed. “The mass of crystals is broken up and plopped into a Buchner funnel to be vacuum fikered. The filter cake is washed with a litle extra acetic acid or water. All of the filtrate is saved. These f-nittopropene crystals the chemist_now has can be alrdried and used asis, but thats not advisable. What ihey need is a little more cleaning up, and one does this by performing re- crystallization. To do this the chemist is going to use a solvent that everything in the reaction that the crystals came from ¡s soluble in but that the crystals are not. Get it? No? Well, to demonstrate, the chemist will boil 200m!. of methanol in a beaker and start knockIng chunks of the impure f-nitropropene filter cake into the hal solvent. ¡Fall ol the crystal vil not ássoivei in the 200mL of soon as all the crystals are added and have dissalved, then the chemist turns off he heat and chills the mixtura to 0-5%C. Mat is remain *dissolved in the now cold mnethanal, but all ot the f-nitropropene crystals will 'recrystalliza' when cold. This solution is now vacuum fíiltered and the now clean crystal filter cake ¡js washed with a little bit of extra, cold methanol just to make sure. That extra methanol washing and the filtrate can be reduced in volume by distillation and chilled to retieve a second crop of B-nitropropene crystals (total conversion is around 70%). The final thing to add [s that the chemist has a choice of recrystallization solvents other than methanol. These include hexane, isopropyl alcohol and ethanol. -129 -  You know how just a couple of paragraphs ago where the chemist first filtered the crude crystals from the chilled reaction mixture, then washed them with water or acetic acid? Well all that liquid filtrate has a lot of valuable, unreacted piperonal or benzaldehyde 500mí dH¿O and extracts it with DCM. The DOM is washed with 100mL 5% NaOH solution then vacuum distiled to give a dark oll which is unreacted aldehyde. Heyl That's a lot of good material that can be put through the process again. There are some slight alternatives to this process that, for educa- tional reasons only, Strike is going to lay out for you now. (1) it has been shown that by doubling the amount of nitroethane respective to that of the aldehyde in a ratía of 2 to 1, then the amount of ammonium acetate used can be reduced considerably (2) The cooled reaction mixure can be induced to crystallze lis B-ntropropene paylaad by simply dumping the whole thing in a large volume of ice water [40]. (3) Once the reaction mix has cooled after reflux, S00mL of room temperature dHz0 can be added and the whole solution extracted with DCM. The DCM layer is separated and the salvent removed by distillation to give the A-nitropropene as an oil of all things. crystalline form was [38], (4) Russian articles make some outrageous claims and this one is no different (43,_These mothers claim that piperonal or benzal- dehyde will react with nitroethane by sitting in the dark ai 10"C. with only a couple of drops of efhylenediamine. Almost 100% yield no less! Strike has never tried this nor does Strike fall for Russian science, but if anyone is interested. Once one has the B-Nitroprapene, there are two ways one can — progress. One can take the P-nitroprapene and convert il into final, pleasure-inducing product. Which you can read about ín the next y mí pr iS tum them into P2Ps. The chemist has to do something with the stuff because ¡fit sits around too long if's going ta degrade. This - 130- procedure is really easy and has high yieids [28 p734-735]. 32g elemental (electrolytic) iron (Fe) and 140mL glacial acetic acid are it eaker To arouni or, Ín more vague terms, to the temperature that is as hot as possible without the formation of white precipitates. One might want to do a couple of ture is slowly dripped a solution of 10g MD-nitropropene (that's the P-nitropropane made from piperonal) and 75mL glacial acetic acid. The dripping is adjusted so that the reaction dues not become too violent or foamy. The coior of the reaction will progress from or- ange to a deep red with the formation of white salt precipitates. Atter addition the solution ís heated for an additional 1.5 hours at 70"C "during which time the body of the reaction mixture be- come(s) quite white wit de il clímbing the sides of ne beaker"[28, thanks Dr. Shulgin]. When cool, the reaction mix is added to 2L of dH,O, extracted 2 times with 100mL DCM and the DOM extract washed with 1N NaOH otution. —Ths DOM Tayer Ts vacuum distilled to give —8g of pale yellow MD-P2P, Strike must say that that was a pretty easy one- pot procedure using 2-3 simple chemicals with an 80-90% yield. METHOD 42: This may work on safrole but Strike has never tried it on the molecule. This should make good use of isosafrole and its cis isomer [44]. 769 silver nitrate (AgNO,) and 2549 iodine (find this at some phamacies) are stirred in 600mL ether for 30 gentle breeze of nitrogen from a baby nitrogen tank is blown into the alr space af ihe flask. The nitrogen displaces almospheric oxygen from the flask so that it won't mess with the reaction mix. The solution is stirred at room temperature for 4 hours, vacuum filered, washed with a solution of dilule NaHSO) then washed with saturated sodium chioride solution. The ether is separated, dried through Na¿SO, and removed by simple distillation to afford a dark oil residue which is an iedo-nitro ¡ l Now, Strike could be wrong (and often is) but the way this article Teads gives Strike the distinct impression: that the conversion of this intermediate to the final f-nitropropene can occur in two dif- - led way Is to a mt elher an: mi pyridine to all of the intermediate oil sitting by itself in the fask and -131-  stir it at room temperature for 2 hours. The nitrogen in pyridine plucks the ¡odine of af the intermediate causing an elimination (dan't ask). The solution |s extracted with a large volume of pen- tane and water. The pentane layer is washed repeatedly with Tresh dA¿0, dned rough Na¿SO, and Vacuum distiled lo give There ís an incredible amount of energy in the carbon-nitro bond. has four! Starting to get the picture? product at +50% yield. The other way this may be done is listed a Tetranitromethane was used as a double bond detector and for couple of paragraphs up in the article in the section titled 'Prepa- the detection of tyrosine in protein sequences. As you can guess, ration of 3-Nitro-2-cholestene'_ To the intermediate oil is added Isosafrole's double bond is the point of attack. The problem [s that 119 silver oxide powder and 500mL methanol and then refluxed there is not any accessible chemical company today that makes for 4 hours. After cooling, the solution is vacuum filtered and the this compound anymore, So the rave rat is going to have to make methanol removed by distillation to give product (99%?). There is K herself, and tial's where the trouble begins. The best method also an interesting, simple zinc reduction of the nítro product to for making tetranitromethane is in Organic Synthesis [48] using ketone. — Could this be another way to make P2PSs from fuming nitric acid and acetic antiydride. All the glassware ¡is 8-nitropropenes instead of using Fe that is detailed in Method 141? cleaned with soap and hot water, rinsed Eleusis seemed to think so when asked. So here is the experi- y ñ with acetona then rinsed once more with amount of $-Nitropropene in place of the '3-Nitro-2-onolestene' distilled water. The glassware ls placed o > sido d hostal and P2P as the product: and baked at 425%F for 1 hour. Baking “Reduction of 3-Nitro-2-cholestene . - Zinc dust (800mg) was destroys any remaining organics which added in portions during 1 hr to a stirred warm (40"C) suspension can set off the tetranitromethane to ex- of 250 mg of 3-nitro-2-cholestene in 15mL of acetic acid and 0.5 plode. This glassware washing proce- mt of water. Añer 4 hr refiux, this míxture was Mitered hot and the dure, by tho way, is the preferred way to zinc washed well witih hot HOAc. Addition of water and extraction wash up all of one's glaseware after a long day's experimenting. It is the same procedure used by ali the organics labs METHOD $3:(45-47]-Do not try this method! Strike repeats, do that Strike has been fired from, with ether gave 116mg of product" The apparatus to Use ¡s seen in figure 13 which consists of a burette, thermome- ter, Erlenmeyer flask and a two-holed rubber stopper that has a small V-shaped wedge cut out of one side of the rubber stopper to allow the inside antents to vent 31.59 of orangy-red fuming nitric acid (see chemicals sec- o t pop - and reported in some of the underground literature [8) which uses the most dangerous compound in drug conversion chemistry that Strike is aware of: tetranittomethane. The reason this method keeps hanging around is because one can get clean, hyper ylelds of £-nitropropenes in less than 5 minutes, But the ultimate method can exact the ultimate price (death, bubbal). Rave rats are very tion) is poured into ins Erlenmeyer flask lts bber-stopp ti to buraette Z and thermometer is placed on to the TFiaure 131 to try this, no matter how much they are told not to, then Strike will at least lay down the proper way it ís accomplished. -132- -133-  METHOD 241: (155, 28 p715]Using the setup in fig. 9, the chemist stirs 559 of LiAlHs in 200mL THF and adds dropwise to this a METHOD 42: "Synthesis of Alkvlamines. General Procedures, mixure of 50g f-nitropropene and 100mL THF from the separa- Method (A). The synthesis of f-phenethylamine is representative. tory funnel, Añer addition the solution is refluxed for 24 hours A flame dried, nitrogen-fushed, 100 mi de ——— ig whctr time tere vi bs Tho Tommasón ar a Tot ofalife alos Sopla RL, magnet stiring Dar na af a as minum salt precipitates and the solution will also start to darken. caoled to 0*C. A BHyTHF solution (16 mmol, 9.5 mt of 1.7 M) was The solution ís cooled, 50mL dH,O is added, and the solution ¡s injected into the reaction Mask via a syainge, followed by the slow vacuum-filtered. The chemist washes the filter cake with a little addition of a solution of f-nitrostyrene in THF (4 mmol, 0.6g ín 6 extra THF and discards the filter cake. The filtrate is placed in a mi THF). Alter the addition, the ice-bath was removed and a cate- distillation setup, the THF removed under vacuum and, if desired, Íytic amount (-40 mg) of NaBH, was added to the stirred reaction the dark MDA/amphetamine oil in the bottom can be distilled over mixture by means of a spatula. A moderately exofhermic reaction as well to give clear yellow freebase. _An alternative cleanup ensued. The reaction was then allowed to proceed for 6 days at would be to forget about removing the THF and instead adding the 250 . The reaction mixture was poured on to ice-water mixture solution to 200mL 0.8M H2S0,, extracting it with DCM then re- (50 mi), acidified with 10% HCI (-20 mf) and then stirred at 60- moving the DCM to get the freebase. Reduction using LiAlH, gives 85*C for 2 h, After cooting to room temperature, the acidic layer ylelds from 60-80%, hod—uith—ether (2:50 mi) ami then TRE phenyletaylamine was liberated via the addition of aqueous so- The following methods are all the result of one group of scientists: diurn hydroxide, Solid NaCf was added and the product extracted Rajender S. Varma, Laila H. M. Guindi and George W. Kabalka into ether (3x80 mb. The combined efhereal extracts were dried stal. They produced a series of papers in the 1980's that blew the over anhydrous MgSO, and the solvent removed under reduced fuck out of nitro compound science, Their methods for reducing f- pressure to yleld 0.43 g (88%) of B-phenylethylamine.” Nitropropenes are novel and easy. And the best part is that they almost always used our exact precursor (Phenyl-$-nitropropene) The authors say that the 8 day reaction time at room temp can be as an experimental example. So there ain't gonna he no guessin isi loz as to whether their methods are applicable to our precursors, did not specify how much heat or how much time would be re- They are! duced. om STRE'S Gn, our ETHOD 33: The authors next stepped back and considered the good friend and learned scholar Osmium emalled Strike some of cosmic Imbalance caused by that G-day reaction time. The next the above group's articles and quite a few more that we will get at recipe was what they came up with. in just a bit. The following methods can be read about in the origl- hal articles in which they were published [49-51]. But there ls a “Synthesis of Alkylamines. General Procedures, Method (A), The nice revlew by the same authors in which a representative exam- synthesis of Bphenethylamine is representative. A flame dried, ple of each of their methods is Included [52]. The following were nitrogen-flushea, 100 mi fiask, equipped with a septum inlet, mag- taken from that review. X and speed chemists just substitute an netic stirring bar and reflux condenser was cooled to 0*C. Sodium S , am o S > Ea equimolar amountof their re: apa eto borohydridef8- ol 0-36 placed imine task tolowed by the methods below, Also, it should be obvious that these reduction sequential addition of THE (13-15 mi) and BFy-Et20 (12 mmol, 1.5 methods will work just fine on 2CB and other phenethylamine in- ími) at 0"C, After the addition, the ice bath was removed and the termediates. contents were stirred at room temperature for 15 min, The sotution - 138 - -139-  of gnitrostyrene in THF (2 mmol, 0.39 in 5 mi THE) was then in- jected dropwise into the reaction ask via a syringe and the reac- tion míxture refluxed on an oil bath for 8.5 h. After cooling to room temperature, the reaction was quenched hy careful addition of water (25 mi), the midure acidified (1N HCI, 25 mi), and then heated at 80-85 (oil bath) for 2 h. After cooling to room tem- perature, the product was isolated (75%) as described in method A [from above, folks].” METHOD +4: The last one from this review [52]. The authors tound that reduction occurred using some spacey sounding cata- lyst called lithium tristiyiborohydride. But something interesting occurred in the process. The catalyst reduced the nitro group and all to give only a small amount of the predicted amphetamine. But it also stuck one its ethyls on the nitrogen to give a majority prod- +of_N-elhylamphetaminol ne mr 'H¿CH, o no im O o o == MD-Phenyi-beta-Nitropropene MDEA ñ tie way 0n8 can ge ever lovely MDEA (Methylenedioxyethyl amphetamine, the softer cousin of X). Strike hears you asking “So if one uses líhium tri- group?". Good question. Unfortunately the answer is no. The authors say "Interestingly, N-alkylated products were not produced when other alkylborohydrides were used” Fair enough. Here's the recipe: “Reduction of Nitroalkene with Lithium Triethyiborohydride (Su- perhydride) and borane. General Procedure, The reduction of f- P perhydride (LIESBH) and borane (BHy) is representative. Into a flame dried, nitrogen-Hushed, 100 mi flask, equipped with a sep- tum inlet, magnetic stirring bar and reflux condenser was added a sotution of LIEtBH (10.5 mmol,, 10.5 mi) via a syringo, followed -140- by the addition of a solution of -methyt- f-nitrostyrene (7mmol, 1.4 g in 5 mi of THF). Alter the addition, the reaction midure was stirred at room temperature for 1h. Excess BH9THF (23 mmol, 28 mi) was then added and heated at 60-700 for 15 h. The mixturo p into-ice-weter-end-acidiiedtopH-2—THE TMROrS WAS stirred and heafed at 60-65'C for 2 h and then cooled to room temperature. The acidie water layer was washed with ether (3x30 mi) to remove N-hydroxylamphetamine. The pH was then adjusted to 10 and the product extracted into ether (3x30 mi) and dried [MGSO¿). The solvent was removed under reduced pressure to yield 0.73 g (54%) of N-ethylamphetamine. The hydrochioride salt was prepared and recrystallized from an ethedethano! (20:1) mixture.” METHOD 45: Contributed by Osmium [53]. The paper reads (at least to Strike) that thís reduction method can work to reduce the TormyT Intermediate made in the Leuckart reaction directiy into MDVA insiead of needing to hydrolyze to MDA with HCI (dot ask). For this reaction one substitutes an equimolar amount of f- Nitropropene for the 3,4-dimethoxybenzyicyanide in the repre- sentative experimental below: “NaBH, (4.569, 120mmo0!) was added to a solution of Me3SiC! (26.049, 240mmob) in THE (100mL) and the míxture refiuxed for dimethoxybenzylcyanide (109, 56.4mmol) ín THE (SOmL) was then added over the course of 1Omin. The Solution was refluxod 7 díher 10h. After eooling_10 H were cautious added and the volatiles removed in vacuo. The residue was taken up in dilute HCI and washed with other. The aquenus solution was treated with excess dilute NaOH and then repeatediy extracted CHClz. The organic extracts were combined, dried over NaySOs, and the solvent evaporated to afford 2(3,4 dimethoxyphenyhethylamine, Yield = 9.18g (909).* The authors caution that *MeSiH ¡s formed. lt should therefore be -) can escape from the reaction vessel” -141 -  BROMOSAFROLE 8 PHENYLISOPROPYLBROMIDE —— The third, and last, mejor category of X precursor is the halogen species. In the world of chemistry, scientists look to add things or changa things with a molecule by exploiting 'functional groups. So far we have been exploring the possibilities of the kelone func- tional group (P2P) and the nitro group (8-Nitropropená). And al- though there are lots of different things that can be considered functional groups, the only one left that really has any broad utility for the underground chemist is the halogen called Bromine. When ——— One introduces a bromine into that magic beta carbon of safrole or allylbenzene (or however one can arrive at that point) one will get — re ———Bromosafrole is a great stepping stone to final product and was, in to synthesize MDMA. Until very recently it was the defacto method that most underground chemists started out with (Someone-WWho- Is-Not-Strike included) because, at first glance, ¡t seems so simple and uses basic chemicals and equipment. Once someone has the bromosafrole, all one has to do is just swap out that Br with sim- ple ammonia or methylamine and the dead is done. But one has to get the bromine on the satrole in the first place, right? And that has proven more difficut than most people thought. Not because it is procedurally difficult, but because peo- ple have been misinformed on the subject for a long time. -142- The basic premise for making bromosafrole has been to mix sa- That' . The HBr does what is called a Markovnikov addition re- action whereby the HBr sees the allyl double band of safrole and —— preferentially attaches ¡ts hydrogen to the gamma carbon and ite bromine to the middle beta carbon (dont ask). Mm 17 o. a Br SS Safrole Bromosafrale But the key to success is getting the right form of HBr for the reac- ous 70% HBr as the reagent (this abstract is essentially a rewrite of Merck's original patent) [59]. The following is the write up: “Safrole (5.39) added dropwise at 0”C to 21g. 70%HBr, the mixt. left 14 hrs. at 0”C, poured on ice, exta. with Et¿0, and the ext. Dis- tilled in vacuo yielded 97% 3,4-CH+0,CsH,CH2CHBrMe.” % si y Certainly no place that Strike is aware of. lt does not exist in other words. Nor does Strike know how any of these folks were able to make a supersaturated aqueous solution of HBr. A! commercially available hydrobromic acid solutions are 48% HBr which happens to be the constant boiling poínt percent for that species in water (please don't ask). Some people think that 48% aq, HBr is good enough and, until recently, some underground chemistry texts agreed, But it Ís not The 43% is only strong enough to promote what is called acid calalyzed hyarallon (dom ask) when ¡ne medium is n ls water free radicals. The final mixture gets 500-1000m! of water added. The crude bromosafrole which settles to the bottom ís seporated without adding any organic solvent. If yow cool it ft gets pretty sticky and syrupy so the water layer can be just poured off" One need net inhibit o, to make HI which is even better than Her in any of these recipes. lodine adds much better and swaps out with the amínes much better. Yield are much higher! The other thing to notice is that re- action carries itself out in DMSO. Seems logica! to believe that one could bubble their HBr gasses into this solvent instead of acetic acid. METHOD +3: This is Totrealiy a method. itHismors-obhamides———— Strice and others ho been foying with. Elgusis had been sup. porting the idea thal one could make use of the common 48% aq HBr if one employed t that the water was competing with the Br in the normal 48% solu- tíon. But the literature demonstrates that in conditions such as this, a competing acid can strip away the water (dehydrate) from the beta carbon allowing the Br a second chance to pop In. this modification to his recipe by promoting the idea thal bubbling HCI gas into the safrole/48% ag HBr reac- tion mix one can affe: to occur. Strike does not know ¡f that actually works. Could be, But what Strike and Eleusis draw on are the examples given by Vogel [87 p277). When Vogel wants to brominate something using regular old 48% ag. HBr, he has sulfuric acid already present in the pot. The fol- lowing is a representative recipe from his book, Just read it. Strike does not expect you e plain Strike's interpretation aftenwards. dioxide (from a siphon of íhe fiquified gas) ínto the bromine layer “1,35. Sec-Buty! Bromide (HA-H,SD, Method) - 148 - To 2509. of 48 per cent. hydrobramic acid contained in a 500ml. round-boftomed fask add 75g. (41 ml.) of concentrated sulphuric acid in portions with shaking (1); some hydrogen bromide may be alcohol, followed by 09. (32.5m1.) of concentrated sulphunc acid in several portions with shaking, and finally a few chips of b. condensor to the flask and reflux the mixture gentty on a wire gauze for 2-3 hours; during this period the formation of sec-buty! bromide ís almost complete and a layer separates above the acid. Íf the preparation is carmed out in the open laboratory, fit an ab- somption device (compare Fig. 11,13,8 and Fig.1t 28,1) to the top of the condenser í order to absorb any hydrogen bromide and sulfur dioxide which may have evolved. Allow the contents of the fask to cool, remove the condonsor and set it connect the condenser to the Ñask by means of a wide (7-8mm. ixture until no moro olly drops of sec-bufy! bromide to pass over (30-40 minutes). Transfer the distillate to a separatory funnel and remove the halide which forms the lower layer. Wash ít succossively with water, an equal volume of concentrated hydrochloric acid (2), water, $ per cent. sodium bicarbonate or sodium carbonate solution, and water. Separate the water as completely as possible and dry with 2-39. of anhydrous calcium chioride or anhydrous magnesium sulphate; fithi the bromide for at least 30 minutes and shaken occasionalfy. Filter the dried product through a small funnel supporting a cotton wool plug into a 200m1. distiling flask, add a few chips of porous porcelain and distil either from an air bath (Fig.11,5,3) or on an asbestos-centered wire gauzo. Collect the portion bolling at 100-1030. The yield is 1559. Notes, (1) the acid mixture may be prepared (compare Section 11,49,1) by placing 1209. (37.5m1) of bre ice in a 500mi, fiask, cooling the fatter in ice, and passing sulphur at such a rate that the gas is complef shaken occasionally, and the fiow of gas is. stopped immediately the red colour due to free bromine has disappeared; the mixture - 149 -  will then have a yellow colour. The resulting mixture is equivalent to 2509. of 48 per cent, hydrobromic acid to which 75g. of con- centrated sulphune acid have been added; it need not be distilled for preparation of sec-butyl bromide. Owing to the comparalively negligible difference in the cost of bromine and the equivalent quantity of constant bolling poínt hy- drobromic acid, there is lítle to be gained--apart from the instnic- tionel valuo— in preparing the hydrobromic acid from bromine in the preparation of alkyl bromides. CAUTION. Bromine must be handied with great care and in the fume cupboard, The liquid produces painful burns and the vapour is unpleasant. Bromine bums should be treated immediately with a liberal quantity of glycerine. If the vapour is inhaled, relief may be obtained by soaking handkerchief in alcohol holding it near the nose. (2) The cruda bromide contains a little unchanged alcohol and is said to contain some n-buly! ether (b.p. 141%). The former is re- moved by washing the concentrated hydrochloric acid and this puntication process is satistactory for most purposes. Both the al cohot and the ether are removed by washing with 11-12mi. of concentrated sulphuric acid: the butyl bromide is not affected by ¿his reagent" You see that substrate they were using: “sec-butyl alcohol"? Well to Strike that looks just like MD-P2PoL: Te OH MID-Pheny!-2-Propanol And in the recipe above, Vogel want's to get rid of a secondary alcohol just like the one on MD-F2Pol and replace it with a bro- mine. "Wait a minute!” you may say, “That isn't a double bond like - 150 - sefrole he is starting with. lt is an OH alcohol", That's trus. But in this instance it does not make a difference. We know that at 48% aq concentration an OH is going to end up on the beta carbon anyway, So starting with an alcohol will make no difference, The clíncher is he presence of the H,SO,. It is there not only to strip off the existing OH, but to keep it off so that bromination becomes dominant So if one were to replace sec-butyl alcohol in the recipe above with an equimolar amount of safrole in the above reaction, Strike will wager that a positive brominatíon experience will occur. And all this using the very common 48% aq. HBr! The only differance being that once the reaction mix had cooled, one should do either of two things: (1) distil as described except the bromosafrale will be the last thing to come over (not the first), or (2) food the reao- tion mix with water to bring th: productoutebselut ¿Eb hit it can be physically separated by decanting or sep funnel or some such shit. Anyway, this ¡s just an idea. But ín case one feels inclined to use it or make HBr gas from 48% aq. HBr, Strike has provided quite a Tew recipes for the manufacture of the 48% in the Chemicals sec- tion. -151-  AMPHETAMINES €: METHAMPHETAMINES ROM BROMOSAFROLE 8 PHENYLISOPROPYLBROMIDE With broma or iodo compound in hand it is time to quit and turn one's self over to the proper authorities. Wait! There are a tew who would continue. Most likely in the following manner. METHOD $1: The bromine on the safrole or allyibenzene is in what is called a secondary position. To chemists this means that if one were to try and screw around with that bromine where it is and replace it with something like ammonia (which would give MODA right off the bat) then more bad things than good would oc- cur. Ammonia is a so-so nucleophile and if it tries to muscle the bromine from its spot then the most likely thing that would happen is that an elimination reaction will occur and the double bond will reform (giving safrole and ¡sosafrole as products) or unwanted in- appropriate additions may occur (please don't ask). As it so hap- pens, an azide (Ns) is as good a nucleophle as bromine and will position quí e to be on the safrole or allyibenzene moleculo is certainly a step in the right direction even though it happens to have a couple of ex- tra nitrogens attached to-il_This is-nolgolag-to-ba-too-big-an-ob- stade as yOu will see. fe Tue ó o su oa ca NH, Bromosafrole Safrole-Azide MDA The best azide to use these days is sodium azide (NaN). itís in- expensive and umwatched. All azides have the potential to ex- plode Upon degradation and are toxic to breathe. The methods -152- given here are designed to insure that this will not occur. Even handled carelessly the potential for harm ¡s not as dire as it may seem. Nevertheless, these procedures should be done in the hood and, if possible, performed behind a clear pane of acrylic Relax. Trust in the science and read the articles provided [62-67], The setup used is the one pictured in fig. 9 except there is no ice bath tray. In the reaction flask is stirred a solution of 30g NaN; in 400mL ethanol (Everciear is perfectly ok) or propanol (chemist's cholce) and BOmL dH,O. 1209 of bromo-safrole or 80g bromo-allylbenzene ¡s dripped into the solution from the separa- tory funnel aver a period of 20 minutes. After addition the ther- mometer and separatory funnel are removed, a condenser is attached and the solution slowly brought to reflux over an hours time. The solution is refluxed tor 24 hours, cooled, 100mL ether is hation-stowiy-poured-into-+900mi-ofdHz The upper ether layer is separated, the bottom water layer ex- tracted once with 100mL more ether and the two ether fractions combined and dried through Na¿SOy. The chemist now vacuum distills the ether/azide fraction to get what is now satrole-azide (yield=50%) A much greater yield can be had if the chemist uses carbitol as a solvent instead anol [62] Carbitol ¡s a realh solvent and should not be breathed or placed on one's skin. The reaction proceeds exactly as before except that after 24 hours of reflux and cooling the mixture ¡s slowly poured into 1500mL ¡ce cold 4H20. The upper solvent layers separated and Ihs aquecus layer extracted with 200mL ether which is then combined with that upper solvent layer, The combined solvent portions are vacuum distilled to afford safrole-azide (or phenylisopropytazide for am- phetamine) with the yield rising to 70%. A newer and equally effective way of swapping azides with halides (bromines or iodines) is in e use of phase transfer catalysts [68] Strike ldnt expect d-chemistio-purchase_th exotic catalyst Aliquat 336 nic the investigators in this reference Used to get yields approaching 100% but an alternative catalyst of - 153 -  When whichever reaciion is complete, the excess ammonia and alcohol is distilled off. The exhaust coming from the vacuum or distillation apparatus must be channeled to the out of doors ar bubbled ínto a container of NaOH solution because all that am- METHAMPHETAMINES FROM AMPHETAMINES mona discharge wilbezome devastating. The remarning liquid is acidified with 500ml 10% HCI solution and extracted with 100mL ether. By now you readers realize that the MDA product will re- main in that acid water and extracting with ethár will remove valu- able unreacted safrole, isosafrole and bromo compound. The ether is separated and the water layer, which is normally brownish gray at this point, is basified with concentrated NaOH solution and then. will appear dark brown droplets of you-know-what. You-know-what is extracted from the solution with ether or some other solvent, dried through Naz50, and removed of solvent by distillation to afford you-know-what. Right about now the chemist is probably screaming, "Hey, where the hell is my big yield of you-knowwhat?!". Sorry, Charlie. This way of aminating is easy but chemically i's a crap shoot with yields anywhere from 10-50%. The theoretical odds are against the reaction but ¡ft is done as outlined here, the chances of suc- cess are better. Actually, Strike thinks the yields could be higher because half the problem was probably caused by low bromosa- frole yield which we have hopefully corrected in the preceding METHOD 41: [26]-- 89 of perfectly fine, shauldr't-be-messed with MDA or benzedrine freebase is mixed with 100mL methyiformate In a small pipe bomb. The sealed bomb is placed In bolling water or a 100% oven for 12 hours, cooled and the solvant removed by distillation to give approximately 84 of N-formyl intermediate. Yes, thats the same kind of intermediate that one gets from the Leuckart reaction, and this recipe is going to employ the LiAlHa way of stripping the double bonded oxygen of the formyl side group to give methamphetamine. The 89 of formyl intermediate is dissolved in SOmL ether and added dropwise into a solution of 6g LJAlk;-in-100ml_other-andrefluxed 4h al Jowed to cool, S0mL dH¿O is added, the solution vacuum fitered then extracted with 3N HCI. The MDMA/meth freebase is liber- ated from the acid with NaOH extracted with DCM and removed of solvent to give -8g. METHOD 42: [89]--1M MDA or benzedríne and 1M benzaldehyde is dissolved in 95% ethanol (Everciear), stirred, the solvent re- moved by distilation then the oil vacuum distilled to give 95% yel- sectiont -158- low oll wnich is a Schiff base intermediate. —1M of this intermediate, plus 1M iodomethane, ís sealed in a pipe bomb thats dumped in boling water for 5 hours giving an orangy-red Í its volume E is added and the solution refiuxed for 30 minutes. Next, an equal volume of water is added and the whole solution boiled openty un- til no more odor ef benzaldehyde is detected (smells like almond extract). The solution is acidified with acetic acid, washed with ether (discard ether), the MDMA or meth freebase liberated with NaOH and extracted with ether to afford a yield of 90% for meth and 65% for MDMA. That's not a bad conversion but whal's with having to use another aldehyde can substitute. -159- METHOD +3: [90]--The folks in this article made an acetyl inter- mediate out of an amphetamine to act as a form of protection group so that they could screw around with the molecule without anything happening to tha! precious amine group. This method will end up yielding MDEA or PEA and will use the very walched acetic anhydride. This method is only for the weird. 80mL acetio dium acetate and 300mL dH¿O, which is then shaken until the exothermic reaction ceases. The cooled solution is filtered and extracted with ether to give n-acetyl-MDA, which can be stripped of its oxygen with LiAIH, just like was done in the Leuckart method. ADVANCED SHRIMP PREPARATION TECHNOLOGY Strike has been very disappolnted in the lack of responses re- garding the shrimp recipes from the last edition, Only two people contacied Strike saying they had tried them. Naturaliy it was the best food they had ever had. Strike can't understand what was wrong. Was it a problem with translation for the Europeans (hi “shrimp' in European is 'prawn', possibly 'langoustine)? Was it that all of you can't afford shrimp? Cant cook? If you can't cook then this book is of no use to you. Actually, the problem is clear. If all of you would stop taking am- phetamines you would regain your fucking appetites! Here's the recipes for when you get aut of detox. Shrimp Diablo Jumbo shrimp Jalapeno peppers (seeded and halved) Bacon strips (blanched 1 min in boiling water) Teriyaki sauce -Cut the blanched bacon strips in half. Place one jalapeno half inst-l_sh hab: hi e th -160- 9 pWreaj plece—ant toothpick. Place all of the shrimp 'brochettes' into a bowl and marinated at least 30 minutes covered with teriyakl sauce. Broil 5 minutes and serve, Yum! Shrimp ala Strike Jumbo shrimp Thinly sliced prosciuto or panestta Gruyere cheese -Cut the cheese into french fries-sized pieces, place one piece -181-  with a shrimp and wrap with a slice of prosciuto, Broil this for five minutes and serve as is or with a dipping sauce of butter and lemon. Double yum! the reward is heaven, Shrimp Acapulco Jumbo shrimp Beef sirloin or tenderloín, cut into 1" pieces 1/3 cup peanut ol 2 tablespoons soy sauce the juice of 3-4 limes (or lemons) 1 large shallot, minced 2 sticks Unsalted butter, cut into tiny pieces and put in freezer % tablespoan vinegar 1-2 ounces Grande Marnier (or any orange-favored liqueur) 1-2 tablespoons of crushed pineapple with juice (canned is fine) Y tablespoon soy sauce Altemate beef and shrimp on skewers. Mix the peanut oil, soy sauce and lime juice in a bowl to use a basting sauce. On a nice, hot toal-orwood gli, cook the W-bobs until medium Tare tor to taste) brushing them often with the basting liquid. Put aside and keep warm. After all the butter has been whisked in the sauce will be creamy and warm. If poois of clear butter oil have started pooling up all over the place the sauce has broken. You tailed, Actually, the 1 Omplex. sauce will still taste fine, ít just won't be creamy like a snooty Frenchman would like. The sauce can be kept warm over a hot water bath or by stirring over low heat. Anyway, at this point one slirs in the soy sauce and pineapple into the sauce and drapes it over the k-bobs. Oh God is it the best flavor in the world. You have been warned! In a skíllet or shallow sauce pan heat 1 tablespoon butter, the vinegar and the orange liqueur, add the shallots and saute them lightly for about a minute or until soft. Now the tough part. You're going to make a tricky butter sauce. Luckily for you, Strike is a trained professional chef (true). You're gonna fake the butter pieces out of the freezer and greb a whisk. Now, while the pan and its contents are still warm (but NOT too hot) start adding the butter piece by piece while whisking vigorously. Keep moving the pan off and on the heat source so thal enough heat gets through to melt the bulter and warm the sauce. But not so much heat as to cause the butter to break. - 162 - - 163 -  thermic reaction was allowed to run its course. When the reaction mixture again had cooled to room temperature, it was poured an 2009 of an ice/water mix, and was made slightly basic (pH 7-8) with 5% NaHCO;. The product was extracted into ether, washed Mita saturated NaCtsolution, drisd over NazS0, and the sovent removed under vacuum to give almost pure P2P oxime in 90-95% yield. Ref: G. Kabalka, Synth Comm 18(7), 693-697 (1988) Cleavage of Oximes The classic way of cleaving an oxime to the corresponding carbonyl compound is through acia hydrolysis, or an acid catalyzed exchange resction with excess formaldehyde. This is a crude method. and has often non-Satisfactory yields. Alkaline H20 can also be used, as in Synth Comm 10(5), 465-468 (1980). enyis2-Propanone Oxime Cleavage with Sodium Bisulfite Preparation of MDP2P from safrole 14.9 grams of P2P oxime (0.1 mal) is dissolved in 150ml 50% al- cohol and is refluxed with grams 36.4 grams (0.35 mol) sodium bisulfite for 6 hours, when the reaction had gone to completion. The ethanol was removed under vacuum, and the residue mixed with 25ml DCM ana the mixture was treated with an excess of 2M HCI and stirred until two clear layers formed. The layers were separated, and the aqueous layer was extracted with 2x25 ml DCM, and the organic extracts were combined and the solvent Safrole can be oxidized to safrole epoxide with H¿0z in a two- formed safrole epoxide is then isamerized to MDP2P with Lil nm me o. O. SS) Safrol MD-P2P. Preparation of the catalyst aqueous H¿02 was stimed and heated to 60“C until a colorless solution was obtained. To this solutian, filtered and cocled ta raam temperature, was added 40% w/v H3PO, (0.62ml, ca 2.5 mmol), and the whole was diluted to 30 ml with water. To the resultant soluton, 2.08g of methyltrioctylammonium chloride (97% pure, equiuvalent to 2.0279, 5 mmol) in DCM (40 mi) was added drop- wise with stirring over about 2 min. Stirring was continued for an . : . , over Na¿SO,, filtered, and gentiy evaporated on a rotary evapo- rated under reduced pressure at 40-50%C (bath) to give 3,70 y (98,4%, based on the qustemary ammonium salt chargea) of an almost colorless syrup. Ref: C. Venturello, J. Org. Chem. 53, 1553-1557 (1988) Oxidation of safrole to MDP2P evaporated to give a near quantitative yield uf PZP, wiich, FT has an orangish tinge, can be vacuum distilled to yield a light yellow oil, -168 - In a 100ml three-necked, round-bottomed flask equipped with me- “efi condenser, a vigorousl! stirred mixture of the ábove catalyst (0.79, 0.31 mmol), safrole (13.249, 80mmol), benzene (35 ml) and 40% w/v H¿02 (5,10ml, 60 -169 -  mmol) was heated to 6090 and kept at this temperature for 80 min (External cooling is needed!). The mixture was cooled to room temp, the organic phase was separated and diluted with 30 ml ELO. In order to remove the catalyst, the organic solutian was firat stirred with a solution of Na¿CO, (0.759) and Na;SO, (0.759) in water (10 mi) for a few minutes, then separated, drisd over Na2SO, and passed through a short column (2.5 em diam) of silica gel (509), and —300m! enhydrous EkxO was passed through the column to ensure complete elution of the products. The solvent was evaporated and the residue dissolved in 18 ml of tetraglyme and treated with anhydrous Lil (0.1309, 0.97 mmol) at 13006 for 5h. After cooling, the products were distilled under vacuum, re- covering 5.17 grams safrole (saved for the next run) and collecting 8.25 grams of MDP2P. Sh l MD-Phenyl-2-Nitropropene MDA Reduction with NaBH/NiC|L 3.68 grams NiCL*SH¿O (15.5 mmol) was dissolved in 300 ml MeOH, and 1.769 NaBh, (46.5 mmol) was added portionwise (Caution, frothing!) with stírring to the wonderfully light green solu- tion, and the solution immediately turned black and hydrogen was evolved. The solution was left to stir at room temp for 30 mínutes, and 5.0 grams (31 mmol) phenyi-2-nitropropene was added all at once, followed by 4.1 grams NaBty in small portione over a period Ref: C. Venturello, US Pat 4,731,482 C, Venturello, Synthesis, 1229-1231 (1992) Reduction of nitroalkenes to primary amines NaBH, in methanol, catalyzed by nickel boride, can be used to min at room temp. The nickel boride is prepared in situ from NiCIz*SH20 (nickel chloride hexahydrate) and NaBH¿. The method is general, and can be applied to many conjugated nitroalkenes. Other novel promising methods are catalytic transfer hydrogena- tion with Pd/C (Tet Lett 29(45), 5733-5734 (1988), NaBHa in methanol, followed by Al/Hg (Tet Lett, 1317-1320 (1977), NaBHa and CuSO, (Synlett 419-420 (1990)), and finally NaBH, and tri- methyisilyicnloride in THF (Angew Chem Int Ed Engl 28, 218-220 (1989) 9F 5 minutes, care being taken for the frothing. After 15 minutes, the reaction mixture was filtered through celite to remove the boride and the filter cake was washed with 50 ml MeOH. The sol- vent was removed under vacuum, and the residue taken up in 100mi dilute H,SO,, washed with 3x25 ml CH?Cl, basified with 25% NaOH, and extracted with 3x50 ml CHCl, The pooled ex. tracts Were dried over MgSO,, fitered and the solvent was evapo- rated in vacuum, the residue dissolved in a little [PA, and 37% HCI ed w al ether until tur and left in the freezer until all product had p: eptated The white crystals of amphetamine hydrochloride was ie le eri ; same fashion, just use 6.4 grams of 3,4-methylenedioxyphenyl-2- ritropropene instead of the phenyi-2-nitropropene. Ref: Oaby 8 Ganem, Tet Lett 26(52), 6413-6416 (1985 -170- -171-  Proposed Synthesis of MMDA and Mescaline by Rhodium and Osmium 980519 cold (0”C), 70% metanol, and dried in vacuo at 50*C overnight to give 218.5 grams (95%) of 5-bromavanilin as pale yellow crystals, mp 163-1640. L OM F O Me0. Meo' MeO' NH, 5-Bromovanillin (alternative) [2] To vanillin (15.29, 0.1 mol) in glacial acetic acid (75 mi) is added bromine (17.89, 0.11 mo). After stirring for 1h, the reaction mix- ture is diluted with ice/water (200m), the precipitated solid is fil- tered, washed wilh water, and dried to give 5-bromovaniliin, yield MMDA Mescaline 22,09 (95%) [Rtodiums voice] ome oMe The synthesis of MMDA in Pihkal is one of the.longest and most fedious in the book, If one is going the route via myristicin, the HOLA HOLA book ' da s nutmeg, followed by fractional distillation to purify the myristicin LA - A, fractiortis also added to the labor of the poor chemist. Therefore 1 Br cHo HO: cHo propose a new route to this "essential amphetamine”. » 5-Bromovanillin | Í OMe OMe 5-Hydroxyvanitlln POS, As S-Hydroxyvanillin [3] | =— | AS cu Er So Sodium hydroxide, 61.2 grams (1.53 mol), was dissoed in 750 mi of water in a 2000m1 round-bottomed flask. To the stillwarm Vanilin s-Bromovanilin solution was added 50.09 (0.217 mal) af 5-bromovanilln and 0.5 y 5-Bromovanillin To a stirred, cooled (0%C) solution of 152.159 (1.0 mol) of vanilin in 1000ml of methanol was added during 20 min 176.09 (1.1 mol) of bromine at such a rate that the temperature was kept below 20*C. The mixture was stirred at room temperature for 1h, cooled Stiring was continued for 15 min and the product was collected by filtration. lt was washed with water (4x500 ml), then with 500 ml of -172- of Cu powder. Á white solid precipitated. The reaction mixture was relluxed vigorously under N, and with magnetic stirring. The color changed gradually from yellow to green to dark green and, after ca 8 hours, all solid material was dissoived. After 27 hours of re- fluxing, the reaction was over, and the solution was acidified with 113ml conc HCl to pH -2, and was extracted*) with ether (or other suitable organic solvent), and precipitated as the bisulfite adduct through shaking the organic phase with an excess of saturated cold water, and dissolved in an excess of 10% sodium carbonate solution to release the aldehyde again. The solution was extracted with DCM and evaporated to yield the title compound -173-  Syringaldenyde: (3,5-dlmethoxy-4-hydroxybenzaldehyde): [7] 5-bromovanilline (Smmol) is refluxed with EtOAc (3mmeh and CuBr (1mmol) in 5 M NaOMe/MeOH (10 ml) for 14 hours. Classi- cal work-up (addition of weter and acidification followed by extrac- tíon of the phenol) leads to pure syringaldenyde (95%). When starting from the more soluble 5-bromovanilline dimethy! acetal, reaciion is achieved within 2 hours (yield 98%). Preparation of this acetal is probably not worth the extra work. Substituting EtONa for MeONa seems to work too, producing 2-sthoxy-3-OH-4- methoxybenzaldehyde, useful for athoxy-derivatives of Mesca- line. The above synthesis, although performed on a small scale, is easily scaled up to industrial size (French Pat. 2,689,922, CA 118; P8734u). It is a general procedure tor substituting aryhBr wi OMe or -OEt, giving us the possibility to produce other cam- pounds from already known substances, e.g bromination of MDA yields 5-BrMDA. This is converted by the above procedure to MMDA-2, 18133, active at 25-50mg, 8-12 hrs. Asaronealdehyde (2,4,5-trimethoxy-benzaldehyde) can be pro- Me0-benzene. Do a Vilemeyer aldenyde synthesis with POCIyN- methylformanilide to obtain: 2,4-di-MeO-benzaldohyde. Brominate and treat as described above to obtain asaronaldehyde. Syringaldehyde is easily methylatad or ethylated with the known procedures in high yields forming the highiy-desirable 3,4,5- trimsthoxybenzaldehyde or the 3,5-diMBO-4-EtO-benzaldehyde (Escaline, 472, 40-50 mg, 8-12 hrs.). Me OMe HO. . <= Mao. : SS e 0 Homo 100 Somo 5-Hydroxyvanillin 3,4,5-Trimethoxybenzaldehyde 3,4,5-Trimethoxybenzaldehyde [3] from 6-hydroxyvanillIn: Into a 1-1. round-bottomed flask equipped with a magnetic stirer and a reflux comdenser were placed: 50 g (0.298 mol) 5- hydroxyvanillin, 500 ml acetona, 91.0 g (0.718 mol) dimethylsul- pt A mol 22007! , mi of 10% KOH in methanol. Of course equimolar amounts of anhydrous Na¿CO; or K,CO, can be used. The heterogenous mixture was stirred under vigorous reflux for 24 hours, after which the reflux condenser was replaced with a descending condenser. The sol- vent was distilled at a bath temp. of ca. 100* until the distillation ceased, To the solid resídue was added 400 ml of water and the heterogenous mixture was stired VIGOROUSLY for 2 hours at 2 aaa á light brown crystals were filtered by suction, washed with 3*150 ml of ice water and air dried to constant weight, Yiald 55.19 (94%), m.p. 72.5-74*. After distillation at 0.5mmn/130>, there was obtained a 90% yield of 3,4,5-trimethoxybenzaldehyda, m.p. 73.575, VPC purity 99,3%, (This distillation is probably unnecessary, because the aldehyde is already quite pure). -178- -179-  Syringaldehyde 3,5-Dimethoxy- 4-ethoxybenzaldehyde 3,5-Dimethoxy-4-ethoxybenzaldehyde [8] from syringaldo- hyde: [7] Tetrahedron Letters, Vol. 34, No. 6, pp.1007-1010, (1993) [8] Pihkal, 472 Online - Pinkal can be found at htpi/Awww hyperreal.org/druas/pihical/ A welbstirred suspension of 21.9 y syringaldehyde in 45 mL H20 was heated to reflux in a heating mantle. There wás then added a solution of 15 g NaOH in 80 mL H¿O. The heating and stirring was 10 min, there was added 23 g diethy! sulfate, then refluxing was continued for 1 h. Four additional portions each of 5 g diethyl sul- fate and o! 6 mL 20% NaOH were alternately added to the boiling solution over the course of 2 h. The cooled reaction mixture was extracted with ELO, the extracts pooled and dried over anhydrous MgSO,, decolorized with Norite, and stripped of solvent The crude 3,5-dimethoxy-4-ethoxy-benzaldehyde weíghed 21.8 g and melted at 51-52%. See the same reference in Pihkal for details on how to use ethyl iodide instead of diethyl sulfate. [1] Syn Comm 20(17), 2659-2866 (1990) [2] Synthesis, 308 (1983) BJUS Par 3,855,308 [4] Tet Lott 38, 3351-2364 (1976) [51 JACS 99(2), 498-504 (1977) [6] Pihkal, 4132 (p. 787) - 180- - 181 - For molecules similar ta safrole or alylbenzene we tako the work PROMISING THEORETICAL METHODS done on any terminal altene such es 1-heptene, 1 octene. An- alher term to look for is 'alefin' which is a term for a doublebond containing species, What we then look for are articles about these olefins where the functional grat Articles with terminology Ike "methy! ketones from" (P2P), 'ketones —— GRE and others tavorite pastime is to comb the library for new ——— rom samines trom-etc-Orwterwe want to see about new ways A a and e old to aminate a ketone (make final product from P2P) we look for any methods available (see this entire book), there is always room for article about ketones where amines are formed. Sound like sci- more. Relentiessness drives us to find even cheaper, higher ence fiction ta you? Well, how de yau think we came up with hatt yieiding methods. But the biggest reasan ís to make a buffer zone the recipes in this book!? lt works! of so many options that govemmental restriction is rendered use- less. That is our power. So many committed, dangerously- Every article such as these may have the potential to be useful. intelligent peopie around the worid with far more motivation than Eut it takes a lot of looking. a keen eye and a sense for what is r hope to have. real. The contribulions in this section are just that (real). These have gone through the right chan You're not going to find journal articles with new syntheses written oeste hat brought you the rest of this book. These ara ——Bpecially tor X or speed anymore. The scientists of the world al- ———— comsidered to hrave-the greatest potential and are here for your ready have recipes that work and the access to the restricted consideration to use in legal research of your choice. Be wamed, chemicals necessary to make them work. So why should they look though. The chemistry here ls a lítie hairy and, for the sake of for anything new? They don't. There is no reason for them to do time and Strike's sanity, is not explained as simply as the other 20. recipes in this book. But we have many reasons. ThaCis why the people ofihe Under SEMI-DIRECT AMINATIÓN-OF SAFROLE ground are actually progressing the fields of carbonyl, amine and > amphetamine science. Belleve it or not, the novet applications of journal methods on precursors published research work. Half of the stuff in this book is publish- able, praper science done by people with na funding. lt is actually amazing when you think about it The dream of every X chemist is to get that amine function directly on the safrole mojecule without having ta go thru any intermediate such as the ketone of MD-P2P or the bromine of bromosafrole, But Strike ean tell you right now that that is very, very tough (that is why there ain't no methods for it). About the only articie Strike has ever found for the actual placement of an amine directly on a So like Strike was saying, without any new, direct literature syn- terminal alkene (a.k.a. safrale) is the following [79]: forced to take ideas from wark on ————Á molecules that are similar to our own. Often molecules that one wouid not think have any relatio! “Amination of propyiene: The co, Pylene to ¡sopropylamina and diisopropylamine was shown to take a. 250'C and 850-1000 atm pressure (ref. 7). ln contrast, we have found ifrat these reagents -182- -183-  USPat. 4,694,107 They react 2-phenyloropanal in the gas phase at 300-4000C with zeolithes (silicate) to yietd 86% P2P. Quite hot, yes, but othenwise not tao difficult, 1 think” Strike found this next thing doing an alenighter Chemical Ab- stracts search. Strike does not even want to try to explain it. Just read it. If you understand it, great! If not, don't sweat it. Hell if Strike will ever try the damn thing [88] (Note the P2Pol produc- tion): Pe RO=R5=R'= CF, and R'=R'=H). ll may be prepa. By reaction of diketone ligands RÍCOCHR*COR' with CoCla in the presence of KOH ín HO. Thus, 2 mmol PhCH¿CH¿CH:CH, was oxidized 2 h at 76* and atom O in the presence of 20 mol% MR? =Ró=p= R? = tert-By Ri =R" = H) in 10 mi MesCHOH to give 29% PhCH2CH¿COMe and 71% PhCH¿CH¿CH(OH)Me, Adéni. 39 vatalysts were evaluated for the above oxidn. And 18 other olefíns were oxídized: aos. were obtained as byproducts." This next method for making P2Ps was posted anonymously on the a.d.c. quite awhile ago. Strike is sure most everyone knows who did this, but Strike doesn't to this day. So whoever you are—- Thanks! Although Strike has an original paper copy of this post, o. Strike had no copy on disc. So Strike snagged the text from an ( ss o archived example saved on Rhodiunvs home page. So if you want o e o ss more about this method go aná visit the site where it rests o MD-P2P o o <= TS me E E Satrole o. o Ss 0H — | z L Isosafrole MD-P2P MD-P2Pol using cobalt diketone catajysts. Mukoyama, Mitsuaki: Isayama, Shigeru: Kato, Koji: inoki, Satoru: Yamada, Toru: Takai, Toshiniro (Mitsui Petrochemical industries, Ltd) Jon. Kokai Tokkyo Koho JP 02,121,944 [90,121,944] (C1. CO7C49/04) 09 May 1990, Appl. 88/272,450, 28 Oct 1988; 18pp.. RÍCOCH¿R and R'CH¿COR' [E ¡ RU = (unjsubstituted (cycioJalky! or aryllalky); R = H (un)substituted, alky! or aryiíalky)] are prepd. By reaction of R'CH:CHR' with O-contg. Gas in the presence oFa secondary ale. And a Co (11) cotalyst ¡l; FF, RR RE = H, straight-chain, branched or cyctic C1-10 alkyl, (un)substituted ary! or CONHz , eto; R*, R=H, alkyl, halo, CO¿, alkoxycarbonyl: exoluding RO - 188 - *Subjest: Phenyl acetones by electrolytic oxidation From: "guest" <guestQwebshack-cafe.com> Date: 1997/11/08 Appendix - Phenyl acetones by etectrolytic oxidation. Process for 3,4-dimethoxyphenytacetone preparation European Patent Ap- plication 0247526, Filed: 02.12.87; to LARK 5.p.a. Milan. Example 1. - 189 -  6.27 g of NaBr is dissolved in 25 m] of H¿0 and 125 mf of CH¿CN, the mixture is then sirongly stirred by means of magnetic Stiming, and to it 3.76 y of isoeugenof-methylether (1) is then added. The obtained mixture ís then electrolysed in a 250-mmi not-partitioned electro chemical cell, with a constant current of 850 ma, with two Example 23 graphite anodes with a total surface of about 17 cm2, and a con E as tral stainless-steel cathods having a surface of about 25 om being To a 250-mI notpartitioned electro chemical cel 125 mi of used, with a distance between electrodes of about 1 cm. 5,200 CHsON, 25 mi offt2O, 8.47 g of NaBr and 2.78 y of isoeugenol. Coulombs are passed, with the reaction mixture being ko! al a methylethor (1 is added. The mixturo is electrolysed at a constant temperature of 20" C.From lhe reaction méxture, discharged from Current of 350 mA, with a titanium anode coated with a mixeg Ru- the electrochemica! cell, two phases, Le. the aqueous phase, Ti oxide (50:50 by weight), with a total surface of about 7 cr, and containing Br- lons, and the organic phase, containing acetonitrile a central staintess-steef cathode having a surface of about 15 om2 being used, with a distance between electrodes ofabout 1 cm. and the reaction product, are separated. From the organic phase acetonítrile is evaporated off under reduced pressure, and to the Through the cell 4,000 Coulombs are passed, with the reaction mixturo being kept at the temperature of 20* C.The reaction mix- resulting reaction product 40 mi of ethy! acetate ¡s added. The , si : gas-chromatographic analysis of lhe organic phase shows the ture is fhen processed according to such modalities as reported in presence of epoxide (1) with a >90% punty. Example 1, until the solution of the reaction product in ethylace- tate is obtaíned, to such solution, 337 mg of Lil is added. The 'midture ís then refluxed (at ethyl acetate refuxing temperature) for The reaction mixture in ethyl acetate is then transterred to a 100- 3 hours, and the process is continued as described in Example 1. mi reactor, purged under a nitrogen atmosphere, 340 mg of Lil is until 2.7959 is obtained of ketone (11), with a yield of 92.2% refa- edded, and the whole mass is then healed, with mechanical stir- tively to the olefin (1) used as the starting material. ring, on an oil bath, up to ethyl acetato reflux temperature. The heating is continued for 5 hours, until the disappearance of the instead of 5 hours. In this way, a yield of ketone (II) of 86% rela- tively to the oletín (1) used as the starting material is oblained. epoxide (11), as evidenced by the thin-layer chromatography. Example 4 To—a_—250=mi—rrotpartitioned—etectrocitemicat—velt—125-mi-of The resction product is coofed to room temperature, is washed CHRCn, 25 mi ofiz0, 8.40 9 of NaBr and 2.678 9 of isoaugeno" e ñ iure, kept at 20? C, js electro: ti 10 mi oh to ne pumose el removing linen tido ana methyether () ls ados Ta md e lla over Na 9 is obtamed of dimethoxy- as of Example 1 being used, through the cell 3,625 phenylacetono (11), 8 determined Dy gas chvomaloyraprio anal A Lai DE ParacayS mol, Dong Rossa. The reno. sís with an inner standard of 44*dimethoxybenzophenone. The tion mixture is then transferred to a rotary evaporator, for CHyCN yield of ketone (Ill) relative lo the olefin () used as the starting tobe stripped under vacuum. The resulting reaction product ís then meterla! is of 87.4%. extracted three times with 30 mi of ethyl acetate, and is then dried aver Na»SO,. The organic extract, concentrated to a volume of 25 Example 2 mí, and with 160 mg of added Lil, is refluxed (al ethyl acetate re- Example 14 atad j Lt e de fuxing temperature) for 6 hours. The process ls continued as de- A Pp seribed in Example 1, and 2.54 g is obtained of ketone (1), with e that ín the isomertzation step 250 mg of LÍBr instead ol 340 mg of yleld of 86.5% relatively to the olefin (1) used as the starting male- Lil is used, and that the reaction time results to be of 10 hours, rial - 190- -191-  Example 5 To a 250-mi not-partitioned electrochemical cell, 135 mi of HAC 15 mL oR0,5-20 g-ofNaBr and. 2.82 g-ot ole (Y added. The mixture, kept at 20” C, is electralysed by using the same electrodos as of Example 1, bul with. a constant current density of 1.7 A being used,until through the cell 4,000 Coulombs have been passed. The reaction mixture is then processed as de- scribed in Example 4.2.56 y is obtained of ketone (III), with a yield of 83,2%, as computed retatively to the olefín (1) used as the starting material. Examples 6-9 To a 250-mi not-partitioned etectrochemical cell, 100 ml of DMF, 50 mor H20, 6.72 g of NaBr and 4.25 y of ISosugenor methylether (1) is charged. The módure is then etectrolysed under the same conditions, and by using the same set of electrades as used in Example t, with a total of 5,670 Coulombs being passed. At reaction end, the mixtura is discharged, to it 250 mi is added of 20% aqueous NaC! solution, and it is then extracted four times with 50 rai of ethy! acetato. The extract is washed twice with 50 mt of 20% aqueous NaCI solution, and ís then dried.The organic ex- tract tatect 4 p400-mibythe-solvontbci STUFF THAT DEFIES CLASSIFICATION These last three theoretical methods have no real kinship to any of the major categorias or precursors, The first is the one that ha caused Strike more despair than any other. lt was once a Top Ten recipe in the first edition. But lt was a reckless gamble on Strike's part and Strike paid for it. Here is what Strike wrote last year... lf you read the excellent book called "Recreational Drugs" by Professor Buzz [8] you may come across a little recipe in the am- phetamine section for something called N-acety!-phenethylamine. So wnat the hell is that? Well, actually it happens to be one step away from being an amphetamine but no one makes this clear to all the novices reading the book. Strike means to say that even novices just reading for pleasure need a little help here and there. e PA e . y chemicals and is a more direct way of aminating safrale or allyi- benzene without having to go through the making of an intermedi- ate such as MD-P2P or P2P. Actually, Strike is under the distinct impression that Professor Buzz got this recipe from the progenitor of underground chemistry books: "Psychedelic Chemistry" by Mi- chael Valentine Smith. Unfortunately, both these authors simply copied commentary from the actual scientific article 91] without y evaporated off. On three aliquots, of 20 mi each, of said extract, the isomerization reactions are carried out at the ethyl acetate re- fux temperature, by using the same lithium salis and reaction times as shown in Table 1. From the fourth aliquot of 20 mi of above seíd extract, ethy! acetato ís evaporated off and replaced with the same amount of acetonitrie. The isomerization of the re- action product ís then carried 0ut al acetonitnle rofuxing temn- perature, with the lithium salt and the reaction time being used as shown in Table 1(Table not shown)” -192- ON Sa A, OLE DO 5 o y HE Y 4HONOy, so o, Ss a, NaOH 3% a Naom YO Er l | == (| No MS AZ NacatyiiDA MDA -193-