Aldehydes and Ketones - Assignment 17 | CHE 232.00, Assignments of Organic Chemistry

Download Aldehydes and Ketones - Assignment 17 | CHE 232.00 and more Assignments Organic Chemistry in PDF only on Docsity! © Assoc. Prof. S. R. Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 1 ORGANIC CHEMISTRY: FALL 2008 by Associate Professor Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 1. These problems are derived from Section 17.1 in Vollhardt & Schore textbook. Provide reasonable IUPAC names for the following molecules. Also do problem 71.1. O H O O H O H O O Br O cyclohexanecarbaldehyde cyclohexanone cyclopentanone 4-penten-2-one hexanal 3-methylhexanal 5-bromo-3-hexanone © Assoc. Prof. S. R. Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 2 2. These problems are derived from Section 17.1 in Vollhardt & Schore textbook. Provide reasonable IUPAC names for the following molecules. Also do problem 71.1. H O CH3CH2CHO CH3 O CHO O O O CHO CH3O methyl phenyl ketone or acetophenone pentanal 5-methyl-3-octanone 2-propanone or acetone 2,4-dimethyl-3-pentanone para-methoxybenzaldehyde butanal propanal © Assoc. Prof. S. R. Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 5 9a. Complete the following reactions. If there is no reaction, then write NR. CH2 ozne (O3); Zn CH2 CH3 ozne (O3); Zn H CH3 ozone (O3); Zn H3C CH3 ozone (O3); Zn ozone (O3); Zn ozone (O3); Zn O + H H O O CH3 + H H O O + H3C H O O O + O H3C O 2 2 © Assoc. Prof. S. R. Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 6 9b. Complete the following reactions. Indicate the stereochemical nature of the transformation. All reactions begin with the syn-stereospecific delivery of hydroxyl groups via the osmate ester. The free syn-diol then creates a periodate intermediate that undergoes cleavage to create the carbonyl groups. CH3 CH2 C5H11 CH2 Et cat. OsO4 NaIO4 CH3 cat. OsO4 NaIO4 cat. OsO4 NaIO4 cat. OsO4 NaIO4 Br cat. OsO4 NaIO4 cat. OsO4 NaIO4 cat. OsO4 NaIO4 O CH3 + formaldehyde O Et + formaldehyde O H O C5H11 O CH3 O H O2 O O O + formaldehyde © Assoc. Prof. S. R. Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 7 10. Complete the following reaction by showing the final product. Are these processes Markovnikov or anti-Markovnikov in their behavior? The process is anti-Markovnikov in behavior. C C H C C H H3C C C H H C C H 1. NaNH2, THF 2. (CH3)3CCH2CH2I 1. Cy2BH 2. NaOH, H2O2 C C H C C H OCH3 HO 1. Cy2BH 2. NaOH, H2O2 1. Cy2BH 2. NaOH, H2O2 3. Cy2BH 4. NaOH, H2O2 N(CH3)2 1. Cy2BH 2. NaOH, H2O2 1. Cy2BH 2. NaOH, H2O2 H3C C C H OHH H3C CH C H OH C C H OCH3 OH C C H OCH3 OH HH C C H OHH C C H OH H C C H HO H OH C C H HO H O H CH2 C H N(CH3)2 O H C C CH2CH2C(CH3)3 H C C CH2CH2C(CH3)3 OH H H C C CH2CH2C(CH3) 3 O H H © Assoc. Prof. S. R. Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 10 These problems are derived from Section 17.5. 13. Complete the following reactions concerning the reduction of carbonyl compounds. The hydrogens of the reducing agents (LiAlH4, NaBH4) are referred to as hydrides. These are hydrogens that carry significant charge density and can attack electrophilic carbons. CH2CH3 H O O O O O NaBH4, CH3OH NaBH4, CH3OH 1. LiAlH4, THF 2. dilute HCl H H 1. LiAlH4, THF 2. dilute HCl NaBH4, CH3OH O 1. LiAlH4, THF 2. dilute HCl O NaBH4, CH3OH CH2CH3 OH H OH OH OH H H OH OH HO H H H H H H H © Assoc. Prof. S. R. Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 11 14. Complete the following problems. If there is no reaction, then write NR. The organometallic reagent (the Grignard reagent) carries charge density at the carbon attached to the metal. It is this that makes the connection. 1. O CH2CH3 CH3CH2MgBr, THF1. 2. dilute HCl O CH3 CD3MgBr, THF1. 2. dilute HCl O CH3 1. 2. dilute HCl MgBr O 2. dilute HCl CH2CH2MgBr, THF O 1. CH3CH2CH2MgCl 2. dilute HCl H O CH2CH(CH3)2 1. CH3CH2CH2MgCl 2. dilute HCl OH CH2CH3 CH2CH3 OH CH3 CD3 OH CH3 OH CH2CH2 OH Pr H OH CH2CH(CH3)2Pr Pr = propyl = -CH2CH2CH3 © Assoc. Prof. S. R. Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 12 15. Complete the following integrated problems. Write out the products of each transformation. The last step is an acid quench to help in the removal of inorganic salts. CH3 OH HO OH 1. PCC, CH2Cl2 1. Na2Cr2O7, H2SO4 1. PCC, CH2Cl2 1. K2Cr2O7, H2SO4 1. CrO3, H2SO4 2. CH3MgBr 3. dilute HCl OH 1. PCC, CH2Cl2 2. CH3CD2MgBr 3. dilute HCl 2. MgBr 3. dilute HCl OH 2. (CH3)CHCH2Li 3. dilute HCl 2. CH3MgBr 3. dilute HCl OH Li2. 3. dilute HCl O OH O OH CD2CH3 CH3 O CH3 HO O OH CH2CH(CH3)2 No Reaction. This is a tertiary alcohol that does not have the necessary hydrogens for removal. O OH © Assoc. Prof. S. R. Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 15 19. Complete the following reactions. Be sure to draw out all intermediates that form. Assume that there is a quench/work up for each reaction. O O OCH3 1. CH3OH, cat. HCl 2. LiAlH4, ether 3. HCl, H2O 1. CH3OH, cat. HCl 2. LiAlH4, ether 3. HCl, H2O O CO2CH3 OCH3 O OCH3 H3CO OCH3 OH H3CO OH O OCH3 CO2CH3 H3CO OCH3 CH2OH H3CO CH2OH O © Assoc. Prof. S. R. Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 16 19. Complete the following reactions. Be sure to draw out all intermediates that form. Assume that there is a quench/work up for each reaction. O OH 1. CH3CH2OH, cat. HCl 2. PCC, CH2Cl2 4. HCl, H2O 3. CH3MgBr, THF OH O 1. CH3CH2OH, cat. HCl 2. PCC, CH2Cl2 4. HCl, H2O 3. CH3CH2MgBr, THF OCH2CH3 OH H3CH2CO OCH2CH3 O H3CH2CO OCH2CH3 HO H3CH2CO CH3 HO CH3 O OH OCH2CH3H3CH2CO O OCH2CH3H3CH2CO aldehyde OH OCH2CH3H3CH2CO CH2CH3 OH CH2CH3 O © Assoc. Prof. S. R. Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 17 20. Complete the following reactions. Be sure to draw out all intermediates that form. Assume that there is a quench/work up for each reaction. Br 1. CH3CH2OH, cat. HCl 2. Mg, ether 4. HCl, H2O 3. CH3CHO O H Cl O 1. CH3CH2OH, cat. HCl 2. Li, ether 4. HCl, H2O 3. CH3CH2CHO Br OCH2CH3 H H3CH2CO MgBr OCH2CH3 H H3CH2CO OCH2CH3 H H3CH2CO CH3H OH H CH3H OH O Cl OCH2CH3H3CH2CO Li OCH2CH3H3CH2CO OCH2CH3H3CH2CO CH2CH3 OH CH2CH3 OHO © Assoc. Prof. S. R. Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 20 22. Complete the following reactions. Assume that there is a quench/work up for each reaction. OH3C O N H O H3CH2C N CH2CH3 H N H H O N O H O N O H N N CH2CH3H3CH2C NH2C H N O N O mixture of diastereomers mixture of diastereomers mixture of diastereomers © Assoc. Prof. S. R. Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 21 These problems are derived from Section 17.11. Do problem 17.12. 23. Complete the following reactions. If there is no reaction, then write NR. O H O CHO O O O NaCN, H2O then HCl KCN, H2O then HCl OCH3 NaCN, H2O then HCl CsCN, H2O then H2SO4 NaCN, H2O then HCl KCN, H2O then HCl CNHO H HO CN OCH3 OH CN OH NC OH CN OH CN © Assoc. Prof. S. R. Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 22 These problems are derived from Section 17.12. Do problem 17.13-14. 24. Complete the following reactions. If there is no reaction, then write NR. H O O P C H H Ph Ph Ph P C CH3 H Ph Ph Ph O P C CH3 CH3 Ph Ph Ph H O P C CH2CH2CH3 H Ph Ph Ph O O OEt P Ph Ph Ph O OCH3 P C CH3 CH3 Ph Ph Ph THF THF THF THF THF THF C HH H C CH3H C CH3H3C H HCH3CH2CH2 O OEt NR. Esters do not possess the reactivity as aldehydes and ketones mixture of cis and trans isomers mixture of cis and trans isomers © Assoc. Prof. S. R. Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 25 27. Propose synthetic pathways for synthesizing the following molecules. H3C H H CH3 HH H3C H H CH3 H3C H H CH3O Ph3P HH O Ph3P HH O H H Ph3P O Ph3P H © Assoc. Prof. S. R. Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 26 28. Complete the following reactions. 1. CH3CH2COCl 2. NaBH4, EtOH O O O AlCl3 AlCl3 1. 2. CH3CH2NH2 CH3H3C H3C CH3 1. O3; Zn 2. CH3OH, cat. HCl O O OCH3 1. CH3OH, cat. HCl 2. CH3MgBr, ether 3. HCl, excess H2O OH O OCH3 1. CH3OH, cat. HCl 2. PhMgBr, ether 3. HCl, excess H2O O OH O N CH2CH3 O H3C CH3 H3C CH3 OCH3H3CO O OCH3 H3CO OCH3 OH CH3 H3CO OCH3 CH3 OH CH3CH3 O H O OCH3 OCH3 OCH3 H OH Ph OCH3 OCH3 Ph H OH PhPh O © Assoc. Prof. S. R. Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 27 29. Complete the following reactions. Assume an extraction based-work up for all reactions. There are no “No Reaction” reactions present. Br O 1. CH3OH, cat. HCl 2. Mg, ether 3. CH3CHO 4. Na2Cr2O7, H2SO4 5. PhLi, ether 6. 3M HCl, H2O Br H3CO OCH3 MgBr H3CO OCH3 H3CO OCH3 H HO CH3 H3CO OCH3 O CH3 HO CH3 Ph O 1. BH3-THF; NaOH, H2O2 2. PCC, CH2Cl2 3. CH3CH2MgBr, ether 4. K2Cr2O7, H2SO4 5. CH3CH2CH2NH2 H OH H O H OH CH2CH3 H O CH2CH3 H N CH2CH3 CH2CH2CH3 © Assoc. Prof. S. R. Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 30 30. Complete the following reactions. Assume an extraction based-work up for all reactions. There are no “No Reaction” reactions present. 2. LiAlH4, ether 3. PCC, CH2Cl2 4. CH3CH2MgBr 5. K2Cr2O7, H2SO4 O O OEt 1. EtOH, cat. HCl 6. 3M HCl, H2O OEt C O OEt EtO OEt CH2OH EtO OEt C EtO O H OEt C EtO H HO CH2CH3 OEt C EtO O CH2CH3 C O CH2CH3 O © Assoc. Prof. S. R. Hitchcock, Department of Chemistry, Illinois State University, Normal, IL 61790-4160 31 30. Complete the following reactions. Assume an extraction based-work up for all reactions. There are no “No Reaction” reactions present. 1. O3 (ozone); Zn 2. Ph3P-CH2 3. BH3-THF; NaOH, H2O 4. PCC, CH2Cl2 5. 1. BH3-THF; NaOH; H2O2 2. PCC, CH2Cl2 3. MgClCH3O CH3 NH2 O CH2 H2C OH H C O H H C OH H H OCH3 CH3 OH H CH3 O H CH3 N H