368 ALCOHOLS, DIOLS AND THIOLS 15.11 (b) The substrate is a secondary alcohol and so gives a ketone on oxidation with sodium dichro mate.2-Octanone has been prepared in 92-96%o yield under these reaction conditions CH3 CH(CH2)_CH3 H( Na2C2→CH3C(CH2)CH OH 2-Octanol 2-Octanone (c) The alcohol is primary, and so oxidation can produce either an aldehyde or a carboxylic acid, depending on the reaction conditions. Here the oxidation is carried out under anhydrous condi tions using pyridinium chlorochromate(PCC), and the product is the corresponding aldehyde CHaCHCH,CH, CH,CH,CH,OH CHaCH,CH,CH,,,CH Heptanal 15.12 (b) Biological oxidation of CH,CD,OH leads to loss of one of the C-1 deuterium atoms to NAD The dihydropyridine ring of the reduced form of the coenzyme will bear a single deuterium CNH alcohol CNH CH CD.OH+ - Ch cd+ L.I-Dideuterio- NAD 1-Deuterio NADD ethanal (c) The deuterium atom of CHa CH,OD is lost as D. The reduced form of the coenzyme contains no deuterium CNH, alcohol CNH, CH CHOD CHCH D Ethanol-O-d NAD Ethanal NADH 15.13 (b) Oxidation of the carbon-oxygen bonds to carbonyl groups accompanies their cleav (CH3)2CHCHCH--CHCH,C6H5 HIO:(CH ),CHCH CH+ HCCH2C6H5 I-Phenyl-5-methyl-2, 3-hexanediol 3-Methylbutanal 2-Phenylethanal (c) The Ch,OH group is cleaved from the ring as formaldehyde to leave cyclopentanone O 0+ HCH CHOH Back Forward Main Menu TOC Study Guide Toc Student OLC MHHE Website15.11 (b) The substrate is a secondary alcohol and so gives a ketone on oxidation with sodium dichro￾mate. 2-Octanone has been prepared in 92–96% yield under these reaction conditions. (c) The alcohol is primary, and so oxidation can produce either an aldehyde or a carboxylic acid, depending on the reaction conditions. Here the oxidation is carried out under anhydrous condi￾tions using pyridinium chlorochromate (PCC), and the product is the corresponding aldehyde. 15.12 (b) Biological oxidation of CH3CD2OH leads to loss of one of the C-1 deuterium atoms to NAD. The dihydropyridine ring of the reduced form of the coenzyme will bear a single deuterium. (c) The deuterium atom of CH3CH2OD is lost as D. The reduced form of the coenzyme contains no deuterium. 15.13 (b) Oxidation of the carbon–oxygen bonds to carbonyl groups accompanies their cleavage. (c) The CH2OH group is cleaved from the ring as formaldehyde to leave cyclopentanone. HIO4 OH CH2OH 1-(Hydroxymethyl)- cyclopentanol O Cyclopentanone O HCH Formaldehyde (CH3)2CHCH2CH CHCH2C6H5 OH OH 1-Phenyl-5-methyl-2,3-hexanediol (CH3)2CHCH2CH O HCCH2C6H5 O 3-Methylbutanal 2-Phenylethanal HIO4 CH3CH2OD D CH3CH O alcohol dehydrogenase CNH2 N R O CNH2 H H N R O Ethanol-O-d Ethanal NADH NAD CH3CD2OH H CH3CD O alcohol dehydrogenase CNH2 N R O CNH2 H D N R O 1,1-Dideuterio￾ethanol 1-Deuterio￾ethanal NAD NADD CH3CH2CH2CH2CH2CH2CH2OH 1-Heptanol Heptanal CH3CH2CH2CH2CH2CH2CH O PCC CH2Cl2 CH3CH(CH2)5CH3 OH 2-Octanol CH3C(CH2)5CH3 O 2-Octanone Na2Cr2O7 H2SO4, H2O 368 ALCOHOLS, DIOLS, AND THIOLS Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website