3 Alcohols Cannot Be Oxidized Carbon does not have hydrogen,so oxidation is difficult and involves the breakage of a C-C bond. Chromic acid test is for primary and secondary alcohols because tertiary alcohols do not react.Orange color of Cr(VID)turns green -Cr(IID);3 alcohol is not oxidized, therefore no color change
3° Alcohols Cannot Be Oxidized • Carbon does not have hydrogen, so oxidation is difficult and involves the breakage of a C—C bond. • Chromic acid test is for primary and secondary alcohols because tertiary alcohols do not react. Orange color of Cr(VII) turns green - Cr(III); 3o alcohol is not oxidized, therefore no color change
Sodium Hypochlorite (NaOCl) OH NaOCl H2O+NaCl H20 cyclohexanol cyclohexanone (85%) 20Pearson Eacaton re Sodium hypochlorite (household bleach)can oxidize alcohols without heavy metals or generating hazardous waste. This is a much better option for acid-sensitive compounds 2013 Pearson Education,Inc. Chapter 11
© 2013 Pearson Education, Inc. Chapter 11 12 Sodium Hypochlorite (NaOCl) • Sodium hypochlorite (household bleach) can oxidize alcohols without heavy metals or generating hazardous waste. • This is a much better option for acid-sensitive compounds
Swern Oxidation OH CH;(CH2)s-C-H DMSO,(COCI)2 Bt,N,CH,C,-60C CH3(CH2)s- H H decan-1-ol decanal(85%) Dimethylsulfoxide (DMSO),with oxalyl chloride and hindered base,oxidizes 2 alcohols to ketones and 1 alcohols to aldehydes (same as PCC) 2013 Pearson Education,Inc. Chapter 11 13
© 2013 Pearson Education, Inc. Chapter 11 13 Swern Oxidation • Dimethylsulfoxide (DMSO), with oxalyl chloride and hindered base, oxidizes 2 alcohols to ketones and 1 alcohols to aldehydes (same as PCC)
Oxidation Summary CH2CO2H Na2Cr207 H2S04 ⊕ NH CH2CH2OH CrO3Cl CH2CHO 00 川 CH-CHO DMSO.CICCCI (CH3CH2)3N,in CH2Cl2
Oxidation Summary CH2 CH2OH NH CrO3 C l N a2 C r2O7 H2 SO4 CH2 CHO CH2 CO2H DMSO, ClCCCl OO (CH3 C H2) 3N, in CH2 C l2 CH2 CHO
Reduction Summary 1)LiAIH 4 CH2CO2H 2)H30 CH2CH2OH 1)NaBH CH2CHO 2)H30 or CH-CHO H2,Raney Ni
Reduction Summary CH2 CH2OH CH2CHO CH2CO2H CH2CHO 1) LiAlH 4 2) H3O + 2) H3O + 1) NaBH4 or H2, Raney Ni