TABLE 18-1 Some Common Classes of Carbonyl Compounds Class General Formula Class General Formula O O ' ' ketones R9C9RЈ aldehydes R9C9H O O ' ' carboxylic acids R9C9OH acid chlorides R9C9Cl O O ' ' 9 9 9 Ј 9 9 esters R C O R amides R C NH2 AAALBKS0 Figure Number: 18 00.01 T01 ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E length energy ketone CObond 1.23 Å 178 kcal/mol R (745 kJ/mol) 120° C O R 120° alkene C C bond 1.34 Å 146 kcal/mol (611 kJ/mol) AAALBKU0 Figure Number: 18 00.03 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E R R Ϫ C O ϩC O R R major minor AAALBKV0 Figure Number: 18 00.04 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E O O 9 9 9 9 9 9 9 CH3CH2CH2CH3 CH3 O CH2CH3 CH3CH2 C H CH3 C CH3 CH3CH2CH2 OH butane methoxyethane propanal acetone 1-propanol bp 0°C bp 8°C bp 49°C bp 56°C bp 97°C AAALBLI0 Figure Number: 18 00.17 UN 1-5 ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E about 1685 cmϪ1 O OϪ C C C C ϩ C C O 1685 cmϪ1 O 1690 cmϪ1 O 1745 cmϪ1 O 1815 cmϪ1 C CH3 H acetophenone 2-butenal cyclopentanone cyclopropanone AAALBLM0 Figure Number: 18 00.22 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E a carbon a carbon a carbon O O O Ј R CH2 C H R C CH3 R C CH2R dd2.4 9–d10 d2.1 d2.4 an aldehyde a methyl ketone other ketones AAALBLN0 Figure Number: 18 00.23 UN 1-3 ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E 0Hz 50Hz 0Hz 50Hz O C a bg H CH2 CH2 CH3 7 Hz splitting distance 7 Hz splitting distance 9.8d 9.7d 2.5d 2.4d 10 9 8 7 6 5 4 3 2 1 0 d (ppm) AAALBLO0 Figure Number: 18 01 ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E 44 31 14 24 O 208 23 44 24 31 23 14 30 C H3C CH2CH2CH2CH2CH3 30 208 200 180 160 140 120 100 80 60 40 20 0 AAALBLP0 Figure Number: 18 02 ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E + O . + + . CH3 C CH2CH3 CH3 C O CH2CH3 43 radical cation acylium ion ethyl radical m/z 72 m/z 43 (base peak) loss of 29 + O . + + . CH3 C CH2CH3 CH3CH2 C O CH3 57 radical cation acylium ion methyl radical m/z 72 m/z 57 loss of 15 100 43 80 O 60 CH3 C CH2CH3 40 ϩ abundance M 72 20 57 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 m/z AAALBLT0 Figure Number: 18 03 ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E 100 44 72 80 M Ϫ 28 O 60 ϩ 29 M C abg 40 abundance H CH CH CH 57 2 2 3 20 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 m/z O .+ + + . H C CH2CH2CH3 H C O CH2CH2CH3 29 m/z 72 m/z 29 loss of 43 + . H H O 57 .+ .O +O. + CH + . H C CH2 CH2 CH3 C 2 C CH2 CH3 H C H C loss of 15 H H β, γ cleavage stabilized cation m/z 57 McLafferty rearrangement m/z 72 m/z 44 (base peak) + loss of 28 AAALBLU0 Figure Number: 18 04 ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E g hydrogen OH+ + . O H . H C H H OH.+ H C C H C H H H C = + C C C HH C C C C H H H H H H HH H H H ethylene enol m/z 72 loss of 28 m/z 44 McLafferty rearrangement of butyraldehyde R .+ O H + H R O H + . O C . a b g A B R R' C C C CR = B R' CC + CC C C A B R A A B B R C R' B enol loss of alkene A A McLafferty rearrangement of a general ketone or aldehyde AAALBLW0 Figure Number: 18 05 ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E + − + − p* p* C O CO − + forbidden − + allowed n C O + + p nonbonding C O orbital − − "allowed" transition "forbidden" transition e ≅ 5000 – 200,000 e ≅ 10 – 200 AAALBLZ0 Figure Number: 18 06 ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E H O Na Cr O OH 2 2 7 H2SO4 borneol camphor (88%) Primary alcohols : aldehydes OH O O & 9 [oxidizing agent] 9 9 [overoxidation] 9 9 R CH2 −2 H R C H [O] R C OH primary alcohol aldehyde carboxylic acid AAALBMI0 Figure Number: 18 07.08 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E + CH OH 9 − CHO 2 N H CrO3Cl (PCC) cyclohexylmethanol cyclohexanecarbaldehyde (90%) AAALBMJ0 Figure Number: 18 07.09 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E R RЈ R RЈ (1) O3 CC C O ϩ O C (2) (CH3)2S H RЉ H RЉ AAALBMK0 Figure Number: 18 07.10 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E CH3 CH3 (1) O3 O (2) Me S 2 O H 1-methylcyclohexene 6-oxoheptanal (65%) AAALBML0 Figure Number: 18 07.11 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E G O O O AlCl3 R C Cl ϩ G C R ϩ C R R is alkyl or aryl; G is hydrogen, a halogen, or an activating group. G O O C Cl AlCl3 O2N O2N p-nitrobenzoyl chloride p-nitrobenzophenone (90%) AAALBMM0 Figure Number: 18 07.12 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E R H O H 2+ + Hg , H2SO4 H RCC H CC RCC H H2O HO H H alkyne enol (not isolated) methyl ketone Example H O C HO H C C H SO , Hg2+ + 2 4 CC H CH H 3 H2O ethynylcyclohexane enol cyclohexyl methyl ketone (90%) AAALBMO0 Figure Number: 18 07.14 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E RH O − (1) Sia2BH OH RCC H CC RCH2 C H (2) H2O2, NaOH H OH alkyne enol (not isolated) aldehyde Example H O C C CH2 C H (1) Sia2BH (2) H2O2, NaOH ethynylcyclohexane cyclohexylethanal (65%) AAALBMP0 Figure Number: 18 07.15 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E ϩ ϩ C4H9 —Li C4H10 S S n-butyllithium S Ϫ S butane H H H ϭ 1,3-dithiane, pKa 32 dithiane anion AAALBMY0 Figure Number: 18 07.25 P18.6 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E ϩ H , HgCl2 ϩ R X O H O S S S S 2 Ϫ alkylating agent H R (primary alkyl halide) H R H aldehyde dithiane anion thioacetal AAALBMZ0 Figure Number: 18 07.26 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E ϩ (1) BuLi (1) BuLi H , HgCl2 O 9 S S (2) PhCH2 Br S S (2) CH3CH2CH2Br S S H2O PhCH2 CH2CH2CH3 PhCH2 H PhCH2 CH2CH2CH3 1,3-dithiane thioacetal thioketal ketone AAALBNB0 Figure Number: 18 07.28 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E O O OϪLiϩ OH O ϩ Ϫ LiOH RЈ9Li H3O H2O R9C9OH R9C9O Li R9C9OϪLiϩ R9C9OH R9C9RЈ RЈ RЈ carboxylic acid lithium carboxylate dianion hydrate ketone AAALBNC0 Figure Number: 18 07.29 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E O Li O C OH 2 OLi OH C ϩ Ϫ H3O H2O C OLi C OH (phenyllithium) cyclohexane cyclohexyl phenyl ketone carboxylic acid dianion hydrate AAALBND0 Figure Number: 18 07.30 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E R′ Mg X R′ MgX R′ H R′ ϩ H Oϩ H 3 ϩ ϩ RCN C N C N C O NH4 R R R nucleophilic attack Mg salt of imine imine ketone AAALBNG0 Figure Number: 18 07.34 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E MgBr Example N O CN MgBr H Oϩ ϩ ether 3 benzonitrile phenylmagnesium bromide benzophenone imine benzophenone (magnesium salt) (80%) AAALBNH0 Figure Number: 18 07.35 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E O O Li AlH(O-t-Bu)3 R9C9Cl R9C9H lithium aluminum tri(t-butoxy)hydride acid chloride aldehyde AAALBNK0 Figure Number: 18 07.38 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E Example CH3 O CH3 O CH3 O SOCl Li+ −AlH(O-t-Bu) 9 9 2 9 9 3 9 9 CH3CHCH2 C OH CH3CHCH2 C Cl CH3CHCH2 C H isovaleric acid isovaleroyl chloride isovaleraldehyde (65%) AAALBNL0 Figure Number: 18 07.39 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E O O ' ' + Ј9 9 Ј9 9 + 9 + R2 CuLiR C Cl R C R R Cu LiCl a lithium dialkylcuprate (Gilman reagent) AAALBNN0 Figure Number: 18 07.41 UN ©2003 by Prentice Hall, Inc.