TABLE 18-1 Some Common Classes of Carbonyl Compounds
Class General Formula Class General Formula O O ' ' ketones R9C9R aldehydes R9C9H O O ' ' carboxylic acids R9C9OH acid chlorides R9C9Cl O O ' ' 9 9 9 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 C O C 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 cm 1 O O C C C C C C
O 1685 cm 1 O 1690 cm 1 O 1745 cm 1 O 1815 cm 1 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 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 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 ©2003 by Prentice Hall, Inc. A Pearson Company 160 3 CH . 150 loss of 15 + + 2 140 CH 3 loss of 28
g H 130 C H + CH 2 . . C O 3 CH + 120 2 CH H ab 2 CH 110 CH 57 2 C O z / 44 (base peak) m CH loss of 43 z 100
H . 2 / m + stabilized cation + CH 90 + H C H O z 29 /
80 . C O . z m . . / C M m AAALBLU0 72 72 H z 70 / H m 60 57 28 + + . . 3 3 50 44 M CH CH 2 40 CH 2 57 2 72 CH z 29 / CH 30 m 2 cleavage C O 29 γ 20 CH , β McLafferty rearrangement McLafferty H C O 10 0
80 60 40 20
100 abundance H Figure Number: 18 04 WADE 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 R R R (1) O3 CC C O O C (2) (CH3)2S H R H R
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 G C R 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 C4H9 —Li C4H10 S S n-butyllithium S S butane
H H H 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 H , HgCl2 R X O H O S S S S 2 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 (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 O Li OH O LiOH R 9Li H3O H2O R9C9OH R9C9O Li R9C9O Li R9C9OH R9C9R R R 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 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′ H O H 3 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 O 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 ' ' + 9 9 9 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. WADE A Pearson Company ORGANIC CHEMISTRY, 5E 9 ++ 2RLi CuIR2CuLi LiI
O ' Example O C ' Cl C
(1) Li Cl ( (CuLi (2) CuI 2
80%
AAALBNO0 Figure Number: 18 07.42 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E Nuc. −
Nuc Nuc H R δ+ δ− − H Nuc C O C O C O + Nuc − R R R R R nucleophilic attack alkoxide product
AAALBOC0 Figure Number: 18 07.56 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E H HO CH3 CH3 H CH3 H H C O C O C O H O 2 CH3 CH3 CH3 acetone protonated, activated acetone
CH3 CH3 CH3 H H H O C O O C O H H O C O H H O 2 3 CH3 H2O H CH3 CH3 attack by water loss of H acetone hydrate
AAALBOG0 Figure Number: 18 07.60 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E Basic conditions (strong nucleophile) Step 1: Addition of the nucleophile. Step 2: Protonation. & & & H9Nuc
Nuc C"O Nuc9C9O Nuc9C9O9H Nuc & & & Reverse reaction: & − & Nuc &
Nuc9C9O9H Nuc9C9O Nuc C"O & & &
Acidic conditions (weak nucleophile, activated carbonyl) Step 1: Protonation. Step 2: Addition of the nucleophile.
+ − H H − &
& & & H Nuc & & Nuc
C"O C"O C9O Nuc9C9O9H
& & & &
Reverse reaction:
& H H
& & & & &
Nuc9C9O9H Nuc C"O C O C"O
& & & & Nuc9H
AAALBOI0 Figure Number: 18 07.67 Summ ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E The Wittig reaction
R R Ph CO CPPh R R Ph ketone or aldehyde phosphorus ylide
R R C C Ph3P O R R alkene
AAALBON0 Figure Number: 18 07.68 UN ©2003 by Prentice Hall, Inc. WADE A Pearson Company ORGANIC CHEMISTRY, 5E Ph H d Ph P C d CH 9Li H H 2 Ph R C4H10 Ph Ph CH2CH2CH3 butane Ph P H C X Ph P C H butyllithium Ph Ph R R Ph H LiX triphenylphosphine alkyl halide X Ph P C phosphonium salt Ph R phosphorus ylide
Examples Br 9 Bu Li Ph3P CH3 Br Ph3P CH3 Ph3P CH2 methyltriphenylphosphonium salt ylide