Reactions of aldehydes and ketones:

oxidation
reduction
nucleophilic addition

1) Aldehydes are easily oxidized, ketones are not.

2) Aldehydes are more reactive in nucleophilic additions than
ketones.
alkane alcohol

reduction reduction

aldehyde addition
ketone product
nucleophilic
oxidation addition

carboxylic acid
nucleophilic addition to carbonyl:


O OY
C + Y Z C
 Z
 Mechanism: nucleophilic addition to carbonyl

O RDS O
1) C + Z C
Z

O OY
2) C + Y C
Z Z
Mechanism: nucleophilic addition to carbonyl, acid
catalyzed

O OH
1) C + H C

OH RDS OH
2) C + HZ C
ZH

3) OH OH
C C + H
ZH Z
Aldehydes & ketones, reactions:
1) Oxidation
2) Reduction
3) Addition of cyanide
4) Addition of derivatives of ammonia
5) Addition of alcohols
6) Cannizzaro reaction
7) Addition of Grignard reagents
8) (Alpha-halogenation of ketones)
9) (Addition of carbanions)
1) Oxidation
a) Aldehydes (very easily oxidized!)

CH3CH2CH2CH=O + KMnO4, etc.  CH3CH2CH2COOH

carboxylic acid

CH3CH2CH2CH=O + Ag+  CH3CH2CH2COO- + Ag

Silver mirror
Tollen’s test for easily oxidized compounds like aldehydes.
(AgNO3, NH4OH(aq))
Ketones only oxidize under vigorous conditions via the enol.

+ KMnO4 NR

Cyclohexanone

+ KMnO4, heat HOOCCH2CH2CH2CH2COOH

adipic acid

OH

enol
 b) Methyl ketones:

O O
C + OI- C + CHI3
R CH3 R O-
iodoform
Yellow ppt
test for methyl ketones

O
CH3CH2CH2CCH3 + (xs) NaOI CH3CH2CH2CO2- + CHI3
2-pentanone
2) Reduction:
a) To alcohols

O H2, Ni OH
C C
H

NaBH4 or LiAlH4
then H+
 H2, Pt H
O
OH
cyclopentanol
cyclopentanone

O 1. NaBH4 OH
C CH3 CHCH3
2. H+
acetophenone 1-phenylethanol
 O H2, Pt
C CH2OH
H

benzaldehyde benzyl alcohol

CH3 LiAlH4 CH3

H+
CH3CHCH=O CH3CHCH2OH

isobutyraldehyde isobutyl alcohol

 hydride reduction
mechanism: nucleophilic addition; nucleophile = hydride

O RDS O
1) C + H: Al C + Al
H

O
2) C + Al H C O Al
H

Then + H+  alcohol
Reduction
b) To hydrocarbons

O NH2NH2, OH-
CH2
C
Wolff-Kishner

O Zn(Hg), HCl
C CH2
Clemmensen
O O
AlCl3
Cl +

Zn(Hg), HCl

n-pentylbenzene

cannot be made by Friedel-Crafts alkylation

due to rearrangement of carbocation
3) Addition of cyanide

O 1. CN- OH
C C
2. H+ CN
cyanohydrin

OH
O + NaCN; then H+
CN
 mechanism for addition of cyanide
nucleophilic addition

RDS O
O
1) + C N C
C
C
N

O ONa
2) C + Na+ C then + H+
C C
N N
Cyanohydrins have two functional groups plus one
additional carbon. Nitriles can be hydrolyzed to carboxylic
acids in acid or base:

OH OH
H2O, OH-
CH2CH C N CH2CH COO-
heat

OH
H2O, H+
CH2CH C N C C COOH
heat H H
4) Addition of derivatives of ammonia

O (H+)
+ H2N G + H2O
N G

O
H2N NH2 H2N OH
H2N N NH2
hydrazine hydroxylamine H
semicarbazide

O2N

H2N HN H2N HN NO2

phenylhydrazine

2,4-dinitrophenylhydrazine
 acid catalyzed nucleophilic addition mechanism followed by dehydration

1) O OH
C + H+ C

OH
OH
2) + H2N G C RDS
C
NH2 G

OH
3) C
C + H2O + H+
N
NH2 G G
 CH2 CHO + H2NOH CH2 CH NOH
hydroxylamine
phenylacetaldehyde an oxime

O H+ O
O + H2NHNCNH2 NHNCNH2
semicarbazide
cyclohexanone a semicarbazone

CH3CH2CH2CH2CHO + NH2 NH CH3CH2CH2CH2CH N NH

pentanal a phenylhydrazone
phenylhydrazine
 melting points of derivatives
ketones bp semi- 2,4-dinitro- oxime
carbazone phenylhydrazone

2-nonanone 195 119 56

acetophenone 202 199 240 60
menthone 209 189 146 59
2-methylacetophenone 214 205 159 61
1-phenyl-2-propanone 216 200 156 70
propiophenone 220 174 191 54
3-methylacetophenone 220 198 207 55
isobutyrophenone 222 181 163 94
5) Addition of alcohols

O OR
+ ROH, H+ C
C
OR acetal

OH
C
OR hemiacetal
Mechanism = nucleophilic addition, acid catalyzed

O OH
1) + H C
C

RDS OH
OH2 ROH C
2) +
C HOR

OH OH
3) C C + H
HOR OR
 (xs) EtOH, H+ OEt
CH2CHO CH2 CH
OEt
acetal

OCH3
O (xs) CH3OH, dry HCl
OCH3

ketal
 CHO
H OH H OH H OH
HO HO
HO HO H HO
HO OH H OH HO H
H OH H OH
H H H OH H OH
CH2OH

nucleophilic addition of -OH on carbon 5 to the aldehyde functional group

H OH
CHO HO
CH O HO
H OH HO H
H OH H OH
HO H HO H H OH
H OH 
H OH
H OH HOH2C H H OH
CH2OH OH HO
HO
rotate C-5 OH to rear HO OH 
H OH
H H
6) Cannizzaro reaction. (self oxidation/reduction)
a reaction of aldehydes without α-hydrogens

CHO CH2OH COO-

conc. NaOH
+
Br Br Br

conc. NaOH
H2C=O CH3OH + HCOO-
Formaldehyde is the most easily oxidized aldehyde. When
mixed with another aldehyde that doesn’t have any alpha-
hydrogens and conc. NaOH, all of the formaldehyde is
oxidized and all of the other aldehyde is reduced.
Crossed Cannizzaro:

CH=O CH2OH
conc. NaOH
+ H2C=O + HCOO-
OCH3 OCH3
OH OH
vanillin
7) Addition of Grignard reagents.

O O MgBr
C + RMgX C
R

O MgBr OH
C + H2O C + Mg(OH)Br
R R
larger alcohol
 mechanism = nucleophilic addition

O RDS O
1)
C + RMgBr C + MgBr
R

O OMgBr
2) + MgBr C
C
R R
#3 synthesis of alcohols. Used to build larger molecules
from smaller organic compounds.

O
H+
RMgX + C RCH2OMgX RCH2OH
H H
1o alcohol + 1 C
formaldehyde

O H+
RMgX + R'CHOMgX R'CHOH
C
R' H R
R
other aldehydes 2o alcohol + X C's
 R' R'
O H+
R-MgX + C R-COMgX R-COH
R' R" R"
R"
ketone
3o alcohol + X C's

O H+
RMgX + RCH2CH2OMgX RCH2CH2OH
H2C CH2
ethylene oxide 1o alcohol + 2 C's
Aldehydes & ketones, reactions:
1) Oxidation
2) Reduction
3) Addition of cyanide
4) Addition of derivatives of ammonia
5) Addition of alcohols
6) Cannizzaro reaction
7) Addition of Grignard reagents
8) (Alpha-halogenation of ketones)
9) (Addition of carbanions)
Planning a Grignard synthesis of an alcohol:
a) The alcohol carbon comes from the carbonyl
compound.
b) The new carbon-carbon bond is to the alcohol carbon.

O OH
H+
C + RMgX C
R

New carbon-carbon bond

“The Grignard Song” (sung to the tune of “America the Beautiful”)
Harry Wasserman

The carbonyl is polarized,

the carbon end is plus.
A nucleophile will thus attack
the carbon nucleus.

The Grignard yields an alcohol

of types there are but three.
It makes a bond that corresponds
from “C” to shining “C.”
 CH3 O
H2O
CH3CH2CH2CH2 C CH3 CH3CH2CH2CH2MgBr + CH3CCH3
OH
2-Methyl-2-hexanol

or

CH3 O
H2O
CH3CH2CH2CH2 C CH3 CH3CH2CH2CH2CCH3 + CH3MgBr
OH
2-Methyl-2-hexanol
 HX Mg
ROH RX RMgX

H2O larger
alcohol
ox.
R´OH -C=O
Stockroom:
alcohols of four-carbons or less:
(methanol, ethanol, 1-propanol, 2-propanol, 1-butanol,
2-butanol, 2-methyl-2-propanol, 2-methyl-1-propanol.)
benzene
cyclohexanol
any needed inorganic reagents or solvents.
 Grignard synthesis of 4-methyl-2-pentanol from alcohols of
four-carbons or less:
Step one: determine the carbonyl compound and Grignard
reagent that you would use:

CH3 H2O CH3

CH3CHCH2MgBr + CH3CH=O CH3CHCH2CHCH3
OH

Step two: show the syntheses of the Grignard reagent and

the carbonyl compound from alcohols…
 CH3 HBr CH3 Mg CH3
CH3CHCH2OH CH3CHCH2Br CH3CHCH2MgBr

H+

K2Cr2O7 CH3
CH3CH2OH CH3CH=O CH3CHCH2CHCH3
special cond. OH

4-methyl-2-pentanol
2-phenyl-2-propanol

Br2,Fe Mg
Br MgBr

H2O OH
C CH3
CH3

OH CrO3 O 2-phenyl-2-propanol
CH3CHCH3 CH3CCH3
1-methylcyclohexanol

HBr Mg
CH3OH CH3Br CH3MgBr
H3C OH
H2O
O
H OH
NaOCl
1-Methylcyclohexanol

Cyclohexanol Cyclohexanone
cyclohexylmethanol

H OH H Br H MgBr
HBr Mg

H CH2OH
H2O

K2Cr2O7
CH3OH H2C=O Cyclohexylmethanol
special cond.
 ketone aldehyde RCOOH

ROR ROH

alkene

RX

Alcohols are central

to organic syntheses RH alkyne
 HX Mg
ROH RX RMgX

H2O larger
alcohol
ox.
R´OH -C=O
Using the Grignard synthesis of alcohols we can make any
alcohol that we need from a few simple alcohols. From
those alcohols we can synthesize alkanes, alkenes, alkynes,
alkyl halides, ethers, aldehydes, ketones, carboxylic acids…

eg. Outline all steps in a possible laboratory synthesis of

3-methyl-1-butene from alcohols of four carbons or less.

CH3
CH3CHCH=CH2
Retrosynthesis:
alkenes, syntheses:
1. Dehydrohalogenation of an alkyl halide
2. Dehydration of an alcohol
3. Dehalogenation of a vicinal dihalide
4. Reduction of an alkyne

Methods 3 & 4 start with compounds that are in turn

made from alkenes.
Dehydration of an alcohol?

CH3 H+
CH3CHCHCH3 yields a mixture of alkenes
OH

CH3 H+
CH3CHCH2CH2-OH yields a mixture of alkenes

E1 mechanism via carbocation!

Dehydrohalogenation of an alkyl halide?

CH3 KOH(alc)
CH3CHCHCH3 yields a mixture of alkenes
Br

CH3 KOH(alc) CH3

CH3CHCH2CH2-Br CH3CHCH=CH2

only product 

E2 mechanism, no carbocation, no rearrangement

 CH3 HBr CH3
CH3CHCH2CH2-OH CH3CHCH2CH2-Br

1o alcohol, SN2 mechanism, no rearrangement!

CH3 KOH(alc) CH3

CH3CHCH2CH2-Br CH3CHCH=CH2

Use the Grignard synthesis to synthesize the intermediate

alcohol from the starting materials.
 CH3 PBr3 CH3 Mg CH3
CH3CHCH2-OH CH3CHCH2Br CH3CHCH2MgBr

K2Cr2O7
CH3OH H2C=O
special cond. H2O

CH3
CH3CHCH2CH2-OH

HBr

CH3 KOH(alco) CH3

CH3CHCH=CH2 CH3CHCH2CH2-Br