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Chapter 18

RCHO : aldehyde
RCOR' : ketone
easily oxidized.
diIIicult to be oxidized.
CO carbonyl group
aldehyde is more reactive than
ketone toward nuclophilic
addition.
nomenclature : aldehyde
ketone - one ( p659 & p660 )
aldehyde
ketone
polar, no hydrogen-bonding
lower aldehydes and ketones are soluble in H
2
O
( presumably due to hydrogen-bonding )
Iormaldehyde ( CH
2
O, bp 21
o
) :
C O
R
R'
sp
+
2
Iormalin (aq soln)
solid polylmers
OCH
2
OCH
2
paraIormaldehyde
trioxane
O O
O
CH
2
acetaldehyde ( CH
3
CHO, bp 20
o
) :
CH
3
CH O
O O
O CH
3
H
3
C
CH
3
H


paraldehyde
RCH
2
OH RCHO
PCC
CH
2
Cl
2
ArCH
3
ArCHCl
2
ArCHO
Cl
2
H
2
O
CrO
3
Ac
2
O
ArCH
OAc
OAc
ArCHO
H
2
O
- al
O

RCOCl or ArCOCl
RCHO or ArCHO
LiAlH(OBu )
3
(CH
3
OCH
2
CH
2
)
2
O
78
o
C
RCOOH or ArCOOH PCl
5
PCl
3
SOCl
2
RCHR'
OH
or K
2
Cr
2
O
7
ArH

AlCl
3

HCl : Eriedel CraIts acylation


R C Cl
O

AlCl
3
RC O RC O
CrO
3

AlCl
4

ArH

RC O
Ar
H
C R
O
Ar
H
C R

AlCl
4

C

HCl

AlCl
3
acylium ion
maybe a complex
C R
Cl
O
AlCl
3
O
2
N
C
b a
a

C Cl
PCl
5
HNO
3
H
2
SO
4
COOH
KMnO
4
CH
3
b
no rxn
C Cl
t
R C R'
O
Cl
O
C R
Ar C R
O
O
R Ar
O
O O
O
O
2
N
O
2
N
COOH
O
2
N

C R
Zn(Hg)
HCl
CH
2
R Clemmensen red
N
2
H
4
OH
CH
2
R WolII-Kishner red

R X RLi
CuX
R
2
CuLi
Ar X
Li
Li
ArLi
CuX
Ar
2
CuLi
R'
2
CuLi

R C Cl
O
R C R'
O
cI)
R C Cl
O

R' MgX R C R'


OH
R'
RMgX
RLi
react with NO
2
, CN, C
O
COOR. ,
R
2
CuLi does not. cI) halide
COCl O
2
N Me
2
CuLi

CCH
3
O
2
N
CH
3
OCCH
2
CH
2
COCl
CuLi
2

CH
3
OCCH
2
CH
2
CCH
2
CH
2
CH
CH
3
CH
3
O
H
nucleophilic
addition
acidic proton (deprotonated by strong bases)
+

C
R'
R
O
Z
C
R'
R
O
Z


C R' O
Z
R
H
2
O
C R' OH
Z
R
trigonal
( sterically relatively unhindered )
aldehyde is more reactive than ketone due to electronic and steric Iactors.
tetrahedral
O
O
O O O
R Ph
O
C
vs
R R'
O
C
: Ph is more electronegative
R Ph
O
C Is
more reactive ? no due to resonance eIIect
C
R
O

C
R'
R
H
C
R'
R
Z
C R'
R
Z

+
C R'
R
OH
Z
lower Ea
catalyzed by acids (protic or Lewis acid)
RCHO Ag(NH
3
)
2
RCOO
Ag


to prevent precipitation (Ag
2
O)
in basic conditions,
NH
3
is added.
Tollens' reagent
silver
mirror
1) Ag(NH
3
)
2
2) H

RCH CHCOOH
C C C
OH
H
C C C
O
H H
C C C
OH
H
enol keto
enol
diIIicult to oxidize it.
the double bond oI the enol
Iorm is cleaved in vigorous
oxidation condition.
O OH OH
RCH CH CH O

C C
CH
3
KOCl
C
CH
3
COOH CHCl
3
(haloIorm rxn)
PhCH CH
3
CH
2
C CH
3

O
LiAlH
4
OAlH
3
H O H Al
4
OH
O
O
CH
3
O
PhCH
PhCH


CH
3
CH CH
3
CH
2
CH
2
CH
2
OH
H
2
Ni
CH
3
CH

CH
3
CH
PhCH CHCHO PhCH CH CH
2
O
9-BBN
H
2
NCH
2
CH
2
OH
PhCH CHCH
2
OH
PhCH O

CH
3
CH
B
OH
OH
resorcinol
COOH
ZnCl
2
OH
OH
C(CH
2
)
4
CH
3
O
Zn(Hg), HCl
or NH
2
NH
2
KOH(t BuOK)
OH
OH
C O R MgX
C
R
OMgX

C O
H , CN

C
O
CN C
OH
( a highly acidic medium
retards the rxn)
(cyanohydrin)
H
C
O
2
N
O
H , CN

H
C
O
2
N
CN
OH
HCl
H
C
O
2
N
COOH
OH
Et C
Me
O
H , CN

C
Me
OH
Et
C
Me
OH
Et COOH
H
2
SO
4
C
CH
3
CH
3
CH
COOH
CHCHO
O O
O
CN
CN

C O
H
2
N OH

H
C
OH
NH OH C N OH
hydroxylamine
oxime
H
2
N NH Ph
phenylhydrazine

H
C
OH
H
N
H
N Ph
C N NHPh
phenylhydrazone
H
2
NNH C NH
2
O
H
C
OH
H
N
H
N C
O
NH
2
C N
H
N C NH
2
semicarbazide
semicarbazone
( stored as salts, liberated by adding base :
PhNHNH
3
Cl

CH
3
COONa PhNHNH
2

CH
3
COOH NaCl )

C O

H
C OH
H
2
N G
H
3
N G

H
N
H
H
G
C
H
N G
H
2
O
the right acidity is necessary.
R C
R'
O

2R''OH
dry
HCl
R C
R'
OR''
OR''
acetal
ketal
O
C
HO

R C O

H
R C OH
R'OH
C
hemiacetal
(usually very unstable)

H
R C R C
R'OH
C C
acetal
key intermediate
necessary to remove H
2
O
use benzene, toluene or xylene as a solvent
to Iorm azeotrope.
R C
H
OR'
OR'
H
2
O
RCH

2R'OH

H
very stable toward bases
CH
aq NaOH
ArCH
2
OH

ArCOO (Cannizzaro rxn)
Ar
H
C O OH

Ar C O
OH
H
C O
C O
OH
C O
H
H

H
2
C O CH
3
OH HCOO
O
2
N CHO
50 NaOH
35 NaOH
conc. NaOH

O
2
N CH
2
OH O
2
N COO

H
3
CO CHO HCHO
O
2
N CH
2
OH HCOO
(crossed Cannizzaro rxn)
(others are possible but not Iormed
when an aldehyde is HCHO)
key intermediate
Ar O
Ar
Ar Ar
O
R C OH
HOR'
H H
H
OH R
OR'
H
H
OR'
OR' R
H
OR' H
OR' R
H
OR'
H
OH
2
OR'


RC O
H
RC O
R
aldehyde
ketone
O C

: carbonyl group typical rxn : nucleophilic addition
Nucleophile
electrophile
RX Mg
RMgX
ether
RX Li
RLi
ether
O
R"
R'

R MgX
R Li
or
C OMgX
R"
R
R'
H
2
O
RR'R"COH
generally RLi is more reactive than RMgX
due to more electropositive Li.
MgBr

CH
2
O
OH
CH
3
CH O
OH

O
OH
MgBr
H
2
C CH
2
simple alcohol alkyl halide Grignard reagent
simple alcohol aldehyde or ketone
more complited
alcohol
( explain limitations )
( primary alc )
( secondary alc )
( tertiary alc )
OH
H
3
C
H
3
C
O






CH
3
CH
2
OH
HBr
PCC
CH
3
CH
2
Br
CH
3
CH O
CH
3
CH
2
MgBr
CH
3
CH
2
CHCH
3
OH
PBr
3
CrO
3
CH
3
CH
2
CH
Br
CH
3
Mg
CH
3
CH
2
CH MgBr
CH
3
CH
3
CH
2
C CH
3
O
CH
3
CH
2
CH C CH
2
CH
3
OH
CH
3
CH
3 How can we synthesize CH
3
CH
2
CH
2
CH
2
C CH
3
CH
3
OH
when all alcohols oI Iour carbons or Iewer are available ?
retrosynthetic analysis
CH
3
CH
2
CH
2
CH
2
C CH
3
OH
CH
3
CH
3
CH
2
CH
2
CH
2
MgBr

C
O
CH
3
CH
3
Mg CrO
3
CH
3
CH
2
CH
2
CH
2
OH CH
3
CH
2
CH
2
CH
2
Br CH
3
CHCH
3
OH
Ph
OH
Ph
Ph
OH
OH
OH




CH
3
CH
2
CH
2
CH
2
C CH
3
OH
CH
3
CH
3
CH
2
CH
2
CH
2
C O
CH
3

CH
3
MgBr CH
3
Br
CH
3
OH
CH
3
CH
2
CH
2
CH
2
CHCH
3
OH
CH
3
CH
2
CH
2
CH
2
MgBr
CCH
3
O
alcohol
PBr
3
or PI
3
TsCl
acid
HX
R X
KOH
alkene
R OTs
base
alkene
alkene
R X
maybe not preIIerred due to rearrangment
alkane CH
3
CH
2
CH
2
CH
2
OH
How to synthesize CH
3
CH
CH
3
CH CH
2
Irom alcohols oI Iour carbons or Iewer?
CH
3
CH CH CH
3
CH
3
OH
CH
3
CH CH CH
3
CH
3
Br
H

KOH
CH
3
C CHCH
3
CH
3
major
CH
3
CH CH
2
CH
2
OH
CH
3
H

CH
3
CHCH
2
CH
2
Br
CH
3
alcoholic
KOH
CH
3
CHCH CH
2
CH
3
PBr
3
CH
3
CH CH
2
CH
2
OH
CH
3
CH
2
O CH
3
CHCH
2
MgBr
CH
3
Mg
CH
3
CHCH
2
Br
CH
3
PBr
3
CH
3
CHCH
2
OH
CH
3
ox
CH
3
OH
H
Py
CH
3
C CHCH
3
CH
3

limitations
THP protecting group
tests Ior alc
1
o
OH , 2
o
OH
MnO
4
H
2
CrO
4
dark red
MnO
2
Cr

( brown )
( bluish green )
Lucas test : conc. HCl ZnCl
2
3
o
OH : react immediately ( cloudy soln )
allyl alc reacts immediately
2
o
OH : react within 5 min
1
o
OH : no rxn at RT
NaOH X
2
NaOX
CH
3
C
OH
R
H

NaOX C CH
3
O
R C CX
3
O
R
RCOOH HCX
3
haloIorm
(test)
CH
OH
R CH R'
OH
HIO
4
R'CHO RCHO
CH
O
R CH R'
O
HIO
4
R'COOH RCOOH
CH
OH
R CH CH
OH
R'
OH
HIO
4
RCHO HCOOH R'CHO