18 Wade pdfs - webs.ucm.eswebs.ucm.es/info/btg/personales/jmsanchez/Text_images_18.pdf ·...
55
TABLE 18-1 Some Common Classes of Carbonyl Compounds Class General Formula Class General Formula ketones aldehydes O ' R 9 C 9 R O ' R 9 C 9 H carboxylic acids acid chlorides O ' R 9 C 9 OH O ' R 9 C 9 Cl esters amides O ' R 9 C 9 O 9 R O ' R 9 C 9 NH 2 ©2003 by Prentice Hall, Inc. A Pearson Company Figure Number: 18 00.01 T01 WADE ORGANIC CHEMISTRY, 5E AAALBKS0
Transcript of 18 Wade pdfs - webs.ucm.eswebs.ucm.es/info/btg/personales/jmsanchez/Text_images_18.pdf ·...
TAB
LE 1
8-1
Som
e Co
mm
on
Classes o
f Carb
on
yl Co
mp
ou
nd
s
Class
Gen
eral Form
ula
Class
Gen
eral Form
ula
ketonesaldehydes
O'R
9C
9R
�
O'R
9C
9H
carboxylic acidsacid chlorides
O'R
9C
9O
H
O'R
9C
9C
l
estersam
ides
O'R
9C
9O
9R
�
O'R
9C
9N
H2
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 00.01 T01 W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
KS0
ketoneC
Obond
length
1.23 Å178 kcal/m
ol(745 kJ/m
ol)
energy
alkeneC
Cbond
1.34 Å146 kcal/m
ol(611 kJ/m
ol)
CO
RR 120°120°
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 00.03 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
KU
0
R
CO
R
R�C
R
O�
minor
major
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 00.04 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
KV
0
butanebp 0°C
methoxyethane
bp 8°Cpropanalbp 49°C
acetonebp 56°C
1-propanolbp 97°C
OO
CH
3 CH
2 CH
2 CH
3C
H3 9
O9
CH
2 CH
3C
H3 9
C9
CH
3C
H3 C
H2 C
H2 9
OH
CH
3 CH
2 9C
9H
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 00.17 UN
1-5W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
LI0
O
O
acetophenone
CC
C
O�
CC
C�
about 1685 cm�
1
O
CH
3
OCH
2-butenalcyclopentanone
O
cyclopropanone
1685 cm�
11690 cm
�1
1745 cm�
11815 cm
�1
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 00.22 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
LM0
OCH
2C
R
carbon
H
2.49
–10
an aldehyde
RC O
CH
3
2.1a m
ethyl ketone
RC O
CH2.4
other ketones 2 R�
dd
dd
a
d
carbona
carbona
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 00.23 UN
1-3W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
LN0
01
23
45
67
89
10
d (ppm)
a
O
H
C
CH
2C
H2
CH
3
bg
9.8d
9.7d
0Hz
50Hz
7 Hz splitting distance
2.5d
2.4d
0Hz
50Hz
7 Hz splitting distance
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 01 W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
LO0
200180
160140
120100
8060
4020
0
O
CH
2 CH
2 CH
2 CH
2 CH
3
44
44
208
208
3024
31
2423 14
30
31
2314
H3 C
C
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 02 W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
LP0
160150
140130
120110
10090
8070
6050
4030
2010
10080604020
abundance
m/z
0
O
CH
2 CH
3C
CH
3
O
CH
2 CH
3C
H2 C
H3
CC
H3
O+
+C
CH
343
radical cationm
/z 72acylium
ionm
/z 43 (base peak)ethyl radical
loss of 29
radical cationm
/z 72acylium
ionm
/z 57m
ethyl radicalloss of 15
.
CH
3O
++
CC
H3 C
H2
57
+
O
CH
2 CH
3C
CH
3
. +
43
57
72M
�
.
.
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 03 W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
LT0
.
..
. .
160150
140130
120110
10090
8070
60
57
29
445040
3020
10
10080604020
abundance
m/z
m/z 72
m/z 29
m/z 57
loss of 43
0
72M�
M �
28
O+
CC+
C
O
H
HH
H+
+
C29C
H2 C
H2 C
H3
CH
2 CH
2 CH
3H
O
β, γ cleavagestabilized cation
loss of 15
C
57
CH
2C
H2
CH
2
.
.
.
CC
+O
H
HH
CH
2C
H3
CH
3H
O
. +. ++
HC
H2 C
H2 C
H3
C O
abg
m/z 72
m/z 44 (base peak) + loss of 28
McL
afferty rearrangement
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 04 W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
LU0
m/z 72
CC a
bg
CC
R
R
OH
CC
HH
AA
BB
HH
HH
O
g hydrogen
HH
C C
CC
AA
B
B
HO
RR
C C
CH
H
HH
=
=
+H
OH
H
C
H
C
HH
OH
H
C C
Hethylene
loss of 28 enol
m/z 44
enolloss of alkene
McL
afferty rearrangement of butyraldehyde
McL
afferty rearrangement of a general ketone or aldehyde H H
H
C C
C
R 'C
C HO
+R
CC
RR
AA
BB'
R '
. +. +
. +
. +. +
. +
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 05 W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
LW0
C
allowed
p*p
O
+
+ −
−C
OO
+
+ −
−
nonbondingorbital
C
C
O
"allowed" transition
e ≅ 5000 – 200,000"forbidden" transitione ≅ 10 – 200
+
− +
−
p*n
forbidden
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 06 W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
LZ0
Na2 C
r2 O7
H2 SO
4
OO
H&
[oxidizing agent]−2 H
[overoxidation][O
]carboxylic acid
primary alcohol
R9
CH
2R
9C
9O
H
O
aldehydeR
9C
9H
Prim
ary alcohols : aldehydes
O
camphor
(88%)
HOH
borneol
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.08 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
MI0
CH
2 OH
cyclohexylmethanol
N9
H C
rO3 C
l −+
(PCC
)
CH
O
cyclohexanecarbaldehyde(90%
)©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.09 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
MJ0
H R
R�
R�
CC
(1) O3
(2) (CH
3 )2 SH R
CO
�O
C
R�
R�
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.10 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
MK
0
CH
3(1) O
3
(2) Me2 S
CH
3
H OO
6-oxoheptanal(65%
)1-m
ethylcyclohexene
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.11 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
ML0
OG
AlC
l3AlC
l3
CG
C
G
R
OCC
l�
R�
O
R
R is alkyl or aryl; G
is hydrogen, a halogen, or an activating group.
O2 N
C O
Cl
O2 N
O
p-nitrobenzophenone(90%
)p-nitrobenzoyl chloride
©2003 by Prentice H
all,Inc.A
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pany
Figure Num
ber:18 07.12 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
MM
0
Hg
2+, H2 SO
4
alkyne
Exam
ple
HO R
H H
CC
RC
HC
H2 O
H+
H+
methyl ketone
RC
HC
enol (not isolated)
HH
O
CH
O
H HC
CH
2 O
enol
CH
H3
CC O
cyclohexyl methyl ketone
(90%)
ethynylcyclohexane
H2 SO
4 , Hg
2+
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.14 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
MO
0
(1) Sia2 BH
(2) H2 O
2 , NaO
H
(1) Sia2 BH
(2) H2 O
2 , NaO
H
alkyne
Exam
ple
RH
CC
RC
HC
−OH
aldehyde
RC
HC
enol (not isolated)
H2
O
OH
H
CC
H
ethynylcyclohexane
C
cyclohexylethanal(65%
)
C O
HH
2
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.15 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
MP0
S
1,3-dithiane, pKa
�32
�
HH S
SS
H
�C
4 H9 —
Li
n-butyllithium
dithiane anion
butane�
C4 H
10
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.25 P18.6 UN
WA
DE
OR
GA
NIC
CH
EMISTRY,5E
AA
ALB
MY
0
O
�
SS
Hdithiane anion
�R
X
alkylating agent(prim
ary alkyl halide)
SRH Sthioacetal
HR
aldehyde
H2 O
H�
, HgC
l2
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.26 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
MZ0
H2 O
H�
, HgC
l2(1) B
uLi
(2) CH
3 CH
2 CH
2 Br
(1) BuL
i(2) PhC
H2 9
Br
SS
1,3-dithiane
SH
SthioacetalPhC
H2
O
CH
2 CH
2 CH
3
ketone
PhCH
2
SCH
2 CH
2 CH
3
SthioketalPhC
H2
©2003 by Prentice H
all,Inc.A
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pany
Figure Num
ber:18 07.28 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
NB
0
carboxylic acidlithium
carboxylatedianion
hydrateketone
H3 O
��
H2 O
LiO
HR
�9L
iO
R9
C9
OH
O
R9
C9
R�
O
R9
C9
O�
�Li
R9
C9
O�L
i �
O�L
i �
R�
R�
R9
C9
OH
OH
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.29 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
NC
0
H3 O
��
H2 O
C O
(phenyllithium)
cyclohexanecarboxylic acid O
H
Li
2
C OL
i
OL
i
dianion
C OH
OH
hydrate
C O
cyclohexyl phenyl ketone
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.30 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
ND
0
H�
H3 O
�
R R′
MgX
CR
CN
O
R′
Mg
X
nucleophilic attackM
g salt of imine
N
R R′
H
Cimine N
R R′
C
ketone
�N
H4 �
©2003 by Prentice H
all,Inc.A
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pany
Figure Num
ber:18 07.34 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
NG
0
etherH
3 O�
CN
�
MgB
r
benzonitrilephenylm
agnesium brom
idebenzophenone im
ine(m
agnesium salt)
N
MgB
rE
xample
benzophenone(80%
)
O
©2003 by Prentice H
all,Inc.A
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pany
Figure Num
ber:18 07.35 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
NH
0
lithium alum
inum tri(t-butoxy)hydride
Li �
�A
lH(O
-t-Bu)3
acid chloride
O
R9
C9
Cl
aldehyde
O
R9
C9
H
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.38 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
NK
0
SOC
l2L
i + −AlH
(O-t-B
u)3
Exam
ple
isovaleric acidisovaleroyl chloride
CH
3 CH
CH
2 9C
9O
HC
H3 C
HC
H2 9
C9
Cl
CH
3O
CH
3O
isovaleraldehyde (65%)
CH
3 CH
CH
2 9C
9H
CH
3O
©2003 by Prentice H
all,Inc.A
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pany
Figure Num
ber:18 07.39 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
NL0
CuL
iL
iCl
++
a lithium dialkylcuprate
(Gilm
an reagent)
R�9
C9
Cl
' O
R�9
C9
R' O
R9
Cu
+2
R
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.41 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
NN
0
Exam
ple
Cl
2R
9L
i+
+R
2 CuL
iC
uIL
iI
CuL
i(
((1) L
i(2) C
uI
C O80%
'C
Cl
O'
2
©2003 by Prentice H
all,Inc.A
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pany
Figure Num
ber:18 07.42 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
NO
0
RRδ+
CRR
product
C+
RR
CH
Nuc
Oδ−
O−
Nuc −. .
Nuc −
OH
Nuc
Nuc
nucleophilic attackalkoxide
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.56 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
OC
0
C C
C
H3
H3
O
acetone
HO
HH
�
C C
C
H3
H3
O
H
�
C C
C
H3
H3
O
H
��
H2 O
protonated, activated acetone
C C
C
H3
H3
O
H
�O
H2
attack by water
OH
2H H
OCC
H3
CH
3OH
�H
OCC
H3
CH
3OH
loss of H�
acetone hydrate
�H
3 O�
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.60 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
OG
0
Basic conditions (strong nucleophile)
Step 1: Addition of the nucleophile.
Step 2: Protonation.
Step 1: Protonation.Step 2: A
ddition of the nucleophile.
Acidic conditions (w
eak nucleophile, activated carbonyl)
Reverse reaction:
Reverse reaction:
Nuc
9C
9O
9H
Nuc
�N
uc9
C9
O�
�C
"O
Nuc
�
Nuc
�
Nuc
�N
uc −
H+
Nuc
−N
uc−
&&
C"
O
&&
C"
O
&&
C"
O
&&
C"
O�
&
&
&
&&
Nuc
9C
9O
�&&
Nuc
9C
9O
9H
&&
Nuc
9C
9O
9H
&
Nuc
9C
9O
9H
Nuc
9H
&&
&
&&
H9
Nuc
H
C9
O
&
&
&
H�
C"
O�
&
&
&
H
C O
&
&
&
H�
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.67 Summ
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
OI0
R R
CO
�
ketone or aldehydeR
�
R
The W
ittig reaction
�
CP �
Ph
Ph
R R
R�
R�
CC
phosphorus ylide
�P
h3 P
O
alkene
Ph
�
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.68 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
ON
0
�P
Ph
Ph
triphenylphosphine
Ph
alkyl halide
HC
X
HR
PP
h
Ph
phosphonium salt
Ph
CH
HR
�
X�
�
�P
Ph
Ph
Ph
C�
HR
�
PP
h
Ph
Ph
CHR
phosphorus ylide
��
C4 H
10
LiX
butane
dd
methyltriphenylphosphonium
saltP
h3 P
Exam
ples�C
H3
Br
Ph3 P
CH
3
�
Ph
3 PC
H2
��
�Br
ylide
�Br
benzyltriphenylphosphonium salt
Ph
3 PC
H2
�
Ph
Ph
3 PC
H�
�
ylideP
hC
H2
Br
Ph
Ph
3 P�
Bu
9L
i
CH
2 CH
2 CH
3
butyllithium
CH
2 9L
i
Bu
9L
i
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.69 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
OO
0
Ph
3 PC
�
R H�
ylide
R�
R�
CO
ketone or aldehyde
HC
CR
�
R�
R
Ph
3 P �
O�
a betaine
HC
CR
�
R�
R
Ph
3 PO
oxaphosphetane
Step 1: The ylide attacks the carbonyl.
Step 2: The betaine closes to
a 4-mem
bered ring.
©2003 by Prentice H
all,Inc.A
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pany
Figure Num
ber:18 07.70 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
OP0
CC
R�
R�
R
O
four-mem
bered ring
R H
R�
R�
CC
triphenylphosphine oxide�
alkene
Ph
3 PO
H
Ph
3 P
Step 3: The ring collapses to products.
©2003 by Prentice H
all,Inc.A
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pany
Figure Num
ber:18 07.71 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
OQ
0
R R
CO
�H
2 O
R R
OH
O
CK
�[hydrate]
[ketone][H2 O
]
keto formhydrate
(a geminal diol)
H
O
CH
Exam
ple
3C
CH
3�
H2 O
CH
3C
CH
3
HO
HO
acetone hydrateacetone
K �
0.002
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.78 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
OX
0
RR
C O
In acid
RR
C O�
HH
HH
H2 O
H2 O
RC
R
O�
O
RC
R
O OH
H3 O
�
H
H3 O
�
Step 1: Protonation.Step 2: W
ater adds.Step 3: D
eprotonation.
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.79 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
OY
0
In baseRR
C OH
O�
HO
CR
R O�
HO
HH
OC
R
OR
H
��O
H
Step 1: Hydroxide adds.
Step 2: Protonation.
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.80 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
OZ0
O
ketone or aldehyde
CR
R�
CN
CN
RC
R�
O�
intermediate
CN
H
CN
RC
R�
O
cyanohydrin H�
Step 1: Cyanide adds.
Step 2: Protonation.
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.84 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
PD0
O
ketone or aldehyde
H�
C�
RN
H2
CNR
OH
H
CNR
�H
2 Oprim
ary amine
carbinolamine
imine
(Schiff base)©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.89 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
PI0
OCCN
RH
O�
H
CNR
H
OH
H2 O
RN
H2
nucleophilic attackfast proton transfer
carbinolamine
�
H3 O
�
Step 1: The am
ine adds to the carbonyl.Step 2: Protonation and deprotonation.
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.90 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
PJ0
CN
RH
O
H
H+
CN
RH
O�
HH
N
RH
C
minor
major
�
R
N�
H
C
�H
2 O
R
N C
�H
3 O�
carbinolamine
protonatedinterm
ediate (all octets filled)im
ine
Step 3: Protonation of hydroxyl.Step 4: L
oss of water.
Step 5: Deprotonation.
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 07.91 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
PK0
H+
C"
O
&&
C"
N9
Z
&&
��
H2 N
9Z
H2 O
Product
Reagent
Z in Z
9N
H2
9H
H2 N
9H
amm
oniaC
"N
9H
an imine
&&
9R
H2 N
9R
primary am
ineC
"N
9R
an imine (Schiff base)
&&
9O
HH
2 N9
OH
hydroxylamine
C"
N9
OH
an oxime
&&
9N
H2
H2 N
9N
H2 hydrazine
C"
N9
NH
2a hydrazone
&&
9N
HPh
H2 N
9N
HPh phenylhydrazine
C"
N9
NH
Pha phenylhydrazone
&&
9N
HC
NH
2H
2 N9
NH
9C
9N
H2
C"
N9
NH
9C
9N
H2
semicarbazide
a semicarbazone
&&
O'O'
O'
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 08.009 Summ
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
PT0
C
aldehyde
O
RH
�2
R�
OH
H+H+
C
acetalR
H
R�O
OR
��
H2 O
C
ketone
O
RR
��
2R
�O
HC
acetal (IUPA
C)
ketal (comm
on)
RR
�
R�O
OR
��
H2 O
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 08.018 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
QE0
ketone
O
H9
OT
s
�OH
HO�
protonated (activated) ketone
OC
H3
HH
OO
�
H
CH
3
CH
3O
H
HOhem
iacetal
OC
H3
The first half is an acid-catalyzed addition to the carbonyl
Step 1: Protonation.Step 2: A
lcohol adds.Step 3: D
eprotonation.
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 08.020 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
QG
0
hemiacetal
OC
H3
OH
H+
OC
H3
OH
� HC
H3
O�
O
CH
3�
�H
2 O
CH
3 9O
9H
protonation, loss of water
resonance-stabilized carbocation
CH
3
O�
attack by methanol
OC
H3
H
OC
H3
OC
H3
�
HO
CH
3
H
acetal
OC
H3
OC
H3
�
�
H
The second half begins like an acid-catalyzed dehydration
Step 4: Protonation.Step 5: L
oss of water.
Step 6: Second alcohol adds.Step 7: D
eprotonation.
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 08.021 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
QH
0
OCH
�H
CC
H
H
H
OO
HH
�
CH
H
OO
CC
H
HH
�H
2 O
benzaldehydeethylene acetal
benzaldehydeethylene glycol
H
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 08.024 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
QK
0
H2 O
��
H�
C O
HH
formaldehyde
propane-1,3-dithiol
SHSH
dithiane
SS
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 08.025 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
CY
MM
G0
O
R9
C9
H
Exam
ples
O
R9
C9
OH
Ag
2 O
TH
F/H2 O
Na2 C
r2 O7
dil H2 SO
4 [O]
(oxidizing agent)
C CC
H3
CH
O
H
isobutyraldehyde
CC
H3
CH
O
OH
isobutyric acid (90%)
CH
3C
H3
H
O
CO
H
O
(97%)
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 08.051 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
RG
0
NaB
H4
or LiA
lH4
(1) TsC
l
(2) LiA
lH4
R
OCR
�R
CR
�
HH
ketonem
ethylene groupR
CR
�
HO
H
alcohol
deoxygenation
Zn(H
g), HC
l or H2 N
NH
2 , KO
H
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 08.059 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
RO0
CN
NR
�
R
O −HH
CN
NR
�
RH
�
�CN
NR
�H
H2 O
CN
NR
�
RH
hydrazonerem
ove proton from N
replace proton on C
H
��O
H
H
R
Step 1: Deprotonation from
N.
Step 2: Reprotonation on C
.
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 08.063 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
RS0
CN
NR
�
R
R�
R
R�
R
R�
RH
HO −
HC
NN
HC
H� N
NH
2 OC
HH
��O
H
carbanionproduct
�
Step 3: Rem
ove second proton from N
.Step 4: L
ose N2 .
Step 5: Protonate.
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 08.064 UN
W
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
ALB
RT0
N
NH
2
NO
HO
H
HH
H
HO
H C2H
O
deoxycytidine
N
N
N
NH
2
NO
HO
H
HH
HH
deoxyadenosine
HO
H C2
©2003 by Prentice H
all,Inc.A
Pearson Com
pany
Figure Num
ber:18 08.145 SP18.76 bW
AD
EO
RG
AN
IC C
HEM
ISTRY,5E
AA
CY
MM
N0
