反応例
10.3
アルコールとアルデヒドの酸化反応
第二級アルコールからケトンの生成
OH
Cl
O
Na2Cr2O7
Cl
Cl
H2SO4 , H2O
Cl
68~75%
J.B. Conant, O.R. Quayle, Org. Synth., Coll. Vol. 1, 211 (1941).
OH
O
CrO3, H 2SO4
H 2O, acetone
HO
OH
92~96%
O
CrO3, H2 SO4
O
aq. CH 2Cl2, 0 ˚C
E.J. Eisenbraun,
Org. Synth., Coll. Vol. 5, 310 (1973).
G.H. Rasmusson, et al.,
Org. Synth., Coll. Vol. 5, 324!(1973).
39~50%
CH3
CH3
Na2Cr2O7
OH
CH3
H 2SO4, H2O
CH3
O
O
KMnO4
Ph
CO 2H aq. NaOH, –3 ˚C
OH
CH3
CO 2Et
CH3 83~85%
CH3
OH
Ph
CO2H
B.B. Corson, et al.,
Org. Synth., Coll. Vol. 1, 241 (1941).
O
KMnO4
aq. HaH 2PO4
pet. ether
L.T. Sandborn,
Org. Synth., Coll. Vol. 1, 340 (1941).
CH3
CO2Et
51~54%
J.W. Cornforth,
Org. Synth., Coll. Vol. 4, 467 (1963).
C8H17
C8H17
Na2Cr2O7
H2SO4, HOAc
HO
H 2O, C6H 6
dihydrocholesterol
O
83~84%
W.F. Bruice, Org. Synth., Coll. Vol. 2, 139 (1943).
C8H17
C8H17
Na2Cr2O7
HOAc, C6H 6
HO
O
39~40%
O
L.F. Fieser, Org. Synth., Coll. Vol. 4, 189 (1963).
cholesterol
C8H17
C8H17
(a) (t-BuO)3Al,
acetone, benzene
!
(a) 70~81%
(b) (i-PrO)3Al,
cyclohexanone
toluene
HO
cholesterol
O
(b) 81~93%
(a) R.V. Oppenauer, Org. Synth., Coll. Vol. 3, 207 (1955).
(b) J.F. Eastham, R. Teranishi, Org. Synth., Coll. Vol. 4, 192 (1963).
C8H17
C8H17
Br2, HOAc,
NaOAc, Et 2O
HO
cholesterol
Zn, Et2O
Na2Cr2 O7
HOAc
HO
Br
!"#$%&'()*+,
C8H17
Br
Br
(81% from cholesterol)
C8H17
C8H17
(CO2H)2
Zn
O
Br
O
O
(71% from cholesterol)
(68% from cholesterol)
L.F. Fieser, Org. Synth., Coll. Vol. 4, 195 (1963).
OH
O
CrO3, H 2SO4
H 2O, acetone
CH2OH
J. Meinwald, J. Crandall, W.E. Hymans,
Org. Synth., Coll. Vol. 5, 866 (1973).
OH
H+, H 2O
100 ˚C
!"#$
OH
O
CrO3, (CO2H)2
H2O, 10~15 ˚C
M. Krumpolc, J. Rocek,
Org. Synth., Coll. Vol. 7, 114 (1990).
31~35%
(from cyclopropylmethanol)
第一級アルコールか らカルボン酸 の生成
O
OH
Na2Cr2 O7
O
41~47%
G.R. Robertson, Org. Synth., Coll. Vol. 1, 138 (1941).
H 2SO4, H 2O
CH3
CH3
CuCr2O4/BaCr2O4
OH
200 ˚C
OH
O
O
90~95%
F
CH3(CH2) 4 C CH2Br
H
!
(SN2: NaI catalyst)
F
CH3(CH2)4
C CH2OAc
H
NaOAc, NaI
DMF
HNO3
R.I. Longley, Jr., W.S. Emerson,
Org. Synth., Coll. Vol. 4, 677 (1963).
F
CH3(CH2) 4 C CH2OAc
H
63~78%
F
CH3(CH2)4 C CO 2H
78~94%
H
F.H. Dean, J.H. Amin, F.L.M. Pattiso, Org. Synth., Coll. Vol. 5, 580 (1973).
HOAc, 50 ˚C
第一級アルコールか らアルデヒド の生成
K2Cr2O7
OH
O
H 2SO4, H2 O
OH
H
46~49%
!
C.D. Hurd, R.N. Meinert,
Org. Synth., Coll. Vol. 2, 541 (1943).
!"#$%&'()*+,-./012
H
CrO3, H 2SO4
CH2OH
H
H2O, 5 ˚C
CHO J.C. Sauer,
Org. Synth., Coll. Vol. 4, 813 (1963).
35~41%
(Moffatt!!"#
CH2OH
CHO
C6H 11N C NC6H 11
pyridine, CF3CO2H
DMSO, benzene
J.G. Moffatt, Org. Synth., Coll. Vol. 5, 242 (1973).
CH3(CH2)8–CH2OH
CrO3 ·(pyridine)2
CH3(CH2)8–CHO
CH2Cl2
63~66%
R.W. Ratcliffe, Org. Synth., Coll. Vol. 6, 373 (1988).
CH3(CH2)5–CH2OH
CrO3·(pyridine)2
CH2Cl2, 25 ˚C
CH3(CH2)5–CHO
70~84%
J.C. Collins, W.W. Hess, Org. Synth., Coll. Vol. 6, 644 (1988).
aq. NaOCl (pH 9.5),
CH 2Cl2 KBr (cat.)
O
H
OH
0~15 ˚C
N O
(cat.)
82~84%
P.L. Anelli, F. Montanari, S. Quici,
Org. Synth., Coll. Vol. 8, 367 (1993).
アルデヒドからカル ボン酸の生成
O
O
KMnO4
H
OH
H 2SO4 , H2O
85~90%
J.R. Ruhoff, Org. Synth., Coll. Vol. 2, 315 (1943).
O
O
O
O
KMnO4
CHO
H2O, 75 ˚C
CO 2H
R.L. Shriner, E.C. Kleiderer,
Org. Synth., Coll. Vol. 2, 358 (1943).
78~84%
O
O
HCl
H
–15 ~ –10 ˚C
Cl
H
O
O
HNO3
Cl
H
Cl
OH
C. Moureu, R. Chaux,
Org. Synth., Coll. Vol. 1, 166 (1941).
60~65%
CHO
HO
1) Ag2O, 55 ˚C
NaOH, H 2O
CO 2H
HO
2) HCl, H2 O
OMe
vanillin
OMe
90~97%
CHO
CO 2H
Ag2O
S
I.A. Pearl,
Org. Synth., Coll. Vol. 4, 972 (1963).
NaOH, H2O
S
95~97%
E. Campaigne, W.M. LeSuer,
Org. Synth., Coll. Vol. 4, 919 (1963).
1) O2 , Cu2O, Ag2O
NaOH, H 2O
CHO
O
NaClO3
V2 O5 (cat.)
CHO
O
CO 2H
HO 2C
H 2O, 75 ˚C
R.J. Harrisson, M. Moyle,
Org. Synth., Coll. Vol. 4, 493 (1963).
CO 2H
O
86~90%
2) H2 SO4
50~58%
N.A. Milas,
Org. Synth., Coll. Vol. 2, 302 (1943).
ジオールとα−ヒド ロキシケトン の酸化と 開裂
C
HIO4 or Pb(OAc)4
C
O + O
OH OH
OH
t-Bu-O 2C
O
Pb(OAc)4
CO 2-t- Bu
H
benzene
OH
O
OSiMe3
CO 2-t-Bu F.J. Wolf, J. Weijlard,
Org. Synth., Coll. Vol. 4, 124 (1963).
77~87%
OH
1) LDA, THF, –78 ˚C
2)
O
OSiMe3
O
!"#$%#&'(
H
OH
OH
O
OSiMe 3
O
H5 IO6
OH
THF, 25 ˚C
B. Bal, C.T. Buse, K. Smith, Org. Synth., Coll. Vol. 7, 185 (1990).
O
(CH2) 8
OH
Cu(OAc)2, MeOH
aq. HOAc, !
O
(CH2)8
O
88~89%
A.T. Blomquist, A. Goldstein,
Org. Synth., Coll. Vol. 4, 838 (1963).