Page 1
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
Cl
OH
Cl Cl
ONa2Cr2O7
H2SO4, H2O68~75%
J.B. Conant, O.R. Quayle, Org. Synth., Coll. Vol. 1, 211 (1941).
Cl
OH OCrO3, H2SO4
H2O, acetone
92~96%
E.J. Eisenbraun,
Org. Synth., Coll. Vol. 5, 310 (1973).
OHHO OOCrO3, H2SO4
aq. CH2Cl2, 0 ˚CG.H. Rasmusson, et al.,
Org. Synth., Coll. Vol. 5, 324!(1973).39~50%
CH3
OH
CH3CH3
Na2Cr2O7
H2SO4, H2O
CH3
O
CH3CH383~85%
L.T. Sandborn,
Org. Synth., Coll. Vol. 1, 340 (1941).
Ph CO2H
OH
Ph CO2H
O
aq. NaOH, –3 ˚CB.B. Corson, et al., Org. Synth., Coll. Vol. 1, 241 (1941).
KMnO4
CO2Et
OH
CH3 CH3 CO2Et
Oaq. HaH2PO4 J.W. Cornforth,
Org. Synth., Coll. Vol. 4, 467 (1963).pet. ether
51~54%
KMnO4
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HO
C8H17
O
C8H17
dihydrocholesterol
Na2Cr2O7
H2SO4, HOAc
H2O, C6H683~84%
W.F. Bruice, Org. Synth., Coll. Vol. 2, 139 (1943).
HO
C8H17
O
C8H17
Ocholesterol
Na2Cr2O7
HOAc, C6H6
39~40%
L.F. Fieser, Org. Synth., Coll. Vol. 4, 189 (1963).
HO
C8H17
!
O
C8H17
cholesterol
(a) (t-BuO)3Al, acetone, benzene
(b) (i-PrO)3Al, cyclohexanone toluene
(a) 70~81%
(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).
HO
C8H17
BrBr
Zn
O
C8H17
O
C8H17
(CO2H)2
HO
C8H17
O
C8H17
BrBr
cholesterol
Br2, HOAc,NaOAc, Et2O
Zn, Et2O
!"#$%&'()*+,
Na2Cr2O7
(81% from cholesterol)(71% from cholesterol) (68% from cholesterol)
L.F. Fieser, Org. Synth., Coll. Vol. 4, 195 (1963).
HOAc
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OH OCrO3, H2SO4
H2O, acetone
J. Meinwald, J. Crandall, W.E. Hymans, Org. Synth., Coll. Vol. 5, 866 (1973).
OH
CH2OH
O
OHH+, H2O
100 ˚C
!"#$
CrO3, (CO2H)2
H2O, 10~15 ˚C
31~35% (from cyclopropylmethanol)
M. Krumpolc, J. Rocek, Org. Synth., Coll. Vol. 7, 114 (1990).
第一級アルコールからカルボン酸の生成
OHNa2Cr2O7
H2SO4, H2OO
O
41~47%
G.R. Robertson, Org. Synth., Coll. Vol. 1, 138 (1941).
OH OH
CH3
CuCr2O4/BaCr2O4
200 ̊ CO
CH3
O
90~95%
R.I. Longley, Jr., W.S. Emerson, Org. Synth., Coll. Vol. 4, 677 (1963).
CH3(CH2)4 C
F
CH2Br
H
CH3(CH2)4 C
F
CH2OAc
H
!CH3(CH2)4 C
F
CH2OAc
H
CH3(CH2)4 C
F
CO2H
H
NaOAc, NaI
(SN2: NaI catalyst)
HOAc, 50 ˚C
F.H. Dean, J.H. Amin, F.L.M. Pattiso, Org. Synth., Coll. Vol. 5, 580 (1973).
78~94%
63~78%DMF
HNO3
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第一級アルコールからアルデヒドの生成
K2Cr2O7
H2SO4, H2O
C.D. Hurd, R.N. Meinert,
Org. Synth., Coll. Vol. 2, 541 (1943).
H
O
OHOH !
46~49%
!"#$%&'()*+,-./012
H CH2OH H CHOCrO3, H2SO4
H2O, 5 ̊ CJ.C. Sauer,
Org. Synth., Coll. Vol. 4, 813 (1963).35~41%
CH2OH
C6H11N C NC6H11
CHO
pyridine, CF3CO2H
DMSO, benzene
J.G. Moffatt, Org. Synth., Coll. Vol. 5, 242 (1973).
(Moffatt!!"#
CH2Cl2CH3(CH2)8–CH2OH CH3(CH2)8–CHO
CrO3·(pyridine)2
R.W. Ratcliffe, Org. Synth., Coll. Vol. 6, 373 (1988).
63~66%
CH3(CH2)5–CH2OH CH3(CH2)5–CHO
CrO3·(pyridine)2
CH2Cl2, 25 ̊ C
J.C. Collins, W.W. Hess, Org. Synth., Coll. Vol. 6, 644 (1988).
70~84%
OH H
O
N O
(cat.)
KBr (cat.)aq. NaOCl (pH 9.5), CH2Cl2
0~15 ̊ C 82~84%
P.L. Anelli, F. Montanari, S. Quici,
Org. Synth., Coll. Vol. 8, 367 (1993).
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アルデヒドからカルボン酸の生成
H
OKMnO4
OH
O
H2SO4, H2O
85~90%
J.R. Ruhoff, Org. Synth., Coll. Vol. 2, 315 (1943).
O
O
CHO
KMnO4
O
O
CO2HH2O, 75 ˚C
78~84%
R.L. Shriner, E.C. Kleiderer,
Org. Synth., Coll. Vol. 2, 358 (1943).
H
O
HCl
Cl H
O
HNO3
Cl H
O
Cl OH
O
–15 ~ –10 ̊ C
60~65%
C. Moureu, R. Chaux,
Org. Synth., Coll. Vol. 1, 166 (1941).
CHO
HO
OMe
NaOH, H2O
Ag2O, 55 ˚C
HCl, H2O
CO2H
HO
OMe
vanillin
1)
2)
I.A. Pearl,
Org. Synth., Coll. Vol. 4, 972 (1963).90~97%
S
CHO
Ag2O
NaOH, H2O S
CO2H
E. Campaigne, W.M. LeSuer, Org. Synth., Coll. Vol. 4, 919 (1963).
95~97%
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O CHO
O2,
NaOH, H2O
Cu2O, Ag2O
H2SO4O CO2H
1)
2)
R.J. Harrisson, M. Moyle, Org. Synth., Coll. Vol. 4, 493 (1963).
86~90%
CHOO
NaClO3V2O5 (cat.)
HO2CCO2H
H2O, 75 ̊ C50~58%
N.A. Milas, Org. Synth., Coll. Vol. 2, 302 (1943).
ジオールとα-ヒドロキシケトンの酸化と開裂
C C
OHOH
HIO4 or Pb(OAc)4O O+
t-Bu-O2CCO2-t-Bu
OH
OH
Pb(OAc)4
benzene H CO2-t-Bu
O
77~87%
F.J. Wolf, J. Weijlard,
Org. Synth., Coll. Vol. 4, 124 (1963).
O
OSiMe3
O
OSiMe3
OHH5IO6
H
O
OH
OOH
O
OSiMe3
OH
THF, 25 ˚C
1) LDA, THF, –78 ˚C
2)
B. Bal, C.T. Buse, K. Smith, Org. Synth., Coll. Vol. 7, 185 (1990).
!"#$%#&'(
(CH2)8
O
OH
Cu(OAc)2, MeOH(CH2)8
O
Oaq. HOAc, !
88~89%
A.T. Blomquist, A. Goldstein,
Org. Synth., Coll. Vol. 4, 838 (1963).