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反応例 10.3...
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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 O Na 2 Cr 2 O 7 H 2 SO 4 , H 2 O 68~75% J.B. Conant, O.R. Quayle, Org. Synth. , Coll. Vol. 1 , 211 (1941). Cl OH O CrO 3 , H 2 SO 4 H 2 O, acetone 92~96% E.J. Eisenbraun, Org. Synth. , Coll. Vol. 5, 310 (1973). OH HO O O CrO 3 , H 2 SO 4 aq. CH 2 Cl 2 , 0 ˚C G.H. Rasmusson, et al., Org. Synth. , Coll. Vol. 5 , 324 (1973). 39~50% CH 3 OH CH 3 CH 3 Na 2 Cr 2 O 7 H 2 SO 4 , H 2 O CH 3 O CH 3 CH 3 83~85% L.T. Sandborn, Org. Synth. , Coll. Vol. 1 , 340 (1941). Ph CO 2 H OH Ph CO 2 H O aq. NaOH, –3 ˚C B.B. Corson, et al., Org. Synth. , Coll. Vol. 1 , 241 (1941). KMnO 4 CO 2 Et OH CH 3 CH 3 CO 2 Et O aq. HaH 2 PO 4 J.W. Cornforth, Org. Synth. , Coll. Vol. 4, 467 (1963). pet. ether 51~54% KMnO 4
Transcript of 反応例 10.3...
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
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
!"#$%&'()*+,
Na2Cr2O7
(81% from cholesterol)(71% from cholesterol) (68% from cholesterol)
L.F. Fieser, Org. Synth., Coll. Vol. 4, 195 (1963).
HOAc
OH OCrO3, H2SO4
H2O, acetone
J. Meinwald, J. Crandall, W.E. Hymans, Org. Synth., Coll. Vol. 5, 866 (1973).
OH
CH2OH
O
OHH+, H2O
100 ˚C
!"#$
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
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%
!"#$%&'()*+,-./012
H CH2OH H CHOCrO3, H2SO4
H2O, 5 ̊ CJ.C. Sauer,
Org. Synth., Coll. Vol. 4, 813 (1963).35~41%
CH2OH
C6H11N C NC6H11
CHO
pyridine, CF3CO2H
DMSO, benzene
J.G. Moffatt, Org. Synth., Coll. Vol. 5, 242 (1973).
(Moffatt!!"#
CH2Cl2CH3(CH2)8–CH2OH CH3(CH2)8–CHO
CrO3·(pyridine)2
R.W. Ratcliffe, Org. Synth., Coll. Vol. 6, 373 (1988).
63~66%
CH3(CH2)5–CH2OH CH3(CH2)5–CHO
CrO3·(pyridine)2
CH2Cl2, 25 ̊ C
J.C. Collins, W.W. Hess, Org. Synth., Coll. Vol. 6, 644 (1988).
70~84%
OH H
O
N O
(cat.)
KBr (cat.)aq. NaOCl (pH 9.5), CH2Cl2
0~15 ̊ C 82~84%
P.L. Anelli, F. Montanari, S. Quici,
Org. Synth., Coll. Vol. 8, 367 (1993).
アルデヒドからカルボン酸の生成
H
OKMnO4
OH
O
H2SO4, H2O
85~90%
J.R. Ruhoff, Org. Synth., Coll. Vol. 2, 315 (1943).
O
O
CHO
KMnO4
O
O
CO2HH2O, 75 ˚C
78~84%
R.L. Shriner, E.C. Kleiderer,
Org. Synth., Coll. Vol. 2, 358 (1943).
H
O
HCl
Cl H
O
HNO3
Cl H
O
Cl OH
O
–15 ~ –10 ̊ C
60~65%
C. Moureu, R. Chaux,
Org. Synth., Coll. Vol. 1, 166 (1941).
CHO
HO
OMe
NaOH, H2O
Ag2O, 55 ˚C
HCl, H2O
CO2H
HO
OMe
vanillin
1)
2)
I.A. Pearl,
Org. Synth., Coll. Vol. 4, 972 (1963).90~97%
S
CHO
Ag2O
NaOH, H2O S
CO2H
E. Campaigne, W.M. LeSuer, Org. Synth., Coll. Vol. 4, 919 (1963).
95~97%
O CHO
O2,
NaOH, H2O
Cu2O, Ag2O
H2SO4O CO2H
1)
2)
R.J. Harrisson, M. Moyle, Org. Synth., Coll. Vol. 4, 493 (1963).
86~90%
CHOO
NaClO3V2O5 (cat.)
HO2CCO2H
H2O, 75 ̊ C50~58%
N.A. Milas, Org. Synth., Coll. Vol. 2, 302 (1943).
ジオールとα－ヒドロキシケトンの酸化と開裂
C C
OHOH
HIO4 or Pb(OAc)4O O+
t-Bu-O2CCO2-t-Bu
OH
OH
Pb(OAc)4
benzene H CO2-t-Bu
O
77~87%
F.J. Wolf, J. Weijlard,
Org. Synth., Coll. Vol. 4, 124 (1963).
O
OSiMe3
O
OSiMe3
OHH5IO6
H
O
OH
OOH
O
OSiMe3
OH
THF, 25 ˚C
1) LDA, THF, –78 ˚C
2)
B. Bal, C.T. Buse, K. Smith, Org. Synth., Coll. Vol. 7, 185 (1990).
!"#$%#&'(
(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).
