Page 1154 - Advanced Organic Chemistry Part B - Reactions & Synthesis

1130 Scheme 12.19. Ozonolysis Reactions

CHAPTER 12 A. Reductive workup
1 a
Oxidations
1) O 3
CH 3 N CH CH2 2) Na SO 3 CH 3 N CH O
2
80%
2 b CH O
CH CH CHCH Cl 1) O 3 CH 2
2
2
2) NaI
NO 2 NO 2 89%
O
3 c CH 2 1) O 3
2) Me S N O
2
N O 66%
CH 3
CH 3
4 d CH 3 CH 3
1) O 3
2) (CH ) S
3 2
H C Cl O Cl 84%
2
B. Oxidative workup
5 e O HO C
2
1) O , HCO H CO H
2
2
3
O CO 2 H
2) H 2 O 2 HO C
2
95%
O
6 f O O
1) O 3
PhP(CH CH CH ) PhP(CH CO H) 2
2
2
2 3
2
2) HCO 2 H, H 2 O 2
83%
7 g OCH Ph
OCH Ph O , –78°C 2
3
2
2.5 M NaOH, CH (CH ) CHCO CH
CH (CH ) CHCH CH 2 CH 3 OH, CH 2 Cl 2 3 2 5 2 3 78%
3
2 5
a. R. H. Callighan and M. H. Wilt, J. Org. Chem., 26, 4912 (1961).
b. W. E. Noland and J. H. Sellstedt, J. Org. Chem., 31, 345 (1966).
c. M. L. Rueppel and H. Rapoport, J. Am. Chem. Soc., 94, 3877 (1972).
d. J. V. Paukstelis and B. W. Macharia, J. Org. Chem., 38, 646 (1973).
e. J. E. Franz, W. S. Knowles, and C. Ousch, J. Org. Chem., 30, 4328 (1965).
f. J. L. Eichelberger and J. K. Stille, J. Org. Chem., 36, 1840 (1971).
g. J. A. Marshall and A. W. Garofalo, J. Org. Chem., 58, 3675 (1993).
isolated. If the reaction mixture is then treated with dimethyl sulfide, the hydroperoxide
is reduced and the second carbonyl compound is also formed in good yield. 203
+
–
R C O O + CH OH R COOH
3
2
2
OCH 3
O 3
PhCH CH 2 PhCHOOH + CH 2 OOH + PhCH O + CH 2 O
CH 3 OH
OCH 27%
OCH 3 31% 3 23% 26%
Ozonolysis in the presence of NaOH or NaOCH in methanol with CH Cl as a
3 2 2
cosolvent leads to formation of esters. This transformation proceeds by trapping both
203
J. J. Pappas, W. P. Keaveney, E. Gancher, and M. Berger, Tetrahedron Lett., 4273 (1966).