Organic Chemistry

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864 CHAPTER 20 More About Oxidation–Reduction Reactions

PROBLEM 24

a. What alkene would give only acetone as a product of ozonolysis?
b. What alkenes would give only butanal as a product of ozonolysis?

PROBLEM 25 SOLVED

The following products were obtained from ozonolysis of a diene followed by work-up
under reducing conditions. Give the structure of the diene.

SOLUTION The five-carbon dicarbonyl compound indicates that the diene must contain
five carbons flanked by two double bonds.

One of the carbonyl compounds obtained from ozonolysis has one carbon atom, and the
other has three carbon atoms. Therefore, one carbon has to be added to one end of the
diene, and three carbons have to be added to the other end.

PROBLEM 26

What aspect of the structure of the alkene does ozonolysis not tell you?

Permanganate Cleavage
We have seen that alkenes are oxidized to 1,2-diols by a basic solution of potassium
permanganate at room temperature or below, and the 1,2-diols can subsequently be
cleaved by periodic acid to form aldehydes and/or ketones (Sections 20.6 and 20.7). If,
however, the basic solution of potassium permanganate is heated or if the solution is
acidic, the reaction will not stop at the diol. Instead, the alkene will be cleaved, and the
reaction products will be ketones and carboxylic acids. If the reaction is carried out
under basic conditions, any carboxylic acid product will be in its basic form
if the reaction is carried out under acidic conditions, any carboxylic acid
product will be in its acidic form (RCOOH) (Section 1.20). Terminal alkenes form
as a product.

The various methods used to oxidize an alkene are summarized in Table 20.1.

CH 3 CH 2 C

CH 3

CHCH 3

CH 2

KMnO 4 , HO−

O


KMnO 4 , HO−

CH 3 CH 2 CH CH 2 +

KMnO 4
H+ CO^2

+ CO 2

CH 3 CH 2

CH 3
C O O C
O−

+

CH 3

CH 3 CH 2

HO

C O

CO 2

(RCOO-);

CH 2 “CHCH 2 CH 2 CH 2 CH“CHCH 2 CH 3

O O

HCCH 2 CH 2 CH 2 CH CHCH 2 CH 2 CH 2 CH

OOO O

HCCH 2 CH 2 CH 2 CH + HCH + CH 3 CH 2 CH

A peroxyacid, and (cold basic)
break only the bond of the
alkene. Ozone and acidic (or hot basic)
break both the bond and the
Sbond.

KMnO 4 P

KMnO 4 P

OsO 4 ,

BRUI20_841_882r3 01-04-2003 1:11 PM Page 864

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