Organic Reactions Volume 4 - Sciencemadness Dot Org

202 ORGANIC REACTIONS
fraction boiling at 235-245° being collected. The yield is 11.5-12 g.
(77-81%).
If 22 g. (0.30 mole) of butyraldehyde is used and the reduction is then
allowed to run eighteen hours, the yield rises to 13.7-14.3 g. (92-96%).
This method is time-consuming and more costly because of the larger
amount of aldehyde used, even though the yield is higher.
N,N-Di~n-Butylaniline. 2 If, in the preparation just described, 22 g.
(0.30 mole) of butyraldehyde is used and 10 ml of glacial acetic acid is
substituted for the sodium acetate and 0.1 g. of platinum oxide 81 for
the Raney nickel, 0.66 mole of hydrogen is absorbed in ninety-six hours.
The reaction mixture is worked up in the same manner to obtain 14.5
g. (69%) of N,N-di-n-butylaniline, b.p. 265-275°.
TABLE I
PREPABATION OF n-HEPTYLAMINB
Method
Reductive alkylation of ammonia with n-heptaldehyde
Reductive alkylation of ammonia with n-heptaldehydo
Reductive alkylation of ammonia with n-hcptaldehydo
Reduction of n-heptaldoximc with ammonium amalgam
Reduction of n-heptaldoximo with sodium and ethanol
Reduction of w-heptaldoxime with sodium and ethanol
Reduction of n-heptaldoxime with hydrogen and Raney nickel
Reduction of n-heptaldchyde phenylhydrazone with sodium amalgam
and acetic acid
Hofmann reaction with caprylamide
Reduction of heptylamide with hydrogen and copper chromite
Reaction of n-heptyl bromide with ammonia
* References 84-91 are listed on p. 254.
t There is also formed 16% of di-n-heptylamine.
t There is also formed 58% of di-n-heptylamine,
§ There is also formed 37% of di-n-heptylamine.
Yield, %
60
59
53-63
93
60-73
69
64 f
23
30
39 %
47 §
Ref.*
5
1
14
84
85
86
87
88
89
90
91