J. CHEM. RESEARCH (S), 1999 727
be achieved within 10^13 h of reaction. Products were
isolated by usual work-up and puri¢cation was by distil-
lation or recrystallization. Results on the transformations
are summarized in Table 1.
Furthermore, the results suggest that this procedure
shows considerable chemoselectivity for the oxidation of
various primary amines. Other functionalities such as
isolated double bond (1v) or ethers (1n, o, 1q^s) are all com-
patible with the reaction conditions.
It is noteworthy that the presence of nickel copper for-
mate was essential for the dehydrogenation of amines to
nitriles, no nitriles were obtained in its absence and
reactions did not go to completion when reduced amounts
of nickel copper formate catalyst were used.
In conclusion, this new procedure has the following prac-
tical advantages compared with the previously reported
preparation of nitriles from primary amines: (i) our proce-
dure is quite simple with the reagents being simply mixed
together at the beginning of reaction, (ii) the reaction con-
ditions are mild enough to allow the preparation of rather
unstable nitriles; (iii) the yields are excellent in all cases,
(iv) there are virtually no side reactions which complicate
isolation and puri¢cation of the products.
Received, 10th August 1999; Accepted, 10th September 1999
Paper E/9/06485K
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Experimental
Mps and bps are uncorrected. IR spectra were recorded on a
Nicolet FI-IR 360 spectrophotometer; 1H NMR spectra were
measured on a JEOL FX-90Q instrument using CDCl3 as solvent
and TMS as internal standard; elemental analyses (C, H, N) were
performed on a Carlo Erba 1106-type analyzer.
Nickel copper formate (non-hydrate) was purchased from
Shanghai Chemical Reagent Company. All primary amines (1a^v)
are commercially available. (NBun S2O8 was prepared according
4
2
to the known procedure.4a
General Procedure for the Oxidation of Primary Amines (1a^v) to
Nitriles (2a^v).öTo a solution of nickel copper formate (1 mmol)
in H2O (10 ml) was added, dropwise, a primary amine 1a^v (100 mol)
in CH2ClCH2Cl or CH2Cl2 (100 ml), (NBun42S2O8 (125 mmol) in
CH2ClCH2Cl or CH2Cl2 (275 ml) and KOH (125 mmol) in H2O
(300 ml). The mixture was stirred at room temperature for 10^13 h
(Table 1). Insoluble compounds (NiO2 and CuO) were then ¢ltered
o¡ and the ¢ltrate was poured into H2O (100 ml) and extracted with
CH2ClCH2Cl or CH2Cl2 ꢀ2 Â 75 ml). The combined extracts were
washed with brine ꢀ3 Â 100 ml), dried ꢀNa2SO4 and evaporated under
reduced pressure. The crude product was puri¢ed by distillation or
recrystallization to give pure nitriles 2a^v in 87^95% yield.
6
7
8
9
10 B. Kokel, G. Menichi and M. Hubert-Habart, Synthesis, 1985,
201.