Dehydrogenation of Amines to Nitriles in Aqueous Micelles
FULL PAPER
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then with brine until a neutral solution was obtained. The extracts
were then dried, and the solvent removed by evaporation under
reduced pressure to give the crude product, which was pure by GC,
which was then weighed.
Reactions in Biphasic Water/Dichloromethane Solution: Reactions
were carried out in 50-mL round-bottomed flasks. Potassium per-
sulfate (0.96 mmol) was dissolved in NaOH solution (8 mL).
Amine (0.38 mmol) was then dissolved in CH2Cl2 (3 mL) and this
solution was added to the aqueous persulfate solution. A solution
of NiSO4 (0.0057 mmol) was then added under magnetic stirring
and a suspension of fine black particles of nickel peroxide was pro-
duced. The resulting mixture was stirred at room temperature. At
the end of the reaction, the reaction work-up was carried out as
described for the reactions in aqueous solutions.
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Product Analysis: Reaction products were analyzed quantitatively
by GLC on an HP 35 MS instrument (FID) with a column injec-
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film thickness. Response factors were determined by using known
mixtures of the products. All analyses were made in duplicate and
errors of Ͻ5 mol-% were obtained.
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Preparation and Characterization of the Products: Tetradecaneni-
trile and hexadecanenitrile were prepared from tetradecylamine
and hexadecylamine, respectively, and oxidized in DDAO as de-
scribed above: the corresponding nitriles were obtained with yields
by weight of 92 and 94%, respectively, and characterized by 1H
NMR spectrum (200 MHz, CDCl3, room temp.): δ = 0.88 (t, 3 H,
CH3), 1.26–1.47 (m, 16 H, chain), 1.66 (m, 2 H, CH2CH2CN), 2.33
(t, 2 H, CH2CN) ppm.
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N-n-Octylidene-n-octylamine was prepared by the condensation of
octane and n-octylamine in Et2O: the reaction was completed
within a few minutes. It was also prepared from the reaction of
octylamine in AgNO3 and the product was characterized from its
1H NMR spectrum (200 MHz, CDCl3, room temp.): δ = 0.89 (t, 6
H, CH3), 1.24–1.61 (m, 22 H, chain), 2.21 (m, 2 H, CH2C=N), 3.37
(t, 2 H, CH2N), 7.61 (t, 1 H, CH=N) ppm.
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Acknowledgments
Support of this work by the Ministero dell’Istruzione, Università e
Ricerca (MIUR), Rome, is gratefully acknowledged.
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Received: January 19, 2005
Eur. J. Org. Chem. 2005, 3060–3063
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