Attempted Hydrogenolysis of Amines with Triphenyltin Hydride¹

Abstract

2Rk3nN(C2H5)2 + Con + H 2 0 + (Rdh)?COs + 2(C2H6),NH (3) ( R = GH6, n-CaH7, or n-GHg) Infrared absorptions characteristic to the diethylaminotin grouping, Sn--N (C2H&, were observed a t 1290 (m), 1173 (vs), 1010 (s), 880 (s), and 780 (s) cm.-l, all being common to the three trialkyl(diethylamin0) tins herein described. These bands completely disappeared on exposure of the sample to air for several minutes on a sodium chloride plate, when characteristic bands of organotin carbonate appeared at 1560-1520 (vs), 1370 (vs), 1070 (m), and 840 (m) cm.-' instead.These results show that the organotin-nitrogen bonding is rather stable to heating, as indicated by no change upon distillation, but is highly reactive toward proton-containing reagents. ExperimentalAnalyses .-A microelementary analysis for carbon and hydrogen waa given up because of the too high sensitivity of the sample to air (equation 3). As soon as a sealed ampoule was cut, diethylamine which was recognized by the strong odor vaporized.Nitrogen was analyzed by titration according to equation 2: an exactly weighed sealed ampoule containing about 2.0 g. of the sample waa crushed with a glass rod in 30 ml. of standardized 0.5 N hydrochloric acid, and the excess acid was back-titrated with 0.5 N sodium carbonate with methyl orange as an indicator.Tin analyses were carried out according to Farnsworth and Pekola.9 In this case the vaporization of diethylamine has no effect on the analytical values of tin. Triethyl(diethy1amino)tin.-A tetrahydrofuran solutionof diethylaminomagnesium bromide prepared from 2.9 g. (0.12 g.-atom) of magnesium, 10.9 g. (0.1 mole) of ethyl bromide, and 7.3 g. (0.1 mo!e) of diethylamine in 50 ml. of tetrahydrofuran was added dropwise to a solution of 14.5 g. (0.06 mole) of triethyltin chloride10 (b.p. 86-88'/9 mm.) dissolved in 50 ml. of tetrahydrofuran. An exothermic reaction was observed during this procedure. After refluxing for 4 hr. the solvent was distilled and the reaction product, was fractionated under reduced pressure. A fraction boiling a t 72-88'/11 mm. was collected; yield, 10.5 g. (6370). Redistillation gave 9.5 g. of an analytically pure fraction boiling a t 114-117'/23 mm. All procedures were carried out in a nitrogen atmosphere. This sample gave a negative Beilstein test for halogen. The product was stored in sealed ampoules under nitrogen.Anal. Calcd. for CloH~5KSn: Sn, 42.69; N, 5.04. Found: Sn,42.64,42.98,42.45; N,4.92. Tri-n-propyl(diethy1amino)tin and tri-n-butyl(diethy1amino)tin were also obtained in about 707, yields by an analogous way from tri-n-propyltin chloride10 (b.p. 122-123"/10 mm.) and tri-n-butyltin chloride10 (b.p. 130-132'/4 mm. ), respectively.Tri-n-propyl(diethy1amino)tin had b .p. 11&120°/13 mm .Anal. Calcd. for C13HslNSn: Sn, 36.97; ?;, 4.36.Found: Sn, 37.41; N, 3.96.Tri-%-butyl( diethy1amino)tin distilled a t 124-1 34 O / 8 mm.

Notes

“…Anal. Caled, for C8H5N03: C, 58.9; H, 8.6; N, 3.1. Found: C, 60.0; H, 8.3; N, 3.1. Ethyl N-Benzyloxycarbonyl-D L-alanylglycylglycinate.-A 5-g. sample (0.017 mole) of N-benzyloxycarbonyl-DL-alanylglycylhydroxamic acid was dispersed with 2.8 g. (0.02 mole) of ethyl (13) S. Goldschmidt and H. Lautenschlager, Ann,, 680, 68 (1953). ( 14) G. H. L. Nefkens and G. I. Tesser, J.…”

“…Anal. Caled, for Ci3HnN02: C, 73.22; , 5.20; N, 6.57. Found: C, 73.28; H, 5.24; N, 6.69. The infrared spectrum of N-carbophenoxyazepine (10% in carbon tetrachloride, carbon disulfide) possessed the following significant absorptions: 5.80 (s); 6.06 (m), 6.17 (m), 7.5 (s), 7.66 (s-m), 9.32 (m), 10.82 (m), 13.80 µ (s). Ultraviolet spectrum showed X"°H 219.5 µ (e 20,400), 242 (sh) (5060), 303 (910); X"Tk"""• 325 µ (« 640).…”

Comparisons of organic Group IVB lithium compounds

“…Reactions of triorganotin hydrides with amines lead to the corresponding ditin (88)(89)(90)(91)(92). It was originally thought that the reaction was a deamination, but more recent work indicates that the action of the amine is catalytic, no hydrocarbon or ammonia being formed (91,92).…”