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GOLDSTEIN, HAMILTON, HUFFMAN, AND SMITH
methylenediamine in 6 ml. of anhydrous ether was added to 7.4g. (0.078 mole) of trifluoroacetonitrile. The excess nitrile was allowed to reflux for 45 min. then removed by distillation. Dry hexane (40 ml.) was added and the mixture filtered to give 4.4 g. (88%) of product. This solid was dissolved in 50 ml. of anhydrous ether followed by the addition of 70 ml. of hexane. After 34 hr., a white solid had formed on the bottom of the flask. It melted a t 9091.5'. Anal. Calcd. for CI1Hl8N4Fs: C, 41.24; H , 5.66; N, 17.49; F, 35.59. Found: C, 41.21; H , 5.56; N, 17.65; F, 35.42. The Hydrochloride Salt.-Dry hydrogen chloride was bubbled into a solution of 1.0 g. (0.0031 mole) of the free base in 5 ml. of anhydrous ethanol and 20 ml. of anhydrous ether. Then, 50 ml. of anhydrous ether was added to bring about the separation of a colorless oil. After 20 hr., as much as possible of the solvent was decanted. The remainder was removed under vacuum leaving a white solid. It appeared to be extremely hygroscopic and slowly evolved a gas when heated. The analytical sample was dried a t 100" in vacuo over phosphorus pentoxide. Anal. Calcd. for CllH20N4C12F6: C1, 18.03. Found: C1, 18.31. N,N-Dimethylethylenediamine. (a) N-@Dimethylaminoethy1)triiluoroacetamidine [CFsC(=NH) NH( CH2)zN(CH&] .-In a flask equipped with a Dry Ice-acetone reflux condenser and a magnetic stirrer was placed 3.1 g. (0.035 mole) of N,N-dimethylethylenediamine in 10 ml. of anhydrous ether. Trifluoroacetonitrile (5.1 g.; 0.054 mole) was distilled into the system. The nitrile was refluxed for 90 min., then removed. The solid product was recrystallized from chloroform and then sublimed to give 5.1 g. (78%) of a white substance melting a t 10&109' (with sublimation). The solid was quite unstable, decomposing into a brown tar. Anal. Calcd. for CaH12N3Fs: C, 39.34; H , 6.60; N,
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22.94; F, 31.11. Found: C, 36.60; H, 6.68; N, 22.63; F, 29.65. The hydrochloride salt was prepared as follows: A solution containing 285 mg. (0.00156mole) of the amidine dissolved in 50 ml. of anhydrous ether was added to a solution of anhydrous ether saturated with dry hydrogen chloride. Immediately a white precipitate formed. The mixture was stirred for 20 min. before the solvent was decanted. The product was dried under vacuum. The salt decomposed a t approximately 205' (with evolution of a gas). It was hygroscopic. Anal. Calcd. for C8HI4N3C12Fa:C, 28.14; H , 5.10; C1, 27.69; F, 22.26. Found: C, 25.38; H, 6.40; C1, 27.5; F,18.83. N,N-Di-n-butylethylenediamine. (a) N-(8-di-n-butylaminoethy1)trifluoroacetamidine [ CF&( =NH)NH( CHz)*N(C,H&] .-Trifluoroacetonitrile (10.5g.; 0.11 mole) was distilled into a flask (equipped with a Dry Ice-acetone reflux condenser and a magnetic stirrer) containing 8.6 g. (0.05 mole) of N,N-di-n-butylethylenediamine dissolved in 10 ml. of anhydrous ether. The excess nitrile was allowed to reflux for 1 hr. and then removed. The solution, light yellow in color, was kept at about 4' for 2 hr. whereupon light yellow crystals formed. The filtrate was evaporated to yield more of the product. The solid was recrystallized from hexane, the analytical sample from a hexane-ether mixture (5:l). The over-all yield was 10.9 g. (81%) of material melting a t 50-51 '. Anal. Calcd. for C12Hz4N3F~: C, 53.90; H , 9.05; K, 15.73; F, 21.32. Found: C, 53.65; H , 8.86; N, 15.53; F, 21.06. After a few months, the solid had decomposed into a light yellow liquid. The hydrochloride salt was mepared as above. It - melted a t 165.5-167'. Anal. Calcd. for C12Hz6N3C12F3:C1, 20.81. Found: 20.84.
Reduction of the Products of Periodate Oxidation of Carbohydrates. XII. Methylation Studies on Cellulose Polyalcohol' I. J. GOLDSTEIN, J. E
