Arsines tris arsine

Si3AsC9H27, Arsine, tris(trimethylsilyl)-, [17729-30-5], 31 151 Si3N2Cl6H32, Benzenecarboximidamide,... 

Tris(dimethyIamino)arsine is prepared by dimethylaminolysis of arsenic(III) chloride in a suitable solvent. The reaction is generally applicable since arsenic(III) iodide and alkyl-haloarsines of the general formula R AsX3 (ra = 1 or 2, X = Cl, Br, or I) have been reported to react similarly with secondary amines. In addition to dimethylamine, other secondary amines, such as diethylamine, have been used to prepare the corresponding tris(dialkylamino)arsine. Tris(dialkyl-amino) arsines have also been prepared by transamination of tris(dimethylamino) arsine with higher-boiling secondary amines such as diethylamine, di-n-butylamine, or piperidine. 

C 7H,40, l,4-pentadien-3-one, 1,5-diphenyl-, palladium complex, 28 110 CjgHtjAs, Arsine, tri]riienyl-, iron complex, 26 61... 

Trimethylarsine gives a 98% yield of trimethylarsine difluoride when treated with xenon difluoride [102] in fluorotrichloromelhane. and tnsfpentafluorophen-yl)arsine gives a 94% yield of tris(pentafluornphenyl)arsme difluoride after reaction with dilute fluorine in fluorotnchloromethane at 0 C [106] Other trivalent arsenic compounds have also been fluorinated with xenon difluoride [103] In addition, arsines have been oxidatively fluorinated by iodine pentafluoride [107] or electrochemically in 26-34% yield [108]... 

Both von Hirsch 1U) and Weingarten and White 39) have reported the amination of aldehydes and ketones by tris(dimethylamino)arsine (142) to yield the corresponding gem diamine (143) or enamine (144). Von Hirsch s... 

A reagent more reactive than tris(dimethylamino)arsine employed by Weingarten and White 39) was tetrakis(dimethylamino)titanium (145). With this compound it was possible to prepare N,N-dimethyl(l-isopropyl-2-methylpropcnyl)amine (147) from diisopropyl ketone. Weingarten and White 39) have suggested a possible mechanism for this reaction (see p. 88). If benzaldehyde 39,111), formaldehyde 111), or acetaldehyde 39) is used, the corresponding gem diamine or aminal (143) is formed. 

A. Preparation.—The first reverse Wittig olefin synthesis has been reported. Triphenylphosphine oxide and dicyanoacetylene at 160 °C gave the stable ylide (1 78%) the reaction was reversed at 300 °C. No comparable reaction was observed with a variety of other activated acetylenes but tri phenyl arsine oxide gave the corresponding stable arsoranes with dicyanoacetylene (— 70 °C), methyl propiolate, hexafluorobut-2-yne, dimethyl acetylene dicarboxylate, and ethyl phenylpropiolate (130 °C). 

The arsenic compounds most commonly found in environmental and biological materials, and in working places, are arsenite and arsenate ions [As(III) and As(V)], monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsine, di- and tri-... 

The reaction is complete when the clear supernatant solution in the reaction vessel no longer contains chlorine as detected by the addition of dilute nitric acid and silver nitrate solution to ca. 1-ml. of the clear solution withdrawn from the reaction flask. After the reaction is complete, the ice bath is removed, and stirring is continued for 2 hours at room temperature. After standing overnight, the dimethylammonium chloride is filtered and washed with n-hexane, with careful exclusion of the moisture of the atmosphere. The combined filtrates are distilled at atmospheric pressure to remove the solvent. The tris(dimethylamino)arsine distills at 36°/2 mm. (55 to 57°/10 mm.). The yield is 402 g. (78%). 

Tris(dimethylamino)arsine (d2o 1.1248 nd 1.4848)3 is a colorless liquid which is readily hydrolyzed to form arsenic (III) oxide and dimethylamine when brought into contact with water. The compound is soluble in ethers and hydrocarbons. The product is at least 99.5% pure (with respect to hydrogen-containing impurities) as evidenced by the single sharp peak at —2.533 p.p.m. (relative to tetramethylsilane) seen in the proton nuclear magnetic resonance spectrum of the neat liquid. 

---