Volume 1

Watts' dictionary of chemistry / revised and entirely rewritten by H. Forster Morley and M.M. Pattison Muir ; assisted by eminent contributors.

Date:: 1888-1894

Credit: Watts' dictionary of chemistry / revised and entirely rewritten by H. Forster Morley and M.M. Pattison Muir ; assisted by eminent contributors. Source: Wellcome Collection.

Provider: This material has been provided by the Royal College of Physicians of Edinburgh. The original may be consulted at the Royal College of Physicians of Edinburgh.

54/796 page 28

$^-Oxy-benzylidene-di-acetonamine ,CH„ . COx HO.CBH4.CH< * >CH2. XNH.CMe/ From di-acetonamine oxalate (5 pts.), p-oxj- benzoic aldehyde (4 pts.), and alcohol (20 pts.) Acid oxalate B'H,C204. Methyl derivative .CH2. COv MeO.C6H4.CH< >CH2. \NH.CMe./ From anisaldehyde and di-acetonamine oxalate. Oxalate B'2H,C,0, [210°]. Cinnamylidene-di-acetonamine X!H2. COv Ph.CH: CH.CH< >CH, § aq. [49°]. XNH.CMe./ From cinnamie aldehyde, diacetonamine, and boiling alcohol. Yellow needles (from alcohol). Easily soluble in ether, light petroleum, chloro- form and benzene, sparingly in water. Vanillo-di-acetonamine C^H^NCXj i.e. .CH, . COv C6H3(OMe)(OH)CH< >CH, vNH.CMe./ is obtained by boiling equal parts of vanillin and acid diacetonamine oxalate in 10 pts. al- cohol, whereby normal vanillo-diacetonamine oxalate is thrown down. This salt forms either a white powder or yellowish crystalline crusts ; si. sol. water, insol. alcohol and ether. The free base is an alkaline oil, slightly soluble in water.—CnH^NO,,!!CI is easily soluble in al- cohol, and. precipitated therefrom by ether.— (Of,H19N03HCl),PtCl4.—C14H19N03HN03. Very small crystals, m. sol. water, and cold alcohol, (C14H,9N03)2H,S04: laminse. (CuH19N03)2C2H204: crystalline, v. si. sol. water, insol. alcohol (Heintz, A. 194, 53). ALKYL-DI-ACETONAMINES. Methyl di-acetonamine C,H15NO i.e. COMe.CH2.CMe2.NHMe, is formed, together with other bases, when acetone saturated with methylamine is left to itself for several weeks. The base is ppd. as acid oxalate, and purified by conversion into platino- chloride.—Free methyldiacetonamine is very un- stable, quickly splitting up into methylamine and mesityl oxide. The hydrochloride is deliquescent. The platinochloride (C7H15NOHCl),PtCl4 crys- tallises in large light-red rhombic prisms, easily soluble in water, nearly insoluble in alcohol. The platinosochloride (C7H15NOHCl),PtCl2, pro- duced simultaneously with the platinochloride, forms dark red crystals. The aurochloride C;H,5NO,HCl,AuCl3, forms short prisms, m. sol. cold, v. sol. hot, water, alcohol, and ether. The normal oxalate (C7HIVNO)2C2H204 forms indis- tinct very deliquescent crystals, very soluble in absolute alcohol; the acid oxalate C,H15NOC2H204 crystallises in small prisms, m. sol. absolute alcohol. The picrate forms yellow needles (Gotschmann, A. 197, 38). Dimethyldiacetonamine C8H17NO i.e. COMe.CH2.CMe.,.NMe2, is formed on heating a solution of dimethyla- mine in acetone at 100°-105° in a sealed tube. Free dimethyldiacetonamine has not been ob- tained as it very easily splits up into dimethyl- amine and mesityl oxide. The platino-chloride (C8H,.NOHCl)2PtCl4 crystallises in small tablets ; the auro-chloride in golden needles, si. sol. water; the nitrate and sulphate in long colour- less deliquescent needles v. sol. alcohol. The acid oxalate, C8H17NOC2H204, is crystalline, v. sol. water and alcohol, nearly insoluble in ether (Gotschmann, A. 197, 27). Ethyldiacetonamine C9H„NO i.e. MeCO.CH2.CMe2.NHEt, is obtained by heating a solution of ethylamine in acetone at 80° for six hours. C16H36N202PtCl6, light red hexagonal plates, insol. ether and alcohol, soluble in alcohol containing HC1. S. 1-16 at 16°. Platinosochloride: C,6H36N202PtCl2; dark red prisms. S. 6-62 at 21°, insoluble in ether and in alcohol. —C8H17N0HC1 forms hy- groscopic microcrystals decomposing at 150°.— C8H18NOAuCl4 crystallises in large lemon-yellow rhombic plates. S. 2-48 at 22°; easily soluble in alcohol and ether; melts under water at about 70°.—The nitrate forms small needles.— (C8H„N0),H2S04 forms tufts of needles.— (CsHuN0),C,H204, concentric groups of hygro- scopic needles.—C8H]7NOC,H,04; needles.—The picrate C8Hl7NO,C6H2(N02)3OH forms short needle-shaped prisms v. sol. water, insol. alcohol and ether. Free ethyldiacetonamine splits up even in the cold into ethylamine and mesityl oxide (Eppinger, A. 204, 50). The prolonged heating of ethylamine with acetone gives rise only to ethyl-diacetonamine, not to any base analogous to triacetonamine. Diethylamine does not appear to form any compound with acetone (Eppinger). Dehydrodiacetonamine CjHuN(?) contained in the mother-liquors of the preparation of acid diacetonamine oxalate, and passes over on dis- tilling them with an alkali. The platinochloride forms slightly sol. laminre (Heintz, A. 183, 276). Triacetonamine C9H17NO i.e. .CMe2.CH2X NH< >CO \CMe2.CH2/ Oxy - tetra - methyl - tetra - hydro -pyridine [58°] (hydrated); [39*6°] (dry). Formation—1. To- gether with diacetonamine, by the action of ammonia on acetone, especially at high tempera- tures (Heintz, A. 174, 133).—2. By prolonged boiling of acetone with a solution of diaceto- namine : C6H13NO + C3H60 = C9H17NO + H,0 (Heintz, A. 178, 305). This, according to Heintz, is the best mode of preparing triacetonamine. It is purified by crystallisation of the oxalate. Triacetonamine separates from a solution of the normal oxalate mixed with KOH, as a hydrate C9H17NO,H20, which crystallises from anhydrous ether in large square tablets, and the mother- liquor on further evaporation and cooling to a very low temperature yields long needle-shaped crystals of anhydrous triacetonamine. Hydrated crystals rhombic a : b : c = 0-9586 : 0-9768 : 1. Triacetonamine sublimes slowly, even at ord. temp. Distils without alteration. Decomposed at 150°-200° by H2S04 or P205, but does not yield definite products. Heated at 100° for 16 hours with fuming hydrochloric acid it yields diacetonamine, dehydropentacetonamine and other products. With chromic acid mixture it gives isopropyl-butyl-amine di-carboxylic acid: C9H]7N04 i.e. C02H.CMe2.NH.CMe.,.CH2.CO.,H (Heintz, A. 198, 69). With ethyl iodide it yields NH2Et, NHEt2, NEt„ NEt4I, dehydrotriacetona-$