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.

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$namine hydrochloride heated for ten hours at 120' with aqueous hydrocyanic acid forms the hydrochlorides of diacetonamine cyanhydrin and of nitrilo-diacetonaniine, together with a little amido-iso-butyric acid (Heintz, A. 189, 231; 192,340).—5. Diacetonamine oxalate boiled with alcoholic solutions of aldehydes forms condensation products.—6. Sodium amalgam reduces di-acetonamine to a secondary amido- iso-hexyl alcohol CH3.CH(OH).CH,.CMe.,NH„. CYANHYDRINS. Di-Acetonamine cyaDhydrin CjHuN.O or Me.C(OH)(CN).CH2.CMe2.NH2. Carbylo-di-acetonamine.—Prepared as de- scribed above (Reaction 4).—Trimetrie prisms. V. sol. water. Decomposed by boiling alcohol into HCN and diacetonamine. Boiling HC1 saponifies it, forming Oxy-amido-heptoic acid (q. v.), Me.C(0H)(C02H).CH,.CMe2NH,, the greater part of which changes to its anhydride, di-oxy-tri-methyl-pyrroline, .CO — NH MeC(OH)< | \CH„— CMe., (Heintz, A. 192, 329 ; Weil, A. 232, 208 v. Pyebo- line). Nitrilo-di-Acetonamine C;H14N,0. The hy- drochloride is obtained, as above stated, to- gether with its isomeride. The free base is crys- talline, easily soluble in water, sparingly in ether, and absorbs C02 from the air. Distinguished from carbylodiacetonamine by remaining un- altered when heated to 100°-110° with fuming hydrochloric acid. Resolved by boiling with baryta water into NH3 and amido-trimethyl- oxybutyric acid C,HlvNO.t or its anhydride. The platinochloride (CIH,.1N.,0,HCl),PtCl,l forms yellow rhombic prisms slightly soluble in water. The oxalate C,HnN20,C2H.,04 forms small crys- tals m. sol. water, insol. alcohol (Heintz, A. 192, 342). PRODUCTS FROM ALDEHYDES. Ethylidene-di-acetonamine CKH15N0 or OH ,CH,. COv .CH< >CH, NNH.CMe./ [27°] (200°) vinyl-di-acetonamine; oxy-tri-meth yl- tetra-hydro'-pyridine. Formation.—Together with tri-acetonamine by action of aldehyde and ammonia on acetone. In larger quantity as oxalate, by boiling the acid oxalate of diacetonamine (10 g.) for sixty hours in a reflux apparatus with aldehyde (10 g.) and alcohol (120 g.). The oxalate is washed with hot alcohol, and the free bases separated by potash (Heintz,^. 178, 326 ; 189,214; 191,122). Preparation.—By boiling an alcoholic solu- tion of di-acetonamine oxalate with paralde- hyde (E. Fischer, B. 17, 1793). Properties.—Solidifies at -15° to rectangular or six-sided plates or long prisms. Is deli- quescent. Has a burning taste, smells like tri- methylamine, but when warmed, like camphor. Reduced by sodium amalgam to its dihydride or ethenyl-di-acetone-alcamine. Salts.—(B'HCl).,PtCl,3aq. Flat prisms.— B'2H.,S04. Minute needles, v. sol. water, si. sol. al- cohol'.—B'2H.,C204. SI. sol. alcohol.—B'4 3H,,C.,04. A platino-chloride of vinyl-di-acetonamine and tri-acetonamine (C8H15N0.HC1 + C9H,TNO.HCl)PtCl4 + 2H20 is formed by direct combination of its constituents. 100 pts. water at 14° dissolve 8-65 pts. of the anhydrous salt (Heintz, J. 1877, 442). Pentylidene-di-acetonamine CuH21NO or yCll.y . COx CHMe.,.CH.>.CH<; >CH2 Mm.CMe./ Valcral-di-acetonamine; oxy-di-mcthyl-iso-butijl- tctra-hydro-pyridine [15°-22°]. From valeric aldehyde and alcoholic di-acetonamine oxalate (Antrick, A. 227, 3(37). Needles in stars (from ether). Insol. water, sol. alcohol, ether, benzene, and petroleum. Salts.—B',H.,C.,04. Needles [190°]. V. si. sol. cold water or alcohol.—(B'HCl).PtCl, [205°]. Heptylidene-di-acetonamine C13H,5N0 or ,CH., . COv c6h13.ch<; >CH2 ^NH.CMe./ Oxy-di-methyl-hexyl-tetra-hydro-pyridine [29-5°]. From cenanth-aldehyde and alcoholic di-acetonamine oxalate (Antrick, A. 227, 370). Needles (from ether). Oxalate B'2 H2C204 [c. 150°]. Benzylidene-di-acetonamine C13Hl;NO or ,CH,. COv Ph.CH< >CH, \NH.CMe./ Oxy-phenyl-di-viethyl-tetra-hydro-pyridine [61°] (230°). Obtained as oxalate, by boiling 1 pt. benzaldehyde, 1 pt. acid diacetonamine oxalate, and 12 pts. alcohol, gradually separating as a powder which may be purified by crystallisation from water. Colourless needles or monoclinic prisms (from ether). V. sol. alcohol and ether; si. sol. water. Tasteless, has a faint aro- matic odour. Forms normal and acid salts.— Cr)Hl7NOHCl. Crusts or druses of crystals.— (C,.,H„NO.HCl),PtCl4. Warty groups of crys- tals, or when separated from alcohol on ad- dition of ether, elongated six-sided tablets. Slightly soluble in hot, insol. in cold alcohol. The aurochloride forms pale-yellow crystals.— C13Hl;NOHN03 + 2H20 (?). Small crystals, mode- rately soluble in cold water.—(C13Hl7NO),H.,S04. Small crystals, easily soluble in water, very slightly in absolute alcohol.—(C13HnNO)2,C2H,0,. Microscopic crystals, nearly insoluble in alcohol, v. si. sol. water (R. Schiff, A. 193, 62). w-Amido-benzylidene-di-acetonamine /CH, . COx NH,.CUH4.CH< >CH, \NH.CMe./ From the nitro-derivative by reduction with SnCl2. Oil. Salts.—BH,C,,0, [113°]. p-Amido-benzylidene-di-acetonamine.—From the nitro-derivative by SnCL,. Salt.—BH.,C204. o-Nitro-benzylidene-di-acetonamine /CH, . CO. NO.,.C0H,.CH< >CH2. \NH.CMe./ From o-nitrobenzoic aldehyde and alcoholic di- acetonamine oxalate. Salts.—B'., H,,C204.— B'HC1.-(B' HCl),PtCl4. m-Nitro-benzylidene-di-acetonamine. Salts.—B'HCl [208°].-(B'HCl)2PtCl4 [203°]. p-Nitro-benzylidene-di-acetonamine [142-5°]. Needles (from ether). Nearly insol. light petro- leum. Salts.—B'HCl aq. [c. 200°].—(B'HCl)2PtCl4.$