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
Catalogue details

Licence: Public Domain Mark

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.

    706/796 (page 680)
    urethane in absolute ether, treated with K or Na gives the derivatives KNH.COJEt, and NaNH.C02Et. Of these, the Na derivative is sufficiently stable for analysis. It is v. sol. abso- lute alcohol, insol. absolute ether. With alco- holic potash containing water K,03 is obtained. The body HgN.CO.OEt is obtained by mixing alcoholic solutions of urethane, HgCL, and KHO (Mulder, B. T. C. 6, 170). Acetyl derivative NHAe.COJEt. [78°] (Conrad a. Salomon, J. pr. [2] 10, 28). Chloro -ethyl ether H2N.C02.C.,H,C1. [76°]. From NH3 and the chloro-ethyl ether of chloroformic acid. Prisms. V. sol. water, alco- hol and ether (Nemirowsky, J. pr. [2] 31, 174). n-Bropyl ether PrA'. [53°]. (195°) (Ca- hours, J. 1873, 748; Eoemer, B. 6, 1102). Long prisms. Isobutyl ether C4H9A'. [55°]. (207°) (Mylius, B. 5, 973 ; Humann, A. Ch. [3] 44, 340 ; A. 95, 372). Isoamyl ether C5HnA'. [60°]. (220°) (Medlock, A. 71, 106; Wurtz, J. Ph. [3] 20, 22). NggcIIgs. Octyl ether CSH17A'. [55°]. (135°) at 25 mm.; (231°) at 760 mm. On distillation it is partially converted into cyanuric acid (Arth, C. B. 102, 977). Bornyl carbamate v. p. 523. Menthyl carbamate v. Menthol. CARBAMIDE v. Ukea. CARBAMIDO- v. Ubamido-. CARBAMINES. Carbylamincs. Iso-nitriles. Compounds of the formula R.N:C. Formation.—1. By distilling primary mon- amines with chloroform and alcoholic potash : BNK, + CHC13 + 3KOH = 3KC1 + ENC + 3H,0 (Hofmann, A. 144, 114; 146, 107). —2. By treating an alkyl iodide (1 mol.) with silver cyan- ide (2 mols.) a double salt RNCAgCy is formed ; on distilling this compound with cone, aqueous KCy there is formed KCyAgCy and the carb- amine passes over (Gautier, A. 146, 119; 149, 29, 155 ; 151, 239). HgCy2 and ZnCy, may also be used in preparing carbamines (Calmels, Bl. [2] 43, 82).—3. In small quantity in preparing nitriles by distilling potassium alkyl sulphates with potassium cyanide.—4. By distilling the compounds of thio-carbimides with tri-ethyl- phosphine (Hofmann, B. 3, 766 ; Z. 7, 29). Broperties.—Volatile stinking poisonous oils. Beactions.—l. Alkalis have no action.—2. Mineral acids instantly convert them into alkylamines and formic acid: BNC + 2H,0 = ENH, + H.CO,H. Water at 180° acts similarly. 3. Dry HC1 forms a compound, quickly decom- posed by water as in 2.—4. Organic acids form alkyl-formamides.—5. EtI forms a compound (difference from nitriles).—6. HgO oxidises them to alkyl cyanates E.N:CO, alkyl- form- amides being also formed (Gautier, A. 149, 311). CARBAMINE-CYAMIDE or CARBAMINE- CYANAMIDE so called is described as Amido- di-cyanic acid. Its derivatives are described as Ethyl-carbimido-ubea, Caebimido-ethyl-ueea, &c. C ARB ANIL v. Phenyl cyanate. CARBANILIC ACID v. Phenyl - oaebamic ACID. CAREANILIDE v. s-Di-phenyl-drea. CARBANILIDO- v. Phenyl-ueamido-. CARBAZOLE C12H9N i.e. <^]|'>NH. Mol. w. 167. [238°]. (352° cor.). V.D. 5-86 (calc. 585). S. (alcohol -92 at 14° ; 3-88 at 78°. S. (toluene) -55 at 16-5; 5-46 at 100° (Bechi, B. 12, 1978). Occurrence.—Among the products of the dis- tillation of coal tar; hence it occurs in crude anthracene (Graebe a. Glaser, B. 5, 12, 376 ; A. 163, 343 ; 167,125 ; 174,180 ; 202, 21; Zeidler, A. 191, 297). Formation.—1. Bypassing vapour of aniline or diphenylamine through a red-hot tube.— 2. From imido-di-phenyl sulphide (thio-di- C H phenyl-amine) by boiling HN^^'^'^S with freshly reduced copper for 2 or 3 hours ; the yield is about 60 p.c. (Goske, B. 20, 233). Properties.—White lamina or tables. Easily sublimes. A solution in cone. H,SO., is turned green by HN03. May be distilled, over red-hot zinc-dust without change. Although an imide, it forms a compound with picric acid and its acetyl derivative is obtained with difficulty. Beactions. — 1. It is not affected by cone. HClAq or alcoholic KOH even at 300°. Cold cone. H2SO, dissolves it without change, but at 100° a di-sulphonic acid results. — 2. HN03 forms nitro- compounds.—3. Sodium-amalgam does not reduce it in alcoholic solution, but HI and P at 210° reduce it to carbazoline Cl2HnN.— 4. By exhaustive chlorination with SbCl5 it yields per - chloro - diphenyl or per - chloro- benzene according to circumstances as yet un- determined (Merz a. Weith, B. 16, 2875).— 5. By heating with oxalic acid the compound C3,H25N30 or H0.C(C6H3<(?^ »3 is obtained. It forms minute crystals which very readily yield blue solutions (carbazole blue) on oxidation (Suida, B. 12, 1403; Bamberger a. Miiller, B. 20, 1903). Potassium derivative C12H„NK. From carbazole and KOH at 230°. Picric acid compound CI2H,N C6H2(NO,)3OH. [182°]. From carbazole (1 pt.) and picric acid (1| pts.) in toluene. Red prisms; v. si. sol. cold benz- ene or alcohol. Decomposed by a large quan- tity of alcohol, by water, and by alkalis. Nitrosamine C12HsN.NO. [82°J. Nitrous acid in an alcoholic solution of carbazole forms mono- and di-nitro-carbazole. If carbazole (3 g.) be mixed with acetic acid (60 g. of S.G. T04) and ether (60 g.) be poured in, on adding KN02 the nitrosamine is dissolved in the ether as fast as it is formed, and crystallises out on evaporation. Long flat golden needles. Soluble in ether, CS2, chloroform, glacial acetic acid and benzene. It is decomposed if heated with alcohol mixed with an acid, carbazole being regenerated. Alcoholic KOH turns it blood-red. Reducing agents regenerate carbazole. Cone. H.,SO, gives a dark-green colour (Zeidler, A. 191, 305). Acetyl derivative C12H8NAc. [69°]. (above 360°). From carbazole and Ac,0 at 250°. Slender needles (from water); v. si. sol. water, v. e. sol. alcohol. Erdmann's solution does not turn it green. Its picric acid compound is orange.