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
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.
705/796 (page 679)
![observers have arrived at somewhat different results, indeed the nature of the resulting pro- ducts depends upon the temperature used in preparing them (Peligot, A. Ch. [2] 67, 172; VOlckel, A. 85, 59 ; Maumene, C. B. 39, 422 ; Graham, C. J. 15, 258; Thomson a. Sherlock, C. N. 25, 242, 282). CARAWAY OIL. Oil of caraway contains a terpene (q. v.) C10H16 identical with oitrene, and carvol (q. v.) C,„HM0. CARB-ACETO-ACETIC ETHER is mesitene- lactone carboxylic acid, p. 20. CARBACETOXYLIC ACID C3H,0,. A syrupy acid, said to be formed by the action of moist Ag.,0 on /3-chloro-propionic acid and on aa-di- chloro-propionic ether. Reduced by sodium- amalgam to glyceric acid, and by HI to pyru- vic acid (Wichelhaus, A. 143, 7; 144, 351; Klimenko, B. 3, 4G8; 5, 477; 7, 1406; cf. Beckurts a. Otto, B. 10, 2039). TRI-CARBALLYLIC ACID C.H^O, i.e. CO.,H.CH(CH,.CO.,H).,. s-Propane tricarboxylic acid. Mol. w. 176. [158°]. S. 40-5 at 14°. Formation.—1. In the preparation of sugar from beet-root (Lippmann, B. 11, 707; 12,1649; Weyer, C. J. 38, 864).—2. By the saponification of its nitrile which is prepared by the action of KCy on s -tri - bromo - propane in alcohol (M. Simpson, Pr. 12, 236; 14, 77 ; C. J. 18, 331).— 3. By reducing aconitic acid or its ether with sodium-amalgam (Dessaignes, C. B. 55, 510 ; Wichelhaus, A. 132, 61; Hlasiwetz, Z. 1864, 734).—4. By the action of potash on the product of the action of KCy on /3-chloro-isocrotonic ether (obtained from aceto-acetic ether and PC15) (Claus a. Lischke, B. 14, 1089).—5. In the same way from a-chloro-crotonic ether or from di - chloro - propylene (epidichlorhydrin) (Claus, B. 5, 358; 9, 223; A. 170, 131; 191, 63).—6. Appears to be formed by the action of HC1 and KC10:I on gallic acid (Schreder, A. 177, 292).—7. Acetyl-succinic ether is con- verted by Na into acetyl-tri-carballylic ether CH3CO.C(CH2.CO.,Et).,.C02Et whence alcoholic KOH or baryta-water produce tri-carballylic acid (Miehle, A. 190, 322).—8. By the oxidation of di-allyl-acetic acid by dilute HN03 (Wolff, A. 201, 53).—9. By boiling citraconic acid with zinc and HC1 (Behrmann a. Hofmann, B. 17, 2692).—10. From propane tetra-carboxylic acid (CO,H.CH,).,C(CO.,H)., by heat (Bischoff, A. 214, 66). Properties.—Hard short trimetric prisms (from water); v. sol. water and alcohol, si. sol. ether. The ammonium salt gives with BaCL or CaCL no pp., even on adding NH:j. Pb(OAc)2 gives a white pp. Fe„Cl6 gives a red pp. Salts. — Na,HA' 2aq(?) — KH..A'. — Ca,A'„ 4aq.—BaHA'.—Ba,A'2 6aq.—Pb3A'.,— Cu.(A'o.—Ag3A'. Tri-ethyl ether Et,A' (c. 300°). Tri-isoamylethcr(C,Hu)3A.'(a,bove3&0°). CARBAMIC ACID CH.,N02 i.e. NH,.C02H. Amido-formic acid. Amide of carbonic acid. Not known in the free state. The ammonium salt is formed by the union of dry or moist CO., (1 vol.) with gaseous NH, (2 vols.) (J. Davy, N. Ed. P. J. 16, 345 ; Bose, P. 46, 352 ; A. 30, 47). Formed also by sublimation of neutral ammonium carbonate, and therefore occurs in commercial ammonium carbonate. Formed also by oxidising glycocoll, leucine, tyrosine, and albumen, with alkaline KMnO, (Drechsel, J pr. [2] 12, 417 ; cf. Hofmeister, pr. [2] 14, 173). It may be conveniently prepared by digesting commercial ammonium carbonate with saturated aqueous NH, for 30 or 40 hours at 20°-25° (Divers, C. J. 23, 215; (/. Kolbe a. Basaroff, C. J. 21, 194). Beactions.—1. Acids decompose carbamates with formation of CO., and NH.,.—2. Boiling water converts carbamates into carbonates.—■ 3. Strongly heating converts the Na salt into sodium cyanate and H,0 (Drechsel, J.pr. [2] 16, 199). Salts.—The carbamates arc soluble in water (difference from most carbonates).—NH,A' (v. supra). Deliquescent plates. Its aqueous solu- tion quickly changes to carbonate, but it is stable in presence of excess of NH3 in the cold. At 60° it is completely split up into CO.. and NH, (Nau- mann, A. 160, 1; B. 18, 1157 ;Horstmann, A. 187, 48 ; Erckmann, B. 18, 1154). In a sealed tube at 140° it forms urea.—NaA'a*aq: formed by adding NaOEt to an alcoholic solution of the ammonium salt ; prisms.—KA': deliquescent. —CaA'._, aq : ppd. by adding lime and alcohol to a solution of NH,A' at 0° ; crystalline powder, sol. water, the solution quickly deposits CaCO.,. When strongly heated it leaves calcium cyan- amide.—SrA'2.—BaA'2. Chloride OC(NH,)CL [c. 50°]. (62°). Pre- pared by passing a stream of dry COCL, into NH.Cl heated to about 400°. Long broad needles. Strong odour. On keeping it slowly changes into cyamelide with evolution of HC1. By water it is decomposed into NH,C1 and C02. On vaporisation it probably dissociates into cyanic acid and HC1, which again recombine on cooling. By CaO it is converted into cyanic acid. With aromatic hydrocarbons in presence of A12C1U it gives amides of aromatic acids (Gattermann a. Schmidt, B. 20, 858). Carbamic ethers. Urethanes. Preparation.—1. From chloro-formic ethers and NH.,.—2. From cyanic acid and alcohols.— 3. From cyanogen chloride and alcohols.—4. By heating alcohols with urea nitrate. Properties.—Solid substances, si. sol. water, v. sol. alcohol and ether ; may be distilled. Beactions.—1. Heating with NH3 gives urea. 2. P,05 gives cyanates.—3. Alcoholic KOH acts upon carbamic ethers of the fatty series accord- ing to the equation: NH...CO.,C„H.,n+1 + KOH = KN.CO + C„H,ltlOH + H.O (Arth, Bl. [2] 45, 702 ; A. Ch. [6] 8, 428). Bornyl and menthyl carbamates act similarly. Methyl ether MeA'. [52°]. (177°). S. 217 at 110° ; S. (alcohol) 73 at 15° (Echevarria, A. 79, 110). Ethyl ether EtA'. Urethane. Mol. w. 89. [c. 50°]. (c. 182°). Formed by the above methods (Dumas, A. Ch. [2] 54, 233; A. 10, 284; Liebig a. Wohler, A. 54, 370; 58, 260; Wurtz, A. 79, 286 ; C. B. 22, 503 ; Bunte, Z. [2] 6, 96; A. 151, 181). Also from carbonic ether and NH3 (Cahours, C. B. 21, 629 ; A. 56, 266). Beactions.— Alcoholic potash, at the ordinary temperature, gives large crystals of potassium cyanate. In this case NH..CO..K is not formed as an intermediate product. A solution of](https://iiif.wellcomecollection.org/image/b21995990_0001_0705.jp2/full/800%2C/0/default.jpg)
