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.

696/796 (page 670)

$splits it up into H.,0 and cymene (Alexejeff, J. B. 12, 187).—15. Camphor absorbs S02, becoming liquid.—16. It also absorbs NO,.— 17. Cone. HIAq at 200° forms CI0H„ (103°), 0,H16 (135°-140°), and C,0H,0 (170°-175°) (Weyl, Z. [2] 4, 496; B. 1, 96).—18. Sodium- amalgam has no action.—19. Na acting at 90° on a solution of camphor in toluene forms sodium-camphor and sodium borneol (Baubigny, Z. [2] 2, 408 ; 4, 298) (c/. p. 672).—20. CO, gas passed into the product of the action of Na on camphor in toluene forms the carboxylic acids of camphor and of borneol (Baubigny, Z. [2] 4, 482, 647). Air passed into the same mixture forms camphoric acid (Montgolfier, A. Ch. [5] 14, 75).—21. Camphor does not combine with NaHSO, (Fittig a. Tollens, A. 129, 371).— 22. AcCl has no action.—23. Converted in the animal economy (of a dog) into camphoglycu- ronic acid (q. v.).—24. Melted camphor absorbs BF3 forming C10H)GOBF3 [70°]; when this is heated for 24 hours there is formed cymene and its polymerides, C6H10, C.H12, and other hydro- carbons (Landolph, C. B. 86, 539).—25. Chloral hydrate forms an unstable molecular compound with camphor. It is a viscous liquid, sol. alco- hol and CHC1.,, insol. water (Cazeneuve a. Im- bert, Bl. [2] 34, 209 ; Zeidler, J. 1878, 645).— 26. By heating with ammonium formate at 220°-240° it yields formyl-bornylamine XH2 C8HH<; | (Leuchart a. Bach, B. 20, \CH.NHCHO 104).—27. It does not react with phenyl-cyanate (L. a. B.).—28. Hydroxylamine forms an oxim, v. Camphoroxim. Phenyl-hydrazide C10H1(i:N2HPh. (233°) at 10 mm. From camphor and phenyl-hydra- zine. Oil. Split up by dilute HC1 into cam- phor and phenyl-hydrazine, and by dry HC1 into aniline and the nitrile of campholenic acid (Balbiano, G. 16, 132). Constitution.—The action of hydroxylamine on camphor coupled with the fact that camphor does not combine with NaHS03 indicates that it is a ketone. The ready formation of benzene derivatives indicates a six-carbon ring. Its opti- cal properties are those of a saturated compound, v. also Terpenes. The two following formula; amongst others have been proposed for camphor: CH2.C(C3H,).CH, | (Schiff, A. 226, 249 ; Kanon- CH.,.C(CH3).CO nikoff, J.pr. [2] 32, 511; cf. Kekule, B. 6, 931); CH2.CH2.CH. CH2 | | (Armstrong a. Miller, B. CH3.CH.CH,.CMe.CO 16, 2255). V. also Terpenes. Chloro - camphor C„,H,5C10. [95°]. From camphor and cone. HClOAq (Wheeler, Am. S. [2] 45, 48; A. 146, 81). Crystalline powder (from alcohol); at 200° it gives off HC1. Decomposed by alcoholic AgN03. (a)-Chloro-camphor C,„H,5C10. [84°]. (C.); [93°] (B.). (246°).[a]j = 90°. Formed by passing dry CI into a solution of camphor (760g.) in absolute alcohol (230g.) (Cazeneuve, G. B. 94, 1530; Bl. [2] 38, 9; 44, 161). Formed also by heating chloro-camphor carboxylic acid (Schiff a. Puliti, B. 16, 887 ; Balbiano, G. 17, 95). Hard, brittle, monoclinic needles; smelling like camphor; vola- tile with steam. Not decomposed by alcoholic AgN03. Sodium-amalgam reduces it to cam- phor; the copper-zinc couple, and hot soda- lime, act similarly. Alcoholic KOH at 180° gives borneol. Phenyl - hydrazine forms C10Hr>(N,HPh)(N.,H,Ph) [56°] (B.). (^-CMoro-camphorC^H^ClO. [100°]. (246°). [a]j = 57°. Deposited from the mother-liquor after the preceding has separated (Cazeneuve, C. B. 95, 1358; Bl. [2] 39, 116). Soft, minute, needles, more soluble than the preceding ; mis- cible with boiling alcohol. Not decomposed by alcoholic AgN03) but converted by boiling alco- holic KOH into the preceding body. Phenyl- hydrazine produces the same compound [56°] as with the preceding (B.). (a)-Di-chloro-camphor C10HuCl2O. [96°]. S.G. 4-2. [a]j = 573° (in alcohol or chloroform). Formed by passing dry chlorine for several hours into camphor dissolved in absolute alcohol at 80°-90°. The product is ppd. by water and crystallised from alcohol (Cazeneuve, C. B. 94, 730, 1058; Bl. [2] 37, 454). Trimetric prisms (from alcohol); a:b:c= 1-8358:1:1-4820 ; si. sol. cold, v. sol. hot, alcohol; almost insol. water but rotates upon it. Above 150° it blackens, giving off HC1. Insol. HOAc (difference from camphor). It forms a liquid combination with aldehyde. (/3)-Di-chloro-camphor C10H,,Cl,O. [77°]. [o]j = 57-4° (in alcohol); 60 6° (in CHCl,). Ppd. by adding water to the mother liquor from which the preceding has crystallised (Cazeneuve, C. B. 94, 1360 ; Bl. [2] 38, 8). Crystallises from al- cohol with difficulty; v. e. sol. alcohol, ether, and chloroform; liquefied by chloral hydrate (difference from the preceding). Tri-chloro-camphor C10H13Cl3O. [54°]. [a]. = 64° (in alcohol). Formed by saturating chloro- camphor with chlorine at 100° (Cazeneuve, C. B. 99, 609). Minute crystals, insol. water, sol. other menstrua. Gives off HC1 when heated. Bromo-camphor Cl(1H)5BrO. [76°]. (274°). S.G. 1-44 Boo 8S-5 (in a 737 p.c. alcoholic solution) (Kanonnikoff, J. pr. [2] 32, 504). [a]D = 139°. Formed by heating camphor di- bromide at 100° (Perkin, C. J. 18, 92 ; Maisch, C. C. 1873, 437). Monoclinic prisms (from alcohol); m. sol. alcohol, v. sol. CHC13 and benzene ; may be sublimed (Montgolfier, Bl. [2] 23, 253). Beactions.—1. Sodium-amalgam reduces it, in alcoholic solution, to camphor; alcoholic KOH also gives camphor. Sodium added to its solution in toluene gives sodium camphor (K. Schiff, B. 13, 1407).—2. PC15 has no action even at 100° (Schiff, B. 14, 1378; Kachler a. Spitzer, M. 3, 205).—3. Heating with ZnCl2 at 160° gives a mixture of p-xylene hexahydride and a phenol C10H14O apparently identical with the carvacrol obtained by the action of I on camphor (B. Schiff, B. 13,1407).—4. Nitric acid forms bromo-nitro-camphor and camphoric acid (Armstrong, B. 12, 1358; B. Schiff a. Maissen, G. 10, 317).—5. Phenyl - hydrazine forms C10Hr(N2PhH)(N,PhH2), [56°] (Balbiano, G. 17, 95, 155). (a)-Di-bromo-camphor Ci0B.^t2O. [115°]. Formed, together with the preceding, by heating bromo-camphor (1 mol.) with Br (2 mols.) for 11$