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.

698/796 (page 672)

$An ' oxy-camphor' [61°] is formed by oxi- dising camphene (v. Terpenes) (Kachler a. Spitzer, A. 200, 358). V. also Campholenic acid. ' Nitro-oxy-camphor,' v. Niteo-campholenic ACID. Cyano-camphor v. Nitrite of Camphor car- BOXYLIC ACID. Ethyl-camphor C1(lH15EtO. (228°). S.G. ^ -946. [a]i = 161°. From sodium-camphor and EtI (Baubigny, Z. [2] 4, 481). Oil. Isoamyl-camphor C„1Hl5(C5HM)0. (278° cor.). [a]j = 59-4°. From sodium-camphor and isoamyl iodide (B.). ' Nitroheptoic acid' C6Hn(NO„)0., i.e. Me.CH(NO,).CMe2.C02H(?) [115°]. From dinitro- heptoic acid and sodium-amalgam (Kullhem, A. 167, 45; Kachler, A. 191, 157). Eectangular four-sided columns (from water). Monoclinic; b:c = 1: -6115 ; 13 = 83° 30'. After several fusions it melts at 111-5°. Quickly heated, it explodes. Reactions.—1. Dissolved in a little aqueous KOH, mixed with KN02 and dilute H,SO., a fine blue colour is formed. This colour is taken up by ether; hence the body is probably akin to pseudo-nitroles.—2. Sn and HC1 produce methyl- isopropyl ketone, hydroxylamine, and C02.—3. Baryta in sealed tubes at 95° does not decom- pose it, but forms the basic salt C,H9BaN04. Dinitroheptoic acid C, H,„(NO,)20.,? i.e. MeC(N20J).CMe,.CO.,H(?) [215°]. Got by Kullhem by treating the residues in the pre- paration of camphoric acid with strong HN03 (A. 163, 231; Kachler, A. 191, 155). Mono- clinic plates; a:b:c = -5735:1: -6024; 0 = 70° 42'. M. sol. cold water, v. sol. hot water. Explodes when rapidly heated. Its ammonium salt gives with cuprie acetate a bluish pp. sol. excess of the acetate (difference from camphoric acid). The free acid does not pp. cupric or lead acetate. The neutral salts give a flocculent pp. with lead acetate. Salt.—BaA'23aq. Needles. Reactions.—1. Keduced in alcoholic solution by sodium amalgam to mononitroheptoic acid. 2. Beduced by Sn and HC1 to methyl iso-propyl ketone and hydroxylamine.—3. Potash and baryta heated with the aqueous acid in sealed tubes produce both nitro-heptoic acid and methyl isopropyl ketone. Hydro-oxycamphoronic acid CjH,^. [164-5°] (Kachler, A. 191, 148). Needles. Sol. cold water. Tribasic acid. Gives no pp. with BaCl2 or CaCl, and NH3, even on boiling (difference from camphoronic acid). Cupric acetate gives no pp. until boiled when a bluish-green cuprie salt is ppd. Lead acetate gives a white pp. soluble in excess. AgN03 gives a white pp. soluble in hot water. Salt s.—NH4H2A'.—CaHA' 2aq.—Ca3A'2. —Ba3A'2.—Cu3A'2.—Ag3A'. ISOMERIDES OF CAMPHOR. Laevorotatory camphor Cl0HlcO. [172° cor.] (B.); [175°] (C). (204°). S.G. ^ -9853 (C). [o]j=-47° (C); -42° (H.). Occurs together with a terpene in the ethereal oil obtained from the leaves of fever-few, Matricaria Parthenium (Chautard, C. R. 37, 166). Apparently formed also by oxidising the laworotatory terpene ob- tained by treating with alcoholic KOH the pro- duet of the action of HC1 on lfevorotatory oil of terpentine (Biban, Bl. 24, 19). Obtained also by oxidising the borneols of madder, valerian, Ngai, and Bang-Phien (Haller, C. R. 103, 64; 104 ,66). HN03 gives laevorotatory camphoric acid [a]j=—46°. The corresponding bromo- camphor is also lsevorotatory, [a]i = —128°. Inactive camphor CH1H](jO. [173°]. Got by oxidising inactive borneol (g.v.) with cold HN03 and then adding water (Armstrong a. Tilden, C. J. 35, 752). Also by oxidising inactive camphene with H2SO., and K,Cr207. Heated with HN03 it forms a camphoric acid, [203°] and giving when heated alone an anhydride, [223°]. Inactive camphor. From Oil of Sage. C,„H1(iO. [174°]. (205° uncor.). When oil of sage is dis- tilled, the fraction 205°-208° deposits this camphor. It apparently only differs from ordi- nary camphor in being inactive, for:—1. PC15 gives an oil which is converted by water into a wax-like solid, [80°] whence Na forms a white solid.—2. Boiled with HN03 (2:1) it forms in- active camphoric acid [186°].—3. Dissolved in toluene and treated with Na and C02 it forms inactive borneol, [200°].—4. Distilled with P2S5 it forms cymene (M. M. P. Muir, C. J. 37, 685). 'Racemic' camphor C20H32O2 (?). [179°]. This name is given to the product of the oxi- dation of a mixture of equivalent quantities of lajvo- and dextro- rotatory borneol, and is therefore inactive by compensation, as racemic acid is (Haller, G. R. 105, 66). It gives a bromo- derivative [51°] and a camphoric acid [205°]. The ' racemic' camphor, bromo-camphor, and camphoric acid were also prepared by mixture and found to be identical with the above. They differ in solubility as well as in melting-point from the active compounds. The borneol of amber, and consequently the camphor derived therefrom, appear to be a mixture of dextro - and laevo-rotatory varieties in unequal propor- tions. Camphors, or bodies resembling camphor, have been found in many essential oils, e.g. oils of alant (p. 94), absinthe (p. 2), chamomile, eucalyptus, lavender, nutmeg, rosemary, &c. When a camphor is converted into borneol, the rotatory power of the resulting borneol varies with each operation, but the camphor regene- rated by oxidising the borneol has in each case the rotatory power of the original camphor (Montgolfier). According to Haller (C. R. 105, 228) this may be explained by supposing that the resulting borneol is always a mixture of a stable borneol rotating in the same direction as the original camphor and of an unstable borneol rotating in the opposite direction. CAMPHOR-CARBOXYLIC ACID CuHI(JOs' [129°]. Formed as a by-product in the pre- paration of borneol from camphor by the action of Na on a solution of camphor in toluene, the product being treated with C02. It is produced by the union of C02 with sodium- camphor (Baubigny, Z. [2] 4, 481, 647 ; A. Ch. [4] 19, 221; Kachler a. Spitzer, B. 13, 1412; M. 2, 233). Long colourless monoclinic pyra- mids. Sol. water. Decomposes below 100° into C02 and camphor. Reactions.—1. Boiling AcCl forms C22H2S0., [196°], crystallising in needles.—2. P205) acting$