Carbon bisulphide combines with primary amines to form alkyl dithiocarbamates, which when heated lose sulphuretted hydrogen and leave a residue of a dialkyl thio-urea, CS 2 +2R NH 2 - R NH CSS NH 3 RCS(NHR)2+H2S; or if the aqueous solution of the dithiocarbamate be boiled with mercuric chloride or silver nitrate solution, a mustard oil (q.v.) is formed, R.NH CSS NH3R+HgC12-Hg(R NH CSS)2->2RNCS-}-HgS+H2S.
Thus the thio-alcohols or mercaptans (q.v.) contain the group - CH2 SH; and the elimination of the elements of sulphuretted hydrogen between two molecules of a thio-alcohol results in the formation of a thio-ether or sulphide, R 2 S.
Oxidation of thio-ethers results in the formation of sulphoxides, R2: S: 0, and sulphones, R2: S02; oxidation of mercaptans yields sulphonic acids, R S0 3 H, and of sodium mercaptides sulphinic acids, R S0(OH).
We may also notice that thio-ethers combine with alkyl iodides to form sulphide or sulphonium compounds, R3; SI.
Thio-aldehydes, thio-ketones and thio-acids also exist.
Considering derivatives primarily concerned with transformations of the hydroxyl group, we may regard our typical acid as a fusion of a radical R CO - (named acetyl, propionyl, butyl, &c., generally according to the name of the hydrocarbon containing the same number of carbon atoms) and a hydroxyl group. By replacing the hydroxyl group by a halogen, acid-haloids result; by the elimination of the elements of water between two molecules, acid-anhydrides, which may be oxidized to acid-peroxides; by replacing the hydroxyl group by the group. SH, thio-acids; by replacing it by the amino group, acid-amides (q.v.); by replacing it by the group - NH NH2, acid-hydrazides.
OH; R.CO Cl; (R.CO)20; R.CO SH; acid; acid-chloride; acid-anhydride; thio-acid; R CO NH 2 i R CO NH NH2.
Cystin (stone-cystin), or a-thio-/3-aminoglyceric acid " disulphide," (NH 2 ï¿½ CH 2 ï¿½ CH: S.
They are prepared by condensing thio-amides with a-haloid ketones or aldehydes, the thio-amide reacting as the tautomeric thio-imino acid.
Amino derivatives similarly result from thio-ureas and a-haloid ketones; the oxy derivatives from a-sulphocyanoketones by the action of caustic alkali; and the carboxylic acids from chloro-aceto-acetic ester, &c. and thioamides.
Dihydrothiazoles, or thiazolines, are obtained by condensing ethylene dibromides with thio-amides; by the action of a-haloid alkylamines on thio-amides (S.
CYANAMIDE, NC NH 2j the amide of normal cyanic acid, obtained by the action of ammonia on cyanogen chloride, bromide or iodide, or by the desulphurization of thio-urea with, mercuric oxide; it is generally prepared by the latter process.
They behave in most respects as unsaturated compounds; they combine with hydrogen to form amines; with water to form acidamides; with sulphuretted hydrogen to form thio-amides; with alcohols, in the presence of acids, to form imido-ethers R C(:NH) OR'; with ammonia and primary amines to form amidines R C(:NH) NH 2 i and with hydroxylamine to form amidoximes, R C(:NOH) NH 2.
On passing a current of dry carbon dioxide over the reagent,- the gas is absorbed and the resulting compound, when decomposed by dilute acids, yields an organic acid, and similarly with carbon oxysulphide a thio-acid is obtained: RMgX-R CO 2 MgX?R CO 2 H; COS-CS(OMgX) R--R Csoh.
By the condensation of ortho-aminophenols with phosgene or thiophosgene, oxy and thio-derivatives are obtained, the (OH) and (SH) groups being situated in the t t position, and these compounds on treatment with amines yield amino derivatives.
Sulphides and Thio-acids.-Phosphorus and sulphur combine energetically with considerable rise of temperature to form sulphides.