Nitroso-tertiary butane, (CH 3) 3 C NO, is formed when the corresponding hydroxylamine is oxidized by sulphuric monoper acid (E.
It forms a well-crystallized hydrazone with phenylhydrazine; and a-nitroso propionic acid with hydroxylamine.
On the nitroso, nitroso-ammonium and nitroso-diammonium compounds see C. E.
The first class includes those substances which require no preliminary treatment, and comprises the amides and ammonium compounds, pyridines, quinolines, alkaloids, albumens and related bodies; the second class requires preliminary treatment and comprises, with few exceptions, the nitro-, nitroso-, azo-, diazoand amidoazo-compounds, hydrazines, derivatives of nitric and nitrous acids, and probably cyanogen compounds.
The principal chromophores are the azo, -N = N -, azoxy, = N 2 O, nitro, - N02, nitroso, - NO, and carbonyl, = CO, groups.
The nitroso group is less important.
Hantzsch, Ann., 1896, 2 9 2, p. 3 1 7); by the action of hydroxylamine sulphate on alkaline nitrites in the presence of lime or calcium carbonate, the mixture being rapidly heated to 60° C.; or by the hydrolysis of dimethyl nitroso-oxyurea, (CH 3) 2 N CO N(NO) OH (A.
Tertiary nitro compounds may also be obtained by the oxidation of the corresponding amino-, hydroxyl amino-, and nitroso-hydrocarbons with monopersulphuric acid (E.
The pseudo-nitrols, RR':C(NO)(NO 2), may be obtained by the action of nitrous acid on the secondary nitroparaffins; by the action of silver nitrite on such bromnitrosoparaffins as contain the bromine and the nitroso group united to the same carbon atom (0.
Numerous nitroso compounds are met with in the aromatic series.
They may also be obtained by the reduction of nitroso compounds and of hydrazo compounds and of hydrazones (J.
Zinc and hydrochloric acid in the cold convert it into alloxantin, hydroxylamine gives nitroso-barbituric acid, C 4 H 2 N 2 0 3: NOH, baryta water gives alloxanic acid, C 4 H 4 N 2 0 5, hot dilute nitric acid oxidizes it to parabanic acid, hot potassium hydroxide solution hydrolyses it to urea and mesoxalic acid and zinc and hot hydrochloric acid convert it into dialuric acid, C4H4N204.
Azoxy Compounds, R N O N R', are usually yellow or red crystalline solids which result from the reduction of nitro or nitroso compounds by heating them with alcoholic potash (preferably using methyl alcohol).
Two are known, namely 4-nitroso-a-naphthol or 13; a-naphthoquinone-oxime, formed by the action of nitrous acid on a-naphthol or of hydroxylamine hydrochloride on a-naphthoquinone (H.
It is prepared by the action of aqueous or alcoholic solutions of the caustic alkalis on the nitroso-acidyl derivatives of methylamine (such, for example, as nitrosomethyl urethane, NO.
It yields a nitroso derivative, is nitrated by nitric acid to dilituric acid and brominated by bromine.
Knorre (Ber., 1885, 18, p. 169) separate the metals by adding nitros01 3-naphthol in the presence of 50% acetic acid, a precipitate of cobalti nitroso-13-naphthol, [C 10 H 6 0(NO)] 3 Co, insoluble in hydrochloric acid, being formed, whilst the corresponding nickel compound dissolves in hydrochloric acid.
Nitrification; one of these, which he terms the Nitroso-bacteria., is only capable of bringing about the oxidation of the ammonia to nitrous acid, and the astonishing result was obtained that 12.42.1140, 10.01 10;3U 2.13, 2.35 2.58 4.52 3.43 :` 4.3 0 4.12 this can be done, in the dark, by bacteria to which only pure mineral salts - e.g.
The Nitro-bacteria are smaller, finer and quite different from the nitroso-bacteria, and are incapable of attacking and utilizing ammonium carbonate.
To celebrate his seventieth birthday his scientific papers were collected and published in two volumes (Gesammelte Werke, Brunswick, 1905), and the names of the headings under which they are grouped give some idea of the range and extent of his chemical work: (1) organic arsenic compounds, (2) uric acid group, (3) indigo, (4) papers arising from indigo researches, (5) pyrrol and pyridine bases, (6) experiments on the elimination of water and on condensation, (7) the phthaleins, (8) the hydro-aromatic compounds, (9) the terpenes, (io) nitroso compounds, (11) furfurol, (12) acetylene compounds and "strain" (Spannungs) theory, (13) peroxides, (14) basic properties of oxygen, (15) dibenzalacetone and triphenylamine, (16) various researches on the aromatic and (17) the aliphatic series.
It is oxidized to pyridine by heating with concentrated sulphuric acid to 300° C., or with nitrobenzene to 250° C., or with silver acetate to 180° C. Being an imide it readily yields a nitroso derivative, and N-alkyl and acidyl derivatives.
(Ethyl benzoate may be employed instead of benzoyl glycollic acid for this reaction.) This compound gave a nitroso compound with nitrous acid, which changed spontaneously into benzoylazoimide by loss of water: C 6 H 5 CO NH.
Where the nitrous fumes prevail and there is less water present, sulphur dioxide combines with nitrous acid and oxygen to form nitroso-sulphuric acid, a crystalline substance of the formula SO 2 (OH)(ONO).
The NO 2 (or NO + 0) reacts upon SO 2 + H20, forming SO 5 NH 21 which, being extremely unstable, is at once oxidized to SO 5 NH (nitroso-sulphuric acid).
For similar reasons it is necessary to employ much more water than is required to form H 2 SO 4; and this is all the more necessary as strong sulphuric acid dissolves the nitrous compounds in the shape of nitroso-sulphuric acid, and thus withdraws these oxygen carriers from the gas-space of the chambers where the necessary reactions take place.
The first step towards securing this requirement was taken as early as 1827 by Gay-Lussac, who discovered that the nitrous fumes, otherwise carried away from the lead chambers by the waste atmospheric nitrogen and oxygen, could be retained by bringing the gases into contact with moderately strong sulphuric acid, the result being the formation of nitroso-sulphuric acid: 2H 2 SO 4 + N203 = 2S0 2 (OH) (ONO) + H 2 O, and the latter remaining dissolved in sulphuric acid as "nitrous vitriol."
Canine is a secondary base, forming a nitroso derivative with nitrous acid, a urethane with chlorcarbonic ester and a tertiary base (methyl conine) with methyl iodide; reactions which point to the presence of the = NH group in the molecule.