Chloraloxime, CC1 3 CH: NOH, is obtained when one molecular proportion of chloral hydrate is warmed with four molecular proportions of hydroxylamine hydrochloride and a little water.
Nascent hydrogen reduces it to hydroxylamine (q.v.), whilst solutions of hypochlorites oxidize it to nitric acid.
They may also be prepared by the action of mercuric or cupric oxides on alkaline solutions of hydroxylamine (A.
Pure anhydrous .hydroxylamine has been obtained by C. A.
Meyer, Ber., 1900, 33, p. 2580), and this latter compound condenses with hydroxylamine to form xanthone oxime.
By the action of hydroxylamine or phenylhydrazine on aldehydes or ketones, condensation occurs between the carbonyl oxygen of the aldehyde or ketone and the amino group of the hydroxylamine or hydrazine.
Hydroxylamine gives the dioxime of succinic aldehyde.
Reduction of this ester leads to the formation of ammonia, hydroxylamine, and dimethyl pyrrol dicarboxylic ester, C(CH3): C C02R HN< C(CO 2 R) :C CH3.
They are hydrolysed by dilute mineral acids yielding hydroxylamine and the parent aldehyde or ketone.
Beckmann, Ber., 1886, 1 9, p. 9 8 9; 188 7, 20, p. 2580), yielding as final products an acid-amide or anilide, thus: RC(:N OH)R'-RC(OH) :NR' ---> As regards the constitution of the oximes, two possibilities exist, namely >C: NOH, or > C' ?, and the first of these is presumably correct, since on alkylation and subsequent hydrolysis an alkyl hydroxylamine of the type NH 2 OR is obtained, and consequently it is to be presumed that in the alkylated oxime, the alkyl group is attached to oxygen, and the oxime itself therefore contains the hydroxyl group. It is to be noted that the oximes of aromatic aldehydes and of unsymmetrical aromatic ketones frequently exist in isomeric forms. This isomerism is explained by the HantzschWerner hypothesis (Ber., 1890, 23, p. II) in which the assumption is made that the three valencies of the nitrogen atom do not lie in the same plane.
HO N Aldoximes are generally obtained by the action of hydroxylamine hydrochloride on the aldehyde in presence of sodium carbonate; the oxime being then usually extracted from the solution by ether.
They may also be prepared by the reduction of primary nitro compounds with stannous chloride and concentrated hydrochloric acid; by the reduction of unsaturated nitro compounds with minium amalgam or zinc dust in the presence of dilute acetic acid' Bouveault, Comptes rendus, 1902, 134, p. 1145):R2C:[[Chno 2 -R 2 C: Ch Nhoh - R 2 Ch Ch: Noh]], and by the action of alkyl iodides on the sodium salt of nitro-hydroxylamine (A.
Soc., 18 9 8, 73, p. 35 2) as a colourless liquid by the addition of hydroxylamine hydrochloride to an aqueous solution of formaldehyde in the presence of sodium carbonate; the resulting solution was extracted with ether and the oxime hydrochloride precipitated by gaseous hydrochloric acid, the precipitate being then dissolved in water, the solution exactly neutralized and distilled.
It behaves as a powerful reducing agent, and on hydrolysis with dilute mineral acids is decomposed into formaldehyde and hydroxylamine, together with some formic acid and ammonia, the amount of each product formed varying with temperature, time of reaction, amount of water present, &c. This latter reaction is probably due to some of the oxime existing in the form of the isomeric formamide HCO NH 2.
It crystallizes in prisms which melt at 39° C. A chloral hydroxylamine, CC1 3 [[Choh Nhoh]], melting at 98° C. is obtained by allowing a mixture of one molecular proportion of chloral hydrate with two molecular proportions of hydroxylamine hydrochloride and one of sodium carbonate to stand for some time in a desiccator.
Glyoxime, HON: CH CH: NOH, obtained from glyoxal and hydroxylamine, or by boiling amidothiazole with excess of hydroxylamine hydrochloride and water, melts at 178° C. and is readily soluble in hot water.
Succinic aldehyde dioxime, HON: CH CH2 CH2 CH: NOH, is obtained by boiling an alcoholic solution of pyrrol with hydroxylamine hydrochloride and anhydrous sodium carbonate (G.
Benzaldoximes.-The a-oxime (benz-anti-aldoxime) is formed by the action of hydroxylamine on benzaldehyde.
The 0-form is obtained by the direct action of hydroxylamine hydrochloride on mesityl oxide, the hydrochloride so formed being decomposed by sodium carbonate.
By the direct action of hydroxylamine on a methyl alcohol solution of mesityl oxide in the presence of sodium methylate a hydr oxylamino - ketone, diacetone hydroxylamine, (CH 3) 2 C(Nhoh) CH20OCH3,is formed.
In a similar manner phorone gives rise to triacetone hydroxylamine, CO :[CH2 C(CH3)2]2:NOH.
Arndt, Ber., 1899, 32, p. 2136); by the oxidation of hydroxylamine (ibid., 1900, 33, p. 30); and by the electrolysis of hydrazine and its salts (E.
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.
They react with hydroxylamine and phenylhydrazine, with the formation of aldoximes and hydrazones.
Meyer, Ber., 1891, 24, p. 3530), whilst the primary nitro cornpdunds on heating with hydrochloric acid yield hydroxylamine and an acid: CH 3 CH 2 NO 2 +H 2 0 = CH3 C02H+NH20H (V.
C (: NOH)NO 2, may be prepared by the action of nitrous acid on the primary nitroparaffins; by the action of hydroxylamine on the dibromnitroparaffins; and by the action of nitrogen peroxide on the a-isonitroso fatty acids (G.
On oxidation with chromic acid they yield dinitrohydrocarbons, and on reduction with hydroxylamine (in alkaline solution) or with potassium sulphydrate give ketoximes, RR': C: NOH (R.
Nitroso-tertiary butane, (CH 3) 3 C NO, is formed when the corresponding hydroxylamine is oxidized by sulphuric monoper acid (E.
The remaining oxygen atom is aldehydic or ketonic, for the sugars combine with hydrocyanic acid, hydroxylamine and phenylhydrazine.
It behaves more as a ketone than as a quinone, since with hydroxylamine it yields an oxime, and on reduction with zinc dust and caustic soda it yields a secondary alcohol, whilst it cannot be reduced by means of sulphurous acid.
They are readily reduced to the corresponding hydroquinones or para-dihydroxy-benzenes, and also combine with hydroxylamine hydrochloride to form nitrosophenols, ON C 6 H 4.
HYDROXYLAMINE, NH 2 OH, or hydroxy-ammonia, a compound prepared in 1865 by W.
The residue is extracted by absolute alcohol, which dissolves the hydroxylamine hydrochloride and a little ammonium chloride; this last substance is removed as ammonium platinochloride, and the residual hydroxylamine hydrochloride is recrystallized.
After standing for twenty-four hours, hydroxylamine potassium disulphonate crystallizes out.
The precipitated sodium chloride is filtered, and the solution of hydroxylamine distilled in order to remove methyl alcohol, and finally fractionated under reduced pressure.
Soc., 18 99, 75, p. 79 2) found that the addition of methyl iodide to a methyl alcohol solution of hydroxylamine resulted in the formation of trimethyloxamine, N(CH3)30.
For example, on reduction with zinc and alcoholic potash, the a/' compounds give saturated ketones and also bi-molecular compounds, the Jay being unaffected; the Jay series react with hydroxylamine in a normal manner, the a/3 yield oxamino-oximes.
It undoubtedly contains a keto-group, for it reacts with hydrocyanic acid, hydroxylamine, phenylhydrazine and ammonia; sodium bisulphite also combines with it to form a crystalline compound, hence it contains the grouping CH 3 ï¿½CO-.
It combines with aromatic amines to form azocompounds, with arylhydroxylamines to form azoxy compounds, and with hydroxylamine it gives isodiazobenzene.
Hydroxy-urea, N H2 CO NH OH, is produced from hydroxylamine and cyanic acid (W.
When heated with ammonia it yields ethylamine nitrate, and when reduced with tin and hydrochloric acid it forms hydroxylamine (W.
Mohlau,Ber., 1883, 16, p. 3080), and by the action of hydroxylamine on nitrosobenzenes.