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.
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.
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.
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.
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.
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.
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.
Free hydroxylamine reduces it to hydroquinone.
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.
They may be prepared by converting nitriles into amidoximes by the action of hydroxylamine, the amidoximes so formed being then acylated by acid chlorides or anhydrides.
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.
It may be prepared by the action of ammonia on diazobenzene perbromide; by the action of hydroxylamine on a diazonium sulphate (K.
Curtius), and with hydroxylamine ketoximes.
Posner, Ber., 1901, 34, P. 3975); with hydroxylamine they form isoxazoles, and with phenylhydrazine pyrazoles.
Those in which the keto groups are in combination with phenyl residues give pyridine derivatives on treatment with hydroxylamine, thus benzamarone, C 6 H 5 CH[CH(C 6 H 5) CO.
Mohlau,Ber., 1883, 16, p. 3080), and by the action of hydroxylamine on nitrosobenzenes.
Diazoimino compounds, R N3, may be regarded as derivatives of azoimide; they are formed by the action of ammonia on the diazoperbromides,or by the action of hydroxylamine on the diazonium sulphates (J.
Well-dried hydroxylamine hydrochloride is dissolved in methyl alcohol and mixed with sodium methylate; a solution of methyldichloramine in absolute ether is then added and an ethereal solution of diazomethane distils over.
When heated with ammonia it yields ethylamine nitrate, and when reduced with tin and hydrochloric acid it forms hydroxylamine (W.
Hydroxy-urea, N H2 CO NH OH, is produced from hydroxylamine and cyanic acid (W.
It combines with aromatic amines to form azocompounds, with arylhydroxylamines to form azoxy compounds, and with hydroxylamine it gives isodiazobenzene.
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-.
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.
HYDROXYLAMINE, NH 2 OH, or hydroxy-ammonia, a compound prepared in 1865 by W.
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.
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.