With hydroxylamine it yields an oxime, which by the action of concentrated sulphuric acid rearranges itself to N-methylsuccinimide [CH2 C0]2N CH3.
It does not combine with hydroxylamine, as does the isomeric phloroglucin which yields a trioxime(see Polymethy1.Enes).'
Nef based his formula, which involves bivalent carbon, on many reactions; in particular, that silver fulminate with hydrochloric acid gave salts of formylchloridoxime, which with water gave hydroxylamine and formic acid, thus - C: NO OAg -)HC?C?
Jowitschitsch (Ann., 1906, 347, p. 2 33) inclines to Scholl's formula; he found that the synthetic silver salt of glyoxime peroxide resembled silver fulminate in yielding hydroxylamine with hydrochloric acid, but differed in being less explosive, and in being soluble in nitric acid.
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.
Thus with hydroxylamine aldehydes yield aldoximes, R CH: N OH, and ketones, ketoximes, R 2 C: N OH (see Oximes), while phenyl hydrazine gives phenylhydrazones, R 2 C:N NH C 6 H 5 (see Hydrazones).
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.
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.
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.
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.
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.
On the addition of phenylhydrazine it gives a phenylhydrazone, and with hydroxylamine furnishes an oxime C6H5.CH3.C=N.OH melting at S9°C. This oxime undergoes a peculiar rearrangement when it is dissolved in ether and phosphorus pentachloride is added to the ethereal solution, the excess of ether distilled off and water added to the residue being converted into the isomeric substance acetanilide, C6H5NHCOCH3, a behaviour shown by many ketoximes and known as the Beckmann change (see Berichte, 1886, 19, p. 988).
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.
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.
The oxime of benzaldehyde (C 6 H 5 CH: N OH), formed by the addition of hydroxylamine to the aldehyde, exhibits a characteristic behaviour when hydrochloric acid gas is passed into its ethereal solution, a second modification being produced.
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.
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.
Schmidt, Ber., 1884, 17 p. 2064); and 2-nitrouo-a-naphthol (, -naphthoquinone-oxime), formed by the action of hydroxylamine hydrochloride on 13-naphthoquinone.
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.