The carbonyl oxygen may also be replaced by the oxime group,: N OH; thus the acids yield the hydroxamic acids, R C(OH): NOH, and the acid-amides the amidoximes, R C(NH 2): NOH.
The aldoximes are converted by the action of dehydrating agents into nitriles: RCH: NOH-->R C: N+H 2 0.
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.
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.
Formaldoxime, CH 2: NOH, was obtained by W.
It is readily transformed into a solid polymer, probably (CH 2: NOH)3.
In the absence of water, it forms salts of the type (CH 2: NOH)3 HC1 with acids.
Acetaldoxime, CH 3 CH: NOH, crystallizes in needles which melt at 47° C. On continued fusion the melting point gradually sinks to about 13° C., probably owing to conversion into a polymeric form.
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.
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.
Acetoxime, (CH 3) 2 C:NOH, melts at 58-59° C. and is readily soluble in water.
Mesityl oxime, (CH 3) 2 C: CH C(: NOH)CH 3, exists in two modifications.
Acetophenoneoxime, C 6 H 5 C(:NOH) CH3, melts at 59° C. In glacial acetic acid solution, on the addition of concentrated sulphuric acid, it is converted into acetanilide.
Benzophenone oxime, CeHSC (:NOH)C 6 H 5, exists only in one modification which melts at 140° C.; whereas the unsymmetrical benzophenones each yield two oximes.
Wallach (Ann., 1900, 312, p. 171) has shown that the saturated cyclic ketones yield oximes which by an application of the Beckmann reaction are converted into isoximes, and these latter on hydrolysis with dilute mineral acids are transformed into acyclic amino-acids; thus from cyclohexanone, e-amidocaproic acid (e-leucine) may be obtained: CH2" C NOH C CH 2 CH 2 7: ?12?CH2 CH2 NH /CH2 CH2 C02H CH2', An ingenious application of the fact that oximes easily lose the elements of water and form nitriles was used by A.
The pentose is then obtained from the acetylated compound by successive treatment with ammonia and dilute acids: CH 2 OH ([[Choh) 3 Choh Ch: Noh -)Ch20h (Choh)3 Choh Cn - Ch 2 Oh (Choh) 3 Cho]].
The primary compounds form nitrolic acids of the type R C (: NOH) NO, the secondary yield pseudo-nitrols of the type RR': C(NO)(NO 2), whilst the tertiary nitro compounds are not acted upon by nitrous acid.
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.
C(: NOH)NO 2 +2HCI=HNO 2 +CH 3 C(: NOH)C1.HCI.
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.
CH 2 OH CH20H CH20H CH20H (CH OH) 3 -> 01 OH) 3 -> (CH OH) 3 --> (CH OH)3 CH OH CH OH CH OH CHO CHO CH:NOH CN Hexose -p Oxime -> Nitrile -> Pentose.
The ketone, dihydroxyacetone, CH 2 OH CO CH 2 OH, was obtained by Piloty by condensing formaldehyde with nitromethane, reducing to a hydroxylamino compound, which is oxidized to the oxime of dihydroxyacetone; the ketone is liberated by oxidation with bromine water: 3H CHO + CH 3 NO 2 -- (CH 2 OH) 3 C NO 2 - (CH 2 OH) 3 C NH OH -- (CH 2 OH) 2 C: NOH - > (CH20H)2CO.
Quinone-dioxime, HON: C 6 H 4: NOH, crystallizes in colourless or yellow needles, which decompose when heated to about 240° C. Potassium ferrocyanide in alkaline solution oxidizes it to dinitrosobenzene, whilst cold concentrated nitric acid oxidizes it to para-dinitrobenzene.
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 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.
The latter readily undergo the " Beckmann " transformation on treatment with acid chlorides, yielding substituted acid amides, RR' C:NOH -› RC(NR') OH - R CO NHR' (see OxIMES, also A.
With nitrous acid (obtained from amyl nitrite and gaseous hydrochloric acid, the ketone being dissolved in acetic acid) they form isonitroso-ketones, R CO CH:NOH (L.
Manasse, Ber., 1888, 21, p. 2177), C2H5 CO C :(NOH) CH 3 -I-11C5HONO = C 2 H 5 CO.
It forms needles which melt at 160° C. (3-Naphthoic acid, obtained b y boiling 0-methylnaphthalene with dilute nitric acid, or by hydrolysis of its nitrile (formed when formyl-0-naphthalide is heated with zinc dust), crystallizes from alcohol in needles which Nitrosonaplithols or naphthoquinone-oxames, C 1 oH 6 (OH)(NO) or melt at 184° C. C 1 oH 6 (: NOH): 0.
Most articles are bought and sold by a weight called batman, or man, of which there are several kinds, the principal being: Man-i-Tabriz=8 abbasis = 640 miskals = 6-49 lb Man-i-Noh abbasi=9 abbasis = 720, , = 730
Bamberger, Ber., 94, 7, 1955), C,H 5 CH: CH CH: NOH --4[C 6 H 5 CH: CH NH COH] -*C,H,N; by the action of hydriodic acid on the oxydichlorisoquinoline formed when phosphorus pentachloride reacts with hippuric acid; by the distillation of homophthalimide over zinc dust (M.