Amide Oxime Research Articles

Thermal properties of copoly(1,4‐arylene‐1,2,4‐oxadiazole)s having n‐alkyloxymethyl side branches

AbstractTwo series of copoly(1,4‐arylene‐1,2,4‐oxadiazole)s (co‐PAOs) having n‐butyloxymethyl and n‐octyloxymethyl side branch were prepared by solution cyclodehydration of the corresponding precursor copoly(1,4‐arylene terephthaloyl amide oxime)s (co‐PAAs) obtained by solution polycondensation of mixtures of 2,5‐bis(n‐alkyloxymethyl)‐1,4‐benzenediamide oximes (DIS‐TADO) and terephthaldiamide oxime (TADO) with terephthaloyl chloride. Thermal properties of the copolymers were investigated and discussed in connection with the length and the content of side branches. All the copolymers are crystalline.

Amidoxim‐Nachbargruppen in Cyclodehydrierungsreaktionen

Amide Oxime Functions as Neighbouring Groups in Cyclodehydrogenation ReactionsDehydrogenation of the o‐(tertiary amino)benzamide oximes 4, which are monosubstituted at the amide N atom of the neighbouring group, by the mercury edta complex yields tricyclic amino nitrones 9 with a quinazoline 3‐oxide moiety or lactams 8. Product formation depends on the nature of the N substituent, the size of the amine ring, and the reaction conditions. The configuration of the amide oximes and the conformation of the tricyclic systems is determined by NMR‐spectroscopic methods.

The synthesis of pyrimidine 1-oxides: a new transformation of amide oximes

The title N-oxides were prepared from several carboxamide oximes on treatment with 1,3-dicarbonyl derivatives.

Application of surface-active amide oximes to the collectors for gallium ion in an ion-flotation system

Utilisation de ces oximes comme collecteurs presentant des proprietes chelatante et moussante pour la flottation ionique d'une solution aqueuse mixte d'ions d'aluminium et de gallium dans differentes conditions operatoires. Etude des effets des concentrations d'acide, de base ou des collecteurs dans la solution du temps de bullage et de la structure des collecteurs sur la flottabilite

ChemInform Abstract: Preparation and Surface Active Properties of Alcohol Ethoxylates with an Amide Oxime Terminal Group.

AbstractBase‐catalyzed cyanoethylation of polyglycol ethers such as (III) gives the cyanoethyl derivative (V) which reacts with free hydroxylamine (VI), forming the amidoxime (VII).

Preparation and surface active properties of alcohol ethoxylates with an amide oxime terminal group

AbstractAmide oxime compounds have become of major interest because they can complex with uranium, gallium and various transition metal ions. In this work surface active amide oximes were prepared to make some functions of the amide oxime group exhibit as molecular aggregates in aqueous media. Amide oximes were obtained from nitriles which were prepared by the cyanoethylation of alcohol ethoxylates with a monodispersed oligo(oxyethylene) group. Surface active properties of these compounds were measured under various conditions and were compared with nonionics of the alcohol ethoxylate type. The pKa1 values of these amide oximes were about five, and they acted as cationic surfactants under acidic conditions and nonionic ones under neutral and basic conditions. When they served as nonionics, the cloud point, CMC, γCMC and foaming properties of surface active amide oximes were similar to other alcohol ethoxylate nonionics.

Simple Procedure for the Synthesis of Pyridinecarbohydroximoyl Chlorides and Bromides

Abstract A convenient synthesis of 2-, 3- and 4-pyridine-carbohydroximoyl chlorides and bromides is described, This method involves reaction of appropriate amide oxime with sodium nitrite in the presence of hydrochloric or hydrobromic acid.

放射線グラフト重合法によるウラン吸着用中空糸状アミドオキシム樹脂の合成

中空糸状の多孔性ポリエチレン樹脂を基材とし,放射線グラフト重合法によりシアノ基を導入しグラフト率が79%から127%の4種類のアクリロニトリル樹脂を得た。それぞれをヒドロキシルアミン溶液と反応させてアミドオキシム型キレート樹脂を合成した。元素分析によりアミドキシム化反応における窒素導入量を求めたところ19基材あたり4.3mmo1から8.5mmolであった。導入された窒素の大部分はアミドオキシム基になっていると考えられる。基材において広範囲に分布する細孔半径は,グのラフト反応により分布が狭くなり1000Åあたりに集中した。19樹脂あたりの細孔容積は,2.5cm3/gからおよそ半分に減少したが,1g基材あたりの細孔容積はグラフト率とともに増大し,グラフト率が127%のとき4.5cm3/g-基材となった。比表面積は基材の場合30m2/gであるがグラフト率の増大にともなって減少し,グラフト率が127%のとき15m2/gとなった。アミドキシム化反応における窒素導入量に対し,塩酸および銅はいずれも1.5倍の吸着量を示した。IR測定の結果をも考慮して副反応による酸アミド,ヒドロキサム酸の生成を推定した。導入窒素1原子に対しウラン吸着量は0.64原子の割合であった。

Synthesis of a new chelate resin for uranium adsorption from seawater. Polystyrene resin containing two amide oxime functions in the repeating unit

AbstractDicyanoethylated polystyrene, poly{1‐[4‐(2,2‐dicyanoethyl)phenyl]ethylene} (2), which was obtained from the reaction of chloromethylated polystyrene, poly[1‐(4‐chloromethylphenyl)‐ethylene] (1) with malononitrile under phase transfer reaction conditions, was treated with hydroxylamine in methanol to afford a polystyrene resin 3 with two amide oxime functions in the repeating unit. Resins 3 exhibit a higher adsorptivity of uranium in seawater than a corresponding resin 5 with one amide oxime function in the repeating unit. The effective adsorption of uranyl ions by resins 3 is attributed to the close proximity of the two amide oxime functions in the styrene monomeric unit, which can effectively coordinate to a uranyl ion.

Synthesis of 3-Substituted 5,6-Diphenylpyrimidin-4-ones from Diphenylcyclopropenone and N-Substituted Amide Oximes

Synthesis of 3-Substituted 5,6-Diphenylpyrimidin-4-ones from Diphenylcyclopropenone and N-Substituted Amide Oximes

Preparation of Sydnone-4-carboxamide Oximes and Their Conversion into 4-(1,2,4-Oxadiazol-3-yl)sydnones

Abstract 3-Arylsydnone-4-carboxamide oximes (2) were prepared from the corresponding 3-arylsydnone-4-carbonitriles and hydroxylamine in high yields. The amide oximes 2 reacted with orthoesters to give 3-aryl-4-(1,2,4-oxadiazol-3-yl)sydnones.

Synthesis of 1,2,4‐oxadiazines and their rearrangement to pyrimidines

AbstractSeveral amide oximes underwent condensation reactions with dimethyl acetylene dicarboxylate to afford 1:1 adducts. Under basic conditions, these adducts underwent ring closure to afford several methyl [3‐(substituted)‐4,5‐dihydro‐5‐oxo‐6H‐1,2,4‐oxadiazin‐6‐ylidene]acetates. The reactions of these compounds with a variety of amines resulted in addition‐rearrangement reactions with the formation of the corresponding methyl 2‐substituted‐5‐substituted amino‐1,6‐dihydro‐6‐oxo‐4‐pyrimidine carboxylates.

The Reaction of Phosphylated Amide Oximes in Alkaline Solution

AbstractAmide oximes react rapidly with phosphoryl compounds in neutral solution to give the corresponding O‐phosphorylated products 1–3. These decompose in dilute alkaline solution by several routes depending on the substituents at phosphorus (Tables 1 and 2). — The di‐O‐alkyl phosphates 3 undergo a 1,2 rearrangement to give the cyanamide which reacts further as in the Lossen and Tiemann rearrangements. O‐Alkyl phenylphosphonates however rearrange in a more complex manner with the rapid release of the corresponding alcohol. The cyclic phosphonoamidate then rapidly hydrolyses to give the N‐phosphorylated amide oxime which then rearranges slowly to the O‐phosphonylated isomer. The significance of this rearrangement is discussed in terms of current views of pseudorotation of cyclic phosphorus compounds.

Phosphorus derivatives of amide oximes. Part 1. Synthesis of N 2-[bis(dimethylamino)phosphinoyl]amidines, 4,6-disubstituted 2,5-dihydro-1,3,5,2-triazaphosphorine 2-oxides, and 3-dialkylamino-1-dimethylamino-1H-2,1-benzazaphosphole 2-oxides

The reactions of tris(dimethylamino)phosphine with amide oximes gave three types of compound, depending on the amide oxime substituents and the temperature: N2-[bis(dimethylamino)phosphinoyl]amidines (1), 4,6-disubstituted 2,5-dihydro-1,3,5,2-triazaphosphorine 2-oxides (2), and 3-dialkylamino-1-dimethylamino-1H-2,1-benzazaphosphole 2-oxides (3). With unsubstituted amide oximes only compounds (1) were formed at room temperature; at 80 °C a 1 : 1 mixture of (1) and (2) was obtained. Compounds (3) were obtained only with N-alkylbenzamide oximes. The formation of compounds (1)–(3) can be explained in terms of an unstable CN–O–PIII intermediate. 31P CIDNP effects were observed during the formation of compounds (3), in support of a radical mechanism. 1H N.m.r. and i.r. data are discussed.

Synthetic reactions using transition metal complexes. Conversion of amide oximes into amidines by pentacarbonyliron and evidence for imine intermediates in the deoximation of ketoximes

N-Alkyl and N-arylbenzamide oximes, when treated with pentacarbonyliron in dry tetrahydrofuran undergo reductive fission of the N–O linkage to give the corresponding amidines in high yields; an identical reaction takes place with methyl mesityl ketoxime which gives the corresponding imine.

Syntheses of bis(η‐cyclopentadienyl)titanio derivatives of poly(amide oxime)s

AbstractBis(η‐cyclopentadienyl)titanio derivatives of poly(amide oxime)s (3) were synthesized via the condensation of amide oximes (1a–g) with (Cp)2TiCl2 (2) utilizing both the interfacial and solution techniques. The reaction was found to be rapid, occuring in generally less than 90s and to increase with the stirring rate in the region of 8000 to 24 000rpm but with yield remaining constant above 12 000rpm.

Metal derivatives of amide oximes. III. Products of the reaction between dialkyldichlorosilanes and amide oximes

The reaction of dialkyldichlorosilanes with amide oximes leads to cyclic products whose monomeric form has an l-oxa-3,5-diaza-2-silacyclopent-4-ene structure. These compounds exist mostly in adimeric form, occasionally monomeric or trimeric. Their infrared spectra have been interpreted. The secondary amino group of the compounds has been trisilylated.

Heterocyclic imines and amines. Part XVI. 2,6-Diaminopyrazine and its 1-oxide from iminodiacetonitrile

With palladium–charcoal, 2,6-bishydroxyiminopiperazine (made from iminodiacetonitrile and hydroxylamine at 70°) underwent hydrogen transfer to yield 2,6-diaminopyrazine, characterised as the diacetyl derivative. From iminodiacetonitrile and hydroxylamine in the cold, the bis(amide oxime) resulted but in the hot with added hydroxylamine hydrochloride—conditions which effected a cycloaddition even to nitrilotriacetonitrile—a hydrated complex of 2,6-bishydroxyiminopiperazine and hydroxylamine hydrochloride was formed, together with 2-amino-6-hydroxyaminopyrazine 1-oxide. Reduction of the latter afforded 2,6-diaminopyrazine 1-oxide, which was acetylated to 2,6-diacetamidopyrazine 1-oxide; the latter was deoxygenated to 2,6-diacetamidopyrazine. Attempts to prepare the mono(amide oxime) of iminodiacetonitrile led to a self-condensation product of aminoacetamide oxime, namely 2,5-bishydroxyiminopiperazine. In comparative experiments, o-cyanobenzyl cyanide gave with hydroxylamine 1-amino-3-hydroxyaminoisoquinoline, and with a mixture of hydroxylamine and its hydrochloride in the hot, 1,2,3,4-tetrahydro-1,3-bishydroxyiminoisoquinoline. Aspects of the mass spectra of the various compounds are reported.

Some 5-unsubstituted acetylenic and vinylic 1,2,4-oxadiazoles

3-trans-Styryl-1,2,4-oxadiazoles (2) have been prepared by treating unsaturated amide oximes with trialkyl orthoformates or dimethylformamide dimethyl acetal, and from 1,2,4-oxadiazol-3-ylmethylene(triphenyl)phosphonium chloride (12). Phenylpropiolamide oxime with formyl fluoride gives 3-phenylethynyl-1,2,4-oxadiazole which, on nitration, gives as the main product 3-p-nitrophenylethynyl-1,2,4-oxadiazole (4; R = NO2). This compound has been converted into (4; R = Cl). p-Chlorophenylpropiolonitrile gives only 3-amino-5-p-chloro-phenylisoxazole (15) when treated with hydroxylamine, trans-3-(2- and -3-Thienyl)acrylonitrile react more readily with hydroxylamine than do the cis-acrylonitriles. Some cis-3-styryl-1,2,4-oxadiazoles have been obtained from the corresponding trans-compounds by photoisomerization.

Heterocyclic imines and amines. Part XII. Imino-derivatives of piperazine

Sodamide in formamide effected addition of ammonia to N-benzyliminodiacetonitrile (1a) to yield 4-benzyl-2,6-di-iminopiperazine (4), which underwent displacement reactions with water and hydroxylamine, the latter giving 4-benzyl-2,6-dihydroxyiminopiperazine (5a). Similar addition of aniline and 2-aminopyridine to the dinitrile (1a) yielded the 2-imino-6-arylimino-derivatives of (4) which again gave the dioxime (5a) with hydroxylamine. N-Benzoyl-, acetyl-, and unsubstituted-iminodiacetonitrile gave the corresponding 2,6-dihydroxyiminopiperazines. Sodamide in formamide with iminodiacetonitrile provided 2,6-bisformyliminopiperazine, and with nitrilotriaceto-nitrile (10) gave 3,5-di-iminopiperazin-1-ylacetonitrile, which with hydroxylamine produced 3,5-dihydroxyimino-piperazin-1-ylacetamide oxime. The trinitrile (10) with hydroxylamine gave only the acyclic tris(amide oxime).