Synthesis of several cyclopalladated biacetylmonoxime arylhydrazones

Palladium(II) complexes of biacetylmonoxime arylhydrazones (HL, aryl = phenyl, o-, m-, and p-tolyl, p-chloro- and p-nitrophenyl) and biacetylmonoxime N′-methyl-phenylhydrazone (HL′) have been prepared and characterized. The hydrazomines, HL and HL′, are coordinated through oxime- and hydrazone-nitrogen atoms as a bidentate ligand in the complexes [PdX₂(HL or HL′)] (X = halogen atom) formed under neutral conditions. Under basic conditions the deprotonated complexes [PdX(L or L′)] are obtained. Deprotonation occurs at the oxime group of HL′ and the ligand remains coordinated through oxime- and hydrazone-nitrogen atoms. The other hydrazoximes (HL) are cyclopalladated at the ortho position of the benzene rings and act as an NNC terdentate ligand in the deprotonated complexes [PdXL].     

Studies on arylhydrazones of ethyl arylsulfonylglyoxylates

The reaction of arylhydrazones of 4-arylthiosemicarbazides of arylsulfonylglyoxylic acid with ω-bromoacetophenone has given arylhydrazones of N-(3-aryl-4-phenyl-2-thiazolinylidene)hydrazides of arylsulfonylglyoxylic acids. The reaction of ethyl p-toluenesulfonate with o-aminothiophenol and o-phenylenediamine in polyphosphoric acid has given 2-(p-tolylsulfonyl)methylbenzothiazole and 2-(p-tolylsulfonyl)methylbenzimidazole. From 2-(p-tolylsulfonyl)methylbenzothiazole, a styryl and the corresponding carbocyanine with a substituted indoline have been obtained. The considerable hypsochromic shift of the absorption maxima of the latter is explained by the influence of the voluminous electronegative group SO₂R in the position α to the heterocyclic nuclei.     

邻甲基取代杂萘联苯型聚芳酰胺的合成与性能

二氮杂萘酮;物理性能;邻甲基取代杂萘联苯型聚芳酰胺的合成与性能     

Research on arylhydrazones of substituted glyoxylic acids

Reaction of the hydrazides and acetylhydrazides of cyanoacetic acid with aryldiazonium chlorides gives arylhydrazones of the hydrazide and acetylhydrazide of cyanoglyoxylic acid. 2-Acetyl-3-imino-4-arylpyrazol-5-ones and 3-imino-4-arylazopyrazol-5-ones are obtained by cyclizing the arylhydrazones.For Part IX see [1].     

Studies on arylhydrazones of ethyl arylsulfonylglyoxylates

The reaction of arylhydrazones of 4-arylthiosemicarbazides of arylsulfonylglyoxylic acid with -bromoacetophenone has given arylhydrazones of N-(3-aryl-4-phenyl-2-thiazolinylidene)hydrazides of arylsulfonylglyoxylic acids. The reaction of ethyl p-toluenesulfonate with o-aminothiophenol and o-phenylenediamine in polyphosphoric acid has given 2-(p-tolylsulfonyl)methylbenzothiazole and 2-(p-tolylsulfonyl)methylbenzimidazole. From 2-(p-tolylsulfonyl)methylbenzothiazole, a styryl and the corresponding carbocyanine with a substituted indoline have been obtained. The considerable hypsochromic shift of the absorption maxima of the latter is explained by the influence of the voluminous electronegative group SO₂R in the position to the heterocyclic nuclei.     

Investigations on arylhydrazones of substituted glyoxylic acids

The reaction of arylhydrazones of ethyl cyanoglyoxylate with hydroxylamine hydrochloride in aqueous ethanolic solution in the presence of sodium acetate at the boil has given 3-amino-4-arylazoisoxazol-5-ones. The reaction of arylhydrazones of ethy cyanoglyoxylate with hydroxylamine in the presence of sodium ethoxide in the cold has given arylhydrazones of the amide-oxime of ethyl mesoxalate. The action of acetic anhydride or aryl isothiocyanates on arylhydrazones of the amide oxime of ethyl mesoxalate has given arylhydrazones of the ethyl esters of 5-substituted 1,2,4-oxadiazolyl- or 1,2, 4-thiadiazolylglyoxylic acids.For part XI, see [11].     

Cyclization of arylhydrazones of nitroformaldehyde and its derivatives

2,3,4,5-Tetrahydro-1,2,4-triazine derivatives are obtained when nitroformaldehyde arylhydrazones are heated with formaldehyde and aromatic amines. Bromonitroformaldehyde arylhydrazones react with thiourea to give substituted 5-inimo-4,5-dlhydro-1,3,4-thiadiazoles and react with sodioacetoacetic ester to give 1-aryl-3-nitro-4-acetyl-5-pyrazolones. The action of chlorosulfonic acid on cyanonitroformaldehyde arylhydrazones leads to ring closing to the corresponding 1,3,5-triazines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 425–427, March, 1974.     

含杂萘联苯结构聚醚酰亚胺共聚物的物理性能

二氮杂萘酮;含杂萘联苯结构聚醚酰亚胺共聚物的物理性能     

Research on arylhydrazones of substituted glyoxylic acids

3-Aryl-4-(arylhydrazonochloroformyl)-2-[(carbethoxy or carbarnoyl)cyanomethylene]-4-thiazolines were obtained by condensation of arylhydrazones of chloromethylglyoxylic chloride with arylamides of cyanomonothiomalonic acid ethyl ester or amide. The chlorine atom in these compounds is readily exchanged by a hydrazino group to give 3-aryl-4-(arylhydrazonohydrazinoformyl)-2-[(carbethoxy or carbamoyl)cyanomethylene]-4-thiazolines. 2-(Arylhydrazonocarbethoxyformyl)-4-(arylhydrazonochloroformyl)thiazoles were obtained by reaction of arylhydrazones of chloromethylglyoxylic chlorides with arylhydrazones of monothiomesoxalic acid ethyl ester amide. Arylhydrazones of ethyl 1H-tetrazolyl-5-glyoxylate were synthesized by condensation of arylhydrazones of ethyl cyanoglyoxylate with ammonium azide in dimethylformamide.     

Research on arylhydrazones of substituted glyoxylic acids

Substituted 2-benzalhydrazono-3-phenyl-4-(arylhydrazonochloroformyl)-4-thiazo-lines and 2,2′-azinobis[3-aryl-4-(arylhydrazonochloroformyl)-4-thiazolines], respectively, are formed in the condensation of arylhydrazones of chloromethylgly-oxyloyl chloride with 4-phenylthiosemicarbazones and 1, 6-diarylhydrazodithiocar-bonamides.     

Antioxidant activity of arylhydrazones in sunflower oil oxidation

Antioxidant properties of arylhydrazones in sunflower oil oxidation and regular trends in variation of the antioxidant activity of arylhydrazones in the process in comparison with ethybenzene oxidation were examined.     

Fischer synthesis of indoles from 2,6-disubstituted arylhydrazones

A review of the literature data on the Fischer synthesis of indoles from 2,6-disubstituted arylhydrazones is given. As a result of their own experimental studies of the indolization of hydrazones from 8-R-N-amino-1,2,3,4-tetrahydroquinolines the authors established that no less than five different transformations of the cyclohexadienoneimine intermediate, including 1,2 and 1,4 shifts and splitting out of the substituent, may follow attack on the 8 position of the tetrahydroquinoline ring. Attack in the 10 position of the tetrahydroquinoline ring leads to another cyclohexadienoneimine, which undergoes indolization with the loss of apropylamine chain via a different mechanism. It was proved by experiments with labeled compounds that 1,3 migration of the methyl group (R=CH₃) is the result of a double 1,2 shift, while the 1,4 shift is a direct reaction.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 200–216, February, 1978.     

Nickel(II) complexes of β-N-alkylimme arylhydrazones

Summary -N-alkylimine arylhydrazone ligand complexes of nickel(II) have been synthesised by metal template reactions. The azomethine nitrogen and the a-nitrogen of the arylhydrazone coordinate to the metal with square-planar geometry around the nickel(II) ion. Structures have been proposed based on the spectral properties of the complexes.Reprints of this article are not available.     

A novel reaction of ketone arylhydrazones with nitric oxide

The reaction of ketone arylhydrazone (1) with nitric oxide affords C1′-nitro azo-compounds (2) in good yields. Products were identified by NMR, IR, MS, and X-ray crystallography. The reaction is assumed to be most likely initiated by an electrophilic addition of NO₂ to the carbon atom of the carbonnitrogen double bond.     

Heterogeneously catalytic cyclization of arylhydrazones to indoles (review)

The principles and peculiarities of the heterogeneously catalytic cyclization of arylhydrazones to indoles are examined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1443–1452, November, 1988.     

Synthesis of substituted 2,3,4,5-tetrahydro-1,2,4-triazines from nitroformaldehyde arylhydrazones

2,3,4,5-Tetrahydro-1,2,4-triazines were obtained by condensation of nitroformaldehyde arylhydrazones with aldehydes and ammonia or primary amines.