Reaction of a 2H-1,2,3-Diazaphosphole with Ethane-1,2-Dithiol

Abstract

Reaction of 2-acetyl-5-methyl-2H-1,2,3-diazaphosphole with ethane-1,2-dithiol at ?30°C leads to the formation of 2-acetyl-3-(β-mercaptoethylthio)-5-methyl-1,2,3-diaza-phospholene. On heating, this product forms 2-(β-mercaptoethylthio)-1,3,2-dithia-phospholane, 1,2-bis(1,3,2-dithiaphospholanyl)-dithioethane, and N-acetyl-N′-isopropilidene-hydrazine.     

Reactions of compounds containing dicoordinated phosphorus with isocyanates

Conclusions Reaction of 2-acetyl-5-methyl-1,2,3-diazaphosphole with phenyl, trichloroacetyl, anaphthyl, and trimethylsilyl isocyanates gives the 4-substituted diazaphospholes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 169–171, January, 1986.     

Mechanism of the reactions of diazaphospholes with diazo compounds

Conclusions Diazaphospholes react with diazo compounds by the mechanism of 1,3-dipolar cycloaddition. The reaction of 2-acetyl-5-methyl-1,2,3-diazaphosphole with diphenyldiazomethane proceeds via the intermediate formation of the product of [2 + 3]-cycloaddition.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1376–1380, June, 1987.     

Reactions of diazaphospholes with phenyldiazomethane

Conclusions The action of 2-acetyl-5-methyl-1, 2, 3-diazaphosphole on phenyldiazomethane at –15°C in hexane leads to 2-acetyl-4-methyl-8-phenyl-1-phospha-2,3,7,8-tetraazabicyclo[3.3.0]octa-3,7-diene. The inverse action of phenyldiazomethane on 2-acetyl-5-methyl-1,2, 3-diazaphosphole at 0°C in ether gives 4, 11-diacetyl-6,7-dimethyl-2-phenyl-4,5,10,11-tetraaza-1,3-diphosphatricyclo[6.3.0.0^3,7]undeca-5, 9-diene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 412–418, February, 1986.     

Structure of the UV irradiation product of 5-methyl-2-phenyl-1,2,3-diazaphosphole

Conclusion UV irradiation of 5-methyl-2-phenyl-1,2,3-diazaphosphole leads to 4,4-didehydro-bis(5-methyl-2-phenyl-1,2,3-diazaphosphole).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 633–636, March, 1987.The authors thank A. V. Il'yasov and K. M. Enikeev for discussion of the¹³C NMR spectra.     

2-乙酰基-5-甲基-1,2,3-二氮磷杂环戊二烯同丙炔醇反应研究

用付里叶变换红外光谱及³¹PNMR,探索了2-乙酰基-5-甲基-1,2,3-二氮磷杂环戊二烯同丙炔醇的动态反应过程,推测了可能的反应机理,并通过对二配位磷化物对应的三配位磷化物(2-乙酰基-3-氯-5-甲基-1,2,3-二氮磷杂环戊烯)同丙炔醇反应的研究,验证了二配位磷化物反应机理的可能性。     

Mass spectra of indazolones and pyrazolones—II: 5-pyrazolones

The mass spectral fragmentations of 3-methyl-5-pyrazolone (I), 3-methyl-5-pyrazolone-1-d₁ (II), 3-methyl-5-pyrazolone-1,4,4-d₃ (III), 1-acetyl-3-methyl-5-pyrazolone (IV), 3-methyl-5-ethoxy-pyrazole (V), 3,4-dimethyl-5-pyrazolone (VI), 1,3-dimethyl-5-pyrazolone (VII), 1-acetyl-5-acetoxy-3,4-dimethylpyrazole (VIII), 1,2,3-trimethyl-5-pyrazolone (IX), 3,4,4-trimethyl-5-pyrazolone (X), 3,4,4-trimethyl-5-pyrazolone-1-d₁ (XI), 3-phenyl-5-pyrazolone (XII), 2-acetyl-3-phenyl-5-pyrazolone (XIII) and 5-acetoxy-3-phenylpyrazole (XIV) are reported. Comparison is made between the mass spectra of 5-pyrazolones and 3-indazolones. As for the latter compounds initial loss of ·N₂R is preferred to loss of ·CHO, and is followed by loss of CO. The [M ? 1]ions are intense in the C-methyl substituted pyrazolones, and unlike the 3-indazolones, the pyrazolones do not show any significant loss of HCN from these ions. The mass spectra distinguish between certain isomeric 5-pyrazolones.     

Synthesis of derivatives of 5-amino-4-acyl-1,2,3-triazole, 8-azapurine,and 1,2,3-triazolo[4,5-b]pyridin-7-one using N,N-acetals of acylketenes and tosylazide

By reaction of N,N-acetals of acylketenes with tosylazide there were synthesized 5-amino-4-acyl-1,2,3-triazoles substituted at the endo(N¹)- or exocyclic nitrogen atom. Triazoles containing a free NH₂ group were used in the synthesis of the corresponding 8-azapurines and 4-acetyl-5-benzoylamino-1,2,3-triazole afforded 2-methyl-2H,4H-1,2,3-triazolo[4,5-b]pyridin-7-one.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1392–1397, June, 1990.     

2H-1,2,3-Diazaphospholes in Addition Reactions

Abstract

2H-1,2,3-Diazaphospholes activity depends on the nature of substituents in 2,4,5-positions of the diazaphosphole ring. 5-Methy1-2-pheny1 (acety1)-1,2,3-diazaphospholes 1,2 react with the alcohols at room temperature, and 2-cyclohexyl-4,5-tetramethylen-1,2,3-diazaphosphole -3-at 65°C. The adduct 4 degrades to cyclohexanon-N-cyclohexyl-N-methyl-nydrasone 5.     

Introduction of substituents in the pyridine proton of 7-azaindoline

Electropilic substitution (nitration, bromination, and chlorination) of 4-methyl-6-chloro-7-azaindoline (and its N-acetyl derivative) takes place in the 5 position. 4-Methyl-5-amino-7-azaindoline, 4-methyl-5-nitro-7-azaindoline, and 1-acetyl-4-methyl-5-amino-6-chloro-7-azaindoline were obtained by reduction of 1-acetyl-4-methyl-5-nitro-6-chloro-7-azaindoline under various conditions. A method was developed for the preparation of a new three-ring system — 1,2,3-oxadiazolo[5,4-b]-pyrrolo[2,3-e]pyridine.Communication L from the series Derivatives of Azaindoles. See [1] for communication XLIX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 380–384, March, 1977.     

Functionalization of methyl 3-acetyl-5-[(methoxycarbonyl)amino]-2-methyl-1<Emphasis Type="Italic">H</Emphasis>-indole-1-carboxylate

Oxidative heterocyclization of methyl 3-{1-[2-(carbamoylhydrazinylidene)]ethyl}-2-methyl-5-[(methoxycarbonyl)amino]-1H-indole-1-carboxylate by the action of selenium dioxide in acetic acid and heating of the corresponding thiosemicarbazone in boiling acetic anhydride gave 1,2,3-selenadiazole and 2,3-dihydro-1,3,4-thiadiazole derivatives, respectively. Methyl 3-acetyl-2-methyl-5-[(methoxycarbonyl)amino]-1H-indole-1-carboxylate reacted with selenium dioxide in dioxane–water (30: 1) at 80?90°C to form methyl 5-[(methoxycarbonyl)amino]-2-methyl-3-(2-oxoacetyl)-1H-indole-1-carboxylate whose condensation with o-phenylenediamine afforded methyl 2-methyl-5-[(methoxycarbonyl)amino]-3-(quinoxalin-2-yl)-1H-indole-1-carboxylate.     

Synthesis and reactions of halo-, nitro-, and arylazo-substituted 3-acetyltropolones. Formation of heterocycle-fused troponoid compounds

3-Acetyltropolone ( 1 ) reacted with bromine, iodine, and nitric acid to afford respectively 3-acetyl-5,7-di-bromotropolone ( 2 ), 3-acetyl-7-iodotropolone ( 3 ), and 3-acetyl-5-nitro- ( 4 ) and 3-acetyl-5,7-dinitrotropolone ( 5 ). Azo-coupling reactions of 1 gave 3-acetyl-5-arylazotropolones 7a-f. The Schmidt reactions of 2 and 3 gave respectively 5,7-dibromo- ( 9 ) and 7-iodo-2-methyl-8H-cyclohept[d]oxazol-8-one ( 10 ), while 4 gave 3-acetamido-5-nitrotropolone ( 11 ). Compounds 2 and 4 reacted with hydroxylamine to give 3-methyl-8H-cyclohept[d]isoxazol-8-ones 12 and 13. The reactions of 2 , 3 , and 4 with hydrazine gave 3-methyl-1,8-dihydrocycloheptapyrazol-8-ones 15 , 16 , and 17.     

Formation of carbon-carbon single bonds from isocyanates and cyclic pentaoxyphosphoranes—VI : Synthesis of 4-oxazolones and 4-thiazolones,and a new type of chapman rearrangement

The reaction of 4,5-dimethyl-2,2,2-trimethoxy-2,2-dihydro-1,3,2-dioxaphospholene with carbomethoxy, carbopropoxy and N,N-diphenylcarbamyl isocyanates yields, respectively, 2-methoxy-, 2-propoxy- and 2- diphenylamino-5-acetyl-5-methyl-2-oxazolin-4-one. The reaction with carbophenoxy isocyanate gives two products in a proportion which depends on experimental conditions: 2-phenoxy-5-acetyl-5-methyl-2-oxalin-4-one (1:1 stoichiometry) and 1,3-dicarbophenoxy-5-acetyl-5-methyl-hydantoin (1:2 stoichiometry). The 2-substituted 4- oxazolones are hydrolyzed to 5-acetyl-5-methyl-oxazolidin-2,4-dione. The alkyl group of the 2-alkoxy-4-oxazolones migrates to the adjacent nitrogen to give 3-alkyl-5-acetyl-5-methyl-oxazolidin-2,4-diones. The dioxaphospholene reacts with 2-substituted 2-thiazolin-4,5-diones to give 2-substituted 5-acetyl-5-methyl-2-thiazolin-4-ones, including rhodanine derivatives.     

Synthesis and oxidative aromatization of 5-acetyl-2-cyanoimino-6-methyl-4-phenyl-1,2,3,4-tetrahydropyrimidine with manganese dioxide

The synthesis of 5-acetyl-2-cyanoimino-6-methyl-4-phenyl-1,2,3,4-tetrahydropyrimidine has been carried out by reaction of N-[(tosyl)(phenyl)methyl]-N′-cyanoguanidine with acetylacetone in the presence of sodium hydride with subsequent acid catalyzed dehydration of the 4-hydroxy-2-imino-hexahydropyrimidine obtained. The oxidative aromatization of the tetrahydropyrimidine synthesized using manganese dioxide has been studied. It was found that the products formed depend on the reaction temperature and are either 5-acetyl-2-carbamoylamino-4-methyl-6-phenylpyrimidine or 5-acetyl-2-amino-4-methyl-6-phenylpyrimidine or a mixture of both.     

Ring transformation of 5-acylpyrimidines into 4-acylpyrazoles with hydrazine and phenylhydrazine in acidic medium

5-Benzoyl-4-methylpyrimidines 4a,b and 5-acetyl-4-phenylpyrimidines 5a,b reacted with hydrazines in alcoholic acidic medium to give respectively 4-acetyl-3-phenylpyrazoles 7, 9 and 10 and 4-benzoyl-3-methylpyrazoles 6, 8 and 11 . In the reaction with phenylhydrazine, 5-benzoyl-4-methyl-2-methylthiopyrimidine ( 4a ) led exclusively to 4-acetyl-1,3-diphenylpyrazole ( 10 ) as 5-acetyl4-phenyl-2-methylthiopyrimidine ( 5a ) led to 4-benzoyl-3-methyl-1-phenylpyrazole ( 11 ) via the initial formation of phenylhydrazones of pyrimidines 4a and 5a . However, 5-benzoyl-4-methyl-2-phenylpyrimidine ( 4b ) and 5-acetyl-2,4-diphenylpyrimidine ( 5b ) reacted with phenylhydrazine to afford, each of them, a mixture of two isomeric pyrazoles. The mechanism of these ring contraction reactions is discussed.     

Synthesis of 1,8- and 2,8-dihydrocycloheptapyrazol-8-one derivatives by the reactions of 3-acetyltropolone and its methyl ethers with phenylhydrazine

3-Acetyltropolone ( 1 ) reacted with phenylhydrazine to give 3-acetyltropolone phenylhydrazone ( 3 ) and 3-methyl-1-phenyl-1,8-dihydrocycloheptapyrazol-8-one ( 4 ). The former ( 3 ) cyclized to afford the latter ( 4 ). The reaction of 3-acetyl-2-methoxytropone ( 2a ) with phenylhydrazine gave 4 , 3-methyl-2-phenyl-2,8-dihydrocyclo-heptapyrazol-8-one ( 5 ), and 3-methyl-2-phenyl-2,8-dihydrocycloheptapyrazol-8-one phenylhydrazone ( 6 ). The compound ( 5 ) reacted with phenylhydrazine to afford 6 . The reaction of 7-acetyl-2-methoxytropone ( 2b ) with phenylhydrazone gave 7-acetyl-2-methoxytropone phenylhydrazone ( 7 ), 7-acetyl-2-(N′-phenylhydrazino)-tropone phenylhydrazone ( 8 ), 3-methyl-1-phenyl-1,8-dihydrocycloheptapyrazol-8-one phenylhydrazone ( 9 ), and 6 . The compound ( 7 ) was heated to afford 4 and reacted with phenylhydrazine to afford 8 and 9 . The compound ( 8 ) was also refluxed to give 9 .     

Multicomponent condensation of 6-acetyl-5,7-dihydroxy-4-methylchromen-2-one with aldehydes and Meldrum´s acid

Previously unknown 6-acetyl-10-aryl-5-hydroxy-4-methyl-9,10-dihydropyrano[2,3-f]-chromene-2,8-diones were synthesized by multicomponent condensation of 6-acetyl-5,7-dihydroxy-4-methylchromen-2-one, aromatic aldehydes, and Meldrum´s acid. A fundamen-tal possibility of interconversion of substituted 6-acetyl-10-aryl-5-hydroxy-4-methyl-9,10-dihydropyrano[2,3-f]chromene-2,8-diones and methyl 3-(6-acetyl-5,7-dihydroxy-4-meth-yl-2-oxo-2H-chromen-8-yl)-3-arylpropionates was demonstrated.     

Recyclization of 5-carbethoxy-4-methyl-2-mercapto(amino,hydroxy) pyrimidines to give 5-acetyl-2-mercapto(amino,hydroxy)-4-hydroxypyrimidines

Conditions for the selective preparation of 5-carbethoxy-4-methyl-2-substituted pyrimidines or 5-acetyl-4-hydroxy-2-substituted pyrimidines by condensation of ethoxymethyleneacetoacetic ester with 1,3-binucleophiles are proposed. It is shown that under the influence of sodium ethoxide 5-carbethoxy-4-methyl-2-substituted pyrimidines undergo rearrangement to 5-acetyl-4-hydroxy-2-substituted pyrimidines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1558–1559, November, 1982.     

A new way of synthesizing heterocyclic primary sulfonamide probes for carbonic anhydrase

An N,N-bis(p-methoxybenzyl)-protected α-acetyl-α-diazo-methane sulfonamide proved to be a useful building block for accessing new 5-methyl-1,2,3-thiadiazole-4-sulfonamide as well as methyl 3-sulfamoyl-1H-pyrazole-5-carboxylate. The latter was further subjected to N-alkylation and N-arylation reactions. All resulting compounds showed potent inhibition of I, II and particularly of cancer-related IX and XII isoforms of human carbonic anhydrase.     

Synthesis and selected transformations of 1-(5-methyl-1-aryl-1H-1,2,3-triazol-4-yl)ethanones and 1-[4-(4-R-5-methyl-1H-1,2,3-triazol-1-yl)phenyl]ethanones

By cycloaddition of arylazides to acetylacetone are obtained derivatives of 1,2,3-triazole. In the reaction of 1-[5-methyl-1-(R-phenyl)-1H-1,2,3-triazol-4-yl] ethanones (IIa–IIe) and 1-[4-(4-R-5-methyl-1H-1,2,3-triazol-1-yl)phenyl] ethanones (VIIa-VIIe) with isatin are obtained 2-[1-(R-phenyl)-5-methyl-1H-1,2,3-triazol-4-yl]-4-quinolinecarboxylic acids (IIIa–IIIe) and 2-[4-(4-R-5-methyl-1H-1,2,3-triazol-1-yl)phenyl] -4-quinolinecarboxylic acids (IXa, IXb), respectively. We found that 1-[5-methyl-1-(R-phenyl)-1H-1,2,3-triazol-4-yl] ethanones (IIa–IIe) readily transform into [5-methyl-1-(R-phenyl)-1H-1,2,3-triazol-4-yl] acetic acids (IVa–IVc) by the method of Wilgerodt-Kindler. The (5-methyl-1-phenyl-1H-1,2,3-triazol-4-yl)acetic acid reacts with 5-phenyl-4-amino-4H-1,2,4-triazol-3-thiol affording 6-[(5-methyl-1-phenyl-1H-1,2,3-triazol-4-yl) methyl]-3-phenyl[1,2,4] triazolo[3,4-b] [1,3,4] thiadiazole (VI). Original Russian Text ? N.T. Pokhodylo, R.D. Savka, V.S. Matiichuk, N.D. Obushak, 2009, published in Zhurnal Obshchei Khimii, 2009, vol. 79, no. 2, pp. 320–325.