Diazo reactions with unsaturated compounds: XIII. Reactions of p-(buta-1,3-dien-1-ylsulfonyl)benzenesulfonamide with arenediazonium chlorides, 1-aryl-3,3-dimethyltriaz-1-enes, and arenediazonium tetrachlorocuprates(II)

p-(Buta-1,3-dien-1-ylsulfonyl)benzenesulfonamide reacted with arenediazonium chlorides, 1-aryl-3,3-dimethyltriaz-1-enes, and arenediazonium tetrachlorocuprates(II) in aqueous acetone in the presence of copper(II) chloride to give the corresponding p-(4-aryl-3-chlorobut-1-en-1-ylsulfonyl)benzenesulfonamides.     

Diazo reactions with unsaturated compounds: XII. Reaction of 1-(<Emphasis Type="Italic">p</Emphasis>-Carboxybenzenesulfonyl)-1,3-butadiene with aryldiazonium chlorides, 1-aryl-3,3-dimethyl-1-triazenes,and aryldiazonium tetrachlorocuprates(II)

1-(p-Carboxybenzenesulfonyl)-1,3-butadiene reacts in aqueous acetone with aryldiazonium chlorides and 1-aryl-3,3-dimethyl-1-triazenes in the presence of copper(II) chloride and with tetrachlorocuprates(II) to form 1-(p-carboxybenzenesulfonyl)-4-aryl-3-chloro-1-butenes.     

Diazo Reactions with Unsaturated Compounds: X. Reactions of <Emphasis Type="Italic">p</Emphasis>-Chloro- and <Emphasis Type="Italic">p</Emphasis>-Bromophenysulfonyl-1,3-Butadienes with Aryldiazonium Chlorides and 1-Aryl-3,3-dimethyl-1-triazenes

1-(p-Chlorophenylsulfonyl)- and 1-(p-bromophenylsulfonyl)-1,3-butadienes in aqueous acetone solutions in the presence of cuprous chloride or cupric chloride react with aryldiazonium chlorides and 1-aryl-3,3-dimethyl-1-triazenes to form 1-(p-chlorophenylsulphonyl)- and 1-(p-bromophenylsulfonyl)-4-aryl-3-chloro-1-butenes, respectively.     

Diazo Reactions with Unsaturated Compounds: VI. Reaction of 1-(p-Nitrophenylsulfonyl)buta-1,3-diene with Arenediazonium Chlorides

1-(p-Nitrophenylsulfonyl)buta-1,3-diene reacts with arenediazonium chlorides in aqueous acetone in the presence of catalytic amounts of CuCl₂·2H₂O to form 1-(p-nitrophenylsulfonyl)-4-aryl-3-chloro-1-bu- tenes. In the presence of SO₂, 1-(p-nitrophenylsulfonyl)buta-1,3-diene does not react with arenediazonium chlorides.     

Diazo Reactions with Unsaturated Compounds: IX. <Emphasis Type="Italic">ortho</Emphasis>-, <Emphasis Type="Italic">meta</Emphasis>-, and <Emphasis Type="Italic">para</Emphasis>-Nitrophenylsulfonyl-1,3-butadienes in Reaction with 1-Aryl-3,3-dimethyl-1-triazenes

1-(m-Nitrophenylsulfonyl)- and 1-(p-nitrophenylsulfonyl)-1,3-butadienes in aqueous acetone in the presence of HCl and copper(I) or copper(II) chloride react with 1-aryl-3,3-dimethyl-1-triaenes to form 1-(m-nitrophenylsulfonyl)- and 1-(p-nitrophenylsulfonyl)-4-aryl-3-chloro-1-butenes, respectively. 1-(o-Nitro-phenylsulfonyl)-1,3-butadiene fails to react in similar conditions.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 4, 2005, pp. 619–621.Original Russian Text Copyright © 2005 by Naidan, Smalius.For communication VIII, see [1].     

Cycloacylation of N-phenyl-N′-R-thioureas with 3-aryl-2-propenoyl chlorides

Cycloalkylation of N-phenyl-N′-R-thiourea with 3-aryl-2-propenoyl chlorides in acetone gives as products 6-aryl-3-phenyl-2-(R-imino)-2,3,5,6-tetrahydro-4H-1,3-thiazin-4-one and their hydrochlorides. The same reaction carried out in acetone in the presence of K₂CO₃ leads to the formation of 6-aryl-3-phenyl-2-(R-imino)-2,3,5,6-tetrahydro-4H-1,3-thiazin-4-ones, N-(3-aryl-2-propenoyl)-N-phenylthioureas, 3-aryl-2-propenoylanilides, and phenyl isothiocyanate.     

Reaction of methyl 1-bromocyclopentane- and -cyclohexanecarboxylates with zinc and 2-arylmethylideneindan-1,3-diones

Methyl 1-bromocyclopentanecarboxylate and methyl 1-bromocyclohexanecarboxylate reacted with zinc and 2-arylmethylideneindan-1,3-diones to give methyl-1-[(aryl)(1,3-dioxo-2,3-dihydro-1H-inden-2-yl)-methyl]cyclopentane(or cyclohexane)carboxylates and 4′-aryl-2′H-spiro[cyclopentane(or cyclohexane)-1,3′-indeno[ 1,2-b]pyran]-2′,5′(4′H)-diones.     

Heterocyclization of functionalized heterocumulenes with C,N-, C,O-, and C,S-binucleophiles: VIII. Synthesis of pyrano(chromeno)[3,4-e][1,3]oxazines by condensation of 1-chloroalkyl isocyanates with 4-hydroxy-6-methylpyran-2-one and 4-hydroxycoumarin

1-Chlorobenzyl isocyanates react with 4-hydroxy-6-methylpyran-2-one and 4-hydroxycoumarin forming 4-aryl-3,4-dihydro-2H,5H-pyrano(chromeno)[3,4-e][1,3]oxazine-2,5-diones. The reaction of 1-aryl-2,2,2-trifluoro-1-chloroethyl isocyanates with the above substrates gives rise to structurally isomeric 2-aryl-2-trifluoromethyl-2,3-dihydro-2H,5H-pyrano(chromeno)[3,4-e][1,3]-oxazine-4,5-diones.     

New synthesis of 4-(1-adamantyl)-2-aryl-1,3-thiazoles from 4-(1-adamantyl)-1,2,3-thiadiazole

Treatment of 4-(1-adamantyl)-1,2,3-thiadiazole with potassium tert-butoxide generated potassium 2-(1-adamantyl)ethynethiolate which reacted with aromatic carboxylic acid chlorides to give unstable S-[2-(1-adamantyl)ethynyl] arenecarbothioates whose acid hydrolysis afforded S-[2-(1-adamantyl)-2-oxoethyl] arenecarbothioates. The latter reacted with ammonium acetate in acetic acid yielding 4-(1-adamantyl)-2-aryl-1,3-thiadiazoles. Reactions of 4-(1-adamantyl)-2-(4-chloro-3-nitrophenyl)-1,3-thiadiazole with cyclic secondary amines gave the corresponding products of nucleophilic replacement of the chlorine atom in the aromatic ring.     

Synthesis of 2-aryl-4-cyano-1,3-oxazole-5-sulfonyl chlorides and N-substituted sulfonamides

Oxidative chlorination of 2-aryl-5-benzylsulfanyl-1,3-oxazole-4-carbonitrile results in the previously unknown 4-cyano-1,3-oxazole-5-sulfonyl chlorides and N-substituted sulfonamides.     

Synthesis of 1,2,4- and 1,3,4-oxadiazoles from 1-aryl-5-methyl-1<Emphasis Type="Italic">H</Emphasis>-1,2,3-triazole-4-carbonyl chlorides

5-Substituted 2-(1-aryl-5-methyl-1H-1,2,3-triazol-4-yl)-1,3,4-oxadiazoles were synthesized by reaction of 1-aryl-5-methyl-1H-1,2,3-triazole-4-carbonyl chlorides with the corresponding 5-substituted 1H-tetrazoles. 5-Methyl-1-phenyl-1H-1,2,3-triazole-4-carbonyl chloride reacted with N′-hydroxybenzimidamides to give 3-aryl-5-(5-methyl-1-phenyl-1H-1,2,3-triazol-4-yl)-1,2,4-oxadiazoles. Reactions of 4-(5-methyl-1H-1,2,3-triazol-1-yl)benzoic acid with N′-hydroxybenzimidamides resulted in the formation of 3-aryl-5-[4-(5-methyl-1H-1,2,3-triazol-1-yl)phenyl]-1,2,4-oxadiazoles.     

Cyclization of 1,3-diaryl-3-phenylsulfanyl-1-propanols to thiochromans with the participation of [1,3]-PhS shift

Optically active (3R,1RS)-3-aryl-1-phenyl-3-phenylsulfanyl-1-propanols were easily dehydrated forming mainly rac-cis-2-aryl-4-phenylthiochroman, and rac-cis-4-aryl-2-phenylthiochroman along with the corresponding trans-isomers. The observed reaction outcome (rearrangement and racemisation) apparently results from the S_EAr reaction involving the unusual 1,3-phenylsulfanyl group migration. This interpretation is supported by the results of theoretical studies (DFT) on the supposed intermediates.     

Cycloacylation of 3-oxo-3-R1-N-R2-propanethioamides by 3-aryl-2-propenoyl chlorides

The products of cyclocondensation of 3-oxo-3-R¹-N-R²-propanethioamides with 3-aryl-2-propenoyl chlorides in acetone in the presence of potassium carbonate are 5-acyl-1-aryl(alkyl)-4-aryl-6-thioxopiperidin-2-ones, 5-acyl-2-aryl-6-aryl(alkyl)amino-2,3-dihydro-4H-thiopyran-4-ones, and 2-acetonylidene-3,6-diaryl-5,6-dihydro-4H-1,3-thiazin-4-ones, the structure of which is proven by both spectral methods and chemical conversions. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 623–628, April, 2006     

5-Aryl-2-furaldehydes in the Synthesis of 2-Substituted 1,3-Benzazoles

2-[2-(5-Aryl-2-furyl)ethenyl]-1,3-benzazoles were synthesized by reaction of 5-aryl-2-furaldehydes with 2-methylbenzoxazole, 2-methylbenzothiazole, 2-methylbenzimidazole, and 2-cyanomethylbenzimidazole. The corresponding benzazoles were also obtained by reaction of N-(5-arylfurfurylidene)anilines with 2-methylbenzoxazoles and of 3-(5-aryl-2-furyl)-2-cyanopropenoyl chlorides with o-phenylenediamine. The acylation of o-aminophenol with 3-(5-aryl-2-furyl)-2-cyanopropenoyl chlorides occurs at the amino group without subsequent oxazole ring closure.     

N-Arylation of 4-fluoro-5-trimethylsilyl-1H-pyrazole

The 1,3-dipolar cycloaddition reaction of fluoro(trimethylsilyl)acetylene prepared in situ with an excess of diazomethane smoothly proceeded to give the corresponding 4-fluoro-5-trimethylsilyl-1H-pyrazole in 84% yield. The copper iodide-catalyzed N-arylation of the fluorinated pyrazole with a variety of aryl iodides afforded N-aryl-4-fluoropyrazoles as desilylation products in good to excellent yields.     

1-Aryl-1-chloro-2,2,2-trifluoroethylisocyanates—convenient reagents for synthesis of 2-aryl-2-trifluoromethyl-2,3-dihydro-4H-benzo[e][1,3]oxazin-4-ones

1-Aryl-1-chloro-2,2,2-trifluoroethylisocyanates react with 3-alkoxyphenols to form N-(1-aryl-2,2,2-trifluoroethylidene)-O-(3-alkoxyphenyl)urethanes, which undergo intramolecular thermal cyclization into derivatives of 2-aryl-2-trifluoromethyl-2,3-dihydro-4H-benzo[e][1,3]oxazin-4-ones.     

Heterocyclizations of Functionalized Heterocumulenes with C,N- and C,O-Dinucleophiles: III.* Cyclization of N-(1-Aryl-1-chloro-2,2,2-trifluoroethyl)-N'-arylcarbodiimides with 3-Substituted 1-Phenylpyrazol-5-ones

Cyclization of N-(1-aryl-1-chloro-2,2,2-trifluoroethyl)-N'-arylcarbodiimides with 3-substituted 1-phenylpyrazol-5-ones yields 6-aryl-4-arylimino-1-phenyl-6-trifluoromethyl-1,4,5,6-tetrahydropyrazolo[4,3-e][1,3]oxazines.     

Synthesis of 1,4,5-trisubstituted-1,2,3-triazoles via coupling reaction of diaminomaleonitrile with aromatic diazonium salts

A mild procedure for the preparation of 2-(5-amino-1-aryl-1H-1,2,3-triazol-4-yl)-2-iminoacetonitriles and 2-(5-amino-1-aryl-1H-1,2,3-triazol-4-yl)-2-oxoacetonitriles was achieved by the reaction of diaminomaleonitrile and phenyl/substituted phenyl diazonium chlorides. 4-Nitrophenyl diazonium chloride afforded 2-amino-3-(3-(4-nitrophenyl)triaz-1-en-1-yl)maleonitrile. Triazole iminoacetonitrile and maleonitrile derivatives were reacted further with excess acetone and benzaldehyde with a catalytic amount of 1,8-diazabicyclo[5.4.0]undec-7-ene to yield 5-(5-imino-2,2-dimethyl-2,5-dihydrooxazol-4-yl)-3-aryl-3H-1,2,3-triazol-4-amine and (E)-N-benzylidene-5-(5-imino-2-aryl-2,5-dihydrooxazol-4-yl)-3-aryl-3H-1,2,3-triazol-4-amine, respectively. Two competitive reactions, i.e., nucleophilic substitution and nucleophilic addition, were observed when triazole oxoacetonitrile and maleonitrile derivatives were reacted with hydroxylamine hydrochloride in the presence of sodium acetate.     

Intramolecular electrophilic cyclization of functional derivatives of unsaturated compounds: III. Reaction of N,4-Diarylbut-3-enamides with arenesulfenyl chlorides. Synthesis of 5-aryl-4-arylsulfanyl-2,3,4,5-tetrahydro-1H-1-benzazepin-2-ones

N-Aryl-4-phenylbut-3-enamides reacted with arenesulfenyl chlorides in chloroform to give N,4-diaryl-3-arylsulfanyl-4-chlorobutanamides, whereas in acetic acid in the presence of lithium perchlorate N-[4-arylsulfanyl-5-phenyltetrahydrofuran-2-ylidene]arenaminium perchlorates were obtained. Reactions of arenesulfenyl chlorides with N,4-diarylbut-3-enamides having strong electron-donating groups in positions 3 and 4 of the N-aryl substituent afforded 5-aryl-4-arylsulfanyl-2,3,4,5-tetrahydro-1H-1-benzazepin-2-ones.     

Reactions of 1,1,4,4-tetramethylsemicarbazide with prop-2-ynyl bromide, allyl bromide, and 1,3-dibromoprop-1-yne

1,1,4,4-Tetramethylsemicarbazide readily undergoes alkylation with prop-2-ynyl bromide and allyl bromide at the tertiary nitrogen atom of the hydrazine fragment to give 1-(prop-2-yn-1-yl)-and 1-(prop-2-en-1-yl)-1,1-dimethyl-2-(dimethylaminocarbonyl)hydrazinium bromides, respectively. A new procedure was proposed for the synthesis of 6-bromomethylidene-2-dimethylamino-4,4-dimethyl-5,6-dihydro-4H-1,3,4-oxadiazin-4-ium bromide by reaction of 1,1,4,4-tetramethylsemicarbazide with 1,3-dibromoprop-1-yne in acetonitrile.