2-Acyl(aroyl)-1,1,3,3-tetracyanopropenides: III. Heterocyclization by the action of hydrogen halides

2-Acyl(aroyl)-1,1,3,3-tetracyanopropenides reacted with hydrogen halides along two concurrent pathways with formation of furan or pyridine derivatives. The reaction in butan-2-ol afforded 2-amino-4-acyl-(aroyl)-6-halopyridine-3,5-dicarbonitriles, whereas the major products in the reactions with HCl and HBr in aqueous solution were the corresponding 2-(5-amino-2-aryl-2-chloro(bromo)-4-cyano-2,3-dihydrofuran-3-ylidene)malononitriles. The reaction with aqueous hydrogen iodide was accompanied by reductive deiodination and produced 2-(5-amino-2-aryl-4-cyano-2,3-dihydrofuran-3-ylidene)malononitriles.     

2-acyl(aroyl)-1,1,3,3-tetracyanopropenides: V. Reaction with hydrazine hydrate

Reactions of 2-acyl(aroyl)-1,1,3,3-tetracyanopropenides with hydrazine hydrate followed by neutralization led to the formation of 2-amino-4-[hydrazono(aryl)methyl]-2-oxo-1,2-dihydropyridine-3,5-dicarbonitriles.     

2-Acyl(aroyl)-1,1,3,3-tetracyanopropenides: I. Synthesis of 2-[5-amino-2-aryl-2-chloro-4-cyanofuran-3(2H)-ylidene]-propanedinitriles by reaction of potassium 2-aroyl-1,1,3,3-tetracyanopropenides with concentrated hydrochloric acid

Potassium 2-aroyl-1,1,3,3-tetracyanopropenides reacted with concentrated hydrochloric acid to give the corresponding 2-[5-amino-2-aryl-2-chloro-4-cyanofuran-3(2H)-ylidene]propanedinitriles.     

2-Acyl(aroyl)-1,1,3,3-tetracyanopropenides: II. Synthesis of 2-[2-(alkylsulfanyl)-5-amino-2-aryl-4-cyano-2,3-dihydrofuran-3-ylidenepropanedinitriles by reaction with thiols

Reactions of 2-aroyl-1,1,3,3-tetracyanopropenides with thiols in acid medium led to the formation of the corresponding 2-alkylsulfanyl-substituted 2-(5-amino-2-aryl-4-cyano-2,3-dihydrofuran-3-ylidene)propanedinitriles.     

2-Acyl(aroyl)-1,1,3,3-tetracyanopropenides: IV. Synthesis of 1-alkyl(aryl)-4-amino-6-iodo-3-oxo-1,3-dihydrofuro[3,4-c]pyridine-7-carbonitriles

The reaction of sodium 2-acyl(aroyl)-1,1,3,3-tetracyanopropenides with hydroiodic acid at heating led to the formation of 1-alkyl(aryl)-4-amino-6-iodo-3-oxo-1,3-dihydrofuro[3,4-c]pyridine-7-carbonitriles.     

Reaction of Potassium 1,1,3,3-Tetracyano-2-(2,2-dimethylpropanoyl)propenide with 2-Sulfanylethanol

The reaction of potassium 2-(2,2-dimethylpropanoyl)-1,1,3,3-tetracyanopropenide with an equimolar amount of 2-sulfanylethanol afforded 2-{5-amino-2-(tert-butyl)-4-cyano-2-[(2-hydroxyethyl)sulfanyl]- 2,3-dihydrofuran-3-ylidene}propanedinitrile, whereas 4-amino-1-(tert-butyl)-1,6-bis[(2-hydroxyethyl)- sulfanyl]-3-imino-1,3-dihydrofuro[3,4-c]pyridine-7-carbonitrile was obtained in the reaction with excess 2-sulfanylethanol.     

Reaction of acyl(aroyl) isocyanates with dimedon

Conclusions The benzoyl and trichloroacetyl isocyanates react with dimedon to give the [4 + 2]-cycloadducts and the O- and C-addition products, whereas trifluoroacetyl isocyanate reacts to give the acid azomethine.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2788–2790, December, 1981.     

Reaction of bis(trimethylsilyl) sulfate with hydrogen halides and with phosphorus and sulfur halides and oxyhalides

Conclusions The reaction of bis(trimethylsilyl) sulfate (BTS) with HBr leads to trimethylbromosilane, hexamethyldisiloxane, and free bromine. Its reaction products with HI are hexamethyldisiloxane and free iodine. The reaction of BTS with PCl₃ leads to the formation of Me₃SiCl, SO₂, and a polymeric product whose composition approximates [(CH₃)₃SiO]₈Cl₂O₂₇P₈S₄. The reaction of SOCl₂ with BTS gives in high yield Me₃SiOSO₂Cl, Me₃SiCl, and SO₂. POCl₃ and SO₂Cl₂ do not react with BTS under analogous conditions.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 696–698, March, 1982.     

Contributions to the chemistry of halosilane adducts: XVIII. On the nature of compounds of trimethylhalosilanes with 1,1,3,3-tetramethylguanidine and 2-trimethylsilyl-1,1,3,3-tetramethylguanidine: preparation and characterization of mono- and bis-(2-trimethylsilyl)-1,1,3,3-tetramethylguanidinium halides

1,1,3,3-Tetramethylguanidine (TMG) and 2-(trimethylsilyl)-1,1,3,3-tetramethylguanidine (TMSTMG) react with trimethylhalosilanes Me₃SiHal in equimolar ratio with ionization of the Sihalogen bond to give the stable guanidinium salts [(Me₂N)₂CNHSiMe₃]Hal (Hal  Cl (1), Br (2)) and [(Me₂N)₂CN(SiMe₃)₂]Hal (Hal  Cl (3), Br (4), I (5)), respectively, involving tetracoordinate silicon. No reaction occurs with Me₃SiF. The same ionic species are present in CHCl₃ or CH₃CN solutions (IR, ¹H, ²⁹Si NMR), thus establishing for the first time, the formation of an ionic solid derivative of Me₃SiCl stable towards dissociation. Reaction with an excess of TMG gives an equilibrium mixture of TMSTMG and TMG · HHal. The bis(silyl)guanidinium salts are less stable towards dissociation than the mono(silyl) derivatives, the stability sequence being Cl⁻ < Br⁻ < I⁻ within the series. The reactions of both types of compound have been investigated. The implications of the present and earlier results for the mechanisms of racemization and nucleophilic substitution at silicon are discussed.     

Reaction of 2-chloro(bromo)-3-phenyl-1,3,2-oxazaphospholanes with acyl halides

Conclusions The 2-chloro(bromo)-3-phenyl-1,3,2-oxazaphospholanes react with acyl halides, with opening of the oxazaphospholane ring and the formation of alkyl dihalophosphite derivatives. The latter are heat unstable and when heated they decompose with the liberation of the N-phenyl-N-(-haloethyl)acetamide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2161–2163, September, 1977.     

Organotellurium(VI) azides and halides

The reaction of azide with organotellurium(VI) halides Ph(5)TeBr and cis-(biphen)(2)TeF(2) (biphen = 2,2'-biphenyldiyl) resulted in the formation and isolation of Ph(5)TeN(3) (1) and cis-(biphen)(2)Te(N(3))(2) (2), which are the first tellurium(VI)-azide species. In addition to spectroscopic data, both crystal structures have been determined. Furthermore, the stability of possible Te(VI) species with higher azide contents Ph(x)()Te(N(3))(6)(-)(x)() and Me(x)()Te(N(3))(6)(-)(x)() as well as the syntheses and properties of their Ph/Me(x)()TeF(y)() precursors was investigated, including the crystal structure determination of trans-Ph(2)TeF(4) (3). Ab initio and density functional studies of all molecules regarding the structures and electronic populations were performed.     

Reaction of aryl-β-nitrovinyl ketones with hydrogen halides. Preparation of isoxazoles

A study is made of the reactions of aryl--nitrovinyl ketones with hydrogen chloride, hydrogen bromide, and hydriodic acid. It is shown that reaction leads to cyclization forming substituted isoxazoles, and that with hydrogen bromide and hydriodic acid, cyclization is accompanied by reduction. The action of hydrogen chloride on phenyl--nitrovinyl ketone gives 3, 4-dichloro-5-phenylisoxazole, while hydrogen bromide gives 5-phenyl- and 3-bromo-5-phenylisoxazoles, and hydriodic acid 5-phenylisoxazole. Chlorination of 3-chioro-5-phenylisoxazole and bromination of 3-bromo-5-phenyl-isoxazole are methods of synthesizing 3, 4-dichloro- and 3, 4-dibromo-5-phenylisoxazole, respectively. The general equations for the reactions are given.     

Reaction of bis(phenylethynyl)itterbium with tetraphenylantimony halides

Phenylethynyl itterbium derivative (PhC≡C)₂Yb(THF)₂ reacts with tetraphenylantimony halides in tetrahydrofuran (THF) at room temperature to form triphenylantimony, phenylacetylene, benzene, and phenylethynylitterbium PhC≡CYbX(THF)₄ and itterbium YbX₂(THF)₄ halides; X = Cl, Br, I. The reduction of the antimony derivative is accompanied with the generation of phenyl and phenylethynyl radicals     

Reaction of 2-cyanomethylbenzimidazole with alkyl halides

Refluxing 2-cyanomethylbenzimidazole in alcohol with alkyl halides led to low yields of N-alkylated products. Addition of base to the reaction mixture shifted the course of the reaction to form mainly N,C-dialkyl substituted products. In DMF or with an excess of alkyl halide at elevated temperature both N-mono- and N,N-dialkyl substituted materials were formed together.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 24, No. 3, pp. 345–349, March, 1988.     

Reaction of bis (2-oxocyclohexyl)methane with hydrogen selenide

Bis (2-oxocyclohexyl) methane reacts with hydrogen selenide in polar solvents without a catalyst to give a product of nucleophilic addition of hydrogen selenide at one of the carbonyl groups, which exists in the form of three equilibrium forms, viz., 2-hemolselenolcyclohexyl-2-cyclohexanonylmethane, perhydroselenoxanthene-11,13-diol, and perhydro-11-xanthenol-13-selenol. The latter under the influence of an alcohol solution of alkali form 2,3-tetramethylenebicyclo[3.3.1]nonanon-9-ol, with hydrogen chloride; they react with hydrogen chloride to give sym-octahydroselenoxanthene, and trifluoroacetic acid converts them to a mixture of sym-octa-hydroselenoxanthylium trifluoroacetate and perhydroselenoxanthene. The trifluoroacetate reacts with perchloric acid to give sym-octahydroselenoxanthylium perchlorate.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 640–642, May, 1981.     

Mixed ligand complexes of tungsten(VI) containing aroyl hydrazones and isothiocyanate

Five complexes [WO(NCS)₄L–L] (where L–L = benzoic acid[1-(Furan-2-yl)methylene]hydrazide(BFMH), benzoic acid[(thiophen-2-yl)methylene]hydrazide(BTMH), benzoic acid[1-(thiophen-2-yl)ethylidene]hydrazide(BTEH), benzoic acid(phenylmethylene)hydrazide(BPMH) and benzoic acid[1-(anisol-3-yl) methylene]hydrazide(BAMH)) have been prepared by reaction of ammonium tetraisothiocyanatodioxotungstate(VI) with the corresponding ligand in aqueous medium in the presence of hydrochloric acid. The complexes have been characterized by elemental analysis, molar conductivity, magnetic moment measurements, IR, electronic spectra, thermogravimetric analysis TGA/DTA and ¹H NMR.     

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.     

C-Phosphorylated pyrazoles. Reaction of N-methyl- and N-phenylpyrazoles with phosphorus(III) halides

The reactions of N-methyl- and N-phenylpyrazole derivatives with phosphorus(III) halides have been studied. The preparative method for synthesis of a variety of 4-phosphorylated pyrazoles, including pyrazolyl substituted halo- and dihalophosphines, has been elaborated. Migration of an alkyl group from O to P(III) in 4-phosphorylated 5-alkoxypyrazoles was found to give a P-ylides in a vinylogous manner with respect to the Arbuzov reaction. © 1995 John Wiley & Sons, Inc.