Synthesis of C-phosphorylated benzenesulfonyl-containing acetamidines

Reactions of sodium derivatives of C-phosphorylated acetamidines with benzenesulfonyl chloride were studied. The reactions proceed selectively to form benzenesulfonyl-containing acetamidine derivatives. A convenient method for the synthesis of a new type of C-phosphorylated acetamidines was developed utilizing CH-acid properties.     

Reactions of C-phosphorylated acetimidates and acetamidines,involving the CH-acid methylene group

Organophosphorus compounds are widely used in the synthesis of pharmaceuticals, fungicides, pesticides, and other biologically active compounds. The review presents the main methods of synthesis of C-phosphorylated acetimidates and acetamidines containing a CH-acid methylene group, as well as reactions involving this group.     

Synthesis of C-phosphorylated acetamidines containing CH-acidic methylene group

C-Phosphorylated acetamidines with the methylene group linked to dialkoxyphosphoryl and amidine groups possessing CH-acidic properties were obtained and characterized. At the reaction of these amidines with sodium one hydrogen atom is substituted to form sodium derivatives interesting as intermediates for the syntheses of the organophosphorus compounds of versatile nature. Based on the CH-acidity of C-phosphorylated acetamidines a convenient method is developed for the synthesis of C-phosphorylated bromoacetamidines.     

Alkylation and acylation of C-phosphorylated acetamidines involving CH-acidic methylene group

Reactions of sodium derivatives of C-phosphorylated acetamidines containing CH-acidic methylene group with alkyl and acyl halides were studied. The interaction occurs selectively to form the products of alkylation and acylation of methylene group, respectively. A convenient method for the synthesis of C-alkylated and C-acylated derivatives of C-phosphorylated acetamidines was developed.     

Reaction of CH-acidic phosphorylated acetamidines with chlorotrimethylsilane

A reaction of sodium derivatives of C-phosphorylated acetamidines with clorotrimethylsilane was investigated. The reaction proceeds selectively with the formation of the acetamidines silylated derivatives. Using the CH-acid properties of C-phosphorylated acetamidines a convenient method was developed for the synthesis of a new type of organophosphorus-silicon amidines.     

A synthesis of acetamidines

The condensation of primary amine with N,N-dimethylacetamide dimethyl acetal yields a mixture of acetamidine and imidate ester. The product distribution in this reaction depends on the temperature, solvent, and structure of the primary amine. It is possible to suppress the formation of imidate ester by performing the reaction in the presence of excess dimethyl amine, yielding acetamidine as the exclusive product. For acetamidines that cannot be purified either by crystallization or distillation, this new method is necessary for the generation of pure acetamidines in good yields.     

Novel C-phosphorylated heterodienes based on pentachloroethyl isocyanate

A preparative method for the synthesis of novel N-phosphorylcarbonyl-and N-alkoxycarbonyltrichloroacetimidoylphosphonates from accessible pentachloroethyl isocyanate was developed. Factors that determine the C/N-selectivity of the phosphorylation of trichloroacetimidoyl chlorides were revealed: phenyl substituents at the P atom and an electron-withdrawing N-alkoxycarbonyl group in imidoyl chloride favored N-phosphorylation, while reactions with silyl phosphite gave exclusively C-phosphorylation products. Dedicated to the Corresponding Member of the Russian Academy of Sciences T. A. Mastryukova. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2563–2566, November, 2005.     

C-phosphorylated furazano-[3,4-b]piperazines

The reaction of phosphorylated α-chloroacetaldehydes with 3,4-diaminofurazane gives enamines, bisenamines, semiaminals, and O,N-acetals, whose cyclization leads to previously unreported phosphorylated furazano[3,4-b]piperazines. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1220–1229, August, 2006.     

Reactions with Molecular Oxygen

Molecular oxygen is an important oxidizing agent both in industrial and in biological processes. In many of these processe, the O₂ molecule reacts preferentially with free radicals, which are frequently paramagnetic metal ions. Homogeneous systems of this type that are described in the literature are discussed, and an attempt is made to establish the factors that determine the course and mechanism of the reaction.     

Reactions with N-Carbonylsulfamoyl Chloride

N-Carbonylsulfamoyl chloride (NCSA) is an intermediate that can be obtained from cyanogen chloride and sulfur trioxide, and which reacts with many compounds, via electrophilic substitution, much more readily than other isocyanates. Reactions with compounds containing hydroxyl, amino, or carboxyl groups lead to N-chlorosulfonylurethanes, -ureas, and -amides, respectively. This group of products also includes the parent substance sulfamoyl chloride (amidosulfonyl chloride). The reaction of N-carbonylsulfamoyl chloride with olefins provides an easy route, not only to derivatives of β-amino acids and unsaturated carboxylic acids, but also to many β-lactams. New, very reactive sulfonylisocyanates of several types can be obtained by further reactions of primary products obtained from N-carbonylsulfamoyl chloride and by the reaction of N-carbonylsulfamoyl chloride with olefins in the presence of free-radical formers. When allowed to react with a number of compounds, NCSA undergoes loss of carbon dioxide to form products containing the grouping = N? SO₂Cl.     

Reactions of mercaptobenzimidazole with allenylphosphonates

Abstract  

Reactions of 2-mercaptobenzimidazole with 3-methylbuta-1,2-dienylphosphonates involve the mercapto group of the heterocyclic compound and the 1,2-double bond of allenylphosphonate.     

Reactions of hydroxybenzophenone with hydrazines

The reaction of 2,2′,4,4′-tetrahydroxybenzophenone with hydrazines under different conditions gave the corresponding indazol-1,3-benzenediol derivatives. It is an interesting and unique approach to the synthesis of indazoles. However, the reactions of 2-hydroxybenzophenone and 2,2′-dihydroxybenzophenone under the same conditions yielded only the hydrazones.     

Reactions of alkylenebisbromomalonates with nucleophiles

Treatment of alkylenebisbromomalonates with nucleophiles (AcOK, AgOH, KHCO₃, 1,8-diazabicyclo[5.4.0]undec-7-ene, or Ph₃P) results mainly in their debromination to give cycloalkane-1,1,2,2-tetracarboxylates. When H₂O and acids are present, the reaction gives products of the substitution of one or two bromine atoms by hydrogen. Alkaline hydrolysis results in oxacycloalkane-α,α,α′,α′-tetracarboxylic acids. The reaction mechanism is discussed.     

Reactions of vinylphosphiranes with methylenetrimethylphosphorane

The reaction of methylenetrimethylphosphorane with isomeric mixtures of cis and trans 1-t-butyl- or l-cyclohexyl-2-vinylphosphirane produce new phosphino-substituted phosphorus ylids via ring-opening and proton transfer. The products are fully characterized by NMR.     

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.     

Reactions of dodecacarbonyltriruthenium with oxadienes

The results of the studies of thermal reactions of Ru₃(CO)₁₂ with oxadienes (4-methylchalcone and benzylideneacetone) have been surveyed. The reactions yield a number of hitherto unknown bi- and polynuclear complexes, whose structures were determined by X-ray diffraction analysis, NMR, and IR spectroscopy. The complexes obtained contain ³-coordinated structural moieties,viz., five-membered chelate oxaruthena rings and/or dihydropyranyl rings. The fundamental differences in the chemical behavior of Ru and Fe carbonyls in the reactions with oxadienes and the differences between the reactions of Ru carbonyls with oxa- and azadienes have been discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 159–166, January, 1995.The authors are grateful to A. S. Batsanov who determined the structure of4a.This work was carried out with the financial support of the Russian Foundation for Basic Research (Projects No. 93-03-4028 and 94-03-08338).     

Reactions of N-bromohexamethyldisilazane with triorganylsilanes

Reactions of N-bromohexamethyldisilazane (Me₃Si)₂NBr with Si-H compounds of the general formula RR′₂SiH yield up to 90% of unsymmetrical disilazanes (Me₃Si)₂NSiRR′₂ and bromotrimethylsilane. An unexpected solvent effect on the reaction conditions is revealed: In benzene the products are formed already on mixing, whereas in cyclohexane, under UV irradiation only.     

Reactions of perfluoroalkylcarbanions with sulphur

The interaction of perfluoroalkylcarbanions generated (a) by the addition of the fluoride ion to fluoro-olefines and (b) from bis-perfluoroalkyl mercurials in the presence of the fluoride ion with elementary sulphur has been investigated and various transformations of the resulting perfluoroalkylmercaptide anions are shown.