S,S-Alkyl S′-alkyl(4-methoxyphenyl)phosphonotrithiolothionates

A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1932–1933, August, 1992.     

Crystal and molecular structure of 4-amino-3-phenyl-and 4-dimethylfuleinylimino-3-phenylfuroxanes

Institute of Organic and Physical Chemistry, Kazan Branch, Academy of Sciences of the USSR, Kazan. Translated from Zhurnal Strukturnoi Khimii, Vol. 32, No. 3, pp. 148–151, May–June, 1991.     

Thiocyanatoalcohols as oxidants of some P(III) derivatives

A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan, Tatarstan, Russia. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2816–2817, December, 1992.     

Transformations of thiocyanoalkyl phosphites and amidophosphites

The ratio of the alkoxy and dialkylamido groups in thiocyanoalkyl phosphites determines the structure of the transformation products of these compounds.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2673–2675, November, 1992.     

Synthesis of acyclic pentaalkoxyphosphoranes from tris(hexafluoroisopropoxy)dihalophosphoranes and chloral

Tris(hexafluoroisopropoxy)-bis(1-halo-2,2,2-trichloroethoxy)phosphoranes were obtained by addition of chloral to tris(hexafluoroisopropoxy)dibromo- and dichlorophosphoranes. The intermediate tris(1,1,1,3,3,3-hexafluoroisopropoxy)-1,2,2,2-tetrachloroethoxychlorophosphorane was also isolated in this reaction.V. I. Ul'yanov-Lenin Kazan State University, 420008 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 683–687, March, 1992.     

Reaction of tetraethyldiamidochlorophosphite with thiocyanoalcohols

The reaction of tetraethyldiamidochlorophosphite with 1-thiocyano-3-butanol in the presence of triethylamine at low temperature leads to the formation of tetraethyldiamidocyanophosphine.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2678–2680, November, 1992.     

Synthesis and reaction of N-butyl-N-isobutenyl-aminotrimethylsilane with 4,5-benzo-2-chloro-1,3,2-dioxaphospholane

The reaction of N-butylisobutyraldimine with trimethyliodosilane obtained in situ proceeds to give N-butyl-N-isobutenylaminotrimethylsilane, which reacts with 4,5-benzo-2-chloro-1,3,2-dioxaphospholane to yield 2-(N-butyl-N-isobutenylamino)-4,5-benzo-1,3,2-dioxaphospholane.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1923–1924, August, 1992.     

Reactions of 5-cyano-1,4,6,9-trioxathia-5-phosphaspiro[4,4]nonanes with compounds containing a labile hydrogen atom

All the investigated reactions of 5-cyano-1,4,6,9-trioxathia-5-phosphaspiro[4,4]nonanes with compounds containing a labile hydrogen atom proceed with the loss of HCN, predominant opening of the oxathiophospholane ring, and formation of 2-oxo-1,3,2-dioxaphospholane derivatives.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, p. 2670–2673, November, 1992.     

Competition of the Hantzsch and boese reactions in the interaction of 1-thiocarbamoylthiosemicarbazide and phenylchloropyruvic acid methyl ester

1-Thiocarbamoylthiosemicarbazide, the synthetic equivalent of thiourea and thiosemicarbazide, reacts with phenylchoropyruvic acid methyl ester exclusively as thiourea (Hantzsch reaction) forming 2-hydrazo-4-methoxycarbonyl-5-phenylthiazole. Diacetylation and reductive fission of this hydrazo compound was carried out, and also oxidation to the corresponding azo compound, readily accomplished with using dimethyl sulfoxide.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, Kazan 420088; Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1554–1560, November, 1999.     

(3,5-Diallylisocyanuratomethyl)phosphine oxides and some of their properties

Reaction of sodium diallylisocyanurate with tris(chloromethyl)-, bis(chloromethyl)phenyl-, and (chloromethyl)diphenylphosphine oxides yields, depending on the stoichiometric ratio of the reagents, mono-, bis-, and tris(3,5-diallylisocyanuratomethyl)phosphine oxides.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan, Tatarstan, Russia. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2773–2777, December, 1992.     

Synthesis and some properties of 2-acetylamido-4,5-benzo-1,3,2-dioxaphospholane

The reaction of pyrocatechol chlorophosphite with N-trimethylsilylacetamide gave 2-acetamido-4,5-benzo-1,3,2-dioxaphospholane. The reaction of this product with hexamethyldisilazane leads to 2-trimethylsiloxy-4,5-benzo-1,3,2-dioxaphospholane, while its reactions with diethylamine, trimethylsilyldiethylamine, and bis(dimethylamino)methane give 2-dialkylamino-4,5-benzo-1,3,2-dioxaphospholanes.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Branch, Russian Academy of Sciences, 420008 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 220–222, January, 1992.     

Kinetics of the transesterification of para-nitrophenyl esters of phosphorus acids in water and aqueous hexamethylphosphorotriamide

The rate constants for the substitution of the para-nitrophenoxide ion by the phenoxide and hydroxide ions in phosphates and phosphonates are enhanced upon the addition of hexamethylphosphorotriamide (HMPTA) to water. The lack of alkaline hydrolysis of the esters in 90% aqueous HMPTA containing PhONa is a consequence of the formation of the PhOH... OH complex, which is nonreactive.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 456–459, February, 1992.     

Conformational analysis of 2-oxo(thio)-1,3,2-dioxaphosphorinanes with a P-H bond from vibrational spectroscopic data

The steric structure of four 2-hydro-2-oxo(thio)-1,3,2-dioxaphosphorinane (DOP) molecules has been studied by means of Raman and IR spectroscopy. A characteristic feature of these compounds is the presence of a hydrogen atom as a "light" exocyclic substituent whose vibration is not mixed with the vibrations of the molecular skeleton.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, 420083 Kazan, Tatarstan, Russia. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2725–2730, December, 1992.     

Synthesis of some new annellated 1,2,4-Triazole systems from methyl 5-phenyl-2-hydrazinothiazolecarboxylate

The heterocyclization of hydrazides, prepared from methyl 5-phenyl-2-hydrozinothiazole-4-carboxylate and organic acids or their anhydrides, leads to the production of thiazolo[2,3-c]triazoles which do not undergo rearrangement to the corresponding thiazolo[3, 2-b]triazoles under the action of mineral acids. The 2-trifluoroacetylhydrazine derivative does not cyclize, even under severe conditions.A. E. Arbuzov Institute of Organic and Physical Chemistry of the Kazan Science Center, Russian Academy of Sciences, Kazan 420083. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 406–409, March, 1995. Original article submitted February 12, 1995.     

Electronic structure and conformation of N-amino-2,5-dimethylpyrrole derivatives and N-formylaniline

From photoelectronic spectroscopy data N-amino-, N-dimethyl-, N-methylphenyl-, and N-methylformylamino-2,5-dimethylpyrrole molecules were found to have an acoplanar-oriented fragment conformation in the gas phase, while N-formylaniline had a planar structure. In aminopyrroles the n-n repulsion energy of unshared pairs exceeded the n-* conjugation energy.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, Kazan 420083. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 602–606, March, 1992.     

Reaction of 2,2-dichloroacetophenone and benzaldehydes under conditions of the darzens condensation

The reaction of 2,2-dichloroacetophenone with benzaldehydes was studied under Darzens condensation conditions. Benzaldehyde, p-bromobenzaldehyde, and o,p-dichlorobenzaldehyde condensed with 2,2-dichloroacetophenone to give 1-phenyl-3-aryl-3-chloro-1,2-propanediones. In the case of p-nitrobenzaldehyde, 1-phenyl-2-chloro-3-(p-nitrophenyl)-2,3-epoxy-1-propanone, which is the product of the first step of the Darzens condensation, was isolated.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 204–206, January, 1992.     

Phosphorylnitrile oxides. 5. Reactions of 3-(dialkoxyphosphoryl)isoxazoles and -isoxazolines with nucleophilic reagents

3-Phosphotylated isoxazoles and isoxazolines react with nucleophiles either with cleavage of the P-C bond and subsequent ring opening or with retention of the heterocyclic ring depending on the structure of the ring substituents, nature of the nucleophile, and reaction conditions. This permits the selective chemical modification of the starting compounds.Kazan State Technological University, Kazan 420015. Institute of Physiologically Active Compounds, Russian Academy of Sciences, Chernogolovka 142432. A. I. Gertsen Russian State Pedogogical University, St. Petersburg 191186. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 821–828, June, 1994. Original article submitted April 28, 1994.     

Molecular structure of 1-phenyl-2-chloro-3-(meta-nitrophenyl)-2,3-epoxypropanone

X-ray analysis was used to determined the structure of 1-phenyl-2-chloro-3-(m-nitrophenyl)-2,3-epoxypropanone, obtained by reacting phenacyl dihydrochloride with metanitrobenzaldehyde under Darzen's reaction conditions. The bulky m-nitrophenyl and benzoyl substituents were located in the trans position relative to the chloroepoxide fragment, which was found to stabilize when the m-nitrophenyl substituent was introduced.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, Kazan 420083. Translated from Khimiya Geterotsiklicheskikh Soedinennii, No. 9, pp. 1172–1175, September, 1994. Original article submitted May 5, 1994.     

Reaction of 1,2-borylphosphinoethene with thiocyanates. Molecular and crystal structure of 2,2,3-tributyl-4,5,5-triphenyl-6-methylthio-1,5,2-azaphosphoniaboratacyclohexa-3,6-diene

The reaction of 1,2-borylphosphinoethenes with alkylthiocyanates leads to formation of substances having the structure of 6-alkylthio-1,5,2-azaphosphoniaboratacyclohexa-3,6-dienes in the crystal state. The structure of the compounds has been proven by x-ray diffraction analysis of 2,2,3-tributyl-4,4,5-triphenyl-5-methylthio-1,5,2-azaphosphoniaboratacyclohexa-3,6-diene. The heterocyclic moiety of the molecule is planar within 0.010(2) Å. The methylthio group lies practically in the plane of the heterocycle.Deceased.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, 420083 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1638–1644, July, 1992.     

Synthesis of 4,5-dihydro-2-diethylamino-4-thioxo-4-phenoxy-5-chloro-1,3,4-thiazaphosphole and 3,7-bis(diisopropylamino)-1-thioxobicyclo[3.3.0]-4,6-dithia-2,8-diaza-1-phosphaocta-2,7-diene

The product of the reaction of 0-phenylisothiocyanatodichloromethylthiophosphonate with diethylamine in the presence of Et₃N is 4,5-dihydro-2-diethyl-amino-4-thioxo-4-phenoxy-5-chloro-1,3,4-thiazaphosphole. 3,7-Bis(diisopropyl-amino)-1-thioxobicyclo-[3.3.0]-4,6-dithia-2,8-diaza-1-phosphaocta-2,7-diene was obtained as the result of the reaction of diisothiocyanatodichloromethylthiophosphonate with diisopropylamine and triethylamine. IR, PMR, and³¹P NMR spectroscopy was used to demonstrate the structures of the products synthesized.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 462–463, February, 1992.