Reactions of 2-[N,N-bis(trimethylsilyl)]amino-4,5-benzo-1,3,2-dioxaphospholane with carboxylic and phosphorous acids and acetic anhydride

The reactions of 2-(N,N-bis(trimethylsilyl)]amino-4,5-benzo-1,3,2-dioxaphospholane with acetic acid, benzoic acid, and acetic anhydride yield 2-trimethylsiloxy-4,5-benzo-1,3,2-dioxaphospholane. Upon reaction with dialkyl phosphites, the silylamido-phosphite acts as a silylating agent.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 232–235, January, 1991.     

Reaction of 2-tert-butoxy-4,5-benzo-1,3,2-dioxaphospholane with tribromoacetaldehyde

The reaction of 2-tert-butoxy-4,5-benzo-1,3,2-dioxaphospholane with tribromo-acetaldehyde proceeds by initial halophilic attack on the bromine atom, leading to a product with retention of the P-Br bond (pyrocatechol bromophosphate) and an anion exchange product (pyrocatechol dibromovinylphosphate), and by initial attack at the carbon atom of the C=O group, which is accompanied by the elimination of isobutylene to form an -hydroxyphosphonate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1909–1912, August, 1989.     

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.     

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.     

Reaction of 2-ethyl-4,5-benzo-1,3,2-oxazaphospholane with mercaptans

Conclusions The reaction of 2-ethyl-4,5-benzo-1,3,2-oxazaphospholane with mercaptan proceeds to give the monocyclic phosphorane with a P-N bond and the thioamidophosphonite, the product of opening the oxazaphospholane ring at the oxygen-phosphorus bond.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 224–226, January, 1977.     

Reaction of 2-phenyl-3-acetyl-4,5 -benzo-1,3,2-oxazaphospholane with dienes

Russian Chemical Bulletin - 2-Phenyl-3-acetyl-4,5-benzo-1,3,2-oxazaphospholane reacts with conjugated dienic hydrocarbons to give phospholenes and 2-methylbenzoxazole.     

Reaction of 2-phenylamino-1,3,2-dioxaphospholane with phenyl isocyanate

Conclusions The reaction of 2-N-phenylamino-1,3,2-dioxaphospholane with phenyl isocyanate proceeds to give N,N-bis(1,3,2-dioxaphospholanyl)phenylamine and diphenylurea due to the reversible disproportionation of the starting amidophosphite to N,N-bis(1,3,2-dioxaphospholanyl)phenyl-amine and aniline.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 216–218, January, 1978.     

Reaction of 2-ethyl-4,5-benz o-1,3,2-oxazaphospholane with carboxylic acids

Conclusions 2-Ethyl-4,5-benzo-1,3,2-oxazaphospholane is oxidized by carboxylic acids to 2-ethyl-2-oxo-4,5-benzo1,3,2-oxazaphospholane, and, gives spirophosphoranes when reacted with ,-unsaturated carboxylic acids.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1152–1155, May, 1979.     

Reaction of some 2-(N-trimethylsilyl) amino-1,3,2-oxazaphospholanes with benzaldehyde

Conclusions The reaction of 2-(N-trimethylsilyl)amido-1,3,2-oxazaphospholanes with benzaldehyde proceeds on the phosphorus atom with migration of the trimethylsilyl group onto the carbonyl oxygen and the formation of cyclic imidophosphonates. The latter, depending on the character of the substituent at the imide nitrogen atom and the conditions of carrying out the reaction, can be converted into phosphonates or decomposed into the original reactants.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1093–1097, May, 1979.     

Reaction of 2-Isopropyl-5,6-benzo-1,3,2-oxazaborepane with Acetonitrile

Russian Journal of General Chemistry -     

Caged phosphorane with P-C bond based on chloral and 4,5-dimethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane

The key methods of caged phosphoranes synthesis are analyzed. Reaction of 4,5-dimethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane (prepared from the meso-form of 2,3-butanediol) with chloral has yielded the caged phosphorane containing a phosphorus-carbon bond: 1,1-(1,2-dimethylethylenedioxy)-3,4-diphenyl-6-trichloromethyl-2,5,7,1-trioxaphosphabicyclo[2.2.1^1,4]heptane; spatial structure of the product has been elucidated with X-ray diffraction analysis.

     

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.     

Reaction of 2-Tetrafluoropropoxy-5,6-benzo-1,3,2-dioxaphosphorinan-4-one with Pyruvonitrile

The reaction of pyruvonitrile with 2-tetrafluoropropoxy-5,6-benzo-1,3,2-dioxaphosphorinan-4-one results mainly in the enlargement of the starting heteroring to form 4-cyano-4-methyl-2-tetrafluoropropoxy-6,7-benzo-1,3,2⁵-dioxaphosphepin-5-one 2-oxide as a mixture of two diastereomers (14:1) along with minor amounts of 3-cyano-3-methyl-2-tetrafluoropropoxy-6,7-benzo-1,4,2⁵-dioxaphosphepin-5-one 2-oxide.     

N,N-bis (2-chloroethyl) amides and N,N-bis(2-chloroethyl) hydrazides of carboxylic acids of the furan series

Reaction of N, N-bis(2-chloroethyl)amine hydrochloride with chloroanhydrides of carboxylic acids of the furan series, in chloroform in the presence of pyridine gives N, N-bis(2-chloroethyl)amides of furan carboxylic acid, furylacrylic acid, 5-nitrofuran carboxylic acid, and 5-nitrofurylacrylic acid.N, N-bis(2-chloroethyl)hydrazides of furan carboxylic acid, furyl carboxylic acid, 5-nitrofuran carboxylic acid, and 5-nitrofurylacrylic acid were obtained in 78–88% yields by reacting N, N-bis(2-chloroethyl)hydrazine hydrochloride with the chloroanhydrides of the appropriate acids in chloroform in the presence of pyridine. The last two hydrazides were prepared in 31 % and 56 % yield, respectively, using anhydrous sodium acetate in place of pyridine.