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-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.     

2-氯-1,3,2-二氧磷杂环戊烷的合成

合成了重要的有机中间体2 氯 1,3,2 二氧磷杂环戊烷.利用正交设计方法研究了反应温度、原料摩尔比、乙二醇滴加时间对反应收率的影响.实验结果表明:三氯化磷与乙二醇的最佳摩尔比为1.1∶1、最佳反应温度为4～6℃、加料时间为60～80min时,收率最高达到84.8%,远高于文献的报道(<70%).用元素分析和1HNMR表征了产物结构.     

Reactions of 1,3,2-dioxaphospholane derivatives with thiocyanatoalcohols

The reactions of 2-dimethylamino-, 2-methoxy-, 2-chloro-4,5-dimethyl-1,3,2-dioxaphos-pholanes with 4-thiocyanato-2-butanol in all cases yield 2-(1-methyl-3-thiocyanatopropoxy)-4,5-dimethyl-1,3,2-dioxaphospholane. The latter reacts with elemental sulfur to form the corresponding thiophosphate.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2130–2131, December, 1993.     

Synthesis of polyfluoralkylated 1,3,2-dioxaphospholane and 1,3,2-dioxaphosphorinane oxides

Polyfluoroalkyl dichlorophosphates easily react with 1,2- or 1,3-alkanediols in a system pyridine–diethyl ether and afford 2-polyfluoroalkoxy-1,3,2-dioxaphospholane oxides or 2-polyfluoroalkoxy-1,3,2-dioxaphosphorinane oxides. In similar conditions the reaction of methyl dichlorophosphate with 1,2- and 1,3-alkanediols proceeds less effectively.     

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.     

Reaction of 2-[N,N-bis(Trimethylsilyl)]amino-4,5-benzo-1,3,2-dioxaphospholane with carboxylic acid halides

Conclusion The reaction of 2-[N,N-bis(trimethylsilyl)]amino-4,5-benzo-1,3,2-dioxaphospholane with acetyl and benzoyl chlorides leads to the formation of silicon-containing diazadiphospheti-dines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 939–940, April, 1986.     

Molecular structure of 2-bromo-1,3,2-dioxarsenane

A calculation was carried out for the normal mode frequencies and forms of 2-bromo- and 2-chloro-1,3,2-dioxarsenanes. Gaseous electron diffraction was used to determine the r_a structure of 2-chloro-1,3,2-dioxarsenane. In accord with the results of other physical measurements, we established the chair conformation with axial orientation of the bromine atom.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Branch, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 5, pp. 55–60, September–October, 1989.     

Thermal decomposition of 2,4,4,5,5-pentaphenyl-1,3,2-dioxaphospholane

Certain five-membered dioxaheterocyclic compounds (hetero atoms may be P, Si, S, etc.) contain a strained carbon–carbon bond which may undergo homolytic thermolysis at modest temperatures to generate a diradical capable of initiating vinyl polymerization. If substituents contain flame-retarding moieties this represents a convenient method for imparting flame retrdancy to a polymeric material. Of particular interest has been 2,4,4,5,5-pentaphenyl-1,3,2-dioxaphospholane. The thermal degradation of this compound has been studied using ¹³C NMR spectroscopy. This may conveniently be done by monitoring the intensity of the signal for the benzylic carbon atom as a function of time and temperature. A simple transformation is the conversion of the cyclic compound to the linear polymer.     

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.     

Conversions of 2-Phenyl-1,3,2-dioxaphospholane Under the Action of Hydrogen Chloride

The reaction of 2-phenyl-1,3,2-dioxaphospholane with HCl gives a mixture of phenylphosphinic acid, bis(2-chloroethyl) phenylphosphonate, and phenylphosphine; therewith, intermediate oligomeric phosphonites, hydrophosphoryl compounds, and phosphoranes were detected. Thermal treatment of the reaction mixture results in formation of ethylene phenylphosphonate and (2-chloroethyl)phenylphosphinate.     

Chiral 1,3,2-dioxaphospholane amidophosphite in the palladium-catalyzed enantioselective allylation

Phosphorylation of (S)-1,1,2-triphenylethane-1,2-diol furnishes cyclic P*-chiral amidophosphite, whose application as a ligand in the Pd-catalyzed allyl substitution in 1,3-diphenylallyl acetate provides the products ee up to 70%.     

Reaction of o-aminothiophenol with 1-bromo-2-acylacetylenes

Conclusions The reaction of o-aminothiophenol with 2-benzoyl- or 2-thenoyl-1-bromoacetylenes gives, depending on conditions, hydrobromides of 1-acyl-2-(2-aminophenylthio)acetylenes and 1,1-bis(2-aminophenylthio)-2-acylethylenes. The latter can act as ligands in the formation of coordination complexes of metals (Co, Cu, Zn, Cd).Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 858–861, April, 1985.     

Reaction of 1-bromo-2-acylacetylenes with thiobenzhydrazide

Conclusions The reactions of 1-bromo-2-acylacetylenes with thiobenzhydrazide at from –10 to –30°C in ether, acetonitrile, methanol without catalyst, or methanol in the presence of triethylamine gave 2-acylmethyl-5-phenyl-1,3,4-thiadiazoles and their hydrobromide salts.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2637–2638, November, 1988.     

Reaction of tetramethyl-1,2-dioxetane with triphenylphosphine: Activation parameters for the formation of 2,2-dihydro-4,4,5,5-tetramethyl-2,2,2-triphenyl-1,3,2-dioxaphospholane

The reaction of tetramethyl-1,2-dioxetane ( 1 ) and triphenylphosphine ( 2 ) in benzene-d₆ produced 2,2-dihydro-4,4,5,5-tetramethyl-2,2,2-triphenyl-1,3,2-dioxaphospholane ( 3 ) in ?90% yield over the temperature range of 6–60°. Pinacolone and triphenylphosphine oxide ( 4 ) were the major side products [additionally acetone (from thermolysis of 1 ) and tetramethyloxirane ( 5 ) were noted at the higher temperatures]. Thermal decomposition of 3 produced only 4 and 5 . Kinetic studies were carried out by the chemiluminescence method. The rate of phosphorane was found to be first order with respect to each reagent. The activation parameters for the reaction of 1 and 2 were: Ea ? 9.8 ± 0.6 kcal/mole; ΔS^≠ = ?28 eu; k_30° = 1.8 m^?1sec^?1 (range = 10–60°). Preliminary results for the reaction of 1 and tris (p-chlorophenyl)phosphine were: Ea ? 11 kcal/mole, ΔS^≠ = ?24 eu, k_30° = 1.3 M^?1sec^?1 while those for the reaction of 1 and tris(p-anisyl)phosphine were: Ea ? 8.6 kcal/mole, ΔS^≠ = ?29 eu, k_30° = 4.9 M^?1 sec^?1.