Stereospecificity of alkylation of phosphite anion in electrochemical version of the Michaelis-Becker reaction

Benzylation ofcis2-hydro-2-oxo-4-methyl-1,3,2-dioxaphosphorinane in the electro-chemical version of the Michaelis-Becker reaction occurs stereospecifically with retention of the stereochemistry of the hydrophosphoryl center and affords stereochemically pure 2-benzyl-2-oxo-4-methyl-1,3,2-dioxaphosphorinane (yield 60–70 %). The structure of this compound was determined by X-ray diffraction analysis. The mechanism of the process was discussed.Translated fromIzvestiya Akademii Nauk. Seriva Khimicheskaya, No. 2, pp. 444–446, February, 1996.     

Reactions of some 2-oxo-1,3,2-oxathiaphospholanes and 2-oxo-1,3,2-phosphorinanes with phosphorus pentachloride

2-Phenoxy- and 2-dialkylamino-2-oxa-1,3,2-oxathiaphospholanes react with PCl₅ with ring opening and formation of the corresponding acid chlorides of thiophosphoric acid. Under analogous conditions, 2-phenoxy-2-oxo-1,3,2-oxathiaphosphorinanes do not react with PCl₅, while acid chlorides of thiophosphoric acid are formed in low yield along with other products in the reaction of 2-dialkylamino-2-oxo-1,3,2-oxthiaphosphorinanes with PCl₅.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. 2676–2678, November, 1992.     

Synthesis and Properties of 2-Alkylene/Dialkyl Dithiophosphato-2-oxo-1,3,2-dioxaphosphorinanes

Reactions of 2-chloro-2-oxo-1,3,2-dioxaphosphorinanes with ammonium alkylene/dialkyl dithiophosphates in a 1:1 molar ratio in refluxing benzene solution yields nonvolatile, yellow viscous liquids of the type (S)S(O) and (RO)₂ P(S)S(O) , respectively. [G = ? CH₂CH₂CHCH₃?,. ? C(CH₃)₂CH₂CHCH₃?,. ? CH₂C(CH₃)₂CH₂; R = i-C₃H₇, C₂H₅].

These compounds are hygroscopic and monomeric in nature. The newly synthesized derivatives have been characterized by physicochemical and spectroscopic techniques (IR, NMR [¹H&³¹P], and M.W).     

DL－丙交酯与2－氢－2－氧－1，3，2－二氧磷杂环己烷的开环共聚合研究

在三异丁基铝催化下ＤＬ－丙交酯与２－氢－２－氧－１，３，２－二氧磷杂环己烷开环共聚，制备了一类新型水溶性共聚物Ｐ（ＬＡ－ｃｏ－ＴＭＰ）。用１ＨＮＭＲ、ＩＲ谱对其结构进行了表征，并研究了催化剂用量及不同单体配比对总转化率、共聚物组成及特性粘度的影响。     

New substituted 2-aminomethyl-2-oxo-2λ5-perhydro-[1,3,2]oxazaphospholo [3,4-a]pyridine: Design,synthesis and antimicrobial activity

The synthesis of a new series of P-heterocyclic compounds, substituted 2-aminomethyl-2-oxo-2λ⁵-perhydro-[1,3,2]oxazaphospholo[3,4-a]pyridine derivatives 8(a-j), was accomplished. A key intermediate, 2-(chloromethyl)-2-oxo-2λ⁵-perhydro-[1,3,2]oxazaphospholo[3,4-a]pyridine (6) was primarily synthesized by the condensation of (±)-2-piperidinemethanol (4) and chloromethylphosphonic dichloride (5); subsequently, it was treated with various heterocyclic amines/benzylamines/aminoacid esters, 7(a-j) to obtain the desired products. The structures of the newly synthesized compounds were elucidated by ¹H, ¹³C, and ³¹P NMR spectroscopy, mass spectra and elemental analyses. The biological potency of title products was investigated by screening in vitro antimicrobial activity. The bio-screening data revealed that most of the synthesized derivatives showed potent growth of inhibition against fungi while compared with bacteria. Particularly, compounds 8c and 8i against bacterial strains, and 8a and 8f against fungi exhibited promising activity.     

Oxydative Derivatisierung von 1,3,2-Dioxaphosphorinanen unter Verwendung von Tetrachlormethan als Oxydans

Oxidative Derivatization of 1,3,2-Dioxaphosphorinanes Using Carbon Tetrachloride as Oxidant 2-Alkoxy- and 2-dialkylamido-1,3,2-dioxaphosphorinanes react with CCl₄ in presence or absence of protic nucleophiles under ring opening forming acyclic derivatives of phosphates. 2-Anilido-1,3,2-dioxaphosphorinane, however, forms 2-amido-2-phenylimido-1,3,2-dioxaphosphorinanes ( 6 ) retaining the heterocyclic ring system. The latter are also obtained in the reaction of 2-dialkylamido-1,3,2-dioxaphosphorinanes with CCl₄ and aniline. 2-Amino-2-oxo-1,3,2-dioxaphosphorinanes ( 8 ) are prepared from 2-hydrido-2-oxo-1,3,2-dioxaphosphorinane ( 7 ) by means of the Atherton-Todd reaction. In combination with the Staudinger reaction the latter yields N(2-oxo-1,3,2-dioxaphosphorinanyl)phosphazenes ( 10 ).     

Synthesis of Some New 1,3,2-Oxazaphosphinine, 1,3,2-Diazaphosphinine,Acyclic, and/or Cyclic α-Aminophosphonate Derivatives Containing the Chromone Moiety

The synthesis of some new 1,3,2-oxazaphosphinine 18, 1,3,2-diazaphosphinine 19, acyclic, and cyclic α-aminophosphonate derivatives 3–17 containing the chromone moiety have been achieved via reaction of 3-(phenyliminomethyl)chromone (1), 3-(phenylaminomethylene)-2-hydroxychromanone (4), and/or 3-(phenylamino-methylene)-2-(phenylamino)chromanone (5) with diethyl phosphite, tris(2-chloroethyl)phosphite, and phenylphosphonic dichloride. Structures of the products were verified on the basis of their elemental analyses, IR, ¹H, and ³¹P NMR spectral data.     

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 and physiological activity of new organophosphorus pesticides of 1,3,2-oxazaphosphorinane series

Methods for the synthesis of 2-aryloxy(arylthio)- and 2-alkoxy(alkylthio)-2-thio(oxo)-1,3,2-oxazaphosphorinanes and theirN-substituted derivatives based on the reactions of the corresponding dichlorophosphates, dichlorothio-, and dithiophosphates with 3-aminopropan-1-ol or its substituted derivatives in the presence of Et₃N or aqueous alkali under phase transfer catalysis conditions, as well as by the reaction of the tetramethylammonium salt of 2-hydroxy-2-thio-1,3,2-oxazaphosphorinane with alkyl- and acyl halides, by that of 2-chloro-2-thio-1,3,2-oxazaphosphorinane with sodium thiolates, and by other methods, were developed. The compounds obtained exhibit high nematocide activity but low toxicity for mammals. Some active synergists for permethrine were found among these compounds.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2241–2249, November, 1995.This study was financially supported in part by the International Science Foundation (Grant Nos. NDO 000 and NDO 300) and by the Russian Foundation for Basic Research (Grant No. 93-03-0451). The authors are grateful for this support.     

REACTION BETWEEN [PdCl4]2- AND 5,5-DIMETHYL-2-THIOXOIMIDAZOLIDIN-4-ONE

Abstract

The reaction between 5,5-dimethyl-2-thioxoimidazolidin-4-one (H2L) and [PdCl₄]^2- has been studied in aqueous solution by potentiometric and spectrophotometric measurements. In the presence of the palladium salt, H₂L is completely monodeprotonated (HL^?); from spectrophotometric measurements, only two complexes having 1:1 and 1:2 Pd/ligand mol ratios have been identified. Potentiometric titrations, carried out on solutions with 1:1, 1:2, 1:3 and 1:4 metal/ligand mol ratios, show that these complexes must be formulated as Pd(HL)₂ and [Pd₂(HL)₂(μ-H₂O)(μ-OH)]⁺. Ionization constants of the pure ligand and formation constants of the complexes give pH distribution curves of the various species and the spectra of the two complexes. From MeOH, S-coordinated Pd(H₂L)_nCl₂ (n = 2–4) complexes have been separated in the solid state; from water, two complexes of formula Pd(H₂L)(HL)Cl and Pd(HL)Cl have been obtained with HL^? N,S-coordinated to the metal.     

Reaction of 2-substituted 4-oxo-5, 6-benzo-1, 3, 2-dioxaphosphorinanes with ethyl pyruvate

The reaction of 2-substituted 4-oxo-5, 6-benzo-1, 3, 2-dioxaphosphorinanes with ethyl pyruvate affords ring-expansion products, i.e., diastereomeric 2-substituted 2, 5-dioxo-6, 7benzo-1, 3, 2-dioxaphosphepanes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 565–567, March, 1993.The authors are grateful to Ye.I.Gol'dfarb for recording the 31_P-(1_H) NMR spectra.     

Axial and Equatorial Dimethylamine Substitution on Phosphorus in the 1,3,2-Oxazaphosphorinane Ring System: Structures of 2-Dimethylamino-4-Phenyl-2H-1,3,2-Oxazaphosphorinane-2-Oxides

Single crystal x-ray structures of the diastereomeric 2-dimethylamino-4-phenyl-2H-1,3,2-oxazaphosphorinane-2-oxides, 5c and 6c, have been determined. The pair has been prepared in a straightforward manner by reaction of 3-amino-3-phenylpropanol with Mo₂P(O)Cl₂, and separated into pure forms by column chromatography. Crystal data of 5c: space group P2₁/n, a = 11.087(3), b = 6.087(6), c = 18.465(6)Å, β = 98.40(3)°, R = 0.035 for 1845 reflections. Crystal data of 6c: space group P2₁/n, a = 11.176(2), b = 6.893(2), c = 16.673(3)Å, β = 95.29(1)°, R = 0.037 for 1253 reflections. The fast-migrating 5c is cis (Ph and P = O group cis) with the configuration of 2RS, 4SR. The slow migrating 6c is trans with the configuration of 2RS, 4RS. In both structures the 1,3,2-oxazaphosphorinane rings are chair like with the P-end essentially flattened, The skeleton made up with 4-phenyl-1,3,2-oxazaphosphorinane is essentially the same. With a conformationally demanding 4-phenyl substituent, 5c has an axial Mc₂N whereas 6c has an equatorial Me₂N. For 6c, the exocyclic P-N bond has a partial double bond character the geometry about exocyclic N is planar. On the other hand, for 5c, the geometry about exocyclic N deviates considerably from planarity, the sum of the angles around N being 348.1°. In the crystalline state, the screw-related 5c molecules are hydrogen bonded whereas in the crystalline state, the centro-symmetrically related 6c molecules are paired-up by hydrogen bonds, both through the N-H and P = O system.     

Reaction of 2-cyano[(4-oxo-4H-chromen-3-yl)methylidene]acetohydrazide with phosphorus reagents: Synthesis and evaluation of anticancer activities of some novel 1,2-azaphospholes, 1,2,3-diazaphospholidine,and 1,3,2-diaza-phosphinanes bearing a chromone ring

A series of 1,2-azaphospholes, 1,2,3-diazaphospholidine, 1,3,2-diaza-phosphinanes bearing a chromone ring as well as dialkyl pyrazolopyrimidine phosphonates have been synthesized from treatment of multifunctional 2-cyano[(4-oxo-4H-chromen-3-yl)methylidene]acetohydrazide (2), some phosphorus reagents such as phosphonic acid and its esters, and phosphorus sulfides as well as phosphorus halides in dry dioxane. The isolated products were evaluated for their anticancer activities and on the expression of vascular endothelial growth factor (VEGF) inhibition. Among the isolated products, compounds 3 and 10 exhibited higher effect against breast cancer cells than the reference drug and on the expression of VEGF inhibition.     

3-(羟基-p-甲磺酰苯甲撑基)-5-氯-2-吲哚酮-1-羧酰胺类化合物的合成及生物活性研究

为了寻找高效低毒的非甾体抗炎药物, 将5-氯-2-吲哚酮与氯甲酸苯酯经酯化及水解制得1-苯氧羰基-5-氯-2-吲哚酮, 在4-N,N-二甲氨基吡啶作用下与对甲磺酰基苯甲酰氯反应, 经酸化得1-苯氧羰基-3-[羟基-(p-甲磺酰基)苯甲撑基]-5-氯-2-吲哚酮(II₁), 最后与相应的胺(氨)反应, 经盐酸中和制得未见文献报道的目标化合物II₂～II₁₅, 其结构经IR, ¹H NMR, MS和元素分析确证. 二甲苯致小鼠耳肿胀模型测试显示II₁₀, II₁₁, II₁₅具有明显的抗炎活性; 角叉菜胶致大鼠足跖肿胀模型试验结果表明, II₁₀, II₁₁抗炎活性与双氯芬酸钠和替尼达普钠相当(P＞0.05); 其中II₁₁的胃肠道副作用显著小于双氯芬酸钠(P＜0.05)和替尼达普钠(P＜0.01).     

4-hydroxy-2-quinolones. 109. Alkylation of 4-substituted ethyl 2-oxo-1,2-dihydro-quinoline-3-carboxylates

The alkylation of the ethyl esters of 4-methyl, 4-chloro-, and 4-amino substituted 2-oxo-1,2-dihydroquinoline-3-carboxylic acid by ethyl iodide in the system DMF/K₂CO₃ has been studied. Features of the structure of the starting compounds and their effect on the ratio of the N-and O-alkyl products formed are discussed. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1502–1507, October, 2006.     

Phosphorinane and Enol Rings in One Molecule. Evidence for Reciprocal Stabilization of Half-Chair Conformations

Abstract.

The X-ray crystal structure of 2-(2′,4′-dioxo-3′-pentyl)-5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinane (2) reveals significant half-chair distortion of the axially oriented cisenol ring. The molecule also undergoes in-plane deformations. R(O...O) = 2.410 Å in the enol moiety indicates a very strong hydrogen bonding. The enol content, δ_OH and thermodynamic parameters for the axial-equatorial conformational and keto-enol equilibriums were obtained from ¹H, ³¹P NMR and IR measurements in comparison with the planar 4,6-dimethyl isomer (1) containing equatorially oriented enol ring. The X-ray single crystal structure of 5,5-dimethyl-2-(methoxycarbonyl-3′-oxo-2′-butyl)-2-oxo-1,3,2-dioxaphosphorinane (3) reveals the unusual half-chair conformation of the dioxaphosphorinane cycle disposed a trans-enol ring substituent. ¹H, ³¹P NMR and IR solution data support the same structure displays a strong conformational preference while the minor forms are chair conformers with an axial or equatorial cis-enol ring.     

An Efficient Route for the Synthesis of 3-(4-Bromophenyl)-2-Phenyl-3,4-Dihydro-2H-Benzo[E][,32,]Oxazaphosphinine,its P-Chalcogenides and Metal Complexes

Abstract

2-[(4-bromophenylamino)-methyl]-phenol (1) gave substantially pure 3-(4-bromophenyl)-2-phenyl-3,4-dihydro-2H-benzo[e][1,3,2]- oxazaphosphinine (2) on cyclization with phenyldichlorophosphine in toluene at 0 °C. Reaction of 2 with H₂O₂ in dichloromethane gave selectively 3. P-chalcogenides (4 and 5) were prepared by reacting 2 with elemental S and Se powder in toluene, whereas the tungsten pentacarbonyl complex 6 was prepared by reacting 2 with [W(CO)₅(CH₃CN)] in tetrahydrofuran at 25 °C.

Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional figures.     

One-Pot Synthesis and Methylation of 3-[2-(1H-Benzimidazol-2-yl-Sulfanyl)-Acetyl]-Chromen-2-Ones

Abstract

3-(2-Bromoacetyl)coumarins (I), when treated with 2-mercatobenzimidazole (II) in acetone containing K₂CO₃ (mild base) and tetrabutylammonium bromide (TBAB) as a phase transfer catalyst, at room temperature yielded the title compound 3-[2-(1H-benzimidazole-2-yl-sufanyl)-acetyl]-chromen-2-one (III) in a one-pot synthesis. Alternatively, III could also be prepared by treating dithiocarbonic acid O-ethyl ester, S-[2-oxo-2-(2-oxo-2H-chromen3-yl)-ethyl] ester (V), with o-phenylenediamine (VI). The methylation of the title compound III was performed with dimethyl sulfate (DMS), in acetonitrile containing TBAB and K₂CO₃ at room temperature, resulting in 3-[2-(N-methyl-benzimidazol-2-yl-sulfanyl)]-acetyl-chromen-2-ones (VII). Alternatively, methylation of III could also be performed with DMS in acetonitrile containing K₂CO₃ as base and clay as surface catalyst. All the compounds were synthesized in good yields and their structures were confirmed by spectral and analytical data.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: ¹H NMR of IIIB, VB and VIIB]     

Structure and spectra of 1,3,2-dioxaphospholenes. 1. Microwave spectra of 2-chloro-4,5-dimethyl-1,3,2-dioxaphospholene and its isotopomers in the ground and excited vibrational states

The microwave spectrum of 2-chloro-4,5-dimethyl-1,3,2-dioxaphospholene (1) was studied in the frequency range from 7 to 53 GHz. Rotational transitions of the parent molecule in the ground and eleven excited vibrational states and those of its mono-substituted ³⁷Cl, ¹³C_Me, and ¹³C_Cycle isotopomers in the ground vibrational state were identified. Rotational constants and partial r _s-structure were obtained. The quartic centrifugal distortion constants, dipole moment components _a = 3.8D and _c = 0.24D (the total dipole moment is 3.81D), and the ³⁵Cl quadrupole coupling constants were determined for the parent molecule. The fine structure of the microwave transitions in the parent molecule was analyzed under the assumption of noninteracting methyl groups. The height of the barrier to internal rotation (V ₃₀ = V ₀₃ = 665 cm^–1) and the frequency of torsional vibrations ( = 167 cm^–1) were found. The frequencies of two lowest vibrational modes corresponding to deformation vibrations of the five-membered ring were estimated (100 cm^–1) from the relative intensities of rotational transitions for different vibrational states.