DERIVATE DER 1-PHENYL-1,3-DIHYDRO-2Λ5-BENZOPHOSPHOLSÄURE

Abstract

Synthesis, properties, NMR, and IR spectra of the chloride, fluoride, anhydride, and the methylester of the title compound as well as those of 1-phenyl-2-chloro-isophosphindoline are described.

Synthese, Eigenschaften, NMR-und IR-Spektren des Chlorids, Fluorids, Anhydrids und Methylesters der Titelverbindung sowie des 1-Phenyl-2-chlor-isophosphindolins werden beschrieben.     

STUDIES ON DERIVATIVES OF 2,3-DIHYDRO-4H-1,3,2-BENZOXAZAPHOSPHORINE——SYNTHESIS AND STRUCTURE ANALYSIS OF 2,3-DISUBSTITUTED-2,3-DIHYDRO-4H-1,3,2-BENZOXAZAPHOSPHORIN-4-ONE-(THIONE)-2-SULFIDE(OXIDE)

A series of novel organocyclophosphorus compounds including twenty-three 2, 3-disubsti-tuted-2,3-dihydro-4H-1,3,2-benzoxazaphosphorin-4-one-2-sulfide (compounds Ⅰ) and three 2, 3-disubstituted-2,3,-dihydro-4H-1,3,2-benzoxazaphosphorin-4-thione-2-oxide (compounds Ⅱ) havebeen synthesized. Their structures were determined by IR, UV, HNMR, X-ray diffractionand elemental analysis. Each of compounds Ⅰ showed a strong absorption between 1290-1319em~(-1) in the IR spectrum. Comprehensive studies of the spectral data and experimental re-sults indicated that this strong characteristic absorption is different from that of the P = Olinkage and thus could be considered as a result of the stretching vibration of (unsaturatedC)-N single bond. In the course of synthesis of the compounds, an abnormal productisomers could be made predominantly in yield and be readily isolated from the other byrecrystallizing for several times from appropriate solvent. Data for the melting point, IR,UV and HNMR spectra of three pairs o     

Reactivity and Synthetic Utility of 1,3,2λ5-Dioxaphospholanes

Abstract

The kinetics of Lewis acid-mediated decomposition and definitions of the synthetic applicability of 1,3,2λ⁵-dioxaphospholanes for (i) the syntheses of highly-hindered epoxides, and (ii) the stereospecific functionalizations of stereocenters in 1,2-diol arrays are described.     

Structure of 2-chloromethyl-2λ5-2,2′(3h,3′h)-spirobis[1,3,2- benzoxazaphosphole]

In 2-chloromethyl-2⁵-2,2(3H,3H)-spirobis[1,3,2-benzoxazaphosphole], which has been investigated by x-ray diffraction, the P atom has a distorted trigonal-bipyramidal coordination with O atoms in axial positions; the angle between the two planes of the 3H-1,3,2-benzoxazaphosphole fragments is 128.8°.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1523–1526, July, 1991.     

Molecular and crystal structure of 2-phenoxy-2λ5-2,2′(3H,3′H)-spirobi[1,3,2-benzoxazaphosphole]

The crystal and molecular structure of 2-phenoxy-2⁵-2,2(3H,3H)-spirobi[1,3,2-benzoxazaphosphole] has been determined using X-ray diffraction structure analysis. The P atom in the molecule in question has a distorted trigonal bipyramidal coordination, with the bond lengths P-O_ax=1.701(1) and 1.700(1) Å, P-O_eq (Ph)=1.625 Å, P-N_eq=1.654(2) and 1.645(1) Å, and bond angles (O-P-O)_ax=175.69(7)° and (N-P-N)_eq = 132.38(7)°.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 876–879, May, 1993.     

The Structure of 2,4-Diorganyl-2,4-Dithioxo-1,3,2λ5,4λ5-Dithiadiphosphetanes in Solution

Abstract

Compounds of the overall composition RPS₂, so called perthiophosphonic acid anhydrides, prefer a dimeric structure in szlution, as it has already been known for the solid compounds. Following compounds [RP(S)S]₂ with R=methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclohexyl, phenyl, 4-methoxy-phenyl and 3,5-dimethyl-piienyl were prepared and characterized by iJJR spectroscopy. The 3,5-ditert-butyl-4-hydroxy-phenyl-compound [1] was also investigated. NHR investigations give evidence for the existence of conligurational isomers of the 2,4-Diorganyl-2,4-dithi-oxo-1,3,2λ⁵,4λ⁵-dithiadiphosphetanes. In solutions an equllibrium between cis and trans isomers is established. The concentration of the two isomers depends on the kind of P and the solvent used. In general the trans isomer has a nigher concentration than the cis isomer. The easy preparation of unsymmetrical compounds by mixing solutions of compounds with different R shows a continous dissociation and association process of the PSPS-ring. This result underlines the existence of a monomeric compound of low concentration as intermediate. An interesting result is obtained for the isopropyl compound. After dissolving e.g. in CDC1₃ almost 90% of the compound is transformed into the other isomer. The progress of the transformation can be followed by NXR spectroscopy. In all other cases the equilibrium state is immediately achieved after preparation of the solution.     

EINIGE NEUE THIOPHOSPHINSÄUREAMIDE R2P(S)NHR': SYNTHESE UND KERNRESONANZSPEKTROSKOPISCHE UNTERSUCHUNGEN

Abstract

P.P-Dialkylthiophosphinsäureamide R₂P(S)NHR' (R=Me, 'Pr, 'Bu; R'=Me, Et, ⁱPr. ^cHex. ^tBu. Ph. etc.) wurden erhalten durch Umsetzung von R₂PNHR' mit Schwefel oder durch Reaktion von Me₂P(S)CI mit primaren Aminen. Ihre ³¹P- und ¹³C-NMR-Spektren werden diskutiert. Insbesondere die Di-t-butylthiophosphinsäureamide sind auszilg;ergewöhnlich stabil gegen Hydrolyse und Luftsauerstoff. P,P-Dialkylthiophosphinic acid amides R₂P(S)NHR' (R=Me. ⁱPr. ^tBu; R'=Me, Et, ⁱPr, ^cHex. ^tBu, Ph. etc.) have been obtained by reaction of the corresponding aminophosphines with sulfur or by reaction of dimethylthiophosphorylhalides with primary amines. Their ³¹P- and ¹³C-NMR spectra are discussed. The di-t-butylthiophosphinic compounds proved to be remarkably stable against moisture and oxygen.     

2-(5-O-nitro-1,4:3,6-dianhydro-D-glucit-2-yloxy)-5-R-5-nitro-2-oxo-1,3,2-λ5-dioxaphosphorinanes: synthesis and structure

5,5-Disubstituted 1,3,2-dioxaphosphorinanes were synthesized by the reaction of (5-O-nitro-1,4:3,6-dianhydro-D-glucit-2-yl) phosphochloridate with 2-nitro-2-R-propane-1,3-diols in the presence of organic bases. The structure of 5-bromo-5-nitro-2-(5-O-nitro-1,4:3,6-dianhydro-d-glucit-2-yloxy)-2-oxo-1,3,2-λ⁵-dioxaphosphorinane was established by X-ray diffraction.     

DER OXIDATIVE ABBAU VON THIOPHOSPHIN- THIOPHOSPHON- UND THIOPHOSPHORSÄUREESTERN MIT HYPOCHLORIT

Abstract

The thioesters R¹R²P(X)SR (X=O,S) 1 to 4 are degradated oxidatively forming R¹R²P(O)OH and R-SO³H. The influence of the following parameters on the oxidation course is investigated using standard conditions: pH, concentration of the hypochlorite, quality of the organic phase and cooperation of phase transfer catalysts and hypochlorite cations.

The thioesters 1 to 4 are degradated by hypochlorite with different rates depending on the type of the ligands R¹ and R² and the employment of an optimal pH. An analytical evaluation is possible.

Die Thioester R¹R²P(X)SR (X=O,S) 1 bis 4 werden durch Hypochlorit oxidativ zu R¹R²P(O)OH und RSO₃H abgebaut. Der Einfluß folgender Parameter auf den Oxidationsverlauf unter Standardbedingungen wird untersucht: pH, Hypochloritkonzentration, Art der organischen Phase, Mitwirkung von Phasentransfer-Katalysatoren und der Hypochlorit Kationen.

Die Thioester 1 bis 4 werden mit Hypochlorit in Abhängigkeit vom Typ der Liganden R¹ und R² und nach Einstellen eines optimalen pH-Wertes unterschiedlich schnell abgebaut. Dieser Unterschied ist analytisch auswertbar.     

CRYSTAL STRUCTURE OF THE NOVEL COMPOUND (1α, 3bT, 5α)-1,3-DIPHENYL-5-HYDRIDO-5-ISOPROPOXY-1λ6, 3λ6,2,4,6,5λ5-DITHIATRIAZAPHOSPHORINE-1,3-DIOXIDE. A COMPARISON WITH RELATED STRUCTURES

Abstract

The title compound (1α, 3β, 5α)-(NSOPh)₂NP(H)O-i-Pr crystallizes in the spacegroup P2₁/n with cell dimensions: a = 12. 150(2), b = 8.911(1), c = 17.614(3) Å, β = 107.52(1)^o; Z = 4. The structure was solved by direct methods and refined by least-squares techniques to an R value of 0.048 for 2420 independent reflections (collected at room temperature) with I > 2.5 σ(I). The unit cell contains dimeric units which are formed by unprecedented P[sbnd]H…O[dbnd]S bridges. The conformation of the inorganic ring skeleton can be described as a boat; phosphorus and sulfur atoms show a distorted tetrahedral geometry. The S[sbnd]N bond lengths differ slightly, ranging from 1.547(3) to 1.588(2) Å. The exocyclic bond lengths are P[sbnd]H = 1.34(2), P[sbnd]O = 1.553(2), S[sbnd]O = 1.439(2) (mean value), and S[sbnd]C = 1.767(4) (mean value) Å. From a comparison with analogous structures the degree of asymmetry (ΔI = {[P[sbnd]N]-[S[sbnd]N]}Å) in the SNP unit is related to the difference in electronegativity between the sulfur and phosphorus centres.     

Synthesis of 3-(arylamino)-5-bromo-2-phenyl-2,3-dihydro-2λ5-benzo[d][1,2]-oxaphosphol-2-oxides

An efficient synthesis of cis-3-(arylamino)-5-bromo-2-phenyl-2,3-dihydro-2λ⁵-benzo[d][1,2]-oxaphosphol-2-oxides 4a–h is described involving a three-component reaction of dichlorophenylphosphine (2), 5-bromosalicylaldehyde (1), and different substituted aromatic primary amines (3) in anhydrous benzene. The product structures were characterized by IR and NMR spectral data.     

Reactions of phenylenedioxytrihalophosphoranes with arylacetylenes: XIII. Reaction of 5-tert-butyl-2,2,2-trihalo-1,3,2λ5-benzodioxaphospholes with acetylenes

Reactions of 5-tert-butyl-2,2,2-trichloro-, 2,2,2-tribromo-5-tert-butyl-, and 2,2-dibromo-5-tert-butyl-2-fluoro-1,3,2λ⁵-benzodioxaphospholes with aryl- and alkylacetylenes lead to quantitative formation of 2-halo-1,2λ⁵-benzoxaphosphinine 2-oxides which may be regarded as phosphorus analogs of natural heterocyclic compounds, coumarin and chromene. The major products (>70%) are 4-aryl-7-tert-butyl-2,6-dichloro-, 4-aryl-2-bromo-7-tert-butyl-, and 4-aryl-7-tert-butyl-2-fluoro-1,2λ⁵-benzoxaphosphinine 2-oxides. Hydrolysis of these compounds and their treatment with amines gives the corresponding 2-hydroxy and 2-amino derivatives, as well as ammonium salts. The structure of some compounds was proved by X-ray analysis.     

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.     

SYNTHESIS AND POLYMERIZATION OF 2-OXO-3-METHYLENE-5, 6-DIPHENYL-1,4-DIOXAN

A new cyclic monomer, 2-oxo-3-methylene-5, 6-diphenyl-1, 4-dioxan, was synthesized. Thestructure of the intermediates and the monomer were determined by IR,~1H NMR,~(13)C NMR andelemental analysis. This new monomer is different from other cyclic monomers in this series,it isa solid (mp 108--109℃)and not very reactive, but still can undergo free radical ring-openingpolymerization. The free radical polymerization was carried out at 130℃. The structure of theresulting polymer was discussed and charaterized by IR, ~1H NMR, ~(13)C NMR and elementalanalysis. The molecular weight of the polymer was estimated by viscosity determination.     

Peculiar Features of Reaction of 2-tert-Butoxy-5,6-benzo-1,3,2-dioxaphosphinin-4-one with Chloral. Steric Structure of 2-Chloro-3-trichloromethyl-6,7-benzo-1,4,2λ5-dioxaphopshepin-5-one 2-Oxide

The reaction of 2-tert-butoxy-5,6-benzo-1,3,2-dioxaphosphinin-4-one with chloral involves expansion of the six-membered heteroring to form 2-hydroxy-3-trichloromethyl-6,7-benzo-1,4,2⁵-dioxaphosphepin-5-one 2-oxide as a single diastereomer. The product was chlorinated with thionyl chloride to obtain (RS,SR)-2-chloro-3-trichloromethyl-6,7-benzo-1,4,2⁵-dioxaphosphepin-5-one 2-oxide.     

SYNTHESIS AND STRUCTURE OF ADDUCT OF 1, 9-DIHYDRO-8,9-DIPHENYL-1, 2, 4-TRIAZOLO [4, 3-d] 1, 2, 4-TRIAZINE-3, 5-DITHIONE WITH TRIETHYLAMINE

<正> C16H13N5S2· (C2H5)3N: Mr = 440. 64, monoclinic, space group C2/c with a = 18.956(7)(?), b = 12. 866(7)(?), c = 20. 830(9)(?) , β=115. 63(3)°; Z=8; V = 4580(7)(?)3; Dc = 1. 278gcm-3; F (000) = 1872, μ= 2. 423cm-1 (MoKa). Final R is 0. 069. C16H13N5S2is non-planar with two rings, a five-member and a six-member with conformations of envelope and twist boat forms respectively, and the two substituted phenyl groups are in equatorial and axial positions.     

Synthesis and steric structure of 3,4-dimethyl-2-(3-methyl-1-phenylbuta-1,2-dienyl)-5-phenyl-1,3,2λ<Superscript>5</Superscript>-oxazaphospholane 2-oxide

Allenic 1,3,2-oxazaphospholanes on the basis of d-pseudoephedrine were synthesized. The steric structure of 3,4-dimethyl-2-(3-methyl-1-phenylbuta-1,2-dienyl)-5-phenyl-1,3,2λ⁵-oxazaphospholane 2-oxide was determined by X-ray diffraction.     

CRYSTAL STRUCTURE OF 2-METHYL-4-(ρ-)METHYLPHENYL-2,3-DIHYDRO- BENZO-(l,5)-DIAZEPINE(C_(17)H_(18)N_2)

<正> INTRODUCTION. The study of the title compound is a part of our systematic investigations on the 2,4-substituted derivatives of benzo- seven-membered heterocyclic system, in recent years. The comparison of conformations of seven-membered heterocyclic rings in thiazepines and diaze-