Reactions of 2-(5-methyl-2-phenyl-2H-1,2,3-diazaphosphol-4-yl)- 4H-1,3,2-benzodioxaphosphinin-4-one with chloral and hexafluoroacetone

Reaction of 2-(5-methyl-2-phenyl-2H-1,2,3-diazaphosphol-4-yl)-4H-1,3,2-benzodioxaphosphinin-4-one with chloral occurs at Piii atom of the 1,3,2-dioxaphosphinine cycle giving mostly 2-chlorocarbonylphenyl 2,2-dichlorovinyl (5-methyl-2-phenyl-2H-1,2,3-diazaphosphol-4-yl)phosphonate, whereas hexafluoroacetone incorporates into the 1,3,2-dioxaphosphorine cycle affording the corresponding 1,3,2-benzodioxaphosphepine.     

The interaction of 2-(5-methyl-2-phenyl-2h-1,2,3-diazaphosphol-4-yl)-4h-benzo[e]-1,3,2-dioxaphosphinin-4-one with activated carbonyl compounds. Synthesis of bis-heterocyclic systems containing di- and tetracoordinated phosphorus

The interaction of 2-(5-methyl-2-phenyl-2H-1,2,3-diazaphosphol-4-yl)-4H-benzo[e]-1,3,2-dioxaphosphinin-4-one with mesoxalic and trifluoropyruvic acids ethyl and diethyl esters, hexafluoroacetone and chloral proceeds with an exclusive participation of P(III) atom and allows to obtain 2-(5-methyl-2-phenyl-2H-1,2,3-diazaphosphol-4-yl)-derivatives of 1,4,2- and 1,3,2-dioxaphosphepines as well as dichlorovinylphosphonate, being the product of Perkow reaction in the case of chloral.     

Reaction of 2,2,2-trichlorobenzo[d]-1,3,2-dioxaphosphole-5-carbonylchloride with phenylacetylene: predominant formation of 2-(2-chloro-2-phenylethenyl)-2,2-dichlorobenzo[d]-1,3,2-dioxaphosphole-5-carbonylchloride

The reaction of 2,2,2-trichlorobenzo[d]-1,3,2-dioxaphosphole-5-carbonylchloride with phenylacetylene in benzene (80 °C) afforded 2-(2-chloro-2-phenylethenyl)-2,2-dichlorobenzo[d]-1,3,2-dioxaphosphole-5-carbonylchloride (yield >95%) as a result of the electrophilic cis-addition of the phosphorus(v) derivative at the triple bond of acetylene with retention of coordination of the P atom. Hydrolysis of this compound affords predominantly 2-hydroxy-5-(hydroxycarbonyl)phenyl (2-chloro-2-phenylethenyl)phosphonate. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 377–379, February, 2006.     

Microwave-assisted Suzuki-Miyaura cross-coupling of 2-alkyl and 2-alkenyl-benzo-1,3,2-diazaborolanes

Nitrogen-based boronate esters, such as 2-octyl-benzo-1,3,2-diazaborolane, 2-phenethyl-benzo-1,3,2-diazaborolane, and 2-{(1E)-hexenyl}-benzo-1,3,2-diazaborolane have been shown to be suitable coupling partners with arylhalides in microwave accelerated Suzuki cross-coupling reactions. Reaction yields of up to 89% were achieved. The use of a silicon group attached to the nitrogen atom, proved to enhance the reactivity of 2-octyl-benzo-1,3,2-diazaborolane.     

Stereochemistry of organophosphorus cyclic compounds—II : Stereospecific synthesis of cis- and trans 2-halogeno-2-oxo-4-methyl-1,3,2-dioxaphosphorinans and their chemical transformations

cis- and trans-2-Chloro-2-oxo-4-methyl-1,3,2-dioxaphosphorinans have been obtained by stereospecific reactions of diastereomerically pure 2-methoxy-4-methyl-1,3,2-dioxaphosphorinans or 2-hydrogen-2-oxo-4-methyl-1,3,2-dioxaphosphorinans with chlorine and sulphuryl chloride, respectively. Similarly, the action of the corresponding brominating agents on isomeric phosphites and phosphonates afforded pure cis- and trans-2-bromo-2-oxo-4-methyl-1,3,2-dioxaphosphorinans. It has been shown that halogenolysis proceeds with retention of configuration at the P atom. On the basis of the ¹H- and ³¹P-NMR spectra conformation of the halogenoanhydrides obtained has been discussed briefly.It has been also found that model nucleophilic substitution reactions occur with inversion of configuration at the P atom in the cyclic halogenoanhydrides.     

Darstellung und Sulfurierung von 4,5-Benzo-2-{[2-(dimethylamino)ethyl]methyl-amino}-3-methyl-1,3,2-oxazaphosphorinan-6-on; Molekülstruktur eines Tetracarbonylmolybdän(0)-Chelatkomplexes

4,5-Benzo-2-{[2-(dimethylamino)ethyl]methylamino}-3-methyl-1,3,2-oxazaphosphorinan-6-one – Preparation, Sulfuration, and Molecular Structure of a Tetracarbonyl Molybdenum Derivative The synthesis of the title compound 4 is described. It reacts with sulfur to yield the thiophosphoryl derivative 5 . The structure of the molybdenum(0) complex 6 , containing 4 as a bidentate ligand, was established by X-ray analysis and is compared to that of the related 2-{[2-(dimethylamino)ethyl]methyl-amino}-1,3,2-benzodioxaphosphole-tetracarbonylchromium(0)-complex 7 [1]. 6 , similarly to 7 , shows a nearly rectangular ?bite”? angle, with 4 functioning as a chelating ligand, coordinating to Mo(0) via P(III) and the nitrogen atom of the NMe₂ group. The heterocyclic part of the ligand displays a distorted envelope configuration.     

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.     

Crystal and molecular structure of 5,5-BIS(hydroxymethyl)-2-OXO-2-[l-(2-trifluoromethyl-3,3,3-trifluoropropioneamido)-1-trifluoromethyl-2,2,2-trifluoroethyl]-1,3,2-dioxaphosphorinane

The crystal and molecular structure of 5,5-bis(hydroxymethyl)-2-oxo-2-[1-(2-trifluoromethyl-3,3,3-tri-fluoropropioneamido)-1-trifluoromethyl-2,2,2-trifluoroethyl]-1,3,2-dioxaphosphorinane (I) - an effective inhibitor of phosphorolytic enzymes - has been determined by X-ray diffractometry. Crystals I are monoclinic: space group P2₁/c, a = 9.962(3), b = 20.468(3), c = 9.527(3) å, Β = 108.04(2)?, Z = 4; R = 0.061 for 3065 independent reflections with I ≥ 3Σ. In a sterically strained molecule I, the coordination polyhedron of the P atom is a distorted tetrahedron with an elongated exocyclic P-C bond [1.906(2) å]. The six-membered heterocycle of I has a distorted chair conformation with a significantly flattened angle at the P atom. In the crystal structure, molecules I are linked into centrosymmetric H-dimers by a pair of strong H-bonds of O-H...O=P type and also into infinite (along the z axis) chains by H-bonds of N-H...O = C and C-H...O = C type.     

Three-dimensional structures of phosphorus-containing heterocycles 50. 2-dimethylamino-2-oxo- and -2-thiono-1,3,2-oxathiaphosphorinanes

Conclusions A chair conformation with an axial orientation of the phosphoryl or thiophosphoryl group is preferable for 2-dimethylamino-2-oxo- and-2-thiono-1,3,2-oxathiaphosphorinanes. The cis isomer of 2-dimethylamino-2-oxo-4-methyl-1,3,2-oxathiaphosphorinane has a similar structure with an equatorial orientation of the 4-methyl group, while the corresponding sulfide is characterized by a trans configuration with a reoriented positioning of the substituents attached to the phosphorus atom.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1369–1374, June, 1989.The authors thank I. A. Litvinov and V. A. Naumov for carrying out the x-ray diffraction analysis.     

MOLECULAR STRUCTURE OF 2-[BIS(2-CHLOROETHYL)-AMINO]-6-BUTYLOXYMETHYL-TETRAHYDRO-2H-1, 3,2-OXA-ZAPHOSPHORINE-2-OXIDE

<正> The molecular structure of 2-[bis(2-chloroethyl)-amino]-6-t-butyloxymethyl-tetrahydro-2H-1,3,2-oxazaphosphorine-2-oxide has been determined by X-ray diffraction method.The crystal(C12H25Cl2NaO3P)is monoclinic with space group P21/a,a=11.965(2),b=10.335(3),c=14.543(5)A,β=102.24(2)°,V=1758(2)A3,Mr=347.22,Z=4,Dx=1.31 g/cm3,μ=4.66 cm-1,F(000)=736,R=0.051,Rw=0.054.The six-membered ring in this compound is in a distorted chair conformation with the t-butyloxymethyl group and the phosphoryl oxygen atom in equatorial positions which lead to cis-configuration.     

Synthesis and Comparative Analysis of the Steric and Supramolecular Structures of Diastereomers of 4,4-Bis(trifluoromethyl)-2-(fluoroalkoxy)-6,7-benzo-1,3,2λ5- dioxaphosphepin-5-one 2-Oxides

Reaction with hexafluoroacetone of 2-fluoroalkoxy-5,6-benzo-1,3,2-dioxophosphorinan-5-ones containing a chiral fluorinated exocyclic substituent on the phosphorus atom, with hexafluoroacetone leads to formation of 4,4-bis(trifluoromethyl)-6,7-benzo-1,4,2-dioxaphosphepines with a high regio- and stereoselectivity. The configuration of all isolated individual diastereomers was established by X-ray diffraction. The molecular and supramolecular structure of the compounds were examined in terms of the proposed model that takes account of the revealed effect of separation of hydrophilic and lipophilic regions in the crystal.     

Synthesis and Some Properties of 2-(5-Methyl-2-Phenyl-2H-1,2,3-Diazaphosphol-4-yl)-4H-Benzo[d]-1,3,2-Dioxaphosphorin-4-One

Abstract

2-(5-Methyl-2-phenyl-2Н-1,2,3-diazaphosphol-4-yl)-4H-benzo[d]-1,3,2-dioxaphosphorin-4-one 1 readily reacts with hexafluoroacetone, mesoxalic acid diethyl ester, trifluoropyruvic acid ethyl ester and chloral to give 2-(5-methyl-2-phenyl-2H-1,2,3-dizaphosphole-4-yl)-derivatives of 1,3,2- and 1,4,2-dioxaphosphepines.     

Boron-nitrogen compounds: XCVIII. Preparation and reactions of 2-(azol-1′-yl)-1,3,2-diazaboracycloalkanes

The preparation of several 1,3-dimethyl-2-(azol-l′-yl)-1,3,2-diazaboracyclohexanes is described and their NMR spectra are interpreted. The reaction of 2-(pyrazol-1′-yl)-1,3,2,-diazaboracyclohexanes with pyrazoles was found to lead to 1/1 molar adducts which exist in equlibrium with the uncomplexed species, whereas B-tetraalkylpyrazaboles are obtained on reaction with (dimethylamino)dialkylboranes. Similar reactions of 2-(pyrazol-l′-yl)-1,3,2-diazaboracyclopentanes with several other nitrogen donor molecules were examined. The chemistry of the various species was found to be greatly affected by the NBN bond angle of the 1,3,2-diazaboracycloalkane ring. The reaction of pyrazabole with monoamines requires very high temperatures which, however, promote extensive ligand redistribution; no monomeric pyrazol-l-ylboranes could be obtained from the process.     

Reactions of 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2-benzodioxaphosphepin-5-one with phenanthrenequinone and dibenzoyl

Reactions of 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2-benzodioxaphosphepin-5-one with 9,10-phenanthrenequinone and dibenzoyl gave hydrolytically unstable spirophosphoranes with five- and seven-membered rings, 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydrospiro[[1,3,2]benzodioxaphosphepine-2,2′-phenanthro[9,10-d][1,3,2]dioxaphosphol]-5-one and 2,4′,5′-triphenyl-4,4-bis(trifluoromethyl)-4,5-dihydrospiro[[1,3,2]benzodioxaphosphepine-2,2′-[1,3,2]dioxaphosphol]-5-one. The structure of the first of these was proved by X-ray analysis.     

Specific Features of Reaction of 2-R-Benzo[e][1,3,2]dioxaphosphinin-4-ones with Perfluorodiacetyl. Synthesis and Steric Structure of 4′,5′-Bis(trifluoromethyl)-4-oxo-2-(2,2,3,3-tetrafluoropropoxy)-2λ 5-spiro[benzo[e][1,3,2]dioxaphosphinine-2,2′-[1,3,2]dioxaphosphole]

2-R-benzo[e][1,3,2]dioxaphosphinin-4-ones react with perfluorodiacetyl under mild conditions to form relatively labile spirophosphoranes containing a 1,3,2-dioxaphosphole ring. These compounds gradually convert to more stable 2-R-4,5-bis(trifluoromethyl)-1,3,2λ⁵-dioxaphosphole 2-oxides and diastereometic 2-R-4-(trifluoroacetyl)-4-(trifluoromethyl)benzo[f][1,3,2λ⁵]dioxaphosphepine 2-oxides, whose structure was confirmed by means of NMR and IR spectroscopy. The structure of 4′,5′ -bis(trifluoromethyl)-4-oxo-2-(2,2,3,3-tetrafluoropropoxy)-2λ ⁵-spiro[benzo[e][1,3,2]dioxaphosphinine-2,2′-[1,3,2]dioxaphosphole] was confirmed by X-ray diffraction analysis.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 4, 2005, pp. 587–599.Original Russian Text Copyright © 2005 by Konovalova, Mironov, Ivkova, Zagidullina, Gubaidullin, Litvinov, Kurykin.     

Formation of cage phosphonate via hydrolysis of 2-(5-methyl-2-phenyl-2<Emphasis Type="Italic">H</Emphasis>-1,2,3-diazaphosphol-4-yl)-1,5-dioxo-4-trifluoromethyl-4-ethoxycarbonylbenzo[<Emphasis Type="Italic">f</Emphasis>]-1,3,2-dioxaphosphepine

A new approach to obtaining of caged bicyclic phosphonate, 4-hydroxy-3-trifluoromethyl-3-ethoxycarbonyl-8-(1-phenylhydrazonoethyl)-5,6-benzo-2,7,1-dioxaphosphabicyclo[3.2.1^1.5]octane, based on hydrolysis of 2,5-dioxobenzo[f]1,3,2-dioxaphosphepine derivative bearing 5-methyl-2-phenyl-2H-1,2,3-diazaphosphol-4-yl substituent at the phosphorus was developed. The hydrolysis process includes elimination of P(II) atom and intramolecular cyclization involving endocyclic carbonyl group of the phosphepine. Structure of the caged phosphonate was established by NMR and XRD methods.     

Features of Reaction of 2-(5-Methyl-2-phenyl-2<Emphasis Type="Italic">H</Emphasis>-1,2,3-diazaphosphol-4-yl)-4<Emphasis Type="Italic">H</Emphasis>-benzo[<Emphasis Type="Italic">e</Emphasis>]-1,3,2-dioxaphosphorin-4-one with 1,2-Dicarbonyl Compounds

2-(5-Methyl-2-phenyl-2H-1,2,3-diazaphosphol-4-yl)-4H-benzo[e]-1,3,2-dioxaphosphorin-4-one reacts with perfluorodiacetyl, 3,6-di(tert-butyl)-1,2-benzoquinone and phenanthrenequinone only with the participation of a three-coordinated phosphorus atom to form spirophosphoranes containing acyclic 5-methyl-2- phenyl-2H-1,2,3-diazaphosphol-4-yl substituent, whereas the interaction with tetrachloro-1,2-benzoquinone proceeds via expanding the six-membered heterocycle to the nine-membered one to form 2-(2-phenyl-2H-1,2,3-diazaphosphol-4-yl)-2,9-dioxo-4,5,6,7-tetrachlorodibenzo[d,h]-1,3,8-trioxaphosphonine.     

1,2-2(H)-1,3,2-Benzoxazaphosphorine-2-Sulfide

Abstract

Reports [1-5] concerning the preparation of benzo-1,3,2-benzoxazaphosphonaline containing a substituent on nitrogen have been published. The synthesis of parent compund, 1,2-dinydro-1,3,2-benzoxazaphosphorine, has not been reported. We found that it can be easily synthesized pY the reaction of salicylic aldehyde with O-alkyl-phosphoryl dichlorides and ammonia.     

Caged C-P phosphoranes based on 2-(2-methyl-4-oxopent-2-yloxy)- and 2-[2-(methylcarbonyl)-1-phenoxy]-1,3,2-benzodioxaphospholes and diethyl mesoxalate

Russian Journal of General Chemistry - Cascade reactions of 2-(2-methyl-4-oxopent-2-yloxy)- and 2-[2-(methylcarbonyl)-1-phenoxy]-1,3,2-benzodioxaphospholes with diethyl mesoxalate yield caged...     

Conformational behavior of 2-, 2,3-, 2,5-, and 2,3,5-alkyl-substituted 1,3,2-oxazaborinanes

The molecules of 2- and 2,3-substituted 1,3,2-oxazaborinanes exist in a state of interconversion of the heterocycle that is rapid on the NMR time scale; the molecules of 2,5- and 2,3,5-substituted 1,3,2-oxazaborinanes exist primarily in the sofa conformation.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1424–1427, October, 1990.