Reaction of 5-oxo-2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2-benzodioxaphosphepine with chloral. The synthesis and spatial structure of 5-carbaphosphatrane containing a four-membered ring

Phosphorylation of 2-hydroxyphenyl 2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl ketone with dichloro(phenyl)phosphine gave 5-oxo-2-phenyl-4,4-bis(trifluoromethyl)-4,5-di-hydro-1,3,2-benzodioxaphosphepine. Heating of the latter initiated an intramolecular interaction of the P atom with the carbonyl group. Hydrolysis of the intermediate product yielded 3-hydroxy-2-oxo-2-phenyl-3-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-2,3-di-hydro-1,2λ⁵-benzo[d]oxaphosphole. The reaction was highly stereoselective (P_RC_S/P_SC_R). The reaction of the starting phosphepine with chloral proceeded highly stereoselectively (P_RC_SC_S/P_SC_RC_R) to give a 5-carbaphosphatrane derivative containing a four-membered ring, namely, 1-phenyl-3-trichloromethyl-10,10-bis(trifluoromethyl)-6,7-benzo-2,4,8,9-tetraoxa-1λ⁵-phosphatricyclo[3.3.2.0¹,⁵]decene. The trigonal bipyramid of the 5-carbaphosphatrane derivative is made up of the equatorial O atoms and the apical C atoms.     

Synthesis of 2-amino-4,4-bis(trifluoromethyl)-3-cyano-4,5-dihydro-1H-1,5-benzodiazepine

Conclusions The reaction of 1,2-phenylenediamine with 2,2-bis(trifluoromethyl)-1,1-dicyanoethylene leads to the formation of 2-amino-4,4-bis(trifluoromethyl)-3-cyano-4,5-dihydro-lH-l,5-benzodiazepine, whose structure was established by x-ray diffraction analysis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1920–1922, August, 1988.     

New 4,4-bis(trifluoromethyl)-4H-1,3,2-benzodioxaphosphinine 2-oxides(sulfides)

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Preparation and steric structure of 2-Alkoxy-2,5-dioxo-4,4-bis(trifluoromethyl)-7(8)-chloro-1,3,2λ5-benzodioxaphosphepins

The reaction of hexafluoroacetone with 2-alkoxy-6(7)-chloro-1,3,2-benzodioxaphosphorin-4-ones yielded 7-and 8-chloro-substituted 2-alkoxy-2,5-dioxo-4,4-bis(trifluoromethyl)-1,3,2λ⁵-benzodioxaphosphepines. Their steric structure was studied by single-crystal X-ray diffraction. The effect of fluorinated substituents on the crystal packing of the benzophosphepines was demonstrated. Hydrolysis of these compounds gave the corresponding 4-and 5-chloro-substituted 2-(2-hydroxyphenyl)-2-oxo-1,1-bis(trifluoromethyl)-ethanols; the structure of 2-(2-hydroxy-5-chlorophenyl)-2-oxo-1,1-bis(trifluoromethyl)ethanol was also proved by single-crystal X-ray diffraction.     

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.     

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.     

Formation and structure of 1-Amino-4-methyl-4-(4-methyl-5-phenyl-1H-pyrazol-3-ylamino)-3-phenyl-4,5-dihydro-1H-pyrazol-5-one

The title compound 3 was obtained during the rearrangement of isoxazol-5-yl hydrazine 1 to 1-aminopyrazolone 2 at 115°. X-ray analysis of the corresponding benzylidene derivative allowed us to achieve the structure assignment.     

新型(4R,5R)-2-苯基-1,3-二氧戊环-4,5-二(2-吡啶甲氧基)甲烷的合成

设计并合成了一种新型以L-酒石酸为手性源的具有C2-对称轴的吡啶衍生物手性配体——(4R,5R)-2-苯基-1,3-二氧戊环-4,5-二(2-吡啶甲氧基)甲烷,其结构经1H NMR和MS表征。