Showing papers by "Rashid Z. Musin published in 2010"

Facile Synthesis of 1,1′-Dialkylisoindigosthrough Deoxygenation Reaction of Isatins and Tris(diethylamino)phosphine

Abstract: A convenient one-step synthesis of symmetrical 1,1’-dialkyl derivatives of isoindigo is described Key words carbenes, deoxygenation, heterocycles, regioselectivity, phosphorus In the last years, isoindigo [1H,1’H-bis(indolin-3-yliden)-2,2’-dione] and especially it’s N- and N,N’-derivatives attract great attention not only as dyes, but as substances which possess a specific biological activity (anti-leukemia, antiproliferative, anti-inflammatory etc) 1-4 Thus, 1-(β-D-glucopyranosyl)-isoindigo was found to be an anti-leukemia drug 2-4 It has to be noted that the synthesis of 1-substituted isoindigo often is a multistep procedure The best approach to the synthesis of isoindigo derivatives seems to be the dimerization of ketocarbenes generated from isatin derivatives It has been assumed 5,6 that mixture of 3-(triphenylphosphoranyliden)-2,3-dihydro-1H-indol-2-one and isoindigo is formed with moderate yield by the reaction of triphenylphosphine with isatin and 1-methylisatin through intermediate carbene formation However, generation of carbenes from heterocyclic -diketones under the action of trivalent phosphorus deriv-atives has been insufficiently studied

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

Abstract: 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 (PRCS/PSCR). The reaction of the starting phosphepine with chloral proceeded highly stereoselectively (PRCSCS/PSCRCR) 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 and oxidation of (4-hydroxy-3,5-di- tert -butylphenyl)-methanebis[diethyl(diphenyl)phosphine oxides]

Abstract: The phosphorylated sterically hindered phenols and methylenequinones are potential inhibitors of oxidation of organic materials like polymers, petrochemical products, and biological systems [1–2]. In extension of studying the reaction of geminal polyhalides with aprotic nucleophilic reagents [3–5] we studied the reaction of 4-hydroxy-3,5-di-tert-butylbenzal chloride I with diethyl and diphenyl chlorophosphines. The reaction of dichloride I with diethyl chlorophosphine was found to proceed at keeping the hexane solution of reagents taken in the ratio 1:2 at room temperature for 24 h. The reaction of dichloride I with diphenyl chlorophosphine requires the heating of the reagents mixture at 100–110°С for 3 h. Adducts III form in high yields as colorless hygroscopic viscous products, weakly fuming in the air. According to the Р NMR spectra, compounds IIIa (δP 69.36 ppm) and IIIb (δP 71.02 ppm) have phosphonium structure in keeping with the literature data [6, 7]. The treatment of adducts IIIa and IIIb with anhydrous ethanol followed by evaporating of the solvents in a vacuum gives the corresponding bisphosphine oxides IV. DOI: 10.1134/S1070363210030278

Reaction of β-iminoalcohols with sulfur dioxide. Synthesis of (±)-(2-hydroxyalkylamino)phenyl(isopropyl)-methanesulfonic acids

Abstract: Reactions of 2-(N-isopropylidene)amino-2-methylpropanol, 2-(N-benzylidene)-, and 2-(N-isopropylidene) aminoethanols with sulfur dioxide in aqueous ethanol medium produce (±)-(2-hydroxyalkylamino)-phenyl(isopropyl)methanesulfonic acids. Structure of (±)-(2-hydroxyethylamino)phenylmethanesulfonic acid was determined by X-ray diffraction method.

Reaction of 3,6-Di(tert-butyl)-1,2-benzoquinone with Terminal Alkylacetylenes in the Presence of Phosphorus Trichloride.

Abstract: Benzo[e][1,2]oxaphosphinine 2-oxide derivatives are obtained in the reaction of alkyl- and haloalkylacetylenes with sterically hindered benzoquinone (I) in the presence of phosphorous trichloride.

An Unusual Cascade Reaction of 4,5-Dihydro-4,4-bis(trifluoromethyl)-2-phenyl-6,7-(4-chlorobenzo) [e]-1,3,2-dioxaphosphepin-5-one with Chloral.

Abstract: The reaction of 4,5-dihydro-4,4-bis(trifluoromethyl)-2-phenyl-6,7-(4-chlorobenzo)[e]-1,3,2-dioxaphosphepin-5-one with chloral (1:2) proceeds with evolving hexafluoroacetone and gives spiro{2-oxo-4-trichloromethyl-4,5-dihydro-2-phenyl-6,7-(4-chlorobenzo)[f]-1,3,2-dioxaphosphepine-5,2’-(3’-trichloromethyl)oxirane} with a high stereoselectivity. Configuration of the four chiral centres (P2SC4SC5SC3'S /P2RC4RC5RC3’R) was determined by a single crystal X-ray diffraction.

Stereoselective Synthesis of Spirophosphoranes with a Phosphorus—Carbon Bond Based on 2-(2-Acetylphenoxy)benzo-1,3,2-dioxaphosphole.

Abstract: The reactions of 2-(2-acetylphenoxy)benzo-1,3,2-dioxaphosphole containing the carbonyl group in the δ position with respect to the phosphorus atom with chloral and hexafluoroacetone afford tricyclic spirophosphoranes containing a phosphorus—carbon bond with high regio and stereoselectivity. The structures of the spirophosphoranes were established by X-ray diffraction.