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.     

Synthesis,Crystal Structure,and Flame Retardance of 2-(3-Silatranyl-Propylamino)-4-(2,4-Dichlorophenyl)-5,5-Dimethyl-1,3,2-Dioxaphosphinane-2-Sulfide

Abstract

2-(3-Silatranylpropylamino)-4-(2,4-dichlorophenyl)-5,5-dimethyl-1,3,2-dioxa phosphinane-2-sulfide 4 was synthesized by a nucleophilic substitution reaction of 2-chloro-1,3,2-dioxaphosphinane-2-sulfide 2 with γ-aminopropylsilatrane 3, which was prepared by the cyclization reaction of triethanolamine and γ-aminopropyltriethoxysilane. The structure of the title compound was confirmed by IR, ¹H NMR, ³¹P NMR, EI-MS, and elemental analysis as well as by single crystal X-ray diffraction and its thermal properties were studied by thermogravimetry (TG) and differential scanning calorimetry (DSC). Thermal analysis and preliminary fire retardance testing suggest that compound 4 should function as a good flame retardant.     

Synthesis and mesomorphic properties of cyano derivatives of 2-(4-carbohydroxy-3-halogenphenyl)-5-alkyl-1,3,2-dioxaborinanes

Abstract

Cyano derivatives of 2-(4-carbohydroxy-3-halogenphenyl)-5-alkyl-1,3,2-dioxaborinane have been synthesized. These compounds are characterized by low nematic-isotropic transition temperatures and a high positive dielectric anisotropy; they are promising for use in liquid-crystalline mixtures intended for high information electrooptic display devices.     

PHOSPHORUS-NITROGEN COMPOUNDS. PART 52.1 THE SYNTHESIS OF SOME 1,3,2-BENZODIAZAPHOSPHORINE 2-OXIDES AND 2-SULPHIDES

Abstract

The reactions of 4-methyl-2-[N-(p-toluidinyl)methyl]aniline with phosphorus oxychloride, thiophosphoryl chloride, and their derivatives yield 1,3,2-benzodiazaphosphorine 2-oxides and 2-sulphides. Their ¹H NMR and infrared spectra are discussed. Related 1,3,2-benzodiazophosphorine and 1,3,2-dibenzodiazaphosphocine 2-oxides and 2-sulphides are compared.     

On the condensation of 2,2-difluoro-4-methyl-benzo[d]-1,3,2-dioxaborines with cyano acetic acid derivatives. Formation and transformation of 3-cyano-4-methyl-benzo[b]pyran-2-ones and their 2-imine precursors

Summary By condensation of 2,2-difluoro-4-methyl-benzo[d]-1,3,2-2H-dioxaborines (12) with cyano acetic acid derivatives in presence of weak bases, 3-cyano-4-methyl-benzo[b]pyran-2-ones (13) or their 3-cyano-4-methyl-benzo[b]pyran-2-imine precursors (14) are available in satisfactory yields.

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Zur Kondensation von 2,2-Difluor-4-methyl-benzo[d]-1,3,2-2H-dioxaborinen mit Cyanessigsäure- Derivaten. Bildung und Umwandlung von 3-Cyano-4-methyl-benzo[b]pyran-2-onen und ihrer 2-Imino-Vorstufen

Zusammenfassung Durch Kondensation von 2,2-Difluor-4-methyl-benzo[d]-1,3,2-2H-dioxaborinen (12) mit Cyanessigsäure-Derivaten in Gegenwart von Hilfsbasen entstehen in befriedigenden Ausbeuten 3-Cyan-4-methyl-benzo[b]pyran-2-one (13) oder ihre 3-Cyan-4-methyl-benzo[b]pyran-2-imino-Vorstufen (14).

     

Triphenylethanediol-Derived 2-Chloro-1,3,2- dioxaphospholane: Synthesis,Structure, and Reaction with Chiral Alcohols

The reaction of (S)-1,1,2-triphenylethanediol (3) with phosphorus trichloride leads to the diastereoselective formation of (S _C,R _P)-2-chloro-1,3,2-dioxaphospholane (2). Its configuration has been determined by single crystal X-ray diffraction. When reacted with racemic secondary alcohols, diastereomeric phosphites are obtained, which display substantial shift differences in the ³¹P NMR spectra. Thus, chlorodioxaphospholane 2 can serve as derivatizing reagent for chiral secondary alcohols permitting to determine their enantiomeric excess.     

STRUCTURE STERIQUE DES COMPOSES CYCLIQUES DU PHOSPHORE. XIII. ETUDE PAR MOMENT DIPOLAIRE DES OXO-2 ET THIO-2 PERHYDRO OXAZAPHOSPHORINES-1,3,2

Abstract

L'étude par moment dipolaire de la conformation de huit perhydro oxazaphosphorines-1,3,2 est décrite. The conformation of eight perhydro 1,3,2-oxazaphosphorines is studied by means of dipole moments.     

THE MOLECULAR STRUCTURE OF CIS-2-t-BUTYLAMINO-2-SELENO-4,4,6-TRIMETHYL-1,3,2-DIOXAPHOSPHORINANE C10H22NO2PSe,AN EXAMPLE OF THE TWIST-BOAT CONFORMATION

Abstract

Diastereoisomeric 2-t-butylamino-2-seleno-4,4,6-trimethyl-1,3,2-dioxaphosphorinans have been prepared and separated into pure cis- and trans-isomers. The minor isomer (cis) was investigated by means of x-ray crystallography and its has been demonstrated, that in solid state is possesses twist-boat conformation.     

CYCLIC ORGANOPHOSPHORUS COMPOUNDS. PART XVI1. MASS SPECTROMETRIC FRAGMENTATION OF SOME 5,5-DIMETHYL-1,3,2-DIOXAPHOSPHORINAN 2-OXIDES AND 2-SULPHIDES

Abstract

The mass spectra of seventeen 5,5-dimethyl-1,3,2-dioxaphosphorinan 2-oxides and nineteen 5,5-dimethyl-1,3,2-dioxa-phosphorinan 2-sulphides, mostly with amino substituents on phosphorus, have been determined. In some cases, interpretation of the spectra was aided by accurate mass measurements and by the examination of deuterated compounds. For the 2-sulphides, sulphur is lost either as such or as the thiol radical, both processes often being of weak intensity, and the thiol hydrogen appears to be derivable from either a ring methylene group or a C-5 methyl group. Loss of S or HS occurs more strongly for the phosphoramidothionates which, together with the phosphoramidates, also fragment to an important extent in the amido substituent with retention of the dioxaphosphorinan ring; P[sbnd]N bond cleavage is also observed. For the 2-thiones, the ions at m/e 165 (14; R[dbnd]H) and 133 (15; R[dbnd]H) are characteristic.     

AN UNUSUAL ADDITION AND RING-CLOSURE REACTION OF 1-(2-BROMOETHYL)-2,3-DIHYDRO- 3-PROPYL-1,3,2-BENZO-DIAZAPHOSPHORIN-4(1H)-ONE 2-OXIDE WITH CARBON DISULFIDE FOR A NEW AND CONVENIENT SYNTHESIS OF THE FUSED PHOSPHORUS HETEROCYCLIC COMPOUND

ABSTRACT

The reaction of 1-(2-bromoethyl)-2,3-dihydro-3-propyl-1,3,2-benzodiazaphosphorin-4(1H)-one 2-oxide with carbon disulfide takes an alternative pathway in the use of different bases. The sodium hydride mediated reaction leads to the formation of the tricyclic fused 1,2,3,4,4a,4b,5,6-octahydro-6-oxo-5-propyl-4-thia-3,4b,4a-thiazphosphaphenanthridine 4a-oxide via addition of H-P bond across the double bond of carbon disulfide followed by intramolecular cyclization. In the presence of triethylamine, refluxing a mixture of 1-(2-bromoethyl)-2,3-dihydro-3-propyl-1,3,2-benzodiazaphosphorin-4(1H)-one 2-oxide with carbon disulfide in benzene takes an unusual course with formation in excellent yield of the first example of fused phosphorus heterocyclic 4-[1′-(β-bromoethyl)-4′-oxo- 3′-propyl-1′,2′,3′,4′-tetrahydro-1,3,2-benzodiazaphosphorin-2′- sulfide]-1,2,3,4,4a,4b,5,6-octahydro-6-oxo-5-propyl-3,4b, 4a-thiazphosphaphenanthridine 4a,2′-dioxide, which was confirmed by spectroscopic methods, microanalyses and single crystal X-ray structure determination.     

THE STUDY OF 2-CHLORO-5,5-DIMETHYL-2-OXO-1,3,2-DIOXAPHOSPHORINANE IN SOLUTIONS BY MOLECULAR DYNAMICS METHODS USING IR AND RAMAN SPECTROSCOPY

Abstract

2-Chloro-5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinane has been studied in CCl₄, CHCl₃ and CD₃CN solutions by IR and Raman line shape analysis. Equilibrium process of dimerization and ring conversion in CCl₄ solutions have been considered. On the contrary to the commonly expected dominance of the conformer with the equatorial oriented P[dbnd]O bond for 2-halo-2-oxo-1,3,2-dioxaphosphorinanes, it was found that for the 2-chloro derivative both conformers are nearly equally distributed. It has been shown that the interactions induced absorption is an important mechanism of relaxation in the studied compound and this mechanism gives significant contribution to the total IR band broadening, while the interaction induced light scattering is negligible. The obtained results show that the molecular dynamics method can be useful in studying cyclic compounds in solutions.     

Unusual behavior of 3-(dimethylamino)-1-(2-hydroxyphenyl)prop-2-en-1-one towards some phosphorus reagents: Synthesis of novel diethyl 2-phosphonochromone,diethyl 3-phosphonopyrone and 1,3,2-oxathiaphosphinines

The chemical reactivity of 3-(dimethylamino)-1-(2-hydroxyphenyl)prop-2-en-1-one (1) towards some phosphorus reagents was studied. The enaminone 1 was cyclized into diethyl 2-phosphonochromone 2 via its treatment with diethyl phosphite in basic medium. However, its reaction with triethoxy phosphonoacetate gave the substituted pyrone phosphonate 3. In addition, two novel examples of 4-(dimethylamino)-6-(2-hydroxyphenyl)-2-sulfido-4H-1,3,2-oxathia-phosphinines 6 and 7 were obtained from treatment of enaminone 1 with O,O-diethyl dithiophosphoric acid and Lawesson’s reagent. When enaminone 1 was also treated with phosphorus decasulfide, it was turned into 4H-thiochromene-4-thione while its treatment with phosphorus tribromide, phosphorus oxychloride, or phenylphosphonic dichloride, 4H-4-oxo-chromene was isolated in all cases. The possible reaction mechanisms of the formation of these products were discussed. The structures of newly isolated products were established by elemental analysis and spectral tools.     

STUDIES ON ORGANOPHOSPHORUS COMPOUNDS XXX. MASS SPECTROSCOPIC INVESTIGATION OF 2-ALKYL-2-OXO-1,3,2-DIOXA-PHOSPHORINANE AND-PHOSPHEPANE

Abstract

The mass spectra of 2-alkyl-2-oxo-1,3,2-dioxa-phosphorinane and-phosphepane showed that the ring opening was in competition with the cleavage of the P[sbnd]C bond. According to the fragmentation pathway, which was dependent on the structure of exocyclic substituents on phosphorus, the 2-alkyl-2-oxo-1,3,2-di-oxa-phosphorinanes can be classified in two categories. The main process in category A was the ring opening and/or C[sbnd]C bond cleavage. While in category B the cleavage of P[sbnd]C bond was predominant. However, for 2-alkyl-2-oxo-1,3,2-dioxa-phosphepane. no matter how the structure of 2-alkyl group was, the ring opening was a dominant process.     

Reaction of a 2H-1,2,3-Diazaphosphole with Ethane-1,2-Dithiol

Abstract

Reaction of 2-acetyl-5-methyl-2H-1,2,3-diazaphosphole with ethane-1,2-dithiol at ?30°C leads to the formation of 2-acetyl-3-(β-mercaptoethylthio)-5-methyl-1,2,3-diaza-phospholene. On heating, this product forms 2-(β-mercaptoethylthio)-1,3,2-dithia-phospholane, 1,2-bis(1,3,2-dithiaphospholanyl)-dithioethane, and N-acetyl-N′-isopropilidene-hydrazine.     

Synthesis and Properties of Phosphorylated and Silylated α-Mercaptocarbonyl Compounds

Abstract

Phosphorylation and silylation of α -mercaptooarbonyl compounds have been investigated. A novel type of 1.4 S-O migration trimethylsilyl and P(III) groups has been discovered. The thiophosphite-thiophosphonate rearrangement when exposed to oxygen as well as heterocyclization with the formation of 1,3,2-oxathiaphospholenes and 1,3,2-oxathiasilalenes were also found. Some regularities of these processes and the properties of heterocycles synthesized have also been brought out.     

1,3,5-Triaza-2-phosphapentalenes

Abstract

Refluxing a dialkylammonium 4,5-dicyano-1,3,2-diazaphospholate¹ with a dialkyl-amine in chloroform gives a 4,6-bis(dialkylamino)-1,3,5-triaza-2-phosphapentalene¹ in good yield as the only reaction product. Unsymmetrically substituted representatives are accessible this way too.     

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.     

SOME MONOCYCLIC AND SPIROCYCLIC FLUOROPHOSPHORANES CONTAINING 6- AND 7-MEMBERED RINGS

Abstract

The reaction of 2,2-dimethyl-(1,8-naphtho[c,d])-1,3,2-dioxysilenin (3) and 2,2-dimethyldibenzo-1,3,2-dioxysilepin (4) with (C₆H₅)₂PF₃ gave the expected monocyclic fluorophosphoranes. Reaction of the same siloxy compounds with PF₅ gave products which could not be purified but whose ¹⁹F nmr spectra suggested that the desired spirocyclic compounds were present in the impure products. Reaction of the siloxy compounds with C₆H₅PF₄ did not yield identifiable products. The ¹⁹F nmr spectra of the products obtained are discussed and structures are tentatively assigned.     

Conformational transformations and autooxidation of 5-bromo-2-(2-methylpropyl)-5-nitro-1,3,2-dioxaborinane

Conformational study of 5-bromo-2-(2-methylpropyl)-5-nitro-1,3,2-dioxaborinane at the DFT PBE/3ξ level of theory revealed the only sofa–sofa interconversion pathway through a transition state corresponding to 2,5-twist conformer. The barrier to internal rotation of the axial nitro group is several times higher than that for the equatorial nitro group. According to the ¹H, ¹³C, and ¹¹B NMR, IR, and X-ray diffraction data, the main autooxidation products of 5-bromo-2-(2-methylpropyl)-5-nitro-1,3,2-dioxaborinane are 2-bromo-2-nitropropane-1,3-diol and boric acid.     

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.