Spectroscopic study of the conformation of 1,3,2-dioxaphosphorinanes with a P=S bond

5,5- Dimethyl-2-thio-2-phenoxy- and 5,5-dimethyl-2-thio-2-ethoxy-1,3,2-dioxaphosphorinanes exist in the liquid state and in solution in a three-component equilibrium featuring two chair forms with equatorial orientation of the P=S bond differing in the orientation of the OPh or OEt groups and a chair form with an axial P=S bond. The P=S bond in 4-methyl-2-thio-2-phenoxy-1,3,2-dioxaphosphorinane occupies the equatorial position.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 479–482, February, 1990.     

Synthesis and antienzyme activity of 2-OXO-2SR-4-methyl-1,3,2-dioxaphosphorinanes containing salsoline,salsolidine, cytisine,and decahydroquinoline residues

New derivatives of 2-oxo-4-methyl-1,3,2-dioxaphosphorinane containing residues of salsoline, salsolidine, cytisine, and decahydroquinoline have been synthesized, and their antienzyme activities have been investigated. The new compounds are irreversible inhibitors of the ACNE, BuChE, and CBE of warm-blooded animals and of insects: the antienzyme activities of the compounds depend substantially on the structure of the alkaloid component of the inhibitor molecule.A. S. Sadykov Institute of Biorganic Chemistry, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 62 70 71. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 572–575, July–August, 1996. Original article submitted October 4, 1995.     

Oxydative Derivatisierung von 1,3,2-Dioxaphosphorinanen unter Verwendung von Tetrachlormethan als Oxydans

Oxidative Derivatization of 1,3,2-Dioxaphosphorinanes Using Carbon Tetrachloride as Oxidant 2-Alkoxy- and 2-dialkylamido-1,3,2-dioxaphosphorinanes react with CCl₄ in presence or absence of protic nucleophiles under ring opening forming acyclic derivatives of phosphates. 2-Anilido-1,3,2-dioxaphosphorinane, however, forms 2-amido-2-phenylimido-1,3,2-dioxaphosphorinanes ( 6 ) retaining the heterocyclic ring system. The latter are also obtained in the reaction of 2-dialkylamido-1,3,2-dioxaphosphorinanes with CCl₄ and aniline. 2-Amino-2-oxo-1,3,2-dioxaphosphorinanes ( 8 ) are prepared from 2-hydrido-2-oxo-1,3,2-dioxaphosphorinane ( 7 ) by means of the Atherton-Todd reaction. In combination with the Staudinger reaction the latter yields N(2-oxo-1,3,2-dioxaphosphorinanyl)phosphazenes ( 10 ).     

Thermochemistry of Heteroatomic Compounds XXI: Heat Capacities of Some Derivatives of Methylphosphonic and Dithiophosphorus Acids

The heat capacities of 2,4-dimethyl-2-oxo-(I)-, 2,5,5-trimethyl-2-oxo(II)-1,3,2-dioxaphosphorinanes, methylphosphonic acid (III), O,O-dimethyl(IV)-, O,O-diethyl(V)-, O,O-di-isopropyl(VI)esters of dithiophosphorus acid, 4,5-dimethyl-2-thiono-2-mercapto-1,3,2-dioxaphospholane(VII), and 4-methyl-2-thiono-2-mercapto-1,3,2-dioxaphosphorinane(VIII) were determined using the scanning calorimetry.     

The reaction of 1,3-dibutyl-2-ethoxy-4,5-dimethyl-2-oxo-1,3,2-diazaphosphol-4-ene with tetracyanoethylene

The reaction of 1,3-dibutyl-2-ethoxy-4,5-dimethyl-2-oxo-1,3,2-diazaphosphol-4-ene with tetracyanoethylene gives 6-amino-1,3-dibutyl-5-cyano-2-ethoxy-4-(1-imino-2-cyanoethyl)-2-oxo-1,3,2-diazaphosphindane.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 303–305, February, 1994.     

Reactions of 1,3,2-dioxaphospholane derivatives with thiocyanatoalcohols

The reactions of 2-dimethylamino-, 2-methoxy-, 2-chloro-4,5-dimethyl-1,3,2-dioxaphos-pholanes with 4-thiocyanato-2-butanol in all cases yield 2-(1-methyl-3-thiocyanatopropoxy)-4,5-dimethyl-1,3,2-dioxaphospholane. The latter reacts with elemental sulfur to form the corresponding thiophosphate.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2130–2131, December, 1993.     

Benzaldehyde N,N-Dimethylhydrazone in the Reaction with 4-Oxo-2-pentafluorophenoxy-5,6-benzo- 1,3,2-dioxaphosphorinane. Preparation and Spatial Structure of 4-Dimethylamino-2,5-dioxo-2-pentafluorophenoxy-3-phenyldihydro-6,7-benzo-1,4,2-oxazaphosphepine

Benzaldehyde N,N-dimethylhydrazone with 4-oxo-2-pentafluorophenoxy-5,6-benzo-1,3,2-dioxaphosphorinane is capable to yield with high stereoselectivity a product of the phosphorus heterocycle expansion: unstable to hydrolysis 4-dimethylamino-2,5-dioxo-2-pentafluorophenoxy-3-phenyldihydro-6,7-benzo-1,4,2-oxazaphosphepine. The configuration of the prevailing isomer of the latter was determined by X-ray diffraction study.     

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.     

Synthesis and Biological Activity of 4-Chloromethyl-substituted 1,3,2-Dioxaphosphorinanes Phosphates and Amidophosphates

A series of 2-N and 2-O-substituted 2-oxo-4-chloromethyl-1,3,2-dioxaphosphorinanes were prepared by reaction of amines and alcohols with 2-oxo-2-chloro-4-chloromethyl-1,3,2-dioxaphosphorinane. The structure of compounds obtained was proved by means of ¹H and ^{1 3}C NMR spectroscopy. Some cyclic amidocyclophosphates possessed biological activity as inhibitors of mitotic fission and of Na⁺/H⁺ exchange.     

The preparation of some cyclic phosphonates and their use in olefin synthesis

The preparation and the use in olefin synthesis of two 5-membered cyclic phosphonates, 2-carbethoxy-methyl 4,5-dimethyle-2-oxo-1,3,2-dioxaphospholane (4b) and 2-cyanomethyl-4,5-dimethyl-2-oxo-1,3,2-diox-aphospholane (4c) and the 6-membered phosphonates, 2-carbalkoxymethyl-5,5-dimethyl-2-oxo-1,3,2-diox-aphosphorinanes (5a and 5b) and 2-cyanomethyl-5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinane (5c) are described. Reactions of 4b with aromatic and aliphatic aldehydes lead to preferential formation of cis-olefins. Reactions of the other cyclic phosphonates with aldehydes lead to various mixtures of cis and trans olefins.     

Synthesis and biological activity of some 1,3,2-diheteraphosphorinanes and their acyclic analogs

Methods were developed for the synthesis of 2-butylthio-2-oxo-1,3,2-oxazaphosphorinane, 2-butylthio-2-thioxo-1,3,2-dioxaphosphorinane, and 2-butylthio-2-thioxo-1,3,2-diazaphosphorinane, as well as of acyclicS-butylO-ethyl (diethylamido)phosphorothioates and-dithioates andS-butyl bis(diethylamido)phosphorodithioate. These compounds can serve as models of possible metabolites of cyclic compounds. Based on the data obtained in studies of the antiesterase activity of the resulting compounds and their synergistic activity in mixtures with permethrine, a possible mechanism ofin vitro andin vivo biological action of diheteraphosphorinanes was proposed.     

Reactions of some 2-oxo-1,3,2-oxathiaphospholanes and 2-oxo-1,3,2-phosphorinanes with phosphorus pentachloride

2-Phenoxy- and 2-dialkylamino-2-oxa-1,3,2-oxathiaphospholanes react with PCl₅ with ring opening and formation of the corresponding acid chlorides of thiophosphoric acid. Under analogous conditions, 2-phenoxy-2-oxo-1,3,2-oxathiaphosphorinanes do not react with PCl₅, while acid chlorides of thiophosphoric acid are formed in low yield along with other products in the reaction of 2-dialkylamino-2-oxo-1,3,2-oxthiaphosphorinanes with PCl₅.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2676–2678, November, 1992.     

Reaction of propylene oxide with tetramethyldiamidothiophosphoric acid

Conclusions The reaction of tetramethyldiamidothiophosphoric acid with propylene oxide proceeds under more drastic conditions than the analogous reactions with dialkylthiophosphoric acids, and leads to 2-dimethylamino-2-oxo-4-methyl-1,3,2-thiaoxaphospholane.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1659–1660, July, 1982.     

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.     

Reaction of 2-methoxy-1,3,2-dioxaphosphorino[4,5-<Emphasis Type="Italic">b</Emphasis>]pyridin-4(4<Emphasis Type="Italic">H</Emphasis>)-one with hexafluoroacetone

The reaction of the di-O-trimethylsilyl derivative of 2-hydroxynicotinic acid with methyl phosphodichloridite afforded 2-methoxy-1,3,2-dioxaphosphorino[4,5-b]pyridin-4(4H )-one. The NMR spectrkscopic data suggest that the reaction of the latter with hexafluoroacetone produces unstable 2-methoxy-2,5-dioxo-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2-dioxaphosphepino[4,5-b]pyridine, which is readily transformed into 9-methyl-2,5-dioxo-4,4- bis(trifluoromethyl)-4,5-dihydro-1,3,2-dioxaphosphepino[4,5-b]pyrid-9-inium-2-oate. The structure of the hydrolysis product of the latter, viz., 1-methyl-3-(2-hydroxy-3,3,3-trifluoro-2- trifluoromethylpropanoyl)pyridin-2-one, was established by X-ray diffraction analysis.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1640–1646, August, 2004.     

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.     

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.     

Synthesis and crystal structure of ethyl 1-benzyl-2-hydroxy-5-methyl-3-oxo-2-phenacyl-2,3-dihydropyrrole-4-carboxylate

Reaction of 5-phenyl-2,3-dihydro-2,3-furandione with ethyl 3-benzylamino-2-butenoate, resulting in ethyl 1-benzyl-2-hydroxy-5-methyl-3-oxo-2-phenacyl-2,3-dihydropyrrole-4-carboxylate and benzylamide ofN-benzoylpyruvic acid, was studied. The structure of the pyrrole derivative was confirmed by X-ray analysis.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1552–1555, August, 1995.     

Phosphorinane and Enol Rings in One Molecule. Evidence for Reciprocal Stabilization of Half-Chair Conformations

Abstract.

The X-ray crystal structure of 2-(2′,4′-dioxo-3′-pentyl)-5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinane (2) reveals significant half-chair distortion of the axially oriented cisenol ring. The molecule also undergoes in-plane deformations. R(O...O) = 2.410 Å in the enol moiety indicates a very strong hydrogen bonding. The enol content, δ_OH and thermodynamic parameters for the axial-equatorial conformational and keto-enol equilibriums were obtained from ¹H, ³¹P NMR and IR measurements in comparison with the planar 4,6-dimethyl isomer (1) containing equatorially oriented enol ring. The X-ray single crystal structure of 5,5-dimethyl-2-(methoxycarbonyl-3′-oxo-2′-butyl)-2-oxo-1,3,2-dioxaphosphorinane (3) reveals the unusual half-chair conformation of the dioxaphosphorinane cycle disposed a trans-enol ring substituent. ¹H, ³¹P NMR and IR solution data support the same structure displays a strong conformational preference while the minor forms are chair conformers with an axial or equatorial cis-enol ring.     

Alternating copolymerisations of dioxaphospholane and dioxaphosphorinane with γ-butyrolactone and ethylene oxide

Alternating copolymers containing phosphorus were prepared from 2-phenyl-1,3,2-dioxaphospholane, 2-phenyl-4-oxo-5,6-benzo-1,3,2-dioxaphosphorinane with ethylene oxide and γ-butyrolactone. The polymerisations took place without added catalyst. The copolymers were characterised by i.r. and NMR spectroscopy, viscosity measurements and phosphorus estimation. Key intermediates responsible for initiation and propagation of the copolymerisations were isolated and the mechanism of copolymerisation is discussed.