Synthesis of polyfluoralkylated 1,3,2-dioxaphospholane and 1,3,2-dioxaphosphorinane oxides

Polyfluoroalkyl dichlorophosphates easily react with 1,2- or 1,3-alkanediols in a system pyridine–diethyl ether and afford 2-polyfluoroalkoxy-1,3,2-dioxaphospholane oxides or 2-polyfluoroalkoxy-1,3,2-dioxaphosphorinane oxides. In similar conditions the reaction of methyl dichlorophosphate with 1,2- and 1,3-alkanediols proceeds less effectively.     

N-phosphorylated 1,3,2-diheterophospholanes

Conclusions Methods have been proposed for phosphorylation of 4,5-benzo-1,3,2-oxazaphospholanes. Novel N-phosphorylated 1,3,2-oxaza- and -thiazaphospholanes have been synthesized.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1624–1627, July, 1982.     

2-Alkylperhydro-1,3,2-dioxazepines

Perhydro-1,3,2-dioxazepines were obtained for the first time by the acid-catalyzed cyclization of acyclic N,N-dialkoxyamines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2382–2384, October, 1989.     

4,5-Benzo-1,3,2-thiazaphospholanes

Conclusions 2-Substituted 3-methyl-4,5-benzo-l,3,2-thiazaphospholanes were obtained in high yields by the reaction of N-methyl-o-aminothiophenol with phosphorous acid di- and triamides.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2837–2839, December, 1976.     

1，3，2—二氮磷杂环戊烷类化合物的合成

为了寻找新的除草剂,我们研究了N,N′-二取代苯磺酰乙二胺与不同类型磷化合物的反应(图1)。实验表明取代乙二胺不能与亚磷酸酯反应,而与亚磷酰胺反应,发现产物及其硫化物具有一定的除草活性。     

2-Polyfluoroalkoxy-1,3,2-dioxaphosphorinanes

2-Polyfluoroalkoxy-1,3,2-dioxaphosphorinanes and related phosphocyclic compounds were prepared by alcoholysis of 2-amino-1,3,2-dioxaphosphorinanes with polyfluorinated alcohols. Principal chemical properties of the products were studied. For the first time copper complexes of fluorine-containing normal phosphites were prepared. A difference in the ligation of copper with fluorinated and nonfluorinated phosphites was shown.     

The chemistry of 1,3,2-diazaborolines (2,3-dihydro-1H-1,3,2-diazaboroles)

1,3,2-Diazaborolines (2,3-dihydro-1H-1,3,2-diazaboroles) are at the interface between inorganic, organometallic and organic chemistry. The planar rings with 6π-electrons may be regarded as heteroarenes, as evidenced by NMR and photoelectron spectra and confirmed by quantum mechanical calculations. The capability of 1,3,2-diazaborolines to act as η⁵-ligands adds chemical proof to this idea. High-yield syntheses of 1,3,2-diazaborolines with functional groups at boron have recently become available, providing a rich area of chemistry ranging from substitution processes via borylstannations to their conversion into oxazaborolidines.     

1,3,2-DIAZAPHOSPHORINANES. IV. PREPARATION AND CONVERSIONS OF 4-OXO-1,3,2-DIAZAPHOSPHORINANES

Abstract

Novel 1,3,2-diazaphosphorinanes containing the carbonyl group in the ring have been obtained and their properties investigated. The structures of the products were identified by IR-and ³¹P and ¹³C NMR spectroscopy.     

Chemical ionization induced fragmentations of 2-phenyl-1,3,2-dioxaborolanes and 2-phenyl-1,3,2-dioxaborinanes

Chemical ionization induced fragmentations (with 2-methylpropane as reagent gas) of 4-methyl- and 4,5-dimethyl-2-phenyl-1,3,2-dioxaborolane and 4-methyl-2-phenyl-1,3,2-dioxaborinane gave in each case two fragments, a hydrocarbon ion and metaboric acid. Propeae and thence metaboric acid are eliminated from 4,6-dimethyl-2-phenyl-1,3,2-dioxaborinane. The mechanisms of the fragmentations are discussed. Under the conditions used 2-phenyl-1,3,2-dioxaborolane and 2-phenyl-1,3,2-dioxaborinane do not fragment.     

Conformational analysis of 1,3,2-dioxaphospholan-yl and 4,5-benzo-1,3,2-dioxaphosphol-2-yl 2,2,2-trifluoroacetate

Conformational analysis of 1,3,2-dioxaphospholan-2-yl 2,2,2-trifluoroacetate and 4,5-benzo-1,3,2-dioxaphosphol-2-yl 2,2,2-trifluoroacetate was carried out using the method of dipole moments and quantumchemical calculations (DFT B3LYP/6-31G*). Both compounds are found to exist as an axial conformer with preferably syn arrangement of the carbonyl group and the lone electron pair.     

Über 1,3,2-Benzoxathiaborole

On 1,3,2-Benzoxythioborols 2-Mercapto-4-methoxyphenol reacts with BCl₃ giving the 2-Chloro-5-methoxy-1,3,2-benzoxythioborol. This compound reacts with phenol, thiophenol, 2-mercapto-4-methoxyphenol, sec. amines, lithium butyl and lithium phenyl and the corresponding 2-substituted products are obtained. With sodium two borol rings are connected resulting a boron-boron bond. The Lewis-acid behaviour of some of this compounds is investigated.     

Bistabilities in 1,3,2-dithiazolyl radicals

New synthetic methods for heterocyclic 1,3,2-dithiazolyl (DTA) radicals have been developed, and trends in the molecular spin distributions and electrochemical properties of a series of DTA radicals are reported. The crystal structures of [1,2,5]thiadiazolo[3,4-f][1,3,2]benzodithiazol-2-yl (TBDTA) and [1,3,2]pyrazinodithiazol-2-yl (PDTA) have been determined. The structure of TBDTA (at 293 and 95 K) contains two molecules in the asymmetric unit, each of which generates pi-stacked arrays, one consisting of antiparallel chains of centrosymmetrically associated dimers, the other comprising parallel chains of unassociated radicals. The structure of PDTA (at 293 and 95 K) is simpler, consisting of slipped stacks of pi-dimers. Variable-temperature magnetic susceptibility (chi(P)) measurements on TBDTA indicate essentially paramagnetic behavior for the unassociated radical pi-stacks over the range 5-400 K. By contrast PDTA is diamagnetic at all temperatures below 300 K, but between 300 and 350 K the value of chi(P) follows a sharp and well-defined hysteresis loop, with T(C) downward arrow = 297 K and T(C) upward arrow = 343 K. These features are symptomatic of a regime of bistability involving the observed low temperature pi-dimer structure and a putative high-temperature radical pi-stack. A mechanism for the interconversion of the two phases of PDTA and related structures is proposed in which hysteretic behavior arises from cooperative effects associated with the breaking and making of a lattice-wide network of intermolecular S- - -N' and/or S- - -S' interactions.     

Transition metal 1,3,2-diazagallol derivatives

Reduction of digallane (dpp-bian)Ga—Ga(dpp-bian) (1) (dpp-bian is the 1,2-bis[(2,6-di-isopropylphenyl)imino]acenaphthene dianion) with metallic sodium in THF leads to the formation of gallylsodium (dpp-bian)Ga—Na(thf)₄ (2). Reduction of digallane 1 with dicyclopentadienyltetracarbonyldiiron, vanadocene, and nickelocene furnishes the corresponding gallyl complexes (dpp-bian)Ga—FeCp(CO)₂ (3), (dpp-bian)Ga—VCp₂ (4) and [(dpp-bian)Ga]₂NiCp (5). The reaction of 1 with Cp₂Mn gives a gallium-free complex (dpp-bian)MnCp(dme) (6). Carbonylates [{(dpp-bian)Ga—M(CO)₅}{Na(thf)₂}]₂ (M = Cr (7), W (8)) and [{(dppbian)Ga}₂FeCp(CO)][Na(dme)₃] (9) were obtained by the reaction of carbonyls Cr(CO)₆, W(CO)₆, and [CpFe(CO)₂]₂ with compound 2. Diamagnetic derivatives 3, 7, 8, and 9 were characterized by ¹H NMR spectra. The structures of products 3—9 were established by single crystal X-ray diffraction.     

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.     

Preparation of some 4H-1,3,2-benzothioxaborine and 1H,4H-1,3,2-benzazoxaborine

The preparation of some 2-substituted-4H-1,3,2-benzothioxaborine and 2-substituted-1H,4H-1,3,2-benzazoxaborine is described.