Studies on the synthesis of heterocyclic compounds. III. Synthesis of 1,3,2-benzodioxa- and 1,3,2-benzoxathiarsole derivatives

The preparation and reaction of 1,3,2-benzodioxa- and 1,3,2-benzoxathiarsoles (IIa-b) are described. Spiran derivatives Va-c are obtained by treating IIa-b with Ia-b and triethylamine, while the reaction of IIa-b with sodium hydroxide, ethoxide and p-cresolate gives the compounds VIa-b, VIIa-b and VIIIa-b, that can evolve to Xa-b. Reaction of IIa-b with sodium p-toluenethio-late and n-butyllithium gave the compounds IXa-b and XIa-b respectively. The structure of the prepared compounds has been determined by elemental analysis and spectroscopic data.     

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.     

A Convenient Method for the Synthesis of 1,3,2-Oxazaphospholidin-[3,2-a]-8-oxo-10-thio(or seleno)-[1,3,2]-benzodiazaphosphorines

Tris(diethylamino)phosphine was widely used as a cyclizing reagent in the synthesis of different phosphorusheterocycles1,2,3,4, however, it was seldom reported that P(NEt2)3 acted as a cyclocondensation reagent for compounds with groups of which one being quite different from the others in reactivity. Usually, the fused phosphorusheterocycles were prepared step by step in the ring closure 5,6, while this paper focused on the utilization of P(NEt2)3 for the synthesis of the fused heterocycles…     

Syntheses, structures, luminescence and electrochemistry of benzene- and biphenyl-centered bis- and tris-1,3,2-diazaboroles and -1,3,2-diazaborolidines

Reaction of 1,4-bis(dibromoboryl)benzene (1a) with 2 equiv. of the diazabutadiene tBuN=CH-CH=NtBu and subsequent reduction of the obtained bis(1,3,2-diazaborolium)salt 2a with sodium amalgam afforded the 1,4-bis(1,3,2-diazaborolyl)benzene 3a. Similarly, 1,3-bis(dibromoboryl)benzene (1b), 1,3,5-tris(dibromoboryl)benzene (1c) and 4,4'-bis(dibromoboryl)biphenyl (1d) were converted into compounds 3b, 3c and 3d which contain two or three diazaborolyl substituents at the arene core. Treatment of precursors 1a,b,d with two equiv. or with three equiv. of N,N'-di-tert-butylethane-1,2-diamine in the presence of an excess of NEt3 gave rise to the diazaborolidine derivatives 4a-4d. Reaction of 1,3-bis(diiodoboryl)benzene with two equivalents of N,N'-dimethylethane-1,2-diamine in the presence of NEt3 furnished the corresponding 1,3-bis(diazaborolidinyl)benzene 4e. The novel compounds were characterized by elemental analyses and spectroscopy (1H, 13C, 11B NMR, MS). The molecular structures of 3c, 4a and 4e were eludicated by X-ray-diffraction analyses. In addition to this, the oxidative cyclovoltammograms and blue emission spectra of these novel compounds were discussed. Here, the electronic communication between boron heterocycles on the different spacer-units and the luminescence of the oligo-diazaborolylarenes were of interest.     

Synthesis and characterization of the first examples of 1,3,2‐diazastibole and 1,3,2‐diazabismole ring compounds

Reaction of either 9,10‐phenanthrenedione (phenanthrenequinone) or diphenylethanedione (benzil) with two equivalents of Li[N(SiMe₃)₂], followed by quenching of the reaction with excess ClSiMe₃, produces the corresponding N,N′‐bis(trimethylsilyl)‐α‐diimines in high yields (85–95%). Subsequent dehalosilylation/ring‐closure reactions with SbCl₃ and BiCl₃ produce, in 90–95% yields, the first examples of 1,3,2‐diazaheterole ring compounds containing antimony or bismuth. These 2‐chloro‐1,3,2‐diazaheteroles can be further functionalized at the pnictogen by reaction with, for example, Li[N(SiMe₃)₂], to produce the corresponding 2‐bis(trimethylsilyl)amido‐1,3,2‐diazaheteroles. All of these new main group element–containing heterocycles have been characterized through ¹H and ¹³C NMR, elemental analysis, and two of the diazastiboles have been structurally characterized by single‐crystal X‐ray analysis, confirming the ring structures. Both of these diazastiboles exist as associated dimers in the solid state; half of the dimer represents the asymmetric unit. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 423–429, 1999     

Synthesis and physiological activity of new organophosphorus pesticides of 1,3,2-oxazaphosphorinane series

Methods for the synthesis of 2-aryloxy(arylthio)- and 2-alkoxy(alkylthio)-2-thio(oxo)-1,3,2-oxazaphosphorinanes and theirN-substituted derivatives based on the reactions of the corresponding dichlorophosphates, dichlorothio-, and dithiophosphates with 3-aminopropan-1-ol or its substituted derivatives in the presence of Et₃N or aqueous alkali under phase transfer catalysis conditions, as well as by the reaction of the tetramethylammonium salt of 2-hydroxy-2-thio-1,3,2-oxazaphosphorinane with alkyl- and acyl halides, by that of 2-chloro-2-thio-1,3,2-oxazaphosphorinane with sodium thiolates, and by other methods, were developed. The compounds obtained exhibit high nematocide activity but low toxicity for mammals. Some active synergists for permethrine were found among these compounds.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2241–2249, November, 1995.This study was financially supported in part by the International Science Foundation (Grant Nos. NDO 000 and NDO 300) and by the Russian Foundation for Basic Research (Grant No. 93-03-0451). The authors are grateful for this support.     

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 ).     

Studies on the synthesis of heterocyclic compounds. V. Preparation of 1,3,2-benzoxathiaphosphole,arsole and stibole derivatives by exchange methods

A new convenient method for synthesis of heterocyclic compounds of five-membered rings containing an O-M-S (M = P, As, Sb) linkage is described. The compounds IIIa-c, IVa-b, Va-b, Viand VII were prepared starting from 2,2-dimethyl-1,3,2-benzoxathiastannole (II) and derivatives of phosphorus, arsenic and antimony. The structures of newly prepared compounds was determined by elemental analysis, spectroscopic methods (ir, nmr and ms) and comparison with authentic samples obtained via a different manner.     

Chlorinations of derivatives of 2,2,2-trichlorobenzo-1,3,2-dioxaphospholes

By ³¹P, ¹³C, ¹³C-{¹H}, and ¹H NMR spectroscopy the chlorination of 4-and 5-methyl-2,2,2-trichlorobenzo-1,3,2-dioxaphosphols was shown to provide in quantitative yield 4-methyl-2,2,2,5-tetrachloroand 6-methyl-2,2,2,5-tetrachlorobenzo-1,3,2-dioxaphosphols. Their hydrolysis led to the formation of difficultly available 4-methyl-5-chloro-and 3-methyl-4-chloro-1,2-dihydroxybenzenes. The structure of the latter compound was established by XRD analysis. The 5-methyl-2-chlorobenzo-1,3,2-dioxaphosphol treated with excess chlorine was converted in succession into 5-methyl-2,3,4,5,6,6-hexachlorocyclohex-1-en-3-yl dichlorophosphate and 5-methyl-1,2,4,4,5,6-hexachlorocyclohex-1-en-3-yl dichlorophosphate. The hydrolysis resulted in 5-methyl-2,3,4,5,6,6-hexachlorocyclohex-2-en-1-yl dihydrophosphate. The configuration of three chiral carbon atoms in the latter was established by XRD study. In the course of the chlorination the aromaticity of the ortho-phenylene fragment was distorted and 3,3-sigmatropic shift of the dichlorophosphoryl group occurred. The reaction with chlorine of 5-tert-butyl-2,2,2-trichlorobenzo-1,3,2-dioxaphosphol and 2,2,2-trichloro-benzo-1,3,2-dioxaphosphol was not selective: The reaction product obtained in excess chlorine transformed on hydrolysis into tetrachloropyrocatechol. Its solvates with water and dioxane were studies by XRD analysis.     

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.     

Synthesis and Properties of Some New 1,3,2-Oxazaphospholane Derivatives

Abstract

A series of new 1,3,2-oxazaphospholane derivatives(I) have been synthesized by the reaction of P(NEt₂)₃ with RNHCH₂O₂OH at 80°C. When they were refluxed with sulfur in benzene, compounds II were obtained conveniently.     

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.     

Novel buron heterocycles. I. 2,3-dihydro-1,3,2-benzodiazaborin-4(III)-ones and 1,2-dihydro- 1,3,2-benzodiazaborines

A series of 2,3-dihydro-1,3,2-benzodiazaborin-4(IH)-ones have been prepared and their ir spectra compared with those of their carbon isosteres. Solvolysis of these boron compounds in ethanol has been followed by uv and reveals a relationship between structure and rates of ethanol-ysis. Unexpectedly, these boron heterocycles, in contrast to their carbon isosteres, dissolve in aqueous alkali to form stable anions and the significance of this is discussed. The 1 :1 adducts of 1 and phosphorus oxychloride has been utilized to prepare two derivatives of the very stable 1,2-dihydro-2-phenyl-1,3,2-benzodiazaborin heterocycle.     

Boron-nitrogen compounds: XCVIII. Preparation and reactions of 2-(azol-1′-yl)-1,3,2-diazaboracycloalkanes

The preparation of several 1,3-dimethyl-2-(azol-l′-yl)-1,3,2-diazaboracyclohexanes is described and their NMR spectra are interpreted. The reaction of 2-(pyrazol-1′-yl)-1,3,2,-diazaboracyclohexanes with pyrazoles was found to lead to 1/1 molar adducts which exist in equlibrium with the uncomplexed species, whereas B-tetraalkylpyrazaboles are obtained on reaction with (dimethylamino)dialkylboranes. Similar reactions of 2-(pyrazol-l′-yl)-1,3,2-diazaboracyclopentanes with several other nitrogen donor molecules were examined. The chemistry of the various species was found to be greatly affected by the NBN bond angle of the 1,3,2-diazaboracycloalkane ring. The reaction of pyrazabole with monoamines requires very high temperatures which, however, promote extensive ligand redistribution; no monomeric pyrazol-l-ylboranes could be obtained from the process.     

Conversions of 2-Phenyl-1,3,2-dioxaphospholane Under the Action of Hydrogen Chloride

The reaction of 2-phenyl-1,3,2-dioxaphospholane with HCl gives a mixture of phenylphosphinic acid, bis(2-chloroethyl) phenylphosphonate, and phenylphosphine; therewith, intermediate oligomeric phosphonites, hydrophosphoryl compounds, and phosphoranes were detected. Thermal treatment of the reaction mixture results in formation of ethylene phenylphosphonate and (2-chloroethyl)phenylphosphinate.     

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.     

Synthesis and characterization of a rare arsenic trithiolate with an organic disulfide linkage and 2-chloro-benzo-1,3,2-dithiastibole

The synthesis and structural characterization of bis(2-(1,3,2-benzodithiarsol-2ylsulfanyl)-benzenesulfide) (1) and 2-chloro-benzo-1,3,2-dithiastibole (2) are reported. Both compounds contain a five-membered ring with sulfur bound to the central group 15 atom. In compound 1, the centroidal distance between each opposing arene is 3.819 Å. An alternating arene sandwich structure is created in the solid state with an intramolecular centroid distance between each set of stacked rings of 5.467 Å. Compound 2 is an example of a three coordinate antimony dithiolate. It does not possess any of the secondary interactions seen in 1. Compound 2 demonstrates trigonal bypyramidal geometry around the antimony if secondary interactions are considered.     

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.     

Simultaneous Formation of Cage and Spirane Pentaalkoxyphosphoranes in Reaction of 5,5-Dimethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphosphorinane with Hexafluoroacetone

Russian Journal of General Chemistry - The reaction of hexafluoroacetone with 5,5-dimethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphosphorinane occurs in two simultaneous directions: through the...     

Synthese,Struktur, Elektrochemie und optische Eigenschaften von alkinylfunktionalisierten 1,3,2‐Diazaborolen und 1,3,2‐Diazaborolidinen

Syntheses, Structures, Electrochemistry and Optical Properties of Alkyne‐Functionalized 1,3,2‐Diazaboroles and 1,3,2‐Diazaborolidenes The reaction of 2‐bromo‐1,3‐ditert‐butyl‐2,3‐dihydro‐1H‐1,3,2‐diazaborole ( 3 ) with lithiated tert‐butyl‐acetylene and lithiated phenylacetylene affords the 2‐alkynyl‐functionalized 1,3,2‐diazaboroles 4 and 5 as a thermolabile colorless oil ( 4 ) or a solid ( 5 ). Similarly 2‐bromo‐1,3‐diethyl‐2,3‐dihydro‐1H‐1,3,2‐benzodiazaborole ( 6 ) was converted into the crystalline 2‐alkynyl‐benzo‐1,3,2‐diazaboroles 7 and 8 by treatment with LiC≡C–tBu or LiC≡CPh, respectively. 2‐Ethynyl‐1,3‐ditert‐butyl‐2,3‐dihydro‐1H‐1,3,2‐diazaborole ( 2 ) was metalated with tert‐butyl‐lithium and subsequently coupled with 2‐bromo‐1,3,‐ditert‐butyl‐2,3‐dihydro‐1H‐1,3,2‐diazaborole ( 3 ) to afford bis(1,3‐ditert‐butyl‐2,3‐dihydro‐1H‐1,3,2‐diazaborol‐2‐yl)acetylene ( 9 ) as thermolabile colorless crystals. Analogously coupling of the lithiated species with 6 or with 2‐bromo‐1,3‐ditert‐butyl‐1,3,2‐diazaborolidine ( 11 ) gave the unsymmetrically substituted acetylenes 10 or 12 , respectively, as colorless solids. Compounds 4 , 5 , 7 – 10 and 12 are characterized by elemental analyses and spectroscopy (IR, ¹H‐, ¹¹B{¹H}, ¹³C{¹H}‐NMR, MS). The molecular structures of 5 , 8 and 9 were elucidated by X‐ray diffraction analyses.