Thermal decomposition of 2-hydroxyalkylthiol esters of phosphorus acids

Conclusions The decomposition of the 2-hydroxyalkylthiol esters of phosphorus acids at atmospheric pressure leads to alkylene sulfides and the corresponding phosphorus acids. The direction of the reaction for the thermal decomposition of these esters in vacuo depends on the structure of the substituents on the phosphorus atom.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2625–2627, November, 1976.     

Synthesis of o-Carboranyl Containing Esters of Pentavalent Phosphorus Acids

Abstract

A new method for the synthesis of o-carboranyl containing phosphoric, phosphonic and phosphinic acid esters, where the o-carboranil group is in the ester group, has been developed. The propargyl esters of these acids were prapared in two ways: by the reaction of phosphorus acid salts with propargyl chlorid and by interaction of propargyl alcohol with acid chlorides in the presence of Et₃N. The propargyl esters have been converted into carboranyl containing compounds upon treatment with decaborane and dimethyl aniline     

Stability of 2-hydroxyalkyl esters of thiophosphoric acids with one bulky substituent on phosphorus

Conclusions The hydroxy-thiol rearrangement of the 2-hydroxyalkyl esters of dialkylthiophosphoric acids is retarded when one bulky substituent, and specifically the 1,1-dimethyl-2,2,2-trichloroethoxy group, is inserted on the phosphorus atom. Stabilization fails to occur when one phenoxyl substituent in the 2-hydroxyalkyl esters of diphenylthiophosphoric acid is replaced by this group.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 429–431, February, 1984.     

Synthesis and Reactivity of the New Trimethylsilyl Esters of Aminomethylenebisorganophosphorus Acids

The interaction of trimethylsilyl esters of trivalent organophosphorus acids containing PH and POSiMe₃ fragments in the presence of trimethylsilyl trifluoromethanesulfonate as catalyst is proposed as a convenient method for the synthesis of new trimethylsilyl esters of aminomethylenebisorganophosphorus acids with three and four coordinated phosphorus. Also the new functionalized derivatives of the aminomethylenebisphosphinic acids with substituted hydroxymethyl moieties are synthesized, and some properties of the obtained compounds are presented.     

Synthesis of the New Types of N‐Unsubstituted Aminomethylenebisorganophosphorus Acids and Their Derivatives

The interaction of trimethylsilyl esters of trivalent organophosphorus acids containing PH and POSiMe₃ groups with hydrochlorides of ethoxymethylene imines is a convenient method for the synthesis of new trimethylsilyl esters of N‐unsubstituted aminomethylenebisorganophosphorus acids with three and four coordinated phosphorus. Also trimethylsilyl trifluoromethanesulfonate as effective catalyst is used for the similar interaction of hydrochlorides of ethoxymethylene imines with tris(trimethylsilyl)phosphite. The corresponding bisorganophosphorus acids and their derivatives are presented.     

Isomerization of S-2-hydroxyalkyl esters of cyclic phosphorus thioacids

Conclusions The S-2-hydroxyalkyl esters of cyclic P(V) thioacids, which were obtained by reacting a cyclic phosphorus monothioacid with an alkylene oxide, are converted to the 2-mercaptoalkyl esters of cyclic phosphorus acids independent of the size of the ring.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2594–2596, November, 1980.     

Synthesis of carborane-containing phosphates by catalytic phosphorylation

The catalytic phosphorylation ofo-carboranylmethanol with different phosphorus acid chlorides has been studied. This method makes it possible to obtain esters of phosphorus acids and esters of the corresponding phosphorus acid chlorides containing carboranylmethyl groups. The catalytic phosphorylation of 1,2-bis(hydroxymethyl)-o-carborane affords both acyclic and cyclic phosphate esters. The structure of the synthesizedo-carborano[1,2-e]-1,3,2-dioxaphosphepane was confirmed by X-ray diffraction analysis.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 145–149, January, 1995.     

Thermal stability of perfluoroalkanesulfonic acids and their anhydrides. New and easy approach to RFSO2ORF esters.

Perfluoroalkanesulfonic anhydrides (R_FSO₂)₂O when mixed with acids decompose into perfluoroalkanesulfonic esters R_FSO₂OR_F, thereby providing a new facile synthesis of these esters from perfluoroalkanesulfonic acids and phosphorus pentoxide.     

Structure of some organic compounds containing tin and phosphorus

Summary On the basis of Malatesta's results and of our confirmatory experiments, it must be considered that the organic compounds of tine and phosphorus under consideration are esters of phosphorus acids in which tine is linked to phosphorus through oxygen.     

Unsaturated Analogues of Phosphorylcholines

Abstract

The vinyl esters of phosphorus acids, containing onium group in β-position, for example, betaines type A and B (X = N, P), have a number of features, attracting to them significant atlention of researchers.^[] First of all, these compounds are interesting as examples of hydrolytically stable inhibitors of acetylcholinesteraze, posessing complex action.     

Isomerization of S-2-hydroxyalkyl esters of phosphorus acids

Conclusions Based on the³¹P NMR spectral data, the isomerization of the S-2-hydroxyalkyl esters of thiophosphoric and thiophosphonic acids to the corresponding 2-mercaptoalkyl esters of phosphoric and phosphonic acids proceeds with the formation of stable intermediate compounds, which, in all probability, contain the 1,3,2-thiaoxaphospholane ring. The 2-mercaptoalkyl esters of phosphorus acids decompose to either the dialkylphosphoric or phosphonic acid and alkylene sulfide. Compounds of the 1,3,2-thiaoxaphospholane series are not formed during the decomposition.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2142–2144, September, 1978.     

Preparation of peptides and active esters by a hydrolysis-dehydration reaction with phosphonites,and the application of the reaction to polymer synthesis

Dehydration reactions accompanied by hydrolysis of the condensation reagent itself, generalized as “hydrolysis-dehydration,” are seen in the formation of amides and esters using phosphites. The proposed concept was shown to be applicable also to the reactions with other phosphorus compounds, such as phosphinites, phosphonites and phosphonates. Aryl esters of these phosphorus compounds were effective for producing amides and esters, whereas alkyl esters were ineffective. Several peptides and active esters of amino acids were prepared using diphenyl phosphonites in the presence of tertiary amines and extended to the preparation of polypeptides and polyamides. Linear polypeptides and high molecular weight polyamides were obtained by means of diphenyl ethylphosphonite in N-methylpyrrolidone containing pyridine.     

Stability of 2-hydroxyalkyl esters of thio- and selenophosphoric acids with two 1,1-dimethyl-2,2,2-trichloroethoxy substituents at the phosphorus atom

Conclusions The introduction of two 1,1-dimethyl-2,2,2-trichloroethoxy groups at the phosphorus atom in 2-hydroxyalkyl esters of dialkylthio- or dialkylselenophosphoric acids prevents the hydroxy-thiol and hydroxy-selenol rearrangements of these esters.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2134–2136, September, 1984.     

有机磷化合物的研究 X:五价膦(磷)酸酯与卤代烷在卤化钠存在下的酯烷基交换反应

A detailed study on the ester alkyl exchange reaction of various types of quinique-valent phosphorus esters with alkyl halide in the presence of sodium bromides was reported. This ester alkyl exchange reaction was evidently influenced by the structure of phosphorus esters and alkyl halides as well as by the nature of the halides of metal ions. In contrast with the reaction without sodium hadlide, the alkyl phosphinmate is more reactive than phosphonate and phosphate by treatment with alkyl halide in the presence of sodium halide. This is consistent with the high nucleophilicity of >P(CO)O- as leaving group. The reactivity of butyl halides was decreased in the following order: n-BuBr>i-BuBr=s-BuBr>t-BuBr. Alkyl iodide was proved to be more reactive than the corresponding bromide and chloride. However, the use of iodioe is limited by the formation of alkene resulted from the elimination of HI. These structural effects show the general characteristics of a nucleophilic substitution reaction. A reaction mechanism involving the formation of sodium salt intermecutiate was proposed based on the concept of HSAB principle. This reaction may, however, be used as a convenient method for the preparation of mixed esters of quinque-valent phosphorus acids.     

Synthesis of the esters of 1-alkyl-2-aminoindolyl-3-acetic acids by the kost reaction

The reaction of the esters of N-alkyl-N-phenylhydrazinocarbonylpropionic acids with phosphorus oxychloride in dioxane or with phosgene in benzene leads to the formation of the esters of 1-alkyl-2-aminoindolyl-3-acetic acids and of the corresponding N-alkyl-N-phenylaminosuccinimides.All-Russian Center for the Safety of Biologically Active Substances (ARC BAS), Kupavna, Moscow Oblast 142450. Translated from Khimiya Geterots iklicheskikh Soedinenii, No. 11, pp. 1502–1506, November, 1995. Original article submitted September 2, 1995.     

Thermal degradation of flame-retardant compounds derived from castor oil

Castor oil is a non-edible plant oil produced in a large quantity annually. It is a triglyceride of primarily (approximately 90%) ricinoleic acid. The acid residues contain both a hydroxyl group and a double bond which permit ready functionalization. The hydroxyl group may be converted to phosphorus esters of varied structure while the unsaturation readily undergoes addition of bromine. Derivatives of castor oil containing phosphorus, bromine, or phosphorus and bromine have been prepared and fully characterized using spectroscopic and thermal methods. The thermal stability and mode of degradation for these compounds have been assessed using thermogravimetry and infrared spectroscopy. The primary mode of degradation for the phosphorus esters is elimination of the corresponding phosphorus acid (phosphates more readily than phosphonates). Brominated castor oil undergoes thermally induced dehydrobromination at relatively modest temperatures and this promotes dehydration (at temperatures well below that required for dehydration of unmodified castor oil). Brominated phosphorus esters of castor oil undergo degradation initiated by dehydrobromination.

     

Synthesis of thiazole aminophosphine oxides, aminophosphonic and aminophosphinic acids and Cu(II) binding abilities of thiazole aminophosphonic acids

A series of new aminophosphine oxides, aminophosphonic and aminophosphinic acids derived from thiazole was synthesized by addition of phosphine oxides or silylated phosphorus esters to the corresponding thiazole aldimines. The thiazole aldimines were obtained from 2-thiazole aldehyde and primary amines by a standard procedure. The corresponding phosphine oxides were obtained by alkylation of diethyl phosphite or ethyl phenylphosphinate with the appropriate Grignard reagents. The silylated phosphorus esters were prepared from trimethyl phosphite and from methyl- or phenylphosphinic ethyl ester by treatment with bromotrimethylsilane. The coordination ability towards Cu(II) ions are described for two obtained aminophosphonate ligands.     

o-Carboranyl-containing esters of pentavalent phosphorus acids

Conclusions Some new carboranyl esters of pentavalent phosphorus acids were synthesized from the appropriate propargyl esters and decaborane.See [1] for preliminary communication.Translated from Izvestiya Akademii NaukSSSR, Seriya Khimicheskaya, No. 11, pp. 2640–2644, November, 1983.     

Synthesis of New Functionalized Organophosphorus Acids and their Derivatives

Abstract

Functionalized organophosphorus acids and their derivatives are of great interest as chelating ligands, bioactive substances with various properties and the key compounds for the synthesis of phosphorus containing peptides. We have developed the convenient methods of the synthesis of new functionalized organophosphorus acids and their derivatives using a series of PH-acids and their esters with highly reactive fragments PH and POSi as well as phosphorus containing arnines with fragments PCHNH and PCHNSi. These organophosphorus synthons react smoothly with α-heterosubstituted derivatives of various amines and amides, functionalized alkenes and their oxides, as well as with acyl and sulfonyl chlorides giving the perspective compounds with high yields. New available types of new functionalized organophosphorus acids and their derivatives are presented below.     

Modification of Epoxy Binders for Glass- and Basalt-Reinforced Plastics

The process parameters of production of epoxy binders modified with glycidyl esters of phosphorus acids were studied, and the performance characteristics of glass- and basalt-reinforced plastics on their basis were determined.