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1. The acid chloride of chloromethyl-β-chloroformylvinylphosphinic acid is formed as the result of reacting chloromethyldichlorophosphine with propiolic acid. 2. The acid chloride of chloromethyl-β-chloroformylvinylphosphinic acid when reacted with an alcohol gives the ester of chloromethyl-β-carbethoxyvinylphosphinic acid, and when treated with acetic anhydride it is converted to 2-chloromethyl-2,5-dioxo-1,2-oxa-3-phospholene. 3. Only the ethoxyl group attached to phosphorus is replaced by the chlorine atom when the ethyl ester of chloromethyl-β-carbethoxyvinylphosphinic acid is treated with PC15. 4. 2-Chloromethyl-2,5-dioxo-1,2-oxa-3-phospholene easily enters into the diene synthesis reaction with 2,3-dimethyl-1,3-butadiene to give 5,6-dimethyl-1-chloromethyl-1,3-dioxo-2-oxaphosphabicyclo[3,0,4]-5,6-nonene. 5. The alcoholysis of 2-chloromethyl-2,5-dioxo-1,2-oxa-3-phospholene and 5,6-dimethyl-1-chloromethyl-1,3-dioxo-2-oxa-1-phosphabicycle[3,0,4]-5,6-nonene proceeds differently. In the first case the attack by the alcohol is directed to the phosphorus atom, while in the second case it is directed to the carbon atom of the carbonyl group.

1. Dibutyl vinylphosphonate has been synthesized. 2. It has been shown that vinylphosphonic esters combine at the double bond with hydrogen sulfide and with mercaptans, yielding the corresponding dialkyl 2-mercaptoethylphosphonates and dialkyl 2 alkylmercaptoethylphosphonates respectively. 3. It has been shown that vinylphosphonic esters maybe used as dienophiles in diene-synthesis reactions. A method has been developed for the preparation of esters of homologs and derivatives of cyclohexenylphosphonic acid.

The N-arylamides of dialkylphosphorous and diarylphosphlnous acids react with benzil to give the corresponding imidophosphites and imidophosphonates.

The review describes the reactions of fully esterified phosphorous acids, phosphoramidites, and the mixed anhydrides of dialkylphosphorous and carboxylic acids with carbonyl compounds not containing halogens: unsaturated and saturated aldehydes and ketones, α-diketones, and carbonyl compounds activated by ethoxycarbonyl, phosphoryl, nitrile, or any other electronegative group. The modes and mechanisms of these extremely varied and interesting reactions, which are important for progress in the chemistry of organophosphorus compounds and theoretical organic chemistry, have been examined. The bibliography includes 188 references.

1. It has been shown that O,O-diethyl hydrogen phosphorothioitein presence of sodium ethoxide reacts readily at the double bond of unsaturated ketones with formation of keto phosphonothionic esters. It adds to saturated ketones at, the carbonyl group with formation of α -hydroxy phosphonothionic esters. 2. O,O-Diethyl hydrogen phosphorothiotte -adds at the carbonyl group of unsaturated and saturated aldehydes with formation, respectively, of unsaturated and saturated α-hydroxy phosphonothionic esters. 3. A method .has been developed for the synthesis of keto phosphonothionic esters and of unsaturated and saturated α-hydroxy phosphonothionic esters.

The reaction of substituted 2,5-dioxo-1,2-oxaphospholanes with mercaptans goes to a large degree contrary to the principle of hard and soft acids and bases, with attack of the mercaptan on the carbonyl group.

1. β-Chloroformylvinyl(phenyl)phosphinic chloride has been obtained by the reaction of phenyldichlorophosphine with propiolic acid. 2. β-Chloroformylvinyl(phenyl)phosphinic chloride is converted on treatment with acetic anhydride into 2,5-dioxo-2-phenyl-1,2-oxaphosphol-3-ene. 3. On hydrolysis, 2,5-dioxo-2-phenyl-1,2-oxaphosphol-3-ene givesβ-carboxyvinyl(phenyl)phosphinic acid, and on alcoholysis it givesβ-ethoxycarbonylvmyl(phenyl)phosphinic acid. 4. The treatment of ethylβ-ethoxycarbonylvinyl(phenyl)phosphinate with phosphorus pentachloride givesβ-ethoxyearbonylvinyl(phenyl)phosphinic chloride.

1. It has been shown that, in presence of alkali-metal alkoxides, dialkylphosphorous acids readily add to maleic acid and to maleic and fumaric esters. The addition products, have been obtained ,in good. yield (dialk-oxyphosphinylsuccinic acids and their eskers). 2. It As been shown that under the same conditions, dialkylphosphorous acids add to diethyl acetylenedicarboxylate, and the products formed by addition of two molecules of dialkylphosphorous acid [bis(dialkoxyphos-phinyl)succinic esters] have been isolated.

1. Addition of diethylthiophosphorous acid to men of acrylic, methacrylic, cinnamic and maleic acids gave high yields of esters of dialkylthiophosphonopropionic, dialkylthiophosphonoisobutyric, dialkylthiophosphonophenylproplonic and dialkylthlophosphonosuccinic acids. 2. Addition was effected of esters of ethyl- and phenylphosphorous acids to esters of crotonic, cinnamic and maleic acids. 3. Addition of dialkylphosphorous acids, of ethylethylphosphonite and of ethyl diethlthiophosphorite to esters of phenylpropiolic and acetylenedicarboxylic acids gave esters of dialkylphosphono- and dialkylthiophosphono- cinnamic acid, esters of di-(dialkylphosphono)- and di-(diethylthiophmphono)- phenylpropionic acid and esters of di-(diethyl-thiophosphono)-succinic acid.

1. Diethyl esters of certain substituted benzoylphosphonic acids and diethyl(diphenyl)benzoylphosphine oxides were synthesized, and their dipole moments were determined. 2. The steric structure of the investigated compounds was established. 3. Interaction of the substituents in the benzene ring of diethyl esters of benzoylphosphonic acids with the diethoxyphosphono group was detected.

1. The counter synthesis of 5-methyl-2-ethyl-4-chloro-2-oxo-l,2-oxa-4-phospholene was accomplished. 2. The 4-methyl-2-ethyl- and 4-methyl-2-phenyl-5-methylene-2-oxo-1,2-oxa-3-phospholenes were obtained by the chlorination and dehydrochlorination of the 4,5-dimethy1-2-ethyl- and 4,5-dimethy1-2-pheny1-2-oxo-1,2-oxa-4-phospholenes. 3. The 4-methyl-2-ethyl (or phenyl)-5-methylene-2-oxo-1,2-oxa-3-phospolenes when treated with water or alcohols are converted to the corresponding phosphorylatedα,β-unsaturated ketones.

1. The kinetics of the alkaline and neutral aqueous hydrolysis of a number of phosphinic esters was investigated, and the rate constants and parameters of the Arrhenius equation were determined. 2. The rate constants of the reactions with water and the OH− ion are correlated with the sum of Taft σ* constants, as well as with the sum of the Kabachnik constants τf for the substituents at the phosphorus. 3. The secondary butyl ester of bis(chloromethyl)phosphinic acid has an unusually high rate of hydrolysis in the reaction with ester, which is explained by the SN1 mechanism for this ester.

1. The kinetics of neutral aqueous hydrolysis of a number of dialkyl phosphites and monoethyl phosphite was studied. 2. The rate constants decrease with increasing size and branching of the alkyl radicals. Di (tert-butyl) phosphite has an unusually high rate of hydrolysis, which is explained by its decomposition according to an SN1 mechanism. For other unsubstituted dialkyl phosphites, monomolecular heterolysis of a P-O bond is probable. 3. The rate constants of unsubstituted dialkyl phosphites are correlated with the sum of the Taft induction constants for alkyl radicals.

The application of DTA with the simultaneous recording of electrical conductivity variation in the study of the thermal behaviour ofα-oxyalkylphosphonates and their analogues is considered. The investigation of electrical conductivity variation during a reaction helps clarify certain problems of the phosphonate-phosphate rearrangement and the decomposition ofα-oxyalkylphosphonates to their components.

1. A simple and convenient method was found for obtaining the mixed anhydrides of alkylmethylphosphonic (thiophosphonic) and amidophosphorous acids by the reaction of alkylmethylphosphonic (thiophosphonic) acids with amidophosphites. The reactions proceed with the liberation of diethylamine and the formation of mixed anhydrides in 70–85% yield. The alkylmethylthiophosphonic acids react in the thiono form. 2. A study was made of some of the properties of the obtained mixed anhydrides. They are hydro-lyzed by water with the formation of the diethylammonium salt of phosphorous acid, and they add sulfur with the evolution of heat, forming pyrophosphonato thiophosphates.

1. The addition of trialkyl phosphites toα,β-unsaturated acids can proceed via the prior protonization of the trialkyl phosphites by the unsaturated acid. The dialkylphosphorous acids and unsaturated acid esters that are formed here react with each other to give the trialkyl esters of the correspondingβ-phosphonocarboxylic acids. 2. Not excluded is the possibility that the above indicated reaction can also proceed simultaneously by the mechanism proposed by Kukhtin and Kamai, but without the formation of the cyclic phosphorane as the intermediate step. 3. Together with the trimethyl ester ofβ-phosphonopropionic acid, the cyclic anhydride of the methyl ester ofβ-phosphonopropionic acid is formed when trimethyl phosphite is reacted with acrylic acid. The cyclic anhydride is obtained in much larger amounts in the presence of acetic acid. The corresponding cyclic anhydride was isolated in the same manner when triethyl phosphite was reacted with methacrylic acid.

1. The reaction of methyl 2,2,2-trichloro-1,1-dimethylethyl phosphorochloridite with acrylic acid goes with elimination of methyl chloride and formation of 2-(2,2,2-trichloro-1,1-dimethylethoxy)-1,2-oxaphospholan-5-one-2-oxide. 2. The reactions of bis(2,2,2-trichloro-1,1-dimethylethyl) and phenyl 2,2,2-trichloro-1,1-dimethylethyl phosphorochloridites with acrylic acid go with the formation of the corresponding esters of 3-phosphonopropionyl chloride. 3. In the reaction of 2,2,2-trichloro-1,1-dimethylethyl phosphorodichloridite with acrylic acid 3-chloropropionyl chloride and 3-[chloro(2,2,2-trichloro-1,1-dimethylethoxy)phosphinyl]propionyl chloride. are formed.

1. Dialkylphosphorous acids add on to methacrylamide, to give dialkylphosphoneisobutyramides. 2. The products of addition of higher dialkylphosphorous acids to methyl methacrylate, and of diethylphosphorous acid to alkyl methacrylates are described.

1. The reaction of the acid chlorides of ethyl-(β-carbethoxyalkyl)- and ethyl-(β-cyanoalkyl)phosphinic acids with phosphorus pentasulfide gave the acid chlorides of ethyl-(β-carbethoxyalkyl)- and ethyl-(β-cyanoalkyl) thiophosphinic acids. 2. The acid chlorides of ethyl-(β-carbethoxyalkyl)thiophosphinic acids when reacted with phosphorus pentachloride are converted to the acid chlorides of ethyl-(β-carbethoxyalkylene)thiophosphinic acids. 3. The acid chlorides of ethyl-(β-carbethoxyalkyl)- and ethyl-(β-cyanoalkyl)thiophosphinic acids when heated with triphenylphosphine are reduced to give ethyl-(β-carbethoxyalkyl)- and ethyl-(β-cyano-alkyl) chlorophosphines.

1. A simple and convenient method was found for the synthesis of the ester-amides of sub(thio)-phosphoric acid as the result of reacting dialkyl(thio)phosphoric acids with amidophosphites. It was proved that this reaction is reversible. 2. A simple and convenient method was found for the synthesis of the ester-amides of thio- and dithiopyrophosphoric acids by the reaction of dialkyl(thio)phosphoric acids with amidophosphites and sulfur.

A new method has been developed for the synthesis of amino phosphonics acids. It consists in the addition.of dialkylphosphorous acids to anils in presence of alkali-metal alkoxides.

1. Ethyldichlorophosphine reacts with acrylic acid esters via initial nucleophilic attack of theβ-carbon atom of the unsaturated ester by the tricoordinated phosphorus atom. 2. When the reaction is run in the presence of acetic acid the main reaction products are the ethyl-(β-carbalkoxyethyl) phosphinyl chlorides.

1. The reactions of methyl-, ethyl-, and phenyldichlorophosphine with cis-β-chloroacrylic acid lead to the formation of the acid chlorides of methyl-, ethyl-, and phenyl-(β-chloroformylvinyl)phosphinic acid. 2. With trans-β-chloroacrylic acid the reaction proceeds with the formation of the acid chloride of trans-β-chloroacrylic acid.

1. The methyl, ethyl, isopropyl, isobutyl, hexyl, heptyl, octyl, and nonyl partial esters of phenylphosphonous acid have been synthesized. 2. It has been shown that, in presence of alkali-metal alkoxides, partial esters of phenylphosphonous and alkylphosphonous acids readily add on to methacrylic and acrylic esters. 3. Various esters of (2-alkoxycarbonylethyl)phenyl-, (2 alkoxycarbonylethyl)ethyl-, (2-alkoxycarbonylpropyl)phenyl-, and (2-alkoxycarbonylpropyl)ethyl-phosphinic acids have been synthesized.

1. The corresponding adducts of the diene synthesis reaction were obtained as the result of the reaction of 2-ethyl-2,5-dioxo-1,2-oxa-3-phospholene and 3-methyl-2-ethyl-2,5-dioxo-1,2-oxa-3-phospholene with 2,3-dimethyl-1,3-butadiene. 2. The alcoholysis of 5,6-dimethyl-1-ethyl-1,3-dioxo-2-oxa-1-phosphabicyclo[3,0,4]-5,6-nonene proceeds contrary to the Pearson rule, with the alcohol attacking the carbon of the carbonyl group.

1. The dipole moments of the diethyl- and diphenylcyanomethylphosphine oxides were determined, and from them was found the ratio of the conformers. 2. The relative stability of the conformers is determined by electrostatic interactions.

1. The crude products of the reactions of ethyl and 1,3-dichloropropylethylphosphonochloridites with acrylic acid are the corresponding ethyl and 1,3-dichloroisopropyl (β-chlorocarbonylethyl)ethylphosphinates. On distillation, they lose the corresponding alkyl chlorides and are converted into one and the same 4-oxo-4-hydroxy-4-phosphacaproic acid anhydride. 2. The reaction of diethyl phosphorochloridite with methacrylic acid has given 2-methyl-4-oxo-4-hydroxy-5-oxa-4-phosphaenanthic acid anhydride.

Anilides of dialkylphosphorous acids react with p-nitrobenzaldehyde to form O,O-dialkyl-O-p-nitrobenzyl-N-phenylimidophosphates.

The reaction of neutral phosphites with acrylic acid N-arylamides took place with participation of the carbamide group and led to the formation of dialkyl esters of N,N-alkylarylcarbamoylethyl phosphonic acid.

The reaction of alkyl ethylphosphonochloridites and arylphosphonochloridites with acrylamide and methacrylamide forms esters of ethyl-and aryl-β-cyanoalkylphosphmic acids.

1. The reaction of primary amines and the acid chloride of phenyl-β-chloroformylethylphosphonic acid yields N-substituted 2-phenyl-2, 5-dioxo-1, 2-azaphospholanes. 2. Hydrolysis of N-substituted 2-phenyl-2, 5-dioxo-1, 2-azaphospholanes yields phenyl-β-(N-substituted-carbamoylethyl)phosphonic acids and alcoholysis yields the esters of these acids.

1. Methyldichlorophosphine reacts withα-crotonic acid and gives methyl-(β-chIoroformylisopropyl) phosphinic acid chloride. 2. The hydrolysis of methyl-(β-chloroformylisopropyl)phosphinic acid chloride gives methyl-(β-carboxyisopropyl)phosphinic acid, the alcoholysis gives the complete ester of this acid; its reaction with acetic anhydride leads to the formation of 2,3-dimethyl-2, 5-dioxo-1, 2-oxaphospholane. 3. The reaction of 2, 3-dimethyl-2, 5-dioxo-1, 2-oxaphospholane with ethanol gives the ethyl ester of methyl-(β-carboxyisopropyl)phosphinic acid, the reaction with aniline gives methyl-(β-phenyl-carbamoyl-isopropyl)phosphinic acid. 4. The ethyl ester of methyl-(β-carbethoxyisopropyl)phosphinic acid with PCl5 gives methyl-(β-carbethoxyisopropyl)phosphinic acid chloride.

1. Treatment of the products of the reaction of ethyl- (or aryl)alkoxychlorophosphines and propiolic acid with alcohol or butyl mercaptan yielded the corresponding esters of ethyl- (or aryl)(β-carbethoxyvinyl) phosphinic or ethyl- (or phenyl)(β-carbobutylthiovinyl)phosphinic acids. 2. The adduct of phenyltert-(1,1,1-trichloro)butoxychlorophosphine and propiolic acid underwent transformation to 2-phenyl-2,5-dioxo-1,2-oxaphosphol-3-ene during distillation.

1. The following compounds are formed by the reaction of methyl dichlorophosphine with acrylamide: methyl-β-cyanoethylphosphonyl chloride (36.6%),β-chloropropionitrile (16.2%) and methyl-β-cyanoettylphosphonic acid (3.4%). 2. The reaction of methyl-β-cyanoethylphosphonyl chloride with water (2∶1) gave methyl-β-cyanoethylphosphonic acid anhydride. 3. By reacting methyl-β-cyanoethylphosphonyl chloride with alcohols and diethylamine, we have obtained a number of esters and the diethylamide of methyl-β-cyanoethylphosphonic acid.