The method of obtaining di-(-chloroethyl)vinylphosphonate


(57) Abstract:

The invention relates to the chemistry of organophosphorus compounds, specifically to methods for di (chloroethyl)vinylphosphonate (Vinnitsa) by dehydrochlorination di (chloroethyl)- -chloroethylphosphonic (isomerate) in the presence of a nucleophilic reagent by heating. The purpose of the invention is the simplification of the existing method, improved manufacturability. This is accomplished by using in the synthesis of Vinitsa as a nucleophilic reagent anhydrous sodium carbonate in a molar ratio of isomerizate:Na2CO3=1:1.1 to 1.4. The reaction dehydrochlorinating carried out at 115-125oC for 5-7 h 1 table.

The invention relates to the chemistry of organophosphorus compounds, specifically to methods for di (chloroethyl)-vinylphosphonate structural formula:

< / BR>
shows the properties of a reactive monomer flame retardant, known as the "vinito".

Ways of getting Vinitsa based on the dehydrochlorination di (chloroethyl)(b-chloroethylphosphonic (isomerate) in the presence of various nucleophilic reagents [1-4] In most cases as nucleophilic reagents used carbonates or bicarbonates society nucleophilic reagent may use aqueous solutions of KOH or NaOH [4] Reaction dihydrochloride was carried out at 25-225oC, usually in the presence of catalysts AcCOOH, PhCOOH, dialkylphosphate, salts of organic acids. Often for the method of obtaining Vinitsa using solvent either in the synthesis or for washing; the reaction is carried out in the stream of nitrogen.

Closest to the claimed is a method of obtaining Vinitsa, in which [5] as a nucleophilic reagent used carbonate or sodium bicarbonate in a molar ratio of isomerizate:sodium bicarbonate 1:about 0.6-0.7. As catalysts for use phenols or organic acids, the reaction is carried out in the presence of a solvent [5] this method of obtaining Vinitsa is difficult to implement, catalysts, solvent requires washing and additional purification of the final product.

The aim of the invention is to simplify the way, improving its maintainability.

The objective is achieved by the fact that, as the nucleophilic reagent used is anhydrous sodium carbonate (soda ash) in a molar ratio of isomerizate:sodium carbonate is 1:1.2 to 1.4 and reaction are 5-7 PM

The reaction equation:

< / BR>
The synthesis is carried out at a temperature of 115-125oC. Dry soda ash load when razmeshenie; mode mixing turbulent, the Reynolds criterion centrifugal Rey50. After exposure of the reaction mass is distilled water at 10-30 mm RT.article and 90-100oC for 1 h After cooling to 25-30oC the mass is filtered at POST=20-30 mm RT. Art. from the precipitate salts. The finished product is a colorless mobile liquid, soluble in water and common organic solvents: alcohol, benzene, acetone, chloroform. The structure and personality of the obtained compounds were confirmed by elemental analysis, titration to the double bond using a acetate mercury and using IR spectroscopy.

Using the proposed method allows us to simplify the process of obtaining Vinitsa by eliminating the use of catalyst and solvent, which in turn allows us to simplify the selection of the target product, which does not require additional purification.

The decrease in the molar ratio of sodium carbonate to the isomerized product below 1.1 and the reaction time less than 5 hours leads to lower output <90% Increase in same molar ratio above 1.4 and reaction time more than 7 hours leads to resinification of the target product with a color change to 10 Hazen units.

Example 1. In Chernogo isomerate then, while stirring 46,5 g (0,439 mole) of dry soda ash. Raise the temperature to 120oC and incubated the reaction mass with stirring and this temperature for 5 hours Mode of turbulent mixing (Rey50). After the exposure temperature is reduced to 110-115oC, stirring off and distilled from the reaction mass of water at 20-30 mm RT.article within 1 h after cooling to 25-30oC mass filter for P leave 20 mm RT.article on a glass filter from SCHOTT precipitate salts. The finished product is a colorless mobile liquid. The product yield in the synthesis 108,5, the Content of Vinitsa on the results of the titration on the double bond using acetate of mercury in terms of winits of 76.5 wt. The output in terms of isomerizate is 99%


Found, P 12,94.

Calculated P 13,30.



IR spectrum (cm-1):

The color scale Hazen, Hazen units: 1.

Examples 2-7. The process is conducted analogously to example 1, by changing the ratio of reagents and time of the reaction. The completeness of the reaction was determined by the residual isomerate in the reaction mass chromatogr amosorb WHP", stationary phase methanesiliconic elastomer brand E-301. Identification of the final product was carried out by gas chromatography-infrared spectroscopy on the complex, including a gas chromatograph Perkin-Elmer 8700 and IR-spectrometer with Fourier transform "Perkin-Elmer 1720X".

The results are presented in the table.

The resulting winits can be used as a feedstock in the synthesis of oligomeric products intended for use as components of various polymers.

The sources of information.

1. Di b-chlorotalonil ether vinylphosphonic acid. Gefter B. L. P. Moshkin A. Zhuravlev S. S. getter chem. chemicals", Vol. 18. M. Chemistry, 1969, S. 108-11.

2. U.S. patent N 3584040, class C 07 F 9/38, publ. 15.12.70.

3. About how to obtain bis -(b-chloroethyl)vinylphosphonate. Abramov I. A. Balyasnikov I.e. Gefter E. L. Zhuravleva HP Raev E. F. I. Rogachev A. - Journal of applied chemistry, 1974, 47, N 3, 676-677.

4. Japan's bid N 52-31853, class C 07 F 9/40, publ. 17.08.77.

5. U.S. patent N 3694527, class C 07 F 9/40 publ. 26.09.72 (prototype).

The method of obtaining di-(chloroethyl)-vinylphosphonate the dehydrochlorination di-chloroethyl--chloroethylphosphonic at 115 125oIn the presence of anhydrous carb and di-chloroethyl--chloroethylphosphonic and sodium carbonate 1 1,1 1,4 within 5 to 7 PM


Same patents:

The invention relates to 2-sharonlee - 4,5,6,7 - tetrahydro-2-sharinaletisha-phosphonates and-Phosphinates, inhibiting enzymatic activity; to compositions containing these compounds, their use and the treatment of disruptive disorders, and to methods for their preparation

The invention relates to new derivatives methylenephosphonic acid of General formula I

< / BR>
in which R1, R2, R3and R4independently are C1-C10the alkyl straight or branched chain, optionally unsaturated, C3-C10-cycloalkyl, optionally unsaturated, aryl, aralkyl, silicom SiR3or hydrogen, in formula I, at least one of the groups R1, R2, R3and R4is hydrogen and at least one of the groups R1, R2, R3and R4different from hydrogen

The invention relates to a technology for obtaining esters vinylphosphonic acid, which finds wide use as a reactive flame retardants and plasticizers in the production of various polymer materials

The invention relates to the chemistry of phosphorus - organic compounds, and in particular to a new method of obtaining S-triphenylcarbinol esters of dealkylation and tetrathiofulvalene acids of General formula (I)

(RX)SGePh3where R is lower alkyl; X Is 0, S

The invention relates to new phosphorylated to Surinam General formula


(I) where R is a saturated or unsaturated aliphatic hydrocarbon residue with a straight or branched chain, containing 6-30 carbon atoms which may be substituted with halogen, -OR, - SR1or-NR1R2group, where R1and R2lowest alkali

The invention relates to organic chemistry and can be used to obtain phosphonates, which can be used to reduce the Flammability of polymer materials

FIELD: organic chemistry, in particular improved method for production of phosphorinated and chlorinated methacrylates.

SUBSTANCE: invention relates to method for production of compounds having general formula , wherein R is lower alkyl and R1 is lower alkoxyl, phenoxyl, or group of formula . Claimed method includes reaction of pentavalent phosphorous acid chloroanhydride with glycydil methacrylate at 20-50°C in presence of titanium tetrachloride as catalyst in amount of 0.02-0.05 % calculated as reagent mass.

EFFECT: one-step method for production of phosphorous and chlorine containing methacrylates with improved water resistance.

2 tbl, 7 ex

FIELD: chemistry of organophosphorus compounds.

SUBSTANCE: invention relates to compounds with the bond C-P, namely to phosphorus-boron-containing methacrylate that can be used as inhibitor of combustion of polyvinyl alcohol-base film materials. Invention describes phosphorus-boron-containing methacrylate of the following formula: wherein n = 4-8. Polyvinyl alcohol films modified with indicated phosphorus-boron-containing methacrylate shows the enhanced refractoriness, rupture strength up to 206 kgf/cm2, water absorption up to 240% and relative elongation up to 12%.

EFFECT: valuable properties of substance.

1 tbl, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing N-phosphonomethylglycine. Method involves interaction of derivative of hexahydrotriazine of the formula (II):

wherein X represents CN, COOZ, CH2OY and others; Z and Y represent hydrogen atom and others with triacylphosphite of the formula: P(OCOR3)3 (III) wherein R3 means (C1-C18)-alkyl or aryl that can be substituted. The prepared product is hydrolyzed and (if X represents CH2OY) oxidized. The proposed method is a simple in realization, economy and provides high degree of the end product purity.

EFFECT: improved preparing method.

19 cl, 11 ex

FIELD: organic chemistry, chemical technology, medicine.

SUBSTANCE: invention relates to acyclic nucleoside phosphonate derivatives of the formula (1): wherein means a simple or double bond; R1 means hydrogen atom; R2 and R3 mean hydrogen atom or (C1-C7)-alkyl; R7 and R8 mean hydrogen atom or (C1-C4)-alkyl; R4 and R5 mean hydrogen atom or (C1-C4)-alkyl possibly substituted with one or more halogen atoms, or -(CH2)m-OC(=O)-R6 wherein m means a whole number from 1 to 5; R6 means (C1-C7)-alkyl or 3-6-membered heterocycle comprising 1 or 2 heteroatoms taken among the group consisting of nitrogen (N) and oxygen (O) atoms; Y means -O-, -CH(Z)-, =C(Z)-, -N(Z)- wherein Z means hydrogen atom, hydroxy-group or halogen atom, or (C1-C7)-alkyl; Q (see the claim invention); its pharmaceutically acceptable salts or stereoisomers. Also, invention proposes methods for preparing compounds of the formula (1) and their using in treatment of hepatitis B or preparing a medicinal agent designated for this aim.

EFFECT: improved preparing method, valuable medicinal properties of compounds and agent.

16 cl, 10 tbl, 87 ex

FIELD: chemistry of organophosphorus compounds.

SUBSTANCE: invention relates to the improved method for synthesis phosphorus-chlorine-containing methacrylates that can be used in synthesis of polymeric, among them, uncolored, optically transparent and composition materials with reduced inflammability. Invention describes a method for synthesis of phosphorus-chlorine-containing methacrylates of the general formula:

wherein R means lower alkyl, chloroalkyl, alkoxyl, phenoxyl or group of the formula:

R1 means lower alkoxyl, phenoxyl or group of the formula:

Method involves interaction of phosphoric pentavalent acid chloroanhydrides with methacrylic acid glycidyl ester at heating in the presence of hexamethylenephosphorotriamide or dimethylformamide as a catalyst wherein catalyst is taken in the amount 0.3-0.6% of reagents mass, and process is carried out at rise of temperature from 40°C to 80°C in the presence of compound chosen from the group: alkyl- or alkoxy-substituted phenols taken in the amount 0.03-0.3% of reagents mass. Method provides decreasing water absorption of (co)polymerization products of synthesized phosphorus-chlorine-containing methacrylates and reducing retention time of surface stickiness of fiber glass synthesized on their basis and at retention the level of other properties, among them transparence and colorless.

EFFECT: improved method of synthesis, improved and valuable properties of compounds.

2 tbl, 10 ex

FIELD: organic chemistry, biochemistry, medicine.

SUBSTANCE: invention relates to phosphonic acid compounds used as inhibitors of serine proteinase of the general formula (I): wherein R1 is chosen from group comprising piperidinyl, pyrrolidinyl and 1,3,8-triazaspiro[4,5]dec-8-yl (wherein heterocyclic ring as added to nitrogen atom in ring) and -N(R7R80 wherein this heterocyclic ring is substituted optionally with one or two substitutes chosen independently from group comprising the following compounds: (a) C1-C8)-alkyl substituted optionally at terminal carbon atom with a substitute chosen from group comprising aryl, heteroaryl; c) phenyl and naphthalenyl; i) benzothiazolyl; R7 is chosen from group comprising hydrogen atom and (C1-C8)-alkyl; R8 is chosen from group comprising: (aa) (C1-C8)-alkyl; (ab) cycloalkyl; (ac) cycloalkenyl, and (ad) heterocyclyl (wherein R8 is added to carbon atom in ring) wherein (ab) cycloalkyl; (ac) cycloalkenyl, and (ad) heterocyclyl (wherein heterocyclyl (ad) comprises at least one cyclic nitrogen atom) substitutes and cycloalkyl moiety (aa) of a substitute is substituted optionally with substitutes chosen independently from group comprising: (ba) (C1-C8)-alkyl substituted at terminal carbon atom with a substitute chosen from group comprising amino-group (with two substitutes chosen independently from group comprising hydrogen atom and (C1-C8)-alkyl); (bb) (C1-C8)-alkoxy-group substituted at terminal carbon atom with a substitute chosen from group comprising carboxyl; (bc) carbonyl substituted with a substitute chosen from group comprising (C1-C8)-alkyl, aryl, aryl-(C2-C8)-alkenyl; (bd) aryl; (be) heteroaryl; (bf) amino-group substituted with two substitutes chosen independently from group comprising hydrogen atom and (C1-C8)-alkyl; (bh) halogen atom; (bi) hydroxy-group; (bk) heterocyclyl wherein (bd) is aryl substitute, and heteroaryl moiety (bc) comprise a substitute (halogen atom)1-3; R4 is chosen from group comprising aryl and heteroaryl wherein heteroaryl comprises halogen atom as a substitute; R2 and R3 are bound with benzene ring and represent hydrogen atom, and R2 and R3 form in common optionally at least one ring condensed with benzene ring forming polycyclic system wherein this polycyclic system is chosen from group comprising (C9-C14)-benzocondensed cycloalkenyl, (C9-C14)-benzocondensed phenyl; R5 is chosen from group comprising hydrogen atom and (C1-C8)-alkyl; R6 is chosen from group comprising (C1-C8)-alkyl and hydroxy-group; Y is absent, and X represents a single substitute that is added by a double bond and represents oxygen atom (O), and Z is chosen from group comprising a bond, hydrogen atom, and its salts. Also, invention relates to a method for synthesis of these compounds, to their composition inhibiting serine proteinase and to a method for its preparing. Proposed invention describes a method for treatment of inflammatory or serine proteinase-mediated disorder.

EFFECT: valuable biochemical and medicinal properties of compounds.

64 cl, 5 tbl, 38 ex

FIELD: organic chemistry, medicine, biochemistry.

SUBSTANCE: invention describes compound of the formula (I): wherein R1 means hydrogen atom (H); R2 means -SH, -S-C(O)-R8, -P(O)(OR5)2, -P(O)(OR5)R6, -P(O)(OR5)-R7-C(O)-R8, -P(O)(OR5)-R7-N(R5)-S(O)2-R9 or -P(O)(OR5)-R7-N(R5)-C(S)-N(R6)2; R3 means tetrazole, -C(O)OR6, -C(O)O-R7-OC(O)R5; R4 means optionally substituted aryl, or R4 means N-heterocyclyl. Also, invention describes compounds of the formula (II): and (III): wherein X means -CH2- or -O-, and pharmaceutical compositions comprising indicated compounds. Proposed compounds possess inhibitory effect on activity of plasma carboxypeptidase B and used as anti-thrombosis agents.

EFFECT: valuable medicinal and biochemical properties of compounds.

34 cl, 19 ex

FIELD: chemistry.

SUBSTANCE: invention concerns process of production of diisopropyl {[1-(hydroxymethyl)-cyclopropyl]oxy}methylphosphonate represented by the formula , which is the key intermediate compound in synthesis of antiviral nucleoside analogue. The invention also concerns new intermediate compounds of formulae and , and their production of compound (2) obtained under this invention, which is an antiviral nucleoside analogue (especially against hepatitis B virus) represented by the formula .

EFFECT: high purity grade and high output.

4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to protection of metals from corrosion using lacquer coating. This engineering problem can be solved by using calcium hydroxyethylidenediphosphonate with formula CH3(OH)C(PO3)2Ca2 as an anti-corrosion pigment, with higher anti-corrosion activity as compared to the prototype - protonated zinc hydroxyethylidenediphosphonate and a control specimen - zinc tetraoxychromate.

EFFECT: low-toxic high performance anti-corrosion pigment.

1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention refers to method of production of C-phosphorylated alkylamidines serving as parent compounds of biologically active compounds for medicine and agriculture, of formula: where R1=C3-C4alkyl or isoalkyl; R2=CH3, C6H5; R3=C2-C4-alkyl or isoalkyl; R4=H, CH3, C3H7, C6H5, COOC2H5. Method includes in production of sodium derivatives of C-phosphorylated alkylamidines resulted from reaction of C-phosphorylated acetamidine with sodium. Produced sodium derivative is alkylated with alkylhalogenide in dioxane medium at mole ratio sodium:C-phosphorylated acetamidine:alkylhalogenide (1:1:1÷1.1), respectvely at temperature 20÷50°C.

EFFECT: production of new C-phosphorylated alkylamidines with high yield exceeding 78%.

1 cl, 9 ex