Method for preparing complexes of 2-isopropoxy-2-methylvinyl trichlorophosphonium hexachlorometals

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for preparing complexes of 2-isopropoxy-2-methylvinyl trichlorophosphonium hexachlorometals of the general formula: [(I-PrO-C(CH3)=CHP+Cl3)nMCln-6] wherein M means Sn; n = 2; M means Sb or Bi; n = 3. Method involves interaction of diisopropyl ester with phosphorus pentachloride in the inert solvent medium followed by treatment of formed compound with tin, antimony of bismuth dichloride. Before treatment of formed compound with the corresponding anhydrous metal dichloride nitromethane as a polar solvent is added to its in the amount 1.1-1.25 mole per 1 mole of phosphorus pentachloride, and mixture is heated to temperature above 55°C up to formation of the end product. Method provides increasing yield of the end product.

EFFECT: improved preparing method.

3 ex

 

The invention relates to the chemistry of organophosphorus compounds with carbon-phosphorus bond, namely complexes containing 2-isopropoxy-2-methylphenyl-1-trichlorophenate and hexachlorethane anions of General formula

where M=Sn, n=2; M=Sb or Bi, n=3,

which can find application as catalysts for polymerization processes, the starting compounds to obtain phosphorofluoridic monomers, oligomers, polymers, etc.

A method of obtaining complex compounds of trichloride aluminum and trichloride phosphorus halide with alkilani [Durdel, Rwilco. Chemistry of organic compounds of phosphorus. M., "Chemistry", 1972, s, 271, 379].

The structure of these complexes with trichloride aluminum in many cases not fully elucidated [Aheneghana. The chemistry of organophosphorus compounds. MSU. 1971, s; van Weser. Phosphorus and its compounds. M., "IL", 1962, p.189-192], and a similar reaction with chlorides of tin, antimony and bismuth are not described.

The closest in technical essence and the achieved result is a method of obtaining complexes of 2-isopropoxy-2-methylphenyldichlorosilane (1), including the interaction of diisopropyl ether with pentachloride phosphorus obtaining a complex of (A)

adding to the resulting set is SIC nonpolar organic solvent (benzene, carbon tetrachloride) dichloride and tin, or antimony, or bismuth with formation of a mixture of different compounds, which significantly reduces the yield of the target compound [Lowbrow, Arm, Affidare. Abstracts of all-Union conference "Chemistry of unsaturated compounds". Kazan, 1986, 1, s - prototype].

However, the use of non-polar organic solvent after receiving complex And leads to the formation of mixtures of different products, thus reducing the yield obtained of the target property.

The compositional process of the prototype represented by the following scheme:

The reaction product of pentachloride phosphorus with diisopropyl ether interacts with antimony, bismuth and tin dichloride with education niewyk compounds - POLYHALOGENATED metals with 2-isopropoxyphenyl-1 trichloroethane (I, II, VI), and 2-isopropoxyphenyl-1 chlorophonia (III, IV) and 2-isopropoxyphenyl-1 dichlorophosphino (V) in the case of bismuth and antimony.

The claimed invention is directed to an improvement of the method and increase the yield of the target product.

This is achieved by a method of producing complexes of 2-isopropoxy-2-methylphenyldichlorosilane General formula

[(i-Pr-O-(CH3)CHP+Cl3)nMCl6n]

where M=Sn, n=2; M=Sb or Bi, n=3,

in the interaction with diisopropyl ether with pentachloride phosphorus in an inert solvent followed by treatment of the compounds formed by the dichloride tin or antimony, or bismuth, before processing the compounds formed anhydrous dichloride suitable metal to it add the polar alwatany solvent is nitromethane in the amount of 1.1-1.25 mol per 1 mol petaluridae phosphorus and the mixture is heated to a temperature not exceeding 55°before the formation of the target product

The formation of complexes of the structure of 2-isopropoxy-2-methylvinyl of trichlorovinylsilane tin, antimony and bismuth previously studied processes is not obvious

The use according to the invention as a co-solvent silnopologo connection - nitromethane, unlike the prototype, leads to the restoration of the complex And extremely hexachlorostannate anion, without affecting arginyltransferase cation.

The mechanism of such influence nitromethane requires special studies, however, we can assume a stabilizing effect on his arginyltransferase cation due to donor-acceptor interaction.

The use of nitromethane allows the reaction without side processes with increased yield of the target product.

Heated to 55°enough to produce the maximum yield of the target product, at a lower temperature formation of the target product is also happening, but slowly, which lengthens the process.

Nitromethane, personalit is camping in the reaction system of calculation from 1.1 to 1.25 mol per 1 mol petaluridae phosphorus. The use of large quantities of nitromethane did not affect the yield of the final product.

The method is illustrated by the following examples.

Example 1. Obtaining bis-(2-isopropoxy-2-methylvinyl-trichlorophenyl)-hexachlorophene. To the dispersion 125,2 g (0.6 mol) of pentachloride phosphorus in 100 ml of carbon tetrachloride was added 20.4 g (0.2 mol) diisopropyl ether, stirred for 12 h at room temperature and 4 hours at 50°s to stop shedding chloride and education complex (A). After cooling the reaction mass to room temperature, add 35 ml (0.66 mol) of nitromethane, and then of 37.9 g (0.2 mol) of tin dichloride and heated to a temperature of 20°until the complete disappearance of the complex A. the Process ends with the formation of two-layer liquid mixture. The bottom layer is separated, cooled to 0-5°for precipitation of crystals, which are filtered off and recrystallized from nitromethane. The yield of the target product 76 g (86%).

The IR spectrum of the obtained compound provides the characteristic absorption bands in the regions 1570 cm-1(C=C), 1190-1170 cm-1(C-O-C), 552-526 cm-1(P-Cl).

An NMR spectrum1N has a resonance signals: doublet with δ=1,13 ppm and septet with δ=4,7 ppm and coupling constants3JNN=6,0 Hz [(CH3(CH3)CH)]; doublet δ=2,1 ppm4JHp=3,6 Hz (CH3-C=C-R); doublet δ=5,3 ppm3JHP=44,7 Hz (=CH-R). Chemical shift δ31R is 83 ppm relative to 95% N3PO4(Methods AMDR1N-[31P] and NMR31P.

The formula is:

Example 2. Obtaining Tris (2-isopropoxy-2-methylphenyl-1-trichloroethane) hexachlorophene. Same as described above in example 1 to the obtained product And 125,2 g (0.6 mol) PC I5(0.2 mol) diisopropyl ether add 40 ml (0.75 mol) of nitromethane, then 16.2 g (0.133 mol) of powdered antimony, heated to 40°until the complete disappearance of the complex And separate the bottom layer and distilled volatile compounds (CCl4, PCl3CH3, NO2).

The target product is released in the form of a thick oil output and 63.3 g (91% of theoretical amount).

IR-spectrum: 1555-1545 cm-1(C=C), 1200 cm-1(C-O-C), 550-525 cm-1(P-Cl). An NMR spectrum1N doublet with δ=1,15 ppm and septet with δ=4,8 M.D. and XW3JNN=6,0 Hz (CH3(CH3)CH); doublet δ=2,20 ppm and coupling constants4JHP=3.8 Hz (CH3)=S-R); doublet δ=of 5.53 ppm and2JHP.=44,8 Hz (=CH-R). The chemical shift of 84 ppm relative to 95% N3PO4. (AMDR1N-[31R] and NMR [31P]). The formula [(i-Pr-O-C(CH3)=CHP+Cl3)3SbCl63-].

Example 3. Obtaining Tris (2-isopropoxy-2-methylphenyl-1-trichlorophenyl)-hexachlorobuta. Similar is the rule described above in examples 1 and 2 to the product And, obtained from 125,2 g (0.6 mol) PCl5and of 20.4 g (0.2 mol) diisopropyl ether, add 40 ml of nitromethane, and then 27.9 g (0.133 mol) of powdered bismuth is heated to 40°until the complete disappearance of the complex A. the Target product is released in the form of a thick oil with a yield of 105.2 g (93% of theoretical amount).

IR-spectrum: 1555-1545 cm-1(OS), 1200 cm-1(C-O-C), 552-523 cm-1(P-Cl). An NMR spectrum1N: doublet with δ=1,12 ppm and septet with δ=4,8 ppm and coupling constants3JHH=6,0 Hz (CH3(CH3)CH), doublet δ=2,21 ppm and coupling constants4JHP=3,6 Hz (CH3)=S-R); doublet δ=5,58 ppm and coupling constants2JHP=45,8 Hz (=CH-C-R). The chemical shift is δ[31P]=84 ppm relative to 95% of phosphoric acid. (AMDR1N-[31R] and NMR [31P]).

Formula

Thus, the proposed method allows to obtain the target compound using the pattern

where R=i-Pr-O-(CH3)=CH-; M=Sb or Bi

with good outputs in mild conditions does not require complex hardware design.

The target compounds can be used in addition to those mentioned above, for various syntheses of derivatives of phosphorus, tin, antimony and bismuth different coordinate.

The method of obtaining complexes of 2-isopropoxy-2-methylin is trichloromonofluoromethane General formula

where M=Sn, n=2; M=Sb or Bi, n=3,

including interaction diisopropyl ether with pentachloride phosphorus in an inert solvent followed by treatment of the compounds formed by the dichloride tin, or antimony, or bismuth, wherein before processing the compounds formed anhydrous dichloride suitable metal to it add the polar aprotic solvent is nitromethane in the amount of 1.1-1.25 mol per 1 mol petaluridae phosphorus and the mixture is heated to a temperature not exceeding 55°before the formation of the target product.



 

Same patents:
The invention relates to an improved method for producing a water-soluble amino acid derivatives of fullerene that can be used in pharmacology and Microbiology

The invention relates to methods of producing salts of bismuth

The invention relates to salts formed by ranitidine and a complex of bismuth with a carboxylic acid, and the solvate of these salts
The invention relates to an improved method for producing a water-soluble amino acid derivatives of fullerene that can be used in pharmacology and Microbiology

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to new compounds of the general formula: {[R1]yKt}+-N(CF3)2 (I) representing stable salts used as precursors of organic compounds. In the formula (I) Kt means nitrogen atom (N), phosphorus atom (P); R1 means similar or different values and each means unsubstituted or substituted with phenyl (CnH2n+1)-alkyl, unsubstituted phenyl; groups bound with Kt can be similar or different and wherein n = 1-18; y = 4 with exception for (C2H5)4N+ -N(CF3)2. Also, invention relates to a method for preparing these compounds wherein compound of the formula: D+-N(CF3)2 (II) wherein D is taken among group including alkaline metals, or compound of the formula: GN(CF3)2 (IV) wherein G represents fluorinated sulfonamides are subjected for interaction with salt of the general formula: {[R1]yKt}+-E (III) in polar organic solvent and wherein -E means F-, Cl-, Br-, J-, BF-4, ClO-4, AsF-6, SbF-6 or PF-6.

EFFECT: improved method for preparing.

6 cl, 6 ex

The invention relates to a method for producing 1-phenyl-TRANS-3,4-dialkylphosphorous General formula

< / BR>
where R = n-C4H9the h6H13n-C8H17that is in interaction-olefins with atelecommunications and metallic magnesium in the presence of a catalyst Cp2ZrCl2in an argon atmosphere in the environment of the solvent for 8 h followed by the addition at a temperature of -15oWith CuCl as catalyst and phenyldichlorophosphine, followed by stirring the reaction mass for 8-12 h at room temperature

The invention relates to a method for producing salts retinylidene, which are intermediates in the production of-carotene and other carotenoids, and may find application in pharmaceutical industry

Ionic liquids ii // 2272043

FIELD: organic chemistry.

SUBSTANCE: invention relates to new ionic liquids designated for using in electrochemical cells and in organic synthesis. Invention describes ionic liquids of the general formula: K+A- (I) wherein K+ represents one of cations of the group consisting of the following formulae: wherein R1-R5 can be similar or different and can be bound to one another by a simple or double bond also, and each of them separately or in common can represent the following values: hydrogen atom (H), halogen atom, (C1-C8)-alkyl radical that can be partially or completely substituted with the following groups but preferably with fluorine atom (F), chlorine atom (Cl), N-[CnF(2n+1-x)Hx]2, O-[CnF(2n+1-x)Hx], SO2-[CnF(2n+1-x)Hx] or CnF(2n+1-x)Hx wherein 1 < n < 6 and 0 < x < 2n+1; A- means anion taken among the group consisting of [PFx(CyF(2y+1-z)Hz)6-x]- wherein 1 ≤ x ≤ 6, 1 ≤ y ≤ 8 and 0 ≤ z ≤ 2y+1. Invention provides the development of ionic liquids showing broad range of liquid state, high thermal resistance and low corrosive activity.

EFFECT: improved and valuable properties of ionic liquids.

3 ex

The invention relates to an improved process for the preparation of organometallosiloksanov General formula YAlk2SnOMnRmYn-m-1[where M is a metal selected from the group of CA, Zn, Cu, Al, Si, Ge, Sn, Ti, Fe, Mn, Co, Cr; Y=OR' (R'is alkyl 1 - 4C) or O2CR '(R" is alkyl, cycloalkyl with 6-11C); R is alkyl with 1 to 4C, vinyl, phenyl; n is the valence of the metal M, m=0-2, m-n1] by the interaction of dialkanolamides with alkoxides or acylate the above metals M

The invention relates to a method of extracting complex diesters distannoxane from reaction mixtures containing these compounds

The invention relates to the production of products based on rosin and ORGANOMETALLIC compounds and can be used in chemical, pulp and paper industry, health, agriculture, etc

The invention relates to a new method of obtaining previously unknown trialkylsilyl(2 trialkylamines-2-phenyl)acetates of the General formula C6H5CH[OSn(R13)] COOGe(R)3where R and R' is lower alkyl, which can be used as synthetic monomers to build biopolymer structures, and may be of interest for search pharmaceutical drugs with antitumor activity

The invention relates to the chemistry of organophosphorus compounds, namely to a new method of obtaining S-trialkylsilyl - ash and stanilova esters of 4-methoxyphenylacetic or triiodobenzoic acids of General formula I 4-MeOC6Hwhere R, R1is lower alkyl; E is Si, Sn; X Is O, S

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for preparing complexes of 2-isopropoxy-2-methylvinyl trichlorophosphonium hexachlorometals of the general formula: [(I-PrO-C(CH3)=CHP+Cl3)nMCln-6] wherein M means Sn; n = 2; M means Sb or Bi; n = 3. Method involves interaction of diisopropyl ester with phosphorus pentachloride in the inert solvent medium followed by treatment of formed compound with tin, antimony of bismuth dichloride. Before treatment of formed compound with the corresponding anhydrous metal dichloride nitromethane as a polar solvent is added to its in the amount 1.1-1.25 mole per 1 mole of phosphorus pentachloride, and mixture is heated to temperature above 55°C up to formation of the end product. Method provides increasing yield of the end product.

EFFECT: improved preparing method.

3 ex

Up!