Method for preparing monohydroperfluoroalkanes, bis-(perfluoroalkyl)phosphinates and perfluoroalkylphosphonates

FIELD: chemistry of organophosphorus compounds, chemical technology.

SUBSTANCE: invention describes a method for synthesis of monohydroperfluoroalkanes, bis-(perfluoroalkyl)phosphinates and perfluoroalkylphosphonates. Method involves treatment of at least one perfluoroalkylphosphorane with at least one base wherein base(s) are chosen from group consisting of alkali-earth metal hydroxides, metalloorganic compound in useful solvent or at least one organic base and an acid in useful reaction medium. Also, invention describes novel perfluoroalkylphosphonates and bis-(perfluoroalkyl)phosphinates, using novel perfluoroalkylphosphonates and bis-(perfluoroalyl)phosphinates as ionic liquids, catalysts of phase transfer or surfactants.

EFFECT: improved method of synthesis.

18 cl, 19 ex

 

The presented invention relates to a method of obtaining monohydroperoxide, bis(perfluoroalkyl)Phosphinates and perforaciones, which includes at least processing at least one of performancehistory at least one base in a suitable reaction medium.

Monohydroperoxide known for some time and have found wide application in various fields of, inter alia, as ozonobezopastny refrigerants (WO 01/40400, WO 01/23494, WO 01/23491, WO 99/36485, WO 98/08913)as detergents (WO 01/32323)as disinfectants in microelectronics (US 2001/0005637, US 6228775), fire extinguishers (WO 01/05468, Combust. Flame, 121, No. 3 (2000) SS-487, CN 1218702)as blowing agents for foams (US 6225365, WO 01/18098) and to obtain polymeric materials and as strong painkillers (Anesth. Play mode display (N.Y.), 79, №2 (1994), s-251, .Hudlicky et al., J. of Fluorine Chem., 59, №1 (1992), p.9-14).

Some of these monohydroperoxide, such as, for example, pentaborate, it is easy to obtain on an industrial scale with a ton outputs, obtaining is usually carried out by catalytic hydroperiodide chlorinated hydrocarbons (WO 01/77048, EP 1052235).

The disadvantage of the above method is, first, the risk associated with the use of fluoride at relatively high temperatures. In addition, the methods require special catalysts that get in front of a relatively complex about what Asami. The next drawback of these methods is that when receiving chlorinated hydrocarbons chlorine is used, which is environmentally hazardous, and additionally increases the cost of production. In the end, the known methods of obtaining Pentafluoroethane not suitable for the production of long-chain monohydroperoxide, such as, for example, 1-gidromonitornoyj.

In addition, some of the other ways in which receive pentaverate, using fluorinating agents, such as, for example, BrF3(R.A.Devis, J. Org. Chem. 32 (1967), page 3478), XeF2(JP 2000/119201), SF4(G.Siegemund, Liebigs Ann. Chem., 1979, page 1280, E.R.Bissell, J. of Organic Chem., 29, (1964), page 1591), SbF5(Ani and others, Izv. Acad. Nauk SSSR, Ser. Chem., 1972, page 983, Chem. Abstr. 77 (1972) 75296, Afernoon etc., J. Org. Chem., 17 (1981), page 2239, J. Org. Chem. USSR (Engl. Translation), 17 (1981), page 1999, US 2426172), MoF6(Ldest etc., J. General Chem., 53 (1983), page 103, J. Gen. Chem. USSR (Engl. translation), 53 (1983), page 85) and CoF3(US 6162955).

However, the above methods do not have industrial significance, and because the corresponding starting compound, and fluorinating agents is themselves are very expensive.

In contrast, we only know a few ways to get long chain of monohydroperoxide.

In accordance with the first method monohydroperoxide get the ay decarboxylation salts of perfluorinated carboxylic acids (J.D.LaZerte et al., J. Am. Chem. Soc, 75 (1953), page 4525; R.N.Haszeldine, J. Chem. Soc. 1953, page 1548) or the corresponding esters (Evermap, J.Org. Chem., 23, (1958) page 476) by treatment with a strong base, such as, for example, ethoxide sodium.

In accordance with another way monohydroperoxide obtained by processing perforated ketones having triptorelin group on the carbonyl carbon atom, aqueous alkali (Lowcalorie and others, Izv. Acad. Nauk SSSR, Ser. Chem., 1984, No. 5, pages 1114-1116, Chem. Abstr. 101 (1984) h). These methods also have disadvantages, which need the use of expensive raw materials and high temperatures.

In addition, 1-hydro-n-nonattribute obtained by recovery of performativity using different reducing agents, such as, for example, zinc dust in methanol (.Hudlicky et al., J. of Fluorine Chem., 59, №1 (1992), SS-14), sodium methoxide (J.L.Howell et al., J. of Fluorine Chem., 72, №1 (1995), SS-68), using hydrogen in the gas phase at high temperatures (EP 632001) and using complex thallium [TSR2(C2H4)N] (..Russel et al., Polyhedron 17, No. 7 (1998), SS-1043).

However, these methods also have the disadvantage that consists in using as the starting compound of performativity, which can be obtained only with the use of comparatively expensive methods.

The aim of the presented invention was the provision of a method suitable for simple and inexpensive obtain monohydroperoxide with good outputs. Monohydroperoxide preferably should be obtained with high purity. The next objective was to obtain the bis(perfluoroalkyl)Phosphinates and PerformancePoint.

This goal is achieved by using a method in accordance with the invention receipt of monohydroperoxide General formula CnHF2n+1where 1≤n≤8, preferably 1≤n≤4, bis(perfluoroalkyl)Phosphinates and perforaciones, which includes at least processing at least one of performancehistory at least one base in a suitable reaction medium.

In accordance with the invention, the obtaining of monohydroperoxide using the method in accordance with the invention can in each case is carried out using performancehistory or a mixture of two or more perftoruglerodov. Preferably only one performancehistory in each case engages in the method in accordance with the invention.

Performancehistory used in the method in accordance with the invention, can be obtained using conventional methods known to the average person skilled in the technical field.

Performancehistory preferably obtained by electrochemical fluorination suitable starting compounds, as described Vasemagi and others, Zhur. About. Chem., 55, №12 (1985), Stra the Itza 2716-2720; N.Ignatiev, J. of Fluorine Chem., 103 (2000), c.c.57-61 and WO 00/21969. Corresponding descriptions, therefore, included here as a reference and considered part of the description.

In the preferred embodiment of the method in accordance with the invention is applied, at least one performancehistory General formula I

in which 1≤n≤8, preferably 1≤n≤4, and m in each case is 1, 2 or 3.

Particularly preferably perftoruglerodov compounds chosen from the group which includes Deportes(pentafluoroethyl)fastran, Deportes(n-nonattributed)fastran, Deportes(n-heptafluoropropyl)fastran and triformis(n-nonattributed)fastran.

Processing performancetherefore connection(s) using the method in accordance with the invention preferably in each case carried out using only one base. But, of course, you can also use a mixture of two or more bases in the method in accordance with the invention. Appropriate bases can also be used in the form of a corresponding solvate, preferably in the form of the corresponding hydrates, or in the form of regular adducts, well known to the average person skilled in the technical field.

In the following preferred embodiment of the method in accordance with the invention when the floor is the situation of monohydroperoxide commonly used base (a), preferably inorganic base (b) or organic base (in). Inorganic base (b) is preferably chosen from the group comprising hydroxides of alkali metals and hydroxides of alkaline earth metals.

If the base (b) in the method in accordance with the invention uses a hydroxide of an alkali metal, it can preferably be selected from the group including lithium hydroxide, monohydrate of lithium hydroxide, sodium hydroxide and potassium hydroxide.

If the base (b) in the method in accordance with the invention uses a hydroxide of alkaline earth metal, it can preferably be selected from the group including barium hydroxide, octahydrate barium hydroxide and calcium hydroxide.

The method of receiving monohydroperoxide in accordance with the invention also preferably can be made using organic base (in) or organo-metallic compound. Base (b) preferably can be selected from the group comprising hydroxides of alkylamine, hydroxides of arylamine, hydroxides of alkylsilane, hydroxides alkylphosphine, hydroxides arylphosphine, hydroxides alkylarylsulfonate, bonds alkylamines, arylamines, alkylsilane, alkylphosphine, arylphosphine and alkylarylphosphites.

The preferred organo-metallic compound can be selected from groups including the cabbage soup alkoxides of metals, preferably alkoxides of alkali metals, aryloxides metals, alkylthiomethyl metals, arylthiols metals, alkylbetaine connection arylmethylidene compounds and Grignard reagents.

If one of the above classes of bases contains alkyl radical, it may preferably contain from 1 to 4 carbon atoms. If the corresponding base contains two or more alkyl radical, they may in each case be identical or different, are the same alkyl radicals are preferred.

If one of the above classes of bases contains aryl radical, it can be preferably unsubstituted or at least monosubstituted phenyl radical.

If the alkali metal alkoxide is used in the method in accordance with the invention, it may preferably be a derivative of sodium and may preferably have from 1 to 3 carbon atoms.

Suitable reaction medium for use in the method in accordance with the invention is a normal reaction medium, which is known to the average expert in the field of technology, provided that it does not undergo irreversible chemical interaction with the appropriate base or with a corresponding received by monohydroperoxide.

In the following preferred the oploschenii method in accordance with the invention, the reaction medium is water, if desired mixed with one or more organic solvents, which also in accordance with the invention included a two-phase system, such as, for example, a mixture of water and hydrocarbons.

The method of receiving monohydroperoxide in accordance with the invention also preferably can be made using one or more organic solvents, where, when used, at least two solvents, they optionally can be in the form of a two-phase system.

Suitable organic solvents that are used in the method in accordance with the invention, in each case individually or in any desired combination with each other, optionally mixed with water, can preferably be selected from the group comprising alcohols, ethers, acylamide, sulfoxidov, sulfones, NITRILES and hydrocarbons.

The preferred alcohols are compounds which have from 1 to 4 carbon atoms in the alkyl part. The corresponding alcohols may preferably be selected from the group comprising methanol, ethanol, isopropanol and mixtures of at least two of the abovementioned alcohols.

The number monohydroperoxide formed from the corresponding used performancehistory(s) and the type of the addition the reaction products can be controlled in order to airavat in the target method in accordance with the method in accordance with the invention, for example, through temperature and/or pressure during the reaction or after the molar ratio of performancehistory and alkane.

For example, by selecting parameters specific to split one, two or three performanceline group in the corresponding used deferredmediaselection.

If you delete one perforaciones group of the corresponding deferredmediaselection, also, inter alia, form the corresponding bis(perfluoroalkyl)phosphinate, in addition to the desired monohydroperoxide.

When you remove the two performanceline groups from the corresponding deferredmediaselection, also, inter alia, is formed corresponding PerformancePoint, in addition to the desired monohydroperoxide.

If removed three performanceline group in the corresponding deferredmediaselection, also, inter alia, is formed corresponding phosphate, in addition to the desired monohydroperoxide.

The appropriate choice of optimal parameters for the desired combination of the corresponding monohydroperoxide, quantity, and appropriate additional reaction products can be determined by the average expert in the art using a simple preliminary experiments.

For example, if you plan to remove one perforaciones the group in the appropriate use deferredmediaselection, the method in accordance with the invention can preferably carried out at temperatures from -10 to 100°and the mole-equivalent ratio of deferredmediaselection to the base of 1:3.

For example, if you plan to remove two performanceline groups in the appropriate use deferredmediaselection, the method in accordance with the invention can preferably carried out at temperatures from 50 to 150°and the mole-equivalent ratio of deferredmediaselection and grounds 1:4.

For example, if you plan to remove three performanceline groups in the appropriate use deferredmediaselection, the method in accordance with the invention can preferably carried out at temperatures from 100 to 250°and the mole-equivalent ratio of deferredmediaselection and grounds 1:5.

Monohydroperoxide obtained using the method in accordance with the invention can, if necessary, to allocate and, if necessary, be purified by conventional methods known to the average person skilled in the technical field.

If they are volatile compounds, they can be isolated from the reaction mixture by, for example, condensation in one or more cold traps, which are preferably cooled with liquid nitrogen or dry the m ice.

Any selection and purification of additional products of the reaction is also carried out by using conventional methods well known to the average expert in the art, such as, for example, by means of fractional crystallization or extraction with suitable solvents.

If performancehistory reacts with inorganic base (b)formed so bis(perfluoroalkyl)phosphinate and PerformancePoint can be converted directly or after extraction using an acid, preferably with sulfuric acid, into the corresponding bis(perfluoroalkyl)phosphinic acids and perforaciones acid.

Bis(perfluoroalkyl)phosphinic acids and perforaciones acid obtained in this way can be converted to a salt by neutralization, preferably using an organic base ().

By selection of suitable bases are preferably receive partially alkylated and parallelomania ammonium, postname, sulfonate, pyridinium, pyridazines, pyrimidines, pyrazinamide, imidazoline, pyrazoline, thiazoline, oxazoline and triazolam salt.

Particular preference is given to obtaining salts having cations selected from the group including

where R1-R5are the same Il is different, not necessarily linked to each other using simple or double bond, and each, individually or together, has the meaning set forth:

-N,

- halogen, where halogen is not directly connected to the N atom,

is an alkyl radical (C1-C8), which may be partially or fully substituted preferably the following groups: F, Cl, N(CnF(2n+1-x)Hx)2, O(CnF(2n+1-x)Hx), SO2(CnF(2n+1-x)Hx), CnF(2n+1-x)Hxwhere 1<n<6 and 0<x≤2n+1.

These salts can also be obtained if the salt obtained after the reaction of performancehistory with inorganic base (b), subjected to the exchange of salt, either directly or after separation.

Currency salts can be carried out with an aryl-, alkyl - or alkylaryl-ammonium or-phosphonium salts. Preference is given to using hexaflurophosphate, tetrafluoroborate, hexafluoroarsenate, sulfates, fluorides, chlorides or bromides.

Salt thus obtained can be processed using conventional techniques well known to the average person skilled in the technical field.

The method of receiving monohydroperoxide in accordance with the invention allows simple, inexpensive and reliable to obtain these compounds with very good yields. In particular, performancehistory used is passed as the parent compound, you can get in unexpectedly large numbers.

In addition, the advantage is that the by-products obtained in the method in accordance with the invention, such as, for example, bis(perfluoroalkyl)phosphinate and PerformancePoint itself are raw materials, which are suitable, inter alia, to obtain the corresponding bis(perfluoroalkyl)phosphinic acids and perforaciones acids and, therefore, can be economically useful. Neutralization using suitable bases allows to obtain, for example, bis(perfluoroalkyl)phosphinate and PerformancePoint, which are suitable for use as ionic liquids, surfactants or catalysts phase transfer.

Another advantage is that the impact on the environment in the reaction method in accordance with the invention is minimal, which also has a positive impact on the cost of production we get monohydroperoxide using the method in accordance with the invention.

In addition, relevant monohydroperoxide get high purity immediately after carrying out the reaction as they are received, i.e. without complex stages of refinement.

The invention is explained below with reference to examples. These examples serve only to explain izaberete the Oia and do not restrict the General inventive concept.

EXAMPLES

Example 1

the 10.40 g (185,4 mmol) of potassium hydroxide are dissolved in 330 cm3water in the flask and the resulting solution is cooled with a bath temperature of -5°C. Subsequently, through an addition funnel over 15 minutes with stirring add 25,53 g (59,9 mmol) Deportes(pentafluoroethyl)phosphorane. The reaction mixture is subsequently brought to room temperature. Gaseous pentaverate formed by alkaline hydrolysis Deportes(pentafluoroethyl)phosphorane, collected in two subsequent traps, each of which is cooled with liquid nitrogen. Cooled traps get to 6.67 g of solid Pentafluoroethane, having a boiling point of -48°C. This value corresponds to the value specified in the literature (L.Conte et al. in J. Fluor. Chem., 38 (1988), c.319-326.

The output Pentafluoroethane is 92,8%, based on panafcortelone groups in remote Deportes(pentafluoroethyl)phosphorane under these conditions.

The reaction mixture in the flask also contains a solution of bis(pentafluoroethyl)phosphinate potassium ((C2F5)2P(O)OK) and potassium fluoride. To highlight bis(pentafluoroethyl)phosphinate potassium, first neutralize the excess of potassium hydroxide, using a few drops of an aqueous solution of hydrogen fluoride and water are removed under reduced pressure. The obtained solid residue is dried under reduced pressure of 120 PA, and is the temperature of the bath 100° With over two hours.

Bis(pentafluoroethyl)phosphinate potassium is extracted from the dried residue, using 150 cm3of methanol. The methanol is subsequently distilled off under reduced pressure of 120 PA, and the solid residue of bis(pentafluoroethyl)phosphinate dried potassium. The output is 19,0 g, which corresponds to 93,2%, based on the used Deportes(pentafluoroethyl)phosphorane.

Pentaverate characterized using1The h and19F-NMR spectroscopy and bis(pentafluoroethyl)phosphinate potassium use19F and 31P-NMR spectroscopy.

Pentaverate

1The h and19F-NMR spectra shoot spectrometer Bruker WP 80 SY at frequencies of 80.1 MHz to1N and 75.4 MHz for19F and -70°C. for this purpose, use FEP (peretyanuty polymer) tube, inside which is a thin 5 mm NMR tube with acetone-D6film as an external shutter and TMS or CCl3F, dissolved in acetone-D6film, as an external standard.

1H-NMR spectrum (acetone-D6the film, relative to TMS in the film, δ, M.Ch.): 5,80 TC;2JH, F=52,3 Hz;3JH, F=2,1 Hz.

19F-NMR spectrum (acetone-D6the film, relative to the CCl3F in the film, δ, M.Ch.):

-86,54 (CF3); -138,55 d (CHF2);2JH, F=52,5 Hz.

The data obtained correspond to the values described in the literature. M.D.Barberger et al. in Tetrahedron, 53, No. 29 (1997), s-9880, and N.Ignatiev et al. in Acta Chem. Scand. 53, No. 12 (1999), s-1116.

Bis(pentafluoroethyl)phosphinate potassium ((C2F5)2P(O)OK)

19F and31P-NMR spectra shoot spectrometer Broker Avance 300 at frequencies 282,4 MHz to19F and 121.5 MHz for31R.

19F-NMR spectrum (solvent acetone-D6internal standard CCl3F δ, M.Ch.): -80,38 m (CF3); -125,12 DM (CF2);2JH,F=67,3 Hz.

31P-NMR spectrum (solvent acetone-D6relative to 85 wt.% H3PO4in D2O δ, M.Ch.): 0,72 Queen;2JP, F=67.2 per Hz.

Example 2

of 5.99 g (of 142.8 mmol) of the monohydrate of lithium hydroxide dissolved in 150 cm3water in the flask and the resulting solution is cooled with a bath temperature of -10°C. Subsequently, through an addition funnel over 15 minutes with stirring add 19,30 g (45,3 mmol) Deportes(pentafluoroethyl)phosphorane. The reaction mixture is subsequently brought to room temperature. Gaseous pentaverate formed due to hydrolysis Deportes(pentafluoroethyl)phosphorane, collected in two subsequent traps, each of which is cooled with liquid nitrogen. Cooled traps get 4,95 g Pentafluoroethane as a solid. The output Pentafluoroethane is 91,2%, based on panafcortelone groups in remote Deportes(pentafluoroethyl)fastran is under these conditions.

In addition, the reaction mixture in the flask contains a solution of bis(pentafluoroethyl)phosphinate lithium ((C2F5)2P(O)OLi) and lithium fluoride. To highlight bis(pentafluoroethyl)phosphinate lithium, first neutralize the excess of lithium hydroxide, using a few drops of an aqueous solution of hydrogen fluoride, the precipitate of lithium fluoride is filtered and the water removed under reduced pressure. The obtained white solid, bis(pentafluoroethyl)phosphinate lithium, dried under reduced pressure of 120 PA and a bath temperature of 100°C for two hours. Get to 13.1 g of bis(pentafluoroethyl)phosphinate lithium containing approximately 2 wt.% lithium fluoride, which corresponds to the output 93,7%, based on the used Deportes(pentafluoroethyl)phosphorane.

Pentaverate characterized using1The h and19F-NMR spectroscopy and bis(pentafluoroethyl)phosphinate lithium using19F and31P-NMR spectroscopy.

Chemical shifts defined for Pentafluoroethane, correspond to the values indicated in Example 1.

Bis(pentafluoroethyl)phosphinate lithium

19F and31P-NMR spectra shoot spectrometer Bruker Avance 300 at frequencies 282,4 MHz to19F and 121.5 MHz for31R.

19F-NMR spectrum (solvent acetone-D6internal standard CCl3F δ, M.Ch.):

-80,32 m (CF3); -125,08 DM (CF2);2 JP, F=72,6 Hz.

31P-NMR spectrum (solvent acetone-D6relative to 85 wt.% H3PO4- 15 wt.% D2O in acetone-D6that δ, M.Ch.): 0.27 Queen;2JP, F=72,7 Hz.

Example 3

4.1 g (73,1 mmol) of potassium hydroxide dissolved in 150 cm3water in the flask and the resulting solution is cooled with a bath temperature of 0°C. Subsequently, through an addition funnel over 3 minutes under stirring add 16,87 g (23.2 mmol) Deportes(n-nonattributed)phosphorane. The reaction mixture is subsequently brought to room temperature, stirred at this temperature for eight hours and subsequently heated under reflux for eight hours. Gaseous 1H-nomatter-n-butane, which is formed due to hydrolysis Deportes(n-nonattributed)phosphorane, collected in subsequent trap cooled with dry ice. The cooled trap get 3,63 g of liquid 1H-nomatter-n-butane, having a boiling point of 14°C.

The output of the 1H-n-nonattribution is 71.2%, based on the n-nonafterburning groups in remote Deportes(n-nonattributed)phosphorane under these conditions.

The solution remaining in the flask is separated from the viscous residue remaining in the flask and neutralized using herodotou acid. To highlight bis(n-nonattributed)phosphinate potassium, water UDA is Aut under reduced pressure. The obtained solid residue is dried under reduced pressure of 120 PA and a bath temperature of 100°C for two hours. The dried residue is subsequently extracted with three portions of methanol at 50 cm3each faction unite, subsequently distilled under reduced pressure of 125 PA and the solid residue is dried. The yield of bis(n-nonattributed)phosphinate potassium is 7,88 g, which corresponds to 62.9%, based on the used Deportes(n-nonattributed)phosphorane.

1H-n-Nonattribute characterized using1The h and19F-NMR spectroscopy and bis(n-nonattributed)phosphinate potassium use19F and31P-NMR spectroscopy.

1H-Nonattribute

1The h and19F-NMR spectra shoot spectrometer Bruker WP 80 SY at frequencies of 80.1 MHz to1N and 75.4 MHz for19F and the temperature of -60°C. for this purpose, use FEP (peretyanuty polymer) tube, inside which is a thin 5 mm NMR tube with acetone-D6film as an external shutter and TMS or CCl3F, dissolved in acetone-D6film as an external standard.

1H-NMR spectrum (acetone-D6the film, relative to TMS in the film, δ, M.Ch.): 6,14 TT;2JH, F=52,0 Hz;3JH, F=5,0 Hz.

19P-NMR spectrum (acetone-D6the film, CCl3F in the film, δ, M.Ch.): -81,31 t (CF3); -127,93 m (CF2); -131,06 m (CF2); -137,9 DM (CF 2);2JH, F=52,0 Hz.

The data obtained correspond to the values described in the literature (.Hudlicky et al. in J. of Fluorine Chem., 59, №1 (1992), c.9-14.

Bis(n-nonattributed)phosphinate potassium

19F and31P-NMR spectra shoot spectrometer Bruker Avance 300 at frequencies 282,4 MHz to19F and 121.5 MHz for31R.

19F-NMR spectrum (solvent D2O relatively CF3COOH in D2O=76,53 M.Ch., δ, M.Ch.):

-82,69 TT (CF3); -122,33 m (CF2); -123,31 DM (CF2); -127,46 TM (CF2);2JH,F=79,5 Hz;4JF,F=9.6 Hz;4JF,F=12.0 Hz; JF,F=1.5 Hz.

31P-NMR spectrum (solvent D2O, internal standard 85 wt.% H3PO4, M.Ch.): 4,81 Queen;2JP,F=78,9 Hz.

Example 4

7.0 g (of 124.8 mmol) of potassium hydroxide dissolved in 10 cm3water in the flask and the resulting solution was heated at a bath temperature of 70-80°C. Subsequently, through an addition funnel over 20 minutes with stirring add 12,18 g (16,8 mmol) Deportes(n-nonattributed)phosphorane. The reaction mixture is subsequently heated at a bath temperature of 150°C and stirred at this temperature for another two hours.

Gaseous 1H-n-nonattribute formed due to hydrolysis Deportes(n-nonattributed)phosphorane, collected in subsequent trap cooled with dry ice. Cool is th trap get 6,12 g of liquid 1H-n-nonattribution. The output of the 1H-n-nonattribution 82.9%, based on the n-nonafterburning groups in remote Deportes(n-nonattributed)phosphorane under these conditions.

The residue remaining in the flask, dissolve in 50 cm of water and an excess of potassium hydroxide is neutralized using an aqueous solution of hydrogen fluoride. To highlight dicale(n-nonattributed)phosphonate, water is removed under reduced pressure. The obtained solid residue is dried under reduced pressure of 120 PA and a bath temperature of 100°C for two hours. Dicale(n-nonattributed)phosphonate, C4F9P(O)(OK)2subsequently extracted from the dried residue using two portions of methanol at 50 cm3each fraction are combined and the methanol is distilled off. The solid residue is subsequently dried under reduced pressure of 125 PA. Output dicale(n-nonattributed)phosphonate is 5.0 g, which corresponds to the output 79,2%, based on the used Deportes(n-nonattributed)phosphorane.

1H-n-Nonattribute characterized using1The h and19F-NMR spectroscopy and dicale (n-nonattributed)phosphonate using19F and31P-NMR spectroscopy.

Chemical shifts defined for 1H-n-nonattribution, correspond to the values shown in Example 3.

Dicale(n-nonattributed)phosphonate,4F9P(O)(OK)2

19F and31P-NMR spectra of the NIMA spectrometer Bruker Avance 300 at frequencies 282,4 MHz to 19F and 121.5 MHz for31R.

19P-NMR spectrum (solvent D2O relatively CF3COOH in D2O=76,53 M.Ch., δ, M.Ch.): -81,64 TT (CF3); -121,94 m (CF2); -122,86 DM (CF2); -126,66 TM (CF2);2JP, F=68,9 Hz;4JF, F=9.6 Hz;4JF, F=13,4 Hz; JF, F=3,9 Hz.

31P-NMR spectrum (solvent D2O, relative to 85 wt.% H3PO4in D2O δ, M.Ch.): 4,00 TT;2JP, F=68,8 Hz;3JP, F=3,4 Hz.

Example 5

8.0 g (to 190.5 mmol) of the monohydrate of lithium hydroxide are suspended in 15 cm3water in the flask and the resulting suspension heated at a bath temperature of 70-80 °C. Subsequently, through an addition funnel over 30 minutes under stirring add 21,21 g (29.2 mmol) Deportes(n-nonattributed)phosphorane. The reaction mixture is subsequently heated to a temperature bath of 150°C and stirred at this temperature for another two hours.

Gaseous 1H-n-nonattribute formed due to hydrolysis Deportes(n-nonattributed)phosphorane, collected in subsequent trap cooled with dry ice. The cooled trap collected from 7.24 g of liquid 1H-n-nonattribution. The output of the 1H-n-nonattribution is 56,3%, based on the n-nonafterburning groups in remote Deportes(n-nonattributed)phosphorane under these conditions.

The residue remaining in the flask is dissolved in 50 cm 3water and excess potassium hydroxide is neutralized using an aqueous solution of hydrogen fluoride, and the resulting precipitate of lithium fluoride filtered. In order to allocate delity(n-nonattributed)phosphonate, C4F9P(O)(OLi)2water is removed under reduced pressure. The obtained white solid is dried under reduced pressure (120 PA) and a bath temperature of 100°C for two hours. Obtain 8.0 g of delity-nonoperational, which corresponds to a yield of 87.8%, based on the used Deportes(n-nonattributed)phosphorane.

1H-n-Nonattribute characterized using1The h and19F-NMR spectroscopy and delity(n-nonattributed)phosphonate using19F and31P-NMR spectroscopy.

Chemical shifts defined for 1H-n-nonattribution, correspond to the values specified in Example 3.

Delity-nonoperational

19F and31P-NMR spectra shoot spectrometer Bruker Avance 300 at frequencies 282,4 MHz to19F and 121.5 MHz for31R.

19F-NMR spectrum (solvent D2O relatively CF3COOH in D2O=76,53 M.Ch., δ, M.Ch.): -81,85 TT (CF3); -122,03 m (CF2); -123,06 DM (CF2); -126,79 TM (CF2);2JP, F=70.1 Hz;4JF, F=9.5 Hz;4JF, F=14,2 Hz; JF, F=3,9 Hz;

(solvent acetone-D6internal standard CCl3F &x003B4; , M.Ch.): -80,92 m (CF3); -120,66 m (CF2); -122,70 DM (CF2); -125,62 TM (CF2);2JP, F=78,6 Hz;4JF, F=9.9 Hz;4JF, F=14,5 Hz; JF, F=3,2 Hz.

31P-NMR spectrum (solvent D2O, relative to 85 wt.% H3PO4in D2O δ, M.Ch.): 3,81 TT;2JP, F=70.1 Hz;3JP, F=3.3 Hz;

(solvent acetone-D6relative to 85 wt.% H3PO4-15% D2O in acetone-D6that δ, M.Ch.): -0,28 t;2JP, F=78,1 Hz.

Example 6

10,24 g (182,5 mmol) of potassium hydroxide dissolved in 10 cm3water in the flask and the resulting solution was heated at a bath temperature of 65-70°C. Subsequently, through an addition funnel over 60 minutes under stirring add 18,70 g (43,9 mmol) Deportes(pentafluoroethyl)phosphorane. The reaction mixture is subsequently heated at a bath temperature of 120°C and stirred at this temperature for another one hour.

Gaseous pentaverate formed due to hydrolysis Deportes(pentafluoroethyl)phosphorane, collected in subsequent trap, cooled with liquid nitrogen.

Get 9,99 g of solid Pentafluoroethane in a cooled trap. The output Pentafluoroethane is 94,8%, based on the two panafcortelone groups in remote Deportes(pentafluoroethyl)phosphorane under these conditions.

The residue remaining in the flask, RA is tworay 40 cm 3water and excess potassium hydroxide is neutralized with a few drops of an aqueous solution of hydrogen fluoride.

To highlight disalienation, water is removed under reduced pressure. The obtained solid is dried under reduced pressure (120 PA) and a bath temperature of 100°C for one hour. Disalienation subsequently extracted from the solid residue by using two portions of methanol at 50 cm3each faction unite, the methanol is distilled off and the obtained residue is dried under reduced pressure (120 PA).

Get 16,54 g di(potassium fluoride) disalienation, (C2F5P(O)(OK)2)·2KF, which corresponds to the output 96,1%, based on the used Deportes(pentafluoroethyl)phosphorane.

Pentaverate characterized using1The h and19F-NMR spectroscopy and di(potassium fluoride) disalienation using19F and31P-NMR spectroscopy.

Chemical shifts defined for Pentafluoroethane, correspond to the values indicated in Example 1.

Di(potassium fluoride) disalienation

19F-NMR spectrum

(solvent D2O relatively CF3COOH in D2O=76,53 M.Ch., δ, M.Ch.):

-81,86 t (CF3); -125,91 to (CF2); -122,70 (2KF);2JP, F=68,4 Hz;3JF, F=1,6 Hz.

31The NMR spectrum (solvent D 2O, relative to 85 wt.% H3PO4in D2O δ, M.Ch.): 3,17 t;2JP, F=68,4 Hz.

Example 7

of 8.50 g (151,5 mmol) of potassium hydroxide dissolved in 8.8 cm3water in the flask and the resulting solution was heated at a bath temperature of 70-80°C. Subsequently, through an addition funnel over 90 minutes under stirring add 15,77 g (37,0 mmol) Deportes(pentafluoroethyl)phosphorane.

Gaseous pentaverate formed due to hydrolysis Deportes(pentafluoroethyl)phosphorane, collected in subsequent trap, cooled with liquid nitrogen.

Get 8,30 g of solid Pentafluoroethane in a cooled trap. The output Pentafluoroethane accounts for 93.4%, based on the two panafcortelone groups in remote Deportes(pentafluoroethyl)phosphorane under these conditions.

Chemical shifts defined for Pentafluoroethane, correspond to the values specified in Example 1.

Example 8

6,23 g (111,0 mmol) of potassium hydroxide dissolved in 12,18 g of a mixture of ethanol/water (1:1 weight parts) in the flask and the resulting solution was heated at a bath temperature of 55-60°C. Subsequently, through an addition funnel over 45 minutes with stirring, add 11,43 g (26.8 mmol) Deportes(pentafluoroethyl)phosphorane and the reaction mixture is heated at 80°C for 10 minutes.

Gaseous pentaverate produced as a result of the guide is Alisa Deportes(pentafluoroethyl)phosphorane, collected in subsequent trap, cooled with liquid nitrogen.

Get 5,23 g of solid Pentafluoroethane in a cooled trap. The output Pentafluoroethane is 81,3%, based on the two panafcortelone groups in remote Deportes(pentafluoroethyl)phosphorane under these conditions.

Chemical shifts defined for Pentafluoroethane, correspond to the values indicated in Example 1.

Example 9

13,46 g (of 31.6 mmol) Deportes(pentafluoroethyl)phosphorane added through the addition funnel with stirring for one hour at room temperature to of 96.5 g (RB 131.1 mmol) of 20 wt.% an aqueous solution of hydroxide of tetraethylammonium. During this operation, there is heating of the reaction mixture. The reaction mixture is subsequently heated at 80°C for 30 minutes. Gaseous pentaverate formed due to hydrolysis Deportes(pentafluoroethyl)phosphorane, collected in subsequent trap, cooled with liquid nitrogen. Get 7,49 g of solid Pentafluoroethane in a cooled trap. The output Pentafluoroethane is 98.8%, based on the two remote panafcortelone groups.

Chemical shifts defined for Pentafluoroethane, correspond to the values specified in Example 1.

The solution remaining in the flask, evaporated on a rotary evaporator and the resulting solid is dried under reduced pressure (120 P is) and a temperature of 100° With, 24,67 g of white crystalline [(C2H5)4N]2[C2F5PO3]•2[(C2H5)4N]F•8H2O.

[(C2H5)4N]2[C2F5PO3]•2[(C2H5)4N]F•8H2O characterize using1H,19F and19F31P-NMR spectroscopy and elemental analysis.

19F-,1The h and31P-NMR spectra shoot spectrometer Bruker Avance 300 at frequencies 282,4 MHz to19F and 121.5 MHz for31R.

19P-NMR spectrum (solvent acetonitrile-D3regarding CCl3F δ, M.Ch.): -79,41 dt (CF3); -126,74 DK (CF2); -111,74 (2F-);2JP, F=54,0 Hz;3JP,F=1.1 Hz;3JF, F=1.0 Hz.

1H-NMR spectrum (solvent acetonitrile-D3relative to TMS, δ, M.Ch.): 1,21 TM (CH3); 3,28 (CH2);3JH, H=7,3 Hz.

The exchange of the proton in the molecule H2O for deuterium solvent.

31P-NMR spectrum

(solvent acetonitrile-D3relative to 85 wt.% H3PO4- 15% D2O in acetonitrile-D3that δ, M.Ch.): -1,77 t;2JP, F=54,2 Hz.

Elemental analysis:

calculated for C34H96F5N4O11R: 47,31%; N 11,21%; N of 6.49%;

found: 47.37 per cent; N 10,80%; N 6,40%.

Example 10

50,38 g (159,7 mmol) octahydrate hydroxide bar which I suspended in 100 cm 3water in the flask and the resulting suspension heated at a bath temperature of 65-70°C. Subsequently, through an addition funnel over 30 minutes under stirring add 22,68 g (53.2 mmol) Deportes(pentafluoroethyl)phosphorane. The reaction mixture is subsequently heated to a temperature of 150°C and stirred at this temperature for two hours.

Gaseous pentaverate formed due to hydrolysis Deportes(pentafluoroethyl)phosphorane, collected in subsequent trap cooled with dry ice.

Get 10,00 g of liquid Pentafluoroethane in a cooled trap. The output Pentafluoroethane is to 78.3%, based on the two panafcortelone groups in remote Deportes(pentafluoroethyl)phosphorane under these conditions.

The residue remaining in the flask is transferred into a 50 cm3water and neutralized using an aqueous solution of hydrogen fluoride. Filtered off the precipitate of barium fluoride.

To highlight panafcortelone barium, water is removed under reduced pressure. The obtained white substance is dried under reduced pressure (120 PA) and a bath temperature of 100°C for one hour. Get 10.6 g pentaphosphate barium ([C2F5P(O)O2]Ba), which contains the setting just over 2 wt.% barium fluoride, which corresponds to the output 59,2%, based on the used Deportes(pentaf oratel)phosphorane.

Pentaverate characterized using1The h and19F-NMR spectroscopy and pentaphosphate barium using19F and31P-NMR spectroscopy.

Chemical shifts defined for Pentafluoroethane, correspond to the values specified in Example 1.

Panafcortelone barium

19F-,1The h and31P-NMR spectra shoot spectrometer Bruker Avance 300 at frequencies 282,4 MHz to19F and 121.5 MHz for31R.

19F-NMR spectrum (solvent D2O relatively CF3COOH in D2About=76,53 M.Ch., δ, M.Ch.): -81,99 TD (CF3); -126,25 DK (CF2);2JP, F=70,5 Hz;3JF, F=1,8 Hz;3JP, F=0.5 Hz.

31P-NMR spectrum (solvent D2O, relative to 85 wt.% H3PO4in D2O δ, M.Ch.):

2,88 t;2JP, F=70,3 Hz.

Example 11

16,70 g (52,9 mmol) octahydrate barium hydroxide suspended in 20 cm3water in the flask and the resulting suspension heated at a bath temperature of 70-80°C. Subsequently, through an addition funnel over 30 minutes under stirring add 17,79 g (24.5 mmol) Deportes(n-nonattributed)phosphorane. The reaction mixture is subsequently heated at a bath temperature of 120°C and stirred at this temperature for one hour.

Gaseous 1H-n-nonattribute formed due to hydrolysis divert the IP(n-nonattributed)phosphorane, collected in the subsequent trap, cooled with liquid nitrogen.

Get 7,72 g solid 1H-n-nonattribution in a cooled trap. The output of the 1H-n-nonattribution is 71.6%, based on the two n-nonafterburning groups deleted in Deportes(n-nonattributed)phosphorane under these conditions.

The residue remaining in the flask is transferred into a 50 cm3water and neutralized using an aqueous solution of hydrogen fluoride. Filtered off the precipitate of barium fluoride.

In order to distinguish n-nonoperational barium, water is removed under reduced pressure. The obtained white substance is dried under reduced pressure (120 PA) and a bath temperature of 100°C for one hour. Obtain 7.0 g of n-nonoperational barium ([n-s4F9P(O)O2]VA), which contains about 2 wt.% barium fluoride, which corresponds to the output 64,87%, based on the used Deportes(pentafluoroethyl)phosphorane.

1H-n-Nonattribute characterized using1The h and19F-NMR spectroscopy and n-nonoperational barium using19F and31P-NMR spectroscopy.

Chemical shifts defined for 1H-nonattribution, correspond to the values specified in Example 3.

n-Nonoperational barium

19F-NMR spectrum (solvent D2O relatively CF3COOH in D2O=76,53 M.Ch., δ, M.Ch.): -8177 TT (CF 3); -122,29 m (CF2); -123,66 DTM (CF2); -126,76 TM (CF2);2JP, F=75,8 Hz;4JF, F=9.7 Hz;4JF, F=13,8 Hz; JF, F=3,6 Hz.

31P-NMR spectrum (solvent D2O, relative to 85 wt.% H3PO4in D2O δ, M.Ch.): 2,22 t;2JP, F=76,1 Hz.

Example 12

10,32 g (183,9 mmol) of potassium hydroxide and 20 cm3water is brought into an autoclave having a volume of 100 cm3. The autoclave is cooled to -30°and add to 9.70 g (of 22.8 mmol) Deportes(pentafluoroethyl)phosphorane. The autoclave is subsequently closed and heated at 200-210°for eight hours using an oil bath. The autoclave is then brought to room temperature and the outlet of the autoclave, is attached to the cold trap, cooled with liquid nitrogen.

Receive EUR 7.57 g of pure Pentafluoroethane, which corresponds to a yield of 92.2%, based on the three panafcortelone groups deleted in used Deportes(pentafluoroethyl)phosphorane under these conditions.

Chemical shifts defined for Pentafluoroethane, correspond to the values specified in Example 1.

Example 13

of 51.0 g of potassium hydroxide and 50 cm3water is brought into an autoclave having a volume of 350 cm3. The autoclave is cooled to -30°and add 95,9 g of a mixture of triformis(n-nonattributed)phosphorane (60 mol.%) and Deportes(n-nonattributed)phosphorane (40 mol.%). The autoclave is subsequently closed the societal and heated at 200-210° C for 18 hours using an oil bath. The autoclave is then brought to room temperature and the outlet of the autoclave attached to a cold trap cooled with dry ice.

Get to 68.0 g of pure 1H-nomatter-n-butane, which corresponds to the output is 95.2%, based on the two n-nonafterburning groups to be deleted in your triformis(n-nonattributed)phosphorane and Deportes(n-nonattributed)phosphorane under these conditions.

1H-Nomatter-n-butane characterized using1The h and19F-NMR spectroscopy.

Chemical shifts defined for 1H-nomatter-n-butane, correspond to the values specified in Example 3.

Example 14

Bis(pentafluoroethyl)phosphinic acid

4.09 g (12,0 mmol) bis(pentafluoroethyl)phosphinate potassium is introduced into distilation flask from 8.71 g (88,9 mmol) of 100% sulfuric acid, H2SO4and the resulting bis(pentafluoroethyl)phosphinic acid is distilled under reduced pressure (400 PA) and an oil bath temperature of 90-120°C. Obtain 3.25 g of a transparent and colorless liquid bis(pentafluoroethyl)phosphinic acid, (C2F5)2P(O)OH, which corresponds to the output to 89.5%.

The values of chemical shifts correspond to the values described in the publication .Mahmood, Inorganic Chemistry, 25 (1986), s-3131.

Example 15

1.0 g (10.2 mmol) of 100% sulfuric acid, H2SO4added to a mixed solution of 3.42 is (10.2 mmol) panafcortelone barium 50 cm 3water. A precipitate of barium sulphate, which is separated by filtration. The obtained filtrate is completely evaporated under reduced pressure and dried at 125 PA and an oil bath temperature of 100°during the next 6 hours. Get a 1.75 g of viscous liquid pentafluorothiophenol acid C2F5P(O)(OH)2that corresponds to the output of 83.8 percent.

19F-NMR spectrum (solvent: acetonitrile-D3regarding CCl3F δ, M.Ch.): -81,03 t (CF3); -126,74 DK (CF2); J2P, F=89,4 Hz, J3F, F=1,6 Hz.

1H-NMR spectrum (solvent: acetonitrile-D3relative to TMS, δ, M.Ch.): of 11.26 sh. c (HE).

31P-NMR spectrum (solvent: acetonitrile-D3; relative to 85 wt.% H3PO4-15 wt.% D2O in acetonitrile-D3): -3,40 t, J2P, F=89,6 Hz.

These data correspond to the values described in the literature (.Mahmood and J.M.Shreeve, in Inorg. Chem., 25 (1986), c.3128-3131).

Example 16

The solution 0,492 g (2,46 mmol) pentafluorothiophenol acid was obtained as described in Example 15, 10 cm3water is neutralized by slow addition at room temperature under stirring 3,015 g of 20 wt.% aqueous hydroxide of tetraethylammonium. The water evaporated under reduced pressure and the resulting residue is dried under reduced pressure (120 PA) and a bath temperature of 50°Sleep for 2 hours.

Get 1,115 g of a white solid bis(tetraethylammonium)pentafluoropropionate. The output is 99.0%, based on the used pentafluorothiophenol acid.

Bis(tetraethylammonium)panafcortelone characterized using19F,31P and1H-NMR spectroscopy.

19F NMR spectrum, M.Ch. (solvent: acetonitrile-D3; relatively CCl3F): -79,49 (CF3); -122,10 d (CF2); J2P, F=54,6 Hz.

1H NMR spectrum, M.Ch. (solvent: acetonitrile-D3; relative to TMS): 1,20 TM (N, SN3); 3,29 (8H, SN2); J3H, H=7,3 Hz.

31P NMR spectrum, M.Ch. (solvent: acetonitrile-D3; relative to 85% H3PO4): -2,28 t; J2P, F=54.9 Hz.

Example 17

The solution nonfor-n-butylphosphonic acid, obtained as described in Example 15, of 3.73 g (to 8.57 mmol) nonfor-n-butylphosphonate barium and 0,839 g 15 100 wt.% sulfuric acid in 20 cm3water, neutralized (pH=7) by slow addition at room temperature with stirring to 20 wt.% aqueous hydroxide of tetraethylammonium. The water evaporated under reduced pressure and the resulting residue is dried under reduced pressure (120 PA) and the bath temperature 60°With over 2 hours.

Get 4.59 g of solid nonfor-n-butylphosphonate bis(tetraethylammonium). The output is 96,0%, based on the C used nonfor-n-butylphosphonate barium.

Nonfor-n-butylphosphonium bis(tetraethylammonium) characterize using19F,31R1H-NMR spectroscopy.

19F NMR spectrum, M.Ch. (solvent: acetonitrile-D3; relatively CCl3F): -80,37 TT (CF3); -119,57 m (CF2); -119,72 DM (CF2); -124,80 m (CF2); J2P, F=55,6 Hz; J3F, F=4,3 Hz; J4F, F=9.5 Hz.

1H NMR spectrum, M.Ch. (solvent: acetonitrile-D3; relative to TMS): 1,23 TM (N, SN3); 3,27 (8H, SN2); J3H,H=7,4 Hz.

31P NMR spectrum, M.Ch. (solvent: acetonitrile-D3; relative to 85% H3PO4): -2,06 t; J2P, F=56,5 Hz.

Example 18

1,43 g pentafluorothiophenol acid, obtained as described in Example 15, was dissolved in 15 cm3water and neutralized (pH=7) by slow addition at room temperature under stirring to 10 wt.% aqueous potassium hydroxide. To the obtained aqueous solution of Dikili panafcortelone with constant stirring at room temperature was added a solution of 2.09 g (11.9 mmol) of the chloride of 1-ethyl-C-methylimidazole 3 cm3water. The water evaporated under reduced pressure and the resulting residue is dried under reduced pressure (120 PA) and the bath temperature 60°C for 1 hour. Subsequently, to the residue add 10 cm3isopr delovogo alcohol, white precipitate is filtered off and washed twice with 5 cm3isopropyl alcohol. Isopropyl alcohol is evaporated under reduced pressure and the resulting residue is dried under reduced pressure (1,4 PA) and a bath temperature of 80°C for 1.5 hours.

Gain of 2.56 g of oily liquid panafcortelone di(1-ethyl-3-methylimidazole). The output is 85,0%, based on the used pentafluorothiophenol acid.

Panafcortelone di(1-ethyl-3-methylimidazole) characterize using19F,31R1H-NMR spectroscopy.

19F NMR spectrum, M.Ch. (solvent: acetonitrile-D3; relatively CCl3F): -79,68 (CF3); -123,22 d (CF2); J2P, F=57,9 Hz.

1H NMR spectrum, M.Ch. (solvent: acetonitrile-D3; relative to TMS): 1,38 t (3H, CH3); of 3.94 (3H, CH3); the 4.29 (2H, CH2); 7,70 s (1H); 7,75 s (1H); was 10.82 (1H); J3H, H=7,2 Hz.

31P NMR spectrum, M.Ch. (solvent: acetonitrile-D3; relative to 85% H3PO4): -1,28 t; J3P, F=57.4 Hz.

Example 19

A solution of 2.4 g (12,0 mmol) pentafluorothiophenol acid, obtained as described in Example 15, 13 cm3water is neutralized (pH=7) by slow addition at room temperature under stirring 14,86 g to about 40 wt.% water the hydroxide tetrabutyltin one. The water evaporated under reduced pressure and the resulting residue is dried under reduced pressure (1,4 PA) and a bath temperature of 70°With over 2 hours.

Get to 7.95 g of a highly viscous liquid which slowly crystallized to a white solid panafcortelone bis(tetrabutylphosphonium). The output is 92,4%, based on the used pentafluorothiophenol acid.

Melting point 76-79°C.

Panafcortelone bis(tetrabutylphosphonium),

[(C4H9)4P+]2C2F5P(O)O22-characterize using19F,31P and1H-NMR spectroscopy.

19F NMR spectrum, M.Ch. (solvent: acetonitrile-D3; relatively CCl3F): -79,39 (CF3); -121,98 d (CF2); J2P, F=54,2 Hz.

1H NMR spectrum, M.Ch. (solvent: acetonitrile-D3; relative to TMS): 0,93 t (N, SN3); 1.45 m (N, 8CH2); 2.37 (8H, SN2); J3H, H=7,1 Hz.

31P NMR spectrum, M.Ch.

(solvent: acetonitrile-D3; relative to 85% H3PO4): -1,84 t (1P); 32,73 m (2P); J2P, F=54,6 Hz.

1. The method of receiving monohydroperoxide, bis(perfluoroalkyl)Phosphinates and perforaciones, including at least processing at least one of performancehistory at least one of the a subject, where the basis of(I) selected from the group consisting of hydroxides of alkaline earth metals, organo-metallic compound in a suitable solvent or at least one organic base and, if desired acid in a suitable reaction medium.

2. The method of obtaining bis(perfluoroalkyl)Phosphinates and perforaciones in accordance with claim 1, characterized in that at least one performancehistory interacts with at least one base, where the base(I) is selected from the group consisting of hydroxides of alkaline earth metals in a suitable solvent, bis(perfluoroalkyl)phosphinate and PerformancePoint formed in addition to monohydroperoxide, converted into the corresponding bis(perfluoroalkyl)phosphinic acids and perforaciones acid directly or after isolation by sharing salt or subsequent treatment with acid, preferably sulfuric acid, and the salts subsequently neutralized, preferably using organic bases.

3. The method in accordance with claim 1 or 2, characterized in that the method of receiving monohydroperoxide carried out at a temperature from 100 to 250°C.

4. The method in accordance with claim 1 or 2, characterized in that the method of obtaining bis(perfluoroalkyl)Phosphinates carried out at tempera is ur -10 to 100° C.

5. The method in accordance with claim 1 or 2, characterized in that the method of obtaining perforaciones carried out at a temperature from 50 to 150°C.

6. The method in accordance with claim 1 or 2, characterized in that used by performancelogginon is a compound of General formula I

in which 1≤n≤8, preferably 1≤n≤4, and m in each case is 1, 2 or 3.

7. The method in accordance with claim 1 or 2, characterized in that performancehistory chosen from the group comprising Deportes(pentafluoroethyl)fastran, Deportes(n-nonattributed)fastran, Deportes(n-heptafluoropropyl)fastran and triformis(n-nonattributed)fastran.

8. The method in accordance with claim 1 or 2, characterized in that the organic base(I) is chosen from the group comprising hydroxides of alkylamine, hydroxides of arylamine, hydroxides of alkylsilane, hydroxides alkylphosphine, hydroxides arylphosphine, hydroxides alkylarylsulfonate, bonds alkylamines, arylamines, alkylsilane, alkylphosphine, arylphosphine, alkylarylphosphites.

9. The method in accordance with claim 1 or 2, characterized in that the hydroxide of alkaline earth metal chosen from the group comprising barium hydroxide, octahydrate barium hydroxide and calcium hydroxide.

10. The method in accordance with claim 1, characterized in that org is but-metallic compound selected from the group include alkoxides of metals, preferably alkoxides of alkali metals, aryloxides metals, alkylthiomethyl metals, arylthiols metals, alkylbetaine connection arylmethylidene compounds and Grignard reagents.

11. The method in accordance with claim 1 or 2, characterized in that the reaction medium is water, optionally mixed with one or more organic solvents.

12. The method in accordance with claim 1 or 2, characterized in that the reaction medium is one or more organic solvents.

13. The method in accordance with claim 11 or 12, characterized in that the organic solvent is chosen from the group comprising alcohols, ethers, acylamide, sulfoxidov, sulfones, NITRILES and hydrocarbons.

14. Method according to item 13, wherein the alcohol has from one to four carbon atoms in the alkyl part and, preferably, selected from the group comprising methanol, ethanol, isopropanol and mixtures of at least two of these alcohols.

15. PerformancePoint and bis(perfluoroalkyl)phosphinate, which is selected from the group comprising partially alkylated and parallelomania ammonium, postname, sulfonate, pyridinium, pyridazines, pyrimidines, pyrazinamide, imidazoline, pyrazoline, thiazolium is e, oxazoline and triazolam salts of these compounds, with the exception of bis(heptafluoropropyl)phosphinate N-methyl-2-triftormetilfosfinov and bis(heptafluoropropyl)Phosphinates and triethylmethylammonium.

16. PerformancePoint and bis(perfluoroalkyl)phosphinate in accordance with § 15, having a cation chosen from the group including

where R1-R5are the same or different, are not necessarily associated directly with each other using simple or double bond and each, individually or together, has the meaning set forth:

N

halogen, where halogen is not directly connected to the N atom,

alkyl radical (C1-C8), which can be partially or completely substituted by the following groups, preferably F, Cl, N(CnF(2n+1-x)Hx)2, O(CnF(2n+1-x)Hx), SO2(CnF(2n+1-x)Hx), CnF(2n+1-x)Hxwhere 1<n<6 and 0<x<2n+1, with the exception of bis(heptafluoropropyl)phosphinate N-methyl-2-triftormetilfosfinov and the IP(heptafluoropropyl)Phosphinates and triethylmethylammonium.

17. Application perforaciones and bis(perfluoroalkyl)phosphinate in accordance with clause 15 or 16, as ionic liquids.

18. Application perforaciones and bis(perfluoroalkyl)phosphinate in accordance with clause 15 or 16, as catalysts phase transfer or surface-active substances.



 

Same patents:

FIELD: chemistry of metalloorganic compounds, chemical technology.

SUBSTANCE: invention relates to a method for preparing copper (II), zinc (II), nickel (II) and cobalt (II) nitrilotri-(methylenephosphonates)(2-) that involves crystallization from aqueous solutions prepared by interaction of metal (II) compound with nitrilotri-(methylenephosphonic) acid or its salt with sodium potassium or ammonium in aqueous medium at temperature from -5°C to 105°C under atmosphere pressure. As a reactive of the metal (II) compound source the waste from manufacturing printing plates and galvanic covers can be used. The end products can be used in preparing the complex electrolytes and solutions for applying metallic covers by electrochemical and chemical methods in aims for inhibition against the equipment corrosion, and for preparing other compounds of metals with nitrilotri-(methylenephosphonic) acid.

EFFECT: improved method of synthesis.

16 cl, 1 tbl, 19 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, chemical technology.

SUBSTANCE: invention relates to a novel method for synthesis of N-phosphonomethylglycine. Method involves interaction of hexahydrotriazine compound with triacyl phosphite in organic solvent, saponification of formed phosphonic compound after preliminary extraction into aqueous phase, separation of organic phase and precipitation of N-phosphonomethylglycine by pH value control in the range from 0.5 to 2.0. Invention prevents decomposition of an organic solvent in saponification.

EFFECT: improved method of synthesis.

8 cl, 3 tbl, 4 ex

FIELD: chemical industry; methods of production of the water solution of disodium or dipotassium salt of zinc oxyethyledene phosphonate.

SUBSTANCE: the invention is pertaining to the method of production of the water solutions of disodium or dipotassium salt of zinc oxyethyledene phosohonate with concentration of 15-23 % used as the mineral salts sediments inhibitors and as the microfertilizers and having the properties to inhibit corrosion. The method provides for interaction of the water solution of the sodium zincate or the potassium zincate with the 20-60 % water solution of the oxyethyledenephosphonic acid at the temperature of 60-80°С. As a rule, the sodium zincate or the potassium zincate are produced by interaction of 5-20 % water solution of the sodium hydroxide or the potassium hydroxide with zinc oxide at the temperature of 50-75°С at the molar relation of 2:1.

EFFECT: the invention ensures, that as the rule the sodium zincate or the potassium zincate are produced by interaction of the low-concentration water solutions of the sodium hydroxide or the potassium hydroxide with zinc oxide at the temperature of 50-75°С at the molar relation of 2:1.

2 cl, 1 tbl, 11 ex

FIELD: industrial and waste water treatment.

SUBSTANCE: composition contains 10-25% sodium alkylaminophosphonates having general formula: , in which n=9-19, 1-5% sodium chloride, and 70-89% water. Composition is prepared by heat treatment of industrial-grade aliphatic amines with phosphorous acid and formaldehyde. In particular, treatment of aliphatic amines of formula CH3-(CH2)-NH2 (n=9-19) is carried out in presence of hydrochloric acid as catalyst at 95-105°C for 1.5-3.0 h followed by cooling and neutralization with sodium alkali to pH 10.

EFFECT: enhanced treatment efficiency.

2 cl, 1 tbl

FIELD: chemical technology.

SUBSTANCE: invention relates to technology for synthesis of crystalline nitrilotrimethylphosphonic acid sodium salts. For synthesis of nitrilotrimethylphosphonic acid disodium salt monohydrate the method involves preliminary synthesis of nitrilotrimethylphosphonic acid by interaction of phosphorus trichloride, formaldehyde and ammonia or its derivative followed by neutralization with sodium hydroxide in the content in the reaction mass 46-54 wt.-% of nitrilotrimethylphosphonic acid and 6.0-16.0 wt.-% of hydrogen chloride up to pH value 2.5-4.5, and isolation of the end compound by crystallization. The mass part of the main substance in synthesized product is 88-95%, the content of chloride ions is 1.2-2.0%, yield is 50-60% as measured for PCl3. Synthesized compound is recommended for using as chelate compounds as a component of detergents, anti-rheological additive in drilling solutions, plasticizing agents for building concretes, in wine-making industry, as inhibitors of salt depositions in heat and power engineering and others fields.

EFFECT: improved method of synthesis.

2 tbl, 12 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to the improved method for preparing bis-(1-hydroxyethane-1,1-diphosphonate(1-)) zinc (II). Method involves interaction of zinc-containing reagent and 1-hydroxyethane-1,1-diphosphonic acid in a solvent medium, crystallization of the end product from solution, separation of deposit from solution and drying the deposit. Method involves using water-soluble zinc (II) salt with anion of strong acid as a zinc-containing reagent and preparing the solution with the concentration of zinc (II) salt from 0.2 to 2.2 mole/l and the concentration of 1-hydroxyethane-1,1-diphosphonic acid from 0.4 to 5.0 mole/l. The end product prepared by proposed method can be used in preparing phosphonate electrolytes for galvanic zinc-plating, for preparing zinc-phosphate inhibitors of steel corrosion, as trace supplement to vitamin preparations and fodders for animals, as a zinc microfertilizer in agriculture and for preparing other compounds of zinc (II). Invention provides enhancing purity and uniformity of the end product, increasing its yield, improved technological effectiveness of process, utilizing toxic waste in galvanic manufacturing.

EFFECT: improved preparing method.

8 cl, 1 tbl, 6 ex

FIELD: chemistry of organophosphorus compounds, agriculture, pesticides.

SUBSTANCE: invention describes bis-(diethylammonium)-dihydrogen-1-hydroxyethyl-1,1diphosphonate monohydrate of the formula (I) showing properties of stimulator of growth o agricultural root crop plants. Invention provides enhancing productivity of root crops beet and carrot and expanding assortment of agents for this designation.

EFFECT: valuable agricultural properties of agent.

1 tbl, 2 ex

FIELD: organophosphorus compounds, chemical technology.

SUBSTANCE: invention relates to technology of organic substances, in particular, to the improved method for preparing copper (II) bis-(1-hydroxyethane-1,1-diphosphonate (1-)). The final copper (II) bis-(1-hydroxyethane-1,1-diphosphonate (1-)) is prepared by crystallization from aqueous solution with concentrations of copper salt (II) from 0.5 to 2.0 mole/l and 1-hydroxyethane-1,1-diphosphonic acid with concentration from 2.0 to 6.0 mole/l prepared by using copper-containing waste in galvanic and electronic engineering manufacture, or by using a semi-finished product from production of 1-hydroxyethane-1,1-diphosphonic acid. Invention provides reducing cost in production of copper (I) bis-(1-hydroxyethane-1,1-diphosphonate (1-)) in combination with retaining purity, expanded raw base for preparing the end product and utilization of manufacture waste.

EFFECT: improved preparing method.

9 cl, 1 tbl, 8 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing N-phosphonomethylglycine. Invention describes a method for preparing N-phosphonomethylglycine from an aqueous mixture containing dissolved N-phosphonomethylglycine, ammonium halides, alkali or earth-alkali metal halides and, optionally, organic impurities. Method involves (a) using a mixture with pH value from 2 to 8; (b) separation of mixture is carried out on a selective nanofiltration membrane, and retentate enriched with N-phosphonomethylglycine and depleted with halides and permeate depleted with N-phosphonomethylglycine are obtained, and (c) N-phosphonomethylglycine is isolated from retentate. Method provides preparing N-phosphonomethylglycine in simultaneous separation of halide salts.

EFFECT: improved preparing method.

13 cl, 5 dwg, 2 tbl, 2 ex

FIELD: organic chemistry, medicine.

SUBSTANCE: disclosed are bis(oxymethyl)phosphinic acid salt of formula I and method for production thereof.

EFFECT: antituberculosis agent of decreased toxicity without losses of therapeutic activity.

3 cl, 3 dwg, 9 tbl, 1 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing -amino-4-[hydroxy(methyl)phosphinyl]butyric acid of the formula (I): wherein R* means hydrogen atom or alkyl with 1-4 carbon atoms, or its salts with acid and bases. Method involves the following stages: a) (stage 1) trivalent methylphosphorus compound of the formula (II): wherein R1 and R2 mean independently halogen atom, (C1-C18)-alkoxy-, benzyloxy- or phenoxy-group that can be substituted, or one radical among R1 or R2 means hydroxy-group is subjected for interaction with unsaturated aldehyde or ketone of the formula (III): wherein R* has the abovementioned value in the presence of carboxylic acid anhydride and if necessary alcohols; b) (stage 2) the reaction mixture obtained at stage 1 is treated with ammonia/ammonium chloride and sodium cyanide, or with a mixture consisting of ammonia and hydrocyanic acid, or with a mixture consisting of ammonia and cyanide, if necessary, in the presence of ammonium chloride, and c) (stage 3) the reaction mixture obtained at stage 2 is hydrolyzed. The proposed method provides enhancing yield of compound of the formula (I) from 50% (by the known method) to 90%.

EFFECT: improved preparing method.

8 cl, 7 ex

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention proposes (aminopropyl)methylphosphinic acids of the general formula (I): with exception of the following compounds: (1) (3-amino-2-hydroxypropyl)methylphosphinic acid racemate; (2) (S)-(3-amino-2-hydroxypropyl)methylphosphinic acid; (3) (R)-(3-amino-2-hydroxypropyl)methylphosphinic acid; (4) (3-amino-2-hydroxypropyl)difluoromethylphosphinic acid, and (5) (3-amino-2-oxopropyl)methylphosphinic acid showing affinity to one or more GABAe (γ-aminobutyric acid) receptor. Also, invention proposes their pharmaceutically acceptable salts, solvates and stereoisomers, and pharmaceutical compositions comprising indicated therapeutically active compounds and using indicated compounds for aims of therapy.

EFFECT: valuable medicinal properties of compounds and compositions.

12 cl, 15 ex

FIELD: chemistry of organophosphorus compounds, medicine, pharmacy.

SUBSTANCE: invention relates to new compounds of the formula (1) showing affinity to one or more GABAB receptors and their pharmaceutically acceptable salts, solvates and stereoisomers but with exception for racemate of (3-amino-2-hydroxypropyl)-phosphinic acid. Invention provides increasing the therapeutic index value.

EFFECT: improved and valuable properties of compounds.

14 cl, 1 tbl, 21 ex

The invention relates to derivatives of phosphinic and phosphonic acids of the formula (I)

where R1means unsubstituted or substituted phenyl, -O-(C1-C6)-alkyl, R2means hydrogen, RR3mean hydrogen, alkyl, unsubstituted or substituted phenyl, COOH group or - (CH2)2-CH(COOH)-NH-SO2-C6H4-C6H4-Cl(n), t stands for an integer of 1-4, And is a covalent bond, X is a group-CH=CH -, - group,- (CH2)about- where is 0,1,2 or 3, Y1and Y2mean-OH, -(C1-C4)-alkyl, -O-(C1-C4)-alkyl, and/or their stereoisomeric forms and/or physiologically acceptable salts

The invention relates to new compounds which can be used as inhibitors of matrix metalloprotease, in particular interstitial collagenases, and which is effective for the treatment of painful condition caused by excessive activity of matrix metalloprotease

The invention relates to heterocyclic chemistry and organo-phosphorus compounds, namely melamine salt of bis(oxymethyl)phosphinic acid of formula I (hereinafter referred to as Melafen") and how you can get it

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The specified connection is a regulator of growth and development of plants and may find application in agriculture and horticulture

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention relates to using phenylethenyl- or phenylethynyl-derivatives as antagonists of glutamates receptors. Invention describes using compound of the general formula (I):

wherein each among R1, R2, R3, R4 and R5 means independently of one another hydrogen atom, (C1-C6)-alkyl, -(CH2)n-halogen, (C1-C6)-alkoxy-group, -(CH2)n-NRR', -(CH2)n-N(R)-C(O)-C1-C6)-alkyl, phenyl or pyrrolyl that can be unsubstituted or substituted with one or more (C1-C6)-alkyl; each among R, R' and R'' means independently of one another hydrogen atom or (C1-C6)-alkyl; A means -CH=CH- or C≡C; B means ,, , , or wherein R6 means hydrogen atom, (C1-C)-alkyl, -(CH2)n-C(O)OR, or halogen atom; R7 means hydrogen atom, (C1-C6)-alkyl, -(CH2)n-C(O)OR', halogen atom, nitro-group or oxodiazolyl group that can be unsubstituted or substituted with (C1-C6)-alkyl or cycloalkyl; R8 means hydrogen atom, (C1-C6)-alkyl, -(CH2)n-OH, -(CH2)n-C(O)OR'' or phenyl; R9 means (C1-C6)-alkyl; R10 and R11 mean hydrogen atom; R12 means -(CH2)n-N(R)-C(O)-(C1-C6)-alkyl; R13 means hydrogen atom; each R14, R15, R16 and R17 independently of one another means hydrogen atom or (C1-C6)-alkoxy-group; each R18, R19 and R20 independently of one another means hydrogen atom; R21 means hydrogen atom or (C1-C6)-alkyl; R22 means hydrogen atom, (C1-C6)-alkyl or (C1-C6)-alkyl comprising one or more substitutes chosen from groups hydroxy- or halogen atom; R23 means hydrogen atom, (C1-C6)-alkanoyl or nitro-group; each among R24, R25 and R26 independently of one another means hydrogen atom or (C1-C6)-alkyl; n = 0, 1, 2, 3, 4, 5 or 6; X means -O- or -S-; Y means -CH= or -N=, and its pharmaceutically acceptable salts used in preparing medicinal agents designates for treatment or prophylaxis of disorders mediated by mGluR5-receptors. Also, invention describes compounds of the formula (I-A), compound of the formula (I-B-1) given in the invention description, and a medicinal agent used in treatment or prophylaxis of disorders mediated by mGluR5-receptors.

EFFECT: valuable medicinal properties of compounds.

44 cl, 1 tbl, 44 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to derivatives of adamantine, in particular, to a new method for preparing adamant-1-yl-containing azoles of the general formula I-VIII: wherein R1 means ; R2 means ; R3 means ; R4 means ; R5 means ; R6 means ; R7 means , and R8 means . Indicated derivatives of adamantine are semifinished products used in synthesis of biologically active substances. Proposed method for preparing these compounds involves using a new method for synthesis of adamant-1-yl-containing azoles that includes the addition reaction of azoles: 2-methylimidazole, 3(5)-methylpyrazole and 4-methylpyrazole, 3,4-dinitropyrazole, 1,2,4-triazole, 3-methylpyrazole, 3-nitro-1,2,4-triazole and 5-methyltetrazole to 1,3-dehydroadamantane in the mole ratio of 1,3-dehydroadamantane to azole = 1:1 in diethyl ether medium at temperature 100°C for 4-5 h.

EFFECT: improved preparing method.

8 ex

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