Method of obtaining highly fluorinated carboxylic acids and their salts

FIELD: chemistry.

SUBSTANCE: invention relates to a method of obtaining highly fluorinated carboxylic acids and their salts, as well as substances-precursors, which includes an impact on a highly fluorinated olefin, which has the general formula (I): Rf-(O)n-(CF2)m-CF=CF2 of a formic acid derivative in accordance with the general formula (II): HCOR in the presence of a radical initiator to form a substance-precursor of carboxylic acid in the form of O-ethers, S-ethers or an amide adduct of the general formula (III): Rf-(O)n-(CF2)m-CFH-CF2-COO and, optionally, in case of an acid obtaining, hydrolysis of an adduct of formula (III) to form carboxylic acid or its salts with the general formula (IV): Rf-(O)n-(CF2)m-CFH-CF2-COO-M+, where in formulas (II) and (III) R represents a residue O-M+, S-M+, OR' or SR' or NR'R", where R' and R" are independent on each other linear or branched or cyclic aliphatic residues, which contain at least one carbon atom and which do not have an alpha-H-atom, where the alpha-H-atom represents a hydrogen atom, bond with a carbon atom, bound with O, S or N in groups OR', SR' or NR'R", and where in formulas (I), (III), (IV) Rf represents H, either a perfluorinated or fluorinated linear or branched alkyl residue which can contain one or several catenary oxygen atoms, and n constitutes 1 or 0, m represents a number from 0 to 6, and M+ represents a cation.

EFFECT: method makes it possible to obtain target compounds with the high output.

8 cl, 7 ex

 

Scope

This information relates to a method for producing vysokotirazhnyh carboxylic acids and their salts.

Prior art

Vysokopetrovsky carboxylic acids useful as emulsifiers in the polymerization of an aqueous emulsion of fluorine-containing monomers. In the past, were used for this purpose perfluorinated low molecular weight carboxylic acids of the General formula CF3-CF2-COO-M+where M+is a cation and n is an integer from 4 to 8.

However, for various reasons, began to arouse the interest of alternative fluorinated emulsifiers that are more legaliseerimise.

Fluorinated polyether carboxylic acids and partially fluorinated carboxylic acids have been proposed as alternative emulsifiers. In particular, vysokopetrovsky pcoralcalciumonline acid of the General formula [Rf-0-L-COO-]-Xi+described in (U.S. Patent No. 2007/0015937 issued to Hintzer, etc.) where L is alkylenes group or groups of aliphatic hydrocarbons, Rfrepresents a linear partially or fully fluorinated aliphatic group interrupted by one or more oxygen atoms, Xi+represents a cation with a valence of i, p�eacham i equals 1, 2 or 3; as a result, these acids have been found useful alternatives to the commonly used perfluorinated alkane acids.

To prepare data vysokotirazhnyh carboxylic acids have been described various ways. For example (Patent application U.S. No. 2006/0281946 for Morita, etc.), describes a process based on the reaction of the disclosure cycle tetrafluroethane to create acid fluoride, which is then converted to a carboxylic acid. However, this process is cumbersome and involves a different response. In the patent application U.S. No. 2007/0025902 filed by Jintara, etc., describes the preparation of fluorinated carboxylic acids from alcohols, using strong oxidants such as RuO4, OsO4, permanganates or oxides of chromium (VI). Although this reaction can be successfully implemented on an industrial scale with getting good income, residues of heavy metals resulting from oxidizing agents should be avoided for environmental reasons, which makes the process expensive. Thus, there is a need to develop alternative way to get vysokotirazhnyh carboxylic acids.

Summary of the invention

The researchers found that the fluorinated carboxylic acids can be easily p�obtained by radical addition of derivatives of formic acid to fluorinated ethylene hydrocarbons, with subsequent hydrolysis of the obtained adduct. The reaction may be conducted in the form of a one-step reaction carried out in one reaction vessel without isolation of intermediates. The methods provided herein, does not require the use of heavy metals and thus are environmentally friendly. The methods presented here allow us to produce acid in sufficient quantities even at moderate temperatures and, thus, are also economical.

Thus, he proposed a method of producing vysokotirazhnyh carboxylic acids and their salts and their precursors, including the impact on vysokoporodistye olefins with the General formula (I):

derivatives of formic acid in accordance with the General formula (II):

in the presence of a radical initiator and the intensification of radical initiators to the formation of O-ester, S-ester or amide adduct with the General formula (III):

and possibly, if the acid was obtained by hydrolysis of the adduct having the formula (III), with the formation of carboxylic acids or its salts with the General formula (IV):

where in the formulae (II) and (III) R represents the residue of O-M+ , S-M+, OR' or SR' or NR'R" where R' and R" are independent from each other linear or branched or cyclic aliphatic or aromatic residues, which contain at least one carbon atom and which do not have alpha-N-atom, a Rfrepresents H or perforated or partially fluorinated, linear or branched, aliphatic or aromatic carbon atoms containing residues or hydrogen, n is 1 or 0; t is a number from 0 to 6, and M+represents a cation including N+.

A detailed description of the invention

Before a detailed description of plans for the implementation of this invention it should be borne in mind that the invention is not limited in its application only by the details set forth in the following description. The invention may have other embodiments of and implemented or carried out in various ways.

In addition, it should be understood that the phraseology and terminology used herein is used for descriptive purposes and should not be construed as limiting. Unlike the use of "containing" terms that are designed to limit, the terms with the meaning of "including", "containing", "including" or "having" and not p�rednaznachenie for limiting and are intended to encompass the items listed thereafter and equivalents) and additional concepts. The term "comprising" is used to refer to the items listed below (or their equivalents), but not any additional concepts. The use of any English indefinite articles in the original text is intended to encompass one or more concepts. Any numerical range, shown here, is designed to shorten and open inclusion of all values from the lower value to the upper value of the range. For example, the range of concentrations from 1% to 50% is intended to reduce obvious and include all values between 1% and 50%, such as, for example, 2%, 40%, 10%, 30%, 1,5%, 3, 9% and so on. The methods presented herein allow for the synthesis of fluorinated carboxylic acids by the General formula (IV):

Rf(O)n-(CF2)m-CFH-CF2-COO-M+(IV)

Where n matches� 1 or 0, m represents an integer from 0 to 6 (for example, 1, 2, 3, 4, 5 and 6) and Rfrepresents H or perfluorinated or partially fluorinated, linear or branched, aliphatic or aromatic carbon atoms containing residues or hydrogen, n is 1 or 0; t is a number from 0 to 6, and M+represents a cation including N+. The term "perfluorinated" means that all hydrogen atoms in the residue substituted by fluorine atoms. For example, the remains of the F3C or F3C - 0 are perfluoromethylvinyl or perfluoromethylene residues. Usually Rfrepresents a linear or branched alkyl residue which may contain one or more catenary oxygen atoms. Catenary oxygen atoms are oxygen atoms interrupting the carbon-carbon chain alkyl residues.

Examples for Rfinclude, but are not limited to these choices, perfluorinated alkyl, perfluorinated oxoalkyl, perfluorinated polyoxyalkylene, partially fluorinated alkyl, partially fluorinated oxoalkyl, partially fluorinated polyoxyalkylene residues that may be linear, cyclic or branched. Typically, Rfmay contain from 1 to 14 carbon atoms. Specific Prim�ry R finclude, but are not limited to these choices, F3C-, F3CO-, F3CFHC-, F5C2-, F3COF2C-, F3COF2CO-, F7C3-, F9C4-, F11C5-, -F2HC.

Other examples include balances:

Rf-O-(CF2)n'-,

Rf-(CF2)n'-,

Rf-(O-CF2)n'-,

Rf-(O-CF2-CF2)n'-,

Rf-(O-CF2CF(CF3)n'-,

Rf-(O-CF(CF3)-CF2)n'-,

where Rfrepresents H or perfluorinated or partially fluorinated, linear or branched, aliphatic or aromatic carbon atoms containing residues or hydrogen, n is 1 or 0; t is a number from 0 to 6, and M+represents a cation including N+and containing from 1 to 12 carbon atoms, and one or several catenary oxygen atoms and where n'represents 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

Rffor the most part is an F3C-, F3COF2C-, F7C3-, F9C4-, -F11C5.

M+in the formula (IV) represents the H+(in the case of formation of the free acid) or cations, such as, for example, not limited to these choices, the metal cations or organic cations (in case the acid before�provided in the form of its salts). Cations of metals include, but are not limited to these choices, Na+ and K+. Organic cations include, but are not limited to these choices, ammonium (NH4+), alkylammoniums, alkylphosphoniums and so on.

These acids and their salts can be obtained by radical addition of derivatives of formic acid to the fluorine-containing olefins or olefin ether having the General formula (I):

In the formula (I), n, m and Rfhave the same meaning as described above in connection with Formula (IV). It is implied that these units do not change during the reaction and, therefore, the choice of Rfn and m from the source material (I) are the same as in the final reaction product (IV).

Derivatives of formic acid are those in which the group HE formic acid (SOON) was substituted by a group R. Thus, derivatives of formic acid can be represented by the General formula HCOR (II).

It is understood that in formula (II) represents a carbonyl group, and not the ester group. The group R in the formula (II) are groups Of+M-, S-M+, OR'SR'and NR'R"where M+represents a cation identical to that described above in regard to M+in the formula (IV). R'and R"may be identical or different and R�ablaut a, independently from each other, a linear, cyclic or branched, aromatic or aliphatic residues which contain at least one carbon atom and in which the balance does not have alpha-N-atom. Alpha-N-atom represents a hydrogen atom that is bound to a carbon atom that is associated with the atoms O, N or S in groups OR'SR'and NR'R"respectively.

Residues R'and R"for the most part, represent a branched alkyl group, such as, for example, tert-butyl (TBU - tBU), isopropyl (IPR - iPr) or adamantylamine group or alkyl group, such as halogen alkali, the alkoxylic one alkali, sulfonylurea alkali or combinations thereof, for example but not limited to these choices, -CCl3, -SO2-R'"where R'"is alkyl (e.g. tert-butyl or halogenoalkane group (such as, for example, a group of CF3).

For the most part, options include R - O - TBU, - O - IPR, -O-adamantyl, - O - CCl3That Oh - SO2CF3, -O-SO2-OTB, -O-Na+and O-K+

To achieve the radical addition of the radical initiator is added to the initial material. The most suitable radical initiators are compounds which decompose to form radicals. Decomposition can be initiate�ANO, for example, thermally or IR - and UV-irradiation or actinic radiation, which is known in the art.

Useful radical initiators or photoinitiators include, for example, those known as useful in actinic method, the irradiation or electron beam irradiation compositions cross-linked, containing the ethylene-unsaturated monomers. Such initiators include benzophenone and its derivatives, benzoin, alpha-methylbenzoyl, alpha feiveson, alpha allylbenzene, alpha benzylbenzoate and benzinovie esters, such as benzyldimethylamine (sold under the trademark "IRGACURE™ 651" (IRGACURE™ 651) Ciba Specialty Chemicals Corporation, Tarrytown, NY), antinomy methyl ester, antinomy ethyl ether, antinomy n-butyl ether, acetophenone and its derivatives, such as 2-hydroxy-2-methyl-1-phenyl-1-propanone (sold under the trademark "DAROKAR™ 1173" (DAROCUR™ 1173) manufactured by Ciba Specialty Chemicals Corporation) and 1-phenylhydroxylamine phenylketone (sold under the trademark "IRGACURE™ 184" (IRGACURETM184), and also from Ciba Specialty Chemicals Corporation); 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, under the trademark "IRGACURETM907" (IRGACURE™ 907) also produced by the company Ciba Specialty Chemicals Corporation), 2-benzyl-2-(dimethylamino)-L-[4-(4-morpholinyl) phenyl]-l-butanone sales �commercial brand "ONGAKU TM369" (IRGACURETM369) manufactured by Ciba Specialty Chemicals Corporation), aromatic ketones such as benzophenone and its derivatives, and anthraquinone and its derivatives; onium salts such as salts of diakonia, salt iodine, sulfonate salts, titanium complexes, such as, for example, compounds that are commercially available under the trademark "CGI™ 784 DC", also produced by the company Ciba Specialty Chemicals Corporation); geometricshapes; and, finally, mono - and bis - allfashion, similar to those available in production by the company Ciba Specialty Chemicals Corporation under the trademarks " IRGACURETM1700" (IRGACURETM1700)," IRGACURETM1800" (IRGACURETM1800), " IRGACURETM1850" (IRGACURETM1850), "IRGACURETM819", "IRGACURETM2005", "IRGACURETM2010 "," IRGACURETM2020 "and" DAROCURTM4265 ". Can be used in combination of two or more photoinitiators. Examples include a mixture of benzophenone with IRGACURETM184 (IrgacureTM184), commercially available under the trade name " IRGACURETM500" (IRGACURETM500).

Useful thermal initiators include azo-compounds such as azobisisobutyronitrile (ABBN), azo-2-cyanovalerianic acid, etc., hydroperoxides, such as cumene hydroperoxide, tert-butyl and tert-amyl hydroperoxides, valkirye pen�seeds, such as di-tert-butyl-and dicumylperoxide, paroxetine, such as T-butylperbenzoate and di-tert-butylperoxide, t-amyl peroxypivalate, diazepamonline, such as benzoyl peroxide and peroxide lauroyl. Preferred thermal initiators are initiators and of these initiators are preferred are those that can be activated (i.e. those which decompose to form radicals) at moderate temperatures, preferably at a temperature of about 40°C and 100°C.

The action of the radicals may also be initiated electrochemically, for example, in the electrochemical cell, and in this case, the radicals formed using a high voltage. The initiators can also be chemical radicals, or redox systems such as, for example, nitroxyl radicals, such as TEMP.

The amount of radical initiator will depend on the particular reaction. Typically, a suitable concentration of the initiator, typically ranges from about 0.5 to about 40%, preferably from 5 to 15% (mol) and the unsaturated ether. The radical initiators may be added at once, continuously, or periodically, for example, in divided doses over a specified period of time. Instead of a single initiator can be used, or some combination of the initiator�in, or different initiators can be used at different times.

Derivatives of formic acid are generally used in a molar excess relative to the unsaturated ether. Generally, derivatives are used in a 3-5-fold molar excess. In the cases where derivatives are used as reagents and solvents, the molar excess can be much more.

Further, the reaction can be carried out without using a solvent, although a solvent may also be used. Typical solvents include polar organic solvents and/or water and its combination. Suitable solvents include, for example, acetonitrile, dimethylsulfoxide, fumarate and the like, which can be used by including in the aqueous solution. The ratio of water to solvent that can be mixed with water (for example, N2A:acetonitrile), at a ratio of from 1:1 to 4:1, preferably in a ratio of 1.5:1 based on volume, was considered appropriate. It is also assumed that the reaction can be carried out with the use of supercritical fluids (for example, soluble concentrate WITH2) or ionic liquids.

The reaction conditions are selected depending on the type of initiator and they must ensure that the activation of a radical initiator. After the act�Vali reaction, as a rule, is carried out at moderate temperatures, typically in the range between 30°C and 100°C. Preferably, the use of radical initiators that can be thermally activated at a temperature between 30°C and 100°C to save energy costs low. The reaction time usually takes from 6 to 24 hours. The reaction can be carried out at ambient pressure or elevated pressure, for example, when the gaseous olefins are used as reagents. Radical addition of a derivative of formic acid to unsaturated fluorinated ether leads to the appearance of precursors of carboxylic acids. Depending on the type of the derivative of formic acid, the precursor may be (oxygen) ether, thioether or amide. Typically, precursors correspond to the General formula:

Rf-(O)n-(CF2)m-CFH-CF2-COR(III),

in which n, m and Rfdetermined by OPI�specified above. It is clear that Rfn and m used in the starting compounds (unsaturated ester), will remain unchanged throughout the reaction.

Substance-precursors can be isolated by known methods of preparative chemistry, such as, for example, distillation. Typically, substance precursor is directly converted into carboxylic acids or their corresponding salts without their separation due to the hydrolysis in a mixture used in the reaction. Usually this can be achieved by adding the base. As a rule, can be used aqueous solutions of bases, such as sodium hydroxide or potassium hydroxide.

Obtained by reaction of the acid can be selected by adjustment of the acid in its free acid form (by sufficient reduction of the pH, if necessary), the release of acids formed during the aqueous phase, and purification by distillation. You can also extract acid with not water-miscible organic solvents. Esters are formed as reaction products may also be separated from the reaction medium by means of fractional distillation. The advantage of open at the moment reaction is that it can be carried out as a one-step reaction carried out in one reaction vessel without isolation of the intermediate compounds�eny. The methods presented herein do not require the use of heavy metals and thus are environmentally friendly. The methods presented here allow to obtain a good yield of acids, for example more than 50%, more than 70% or even 80% (depending on the molar mass of the olefin used as the reagent). Such an output can be obtained even at moderate temperatures (for example between 30°C and 100°C).

The following examples are intended to further illustrate the invention, but in any case not intended to limit it.

Reagents and chemicals

TAPPI-75-AL = t-amyl peroxypivalate 75% solution in alfatah (decision of the American chemical society No. 029240-17-3; (Degussa Initiators, Pullach, Germany: directionalities 125-C75, product code 436321).

PERKADOX 16S = 96% di (4-tert-butylcyclohexyl) PEROXYDICARBONATE (decision of the American chemical society No. 015520-11-3, Akzo Nobel, product code 661041).

TRIGONOX 21S = 99% Astor tert-BUTYLPEROXY-2-ethylhexanoate (decision of the American chemical society No. 003006-82-4; Akzo Nobel; product code 658151).

MV-31=1,1,2,2,3,3-hexaplar-1 triptoreline-3-triptoreline-propane (LLC "Dineen", Burgkirchen).

MA-31=1,1,2,3,3-pendaftar-3-[l,1,2,2,3,3-hexaplar-3- (Triptoreline) propoxy] prop-1-ene (LLC "�Inon, Burgkirchen).

DONA=2,2,3-Cryptor-3-[1,1,2,2,3,3-hexaplar-3-(triptoreline) propoxy] propane acid (LLC "Dineen", Burgkirchen).

t-butyl Formate (decision of the American chemical society No. 762-75-4;. Fluka, category room 06513).

Sodium formate (decision of the American chemical society No. 141-53-7, Sigma Aldrich 71541).

Measurements

Measurements using nuclear magnetic resonance1N was performed using a raster graphics Bruker (Bruker) 200 MHz operating at 200, 13 MHz for AMG-1H (thulium - TMS) and 188,31 MHz to19F AMG (CFCl3).

Example 1:

Tert-butyl 2,2,3-Cryptor-3-[1,1,2,2,3,3-hexaplar-3-(triptoreline)propoxy]propanoate CF3OCF2CF2CF2OCFHCF2C(O)OC(CH3)324,90 g (75 mmol) MV-31 were mixed with 76,57 g (0.75 mol) of tert-butyl formate and 3 ml (10.5 mmol) TAPPI-75-AL. The mixture was stirred for 18 h at 60°C. and Then tert-butyl formate isolated from the reaction mixture using 200 mm of a distillation column, and again the resulting product was distilled under vacuum to obtain 23,90 r (55,05 mmol) clear, colorless liquid; boiling point = 94-96°C under a pressure of 75 mm Hg.St. The output is 73%.

Example 2:

Tert-butyl 2,2,3-Cryptor-3-[1,1,2,2,3,3-hexaplar-3-(triptoreline) propoxy] propanoate CF3OCF2CF2CF2OCFHCF C(O)OC(CH3)3

108,37 g (0.33 mole) MV-31 were mixed with 200 g (1,96 mol) of tert-butyl formate and 13 g (a 32.6 mmol) Perkadox 16S. The mixture was stirred for 24 h at a temperature of 52-55°C. Then t - butyl formate isolated from the reaction mixture, and again the resulting product was distilled under vacuum to obtain 131,25 g (0.3 mole) of clear, colorless liquid. The yield was 93%.

Example 3:

Tert-butyl 2,2,3,4,4-pendaftar-4-[1,1,2,2,3,3-hexaplar-3-(triptoreline)propoxy]butanoate CF3OCF2CF2CF2OCF2CFHCF2C(O)OC(CH3)3

18 g (47 mmol) MA-31 were mixed from 25.1 g (0.25 mol) of tert-butyl formate and 2 g (5 mmol) Perkadox 16S. The mixture was stirred for 17 h at a temperature of 55 to 58°C. were Then added 2 g (5 mmol) Perkadox 16S, and the reaction mixture was stirred at the same temperature range for a further 15 h. Tert-butyl formate isolated from the reaction mixture, and again the resulting product was distilled under vacuum to obtain 18.94 g (39,12 mmol) clear, colorless liquid; boiling point = 102°C under a pressure of 75 mm Hg.St. In the obtained product were to be found only traces of the corresponding /so-derivative, see example 6. The yield was 83%.

Example 4:

2,2,3-Cryptor-3-(1,1,2,2,3,3-hexaplar-3-triptoreline-propoxy)-propionic acid CF3OCF2CF2CF2OCFHCF2C(O)OH

To Rast�Ouro 37,1 g (of 0.54 mol) of sodium formate in the mixture, consisting of 200 ml of distilled water and 150 ml of acetonitrile, were added to 60.2 g (181,30 mmol) MV-31 and 8 ml (28 mmol) TAPPI-75-AL. The mixture was stirred for 18 h at a temperature 54-58°C with the outflow, while the temperature of the reaction mixture increased during the formation of the product; an additional 8 ml TAPPI-75-AL and the reaction mixture was stirred at a temperature of 58 to 65°C for 16 hours. In the reaction mixture was added sulfuric acid to pH 1, and the resulting lower phase was separated and washed with 10% sulfuric acid solution three times (3×100 ml). Again the resulting product was distilled under vacuum to obtain 58,82 g (155,30 mol) acid; boiling point = 87,7°C at 15 mm Hg.St. The yield was 85%.

Example 5:

2,2,3-Cryptor-3-(1,1,2,2,3,3-hexaplar-3-triptoreline-propoxy)-propionic acid CF3OCF2CF2CF2OCFHCF2C(O)OH

The reaction described in example 4 was repeated using Trigonox 21S (2×8 g, 74 mmol) in the form of a radical initiator instead TAPPI-75-AL. Trigonox 21S was added in two parts with an interval of 16 hours, the reaction Temperature did not change significantly during the reaction process and preserved between 53-55°C at a constant outflow. The formation of the product was followed by NMR19F.

Example 6:

2,2,3,4,4-Pendaftar-4-[1,1,2,2,3,3-hexaplar-3-(triptoreline) propoxy] butane acid

CF3OCF2CF2CF2OCF2CFHCF2C(O)OH {and

ISO=CF3OCF2CF2CF2OCF2CF(CF2H)-C(O)OH {In}

11 g (162 mmol) of sodium formate were dissolved in a mixture consisting of 67 ml of distilled water and 50 ml of acetonitrile. To this mixture were added to 20.4 g (of 53.4 mmol)MA-31 and 6 ml (21 mmol) TAPPI-75-AL, and the mixture was stirred at 6°C for 24 h. the reaction Products were not isolated. Spectral and gas chromatograms NMR19F to the reaction mixture showed almost quantitative conversion of the source allyl ether and the formation of two acids having isomeric structure: A/b=1,8/1.

Example 7:

2,2,3-Cryptor-3-[1,1,2,2,3,3-hexaplar-3-(triptoreline)propoxy]propanamide CF3OCF2CF2CF2OCFHCF2C(O)NH2

A mixture consisting of 57,32 g (172,63 mmol) MV-31, 150 ml of formamide, 70 ml of acetonitrile and 8,53 ml (29.8 mmol) TAPPI-75-AL, was stirred for 18 h at a temperature of 55 to 57°C. the amide Formation was observed using19F NMR spectrometry and gas chromatography.

1. A method of producing vysokotirazhnyh carboxylic acids and their salts and their precursors, including
impact on vysokopetrovsky olefin having the General formula (I):

the derivative of formic acid in accordance with the General formula (II):

in the presence radikalna� initiator for the formation of the precursor carboxylic acid in the form Of ethers, S-esters or amide adduct of the General formula (III):

and, optionally, in the case of acid hydrolysis of the adduct of formula (III) to form a carboxylic acid or its salts with the General formula (IV):

where in the formulae (II) and (III) R represents the residue of O-M+, S-M+, OR' or SR' or NR'R", where R' and R" are independent from each other linear or branched or cyclic aliphatic residues which contain at least one carbon atom and which do not have alpha-N-atom, where alpha-N-atom represents a hydrogen atom that is linked to a carbon atom linked to O, S, or N in groups OR', SR' or NR'R", and where in formulas (I), (III) and (IV) Rfrepresents H or perfluorinated or fluorinated linear or branched alkyl residue which may contain one or more catenary oxygen atoms, and n is 1 or 0, m is a number from 0 to 6, and M+represents a cation.

2. A method according to claim 1, characterized in that Rfrepresents one of the following:






where Rf'�predstavljaet fluorinated or perforated, linear or branched alkyl residue containing from 1 to 12 carbon atoms, and any one or more catenary oxygen atoms, and where n' is a 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

3. A method according to claim 1, characterized in that Rfcontains from 1 to 12 carbon atoms.

4. A method according to claim 1, characterized in that R represents an-OR', a R' represents a branched alkyl chain or branched halogenating group.

5. A method according to claim 1, characterized in that the hydrolysis is carried out by adding a base.

6. A method according to claim 1, wherein the radical initiator is activated thermally.

7. A method according to claim 6, wherein the radical initiator is activated at a temperature from about 30°to about 100°C.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to efficient method of purifying fluorinated compound, which includes distillation of liquid, which contains, at least, one member, selected from group, consisting of fluorinated compound, represented by the following formula (1), and fluorinated compound, represented by the following formula (2), keeping it at temperature of heating not higher than 150°C, where temperature of heating is internal temperature of distillation column boiler: RFOR1COOH, (1), RFOR1COOR2, (2) in which RF represents fluorinated alkyl group, which can have simple ether atom of oxygen in its main chain, R1 represents perfluoroalkylene group, and R2 represents C1-C3alkyl group, and in which liquid represents liquid obtained from any liquid waste product after coagulation of fluoropolymer water emulsion and separation of fluoropolymer, water liquid, obtained by washing of discharge gas at the stage of drying and/or stage of thermal processing of a separate fluoropolymer, or liquid, obtained by washing with alkali water solution of anion-exchange resin, which was brought in contact with liquid waste product or water dispersion, obtained from fluoropolymer water emulsion.

EFFECT: increased efficiency of purification.

6 cl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to perfection of the method of obtaining alkylsalicylic acids. The method involves reaction of salicylic acid with an olefin, containing at least four carbon atoms, at high temperature in the presence of alkylsulfonic acid as a catalyst. The invention also pertains to a composition for obtaining additives to lubrication oils, containing alkylsalicylic acid obtained using the above mentioned method. The obtained product has low content of alkylphenols and good colour. Its acid number is 60-95% of the theoretical value. The values of the results of PDSC testing (pressure differential scanning calorimetry) and "panel coker" test are comparable with or surpass the corresponding values for the control salicylic detergents produced in the industries.

EFFECT: obtaining a product of alkylation of salicylic acid with low content of alkylphenols and good colour.

20 cl, 12 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of fluorinated ester. The process involves the re-esterification step wherein compound of the formula: RAF-COOCF2-RAF and compound of the formula: RA-CH2OH are subjected for the re-esterification reaction in the molar ratio = 1:(1-2) to yield RAF-COOCH2-RA, and the fluorination step wherein the synthesized compound is fluorinated with yielding the reaction product in the amount exceeding the mole amount before the re-esterification reaction and comprising compound of the formula: RAF-COOCF2-RAF wherein RA means a monovalent (C1-C20)-hydrocarbon group, monovalent halogen-containing (C1-C20)-hydroarbon group, monovalent heteroatom-containing (C1-C20)-hydrocarbon group or monovalent (C1-C20)-hydrocarbon group containing halogen atom and heteroatom, and RAF means the same group as RA group or monovalent hydrocarbon group prepared by fluorination of RA group.

EFFECT: improved method of synthesis.

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for synthesis of ester perfluorinated derivative by using a chemical reaction. This reaction represents the fluorination reaction of the parent compound as a raw, the reaction of chemical conversion of fragment of ester perfluorinated derivative to yield another ester perfluorinated derivative or the interaction reaction of carboxylic acid with alcohol under condition that at least one or reagent, i. e. carboxylic acid or alcohol, represents a perfluorinated compound wherein indicated perfluorinated derivative of ester represents a compound comprising a fragment of the formula (1):

with a boiling point 400°C, not above. The reaction time for carrying out abovementioned chemical reaction is sufficient to provide the required yield of ester perfluorinated derivative and wherein this yield of ester perfluorinated compound is determined by the gas chromatography method by using a nonpolar column. Also, invention relates to a method for pyrolysis of ester perfluorinated derivative with a boiling point 400°C, not above, to yield the dissociation product wherein this product represents a derivative of acyl fluoride or ketone and wherein pyrolysis time is sufficient to provide the required degree of conversion of ester perfluorinated derivative and wherein the indicated conversion degree of ester perfluorinated derivative is determined by gas chromatography method by using a nonpolar column. Also, invention relates to a method for analysis of ester perfluorinated derivative with a boiling point 400°C, not above, that involves analysis of ester perfluorinated derivative in a sample containing ester perfluorinated derivative by gas chromatography method by using a nonpolar column wherein ester perfluorinated derivative represents compound comprising a fragment of above given formula (1).

EFFECT: improved method of synthesis.

8 cl, 1 dwg, 2 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to industrially useful fluorine-containing compounds such as fluorinated ester compounds and acyl fluoride compounds. Invention, in particular, provides ester compound wherein all C-H groups are fluorinated and which is depicted by general formula RAFCFR1FOCORBF (4), where RAF, CFR1, and RBF are specified elsewhere. Preparation of the ester compound comprises fluorination of ester (4), which has hydroxyl group(s), acyl fluoride group(s) and which has a structure allowing compound to be fluorinated in liquid phase, fluorination being effected in mixture of ester compound and compound having acyl fluoride group(s). Method does not involve environmentally unfriendly solvent such as, for instance, R-113.

EFFECT: enabled fluorination requiring no specific solvent for each reaction and which can be carried out without separation of solvent before next stage.

9 cl, 8 ex

FIELD: organic chemistry, in particular polymers.

SUBSTANCE: invention relates to new method for production of vic-dichlorofluoroanhydride useful as intermediate of starting monomer for fluorinated polymers with good yield from available raw material. Claimed method includes fluorination of starting material (I): (RH1-EH1-)CRH2RH3CH2-0CORHB in liquid phase to form compound of formula (II): (CF2ClCFCl-EF1-)CRF2RF3CF2-OCORFB; ester bond splitting of formula (II) in gaseous phase under solvent absence to form compound of formula (III): (CF2ClCFCl-EF1-)CRF2RF3COF or compound of formula (III) and compound of formula (IV): FCORFB, wherein RH1 is CX1X2ClCX3Cl- or CClX4=CCl, wherein each X1-X4 independently is hydrogen; RH2 and RH3 independently are hydrogen or linear or branched alkyl, optionally substituted with one or more oxygen; EH1 is alkylene, optionally substituted with one or more oxygen; EF1 = EH1 wherein perfluoroalkylene group is optionally substituted with one or more oxygen; RHB = RFB and are linear or branched perfluoroalkyl group, optionally substituted with chlorine one or more oxygen; RF2 is fluorinated RH2; RF3 is fluorinated RH3; with the proviso, that RF2 is fluorinated RH2; RF3 is fluorinated RH3, i.e. RF2 and RF3 represent RH2 or RH3 with at least one fluorinated hydrogen. Also disclosed are new compounds, represented in claims of invention.

EFFECT: new intermediates useful in polymer fluorination.

11 cl, 7 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention provides improved process for production of a fluorine-containing compound useful as starting material for manufacture of a variety of fluoropolymers with high output when performing short process and using inexpensive and easily accessible chemicals. Process comprises: (i) interaction of indicated below compound 1 with indicated below compound 2 to form indicated below desired compound 3, which is a compound, wherein content of fluorine is at least 30 wt % and which has hydrogen atom or multiple bond capable of being fluorinated; and (ii) liquid-phase fluorination of compound 3 to give indicated below compound 4 followed by (iii) cleaving group EF in compound 4 to produce compound 5 and compound 6: E1-RA-E1 (1), E2-RB (2), RB-E-RA-E-RB (3),

RBF-EF-RAF-EF-RBF (4), EF1-RAF-EF1 (5),

and RBF-EF2 (6), where RAF represents fluorine-containing bivalent saturated, linear or branched hydrocarbon group optionally containing halogen atom other than fluorine and optionally containing one or several ether oxygen atoms; RA represents group, which is the same as group RAF or bivalent organic group capable of being converted into group RAF using fluorination reaction; RBF represents fluorine-containing polyvalent saturated, linear or branched hydrocarbon group optionally containing halogen atom other than fluorine and optionally containing one or several ether or carbonyl oxygen atoms; RB represents group, which is the same as group RBF or polyvalent organic group capable of being converted into group RBF using fluorination reaction; E1 and E2 are such that, when group E1 is -CH2OH or Q1-CH2OH group, then group E2 is -COX or -SO2X group and, when group E2 is -CH2OH or -Q2-CH2OH group, then group E1 is -COX or -SO2X group, where X is halogen atom and Q1 and Q2 may be identical or different and represent -CH(CH3)- or -CH2CH2- group; E represents group -CH2OCO-, -CH2OSO2-, -Q1-CH2OCO-, -Q2-CH2OCO-, -Q1-CH2OSO2-, or -Q2-CH2OSO2-; EF represents group, which is the same as group E or group obtained by fluorination if group E on conditions that at least one group RAF, RBF, or EF is a group formed by fluorination reaction and groups EF1 and EF2 are groups formed by cleaving group EF. Invention also relates to novel fluorine-containing compounds of formulas 3-12, 3-13, 3-14, 3-15, 3-16, 4-12, 4-13, 4-14, 4-15, 4-16, 5-16, which are indicated in description.

EFFECT: increased resource of raw materials for production of fluoropolymers.

8 cl, 23 ex

The invention relates to the production of fluorine-containing compounds, such as industrial useful derived foramerica acid

The invention relates to new liquid under normal conditions of omega-hygrophoraceae esters, which have the properties of surfactants and can be used to displace water from the surface, in compositions for the removal of pollutant products, compositions for fire extinguishing, foam fabrication, when soldering in the vapor phase

The invention relates to ester compounds, method of their production and their use as a means for spooling the fiber

Organic lubricant // 2514434

FIELD: chemistry.

SUBSTANCE: invention relates to an organic lubricant in form of fine particles of human or animal hair, wherein said lubricant is placed on the friction surface of a rotating disc with a helical groove running from the edge of the disc to the centre with a "no" outlet at the centre and the tail of the disc for performing rotation.

EFFECT: cheap technique of producing organic lubricant material which, owing to tribological properties thereof, considerably reduces stress in surface of layers of friction pairs, provides high adhesion to the friction surface without increasing corrosive wear.

5 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a stereoselective method of obtaining a fluorinated molecule having a fluorine atom with asymmetrical carbon (R) or (S) configuration in the α position relative an ester or ketone group in which: (i) a fluorosulphite compound of given configuration on C* which carries the fluorosulphite group of formula (III) is put into a reactor, (2i) the fluorosulphite compound is thermally decomposed in the presence of a nucleophilic catalyst which contains a tertiary nitrogen atom, at temperature ranging from 60°C to 180°C, (3i) a fluorinated molecule having reverse configuration of formula (IV) is obtained, provided that: -R1 denotes alkyl, alkenyl, alkynyl, where these groups can be straight or branched, aryl, cycloalkyl, alkylcycloalkyl, CO2R5, - (CH2)n-CO2R5, -COR5, -SOR5, -SO2R5, where n is an integer from 1 to 12, R5 denotes hydrogen or alkyl, alkenyl, alkynyl, where these groups can be straight or branched, cycloalkyl, alkylcycloalkyl, aryl, particularly substituted aryl; R1 can also form an aromatic or not a heterocycle containing, instead of one or more carbon atoms, one or more heteroatoms selected from oxygen, sulphur or nitrogen; -R2 denotes hydrogen or a group corresponding to definition given for R1; - R1 and R2 are different; - R3 denotes hydrogen or a R6 or -OR6 group, where R6 is selected a list given for R5; where R6 and R1 can be identical or different.

EFFECT: use of the present method enables to stereoselectively obtain fluorinated molecules with good output using cheap and reagents which do not lead to large amounts of effluent.

40 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of regenerating surfactants based on fluorinated acids or their salt from adsorbent particles on which the said surfactants are adsorbed, based on fluorinated acids, involving saturation of adsorbing particles with surfactants based on fluorinated acids or their salt, washing particles of adsorbent on which the surfactant based on fluorinated acid or its salt is adsorbed with water; mixing particles of the adsorbent on which the surfactant based on fluorinated acid or its salt is adsorbed with alcohol or inorganic acid in the presence of water, initiation of etherification of the said surfactant based on fluorinated acid or its salt with the said alcohol to obtain an ether derivative of the said fluorinated surfactant, distillation of the said mixture to obtain a distillate containing the said ether derivative, separation of the said ether derivative from the said distillate and optional return of the remaining distillate to the said mixture and optional conversion of the said ether derivative to the corresponding surfactant based on fluorinated acid or its salt.

EFFECT: efficient method enables use of minimal amount of regenerating liquid and leads to obtaining regenerated particles of adsorbent which can be used repeatedly.

8 cl, 18 ex

FIELD: chemistry.

SUBSTANCE: invention relates to field of organic chemistry, namely to additives and/or additions to industrial oils, which are mixtures of fluorine-containing esters of compositions [RFC(O)OCH2C(CH2OH)3:(RFC(O)OCH2)2C(CH2OH)2:(RFC(O)OCH2)3CCH2OH :(RF C(O)OCH2)4C] (at RF= C6F13 component ratio equals 5 : 11 : 15 : 69, at RF=ClC8F16 component ratio equals 4 : 10 : 14 : 72, at RF=C3F7OCF(CF3)CF2OCF(CF3) component ratio equals 2 : 8 : 16 : 74 ); [RFC(O)OCH2C(CH2OH)2C2H5 :(RFC(O)OCH2)2C(CH2OH)C2H5 :(RFC(O)OCH2)3CC2H5] (at RF= C3F7 component ratio equals 3 : 8 : 89, at RF= C4F9 component ratio equals 5 : 10 : 85, at RF= C6F13 component ratio equals 4:10:86, at RF = ClC6F12 ratio equals 6 : 12 : 82, at RF= C8F17 component ratio 4 : 9 : 87, at RF = CIC8F16 component ratio equals 3 : 11 : 86, at R = C3F7OCF(CF3)CF2OCF(CF3) component ratio equals 4 : 12 : 84); [RFC(O)OCH2C(CH2OH)(CH3)2 : (RFC(O)OCH2)2C(CH3)2] (where RF = C3F7 component ratio equals 4 : 96, at R = C4F9 component ratio equals 5 : 95, at RF= C6P13 component ratio equals 3 : 97, at R = CIC6F12 ratio equals 2 : 98, at RF = C8F17 component ratio equals 2 : 98).

EFFECT: simplification of industrial oils with additives and/or additions producing, as well as improvement of those antifriction and antiwear properties.

1 cl, 55 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention pertains to perfection of the method of obtaining alkylsalicylic acids. The method involves reaction of salicylic acid with an olefin, containing at least four carbon atoms, at high temperature in the presence of alkylsulfonic acid as a catalyst. The invention also pertains to a composition for obtaining additives to lubrication oils, containing alkylsalicylic acid obtained using the above mentioned method. The obtained product has low content of alkylphenols and good colour. Its acid number is 60-95% of the theoretical value. The values of the results of PDSC testing (pressure differential scanning calorimetry) and "panel coker" test are comparable with or surpass the corresponding values for the control salicylic detergents produced in the industries.

EFFECT: obtaining a product of alkylation of salicylic acid with low content of alkylphenols and good colour.

20 cl, 12 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to chemistry of adamantane derivatives, namely, to a novel method for synthesis of 3-halogen-1-(ethoxycarbonyl)-alkyladamantanes of the general formula: wherein Hal means bromine atom (Br); R means hydrogen atom (H), -CH3, -C2H5, -C3H7; Hal means Br; R means -CH3; R1 means -CH3; Hal means chlorine atom (Cl); R means Cl; R1 means Cl that can be used as intermediate compounds used for synthesis of some biologically active substances. Method involves interaction of 1,3-dehydroadamantane with α-halogenalkane carboxylic acids ethyl esters chosen from the following group: ethyl-2-bromoacetate, ethyl-2-bromopropionate, ethyl-2-bromobutyrate, ethyl-2-bromovalerate, ethyl-2-bromo-2-methylpropionate and ethyl-2,2,2-trichloroacetate taken in the mole ratio = 1:(3-5), respectively, in the parent α-halogenalkane carboxylic acid ethyl esters medium, at temperature 50-60°C for 4-6 h. Invention provides expanding assortment of chemical compounds, in particular, synthesis of novel 3-halogen-1-(ethoxycarbonyl)-alkyladamantanes with the high yield.

EFFECT: improved method of synthesis.

6 ex

FIELD: chemical industry; method of production of the fluorine-containing compounds.

SUBSTANCE: the invention is pertaining to the chemical industry, in particular, to the improved method of production of fluorine-containing compounds from the halogen-containing, compounds, preferably, from chlorine-containing compounds due to an exchange of halogen for fluorine at presence of the HF-additional compound of the mono- or bicyclic amine with at least two atoms of nitrogen. At that at least one atom of nitrogen is built in the cyclic system as the fluorating agent; or at presence of anhydrous hydrogen fluoride - as the fluorating agent and the indicated HF-additional compound of the mono- or bicyclic amine as the catalyst. At usage of the applicable solvents the reaction mixtures can be divided into two phases and thus to simplify the reprocessing of the products. The invention also is pertaining to the HF-additional compounds of 1.5-diazabicyclo[4.3.0]non-5-en and N,N-dialkylaminopiridin, where alkyl represents C1-C4alkyl and where the molar ratio of HF to amine makes 1:1, and to HF- additional compounds 1.8- diazabicyclo[5.4.0]undecyl-7-ene, where the molar ratio of HF to amine compounds more than 1:1.

EFFECT: the invention ensures at usage of the applicable solvents to divide the reaction mixture into two phases and thus to simplify reprocessing of the products.

17 cl, 13 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to a method for preparation of multivalent carbonyl compounds and to a novel polyvalent carbonyl compound, which may be useful, for example, as intermediate in production of various fluorinated compounds. Polyvalent carbonyl compound is prepared through economically advantageous way from inexpensive substances and with no need of using any complex synthesis stage. In particular, polyvalent alcohol, including alcohols with at least two structures selected from primary, secondary, and tertiary structures, is brought into reaction with acid halide to form polyvalent ester, which is then fluorinated in liquid phase to form perfluorinated polyvalent ester, in which ester bonds, provided by reaction with primary and secondary alcohols, are further cleaved.

EFFECT: expanded synthetic possibilities in organofluoric compound area.

8 cl, 3 dwg, 2 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to industrially useful fluorine-containing compounds such as fluorinated ester compounds and acyl fluoride compounds. Invention, in particular, provides ester compound wherein all C-H groups are fluorinated and which is depicted by general formula RAFCFR1FOCORBF (4), where RAF, CFR1, and RBF are specified elsewhere. Preparation of the ester compound comprises fluorination of ester (4), which has hydroxyl group(s), acyl fluoride group(s) and which has a structure allowing compound to be fluorinated in liquid phase, fluorination being effected in mixture of ester compound and compound having acyl fluoride group(s). Method does not involve environmentally unfriendly solvent such as, for instance, R-113.

EFFECT: enabled fluorination requiring no specific solvent for each reaction and which can be carried out without separation of solvent before next stage.

9 cl, 8 ex

FIELD: organic chemistry, in particular polymers.

SUBSTANCE: invention relates to new method for production of vic-dichlorofluoroanhydride useful as intermediate of starting monomer for fluorinated polymers with good yield from available raw material. Claimed method includes fluorination of starting material (I): (RH1-EH1-)CRH2RH3CH2-0CORHB in liquid phase to form compound of formula (II): (CF2ClCFCl-EF1-)CRF2RF3CF2-OCORFB; ester bond splitting of formula (II) in gaseous phase under solvent absence to form compound of formula (III): (CF2ClCFCl-EF1-)CRF2RF3COF or compound of formula (III) and compound of formula (IV): FCORFB, wherein RH1 is CX1X2ClCX3Cl- or CClX4=CCl, wherein each X1-X4 independently is hydrogen; RH2 and RH3 independently are hydrogen or linear or branched alkyl, optionally substituted with one or more oxygen; EH1 is alkylene, optionally substituted with one or more oxygen; EF1 = EH1 wherein perfluoroalkylene group is optionally substituted with one or more oxygen; RHB = RFB and are linear or branched perfluoroalkyl group, optionally substituted with chlorine one or more oxygen; RF2 is fluorinated RH2; RF3 is fluorinated RH3; with the proviso, that RF2 is fluorinated RH2; RF3 is fluorinated RH3, i.e. RF2 and RF3 represent RH2 or RH3 with at least one fluorinated hydrogen. Also disclosed are new compounds, represented in claims of invention.

EFFECT: new intermediates useful in polymer fluorination.

11 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of obtaining alicyclic alcohol of structural formula (III) The method includes obtaining a cyclohexanecarbonyl compound, represented by general formula (II) carbonylation of unsaturated hydrocarbon, represented by general formula (I) with the application of carbon monoxide in the presence of HF with further obtaining alicyclic alcohol, represented by general formula (III), and reduction of the said cyclohexanecarbonyl compound, represented by general formula (II). In structural formulas (I)-(III) R1 represents an alkyl group, containing 1-4 carbon atoms, R2 represents an alkyl group, containing 1-4 carbon atoms, R3 represents an OH group, fluorine or an OR4 group, and R4 represents an alkyl group, containing 1-4 carbon atoms.

EFFECT: method makes it possible to obtain the product with low expenditures, high output and high purity of the cis-form.

11 cl, 2 ex

Up!