TW201326101A - Fluoroalkyl S-(fluoro)alkyl thiocarbonates, a method for the preparation of fluoroalkyl S-(fluoro)alkyl thiocarbonates, and their use - Google Patents

Abstract

Fluoroalkyl S-alkyl thiocarbonates and fluoroalkyl S-fluoroalkylthiocarbonates which are suitable as additives or solvents in lithium ion batteries are prepared from fluoroalkyl fluoroformates and the respective thioalcohol. Methanethiol, allyl thiol and 2, 2, 2-trifluorothiol are the preferred thioalcohol. Fluoromethyl S-methyl thiocarbonate, fluoromethyl S-allyl thiocarbonate, fluoromethyl S-2, 2, 2-trifluoroethyl thiocarbonate and fluoromethyl S-allyl thiocarbonate are the preferred compound to be produced.

Description

Preparation method of fluoroalkyl sulphate S-(fluoro)alkyl ester, fluoroalkyl sulphate S-(fluoro)alkyl ester, and use thereof

The present application claims the priority of the European Patent Application No. 1 117 867 2.9 filed on Aug. 24, 2011, the entire disclosure of which is hereby incorporated by reference.

The present invention relates to a fluoroalkyl thiocarbonate S-(fluoro)alkyl ester for the preparation of a fluoroalkyl sulphate S-(fluoro)alkyl ester (ie, a fluoroalkyl sulphate S-alkyl ester and A fluoroalkyl sulphate S-fluoroalkyl ester, the term in parentheses means a free fluorine substitution, in particular a method of fluoromethyl thiocarbonate-S-methyl ester, and as a solvent The use of additives in Li-ion batteries.

US 6,232,020 B1 describes S-alkyl thiocarbonate as a solvent additive for lithium ion batteries.

It is an object of the present invention to provide a novel additive for a Li ion battery solvent. The present invention has attained a number of objects, including the above and other objects, and in particular, permits the selective manufacture of monofluorinated fluoroalkyl thiocarbonate S-alkyl sulphate and monofluorinated S-fluoroalkyl thiocarbonate. (A method of fluoroalkyl sulphate S-alkyl ester and, in particular, fluoromethyl sulphate S-methyl ester).

One aspect of the invention relates to a fluoroalkyl sulphate S-(fluoro)alkyl ester having the general formula (I): FCHR-OC(O)-SR', wherein R represents H; has from 1 to 5 C atoms a linear or branched alkyl group, CH(CH ₃ )=CH, C(CH ₃ ) ₂ =CH, CH ₂ =CHX, wherein X is CH ₂ , C ₂ H ₄ , or CH=CHY, wherein Y is H, CH ₃ or C ₂ H ₅ ; and R' represents a linear or branched alkyl group having 1 to 7 carbon atoms; a straight having 2 to 7 carbon atoms substituted by at least one fluorine atom A chain or branched alkyl group; CH ₂ =CHX, wherein X is CH ₂ , C ₂ H ₄ ; phenyl; phenyl substituted by one or more C 1 to C 3 alkyl group atoms; a phenyl group substituted with a plurality of chlorine atoms or fluorine atoms; or a benzyl group.

R is preferably H, allyl, methyl, ethyl or isopropyl.

Preferably, R' represents a C1 to C5 alkyl group, an allyl group or a 2,2,2-trifluoroethyl group.

Preferably, R' is methyl, ethyl or n-propyl, isopropyl, propenyl or 2,2,2-trifluoroethyl.

The most preferred compounds are: fluoromethyl sulphate S-methyl ester, sulphuric acid alpha-fluoroethyl ester S-methyl ester, fluorocarbonic acid fluoromethyl ester S-2, 2, 2-trifluoroethyl Base ester, α-fluoroethyl sulphate, S-2,2,2-trifluoroethyl ester, and fluoromethyl sulphate S-allyl ester.

Another aspect of the invention relates to a process for the manufacture of a fluoroalkyl thiocarbonate S-(fluoro)alkyl ester having the general formula (I): FCHR-OC(O)-SR', wherein R represents H; a linear or branched alkyl group of 5 C atoms, CH(CH ₃ )=CH, C(CH ₃ ) ₂ =CH, CH ₂ =CHX (wherein X is CH ₂ , C ₂ H ₄ ), or CH=CHY (wherein Y is H, CH ₃ or C ₂ H ₅ ); and R' represents a linear or branched alkyl group having 1 to 7 carbon atoms; having 2 to 2 substituted by at least one fluorine atom a linear or branched alkyl group of 7 carbon atoms; CH ₂ =CHX (wherein X is CH ₂ , C ₂ H ₄ ); phenyl; substituted by one or more C1 to C3 alkyl group atoms a phenyl group, or a phenyl group substituted with one or more chlorine atoms or fluorine atoms; or a benzyl group. The method comprises the steps of: fluoroalkyl fluoroformate having the formula (II), FCHROC(O)F, Or a fluoroalkyl chloroformate having the formula (II'), FCHROC(O)Cl, is reacted with a thiol having the formula (III), R'SH, wherein R and R' have the meanings given above, Or the method comprises the steps of: subjecting a fluorine having the formula (IV), ClCHROC(O)F A chloroalkyl acrylate or a chloroalkyl chloroformate having the formula (IV'), ClCHROC(O)Cl, wherein R has the meaning given above, and a sulphur having the formula (III), R'SH An alcohol wherein R' has the meaning given above, carries out the reaction, and subsequent chlorine-fluorine exchange.

Preferably, the process according to the present invention provides a process for the manufacture of a fluoroalkyl thiocarbonate S-(fluoro)alkyl ester having the general formula (I), FCHR-OC(O)-SR', wherein R represents H or a linear or branched alkyl group having 1 to 5 C atoms, and R' represents a linear or branched alkyl group having 1 to 7 carbon atoms; substituted by at least one fluorine atom a linear or branched alkyl group having 2 to 7 carbon atoms; allyl group; phenyl group; phenyl group substituted by 1 or more C1 to C3 alkyl group atoms, or 1 or more chlorine groups Or a phenyl group substituted with a fluorine atom; or a benzyl group The manufacturing method comprises the steps of: fluoroalkyl fluoroformate having the formula (II), FCHROC(O)F, or a fluoroalkyl chloroformate having the formula (II'), FCHROC(O)Cl Reacting with a thiol having the formula (III), R'SH, wherein R and R' have the meanings given above, or the method of manufacture comprises the steps of: having the formula (IV), ClCHROC (O) a chloroalkyl fluoroformate or a chloroalkyl chloroformate of the formula (IV'), ClCHROC(O)Cl, wherein R has the meaning given above, and has the formula (III), R A thiol of 'SH, wherein R' has the meaning given above, carries out the reaction, and a subsequent chloro-fluorine exchange.

A particularly preferred embodiment of the present invention provides a process for the manufacture of a fluoroalkyl thiocarbonate S-(fluoro)alkyl ester having the general formula (I): FCHR-OC(O)-OR', wherein A process for producing a fluoroalkyl thiocarbonate S-(fluoro)alkyl ester of the formula (I), FCHR-OC(O)-SR', wherein R represents a linear or 1 to 5 C atom Branched alkyl, CH(CH ₃ )=CH, C(CH ₃ ) ₂ =CH, CH ₂ =CHX (where X is CH ₂ , C ₂ H ₄ ); and R' represents 1 to 7 carbons a linear or branched alkyl group of an atom; an allyl group; a linear or branched alkyl group having 2 to 7 carbon atoms substituted by at least one fluorine atom; a phenyl group; one or more a phenyl group substituted with a C1 to C3 alkyl group atom, or a phenyl group substituted with one or more chlorine or fluorine atoms; or a benzyl group comprising the steps of: a compound of formula (II), FCHROC(O)F Fluoroalkyl fluoroformate, or a fluoroalkyl chloroformate of formula (II'), FCHROC(O)Cl, reacted with a thiol of formula (III), R'SH, wherein R and R 'has the meaning given above.

The term "(fluoro)alkyl" preferably denotes an alkyl group consisting of having the structure CH(CH ₃ )=CH, C(CH ₃ ) ₂ =CH, CH ₂ =CHX (where X is a single a group substituted with a group of a bond, CH ₂ , or C ₂ H ₄ ); a propenyl group of the formula CH ₂ =CHX wherein X is CH ₂ , C ₂ H ₄ ; and substituted by at least one fluorine atom Alkyl group. Accordingly, the present invention provides a monofluoro-substituted fluoroalkyl sulphate S-alkyl ester and a fluoroalkyl sulphate S-fluoroalkyl ester, wherein one fluoroalkyl group is monosubstituted and the other fluoroalkyl group It may be substituted by one or more fluorine atoms. In the fluoroalkyl thiocarbonate S-fluoroalkyl ester, the fluoroalkyl groups may be the same or different, and at least one of the fluoroalkyl groups is monofluorinated.

Instead of or in addition to the thiol, a corresponding alkali metal thiolate, for example a corresponding lithium, sodium, potassium or cesium thiolate, may be employed. It is preferred to produce a thiocarbonate wherein R represents a C1 to C3 alkyl group, CH ₂ =CH-CH ₂ , CH(CH ₃ )=CH, C(CH ₃ ) ₂ =CH, or H, and more preferably Yes, C1 to C3 alkyl or H.

Particularly preferred R in the thiocarbonate is H. According to this preferred embodiment, there is provided a process for the manufacture of a fluoroalkyl sulphate S-(fluoro)alkyl ester, the process comprising the steps of: fluoromethyl fluoroformate or chloroformic acid fluoride The methyl ester is reacted with a thiol or, in an alternative, the chloromethoxy chloroformate is reacted with a thiol and a subsequent chlorofluoro exchange is carried out. It is especially preferred to use fluoromethyl fluoroformate having the formula FCH ₂ -OC(O)F.

The present invention will now be explained in detail with respect to this preferred alternative (i.e., the preparation of a fluoroalkyl sulphate S-(fluoro)alkyl ester with fluoromethyl fluoroformate and a thiol); again in this embodiment In this case, the thiol may be partially or wholly replaced by a corresponding alkali metal thiolate (for example, a thiol of lithium, sodium, potassium or rubidium). The thiol preferably means a C1 to C5 thiol; a C2 to C5 thiol substituted with at least one fluorine atom; an allyl thiol. Preferably, R' is a linear or branched C1 to C5 alkyl group, and thus the thiol is a C1 to C5 alkanethiol, more preferably a methyl mercaptan, an ethyl mercaptan or a n-propyl mercaptan. , isopropyl mercaptan, allyl mercaptan, n-butyl mercaptan, isobutyl mercaptan, 2-methyl propane mercaptan, n-pentyl mercaptan, isoamyl mercaptan or 2,2,2-trifluoroethane sulfur alcohol. If trifluoroethane thiol is used, it is possible to produce thiocarbonates including fluorine substituents on two substituent groups, such as fluoromethoxy-S-(2,2,2-trifluoroethyl) Carbonate or (1-fluoroethyl)-(2,2,2-trifluoroethyl)carbonate. Particularly preferred of the mercaptans are methyl mercaptan, ethyl mercaptan, allyl mercaptan, n-propyl mercaptan and isopropyl mercaptan. The most preferred thiol is methyl mercaptan.

If desired, a mixture of multiple thiols can be used in the desired molar ratio. For example, a mixture of methyl mercaptan and ethanethiol can be applied at a molar ratio of 1:1. In this case, a corresponding thiocarbonate substituted by a methyl group and a thiocarbonate substituted by an ethyl group are obtained.

The thiol reaction can be carried out in the presence of an HF scavenger such as LiF, NaF, KF or CsF, or in a base such as in the presence of ammonia or a primary, secondary or tertiary amine such as triethylamine or pyridine. In the presence of. Preferably, it is carried out without a base.

Preferably, the molar between the thiol and the formate is equal to or greater than 0.9:1. Preferably, it is equal to or less than 5:1. Very good results were obtained when the ratio of alcohol to formate was in the range of from 0.95:1 to 1.2:1.

The reaction temperature during the thiol reaction is not critical. Often, this reaction is exothermic, so it is desirable to even cool the reaction mixture (especially if an alkali metal thiolate is used). The temperature during the thiol hydrolysis is preferably equal to or higher than -80 ° C, and more preferably equal to or higher than -78 ° C. The upper limit temperature can be dependent on the pressure and boiling point of the starting material, such as the boiling point of the mercaptan. Often, this temperature is equal to or lower than 85 °C.

The reaction can be carried out in any suitable reactor, such as in an autoclave.

The reaction can be carried out batchwise or continuously.

The resulting reaction mixture can be separated by a variety of known methods (e.g., by distillation, precipitation, and/or crystallization). If desired, the reaction mixture can be contacted with an aqueous phase to remove water soluble components. Due to the specific type of reaction, organic carbonates with a higher degree of fluorination are formed, and if this does occur, they are only in very small proportions.

According to another alternative, a fluoroalkyl thiocarbonate S-(fluoro)alkyl ester having the general formula (I), FCHR-OC(O)-SR', wherein R and R' are prepared, is prepared in a process Having the meaning given above includes the steps of: chloroalkyl fluoroformate having the formula (IV), ClCHROC(O)F or having the formula (IV'), ClCHROC(O)Cl a chloroalkyl chloroformate, wherein R has the meaning given above, reacts with a thiol of formula (III), R'SH, wherein R' has the meaning given above, and subsequently Chlorine-fluorine exchange.

Thus, in a first step, an intermediate thiocarbonate having the formula (V), ClCHR-OC(O)-SR' is produced. In the formula (V), R and R' have the meanings given above. The intermediate thiocarbonate is then reacted with a reactant capable of replacing a chlorine atom with a fluorine atom. This reaction is called the "Halex" reaction. Reactants suitable for chlorine-fluorine exchange are generally known. Particularly suitable as such a reactant are alkali metal fluorides or alkaline earth metal fluorides of the formula (IX), N(R ¹ ) ₄ F, ammonium fluorides, hydrofluorinated amines, wherein the substituents R ¹ The same or different groups and representing H or C1 to C5, provided that at least one substituent R ¹ is a C1 to C5 alkyl group. Hydrofluorinated amines are also suitable, in which the nitrogen atom is a heterocyclic system (for example, pyridine hydrofluoride, 1,8-diazabicyclo[5.4.0] eleven-7 a part of a olefin, and 1,5-diaza-bicyclo[4.3.0]non-5-ene. As an alternative to, or in addition to, the fluorides, hydrofluoride adducts can be used in the Halex reaction, such as CsF. HF. Other fluorides are also suitable as reactants, such as AgF. The Halex reaction can be carried out in the absence or presence of a solvent, for example, in the presence of a nitrile. Often, the reaction is carried out at elevated temperatures, for example at temperatures equal to or above 50 °C.

The working course of the reaction mixture is carried out in a known manner, the reaction mixture comprising a possible excess of fluoride salt of the chloride salt and the fluorinated reactant And fluorinated carbonates and possibly unreacted starting materials. For example, the solids are removed by filtration and the liquid phase is subjected to fractional distillation or precipitation after removal of any solvent.

The fluorinated organic thiocarbonates produced by the process of the present invention are useful as additives or solvents for lithium ion batteries, lithium air batteries, and lithium-sulfur batteries. They offer a number of advantages (such as modified viscosity), reduce flammability and appear to modify the electrode under the formation of beneficial film types. Accordingly, another aspect of the invention relates to a fluoroalkyl thiocarbonate S-(fluoro)alkyl ester having the general formula (I), FCHR-OC(O)-SR', wherein R represents H, has from 1 to 5 a linear or branched alkyl group of C atoms, CH ₂ =CHX (wherein X is CH ₂ , C ₂ H ₄ ); CH(CH ₃ )=CH, C(CH ₃ ) ₂ =CH; or CH =CHY (wherein Y is H, CH ₃ or C ₂ H ₅ ); and R' represents a linear or branched alkyl group having 1 to 7 carbon atoms; having 1 to 1 substituted by at least one fluorine atom a linear or branched alkyl group of 7 carbon atoms; a phenyl group; a phenyl group substituted by one or more C1 to C3 alkyl group atoms, or a phenyl group substituted by one or more chlorine or fluorine atoms. Or benzyl,

Use as an additive or solvent for lithium ion batteries, lithium air batteries, and lithium-sulfur batteries.

Compounds of formula (II), FCHROC(O)F can be prepared from the corresponding chloroalkyl chloroformate in a "Halex" type reaction, ie by means of fluorinating agents (as already explained above, for example Using a fluorinated reactant such as an alkali metal fluoride or an alkaline earth metal fluoride such as LiF, KF, CsF, NaF, NH ₄ F or a hydrofluorinated amine, or a corresponding HF adduct) with a fluorine atom Replace these chlorine atoms. The chloroalkyl chloroformate itself is available by the reaction between carbonium chloride and an aldehyde as described in U.S. Patent 5,712,407. It is preferred to produce an intermediate compound of the formula (II), FCHROC(O)F from carbonium fluoride and an aldehyde. Accordingly, another aspect of the present invention relates to the manufacture of an aldehyde having carbon fluorofluoride and a chemical formula of RC(O)H wherein R represents a linear or branched alkyl group having 1 to 5 C atoms or H) A method of intermediate compound of formula (II), FCHROC(O)F. Preferably, it represents H; here, the aldehyde is formaldehyde. The formaldehyde can be applied in the form of paraformaldehyde or trioxane, which must be cleaved (e.g., thermally cracked) to form a monomeric formaldehyde.

The molar ratio between the carbonium fluoride and the aldehyde is preferably equal to or greater than 0.9:1. It is preferably equal to or less than 5:1.

Preferably, the molar ratio between the carbonium fluoride and the aldehyde is in the range of from 0.9:1 to 5:1. More preferably, the molar ratio between the carbonium fluoride and the aldehyde is in the range of from 0.9:1 to 3:1.

Preferably, for example, F ^- the reaction between fluorine and carbon acyl aldehyde catalyzed. For example, the reaction can be catalyzed by HF, and HF can be added as it is or by in situ addition by adding a small amount of water.

Preferred catalysts are those containing a fluoride anion, for example, an alkaline earth metal fluoride or an alkali metal fluoride such as CsF, or a catalyst containing a fluoride ion formed from carbonium fluoride and a precatalyst. Preferred precatalysts are dialkylformammines, especially dimethylformamide. It is assumed that methotrexate forms a "naked" fluoride ion with carbonium fluoride, which initiates a nucleophilic reaction on the aldehyde. The negatively charged oxygen of the adduct formed by the fluoride ion and the aldehyde molecule is then reacted with a carbon fluorene molecule. Fluoromethyl formate or fluoroalkyl fluoroformate is formed in general.

Pyridine, advantageously 4-dialkylaminopyridine, especially 4-dimethylaminopyridine, is also considered a suitable precatalyst.

The reaction is preferably carried out batchwise, such as in an autoclave. Alternatively, it can be carried out continuously.

The reaction temperature can be varied. For example, when a very effective catalyst is employed, the reaction can be carried out even at ambient temperature. However, it must be borne in mind that in the case of formaldehyde as the starting material, the monomer form must be provided by the cleavage of paraformaldehyde or 1,3,5-trioxane. Therefore, although the reaction can often be carried out at a low temperature as it is, heating must be applied for the cleavage.

In the case where formaldehyde is used as the starting material, the reaction is preferably carried out at a temperature equal to or higher than 100 °C. It is preferably carried out at a temperature equal to or lower than 300 °C. When an aldehyde is used as a starting material (it must not be thermally cracked), the reaction can be carried out at a temperature equal to or greater than 0 ° C and equal to or lower than 200 ° C. It is preferred to carry out the reaction at such elevated temperatures and/or for a sufficient period of time until the desired conversion has taken place.

It is preferably carried out in the liquid phase or under a plurality of supercritical conditions. The pressure is selected such that at least a portion of the carbonium fluoride is present in the liquid phase. The pressure depends on the reaction temperature; the higher the reaction temperature, the higher the pressure in the reactor. The reaction can be carried out at ambient pressure (absolute value of about 1 bar). For example, COF ₂ can be introduced into the liquid reaction mixture or starting material through a submerged tube. Preferably, the reaction is carried out at a pressure equal to or greater than 5 bar (absolute). Preferably, the reaction is carried out at a pressure equal to or lower than 50 bar (absolute). As was done in an example, if the reaction temperature is sufficiently high, the contents of the reactor are in a supercritical state. If desired, the reactor can be pressurized with an inert gas, especially with nitrogen.

If desired, the fluoroalkyl fluoroformate (and especially the fluoromethyl fluoroformate) can be separated from the reaction mixture according to various methods known in the art, such as by distillation. These formed, fluorine-substituted formates can be used for any purpose to achieve the use of a compound having one C(O)F function or one FCH ₂ O function. For example, they can be used as fluorinating agents or to introduce a protective group into a plurality of amino acids or peptides. In a preferred embodiment, the isocyanates are reacted with a thiol as described above to form a fluoromethyl S-alkyl ester of thiocarbonate, an allyl ester or a 2,2,2-three Fluoroethyl ester.

A preferred aspect of the invention relates to a process comprising the manufacture of two or three steps of a compound of formula (I), FCHROC(O)-SR', wherein R represents H, has from 1 to 5 a linear or branched alkyl group of C atom or H, and R' represents a linear or branched alkyl group having 1 to 7 carbon atoms; 2 to 7 substituted by at least one fluorine atom a linear or branched alkyl group of one carbon atom; CH ₂ =CHX (wherein X is CH ₂ , C ₂ H ₄ ); phenyl; benzyl; one or more C1 to C3 alkyl group atoms Substituted phenyl, or phenyl substituted by one or more chlorine or fluorine atoms. The method is carried out according to two alternatives.

The first alternative includes: an aldehyde with carbon fluorene and RC(O)H (wherein R represents 1) a linear or branched alkyl group of 5 C atoms or H) a step of preparing a fluoroalkyl fluoroformate having the formula (II), FCHROC(O)F; and a fluorine having the formula (II) A step of the reaction is carried out with a fluoroalkyl formate and a thiol having the formula (III), R'SH, wherein R and R' have the meanings given above.

Instead of or in addition to the thiol, the corresponding alkali metal thiolate, for example the corresponding potassium or sodium thiolate, may be employed.

Also herein, the group R preferably represents H and is involved in the aldehyde formaldehyde. The formaldehyde can be applied in the form of paraformaldehyde or 1,3,5-trioxane, which must be cleaved (e.g., thermally cracked) to form a monomeric formaldehyde.

A preferred embodiment of the 2-step process according to the present invention provides a process for the manufacture of fluoromethyl alkyl carbonate, the process comprising: using carbon fluorene and formaldehyde, 1,3,5-trioxane or poly a step of preparing fluoromethyl fluoroformate from formaldehyde, and with or without separation, and subsequently, a step of reacting the fluoromethyl fluoroformate with a thiol having the formula (III), R'SH, Wherein R' preferably denotes a straight or branched alkyl group having 1 to 7 C atoms; CH ₂ =CHX (wherein X is CH ₂ or C ₂ H ₄ ); CH(CH ₃ )=CH And C(CH ₃ ) ₂ =CH; phenyl; phenyl substituted by 1 or more C1 to C3 alkyl group atoms, or phenyl substituted by 1 or more chlorine or fluorine. Preferably, the thiol is selected from the group consisting of methyl mercaptan, ethanethiol, n-propyl mercaptan, isopropyl mercaptan, allyl mercaptan, n-butyl mercaptan and n-pentyl mercaptan. The thiol is particularly preferably allyl mercaptan, methyl mercaptan, 2,2,2-trifluoroethane thiol, or ethane thiol, and most preferably methyl mercaptan.

Preferred embodiments of the steps are those already described above, and in particular to the preferred use of a catalyst (using a formamide, especially dimethylformamide as a preferred pre-stage in the first step) Catalyst), pressure and temperature in the first and second steps, optional use of a base in the second step, corresponding pressure, reaction temperature, etc.; described above with respect to the steps of the respective reactions These preferred embodiments are also applicable to the 2-step method of the present invention.

A further alternative includes a method comprising a Harlex reaction.

In this alternative, in a first step, carbonium chloride (phosgene) is reacted with RC(O)H, wherein R represents a linear or branched alkyl group having from 1 to 5 C atoms or H. The intermediate chloroalkyl chloroformate formed (having the formula (IV'), ClCHRC(O)Cl, wherein R has the meaning given above) is then subjected to a Harlex reaction to form the formic acid fluoride of formula (I) An alkyl ester which is then reacted with a thiol or a thiolate as described above to produce a fluoroalkyl thiocarbonate S-(fluoro)alkyl ester of formula (I); or an intermediate chloroformic acid formed a chloroalkyl ester (having the formula (VII), ClCHROC(O)Cl, wherein R has the meaning given above) is then reacted with a thiol or a thiolate as described above to produce a thiocarbonate having the formula (V) The fluoroalkyl ester S-(fluoro)alkyl ester is then subjected to a Harlex reaction as described above to produce a fluoroalkyl thiocarbonate S-(fluoro)alkyl ester of formula (I).

Another embodiment of the present invention is a chloroalkyl sulphate S-fluoroalkyl ester intermediate having the formula (V'), ClCHROC(O)SR", wherein R represents H or has 1 to 5 C atoms. A linear or branched alkyl group, and wherein R" represents a linear or branched alkyl group having 1 to 7 carbon atoms which is substituted by at least one fluorine atom. Preferably, in the compound of formula (V'), R represents CH ₃ or H, and R" represents S-2,2,2-trifluoroethyl.

The intermediates may be lithium, sodium, potassium or rubidium with 1-chloroalkyl chloroformate and a fluorinated thiol and a fluorinated thiol or thiolate (eg a fluorinated thiol) Prepared by the thiolate); the trifluorothioethanolate may be unstable. These intermediates can be used as starting materials (as illustrated) to produce the fluoroalkyl thiocarbonate S-alkyl esters of the present invention. They can also be used as intermediates in chemical synthesis.

The process of the invention (involving the preparation of a fluoroalkyl sulphate S-alkyl ester) allows for the selective production of a monofluorinated product; similarly, the preparation of a fluoroalkyl sulphate S-alkyl ester allows for selectivity Sulphur carbonates are produced in which both substituents are replaced by a certain amount of F ions; even if an undesirably higher fluoro product is formed, it will only be a small amount.

Since a major field of application for such compounds of formula (I) is used as a solvent or additive in lithium ion batteries, it is preferred not to start with chlorinated compounds since chlorine is used in the art as a Impurities are undesirable. Therefore, it is preferred that there is no reaction path necessary for the Halex reaction.

These compounds may be used undiluted as a solvent in a Li-ion battery or preferably as a kind of addition together with one or more other solvents. Additives, for example, are used to reduce the viscosity of the solvent. The amount as an additive is, for example, in the range of from 0.5% to 60% by weight.

Suitable solvents are known. Some preferred such solvents are given below.

Organic carbonates, especially dialkyl carbonates such as dimethyl carbonate or diethyl carbonate, methyl ethyl carbonate, alkyl alkyl carbonates such as ethyl or ethyl propylene carbonate, fluorinated solvents For example, mono-, di-, tri-, and/or tetrafluoro-ethyl carbonates are very suitable. Alternatively or additionally, extraction of LiPO ₂ F ₂ from a mixture with LiF or corresponding extraction of LiPF ₆ from a mixture comprising LiPO ₂ F ₂ may be carried out using other solvents, such as lactones, formamide, pyrrolidone, oxazole Alkanone, nitroalkane, N,N-substituted carbamate, cyclobutyl hydrazine, dialkyl hydrazine, dialkyl sulfite (as disclosed in M. Ue et al. J. Electrochem. Soc .Vol. 141 (1994), described on pages 2989 to 2996), or a trialkyl phosphate or alkoxy ester, as described in DE-A 10016816.

Alkyl carbonates having straight-chain and branched alkyl groups and alkylene carbonates are particularly suitable for, for example, correspondingly dissolving LiPO ₂ F ₂ in a mixture comprising LiF and containing LiPO ₂ F LiPF ₆ is preferentially dissolved in the mixture of ₂ , which are correspondingly, for example, ethyl carbonate, methyl dimethyl carbonate, methyl ethyl carbonate (EMC), diethyl carbonate and propyl carbonate (PC), see EP-A-0 643 433. Pyrocarbonates are also useful, see US-A 5,427,874. Alkyl acetates such as ethyl acetate, N,N-disubstituted acetamide, hydrazine, nitrile, glycol ethers and ethers are also useful, see EP-A-0 662 729. Mixtures of such solvents are often employed. Dioxolane is a useful solvent, see EP-A-0 385 724. For lithium bis-(trifluoromethanesulfonate) imide, 1,2-bis-(trifluoroacetoxy)ethane and N,N-dimethyltrifluoroacetamide can be used as a solvent, see ITE Battery Letters Vol. 1 (1999), pp. 105-109. In the above, the term "alkyl" preferably denotes a saturated straight-chain or branched C1 to C4 alkyl group, and the term "alkylene group" preferably denotes an alkylene group of C2 to C7. The group includes a vinyl group, wherein the alkyl group preferably comprises a bridge of 2 carbon atoms between the oxygen atoms of -OC(O)-O-, thereby forming a 5-membered ring.

The fluorine-substituted compound is also a suitable solvent correspondingly for dissolving LiPO ₂ F ₂ or LiPF ₆ , such as a fluorinated carbonate, which is selected from the group consisting of fluorine substitution. Ethyl carbonate, fluorine-substituted dimethyl carbonate, fluorine-substituted methyl ethyl carbonate, and fluorine-substituted diethyl carbonate. They can be applied in the form of a mixture with a non-fluorinated solvent. For example, the non-fluorinated organic carbonates mentioned above are very suitable.

Preferred fluorine-substituted carbonates are: ethyl monofluorocarbonate, ethyl 4,4-difluorocarbonate, ethyl 4,5-difluorocarbonate, 4-fluoro-4-methyl Ethyl carbonate, 4,5-difluoro-4-methylcarbonate ethyl ester, 4-fluoro-5-methylcarbonate ethyl ester, 4,4-difluoro-5-methylcarbonate ethyl ester, 4-(fluoromethyl)-ethyl carbonate, 4-(difluoromethyl)-carbonic acid ethyl ester, 4-(trifluoromethyl)-carbonic acid ethyl ester, 4-(fluoromethyl)-4 - fluorocarbonic acid ethyl ester, 4-(fluoromethyl)-5-fluorocarbonic acid ethyl ester, 4-fluoro-4,5-dimethyl carbonate ethyl ester, 4,5-difluoro-4, 5-dimethyl carbonate ethyl ester and 4,4-difluoro-5,5-dimethyl carbonate ethyl ester ; dimethyl carbonate derivatives, including fluoromethyl carbonate. Methyl ester, difluoromethyl carbonate. Methyl ester, trifluoromethyl carbonate. Methyl ester, bis(fluoromethyl) carbonate, bis(difluoro)methyl carbonate, and bis(trifluoro)methyl carbonate; methyl carbonate. Ethyl ester derivatives, including 2-fluoroethyl carbonate. Methyl ester, ethyl fluoride. Methyl ester, 2,2-difluoroethyl carbonate. Methyl ester, 2-fluoroethyl carbonate. Fluoromethyl ester, ethyl carbonate. Difluoromethyl ester, 2,2,2-trifluoroethyl carbonate. Methyl ester, 2,2-difluoroethyl carbonate. Fluoromethyl ester, 2-fluoroethyl carbonate. Difluoromethyl ester, and ethyl carbonate. Trifluoromethyl ester; and diethyl carbonate derivatives, including carbonic acid (2-fluoroethyl). Ethyl ester, carbonic acid (2,2-difluoroethyl). Ethyl ester, bis(2-fluoroethyl) carbonate, (2,2,2-trifluoroethyl). Ethyl ester, 2,2-difluoroethyl carbonate. 2'-fluoroethyl ester, bis(2,2-difluoroethyl) carbonate, 2,2,2-trifluoroethyl carbonate. 2'-fluoroethyl ester, 2,2,2-trifluoroethyl carbonate. 2', 2'-difluoroethyl ester, and bis(2,2,2-trifluoroethyl) carbonate.

It is also possible to use a carbonate having both an unsaturated bond and a fluorine atom (hereinafter abbreviated as "fluorinated unsaturated carbonate") as a solvent to remove LiPF ₆ from its mixture with LiPO ₂ F ₂ or LiPO ₂ F _{2 is} dissolved to separate it from impurities such as impurities such as LiF. Such fluorinated unsaturated carbonates include any fluorinated unsaturated carbonate that does not significantly impair the advantages of the present invention.

Examples of the fluorinated unsaturated carbonate include a fluorine-substituted carbonic acid vinyl ester derivative, a fluorine-substituted ethylene carbonate derivative substituted with a substituent having an aromatic ring or a carbon-carbon unsaturated bond, and Fluorine substituted allyl carbonate.

Examples of the carbonic acid-extended vinyl ester derivative include vinyl fluorocarbonate, 4-fluoro-5-methylvinyl carbonate, and 4-fluoro-5phenyl-extended vinyl carbonate.

Examples of the ethyl carbonate derivative substituted by a substituent having an aromatic ring or a carbon-carbon unsaturated bond include 4-fluoro-4-vinylcarbonate ethyl ester and 4-fluoro-5-vinyl carbonate Ethyl ester, 4,4-difluoro-4-vinylcarbonate ethyl ester, 4,5-difluoro-4-vinylcarbonate ethyl ester, 4-fluoro-4,5-divinyl carbonate ethyl ester , 4,5-difluoro-4,5-divinylcarbonate ethyl ester, 4-fluoro-4-phenylcarbonic acid ethyl ester, 4-fluoro-5-phenylethyl carbonate ethyl ester, 4,4- Difluoro-5-phenylcarbonic acid ethyl ester, 4,5-difluoro-4-phenylcarbonic acid ethyl ester and 4,5-difluoro-4,5-diphenylcarbonic acid ethyl ester.

Examples of the fluorine-substituted phenyl carbonate include fluoromethylphenyl carbonate, 2-fluoroethylphenyl carbonate, 2,2-difluoroethylphenyl carbonate, and 2,2,2-trifluorocarbonate. Ethyl phenyl ester.

Examples of the fluorine-substituted vinyl carbonate include fluoromethyl vinyl carbonate, 2-fluoroethyl vinyl carbonate, 2,2-difluoroethyl vinyl carbonate, and 2,2,2-trifluorocarbonate. Ethyl vinyl ester.

Examples of the fluorine-substituted allyl carbonate include fluoromethyl allyl carbonate, 2-fluoroethyl allyl carbonate, 2,2-difluoroethyl allyl carbonate, and carbonic acid 2,2, 2-Trifluoroethyl allyl ester.

The sulfur-containing compound of the present invention has a specific taste. Therefore, they can be used as an additive with a warning function to indicate damage to the battery case.

In the event that any disclosure of patents, patent applications, and publications incorporated herein by reference is inconsistent with the description of the present application to the extent that it may make the term unclear, this description should be preferred.

The invention will now be further illustrated by a number of examples without intending to limit it.

In the event that any disclosure of patents, patent applications, and publications incorporated herein by reference is inconsistent with the description of the present application to the extent that it may make the term unclear, this description should be preferred.

Example: Example 1: Preparation of fluoromethyl fluoroformate

Paraformaldehyde (10.2 g; 340 mmol) and dimethylformamide (1.5 g; 71 mmol) were charged to an autoclave having an internal volume of about 500 ml. The autoclave was closed, evacuated and pressurized to about 5 bar (absolute) with dry nitrogen and evacuated again. Then, carbonium fluoride (32 g; 485 mmol) was charged into the autoclave. The autoclave was heated overnight to about 230 ° C; the pressure was raised to about 35 bar (absolute). The autoclave was then cooled to ambient temperature; the pressure now drops to about 10 bar (absolute). The gaseous components of the autoclave were purged through a washing machine. The autoclave was then pressurized twice with nitrogen, each time up to a pressure of about 5 bar (absolute).

If desired, the formed fluoromethyl fluoroformate can be separated by distillation.

Example 2: Preparation of O-fluoromethyl S-thioethyl carbonate

The fluoroethyl fluoroformate (50.0 g) was cooled to 0 °C. Add under stirring A mixture of pyridine (12.0 g) and ethanethiol (28.2 g). The reaction process was monitored by GC analysis. After 18 hours, 50 mL of water was added. After phase separation, the organic phase was washed with water and a saturated sodium chloride solution. The product was obtained after drying over sodium sulfate as a pale yellow liquid (45 g). The purity was 73.5% without any purification step. This product can be further purified by distillation.

Example 3: Preparation of fluoroethyl ester of α-fluoroformic acid

Acetaldehyde (12 g; 272 mmol) and dimethylformamide (200 mg; 71 mmol) were charged to an autoclave having an internal volume of about 40 ml. The autoclave was closed, evacuated and pressurized to about 5 bar (absolute) with dry nitrogen and evacuated again. Then, carbonium fluoride (18 g; 272 mmol) was charged into the autoclave over a period of 30 minutes. The mixture was stirred at room temperature for 30 minutes, after which time the pressure was reduced from 20 bar to 0 bar. The autoclave was then pressurized twice with nitrogen, each time up to a pressure of about 5 bar (absolute).

If desired, the formed fluoroethyl fluoroformate can be separated by distillation.

Example 4: Preparation of O-α-fluoromethyl ester S-methyl ester of sulphuric acid

The fluoroethyl α-fluoroformate (24.7 g, 225 mmol) was cooled to 0 ° C in a 100 mL PFA flask. Methyl mercaptan (310 mmol) was added over a period of 15 minutes. The mixture was stirred at -78 °C for 30 minutes. After warming to room temperature, the reaction was stirred for another 16 hours. The resulting mixture was washed with water (3 x 10 ml) and added to molecular sieves (0.4 Nm), and after stirring at room temperature for 4 hours, all solids were removed by filtration. The resulting crude product was purified by distillation under reduced pressure.

Example 5: Preparation of α-fluoroethyl S-thioethyl carbonate

Fluoroethyl α-fluoroformate (27.0 g, 245 mmol) was added to dry NaF (15 g; 357 mmol) in a 100 mL PFA flask. After the mixture was cooled to 0 ° C, ethanethiol (310 mmol) was added over a period of 15 minutes. The mixture was stirred at 0 ° C for 30 minutes. After warming to room temperature, the reaction was stirred for another 16 hours. After adding 5 g of molecular sieves (0.4 nm) and stirring at room temperature for 4 hours, all the solids were removed by filtration. The resulting crude product was purified by distillation under reduced pressure.

Example 6: Electrolyte composition comprising a F-alkyl ester of S-alkyl thiocarbonate

To obtain such an electrolyte composition, in a first step, the solvent component of the basic solvent (possibly a mixture of a plurality of components) and the corresponding thiosulfate shown in Table 1 are mixed under stirring; The electrolyte salt was then added with stirring and allowed to dissolve. All operations were carried out under dry N ₂ or Ar.

* A certain amount of LiPF ₆ was added to the solvent composition to a concentration of 1 mole. If LiPO ₂ F _{2 is added} as an electrolyte salt additive, its content in the electrolyte composition after addition should be 1% by weight (when the composition containing all the solvent and electrolyte salt components is set to 100 by weight) %).

According to the following reaction, the reaction of POF ₃ and Li ₃ PO ₄ can easily produce LiPO ₂ F ₂ : 2POF ₃ + Li = 3PO ₄ → 3LiPO ₂ F ₂

This reaction is illustrated in the unpublished EP patent application N 10188108.4 filed on October 19, 2010. Other methods are also known. EP-A-2,065,339 discloses how to make a mixture of LiPF ₆ and LiPO ₂ F ₂ from a halide other than fluoride, LiPF ₆ and water. The resulting salt mixture is dissolved in an aprotic solvent and used as an electrolyte solution for a lithium ion battery. EP-A-2 061 115 describes LiPO ₂ F ₂ from P ₂ O ₃ F ₄ and Li compounds as a conventional technique at the time; and as described in the invention, a compound from LiPF ₆ and having a Si-O-Si bond (for example, a siloxane) to produce LiPO ₂ F ₂ . US-A 2008-305402 also discloses the preparation of LiPO ₂ F ₂ from LiPF ₆ with a carbonate compound.

Claims (10)

A fluoroalkyl sulphate S-(fluoro)alkyl ester having the general formula (I): FCHR-OC(O)-SR', wherein R represents H, a linear or 1 to 5 C atom Branched alkyl, CH ₂ =CHX (where X is CH ₂ , C ₂ H ₄ ), CH(CH ₃ )=CH, C(CH ₃ ) ₂ =CH, or CH=CHY (where Y is H, CH ₃ or C ₂ H ₅ ); and R' represents a linear or branched alkyl group having 1 to 7 carbon atoms, a linear or 1 to 7 carbon atom substituted by at least one fluorine atom Branched alkyl, CH ₂ =CHX (wherein X is CH ₂ , C ₂ H ₄ ), phenyl, phenyl substituted by one or more C1 to C3 alkyl group atoms or by one or more chlorine Or a phenyl group substituted with a fluorine atom, or a benzyl group. A thiocarbonate according to claim 1, wherein R is H, allyl, methyl, ethyl or isopropyl. A thiocarbonate according to claim 2, wherein R' is methyl, ethyl, or n-propyl, isopropyl, allyl or 2,2,2-trifluoroethyl. A process for producing a fluoroalkyl thiocarbonate S-(fluoro)alkyl ester having the general formula (I): FCHR-OC(O)-SR', wherein R represents H, having a straightness of 1 to 5 C atoms A chain or branched alkyl group, CH ₂ =CHX (wherein X is CH ₂ , C ₂ H ₄ ), CH(CH ₃ )=CH, C(CH ₃ ) ₂ =CH, CH ₂ =CHX (where X a CH ₂ , C ₂ H ₄ ); and R' represents a linear or branched alkyl group having 1 to 7 carbon atoms, a linear chain having 1 to 7 carbon atoms substituted by at least one fluorine atom Or branched alkyl, CH ₂ =CHX (wherein X is CH ₂ , C ₂ H ₄ ), phenyl, phenyl substituted by one or more C1 to C3 alkyl group atoms or by one or more a phenyl group substituted with a chlorine atom or a fluorine atom, or a benzyl group, wherein the method comprises the steps of: fluoroalkyl fluoroformate having the formula (II): FCHROC(O)F, or having the formula (II'): The fluoroalkyl chloroformate of FCHROC(O)Cl(II') is reacted with a thiol of formula (III): R'SH, wherein R and R' have the meanings given above, or include the following steps: A chloroalkyl fluoroformate having the formula (IV): ClCHROC(O)F or having the formula (IV'): ClCHROC (O a chloroalkyl chloroformate of Cl (wherein R has the meaning given above) is reacted with a thiol of formula (III): R'SH (wherein R' has the meaning given above), and subsequently Chlorine-fluorine exchange. A method for producing a fluoroalkyl thiocarbonate S-(fluoro)alkyl ester having the general formula (I): FCHR-OC(O)-SR', as in claim 4, wherein R represents H, a linear or branched alkyl group having 1 to 5 C atoms, CH(CH ₃ )=CH, C(CH ₃ ) ₂ =CH, CH ₂ =CHX (wherein X system CH ₂ , C ₂ H ₄ ), or CH=CHY (wherein Y represents a C1 to C3 alkyl group); and R' represents a linear or branched alkyl group having 1 to 7 carbon atoms, having 1 to 7 substituted by at least one fluorine atom a linear or branched alkyl group of a carbon atom, a benzyl group, a phenyl group, a phenyl group substituted with one or more C1 to C3 alkyl group atoms or a benzene substituted with one or more chlorine or fluorine atoms. Base, the method comprising the steps of: fluoroalkyl fluoroformate having the formula (II): FCHROC(O)F or a fluoroalkyl chloroformate having the formula (II'): FCHROC(O)Cl Chemical formula (III): a thiol of R'SH is reacted, wherein R and R' have the meanings given above, or the method comprises the steps of: chlorofluorocarbon having the formula (IV): ClCHROC(O)F Alkyl ester or chloroalkyl chloroformate of formula (IV'): ClCHROC(O)Cl The ester (wherein R has the meaning given above) is reacted with a thiol of formula (III): R'SH (wherein R' has the meaning given above), and subsequently includes a chlorine-fluorine exchange reaction step. Use of a fluoroalkyl thiocarbonate S-(fluoro)alkyl ester of the formula (I): FCHR-OC(O)-SR', wherein R represents H, a linear chain having 1 to 5 C atoms Or branched alkyl, CH ₂ =CHX (where X is CH ₂ , C ₂ H ₄ ), CH(CH ₃ )=CH, C(CH ₃ ) ₂ =CH, or CH=CHY (where Y is H, CH ₃ or C ₂ H ₅ ); and R' represents a linear or branched alkyl group having 1 to 7 carbon atoms, a linear chain having 1 to 7 carbon atoms substituted by at least one fluorine atom Or branched alkyl, phenyl, phenyl substituted by one or more C1 to C3 alkyl group atoms or phenyl substituted by one or more chlorine or fluorine atoms, or benzyl, as Li Additives or solvents for ion batteries, Li air batteries, and Li sulfur batteries. A Li-ion battery comprising, as an additive, a fluoroalkyl thiocarbonate S-(fluoro)alkyl ester having the general formula (I): FCHR-OC(O)-SR', wherein R represents H and has 1 to 5 A linear or branched alkyl group of a C atom, CH ₂ =CHX (wherein X is CH ₂ , C ₂ H ₄ ), CH(CH ₃ )=CH, C(CH ₃ ) ₂ =CH, or CH= CHY (wherein Y is H, CH ₃ or C ₂ H ₅ ); and R' represents a linear or branched alkyl group having 1 to 7 carbon atoms, and 1 to 7 substituted by at least one fluorine atom a linear or branched alkyl group of a carbon atom, CH ₂ =CHX (wherein X is CH ₂ , C ₂ H ₄ ), a phenyl group, a phenyl group substituted by one or more C1 to C3 alkyl group atoms Or a phenyl group substituted with one or more chlorine or fluorine atoms, or a benzyl group. A chloroalkyl sulphate S-fluoroalkyl ester compound having the formula (V'): ClCHROC(O)SR", wherein R represents H, a linear or branched alkane having 1 to 5 C atoms Base, CH(CH ₃ )=CH, C(CH ₃ ) ₂ =CH, CH ₂ =CHX (where X is CH ₂ , C ₂ H ₄ ), or CH=CHY (where Y is H, CH ₃ or C ₂ H ₅ ); and wherein R” represents a linear or branched alkyl group having 1 to 7 carbon atoms which is substituted by at least one fluorine atom. A compound according to claim 8 wherein R represents H or CH ₃ and R" represents 2,2,2-trifluoroethyl. Use of a fluoroalkyl thiocarbonate S-(fluoro)alkyl ester of the formula (I): FCHR-OC(O)-SR', wherein R represents H, a linear chain having 1 to 5 C atoms Or branched alkyl, CH ₂ =CHX (where X is CH ₂ , C ₂ H ₄ ), CH(CH ₃ )=CH, C(CH ₃ ) ₂ =CH, or CH=CHY (where Y is H, CH ₃ or C ₂ H ₅ ); and R' represents a linear or branched alkyl group having 1 to 7 carbon atoms, a linear chain having 1 to 7 carbon atoms substituted by at least one fluorine atom Or branched alkyl, CH ₂ =CHX (wherein X is CH ₂ , C ₂ H ₄ ), phenyl, phenyl substituted by one or more C1 to C3 alkyl group atoms or by one or more A phenyl or benzyl group substituted with a chlorine or fluorine atom serves as an additive with a warning to indicate damage to the outer casing of the battery.