Patent Application
20120184763
The present invention relates to a method for producing a perfluorosulfonic acid having an ether structure (perfluoroalkoxy/perfluoroalkylsulfonic acid), a derivative thereof and a starting compound thereof, and to a surfactant containing a fluorine-containing ether sulfonic acid compound and a derivative thereof.
The present application claims priority on the basis of Japanese Patent Application No. 2009-223975, filed on Sep. 29, 2009, the contents of which are incorporated herein by reference.
Perfluorosulfonic acid and derivatives thereof (RFSO2X: wherein, RF represents a group in which a hydrogen atom of the reacting hydrocarbon group is substituted with a fluorine atom, and X represents, for example, —OH or a halogen atom) have been used in surfactants, acid generators, ionic liquids, catalysts and the like. Among perfluorosulfonic acids, in particular, those having a perfluorooctane sulfonyl (C8F17SO2—) structure having 8 carbon atoms are chemically stable; however, they have problems consisting of being resistant to degradation and accumulation in the body as a result thereof, and for this reason have begun to be restricted. In addition, similar restrictions have been enacted in the U.S. on perfluorosulfonic acids having 6 or more carbon atoms. Consequently, there is a need for an alternative compound that has less of an effect on the environment while maintaining the performance thereof.
One possible candidate for such an alternative compound is a compound obtained by introducing an ether structure into the aforementioned RF group to obtain an RF2ORF1— structure.
Here, RF1 and RF2 represent groups in which hydrogen atoms of the each of the corresponding reacting hydrocarbon groups are substituted with fluorine atoms. A known example of a method used to produce these compounds consists of an RF2ORF1SO2X production method that uses perfluorovinylsulfonyl fluoride (CF2═CFSO2F) and perfluorohypofluorite (RFOF) (Patent Document 1: Japanese Unexamined Patent Application, First Publication No. H6-128216). However, methods using perfluorovinylsulfonyl fluoride (CF2═CFSO2F) and perfluorohypofluorite (RFOF) have problems consisting of using expensive fluorinated raw materials, requiring that the procedure be carried out at an extremely low temperature due to the low boiling point of the raw materials, being unable to arbitrarily select the ratio of the linear form (n-form) to isomer (i-form), and actually only obtaining a basic ethanesulfonyl structure.
With respect to other compounds, a method involving the synthesis of ether from alkoxide and alkyl halide (sulfonic acid) is commonly known as the Williamson method. However, in the case of producing a perfluoro compound by the Williamson method, the respective perfluorinated compounds are conventionally used as raw materials, thereby resulting in the same problems as those applicable to Patent Document 1.
In order to solve the aforementioned problems, an object of the present invention is to provide a method for producing a perfluorosulfonic acid having an ether structure (perfluoroalkoxy/perfluoroalkylsulfonic acid) that enables a compound of a target structure to be produced inexpensively without causing isomerization and the like, a derivative thereof, and a starting compound thereof.
In addition, an object of the present invention is to provide a surfactant containing that derivative.
The inventors of the present invention found that a perfluorosulfonic acid having an ether structure other than an ethanesulfonyl structure (perfluoroalkoxy/perfluoroalkyl-sulfonic acid), and a derivative thereof, which were unable to be produced in the past, can be produced by forming a hydrocarbon compound having a desired carbon backbone and fluorinating that compound instead of forming a compound having an RF2ORF1— structure using a fluorinated raw material.
In addition, the inventors of the present invention found that fluorination can be carried out safely and a compound of a target structure can be produced inexpensively without causing isomerization and the like by adding RH2ORH1SO2F to hydrofluoric acid to obtain a concentrated solution (hydrogen bonded complex), and either supplying this directly to a liquid phase reaction system that uses F2 gas, or adding hydrofluoric acid to RH2ORH1SO2Cl, discharging HCl to convert to RH1ORH2SO2F, and then supplying this to a liquid phase reaction system that uses F2 gas.
On the basis of the aforementioned findings, the present invention provides a method for inexpensively producing a compound of a target structure without causing isomerization and the like for a perfluorosulfonic acid having an ether structure (perfluoroalkoxy/perfluoroalkylsulfonic acid) and a derivative thereof (RF2ORF1SO2X). In addition, the present invention provides a method for producing starting compounds consisting of RH2ORH1SO2F and RH2ORH1SO2Cl. Moreover, the present invention provides a surfactant containing a derivative (RF2ORF1SO3M).
According to the present invention, a method is provided for producing compounds having the structures indicated below.
[1] A method for producing a fluorine-containing ether sulfonic acid compound comprising producing a perfluorosulfonic acid having an ether structure and a derivative RF1ORF2SO2X thereof (wherein, RF1 and RF2 represent groups in which hydrogen atoms in the RH1 and RH2 groups have been substituted with fluorine atoms and X represents —OH, an alkoxy group or a halogen) by perfluorinating a sulfonyl halide represented by the general formula RH2ORH1SO2Y (wherein, RH1 and RH2 respectively represent a hydrocarbon group having 1 to 4 carbon atoms and Y represents fluorine or chlorine).
[2] The method for producing a fluorine-containing ether sulfonic acid compound described in [1] above, wherein the sulfonyl halide is such that:
the RH1 is a hydrocarbon group (linear or branched) having 3 carbon atoms in the case the RH2 is a hydrocarbon group having 1 carbon atom,
the RH1 is a hydrocarbon group having 1 carbon atom, hydrocarbon group (linear or branched) having 3 carbon atoms or hydrocarbon group (linear or branched) having 4 carbon atoms in the case the RH2 is a hydrocarbon group (linear or branched) having 3 carbon atoms, and
the RH1 is a hydrocarbon group having 1 carbon atom or a hydrocarbon group (linear or branched) having 3 carbon atoms in the case the RH2 is a hydrocarbon group (linear or branched) having 4 carbon atoms.
[3] The method for producing a fluorine-containing ether sulfonic acid compound described in [1] or [2] above, wherein the sulfonyl fluoride (RH2ORH1SO2F) described in [1] or [2] above is added to hydrofluoric acid to obtain a solution containing a hydrogen bonded complex, and this is supplied to a reaction solvent together with F2 gas and then perfluorinated in a liquid phase to produce perfluorosulfonic acid having an ether structure and a derivative RF1ORF2SO2X thereof (wherein, RF1 and RF2 represent groups in which hydrogen atoms in the RH1 and RH2 groups have been substituted with fluorine atoms and X represents —OH, an alkoxy group or a halogen).
[4] The method for producing a fluorine-containing ether sulfonic acid compound described in [1] or [2] above, wherein the sulfonyl chloride (RH2ORH1SO2Cl) described in [1] or [2] above is added to hydrofluoric acid to convert to sulfonyl fluoride and obtain a solution containing a hydrogen bonded complex, and this is supplied to a reaction solvent together with F2 gas and then perfluorinated in a liquid phase to produce a perfluorosulfonic acid having an ether structure and a derivative RF1ORF2SO2X thereof (wherein, RF1 and RF2 represent groups in which hydrogen atoms in the RH1 and RH2 groups have been substituted with fluorine atoms and X represents —OH, an alkoxy group or a halogen).
[5] The method for producing a fluorine-containing ether sulfonic acid compound described in [1] or [2] above, wherein the perfluorination is carried out by electrolytically fluorinating the sulfonyl fluoride (RH2ORH1SO2R) described in [1] or [2] above in anhydrous hydrofluoric acid.
[6] A production method of the perfluorosulfonic acid having an ether structure and a derivative RF1ORF2SO2X thereof described in [3] or [4] above, comprising carrying out the reaction by preliminarily adding and suspending NaF or KF in the liquid phase fluorination reaction liquid as an adsorbent of hydrofluoric acid.
[7] A production method of the perfluorosulfonic acid having an ether structure and a derivative RF1ORF2SO2X thereof described in any of [1] to [6] above, comprising converting a fluorination reaction product (RF2ORF1SO2F) in the reaction liquid to a sulfonic acid ester (RF2ORF1SO2OR3) using a base and an alcohol R3OH, and then separating and purifying by distillation.
In addition, the present invention provides a method for producing a hydrocarbon sulfonyl fluoride having an ether structure (alkoxyalkylsulfonyl fluoride) composed in the manner described below that is useful as a starting compound of the production methods described in [1] to [7] above.
[8] A method for producing a hydrocarbon sulfonyl fluoride having an ether structure (alkoxyalkylsulfonyl fluoride), comprising a step wherein an alkoxide, obtained by reacting CH3OM, C2H5OM or a linear or branched alcohol having 3 to 4 carbon atoms with a metal M, M-H or CH3OM (wherein, M represents Na, K or Li), is reacted with X1—RH1—SO2—X2 (wherein, X1 represents Cl or Br, RH1 represents a linear alkyl group having 1 to 4 carbon atoms, and X2 represents ONa, OK, Cl or Br) to synthesize R2—O—RH1—SO2—X2 (wherein, R2—O— represents an alkoxy group equivalent to the alkoxide), followed by subjecting to the action of a chlorinating agent to obtain RH2—O—RH1—SO2—Cl, and further converting to RH2—O—RH1—SO2—F in an aqueous solution containing KF.
[9] A method for producing a hydrocarbon sulfonyl fluoride having an ether structure (alkoxyalkylsulfonyl fluoride), comprising a step wherein CH3OH, C2H5OH or a linear or branched alcohol having 3 to 4 carbon atoms is reacted directly with 1,3-propane sultone or 1,4-butane sultone to synthesize R2—O—RH1—SO2—OH (wherein, R2—O— represents an alkoxy group equivalent to the alkoxide, and RH1 represents a linear alkylene derived from the sultone), followed by subjecting to the action of a chlorinating agent to obtain RH2—O—RH1—SO2—Cl, and further converting to RH2—O—RH1—SO2—F in a KF-organic solvent-water system.
[10] A method for producing a hydrocarbon sulfonyl fluoride having an ether structure (alkoxyalkylsulfonyl fluoride), comprising a step wherein an alkoxide, obtained by reacting CH3OM, C2H5OM or a linear or branched alcohol having 3 to 4 carbon atoms with a metal M, M-H or CH3OM (wherein, M represents Na, K or Li), is reacted directly with 1,3-propane sultone or 1,4-butane sultone to synthesize R2—O—RH1—SO2—OM (wherein, R2—O— represents an alkoxy group equivalent to the alkoxide, and RH1 represents a linear alkylene derived from the sultone), followed by subjecting to the action of a chlorinating agent to obtain RH2—O—RH1—SO2—Cl, and further converting to RH2—O—RH1—SO2—F in an aqueous solution containing KF.
[11] A fluorine-containing ether sulfonic acid compound that is a compound represented by general formula RF1ORF2SO2X (wherein, RF1 and RF2 respectively represent a perfluoroalkyl group having 1 to 4 carbon atoms, and X represents —OH, an alkoxy or a halogen), wherein
the RF1 is a perfluoroalkyl group (linear or branched) having 3 carbon atoms in the case the RF2 is a perfluoroalkyl group having 1 carbon atom, the RF1 is a perfluoroalkyl group having 1 carbon atom, a perfluoroalkyl group (linear or branched) having 3 carbon atoms or a perfluoroalkyl group (linear or branched) having 4 carbon atoms in the case the RF2 is a perfluoroalkyl group (linear) having 3 carbon atoms, and
the RF1 is a perfluoroalkyl group having 1 carbon atom or a perfluoroalkyl group (linear or branched) having 3 carbon atoms in the case the RF2 is a perfluoroalkyl group (linear) having 4 carbon atoms.
[12] A surfactant that contains a compound represented by general formula RF1ORF2SO3M (wherein, RF1 and RF2 respectively represent a perfluoroalkyl group having 1 to 4 carbon atoms, and M represents Li, Na, K or NH4), wherein
the RF1 is a perfluoroalkyl group (linear or branched) having 3 carbon atoms in the case the RF2 is a perfluoroalkyl group having 1 carbon atom,
the RF1 is a perfluoroalkyl group having 1 carbon atom, a perfluoroalkyl group (linear or branched) having 3 carbon atoms or a perfluoroalkyl group (linear or branched) having 4 carbon atoms in the case the RF2 is a perfluoroalkyl group (linear) having 3 carbon atoms, and
the RF1 is a perfluoroalkyl group having 1 carbon atom or a perfluoroalkyl group (linear or branched) having 3 carbon atoms in the case the RF2 is a perfluoroalkyl group (linear) having 4 carbon atoms.
According to the present invention, molecular design can be carried out with a comparatively inexpensive hydrocarbon compound, and a perfluoro compound can be obtained while maintaining the structure thereof. In addition, not only is the cost low, but the yield is favorable. Consequently, the present invention is highly useful as a method for synthesizing a diverse range of novel compounds for use as alternative compounds to conventional perfluoroalkylsulfonic acids and derivatives thereof.
In addition, the present invention is also able to provide a surfactant containing a novel compound.
The following provides a detailed explanation of the present invention.
[Perfluorination]
(First Aspect)
In a basic aspect of the present invention, a sulfonyl fluoride RH2ORH1SO2F (wherein, RH1 and RH2 respectively represent a hydrocarbon group having 1 to 4 carbon atoms) is added to hydrofluoric acid to obtain a solution containing a hydrogen bonded complex. F2 gas is supplied to a reaction solvent that is stable with respect to F2 gas and this is supplied to the aforementioned solution followed by carrying out perfluorination in a liquid phase. Furthermore, although perfluorination can also actually be carried out by a method consisting of reacting directly with F2 gas without using a solvent or by a solid phase reaction using CoF3, since it is difficult to control the reaction and there is typically the problem of low yield attributable to decomposition and the like, perfluorination is advantageously carried out in the liquid phase.
Here, the hydrofluoric acid may be anhydrous hydrofluoric acid or may contain water up to about 10% by weight. The amount of the hydrofluoric acid is preferably 0.5 to 10 times the number of moles of the raw material and particularly preferably 1 to 3 times the number of moles of the raw material.
Examples of reaction solvents that are stable with respect to F2 gas include perfluoroalkanes, perfluoroethers, perfluoropolyethers and perfluorotrialkylamines that can be acquired as industrial products or reagents, and these can be used alone or as a mixture thereof. Although chlorofluorocarbons can also be used, these have a considerable effect on the environment in comparison with the aforementioned solvents, thereby making them undesirable. The amount of the reaction solvent is preferably 0.5 mol/L to 0.01 mol/L and more preferably 0.2 mol/L to 0.05 mol/L based on the raw material.
In addition, a compound capable of being fluorinated may also be present for the purpose of regulating the reaction. Compounds having a double bond between carbon atoms such as benzene or hexafluorobenzene can be used. The amount thereof is preferably 1 to 50 mol % based on the raw material, and may be added to the starting solution or may be supplied to the reaction liquid after separately dissolving in the reaction solvent. In addition, ultraviolet light may also be radiated for the same purpose.
The F2 gas may be diluted with an inert gas. Examples of such inert gases that can be used include nitrogen gas, helium gas and argon gas. Among these, nitrogen gas is economically preferable. The concentration of F2 in the gas is determined so that the reaction proceeds suitably, and may be changed corresponding to the progression of the reaction. The concentration of the F2 gas is preferably 1 to 50 vol % and more preferably 10 to 30 vol %. The reaction temperature is preferably from −80° C. to equal to or lower than the boiling point of the solvent and more preferably −30° C. to 30° C. from the viewpoint of control.
[Second Aspect]
Perfluorination may be carried out by adding a sulfonyl chloride RH2ORH1SO2Cl to hydrofluoric acid to convert to RH1ORH2SO2F and obtain a solution containing a hydrogen bonded complex in a second aspect instead of the aforementioned first aspect. Perfluorination can be carried out safely by converting the sulfonyl chloride RH2ORH1SO2Cl to sulfonyl fluoride RH1ORH2SO2F by discharging HCl in a reaction with hydrofluoric acid, or by supplying directly to a liquid phase reaction using F2 gas.
The hydrofluoric acid produced as a by-product in the liquid phase reaction that uses F2 and the hydrofluoric acid added to the starting solution are preferably promptly removed. A column packed with NaF pellets may be attached to the exhaust gas line of the reaction apparatus to adsorb hydrofluoric acid, and a condenser may be provided in the backflow thereof followed by returning the reaction liquid to the reactor. In addition, the reaction is more preferably carried out by preliminarily adding NaF or KF to a liquid phase fluorination reaction liquid and suspending therein. Yield can be improved by adding and suspending NaF and the like. The NaF and the like can be used in any of the forms of powder, pellets or crystals. The amount of NaF and the like added is preferably 0.5 to 10 times the number of moles of the hydrofluoric acid produced as a by-product in the reaction and the hydrofluoric acid added to the starting solution, and particularly preferably 1 to 3 times that number of moles. If the added amount is excessively low, progression of the reaction is inhibited, and it becomes necessary to provide a separately step for removing the excess hydrofluoric acid. If the amount added is excessively high, the process becomes uneconomical and the burden on filtration or other equipment or apparatuses increases.
The fluorination reaction product (RF2ORF1SO2F) present in the reaction liquid obtained in this manner may be further converted to a sulfonic acid ester (RF2ORF1SO2OR3) using a base (carbonate of alkaline metal or organic base such as triethylamine) and an alcohol R3OH. Separation and purification by distillation can be carried out easily as a result of converting to this ester compound. In addition, the fluorination reaction product may also be isolated as RF2ORF1SO3M by allowing MOH (where, M represents an alkaline metal) to act on a perfluorosulfonic acid ester (RF2ORF1SO2OR3), or may be isolated as RF2ORF1SO3H by treating with a mineral acid (such as H2SO4 or HCl).
Alternatively, the fluorination reaction product (RF2ORF1SO2F) may be isolated as RF2ORF1SO3M by allowing MOH (where, M represents an alkaline metal) or may be isolated as RFORF1SO3H by treating with a mineral acid (such as H2SO4 or HCl) at the stage the fluorination reaction product is present in the reaction liquid.
(Third Aspect)
Perfluorination may also be carried out by electrolytically fluorinating a sulfonyl fluoride RH2ORH1SO2F in anhydrous hydrofluoric acid as a third aspect instead of the aforementioned first aspect and second aspect. Here, the sulfonyl fluoride used as an electrolysis raw material can be easily produced by fluorine replacement by adding potassium fluoride (KF) and the like to sulfonyl chloride RH2ORH1SO2Cl.
Electrolytic fluorination specifically consists of using sulfonyl fluoride RH2ORH1SO2F as a raw material, introducing this into an electrolytic bath along with hydrofluoric acid, and then electrolyzing under normal pressure in a nitrogen gas atmosphere. As a result, the hydrocarbon groups RH1 and RH2 of the sulfonyl fluoride are replaced with fluorine resulting in the formation of a fluorination reaction product (RF2ORFSO2F).
As has been described above, according to the present invention, any of perfluorosulfonic acid having an ether structure and a derivative RF1ORF2SO2X thereof (wherein, RF1 and RF2 represent groups in which hydrogen atoms in the aforementioned RH1 and RH2 groups are substituted with fluorine, and X represents —OH, an alkoxy group or a halogen) can be produced.
The following lists specific examples of compounds produced according to the production method of the present invention (and X in the compounds is the same as defined above). All of the compounds listed here are thought to be novel compounds.
CF3O(CF2)3SO2X, n-C3F7O(CF2)3SO2X, CF3O(CF2)4SO2X, CF3OCF2SO2X, n-C3F7OCF2SO2X, CF3CF (CF3) OCF2SO2X, n-C4F9OCF2SO2X, C2F5CF(CF3)OCF2SO2X, (CF3)3COCF2SO2X, n-C3F7O(CF2)2SO2X, CF3CF(CF3)O(CF2)3SO2X, n-C4F9(CF2)3SO2X, C2F5CF(CF3)O(CF2)3SO2X, (CF3)3CO(CF2)3SO2X, n-C3F7O(CF2)4SO2X, CF3CF(CF3)O(CF2)4SO2X
[Surfactant]
A compound (salt of perfluorosulfonic acid) that is a derivative of perfluorosulfonic acid represented by the general formula RF1ORF2SO3M (wherein, RF1 and RF2 respectively represent a perfluoroalkyl group having 1 to 4 carbon atoms, and M represents Li, Na, K, or NH4) is formed by hydrolyzing the aforementioned derivative RF1ORF2SO2X (wherein, RF1 and RF2 represent groups in which hydrogen atoms in the aforementioned RH1 and RH2 groups are substituted with fluorine atoms, and X represents —OH, an alkoxy group or a halogen) with an aqueous alkaline solution.
Here, the basic carbon backbone of the aforementioned derivative RF1ORF2SO2X is such that:
RF1 is preferably a perfluoroalkyl group (linear or branched) in the case RF2 is a perfluoroalkyl group having 1 carbon atom,
RF1 is preferably a perfluoroalkyl group having 1 carbon atom, a perfluoroalkyl group (linear or branched) having 3 carbon atoms or a perfluoroalkyl group (linear or branched) having 4 carbon atoms in the case RF2 is a perfluoroalkyl group (linear) having 3 carbon atoms, and
RF1 is preferably a perfluoroalkyl group having 1 carbon atom or a perfluoroalkyl group (linear or branched) having 3 carbon atoms in the case RF2 is a perfluoroalkyl group (linear) having 4 carbon atoms.
In addition, examples of the aqueous alkaline solution that can be used include aqueous lithium hydroxide (LiOH), aqueous sodium hydroxide (NaOH), aqueous potassium hydroxide (KOH) and aqueous ammonia (NH3).
An aqueous solution of a salt of perfluorosulfonic acid represented by the general formula RF1ORF2SO3M (wherein, RF1 and RF2 respectively represent a perfluoroalkyl group having 1 to 4 carbon atoms, and M represents Li, Na, K, or NH4) can be used as a surfactant with respect to water.
[Starting Compound]
Although an alkylsulfonic acid derivative having an ether structure serving as the starting compound of the perfluorosulfonic acid derivative having an ether structure according to the present invention as previously described can be produced by various methods, an aspect of the present invention provides the production methods described below. Furthermore, an example of a chlorinating agent used in the following production methods is SOCl2.
A first production method is as described below.
A method for producing a hydrocarbon sulfonyl fluoride having an ether structure (alkoxyalkylsulfonyl fluoride), comprising a step wherein an alkoxide, obtained by reacting CH3OM, C2H5OM or a linear or branched alcohol having 3 to 4 carbon atoms and a metal M, M-H or CH3OM (wherein, M represents Na, K or Li), is reacted with X1—RH1—SO2—X2 (wherein, X1 represents Cl or Br, RH1 represents a linear alkyl group having 1 to 4 carbon atoms, and X2 represents ONa, OK, Cl or Br) to synthesize R2—O—RH1—SO2—X2 (wherein, R2—O— represents an alkoxy group equivalent to the alkoxide), followed by subjecting to the action of a chlorinating agent to obtain RH2—O—RH1—SO2—Cl, and further converting to RH2—O—RH1—SO2—F in an aqueous solution containing KF.
A second production method is as described below.
A method for producing a hydrocarbon sulfonyl fluoride having an ether structure (alkoxyalkylsulfonyl fluoride), comprising a step wherein a CH3OH, C2H3OH or a linear or branched alcohol having 3 to 4 carbon atoms is reacted directly with 1,3-propane sultone or 1,4-butane sultone to synthesize R2—O—RH1—SO2—OH (wherein, R2—O— represents an alkoxy group equivalent to the alkoxide, and RH1 represents a linear alkylene derived from the sultone), followed by subjecting to the action of a chlorinating agent to obtain RH2—O—RH1—SO2—Cl, and further converting to RH2—O—RH1—SO2—F in a KF-organic solvent-water system. An acid catalyst such as CF3SO3H may be added during the reaction between the alcohol and sultone.
A third production method is as described below.
A method for producing a hydrocarbon sulfonyl fluoride having an ether structure (alkoxyalkylsulfonyl fluoride), comprising a step wherein an alkoxide, obtained by reacting CH3OM, C2H5OM or a linear or branched alcohol having 3 to 4 carbon atoms and a metal M, M-H or CH3OM (wherein, M represents Na, K or Li), is reacted directly with 1,3-propane sultone or 1,4-butane sultone to synthesize R2—O—RH1—SO2—OM (wherein, R2—O— represents an alkoxy group equivalent to the alkoxide, and RH1 represents a linear alkylene derived from the sultone), followed by subjecting to the action of a chlorinating agent to obtain RH2—O—RH1—SO2—Cl, and further converting to RH2—O—RH1—SO2—F in an aqueous solution containing KF.
The following lists specific examples of the RH2ORH1SO2X produced according to the methods described above. In the following chemical formulas, X is the same as previously defined, and is a halogen, for example. Examples of halogens include F and Cl.
CH3OCH2SO2X, n-C3H7OCH2SO2X, CH3CH(CH3)OCH2SO2X, n-C4H9OCH2SO2X, C2H5CH(CH3) OCH2SO2X, (CH3)3COCH2SO2X, n-C3H7O(CH2)2SO2X, CH3CH(CH3)O(CH2)2SO2X, C2H5CH(CH3)O(CH2)2SO2X, (CH3)3CO(CH2)2SO2X, CH3CH(CH3)O(CH2)3SO2X, C2H5CH(CH3)O(CH2)3SO2X, (CH3)3CO(CH2)3SO2X, n-C3H7O(CH2)4SO2X, CH3CH(CH3)O(CH2)4SO2X, C2H5CH(CH3)O(CH2)4SO2X, (CH3)3CO(CH2)4SO2X, and so on.
The following provides a detailed description of the present invention using examples and reference examples. Furthermore, the present invention is not limited to these examples. In the following examples, identification and confirmation of the products were carried out by GC-MS (EI, 70 eV) and 1H-NMR (270 MHz, TMS standard)/19F-NMR (254 MHz, CCl3F standard) unless specifically stated otherwise. A Teflon® vessel made of PFA was used for the reaction vessel.
11.25 g (50 mmol) of sodium 3-bromopropanesulfonate and 50 ml of methanol were charged into a 200 ml glass four-mouth flask equipped with a reflux condenser, thermometer and stirrer followed by heating and refluxing in an oil bath. 75 g (75 mmol) of 28% sodium methylate were dropped therein over the course of 1 hour and further allowed to react for 22 hours while continuing to reflux. After allowing the reactants to cool, water was added until the liquid became transparent followed by neutralizing in 1:1 dilute hydrochloric acid, transferring to a recovery flask, and concentrating and drying with a rotary evaporator. 60 g of chloroform and 0.3 g of N,N-dimethylformamide (DMF) as catalyst were added to the dried product, a forked connecting pipe was attached, and 23.8 g (200 mmol) of thionyl chloride were dropped in at room temperature followed by allowing to react for 17 hours while heating and refluxing in an oil bath. After concentrating the reaction liquid under reduced pressure, a solution containing 50 g of chloroform and 4.35 g (75 mmol) of potassium fluoride dissolved in 30 g of water was added, followed by stirring for 24 hours at room temperature. The reaction liquid was separated, the chloroform layer was washed 3 times with water, dried with anhydrous magnesium sulfate and concentrated with a rotary evaporator to obtain the target compound by vacuum distillation using a packed column. The amount obtained was 4.81 g, GC purity was 99%, yield was 61% and the boiling point was 87° C. to 89° C. at 2.67 kPa. 1H-NMR (solvent: CDCl3, ppm): 2.18 (m, 2H), 3.35 (s, 3H), 3.51 (m, 4H). 19F-NMR (solvent: CDCl3, ppm): 52.73 (t, 1F).
25.6 g (0.8 mol) of methanol and 24.4 g (0.2 mol) of 1,3-propane sultone were charged into the same apparatus as that of Example 1-1-1 and allowed to react for 3 days while refluxing. The reactants were transferred to a recovery flask and concentrated with a rotary evaporator to obtain a viscous liquid. 150 g of chloroform and 1 g of N,N-dimethylformamide (DMF) as catalyst were added thereto, a forked connecting tube was attached and 95.2 g (0.8 mol) of thionyl chloride were dropped in at room temperature, followed by reacting for 17 hours while heating and refluxing in an oil bath. After concentrating the reaction liquid under reduced pressure, a solution containing 150 g of chloroform and 17.4 g (0.3 mol) of potassium fluoride dissolved in 80 g of water was added followed by stirring for 24 hours at room temperature. The reaction liquid was separated, the chloroform layer was washed 3 times with water, dried with anhydrous magnesium sulfate and concentrated with a rotary evaporator to obtain the target compound by vacuum distillation using a packed column. The amount obtained was 13.41 g, GC purity was 98.5%, and yield was 78%.
0.44 g (22 mmol) of anhydrous hydrofluoric acid were placed in a fluorine resin PFA container having a volume of 7 ml in an ice bath, followed by slowly dropping in 1.56 g (10 mmol) of the starting compound CH3O(CH2)3SO2F produced in Example 1-1-1 while stirring. After further adding 0.08 (1 mmol) of benzene to the resulting homogeneous liquid and stirring, the liquid was transferred to a plastic syringe (starting solution, total volume: 1.75 ml).
On the other hand, 100 ml of perfluorohexane were charged into a 180 ml reaction vessel equipped with a 0° C. and −78° C. two-stage condenser equipped with a gas access port, raw material feed port and an NaF pellet filling pipe and reaction liquid return pipe in between followed by blowing N2 gas into the liquid for 0.5 hours at a flow rate of 3 L/Hr. Subsequently, the N2 gas was replaced with F2N2 mixed gas (F2: 20%, N2: 80%) and blown in for 0.5 hours at a flow rate of 2.77 L/Hr.
The aforementioned starting solution was supplied to the reaction vessel over the course of 8 hours while maintaining the flow rate of the F2N2 mixed gas, after which the gas was blown in for 0.5 hours. The temperature of the reaction liquid was controlled to 18° C. to 22° C. Next, 0.56 g (3 mmol) of hexafluorobenzene was dissolved in perfluorohexane and brought to a final volume of 10 ml, and this solution was supplied to the reaction vessel over the course of 2 hours while blowing in the F2N2 mixed gas at a flow rate of 1 L/Hr, followed by further blowing in the gas for 0.5 hours. Next, the F2N2 mixed gas was changed to N2 gas, and the reactor was purged by blowing the N2 gas into the liquid for 1 hour at a flow rate of 3 L/Hr. The temperature of the reaction liquid was controlled to 21° C. to 22° C. GC analysis was carried out on the reaction liquid and CF3O(CF2)3SO2F was confirmed to have been formed.
GC-MS mass numbers (relative intensity): 69 (100), 67 (20.5), 119 (8.3), 100 (4.6), 169 (4.1), 50 (1.5), 135 (1.2)
Next, 2.76 g (20 mmol) of potassium carbonate were added to a reaction vessel at room temperature followed by dropping in 3 g (30 mmol) of CF3CH2OH while stirring and then stirring for 4 hours to carry out esterification and obtain CF3O(CF2)3SO2OCH2CF3. The reaction liquid was filtered using celite as a filtration assistant, washed with water and dried with anhydrous magnesium sulfate. After concentrating, the residue was further vacuum-distilled to fractionate a fraction obtained at 59° C. to 61° C. at 4.0 kPa and obtain the target compound at a yield of 39%.
1H-NMR (solvent: CDCl3, ppm): 4.72 (q, 2H)
19F-NMR (solvent: CDCl3, ppm): −124.44 (s, 2F), −110.52 (d, 2F), −85.38 (q, 2F), −74.95 (t, 3F), −55.52 (t, 3F)
Production was carried out in the same manner as Example 1-2-1 using 0.6 g (30 mmol) of anhydrous hydrofluoric acid, 3.12 g (20 mmol) of the starting compound CH3O(CH2)3SO2F and 0.16 g (2 mmol) of benzene (starting solution total volume: 3.2 ml). However, a −78° C. single stage condenser was used for the condenser, the reaction liquid return pipe was omitted from the apparatus of Example 1-2-1, the reaction vessel was changed to that having a volume of 300 ml, and 200 ml of perfluorohexane and 14 g (0133 mmol) of sodium fluoride pellets were charged into the reaction vessel followed by blowing N2 gas into the liquid for 1 hour at the rate of 3 L/Hr. The N2 gas was replaced with F2N2 mixed gas (F2: 30%, N2: 70%) and blown in for 0.5 hours at a flow rate of 3.03 L/Hr.
The aforementioned starting solution was supplied to the reaction vessel over the course of 8 hours while maintaining the flow rate of the F2N2 mixed gas, after which the gas was further blown in for 0.5 hours. The temperature of the reaction liquid was controlled to 14° C. to 16° C. Next, 0.93 g (5 mmol) of hexafluorobenzene was dissolved in perfluorohexane and brought to a final volume of 10 ml, and this solution was supplied to the reaction vessel over the course of 2 hours while blowing in the F2N2 mixed gas at a flow rate of 1.13 L/Hr, followed by further blowing in the gas for 0.5 hours. Next, the F2N2 mixed gas was changed to N2 gas, and the reactor was purged by blowing the N2 gas into the liquid for 1 hour at a flow rate of 3 L/Hr. The temperature of the reaction liquid was controlled to 14° C. to 16° C. GC-MS analysis was carried out on the reaction liquid and CF2O(CF2)2SO2F was confirmed to have been formed.
Next, after removing the acidic sodium fluoride (NaHF2) by filtering the reaction liquid under pressure, 6.9 g (50 mmol) of potassium carbonate were added to a reaction vessel at room temperature followed by dropping in 4 g (40 mmol) of CF3CH2OH while stirring and then stirring for 4 hours to carry out esterification. The reaction liquid was filtered using celite as a filtration assistant, washed with water and dried with anhydrous magnesium sulfate. After concentrating, the residue was further vacuum-distilled to obtain the target compound at a yield of 49%.
Production of the target compound containing an epoxy group was carried out by roughly the same procedure as Example 1-1-2 with the exception of changing the alcohol from methanol to ethanol. Namely, 18.4 g (0.4 mol) of ethanol and 24.4 g (0.2 mol) of 1,3-propane sultone were charged into the same apparatus as Example 1-1-1 and allowed to react for 4 days while refluxing. The reactants were transferred to a recovery flask and concentrated with a rotary evaporator to obtain a viscous liquid. 100 g of chloroform and 0.6 g of N,N-dimethylformamide (DMF) as catalyst were added thereto, a forked connecting tube and a reflux condenser were attached and 47.6 g (0.4 mol) of thionyl chloride were dropped in at room temperature, followed by reacting for 15.5 hours while heating and refluxing in an oil bath. After concentrating the reaction liquid under reduced pressure, a solution containing 100 g of chloroform and 11.6 g (0.2 mol) of potassium fluoride dissolved in 50 g of water was added followed by stirring for 5 days at room temperature. The reaction liquid was separated, the chloroform layer was washed 3 times with water, dried with anhydrous magnesium sulfate and concentrated with a rotary evaporator to obtain the target compound by vacuum distillation using a packed column. The amount obtained was 15.42 g, GC purity was 98.5%, yield was 89% and the boiling point was 92° C. to 95° C. at 2.67 kPa.
1H-NMR (solvent: CDCl3, ppm): 1.19 (t, 3H), 2.18 (m, 2H), 3.52 (m, 6H).
19F-NMR (solvent: CDCl3, ppm): 52.75 (m, 1F).
Preparation was carried out in the same manner as Example 1-2-1 using 3.4 g (20 mmol) of the starting compound C2H5O(CH2)3SO2F (starting solution total volume: 3.6 ml). Using the same apparatus configuration as Example 1-2-2, the same procedure as Example 1-2-2 was carried out with the exception of using 14.62 g (0.35 mol) of powdered sodium fluoride, changing the flow rate of the F2N2 mixed gas (F2: 30%, N2: 70%) to 3.59 L/Hr, changing the temperature of the reaction liquid to 14° C. to 17° C., and changing the temperature of the reaction liquid during introduction of hexafluorobenzene to 12° C. to 16° C. to obtain the target compound at a yield of 45%. The boiling point was 62° C. to 63° C. at 2.80 kPa.
GC-MS mass numbers (relative intensity): 119 (100), 69 (59.6), 67 (54.8), 100 (11.9), 31 (10.9), 169 (9.7), 50 (3.2), 147 (2.8)
1H-NMR (solvent: CDCl3, ppm): 4.72 (q, 2H)
19F-NMR (solvent: CDCl3, ppm): −124.47 (s, 2F), −110.65 (t, 2F), −88.79 (t, 2F), −87.29 (s, 3F), −83.37 (m, 2F), −74.97 (q, 3F)
The same reaction procedure as Example 1-1-2 was carried out with the exception of using 24 g (0.4 mol) of n-propyl alcohol for the alcohol, 100 g of chloroform, 0.6 g of N,N-dimethylformamide (DMF) and 47.6 g (0.4 mol) of thionyl chloride and changing the reaction time to 5 Hr, and changing the chloroform to 40 ml of acetonitrile, changing the amount of water to 40 g and changing the reaction time to 3 days. The amount obtained was 15.163 g, GC purity was 99.13%, yield was 84% and the boiling point was 97° C. to 98° C. at 2.0 kPa.
1H-NMR (solvent: CDCl3, ppm): 0.92 (t, 3H), 1.15 (m, 2H), 2.19 (m, 2H), 3.39 (t, 2H), 3.53 (m, 4H)
19F-NMR (solvent: CDCl3, ppm): 52.72 (m, 1F)
Preparation was carried out in the same manner as Example 1-2-1 with the exception of changing to 3.8 g (20 mmol) of the starting compound n-C2H7O(CH2)2SO2F and 0.93 g (5 mmol) of hexafluorobenzene (starting solution total volume: 4.2 ml). Using the same apparatus configuration as Example 1-2-2, the same procedure as Example 1-2-2 was carried out with the exception of using 18 g (0.43 mol) of powdered sodium fluoride, changing the flow rate of the F2N2 mixed gas (F2: 30%, N2: 70%) to 5.13 L/Hr, changing the temperature of the reaction liquid to 16° C. to 17° C., and changing the temperature of the reaction liquid during introduction of hexafluorobenzene to 15° C. to 16° C. to obtain the target compound at a yield of 47%. The boiling point was 73° C. to 75° C. at 2.80 kPa.
GC-MS mass numbers (relative intensity): 69 (100), 67 (78.6), 169 (71.8), 100 (17.5), 50 (3.2), 233 (0.5), 235 (0.4)
1H-NMR (solvent: CDCl3, ppm): 4.71 (q, 2H)
19F-NMR (solvent: CDCl3, ppm): −130.42 (s, 2F), −124.42 (d, 2F), −110.69 (s, 2F), −84.67 (m, 2F), −83.24 (m, 2F), −81.992 (t, 3F), −75.04 (t, 3F)
The same reaction procedure as Example 1-1-2 was carried out with the exception of using 33.6 g (1.05 mol) of methanol, 35.6 g (0.26 mol) of 1,4-butane sultone and 5 drops (catalytic amount) of CF3SO3H, refluxing for 10 days, using 160 g of chloroform, 1 g of N,N-dimethylformamide (DMF) and 119 g (1 mol) of thionyl chloride, changing the reaction time to 5 Hr, changing the chloroform to 228 ml of acetonitrile, using 30.16 g (0.52 mol) of potassium fluoride, changing the amount of water to 171 g and changing the reaction time to 1 day. The amount obtained was 32.5 g, GC purity was 99.1%, yield was 72% and the boiling point was 104° C. to 106° C. at 2.53 kPa.
1H-NMR (solvent: CDCl3, ppm): 1.75 (m, 2H), 2.04 (m, 2H), 3.33 (s, 3H), 3.45 (m, 4H)
19F-NMR (solvent: CDCl3, ppm): 52.45 (m, 1F)
Preparation was carried out in the same manner as Example 1-2-1 with the exception of changing to 3.4 g (20 mmol) of the starting compound CH3O(CH2)4SO2F and changing the benzene to 0.93 g (5 mmol) of hexafluorobenzene (starting solution total volume: 3.9 ml). Using the same apparatus configuration as Example 1-2-2, the same procedure as Example 1-2-2 was carried out with the exception of using 15.7 g (0.37 mol) of powdered sodium fluoride, changing the flow rate of the F2N2 mixed gas (F2: 30%, N2: 70%) to 4.39 L/Hr, changing the duration of supplying the starting solution to 6 Hr, changing the temperature of the reaction liquid to 14° C. to 18° C., and changing the temperature of the reaction liquid during introduction of hexafluorobenzene to 14° C. to 16° C. to obtain the target compound at a yield of 40%. The boiling point was 67° C. to 69° C. at 2.80 kPa.
GC-MS mass numbers (relative intensity): 69 (100), 67 (22.4), 169 (7.7), 100 (5.7), 119 (1.9), 131 (1.6), 135 (1.4)
1H-NMR (solvent: CDCl3, ppm): 4.72 (q, 2H)
19F-NMR (solvent: CDCl3, ppm): −125.70 (m, 2F), −120.99 (q, 2F), −110.24 (t, 2F), −85.56 (q, 2F), −74.99 (t, 3F), −55.62 (t, 3F)
Using an electrolysis bath made of SUS316L and having an effective volume of 480 ml for the electrolysis bath, and using a condenser made of SUS316L for the condenser, the electrolysis bath and condenser were cooled to −21° C. with a coolant. Electrodes made of nickel plates having an effective surface area of 0.75 dm2/plate were used for the electrodes, and the electrodes were arranged by mutually separating by a gap of 2 mm.
4.8 g of C3H7O(CH2)3SO2F were dissolved in 480 g of anhydrous hydrofluoric acid, and together with a passing a current through electrodes consisting of 8 cathodes and 9 anodes at 9 Ahr, C3H7O(CH2)3SO2F was continuously supplied using a pump to carry out electrolytic fluorination. The total amount of raw materials added was 255.47 g, the total amount of current applied was 1209 Ahr, the voltage (when stable) was 5 V to 5.2 V, and the temperature inside the electrolysis bath was 4° C. to 6° C.
The perfluorination product was extracted at suitable times from a valve located in the bottom of the electrolysis bath, and a total of 207.9 g were extracted. As a result of analyzing the perfluorination product with a gas chromatograph (capillary column: DB-200), C3F7O(CF2)3SO2F was contained at 80.36% as a mixture of the n- and i-forms, and the yield was 29.2%.
The mixture was distilled, a fraction appearing from the top of a distillation column at 109° C. to 110° C. was collected, and as a result of analyzing the fraction with a gas chromatograph, the n-form accounted for 88.83%, the i-form for 10.06%, and the total amount of C3F7O(CF2)3SO2F was 98.89%.
19F-NMR (solvent: CDCl3, ppm): —130.08 (s, 2F), −124.10 (s, 2F), −108.54 (s, 2F), −84.33 (m, 2F), −82.82 (m, 2F), −81.62 (t, 3F), 46.32 (m, 1F)
Electrolytic fluorination was carried out in the same manner as Example 5 with the exception of changing to 6 cathodes and 7 anodes and changing the current flow to 6.75 Ahr from the conditions of Example 5.
The total amount of raw materials added was 272.71 g, the total amount of current applied was 1134 Ahr, the voltage (when stable) was 5.2 V to 5.4 V, and the temperature inside the electrolysis bath was 4° C. to 6° C.
The perfluorination product was extracted in the same manner as Example 5, and a total of 138.9 g were extracted. As a result of analyzing the perfluorination product with a gas chromatograph, C4F9O(CF2)3SO2F was contained at 81.76% as a mixture of the n- and i-forms, and the yield was 17.6%.
The C4F9O(CF2)3SO2F was distilled, a fraction appearing from the top of a distillation column at 130° C. to 131° C. was collected, and as a result of analyzing the fraction with a gas chromatograph, the n-form accounted for 84.89%, the i-form for 12.94%, and the total amount of C4F9O(CF2)3SO2F was 97.83%.
19F-NMR (solvent: CDCl3, ppm): −127.11 (s, 4F), −126.88 (d, 2F), −108.82 (s, 2F), −83.58 (m, 2F), −82.98 (m, 2F), −81.68 (t, 3F), 46.03 (m, 1F)
First, C3F7O(CF2)3SO2F was treated for 24 hours at 80° C. in a 20% aqueous KOH solution. Next, the reaction liquid was cooled on standing and further cooled with ice water, and after crystals had adequately precipitated, the crystals were filtered out. Moreover, recrystallization was carried out with water, the resulting crystals were adequately dried and then dissolved in acetone, and the filtrate obtained by filtering with a 0.2 μm filter was concentrated and dried with a rotary evaporator followed by vacuum-drying for 24 hours at room temperature.
19F-NMR (solvent: DMSO-d6, ppm): −129.32 (s, 2F), −123.77 (s, 2F), −114.59 (s, 2F), −83.81 (s, 2F), −82.44 (m, 2F), −81.55 (t, 3F)
Thermal analysis (TG-DTA) result: 397.0° C. (decomposition starting temperature)
The same procedure was carried out for the case of C4F9O(CF2)3SO2F
19F-NMR (solvent: DMSO-d6, ppm): −126.01 (d, 4F), −123.79 (s, 2F), −111.16 (s, 2F), −82.87 (s, 2F), −82.44 (m, 2F), −80.47 (t, 3F)
Thermal analysis (TG-DTA) result: 402.9° C. (decomposition starting temperature)
The surface tension of C3F5O(CF2)3SO3K and C4F9O(CF2)3SO3K as well as C2F5O(CF2)3SO3K and C4F9SO3K serving as comparative examples was measured in ion exchange water.
Surface tension was measured using for the measuring instrument the Model CBVP-Z Wilhelmy Automated Surface Tensiometer (Kyowa Interface Science Co., Ltd.), and the measuring temperature was 23° C. The results are shown in Table 1.
As shown in Table 1, C3F7O(CF2)3SO3K and C4F9O(CF2)3SO3K were clearly determined to demonstrate a high ability to lower surface tension in comparison with C2F5O(CF2)3SO3K and C4F9SO3K.
According to the present invention, molecular design can be carried out with comparative inexpensive hydrocarbon compounds, and perfluorinated compounds can be obtained while retaining the structure thereof. In addition, in addition to the low cost, yield is favorable. Consequently, the present invention in highly useful as a method for synthesizing various novel compounds by using alternative compounds to conventional perfluoroalkylsulfonic acids and derivatives thereof.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2009-223975 | Sep 2009 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2010/067002 | 9/29/2010 | WO | 00 | 3/28/2012 |
