JP2649343B2 - Method for producing phosphate ester - Google Patents

Description

The present invention relates to a method for producing a phosphate ester.

[Problems to be Solved by the Prior Art and the Invention] Phospholipids are deeply involved in functions such as cell compartment formation and mass transport as constituents of cell membranes in vivo, and are also important in various biological activities. It is becoming clear that they are playing important roles.

Phosphatidylglycerol, which is one of the phosphate esters having a glyceryl group, is also a kind of phospholipid,
It has a structure like the formula (IV).

On the other hand, the phosphoric acid ester of the organic hydroxy compound is a detergent, a fiber treatment agent, an emulsifier, a rust inhibitor, a liquid Ein exchanger,
Or it is used in a wide range of fields as pharmaceuticals. For example, phosphate monoester salts of long-chain alkyl alcohols have good foaming power, detergency, low toxicity and low skin irritation, so that conventional alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, α
-It has excellent properties as a detergent replacing olefin sulfonate.

However, with the recent rise in living standards, there has been a demand for the development of cosmetics and cosmetics raw materials having higher safety consciousness and higher safety for the human body. by the way,
Compounds having a structure similar to the phospholipids derived from living organisms shown above are expected to be less irritating to living organisms. However, these reactions are complicated and multi-step reactions, and often require raw materials that are difficult to synthesize or difficult to separate the desired product after the reaction. It was difficult to obtain industrially.

Under such circumstances, the present inventors have made the following general formula (V) simple operation first. (Where b is 0 or 1, and when b is 0, R ³ is a linear or branched alkyl or alkenyl group having 1 to 36 carbon atoms, or a linear or branched chain having 1 to 15 carbon atoms. A phenyl group substituted by a chain alkyl group, R ⁴ is an alkylene group having 2 to 3 carbon atoms, c is 0 to 30. When b is 1, c is 0 and a is 0 Or 1, when b is 1 and a is 0, R ³ is a straight-chain alkyl group having 1 to 22 carbon atoms, and when b is 1 and a is 1, R ³ is 1 to 36 carbon atoms. It is a linear or branched alkyl or alkenyl group.
M 'indicates that the salt is an alkali metal salt. ) Was found to be able to be obtained. That is, the compound represented by the formula (V) is represented by the following general formula (VI): (Wherein, R ³ , R ⁴ , a, b, c and M ′ are the same as those described above), and the following general formula (VI
I) Can be easily produced by reacting with a compound represented by the formula (glycidol), and the obtained compound shows almost the same foam as the corresponding alkali metal salt of phosphoric acid monoester, , Found that the craft point was even lower. The low kraft point means that when these phosphate esters are used as a raw material for cosmetics and cosmetics, they can be easily used as a liquid cleaning base and their use can be expanded. However, in the case of industrial production, there has been a demand for a method of obtaining it at lower cost.

[Means for solving the problem]

Under such circumstances, the present inventors have conducted further intensive studies. As a result, the following general formula (III) was obtained by using a more inexpensive and easily available raw material and by a simple operation. (In the formula, m is 0 or 1, and when m is 0, R ¹ is a linear or branched C1-C36 alkyl group in which a hydrogen atom may be substituted with a fluorine atom or An alkenyl group or a phenyl group substituted with a linear or branched alkyl group having 1 to 15 carbon atoms, wherein R ² has 2 to 3 carbon atoms;
And n is 0 to 30. When m is 1, n is 0, l is 0 or 1, and m is 1, l
Is 0, R ¹ is a linear alkyl group having 1 to 22 carbon atoms,
When m is 1 and l is 1, R ¹ is a linear or branched alkyl or alkenyl group having 1 to 36 carbon atoms. M indicates that it is a salt of an alkali metal. The inventors have found that a phosphoric ester represented by the formula (1) can be produced, and have completed the present invention.

That is, the present invention provides the following general formula (I) (Wherein, R ¹ , R ² , l, m, n and M are the same as described above), and a phosphoric acid monoester salt represented by the following general formula (II) (Wherein X represents a halogen atom). A general formula (I) characterized by reacting epihalohydrin represented by the following formula (first step) and then reacting a basic compound and water (second step). ) Is provided (Scheme I).

(Wherein R ¹ , R ² , l, m, n and M are the same as described above) Examples of the phosphoric acid monoester salt represented by the formula (I) used in the present invention include monoethyl phosphate, monobutyl phosphate , Monooctyl phosphate, monododecyl phosphate, monohexadecyl phosphate, monooctadecyl phosphate, monotetracosyl phosphate, mono-2-ethylhexyl phosphate, mono-2-hexyldecyl phosphate, Mono 2-octyl dodecyl phosphate, mono 2-tetradecyl octadecyl phosphate, mono monomethyl branched isostearyl phosphate, mono octenyl phosphate, monodecenyl phosphate, mono dodecenyl phosphate, monohexadec Senyl phosphate, monooctadecenyl phosphate, monotetracosenyl phosphate, monotricontenyl phosphate,
Monotridecafluorooctyl phosphate, monoheptadecafluorodecyl phosphate, monophenicosafluorododecyl phosphate, monopentacosafluorotetradecyl phosphate, monononacosafluorohexadecyl phosphate, monotriaconta Fluorooctadecyl phosphate,
Mono 2-pentafluoroethyl pentafluorohexyl phosphate, mono 2-tridecafluorohexyl tridecafluorodecyl phosphate, mono-2-heptadecafluorooctylheptadecafluorododecyl phosphate, mono2
Mono- or branched-chain alkyl or alkenyl phosphates such as hen eicosafluorodecyl hen eicosafluorotetradecyl phosphate [R ¹ in formula (I)
Is an alkyl group or an alkenyl group in which a hydrogen atom may be substituted with a fluorine atom, wherein m is 0 and n is 0, which is a linear or branched carbon atom having 1 to 36 carbon atoms; monooctylphenyl phosphoric acid Salts, monoalkyl phenyl phosphates such as monononyl phenyl phosphate [In the formula (I), R ¹ is a phenyl group substituted with a linear or branched alkyl group having 1 to 15 carbon atoms, m is 0, n is 0]; monopolyoxyethylene (3 mol) dodecyl ether phosphate, monopolyoxypropylene (3 mol) decyl ether phosphate, monopolyoxyethylene (8 mol) polyoxypropylene (3 mol) dodecyl Ether phosphate, monopolyoxyethylene (4 mol) octadecenyl ether phosphate, monopolyoxyethylene (3 mol) tridecafluorooctylate Phosphate, monopolyoxyethylene (5 mol) heptadecafluorodecyl ether phosphate, monopolyoxyethylene (3 mol) heneicosafluorododecyl ether phosphate, monopolyoxyethylene (5 mol) 2-tridecafluorohexyl Monopolyoxyalkylene alkyl ether phosphate such as tridecafluorodecyl ether phosphate or monopolyoxyalkylene alkenyl ether phosphate [formula (I)
R ¹ is a linear or branched C1-C36 alkyl or alkenyl group in which a hydrogen atom may be substituted with a fluorine atom, m is 0, n is greater than 0 and 30 or less. Case); monopolyoxyalkylene alkyl phenyl ether phosphate such as monopolyoxyethylene (5 mol) nonylphenyl ether phosphate, monopolyoxypropylene (2 mol) octyl phenyl ether phosphate [in the formula (I), ¹ is a phenyl group substituted with a linear or branched alkyl group having 1 to 15 carbon atoms, m is 0,
when n is a number greater than or equal to 30]; mono-2-hydroxydodecyl phosphate, mono-2-hydroxyhexadecyl phosphate, mono-2-hydroxytridecafluorononyl phosphate, mono-2-hydroxypentadecafluoro Mono-2-hydroxyalkyl phosphates such as decyl phosphate and mono-2-hydroxyheptadecafluoroundecyl phosphate [in the formula (I), R ¹ has ¹ to 22 carbon atoms and a hydrogen atom is a fluorine atom; A linear alkyl group which may be substituted, when l is 0, m is 1, and n is 0]; mono-2-hydroxy-3-dodecyloxypropyl phosphate, mono-2-
Hydroxy-3-monomethyl branched isostearyloxypropyl phosphate, mono-2-hydroxy-3-octadecenyloxypropyl phosphate, mono-2-hydroxy-
Mono-2-hydroxy-3-alkyloxyl phosphate such as 3-heptadecafluorodecyloxypropyl phosphate, mono-2-hydroxy-3- (2-pentafluoroethylpentafluorohexyloxy) propyl phosphate or mono 2-hydroxy-3-alkenyloxypropyl phosphate [In the formula (I), R ¹ has ¹ to 36 carbon atoms.
Alkyl or alkenyl group in which a hydrogen atom of a straight or branched chain may be substituted with a fluorine atom, l is 1, m is 1, and n is 0].

As the alkali metal salt, a sodium salt and a potassium salt are preferable.

The monoalkali metal salt of a phosphoric acid monoester represented by the general formula (I) used in the present invention can be produced, for example, by obtaining a phosphoric acid monoester by any of the following methods and then neutralizing the phosphoric acid monoester. That is, when m is 0, a phosphorylating agent such as phosphorus pentoxide, phosphorus oxychloride, or polyphosphoric acid is reacted with the corresponding organic hydroxy compound to obtain a phosphoric acid monoester. When 1 is 0 and m is 1, a phosphoric acid monoester having a 2-hydroxyalkyl group by reacting a phosphorylating agent such as phosphoric acid or polyphosphoric acid with α-olefin epoxide having a corresponding hydrocarbon group Get. When 1 is 1 and m is 1, a phosphorylating agent such as phosphoric acid or polyphosphoric acid is reacted with an alkyl glycidyl ether or alkenyl glycidyl ether having a corresponding hydrocarbon group to obtain a phosphoric acid monoester.

The phosphoric acid monoester salt (I) used in the present invention preferably has high purity. That is, when a phosphoric diester salt by-produced when phosphorus pentoxide or phosphorus oxychloride is used as a phosphorylating agent is contained, the surface activity as a phosphoric acid monoester decreases or disappears, and further the next epoxy compound and In the above reaction, the purity of the target compound is reduced, and purification for obtaining a high-purity target compound becomes difficult. In addition, orthophosphate produced as a by-product when polyphosphoric acid is used as a phosphorylating agent also reduces the yield of the target reaction in the reaction with the epoxy compound, further reduces the purity of the target compound, and increases the purity of the target compound. Purification becomes difficult. Therefore, it is preferable to use the phosphoric acid monoester salt (I) having a purity of 90% by weight or more.

Examples of the compound represented by the formula (II) used in the present invention include epichlorohydrin (X = Cl in the formula (II)),
Epibromohydrin (X = Br in the formula (II)) and the like are mentioned, and epichlorohydrin is preferred from the viewpoint of price and supply.

The reaction between the monoalkali metal salt of the phosphoric acid monoester of the formula (I) and the epihalohydrin of the formula (II), which is the first step of the production method of the present invention, is carried out by converting epihalohydrin into a monoester of a phosphoric acid monoester. It is preferable to react 1 to 10 mol, particularly 3 to 5 mol, per 1 mol of the alkali metal salt (I).

When the reaction is carried out without converting the phosphoric acid monoester into a monoalkali metal salt, not only the target compound but also a phosphoric acid triester to which one mole of the epihalohydrin has reacted further reduces the yield of the target compound. Absent.
Therefore, when performing this reaction, it is necessary to use the phosphoric acid monoester in the form of the monoalkali metal salt (I).

As the solvent used for the reaction, an inert polar solvent is preferable, and examples thereof include water, methyl alcohol, and ethyl alcohol. Among them, water is preferable. The fact that this water can be used as a solvent is extremely preferable from the viewpoint of safety in the case of industrial production.

It is preferable to carry out the reaction at a reaction temperature of 30 to 100 ° C, particularly preferably 50 to 90 ° C.

The obtained reaction solution contains unreacted epihalohydrin or a hydrolyzate thereof in addition to the target phosphoric acid ester salt represented by the formula (VIII) as shown in Scheme I. Depending on the intended use, the reaction product thus obtained can be used as it is, or can be used for the reaction with the next basic compound, which is the second step, by distilling off a portion of unreacted epihalohydrin and the like. After obtaining a further purified intermediate (VIII), it is also possible to proceed to the next second step. For example, sodium dodecylphosphate (R ¹ = C ₁₂ H ₂₅ , m = 0, n =
0, M = Na) and epichlorohydrin (X = Cl in the compound of formula (II)), the epichlorohydrin is reacted with an aqueous solution of sodium dodecyl phosphate, and then water is distilled off or the reaction is allowed to proceed. An organic substance saturated with an electrolyte such as sodium chloride or potassium chloride is extracted into an organic solvent such as ethyl ether, and then ethyl ether is distilled off to separate from water. Acetone is added to the solution to form dodecyl 2-hydroxy-3. -Sodium chloropropyl phosphate (R ¹ = C in the compound represented by the formula (VIII)
₁₂ H ₂₅ , m = n = 0, M = Na, X = Cl)
The intermediate (VIII) having high purity can be obtained by separating from epichlorohydrin soluble in acetone and its hydrolyzate.

In the reaction of the second step, basic compounds include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide, and organic amines. Of these, sodium hydroxide and potassium hydroxide are preferred, and water is used as an aqueous solution of these basic compounds. Accordingly, the reaction is carried out using water as a solvent. However, at this time, a solvent other than water may be mixed and used, and for example, a mixture of a lower alcohol and an ether may be used without any problem.

The second step may be carried out by reacting the obtained compound represented by the formula (VIII) with an equimolar amount or more of a basic compound and water, and 1 mol to 1 mol of the compound represented by the formula (VIII).
5 mol, preferably 1.1 to 2 mol of the basic compound and water may be reacted. However, when the compound of the formula (VIII) is subjected to the reaction of the second step without purification and isolation in the reaction of the first step, it is necessary to take into account the hydrolyzate of epihalohydrin present in the system. It is necessary to further add a basic compound at least equimolar to the hydrolyzate of epihalohydrin and water.

The reaction temperature is preferably 30 to 100 ° C, particularly preferably 50 to 90 ° C.

〔The invention's effect〕

ADVANTAGE OF THE INVENTION According to this invention, the phosphate which is highly safe with respect to a human body and can be widely used in the fields of cosmetics and cosmetics can be produced industrially very advantageously.

Furthermore, the compounds of formula (III) prepared according to the present invention are useful as intermediates in the synthesis of phosphatidylglycerol analogs. For example, the 2-hydroxyl group of 2-hydroxyoctadecyl phosphate (in the compound represented by formula (I), m = 1, 1 = 0, R ¹ = C ₁₆ H ₃₂ , n = 0, M = H) By acylation, a compound similar to a biological phospholipid can be obtained, and its use can be widely used other than cosmetics and cosmetics.

〔Example〕

 Next, an example will be described.

Example 1 In a reactor, 200 g of monododecyl phosphoric acid having a purity of 97% (0.73 mol; AV1 of this sample (mg of KOH required to neutralize 1 g of a sample of the present phosphoric acid monoester to the first equivalent point) ,
The same applies to the following) = 210.3, AV2 (mg number of KOH required to neutralize 1 g of a sample of the present phosphoric acid monoester to the second equivalent point,
(The same applies to the following.) = 420.8), 750 ml of a 1N aqueous sodium hydroxide solution was added, and the mixture was stirred and heated to 80 ° C. to be uniform. At this time, the acid value of the reaction system (mg number of KOH required to neutralize 1 g of the sample, the same applies hereinafter) was 42.9. Next, while maintaining the reaction system at 80 ° C., 347 g (3.75 mol) of epichlorohydrin was gradually added, and the mixture was stirred at this temperature for 4 hours. At this time, the acid value of the reaction system was almost 0, indicating that the reaction was completed. Next, 1000 ml of acetone was added to the non-volatile liquid residue obtained by freeze-drying the reaction solution, and the mixture was refrigerated at 5 ° C. One day later, the precipitated crystals were collected and recrystallized from acetone to give 193 g of white crystals of sodium dodecyl 2-hydroxy-3-chloropropylphosphate (yield: 69).
%)was gotten.

193 g of the obtained sodium dodecyl 2-hydroxy-3-chloropropylphosphate was dissolved in 500 g of water, and a 30% aqueous solution of 25 g (0.5 mol) of sodium hydroxide was added.
The mixture was heated and stirred for an hour. When the reaction was followed by high performance liquid chromatography (hereinafter, HPLC), the peak of sodium dodecyl 2-hydroxy-3-chloropropylphosphate disappeared, and a new peak appeared. After the water in the reaction system was replaced with ethanol and the precipitated salt was filtered off, the ethanol was distilled off under reduced pressure and poured into a large amount of acetone to obtain 165 g of white crystals. ¹ H-NMR spectrum of this crystal,
From the results of the analysis and elemental analysis, the obtained crystal was found to be
It was confirmed to be sodium dihydroxypropyl phosphate. ¹ H-NMR (D ₂ O, internal standard: sodium 3-trimethylsilylpropanesulfonate); δ 0.8 ppm (t, 3H, -P-OCH ₂ (CH ₂ ) ₁₀ CH ₃ ) δ 1.3 ppm (brord s, 20H) , -P-OCH ₂ (CH ₂ ) ₁₀ CH ₃ ) δ 3.4 to 3.9 ppm (m, 9H, HO-CH ₂ CH (OH) CH ₂ OPOCH _2- ) Example 2 As in Example 1, 21 g of epichlorohydrin was added to a solution of 20 g of monododecyl phosphate and 75 ml of 1N sodium hydroxide.
Was added and reacted at 80 ° C. for 10 hours. At this time, the acid value of the reaction system was almost 0. Next, a 30% aqueous solution of 9.5 g of sodium hydroxide is added to the reaction solution, and the mixture is further reacted at 80 ° C. for 5 hours. When the reaction system was analyzed by HPLC, it was found that the sodium dodecyl 2,3-dihydroxypropylphosphate obtained in Example 1 was formed. After the system was neutralized with hydrochloric acid, the water in the reaction system was replaced with ethanol, and the precipitated salt was separated by filtration. , 3−
16.5 g of sodium dihydroxypropyl phosphate was obtained.

Example 3 50% of 98% pure 2-decyltetradecyl phosphate was placed in a reactor.
g (0.11 mol, AV1 of this sample = 126.5, AV2 = 253.
1) was added, 113 ml of a 1 N aqueous solution of sodium hydroxide was added, and the mixture was stirred, heated to 80 ° C., and made uniform. At this time, the acid value of the reaction system was 37.7. Next, while maintaining the reaction system at 80 ° C, 52 g (0.56 mol) of epichlorohydrin was gradually added,
Stirred at this temperature for 6 hours. At this time, the acid value of the reaction system was almost 0. Then, 56 g of a residue obtained by distilling water, unreacted epichlorohydrin and its environmental substances under reduced pressure are dissolved in 100 ml of tetrahydrofuran, 230 ml of 1N sodium hydroxide is added, and the mixture is refluxed for 10 hours. The obtained reaction solution was extracted twice with a solution of chloroform / methanol / water = 10/10/9 (volume ratio), the solvent was distilled off from the obtained organic solvent layer, and the obtained residue was washed with 500 ml of acetone. After washing twice, 49 g of sodium 2-decyltetradecyl 2,3-dihydroxypropylphosphate was obtained.

Example 4 20 g of mono 2-hydroxydodecyl phosphate having a purity of 95%
(0.067 mol, where AV1 = 200.2, AV2 = 400.
5) was added to and dissolved in 71.4 ml of a 1 N aqueous solution of sodium hydroxide (the acid value of the reaction system was 42.4 at this time), and 25 g (0.27 mol) of epichlorohydrin was gradually added at 70 ° C. Stirred for hours. At this time, the acid value of the reaction system was almost 0. Further, a 30% aqueous solution of 11 g (0.28 mol) of sodium hydroxide was added to the reaction mixture, and the mixture was reacted at 80 ° C. for 5 hours. When the obtained reaction solution was analyzed by HPLC, a new product peak was observed. After neutralizing the system with hydrochloric acid, this was separated by HPLC and the solvent was distilled off under reduced pressure. 19.5 g of -hydroxydodecyl 2,3-dihydroxypropyl sodium phosphate was obtained.

Example 5 20 g of monotrioxyethylene dodecyl ether phosphoric acid having a purity of 98% (0.049 mol, except that AV1 of this sample was 142.8,
AV2 = 288.2) was added to and dissolved in 50.9 ml of a 1 N aqueous solution of sodium hydroxide (the acid value of the reaction system was 39.8 at this time), and 18 g (0.19 mol) of epichlorohydrin was gradually added at 70 ° C. For 20 hours. At this time, the acid value of the reaction system was almost 0. Further, a 30% aqueous solution of 8 g (0.2 mol) of sodium hydroxide was added to the reaction mixture,
The reaction was carried out at 5 ° C. for 5 hours. When the obtained reaction solution was analyzed by HPLC, a peak of a new product was observed.The system was neutralized with hydrochloric acid, and this was separated by HPLC, and the solvent was distilled off under reduced pressure. Oxyethylene dodecyl ether
18.2 g of sodium 2,3-dihydroxypropyl phosphate
Obtained.

Example 6 20 g of monononylphenylphosphoric acid having a purity of 95% (0.064 mol,
However, AV1 = 179.3 and AV2 = 359.0 of this sample were added and dissolved in 63.9 ml of 1N aqueous sodium hydroxide solution (the acid value of the reaction system was 41.5 at this time), and epichlorohydrin 24 g (0.26 mol ) Was added slowly and stirred at this temperature for 20 hours. At this time, the acid value of the reaction system was almost 0. Further, a 30% aqueous solution of 11 g (0.28 mol) of sodium hydroxide was added to the reaction mixture, and the mixture was reacted at 80 ° C. for 10 hours. When the obtained reaction solution was analyzed by HPLC, a new product peak was observed.The system was neutralized with hydrochloric acid, and then separated by HPLC.The solvent was distilled off under reduced pressure to obtain the desired compound, nonylphenyl. 15.7 g of sodium 2,3-dihydroxypropyl phosphate was obtained.

Example 7 20 g of monoheptadecafluorodecyl phosphate having a purity of 97%
(0.036 mol, where AV1 = 108.9, AV2 = 217.
0) was added to and dissolved in 38.8 ml of 1N aqueous sodium hydroxide solution (the acid value of the reaction system was 35.7 at this time), and 13 g (0.14 mol) of epichlorohydrin was gradually added at 70 ° C. Stirred for hours. At this time, the acid value of the reaction system was almost 0. Further, a 30% aqueous solution of 6 g (0.15 mol) of sodium hydroxide was added to the reaction mixture, and the mixture was reacted at 80 ° C. for 10 hours. When the obtained reaction solution was analyzed by HPLC, a peak of a new product was observed.The system was neutralized with hydrochloric acid, and this was fractionated by HPLC. 17.3 g of sodium decafluorodecyl 2,3-dihydroxypropyl phosphate was obtained.

Example 8 20 g of mono 2-hydroxy-3-dodecyloxypropyl phosphoric acid having a purity of 95% (0.056 mol;
= 156.6, AV2 = 312.5) was added to and dissolved in 55.8 ml of a 1 N aqueous sodium hydroxide solution (the acid value of the reaction system at this time was 39.8).
Then, 21 g (0.23 mol) of epichlorohydrin was gradually added at 70 ° C., and the mixture was stirred at this temperature for 20 hours. At this time, the acid value of the reaction system was almost 0. Further, to this reaction mixture, a 30% aqueous solution of 9.5 g (0.24 mol) of sodium hydroxide was added and reacted at 80 ° C. for 5 hours. The obtained reaction solution is subjected to HPLC
As a result, a new product peak was observed. The system was neutralized with hydrochloric acid and then separated by HPLC. The solvent was distilled off under reduced pressure to obtain the desired compound 2-hydroxy-3-dodecyloxy. 19.5 g of sodium propyl 2,3-dihydroxypropyl phosphate was obtained.

Claims (1)

(57) [Claims] 1. The following general formula (I) (In the formula, m is 0 or 1, and when m is 0, R ¹ is a linear or branched C1-C36 alkyl group in which a hydrogen atom may be substituted with a fluorine atom or An alkenyl group or a phenyl group substituted with a linear or branched alkyl group having 1 to 15 carbon atoms, wherein R ² has 2 to 3 carbon atoms;
And n is 0 to 30. When m is 1, n is 0, l is 0 or 1, and m is 1, l
Is 0, R ¹ is a straight-chain alkyl group having 1 to 22 carbon atoms and a hydrogen atom optionally substituted with a fluorine atom. When m is 1 and 1 is 1, R ¹ is 1 to 36 linear or branched alkyl or alkenyl groups in which a hydrogen atom may be substituted with a fluorine atom. M indicates that it is a salt of an alkali metal. ) And a phosphoric acid monoester salt represented by the following general formula (II) (Wherein X represents a halogen atom), wherein an epihalohydrin represented by the following formula is reacted, and then a basic compound and water are reacted. (Wherein, R ¹ , R ² , l, m, n and M are the same as described above).