JPH08188552A - Process for producing acyloxybenzoic acid or salt thereof - Google Patents

Abstract

(57) [Summary] [Objective] To provide an industrial production method capable of producing acyloxybenzoic acid or a salt thereof at a low cost with high selectivity and high yield. [Structure] When compound (2) is produced by reacting hydroxybenzoic acid (salt) with an acylating agent, the reaction is carried out in the presence of compound (3) or (4). Embedded image (R ¹ is a C _1-21 alkyl group or the like, h is 1 to 3, i is m−h
, M is 1 to 3, M ¹ and M ² are hydrogen atoms or alkali metals, etc.) (R ² is a hydrogen atom or a C _1-22 alkyl group, R ³ is C _1-21
R ⁴ is a hydrogen atom or a C _1-22 alkyl group, B is a C _2-4 alkylene group, and p and q are numbers from 5 to 200. )

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a process for producing an acyloxybenzoic acid or a salt thereof which is useful as a bleaching activator in an oxygen-based bleaching agent. More specifically, an acylating agent is allowed to act on hydroxybenzoic acid or a salt thereof to promote the esterification reaction by allowing a specific alkylene oxide adduct to coexist when producing an acyloxybenzoic acid or a salt thereof. As a result, a good quality acyloxybenzoic acid or a salt thereof with less side reaction products is obtained, and at the same time, the alkylene oxide adduct acts as a solubilizing agent so that a good water-soluble acyloxybenzoic acid or a salt thereof is obtained. The present invention relates to a method of manufacturing.

[0002]

2. Description of the Related Art Acyloxybenzoates are similar to acyloxybenzene sulfonates in hydrogen peroxide and hydrogen peroxide-generating substrates such as PC (sodium percarbonate) and PB (sodium perborate). By contacting it, it easily produces organic peracid even at low temperatures, and
It is a particularly useful compound as a bleach activator because it effectively exhibits bleaching performance against stain stains (JP-A-6-21).
1746, JP-A-6-145697). In any of the methods described in the above publications, a high-purity product cannot be obtained in this method for producing an acyloxybenzoate, and a refining operation using a solvent is indispensable, which is unsuitable as a commercial production process.

Therefore, it has been desired to develop a method capable of industrially producing acyloxybenzoic acid and its salt with high selectivity and high yield. An object of the present invention is to provide an industrial production method capable of producing an acyloxybenzoic acid or a salt thereof at high cost with high selectivity in producing a highly pure acyloxybenzoic acid or a salt thereof. It is in.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have earnestly studied the reaction between hydroxybenzoic acid or a salt thereof and an acylating agent, and as a result, in the presence of a specific alkylene oxide adduct. Surprisingly, the desired esterification reaction is greatly accelerated,
It has been found that a high conversion and selectivity can be obtained at a low temperature unprecedented, and an acyloxybenzoic acid or a salt thereof which has a high purity even in an unpurified state and whose water solubility is greatly improved by the coexistence of the above-mentioned alkylene oxide adduct. They have found that they can be obtained and have completed the present invention. That is, the present invention is
General formula (1)

[0005]

Embedded image

[Wherein M ¹ and M ^{2 represent a} hydrogen atom or an alkali metal, alkaline earth metal, ammonium, substituted ammonium or quaternary ammonium, and M ¹ and M ² may be the same or different. Good. m: Indicates the number of 1 to 3. ] The hydroxy benzoic acid represented by the following formula or a salt thereof or a mixture thereof is reacted with an acylating agent to give a compound represented by the general formula (2):

[0007]

[Chemical 9]

[Wherein M ¹ and M ² have the same meanings as described above] R ¹ : a linear or branched alkyl group or alkenyl group having ^{1 to} 21 carbon atoms, which may be substituted with halogen, and may have an ester group, an amide group, an ether group or a phenylene group inserted, or Unsubstituted or linear or branched alkyl or alkenyl groups or halogens having 1 to 22 carbon atoms, which may be substituted with halogen, and in which an ester group, amide group, ether group or phenylene group may be inserted. Represents a phenyl group which may be substituted with. h: shows the number of 1-3. i: Indicates the number obtained by subtracting h from m. Here, m has the same meaning as described above. ] When manufacturing the acyloxy benzoic acid represented by these, its salt, or its mixture, General formula (3) or (4)

[0009]

[Chemical 10]

[In the above formulas (3) and (4), R ^{2 is a} hydrogen atom or may be substituted with a halogen atom having 1 to 22 carbon atoms, and an ester group, an amide group, an ether group or a phenylene group may be substituted. A linear or branched alkyl group or alkenyl group which may be inserted, or an unsubstituted or C1-C22 alkyl group which may be substituted with a halogen, and which may be an ester group, an amide group, an ether group or a phenylene group. It represents a linear or branched alkyl or alkenyl group which may be inserted, a phenyl group which may be substituted with a halogen, or a polyhydric alcohol residue. R ^3: 1 to 21 carbon atoms, may be substituted by halogen, an ester group, an amide group, a linear optionally an ether group or a phenylene group is inserted or branched chain alkyl or alkenyl group or, Unsubstituted or linear or branched alkyl or alkenyl groups or halogens having 1 to 22 carbon atoms, which may be substituted with halogen, and in which an ester group, amide group, ether group or phenylene group may be inserted. Represents a phenyl group which may be substituted with. R ^4: a hydrogen atom or 1 to 22 carbon atoms, may be substituted with a halogen, an ester group, an amide group, or an alkyl group which may linear be an ether group or a phenylene group is inserted or branched chain An alkenyl group, or a straight-chain or branched-chain alkyl group which is unsubstituted or has 1 to 22 carbon atoms and which may be substituted with a halogen, and which may have an ester group, an amide group, an ether group or a phenylene group inserted, or Alkenyl group or phenyl group optionally substituted by halogen, polyhydric alcohol residue, or formula

[0011]

[Chemical 11]

(In the formula, R ³ has the same meaning as described above, and two R ³ may be the same or different.) B: A linear or branched alkylene group having 2 to 4 carbon atoms is shown, and p B's or q B's may be the same or different. p and q: each is a number of 5 to 200 indicating the average number of moles of alkylene oxide added, and may be the same or different. ] The method for producing acyloxybenzoic acid or a salt thereof is characterized by carrying out the reaction in the presence of one or two or more selected from the alkylene oxide adducts represented by:

Hereinafter, the present invention will be described in detail. The hydroxybenzoic acid or a salt thereof as the raw material of the present invention is represented by the above general formula (1), wherein M ¹ and M ² are hydrogen atom, alkali metal, alkaline earth metal, ammonium, substituted ammonium. Or quaternary ammonium, but M ¹ , M ²
May be the same or different. Examples of alkali metals include Li, Na and K, and examples of alkaline earth metals include M.
Examples include g and Ca. Specific examples of the substituted ammonium include monomethylammonium, dimethylamine, trimethylamine, monoalkylamine having 2 to 14 carbon atoms or monoalkyldimethylamine, triethanolamine, monoethanolamine, methylmonoethanolamine, dimethylmonoethanol. Amine, diethanolamine, methyldiethanolamine, carbon number 2
Examples include 16 monoalkyl monoethanolamines, as well as ammoniums such as monoalkyldiethanolamine, pyridine, piperidine, ethylenediamine, diethylenetriamine, N, N-dimethylaminopropylamine and aminoethylethanolamine. However, ethanolamines that can easily react with an acylating agent even under acidic conditions during the esterification reaction may complicate the reaction and may give unfavorable results depending on the purpose. Specific examples of the quaternary ammonium include monoalkyltrimethylammonium having 1 to 24 carbon atoms, which may be single or mixed, and which may be unsaturated, single or mixed carbon atoms having 1 to 20. And dialkyl dimethyl ammonium, which may be unsaturated, or tetraalkyl ammonium having 1 to 4 carbon atoms. Among them, in view of water solubility and performance of the target acyloxybenzoic acid or a salt thereof, Li, K, Na, Mg, ammonium (NH ₄ ⁺ )
Are preferred, and Li, K, and Na are particularly preferred. Further, the number m of substituents at the active site capable of reacting with an acylating agent is 1 to 3, and can be selected according to the water solubility of the target substance.
It is preferably 1.

Specific examples of the hydroxybenzoic acid represented by the general formula (1) or a salt thereof include salicylic acid, p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid and 2,5-
Examples thereof include dihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, or its Na salt, K salt, Li salt, Mg salt and the like.
Among these, salicylic acid, p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid or its Na
The use of salt, K salt or Mg salt is preferable and practical.
Further, salicylic acid, p-hydroxybenzoic acid or its Na salt, K salt or Mg salt is particularly preferable in terms of raw material cost.

The hydroxybenzoic acid represented by the general formula (1) or a salt thereof is commercially available in the form of a corresponding acid or salt, and any of them can be used. Incidentally, dehydration of this hydroxybenzoic acid or a salt thereof generally requires conditions such as high temperature under an inert gas stream or azeotropic dehydration, and its improvement is desired, but it is used for the reaction of the present invention as described later. By adding the alkylene oxide adduct represented by the general formula (3) or (4) before or after neutralization, the hydroxybenzoic acid or its salt can be dried extremely in terms of physical properties and equipment compatibility. It is good and preferable.

The hydroxybenzoic acid represented by the general formula (1) or a salt thereof used in the present invention is preferably used in a substantially anhydrous form. Here, “substantially anhydrous” does not mean a completely anhydrous state, but a small amount of water contained in the raw material itself, for example, 0.5% by weight or less of water is substantially anhydrous. If a substantial amount of water is present, hydrolysis of the acylating agent will occur and the reaction yield will decrease. Dehydration is carried out if necessary, and specifically, in that case, for example, 0.05 to 1 part by weight of hydroxybenzoic acid represented by the general formula (1) or a salt thereof before or after neutralization is added.
Add 20 parts by weight of one or more alkylene oxide adducts represented by the general formula (3) or the general formula (4), mix by stirring or kneading, and disperse well, 1
The treatment may be performed at 10 to 200 ° C. under a reduced pressure of 0.01 to 500 Torr for 1 to 10 hours, and a water content of 0.5% by weight or less can be easily obtained by the above treatment.

R ^{2 in} the formula of the alkylene oxide adduct represented by the general formula (3) used in the present invention may be substituted with a hydrogen atom or a halogen having 1 to 22 carbon atoms, Ester group, amide group, ether group or phenylene group may be inserted linear or branched alkyl group or alkenyl group, or unsubstituted or having 1 to 22 carbon atoms, may be substituted with halogen, It represents a linear or branched alkyl or alkenyl group in which an ester group, an amide group, an ether group or a phenylene group may be inserted, or a phenyl group which may be substituted with halogen, or a polyhydric alcohol residue.
As the substituent of the phenyl group, an alkyl group having 1 to 4 carbon atoms or halogen is preferable. R ² is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 22 carbon atoms. B represents a linear or branched alkylene group having 2 to 4 carbon atoms, preferably ethylene group or propylene group, and more preferably ethylene group. In addition, p represents the average number of moles of alkylene oxide added, 5 to 200
, Preferably 5 to 120, more preferably 5 to 60, and p B's may be the same or different.

Specific examples of the alkylene oxide adduct represented by the general formula (3) include those having an average molecular weight of about 200 to about.
9000 polyethylene glycol (PEG), polypropylene glycol, polybutylene glycol, polyoxyethylene polypropylene glycol, polyoxypropylene polyethylene glycol, polyoxyethylene polybutylene glycol, or neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, Sorbitan, glucose,
Alkylene oxide adducts of polyhydric alcohols such as maltose, or polyoxyalkylene ethers of alcohols having 1 to 22 carbon atoms (for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i- of polyoxyethylene). Butyl, t-butyl, n-octyl, 2-ethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-octadecyl, oleyl ether and the like).

In addition, in the alkylene oxide adduct represented by the general formula (4), R ³ in the formula is 1 to 21 carbon atoms,
It may be substituted with halogen, a linear or branched alkyl group or alkenyl group which may have an ester group, an amide group, an ether group or a phenylene group inserted therein, or an unsubstituted group or a carbon number of 1 to 22, It may be substituted with halogen, and a linear or branched alkyl group or alkenyl group which may have an ester group, amide group, ether group or phenylene group inserted or a phenyl group which may be substituted with halogen may be substituted. Show. As the substituent of the phenyl group, an alkyl group having 1 to 4 carbon atoms or halogen is preferable. R ³ is preferably a linear or branched alkyl group having 1 to 21 carbon atoms. R ⁴ is a hydrogen atom, or a linear or branched alkyl group having 1 to 22 carbon atoms, which may be substituted with halogen, and which may have an ester group, an amide group, an ether group or a phenylene group inserted therein. Or an alkenyl group, or a straight-chain or branched-chain alkyl group which is unsubstituted or has 1 to 22 carbon atoms and which may be substituted with a halogen, and in which an ester group, an amide group, an ether group or a phenylene group may be inserted. Or an alkenyl group, a phenyl group which may be substituted with halogen, a polyhydric alcohol residue, or R ³
A carboxylic acid residue represented by CO- is shown. As the substituent of the phenyl group, an alkyl group having 1 to 4 carbon atoms or halogen is preferable. Further, as R ⁴ , a hydrogen atom or a carbon number of 1 to 22
The straight chain or branched chain alkyl group of is preferable. In addition, as for B, the same as described above, q represents the average number of moles of alkylene oxide added, 5 to 200, preferably 5 to 120.
, And more preferably 5 to 60, and q B's may be the same or different.

Specific examples of the alkylene oxide adduct represented by the general formula (4) include those having an average molecular weight of about 200 to about.
So-called carboxylic acid monoesters of glycols such as 9000 polyethylene glycol, polypropylene glycol, polybutylene glycol, polyoxyethylene polypropylene glycol, polyoxypropylene polyethylene glycol, polyoxyethylene polybutylene glycol or glycols with mixed alkylene oxide (exemplified by PEG Then, PEG monoacetate, P
EG monopropionate, PEG monobutyrate, PE
G monohexanoate, PEG monoheptanoate, P
EG monooctanoate, PEG monononanoate, P
EG monodecanoate, PEG monoundecanoate,
PEG monolaurate, PEG monomyristate, PE
G monopalmitate, PEG monostearate, PEG
Monooleate, PEG monobehenate, etc.), carboxylic acid diesters of the above glycols (acetic acid, propionic acid,
One or more carboxylic acid residue arbitrarily selected from carboxylic acids such as butyric acid, caproic acid, caprylic acid, pelargonic acid, isononanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid Or a carboxylic acid ester of an alkylene oxide adduct of an alcohol having 1 to 22 carbon atoms, such as a polyoxyalkylene alkyl ether or a polyoxyalkylene alkenyl ether having an alkyl or alkenyl group having 1 to 22 carbon atoms. Examples thereof include carboxylic acid esters.

Among the alkylene oxide adducts represented by the above general formula (4), preferred are carboxylic acid esters of alcohol alkylene oxide adducts having 1 to 22 carbon atoms, specifically, for example, Methyl alcohol, ethyl alcohol, n-propyl alcohol, i-
Propyl alcohol, n-butyl alcohol, i-butyl alcohol, t-butyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, n-decyl alcohol, n-dodecyl alcohol, n-tetradecyl alcohol, n-octadecyl alcohol or oleyl. Polyoxyalkylene adducts of alcohols such as alcohol, acetic acid, propionic acid, butyric acid, caproic acid,
Caprylic acid, pelargonic acid, isononanoic acid such as 3,5,5-trimethylcaproic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid,
Examples thereof include esters of carboxylic acids represented by behenic acid, 6-chlorocaproic acid, lauroyloxyacetic acid, N-lauroylaminopropionic acid and the like. Among these,
In terms of detergency of the base itself and solubilization of the acyloxybenzoate, an ester of an alkylene oxide adduct of an alcohol having 1 to 4 carbon atoms and an aliphatic carboxylic acid having 2 to 22 carbon atoms is It is preferable from the viewpoint of solubilization of acyloxybenzoate. Particularly preferably, methanol or ethanol having a higher solubilizing ability as described above, particularly acetic acid of alkylene oxide adduct of methanol,
Propionic acid, butyric acid, caproic acid, caprylic acid, pelargonic acid, 3,5,5-trimethylcaproic acid, capric acid,
Carboxylic acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and behenic acid, more preferably linear or branched aliphatic carboxylic acids having 2 to 16 carbon atoms, and particularly preferably 6 to 6 carbon atoms. 12 straight-chain saturated aliphatic carboxylic acid esters are preferable, and in particular, in view of the above-mentioned solubilizing ability, as the kind of alkylene oxide adduct, ethylene oxide adduct or other alkylene oxide and ethylene oxide block or random addition is used. The thing is preferable.

Here, the alkylene oxide adduct represented by the general formula (3) or the general formula (4) is optional as long as it promotes the solubilization of the target acyloxybenzoic acid or its salt. However, in the esterification reaction, the carboxylic acid residue usually causes a transesterification reaction to easily react with the carboxylic acid residue in the alkylene oxide adduct and the carboxylic acid residue in the acyloxybenzoate. The residues are mixed. Therefore, the carboxylic acid residue uses an alkylene oxide adduct composed of the same carboxylic acid residue as the carboxylic acid residue of the acylating agent also from the viewpoint of improving the yield of the target acyloxybenzoic acid or a salt thereof. Preferably.

The acylating agent used in the esterification of the present invention is represented by the general formula (5)

[0024]

[Chemical 12]

[Wherein R ¹ has the same meaning as described above. X: Indicates a halogen atom. ] Or a carboxylic acid halide represented by the general formula (6)

[0026]

[Chemical 13]

[Wherein R ¹ has the same meaning as described above. R ⁵ : a straight-chain or branched alkyl group or alkenyl group having 1 to 21 carbon atoms, which may be substituted with halogen, and in which an ester group, an amide group, an ether group or a phenylene group may be inserted, or Unsubstituted or linear or branched alkyl or alkenyl groups or halogens having 1 to 22 carbon atoms, which may be substituted with halogen, and in which an ester group, amide group, ether group or phenylene group may be inserted. Represents a phenyl group which may be substituted with and may be the same as or different from R ¹ . ] The carboxylic acid anhydride represented by these can be used.

Among these acylating agents, as mentioned above, the transesterification reaction usually occurs during the esterification reaction, so that the desired acyloxybenzoic acid having a carboxylic acid residue and its salt can be obtained without lowering the yield. For this purpose, the use of the same carboxylic acid residue as the alkylene oxide adduct represented by the general formula (4) gives preferable results.
Further, as the carbon chain length, those having a longest carbon chain length of 2 to 16 containing carbonyl carbon are good for the purpose of, for example, a bleach activator. Further, it forms an organic peracid that exerts a well-balanced effect on both hydrophilic stains such as black tea and yellowing of underwear, stains on collar sleeves, lipophilic stains such as ketchup, curry and urine. For the purpose, those having a linear or branched carboxylic acid residue having 6 to 12 carbon atoms, particularly those having a linear carboxylic acid residue having 12 carbon atoms are particularly effective. The carboxylic acid residue, specifically, acetic acid, propionic acid, butyric acid, caproic acid, isoheptanoic acid, caprylic acid, isooctanoic acid, pelargonic acid, isononanoic acid such as 3,5,5-trimethylcaproic acid, capric acid, Residues of lauric acid, myristic acid, and palmitic acid are preferable, and more preferably caproic acid, isoheptanoic acid, caprylic acid, isooctanoic acid, pelargonic acid, and 3, for the reasons described above.
Residues of 5,5-trimethylcaproic acid, isoperargonic acid, capric acid and lauric acid, particularly lauric acid residue, are preferred.

The halide of the carboxylic acid halide represented by the general formula (5) may be any of F, Cl, Br, I, etc. because there is no difference in the reaction, but it is an industrial general-purpose raw material. Certain carboxylic acid chlorides have cost advantages. The carboxylic acid halide may be either a non-distilled product or a distilled product, but in the hue of the target product, acyloxybenzoic acid or a salt thereof, it is preferable to use a distilled product, from the viewpoint of cost. Is preferably a non-distilled product.

Another acylating agent of the general formula (6)
The two carboxylic acid residues in the carboxylic acid anhydride represented by are selected from the same carboxylic acid residues in the above-mentioned carboxylic acid halide, but the two carboxylic acid residues are They may be the same or different depending on the purpose. Any of the above acylating agents may be used alone or as a mixture, but it is preferable to use a carboxylic acid halide which produces less carboxylic acid as a by-product.

According to the present invention, the amount of the alkylene oxide adduct represented by the general formula (3) or (4) used is the total amount of the hydroxybenzoic acid represented by the general formula (1) or the hydroxybenzoic acid represented by the general formula (1). In general, 0.1 part by weight of salt is used.
Good results are obtained with ~ 20 parts by weight. If the amount is less than 0.1 part by weight, the effect of promoting the esterification reaction, the effect of improving the physical properties, and the function of promoting the dissolution of acyloxybenzoic acid or a salt thereof may not be sufficiently exhibited. On the other hand, if the amount exceeds 20 parts by weight, the above-mentioned functions are not problematic and may be improved with an increase in the amount used, but in actual use, the desired acyloxybenzoic acid or a salt thereof is used in the product. It cannot be said to be preferable because the content rate decreases. Allowing a high content of acyloxybenzoic acid or its salt while maintaining the respective effects of promoting reaction and improving reaction physical properties during esterification, and improving solubility of acyloxybenzoic acid or its salt in water, or acyloxybenzoic acid Alternatively, in order to avoid unnecessary dilution of the salt thereof, the total amount of the alkylene oxide adduct is preferably 0.2 to 5 parts by weight with respect to 1 part by weight of hydroxybenzoic acid or a salt thereof,
Particularly preferably, it is 0.5 to 2 parts by weight.

The alkylene oxide adduct represented by the general formula (3) and the alkylene oxide adduct represented by the general formula (4) can be used alone or as a mixture of two or more kinds, The weight ratio of these is not particularly limited and can be 0/100 to 100/0.

In the present invention, the reaction of the present invention can be carried out basically without using any solvent, but if necessary, for example, toluene, xylene, ethylbenzene, cumene, 1,2-dichloroethane, trichloroethane, Tetrachloroethane, trichloroethylene, tetrachloroethylene, carbon tetrachloride, N, N-dimethylformamide,
Solvents such as N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, hexane and cyclohexane are 0.1 to 20 times by weight that of the hydroxybenzoic acid represented by the general formula (1) or a salt thereof. May be used.

Further, the acylating agent such as the carboxylic acid halide represented by the general formula (5) and the carboxylic acid anhydride represented by the general formula (6) is a hydroxybenzoic acid represented by the general formula (1). Or, it is usually used in an amount of 0.5 to 2.0 times the molar amount of the salt. Preferably, the molar ratio calculated by the following formula is 0.5 to
When 1.3, it gives a good reaction yield.

[0035]

[Equation 1]

Further, when the above molar ratio is 0.8 to 1.05,
A high reaction rate and high selectivity of a carboxylic acid halide or a carboxylic acid anhydride can be obtained, which is particularly preferable. In addition, in one of the raw materials, monohydroxybenzoate,
Salicylates, which are generally o-forms, have lower reactivity with acylating agents than p-hydroxybenzoates. Therefore, when salicylate is used as a raw material, it is necessary to take measures such as carrying out reaction for a long time.

In the present invention, as the acylating agent, the hydroxybenzoic acid represented by the general formula (1) or a salt thereof is well dispersed or partially dispersed in the alkylene oxide adduct represented by the general formula (3) or (4). Add dropwise to the dissolved slurry. The addition of these acylating agents can be carried out at a temperature above the melting point of the alkylene oxide adduct used. In particular, when the carboxylic acid halide represented by the general formula (5) is used as the acylating agent, the temperature at the dropping is 150 ° C. in order to suppress side reactions derived from the carboxylic acid halide.
The following are preferred. Considering the hues of both the target acyloxybenzoic acid or its salt and the alkylene oxide adduct and the thermal stability of the base itself, 120 ° C. or lower gives a more preferable result. Furthermore, 60 to 100 ° C. is most preferable. The dropping time can be basically set within a range in which the above temperature can be maintained. Further, when the carboxylic acid halide represented by the general formula (5) is used as the acylating agent, hydrogen halide such as HCl is by-produced along with the dropping, and the dropping time is adjusted so that it can be removed sufficiently. It is desirable to do. Specifically, in the case of a batch type reaction apparatus, it is 1 minute to 10 hours depending on the type of reaction scale, reaction tank, and stirrer, but there is no particular limitation. In addition to the batch reactor, a continuous reactor such as a continuous extrusion kneader may be used. In this case, the temperature control of the dropping zone of the acylating agent, and the temperature control of the aging zone,
Good results can be obtained by dividing into multiple zones and controlling them arbitrarily.

In the reaction of the present invention, the aging temperature is preferably not lower than the melting point of the alkylene oxide adduct used and not higher than 150 ° C. From the viewpoint of terminating the reaction in a short time and suppressing side reactions, 120 ° C or lower is more preferable. Furthermore, considering the quality such as the hue of acyloxybenzoic acid or its salt and the stability of the alkylene oxide adduct, 60
Particularly preferred is -100 ° C. The aging time depends on the aging temperature, but for example, about 150 ° C. for about 1 hour, 100 ° C. for about 1 to 4 hours, and 80 ° C. for about 1 to 6 hours are suitable.

[0039]

FUNCTION AND EFFECT OF THE INVENTION In the esterification reaction of the hydroxybenzoic acid represented by the general formula (1) or its salt with an acylating agent, the compound represented by the general formula (3) or (4) is used. By the alkylene oxide adduct,
Although the mechanism by which the reaction is promoted and side reactions are suppressed is not yet clear, the solubility of hydroxybenzoic acid or a salt thereof in an alkylene oxide adduct is one of the factors involved in promoting the reaction. Has been suggested. Hydroxybenzoic acid or a salt thereof, and the product acyloxybenzoic acid or a salt thereof are both insoluble or partially dissolved in the amount of the alkylene oxide adduct used in the present invention, and become a slurry or paste. ing. That is, when hydroxybenzoic acid or a salt thereof is substantially or partially dissolved in an alkylene oxide adduct, the reaction with an acylating agent existing as a liquid phase proceeds favorably. It is presumed that it plays a role of a reaction substrate carrier between the phases. This effect is significant when using hydroxybenzoate. In the present invention, basically, an organic solvent such as a halogenated hydrocarbon-based solvent, a hydrocarbon-based solvent or an aromatic hydrocarbon-based solvent is not used. However, even in these solvent systems, use of the alkylene oxide adduct of the present invention This improves the esterification reaction rate.

Regarding the reaction selectivity in the esterification reaction, when an ester type alkylene oxide adduct is used, the selectivity is further improved by using the one having the same carboxylic acid residue. You can It is speculated that this is due to the increased mole fraction of the target acyl group of the same type in the transesterification reaction occurring during the reaction.

Due to the above reaction-promoting action, it is possible to significantly increase the reaction in the same manner as in a reaction using a polar solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, or 1,3-dimethyl-2-imidazolidinone. The target esterification reaction can be allowed to proceed under extremely mild conditions.
As a result, it is presumed that undesired side reactions are relatively reduced and the selectivity of the reaction is improved. Further, among the acyloxybenzoic acids represented by the general formula (2) or salts thereof, those having low solubility in water as they are, for example, acyloxybenzoic acid having a carboxylic acid residue having 10 or more carbon atoms or a salt thereof, Particularly, those which do not form a salt usually have a very low solubility in water at a low temperature of 20 ° C. or lower, and the original performance cannot be sufficiently exhibited. Also for these, the solubility in water is significantly improved by using the alkylene oxide adduct, that is, the alkylene oxide adduct acts as a good solubilizing agent of acyloxybenzoic acid or a salt thereof, The function as a bleach activator was significantly enhanced.

[0042]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples,% is based on weight unless otherwise specified.

Example 1 High-viscosity stirring blade (full zone stirring device), thermometer,
In a four-necked flask equipped with a nitrogen gas blowing tube, a dropping funnel for carboxylic acid halide equipped with a drying tube filled with granular calcium chloride, and a Dimroth cooling tube, p-hydroxybenzoic acid Na (Wako Pure Chemical ( Ltd., 99.5%) 200.
02.5 g (1.24 mol), lauric acid ester of polyoxyethylene (EO = 10) methanol (abbreviated as POE (EO = 10) methanol hereinafter) (acid value 0.2, hydroxyl value 0.5) 402.5 g
Was weighed and heated to 80 ° C. in an oil bath whose temperature could be adjusted while stirring. After reaching 80 ° C., 274.7 g (1.25 mol) of lauric acid chloride distilled by the phosphorus trichloride method was added dropwise over about 15 minutes. Nitrogen gas was circulated at a supply rate of about 0.5 liter / min throughout the reaction before the dropping. After completion of dropping, aging was carried out at 80 ° C. for 4 hours. While maintaining the temperature at 80 ° C, the pressure was gradually reduced to 200 Torr to remove hydrochloric acid over 1 hour. As a result of quantification by liquid chromatography analysis,
The target substance, sodium p-dodecanoyloxybenzoate and the like was obtained in a yield of 97%. The yield of Na p-dodecanoyloxybenzoate was 92.5%. The hue was APHA 40.

The reaction products were analyzed by liquid chromatography using the following columns, eluents and detectors. Column: Merck Recloth Fur 100 RP-18 (5 μm),
250mm × 4mmφ Eluent: Gradient method using the following solutions A and B Solution A: 0.1M NaClO ₄ in CH ₃ CN / water = 30/70 (vol / vol) Solution B: CH ₃ CN 100% Detector: UV 260nm The hue is 5% solid content, in the case of salt: acetonitrile / water = 40/60 (vol / vol) solution, in the case of acid type: acetonitrile / water = 80/20 (vol / vol) solution , And measured by comparing with APHA standard solution.

Example 2 Using the same equipment as in Example 1, salicylic acid (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5%) 200.0 g (1.44 mol), and PO
E (EO = 50) Methanol lauric acid ester (acid value 0.5,
Hydroxyl value 0.9) 280.3g (1.4 times weight to salicylic acid) is weighed and stirred in an oil bath with adjustable temperature.
Heated to 80 ° C. After reaching 80 ° C, undistilled lauric chloride by the phosphorus trichloride method (manufactured by Nippon Seika Co., Ltd., purity 98.1%)
324.5 g (1.46 mol) was added dropwise over about 20 minutes. Nitrogen gas is about 0.5 liters /
It was distributed at a supply rate of minutes. After completion of dropping, aging was carried out at 80 ° C. for 4 hours. While maintaining the temperature at 80 ° C, the pressure was gradually reduced to 100 Torr to remove hydrochloric acid over 1 hour. As a result of quantification by liquid chromatography analysis, the objective substance such as o-dodecanoyloxybenzoic acid was esterified at a yield of 98
Obtained in% yield. The yield of o-dodecanoyloxybenzoic acid was 87.5%. The hue was APHA 40.

Example 3 Instead of lauric chloride, lauric anhydride (manufactured by Tokyo Kasei Co., Ltd., with 100% purity) 562.0 g (1.
47 mol) was used. Using the same device as in Example 1,
Salicylic acid (Wako Pure Chemical Industries, Ltd., purity 99.5%) 200.0 g
(1.44 mol) and POE (EO = 50) Methanol lauric acid ester (acid value 0.3, hydroxyl value 0.8) 280.0 g (1.4 times by weight salicylic acid) are weighed and stirred in an oil bath with adjustable temperature. Heated to 80 ° C. After reaching 80 ℃,
Approximately 562.0 g of lauric anhydride dissolved at about 50 ° C
Dropped in 10 minutes. Nitrogen gas was circulated at a supply rate of about 0.1 l / min throughout the reaction before the dropping. After the completion of dropping, the mixture was aged at 80 ° C. for 6 hours. As a result of quantification by liquid chromatography analysis, the target substance o-dodecanoyloxybenzoic acid or the like was obtained as an esterification yield,
Obtained in a yield of 97%. The yield of o-dodecanoyloxybenzoic acid was 93.3%. The hue was APHA 50.

Examples 4 to 12: Effect of carboxylic acid species Na salicylate and Table 1 were prepared under the same equipment and conditions as in Example 1.
The reactivity was confirmed by using the carboxylic acid halide shown in and the carboxylic acid ester of POE (EO = 10) methanol. The results are summarized in Table 1.

[0048]

[Table 1]

Note) * 1: Weight multiple of Na salicylate effective component * 2: Acylation yield * 3: Acylated Na salicylate by corresponding carboxylic acid species
Comparative Example 1 and Examples 13 to 17: Effect of Addition Amount of Alkylene Oxide Adduct POE (EO = 25) with respect to salicylic acid at the addition amount shown in Table 2 as in Example 2. Example 2 except that the lauric acid ester of methanol was added to extend the aging time at 80 ° C.
The reaction was carried out under the same reaction apparatus and conditions as above, and the yield was calculated by liquid chromatography analysis. Table 2 shows the results.
Further, the hue of the reaction product and the solubility in water were evaluated. The results are also shown in Table 2.

[0050]

[Table 2]

Note) * 1: Weight ratio to salicylic acid (effective content) * 2: Salicylic acid reaction rate (80 ° C / 6 hours) * 3: Yield% of o-lauroyloxybenzoic acid * 4: Salicylic acid reaction rate 80 ℃ required to reach> 90%
Aging time (hours) * 5: 2% sodium percarbonate aqueous solution 100g, effective amount 1g equivalent state after stirring at 20 ° C for about 15 minutes x: Undissolved, △: Partially undissolved, ○: Slightly undissolved residue, ◎: Complete dissolution * 6: N, N-dimethylacetamide * 7: Lauric acid chloride per 1 mol of salicylic acid
Use of 1.15 mol * 8: A batch type kneader was used instead of the apparatus of Example 2.

Examples 18 to 24: Effect of the type of alkylene oxide adduct Various alkylene oxide adducts listed in Table 3 were used for p-hydroxybenzoic acid in an amount of 1.5 times the weight of p-hydroxybenzoic acid. The reaction was performed in the same manner as in 13 to 17, and the yield was calculated by liquid chromatography analysis. The results are shown in Table 3. A batch type kneader was used as the reactor.

[0053]

[Table 3]

Note) * 1: Alkylene oxide adduct A: POE (EO = 25) lauric acid ester of methanol B: Lauric acid ester of random adduct of 40 mol of EO and 10 mol of PO C: POE (EO = 50) Methanol D: Polyethylene glycol (average molecular weight 8700) E: Polyethylene glycol (average molecular weight 2000) monolauric acid ester (mixture of polyethylene glycol, its monoester and diester) F: n-butanol PO 5 mol, EO 20 mol block adduct Lauric acid ester G: POE (EO = 50) Acetic acid ester of lauryl alcohol (Calcol 1298 manufactured by Kao Corporation) * 2: p-hydroxybenzoic acid reaction rate * 3: Yield% of p-lauroyloxybenzoic acid * 4: A state in which 100 g of a 2% sodium percarbonate aqueous solution and 1 g of the effective component were stirred at 20 ° C. for about 15 minutes Δ: Partially undissolved, : Yes remaining melted slightly,
⊚: Complete dissolution Examples 25 to 28: Influence of counterion The reaction was carried out under the same conditions as in Example 1 except that the counterion of p-hydroxybenzoic acid was changed to that shown in Table 4. The results are summarized in Table 4.

[0055]

[Table 4]

Note) * 1: p-hydroxybenzoate reaction rate * 2: Acyloxybenzoate yield Examples 29 to 32: Effect of hydroxybenzoic acid species 2,4-dihydroxybenzoic acid as hydroxybenzoic acid 3,4,5-trihydroxybenzoic acid was used, and the reaction was carried out under the same conditions as in Example 2 except that the addition molar ratio of lauric chloride was changed as shown in Table 5. The results are summarized in Table 5.

[0057]

[Table 5]

Note) * 1: Hydroxyl group of lauric acid chloride / hydroxybenzoic acid * 2: Average esterification rate of hydroxyl group of hydroxybenzoic acid * 3: Degree of esterification in one molecule of each hydroxybenzoic acid from the esterification rate Was calculated.

Examples 33 to 38: Effect of Species of Acylating Agents 2,4-Dihydroxybenzoic acid and 3,4,5-trihydroxybenzoic acid as hydroxybenzoic acid, acetic anhydride and capric acid as acylating agents Chloride was used. Using the same device as in Example 1, PO was added to 1.0 mol of hydroxybenzoic acid (manufactured by Wako Pure Chemical Industries, Ltd.) shown in Table 6.
E (EO = 50) Methanol corresponding carboxylic acid ester was weighed in an amount of 2 times by weight, and heated to 80 ° C. in an oil bath whose temperature could be adjusted while stirring. After reaching 80 ° C., the amount of the acylating agent shown in Table 6 shown in Table 6 was added dropwise over about 20 minutes. Nitrogen gas was circulated at a supply rate of about 0.5 liter / min throughout the reaction before the dropping. For the aging, in the example using capric acid chloride, after completion of the dropping, aging was carried out at 80 ° C. for 5 hours, and then gradually maintained at 100 Torr while being kept at 80 ° C.
The pressure was reduced to 1, and hydrochloric acid was removed over 1 hour. In the examples using acetic anhydride, aging was carried out at 80 ° C. for 6 hours after completion of dropping. In each case, quantification was performed by liquid chromatography analysis. The results are summarized in Table 6.

[0060]

[Table 6]

Note) * 1: Acylating agent / hydroxyl group of hydroxybenzoic acid * 2: Average esterification rate of hydroxyl group of hydroxybenzoic acid * 3: Degree of esterification in one molecule of each hydroxybenzoic acid from the esterification rate Was calculated.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 69/52 69/58 69/612 9546-4H 69/614 69/62 69/67 69/773 233/47 9547-4H // C11D 3/395 7/26 7/54

Claims (7)

[Claims] 1. A compound represented by the general formula (1): [In the formula, M ¹ and M ^{2 represent a} hydrogen atom or an alkali metal, an alkaline earth metal, ammonium, a substituted ammonium or a quaternary ammonium, and M ¹ and M ² may be the same or different. m: Indicates the number of 1 to 3. ] The hydroxybenzoic acid represented by the following formula or a salt thereof or a mixture thereof is reacted with an acylating agent to give a compound represented by the general formula (2): [Wherein M ¹ and M ² have the same meanings as described above]. R ¹ : a linear or branched alkyl group or alkenyl group having ^{1 to} 21 carbon atoms, which may be substituted with halogen, and may have an ester group, an amide group, an ether group or a phenylene group inserted, or Unsubstituted or linear or branched alkyl or alkenyl groups or halogens having 1 to 22 carbon atoms, which may be substituted with halogen, and in which an ester group, amide group, ether group or phenylene group may be inserted. Represents a phenyl group which may be substituted with. h: shows the number of 1-3. i: Indicates the number obtained by subtracting h from m. Here, m has the same meaning as described above. ] In producing the acyloxybenzoic acid represented by the following formula or a salt thereof or a mixture thereof, a compound represented by the general formula (3) or (4): [In the above formulas (3) and (4), R ^{2 is a} hydrogen atom or may be substituted with a halogen having 1 to 22 carbon atoms, and an ester group, an amide group, an ether group or a phenylene group is inserted. It may be a linear or branched alkyl group or alkenyl group, or may be unsubstituted or substituted with a halogen having 1 to 22 carbon atoms, and an ester group, an amide group, an ether group or a phenylene group is inserted. A linear or branched alkyl group or alkenyl group which may be substituted, a phenyl group which may be substituted with halogen, or a polyhydric alcohol residue is shown. R ^3: 1 to 21 carbon atoms, may be substituted by halogen, an ester group, an amide group, a linear optionally an ether group or a phenylene group is inserted or branched chain alkyl or alkenyl group or, Unsubstituted or linear or branched alkyl or alkenyl groups or halogens having 1 to 22 carbon atoms, which may be substituted with halogen, and in which an ester group, amide group, ether group or phenylene group may be inserted. Represents a phenyl group which may be substituted with. R ^4: a hydrogen atom or 1 to 22 carbon atoms, may be substituted with a halogen, an ester group, an amide group, or an alkyl group which may linear be an ether group or a phenylene group is inserted or branched chain An alkenyl group, or a straight-chain or branched-chain alkyl group which is unsubstituted or has 1 to 22 carbon atoms and which may be substituted with a halogen, and which may have an ester group, an amide group, an ether group or a phenylene group inserted, or An alkenyl group, a phenyl group which may be substituted with halogen, a polyhydric alcohol residue, or a compound of the formula: (In the formula, R ³ has the same meaning as described above and two R ³ may be the same or different.) B: A linear or branched alkylene group having 2 to 4 carbon atoms is shown, and p B's or q B's may be the same or different. p and q: each is a number of 5 to 200 indicating the average number of moles of alkylene oxide added, and may be the same or different. ] It reacts in presence of 1 type (s) or 2 or more types selected from the alkylene oxide adduct represented by these, The manufacturing method of the acyloxy benzoic acid or its salt characterized by the above-mentioned. 2. An alkylene oxide adduct represented by the general formula (3) or (4) per 1 part by weight of a hydroxybenzoic acid represented by the general formula (1) or a salt thereof or a mixture thereof. 0.1 or more in total
20 weight part is used, The manufacturing method of the acyloxy benzoic acid or its salt of Claim 1 characterized by the above-mentioned. 3. The carboxylic acid residue of the alkylene oxide adduct represented by the general formula (4) is the same as the carboxylic acid residue of the acylating agent.
A method for producing the acyloxybenzoic acid or a salt thereof described. 4. An alkylene oxide adduct represented by the general formula (4) is an aliphatic carboxylic acid having 2 to 22 carbon atoms,
The method according to any one of claims 1 to 3, which is an ester of an alkylene oxide adduct of an alcohol having 1 to 4 carbon atoms (average number of moles of alkylene oxide added: 5 to 120). 5. The acylating agent has the general formula (5): [In the formula, R ¹ represents the same meaning as described above. X: Indicates a halogen atom. ] Or a carboxylic acid halide represented by the general formula (6) [In the formula, R ¹ represents the same meaning as described above. R ⁵ : a straight-chain or branched alkyl group or alkenyl group having 1 to 21 carbon atoms, which may be substituted with halogen, and in which an ester group, an amide group, an ether group or a phenylene group may be inserted, or Unsubstituted or linear or branched alkyl or alkenyl groups or halogens having 1 to 22 carbon atoms, which may be substituted with halogen, and in which an ester group, amide group, ether group or phenylene group may be inserted. Represents a phenyl group which may be substituted with and may be the same as or different from R ¹ . ] It is a carboxylic acid anhydride represented by these, The manufacturing method of the acyloxy benzoic acid or its salt as described in any one of Claims 1-4. 6. The formula: The group represented by R ¹ and R ³ in the carboxylic acid residue represented by is a linear or branched alkyl group having 1 to 21 carbon atoms. A method for producing the acyloxybenzoic acid or a salt thereof according to any one of claims. 7. The group represented by R ¹ and R ³ has 1 to 15 carbon atoms.
7. The method for producing an acyloxybenzoic acid or a salt thereof according to claim 6, which is a linear or branched alkyl group.