JP2002161097A - Method for producing hydroxyphenylpropionic acid ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method capable of relatively simply producing a hydroxyphenylpropionic acid ester (I) in slight amount of a compound by- produced even when a spiroglycol (II) containing an acid is used. SOLUTION: This method for producing the hydroxyphenylpropionic acid ester (I) comprises bringing the spiroglycol (II) into contact with an alkali compound and successively reacting the treated spiroglycol (II) with propionic acid esters (III). A compound obtained by reacting pentaerythritol with hydroxypivalic aldehyde in the presence of an acid catalyst can be used without producing a by-product as the spiroglycol (II). An alkali metal carbonate, an alkali metal bicarbonate, an alkali metal hydroxide, an alkaline earth metal carbonate or an alkaline earth metal hydroxide is used as the alkali compound. The spiroglycol is usually brought into contact with the alkali compound in melted state. The reaction is usually carried out in the presence of an organotin catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing hydroxyphenylpropionate.

[0002]

2. Description of the Related Art 3,9-Bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethane] -2,4
8,10-Tetraoxaspiro {5,5} undecane has the formula (I) (Hereinafter referred to as hydroxyphenylpropionate), for example, polyethylene,
Polyolefins such as polypropylene, polystyrene,
Styrene resin such as impact-resistant polystyrene, acrylonitrile-butadiene-styrene copolymer, polyacetal, engineering plastics such as polyamide,
Compounds useful as stabilizers such as polyurethane (JP-A-53-25826, JP-A-59-231)
089, JP-A-61-197747, etc.).

A method for producing such a hydroxyphenylpropionic acid ester includes, for example, a compound represented by the formula (II) 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane (hereinafter referred to as spiroglycol) represented by the general formula ( III) (Wherein, R ¹ represents an alkyl group having 1 to 3 carbon atoms). A method of reacting with propionate esters represented by the following formulas is known (JP-A-59-25826, JP-A-59-25826).
0-197747, JP-A-8-87860, etc.). Here, spiroglycol (II) is a compound that can be produced, for example, by reacting pentaerythritol and hydroxypivalaldehyde in the presence of an acid (JP-A-3-28711, JP-A-64-61).
485, JP-A-64-61486, etc.).

According to such a method, spiroglycol can be obtained from the reaction mixture after the reaction by crystallization or the like. However, the spiroglycol thus obtained contains an acid used as an impurity. When this is directly reacted with propionates (III), the compound of formula (IV) (Hereinafter referred to as compound (IV)) as a by-product as a byproduct.

In order to solve such a problem, the obtained spiroglycol may be purified and used. For example, a method of heat-treating spiroglycol to a high temperature (JP-A-3-27
No. 384, JP-A-7-215987) and a recrystallization method (JP-A-11-228577) are known. However, these methods have a problem that the steps are complicated.

[0006]

Accordingly, the present inventors have found that even when spiroglycol containing an acid is used, the amount of compound (IV) produced is small and the hydroxyphenylpropionate can be prepared relatively easily. As a result of intensive studies to develop a method capable of producing (I), it was found that when spiroglycol was brought into contact with an alkali compound and reacted with propionates (III), the amount of compound (IV) produced was small. This has led to the present invention.

[0007]

That is, the present invention relates to a method for preparing a compound of the formula (II)
It is intended to provide a process for producing a hydroxyphenylpropionate, which is characterized by reacting with a propionate represented by I).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The spiroglycol applied to the production method of the present invention may contain an acid, and a spiroglycol containing a relatively large amount of an acid, for example, having an acid content of 0.1% by weight or more. It is preferably applied to spiroglycol. Examples of the acid include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid, and organic acids such as p-toluenesulfonic acid, methanesulfonic acid, formic acid, and butyric acid.

Such spiroglycol is obtained, for example, by reacting pentaerythritol and hydroxypivalaldehyde in the presence of an acid. The acid contained in the spiroglycol applied to the production method of the present invention is: Usually, it is the acid used in such a reaction.

The amount of the acid used in such a reaction is usually from 0.01 to 0.6 mole times, preferably from 0.03 to 0.3 mole times, relative to pentaerythritol.

[0011] Hydroxypivalaldehyde can be produced, for example, by a method of reacting isobutyraldehyde and formaldehyde in a solvent. As the solvent, for example, water is used. The reaction may be performed in the presence of a catalyst. Examples of the catalyst include tertiary alkylamines such as triethylamine, tributylamine, and N-methylpiperidine. Hydroxypivalaldehyde may be used after being taken out of the reaction mixture after the reaction, or may be used as it is contained in the reaction mixture.

The amount of hydroxypivalaldehyde used is
The stoichiometry is 0.5 mole times that of pentaerythritol, but it is usually in the range of 0.3 mole times to 0.6 mole times. If it is less than 0.3 mole times, many impurities tend to be produced or the yield tends to decrease. Preferably, it is 0.4 mole times or more. It tends to increase or decrease the yield, and is preferably 0.5 mol times or less.

The reaction between pentaerythritol and hydroxypivalaldehyde is usually carried out in a solvent, for example, water or a mixed solvent of water and an organic solvent. When a mixed solvent of water and an organic solvent is used, the organic solvent may be a hydrophobic organic solvent immiscible with water, for example, xylene, toluene, ethylbenzene, aromatic hydrocarbons such as monochlorobenzene, hexane, cyclohexane, Aliphatic hydrocarbons such as heptane and octane can be used. Among such hydrophobic organic solvents, xylene, toluene, hexane, heptane and the like are preferably used.

When water is used alone as a solvent, the amount of the solvent used is usually 2 to 20 times by weight based on pentaerythritol used. When a mixed solvent of water and an organic solvent is used as the solvent, it is usually at least 3 times by weight, preferably at least 5 times by weight and at most 25 times by weight, based on pentaerythritol.

When a mixed solvent of water and an organic solvent is used as the solvent, the amount of the organic solvent used in the mixed solvent is usually not more than 2 times the weight of pentaerythritol. 2
When the weight is more than the weight, the particle diameter of the obtained spiro glycol tends to be small, and it may be difficult to remove the spiro glycol from the reaction mixture after the reaction by filtration or the like, and it is preferably 1 weight or less. . Also,
The amount of the organic solvent used is 0.05 weight times or more, and more preferably 0.1 weight times or more in that the obtained spiroglycol has a relatively large particle size and spiroglycol is easily removed from the reaction mixture after the reaction by filtration or the like. It is preferred that

The reaction may be carried out, for example, by reacting pentaerythritol, hydroxypivalaldehyde and an acid in a solvent, and the reaction temperature is usually 40 ° C. to 80 ° C., preferably 50 ° C. to 75 ° C.

To react pentaerythritol, hydroxypivalaldehyde and an acid in a solvent, for example, pentaerythritol, hydroxypivalaldehyde,
After mixing the acid and the solvent, the mixture may be heated to the reaction temperature. The reaction time is usually from 8 hours to 24 hours.

The acid may be continuously or intermittently added to the mixture of pentaerythritol, hydroxypivalaldehyde and the solvent at the reaction temperature, or hydroxypivalaldehyde may be added to the mixture of pentaerythritol and the solvent at the reaction temperature. And acid may be added continuously or intermittently, hydroxypivalaldehyde may be added continuously or intermittently to the mixture of pentaerythritol, water and acid at the reaction temperature, And pentaerythritol and an acid may be continuously or intermittently added to the mixture of the solvent at the reaction temperature, or pentaerythritol may be continuously or intermittently added to the mixture of the hydroxypivalaldehyde, the solvent and the acid at the reaction temperature. May be. In these methods, after the addition, the reaction mixture is kept at the reaction temperature with stirring. The heat retaining temperature is usually about 8 hours to 24 hours.

After the reaction, the reaction mixture is neutralized by adding a base thereto. As the base, for example, sodium hydroxide, sodium carbonate and the like are used, and these are usually added as an aqueous solution. After neutralization, the target spiroglycol can be obtained by collecting the precipitate by filtration such as filtration.

The spiroglycol thus obtained may contain the acid used in the reaction. In the production method of the present invention, spiroglycol containing such an acid can be used.

In the production method of the present invention, spiro glycol is contacted with an alkali compound. Examples of the alkali compound include alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Examples of the metal compound include alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, and the like. Alkali metal carbonates, alkaline earth metal bicarbonates, and the like are preferable in that the impurity content of the acid ester is small.

The amount of the alkali compound used is usually at least 1 mole, preferably at least 3 mole times the ionizable hydrogen atom of the acid contained in the spiroglycol, and the amount of compound (IV) produced is small. In this respect, the molar ratio is preferably 30 mol times or less, more preferably 15 mol times or less.

In order to contact spiroglycol with an alkali compound, for example, spiroglycol and an alkali compound may be mixed. The alkali compound may be used in a solid state, or may be used in a state of being mixed with a solvent. As such a solvent, for example, a water-soluble organic solvent such as water and alcohol, and a hydrophobic organic solvent such as aromatic hydrocarbon and aliphatic hydrocarbon are used. Examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, butanol and the like.
As the aromatic hydrocarbon, for example, toluene, xylene,
Examples include ethylbenzene, cymene, and monochlorobenzene. As the aliphatic hydrocarbon, for example, hexane,
Heptane, cyclohexane, octane and the like can be mentioned. When an alkali metal carbonate, an alkali metal bicarbonate, an alkaline earth metal carbonate, an alkaline earth metal hydroxide or the like is used as the alkali compound, water is preferably used, and the alkali metal hydroxide is preferably used as the alkali compound. When such a solvent is used, a hydrophilic solvent such as an alcohol is preferably used. When using a solvent,
The alkali compound may be dissolved in a solvent or may be suspended in the solvent.

In order to mix spiroglycol with an alkali compound, spiroglycol may be added to the alkali compound, or an alkali compound may be added to spiroglycol.

When contacting spiroglycol with an alkali compound, propionates (III) may be present. In this case, for example, after mixing spiroglycol and propionate, the alkali compound is added to the mixture. Although mixing may be performed, it is preferable to mix spiroglycol after mixing the alkali compound and propionic acid esters.

The spiro glycol and the alkali compound are
For example, the contact is performed at a temperature of 0 ° C. or more and 180 ° C. or less, preferably a temperature at which spiroglycol is in a molten state,
The contact is made at a temperature of 0 ° C. or higher and at a temperature of 160 ° C. or lower. Spiroglycol may be at least partially in a molten state at a temperature of 70 ° C. or higher. When the spiroglycol and the alkali compound are mixed and brought into contact with each other, the mixture is usually mixed at a temperature of 130 ° C or lower, and then at a temperature of 80 ° C or higher and 180 ° C or lower, preferably 110 ° C or higher and 160 ° C or lower, more preferably 150 ° C or lower. Keep warm.
The heat retention time is usually 30 minutes or more. If the heat retention time is less than 30 minutes, the contact of spiroglycol with the alkali compound becomes insufficient, and the resulting hydroxyphenylpropionate tends to have an increased impurity content or a reduced yield.

It is preferable that the spiroglycol and the alkali compound are brought into contact with each other in a state where oxygen is cut off. For this purpose, the spiroglycol and the alkali compound may be brought into contact with each other under an atmosphere of an inert gas such as nitrogen gas or Ar gas under reduced pressure. .

In the production method of the present invention, spiroglycol (II) is brought into contact with an alkali compound and reacted with propionates (III). Spiroglycol contacted with an alkali compound can be used for the reaction with propionates without being taken out of the mixture after the contact.

In the propionic esters represented by the general formula (III), R ¹ represents a methyl group, an ethyl group, an n-
An alkyl group having 1 to 3 carbon atoms such as a propyl group and an isopropyl group. Such propionates (III)
Is, for example, 3- (3-t-butyl-t-hydroxy-5)
-Methylphenyl) propionic acid, such as methyl ester, ethyl ester, n-propyl ester and isopropyl ester, and preferably methyl ester.

The amount of propionic acid ester (III) used is usually at least 2 times, preferably at least 2.1 times the mole of spiroglycol (II). The larger the amount of propionate (III) used, the shorter the reaction time and the higher the reaction yield. However, if the amount exceeds 6 moles, the obtained hydroxyphenylpropionate (I) is crystallized. Since it tends to be relatively difficult to remove from the reaction mixture by such a method as above, it is usually at most 6 mol times, preferably at most 2.5 mol times.

The propionic acid ester may be supplied when spiroglycol is brought into contact with an alkali compound, or may be supplied after contacting spiroglycol with an alkali compound. When spiroglycol is brought into contact with an alkali compound in the presence of propionates, spiroglycol may be reacted with propionates as it is.

The reaction may be carried out without solvent or in a solvent. Examples of the solvent include a non-polar solvent such as an aromatic hydrocarbon as described above, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, N, N
Polar solvents such as N-dimethylacetamide and N-methylpyrrolidone can also be used, and aromatic hydrocarbons,
Polar solvents are preferably used. The reaction temperature is usually 14
0 ° C to 250 ° C, preferably 170 ° C to 210
It is below ° C.

The reaction may be carried out in the atmosphere. However, the reaction may be carried out in an atmosphere of an inert gas such as nitrogen gas or Ar gas or under reduced pressure, since the resulting hydroxyphenylpropionate has few impurities. More preferably, the reaction is performed under reduced pressure under an inert gas atmosphere.

In the reaction, the compound represented by the general formula (V) (Wherein R ¹ has the same meaning as described above), and the reaction is preferably carried out while removing the alcohol outside the system. In order to carry out the reaction while removing the alcohol out of the system, for example, the reaction may be carried out in a solvent under atmospheric pressure, and the alcohol (IV) generated in the solvent may be allowed to evaporate out of the system together with the produced alcohol (IV). Further, the reaction may be carried out under reduced pressure, and the alcohol (IV) produced may be volatilized and led out of the system. Further, the reaction may be performed under the flow of an inert gas, and the generated alcohol (IV) may be led out of the system together with the inert gas. Examples of the inert gas include a nitrogen gas, a helium gas, an argon gas and the like, and an organic compound inert to the reaction can also be used. When the reaction is performed without a solvent, for example, after maintaining at atmospheric pressure for about 10 to 60 minutes, the reaction may be maintained under reduced pressure, for example, at a pressure of about 1 kPa to 100 kPa until the reaction is completed.

The reaction is carried out, for example, until the production of alcohol (IV) is completed. The reaction time is usually 1 hour or more and 20 hours.
Less than an hour.

The spiroglycol and propionates are usually reacted in the presence of an organotin compound.
Examples of the organotin compound include dialkyltin oxide, dialkyltin dialkoxide, dialkyltin carboxylate, and the like. Examples of the dialkyltin oxide include dibutyltin oxide and dioctyltin oxide, and dibutyltin oxide is preferably used. As the dialkyltin dialkoxide, for example, dibutyltin dimethoxide and the like are preferably used. As the dialkyltin carboxylate, for example, dibutyltin diacetate, dibutyltin malate, dibutyltin dioctanoate, dibutyltin dilaurate, dioctyltin laurate and the like are preferably used. Such organotin compounds are used alone or in combination of two or more. When such an organotin compound is used, its use amount is usually about 0.001 mole times or more and 0.2 mole times or less of spiroglycol. If it is less than 0.001 mole, the reaction rate tends to be slow, and preferably 0.006 mole or more. On the other hand, if it exceeds 0.2 mol times, the content of impurities tends to increase, preferably 0.02 mol times or less.

The organotin compound may be added when spiroglycol is reacted with propionates or when spiroglycol is brought into contact with an alkali compound.

Thus, a reaction mixture containing the desired hydroxyphenylpropionate (III) is obtained. However, since the production method of the present invention produces little compound (IV), the reaction mixture contains the compound (III) contained therein. IV) content is low.

The obtained hydroxyphenylpropionic acid ester can be removed from the reaction mixture after the reaction, for example, by crystallization or the like.

When an organotin compound is used in the reaction, crystallization may be performed without removing the organotin compound from the reaction mixture after the reaction, or crystallization is preferably performed after removing the organotin compound.

In order to remove the organotin compound from the reaction mixture after the reaction, for example, the reaction mixture may be brought into contact with hydrogen chloride gas or an aqueous solution of hydrogen chloride. When a solvent is used in the reaction, the solvent may be brought into contact with hydrogen chloride gas or an aqueous solution of hydrogen chloride without distilling off the solvent, or the solvent may be distilled off and then contacted with an aqueous solution of hydrogen chloride gas or an aqueous solution of hydrogen chloride. Alternatively, the residue obtained after distilling off the solvent may be dissolved again in the solvent, and then contacted with a hydrogen chloride gas or an aqueous solution of hydrogen chloride. When an aqueous hydrogen chloride solution is used, the concentration of the hydrogen chloride is generally from 1% by weight to 35% by weight, preferably from 5% by weight to 15% by weight.

Examples of the solvent used for contacting with hydrogen chloride gas or an aqueous solution of hydrogen chloride include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene, cymene and monochlorobenzene, and chains such as n-hexane and n-heptane. Aliphatic hydrocarbons, cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane, alcohols such as methanol and ethanol, aliphatic ketones such as acetone, and aliphatic nitriles such as acetonitrile. No.

The contact can be carried out, for example, by blowing hydrogen chloride gas into the reaction mixture while stirring the mixture at a temperature of 80 ° C. or lower,
Alternatively, it may be mixed with an aqueous hydrogen chloride solution. At a temperature of 80 ° C. or higher, the generated hydroxyphenylpropionate may be hydrolyzed. The lower limit of the temperature may be a temperature at which the reaction mixture does not solidify, for example, 0 ° C. or higher.

When a solvent that does not dissolve in water is used as a solvent, the solvent may be separated into two layers, that is, an aqueous layer and an organic layer. In this case, liquid separation is performed to remove the aqueous layer. Good.
After removing the aqueous layer, the organic layer may be washed with water.
Thus, the organotin compound can be removed.

In the crystallization, when a solvent is used for the reaction, the solvent may be used as it is as the crystallization solvent, or the solvent used for the reaction is distilled off, and the residue is dissolved again in the crystallization solvent. Is also good. The solvent used when removing the organotin compound may be used as it is as the crystallization solvent.

As the crystallization solvent, the same aromatic hydrocarbons, chain aliphatic hydrocarbons, cycloaliphatic hydrocarbons, alcohols, aliphatic ketones, and aliphatic nitriles as described above for the removal of the organotin compound can be used. And the like. These solvents can be used alone or in combination of two or more. When a water-soluble solvent is used as the solvent, it is preferable to use a mixture of water.

The crystallization is performed, for example, by cooling from a state in which the hydroxyphenylpropionate is dissolved. By cooling, hydroxyphenylpropionate is precipitated, but if precipitation is difficult, a seed crystal may be added.

An aromatic hydrocarbon may be used as a solvent, and in a state in which the hydroxyphenylpropionic acid ester is dissolved, an aliphatic hydrocarbon may be added for precipitation. In this case, it is preferable to further add alcohols.

The precipitate is separated by filtration from the mother liquor, washed,
By drying, the desired hydroxyphenylpropionate (III) can be obtained. The hydroxyphenylpropionic acid ester thus obtained may be further purified by a method such as recrystallization.

[0050]

According to the production method of the present invention, spiroglycol (II) containing an acid is converted to a propionate (II)
Even when reacted with I), since the amount of compound (IV) produced is small, for example, spiroglycol obtained by reacting pentaerythritol and hydroxypivalaldehyde in the presence of an acid can be used as a raw material without further purification. Even when used, hydroxyphenylpropionate (I) having a low content of the compound (IV) as an impurity can be produced.

[0051]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Reference Example 1 450 parts by weight of isobutyraldehyde and 25.2 parts by weight of triethylamine were charged into a reaction vessel equipped with a thermometer, a stirrer, and a cooling tube, and heated to 55 ° C.
Formalin (formaldehyde 3
Aqueous solution which is 7% by weight, contains a small amount of methanol)
525 parts by weight were gradually added over 3 hours. Then 70
C. and kept at the same temperature for 4 hours to obtain 996 parts by weight of a reaction mixture containing hydroxypivalaldehyde. The composition of the reaction mixture was hydroxypivalaldehyde 5
8.2% by weight, 2.5% by weight of triethylamine, water 3
It was 1.6% by weight, and the total amount of formaldehyde, methanol and impurity components was 7% by weight.

Example 1 (Production of Spiroglycol) 600 parts by weight of water, 60 parts by weight of n-heptane and 150 parts by weight of pentaerythritol were charged into a reaction vessel equipped with a thermometer, a stirrer and a cooling tube, and heated to 60 ° C. While stirring while heating, 402 parts by weight of the reaction mixture obtained in Reference Example 1 was added, and 12 parts by weight of concentrated sulfuric acid (98% concentration) was added dropwise at the same temperature over 90 minutes. Thereafter, while maintaining the temperature range of 58 ° C to 62 ° C, 6
After keeping the temperature for 1.5 hours, 1.5 parts by weight of concentrated sulfuric acid (98% concentration) was added, and the temperature was kept for 6 hours in the same temperature range. Thereafter, an aqueous solution of caustic soda was added for neutralization, and after cooling to room temperature, the precipitated crystals were separated by filtration, washed with water, and washed with n-heptane,
After drying, 310 parts by weight of spiroglycol (purity 91.9% by weight, sulfuric acid content 0.242% by weight) was obtained.

(Production of hydroxyphenyl propionate) A reaction vessel equipped with a thermometer, a stirrer and a condenser for distillation was charged with methyl 3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate. 83.3 parts by weight were added and melted at 130 ° C. with stirring. Under a nitrogen gas atmosphere, 1.16 parts by weight of sodium carbonate, 0.27 parts by weight of dibutyltin oxide and 44.7 parts by weight of the spiroglycol obtained above were obtained. Were introduced in this order. Next, 13 kPa (100 mm
Hg) while heating to 150 ° C while reducing the pressure to 145 ° C.
Incubated at ~ 150 ° C for 30 minutes. In addition, the sodium carbonate used was 9.2 with respect to sulfuric acid contained in spiroglycol.
It is 9 mole times. Thereafter, the mixture is heated to 195 ° C. at the same pressure, and then gradually reduced to 1.3 kPa, and is kept at a temperature in a range of 195 ° C. to 200 ° C. for 4 hours while distilling off generated methanol. 119.5 parts by weight were obtained. The yield of hydroxyphenylpropionate contained in this melt with respect to spiroglycol was 96.2%, and the yield of compound (IV) with respect to spiroglycol was 0.4%.

After the reaction, the mixture was gradually cooled while stirring.
The temperature was adjusted to 0 ° C., 58 parts by weight of xylene was added, and further cooled to 70 ° C., and 41 parts by weight of n-hexane was added. 60 ° C
Dilute hydrochloric acid (hydrogen chloride concentration 10% by weight)
Aqueous solution) and then twice with 27 parts by weight of water. To the organic layer after washing, 50 parts by weight of n-hexane and a small amount of hydroxyphenylpropionate crystals were added, followed by cooling to precipitate crystals. The precipitated crystals were separated by filtration, washed with n-hexane, and dried to obtain 95.1 parts by weight of white crystals (hydroxyphenylpropionate).

Comparative Example 1 (Production of hydroxyphenylpropionate without using sodium carbonate) The same operation as in Example 1 was carried out except that sodium carbonate was not used, and a pale yellow transparent melt was obtained at 117.9% by weight. And 85.1 parts by weight of white crystals were obtained. Table 1 shows the results.

REFERENCE EXAMPLE 2 (Production of hydroxypivalaldehyde) A reference was made except that the amount of isobutyraldehyde was 460 parts by weight, the amount of triethylamine was 25.6 parts by weight, and the amount of formalin was 543 parts by weight. Operating as in Example 1,
Reaction mixture 1024 containing hydroxypivalaldehyde
Parts by weight were obtained. The composition of the reaction mixture was hydroxypivalaldehyde 57.9% by weight, triethylamine 2.
5% by weight and 31.6% by weight of water, and the total amount of formaldehyde, methanol and impurities was 8% by weight.

Example 2 (Production of spiroglycol) 600 parts by weight of water, 30 parts by weight of n-heptane, pentaerythritol 1
Spiroglycol (purity 9) was prepared in the same manner as in Example 1 except that 50 parts by weight and 400 parts by weight of the reaction mixture containing hydroxypivalaldehyde obtained in Reference Example 2 were added.
(4.8% by weight, sulfuric acid content: 0.015% by weight) 301
Parts by weight were obtained.

(Production of hydroxyphenylpropionate) In place of the spiroglycol obtained in Example 1, 43.4 parts by weight of the spiroglycol obtained above was used, and the amount of sodium carbonate used was changed to 0.043 part by weight (spiroglycol). The procedure was the same as in Example 1 except that the amount of sulfuric acid contained in the glycol was 6.3 mol times, to obtain a pale yellow transparent melt 11
8.4 parts by weight were obtained, and 97.3 parts by weight of white crystals of hydroxyphenylpropionate were obtained. Table 1 shows the results.

Comparative Example 2 (Production of hydroxyphenyl propionate without using sodium carbonate) The same operation as in Example 2 was carried out except that sodium carbonate was not used, to obtain a light yellow transparent melt having a weight of 118.7%. And 96.3 parts by weight of white crystals were obtained. Table 1 shows the results.

Comparative Example 3 (Production of hydroxyphenylpropionate using tributylamine) Except that 0.15 parts by weight of tributylamine was used in place of sodium carbonate and the mixture was heated to 150 ° C. in a nitrogen gas atmosphere without reducing pressure. Is Example 2
In the same manner as in the above, 117.3 parts by weight of a pale yellow transparent melt was obtained. The amount of tributylamine used is 12.5 moles per 1 mol of sulfuric acid contained in spiroglycol. Table 1 shows the results.

Comparative Example 4 (Production of Hydroxyphenylpropionate Using Ammonia) Instead of sodium carbonate, 0.06 parts by weight of aqueous ammonia (ammonia content: 25% by weight) was used, and a nitrogen gas atmosphere was used without decompression. The same operation as in Example 2 was carried out except that the temperature was lowered to 150 ° C., to obtain 117.6 parts by weight of a pale yellow transparent melt. The amount of ammonia used is 13.6 mole times the sulfuric acid contained in spiroglycol. Table 1 shows the results.

Comparative Example 5 (Production of hydroxyphenylpropionate using aniline) Instead of sodium carbonate, aniline 0.0
117.4 parts by weight of a brown melt was obtained by operating in the same manner as in Example 2 except that 8 parts by weight were used and heated to 150 ° C. in a nitrogen gas atmosphere without reducing pressure. The amount of aniline used is 1 to sulfuric acid contained in spiroglycol.
It is 3.2 mole times. Table 1 shows the results.

Reference Example 3 (Production of hydroxypivalaldehyde) The reference was made except that the amount of isobutyraldehyde was 460 parts by weight, the amount of triethylamine was 25.7 parts by weight, and the amount of formalin was 537 parts by weight. Operating as in Example 1,
Reaction mixture 1018 containing hydroxypivalaldehyde
Parts by weight were obtained. The composition of the reaction mixture was hydroxypivalaldehyde 58.5% by weight, triethylamine 2.
5% by weight, 31.6% by weight of water, and the total amount of formaldehyde, methanol and impurities was 6.87% by weight.
Met.

Example 3 (Production of hydroxyphenylpropionate) A reaction mixture containing 600 parts by weight of water, 18 parts by weight of n-heptane, 150 parts by weight of pentaerythritol and hydroxypivalaldehyde obtained in Reference Example 3 in a reaction vessel. Spiroglycol (purity 93.7% by weight, sulfuric acid content: 0.3% by weight) was operated in the same manner as in Example 1 except that 402 parts by weight was charged.
(007% by weight) 304.4 parts by weight.

(Production of hydroxyphenylpropionic acid ester) A melt is obtained by operating in the same manner as in Example 1 except that the spiroglycol obtained above is used instead of the spiroglycol obtained in Example 1. The yield of hydroxyphenylpropionate contained in this melt with respect to spiroglycol is high, and the yield of compound (IV) with respect to spiroglycol is sufficiently low. Next, white crystals of hydroxyphenylpropionic acid ester are obtained by operating this melt in the same manner as in Example 1.

[0067]

[Table 1]

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Junichi Ishikawa 3-1-198 Kasuganaka, Konohana-ku, Osaka Sumitomo Chemical Co., Ltd. F-term (reference) 4C071 AA04 BB01 CC14 DD27 EE06 FF16 GG03 JJ01 KK14 LL03 4H039 CA66 CE10

Claims (7)

[Claims] (1) 3,9-bis (2-hydroxy-1,1-
(Dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane is brought into contact with an alkali compound to obtain a compound represented by the general formula (III): (Wherein, R ¹ represents an alkyl group having 1 to 3 carbon atoms.) 3,9-bis [2- {3- (3-t- Butyl-
4-hydroxy-5-methylphenyl) propionyloxy {-1,1-dimethylethane] -2,4,8,10
-A method for producing tetraoxaspiro {5,5} undecane. 2. A method according to claim 2, wherein the 3,9-bis (2-hydroxy-1,1-
The process according to claim 1, wherein dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane is obtained by reacting pentaerythritol and hydroxypivalaldehyde in the presence of an acid. 3. The method of claim 3, wherein the 3,9-bis (2-hydroxy-1,1-
Dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane having an acid content of 0.1% by weight
The manufacturing method according to claim 1 or 2, which is as described above. 4. An alkali compound comprising an alkali metal carbonate, an alkali metal bicarbonate, an alkali metal hydroxide,
4. A compound selected from the group consisting of alkaline earth metal carbonates and alkaline earth metal hydroxides.
The production method according to any one of the above. 5. The production method according to claim 4, wherein the amount of the alkali compound used is usually at least 1 mole times the ionizable hydrogen atom of the acid. 6. A method according to claim 1, wherein the 3,9-bis (2-hydroxy-1,1-
(Dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane and an alkali compound
-Bis (2-hydroxy-1,1-dimethylethyl)-
The production method according to any one of claims 1 to 5, wherein 2,4,8,10-tetraoxaspiro [5.5] undecane is brought into contact at a temperature at which it is in a molten state. 7. The production method according to claim 1, wherein the reaction is carried out in the presence of an organotin catalyst.