JP2000273096A - Production of cyclic phenol sulfide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound in high yield by previously reacting a linear polyphenol sulfide with a specific amount of a metal reagent, removing the water in the reaction system, and further reacting the product by adding simple sulfur thereto. SOLUTION: (A) A liner polyphenol sulfide of formula I [R is H or a hydrocarbon; (a) and b are each 0 or 1; m is 1-7; p is an integer of >=2] is previously reacted with (B) at least one metal reagent selected from oxide or hydroxide reagents of alkali (ne earth) metals in an amount of >=0.05 g-equivalent per g-equivalent of the phenol skeleton constituting the component A to provide (C) a linear sulfide of a phenoxide, removing water from the reaction system, and further reacting the product with (D) simple sulfur in an amount of >=0.05 g-equivalent per g-equivalent of the phenol skeleton constituting the component C to provide (E) the objective cyclic phenol sulfide of formula II (n is an integer of >=3). As a result, the objective compound can be obtained from an inexpensive raw material in high yield.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an antioxidant, a catalyst, a metal scavenger, an ion sensor, a separation membrane material, a polymer material, a light energy conversion material or other functionalities utilizing the function of recognizing ions or molecules. The present invention relates to a method for producing a novel cyclic phenol sulfide which can be used as a molecular intermediate or the like.

[0002]

2. Description of the Related Art Conventionally, alkylphenol sulfide has been used as an antioxidant (for example, US Pat. No. 2,239,534,
U.S. Pat. No. 3,377,334, rubber sulfurizing agents (e.g., U.S. Pat. No. 3,468,961 and U.S. Pat. No. 3,647,885, etc.), polymer stabilizers (e.g., U.S. Pat. No. 3,882,082 and U.S. Pat.
5,013, etc.) or an anticorrosive (eg, U.S. Pat. No. 3,684,587), and a raw material of phenate as a lubricant additive (Hori et al., Journal of the Petroleum Institute, 1991, 34, 446).
It is used as a reaction method using phenols and elemental sulfur (for example,
A. J. Neale et al., Tet rahedron, 1969, 25, 4593), a method using phenols, elemental sulfur and a base catalyst as a reaction raw material (for example, US Pat. No. 3,468,961), phenols, elemental sulfur and molecular halogen (For example, B. Hortling et al., Polym. Bull.,
1982, 8, 1), a method of reacting a phenol with an aryl disulfide under a base catalyst (for example, T. Fujisawa)
J. et al. 0rg. Chem. , 1973, 33, 687), a method using phenols and sulfur halide as reaction raw materials (for example, US Pat. No. 2,239,534), and a method of reacting halogenated phenols with an alkali metal sulfide reagent. Was known.

However, these are 2,2'-thiobis (4-alkylphenol) (dimer), 2- [3- (2
-Hydroxy-5-alkylphenylthio) -2-hydroxy-5-alkylphenylthio] -4-alkylphenol (trimer) or 2- [3- [3- (2-hydroxy-5-alkylphenylthio)- 2-hydroxy-5
An oligomer alone containing monoalkylphenylthio] -2-hydroxy-5-alkylphenylthio] -4-alkylphenol (tetramer) or the like, or a composition containing them, all of which are acyclic alkylphenol sulfides; In addition, the present invention relates to a method for producing the same, and there is no speculation about the existence and production method of cyclic phenol sulfide. As a result of pioneering research, the present inventors found that cyclic phenol sulfides are completely different from acyclic, thiobisalkylphenol dimer, trimer or oligomer compositions, and have a phenol skeleton as the basic skeleton. The development of a novel cyclic phenol sulfide containing three or more and the production method thereof have been developed (JP-A-10-81680, etc.). Although it was an epoch-making technology in the sense of making it possible, the provision of a higher-yield synthesis method was demanded in order to promote industrial use.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing cyclic phenol sulfide from inexpensive raw materials in high yield.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have previously prepared a reaction between a linear polyphenol sulfide represented by the general formula (1) and a specific amount of elemental sulfur by a specific amount of an oxidized or alkali metal hydroxide reagent. It has been found that the above-mentioned cyclic phenol sulfide can be produced by reacting in the presence of at least one metal reagent selected from oxidized or alkaline earth metal reagents. As a result of examining the sulfidation reaction in more detail to achieve
The raw material chain polyphenol sulfide and a specific amount of an oxidized or alkali metal hydroxide reagent and at least one metal reagent selected from an oxidized or alkaline earth metal reagent are reacted in advance, and after removing water in the reaction system, By starting the substantial reaction by adding elemental sulfur,
It has been discovered that a significant improvement in yield can be achieved, leading to the completion of the present invention. That is, the present invention provides a compound represented by the general formula (1):

[0006]

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Wherein R is a hydrogen atom or a hydrocarbon group, a plurality of Rs may be the same or different, a and b are 0 or 1, and m is 1-7.
And a plurality of m may be the same or different, and p is an integer of 2 or more), and a phenol constituting the linear polyphenol sulfide After reacting at least one metal reagent selected from an oxidized or alkaline metal hydroxide reagent and an oxidized or alkaline earth metal reagent in an amount of 0.05 gram equivalent or more per gram equivalent of the skeleton, and removing water in the reaction system, The reaction is carried out by reacting 0.05 g equivalent or more of elemental sulfur per 1 g equivalent of the phenol skeleton constituting the chain sulfurized phenoxide by the general formula (2)

[0008]

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Wherein R is a hydrogen atom or a hydrocarbon group, a plurality of Rs may be the same or different, m is an integer of 1 to 7, and a plurality of m are the same Or n may be different, and n is an integer of 3 or more). A method for producing a cyclic phenol sulfide represented by the formula: Hereinafter, the present invention will be described in detail.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The raw material of the present invention is a linear polyphenol sulfide represented by the above general formula (1). In the general formula (1), R is a hydrogen atom or a hydrocarbon group, which may be the same or different. The number of carbon atoms in the hydrocarbon group is not particularly limited as long as it is 1 or more, but is preferably 1 to 50, and particularly preferably 1 to 18. These hydrocarbon groups include, for example, saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, alicyclic monoaliphatic hydrocarbon groups, aromatic hydrocarbon groups, and aromatic hydrocarbon groups. And aliphatic hydrocarbon groups. Suitable specific examples of the saturated aliphatic hydrocarbon group include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 2-methylbutyl N-hexyl, isohexyl, 3-methylpentyl, ethylbutyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, isononyl, 1
-Methyloctyl, ethylheptyl, n-decyl, 1-methylnonyl, n-undecyl, 1,1-dimethylnonyl, n
-Dodecyl, n-tetradecyl, n-heptadecyl, n-
And hydrocarbon groups such as octadecyl and a group consisting of a polymer of ethylene, propylene or butylene or a copolymer thereof.

Suitable specific examples of the unsaturated aliphatic hydrocarbon group include, for example, vinyl, allyl, isopropenyl, 2-
Butynyl, 2-methylallyl, 1,1-dimethylallyl, 3
-Methyl-2-butynyl, 3-methyl-3-butynyl, 4-pentynyl, hexenyl, octenyl, nonenyl, decenyl groups, and groups formed from acetylene, butadiene, isopropylene polymers or copolymers thereof. Suitable specific examples of the alicyclic hydrocarbon group include:
For example, cyclobrovir, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 2-methylcyclooctyl, cyclopropenyl, cyclobutenyl, cyclopentynyl, cyclohexenyl, cyclopentynyl , Cyclooctenyl, 4-methylcyclohexenyl, 4-ethylcyclohexenyl group and the like.

Suitable specific examples of the alicyclic monoaliphatic hydrocarbon group include, for example, cyclopropylethyl, cyclobutylethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl, cycloheptylmethyl, cyclooctylethyl, 3-methylcyclohexyl Propyl, 4-methylcyclohexylethyl, 4-ethylcyclohexylethyl, 2-methylcyclooctylethyl, cyclopropenylbutyl, cyclobutenylethyl, cyclopentynylethyl, cyclohexenylmethyl, cycloheptynylmethyl, cyclooctenylethyl, 4-methylcyclohexenylpropyl, 4-ethylcyclohexenylpentyl and the like. Suitable specific examples of the aromatic hydrocarbon group include aryl groups such as phenyl and naphthyl, 4-methylphenyl, 3,4-dimethylphenyl, 3,4,5-trimethylphenyl, 2-ethylphenyl, n- Butylphenyl, tert-butylphenyl, amylphenyl, hexylphenyl, nonylphenyl, 2-t
and aryl groups such as ert-butyl-5-methylphenyl, cyclohexylphenyl, cresyl, oxyethylcresyl, 2-methoxy-4-tert-butylphenyl, dodecylphenyl and the like.

Specific examples of the aromatic monoaliphatic hydrocarbon group include, for example, benzyl, 1-phenylethyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenyl Pentyl, 6-phenylhexyl, 1- (4-methylphenyl) ethyl, 2
1- (4-methylphenyl) ethyl, 2-methylbenzyl,
Examples thereof include a 1,1-dimethyl-2-phenylethyl group. These phenols may be used alone or in combination of two or more. In the general formula (1), m is an integer of 1 to 7, and a plurality of m may be the same or different, and a
And b is 0 or 1. p is an integer of 2 or more. The upper limit of p is not particularly limited, but a value of 16 or less is more likely to produce cyclic phenol sulfide, and a value of 12 or less is more likely to produce cyclic phenol sulfide. The chain polyphenol sulfide of the general formula (1) may be used alone or in combination of two or more.

The chain polyphenol sulfide may be produced by any production method. For example, it may be produced by reacting a halogenated phenol with an alkali metal sulfide reagent, or by reacting a phenol with a sulfur halide. Reaction, phenols, elemental sulfur and molecular halogen as the reaction raw material, phenols and elemental sulfur as the reaction raw material, phenols and elemental sulfur as acid One produced by reacting in the presence of a catalyst, one produced by reacting phenols with elemental sulfur in the presence of a base catalyst, or one reacting phenols with aryldisulphides under a base catalyst What was manufactured by the method of making it possible to use can be used.

The reaction of the present invention comprises a reaction between a substantially linear polyphenol sulfide and a metal reagent (hereinafter, referred to as a phenoxydation reaction), and a reaction between the linear sulfide phenoxide produced by this reaction and simple sulfur (hereinafter, referred to as a sulfide). Reaction). The oxidized or alkali metal hydroxide reagent used in the phenoxidation reaction includes oxides or hydroxides such as lithium, sodium, potassium, rubidium, and cesium.
Oxides or hydroxides such as cesium are preferred. Also, as the oxidized or alkaline earth metal hydroxide reagent,
Oxides or hydroxides such as magnesium, calcium, strontium and barium are mentioned, and oxides or hydroxides such as calcium and barium are preferred.
These metal reagents may be used alone or in a combination of two or more. When two or more metal reagents are used in combination, the above oxides may be used,
The above hydroxides may be used together, or a combination of the above oxides and the above hydroxides may be used.

The amount of the metal reagent used is based on 1 gram equivalent of the phenol skeleton constituting the linear polyphenol sulfide.
It is at least 0.05 g equivalent, preferably at least 0.08 g equivalent. The upper limit of the amount of the metal reagent is not particularly limited, but is preferably 10 gram equivalent or less, particularly preferably 5 gram equivalent or less. The phenol skeleton constituting the chain polyphenol sulfide is a phenol skeleton which is a repeating unit of the chain polyphenol sulfide, and is specifically phenol or phenol in which a hydrocarbon group is substituted at the p-position. In addition, in order to homogenize the reaction raw materials,
Water or the like may be added at the beginning of the reaction. The reaction between the metal reagent and the chain polyphenol sulfide is not particularly limited as long as the reaction system does not solidify. However, in order to suppress the time required for the reaction and the useless thermal decomposition reaction, the reaction is carried out at 25 ° C or higher.
0 ° C or lower is preferable, and 50 ° C or higher and 150 ° C or lower is particularly preferable. In the present invention, the water of the reaction system is removed by a phenoxydation reaction. The phenoxidation reaction produces water as a by-product. The produced water is preferably removed at the reaction temperature. For efficient removal of water, it is preferable to distill off water under reduced pressure in the reaction system. In this case, the pressure is preferably 100 mmHg or less, particularly preferably 50 mmHg or less. If water or the like is added at the beginning of the reaction in order to homogenize the reaction raw materials, it goes without saying that this is removed together with the water produced by the reaction in this operation.

The removal of water is not particularly limited as long as it is before the addition of elemental sulfur, and may be carried out throughout the phenoxidation reaction or after the phenoxidation reaction. Preferably, the water in the reaction system is substantially removed from the water in the reaction system, and the water content in the reaction system is 10% or less of the theoretical amount generated from the reaction between the linear polyphenol sulfide and the metal reagent. It is particularly preferable that the content be 1% or less. (In other words, the amount is preferably 0.1 mol or less, particularly preferably 0.01 mol or less, per 1 g equivalent of the phenol skeleton constituting the chain polyphenol sulfide.) The phenoxydation reaction of the present invention is carried out under an inert gas atmosphere. It is preferred to do so. As an inert gas,
For example, nitrogen, argon, helium and the like can be mentioned.

In the sulfurization reaction of the present invention, the raw material charge ratio of the obtained chain sulfide phenoxide to elemental sulfur is 0.05 g of elemental sulfur to 1 gram equivalent of the phenol skeleton constituting the chain sulfide phenoxide. At least equivalent, preferably at least 0.1 gram equivalent. The upper limit of the raw material charge ratio of the elemental sulfur is not particularly limited, but is preferably not more than 20 gram equivalents, particularly preferably not more than 10 gram equivalents per gram equivalent of the phenol skeleton constituting the chain sulfurized phenoxide. The sulfurization reaction is also preferably performed in an inert gas atmosphere, and the sulfurization reaction is preferably performed while removing hydrogen sulfide generated during the reaction. Examples of the inert gas include, for example, nitrogen, argon, helium, and the like as in the phenoxydation reaction in the preceding stage. The reaction temperature of this sulfidation reaction is preferably 80 ° C or higher, and more preferably 100 ° C
The above is preferable, and 120 ° C. or higher is particularly preferable. The upper limit of the reaction temperature is not particularly limited, but is preferably 300 ° C or lower, particularly preferably 280 ° C or lower. The reaction time of the sulfidation reaction is not particularly limited, but may be usually 1 to 24 hours. In addition, it is preferable to use a solvent as necessary for the sulfurization reaction. As the solvent, any solvent may be used as long as it has a boiling point of the reaction temperature or lower and the solvent itself is not easily sulfided. Suitable solvents include, for example, aliphatic hydrocarbons such as hexadecane and tetradecane, and aromatic hydrocarbons such as cymene and pseudocumene. And ethers such as diphenyl ether, hexyl ether, triethylene glycol diethyl ether and tetraethylene glycol dimethyl ether, sulfides such as diphenyl sulfide, dihydric alcohols such as ethylene glycol and diethylene glycol, and mixtures thereof. Further, other solvents can be used as long as they are harmless at the time of reaction and in the application of the product.

A reaction product is obtained by hydrolyzing the reaction mixture of the above reaction with an acidic aqueous solution such as an aqueous sulfuric acid solution or an aqueous hydrochloric acid solution. When the reaction product is a mixture of two or more cyclic phenol sulfides, the reaction product can be separated and purified by ordinary separation and purification means, for example, column chromatography, a recrystallization method, or a combination thereof. I just need. The product of the present invention is a cyclic phenol sulfide represented by the general formula (2). In the general formula (2), R is a hydrogen atom or a hydrocarbon group,
This is the same as in the general formula (1). In general formula (2), R
Are present three or more times in one molecule, and their Rs may be the same or different. In the general formula (2), m is an integer of 1 to 7, but 1 to 5 is easily generated. In the general formula (2), there are three or more Sm in one molecule, and each m of the Sm may be the same or different. n is an integer of 3 or more.
The upper limit of n is not particularly limited, but it is easy to generate 30 or less, and 16
The following are easier to generate, especially 12 or less.

[0020]

EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited by these examples. Production Example 1 110.9 g of sulfur alone in 130.3 g of 4-tert-butylphenol
g, potassium hydroxide 28.3 g, and tetraethylene glycol dimethyl ether 40 ml. The suspension was kept at 130 ° C. while stirring in a nitrogen stream, and reacted for 2 hours while removing water and hydrogen sulfide generated by the reaction, and further reacted for 180 hours.
The temperature was raised to 0 ° C., and the reaction was carried out for 4 hours while removing water and hydrogen sulfide generated in the reaction. The reaction mixture was cooled to room temperature, added with 1500 ml of ether, and hydrolyzed with 2N diluted sulfuric acid. Wash the ether layer with water to remove sulfuric acid,
The reaction product obtained by distilling off the ether under reduced pressure was analyzed. In the general formula (1), P = 2 to 11, m ± 1 to 3, a
= 0 to 1, b = 0 to 1 and R = tert-butyl, a mixture of linear polyphenol sulfides.
As analyzed by C, the conversion to linear polyphenol sulfide based on 4-tert-butylphenol was about 80%.

Production Example 2 The linear polyphenol sulfide obtained in Production Example 1, that is, p = 2 to 11, m = 1 to 3, a = 0 to 1, b in the general formula (1)
= 0 to 1, 300 ml of acetic acid was added to 50 g of a mixture of linear polyphenol sulfides in which R = tert-butyl, and the precipitated solid was separated by filtration and dried, and P = 3 to 11 in the general formula (1). , M ±
1-3, a = 0-1, b = 0-1, R = tert-butyl;
= 5 to 9 as a main component to obtain a mixture of powdery polyphenol sulfides.

Example 1 The chain polyphenol sulfide obtained in Production Example 1, that is, p = 2 to 11, m = 1 to 3, a = 0 to 1, b in the general formula (1)
= 0 to 1 and a mixture of linear polyphenol sulfides in which R = tert-butyl 30.0 g (0.16 to phenol skeleton equivalent)
0.14 gram equivalent) and 3.44 g of sodium hydroxide
(0.086 gram equivalent), 55.1 g of diphenyl ether
Was added and the temperature was raised to 110 ° C. in a nitrogen stream with stirring for 30 minutes. After the temperature of the reaction system reached 110 ° C., the generated water was distilled off under a reduced pressure of 15 mmHg, and about 3 ml of water was removed from the system in 30 minutes. At this time, almost 100% of the theoretical amount was removed from the system, and 1 mol per 1 gram equivalent of the phenol skeleton constituting the chain polyphenol sulfide was used.
Of water was removed. Next, simple sulfur 2.
20 g (0.069 gram equivalent) was added, the suspension was heated to 220 ° C. while stirring in a nitrogen stream, and reacted for 2 hours while removing hydrogen sulfide with a nitrogen stream. The reaction mixture was cooled to room temperature, 100 ml each of toluene and ether was added thereto, and the mixture was hydrolyzed with 2N diluted sulfuric acid. The mixed solution was allowed to stand at about 20 ° C. for 12 hours, and the precipitated crystals were separated by filtration and washed with 100 ml of ether and 100 ml of cold water to obtain 8.9 g of white crystals. Analysis of this crystal showed that, in the general formula (2), n = 4 and 6, m = 1, R = tert
It was confirmed to be a mixture of cyclic phenol sulfides which were -butyl. The yield in terms of tert-butylphenol is about 30%. The organic layer was recovered from the solution after filtering off the crystal fraction, washed with water to remove sulfuric acid, and the reaction product obtained by distilling off ether / toluene under reduced pressure was analyzed.
In the general formula (2), the formation of a mixture of cyclic phenol sulfides having n = 4, m = 1, R = tert-butyl as main components, and having distributions of n = 3 to 10, m = 1 to 3 is recognized. Was. Silica gel column chromatography (n-hexane-chloroform)
As a result, the yield was 6.9 g. The yield in terms of tert-butylphenol is about 23%, and the total yield combined with the above crystal components is about 53%.

Example 2 The chain polyphenol sulfide obtained in Production Example 2, that is, P = 3 to 11, m = 1 to 3, a = 0 to 1, b = in the general formula (1)
0 to 1, R = tert-butyl, and 30.0 g (0.17 to 0.18 gram equivalent in terms of phenol skeleton) of a mixture of powdered polyphenol sulfide having P = 5 to 9 as a main component was used as a raw material. Other than that, it carried out similarly to Example 1. When the reaction product obtained as crystals was analyzed, in the general formula (2), n = 4 and 6, m = 1, R = tert-butyl as a main component,
Formation of a mixture of cyclic phenol sulfides having distributions of n = 4 to 10 and m = 1 to 3 was observed. The yield was 9.9 g. te
The yield in terms of rt-butylphenol is about 33%. In the general formula (2), n = 4, m = 1, and R = tert-, which were recovered by chromatography from the organic layer of the solution after filtering off the crystal fraction.
7.0 g of a mixture of cyclic phenol sulfides containing butyl as a main component and having distributions of n = 3 to 10 and m = 1 to 3 was obtained. tert-
The yield in terms of butylphenol is about 23%, and the total yield in combination with the above crystal components is about 56%.

Comparative Example 1 30.0 g of the linear polyphenol sulfide obtained in Production Example 2
(Phenol skeleton equivalent 0.17-0.18 gram equivalent)
With 3.44 g (0.086 gram equivalent) of sodium hydroxide, 55.1 g of diphenyl ether, 2.20 g of elemental sulfur
(0.069 gram equivalent) and the temperature was raised to 110 ° C. in a nitrogen stream with stirring for 30 minutes. After the temperature of the reaction system reached 110 ° C, the mixture was stirred for 1 hour, and then the suspension was cooled to 220 ° C.
, And reacted for 2 hours while removing hydrogen sulfide with a nitrogen stream. At this time, about 1.5 ml of water distilled out into the exhaust line. This means that about 50% of the theoretical amount was removed from the system, which corresponds to the removal of 0.5 mol of water per gram equivalent of the phenol skeleton constituting the chain polyphenol sulfide. The reaction mixture was cooled to room temperature, 100 ml each of toluene and ether was added thereto, and the mixture was hydrolyzed with 2N diluted sulfuric acid. After recovering the organic layer, the product was washed with water to remove sulfuric acid, and ether / toluene was distilled off under reduced pressure. The obtained reaction product was analyzed. In the general formula (2), n = 6, m = 1, The formation of a mixture of cyclic phenol sulfides having R = tert-butyl as a main component and having distributions of n = 3 to 10 and m = 1 to 3 was observed. The yield was 5.7 g. The yield in terms of tert-butylphenol is about 19%. In the general formula (2), n = 4, m = 1, R recovered by chromatography from the organic layer of the solution after filtering off the crystal fraction.
= 3.8 g of a mixture of cyclic phenol sulfides having tert-butyl as a main component and having distributions of n = 3 to 10 and m = 1 to 3. The yield in terms of tert-butylphenol is about 13%, and the total yield combined with the above-mentioned crystal components is about 32%.

Comparative Example 2 30.0 g of the chain polyphenol sulfide obtained in Production Example 2
(Phenol skeleton equivalent 0.17-0.18 gram equivalent)
With 3.44 g (0.086 gram equivalent) of sodium hydroxide, 55.1 g of diphenyl ether, 2.20 g of elemental sulfur
(0.069 gram equivalent) and the temperature was raised to 110 ° C. in a nitrogen stream with stirring for 30 minutes. After the temperature of the reaction system reached 110 ° C, the mixture was stirred for 1 hour, and then the suspension was cooled to 220 ° C.
, And reacted for 2 hours while removing hydrogen sulfide with a nitrogen stream. During this time, a water-cooled reflux condenser was installed at the gas exhaust port of the reaction vessel to suppress discharge of generated water outside the system.
At this time, it corresponds to 100% of the theoretical production amount, that is, 1 mol of water was contained in the system per 1 gram equivalent of the phenol skeleton constituting the chain polyphenol sulfide. The reaction mixture was cooled to room temperature, 100 ml each of toluene and ether was added thereto, and the mixture was hydrolyzed with 2N diluted sulfuric acid. After recovering the organic layer, the product was washed with water to remove sulfuric acid, and ether / toluene was distilled off under reduced pressure. The obtained reaction product was analyzed. In the general formula (2), n = 6, m
= 1, R = tert-butyl as a main component, n = 3-10, m = 1-
The formation of a mixture of cyclic phenol sulfides with a distribution of 3 was observed. The yield was 2.7 g. The yield in terms of tert-butylphenol is about 9%. In the general formula (2), n = 4, m = 1, R = tert-butyl as a main component, and n = 3 to 10, which were recovered by chromatography from the organic layer of the solution after filtering off the crystal fraction. The mixture of cyclic phenol sulfides having a distribution of m = 1 to 3 was 3.0 g. The yield in terms of tert-butylphenol is about 10%, and the total yield in combination with the above crystal components is about 19%.

[0026]

According to the method of the present invention, a cyclic phenol sulfide containing at least three phenol skeletons in the basic skeleton can be efficiently produced.

Continued on the front page (72) Inventor Hitoshi Kumagai 1134-2, Gongendo, Satte City, Saitama Prefecture Inside the R & D Center of Sumo Research Institute, Inc. (72) Haruhiko Takeya 1134-2, Gongendo, Satte City, Saitama Prefecture In the R & D Center of Sumo Research Institute (72) Inventor Hiroaki Kaneko 1134-2 Gongendo, Satte City, Saitama Prefecture In the R & D Center of Kosmo Research Institute Co., Ltd.

Claims (1)

[Claims] 1. A compound of the general formula (1) (Wherein, R is a hydrogen atom or a hydrocarbon group, and a plurality of Rs may be the same or different,
a and b are 0 or 1, m is an integer of 1 to 7, a plurality of m may be the same or different, and p
Is an integer of 2 or more) and an oxidation or alkali metal hydroxide reagent of at least 0.05 gram equivalent per gram equivalent of a phenol skeleton constituting the chain polyphenol sulfide, and Alternatively, after reacting at least one metal reagent selected from alkaline earth metal hydroxide reagents and removing water in the reaction system, 0.05 g equivalent or more of a simple substance per 1 g equivalent of the phenol skeleton constituting the chain sulfide sulfide is used. Reaction of sulfur with general formula (2) (Wherein, R is a hydrogen atom or a hydrocarbon group, and a plurality of Rs may be the same or different,
m is an integer of 1 to 7, a plurality of m may be the same or different, and n is an integer of 3 or more). A method for producing a cyclic phenol sulfide.