JPH1081681A - Production of cyclic phenol sulfide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently obtain the subject compound capable of being utilized as an intermediate for functional molecules utilizing ion or molecule-recognizing abilities by preliminarily producing a metal phenoxide compound from a metal reagent and a phenol compound and subsequently reacting the reaction product with a specific amount of simple sulfur body. SOLUTION: (A) A phenol compound of formula I (Y<1> is H, a hydrocarbon) is reacted with (B) at least a metal reagent selected from a cesium metal reagent, a calcium metal reagent and a barium metal reagent in an amount of >=0.1g equivalent per g equivalent of the compound A to produce a metal phenoxide compound, which is reacted with (C) simple sulfur body in an amount of >=0.5g equivalent per g equivalent of the component A to produce a cyclic phenol sulfide of formula II [Y<2> is H, a hydrocarbon; (n) is an integer of 6-16; (m) is an integer of 1-7]. Thereby, the objective compound especially containing six or more phenol skeletons in the basic skeleton can further effectively be produced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an antioxidant, a catalyst, a metal supplement, an optical sensor, an ion sensor, a substrate specificity sensor, a separation membrane material, a polymer material, a phase transfer catalyst, an artificial enzyme, and light energy conversion. Material or other,
The present invention relates to a novel method for selectively producing a cyclic phenol sulfide which can be used as an intermediate of a functional molecule utilizing the ability to recognize ions and molecules.

[0002]

2. Description of the Related Art Heretofore, sulfides of alkylphenols have been used as antioxidants (for example, US Pat. No. 2,239,239).
No. 534 and U.S. Pat. No. 3,337,334) and rubber sulphides (e.g. U.S. Pat. No. 3,468,961).
And US Pat. No. 3,647,885), polymer stabilizers (eg, US Pat. No. 3,882,082).
No. 3,845,013, U.S. Pat. No. 3,843,600), or an anticorrosive (eg, U.S. Pat. No. 3,684,587), and a lubricant additive. It is known as a raw material of phenate (Hori et al., Journal of the Petroleum Institute of Japan, 1991, 34, 446), and these include 2,2′-thiobis (4-alkylphenols) (dimer), 2- [3- (2-hydroxy-5
-Alkylphenylthio) -2-hydroxy-5-alkylphenylthio] -4-alkylphenols (trimer) or 2- [3- [3- (2-hydroxy-5
-Alkylphenylthio) -2-hydroxy-5-alkylphenylthio] -2-hydroxy-5-alkylphenylthio] -4-alkylphenols (tetramer) alone or in a composition containing them All were acyclic alkylphenol sulfides.

[0003]

We have previously found the existence of a cyclic phenol sulfide containing at least three phenol skeletons in the basic skeleton and a method for producing the same (Japanese Patent Application No. 8-7090).
2) In the present invention, it is an object of the present invention to provide a more efficient method for producing a cyclic phenol sulfide containing a phenol skeleton as a basic skeleton, particularly from 6 to 16 inclusive.

[0004]

Means for Solving the Problems In order to achieve the above object, the present inventors have investigated the metal phenoxide formation reaction and the sulfurization reaction of various phenols. A phenol having a hydrocarbon group at the 4-position of, a cesium metal reagent,
At least one specific amount of a metal reagent selected from a calcium metal reagent and a barium metal reagent is reacted, and after a metal phenoxide of the metal reagent and the phenol is generated in advance, a specific amount of elemental sulfur is reacted. As a result, an efficient method for producing a cyclic phenol sulfide containing 6 to 16 phenol skeletons as a basic skeleton in the above-mentioned cyclic phenol sulfide has been found, and the present invention has been completed. That is, the present invention provides a compound represented by the general formula (1):

[0005]

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(Wherein Y ¹ is a hydrogen atom or a hydrocarbon group), and a cesium metal reagent and a calcium metal reagent in an amount of 0.1 gram equivalent or more per 1 gram equivalent of the phenol And at least one metal reagent selected from barium metal reagents to form metal phenoxides of the metal reagents and the phenols in advance, and then 0.5 g equivalent or more per 1 g equivalent of the phenols Reaction of the elemental sulfur of the general formula (2)

[0007]

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(Wherein Y ² is a hydrogen or hydrocarbon group, n is an integer of 6 or more and 16 or less, m is an integer of 1 to 7, and m of a plurality of Sm is the same. And a plurality of Y ^{2 s} may be the same or different, respectively, to produce a cyclic phenol sulfide represented by the formula (1): The present invention provides a method for producing sulfide. Hereinafter, the present invention will be described in detail.

The phenol used in the present invention is a compound represented by the general formula (1), wherein Y ¹ is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group has at least one carbon atom. Is not particularly limited, preferably 1 to 50
And particularly preferably 1 to 18. Examples of these hydrocarbon groups include a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an alicyclic-aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an aromatic-hydrocarbon group. And aliphatic hydrocarbon groups. 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, and hydrocarbon groups such as n-octadecyl and a group consisting of a polymer of ethylene, propylene or butylene or a copolymer thereof.

Suitable examples of unsaturated aliphatic hydrocarbon groups include, for example, vinyl, allyl, isopropenyl, 2-
Butenyl, 2-methylallyl, 1,1-dimethylallyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 4-pentenyl, hexenyl, octenyl, nonenyl, decenyl groups, and acetylene, butadiene, and isopropylene Examples include a group formed of a polymer or a copolymer thereof. Suitable specific examples of the alicyclic hydrocarbon group include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 2-methylcyclooctyl , Cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclopentenyl, cyclooctenyl, 4-methylcyclohexenyl,
4-ethylcyclohexenyl group and the like. Suitable specific examples of the alicyclic-aliphatic hydrocarbon group include, for example, cyclopropylethyl, cyclobutylethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl, cycloheptylmethyl, cyclooctylethyl, 3-methylcyclohexylpropyl, -Methylcyclohexylethyl, 4-ethylcyclohexylethyl, 2-methylcyclooctylethyl, cyclopropenylbutyl, cyclobutenylethyl, cyclopentenylethyl, cyclohexenylmethyl, cycloheptenylmethyl, cyclooctenylethyl, 4-methylcyclohexenyl Propyl, 4-ethylcyclohexenylpentyl and the like.

Suitable examples of the aromatic hydrocarbon group include an aryl group such as phenyl and naphthyl;
Methylphenyl, 3,4-dimethylphenyl, 3,4
5-trimethylphenyl, 2-ethylphenyl, n-butylphenyl, tert-butylphenyl, amylphenyl, hexylphenyl, nonylphenyl, 2-ter
and aryl groups such as t-butyl-5-methylphenyl, cyclohexylphenyl, cresyl, oxyethylcresyl, 2-methoxy-4-tert-butylphenyl and dodecylphenyl. Specific examples of the aromatic-aliphatic hydrocarbon group include, for example, benzyl, 1-phenylethyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 4-phenylbutyl,
-Phenylpentyl, 6-phenylhexyl, 1- (4
-Methylphenyl) ethyl, 2- (4-methylphenyl) ethyl, 2-methylbenzyl, 1,1-dimethyl-
A 2-phenylethyl group and the like. These phenols may be used alone or in combination of two or more.

Suitable examples of the cesium metal reagent, calcium metal reagent and barium metal reagent used in the present invention include, for example, simple cesium metal, cesium hydroxide and its hydrate, cesium hydrogen carbonate, cesium carbonate,
Cesium ethoxide, cesium propoxide, cesium butoxide, calcium metal simple substance, calcium hydride,
Calcium oxide, calcium carbonate, barium metal alone,
Examples thereof include barium oxide, barium carbonate, barium hydroxide and hydrates thereof. Of these, cesium hydroxide monohydrate, calcium metal alone, calcium hydride, calcium oxide, barium oxide, and barium hydroxide 8 are preferred.
Hydrates, particularly preferably cesium hydroxide monohydrate, calcium oxide, and barium hydroxide octahydrate.
These metal reagents may be used alone or in combination of two or more. The amount of the metal reagent used is
It is at least 0.1 gram equivalent, preferably at least 0.2 gram equivalent, per gram equivalent of phenols. The upper limit of the amount of the metal reagent used is not particularly limited, but is preferably 10
It is at most gram equivalent, particularly preferably at most 5 gram equivalent.

The metal of the metal reagent used is phenols 1
It is preferred that the metal of all metal reagents be reacted with phenols to form metal phenoxides in a portion of 1 gram equivalent or less per gram equivalent. In addition, since phenoxide is usually generated by removing water, alcohols, carbon dioxide gas or hydrogen generated during this reaction, the pressure in the reaction system is gradually reduced to distill them, or an inert gas is used. It is preferable to drive them out under an air stream or remove them in combination. The degree to which water, alcohols, carbon dioxide or hydrogen generated during this reaction is removed depends on the metal reagent used and the reaction conditions. For water, at least 70 mol% of the theoretical amount of water generated is removed. It is particularly preferable to remove 80 mol% or more. As for alcohols, the theoretical amount of alcohol to be produced is 80%.
It is preferable to remove at least 90 mol%, particularly preferably at least 90 mol%. As for the carbon dioxide gas, it is preferable to remove 70 mol% or more of the theoretical amount of the generated carbon dioxide gas, and it is particularly preferable to remove 80 mol% or more. With respect to hydrogen, it is preferable to remove 90 mol% or more of the theoretical amount of hydrogen generated in the reaction, and in particular, 95%
It is preferred to remove at least mol%.

In the present invention, water or alcohols may be added at the beginning of the reaction in order to homogenize the reaction raw materials. Examples of the alcohols include monohydric alcohols such as methanol, ethanol, propanol and butanol, ethylene glycol, propylene glycol,
Examples thereof include dihydric alcohols such as 3-propanediol, 1,4-butanediol, and diethylene glycol. When water or the above-mentioned alcohols used for homogenizing the reaction raw materials is used, the amount of use is not particularly limited, but is preferably 0.1 to 10 mol with respect to 1 gram equivalent of the metal reagent used. Preferably it is 0.5-5 mol. Also in this case, it is preferable to remove water or the alcohols used at the beginning of the reaction in order to homogenize the reaction raw materials in order to more efficiently generate metal phenoxides. In this removal, the pressure in the reaction system may be gradually reduced to distill them, or they may be driven out under an inert gas stream, or they may be removed in combination. Further, water, alcohols, carbon dioxide or hydrogen generated in the metal phenoxides formation reaction and water used at the beginning of the reaction to homogenize the reaction raw materials or the alcohols may be simultaneously removed.

With respect to water or the alcohols used at the beginning of the reaction to homogenize the reaction raw materials, it is preferable to remove 80% by mass or more of water used at the beginning of the reaction, especially 90% by mass or more. Is preferred. For monohydric alcohols such as methanol, ethanol, propanol, and butanol, it is preferable to remove 90% by mass or more of the monohydric alcohol used at the beginning of the reaction, and it is particularly preferable to remove 95% by mass or more. For dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, and diethylene glycol, it is preferable to remove 70% by mass or more of the dihydric alcohol used at the beginning of the reaction. Particularly, it is preferable to remove 80% by mass or more. In the present invention, the reaction temperature in the metal phenoxides-forming reaction between the metal reagents and the phenol is preferably room temperature or higher, and particularly preferably 50 ° C. or higher. The upper limit of the reaction temperature at this time is not particularly limited, but is preferably 300 ° C. or lower, particularly preferably 250 ° C. or lower. The reaction time varies depending on the concentration of the metal reagent used and the use of water or alcohols for homogenizing the reaction raw materials.
5 to 24 hours are preferred.

The phenoxide thus produced, or a reaction mixture from which water, alcohols, carbon dioxide or hydrogen produced in the reaction between the phenols and the metal reagent were removed, or used to homogenize the reaction raw materials. To the reaction mixture from which the solvent had been removed in advance, 0.5 g of elemental sulfur was added to 1 gram equivalent of phenols charged at the beginning of the reaction.
Reaction of elemental sulfur over gram equivalent. The upper limit of the raw material charging ratio of the elemental sulfur is not particularly limited, but is preferably 20 gram equivalent or less, particularly preferably 10 gram equivalent or less, based on 1 gram equivalent of the phenol initially charged. The temperature of the reaction mixture at the time of adding elemental sulfur is not particularly limited, but is preferably in the range of room temperature to 200 ° C, and particularly preferably in the range of room temperature to 150 ° C. In the present invention, the sulfidation reaction temperature after the addition of simple sulfur is preferably 80 ° C. or higher, and particularly preferably 100 ° C. or higher. Further, the upper limit of the sulfidation reaction temperature is preferably 300 ° C. or lower, particularly preferably 280 ° C. or lower. The sulfurization reaction time varies depending on the concentration of the metal reagent and the reaction temperature, but is generally preferably 0.5 to 24 hours.

The reaction of the present invention is preferably carried out in an inert gas atmosphere. As the inert gas, for example, nitrogen,
An inert gas such as argon and helium is used. In addition, the reaction of the present invention is preferably performed while removing hydrogen sulfide generated during the reaction. In order to remove hydrogen sulfide generated during the reaction, the reaction is preferably performed under an inert gas stream. Further, in the present invention, it is preferable to use a solvent as necessary through the metal phenoxide generation reaction and the sulfurization reaction. The solvent is not particularly limited, but preferred solvents are, for example, aliphatic hydrocarbons such as hexadecane and tetradecane, aromatic hydrocarbons such as cymene and pseudocumene, diphenyl ether, hexyl ether, triethylene glycol diethyl ether, and tetraethylene glycol dimethyl ether. And the like, disulfides such as diphenyl sulfide, and mixtures thereof. Further, other solvents can be used as long as they are harmless during the reaction and in terms of the use of the product. The reaction product of the present invention 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, it may be separated and purified by a usual separation means, for example, column chromatography, a recrystallization method, or a combination thereof.

[0018]

Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by these examples. Example 1 To 150.16 g of 4-tert-butylphenols,
Ethylene glycol (28 mL), tetraethylene glycol dimethyl ether (44 mL) and calcium oxide (14.61 g) were added, and the pressure was reduced while stirring in a nitrogen gas stream. The temperature was gradually increased to 120 ° C. and 2 mbar over 7 hours to remove water and ethylene glycol produced in the reaction. did.
The total amount of water distilled during the reaction, ethylene glycol, and 4-tert-butylphenols mixed with these was 43.68 g, which was initially 82% by mol of the theoretical amount of water formed in the reaction and water. Ethylene glycol of 88% by mass of the ethylene glycol used was removed. After the pressure in the reaction system was returned to normal pressure with nitrogen, simple sulfur was 48.17.
g, and gradually heated to 230 ° C. over 4 hours while stirring in a nitrogen stream, and further continued stirring for 3 hours. During this time, the reaction was performed while removing hydrogen sulfide generated by the reaction. The amount of hydrogen sulfide generated by the reaction was 32 g. The color of the reaction mixture is very dark yellow-red (5YR 2/1
The color name was JISZ8102 compliant). The reaction mixture was cooled to room temperature, added with 500 mL of ether, and sufficiently hydrolyzed with 1N diluted sulfuric acid. As a result of mass spectrometry of the reaction mixture obtained by removing ether from the separated ether layer, n = 10 and m =
1, Y ² = tert-butyl as a main component, n = 6-1
The formation of a mixture of cyclic phenol sulfides having a distribution of 2 was observed. The reaction mixture was further separated by silica gel chromatography (toluene-toluene / chloroform) and recrystallized from 1,4-dioxane. In the general formula (2), n = 10, m = 1, and Y ² = ter
The cyclic phenol sulfide which is t-butyl is tert-butyl.
8.2% was obtained in an isolated yield based on butylphenols. The physical properties are shown below. MS m / z: 1800 (M +), Elemental analysis% theory _{for C 100 H 120 O 10 S} 10: C, 66.63;
H, 6.71; S, 17.79, found: C, 66.4.
9; H, 6.66; S, 17.17.

Example 2 32 mL of tetraethylene glycol dimethyl ether
Water and ethylene glycol produced by the reaction were removed in the same manner as in Example 1 except that the reaction was carried out. Distilled water, ethylene glycol and 4 mixed with them
The total amount of -tert-butylphenols is 41.19 g.
As a result, 75 mol% of the theoretical amount of water produced by the reaction and 82% by mass of ethylene glycol of the ethylene glycol used at the beginning of the reaction were removed. After the inside of the reaction system was returned to normal pressure with nitrogen, 64.23 g of elemental sulfur was added, the mixture was heated to 200 ° C. over 30 minutes while stirring in a nitrogen stream, and stirring was continued at this temperature for 1 hour and 30 minutes. . During this time, the reaction was performed while removing hydrogen sulfide generated by the reaction. The amount of hydrogen sulfide generated by the reaction was about 27 g. The reaction mixture was cooled to room temperature, 500 mL of ether was added,
It was hydrolyzed with 1N diluted sulfuric acid. FD-MS of the reaction mixture obtained by removing ether from the separated ether layer
As a result of the spectrum analysis, n = 7 in the general formula (2),
The formation of a mixture of cyclic phenol sulfides having m = 1 and Y ² = tert-butyl as a main component and having distributions of n = 6 to 16 and m = 1 to 2 was observed.

Example 3 To 60.11 g of 4-tert-butylphenols, 17 mL of tetraethylene glycol dimethyl ether and 33.69 g of cesium hydroxide monohydrate were added, and the pressure was reduced while stirring in a nitrogen gas stream over 7 hours. Gradually 120
C., 3 mmHg, and water generated by the reaction was removed. Water distilled during the reaction and 4-t mixed with the water
The total amount of tert-butylphenols was 7.31 g, and 79 mol% of the theoretical amount of water generated in the reaction was removed. After returning the pressure in the reaction system to normal pressure with nitrogen, 2
5.66 g was added, and the mixture was gradually heated to 230 ° C. over 4 hours while stirring in a nitrogen stream, and stirring was further continued for 3 hours. During this time, the reaction was performed while removing hydrogen sulfide generated by the reaction. The hydrogen sulfide generated by the reaction was 7.3.
g. The color of the reaction mixture is very dark yellow-red (5YR
2/1 color name was based on JIS Z8102). The reaction mixture was cooled to room temperature and ether 50
0 mL was added, and the mixture was sufficiently hydrolyzed with 1N diluted sulfuric acid. The reaction mixture obtained by distilling ether from the separated ether layer was separated by silica gel column chromatography (toluene-toluene / chloroform). As a result, in the general formula (2), n = 8, m = 1, Y ² =
The cyclic phenol sulfide, tert-butyl, is
An isolation yield of 5.3% was obtained based on rt-butylphenols. The physical properties are shown below. MS m / z: 1440 (M +), Elemental analysis% theory _{for C 80 H 96 O 8 S} 8: C, 66.63; H,
6.71; S, 17.79; Found: C, 66.30;
H, 6.61; S, 17.55

Example 4 To 153.32 g of 4-tert-butylphenols,
32 mL of tetraethylene glycol dimethyl ether and 80.62 g of barium hydroxide octahydrate were added, the pressure was reduced while stirring in a nitrogen stream, and 12
The temperature was adjusted to 0 ° C. and 4 mmHg to remove water generated by the reaction.
The water distilled during the reaction and the 4-
The total amount of tert-butylphenols is 34.19 g.
Thus, 71 mol% of the theoretical amount of water produced in the reaction was removed. After the pressure in the reaction system was returned to normal pressure with nitrogen, 48.35 g of elemental sulfur was added, and the mixture was gradually heated to 230 ° C. over 4 hours while stirring in a nitrogen stream, and further stirred for 3 hours. During this time, the reaction was performed while removing hydrogen sulfide generated by the reaction. The amount of hydrogen sulfide generated by the reaction was 6.7 g. The reaction mixture was cooled to room temperature, added with 500 mL of ether, and sufficiently hydrolyzed with 1N diluted sulfuric acid. As a result of FD-MS spectrum analysis of a reaction mixture obtained by removing ether from the separated ether layer, n = 10, m = 1, and Y ² = in the general formula (2).
Formation of a mixture of cyclic phenol sulfides containing tert-butyl as a main component and having a distribution of n = 6 to 12 was observed.

[0022]

According to the method of the present invention, it is possible to efficiently produce a cyclic phenol sulfide containing a phenol skeleton in the basic skeleton, particularly from 6 to 16 inclusive.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoko Sato 1134-2 Gongendo, Satte City, Saitama Prefecture, Cosmo Research Institute R & D Center

Claims (3)

[Claims] 1. A compound of the general formula (1) Wherein Y ¹ is a hydrogen atom or a hydrocarbon group; and 0.1 g equivalent or more of a cesium metal reagent, a calcium metal reagent and a barium metal in an amount of 0.1 gram equivalent or more per gram equivalent of the phenol. Reacting with at least one metal reagent selected from reagents to generate metal phenoxides of the metal reagent and the phenol in advance, and then adding 0.5 gram equivalent or more of simple sulfur to 1 gram equivalent of the phenol; And reacting with the general formula (2) (Wherein, Y ² is a hydrogen or hydrocarbon group, n is an integer of 6 or more and 16 or less, m is an integer of 1 to 7, and m of a plurality of Sm may be the same. And a plurality of Y ^{2 s} may be the same or different, respectively, to produce a cyclic phenol sulfide represented by the following formula: Manufacturing method. 2. After reacting a phenol with a metal reagent, removing water, alcohols, carbon dioxide or hydrogen generated by the reaction in advance to form a metal phenoxide with the metal reagent and the phenol. The method for producing a cyclic phenol sulfide according to claim 1, wherein elemental sulfur is reacted. 3. A phenol and a metal reagent are reacted in the presence of a solvent used to homogenize the reaction raw material, and water, alcohols, carbon dioxide or hydrogen produced by the reaction are homogenized with the reaction raw material. 2. The method for producing a cyclic phenol sulfide according to claim 1, wherein the solvent used is removed in advance to produce a metal phenoxide with the metal reagent and the phenol, and then the elemental sulfur is reacted.