JPH1077281A - Method for producing halogenated cyclic phenol sulfide - Google Patents

Abstract

(57) [Problem] To provide a method for efficiently producing a halogenated cyclic phenol sulfide. SOLUTION: General formula (1) (Wherein, R is a hydrogen atom, a hydrocarbon group, or an acyl group, m is an integer of 1 to 7, and a plurality of m and R may be the same or different, and n is 3 ~
It is an integer of 12. A) reacting a cyclic phenol sulfide represented by the formula (1) with a halogenating agent to form a halogenated cyclic phenol sulfide having at least one halogen atom at the 3- to 5-position of the benzene ring with respect to the OR group of the general formula (1). Manufacturing things.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a novel halogenated cyclic phenol sulfide by reacting a cyclic phenol sulfide with a halogenating agent.

[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 Petroleum Institute, 1991, 34, 446), and 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-alkylphenylthio] -2-hydroxy-5-alkylphenylthio] -4-alkylphenol (tetramer) alone or a composition containing them. All were acyclic alkylphenol sulfides.

[0003]

SUMMARY OF THE INVENTION We have previously found cyclic phenol sulfide groups containing at least three phenol skeletons in the basic skeleton (Japanese Patent Application No. 8-70902). Metal capture agents, ion sensors, substrate specificity sensors, separation membrane materials, polymer materials,
It has also been found that it is useful as an oxidation catalyst, a phase transfer catalyst, an artificial enzyme, a light energy conversion material, or an intermediate of a functional molecule utilizing recognition of ions or molecules. These cyclic phenol sulfide groups include those having a halogen atom at the 4-position of the benzene ring with respect to the hydroxyl group or a derivative thereof. As a result of further study on the compound, it was found that a cyclic phenol sulfide having a halogen atom at the 3- to 5-position of the benzene ring with respect to the hydroxyl group or its derivative group is useful for the same applications as the above-mentioned cyclic phenol sulfide group. I found Therefore, the present invention
3 to 5 benzene rings relative to the hydroxyl group or its derivative group
It is an object of the present invention to provide a method for efficiently and easily producing a cyclic phenol sulfide having at least one halogen atom at each position.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, they have no substituent at the 3 to 5 position of the benzene ring with respect to the hydroxyl group or its derivative group. By using a cyclic phenol sulfide having phenols as a part of its constituent unit as a raw material and reacting the cyclic phenol sulfide with a halogenating agent, the halogenated cyclic phenol sulfide containing at least one halogen atom described above is obtained. And found a method for efficiently producing the same, thereby completing the present invention. That is, the present invention provides a compound represented by the general formula (1):

[0005]

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Wherein R is a hydrogen atom, a hydrocarbon group or an acyl group, m is an integer of 1 to 7, and a plurality of m and R may be the same or different. N is an integer of 3 to 12), and a halogenating agent is reacted with a cyclic phenol sulfide represented by the general formula (2):

[0007]

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Wherein R is a hydrogen atom, a hydrocarbon group or an acyl group, X, Y, and Z are a hydrogen atom or a halogen atom, and at least one of 3n X, Y, and Z is M is an integer of 1 to 7, and a plurality of R, X, Y, Z and m may be the same or different, and n is an integer of 3 to 12. .)
And a method for producing a halogenated cyclic phenol sulfide characterized by producing a halogenated cyclic phenol sulfide represented by the formula: Hereinafter, the present invention will be described in detail.

The raw material used in the present invention is a cyclic phenol sulfide represented by the above general formula (1). General formula (1)
R in the above is a hydrogen atom, a hydrocarbon group or an acyl group.
The carbon number of the hydrocarbon group is not particularly limited as long as it is 1 or more, but is preferably 1 to 50. 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, te
rt-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, isononyl, 1-methyloctyl,
Ethylheptyl, n-decyl, 1-methylnonyl, n-
Undecyl, 1,1-dimethylnonyl, n-dodecyl,
Examples include hydrocarbon groups such as n-tetradecyl, n-heptadecyl, 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 alicyclic-aliphatic hydrocarbon groups include, for example, cyclopropylethyl, cyclobutylethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl, cycloheptylmethyl, cyclooctylethyl, 3-methylcyclohexyl Propyl, 4-methylcyclohexylethyl, 4-ethylcyclohexylethyl, 2-methylcyclooctylethyl,
Cyclopropenylbutyl, cyclobutenylethyl, cyclopentenylethyl, cyclohexenylmethyl, cycloheptenylmethyl, 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-tert-butyl-5-methylphenyl,
Cyclohexylphenyl, cresyl, oxyethylcresyl, 2-methoxy-4-tert-butylphenyl,
And aryl groups such as dodecylphenyl.

Specific examples of the aromatic-aliphatic 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- (4-methylphenyl) ethyl, 2-methylbenzyl, 1,1-dimethyl-2-phenylethyl and the like. The number of carbon atoms of the acyl group is not particularly limited as long as it is 1 or more, but is preferably 1 to 40. Suitable examples of acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, oxalyl, succinyl, pivaloyl, stearoyl, benzoyl, phenylpropionyl, toluoyl, naphthoyl, phthaloyl, indancarbonyl, p-methylbenzoyl, And a cyclohexylcarbonyl group. In the general formula (1), R
Are present in one molecule, and their R may be the same or different.

Next, a method for producing a cyclic phenol sulfide represented by the general formula (1) as a raw material will be described. The production example of the cyclic phenol sulfide represented by the general formula (1) is disclosed in Japanese Patent Application No. Hei.
No. 70902. As a suitable example of production, first, the general formula (3)

[0013]

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(Wherein, Y is an alkyl group) having an alkyl group at the 4-position and an appropriate amount of elemental sulfur are converted from an appropriate amount of an alkali metal reagent and an alkaline earth metal reagent. In this method, a cyclic alkylphenol sulfide is produced by reacting in the presence of at least one selected metal reagent, and the resulting cyclic alkylphenol sulfide is dealkylated in the presence of an acid catalyst. The raw material charge ratio of alkylphenols and elemental sulfur is 0.1 g of alkylphenols and 0.1 g of elemental sulfur.
It is at least gram equivalent, preferably at least 0.35 gram equivalent. The upper limit of the raw material charge ratio of the elemental sulfur is not particularly limited, but is preferably 20 gram equivalent or less, particularly preferably 10 gram equivalent or less, per 1 gram equivalent of the alkylphenol. Examples of the alkali metal reagent include a simple alkali metal, an alkali metal hydride, an alkali metal hydroxide, an alkali metal carbonate, an alkali metal alkoxide, and an alkali metal halide. Also,
As the alkaline earth metal reagent, for example, alkaline earth metal alone, alkaline earth metal hydride, alkaline earth metal hydroxide, alkaline earth metal oxide, alkaline earth metal carbonate,
Alkaline earth metal alkoxides, alkali earth metal halides and the like can be mentioned. The amount of the alkali metal reagent or alkaline earth metal reagent used is 1
It is at least 0.005 gram equivalent to gram equivalent, preferably at least 0.01 gram equivalent. The upper limit of the amount of the alkali metal reagent or alkaline earth metal reagent used is not particularly limited, but is preferably 10 gram equivalent or less, particularly preferably 5 gram equivalent or less. As the acid catalyst used for the dealkylation, a Friedel-Crafts catalyst can be used. Examples of suitable catalysts include Lewis acids, protic acids or solid acids. Of these,
Suitable specific examples of Lewis acids include AlCl ₃ , AlB
r ₃ , BeCl ₂ , CdCl ₂ , ZnCl ₂ , BF ₃ , BC
l ₃ , BBr ₃ , GaCl ₃ , GaBr ₃ , TiCl ₄ , T
iBr ₄ , ZrCl ₄ , SnCl ₄ , SnBr ₄ , SbCl
₅ , SbCl ₃ , BiCl ₃ , FeCl _{3 and the} like. Suitable specific examples of the protonic acid include sulfuric acid, hydrogen fluoride, perchloric acid, chloroacetic acid, trifluoroacetic acid, phosphoric acid, polyphosphoric acid, and aromatic sulfonic acids such as p-toluenesulfonic acid. Super strong acids can also be used as suitable catalysts. Suitable examples of super _{acid, H2SO4 / SO 3, HF /} BF 3, ClSO 3 H,
FSO ₃ H, FSO ₃ H / SbF ₅ , CF ₃ SO ₃ H, HF
/ SbF _{5 and the} like. Solid superacids can also be used as suitable catalysts. Suitable specific examples of the solid superacid include, but are not limited to, BF ₃ , TaF _5, or SbF ₅
l ₂ O ₃ , SiO ₂ / Al ₂ O ₃ , SiO ₂ / TiO ₂ , Si
Fluorinated sulfonic acid resins such as O ₂ / ZrO _{2 and} graphite. These catalysts may be used alone or in a combination of two or more. The hydroxyl group of this cyclic phenol sulfide may be left as it is, or the hydrogen atom of the hydroxyl group may be replaced with a hydrocarbon group or an acyl group by etherification or acylation.

By halogenating the cyclic phenol sulfide represented by the general formula (1) thus obtained, a halogenated cyclic phenol sulfide represented by the general formula (2) can be synthesized. it can. Examples of the halogenating agent used in this reaction include a fluorinating agent, a chlorinating agent, a brominating agent and an iodinating agent, and preferably a chlorinating agent, a brominating agent and an iodinating agent. As the chlorinating agent or brominating agent, for example, Cl ₂ , Br ₂ , C
l ₂ aqueous solution, Br ₂ aqueous solution, HOCl, HOBr, N
-Chloroamides, N-bromoamides, BrCl, I
Br, t-BuOCl and PhSO ₂ NBr _{2, and the} like, preferably an aqueous solution of Cl _2, an aqueous solution of Br ₂ ,
-Chloroamides, N-bromoamides, HOCl, H
OBr, IBr and the like. The iodinating agent, for example, I _2, such as N- Yodoamido acids are exemplified, As the fluorinating agent, and the like AgF. When it is desired to selectively perform halogenation only at the 4-position to the hydroxyl group or its derivative group, N-chlorosuccinimide (NCS) is used as the chlorinating agent, and
N-bromosuccinimide (NBS) as a brominating agent
Is preferred. These halogenating agents can be used alone or in combination of two or more. The amount of the halogenating agent used in the reaction is not particularly limited, but it is preferable to use an amount theoretically necessary for synthesizing the target halogenated cyclic phenol sulfide.

A catalyst may be used in the reaction of the present invention, if necessary. Examples of the catalyst for chlorination and bromination include Lewis acid catalysts such as metal halides, and preferably include iron (III) chloride, titanium tetrachloride, and aluminum chloride. In addition, a simple metal such as iron powder and tin powder or a simple iodine can be used as a catalyst. Examples of the catalyst for iodination include SbCl ₅ , aluminum chloride, copper chloride and the like. The amount of the catalyst is not particularly limited, but a preferable amount of the catalyst is 0.05 equivalent or more and 10 equivalents or less with respect to one phenol skeleton of the cyclic phenol sulfide when a Lewis acid is used as a catalyst, Particularly preferably, it is 1 equivalent or more and 5 equivalents or less. When a simple metal or a simple iodine is used as a catalyst, the amount is preferably 0.001 equivalent or more and 10 equivalents or less, and particularly preferably 0.01 equivalent or more and 1 equivalent or less, per one phenol skeleton of the cyclic phenol sulfide. .

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 the reaction of the present invention, it is desirable to use a solvent as necessary. The solvent is not particularly limited, but preferred solvents are, for example, benzene, aromatic hydrocarbons such as toluene, carbon tetrachloride, halogenated hydrocarbons such as chloroform, pyridine, tetrahydrofuran, heterocyclic solvents such as dioxane, Or a mixed solvent 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. The solvent is 1
Species or a combination of two or more can be used. Although the reaction temperature of this reaction is not particularly limited, a preferable reaction temperature is −80 ° C. to 250 ° C., and particularly preferably, when no catalyst is used, room temperature or higher and the boiling point of the solvent used, When a catalyst is used, the temperature is 0 ° C. or more and 6
0 ° C. or lower is preferred. Also, under light irradiation conditions,
Since the halogenation of the alkyl side chain proceeds, the reaction of the present invention is preferably carried out while light is blocked.

The reaction product of the present invention can be obtained by treating the reaction mixture of the above reaction with water, an aqueous alkaline solution or the like. The alkaline aqueous solution is not particularly limited,
A weakly alkaline aqueous solution such as an aqueous NaHSO ₃ solution is preferred. Also, there is no particular limitation on the amount used,
It is preferable to use an equivalent or more of the halogenating agent used. When the reaction product is a mixture of two or more halogenated cyclic phenol sulfides,
For example, separation and purification can be performed by column chromatography, a recrystallization method, or a combination thereof. The product of the present invention is a cyclic phenol sulfide represented by the general formula (2). In the general formula (2), R, m and n are the same as those in the general formula (1). In the general formula (2), X, Y, and Z are a hydrogen atom or a halogen atom, and at least one of 3n X, Y, and Z is a halogen atom. A plurality of X, Y and Z may be the same or different.

[0019]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Production Example 1 To 64.5 g of 4-tert-butylphenol, 27.5 g of elemental sulfur and 17.2 g of sodium hydroxide were added.
In a solvent of 19 mL of tetraethylene glycol dimethyl ether, the mixture was gradually heated to 230 ° C. over 4 hours while stirring in a nitrogen stream, and further stirred for 2 hours. During this time, water and hydrogen sulfide generated by the reaction were removed. The reaction mixture was cooled to room temperature, added with 500 mL of ether, and sufficiently hydrolyzed with 1 N sulfuric acid. After ether extraction, a separation operation was performed by a combination of column chromatography (hexane / chloroform) and recrystallization from chloroform / acetone. As a result, colorless and transparent crystals of 5,11,17,23-tetra-tert-butyl were obtained. -2
5,26,27,28-tetrahydroxy-2,8,1
4,20- Tetorachia [19.3.1.1 ^3,7 1 ^9,13 1
^15,19 ] octacosa-1 (25), 3,5,7 (2
8), 9, 11, 13 (27), 15, 17, 19 (2
6), 21,23 Dodecaene 37.9 g was obtained.
This product is represented by the general formula (2) where n = 4, m = 1,
X, Z, R = H, Y = tert-butyl cyclic alkylphenol sulfide.

Production Example 2 The cyclic alkylphenol sulfide obtained in Production Example 1, that is, 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrahydroxy-
2,8,14,20-tetrathia [19.3.1.1]
^3,7 1 ^9,13 1 ^15,19] Okutakosa -1 (25), 3,5,
7 (28), 9, 11, 13 (27), 15, 17, 1
37.9 g of 9 (26), 21,23-dodecaene and 10.0 g of aluminum chloride were added to 2000 ml of toluene. This solution was reacted at 55 ° C. for 24 hours. This is because, from the measurement of the FD-MS spectrum, in the general formula (2), among n = 4, m = 1, R = H, X, Z = H, and four Ys, 1, 2, 3 and 4 respectively. It was confirmed that the mixture was a mixture of separated compounds. This solution was crystallized from a large amount of ether, and the obtained crystals were separated by filtration, recrystallized from toluene, and the solvent was removed under reduced pressure to give 25,26,27,28-tetrahydroxy-.
2,8,14,20-tetrathia [19.3.1.1]
^3,7 1 ^9,13 1 ^15,19] Okutakosa -1 (25), 3,5,
7 (28), 9, 11, 13 (27), 15, 17, 1
0.50 g of 9 (26), 21,23-dodecaene was obtained. This product is represented by the formula (1) where n = 4 and m =
1. A cyclic phenol sulfide in which R = H. The physical properties of this product are shown below. White crystal, MS m / z: 4
96 (M ⁺ ), ¹ H NMR: (δ, ppm, CDCl
₃ ) 9.45 (s, 4H, OH), 7.61 (d, 8
H, ArH), 6.75 (t, 4H, ArH), ¹³ C
NMR: (δ, ppm, CDCl ₃ ) 157.9,1
39.3,121.7,120.9 (Ar), Elemental analysis% theory _{for C 24 H 16 O 4 S} 4: C, 58.
04; H, 3.25; S, 25.83, found: C, 5
8.60; H, 3.40; S, 24.97

Example 1 The cyclic phenol sulfide obtained in Production Example 2, ie,
25,26,27,28-tetrahydroxy-2,8,
14,20- Tetorachia [19.3.1.1 ^3,7 1 ^9,13
1 ^15,19 ] octacosa-1 (25), 3,5,7 (2
8), 9, 11, 13 (27), 15, 17, 19 (2
6) 0.49 g of 21,21-dodecaene was dissolved in 75 ml of chloroform. To this solution, a solution of 0.80 g of simple bromine in 2 ml of chloroform was added dropwise over 20 minutes. Thereafter, the mixture was stirred for 20 hours under room temperature conditions. This was treated with distilled water, and the obtained precipitate was filtered to obtain 0.53 g of a reaction mixture. This product is
Analysis of the D-MS spectrum showed that the general formula (4) and the general formula (5)

[0022]

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[0023]

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(In the formula (4), n = 1 to 4, and in the formula (5), p = 1 to 4.) It was confirmed that the mixture was a mixture composed of eight kinds of compounds represented by the following formulas. Was.

Example 2 25,26,27,28-Tetrahydroxy-2,8,
14,20- Tetorachia [19.3.1.1 ^3,7 1 ^9,13
1 ^15,19 ] octacosa-1 (25), 3,5,7 (2
8), 9, 11, 13 (27), 15, 17, 19 (2
6) 0.49 g of 21,21-dodecaene was dissolved in 75 ml of chloroform. This chloroform solution was added with N-
Bromosuccinimide (NBS) 2.30 g was added and after stirring for 14 hours at room temperature, 5 wt% NaHSO ₃
By treating with water and filtering the resulting precipitate,
5,11,17,23-tetrabromo-25,26,2
7,28- tetrahydroxy--2,8,14,20- Tetorachia [19.3.1.1 ^3,7 1 ^9,13 1 ^15,19] Okutakosa -1 (25), 3,5,7 (28 ), 9, 11, 1
3 (27), 15, 17, 19 (26), 21, 23
0.60 g of dodecaene was obtained. This product is represented by the formula (2) where R, X, Z = H and Y = Br, m =
1, n = 4 bromocyclic phenol sulfide. Orange crystal, MS m / z: 808 (M ⁺ ), 810 (M ⁺ +)
2), 812 (M ⁺ +4), 814 (M ⁺ +6), 816
(M ⁺ +8), ¹ H-NMR: (δ, ppm, CDCl
₃ ) 7.77 (s, 8H, ArH), elemental analysis%
Theory _{for C 24 H 12 Br 4 O} 4 S 4: C, 35.4
9; H, 1.49; Br, 39.35; S, 15.7
9, measured: C, 35.29; H, 1.51; Br, 3.
9.40; S, 15.72

Example 3 25,26,27,28-Tetrahydroxy-2,8,
14,20- Tetorachia [19.3.1.1 ^3,7 1 ^9,13
1 ^15,19 ] octacosa-1 (25), 3,5,7 (2
8), 9, 11, 13 (27), 15, 17, 19 (2
6) 0.17 g of 21,21-dodecaene was dissolved in 25 ml of chloroform. This chloroform solution was added with N-
After adding 0.35 g of chlorosuccinimide (NCS) and stirring at room temperature for 4 hours, this was treated with 5% by mass of aqueous NaHSO ₃ and the obtained precipitate was filtered to obtain 0.15 g of a reaction mixture. . This product was analyzed by FD-MS spectrum to find that the product represented by the general formula (6)

[0027]

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(In the formula (6), n = 1 to 4) It was confirmed that the mixture was composed of four kinds of compounds containing the compound of n = 3 represented as the main product.

[0029]

According to the method of the present invention, a halogenated cyclic phenol sulfide can be produced efficiently and easily.

Continued on the front page (72) Inventor Hitoshi Kumagai 1134-2 Gongendo, Satte City, Saitama Prefecture Cosmo Research Institute R & D Center

Claims (4)

[Claims] 1. A compound of the general formula (1) (Wherein, R is a hydrogen atom, a hydrocarbon group, or an acyl group, m is an integer of 1 to 7, and a plurality of m and R may be the same or different, and n is 3 ~
It is an integer of 12. ) Is reacted with a halogenating agent to obtain a compound represented by the general formula (2): (Wherein, R is a hydrogen atom, a hydrocarbon group or an acyl group, X, Y, and Z are a hydrogen atom or a halogen atom;
At least one of the 3n X, Y, and Z is a halogen atom. m is an integer of 1 to 7, and a plurality of R, X,
Y, Z and m may be the same or different. n is an integer of 3 to 12. A) producing a halogenated cyclic phenol sulfide represented by the formula (1). 2. The method for producing a halogenated cyclic phenol sulfide according to claim 1, wherein the halogenating agent is at least one selected from a chlorinating agent, a brominating agent and an iodizing agent. 3. The method for producing a chlorinated cyclic phenol sulfide according to claim 1, wherein the halogenating agent is at least one selected from N-chlorosuccinimide, Cl ₂ and HOCl. 4. The method according to claim 1, wherein the halogenating agent is N-bromosuccinimide, Br ₂ . The method for producing a brominated cyclic phenol sulfide according to claim 1, wherein the method is at least one selected from HOBr and IBr.