JP2014177433A - Production method of cyclic phenol sulfide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a cyclic phenol sulfide, with which a macrocyclic phenol sulfide equal to or larger than a hexamer can be efficiently produced with a high yield.SOLUTION: A production method of a cyclic phenol sulfide includes: a first reaction step to mix an alkyl phenol compound, a solvent, sulfur, and an alkali metal compound with one another and make the mixture react at 160-190°C for 10 hours or more; and a second reaction step to add sulfur and the alkali metal compound further to the reaction mixture after the first reaction step and make the mixture react at 210-240°C.

Description

  The present invention relates to a method for producing a cyclic phenol sulfide.

Conventionally, a method for producing cyclic phenol sulfide by adding diphenyl ether to p-tert-butylphenol, sulfur, and sodium hydroxide, raising the temperature to 230 ° C. while stirring, and reacting at 230 ° C. has been proposed. (For example, see Patent Documents 1 and 2). In these proposed methods, the cyclic phenol sulfide tetramer can be produced in a high yield, but the yield of the cyclic phenol sulfide octamer was about 4.7%.
Further, in Non-Patent Documents 1, 2, and 3, experiments were conducted by appropriately changing the reaction conditions and the results were reported, but both yielded a high yield and yield of tetramer. The yield of macrocyclic phenol sulfides of hexamer or higher was several g to about 10 g at most, and the yield was several percent.
As described above, in the technique described in the prior art document, there is a problem that a macrocyclic phenol sulfide having a hexamer or higher can be obtained only slightly compared to the cyclic phenol sulfide tetramer.

  In addition, a method for producing a cyclic phenol sulfide including a step of producing a chain-like cyclic phenol sulfide intermediate oligomer and a step of obtaining a cyclic phenol sulfide by cyclization has been proposed (for example, Patent Documents). 3 and 4). According to these proposed methods, a macrocyclic phenol sulfide having a hexamer or more can be produced, but it is industrially unsuitable because it is divided into two independent steps, and the synthesis takes one week. There is a problem that productivity is extremely bad.

  Therefore, provision of the manufacturing method of the cyclic phenol sulfide which can manufacture the macrocyclic phenol sulfide more than a hexamer efficiently with a high yield is desired.

International Publication No. 2008/026636 Pamphlet JP 2002-193963 A JP 2000-273096 A Japanese Patent Laid-Open No. 2002-255961

H. Kumagai, M .; Hasegawa, S .; Miyanari, Y. et al. Sugawa, Y .; Sato, T .; Hori, S .; Ueda, H .; Kamiya, S .; Miyano, Tetrahedron Lett. 38, 3971 (1997). N. Kon, N .; Iki, S .; Miyano, Tetrahedron Lett. 43, 2231 (2002). Yoshihiko Kondo and Fumio Hamada, J. Am. Incl. Phenom. Macrocyclic Chem. 58, 123-126 (2007).

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a method for producing a cyclic phenol sulfide capable of efficiently producing a macrocyclic phenol sulfide having a hexamer or higher in a high yield.

  As a result of intensive studies by the present inventors in order to solve the above-mentioned problems, a first alkylphenol compound, a solvent, sulfur and an alkali metal compound are mixed and reacted at 160 ° C. to 190 ° C. for 10 hours or more. It includes two steps of a reaction step and a second reaction step in which sulfur and an alkali metal compound are further added and reacted at 210 ° C. to 240 ° C. after the first reaction step, preferably the first step In this reaction step, the addition amount of the alkali metal compound to the alkylphenol compound is less than the addition amount of the alkali metal compound to the alkylphenol compound in the second reaction step, so that the long chain of the alkylphenol compound is inhibited while inhibiting the cyclization reaction. Polymerization is promoted, and macrocyclic phenol sulfides of hexamer or higher can be efficiently produced with high yield. It was seen.

This invention is based on the said knowledge by this inventor, The manufacturing method of the cyclic phenol sulfide of this invention as a means for solving the said subject is an alkylphenol compound, a solvent, sulfur, and an alkali metal. A first reaction step of mixing the compound and reacting at 160 ° C. to 190 ° C. for 10 hours or more;
After the 1st reaction process, sulfur and an alkali metal compound are further added, and the 2nd reaction process made to react at 210 ° C-240 ° C is included.

  According to the present invention, the above-mentioned problems can be solved and the above-mentioned object can be achieved, and a cyclic phenol sulfide capable of efficiently producing a hexacyclic or higher macrocyclic phenol sulfide in a high yield. The manufacturing method of can be provided.

FIG. 1 is a diagram showing the results of MALDI-TOFMD when the reaction time in the first reaction step is 1 hour. FIG. 2 is a diagram showing the results of MALDI-TOFMD when the reaction time in the first reaction step is 4 hours. FIG. 3 is a diagram showing the results of MALDI-TOFMD when the reaction time in the first reaction step is 8 hours. FIG. 4 is a diagram showing the results of MALDI-TOFMD when the reaction time in the first reaction step is 12 hours. FIG. 5 is a diagram showing the results of MALDI-TOFMD when the reaction time in the first reaction step is 24 hours. 6 is a diagram showing ¹ H-NMR results of the product in Example 1. FIG. FIG. 7 is a view showing ¹ H-NMR results of the product in Example 2. FIG. 8 is a diagram showing ¹ H-NMR results of the product in Example 3. FIG. 9 is a diagram showing ¹ H-NMR results of the product in Example 4.

(Method for producing cyclic phenol sulfide)
The method for producing a cyclic phenol sulfide of the present invention includes a first reaction step and a second reaction step, and further includes other steps as necessary.
The first reaction step and the second reaction step can be performed in one reaction system (one-stage reaction system), and a macrocyclic phenol sulfide having a hexamer or more can be efficiently produced in a high yield. Can be manufactured.

<First reaction step>
The first reaction step is a step in which an alkylphenol compound, a solvent, sulfur, and an alkali metal compound are mixed and reacted at 160 ° C. to 190 ° C. for 10 hours or longer.
In the first reaction step, a long-chain polymerization reaction of an alkylphenol compound is performed.

-Alkylphenol compounds-
There is no restriction | limiting in particular as said alkylphenol compound, Although it can select suitably according to the objective, The compound represented by following General formula (1) is suitable.
In the general formula (1), ^{R 1} represents an alkyl group having 1 to 6 carbon atoms.

R ¹ in the general formula (1) is a linear or branched alkyl group having 1 to 6 carbon atoms, for example, methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl. Group, sec-butyl group, 2-methylpropyl group, tert-butyl group, n-pentyl group, 1-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group, 1,2 -Dimethylbutyl group, 1,3-dimethylbutyl group, 1,4-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethyl -2-methylpropyl group, 1,1,2-trimethylpropyl group, and the like. Among these, a tert-butyl group is preferable from the viewpoint of cost and ease of synthesis. Therefore, p-tert-butylphenol is suitable as the alkylphenol compound.

-Alkali metal compounds-
There is no restriction | limiting in particular as said alkali metal compound, According to the objective, it can select suitably, For example, an alkali metal simple substance, an alkali metal hydride, an alkali metal carbonate, an alkali metal alkoxide, etc. are mentioned. Among these, alkali metal hydroxide is preferable.
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like. Among these, sodium hydroxide is preferable from the viewpoints of price and availability.
There is no restriction | limiting in particular in the addition amount of the alkali metal compound in a said 1st reaction process, Although it can select suitably according to the objective, 0.01 mol-0.05 mol with respect to 1 mol of said alkylphenol compounds. Is preferable, and 0.02 mol to 0.03 mol is more preferable.
If the addition amount of the alkali metal compound is less than 0.01 mol, it may take time for the long-chain polymerization of the alkylphenol compound to proceed, and if it exceeds 0.05 mol, the cyclization reaction is promoted, May inhibit the progress of chain polymerization.

-Solvent-
The solvent is not particularly limited and may be appropriately selected depending on the intended purpose.For example, saturated aliphatic ether, aromatic ether, saturated aliphatic thioether, aromatic thioether, saturated aliphatic hydrocarbon, aromatic carbonization And hydrogen. Among these, aromatic ethers, aromatic thioethers, and aromatic hydrocarbons are preferable, and diphenyl ether is more preferable from the viewpoint of reaction temperature.
There is no restriction | limiting in particular in the addition amount of the said solvent, Although it can select suitably according to the objective, The quantity which all the alkylphenol compounds melt | dissolve is preferable.

  There is no restriction | limiting in particular in the addition amount of sulfur in a said 1st reaction process, Although it can select suitably according to the objective, It is preferable that it is 1 mol-2 mol with respect to 1 mol of said alkylphenol compounds.

The first reaction step is preferably performed in an inert gas atmosphere and further while an inert gas is passed through the reaction system. Examples of the inert gas include nitrogen, helium, argon, and the like.
In the first reaction step, it is necessary to react at 160 ° C. to 190 ° C. for 10 hours or longer, and more preferably at 160 ° C. to 190 ° C. for 12 hours to 24 hours.
When the reaction temperature is 180 ° C., the reaction is preferably performed for 12 hours or more, and more preferably at 12O 0 C for 12 hours to 24 hours.
When the reaction time in the first reaction step is 160 ° C. to 190 ° C. and less than 10 hours, long-chain polymerization becomes insufficient, resulting in the synthesis of a large amount of tetramers and the yield of macrocycles. May get worse.

<Second reaction step>
The second reaction step is a step in which sulfur and an alkali metal compound are further added after the first reaction step and reacted at 210 ° C to 240 ° C.
In the second reaction step, a cyclization reaction of the alkylphenol compound that has been elongated in the first reaction step is performed.

As the alkali metal compound to be added in the second reaction step, the same one as in the first reaction step can be used.
In this invention, it is preferable that the addition amount with respect to the alkylphenol compound of the alkali metal compound in the said 1st reaction process is smaller than the addition amount with respect to the alkylphenol compound of the alkali metal compound in the said 2nd reaction process. When the addition amount of the alkali metal compound to the alkylphenol compound in the first reaction step is larger than the addition amount of the alkali metal compound to the alkylphenol compound in the second reaction step, the cyclization reaction is promoted more than the long-chain polymerization. As a result, a large amount of tetramer may be synthesized.
The addition amount of the alkali metal compound in the second reaction step is not particularly limited and may be appropriately selected depending on the intended purpose, but is 0.3 mol to 0.6 mol with respect to 1 mol of the alkylphenol compound. preferable.
There is no restriction | limiting in particular in the addition amount of sulfur in a said 2nd reaction process, Although it can select suitably according to the objective, 0.5 mol-1.0 mol are preferable with respect to 1 mol of alkylphenol compounds.

The second reaction step is preferably performed in an inert gas atmosphere, and further while passing an inert gas through the reaction system. Examples of the inert gas include nitrogen, helium, argon, and the like.
In the second reaction step, it is necessary to react at 210 ° C to 240 ° C, and 230 ° C is preferable.
When the reaction temperature is less than 210 ° C, the cyclization reaction does not proceed so much and the yield may be lowered. When the reaction temperature exceeds 240 ° C, the synthesized macrocyclic phenol sulfide is decomposed. May change to a mass.
The reaction time in the second reaction step is not particularly limited and may be appropriately selected depending on the intended purpose. However, the reaction is preferably performed at 210 ° C. to 240 ° C. for 5 hours or longer, and 210 ° C. to 240 ° C. for 5 hours. More preferably, the reaction is performed for 10 hours. Among these, it is particularly preferable to react at a reaction temperature of 230 ° C. for 5 hours or more.

  In the first reaction step and the second reaction step, synthesis is performed while removing generated water and hydrogen sulfide. The generated water and hydrogen sulfide are removed from the system by passing an inert gas through the system or by suction under a slightly reduced pressure within the range where the solvent does not boil. It can be continuously captured by absorption into an amine solution, or adsorption onto activated carbon, molecular sieve, iron oxide, zinc oxide, and the like.

  Next, an aqueous solution of a mineral acid is added to the reaction product in the second reaction step to obtain the target cyclic phenol sulfide. There is no restriction | limiting in particular as said mineral acid, According to the objective, it can select suitably, For example, a sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, boric acid etc. are mentioned. Of these, sulfuric acid is preferred. There is no restriction | limiting in particular in the addition amount of the said mineral acid, Although it can select suitably according to the objective, 0.5 mol-3.0 mol are preferable with respect to 1 mol of said alkylphenol compounds.

<Other processes>
There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, a isolation | separation process, a refinement | purification process, etc. are mentioned.

The separation step is a step of separating a tetrameric cyclic phenol sulfide from a hexameric or higher cyclic phenol sulfide, and can be performed by a separation means.
There is no restriction | limiting in particular as said separation means, According to the objective, it can select suitably, For example, column chromatography, a recrystallization method, or these combination etc. are mentioned.

Here, an example of the manufacturing method of the cyclic phenol sulfide of this invention is demonstrated concretely.

As shown in the reaction formula, p-tert-butylphenol and diphenyl ether are placed in a reaction vessel and dissolved at 100 ° C. under a nitrogen stream. After dissolution, sulfur and NaOH are added and reacted at 130 ° C. for 2 hours. Next, the temperature is raised to 180 ° C., and the reaction is performed at 180 ° C. for 24 hours (first reaction step). Then, it is allowed to cool to near 100 ° C., sulfur and NaOH are added, and reacted at 230 ° C. for 5 hours (second reaction step). After the reaction, the mixture is allowed to cool, and toluene is added to lower the viscosity, and 2N-sulfuric acid is added to quench. Then, twice with saturated aqueous _Na 2 SO ₄ using a separatory funnel, washed once with distilled water. After washing, the organic phase is concentrated and diphenyl ether is removed under reduced pressure. After removal, acetone is added, and the mixture is allowed to stand overnight, and the resulting precipitate is collected by filtration. By the above, the target cyclic phenol sulfide can be manufactured.

<Application>
The hexacyclic or higher macrocyclic phenol sulfide produced by the method for producing the cyclic phenol sulfide of the present invention has a larger cyclic structure than the tetramer and has a flexible structure. Metal extractants and immobilizing agents that use the ability to capture metal ions, gas storage, biological activity, photosensors that use the ability to recognize ions and molecules, ion sensors, substrate specificity sensors, separation membrane materials, or their intermediates , A charge control agent, a catalyst, and the like. Among these, the structure can be changed in accordance with the metal species, and one type of macrocyclic phenol sulfide can be combined with many metal species, so that it is particularly useful as a metal extractant.

  EXAMPLES The present invention will be specifically described below with reference to examples of the present invention, but the present invention is not limited to these examples.

<Setting of reaction conditions in one-step synthesis method of macrocyclic thiacalixarene>

In a reaction vessel, 30 g (0.200 mol) of p-tert-butylphenol and 50 mL of diphenyl ether were added and dissolved at 100 ° C. under a nitrogen stream. After dissolution, 10.68 g (0.333 mol) of sulfur and 0.16 g (0.004 mol) of NaOH were added and reacted at 130 ° C. for 2 hours. After the reaction for 2 hours, the temperature was raised to 180 ° C., and the reaction was performed at 180 ° C. for 1 hour, 4 hours, 8 hours, 12 hours, or 24 hours (first reaction step). The results of MALDI-TOFMD with different reaction times are shown in FIGS.
Next, after completion of the reaction, the mixture was allowed to cool to nearly 100 ° C., 5 g (0.156 mol) of sulfur and 3.99 g (0.100 mol) of NaOH were added, and the mixture was reacted at 230 ° C. for 5 hours (second reaction) Process). After the reaction, the mixture was allowed to cool, and 100 mL of toluene was added to lower the viscosity, followed by quenching by adding 100 mL of 2N sulfuric acid. Then, twice with saturated aqueous _Na 2 SO ₄ using a separatory funnel, and washed once with distilled water. After washing, the organic phase was concentrated and diphenyl ether was removed under reduced pressure. After removal, acetone was added, and the mixture was allowed to stand overnight, and the resulting precipitate was collected by filtration.

From the results of FIGS. 1 to 5, it was found that as the reaction time becomes longer, more peaks appear on the high molecular weight side (right side). Since the production of a long-chain polymer proceeds by performing the reaction for a long time in this way, the reaction time at a reaction temperature of 180 ° C. is preferably 12 hours or longer (12 hours to 24 hours).
As for the reaction temperature in the first reaction step and the second reaction step, the cyclization reaction does not proceed at 180 ° C., but the cyclization reaction proceeds rapidly at 230 ° C., so that a tetramer is formed. I understood that.

In the following examples, the yield of the product cyclic phenol sulfide was determined as follows.
<Calculation method of yield>
The cyclic phenol sulfide finally obtained was subjected to ¹ H-NMR measurement, and thiacalix [4] arene (tetramer), thiacalix [6] arene (hexamer), and thiacalix [8] arene ( It was calculated from the integrated value of the peak specific to each of the octamers). ¹ H-NMR was measured using DPX-300 manufactured by Bruker BioSpin Corporation.
Thiacarix [4] arene (TC4A) Hydroxyl group (—OH): 9.6 ppm, benzene ring—H: 7.61 ppm
Thiacarix [6] arene (TC6A) Hydroxyl group (-OH): 9.1 ppm, benzene ring -H: 7.57 ppm
Thiacarix [8] arene (TC8A) Hydroxyl group (—OH): 8.6 ppm, benzene ring—H: 7.54 ppm
Since the hydroxyl group can be easily identified, the calculation was performed based on the integrated value of the hydroxyl group.

<< Detailed calculation method >>
^{In 1} H-NMR, the number of protons (H) is expressed as an integrated value of peaks, and each integrated value of peaks represents the ratio of protons.
Since TCnA has n hydroxyl groups, when the number of moles is X, the number of hydroxyl groups is Xn. Since this is expressed as an integral value, if the integral value is I, there is a correlation between Xn and I.
^From the measurement result of ¹ H-NMR, when the integrated value of the hydroxyl group of TC4A is x and the integrated value of the hydroxyl group of TC6A is y, the integrated value is X when the number of moles of TC4A is Y and the number of moles of TC6A is Y. It is the ratio of each molecular weight.
Since x: y = 4X: 6Y → x / 4: y / 6 = X: Y, the molar ratio in the ¹ H-NMR measurement sample was determined. From the above calculation formula, thiacalix [4] arene (tetramer), thiacalix [6] arene (hexamer), and thiacalix [8] arene (octamer) in the obtained cyclic phenol sulfide The abundance ratio (molar ratio) was calculated.

Example 1

In a reaction vessel, 30 g (0.200 mol) of p-tert-butylphenol and 50 mL of diphenyl ether were added and dissolved at 100 ° C. under a nitrogen stream. After dissolution, 10.68 g (0.333 mol) of sulfur and 0.16 g (0.004 mol) of NaOH were added and reacted at 130 ° C. for 2 hours. Next, the temperature was raised to 180 ° C. and reacted at 180 ° C. for 24 hours (first reaction step). Then, it stood to cool to near 100 degreeC, 5 g (0.156 mol) of sulfur and 3.99 g (0.100 mol) of NaOH were added, and it was made to react at 230 degreeC for 5 hours (2nd reaction process). After the reaction, the mixture was allowed to cool, and 100 mL of toluene was added to lower the viscosity, followed by quenching by adding 100 mL of 2N sulfuric acid. Then, twice with saturated aqueous _Na 2 SO ₄ using a separatory funnel, and washed once with distilled water. After washing, the organic phase was concentrated and diphenyl ether was removed under reduced pressure. After removal, acetone was added, and the mixture was allowed to stand overnight, and the resulting precipitate was collected by filtration.

The yield of the obtained cyclic phenol sulfide was 10.161 g. The molar ratio (TC4A: TC6A) of thiacalix [4] arene (TC4A) to thiacalix [6] arene (TC6A) in the yield of cyclic phenol sulfide was 5: 6.
When the yield of cyclic phenol sulfide was calculated based on p-tert-butylphenol, it was (10.161 / 30) × 100 = 34%.
Therefore, the yield of thiacalix [6] arene (TC6A) based on p-tert-butylphenol was 18%.
FIG. 6 shows the ¹ H-NMR result of Example 1.
From the results of Example 1, it was found that the first reaction step (long chain polymerization reaction) and the second reaction step (cyclization reaction) can be carried out in one reaction system.

(Example 2)
In a reaction vessel, 30 g (0.200 mol) of p-tert-butylphenol and 50 mL of diphenyl ether were added and dissolved at 100 ° C. under a nitrogen stream. After dissolution, 10.68 g (0.333 mol) of sulfur and 0.16 g (0.004 mol) of NaOH were added and reacted at 130 ° C. for 2 hours. Next, the temperature was raised to 180 ° C. and reacted at 180 ° C. for 24 hours. Then, it stood to cool near 100 degreeC, NaOH 0.16g (0.004 mol) was added, and it heat-stirred at 180 degreeC for 6 hours (1st reaction process). Thereafter, 5 g (0.156 mol) of sulfur and 3.99 g (0.100 mol) of NaOH were added and reacted at 230 ° C. for 5 hours (second reaction step). After the reaction, the mixture was allowed to cool, and 100 mL of toluene was added to lower the viscosity, followed by quenching by adding 100 mL of 2N sulfuric acid. Then, twice with saturated aqueous _Na 2 SO ₄ using a separatory funnel, and washed once with distilled water. After washing, the organic phase was concentrated and diphenyl ether was removed under reduced pressure. After removal, acetone was added, and the mixture was allowed to stand overnight, and the resulting precipitate was collected by filtration.

The yield of the obtained cyclic phenol sulfide was 14.153 g. The molar ratio (TC4A: TC6A) of thiacalix [4] arene (TC4A) to thiacalix [6] arene (TC6A) in the yield of cyclic phenol sulfide was 25: 8.8.
When the yield of cyclic phenol sulfide was calculated based on p-tert-butylphenol, it was (14.153 / 30) × 100 = 47%.
Therefore, the yield of thiacalix [6] arene (TC6A) based on p-tert-butylphenol was 13.6%.
FIG. 7 shows the result of 1H-NMR of Example 2.
From the results of Example 2, in the first reaction step (long chain polymerization reaction), an alkali metal compound was further added to promote the long chain polymerization reaction. [6] Formation of arene (TC6A) was confirmed.

  From the above results, according to the method for producing a cyclic phenol sulfide of the present invention, the first reaction step (long-chain polymerization reaction) and the second reaction step are performed in one reaction system (one-stage reaction system). (Cyclization reaction) can proceed, and by adjusting conditions such as the temperature and time of each reaction, it is understood that a macrocyclic thiacalixarene of hexamer or higher can be obtained efficiently in high yield. It was.

(Example 3)
In Example 1, cyclic phenol sulfide was obtained in the same manner as in Example 1 except that 0.16 g (0.004 mol) of NaOH in the first reaction step was changed to 0.08 g (0.002 mol) of NaOH. Synthesized. That is, the amount of NaOH added to 1 mol of p-tert-butylphenol in the first reaction step was reduced from 0.02 mol to 0.01 mol.
The yield of the obtained cyclic phenol sulfide was 9.969 g. The mass ratio (TC4A: TC6A) of thiacalix [4] arene (TC4A) to thiacalix [6] arene (TC6A) in the yield of the cyclic phenol sulfide was 5.417 g (54.2% by mass): It was 4.551 g (35.8 mass%).
The yield based on p-tert-butylphenol of thiacalix [6] arene (TC6A) was 12.6%.
FIG. 8 shows the ¹ H-NMR result of Example 3.

Example 4
In Example 1, cyclic phenol sulfide was obtained in the same manner as in Example 1 except that 0.16 g (0.004 mol) of NaOH in the first reaction step was changed to 0.8 g (0.02 mol) of NaOH. Synthesized. That is, the amount of NaOH added to 1 mol of p-tert-butyphenol in the first reaction step was increased from 0.02 mol to 0.1 mol.
The yield of the obtained cyclic phenol sulfide was 13.547 g. The mass ratio (TC4A: TC6A: TC8A) of thiacalix [4] arene (TC4A), thiacalix [6] arene (TC6A) and thiacalix [8] arene (TC8A) in the yield of this cyclic phenol sulfide is: It was 10.584 g (73.13 mass%): 2.858 g (21.10 mass%): 0.105 g (0.77 mass%).
The yield based on p-tert-butylphenol of thiacalix [6] arene (TC6A) was 7.9%.
FIG. 9 shows the ¹ H-NMR result of Example 4.

  Next, Table 2 shows the yield of each thiacalix [n] arene (TCnA) in terms of p-tert-butylphenol.

From the results of Table 2, TC6A can be synthesized in Example 3 in which the molar ratio of NaOH to p-tert-butylphenol in the first reaction step is 1/100, but relative to p-tert-butylphenol in the first reaction step. It was found that the molar ratio of NaOH was less than in Example 1 where 1/50. In Example 4 where the molar ratio of NaOH to p-tert-butylphenol in the first reaction step is 1/10, the total yield increases, but the cyclization reaction proceeds, so the yield of TC6A decreases. I found out.

As an aspect of this invention, it is as follows, for example.
<1> a first reaction step in which an alkylphenol compound, a solvent, sulfur, and an alkali metal compound are mixed and reacted at 160 ° C. to 190 ° C. for 10 hours or more;
And a second reaction step in which sulfur and an alkali metal compound are further added and reacted at 210 ° C. to 240 ° C. after the first reaction step. .
<2> The method for producing a cyclic phenol sulfide according to <1>, wherein the reaction is performed at 180 ° C. for 12 hours to 24 hours in the first reaction step.
<3> The amount of the alkali metal compound added to the alkylphenol compound in the first reaction step is less than the amount of the alkali metal compound added to the alkylphenol compound in the second reaction step. It is a manufacturing method of the described cyclic phenol sulfide.
<4> The method for producing a cyclic phenol sulfide according to <3>, wherein the addition amount of the alkali metal compound in the first reaction step is 0.01 mol to 0.05 mol with respect to 1 mol of the alkylphenol compound. It is.
<5> In the second reaction step, the cyclic phenol production method according to any one of <1> to <4>, wherein the reaction is performed at 210 ° C. to 240 ° C. for 5 hours or more.
<6> The method for producing a cyclic phenol sulfide according to any one of <1> to <5>, wherein the alkylphenol compound is p-tert-butylphenol and the alkali metal compound is sodium hydroxide.

Claims (6)

A first reaction step in which an alkylphenol compound, a solvent, sulfur, and an alkali metal compound are mixed and reacted at 160 ° C. to 190 ° C. for 10 hours or more;
And a second reaction step in which sulfur and an alkali metal compound are further added and reacted at 210 ° C. to 240 ° C. after the first reaction step.   The method for producing a cyclic phenol sulfide according to claim 1, wherein the reaction is performed at 180 ° C. for 12 hours to 24 hours in the first reaction step.   The cyclic phenol sulfide according to claim 1, wherein the addition amount of the alkali metal compound to the alkylphenol compound in the first reaction step is smaller than the addition amount of the alkali metal compound to the alkylphenol compound in the second reaction step. Manufacturing method.   The method for producing a cyclic phenol sulfide according to claim 3, wherein the addition amount of the alkali metal compound in the first reaction step is 0.01 mol to 0.05 mol with respect to 1 mol of the alkylphenol compound.   The method for producing a cyclic phenol according to any one of claims 1 to 4, wherein in the second reaction step, the reaction is performed at 210 ° C to 240 ° C for 5 hours or more.   The method for producing a cyclic phenol sulfide according to any one of claims 1 to 5, wherein the alkylphenol compound is p-tert-butylphenol and the alkali metal compound is sodium hydroxide.