TW201412693A - Method for producing selenol - Google Patents

Abstract

The main purpose of the present invention is to provide a method for producing a selenol with high yield without causing the fluctuations in yield among production lots. The purpose can be achieved by a method for producing a selenol, which comprises steps (1) and (2): (1) a step of reacting a Grignard reagent represented by general formula (1) with selenium to produce a reaction solution containing a selenomagnesium halide represented by general formula (2); and (2) a step of adding the reaction solution produced in step (1) mentioned above to an acidic solution dropwisely to produce a selenol represented by general formula (3).

Description

Method for producing selenol Field of invention

The present invention relates to a method of producing a selenol in a high yield with little change in yield per batch of the manufacturing lot.

Background of the invention

Selenols are indispensable compounds in the field of electronic materials and medicines, and there have been many studies on their physical properties or methods of utilization. Although there are many synthetic methods for selenol, it is generally known that a method in which a Grignard reagent is reacted with selenium and protonated to synthesize it. For example, in Non-Patent Document 1, a method for synthesizing phenyl selenol is disclosed, which discloses that after dissolving magnesium and bromobenzene in anhydrous diethyl ether and preparing a Grignard reagent, the selenium powder is slowly added to maintain a slow countercurrent state, and the preparation is contained. A reaction solution of a selenium magnesium halide. Next, the obtained reaction liquid was poured into ice water, and a method of obtaining phenyl selenol by adding hydrochloric acid to the reaction liquid was further carried out.

However, in the method of Non-Patent Document 1, there is a disadvantage that the yield of selenol is low. Further, in the method of Non-Patent Document 1, since the yield varies with each manufacturing, the yield of the finally obtained selenol cannot be predicted in advance, and there is also a problem in the commercial production of selenol. In fact, in Non-Patent Document 1, it is shown that the yield of selenol is in the range of 57 to 71%. Change between.

Against the background of such conventional techniques, it is highly desirable to establish a method for producing selenol in a high yield with little change in yield per manufacturing lot.

[Previous Technical Literature] Non-patent literature

Non-Patent Document 1: Organic Synthesis, Coll. Vol. 3, p. 771 (1955); Vol. 24, p. 89 (1944).

Summary of invention

SUMMARY OF THE INVENTION The main object of the present invention is to provide a method for producing a selenol, which is a method for producing selenol in a small yield per batch of manufacturing batches and capable of producing a selenol in high yield.

The inventors of the present invention conducted various reviews on a method for producing selenol which has a high yield and a small change in the yield of each batch, and obtained the following findings. That is, selenium-magnesium halides and selenols are very easily oxidized, and if they are exposed to an oxidation source, they will be diselenized. Therefore, in order to increase the yield of selenol, it is important to suppress oxidation of selenium-magnesium halides and selenols. In the method of Non-Patent Document 1, the reaction solution in which selenium is added is poured into ice water, but at this time, the reaction liquid becomes alkaline due to the remaining Grignard reagent or the selenium-magnesium halide. Since the oxidation reaction is easy to proceed under alkaline conditions, it is an undesired condition for preventing selenization. This results in an unstable yield of selenol.

Then, the inventors of the present invention have repeatedly and carefully reviewed and found that the reaction liquid containing the selenium-magnesium halide is obtained by reacting the Grignard reagent with selenium, and the reaction is dropped into an acidic solution, thereby preventing the selenium-magnesium halide and The oxidation of selenols can obtain selenols in high yield. It has also been found that by using such a manufacturing method, selenol can be produced with a small change in the yield of the manufacturing lot each time and can be stably set. The present invention is based on the findings of such a discovery and further review of the results of the completion.

That is, the present invention provides a method for producing selenols as described below.

Item 1, a method for producing a selenol, comprising the following steps 1 and 2: Step 1: by reacting a selenium with a Grignard reagent of the following formula (1) to obtain the following a step of containing a reaction solution of a selenium-magnesium halide represented by the formula (2); and [Chemical Formula 1] R-MgX (1) [In the formula (1), R represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, An aralkyl group or a heterocyclic group, and X represents a chlorine atom, a bromine atom or an iodine atom]

[Chem. 2] R-SeMgX (2) [wherein R and X are the same as above]; and Step 2: by dropping the reaction obtained in the above step 1 into an acidic solution, the following formula (3) is produced. a step of indicating selenols; [Chemical 3] R-SeH (3) [wherein R is the same as above].

The production method according to Item 1, wherein in the above formula (1), R is an aromatic group.

The production method according to Item 1, wherein, in the above formula (1), R is a phenyl group or a p-tolyl group, and X is a chlorine atom or a bromine atom.

The method of any one of items 1 to 3, wherein in the step 1 described above, selenium in a ratio of 0.5 to 10.0 mol is used with respect to the Grignard reagent 1 mol.

The production method according to any one of items 1 to 4, wherein the acid contained in the acidic solution is an inorganic acid.

The production method according to any one of the items 1 to 5, wherein the solvent contained in the acidic solution is water, an organic solvent capable of dissolving an acid, or a mixture thereof.

The production method according to any one of items 1 to 6, wherein in the step 1, the reaction of the Grignard reagent with selenium is carried out at -30 to 30 °C.

The manufacturing method according to any one of items 1 to 7, wherein in the above step 2, the acid solution contains 0.5 to 10.0 mol of the Grignard reagent 1 mol with respect to the step 1. .

According to the present invention, the production of selenol can be carried out in a high yield. Further, according to the production method of the present invention, oxidation of selenium-magnesium halide or selenol can be prevented, and the difference in yield of each batch of selenol can be suppressed. Therefore, by using the production method of the present invention, selenol can be produced in a high yield and stable, and it has high practicability in commercial production of selenol.

Used to implement the type of invention

The method for producing a selenol according to the present invention is characterized by comprising the following steps 1 and 2.

Step 1: a step of reacting a Grignard reagent represented by the general formula (1) with selenium to obtain a reaction liquid containing the selenium magnesium halide represented by the general formula (2); and a step 2: a reaction obtained in the above step 1. The step of forming a selenol represented by the formula (3) by dropping the droplet into an acidic solution.

Hereinafter, each step will be described with respect to the production method of the present invention.

step 1

In the first step, a reaction solution containing a selenium-magnesium halide is obtained by reacting a Grignard reagent represented by the following formula (1) with selenium.

[Chemical 4] R-MgX (1)

In the above formula (1), R represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an arylalkyl group or a heterocyclic group.

The alkyl group may be any of a linear chain, a branched chain or a cyclic chain. Further, the carbon number of the alkyl group is not particularly limited, and may be, for example, 1 to 12, and preferably 2 to 10, and more preferably 4 to 8. Specific examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a n-pentyl group, and an isopentyl group. Secondary pentyl, tertiary pentyl, neopentyl, 1-methylpentyl, n-hexyl, isohexyl, secondary hexyl, tertiary hexyl, neohexyl, n-heptyl, isoheptyl, secondary heptyl , tertiary heptyl, neoheptyl, n-octyl, isooctyl, secondary octyl, tertiary octyl, neooctyl, n-decyl, isodecyl, secondary fluorenyl, tertiary sulfhydryl, New sulfhydryl, n-decyl, isothiol, Second sulfhydryl, tertiary sulfhydryl, neodecyl, n-decyl, isodecyl, undecyl, tert-decyl, neodecyl, cyclopropyl, cyclobutyl , cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cyclodecyl, cyclododeyl and the like. Among these alkyl groups, n-butyl group, n-pentyl group and isohexyl group are preferable.

The above alkenyl group may be any of a linear chain, a branched chain or a cyclic chain. Further, the carbon number of the alkenyl group is not particularly limited, and may be 2 to 12, and preferably 3 to 10, more preferably 4 to 8. Specific examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, and a 2-methylallyl group. , 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 2-methyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3 -hexenyl, 5-hexenyl, 2-methyl 2-pentenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 5-heptenyl , 6-heptenyl, 1-dodecenyl, 2-dodecenyl, 3-dodecenyl, 4-dodecenyl, 5-dodecenyl, 6-dodecenyl, 8 - dodecenyl, 9-dodecenyl, 10-dodecenyl, 11-dodecenyl, 1-cyclobutenyl, 1-cyclopentenyl, 1-cyclohexenyl, and the like. Further, among these alkenyl groups, 1-butenyl, 1-hexenyl and 2-heptenyl are preferred.

The alkynyl group may be any of a linear chain, a branched chain or a cyclic chain. Further, the carbon number of the alkenyl group is not particularly limited, and may be 2 to 12, and preferably 2 to 10, more preferably 4 to 8. Specific examples of the alkenyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, and a 1-methyl-2- group. Propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 1-hexynyl, 2-hexynyl , 3-hexynyl, 4-hexynyl, 5-hexynyl, 2-methyl-4-heptynyl, 1-heptynyl, 2-heptyne , 3-heptynyl, 4-heptynyl, 5-heptynyl, 6-heptynyl, 1-octynyl, 2-octynyl, 3-octynyl, 4-octynyl, 5-octynyl, 6-octynyl, 7-octynyl, 1-decynyl, 2-decynyl, 3-decynyl, 4-nonynyl, 5-decynyl, 6-壬 alkynyl, 7-decynyl, 8-decynyl, 1-decynyl, 2-decynyl, 3-decynyl, 4-decynyl, 5-decynyl, 6-decyne , 7-decynyl, 7-decynyl, 8-decynyl, 9-decynyl, 1-undynyl, 2-undynyl, 3-undynyl, 4-ten Alkynyl, 5-undecynyl, 6-undynthynyl, 7-undecynyl, 8-undynyl, 9-undecynyl, 10-undynyl, 1-12 Alkyl, 2-dodecyl, 3-dodecyl, 4-dodecyl, 5-dodecyl, 6-dodecyl, 7-dodecyl, 8-dodecane Base, 9-dodecyl, 10-dodecyl, 11-dodecyl and the like. Among these alkynyl groups, 1-butynyl group, 1-pentynyl group and 1-octynyl group are preferred.

The carbon number of the above aryl group is not particularly limited, and may be, for example, 6 to 14, and preferably 6 to 12, more preferably 6 to 10. Specific examples of the aryl group include a phenyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, an o-xylylene group, a m-xylylene group, a p-xylylene group, a naphthyl group, and an anthracenyl group. Among these aryl groups, a phenyl group, an o-tolyl group, a m-tolyl group, and a p-tolyl group are preferable.

The carbon number of the above aralkyl group is not particularly limited, and may be, for example, 7 to 15, and preferably 7 to 13, more preferably 7 to 11. Specific examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthylmethyl group. Among these aralkyl groups, a benzyl group or a phenethyl group is preferred.

The carbon number of the above heterocyclic group is not particularly limited, and may be, for example, 3 to 14, and preferably 3 to 10. The number of hetero atoms of the heterocyclic group is not particularly limited, and may be 1 to 4, and preferably 1 to 2. Specific examples of the heterocyclic group include a thienyl group, a furyl group, a pyronyl group, a fluorenyl group, and Azolyl, thiazolyl, fluorenyl and the like. Among these aralkyl groups, a thienyl group or a thiazolyl group is preferred.

In the above formula (1), R is preferably an aryl group, and a phenyl group or a p-benzyl group is more preferable.

In the above formula (1), X may, for example, be a chlorine atom, a bromine atom or an iodine atom, and is preferably a chlorine atom or a bromine atom.

As the Grignard reagent used in the present invention, in the above formula (1), R is exemplified as an aryl group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or a heterocyclic group, and X is a chlorine atom, a bromine atom or an iodine. The atom is appropriate. Further, as a more preferable one, R is an aryl group, and X is a chlorine atom, a bromine atom or an iodine atom, and more preferably R is a phenyl group or a p-tolyl group, and X is a chlorine atom or a bromine atom. Still further, R is a p-tolyl group, and X is a bromine atom (i.e., p-toluene magnesium bromide) is particularly suitable as the Grignard reagent of the present invention.

The method for preparing the Grignard reagent represented by the above formula (1) is not particularly limited, and it may be prepared by any one of the methods. The method of preparing the Grignard reagent is, for example, a method in which a Grignard reaction is carried out by heating at 30 to 50 ° C using magnesium and a halogenated aromatic hydrocarbon (for example, p-bromotoluene) in a polar solvent such as diethyl ether. Further, a commercially available product can also be used as the Grignard reagent.

The amount of selenium used in the selenization reaction is not particularly limited, and is preferably from 0.5 to 10.0 mol, more preferably from 0.8 to 2.0 mol, relative to 1.0 g of the Grignard reagent. By setting the amount of selenium used to such a range, selenol can be obtained more efficiently. That is, if the amount of selenium used is 0.5 mol or more relative to the Grignard reagent 1.0 m, the remaining unreacted green in the reaction system can be reduced. It is economical to use the amount of reagents without undesired side reactions. Further, by using the amount of selenium in an amount of 10.0 mol or less relative to the Grenner reagent of 1.0 mol, it is economically advantageous in terms of obtaining an effect in accordance with the amount of use.

Further, the solvent used in the selenization reaction is not particularly limited, and the solvent used in the preparation of the Grignard reagent may be used as it is, and a solvent may be added as long as it does not inhibit the reaction. As the solvent which can be used in the selenization reaction, diethyl ether, tetrahydrofuran, toluene, xylene, 1,4-two Alkane, etc.

The amount of the solvent to be used in the selenization reaction is not particularly limited, and is preferably from 100 to 1,500 g, and preferably from 200 to 700 g, per 1.0 mol of the Grignard reagent represented by the formula (1).

The selenization reaction is carried out by dropping selenium into the Grignard reagent. Regarding the dropping rate of selenium to the Grignard reagent, the size of the reaction tank, the amount of use of the Grignard reagent, and the like may be considered, and the range of the reaction temperature to be described later may be appropriately set.

The reaction temperature at the time of the selenization reaction is not particularly limited, and is preferably -50 to 120 ° C, and more preferably -30 to 50 ° C. By setting the reaction temperature to such a range, selenol can be obtained more efficiently and in high yield. That is, when the reaction temperature is -50 ° C or higher, the selenization reaction proceeds well, and if it is 120 ° C or lower, the progress of the side reaction can be suppressed, so that the yield of selenol can be further improved.

In order to prevent the entry of the oxidation source in the reaction system, this step 1 is usually carried out under an inert gas atmosphere such as nitrogen.

Thus, by reacting selenium with a Grignard reagent, a reaction liquid containing a selenium magnesium halide represented by the following formula (2) can be obtained. The obtained reaction liquid can be supplied to the following step 2.

[Chem. 5] R-SeMgX (2) [wherein R and X are the same as defined above].

Step 2

In the second step, the reaction liquid obtained in the above step 1 is dropped into an acidic solution to produce a selenol of the target substance.

The type of the acid of the acidic solution used in this step is not particularly limited, and may be an organic acid or a mineral acid. Specific examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; and organic acids such as phosphoric acid, acetic acid, carbonic acid, and citric acid. Among these acids, a mineral acid is preferred, and hydrochloric acid is more preferred. These may be used alone or in combination of two or more.

Further, the amount of the acid to be used is not particularly limited, and the amount of the acid used is, for example, 0.5 to 100 mol, and preferably 1 to 10 mol, based on 1 g of the Grignard reagent used in the above step 1. By making the amount of the acid in the acidic solution into the above range, the oxidation of the selenium-magnesium halide is suppressed, and the yield of the selenol is further increased. That is, with respect to 1 gram of the Grignard reagent, if the acid is used in an amount of 0.5 mol or more, even after the reaction droplet containing the selenium-containing magnesium halide, the pH of the acidic solution does not tend to be alkaline, but may be By maintaining the solution in an acidic range to the extent that the reaction can proceed smoothly, the oxidation reaction of the selenium-magnesium halide can be effectively suppressed. Further, if the amount of the acid used is 100 m or less, the effect of the use amount can be obtained, which is quite economical.

The above acid is dissolved in a solvent and used as an acidic solution. In the second step, the synthesis reaction of the selenol and the prevention of oxidation are simultaneously carried out by dropping the reaction solution into the proton-rich solution. From this point of view, as long as it is used, the acid can be dissolved and the proton rich is prepared. The solvent of the solution can be used. Examples of such a solvent include water, an organic solvent capable of dissolving the above acid, and a mixture thereof. More specifically, water; ether, tetrahydrofuran, toluene, xylene, 1,4-two An organic solvent such as an alkane; a mixture of these. These solvents may be used alone or in combination of two or more.

The amount of the solvent to be used is not particularly limited, and it is from the viewpoint of further increasing the yield of the selenol by allowing protons to be present in the acidic solution at a high concentration, and more effectively suppressing the change in the yield per batch. It is 50 to 5000 parts by mass, and preferably 80 to 3000 parts by mass, based on 100 parts by mass of the Grignard reagent.

The dropping speed of the acidic solution in the reaction solution obtained in the above step 1 is not particularly limited, and the temperature of the acidic solution may be appropriately set in consideration of the size of the reaction vessel and the amount of the acidic solution.

The temperature of the acidic solution when the reaction droplet obtained in the above step 1 is not particularly limited is preferably -50 to 120 ° C, and more preferably -30 to 50 ° C. By adjusting to such a temperature range, the reaction can be carried out more efficiently. In other words, when the reaction temperature is -50 ° C or higher, there is no reaction to cause stagnation, and if it is 120 ° C or lower, there is no possibility of side reaction.

In order to prevent the oxidation source from entering the reaction system, this step 2 is usually carried out under an inert gas atmosphere such as nitrogen.

When the reaction is dropped, it may be stirred as needed. Further, in order to further increase the yield of the target after the reaction droplets are lowered, the heat may be maintained, or the mixture may be stirred while being kept warm. The holding time is not particularly limited, and is usually 0.1 to 24 hours, and preferably 1 to 8 hours.

In the reaction liquid thus obtained, selenols represented by the following formula (3) of the target are produced.

[Chem. 6] R-SeH (3) [wherein R is the same as above].

The organic layer is separated from the reaction liquid obtained in the second step, and the solvent is distilled off from the organic layer, whereby the selenol can be recovered. Further, if necessary, separation may be carried out by a conventionally known method such as crystallization, distillation or column chromatography to obtain purified selenol.

The selenols thus obtained can be similarly used in various fields in which selenols are used.

Detailed description of the preferred embodiment Example

Hereinafter, the present invention will be more specifically described by way of Examples, but the present invention is not limited to the Examples. All operations were carried out under a nitrogen atmosphere.

Manufacturing example 1

Four necks with 3L capacity for mixer, thermometer and return cooling tube The flask was charged with 194.5 g (8.00 mol) of magnesium and 601.6 g of diethyl ether. In the preparation, 1368.2 g (8.00 mol) of p-bromotoluene was dissolved in a solution of 600.0 g of diethyl bromide in diethyl ether, and one-tenth of the amount was added to the above-mentioned four-necked flask. The reaction solution was heated to 40 ° C using an oil bath to initiate the Grignard reaction. Thereafter, the remaining p-bromotoluene solution was added dropwise, and the reaction was carried out for 1 hour to obtain 2764.4 g (1547.1 g, 7.92 mol of pure component) of a p-toluene magnesium bromide solution.

Example 1

Into a four-necked flask of 500 mL capacity equipped with a stirrer, a thermometer and a reflux cooling tube, 174.5 g (97.6 g, 0.50 mol of pure component) of the p-toluene magnesium bromide solution obtained in Preparation Example 1 was placed, and the reaction liquid was cooled. After the temperature to 0 ° C, the temperature of 47.7 g (0.50 mol) of the selenium powder was kept in the range of 0 to 10 ° C to obtain a reaction liquid containing selenium magnesium halide. A four-necked flask of 500 mL capacity equipped with a stirrer, a thermometer and a reflux cooling tube was placed in a mixture of 83.3 g (0.80 mol) of hydrochloric acid and 200.8 g of pure water (less than pH 1), and the obtained reaction liquid was obtained. After the whole amount was dropped in a range not exceeding 0 to 30 ° C, the organic layer was recovered by continuous stirring for about 1 hour.

The analysis of the absolute calibration curve method for gas chromatography based on the recovered organic layer did not detect di-p-tolyl selenium as an oxidizing substance of p-toluene selenol. Further, the low-boiling component of the organic layer was distilled off, and then 73.7 g (0.43 mol) of a p-toluene-selenol colorless solid was obtained by distillation under reduced pressure. The yield was 86.1% relative to the Grenner reagent. Further, the solid obtained was p-toluene selenol, which was judged by its melting point of 47 °C.

Example 2

The results of producing p-toluene selenol 4 times were carried out under the same conditions as in Example 1. The yield was 85.7%, 86.3%, 85.3%, 85.8% relative to the Grenner reagent. That is, from the present results, it was confirmed that, by the production method of the present invention, there is no difference in the yield of each batch of the manufacturing lot, and p-toluene selenol can be produced in a high yield and in a stable manner.

Comparative example 1

The synthesis of p-toluene selenol was carried out in accordance with the production method described in Non-Patent Document 1. 172.8 g (97.7 g, 0.50 mol of pure component) of the p-toluene magnesium bromide solution obtained in Preparation Example 1 was placed in a 300 mL-capacity four-necked flask equipped with a stirrer, a thermometer and a reflux cooling tube, and the reaction liquid was heated to 40 ° C, allowing it to slowly reflux. Thereafter, the heating was stopped, and 47.4 g (0.50 mol) of selenium powder was added and maintained under reflux by the reaction heat to obtain a reaction liquid containing selenium magnesium halide. 600 g of crushed ice was weighed and taken to a four-necked flask of 1 L capacity equipped with a stirrer, a thermometer and a reflux cooling tube, and the obtained reaction liquid was all added thereto. Thereafter, 88.5 g (0.85 mol) of an aqueous solution of 35% by mass of hydrochloric acid was dropped at a temperature not exceeding 0 to 30 ° C, and the organic layer was recovered by continuously stirring for about 1 hour and keeping warm.

When the recovered organic layer was subjected to an absolute calibration curve method by gas chromatography, it was found that bis-p-toluene diselenene was 0.07 mol. Then, the low-boiling component of the organic layer was distilled off, and then 51.3 g (0.30 mol) of p-toluene selenol as a colorless solid was obtained by distillation under reduced pressure. The yield was 60.1% relative to the Grignard reagent. The solid obtained was p-toluene selenol, which was judged by its melting point of 47 °C.

Manufacturing Example 2

Four necks with 3L capacity for mixer, thermometer and return cooling tube The flask was charged with 194.5 g (8.00 mol) of magnesium and 600.2 g of diethyl ether. In the preparation, 900.2 g (8.00 mol) of chlorobenzene was dissolved in 600.8 g of a chlorobenzene solution of diethyl ether, and one-tenth of the amount was added to the above-mentioned four-necked flask. The reaction solution was heated to 40 ° C using an oil bath to initiate the Grignard reaction. Thereafter, the remaining chlorobenzene solution was dropped, and then reacted for 6 hours to obtain 2101.1 g (1029.2 g, 7.52 mol of pure component) of the phenylmagnesium chloride solution.

Example 3

140.1 g (68.4 g, 0.50 mol of pure component) of the phenylmagnesium chloride solution obtained in Production Example 2 was placed in a 500 mL-capacity four-necked flask equipped with a stirrer, a thermometer, and a reflux cooling tube, and the reaction liquid was cooled to 0 ° C. While maintaining the temperature of 47.7 g (0.50 mol) of selenium powder in the range of 0 to 10 ° C, a reaction liquid containing selenium magnesium halide was obtained. A four-necked flask of 500 mL capacity equipped with a stirrer, a thermometer and a reflux cooling tube was placed in a mixture of 83.3 g (0.80 mol) of hydrochloric acid and 200.8 g of pure water (less than pH 1), and the total amount of the reaction liquid obtained was obtained. After dropping in a range not exceeding 0 to 30 ° C, the organic layer was recovered by continuous stirring for about 1 hour.

For the recovered organic layer, an absolute calibration curve method based on gas chromatographic analysis was carried out, and the selenium dibenzene of the oxidized substance of phenylselenol was not examined. Further, the low-boiling component of the organic layer was distilled off, and then 68.4 g (0.44 mol) of a phenylselenol colorless liquid was obtained by distillation under reduced pressure. The yield was 85.8% relative to the Grenner reagent. Further, the obtained liquid was phenyl selenol, and its boiling point was judged to be 79 ° C (25 mmHg).

Claims (8)

A method for producing a selenol, comprising the following steps 1 and 2: Step 1: By reacting a Grenner reagent represented by the following formula (1) with selenium, the following formula (2) is obtained. a step of containing a reaction solution of a selenium-magnesium halide; and [Chemical Formula 1] R-MgX (1) [In the formula (1), R represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an arylalkyl group or a hetero a ring group, X represents a chlorine atom, a bromine atom or an iodine atom] [Chem. 2] R-SeMgX (2) [wherein, R, X are the same as above]; and Step 2: by substituting the reaction obtained in the above step 1 In the acidic solution, a step of producing a selenol represented by the following formula (3); [Chemical Formula 3] R-SeH (3) [wherein R is as defined above]. The production method of claim 1, wherein in the above formula (1), R is an aromatic group. The process according to claim 1 or 2, wherein in the above formula (1), R is a phenyl group or a p-tolyl group, and X is a chlorine atom or a bromine atom. The manufacturing method according to any one of claims 1 to 3, which is the aforementioned step 1 In the case of 1 molar of the Grenner reagent, selenium in a ratio of 0.5 to 10.0 mol is used. The production method according to any one of claims 1 to 4, wherein the acid contained in the aforementioned acidic solution is a mineral acid. The production method according to any one of claims 1 to 5, wherein the solvent contained in the acidic solution is water, an organic solvent capable of dissolving an acid, or a mixture thereof. The production method according to any one of claims 1 to 6, wherein in the aforementioned step 1, the reaction of the Grignard reagent with selenium is carried out at -30 to 30 °C. The manufacturing method according to any one of claims 1 to 7, wherein in the aforementioned step 2, the acid contained in the acidic solution is 0.5 to 10.0 mol with respect to the Grignard reagent 1 mol used in the step 1.