KR20150060739A - Method for producing selenol - Google Patents

Abstract

The main object of the present invention is to provide a method for producing a selenol with a small yield change per production lot and at a high yield. The above object is achieved by a process for producing selenols 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 solution containing a selenomagnesium halide represented by the general formula (2); And Step 2: The step of dropping the reaction solution obtained in Step 1 into an acidic solution to produce a selenol derivative represented by the general formula (3).

Description

METHOD FOR PRODUCING SELENOL < RTI ID = 0.0 >

The present invention relates to a method capable of producing a selenol with a small yield change per production lot and at a high yield.

Selenol is an indispensable compound in the field of electronic materials and medicine, and many studies have been conducted on the properties and methods of use. Although there are many methods for synthesizing selenols, a method of reacting Grignard reagents with selenium and then protonizing them is generally well known. For example, Non-Patent Document 1 discloses a method for synthesizing benzene selenol. After preparing Grignard reagent by reacting magnesium bromide and bromobenzene in anhydrous ether, selenium powder is added to maintain a smooth reflux state Respectively, to prepare a reaction solution containing the selenomagnesium halide. Then, the obtained reaction solution is poured into ice water, and hydrochloric acid is added to the reaction solution to obtain benzene selenol.

However, the method of Non-Patent Document 1 has a drawback that the yield of selenols is low. Moreover, since the yield of the production varies with each production method in the method of Non-Patent Document 1, the yield of selenols ultimately obtained can not be predicted in advance, and there is also a problem in commercial production of selenols. In fact, non-patent document 1 shows that the yield of selenols fluctuates in the range of 57 to 71%.

With the background of such prior arts, there has been a desperation to establish a method for producing selenophores with a small yield change per production lot and at a high yield.

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

The main object of the present invention is to provide a method for producing selenol with a small yield change per production lot and at a high yield.

The inventors of the present invention have obtained the following findings while carrying out various studies on a method for producing selenophores with a high yield, and also with little change in the yield per production lot. That is, selenomagnesium halide, and selenoenes are susceptible to oxidation abnormally and rapidly desensitize upon contact with an oxidizing source. Therefore, in order to increase the yield of selenoenes, it is important to inhibit the oxidation of selenomagnesium halide, selenol. In the above-described method of Non-Patent Document 1, the reaction solution after the addition of selenium is poured into ice water. At this time, the reaction solution becomes basic due to the residual Grignard reagent or selenomagnesium halide. Under basic conditions, the chlorination reaction tends to proceed, which is an undesirable condition for the prevention of des-selenide formation. As a result, the yield of selenols is not stable.

Thus, the present inventors have further intensively studied to obtain a reaction solution containing a selenomagnesium halide by reacting a Grignard reagent with selenium, and dropping the reaction solution in an acidic solution to obtain a selenomagnesium halide, And oxidation of selenophores are prevented, and selenophenols can be obtained at a high yield. In addition, by adopting such a production method, the change in the yield of selenophores per production lot was small, and it was also found that selenophores could be stably produced. The present invention has been completed as a result of further examination based on such findings.

That is, the present invention provides a process for producing selenophores of the following embodiments.

Item 1. A process for producing selenols comprising the following steps 1 and 2:

Step 1: A Grignard reagent represented by the following general formula (1)

[In the general 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]

To obtain a reaction solution containing a selenomagnesium halide represented by the following general formula (2)

[Wherein R and X are as defined above]; And

Step 2: By dropping the reaction solution obtained in Step 1 into the acidic solution,

A process for producing selenophores represented by the following general formula (3)

Wherein R is as defined above.

[3] The method according to item 2,

Wherein, in the general formula (1), R is an aryl group.

Item 3. The method according to item 1 or 2,

Wherein R is a phenyl group or a p-tolyl group, and X is a chlorine atom or a bromine atom in the general formula (1).

Item 4. The method according to any one of claims 1 to 3,

Wherein the selenium is used in a proportion of 0.5 to 10.0 mol based on 1 mol of the Grignard reagent in the step 1.

Item 5. The method according to any one of claims 1 to 4,

Wherein the acid contained in the acidic solution is an inorganic acid.

Item 6. The 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.

Item 7. The method according to any one of claims 1 to 6,

Wherein in step 1, the reaction of the Grignard reagent and selenium is carried out at -30 to 30 占 폚.

Item 8. The method according to any one of claims 1 to 7,

Wherein the acid contained in the acid solution is 0.5 to 10.0 mol based on 1 mol of the Grignard reagent used in the step 1 in the step 2.

According to the present invention, the production of selenols can be carried out at a high yield. Further, according to the production method of the present invention, it is possible to prevent oxidation of selenomagnesium halide and selenophores, and to suppress variation in the yield of selenophores for each production lot. Therefore, according to the production method of the present invention, it is possible to stably produce selenol at a high yield, and is highly practical in the commercial production of selenols.

The method for producing a selenol of 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 solution containing a selenomagnesium halide represented by the general formula (2); And

Step 2: A step of dropping the reaction solution obtained in the above step 1 into an acidic solution to produce a selenol derivative represented by the general formula (3).

Hereinafter, the manufacturing method of the present invention will be described step by step.

Process 1

In the present Step 1, a reaction solution containing a selenomagnesium halide is obtained by reacting a Grignard reagent represented by the following general formula (1) with selenium.

In the general formula (1), R represents an alkyl group, an alkenyl group, an alkynyl group, an allyl group, an aralkyl group or a heterocyclic group.

The alkyl group may be linear, branched or cyclic. The number of carbon atoms of the alkyl group is not particularly limited, but may be 1 to 12, preferably 2 to 10, more preferably 4 to 8, for example. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- Hexyl group, tert-hexyl group, neohexyl group, n-heptyl group, isoheptyl group, n-hexyl group, isohexyl group, heptyl group, n-octyl group, isononyl group, sec-nonyl group, iso-octyl group, isoheptyl group, sec-octyl group, an n-decyl group, an iso-decyl group, a sec-undecyl group, a tert-undecyl group, an iso-decyl group, a tert- , A neoundecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclododecyl group, and a cyclododecyl group. Among these alkyl groups, an n-butyl group, an n-pentyl group and an isohexyl group are preferable.

The alkenyl group may be linear, branched, or cyclic. The number of carbon atoms of the alkenyl group is not particularly limited, but is, for example, 2 to 12, preferably 3 to 10, and 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, Pentenyl group, a 4-pentenyl group, a 2-methyl-2-butenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, Heptenyl, 3-heptenyl, 4-heptenyl, 5-heptenyl, 6-heptenyl, 1-dodecenyl, 2-dodecenyl, 3- Dodecenyl, 6-dodecenyl, 8-dodecenyl, 9-dodecenyl, 10-dodecenyl, 11-dodecenyl, A 1-cyclopentenyl group, a 1-cyclohexenyl group, and the like. Of these alkenyl groups, preferred are 1-butenyl group, 1-hexenyl group and 2-heptenyl group.

The alkynyl group may be linear, branched, or cyclic. The number of carbon atoms of the alkenyl group is not particularly limited, but is, for example, 2 to 12, preferably 2 to 10, and more preferably 4 to 8. Specific examples of the alkynyl group include an ethynyl group, an 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 2-heptynyl, 3-heptynyl, 4-heptynyl, 5-heptynyl, 6-heptynyl, 1-octynyl, 2-octynyl, 3- Octynyl group, 4-nonynyl group, 5-nonynyl group, 6-octynyl group, 1-nonynyl group, Decynyl group, 8-nonynyl group, 8-nonynyl group, 1-decynyl group, 2-decynyl group, 3-decynyl group, 4-decynyl group, A decenyl group, a 3-decenyl group, a 4-decenyl group, a 4-decenyl group, a 4-decenyl group, 8-undecenyl group, 9- Dodecyl group, 3-dodecyl group, 4-dodecyl group, 5-dodecyl group, 6-dodecyl group, 7-dodecyl group, 8-dodecyl group, 9-dodecyl group, A dodecyl group, a 10-dodecyl group, and an 11-dodecyl group. Among these alkynyl groups, preferred are 1-butynyl group, 1-pentynyl group and 1-octynyl group.

The number of carbon atoms of the aryl group is not particularly limited, but is, for example, 6 to 14, preferably 6 to 12, more preferably 6 to 10. Specific examples of the aryl group include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, o-xylyl group, m-xylyl group, p-xylyl group, naphthyl group, . Of these aryl groups, preferred are phenyl, o-tolyl, m-tolyl and p-tolyl groups.

The number of carbon atoms of the aralkyl group is not particularly limited, and is, for example, 7 to 15, preferably 7 to 13, and 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 and a phenethyl group are preferable.

The number of carbon atoms in the heterocyclic group is not particularly limited, and is, for example, 3 to 14, preferably 3 to 10 carbon atoms. The number of heteroatoms in the heterocyclic group is not particularly limited, but is, for example, 1 to 4, preferably 1 to 2. Specific examples of the heterocyclic group include a thienyl group, a pranyl group, a pyrrolyl group, an indyl group, an oxazolyl group, a thiazolyl group and a prynyl group. Among these aralkyl groups, a thienyl group and a thiazolyl group are preferable.

In the general formula (1), R is preferably an aryl group, more preferably a phenyl group or a p-tolyl group.

In the above general formula (1), X may be a chlorine atom, a bromine atom or an iodine atom, but preferably a chlorine atom or a bromine atom.

More preferable examples of the Grignard reagent used in the present invention are those wherein R is an aryl group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a heterocyclic group, and X is a chlorine atom, bromine An atom or an iodine atom. It is more preferable that R is an aryl group and X is a chlorine atom, a bromine atom or an iodine atom, more preferably a compound wherein R is a phenyl group or a p-tolyl group, and X is a chlorine atom or a bromine atom . Furthermore, R is a p-tolyl group, and X is a bromine atom (i.e., p-trilmagnesium bromide) can be mentioned as a particularly suitable Grignard reagent in the present invention.

The method of preparing the Grignard reagent represented by the general formula (1) is not particularly limited and may be prepared by any known method. As a method for preparing the Grignard reagent, for example, heating at 30 to 50 ° C using magnesium and halogenated aromatic hydrocarbons (for example, p-bromotoluene) in a polar solvent such as diethyl ether, Is carried out. A commercially available product may be used as the Grignard reagent.

The amount of selenene used in the selenization reaction is not particularly limited, but is preferably 0.5 to 10.0 mols, more preferably 0.8 to 2.0 mols, per 1.0 mol of the Grignard reagent. By setting the amount of selenium to be used in this range, it is possible to obtain a more selenium gradient. That is, when the amount of selenium is 0.5 mol or more with respect to 1.0 mol of the Grignard reagent, the amount of the unreacted Grignard reagent remaining in the reaction system can be reduced, and an undesirable side reaction does not progress and it is economical. In addition, the use of selenium in an amount of 10.0 mol or less with respect to 1.0 mol of the Grignard reagent has an economical advantage in that an effect suited to the amount of use can be obtained.

The solvent used in the selenization reaction is not particularly limited. The solvent used when preparing the Grignard reagent may be used as it is, or other solvent may be added as long as it does not inhibit the reaction. Examples of usable solvents in the selenization reaction include diethyl ether, tetrahydrofuran, toluene, xylene, 1,4-dioxane, and the like.

The amount of the solvent used in the selenization reaction is not particularly limited, but is preferably 100 to 1500 g, more preferably 200 to 700 g, per 1.0 mol of the Grignard reagent represented by the general formula (1).

The selenization reaction is carried out by dropping selenium in a Grignard reagent. The dropping rate of selenium to the Grignard reagent may be appropriately set within a range in which the reaction temperature described later can be maintained in consideration of the size of the reaction tank and the amount of Grignard reagent used.

The reaction temperature in the selenization reaction is not particularly limited, but is preferably -50 to 120 ° C, more preferably -30 to 50 ° C. By setting the reaction temperature within this range, it is possible to obtain selenols with higher efficiency and higher yield. That is, if the reaction temperature is -50 ° C or higher, the progress of the selenization reaction is appropriate. If the reaction temperature is lower than 120 ° C, the progress of the side reaction is suppressed, so that the yield of selenophenols can be further improved.

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

Thus, a reaction solution containing a selenomagnesium halide represented by the following general formula (2) can be obtained by reacting a Grignard reagent with selenium. The obtained reaction solution is provided in Step 2 to be described later.

[Wherein R and X are as defined above].

Step 2

In this Step 2, the reaction liquid obtained in the above Step 1 is dropped into the acidic solution to produce the target selenol.

The kind of acid of the acid solution used in step 2 is not particularly limited, and it may be an organic acid or an inorganic acid. Specifically, 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. Of these acids, an inorganic acid is preferable, and hydrochloric acid is more preferable. These may be used alone or in combination of two or more.

The amount of acid to be used is not particularly limited, but may be, for example, 0.5 to 100 mol, preferably 1 to 10 mol, as the amount of acid to 1 mol of Grignard reagent used in step 1 above. When the amount of the acid used in the acidic solution is within the above range, oxidation of the selenomagnesium halide is inhibited, and the yield of selenols can be further improved. That is, when the amount of the acid used is more than 0.5 mol per 1 mol of the Grignard reagent, the pH of the acidic solution is not inclined to the basicity even after dropping the reaction solution containing the selenomagnesium halide, The solution can be maintained in the acidic region of the selenomagnesium halide and the oxidation reaction of the selenomagnesium halide can be effectively inhibited. When the amount of the acid used is less than 100 mol, an effect suited to the amount of use can be obtained and it is economical.

The above acid is used as an acidic solution dissolved in a solvent. In the present Step 2, a solvent capable of dissolving the above-mentioned acid to prepare a proton-rich solution may be used from the viewpoint of simultaneously achieving the synthesis of selenols and the prevention of oxidation by dropping the reaction solution in a proton-rich solution. Examples of such a solvent include water, an organic solvent capable of dissolving the above-mentioned acid, and mixtures thereof. More specifically, water; Organic solvents such as diethyl ether, tetrahydrofuran, toluene, xylene, 1,4-dioxane and the like; And mixtures thereof. These solvents may be used singly or in combination of two or more kinds.

The amount of the solvent to be used is not particularly limited, but from the viewpoint of increasing the yield of selenols and effectively suppressing a change in the yield per production lot by presenting a proton at a high concentration in an acidic solution, And 50 to 5000 parts by mass, preferably 80 to 3,000 parts by mass, per 100 parts by mass of the reagent.

The dropping rate of the reaction solution obtained in the above Step 1 for the acidic solution is not particularly limited but may be suitably set within a range in which the temperature of the acidic solution described below can be maintained in consideration of the size of the reaction tank and the amount of the acidic solution good.

The temperature of the acid solution at the time of dropping the reaction solution obtained in Step 1 is not particularly limited, but is preferably -50 to 120 占 폚, and more preferably -30 to 50 占 폚. By adjusting in this temperature range, the reaction can proceed more efficiently. That is, if the temperature is higher than -50 ° C, the progress of the reaction is not likely to be stagnated, and if the temperature is lower than 120 ° C, there is no possibility of causing a side reaction.

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

When the reaction liquid is added dropwise, stirring may be carried out if necessary. Further, after the dropwise addition of the reaction liquid, an incubation may be carried out to further increase the yield of the target product, or the incubation of the incubate may be performed. The incubation time is not particularly limited, but is usually 0.1 to 24 hours, preferably 1 to 8 hours.

In the reaction solution thus obtained, a selenol derivative represented by the following general formula (3) is produced.

[Wherein R is as defined above].

From the reaction solution obtained by carrying out Step 2, the selenol is recovered by separating from the organic layer and distilling the solvent from the organic layer. If necessary, purified selenoles can also be obtained by isolation by conventional methods such as stones, distillation, column chromatography and the like.

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

[Example]

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

[Production Example 1]

194.5g (8.00mol) of magnesium and 601.6g of diethyl ether were placed in a 3L sized neat flask equipped with a stirrer, a thermometer and a reflux condenser. A p-bromotoluene solution in which 1368.2 g (8.00 mol) of p-bromotoluene was dissolved in 600.0 g of diethyl ether was prepared, and one-tenth of the p-bromotoluene solution was added to the above-mentioned four-necked flask. The reaction solution was heated to 40 DEG C using an oil bath to initiate the Grignard reaction. Thereafter, the remaining p-bromotoluene solution was added dropwise, and the reaction was conducted for 1 hour to obtain 2764.4 g (1547.1 g, 7.92 mol) of p-trilmagnesium bromide solution.

[Example 1]

174.5 g (97.6 g, 0.50 mol) of the p-trilmagnesium bromide solution obtained in Production Example 1 (97.6 g, 0.50 mol) obtained in Preparation Example 1 was placed in a 500 ml three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 47.4 g (0.50 mol) of selenium powder was added while maintaining the temperature in the range of 0 to 10 ° C to obtain a reaction solution containing selenomagnesium halide. (0.80 mol) of 35% by mass hydrochloric acid and 200.8 g of pure water was immersed in a 500 mL three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and the total amount of the obtained reaction solution was adjusted to 0 to 30 Deg.] C, and the mixture was incubated by continuous stirring for about 1 hour, and the organic layer was recovered.

The recovered organic layer was analyzed by an absolute calibration curve method of gas chromatography, but no di-p-trilyselenanide as an oxidizing substance of p-trilecelenol was detected. Further, the low-boiling point component of the recovered organic layer was distilled off, and 73.7 g (0.43 mol) of a colorless solid of p-trilecelenol was obtained by distillation under reduced pressure. The yield was 86.1% for the Grignard reagent. That is, it was judged that the obtained solid was p-trilcelenol because the melting point was 47 ° C.

[Example 2]

The yield of p-trilecelenol was 85.7%, 86.3%, 85.3% and 85.8%, respectively, with respect to the Grignard reagent under the same conditions as in Example 1. That is, from the results, it was confirmed that according to the production method of the present invention, p-trilecelenol can be stably produced at a high yield without any variation in yield per production lot.

[Comparative Example 1]

P-Trilecenol was synthesized according to the production method described in Non-Patent Document 1. 172.8 g (97.7 g, 0.50 mol) of the p-trilmagnesium bromide solution obtained in Production Example 1 (97.7 g, 0.50 mol) obtained in Preparation Example 1 was placed in a 300 mL three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, Lt; / RTI > Thereafter, heating was stopped, and 47.4 g (0.50 mol) of selenium powder was added so as to maintain the reflux state by the heat of reaction to obtain a reaction solution containing the selenomagnesium halide. 600 g of the pieces of ice cubes were weighed in a 1 L sized neat flask equipped with a stirrer, a thermometer and a reflux condenser, and the whole amount of the reaction solution obtained was added thereto. Subsequently, an aqueous solution of 88.5 g (0.85 mol) of 35 mass% hydrochloric acid was added dropwise over the range of 0 to 30 占 폚, and stirring was continued for about 1 hour to obtain an organic layer.

When the recovered organic layer was analyzed by an absolute calibration curve method of gas chromatography, it was found that 0.07 mol of di-p-trilysedelenide was produced. Subsequently, the low boiling point component of the recovered organic layer was distilled off, and 51.3 g (0.30 mol) of p-trilcelenol colorless solid was obtained by distillation under reduced pressure. The yield was 60.1% for the Grignard reagent. It was judged from the fact that the obtained solid was p-trilcelenol having a melting point of 47 캜.

[Production Example 2]

194.5g (8.00mol) of magnesium and 600.2g of diethyl ether were placed in a 3L sized neat flask equipped with a stirrer, a thermometer and a reflux condenser. A monochlorobenzene solution in which 900.2 g (8.00 mol) of monochlorobenzene was dissolved in 600.8 g of diethyl ether was prepared, and one-tenth of the solution was added to the above-mentioned four-necked flask. The reaction solution was heated to 40 DEG C using an oil bath to initiate the Grignard reaction. Thereafter, the remaining monochlorobenzene solution was added dropwise, and the reaction was carried out for 6 hours to obtain 2101.1 g of a phenylmagnesium chloride solution (1029.2 g of pure substance, 7.52 mol).

[Example 3]

In a 500 mL three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 140.1 g (pure water: 68.4 g, 0.50 mol) of the phenylmagnesium chloride obtained in Preparation Example 2 was added and the reaction solution was cooled to 0 캜. 47.4 g (0.50 mol) of the reaction solution was added thereto while maintaining the temperature within the range of 0 to 10 ° C to obtain a reaction solution containing the selenomagnesium halide. A mixed solution (less than pH 1) of 83.3 g (0.80 mol) of 35 mass% hydrochloric acid and 200.8 g of pure water was placed in a 500 mL three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, Deg.] C, and the mixture was incubated by continuing stirring for about 1 hour to recover the organic layer.

The recovered organic layer was analyzed by gas chromatography using an absolute calibration curve method, but diphenyl diselenide as an oxidizing substance of benzene selenol was not detected. The low boiling point component of the recovered organic layer was distilled off, and 68.4 g (0.44 mol) of a colorless liquid of benzene selenol was obtained by distillation under reduced pressure. The yield was 85.8% for the Grignard reagent. In addition, it was judged that the obtained liquid was benzene selenol because the boiling point was 79 캜 (25 mmHg).

Claims (8)

A process for producing a selenol comprising the following steps 1 and 2:
Step 1: A Grignard reagent represented by the following general formula (1)
[Chemical Formula 1]

(One)
[In the general 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]
To obtain a reaction solution containing a selenomagnesium halide represented by the following general formula (2)
(2)

(2)
[Wherein R and X are as defined above]; And
Step 2: By dropping the reaction solution obtained in Step 1 into the acidic solution,
A process for producing selenophores represented by the following general formula (3)
(3)

(3)
Wherein R is as defined above.
The method according to claim 1,
Wherein, in the general formula (1), R is an aryl group. 3. The method according to claim 1 or 2,
Wherein R is a phenyl group or a p-tolyl group, and X is a chlorine atom or a bromine atom in the general formula (1). 4. The method according to any one of claims 1 to 3,
Wherein the selenium is used in a proportion of 0.5 to 10.0 mol based on 1 mol of the Grignard reagent in the step 1. 5. The method according to any one of claims 1 to 4,
Wherein the acid contained in the acidic solution is an inorganic acid. 6. The 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. 7. The method according to any one of claims 1 to 6,
Wherein in step 1, the reaction of the Grignard reagent and selenium is carried out at -30 to 30 占 폚. 8. The method according to any one of claims 1 to 7,
Wherein the acid contained in the acid solution is 0.5 to 10.0 mol based on 1 mol of the Grignard reagent used in the step 1 in the step 2.