JP2007106680A - Method for producing halogenoacetoxyadamantane compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing a halogenoacetoxyadamantane compound useful as a resin modifier for functional materials and electronic materials, an intermediate for medicines and agrochemicals and a raw material for various inductrial products. <P>SOLUTION: The method for producing the halogenoacetoxyadamantane compound, e.g. 2-methyl-2-adamanylbromoacetate comprises reacting an adamantanol compound, e.g. 2-methyl-2-adamantanol with a halogenoacetyl halide compound e.g. bromoacetyl bromide. In the production method, the above reaction is carried out in the presence of an amine compound such as pyridine and a radical scavenger such as phenothiazine. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a halogenoacetoxyadamantane compound useful as a resin modifier for functional materials and electronic materials, medical and agrochemical intermediates, and raw materials for various industrial products.

  Since adamantane derivatives have excellent heat resistance and transparency, they are expected to be applied to highly functional materials such as heat resistant polymers and electronic materials such as semiconductor resists. Among these, halogenoacetoxyadamantane compounds are useful compounds as functional materials, resin modifiers for electronic materials, medical and agrochemical intermediates, and raw materials for various industrial products.

  So far, as a method for producing a halogenoacetoxyadamantane compound, a method in which a halogenoacetyl halide is directly reacted with a hydroxyl group of an adamantane skeleton (see Patent Document 1), and 2-methyleneadamantane and halogenoacetic acid are reacted in an acid catalyst. There is known a method (see Patent Document 2). In the former method, if the reaction is carried out at a high concentration in order to increase the yield of the kettle and shorten the reaction time, there is a problem that a large amount of impurities may be by-produced as the reaction proceeds. In the method, since 2-adamantanol is used as a starting material and a halogenoacetoxyadamantane compound is obtained via 2-methyleneadamantane, the reaction process is complicated, and 2-methyleneadamantane is 5 to 10% after completion of the reaction. The problem was that it remained. Further, the above two methods have a problem that it is necessary to use two or more reaction kettles.

JP 2004-26798 A JP 2004-244340 A

  As described above, the known methods for producing halogenoacetoxyadamantane have a problem that the by-products during the reaction increase and the reaction process is complicated, and an industrially superior production method is desired. It was rare.

  Under such circumstances, an object of the present invention is to provide a method for efficiently producing a halogenoacetoxyadamantane compound.

  The present inventor has intensively studied to solve the above problems. As a result, by successfully reacting an adamantanol compound and a halogenoacetyl halide compound in the presence of an amine compound and a radical scavenger, the halogenoacetoxyadamantane compound was successfully obtained, and the present invention was completed. It was.

  That is, the present invention provides the following formula (1):

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X is fluorine, chlorine, bromine or iodine. is there.)
A method for producing a halogenoacetoxyadamantane compound represented by the following:
Following formula (2)

{Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings as those in formula (1). }
An adamantanol compound represented by formula (3):

(In the formula, X is fluorine, chlorine, bromine, or iodine.)
And a halogenoacetyl halide compound represented by formula (I), wherein the compound is reacted in the presence of an amine compound and a radical scavenger.
According to this method, the amount of impurities produced with the progress of the reaction is small, and the target product can be obtained efficiently.

  The present invention provides a method for producing a halogenoacetoxyadamantane compound characterized by adding a radical scavenger, and is an excellent method for suppressing the amount of impurities produced as the reaction proceeds. For example, in the conventional method in which esterification is performed using an adamantanol compound and a halogenoacetyl halide compound, it is necessary to perform the reaction at a temperature under ice cooling in order to suppress impurity generation. Since the impurities can be reduced by using the radical scavenger, there is an advantage that the reaction can be performed at a temperature of 20 ° C. or more and the reaction time can be shortened.

  The present invention includes a step of reacting the adamantanol compound represented by the formula (2) and the halogenoacetyl halide compound represented by the formula (3) in the presence of an amine compound and a radical scavenger. A halogenoacetoxyadamantane compound represented by (1) is produced. Hereinafter, the reactants (reactant: reaction raw material, catalyst, etc.) used in the method, reaction conditions, reaction procedures, etc. will be described in detail.

(Adamantanol compound)
In the present invention, an adamantanol compound represented by the following formula (2) is used as a raw material.

In the formula (2), R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and t-butyl group. , N-pentyl group, sec-pentyl group, isopentyl group and the like.

  Specific examples of adamantanol compounds that can be suitably used in the present invention include 2-adamantanol, 5-methyl-2-adamantanol, 5,7-dimethyl-2-adamantanol, and 5,7-diethyl- 2-adamantanol, 2-methyl-2-adamantanol, 2-ethyl-2-adamantanol, 2,5-dimethyl-2-adamantanol, 2,5,7-trimethyl-2-adamantanol, 5-ethyl 2-methyl-2-adamantanol, 5,7-diethyl-2-methyl-2-adamantanol, 2-ethyl-5-methyl-2-adamantanol, 2-ethyl-5,7-dimethyl-2- And adamantanol, 2,5-diethyl-2-adamantanol, 2,5,7-triethyl-2-adamantanol, etc. . Among these compounds, 2-methyl-2-adamantanol and 2-ethyl-2-adamantanol are preferable from the viewpoint of the usefulness of the product.

(Halogenoacetyl halide compounds)
The organometallic compound used as a raw material in the present invention is represented by the following formula (3).

In the formula (3), X is a halogen atom, and is fluorine, chlorine, bromine, or iodine. Of these halogen atoms, chlorine and bromine are preferable from the viewpoint of availability and usefulness of the product, and bromine is particularly preferable. The two Xs present in the molecule may be different or the same, but are preferably the same from the standpoint of availability and the high purity of the product.

  Specific examples of the halogenoacetyl halide compound represented by the formula (3) that are publicly used include fluoroacetyl fluoride, fluoroacetyl chloride, fluoroacetyl bromide, chloroacetyl chloride, chloroacetyl bromide, and bromoacetyl chloride. And bromoacetyl bromide. Of these, chloroacetyl chloride and bromoacetyl bromide are preferred, and bromoacetyl bromide is particularly preferred from the standpoint of availability and usefulness of the product.

  The amount of the halogenoacetyl halide compound used in the method of the present invention is not particularly limited, but from the viewpoint that the amount of impurities by-produced is small, ease of post-treatment, etc., 1 to 10 mol with respect to 1 mol of the adamantanol compound, It is particularly preferable to use 1 to 5 mol.

(Amine compound)
In the method of the present invention, when an adamantanol compound and a halogenoacetyl halide compound are reacted, hydrogen halide corresponding to each structure is generated. Therefore, it is necessary to add an amine compound in order to remove (trap) the hydrogen halide. By adding an amine compound, it is possible to prevent decomposition of raw materials and products due to the generated hydrogen halide, and to precipitate the hydrogen halide as an amine salt, thereby increasing the reaction rate.

As the amine compound, known amine compounds can be used without limitation, but trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-sec-butylamine, due to availability and few impurities. Amines containing aliphatic hydrocarbon groups such as tri-t-butylamine; Amines having aromatic hydrocarbons such as N, N-dimethylaniline, N, N-diethylaniline, N-methyldiphenylamine, N-ethyldiphenylamine Pyrrole, pyrrolidine, N-methylpyrrolidine, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,6-dimethylpyridine, 4-dimethylaminopyridine, N-methylpiperidine, pyrimidine, pyrazine, 1 , 4-Dimethylpipera Down, condensed heterocyclic amines such as N- methylmorpholine can be mentioned. Of these, pyridine and N, N-dimethylaniline are preferred because of their high reactivity. These amine compounds may be used alone or in combination of two or more.
Although the amount of the amine compound used in the method of the present invention is not particularly limited, it is preferable to use 1 to 10 mol, particularly 1 to 5 mol, with respect to 1 mol of the adamantanol compound from the viewpoint of easiness of post-treatment.

(Radical scavenger)
In the method of the present invention, when an adamantanol compound and a halogenoacetyl halide compound are reacted in the presence of an amine compound, hydrogen halide, halogen molecules, halogen radicals, etc. (hereinafter referred to as impurity-causing substances) derived from the halogenoacetyl halide are secondary substances. In some cases, an adamantanol compound as a raw material and a halogenoacetoxyadamantane compound as a target compound are decomposed.

  In general, it is known that the methyl position of an acetyl group undergoes a radical reaction with a halogen molecule such as bromine by heat, light or the like, and is converted to a bromoacetyl group.

  For example, when 2-methyl-2-adamantanol and bromoacetyl bromide are reacted in an organic solvent in the presence of pyridine, in some cases, 2-methyl-2-adamantanol is a dehydrated compound, A large amount of impurities estimated to be methylene adamantane (hereinafter referred to as impurity A) and impurities estimated to be 2-bromomethylene adamantane (hereinafter referred to as impurity B), which is a compound in which bromine is bonded to 2-methylene adamantane May be generated. A radical scavenger is effective for suppressing the by-production of impurities A and B.

  In addition, the use of a radical scavenger has the effect of reducing impurities and reducing the degree of coloration of the target product obtained.

  As the radical scavenger, known compounds generally used as polymerization inhibitors, thermal degradation inhibitors, oxidation degradation inhibitors, and photodegradation inhibitors used for preventing polymerization of polymerizable monomers can be used without limitation. From the availability, hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-4-methylphenol, trade name “Sumilyzer GM” manufactured by Sumitomo Chemical Co., Ltd. [compound name: 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate] and the like; quinone compounds such as benzoquinone and naphthoquinone; 2,2,6,6-tetramethylpiperidine- N-oxyl, 2,2,6,6-tetramethylpiperidine, 2,2,4,6,6-pentamethylpiperidine, 4-ethyl- , 2,6,6-tetramethylpiperidine, 4-propyl-2,2,6,6-tetramethylpiperidine, 4-butyl-2,2,6,6-tetramethylpiperidine and other HALS compounds; phenothiazine, Sumitomo Product name “Sumilyzer TP-D” [compound name: pentaerythritol tetrakis (3-laurylthiopropionate)] manufactured by Kagaku Co., Ltd., product name “Sumilyzer WX-R” [compound name: 4] manufactured by Sumitomo Chemical Co., Ltd. , 4′-thiobis (6-t-butyl-3-methylphenol)] and the like, phosphorus compounds; oxygen and the like. Of these, hydroquinone monomethyl ether, 2,6-di-t-butyl-4-methylphenol, and phenothiazine are preferred because of the high effect of reducing impurities. Two or more of these radical scavengers may be mixed and used.

  The amount of the radical scavenger used is not particularly limited, but it is preferably used in an amount of 0.001 to 10% by mass, particularly 0.01 to 5% by mass with respect to 1 part by mass of the adamantanol compound from the viewpoint of ease of post-treatment. .

(Reaction conditions and reaction procedure)
In the present invention, a halogenoacetoxyadamantane compound represented by the above formula (1) is obtained by including a step of reacting an adamantanol compound and a halogenoacetyl halide compound in the presence of an amine compound and a radical scavenger. From the viewpoint of easy control of reaction conditions and yield, the above reaction is preferably carried out in an organic solvent. Known organic solvents can be used without limitation, but diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, ethylene glycol dimethyl ether from the viewpoint of easy availability and a large amount of the desired product. Ethers such as hexane, heptane, octane and cyclohexane; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; aromatics such as benzene, toluene and xylene It is preferable to use hydrocarbons and the like. Among these, it is particularly preferable to use at least one selected from the group consisting of dichloromethane, benzene, and toluene. These organic solvents may be used as a mixture of two or more. The amount of the organic solvent to be used is not particularly limited, but it is preferable to use 1 to 100 parts by weight, particularly 2 to 50 parts by weight with respect to 1 part by weight of the adamantanol compound because of ease of post-treatment.

  The above reaction can be suitably performed, for example, by introducing a predetermined amount of each reactant (reactant) or solvent into the reaction vessel while stirring the temperature and stirring. At this time, the order of introduction of the reactants is not particularly limited, but when the adamantanol compound and the halogenoacetyl halide compound are contacted at a high concentration, the adamantanol compound may by-produce a dehydrated compound. It is preferable to add the halogenoacetyl halide compound to the solution of the amine compound and the radical scavenger.

  The reaction can be carried out under pressure, under reduced pressure, or under normal pressure, but it is preferable to carry out under normal pressure for simplicity. In this reaction, if water is mixed in the reaction solution, the reaction may not be completed. Therefore, after sufficiently replacing with an inert gas such as nitrogen or argon, the reaction is performed while venting the inert gas. Is preferably performed.

  The reaction temperature of the above reaction is preferably 0 to 100 ° C., particularly 20 to 50 ° C. from the viewpoint of suppressing by-products.

  In the conventional method of performing esterification using an adamantanol compound and a halogenoacetyl halide compound, it was necessary to carry out at a temperature under ice cooling, but according to the method of the present invention, a radical scavenger is used. Therefore, there is an advantage that the reaction can be performed at a temperature of 20 ° C. or more and the reaction time can be shortened.

The reaction time may be appropriately determined while confirming the progress of the reaction according to other reaction conditions, but a sufficient conversion rate can usually be obtained in 0.5 hours to 24 hours.
(Halogenoacetoxy adamantane compound)
By carrying out the reaction in this way, a halogenoacetoxyadamantane compound represented by the following formula (1) is produced as a reaction product.

(Wherein R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X is fluorine, chlorine, bromine, or iodine. .)
Among the halogenoacetoxyadamantane compounds represented by the formula (1), specific examples of suitable compounds include 2-chloroacetyloxyadamantane, 2-bromoacetyloxyadamantane, 2-methyl-2-adamantylchloroacetate, 2-methyl-2-adamantyl bromoacetate, 2-ethyl-2-adamantyl chloroacetate, 2-ethyl-2-adamantyl bromoacetate, 2,5-dimethyl-2-adamantyl chloroacetate, 2,5-dimethyl-2- Adamantyl bromoacetate, 2,5,7-trimethyl-2-adamantyl chloroacetate, 2,5,7-trimethyl-2-adamantyl bromoacetate, 5-ethyl-2-methyl-2-adamantyl chloroacetate, 5-ethyl- 2-methyl-2-a Mantyl bromoacetate, 5,7-diethyl-2-methyl-2-adamantyl chloroacetate, 5,7-diethyl-2-methyl-2-adamantyl bromoacetate, 2,5-diethyl-2-adamantyl chloroacetate, 2 , 5-diethyl-2-adamantyl bromoacetate, 2,5,7-triethyl-2-adamantyl chloroacetate, 2,5,7-triethyl-2-adamantyl bromoacetate and the like. Among these compounds, from the viewpoint of usefulness of the product, 2-methyl-2-adamantyl chloroacetate, 2-methyl-2-adamantyl bromoacetate, 2-ethyl-2-adamantyl chloroacetate, 2-ethyl-2- Adamantyl bromoacetate is preferred, and 2-methyl-2-adamantyl bromoacetate is particularly preferred.

(Separation and purification method)
Although the method for separating the target halogenoacetoxyadamantane compound from the reaction solution obtained in the reaction step is not particularly limited, for example, it can be suitably separated by the following method.

  That is, after completion of the reaction, water is added to remove the by-produced amine salt, and then the remaining halogenoacetyl halide compound is removed by washing with an alkaline aqueous solution such as an aqueous sodium carbonate solution. Thereafter, the organic layer was washed with water until the pH became neutral, and then the colored components in the solution were removed by adsorption treatment such as activated carbon treatment, silica treatment, and alumina treatment as necessary. Water in the organic layer is removed by an adsorption treatment such as sodium sulfate. Thereafter, by removing the organic solvent, a crude product in which the content of the target halogenoacetoxyadamantane compound is usually 95% by mass or more can be obtained. In addition, the purity of the target product can be confirmed by measurement by gas chromatography (GC).

  The crude product thus obtained can be purified further by a known method such as crystallization (recrystallization), vacuum distillation, steam distillation, sublimation purification or the like to obtain a high-purity target product. As a purification method, it is preferable to employ a crystallization method using a solvent containing at least an alcohol as a crystallization solvent because a highly pure target product can be obtained simply and efficiently. Since the target halogenoacetoxyadamantane compound is dissolved in a wide range of polar organic solvents from high polarity to low polarity, a mixed solvent of alcohol and water is used as a crystallization solvent in some cases. At this time, the mixing ratio (mass ratio) of alcohol and water in the mixed solution serving as a crystallization solvent is not particularly limited, but alcohol: water = 1: 0.01 to 1: 1, particularly 1: 0.1 to 0.1. It is preferably used at 1: 0.5.

  As the alcohol used in the crystallization solvent, known alcohols can be used without limitation, but from the viewpoint of availability, methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, t-butanol, n-pentanol. It is preferable to use at least one selected from the group consisting of n-hexanol and cyclohexanol. Of these, methanol, ethanol, and isopropyl alcohol are particularly preferable, and methanol is particularly preferable because of its low price and high purity of the obtained target product.

  The amount of the crystallization solvent to be used is not particularly limited, but from the viewpoint of recovery efficiency, it is preferable to use 0.5 to 20 parts by mass, particularly 1 to 10 parts by mass with respect to 1 part by mass of the raw material adamantanol compound.

  The temperature at which crystallization is performed is not particularly limited, but is preferably 20 ° C. or less, particularly 10 ° C. or less, because there are many objects to be obtained, and the crystallization time is not particularly limited. In general, the target product can be obtained in high yield and purity in 0.5 to 24 hours. For example, after adding methanol to the crude body, it was once heated to 30 to 35 ° C. to obtain a uniform solution, cooled to 10 ° C. or less to precipitate crystals, and then aged for about 1 to 2 hours. By recovering the crystals by filtration or the like, a halogenoacetoxyadamantane compound having a purity of 98% by mass or more can be obtained.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1
The inside of the 100 ml four-necked flask was sufficiently replaced with nitrogen gas and vented. 3.33 g (0.020 mol) of 2-methyl-2-adamantanol, 16.7 g which is 5 times the weight of 2-methyl-2-adamantanol which is toluene as a solvent and 2-pyridine which is a raw material 1.74 g (0.022 mol) which is 1.1 mol times of methyl-2-adamantanol, and 0.5 mass% of 2-methyl-2-adamantanol which is a raw material of phenothiazine as a radical scavenger. 0167 g was added, stirred and heated to 40 ° C. Then, 6.46 g (0.032 mol), which is 1.6 mol times that of 2-methyl-2-adamantanol, which is a raw material of bromoacetyl bromide, is carefully added so that the temperature of the reaction solution becomes 42 ° C. or less. It was dripped. Salt precipitation was observed immediately after the start of dropping. After stirring at 40 ° C. for 3 hours, 16.7 g of tap water was added, and the organic layer was washed with 16.7 g of 5% aqueous sodium carbonate solution and then washed 4 times with 16.7 g of ion-exchanged water to neutralize the pH. Thereafter, the toluene layer was concentrated under reduced pressure to obtain 5.7 g of a pale yellow viscous substance. As a result of the GC analysis of the viscous material, the raw material 2-methyl-2-adamantanol was 0%, the impurity A was 3%, the impurity B was 2%, and the target product, 2-methyl-2-adamantyl bromo It contained 95% acetate.

Examples 2-4
The operation was performed in the same manner as in Example 1 except that the radical scavenger was changed to that shown in Table 1. The results are shown in Table 1.

Example 5
6.66 g of methanol was added to 5.7 g of the pale yellow viscous material obtained in Example 1, and the mixture was once heated to 35 ° C., then cooled to 2 ° C. to precipitate a solid, and the mixture was precipitated at 2 ° C. for 1 hour. Aged. The obtained solid was filtered to obtain 4.0 g of a white solid (yield 70% in terms of 2-methyl-2-adamantanol). As a result of analysis by GC of the obtained solid, the content of 2-methyl-2-adamantyl bromoacetate was GC purity 99%.

Example 6
The inside of the 100 ml four-necked flask was sufficiently replaced with nitrogen gas and vented. 3.33 g (0.020 mol) of 2-methyl-2-adamantanol, 16.7 g which is 5 times the weight of 2-methyl-2-adamantanol which is toluene as a solvent, and N, N-dimethylaniline 2.91 g (0.024 mol) which is 1.2 mol times the raw material 2-methyl-2-adamantanol, and 0.5 mass of 2-methyl-2-adamantanol which is phenothiazine as a radical scavenger. % 0.0167g was added, stirred and heated to 40 ° C. Then, 4.85 g (0.024 mol), which is 1.2 mol times 2-methyl-2-adamantanol, which is the raw material of bromoacetyl bromide, was carefully added so that the temperature of the reaction solution was 42 ° C. or lower. It was dripped. After stirring at 40 ° C. for 2 hours, 16.7 g of tap water was added, and the organic layer was washed with 16.7 g of 5% aqueous sodium carbonate solution and then washed 4 times with 16.7 g of ion-exchanged water to neutralize the pH. Thereafter, the toluene layer was concentrated under reduced pressure to obtain 5.7 g of a pale yellow viscous substance. As a result of GC analysis of the viscous material, the raw material 2-methyl-2-adamantanol was 0%, the impurity A was 2%, the impurity B was 1%, and the target product, 2-methyl-2-adamantyl bromo It contained 97% acetate.

Examples 7-9
The operation was performed in the same manner as in Example 6 except that the radical scavenger was changed to that shown in Table 2. The results are shown in Table 2.

Example 10
6.66 g of methanol was added to 5.7 g of the pale yellow viscous material obtained in Example 6, and the mixture was once heated to 35 ° C., then cooled to 2 ° C. to precipitate a solid, and the mixture was precipitated at 2 ° C. for 1 hour. Aged. When the obtained solid was filtered, it was obtained as 4.2 g of a white solid (yield 73% in terms of 2-methyl-2-adamantanol). As a result of analysis by GC of the obtained solid, the content of 2-methyl-2-adamantyl bromoacetate was GC purity 99%.

Example 11
The same operation was performed except that the reaction temperature was changed to 30 ° C. in Example 6. After stirring at 30 ° C. for 2 hours, 16.7 g of tap water was added, and the organic layer was washed with 16.7 g of 5% aqueous sodium carbonate solution and then washed 4 times with 16.7 g of ion-exchanged water to neutralize the pH. Thereafter, the toluene layer was concentrated under reduced pressure to obtain 5.7 g of a pale yellow viscous substance. As a result of GC analysis of the viscous material, the raw material 2-methyl-2-adamantanol was 0%, the impurity A was 1%, the impurity B was 1%, and the target product, 2-methyl-2-adamantyl bromo It contained 98% acetate.

Examples 12-14
The operation was performed in the same manner as in Example 11 except that the radical scavenger was changed to that shown in Table 3. The results are shown in Table 3.

Example 15
6.66 g of methanol was added to 5.7 g of the pale yellow viscous material obtained in Example 11, and the mixture was once heated to 35 ° C., then cooled to 2 ° C. to precipitate a solid, and the mixture was precipitated at 2 ° C. for 1 hour. Aged. The obtained solid was filtered to obtain 4.3 g of a white solid (yield 75% in terms of 2-methyl-2-adamantanol). As a result of analysis by GC of the obtained solid, the content of 2-methyl-2-adamantyl bromoacetate was GC purity 99%.

Example 16
To the 5.7 g of pale yellow viscous material obtained in the same manner as in Example 11, 9.99 g of a mixed solution of methanol / water = 95/5 was added and once heated to 35 ° C., then cooled to 2 ° C. A solid was precipitated and aged at 2 ° C. for 1 hour. When the obtained solid was filtered, it was obtained as 4.4 g of a white solid (yield 77% in terms of 2-methyl-2-adamantanol). As a result of analysis by GC of the obtained solid, the content of 2-methyl-2-adamantyl bromoacetate was GC purity 99%.

Comparative Example 1
The inside of the 100 ml four-necked flask was sufficiently replaced with nitrogen gas and vented. 3.33 g (0.020 mol) of 2-methyl-2-adamantanol, 16.7 g which is 5 times the weight of 2-methyl-2-adamantanol which is toluene as a solvent and 2-pyridine which is a raw material 1.74 g (0.022 mol) which is 1.1 mol times of methyl-2-adamantanol was added, stirred and heated to 40 ° C. Then, 6.46 g (0.032 mol), which is 1.6 mol times that of 2-methyl-2-adamantanol, which is a raw material of bromoacetyl bromide, is carefully added so that the temperature of the reaction solution becomes 42 ° C. or less. It was dripped. Salt precipitation was observed immediately after the start of dropping. After stirring at 40 ° C. for 3 hours, 16.7 g of tap water was added, and the organic layer was washed with 16.7 g of 5% aqueous sodium carbonate solution and then washed 4 times with 16.7 g of ion-exchanged water to neutralize the pH. Thereafter, the toluene layer was concentrated under reduced pressure to obtain 5.6 g of a brown viscous substance. As a result of GC analysis of the viscous material, the raw material 2-methyl-2-adamantanol was 0%, the impurity A was 5%, the impurity B was 15%, and the target product, 2-methyl-2-adamantyl bromo It contained 80% acetate.

Claims (2)

Following formula (1)

(Wherein R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X is fluorine, chlorine, bromine, or iodine. .)
A method for producing a halogenoacetoxyadamantane compound represented by the following:
Following formula (2)

{Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings as those in formula (1). }
An adamantanol compound represented by formula (3):

(In the formula, X is fluorine, chlorine, bromine, or iodine.)
And a reaction step of reacting the halogenoacetyl halide compound represented by the above with an amine compound and a radical scavenger. 2. The method according to claim 1, further comprising a generation step of crystallizing the crude product obtained in the reaction step using alcohol or a mixed solution of alcohol and water.