TW201722891A - Method for producing bromoalkyladamantane - Google Patents

Abstract

One embodiment of the present invention provides a method for producing a bromoalkyladamantane, which includes causing a reaction between an alkyladamantane and bromine, and wherein: the reaction is carried out in the presence of a Lewis acid catalyst under solvent-free conditions; the alkyladamantane has a melting point of 50 DEG C or less; and the supply amount (a mol) of the alkyladamantane and the supply amount (b mol) of bromine to a reactor satisfy the following condition. 1 ≤ b/a ≤ 1.75.

Description

Method for producing bromoalkyladamantane

The present invention relates to a process for producing a bromoalkyladamantane which can be used as a raw material for a functional material or an electronic material.

Since the adamantane derivative is excellent in heat resistance and has high transparency, it is expected to be applied to a functional material such as a heat resistant polymer or an electronic material such as a resist for a semiconductor. Among them, alkyladamantane derivatives are known for their use in the above applications. a portion of the adamantane skeleton in which the reactivity of the bridgehead is high, and a bromoalkyladamantane (especially monobromoalkyladamantane and dibromoalkyladamantane) having a bromine atom introduced into the bridgehead of the alkyladamantane It is important as a raw material for synthesizing various alkyladamantane derivatives.

A method of brominating adamantane is described in Patent Document 1 in a halogenated hydrocarbon solvent such as dichloromethane, in the presence of anhydrous ferric chloride and/or anhydrous iron bromide, in a reaction time of 15 hours. A method of producing 1,3-dibromoadamantane by reacting bromine with adamantane.

Patent Document 2 describes that in the presence of a Lewis acid such as boron tribromide or aluminum bromide, the reaction temperature is 65 ° C, relative to the 1,3-dimethyl fund. A method of producing 1,3-dibromo-5,7-dimethyladamantane by reacting hexane with 2 to 4 moles of hexane.

Further, Patent Document 3 describes a method of producing a dihalogenated adamantane by reacting 5 to 15 moles of halosulfonic acid with respect to adamantane.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2002-145809

[Patent Document 2] Japanese Patent Laid-Open No. Hei 2-138139

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2003-146916

In the method for producing dibromodamantane described in Patent Document 1, it is necessary to use a halogenated hydrocarbon specified by a chemical substance discharge management management method or the like as a solvent, and the burden on the human body and the environment is not good. Further, in the case of review by the present inventors, in the case where 1,3-dimethyladamantane is brominated by the production method instead of adamantane, a large amount of carbon atoms other than the bridgehead position in the adamantane skeleton are formed. Brominated monobromoalkyladamantane isomer (hereinafter referred to as monobromo isomer) and dibromoalkyladamantane isomer (hereinafter referred to as dibromo isomer) (hereinafter monobromo isomerization) The substance and the dibromo isomer are collectively referred to as "bromine isomers". Moreover, these isomers Since the intended product is only an isomer having a different substitution position at the bromine atom, the trait is similar to the intended product. Therefore, it is not easy to separate the target product from the bromine isomer, and it is difficult to obtain the bromoalkyladamantane of the intended product in high purity.

Further, in the method for producing bromoalkyladamantane described in Patent Document 2, it is necessary to remove an excessive amount of bromine and boron tribromide remaining after the reaction, and the production cost and workability are not good.

Further, in the method for producing dihalogenated adamantane described in Patent Document 3, it is necessary to use 5 to 15 moles of excess halosulfonic acid with respect to adamantane, and the pot efficiency and waste treatment are not good. .

Therefore, it is required to reduce the formation of bromine isomers, and it is possible to obtain a method of producing a brominated alkyl adamantane having a carbon atom at the bridging position of the bridgehead for the purpose of production. Further, it has been demanded to develop an industrially advantageous production method which does not require the steps and equipment for recovering excess bromine or the like, and which does not use a halogenated hydrocarbon having a high burden on the human body and the environment as a solvent.

The inventors of the present invention have found a method for producing a bromoalkyladamantane which is industrially advantageous in order to solve the above problems, and have achieved the present invention.

The present invention has been completed based on this finding.

That is, the present invention is as follows, for example.

[1] A method for producing a bromoalkyladamantane, which comprises reacting an alkyladamantane with bromine, The reaction is carried out in the absence of a solvent and in the presence of a Lewis acid catalyst. The alkyl adamantane has a melting point of 50 ° C or less, and the supply of the alkyl adamantane to the reactor (a mole) and the supply of bromine. The amount (b mole) satisfies the following conditions, 1 ≦ b / a ≦ 1.75.

[2] The method for producing a bromoalkyladamantane according to [1], wherein the Lewis acid catalyst is at least one selected from the group consisting of an iron halide and an aluminum halide, and the Lewis acid catalyst is used in an amount relative to the aforementioned alkyl gold The supply amount of the alkane is in the range of 0.01 to 0.20 times the molar amount.

[3] A method for producing a bromoalkyladamantane, which is a reaction of an alkyl adamantane and a bridgehead carbon atom of the alkyl adamantane with a brominated monobromoalkyladamantane and bromine, The reaction is carried out in the absence of a solvent and in the presence of a Lewis acid catalyst. The alkyl adamantane has a melting point of 50 ° C or less, and the amount of alkyl adamantane supplied to the reactor (a mole), monobromoalkyl gold The supply amount of crotane (c mole) and the supply amount of bromine (b mole) satisfy the following conditions, 1 ≦ b / (a + c / 2) ≦ 1.75.

[4] The method for producing a bromoalkyladamantane according to [3], wherein the Lewis acid catalyst is at least one selected from the group consisting of an iron halide and an aluminum halide, and the Lewis acid catalyst is used in an amount relative to the aforementioned alkyl gold The sum of the supply amount of the alkane and the supply amount of the aforementioned monobromoalkyladamantane is 0.01 to 0.20 times the molar amount. Wai.

[5] The method for producing a bromoalkyladamantane according to any one of [1] to [4] wherein the alkyladamantane is a dialkyladamantane.

[6] The method for producing a bromoalkyladamantane according to any one of [1] to [4] wherein the alkyladamantane is a monoalkyladamantane.

[7] The method for producing a bromoalkyladamantane according to any one of [1] to [6] wherein the reaction temperature is in the range of not less than the melting point of the alkyladamantane and not more than 58 °C.

[7-1] The method for producing a bromoalkyladamantane according to [7], wherein the alkyl adamantane is 1,3-dimethyladamantane or 1-ethyladamantane, and the reaction temperature is 0 to 58. °C.

[8] The method for producing a bromoalkyladamantane according to any one of [3] to [7-1], which further comprises a monobromoalkyladamantane obtained from the bromoalkyladamantane obtained by the foregoing reaction. Separation, the monobromoalkyladamantane is recycled in the aforementioned reactor.

[8] The method for producing a bromoalkyladamantane according to any one of [1] to [8] wherein the conversion ratio of the alkyl adamantane is from 90 to 100%.

[8-2] The method for producing a bromoalkyladamantane according to any one of [1] to [8-1], wherein the content of the dibromoalkyladamantane in the product is relative to the product The total weight of the alkyladamantane and the monobromoalkyladamantane is 0.2 times or more and 4.0 times or less by weight.

[8-3] The method for producing a bromoalkyladamantane according to any one of [1] to [8-2], wherein a ratio of a bromine isomer to a bromoalkyladamantane in the product is generated The ratio of monobromo isomers in the product (% by mole) + two of the products Ratio of bromine isomer (% by mole)} / { ratio of monobromoalkyladamantane in the product (% by mole) + ratio of dibromoalkyladamantane in the product (% by mole)} ×100 is 20.0 or less.

[9] A method for producing a bromoalkyladamantane obtained by reacting an alkyladamantane having a melting point of 50 ° C or less with bromine in the absence of a solvent and a Lewis acid catalyst, wherein the reactor is The supply amount of alkyl adamantane (a mole) and the supply amount of bromine (b mole) satisfy the following conditions.

1≦b/a<2

[10] The method for producing a bromoalkyladamantane according to [9], wherein the Lewis acid catalyst is at least one selected from the group consisting of an iron halide and an aluminum halide, and the Lewis acid catalyst is used in an amount relative to the aforementioned alkyl gold The supply of the alkane is in the range of 0.01 to 0.20 moles.

[11] A method comprising bromination of an alkyl adamantane having a melting point of 50 ° C or less and a carbon atom at a bridgehead position of the alkyl adamantane in the absence of a solvent and a Lewis acid catalyst A method for producing a bromoalkyladamantane obtained by reacting a brominated alkyl adamantane with bromine, wherein a supply amount of alkyl adamantane to the reactor (a mole), a supply amount of monobromoalkyladamantane (c mole) And the supply amount of bromine (b mole) is to satisfy the following conditions.

0.5≦b/(a+c/2)<2

[12] The method for producing a bromoalkyladamantane according to [11], wherein the Lewis acid catalyst is at least one selected from the group consisting of an iron halide and an aluminum halide, and the Lewis acid catalyst is used in an amount relative to the aforementioned alkyl gold The total amount of the supply of the alkane and the supply amount of the aforementioned monobromoalkyladamantane is 0.01 to 0.20 times the molar amount. range.

[13] The method for producing a bromoalkyladamantane according to any one of [9] to [12] wherein the alkyladamantane is a dialkyladamantane.

[14] The method for producing a bromoalkyladamantane according to any one of [9] to [12] wherein the alkyladamantane is a monoalkyladamantane.

[15] The method for producing a bromoalkyladamantane according to any one of [9] to [14] wherein the reaction temperature is in the range of 58 ° C or lower of the melting point of the alkyl adamantane.

[16] The method for producing a bromoalkyladamantane according to any one of [11] to [15], which further comprises separating the monobromoalkyladamantane from the bromoalkyladamantane obtained by the foregoing reaction, The monobromoalkyladamantane is recycled in the aforementioned reactor.

According to the embodiment of the present invention, a method for producing a bromoalkyladamantane which is used as a raw material of a functional material or an electronic material can be provided, and when a desired bromoalkyladamantane is synthesized, bromine isomerism which is a cause of impurities is reduced. For the formation of the species, a method of obtaining a brominated alkyl adamantane having a carbon atom at the head of the bridge by bromination can be obtained in a good yield. Further, it is an industrially advantageous production method that provides a halogenated hydrocarbon which does not have a high burden on the human body and the environment.

[Formation of the Invention]

The form of the present invention will be described below (hereinafter simply referred to as "this embodiment"). The following embodiment is illustrative of the present invention. For example, the present invention is not limited to the following. The present invention can be carried out within the scope of the gist of the invention.

As described above, according to the method for producing a bromoalkyladamantane of the present embodiment, the alkyl adamantane having a specific melting point is used, and the ratio of the amount of bromine to the alkyladamantane is set to a specific range, and the impurity can be suppressed. The amount of bromine isomers produced, while producing the desired bromoalkyladamantane with good efficiency. Here, "bromoalkyladamantane" means an alkyl adamantane which is brominated only at the bridgehead position of the adamantane skeleton, and particularly refers to one or two carbon atoms of the bridgehead position of the adamantane skeleton. Brominated monobromoalkyladamantane and dibromoalkyladamantane. Further, the "bromine isomer" means one or more brominated bromoalkyladamantanes having a carbon atom other than the bridgehead position of the adamantane skeleton. Thus, for example, a carbon atom at the bridgehead position of the adamantane skeleton and a dibromoalkyladamantane which is brominated at a carbon atom other than the bridgehead position are classified as bromine isomers. In the present specification, the description of "the bromination of a carbon atom at the bridgehead position" means that only the carbon atom of the bridgehead is brominated, and the hydrogen atom of the carbon atom bonded to the bridgehead is substituted by bromine.

The monobromoalkyladamantane and the dibromoalkyladamantane obtained by the method of the present embodiment can be used, for example, as a synthetic raw material of an alkyladamantane derivative useful as a raw material of a functional material or an electronic material, particularly dibromo Alkyl adamantane is highly useful. As described above, the separation of the dibromoalkyladamantane from the bromine isomers is not simple due to the structural similarity, so that the dibromoalkyladamantane is intentionally obtained in a state where the impurities are small.

Further, in the method of the present embodiment, the monobromoalkyladamantane-based liquid formed together with the dibromoalkyladamantane can also be used as a reaction. The solvent acts. Therefore, it is not necessary to use a harmful substance such as a halogenated hydrocarbon as a solvent, and therefore, the method of the present embodiment is also excellent in safety. The monobromoalkyladamantane as a solvent is preliminarily present in the reaction system, and is preferred from the viewpoint of smooth reaction.

The monobromoalkyladamantane remaining by reaction or reaction is reused by separation as a solvent for the next reaction. Further, in the method of the present embodiment, the amount of bromine used is relatively small, and it is not necessary to post-treat an excessive amount of bromine. Further, the number of reaction steps is small, and it is not necessary to carry out the reaction under severe conditions such as high temperature or high pressure. Therefore, the method of the present embodiment is simple and excellent in terms of economy.

The manufacturing method of this embodiment will be specifically described below.

In the production method of the present embodiment, an alkyladamantane having a melting point of 50 ° C or less, an alkyladamantane having a melting point of 50 ° C or less, and the alkyladamantane are used in the absence of a solvent and a Lewis acid catalyst. A process for the production of a bromoalkyladamantane characterized by the reaction of a brominated monobromoalkyladamantane with bromine at the head of the bridge.

The brominated monobromoalkyladamantane of the carbon atom at the bridgehead position of the bromoalkyladamantane adamantane skeleton obtained by the production method of the present embodiment, and the two carbon atoms of the bridgehead are brominated The bromoalkyladamantane is more preferably a dibromoalkyladamantane which is brominated by two carbon atoms at the bridgehead position.

In the present embodiment, the alkyl adamantane having a melting point of 50 ° C or less used as a raw material may, for example, be 1-ethyladamantane (melting point - 60 ° C), 1-propyladamantane (melting point - 1 ° C), or 1-isomeric. Propyl adamantane (melting point -20 ° C , a monoalkyladamantane such as 1-butane adamane (melting point -12 ° C), and a dialkyladamantane such as 1,3-dimethyladamantane (melting point -29.96 ° C).

In the production method of the present embodiment, the amount of bromine used in the bromination reaction of alkyl adamantane is the amount of alkyl adamantane supplied to the reactor (a mole), and the amount of bromine supplied (b mole). It is preferable that the amount satisfying the range of 1 ≦ b / a ≦ 1.75 is preferable, and the amount satisfying the range of 1.3 ≦ b / a ≦ 1.75 is more preferable. Further, when the alkyladamantane is supplied to the reactor together with the monobromoalkyladamantane to carry out the reaction, the supply amount of the alkyladamantane (a mole) and the supply amount of the monobromoalkyladamantane (c mole) And the supply amount of bromine (b mole) is preferably set to satisfy the range of 1 ≦ b / (a + c / 2) ≦ 1.75, and is set to satisfy 1.2 ≦ b / (a + c / 2) The amount of bromine used in the range of ≦1.75 is better, and the amount of bromine used in the range of 1.3≦b/(a+c/2)≦1.70 is particularly good. When the amount of bromine used is less than the above range, unreacted alkyladamantane or monobromoalkyladamantane remains, and the efficiency of the reaction is poor. On the other hand, when it is more than the above range, a large amount of dibromoalkyladamantane is formed, and the amount of monobromoalkyladamantane produced as a solvent is reduced. Therefore, the reaction liquid is firmly solidified during the reaction, and it is impossible to stir or the like, and it is difficult to stabilize the production.

The bromination reaction of the alkyladamantane of the present embodiment is preferably carried out without a solvent. As described in JP-A-2002-145809, when a halogenated hydrocarbon is used as a solvent, the amount of by-products of bromine isomers is greatly increased, and many monobromoalkyladamantane remain, so monobromine must be recovered. Fundaneane and recycling. The recovery/recycling step can be omitted by converting all of the monobromoalkyladamantane to dibromoalkyladamantane, but At the time of conversion, it is necessary to supply an excessive amount of bromine or to greatly elongate the reaction time, which causes problems such as an increase in raw material cost or deterioration in productivity.

Further, it is also considered to use a saturated hydrocarbon as a solvent, but the reaction rate is slow, and the dibromoalkyladamantane is only slightly traced.

The Lewis acid catalyst of the present embodiment is preferably an iron halide such as an iron (III) anhydrate or an iron (III) anhydrate, or an aluminum halide such as anhydrous aluminum chloride or anhydrous aluminum bromide. Preferably, it is an anhydrous substance of iron (III) chloride and anhydrous aluminum chloride.

The Lewis acid catalyst usage amount (mole) is preferably 0.01 to 0.20 times moles, more preferably 0.01 to 0.20 times moles, based on the total amount of the alkyl adamantane supplied and the amount of the monobromoalkyladamantane supplied. It is 0.02~0.10 times Mo, especially 0.03~0.10 times Mo. When the amount of the catalyst used is 0.01 times or more based on the total amount of the alkyl adamantane and the supply amount of the monobromoalkyladamantane, a sufficient reaction rate can be obtained, and the unreacted alkyl gold can be reduced. Ranane or monobromoalkyladamantane. By using the catalyst amount in an amount of 0.20 times or less relative to the supply amount of the alkyladamantane and the supply amount of the monobromoalkyladamantane, the amount of catalyst remaining as waste can be suppressed. Therefore, it is better. Selecting the type and amount of the catalyst to increase the conversion rate of the alkyl adamantane of the raw material, preferably the conversion is 90 to 100%, more preferably 95 to 100%, and particularly preferably 98 to 100%. . Here, the conversion ratio of the alkyladamantane means the ratio (mol%) of the consumption amount of the alkyladamantane input.

The reaction temperature in the present embodiment is not particularly limited, and can be set in a wide range from the melting point of the alkyladamantane to the boiling point of the bromine. But the higher The temperature and the amount of by-product formation of the bromine isomer increase, so the reaction temperature is preferably 58 ° C or less of the melting point of the alkyl adamantane, more preferably 50 ° C or less of the melting point of the alkyl adamantane. When the melting point of the alkyl adamantane is 30 ° C or less, the reaction temperature is preferably 30 ° C or less above the melting point of the alkyl adamantane, and the melting point of the alkyl adamantane is less than 0 ° C, and the reaction temperature is particularly preferably 0 to 30. °C.

For example, when the alkyladamantane is 1,3-dimethyladamantane (melting point -29.96 ° C) or 1-ethyladamantane (melting point -60 ° C), the reaction temperature is preferably 0 to 58 ° C, more preferably 20~55°C, more preferably 20~30°C, especially better 20~25°C.

Further, the temperature at the time of adding bromine may be arbitrarily selected, but it is usually carried out at the same temperature as the above reaction temperature. The addition time is also not particularly limited, and by dropping the bromine, the dropping is usually completed in 30 to 60 minutes. When the dropping speed is too fast, the temperature rises too high due to the heat of reaction, and together with the by-produced hydrogen bromide, the dropped bromine is discharged to the outside of the system. Conversely, when the dropping speed is too slow, the overall reaction time becomes long and the efficiency is not good.

The reaction time in the present embodiment is not so much determined by the reaction temperature or the like, and is usually about 1 to 5 hours.

The reaction method of the present embodiment is not particularly limited, and may be carried out under pressure, but it is most convenient to carry out under normal pressure. For example, a reaction method in which a mixture of an alkyl adamantane and a Lewis acid catalyst of a raw material is introduced into a reactor under a normal pressure, a bromine is dropped at a specific reaction temperature, and a semi-batch reaction is carried out.

Dibromoalkane in the product obtained by the reaction of this embodiment The content of the adamantane is preferably 0.2 times or more and 4.0 times or less, more preferably 0.7 times or more, based on the total weight of the alkyladamantane and the monobromoalkyladamantane in the resulting product. It is 3.5 times or less, more preferably 1.0 times or more and 3.5 times or less, and particularly preferably 2.0 times or more and 3.5 times or less. When it is in the above range, the fluidity of the reaction product can be maintained even in the absence of a solvent, and the bromoalkyladamantane can be stably produced.

As described above, the method of the present embodiment is excellent in suppressing the amount of formation of bromine isomers of impurities and efficiently producing a desired bromoalkyladamantane. Specifically, the desired ratio of bromine isomers to bromoalkyladamantane in the product {ratio of monobromo isomers in the product (% by mole) + dibromo isomerization in the product Ratio of material (% by mole)} / { ratio of monobromoalkyladamantane in the product (% by mole) + ratio of dibromoalkyladamantane in the product (% by mole)} × 100, It is preferably 20.0 or less (for example, 1.0 to 20.0), more preferably 12.0 or less (for example, 1.0 to 12.0), still more preferably 8.0 or less (for example, 1.0 to 8.0), and particularly preferably 4.0 or less (for example, 1.0 to 4.0).

The product obtained by the reaction of the present embodiment can be purified by a usual method such as crystallization, distillation, extraction or column chromatography. Specifically, pure water is added to the obtained reaction liquid, and then extraction with n-heptane is carried out to carry out neutralization, reduction of a trace amount of residual bromine, and washing with water. Next, the n-heptane solvent is distilled off, and the crystal is precipitated by using a weak solvent such as methanol, and the dibromoalkyladamantane obtained by bromination of the carbon atom of the desired bridgehead is obtained by solid-liquid separation.

Further, a brominated monobromoalkyladamantane having a carbon atom at the head of the bridge may be obtained from a filtrate obtained by separating a n-heptane phase or a solid-liquid phase. It is recovered by a conventional method such as distillation, extraction, column chromatography, or the like. The recovered monobromoalkyladamantane can be used as a raw material and reused in the reaction.

[Examples]

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

<Example 1>

In a 100 ml three-necked flask equipped with a stirrer, a thermometer, and a Dairy cooling tube, 1,3-dimethyladamantane (1,3-DMA) 15.0 g (91.3 mmol) and ferric chloride (III) were charged. Anhydrous (FeCl ₃ ) 0.59 g (3.6 mmol) was subjected to nitrogen substitution. Then, stirring was carried out while 25 g of bromine (156.4 mmol) was dropped by dropping the funnel. At this time, the flask was cooled in a water bath while adjusting to maintain the internal temperature at 20 to 25 ° C, and bromine was dropped for 30 to 60 minutes. After the completion of the dropwise addition, after aging at 20 to 25 ° C for 2 hours, water was added, followed by extraction with n-heptane. The n-heptane phase obtained by decantation is neutralized, and a trace amount of residual bromine is reduced and washed with water. The n-heptane phase was quantified using internal standard gas chromatography, and the conversion of 1,3-DMA was 99 mol%. Here, the conversion ratio of 1,3-DMA was calculated by the formula {consuming 1,3-DMA (mole) / input 1,3-DMA (mole)} × 100.

Further, the yield of 1-bromo-3,5-dimethyladamantane (DMA-mBr) of the 1,3-DMA standard was 27.9 mol%, and the 1,3-dibromo-5,7-dimethyl fund The yield of the cycloalkane (DMA-dBr) was 65.9 mol%, the yield of the monobromo isomer of the carbon atom other than the bridgehead was brominated to 0.9 mol%, and the yield of the dibromo isomer was 1.2 mol%. . The reaction solution becomes a viscous liquid ~ semi-cured, but can be stirred. Here, the DMA-mBr yield is calculated by the formula [ DMA-mBr (mole in the product - input DMA-mBr (mole)] / input 1,3-DMA (mole)] × 100 . The yield of the other component is, for example, the case of the DMA-dBr yield, and is calculated by the formula {DMA-dBr (mole) / input 1,3-DMA (mole)} × 100. The ETA-mBr yield and the ETA-dBr yield in the following Example 7 and Comparative Example 5 were also calculated in the same manner as the above DMA-dBr yield.

<Example 2>

The same operation as in Example 1 was carried out except that the amount of 1,3-DMA was changed to 17.0 g (103.5 mmol), and the amount of the iron (III) anhydrate was changed to 0.67 g (4.1 mmol). . The reaction solution is liquid and can be easily stirred. The results are shown in Table 1.

<Example 3>

The same operation as in Example 1 was carried out except that the amount of the iron (III) chloride anhydrate was changed to 0.30 g (1.8 mmol). The reaction solution is liquid and can be easily stirred. The results are shown in Table 1.

<Example 4>

In addition to changing the amount of iron (III) chloride anhydrate to 1.48g (9.1 The same operation as in Example 1 was carried out except that it was a millimolar. The reaction solution becomes a viscous liquid ~ semi-cured, but can be stirred. The results are shown in Table 1.

<Example 5>

The same operation as in Example 1 was carried out except that the reaction temperature was changed to 50 to 55 °C. The reaction solution becomes a viscous liquid ~ semi-cured, but can be stirred. The results are shown in Table 1.

<Example 6>

In addition to the substitution of 1,3-DMA, anhydrous iron (III) anhydrate was used using a mixed raw material containing 1,3-DMA 13.5 g (82.2 mmol) and DMA-mBr 6.0 g (24.7 mmol). The same operation as in Example 1 was carried out except that the amount was 0.59 g (3.6 mTorr). The reaction solution becomes a viscous liquid ~ semi-cured, but can be stirred. The results are shown in Table 1.

<Example 7>

The same operation as in Example 1 was carried out except that 1,3-DMA was changed to 1-ethyladamantane (1-ETA). The conversion of 1-ETA was 100%, and the yield of 1-bromo-3-ethyladamantane (ETA-mBr) based on 1-ETA was 31.1%, 1,3-dibromo-5-ethyladamantane ( The yield of ETA-dBr) was 56.1%, the yield of the monobromo isomer of the carbon atom other than the bridgehead was brominated to 0.9%, and the yield of the dibromo isomer was 8.2%. Here, the conversion rate and each yield were calculated in the same manner as in Example 1. The reaction solution is liquid and can be easily stirred. The results are shown in Table 1.

<Example 8>

The same operation as in Example 1 was carried out except that the iron (III) chloride anhydrate was changed to anhydrous aluminum chloride (AlCl ₃ ) of 0.48 g (3.6 mmol). The reaction solution becomes a viscous liquid ~ semi-cured, but can be stirred. The results are shown in Table 1.

<Example 9>

The same operation as in Example 1 was carried out, except that the amount of 1,3-DMA was changed to 23.4 g (142.4 mmol), and the amount of the iron (III) chloride anhydrate was changed to 0.94 g (5.8 mmol). . The reaction solution is liquid and can be easily stirred. The results are shown in Table 1.

<Example 10>

The amount of iron (III) chloride anhydrate was used in addition to 1,3-DMA using a mixed raw material containing 1,3-DMA 20.3 g (123.7 mmol) and DMA-mBr 9.07 g (37.3 mmol). The same operation as in Example 1 was carried out except that the change was 1.06 g (6.5 mTorr). The reaction solution is liquid and can be easily stirred. The results are shown in Table 1.

<Example 11>

The amount of iron (III) chloride anhydrate was used in addition to 1,3-DMA using a mixed raw material containing 1,3-DMA 17.2 g (104.6 mmol) and DMA-mBr 7.64 g (31.4 mmol). Changed to 0.89g (5.5 The same operation as in Example 1 was carried out except that it was a millimolar. The reaction solution is liquid and can be easily stirred. The results are shown in Table 1.

<Comparative Example 1>

The same operation as in Example 1 was carried out, except that the amount of 1,3-DMA was changed to 12.8 g (77.9 mmol), and the amount of the iron (III) chloride anhydrate was changed to 0.51 g (3.1 mmol). . The reaction liquid was solidified for 1 hour after the completion of the dropwise drop of bromine to make it impossible to stir. The results are shown in Table 2.

<Comparative Example 2>

In a 100 ml three-necked flask equipped with a stirrer, a thermometer, and a Dimroth cooling tube, 1,3-DMA 15.0 g (91.3 mmol) and iron(III) chloride anhydrate 0.59 g (3.6 mmol) were charged. Ear), 60.0 g of dichloromethane (CH ₂ Cl ₂ ), was subjected to nitrogen substitution. Then, stirring was carried out while 25 g of bromine (156.4 mmol) was dropped by dropping the funnel. At this time, the flask was cooled in a water bath while adjusting to maintain the internal temperature at 20 to 25 ° C, and bromine was dropped for 30 to 60 minutes. After the completion of the dropwise addition, the mixture was aged at 20 to 25 ° C for 2 hours, and then water was added thereto to neutralize the dichloromethane phase obtained by decantation, and a small amount of residual bromine was reduced and washed with water. The methylene chloride phase was quantified using internal standard gas chromatography. The reaction solution is liquid and can be easily stirred. The results are shown in Table 2.

<Comparative Example 3>

In addition to changing the amount of 1,3-DMA to 10.0 g (60.9 mmol), the amount of iron (III) chloride anhydrate was changed to 0.79 g (4.9 mmol). The same operation as in Comparative Example 2 was carried out except that the amount of dichloromethane was changed to 40.0 g and the reaction time was changed to 5 hours. The reaction solution is liquid and can be easily stirred. The results are shown in Table 2.

<Comparative Example 4>

In addition to changing the amount of 1,3-DMA to 10.0 g (60.9 mmol), the iron(III) chloride anhydrate was changed to 0.16 g (1.2 mmol) of anhydrous aluminum chloride, and the amount of dichloromethane was changed to The same operation as in Comparative Example 2 was carried out except that 40.0 g and the reaction time were changed to 5 hours. The reaction solution is liquid and can be easily stirred. The results are shown in Table 2.

<Comparative Example 5>

In addition to the substitution of 1,3-DMA, 1-ETA 12.8g (77.9 mmol) was used, and the amount of the iron (III) anhydrate was changed to 0.51 g (3.1 mmol), and the amount of dichloromethane was changed to The same operation as in Comparative Example 2 was carried out except for 51.2 g. The reaction solution is liquid and can be easily stirred. The results are shown in Table 2.

<Comparative Example 6>

In addition to changing the amount of 1,3-DMA to 13.0 g (79.1 mmol), the amount of iron (III) chloride anhydrate was changed to 1.02 g (6.3 mmol), and n-heptane was used instead of dichloromethane. The same operation as in Comparative Example 2 was carried out except that (n-Hep) was 6.5 g. The reaction solution is liquid and can be easily stirred. The results are shown in Table 2.

<Comparative Example 7>

A three-necked flask of 100 ml equipped with a stirrer, a thermometer, and a Dairy cooling tube was charged with 1,3-dimethyladamantane (1,3-DMA) 8.3 g (50.5 mmol) to carry out nitrogen substitution. Then, boron tribromide (BBr ₃ ) 3.1 g (12.4 mmol) and aluminum bromide (AlBr ₃ ) 2.5 mg (0.01 mmol) were added. The same operation as in Example 1 was carried out except for the bromine dropping step. The reaction solution is liquid and can be easily stirred. The results are shown in Table 2.

<Comparative Example 8>

The same operation as in Example 1 was carried out except that the amount of 1,3-DMA was changed to 14.3 g (87.2 mmol), and the amount of the iron (III) anhydrate was changed to 0.55 g (3.4 mmol). . The reaction liquid was solidified for 1 hour after the completion of the dropwise drop of bromine to make it impossible to stir. The results are shown in Table 2.

<Comparative Example 9>

The same operation as in Example 1 was carried out, except that the amount of 1,3-DMA was changed to 28.5 g (173.6 mmol), and the amount of the iron (III) chloride anhydrate was changed to 1.13 g (7.0 mmol). . The reaction solution is liquid and can be easily stirred. The results are shown in Table 2.

<Comparative Example 10>

In addition to replacing 1,3-DMA, use 1,3-DMA 15.4g (93.5 Mixing material of millimolar) and DMA-mBr 30.7g (126.2 millimolar), the amount of iron (III) anhydrate was changed to 1.43 g (8.8 mmol), and the amount of bromine was changed to 10.2 g ( The same operation as in Example 1 was carried out except that 64.0 millimoles. The reaction solution is liquid and can be easily stirred. The results are shown in Table 2.

<Comparative Example 11>

The amount of iron (III) chloride anhydrate was used in addition to 1,3-DMA using a mixed raw material containing 1,3-DMA 13.9 g (84.5 mmol) and DMA-mBr 1.4 g (5.7 mmol). The same operation as in Example 1 was carried out except that it was changed to 0.60 g (3.7 mTorr). After 1 hour passed at the end of the bromine drop, the mixture was solidified so as not to be stirred. The results are shown in Table 2.

<Comparative Example 12>

The amount of iron (III) ferric chloride was used in addition to 1,3-DMA using a mixed raw material containing 1,3-DMA 27.4 g (167.0 mmol) and DMA-mBr 45.9 g (188.8 mmol). The same operation as in Example 1 was carried out except that the amount was changed to 2.31 g (14.2 mmol) and the amount of bromine was changed to 23.2 g (145.0 mmol). The reaction solution is liquid and can be easily stirred. The results are shown in Table 2.

<Comparative Example 13>

In addition to replacing 1,3-DMA, a mixed raw material containing 1,3-DMA 24.8 (151.1 mmol) and DMA-mBr 11.3 g (46.5 mmol) was used. The same operation as in Example 1 was carried out except that the amount of the iron (III) chloride anhydrate was changed to 1.32 g (8.1 mmol). The reaction solution is liquid and can be easily stirred. The results are shown in Table 2.

From the above results, it is understood that the conversion ratio of the alkyl adamantane of the raw material can be improved by the method of the embodiment, and the production rate of the bromine isomers can be reduced. Further, even when compared with the case of using a solvent (Comparative Examples 2 to 6), the conversion ratio of the alkyl amantadine of the same or more and the production ratio of the bromine isomers of the same or less can be obtained. Therefore, according to the method of the embodiment, it is possible to obtain a desired bromoalkyladamantane in a state where the amount of impurities is small and the efficiency is good without using a harmful substance such as a halogenated hydrocarbon as a solvent. Further, the amount of bromine added can be relatively small, so that it is not necessary to recover excess bromine remaining after the reaction.

Claims (8)

A method for producing a bromoalkyladamantane, which comprises reacting an alkyladamantane with bromine, wherein the reaction is carried out in the absence of a solvent and in the presence of a Lewis acid catalyst, and the alkyl adamantane has a melting point of 50 Below °C, the supply amount of the alkyladamantane in the reactor (a mole) and the supply amount of bromine (b mole) satisfy the following conditions, 1 ≦ b / a ≦ 1.75. The method for producing a bromoalkyladamantane according to the first aspect of the invention, wherein the Lewis acid catalyst is at least one selected from the group consisting of an iron halide and an aluminum halide, and the Lewis acid catalyst is used in an amount relative to the aforementioned alkyl gold The supply amount of the alkane is in the range of 0.01 to 0.20 times the molar amount. A method for producing a bromoalkyladamantane, which is a reaction of an alkyl adamantane and a bridgehead carbon atom of the alkyl adamantane with a brominated monobromoalkyladamantane and bromine. The solvent is used in the presence of a Lewis acid catalyst, and the alkyl adamantane has a melting point of 50 ° C or less, and the amount of alkyl adamantane supplied to the reactor (a mole) or monobromoalkyladamantane The supply amount (c mole) and the supply amount of bromine (b mole) satisfy the following conditions, 1 ≦ b / (a + c / 2) ≦ 1.75. For example, the manufacturer of bromoalkyladamantane in the third paragraph of the patent application scope The method wherein the Lewis acid catalyst is at least one selected from the group consisting of an iron halide and an aluminum halide, and the Lewis acid catalyst is used in an amount relative to the supply amount of the alkyl adamantane and the supply amount of the monobromoalkyladamantane. The total is 0.01 to 0.20 times the range of moles. The method for producing a bromoalkyladamantane according to any one of claims 1 to 4, wherein the alkyladamantane is a dialkyladamantane. The method for producing a bromoalkyladamantane according to any one of claims 1 to 4, wherein the alkyladamantane is a monoalkyladamantane. The method for producing a bromoalkyladamantane according to any one of claims 1 to 6, wherein the reaction temperature is in the range of not less than the melting point of the alkyladamantane and not more than 58 °C. The method for producing a bromoalkyladamantane according to any one of claims 3 to 7, further comprising separating the monobromoalkyladamantane from the bromoalkyladamantane obtained by the foregoing reaction, the single The bromoalkyladamantane is recycled in the aforementioned reactor.