JP2003252805A - Method for producing halogenated adamantanes - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing halogenated adamantanes which are important raw materials for highly functional materials such as a heat- resistant polymer or electronic materials such as resist for semiconductors in a high yield and purity. <P>SOLUTION: The method for producing the halogenated adamantanes comprises reacting the adamantanes or low-order halogenated adamantanes and a halosulfonic acid are reacted in a state of a halosulfonate present by addition, etc., of an inorganic salt of an alkaline earth metal normal salt to a reacrional system. Thereby, the halogenated adamantanes (high-order halogenated adamantanes when the low-order halogenated adamantanes are raw materials) are produced. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a halogenated adamantane which is useful as a raw material for functional materials and electronic materials.

[0002]

2. Description of the Related Art Adamantane derivatives are compounds that are expected to be applied to highly functional materials such as heat resistant polymers and electronic materials such as semiconductor resists because they have excellent heat resistance and high transparency. is there. Among them, halogenated adamantanes, that is, one or more, preferably 2 to 4 of hydrogen atoms of an adamantane ring such as monohalogenated adamantane, dihalogenated adamantane, trihalogenated adamantane, tetrahalogenated adamantane and the like. A compound substituted with a halogen atom is important as a raw material for synthesizing various adamantane derivatives.

Conventionally, as a suitable method for producing such halogenated adamantanes, a method in which adamantane and chlorosulfonic acid are mixed at a specific ratio and reacted [Tetrah
edron Letters 31,3191-3192 (1972)] has been reported. This method is preferable because halogenated adamantanes such as dichloroadamantane and trichloroadamantane can be obtained from adamantane in a high yield.

[0004]

However, the halogenated adamantane obtained by the above method is not yet sufficient in purity and is usually colored brown or blackish brown. In order to perform these decolorizations, purification by recrystallization or column chromatography must be performed, but in recrystallization, it is often necessary to repeat several times for complete decolorization. Since only a small amount can be processed at one time, productivity is low and it takes time, which is unsuitable for producing a large amount of the target product. Such coloring is particularly remarkable when the target compound is a higher halogenated compound such as a trihalogenated adamantane having a higher degree of halogenation, and improvement has been desired.

Further, the above reaction is
There was room for improvement. That is, when obtaining a higher halogenated compound having a high degree of halogenation such as trihalogenated adamantane, the compound cannot be obtained in a sufficient yield, and particularly,
Compounds halogenated more than tetrachloroadamantane were produced in a small amount even when reacted for a long time.

Against the above background, the present invention provides a method for obtaining a target compound with high yield and high purity when halogenating the starting compound by reacting adamantane or lower adamantane with halosulfonic acid. The purpose is to provide.

[0007]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems. As a result, it is speculated that the sulfuric acid by-produced during the reaction of adamantane or lower adamantane with halosulfonic acid induces a side reaction and destabilizes the halogenation reaction. They have found that the presence of an acid salt can prevent it, and have completed the present invention.

That is, the present invention is a method for producing a halogenated adamantane, which comprises reacting an adamantane with a halosulfonic acid in the presence of a halosulfonate.

The present invention also provides a halogenated adamantane which is characterized by reacting a lower halogenated adamantane and a halosulfonic acid in the presence of a halosulfonate to produce a higher halogenated adamantane. A manufacturing method is also provided.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the adamantane which is a starting material compound is a compound having a substituent such as adamantane which is not substituted and a kind and number which do not inhibit the halogenation reaction of the adamantane ring. As a substituent, a methyl group, an ethyl group, a propyl group or the like having 1 to 4 carbon atoms
Is preferably an alkyl group, more preferably a methyl group. The number of substitutions is usually 1 to 3, and it is preferable that one is substituted at the 1-position.

The low-order halogenated adamantane is a halogenated adamantane of these adamantanes, which is lower in order than the desired halogenated adamantane, and is usually a monohalide or a dihalide. Is the target.

The halosulfonic acid used in the present invention is a compound represented by XSO ₃ H (wherein X represents halogen). Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like. Specifically, as halosulfonic acid,
Examples thereof include chlorosulfonic acid, bromosulfonic acid, and iodosulfonic acid, and chlorosulfonic acid is particularly preferable because it is easily available.

In the present invention, when the starting compound is the above-mentioned adamantane, a halogenated adamantane which is halogenated is produced, and when the starting compound is a lower halogenated adamantane, this is Higher-order halogenated adamantane that is halogenated higher than the order is produced. If the raw material compound consisting of adamantane and lower halogenated adamantane (hereinafter, these are also abbreviated as “raw material adamantane”) is adamantane, monohalogenated adamantane, dihalogenated adamantane, trihalogenated adamantane, tetrahalogen Adamantane and the like are produced. Further, in the case of methyl adamantane, monohalogenated methyl adamantane, dihalogenated methyl adamantane, trihalogenated methyl adamantane and the like are produced. Further, even when the raw material adamantane is a low-order halogenated adamantane, in these exemplified compounds, a halogenated compound having a higher degree than the raw material adamantane used is produced.

From the viewpoint that the effect of the present invention is remarkably exhibited, the halogenated adamantane to be produced is a halogenated adamantane which is halogenated at a higher order than the second order of the compound used as the raw material adamantane. Preferably. In particular, when adamantane is used as the raw material adamantane, a halogenated compound having a higher order of dihalogenated adamantane or higher, and most preferably a halogenated product of a higher order than trihalogenated adamantane. Is effective.

In the present invention, the amount of the halosulfonic acid used with respect to the adamantane is not particularly limited, but is substituted with respect to the adamantane except for the amount consumed to form the halosulfonate described below. It is preferable to use a molar amount of 2 times or more, preferably 2 to 5 times the number of halogens. When the raw material adamantane is an adamantane, if the target compound is a dihalogenated compound, it is used in an amount of 4 to 10 times the molar amount of the adamantane except the production amount of the halosulfonate. If the target compound is a trihalogenated compound, it is used in a 6 to 15-fold molar amount relative to the adamantane, and similarly, if the target compound is a tetrahalogenated compound, it is used in an 8 to 20-fold molar amount relative to the adamantane It is generally used in a quantity.

The mixing of the adamantane and the halosulfonic acid may be carried out by any method, but it is usually preferable to add the halosulfonic acid dropwise to the adamantane or an organic solution thereof.

The reaction between the adamantane and the halosulfonic acid may or may not use an organic solvent.
When an organic solvent is used, it can be used without limitation as long as it does not inhibit the halogenation reaction. Specifically, it is preferable to use a chlorine-based solvent such as dichloromethane or 1,2-dichloroethane.

The present invention is most characterized by the presence of a halosulfonic acid salt in the reaction system when the above-mentioned starting adamantane is reacted with halosulfonic acid to halogenate the starting adamantane. It is presumed that the halosulfonate has some influence on the by-produced sulfuric acid and weakens its oxidative reactivity. Therefore, in the present invention, the purity of the halogenated adamantane to be produced is improved, and coloring etc. It will not occur. Further, the reactivity is also improved, and in particular, in the case of producing a compound having a higher degree of halogenation such as trihalogenated adamantane and further tetrahalogenated adamantane, the reaction can be carried out in a high yield. Become.

The halosulfonic acid salt is present in the reaction system not only at the start of the reaction but also during the reaction, that is,
It may be after the point of time when the sulfuric acid concentration in the reaction solution is so high that it adversely affects the halogenation reaction.

Here, in the method of allowing the halosulfonic acid salt to be present in the reaction system, the halosulfonic acid salt may be directly added to the reaction system, but a part of the halosulfonic acid as a reaction reagent may be added before or during the reaction. It is efficient to change the salt to the above salt and to be present. As a method for converting halosulfonic acid into a salt, a known salt formation method can be adopted without limitation. For example, the most general-purpose salt formation method is a method of adding an alkali such as sodium hydroxide or potassium hydroxide. You may implement. In this case, water is by-produced together with the salt, and the water reacts with the halosulfonic acid to consume the halosulfonic acid excessively. Therefore, in the present invention, as described in detail below, an inorganic salt of a weaker acid than the halosulfonic acid ( Hereinafter, these are simply abbreviated as "inorganic salt"), and it is preferable to form a halosulfonate. It should be noted that an inorganic salt having a stronger acid than halosulfonic acid does not form a salt even when mixed with halosulfonic acid, and the object of the present invention is hardly achieved.

As the inorganic salt of a weaker acid than the above halosulfonic acid, known ones can be used without limitation. Specifically, sodium chloride, potassium chloride, sodium sulfate,
Alkali metal normal salts such as sodium carbonate, potassium carbonate, sodium nitrate, sodium phosphate; alkaline earth metal normal salts such as magnesium chloride, calcium chloride, magnesium sulfate, barium sulfate, calcium carbonate; copper chloride, copper sulfate, zinc chloride , Transition metal normal salts such as zinc sulfate, iron chloride and iron sulfate; inorganic normal salts such as ammonium chloride and ammonium normal salts such as ammonium chloride and ammonium sulfate. Also,
As the inorganic salt, although there is a problem that water is generated as in the case of the above-mentioned alkali, an inorganic hydroxide salt such as copper chloride hydroxide or lead chloride hydroxide can be sufficiently used. Further, as the inorganic salt, hydrogen salts such as sodium hydrogen carbonate and sodium dihydrogen phosphate can also be used. Among the above-mentioned inorganic salts, it is preferable to use an inorganic normal salt, in addition to good cost and operability, an alkali metal normal salt from the viewpoint of easy reaction with halosulfonic acid, and in particular, an alkali metal sulfate or an alkali metal halogen. It is preferable to use a compound.

Many of the above-mentioned inorganic salts are volatile acids (for example, HCl when a salt of hydrochloric acid is used as an inorganic salt) and gas when they react with halosulfonic acid to form a halosulfonic acid salt. Since an acidic oxide (for example, CO ₂ when a carbonate is used as an inorganic salt) is generated, when such an inorganic salt is used, the liquid foams at the time of addition and generally causes heat generation or heat absorption, and the temperature fluctuates. Therefore, the halogenation reaction may become unstable. Therefore, when an inorganic salt having such a property is used, it is preferable that the inorganic salt is not added during the reaction but is added before the start of the reaction to previously form the halosulfonate.

On the other hand, in the case of a sulfate such as sodium sulfate or a nitrate such as potassium nitrate, which gently reacts with halosulfonic acid, it may be added during the reaction.
However, even if the addition time of the inorganic salt is too late, it is difficult to sufficiently exert the effects of the present invention, so the inorganic salt is added at least before the halogenation reaction at the final stage begins to actively occur. Preferably. Therefore, for example, if the raw material adamantane is an adamantane and the target compound is a dihalogenated adamantane, it is preferable to add it before the crude adamantane charged is halogenated to a monohalogenated adamantane. become. If the target compound is a further halogenated trihalogenated adamantane, the inorganic salt is
It is effective to add it until the dihalogenation reaction is almost completed and the trihalogenation reaction is actively occurring.

The progress of the halogenation reaction may be confirmed by sampling the reaction solution with time and analyzing it by gas chromatography or the like. When adamantane is used as the raw material adamantane and a halogenated adamantane having a higher degree of halogenation than a dihalogenated adamantane is produced without using an organic solvent, the reaction liquid should be described in detail below. The degree of progress of halogenation can be easily confirmed by observing the appearance.

That is, halosulfonic acid has a peculiar solubility property in which the solubility of adamantanes and dihalogenated adamantanes is extremely low near room temperature, whereas the solubility of monohalogenated adamantane is large at room temperature. . Therefore, when the reaction is carried out using halosulfonic acid, which is a reaction reagent, without using an organic solvent, the reaction solution is in a suspended state at the beginning of the reaction, but halogenation proceeds and monohalogenated adamantane is produced. When it comes in, it is dissolved in halosulfonic acid, and the reaction solution changes to a transparent homogeneous solution. Therefore, by observing this time, it is possible to confirm the time when the crude adamantane was halogenated to the monohalogenated adamantane.

Also, confirm that the time when the dihalogenation reaction is almost completed is the time when the reaction liquid becomes suspended again because a large amount of dihalogenated adamantane insoluble in halosulfonic acid is produced at 50 ° C. or lower. You can

The method of adding these inorganic salts is not particularly limited and may be appropriately performed. In the case of adding at the start of the reaction, the adamantane and the inorganic salt may be mixed in advance, and the halosulfonic acid may be mixed therein by a method such as the above-mentioned dropping. Further, when it is added during the reaction, it may be added to the reaction solution at a desired time, once or gradually. The inorganic salt may be first mixed with halosulfonic acid to form a halosulfonic acid salt, and then mixed with atamantanes as a mixture with the remaining halosulfonic acid. In the present invention, the amount of the halosulfonic acid salt present is not particularly limited, but is at least a molar amount of by-produced sulfuric acid, and preferably from an equivalent amount to 1.2 times the molar amount of the sulfuric acid. Is preferred. For example, when adamantane is used as a starting adamantane and trihalogenated adamantane is obtained, it is preferably present in an amount of 3 to 4 times the molar amount of adamantane.

In the present invention, the reaction temperature is not particularly limited, and the optimum temperature may be selected according to the method for allowing the target compound and the halosulfonate to exist.
For example, the raw material adamantane is adamantane,
If an inorganic salt is added to the reaction system at the start of the reaction,
Until the crude adamantane charged is halogenated to a monohalogenated adamantane, the reaction is carried out at 30 to 40 ° C. to prevent sublimation of the adamantane, and when the target compound is a higher halogenated compound. Then 75
It suffices to raise the temperature to -80 ° C and continue the higher-order halogenation reaction. If an inorganic salt is added during the reaction, the reaction is initially carried out at 0 to 10 ° C. in order to suppress a side reaction due to by-product sulfuric acid until the above-mentioned monohalogenated product is formed, and the inorganic salt After adding, the higher order halogenation reaction may be performed under the same temperature condition as described above.

The reaction time is not particularly limited and may be carried out until the reaction reaches a sufficient conversion rate. Usually, a sufficient conversion rate can be obtained in 8 to 24 hours.

Isolation of the produced halogenated adamantane from the reaction solution is not particularly limited, and a known isolation technique may be appropriately carried out. Usually, ice water is added to decompose halosulfonic acid, followed by extraction with an organic solvent such as chloroform, washing with water, evaporation of the solvent and drying, and if necessary, treatment with activated carbon with an organic solvent such as hexane,
It is preferable to carry out the method by drying after distilling off the solvent. The precipitate of halogenated adamantane obtained by such a method may be further highly purified by further washing with water, solvent extraction, crystallization and the like.

The equipment used for the above reaction preferably has a structure that cuts off contact with the atmosphere in order to prevent the halosulfonic acid from reacting with water to decompose and generate an acidic gas. In addition, it is preferable that the inside of the equipment is sufficiently replaced with an inert gas such as nitrogen and dried in advance, and the reaction is carried out by sealing during the reaction or ventilating an inert gas such as nitrogen.

[0032]

Industrial Applicability According to the method of the present invention, it is possible to produce halogenated adamantane having high purity and no coloration. Further, the reactivity is also improved, and the halogenated adamantane compound can be produced in high yield. In particular, the use of adamantane as the raw material adamantane, the effect is remarkable when producing a higher halogenated adamantane higher than the dihalogenated adamantane, for example, in the halogenation reaction from the conventional adamantane, almost significant Tetrachloroadamantane, which was difficult to produce in a large amount, can also be obtained in a high yield.

The halogenated adamantane obtained by the method of the present invention can be effectively used as a raw material for functional materials such as heat resistant polymers and electronic materials such as resists by forming alcohols or amine derivatives. You can

[0034]

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 Adamantane 5.0 g (0.037 mol) was added to 100 m.
It was placed in a 3-neck flask of 1 l and dried by passing nitrogen gas. Next, the temperature was cooled to 0 ° C. while connecting to a T-tube and flowing nitrogen, and chlorosulfonic acid 34.3 was used.
g (0.29 mol) was added dropwise. When the temperature of the suspended reaction liquid was raised to 10 ° C., the solution became transparent and uniform after 2 hours.

At this point, sodium sulfate was added to the reaction solution 8.
5 g (0.060 mol, 0.12 for sodium)
mol) was added, the temperature was raised to 40 ° C., and the reaction was carried out for 8 hours. The reaction solution was poured into ice water and neutralized with sodium hydroxide, followed by extraction with chloroform, solvent substitution with hexane, addition of activated carbon and filtration, evaporation of the solvent and drying to give 7.1 g.
A white solid (yield 94%) was obtained. In addition, in the above operation, when sodium sulfate was added, a slight exotherm was observed and dissolved, which suggests that sodium chlorosulfonate was formed in the reaction solution.

When the white solid was analyzed by gas chromatography and GC / MS, dichloroadamantane was 96%, and monochloroadamantane and trichloroadamantane were 2% each.

Comparative Example 1 The procedure of Example 1 was repeated except that sodium sulfate was not added when the reaction solution became transparent, and 7.0 g (yield 93%) of a solid was obtained. It was The solid was pale yellow.

The results of analysis of this solid were that dichloroadamantane was 92%, monochloroadamantane was 2%,
Trichloroadamantane was 5%.

Example 2 In the same manner as in Example 1 except that 10.6 g of potassium sulfate was used instead of sodium sulfate, 7.1 g (yield 94%) of a white solid was obtained. It was When potassium sulfate was added to the reaction solution, a slight amount of heat was generated.

The analysis result of the above white solid was that dichloroadamantane was 95% and monochloroadamantane was 3%.
%, And trichloroadamantane was 2%.

Example 3 8.6 g (0.15 mol) of sodium chloride was added to 100 m
It was placed in a 3-neck flask of 1 l and dried by passing nitrogen gas. Next, 51.7 g (0.44 mol) of chlorosulfonic acid was added dropwise while the nitrogen was flown while being connected to the T-shaped tube. After the addition, after bubbling of the mixed solution subsided, 5.0 g (0.037 mol) of adamantane was added thereto,
The temperature was raised to 35 ° C. and the reaction was carried out for 2 hours. Then, the temperature was raised to 80 ° C. and the reaction was continued for 8 hours. The reaction solution was poured into ice water and neutralized with sodium hydroxide, followed by extraction with chloroform, solvent substitution with hexane, addition of activated carbon, filtration, evaporation of the solvent and drying to obtain 8.0 g (yield 91%).
Was obtained as a white solid. In the above operation, when sodium chloride was added, heat was generated to generate hydrogen chloride gas, which suggests that sodium chlorosulfonate was formed in the reaction solution.

The analysis result of this white solid was that trichloroadamantane was 95% and dichloroadamantane was 5%.
%Met.

COMPARATIVE EXAMPLE 2 The procedure of Example 2 was repeated except that chlorosulfonic acid was not added dropwise except that sodium chloride was not added, and a 7.7 g (yield 87%) thin film was obtained. A brown solid was obtained.

As a result of analysis of this solid, trichloroadamantane was 92% and monochloroadamantane was 2%.
%, And dichloroadamantane was 6%.

Example 4 7.9 g (yield 90%) was carried out in the same manner as in Example 3, except that sodium chloride was dropped into the reaction system after the reaction solution became transparent. %) Of a white solid.

As a result of analysis of this white solid, trichloroadamantane was 96% and dichloroadamantane was 4%.
%Met.

Example 5 The procedure of Example 1 was repeated except that the chlorosulfonic acid was changed to 59.6 g (0.37 mol) of bromosulfonic acid. 9.7 g (yield 90%) of white chlorosulfonic acid was obtained. A solid was obtained.

As a result of analysis of the obtained white solid, dibromoadamantane was 95%, monobromoadamantane was 3%, and tribromoadamantane was 2%.

Example 6 In Example 3, the amount of sodium chloride was 4.3 g.
The same operation as in Example 3 was carried out except that the amount was (0.074 mol) to obtain 7.9 g (yield 90%) of a white solid.

The analysis result of this white solid was that trichloroadamantane was 94% and dichloroadamantane was 6%.
%Met.

Example 7 8.6 g (0.15 mol) of sodium chloride was added to 100 m.
It was placed in a 3-neck flask of 1 l and dried by passing nitrogen gas. Next, 87.6 g (0.74 mol) of chlorosulfonic acid was added dropwise while the nitrogen was flown while being connected to the T-shaped tube. After the addition, after bubbling of the mixed solution subsided, 5.0 g (0.037 mol) of adamantane was added thereto,
The temperature was raised to 35 ° C. and the reaction was carried out for 2 hours. Then, the temperature was raised to 80 ° C. and the reaction was continued for 8 hours, then the temperature was raised to 120 ° C. and the reaction was continued for 8 hours while stirring vigorously. The reaction solution was poured into ice water, neutralized with sodium hydroxide, then extracted with chloroform, the solvent was replaced with hexane, activated carbon was added, the mixture was filtered, the solvent was evaporated, and the mixture was dried.
2 g (yield 91%) of white solid was obtained. In the above operation, when sodium chloride was added, heat was generated to generate hydrogen chloride gas, which suggests that sodium chlorosulfonate was formed in the reaction solution.

As a result of analysis of this white solid, tetrachloroadamantane was 89% and trichloroadamantane was 10%.

Example 8 The procedure of Example 1 was repeated except that the adamantane was changed to 5.5 g of 1-methyladamantane. As a result, 7.5 g (yield 93%) of a white solid was obtained.

As a result of analysis of the obtained white solid, dichloromethyl adamantane was 95%, monochloromethyl adamantane was 3%, and trichloromethyl adamantane was 1%.

Example 9 The amount of sodium chloride used in Example 3 was 6.5 g.
(0.11 mol), and the amount of adamantane and its amount used was 6.3 g of 1-chloroadamantane (0.
The procedure of Example 3 was repeated except that the amount was changed to 037 mol) to obtain 8.1 g (yield 92%) of a white solid.

The analysis result of this white solid was that trichloroadamantane was 95% and dichloroadamantane was 5%.
%Met.

Claims (5)

[Claims] 1. An adamantane and a halosulfonic acid,
A method for producing a halogenated adamantane, which comprises reacting in the presence of a halosulfonate. 2. The method for producing a halogenated adamantane according to claim 1, wherein the adamantane is reacted with a halosulfonic acid to produce a higher halogenated adamantane higher than the dihalogenated adamantane. 3. A method for producing a halogenated adamantane, which comprises reacting a lower halogenated adamantane with a halosulfonic acid in the presence of a halosulfonate to produce a higher halogenated adamantane. 4. The halogenated adamantane according to claim 1, wherein an inorganic salt of a weaker acid than halosulfonic acid is added to the reaction system so that the halosulfonic acid salt is present. Manufacturing method. 5. The method for producing a halogenated adamantane according to any one of claims 1 to 4, wherein the inorganic salt of a weaker acid than halosulfonic acid is an alkali metal normal salt.