JP2011201787A - 2,5-diaminomethyl-bicyclo[2,2,1]heptane and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide highly pure 2,5-diaminomethyl-bicyclo[2,2,1]heptane substantially free of isomers, and a method for producing the same.SOLUTION: The 2,5-diaminomethyl-bicyclo[2,2,1]heptane represented by formula (I) or (II) having purity of ≥95% when analyzed by gas chromatography is produced by: protecting amino groups in individual compounds included in an isomer mixture with protective groups; separating the isomers; and deprotecting the protective groups in the separated isomers.

Description

  The present invention relates to high-purity 2,5-diaminomethyl-bicyclo [2,2,1] heptane and a method for producing the same.

  2,5 (or 6) -diaminomethyl-bicyclo [2,2,1] heptane (hereinafter also referred to as “NBDA”) is a monomer such as polyimide and polyamide, and a raw material such as epoxy resin, bismaleimide and diisocyanate. Or a diamine compound extremely useful as a curing agent thereof. In addition, it is known that a polyimide having a good light transmittance (highly colorless and transparent) can be obtained by using this NBDA as a raw material (see, for example, Patent Documents 1 and 2).

  NBDA has conventionally been prepared by adding hydrogen cyanide to bicyclo [2,2,1] -5-heptene-2-carbonitrile in the presence of a palladium catalyst and triphenyl phosphite or a zerovalent nickel complex catalyst to form a dicyano compound. Then, it is manufactured by catalytic hydrogenation (see, for example, Patent Documents 3 and 4). The NBDA thus produced has 2,5-diaminomethyl-bicyclo [2,2,1] heptane as isomers having different aminomethyl group substitution positions in the bicyclo [2,2,1] heptane ring. (Hereinafter also referred to as “2,5-NBDA”) and 2,6-diaminomethyl-bicyclo [2,2,1] heptane (hereinafter also referred to as “2,6-NBDA”).

  These isomers are known to be very difficult to separate by ordinary separation means such as distillation. Furthermore, optical isomers also exist in each of 2,5-NBDA and 2,6-NBDA. For this reason, NBDA produced as described above is an isomer mixture containing four types of isomers that are difficult to separate by general separation means.

  As a method of separating the four isomers contained in NBDA, the difference in melting point of each isomer is used, and fractionated into fractions rich in each isomer while gradually raising the temperature of the solidified NBDA. Is disclosed (see, for example, Patent Document 5).

Japanese Patent Laid-Open No. 10-7906 International Publication No. 1998/029471 Japanese Patent No. 2713612 JP 2002-69043 A International Publication No. 2002/010253

  According to the isomer separation method disclosed in Patent Document 5, it was possible to control to some extent the amount ratio of isomers contained in each fraction. However, it has been extremely difficult to separate and purify a high-purity compound substantially free from other isomers.

  The present invention has been made in view of such problems of the prior art, and the object of the present invention is high-purity 2,5-diaminomethyl-bicyclo [2,2,1] heptane, and It is in providing the manufacturing method.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have protected the amino group of each compound contained in the isomer mixture of diaminomethyl-bicyclo [2,2,1] heptane as a raw material with a protecting group. Later, it was found that the above-mentioned problems could be achieved by separating the isomers and then deprotecting the protecting groups of the separated isomers, and the present invention was completed.

  That is, according to the present invention, the following methods for producing 2,5-diaminomethyl-bicyclo [2,2,1] heptane and 2,5-diaminomethyl-bicyclo [2,2,1] heptane are provided. Is done.

  [1] 2,5-diaminomethyl-bicyclo [2,2,1] heptane represented by the following formula (I) or (II) and having a purity analyzed by gas chromatography of 95% or more.

  [2] Diamino containing a compound represented by the following formula (I), a compound represented by the following formula (II), a compound represented by the following formula (III), and a compound represented by the following formula (IV) After protecting the amino group of each compound contained in the isomer mixture of methyl-bicyclo [2,2,1] heptane with a protecting group, isomers derived from the compound represented by the following formula (I) or (II) Gas chromatography represented by the following formula (I) or (II), which comprises separating the product by a separation operation including crystallization and solid-liquid separation, and then deprotecting the protecting group of the separated isomer A method for producing 2,5-diaminomethyl-bicyclo [2,2,1] heptane having a purity analyzed by chromatography of 95% or more.

  [3] The production method according to [2], wherein the protective group is a phthalimide group, a t-butyloxycarbonyl group, or a benzyloxycarbonyl group.

  The 2,5-diaminomethyl-bicyclo [2,2,1] heptane of the present invention is a high-purity compound that has a purity of 95% or more analyzed by gas chromatography and substantially does not contain an isomer, As a raw material for various resin materials and chemical products, it is particularly useful as a raw material for forming a polyimide film used as a constituent material for electronic parts.

  According to the production method of the present invention, high-purity 2,5-diaminomethyl-bicyclo [2,2,1] heptane having a purity analyzed by gas chromatography of 95% or more and substantially free of isomers Can be produced by a simple operation that can be applied industrially.

2 is a ¹³ C-NMR chart of 2,5-diexo-bisphthalimidomethyl-bicyclo [2,2,1] heptane obtained in Example 1. FIG. 2 is a ¹³ C-NMR chart of 2,5-diexo-diaminomethyl-bicyclo [2,2,1] heptane obtained in Example 1. FIG. It is a gas chromatography (GC) chart of diaminomethyl-bicyclo [2,2,1] heptane as a raw material. 2 is a gas chromatography (GC) chart of 2,5-diexo-diaminomethyl-bicyclo [2,2,1] heptane obtained in Example 1. FIG. 2 is a ¹³ C-NMR chart of 2-endo-5-exo-bisphthalimidomethyl-bicyclo [2,2,1] heptane obtained in Example 2. FIG. 2 is a ¹³ C-NMR chart of 2-endo-5-exo-diaminomethyl-bicyclo [2,2,1] heptane obtained in Example 2. FIG. 2 is a gas chromatography (GC) chart of 2-endo-5-exo-diaminomethyl-bicyclo [2,2,1] heptane obtained in Example 2. FIG.

  Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments.

[1] 2,5-Diaminomethyl-bicyclo [2,2,1] heptane:
2,5-Diaminomethyl-bicyclo [2,2,1] heptane (hereinafter also referred to as “2,5-NBDA”) of the present invention is a diamine compound represented by the following formula (I) or (II). is there. The diamine compound represented by the following formula (I) is 2,5-diexo-diaminomethyl-bicyclo [2,2,1] heptane (hereinafter also referred to as “2,5-diexo-NBDA”). . Further, the diamine compound represented by the following formula (II) is 2-endo-5-exo-diaminomethyl-bicyclo [2,2,1] heptane (hereinafter referred to as “2-endo-5-exo-NBDA”). It is noted).

  The 2,5-diexo-NBDA represented by the formula (I) and the 2-endo-5-exo-NBDA represented by the formula (II) are substantially free of other isomers. However, it is highly pure. More specifically, the purity of 2,5-diexo-NBDA and 2-endo-5-exo-NBDA calculated based on the area of the chart obtained by analysis by gas chromatography (GC) is both It is 95% or more, preferably 97.0% or more, more preferably 99.0% or more, and particularly preferably 100%.

  2,5-NBDA of the present invention is an unprecedented high-purity diamine compound that is substantially free of other isomers. For this reason, it is expected to be used as a raw material for various resin materials and chemical products, or electric / electronic materials, optical materials, paint / adhesive materials, structural members, heat insulating materials, etc. It is useful as a raw material for forming a polyimide film used as the above.

[2] Method for producing 2,5-diaminomethyl-bicyclo [2,2,1] heptane:
The method for producing 2,5-NBDA of the present invention includes crystallization and solid-liquid separation of isomers derived from 2,5-NBDA after protecting the amino group of each compound contained in NBDA with a protecting group. It is a production method including separation by a separation operation and then deprotecting the protecting group of the separated isomer. The difference in crystallinity between compounds obtained by protecting the amino group of a compound contained in NBDA with a protecting group is larger than the difference in crystallinity between compounds before protection. That is, according to the production method of the present invention, by protecting amino groups, isomers can be separated by a separation operation including simple crystallization and solid-liquid separation that can be sufficiently put into practical use industrially. it can.

  NBDA includes 2,5-diexo-NBDA represented by the following formula (I), 2-endo-5-exo-NBDA represented by the following formula (II), and 2- exo-6-exo-diaminomethyl-bicyclo [2,2,1] heptane (hereinafter also referred to as “2,6-diexo-NBDA”) and 2-endo-6-6 represented by the following formula (IV) An isomeric mixture containing exo-diaminomethyl-bicyclo [2,2,1] heptane (also referred to as “2-endo-6-exo-NBDA”).

[2-1] NBDA:
As NBDA which is a mixture of isomers as a raw material, those produced according to a conventionally known method can be used. Specifically, hydrogen cyanide is added to bicyclo [2,2,1] -5-heptene-2-carbonitrile in the presence of a palladium catalyst and triphenyl phosphite or a zero-valent nickel complex catalyst to form a dicyano compound. After that, those produced by catalytic hydrogenation can be used. As a commercially available product, there is a trade name “NBDA” manufactured by Mitsui Chemicals. These NBDAs are typically about 26% by weight of 2,5-diexo-NBDA, about 36% by weight of 2-endo-5-exo-NBDA, about 20% by weight of 2,6-diexo-NBDA, and 2-endo-6-exo-NBDA is contained at a ratio of about 18% by mass.

[2-2] Protection of amino group:
First, the amino group of each compound contained in NBDA is protected with a protecting group. The kind of the protecting group is not particularly limited as long as it is a protecting group capable of protecting the primary amino group. However, from the viewpoint of the handleability of reagents and the separability when separating protected compounds (isomers) based on their crystallinity differences, phthalimide groups, t-butyloxycarbonyl groups (t-BOC) Group) or a benzyloxycarbonyl group (Z-group) is preferable. In addition, when the protecting group of the amino group is a phthalimide group, the difference in crystallinity between the protected isomers increases, so that it becomes easier to separate the isomers by crystallization and solid-liquid separation. Is preferable.

[2-3] Isomeric separation:
Next, among isomers whose amino group is protected by a protecting group, isomers derived from 2,5-diexo-NBDA and 2-endo-5-exo-NBDA are separated including crystallization and solid-liquid separation. Separate by operation. Taking the case where the type of protecting group is a phthalimide group, a t-BOC group, and a Z-group as examples, the following formulas (I-1) to (I-3) and the following formulas (II-1) to ( The isomers represented by II-3) are separated.

  For example, isomers with amino groups protected can be separated by performing solid-liquid separation or recrystallization using various solvents. At this time, by appropriately selecting and setting the type and temperature of the solvent to be used, a fraction containing substantially only an isomer derived from 2,5-diexo-NBDA, or 2-endo-5-exo- A fraction containing substantially only the isomer derived from NBDA can be obtained.

[2-4] Deprotection:
The desired 2,5-diexo-NBDA and 2-endo-5-exo-NBDA can be obtained by deprotecting the protecting groups of the separated isomers. The protecting group can be deprotected according to a conventionally known method depending on the kind of the protecting group. For example, when the protecting group is a phthalimide group, it can be deprotected by treatment with hydrazine or the like. When the protecting group is a t-BOC group, it can be deprotected by treatment with trifluoroacetic acid or the like. Further, when the protecting group is a Z-group, it can be deprotected by hydrogenation in the presence of a palladium catalyst.

  In addition, after deprotecting a protecting group, it is preferable to refine | purify as needed and to raise the purity of the target 2, 5- diexo-NBDA and 2-endo-5-exo-NBDA. The purification method is not particularly limited, and preferred examples include vacuum distillation, column separation, recrystallization, and the like.

  The purity of the thus obtained 2,5-diexo-NBDA and 2-endo-5-exo-NBDA analyzed by gas chromatography is 95% or more. Note that 2,5-diexo-NBDA and 2-endo-5-exo-NBDA having a purity of 100% are both liquid (oil-like) at normal temperature and normal pressure.

[2-5] Production of 2,5-NBDA:
Hereafter, the case where the kind of protecting group is a phthalimide group is mentioned as an example, and the further detail of the manufacturing method of 2, 5-NBDA is demonstrated. First, NBDA and phthalic anhydride as raw materials are dehydrated and condensed by heating in an organic solvent in the presence of a suitable catalyst such as p-toluenesulfonic acid. Specific examples of the organic solvent include toluene and DMF. The reaction is preferably performed while draining water out of the system.

[2-5-1] Production of 2,5-diexo-NBDA:
After the reaction between NBDA and phthalic anhydride is completed, the mixture is cooled to room temperature (25 ° C.), and the precipitated crystals are collected by filtration. The obtained crystals are preferably recrystallized using an appropriate organic solvent or purified by a sludge treatment in which a slurry dispersed in the organic solvent is heated. Specific examples of the organic solvent used for the recrystallization and sludge treatment include toluene, acetonitrile, xylene, methyl cellosolve, ethyl acetate and the like. The isomer represented by the formula (I-1) can be obtained by performing purification by recrystallization and / or sludge treatment preferably twice or more.

  Next, when the isomer represented by the formula (I-1) is reacted with hydrazine monohydrate under a heating condition in a solvent such as isopropyl alcohol, methanol, methyl cellosolve, etc., 2,5-diexo- NBDA phthalazinedione salt precipitates in the reaction system. 2,5-diexo-NBDA is obtained by treating the phthalazinedione salt of 2,5-diexo-NBDA with an acid such as hydrochloric acid and then neutralizing it with a base such as sodium hydroxide. The crude product can be obtained. Then, if it refine | purifies by extraction by an organic solvent, distillation under reduced pressure, etc., the target highly purified 2, 5- diexo-NBDA can be obtained.

[2-5-2] Production of 2-endo-5-exo-NBDA:
After the reaction between NBDA and phthalic anhydride is completed, the mixture is cooled to room temperature (25 ° C.), and the precipitated crystals are separated by filtration to obtain a filtrate. The obtained filtrate is gradually poured into water, and the precipitated crystals are collected by filtration. The obtained crystals are dried and then dissolved in an organic solvent heated to around 100 ° C. As the organic solvent, toluene, xylene, mesitylene, methyl cellosolve, methyl ethyl ketone and the like can be used, and among these, toluene is preferable. A solution obtained by dissolving crystals in an organic solvent is cooled to room temperature (25 ° C.), and the precipitated crystals are separated by filtration. After concentrating the obtained filtrate under heating conditions, it is preferably cooled to 0 to 50 ° C., and the precipitated crystals are collected by filtration. By recrystallizing the obtained crystal using an organic solvent such as DMF as necessary, an isomer represented by the formula (II-1) can be obtained.

  Next, the isomer represented by the formula (II-1) is reacted with hydrazine monohydrate under a heating condition in a solvent such as isopropyl alcohol, methanol, methyl cellosolve, and the like, thereby protecting the amino group. Deprotect. After the produced phthalazinedione crystals are filtered off, the filtrate is concentrated to obtain a crude product of 2-endo-5-exo-NBDA. Then, if it refine | purifies by vacuum distillation etc., the target high purity 2-endo-5-exo-NBDA can be obtained.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

(Example 1: Production of 2,5-diexo-NBDA)
(1) Protection of amino group (phthalimidation):
In a 300 ml glass reactor equipped with a stirrer, dropping funnel, thermometer, condenser, nitrogen inlet tube, and Dean-Stark water separator, 325.9 g (2.2 mol) of phthalic anhydride, p-toluenesulfonic acid 0.8. 75 g, N, N-dimethylformamide 1250 g, and toluene 250 g were charged, and the temperature was raised to 140 ° C. with stirring in a nitrogen atmosphere. While maintaining 140 to 145 ° C. under reflux of toluene, 154.3 g (1 name: diaminomethyl-bicyclo [2,2,1] heptane (trade name: NBDA, manufactured by Mitsui Chemicals), which is a mixture of four isomers 0.0 mol) and a mixed solution of N, N-dimethylformamide 154.3 g were gradually added dropwise over 90 minutes. The water produced during the reaction was discharged out of the system by a Dean-Stark water separator by azeotropy with toluene, and toluene was returned to the system. After completion of the dropping, the temperature was maintained for 6 hours and the reaction was allowed to proceed sufficiently. Then, the mixture was allowed to cool to room temperature, and the precipitated white crystals were collected by filtration. The reaction formula for phthalimidating the amino group of NBDA is shown below.

  The obtained white crystals were analyzed by HPLC and found to be a mixture containing 83.7 area% of the main component. The yield was 97.5 g. On the other hand, when the filtrate (hereinafter referred to as “filtrate A”) was analyzed by HPLC, this filtrate A contained a very small amount of three main products and a peak that eluted at the same retention time as the white crystals. It was found that the mixture was contained.

The obtained white crystals were dispersed in 400 g of acetonitrile to form a slurry, heated in the slurry state and refluxed for 30 minutes. After cooling to room temperature, 85.0 g of white crystals were obtained. The purity (based on area area) of the resulting white crystals analyzed by HPLC was 97.3%. The obtained white crystals were dispersed in 450 g of toluene to form a slurry, heated in the slurry state and sludged at 70 ° C. for 1 hour, and then hot filtered at 60 to 65 ° C. to obtain white crystals. . The purity (based on area area) of the resulting white crystals analyzed by HPLC was 100.0%, the yield was 73.0 g, and the yield from NBDA was 17.6%. Moreover, the ¹³ C-NMR chart of the obtained white crystal is shown in FIG. From the ¹³ C-NMR chart shown in FIG. 1, the obtained white crystal is 2,5-diexo-bisphthalimidomethyl-bicyclo [2,2,1] heptane represented by the formula (I-1). There was found. ¹³ C-NMR was measured using “ECA500” (500 MHz) manufactured by JEOL Ltd. and deuterated chloroform as a solvent.

(2) Deprotection:
2,5-diexo-bisphthalimidomethyl-bicyclo obtained by repeating the above operation (1) in a 1000 ml glass reactor equipped with a stirrer, thermometer, thermometer, nitrogen inlet tube and condenser. 2,2,1] heptane 124.4 g (0.3 mol) and isopropyl alcohol 1200 g were charged and heated to 60 ° C. with stirring. While maintaining the same temperature, 90.0 g (1.8 mol) of 96% hydrazine (monohydrate) was added dropwise over 1 hour. The mixture was further stirred for 3 hours while maintaining the same temperature to complete the reaction. The completion (end point) of the reaction was confirmed by confirming the disappearance of 2,5-diexo-bisphthalimidomethyl-bicyclo [2,2,1] heptane by HPLC. After completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitated phthalazine dione salt of 2,5-diexo-NBDA (hereinafter simply referred to as “phthalazine dione salt”) was isolated by filtration.

  The isolated phthalazinedione salt was charged into a 3000 ml glass reactor equipped with a stirrer, a thermometer, and a dropping funnel, and 340 g of water was added and stirred to form a slurry. While stirring, 840 g (3.26 mol) of a 14.2 mass% hydrogen chloride aqueous solution was added dropwise over 1 hour, and the salt was acid-decomposed to give 2,5-diexo-NBDA hydrochloride. Subsequently, 520.8 g of a 30% by mass aqueous sodium hydroxide solution was added dropwise over 1 hour to neutralize 2,5-diexo-NBDA hydrochloride, and then the solid content was filtered. The filtrate was concentrated using a rotary evaporator to give a pale yellow mass containing sodium chloride, phthalazinedione, a small amount of sodium hydroxide, and 2,5-diexo-NBDA. The reaction formula for deprotecting the phthalimide group is shown below.

To the obtained mass, 600 g of toluene was added and stirred well, and the target product, 2,5-diexo-NBDA, was dissolved in toluene. After filtering off the solid content, the filtrate was concentrated using a rotary evaporator to obtain 41.5 g of a pale yellow liquid containing a small amount of toluene. When the obtained liquid was distilled under reduced pressure at a reduced pressure of 2.8 to 3.5 kPa in an oil bath heated to 170 to 175 ° C., 30.2 g of colorless and transparent 2,5-diexo-NBDA was obtained. . The purity of 2,5-diexo-NBDA analyzed by gas chromatography was 100%, and the yield from 2,5-diexo-bisphthalimidomethyl-bicyclo [2,2,1] heptane was 65.3%. there were. Further, when the melting point was measured by DSC, it did not crystallize even at -20 ° C. FIG. 2 shows a ¹³ C-NMR chart of the obtained 2,5-diexo-NBDA. Moreover, the gas chromatography (GC) chart of NBDA which is a raw material, and the obtained 2, 5- diexo-NBDA is shown to FIG. 3 and 4, respectively. The conditions for gas chromatography are shown below.

Column type: nonpolar column, trade name “ZB-1”, manufactured by Phenomenex Co., Ltd. Column size: inner diameter × length × film thickness = 0.53 mm × 30 m × 3 μm
Carrier gas: Helium Column pressure: Constant pressure mode 20 kPa
Column temperature: 160 ° C
Sample vaporization chamber and detector temperature: 280 ° C

(Example 2: Production of 2-endo-5-exo-NBDA)
(3) Protection of amino group (phthalimidation):
The filtrate A obtained by the operation of (1) in Example 1 was dropped over 30 minutes into a glass reactor equipped with a stirrer, a dropping funnel, and a thermometer and charged with 3500 g of water, and crystals were obtained. Precipitated. The precipitated crystals were separated by filtration and dried, and then dissolved in 800 g of toluene heated to 100 ° C. The resulting solution was allowed to cool, cooled to room temperature (25 ° C.), and the resulting crystals were filtered off. Using a rotary evaporator, the filtrate was concentrated to about 400 ml. When the concentrated filtrate was allowed to cool, white crystals gradually precipitated. The solution was cooled to 50 ° C. and filtered to obtain 85.0 g of white crystals. The obtained white crystals were analyzed by HPLC and found to be a mixture containing 88.4 area% of the main component. The total amount of this mixture (white crystals) was dissolved in 420 g of N, N-dimethylformamide and recrystallized to obtain 56.0 g of white crystals. The purity of the obtained white crystals analyzed by HPLC (based on the area of the area) was 100.0%, and the yield from NBDA was 9.0%. Moreover, the ¹³ C-NMR chart of the obtained white crystal is shown in FIG. From the ¹³ C-NMR chart shown in FIG. 5, the obtained white crystals were 2-endo-5-exo-bisphthalimidomethyl-bicyclo [2,2,1] heptane represented by the formula (II-1). It turned out to be.

(4) Deprotection:
2-endo-5-exo-bisphthalimidomethyl- obtained by repeating the above operation (3) in a 1000 ml glass reactor equipped with a stirrer, thermometer, thermometer, nitrogen inlet tube and condenser. 124.4 g (0.3 mol) of bicyclo [2,2,1] heptane and 1000 g of isopropyl alcohol were charged and heated to 60 ° C. with stirring. While maintaining the same temperature, 90.1 g (1.8 mol) of 96% hydrazine (monohydrate) was added dropwise over 1 hour. The mixture was further stirred for 3 hours while maintaining the same temperature to complete the reaction. The completion (end point) of the reaction was confirmed by confirming the disappearance of 2-endo-5-exo-bisphthalimidomethyl-bicyclo [2,2,1] heptane by HPLC. After completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitated phthalazinedione was separated by filtration. Moreover, it confirmed by analyzing by gas chromatography that the target object 2-endo-5-exo-NBDA was present in the filtrate. The reaction formula for deprotecting the phthalimide group is shown below.

The filtrate was concentrated using a rotary evaporator to give 41.9 g of a pale yellow liquid containing a small amount of solvent and hydrazine. When the obtained liquid was subjected to vacuum distillation at a reduced pressure of 2.8 to 3.5 kPa in an oil bath heated to 170 to 175 ° C., 35.7 g of colorless and transparent 2-endo-5-exo-NBDA was obtained. Obtained. The purity of 2-endo-5-exo-NBDA analyzed by gas chromatography was 100%, and the yield from 2-endo-5-exo-bisphthalimidomethyl-bicyclo [2,2,1] heptane was 77%. 2%. Further, when the melting point was measured by DSC, it did not crystallize even at -20 ° C. FIG. 6 shows a ¹³ C-NMR chart of the obtained 2-endo-5-exo-NBDA. Moreover, the gas chromatography (GC) chart of obtained 2-endo-5-exo-NBDA is shown in FIG.

The 2,5-diaminomethyl-bicyclo [2,2,1] heptane of the present invention is useful as a raw material for polyimides, epoxy resins, urethane resins, polyisocyanates, and the like, and is particularly used as a constituent material for electronic components. It is suitable as a raw material for forming a polyimide film.

Claims (3)

2,5-Diaminomethyl-bicyclo [2,2,1] heptane represented by the following formula (I) or (II) and having a purity analyzed by gas chromatography of 95% or more.

Diaminomethyl-bicyclo containing a compound represented by the following formula (I), a compound represented by the following formula (II), a compound represented by the following formula (III), and a compound represented by the following formula (IV) After protecting the amino group of each compound contained in the isomer mixture of [2,2,1] heptane with a protecting group,
Separating an isomer derived from a compound represented by the following formula (I) or (II) by a separation operation including crystallization and solid-liquid separation, and then deprotecting the protecting group of the separated isomer. A method for producing 2,5-diaminomethyl-bicyclo [2,2,1] heptane represented by the following formula (I) or (II) and having a purity analyzed by gas chromatography of 95% or more.

  The production method according to claim 2, wherein the protecting group is a phthalimide group, a t-butyloxycarbonyl group, or a benzyloxycarbonyl group.

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