JP2002322120A - rac-trans-dicyclohexyl-3,3 ', 4,4'-tetracarboxylic acid, dianhydride and their preparation - Google Patents

Abstract

(57) [Abstract] (Modified) [Problem] (1S, 1 ') useful for polyimide resin raw materials
S, 3S, 3'S, 4S, 4'S) -Dicyclohexyl-3,3 ', 4,4'-tetracarboxylic dianhydride (t
rans-DCDA-2) and (1R, 1′R, 3R,
3′R, 4R, 4′R) -dicyclohexyl-3,
3 ', 4,4'-tetracarboxylic dianhydride (tran
racemate with s-DCDA-3) and its precursor (corresponding tetracarboxylic acid (trans-DCTA-
2 and trans-DCTA-3) as racemates, and methods for their preparation. A trans-DCTA-2 and a trans-DCTA-2 are provided.
The racemate of the methyl ester of DCTA-3 is hydrolyzed to give trans-DCTA-2 and trans-DCTA.
To give a racemate with -3. This racemate is dehydrated,
trans-DCDA-2 and trans-DCDA-3
To get the racemic form.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to (1S, 1 ')
S, 3S, 3 ′S, 4S, 4 ′S) -Dicyclohexyl-3,3 ′, 4,4′-tetracarboxylic acid (hereinafter tr
ans-DCTA-2) and (1
R, 1′R, 3R, 3′R, 4R, 4′R) -Dicyclohexyl-3,3 ′, 4,4′-tetracarboxylic acid (hereinafter sometimes abbreviated as trans-DCTA-3)
(Equivalent mixture) and (1S, 1 ′
S, 3S, 3'S, 4S, 4'S) -Dicyclohexyl-3,3 ', 4,4'-tetracarboxylic dianhydride (hereinafter sometimes abbreviated as trans-DCDA-2)
And (1R, 1′R, 3R, 3′R, 4R, 4′R) -dicyclohexyl-3,3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter abbreviated as trans-DCDA-3) In some cases) and its production process.

[0002]

2. Description of the Related Art Tetracarboxylic dianhydride and its precursor, tetracarboxylic acid, are very useful as a raw material for a polyimide resin having excellent heat resistance. Conversion of a benzene ring to a cyclohexane ring by hydrogen reduction is well known, and is, for example, a synthetic communication.
, 25 , 2079 (1995),
-36320, JP-A-11-189568, JP-A-11-349535, and JP-A-10-2
No. 04002, Japanese Patent Publication No. 8-30045, and the like.

When hydrogen reduction of biphenyl-3,3 ', 4,4'-tetramethyl tetracarboxylate (hereinafter sometimes abbreviated as BPTM) occurs, the product has six asymmetric carbons, Thus, ²⁶ isomers are possible. B
Dicyclohexyl-3,3 ',
Tetramethyl 4,4′-tetracarboxylate (hereinafter DC
The following is a reaction formula for producing an isomer of (TM). In the formula, Me represents a methyl group.

Embedded image

[0004] The hydrogen reduction of BPTM is described in
JP-A-215912, JP-A-8-325196, JP-A-8-325201 and the like have been reported. However, these reports do not mention any isomers. That is, without separating a mixture of a large number of hydrogen-reduced isomers, a mixture of isomers of tetracarboxylic acid is hydrolyzed to synthesize a mixture of isomers of tetracarboxylic dianhydride. I have. On the other hand, the inventor of the present invention (1S, 1'S, 3S, 3 '
S, 4S, 4'S) -Dicyclohexyl-3,3 ',
Tetramethyl 4,4′-tetracarboxylate and (1R,
For a racemate with 1′R, 3R, 3′R, 4R, 4′R) -dicyclohexyl-3,3 ′, 4,4′-tetramethyltetracarboxylate, refer to Japanese Patent Application No. 2000-19105.
A patent application has been filed as No. 1. In addition, the inventor of the present invention provides (1R, 1'S, 3R, 3'S, 4R, 4'S)-
Dicyclohexyl-3,3 ', 4,4'-tetracarboxylic acid (hereinafter sometimes abbreviated as trans-DCTA-1) and (1R, 1'S, 3R, 3'S, 4R,
4'S) -Dicyclohexyl-3,3 ', 4,4'-tetracarboxylic dianhydride (hereinafter trans-DCDA
-1 is sometimes abbreviated as -1).
Patent application No. 209479.

[0005]

SUMMARY OF THE INVENTION The present invention provides a novel tetracarboxylic acid and its dianhydride comprising not a mixture of many isomers but an equal mixture (racemate) of specific isomers. The purpose is to:

[0006]

That is, the present invention provides:
trans-DCTA-2 and trans-DCTA-3
(Equivalent mixture) and trans-D
The present invention relates to a racemate (equivalent mixture) of CDA-2 and trans-DCDA-3, and a method for producing them.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION (1S, 1 ')
S, 3S, 3 ′S, 4S, 4 ′S) -Dicyclohexyl-3,3 ′, 4,4′-tetramethyltetracarboxylate (hereinafter sometimes abbreviated as trans-DCTM-2) and (1R , 1'R, 3R, 3'R, 4R, 4'R)
-Dicyclohexyl-3,3 ', 4,4'-tetramethyl tetracarboxylate (hereinafter trans-DCTM-3
(Sometimes abbreviated as) (hereinafter tran)
abbreviated as s-DCTM-2 / 3 racemate)
Can be suitably obtained by the method described in Japanese Patent Application No. 2000-191051. That is, BPT
The product obtained by hydrogenating M (DCTM) is recrystallized to preferentially separate isomers having a cis structure,
The isomers of the structure are isomerized in methanol in the presence of an alkali metal alcoholate catalyst, and (1R, 1S, 3R, 3'S, 4R, 4'S) -3,
A trans-DCTM-2 / 3 racemate can be obtained by separating a crystal of 3 ', 4,4'-tetramethyl tetracarboxylate and separating a single crystal from the remaining methanol solution. Further, an alkali metal alcoholate catalyst is added to a reaction solution containing a product (DCTM) obtained by hydrogen reduction of BPTM (without separating an isomer having a cis structure) to be isomerized, and tran is directly transferred from the reaction solution.
The racemic s-DCTM-2 / 3 can also be separated and obtained.

The trans-DCTM-2 / 3 racemate is dissolved in a solvent and hydrolyzed in the presence of water and an acid catalyst or an alkali catalyst. Then, while adding water to the reaction system, the solvent, the desorbed methanol or By removing the methyl carboxylate and water produced by the transesterification to the outside of the reaction system, trans-DCTA-2 and trans
Racemate with DCTA-3 (hereinafter trans-DC
TA-2 / 3 racemate).

In the hydrolysis in the presence of an alkali catalyst, the solvent to be used may be any solvent capable of dissolving the above-mentioned trans-DCTM-2 / 3 racemate, such as n-butanol and n-propanol. The amount of solvent used is trans-
A sufficient amount to dissolve the racemic DCTM-2 / 3 is required, and usually 40 to 10 per 10 g of the racemic.
0 ml. Excess solvent is not required, but if the amount is too small, the reaction does not proceed or hydrolysis is incomplete. As the alkali catalyst, caustic soda, caustic potash and the like can be used.
4 to 8 equivalents per mole of / 3 racemate is preferred. 4
If it is less than the equivalent, hydrolysis may be incomplete. Usually, the hydrolysis is completed using an excess of 4 equivalents or more. The reaction is preferably carried out by refluxing for 0.5 to 10 hours, preferably for 1 to 4 hours, and then removing the solvent, desorbed methanol, and water from the reaction system while adding water to the reaction system. It is performed in. At the end of the reaction, the product is t
Although the trans-DCTA-2 / 3 racemic alkali salt is dissolved in water, if the amount of water is small, the alkali salt may precipitate. Normally, a uniform solution is obtained if the amount of water is 80 ml or more per 10 g of the alkali salt. When an acid such as concentrated hydrochloric acid is added to the solution to make it acidic,
The ns-DCTA-2 / 3 racemate precipitates. This is washed with water to obtain the desired product.

In the hydrolysis in the presence of an acid catalyst, the solvent used is, for example, acetic acid, propionic acid, etc.
-What can be transesterified as long as it dissolves the racemic DCTM-2 / 3. The amount of solvent used is t
trans-DCTM-2 / 3 is required in an amount sufficient to dissolve the racemic form, and usually the trans-DCTM
It is 20 to 100 ml per 10 g of -2/3 racemate. Excess solvent is not required, but if the amount is too small, the reaction does not proceed or hydrolysis is incomplete. As the acid catalyst, a catalytic amount of hydrochloric acid, sulfuric acid, p-toluenesulfonic acid or the like can be suitably used. The reaction is refluxed for 0.5 to 10 hours, preferably 3 to 6 hours, and then, while adding water to the reaction system, the solvent, methyl carboxylate generated by transesterification, and water are removed out of the reaction system. This is suitably performed. As the reaction proceeds, trans-DC
A racemic TA-2 / 3 precipitates. This is washed with water to obtain the desired product.

The above-mentioned racemic trans-DCTA-2 / 3 is dehydrated by dehydration using a dehydrating agent such as acetic anhydride, propionic anhydride, acetyl chloride or the like, and cyclized to obtain trans-DCDA-2 and trans-DCD.
Racemic form with A-3 (hereinafter trans-DCDA-2)
/ 3 racemate).

The amount of the dehydrating agent used is trans-D
2 to 100 equivalents per mole of racemic CTA-2 / 3,
Particularly, 30 to 80 equivalents are preferable. If it is less than 2 equivalents, the dehydration may be incomplete. Usually, it is preferable to complete the dehydration using an excess amount of 2 equivalents or more. This reaction can be suitably carried out at a reaction temperature of 40 to 60 ° C. and a reaction time of 5 to 30 hours, particularly 12 to 24 hours. If the reaction temperature of this cyclization is too high, the trans-configuration changes and may change to other isomers. Therefore, special attention must be paid to the control of the reaction temperature.

The (1S, 1'S, 3S, 3 ') of the present invention
S, 4S, 4'S) -Dicyclohexyl-3,3 ',
4,4'-tetracarboxylic acid (trans-DCTA-
The chemical formula of 2) is shown below.

Embedded image

The (1R, 1'R, 3R, 3 ') of the present invention
R, 4R, 4'R) -dicyclohexyl-3,3 ',
4,4'-tetracarboxylic acid (trans-DCTA-
The chemical formula of 3) is shown below.

Embedded image

The (1S, 1'S, 3S, 3 ') of the present invention
S, 4S, 4'S) -Dicyclohexyl-3,3 ',
4,4'-tetracarboxylic dianhydride (trans-D
The chemical formula of CDA-2) is shown below.

Embedded image

The (1R, 1'R, 3R, 3 ') of the present invention
R, 4R, 4'R) -dicyclohexyl-3,3 ',
4,4'-tetracarboxylic dianhydride (trans-D
The chemical formula of CDA-3) is shown below.

Embedded image

[0017]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

In the following examples, high performance liquid chromatography was performed using Shimadzu SCL-10A, column: Chira.
lpak AS (Daicel Chemical Industries) 0.46 cmφ,
25 cm, 20 ° C., EtOH / n-hexane (10
/ 90) and 0.5 ml / min. ^{The 1} H NMR spectrum (400 MHz) was obtained from JEOL JEOL 400
X, _{DMSO-d 6} solution was measured at 25 ° C.. ¹³ C
The NMR spectrum (100 MHz) was obtained from JEOL JEOL
400X, _{DMSO-d 6} solution was measured at 25 ° C.. FTIR spectrum is JIR-5500, JEOL
It was measured by the KBr tablet method.

Example 1 A 300 ml three-necked flask was equipped with a stirrer and a reflux condenser, and 10 g of tr was added thereto.
Ans-DCTM-2 / 3 racemate (25.1 mmol) and 50 ml of n-butanol were dissolved by heating.
To this, 64 g (161 ml) of a 10 wt% NaOH aqueous solution
Was added and refluxed for 3 hours. Thereafter, the reflux condenser was replaced with a Liebig condenser, and n-butanol, the removed methanol, and water were distilled off while adding 200 ml of water from a dropper attached to the flask. The total amount distilled off was 140 ml. The residual solution in the flask was once filtered, and the filtrate was 80 ml. When the pH was adjusted to 1 by adding 15 ml of concentrated hydrochloric acid to this aqueous solution, a white precipitate was deposited. The precipitate was filtered and washed with water until no Cl ion was detected. This was vacuum-dried at a temperature of 100 ° C. to obtain 7.13 g of trans-DCTA-2 / 3 racemate (83% yield). Elemental analysis values are as follows. C
_{16 H 22 O 8 (342.35)} : calculated values, C56.
1, H6.5, measured values were C55.9, H6.5, mp
Is 249-250 ° C., IR is ν (CO) 1701 cm
^-1 . FIG. 1 shows the ¹ H NMR spectrum and FIG.
Figure ¹³ shows the measurement results of the ¹³ C NMR spectrum.

(Example 2) Trans- obtained in Example 1
3 g of racemic DCTA-2 / 3 and 30 ml of acetic anhydride were placed in a round bottom flask and heated at 50 ° C. for 7 hours. After 5 hours in the heating, a homogeneous solution was obtained. Temperature 50
Evaporate under reduced pressure at ℃, add 30 ml of acetic anhydride to the residue and heat again at 50 ℃ for 7 hours. This heating quickly resulted in a homogeneous solution. Evaporate under reduced pressure at a temperature of 50 ° C., add 30 ml of acetic anhydride to the residue,
It was heated again at a temperature of 50 ° C. for 7 hours. At this time, a uniform solution was immediately obtained. This solution was cooled in a refrigerator, and the precipitated needle crystals were filtered and dried at 50 ° C. in vacuo.
86 g of trans-DCDA-2 / 3 racemate (69% yield) was obtained. The racemate can be further recovered by partially concentrating the filtrate. Elemental analysis values are as follows. C ₁₆
H ₁₈ O ₆ (306.32): Calculated C62.7,
H5.9, measured values are C62.1, H5.8, mp is 1.
14-116 ° C, IR has ν (CO) of 1859, 179
It was 0 cm ^-1 . FIG. 3 shows the measurement results of the ¹ H NMR spectrum and FIG. 4 shows the measurement results of the ¹³ C NMR spectrum.

Trans-DCTA-2, trans-
DCTA-3, trans-DCDA-2, trans
-Confirmation of the structure by NMR spectrum of DCDA-3
The t shown in the aforementioned Japanese Patent Application No. 2000-209479 is disclosed.
trans-DCTA-1 and trans-DCDA-
This was done by assigning each signal with reference to the NMR spectrum of No. 1. Table 1 ( ¹ HNMR spectrum) and Table 2 ( ¹³ CNMR
Spectrum).

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

The present invention is very useful (1S, 1'S, 3S, 3'S, 4
(S, 4'S) -Dicyclohexyl-3,3 ', 4,4'
-Tetracarboxylic dianhydride and (1R, 1'R, 3R,
3′R, 4R, 4′R) -dicyclohexyl-3,
Racemic with 3 ', 4,4'-tetracarboxylic dianhydride and its precursor (1S, 1'S, 3S,
3 ′S, 4S, 4 ′S) -Dicyclohexyl-3,
3 ′, 4,4′-tetracarboxylic acid and (1R, 1′R,
3R, 3'R, 4R, 4'R) -Dicyclohexyl-
Racemic with 3,3 ', 4,4'-tetracarboxylic acid,
In addition, methods for producing the same are provided.

[Brief description of the drawings]

FIG. 1 shows the trans-DC obtained in Example 1.
It is ¹ HNMR spectrum of a racemic TA-2 / 3.

FIG. 2 shows the trans-DC obtained in Example 1.
It is ¹³ CNMR spectrum of a racemic TA-2 / 3.

FIG. 3 shows trans-DC obtained in Example 2.
It is a ¹ HNMR spectrum of the DA-2/3 racemates.

FIG. 4 shows trans-DC obtained in Example 2.
It is a ¹³ CNMR spectrum of a racemic DA-2 / 3.

Claims (4)

[Claims] 1. The method according to claim 1, wherein (1S, 1'S, 3S, 3'S, 4S,
4 ′S) -Dicyclohexyl-3,3 ′, 4,4′-tetracarboxylic acid and (1R, 1′R, 3R, 3′R, 4
R, 4'R) -Dicyclohexyl-3,3 ', 4,4'
-Racemic with tetracarboxylic acid. 2. (1S, 1'S, 3S, 3'S, 4S,
4 ′S) -Dicyclohexyl-3,3 ′, 4,4′-tetracarboxylic dianhydride and (1R, 1′R, 3R, 3 ′)
R, 4R, 4'R) -dicyclohexyl-3,3 ',
Racemic with 4,4'-tetracarboxylic dianhydride. 3. The method of claim 1, wherein (1S, 1'S, 3S, 3'S, 4S,
4 ′S) -Dicyclohexyl-3,3 ′, 4,4′-tetramethyltetracarboxylate and (1R, 1′R, 3R,
3′R, 4R, 4′R) -dicyclohexyl-3,
(1S, 1 ') hydrolyzing a racemate with 3', 4,4'-tetramethyl tetracarboxylate
S, 3S, 3 ′S, 4S, 4 ′S) -Dicyclohexyl-3,3 ′, 4,4′-tetracarboxylic acid and (1R,
A process for producing a racemic form with 1′R, 3R, 3′R, 4R, 4′R) -dicyclohexyl-3,3 ′, 4,4′-tetracarboxylic acid. 4. (1S, 1'S, 3S, 3'S, 4S,
4 ′S) -Dicyclohexyl-3,3 ′, 4,4′-tetramethyltetracarboxylate and (1R, 1′R, 3R,
3′R, 4R, 4′R) -dicyclohexyl-3,
Hydrolysis of the racemate with 3 ', 4,4'-tetramethyltetracarboxylate gives (1S, 1'S, 3S, 3'
S, 4S, 4'S) -Dicyclohexyl-3,3 ',
4,4'-tetracarboxylic acid and (1R, 1'R, 3R,
3′R, 4R, 4′R) -dicyclohexyl-3,
(1S, 1'S, 3S, 3'S, 4S, 4) characterized in that a racemate with 3 ', 4,4'-tetracarboxylic acid is formed, and then the racemate is dehydrated. 'S)-
Dicyclohexyl-3,3 ′, 4,4′-tetracarboxylic dianhydride and (1R, 1′R, 3R, 3′R, 4R,
A process for producing a racemate with 4'R) -dicyclohexyl-3,3 ', 4,4'-tetracarboxylic dianhydride.