JPH08803B2 - Method for producing fluorine-containing phthalonitrile derivative - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to the following general formula (II):

[0002]

[Chemical 5]

(In the formula, X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom, a sulfur atom,

[0004]

[Chemical 6]

The present invention relates to a method for producing a fluorine-containing phthalonitrile derivative represented by

The fluorine-containing phthalonitrile derivative according to the present invention is useful as an intermediate raw material for optical materials, wiring board materials, photosensitive materials, liquid crystal materials and the like. In particular, it is useful as an intermediate for fluorine-containing polyimide used as an optical material and a wiring substrate material.

[0007]

2. Description of the Related Art No description is found in the literature regarding the method for producing the fluorine-containing phthalonitrile derivative represented by the above general formula (II) according to the present invention.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a fluorine-containing phthalonitrile derivative with high yield, high purity and high efficiency.

[0009]

SUMMARY OF THE INVENTION The present invention is directed to 3, 4, 5,
6-tetrafluorophthalonitrile is represented by the following general formula (I):

[0010]

[Chemical 7]

(Wherein X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom, a sulfur atom,

[0012]

Embedded image

And a nucleophilic substitution product represented by the formula (I) in the presence of a basic substance in an organic solvent.
I):

[0014]

[Chemical 9]

(Wherein X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom, a sulfur atom,

[0016]

[Chemical 10]

In the production of the fluorine-containing phthalonitrile derivative represented by (1), at least 8 mol parts of 3,4,5,6-tetrafluorophthalonitrile are used with respect to 1 mol part of the nucleophilic substitution product. A method for producing a fluorine-containing phthalonitrile derivative, which is characterized by the above.

The fluorine-containing phthalonitrile derivative represented by the general formula (II) is obtained according to the reaction route shown in the following scheme (A). However, when the reaction route shown in the following scheme (B) is followed, a by-product shown in the following general formula (III) is produced.

[0019]

[Chemical 11]

[0020]

[Chemical 12]

(However, X and Y in each scheme have the same meanings as described above.) The inventors of the present invention have shown that the compound represented by the general formula (I) is 3,4,5,6-tetra- By using a large excess of fluorophthalonitrile, it is possible to suppress the formation of the compound represented by the general formula (III) that is sequentially produced during the reaction, the target compound represented by the general formula (II) Was found to be obtained in high yield and high purity. Specifically, at the time of reaction, it is preferable to use at least 8 mol parts of 3,4,5,6-tetrafluorophthalonitrile with respect to 1 mol part of the compound represented by the general formula (I). . The amount of the upper limit is not particularly limited, but it is preferably used in the range of 8 to 50 parts by mol, particularly 15 to 30 parts by mol in view of reaction efficiency and the like. When the amount of 3,4,5,6-tetrafluorophthalonitrile used is small, the production ratio of the by-product represented by the general formula (III) mainly increases and the by-product represented by the general formula (II) increases. The yield and the purity of the fluorinated phthalonitrile derivative are reduced. When the amount used is large, the method for purifying unreacted 3,4,5,6-tetrafluorophthalonitrile becomes complicated, and
It is not preferable because it lowers the production efficiency.

The reaction is preferably carried out by dropping the solution of the above general formula (I) into a 3,4,5,6-tetrafluorophthalonitrile solution containing a basic substance. By this method, 3,4,5,6-tetrafluorophthalonitrile can always be kept in an excessive state, and the production of by-products represented by the general formula (III) can be suppressed.

The reaction temperature is preferably -5 to 150 ° C, more preferably 40 to 100 ° C. When the reaction temperature is low, the production efficiency decreases. When the temperature is high, it is difficult to control the reaction, which is not preferable.

The reaction time varies depending on the solvent used, the reaction temperature and the like, but it is usually desirable to carry out the reaction within the range of 1 to 26 hours.

In the present invention, a compound represented by the above general formula (I), which is a starting material to be reacted with 3,4,5,6-tetrafluorophthalonitrile, and the above general formula (II) obtained by the reaction, When the compound represented is specifically shown,
1,4-bis (3,4-dicyano-2,5,6-trifluorophenoxy) tetrafluorobenzene was obtained from tetrafluorohydroquinone as a starting material,
Similarly, from tetrafluoro-p-benzenedithiol, 1,4-bis (3,4-dicyano-2,5,6-
Trifluorophenylthio) tetrafluorobenzene is obtained, 4,4′-dihydroxy-2,2 ′, 3,3
From 4,5 ', 5,5', 6,6'-octafluorobiphenyl, 4,4'-bis (3,4-dicyano-2,5,6-
Trifluorophenoxy) octafluorobiphenyl is obtained, 4,4′-dimercapto-2,2 ′, 3,3
From 4,5 ', 5,5', 6,6'-octafluorobiphenyl, 4,4'-bis (3,4-dicyano-2,5,6-
Trifluorophenylthio) octafluorobiphenyl is obtained respectively.

In the present invention, the organic solvent is 3,
An organic solvent inert to 4,5,6-tetrafluorophthalonitrile, the compound represented by the general formula (I) and the compound represented by the general formula (II) which is a reaction target substance is used. For example, it is preferable to use an organic solvent such as acetonitrile, benzonitrile, diethyl ether, isopropyl ether, etc. In particular, use of acetonitrile is preferable because the reaction yield is increased.

The combined concentration of 3,4,5,6-tetrafluorophthalonitrile and the compound represented by the above general formula (I) in the solvent is 5% by weight or more and 45% by weight or less. Is preferable, and particularly 10% by weight or more and 35% by weight
It is preferably used below. If the concentration is low, the production efficiency will decrease. If the reaction is carried out at a high concentration, the reaction starting materials are not dissolved and the reaction rate decreases, which is not preferable.

The basic substance used in the present invention is not particularly limited as long as it does not inhibit this reaction, and examples thereof include alkali metal fluorides such as sodium fluoride and potassium fluoride, and calcium fluoride. It is preferable to use a fluoride of an alkaline earth metal such as, or a tertiary amine such as trimethylamine or triethylamine, and it is particularly preferable to use potassium fluoride.

After completion of the reaction, for example, as a basic substance,
When an alkali metal fluoride or an alkaline earth metal fluoride is used, the reaction solution is filtered to separate the basic substance and its salt, and the filtrate is evaporated to dryness. By removing the 4,4,5,6-tetrafluorophthalonitrile by distillation, the fluorinated phthalonitrile derivative represented by the general formula (II) can be obtained. Further, for example, when a tertiary amine is used as the basic substance, the reaction solvent is distilled off from the reaction solution, the product is dissolved in a solvent such as ethyl acetate, and the solution is washed with water. . Thereafter, the solvent and the unreacted 3,4,5,6-tetrafluorophthalonitrile are distilled off by distillation to obtain the fluorine-containing phthalonitrile derivative represented by the general formula (II). The obtained fluorinated phthalonitrile derivative can be easily purified to a high purity by a known means such as column chromatography or recrystallization.

Hereinafter, the present invention will be described more specifically by way of examples.

[0031]

【Example】

Example 1 3 equipped with a stirrer, a cooling reflux pipe, a thermometer and a dropping device
In a 00 ml four-necked flask, 4,4.0 g (0.22 mol) of 3,4,5,6-tetrafluorophthalonitrile
(Used in a 20-fold molar amount relative to tetrafluorohydroquinone), 1.4 g (0.024 mol) of potassium fluoride and 130 g of acetonitrile were added, and the reflux temperature (82 to 8) was added.
It heated to (4.5 degreeC). After that, from the dropping device, tetrafluorohydroquinone 2.0 g (0.011 mol)
Was dissolved in 20 g of acetonitrile, and the solution was added dropwise over 1 hour. Then, the mixture was further reacted at reflux temperature for 4 hours. After completion of the reaction, potassium fluoride and its salt are filtered off, the filtrate is evaporated to dryness, and unreacted 3,4,5,6-tetrafluorophthalonitrile is removed by distillation,
Crude product of 4-bis (3,4-dicyano-2,5,6-trifluorophenoxy) tetrafluorobenzene 5.9
g (relative to tetrafluorohydroquinone crude yield 99)
mol%).

The purity of the obtained compound was 95% as measured by liquid chromatography. The obtained compound was purified by column chromatography to obtain the above-mentioned fluorine-containing phthalonitrile derivative having a purity of 99%. The physical properties of the purified compound are as follows.

[0033] MS spectrum (EI): m / e 542, 361, 1
81 Example 2 Using the same apparatus as in Example 1, 33.0 g (0.17 mol) of 3,4,5,6-tetrafluorophthalonitrile
(Used in a 15-fold molar amount relative to tetrafluorohydroquinone), 1.4 g (0.024 mol) of potassium fluoride and 60 g of acetonitrile were added, and the reflux temperature (82 to 84.
Heated to 5 ° C). Then, a solution prepared by dissolving 2.0 g (0.011 mol) of tetrafluorohydroquinone in 20 g of acetonitrile was dropped from the dropping device in 1 hour. Then, the mixture was further reacted at reflux temperature for 4 hours. After completion of the reaction, potassium fluoride and its salt are filtered off, the filtrate is evaporated to dryness, and unreacted 3,4,5,6-tetrafluorophthalonitrile is removed by distillation to give 1,4-
5.6 g of a crude product of bis (3,4-dicyano-2,5,6-trifluorophenoxy) tetrafluorobenzene was obtained (relative to tetrafluorohydroquinone crude yield 94mo).
1%).

The purity of the obtained compound was 93% as measured by liquid chromatography. The obtained compound was purified by column chromatography to obtain the above-mentioned fluorine-containing phthalonitrile derivative having a purity of 99%.

Example 3 Using the same apparatus as in Example 1, 66.0 g (0.33 mol) of 3,4,5,6-tetrafluorophthalonitrile was used.
(30 moles used with respect to tetrafluorohydroquinone), 1.4 g (0.024 mol) of potassium fluoride and 400 g of acetonitrile were added and heated to 50 ° C.
After that, 20 g of tetrafluorohydroquinone (2.0 g (0.011 mol)) was added from a dropping device to acetonitrile.
The solution dissolved in was added dropwise over 1 hour. Then 5 more
The reaction was carried out at 0 ° C for 4 hours. After completion of the reaction, potassium fluoride and its salt are filtered off, the filtrate is evaporated to dryness, and unreacted 3,4,5,6-tetrafluorophthalonitrile is removed by distillation to give 1,4- 5.6 g of a crude product of bis (3,4-dicyano-2,5,6-trifluorophenoxy) tetrafluorobenzene was obtained (relative yield of tetrafluorohydroquinone: 94 mol%).

The purity of the obtained compound was 97% as measured by liquid chromatography. The obtained compound was purified by column chromatography to obtain the above-mentioned fluorine-containing phthalonitrile derivative having a purity of 99%.

Example 4 Using the same apparatus as in Example 1, 37.4 g (0.19 mol) of 3,4,5,6-tetrafluorophthalonitrile was used.
(20 with respect to tetrafluoro-p-benzenedithiol
Double mole used), potassium fluoride 1.2g (0.021m
ol) and 100 g of acetonitrile are added, and the reflux temperature (8
2 to 84.5 ° C). Then from the dropping device,
Tetrafluoro-p-benzenedithiol 2.0g
A solution of (0.009 mol) dissolved in 20 g of acetonitrile was added dropwise over 1 hour. Then, the mixture was further reacted at reflux temperature for 4 hours. After completion of the reaction, potassium fluoride and its salt were filtered off and the filtrate was evaporated to dryness.
By removing 4,5,6-tetrafluorophthalonitrile by distillation, 1,4-bis (3,4-dicyano-
5.0 g of a crude product of 2,5,6-trifluorophenylthio) tetrafluorobenzene was obtained (crude yield based on tetrafluoro-p-benzenedithiol: 93 mol%).

The purity of the obtained compound was 94% as measured by liquid chromatography. The obtained compound was purified by column chromatography to obtain the above-mentioned fluorine-containing phthalonitrile derivative having a purity of 99%. The physical properties of the purified compound are as follows.

Elemental analysis value (C22F10N4S2) C N F S calculated value (%) 46.00 9.75 33.08 11.16 Actual value (%) 45.65 10.18 32.68 10.76 MS spectrum ( EI): m / e 574,393 Example 5 Using the same apparatus as in Example 1, 24.2 g (0.12 mol) of 3,4,5,6-tetrafluorophthalonitrile.
(4,4'-dihydroxy-2,2 ', 3,3', 5
2 for 5 ', 6,6'-octafluorobiphenyl
0 times mole used), potassium fluoride 0.77 g (0.01
(3 mol) and 80 g of acetonitrile were added, and the mixture was heated to the reflux temperature (82-84.5 ° C). Then, from the dropping device, 4,4'-dihydroxy-2,2 ', 3,3',
5,5 ', 6,6'-octafluorobiphenyl 2.0
A solution prepared by dissolving g (0.006 mol) in 20 g of acetonitrile was added dropwise over 1 hour. Then, the mixture was further reacted at reflux temperature for 4 hours. After completion of the reaction, potassium fluoride and its salt were filtered off and the filtrate was evaporated to dryness.
4.1 g of a crude product of 4,4′-bis (3,4-dicyano-2,5,6-trifluorophenoxy) octafluorobiphenyl was obtained by removing 4,5,6-tetrafluorophthalonitrile by distillation. Was obtained (vs. 4,4'-dihydroxy-2,2 ', 3,3', 5,5 ', 6,6'
-Octafluorobiphenyl crude yield 98 mol%).

The purity of the obtained compound was 93% as measured by liquid chromatography. The obtained compound was purified by column chromatography to obtain the above-mentioned fluorine-containing phthalonitrile derivative having a purity of 99%. The physical properties of the purified compound are as follows.

[0041] MS spectrum (EI): m / e 690,509 Example 6 Using the same apparatus as in Example 1, 22.1 g (0.11 mol) of 3,4,5,6-tetrafluorophthalonitrile was used.
(4,4'-dimercapto-2,2 ', 3,3', 5,
2 for 5 ', 6,6'-octafluorobiphenyl
0 times mole), 0.77 g of potassium fluoride (0.013 m
ol) and 80 g of acetonitrile are added, and the reflux temperature (82-
84.5 ° C). Then, from the dropping device,
4'-dimercapto-2,2 ', 3,3', 5,5 ',
2.0 g of 6,6'-octafluorobiphenyl (0.0
A solution prepared by dissolving (06 mol) in 20 g of acetonitrile was added dropwise over 1 hour. Then, the mixture was further reacted at reflux temperature for 4 hours. After the reaction was completed, potassium fluoride and its salt were filtered off, the filtrate was evaporated to dryness, and the unreacted 3,4,5,6
-By removing tetrafluorophthalonitrile by distillation, 4,4'-bis (3,4-dicyano-2,5,
3.8 g of a crude product of 6-trifluorophenylthio) octafluorobiphenyl was obtained (vs. 4,4'-dimercapto-2,2 ', 3,3', 5,5 ', 6,6'-octafluoro). Biphenyl crude yield 95 mol%).

The purity of the obtained compound was 95% as measured by liquid chromatography. The obtained compound was purified by column chromatography to obtain the above-mentioned fluorine-containing phthalonitrile derivative having a purity of 99%. The physical properties of the purified compound are as follows.

Elemental analysis value (C28F14N4S2) C N F S calculated value (%) 46.55 7.76 36.82 8.88 Measured value (%) 47.18 8.03 37.48 8.95 MS spectrum (%) EI): m / e 722,541 Example 7 44.0 g (0.22 mol) of 3,4,5,6-tetrafluorophthalonitrile was prepared using the same apparatus as in Example 1.
(20 times mol relative to tetrafluorohydroquinone), triethylamine 2.4 g (0.024 mol)
And 130 g of acetonitrile were added, and the reflux temperature (82-8
It heated to (4.5 degreeC). After that, from the dropping device, tetrafluorohydroquinone 2.0 g (0.011 mol)
Was dissolved in 20 g of acetonitrile, and the solution was added dropwise over 1 hour. Then, the mixture was further reacted at reflux temperature for 4 hours. After completion of the reaction, the hydrogen fluoride salt of triethylamine is removed,
By evaporating to dryness and further removing unreacted 3,4,5,6-tetrafluorophthalonitrile by distillation,
5.8 g of crude product of 1,4-bis (3,4-dicyano-2,5,6-trifluorophenoxy) tetrafluorobenzene was obtained (relative to tetrafluorohydroquinone crude yield 97 mol%).

The purity of the obtained compound was 94% as measured by liquid chromatography. The obtained compound was purified by column chromatography to obtain the above fluorine-containing tetrafluorophthalonitrile derivative having a purity of 99%.

Comparative Example 1 1 equipped with a stirring device, a cooling reflux pipe, a thermometer and a dropping device
In a 00 ml four-necked flask, 4.4 g (0.022 mol) of 3,4,5,6-tetrafluorophthalonitrile
(2 times the molar amount of tetrafluorohydroquinone),
To the mixture, 1.4 g (0.024 mol) of potassium fluoride and 40 g of acetonitrile were added and stirred at room temperature, and then 2.0 g (0.0
A solution prepared by dissolving 11 mol) in 20 g of acetonitrile was added dropwise over 1 hour. Then, the mixture was further reacted at room temperature for 1 hour. After completion of the reaction, potassium fluoride and its salt are filtered off,
The filtrate was evaporated to dryness, and unreacted 3,4,5,6-tetrafluorophthalonitrile was removed by distillation to give 1,4-bis (3,4-dicyano-2,5,6-tritriene. 5.6 g of a crude product of fluorophenoxy) tetrafluorobenzene was obtained (relative yield of tetrafluorohydroquinone: 94 mol%).

The purity of the obtained compound was 45% as measured by liquid chromatography.

[0047]

Industrial Applicability According to the present invention, there is provided a method for producing a fluorine-containing phthalonitrile derivative represented by the general formula (II) with high yield, good purity and high efficiency.

That is, as shown in Comparative Example 1, with respect to 1 mol part of tetrafluorohydroquinone, 3,4
When the reaction is carried out using 2 mol parts of 5,6-tetrafluorophthalonitrile, the purity of the obtained crude product is as low as 45%. On the other hand, as shown in Examples 1 to 7, with respect to 1 mol part of the compound of the general formula (I),
According to the present invention in which the reaction is carried out using at least 8 mol parts, preferably 15 to 30 mol parts of 4,5,6-tetrafluorophthalonitrile, the purity of the obtained crude product is 93 to 9
It is 7%, and by subsequent purification by column chromatography, a high-purity fluorine-containing phthalonitrile derivative of 99% or more can be obtained in a high yield.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location B01J 31/02 102 X C07B 61/00 300

Claims (2)

[Claims] 1. 3,4,5,6-tetrafluorophthalonitrile is represented by the following general formula (I): (In the formula, X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom, a sulfur atom, or And a nucleophilic substitution product represented by the following general formula (II): embedded image in the presence of a basic substance in an organic solvent. (In the formula, X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom, a sulfur atom, or In the production of a fluorinated phthalonitrile derivative represented by
A method for producing a fluorinated phthalonitrile derivative, which comprises using at least 8 mol parts of 4,5,6-tetrafluorophthalonitrile. 2. The method for producing a fluorinated phthalonitrile derivative according to claim 1, wherein the reaction is carried out in a temperature range of 40 ° C. to 100 ° C.