JP3366508B2 - Method for producing phthalonitrile compound - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a phthalonitrile compound having an ether group. More specifically, the present invention relates to a method for producing a phthalonitrile compound useful as an intermediate for a phthalocyanine compound used in optical recording media, near infrared absorption filters, OPC for electrophotography, and the like.

[0002]

2. Description of the Related Art Conventionally, as a method of synthesizing an alkoxybenzene derivative from a nitrobenzene derivative, a method of substituting a nitro group of the nitrobenzene derivative with a nucleophilic reagent such as sodium alkoxide has been known. For example, Journal of Organic Chemistry Vol. 39, No. 13, 18
39-1841 (1974) describes the following reaction of reacting sodium methoxide in dimethylformamide.

[0003]

[Chemical 3]

In these methods, the nucleophilic reagent is a lower alkoxide such as methoxide or ethoxide, and as long as the corresponding lower alkoxybenzene derivative is produced, problems such as purity and yield of the target product are small, but When the method is applied to the method for producing the phthalonitrile compound represented by the general formula (II) of the present invention, the obtained target product has low purity,
The yield is low and there are many by-products and unreacted substances.

As a method for producing a 4-alkoxyphthalonitrile derivative having a substitution position of an alkoxy group different from that of the phthalonitrile compound of the present invention, there is disclosed in JP-A-61-27363.
Japanese Patent Publication No. 5 discloses a method of reacting 4-nitrophthalonitrile and alcohols at 50 to 100 ° C. using a highly basic tertiary amine soluble in a reaction solvent as a catalyst. For example, Example 8 on page 6 of the same publication
In the above, 4-phthalonitrile and 1,1-dimethylbutanol were used, tripropylamine was used as a catalyst, and DMF was used as a solvent.
It is described that (1,1-dimethylbutoxy) -1,2-phthalonitrile is obtained in a yield of 92%.

However, when this production method is applied to 3-nitrophthalonitrile, it is considered that it is probably due to steric hindrance of the substitution reaction for 3-nitrophthalonitrile. The phthalonitrile compound (1) has a low yield and a low purity. In particular,
A large amount of unreacted raw material remains, and when the reaction temperature is raised, a large amount of tar-like by-products are produced.

Japanese Unexamined Patent Publication No. 3-215466 discloses 3-
Disclosed is a method for producing 3-alkoxyphthalonitrile by reacting nitrophthalonitrile with an alcohol in an aprotic polar solvent in the presence of a catalyst. Specifically, for example, in Example 1 on page 6 of the same publication, 2-dodecanol is dissolved in DMF, and after adding 60% sodium hydride, a mixed solution of 3-nitrophthalonitrile and DMF is added at 10 to 15 ° C. Was added dropwise and reacted for 24 hours, the reaction mixture was discharged into dilute hydrochloric acid, extracted with toluene, and purified by column chromatography to obtain 3- (1-methylundecyloxy) phthalonitrile in a yield of 53%.

However, in this production method, a large amount of by-products are produced, unreacted raw materials remain, the yield of the desired 3-alkoxyphthalonitrile is low, and a complicated purification process is required. Furthermore, when sodium hydride is added, depending on the type of alcohol, the reaction in which sodium alkoxide is produced from alcohol and sodium hydride is vigorous, and a large amount of hydrogen is generated during stirring and dispersion, and a dangerous state in manufacturing operation occurs such as heat generation. In some cases.

In Japanese Unexamined Patent Publication No. 6-234721, the structure of which is completely different from that of the method of the present invention, but a secondary or tertiary alkoxide and nitrophthalonitrile are used as reaction solvents in water at any ratio. However, a method for producing a corresponding alkoxyphthalonitrile by reacting with a mixed solvent composed of a dehydrated solvent that is mixed and a solvent that separates water is disclosed. The alkoxide used here is produced from alcohols and potassium hydroxide or sodium hydroxide.

However, in this production method, the production process is complicated, and not only a very large amount of energy and time are required for the dehydration treatment of the reaction solvent, but also a trace amount of water in the solvent influences the reactivity and the yield is reduced. It has the drawback of large fluctuations in rate and purity.

[0011]

The object of the present invention is to
An object of the present invention is to provide a method for easily and safely producing a corresponding 3-alkoxyphthalonitrile in high yield and high purity from nitrophthalonitrile and alcohols.

[0012]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the order of addition of each raw material, the operation, the temperature at the time of addition and reaction, particularly the conditions at the time of dispersing a basic catalyst. It has been found that the object of the present invention can be achieved by strictly defining

In the present invention, 3-nitrophthalonitrile and an alcohol represented by the following general formula (I) are selected from alkali metal hydrides and alkaline earth metal hydrides.
In the method of producing a phthalonitrile compound represented by the following general formula (II) by reacting in an aprotic polar solvent in the presence of one or more basic catalysts, a compound represented by the following general formula (I) Characterized in that the basic catalyst is dispersed while maintaining a state in which substantially no hydrogen is generated in a mixture of an alcohol and an aprotic polar solvent, and then 3-nitrophthalonitrile is added at 25 ° C. or lower. The present invention relates to a method for producing a phthalonitrile compound represented by the following general formula (II).

[0014]

[Chemical 4]

[0015]

[Chemical 5] (In the formulas (I) and (II), R is an unsubstituted alkyl group having a secondary or tertiary carbon atom bonded to an oxygen atom and having 4 or more carbon atoms, and a secondary or tertiary carbon atom bonded to an oxygen atom. Shows a substituted alkyl group having a total carbon number of 4 or more and an unsubstituted or substituted cycloalkyl group having a carbon number of 5 or more , and a bridged cyclic hydrocarbon residue.
Excluding the group . )

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the above formula (I) is used.
Before adding 3-nitrophthalonitrile in the step of dispersing one or more basic catalysts selected from alkali metal hydrides or alkaline earth metal hydrides in a mixture of the above alcohol and aprotic polar solvent. It is necessary that substantially no hydrogen be generated.

This is probably due to the above formula (I) of the present invention.
With relatively bulky alcohols such as
In the substitution reaction with nitrophthalonitrile, when an alkoxide is generated in advance, that is, when hydrogen is substantially generated in the step of dispersing the basic catalyst in a mixture of an alcohol and an aprotic polar solvent, the reaction is performed. Since the basicity of the system becomes high, the so-called Vicarious Nucleophilic Substitution reaction of aromatics proceeds competitively, producing a large number of by-products in which hydrogen in the benzene nucleus is replaced with an alkoxy group. It is presumed that the yield and purity of the target phthalonitrile compound are low.

In the alcohol represented by the above general formula (I), R is an unsubstituted alkyl group having 4 or more carbon atoms and having a secondary or tertiary carbon atom bonded to an oxygen atom, which has 4 carbon atoms. It is preferable that it is -16, especially what is a C4-C16 unsubstituted branched alkyl group.

When R is a substituted alkyl group having a secondary or tertiary carbon atom bonded to an oxygen atom and having a total carbon number of 4 or more, those having a total carbon number of 4 to 20 are preferable, and the total carbon is particularly preferable. Those having a substituted branched alkyl group of the number 4 to 20 are preferable. Examples of the substituent include an alkoxy group, an alkylthio group, a substituted amino group, a halogen atom and the like.

[0020] as R is an unsubstituted or substituted cycloalkyl group having 5 or more carbon atoms are those preferably several 5 to 4 carbon atoms. Examples of the substituent include an alkyl group, an alkoxy group, a substituted amino group and the like.

Specific examples of the alcohols represented by the above general formula (I) are those in which R is an unsubstituted alkyl group having 4 or more carbon atoms in which the carbon atom bonded to the oxygen atom is secondary or tertiary. , 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 2-heptanol, 3-heptanol, 4-heptanol, 2-octanol, 3-octanol, 4
-Octanol, 2-nonanol, 3-nonanol, 2
-Decanol, 3-decanol, 4-decanol, 5-
Decanol, 2-dodecanol, 3-tetradecanol, 4-hexadecanol, isobutyl alcohol, 1
-Ethyl-1-propanol, 2-ethyl-1-propanol, 1-methyl-1-butanol, 2-ethyl-3
-Butanol, isopentanol, neopentyl alcohol, 1,2-dimethyl-1-propanol, 1,3-
Diethyl-1-butanol, 2-n-propyl-1-butanol, 1-ethyl-2-methyl-1-propanol, 2-methyl-1-pentanol, 3-methyl-1-
Pentanol, 4-methyl-2-pentanol, 3-ethyl-2-pentanol, 2,4-dimethyl-3-pentanol, 3-methyl-4-ethyl-2-pentanol, 1-isopropyl-3 -Methyl-1-pentanol, 2,2,4-trimethyl-3-pentanol, 2,
2,4,4-Tetramethyl-3-pentanol, 3-methyl-3-pentanol, 2,6-dimethyl-3-heptanol, 2,6-dimethyl-4-heptanol, 2-
Ethyl-6-methyl-3-heptanol, 2-ethyl-
6-methyl-4-heptanol, 2-ethyl-6-methyl-5-heptanol and the like can be mentioned.

R is a substituted alkyl group having a total carbon number of 4 or more in which the carbon atom bonded to the oxygen atom is secondary or tertiary, and the above alcohols are substituted with an alkoxy group, an alkylthio group or a substituted group. Examples thereof further include those having an amino group, a halogen atom or the like, or those having a similar substituent to 2-propanol.
Ethoxy-1-butanol, 2,4-dimethoxy-3-
Pentanol, 1-ethoxymethoxy-3-pentanol, 2,4-dimethylthio-3-hexanol, 1-ethylthio-3-pentanol, 1- (t-butylthio)
-3-Pentanol, 1-dimethylamino-3-butanol, 2-diethylamino-3-pentanol, 1-diethylamino-2-propanol, 1-chloro-5-methyl-3-hexanol, 2,4-dichloro- 3-pentanol, 2,5-dichloro-3-pentanol, 1,
5-dibromo-3-pentanol, 1,1,1-trifluoro-3-pentanol, 1,1,5,5-tetrafluoro-3-pentanol and the like can be mentioned.

Specific examples of R being an unsubstituted or substituted cycloalkyl group having 5 or more carbon atoms include cyclohexanol, cyclopentanol, cyclooctanol, 2
-Methylcyclohexanol, 4-methylcyclohexanol, 4-ethylcyclohexanol, 4-t-butylcyclohexyl alcohol, 4- (2-ethylcyclohexyl) cyclohexanol and the like can be mentioned.

Examples of the aprotic polar solvent include dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone and 1,3-dimethyl-2.
-Imidazolidinone, sulfolane, hexamethylphosphoric triamide and the like can be used, but dimethylformamide, dimethylacetamide and dimethylsulfoxide are particularly preferable.

As the alkali metal hydride, sodium hydride, potassium hydride and lithium hydride can be used. As the alkaline earth metal hydride, calcium hydride and magnesium hydride can be used, but sodium hydride and potassium hydride are particularly preferable. It is also possible to use mixtures of these. When potassium carbonate or potassium hydroxide, which is generally used as a basic catalyst in a similar substitution reaction, is used in the present invention, the yield and purity are lowered.

In the mixture of the alcohol of the formula (I) and the aprotic polar solvent, one or more basic catalysts selected from alkali metal hydrides or alkaline earth metal hydrides (hereinafter referred to as "the base In the step of dispersing the organic catalyst), in order not to substantially generate hydrogen,
It is effective to mainly control the temperature. Specifically, it is desirable that the internal temperature is 25 ° C. or lower, more preferably 20 ° C. or lower throughout the steps of adding and dispersing the basic catalyst. If the internal temperature exceeds 25 ° C. in this step, the yield and purity of the target product will decrease as a result.

The basic catalysts, such as sodium hydride and potassium hydride, are usually clay-like because they contain liquid paraffin as a protective medium, and they are aprotic with the alcohol of the formula (I). After adding to the mixture of polar solvents, it is preferable to stir for a certain period of time to disperse. Even if the internal temperature at the time of adding the basic catalyst is 25 ° C. or lower, if continuous cooling is not performed, the reaction of forming an alkoxide from the alcohol of the formula (I) and the basic catalyst during dispersion is Since heat is generated and the internal temperature rises above 25 ° C., the alkoxide generation reaction is accelerated and further heat generation and hydrogen generation occur.

The dispersion time of the basic catalyst varies depending on the reaction scale, but is usually 10 minutes to several hours.

It is speculated that the generation of hydrogen in this step is due to the progress of the formation of alkoxide due to the reaction between the alcohol of formula (I) and the basic catalyst as described above. Conventionally, in this kind of substitution reaction, the above-mentioned JP-A-61-207365 and JP-A-6-23 have been used.
As described in Japanese Patent No. 4721, since it is common knowledge that a nitro group is substituted with an alkoxide, or the presence of an alkoxide ion promotes a substitution reaction, an alkoxide is generated in advance in the above step. In other words, it is customary to generate hydrogen rather positively. In addition, JP-A-3-2
Also in 15466, it is considered that unreacted raw materials remain and the yield and purity are low, because the reaction is carried out through the formation of alkoxide under the same common general knowledge.

The present inventors have conducted various studies in the production of the phthalonitrile compound of the general formula (II). As a result, the alcohol of the formula (I) is added to the mixture of the aprotic polar solvent and the basic catalyst. When a large amount of hydrogen is generated during dispersion, the final formula (I
It has been found that the yield and purity of the phthalonitrile compound of I) are reduced. In this case, many compounds in which hydrogen in the benzene nucleus was substituted with an alkoxy group were confirmed, not those in which the nitro group in the benzene nucleus was substituted.

There is no particular lower limit to the temperature at which the basic catalyst is dispersed in the mixture of the alcohol of formula (I) and the aprotic polar solvent, but in the manufacturing process, it is -30 ° C or higher, preferably -20 ° C.
The above is desirable. Further, depending on the type of the mixture of the alcohol of the formula (I) and the aprotic polar solvent, there are some which have a freezing point at −30 ° C. or higher. In such a case, the lower limit of the dispersion temperature is the freezing point.

The temperature at which 3-nitrophthalonitrile is added after dispersing the basic catalyst is 25 ° C. or lower, preferably 20 ° C. or lower. Although there is no particular lower limit, at a temperature lower than -30 ° C, the progress of the intended substitution reaction is delayed, which is disadvantageous in the production process. Therefore, it is -30 ° C or higher, preferably -2 ° C.
0 ° C or higher is desirable. If the temperature at which 3-nitrophthalonitrile is added exceeds 25 ° C., the yield of the desired product is
Purity decreases.

As a method for adding 3-nitrophthalonitrile, a solution obtained by dissolving 3-nitrophthalonitrile in an aprotic polar solvent may be added dropwise, but a powdery or granular solid 3 which can be divided is used. More preferably, nitrophthalonitrile is added while adjusting the addition rate to some extent. In the case of the method of dropping a solution dissolved in an aprotic polar solvent, the yield of the target product may decrease because it is easily affected by water in the aprotic polar solvent.

The time for adding 3-nitrophthalonitrile is preferably such that the amount of hydrogen generated by the addition does not become a dangerous amount and as short as possible. This optimum time varies depending on the reaction scale, but is usually 1.
5 minutes to several hours.

After the addition of 3-nitrophthalonitrile was completed,
Further, -30 ° C to 25 ° C, preferably -20 ° C to 20 ° C
The reaction is carried out for 0.5 to 15 hours, preferably 1.0 to 10 hours.

Contrary to the method of the present invention, a solution of 3-nitrophthalonitrile in an aprotic polar solvent is mixed with an alcohol of formula (I) and a basic catalyst in an aprotic polar solvent, There is also a method of adding in a dispersed manner, but in this case, not only there is a problem such as clogging of the dropping valve, but also the yield and purity of the target product are lowered.

After the reaction is completed, the reaction mixture is discharged into water or a dilute aqueous alkali solution to remove by-products dissolved in the aqueous alkali solution, and the desired general formula (II)
Alkoxyphthalonitrile of is directly obtained in high purity.
As the alkali, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate or the like can be used.

The discharge of the reaction mixture is carried out by the method described in JP-A-3-215466 and JP-A-6-234721, that is, the reaction mixture is discharged into dilute hydrochloric acid and the solvent such as benzene, toluene and xylene is discharged. When the method of extracting by the method is used, it is difficult to directly obtain a high-purity target product because the by-product is difficult to remove.

Specific examples of the 3-alkoxyphthalonitrile obtained by the present invention include the products derived from the above-mentioned alcohols of the general formula (I), but especially 3
-(2,4-dimethyl-3-pentyloxy) phthalonitrile, 3- (2,6-dimethyl-4-heptyloxy) phthalonitrile, 3- (2,5-dimethyl-3-hexyloxy) phthalonitrile, 3- (4-methyl-2)
-Pentyloxy) phthalonitrile, 3- (2-methyl-3-pentyloxy) phthalonitrile, 3- (3-methyl-2-pentyloxy) phthalonitrile, 3-
(2,2,4-Trimethyl-3-pentyloxy) phthalonitrile, 3- (2,4-dimethyl-3-hexyloxy) phthalonitrile, 3- (2-methyl-3-hexyloxy) phthalonitrile, 3 -(3-Methyl-3-pentyloxy) phthalonitrile, 3- (4-dodecyloxy) phthalonitrile, 3- (2-ethyl-3-hexyloxy) phthalonitrile, 3- (2-ethyl-4-hexyl) (Oxy) phthalonitrile, 3- (4-t-butylcyclohexyloxy) phthalonitrile, 3- (cyclohexyloxy) phthalonitrile, 3- [4- (2-ethylhexyl) cyclohexyloxy) phthalonitrile, 3- (1-diethylamino) -2-propyloxy)
Examples thereof include phthalonitrile.

[0040]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. In the examples and comparative examples, "part" means "part by weight".

Example 1 3- (2,4-dimethyl-3-
Preparation of pentyloxy) phthalonitrile 2,4-dimethyl-3-pentanol 1 under nitrogen atmosphere
Dissolve 0.0 part in 60 parts of dimethylformamide-5
Cooled to ~ 0 ° C. At the same temperature, 2.5 parts of 60% sodium hydride was added, and the mixture was stirred and dispersed at the same temperature for 30 minutes. During this time, generation of hydrogen was not observed in the reaction solution.
Next, 10.0 parts of powdered 3-nitrophthalonitrile was added over 1 hour while maintaining -5 to 0 ° C, and the mixture was stirred at the same temperature for 2 hours. The reaction mixture was discharged into 500 parts of water, 160 parts of toluene was added to the discharged liquid, and after the extraction treatment, the toluene layer was washed successively with 200 parts of 0.05% aqueous sodium hydroxide solution and 200 parts of water × 3 times. After distilling toluene off from the toluene layer, 55 parts of n-hexane was added to the residue under reflux 1
Stir for hours. After cooling, the crystals were collected by filtration and dried to obtain 12.9 parts (yield 92.1%) of 3- (2,4-dimethyl-3-pentyloxy) phthalonitrile having the following structural formula.

[0042]

[Chemical 6]

The elemental analysis value, mass analysis value, melting point and purity analysis result by high performance liquid chromatography of this crystal were as follows. The infrared absorption spectrum of this compound is shown in FIG. MS (m / e): 242 (M ⁺ ) Melting point: 81.0-83.0 ° C Purity: 99.2% by weight

Example 2 3- (2,4-dimethyl-3-
Preparation of pentyloxy) phthalonitrile 2,4-dimethyl-3-pentanol 1 under nitrogen atmosphere
Dissolve 7.4 parts in 55 parts of dimethylformamide-1
Cooled to 5-10 ° C. At the same temperature, 4.40 parts of 60% sodium hydride was added, and the mixture was stirred and dispersed at the same temperature for 30 minutes. During this time, generation of hydrogen was not observed in the reaction solution. Then, maintaining -15 to -10 ° C, 17.3 parts of 3-nitrophthalonitrile was added to dimethylformamide 5
A solution that was dissolved in 5 parts and kept cold at 5 ° C or lower was added dropwise over 1 hour,
Further, the mixture was stirred at -15 to -10 ° C for 30 minutes. Then, slowly raise the temperature to 20 ° C., and then stir at the same temperature for 2 hours.
It was discharged to the department. The precipitated crystals are collected by filtration, washed with water and dried,
21.7 parts (yield 89.6%) of 3- (2,4-dimethyl-3-pentyloxy) phthalonitrile were obtained.

The elemental analysis value, mass analysis value, melting point and purity analysis result by high performance liquid chromatography of this crystal were as follows. The infrared absorption spectrum of this compound was similar to that obtained in Example 1. MS (m / e): 242 (M ⁺ ) Melting point: 80.0-83.0 ° C Purity: 98.1% by weight

Example 3 3- (2,4-dimethyl-3-
Preparation of pentyloxy) phthalonitrile 2,4-dimethyl-3-pentanol 1 under nitrogen atmosphere
Dissolve 7.4 parts in 55 parts of dimethylformamide 10
Cooled to ~ 15 ° C. At the same temperature, 4.40 parts of 60% sodium hydride was added, and the mixture was stirred and dispersed at the same temperature for 30 minutes. During this time, generation of hydrogen was not observed in the reaction solution. Next, while maintaining the temperature at 10 to 15 ° C., 17.3 parts of 3-nitrophthalonitrile was dissolved in 55 parts of dimethylformamide, and the liquid cooled at 5 ° C. or lower was added dropwise over 1 hour.
The mixture was stirred at 0 to 15 ° C for 30 minutes and discharged into 900 parts of water. 250 parts of toluene was added to the discharged liquid, and after extraction treatment, the toluene layer was washed successively with 150 parts of water × 3 times. After toluene was distilled off from the toluene layer, 200 parts of n-hexane was added to the residue and the mixture was stirred under reflux for 1 hour. After cooling, the crystals are filtered and dried,
21.0 parts (yield 86.6%) of 3- (2,4-dimethyl-3-pentyloxy) phthalonitrile was obtained.

The elemental analysis value, mass analysis value, melting point and purity analysis result by high performance liquid chromatography of this crystal were as follows. The infrared absorption spectrum of this compound was similar to that obtained in Example 1. MS (m / e): 242 (M ⁺ ) Melting point: 81.0-83.0 ° C Purity: 98.6% by weight

Example 4 3- (2,6-dimethyl-4-)
Production of heptyloxy) phthalonitrile The same operation as in Example 1 except that 12.4 parts of 2,6-dimethyl-4-heptanol was used instead of 10.0 parts of 2,4-dimethyl-3-pentanol. Go to
14.3 parts of 3- (2,6-dimethyl-4-heptoxy) phthalonitrile of the following structural formula as a yellow oil (yield 9
1.3%) was obtained.

[0049]

[Chemical 7]

The elemental analysis value, the mass analysis value and the purity analysis result by high performance liquid chromatography of this yellow oily substance are as follows. The infrared absorption spectrum of this compound is shown in FIG. MS (m / e): 270 (M ⁺ ) Purity: 98.2% by weight

Example 5 Preparation of 3- (2,2,4-trimethyl-3-pentyloxy) phthalonitrile In Example 1, 2 parts of 2,4-dimethyl-3-pentanol was replaced by 2 parts. , 2,4-trimethyl-3
-A similar operation was performed except that 11.2 parts of pentanol was used, and 3- (2,2,4-trimethyl-
12.8 parts (yield 86.3%) of 3-pentyloxy) phthalonitrile were obtained.

[0052]

[Chemical 8]

The elemental analysis value, mass analysis value, melting point and purity analysis result by high performance liquid chromatography of this crystal were as follows. The infrared absorption spectrum of this compound is shown in FIG. MS (m / e): 256 (M ⁺ ) Melting point: 73 to 75 ° C. Purity: 98.9% by weight

Example 6 3- (2,4-dimethyl-3-
Production of Hexyloxy) phthalonitrile Similar to Example 1 except that 10.0 parts of 2,4-dimethyl-3-pentanol was replaced with 11.2 parts of 2,4-dimethyl-3-hexanol. By operation, 13.3 parts of 3- (2,4-dimethyl-3-hexyloxy) phthalonitrile of the following structural formula (yield 89.5%)
Got

[0055]

[Chemical 9]

The elemental analysis value, mass analysis value, melting point and purity analysis result by high performance liquid chromatography of this crystal were as follows. This compound was confirmed by infrared absorption spectrum. MS (m / e): 256 (M ⁺ ) Melting point: 59 to 61 ° C Purity: 98.8% by weight

Example 7 Preparation of 3- (3-methyl-3-pentyloxy) phthalonitrile In Example 1, instead of 10.0 parts of 2,4-dimethyl-3-pentanol, 3-methyl-3 was used. The same operation was carried out except that 8.79 parts of pentanol was used, and 11.3 parts of an oily product of 3- (3-methyl-3-pentyloxy) phthalonitrile having the following structural formula (yield: 85.8). %) Was obtained. The obtained oily substance solidified over time.

[0058]

[Chemical 10]

The elemental analysis value, the mass analysis value and the purity analysis result by high performance liquid chromatography of this solid were as follows. This compound was confirmed by infrared absorption spectrum. MS (m / e): 228 (M ⁺ ) Purity: 98.3% by weight

Example 8 Preparation of 3- (4-t-butylcyclohexyloxy) phthalonitrile In the Example 1, 4-t-butylcyclohexanol was used instead of 10.0 parts of 2,4-dimethyl-3-pentanol. The same operation was carried out except that 12.9 parts were used to prepare 3- (4-t-butylcyclohexyloxy) having the following structural formula.
13.9 parts (yield 85.3%) of phthalonitrile were obtained.

[0061]

[Chemical 11]

The elemental analysis value, mass analysis value, melting point and purity analysis result by high performance liquid chromatography of this crystal were as follows. This compound was confirmed by infrared absorption spectrum. MS (m / e): 282 (M ⁺ ) Melting point: 172 to 175 ° C Purity: 98.8% by weight

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

Example 9 Preparation of 3- (1-diethylamino-2-propoxy) phthalonitrile In Example 1, 2,4-dimethyl-3
-Using the same procedure except that 11.3 parts of 1-diethylamino-2-propanol was used instead of 10.0 parts of pentanol, 3- (1-diethylamino-2-propoxy) phthalonitrile of the following structural formula was obtained. 13.0 parts (yield 8
7.3%).

[0070]

[Chemical 14]

The elemental analysis value, mass analysis value, melting point and purity analysis result by high performance liquid chromatography of this crystal were as follows. This compound was confirmed by infrared absorption spectrum. MS (m / e): 257 (M ⁺ ) Melting point: 75 to 77 ° C Purity: 98.2% by weight

Comparative Example 1 3- (2,4-dimethyl-3-
Preparation of pentyloxy) phthalonitrile 2,4-dimethyl-3-pentanol 1 under nitrogen atmosphere
Dissolve 3.0 parts in 55 parts of dimethylformamide,
Add 4.40 parts of 60% sodium hydride at 5 ° C and add 3
The mixture was stirred and dispersed for 0 minutes. The internal temperature gradually rises to 27-
Vigorous evolution of hydrogen was observed at 30 ° C. After the generation of hydrogen was almost no longer recognized, the internal temperature was changed from -15 to -1.
The solution was cooled to 0 ° C., 17.3 parts of 3-nitrophthalonitrile was dissolved in 55 parts of dimethylformamide, and the solution kept cold at 5 ° C. or lower was added dropwise over 1 hour, and further at −15 to −10 ° C. for 3 hours.
Stir for 0 minutes. After slowly raising the temperature to 20 ° C., the mixture was stirred at the same temperature for 2 hours. When the reaction solution was discharged into 900 parts of water and the same post-treatment as in Example 1 was carried out, a brownish tar-like substance was deposited. After cooling, the tar-like substance was collected by filtration, washed with water and dried to obtain 12.5 parts of a brownish tar-like substance (crude yield 56.1%).

The purity of this brownish tar-like substance was analyzed by high performance liquid chromatography, and as a result, 3
The content of-(2,4-dimethyl-3-pentyloxy) phthalonitrile was 38% by weight.

The brownish tar-like substance contained 56% by weight of a compound having the following structural formula as a by-product, high performance liquid chromatography, elemental analysis value, mass analysis value and NMR.
Confirmed by analysis.

[0075]

[Chemical 15]

[0076] MS (m / e): 287 (M ⁺ ) Melting point: 172 to 175 ° C

Comparative Example 2 3- (2,4-dimethyl-3-
Preparation of Pentyloxy) phthalonitrile Under a nitrogen atmosphere, 17.4 parts of 2,4-dimethyl-3-pentyl alcohol were dissolved in 55 parts of dimethylformamide, and 1,8-diazabicyclo [5,4,4] at 20 to 30 ° C.
0] -7-undecene (DBU) (15 parts) was charged, and the mixture was stirred for 30 minutes. After cooling to 5 ° C or lower, 17.3 parts of 3-nitrophthalonitrile was charged, and the mixture was stirred at 0 to 5 ° C for 2 hours. During this time, as a result of high performance liquid chromatography analysis of the reaction liquid, almost no reaction proceeded. After the temperature was raised to 60 ° C., the reaction was carried out at the same temperature for 24 hours, and the mixture was discharged into 900 parts of diluted hydrochloric acid water. To the discharged liquid, 250 parts of toluene was charged, and after extraction treatment, the toluene layer was washed with 150 parts of water three times. After distilling toluene off from the toluene layer, 200 parts of hexane was added and the mixture was stirred under reflux for 1 hour. After cooling, a tar-like substance was precipitated, separated by filtration and dried to obtain 12.7 parts (yield 52.3%) of a yellowish brown solid substance. High performance liquid chromatography of this tan solid
The result of the purity analysis by is 3- (2,4-dimethyl-3-
As pentyloxy) phthalonitrile, the purity was 12% by weight, and 72% by weight of 3-nitrophthalonitrile as a raw material was contained (raw material recovery rate: 52.8%).

[0078]

Industrial Applicability According to the present invention, it has become possible to simply and safely produce the corresponding 3-alkoxyphthalonitrile from 3-nitrophthalonitrile and alcohols in high yield and high purity.

[Brief description of drawings]

1 is the 3- (2,4-dimethyl-produced in Example 1;
It is an infrared absorption spectrum of 3-pentyloxy) phthalonitrile.

2 is the 3- (2,6-dimethyl-prepared in Example 4; FIG.
It is an infrared absorption spectrum of 4-heptyloxy) phthalonitrile.

FIG. 3 is an infrared absorption spectrum of 3- (2,2,4-trimethyl-3-pentyloxy) phthalonitrile produced in Example 5.

─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Toshihiro Masaoka 1-43 Minami, Yuge-cho, Yao-shi, Osaka Yamamoto Kasei Co., Ltd. (72) Hiroyuki Sasaki 1-43 Minami, Yuge-cho, Yao-shi, Osaka Yamamoto Kasei Incorporated (72) Inventor Junichi Taniguchi 1-43 Minami, Yugemachi, Yao-shi, Osaka Yamamoto Kasei Co., Ltd. (56) Reference JP-A-8-217738 (JP, A) (58) Fields investigated (Int .Cl. ⁷ , DB name) C07C 253/30 C07C 255/54 C07B 61/00 300 B01J 31/12

Claims (8)

(57) [Claims] 1. Nitrophthalonitrile and an alcohol represented by the following general formula (I) are selected from the group consisting of alkali metal hydrides and alkaline earth metal hydrides, or 2
In the method for producing a phthalonitrile compound represented by the following general formula (II) by reacting in an aprotic polar solvent in the presence of one or more basic catalysts, an alcohol represented by the following general formula (I) The following general formula, characterized in that the basic catalyst is dispersed in a mixture of aprotic polar solvents while maintaining a state in which substantially no hydrogen is generated, and then 3-nitrophthalonitrile is added at 25 ° C or lower. A method for producing a phthalonitrile compound represented by (II). [Chemical formula 1] [Chemical formula 2] (In the formulas (I) and (II), R is an unsubstituted alkyl group having a secondary or tertiary carbon atom bonded to an oxygen atom and having 4 or more carbon atoms, and a secondary or tertiary carbon atom bonded to an oxygen atom. Shows a substituted alkyl group having a total carbon number of 4 or more and an unsubstituted or substituted cycloalkyl group having a carbon number of 5 or more , and a bridged cyclic hydrocarbon residue.
Excluding the group . ) 2. The method for producing a phthalonitrile compound according to claim 1, wherein the basic catalyst is dispersed at 25 ° C. or lower. Wherein formula (I), the said R in Formula (II),
Except for a bridged cyclic hydrocarbon residue, a carbon atom bonded to an oxygen atom is a secondary or tertiary unsubstituted alkyl group having 4 to 16 carbon atoms, and a carbon atom bonded to an oxygen atom is a secondary or tertiary carbon atom. method for producing a substituted alkyl group, claim 1 or 2 phthalonitrile compound is unsubstituted or substituted cycloalkyl group having a carbon number of 5 to 1 4 4 to 20 carbon atoms. 4. The method for producing a phthalonitrile compound according to any one of claims 1 to 3, wherein 3-nitrophthalonitrile is dispersed as a solid such as powder or granules which can be divided and added. 5. The method for producing a phthalonitrile compound according to claim 1, wherein the basic catalyst is sodium hydride or potassium hydride. 6. The method for producing a phthalonitrile compound according to claim 1, wherein the dispersion temperature of the basic catalyst is 20 ° C. or lower. 7. The method for producing a phthalonitrile compound according to claim 1, wherein the addition temperature of 3-nitrophthalonitrile is 20 ° C. or lower. 8. The method for producing a phthalonitrile compound according to claim 1, wherein the desired product is isolated without acidifying the reaction solution after the reaction.