JP2667414B2 - Method for producing 2,3-dicyanonaphthalene - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing 2,3-dicyanonaphthalene. More specifically, the first invention of the present invention is a method for producing 2,3-dicyanonaphthalene, comprising dehydrating 2,3-naphthalenedicarboxylic acid diamide in a nitrogen-containing organic solvent in the presence of a dehydrating agent. In the second invention, the imidization reaction of 2,3-naphthalenedicarboxylic anhydride with urea
To produce 3-naphthalenedicarboxylic acid imide, then to produce 2,3-naphthalenedicarboxylic acid diamide by amidation reaction with ammonia, and then in a nitrogen-containing organic solvent,
The present invention relates to a method for producing 2,3-dicyanonaphthalene by dehydration in the presence of a dehydrating agent. 2,3-Dicyanonaphthalene, an object compound of the present invention, is a compound useful as a starting material for a naphthalocyanine compound which is an organic dye having absorption in the near infrared region. <Prior Art> With respect to the production of 2,3-dicyanonaphthalene, α, α, α′α′-tetrabromo-o is used in the presence of sodium iodide.
-A method by a cyclization / dehydrobromination reaction with xylene and fumaronitrile, or a method by a gas phase catalytic reaction of 2,3-naphthalene dicarboxylic acid imide in a stream of ammonia in the presence of a thorium oxide-based catalyst at a temperature of 400 to 500 ° C. Are known. However, in the former method, one of the starting materials α, α, α ′, α′-tetrabromo-o-xylene is toxic to α, α′-dibromo when the bromination reaction of o-xylene is carried out. -O-xylene is by-produced, while fumaronitrile itself is not only a toxic substance, but its synthesis method is complicated, and therefore both of them have to be expensive. Therefore, the process cannot be an economical process for producing 2,3-dicyannanaphthalene due to difficulties in handling the starting materials and high cost. In the latter production method, the performance of the catalyst used is remarkably deteriorated, and the equipment requires a great deal of cost. As a result, the resulting 2,3-dicyanonaphthalene must be expensive. <Problems to be Solved by the Invention> Accordingly, an object of the present invention is to provide 2,3-dicyanonaphthalene, a compound useful as a starting material of a naphthalocyanine compound which is an organic dye having absorption in the near infrared region, economically. It is an object of the present invention to provide a method which is advantageous in production. <Means for Solving the Problems> According to a first aspect of the present invention, the object is to dehydrate 2,3-naphthalenedicarboxylic diamide in a nitrogen-containing organic solvent in the presence of a dehydrating agent. This is achieved by a method for producing 2,3-dicyanonaphthalene. The starting material 2,3-naphthalenedicarboxylic acid diamide is a novel compound synthesized for the first time by the present inventors, and can be produced, for example, by subjecting 2,3-naphthalenedicarboxylic acid imide and ammonia to an amidation reaction. . In producing 2,3-dicyanonaphthalene from 2,3-naphthalenedicarboxylic acid diamide, it is important to use a nitrogen-containing organic solvent as a reaction solvent, and the dehydration reaction does not proceed at all in other solvents, or The formation of 2,3-dicyanonaphthalene is very small. Specific examples of the nitrogen-containing organic solvent include pyridine, picoline, quinoline and the like, of which pyridine is preferable. As the dehydrating agent, phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, phosphorus pentoxide, thionyl chloride, sulfuryl chloride and the like can be used, but phosphorus oxychloride is preferred. When phosphorus oxychloride is used as the dehydrating agent, the amount used is in the range of 2 to 5 mol per mol of 2,3-naphthalenedicarboxylic acid diamide, and the dehydration reaction is carried out by dispersing in a nitrogen-containing organic solvent. The reaction is carried out while dropwise adding phosphorus oxychloride to a solution of 3,3-naphthalenedicarboxylic acid diamide. At that time, the reaction temperature is in the range of 30 to 90 ° C., and the dehydration reaction is completed in a short time after the dropwise addition of the phosphorus oxychloride.
Time range. After the completion of the dehydration reaction, the generated reaction solution containing 2,3-dicyanonaphthalene is immediately poured into a large amount of ice water, and the precipitated 2,3-dicyanonaphthalene is recovered. As a result, most of the 2,3-naphthalenedicarboxylic diamide is converted to give 2,3-dicyanonaphthalene in high yield. Next, the present inventors have conducted various studies on a method for producing 2,3-dicyanonaphthalene from 2,3-naphthalenedicarboxylic anhydride with good yield, and as a result, completed the second invention of the present invention. That is, in the second invention, an imidation reaction of 2,3-naphthalenedicarboxylic acid anhydride and urea is performed to produce 2,3-naphthalenedicarboxylic acid imide, and then the 2,3-naphthalenedicarboxylic acid imide and ammonia are amide-treated. Reaction to produce 2,3-naphthalenedicarboxylic acid diamide, and then dehydrating the 2,3-naphthalenedicarboxylic acid diamide in a nitrogen-containing organic solvent in the presence of a dehydrating agent, 2,3-dicyanonaphthalene. It is a manufacturing method of. The process diagram is as follows. The first step of the present invention is the production of 2,3-naphthalenedicarboxylic imide by an imidation reaction of 2,3-naphthalenedicarboxylic anhydride with urea. The imidization reaction is a decomposition reaction of urea accompanied with the generation of ammonia and carbon dioxide.Therefore, the reaction is usually performed under normal pressure, but if the generated ammonia gas and carbon dioxide gas can be discharged out of the reaction system, the reaction is performed under pressure or under reduced pressure. Of course, it is also possible to carry out. At that time, the reaction temperature is in the range of 120 to 250 ° C.
In order to obtain naphthalenedicarboxylic acid imide in a high yield, it is preferable to maintain the reaction temperature at 120 ° C. or higher.If the temperature is lower than this, not only the yield of 2,3-naphthalenedicarboxylic imide is reduced, but also the reaction temperature is lowered. It takes a long time to complete. Therefore, as a solvent used in the imidization reaction, an organic solvent having a boiling point at normal pressure of 120 ° C. or higher, preferably 150 ° C. or higher is desirable. Specific examples thereof include aliphatic hydrocarbons such as octane, nonane, decane and dodecane,
Examples include aromatic hydrocarbons such as xylene, mesitylene, cumene, and tetralin; halogenated aromatic hydrocarbons such as dichlorobenzene and chlorotoluene; and ethers such as dialkyl ether and alkylphenyl ether.
The time required to carry out the imidization reaction in the temperature range of 120 to 250 ° C. using these organic solvents is 2 to 24 hours. The amount of urea used as an imidizing agent may be at least a stoichiometric amount based on 2,3-naphthalenedicarboxylic anhydride, more preferably 1 mole of 2,3-naphthalenedicarboxylic anhydride. In contrast, it is in the range of 1.1 to 1.8 mol. As a result, most of the 2,3-naphthalenedicarboxylic anhydride is converted to 2,3-naphthalenedicarboxylic imide,
2,3-Naphthalenedicarboxylic imide is obtained in high yield. The second step of the present invention is the production of 2,3-naphthalenedicarboxylic diamide by an amidation reaction between 2,3-naphthalenedicarboxylic imide and ammonia. Usually, the use of aqueous ammonia is common for the amidation reaction of organic dicarboxylic acids, but as a result of intensive studies conducted by the present inventors, it is necessary to obtain 2,3-naphthalenedicarboxylic diamide in a high yield in the reaction system. It is important to eliminate the presence of water as much as possible. The presence of water reduces the selectivity to the target compound 2,3-naphthalenedicarboxylic acid diamide,
It was found to increase the by-product of 3-carbamoyl-2-naphthoic acid. That is, it is preferable to use so-called liquid ammonia containing no water as ammonia, and it is also possible to use an organic solvent in which ammonia is dissolved. The amount of ammonia used may be a stoichiometric amount or more with respect to 2,3-naphthalenedicarboxylic acid imide, but 3 to 50 mol, preferably 5 to 5 mol per mol of 2,3-naphthalenedicarboxylic acid imide. It is in the range of 30 moles. The amidation reaction of 2,3-naphthalenedicarboxylic acid imide is usually performed under pressure with liquid ammonia in an autoclave, but not only liquid ammonia itself can be used as a reaction solvent, but also an organic solvent which is inert in the reaction system. It is also possible to do it inside. The use of an organic solvent not only promotes the amidation reaction by dispersing and dissolving 2,3-naphthalenedicarboxylic acid imide, but also lowers the pressure in the reaction system as compared with the case where liquid ammonia itself is used as the reaction solvent. It also has the effect. An additional advantage of using an organic solvent is that after releasing excess ammonia after the end of the amidation reaction, the generated 2,3-naphthalenedicarboxylic diamide can be easily removed from the autoclave of the reactor in a slurry state. And the use of organic solvents is essential in the continuous process for the preparation of 2,3-naphthalenedicarboxylic acid diamides. As a specific example of the organic solvent used, carbon atoms 5 to 16
Aliphatic hydrocarbons, (alkyl) cyclopentane,
Alicyclic hydrocarbons such as (alkyl) cyclohexane, aromatic hydrocarbons such as benzene, alkylbenzene, and tetralin; chloro or bromo saturated or unsaturated aliphatic hydrocarbons having 2 to 5 carbon atoms; chloro or bromobenzene; Halogenated aromatic hydrocarbons such as alkylbenzene, alcohols having 1 to 12 carbon atoms such as methanol, ethanol, and propanol, alcohols including diols such as ethylene glycol and propylene glycol, and aliphatic acids such as acetic acid and propionic acid Esters such as alkyl esters of organic acids, dialkyl ethers such as diethyl ether and diisopropyl ether, dioxane,
Examples include cyclic ethers such as tetrahydrofuran, ethers such as ethylene glycol dialkyl ether, and ketones such as dialkyl ketone and cyclic ketone. The amount used is not particularly limited as long as the contents can be easily stirred.
It is in the range of 2 to 10 parts by weight based on 1 part by weight of 2,3-naphthalenedicarboxylic acid imide. The reaction temperature is in the range of room temperature to 100 ° C., preferably in the range of 10 to 80 ° C., and the reaction time requires 3 to 16 hours. As a result, most of the 2,3-naphthalenedicarboxylic imide is converted to 2,3-naphthalenedicarboxylic diamide, and 2,3-naphthalenedicarboxylic diamide is obtained in high yield. As described above, the third step of the present invention is a step of producing 2,3-dicyanonaphthalene by dehydrating 2,3-naphthalenedicarboxylic acid diamide in a nitrogen-containing organic solvent in the presence of a dehydrating agent. <Example> Hereinafter, the present invention will be described in detail with reference to specific examples, but it is needless to say that the present invention is not limited to the examples. The method for analyzing the contents in the examples is gas chromatography for the production of 2,3-naphthalenedicarboxylic imide, high performance liquid chromatography for the production method of 2,3-naphthalenedicarboxylic diamide, 2,3-
The method for producing dicyanonaphthalene was performed by gas chromatography and high performance liquid chromatography. In the examples, 2,3-naphthalenedicarboxylic acid anhydride conversion rate and 2,3-naphthalenedicarboxylic acid imide selectivity, 2,3-naphthalenedicarboxylic acid imide conversion rate and 2,3-naphthalenedicarboxylic acid diamide selectivity. , 2,3-
The naphthalene dicarboxylic acid diamide conversion rate and the 2,3-dicyanonaphthalene selectivity are defined as follows. Example 1 a) Preparation of 2,3-naphthalenedicarboxylic acid imide 99.2%
2,3-naphthalenedicarboxylic anhydride 159.6 g, urea 71.
8 g and 640 ml of o-dichlorobenzene were charged into a 1,000 ml glass round bottom flask equipped with a stirrer, a thermometer and a condenser, and stirred vigorously at 135 ° C. for 2 hours and 160 hours over 4 hours.
The temperature was raised to ° C. At this time, the conversion of 2,3-naphthalenedicarboxylic anhydride was 9
9.7%, selectivity for 2,3-naphthalenedicarboxylic imide is 9
The content was cooled and filtered, and the crystal was dried to obtain a crude 2,3-naphthalenedicarboxylic imide containing 81.7% of 2,3-naphthalenedicarboxylic imide.
5.0 g were obtained. b) Production of 2,3-naphthalenedicarboxylic acid diamide 72.3 g of the crude 2,3-naphthalenedicarboxylic acid imide obtained in a), 300 ml of o-dichlorobenzene and 40.6 g of liquid ammonia were charged into a stainless steel autoclave and the temperature was adjusted to 60. The mixture was stirred for 10 hours while maintaining the temperature. At this time, the conversion of 2,3-naphthalenedicarboxylic acid imide was 9
9.4%, selectivity for 2,3-naphthalenedicarboxylic diamide
The content was 96.0%, and the content was cooled and filtered, and the crystal was dried to obtain 74.6 g of crude 2,3-naphthalenedicarboxylic diamide containing 82.5% of 2,3-naphthalenedicarboxylic diamide. c) Production of 2,3-dicyanonaphthalene 51.9 g of the crude 2,3-naphthalene dicarboxylic acid diamide obtained in b) and 300 ml of pyridine were charged into a 500 ml glass round bottom flask equipped with a stirrer, a thermometer and a condenser, and the contents were The mixture was stirred vigorously, and while maintaining the temperature at 60 ° C., 52 ml of phosphorus oxychloride was added dropwise over 5 minutes and maintained for another 30 minutes. At this time, the conversion rate of 2,3-naphthalenedicarboxylic acid diamide was 100%, and the selectivity of 2,3-dicyanonaphthalene was 91.5% .The content of 2,3-dicyanonaphthalene produced by pouring the content into 600 ml of ice water was used. Crystallization, filtration and drying of the crystals yielded 37.9 g of crude 2,3-dicyanonaphthalene containing 84.7% 2,3-dicyanonaphthalene. Example 2 a) Preparation of 2,3-naphthalenedicarboxylic acid imide 99.2% of 2,3-naphthalenedicarboxylic anhydride 79.8 g,
35.9 g of urea and 320 ml of decane were charged into a 500 ml glass round bottom flask equipped with a stirrer, a thermometer and a condenser, and heated to 135 ° C. with vigorous stirring at 135 ° C. for 2 hours and further for 4 hours to 160 ° C. At this time, the conversion of 2,3-naphthalenedicarboxylic anhydride was 9
9.3%, selectivity of 2,3-naphthalenedicarboxylic imide is 9
The content was cooled and filtered to obtain a crude 2,3-naphthalenedicarboxylic acid imide containing 83.0% of 2,3-naphthalenedicarboxylic acid imide 91.
1 g was obtained. b) Preparation of 2,3-naphthalenedicarboxylic acid diamide 71.2 g of crude 2,3-naphthalenedicarboxylic acid imide obtained in a), 300 ml of ethanol and 40.6 g of liquid ammonia
Was charged into a stainless steel autoclave, and the mixture was stirred for 10 hours while maintaining the temperature at 60 ° C. At this time, the conversion of 2,3-naphthalenedicarboxylic acid imide was 9
9.0%, selectivity for 2,3-naphthalenedicarboxylic diamide
The content was 98.1%, the content was cooled and filtered, and the crystal was dried to obtain 66.9 g of crude 2,3-naphthalenedicarboxylic diamide containing 92.5% of 2,3-naphthalenedicarboxylic diamide. c) Production of 2,3-dicyanonaphthalene 46.3 g of the crude 2,3-naphthalene dicarboxylic acid diamide obtained in b) and 300 ml of pyridine were charged into a 500 ml glass round-bottomed flask equipped with a stirrer, a thermometer and a cooler. The mixture was vigorously stirred to maintain the temperature at 60 ° C., and 52 ml of phosphorus oxychloride was added dropwise over 15 minutes, followed by a further 30 minutes. At this time, the conversion rate of 2,3-naphthalene dicarboxylic acid diamide was 100%, and the selectivity of 2,3-dicyanonaphthalene was 78.8% .The content of 2,3-dicyanonaphthalene produced by pouring the content into 600 ml of ice water was used. After crystallization, filtration and drying of the crystal, 32.9 g of crude 2,3-dicyanonaphthalene containing 83.3% of 2,3-dicyanonaphthalene was obtained. Example 3 a) Preparation of 2,3-naphthalenedicarboxylic acid imide 99.2% of 2,3-naphthalenedicarboxylic anhydride 79.8 g,
35.9 g of urea and 320 ml of tetralin were charged into a 500 ml glass round bottom flask equipped with a stirrer, a thermometer and a condenser, and heated at 145 ° C. for 1 hour with vigorous stirring to 170 ° C. over 3 hours. At this time, the conversion of 2,3-naphthalenedicarboxylic anhydride was 9
9.8%, selectivity for 2,3-naphthalenedicarboxylic imide is 9
The content was 7.1%, the content was cooled and filtered, and the crystal was dried to obtain crude 2,3-naphthalenedicarboxylic acid imide containing 83.1% of 2,3-naphthalenedicarboxylic acid imide 91.
7 g were obtained. b) Production of 2,3-naphthalenedicarboxylic acid diamide 71.1 g of the crude 2,3-naphthalenedicarboxylic acid imide obtained in a), 300 ml of benzene and 40.6 g of liquid ammonia were charged into a stainless steel autoclave and the temperature was maintained at 60 ° C. While stirring for 10 hours. At this time, the conversion of 2,3-naphthalenedicarboxylic acid imide was 9
9.4%, selectivity for 2,3-naphthalenedicarboxylic diamide
The content was 96.8%, the content was cooled and filtered, and the crystal was dried to obtain 76.3 g of crude 2,3-naphthalenedicarboxylic diamide containing 80.8% of 2,3-naphthalenedicarboxylic diamide. c) Production of 2,3-dicyanonaphthalene 53.0 g of the crude 2,3-naphthalenedicarboxylic diamide obtained in b) and 300 ml of dimethylformamide were stirred,
A 500 ml glass round bottom flask equipped with a thermometer and a condenser was charged, and the contents were vigorously stirred to keep the temperature at 60 ° C., and 52 ml of phosphorus oxychloride was added dropwise over 5 minutes, and further maintained for 30 minutes. At this time, the conversion rate of 2,3-naphthalenedicarboxylic acid diamide was 100%, and the selectivity of 2,3-dicyanonaphthalene was 87.6% .The content of 2,3-dicyanonaphthalene produced by pouring the content into 600 ml of ice water was used. Crystallization, filtration and drying of the crystals yielded 40.0 g of crude 2,3-dicyanonaphthalene containing 80.2% 2,3-dicyanonaphthalene. Example 4 a) Preparation of 2,3-naphthalenedicarboxylic acid imide 99.2% of 2,3-naphthalenedicarboxylic anhydride 79.8 g,
35.9 g of urea and 320 ml of mesitylene were charged into a 500 ml glass round bottom flask equipped with a stirrer, a thermometer and a condenser, and heated at 135 ° C. for 2 hours with vigorous stirring to 160 ° C. over 4 hours. At this time, the conversion of 2,3-naphthalenedicarboxylic anhydride was 9
9.0%, selectivity for 2,3-naphthalenedicarboxylic imide is 9
The content was cooled and filtered, and the crystal was dried to give crude 2,3-naphthalenedicarboxylic imide containing 80.5% of 2,3-naphthalenedicarboxylic imide 93.
3 g were obtained. b) Production of 2,3-naphthalene dicarboxylic acid diamide 73.4 g of the crude 2,3-naphthalene dicarboxylic acid imide obtained in a) and 102.0 g of liquid ammonia were charged into a stainless steel autoclave and the temperature was maintained at 60 ° C. Stirred for hours. At this time, the conversion of 2,3-naphthalenedicarboxylic acid imide was 9
9.8%, selectivity for 2,3-naphthalenedicarboxylic diamide 9
The content was cooled to 7.4%, and the content was cooled and filtered, and the crystal was dried to obtain 78.2 g of crude 2,3-naphthalenedicarboxylic diamide containing 78.8% of 2,3-naphthalenedicarboxylic diamide. c) Preparation of 2,3-dicyanonaphthalene 54.3 g of the crude 2,3-naphthalenedicarboxylic diamide obtained in b) and 300 ml of dimethylformamide are stirred,
A 500 ml glass round bottom flask equipped with a thermometer and a condenser was charged, and the contents were vigorously stirred to maintain the temperature at 60 ° C., and 52 ml of phosphorus oxychloride was added dropwise over 15 minutes, and further maintained for 30 minutes. At this time, the conversion rate of 2,3-naphthalenedicarboxylic acid diamide was 100%, and the selectivity of 2,3-dicyanonaphthalene was 72.0% .The content of 2,3-dicyanonaphthalene produced by pouring the content into 600 ml of ice water was used. Crystallization, filtration and drying of the crystal yielded 30.9 g of crude 2,3-dicyanonaphthalene containing 80.2% of 2,3-dicyanonaphthalene.

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Naoji Kurata               9-23 Atagoyama, Nishinomiya City, Hyogo Prefecture                (56) References SYNTHETIC COMMUNI               CATIONS, VOL. 11, No. 5               (1981) p. 351-363

Claims (1)

(57) [Claims] 1. It is characterized in that 2,3-naphthalenedicarboxylic diamide is dehydrated in a nitrogen-containing organic solvent in the presence of a dehydrating agent.
A method for producing 2,3-dicyanonaphthalene. 2. The method according to claim 1, wherein the dehydrating agent is phosphorus oxychloride. 3. 2,3-naphthalenedicarboxylic acid anhydride and urea are imidized to produce 2,3-naphthalenedicarboxylic acid imide, and then the 2,3-naphthalenedicarboxylic acid imide and ammonia are subjected to amidation reaction. 2,3-naphthalenedicarboxylic acid diamide, and then dehydrating the 2,3-naphthalenedicarboxylic acid diamide in a nitrogen-containing organic solvent in the presence of a dehydrating agent. Production method.