JP2003055327A - Method for producing dicyanonorbornanes - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing dicyanonorbornanes by which a catalyst effectively is made to act and which is sufficiently adoptable also in industrial scale when producing dicyanonorbornane(bicyclo[2.2.1]heptane- dicarbonitrile) by reacting cyanonorbornene(bicyclo[2.2.1]-5-heptene-2-carbonitrile) with hydrogen cyanide in the presence of a zero-valent nickel complex catalyst. SOLUTION: In this method for producing dicyanonorbornanes, the reaction is carried out in the presence of acrylonitrile in an amount of <=0.1 wt.% based on cyanonorbornene.

Description

Description: TECHNICAL FIELD [0001] The present invention relates to a method for producing dicyanonorbornanes. More specifically,
In the presence of a zero-valent nickel complex catalyst, cyano norbornene (bicyclo [2.2.1] -5-heptene-2-carbonitrile; hereinafter abbreviated as CNN) is reacted with hydrogen cyanide to give 2,5-dicyano. Norbornane (bicyclo [2.2.1] heptane-2,5-dicarbonitrile) and 2,6-dicyanonorbornane (bicyclo [2.2.
1] A method for producing dicyanonorbornane (bicyclo [2.2.1] heptanedicarbonitrile, hereinafter abbreviated as DCN) having heptane-2,6-dicarbonitrile as a main component. . 2. Description of the Related Art Conventionally, DNN by hydrocyanation of CNN has been known.
Examples of the method for producing CN include: i) a method using a cobalt carbonyl catalyst and triphenylphosphine as a catalyst system (US Pat. No. 2,666,780); ii) a catalyst system using tetrakis (triarylphosphite) palladium and triphenylphosphite. Method (J.
Am. Chem. Soc., 112 (1969)), iii) A method using a catalyst system comprising an isolated and purified zero-valent nickel complex catalyst and a Lewis acid (JP-A-3-95151) iv) Zero-valent nickel complex catalyst There have been proposed techniques relating to the type of catalyst and a method for producing the catalyst, such as a method of using a Lewis acid as a catalyst without isolation and purification (Japanese Patent No. 2866270). [0003] However, according to the study of the present inventors, when hydrogen cyanide is reacted with CNN in the presence of a zero-valent nickel complex catalyst, depending on the type of impurities introduced from the raw material. It was found that the catalyst lost its activity. [0004] That is, the present inventors have found that when acrylonitrile is present in the reaction of CNN with hydrogen cyanide in the presence of a zero-valent nickel complex catalyst, the activity of the catalyst is reduced. [0005] By the way, as the main raw materials used for producing DCNs, that is, CNN and hydrogen cyanide, it is economically industrial to use those produced by the following production method. That is, CNN is prepared by reacting acrylonitrile with cyclopentadiene or dicyclopentadiene (Japanese Patent Publication No. 52-49437, Japanese Patent Application Laid-open No. Sho 49-4).
No. 8650, Patent No. 2873100) are industrially effective methods. On the other hand, as for hydrogen cyanide, in addition to the ammoxidation method using methane, ammonia and air, the one produced as a by-product when producing acrylonitrile by the ammoxidation method using propylene, ammonia and air can be used. However, in the above-mentioned industrial production method of the main raw material, there is a possibility that acrylonitrile is contained as an impurity in both the raw material of CNN and hydrogen cyanide, or in at least one of the raw materials. However, in the conventional techniques i) to iv), only the type of catalyst for adding hydrogen cyanide to CNN and the method for producing the catalyst are described, and the influence of impurities introduced from the raw material is considered. For clarification, no industrially satisfactory method for producing DCNs has been provided. An object of the present invention is to produce DCNs by reacting CNN with hydrogen cyanide in the presence of a zero-valent nickel complex catalyst to produce DCNs by effectively using the catalysts. It is to provide a method. The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, the present invention is characterized in that, in producing DCNs by reacting hydrogen cyanide with CNN in the presence of a zero-valent nickel complex catalyst, the amount of acrylonitrile coexisting during the reaction is 0.1% by weight or less based on CNN. This is a method for producing DCNs. DETAILED DESCRIPTION OF THE INVENTION CNN used in the present invention
As for, those industrially produced by a Diels-Alder reaction between acrylonitrile and cyclopentadiene or dicyclopentadiene can be used. On the other hand, the hydrogen cyanide used in the present invention is a by-product produced when acrylonitrile is produced by an ammoxidation method using methane, ammonia and air as raw materials or an ammoxidation method using propylene, ammonia and air. By taking out
Those manufactured industrially can be used. In the present invention, the amount of acrylonitrile coexisting during the reaction between CNN and hydrogen cyanide is 0.1% by weight or less, preferably 0.07% by weight or less, more preferably 0.04% by weight or less based on CNN. 0.1
When the amount is less than the weight%, the catalyst works effectively with an economical amount of catalyst used. At this time, acrylonitrile may be brought in from the raw material CNN, may be brought in from the other raw material, hydrogen cyanide, or may be brought in from both the CNN and hydrogen cyanide raw materials. The zero-valent nickel complex catalyst and Lewis acid promoter used in the present invention are synthesized according to the following chemical reaction formula (I). NiX ₂ + M + 4L → NiL ₄ + MX ₂ (I) Nickel halodihydride Cellovalent nickel complex Lewis acid However, in the above reaction formula and formula (I), X is a halogen atom, M is zinc, cadmium, At least one selected from beryllium, aluminum, iron, and cobalt
L is a ligand P (x) (y) (z) (P is a phosphorus atom, x, y and z are each R or OR,
R represents an alkyl group or an aryl group having 18 or less carbon atoms. ). When M is aluminum, it is synthesized according to the following chemical reaction formula (II). 3NiX ₂ + 2Al + 12L → 3NiL ₄ + 2AlX ₃ (II) In the present invention, the nickel halide is converted to zinc, cadmium, beryllium, aluminum, iron, cobalt by the chemical reaction formula (I) or (II). The synthesis of the zero-valent nickel complex catalyst and the Lewis acid cocatalyst by reduction with at least one metal selected from the above is performed in the presence of water. As for the method of adding water, water can be added as it is, but when the nickel halide is a hydrate, the water can also be used. In the present invention, the amount of water present during the synthesis of the catalyst is preferably 0.5 to 40 mol per mol of nickel atom contained in the nickel halide,
More preferably, it is 0.8 to 30 mol, and further preferably, it is 1 to 20 mol. If it is 0.5 mol or more, a high catalyst synthesis yield can be obtained. When it is less than 40 mol, a high catalyst synthesis yield can be obtained, and a high catalyst stability at the time of performing hydrocyanation of CNN can be obtained. The zero-valent nickel complex catalyst in the present invention is represented by the following general formula (III). NiL ₄ (III) The four Ls in the general formula (III) may be the same or different. L represents a ligand having the general formula (IV) P (x) (y) (z) (IV), P is a phosphorus atom, and x, y,
z represents R or OR, and R represents an alkyl or aryl group having 18 or less carbon atoms selected from the group consisting of: As the ligand, for example, triphenyl phosphite, tri (m- or p-chlorophenyl) phosphite, tri (m- or p-methoxyphenyl) phosphite, tri (m- or p-cresyl) Triaryl phosphites such as phosphite and tri (m- or p-nonylcyphenyl) phosphite; trialkyl phosphites such as triethyl phosphite, triisopropyl phosphite and tributyl phosphite; triphenyl phosphine; m- or p-chlorophenyl)
Phosphine, tri (m- or p-methoxyphenyl) phosphine, tri (m- or p-cresyl) phosphine,
Triarylphosphines such as tri (m- or p-nonylcyphenyl) phosphine; trialkylphosphines such as triethylphosphine, triisopropylphosphine and tributylphosphine; and mixtures thereof, preferably triarylphosphite. And triarylphosphines, more preferably triphenylphosphite, tri (m- or p-cresyl) phosphite, tri (m- or p-nonylcyphenyl) phosphite, triphenylphosphine, tri ( m
-Or p-cresyl) phosphine, tri (m- or p-
Nonylcyphenyl) phosphine and the like. The nickel halide in the present invention is:
For example, nickel chloride, nickel bromide, nickel iodide can be mentioned, and anhydrous salts or hydrates are used. The reducing agent for reducing nickel halide in the present invention generates a Lewis acid cocatalyst as a result of a reduction reaction, and at least one selected from zinc, cadmium, beryllium, aluminum, iron and cobalt. One type of metal, the most preferred reducing agent is zinc. The amount of the reducing agent used is preferably larger than the hydrate of nickel halide in order to increase the yield of the zero-valent nickel complex catalyst. More preferably, the molar ratio of nickel halide: reducing agent = 1: 1 to 1: 6. The unreacted portion of the used reducing agent is recovered by filtration or the like, and can be reused in the next reduction reaction. The amount of the ligand in the present invention may be about 4 times the molar amount (chemical equivalent) of the nickel halide, and there is no problem in the yield of the zero-valent nickel complex. However, in order to increase the activity and life during the hydrocyanation reaction, the ligand is preferably at least 5 mol, more preferably at least 6 mol, based on 1 mol of the nickel halide used.
It is used in a range of from .about.36 mol, more preferably from 8 to 20 mol. If the amount exceeds 36 moles, the reaction is not hindered, but it is not necessarily economical in consideration of the loss of ligand recovery during work-up and purification of the hydrocyanation reaction solution. In the synthesis of the zero-valent nickel complex catalyst, the above-mentioned neutral ligand can play the role of a solvent, but other solvents may be used without any problem. Examples of the solvent used include aryl compounds having at least one hydroxyl group and having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, such as fluorine, chlorine, bromine, iodine, nitro, cyano, and carbon. The above-mentioned aryl compound having one or more substituents selected from the group consisting of the hydrocarbon groups of Formulas 1 to 9 may be used. For example, phenol, p-cresol, resorcin, β-naphthol, p-chlorophenol, p-nitrophenol, p-butylphenol and similar compounds. Other solvents include, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; nitriles such as acetonitrile and benzonitrile; ethers such as dioxane, o-dimethoxybenzene, tetrahydrofuran, dimethoxyethane, and diethoxyethane. , Chloroaromatic hydrocarbons such as o-dichlorobenzene and p-dichlorobenzene, and similar compounds. Also, CNN can be used as a solvent. Regarding the conditions for synthesizing the zero-valent nickel complex catalyst, the nickel content in the nickel halide is not particularly limited, but is desirably 0.1 to 2% with respect to the total charge. The temperature condition is usually in the range of 0 to 150 ° C, preferably 40 to 100 ° C. The reaction time is generally 1 to 10 hours, preferably 1 hour.
It takes about 3 hours. The hydrocyanation of CNN in the present invention is carried out, for example, by introducing a predetermined amount of CNN into the reactor after synthesizing the above zero-valent nickel complex catalyst, and then introducing hydrogen cyanide with stirring at a predetermined temperature. .
As for the charging ratio of the zero-valent nickel complex catalyst synthesizing solution and CNN, the molar ratio of the zero-valent nickel complex catalyst synthesizing solution to CNN is usually 1: 5000 to 1:20, preferably 1: 2000 to
The range is 1: 100. The amount of hydrogen cyanide to be used can be any molar amount with respect to 1 mol of CNN, but is usually 1 mol. The reaction temperature of hydrocyanation of CNN is as follows:
The temperature is preferably from -20 to 200C, more preferably from 0 to 130C, and still more preferably from 20 to 100C. The reaction can be carried out under normal pressure or under pressure, but since there is no remarkable reaction promoting effect by increasing the pressure, it is usually carried out under normal pressure. In the present invention, the reaction mode of hydrocyanation of CNN is usually a batch system, but the reaction is carried out by continuously supplying CNN, hydrogen cyanide, a zero-valent nickel complex catalyst synthesis solution, and, if necessary, a solvent. A continuous type is also adopted. The DCNs produced according to the present invention are 2,5
It is obtained as a mixture containing -dicyanorbornane and 2,6-dicyanonorbornane as main components. The present invention will be described in more detail with reference to the following examples. Example 1 Acrylonitrile was added to a 0.5 L glass flat bottom separable flask equipped with a stirrer, a thermometer, a nitrogen inlet, a hydrogen cyanide inlet, a cooler, and the like.
99.13 g (0.831 mol) of CNN containing 05% by weight, 100.0 g of toluene, tetrakis (triphenyl phosphite)
Nickel 2.00 g (1.54 mmol), zinc chloride 0.21 g (1.53 mm
ol) and 1.92 g (6.19 mmol) of triphenyl phosphite, and the gas phase was replaced with nitrogen at room temperature, and then the temperature was raised to 60 ° C. Next, 22.38 g of liquid hydrogen cyanide (0.828mo
l) was fed over one hour. The reaction solution after the supply of hydrogen cyanide was analyzed by gas chromatography. As a result, the conversion of CNN was 99.6 mol% and the selectivity of DCNs was 1
It was 00 mol%. Further, as a result of analyzing the reaction solution using liquid chromatography, the residual ratio of tetrakis (triphenylphosphite) nickel was 11 mol%. Example 2 The same operation as in Example 1 was carried out except that CNN containing 0.01% by weight of acrylonitrile was used, and 22.42 g (0.829 mol) of hydrogen cyanide was supplied over 1 hour. As a result, the conversion of CNN was 99.8 mol%, the selectivity of DCNs was 100 mol%, and the residual ratio of tetrakis (triphenylphosphite) nickel was
It was 66 mol%. (Example 3) A 50 mL glass round bottom flask equipped with a stirrer, a thermometer, a nitrogen inlet, a cooler, and the like,
Nickel chloride hexahydrate 1.32 g (5.5 mmol) zinc powder 0.73
g (11.1 mmol), triphenyl phosphite 11.17 g (3
6.0 mmol) and CNN 30.55 g (256.4 mmol) were charged, the atmosphere in the gas phase was replaced with nitrogen at room temperature, and the mixture was reacted at 60 ° C. for 2 hours with stirring. As a result of analyzing the reaction solution using high performance liquid chromatography, a tetrakis (triphenylphosphite) nickel catalyst was obtained in a yield of 89.5 mol%. Next, 284.4 g (2.39 mol) of CNN and 83.9 g of toluene were charged into a 1-L glass flat-bottom separable flask equipped with a stirrer, thermometer, nitrogen inlet, hydrogen cyanide inlet, cooler, and the like. Was replaced with nitrogen, and then the temperature was raised to 60 ° C. Next, the entire amount of the catalyst synthesis solution obtained above was added, and 71.57 g (2.64 mol) of liquid hydrogen cyanide containing 0.3% by weight of acrylonitrile was supplied over 4 hours. The amount of acrylonitrile supplied at this time corresponds to about 0.07% by weight based on the raw material CNN. As a result, C
The conversion of NN is 99.9 mol%, and the selectivity of DCNs is 100 mol.
%, And the residual ratio of nickel tetrakis (triphenylphosphite) was 23 mol%. Example 4 The same operation as in Example 3 was carried out except that liquid hydrogen cyanide containing 0.15% by weight of acrylonitrile was used and 71.20 g (2.63 mol) of hydrogen cyanide was supplied over 4 hours. The amount of acrylonitrile supplied at this time was about 0.
034% by weight. As a result, the conversion of CNN was 99.
5 mol%, selectivity of DCNs is 100 mol%, residual ratio of tetrakis (triphenylphosphite) nickel is 61 mol%
Met. Example 5 The same operation as in Example 3 was carried out except that acrylonitrile-free liquid hydrogen cyanide was used and 71.36 g (2.64 mol) of hydrogen cyanide was supplied over 4 hours. As a result, the conversion of CNN was 99.9 mol%, the selectivity of DCNs was 100 mol%, and the residual ratio of tetrakis (triphenylphosphite) nickel was
78 mol%. Comparative Example 1 The procedure of Example 1 was repeated except that CNN containing 0.15% by weight of acrylonitrile was used. As a result, hydrogen cyanide is reduced to 0.
Since the reaction was stopped at the time of the supply over 5 hours, the supply of hydrogen cyanide was stopped. As a result, the conversion of CNN was 53 mol%, and no tetrakis (triphenylphosphite) nickel remained. Comparative Example 2 The same operation as in Example 3 was carried out except that liquid hydrogen cyanide containing 0.57% by weight of acrylonitrile was used. The amount of acrylonitrile supplied at this time corresponds to about 0.13% by weight based on the starting CNN. As a result, the reaction was stopped when hydrogen cyanide was supplied for 3.2 hours, so the supply of hydrogen cyanide was stopped. As a result, the conversion of CNN was 79 mol.
%, And no tetrakis (triphenylphosphite) nickel remained. According to the method described in the present invention, CNN and hydrogen cyanide can be reacted effectively by the action of a zero-valent nickel complex catalyst.
It can be said that this is a method for producing CNs.

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Claims (1)

Claims: 1. A cyano norbornene (bicyclo [2.2.1] -5-heptene) in the presence of a zero-valent nickel complex catalyst.
-2-carbonitrile) with hydrogen cyanide to produce dicyanonorbornanes, the amount of acrylonitrile coexisting during the reaction is
A method for producing dicyano norbornanes, which is 0.1% by weight or less.