JPH0560459B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of the Invention] The present invention relates to the reaction of 4-nitrophthalonitrile with an aliphatic, cycloaliphatic, aralkyl, or aromatic primary, secondary, or tertiary monool or diol using a tertiary amine as a catalyst. A method for producing a 4-alkoxyphthalonitrile derivative represented by the following general formula, wherein the tertiary amine is an alicyclic amine having a total carbon number of 12 or less, an aromatic amine having a total carbon number of 12 or less. The present invention relates to a method for producing a 4-alkoxyphthalonitrile derivative, characterized in that the 4-alkoxyphthalonitrile derivative is selected from the group consisting of 4-alkoxyphthalonitrile amines and aliphatic amines having a total carbon number of 12 or less. Here, R is selected from alkylene, cycloalkylene, aralkylene or arylene groups, R has 20 or less carbon atoms, and X represents hydrogen, a hydroxyl group, or a 1',2'-dicyano-4'-phenoxy group. [Prior Art] A method for producing the 4-alkoxyphthalonitrile derivative of formula (1) by reacting 4-nitrophthalonitrile with the alcohols described above is known from "TM Keller (TM
Keller et al. Synthesis 613 (1980)”
It is described in. This reaction is expressed by the following formula (2).

[Problem to be solved by the invention] By the way, this reaction can be carried out under an inert gas atmosphere in order to prevent the by-produced HNO ₂ from being oxidized to HNO ₃ and acting as an oxidizing agent. is necessary. Additionally, a basic catalyst is used to remove _HNO2 from the reaction system. As such basic catalysts, alkali metal carbonates such as anhydrous K ₂ CO ₃ and anhydrous Na ₂ CO ₃ are conventionally used. However, since alkali metal carbonates are poorly soluble in the above solvents, their ability to remove HNO ₂ is low, and there is a high possibility that side reactions caused by HNO ₂ will occur, such as the production of dark brown tar-like substances. In particular, as stated in the above literature, MOH, which is likely to be produced by the reaction of formula (3), interferes with the reaction of formula (2). HNO ₂ +M ₂ CO ₃ →M・NO ₂ +M・HCO ₃ M・HCO ₃ →thermal MOH + CO ₂ (3) (where M represents an alkali metal ion) Furthermore, basic catalysts simply remove HNO ₂ In addition, due to the equilibrium in formula (4), the alkoxide anion -R-O ^- is induced and the substitution reaction in formula (2) proceeds smoothly. Due to its solubility and low basicity, the equilibrium of formula (4) is difficult to occur, and therefore a high temperature and long reaction time is required. A drawback is that side reactions such as condensation of certain 4-alkoxy-1,2-phthalonitrile derivatives occur. Y−R−OH+M・₂ CO ₃ Y−R−O ⁻ +M ⁺ +MHCO ₃ or Y−R−OH+BY−R−O ⁻ +BH ⁺ (4) (here, Y and R are synonymous with formula (2), M is synonymous with formula (3), and B represents the tertiary amines mentioned above.) In this way, in the conventional method using an alkali metal carbonate as a catalyst, the reaction system becomes heterogeneous, and in order to increase the yield, requires strong stirring and high temperatures. Furthermore, since the surface of the catalyst gradually becomes covered with by-products and loses its activity, it is necessary to add an excessive amount in several portions. In particular, when the partner reactant is a lower alcohol with a low boiling point of about _C1 to _C3 , it must be stirred for a long time below its boiling point under a stream of inert gas, or stirred at high temperature in a pressure-resistant closed container in an inert gas atmosphere. A reaction must be carried out. Such reaction conditions generally cause condensation of phthalonitrile derivatives, resulting in not only a low yield of the target product but also the disadvantage of contaminating large amounts of by-products. [Means for solving problems]

The present inventor provides that the catalyst for the above reaction is selected from the group consisting of alicyclic amines having a total carbon number of 12 or less, aromatic amines having a total carbon number of 12 or less, and aliphatic amines having a total carbon number of 12 or less. The inventors have discovered that the above problems can be solved by using a tertiary amine, and have completed the present invention. The present invention involves the reaction of 4-nitrophthalonitrile with an aliphatic, alicyclic, aralkyl, or aromatic primary, secondary, or tertiary monool or diol using a tertiary amine as a catalyst. A method for producing a 4-alkoxyphthalonitrile derivative represented by the formula, wherein the tertiary amine is an alicyclic amine having a total carbon number of 12 or less, an aromatic amine having a total carbon number of 12 or less, and a total carbon This is a method for producing a 4-alkoxyphthalonitrile derivative, characterized in that the 4-alkoxyphthalonitrile derivative is selected from the group consisting of aliphatic amines having a number of 12 or less. The present invention greatly improves the drawbacks of the conventional technology using carbonates, and uses the above-mentioned tertiary amines, which are soluble in the reaction solvent and highly basic, as a catalyst, and is 100℃, preferably 60℃~90℃,
Short time, for example 1 hour to 30 hours, preferably 2 to 30 hours
The desired product is produced in good yield under mild conditions for 25 hours,
Furthermore, since there are very few side reactions, the unreacted and expensive starting material 4-nitro-1,2-phthalonitrile can be recovered almost quantitatively. The tertiary amines used in the present invention have 12 or less carbon atoms, and if the number of carbon atoms is 13 or more, the molecular weight becomes large and the catalytic ability decreases. These tertiary amines can be divided into the following three groups based on their basicity. A Highly basic group Dinitrogen-containing dialicyclic compounds: 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]nonene-(5), 1,
8-diazabicyclo[5,4,0]undecene-(7), etc., and 4-dimethylaminopyridine, 2-
Dimethylaminopyridine B Medium basic group Nitrogen-containing alicyclic compounds: 1,4-dimethylpiperazine, 1-methylpiperidine, 1-methylmorpholine, etc. Aliphatic amines: triethylamine, tripropylamine, etc. C Low basic group Contains Nitrogen aromatic compound: pyridine, 2- or 4
-methylpyridine, 2,4- or 2,6-
Dimethylpyridine, 2,4,6-trimethylpyridine, etc. There is no significant difference in the catalytic ability of these three groups when reacting with Y-R-OH, which tends to form alkoxide anions, such as tert-butanol. However, it is difficult to form alkoxide anions such as methanol, and Y-R-OH has a low boiling point, so the reaction must be carried out at a low temperature of about 60°C.
When targeting , the target product can be obtained in a relatively short time and in good yield by using a group A catalyst.
Preferred examples of combinations of Y-R-OH and catalysts are shown below. Highly basic catalyst group - methanol, ethanol, n
- Propyl alcohol, etc. Medium basic catalyst group - Ethylene glycol, propylene glycol, n-alcohols with _C4 or more, etc. Low basic catalyst group - Phenol, benzyl alcohol, hydroquinone, etc. [Effects of the Invention] In the present invention, an alicyclic amine having a total carbon number of 12 or less, which is soluble in a reaction solvent such as DMF or DMSO,
Aromatic amines with a total carbon number of 12 or less and
Since the catalyst is a tertiary amine selected from the group consisting of aliphatic amines of 12 or less, the reaction system becomes homogeneous, and the reaction proceeds smoothly even at low temperatures of about 50 to 60 degrees Celsius, resulting in a high yield of the target product. In addition, separation is easy because side reactions such as condensation of phthalonitrile derivatives do not occur, and in particular, unreacted and expensive 4-nitrophthalonitrile can be recovered almost quantitatively. As described above, the production method of the present invention has the characteristics of improving reaction conditions, shortening reaction time, facilitating separation and purification, and making it possible to extremely increase the yield of the target product and the recovery rate of unreacted starting materials. The phthalonitrile derivative can be used as it is or after being reacted with ammonia to form a diiminoisoindoline derivative, it can be reacted with a basic medium (e.g. dimethylamino-2-ethanol) in the presence or absence of an alkaline earth or transition metal salt. The heating reaction inside produces (metal) phthalocyanine derivatives, which are used in pigments, electronic materials, redox catalysts, etc. However, although unsubstituted (metallic) phthalocyanine is chemically stable, it is only slightly soluble in concentrated sulfuric acid or boiling DMF, and can only be purified by sublimation, and its usage conditions are extremely limited. ing. The corresponding (metal) phthalocyanine derivative obtained from the compound of formula (1) obtained in the present invention in the same manner as described above becomes solvent soluble due to the presence of the R group shown in formula (1), and is easy to purify. Not, but
Painting, cast coating, vapor deposition coating, spatter coating,
Molding by various methods such as mixing with other substances,
It is possible to form a film and is extremely useful as a member for dyes, electronic materials, redox catalysts, etc. In addition, the (metal) phthalocyanine derivative has the characteristic that it can be reacted with various reagents in a homogeneous solution to perform various chemical modifications. In this way, the present invention has demonstrated that the formula (1) is an important intermediate raw material for solvent-soluble (metal) phthalocyanine derivatives.
The object of the present invention is to provide a novel manufacturing method for producing 4-alkoxyphthalonitrile derivatives with good yield. [Example] Next, the present invention will be explained in more detail with reference to Examples. Example 1 4-nitro-1,2-phthalonitrile (hereinafter referred to as
(abbreviated as NPN) 50g (0.29mol), methanol 14.23
ml (0.35 mol) in 100 ml dehydrated DMF,
Place _CaCl2 into a 300 ml four-necked flask equipped with a reflux tube with a drying tube, a nitrogen inlet tube, and a stirring device, and place 1,8-diazabicyclo[5,4,0]undecene-(7) (hereinafter referred to as 1,8-diazabicyclo[5,4,0]undecene-(7) 43.07 ml (0.29 mol) of DBU (abbreviated as DBU) was added thereto, and the mixture was reacted at 60°C for 24 hours. After cooling, remove the solvent under reduced pressure at 40℃ or less, add an appropriate amount of chloroform and dissolve, 600ml.
of ice-cold 6N-HCl, and the chloroform phase was separated. The aqueous phase was extracted three times with 100 ml of chloroform, combined with the previous chloroform phase, dried over anhydrous sodium sulfate, filtered, and decolorized with activated carbon, and the solvent was concentrated under reduced pressure. After cooling, the precipitated yellow crystals were collected by filtration, the mother liquor was further concentrated and recrystallized, and the white crystals were collected by filtration. As a result of analysis, the yellow crystals are NPN, the raw material.
(Recovered amount: 2.1 g, 4.2%), and the white crystals are the desired 4-methoxy-1,2-phthalonitrile (yield:
42.3g, 93.4%). Note that the sum of the recovery rate of NPN and the yield of the target product will be hereinafter referred to as the total recovery rate (4.2+93.4=97.6% in this example). 4-methoxy-1,2-phthalonitrile NMR (CDCl ₃ , δppm): Ha7.1, 7.2 (1H),
Hb7.2 (1H), Hc7.65, 7.7 (1H), CH ₃ 3.9 (3H) IR (KBr tablet, cm ^-1 ): νφ _-H 3100, 3050, 3000,
ν _CH3 2950, 2850, ν _C ≡ _N 2250 Rf (chloroform, silica gel thin film chromatography): 0.40 Reference example 1 NPN 50g (0.29 mol), methanol 14.23ml
(0.35 mol) and 100 ml of DMF were placed in the same apparatus as in Example 1, and anhydrous K ₂ CO ₃ was added at 60°C under a dry nitrogen atmosphere.
Immediately after heating, 10 g of the solution was added a total of 6 times every 3 hours, and the reaction was allowed to proceed for 24 hours. After that, the same procedure as in Example 1 was carried out to obtain 10.6 g (22.3%) of the target 4-methoxy-1,2-phthalonitrile and 4.3 g of unreacted NPN.
(8.6%) obtained. The total recovery rate was 30.9%, which is significantly lower than the results of Example 1. The remaining 70% was a pale green insoluble material, and IR analysis suggested that it was a condensate that had lost the nitrile group. Examples 2 to 10 Various alcohols and catalysts were used as shown in Table 1, and the reaction conditions were as shown in Table 1.
The reaction was carried out in the same manner as in Example 1, and the corresponding target product was obtained. Confirmation of the target object is through the disappearance of their common IR spectral characteristic absorption band: ν _NO2 1550, 1330 cm ^-1 ,
Appearance of ν _CH2 , ν _CH , ν _CH3 from 2800 to 3080 cm ⁻¹ , ν _C ≡ _N
retention of 2250, ν _COC 1210, appearance of 1100, and
This was performed using FD-Mass spectrum (described as m/e value in Table 1).

[Table] Example 11 NPN 50g (0.29 mol), ethylene glycol 93
g (1.5 mol), pyridine 22.9 g (0.29 mol),
100 ml of DMF was reacted at 80°C for 2 hours in the same manner as in Example 1, and the crude product obtained by performing the same hydrochloric acid treatment and extraction procedure was applied to a silica gel column (φ10 × 30 cm,
100 mesh, chloroform/methanol = 10/1)
to obtain three components of Rf=0.95, 0.62, and 0.38. As a result of analysis, the first component was 1,2-bis[4'-
(1',2'-dicyanophenyloxy)]ethane 1.2g
(2.6%), the second component is 4-(2'-hydroxyethyloxy)1,2-phthalonitrile 50.8g (93.4%)
%), and the third component was 1.1 g (2.2%) of unreacted NPN. However, the yield is based on NPN. 1,2-bis[4'-(1',2'-dicyanophenyloxy)]ethane NMR (CDCl ₃ , δppm): φ-H7.1, 7.2, 7.65,
7.7 (6H), CH ₂ 4.2 (4H) IR (KBr tablet, cm ^-1 ): ν _-H 3100, 3050, 3000,
ν _CH2 2955, 2853, ν _C ≡ _N 2250 Elemental analysis (wt%, calculated value in Katsuko):: C68.55
(68.78), H3.18 (3.21), N17.86 (17.82) 4-(2'-hydroxyethyloxy)-1,2-
Phthalonitrile NMR (CDCl ₃ , δppm): φ−H7.15, 7.22,
7.65, 7.7 (3H), CH ₂ 3.8, 4.15 (4H), OH4.7
(1H) IR (KBr tablet, cm ^-1 ): ν _OH 3430, ν〓 _-H 3100,
3055, 3025, ν _CH2 2950, 2845, ν _C ≡ _N 2245 Elemental analysis (wt%, calculated value in Katsuko): C63.95
(63.82), H4.41 (4.28), N14.85 (14.89) Example 12 Processed in exactly the same manner as in Example 11, except that the amount of ethylene glycol charged was 9 g (0.15 mol),
1,2-bis[4'-
(1′,2′-dicyanophenyloxy)]ethane 42.43
g (93.1%), 4-(2'-hydroxyethyloxy)-1,2-phthalonitrile 0.8 g as the second component
(1.5%), 1.7 g of unreacted NPN (3.4
%) was obtained. However, the yield is based on NPN. Example 13 The same procedure as in Example 11 was carried out except that 177 g (1.5 mol) of 2,5-hexanediol was used, and three components with Rf=0.98, 0.73, and 0.38 were obtained by column chromatography separation. As a result of analysis, the first component was 6.5 g (13.1%) of 2,5-bis[4'-(1',2'-dicyanophenyloxy)]hexane, and the second component was 4-[2'-(5 '-Hydroxyhexyloxy)]-1,2-phthalonitrile 58.6g (83.0%), the third component is unreacted
The amount of NPN was 1.8g (3.6%). In addition, 4-[5′-(2′-hydroxyhexyloxy)]-
A slight amount of a substance presumed to be 1,2-phthalonitrile was observed. Both the first component and the second component are very similar to the corresponding first and second component IRs already described in Example 12, and differ only in the depth of the ν _CH2 vibration band. 2,5-bis-[4'-(1',2'-dicyanophenyloxy)]hexane Elemental analysis (wt%, calculated value in cutlet): C71.45
(71.34), H4.95 (4.90), N14.97 (15.13) 4-(2'-(5'-hydroxyhexyloxy)]-
1,2-phthalonitrile Elemental analysis (wt%, calculated value in Katsuko): C68.76
(68.83), H6.60 (6.60), N11.52 (11.47) Example 14 NPN50g (0.29mol), benzyl alcohol
37.63g (0.35mol), 4-methylpyridine 27.0g
(0.29 mol) was reacted at 80°C for 2 hours in the same apparatus as in Example 1, and fractionally recrystallized in the same manner. As a result of the analysis, 63.25g (93.1%) of the main product as white crystals was the desired 4-benzyloxy-1,2-phthalonitrile, and unreacted as pale yellow crystals.
1.1 g (2.2%) of NPN was recovered. 4-Benzyloxy-1,2-phthalonitrile Elemental analysis (wt%, calculated value in Katsuko): C76.55
(76.91), H4.39 (4.30), N12.20 (11.96) Example 15 NPN50g (0.29mol), Hydroquinone 16.52g
(0.15 mol) and 27.0 g (0.29 mol) of 2-methylpyridine were treated in the same manner as in Example 11, and three components with Rf = 0.83, 0.44, and 0.38 were obtained by column chromatography separation.
As a result of the analysis, the first component was p-di[4-(1,2-
Dicyanophenyloxy) Phenylene 47.11g
(89.7%), the second component is 4-[4'-(hydroxyphenyloxy)]-1,2-phthalonitrile 2.36g
(3.4%), the third component is unreacted NPN2.2g (4.4%)
It was hot. p-di[4-(1,2-dicyanophenyloxy)]phenylene Elemental analysis (wt%, calculated value in cutlet): C72.88
(72.92), H2.69 (2.78), N15.55 (15.46) 4-[4′-(hydroxyphenyloxy)]-1,
2-phthalonitrile Elemental analysis (wt%, calculated value in Katsuko): C71.36
(71.18), H3.36 (3.41), N11.92 (11.86) Reference Example 2 4-(octyloxy)- obtained in Example 9
27.2 g of 1,4-phthalonitrile was added to the gas introduction pipe,
Place in a 300ml four-necked flask equipped with a reflux tube with a drying tube and a dropping funnel, and add 0.2g of metallic sodium and 200ml of dehydrated methanol into the dropping funnel. A methanol solution was added over about 3 minutes while vigorously passing dehydrated ammonia gas through the mixture, and the mixture was stirred at room temperature for 2 hours and under boiling reflux for 1 hour. After cooling on ice, the precipitated crystals were collected by filtration and dried under reduced pressure to obtain 5-(octyloxy)diiminoisoindoline in a yield of about 95%. This material is strongly hygroscopic, and nitrile disappears under IR.
This was confirmed by the appearance of absorption bands specific to iminoisoindoline at 1570, 1650, and 3450 cm ^-1 . 14.5 g (approximately 0.05 mol) of the above diiminoisoindoline was dissolved in 80 ml of N,N-dimethylamino-2-ethanol, reacted for 5 hours under boiling reflux while passing dry nitrogen, and after cooling, the mixture was poured into a large amount of methanol. The green precipitate was collected by filtration and dried under reduced pressure to obtain 3.2 g (20%) of tetra(octyloxy)phthalocyanine.
I got it. The visible absorption spectrum (CHCl ₃ ) is 668,
The maximum absorption is at 702 nm, logε=5.10, respectively.
4.98, which is very similar to ordinary unsubstituted phthalocyanine. Furthermore, in the closure reaction of diiminoisoindoline, if a divalent metal salt is present, a phthalocyanine derivative having a central metal can be obtained in a yield of 30 to 40%. Tetra(octyloxy)phthalocyanine is soluble in almost all organic solvents except lower aliphatic alcohols, and the corresponding metal salts are also soluble in chloroform,
Soluble in benzene, tetrahydrofuran, etc.
Furthermore, if the alkoxy substituent is C ₃ or more, it is soluble at least in chloroform regardless of the presence or absence of a central metal.

Claims (1)

[Claims] 1 4-nitrophthalonitrile and an aliphatic, alicyclic, aralkyl, or aromatic primary, secondary, or tertiary monool or diol are reacted using a tertiary amine as a catalyst. A method for producing a 4-alkoxyphthalonitrile derivative represented by the following general formula, wherein the tertiary amine is an alicyclic amine having a total carbon number of 12 or less, an aromatic amine having a total carbon number of 12 or less and aliphatic amines having a total carbon number of 12 or less. (Here, R is alkylene, cycloalkylene,
selected from aralkylene or arylene group, R
has 20 or less carbon atoms, and X represents hydrogen, a hydroxyl group, or a 1',2'-dicyano-4'-phenoxy group. 2. The method according to claim 1, wherein the catalyst is a pyridine derivative. 3 Pyridine derivatives include pyridine, 2-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, 2,4,
The method according to claim 1 or 2, characterized in that the pyridine is selected from 6-trimethylpyridine or 4-dimethylaminopyridine. 4 The catalyst is 1,4-diazabicyclo[2,2,
2] Octane, 1,5-diazabicyclo[4,
3,0]nonene-5 or 1,8-diazabicyclo[5,4,0]undecene-(7).