JPS61287964A - Production of t-butyl-substituted phthalocyanine and its intermediate - Google Patents

Abstract

PURPOSE:To obtain the titled cyanine under mild conditions with less synthetic steps by starting with inexpensive starting materials, by reacting a specified compd. with 4-t-butyl-1,2-cyanobenzene in the presence of a strong org. base in an org. solvent. CONSTITUTION:t-Butylbenzene is reacted with bromine in the presence of a catalyst. The resulting 4-t-butyl-1,2-dibromobenzene is reacted with a metal cyanide in an org. solvent. The resulting 4-t-butyl-1,2-dicyanobenzene is reacted with a compd. of the formula MX2 or MOR (wherein M is H, metal; X is chlorine, iodine; R is alkyl) in the presence of a strong org. base in an org. solvent to obtain the desired t-butyl-substd. phthalocyanine of the formula (wherein t-Bu is t-butyl).

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides a method for producing t-butyl-substituted phthalonitrile in just two steps starting from industrially easily available raw materials, and The present invention relates to a method for producing t-butyl-substituted phthalocyanines.

[Conventional technology]

Conventionally, t-butyl-substituted phthalonitrile has been produced starting from 0-xylene, which is industrially easily available, through six steps as shown below. [Mikarenko (El, A, Mikh & -1enkO) et al.
Zurnar Obshai Kimmy (Zh, 0bah
ch, Khim) Volume 41, Page 2735 (1971
), French Painting Patent No. 1580685, Lerner (B
, W. Larner) et al. Journal of the Chemical Society (J.

Chem, Soc, ) Vol. 1952, p. 680; Hanack, M. et al.;
(1982)] Although this method starts with inexpensive 0-xylene,
The reaction conditions at each stage are quite strict, and purification is not easy.
Also, six stages were required.

[Problem that the invention seeks to solve]

In addition, t-butyl-substituted phthalocyanine has conventionally been synthesized by a melting method with a metal chloride or by reaction in 1-chloronaphthalene [Jihanak et al., Ohem.

Bar), Vol. 115, p. 2836 (1982)].

In this method, chlorine of the metal chloride is eliminated during the reaction and t-
There is a large possibility that the butyl group is chlorinated, and in fact, the actual measured values and calculated values for the elemental analysis in the above paper do not agree well.

The object of the present invention is to provide a method for producing t-butyl 7-talonitrile starting from inexpensive raw materials, in a milder manner and with fewer synthetic steps, and in which the t-butyl group is not chlorinated.
An object of the present invention is to provide a method for producing butyl-substituted 7-thalocyanines.

[Means for solving problems]

To summarize the present invention, the first invention of the present invention relates to a method for producing at-butyl-1,2-dibromobenzene, in which t-butylbenzene is reacted with bromine in the presence of a catalyst. It is characterized by causing

Moreover, the second invention of the present invention is 4-t-butyl-1,2-
An invention relating to a method for producing dicyanobenzene, comprising:
It is characterized by reacting -t-butyl-1,2-dibromobenzene with a metal cyanide in an organic solvent.

And, the third invention of the present invention is the following general formula I: (in the formula M
(means hydrogen or metal, t-Bu means t-butyl group)
The invention relates to a method for producing t-butyl-substituted phthalocyanines represented by formula MX2 or MOR (formula M is hydrogen or metal, x is chlorine,
It is characterized by reacting a compound represented by bromine or iodine (R represents an alkyl group).

Furthermore, the fourth invention of the present invention relates to a method for producing a tetra-1-butyl phthalocyanino copper complex, in which cyanide is added to 4-t-butyl-1,2-dibromobenzene in an organic solvent. Particularly, in the dibromination reaction of the first invention, which is characterized by reacting cuprous, bromine is reacted at around room temperature in the presence of a catalyst such as iron and/or iodine, and a yield of 76% or more is obtained. The dibromo form is obtained.

In the dicyanation reaction of the second invention, cyanide-
A metal cyanide such as copper is heated to reflux to react. Alternatively, potassium cyanide may be subjected to a heating reflux reaction in alcohol in the presence of a catalyst such as tetrakis(tetraphenylphosphine)palladium complex.

Further, cupric cyanide and sodium cyanide may be mixed and used in a ratio of 1=1.

Examples of strong organic bases used in the method for producing t-butyl-substituted 7-talocyanines of the third invention include pKa 10
Organic bases such as 1,8-diazabicyclo(5,4,0)-7-undecene (DBU) and 4-
Dimethylaminopyridine is mentioned. Examples of metals in metal halides or metal alcolades include Ti,
V, Co, Ni, Ou, Zn, transition metals such as rare earths, A/, Ga.

Engineering n, Si, Go, Sn, Pb, M
Examples include typical elements such as g. Further, examples of Al-+A4 in Alcolade include methyl, ethyl, and 1-pentyl groups. The reaction is carried out in an alcoholic solvent at a temperature of 100-200°C or in a high-boiling solvent such as a halogenated aromatic hydrocarbon or quinoline at 180 °C.
Preferably it is carried out at a temperature of -220°C. This method saves energy because the temperature is lower than that of the conventional method.

In the reaction of the fourth invention, in the second invention, when a large amount of cupric cyanide is used as the metal cyanide and the reaction is carried out for a longer time, - the tetra-t-butylphthalocyanine copper complex is removed from the scales. I can do that.

〔Example〕

The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to these Examples.

Practical example 1 a-t--1 thyl-1,2-dibromobenzene t-butylbenzene 154? , 1 ton each of iron powder and iodine were added to 500 wj of carbon disulfide, and 120-bromine was added dropwise while stirring at room temperature. After reacting for 4 hours, it was neutralized and dried, and then distilled under reduced pressure to obtain 4-t-butyl-
Obtained 1,2-cypromobenzene.

boiling point? ? -102°/31111IIg1 yield 222f
(Yield 76%) 'H-NMR (200MH, Z, δppm), 7.6
2 (singlet, 1H), 7.54 (doublet,
1H), 7.19 (doublet, 1H), 1.28 (
Singlet, 9H) Example 24-t-butyl-1,2-dicyanobenzene (
a-t-butyl phthalonitrile) a-t-butyl-1,
2-dibromobenzene 1461', cupric cyanide 15
69. 'kl, H-dimethylformamide (DMIF)
2/ was refluxed at 165°C for 4 hours. After cooling, the mixture was poured into 21ml of water, 500ml of ammonia water was added thereto, and air was bubbled into the mixture for 1 day. The deposited precipitate was separated by suction F, redissolved in chloroform, washed and neutralized, and the solvent was concentrated. The residue was recrystallized (methylcyclohexane). Rough amount 42f
(Yield 45%) The product was further purified by vacuum sublimation to obtain pure at-butyl-1,2-dicyanobenzene.

Yield: 371°” H-NMR (200MH, z, δpp
m), 7.80 (Cimbrella), 1H), 7.75 (
Shiff bullet, 2H), 1.35 (singlet, 9H)
) Example 3 Tetra(4-t-butyl)7thalcyaninonite a-t-butyl-1,2-dicyanobenzene 9.2t1
Nickel chloride 52PXn-butanol 250-11,8
-diazabicyclo(5,4,0) -7-undecene(
DBU) 11 t of the mixed solution was refluxed for 1 day.

The solvent was distilled off under reduced pressure, and the residue was purified by chromatography to obtain tetra(
At-butyl) phthalocyaninonickel was obtained. Yield 2.5? (Yield 63%) Elemental analysis value (%) Actual value 0 near 2.55, Hlol, N: 14.12, Cl: α0 Theoretical value C near 2.46, H: &08, N: 14
．． Q8, OA': 0 Similarly, other central metal Co
, transition metal members such as Cu, εn, and typical elements such as Pb are respectively corresponding chlorides, 0oC1,, Cuot, B
A tetra-1-butyl-substituted metal-7 talocyanine was obtained by reacting with nOIH1P'bOl, etc.

Elemental analysis: Similar to N1, a pure product free of chlorine was obtained. Metal-free products were obtained by adding sodium methoxide to this system instead of metal salts and performing hydrolysis to obtain pure products.

Example 4 Tetra-t-butylphthalocyanine copper complex 4
- Starting from t-butylbenzene, 1 mole of cupric cyanide is refluxed for 1 day at 10 times the mole of DM? A tetra-butylphthalocyanino copper complex was obtained in two steps.

〔Effect of the invention〕

As explained above, according to the method of the present invention, it is possible to synthesize pure tetra-t-butyl-7-talocyanine that is not chlorinated, and the raw material 4-t-butyl-1,2-thalocyanine can be synthesized.
-Dicyanobenzene can be produced in high yield in two steps using inexpensive at-butylbenzene as a starting material. 4-1-Butyl-1,2-dicyanobenzene can be produced by a cyclization reaction with other substituted phthalonitriles or phthalonitriles to form asymmetric J, t-butyl groups, unsubstituted or containing other substituents. It is also useful in the synthesis of substituted phthalocyanines. Phthalocyanines are a group of compounds that have been expected to be used in organic photoreceptors, organic conductors, electrophotographic photoreceptors, solar cells, etc.; form or
It could only be dispersed in the polymer and had poor processability. However, by introducing a t-butyl group into the ring, the solubility is dramatically improved, and it is possible to control the molecular size of a thin film by using the Langmuir-Blodgett method, as well as the vapor deposition method. Phthalocyanines are known to have the potential to further enhance their electronic functions. The method of the present invention can easily provide t-butyl-substituted phthalocyanines in high yield, under mild conditions, and with a short number of steps, so the cost is 1/20 to 1/10,000 compared to conventional methods. It has the advantage of decreasing.

Claims (1)

[Scope of Claims] A method for producing 4-t-butyl-1,2-dibromobenzene, which comprises reacting 1,t-butylbenzene with bromine in the presence of a catalyst. A method for producing 4-t-butyl-1,2-dicyanobenzene, which comprises reacting 2,4-t-butyl-1,2-dibromobenzene with a metal cyanide in an organic solvent. 3,4-t-butyl-1,2-dicyanobenzene is dissolved in an organic solvent in the presence of a strong organic base to form a compound of the formula MX_2 or MOR (where M is hydrogen or metal, X is chlorine, bromine or iodine, and R is The following general formula I is characterized by reacting a compound represented by (representing an alkyl group): ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (In the formula, M has the same meaning as above, t-Bu means t-butyl group). A method for producing a tetra-t-butylphthalocyanino copper complex, which comprises reacting 4,4-t-butyl-1,2-dibromobenzene with cuprous cyanide in an organic solvent.