JPH05178616A - Production of zinc phthalocyanine sulfonyl chloride - Google Patents

Abstract

PURPOSE:To attain the improvement of yield by adding zinc phthalocyanine into chlorosulfonic acid to proceed the reaction by heating to a specific temp. and allowing to react with thionyl chloride at a temp. lowered to a prescribed temp. CONSTITUTION:A specific quantity of zinc phthalocyanine is added little by little at <=30 deg.C into chlorosulfonic acid, is mixed at a temp. raised to 60-75 deg.C for a prescribed time and, after that, is kept at a temp. raised to 100-120 deg.C for a prescribed time to proceed the sulfonyl chloridizing reaction of zinc phthalocyanine. After allowing to react at a temp. lowered to 50-70 deg.C, it is cooled to room temp., is added into ice water and the deposited precipitate is filtrated. The filtrated precipitate is washed to make neutral, is dried and zinc phthalocyanine sulfonyl chloride is obtained in high yield.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a sulfonyl chloride of zinc phthalocyanine.

[0002]

2. Description of the Related Art As a method for producing a sulfonyl chloride of a metal phthalocyanine, methods disclosed in US Pat. No. 22,19330 and US Pat. No. 2897207 are known. According to these methods, first, copper phthalocyanine is put into chlorosulfonic acid at 30 ° C or lower, heated to 70 to 75 ° C and stirred for 1 hour, and then 130 to 135 ° C over 1.5 hours.
The temperature is raised to 130 ° C., and the mixture is stirred at 130 to 135 ° C. for 4 hours to promote the sulfonyl chloride formation reaction of copper phthalocyanine. Next, the temperature is lowered to 80 ° C., thionyl chloride is added and reacted at 75 to 80 ° C. for 4 hours, and then cooled to room temperature. After cooling, the mixture is poured into ice water and the deposited precipitate is filtered. The precipitate obtained by filtration is thoroughly washed with ice water until it becomes neutral to obtain a sulfonyl chloride form of copper phthalocyanine.

However, according to the above method, the sulfonyl chloride form of copper phthalocyanine can be obtained in high yield, but the sulfonyl chloride form of zinc phthalocyanine cannot be obtained at all, or the yield is extremely low. was there.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a method for producing a sulfonyl chloride of zinc phthalocyanine, which solves the problems of the above-mentioned conventional techniques and can obtain a sulfonyl chloride of zinc phthalocyanine in a high yield. The purpose is to

[0005]

Means for Solving the Problems As a result of earnest studies for achieving the above object, the inventors of the present invention have found that zinc phthalocyanine added to chlorosulfonic acid at room temperature has a relatively low temperature of about 100 to 120.degree. React for about a time to form sulfonyl chloride, then add thionyl chloride and add 50-70 ° C.
It was found that a sulfonyl chloride of zinc phthalocyanine can be obtained in high yield by reacting for about 2 hours, and based on this, the reaction conditions are studied in more detail to reach the present invention described in detail below. did.

That is, according to the present invention, first, zinc phthalocyanine is added to chlorosulfonic acid at 30 ° C. or lower,
After heating to 75 ° C and stirring for 1 to 1.5 hours, 100 to 120
C., preferably 110 to 120.degree. C., and stirred at that temperature for 2.5 to 5.0 hours, preferably 3 hours to promote the sulfonyl chloride formation reaction of zinc phthalocyanine, and then to 70.degree. Then, thionyl chloride is added to the mixture at 50 to 70 ° C, preferably 60 to 70 ° C for 1.0 to 2.5 hours,
Preferably, the reaction is performed for 2 hours, then cooled to room temperature, cooled, poured into ice water, the deposited precipitate is filtered, and the obtained precipitate is washed well with ice water until neutral. The present invention provides a method for producing zinc phthalocyanine sulfonyl chloride.

[0007]

According to the conventional method for producing a sulfonyl chloride of metal phthalocyanine, the yield of the sulfonyl chloride of zinc phthalocyanine was about 0 to 10%. This is because when a zinc phthalocyanine charged in chlorosulfonic acid is subjected to a sulfonyl chloride reaction at 130 to 135 ° C for 4 hours, a decomposition reaction of zinc phthalocyanine, that is, a dezincification reaction occurs, and further an azaporphine ring is decomposed. It is presumed that this is because the yield was significantly reduced because the reaction proceeded.

That is, in the method of the present invention, the temperature at which the sulfonyl chloride-forming reaction of zinc phthalocyanine proceeds is 130 to 135 ° C. to 100 to 120 ° C., preferably 110 to 120 ° C.
The effect of lowering the temperature to 120 ° C was advantageous, the decomposition reaction of zinc phthalocyanine was prevented, the sulfonyl chloride formation proceeded smoothly, and the unexpected effect of improving the yield of the sulfonyl chloride form of zinc phthalocyanine was brought about. It is believed that

Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by the following examples.

[0010]

EXAMPLES An example of the method for producing zinc phthalocyanine sulfonyl chloride of the present invention is shown below.

First, 5.78 g of zinc phthalocyanine (manufactured by Tokyo Kasei Co., Ltd.) was added little by little to 45 g of chlorosulfonic acid at 30 ° C. or lower. Then, this is heated to 70 to 75 ° C., stirred at the temperature for 1 hour, and then 110 to 1 over 1 hour.
The temperature was raised to 20 ° C., and the mixture was stirred at this temperature for 3 hours to proceed the sulfonyl chloride formation reaction of zinc phthalocyanine. Next, this was cooled to 70 ° C., 18 g of thionyl chloride was added little by little, and the mixture was stirred at 60 to 70 ° C. for 2 hours. Next, this was cooled to room temperature and then poured into 400 g of ice water, and the deposited precipitate was filtered. After filtration, the resulting precipitate was thoroughly washed with ice water until it became neutral to obtain a sulfonyl chloride of zinc phthalocyanine (wet weight 32 g). Then, it was vacuum dried in a desiccator to obtain 8.7 g of a dried product.

The sulfonyl chloride derivative of zinc phthalocyanine produced as described above has a yield of 8 assuming that three sulfonyl chlorides are substituted.
It was 9.7%. In addition, C when three Cl are substituted
The theoretical value of 1% is 12.14, but the analytical value of Cl was 12.20%, so the above assumption can be said to be correct.

[0013]

[Comparative Example 1] As a comparative example with the method of the present invention, the progress temperature of the sulfonyl chloride formation reaction of zinc phthalocyanine was
A sulfonyl chloride of zinc phthalocyanine was produced in the same manner as in Example except that the temperature was changed to 130 to 135 ° C instead of 10 to 120 ° C. As a result, the yield of sulfonyl chloride of zinc phthalocyanine was 7 g in wet weight.
Met.

[0014]

With the development of the method of the present invention, the conventional method has
The sulfonyl chloride form of zinc phthalocyanine, which could be obtained only in a yield of about 10%, can be obtained in a yield of 70 to 90%.

Claims (1)

[Claims] 1. Zinc phthalocyanine is added to chlorosulfonic acid at 30 ° C. or lower, the temperature is raised to 100 to 120 ° C. to proceed the sulfonyl chloride formation reaction of zinc phthalocyanine, and then the temperature is lowered to 50 to 70 ° C. A method for producing zinc phthalocyanine sulfonyl chloride, which comprises reacting with thionyl chloride.