Organic compounds -- part of the class 532-570 series – Organic compounds – Diazooxide or diazotate
Reexamination Certificate
2000-04-11
2001-08-14
Powers, Fiona T. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Diazooxide or diazotate
Reexamination Certificate
active
06274714
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method for producing 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride, which is an important starting material for preparing a radiation-sensitive positive photoresist composition, a photosensitive component of a positive photosensitive lithographic printing master plate, etc.
2. Background Art
1,2-Naphthoquinone-2-diazide-4-sulfonyl chloride has a chemical structure represented by the following formula (1). This compound has a melting point of 146-148° C. (decomposition). In “Chemical Abstracts,” an abstract journal issued by the American Chemical Society, this compound is called 3-diazo-3,4-dihydro-4-oxo-1-naphthalenesulfonyl chloride, and the CAS registry number of the compound is “36451-09-9.”
Methods for producing 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride are divided into the following two types, (a) and (b), on the basis of the sequence of steps. Methods of type (a) are industrially employed at the present time. However, since methods of this type are not necessarily directly related to the method of the present invention, they will be briefly described only in outline form. Methods of type (b) are not industrially employed at the present time. However, since the method of the present invention is categorized under method (b), essential points of a typical known method categorized under method (b) will be described.
Methods of type (a) are drawn to a process in which sodium 1,2-naphthoquinone-2-diazide-4-sulfonate (CAS registry number: 64173-96-2) is synthesized (first step) and then converted to a compound of the above-described formula (1) (second step) (see, for example, DRP171024, DRP175593, German Patent Nos. 246573 and 246574, Japanese Patent Application Laid-Open (kokai) No. 196860/1984, and Japanese Patent Application Laid-Open (kokai) No. 27098/1996). According to such a method, many difficulties are encountered in the first step; i.e., in the synthesis of the compound of CAS registry number 64173-96-2. Particularly, synthesis of this compound is carried out by diazotization of sodium 3-amino-4-hydroxynaphthalene-1-sulfonate in the presence of a salt of a heavy metal such as copper, and therefore, the product is contaminated with a heavy metal salt. Thus, in order to make the compound usable as a photosensitizer for use in photoresist, the heavy metals must be eliminated. Practicing the elimination process for heavy metals on an industrial scale is considerably burdensome, and hence demand remains for a more effective method for producing the compound of formula (1).
Methods of type (b) are drawn to a process in which 1,2-naphthoquinone-2-diazide is treated with chlorosulfuric acid and thionyl chloride, to thereby yield the compound represented by formula (1). The method of the present invention is a method of this type. According to “Chemical Abstracts,” 1,2-naphthoquinone-2-diazide is named 2-diazo-1(2H)-naphthalenone, and the CAS registry number of the compound is 879-15-2. The compound has a chemical structure represented by the following formula (2).
Methods of type (b) are industrially promising, but thus far there have been disclosed very few study examples thereof. The main reason is failure to establish effective methods for producing the compound represented by the above-described formula (2). The present inventors previously invented a significantly effective method for producing the compound described below (Japanese Patent Application No. 166744/1998). They continued studies on methods of type (b) in great detail, to thereby complete the present invention.
Very few published documents mention methods of type (b). E. Sauer et al. disclose a method in which 1,2-naphthoquinone-2-diazide is reacted with chlorosulfuric acid at 63° C. for 80 minutes, to thereby obtain a mixture of a sulfonated compound and a chlorosulfonated compound of the diazide. In this method, the theoretical yields of 1,2-naphthoquinone-2-diazide-4-sulfonic acid and 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride are about 45% and about 50% respectively (
J. Prakt. Chem
. 333, 467 (1991)). B. I. Below et al. disclose a method in which 1,2-naphthoquinone-2-diazide is reacted in chlorosulfuric acid (14.3 times (by mol) the amount of the diazide) at 70° C. for two hours to thereby obtain crystals having a melting point of 138-139° C., and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride is obtained at a yield of 70% (U.S.S.R Pat. 173,756 (1964)). However, judging from the melting point of the crystals and the results of an experiment conducted by E. Sauer et al., the crystals are believed to be a mixture of the compound represented by formula (1), which serves as a main component, and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride. In addition, Wolter, Gerhard, et al. disclose a method in which 1,2-naphthoquinone-2-diazide is treated with a mixture of chlorosulfuric acid and thionyl chloride, to thereby obtain 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride at a favorable yield (Ger. (East) Pat. DD 269,846 (1989)). The method disclosed by Wolter, Gerhard, et al. is outlined as follows.
A mixture consisting of 6-10 mol of chlorosulfuric acid and 2-5 mol of thionyl chloride based on 1 mol of 1,2-naphthoquinone-2-diazide is cooled, and crystals of 1,2-naphthoquinone-2-diazide are added thereto portionwise. The mixture is reacted at 35-60° C. for 1-3 hours, cooled to room temperature, and poured into a mixture of water and ice. The precipitated crude product is separated and purified through crystallization from acetone at a temperature between −5° C. and −10° C. inclusive. 1,2-Naphthoquinone-2-diazide-4-sulfonyl chloride is described as having a theoretical yield of 70-75%.
The present inventors considered the aforementioned methods of type (b), in which 1,2-naphthoquinone-2-diazide is used as a starting material, to be promising for industrial production of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride, and re-examined a method disclosed in the aforementioned DD 269,846, which is the sole known document mentioning the above method. As a result, the inventors have found that such problems as (1), (2), and (3) described below remain unsolved and that solution of the problems is outstanding.
(1) Problems Involved in Reaction with Thionyl Chloride
In the method disclosed in DD 269,846, 1,2-naphthoquinone-2-diazide is added to a mixture of chlorosulfuric acid and thionyl chloride, and the resultant mixture is allowed to react. However, after studying the method the present inventors have found that the method is unfavorable in the following ways. Crude crystals obtained by treating 1,2-naphthoquinone-2-diazide with a mixture of chlorosulfuric acid and thionyl chloride in accordance with the Example disclosed in DD 269,846 exhibit strong color, the yield of the target compound is poor, and the target compound contains many kinds of impurities. Chlorosulfonation of an aromatic compound making use of a mixture of chlorosulfuric acid and thionyl chloride is generally and widely employed. For example, Blank, Heinz Ulrich discloses a method in which benzene is treated with a mixture of chlorosulfuric acid and thionyl chloride at 50° C. for four hours, to thereby obtain benzenesulfonyl chloride at high purity (Ger. Offen, 2,635,279 (1978)). Sasaki et al. disclose a method in which sodium 1,2-naphthoquinone-2-diazide-4-sulfonic acid is treated with a mixture of chlorosulfuric acid and thionyl chloride at 70° C. for eight hours, to thereby obtain 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride at a yield of 80% (Japanese Patent Application Laid-Open (kokai) No. 27098/1996). Thus, a mixture of chlorosulfuric acid and thionyl chloride is excellent for use as a chlorosulfonation agent for an aromatic compound. However, the present inventors have unexpectedly found that the mixture cannot favorably be applied to 1,2-naphthoquinone-2-diazide. The present inventors have extensively studied the reactivity of 1,2-naphthoquinone-2-diazide and found that, surprisingly, the diazide reacts quite
Hagiwara Yu-ichi
Hotta Yuki
Iida Hirotada
Itahana Toshio
Sato Naoki
Huntley & Associates
Powers Fiona T.
Toyo Gosei Kogyo Co. Ltd.
LandOfFree
Method for producing 1,2-naphthoquinone-2-diazide-4-sulfonyl... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Method for producing 1,2-naphthoquinone-2-diazide-4-sulfonyl..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Method for producing 1,2-naphthoquinone-2-diazide-4-sulfonyl... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2445861