KR100377563B1 - Process for preparing 2-nitro-2'-hydroxy azobenzene derivatives - Google Patents
Process for preparing 2-nitro-2'-hydroxy azobenzene derivatives Download PDFInfo
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- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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Abstract
본 발명은 하기 화학식 2의 디아조늄염 유도체를 pH 2 이하의 산수용액중에서 분산제인 C8-C20-알킬아릴설폰산의 알칼리금속염 및 폴리에틸렌글리콜의 존재하에 하기 화학식 3의 페놀유도체와 반응시킴을 특징으로하여 하기 화학식 1의 아조벤젠 유도체를 제조하는 방법에 관한 것이다 :The present invention is to react the diazonium salt derivative of formula (2) with a phenol derivative of formula (3) in the presence of alkali metal salts and polyethylene glycol of C 8 -C 20 -alkylarylsulfonic acid as a dispersing agent in an acid solution of pH 2 or less Characterized in that the method for preparing azobenzene derivative of the formula
상기식에서 R1및 R2는 C1-C5알킬을 나타내고,Wherein R 1 and R 2 represent C 1 -C 5 alkyl,
R3는 수소 또는 할로겐을 나타낸다.R 3 represents hydrogen or halogen.
Description
본 발명은 하기 화학식 1로 표시되는 2-니트로-2'-하이드록시 아조벤젠 유도체의 새로운 제조방법에 관한 것이다 :The present invention relates to a novel process for preparing 2-nitro-2'-hydroxy azobenzene derivative represented by the following general formula (1):
화학식 1Formula 1
상기식에서In the above formula
R1및 R2는 C1-C5알킬을 나타내고R 1 and R 2 represent C 1 -C 5 alkyl
R3는 수소 또는 할로겐을 나타낸다.R 3 represents hydrogen or halogen.
좀더 구체적으로, 본 발명은 하기 화학식 2의 디아조늄염 유도체를 산수용액중에서 적당한 분산제의 존재하에 하기 화학식 3의 페놀유도체와 반응시킴을 특징으로하여 화학식 1의 화합물을 고순도 및 고수율로 제조하는 방법에 관한 것이다 :More specifically, the present invention is characterized in that the diazonium salt derivative of formula (2) is reacted with a phenol derivative of formula (3) in the presence of a suitable dispersant in an acid solution to prepare a compound of formula (1) in high purity and high yield It is about:
화학식 2Formula 2
화학식 3Formula 3
상기 화학식 2 및 3에서 R1, R2및 R3는 앞에서 정의한 바와 같다.In Formulas 2 and 3, R 1 , R 2 and R 3 are as defined above.
종래 아조벤젠 유도체를 합성하는 방법으로는 중성수용액과 pH 8 내지 11의 알칼리수용액에 대한 상기 화학식 3의 페놀유도체의 용해도가 낮기 때문에 유기용매와 적당한 분산제를 같이 사용하는 것이 일반적으로 알려져 있다. 예를들어, 일본 공개특허소 56-115757 호에서는 유기용매로 메탄올을 사용하고 있고, 일본 공개특허소 53-37628 호에서는 용매로 클로로벤젠을 사용하고 분산제로 알킬아릴설포네이트 나트륨염을 사용하고 있다. 그러나, 이러한 유기용매와 분산제를 사용한 아조 커플링 방법은 고수율로 고순도의 화합물을 얻을 수 있다는 장점은 있지만, 용매회수 및 폐수처리에 따르는 환경문제를 야기시키므로 산업적으로 이용하기에 바람직하지 못하였다. 한편, 미합중국 특허 제 3,998,804 호에서는 수용성인 화학식 2의 디아조늄염 유도체와 불용성인 화학식 3의 페놀유도체의 효과적인 분산을 위해 유기용매를 사용하지 않는 대신에 pH 2 이하의 산수용액중에서 아릴설폰산 및 폴리글리콜에테르와 혼합된 설폰산 금속염을 분산제로서 약 50중량%를 사용하여 아조벤젠 유도체를 합성하는 방법에 대해서 보고하고 있다. 또한, 상기 미합중국 특허의 개선된 방법으로서, 미합중국 특허 제 5,436,322 호에서는 분산제로서 알킬설폰산 또는 알킬설포네이트와 폴리비닐알콜의 혼합물을 사용하여 반응에 필요한 분산제의 사용량을 현저하게 줄이면서도 고수율로 아조벤젠 화합물을 제조하는 방법에 대해 보고하고 있다.As a conventional method for synthesizing azobenzene derivatives, it is generally known to use an organic solvent and a suitable dispersant because the solubility of the phenol derivative of Formula 3 in a neutral aqueous solution and an alkaline aqueous solution of pH 8 to 11 is low. For example, Japanese Patent Application Laid-Open No. 56-115757 uses methanol as an organic solvent, Japanese Patent Application Laid-Open No. 53-37628 uses chlorobenzene as a solvent and alkylarylsulfonate sodium salt as a dispersant. . However, the azo coupling method using such an organic solvent and a dispersant has the advantage of obtaining a high purity compound in a high yield, but it is not preferable for industrial use because it causes an environmental problem due to solvent recovery and wastewater treatment. On the other hand, U. S. Patent No. 3,998, 804 discloses an arylsulfonic acid and a polyphosphate in an aqueous acid solution of pH 2 or less instead of using an organic solvent for effective dispersion of the water-soluble diazonium salt derivative of formula (2) and the insoluble phenol derivative of formula (3). A method for synthesizing azobenzene derivatives using about 50% by weight of sulfonic acid metal salt mixed with glycol ether as a dispersant is reported. In addition, as an improved method of the above-mentioned US patent, US Pat. No. 5,436,322 uses alkylsulfonic acid or a mixture of alkylsulfonate and polyvinyl alcohol as a dispersant to significantly reduce the amount of dispersant required for the reaction and at high yield. A method for preparing a compound is reported.
이와 같이 지금까지 아조벤젠 유도체를 제조하는 다양한 방법이 개발되어 왔지만 그 제조방법을 산업적으로 적용하기에 만족스러운 정도의 것은 없었으며, 이에 따라 본 발명자들은 경제적이고 용이하게 구할 수 있는 새로운 분산제를 사용하는 보다 개선된 제조방법을 개발하여 고순도의 아조벤젠 유도체를 고수율로 제조하고자 노력하였다. 그 결과, 본 발명자들은 C8-C20-알킬아릴설폰산의 알칼리금속염을 폴리에틸렌글리콜과 함께 분산제로서 사용하면 이러한 종래의 문제를 해결하고 본 발명의 소기목적을 달성할 수 있음을 발견하여 본 발명을 완성하게 되었다. 이하, 본 발명의 구성을 상세히 설명한다.As such, various methods for preparing azobenzene derivatives have been developed so far, but there is no satisfactory level for industrial application of the preparation method. Accordingly, the present inventors have more economical and easily available new dispersant. Efforts have been made to develop high purity azobenzene derivatives by developing improved production methods. As a result, the present inventors have found that by using an alkali metal salt of C8-C20-alkylarylsulfonic acid together with polyethylene glycol as a dispersant, this conventional problem can be solved and the desired object of the present invention can be achieved. Was done. Hereinafter, the configuration of the present invention will be described in detail.
본 발명은 하기 화학식 2의 디아조늄염 유도체를 pH 2 이하의 산수용액중에서 분산제인 C8-C20-알킬아릴설폰산의 알칼리금속염 및 폴리에틸렌글리콜의 존재하에 하기 화학식 3의 페놀유도체와 반응시킴을 특징으로하여 화학식 1의 화합물을고순도 및 고수율로 제조하는 방법에 관한 것이다 :The present invention is to react the diazonium salt derivative of formula (2) with a phenol derivative of formula (3) in the presence of alkali metal salts and polyethylene glycol of C 8 -C 20 -alkylarylsulfonic acid as a dispersing agent in an acid solution of pH 2 or less Characterized by a process for the preparation of the compound of formula 1 in high purity and high yield:
화학식 2Formula 2
화학식 3Formula 3
화학식 1Formula 1
상기식에서In the above formula
R1및 R2는 C1-C5알킬을 나타내고R 1 and R 2 represent C 1 -C 5 alkyl
R3는 수소 또는 할로겐을 나타낸다.R 3 represents hydrogen or halogen.
본 발명에서 출발물질로 사용한 상기 화학식 2의 디아조늄염 유도체는 하기 화학식 4의 2-니트로아닐린 유도체로부터 제조된 것을 사용한다.The diazonium salt derivative of Chemical Formula 2 used as a starting material in the present invention uses the one prepared from 2-nitroaniline derivative of Chemical Formula 4 below.
상기식에서In the above formula
R3는 앞에서 정의한 바와 같다.R 3 is as defined above.
본 발명에서 분산제로 사용한 C8-C20-알킬아릴설폰산의 알칼리금속염으로서 가장 바람직하게 사용될 수 있는 것으로는 도데실벤젠설폰산 나트륨염을 언급할 수 있고, 통상 알칼리금속염으로는 나트륨염 또는 칼륨염을 사용한다. 이들은 분산제로서의 역할 뿐아니라 화학식 2의 디아조늄염 유도체의 안정화에도 중요한 역활을 수행한다.As the alkali metal salt of C 8 -C 20 -alkylarylsulfonic acid used as a dispersant in the present invention, dodecylbenzenesulfonic acid sodium salt can be mentioned most preferably. As the alkali metal salt, sodium salt or potassium is usually used. Salts are used. They play an important role not only as dispersants but also for stabilization of diazonium salt derivatives of formula (2).
또다른 분산제로 사용한 폴리에틸렌글리콜은 대량생산 품목으로 대표적인 수용성 고분자이며, 저렴하므로 경제적이다. 폴리에틸렌글리콜의 분자량에 따라서 반응물들의 분산효과가 크게 영향을 받을 수 있는데, 일반적으로 본 발명에 따른 반응에 사용된 폴리에틸렌글리콜의 분자량은 1,000 내지 20,000 이며, 특히 분자량 6,000 내지 15,000 의 폴리에틸렌글리콜이 균일한 분산에 효과적으로 사용될 수 있다.Polyethylene glycol, which is used as another dispersant, is a representative water-soluble polymer for mass production, and is economical because it is inexpensive. Depending on the molecular weight of polyethylene glycol, the dispersing effect of the reactants may be greatly affected. Generally, the polyethylene glycol used in the reaction according to the present invention has a molecular weight of 1,000 to 20,000, in particular, a uniform dispersion of polyethylene glycol having a molecular weight of 6,000 to 15,000. Can be used effectively.
분산효과 및 생성되는 입자의 균일성은 생성물의 수율과 순도에 직접 관계되는데, 이와 같은 분산효과는 분산제의 사용량에 따라서 크게 영향을 받는다. 본 발명에서 C8-C20-알킬아릴설폰산의 알칼리금속염은 화학식 3의 페놀유도체를 기준으로 하여 0.1 내지 5.0중량% 사용하는 것이 바람직하다. 0.1중량% 미만으로 사용하면 균일한 분산이 이루어지지 않아 원하는 수율로 생성물을 얻을 수 없고, 5.0중량% 초과사용시에는 경제적인 측면에서 바람직하지 못하기 때문이다. 가장 바람직하게는 0.4 내지 2.0중량% 범위로 사용한다. 한편, 폴리에틸렌글리콜 역시 화학식 3의 페놀유도체를 기준으로 하여 0.01 내지 2.0중량% 사용하는 것이 바람직하다. 사용량이 0.01중량% 미만인 경우에는 분산효과가 작아 원하는 수율 및 순도의 생성물을 얻을 수 없고, 2.0중량%를 초과하여 사용하는 경우에는 생성물이 입자화되지 않아 원하는 생성물을 분리하기가 용이하지 않기 때문이다. 가장 바람직하게는 0.1 내지 0.5중량% 범위로 사용한다.The dispersing effect and the uniformity of the particles produced are directly related to the yield and purity of the product, which are greatly influenced by the amount of dispersant used. The alkali metal salt of C 8 -C 20 -alkylarylsulfonic acid in the present invention is preferably used 0.1 to 5.0% by weight based on the phenol derivative of the formula (3). If the amount is less than 0.1% by weight, it is not possible to obtain a product in a desired yield because it is not uniformly dispersed, and when used in excess of 5.0% by weight, it is not preferable economically. Most preferably, it is used in the range of 0.4 to 2.0 weight%. On the other hand, polyethylene glycol is also preferably used 0.01 to 2.0% by weight based on the phenol derivative of the formula (3). If the amount used is less than 0.01% by weight, the dispersion effect is small, so that a product of desired yield and purity cannot be obtained. If the amount is used more than 2.0% by weight, the product is not granulated, so that it is not easy to separate the desired product. . Most preferably, it is used in the range of 0.1 to 0.5% by weight.
한편, 본 발명에서 반응물질로 사용하는 화학식 3의 페놀유도체는 분산제를 사용하여도 상온에서는 물에 잘 분산되지 않기 때문에 효율적인 분산을 위해 30 내지 70℃ 정도로 가열을 하는 것이 필요하다. 또한, 본 발명에서 분산제로 사용한폴리에틸렌글리콜의 분산효과가 온도에 따라 영향을 받을 수 있으므로 적절한 반응온도 설정이 매우 중요하다. 따라서, 이러한 두가지 요소를 고려하여 실험을 수행한 결과 본 발명에 따른 방법에서 반응온도는 35 내지 60℃ 범위가 적당한 것으로 확인되었다. 따라서, 디아조늄염의 분해가 일어나지 않도록 화학식 2의 디아조늄염 수용액 온도를 5 내지 15℃ 범위로 유지하면서, 화학식 3 페놀유도체 및 분산제가 물에 잘 분산된 반응물에 천천히 적가하는데, 이때 반응온도가 35 내지 60℃로 유지되도록 적가 속도를 조절하는 것이 좋다.On the other hand, the phenol derivative of the formula (3) used as a reactant in the present invention is not well dispersed in water at room temperature even if a dispersant is used, it is necessary to heat about 30 to 70 ℃ for efficient dispersion. In addition, since the dispersion effect of the polyethylene glycol used as the dispersant in the present invention may be affected by the temperature, setting the appropriate reaction temperature is very important. Therefore, the experiment was carried out in consideration of these two factors, the reaction temperature in the method according to the present invention was found to be in the appropriate range of 35 to 60 ℃. Therefore, while maintaining the diazonium salt aqueous solution temperature of 5 to 15 ℃ range to prevent decomposition of the diazonium salt, the formula 3 phenol derivative and the dispersant are slowly added dropwise to the reactant well dispersed in water, wherein the reaction temperature is 35 It is preferable to adjust the dropping rate to maintain the temperature to 60 ℃.
이하, 본 발명을 하기 실시예에 의거하여 보다 구체적으로 설명한다. 그러나, 이들 실시예는 본 발명에 대한 이해를 돕기위한 것일 뿐, 어떤 의미로든 본 발명의 범위가 이들 실시예로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the following examples. However, these examples are only for the understanding of the present invention, and the scope of the present invention in any sense is not limited to these examples.
실시예 1:Example 1: 2-니트로-4-클로로-2'-하이드록시-3'5'-디-t-부틸아조벤젠의 합성Synthesis of 2-nitro-4-chloro-2'-hydroxy-3'5'-di-t-butylazobenzene
(1) 디아조늄염 수용액의 제조(1) Preparation of Diazonium Salt Aqueous Solution
3ℓ 용량의 반응용기에 물 400g, 4-클로로-2-니트로아닐린 345.1g을 가하고 30분 동안 잘 교반하였다. 반응기 내부온도가 50℃ 이상 되지않게 얼음 640.0g과 황산(95%) 619.4g을 천천히 가하고 잘 저어주면서 반응기 내부온도를 5 내지 10℃로 냉각시켰다. 반응기 내부온도를 동온도로 유지시키면서 30% 나이트라이트 나트륨 수용액 469.2g을 2 시간동안 적가하였다. 적가 완료후 30분 동안 더 반응 시키면 투명한 흑갈색의 디아조늄 수용액이 얻어진다. 반응의 완결은 고압액체 크로마토그래피(HPLC)로 확인하고, 반응하지 않고 남은 과량의 나이트라이트는 설팜산(H2NSO3H) 4.85g을 가하여 불활성화시켰다.400 g of water and 345.1 g of 4-chloro-2-nitroaniline were added to a 3 L reaction vessel, and the mixture was stirred well for 30 minutes. 640.0 g of ice and 619.4 g of sulfuric acid (95%) were slowly added and stirred well so that the temperature inside the reactor was cooled to 5 to 10 ° C. so that the temperature inside the reactor was not higher than 50 ° C. 469.2 g of an aqueous 30% sodium nitrite solution was added dropwise for 2 hours while maintaining the temperature inside the reactor at the same temperature. After completion of the addition, the reaction is further performed for 30 minutes to obtain a clear dark brown diazonium aqueous solution. The completion of the reaction was confirmed by high pressure liquid chromatography (HPLC), and the excess nitrite remaining unreacted was inactivated by adding 4.85 g of sulfamic acid (H 2 NSO 3 H).
(2) 아조 커플링(2) azo coupling
5ℓ 용량의 반응용기에 물 600g, 폴리에틸렌글리콜(분자량 MW=10,000) 1.6g 및 도데실벤젠설폰산 나트륨염 6.4g을 가하고 10분 동안 교반하면 투명한 수용액이 수득된다. 여기에 2,4-디-t-부틸-페놀 335.1g을 가하고 빠르게 교반하면서 50℃로 가열하면 2,4-디-t-부틸-페놀이 녹으면서 첨가된 분산제에 의해 물에 잘 분산된 혼합물이 된다(커플러 용액). 잘 분산된 커플러 용액의 온도가 35 내지 45℃로 유지되도록 하면서 상기 (1)에서 수득한 디아조늄염 수용액(5 내지 10℃ 온도 유지)을 4 시간 동안 적가하였다. 디아조늄염 수용액을 모두 적가한 후 45℃에서 1시간동안 더 반응시켜 반응을 완료시키고, 동온도에서 반응물을 여과하였다. 여과후 45℃의 물 4000g으로 세척하고, 진공건조하여 791.8g의 2-니트로-4-클로로-2'-하이드록시-3',5'-디-t-부틸아조벤젠을 수득하였다. 생성물의 순도는 94.1%(HPLC)였고, 수율은 95.5%이었으며, 융점은 196 내지 210℃로 나타났다.600 g of water, 1.6 g of polyethylene glycol (molecular weight MW = 10,000) and 6.4 g of sodium dodecylbenzenesulfonic acid salt were added to a 5 L reaction vessel, and stirred for 10 minutes to obtain a clear aqueous solution. To this was added 335.1 g of 2,4-di-t-butyl-phenol and heated to 50 ° C. under rapid stirring, the mixture well dispersed in water by the dispersant added while the 2,4-di-t-butyl-phenol was dissolved. It becomes (coupler solution). The aqueous diazonium salt solution obtained in (1) (maintained at 5 to 10 ° C.) was added dropwise for 4 hours while maintaining the temperature of the well dispersed coupler solution at 35 to 45 ° C. After all of the diazonium salt solution was added dropwise, the reaction was completed by further reacting at 45 ° C. for 1 hour, and the reaction product was filtered at the same temperature. After filtration, washing with 4000 g of 45 ° C. water, and drying in vacuo yielded 791.8 g of 2-nitro-4-chloro-2'-hydroxy-3 ', 5'-di-t-butylazobenzene. The product had a purity of 94.1% (HPLC), a yield of 95.5% and a melting point of 196-210 ° C.
실시예 2: 2-니트로-4-클로로-2'-하이드록시-3'-t-부틸-5'-메틸아조벤젠의 합성Example 2: Synthesis of 2-nitro-4-chloro-2'-hydroxy-3'-t-butyl-5'-methylazobenzene
5ℓ 용량의 반응용기에 물 600g, 폴리에틸렌글리콜(분자량 MW=10,000) 1.6g 및 도데실벤젠설폰산 나트륨염 13.9g을 가하고 10분 동안 교반하면 투명한 수용액이 수득된다. 여기에 2-t-부틸-4-메틸페놀 331.8g을 가하고 빠르게 교반하면서 50℃로 가열하면 2-t-부틸-4-메틸페놀이 녹으면서 첨가된 분산제에 의해 물에 잘 분산된 혼합물이 된다(커플러 용액). 잘 분산된 커플러 용액의 온도가 28 내지 34℃로 유지되도록 하면서 실시예 1의 (1)에서 수득한 디아조늄염 수용액(5 내지 10℃ 온도 유지)을 4 시간 동안 적가하였다. 디아조늄염 수용액을 모두 적가한 후 45℃에서 1시간동안 더 반응시켜 반응을 완료시키고, 동온도에서 반응물을 여과하였다. 여과 후 45℃의 물 4000g으로 세척하고, 진공건조하여 665.0g의 2-니트로- 4-클로로-2'-하이드록시-3'-t-부틸-5'-메틸아조벤젠을 수득하였다. 생성물의 순도는 93.3%(HPLC)였고, 수율은 89.2%이었으며, 융점은 162 내지 181℃로 나타났다.600 g of water, 1.6 g of polyethylene glycol (molecular weight MW = 10,000) and 13.9 g of sodium dodecylbenzenesulfonic acid salt were added to a 5 L reaction vessel, and stirred for 10 minutes to obtain a clear aqueous solution. 331.8 g of 2-t-butyl-4-methylphenol was added thereto, and the mixture was heated to 50 DEG C while rapidly stirring to obtain a mixture well dispersed in water by the dispersant added while the 2-t-butyl-4-methylphenol was dissolved. (Coupler solution). The aqueous diazonium salt solution obtained in (1) of Example 1 (maintained at 5 to 10 ° C.) was added dropwise for 4 hours while maintaining the temperature of the well dispersed coupler solution at 28 to 34 ° C. After all of the diazonium salt solution was added dropwise, the reaction was completed by further reacting at 45 ° C. for 1 hour, and the reaction product was filtered at the same temperature. After filtration, washing with 4000 g of water at 45 ° C., and drying in vacuo yielded 665.0 g of 2-nitro-4-chloro-2′-hydroxy-3′-t-butyl-5′-methylazobenzene. The product had a purity of 93.3% (HPLC), a yield of 89.2% and a melting point of 162 to 181 ° C.
이상 설명한 바와 같이, 본 발명은 경제적으로 용이하게 구할 수 있는 새로운 분산제로서 C8-C20-알킬아릴설폰산의 알칼리금속염을 폴리에틸렌글리콜과 함께 사용함으로써 분산효과를 극대화시켜 화학식 1의 아조벤젠 유도체를 고순도 및 고수율로 제조하는데 매우 효과적으로 이용될 수 있으리라 기대된다.As described above, the present invention maximizes the dispersing effect by using an alkali metal salt of C 8 -C 20 -alkylarylsulfonic acid together with polyethylene glycol as a new dispersant that can be easily obtained economically to obtain azobenzene derivative of Formula 1 And it is expected that it can be used very effectively to manufacture in high yield.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4959131A (en) * | 1972-07-11 | 1974-06-08 | ||
| US3998804A (en) * | 1972-07-11 | 1976-12-21 | Ciba-Geigy Corporation | Process for coupling of water-insoluble 2,4-disubstituted phenols with diazotized o-nitroanilines |
| JPS56125455A (en) * | 1980-03-07 | 1981-10-01 | Shipuro Kasei Kk | Preparation of azo compound |
| JPH09157240A (en) * | 1995-12-01 | 1997-06-17 | Toray Ind Inc | Production of azo compound |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4959131A (en) * | 1972-07-11 | 1974-06-08 | ||
| US3998804A (en) * | 1972-07-11 | 1976-12-21 | Ciba-Geigy Corporation | Process for coupling of water-insoluble 2,4-disubstituted phenols with diazotized o-nitroanilines |
| JPS56125455A (en) * | 1980-03-07 | 1981-10-01 | Shipuro Kasei Kk | Preparation of azo compound |
| JPH09157240A (en) * | 1995-12-01 | 1997-06-17 | Toray Ind Inc | Production of azo compound |
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