KR100620410B1 - Process for the preparation of anisothiazolanthrone compound - Google Patents
Process for the preparation of anisothiazolanthrone compound Download PDFInfo
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- KR100620410B1 KR100620410B1 KR1020010005639A KR20010005639A KR100620410B1 KR 100620410 B1 KR100620410 B1 KR 100620410B1 KR 1020010005639 A KR1020010005639 A KR 1020010005639A KR 20010005639 A KR20010005639 A KR 20010005639A KR 100620410 B1 KR100620410 B1 KR 100620410B1
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- 0 *c1cccc(C(c2c3cccc2N=O)=O)c1C3=O Chemical compound *c1cccc(C(c2c3cccc2N=O)=O)c1C3=O 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
- C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
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- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/52—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton the carbon skeleton being further substituted by doubly-bound oxygen atoms
- C07C309/53—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton the carbon skeleton being further substituted by doubly-bound oxygen atoms the carbon skeleton containing carbon atoms of quinone rings
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Abstract
본 발명은 하기 화학식(4)의 화합물을 출발물질로 하여 용매 및 강염기 촉매 존재 하에서 소듐 설파이드, 유황 및 아민화제와 고압반응기가 아닌 상압에서 반응시킴을 특징으로 하여 상기 화학식(2)의 이소티아졸안트론 화합물을 제조하는 방법에 관한 것이다.The present invention is characterized in that the compound of formula (4) is reacted with sodium sulfide, sulfur, and amination agent at normal pressure, not in a high pressure reactor, in the presence of a solvent and a strong base catalyst. It relates to a method for preparing a tron compound.
Description
본 발명은 하기 화학식(1)의 화합물의 제조에 유용한 하기 화학식(2)의 이소티아졸안트론 화합물의 신규한 제조방법에 관한 것이다.The present invention relates to a novel process for the preparation of isothiazoleanthrone compounds of formula (2) which is useful for the preparation of compounds of formula (1).
[화학식 1][Formula 1]
[화학식 2][Formula 2]
상기식에서, In the above formula,
R은 알킬기, 페닐기 또는 치환된 페닐기를 나타낸다.R represents an alkyl group, a phenyl group or a substituted phenyl group.
일광에 장시간 노출되는 섬유제품, 특히 카시트, 커튼, 소파 등에 사용되는 섬유제품에 대하여 좀 더 일광견뢰도가 향상되고 이 섬유제품들의 사용 중에 색상이 퇴색될 때 같은 색조를 유지되어야 한다는 소비자들의 요구가 커지고 있다.For textile products that are exposed to sunlight for a long time, especially textiles used in car seats, curtains, sofas, etc., there is a greater demand for sunlight fastness and the demand for consumers to maintain the same color tones when they fade. have.
또한 후처리 가공시 소재로 사용된 염색된 섬유는 비교적 고온의 상태를 거치게 되는데 이때 염색된 일부의 염료가 섬유 표면으로 이동(migration)하여 섬유제품의 마찰견뢰도를 저하시키는 단점이 지적되어 왔다.In addition, the dyed fiber used as a material during the post-treatment process is subjected to a relatively high temperature state, in which some of the dyes have been pointed out to reduce the friction fastness of the fiber product by migrating to the fiber surface (migration).
화학식(1)의 화합물은 소수성 섬유의 침염 또는 날염에 유용하고, 특히 폴리에스터 섬유, 폴리에스터-면 등의 폴리에스터를 포함하는 혼방섬유의 염색에 적합한 것으로 알려져 있다. 또한 이 화합물은 우수한 일광견뢰도를 나타내고, 이 화합물로 염색한 섬유제품의 일광에 대한 퇴색시 색조가 일정하게 유지되고, 후가공시 고온에서의 섬유표면으로의 이동현상을 현저하게 감소시켜 우수한 마찰견뢰도를 나타냄으로써 카시트, 커튼, 소파 등의 염색에 특히 적합한 것으로 알려져 있다.Compounds of formula (1) are known to be useful for dyeing or printing hydrophobic fibers, and are particularly suitable for dyeing blended fibers comprising polyester such as polyester fibers, polyester-cotton and the like. In addition, the compound exhibits excellent daylight fastness, the color tone of the textile products dyed with this compound is kept constant during fading, and remarkably reduces migration to the fiber surface at high temperatures during post-processing, thereby providing excellent friction fastness. It is known to be particularly suitable for dyeing car seats, curtains, sofas and the like.
화학식(1)의 화합물은 화학식(2)의 이소티아졸안트론 화합물로부터 반응도식 1에 나타낸 방법에 따라 일반적인 유기화학 반응으로 쉽게 합성할 수 있다.The compound of formula (1) can be easily synthesized from the isothiazoleanthrone compound of formula (2) by a general organic chemical reaction according to the method shown in Scheme 1.
[반응도식 1]Scheme 1
R은 알킬기, 페닐기 또는 치환된 페닐기를 나타낸다.R represents an alkyl group, a phenyl group or a substituted phenyl group.
상기 화학식(2)의 이소티아졸안트론 화합물을 제조하는 방법은 독일특허 216,306호 및 Liebigs.ANN. 393, 113(1912) 에 소개되어 있다. 이러한 특허 및 문헌에서는 하기 반응도식2에 나타낸 방법에 따라 화학식(3)의 포타슘 염과 소듐 설파이드, 유황 및 암모니아수를 혼합하여 고압반응기를 사용하여 고압에서 반응을 시키므로 대규모 상업적인 유용성이 부족하다.The method for preparing the isothiazolanthrone compound of formula (2) is described in German Patent No. 216,306 and Liebigs. 393 , 113 (1912). In these patents and documents, the potassium salt of formula (3) and sodium sulfide, sulfur, and ammonia water are mixed according to the method shown in Scheme 2, and then reacted at a high pressure using a high pressure reactor, thereby lacking large scale commercial utility.
[반응도식 2]Scheme 2
이에 본 발명자들은 상기 문제점들을 해결하기 위하여 광범위한 연구를 수행한 결과 보다 우수한 방법, 즉 보다 온화한 상압조건에서 고순도의 화학식(2)의 이소티아졸안트론 화합물을 부산물의 생성없이 경제적인 방법으로 합성할 수 있는 방법을 개발하게 되었다.Accordingly, the present inventors have conducted extensive research to solve the above problems. As a result, the present inventors can synthesize isothiazoleanthrone compound of formula (2) of high purity under milder atmospheric pressure in an economical manner without generation of by-products. I developed a way to.
본 발명은 하기 화학식(4)의 화합물을 출발물질로 하여 용매 및 촉매 존재 하에서 소듐 설파이드, 유황 및 아민화제와 고압반응기가 아닌 상압에서 반응시킴을 특징으로 하여 상기 화학식(2)의 이소티아졸안트론 화합물을 제조하는 방법에 관한 것이다.The isothiazoleanthrone of formula (2) is characterized in that the compound of formula (4) is reacted with sodium sulfide, sulfur, and amination agent at normal pressure, not in a high pressure reactor, in the presence of a solvent and a catalyst. The present invention relates to a method for preparing a compound.
[화학식 4][Formula 4]
상기식에서 In the above formula
M은 소듐, 포타슘 또는 암모늄을 나타낸다.M represents sodium, potassium or ammonium.
본 발명에 따른 화학식(2)의 이소티아졸안트론 화합물의 제조방법은 하기 반응도식 3으로 나타낼 수 있다.Method for producing the isothiazoleanthrone compound of formula (2) according to the present invention can be represented by the following scheme 3.
[반응도식 3]Scheme 3
화학식(4)의 화합물과 강염기 촉매 존재 하에서 소듐설파이드, 유황 및 아민화제와 반응시켜 본 발명에서 목적하는 화학식(2)의 화합물을 제조하는데 있어서, 환원제로 사용하는 소듐 설파이드는 화학식(4)의 화합물에 대해 1.7 내지 3.3 몰배의 사용량으로 반응시키는 것이 바람직하며, 유황 사용량을 화학식(4)의 화합물에 대해 3.0 내지 6.0 몰배량을 사용하는 것이 좋다.In the preparation of the compound of formula (2) as desired in the present invention by reacting with a compound of formula (4) with sodium sulfide, sulfur and an aminating agent in the presence of a strong base catalyst, sodium sulfide used as a reducing agent is a compound of formula (4) It is preferable to react with 1.7 to 3.3 mole times with respect to the sulfur content, and it is preferable to use sulfur with 3.0 to 6.0 mole times with respect to the compound of Formula (4).
아민화제로는 수산화 암모늄, 탄산 암모늄 등이 사용 가능한데 사용량은 화학식(4)의 화합물에 대해 3.0 내지 4.0 몰배량을 사용하는 것이 좋다. Ammonium hydroxide, ammonium carbonate, etc. can be used as an aminizing agent, but it is good to use 3.0-4.0 molar amount with respect to the compound of General formula (4).
또한, 상기 화학식(4)의 화합물과 소듐 설파이드, 유황 및 아민화제와 반응시키는 경우에 반응온도를 90℃ 이하로 낮추면 반응온도가 느려지거나 반응이 완결되지 않을 염려가 있으므로 95 내지 100℃에서 반응을 시키는 것이 바람직하다. 이때 사용 가능한 용매로는 물이다. In addition, when reacting the compound of Formula (4) with sodium sulfide, sulfur and aminating agent, if the reaction temperature is lowered to 90 ° C. or lower, the reaction temperature may be slowed down or the reaction may not be completed. It is preferable to make it. At this time, the solvent that can be used is water.
특히, 상기 반응 조건에서 가성소다 등의 강염기를 소량 첨가시켜 반응을 촉진시키는 것이 바람직하며, 이때의 염기 촉매의 사용량은 일반식(4)의 화합물에 대해 0.6 내지 1.2 몰배량을 사용하는 것이 좋다.In particular, it is preferable to accelerate the reaction by adding a small amount of a strong base such as caustic soda under the above reaction conditions, and the amount of the base catalyst used at this time is preferably 0.6 to 1.2 molar times based on the compound of the formula (4).
반응이 완료된후 생성된 화학식(2)의 이소티아졸안트론 화합물은 별다른 정제과정 없이 고순도로 분리할 수 있는데, 반응액을 냉각한 후 여과하여 고체로서 얻을 수 있다.After completion of the reaction, the isothiazolanthrone compound of formula (2) can be separated with high purity without further purification. The reaction solution can be cooled and then filtered to obtain a solid.
따라서, 본 발명은 지금까지의 문헌에 공지된 방법들에 비해 훨씬 온화한 조건하에 반응을 진행시켜 점점 그 필요성이 증가되고 있는 화학식(1)의 제조에 유용한 화학식(2)의 이소티아졸안트론 화합물을 고순도로 수득할 수 있는 방법으로서, 앞으로 이 분야에 유용하게 이용될 것으로 기대된다.Accordingly, the present invention provides an isothiazolanthrone compound of formula (2) which is useful for the preparation of formula (1), which proceeds under much milder conditions than the methods known in the literature. As a method that can be obtained with high purity, it is expected to be usefully used in this field in the future.
이하, 본 발명을 하기 실시예에 의거하여 더욱 구체적으로 설명한다. 그러나, 이들 실시예는 본 발명을 설명하기 위한 것일 뿐 어떤 형태로든 본 발명의 기술적 범위가 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the following examples. However, these examples are only for illustrating the present invention, and the technical scope of the present invention in any form is not limited to the embodiments.
실시예 1:Example 1:
하기 화학식(5)의 화합물 50g, 소듐 설파이드 63g, 유황 16g 및 가성소다 6.8g을 물 125ml에 가하고 상압에서 교반하면서, 28% 수산화 암모늄 69ml를 적가한 다음 내부온도를 95 내지 100℃로 승온하여 30시간 동안 반응시켰다. 반응이 완결된 후 내부온도를 60℃로 냉각시켰다. 반응혼합물을 여과한 다음 냉수 625ml로 세척하고 건조시켜 화학식(2)의 이소티아졸안트론 화합물을 수율 74%, 순도 98%로 수득하였다.50 g of a compound of the formula (5), 63 g of sodium sulfide, 16 g of sulfur, and 6.8 g of caustic soda were added to 125 ml of water, and 69 ml of 28% ammonium hydroxide was added dropwise while stirring at normal pressure, and then the internal temperature was increased to 95 to 100 ° C. to 30 The reaction was carried out for a time. After the reaction was completed the internal temperature was cooled to 60 ℃. The reaction mixture was filtered, washed with 625 ml of cold water, and dried to obtain an isothiazolanthrone compound of formula (2) in a yield of 74% and a purity of 98%.
[화학식 5][Formula 5]
실시예 2:Example 2:
하기 화학식(6)의 화합물 48.5g, 소듐 설파이드 120g, 유황 29.2g 및 가성소다 6.5g을 물 125ml에 가하고 상압에서 교반하면서, 28% 수산화 암모늄 72ml를 적가한 다음 내부온도를 95 내지 100℃로 승온하여 30시간 동안 반응시켰다. 반응이 완결된 후 내부온도를 60℃로 냉각시켰다. 반응혼합물을 여과한 다음 냉수 625ml로 세척하고 건조시켜 화학식(2)의 이소티아졸안트론 화합물을 수율 70%, 순도 95%로 수득하였다. 48.5 g of the compound of formula (6), 120 g of sodium sulfide, 29.2 g of sulfur, and 6.5 g of caustic soda were added to 125 ml of water, and 72 ml of 28% ammonium hydroxide was added dropwise while stirring at normal pressure, and the internal temperature was raised to 95 to 100 ° C. The reaction was carried out for 30 hours. After the reaction was completed the internal temperature was cooled to 60 ℃. The reaction mixture was filtered, washed with 625 ml of cold water and dried to obtain the isothiazolanthrone compound of formula (2) in a yield of 70% and purity of 95%.
[화학식 6][Formula 6]
실시예 3:Example 3:
상기 화학식(5)의 화합물 50g, 소듐 설파이드 63g, 유황 15g, 탄산암모늄 47g 및 가성소다 6g을 물 125ml에 가하고 상압에서 교반하면서 내부온도를 95 내지 100℃로 승온하여 30시간 동안 반응시켰다. 반응이 완결된 후 내부온도를 60℃fh 냉각시켰다. 반응혼합물을 여과한 다음 냉수 625ml로 세척하고 건조시켜 화학식 (2)의 이소티아졸안트론 화합물을 수율 55%, 순도 97%로 수득하였다.50 g of the compound of formula (5), 63 g of sodium sulfide, 15 g of sulfur, 47 g of ammonium carbonate, and 6 g of caustic soda were added to 125 ml of water, and the reaction mixture was reacted for 30 hours by raising the internal temperature to 95 to 100 ° C. while stirring at atmospheric pressure. After the reaction was completed the internal temperature was cooled to 60 ℃ fh. The reaction mixture was filtered, washed with 625 ml of cold water and dried to obtain the isothiazolanthrone compound of formula (2) in a yield of 55% and purity of 97%.
실시예 4:Example 4:
상기 화학식(6)의 화합물 40g, 소듐 설파이드 51g, 유황 13g, 탄산 암모늄 38g 및 가성소다 5g을 물 100ml에 가하고 상압에서 교반하면서 내부온도를 95 내지 100℃로 승온하여 30시간 동안 반응시켰다. 반응이 완결된 후 내부온도를 60℃로 냉각시켰다. 반응혼합물을 여과한 다음 냉수 625ml로 세척하고 건조시켜 화학식 (2)의 이소티아졸안트론 화합물을 수율 54%, 순도 95%로 수득하였다.40 g of the compound of Formula 6, 51 g of sodium sulfide, 13 g of sulfur, 38 g of ammonium carbonate, and 5 g of caustic soda were added to 100 ml of water, and the reaction mixture was reacted for 30 hours by raising the internal temperature to 95 to 100 ° C. while stirring at normal pressure. After the reaction was completed the internal temperature was cooled to 60 ℃. The reaction mixture was filtered, washed with 625 ml of cold water and dried to obtain an isothiazolanthrone compound of formula (2) in a yield of 54% and purity of 95%.
본 발명에 따르면 화학식(4)의 화합물로 부터 고압반응기가 아닌 상압하에 화학식(2)의 이소티아졸안트론화합물을 부산물의 생성없이 경제적으로 합성할 수 있다.
According to the present invention, the isothiazoleanthrone compound of formula (2) can be economically synthesized from the compound of formula (4) under normal pressure and not under high pressure reactor without generation of by-products.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3972881A (en) * | 1973-08-22 | 1976-08-03 | Ciba-Geigy Corporation | Triazinyl dyes |
| US4199317A (en) * | 1973-12-13 | 1980-04-22 | Sublistatic Holding Sa | Printing process |
| JPS5693761A (en) * | 1979-12-18 | 1981-07-29 | Bayer Ag | Production of triazinyl aminoanthraquinone |
| JPS6092355A (en) * | 1983-10-25 | 1985-05-23 | Mitsubishi Chem Ind Ltd | Isothiazoleanthrone dye |
| US4845220A (en) * | 1987-01-09 | 1989-07-04 | Hans Altermatt | Vattable 2-aryl-4,6-diaminopyrimidines |
| KR0128107B1 (en) * | 1994-08-12 | 1998-04-04 | 강박광 | Process for benzanthrone |
-
2001
- 2001-02-06 KR KR1020010005639A patent/KR100620410B1/en active IP Right Grant
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3972881A (en) * | 1973-08-22 | 1976-08-03 | Ciba-Geigy Corporation | Triazinyl dyes |
| US4199317A (en) * | 1973-12-13 | 1980-04-22 | Sublistatic Holding Sa | Printing process |
| JPS5693761A (en) * | 1979-12-18 | 1981-07-29 | Bayer Ag | Production of triazinyl aminoanthraquinone |
| JPS6092355A (en) * | 1983-10-25 | 1985-05-23 | Mitsubishi Chem Ind Ltd | Isothiazoleanthrone dye |
| US4845220A (en) * | 1987-01-09 | 1989-07-04 | Hans Altermatt | Vattable 2-aryl-4,6-diaminopyrimidines |
| KR0128107B1 (en) * | 1994-08-12 | 1998-04-04 | 강박광 | Process for benzanthrone |
Non-Patent Citations (2)
| Title |
|---|
| 56093761 |
| 60092355 |
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|---|---|
| KR20020065216A (en) | 2002-08-13 |
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