KR0161208B1 - Process for preparing anthraquinone red disperse dye - Google Patents
Process for preparing anthraquinone red disperse dye Download PDFInfo
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- KR0161208B1 KR0161208B1 KR1019960004878A KR19960004878A KR0161208B1 KR 0161208 B1 KR0161208 B1 KR 0161208B1 KR 1019960004878 A KR1019960004878 A KR 1019960004878A KR 19960004878 A KR19960004878 A KR 19960004878A KR 0161208 B1 KR0161208 B1 KR 0161208B1
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- Prior art keywords
- amino
- phenoxy
- hexanediol
- hydroxyanthraquinone
- anthraquinone red
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/503—Amino-hydroxy-anthraquinones; Ethers and esters thereof unsubstituted amino-hydroxy anthraquinone
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/008—Preparations of disperse dyes or solvent dyes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
본 발명은 하기 일반식(II)의 1-아미노-2-페녹시-4-하이드록시안트라퀴논을 폴리에틸렌 글리콜 및 염기의 존재하에서 1,6-헥산디올과 반응시킴을 특징으로 하여, 하기 구조식(I)의 1-아미노-4-하이드록시-2-(6-하이드록시헥스옥시)안트라퀴논 적색 분산염료를 제조하는 신규한 방법에 관한 것이다.The present invention is characterized by reacting 1-amino-2-phenoxy-4-hydroxyanthraquinone of the following general formula (II) with 1,6-hexanediol in the presence of polyethylene glycol and a base. A novel process for preparing 1-amino-4-hydroxy-2- (6-hydroxyhexoxy) anthraquinone red dispersion dye of I).
상기식에서,In the above formula,
R은 H 또는 OCH3을 나타낸다.R represents H or OCH 3 .
Description
본 발명은 안트라퀴논 적색 분산염료의 신규한 제조방법에 관한 것으로, 특히 하기 구조식(I)의 1-아미노-4-하이드록시-2-(6-하이드록시헥스옥시)안트라퀴논 화합물의 신규한 제조방법에 관한 것이다.The present invention relates to a novel process for preparing anthraquinone red dispersion dyes, and in particular to the novel preparation of 1-amino-4-hydroxy-2- (6-hydroxyhexoxy) anthraquinone compounds of formula (I) It is about a method.
더 구체적으로 본 발명은 하기 일반식(II)의 안트라퀴논으로부터 구조식(I)의 2-하이드록시헥스옥시 안트라퀴논을 제조하는 개량된 방법에 관한 것이다.More specifically, the present invention relates to an improved process for preparing 2-hydroxyhexoxy anthraquinone of formula (I) from anthraquinone of formula (II).
상기식에서,In the above formula,
R은 H 또는 OCH3을 나타낸다.R represents H or OCH 3 .
1-아미노-4-하이드록시-2-(6-하이드록시헥스옥시)안트라퀴논 분산염료는 폴리에스테르 섬유에 대하여 일광, 습윤, 승화 견뢰도가 우수한 염료로서, 그의 여러 가지 합성법이 보고된 바 있다.1-amino-4-hydroxy-2- (6-hydroxyhexoxy) anthraquinone dispersion dye is a dye having excellent daylight, wetting, and sublimation fastness to polyester fibers, and various synthetic methods thereof have been reported.
종래 페녹시안트라퀴논으로부터 직접 하이드록시헥스옥시안트라퀴논을 제조하는 방법으로는 페녹시 그룹을 헥사메틸포스포릭트리아마이드(HMPA) 존재하에서 헥산디올로 치환시키는 방법이 알려져 있다(일본 특허공고 (소) 48-13698호).Conventionally, a method of preparing hydroxyhexoxyanthraquinone directly from phenoxycyantriquinone is known in which phenoxy group is substituted with hexanediol in the presence of hexamethylphosphoric triamide (HMPA) (Japanese Patent Publication (S)). 48-13698).
그러나, 이 방법은 첫째, 독성이 강하고 발암물질중에서도 가장 위험하다고 널리 알려진 헥사메틸포스포릭트리아마이드를 과량 사용하고, 둘째, 비싼 가격의 헥산디올을 8당량 이상 사용하고, 셋째, 20시간의 오랜 반응 시간을 필요로 하고, 넷째, 수율이 70%에 불과하므로, 비현실적이고 비경제적인 방법이다.However, this method first uses an excess of hexamethylphosphoric triamide, which is widely known to be toxic and the most dangerous among carcinogens, and secondly, uses more than 8 equivalents of expensive hexanediol, and third, a long reaction of 20 hours. It requires time and, fourthly, yields of only 70%, making it impractical and uneconomical.
한편, 가장 최근에 보고된 방법으로 2-페녹시안트라퀴논과 12 당량의 헥산디올만을 사용한 경우에도 수율이 매우 낮고 이합체만 과량 생성되었다. 이 경우 크로마토그래피 분석 결과는 목적물과 이합체가 35%와 65%로 나타나 이 또한 적합한 합성법이 아니다(유럽특허 데-88-303185호).On the other hand, when only 2-phenoxycyantraquinone and 12 equivalents of hexanediol were used as the most recently reported method, the yield was very low and only dimers were excessively produced. In this case, the chromatographic analysis resulted in 35% and 65% of the target and dimer, which is not a suitable synthesis method (European Patent De-88-303185).
페녹시안트라퀴논 대신 1-아미노 2-클로로(혹은 브로모)-4-하이드록시-안트라퀴논을 사용했을 때에도 이합체를 제거하기 위해서는 고온에서 오랫동안 반응시켜야 하는 결점이 있다(유럽특허 EP-88-303185호).Even when 1-amino 2-chloro (or bromo) -4-hydroxy-anthraquinone is used in place of phenoxycyanquinone, there is a drawback that a long reaction at high temperature is required to remove the dimer (European Patent EP-88-303185). number).
본 발명자들은 이와 같은 종래 방법중에 포함된 결점들을 해결하기 위해 광범위하게 연구한 결과 상기의 문제점을 해결하여 본 발명을 완성하게 되었다.The present inventors have extensively researched to solve the drawbacks included in such a conventional method, thereby completing the present invention by solving the above problems.
본 발명의 목적은 폴리에틸렌글리콜을 용매로 사용하고 페녹시안트라퀴논과 최소량의 헥산디올을 반응시켜 비교적 높은 수율과 높은 순도의 안트라퀴논 적색 분산염료를 제조하는 것이다.An object of the present invention is to prepare an anthraquinone red dispersion dye of relatively high yield and high purity by using polyethylene glycol as a solvent and reacting phenoxycyanquinone with a minimum amount of hexanediol.
즉, 본 발명은 일반식(II)의 1-아미노-2-페녹시-4-하이드록시안트라퀴논을 폴리에틸렌 글리콜 및 염기의 존재하에서 1,6-헥산디올과 반응시킴을 특징으로 하여, 구조식(I)의 1-아미노-4-하이드록시-2-(6-하이드록시헥스옥시)안트라퀴논 적색 분산염료를 제조하는 신규한 방법에 관한 것이다.That is, the present invention is characterized by reacting 1-amino-2-phenoxy-4-hydroxyanthraquinone of general formula (II) with 1,6-hexanediol in the presence of polyethylene glycol and a base. A novel process for preparing 1-amino-4-hydroxy-2- (6-hydroxyhexoxy) anthraquinone red dispersion dye of I).
상기식에서,In the above formula,
R은 H 또는 OCH3을 나타낸다.R represents H or OCH 3 .
이하, 본 발명의 제조방법은 구체적으로 설명한다.Hereinafter, the manufacturing method of the present invention will be described in detail.
본 발명에서 반응 온도는 120 내지 140℃가 적당하며 반응은 6시간 이내에 종료된다. 저온일 경우 반응시간이 길어지게 된다. 사용되는 염기로는 1당량 이내의 수산화나트륨과 수산화칼륨을 사용할 수 있다. 폴리에틸렌글리콜은 1-아미노-2-페녹시-4-하이드록시안트라퀴논에 대한 중량비로 1.5에서 2배 정도 사용되고, 중점도의 폴리에틸렌글리콜 200-600이 적합하다. 폴리에틸렌글리콜을 소량 사용하였을 때는 교반이 어렵게 되고, 과량 사용시는 교반이 쉽지만 부반응이 많이 발생된다. 또한, 낮은 점도의 폴리에틸렌글리콜 사용시에도 부반응이 많이 발생된다. 이상적인 1,6-헥산디올 사용량은 1-아미노-2-페녹시-4-하이드록시안트라퀴논 1몰당 3내지 4몰이고, 중량비로는 1내지 1.5배 이내가 된다. 페녹시 그룹의 4번 위치가 메톡시로 치환된 경우인 2-(4-메톡시페녹시)안트라퀴논에서도 치환기가 없는 페녹시 경우와 비교하여 동일한 결과를 얻을 수 있었다. 하기 표에서 나타난 바와 같이 헥산디올을 2당량 이내로 적게 사용할 시에는 수율이 감소하지만, 4당량 이상 과량 사용시 수율이 별로 증가하지 못하고 경제성만 저하된다. 반응의 부산물은 제거가 용이하고, 고성능 액상 크로마토그래피(HPLC) 분석에 의하면 목적물의 순도는 98%이상이며, 이합체는 검출되지 않았다.In the present invention, the reaction temperature is suitable 120 to 140 ℃ and the reaction is completed within 6 hours. At low temperatures, the reaction time is long. As the base used, sodium hydroxide and potassium hydroxide within 1 equivalent may be used. Polyethyleneglycol is used in a weight ratio of 1-amino-2-phenoxy-4-hydroxyanthraquinone in the range of 1.5 to 2 times, and polyethylene glycol 200-600 of medium viscosity is suitable. When a small amount of polyethylene glycol is used, stirring becomes difficult, and when used in an excessive amount, stirring is easy but many side reactions occur. In addition, many side reactions occur even when polyethylene glycol of low viscosity is used. The ideal amount of 1,6-hexanediol is 3 to 4 moles per 1 mole of 1-amino-2-phenoxy-4-hydroxyanthraquinone, and the weight ratio is within 1 to 1.5 times. The same result was obtained in 2- (4-methoxyphenoxy) anthraquinone, in which the position 4 of the phenoxy group was substituted with methoxy, compared with the case of phenoxy without a substituent. As shown in the following table, when using less than 2 equivalents of hexanediol, the yield decreases, but when using more than 4 equivalents, the yield does not increase very much and the economical efficiency is lowered. By-products of the reaction were easily removed, and high performance liquid chromatography (HPLC) analysis showed that the purity of the target product was 98% or more, and no dimers were detected.
또한, 기존의 보고된 합성방법은 질소와 무수조건 상태에서 진행되어야 했지만, 본 발명에서는 출발물질, 반응물질 및 대기중에 함유된 수분과 공기가 실질적으로 중요한 역할을 미치지 않으므로 특별한 탈수처리 없이 공정을 단축시킬 수 있다.In addition, the existing reported synthetic method had to proceed in an anhydrous condition with nitrogen, but in the present invention, since the water and air contained in the starting materials, the reactants, and the atmosphere do not play a significant role, the process is shortened without special dehydration treatment. You can.
한편, 구조식(I)의 화합물을 제조함에 있어 출발물질로 사용된 페녹시안 트라퀴논은 그 자체가 폴리에스테르용 분산 염료로도 사용되고, 그외 분산염료용 원료로서 다량으로 사용되고 있어 경제적 장점이 있다. 이와 같이 하여 종래의 방법과 비교할 때, 본 방법은 공정이 안전하고 이에 대한 경제적, 공업적 가치는 지대한 것이다.On the other hand, the phenoxane traquinone used as a starting material in the preparation of the compound of formula (I) is itself used as a disperse dye for polyester, it is also used in large quantities as a raw material for disperse dyes there is an economic advantage. In this way, when compared with the conventional method, the process is safe and its economic and industrial value is enormous.
이하, 본 발명을 하기 실시예에 의거하여 보다 구체적으로 설명하지만, 본 발명의 기술적 범위가 이들로 한정되는 것은 아니다.Hereinafter, although this invention is demonstrated further more concretely based on the following Example, the technical scope of this invention is not limited to these.
[실시예 1]Example 1
1-아미노-2-페녹시-4-하이드록시안트라퀴논 66.26g, 1,6-헥산디올 82.73g, 및 수산화나트륨 6.4g에 폴리에틸렌글리콜 133g을 가하고, 이 화합물을 135℃에서 6시간 동안 교반하였다. 반응종료 후 반응 혼합물 온도를 100℃로 낮춘 후 서서히 물 250g을 가하고 초산 25㎖을 가하여 약산성이 되게한 후 1내지 2시간 더 교반하였다. 이와 같이 하여 침전된 결정을 70℃ 정도에서 여과하고 물로써 충분히 세척, 건조시킨 후 157 내지 158℃에서 용융하는 황적색의 목적물 60.0g을 얻었다.133 g of polyethylene glycol was added to 66.26 g of 1-amino-2-phenoxy-4-hydroxyanthraquinone, 82.73 g of 1,6-hexanediol, and 6.4 g of sodium hydroxide, and the compound was stirred at 135 ° C. for 6 hours. . After completion of the reaction, the reaction mixture temperature was lowered to 100 ° C., 250 g of water was added slowly, and 25 ml of acetic acid was added to make it slightly acidic, followed by further stirring for 1 to 2 hours. The precipitated crystals were filtered at about 70 ° C., washed well with water, dried, and 60.0 g of a yellowish red target product was melted at 157 to 158 ° C.
융점 156내지 158℃, 수율 84.4%.Melting point 156-158 DEG C, yield 84.4%.
[실시예 2]Example 2
1-아미노-4-하이드록시-2-(4-메톡시)페녹시안트라퀴논 36.1g을 사용한 것 이외에는 실시예 1에 기술한 것과 동일한 방법으로 수행하여 목적물을 85.0% 수율로 얻었다.The target product was obtained in 85.0% yield by the same method as described in Example 1, except that 36.1 g of 1-amino-4-hydroxy-2- (4-methoxy) phenoxytriquinone was used.
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