KR960014048B1 - Process for the production of pyrimidine type reactive dye - Google Patents

Process for the production of pyrimidine type reactive dye Download PDF

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KR960014048B1
KR960014048B1 KR1019930022655A KR930022655A KR960014048B1 KR 960014048 B1 KR960014048 B1 KR 960014048B1 KR 1019930022655 A KR1019930022655 A KR 1019930022655A KR 930022655 A KR930022655 A KR 930022655A KR 960014048 B1 KR960014048 B1 KR 960014048B1
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disulfonic acid
amino
hydroxynaphthalene
general formula
acid
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KR1019930022655A
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Korean (ko)
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KR950011558A (en
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박상우
김동진
박웅서
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한국과학기술연구원
김은영
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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
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/20—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a pyrimidine ring
    • C09B62/24—Azo dyes
    • C09B62/245—Monoazo dyes
    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C09B29/0029—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom
    • C09B29/0051—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom containing a six-membered heterocyclic ring with two nitrogen atoms
    • 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

Abstract

The dye composite(I) is made by preparing the azo compound with formula(V) by diazo coupling reaction of the amino compounds(II) and (IV); dissolving 5-chloro-2,4,6-trifluoropyrimidine in a solvent and doping its solution into the azo compound to be pH5-9. The solvent comprises acetonitrile, dioxane or acetone, and pH is controlled by lithium hydroxide.

Description

피리미딘계 반응성 염료의 제조방법Method for preparing pyrimidine-based reactive dye

본 발명은 5-클로로-2,4,6-틀리플루오로피리미딘을 반응성분으로 하는 다음 일반식(Ⅰ)로 표시되는 피리미딘계 반응성염료의 제조방법에 관한 것이다.The present invention relates to a method for producing a pyrimidine-based reactive dye represented by the following general formula (I) using 5-chloro-2,4,6-trifluoropyrimidine as a reactive component.

상기 일반식(Ⅰ)에서 각 관능기별 특징을 살펴보면, A-N=N-B-(CH2)n-NMR은 색소(1)를,Looking at the characteristics of each functional group in the general formula (I), AN = NB- (CH 2 ) n-NMR is a pigment (1),

은 반응기(2)를 각각 나타낸다. 여기서 A는 디아조늄염의 출발물질이나 또는 커플링 성분이며, B역시 디아조늄염의 출발물질이나 커플링 성분이다. 또한 n은 0 또는 1이며, R은 H 또는 CH3이다. Represents the reactor 2, respectively. Here, A is a starting material or coupling component of the diazonium salt, and B is also a starting material or coupling component of the diazonium salt. And n is 0 or 1 and R is H or CH 3 .

A는 벤젠핵 또는 나프탈렌핵을 표시하며 디아조늄염의 출발물질일 경우, 2-아미노나프틸렌-1,5-디술폰산, 2-아미노나프틸렌-4,8-디술폰산, 2-아미노나프틸렌-6.8-디술폰산, 2-아미노나프틸렌-3,6,8-디술폰산, 2-아미노나프틸렌-4,6,8-디술폰산, 2-아미노벤젠술폰산, 4-메톡시아닐린-2-술폰산, 4-메톡시아닐린-2,5-디술폰산, 4-메틸아닐린-2,5-디술폰산을 말하며, 커플링 성분일 경우, 3-카바모A represents a benzene nucleus or a naphthalene nucleus, and as a starting material of a diazonium salt, 2-aminonaphthylene-1,5-disulfonic acid, 2-aminonaphthylene-4,8-disulfonic acid, 2-aminonaphthylene- 6.8-disulfonic acid, 2-aminonaphthylene-3,6,8-disulfonic acid, 2-aminonaphthylene-4,6,8-disulfonic acid, 2-aminobenzenesulfonic acid, 4-methoxyaniline-2-sulfonic acid , 4-methoxyaniline-2,5-disulfonic acid, 4-methylaniline-2,5-disulfonic acid, and in the case of a coupling component, 3-carbamo

다음은 본 발명의 이해를 돕기 위해서 실제로 디아조커플링 반응을 통해서 아조화합물을 합성한 다음, 5-클로로-2,4,6-트리플루오로피리미딘과 축합하여 최종 염료를 제조하는 과정을 반응단계별 화학식으로 표시한 것이다.Next, to aid the understanding of the present invention, the process of synthesizing an azo compound through a diazo coupling reaction and then condensing with 5-chloro-2,4,6-trifluoropyrimidine to produce a final dye is carried out. It is represented by the chemical formula in each step.

(1)디아조화(1) diaphragmization

(2)커플링(2) coupling

(3)축합(3) condensation

한편, 커플링 성분의 아미노기와 5-클로로-2,4,6-트리플루오로피리미딘을 먼저 축합하고 디아조커플링시켜 최종 염료를 제조하는 경우에는, 일반식(Ⅳ)의 아미노화합물을 5-클로로-2,4,6-트리플루오로피리미딘과 축합하여 일반식 (Ⅳ)의 피리미딘화합물을 합성한다. 이때 온도는 5-15℃, pH는 4-7이 적당하며, 5-클로로-2,4,6-트리플루오로피리미딘을 아세토니트릴, 디옥산,아세톤과 같은 유기용매에 희석하여 적하시키고 수산화리튬을 이용하여 pH를 약산성으로 일정하게 유지하게 유지하여 줌으로써 부반응이 일어나는 것을 억제하였다. 이를 반응식으로 표시하면 다음과 같다.On the other hand, in the case of preparing a final dye by first condensing the amino group of the coupling component with 5-chloro-2,4,6-trifluoropyrimidine and diazo coupling, the amino compound of the general formula (IV) is 5 A pyrimidine compound of the general formula (IV) is synthesized by condensation with -chloro-2,4,6-trifluoropyrimidine. At this time, temperature is 5-15 ℃, pH is 4-7, and 5-chloro-2,4,6-trifluoropyrimidine is added dropwise by diluting with organic solvents such as acetonitrile, dioxane, acetone, and hydroxide. By using lithium to keep the pH constant at a weak acidity to suppress the side reactions occur. This is expressed as a reaction scheme as follows.

이렇게 하여 합성된 일반식(Ⅳ)의 피리미딘화합물은 분리하지 않은, 채, 일반식(Ⅱ)의 아미노화합물을 앞서와 동일한 방법으로 디아조화한 일반식(Ⅲ)의 디아조늄염과 이다조커플링시켜 일반식(Ⅰ)의 최종 염료를 제조한다. 이를 반응식으로 표시하면 다음과 같다.The pyrimidine compound of the general formula (IV) thus synthesized is not separated, and the diazonium salt of the general formula (III) and the isidazo couple are diazotized to the amino compound of the general formula (II) in the same manner as before. Ring to prepare the final dye of formula (I). This is expressed as a reaction scheme as follows.

실시예 16Example 16

2-아미노-5-아미노메틸나프탈렌-1-술폰산 25.2부를 물 200부에 가하여 용해시키고 2N NaNO250부를 가한다. 온도를 0-5℃로 유지하면서 35% 염산 30부를 서서히 가하고 30분 동안 교반한 후, 1부의 요소를 가하여 과량의 아질산을 파괴시켜 디아조늄으로 만든다. 8-벤조일아미노-1-히드록시나프탈렌-3,5-디술폰산 42.3부를 물 300부에 가하고 2N Na2CO3수용액으로 pH를 8.0으로 조정하여 완전히 용해시킨 후, 앞서 준비한 디아조늄염 용액을 약 20분에 걸쳐서 가한다. 이때 온도는 5-10℃, pH는 2N Na2CO3수용액을 이용하여 7-8로 유지한다. 1시간동안 교반한 후, 5-클로로-2,4,6-트리플루오로피리미딘 20부를 아세토니트릴 40부에 희석하여 천천히 적하한다. 이때 온도는 20℃, pH는 5% LiOH 수용액으로 7.5-8.0으로 유지한다. 1시간동안 교반하여 반응이 완결되면 염화나트륨으로 염석하고 여과, 건조시켜 적색계통의 반응성 염료(73g, 수율 88%)를 얻는다.25.2 parts of 2-amino-5-aminomethylnaphthalene-1-sulfonic acid are added to 200 parts of water to dissolve and 50 parts of 2N NaNO 2 are added. Slowly add 30 parts of 35% hydrochloric acid and stir for 30 minutes while maintaining the temperature at 0-5 ° C., and then add 1 part of urea to break excess nitrite into diazonium. 42.3 parts of 8-benzoylamino-1-hydroxynaphthalene-3,5-disulfonic acid was added to 300 parts of water, and dissolved completely by adjusting the pH to 8.0 with a 2N Na 2 CO 3 aqueous solution. Apply over 20 minutes. At this time, the temperature is 5-10 ℃, pH is maintained at 7-8 using 2N Na 2 CO 3 aqueous solution. After stirring for 1 hour, 20 parts of 5-chloro-2,4,6-trifluoropyrimidine are diluted in 40 parts of acetonitrile and slowly added dropwise thereto. At this time, the temperature is 20 ℃, pH is maintained at 7.5-8.0 in 5% aqueous LiOH solution. When the reaction was completed by stirring for 1 hour, the reaction mixture was salted with sodium chloride, filtered and dried to give a red dye (73 g, yield 88%).

실시예 17-20Example 17-20

디아조성분과 커플링 성분을 다음 표에 제시한 대로 사용한 것을 제외하고 실시예 16과 동일하게 반응시켰다.The diazo component and the coupling component were reacted in the same manner as in Example 16 except that the diazo component and the coupling component were used as shown in the following table.

Claims (6)

일반식(Ⅱ)와 일반식(Ⅳ)의 아미노화합물의 디아조커플링 반응을 통해서 염석, 여과, 건조과정없이 일반식(Ⅴ)의 아조화합물을 얻은 후, 5-클로로-2,4,6-트리플루오로피리미딘을 유기용매에 희석시키고, 얻어진 용액을 일반식(Ⅴ)의 아조화합물에 적하하여 pH를 5~9에서 반응시키는 것을 특징으로 하는 일반식(Ⅰ)로 표시하는 피리미딘계 반응성 염료의 제조방법.After obtaining the azo compound of the general formula (V) without the salting out, filtration and drying process through the diazo coupling reaction of the amino compound of the general formula (II) and the general formula (IV), 5-chloro-2,4,6 The trifluoropyrimidine is diluted in an organic solvent and the resulting solution is added dropwise to the azo compound of the general formula (V) to react the pH at 5 to 9, wherein the pyrimidine system represented by the general formula (I) Process for preparing reactive dyes. A-NH2(Ⅱ)A-NH 2 (II) B-(CH2)n-NHR (Ⅳ)B- (CH 2 ) n-NHR (IV) A-N=N-B-(CH2)n-NHR (Ⅴ)AN = NB- (CH 2 ) n-NHR (Ⅴ) 여기서 A는 디아조늄염의 출발물질이나 또는 커플링 성분으로서, 벤젠핵 또는 나프탈렌핵을 표시하며 디아조늄염의 출발물질일 경우, 2-아미노나프탈렌-1,5-디술폰산, 2-아미노나프틸렌-4,8-디술폰산, 2-아미노나프틸렌-6.8-디술폰산, 2-아미노나프틸렌-3,6,8-디술폰산, 2-아미노나프틸렌-4,6,8-디술폰산, 2-아미노벤젠술폰산, 4-메톡시아닐린-2-술폰산, 4-메톡시아닐린-2,5-디술폰산을 말하며, 커플링 성분일 경우, 3-카바모일-1-에틸-6-히드록시-4-메틸-2-피리돈, 8-벤조일아미노-1-히드록시나프탈렌-3,6-디술폰산, 8-벤조일아미노-1-히드록시나프탈렌-3,5-디술폰산, 8-아세틸아미노-1-히드록시나프탈렌-3,6-디술폰산, 8-아세틸아미노-1-히드록시나프탈렌-3,5-디술폰산을 말한다. B 역시 디아조늄염의 출발물질이나 커플링 성분으로서 벤젠핵 또는 나프탈렌핵을 표시하며 디아조늄염의 출발물인 경우, 6-메틸-1,3-디아미노벤젠-4-술폰산, 2-아미노-5-아미노메틸나프탈렌-1-술폰산, 2-아미노-5-아미노메틸나프탈렌-1,7-디술폰산을 말하며, 커플링 성분일 경우, 3-아미노-1-아세트아닐리드, 3-아미노페닐요소, 2-메톡시-5-메틸아닐린, 8-(4'-아미노벤조일)아미노-1-히드록시나프탈렌-3,6-디술폰산, 8-아미노-1-히드록시나프탈렌-3,6-디술폰산, 6-아미노-1-히드록시나프탈렌-3-술폰산, 6-메틸아미노-1-히드록시나프탈렌-3-술폰산, 3-메틸아미노톨루엔Where A represents the starting material or coupling component of the diazonium salt, and represents a benzene nucleus or a naphthalene nucleus, and when the starting material of the diazonium salt is 2-aminonaphthalene-1,5-disulfonic acid, 2-aminonaphthylene-4 , 8-disulfonic acid, 2-aminonaphthylene-6.8-disulfonic acid, 2-aminonaphthylene-3,6,8-disulfonic acid, 2-aminonaphthylene-4,6,8-disulfonic acid, 2-amino Benzenesulfonic acid, 4-methoxyaniline-2-sulfonic acid, 4-methoxyaniline-2,5-disulfonic acid, and, in the case of coupling components, 3-carbamoyl-1-ethyl-6-hydroxy-4- Methyl-2-pyridone, 8-benzoylamino-1-hydroxynaphthalene-3,6-disulfonic acid, 8-benzoylamino-1-hydroxynaphthalene-3,5-disulfonic acid, 8-acetylamino-1- Hydroxynaphthalene-3,6-disulfonic acid and 8-acetylamino-1-hydroxynaphthalene-3,5-disulfonic acid. B also represents benzene nucleus or naphthalene nucleus as starting material or coupling component of diazonium salt, and in case of starting diazonium salt, 6-methyl-1,3-diaminobenzene-4-sulfonic acid, 2-amino-5-amino Methylnaphthalene-1-sulfonic acid, 2-amino-5-aminomethylnaphthalene-1,7-disulfonic acid, in the case of a coupling component, 3-amino-1-acetanilide, 3-aminophenylurea, 2-meth Methoxy-5-methylaniline, 8- (4'-aminobenzoyl) amino-1-hydroxynaphthalene-3,6-disulfonic acid, 8-amino-1-hydroxynaphthalene-3,6-disulfonic acid, 6- Amino-1-hydroxynaphthalene-3-sulfonic acid, 6-methylamino-1-hydroxynaphthalene-3-sulfonic acid, 3-methylaminotoluene 을 말한다. 또한 n은 0 또는 1이며, R은 H 또는 CH3이다.Say And n is 0 or 1 and R is H or CH 3 . 제1항에 있어서, 유기용매로 아세토니트릴, 디옥산 또는 아세톤을 사용하는 것을 특징으로 하는 제조방법.The method according to claim 1, wherein acetonitrile, dioxane or acetone is used as the organic solvent. 제1항에 있어서, pH를 일정하게 조절하기 위해서 수산화리튬(LiOH)을 사용하여 것을 특징으로 하는 제조방법.The method according to claim 1, wherein lithium hydroxide (LiOH) is used to constantly adjust the pH. 5-클로로-2,4,6-트리플루오로피리미딘을 유기용매에서 희석시켜 pH를 4~7에서 일반식(Ⅳ)의 아미노화합물과 반응시켜 일반식(Ⅳ)의 피리미딘 화합물을 얻은 후, 일반식(Ⅱ)의 아미노화합물과 디아조커플링하는 것을 특징으로 하는 일반식(Ⅰ)로 표시되는 피리미딘계 반응성 염료의 제조방법 :Dilute 5-chloro-2,4,6-trifluoropyrimidine in an organic solvent to react with an amino compound of general formula (IV) at pH 4-7 to obtain a pyrimidine compound of general formula (IV). A process for producing a pyrimidine-based reactive dye represented by formula (I), characterized by diazotically coupling with an amino compound of formula (II): A-NH2(Ⅱ)A-NH 2 (II) B-(CH2)n-NHR (Ⅳ)B- (CH 2 ) n-NHR (IV) A-N=N-B-(CH2)n-NHR (Ⅴ)AN = NB- (CH 2 ) n-NHR (Ⅴ) B-(CH2)n-N (Ⅵ)B- (CH2) n-N (VI) A, B, n 및 R은 제1항에 정의된 것과 동일하다.A, B, n and R are the same as defined in claim 1. 제4항에 있어서, 유기용매로 아세토니트릴, 디옥산 또는 아세톤을 사용하는 것을 특징으로 하는 제조방법.5. A process according to claim 4, wherein acetonitrile, dioxane or acetone is used as the organic solvent. 제4항에 있어서, pH를 일정하게 조절하기 위해서 수산화리튬(LiOH)을 사용하는 것을 특징으로 하는 제조방법.The method according to claim 4, wherein lithium hydroxide (LiOH) is used to constantly adjust the pH.
KR1019930022655A 1993-10-28 1993-10-28 Process for the production of pyrimidine type reactive dye KR960014048B1 (en)

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