CN103232409B - Preparation method of disperse dyestuff - Google Patents

Preparation method of disperse dyestuff Download PDF

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CN103232409B
CN103232409B CN201210594524.9A CN201210594524A CN103232409B CN 103232409 B CN103232409 B CN 103232409B CN 201210594524 A CN201210594524 A CN 201210594524A CN 103232409 B CN103232409 B CN 103232409B
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CN103232409A (en
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韩伟鹏
赵敏
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Shanghai Anoky Group Co Ltd
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Abstract

The invention discloses a preparation method of a disperse dyestuff, and provides a preparation of a compound represented by the formula 1. The method comprises the steps that: in a solvent and under an acid catalyzing condition, diazonium salt represented by s formula 3 is subjected to a coupling reaction with a compound represented by a formula 2, such that the compound 1 is obtained, wherein A is Cl<->, CH2COO<->, H2PO4<->, HSO4<->, or NO3<->; R1 is C1-4 alkoxy or hydrogen; R2 is C1-4 acylamino or hydrogen; R3 is C1-4 alkyl; and R4 is C1-4 alkyl; and D is represented as the following. The disperse dyestuff preparation method provided by the invention has the advantages of simple process, easy operation, simple post-treatment method, low raw material toxicity, and environment-friendliness.

Description

A kind of preparation method of dispersed dye
Technical field
The present invention relates to a kind of preparation method of dispersed dye.
Background technology
Dispersed dye are that a class formation is simple, water-soluble low, mainly with the non-ionic dye that molecule is dispersion state existence in dye bath.Just come out as far back as early 1920s, be mainly used in the dyeing of cellulose acetate fibre at that time, be therefore also referred to as cellulose acetate dye.In recent years, along with synthon particularly the developing rapidly of trevira, dispersed dye become one of the fastest dyestuff of modern development gradually.Be mainly used in dyeing and the stamp of trevira at present, also can be used for the dyeing of the hydrophobic textile material such as cellulose acetate fibre and tynex.Along with the raising of people's living standard, human consumer is also more and more higher for the requirement of weaving official ceremonial dress performance, and as required, dyed textiles has higher fastness to sublimation, the multinomial fastness such as sun-resistant.Dispersed dye of some conventional application are as red in C.I. 153, C.I. purple 93, C.I. blue 291 and C.I. orange 288 etc., be then not suitable for requiring higher application to fastness to sublimation.
The reaction of phenol and epoxy chloropropane has the introduction of similar structures compou nd synthesis method in US Patent No. 2010279997A1; In addition, be the explanation also having related methods of synthesis in the CAS database of 122-60-1 at No. CAS.But the synthetic method reaction time that above patent documentation is mentioned is long, post-processing operation is loaded down with trivial details, and needs the participation of a large amount of solvent, very uneconomic environmental protection.
Prepare the reaction of compound 4, in US Patent No. 4448719A, have the introduction of similar structures compou nd synthesis method;
In addition, at document Russian Journal of Organic Chemistry, 43(8), 1176-1179; Also the introduction of dependency structure compound synthetic method is had in 2007.But preparation technology's reaction process of document report is complicated, and post-processing operation is loaded down with trivial details.
Prepare the reaction of compound 2, there is no patent literature at present, only has the reaction of similar acylated hydroxy, at document Russian Journal of Organic Chemistry, 43(8), 1176-1179, has similar reaction in 2007, but is adopt Acetyl Chloride 98Min. to carry out acidylate to hydroxyl in the document; Do reaction raw materials with acyl chlorides, toxicity is large, and requirement of shelter is higher, and in last handling process, environmental pollution is serious.
Summary of the invention
Technical problem to be solved by this invention is the complicated process of preparation in order to overcome existing dyestuff, and material toxicity is large, the defects such as post-processing operation is loaded down with trivial details, and environmental pollution is serious, and provides a kind of preparation method of dispersed dye.Preparation method's technique of dispersed dye of the present invention is simple, easy handling, and post-treating method is simple, and material toxicity is little, environmental friendliness.
The invention provides a kind of compound as shown in Equation 1
Wherein, R 1for C 1-4alkoxyl group or hydrogen; R 2for C 1-4amido or hydrogen; R 3for C 1- 4alkyl; R 4for C 1-4alkyl; D is
Wherein, R 1be preferably methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy or hydrogen.R 2be preferably formamido group, kharophen, propionamido, butyrylamino or hydrogen.R 3be preferably methyl, ethyl, propyl group or butyl.R 4be preferably methyl, ethyl, propyl group or butyl.R 1more preferably methoxyl group, oxyethyl group or hydrogen.R 2more preferably kharophen, propionamido or hydrogen.R 3more preferably methyl or ethyl.R 4more preferably methyl or ethyl.Described compound 1 is a kind of dispersed dye.
Present invention also offers the preparation method of compound as shown in Equation 1, it comprises the following steps: in a solvent, under acid catalyzed condition, diazonium salt as shown in Equation 3 and compound is as shown in Equation 2 carried out coupled reaction, obtains compound 1;
Wherein, A is Cl -, CH 2cOO -, H 2pO 4 -, HSO 4 -or NO 3 -, R 1for C 1-4alkoxyl group or hydrogen; R 2for C 1-4amido or hydrogen; R 3for C 1-4alkyl; R 4for C 1-4alkyl; D is
In the method preparing compound 1, R 1be preferably methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy or hydrogen.R 2be preferably formamido group, kharophen, propionamido, butyrylamino or hydrogen.R 3be preferably methyl, ethyl, propyl group or butyl.R 4be preferably methyl, ethyl, propyl group or butyl.R 1more preferably methoxyl group, oxyethyl group or hydrogen.R 2more preferably kharophen, propionamido or hydrogen.R 3more preferably methyl or ethyl.R 4more preferably methyl or ethyl.
In the method preparing compound 1, described coupled reaction can be carried out according to the ordinary method of such reaction in this area, preferred following reaction conditions and step:
In the method preparing compound 1, described solvent preferably water.
In the method preparing compound 1, the volume mass of described solvent and described compound 2 than preferred 4mL/g ~ 12mL/g, preferred 6mL/g ~ 9mL/g further.
In the method preparing compound 1, one or more in the preferred hydrochloric acid of described acid, acetic acid, phosphoric acid, nitric acid and sulfuric acid, one or more further preferably in hydrochloric acid, acetic acid and sulfuric acid, then preferably sulfuric acid and/or hydrochloric acid further.Described acid can participate in reaction with the form of aqueous acid, the mass percent concentration of described aqueous acid preferably 1% ~ 20%, and further preferably 3% ~ 15%.
In the method preparing compound 1, the volume ratio of described acid and described solvent preferably 0.005 ~ 0.02, further preferably 0.008 ~ 0.012.
In the method preparing compound 1, the preferred 1:1 ~ 1:1.5 of mol ratio of described compound 2 and the diazonium salt of compound 3, further preferred 1:1 ~ 1:1.2.
In the method preparing compound 1, the temperature of described coupled reaction preferably-10 DEG C ~ 30 DEG C, preferred-10 DEG C ~ 10 DEG C further, more preferred-5 DEG C ~ 5 DEG C further.
In the method preparing compound 1, the process of described coupled reaction can be monitored by traditional test methods in this area (as filter paper oozes circle method), and no longer carry out as reaction end to react, the preferred reaction time is 1h ~ 3h, further preferred 2h.
Above-mentioned diazonium salt as shown in Equation 3 can obtain by the following method: under sour existent condition, by nitrite or nitrosyl sulfuric acid, carries out diazotization reaction with aromatic amine as shown in Equation 8, obtains the diazonium salt of compound 3; Compound 1 is obtained again according to the above-mentioned method preparing compound 1;
Wherein, A is Cl -, CH 2cOO -, H 2pO 4 -, HSO 4 -or NO 3 -; D is
Can carry out according to the ordinary method in this area in described diazotization reaction, preferred following reaction conditions:
In described diazotization reaction, described solvent preferably water.
In described diazotization reaction, one or more in the preferred hydrochloric acid of described acid, acetic acid and sulfuric acid, further preferably sulfuric acid and/or hydrochloric acid.Described acid can participate in reaction with the form of aqueous acid, the mass percent concentration of described aqueous acid preferably 10% ~ 90%, and further preferably 20% ~ 80%.
In described diazotization reaction, the preferred Sodium Nitrite of described nitrite.
In described diazotization reaction, the volume mass of described solvent and described aromatic amine as shown in Equation 8 than preferred 1mL/g ~ 10mL/g, preferred 2mL/g ~ 5mL/g further.
In described diazotization reaction, the preferred 1:1 ~ 1:1.2 of mol ratio of described aromatic amine as shown in Equation 8 and described nitrite or nitrosyl sulfuric acid, further preferred 1:1 ~ 1:1.1.
In described diazotization reaction, the temperature of described reaction preferably-10 DEG C ~ 30 DEG C, preferred-10 ~ 20 DEG C further.
The process of described diazotization reaction can by traditional test methods (as TLC) monitoring in this area, and disappear for reaction end with described aromatic amine as shown in Equation 8, the preferred reaction time is 1h ~ 5h, further preferred 2h ~ 3h.
Above-claimed cpd 2 can be obtained by following method: compound 4 and acid anhydrides are as shown in Equation 5 carried out acylation reaction, obtains compound 2;
Prepare compound 3 according to the above-mentioned method preparing compound 3 again, then prepare compound 1 according to the above-mentioned method preparing compound 1; Wherein, R 1for C 1-4alkoxyl group or hydrogen; R 2for C 1-4amido or hydrogen; R 3for C 1-4alkyl; R 4for C 1-4alkyl.
In the method preparing compound 2, R 1be preferably methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy or hydrogen.R 2be preferably formamido group, kharophen, propionamido, butyrylamino or hydrogen.R 3be preferably methyl, ethyl, propyl group or butyl.R 4be preferably methyl, ethyl, propyl group or butyl.R 1more preferably methoxyl group, oxyethyl group or hydrogen.R 2more preferably kharophen, propionamido or hydrogen.R 3more preferably methyl or ethyl.R 4more preferably methyl or ethyl.
In the method preparing compound 2, described acylation reaction can be carried out according to the ordinary method of this area, particularly preferably following reaction conditions in the present invention:
In the method preparing compound 2, described reaction can be carried out in a solvent, also can carry out in the absence of a solvent.The preferred organic acid of described solvent, the preferred acetic acid of described organic acid.
In the method preparing compound 2, the volume mass of described solvent and described compound 4 than preferred 1mL/g ~ 10mL/g, preferred 1mL/g ~ 5mL/g further.
In the method preparing compound 2, described acid anhydrides 5 and the preferred 1:1 ~ 1:1.2 of mol ratio of described compound 4, further preferred 1:1 ~ 1:1.1.
In the method preparing compound 2, the temperature of described acylation reaction preferably 20 DEG C ~ 100 DEG C, preferably 25 DEG C ~ 75 DEG C further, more preferably 50 DEG C further.
In the method preparing compound 2, the process of described acylation reaction can by traditional test methods (as HPLC) monitoring in this area, and reacted for reaction end with compound 4, the preferred reaction time is 2h ~ 6h, further preferred 4 ~ 5h.
Above-claimed cpd 4 can be obtained by following method: compound 6 and amine are as shown in Equation 7 reacted, obtain compound 4;
Obtain compound 2 according to the above-mentioned method preparing compound 2 again, then prepare compound 3 according to the above-mentioned method preparing compound 3, then prepare compound 1 according to the above-mentioned method preparing compound 1; Wherein, R 1for C 1-4alkoxyl group or hydrogen; R 2for C 1-4amido or hydrogen; R 3for C 1-4alkyl.
In the method preparing compound 4, R 1be preferably methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy or hydrogen.R 2be preferably formamido group, kharophen, propionamido, butyrylamino or hydrogen.R 3be preferably methyl, ethyl, propyl group or butyl.R 4be preferably methyl, ethyl, propyl group or butyl.R 1more preferably methoxyl group, oxyethyl group or hydrogen.R 2more preferably kharophen, propionamido or hydrogen.R 3more preferably methyl or ethyl.R 4more preferably methyl or ethyl.
In the method preparing compound 4, described reaction can be carried out according to the ordinary method of this area, particularly preferably following reaction conditions in the present invention:
In the method preparing compound 4, described reaction can be carried out also can carrying out in the absence of a solvent in a solvent.The preferred organic acid of described solvent, the preferred acetic acid of described organic acid.
In the method preparing compound 4, the volume mass of described solvent and described compound 7 than preferred 1mL/g ~ 10mL/g, preferred 1mL/g ~ 5mL/g further.
In the method preparing compound 4, described compound 6 and the preferred 1:1 ~ 1:2 of mol ratio of described compound 7, further preferred 1:1 ~ 1:1.1.
In the method preparing compound 4, the temperature of described reaction preferably 20 DEG C ~ 100 DEG C, preferably 25 DEG C ~ 75 DEG C further, more preferably 50 DEG C further.
In the method preparing compound 4, the process of described reaction can by traditional test methods (as HPLC) monitoring in this area, and reacted for reaction end with compound 7, the preferred reaction time is 1h ~ 5h, further preferred 2h ~ 4h.
Above-claimed cpd 6 can be obtained by following method: in a solvent, under the condition of alkali existence and catalyst, phenol and epoxy chloropropane is reacted, obtains compound 6;
Obtain compound 4 according to the above-mentioned method preparing compound 4 again, obtain compound 2 according to the above-mentioned method preparing compound 2, then prepare compound 3 according to the above-mentioned method preparing compound 3, then prepare compound 1 according to the above-mentioned method preparing compound 1.
In the method preparing compound 6, described reaction can be carried out according to the ordinary method of this area, particularly preferably following reaction conditions in the present invention:
In the method preparing compound 6, described solvent preferably water.
In the method preparing compound 6, the preferred PEG-400(poly(oxyethylene glycol) 400 of described catalyzer).
In the method preparing compound 6, described catalyzer and the mass percent of phenol preferably 1% ~ 30%, further preferably 5% ~ 25%, more further preferably 10%.
In the method preparing compound 6, the volume mass of described solvent and described compound phenol than preferred 1mL/g ~ 10mL/g, preferred 1mL/g ~ 5mL/g further.
In the method preparing compound 6, described phenol and the preferred 1:1 ~ 1:1.8 of the mol ratio of epoxy chloropropane, further preferred 1:1 ~ 1:1.5.
In the method preparing compound 6, the preferred mineral alkali of described alkali, one or more in the preferred sodium hydroxide of described mineral alkali, potassium hydroxide, salt of wormwood, sodium bicarbonate, saleratus and sodium carbonate, further preferred sodium hydroxide.
In the method preparing compound 6, described alkali can participate in reaction with the form of the aqueous solution of alkali, the mass percent concentration of the aqueous solution of described alkali preferably 10% ~ 40%, and further preferably 25% ~ 35%, more further preferably 30%.
In the method preparing compound 6, described alkali and the preferred 1:1 ~ 1:1.2 of the mol ratio of phenol, further preferred 1:1.
In the method preparing compound 6, the temperature of described reaction preferably 0 DEG C ~ 100 DEG C, preferably 20 DEG C ~ 75 DEG C further, more preferably 50 DEG C ~ 55 DEG C further.
In the method preparing compound 6, the process of described reaction can by traditional test methods (as HPLC) monitoring in this area, and complete for reaction end with phenol primitive reaction, the preferred reaction time is 1h ~ 6h, further preferred 2h ~ 5h.
The invention provides a kind of preparation method of compound as shown in Equation 2, it comprises the following steps: compound 4 and acid anhydrides are as shown in Equation 5 carried out acylation reaction, obtains compound 2;
Wherein, R 1for C 1-4alkoxyl group or hydrogen; R 2for C 1-4amido or hydrogen; R 3for C 1- 4alkyl; R 4for C 1-4alkyl.
In the method preparing compound 2, R 1be preferably methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy or hydrogen.R 2be preferably formamido group, kharophen, propionamido, butyrylamino or hydrogen.R 3be preferably methyl, ethyl, propyl group or butyl.R 4be preferably methyl, ethyl, propyl group or butyl.R 1more preferably methoxyl group, oxyethyl group or hydrogen.R 2more preferably kharophen, propionamido or hydrogen.R 3more preferably methyl or ethyl.R 4more preferably methyl or ethyl.
In the method preparing compound 2, described acylation reaction can be carried out according to the ordinary method of this area, particularly preferably following reaction conditions in the present invention:
In the method preparing compound 2, described reaction can be carried out in a solvent, also can carry out in the absence of a solvent.The preferred organic acid of described solvent, the preferred acetic acid of described organic acid.
In the method preparing compound 2, the volume mass of described solvent and described compound 4 than preferred 1mL/g ~ 10mL/g, preferred 1mL/g ~ 5mL/g further.
In the method preparing compound 2, described acid anhydrides 5 and the preferred 1:1 ~ 1:1.2 of mol ratio of described compound 4, further preferred 1:1 ~ 1:1.1.
In the method preparing compound 2, the temperature of described acylation reaction preferably 20 DEG C ~ 100 DEG C, preferably 25 DEG C ~ 75 DEG C further, more preferably 50 DEG C further.
In the method preparing compound 2, the process of described acylation reaction can by traditional test methods (as HPLC) monitoring in this area, and reacted for reaction end with compound 4, the preferred reaction time is 2h ~ 6h, further preferred 4 ~ 5h.
The invention provides the preparation method of compound 1, it preferably comprises the following steps:
Step 1: in a solvent, under the condition of alkali existence and catalyst, reacts phenol and epoxy chloropropane, obtains compound 6;
Step 2: compound 6 obtained in step 1 is reacted with amine as shown in Equation 7, obtains compound 4;
Step 3: compound 4 obtained in step 2 is carried out acylation reaction with acid anhydrides as shown in Equation 5, obtains compound 2;
Step 4: under sour existent condition, carries out diazotization reaction by aromatic amine as shown in Equation 8 and nitrite or nitrosyl sulfuric acid, obtains the diazonium salt of compound 3;
Step 5: in a solvent, under acid catalyzed condition, carries out coupled reaction by compound as shown in Equation 2 obtained in diazonium salt as shown in Equation 3 obtained in step 4 and step 3, obtains compound 1;
Wherein, R 1for C 1-4alkoxyl group or hydrogen; R 2for C 1-4amido or hydrogen; R 3for C 1- 4alkyl; R 4for C 1-4alkyl; D is
Wherein, R 1be preferably methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy or hydrogen.R 2be preferably formamido group, kharophen, propionamido, butyrylamino or hydrogen.R 3be preferably methyl, ethyl, propyl group or butyl.R 4be preferably methyl, ethyl, propyl group or butyl.R 1more preferably methoxyl group, oxyethyl group or hydrogen.R 2more preferably kharophen, propionamido or hydrogen.R 3more preferably methyl or ethyl.R 4more preferably methyl or ethyl.Described compound 1 is a kind of dispersed dye.
In the method preparing compound 6, described reaction can be carried out according to the ordinary method of this area, particularly preferably following reaction conditions in the present invention:
In the method preparing compound 6, described solvent preferably water.
In the method preparing compound 6, the preferred PEG-400(poly(oxyethylene glycol) 400 of described catalyzer).
In the method preparing compound 6, described catalyzer and the mass percent of phenol preferably 1% ~ 30%, further preferably 5% ~ 25%, more further preferably 10%.
In the method preparing compound 6, the volume mass of described solvent and described compound phenol than preferred 1mL/g ~ 10mL/g, preferred 1mL/g ~ 5mL/g further.
In the method preparing compound 6, described phenol and the preferred 1:1 ~ 1:1.8 of the mol ratio of epoxy chloropropane, further preferred 1:1 ~ 1:1.5.
In the method preparing compound 6, the preferred mineral alkali of described alkali, one or more in the preferred sodium hydroxide of described mineral alkali, potassium hydroxide, salt of wormwood, sodium bicarbonate, saleratus and sodium carbonate, further preferred sodium hydroxide.
In the method preparing compound 6, described alkali can participate in reaction with the form of the aqueous solution of alkali, the mass percent concentration of the aqueous solution of described alkali preferably 10% ~ 40%, and further preferably 25% ~ 35%, more further preferably 30%.
In the method preparing compound 6, described alkali and the preferred 1:1 ~ 1:1.2 of the mol ratio of phenol, further preferred 1:1.
In the method preparing compound 6, the temperature of described reaction preferably 0 DEG C ~ 100 DEG C, preferably 20 DEG C ~ 75 DEG C further, more preferably 50 DEG C ~ 55 DEG C further.
In the method preparing compound 6, the process of described reaction can by traditional test methods (as HPLC) monitoring in this area, and complete for reaction end with phenol primitive reaction, the preferred reaction time is 1h ~ 6h, further preferred 2h ~ 5h.
In the method preparing compound 4, described reaction can be carried out according to the ordinary method of this area, particularly preferably following reaction conditions in the present invention:
In the method preparing compound 4, described reaction can be carried out also can carrying out in the absence of a solvent in a solvent.The preferred organic acid of described solvent, the preferred acetic acid of described organic acid.
In the method preparing compound 4, the volume mass of described solvent and described compound 7 than preferred 1mL/g ~ 10mL/g, preferred 1mL/g ~ 5mL/g further.
In the method preparing compound 4, described compound 6 and the preferred 1:1 ~ 1:2 of mol ratio of described compound 7, further preferred 1:1 ~ 1:1.1.
In the method preparing compound 4, the temperature of described reaction preferably 20 DEG C ~ 100 DEG C, preferably 25 DEG C ~ 75 DEG C further, more preferably 50 DEG C further.
In the method preparing compound 4, the process of described reaction can by traditional test methods (as HPLC) monitoring in this area, and reacted for reaction end with compound 7, the preferred reaction time is 1h ~ 5h, further preferred 2h ~ 4h.
In the method preparing compound 2, described acylation reaction can be carried out according to the ordinary method of this area, particularly preferably following reaction conditions in the present invention:
In the method preparing compound 2, described reaction can be carried out in a solvent, also can carry out in the absence of a solvent.The preferred organic acid of described solvent, the preferred acetic acid of described organic acid.
In the method preparing compound 2, the volume mass of described solvent and described compound 4 than preferred 1mL/g ~ 10mL/g, preferred 1mL/g ~ 5mL/g further.
In the method preparing compound 2, described acid anhydrides 5 and the preferred 1:1 ~ 1:1.2 of mol ratio of described compound 4, further preferred 1:1 ~ 1:1.1.
In the method preparing compound 2, the temperature of described acylation reaction preferably 20 DEG C ~ 100 DEG C, preferably 25 DEG C ~ 75 DEG C further, more preferably 50 DEG C further.
In the method preparing compound 2, the process of described acylation reaction can by traditional test methods (as HPLC) monitoring in this area, and reacted for reaction end with compound 4, the preferred reaction time is 2h ~ 6h, further preferred 4 ~ 5h.
Described diazotization reaction can be carried out according to the ordinary method in this area, preferred following reaction conditions:
In described diazotization reaction, described solvent preferably water.
In described diazotization reaction, one or more in the preferred hydrochloric acid of described acid, acetic acid and sulfuric acid, further preferably sulfuric acid and/or hydrochloric acid.Described acid can participate in reaction with the form of aqueous acid, the mass percent concentration of described aqueous acid preferably 10% ~ 90%, and further preferably 20% ~ 80%.
In described diazotization reaction, the preferred Sodium Nitrite of described nitrite.
In described diazotization reaction, the volume mass of described solvent and described aromatic amine as shown in Equation 8 than preferred 1mL/g ~ 10mL/g, preferred 2mL/g ~ 5mL/g further.
In described diazotization reaction, the preferred 1:1 ~ 1:1.2 of mol ratio of described aromatic amine as shown in Equation 8 and described nitrite or nitrosyl sulfuric acid, further preferred 1:1 ~ 1:1.1.
In described diazotization reaction, the temperature of described reaction preferably-10 DEG C ~ 30 DEG C, preferred-10 ~ 20 DEG C further.
Can by traditional test methods (as TLC) monitoring in this area in the process of described diazotization reaction, disappear for reaction end with described aromatic amine as shown in Equation 8, the preferred reaction time is 1h ~ 5h, further preferred 2h ~ 3h.
In the method preparing compound 1, described coupled reaction can be carried out according to the ordinary method of such reaction in this area, preferred following reaction conditions and step:
In the method preparing compound 1, described solvent preferably water.
In the method preparing compound 1, the volume mass of described solvent and described compound 2 than preferred 4mL/g ~ 12mL/g, preferred 6mL/g ~ 9mL/g further.
In the method preparing compound 1, one or more in the preferred hydrochloric acid of described acid, acetic acid, phosphoric acid, nitric acid and sulfuric acid, one or more further preferably in hydrochloric acid, acetic acid and sulfuric acid, then preferably sulfuric acid and/or hydrochloric acid further.Described acid can participate in reaction with the form of aqueous acid, the mass percent concentration of described aqueous acid preferably 10% ~ 20%, and further preferably 3% ~ 15%.
In the method preparing compound 1, the volume ratio of described acid and described solvent preferably 0.005 ~ 0.02, further preferably 0.008 ~ 0.012.
In the method preparing compound 1, the preferred 1:1 ~ 1:1.5 of mol ratio of described compound 2 and the diazonium salt of compound 3, further preferred 1:1 ~ 1:1.2.
In the method preparing compound 1, the temperature of described coupled reaction preferably-10 DEG C ~ 30 DEG C, preferred-10 DEG C ~ 10 DEG C further, more preferred-5 DEG C ~ 5 DEG C further.
In the method preparing compound 1, the process of described coupled reaction can be monitored by traditional test methods in this area (as filter paper oozes circle method), and no longer carry out as reaction end to react, the preferred reaction time is 1h ~ 3h, further preferred 2h.
Present invention also offers above-mentioned compound as shown in Equation 1 as the application of dispersed dye in the dyeing and stamp of fibre product.
Compound 1 of the present invention can process according to the conventional treatment method (as sand milling) in this area, obtains commercialization dispersed dye.
The commercialization dispersed dye that compound of the present invention is obtained, can be applied to dyeing and the stamp of trevira goods or its mixed fibre goods according to the common staining method of this type disperse dye in this area.Described trevira goods or its mixed fibre goods can be trevira goods conventional in this area or its mixed fibre goods; The preferred pet fiber goods of described trevira goods, described mixed fibre goods preferred polyester/cotton or polyester/wool.Dispersed dye of the present invention are preferred for the outdoor activity weaving face fabrics such as swimming suit further; The outdoor activity weaving face fabrics such as described swimming suit are trevira goods or its mixed fibre goods.Described trevira goods or its mixed fibre goods can be the conventional existence form of this area, as fiber, yarn, woven fabrics, knitted fabrics or non-woven fabric.
Present invention also offers a kind of compound as shown in Equation 2:
Wherein, R 1for C 1-4alkoxyl group or hydrogen; R 2for C 1-4amido or hydrogen; R 3for C 1- 4alkyl; R 4for C 1-4alkyl.
Wherein, R 1be preferably methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy or hydrogen.R 2be preferably formamido group, kharophen, propionamido, butyrylamino or hydrogen.R 3be preferably methyl, ethyl, propyl group or butyl.R 4be preferably methyl, ethyl, propyl group or butyl.R 1more preferably methoxyl group, oxyethyl group or hydrogen.R 2more preferably kharophen, propionamido or hydrogen.R 3more preferably methyl or ethyl.R 4more preferably methyl or ethyl.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can arbitrary combination, obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material are all commercially.
Room temperature in the present invention is 10 DEG C ~ 30 DEG C.
Number in the present invention, except specified otherwise, all refers to mass fraction.
LC-MS data described in the present invention are that moving phase is acetonitrile/water system by Waters UPLC-SQD LC-MS instrument, and 60%-90% acetonitrile V/V, tests under the condition that column temperature is 40 DEG C.
Positive progressive effect of the present invention is: preparation method's technique of dispersed dye of the present invention is simple, easy handling, and post-treating method is simple, and material toxicity is little, environmental friendliness.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, conventionally and condition, or selects according to catalogue.
The preparation of embodiment 1 compound 6
At ambient temperature, 67 parts heavy 30% aqueous sodium hydroxide solutions are joined in there-necked flask, then 47 parts of heavy benzol phenol are under agitation added, 5 parts heavy PEG-400, stir, then at ambient temperature, 66 parts heavy epoxy chloropropane are slowly dripped with dropping funnel, about drip 1 ~ 2h, drip and be slowly warming up to 50 DEG C ~ 55 DEG C and react afterwards, after 3h ~ 5h, raw material reaction is complete, the 50mL that adds water makes solid fully dissolve, then stratification, divide phase of anhydrating, the 100mL that adds water again washes, and regulate pH to neutral with a small amount of dilute hydrochloric acid, stir rear stratification, collect oil phase, underpressure distillation removes excessive epoxy chloropropane and water.Obtain following formula: compound 52g, yield 70.5%, HPLC purity 96.4%.LC-MS(ESI)：[M+H] +151.3，[M+Na] +173.3。
Embodiment 2 compound 4(R 1for H, R 2for H, R 3for ethyl) preparation
18 parts of heavy N-ethylanilines and 30 parts heavy acetic acid are joined in there-necked flask, slowly be warming up to 50 DEG C after stirring, then slowly drip 24 parts heavy compounds 6 from constant pressure funnel, about drip 3h ~ 4h, react completely at 50 DEG C of insulation 3h ~ 4h after adding, obtain compound 4(R 1for H, R 2for H, R 3for ethyl) acetum, be directly used in next step reaction.Yield 97.3%, HPLC purity 92.4%, LC-MS (ESI): [M+H] +272.2, [M+Na] +294.2.
Embodiment 3 compound 2-1(R 1for H, R 2for H, R 3for ethyl, R 4for methyl) preparation
By 29 parts heavy compound 4(R 1for H, R 2for H, R 3for ethyl) join in there-necked flask, be slowly warmed up to 50 DEG C, slowly drip 13 parts heavy acetic anhydride from constant pressure funnel at such a temperature, about drip 2h, and 50 DEG C of insulation reaction until raw material reaction is complete, obtain compound 2-1(R 1for H, R 2for H, R 3for ethyl, R 4for ethyl) acetum, yield 96.1%, HPLC purity 94.3%, LC-MS (ESI): [M+H] +314.4, [M+Na] +336.4.
Prepare compound 2-1 ~ 2-12 according to the method for embodiment 1 ~ 3, its relevant experimental data and Structural Identification data are in table 1.
The experimental data of table 1 compound 2-1 ~ 2-12 and Structural Identification data
Embodiment 4 compound 1-1(R 1for H, R 2for H, R 3for ethyl, R 4for methyl, D is ) preparation
144 parts of heavy vitriol oils are joined in reaction flask 1,45 parts heavy 2-amino-5 are added under stirring, 6-dichlorobenzothiazole, then 40 DEG C ~ 45 DEG C are warmed up to, insulation 30min makes to dissolve completely, then cool to about 15 DEG C and add 67 parts heavy nitrosyl sulfuric acids slowly, stir, cool to less than 5 DEG C stand-by.In reaction flask 2, add 92 parts of heavy water, under agitation add 139 parts of heavy vitriol oils and 3 parts heavy nitric acid, stir, cool to less than 0 DEG C, sulfuric acid liquid in slow dropwise reaction bottle 1 under-5 DEG C ~ 0 DEG C condition, slowly drip 72 parts of heavy water simultaneously, about 1h adds, and less than 0 DEG C is incubated 2.5-3h.Then drip in 1h and complete coupling with compound 2-1, by control temperature of reaction on the rocks 0 ~ 5 DEG C, and complete coupling at 0 ~ 5 DEG C of insulation 2h, be naturally stirred to room temperature, filter, washing, dry, obtain compound 1-1(R 1for H, R 2for H, R 3for ethyl, R 4for methyl, D is ) dispersed dye filter cake 83g, yield 76.5%, HPLC purity 92.6%, LC-MS (ESI): [M+H] +544.5, [M+Na] +566.5.
Compound 1-1 ~ 1-76 is prepared according to the method for embodiment 1 ~ 4.Relevant experimental data and Structural Identification data are in table 2.
The experimental data of table 2 compound 1-1 ~ 1-76 and Structural Identification data
Effect example 1
Get commercialization dispersed dye [the compound 1-1(R that 5 grams of embodiments 4 are obtained 1for H, R 2for H, R 3for ethyl, R 4for methyl, D is )] be dispersed in 500 ml waters, draw 20 milliliters and mix with the water of 80 milliliters, adjust dye bath pH to be 4 ~ 5 with acetic acid, be warming up to 70 DEG C to put into 5 grams of polyester fiber cloths simultaneously and dye, in 30 minutes, be warming up to 130 DEG C by 70 DEG C, be incubated 50 minutes, be cooled to less than 90 DEG C draining cleanings.The 100 milliliters of reduction clearing liquid put into by cloth specimen again containing 1 grams per liter caustic soda and 3 grams per liter vat powders clean in 80 DEG C, and the time is 20 minutes.Adopt GB GB/T5718-1997 to test fastness to sublimation, probe temperature is 180 DEG C, and the time is 30 seconds.
Effect example 2
Dye to dispersed dye prepared by compound 1-1 ~ 1-76 according to the method for effect example 1, and test their fastness to sublimation, its test result is in table 3.
The Color data of dispersed dye prepared by table 3 compound 1-1 ~ 1-76

Claims (1)

1. a preparation method for compound as shown in Equation 1, is characterized in that comprising the following steps:
Step (1): in a solvent, under the condition of alkali existence and catalyst, reacts phenol and epoxy chloropropane, obtains compound 6; The temperature of described reaction is 50 DEG C ~ 55 DEG C;
Step (2): the compound 6 step (1) obtained reacts with amine as shown in Equation 7, obtains compound 4;
Step (3): the compound 4 that just step (2) obtains carries out acylation reaction with acid anhydrides as shown in Equation 5, obtains compound 2;
Step (4): under sour existent condition, by nitrite or nitrosyl sulfuric acid, carries out diazotization reaction with aromatic amine as shown in Equation 8, obtains the diazonium salt of compound 3;
Step (5): in a solvent, under acid catalyzed condition, just the diazonium salt as shown in Equation 3 that obtains of step (4) with the compound as shown in Equation 2 that step (3) obtains is carried out coupled reaction, obtain compound 1;
Wherein, A is Cl -, CH 2cOO -, H 2pO 4 -, HSO 4 -or NO 3 -, R 1for C 1-4alkoxyl group or hydrogen; R 2for C 1-4amido or hydrogen; R 3for C 1-4alkyl; R 4for C 1-4alkyl; D
Described compound is as shown in Equation 1 in following table, and general formula is compound 1, and group is the particular compound of the arbitrary situation in numbering 1-1 ~ 1-76:
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