CN103232409A - Preparation method of disperse dyestuff - Google Patents
Preparation method of disperse dyestuff Download PDFInfo
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- CN103232409A CN103232409A CN2012105945249A CN201210594524A CN103232409A CN 103232409 A CN103232409 A CN 103232409A CN 2012105945249 A CN2012105945249 A CN 2012105945249A CN 201210594524 A CN201210594524 A CN 201210594524A CN 103232409 A CN103232409 A CN 103232409A
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- 0 CC(*)CN(*)c1cc(*)ccc1* Chemical compound CC(*)CN(*)c1cc(*)ccc1* 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-O [OH2+]c1ccccc1 Chemical compound [OH2+]c1ccccc1 ISWSIDIOOBJBQZ-UHFFFAOYSA-O 0.000 description 1
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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
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, and are water-soluble low, mainly are the non-ionic dye that dispersion state exists with molecule 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, therefore be also referred to as cellulose acetate dye.In recent years, along with synthon developing rapidly of trevira particularly, 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 hydrophobicity textile materialss such as cellulose acetate fibre and tynex.Along with the raising of people's living standard, the human consumer is also more and more higher for weaving official ceremonial dress performance demands, as requires dyed textiles to have higher fastness to sublimation, multinomial fastness such as sun-resistant.Some conventional dispersed dye of using such as C.I. are red 153, C.I. purple 93, C.I. blue 291 and C.I. orange 288 etc., then are not suitable for the application that fastness to sublimation is had relatively high expectations.
Being reflected at of phenol and epoxy chloropropane has the similar structures compound to synthesize the introduction of method among the US Patent No. 2010279997A1; In addition, be the explanation that related methods of synthesis is also arranged in the CAS database of 122-60-1 at CAS number.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 solvents, very uneconomic environmental protection.
The reaction of preparation compound 4 has the introduction of the synthetic method of similar structures compound in US Patent No. 4448719A;
In addition, at document Russian Journal of Organic Chemistry, 43(8), 1176-1179; The introduction of the synthetic method of dependency structure compound is also arranged in 2007.But preparation technology's reaction process complexity of document report, post-processing operation is loaded down with trivial details.
The reaction of preparation compound 2, still there is not the patent documentation report at present, has only the reaction of similar acylated hydroxy, at document Russian Journal of Organic Chemistry, 43(8), 1176-1179 has similar reaction in 2007, but is to adopt Acetyl Chloride 98Min. to come hydroxyl is carried out acidylate in the document; Do reaction raw materials with acyl chlorides, toxicity is big, and requirement of shelter is higher, and environmental pollution is serious in the last handling process.
Summary of the invention
Defectives such as technical problem to be solved by this invention is in order to overcome the complicated process of preparation of existing dyestuff, and material toxicity is big, and post-processing operation is loaded down with trivial details, and environmental pollution is serious, and a kind of preparation method of dispersed dye is provided.Preparation method's technology 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
1Be C
1-4Alkoxyl group or hydrogen; R
2Be C
1-4Amido or hydrogen; R
3Be C
1-4Alkyl; R
4Be 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.
The present invention also provides the preparation method of compound as shown in Equation 1, and it may further comprise the steps: in solvent, under the acid catalyzed condition, diazonium salt as shown in Equation 3 and as shown in Equation 2 compound are carried out coupled reaction, obtain compound 1 and get final product;
Wherein, A is Cl
-, CH
2COO
-, H
2PO
4 -, HSO
4 -Or NO
3 -, R
1Be C
1-4Alkoxyl group or hydrogen; R
2Be C
1-4Amido or hydrogen; R
3Be C
1-4Alkyl; R
4Be C
1-4Alkyl; D is
In the method for 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 for 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 for preparing compound 1, described solvent preferably water.
In the method for preparing compound 1, the volume mass of described solvent and described compound 2 is than preferred 4mL/g～12mL/g, further preferred 6mL/g～9mL/g.
In the method for preparing compound 1, one or more in the preferred hydrochloric acid of described acid, acetic acid, phosphoric acid, nitric acid and the sulfuric acid, one or more in further preferred hydrochloric acid, acetic acid and the sulfuric acid, further preferably sulfuric acid and/or hydrochloric acid again.Described acid can participate in reaction with the form of aqueous acid, the mass percent concentration of described aqueous acid preferred 1%～20%, further preferred 3%～15%.
In the method for preparing compound 1, the volume ratio of described acid and described solvent preferred 0.005～0.02, further preferred 0.008～0.012.
In the method for preparing compound 1, the preferred 1:1～1:1.5 of mol ratio of the diazonium salt of described compound 2 and compound 3, further preferred 1:1～1:1.2.
In the method for preparing compound 1, preferred-10 ℃～30 ℃ of the temperature of described coupled reaction, further preferred-10 ℃～10 ℃, further preferred-5 ℃～5 ℃ again.
In the method for preparing compound 1, the process of described coupled reaction can be monitored by conventionally test method in this area (oozing the circle method as filter paper), no longer is reaction end with reaction, and the preferred reaction time is 1h～3h, further preferred 2h.
Above-mentioned diazonium salt as shown in Equation 3 can make by the following method: under the condition that acid exists, with nitrite or nitrosyl sulfuric acid, carry out diazotization reaction with as shown in Equation 8 aromatic amine, the diazonium salt that obtains compound 3 gets final product; Making compound 1 according to the above-mentioned method for preparing compound 1 again gets final product;
Wherein, A is Cl
-, CH
2COO
-, H
2PO
4 -, HSO
4 -Or NO
3 -D is
Can carry out preferred following reaction conditions according to the ordinary method in this area in described diazotization reaction:
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 the 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 preferred 10%～90%, further preferred 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 is than preferred 1mL/g～10mL/g, further preferred 2mL/g～5mL/g.
In described diazotization reaction, described aromatic amine and the preferred 1:1～1:1.2 of mol ratio of described nitrite or nitrosyl sulfuric acid, further preferred 1:1～1:1.1 as shown in Equation 8.
In described diazotization reaction, preferred-10 ℃～30 ℃ of the temperature of described reaction, further preferred-10～20 ℃.
The process of described diazotization reaction can be by conventionally test method (as TLC) monitoring in this area, and disappearing with described aromatic amine as shown in Equation 8 is reaction end, and the preferred reaction time is 1h～5h, further preferred 2h ~ 3h.
Above-claimed cpd 2 can make by following method: compound 4 and acid anhydrides are as shown in Equation 5 carried out acylation reaction, obtain compound 2 and get final product;
Prepare compound 3 according to the above-mentioned method for preparing compound 3 again, prepare compound 1 according to the above-mentioned method for preparing compound 1 again and get final product; Wherein, R
1Be C
1-4Alkoxyl group or hydrogen; R
2Be C
1-4Amido or hydrogen; R
3Be C
1-4Alkyl; R
4Be C
1-4Alkyl.
In the method for 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 for preparing compound 2, described acylation reaction can be carried out according to the ordinary method of this area, preferred especially following reaction conditions among the present invention:
In the method for preparing compound 2, described reaction can be carried out in solvent, also can carry out under solvent-free condition.The preferred organic acid of described solvent, the preferred acetic acid of described organic acid.
In the method for preparing compound 2, the volume mass of described solvent and described compound 4 is than preferred 1mL/g～10mL/g, further preferred 1mL/g～5mL/g.
In the method for preparing compound 2, the preferred 1:1～1:1.2 of mol ratio of described acid anhydrides 5 and described compound 4, further preferred 1:1～1:1.1.
In the method for preparing compound 2, preferred 20 ℃～100 ℃ of the temperature of described acylation reaction, further preferred 25 ℃～75 ℃, further preferred 50 ℃ again.
In the method for preparing compound 2, the process of described acylation reaction can be by conventionally test method (as HPLC) monitoring in this area, and having reacted with compound 4 is reaction end, and the preferred reaction time is 2h～6h, further preferred 4～5h.
Above-claimed cpd 4 can make by following method: compound 6 and amine are as shown in Equation 7 reacted, obtain compound 4 and get final product;
Make compound 2 according to the above-mentioned method for preparing compound 2 again, prepare compound 3 according to the above-mentioned method for preparing compound 3 again, prepare compound 1 according to the above-mentioned method for preparing compound 1 again and get final product; Wherein, R
1Be C
1-4Alkoxyl group or hydrogen; R
2Be C
1-4Amido or hydrogen; R
3Be C
1-4Alkyl.
In the method for 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 for preparing compound 4, described reaction can be carried out according to the ordinary method of this area, preferred especially following reaction conditions among the present invention:
In the method for preparing compound 4, described reaction can be carried out also can carrying out under solvent-free condition in solvent.The preferred organic acid of described solvent, the preferred acetic acid of described organic acid.
In the method for preparing compound 4, the volume mass of described solvent and described compound 7 is than preferred 1mL/g～10mL/g, further preferred 1mL/g～5mL/g.
In the method for preparing compound 4, the preferred 1:1～1:2 of mol ratio of described compound 6 and described compound 7, further preferred 1:1～1:1.1.
In the method for preparing compound 4, preferred 20 ℃～100 ℃ of the temperature of described reaction, further preferred 25 ℃～75 ℃, further preferred 50 ℃ again.
In the method for preparing compound 4, the process of described reaction can be by conventionally test method (as HPLC) monitoring in this area, and having reacted with compound 7 is reaction end, and the preferred reaction time is 1h～5h, further preferred 2h～4h.
Above-claimed cpd 6 can make by following method: in solvent, under the condition of alkali existence and catalyst, phenol and epoxy chloropropane are reacted, obtain compound 6 and get final product;
Make compound 4 according to the above-mentioned method for preparing compound 4 again, make compound 2 according to the above-mentioned method for preparing compound 2, prepare compound 3 according to the above-mentioned method for preparing compound 3 again, prepare compound 1 according to the above-mentioned method for preparing compound 1 again and get final product.
In the method for preparing compound 6, described reaction can be carried out according to the ordinary method of this area, preferred especially following reaction conditions among the present invention:
In the method for preparing compound 6, described solvent preferably water.
In the method for preparing compound 6, the preferred PEG-400(poly(oxyethylene glycol) 400 of described catalyzer).
In the method for preparing compound 6, the mass percent of described catalyzer and phenol is preferred 1%～30%, and is further preferred 5%～25%, and more further preferred 10%.
In the method for preparing compound 6, the volume mass of described solvent and described compound phenol is than preferred 1mL/g～10mL/g, further preferred 1mL/g～5mL/g.
In the method for preparing compound 6, the preferred 1:1～1:1.8 of the mol ratio of described phenol and epoxy chloropropane, further preferred 1:1～1:1.5.
In the method for 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 the yellow soda ash, further preferred sodium hydroxide.
In the method for preparing compound 6, described alkali can participate in reaction with the form of the aqueous solution of alkali, and the mass percent concentration of the aqueous solution of described alkali is preferred 10%～40%, and is further preferred 25%～35%, and more further preferred 30%.
In the method for preparing compound 6, the preferred 1:1 ~ 1:1.2 of the mol ratio of described alkali and phenol, further preferred 1:1.
In the method for preparing compound 6, preferred 0 ℃～100 ℃ of the temperature of described reaction, further preferred 20 ℃～75 ℃, further preferred 50 ℃～55 ℃ again.
In the method for preparing compound 6, the process of described reaction can be by conventionally test method (as HPLC) monitoring in this area, and intact with the phenol primitive reaction is reaction end, and 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 may further comprise the steps: compound 4 and acid anhydrides are as shown in Equation 5 carried out acylation reaction, obtain compound 2 and get final product;
Wherein, R
1Be C
1-4Alkoxyl group or hydrogen; R
2Be C
1-4Amido or hydrogen; R
3Be C
1-4Alkyl; R
4Be C
1-4Alkyl.
In the method for 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 for preparing compound 2, described acylation reaction can be carried out according to the ordinary method of this area, preferred especially following reaction conditions among the present invention:
In the method for preparing compound 2, described reaction can be carried out in solvent, also can carry out under solvent-free condition.The preferred organic acid of described solvent, the preferred acetic acid of described organic acid.
In the method for preparing compound 2, the volume mass of described solvent and described compound 4 is than preferred 1mL/g～10mL/g, further preferred 1mL/g～5mL/g.
In the method for preparing compound 2, the preferred 1:1～1:1.2 of mol ratio of described acid anhydrides 5 and described compound 4, further preferred 1:1～1:1.1.
In the method for preparing compound 2, preferred 20 ℃～100 ℃ of the temperature of described acylation reaction, further preferred 25 ℃～75 ℃, further preferred 50 ℃ again.
In the method for preparing compound 2, the process of described acylation reaction can be by conventionally test method (as HPLC) monitoring in this area, and having reacted with compound 4 is reaction end, and the preferred reaction time is 2h～6h, further preferred 4～5h.
The invention provides the preparation method of compound 1, what it was preferable may further comprise the steps:
Step 1: in solvent, under the condition of alkali existence and catalyst, phenol and epoxy chloropropane are reacted, obtain compound 6 and get final product;
Step 2: the compound that makes in the step 16 and as shown in Equation 7 amine are reacted, obtain compound 4 and get final product;
Step 3: the compound that makes in the step 24 and as shown in Equation 5 acid anhydrides are carried out acylation reaction, obtain compound 2 and get final product;
Step 4: under the condition that acid exists, as shown in Equation 8 aromatic amine and nitrite or nitrosyl sulfuric acid are carried out diazotization reaction, the diazonium salt that obtains compound 3 gets final product;
Step 5: in solvent, under the acid catalyzed condition, the compound as shown in Equation 2 that makes in the diazonium salt as shown in Equation 3 that makes in the step 4 and the step 3 is carried out coupled reaction, obtain compound 1 and get final product;
Wherein, R
1Be C
1-4Alkoxyl group or hydrogen; R
2Be C
1-4Amido or hydrogen; R
3Be C
1-4Alkyl; R
4Be 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 for preparing compound 6, described reaction can be carried out according to the ordinary method of this area, preferred especially following reaction conditions among the present invention:
In the method for preparing compound 6, described solvent preferably water.
In the method for preparing compound 6, the preferred PEG-400(poly(oxyethylene glycol) 400 of described catalyzer).
In the method for preparing compound 6, the mass percent of described catalyzer and phenol is preferred 1%～30%, and is further preferred 5%～25%, and more further preferred 10%.
In the method for preparing compound 6, the volume mass of described solvent and described compound phenol is than preferred 1mL/g～10mL/g, further preferred 1mL/g～5mL/g.
In the method for preparing compound 6, the preferred 1:1～1:1.8 of the mol ratio of described phenol and epoxy chloropropane, further preferred 1:1～1:1.5.
In the method for 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 the yellow soda ash, further preferred sodium hydroxide.
In the method for preparing compound 6, described alkali can participate in reaction with the form of the aqueous solution of alkali, and the mass percent concentration of the aqueous solution of described alkali is preferred 10%～40%, and is further preferred 25%～35%, and more further preferred 30%.
In the method for preparing compound 6, the preferred 1:1 ~ 1:1.2 of the mol ratio of described alkali and phenol, further preferred 1:1.
In the method for preparing compound 6, preferred 0 ℃～100 ℃ of the temperature of described reaction, further preferred 20 ℃～75 ℃, further preferred 50 ℃～55 ℃ again.
In the method for preparing compound 6, the process of described reaction can be by conventionally test method (as HPLC) monitoring in this area, and intact with the phenol primitive reaction is reaction end, and the preferred reaction time is 1h～6h, further preferred 2h～5h.
In the method for preparing compound 4, described reaction can be carried out according to the ordinary method of this area, preferred especially following reaction conditions among the present invention:
In the method for preparing compound 4, described reaction can be carried out also can carrying out under solvent-free condition in solvent.The preferred organic acid of described solvent, the preferred acetic acid of described organic acid.
In the method for preparing compound 4, the volume mass of described solvent and described compound 7 is than preferred 1mL/g～10mL/g, further preferred 1mL/g～5mL/g.
In the method for preparing compound 4, the preferred 1:1～1:2 of mol ratio of described compound 6 and described compound 7, further preferred 1:1～1:1.1.
In the method for preparing compound 4, preferred 20 ℃～100 ℃ of the temperature of described reaction, further preferred 25 ℃～75 ℃, further preferred 50 ℃ again.
In the method for preparing compound 4, the process of described reaction can be by conventionally test method (as HPLC) monitoring in this area, and having reacted with compound 7 is reaction end, and the preferred reaction time is 1h～5h, further preferred 2h～4h.
In the method for preparing compound 2, described acylation reaction can be carried out according to the ordinary method of this area, preferred especially following reaction conditions among the present invention:
In the method for preparing compound 2, described reaction can be carried out in solvent, also can carry out under solvent-free condition.The preferred organic acid of described solvent, the preferred acetic acid of described organic acid.
In the method for preparing compound 2, the volume mass of described solvent and described compound 4 is than preferred 1mL/g～10mL/g, further preferred 1mL/g～5mL/g.
In the method for preparing compound 2, the preferred 1:1～1:1.2 of mol ratio of described acid anhydrides 5 and described compound 4, further preferred 1:1～1:1.1.
In the method for preparing compound 2, preferred 20 ℃～100 ℃ of the temperature of described acylation reaction, further preferred 25 ℃～75 ℃, further preferred 50 ℃ again.
In the method for preparing compound 2, the process of described acylation reaction can be by conventionally test method (as HPLC) monitoring in this area, and having reacted with compound 4 is reaction end, and 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 the 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 preferred 10%～90%, further preferred 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 is than preferred 1mL/g～10mL/g, further preferred 2mL/g～5mL/g.
In described diazotization reaction, described aromatic amine and the preferred 1:1～1:1.2 of mol ratio of described nitrite or nitrosyl sulfuric acid, further preferred 1:1～1:1.1 as shown in Equation 8.
In described diazotization reaction, preferred-10 ℃～30 ℃ of the temperature of described reaction, further preferred-10～20 ℃.
Process in described diazotization reaction can be by conventionally test method (as TLC) monitoring in this area, and disappearing with described aromatic amine as shown in Equation 8 is reaction end, and the preferred reaction time is 1h～5h, further preferred 2h ~ 3h.
In the method for 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 for preparing compound 1, described solvent preferably water.
In the method for preparing compound 1, the volume mass of described solvent and described compound 2 is than preferred 4mL/g～12mL/g, further preferred 6mL/g～9mL/g.
In the method for preparing compound 1, one or more in the preferred hydrochloric acid of described acid, acetic acid, phosphoric acid, nitric acid and the sulfuric acid, one or more in further preferred hydrochloric acid, acetic acid and the sulfuric acid, further preferably sulfuric acid and/or hydrochloric acid again.Described acid can participate in reaction with the form of aqueous acid, the mass percent concentration of described aqueous acid preferred 10%～20%, further preferred 3%～15%.
In the method for preparing compound 1, the volume ratio of described acid and described solvent preferred 0.005～0.02, further preferred 0.008～0.012.
In the method for preparing compound 1, the preferred 1:1～1:1.5 of mol ratio of the diazonium salt of described compound 2 and compound 3, further preferred 1:1～1:1.2.
In the method for preparing compound 1, preferred-10 ℃～30 ℃ of the temperature of described coupled reaction, further preferred-10 ℃～10 ℃, further preferred-5 ℃～5 ℃ again.
In the method for preparing compound 1, the process of described coupled reaction can be monitored by conventionally test method in this area (oozing the circle method as filter paper), no longer is reaction end with reaction, and the preferred reaction time is 1h～3h, further preferred 2h.
The present invention also provide above-mentioned compound as shown in Equation 1 as dispersed dye in the dyeing of fibre product and the application in the stamp.
Compound 1 of the present invention can be handled according to the conventional treatment method in this area (as sand milling), obtains the commercialization dispersed dye.
The commercialization dispersed dye that compound of the present invention makes can be applied to dyeing and the stamp of trevira goods or its mixed fibre goods according to the normal dyeing method of this type disperse dye in this area.Described trevira goods or its mixed fibre goods can be trevira goods or its mixed fibre goods conventional in this area; 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 further are preferred for outdoor activity weaving face fabrics such as swimming suit; 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 for the conventional existence form of this area, as fiber, yarn, woven fabrics, knitted fabrics or non-woven fabric.
The present invention also provides a kind of compound as shown in Equation 2:
Wherein, R
1Be C
1-4Alkoxyl group or hydrogen; R
2Be C
1-4Amido or hydrogen; R
3Be C
1-4Alkyl; R
4Be 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, but arbitrary combination namely get the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available getting all.
Room temperature among the present invention is 10 ℃～30 ℃.
Umber among the present invention all refers to mass fraction except specified otherwise.
LC-MS data described in the present invention are that moving phase is the 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 ℃.
Positive progressive effect of the present invention is: preparation method's technology 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 specifies the present invention, but does not therefore limit the present invention among the described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example according to ordinary method and condition, or is selected according to catalogue.
The preparation of embodiment 1 compound 6
At ambient temperature, 67 parts heavy 30% aqueous sodium hydroxide solutions are joined in the there-necked flask, under agitation add 47 parts of heavy benzol phenol then, 5 parts heavy PEG-400, stir, then at ambient temperature, slowly drip 66 parts heavy epoxy chloropropane with dropping funnel, drip 1～2h approximately, slowly being warming up to 50 ℃～55 ℃ after dripping reacts, raw material reaction is complete behind 3h～5h, adds water 50mL solid is fully dissolved, then standing demix, divide the phase of anhydrating, add water 100mL again and wash, and regulate pH to neutral with a small amount of dilute hydrochloric acid, stir the back standing demix, collect oil phase, excessive epoxy chloropropane and water are removed in underpressure distillation.Get 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
1Be H, R
2Be H, R
3Be ethyl) preparation
18 parts of heavy N-ethylanilines and 30 parts heavy acetic acid are joined in the there-necked flask, slowly be warming up to 50 ℃ after stirring, slowly drip 24 parts heavy compounds 6 from constant pressure funnel then, drip 3h～4h approximately, add the back and react completely at 50 ℃ of insulation 3h～4h, get compound 4(R
1Be H, R
2Be H, R
3Be 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
1Be H, R
2Be H, R
3Be ethyl, R
4Be methyl) preparation
With 29 parts heavy compound 4(R
1Be H, R
2Be H, R
3Be ethyl) join in the there-necked flask, slowly be warmed up to 50 ℃, under this temperature, slowly drip 13 parts heavy acetic anhydride from constant pressure funnel, drip 2h approximately, and complete up to raw material reaction 50 ℃ of insulation reaction, get compound 2-1(R
1Be H, R
2Be H, R
3Be ethyl, R
4Be ethyl) acetum, yield 96.1%, HPLC purity 94.3%, LC-MS (ESI): [M+H]
+314.4, [M+Na]
+336.4.
Method according to embodiment 1～3 prepares compound 2-1～2-12, and its related experiment data and structure appraising datum see Table 1.
The experimental data of table 1 compound 2-1～2-12 and structure appraising datum
Embodiment 4 compound 1-1(R
1Be H, R
2Be H, R
3Be ethyl, R
4Be methyl, D is
) preparation
144 parts of heavy vitriol oils are joined in the reaction flask 1, add 45 parts heavy 2-amino-5 down in stirring, the 6-dichlorobenzothiazole, be warmed up to 40 ℃～45 ℃ then, insulation 30min makes dissolving fully, cool to then and add 67 parts heavy nitrosyl sulfuric acids about 15 ℃ slowly, stir, cool to below 5 ℃ 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 below 0 ℃, sulfuric acid liquid in the slow dropwise reaction bottle 1 under-5 ℃～0 ℃ condition slowly drips 72 parts of heavy water simultaneously, about 1h adds, and is incubated 2.5-3h below 0 ℃.Drip in 1h with compound 2-1 then and finish coupling, by 0～5 ℃ of control temperature of reaction on the rocks, and finish coupling at 0～5 ℃ of insulation 2h, be stirred to room temperature naturally, filter, washing is dried, and gets compound 1-1(R
1Be H, R
2Be H, R
3Be ethyl, R
4Be 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.
Method according to embodiment 1～4 prepares compound 1-1～1-76.Related experiment data and structure appraising datum see Table 2.
The experimental data of table 2 compound 1-1～1-76 and structure appraising datum
Effect embodiment 1
Get commercialization dispersed dye [the compound 1-1(R that 5 gram embodiment 4 make
1Be H, R
2Be H, R
3Be ethyl, R
4Be methyl, D is
)] be dispersed in 500 ml waters, draw 20 milliliters of water with 80 milliliters and mix, transferring dye bath pH with acetic acid is 4 ~ 5, being warming up to 70 ℃ puts into 5 gram trevira cloth simultaneously and dyes, in 30 minutes, be warming up to 130 ℃ by 70 ℃, be incubated 50 minutes, be cooled to draining below 90 ℃ and clean.Cloth specimen is put into 100 milliliters of reduction clearing liquid containing 1 grams per liter caustic soda and 3 grams per liter vat powders again and cleaned in 80 ℃, the time is 20 minutes.Adopt GB GB/T5718-1997 test fastness to sublimation, probe temperature is 180 ℃, and the time is 30 seconds.
Effect embodiment 2
Method according to effect embodiment 1 dyes to the dispersed dye that compound 1-1～1-76 prepares, and tests their fastness to sublimation, and its test result sees Table 3.
The Color data of the dispersed dye of table 3 compound 1-1～1-76 preparation
Claims (10)
1. the preparation method of a compound as shown in Equation 1 is characterized in that may further comprise the steps: in solvent, under the acid catalyzed condition, diazonium salt as shown in Equation 3 and as shown in Equation 2 compound are carried out coupled reaction, obtain compound 1 and get final product;
Wherein, A is Cl
-, CH
2COO
-, H
2PO
4 -, HSO
4 -Or NO
3 -, R
1Be C
1-4Alkoxyl group or hydrogen; R
2Be C
1-4Amido or hydrogen; R
3Be C
1-4Alkyl; R
4Be C
1-4Alkyl; D is
2. the preparation method of compound as shown in Equation 1 as claimed in claim 1 is characterized in that: work as R
1Be C
1-4Alkoxyl group the time, described C
1-4Alkoxyl group be methoxyl group, oxyethyl group, propoxy-, isopropoxy or butoxy.
3. the preparation method of compound as shown in Equation 1 as claimed in claim 1 is characterized in that: work as R
2Be C
1-4Amido the time, described C
1-4Amido be formamido group, kharophen, propionamido or butyrylamino.
4. the preparation method of compound as shown in Equation 1 as claimed in claim 1 is characterized in that: R
3Be methyl, ethyl, propyl group or butyl.
5. the preparation method of compound as shown in Equation 1 as claimed in claim 1 is characterized in that: R
4Be methyl, ethyl, propyl group or butyl.
6. the preparation method of compound as shown in Equation 1 as claimed in claim 1, it is characterized in that: described compound as shown in Equation 1 is in the following table, and general formula is compound 1, and group is the particular compound of the arbitrary situation among numbering 1-1～1-76:
7. as the preparation method of each described compound as shown in Equation 1 of claim 1～6, it is characterized in that: diazonium salt as shown in Equation 3 makes by the following method: under the condition that acid exists, with nitrite or nitrosyl sulfuric acid, carry out diazotization reaction with aromatic amine as shown in Equation 8, obtain the diazonium salt of compound 3; Refabrication compound 1 gets final product;
8. as the preparation method of each described compound as shown in Equation 1 of claim 1～6, it is characterized in that: described compound 2 makes by following method: compound 4 and acid anhydrides are as shown in Equation 5 carried out acylation reaction, obtain compound 2; Refabrication compound 1 gets final product;
9. the preparation method of compound as shown in Equation 1 as claimed in claim 8, it is characterized in that: described compound 4 makes by following method: compound 6 and as shown in Equation 7 amine are reacted, obtain compound 4; Refabrication compound 1 gets final product;
10. the preparation method of compound as shown in Equation 1 as claimed in claim 9, it is characterized in that: described compound 6 makes by following method: in solvent, under the condition of alkali existence and catalyst, phenol and epoxy chloropropane are reacted, obtain compound 6; Preparing compound 1 then gets final product;
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418453A (en) * | 2015-12-01 | 2016-03-23 | 浙江闰土研究院有限公司 | Process for diazotizing azo-dye intermediate |
| CN113214185A (en) * | 2021-05-11 | 2021-08-06 | 青海施丹弗化工有限责任公司 | Method for benzothiazole diazo coupling continuous reaction |
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