CN107312353A - A kind of preparation method of azo compound - Google Patents
A kind of preparation method of azo compound Download PDFInfo
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- CN107312353A CN107312353A CN201710487609.XA CN201710487609A CN107312353A CN 107312353 A CN107312353 A CN 107312353A CN 201710487609 A CN201710487609 A CN 201710487609A CN 107312353 A CN107312353 A CN 107312353A
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- 0 *c1ccc(*)c(*)c1 Chemical compound *c1ccc(*)c(*)c1 0.000 description 1
Classifications
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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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/20—Diazonium compounds
-
- 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
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
- C09B29/0833—Amino benzenes characterised by the substituent on the benzene ring excepted the substituents: CH3, C2H5, O-alkyl, NHCO-alkyl, NHCOO-alkyl, NHCO- C6H5, NHCOO-C6H5
- C09B29/0836—Amino benzenes characterised by the substituent on the benzene ring excepted the substituents: CH3, C2H5, O-alkyl, NHCO-alkyl, NHCOO-alkyl, NHCO- C6H5, NHCOO-C6H5 linked through -N=
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method of azo compound.The preparation method for the azo compound that the present invention is provided, comprises the steps：(1) in the aqueous sulfuric acid that mass concentration is 60wt% 80wt%, compound 4 and nitrosyl sulfuric acid is subjected to diazo-reaction, the mixture containing diazol as shown in Equation 2 is made；(2) in presence of water, by the obtained mixture for containing diazol as shown in Equation 2 of step (1), coupling reaction is carried out with compound 3, compound 1 is obtained.This method reaction condition is gentle, environmental protection.
Description
Technical field
The present invention relates to a kind of preparation method of azo compound.
Background technology
Waste acid water in enhancing with people to environmental consciousness, synthetic dyestuffs requires more and more higher.The present invention reduces
The discharge of waste water in synthesis, and cost has been saved, to the coloured light of dyestuff, performance boost is without influence.
The content of the invention
The technical problems to be solved by the invention are the preparation method severe reaction conditions, no of existing azo compound
The defects such as environmental protection, so, the invention provides a kind of preparation method of azo compound, this method reaction condition is gentle (anti-
Answer temperature high, can carry out at normal temperatures), environmentally friendly (discharge capacity for reducing sour water).
The invention provides a kind of preparation method of diazol as shown in Equation 2, it comprises the steps：In mass concentration
In aqueous sulfuric acid for 60wt%-80wt% (in another example 61wt%-75wt%, then such as 61wt%-67wt%), by chemical combination
Thing 4 carries out diazo-reaction with nitrosyl sulfuric acid, obtains compound 2；
Wherein, X is halogen (such as fluorine, chlorine, bromine or iodine).
In described diazo-reaction, described aqueous sulfuric acid and the Molar ratio of described compound 4 can be
The conventional Molar ratio of such reaction of this area, such as 0.5L/mol~1.5L/mol is (in another example 0.8L/mol~1.0L/
mol)。
In described diazo-reaction, sulfuric acid and the mol ratio of described compound 4 in described aqueous sulfuric acid
Can be the conventional mol ratio of such reaction of this area, such as 3.0~6.0 (in another example 3.5~5.0).
In described diazo-reaction, described nitrosyl sulfuric acid and the mol ratio of described compound 4 can be ability
The conventional mol ratio of such reaction of domain, such as 1.5~4.0 (in another example 2.5~3.0).
The feeding mode of described diazo-reaction can be the conventional feeding mode of such reaction of this area, for example：By Asia
Nitryl sulfuric acid is added in " compound 4 and the mixture of aqueous sulfuric acid ".
The temperature of described diazo-reaction can be the conventional temperature of such reaction of this area, and such as -10 DEG C~25 DEG C (again
Such as 0 DEG C~20 DEG C).
The process of described diazo-reaction can be using conventional monitoring method (such as KI of such reaction of this area
Test paper) it is monitored, as reaction end when being typically detected as micro- blue using potassium iodide starch paper, the reaction time can be 4~5h.
Present invention also offers a kind of mixture containing diazol as shown in Equation 2, its according to above-mentioned compound 2 system
Preparation Method is made；
Described preparation method can be free of post-processing step, and (reaction solution that i.e. described diazo-reaction is obtained is without rear place
Reason).
Present invention also offers a kind of preparation method of azo compound as shown in Equation 1, it comprises the steps：
(1) according to the preparation method of above-mentioned compound 2, the mixture containing diazol as shown in Equation 2 is made；
(2) in presence of water, by the obtained mixture for containing diazol as shown in Equation 2 of step (1), with compound 3
Coupling reaction is carried out, compound 1 is obtained；
In described coupling reaction, the Molar ratio of described water and described compound 3 can for this area such
React conventional Molar ratio, such as 2L/mol~5L/mol (in another example 3L/mol~4L/mol).
In described coupling reaction, the mol ratio of described compound 2 and described compound 3 can for this area such
React conventional mol ratio, such as 0.8~1.2 (in another example 1.0~1.1).
Described coupling reaction can be carried out in the presence of surfactant, and described surfactant can be peregal.
Described surfactant and the mass ratio of described compound 3 such can react conventional mass ratio for this area, for example
0.02~0.10 (in another example 0.03~0.05).After described surfactant can be mixed first with described water, then add thereto
Enter described " mixture for containing diazol as shown in Equation 2 ".
Described coupling reaction can be carried out in the presence of nitrous acid depleting agents, and described nitrous acid depleting agents can be urea
And/or sulfamic acid.Described nitrous acid depleting agents and the mass ratio of described compound 3 such can react conventional for this area
Mass ratio, such as 0.010~0.10 (in another example 0.015~0.05).Described nitrous acid depleting agents can first with described water
After mixing, then described " mixture for containing diazol as shown in Equation 2 " is added thereto.
The charging sequence of described coupling reaction can be following charging sequences：(a) by described water and described compound 3
Mixing；(b) described " mixture for containing diazol as shown in Equation 2 " is added in the mixture obtained to step (a) to carry out occasionally
Connection reaction, obtains compound 1.
The temperature of described coupling reaction can be the conventional temperature of such reaction of this area, such as -10 DEG C~20 DEG C (and example
Such as 0 DEG C~20 DEG C, then such as 15 DEG C~20 DEG C).
The process of described coupling reaction can be using such reaction of this area conventional monitoring method (such as TLC, HPLC
Or NMR) be monitored, as reaction end when typically no longer being reacted using compound 3, reaction time such as 6h.
In the preparation method of described compound 1, described " mixture containing diazol as shown in Equation 2 is made " is
Refer to step (1) diazo-reaction terminate after, compound 2 without isolation (for example, obtained reaction solution it is not post-treated or, enter
The simple post processing of row), then carry out the coupling reaction of step (2).
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can be combined, and produce the present invention each preferably
Example.
Agents useful for same and raw material of the present invention are commercially available.
The positive effect of the present invention is：This method reaction condition is gentle, and (reaction temperature is high, can enter at normal temperatures
OK), it is environmentally friendly (discharge capacity for reducing sour water)
Embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality
Apply among a scope.The experimental method of unreceipted actual conditions in the following example, conventionally and condition, or according to business
Product specification is selected.
Embodiment 1
50 gram of 98% sulfuric acid is instilled in 30 grams of water, stirring, less than 25 DEG C 17.3 grams of ortho-chlor-para nitranilines of addition, mashing
30 minutes.Less than 20 DEG C 32.6 grams of nitrosyl sulfuric acids of dropwise addition, drip off, holding 2 hours are dripped off, after diazotising is complete for about 2-3 hours
Wait to be coupled.Detection method：Dip a few drop diazo liquids with glass bar to be put into frozen water, its frozen water is limpid and potassium iodide starch paper is aobvious blue
Color is that terminal is arrived.If terminal is not arrived, continue to stir until terminal is arrived.
Bottom water 300ml, 1 gram of peregal, 48% carbuncle esterifying liquid (N, N diacetyl oxy ethyl are added in 1000ml beakers
M-acetamidoaniline) 65.76 grams, add 0.5 gram of sulfamic acid or urea.Less than 20 DEG C dropwise addition diazols of cooling.One
Hour drips, control temperature no longer on the rocks during dropwise addition.Reaction heats up 70-75 DEG C after 5 hours turns crystalline substance.2 hours filter waters
Neutrality is washed till, that is, obtains target product.
Embodiment 2
60 gram of 98% sulfuric acid is instilled in 28 grams of water, stirring, less than 25 DEG C 17.3 grams of ortho-chlor-para nitranilines of addition, mashing
30 minutes.Less than 20 DEG C 32.6 grams of nitrosyl sulfuric acids of dropwise addition, drip off, holding 2 hours are dripped off, after diazotising is complete for about 2-3 hours
Wait to be coupled.Detection method：Dip a few drop diazo liquids with glass bar to be put into frozen water, its frozen water is limpid and potassium iodide starch paper is aobvious blue
Color is that terminal is arrived.If terminal is not arrived, continue to stir until terminal is arrived.
Bottom water 400ml, 1 gram of peregal, 48% carbuncle esterifying liquid (N, N diacetyl oxy ethyl are added in 1000ml beakers
M-acetamidoaniline) 65.76 grams, add 0.5 gram of sulfamic acid or urea.Less than 20 DEG C dropwise addition diazols of cooling.One
Hour drips, control temperature no longer on the rocks during dropwise addition.Reaction heats up 70-75 DEG C after 5 hours turns crystalline substance.2 hours filter waters
Neutrality is washed till, that is, obtains target product.
Comparative example 1
Stirring under 62 grams of 30% hydrochloric acid, 17.5 grams of ortho-chlor-para nitraniline normal temperature is added in beaker and obtains yellow within 5 hours
Suspension, on the rocks to cool to 0 DEG C or so, the sodium nitrite solution of 24 gram 30% of dropwise addition, 0-5 DEG C of diazotising temperature continues to stir
Add 1 gram of sulfamic acid within 2-3 hours to stir 15 minutes, add 65.76 grams of couplings of carbuncle esterifying liquid of content 48%, temperature is in 5-
10 DEG C are stirred 5 hours, and 70-75 DEG C turn of crystalline substance filters washing and obtain dyestuff after 2 hours.
Effect example：Tint applications performance test
By the dyestuff of Examples 1 and 2, its coloured light intensity is determined by GB/T2397 with the dyestuff of comparative example 1, dispersiveness, resistance to
Washing fastness, fastness to sublimation, the rubbing fastness of resistance to dry grinding and lifting force contrast.
Its result shows：Diazotising is in diluted acid, and coupling is not added with dyestuff (the i.e. dyestuff of Examples 1 and 2 of frozen water temperature control
Product), its properties and product prepared by traditional low temperature coupling are about the same, but production cost is reduced, and has saved energy consumption.
Claims (10)
1. a kind of preparation method of azo compound as shown in Equation 1, it is characterised in that it comprises the steps：
(1) in the aqueous sulfuric acid that mass concentration is 60wt%-80wt%, compound 4 and nitrosyl sulfuric acid are subjected to diazonium
Change reaction, obtain the mixture containing diazol as shown in Equation 2；X is halogen；
(2) in presence of water, the mixture containing diazol as shown in Equation 2 step (1) obtained, is carried out with compound 3
Coupling reaction, obtains compound 1；
2. preparation method as claimed in claim 1, it is characterised in that described halogen is fluorine, chlorine, bromine or iodine；
And/or, the mass concentration of described aqueous sulfuric acid is 61wt%-75wt%；
And/or, described aqueous sulfuric acid and the Molar ratio of described compound 4 are 0.5L/mol~1.5L/mol；
And/or, the mol ratio of sulfuric acid and described compound 4 in described aqueous sulfuric acid is 3.0~6.0；
And/or, described nitrosyl sulfuric acid and the mol ratio of described compound 4 are 1.5~4.0；
And/or, the feeding mode of described diazo-reaction is：Nitrosyl sulfuric acid is added to, compound 4 and aqueous sulfuric acid
Mixture in.
3. preparation method as claimed in claim 2, it is characterised in that described halogen is chlorine；
And/or, the mass concentration of described aqueous sulfuric acid is 61wt%-67wt%；
And/or, described aqueous sulfuric acid and the Molar ratio of described compound 4 are 0.8L/mol~1.0L/mol；
And/or, the mol ratio of sulfuric acid and described compound 4 in described aqueous sulfuric acid is 3.5~5.0；
And/or, described nitrosyl sulfuric acid and the mol ratio of described compound 4 are 2.5~3.0.
4. preparation method as claimed in claim 1, it is characterised in that the temperature of described diazo-reaction is -10 DEG C~25
℃；
And/or, the process of described diazo-reaction using potassium iodide starch paper be detected as micro- blue when as reaction end.
5. preparation method as claimed in claim 4, it is characterised in that the temperature of described diazo-reaction is 0 DEG C~20 DEG C.
6. preparation method as claimed in claim 1, it is characterised in that described water and the Molar of described compound 3
Than for 2L/mol~5L/mol；
And/or, described compound 2 and the mol ratio of described compound 3 are 0.8~1.2；
And/or, described coupling reaction is carried out in the presence of surfactant；
And/or, described coupling reaction is carried out in the presence of nitrous acid depleting agents；
And/or, the temperature of described coupling reaction is -10 DEG C~20 DEG C.
7. preparation method as claimed in claim 6, it is characterised in that described water and the Molar of described compound 3
Than for 3L/mol~4L/mol；
And/or, described compound 2 and the mol ratio of described compound 3 are 1.0~1.1；
And/or, described surfactant is peregal；
And/or, described surfactant and the mass ratio of described compound 3 are 0.02~0.10；
And/or, described nitrous acid depleting agents are urea and/or sulfamic acid；
And/or, described nitrous acid depleting agents and the mass ratio of described compound 3 are 0.010~0.10；
And/or, the temperature of described coupling reaction is 0 DEG C~20 DEG C.
8. preparation method as claimed in claim 1, it is characterised in that the charging sequence of described coupling reaction is：(a) by institute
The water stated is mixed with described compound 3；(b) described " contain as shown in Equation 2 is added in the mixture obtained to step (a)
The mixture of diazol " carries out coupling reaction, obtains compound 1；
And/or, the process of described coupling reaction using compound 3 no longer react when as reaction end；
And/or, in the preparation method of described compound 1, described " mixture containing diazol as shown in Equation 2 is made "
Refer to that the diazo-reaction of step (1) terminates rear, compound 2 and without isolation, then carries out the coupling reaction of step (2).
9. a kind of mixture containing diazol as shown in Equation 2, it is characterised in that it is according to any one of Claims 1 to 5 institute
The step of stating (1) is made；
10. mixture as claimed in claim 9, it is characterised in that described preparation method is free of post-processing step.
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| CN201710487609.XA CN107312353A (en) | 2017-06-23 | 2017-06-23 | A kind of preparation method of azo compound |
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| CN201710487609.XA CN107312353A (en) | 2017-06-23 | 2017-06-23 | A kind of preparation method of azo compound |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101117446A (en) * | 2007-07-24 | 2008-02-06 | 上虞市金冠化工有限公司 | Process for synthesizing azo dispersion dyes monomer compound |
| CN103450699A (en) * | 2013-09-13 | 2013-12-18 | 杭州福莱蒽特精细化工有限公司 | Grinding coupling method for preparing disperse dye |
| CN104559287A (en) * | 2014-12-29 | 2015-04-29 | 浙江龙盛集团股份有限公司 | Disperse dye compound as well as preparation method and application thereof |
| CN106752081A (en) * | 2016-12-30 | 2017-05-31 | 浙江闰土研究院有限公司 | A kind of disperse dye composition and its production and use |
| CN106752079A (en) * | 2016-12-30 | 2017-05-31 | 浙江闰土研究院有限公司 | A kind of disperse dye composition and its production and use |
-
2017
- 2017-06-23 CN CN201710487609.XA patent/CN107312353A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101117446A (en) * | 2007-07-24 | 2008-02-06 | 上虞市金冠化工有限公司 | Process for synthesizing azo dispersion dyes monomer compound |
| CN103450699A (en) * | 2013-09-13 | 2013-12-18 | 杭州福莱蒽特精细化工有限公司 | Grinding coupling method for preparing disperse dye |
| CN104559287A (en) * | 2014-12-29 | 2015-04-29 | 浙江龙盛集团股份有限公司 | Disperse dye compound as well as preparation method and application thereof |
| CN106752081A (en) * | 2016-12-30 | 2017-05-31 | 浙江闰土研究院有限公司 | A kind of disperse dye composition and its production and use |
| CN106752079A (en) * | 2016-12-30 | 2017-05-31 | 浙江闰土研究院有限公司 | A kind of disperse dye composition and its production and use |
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