CN101613305B - Method for preparing o-chloro-p-nitroaniline diazosalt - Google Patents
Method for preparing o-chloro-p-nitroaniline diazosalt Download PDFInfo
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- CN101613305B CN101613305B CN2009103037933A CN200910303793A CN101613305B CN 101613305 B CN101613305 B CN 101613305B CN 2009103037933 A CN2009103037933 A CN 2009103037933A CN 200910303793 A CN200910303793 A CN 200910303793A CN 101613305 B CN101613305 B CN 101613305B
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Abstract
The invention relates to a method for preparing an o-chloro-p-nitroaniline diazosalt and aims to solve a technical problem of extending a process for synthesizing o-chloro-p-nitroaniline into a diazotization process to obtain high-quality and low-cost products. The method comprises the following steps: using paranitroaniline as a raw material to pulp in a 5 to 30 mass percent acid medium; adding a chlorinating agent and a surfactant in an amount of 1 to 5 percent of the dosage of the paranitroaniline for chlorination; and after the chlorination is finished, directly adding a diazotizing agent to complete diazotization to obtain solution of the diazosalt. The molar ratio of the paranitroaniline to the acid medium to the chlorinating agent to the diazotizing agent is 1:2-10:1-1.3:1-1.3. The method has the advantages of simple synthesis method, high yield, small amount of three wastes, and the like.
Description
Technical field
The present invention relates to a kind of preparation method of organic cpds, specifically is a kind of preparation method of ortho-chlor-para nitraniline diazonium salt.
Background technology
Ortho-chlor-para nitraniline is red colour system dispersed dye synthesis materials commonly used; It is applied to dyestuff when synthetic; Must be through diazotization process; The diazotization process of present domestic comparative maturity generally adopts the solid (wet article or dry powder) of ortho-chlor-para nitraniline after rising temperature for dissolving, further to carry out diazotization reaction, and the shortcoming of this technology is that employed ortho-chlor-para nitraniline raw material must purify out through loaded down with trivial details post processing mode to it; This process inevitably produces a large amount of spent acid, waste water, has also improved the manufacturing cost of the finished product when causing industrial pollution.
Summary of the invention
Technical problem to be solved by this invention is to extend to its diazo process to the synthesis technique of ortho-chlor-para nitraniline, thereby obtains high-quality, product cheaply; This technological method is workable, for equipment requirements is not high, three-waste pollution is little, energy consumption is low, possess the condition that realizes industrialization.
For solving above technical problem, the technical scheme that the present invention taked is:
The preparation method of ortho-chlor-para nitraniline diazonium salt of the present invention; It is characterized in that: be raw material with the p-Nitroaniline;, mass percent pulls an oar in being 5～30% acidic medium; With chlorizating agent and consumption is that the tensio-active agent of p-Nitroaniline consumption 1～5% carries out chlorination reaction, directly adds diazotization reagent after chlorination reaction finishes and accomplishes diazotization reaction again, obtains diazonium salt solution; P-Nitroaniline wherein: acidic medium: chlorizating agent: the mol ratio of diazo reagent is 1: 2～10: 1～1.3: 1～1.3;
Described acidic medium is selected from hydrochloric acid, sulfuric acid, acetic acid or phosphoric acid;
Described chlorizating agent is hypochlorous acid and salt (like Youxiaolin, Losantin, potassium hypochlorite) thereof, chloric acid and salt thereof (like VAL-DROP, Potcrate, calcium chlorate) and chlorine;
Described tensio-active agent is a nonionogenic tenside, is selected from AEO, aliphatic acid polyethenoxy ether ester or polyol ester Soxylat A 25-7;
Described diazo reagent is selected from Sodium Nitrite or nitrosyl sulfuric acid.
As preferably, the mass percent of acidic medium is 5～20%, and carrying out beating time is 1～8 hour.
Chlorination reaction temperature is-10～50 ℃ (being preferably-5～30 ℃), and the chlorination reaction time is 0.5～10 hour; The diazotization reaction temperature is-10 ~ 40 ℃ (being preferably-5～20 ℃), and the diazotization reaction time is 1～8 hour.
Because the application of technique scheme, the present invention compared with prior art has advantage:
With the p-Nitroaniline is raw material; At low temperatures, earlier through the synthetic ortho-chlor-para nitraniline of chlorination, without any separation circuit; Directly carry out diazotizing synthetic; That is: save the separation circuit of loaded down with trivial details ortho-chlor-para nitraniline, not only save equipment but also avoid spent acid therebetween, the discharging of waste water, and reduce dyestuff synthetic starting material manufacturing expense; The diazonium salt that utilizes this method gained has no adverse effects for dyestuff quality and yield through repeatedly dyestuff is synthetic.
If no specified otherwise, proportioning according to the invention is the molecule mol ratio, and said content is mass percent.
Embodiment
Below in conjunction with specific embodiment, the present invention is elaborated, but is not limited only to this.
Embodiment 1
P-Nitroaniline 15g is added in the hydrochloric acid soln of 400g 5%, pulled an oar 5 hours down for 10 ℃.Add 0.5g polysorbate60 (belonging to the polyvalent alcohol Soxylat A 25-7); Under 15 ℃, add 5% chlorine bleach liquor 200g, be warming up to 20 ℃ of chlorination reactions 5 hours; Obtain ortho-chlor-para nitraniline hydrochloric acid soln or suspension-s, detecting ortho-chlor-para nitraniline content through performance liquid chromatography is 92.2%; Add 30% sodium nitrite solution 24.5g at 15 ℃ and carry out diazotization reaction, kept 2 hours, obtain the ortho-chlor-para nitraniline diazonium salt solution.
The diazonium salt solution that obtains is by art methods and 35g m-acetamino-N, and the coupling of N-diacetyl oxy ethyl aniline obtains Red 167: 1 (C.I.Disperse Red 167:1) dyestuff 53g, yield does
96.45％。
Embodiment 2
P-Nitroaniline 15g is added in the sulphuric acid soln of 200g 10%, add 10g acetic acid, pulled an oar 1 hour down for 10 ℃, add polyoxyethylene oleic acid ester (belonging to the aliphatic acid polyethenoxy ether ester) 0.5g.Under 10 ℃, add 5% chlorine bleach liquor 200g,, be warming up to 20 ℃ of reactions 5 hours, obtain the ortho-chlor-para nitraniline hydrochloric acid soln, detect ortho-chlor-para nitraniline content 93.2% through performance liquid chromatography; Add 30% sodium nitrite solution 25g at 10 ℃, kept 2 hours, obtain the ortho-chlor-para nitraniline diazonium salt solution.
The diazonium salt solution that obtains is by art methods and 35g m-acetamino-N, and the coupling of N-diacetyl oxy ethyl aniline obtains Red 167: 1 (C.I.Disperse Red 167:1) dyestuff 53.5g, yield 97.36%.
Embodiment 3
P-Nitroaniline 15g is added in the acetum of 200g 30%, add 10g phosphoric acid, pulled an oar 3 hours down for 10 ℃, add oleic acid polyoxyethylene (belonging to the aliphatic acid polyethenoxy ether ester) 0.3g.Under 10 ℃, add 10% chlorine bleach liquor 200g, be warming up to 20 ℃ of reactions 5 hours, obtain the ortho-chlor-para nitraniline hydrochloric acid soln, detect ortho-chlor-para nitraniline content 92.8% through performance liquid chromatography; Add 20% sodium nitrite solution 25.2g at 10 ℃, kept 2 hours, obtain the ortho-chlor-para nitraniline diazonium salt solution.
The diazonium salt solution that obtains is by art methods and 35g m-acetamino-N, and the coupling of N-diacetyl oxy ethyl aniline obtains Red 167: 1 (C.I.Disperse Red 167:1) dyestuff 53.5g, yield 97.36%.
Comparative example 1: industriallization current implementing technology
P-Nitroaniline 15g is added in the hydrochloric acid soln of 400g15%, pulled an oar 1 hour down for 10 ℃, under 10 ℃; Add chlorine bleach liquor 200g; Be warming up to 20 ℃ of reactions 5 hours, obtain the ortho-chlor-para nitraniline hydrochloric acid soln, detecting ortho-chlor-para nitraniline content through performance liquid chromatography is 92.5%; Filter, the filter cake washing is to neutral;
In the diazonium pot, add sulfuric acid 80g, add the ortho-chlor-para nitraniline wet cake 25g that gives money as a gift below 60 ℃, pulled an oar 8 hours, on the rocksly be cooled to 0 ℃, add 30% sodium nitrite solution 36g, and kept 3～5 hours, obtain the ortho-chlor-para nitraniline diazonium salt solution.
The diazonium salt solution that obtains is by ordinary method and 46.7g m-acetamino-N, and the coupling of N-diacetyl oxy ethyl aniline obtains Red 167: 1 (C.I.Disperse Red 167:1) dyestuff 70.6g, yield 96.45%.
With the comparative example contrast, method of the present invention is simple to operate, saves the separation circuit of ortho-chlor-para nitraniline, reduces the running cost and the three wastes, and products obtained therefrom is through synthetic dyestuff checking, and superior in quality, yield is higher.
Claims (4)
1. the preparation method of an ortho-chlor-para nitraniline diazonium salt; It is characterized in that: be raw material with the p-Nitroaniline;, mass percent pulls an oar in being 5～30% acidic medium; With chlorizating agent and consumption is that the tensio-active agent of p-Nitroaniline consumption 1～5% carries out chlorination reaction, directly adds diazotization reagent after chlorination reaction finishes and accomplishes diazotization reaction again, obtains diazonium salt solution; P-Nitroaniline wherein: acidic medium: chlorizating agent: the mol ratio of diazo reagent is 1: 2～10: 1～1.3: 1～1.3;
Described acidic medium is selected from hydrochloric acid, sulfuric acid, acetic acid or phosphoric acid;
Described chlorizating agent is selected from hypochlorous acid, Youxiaolin, Losantin, potassium hypochlorite, chloric acid, VAL-DROP, Potcrate, calcium chlorate or chlorine;
Described tensio-active agent is a nonionogenic tenside, is selected from AEO, or the aliphatic acid polyethenoxy ether ester;
Described diazo reagent is selected from Sodium Nitrite or nitrosyl sulfuric acid.
2. the preparation method of ortho-chlor-para nitraniline diazonium salt according to claim 1 is characterized in that, the mass percent of described acidic medium is 5～20%, and carrying out beating time is 1～8 hour.
3. the preparation method of ortho-chlor-para nitraniline diazonium salt according to claim 1 and 2 is characterized in that described chlorination reaction temperature is-10～50 ℃, and the chlorination reaction time is 0.5～10 hour; Described diazotization reaction temperature is-10～40 ℃, and the diazotization reaction time is 1～8 hour.
4. the preparation method of ortho-chlor-para nitraniline diazonium salt according to claim 3 is characterized in that described chlorination reaction temperature is-5～30 ℃, and described diazotization reaction temperature is-5～20 ℃.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103664683B (en) * | 2012-09-21 | 2018-05-11 | 浙江龙盛集团股份有限公司 | A kind of continuous diazotising production technology of aromatic amine |
| CN108329718A (en) * | 2017-12-20 | 2018-07-27 | 宜兴市新伟隆印染有限公司 | Solve the technique that disperse dyes contaminate bright red claret dyestuff color mark |
| CN109535044B (en) * | 2018-12-18 | 2021-06-15 | 金华双宏化工有限公司 | Diazotization method of aromatic primary amine |
| CN111704806B (en) * | 2020-06-22 | 2021-05-11 | 清华大学 | Continuous preparation method of disperse dye |
| CN115536617A (en) * | 2022-08-31 | 2022-12-30 | 湖南复瑞生物医药技术有限责任公司 | Preparation method of dantrolene intermediate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS225462B1 (en) * | 1982-04-28 | 1984-02-13 | Ruzicka Karel | Continuous manufacture of aromatic diazone compounds |
| CN1793240A (en) * | 2005-09-28 | 2006-06-28 | 杭州吉华化工有限公司 | Dispersing dye mixture and dye products |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS225462B1 (en) * | 1982-04-28 | 1984-02-13 | Ruzicka Karel | Continuous manufacture of aromatic diazone compounds |
| CN1793240A (en) * | 2005-09-28 | 2006-06-28 | 杭州吉华化工有限公司 | Dispersing dye mixture and dye products |
Non-Patent Citations (3)
| Title |
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| Christophe Colas et al..An Efficient Procedure for the Synthesis of Crystalline Aryldiazonium Trifluoroacetates-Synthetic Applications.《Eur. J. Org. Chem.》.1999,1357-1366. * |
| 张树斌等.邻氯对硝基苯胺合成工艺研究.《化工生产与技术》.2004,第11卷(第6期),第20-28页. * |
| 朱正华等.2-氰基-4-硝基-6-卤素苯胺的合成及其在分散染料中的应用.《华东化工学院学报》.1982,(第4期),第429-436页. * |
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