CN1045002C - Preparation of 2,6-dichloroaniline - Google Patents
Preparation of 2,6-dichloroaniline Download PDFInfo
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- CN1045002C CN1045002C CN95102807A CN95102807A CN1045002C CN 1045002 C CN1045002 C CN 1045002C CN 95102807 A CN95102807 A CN 95102807A CN 95102807 A CN95102807 A CN 95102807A CN 1045002 C CN1045002 C CN 1045002C
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- diimino
- phosphinylidyne
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Abstract
The present invention relates to a preparation method of 2, 6-dichloroaniline, which comprises: N, N'-diphenyl urea is used as a raw materials to finally obtain the 2, 6-dichloroaniline through sulfonation, cyclo-chloration, hydrolysis to remove a carbonyl group and hydrolysis to remove a sulfonic group. The reaction conditions for all the steps are disclosed in the specification. Compared with the existing technological method, the present invention has the advantages of simple technology, high yield, low cost, etc. The yield of the 2, 6-dichloroaniline measured by the N, N'-diphenyl urea can reach more than 65 % of the quantity in theory.
Description
The present invention relates to a kind of 2, the preparation method of 6-dichlorphenamide bulk powder, it belongs to the synthetic method of arylamine in the fine chemical product.
2, the 6-dichlorphenamide bulk powder is important medicine intermediate.Its synthetic method is a lot.Existing industrial production process is that sulfonamido method (Deutsches Wirtschafts Patent 00247670 is taken off in chlorination on the ring of sulfanilic amide, hydrolysis; 1987).And sulfanilic amide is generally made through acetylize, chlorosulphonation, ammonification and hydrolysis deacetylation by aniline.Therefore, prepare 2 as stated above by aniline, the reaction formula of 6-dichlorphenamide bulk powder is as follows:
The weak point of aforesaid method is: product yield is low, if in aniline, total recovery has only about 46.50% of theoretical amount; Complex technical process; The product cost height.
At the weak point of aforesaid method, the object of the present invention is to provide a kind of preparation 2, the novel method of 6-dichlorphenamide bulk powder.The characteristics of this method are to simplify from aniline preparation 2, and the technological process of 6-dichlorphenamide bulk powder, and the yield of raising product reduce production costs.
For achieving the above object; synthetic route of the present invention is the N that utilizes the N-phosphinylidyneization by aniline to make, and N '-diphenyl urea is a raw material, with N; N '-diphenyl urea chlorination on sulfonation → ring → hydrolysis decarburization acyl group → hydrolysis desulfonation → and obtain 2, the 6-dichlorphenamide bulk powder.Therefore prepare 2 by aniline by the inventive method, the net reaction of 6-dichlorphenamide bulk powder is as follows: 2
N, N '-diphenyl urea
4,4 '-(phosphinylidyne diimino)-two Phenylsulfonic acids (being N, N '-diphenyl urea-4,4 '-disulfonic acid)
4.4 '-phosphinylidyne diimino)-two-(3, the 5-dichloro) Phenylsulfonic acid
For realizing above-mentioned operational path, the processing condition of each reactions steps of the present invention are:
1.N the reaction conditions that the sulfonation of N '-diphenyl urea generates 4,4 '-(phosphinylidyne diimino)-two Phenylsulfonic acids is: used sulphonating agent is to contain H
2SO
4At the vitriol oil more than 92.5% or contain free SO
3At the oleum below 25%; The consumption of sulphonating agent is N, 3～12 times of N '-diphenyl urea weight; Sulfonation temperature is 0～100 ℃, and the sulfonation time is 1～6 hour.
2.4 the reaction conditions of chlorination generation 4,4 '-(phosphinylidyne diimino)-two-(3, the 5-dichloro) Phenylsulfonic acid is on the ring of 4 '-(phosphinylidyne diimino)-two Phenylsulfonic acids: chlorizating agent is a chlorine, or the hydrogenchloride oxidizer; When carrying out chlorination with chlorine, the chlorination medium is to contain H
2SO
4At the sulfuric acid more than 40%, or contain free SO
3At the oleum below 5%; The consumption of chlorination medium is 4,3～12 times of 4 '-(phosphinylidyne diimino)-two Phenylsulfonic acid weight, and chlorine and 4, the mol ratio of 4 '-(phosphinylidyne diimino)-two Phenylsulfonic acids is 3.8～5.0: 1; When carrying out chlorination with the hydrogenchloride oxidizer, the chlorination medium can be to contain H
2SO
420～50% and contain HCl at 2～10% the aqueous solution, the consumption of chlorination medium is 6～15 times of 4,4 '-(phosphinylidyne diimino)-two Phenylsulfonic acid weight; Used oxygenant can be 10～30% aqueous hydrogen peroxide solutions, or 5～12% aqueous sodium hypochlorite solutions, or 10～30% sodium chlorate aqueous solutions.A kind of consumption and 4 in the above-mentioned oxygenant, the mol ratio of 4 '-(phosphinylidyne diimino)-two Phenylsulfonic acids is respectively 3.8～5.6: 1, or 3.8～5.6: 1 or 1.3～1.8: 1; Adopting above-mentioned various chlorizating agent to carry out the chlorating temperature of reaction is 0～70 ℃; The chlorination reaction time is 1～20 hour.
3.4 the hydrolysis decarburization acyl group of 4 '-(phosphinylidyne diimino)-two-(3, the 5-dichloro) Phenylsulfonic acid generates 4-amino-3, the reaction conditions of 5-dichloro benzosulfonic acid is: hydrolysis medium is to contain H
2SO
410～75% and contain the aqueous solution of HCl below 5 %; The weight of hydrolysis medium is 4,6～20 times of 4 '-(phosphinylidyne diimino)-two-(3, the 5-dichloro)-Phenylsulfonic acid weight; Hydrolysis temperature is 70～140 ℃, and hydrolysis time is 1～5 hour.
4.4-amino-3, the hydrolysis desulfonation of 5-dichloro benzosulfonic acid generates 2, and the reaction conditions of 6-dichlorphenamide bulk powder is: hydrolysis medium is for containing H
2SO
440～75% and contain HCl at the aqueous solution below 2%; Its consumption is a 4-amino-3,4～15 times of 5-dichloro benzosulfonic acid weight; Hydrolysis temperature is 120～170 ℃, and hydrolysis time is 1～6 hour.
The present invention compares with current technology, and reactions steps reduces, and technological process is simplified, and presses N, N '-diphenyl urea meter, and 2, the yield of 6-dichlorphenamide bulk powder crude product can reach more than 75% of theoretical amount.If by aniline, 2, the yield of 6-dichlorphenamide bulk powder crude product can reach more than 73% of theoretical amount, and 2, the yield of 6-dichlorphenamide bulk powder elaboration can reach more than 65% of theoretical amount, far above the yield of current technology, therefore can reduce the cost of product greatly.
Embodiment one:
In the four-hole glass flask, add and contain free SO
320% oleum 150g, under agitation, below 40 ℃, slowly add N, N '-diphenyl urea 21.2g, stirred 3 hours at 40 ℃, at 40 ℃,, in reaction solution, add 300ml water then then with 4 hours feeding chlorine 31.6g, stirred 3 hours at 120 ℃, stirred 3 hours at 150 ℃ then.Contain 2 in the reaction solution, more than the 6-dichlorphenamide bulk powder 24.4g.Press N, N '-diphenyl urea meter, yield are more than 75% of theoretical amount.
Embodiment two:
In 500ml four-hole glass flask, add and contain free SO
320% oleum 150g, under agitation, below 40 ℃, add N, N '-diphenyl urea 21.2g, stirred 3 hours at 40 ℃, in reaction solution, add entry 300ml, 30% concentrated hydrochloric acid 60g, then at 30 ℃ with dripping 30% aqueous hydrogen peroxide solution 60g in 1 hour, stirred 4 hours at 30 ℃ then, stirred 3 hours at 120 ℃ then, stirred 3 hours at 150 ℃ at last.Contain 2 in the reaction solution, more than the 6-dichlorphenamide bulk powder 24.0g.Press N, N '-diphenyl urea meter, yield are more than 74% of theoretical amount.
Embodiment three:
Press embodiment two, replace 60g 30% aqueous hydrogen peroxide solution with the 320g10% chlorine bleach liquor.Contain 2 in the reaction solution, more than the 6-dichlorphenamide bulk powder 23.0g.Press N, N '-diphenyl urea meter, yield are more than 71% of theoretical amount.
Embodiment four:
Press embodiment two, replace the 60g30% aqueous hydrogen peroxide solution with the 55g30% sodium chlorate solution.Contain 2 in the reaction solution, more than the 6-dichlorphenamide bulk powder 23.5g.Press N, N '-diphenyl urea meter, yield are more than 73% of theoretical amount.
Claims (6)
1.2 the preparation method of 6-dichlorphenamide bulk powder is characterized in that with N; N '-diphenyl urea is a raw material; through sulfonation make 4,4 '-(phosphinylidyne diimino)-two Phenylsulfonic acids, make 4 through encircling chlorination again; 4 '-(phosphinylidyne diimino)-two-(3; the 5-dichloro) Phenylsulfonic acid is made 4-amino-3 through hydrolysis decarburization acyl group, the 5-dichloro benzosulfonic acid again; after the hydrolysis desulfonation makes 2, the 6-dichlorphenamide bulk powder.
2. method according to claim 1 is characterized in that N, the sulfonation of N '-diphenyl urea generates 4,4 '-reaction conditions of (phosphinylidyne diimino)-two Phenylsulfonic acids is: sulphonating agent is to contain H
2SO
4At the vitriol oil more than 92.5%, or contain free SO
3At the oleum below 25%; The consumption of sulphonating agent is N, 3～12 times of N '-diphenyl urea weight, and sulfonation temperature is 0～100 ℃; The sulfonation time is 1～6 hour.
3. method according to claim 1, it is characterized in that 4,4 '-ring of (phosphinylidyne diimino)-two Phenylsulfonic acids on chlorination generate 4,4 '-(phosphinylidyne diimino)-two-(3, the 5-dichloro) reaction conditions of Phenylsulfonic acid is: chlorizating agent is a chlorine, and the chlorination medium is to contain H
2SO
4At the sulfuric acid more than 40%, or contain free SO
3At the oleum below 5%; The consumption of sulfuric acid medium is 4,4 '-3～12 times of (phosphinylidyne diimino)-two Phenylsulfonic acid weight; Chlorine and 4,4 '-mol ratio of (phosphinylidyne diimino)-two Phenylsulfonic acids is 3.8～5.0: 1; The chlorating temperature of reaction is 0～70 ℃; The chlorination reaction time is 1～20 hour.
4. method according to claim 1, it is characterized in that 4,4 '-ring of (phosphinylidyne diimino)-two Phenylsulfonic acids on chlorination generate 4,4 '-reaction conditions of (phosphinylidyne diimino)-two-(3, the 5-dichloro) Phenylsulfonic acid is: chlorizating agent is the hydrogenchloride oxidizer; The chlorination medium can be to contain H
2SO
420～50% and contain HCl at 2～10% the aqueous solution; The consumption of chlorination medium is 4,4 '-6～15 times of (phosphinylidyne diimino)-two Phenylsulfonic acids; Used oxygenant can be 10～30% aqueous hydrogen peroxide solutions, or 5～12% aqueous sodium hypochlorite solutions or 10～30% sodium chlorate aqueous solutions.A kind of consumption and 4,4 in the above-mentioned oxygenant '-mol ratio of (phosphinylidyne diimino)-two Phenylsulfonic acids is 3.8～5.6: 1 or 3.8～5.6: 1 or 1.3～1.8: 1; The chlorating temperature of reaction is 0～70 ℃; The chlorination reaction time is 1～20 hour.
5. method according to claim 1, it is characterized in that 4,4 '-the hydrolysis decarburization acyl group of (phosphinylidyne diimino)-two-(3, the 5-dichloro) Phenylsulfonic acid generates 4-amino-3, and the reaction conditions of 5-dichloro benzosulfonic acid is: hydrolysis medium is to contain H
2SO
410～75% and contain HCl at the aqueous solution below 5%, the weight of hydrolysis medium is 4,4 '-6～20 times of (phosphinylidyne diimino)-two-(3, the 5-dichloro) Phenylsulfonic acid weight; Hydrolysis temperature is 70～140 ℃; Hydrolysis time is 1～5 hour.
6. method according to claim 1 is characterized in that 4-amino-3, and the hydrolysis desulfonation of 5-diamino benzene sulfonic acid generates 2, and the reaction conditions of 6-dichlorphenamide bulk powder is: hydrolysis medium is for containing H
2SO
440～75%, and contain HCl at the aqueous solution below 2%, the consumption of hydrolysis medium is a 4-amino-3,4～15 times of 5-dichloro benzosulfonic acid weight; Hydrolysis temperature is 120～170 ℃; Hydrolysis time is 1～6 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95102807A CN1045002C (en) | 1995-03-28 | 1995-03-28 | Preparation of 2,6-dichloroaniline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95102807A CN1045002C (en) | 1995-03-28 | 1995-03-28 | Preparation of 2,6-dichloroaniline |
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|---|---|
| CN1111235A CN1111235A (en) | 1995-11-08 |
| CN1045002C true CN1045002C (en) | 1999-09-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95102807A Expired - Fee Related CN1045002C (en) | 1995-03-28 | 1995-03-28 | Preparation of 2,6-dichloroaniline |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100389104C (en) * | 2006-04-10 | 2008-05-21 | 浙江大学 | Process for preparation of 2,6-dichloroaniline |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328243C (en) * | 2005-08-30 | 2007-07-25 | 谢建伟 | Prepn process of 2,6-dichloroaniline |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86101095A (en) * | 1985-02-11 | 1986-08-06 | 罗纳·布郎克农业化学公司 | The preparation method of substituted phenyl urea |
-
1995
- 1995-03-28 CN CN95102807A patent/CN1045002C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86101095A (en) * | 1985-02-11 | 1986-08-06 | 罗纳·布郎克农业化学公司 | The preparation method of substituted phenyl urea |
Non-Patent Citations (1)
| Title |
|---|
| J.PHARM SOC JAPAN 64 1994.1.1 OBSRTVATIOMS ON DIPHENYLUREA DERIVARIVES(KYOSUKE TSUDA AND SHUSAKU SAKAMOTO) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100389104C (en) * | 2006-04-10 | 2008-05-21 | 浙江大学 | Process for preparation of 2,6-dichloroaniline |
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|---|---|
| CN1111235A (en) | 1995-11-08 |
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Granted publication date: 19990908 Termination date: 20140328 |