CN101643423A - Method for preparing 3,3'-dichlorobenzidine hydrochloride by hydrochloric acid translocation - Google Patents
Method for preparing 3,3'-dichlorobenzidine hydrochloride by hydrochloric acid translocation Download PDFInfo
- Publication number
- CN101643423A CN101643423A CN200810139123A CN200810139123A CN101643423A CN 101643423 A CN101643423 A CN 101643423A CN 200810139123 A CN200810139123 A CN 200810139123A CN 200810139123 A CN200810139123 A CN 200810139123A CN 101643423 A CN101643423 A CN 101643423A
- Authority
- CN
- China
- Prior art keywords
- hydrochloric acid
- dichlorobenzidine hydrochloride
- rare metal
- dichlorohydrazobenzene
- dichlorobenzidine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 3,3'-dichlorobenzidine hydrochloride by hydrochloric acid translocation. The method comprises the following steps: catalytically hydrogenating ortho-nitrochlorobenzene by hydrogen in the presence of catalysts, such as organic solvents, rare metal and the like to prepare 2,2'-dichlorohydrazobenzene; performing a translocation and rearrangement reactionin hydrochloric acid to finally prepare the 3,3'-dichlorobenzidine hydrochloride with yield reaching over 90 percent. The method has reasonable process route; and the finished product prepared by adopting the method has higher yield and purity, and has larger industrial prospect.
Description
Technical field
The present invention relates to a kind of 3, the preparation method of 3 '-dichlorobenzidine hydrochloride.
Background technology
3,3 '-dichlorobenzidine hydrochloride is a kind of important pigment, dyestuff intermediate, and it is water-soluble slightly, dissolve in alcohol, easily oxidation, current preparation 3,3 '-dichlorobenzidine hydrochloride mostly adopts 2, and 2 '-dichlorohydrazobenzene carries out translocation reaction by sulfuric acid or hydrochloric acid and forms.But sometimes in translocation reaction, exist processing step not too rationally, the inaccurate problem of processing parameter, cause that prepared product yield is not high, cost is bigger, and raw material can not be fully utilized.
Summary of the invention
For solving the problem of above existence, the invention provides a kind of hydrochloric acid transposition preparation 3 that utilizes, the method for 3 '-dichlorobenzidine hydrochloride, its technical scheme of taking is:
3,3 '-dichlorobenzidine hydrochloride is prepared from by following steps:
1) in stainless steel autoclave, adds o-Nitrochlorobenzene, organic solvent dimethylbenzene or toluene, 30% sodium hydroxide solution and rare metal catalyzer, use nitrogen replacement three times behind the good seal earlier, use hydrogen exchange again three times, pressure-controlling is at 1.5Mpa, and temperature is controlled at 50～90 ℃, reacted 9～11 hours, generate hydrazobenzene, tell catalyzer after the filtration and repeat to apply mechanically, the filtrate layering, oil phase is 2,2 '-dichlorohydrazobenzene;
2) 31% hydrochloric acid and water are made into 24～26% beginning acid, add 2 then, 2 '-dichlorohydrazobenzene was 0～40 ℃ of insulation reaction 6 hours, get 3,3 '-dichlorobenzidine hydrochloride crude product filters the rear filtrate layering, and organic solvent repeats to apply mechanically, after the making beating of filter cake water, being neutralized to pH value with sodium hydroxide solution again is 7～9, filters then, filter cake is added 5% hydrochloric acid soln, be heated to 85～95 ℃ complete molten, dripped 31% hydrochloric acid soln acid out then 4 hours, acid out finishes, and is cooled to 15～25 ℃ then, filter and promptly get 3,3 '-dichlorobenzidine hydrochloride.
The rare metal catalyzer is made of carrier and the rare metal that is carried on this carrier, carrier comprises gac, silicon-dioxide, aluminum oxide or molecular sieve, rare metal comprises one or more in palladium, platinum, gold, ruthenium or the rhodium, and the rare metal catalyst consumption is every 100g o-Nitrochlorobenzene with 1～10g.
Described organic solvent is and 2 dimethylbenzene that 2 '-dichlorohydrazobenzene dissolves each other or toluene.
With ortho-nitrochlorobenzene in organic solvent and catalyzer such as rare metal in the presence of carry out catalytic hydrogenation with hydrogen, 2, the 2 '-dichlorohydrazobenzene that makes, the position rotaring rearrangement reaction takes place in hydrochloric acid then, finally make 3,3 '-dichlorobenzidine hydrochloride, yield can reach more than 90%.This method operational path is reasonable, adopts the finished product yield and the purity of this method preparation all higher, therefore has bigger industrial prospect.
Embodiment
Below in conjunction with embodiment the present invention is elaborated:
In stainless steel autoclave, add o-Nitrochlorobenzene 200g, dimethylbenzene 90ml, 30% sodium hydroxide solution 166ml, the pt/c5% product 5g that wets.Good seal is used nitrogen replacement three times earlier, uses hydrogen exchange again three times.Pressure-controlling is at 1.5Mpa, temperature is controlled at 50～90 ℃, reacted 10 hours, and generated hydrazobenzene, filter, telling catalyzer repeats to apply mechanically, the filtrate layering, oil phase is 2,2 '-dichlorohydrazobenzene, calculate 2 according to liquid-phase chromatographic analysis, the mole rate of 2 '-dichlorohydrazobenzene is 95%.
31% hydrochloric acid 820g and water 170ml are made into 25% beginning acid, add 2 then, 2 '-dichlorohydrazobenzene is 0～40 ℃ of insulation reaction 6 hours, 3,3 '-dichlorobenzidine hydrochloride crude product (purity 95%).Filter, the filtrate layering, dimethylbenzene repeats to apply mechanically, after the making beating of filter cake water, be neutralized to PH=7～9 with sodium hydroxide solution again, filter then, filter cake is added 5% hydrochloric acid soln 700ml, be heated to 90 ℃ complete molten, dripped 31% hydrochloric acid soln 860ml acid out then 4 hours, acid out finishes, be cooled to 20 ℃ then, filter and promptly get 3,3 '-dichlorobenzidine hydrochloride, the heavy 130g of finished product.
Claims (3)
1, a kind ofly utilize hydrochloric acid transposition preparation 3, the method for 3 '-dichlorobenzidine hydrochloride is characterized in that being prepared from by following steps:
1) in stainless steel autoclave, adds o-Nitrochlorobenzene, organic solvent dimethylbenzene or toluene, 30% sodium hydroxide solution and rare metal catalyzer, use nitrogen replacement three times behind the good seal earlier, use hydrogen exchange again three times, pressure-controlling is at 1.5Mpa, and temperature is controlled at 50～90 ℃, reacted 9～11 hours, generate hydrazobenzene, tell catalyzer after the filtration and repeat to apply mechanically, the filtrate layering, oil phase is 2,2 '-dichlorohydrazobenzene;
2) 31% hydrochloric acid and water are made into 24～26% beginning acid, add 2 then, 2 '-dichlorohydrazobenzene was 0～40 ℃ of insulation reaction 6 hours, get 3,3 '-dichlorobenzidine hydrochloride crude product filters the rear filtrate layering, and organic solvent repeats to apply mechanically, after the making beating of filter cake water, being neutralized to pH value with sodium hydroxide solution again is 7～9, filters then, filter cake is added 5% hydrochloric acid soln, be heated to 85～95 ℃ complete molten, dripped 31% hydrochloric acid soln acid out then 4 hours, acid out finishes, and is cooled to 15～25 ℃ then, filter and promptly get 3,3 '-dichlorobenzidine hydrochloride.
2, utilize the hydrochloric acid transposition to prepare 3 according to claim 1 is described, the method of 3 '-dichlorobenzidine hydrochloride, it is characterized in that: the rare metal catalyzer is made of carrier and the rare metal that is carried on this carrier, carrier comprises gac, silicon-dioxide, aluminum oxide or molecular sieve, rare metal comprises one or more in palladium, platinum, gold, ruthenium or the rhodium, and the rare metal catalyst consumption is every 100g o-Nitrochlorobenzene with 1～10g.
3, utilize the hydrochloric acid transposition to prepare 3 according to claim 1 is described, the method for 3 '-dichlorobenzidine hydrochloride is characterized in that: described organic solvent is dimethylbenzene or the toluene that dissolves each other with 2,2 '-dichlorohydrazobenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810139123A CN101643423A (en) | 2008-08-08 | 2008-08-08 | Method for preparing 3,3'-dichlorobenzidine hydrochloride by hydrochloric acid translocation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810139123A CN101643423A (en) | 2008-08-08 | 2008-08-08 | Method for preparing 3,3'-dichlorobenzidine hydrochloride by hydrochloric acid translocation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101643423A true CN101643423A (en) | 2010-02-10 |
Family
ID=41655513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810139123A Pending CN101643423A (en) | 2008-08-08 | 2008-08-08 | Method for preparing 3,3'-dichlorobenzidine hydrochloride by hydrochloric acid translocation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101643423A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727199A (en) * | 2018-07-13 | 2018-11-02 | 山东隆信药业有限公司 | A kind of method that hexahydrotoluene substitutes toluene production DCB 3,3' dichlorobenzidine hydrochloride |
| CN108976131A (en) * | 2018-07-13 | 2018-12-11 | 山东隆信药业有限公司 | A kind of method of water substitution toluene production DCB 3,3' dichlorobenzidine hydrochloride |
| CN111574380A (en) * | 2020-02-19 | 2020-08-25 | 天津科技大学 | Method for preparing 4,4 '-disubstituted-2, 2' -diaminobiphenyl and hydrochloride thereof by reduction coupling method |
| CN113548972A (en) * | 2021-07-13 | 2021-10-26 | 济宁祥泰和新材料科技有限公司 | Production process of 3, 3' -dichlorobenzidine hydrochloride |
-
2008
- 2008-08-08 CN CN200810139123A patent/CN101643423A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727199A (en) * | 2018-07-13 | 2018-11-02 | 山东隆信药业有限公司 | A kind of method that hexahydrotoluene substitutes toluene production DCB 3,3' dichlorobenzidine hydrochloride |
| CN108976131A (en) * | 2018-07-13 | 2018-12-11 | 山东隆信药业有限公司 | A kind of method of water substitution toluene production DCB 3,3' dichlorobenzidine hydrochloride |
| CN111574380A (en) * | 2020-02-19 | 2020-08-25 | 天津科技大学 | Method for preparing 4,4 '-disubstituted-2, 2' -diaminobiphenyl and hydrochloride thereof by reduction coupling method |
| CN113548972A (en) * | 2021-07-13 | 2021-10-26 | 济宁祥泰和新材料科技有限公司 | Production process of 3, 3' -dichlorobenzidine hydrochloride |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100467432C (en) | Synthesis method of substituted cyclohexanone and/or substituted cyclohexanol | |
| US20110015451A1 (en) | Process for the preparation of an aqueous colloidal precious metal suspension | |
| CN101643423A (en) | Method for preparing 3,3'-dichlorobenzidine hydrochloride by hydrochloric acid translocation | |
| CN101641316B (en) | Process for the preparation of hydroxytyrosol | |
| CN110423190A (en) | A kind of method of iron complex catalysis ketone alpha-alkyl | |
| CN113024385B (en) | Preparation method of 2,2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl | |
| CN107537497A (en) | A kind of preparation method and application for being used to prepare the catalyst of adjacent methyl cyclohexanol | |
| CN102985427B (en) | Method for producing diamino-dianhydro-dideoxy-hexitolene, particularly preferably 2,5-diamino-1,4:3,6-dianhydro-2,5-dideoxy-d-hexitol | |
| CN101643428A (en) | Method for preparing 3,3'-dimethoxybenzidine hydrochloride | |
| CN102212314A (en) | Method for preparing water-white highly-hydrogenated rosin | |
| CN101990528B (en) | Catechol manufacturing method | |
| CN103232455A (en) | Industrial production method of sitagliptin | |
| CN102234240B (en) | Method for synthesizing L-BMAA (Beta-Methylamino L-Alanine) hydrochloride | |
| US9090560B2 (en) | Process for microwave assisted synthesis of N-methyl pyrrolidone | |
| CN112479824A (en) | Method for recovering crystallization mother liquor in production process of 4-chloro-3, 5-dimethylphenol | |
| US6403833B1 (en) | Single step hydrogenation of nitrobenzene to p-aminophenol | |
| WO2008043269A1 (en) | Preparation method for 1-(3-methyloxybenzene)ethylamine with optical activity | |
| CN101870695B (en) | Preparation method of 3-(2-chloroethyl)-6, 7, 8, 9 - tetrahydro-9 - hydroxy - 2 - Methylenetetrahydrofolate - pyrido [1,2-alpha] pyrimidine -4 - ketone | |
| CN111170932A (en) | Preparation method of 2-aminomethyl-5-trifluoromethyl pyridine salt | |
| CN111116378A (en) | Method for synthesizing 1, 8-diaminonaphthalene by selective reduction of 1, 8-dinitronaphthalene | |
| CN101696173B (en) | Method for synthesizing o-amino-p- tert butyl phenol | |
| CN114105780B (en) | Synthesis method of isooctylamine and derivative by one-pot method | |
| CN101643424A (en) | Method for preparing 3,3'-dichlorobenzidine hydrochloride through formaldehyde-hydrazine hydrate reduction | |
| CN114436944B (en) | Synthesis method of ibrutinib intermediate | |
| CN102268048A (en) | Method for preparing D-allose by reducing ketose by catalytic hydrogenation process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20100210 |