CN1045593C - 2,6-dibromo-4-carboxysulfonateacyl aminobenzene and its synthesis - Google Patents
2,6-dibromo-4-carboxysulfonateacyl aminobenzene and its synthesis Download PDFInfo
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- CN1045593C CN1045593C CN96115131A CN96115131A CN1045593C CN 1045593 C CN1045593 C CN 1045593C CN 96115131 A CN96115131 A CN 96115131A CN 96115131 A CN96115131 A CN 96115131A CN 1045593 C CN1045593 C CN 1045593C
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- CN
- China
- Prior art keywords
- aminobenzene
- carboxysulfonateacylaminobenzene
- reaction
- dibromo
- hydrogen peroxide
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims description 38
- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- 238000010189 synthetic method Methods 0.000 claims abstract description 10
- 238000005893 bromination reaction Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- OKNLBTNZLUNRDW-UHFFFAOYSA-N hydrogen peroxide;hydrobromide Chemical compound Br.OO OKNLBTNZLUNRDW-UHFFFAOYSA-N 0.000 claims abstract description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 16
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 238000007171 acid catalysis Methods 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 2
- LCBQHOHHMWNXAS-UHFFFAOYSA-N 2-(4-amino-3,5-dibromophenyl)sulfonylacetic acid Chemical compound NC1=C(Br)C=C(S(=O)(=O)CC(O)=O)C=C1Br LCBQHOHHMWNXAS-UHFFFAOYSA-N 0.000 abstract 1
- AMLVBKKHVPSTBT-UHFFFAOYSA-N [Br].OO Chemical compound [Br].OO AMLVBKKHVPSTBT-UHFFFAOYSA-N 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000003643 water by type Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000000986 disperse dye Substances 0.000 description 4
- 125000001246 bromo group Chemical class Br* 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229960001413 acetanilide Drugs 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- -1 carboxymethyl sulfonyl Chemical group 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides 2, 6-dibromo-4-carboxymethylsulfonylaniline and a synthetic method thereof, wherein a hydrolysis reaction is carried out by 4-carboxymethylsulfonylacetanil in the presence of an acid calalyst without a separation reaction product; a bromination reaction is carried out by a brominating agent, bromine-hydrogen peroxide solution or hydrobromic acid-hydrogen peroxide solution to obtain a product. Through the steps of separation, water washing and drying, the yield of the product can be up to 91 to 98%.
Description
The present invention relates to a kind of amino benzenes compounds and synthetic method thereof, proposed 2 especially, 6-dibromo-4-carboxysulfonateacylaminobenzene aminobenzene and synthetic method thereof.
This new compound is the intermediate of synthetic temporarily water-soluble disperse dye containing carboxymethyl sulfonyl, through diazotization, coupled reaction, can obtain the azo-type temporarily water-soluble disperse dye, further to obtain dark azo-type temporarily water-soluble disperse dye.
Technical scheme of the present invention is as follows: synthetic a kind of carboxysulfonateacylaminobenzene aminobenzene, and 2, the 6-dibromo-4-carboxysulfonateacylaminobenzene aminobenzene, molecular formula is C
8H
7Br
2O
4S, structural formula is
, synthetic route is as follows:
Raw material 4-carboxymethyl sulfonyl Acetanilide can be by known Acetanilide through chlorosulphonation, reduction, obtain with the Mono Chloro Acetic Acid condensation again.
With 4-carboxymethyl sulfonyl Acetanilide (I) reaction that under acid catalysis, is hydrolyzed, obtain 4-carboxysulfonateacylaminobenzene aminobenzene (II), used acid can be hydrochloric acid, Hydrogen bromide or sulfuric acid.Hydrolysising reacting temperature is 80～90 ℃, with 80～87 ℃ be the best, acid concentration is 4～10N, is the best with 4～6N.Reaction times is 0.5～1.5 hour.
Need not separate after the hydrolysis, can directly carry out bromination reaction, reduce the lock out operation between unit process, reduce sour consumption, improve yield.The 4-carboxysulfonateacylaminobenzene aminobenzene that generates is directly carried out bromination reaction with bromo-hydrogen peroxide or Hydrogen bromide-hydrogen peroxide, and temperature of reaction is 55～80 ℃, is the best with 55～65 ℃.Dripping bromine and hydrogen peroxide in the reaction can reach terminal point in 1.5～2 hours.Add and proceed bromination reaction after hydrogen peroxide can make the hydrogen bromide that produces in the reaction process be oxidized to bromine, also can make bromizating agent with Hydrogen bromide-hydrogen peroxide.
The mole proportioning of each material is in the reaction: 4-carboxymethyl sulfonyl Acetanilide: hydrochloric acid (or Hydrogen bromide or sulfuric acid)=1: 1.4; 4-carboxymethyl sulfonyl Acetanilide: bromine: hydrogen peroxide=1: 1.05～1.15: 1.05～1.15; 4-carboxymethyl sulfonyl Acetanilide: Hydrogen bromide: hydrogen peroxide=1: 2.2: 2.2.
The bromination reaction thing is filtered about 20～25 ℃.Filter cake adds water, and with in the alkali and the dissolving, filter out impurities.Filtrate with hcl acidifying to pH be 3～4, separate out solid phase prod, filtration, washing, drying.Through liquid-phase chromatographic analysis, purity is 91～93%, and yield can reach 98%.
The product fusing point is 188～189 ℃ (alcohol-water recrystallizations), and results of elemental analyses is: analytical value % (calculated value %): C25.52 (25.76), H1.92 (1.89), N3.85 (3.76).
2 of the present invention's proposition, 6-dibromo-4-carboxysulfonateacylaminobenzene aminobenzene and synthetic method thereof can successively be finished hydrolysis and bromination reaction in same reactor, and intermediate product need not to separate, and can reduce sour consumption, improves yield, reduces environmental pollution.2, the 6-dibromo-4-carboxysulfonateacylaminobenzene aminobenzene is the important diazo component of the dark azo-type temporarily water-soluble disperse dye of preparation.
The present invention will be further described below in conjunction with embodiment.
Example 1 is added to 13.83 gram raw materials (I) (purity is 92.93%) and 6 milliliter of 36.5% hydrochloric acid and 6 ml waters in the four-hole bottle, stirring, heating in water bath, and 80～82 ℃ of reactions 40 minutes, solution was transparence.Add 40 ml waters, when being cooled to 59 ℃, drip 8.4 gram bromines, after adding in about 20 minutes, begin to drip 5.25 milliliters in hydrogen peroxide (concentration is/100 milliliters of 34 grams), added in about 20 minutes.Being incubated reaction in 45 minutes finishes.Be cooled to 20 ℃ of filtrations.Filter cake adds 60 ml waters, under agitation with 9 milliliter of 30% sodium hydroxide solution neutrality that neutralizes.Filter out impurities, filtrate with 5 milliliter of 36.5% hcl acidifying to pH be 3～4.Filtration, washing, drying get 18.3 gram products, liquid-phase chromatographic analysis purity 91.42%, yield 98%.
Example 2 is with the hydrochloric acid of 41.48 gram raw materials (I) (purity 92.93%) and 17.8 milliliters 36.5%, and 27 ml waters place 500 milliliters of four-hole bottles, stirs and heating, reacts 55 minutes in 82～84 ℃.Add 110 ml waters, be cooled to 58 ℃, begin to drip 25.2 gram bromines, drip 15.8 milliliters of hydrogen peroxide (concentration is/100 milliliters of 34 grams) then, add the back insulation and finished reaction in 45 minutes.Aftertreatment is with embodiment 1.Through liquid-phase chromatographic analysis product purity 93.06%, yield 94.9%.
Example 3 is mixed 13.85 gram raw materials (I) with 16 milliliters of Hydrogen bromides (45%), 6 ml waters, stir and heating,, add 45 ml waters in 82～84 ℃ of reactions 20 minutes, be cooled to 60 ℃ and begin to drip 11 milliliters in hydrogen peroxide (/ 100 milliliters of 34 grams), be incubated 1 hour to reaction end.Aftertreatment is with embodiment 1, and yield is 83%.
Example 4 is with 52 gram raw materials (I) and 15 milliliter of 98% vitriol oil, and 40 ml waters place 500 milliliters of four-hole bottles, are warming up to 87 ℃, hydrolysis 1.5 hours.Be cooled to 60 ℃, drip 36 gram bromines, dripped 20 milliliters in hydrogen peroxide (/ 100 milliliters of 34 grams) then in 1 hour, controlled temperature is below 80 ℃.50 ℃ of insulations 0.5 hour, reaction was finished.Filtering reacting liquid is put into beaker with filter cake, adds about 700 milliliters of water, with 30% sodium hydroxide neutralization, filtering insolubles, filtrate with 36.5% hydrochloric acid acid out to pH3～4, filtration, washing, drying.Yield 82%.
Claims (6)
1. carboxysulfonateacylaminobenzene aminobenzene, 2, the 6-dibromo-4-carboxysulfonateacylaminobenzene aminobenzene, molecular formula is C
8H
7Br
2O
4S, its structural formula is:
2. Synthetic 2, the synthetic method of 6-dibromo-4-carboxysulfonateacylaminobenzene aminobenzene, it is characterized in that: (1) is with the reaction that is hydrolyzed under acid catalysis of 4-carboxymethyl sulfonyl Acetanilide, obtain the 4-carboxysulfonateacylaminobenzene aminobenzene, used acid is hydrochloric acid, Hydrogen bromide or sulfuric acid, hydrolysising reacting temperature is 80～90 ℃, and acid concentration is 4～10N, and the reaction times is 0.5～1.5 hour; (2) the 4-carboxysulfonateacylaminobenzene aminobenzene that generates is carried out bromination reaction with bromo-hydrogen peroxide or Hydrogen bromide-hydrogen peroxide, temperature of reaction is 55～80 ℃, and the reaction times is 1.5～2 hours.
3. according to claim 22, the synthetic method of 6-dibromo-4-carboxysulfonateacylaminobenzene aminobenzene, the mole proportioning of each material is in it is characterized in that reacting: 4-carboxymethyl sulfonyl Acetanilide: hydrochloric acid=1: 1.4; 4-carboxymethyl sulfonyl Acetanilide: Hydrogen bromide=1: 1.4; 4-carboxymethyl sulfonyl Acetanilide: sulfuric acid=1: 1.4; 4-carboxymethyl sulfonyl Acetanilide: bromine: hydrogen peroxide=1: 1.05～1.15: 1.05～1.15,4-carboxymethyl sulfonyl Acetanilide: Hydrogen bromide: hydrogen peroxide=1: 2.2: 2.2.
4. according to claim 22, the synthetic method of 6-dibromo-4-carboxysulfonateacylaminobenzene aminobenzene is characterized in that hydrolysising reacting temperature is 80～87 ℃ with the reaction that is hydrolyzed of 4-carboxymethyl sulfonyl Acetanilide under acid catalysis.
5. according to claim 22, the synthetic method of 6-dibromo-4-carboxysulfonateacylaminobenzene aminobenzene is characterized in that acid concentration is 4～6N with the reaction that is hydrolyzed of 4-carboxymethyl sulfonyl Acetanilide under acid catalysis.
6. according to claim 22, the synthetic method of 6-dibromo-4-carboxysulfonateacylaminobenzene aminobenzene is characterized in that the 4-carboxysulfonateacylaminobenzene aminobenzene that will generate is 55～65 ℃ with the temperature of reaction that bromo-hydrogen peroxide or Hydrogen bromide-hydrogen peroxide carry out bromination reaction.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115131A CN1045593C (en) | 1996-03-01 | 1996-03-01 | 2,6-dibromo-4-carboxysulfonateacyl aminobenzene and its synthesis |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115131A CN1045593C (en) | 1996-03-01 | 1996-03-01 | 2,6-dibromo-4-carboxysulfonateacyl aminobenzene and its synthesis |
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| Publication Number | Publication Date |
|---|---|
| CN1136037A CN1136037A (en) | 1996-11-20 |
| CN1045593C true CN1045593C (en) | 1999-10-13 |
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| CN96115131A Expired - Fee Related CN1045593C (en) | 1996-03-01 | 1996-03-01 | 2,6-dibromo-4-carboxysulfonateacyl aminobenzene and its synthesis |
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| CN111019393A (en) * | 2019-12-25 | 2020-04-17 | 沈阳化工研究院有限公司 | Yellow liquid dye composition for dyeing and printing and application thereof |
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| CN102161833A (en) * | 2011-03-11 | 2011-08-24 | 河南洛染股份有限公司 | Red temporary water-soluble disperse dye and manufacturing method and use thereof |
| CN102174271B (en) * | 2011-03-11 | 2013-06-05 | 河南洛染股份有限公司 | Temporarily water-soluble disperse dye and preparation method and application thereof |
| CN103224452B (en) * | 2012-01-30 | 2015-07-15 | 江苏英力科技发展有限公司 | 2-bromine-4,6-dichloroaniline preparation method |
| CN106187814B (en) * | 2016-06-29 | 2018-09-28 | 浙江闰土研究院有限公司 | A kind of synthetic method of disperse dyes diazol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990006302A1 (en) * | 1988-11-25 | 1990-06-14 | Ici Americas Inc. | Preparation of 2-halo-4-alkylsulfonylbenzoic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990006302A1 (en) * | 1988-11-25 | 1990-06-14 | Ici Americas Inc. | Preparation of 2-halo-4-alkylsulfonylbenzoic acid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019393A (en) * | 2019-12-25 | 2020-04-17 | 沈阳化工研究院有限公司 | Yellow liquid dye composition for dyeing and printing and application thereof |
| CN111019393B (en) * | 2019-12-25 | 2022-02-11 | 沈阳化工研究院有限公司 | Yellow liquid dye composition for dyeing and printing and application thereof |
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| Publication number | Publication date |
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| CN1136037A (en) | 1996-11-20 |
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