CN104402786A - 2,2'-dibenzamido-diphenyl disulfide preparation method - Google Patents
2,2'-dibenzamido-diphenyl disulfide preparation method Download PDFInfo
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- CN104402786A CN104402786A CN201410780723.8A CN201410780723A CN104402786A CN 104402786 A CN104402786 A CN 104402786A CN 201410780723 A CN201410780723 A CN 201410780723A CN 104402786 A CN104402786 A CN 104402786A
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Abstract
The invention discloses a 2,2'-dibenzamido-diphenyl disulfide preparation method, and belongs to the technical field of synthesis of organic compounds. The preparation method comprises the following steps: preparing a 2,2'-diphenylamine disulfide from a sulfide and o-nitro halobenzene as raw materials by adopting a one-pot method, and performing acylation on the 2,2'-diphenylamine disulfide to obtain a 2,2'-dibenzamido-diphenyl disulfide. The process step that an intermediate product, namely 2-amino-4-chloro thiophenol, is separated and purified by adopting the processes of steam distillation, organic solvent extraction and the like in the prior art is omitted, the technological process is simplified, meanwhile, the yield of the intermediate product, namely the 2,2'-diphenylamine disulfide, is improved, and the yield of the 2,2'-dibenzamido-diphenyl disulfide is further improved. The preparation method has the advantages of being short in technological process, simple in operation, less in three wastes emission, environmental-friendly in the production process, high in yield, low in production cost, simple in equipment and small in investment, and facilitates industrial popularization and application.
Description
Technical field
The present invention relates to organic compound synthesis technical field, be specifically related to a kind of 2,2 '-dibenzamidodiphenyl two sulphur preparing process.
Background technology
From 2002, China's rubber-consumer total amount occupies first place in the world always, wherein rubber-consumer total amount in 2013 has reached 8,300,000 tons, estimate that consumption glue amount in 2014 reaches 9,000,000 tons, meanwhile in the course of processing of rubber, add rubber ingredients and improve various performance, China also just becomes the biggest market of rubber ingredients, has reached the industrial scale of 1,000,000 tons in 2012.
In rubber plastic steelmaking process, add peptizer can realize faster reducing molecular weight rubber, increase plasticity number, improve workability, according to the consumption of 0.2 % ~ 3 %, the Present Domestic market requirement is about annual 100000 tons.Now, domestic rubber enterprise commonly uses the phenyl-sulfhydrate compounds such as pentachlorothiophenol, zinc salt of pentachlorothiophenol as peptizer, the synthesis material of this kind of peptizer is Perchlorobenzene, very big to people, animal toxicity, forbidden producing and using in worldwide, phenyl-sulfhydrate compounds own smell is large simultaneously, is difficult to degraded, cause severe contamination, serious to human health damage.With 2, the aryl bisulphide that 2 '-dibenzamidodiphenyl two sulphur (DBD) is representative, owing to having low toxicity, easy degraded and superior processing use properties, be called as environment-friendly type peptizer, ratified to become nontoxic rubber by U.S. food and medicine office (FDA) and process chemical, wide market, it is best rubber peptizer recognized in the world, along with China's environmental pollution management continues to increase, disposal of pollutants problem becomes the bottleneck of enterprise development, around environmental protection, the research and development of energy-conservation and efficient quickening poisonous and harmful rubber ingredients substitute process for cleanly preparing, it is current rubber ingredients industrial expansion direction, thus DBD replacement sulfur phenols peptizer is inexorable trend.
But the complex manufacturing of DBD at present, productive rate is low, production cost is higher, and market value is more than 100,000 yuan/ton, and thiophenols product is only between 4 ~ 50,000 yuan/ton, obvious inferior position is there is in price compared with thiophenols product, therefore, develop a kind of production technique simple, productive rate is high, the DBD preparation method that production cost is low, has great economic implications to the development of rubber industry.
Summary of the invention
In order to overcome the defect of prior art, the object of the present invention is to provide that a kind of production technique is simple, productive rate is high, production cost is low 2,2 '-dibenzamidodiphenyl two sulphur preparing process.
To achieve these goals, the technical solution used in the present invention is as follows:
A kind of 2,2 '-dibenzamidodiphenyl two sulphur preparing process, concrete operation step is:
(1) sulfide, the mixing of adjacent nitro halobenzene add solvent, and add basic solution, reaction, adds oxygenant, isolate solid product, obtain 2,2 '-pentanoic disulphide;
(2) step (1) prepare 2,2 '-pentanoic disulphide and Benzoyl chloride carry out acylation reaction, obtain 2,2 '-dibenzamidodiphenyl two sulphur.
Described adjacent nitro halobenzene is o-Nitrochlorobenzene, adjacent fluoronitrobenzene, adjacent Nitrobromobenzene or adjacent nitro iodobenzene.
Described sulfide is Sodium sulfhydrate, ammonium hydro sulfide, ammonium sulfide or sodium sulphite.
Described solvent is water, ethanol, acetone, acetonitrile or ether.
Sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium tert-butoxide or potassium tert-butoxide solution that described basic solution is is solvent with water, ethanol, acetone, acetonitrile or ether.
Described oxygenant is sodium peroxide, hydrogen peroxide or Potassium peroxide.
The mass ratio of described sulfide, adjacent nitro halobenzene is (1 ~ 2): (2 ~ 4).
The mass ratio of described sulfide, solvent is (1 ~ 2): (5 ~ 10).
The mass ratio of described sulfide, alkali is (20 ~ 40): (1 ~ 8).
The mass ratio of described sulfide, oxygenant is (1 ~ 2): (0.1 ~ 2).
The reaction times of the reaction described in step (1) is 0.2 ~ 10 hour.
When solvent is water in step (1), the final aqueous solution after COD falls in the operations such as SBR pond, Iron carbon reduction, bio anaerobic pond, Aerobic Pond, settling bowl, through through check up to standard after discharge; When solvent is ethanol, acetone, ether organic solvent, solvent is recycled after rectifying steams.
The concrete grammar of the acylation reaction described in step (2) is: 2, and 2 '-pentanoic disulphide adds in solvent, adds catalyzer, adds Benzoyl chloride, collects solid product after reaction, obtains 2,2 '-dibenzamidodiphenyl two sulphur.
Described solvent is methylene dichloride, acetone, chloroform, acetonitrile or ethyl acetate.
Described catalyzer is salt of wormwood, triethylamine or bicarbonate of ammonia.
Described 2, the mass ratio of 2 '-pentanoic disulphide, Benzoyl chloride is (2 ~ 4): (1 ~ 2).
Described 2, the mass ratio of 2 '-pentanoic disulphide, solvent is (1 ~ 2): (5 ~ 10).
Described 2, the mass ratio of 2 '-pentanoic disulphide, catalyzer is (20 ~ 40): (1 ~ 4).
The reaction times of described reaction is 0.1 ~ 2 hour.
The concrete grammar of described collection solid product is: steam solvent, and residue adds organic solvent recrystallization, and after filtration, drying is granulated, and obtains 2,2 '-dibenzamidodiphenyl two sulphur.
Described organic solvent is methylene dichloride, acetone, acetonitrile, chloroform or ethyl acetate.
The present invention 2, 2 '-dibenzamidodiphenyl two sulphur preparation method, with sulfide and adjacent nitro halobenzene for raw material one kettle way prepares 2, 2 '-pentanoic disulphide, again by 2, 2 are obtained after 2 '-pentanoic disulphide acylations, 2 '-dibenzamidodiphenyl two sulphur, compare traditional preparation technology, in preparation 2, one kettle way is adopted to prepare in the process of 2 '-pentanoic disulphide, save in traditional technology through wet distillation, the processing step of the technique separating-purifying intermediate product near amino thiophenols such as organic solvent extraction, the present invention adopts the preparation method of not isolation of intermediate products near amino thiophenols, in the generation structure of near amino thiophenols, directly add oxygenant prepare 2, 2 '-pentanoic disulphide, simplification of flowsheet, reduce solvent waste liquid and exhaust gas emission in separating-purifying process, reduce environmental pollution, improve intermediate product 2 simultaneously, the productive rate of 2 '-pentanoic disulphide, and then improve 2, the productive rate of 2 '-dibenzamidodiphenyl two sulphur.
The present invention 2, and 2 '-dibenzamidodiphenyl two sulphur preparation method technical process is short, simple to operate, institute is with an organic solvent after Distillation recovery, reuse, the treated rear discharge up to standard of a small amount of waste water, three waste discharge is few, production technique environmental protection, productive rate is high, and production cost is low, and equipment is simple, less investment, is easy to technology and applies.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, but does not form any limitation of the invention.
Embodiment 1
The present embodiment 2,2 '-dibenzamidodiphenyl two sulphur preparation method, concrete operation step is as follows:
(1) o-Nitrochlorobenzene 160g, ammonium hydro sulfide 75g are joined in 300ml water, then drip mass concentration 30% aqueous sodium hydroxide solution 30g, after reaction 3h, in this reaction soln, add mass concentration 30% hydrogen peroxide solution 300ml, after reaction 8h, centrifugation.Supernatant liquor, through SBR pond, is degraded in iron carbon, bio anaerobic pond, Aerobic Pond, after settling bowl operation, and qualified discharge; Solid product obtains 2,2 '-pentanoic disulphide after drying, and productive rate is 60%;
(2) 2,2 '-pentanoic disulphide 260g is joined in 1000ml methylene dichloride, add salt of wormwood 50g as catalyzer; the dichloromethane solution 850ml dripping mass concentration 20% Benzoyl chloride carries out acylation reaction; after reaction 6min, methylene dichloride is steamed recycling, and residue utilizes methylene dichloride to carry out recrystallization; after filtration; drying granulation, obtains 2 after test package, 2 '-dibenzamidodiphenyl two sulphur; product fusing point is 139 ~ 140 ° of C, and productive rate is 97%.
The present embodiment 2,2 '-dibenzamidodiphenyl two sulphur total recovery is 58%.
Embodiment 2
The present embodiment 2,2 '-dibenzamidodiphenyl two sulphur preparation method, concrete operation step is as follows:
(1) adjacent Nitrobromobenzene 18g, Sodium sulfhydrate 7g are joined in 200ml acetone, then add potassium hydroxide 0.4g, after reaction 4h, in this reaction soln, add Potassium peroxide 10g, after reaction 10h, centrifugation; Supernatant liquor solvent is acetone, recycles after distillation; Solid product obtains 2,2 '-pentanoic disulphide after drying, and productive rate is 62%;
(2) 2,2 '-pentanoic disulphide 26g is joined in 100ml acetonitrile, add salt of wormwood 5g as catalyzer; the acetonitrile solution 85ml dripping mass concentration 20% Benzoyl chloride carries out acylation reaction; after yellow mercury oxide appears in reaction 20min, acetonitrile is steamed recycling, and residue utilizes methylene dichloride to carry out recrystallization; after filtration; drying granulation, obtains 2 after test package, 2 '-dibenzamidodiphenyl two sulphur; product fusing point is 137 ~ 138 ° of C, and productive rate is 98%.
The present embodiment 2,2 '-dibenzamidodiphenyl two sulphur total recovery is 61%.
Embodiment 3
The present embodiment 2,2 '-dibenzamidodiphenyl two sulphur preparation method, concrete operation step is as follows:
(1) adjacent nitro iodobenzene 38g, sodium sulphite 14g are joined in 80ml ether, then add the potassium tert.-butoxide tetrahydrofuran solution 15ml that mass concentration is 20%, after reaction 12min, in this reaction soln, add Potassium peroxide 20g, after reaction 3h, centrifugation.Supernatant liquor solvent is ether, recycles after distillation; Solid product obtains 2,2 '-pentanoic disulphide after drying, and productive rate is 66%;
(2) 2,2 '-pentanoic disulphide 15g is joined in 100ml ethyl acetate, add triethylamine 3ml as catalyzer; the acetonitrile solution 50ml dripping mass concentration 20% Benzoyl chloride carries out acylation reaction; after reaction 30min, ethyl acetate is steamed recycling, and residue utilizes methylene dichloride to carry out recrystallization; after filtration; drying granulation, obtains 2 after test package, 2 '-dibenzamidodiphenyl two sulphur; product fusing point is 137 ~ 138 ° of C, and productive rate is 98%.
The present embodiment 2,2 '-dibenzamidodiphenyl two sulphur total recovery is 64%.
Embodiment 4
The present embodiment 2,2 '-dibenzamidodiphenyl two sulphur preparation method, concrete operation step is as follows:
(1) adjacent fluoronitrobenzene 30g, ammonium sulfide 10g are joined in 100ml ethanol, then add lithium hydroxide 3g, after reaction 3h, in this reaction soln, add mass concentration 30% hydrogen peroxide solution 10ml, after reaction 10h, centrifugation.Supernatant liquor solvent is ethanol, recycles after distillation; Solid product obtains 2,2 '-pentanoic disulphide after drying, and productive rate is 62%;
(2) 2,2 '-pentanoic disulphide 10g is joined in 50ml chloroform, add triethylamine 1ml as catalyzer; the acetonitrile solution 35ml dripping mass concentration 20% Benzoyl chloride carries out acylation reaction; after reaction 30min, chloroform is steamed recycling, and residue utilizes chloroform to carry out recrystallization; after filtration; drying granulation, obtains 2 after test package, 2 '-dibenzamidodiphenyl two sulphur; product fusing point is 137 ~ 138 ° of C, and productive rate is 95%.
The present embodiment 2,2 '-dibenzamidodiphenyl two sulphur total recovery is 59%.
Embodiment 5
The present embodiment 2,2 '-dibenzamidodiphenyl two sulphur preparation method, concrete operation step is as follows:
(1) o-Nitrochlorobenzene 80g, ammonium hydro sulfide 40g are joined in 150ml water, then drip mass concentration 30% aqueous sodium hydroxide solution 30g, after reaction 10h, in this reaction soln, add mass concentration 30% hydrogen peroxide solution 80ml, after reaction 2h, centrifugation.Supernatant liquor, through SBR pond, is degraded in iron carbon, bio anaerobic pond, Aerobic Pond, after settling bowl operation, and qualified discharge; Solid product obtains 2,2 '-pentanoic disulphide after drying, and productive rate is 62%;
(2) 2,2 '-pentanoic disulphide 70g is joined in 300ml methylene dichloride, add salt of wormwood 15g as catalyzer; the dichloromethane solution 200ml dripping mass concentration 20% Benzoyl chloride carries out acylation reaction; after reaction 2h, methylene dichloride is steamed recycling, and residue utilizes methylene dichloride to carry out recrystallization; after filtration; drying granulation, obtains 2 after test package, 2 '-dibenzamidodiphenyl two sulphur; product fusing point is 139 ~ 140 ° of C, and productive rate is 96%.
The present embodiment 2,2 '-dibenzamidodiphenyl two sulphur total recovery is 60%.
Comparative example
This comparative example 2,2 '-dibenzamidodiphenyl two sulphur preparation method, concrete operation step is as follows:
(1) ammonium sulfide 12g, o-Nitrochlorobenzene 40g are joined in 100ml ethanol, then add sodium hydroxide 0.3g, reaction 3h, this solution is carried out wet distillation, removing byproduct of reaction, then utilize toluene to carry out extractive distillation to reaction soln, obtain near amino thiophenols after drying, yield is 58%;
(2) by near amino thiophenols 15g, join in 300ml water, in this reactant solution, add mass concentration 30% hydrogen peroxide solution 50ml, after reaction 1h, centrifugation, solid product obtains 2,2 ' pentanoic disulphide after drying, and productive rate is 95%;
(3) pentanoic disulphide 12g is joined in methylene dichloride 50ml; add triethylamine 1.5ml as catalyzer, the dichloromethane solution 36ml dripping mass concentration 20% Benzoyl chloride carries out acylation reaction, after reaction 2h; methylene dichloride is steamed recycling; residue utilizes methylene dichloride to carry out recrystallization, after filtration, and drying granulation; 2 are obtained after test package; 2 '-dibenzamidodiphenyl two sulphur product, product fusing point is 137 ~ 138 ° of C, and productive rate is 98%.
The total recovery of this comparative example intermediate product 2,2 ' pentanoic disulphide intermediate product is 55%; 2,2 '-dibenzamidodiphenyl two sulphur total recovery is 54%.
The result of above-mentioned comparative example shows, preparation method of the present invention compares the step that ratio eliminates wet distillation and organic solvent extraction synthesis near amino thiophenols, employing directly adds oxygenant one pot reaction and prepares intermediate product 2 in the generation structure of near amino thiophenols, 2 ' pentanoic disulphide, make intermediate product 2, the productive rate of 2 ' pentanoic disulphide improves 5% ~ 11%, gross product 2, 2 '-dibenzamidodiphenyl two sulphur overall yield is corresponding improves 4% ~ 10%, increase production 2, the economic benefit of 2 '-dibenzamidodiphenyl two sulphur, there is important industrial applications be worth.
Claims (10)
1. one kind 2,2 '-dibenzamidodiphenyl two sulphur preparing process, is characterized in that, comprises following operation steps:
(1) sulfide, adjacent nitro halobenzene are added solvent, add basic solution, after reaction, add oxygenant, isolate solid product, obtain 2,2 '-pentanoic disulphide;
(2) step (1) prepare 2,2 '-pentanoic disulphide and Benzoyl chloride carry out acylation reaction, obtain 2,2 '-dibenzamidodiphenyl two sulphur.
2. as claimed in claim 12,2 '-dibenzamidodiphenyl two sulphur preparing process, is characterized in that, the mass ratio of described sulfide, adjacent nitro halobenzene is (1 ~ 2): (2 ~ 4).
3. as claimed in claim 12,2 '-dibenzamidodiphenyl two sulphur preparing process, is characterized in that, described sulfide is Sodium sulfhydrate, ammonium hydro sulfide, ammonium sulfide or sodium sulphite.
4. as claimed in claim 12,2 '-dibenzamidodiphenyl two sulphur preparing process, is characterized in that, described solvent is water, ethanol, acetone, acetonitrile or ether.
5. as claimed in claim 12,2 '-dibenzamidodiphenyl two sulphur preparing process, it is characterized in that, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium tert-butoxide or potassium tert-butoxide solution that described basic solution is is solvent with water, ethanol, acetone, acetonitrile or ether.
6. as claimed in claim 12,2 '-dibenzamidodiphenyl two sulphur preparing process, is characterized in that, described oxygenant is sodium peroxide, hydrogen peroxide or Potassium peroxide.
7. as claimed in claim 12,2 '-dibenzamidodiphenyl two sulphur preparing process, is characterized in that, the reaction times of step (1) described reaction is 0.2 ~ 10 hour.
8. as claimed in claim 12; 2 '-dibenzamidodiphenyl two sulphur preparing process; it is characterized in that; the concrete grammar of the acylation reaction described in step (2) is: 2, and 2 '-pentanoic disulphide adds in solvent, adds catalyzer; add Benzoyl chloride; collect solid product after reaction, obtain 2,2 '-dibenzamidodiphenyl two sulphur.
9. as claimed in claim 82,2 '-dibenzamidodiphenyl two sulphur preparing process, is characterized in that, described 2, and the mass ratio of 2 '-pentanoic disulphide, Benzoyl chloride is (2 ~ 4): (1 ~ 2).
10. as claimed in claim 82,2 '-dibenzamidodiphenyl two sulphur preparing process, is characterized in that, described catalyzer is salt of wormwood, triethylamine or sodium bicarbonate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774165A (en) * | 2015-03-16 | 2015-07-15 | 菏泽佳成化工有限公司 | Green and industrial preparation method of rubber peptizer DBD |
| CN105237450A (en) * | 2015-10-29 | 2016-01-13 | 浙江黄岩天南化工厂 | Preparation method for rubber peptizer DBD synthesized by using two-phase acylation method |
| CN105712913A (en) * | 2016-01-12 | 2016-06-29 | 濮阳蔚林化工股份有限公司 | Rubber peptizer SS preparation method |
| CN108003075A (en) * | 2017-11-30 | 2018-05-08 | 兰溪市拜高化工有限公司 | A kind of industrialized process for preparing of rubber peptizer DBD |
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| CN102304074A (en) * | 2011-06-21 | 2012-01-04 | 聊城大学 | Method for preparing rubber peptizing agent, namely 2,2'-dibenzamido diphenyl disulfide compound |
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| US1438096A (en) * | 1921-06-01 | 1922-12-05 | Arthur B Coffin | Automatic clutch release for tractors |
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| DE2758786A1 (en) * | 1977-12-29 | 1979-07-12 | Bayer Ag | Bis:aminophenyl di:sulphide cpds. prodn. - from halo-nitrobenzene using gaseous acid anhydride to expel hydrogen sulphide for increased yield and purity |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774165A (en) * | 2015-03-16 | 2015-07-15 | 菏泽佳成化工有限公司 | Green and industrial preparation method of rubber peptizer DBD |
| CN105237450A (en) * | 2015-10-29 | 2016-01-13 | 浙江黄岩天南化工厂 | Preparation method for rubber peptizer DBD synthesized by using two-phase acylation method |
| CN105712913A (en) * | 2016-01-12 | 2016-06-29 | 濮阳蔚林化工股份有限公司 | Rubber peptizer SS preparation method |
| CN105712913B (en) * | 2016-01-12 | 2017-06-23 | 蔚林新材料科技股份有限公司 | A kind of preparation method of rubber peptizer SS |
| CN108003075A (en) * | 2017-11-30 | 2018-05-08 | 兰溪市拜高化工有限公司 | A kind of industrialized process for preparing of rubber peptizer DBD |
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