CN1244555C - Method for hydrolysis of 1,2-bis(3'-nitrobenzene sulphone group )ethane byproduced in the production of 3-(beta-hydroxy ethylsulphonyl)nitrobenzene - Google Patents
Method for hydrolysis of 1,2-bis(3'-nitrobenzene sulphone group )ethane byproduced in the production of 3-(beta-hydroxy ethylsulphonyl)nitrobenzene Download PDFInfo
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- CN1244555C CN1244555C CN 03178523 CN03178523A CN1244555C CN 1244555 C CN1244555 C CN 1244555C CN 03178523 CN03178523 CN 03178523 CN 03178523 A CN03178523 A CN 03178523A CN 1244555 C CN1244555 C CN 1244555C
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- oil
- mirbane
- ethane
- nitrobenzene
- sulfuryl
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Abstract
The present invention relates to a hydrolyzation method of 1, 2-double (3'-nitrobenzene sulfuryl) ethane as a by-product in the preparation of 3-(beta-hydroxyethyl sulfuryl)-nitrobenzene by the addition reaction of 3-nitro benzene sulfinic acid and ethylene oxide. In the hydrolyzation method, a separated by-product is hydrolyzed in an alkaline way in aqueous alkali of which the concentration is from 0.5 to 10% at the reaction temperature of 40 DEG C-100 DEG C; after the hydrolyzation is completed, a 3-(beta-hydroxyehyl sulfuryl)-nitrobenzene filter cake is obtained by cooling and filtering; filter liquid is condensed and crystallized by cooling to obtain 3-sulfinate nitro benzene sulfinate. The hydrolyzation method changes 7 to 10% of by-products into principal products, reduces the production cost and also reduces the pressure for treating three waste.
Description
Technical field the present invention relates in vinyl-sulfone reactive dyes intermediate 3-(β-hydroxyethyl sulfone)-oil of mirbane preparation, by product 1, the method for hydrolysis of 2-two (3 '-oil of mirbane sulfuryl) ethane.
Background technology is well-known, when 3-oil of mirbane-sulfinic acid and oxyethane addition reaction prepare 3-(β-hydroxyethyl sulfone)-oil of mirbane, there are part intermediate product 3-ethene sulfuryl-oil of mirbane and unreacted raw material 3-oil of mirbane-sulfinic acid to add and become by product 1,2-pair (3 '-the oil of mirbane sulfuryl) ethane (hereinafter to be referred as " two sulfone "), that is:
3-ethene sulfuryl oil of mirbane 3-oil of mirbane-sulfinic acid 1,2-pair (3 '-the oil of mirbane sulfuryl) ethane
(" two sulfone ")
Because the strong electrophilic of nitro makes 3-(β-hydroxyethyl sulfone)-oil of mirbane be easy to change into 3-ethene sulfuryl oil of mirbane, therefore, this side reaction is difficult to avoid.Usually " two sulfone " content in product is between 7-10%.This part by product is not only caused the waste of raw material as not recycling, and has improved production cost; And increased the pressure that the three wastes are handled, in addition,, have influence on the quality of next step reduction reaction product 3-(β-hydroxyethyl sulfone) aniline because by product is mingled in the principal product.
When summary of the invention carries out addition reaction and prepares 3-(β-hydroxyethyl sulfone)-oil of mirbane with 3-oil of mirbane-sulfinic acid and oxyethane, after isolating principal product, with by product 1,2-pair (3 '-the oil of mirbane sulfuryl) ethane (i.e. " two sulfone "), under suitable reaction conditions, adopt the method for alkaline hydrolysis, " two sulfone " hydrolysis is transformed into principal product 3-(β-hydroxyethyl sulfone)-oil of mirbane, thereby improve the output of principal product.
In the process of alkaline hydrolysis, in fact, reaction is decomposed earlier and is generated 3-oil of mirbane-sulfinic acid and 3-ethene sulfuryl oil of mirbane, then, the latter again with the water addition, generate 3-(β-hydroxyethyl sulfone) oil of mirbane:
Because under higher temperature and alkaline condition, the addition speed of 3-ethene sulfuryl-oil of mirbane and water is very fast, " two sulfone " alkali decomposes and the water addition is to finish continuously.
Technical scheme of the present invention is achieved like this:
When 3-oil of mirbane-sulfinic acid and oxyethane carry out addition reaction and prepare 3-(β-hydroxyethyl sulfone)-oil of mirbane, after isolating principal product 3-(β-hydroxyethyl sulfone)-oil of mirbane, with by product 1,2-two (3 '-oil of mirbane sulfuryl) ethane is in the alkali aqueous solution of 0.5-10% in concentration, according to alkali and 1, the mol ratio of 2-two (3 '-oil of mirbane sulfuryl) ethane is 1: 0.8-10, temperature of reaction is 40-100 ℃, carry out basic hydrolysis, by product is transformed into 3-(β-hydroxyethyl sulfone)-oil of mirbane, after hydrolysis fully, cooling, filter, obtain 3-(β-hydroxyethyl sulfone)-oil of mirbane filter cake; Concentrating filter liquor, crystallisation by cooling can get 3-oil of mirbane-sulfinate.
1, the used alkali of hydrolysis of 2-two (3 '-oil of mirbane sulfuryl) ethane is sodium hydroxide, potassium hydroxide, calcium hydroxide, yellow soda ash, salt of wormwood.
The present invention is owing to fully recycle the 7-10% by product 1 that generates simultaneously in the addition reaction, 2-pair (3 '-the oil of mirbane sulfuryl) ethane, adopt the method for alkaline hydrolysis, decompose " two sulfone " by product, obtain 3-(β-hydroxyethyl sulfone)-oil of mirbane, not only improved the output and the quality of principal product, reduced production cost, and reduced the pressure that the three wastes are handled, also help 3-(β-hydroxyethyl sulfone)-oil of mirbane and adopt hydrogenation reduction process.
The present invention is described in detail below in conjunction with embodiment.
Embodiment
Embodiment 1
In the 1000mL flask, add 3-oil of mirbane-sulfinic acid 187g, water 500mL drips oxyethane 70g, at 60 ℃ of reaction 8h, the condenses suspension solid content that reaction obtains after finishing is 25-28%, filter 3-in the filter cake (β-hydroxyethyl sulfone)-oil of mirbane 203-210g, two sulfone 22-44g, 2,2 '-two (3 '-nitrophenyl) ether 4-8g, behind methanol extraction nitro thing, the processing that can be hydrolyzed of two sulfones.
Embodiment 2
In the 1000mL there-necked flask, add 0.5% sodium hydroxide 500g, 1,2-pair (3 '-the oil of mirbane sulfuryl) ethane 12.5g, be stirred and heated to 100 ℃, reaction 3h, at this moment, two sulfones are complete hydrolysis.Be cooled to 10 ℃, filter, get 3-(β-hydroxyethyl sulfone)-oil of mirbane 6.9g.Filtrate decompression is concentrated to 30mL, and crystallisation by cooling can get 6.4g m-nitro-sulfinic acid sodium.
Embodiment 3
Replace 0.5% sodium hydroxide among the embodiment 2 with 2% salt of wormwood 300g, reaction conditions and operation then can get 6.6g 3-(β-hydroxyethyl sulfone)-oil of mirbane, 6.3g m-nitro-sulfinic acid potassium with embodiment 2.
Embodiment 4
In the 1000mL there-necked flask, add 10% aqueous sodium carbonate 500g, two sulfone 38g, in 40 ℃, stirring reaction 12h, at this moment, two sulfones hydrolysis are complete.Be cooled to 20 ℃, filter, get 26.3g 3-(β-hydroxyethyl sulfone)-oil of mirbane.Filtrate concentrates, and is cooled to 30 ℃, can get 15.6g 3-nitro benzene sulfinic acid sodium salt.
Embodiment 5
With 0.5% sodium hydroxide 500g among the 1% calcium hydroxide 300mL replacement embodiment 2, all the other can get 6.8g3-(β-hydroxyethyl sulfone)-oil of mirbane with embodiment 2., 6.7g m-nitro-sulfinic acid calcium.
Claims (2)
1, a kind ofly carry out addition reaction at 3-oil of mirbane-sulfinic acid and oxyethane and prepare in 3-(β-hydroxyethyl sulfone)-oil of mirbane, by product 1, the method for hydrolysis of 2-two (3 '-oil of mirbane sulfuryl) ethane, it is characterized in that isolating by product 1,2-two (3 '-oil of mirbane sulfuryl) ethane is in the alkali aqueous solution of 0.5-10% in concentration, according to alkali and 1, the mol ratio of 2-two (3 '-oil of mirbane sulfuryl) ethane is 1: 0.8-10, temperature of reaction is 40-100 ℃, carry out basic hydrolysis, after hydrolysis fully, cooling, filter, obtain 3-(β-hydroxyethyl sulfone)-oil of mirbane filter cake; Concentrating filter liquor, crystallisation by cooling can get 3-oil of mirbane-sulfinate.
2, according to the described by product 1 of claim 1, the method for hydrolysis of 2-two (3 '-oil of mirbane sulfuryl) ethane is characterized in that the used alkali of basic hydrolysis is sodium hydroxide, potassium hydroxide, calcium hydroxide, yellow soda ash or salt of wormwood.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03178523 CN1244555C (en) | 2003-07-17 | 2003-07-17 | Method for hydrolysis of 1,2-bis(3'-nitrobenzene sulphone group )ethane byproduced in the production of 3-(beta-hydroxy ethylsulphonyl)nitrobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03178523 CN1244555C (en) | 2003-07-17 | 2003-07-17 | Method for hydrolysis of 1,2-bis(3'-nitrobenzene sulphone group )ethane byproduced in the production of 3-(beta-hydroxy ethylsulphonyl)nitrobenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1569826A CN1569826A (en) | 2005-01-26 |
| CN1244555C true CN1244555C (en) | 2006-03-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 03178523 Expired - Lifetime CN1244555C (en) | 2003-07-17 | 2003-07-17 | Method for hydrolysis of 1,2-bis(3'-nitrobenzene sulphone group )ethane byproduced in the production of 3-(beta-hydroxy ethylsulphonyl)nitrobenzene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103553988A (en) * | 2013-10-12 | 2014-02-05 | 浙江闰土研究院有限公司 | Synthetic method of 3-(beta-hydroxyethyl sulfonyl)-nitrobenzene |
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- 2003-07-17 CN CN 03178523 patent/CN1244555C/en not_active Expired - Lifetime
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Effective date of registration: 20090109 Address after: Zip code, Yan tou development area, Jiaojiang District, Taizhou, Zhejiang, China: 318000 Co-patentee after: DALIAN University OF TECHNOLOGY Patentee after: TAIZHOU ZHENGANG DYESTUFF Co.,Ltd. Address before: No. 83 Jiefang North Road, Jiaojiang District, Zhejiang, Taizhou Province: 318000 Co-patentee before: Dalian University of Technology Patentee before: Donggang Industry & Trade Group Co.,Ltd. |
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Owner name: TAIZHOU CITY ZHENGANG DYEING MATERIAL CHEMICAL CO. Free format text: FORMER OWNER: DONGGANG INDUSTRY AND TRADE GROUP CO., LTD. Effective date: 20090109 |
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Application publication date: 20050126 Assignee: TAIZHOU QIANJIN CHEMICAL CO.,LTD. Assignor: DALIAN University OF TECHNOLOGY|TAIZHOU ZHENGANG DYESTUFF Co.,Ltd. Contract record no.: 2013330000126 Denomination of invention: Hydrolysis method of by-product 1,2- bis (3 '- nitrobenzene sulfone) ethane in the preparation of 3- (beta hydroxy) - nitrobenzene Granted publication date: 20060308 License type: Exclusive License Record date: 20130506 |
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