CN102617411A - Synthesis method of N-ethyl-N(3'-sulfo) benzyl aniline - Google Patents
Synthesis method of N-ethyl-N(3'-sulfo) benzyl aniline Download PDFInfo
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- CN102617411A CN102617411A CN2012100663068A CN201210066306A CN102617411A CN 102617411 A CN102617411 A CN 102617411A CN 2012100663068 A CN2012100663068 A CN 2012100663068A CN 201210066306 A CN201210066306 A CN 201210066306A CN 102617411 A CN102617411 A CN 102617411A
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Abstract
The invention provides a synthesis method of N-ethyl-N(3'-sulfo) benzyl aniline. N-ethyl-N-benzyl aniline is added into a reaction device, 20 percent to 30 percent fuming sulphuric acid is started to be dripped at 72 DEG C to 78 DEG C, the weight ratio of the N-ethyl-N-benzyl aniline to SO3 in the fuming sulphuric acid is 1:(0.36-0.45), the highest temperature in the dripping process does not exceed 95 DEG C, the dripping time is 1.5 to 2 hours, the heat insulation lasts for 0.5 to 1.0 hour after the dripping completion, the temperature is lowered to the room temperature, then, reaction liquid is slowly diluted into water, when the mass percentage concentration of the sulphuric acid in the water reaches 18 percent to 28 percent, the temperature is lowered to the room temperature so that the materials are naturally separated out, centrifugation filtering, water washing and drying are carried out, and finished products are obtained. The process has the advantages that the quality of products is improved, the purity of the products can reach higher than 99 percent, the back work period adopts the water adding dilution so that the materials are separated out, three wastes are reduced, the filter liquid can be recovered to be cyclically utilized, and the process is more perfect and environment-friendly.
Description
Technical field
The present invention relates to the compound method of N-ethyl-N (3 ＇-sulfonic group) benzylaniline.
Background technology
N-ethyl-N (3 ＇-sulfonic group) benzylaniline is a kind of white or off-white color solid, and it of many uses mainly is used as high-grade dyestuff and medicine intermediate, is a kind of important matching stain midbody.Matching stain is a painted dyestuff in acidic medium, and great majority contain sulfonate sodium, can be water-soluble, and lovely luster, chromatogram is complete.Be mainly used in wool, silk and nylon dyeing, also can be used for the painted of aspects such as leather, paper, ink.No matter matching stain is output or kind quantity, all in dyestuff market, occupies crucial status.Because existing production technique is to drip oleum at 25-32 ℃, drips time 4-5 hour, because the dropping time is long; Temperature is low, in the process that drips, constantly has material to separate out and is bonded at a pot wall; Cause the local reaction temperature too high like this, react inhomogeneous and cause product two sulfonated bodies content higher, surpass 2%; Can not meet all requirement of client, and this technology workshop section's employing sodium hydroxide neutralization reaction liquid after production, material is separated out; Have a large amount of sodium sulfate to produce like this in the mother liquor, discharging can produce pollutes.
Summary of the invention
The present invention is in order to overcome above-mentioned deficiency; A kind of compound method of polluting little, that purity is high N-ethyl-N (3 ＇-sulfonic group) benzylaniline is provided, and main innovation is, changes the temperature and the speed that drip N-ethyl-Phenhenzamine; Shorten the dropping time; N-ethyl-N (3 ＇-sulfonic group) benzylaniline to guarantee in reaction process, to generate is non-crystallizable at the reactor wall, makes reaction evenly, thereby has avoided that the reaction local temperature is too high, reaction is inhomogeneous and it is higher to generate two sulfonated bodies content; On the other hand through changing the method that back workshop section separates out material with the sodium hydroxide neutralization; Use a reaction solution instead and slowly be diluted in the water, the vitriolic percentage concentration in the control water is lowered the temperature when 18%-28%; Material is separated out naturally, centrifuging then, wash wet article.Filtrating has not only been improved the quality of product, and has been avoided the generation of sodium sulfate through concentrating recovery set usefulness.It specifically is to implement like this: the compound method of N-ethyl-N (3 ＇-sulfonic group) benzylaniline; It is characterized in that N-ethyl-Phenhenzamine is joined in the reaction unit; Under 72 ℃-78 ℃, begin to drip the oleum of 20%-30%, SO in said N-ethyl-Phenhenzamine and the oleum
3Weight ratio be 1:0.36-0.45, top temperature is no more than 95 ℃ in the dropping process, the dropping time is 1.5-2 hour; Drip back insulation 0.5-1.0 hour; Cool to room temperature, slowly be diluted to reaction solution in the water then, when the vitriolic mass percentage concentration in the water reaches 18%-28%; Be cooled to room temperature material is separated out naturally, get finished product after centrifuging, washing, the drying.
When the present invention drips oleum, be controlled at the oleum that drips 65-75% in 1 hour earlier, in 0.5-1.0 hour, drip remaining oleum then.Can shorten the reaction times like this, avoid the generation of two sulfonated bodiess, guarantee that the outward appearance of product is better.If it is slow that the front dripped in one hour, the back drips fast, and two sulfonated bodiess are increased, and reduces the quality of product; If totally drip overlong time, can make the product colour jaundice, influence outward appearance.
In this reaction and since oleum activity stronger, ethyl-the Phenhenzamine time can not be oversize for dropping N-under comparatively high temps, otherwise by product increases, the best dropping time of this reaction is 1.5-2 hour.
In this reaction, SO in N-ethyl-Phenhenzamine and the oleum
3The best proportioning of weight ratio be 1:0.36-0.45, if proportioning is too small, can cause raw material N-ethyl-Phenhenzamine reaction not thorough, cause wastage of material, proportioning is excessive, can cause two sulfonated to take place.
After reaction finished, being diluted to the vitriolic mass percentage concentration to reaction solution was 18%-28%, if concentration is low excessively, it is doubly a lot of that the water yield is increased, and strengthens recovery difficult, and influential to product purity; Excessive concentration, it is few to cause product to separate out, and reduces the yield of product.
The present invention is added drop-wise to quantitative oleum and carries out addition reaction in N-ethyl-Phenhenzamine under comparatively high temps and in the short period; Accomplished the synthetic of N-ethyl-N (3 ＇-sulfonic group) benzylaniline; Improved the quality of product, product gas purity can reach more than 99%; Back workshop section adopts thin up that material is separated out, and has reduced the three wastes, and filtrating can be reclaimed recycled, technology lean environmental protection more.
Embodiment
Embodiment 1, in the four-hole reaction flask that the 500ml band stirs, adds 100 gram ethyl-Phenhenzamines, the oleum 180 gram (SO in N-ethyl-Phenhenzamine and the oleum of weighing 20%
3Weight ratio be 1:0.36); Join in the constant voltage addition funnel of 250ml; Be warmed up to 75 ℃ to the N-ethyl-Phenhenzamine in the reaction flask then, begin to drip oleum, drip top temperature and be no more than 95 ℃; Remain on the oleum that drips 117 grams (65%) in 1st hour, remaining 68 grams (35%) dripped in 0.5-1 hour.Be incubated 0.5 hour then, cool to room temperature, reaction solution constantly stir and the situation of cooling under be diluted to that (the vitriolic mass percentage concentration in the water reaches 18%-19% in the 650 gram water;), drop to room temperature then, treat that fully stirring material separates out after; Filter; Filter cake is washed, dries to such an extent that finished product N-ethyl-N (3 ＇-sulfonic group) benzylaniline 135.6 restrains content 99.36%, yield 98.3%.
Embodiment 2, in the four-hole reaction flask that the 500ml band stirs, add 100 gram ethyl-Phenhenzamines, at the oleum gram 160 gram (SO in N-ethyl-Phenhenzamine and the oleum of weighing 25%
3Weight ratio be 1:0.4); Join in the constant voltage addition funnel of 250ml; Be warmed up to 72 ℃ to the N-ethyl-Phenhenzamine in the reaction flask then, begin to drip oleum, drip top temperature and be no more than 95 ℃; Remain on the oleum that drips 112 grams (70%) in 1st hour, remaining 48 grams (30%) dripped in 0.5-1 hour.Be incubated 0.5 hour then; Cool to room temperature, under the situation that constantly stirs and lower the temperature, be diluted to reaction solution in the 450 gram water (the vitriolic mass percentage concentration in the water reaches 21-22%), drop to room temperature then; After treating that fully stirring material separates out; Filter cake is washed, dries to such an extent that finished product N-ethyl-N (3 ＇-sulfonic group) benzylaniline 136.1 restrains content 99.30%, yield 98.7%.
Embodiment 3, in the four-hole reaction flask that the 500ml band stirs, add 100 gram ethyl-Phenhenzamines, at the oleum 140 gram (SO in N-ethyl-Phenhenzamine and the oleum of weighing 30%
3Weight ratio be 1:0.42); Join in the constant voltage addition funnel of 250ml; Be warmed up to 78 ℃ to the N-ethyl-Phenhenzamine in the reaction flask then, begin to drip oleum, drip top temperature and be no more than 95 ℃; Remain on the oleum that drips 105 grams (75%) in 1st hour, remaining 35 grams (25%) dripped in 0.5-1 hour.Be incubated 0.5 hour then, cool to room temperature, under the situation that constantly stirs and lower the temperature, be diluted to reaction solution in the 350 gram water (the vitriolic mass percentage concentration in the water reaches 23-24%); Drop to room temperature then; After treating that fully stirring material separates out, filter, filter cake is washed, dries to such an extent that finished product N-ethyl-N (3 ＇-sulfonic group) benzylaniline 136.4 restrains; Content 99.25%, yield 98.9%.
Embodiment 4, in the four-hole reaction flask that the 500ml band stirs, add 100 gram ethyl-Phenhenzamines, at the oleum 200 gram (SO in N-ethyl-Phenhenzamine and the oleum of weighing 20%
3Weight ratio be 1:0.4); Join in the constant voltage addition funnel of 250ml; Be warmed up to 75 ℃ to the N-ethyl-Phenhenzamine in the reaction flask then, begin to drip oleum, drip top temperature and be no more than 95 ℃; Remain on the oleum that drips 136 grams (68%) in 1st hour, remaining 68 grams (32%) dripped in 0.5-1 hour.Be incubated 0.5 hour then; Cool to room temperature, reaction solution constantly stir and the situation of cooling under be diluted in the 500 gram water (the vitriolic percentage concentration in the water reaches 25-26%), treat that fully stirring material separates out after; Filter; Filter cake is washed, dries to such an extent that finished product N-ethyl-N (3 ＇-sulfonic group) benzylaniline 136.8 restrains content 99.2%, yield 99.2%.
Embodiment 5, in the four-hole reaction flask that the 500ml band stirs, add 100 gram ethyl-Phenhenzamines, at the oleum 180 gram (SO in N-ethyl-Phenhenzamine and the oleum of weighing 25%
3Weight ratio be 1:0.45); Join in the constant voltage addition funnel of 250ml; Be warmed up to 75 ℃ to the N-ethyl-Phenhenzamine in the reaction flask then, begin to drip oleum, drip top temperature and be no more than 95 ℃; Remain on the oleum that drips 135 grams (75%) in 1st hour, remaining 45 grams (25%) dripped in 0.5-1 hour.Be incubated 0.5 hour then; Cool to room temperature; Under the situation of continuous stirring and cooling, be diluted to reaction solution in the 350 gram water (vitriolic mass percentage concentration 27-28% in the water), filter, filter cake is washed, dries to such an extent that finished product N-ethyl-N (3 ＇-sulfonic group) benzylaniline 137.3 restrains; Content 99.16%, yield 99.5%.
Claims (2)
1.N-the compound method of ethyl-N (3 ＇-sulfonic group) benzylaniline; It is characterized in that N-ethyl-Phenhenzamine is joined in the reaction unit; Under 72 ℃-78 ℃, begin to drip the oleum of 20%-30%, SO in said N-ethyl-Phenhenzamine and the oleum
3Weight ratio be 1:0.36-0.45, top temperature is no more than 95 ℃ in the dropping process, the dropping time is 1.5-2 hour; Drip back insulation 0.5-1.0 hour; Cool to room temperature, slowly be diluted to reaction solution in the water then, when the vitriolic mass percentage concentration in the water reaches 18%-28%; Be cooled to room temperature material is separated out naturally, get finished product after centrifuging, washing, the drying.
2. the compound method of N-ethyl-N according to claim 1 (3 ＇-sulfonic group) benzylaniline; When it is characterized in that dripping oleum; Be controlled at the oleum that drips 65-75% in 1 hour earlier, in 0.5-1.0 hour, drip remaining oleum then.
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| CN2012100663068A CN102617411A (en) | 2012-03-14 | 2012-03-14 | Synthesis method of N-ethyl-N(3'-sulfo) benzyl aniline |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348150A (en) * | 2015-09-25 | 2016-02-24 | 恒升化工有限公司 | Clean production process for N-ethly-N-(3'-sulfoacid) benzyl aniline |
| CN111170896A (en) * | 2019-12-31 | 2020-05-19 | 恒升化工有限公司 | Preparation method of N-ethyl-N- (3' -sulfonic acid) benzylaniline |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4552951A (en) * | 1984-01-23 | 1985-11-12 | Eastman Kodak Company | Disperse and acid azo dyes having one or two cinnamoyl substituents on a phenyl diazonium moiety and containing an aniline, tetrahydroquinoline or benzomorpholine coupler |
| US4593087A (en) * | 1983-10-07 | 1986-06-03 | Eastman Kodak Company | Disperse and acid azo dyes having one or two cinnamoyl substituents on a thiazole, isothiazole or thiadiazole diazonium moiety and having an aniline, tetrahydroquinoline or benzomorpholine coupler |
| EP0293744A1 (en) * | 1987-06-01 | 1988-12-07 | BASF Aktiengesellschaft | Process for recovering benzolmonosulfonic acids from aqueous solutions or suspensions |
-
2012
- 2012-03-14 CN CN2012100663068A patent/CN102617411A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4593087A (en) * | 1983-10-07 | 1986-06-03 | Eastman Kodak Company | Disperse and acid azo dyes having one or two cinnamoyl substituents on a thiazole, isothiazole or thiadiazole diazonium moiety and having an aniline, tetrahydroquinoline or benzomorpholine coupler |
| US4552951A (en) * | 1984-01-23 | 1985-11-12 | Eastman Kodak Company | Disperse and acid azo dyes having one or two cinnamoyl substituents on a phenyl diazonium moiety and containing an aniline, tetrahydroquinoline or benzomorpholine coupler |
| EP0293744A1 (en) * | 1987-06-01 | 1988-12-07 | BASF Aktiengesellschaft | Process for recovering benzolmonosulfonic acids from aqueous solutions or suspensions |
Non-Patent Citations (1)
| Title |
|---|
| 丁秋龙 等，: "N-乙基-N-苄基间磺酸胺中异构体的分离研究", 《染料与染色》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348150A (en) * | 2015-09-25 | 2016-02-24 | 恒升化工有限公司 | Clean production process for N-ethly-N-(3'-sulfoacid) benzyl aniline |
| CN111170896A (en) * | 2019-12-31 | 2020-05-19 | 恒升化工有限公司 | Preparation method of N-ethyl-N- (3' -sulfonic acid) benzylaniline |
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Application publication date: 20120801 |