CN101870667A - Synthesis method of sodium nonanoyloxy benzene sulfonate - Google Patents
Synthesis method of sodium nonanoyloxy benzene sulfonate Download PDFInfo
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- CN101870667A CN101870667A CN200910097898A CN200910097898A CN101870667A CN 101870667 A CN101870667 A CN 101870667A CN 200910097898 A CN200910097898 A CN 200910097898A CN 200910097898 A CN200910097898 A CN 200910097898A CN 101870667 A CN101870667 A CN 101870667A
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Abstract
The invention discloses a synthesis method of sodium nonanoyloxy benzene sulfonate, which comprises the following steps that: first, azelaic acid and phosphorus trichloride react under the condition of no solvent to generate an intermediate pelargonyl chloride; then xylene and tetrachloroethane serve as the solvent, tetrabutylammonium bromide serves as a phase-transfer catalyst, and hydroxy sodium chloride and pelargonyl chloride react and reflux for 3 to 6h; cooling the materials to room temperature, filtering after solid is precipitated, and recycling filtrate; and flushing the obtained solid with the recycled filtrate for a plurality of times and then drying to obtain a sodium nonanoyloxy benzene sulfonate product. The synthesis method of sodium nonanoyloxy benzene sulfonate adopts xylene and tetrachloroethane as the mixed solvent, improves the compatibility of reactant, is beneficial to increasing the contact area for the reactant to react, correspondingly improves the reaction probability, greatly improves the product yield, recycles the solvent as the mother liquor, not only saves the production cost, but also improves the product yield. The yield of the product to the sodium nonanoyloxy benzene sulfonate product can reach above 96 percent.
Description
Technical field
The present invention relates to the synthetic field of acyl compounds, particularly a kind of synthetic method to acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems.
Background technology
Be that using maximum in the SYNTHETIC OPTICAL WHITNER is sodium peroxide and Sodium peroxoborate at present at oxygen, but because these two kinds of SYNTHETIC OPTICAL WHITNER have stronger thermostability, has only competence exertion bleaching action when surpassing more than 70 ℃, and a lot of fabrics particularly the fabric of synthon class all can not adapt to, the low-temperature activation agent that therefore must add superoxide reduces its bleaching temperature.
Acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (NOBS) is a kind of use low-temperature activation agent of superoxide comparatively widely, and is stronger than perhydroxyl radical ionic bleaching activity at low temperatures, easy and H
2O
2Solution reaction generates the acid of peroxidation fat.The acid of peroxidation fat is at H
2O
2Play the special role of transmitting available oxygen in the bleaching process, its advantage is water-soluble big, and temperature of reaction is lower, and the whiteness of bleaching is higher.The ninth of the ten Heavenly Stems, the pure product of acyloxy benzene sulfonic acid sodium salt were white powder, and its structural formula is as follows:
To the ninth of the ten Heavenly Stems acyloxy benzene sulfonic acid sodium salt be raw material, synthetic as reaction solvent with n-nonanoic acid, thionyl chloride, p-hydroxy benzenyl sulfonate sodium usually with single organic solvents such as Benzene Chloride, benzene, toluene or tetrahydrofuran (THF)s, yield is not high, substantially about 85%, and the toxicity of these organic solvents is bigger, also can cause certain pollution to environment.
Chinese patent application 200710071082.9 discloses a kind of synthetic method of alkanoyloxy benzene sulfonate, under solvent-free condition, react the generation acyl chlorides by organic carboxyl acid and thionyl chloride, again acyl chlorides and p-hydroxybenzenyl sulfonate salt are reacted in alkali and tetrahydrofuran (THF) mixing solutions, concentration of reaction solution, the refrigeration crystallization, the centrifuging oven dry obtains product alkyloyloxyethyl benzene sulfonic acid sodium salt, and productive rate is 88.49%.This method is synthesized NOBS by aqueous phase solvent, and yield is not high, and also has difficulties aspect the centrifugal and oven dry at product, is difficult to granulation, and solvent mother liquor can't recycled, and the sewage of discharging is more relatively.
European patent EP 402043 discloses the preparation method of acyloxy benzene sulfonic acid sodium salt in a kind of ninth of the ten Heavenly Stems, a DHBS and pelargonyl chloride is reacted obtain 84% acyloxy benzene sulfonic acid sodium salt product in the ninth of the ten Heavenly Stems in xylene solvent.Because the polarity of dimethylbenzene and p-hydroxy benzenyl sulfonate sodium differs greatly, the reaction probability of DHBS and pelargonyl chloride between this has influenced to a certain extent makes the product yield not high.
Summary of the invention
At above-mentioned situation, the object of the present invention is to provide a kind of have advantages such as product yield height, environmental protection to acyloxy benzene sulfonic acid sodium salt synthetic method in the ninth of the ten Heavenly Stems.With n-nonanoic acid, phosphorus trichloride, p-hydroxy benzenyl sulfonate sodium is raw material, and by at first synthetic pelargonyl chloride intermediate, reaction generates acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems again.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of synthetic method to acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems is characterized in that may further comprise the steps:
A. be 1: 1～2 under solvent-free condition with n-nonanoic acid and phosphorus trichloride with mol ratio, 20～60 ℃ of reactions refluxed 1～3 hour, and air distillation goes out unnecessary phosphorus trichloride, and underpressure distillation makes the intermediate pelargonyl chloride then;
B. with dimethylbenzene and tetrachloroethane make solvent, Tetrabutyl amonium bromide is made phase-transfer catalyst, p-hydroxy benzenyl sulfonate sodium is mixed according to mol ratio 1: 1～3 with step a gained pelargonyl chloride, 145 ℃ down reaction refluxed 3～6 hours; After reaction is finished material is cooled to room temperature, treats to carry out suction filtration, filtrate recycle after solid is separated out; With the gained solid with the recycled filtrate flushing for several times, oven dry must be to acyloxy benzene sulfonic acid sodium salt product in the ninth of the ten Heavenly Stems.
Further, the temperature of reaction of n-nonanoic acid and phosphorus trichloride is preferably 40 ℃ among the step a, and reacting reflux time is preferably 2 hours.
The mass ratio of dimethylbenzene and tetrachloroethane is 1: 1 among the step b.
In the process of pelargonyl chloride and p-hydroxy benzenyl sulfonate sodium reaction, adopt dimethylbenzene and tetrachloroethane to make mixed solvent, according to " similar compatibility " principle, this mixed solvent makes the consistency between the reactant that raising preferably arranged, help increasing the contact area that reactant reacts, correspondingly improved the reaction probability, so product yield significantly improves.Relatively poor because of the consistency of dimethylbenzene, tetrachloroethane and water, after reaction was finished, solvent was handled through simple, also can be used as Recycling Mother Solution and applies mechanically, and has not only saved production cost, and has improved product yield.According to the inventive method, the yield of acyloxy benzene sulfonic acid sodium salt product can reach more than 96% to the ninth of the ten Heavenly Stems.
Embodiment
Embodiment 1:
(1) pelargonyl chloride is synthetic:
In the there-necked flask that reflux condensing tube, constant pressure funnel and thermometer are housed, add the 15.82g n-nonanoic acid, begin to stir, drip 20.63g phosphorus trichloride (PCl under the room temperature
3), the control rate of addition dropwises about 30min, is warmed up to react about 20 ℃ to reflux 2 hours, and air distillation goes out unnecessary PCl
3, steam the cut of pelargonyl chloride correspondence then by underpressure distillation, obtain product pelargonyl chloride 17.38g, yield is 98.5%.
(2) synthesizing acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (NOBS):
Add the 19.6g p-hydroxy benzenyl sulfonate sodium in four-hole boiling flask, 33ml dimethylbenzene and 67ml tetrachloroethane (mass ratio is 1: 1) slowly drip the 26.48g pelargonyl chloride under the room temperature, dropwise to add the 0.4g Tetrabutyl amonium bromide, are warming up to about 145 ℃ and reflux 4 hours.The hydrogen chloride gas of water absorption reaction generation simultaneously; After reaction is finished material is cooled to room temperature, treats to carry out suction filtration, filtrate recycle after solid is separated out; With the gained solid with the recycled filtrate flushing for several times, oven dry must be to acyloxy benzene sulfonic acid sodium salt product 28.56g in the ninth of the ten Heavenly Stems.Reclaim solvent 98ml altogether, after testing, dimethylbenzene and tetrachloroethane mass ratio are 1: 1 in the recovered solvent.
Yield to acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (NOBS) is 96.5%.
Embodiment 2:
(1) pelargonyl chloride is synthetic:
Add the 15.82g n-nonanoic acid in the there-necked flask that reflux condensing tube, constant pressure funnel and thermometer are housed, begin to stir, room temperature drips 27.5g PCl
3, the control rate of addition dropwises about 30min, is warmed up to react about 40 ℃ to reflux 3 hours, and air distillation goes out unnecessary PCl
3, steam the cut of pelargonyl chloride correspondence then by underpressure distillation, obtain product pelargonyl chloride 17.54g, yield is 99.4%.
(2) synthesizing acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (NOBS):
Add reuse solvent mother liquor among 19.6g p-hydroxy benzenyl sulfonate sodium, the 98ml embodiment 1 in the four-hole boiling flask, corresponding again interpolation dimethylbenzene and tetrachloroethane 2ml (according to mass ratio 1: 1).Slow Dropwise 35 .5g pelargonyl chloride under the room temperature dropwises adding 0.4g Tetrabutyl amonium bromide, is warming up to about 145 ℃ and refluxes 4 hours.The hydrogen chloride gas of water absorption reaction generation simultaneously; After reaction is finished material is cooled to room temperature, treats to carry out suction filtration, filtrate recycle after solid is separated out; With the gained solid with the recycled filtrate flushing for several times, oven dry must be to acyloxy benzene sulfonic acid sodium salt product 29.48g in the ninth of the ten Heavenly Stems.Reclaim solvent 98ml.
Yield to acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (NOBS) is 99.6%.
Embodiment 3:
(1) pelargonyl chloride is synthetic:
Add the 15.82g n-nonanoic acid in the there-necked flask that reflux condensing tube, constant pressure funnel and thermometer are housed, begin to stir, room temperature drips 13.75g PCl
3, the control rate of addition dropwises about 30min, is warmed up to react about 60 ℃ to reflux 2 hours, and air distillation goes out unnecessary PCl
3, steam the cut of pelargonyl chloride correspondence then by underpressure distillation, obtain product pelargonyl chloride 17.58g, yield is 99.6%.
(2) synthesizing acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (NOBS):
Add the 19.6g p-hydroxy benzenyl sulfonate sodium in the four-hole boiling flask, use reuse solvent mother liquor among the embodiment 2, corresponding again interpolation dimethylbenzene and tetrachloroethane 2ml (according to mass ratio 1: 1).Slowly drip the 44.0g pelargonyl chloride under the room temperature, dropwise adding 0.4g Tetrabutyl amonium bromide, be warming up to about 145 ℃ and refluxed 4 hours.The hydrogen chloride gas of water absorption reaction generation simultaneously; After reaction is finished material is cooled to room temperature, treats to carry out suction filtration, filtrate recycle after solid is separated out; With the gained solid with the recycled filtrate flushing for several times, oven dry must be to acyloxy benzene sulfonic acid sodium salt product 29.54g in the ninth of the ten Heavenly Stems.
Yield to acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (NOBS) is 99.8%.
Claims (3)
1. synthetic method to acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems is characterized in that may further comprise the steps:
A. be 1: 1～2 under solvent-free condition with n-nonanoic acid and phosphorus trichloride with mol ratio, 20～60 ℃ of reactions refluxed 1～3 hour, and air distillation goes out unnecessary phosphorus trichloride, and underpressure distillation makes the intermediate pelargonyl chloride then;
B. with dimethylbenzene and tetrachloroethane make solvent, Tetrabutyl amonium bromide is made phase-transfer catalyst, p-hydroxy benzenyl sulfonate sodium is mixed according to mol ratio 1: 1～3 with step a gained pelargonyl chloride, 145 ℃ down reaction refluxed 3～6 hours; After reaction is finished material is cooled to room temperature, treats to carry out suction filtration, filtrate recycle after solid is separated out; With the gained solid with the recycled filtrate flushing for several times, oven dry must be to acyloxy benzene sulfonic acid sodium salt product in the ninth of the ten Heavenly Stems.
2. the synthetic method to acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems as claimed in claim 1, it is characterized in that among the step a n-nonanoic acid and phosphorus trichloride 40 ℃ down reaction refluxed 2 hours.
3. the synthetic method to acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems as claimed in claim 1 is characterized in that the mass ratio of dimethylbenzene and tetrachloroethane is 1: 1 among the step b.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875425A (en) * | 2012-08-29 | 2013-01-16 | 昆山铁牛衬衫厂 | Preparation method of low-temperature oxidizing assistant |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4704236A (en) * | 1985-09-28 | 1987-11-03 | Interox Chemicals Ltd. | Preparation of sulphophenyl esters |
| US5069828A (en) * | 1989-06-06 | 1991-12-03 | E. I. Du Pont De Nemours And Company | Process for preparing benzenesulfonate salts |
| US20030064906A1 (en) * | 2001-08-11 | 2003-04-03 | Clariant Gmbh | Process for the preparation of acyloxybenzenesulfonates |
| US20040198995A1 (en) * | 2003-01-14 | 2004-10-07 | Clariant Gmbh | Process for preparing acyloxybenzenesulfonates |
| CN101139310A (en) * | 2007-09-04 | 2008-03-12 | 浙江理工大学 | Method for synthesizing albifaction activator alkyl acylorxy radical benzene sulfonate |
-
2009
- 2009-04-23 CN CN200910097898A patent/CN101870667A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4704236A (en) * | 1985-09-28 | 1987-11-03 | Interox Chemicals Ltd. | Preparation of sulphophenyl esters |
| US5069828A (en) * | 1989-06-06 | 1991-12-03 | E. I. Du Pont De Nemours And Company | Process for preparing benzenesulfonate salts |
| US20030064906A1 (en) * | 2001-08-11 | 2003-04-03 | Clariant Gmbh | Process for the preparation of acyloxybenzenesulfonates |
| US20040198995A1 (en) * | 2003-01-14 | 2004-10-07 | Clariant Gmbh | Process for preparing acyloxybenzenesulfonates |
| CN101139310A (en) * | 2007-09-04 | 2008-03-12 | 浙江理工大学 | Method for synthesizing albifaction activator alkyl acylorxy radical benzene sulfonate |
Non-Patent Citations (2)
| Title |
|---|
| VALITOVA, L. A.等: "Interaction of phosphorous trichloride with carboxylic acids", 《IZV. AKAD. NAUK SSSR, SER. KHIM.》 * |
| 张进等: "三氯化磷法合成三甲基乙酰氯的研究", 《沈阳化工学院学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875425A (en) * | 2012-08-29 | 2013-01-16 | 昆山铁牛衬衫厂 | Preparation method of low-temperature oxidizing assistant |
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Effective date of registration: 20110224 Address after: 312369 Shangyu Industrial Park, Hangzhou Bay, Zhejiang Province Applicant after: Zhejiang Jinke Commodity Chemcial Raw Materials Co., Ltd. Address before: 312369 Hangzhou Bay Fine Chemical Industry Park, Zhejiang, Shangyu Applicant before: Zhejiang Jinke Chemicals Co., Ltd. |
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