CN102875383A - Synthetic method of methylparaben - Google Patents
Synthetic method of methylparaben Download PDFInfo
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- CN102875383A CN102875383A CN2012103466339A CN201210346633A CN102875383A CN 102875383 A CN102875383 A CN 102875383A CN 2012103466339 A CN2012103466339 A CN 2012103466339A CN 201210346633 A CN201210346633 A CN 201210346633A CN 102875383 A CN102875383 A CN 102875383A
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- tegosept
- synthetic method
- hydroxybenzoic acid
- methylparaben
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Abstract
The invention provides a synthetic method of methylparaben. The synthetic method comprises the steps as follows: adding p-hydroxybenzoic acid and excessive methanol to a three-port bottle which is provided with an agitating device, a reflux condenser and a thermometer, wherein the ratio of amount of substance of the p-hydroxybenzoic acid to the methanol is 1:(3-5) and the mass ratio of chitosan sulfate to the p-hydroxybenzoic acid is 0.8% to 1.2%; heating to carry out reflux for 4 to 6 hours; then stopping the reaction; slightly cooling; filtering the reacting liquid to separate the chitosan sulfate; processing the reacting liquid in a reduced pressure distillation way; collecting fraction at 104 to 105 DEG C, to obtain the rough product; transferring the rough product into a round-bottom flask with a reflux condensing pipe; adding proper methanol so as to completely dissolve the methylparaben during heating; cooling; and then adding proper active carbon to slightly boil for a moment; then filtering while the mixture is hot; cooling and crystallizing the filtrate; leaching; washing with water; drying in the air; and parching, so as to obtain the methylparaben. The methylparaben synthesized by the synthetic method provided by the invention has the yield up to 93.1%; and the chitosan sulfate catalyst has high catalyzing activity and reusability when being used for synthesizing the methylparaben.
Description
Technical field
The invention belongs to the organic chemical synthesis field, be specifically related to a kind of synthetic method of Tegosept M.
Background technology
Nipagin esters can be used for the anticorrosion of food and medicine and makeup, and its feature is that toxicity is lower than Sodium Benzoate, and bacteriostatic action and pH value are irrelevant, and antimicrobial spectrum is wide, and is therefore extremely important to the seriation research of this series products.The Tegosept E ester synthesis is with P-hydroxybenzoic acid and alcohol reaction, and this reaction can be carried out catalysis with sulfuric acid, tosic acid, aluminium salt, resin, solid super-strong acid, heteropolyacid, mixing acid etc. and finishes, and every kind of catalyzer has its characteristics.
Chitosan Sulfate is the modified product of chitosan, has wide practical use.Compare with traditional catalyzer, Chitosan Sulfate has following advantage: reaction conditions is gentle, is easy to control; Catalytic activity is strong, and selectivity is high, and consumption is few, can avoid the generation of side reaction, and productive rate is high; Catalyst performance stabilised, repeatedly reusable; Aftertreatment is easy, has avoided waste water to the pollution of environment with to the corrosion of equipment.
Summary of the invention
The invention provides a kind of synthetic method of new Tegosept M, take Chitosan Sulfate as catalyzer, catalyzed and synthesized Tegosept M.
The chitosan of getting after the pulverizing places there-necked flask, adds massfraction and be 0.33% NaOH solution.Under stirring, the oil bath heating in 120 ℃ of boiling reflux 3h, is washed to neutrality, and 60 ℃ of oven dry in electrically heated drying cabinet obtain chitosan with high deacetylation degree; High deacetylized chitosan and the vitriol oil are added in the there-necked flask, bathe high speed stirring reaction 3h at cryosel, stop to stir, transfer to NaOH and add people's ethanol after the neutrality and continue to precipitate 1h in cryosel is bathed, centrifugal suction filtration is with a large amount of distilled water washs removal impurity Na
2SO
4, filter cake 70 ℃ of oven dry, is obtained Chitosan Sulfate.
Agitator is being housed, in the there-necked flask of reflux exchanger and thermometer, according to molar ratio 1:3～5 add P-hydroxybenzoic acid and excessive methyl alcohol and with the P-hydroxybenzoic acid mass ratio be 0.8～1.2% Chitosan Sulfate, reflux 4～6h, finish reaction, slightly cold, filtering reacting liquid is isolated Chitosan Sulfate, the underpressure distillation reaction solution, collect 104～105 ℃ cut, get crude product, put in the round-bottomed flask of people with reflux condensing tube, add an amount of methyl alcohol of people, make when heating Tegosept M can all dissolve, an amount of little the boiling a moment of gac of adding after the cooling, filtered while hot, the filtrate crystallisation by cooling, suction filtration, washing, hang, oven dry obtains Tegosept M.
The molar ratio 1:4 of preferred P-hydroxybenzoic acid and methyl alcohol.
The consumption of preferred Chitosan Sulfate is 0.9% of P-hydroxybenzoic acid quality.
Preferred each reactant reflux 4h.
Compare with the synthetic method of traditional Tegosept M, the Tegosept M that synthetic method of the present invention is synthetic, product yield reaches 93.1%, and this chitosan sulfate catalyst has good catalytic activity and reusability for the synthesis of Tegosept M.
Embodiment
Below in conjunction with embodiment the synthetic method of Tegosept M of the present invention is described in detail, thereby so that advantages and features of the invention can be easier to be it will be appreciated by those skilled in the art that protection scope of the present invention is made more explicit defining.
The raw material reagent that the present invention is used: chitosan, technical grade; Other are commercially available analytical pure or chemical pure and through Non-aqueous processing.
Embodiment 1
The chitosan of getting after 10g pulverizes places there-necked flask, and adding 150mL massfraction is 0.33% NaOH solution.Under agitation condition, with the oil bath heating, in 120 ℃ of boiling reflux 3h.Then wash with water to neutrality, 60 ℃ of oven dry obtain chitosan with high deacetylation degree in electrically heated drying cabinet.
Get the high deacetylized chitosan of 5g and the 70mL vitriol oil and add in the there-necked flask, bathe high speed stirring reaction 3h at cryosel.Then stop to stir, transfer to NaOH and add people 35mL ethanol after the neutrality and continue to precipitate 1h in cryosel is bathed, centrifugal suction filtration is with a large amount of distilled water washs removal impurity Na
2SO
4, filter cake 70 ℃ of oven dry, is obtained Chitosan Sulfate 5.33g, productive rate 80.39%.
In the 250mL there-necked flask of agitator, reflux exchanger and thermometer is housed, add 15.19g (0.11mol) P-hydroxybenzoic acid and the methyl alcohol of 0.33mol and the Chitosan Sulfate of 0.12g, reflux 5h.Finish reaction, slightly cold, filtering reacting liquid is isolated Chitosan Sulfate, the underpressure distillation reaction solution, and the cut of collection 104～105 ℃ (5.2kPa) gets crude product.The Tegosept M crude product is put in the round-bottomed flask of people with reflux condensing tube, is added an amount of methyl alcohol of people, make when heating Tegosept M can all dissolve.Add after the cooling that an amount of gac is little to boil a moment filtered while hot.The filtrate crystallisation by cooling, suction filtration, washing hangs, and oven dry obtains Tegosept M 14.61g, transformation efficiency 88.04%, m.P.126～127 ℃, ignition residue 0.04%.
Embodiment 2
The chitosan of getting after 10g pulverizes places there-necked flask, and adding 150mL massfraction is 0.33% NaOH solution.Under agitation condition, with the oil bath heating, in 120 ℃ of boiling reflux 3h.Then wash with water to neutrality, 60 ℃ of oven dry obtain chitosan with high deacetylation degree in electrically heated drying cabinet.
Get the high deacetylized chitosan of 5g and the 70mL vitriol oil and add in the there-necked flask, bathe high speed stirring reaction 3h at cryosel.Then stop to stir, transfer to NaOH and add people 35mL ethanol after the neutrality and continue to precipitate 1h in cryosel is bathed, centrifugal suction filtration is with a large amount of distilled water washs removal impurity Na
2SO
4, filter cake 70 ℃ of oven dry, is obtained Chitosan Sulfate 5.33g, productive rate 80.39%.
In the 250mL there-necked flask of agitator, reflux exchanger and thermometer is housed, add 15.19g (0.11mol) P-hydroxybenzoic acid and the methyl alcohol of 0.55mol and the Chitosan Sulfate of 0.18g, reflux 6h.Finish reaction, slightly cold, filtering reacting liquid is isolated Chitosan Sulfate, the underpressure distillation reaction solution, and the cut of collection 104～105 ℃ (5.2kPa) gets crude product.The Tegosept M crude product is put in the round-bottomed flask of people with reflux condensing tube, is added an amount of methyl alcohol of people, make when heating Tegosept M can all dissolve.Add after the cooling that an amount of gac is little to boil a moment filtered while hot.The filtrate crystallisation by cooling, suction filtration, washing hangs, and oven dry obtains Tegosept M 14.65g, transformation efficiency 88.12%, m.P.126～127 ℃, ignition residue 0.04%.
Embodiment 3
The chitosan of getting after 10g pulverizes places there-necked flask, and adding 150mL massfraction is 0.33% NaOH solution.Under agitation condition, with the oil bath heating, in 120 ℃ of boiling reflux 3h.Then wash with water to neutrality, 60 ℃ of oven dry obtain chitosan with high deacetylation degree in electrically heated drying cabinet.
Get the high deacetylized chitosan of 5g and the 70mL vitriol oil and add in the there-necked flask, bathe high speed stirring reaction 3h at cryosel.Then stop to stir, transfer to NaOH and add people 35mL ethanol after the neutrality and continue to precipitate 1h in cryosel is bathed, centrifugal suction filtration is with a large amount of distilled water washs removal impurity Na
2SO
4, filter cake 70 ℃ of oven dry, is obtained Chitosan Sulfate 5.33g, productive rate 80.39%.
In the 250mL there-necked flask of agitator, reflux exchanger and thermometer is housed, add 15.19g (0.11mol) P-hydroxybenzoic acid and the methyl alcohol of 0.44mol and the Chitosan Sulfate of 0.14g, reflux 4h.Finish reaction, slightly cold, filtering reacting liquid is isolated Chitosan Sulfate, the underpressure distillation reaction solution, and the cut of collection 104～105 ℃ (5.2kPa) gets crude product.The Tegosept M crude product is put in the round-bottomed flask of people with reflux condensing tube, is added an amount of methyl alcohol of people, make when heating Tegosept M can all dissolve.Add after the cooling that an amount of gac is little to boil a moment filtered while hot.The filtrate crystallisation by cooling, suction filtration, washing hangs, and oven dry obtains Tegosept M 14.81g, transformation efficiency 88.47%, m.P.126～127 ℃, ignition residue 0.04%.
Compare with the synthetic method of traditional Tegosept M, the Tegosept M that synthetic method of the present invention is synthetic, product yield reaches 93.1%, and this chitosan sulfate catalyst has good catalytic activity and reusability for the synthesis of Tegosept M.
Claims (4)
1. the synthetic method of a Tegosept M, it may further comprise the steps:
Agitator is being housed, in the there-necked flask of reflux exchanger and thermometer, according to molar ratio 1:3～5 add P-hydroxybenzoic acid and excessive methyl alcohol and with the P-hydroxybenzoic acid mass ratio be 0.8～1.2% Chitosan Sulfate, reflux 4～6h, finish reaction, slightly cold, filtering reacting liquid is isolated Chitosan Sulfate, the underpressure distillation reaction solution, collect 104～105 ℃ cut, get crude product, put in the round-bottomed flask of people with reflux condensing tube, add an amount of methyl alcohol of people, make when heating Tegosept M can all dissolve, an amount of little the boiling a moment of gac of adding after the cooling, filtered while hot, the filtrate crystallisation by cooling, suction filtration, washing, hang, oven dry obtains Tegosept M.
2. the synthetic method of Tegosept M according to claim 1 is characterized in that: the molar ratio 1:4 of described P-hydroxybenzoic acid and methyl alcohol.
3. the synthetic method of Tegosept M according to claim 1, it is characterized in that: the consumption of described Chitosan Sulfate is 0.9% of P-hydroxybenzoic acid quality.
4. the synthetic method of Tegosept M according to claim 1 is characterized in that: described each reactant reflux 4h.
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|---|---|---|---|
| CN2012103466339A CN102875383A (en) | 2012-09-18 | 2012-09-18 | Synthetic method of methylparaben |
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| CN2012103466339A CN102875383A (en) | 2012-09-18 | 2012-09-18 | Synthetic method of methylparaben |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108684686A (en) * | 2018-06-13 | 2018-10-23 | 合肥同佑电子科技有限公司 | A kind of mould inhibitor and preparation method thereof for cable material |
| CN109879753A (en) * | 2019-03-05 | 2019-06-14 | 陕西科技大学 | A method of preparing paraben esters |
| CN109970557A (en) * | 2019-03-26 | 2019-07-05 | 陕西科技大学 | A method of preparing paraben esters |
-
2012
- 2012-09-18 CN CN2012103466339A patent/CN102875383A/en not_active Withdrawn
Non-Patent Citations (2)
| Title |
|---|
| 尹大伟等: "壳聚糖硫酸盐催化合成尼泊金甲酯", 《精细石油化工》 * |
| 陈秀宇等: "壳聚糖硫酸盐的催化酯化反应研究进展", 《福建师范大学福清分院学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108684686A (en) * | 2018-06-13 | 2018-10-23 | 合肥同佑电子科技有限公司 | A kind of mould inhibitor and preparation method thereof for cable material |
| CN109879753A (en) * | 2019-03-05 | 2019-06-14 | 陕西科技大学 | A method of preparing paraben esters |
| CN109970557A (en) * | 2019-03-26 | 2019-07-05 | 陕西科技大学 | A method of preparing paraben esters |
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Application publication date: 20130116 |