CN105985228A - Method for synthesizing 3-(4-methyl benzene methylene) camphor - Google Patents
Method for synthesizing 3-(4-methyl benzene methylene) camphor Download PDFInfo
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- CN105985228A CN105985228A CN201510093937.2A CN201510093937A CN105985228A CN 105985228 A CN105985228 A CN 105985228A CN 201510093937 A CN201510093937 A CN 201510093937A CN 105985228 A CN105985228 A CN 105985228A
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- methyl benzylidene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a method for synthesizing 3-(4-methyl benzene methylene) camphor. The method comprises the following steps that firstly, camphor, a reaction solvent and an immobilized catalyst KOH/Al2O3 are added into a reaction container; secondly, the temperature is raised to a reaction temperature, and p-tolualdehyde is added dropwise; thirdly, after the reaction is finished, the immobilized catalyst KOH/Al2O3 is removed through filtration, washing is carried out through saturated brine, drying is carried out through magnesium sulfate, and the reaction solvent is recycled at normal pressure; fourthly, recrystallization is carried out through an ethanol solution, and by means of drying treatment, the product is obtained. The method for synthesizing the 3-(4-methyl benzene methylene) camphor through the immobilized catalyst KOH/Al2O3 in a catalyzing mode is simple and easy to implement, little liquid waste is caused, the catalyst is recycled easily, and the yield can reach 85%. The purity of the 3-(4-methyl benzene methylene) camphor prepared through the recrystallization post-treatment method can reach 99.5%.
Description
Technical field
The present invention relates to the synthesis of 3-(4-methyl benzylidene) Camphora, specifically use supported catalyst KOH/Al2O3Catalysis Camphora and p-tolyl aldehyde generation aldol reaction, the method obtaining 3-(4-methyl benzylidene) Camphora.
Background technology
Along with the reinforcement of health perception, people's living standard improves constantly, and the luxury goods that cosmetics have maintained from a kind of skin protection become necessary, and wherein sun care preparations occupies critical role especially.Sun care preparations has been not limited to use summer, the most all need sun-proof, sun care preparations adds sunscreen, it it is the ultraviolet in order to absorb in the sun, making human body skin exempt from the sunburn of ultraviolet, OXYBENZONE, ethylhexyl methoxy cinnamate, octocrilene (in terms of acid), 3-(4-methyl benzylidene) Camphora etc. are all conventional component of sun.
3-(4-methyl benzylidene) Camphora is good oil-soluble UV absorber, adds and just can improve SPF (sun protection factor) value on a small quantity, is effective light stabilizer, and this character has made it the organic UV sunscreen commonly used in the commercially available cosmetic that organises.Thus the research to 3-(4-methyl benzylidene) Camphora has important reality and theory significance.Report about the synthesis of 3-(4-methyl benzylidene) Camphora is little at present, and only Takao Saito et al. is at Archive for Organic
Chemistry, 2004 (ii): 152-171 report that employing potassium tert-butoxide synthesizes 3-(4-methyl benzylidene) Camphora as catalyst, but the method complex process, inconvenient operation.
Summary of the invention
It is an object of the invention to find the route of a kind of synthesis 3-(4-methyl benzylidene) Camphora, it is provided that a kind of reaction condition is gentle, easily operated, the 3-of good product purity (4-methyl benzylidene) Camphora preparation method.
The method of synthesis 3-(4-methyl benzylidene) Camphora of the present invention, comprises the steps:
(1) in reaction bulb, add a certain proportion of Camphora, reaction dissolvent and supported catalyst KOH/ A l2O3；
(2) it is warming up to reaction temperature, drips p-tolyl aldehyde；
(3), after reaction terminates, it is filtered to remove supported catalyst KOH/Al2O3, saturated aqueous common salt washs, and magnesium sulfate is dried, and normal pressure reclaims reaction dissolvent；
(4) using ethanol water recrystallization, drying processes and obtains product.
In optimal technical scheme of the present invention, supported catalyst KOH/ A l in step (1)2O3For the 20 ~ 50% of Camphora mole, reaction dissolvent is the one in the tert-butyl alcohol, normal heptane, normal hexane, hexamethylene or ethanol；The amount of reaction dissolvent is 2 ~ 3L/mol of Camphora.
In optimal technical scheme of the present invention, in step (2), reaction temperature is 50 ~ 78 DEG C, and p-tolyl aldehyde is the 50 ~ 100% of Camphora mole, and the response time is 2 ~ 5 h；Drop rate is not higher than 5 drops/sec.
In optimal technical scheme of the present invention, in step (4), baking temperature is not higher than 70 DEG C.
Compared with prior art, the invention have the advantage that
(1) supported catalyst KOH/ A l is used2O3Method is simple for Camphora to catalyze and synthesize 3-(4-methyl benzylidene), and waste liquid is few, and catalyst easily reclaims, and yield can reach 85%.
(2) use 3-(4-methyl benzylidene) the Camphora purity that the post-processing approach of recrystallization prepares up to 99.5%.
Detailed description of the invention
The following examples can make those skilled in the art that the present invention is more fully understood, but limits the present invention never in any form.
Embodiment 1
By 4.56 g Camphoras, 0.948 g supported catalyst KOH/ A l2O3, the 60 mL tert-butyl alcohols be added in the four-hole boiling flask equipped with agitator and thermometer, be heated to 78 DEG C, drip 3.60 g p-tolyl aldehydes, drop rate is not higher than 5 drops/sec.React 4 h.Reaction is filtered to remove supported catalyst KOH/ A l after terminating2O3, saturated aqueous common salt washs, and magnesium sulfate is dried, normal pressure recycling design.Ethanol water recrystallization, dried obtains product, and productivity is 56.8%, and gas chromatographic analysis 3-(4-methyl benzylidene) Camphora purity is 99.50%.
Embodiment 2
By 4.56 g Camphoras, 1.422 g supported catalyst KOH/ A l2O3, the 60 mL tert-butyl alcohols be added in the four-hole boiling flask equipped with agitator and thermometer, be heated to 78 DEG C, be slowly added dropwise 3.60 g p-tolyl aldehydes, drop rate is not higher than 5 drops/sec.React 4 h.Reaction is filtered to remove supported catalyst KOH/ A l after terminating2O3, saturated aqueous common salt washs, and magnesium sulfate is dried, normal pressure recycling design.Ethanol water recrystallization, dried obtains product, and productivity is 76.8%, and gas chromatographic analysis 3-(4-methyl benzylidene) Camphora purity is 99.48%.
Embodiment 3
By 4.56 g Camphoras, 2.370 g supported catalyst KOH/ A l2O3, the 60 mL tert-butyl alcohols be added in the four-hole boiling flask equipped with agitator and thermometer, be heated to 78 DEG C, be slowly added dropwise 3.60 g p-tolyl aldehydes, drop rate is not higher than 5 drops/sec.React 4 h.Reaction is filtered to remove supported catalyst KOH/ A l after terminating2O3, saturated aqueous common salt washs, and magnesium sulfate is dried, normal pressure recycling design.Ethanol water recrystallization, dried obtains product, and productivity is 80.0%, and gas chromatographic analysis 3-(4-methyl benzylidene) Camphora purity is 99.50%.
Embodiment 4
By 4.56 g Camphoras, 2.370 g supported catalyst KOH/ A l2O3, the 90 mL tert-butyl alcohols be added in the four-hole boiling flask equipped with agitator and thermometer, be heated to 78 DEG C, be slowly added dropwise 3.60g p-tolyl aldehyde, drop rate is not higher than 5 drops/sec.React 4 h.Reaction is filtered to remove supported catalyst KOH/ A l after terminating2O3, saturated aqueous common salt washs, and magnesium sulfate is dried, normal pressure recycling design.Ethanol water recrystallization, dried obtains product, and productivity is 81.0%, and gas chromatographic analysis 3-(4-methyl benzylidene) Camphora purity is 99.52%.
Embodiment 5
By 4.56 g Camphoras, 2.370 g supported catalyst KOH/ A l2O3, the 90 mL tert-butyl alcohols be added in the four-hole boiling flask equipped with agitator and thermometer, be heated to 50 DEG C, be slowly added dropwise 3.60g p-tolyl aldehyde, drop rate is not higher than 5 drops/sec.React 4 h.Reaction is filtered to remove supported catalyst KOH/ A l after terminating2O3, saturated aqueous common salt washs, and magnesium sulfate is dried, normal pressure recycling design.Ethanol water recrystallization, dried obtains product, and productivity is 57.0%, and gas chromatographic analysis 3-(4-methyl benzylidene) Camphora purity is 99.42%.
Embodiment 6
By 4.56 g Camphoras, 2.370 g supported catalyst KOH/ A l2O3, the 60 mL tert-butyl alcohols be added in the four-hole boiling flask equipped with agitator and thermometer, be heated to 78 DEG C, be slowly added dropwise 2.25 g p-tolyl aldehydes, drop rate is not higher than 5 drops/sec.React 4 h.Reaction is filtered to remove supported catalyst KOH/ A l after terminating2O3, saturated aqueous common salt washs, and magnesium sulfate is dried, normal pressure recycling design.Ethanol water recrystallization, dried obtains product, and productivity is 85.0%, and gas chromatographic analysis 3-(4-methyl benzylidene) Camphora purity is 99.48%
Embodiment 7
By 4.56 g Camphoras, 2.370 g supported catalyst KOH/ A l2O3, the 60 mL tert-butyl alcohols be added in the four-hole boiling flask equipped with agitator and thermometer, be heated to 78 DEG C, be slowly added dropwise 1.80 g p-tolyl aldehydes, drop rate is not higher than 5 drops/sec.React 4 h.Reaction is filtered to remove supported catalyst KOH/ A l after terminating2O3, saturated aqueous common salt washs, and magnesium sulfate is dried, normal pressure recycling design.Ethanol water recrystallization, dried obtains product, and productivity is 78.0%, and gas chromatographic analysis 3-(4-methyl benzylidene) Camphora purity is 99.49%.
Embodiment 8
By 4.56 g Camphoras, 2.370 g supported catalyst KOH/ A l2O3, the 60 mL tert-butyl alcohols be added in the four-hole boiling flask equipped with agitator and thermometer, be heated to 78 DEG C, be slowly added dropwise 2.25 g p-tolyl aldehydes, drop rate is not higher than 5 drops/sec.React 2 h.Reaction is filtered to remove supported catalyst KOH/ A l after terminating2O3, saturated aqueous common salt washs, and magnesium sulfate is dried, normal pressure recycling design.Ethanol water recrystallization, dried obtains product, and productivity is 54.0%, and gas chromatographic analysis 3-(4-methyl benzylidene) Camphora purity is 99.49%.
Embodiment 9
By 4.56 g Camphoras, 2.370 g supported catalyst KOH/ A l2O3, the 60mL tert-butyl alcohol be added in the four-hole boiling flask equipped with agitator and thermometer, be heated to 78 DEG C, be slowly added dropwise 2.25 g p-tolyl aldehydes, drop rate is not higher than 5 drops/sec.React 5 h.Reaction is filtered to remove supported catalyst KOH/ A l after terminating2O3, saturated aqueous common salt washs, and magnesium sulfate is dried, normal pressure recycling design.Ethanol water recrystallization, dried obtains product, and productivity is 85.0%, and gas chromatographic analysis 3-(4-methyl benzylidene) Camphora purity is 99.48%.
Claims (5)
1. the method for synthesis 3-(4-methyl benzylidene) Camphora, it is characterised in that comprise the steps:
(1) camphorate in reaction vessel, reaction dissolvent and supported catalyst KOH/
A l2O3；
(2) it is warming up to reaction temperature, drips p-tolyl aldehyde；
(3), after reaction terminates, it is filtered to remove supported catalyst KOH/Al2O3, saturated aqueous common salt washs, and magnesium sulfate is dried, and normal pressure reclaims reaction dissolvent；
(4) using ethanol water recrystallization, drying processes and obtains product.
The method synthesizing 3-(4-methyl benzylidene) Camphora the most as claimed in claim 1, it is characterised in that in step (1), supported catalyst KOH/ A l2O3For Camphora mole 20 ~ 50%.
The method synthesizing 3-(4-methyl benzylidene) Camphora the most as claimed in claim 1, it is characterised in that in step (1), reaction dissolvent is the one in the tert-butyl alcohol, normal heptane, normal hexane, hexamethylene or ethanol；The amount of reaction dissolvent is 2 ~ 3L/mol of Camphora.
The method synthesizing 3-(4-methyl benzylidene) Camphora the most as claimed in claim 1, it is characterised in that in step (2), reaction temperature is 50 ~ 78 DEG C, and p-tolyl aldehyde is the 50 ~ 100% of Camphora mole, and the response time is 2 ~ 5 h；Drop rate is not higher than 5 drops/sec.
The method synthesizing 3-(4-methyl benzylidene) Camphora the most as claimed in claim 1, it is characterised in that in step (4), baking temperature is not higher than 70 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107698432A (en) * | 2017-10-31 | 2018-02-16 | 宜都市华阳化工有限责任公司 | A kind of preparation method of ultra-violet absorber 3 (4 methyl benzylidene) camphor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106376C (en) * | 1996-03-13 | 2003-04-23 | Basf公司 | Cinnamylidene camphor derivatives and their use as UV-A protecting agents |
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2015
- 2015-03-03 CN CN201510093937.2A patent/CN105985228A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106376C (en) * | 1996-03-13 | 2003-04-23 | Basf公司 | Cinnamylidene camphor derivatives and their use as UV-A protecting agents |
Non-Patent Citations (1)
| Title |
|---|
| TAKAO SAITO等: "Chiral sulfide-mediated enantioselective epoxidation of aldehyde", 《ARKIVOC FOR ORGANIC CHEMISTRY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107698432A (en) * | 2017-10-31 | 2018-02-16 | 宜都市华阳化工有限责任公司 | A kind of preparation method of ultra-violet absorber 3 (4 methyl benzylidene) camphor |
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