CN104003839A - Preparation method of cinnamic acid or derivatives thereof - Google Patents
Preparation method of cinnamic acid or derivatives thereof Download PDFInfo
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- CN104003839A CN104003839A CN201410245147.7A CN201410245147A CN104003839A CN 104003839 A CN104003839 A CN 104003839A CN 201410245147 A CN201410245147 A CN 201410245147A CN 104003839 A CN104003839 A CN 104003839A
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- C07C67/00—Preparation of carboxylic acid esters
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- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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Abstract
The invention discloses a preparation method of cinnamic acid or derivatives thereof. The method comprises the following steps: adding a dichloromethane solution of triethyl phosphonoacetate, sodium chloride and raw material aldehyde into a reaction container, performing room-temperature reaction, adding a saturated water solution of ammonium chloride, stirring, performing organic phase washing, performing reduced pressure treatment to remove a solvent, and performing column chromatography purification to obtain a light yellow oily product; adding a mixed solution of dichloromethane and methanol into a reaction product, stirring, dropwise adding a methanol solution of sodium hydroxide to generate a large quantity of turbid materials, performing reduced pressure distillation on a reaction solution until the reaction solution is dry, removing impurities, extracting, combining organic phases, drying, performing reduced pressure treatment to remove the solvent, and drying in vacuum to obtain a white or light yellow product. According to the method, triethyl phosphonoacetate is adopted as an activating reagent for condensation esterification with aldehyde and then the product is conveniently prepared through alkaline hydrolysis; the reaction can be carried out at room temperature, and the shortcomings of low yield, high reaction temperature, high toxicity and serious pollution in a conventional process are overcome.
Description
Technical field
The present invention relates to a kind of preparation method of industrial chemicals, particularly a kind of preparation method of styracin or derivatives thereof.
Background technology
Styracin has another name called TRANSCINNAMIC ACID, cinnamic acid, 1, and 3-phenylacrylic acid is one of important organic synthesis Industrial intermediates.Except self, can do spices, be widely used in medicine, plastics, foodstuff additive, prepare photosensitive resin etc.In medicine industry, for the synthesis of satisfying fixed, the mepramidil of the important drugs lactic acid for the treatment of coronary heart disease and the heart, can pacify, and synthetic Spinax and Stutgin; Can be used to manufacture local anesthetic, sterilant, hemostatic drug etc.; Or the effective inhibitor of human lung adenocarcinoma cell, has great using value at anticancer aspect.
In technology, the main synthetic method of styracin has: (1) phenyl aldehyde and diacetyl oxide condensation method (Perkin method) now; (2) phenyl aldehyde-acetone method; (3) benzylidene chloride-sodium acetate, anhydrous method; (4) vinylbenzene-carbon tetrachloride method; (5) phenylacrolein is oxidized to Chinese cassia tree acid system; (6) phenyl aldehyde and propanedioic acid method (Knoevenagel method) etc.Wherein Perkin method and the application of Knoevenagel method are the most general.
Perkin method be take phenyl aldehyde and diacetyl oxide and condensation reaction synthesizing cinnamic acid is occurred under basic catalyst catalysis as raw material, and its reaction scheme is as follows:
Perkin method is because diacetyl oxide activity is low, and temperature of reaction is high, the time is long, causes productive rate low (55%~70%), and phenyl aldehyde need to reclaim by steam distillation, and cost is high, and suitability for industrialized production exists certain drawback.
It is raw material condensation reaction synthesizing cinnamic acid under base catalysis that Knoevenagel method be take phenyl aldehyde and propanedioic acid, and its reaction scheme is as follows:
It is catalyzer that Knoevenagel method need be selected pyridine, piperidines etc., and its strong impulse produces detrimentally affect to neural system and respiratory tract, and it is difficult that phenyl aldehyde and pyridine, piperidines reclaim, and discharge brings serious environmental pollution, and industry's enlarging production exists certain difficulty.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, a kind of high yield is provided, pollutes the preparation method of little styracin or derivatives thereof.
Technical problem to be solved by this invention can also further realize by following technical scheme.The present invention is a kind of preparation method of styracin or derivatives thereof, is characterized in, its step is as follows:
(1) esterification: to the dichloromethane solution that adds phosphine acyl acetic acid three ethyl in reaction vessel, under-5~5 ℃ of stirrings, slowly add sodium hydride, be warming up to 20~30 ℃, add fast raw material aldehyde, room temperature reaction 2~6 hours, add the saturated aqueous solution of ammonium chloride to stir, organic phase is washed with saturated sodium bicarbonate solution, saturated nacl aqueous solution successively, removal of solvent under reduced pressure, and column chromatography purification obtains faint yellow oily matter;
In esterification, the ratio of the amount of raw material is, aldehyde: phosphine acyl acetic acid three ethyl: sodium hydride=1:1.2~1.8:2.5~3.5;
Described aldehyde is selected from phenyl aldehyde, aubepine, 4-chloro-benzaldehyde, p-Fluorobenzenecarboxaldehyde, 2 thiophene carboxaldehyde;
(2) hydrolysis reaction: above walk and add the mixing solutions of methylene dichloride and methyl alcohol to stir in reaction product, the methanol solution that drips sodium hydroxide makes to produce a large amount of muddinesses, after 1.5~3 hours, evaporated under reduced pressure reaction solution, adds water dissolution, and impurity is removed in isopropyl ether extraction, water regulates pH to 2~3, dichloromethane extraction, merges organic phase, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, vacuum-drying obtains white or light yellow product;
In hydrolysis reaction, in the mixing solutions of methylene dichloride and methyl alcohol, the volume ratio of methylene dichloride and methyl alcohol is 8~10:1, and the concentration of methanol solution of sodium hydroxide is 1~3mol/L.
The preparation method of styracin or derivatives thereof of the present invention, its preferred technical scheme steps is as follows:
(1) esterification: to the dichloromethane solution that adds phosphine acyl acetic acid three ethyl in reaction vessel, under 0 ℃ of stirring, slowly add sodium hydride, be warming up to room temperature, add fast raw material aldehyde, room temperature reaction 2~6 hours, add the saturated aqueous solution of ammonium chloride to stir, organic phase is washed with saturated sodium bicarbonate solution, saturated nacl aqueous solution successively, removal of solvent under reduced pressure, and column chromatography purification obtains faint yellow oily matter;
In esterification, the ratio of the amount of raw material is, aldehyde: phosphine acyl acetic acid three ethyl: sodium hydride=1:1.5:3;
(2) hydrolysis reaction: above walk and add the mixing solutions of methylene dichloride and methyl alcohol to stir in reaction product, the methanol solution that drips sodium hydroxide makes to produce a large amount of muddinesses, after 2 hours, evaporated under reduced pressure reaction solution, adds water dissolution, and impurity is removed in isopropyl ether extraction, water regulates pH to 2~3, dichloromethane extraction, merges organic phase, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, vacuum-drying obtains white or light yellow product;
In hydrolysis reaction, in the mixing solutions of methylene dichloride and methyl alcohol, the volume ratio of methylene dichloride and methyl alcohol is 9:1, and the concentration of methanol solution of sodium hydroxide is 2mol/L.
In the preparation method of styracin or derivatives thereof of the present invention, further preferred technical characterictic is:
1. in hydrolysis reaction, regulating pH solution used is 1mol/L aqueous hydrochloric acid;
2. in esterification, the reaction times follows the tracks of to detect according to TLC and determines, TLC developping agent volume ratio used is ethyl acetate: sherwood oil=1:5.
3. during removal of solvent under reduced pressure, reduced pressure is to-0.06Pa~-0.09Pa by atmospheric depressurized.
4. involved extracting operation in method, all through 3 extractions, the volume of each extraction agent used is original solution 2 times.
5. in the anhydrous sodium sulfate drying described in hydrolysis reaction, the consumption of anhydrous sodium sulphate is as the criterion not produce caking.
6. in esterification, involved column chromatography operates, and developping agent volume ratio is in ethyl acetate: sherwood oil=1:5.
Preparation method's of the present invention synthetic route is as follows:
wherein R group is respectively:
a:
b:
c:
d:
e:
The present invention adopts phosphine acyl acetic acid three ethyl as activating reagent and aldehyde condensation esterification, after by basic hydrolysis, conveniently make product, reaction all can at room temperature be carried out, and has overcome that traditional technology yield is low, temperature of reaction is high, toxicity is large, with serious pollution shortcoming.
Compared with prior art, the inventive method obviously improves compared with Perkin method yield, and avoids pyroreaction, easy and simple to handle, cost.Compare with Knoevenagel method, avoided the use of toxicity catalyzer, overcome the problem of raw materials recovery difficulty.
Accompanying drawing explanation
Fig. 1-Fig. 5 is the product that makes of the inventive method
1hNMR spectrogram.
Embodiment
Referring to accompanying drawing, further describe concrete technical scheme of the present invention, so that those skilled in the art understands the present invention further, and do not form the restriction to its right.
Embodiment 1, a kind of preparation method of styracin or derivatives thereof, and its step is as follows:
(1) esterification: to the dichloromethane solution that adds phosphine acyl acetic acid three ethyl in reaction vessel, under-5 ℃ of stirrings, slowly add sodium hydride, be warming up to 20 ℃, add fast raw material aldehyde, room temperature reaction 2~6 hours, add the saturated aqueous solution of ammonium chloride to stir, organic phase is washed with saturated sodium bicarbonate solution, saturated nacl aqueous solution successively, removal of solvent under reduced pressure, and column chromatography purification obtains faint yellow oily matter;
In esterification, the ratio of the amount of raw material is, aldehyde: phosphine acyl acetic acid three ethyl: sodium hydride=1:1.2:2.5;
Described aldehyde is selected from phenyl aldehyde, aubepine, 4-chloro-benzaldehyde, p-Fluorobenzenecarboxaldehyde, 2 thiophene carboxaldehyde;
(2) hydrolysis reaction: above walk and add the mixing solutions of methylene dichloride and methyl alcohol to stir in reaction product, the methanol solution that drips sodium hydroxide makes to produce a large amount of muddinesses, after 1.5 hours, evaporated under reduced pressure reaction solution, adds water dissolution, and impurity is removed in isopropyl ether extraction, water regulates pH to 2, dichloromethane extraction, merges organic phase, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, vacuum-drying obtains white or light yellow product;
In hydrolysis reaction, in the mixing solutions of methylene dichloride and methyl alcohol, the volume ratio of methylene dichloride and methyl alcohol is 8:1, and the concentration of methanol solution of sodium hydroxide is 1mol/L.
Embodiment 2, a kind of preparation method of styracin or derivatives thereof, and its step is as follows:
(1) esterification: to the dichloromethane solution that adds phosphine acyl acetic acid three ethyl in reaction vessel, under 5 ℃ of stirrings, slowly add sodium hydride, be warming up to 30 ℃, add fast raw material aldehyde, room temperature reaction 2~6 hours, add the saturated aqueous solution of ammonium chloride to stir, organic phase is washed with saturated sodium bicarbonate solution, saturated nacl aqueous solution successively, removal of solvent under reduced pressure, and column chromatography purification obtains faint yellow oily matter;
In esterification, the ratio of the amount of raw material is, aldehyde: phosphine acyl acetic acid three ethyl: sodium hydride=1:1.8:3.5;
Described aldehyde is selected from phenyl aldehyde, aubepine, 4-chloro-benzaldehyde, p-Fluorobenzenecarboxaldehyde, 2 thiophene carboxaldehyde;
(2) hydrolysis reaction: above walk and add the mixing solutions of methylene dichloride and methyl alcohol to stir in reaction product, the methanol solution that drips sodium hydroxide makes to produce a large amount of muddinesses, after 3 hours, evaporated under reduced pressure reaction solution, adds water dissolution, and impurity is removed in isopropyl ether extraction, water regulates pH to 3, dichloromethane extraction, merges organic phase, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, vacuum-drying obtains white or light yellow product;
In hydrolysis reaction, in the mixing solutions of methylene dichloride and methyl alcohol, the volume ratio of methylene dichloride and methyl alcohol is 10:1, and the concentration of methanol solution of sodium hydroxide is 3mol/L.
Embodiment 3, a kind of preparation method of styracin or derivatives thereof, and its step is as follows:
(1) esterification: to the dichloromethane solution that adds phosphine acyl acetic acid three ethyl in reaction vessel, under 0 ℃ of stirring, slowly add sodium hydride, be warming up to room temperature, add fast raw material aldehyde, room temperature reaction 2~6 hours, add the saturated aqueous solution of ammonium chloride to stir, organic phase is washed with saturated sodium bicarbonate solution, saturated nacl aqueous solution successively, removal of solvent under reduced pressure, and column chromatography purification obtains faint yellow oily matter;
In esterification, the ratio of the amount of raw material is, aldehyde: phosphine acyl acetic acid three ethyl: sodium hydride=1:1.5:3;
Described aldehyde is selected from phenyl aldehyde, aubepine, 4-chloro-benzaldehyde, p-Fluorobenzenecarboxaldehyde, 2 thiophene carboxaldehyde;
(2) hydrolysis reaction: above walk and add the mixing solutions of methylene dichloride and methyl alcohol to stir in reaction product, the methanol solution that drips sodium hydroxide makes to produce a large amount of muddinesses, after 2 hours, evaporated under reduced pressure reaction solution, adds water dissolution, and impurity is removed in isopropyl ether extraction, water regulates pH to 2~3, dichloromethane extraction, merges organic phase, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, vacuum-drying obtains white or light yellow product;
In hydrolysis reaction, in the mixing solutions of methylene dichloride and methyl alcohol, the volume ratio of methylene dichloride and methyl alcohol is 9:1, and the concentration of methanol solution of sodium hydroxide is 2mol/L.
Embodiment 4, and in the preparation method's of the styracin or derivatives thereof of embodiment 1-3 described in any one hydrolysis reaction, regulating pH solution used is 1mol/L aqueous hydrochloric acid.
Embodiment 5, and in the preparation method's of the styracin or derivatives thereof of embodiment 1-4 described in any one esterification, the reaction times follows the tracks of to detect according to TLC and determines, TLC developping agent volume ratio used is ethyl acetate: sherwood oil=1:5.
Embodiment 6, and in the preparation method of the styracin or derivatives thereof of embodiment 1-5 described in any one, during removal of solvent under reduced pressure, reduced pressure is to-0.06Pa~-0.09Pa by atmospheric depressurized.
Embodiment 7, in the preparation method of the styracin or derivatives thereof of embodiment 1-6 described in any one, involved extracting operation, all through 3 extractions, the volume of each extraction agent used is original solution 2 times.
Embodiment 8, and in the anhydrous sodium sulfate drying described in the preparation method's of the styracin or derivatives thereof of embodiment 1-7 described in any one hydrolysis reaction, the consumption of anhydrous sodium sulphate is as the criterion not produce caking.
Embodiment 9, involved column chromatography operation in the preparation method's of the styracin or derivatives thereof of embodiment 1-8 described in any one esterification, and developping agent volume ratio is ethyl acetate: sherwood oil=1:5.
Embodiment 10, preparation method's experiment of styracin or derivatives thereof:
(1) esterification: in the round-bottomed flask of 100mL, accurately weigh and add phosphine acyl acetic acid three ethyl 7.5mmol, add 10mL methylene dichloride to dissolve, magnetic agitation, at 0 ℃, slowly add sodium hydride 15mmol, be warming up to room temperature, add fast raw material aldehyde (1a~1e, be followed successively by phenyl aldehyde, aubepine, 4-chloro-benzaldehyde, p-Fluorobenzenecarboxaldehyde, 2 thiophene carboxaldehyde) 5mmol, TLC follows the tracks of detection reaction process, after finishing, reaction add saturated ammonium chloride solution 10mL to stir layering, organic phase is used saturated sodium bicarbonate solution successively, saturated nacl aqueous solution washing, removal of solvent under reduced pressure, column chromatography purification obtains faint yellow oily matter.
(2) hydrolysis reaction: get step reaction product 5mmol, add methylene dichloride 36mL, methyl alcohol 4mL, the methanol solution 4mL that adds 2 mol/L sodium hydroxide under stirring, room temperature reaction, after 2 hours, removal of solvent under reduced pressure, adds water 20mL and dissolves, and the ester of hydrolysis is removed in isopropyl ether extraction, water regulates pH to 2~3, dichloromethane extraction, merges organic phase, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, vacuum-drying obtains white or light yellow product.Product is through fusing point test, and nuclear-magnetism, Mass Spectrometric Identification are defined as target product.
Styracin (product
3a): total recovery 92%; 131~133 ℃ of fusing points; MS:148.1(M
+);
1hNMR(CDCl
3): δ=6.46(d, 1H, CH=); 7.4(m, 3H, Ar-H); 7.56(d, 2H, Ar-H); 7.80(d, 1H, CH=).Referring to Fig. 1.
P-methoxycinnamic acid (product
3b): total recovery 98%; 172~173 ℃ of fusing points; MS:178.0(M
+);
1hNMR(CDCl
3): δ=3.85(s, 3H, CH
3o); 6.32(d, 1H, CH=); 6.91(t, 2H, Ar-H); 7.50(t, 2H, Ar-H); 7.74(d, 1H, CH=).Referring to Fig. 2.
To chloro-cinnamic acid (product
3c): total recovery>=99%; 247~249 ℃ of fusing points; MS:182.0(M
+);
1hNMR(CDCl
3): δ=6.41(d, 1H, CH=); 7.29(s, 1H, Ar-H); 7.36(t, 2H, Ar-H); 7.48(d, 1H, Ar-H); 7.72(d, 1H, CH=).Referring to Fig. 3.
To fluoro cinnamic acid (product
3d): total recovery 93%; 209~210 ℃ of fusing points; MS:166.0(M
+);
1hNMR(CDCl
3): δ=6.37(d, 1H, CH=); 7.31(m, 2H, Ar-H); 7.53(q, 2H, Ar-H); 7.75(d, 1H, CH=).Referring to Fig. 4.
3-(2-thiophene) vinylformic acid (product
3e): total recovery 95%; 145~147 ℃ of fusing points; MS:154.1(M
+);
1hNMR(CDCl
3): δ=6.24(d, 1H, CH=); 7.07(m, 1H, CH=); 7.30(t, 1H, CH=); 7.42(d, 1H, CH=); 7.89(d, 1H, CH=).Referring to Fig. 5.
Claims (8)
1. a preparation method for styracin or derivatives thereof, is characterized in that, its step is as follows:
(1) esterification: to the dichloromethane solution that adds phosphine acyl acetic acid three ethyl in reaction vessel, under-5~5 ℃ of stirrings, slowly add sodium hydride, be warming up to 20~30 ℃, add fast raw material aldehyde, room temperature reaction 2~6 hours, add the saturated aqueous solution of ammonium chloride to stir, organic phase is washed with saturated sodium bicarbonate solution, saturated nacl aqueous solution successively, removal of solvent under reduced pressure, and column chromatography purification obtains faint yellow oily matter;
In esterification, the ratio of the amount of raw material is, aldehyde: phosphine acyl acetic acid three ethyl: sodium hydride=1:1.2~1.8:2.5~3.5;
Described aldehyde is selected from phenyl aldehyde, aubepine, 4-chloro-benzaldehyde, p-Fluorobenzenecarboxaldehyde, 2 thiophene carboxaldehyde;
(2) hydrolysis reaction: above walk and add the mixing solutions of methylene dichloride and methyl alcohol to stir in reaction product, the methanol solution that drips sodium hydroxide makes to produce a large amount of muddinesses, after 1.5~3 hours, evaporated under reduced pressure reaction solution, adds water dissolution, and impurity is removed in isopropyl ether extraction, water regulates pH to 2~3, dichloromethane extraction, merges organic phase, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, vacuum-drying obtains white or light yellow product;
In hydrolysis reaction, in the mixing solutions of methylene dichloride and methyl alcohol, the volume ratio of methylene dichloride and methyl alcohol is 8~10:1, and the concentration of methanol solution of sodium hydroxide is 1~3mol/L.
2. the preparation method of styracin or derivatives thereof according to claim 1, is characterized in that, its step is as follows:
(1) esterification: to the dichloromethane solution that adds phosphine acyl acetic acid three ethyl in reaction vessel, under 0 ℃ of stirring, slowly add sodium hydride, be warming up to room temperature, add fast raw material aldehyde, room temperature reaction 2~6 hours, add the saturated aqueous solution of ammonium chloride to stir, organic phase is washed with saturated sodium bicarbonate solution, saturated nacl aqueous solution successively, removal of solvent under reduced pressure, and column chromatography purification obtains faint yellow oily matter;
In esterification, the ratio of the amount of raw material is, aldehyde: phosphine acyl acetic acid three ethyl: sodium hydride=1:1.5:3;
(2) hydrolysis reaction: above walk and add the mixing solutions of methylene dichloride and methyl alcohol to stir in reaction product, the methanol solution that drips sodium hydroxide makes to produce a large amount of muddinesses, after 2 hours, evaporated under reduced pressure reaction solution, adds water dissolution, and impurity is removed in isopropyl ether extraction, water regulates pH to 2~3, dichloromethane extraction, merges organic phase, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, vacuum-drying obtains white or light yellow product;
In hydrolysis reaction, in the mixing solutions of methylene dichloride and methyl alcohol, the volume ratio of methylene dichloride and methyl alcohol is 9:1, and the concentration of methanol solution of sodium hydroxide is 2mol/L.
3. the preparation method of styracin or derivatives thereof according to claim 1 and 2, is characterized in that: in hydrolysis reaction, regulating pH solution used is 1mol/L aqueous hydrochloric acid.
4. the preparation method of styracin or derivatives thereof according to claim 1 and 2, is characterized in that: in esterification, the reaction times follows the tracks of to detect according to TLC and determines, TLC developping agent volume ratio used is ethyl acetate: sherwood oil=1:5.
5. the preparation method of styracin or derivatives thereof according to claim 1 and 2, is characterized in that: during removal of solvent under reduced pressure, reduced pressure is to-0.06Pa~-0.09Pa by atmospheric depressurized.
6. the preparation method of styracin or derivatives thereof according to claim 1 and 2, is characterized in that: involved extracting operation in method, all through 3 extractions, the volume of each extraction agent used is original solution 2 times.
7. the preparation method of styracin or derivatives thereof according to claim 1 and 2, is characterized in that: in the anhydrous sodium sulfate drying described in hydrolysis reaction, the consumption of anhydrous sodium sulphate is as the criterion not produce caking.
8. the preparation method of styracin or derivatives thereof according to claim 1 and 2, is characterized in that: column chromatography involved in esterification operates, and developping agent volume ratio is ethyl acetate: sherwood oil=1:5.
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CN105124716A (en) * | 2015-07-23 | 2015-12-09 | 广西科技大学 | Method of preparing food preservative through extraction waste liquid of cinnamon oil |
CN106146296A (en) * | 2015-04-21 | 2016-11-23 | 昆药集团股份有限公司 | A kind of preparation method of caffeic acid derivative |
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CN102850317A (en) * | 2011-06-27 | 2013-01-02 | 天士力制药集团股份有限公司 | Substituted cinnamide derivative, its preparation method and application |
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Cited By (4)
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CN106146296A (en) * | 2015-04-21 | 2016-11-23 | 昆药集团股份有限公司 | A kind of preparation method of caffeic acid derivative |
CN106146296B (en) * | 2015-04-21 | 2019-02-26 | 昆药集团股份有限公司 | A kind of preparation method of caffeic acid derivative |
CN105124716A (en) * | 2015-07-23 | 2015-12-09 | 广西科技大学 | Method of preparing food preservative through extraction waste liquid of cinnamon oil |
CN105124716B (en) * | 2015-07-23 | 2018-07-17 | 广西科技大学 | The method for preparing food preservative using Chinese cassia tree oil extract waste liquid |
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