CN103724173A - Raspberry ketone synthesis method - Google Patents
Raspberry ketone synthesis method Download PDFInfo
- Publication number
- CN103724173A CN103724173A CN201310669809.9A CN201310669809A CN103724173A CN 103724173 A CN103724173 A CN 103724173A CN 201310669809 A CN201310669809 A CN 201310669809A CN 103724173 A CN103724173 A CN 103724173A
- Authority
- CN
- China
- Prior art keywords
- raspberry ketone
- synthetic method
- reaction
- anisylacetone
- dimethylacetamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- VWMVAQHMFFZQGD-UHFFFAOYSA-N p-Hydroxybenzyl acetone Natural products CC(=O)CC1=CC=C(O)C=C1 VWMVAQHMFFZQGD-UHFFFAOYSA-N 0.000 title claims abstract description 36
- NJGBTKGETPDVIK-UHFFFAOYSA-N raspberry ketone Chemical compound CC(=O)CCC1=CC=C(O)C=C1 NJGBTKGETPDVIK-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000001308 synthesis method Methods 0.000 title abstract 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- PCBSXBYCASFXTM-UHFFFAOYSA-N 4-(4-Methoxyphenyl)-2-butanone Chemical compound COC1=CC=C(CCC(C)=O)C=C1 PCBSXBYCASFXTM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 230000017858 demethylation Effects 0.000 claims abstract description 9
- 238000010520 demethylation reaction Methods 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000013019 agitation Methods 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 238000010189 synthetic method Methods 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical group CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- 230000006837 decompression Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000019476 oil-water mixture Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000005667 attractant Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031902 chemoattractant activity Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a raspberry ketone synthesis method, which comprises the following steps: anisylacetone, potassa, N,N-dimethylacetamide are added into a dry four-mouth bottle equipped with a thermometer, a dropping hopper and a condenser tube, heated, dissolved and slowly dropwise added with a demethylation reagent under the agitation condition, and the solid are completely dissolved; a liquid mixture is transferred to an autoclave and is pressurized to react under the protection of inert gas; the liquid mixture subjected to the reaction is neutralized to be neutral, an oil phase is extracted, and crude raspberry ketone is prepared after decompression distillation; the crude raspberry ketone is dissolved with a dissolvent and then crystallized so as to obtain the pure raspberry ketone. According to the invention, the yield is 85.2 percent and the product purity is 98.5 percent; on the basis of keeping the high reaction yield, the raw material cost is effectively lowered, besides, a large amount of acid waste water are not generated, as a result, the pollutions to the environment isare reduced, and the large-scale industrial production and application of the raspberry ketone are facilitated.
Description
Technical field
The present invention relates generally to a kind of synthetic method, relates in particular to a kind of synthetic method of raspberry ketone.
Background technology
Raspberry ketone is a kind of spices with quiet and tastefully laid out fruital, mainly as fixative, modifier, there is good fat-reducing effect, be widely used at present preparation food flavour and daily chemical essence, but also can be used as the intermediate that synthesizes medicine, dyestuff, it is also a kind of attractant in agricultural in addition.
The synthetic method of raspberry ketone has following two kinds at present:
(1) with the synthetic raspberry ketone of petrochemical material, have kinds of processes route, this raw materials technology source is abundant, and cheap, synthesis step is few, and yield is high, but conventionally can not be for the allotment of natural edible essence.
As in patent CN93120105, disclosing and having used p-Hydroxybenzaldehyde is the method for the synthetic raspberry ketone of raw material, in patent WO2009118755A2, discloses and take the synthetic route that phenol is raw material.Described in these two pieces of patents, method is all used petrochemical material as initial feed, and Product Safety has larger hidden danger, and range of application is limited.
(2) with after the synthetic Anisylacetone of natural matter anisyl aldehyde, use the synthetic route of a large amount of Lewis acid demethylations, this process recovery ratio is lower, and the three wastes are larger, and environmental pollution is serious.
As in patent CN101717328A, disclose and used 40%HBr to prepare raspberry ketone for the methyl on the de-Anisylacetone of raw material; In patent GB1094417A, disclose use 48%HBr and prepared raspberry ketone for raw material takes off Anisylacetone methyl.Method described in these two pieces of patents, all can produce a large amount of acid waste water, and HBr is large to the corrodibility of equipment, seriously polluted, causes larger environmental stress.
Summary of the invention
The object of the invention is just to provide a kind of synthetic method of raspberry ketone.
The present invention is achieved by the following technical solutions:
A synthetic method for raspberry ketone, comprises the following steps:
(1) Anisylacetone, potassium hydroxide and N,N-dimethylacetamide are dissolved in dry four-hole bottle, are heated to dissolve; Under agitation condition, slowly add demethylation reagent, obtain mixing liquid;
(2) above-mentioned mixing liquid is transferred in autoclave, under the condition of protection of inert gas, compressive reaction, reaction pressure is 0.1-2.0MPa, and the reaction times is 24-150h, and the temperature of reaction is 130-170 ℃;
(3) reacted mixing liquid is neutralized to neutrality, extraction oil phase, underpressure distillation, prepares raspberry ketone crude product;
(4) by above-mentioned raspberry ketone crude product dissolution with solvents post crystallization, obtain raspberry ketone sterling.
A synthetic method for raspberry ketone, described reaction environment is alkaline environment, potassium hydroxide and N,N-dimethylacetamide are used as alkaline reagents.
A synthetic method for raspberry ketone, described demethylation reagent is chosen as Thiovanic acid or Thiovanic acid salt.
A kind of synthetic method of raspberry ketone, the mol ratio of described Anisylacetone and described potassium hydroxide is 1:6-12, the mol ratio of described Anisylacetone and described N,N-dimethylacetamide is 1:10-22, and the mol ratio of described Anisylacetone and described demethylation reagent is 1:2-10.
A synthetic method for raspberry ketone, described rare gas element is helium, or nitrogen, or argon gas.
A synthetic method for raspberry ketone, described in step (4), solvent is ethyl formate, ethyl acetate, one or more mixing of 95% ethanol.
Advantage of the present invention is:
The present invention has substituted AlCl
3, HBr, as demethylation reagent, when keeping high reaction yield, has better simply post processing mode, and does not produce a large amount of strongly acid wastewaters, has reduced the pollution to environment, is conducive to industrial large-scale production and application.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
Embodiment 1
The present embodiment relates to a kind of synthetic method of raspberry ketone
In 2L four-hole mouth round-bottomed flask, add the potassium hydroxide of 1mol Anisylacetone, 6mol and the N of 10mol, N-N,N-DIMETHYLACETAMIDE, heated and stirred is to after dissolving, slowly to the Thiovanic acid that drips 2mol in mixture, fully stirring reaction, mixture is transferred in 2L autoclave, air nitrogen replacement in still, control pressure 0.1MPa, 130 ℃ of temperature, reaction 24h, stopped reaction is cooled to room temperature.Add in diluted acid and system after, add toluene to extract this oil-water mixture, after washing oil phase, use anhydrous magnesium sulfate drying.Under normal pressure, solvent toluene is removed in distillation, and then underpressure distillation, collects thick product.Distill out after thick product utilization re-crystallizing in ethyl acetate product purity 98.7%, yield: 56.3%.
embodiment 2
The present embodiment relates to a kind of synthetic method of raspberry ketone
In 2L four-hole round-bottomed flask, add the potassium hydroxide of 1mol Anisylacetone, 12mol and the N of 22mol, N-N,N-DIMETHYLACETAMIDE, heated and stirred is to after dissolving, slowly to the Thiovanic acid that drips 10mol in mixture, fully stirring reaction, mixture is transferred in 2L autoclave, air nitrogen replacement in still, control pressure 2.0MPa, 170 ℃ of temperature, reaction 150h, stopped reaction is cooled to room temperature.Add in diluted acid and system after, add toluene to extract this oil-water mixture, after washing oil phase, use anhydrous magnesium sulfate drying.Under normal pressure, solvent toluene is removed in distillation, and then underpressure distillation, collects thick product.Distill out after thick product utilization re-crystallizing in ethyl acetate product purity 98.0%, yield: 75.6%.
?
embodiment 3
The present embodiment relates to a kind of synthetic method of raspberry ketone
In 2L four-hole round-bottomed flask, add the potassium hydroxide of 1mol Anisylacetone, 7mol and the N of 12mol, N-N,N-DIMETHYLACETAMIDE, heated and stirred is to after dissolving, slowly to the Thiovanic acid that drips 6.5mol in mixture, after solid all dissolves, mixture is transferred in 2L autoclave, air nitrogen replacement in still, control pressure 0.15MPa, 170 ℃ of temperature, reaction 77h, stopped reaction is cooled to room temperature.Add in diluted acid and system after, add toluene to extract this oil-water mixture, after washing oil phase, use anhydrous magnesium sulfate drying.Under normal pressure, solvent toluene is removed in distillation, and then underpressure distillation, collects thick product.Distill out after thick product utilization re-crystallizing in ethyl acetate product purity 98.2%, yield: 81.23%.
Claims (6)
1. a synthetic method for raspberry ketone, is characterized in that, comprises the following steps:
(1) Anisylacetone, potassium hydroxide and N,N-dimethylacetamide are dissolved in dry four-hole bottle, are heated to dissolve; Under agitation condition, slowly add demethylation reagent, obtain mixing liquid;
(2) above-mentioned mixing liquid is transferred in autoclave, under the condition of protection of inert gas, compressive reaction, reaction pressure is 0.1-2.0MPa, and the reaction times is 24-150h, and the temperature of reaction is 130-170 ℃;
(3) reacted mixing liquid is neutralized to neutrality, extraction oil phase, underpressure distillation, prepares raspberry ketone crude product;
(4) by above-mentioned raspberry ketone crude product dissolution with solvents post crystallization, obtain raspberry ketone sterling.
2. the synthetic method of a kind of raspberry ketone according to claim 1, is characterized in that, described reaction environment is alkaline environment, and potassium hydroxide and N,N-dimethylacetamide are used as alkaline reagents.
3. the synthetic method of a kind of raspberry ketone according to claim 1, is characterized in that, described demethylation reagent is chosen as Thiovanic acid or Thiovanic acid salt.
4. the synthetic method of a kind of raspberry ketone according to claim 1, it is characterized in that, the mol ratio of described Anisylacetone and described potassium hydroxide is 1:6-12, described Anisylacetone and described N, the mol ratio of N-N,N-DIMETHYLACETAMIDE is 1:10-22, and the mol ratio of described Anisylacetone and described demethylation reagent is 1:2-10.
5. the synthetic method of a kind of raspberry ketone according to claim 1, is characterized in that described rare gas element is helium, or nitrogen, or argon gas.
6. the synthetic method of a kind of raspberry ketone according to claim 1, is characterized in that, described in step (4), solvent is ethyl formate, ethyl acetate, one or more mixing of 95% ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310669809.9A CN103724173A (en) | 2013-12-11 | 2013-12-11 | Raspberry ketone synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310669809.9A CN103724173A (en) | 2013-12-11 | 2013-12-11 | Raspberry ketone synthesis method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103724173A true CN103724173A (en) | 2014-04-16 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310669809.9A Pending CN103724173A (en) | 2013-12-11 | 2013-12-11 | Raspberry ketone synthesis method |
Country Status (1)
| Country | Link |
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| CN (1) | CN103724173A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105218340A (en) * | 2015-10-29 | 2016-01-06 | 广西万山香料有限责任公司 | A kind of raspberry ketone synthesis technique |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009084038A2 (en) * | 2007-12-28 | 2009-07-09 | Ind-Swift Laboratories Limited | Improved process for the preparation of 0-desmethyl-venlafaxine |
| CN101717328A (en) * | 2009-09-14 | 2010-06-02 | 广西万山香料有限责任公司 | New method for synthesizing raspberry ketone by using natural equivalent anisic aldehyde |
-
2013
- 2013-12-11 CN CN201310669809.9A patent/CN103724173A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009084038A2 (en) * | 2007-12-28 | 2009-07-09 | Ind-Swift Laboratories Limited | Improved process for the preparation of 0-desmethyl-venlafaxine |
| CN101717328A (en) * | 2009-09-14 | 2010-06-02 | 广西万山香料有限责任公司 | New method for synthesizing raspberry ketone by using natural equivalent anisic aldehyde |
Non-Patent Citations (2)
| Title |
|---|
| 史兰香等: "O-去甲基文拉法辛合成的新方法", 《应用化学》 * |
| 谷运璀等: "天然覆盆子酮的制备", 《香料香精化妆品》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105218340A (en) * | 2015-10-29 | 2016-01-06 | 广西万山香料有限责任公司 | A kind of raspberry ketone synthesis technique |
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Application publication date: 20140416 |