CN111302919A - Method for synthesizing high-content dihydrojasmone spice - Google Patents
Method for synthesizing high-content dihydrojasmone spice Download PDFInfo
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- CN111302919A CN111302919A CN202010170865.8A CN202010170865A CN111302919A CN 111302919 A CN111302919 A CN 111302919A CN 202010170865 A CN202010170865 A CN 202010170865A CN 111302919 A CN111302919 A CN 111302919A
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- octanol
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- 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
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/58—One oxygen atom, e.g. butenolide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Abstract
The invention belongs to the technical field of spice synthesis, and particularly relates to a synthesis method of a high-content dihydrojasmone spice, which comprises the steps of taking 2-octanol as a solvent, taking di-tert-butyl peroxide as an initiator, taking boric acid as a catalyst, carrying out radical addition reaction on acrylic acid and 2-octanol, carrying out reflux reaction to separate tert-butanol and water, carrying out reduced pressure distillation to recover and reuse the 2-octanol, collecting 5-methyl-5-hexyl-2 (3H) furanone, then taking white oil as a solvent, and carrying out rearrangement dehydration on 5-methyl-5-hexyl-2 (3H) furanone molecules under the action of a solid acid catalyst to synthesize a dihydrojasmone spice product. The synthesis method provided by the invention has the advantages of relatively simple steps, no generation of acid wastewater and high total yield, and in addition, the content of the dihydrojasmone in the product synthesized by the synthesis method provided by the invention is up to 98% or more through calculation.
Description
Technical Field
The invention belongs to the technical field of spice synthesis, and particularly relates to a synthesis method of a high-content dihydrojasmone spice.
Background
The chemical name of the dihydro jasmone is 2-amyl-3-methyl-2-cyclopentene-1-one, the CAS number is 1128-08-1, the dihydro jasmone is also called tetrahydropyrethrin ketone, the dihydro jasmone has strong and fresh jasmine flower fragrance and fruity fragrance, the dihydro jasmone is bitter and astringent in green when being thick, and the dihydro jasmone has jasmine flower fragrance after being diluted. The dihydrojasmone is colorless to yellowish liquid, has a boiling point of 120 ℃/12mmHg, a flash point of 130 ℃, a relative density of 0.915-0.920 (25/25 ℃), a refractive index of 1.475-1.481 (20 ℃), and is dissolved in 1-10 volume of 70% ethanol or 80% ethanol with the same volume, and is dissolved in oily flavor. Because the dihydrojasmone has strong and lasting jasmine fragrance and strong and mild fruit fragrance, the dihydrojasmone is commonly used as a fragrance raw material of cosmetic essence and is mainly used for preparing floral essences such as jasmine and the like, the dosage of the dihydrojasmone in the jasmine blue type essence can reach 3-5%, and the fragrance of the floral can be improved in the fruit fragrance-floral type, such as jasmine, cananga odorata, lily of the valley, magnolia denudata, tuberose and the like. Trace amount of the perfume is used together with fruit perfume, and pleasant top perfume can be generated; it also has the function of enhancing the fragrance of bergamot, lavender, miscellaneous lavender, clary sage and other herbs; the dihydrojasmone can also be used as food additive, which is recognized as GRAS by FEMA, FEMA number 3763, and is approved to be eaten by the Food and Drug Administration (FDA), and also is listed as food spice allowed to be used by the food additive use standard (GB2760) in China.
In the prior art, the synthesis methods of the dihydrojasmone are various, mainly comprising: (1) jasmone is catalytically reduced, however, the raw material source and cost of the synthesis method are problematic; (2) dihydrojasmone can be prepared by condensation of acrylate and secondary octanol under the catalysis of peroxide and then dehydration rearrangement in the presence of phosphoric acid, but the method will generate a large amount of phosphoric acid waste water; (3) undecanedione method: heating and refluxing 2, 5-undecanedione, ethanol and 2% sodium hydroxide solution for 6h under the protection of nitrogen, concentrating the reaction solution, extracting with petroleum ether, evaporating the extracting solution to remove the solvent, distilling under reduced pressure, and collecting the fraction with 115 ℃ (1.33kPa) of 113-; (4) prepared by the reaction of 3-oxobutyric acid and bromo-3-nonanone; in general, some existing methods for synthesizing dihydrojasmone have the disadvantages of long routes, high cost, harsh reaction conditions, complex operation, low overall yield and the like, and particularly, the content of the synthesized dihydrojasmone is only 90% -95%, so that the synthesis and application of the dihydrojasmone have great limitations.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for synthesizing a high-content dihydrojasmone spice.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing high-content dihydrojasmone spice comprises the following steps:
(1) starting cooling water of a cold and hot integrated exchanger, controlling the temperature to be 15-25 ℃, starting a stirrer, then adding 2-octanol into a flask, then respectively adding acrylic acid, water and di-tert-butyl peroxide, and uniformly stirring to obtain a mixture for later use;
(2) adding 2-octanol into a three-neck flask with a reflux device, starting a magnetic stirrer, then adding a catalyst boric acid, and uniformly stirring;
(3) starting cooling water of a reflux device, starting a cold and hot integrated exchanger, heating, controlling the reaction temperature to be 156-160 ℃, slowly dripping the mixture of the ingredients obtained in the step (1) into the four-neck flask by a peristaltic pump, keeping reflux in the dripping process, and controlling the dripping time to be 4-8 h;
(4) after the dropwise addition is finished, continuously keeping the temperature, stirring and refluxing for 30min, sampling for gas chromatography detection, stopping reaction if the content of acrylic acid is below 0.5%, stopping heating, starting cooling water for cooling, and transferring the reaction liquid into a separating funnel after cooling to normal temperature;
(5) standing for layering for 2h, separating out a water layer, and transferring an organic layer to a rotary evaporator;
(6) starting a rotary evaporator, starting vacuum, heating, distilling under reduced pressure to recover 2-octanol for reuse, and collecting a distillation flask substrate after the completion to obtain 5-methyl-5-hexyl-2 (3H) furanone;
(7) adding solvent No. 90 white oil and a solid acid catalyst into a four-neck flask with a reflux device, starting a stirrer, starting the reflux device to cool water, starting a cold and hot integrated exchanger, heating, controlling the reaction temperature to be 98-102 ℃, dropwise adding the 5-methyl-5-hexyl-2 (3H) furanone obtained in the step (6), keeping reflux in the dropwise adding process, and controlling the dropwise adding time to be 4-6H;
(8) after the dropwise addition is finished, continuously keeping the temperature and stirring and refluxing for 30min, sampling for gas chromatography detection, stopping the reaction if the content of 5-methyl-5-hexyl-2 (3H) furanone is below 0.5%, stopping heating, starting cooling water for cooling, and cooling to normal temperature;
(9) adding clear water into the reaction solution for washing, standing for layering for 2h, separating out a water layer and a solid acid, mechanically applying, and transferring an organic layer to a rotary evaporator;
(10) starting a rotary evaporator, starting vacuum, heating, distilling under reduced pressure, and collecting distillate to obtain the dihydrojasmone.
The synthesis method of the dihydrojasmone provided by the invention has the specific reaction principle that:
according to the invention, in the blending mixture of the step (1), the molar ratio of acrylic acid to 2-octanol is 1: (2-5), more preferably 1: (2.5-3.5); the mass ratio of acrylic acid to water is 1: (0.1-1), more preferably 1: (0.25-0.30); the molar ratio of acrylic acid to di-tert-butyl peroxide is 1: (0.1-0.5), more preferably 1: (0.10-0.15).
According to the present invention, in the present invention, the molar ratio of 2-octanol described in step (2) to acrylic acid in step (1) is (1-5):1, more preferably (3.5-4.0): 1; the mass ratio of the catalyst boric acid to the acrylic acid in the step (1) is (0.01-0.1): 1, more preferably (0.02 to 0.05): 1.
according to the invention, in the step (6), the conditions for recovering 2-octanol by vacuum distillation comprise: the temperature is 95-100 ℃, and the vacuum pressure is 6000 Pa.
According to the invention, in the step (7), the volume ratio of the solvent No. 90 white oil to the 5-methyl-5-hexyl-2 (3H) furanone is (0.1-0.5): 1, more preferably (0.10 to 0.15): 1; the mass ratio of the solid acid catalyst to the 5-methyl-5-hexyl-2 (3H) furanone is (0.01-0.1): 1, more preferably (0.02 to 0.03): 1.
according to the present invention, in the step (10), the conditions for collecting dihydrojasmone by reduced pressure distillation include: the temperature is 120-122 ℃, and the vacuum pressure is 1600 Pa.
Compared with the prior art, the invention has the following technical effects:
the invention provides a synthesis method of a dihydrojasmone spice, which comprises the steps of taking excessive 2-octanol as a solvent, di-tert-butyl peroxide as an initiator and boric acid as a catalyst, carrying out free radical addition reaction and reflux reaction on acrylic acid and 2-octanol to separate tert-butanol and water, then carrying out reduced pressure distillation to recycle the 2-octanol, collecting 5-methyl-5-hexyl-2 (3H) furanone, then taking white oil as a solvent, and carrying out rearrangement dehydration on 5-methyl-5-hexyl-2 (3H) furanone molecules under the action of a solid acid catalyst to synthesize the dihydrojasmone spice product.
The synthesis method provided by the invention has the advantages of relatively simple steps, no generation of acid wastewater and high total yield, and in addition, the content of the dihydrojasmone in the product synthesized by the synthesis method provided by the invention is up to 98% or more through calculation.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is further clarified with the specific embodiments.
All the raw materials in the present invention, the sources of which are not particularly limited, may be either commercially available or prepared according to conventional methods well known to those skilled in the art; all the raw materials used in the present invention are not particularly limited in purity, and the present invention preferably employs a purity which is conventional in the field of analytical purification or composite materials.
Example 1
A synthesis method of a dihydrojasmone spice comprises the following specific steps:
(1) starting cooling water of a cold and hot integrated exchanger, controlling the temperature to be 15-25 ℃, starting a stirrer, adding 280g of 2-octanol into a 500ml flask, then respectively adding 60g of acrylic acid, 15g of water and 14g of di-tert-butyl peroxide, and uniformly stirring to obtain a mixture for preparing a mixture for later use;
(2) adding 380g of 2-octanol into a 1500ml three-neck flask with a reflux device, starting a magnetic stirrer, then adding 1.5g of catalyst boric acid, and uniformly stirring;
(3) starting cooling water of a reflux device, starting a cold and hot integrated exchanger, heating, controlling the reaction temperature to be 156-160 ℃, then slowly dripping the mixture of the ingredients obtained in the step (1) into the three-neck flask by using a peristaltic pump, keeping reflux in the dripping process, and controlling the dripping time to be 4 hours;
(4) after the dropwise addition is finished, continuously keeping the temperature, stirring and refluxing for 30min, sampling for gas chromatography detection, stopping reaction if the content of acrylic acid is below 0.5%, stopping heating, starting cooling water for cooling, and transferring the reaction liquid into a separating funnel after cooling to normal temperature;
(5) standing for layering for 2h, separating out a water layer, and transferring an organic layer to a rotary evaporator;
(6) starting a rotary evaporator, starting vacuum, heating, recovering 461g of 2-octanol through reduced pressure distillation under the conditions that the temperature is 95-100 ℃ and the vacuum pressure is 6000Pa for application, collecting a distillation flask substrate after the completion of the distillation, and obtaining 143g of 5-methyl-5-hexyl-2 (3H) furanone by weighing;
(7) adding 20g of solvent No. 90 white oil and 3.5g of solid acid catalyst into a four-neck reaction flask with a reflux device, starting a stirrer, starting the reflux device to cool water, starting a cold and hot integrated exchanger, heating, controlling the reaction temperature to be 90-100 ℃, dropwise adding the 5-methyl-5-hexyl-2 (3H) furanone obtained in the step (6) by a peristaltic pump, keeping reflux in the dropwise adding process, and controlling the dropwise adding time to be 4 hours;
(8) after the dropwise addition is finished, continuously keeping the temperature and stirring and refluxing for 30min, sampling for gas chromatography detection, stopping the reaction when the content of 5-methyl-5-hexyl-2 (3H) furanone is below 0.5%, stopping heating, starting cooling water for cooling, and cooling to normal temperature;
(9) adding 50ml of clear water into the reaction solution for washing, standing and layering for 2h, separating out a water layer, separating out a solid acid catalyst for reuse, and transferring an organic layer to a rotary evaporator;
(10) starting a rotary evaporator, starting vacuum, heating, distilling under reduced pressure at the temperature of 120-122 ℃ and the vacuum pressure of 1600Pa, and collecting distillate to obtain 105g of dihydrojasmone, wherein the total yield of the reaction is calculated to be 76%;
the synthesized dihydrojasmone is a colorless transparent liquid by visual inspection, has strong and fresh jasmine flower fragrance and fruit fragrance, and has the purity of 98.46 percent by gas chromatography analysis, the detected refractive index (20 ℃) of 1.479 and the relative density (25 ℃) of 0.915, which are consistent with the literature values.
The foregoing shows and describes the general principles, essential features, and inventive features of this invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. A method for synthesizing high-content dihydrojasmone spice is characterized by comprising the following steps:
(1) starting cooling water of a cold and hot integrated exchanger, controlling the temperature to be 15-25 ℃, starting a stirrer, then adding 2-octanol into a flask, then respectively adding acrylic acid, water and di-tert-butyl peroxide, and uniformly stirring to obtain a mixture for later use;
(2) adding 2-octanol into a three-neck flask with a reflux device, starting a magnetic stirrer, then adding a catalyst boric acid, and uniformly stirring;
(3) starting cooling water of a reflux device, starting a cold and hot integrated exchanger, heating, controlling the reaction temperature to be 156-160 ℃, slowly dripping the mixture of the ingredients obtained in the step (1) into the four-neck flask by a peristaltic pump, keeping reflux in the dripping process, and controlling the dripping time to be 4-8 h;
(4) after the dropwise addition is finished, continuously keeping the temperature, stirring and refluxing for 30min, sampling for gas chromatography detection, stopping reaction if the content of acrylic acid is below 0.5%, stopping heating, starting cooling water for cooling, and transferring the reaction liquid into a separating funnel after cooling to normal temperature;
(5) standing for layering for 2h, separating out a water layer, and transferring an organic layer to a rotary evaporator;
(6) starting a rotary evaporator, starting vacuum, heating, distilling under reduced pressure to recover 2-octanol for reuse, and collecting a distillation flask substrate after the completion to obtain 5-methyl-5-hexyl-2 (3H) furanone;
(7) adding solvent No. 90 white oil and a solid acid catalyst into a four-neck flask with a reflux device, starting a stirrer, starting the reflux device to cool water, starting a cold and hot integrated exchanger, heating, controlling the reaction temperature to be 98-102 ℃, dropwise adding the 5-methyl-5-hexyl-2 (3H) furanone obtained in the step (6), keeping reflux in the dropwise adding process, and controlling the dropwise adding time to be 4-6H;
(8) after the dropwise addition is finished, continuously keeping the temperature and stirring and refluxing for 30min, sampling for gas chromatography detection, stopping the reaction if the content of 5-methyl-5-hexyl-2 (3H) furanone is below 0.5%, stopping heating, starting cooling water for cooling, and cooling to normal temperature;
(9) adding clear water into the reaction solution for washing, standing for layering for 2h, separating out a water layer and a solid acid, mechanically applying, and transferring an organic layer to a rotary evaporator;
(10) starting a rotary evaporator, starting vacuum, heating, distilling under reduced pressure, and collecting distillate to obtain the dihydrojasmone.
2. The synthesis process according to claim 1, wherein in the feed mixture of step (1), the molar ratio of acrylic acid to 2-octanol is 1: (2-5); the mass ratio of acrylic acid to water is 1: (0.1-1); the molar ratio of acrylic acid to di-tert-butyl peroxide is 1: (0.1-0.5).
3. The synthesis process of claim 1, wherein the molar ratio of 2-octanol in step (2) to acrylic acid in step (1) is (1-5): 1; the mass ratio of the catalyst boric acid to the acrylic acid in the step (1) is (0.01-0.1): 1.
4. the synthesis method according to claim 1, wherein in the step (6), the conditions for recovering 2-octanol by vacuum distillation comprise: the temperature is 95-100 ℃, and the vacuum pressure is 6000 Pa.
5. The synthesis method of claim 1, wherein in the step (7), the volume ratio of the solvent No. 90 white oil to the 5-methyl-5-hexyl-2 (3H) furanone is (0.1-0.5): 1;
the mass ratio of the solid acid catalyst to the 5-methyl-5-hexyl-2 (3H) furanone is (0.01-0.1): 1.
6. the synthesis method according to claim 1, wherein in the step (10), the conditions for collecting the dihydrojasmone by reduced pressure distillation comprise: the temperature is 120-122 ℃, and the vacuum pressure is 1600 Pa.
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| CN202010170865.8A CN111302919A (en) | 2020-03-12 | 2020-03-12 | Method for synthesizing high-content dihydrojasmone spice |
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| CN202010170865.8A CN111302919A (en) | 2020-03-12 | 2020-03-12 | Method for synthesizing high-content dihydrojasmone spice |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876436A (en) * | 2021-03-01 | 2021-06-01 | 安徽金轩科技有限公司 | Method for preparing furan ammonium salt with high selectivity |
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2020
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876436A (en) * | 2021-03-01 | 2021-06-01 | 安徽金轩科技有限公司 | Method for preparing furan ammonium salt with high selectivity |
| CN112876436B (en) * | 2021-03-01 | 2022-06-21 | 安徽金轩科技有限公司 | Method for preparing furan ammonium salt with high selectivity |
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