CN113816840A - Synthesis method of beta-damascenone - Google Patents

Synthesis method of beta-damascenone Download PDF

Info

Publication number
CN113816840A
CN113816840A CN202111229104.6A CN202111229104A CN113816840A CN 113816840 A CN113816840 A CN 113816840A CN 202111229104 A CN202111229104 A CN 202111229104A CN 113816840 A CN113816840 A CN 113816840A
Authority
CN
China
Prior art keywords
beta
damascenone
stirring
cyclocitral
solution
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.)
Pending
Application number
CN202111229104.6A
Other languages
Chinese (zh)
Inventor
周军学
陈清
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kunshan Yaxiang Spicel Co ltd
Original Assignee
Kunshan Yaxiang Spicel Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kunshan Yaxiang Spicel Co ltd filed Critical Kunshan Yaxiang Spicel Co ltd
Priority to CN202111229104.6A priority Critical patent/CN113816840A/en
Publication of CN113816840A publication Critical patent/CN113816840A/en
Pending legal-status Critical Current

Links

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
    • C07C45/65—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 splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/518—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of sulfur-containing compounds to >C = O groups
    • 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
    • C07C45/63—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 halogen; by substitution of halogen atoms by other halogen atoms
    • 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
    • C07C45/67—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 isomerisation; by change of size of the carbon skeleton
    • 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
    • C07C45/67—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 isomerisation; by change of size of the carbon skeleton
    • C07C45/68—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 isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • 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
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/79—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
    • 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
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • 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
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a synthesis method of beta-damascenone, which comprises the following specific steps: the method comprises the steps of firstly, refining citral, secondly, preparing beta-cyclocitral, thirdly, preparing beta-damascenone, fourthly, preparing beta-damascenone, and dehydrobrominating with diethylaniline to prepare the beta-damascenone. In the process of preparing the beta-damascone, the beta-cyclocitral reacts with allyl chloride and pre-activated magnesium simultaneously, and then the intermediate generates the beta-damascone, chromium trioxide is not used as an oxide in the whole reaction process, so that more solid waste cannot be generated at the end of the reaction.

Description

Synthesis method of beta-damascenone
Technical Field
The invention relates to the technical field of beta-damascenone synthesis, in particular to a synthesis method of beta-damascenone.
Background
The damascone can play a role in improving the fragrance of the roses by adding the damascone into the essence. Has strong fragrance and good diffusion. Is mainly used for preparing high-grade cosmetics and food flavors. Beta-damascone (beta-damascone) is an isomer of damascone, and is a precious fragrance raw material because of attractive rose fragrance and raspberry-like fruit fragrance and diffusibility. The raw material was first discovered by the perfumer g.ohloff as a trace but critical aroma component in the rose oil from gayala damascena.
In recent years, with the development of the perfume industry, the improvement of the synthesis process and the like, the price of beta-damascenone is also reduced, and thus the usage amount is larger and wider. The beta-damascenone perfume is used as a precious perfume material in the preparation of high-grade perfume and cosmetic essence, is applied to food essence, and can improve the lasting appeal of cigarettes in tobacco to make the smoke taste softer and more comfortable.
In the prior art, in the process of synthesizing beta-damascenone by utilizing beta-cyclocitral, the beta-cyclocitral needs to be subjected to 1-bromopropenyl magnesium format reagent or propenyl lithium compound for multiple times of reaction to generate alcohol, then the alcohol generated in the reaction process is oxidized by chromium trioxide to obtain beta-damascenone, and then the beta-damascenone is dehydrogenated to prepare the beta-damascenone.
Disclosure of Invention
Therefore, the invention provides a method for synthesizing beta-damascenone, which comprises the steps of simultaneously reacting beta-cyclocitral with allyl chloride and magnesium activated in advance in the process of preparing the beta-damascenone, and then generating the beta-damascenone from an intermediate, wherein chromium trioxide is not used as an oxide in the whole reaction process, so that more solid wastes cannot be generated at the end of the reaction.
In order to achieve the above object, the embodiments of the present invention provide the following technical solutions: a method for synthesizing beta-damascenone comprises the following specific steps:
step one, refining citral: selecting 30kg of litsea cubeba oil containing 75% of citral, adding the litsea cubeba oil into a mixed solution prepared by 18kg of sodium bicarbonate, 38kg of sodium sulfite and 165kg of clear water under full stirring, stirring and reacting for 5-6 h at room temperature, standing overnight for layering, separating out citral at the lower layer in the form of an adduct, washing the adduct with toluene to remove oil, spin-drying, adding 10% of sodium hydroxide solution, decomposing the citral at room temperature, extracting with benzene, distilling the extract at normal pressure to recover the benzene, distilling under reduced pressure, and collecting fractions at 110-111 ℃ to obtain 15-16 kg of a 98% citral pure product;
step two, preparing beta-cyclocitral: s1, weighing 15.2 g of citral, weighing 40mL of anhydrous ether, transferring the citral into a flask, adding ether, magnetically stirring, adding 9.5mL of newly steamed aniline, stirring at room temperature for 40min, adding anhydrous sodium sulfate when turbidity appears during stirring, and standing to obtain a light yellow clear solution; s2, adding 40mL of concentrated sulfuric acid into a three-neck flask under magnetic stirring, adding 8mL of water into a salt-ice bath, and cooling; s3, stirring and adjusting the temperature of the solution to-5 ℃ through ice salt, adding the solution prepared by the reaction in the step S1 into a constant-pressure separating funnel by using a funnel, and dropwise adding the solution into a flask at the temperature of-2-5 ℃; s4, reacting for 45min after the dropwise adding is finished, pouring the product into a large beaker filled with ice water, and stirring to prevent caking; s5, transferring the mixture to a separating funnel, extracting the mixture for three times by using ethyl acetate, combining reddish brown organic phases on the upper layer, washing the mixture to be neutral by using saturated sodium carbonate, washing the mixture by using saturated sodium chloride, drying the organic phases overnight by using anhydrous sodium sulfate, removing the solvent by reduced pressure distillation to obtain a mixture of alpha-cyclocitral and beta-cyclocitral, and performing column chromatography separation to obtain pure beta-cyclocitral;
step three, preparing beta-damascone: adding 6.7g of metal magnesium which is activated by iodine in advance and 200ml of tetrahydrofuran into a 500ml three-necked bottle with a stirrer and a thermometer sleeve, under the protection of nitrogen, firstly adding chloropropene, rapidly increasing the temperature, starting the stirrer, cooling with ice water, and then adding chloropropene and beta-cyclocitral solution within 1 hour; maintaining the temperature between 10-40 ℃; after the solution is dropwise added, continuously stirring for 1 hour at room temperature, processing to obtain an intermediate, and then carrying out double bond rearrangement and cyclization on the intermediate to generate beta-damascone;
step four, preparing beta-damascenone: the beta-damascenone prepared in the third step is firstly brominated by N-bromosuccinamide and then dehydrobrominated by diethylaniline to prepare the beta-damascenone.
Further, the atmospheric distillation operation temperature in the step one is 80-82 ℃, the atmospheric pressure is set to facilitate the extraction of benzene from the extract, and the pressure of the reduced pressure distillation is 1.47 kPa.
Further, in the operation of S3 in the second step, the dropping speed was kept uniform during the dropping of the solution, and the temperature of the flask was controlled to be not higher than-2 ℃.
Further, the eluent for column chromatography separation was petroleum ether in the S5 operation in step two.
Further, the solution of β -cyclocitral in step III was prepared from 19.8g of chloropropene and 33.2g of β -cyclocitral in 110ml of tetrahydrofuran.
Further, the intermediate obtained in step three was 34.9g, yield 89.9%, boiling point 76-82 deg.C/2 mmHg.
The invention has the following advantages:
1. in the process of preparing the beta-damascone, cyclocitral reacts with allyl chloride and magnesium activated in advance simultaneously, and then the beta-damascone is generated from an intermediate, chromium trioxide is not used as an oxide in the whole reaction process, so that more solid waste cannot be generated at the end of the reaction, and compared with the prior art, the reaction process is cleaner, the generated wastewater and solid waste are less, and the influence on the environment is less;
2. compared with the prior art, the method improves the original two-step reaction into one-step reaction in the process of generating the beta-damascenone, the improved synthesis method not only simplifies the process, but also improves the yield, and the method fully utilizes the existing abundant litsea cubeba oil resources in China, thereby realizing local control, fully utilizing the existing resources in China and effectively reducing the industrial production cost.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a synthesis method of beta-damascenone, which comprises the following specific steps:
step one, refining citral, wherein the citral naturally exists in lemongrass oil, lemon oil, lime oil, citrus oil, litsea cubeba oil and verbena oil, the content of the natural essential oil of the lemongrass oil and the litsea cubeba oil is 70-80%, the citral can be obtained by temperature-dividing distillation from the essential oil, China contains rich litsea cubeba oil resources, and the citral extracted from the litsea cubeba oil can fully utilize natural resources of China, exert resource advantages and make things appropriate for local conditions;
the specific operation for extracting citral is as follows: selecting 30kg of litsea cubeba oil containing 75 percent of citral, adding the litsea cubeba oil into a mixed solution prepared by 18kg of sodium bicarbonate, 38kg of sodium sulfite and 165kg of clear water under full stirring, stirring and reacting for 5-6 h at room temperature, standing overnight for layering, separating out the citral on the lower layer in the form of an adduct, washing the adduct with toluene to remove oil, spin-drying, adding 10 percent of sodium hydroxide solution, decomposing the citral at room temperature, extracting with benzene, distilling and recovering the benzene from the extract at normal pressure, wherein the benzene is a hydrocarbon, namely the simplest aromatic hydrocarbon, is sweet, combustible, cancerogenic, colorless and transparent liquid at normal temperature and has strong aromatic odor, is insoluble in water, is soluble in an organic solvent, can be used as the organic solvent, has a ring system called a benzene ring, and has a structure called the phenyl after one hydrogen atom is removed from the benzene ring, and is represented by Ph, the chemical formula of benzene can therefore also be written as PhH. Benzene is a petrochemical basic raw material, the yield and the production technical level of the benzene are one of the marks of the national petrochemical development level), the atmospheric distillation operation temperature is 80-82 ℃, the atmospheric pressure is set, the benzene is conveniently extracted from the extract, then the reduced pressure distillation is carried out, the pressure of the reduced pressure distillation is 1.47kPa, the fraction at 110-111 ℃ is collected, and the 98% citral pure product is 15-16 kg.
Step two, the beta-cyclocitral is an important intermediate for synthesizing terpenoids such as spices and carotenoids, for example, dihydrodamascone, damascone, carotene and the like are synthesized by taking the cyclocitral as a raw material, and the specific operation for preparing the beta-cyclocitral is as follows:
s1, weighing 15.2 g of citral, weighing 40mL of anhydrous ether, transferring the citral into a flask, adding ether, magnetically stirring, adding 9.5mL of newly steamed aniline, stirring at room temperature for 40min, adding anhydrous sodium sulfate when turbidity appears during stirring, and standing to obtain a light yellow clear solution;
s2, adding 40mL of concentrated sulfuric acid into a three-neck flask under magnetic stirring, adding 8mL of water under the cooling condition of an ice salt bath, wherein a magnetic stirrer is used for magnetic stirring, the magnetic stirrer is an instrument which utilizes the characteristic that like poles of magnetic substances repel each other, pushes a magnetic stirrer to rotate by continuously changing the polarities of two ends of a base, and drives a sample to rotate by means of the rotation of the magnetic stirrer so as to uniformly mix the sample, and the magnetic stirrer is used for heating or heating and stirring simultaneously and is suitable for liquid or solid-liquid mixture with not very high viscosity;
s3, stirring and adjusting the temperature of the solution to-5 ℃ through ice salt, adding the solution prepared by the reaction in the step S1 into a constant-pressure separating funnel by using a funnel (the constant-pressure separating funnel is one of separating funnels, can carry out operations such as separating, extracting and the like other separating funnels, and is different from other separating funnels in that the constant-pressure separating funnel can ensure that the internal pressure is unchanged, so that the inverse suction can be prevented, the liquid in the funnel can smoothly flow down, and the influence of the increased liquid on the gas pressure is reduced, so that the gas volume is more accurate when being measured), dropwise adding the solution into a flask at the temperature of-2-5 ℃, keeping the dropwise adding speed uniform in the dropwise adding process of the solution, and controlling the temperature of the flask to be not higher than-2 ℃;
ice salt, which refers to a mixture of ice and salt solution; the ice salt mixture is an effective cold-starting agent; when the salt is mixed in the crushed ice, the salt is dissolved in the ice to generate heat absorption, so that the temperature of the ice is reduced; the ice salt mixes together and two effects occur at the same time: one is to greatly increase the melting speed of ice, and to absorb a large amount of heat when the ice is melted; the other is that the dissolution of the salt also absorbs the dissolution heat; thus, a large amount of heat can be absorbed in a short time, thereby rapidly lowering the temperature of the ice-salt mixture, which is much lower than that of pure ice;
s4, reacting for 45min after the dropwise adding is finished, pouring the product into a large beaker filled with ice water, stirring simultaneously to prevent caking, and stirring at a constant speed in the stirring process, wherein the product needs to be stirred in the same direction;
s5, transferring the mixture into a separating funnel, extracting the mixture for three times by ethyl acetate, combining reddish brown organic phases on the upper layer, washing the mixture to be neutral by saturated sodium carbonate, washing the mixture by saturated sodium chloride, adding the organic phase, drying the mixture overnight by anhydrous sodium sulfate, distilling the mixture under reduced pressure to remove the solvent to obtain a mixture of alpha-cyclocitral and beta-cyclocitral, and separating the mixture by column chromatography to obtain pure beta-cyclocitral, wherein an eluent for the separation by the column chromatography is petroleum ether which is colorless transparent liquid and has kerosene smell, is mainly a mixture of pentane and hexane, is insoluble in water, is soluble in most organic solvents such as anhydrous ethanol, benzene, chloroform, oils and the like, is flammable and explosive, can strongly react with an oxidant, is mainly used for treating solvents and grease, and is usually prepared by using platinum reforming raffinate oil or straight-run gasoline through fractionation, hydrogenation or other methods.
Step three, preparing beta-damascone: adding 6.7g of magnesium metal activated by iodine and 200ml of tetrahydrofuran into a 500ml three-necked bottle with a stirrer and a thermometer sleeve, under the protection of nitrogen, adding chloropropene, raising the temperature sharply, starting the stirrer, adding ice water into the three-necked bottle, rapidly absorbing the temperature sharply raised in the reaction process by using the ice water, and then adding a chloropropene and beta-cyclocitral solution within 1 hour, wherein the beta-cyclocitral solution is prepared by dissolving 19.8g of chloropropene and 33.2g of beta-cyclocitral in 110ml of tetrahydrofuran; maintaining the temperature between 10-40 ℃; after the solution is dropwise added, stirring is continuously carried out for 1 hour at room temperature, an intermediate is obtained through treatment, the content of the prepared intermediate is 34.9g, the yield is 89.9%, the boiling point is 76-82 ℃/2mmHg, and then the intermediate is subjected to double bond rearrangement and cyclization to generate beta-damascone;
step four, preparing beta-damascenone: the beta-damascenone prepared in the third step is firstly brominated by N-bromosuccinamide and then dehydrobrominated by diethylaniline to prepare the beta-damascenone.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (6)

1. A method for synthesizing beta-damascenone is characterized in that: the method comprises the following specific steps:
step one, refining citral: selecting 30kg of litsea cubeba oil containing 75% of citral, adding the litsea cubeba oil into a mixed solution prepared by 18kg of sodium bicarbonate, 38kg of sodium sulfite and 165kg of clear water under full stirring, stirring and reacting for 5-6 h at room temperature, standing overnight for layering, separating out citral at the lower layer in the form of an adduct, washing the adduct with toluene to remove oil, spin-drying, adding 10% of sodium hydroxide solution, decomposing the citral at room temperature, extracting with benzene, distilling the extract at normal pressure to recover the benzene, distilling under reduced pressure, and collecting fractions at 110-111 ℃ to obtain 15-16 kg of a 98% citral pure product;
step two, preparing beta-cyclocitral: s1, weighing 15.2 g of citral, weighing 40mL of anhydrous ether, transferring the citral into a flask, adding ether, magnetically stirring, adding 9.5mL of newly steamed aniline, stirring at room temperature for 40min, adding anhydrous sodium sulfate when turbidity appears during stirring, and standing to obtain a light yellow clear solution; s2, adding 40mL of concentrated sulfuric acid into a three-neck flask under magnetic stirring, adding 8mL of water into a salt-ice bath, and cooling; s3, stirring and adjusting the temperature of the solution to-5 ℃ through ice salt, adding the solution prepared by the reaction in the step S1 into a constant-pressure separating funnel by using a funnel, and dropwise adding the solution into a flask at the temperature of-2-5 ℃; s4, reacting for 45min after the dropwise adding is finished, pouring the product into a large beaker filled with ice water, and stirring to prevent caking; s5, transferring the mixture to a separating funnel, extracting the mixture for three times by using ethyl acetate, combining reddish brown organic phases on the upper layer, washing the mixture to be neutral by using saturated sodium carbonate, washing the mixture by using saturated sodium chloride, drying the organic phases overnight by using anhydrous sodium sulfate, removing the solvent by reduced pressure distillation to obtain a mixture of alpha-cyclocitral and beta-cyclocitral, and performing column chromatography separation to obtain pure beta-cyclocitral;
step three, preparing beta-damascone: adding 6.7g of metal magnesium which is activated by iodine in advance and 200ml of tetrahydrofuran into a 500ml three-necked bottle with a stirrer and a thermometer sleeve, under the protection of nitrogen, firstly adding chloropropene, rapidly increasing the temperature, starting the stirrer, cooling with ice water, and then adding chloropropene and beta-cyclocitral solution within 1 hour; maintaining the temperature between 10-40 ℃; after the solution is dropwise added, continuously stirring for 1 hour at room temperature, processing to obtain an intermediate, and then carrying out double bond rearrangement and cyclization on the intermediate to generate beta-damascone;
step four, preparing beta-damascenone: the beta-damascenone prepared in the third step is firstly brominated by N-bromosuccinamide and then dehydrobrominated by diethylaniline to prepare the beta-damascenone.
2. The method for synthesizing beta-damascenone according to claim 1, wherein: the operation temperature of the atmospheric distillation in the step one is 80-82 ℃, and the pressure of the reduced pressure distillation is 1.47 kPa.
3. The method for synthesizing beta-damascenone according to claim 1, wherein: in the operation of S3 in the second step, the dropping speed was kept uniform during the dropping of the solution, and the temperature of the flask was controlled to be not higher than-2 ℃.
4. The method for synthesizing beta-damascenone according to claim 1, wherein: the eluent for column chromatography separation in S5 operation in step two is petroleum ether.
5. The method for synthesizing beta-damascenone according to claim 1, wherein: the solution of beta-cyclocitral in step III was prepared from 19.8g of chloropropene and 33.2g of beta-cyclocitral in 110ml of tetrahydrofuran.
6. The method for synthesizing beta-damascenone according to claim 1, wherein: the intermediate obtained in step three was 34.9g, yield 89.9%, boiling point 76-82 deg.C/2 mmHg.
CN202111229104.6A 2021-10-21 2021-10-21 Synthesis method of beta-damascenone Pending CN113816840A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111229104.6A CN113816840A (en) 2021-10-21 2021-10-21 Synthesis method of beta-damascenone

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111229104.6A CN113816840A (en) 2021-10-21 2021-10-21 Synthesis method of beta-damascenone

Publications (1)

Publication Number Publication Date
CN113816840A true CN113816840A (en) 2021-12-21

Family

ID=78917150

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111229104.6A Pending CN113816840A (en) 2021-10-21 2021-10-21 Synthesis method of beta-damascenone

Country Status (1)

Country Link
CN (1) CN113816840A (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101157602A (en) * 2007-10-22 2008-04-09 新疆中基天然植物纯化高新技术研究院有限公司 Method for purifying geranialdehyde
CN101781183A (en) * 2010-01-15 2010-07-21 绍兴文理学院 Preparation method of beta-ionone
CN104450197A (en) * 2014-12-03 2015-03-25 南华大学 Method for extracting litsea cubeba oil and citral
CN106117027A (en) * 2016-06-20 2016-11-16 聊城大学 Utilize the method that micro-structured reactor prepares cyclocitral
CN106316816A (en) * 2016-08-22 2017-01-11 鹰潭中投科技有限公司 Method for preparing natural citral
CN108383702A (en) * 2017-12-15 2018-08-10 永州山香香料有限公司 A method of extracting citronellal from fruit of a cubeb litsea tree hair oil
CN109053407A (en) * 2018-06-28 2018-12-21 厦门欧米克生物科技有限公司 A method of synthesis β-Damascenone
CN110845309A (en) * 2019-11-19 2020-02-28 中南大学 Preparation method of natural citral
WO2020072908A1 (en) * 2018-10-05 2020-04-09 Manus Bio, Inc. Biosynthesis and recovery of secondary metabolites

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101157602A (en) * 2007-10-22 2008-04-09 新疆中基天然植物纯化高新技术研究院有限公司 Method for purifying geranialdehyde
CN101781183A (en) * 2010-01-15 2010-07-21 绍兴文理学院 Preparation method of beta-ionone
CN104450197A (en) * 2014-12-03 2015-03-25 南华大学 Method for extracting litsea cubeba oil and citral
CN106117027A (en) * 2016-06-20 2016-11-16 聊城大学 Utilize the method that micro-structured reactor prepares cyclocitral
CN106316816A (en) * 2016-08-22 2017-01-11 鹰潭中投科技有限公司 Method for preparing natural citral
CN108383702A (en) * 2017-12-15 2018-08-10 永州山香香料有限公司 A method of extracting citronellal from fruit of a cubeb litsea tree hair oil
CN109053407A (en) * 2018-06-28 2018-12-21 厦门欧米克生物科技有限公司 A method of synthesis β-Damascenone
WO2020072908A1 (en) * 2018-10-05 2020-04-09 Manus Bio, Inc. Biosynthesis and recovery of secondary metabolites
CN110845309A (en) * 2019-11-19 2020-02-28 中南大学 Preparation method of natural citral

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PAR E. DEMOLE, P. ENGGIST等: "Structure et synthhse de la damasc6none (trim6thyl-2, 6, 6-trans-crotonoyl-1-cyclohexadi&ne-1, 3), constituant odorant de l’essence de rose bulgare (Rosa darnascena Mill.)", HELVETICA CHIMICA ACTA(1970), vol. 53, no. 3, pages 541 - 551 *

Similar Documents

Publication Publication Date Title
CN104450202B (en) A kind of preparation method of high-purity orange peel essential oil
CN105542966A (en) Method for extracting high-yield citrus essential oil
Hopf et al. Synthesis of Cyclo‐1, 3‐dien‐5‐ynes
CN113816840A (en) Synthesis method of beta-damascenone
CN109369397A (en) A kind of Ag+The method of short-chain polyol coupling extraction and separation methyl linolenate
CN100564356C (en) The synthesis technique of β-Hu Luobusu
CN105695103A (en) Method for extracting refined cane wax from filter mud
CN110002979B (en) Preparation method of damascone
CA1177094A (en) Odorants and/or flavourants
JPS62209029A (en) Manufacture of hexamethyltetracosans
CA1087638A (en) Perfume compositions containing cis-and trans- trimethylcyclohexylethyl ethers and a process for making the trans-ether
CN111302919A (en) Method for synthesizing high-content dihydrojasmone spice
CN110845309A (en) Preparation method of natural citral
JPS62275199A (en) Non-phototoxic orange flower essential oil
Marcos et al. Chemistry of ent-halimic acid: synthesis of [4.3. 3] propellanes
JP3700971B2 (en) Orange oil production method
JPS5924795A (en) Manufacture of deterpenated essential oil
JP2735600B2 (en) Cycloaliphatic ketones, methods for their preparation and methods for imparting, modulating or improving sensory and odor properties
EP0070995B1 (en) Process for the preparation of cycloaliphatic unsaturated ketones
EP0282798B1 (en) Aliphatic bicyclic alcools and their use as flavouring compounds
CN104557815A (en) Isotopically labeled methyl furanone, intermediate and preparation method of isotopically labeled methyl furanone
CN104447178A (en) Synthetic method of 3,4-dibenzanthracene
CN109735133A (en) The separation method of pigment in a kind of idesia oil
CH655099A5 (en) METHOD FOR PRODUCING 4-METHYLJONONE.
CN113088381A (en) Method for reducing peroxide value of walnut oil

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination