CN110746283A - Synthesis process of β -damascone - Google Patents

Synthesis process of β -damascone Download PDF

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CN110746283A
CN110746283A CN201810821715.1A CN201810821715A CN110746283A CN 110746283 A CN110746283 A CN 110746283A CN 201810821715 A CN201810821715 A CN 201810821715A CN 110746283 A CN110746283 A CN 110746283A
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trimethylcyclohex
ethanone
enyl
damascone
reaction
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郭兴永
王锦华
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Xinxiang Boyuan Biological Technology Co Ltd
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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
    • C07C45/61—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
    • C07C45/72—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 by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—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 by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
    • 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
    • C07C45/69—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 by addition to carbon-to-carbon double or triple bonds
    • 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

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention belongs to the technical field of chemical synthesis of spices and essences, and particularly relates to a novel synthesis process for industrially producing β -damascone, wherein 1, 3-pentadiene is used as a starting raw material in AlCl3The synthesis process has the main advantages of low raw material cost and low energy consumption, wherein the olefin isomerization production process adopts a gas phase reaction catalyzed by solid superacid, the product purity is high, no reaction solvent is needed, the waste water and the waste gas are few, and the catalyst has good reusability.

Description

Synthesis process of β -damascone
Technical Field
The invention belongs to the technical field of chemical synthesis of flavors and fragrances, and particularly relates to a novel synthesis process for industrially producing β -damascone.
Background
β -Damascone (β -Damascone, formula 1), also known as β -dihydrodamascone, is a valuable daily perfume, and can also be used as a food perfume (food additive standard, GB 2760-.
Figure BDA0001741546760000011
β -damascone has the advantages of pure fragrance, elegant fragrance, lasting fragrance, no toxicity and the like, and is mainly used for top-grade cosmetics, rare tobaccos, edible essence and the like (Wangzaigang, spice essence cosmetics, 2003,1. Matsunagaga, K.; Kanayama, T.; Konno, K.; Hasegawa, M.; Fuwa, R.; Kondo, T.Patent JP 2010018569,2010,1, 28.). β -damascone has an important status in the field of essence and spice, and the research on the synthetic method has great application value.
(1) The β -cyclocitral method uses β -cyclocitral as raw material, firstly makes addition reaction with allyl magnesium bromide, then makes it pass through MnO2The target compound is obtained by oxidation to β -damascone (Demole, E.; Enggist, P.; Saeuberli, U.; Stoll, M.; Kovats, E.Helv. Chim. acta1970,53,541.), or by an addition reaction with lithium propiolate, followed by oxidation and reduction of the triple bond to obtain β -damascone (Watanabe; Kazunori, Patent JP 2001247504A,2001,9, 11.).
(2) The cycloparaffinate method is characterized in that methyl or ethyl cycloparaffinate is used as a raw material, and is subjected to addition reaction with allyl magnesium chloride, then decomposition reaction is carried out by using strong base, and finally isomerization is carried out under catalysis of p-toluenesulfonic acid, so that the target β -damascone (Snowden, R.L.; Linder, S.M.; Muller, B.L.; Schulte-Elte, K.H.Helv.Chim.acta1987,70,1858. Liqiong, Huang-Adiang, Lu-Wen, Hemsonian, Hemsmin, Chemicals, 2011,74,275. Liqiong, Huang-Adiang, Lu, Hemsyn, patent, CN 101698636A,2013,2,20.) is prepared.
(3) β -ionone method is carried out by reacting β -ionone with hydrazine to generate oxime, reacting with isoketone to obtain final product
Figure BDA0001741546760000021
The oxazoline intermediate was finally reduced with liquid ammonia/sodium to give β -damascone (Buechi, G.; Vederas, J.C.J.Am.chem.Soc.1972,94,9128).Zhanqiangjiang, chengying, xubaohua, zenailu, CN 104003860B,2016,5, 18.); or oxidizing epoxy ketone with hydrogen peroxide, reacting with hydrazine to generate oxime, performing Wharton transposition, and performing MnO treatment2The oxidation gives β -damascone (Dupuy, C.; Luche, J.L.tetrahedron 1989,45,3437.), or the oxidation is carried out with hydrogen peroxide to form epoxy ketone and then NaBH4Reducing, brominating, ring-opening reacting, isomerizing under catalysis of p-toluenesulfonic acid to obtain β -damascone (Sarandeses, L.A.; Luche, J.L.J.org.chem.1992,57,2757).
(4) The diene synthesis method is characterized in that Diels-Alder addition of 1, 3-pentadiene and 4-methyl-3-penten-2-one is used as an initial reaction, olefin isomerization is carried out, and finally the Diels-Alder addition and the Diels-Alder addition react with acetaldehyde to generate β -damascone (Watanabe, S.; Ujihara, H.; Yamamoto, T.; Hagiwara, T.Patent EP 1162190A2,2001, 12.Watanabe, S.; Ujihara H.; Yamamoto, T.; Hagiwara, T.Patent U.S. Pat. No. 20020004615A 1,2002,1, 10.).
Although many researches on the synthesis of β -damascone have been reported, the existing method has the problems of high cost, complex operation and the like, and is difficult to realize industrial production, at present, the research on the industrial production of β -damascone is almost blank, so the research on the synthesis process of β -damascone in industrial production is urgent to solve, and has important practical significance.
Disclosure of Invention
Aiming at the key problem of realizing the industrial production of β -damascone, the invention aims to provide a synthesis process for industrially producing β -damascone, which has low raw material cost, low energy consumption and environmental friendliness, wherein 1, 3-pentadiene (marked as 1 in a formula 2) with low price is used as a starting material in AlCl3Under the catalysis of the method, the method firstly generates Diels-Alder addition reaction with 4-methyl-3-pentene-2-ketone (marked as 2 in a formula 2) to generate 1- (2,6,6, -trimethylcyclohex-3-alkenyl) -ethanone (marked as 3 in the formula 2), then generates olefin isomerization under the catalysis of a solid super acidic catalyst to obtain 1- (2,6,6, -trimethylcyclohex-1-alkenyl) -ethanone (marked as 4 in the formula 2), and finally generates aldol condensation reaction with acetaldehyde to generate target product β -damasconeThe specific synthetic route of β -damascone is shown in formula 2.
Figure BDA0001741546760000022
The invention provides a synthesis process for industrially producing β -damascone, which comprises the following steps:
(1) synthesis of diene for preparing 1- (2,6,6, -trimethyl cyclohex-3-alkenyl) -ethanone
Adding dichloromethane and anhydrous aluminum trichloride into a reaction kettle, uniformly stirring, adding 4-methyl-3-penten-2-one, uniformly stirring again, introducing 1, 3-pentadiene, continuously stirring for reaction, monitoring the reaction by GC, adding ice water after the reaction is finished, performing extraction and quenching reaction, separating liquid, washing an organic phase by using a saturated NaCl aqueous solution, recovering dichloromethane, sending a residual organic phase into a rectifying kettle, and rectifying to obtain 1- (2,6, 6-trimethylcyclohex-3-alkenyl) -ethanone;
(2) isomerization of olefins to 1- (2,6,6, -trimethylcyclohex-1-enyl) -ethanones
Loading a solid super acidic catalyst into a gas phase reactor, heating to 300 ℃ under nitrogen purging, then decompressing, introducing 1- (2,6, 6-trimethylcyclohex-3-enyl) -ethanone into the gas phase reactor, continuing to heat and react at the temperature of 380 ℃ under 300-;
(3) preparation of β -damascone by aldol condensation
Adding a tetrahydrofuran solution of ethyl magnesium bromide into a reaction kettle, cooling to 0 ℃, dropwise adding the tetrahydrofuran solution of N-methylaniline, adding 1- (2,6,6, -trimethylcyclohex-1-enyl) -ethanone under stirring, heating to room temperature, stirring for reaction, slowly adding the tetrahydrofuran solution of acetaldehyde, monitoring the reaction by GC, adding a hydrochloric acid solution, continuously stirring for reaction, separating liquid after the reaction is finished, extracting a water phase with ethyl acetate, combining organic phases, sequentially washing with a NaOH solution and a saturated NaCl aqueous solution, recovering a solvent, and feeding the residual organic phase into a rectifying kettle to prepare β -damascone.
The synthesis process provided by the invention has the main advantages that: the production process has the advantages that the raw material cost is low, the energy consumption is low, the production process for isomerizing the 1- (2,6, 6-trimethylcyclohex-3-enyl) -ethanone into the 1- (2,6, 6-trimethylcyclohex-1-enyl) -ethanone adopts a gas phase reaction catalyzed by solid superacid, the product purity is high, a reaction solvent is not needed, the waste water and the waste gas are few, and the reusability of the catalyst is good.
Detailed Description
Example 1
Synthesis of diene for preparing 1- (2,6,6, -trimethyl cyclohex-3-alkenyl) -ethanone
Adding dichloromethane (200L) and anhydrous aluminum trichloride (319Kg,2400mol) into a reaction kettle, uniformly stirring, dropwise adding a dichloromethane solution (150L) of 4-methyl-3-penten-2-one (294Kg, 3000mol), stirring for 2h, introducing 1, 3-pentadiene, continuously stirring for reaction, monitoring the reaction by GC, and stopping the reaction when the content of the 4-methyl-3-penten-2-one is lower than 1%. Ice water (400L) was added to quench the reaction and the layers were separated. The organic phase was washed with saturated aqueous sodium chloride solution, methylene chloride was recovered by distillation, and the residual organic phase was fed to a rectifying still and rectified to give 1- (2,6,6, -trimethylcyclohex-3-enyl) -ethanone (358Kg, yield 72%).
Example 2
Isomerization of olefins to 1- (2,6,6, -trimethylcyclohex-1-enyl) -ethanones
Adding SO4 2-/ZrO2The solid super acidic catalyst (7.9Kg,36mol) is loaded into a gas phase reactor with the diameter of 0.16 meter and the length of 5 meters, the gas phase reactor is heated to 300 ℃ under the nitrogen purging, then the pressure in the gas phase reactor is reduced to 45mmHg, 1- (2,6,6, -trimethylcyclohex-3-enyl) -ethanone (60Kg,360mol) is introduced into the gas phase reactor at the speed of 7.5Kg/h and continuously maintained at the temperature of 300 ℃ for reaction, after the reaction is finished, the reaction gas enters a cooling tower for cooling, and the cooled mixed solution is sent into a rectifying kettle for rectification to obtain the 1- (2,6,6, -trimethylcyclohex-1-enyl) -ethanone (51Kg, the yield is 85 percent, the conversion rate is 99 percent, and the purity is 95 percent). SO (SO)4 2-/ZrO2The solid super acidic catalyst is continuously recycled for 6 times.
TABLE 1 Effect of catalyst recycle on conversion and yield
Example 3
Preparation of β -damascone by aldol condensation
Adding a tetrahydrofuran solution (1.0M, 1800L) of ethyl magnesium bromide into a reaction kettle, introducing frozen salt water into a cooling jacket of the reaction kettle, cooling the reaction kettle to 0 ℃, dropwise adding a tetrahydrofuran solution (128.5Kg, 1200mol, 500L) of N-methylaniline, uniformly stirring at 0 ℃, adding 1- (2,6,6, -trimethylcyclohex-1-enyl) -ethanone (166Kg, 1000mol), heating the reaction kettle to room temperature, continuously stirring for 5h, slowly adding a tetrahydrofuran solution (39.6Kg, 900mol, 300L) of acetaldehyde, monitoring the reaction by GC, adding a 10% hydrochloric acid solution (1000L) when the content of the 1- (2,6,6, -trimethylcyclohex-1-enyl) -ethanone is lower than 1%, continuously stirring for 1h, stopping the reaction, separating, extracting an aqueous phase with ethyl acetate (1000L multiplied by 2), combining organic phases, sequentially washing with a 5% aqueous solution of NaOH and a saturated aqueous solution of NaCl, recovering the tetrahydrofuran and the ethyl acetate, rectifying the residual organic phase, sending the distilled organic phase into a rectifying furnace, heating the product in a rectifying furnace to obtain 163- β% of the product.

Claims (5)

1. A process for industrially preparing β -damascone includes such steps as preparing 1, 3-pentadiene as initial raw material from AlCl3The method comprises the steps of firstly carrying out Diels-Alder addition reaction with 4-methyl-3-pentene-2-ketone under the catalysis of the (1) methyl-3-pentene-2-ketone to generate 1- (2,6,6, -trimethylcyclohex-3-alkenyl) -ethanone, then carrying out olefin isomerization under the catalysis of a solid super acid catalyst to obtain 1- (2,6,6, -trimethylcyclohex-1-alkenyl) -ethanone, and finally carrying out aldol condensation reaction with acetaldehyde to generate the target product β -damascone.
2. The process for synthesizing β -damascone according to claim 1, wherein the step of synthesizing 1- (2,6, 6-trimethylcyclohex-1-enyl) -ethanone comprises charging a solid superacid catalyst into a gas phase reactor, heating to 300 ℃ under nitrogen purging, reducing pressure, introducing 1- (2,6, 6-trimethylcyclohex-3-enyl) -ethanone into the gas phase reactor, continuing heating at 380 ℃ for reaction, cooling the reaction gas in a cooling tower, and rectifying to obtain 1- (2,6, 6-trimethylcyclohex-1-enyl) -ethanone.
3. The synthetic procedure according to claim 2, characterized in that the solid superacid catalyst used for the synthesis of 1- (2,6,6, -trimethylcyclohex-1-enyl) -ethanone is SO4 2-/ZrO2、SO4 2-/SiO2、SO4 2-/TiO2、SO4 2-/Al2O3、SO4 2-/ZrO2-TiO2、SO4 2-/ZrO2-Al2O3、SO4 2-/ZrO2-SiO2、SO4 2-/TiO2-Al2O3、SO4 2-/SiO2-Al2O3Preferably SO4 2-/ZrO2Solid super acidic catalyst.
4. The synthesis procedure as claimed in claim 2, characterized in that SO is used for the synthesis of 1- (2,6,6, -trimethylcyclohex-1-enyl) -ethanones4 2-/ZrO2The solid superacid catalyst is used in an amount of 5 to 15%, preferably 10%.
5. The synthesis step according to claim 2, characterized in that the temperature range for the synthesis of 1- (2,6,6, -trimethylcyclohex-1-enyl) -ethanone is 300-.
CN201810821715.1A 2018-07-24 2018-07-24 Synthesis process of β -damascone Pending CN110746283A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111440055A (en) * 2020-04-24 2020-07-24 万华化学集团股份有限公司 Synthesis method of β -damascone
CN113387784A (en) * 2021-07-12 2021-09-14 山东新和成药业有限公司 Acid-base catalyst and application thereof in delta-damascenone synthesis

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111440055A (en) * 2020-04-24 2020-07-24 万华化学集团股份有限公司 Synthesis method of β -damascone
CN111440055B (en) * 2020-04-24 2022-11-08 万华化学集团股份有限公司 Synthesis method of beta-damascone
CN113387784A (en) * 2021-07-12 2021-09-14 山东新和成药业有限公司 Acid-base catalyst and application thereof in delta-damascenone synthesis

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