CN115477581A - Preparation method of high-cis methyl dihydrojasmonate - Google Patents

Preparation method of high-cis methyl dihydrojasmonate Download PDF

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CN115477581A
CN115477581A CN202211109157.9A CN202211109157A CN115477581A CN 115477581 A CN115477581 A CN 115477581A CN 202211109157 A CN202211109157 A CN 202211109157A CN 115477581 A CN115477581 A CN 115477581A
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reaction
cis
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methyl dihydrojasmonate
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张晓鹏
杨志健
杨洋
彭兵兵
潘红梅
韩万龙
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Anhui Jinhe Chemical Material Research Institute Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated

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Abstract

The invention discloses a preparation method of high cis methyl dihydrojasmonate, which comprises the steps of adding dehydrogenated methyl jasmonate (compound 1), 0.1-1 wt% of metal supported catalyst and polar solvent (the volume ratio of the compound 1 to the polar solvent is 1-10) into a hydrogenation kettle; replacing with nitrogen and hydrogen for three times respectively, keeping the temperature of the kettle at 45-75 ℃ and the pressure of the kettle at 1.0-3.0 MPa, and continuously introducing hydrogen until the reaction is finished to obtain reaction liquid containing 3-hydroxy-2-pentyl-cyclopentenyl methyl acetate (compound 2). In conclusion, the invention overcomes the defects of the prior art, has reasonable design, adopts the same catalyst, realizes the reduction of ketone group and double bond in the dehydrojasmonic acid methyl ester by changing the temperature and pressure of the reaction through a one-pot method, has novel method, simplifies the reaction steps, and has higher social use value and application prospect.

Description

Preparation method of high-cis methyl dihydrojasmonate
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a preparation method of high-cis methyl dihydrojasmonate.
Background
The cis-methyl dihydrojasmonate is colorless to light yellow liquid, has strong and elegant jasmine fragrance and comfortable lemon fruit fragrance, has a low fragrance threshold value, and has far higher fragrance intensity than common methyl dihydrojasmonate. The preparation method of the compound is various. Patent CN101613277 can convert trans-methyl dihydrojasmonate into cis-methyl dihydrojasmonate by microwave heating under the condition of catalyst, but the conversion ratio is low, the cis isomer ratio is 6% of the raw material, the reaction is finished, and the cis content is only 13-16%. CN101429123 uses common methyl dihydrojasmonate as raw material, amine and metal cation as catalyst, and heats to 120-150 deg.C under nitrogen protection, and keeps the temperature for 8-10 h, and obtains methyl dihydrojasmonate with about 35% cis-isomer content, and the cis-trans ratio is not high.
The method for obtaining cis-methyl dihydrojasmonate by catalytic hydrogenation of dehydrogenated methyl jasmonate is a common method, and for example, the method is disclosed in the document [ Helvetica Chimica Acta,2005,88 (12): 3069-3088], wherein the cis-methyl dihydrojasmonate is prepared by hydrogenation with dehydrogenated methyl jasmonate as a raw material and Pd/C as a catalyst, and the cis-methyl dihydrojasmonate has a cis-to-trans ratio of 62. Although the addition of olefins is a cis addition, the olefins are sterically hindered, complete cis hydrogenation is difficult, and the cis ratio is often limited. Other catalysts, such as ruthenium ligand catalysts, can increase the cis-to-trans ratio of the compounds, but the catalyst preparation process is cumbersome and not conducive to recycling.
Therefore, the inventors have studied and improved the prior art and the deficiency thereof with the experience of design development and actual manufacturing abundant in the related industry for many years, and provide a method for preparing high cis-dihydrojasmonic acid methyl ester, so as to achieve the purpose of more practical value.
Disclosure of Invention
In order to solve the problems mentioned in the background technology, the invention provides a preparation method of high cis-methyl dihydrojasmonate, which greatly improves the proportion of cis-isomers, and has the advantages of simple operation steps, mild reaction conditions, high yield and easy separation.
In order to achieve the purpose, the invention adopts the following technical scheme that the reaction route is as follows:
Figure BDA0003842478820000021
the method takes dehydrogenated methyl jasmonate as a raw material to prepare high cis-form methyl dihydrojasmonate, and comprises three steps of reduction of a ketone group, reduction of a double bond and oxidation of a hydroxyl group in the dehydrogenated methyl jasmonate.
Step S1: adding dehydrogenated methyl jasmonate (compound 1), 0.1-1 wt% of metal supported catalyst and polar solvent (the volume ratio of the compound 1 to the polar solvent is 1-10) into a hydrogenation kettle; replacing three times with nitrogen and three times with hydrogen respectively, maintaining the kettle temperature at 45-75 ℃ and the kettle pressure at 1.0-3.0 MPa, and continuously introducing the hydrogen until the reaction is finished to obtain reaction liquid containing 3-hydroxy-2-pentyl-cyclopentenyl methyl acetate (compound 2);
step S2: adjusting the reaction temperature to 0-50 ℃, keeping the kettle pressure at 2.0-4.0 MPa, continuously introducing hydrogen until the reaction is finished, filtering by using kieselguhr, adding saturated sodium bicarbonate into the filtrate, extracting, and rectifying under reduced pressure to obtain cis-3-hydroxy-2-pentyl-cyclopentyl methyl acetate (compound 3);
and step S3: adding cis-3-hydroxy-2-pentyl-cyclopentyl methyl acetate (compound 3), 0.1-2 wt% of alkaline reagent and dichloromethane (the volume ratio of the compound 3 to the solvent is 1-8) into an open reaction bottle, reacting at 0-70 ℃, and stopping the reaction after the reaction of the raw materials is detected; extracting, distilling under reduced pressure to obtain high cis-methyl dihydrojasmonate (compound 4), and controlling the conditions to obtain cis-methyl dihydrojasmonate with a cis-to-trans ratio of 10-92%.
Preferably, in step S1, the catalyst-supporting metal is palladium, ruthenium, rhodium, platinum, or the like; the carrier is active carbon, alumina, silicon dioxide, etc.; the solvent is polar solvent such as methanol, ethanol, tert-butanol, water, etc.; the addition amount of the catalyst is 0.1-1 wt%; the volume ratio of the compound 1 to the polar solvent is 1-10; the reaction temperature is 45-75 ℃; the kettle pressure is 1.0-3.0 MPa.
Preferably, in step S3, the alkaline agent is a hydroxide, carbonate, hydride of lithium, sodium, potassium, cesium, or the like; the addition amount of the catalyst is 0.1-2 wt%; the volume ratio of the compound 3 to the solvent is 1-8, and the reaction temperature is 10-60 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention adopts the same catalyst, and realizes the reduction of ketone group and double bond in the dehydrojasmonic acid methyl ester by changing the temperature and pressure of the reaction through a one-pot method, the method is novel, and the reaction steps are simplified;
(2) According to the invention, a mode of reducing ketone group in dehydrogenated methyl jasmonate and then reducing double bond is adopted, the reaction condition is mild, and the structure of the compound after double bond reduction is basically cis-isomer;
(3) The cis-methyl dihydrojasmonate is obtained by oxidizing cis-3-hydroxy-2-pentyl-cyclopentyl methyl acetate by controlling reaction conditions, the cis-trans ratio is easy to control, and the yield is high; under mild conditions, the cis-trans ratio can reach 92%, and the high cis-dihydrojasmonic acid methyl ester belongs to high cis-dihydrojasmonic acid methyl ester and has more excellent fragrance intensity.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. 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.
Example 1
Adding 10g of methyl dehydrojasmonate (Compound 1) to a reaction vessel containing 0.05g of 5wt% Pt/C and 10ml of methanol, substituting with nitrogen three times, charging 1MPa of hydrogen, stirring at 50 ℃ until the reaction of the raw materials is completed, and stopping the reaction. To obtain a reaction solution containing methyl 3-hydroxy-2-pentyl-cyclopentenylacetate (compound 2).
And (3) reducing the reaction temperature of the reaction liquid to 10 ℃, adjusting the hydrogen pressure to 2MPa, stirring until the raw materials are reacted, and stopping the reaction. Filtering with celite pad, adding saturated sodium bicarbonate into the filtrate, extracting, rectifying under reduced pressure, and separating to obtain colorless oily cis-3-hydroxy-2-pentyl-cyclopentyl methyl acetate (compound 3) with yield of 95%. H-NMR (400MHz, CDCl3): 0.89 (t, J =7.0,3H); 1.12-1.20 (m, 1H); 1.22-1.38 (m, 7H); 1.47-1.58 (m, 1H); 1.77-1.83 (m, 2H); 1.91-1.98 (m, 1H); 2.02-2.10 (m, 2H); 2.14 (dd, J =10.0,14.6,1H); 2.38 (dd, J =6.2,14.6,1H); 2.58-2.67 (m, 1H); 3.67 (s, 3H); 3.99 (dt, J =4.4,6.8,1H).
8.0g of cis-3-hydroxy-2-pentyl-cyclopentylacetic acid methyl ester (compound 3) was dissolved in 10ml of dichloromethane, 0.1wt% of cesium carbonate was added, the mixture was opened to the atmosphere, the mixture was stirred at 25 ℃ until the reaction was completed, and the reaction was stopped after completion of the reaction of the starting materials was detected. Extraction and reduced pressure distillation are carried out, thus obtaining the cis-methyl dihydrojasmonate (compound 4) of colorless oil, the yield is 90 percent, and the cis-isomer content is 92 percent. H-NMR (400MHz, CDCl3): 0.89 (t, J =7.0Hz, 3H); 1.54-1.11 (m, 6H); 1.58 (m, 1H); 1.86 (m, 1H); 2.27-2.07 (m, 5H); 2.30 (q, J =7.2hz, 1h); 2.42 (dd, J =5.4,15.6hz, 1h); 2.82 (m, 1H); 3.66 (s, 3H).
Example 2
10g of dehydrojasmonic acid methyl ester (Compound 1) was charged into a reaction vessel containing 0.05g of 10wt% Ru/C and 20ml of t-butanol, and the reaction was stopped after replacing the reaction with nitrogen gas three times, charging 2MPa of hydrogen gas, and stirring at 70 ℃ until the reaction of the raw materials was completed. To obtain a reaction solution containing methyl 3-hydroxy-2-pentyl-cyclopentenylacetate (compound 2).
And (3) reducing the reaction temperature of the reaction solution to 0 ℃, stirring until the reaction of the raw materials is finished, and stopping the reaction. Filtering with celite pad, adding saturated sodium bicarbonate into the filtrate, extracting, rectifying under reduced pressure, and separating to obtain colorless oily cis-3-hydroxy-2-pentyl-cyclopentyl methyl acetate (compound 3) with yield of 90%. H-NMR (400MHz, CDCl3): 0.89 (t, J =7.0,3H); 1.12-1.20 (m, 1H); 1.22-1.38 (m, 7H); 1.47-1.58 (m, 1H); 1.77-1.83 (m, 2H); 1.91-1.98 (m, 1H); 2.02-2.10 (m, 2H); 2.14 (dd, J =10.0,14.6,1H); 2.38 (dd, J =6.2,14.6,1H); 2.58-2.67 (m, 1H); 3.67 (s, 3H); 3.99 (dt, J =4.4,6.8,1H).
7.5g of cis-3-hydroxy-2-pentyl-cyclopentylacetic acid methyl ester (compound 3) was dissolved in 10ml of dichloromethane, 0.1wt% of NaH was added, the mixture was opened to the atmosphere, the mixture was stirred at 25 ℃ until the reaction was completed, and the reaction was stopped after completion of the reaction of the starting materials was detected. The mixture was filtered through celite pad, extracted, and distilled under reduced pressure to give methyl cis-dihydrojasmonate (compound 4) as a colorless oil in a yield of 90% and a cis-isomer content of 89%. H-NMR (400MHz, CDCl3): 0.89 (t, J =7.0Hz, 3H); 1.54-1.11 (m, 6H); 1.58 (m, 1H); 1.86 (m, 1H); 2.27-2.07 (m, 5H); 2.30 (q, J =7.2hz, 1h); 2.42 (dd, J =5.4,15.6hz, 1h); 2.82 (m, 1H); 3.66 (s, 3H).
Example 3
10g of methyl dehydrojasmonate (Compound 1) was charged into a reaction vessel containing 0.05g of 5wt% Ru/C and 10ml of n-butanol, nitrogen gas was substituted three times, 2MPa of hydrogen gas was charged, and the reaction was stopped at 70 ℃ until the reaction of the raw materials was completed. To obtain a reaction solution of methyl 3-hydroxy-2-pentyl-cyclopentenylacetate (compound 2).
And (3) reducing the reaction temperature of the reaction liquid to 45 ℃, stirring until the reaction of the raw materials is finished, and stopping the reaction. Filtering with celite pad, adding saturated sodium bicarbonate into the filtrate, extracting, rectifying under reduced pressure, and separating to obtain colorless oily cis-3-hydroxy-2-pentyl-cyclopentyl methyl acetate (compound 3) with yield of 80%. H-NMR (400MHz, CDCl3): 0.89 (t, J =7.0,3H); 1.12-1.20 (m, 1H); 1.22-1.38 (m, 7H); 1.47-1.58 (m, 1H); 1.77-1.83 (m, 2H); 1.91-1.98 (m, 1H); 2.02-2.10 (m, 2H); 2.14 (dd, J =10.0,14.6,1H); 2.38 (dd, J =6.2,14.6,1H); 2.58-2.67 (m, 1H); 3.67 (s, 3H); 3.99 (dt, J =4.4,6.8,1H).
7.5g of cis-3-hydroxy-2-pentyl-cyclopentylacetic acid methyl ester (compound 3) was dissolved in 10ml of dichloromethane, 0.1wt% of K2CO3 was added, the mixture was opened to the atmosphere, the mixture was stirred at 70 ℃ until the reaction was completed, and the reaction was stopped upon completion of the reaction of the starting materials. The mixture was filtered through celite pad, extracted, and distilled under reduced pressure to obtain methyl cis-dihydrojasmonate (compound 4) as colorless oil in 90% yield and 25% cis-isomer content. H-NMR (400MHz, CDCl3): 0.89 (t, J =7.0Hz, 3H); 1.54-1.11 (m, 6H); 1.58 (m, 1H); 1.86 (m, 1H); 2.27-2.07 (m, 5H); 2.30 (q, J =7.2hz, 1h); 2.42 (dd, J =5.4,15.6hz, 1h); 2.82 (m, 1H); 3.66 (s, 3H).
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.

Claims (9)

1. A preparation method of high-cis methyl dihydrojasmonate is characterized by comprising the following steps:
step S1, adding dehydrogenated methyl jasmonate (compound 1), a metal supported catalyst and a polar solvent into a hydrogenation kettle; replacing with nitrogen and hydrogen for three times respectively, keeping the temperature of the kettle at 45-75 ℃ and the pressure of the kettle at 1.0-3.0 MPa, and continuously introducing hydrogen until the reaction is finished to obtain a reaction liquid containing 3-hydroxy-2-pentyl-cyclopentenyl methyl acetate (compound 2);
s2, adjusting the reaction temperature to 0-50 ℃, keeping the kettle pressure to 2.0-4.0 MPa, continuously introducing hydrogen until the reaction is finished, filtering by using diatomite, adding saturated sodium bicarbonate into the filtrate, extracting, and performing rectification under reduced pressure to obtain cis-3-hydroxy-2-pentyl-cyclopentyl methyl acetate (compound 3);
s3, adding cis-3-hydroxy-2-pentyl-cyclopentyl methyl acetate (compound 3), an alkaline reagent and dichloromethane into an open reaction bottle, reacting at 0 to 70 ℃, and stopping the reaction after the detection of the reaction of the raw materials is finished; extracting, and distilling under reduced pressure to obtain high cis-methyl dihydrojasmonate (compound 4).
2. The method for preparing high-cis methyl dihydrojasmonate according to claim 1, wherein the catalyst-supported metal in the reduction step S1-S2 is one or more of palladium, ruthenium, rhodium and platinum, and the carrier is one or more of activated carbon, alumina and silica.
3. The preparation method of high-cis methyl dihydrojasmonate according to claim 1, wherein the amount of the catalyst added in the S1-S2 reduction step is 0.1wt% to 1wt%.
4. The method for preparing high-cis methyl dihydrojasmonate according to claim 1, wherein in the step S1 to S2, a solvent for reaction is methanol, ethanol, tert-butanol or a water polar solvent.
5. The method for preparing high-cis methyl dihydrojasmonate according to claim 1, wherein in the step S1 to S2, the volume ratio of the compound 1 to the polar solvent is 1 to 10.
6. The method of claim 1, wherein the reaction between S1 and S2 is performed in one step.
7. The method for preparing high-cis methyl dihydrojasmonate according to claim 1, wherein the alkaline reagent in the step S3 is a hydroxide, a carbonate or a hydride of lithium, sodium, potassium or cesium.
8. The method for preparing high-cis methyl dihydrojasmonate according to claim 1, wherein the amount of the catalyst added in the step S3 is 0.1-2 wt%.
9. The method for preparing high-cis methyl dihydrojasmonate according to claim 1, wherein the volume ratio of the compound 3 to the solvent in the step S3 is 1~8.
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