CN115477581A - Preparation method of high-cis methyl dihydrojasmonate - Google Patents
Preparation method of high-cis methyl dihydrojasmonate Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- KVWWIYGFBYDJQC-MNOVXSKESA-N methyl 2-[(1r,2s)-3-oxo-2-pentylcyclopentyl]acetate Chemical compound CCCCC[C@H]1[C@@H](CC(=O)OC)CCC1=O KVWWIYGFBYDJQC-MNOVXSKESA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940125904 compound 1 Drugs 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000002798 polar solvent Substances 0.000 claims abstract description 9
- GEWDNTWNSAZUDX-WQMVXFAESA-N (-)-methyl jasmonate Chemical class CC\C=C/C[C@@H]1[C@@H](CC(=O)OC)CCC1=O GEWDNTWNSAZUDX-WQMVXFAESA-N 0.000 claims abstract description 8
- 229940125782 compound 2 Drugs 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- -1 3-hydroxy-2-pentyl-cyclopentenyl methyl Chemical group 0.000 claims abstract description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 229940126214 compound 3 Drugs 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims 1
- 125000000468 ketone group Chemical group 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 150000004702 methyl esters Chemical class 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- KVWWIYGFBYDJQC-UHFFFAOYSA-N methyl dihydrojasmonate Chemical compound CCCCCC1C(CC(=O)OC)CCC1=O KVWWIYGFBYDJQC-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000003205 fragrance Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000012230 colorless oil Substances 0.000 description 3
- DKQFRTZQINXKJI-UHFFFAOYSA-N methyl 2-(3-hydroxy-2-pentylcyclopenten-1-yl)acetate Chemical compound CCCCCC1=C(CC(=O)OC)CCC1O DKQFRTZQINXKJI-UHFFFAOYSA-N 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 235000010254 Jasminum officinale Nutrition 0.000 description 1
- 240000005385 Jasminum sambac Species 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
Classifications
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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
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:
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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