CN100582082C - Synthesizing process of cis-dihydro jasmine keto-acid methyl ester - Google Patents
Synthesizing process of cis-dihydro jasmine keto-acid methyl ester Download PDFInfo
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Abstract
This invention involves a cis-dihydrojasmone acid methyl ester synthetic method. The existing multi-step synthesis method is low yield and product content. This invention takes ordinary dihydrojasmone acid methyl ester as raw material, by enolase reaction and halogenation reaction, to dehalogenate to prepare double bonds jasmonate methyl ester; finally, under the solvent-free state through hydrogenation to obtain cis-dihydrojasmone acid methyl ester.
Description
Technical field
The present invention relates to the preparation of flavor compounds, specifically a kind of synthetic method of cis-dihydro jasmine keto-acid methyl ester.
Background technology
Methyl dihydrojasmonate (chemical name: 2-amyl group-3-carbonyl NSC 60134 methyl esters) have following four kinds of structural formulas.Mainly be the methyl dihydrojasmonate of transconfiguration in the common methyl dihydrojasmonate, it has graceful soft Flower of Arabian Jasmine note and comfortable lemon sample fruital breath, and whole fragrance is merrily and lightheartedly elegant, and lasting is lasting, and blending is effective.
Compare with common methyl dihydrojasmonate, cis-dihydro jasmine keto-acid methyl ester is having a kind of superpower fragrance promoting or transferring effect aspect the pure and fresh modern fragrance of a flower gas, its intensity is far above common methyl dihydrojasmonate, has the strong and famous and precious fragrance of a flower, like jasmine, sweet lasting, powder perfume (or spice) is arranged slightly, diffustivity is good.Because its cis proportion is higher, " dilution effect " that regular grade is produced when having avoided high density to use.
The synthetic route of cis-dihydro jasmine keto-acid methyl ester has following several: utilize two keys under heterogeneous hydrogenation catalyst effect, catalysis contains α, the methyl jasmonate hydrogenation of the two keys of β generates cis-dihydro jasmine keto-acid methyl ester, containing α as having introduced in the U.S. Pat 3978108, the methyl jasmonate of the two keys of β carries out the hydrogenation preparing cis-dihydro jasmine keto-acid methyl ester with catalyst P d/C in alcohols or esters solvent.But this patent is not mentioned α, the source or the preparation method of the methyl jasmonate of the two keys of β; In addition, in order to improve the content of cis-dihydro jasmine keto-acid methyl ester in the product, added an amount of organo-aluminium compound in this patented method, the recovery set that is difficult to of Pd/C is used, and the solvent that adds also can with contain α, the methyl jasmonate of the two keys of β with and the hydrogenation products methyl dihydrojasmonate between transesterification reaction takes place, though do not influence cis-dihydro jasmine keto-acid methyl ester proportion in the product, reduced the yield of cis-dihydro jasmine keto-acid methyl ester.Daniel etc. are at Angew.Chem.Int.Ed.2000, and 39, similar report is also arranged among the 1992-1995, they make hydrogenation catalyst into a kind of complex catalyst of ruthenium.But the problems referred to above still exist.
Introduced in the European patent EP 399788 in common methyl dihydrojasmonate and to have added 1% the carbonate that weight is methyl dihydrojasmonate; under protection of nitrogen gas and 180 ℃ of temperature, react several hrs; directly prepare cis-dihydro jasmine keto-acid methyl ester; content is generally about 10%; again about 10% methyl dihydrojasmonate is carried out rectifying, rectifying goes out the methyl dihydrojasmonate of cis-dihydro jasmine keto-acid methyl ester content at 20-50%.But the temperature of reaction and rectifying is all than higher, decarboxylation can take place and be converted into Dihydrojasmone in the part cis-dihydro jasmine keto-acid methyl ester, and organic matter carbonizing etc., when reducing yield, influence the fragrance stability of product, can not obtain high-load cis-dihydro jasmine keto-acid methyl ester product.
Ernest Wenkert etc. has introduced with cyclopentadiene and valeraldehyde in Chimia 46 (1992) 95-97; also having the ethanoyl maleic anhydride is starting raw material; utilize the cis addition of Diel-Alder reaction; guarantee that two substituting groups are in cis position on the cyclopentanone, through seven steps reaction synthesizing cis-methyl dihydrojasmonate.But whole piece synthetic route reactions steps is many, because the unstable of cis-structure on thermodynamics makes it that problems such as isomerization take place in subsequent step, makes the content of total yield and cis-dihydro jasmine keto-acid methyl ester all lower.
Summary of the invention
The purpose of this invention is to provide a kind of simple to operate, cis-dihydro jasmine keto-acid methyl ester synthetic method that reaction conditions is gentle, improve reaction yield and product content, make reaction safety, environmental protection, realize suitability for industrialized production.
The present invention is a starting raw material with common methyl dihydrojasmonate, and through enolization reaction, halogenating reaction, dehalogenate with hydrogenation forms under solvent-free state, reaction equation is as follows:
Concrete steps of the present invention are as follows:
1) enolization: with common methyl dihydrojasmonate (being Compound I), etherifying agent and/or esterifying agent, synthesizing dihydro methyl jasmonate enol ether and/or methyl dihydrojasmonate alkene ester (being Compound I I) under the catalysis of acid, temperature of reaction is-10～200 ℃, and reaction finishes back weak base neutralizing acid;
2) halogenation: add weak base earlier and drip halogen then and carry out halogenation in methyl dihydrojasmonate enol ether and/or methyl dihydrojasmonate alkene ester, temperature of reaction is-50～150 ℃, and insulation then generates halo methyl dihydrojasmonate (being compound III);
3) dehalogenate: mineral alkali and organic solvent are mixed, heat up, stir, controlled temperature is between 30～250 ℃, drip the 2nd) step product compound III, drip off the back insulation, then cooling, when temperature drops to below 30 ℃, add distilled water wash, drying gets organism, wherein contain α, methyl jasmonate (the being compound IV) content of the two keys of β is more than 97.0%.
4) hydrogenation: compound IV, hydrogenation catalyst and halogen solidifying agent are added in the autoclave, behind nitrogen replacement three times, controlled temperature is between-50～200 ℃, use hydrogen exchange again three times, carry out hydrogenation reaction then, do not reduce to up to pressure and end, filter, get methyl dihydrojasmonate, wherein cis-dihydro jasmine keto-acid methyl ester (being compound V) content reaches more than 80%.
Wherein in the step 1), preferred 50～150 ℃ of temperature of reaction; Described etherifying agent is preferably chlorosilane, monomethyl trichlorosilane, monomethyl dichlorosilane, dimethyldichlorosilane(DMCS) or trimethylchlorosilane; Described esterifying agent is preferably phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, propylene acetate, methylvinyl acetate or vinyl acetate; Described acid is preferably sulfuric acid, hydrochloric acid, phosphoric acid, organic carboxyl acid, sulfonic acid or Zeo-karb, or their mixture; Described weak base is selected salt of weak acid for use, is preferably acetate, carbonate, oxalate or Citrate trianion.
Step 2) in, preferred-20～100 ℃ of temperature of reaction, the preferred 0.05～10hr of dropping time of halogen, the preferred 0.05～10hr of soaking time; Described weak base is selected salt of weak acid for use, is preferably acetate, carbonate, oxalate, Citrate trianion; Described halogen is a kind of in chlorine, bromine, the iodine or their mixture.
In the step 3), preferred 50～180 ℃ of temperature of reaction, preferred 0.05～10hr of dropping time, the preferred 0.05～10hr of soaking time; Described mineral alkali is a yellow soda ash, salt of wormwood, Quilonum Retard, barium carbonate, sodium hydroxide, lithium hydroxide, potassium hydroxide or calcium hydroxide; Described organic solvent is the solvent of boiling point between 30～250 ℃, as heptane series, and octane series, nonane series, benzene, toluene, dimethylbenzene, the oil ethers, solvent oils, DMF, ether, propyl ether, butyl ether, hexyl ether, acetone, butanone, hexanone, tetrahydrofuran (THF), ethyl acetate.
In the step 4), temperature of reaction is preferred-20-120 ℃, and the preferred 0.01～20g/100g compound IV of catalyst consumption, hydrogen pressure 0.1～10.0MPa; Hydrogenation catalyst is selected heterogeneous hydrogenation catalyst for use, is palladium carbon, platinum carbon or Reney nickel; The halogen solidifying agent is a soluble silver salt.
The present invention is to be starting raw material with common methyl dihydrojasmonate, through enolization, halogenation, dehalogenate and under solvent-free state hydrogenation preparing go out cis-dihydro jasmine keto-acid methyl ester, has following beneficial effect: simple to operate, the reaction conditions gentleness, safety, environmental protection, yield height (more than 85%), cis-dihydro jasmine keto-acid methyl ester content height (reaching more than 80%) is easy to suitability for industrialized production.
In order to set forth the present invention better, listed following examples, but protection scope of the present invention is not limited in these embodiment.
Embodiment
Embodiment 1
With the common methyl dihydrojasmonate of 113.60g (0.50mol), 60.00g (0.55mol) trimethylchlorosilane, 1.14g acetic acid joins in the four-hole boiling flask of 250ml successively, mixture under agitation is heated to 60 ℃ of reaction 8hr, in the reaction process, monitor the content of trans-methyl dihydrojasmonate, when the content of trans-methyl dihydrojasmonate drops to 1% when following, add in an amount of yellow soda ash and after, stopped reaction.Reaction is reclaimed excessive trimethylchlorosilane after finishing, and controlled temperature does not surpass 60 ℃, has reclaimed the back naturally cooling, obtains Compound I I, and is standby.
The Compound I I for preparing above is warmed up to 95 ℃, adds the 20.00g sodium-acetate earlier, begin to drip the 42.00g bromine then, 120min drips off, and insulation 260min cools to room temperature then, obtains compound III, and is standby.
In the four-hole boiling flask of 500ml, add 200ml 200 successively
#Solvent oil and 15.00g yellow soda ash stir and are warmed up to 185 ℃, slowly drip compound III then, 2hr drips off, be incubated 2hr down at 185 ℃ then, cooling then is when temperature drops to below 30 ℃, slowly add 200ml water, standing demix behind the stirring 10min divides the phase of anhydrating, and organic phase is washed with distilled water to neutrality, drying, distill the 105.50g compound IV.
In the autoclave of 0.5L, add the 105.50g compound IV successively, 5.00g10%Pt/C, 0.30g Silver monoacetate, close autoclave, use nitrogen replacement three times earlier, cooling is when temperature drops to-15 ℃, use hydrogen exchange again three times, hydrogenation carries out hydrogenation reaction to 10.0MPa then, does not reduce to up to pressure and ends.Exhaust, filtration, washing, drying, rectifying get colourless transparent liquid methyl dihydrojasmonate 98.60g, and wherein cis-dihydro jasmine keto-acid methyl ester content 81.00%, yield 87.26%.
Embodiment 2
With the common methyl dihydrojasmonate of 227.20g (1.0mol), 122.20g (1.2mol) methylvinyl acetate, 1.38g tosic acid and 1.00g acetic acid mixing acid join in the four-hole boiling flask of 500ml successively, mixture under agitation is heated to 80 ℃ of reaction 6hr, in the reaction process, monitor the content of trans-methyl dihydrojasmonate, when the content of trans-methyl dihydrojasmonate drops to 1% when following, add in an amount of potassium oxalate and afterreaction stops.After reaction finished, naturally cooling reclaimed excessive methylvinyl acetate then under vacuum condition, and controlled temperature does not surpass 80 ℃, has reclaimed the back naturally cooling, and is standby.
The Compound I I for preparing above is cooled to 0 ℃, adds the 30.00g potassium oxalate earlier, begin to feed 1.0mol chlorine then, 120min has led to, and is incubated 60min then and is warmed up to room temperature more naturally, and is standby.
In the four-hole boiling flask of 1000ml, add 180ml ethyl acetate and 25.00g lime carbonate successively, stir and be warmed up to 75 ℃, slowly drip compound III then, 2hr drips off, be incubated 2hr down at 75 ℃ then, cooling then is when temperature drops to below 30 ℃, slowly add 400ml water, standing demix behind the stirring 10min divides the phase of anhydrating, and organic phase is washed with distilled water to neutrality, drying, distill the 210.00g compound IV.
In the autoclave of 1.0L, add the 210.00g compound IV successively, 8.00g5%Pt/C, 0.50g Silver monoacetate, close autoclave, use nitrogen replacement three times earlier, when temperature is raised to 80 ℃, use hydrogen exchange again three times, hydrogenation carries out hydrogenation reaction to 5.0MPa then, does not reduce to up to pressure and ends.Cooling, exhaust, filtration, washing, drying, rectifying get colourless transparent liquid methyl dihydrojasmonate 195.60g, and wherein cis-dihydro jasmine keto-acid methyl ester content 81.00%, yield 86.55%.
Embodiment 3
With the common methyl dihydrojasmonate of 113.60g (0.5mol), 77.00g (0.55mol) phosphorus trichloride, 1.14g Phenylsulfonic acid joins in the four-hole boiling flask of 250ml successively, mixture under agitation is heated to 60 ℃ of reaction 8hr, in the reaction process, monitor the content of trans-methyl dihydrojasmonate, when the content of trans-methyl dihydrojasmonate drops to 1% when following, add in an amount of Trisodium Citrate and after, stopped reaction.Reaction is reclaimed excessive phosphorus trichloride after finishing, and controlled temperature does not surpass 60 ℃, has reclaimed the back naturally cooling, obtains Compound I I, and is standby.
The Compound I I for preparing above is warmed up to 55 ℃, adds the 30.00g Trisodium Citrate earlier, begin to add 128.00g iodine then, 30min adds, and is incubated 30min cool to room temperature more then, obtains compound III, and is standby.
In the four-hole boiling flask of 500ml, add 120ml dimethylbenzene and 15.00g sodium hydroxide successively, stir and be warmed up to 135 ℃, slowly drip compound III then, 2hr drips off, be incubated 2hr down at 135 ℃ then, cooling then is when temperature drops to below 30 ℃, slowly add 200ml water, standing demix behind the stirring 10min divides the phase of anhydrating, and organic phase is washed with distilled water to neutrality, drying, distill the 105.50g compound IV.
In the autoclave of 0.5L, add the 105.50g compound IV successively, 5.0gReney nickel, 0.40g Silver Nitrate, close autoclave, use nitrogen replacement three times earlier, when temperature is raised to 120 ℃, use hydrogen exchange again three times, hydrogenation carries out hydrogenation reaction to 2.0MPa then, does not reduce to up to pressure and ends.Cooling, exhaust, filtration, washing, drying, rectifying get colourless transparent liquid methyl dihydrojasmonate 96.60g, and wherein cis-dihydro jasmine keto-acid methyl ester content 85.00%, yield 85.49%.
Embodiment 4
With the common methyl dihydrojasmonate of 1 13.60g (0.50mol), 86.00g (0.55mol) phosphorus oxychloride, the 5.00g37% concentrated hydrochloric acid joins in the four-hole boiling flask of 250ml successively, mixture under agitation is heated to 90 ℃ of reaction 6hr, in the reaction process, monitor the content of trans-methyl dihydrojasmonate, when the content of trans-methyl dihydrojasmonate drops to 1% when following, add in an amount of lithium oxalate and after, stopped reaction.Reaction is reclaimed excessive phosphorus oxychloride after finishing, and controlled temperature does not surpass 90 ℃, has reclaimed the back naturally cooling, obtains Compound I I, and is standby.
The Compound I I for preparing above is cooled to 15 ℃, adds the 35.00g lithium oxalate earlier, begin to add 128.00g iodine then, 60min adds, and is incubated 120min then and is warmed up to room temperature more naturally, obtains compound III, and is standby.
In the four-hole boiling flask of 500ml, add 100ml120 successively
#Solvent oil and 30.00g calcium hydroxide stir and are warmed up to 115 ℃, slowly drip compound III then, 1hr drips off, be incubated 5hr down at 115 ℃ then, cooling then is when temperature drops to below 30 ℃, slowly add 200ml water, standing demix behind the stirring 10min divides the phase of anhydrating, and organic phase is washed with distilled water to neutrality, drying, distill the 108.40g compound IV.
In the autoclave of 0.5L, add the 108.40g compound IV successively, 6.00gReney nickel, 0.40g Silver monoacetate, close autoclave, use nitrogen replacement three times earlier, cooling is when temperature is raised to 65 ℃, use hydrogen exchange again three times, hydrogenation carries out hydrogenation reaction to 6.0MPa then, does not reduce to up to pressure and ends.Cooling, exhaust, filtration, washing, drying, rectifying get colourless transparent liquid methyl dihydrojasmonate 98.60g, and wherein cis-dihydro jasmine keto-acid methyl ester content 84.50%, yield 87.26%.
Embodiment 5
With the common methyl dihydrojasmonate of 454.20g (2.00mol), 312.73g (2.40mol) dimethyldichlorosilane(DMCS), 5.46g phosphoric acid joins in the four-hole boiling flask of 2L successively, mixture under agitation is heated to 70 ℃ of reaction 6hr, in the reaction process, monitor the content of trans-methyl dihydrojasmonate, when the content of trans-methyl dihydrojasmonate drops to 1% when following, add in an amount of Tripotassium Citrate and after, stopped reaction.Reaction is reclaimed excessive dimethyldichlorosilane(DMCS) after finishing, and controlled temperature does not surpass 70 ℃, has reclaimed the back naturally cooling, and is standby.
The Compound I I for preparing above is cooled to 5 ℃, adds the 50.00g Tripotassium Citrate earlier, begin to add the mixture of 1.0mol bromine and 1.0mol iodine then, 120min adds, and is incubated 120min then and is warmed up to room temperature more naturally, and is standby.
In the four-hole boiling flask of 4L, add 400ml sherwood oil and 60.00g salt of wormwood successively, stir and be warmed up to 85 ℃, slowly drip compound III then, 3hr drips off, be incubated 10hr down at 85 ℃ then, cooling then is when temperature drops to below 30 ℃, slowly add 800ml water, standing demix behind the stirring 10min divides the phase of anhydrating, and organic phase is washed with distilled water to neutrality, thousand is dry, distill the 430.55g compound IV.
In the autoclave of 2.0L, add the 430.55g compound IV successively, 20.00g7.5%Pd/C, 1.05g Silver Nitrate, close autoclave, use nitrogen replacement three times earlier, when temperature is raised to 75 ℃, use hydrogen exchange again three times, hydrogenation carries out hydrogenation reaction to 4.0MPa then, does not reduce to up to pressure and ends.Cooling, exhaust, filtration, washing, drying, rectifying get colourless transparent liquid methyl dihydrojasmonate 397.05g, and wherein cis-dihydro jasmine keto-acid methyl ester content 84.00%, yield 87.84%.
Embodiment 6
With the common methyl dihydrojasmonate of 113.60g (0.50mol), 64.00g (0.55mol) monomethyl dichlorosilane, 20ml15% sulfuric acid joins in the four-hole boiling flask of 250ml successively, mixture under agitation is heated to 50 ℃ of reaction 10hr, in the reaction process, monitor the content of trans-methyl dihydrojasmonate, when the content of trans-methyl dihydrojasmonate drops to 1% when following, add in an amount of zinc acetate and after, stopped reaction.Reaction is reclaimed excessive monomethyl dichlorosilane after finishing, and controlled temperature does not surpass 60 ℃, has reclaimed the back naturally cooling, obtains Compound I I, and is standby.
The Compound I I for preparing above is cooled to-10 ℃, adds the 38.00g zinc acetate earlier, begin to add 128.00g iodine then, 120min adds, and is incubated 200min then and is warmed up to room temperature more naturally, obtains compound III, and is standby.
In the four-hole boiling flask of 500ml, add 80ml normal heptane and 25.00g sodium hydroxide successively, stirring is warmed up to 95 ℃, slowly drips compound III then, and 1hr drips off, be incubated 6hr down at 95 ℃ then, cooling when temperature drops to below 30 ℃, slowly adds 200ml water then, standing demix behind the stirring 10min, divide the phase of anhydrating, organic phase is washed with distilled water to neutrality, the dry 106.70g compound IV that gets.
In the autoclave of 0.5L, add the 106.70g compound IV successively, 5.00g5%Pt/C, 0.30g Silver monoacetate, close autoclave, use nitrogen replacement three times earlier, when temperature is raised to 45 ℃, use hydrogen exchange again three times, hydrogenation carries out hydrogenation reaction to 8.0MPa then, does not reduce to up to pressure and ends.Cooling, exhaust, filtration, washing, drying, rectifying get colourless transparent liquid methyl dihydrojasmonate 96.20g, and wherein cis-dihydro jasmine keto-acid methyl ester content 83.20%, yield 85.13%.
Embodiment 7
With the common methyl dihydrojasmonate of 113.60g (0.50mol), 56.00g (0.55mol) propylene acetate, 5.00g Zeo-karb joins in the four-hole boiling flask of 250ml successively, mixture under agitation is heated to 80 ℃ of reaction 8hr, in the reaction process, monitor the content of trans-methyl dihydrojasmonate, when the content of trans-methyl dihydrojasmonate drops to 1% when following, add in an amount of sodium oxalate and after, stopped reaction.Reaction is reclaimed excessive propylene acetate after finishing, and controlled temperature does not surpass 80 ℃, has reclaimed the back naturally cooling, obtains Compound I I, and is standby.
The Compound I I for preparing above is warmed up to 60 ℃, adds 22.00g salt of wormwood earlier, begin to add the 40.00g bromine then, 120min adds, and is incubated 300min then and cools to room temperature more naturally, obtains compound III, and is standby.
In the four-hole boiling flask of 500ml, add 100ml hexyl ether and 25.00g potassium hydroxide successively, stir and be warmed up to 195 ℃, slowly drip compound III then, 1hr drips off, be incubated 3hr down at 195 ℃ then, cooling then is when temperature drops to below 30 ℃, slowly add 200ml water, standing demix behind the stirring 10min divides the phase of anhydrating, and organic phase is washed with distilled water to neutrality, drying, distill the 104.50g compound IV.
In the autoclave of 0.5L, add the 104.50g compound IV successively, 5.00g7.5%Pt/C, 0.2g Silver Nitrate, close autoclave, use nitrogen replacement three times earlier, when temperature is raised to 85 ℃, use hydrogen exchange again three times, hydrogenation carries out hydrogenation reaction to 1.0MPa then, is added to pressure and does not only reduce to.Cooling, exhaust, filtration, washing, drying, rectifying get colourless transparent liquid methyl dihydrojasmonate 97.20g, and wherein cis-dihydro jasmine keto-acid methyl ester content 86.02%, yield 85.13%.
Claims (6)
1, the synthetic method of cis-dihydro jasmine keto-acid methyl ester, its concrete steps are as follows:
1) enolization: use common methyl dihydrojasmonate, etherifying agent and/or esterifying agent, synthesizing dihydro methyl jasmonate enol ether and/or methyl dihydrojasmonate alkene ester under the catalysis of acid, temperature of reaction is-10～200 ℃, reaction finishes back weak base neutralizing acid;
2) halogenation: add weak base earlier in methyl dihydrojasmonate enol ether and/or methyl dihydrojasmonate alkene ester, drip halogen then and carry out halogenation, temperature of reaction is-50～150 ℃, and insulation then generates the halo methyl dihydrojasmonate;
3) dehalogenate: mineral alkali and organic solvent are mixed, heat up, stir, controlled temperature is between 30-250 ℃, drip the 2nd) the step product, drip off the back insulation, and then cooling, when temperature drops to below 30 ℃, add distilled water wash, drying must contain α, the methyl jasmonate of the two keys of β;
4) hydrogenation: will contain α, methyl jasmonate, hydrogenation catalyst and the halogen solidifying agent of the two keys of β carry out hydrogenation reaction under solvent-free state, and temperature of reaction is-50～200 ℃, and reaction finishes after-filtration, obtains cis-dihydro jasmine keto-acid methyl ester;
Wherein the described etherifying agent of step 1) is a chlorosilane, monomethyl trichlorosilane, monomethyl dichlorosilane, dimethyldichlorosilane(DMCS) or trimethylchlorosilane; Described esterifying agent is a phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, propylene acetate, methylvinyl acetate or vinyl acetate; The described acid of step 1) is sulfuric acid, hydrochloric acid, phosphoric acid, organic carboxyl acid, sulfonic acid or Zeo-karb, or their mixture; Step 1) and 2) described weak base is selected salt of weak acid for use; The described mineral alkali of step 3) is a yellow soda ash, salt of wormwood, Quilonum Retard, barium carbonate, sodium hydroxide, lithium hydroxide, potassium hydroxide or calcium hydroxide; In the step 4), hydrogenation catalyst is selected heterogeneous hydrogenation catalyst for use, and the halogen solidifying agent is a soluble silver salt.
2, the synthetic method of cis-dihydro jasmine keto-acid methyl ester according to claim 1, wherein the temperature of reaction of step 1) is 50～150 ℃; Step 2) temperature of reaction is-20～100 ℃, and the dropping time of halogen is 0.05～10hr, and soaking time is 0.05～10hr; The temperature of reaction of step 3) is 50～180 ℃, and the dropping time is 0.05～10hr, and soaking time is 0.05～10hr, and is described; The temperature of reaction of step 4) is-20～120 ℃, and the consumption of hydrogenation catalyst is that 0.01～20g/100g contains α, the methyl jasmonate of the two keys of β, and the hydrogen pressure in the hydrogenation reaction is 0.1～10.0MPa.
3, the synthetic method of cis-dihydro jasmine keto-acid methyl ester according to claim 2, wherein step 1) and 2) described salt of weak acid is acetate, carbonate, oxalate or Citrate trianion.
4, the synthetic method of cis-dihydro jasmine keto-acid methyl ester according to claim 2, wherein step 2) described halogen is a kind of in chlorine, bromine, the iodine or their mixture.
5, the synthetic method of cis-dihydro jasmine keto-acid methyl ester according to claim 2, wherein in the step 3), described organic solvent is the solvent of boiling point between 30～250 ℃.
6, the synthetic method of cis-dihydro jasmine keto-acid methyl ester according to claim 2, wherein in the step 4), hydrogenation catalyst is selected palladium carbon for use, platinum carbon or Raney nickel.
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Assignee: Shandong Xinhecheng Pharmaceutical Co., Ltd. Assignor: Zhejiang Xinhecheng Co., Ltd. Contract record no.: 2010330002240 Denomination of invention: Synthesizing process of cis-dihydro jasmine keto-acid methyl ester Granted publication date: 20100120 License type: Exclusive License Open date: 20070718 Record date: 20101206 |