CN101475480A - Method for synthesizing cis-methyl dihydrojasmonate - Google Patents
Method for synthesizing cis-methyl dihydrojasmonate Download PDFInfo
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- 238000000034 method Methods 0.000 title abstract description 5
- 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 title abstract 4
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 28
- KVWWIYGFBYDJQC-UHFFFAOYSA-N methyl dihydrojasmonate Chemical compound CCCCCC1C(CC(=O)OC)CCC1=O KVWWIYGFBYDJQC-UHFFFAOYSA-N 0.000 claims abstract description 25
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001384 succinic acid Substances 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005917 acylation reaction Methods 0.000 claims abstract description 9
- 238000007259 addition reaction Methods 0.000 claims abstract description 6
- 238000006266 etherification reaction Methods 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005755 formation reaction Methods 0.000 claims abstract description 5
- 241000207840 Jasminum Species 0.000 claims description 26
- 235000010254 Jasminum officinale Nutrition 0.000 claims description 26
- -1 keto-acid methyl ester Chemical class 0.000 claims description 26
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 19
- 238000009413 insulation Methods 0.000 claims description 15
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000010189 synthetic method Methods 0.000 claims description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 7
- 238000005194 fractionation Methods 0.000 claims description 7
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- YCIXWYOBMVNGTB-UHFFFAOYSA-N 3-methyl-2-pentylcyclopent-2-en-1-one Chemical compound CCCCCC1=C(C)CCC1=O YCIXWYOBMVNGTB-UHFFFAOYSA-N 0.000 claims description 3
- BWZHKRSSCFRVIE-UHFFFAOYSA-N 1-n,4-n-dimethyl-2h-pyridine-1,4-diamine Chemical compound CNN1CC=C(NC)C=C1 BWZHKRSSCFRVIE-UHFFFAOYSA-N 0.000 claims description 2
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- UCVODTZQZHMTPN-UHFFFAOYSA-N heptanoyl chloride Chemical compound CCCCCCC(Cl)=O UCVODTZQZHMTPN-UHFFFAOYSA-N 0.000 abstract 4
- WJFHZGWEIOVETL-UHFFFAOYSA-N 2-pentylcyclopentane-1,3-dione Chemical compound CCCCCC1C(=O)CCC1=O WJFHZGWEIOVETL-UHFFFAOYSA-N 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000010790 dilution Methods 0.000 description 7
- 239000012895 dilution Substances 0.000 description 7
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000003205 fragrance Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 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 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- WXIUBYCJAAEOFL-UHFFFAOYSA-N [S].ClOCl Chemical class [S].ClOCl WXIUBYCJAAEOFL-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000010813 municipal solid waste Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- GEWDNTWNSAZUDX-WQMVXFAESA-N (-)-methyl jasmonate Chemical compound CC\C=C/C[C@@H]1[C@@H](CC(=O)OC)CCC1=O GEWDNTWNSAZUDX-WQMVXFAESA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GEWDNTWNSAZUDX-UHFFFAOYSA-N methyl 7-epi-jasmonate Natural products CCC=CCC1C(CC(=O)OC)CCC1=O GEWDNTWNSAZUDX-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing cis methyl dihydrojasmonate, which comprises: firstly, formation reaction of enanthoyl chloride, namely enanthylic acid reacts with thionyl chloride to generate the enanthoyl chloride; secondly, Fridel-Crafts acylation reaction, namely the enanthoyl chloride reacts with succinic acid to generate 2-amyl-1,3-cyclopentanedione; thirdly, etherification reaction, namely the 2-amyl-1,3-cyclopentanedione reacts with methanol to generate 3-methoxyl-2-amyl-cyclopentyl-2-ketene; fourthly, addition reaction, namely the 3-methoxyl-2-amyl-cyclopentyl-2-ketene reacts with dimethyl malonate to generate trans-methyl dihydrojasmonate; and fifthly, hydrogenation reaction, namely the trans-methyl dihydrojasmonate is subjected to hydrogen substitution to prepare methyl dihydrojasmonate which mainly comprises the cis methyl dihydrojasmonate. The method synthesizes and prepares the cis methyl dihydrojasmonate by acylation reaction between the succinic acid and the enanthoyl chloride and etherification reaction, addition reaction and hydrogenation reaction, and has the advantages of short synthesis procedures, mild reaction conditions, simple and convenient operation, low production cost, safety and environmental protection, and easy industrial production.
Description
Technical field
The present invention relates to a kind of synthetic method of flavor compounds, specifically a kind of synthetic method of cis-dihydro jasmine keto-acid methyl ester.
Background technology
Methyl dihydrojasmonate is a kind of colourless to weak yellow liquid (chemical name: 2-amyl group-3-carbonyl NSC 60134 methyl esters), have following four kinds of spatial isomerism structural formulas.
Cis-dihydro jasmine keto-acid methyl ester is trans-methyl dihydrojasmonate
Common methyl dihydrojasmonate mainly is the methyl dihydrojasmonate of transconfiguration, and it has graceful soft Flower of Arabian Jasmine note and comfortable lemon sample fruital breath, and the slim and graceful elegant lasting of whole fragrance 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, have 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, and " 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 the two strong methyl jasmonate hydrogenation of α, β and generates cis-dihydro jasmine keto-acid methyl ester, contain the two strong methyl jasmonates of α, β in alcohols or esters solvent as having introduced in the U.S. Pat 3978108, prepare cis-dihydro jasmine keto-acid methyl ester with the Pd/C shortening, but this patent is not mentioned the source or the preparation method of the two methyl jasmonates of being good for of α, β; Introduced in the European patent EP 399788 in common methyl dihydrojasmonate that to add weight be the carbonate of methyl dihydrojasmonate 1%, at N
2Protect following 180 ℃ of reaction several hrs, directly prepare cis-dihydro jasmine keto-acid methyl ester, cis-dihydro jasmine keto-acid methyl ester content is generally about 10%, again it is carried out rectifying, rectifying goes out cis-dihydro jasmine keto-acid methyl ester content at 20～50% methyl dihydrojasmonate, but the temperature of reaction and rectifying is all higher, decarboxylation can take place and be converted into Dihydrojasmone and organic matter carbonizing etc. in the part cis-dihydro jasmine keto-acid methyl ester, when reducing productive rate, influence the flavouring essence quality of product, can not obtain high-load cis-dihydro jasmine keto-acid methyl ester product; It is raw material that ErnestWenkert etc. have introduced with cyclopentadiene and valeraldehyde in Chimia 46 (1992) 95-97, utilize the cis addition of Diel-Alder reaction to guarantee that two substituting groups are in cis position on the cyclopentanone, through seven step prepared in reaction methyl dihydrojasmonates, but reactions steps is many, and the unstable of cis-structure on thermodynamics, make it that problems such as isomerization take place in subsequent step, make the content of total yield and cis-dihydro jasmine keto-acid methyl ester all lower.
Summary of the invention
The objective of the invention is: a kind of synthetic method of cis-dihydro jasmine keto-acid methyl ester is provided, this synthesising method reacting condition gentleness, easy to operate, improve productive rate and, react safety and environmental protection along body burden, be easy to suitability for industrialized production.
Technical solution of the present invention is: the formation reaction of the first step oenanthyl chloro, and enanthic acid and sulfur oxychloride reaction generate oenanthyl chloro; The second step Fridel-Crafts acylation reaction, oenanthyl chloro and Succinic Acid react 2-amyl group-1, the 3-cyclopentanedione; The 3rd the step etherification reaction, 2-amyl group-1,3-cyclopentanedione and methyl alcohol react 3-methoxyl group-2-amyl group-ring penta-2-ketenes; The 4th the step addition reaction, 3-methoxyl group-2-amyl group-ring penta-2-ketenes and dimethyl malonate react trans methyl dihydrojasmonate; The 5th step hydrogenation, trans methyl dihydrojasmonate hydrogen exchange winner content are the Dihydrojasmone acid methyl alcohol of cis-dihydro jasmine keto-acid methyl ester.
Reaction equation of the present invention is as follows:
Concrete steps of the present invention are as follows:
1) formation reaction of oenanthyl chloro: the positive enanthic acid of mass ratio 1:1.3 and sulfur oxychloride room temperature reaction 4 hours in reactor, be incubated 1.5 hours post-heating to 85 ℃, 85 ℃ of insulations refluxed 5 hours, distill oenanthyl chloro;
2) Fridel-Crafts acylation reaction: in reactor, add nitroethane, anhydrous AlCl
3, Succinic Acid and 4-Dimethylamino pyridine; And then add oenanthyl chloro and carry out acylation reaction, temperature of reaction is 80-85 ℃, backflow insulation reaction 8 hours; Ice is separated, is frozen and analyse and extracting at last, makes 2-amyl group-1,3-cyclopentanedione, i.e. Compound I; Wherein, the mass ratio of Succinic Acid and oenanthyl chloro is 1:1.7, and 4-Dimethylamino pyridine and Succinic Acid mass ratio are 0.03:1,4-Dimethylamino pyridine and anhydrous AlCl
3Mass ratio be 1:20;
3) etherification reaction: in reactor, add Compound I, methyl alcohol, normal hexane and methylsulfonic acid, temperature of reaction 60-65 ℃, back flow reaction 8-10 hour; After reaction finished, with the quadrol neutralization, vacuum rotary steam reclaimed methyl alcohol, normal hexane; Thin up is used n-hexane extraction, and organic phase is through washing, anhydrous MgSO
4The dry crude product that gets; The crude product vacuum fractionation makes 3-methoxyl group-2-amyl group-ring penta-2-ketenes, i.e. Compound I I; Wherein, the mass ratio of methyl alcohol and Compound I is 5～5.5:1, and the mass ratio of methylsulfonic acid and Compound I is 1:11.3;
4) addition reaction: add methyl alcohol, sodium methylate and dimethyl malonate in reactor, be heated to 60-65 ℃, insulation 1hr refluxes; Add Compound I I, back flow reaction 24hr, reaction is chilled to 0-10 ℃ after finishing, and methyl alcohol is reclaimed in the glacial acetic acid neutralization; Thin up, special butyl ether extraction, organic phase is through washing, anhydrous MgSO
4Drying, fractionation make trans methyl dihydrojasmonate, i.e. compound III; Wherein, the mass ratio of dimethyl malonate and Compound I I is 1:1.1, and the mass ratio of sodium methylate and dimethyl malonate is 1:3.3;
5) hydrogenation: compound III, Pd-C catalyzer are dropped in the hydrogenation still, nitrogen replacement repeatedly, more repeatedly with hydrogen exchange, 20～30 ℃ of temperature of reaction, hydrogen pressure 0.1MPa～2.0MPa does not only reduce to until pressure, filter cis-dihydro jasmine keto-acid methyl ester, i.e. compound IV; Wherein the mass ratio of Pd-c catalyzer and compound III is 1:20.
The present invention carries out acylation reaction with Succinic Acid and oenanthyl chloro, and through etherificate, addition, the synthetic cis-dihydro jasmine keto-acid methyl ester that makes of hydrogenation, synthesis step is short again; the reaction conditions gentleness, easy and simple to handle, production cost is low; safety and environmental protection is easy to suitability for industrialized production.
Embodiment
Below in conjunction with concrete example, the present invention is described in further detail.Should be understood that these embodiment just in order to demonstrate the invention, but not limit the scope of the invention by any way.
Embodiment 1:
The positive enanthic acid of 65 grams is dropped into the 250ml four-hole bottle, slowly drips 85 gram sulfur oxychlorides under the room temperature, 4 hours dropping time, at room temperature be incubated 1.5 hours and be heated to 85 ℃, 85 ℃ were refluxed 5 hours, it is few that the PH test paper is measured mouthful acid gas, finishes reaction, distill oenanthyl chloro;
With 30ml nitroethane, the anhydrous AlCl of 8 grams
3, 0.4 gram 4-Dimethylamino pyridine catalyzer and 12 gram Succinic Acid drop into the 150ml there-necked flasks; Add the oenanthyl chloro of the above-mentioned preparation of 20 grams then, be heated to 80 ℃, insulation 8 hours refluxes; Be chilled to below 0 ℃, add 40 gram trash ices fast, put into refrigerator and freeze and analyse 9 hours, suction filtration is washed till white with the 10%NaCl aqueous solution, toluene successively, and oven dry must 12.4 be digested compound I;
With 80 milliliters of anhydrous methanols, 50 ml n-hexanes, 1.1 gram methylsulfonic acids with above-mentionedly make 12.4 and digest compound I and drop into the 250ml there-necked flask, be heated to 60 ℃, reacted 8 hours; Reaction finishes the back with the quadrol neutralization, reclaims methyl alcohol, normal hexane; Add the dilution of 100 ml waters, the 80ml n-hexane extraction, organic phase gets crude product through washing, anhydrous magnesium sulfate drying, and the crude product fractionation gets 10.5 and digests compound II;
70g anhydrous methanol, 3 gram sodium methylates, 10g dimethyl malonate are dropped into the 200ml there-necked flask, be heated to 60 ℃, the insulation 1 hour that refluxes adds 10.5 and digests compound II, and insulation refluxed 23 hours; Ice bath is chilled to 0 ℃, drips the glacial acetic acid neutralization through precooling, reclaims methyl alcohol, adds the dilution of 80ml water, special butyl ether extraction, and organic phase is through washing, anhydrous MgSO
4Drying is distilled to such an extent that 10.9 digest compound III;
0.5g digesting compound III, Pd/C and 10.9 drops into 25ml hydrogenation still, use nitrogen replacement three times earlier, use hydrogen exchange again three times, hydrogen pressure 0.1MPa does not reduce to until pressure and ends under 20 ℃ of conditions of room temperature, exhaust, filtration, washing, drying, rectifying get cis-dihydro jasmine keto-acid methyl ester 10.1 grams, overall yield of reaction 43.9%.
Embodiment 2:
The positive enanthic acid of 65 grams is dropped into the 250ml four-hole bottle, slowly drips 85 gram sulfur oxychlorides under the room temperature, 4 hours dropping time, at room temperature be incubated 1.5 hours, be heated to 85 ℃, 85 ℃ were refluxed 5 hours, it is few that the PH test paper is measured mouthful acid gas, finishes reaction, distill oenanthyl chloro;
With 35ml nitroethane, the anhydrous AlCl of 10 grams
3, 0.4 gram 4-Dimethylamino pyridine catalyzer and 12 gram Succinic Acid drop into the 150ml there-necked flasks; Add the oenanthyl chloro of the above-mentioned preparation of 20 grams then, be heated to 85 ℃, insulation 8 hours refluxes; Be chilled to below 10 ℃, add 50 gram trash ices fast, put into refrigerator and freeze and analyse 12 hours, suction filtration is washed till white with the 10%NaCl aqueous solution, toluene successively, and oven dry must 12.6 be digested compound I;
With 85 milliliters of anhydrous methanols, 50 ml n-hexanes, 1.15 gram methylsulfonic acids with above-mentionedly make 12.6 and digest compound I and drop into the 250ml there-necked flask, be heated to 65 ℃ of reactions 9 hours; Reaction finishes the back with the quadrol neutralization, reclaims methyl alcohol, normal hexane; Add the dilution of 100 ml waters, the 80ml n-hexane extraction, organic phase gets crude product through washing, anhydrous magnesium sulfate drying, and the crude product fractionation gets 10.8 and digests compound II;
75g anhydrous methanol, 3.2 gram sodium methylates, 10.5g dimethyl malonate are dropped into the 200ml there-necked flask, be heated to 62 ℃, the insulation 1 hour that refluxes adds 10.8 and digests compound II, and insulation refluxed 24 hours; Ice bath is chilled to 2 ℃, drips the glacial acetic acid neutralization through precooling, reclaims methyl alcohol; Add the dilution of 80ml water, special butyl ether extraction, organic phase is through washing, anhydrous MgSO
4Drying is distilled to such an extent that 11.3 digest compound III;
0.55g digesting compound III, Pd/C and 11.3 drops into 25ml hydrogenation still, use nitrogen replacement three times earlier, use hydrogen exchange again three times, hydrogen pressure 0.1MPa does not reduce to until pressure and ends under 20 ℃ of conditions of room temperature, exhaust, filtration, washing, drying, rectifying get cis-dihydro jasmine keto-acid methyl ester 10.4 grams, overall yield of reaction 45.1%.
Embodiment 3:
The positive enanthic acid of 65 grams is dropped into the 250ml four-hole bottle, slowly drips 85 gram sulfur oxychlorides under the room temperature, 4 hours dropping time, at room temperature be incubated 1.5 hours, be heated to 85 ℃, 85 ℃ were refluxed 5 hours, it is few that the PH test paper is measured mouthful acid gas, finishes reaction, distill oenanthyl chloro;
With 30ml nitroethane, the anhydrous AlCl of 9 grams
3, 0.42 gram 4-Dimethylamino pyridine catalyzer and 12.5 gram Succinic Acid drop into the 150ml there-necked flasks; Add the oenanthyl chloro of the above-mentioned preparation of 20.6 grams then, be heated to 85 ℃, insulation 9 hours refluxes; Be chilled to below 15 ℃, add 45 gram trash ices fast, put into refrigerator and freeze and analyse 10 hours, suction filtration is washed till white with the 10%NaCl aqueous solution, toluene successively, and oven dry must 12.5 be digested compound I;
With 83 milliliters of anhydrous methanols, 50 ml n-hexanes, 1.15 gram methylsulfonic acids with above-mentionedly make 12.5 and digest compound I and drop into the 250ml there-necked flask, be heated to 66 ℃ of reactions 10 hours; Reaction finishes the back with the quadrol neutralization, reclaims methyl alcohol, normal hexane; Add the dilution of 100 ml waters, the 80ml n-hexane extraction, organic phase gets crude product through washing, anhydrous magnesium sulfate drying, and the crude product fractionation gets 10.7 and digests compound II;
73g anhydrous methanol, 3.5 gram sodium methylates, 10.5g dimethyl malonate are dropped into the 200ml there-necked flask, be heated to 65 ℃, the insulation 1 hour that refluxes adds 10.7 and digests compound II, and insulation refluxed 24 hours; Ice bath is chilled to 5 ℃, drips the glacial acetic acid neutralization through precooling, reclaims methyl alcohol; Add the dilution of 80ml water, special butyl ether extraction, organic phase is through washing, anhydrous MgSO
4Drying is distilled to such an extent that 11.2 digest compound III;
0.5g digesting compound III, Pd/C and 11.2 drops into 25ml hydrogenation still, use nitrogen replacement three times earlier, use hydrogen exchange again three times, hydrogen pressure 1.0MPa does not reduce to until pressure and ends under 20 ℃ of conditions of room temperature, exhaust, filtration, washing, drying, rectifying get cis-dihydro jasmine keto-acid methyl ester 10.3 grams, overall yield of reaction 44.6%.
Claims (3)
1. the synthetic method of a cis-dihydro jasmine keto-acid methyl ester is characterized in that this synthetic method is as follows: the first oenanthyl chloro formation reaction frequently, enanthic acid and sulfur oxychloride reaction generation oenanthyl chloro; The second step Fridel-Crafts acylation reaction, oenanthyl chloro and Succinic Acid react 2-amyl group-1, the 3-cyclopentanedione; The 3rd the step etherification reaction, 2-amyl group-1,3-cyclopentanedione and methyl alcohol react 3-methoxyl group-2-amyl group-ring penta-2-ketenes; The 4th step addition reaction, 3-methoxyl group-2-amyl group-ring penta-2-ketenes and propanedioic acid dicarboxylic acid esters react transly-methyl dihydrojasmonate; The 5th step hydrogenation, trans-methyl dihydrojasmonate hydrogen exchange winner content are the Dihydrojasmone acid first of cis-dihydro jasmine keto-acid methyl ester.
2. the synthetic method of a kind of cis-dihydro jasmine keto-acid methyl ester according to claim 1 is characterized in that reaction equation is as follows:
3. the synthetic method of a kind of cis-dihydro jasmine keto-acid methyl ester according to claim 1 is characterized in that concrete steps are as follows:
1) formation reaction of oenanthyl chloro: the positive enanthic acid of mass ratio 1:1.3 and sulfur oxychloride room temperature reaction 4 hours in reactor, be incubated 1.5 hours post-heating to 85 ℃, 85 ℃ of insulations refluxed 5 hours, distill oenanthyl chloro;
2) Fridel-Crafts acylation reaction: in reactor, add nitroethane, anhydrous AlCl
3, Succinic Acid and 4-Dimethylamino pyridine; And then add oenanthyl chloro and carry out acylation reaction, temperature of reaction is 80-85 ℃, backflow insulation reaction 8 hours; Ice is separated, is frozen and analyse and extracting at last, makes 2-amyl group-1,3-cyclopentanedione, i.e. Compound I; Wherein, the mass ratio of Succinic Acid and oenanthyl chloro is 1:1.7, and 4-Dimethylamino pyridine and Succinic Acid mass ratio are 0.03:1,4-Dimethylamino pyridine and anhydrous AlCl
3Mass ratio be 1:20;
3) etherification reaction: in reactor, add Compound I, methyl alcohol, normal hexane and methylsulfonic acid, temperature of reaction 60-65 ℃, back flow reaction 8-10 hour; After reaction finished, with the quadrol neutralization, vacuum rotary steam reclaimed methyl alcohol, normal hexane; Thin up, with the normal hexane extraction, organic phase is through washing, anhydrous MgSO
4The dry crude product that gets; The crude product vacuum fractionation makes 3-methoxyl group-2-amyl group-ring penta-2-ketenes, i.e. Compound I I; Wherein, the mass ratio of methyl alcohol and Compound I is 5～5.5:1, and the mass ratio of methylsulfonic acid and Compound I is 1:11.3;
4) addition reaction: add methyl alcohol, sodium methylate and dimethyl malonate in reactor, be heated to 60～65 ℃, insulation 1hr refluxes; Add Compound I I, back flow reaction 22～24hr; Reaction finishes, and is chilled to 0-10 ℃, and methyl alcohol is reclaimed in the glacial acetic acid neutralization; Thin up, special butyl ether extraction, organic phase is through washing, anhydrous MgSO
4Drying, fractionation make trans methyl dihydrojasmonate, i.e. compound III; Wherein, the mass ratio of dimethyl malonate and Compound I I is 1:1.1, and the mass ratio of sodium methylate and dimethyl malonate is 1:3.3;
5) hydrogenation: compound III, Pd-C catalyzer are dropped in the hydrogenation still, nitrogen replacement repeatedly, more repeatedly with hydrogen exchange, 20～30 ℃ of temperature of reaction, hydrogen pressure 0.1MPa～2.0MPa does not only reduce to until pressure, filter cis-dihydro jasmine keto-acid methyl ester, i.e. compound IV; Wherein the mass ratio of Pd-c catalyzer and compound III is 1:20.
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