CN102432433A - Method for synthesizing farnesol - Google Patents
Method for synthesizing farnesol Download PDFInfo
- Publication number
- CN102432433A CN102432433A CN201110443259XA CN201110443259A CN102432433A CN 102432433 A CN102432433 A CN 102432433A CN 201110443259X A CN201110443259X A CN 201110443259XA CN 201110443259 A CN201110443259 A CN 201110443259A CN 102432433 A CN102432433 A CN 102432433A
- Authority
- CN
- China
- Prior art keywords
- farnesol
- geranyl
- trimethylammonium
- obtains
- diene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a method for synthesizing farnesol. The method has the characteristics of low cost, safe reaction route, environment friendliness and high purity of an obtained product. The method comprises the following steps of: 1, reacting geraniol (E)-3,7-dimethyl-2,6-octadiene-1-alcohol with dimethyl sulfide and N-chloro succimide in dichloromethane to obtain geranyl chloride; 2, reacting the geranyl chloride with ethyl acetoacetate under the action of potassium carbonate to obtain geranyl ethyl acetoacetate, adding sodium hydroxide after the reaction is finished, heating for decarboxylation, and thus obtaining geranyl acetone; 3, introducing acetylene gas into the geranyl acetone under the action of inorganic base, and reacting to obtain (E)-3,7,11-trimethyl dodecane-6,10-diene-1-alkyne-3-alcohol; 4 and 5, obtaining (E)-3,7,11-trimethyl-1,2,6,10-tetraalkenyl acetate; 6, hydrolyzing the (E)-3,7,11-trimethyl-1,2,6,10-tetraalkenyl acetate to obtain farnesal; and 7, reducing the farnesal in methanol by using sodium borohydride to obtain the farnesol.
Description
Technical field
The present invention relates to a kind of compound method of farnesol, the farnesol formal name used at school is: (E)-2,6, and 10-trimethylammonium-2,6,10-12 carbon triolefin-12-alcohol.
Background technology
Compound
1Shown farnesol is a kind of important spices and foodstuff additive, also is the important starting raw material of many pharmaceutical activity molecules.It is by compound
2Geraniol is through seven step prepared in reaction gained.
Offering report uses Wittig reaction to obtain compound as committed step
1, the linked reaction that also has bibliographical information to use the methyl Tong Shiji is that committed step obtains compound
1
The said method route of document is oversize, and reaction is unstable, and considerable reagent is expensive, can not be used for suitability for industrialized production.
Farnesol is claimed farnesol again, is a kind of colourless sesquiterpenoid that extracts in the plant materials.Farnesol is insoluble in water, but can dissolve each other with oil.Colourless oil liquid.4 kinds of isomer are arranged, directly use with the mixtinite form usually.Molecular weight 222.36.Density 0.89g/cm3.263 ℃ of boiling points.100 ℃ of flash-points.Water insoluble.Be dissolved in most of organic solvents.Be dissolved in 70% ethanol with l:3.Have the flores convallariae fragrance of distinctive blue or green note, and blue or green fragrant and banksia rose note is arranged.
In a lot of essential oils, all contain farnesol.Such as, lemongrass, flores aurantii, Cyclamen persicum, lemongrass, Tuberose, rose, Moschus or the like.Farnesol also is used as the additive of cigarette.
The working method of farnesol: adopt saponification method and synthesis method.Saponification method is to be that raw material Pg acetic anhydride is handled the back and generated peruviol with the cabreuva oil, carries out saponification reaction again and gets.Synthesis method is to be raw material with acetylene, synthesizes earlier to obtain methyl butanol, and the regeneration peruviol gets through saponification at last again.
The purposes of farnesol: alcohols synthetic perfume.Mainly be used as the blending stock that the lily of the valley, cloves, rose, VT, flores aurantii, Cyclamen persicum etc. have fragrance of a flower rhythm essence, also can be used as the compound perfume of east odor type, chypre essence.
Farnesol is the natural insecticide of acarid, also is the pheromone of a lot of insects.
Summary of the invention
The objective of the invention is to: a kind of new methodology of organic synthesis for preparing farnesol is provided, utilizes compound method of the present invention, can simplify the synthesis step of farnesol, reduce the cost of synthetic farnesol.
Realize that technical scheme of the present invention is following: a kind of compound method of farnesol, use Geraniol following as its synthesis step of raw material:
Step 1 is reacted in methylene dichloride with dimethyl thioether and N-chlorosuccinimide with Geraniol (formal name used at school: (E)-3,7-dimethyl--2,6-octadiene-1-alcohol) and to be obtained geranyl chloride;
Step 2, geranyl chloride and methyl aceto acetate can obtain the geranyl methyl aceto acetate under the salt of wormwood effect, and adding sodium hydroxide added thermal decarboxylation and obtains geranyl acetone after reaction finished;
Step 3, geranyl acetone feed acetylene gas under the mineral alkali effect, reaction obtains (E)-3,7,11-trimethyldodecane-6,10-diene-1-alkynes-3-alcohol;
Step 4, (E)-3,7,11-trimethylammonium 12 carbon-6,10-diene-pure and mild diacetyl oxide of 1-alkynes-3-obtains (E)-3,7 under acid catalysis, 11-trimethylammonium 12 carbon-6,10-diene-1-alkynes-3-guanidine-acetic acid fat;
Step 5, (E)-3,7,11-trimethylammonium 12 carbon-6,10-diene-1-alkynes-3-guanidine-acetic acid fat is reset under silver catalyst and is obtained (E)-3,7,11-trimethylammonium-1,2,6,10-apos acetate fat;
Step 6, (E)-3,7,11-trimethylammonium-1,2,6, methanol solution hydrolysis under the inorganic base aqueous solution effect of 10-apos acetate fat obtains farnesal;
Step 7, farnesal use sodium borohydride reduction to be farnesol in methyl alcohol.
On the such scheme basis, in the step 1, said Geraniol is dissolved in the methylene dichloride; Add dimethyl thioether at-20～10 ℃; Add the N-chlorosuccinimide then, elimination succimide after reaction finishes is behind the dichloromethane solution washing and drying in batches; Concentrate and obtain geranyl chloride, directly be used for step reaction down.
On the such scheme basis, said N-chlorosuccinimide adds the back at-5～5 ℃ in batches, stirs 2 hours.
On the such scheme basis, in the step 2, under the room temperature; Methyl aceto acetate is added drop-wise in salt of wormwood and the acetone mixed solution; Stirring adds the acetone soln of geranyl chloride after half a hour, filtering and concentrating after reaction finishes adds entry and aqueous sodium hydroxide solution; Heating in water bath to 50～60 a ℃ decarboxylation obtains geranyl acetone; Distillation purifying obtains the pure article of geranyl acetone, and two step productive rates are common>70%, geranyl chloride and methyl aceto acetate mol ratio are (1,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9 or 2): 1.
On the such scheme basis, in the step 3, acetylene gas is passed in the methyl tertbutyl ether mixture of mineral alkali; 5～10 ℃ of methyl tertbutyl ethereal solutions that drip geranyl acetone of controlled temperature, reaction finishes and goes out with Hydrogen chloride essence, and the MTBE extraction concentrates and obtains (E)-3; 7,11-trimethyldodecane-6,10-diene-1-alkynes-3-alcohol; Distillation yield is common>80%, wherein, described mineral alkali is potassium tert.-butoxide, sodium tert-butoxide or sodium methylate.
On the such scheme basis, in the step 4, diacetyl oxide and acid join (E)-3; 7,11-trimethylammonium 12 carbon-6 are in 10-diene-1-alkynes-3-alcohol; Reaction finishes the back with concentrated (E)-3,7,11-trimethylammonium 12 carbon-6 of obtaining of MTBE extraction; 10-diene-1-alkynes-3-guanidine-acetic acid fat directly is used for down step reaction, and described acid is a kind of in sulfuric acid, phosphoric acid, polyphosphoric acid and the hydrochloric acid.
On the such scheme basis, in the step 5, (E)-3,7; 11-trimethylammonium 12 carbon-6, the ethylene glycol dimethyl ether solution of 10-diene-1-alkynes-3-guanidine-acetic acid fat is added drop-wise in the mixture of silver salt and glycol dimethyl ether, resets to obtain (E)-3,7; 11-trimethylammonium-1,2,6; 10-apos acetate fat directly is used for step reaction down with concentrating with MTBE extraction after the frozen water, and described silver salt is a kind of in silver tetrafluoroborate, silver acetate, Silver monochloride and the hexafluoro-antimonic acid silver.
On the such scheme basis, in the step 6, inorganic base aqueous solution is added drop-wise to (E)-3,7; 11-trimethylammonium-1,2,6; In the methanol solution of 10-apos acetate fat,, contain 10% Z formula isomer with obtaining farnesal with the MTBE extraction after the frozen water; Use sodium sulfite anhy 96 salt forming method purifying to obtain the farnesal of full E formula, productive rate is common>70%, said mineral alkali is yellow soda ash or salt of wormwood.
On the such scheme basis, said step 6 temperature of reaction is 0～20 ℃.
On the such scheme basis, in the said step 7, methyl alcohol joins in the mixture of farnesal, Peng Qinghuana and THF; Adding Hydrogen chloride essence after reaction finishes goes out; With the MTBE extraction, distillation obtains farnesol, and productive rate is common>90%; Wherein, farnesal and Peng Qinghuana proportioning are 1: (1,1.05,1.1,1.15 or 1.2).
Compound method of the present invention have reduce cost, reaction scheme safety, environmental protection, products therefrom purity advantages of higher.
The practical implementation method
How further specify the present invention below in conjunction with concrete embodiment realizes:
Step 1:
In 3000 ml four-hole bottles, add Geraniol 462 g and methylene dichloride 1900 ml, stir and drip 223.2 g dimethyl thioethers down; The maintenance system 0 ℃, insulated and stirred 15 min add NCS 422 g in batches; Be incubated-5～5 ℃ and stir 2 h, TLC tracks to and reacts completely.Filtration obtains filtrating and adds 2000 ml washing; Water adds 500 ml methylene dichloride back extractions, merges organic phase and washes once with 5% sodium bicarbonate aqueous solution, 2000 ml, washes once with 1500 ml sodium chloride aqueous solutions again; Organic phase is dry concentrate geranyl chloride 550g, directly be used for step reaction down.Purity 85%, yield 90%.
Step 2:
In 3000 ml four-hole bottles, nitrogen protection adds acetone 1400 ml and salt of wormwood 431 g down, drips methyl aceto acetate 325 g (molecular weight 130.15), 2.49MOL insulated and stirred 20 min; 21 ℃ of room temperatures begin to drip geranyl chloride 550g (molecular weight 172.72) 3.18MOL is dissolved in the solution of 400 ml acetone, insulated and stirred 1.5 h, and warming-in-water is spent the night to 45-50 ℃ of insulated and stirred, and TLC tracks to and reacts completely.Add 1200 ml water after the filtration rear filtrate concentrates, add 200 g sodium hydroxide/800 ml water, water-bath 50-60 ℃, stir hydrolysis and spend the night, the GC detection reaction is complete.Reduce to room temperature, use ethyl acetate extraction, merge organic phase, the salt solution washing, organic phase is dry concentrate pale brown look bullion, distillation obtains geranyl acetone 430g, purity 95%, productive rate 79%.
Step 3:
In 2000 ml four-hole bottles; Methylate tertbutyl ether 1200 ml; Ice-water bath is cooled to about 10 ℃, adds potassium tert.-butoxide 114.3 g in batches, feeds through vitriol oil exsiccant acetylene gas; Keep logical acetylene 25 min, begin to drip the solution that geranyl acetone 165 g are dissolved in MTBE 400 ml.Drip off insulation and stir 30 min for 5-10 ℃, GC detects to reacting completely.Stir down, reaction solution is poured in the mixed solution of 2 L frozen water+100 ml concentrated hydrochloric acids, stir, the organic phase color glassy yellow that go bad, the repetition measurement aqueous pH values is less than 3, as if less than adding acid; Separatory, water are used 500 ml MTBE back extractions again, merge organic phase, 1.5 L saturated common salt water washings; Organic phase is dry, filter, concentrate bullion (E)-3,7,11-trimethyldodecane-6,10-diene-1-alkynes-3-alcohol; Distillation obtains the 150g product, purity 95%, yield 80%.
Step 4:
In the 500 ml four-hole bottles, add (E)-3,7,11-trimethyldodecane-6; 10-diene-1-alkynes-3-alcohol 123 g, nitrogen protection begins to drip aceticanhydride 71.4 g and phosphoric acid 0.8 g for following 30 ℃, and 30 min dropwise, and are warming up to about 50 ℃; Insulated and stirred 3 h, GC follows the tracks of and reacts completely, and adds the extraction of 600 ml MTBEs and 1000 ml salt solution after the cooling, water 200 ml MTBE back extractions; Merge organic phase, brine wash, dry, filtration, concentrated gets bullion.(E)-3,7,11-trimethylammonium 12 carbon-6,10-diene-1-alkynes-3-guanidine-acetic acid fat 170g, purity 80%, yield 95%.Directly be used for step reaction down.
Step 5:
In the 2000 ml four-hole bottles, add glycol dimethyl ether 1400 ml and silver tetrafluoroborate 4 g, nitrogen protection, 30 ℃ of stirrings of water-bath drip (E)-3,7 down; 11-trimethylammonium 12 carbon-6,10-diene-1-alkynes-3-guanidine-acetic acid fat 170g is dissolved in the solution of 300 ml glycol dimethyl ethers, is warming up to 55-60 ℃ of insulation reaction and spends the night, and TLC follows the tracks of and reacts completely, and adds 5000 ml frozen water and adds the extraction of 1700+700 ml MTBE; Merge the washing of organic phase sodium chloride aqueous solution, organic phase is dry, filters, and concentrates; Get bullion (E)-3,7,11-trimethylammonium-1,2; 6,10-apos acetate fat 165g, unstable products can't detect purity.Directly be used for step reaction down.
Step 6:
In the 3000 ml four-hole bottles, add (E)-3,7,11-trimethylammonium-1,2,6,10-apos acetate fat 165 g, methyl alcohol 1650 ml stir and dissolve clearly; Water bath heat preservation 20-25 ℃ stirring drips aqueous sodium carbonate, and insulated and stirred is spent the night; TLC tracking next day raw material reaction finishes.After adding 3200 ml water dilutions, add the extraction of 1500+1000 ml MTBE, merge organic phase, the saturated common salt water washing, organic phase is dry, filter, concentrate, the bullion farnesal, contain 10% Z formula isomer.With sodium sulfite anhy 96 with it the salt forming method purifies and separates obtain pure farnesal 100g, purity 98%, productive rate 70%.
Step 7:
In the 1000 ml four-hole bottles, add farnesal 100g (molecular weight 221.34), Peng Qinghuana 20g (molecular weight 37.87) and THF 500mL, 100ml methyl alcohol joins in the said mixture; After TLC tracking reaction finishes, carefully add Hydrogen chloride essence and go out, extract with MTBE; The salt washing; Distillation obtains farnesol 90g, purity 98%, productive rate 90% after dry the concentrating.
Claims (10)
1. the compound method of a farnesol, use Geraniol following as its synthesis step of raw material:
Step 1, with Geraniol (E)-3,7-dimethyl--2,6-octadiene-1-alcohol reacts in methylene dichloride with dimethyl thioether and N-chlorosuccinimide and obtains geranyl chloride;
Step 2, geranyl chloride and methyl aceto acetate can obtain the geranyl methyl aceto acetate under the salt of wormwood effect, and adding sodium hydroxide added thermal decarboxylation and obtains geranyl acetone after reaction finished;
Step 3, geranyl acetone feed acetylene gas under the mineral alkali effect, reaction obtains (E)-3,7,11-trimethyldodecane-6,10-diene-1-alkynes-3-alcohol;
Step 4, (E)-3,7,11-trimethylammonium 12 carbon-6,10-diene-pure and mild diacetyl oxide of 1-alkynes-3-obtains (E)-3,7 under acid catalysis, 11-trimethylammonium 12 carbon-6,10-diene-1-alkynes-3-guanidine-acetic acid fat;
Step 5, (E)-3,7,11-trimethylammonium 12 carbon-6,10-diene-1-alkynes-3-guanidine-acetic acid fat is reset under silver catalyst and is obtained (E)-3,7,11-trimethylammonium-1,2,6,10-apos acetate fat;
Step 6, (E)-3,7,11-trimethylammonium-1,2,6, methanol solution hydrolysis under the inorganic base aqueous solution effect of 10-apos acetate fat obtains farnesal;
Step 7, farnesal use sodium borohydride reduction to be farnesol in methyl alcohol.
2. the compound method of farnesol according to claim 1, it is characterized in that: in the step 1, said Geraniol is dissolved in the methylene dichloride; Add dimethyl thioether at-20～10 ℃; Add the N-chlorosuccinimide then, elimination succimide after reaction finishes is behind the dichloromethane solution washing and drying in batches; Concentrate and obtain geranyl chloride, directly be used for step reaction down.
3. the compound method of farnesol according to claim 1 and 2 is characterized in that: at-5～5 ℃, stirred 2 hours after said N-chlorosuccinimide adds in batches.
4. the compound method of farnesol according to claim 1 is characterized in that: in the step 2, under the room temperature; Methyl aceto acetate is added drop-wise in salt of wormwood and the acetone mixed solution, and stirring adds the acetone soln of geranyl chloride, filtering and concentrating after reaction finishes after half a hour; Add entry and aqueous sodium hydroxide solution; Heating in water bath to 50～60 a ℃ decarboxylation obtains geranyl acetone, and distillation purifying obtains the pure article of geranyl acetone, and geranyl chloride and methyl aceto acetate mol ratio are (1～2): 1.
5. the compound method of farnesol according to claim 1, it is characterized in that: in the step 3, acetylene gas is passed in the methyl tertbutyl ether mixture of mineral alkali; 5～10 ℃ of methyl tertbutyl ethereal solutions that drip geranyl acetone of controlled temperature, reaction finishes and goes out with Hydrogen chloride essence, and the MTBE extraction concentrates and obtains (E)-3; 7; 11-trimethyldodecane-6,10-diene-1-alkynes-3-alcohol, described mineral alkali is potassium tert.-butoxide, sodium tert-butoxide or sodium methylate.
6. the compound method of farnesol according to claim 1, it is characterized in that: in the step 4, diacetyl oxide and acid join (E)-3; 7,11-trimethylammonium 12 carbon-6 are in 10-diene-1-alkynes-3-alcohol; Reaction finishes the back with concentrated (E)-3,7,11-trimethylammonium 12 carbon-6 of obtaining of MTBE extraction; 10-diene-1-alkynes-3-guanidine-acetic acid fat, described acid are a kind of in sulfuric acid, phosphoric acid, polyphosphoric acid and the hydrochloric acid.
7. the compound method of farnesol according to claim 1 is characterized in that: in the step 5, (E)-3; 7,11-trimethylammonium 12 carbon-6, the ethylene glycol dimethyl ether solution of 10-diene-1-alkynes-3-guanidine-acetic acid fat is added drop-wise in the mixture of silver salt and glycol dimethyl ether; Rearrangement obtains (E)-3,7,11-trimethylammonium-1; 2,6,10-apos acetate fat; Directly be used for step reaction down with concentrating with MTBE extraction after the frozen water, described silver salt is a kind of in silver tetrafluoroborate, silver acetate, Silver monochloride and the hexafluoro-antimonic acid silver.
8. the compound method of farnesol according to claim 1, it is characterized in that: in the step 6, inorganic base aqueous solution is added drop-wise to (E)-3; 7,11-trimethylammonium-1,2; 6, in the methanol solution of 10-apos acetate fat, with obtaining farnesal with the MTBE extraction after the frozen water; Contain 10% Z formula isomer, use sodium sulfite anhy 96 salt forming method purifying to obtain the farnesal of full E formula, said mineral alkali is yellow soda ash or salt of wormwood.
9. the compound method of farnesol according to claim 8, it is characterized in that: said step 6 temperature of reaction is 0～20 ℃.
10. the compound method of farnesol according to claim 1; It is characterized in that: in the said step 7, methyl alcohol joins in the mixture of farnesal, Peng Qinghuana and THF, adds Hydrogen chloride essence after reaction finishes and goes out; Extract with MTBE; Distillation obtains farnesol, and wherein, farnesal and Peng Qinghuana proportioning are 1:1～1.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110443259XA CN102432433A (en) | 2011-12-27 | 2011-12-27 | Method for synthesizing farnesol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110443259XA CN102432433A (en) | 2011-12-27 | 2011-12-27 | Method for synthesizing farnesol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102432433A true CN102432433A (en) | 2012-05-02 |
Family
ID=45980829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110443259XA Pending CN102432433A (en) | 2011-12-27 | 2011-12-27 | Method for synthesizing farnesol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102432433A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108026006A (en) * | 2015-09-17 | 2018-05-11 | 帝斯曼知识产权资产管理有限公司 | The production of farnesol |
| CN116041157A (en) * | 2022-12-21 | 2023-05-02 | 江苏宏邦化工科技有限公司 | Method for preparing citral by rearrangement of dehydrolinalool |
-
2011
- 2011-12-27 CN CN201110443259XA patent/CN102432433A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108026006A (en) * | 2015-09-17 | 2018-05-11 | 帝斯曼知识产权资产管理有限公司 | The production of farnesol |
| CN116041157A (en) * | 2022-12-21 | 2023-05-02 | 江苏宏邦化工科技有限公司 | Method for preparing citral by rearrangement of dehydrolinalool |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103172504B (en) | Synthetic method of 2,7-dimethyl-2,4,6-octytriene-1,8-dialdehyde | |
| CN103601686A (en) | Method for synthesizing fluorine-containing pyrimidine compounds by virtue of one-pot method | |
| US4107439A (en) | Process for preparing arylalkanoic acid derivatives | |
| CN102432433A (en) | Method for synthesizing farnesol | |
| CN103664923A (en) | Preparation method for nifuratel | |
| CN104211598A (en) | Preparation method of 2-(o-hydroxyphenyl)cyclopropane-1-carboxylic acid | |
| CN102351695A (en) | High-selectivity synthesis method of ethyl alpha-bromoacetate | |
| CN103102264B (en) | Preparation method of salicylic acid compound | |
| DK3250556T3 (en) | PROCEDURES FOR THE PREPARATION OF COMPOUNDS, SUCH AS 3-ARYL BUTANALS THAT CAN BE USED FOR THE SYNTHESIS OF MEDETOMIDINE | |
| CN104909994A (en) | Method for synthesizing ciprofibrate intermediate and the intermediate | |
| CN114349633A (en) | Process for the preparation of diesters of glutaconic acid | |
| IL210353A (en) | Method for producing phenylalkane- 1- ols | |
| CN111116339B (en) | Method for artificially synthesizing curcumin and derivatives thereof | |
| JP2009523716A (en) | Method for producing bisabolol which does not contain farnesol or has a small content of farnesol | |
| CN109503545B (en) | Preparation method of 1, 4-cyclohexanedione monoethylene glycol ketal | |
| WO2021195751A1 (en) | Catalytic cannabigerol processes and precursors | |
| CN104230880A (en) | Simple preparation method of 2-((4R,6R)-6-aminoethyl-2,2-dimethyl-1,3-dioxyhexacyclo-4-yl)acetate | |
| CN105348061A (en) | 2-cyclohexene-1-ketone preparation method | |
| CN114195638B (en) | Preparation method of phenyl o-hydroxybenzoate | |
| CN101555205B (en) | Preparing method of 3-oxo-1-cyclobutane-carboxylic acid | |
| CN101423474A (en) | Method for synthesizing cooling agent L-menthyl 3-hydroxybutyrate | |
| ES2875151T3 (en) | Procedures for the preparation of unsaturated malonates | |
| CN104370868B (en) | Dihydro maltol and dihydro ethyl maltol synthesis method | |
| US4064150A (en) | Synthesis of isoprenoid 1,5-dienes | |
| CN103408406B (en) | A kind of preparation method of eugenol methyl ether |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120502 |