CN103833722A - Method for preparing safrole - Google Patents
Method for preparing safrole Download PDFInfo
- Publication number
- CN103833722A CN103833722A CN201410079934.9A CN201410079934A CN103833722A CN 103833722 A CN103833722 A CN 103833722A CN 201410079934 A CN201410079934 A CN 201410079934A CN 103833722 A CN103833722 A CN 103833722A
- Authority
- CN
- China
- Prior art keywords
- safrole
- piperonyl cyclonene
- preparation
- catalyst
- afion
- 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.)
- Granted
Links
- ZMQAAUBTXCXRIC-UHFFFAOYSA-N safrole Chemical compound C=CCC1=CC=C2OCOC2=C1 ZMQAAUBTXCXRIC-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims description 12
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims abstract description 10
- 238000004440 column chromatography Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- JBVNWTXRFKZNBQ-UHFFFAOYSA-N 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-en-1-one Chemical compound C1C(CCCCCC)=CC(=O)CC1C1=CC=C(OCO2)C2=C1 JBVNWTXRFKZNBQ-UHFFFAOYSA-N 0.000 claims description 33
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000008399 tap water Substances 0.000 claims description 3
- 235000020679 tap water Nutrition 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 238000005292 vacuum distillation Methods 0.000 abstract 1
- 244000009660 Sassafras variifolium Species 0.000 description 9
- 235000004263 Ocotea pretiosa Nutrition 0.000 description 8
- 239000003921 oil Substances 0.000 description 6
- 241000723346 Cinnamomum camphora Species 0.000 description 4
- -1 metal complex compound Chemical class 0.000 description 4
- 239000000341 volatile oil Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000758794 Asarum Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- 241000732800 Cymbidium Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000012550 Pimpinella anisum Nutrition 0.000 description 1
- 240000004760 Pimpinella anisum Species 0.000 description 1
- 235000017325 Sassafras variifolium Nutrition 0.000 description 1
- 244000082946 Tarchonanthus camphoratus Species 0.000 description 1
- 235000005701 Tarchonanthus camphoratus Nutrition 0.000 description 1
- 244000025271 Umbellularia californica Species 0.000 description 1
- 235000008674 Umbellularia californica Nutrition 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 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
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000008935 nutritious Nutrition 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229940081310 piperonal Drugs 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000001101 sassafras albidum Substances 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Fats And Perfumes (AREA)
Abstract
本发明公开一种黄樟素的制备方法，即以市售的烯丙醇和胡椒环为原料，同时以胡椒环兼作溶剂，在催化剂Nafion-H作用下，控制温度为15-50℃，搅拌转速为500-800r/min下进行傅克反应6～10h，所得的反应液经过滤、洗涤、干燥后得到的黄樟素的胡椒环溶液经减压蒸馏除去胡椒环溶剂，然后再进行柱层析，最终得的黄樟素。本发明的一种黄樟素的制备方法，其制备过程简单，生产成本低，适于规模化生产。进一步，本发明的一种黄樟素的制备方法，由于反应的原料胡椒环兼作溶剂可以回收再用，催化剂Nafion-H也可以回收再用，产生的废弃物都少，因此对环境友好。The invention discloses a preparation method of safrole, which uses commercially available allyl alcohol and piperonylcycline as raw materials, and uses piperonylcycline as a solvent at the same time. Under the action of catalyst Nafion-H, the temperature is controlled at 15-50°C and the stirring speed is 500°C. Carry out Friedel-Crafts reaction at -800r/min for 6-10h, the obtained reaction solution is filtered, washed and dried, and the piperonylcycline solution of safrole obtained after vacuum distillation to remove the piperonylcycline solvent is then carried out by column chromatography to obtain the final product Safrole. The preparation method of safrole of the present invention has simple preparation process, low production cost and is suitable for large-scale production. Further, a kind of safrole preparation method of the present invention, because the raw material piperonine of reaction doubles as solvent can be recycled and reused, and catalyst Nafion-H can also be recycled and reused, and the waste that produces is all little, therefore is friendly to the environment.
Description
Technical field
The present invention relates to a kind of preparation method of safrole.
Background technology
Safrole, claims again safrole, English Safrole by name, and colourless or light yellow liquid, has camphorwood smell, and its structural formula is.Be soluble in ethanol, can be miscible with chloroform, ether, water insoluble and glycerine.Relative density 1.096, approximately 11 ℃, zero pour, 232～234 ℃ of boiling points, refractive index 1.538,97 ℃ of flash-points.Safrole be much edible natural essence as yellow camphor tree essential oil, aniseed essential oil and camphor main body of oil, 80%. safrole that account for yellow camphor tree essential oil are with Semen Myristicae, Japanese asarum, also has a small amount of existence in the essence that the spices such as California bay tree are made.The local flavor that yellow camphor tree essential oil is often used as beer and other wine adds into.Sassafras (Sas-safras albidum) tree root skin is also the main component of popular a kind of medicinal nutritious tea-Huang Zhangcha.
It is widely used in the industries such as spices, medicine, agricultural chemicals, and main synthesizing piperonal, vanirone, ethyl chinese cymbidium phenol, piperonyl butoxide etc., be a kind of purposes valuable perfume base very widely, and market outlook are extremely wide.At present, day by day increase take sassafras wood oil rope as the synthetic produce market demand of raw material, the supplydemand relationship of sassafras wood oil rope world market is for a long time in the situation that supply falls short of demand, and world production region mainly contains China, Brazil and South America, and is the extract of natural sassafras.Add in recent years; in order to protect vegetation; avoid the destruction to ecotope; the method that various countries have successively limited by digging sassafras root obtains safrole; Brazil even forbids strictly to damage sassafras; therefore,, in the face of in the increasingly withered exhausted situation of natural sassafras resource, from natural, obtaining merely safrole, to can not meet the market requirement far away growing.
And the method for chemosynthesis is prepared the document of safrole few, Naofumi Tsukada has reported (Synlett, (10), 1431-1434; 2003) be raw material by the p-toluenesulfonic esters of piperonyl cyclonene and vinyl carbinol, adopting rare metal complex compound is that catalyzer is prepared safrole.The rarer costliness of catalyzer that this method is used and being difficult to obtain, and its productive rate is not high yet.
The people such as Lin Bin, Yang Xi has reported (Guangdong chemical industry, 30 (2), 6-7; 2003) be raw material with piperonyl cyclonene, first its bromo become to corresponding bromide, then make Grignard reagent, then prepare safrole with allyl bromine reaction.Although the method raw material is easy to get, reaction conditions is also relatively gentle, but piperonyl cyclonene need to be become to corresponding Grignard reagent, made by grignard reaction again, so inevitably there are a large amount of self coupling by product to produce, bring difficulty to separation, also wasted a large amount of raw materials, and grignard reaction is also stricter to reagent requirement.
The people such as Stefano Protti have reported (Organic & Biomolecular Chemistry, 3 (15), 2868-2871; 2005) be raw material with chloro piperonyl cyclonene and allyltrimethylsilane alkane, under cesium carbonate and trifluoro sulfonation, prepare safrole.The raw material allyltrimethylsilane alkane costliness that the method adopts is on the one hand difficult to obtain, and the singularity of this reaction process on the other hand makes its industrialization be difficult for realizing.
Therefore, the method for an effective full chemosynthesis sassafras wood oil rope of searching becomes the study hotspot of various countries' chemist.
Summary of the invention
The object of the invention is the severe reaction conditions existing in the synthetic method in order to solve above-mentioned safrole, anti-response environment is unfriendly, easily produce waste material and waste liquid, and syntheti c route is long, cause its production cost that a kind of preparation method of safrole, this preparation method's environmental protection are provided compared with high-technology problem, production cost is low, simple to operate, reaction conditions is easy to realize, and is convenient to suitability for industrialized production.
Know-why of the present invention
Take commercially available vinyl carbinol and piperonyl cyclonene as raw material, double as solvent with one of reactant piperonyl cyclonene simultaneously, under catalyst n afion-H effect, make safrole through Friedel-Crafts reaction one step, its reaction process equation is as follows:
Technical scheme of the present invention
A preparation method for safrole, step is as follows:
Piperonyl cyclonene and vinyl carbinol are added in reactor, then add catalyst n afion-H, control temperature is 15-50 ℃, and mixing speed is under 500-800r/min, to carry out Friedel-Crafts reaction 6～10h, obtains reaction solution;
Above-mentioned piperonyl cyclonene used in Friedel-Crafts reaction, the amount of vinyl carbinol of carrying out, calculates i.e. piperonyl cyclonene: vinyl carbinol is 30:1 in molar ratio; The amount of catalyst n afion-H used, calculates i.e. catalyst n afion-H: piperonyl cyclonene is 10:100 by the mass ratio of itself and piperonyl cyclonene;
By the reacting liquid filtering of above-mentioned gained, the filtrate of gained first, with saturated sodium bicarbonate solution washing 2-3 time, then, with after tap water washing 2-3 time, adopts anhydrous sodium sulphate to be dried under room temperature, then remove by filter anhydrous sodium sulphate, the filtrate obtaining is the piperonyl cyclonene solution of safrole;
Be 55-60 ℃ by the piperonyl cyclonene solution control temperature of the safrole of gained, pressure is that 0.012MPa carries out underpressure distillation and removes piperonyl cyclonene solvent, and then carries out column chromatography, finally obtains safrole;
Above-mentioned column chromatography process developping agent used be by sherwood oil and ethyl acetate by volume ratio be that 30:1 mixes.
After above-mentioned reacting liquid filtering, the filter cake of gained is catalyst n afion-H, can manipulation of regeneration to recycle;
The regeneration process of catalyst n afion-H is as follows:
The filter cake of gained after above-mentioned reacting liquid filtering is used to acetone and deionized water wash successively, and then at 105 ℃, dried overnight obtains the catalyst n afion-H after regeneration.
Useful technique effect of the present invention
The preparation method of a kind of safrole of the present invention; because the vinyl carbinol take commercially available and piperonyl cyclonene are raw material; under catalyst n afion-H effect; make safrole through Friedel-Crafts reaction one step, therefore its preparation process is simple, is suitable for large-scale production; simultaneously owing to doubling as solvent with piperonyl cyclonene in preparation process; therefore, material used in preparation process is few, and production cost is low.
Further, the preparation method of a kind of safrole of the present invention, can recycle because the raw material piperonyl cyclonene of reaction doubles as solvent, and catalyst n afion-H also can recycle, and the waste of generation all lacks, therefore environmentally friendly.
Embodiment
Below by embodiment, the present invention is described in further detail, the preparation method of safrole is as follows:
Raw material used in various embodiments of the present invention is except special instruction, and other is commercially available.
Piperonyl cyclonene, vinyl carbinol, chemical pure, Shanghai Chemical Reagent Co., Ltd., Sinopharm Group;
Catalyst n afion-H, Jiangsu Se Kesai thinks resin company limited and produces.
embodiment 1
A preparation method for safrole, concrete steps are as follows:
By 146.54 g(1.2mol) piperonyl cyclonene and 2.33g(0.04mol) vinyl carbinol is added in the there-necked flask glass reactor that thermometer, prolong, drying tube are housed, add again 14.65g catalyst n afion-H, control temperature is 15-50 ℃, mixing speed is under 500-800r/min, to carry out Friedel-Crafts reaction, reaction process detects vinyl carbinol content with the GC6890-MS5973 gas chromatograph of U.S. Aglient, substantially finish to vinyl carbinol reaction, be stopped reaction after Friedel-Crafts reaction 4h, obtain reaction solution;
Above-mentioned piperonyl cyclonene used in Friedel-Crafts reaction, the amount of vinyl carbinol of carrying out, calculates i.e. piperonyl cyclonene: vinyl carbinol is 30:1 in molar ratio; The amount of catalyst n afion-H used, calculates i.e. catalyst n afion-H: piperonyl cyclonene is 10:100 by the mass ratio of itself and piperonyl cyclonene;
The reacting liquid filtering of above-mentioned gained; the filtrate of gained is washed 2-3 time with saturated sodium bicarbonate solution, then with after tap water washing 2-3 time, under room temperature, is dried by anhydrous sodium sulphate; and then removing by filter anhydrous sodium sulphate through Büchner funnel, the filtrate obtaining is the piperonyl cyclonene solution of safrole;
The piperonyl cyclonene solution control temperature of the safrole of gained is 55-60 ℃, and pressure is that 0.012MPa carries out underpressure distillation to remove piperonyl cyclonene solvent, then carries out column chromatography, finally obtains 5.32g product, and its productive rate with respect to raw material vinyl carbinol is 82%;
Above-mentioned column chromatography process developping agent used be by sherwood oil and ethyl acetate by volume ratio be that 30:1 mixes.
The product through column chromatography gained of above-mentioned gained detects through Bruker-AMX 400 type nuclear magnetic resonance analyser, and the data of its nucleus magnetic resonance are as follows:
1H?NMR?(400?MHz,?CDCl
3):?δ6.78?(?d,?J=7.8Hz,?1H),?6.71?(s,?1H),?6.69(d,?J=7.8?Hz,?1H)?5.99-5.92?(m,?3H),?5.13-5.08?(m,?2H),?3.25?(d,?J?=?6.4,2H)。
Can draw the above-mentioned safrole being through the product of column chromatography gained from the data of the nucleus magnetic resonance of above-mentioned gained.
Foregoing is only the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (2)
1. a preparation method for safrole, is characterized in that concrete steps are as follows:
Piperonyl cyclonene and vinyl carbinol are added in reactor, then add catalyst n afion-H, control temperature is 15-50 ℃, and mixing speed is under 500-800r/min, to carry out Friedel-Crafts reaction 6～10h, obtains reaction solution;
Above-mentioned piperonyl cyclonene used in Friedel-Crafts reaction, the amount of vinyl carbinol of carrying out, calculates i.e. piperonyl cyclonene: vinyl carbinol is 30:1 in molar ratio; The amount of catalyst n afion-H used, calculates i.e. catalyst n afion-H: piperonyl cyclonene is 10:100 by the mass ratio of itself and piperonyl cyclonene;
By the reacting liquid filtering of above-mentioned gained, the filtrate of gained first, with saturated sodium bicarbonate solution washing 2-3 time, then, with after tap water washing 2-3 time, adopts anhydrous sodium sulphate to be dried under room temperature, then remove by filter anhydrous sodium sulphate, the filtrate obtaining is the piperonyl cyclonene solution of safrole;
Be 55-60 ℃ by the piperonyl cyclonene solution control temperature of the safrole of gained, pressure is that 0.012MPa carries out underpressure distillation and removes piperonyl cyclonene solvent, and then carries out column chromatography and obtain safrole.
2. the preparation method of a kind of safrole as claimed in claim 1, it is characterized in that described column chromatography process developping agent used be by sherwood oil and ethyl acetate by volume ratio be that 30:1 mixes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410079934.9A CN103833722B (en) | 2014-03-06 | 2014-03-06 | A kind of preparation method of safrole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410079934.9A CN103833722B (en) | 2014-03-06 | 2014-03-06 | A kind of preparation method of safrole |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103833722A true CN103833722A (en) | 2014-06-04 |
| CN103833722B CN103833722B (en) | 2015-12-09 |
Family
ID=50797661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410079934.9A Active CN103833722B (en) | 2014-03-06 | 2014-03-06 | A kind of preparation method of safrole |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103833722B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1907980A (en) * | 2006-08-11 | 2007-02-07 | 贵阳海丰精细化工有限公司 | Method for synthesizing dihydrosafrole |
-
2014
- 2014-03-06 CN CN201410079934.9A patent/CN103833722B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1907980A (en) * | 2006-08-11 | 2007-02-07 | 贵阳海丰精细化工有限公司 | Method for synthesizing dihydrosafrole |
Non-Patent Citations (2)
| Title |
|---|
| TSUKADA, NAOFUMI ET AL: "Rhodium and iridium catalyzed allylation of electron rich arenes with allyl tosylate", 《SYNLETT》 * |
| 林彬等: "黄樟油素的合成眼睛", 《广东化工》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103833722B (en) | 2015-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20130284584A1 (en) | Process for separating ethylene glycol and 1, 2-butanediol | |
| CN104761429B (en) | A kind of method for producing dimethyl carbonate and ethylene glycol | |
| CN104058948B (en) | The method of reclaim(ed) sulfuric acid and trimethylacetic acid from the spent acid of trimethylacetic acid building-up process by-product | |
| CN103524345A (en) | Product separation process for preparing methyl acrylate from methyl acetate | |
| CN101906024B (en) | Method for preparing sandaler | |
| CN106866366B (en) | A kind of method for removing dihydric alcohol or polyhydric alcohol impurity in ethylene glycol and increasing the production of ethylene glycol | |
| CN106146299B (en) | The method for producing acetic acid esters and ethylene glycol | |
| JP2012510450A5 (en) | ||
| CN103833722A (en) | Method for preparing safrole | |
| CN105085335A (en) | Method for preparing 3-mercapto-propionate | |
| CN104592016A (en) | Efficient catalysis method for direct esterification and transesterification | |
| CN101831198A (en) | Preparation method of capsanthin | |
| CN104710285A (en) | Method for recycling ethylene glycol monomethyl ether | |
| CN104829451B (en) | Combined production method for acetic acid ester and glycol | |
| CN103772325A (en) | Novel method for separating and purifying 1,2-epoxybutane | |
| CN105001061A (en) | Methoxy elgenol derivative and preparation method thereof | |
| CN109134197A (en) | A method of using alkanes entrainer from dichlorohydrin hydrochloric acid solution separating dichloropropanol | |
| CN110452198B (en) | Preparation method of feloxicib | |
| CN101456792A (en) | Method for preparing diatomic alcohol compounds by annular carbonic acid esters hydrolysis | |
| CN102432465B (en) | Method for preparing methyl methacrylate | |
| CN104529774B (en) | The preparation method of a kind of tributyl citrate | |
| CN104447262B (en) | Method for synthesizing 1-chloro-1-chloroacetyl-cyclopropane by one-pot method | |
| CN101659612B (en) | Selective esterification method | |
| CN107226802B (en) | A kind of carbonic acid glyceride synthetic method | |
| CN104817453B (en) | A kind of method synthesizing cyclopropanecarboxylic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170213 Address after: 201416 Shanghai city Fengxian District new economic zone Shen Xinlin Highway No. 559 Patentee after: SHANGHAI PU-JIE FRAGRANCE Co.,Ltd. Address before: 200235 Xuhui District, Caobao Road, No. 120, Patentee before: Shanghai Institute of Technology |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 201416 Shanghai city Fengxian District new economic zone Shen Xinlin Highway No. 559 Patentee after: PuJie flavor (Shanghai) Co.,Ltd. Address before: 201416 Shanghai city Fengxian District new economic zone Shen Xinlin Highway No. 559 Patentee before: SHANGHAI PU-JIE FRAGRANCE Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |