CN108129301B - Synthetic method of 3-methyl-2-butene-1-alcohol formate - Google Patents
Synthetic method of 3-methyl-2-butene-1-alcohol formate Download PDFInfo
- Publication number
- CN108129301B CN108129301B CN201711487459.9A CN201711487459A CN108129301B CN 108129301 B CN108129301 B CN 108129301B CN 201711487459 A CN201711487459 A CN 201711487459A CN 108129301 B CN108129301 B CN 108129301B
- Authority
- CN
- China
- Prior art keywords
- methyl
- butene
- bisabolol
- reaction
- formate
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention belongs to the technical field of chemical synthesis, and particularly relates to a synthetic method of 3-methyl-2-butene-1-alcohol formate. According to the synthesis method of the 3-methyl-2-butene-1-alcohol formate, on the basis of the prior art, sodium bisulfite is selected as a catalyst, so that the yield of the 3-methyl-2-butene-1-alcohol formate is further improved, and the reaction is preferably carried out in the presence of the selected ionic liquid, so that the product yield is effectively improved, the reaction time is effectively accelerated, and the higher product yield is obtained in a shorter time.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a synthetic method of 3-methyl-2-butene-1-alcohol formate.
Background
Bisabolol (Bisabolol), also called Bisabolol and ledebouriella seselol, is one of the sesquiterpene compounds existing in nature. The bisabolol has two structures of alpha-body and beta-body, and the alpha-bisabolol is mainly present in chamomile essential oil, gum poplar essential oil and some essential oils of the genera; the beta-bisabolol is mainly contained in cotton bud essential oil, corn oil, camphor oil and mastic oil. The bisabolol has better stability and skin compatibility, and is suitable for being applied to cosmetics; meanwhile, the bisabolol has the drug effects of diminishing inflammation, sterilizing, healing ulcer, dissolving gallstone and the like, so the application of the bisabolol in the pharmaceutical industry is wide; in addition, the bisabolol has light and pleasant fragrance and is a fixative with better stability, so that the application of the bisabolol in the perfume and the essence is increasingly paid attention; bisabolol can protect and heal the skin, prevent the skin from being affected by daily tension, accelerate the healing process of the skin, is particularly suitable for sensitive skin and body, is widely applied to the formulation of personal care (skin and body care solution, after-shave and after-sun care products), and has anti-inflammatory, natural and safe characteristics, so that the bisabolol becomes a common active ingredient for skin care.
In the prior art, bisabolol is mostly prepared by taking 3-methyl-2-butene-1-ol formate as an intermediate and carrying out condensation reaction with dipentene. 3-methyl-2-buten-1-ol formate, also known as prenol formate, is generally synthesized by esterification of 3-methyl-2-buten-1-ol (prenol) with formic acid. However, in the conventional esterification process, the whole reaction usually takes about 6 hours, and the product yield can only reach about 90% at most. More importantly, in the prior art, synthesis of 3-methyl-2-buten-1-ol formate is usually performed in the process of synthesizing bisabolol, for example, chinese patent CN106831322A discloses a method for producing α -bisabolol, i.e., in the process of synthesizing α -bisabolol, prenol and formic acid are esterified to synthesize prenol formate, and dipentene and dichloromethane are directly added to synthesize α -bisabolol. In the whole process, the synthesis time of the prenyl alcohol formate is long, the yield is slightly low, and the synthesis yield of the final product alpha-bisabolol is only 68%, so that the requirement of actual production is difficult to meet.
Disclosure of Invention
Therefore, the technical problem to be solved by the present invention is to provide a method for synthesizing 3-methyl-2-butene-1-ol formate, so as to solve the problems of long synthesis period and low synthesis rate of 3-methyl-2-butene-1-ol formate in the prior art.
In order to solve the technical problem, the synthesis method of the 3-methyl-2-butene-1-alcohol formate comprises the step of uniformly mixing the 3-methyl-2-butene-1-alcohol with formic acid, and adding sulfite as a catalyst to perform esterification reaction.
The molar ratio of the 3-methyl-2-butene-1-ol to the formic acid is 1: 1.3-1.6.
The sulfite is sodium bisulfite.
The amount of sulfite added is 0.5-2 wt% of the amount of 3-methyl-2-buten-1-ol raw material.
The temperature of the esterification reaction is 30-40 ℃.
The reaction is carried out in the presence of an ionic liquid solvent.
The ionic liquid is alkyl guanidine salt ionic liquid.
The ionic liquid is N, N, N ', N ' -tetramethyl-N ' -octyl guanidine trifluoromethyl acetate ([ HOctTMG)]CF3COO)。
The esterification reaction time is 1-6 h.
The invention also discloses a production method of the alpha-bisabolol, which comprises the step of synthesizing the 3-methyl-2-butene-1-ol formate.
According to the synthesis method of the 3-methyl-2-butene-1-alcohol formate, on the basis of the prior art, sodium bisulfite is selected as a catalyst, so that the yield of the 3-methyl-2-butene-1-alcohol formate product is further improved.
The synthesis method of 3-methyl-2-butene-1-alcohol formate disclosed by the invention preferably performs reaction in the presence of the selected ionic liquid, so that the product yield is effectively improved, the reaction time is effectively accelerated, and the higher product yield is obtained in a shorter time; furthermore, it is more surprising that, in the process for preparing α -bisabolol, 3-methyl-2-buten-1-ol formate is prepared in the presence of the selected ionic liquid, and when dipentene is directly added to the system for the preparation of α -bisabolol, the yield of α -bisabolol can be effectively improved in addition to effectively improving the product yield of 3-methyl-2-buten-1-ol formate and shortening the reaction time, and unexpected technical effects are achieved.
Detailed Description
Example 1 preparation of ionic liquids
The ionic liquid required in the following examples of the invention is N, N, N ', N ' -tetramethyl-N ' -octylguanidine trifluoromethyl acetate ionic liquid ([ HOctTMG ]]CF3COO), and the synthesis method comprises the following steps:
(1) 0.30mol of tetramethylurea is dissolved in 175mL of toluene, and freshly distilled 0.31mol of POCl is added dropwise under the protection of nitrogen and with stirring3Reacting for 10 hours at room temperature, dropwise adding 0.70mol of n-octylamine, stirring for 34 hours at room temperature after the reaction is finished, diluting the reaction system with 175mL of water, vigorously stirring for 30 minutes, taking the lower layer solution, adding solid NaOH into the lower layer solution until the system shows alkalinity, and then adding the solid NaOH into the lower layer solution until the system shows alkalinitySeparating the solution into two layers, filtering to remove solid, separating the filtrate, collecting the upper layer solution, dissolving in diethyl ether, and adding anhydrous Na2CO3Drying, filtering, evaporating to remove the solvent, and distilling the residual liquid under reduced pressure to obtain 0.10mol of the target product N, N, N ', N ' -tetramethyl-N ' -octyl guanidine (OctTMG). FTIR (KBr): v max: 2922, 2852, 1611, 1477, 1430, 1383 and 1142cm-1；
(2) Taking 0.30mol of the obtained OctTMG and 0.30mol of CF3COOH is subjected to neutralization reaction to obtain 0.24mol of target product N, N, N ', N ' -tetramethyl-N ' -octylguanidine trifluoromethyl acetate ionic liquid ([ HOctTMG]CF3COO)。FTIR(KBr)：υmax：2929，2857，1706，1652，1513，1497，1394，1256，1178，1154，1037，644cm-1。
Example 2
In a 250mL three-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel, 86g of 3-methyl-2-buten-1-ol and 60g of formic acid (molar ratio 1: 1.3) were charged, 0.43g (0.5 wt%) of sodium hydrogen sulfite was further added as a catalyst, and then the three-necked flask was placed in a heating mantle with magnetic stirring to heat (35 ℃ C.) and turn on magnetic stirring to conduct esterification for 6 hours. After the reaction is finished, washing the reaction product to be neutral, detecting the product according to the prior art method (see the technical research on alpha-bisabolol synthesis by dipentene, imperial jade, and the like), and calculating the yield of the product 3-methyl-2-butene-1-alcohol formate to be 94.3%.
Example 3
In a 250mL three-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel, 86g of 3-methyl-2-buten-1-ol and 64.4g of formic acid (molar ratio 1: 1.4) were charged, 0.86g (1 wt%) of sodium hydrogen sulfite was further added as a catalyst, and then the three-necked flask was placed in a heating mantle with magnetic stirring to heat the reaction (35 ℃ C.) and the magnetic stirring was turned on to conduct esterification for 5 hours. After the reaction is finished, washing the reaction product to be neutral, detecting the product according to the prior art method (see the technical research on alpha-bisabolol synthesis by dipentene, imperial jade, and the like), and calculating the yield of the product 3-methyl-2-butene-1-alcohol formate to be 94%.
Example 4
In a 250mL three-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel, 86g of 3-methyl-2-buten-1-ol and 69g of formic acid (molar ratio 1: 1.5) were charged, 1.29g (1.5 wt%) of sodium hydrogen sulfite was further added as a catalyst, and then the three-necked flask was placed in a heating mantle with magnetic stirring to heat (35 ℃ C.) and turn on the magnetic stirring to conduct esterification for 5 hours. After the reaction is finished, washing the reaction product to be neutral, detecting the product according to the prior art method (see the technical research on alpha-bisabolol synthesis by dipentene, imperial jade, and the like), and calculating the yield of the product 3-methyl-2-butene-1-alcohol formate to be 94%.
Example 5
In a 250mL three-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel, 86g of 3-methyl-2-buten-1-ol and 73.6g of formic acid (molar ratio 1: 1.6) were charged, 1.72g (2 wt%) of sodium hydrogen sulfite was further added as a catalyst, and then the three-necked flask was placed in a heating mantle with magnetic stirring to heat the reaction (35 ℃ C.) and the magnetic stirring was turned on to conduct esterification for 4 hours. After the reaction is finished, washing the reaction product to be neutral, detecting the product according to the prior art method (see the technical research on alpha-bisabolol synthesis by dipentene, imperial jade, and the like), and calculating the yield of the product 3-methyl-2-butene-1-alcohol formate to be 94.1%.
Example 6
In a 250mL three-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel, 100mL of the N, N, N ', N ' -tetramethyl-N ' -octylguanidine trifluoromethyl acetate ionic liquid prepared in example 1 was charged, and 86g of 3-methyl-2-buten-1-ol and 69g of formic acid (molar ratio 1: 1.5) were added, and 1.29g (1.5 wt%) of sodium hydrogen sulfite was further added as a catalyst, and then the three-necked flask was placed in a heating mantle with magnetic stirring to heat up (35 ℃ C.) and turn on the magnetic stirring to perform esterification reaction for 1 hour. After the reaction is finished, washing the reaction product to be neutral, detecting the product according to the prior art method (see the technical research on alpha-bisabolol synthesis by dipentene, imperial jade, and the like), and calculating the yield of the product 3-methyl-2-butene-1-alcohol formate to be 94.6%.
Example 7
In a 250mL three-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel, 100mL of the N, N, N ', N ' -tetramethyl-N ' -octylguanidine trifluoromethyl acetate ionic liquid prepared in example 1 was charged, and 86g of 3-methyl-2-buten-1-ol and 69g of formic acid (molar ratio 1: 1.5) were added, and 1.29g (1.5 wt%) of sodium hydrogen sulfite was further added as a catalyst, and then the three-necked flask was placed in a heating mantle with magnetic stirring to heat up (35 ℃ C.) and turn on the magnetic stirring to perform esterification for 2 hours. After the reaction is finished, washing the reaction product to be neutral, detecting the product according to the prior art method (see the technical research on alpha-bisabolol synthesis by dipentene, imperial jade, and the like), and calculating the yield of the product 3-methyl-2-butene-1-alcohol formate to be 97.3%.
Example 8
In a 250mL three-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel, 100mL of the N, N, N ', N ' -tetramethyl-N ' -octylguanidine trifluoromethyl acetate ionic liquid prepared in example 1 was charged, and 86g of 3-methyl-2-buten-1-ol and 69g of formic acid (molar ratio 1: 1.5) were added, and 1.29g (1.5 wt%) of sodium hydrogen sulfite was further added as a catalyst, and then the three-necked flask was placed in a heating mantle with magnetic stirring to heat up (35 ℃ C.) and turn on the magnetic stirring to perform esterification reaction for 3 hours. After the reaction is finished, washing the reaction product to be neutral, detecting the product according to the prior art method (see the technical research on alpha-bisabolol synthesis by dipentene, imperial jade, and the like), and calculating the yield of the product 3-methyl-2-butene-1-alcohol formate to be 98%.
Example 9
In a 250mL three-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel, 100mL of the N, N, N ', N ' -tetramethyl-N ' -octylguanidine trifluoromethyl acetate ionic liquid prepared in example 1 was charged, and 86g of 3-methyl-2-buten-1-ol and 69g of formic acid (molar ratio 1: 1.5) were added, and 1.29g (1.5 wt%) of sodium hydrogen sulfite was further added as a catalyst, and then the three-necked flask was placed in a heating mantle with magnetic stirring to heat up (35 ℃ C.) and turn on the magnetic stirring to perform esterification for 4 hours. After the reaction is finished, washing the reaction product to be neutral, detecting the product according to the prior art method (see the technical research on alpha-bisabolol synthesis by dipentene, imperial jade, and the like), and calculating the yield of the product 3-methyl-2-butene-1-alcohol formate to be 98.1%.
Example 10
In a 250mL three-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel, 100mL of the N, N, N ', N ' -tetramethyl-N ' -octylguanidine trifluoromethyl acetate ionic liquid prepared in example 1 was charged, and 86g of 3-methyl-2-buten-1-ol and 69g of formic acid (molar ratio 1: 1.5) were added, and 1.29g (1.5 wt%) of sodium hydrogen sulfite was further added as a catalyst, and then the three-necked flask was placed in a heating mantle with magnetic stirring to heat up (35 ℃ C.) and turn on the magnetic stirring to perform esterification for 5 hours. After the reaction is finished, washing the reaction product to be neutral, detecting the product according to the prior art method (see the technical research on alpha-bisabolol synthesis by dipentene, imperial jade, and the like), and calculating the yield of the product 3-methyl-2-butene-1-alcohol formate to be 98.3%.
Example 11
In a 250mL three-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel, 100mL of the N, N, N ', N ' -tetramethyl-N ' -octylguanidine trifluoromethyl acetate ionic liquid prepared in example 1 was charged, and 86g of 3-methyl-2-buten-1-ol and 69g of formic acid (molar ratio 1: 1.5) were added, and 1.29g (1.5 wt%) of sodium hydrogen sulfite was further added as a catalyst, and then the three-necked flask was placed in a heating mantle with magnetic stirring to heat up (35 ℃ C.) and turn on the magnetic stirring to perform esterification for 6 hours. After the reaction is finished, washing the reaction product to be neutral, detecting the product according to the prior art method (see the technical research on alpha-bisabolol synthesis by dipentene, imperial jade, and the like), and calculating the yield of the product 3-methyl-2-butene-1-alcohol formate to be 98.5%.
Comparative example
In a 250mL three-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel, 86g of 3-methyl-2-buten-1-ol and 69g of formic acid (molar ratio: 1: 1.5) were charged, and then the three-necked flask was placed in a heating mantle equipped with magnetic stirring to heat the reaction and the magnetic stirring was turned on to conduct esterification for 6 hours. After the reaction is finished, washing the reaction product to be neutral, detecting the product according to the prior art method (see the technical research on alpha-bisabolol synthesis by dipentene, imperial jade, and the like), and calculating the yield of the product 3-methyl-2-butene-1-alcohol formate to be 92%.
Application example 1 Synthesis of alpha-bisabolol
The esterification reaction was carried out for 5 hours according to the procedure in example 4, after the esterification was completed, 409g of dipentene (dipentene: isopentenol molar ratio ═ 3: 1) and 540g of dichloromethane were added to the reaction system, 30g of catalyst (formic acid and phosphoric acid molar ratio 1: 2) was added dropwise at 75 ℃, the condensation reaction was stirred, and the product was monitored by GC tracing (see "research on process for synthesizing α -bisabolol from dipentene, danesen, etc.), and the yield of α -bisabolol was 70%.
Application example 2 Synthesis of alpha-bisabolol
The esterification reaction was carried out for 5 hours according to the procedure in example 6, after the esterification was completed, 409g of dipentene (dipentene: isopentenol molar ratio ═ 3: 1) and 540g of dichloromethane were added to the reaction system, 30g of catalyst (formic acid and phosphoric acid molar ratio 1: 2) was added dropwise at 75 ℃, the condensation reaction was stirred, and the product was monitored by GC tracing (see "research on process for synthesizing α -bisabolol from dipentene, danesen, etc.), and the yield of α -bisabolol was 81%.
Application example 3 Synthesis of alpha-bisabolol
The esterification reaction was carried out for 5 hours according to the procedure in example 8, after the esterification was completed, 409g of dipentene (dipentene: isopentenol molar ratio ═ 3: 1) and 540g of dichloromethane were added to the reaction system, 30g of catalyst (formic acid and phosphoric acid molar ratio 1: 2) was added dropwise at 75 ℃, the condensation reaction was stirred, and the product was monitored by GC tracing (see "research on process for synthesizing α -bisabolol from dipentene, danesen, etc.), and the yield of α -bisabolol was 83%.
Comparative application example
The esterification reaction is carried out for 6h according to the steps in the comparative example 1, after the esterification is finished, 409g of dipentene (the molar ratio of the dipentene to the isopentenol is 3: 1) and 540g of dichloromethane are added into the reaction system, 30g of catalyst (the molar ratio of formic acid to phosphoric acid is 1: 2) is added dropwise at 75 ℃, the condensation reaction is stirred, products are monitored by GC (see the method for details in research on the synthesis of alpha-bisabolol from dipentene, Dangqian, and the like), and the final yield of the alpha-bisabolol is 68%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (2)
1. A synthetic method of 3-methyl-2-butene-1-alcohol formate is characterized by comprising the steps of uniformly mixing 3-methyl-2-butene-1-alcohol with formic acid, adding sodium bisulfite as a catalyst, and carrying out esterification reaction for 1-6h at 30-40 ℃ in the presence of an N, N, N ', N ' -tetramethyl-N ' -octylguanidine trifluoromethyl acetate ionic liquid solvent;
the molar ratio of the 3-methyl-2-butene-1-ol to the formic acid is 1: 1.3-1.6;
the addition amount of the sodium bisulfite is 0.5-2 wt% of the raw material amount of the 3-methyl-2-butene-1-ol.
2. A method for producing α -bisabolol, comprising the step of synthesizing 3-methyl-2-buten-1-ol formate according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711487459.9A CN108129301B (en) | 2017-12-30 | 2017-12-30 | Synthetic method of 3-methyl-2-butene-1-alcohol formate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711487459.9A CN108129301B (en) | 2017-12-30 | 2017-12-30 | Synthetic method of 3-methyl-2-butene-1-alcohol formate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108129301A CN108129301A (en) | 2018-06-08 |
| CN108129301B true CN108129301B (en) | 2021-03-02 |
Family
ID=62394174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711487459.9A Active CN108129301B (en) | 2017-12-30 | 2017-12-30 | Synthetic method of 3-methyl-2-butene-1-alcohol formate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108129301B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049332A (en) * | 1989-08-08 | 1991-02-20 | 纳贝斯高·布兰股伦有限公司 | The preparation method of neoalkyl triol triesters |
| CN101434639A (en) * | 2008-12-17 | 2009-05-20 | 中国农业科学院油料作物研究所 | Green technological process for preparing sterol fatty acid ester |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831322A (en) * | 2017-01-10 | 2017-06-13 | 南宁辰康生物科技有限公司 | A kind of production method of α bisabolols |
-
2017
- 2017-12-30 CN CN201711487459.9A patent/CN108129301B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049332A (en) * | 1989-08-08 | 1991-02-20 | 纳贝斯高·布兰股伦有限公司 | The preparation method of neoalkyl triol triesters |
| CN101434639A (en) * | 2008-12-17 | 2009-05-20 | 中国农业科学院油料作物研究所 | Green technological process for preparing sterol fatty acid ester |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108129301A (en) | 2018-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2024419C (en) | Novel bivalent metal salts of n,n-di(carboxymethyl)-2-amino-3-cyano-4-carboxymethyl-5-carboxythiophene acid, process for their preparation and pharmaceutical compositions containing them | |
| KR950008082B1 (en) | Cosmetic composition | |
| KR101904127B1 (en) | Novel carboxylic acid ester compound and method for producing same, and fragrance composition | |
| WO1998021176A1 (en) | Novel pseudoceramides, and dermatologic external preparations containing the same | |
| CN112250572B (en) | Method for synthesizing bornyl acetate from turpentine | |
| JP2021517182A (en) | Polyester derivatives, use and method of manufacture thereof | |
| JP6450753B2 (en) | Novel compound and perfume composition containing the compound | |
| CN108129301B (en) | Synthetic method of 3-methyl-2-butene-1-alcohol formate | |
| JPS5976031A (en) | 2,4-dialkylheptanol derivatives | |
| CN101798260B (en) | Method for applying catalyst to synthesize lyral by myrac aldehyde | |
| CN106831322A (en) | A kind of production method of α bisabolols | |
| KR101841910B1 (en) | Novel carboxylate compound and method of producing the same and perfume composition thereof | |
| KR102634263B1 (en) | Novel hydroxy pyranone derivative, preparation method thereof, and cosmetic composition comprising the same | |
| CN107879932B (en) | Synthesis method of o-tert-butylcyclohexyl acetate perfume | |
| CN112645815A (en) | Preparation method for catalytically synthesizing methyl cinnamate based on eutectic solvent | |
| CN107793379A (en) | A kind of Chinese cassia tree acetal diglycidyl ether and preparation method thereof and purposes | |
| JP6606343B2 (en) | Gel-like antiperspirant composition | |
| JP2551471B2 (en) | Glyceryl ether derivative and skin external preparation containing the same | |
| KR102463238B1 (en) | Novel hydroxy pyranone derivative, preparation method thereof, and cosmetic composition comprising the same | |
| CN107698450B (en) | Synthetic method of irisone spice | |
| JPS605582B2 (en) | Process for producing novel alicyclic ketoesters and related compounds | |
| CN115041227B (en) | Metal carboxylic acid based ionic liquid catalyst and preparation method and application thereof | |
| DE3720791C2 (en) | ||
| JP2024059650A (en) | Polyether derivatives, uses and methods for their preparation | |
| RU2624220C1 (en) | Method for acetyling hydroxyarriles with vinylacetate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20180608 Assignee: GUANGXI NANNING LVJING FUNCTIONAL POLYMER MATERIALS Co.,Ltd. Assignor: GUANGXI ZHUANG AUTONOMOUS REGION FORESTRY Research Institute Contract record no.: X2022450000395 Denomination of invention: Synthesis of 3-methyl-2-butene-1-alkoxylate Granted publication date: 20210302 License type: Common License Record date: 20221226 |
|
| EE01 | Entry into force of recordation of patent licensing contract |