CN102531858B - Preparation method of lyral - Google Patents
Preparation method of lyral Download PDFInfo
- Publication number
- CN102531858B CN102531858B CN201010592887.XA CN201010592887A CN102531858B CN 102531858 B CN102531858 B CN 102531858B CN 201010592887 A CN201010592887 A CN 201010592887A CN 102531858 B CN102531858 B CN 102531858B
- Authority
- CN
- China
- Prior art keywords
- lyral
- myrcenol
- propenal
- reaction
- preparation
- 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
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of lyral. The method comprises the following steps of: a) heating myrcenol to 50-130 DEG C; and b) dropwise adding acrolein in the myrcenol obtained in the step a), controlling the temperature to 50-130 DEG C in the dropwise adding process, and continuously reacting after dropwise adding to obtain lyral. By controlling the addition mode and addition temperature of acrolein, myrcenol and acrolein can perform a Diels-Alder reaction without adopting high temperature and high pressure or an Lewis acid catalyst and an organic solvent, the reaction conditions are mild and by-products are fewer. As high temperature and high pressure are not required, the requirements on the reaction equipment are low and the cost of lyral can be increased; and as the Lewis acid catalyst is not required, the complicated post-treatment processes are omitted and a lot of waste acid can not be generated to corrode the equipment and pollute the environment.
Description
Technical field
The invention belongs to biomass processing technical field, relate in particular to a kind of preparation method of LYRAL.
Background technology
LYRAL, English name is Lyral, chemical name be to ()-(4-hydroxy-4-methyl amyl group)-3-cyclohexene-1-formaldehyde, molecular formula is C
12h
22o
2, molecular weight is 210.32, structural formula is suc as formula shown in (I) or formula (II).LYRAL is a kind of colorless viscous liquid, has light, the sweet root of Common Pecteilis fragrance of a flower, has good lily of the valley note, and fragrance is stable and lasting, can be used as the essence of the daily chemical products such as preparation perfume, perfumed soap, washing composition, makeup.
Myrcenol is a kind of compound preparing based on renewable resources; its typical production is as follows: turps separation obtains beta-pinene; after beta-pinene cracking, obtain myrcene; myrcene is converted into myrcene sulfone under the protection of sulfurous gas; after myrcene sulfone and sulfuric acid hydration, reheat and slough sulfurous gas, can obtain myrcenol.The output of myrcenol is not subject to the impact of petroleum resources, and it has formula (III) structure, can with the propenal generation LYRAL that reacts, therefore, be the main raw material of preparation LYRAL.
American documentation literature US4007137 discloses a kind of method that pressure sintering is prepared LYRAL, mainly comprises the following steps: myrcenol, propenal and Resorcinol are joined in enclosed high pressure still, at 150 ℃, react 4.5h, obtain LYRAL.Because myrcenol and propenal are very exothermic reaction, can make reaction system steep temperature rise cause propenal volatilization, so reaction needed carry out under high pressure, air tight condition, not only conversion unit is had relatively high expectations, and increased the cost of LYRAL.The document also discloses that a kind of Louis acid catalysis legal system is for the method for LYRAL, mainly comprise the following steps: after myrcenol, lewis acid catalyst and organic solvent are mixed, heat up, then add propenal, after reaction 1h~10h, obtain LYRAL, wherein, lewis acid catalyst is generally zinc chloride, zinc bromide, tin tetrachloride etc., and organic solvent is generally toluene.Although Louis acid catalysis method can reduce temperature of reaction, need to carry out aftertreatment to reaction product, as removed catalyzer, removing organic solvent etc., complex operation step not only, and can produce a large amount of spent acid etching apparatuses, contaminate environment.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of LYRAL, and method reaction conditions provided by the invention is gentle, by product is less, and without complicated last handling process.
The preparation method who the invention provides a kind of LYRAL, comprises the following steps:
A) myrcenol is warming up to 50 ℃~130 ℃;
B) in myrcenol a) obtaining to step, drip propenal, in dropping process, controlling temperature is 50 ℃~130 ℃, dropwises rear continuation reaction, obtains LYRAL.
Preferably, described step b) in, the time for adding of described propenal is 6h~10h.
Preferably, described step b) in, the temperature of described reaction is 50 ℃~130 ℃.
Preferably, described step b) in, described in dropwise rear continuation reaction time be 1h~2h.
Preferably, the mol ratio of described propenal and described myrcenol is 1.1~1.5: 1.
Preferably, described step b) specifically comprise the following steps:
B1) in myrcenol a) obtaining to step, drip propenal;
B2) by step b1) reaction mixture that obtains washs in deionized water, obtains LYRAL crude product;
B3) described LYRAL crude product is carried out to high vacuum rectification, obtain LYRAL.
Preferably, described step b3) in, the vacuum tightness while carrying out high vacuum rectification is below 2mm mercury column.
Preferably, described step b), in, in described propenal, contain the stopper of 0.1wt%~0.3wt%.
Preferably, described step a) in, in described myrcenol, contain the stopper of 0.1wt%~0.3wt%.
Preferably, described stopper is Resorcinol, 2,6 ditertiary butyl p cresol, 4,4-methylene-bis (2,6 di t butyl phenol) or N-phenyl-2-naphthylamine.
Compared with prior art, first the present invention is warming up to myrcenol 50 ℃~130 ℃, then drips wherein propenal, and in dropping process, controlling temperature is 50 ℃~130 ℃, dropwises rear continuation reaction, obtains LYRAL.First the present invention is warming up to myrcenol 50 ℃~130 ℃, then in dropping mode, adds propenal, makes myrcenol and propenal continue to react, slowly heat release; In dripping the process of propenal, it is 50 ℃~130 ℃ that temperature is controlled all the time, avoids exothermic heat of reaction to cause temperature of reaction system to rise, thereby avoid propenal volatilization, after dropwising, continue reaction and making reaction more complete, can obtain all higher LYRAL of yield and purity.The present invention, by controlling adding mode and adding temperature of propenal, makes myrcenol and propenal without there is Diels-Alder reaction in High Temperature High Pressure or under the condition of lewis acid catalyst and organic solvent, and reaction conditions is gentle, and by product is less.Due to without High Temperature High Pressure, therefore conversion unit is required lowlyer, can not increase the cost of LYRAL; Due to without adding lewis acid catalyst, save loaded down with trivial details postprocessing working procedures, can not produce a large amount of spent acid etching apparatuses, contaminate environment yet.
Accompanying drawing explanation
The gas chromatogram of the LYRAL that Fig. 1 provides for the embodiment of the present invention;
Fig. 2 is the gas chromatogram of the LYRAL standard model of American I FF company.
Embodiment
The preparation method who the invention provides a kind of LYRAL, comprises the following steps:
A) myrcenol is warming up to 50 ℃~130 ℃;
B) in myrcenol a) obtaining to step, drip propenal, in dropping process, controlling temperature is 50 ℃~130 ℃, dropwises rear continuation reaction, obtains LYRAL.
First the present invention is warming up to myrcenol 50 ℃~130 ℃, be warming up to the temperature of reaction of myrcenol and propenal, the propenal of follow-up dropping can be reacted with myrcenol immediately, and described temperature is preferably 70 ℃~120 ℃, more preferably 100 ℃~110 ℃.
Myrcenol is the diene body with conjugated double bond, easily produce self-polymeric reaction, in order to prevent myrcenol generation self-polymeric reaction, described myrcenol preferably contains stopper, described stopper is preferably Resorcinol, 2,6 ditertiary butyl p cresol, 4,4-methylene-bis (2,6-DI-tert-butylphenol compounds) or N-phenyl-2-naphthylamine, more preferably Resorcinol.The quality optimization of described stopper is 0.1%~0.3% of described myrcenol quality, more preferably 0.15%~0.25%.
In the myrcenol after heating up, drip propenal, in dropping process, controlling temperature is 50 ℃~130 ℃, is preferably 70 ℃~120 ℃, more preferably 100 ℃~110 ℃.Owing in advance myrcenol being warming up to 50 ℃~130 ℃, therefore drip after propenal, propenal can react with myrcenol immediately, continues to drip propenal, and propenal can continue to react with myrcenol.In the process that propenal and myrcenol continue to react, also can sustained release reaction heat, the present invention is by controlling the temperature of reaction system in dropping process, and the reaction heat of having avoided reaction to discharge causes system steep temperature rise.The present invention is preferably placed in reaction system freezing tank and realizes the object of controlling temperature.
Because myrcenol and reacting of propenal are very exothermic reaction, only have dropping propenal, make propenal and myrcenol sustained reaction can control the temperature of reaction system, avoid reaction system steep temperature rise; If myrcenol is directly mixed with propenal, moment reacts, and during a large amount of reaction heat of abrupt release, is difficult to control reaction system and remains on 50 ℃~130 ℃.
In the process dripping, there is Diels-Alder with myrcenol and react in propenal, obtains LYRAL, and reaction formula is as follows:
Propenal is dienophile, easily there is self-polymeric reaction, for fear of propenal generation self-polymeric reaction, in described propenal, contain stopper, described stopper is preferably Resorcinol, 2,6 ditertiary butyl p cresol, 4,4-methylene-bis (2,6-DI-tert-butylphenol compounds) or N-phenyl-2-naphthylamine, more preferably Resorcinol.The quality optimization of described stopper is 0.1%~0.3% of described propenal quality, more preferably 0.15%~0.25%.
For the temperature of reaction system is more easily controlled, the time for adding of described propenal is preferably 6h~10h, more preferably 8h~9h.Time for adding is longer, and propenal and myrcenol exothermic heat of reaction are comparatively slow, and the temperature of reaction system is more prone to control, thereby the productive rate of the LYRAL obtaining and purity are higher.
After propenal dropwises, propenal and myrcenol continue reaction makes reaction more abundant, obtains LYRAL.Temperature while continuing reaction is preferably 50 ℃~130 ℃, more preferably 70 ℃~120 ℃, most preferably is 100 ℃~110 ℃; Time is preferably 1h~2h.
In whole reaction, the mol ratio of described propenal and described myrcenol is preferably 1.1~1.5: 1, more preferably 1.1~1.2: 1.
After completion of the reaction, after reaction mixture being washed with deionized water, can obtain LYRAL crude product.The waste water producing in washing process can obtain propenal and water after distillation is processed, and propenal can be used as raw material to be continued to use, and water can be again for washing reaction mixture.
Described LYRAL crude product is carried out to molecular distillation, can obtain the LYRAL that purity is higher.While carrying out molecular distillation, described vacuum tightness is preferably below 2mm mercury column, and after molecular distillation, the cut between collecting 120 ℃~125 ℃, is LYRAL.
Described LYRAL is carried out to gas chromatographic analysis, there is essentially identical gas chromatogram with the LYRAL standard model of American I FF company, therefore, by preparation method provided by the invention, can access LYRAL.From gas chromatogram, the LYRAL purity obtaining by preparation method provided by the invention is more than 99%.
The present invention, by controlling adding mode and adding temperature of propenal, makes myrcenol and propenal without there is Diels-Alder reaction in High Temperature High Pressure or under the condition of lewis acid catalyst and organic solvent, and reaction conditions is gentle, and by product is less.Due to without High Temperature High Pressure, therefore conversion unit is required lowlyer, can not increase the cost of LYRAL; Due to without adding lewis acid catalyst, save loaded down with trivial details postprocessing working procedures, can not produce a large amount of spent acid etching apparatuses, contaminate environment yet.
In order to further illustrate the present invention, below in conjunction with embodiment, the preparation method of LYRAL provided by the invention is described in detail.
Embodiment 1
To being equipped with in the 1000mL four-hole boiling flask of thermometer, mechanical stirring device and reflux exchanger, add 539g (3.5mol) myrcenol and 0.539g Resorcinol, be heated to 110 ℃; In described myrcenol, drip 235g (4.2mol) propenal, drip 6h, in dropping process, described reaction flask is placed in to freezing tank, keep reaction flask temperature at 110 ℃~130 ℃; After propenal dropwises, continue reaction 1h, obtain reaction mixture;
By 200g deionized water wash three times of described reaction mixture, obtain 770g LYRAL crude product, described LYRAL is carried out to gas chromatographic analysis, wherein the content of LYRAL is 96.6%; Described crude product is carried out below vacuum tightness 2mmHg to rectifying, the cut between collecting 120 ℃~125 ℃, obtains 616g LYRAL.
Described LYRAL is carried out to gas chromatographic analysis, and result is referring to Fig. 1 and Fig. 2, the gas chromatogram of the LYRAL that Fig. 1 provides for the embodiment of the present invention, and Fig. 2 is the gas chromatogram of the LYRAL standard model of American I FF company.
In Fig. 2, two peaks that 10.924min and 11.123min occur are respectively the peak of m-(4-hydroxy-4-methyl amyl group)-3-cyclohexene-1-formaldehyde and p-(4-hydroxy-4-methyl amyl group)-3-cyclohexene-1-formaldehyde, and its total content is 97.76%; And in Fig. 1, two main peaks during respectively at 10.991min and 11.190min, have been there are, these two main peaks are the peak of m-(4-hydroxy-4-methyl amyl group)-3-cyclohexene-1-formaldehyde and p-(4-hydroxy-4-methyl amyl group)-3-cyclohexene-1-formaldehyde, and its total content is 99.26%.
From Fig. 1 and Fig. 2, by method provided by the invention, prepared LYRAL, and the purity of the LYRAL obtaining is higher.
Embodiment 2
To being equipped with in the 1000mL four-hole boiling flask of thermometer, mechanical stirring device and reflux exchanger, add 539g (3.5mol) myrcenol and 0.539g Resorcinol, be heated to 110 ℃; In described myrcenol, drip 216g (3.86mol) propenal, drip 6h, in dropping process, described reaction flask is placed in to freezing tank, keep reaction flask temperature at 110 ℃~130 ℃; After propenal dropwises, continue reaction 1h, obtain reaction mixture;
By 180g deionized water wash three times of described reaction mixture, obtain 761g LYRAL crude product, described LYRAL is carried out to gas chromatographic analysis, wherein the content of LYRAL is 95.2%; Described crude product is carried out below vacuum tightness 2mmHg to rectifying, the cut between collecting 120 ℃~125 ℃, obtains 605g LYRAL.
Described LYRAL is carried out to gas chromatographic analysis, and when its main peak comes across 10.990min and 11.191min, total content is 99.30%.
Embodiment 3
To being equipped with in the 1000mL four-hole boiling flask of thermometer, mechanical stirring device and reflux exchanger, add 539g (3.5mol) myrcenol and 0.539g Resorcinol, be heated to 110 ℃; In described myrcenol, drip 196g (3.5mol) propenal, drip 6h, in dropping process, described reaction flask is placed in to freezing tank, keep reaction flask temperature at 110 ℃~130 ℃; After propenal dropwises, continue reaction 1h, obtain reaction mixture;
By 180g deionized water wash three times of described reaction mixture, obtain 755g LYRAL crude product, described LYRAL is carried out to gas chromatographic analysis, wherein the content of LYRAL is 87.4%; Described crude product is carried out below vacuum tightness 2mmHg to rectifying, the cut between collecting 120 ℃~125 ℃, obtains 516g LYRAL.
Described LYRAL is carried out to gas chromatographic analysis, and when its main peak comes across 10.991min and 11.190min, total content is 99.25%.
Embodiment 4
To being equipped with in the 1000mL four-hole boiling flask of thermometer, mechanical stirring device and reflux exchanger, add 539g (3.5mol) myrcenol and 0.539g Resorcinol, be heated to 60 ℃; In described myrcenol, drip 235g (4.2mol) propenal, drip 7h, in dropping process, described reaction flask is placed in to freezing tank, keep reaction flask temperature at 60 ℃~70 ℃; After propenal dropwises, continue reaction 1h, obtain reaction mixture;
By 200g deionized water wash three times of described reaction mixture, obtain 771g LYRAL crude product, described LYRAL is carried out to gas chromatographic analysis, wherein the content of LYRAL is 93.1%; Described crude product is carried out below vacuum tightness 2mmHg to rectifying, the cut between collecting 120 ℃~125 ℃, obtains 612g LYRAL.
Described LYRAL is carried out to gas chromatographic analysis, and when its main peak comes across 10.991min and 11.190min, total content is 99.23%.
Embodiment 5
To being equipped with in the 1000mL four-hole boiling flask of thermometer, mechanical stirring device and reflux exchanger, add 539g (3.5mol) myrcenol and 0.539g Resorcinol, be heated to 60 ℃; In described myrcenol, drip 216g (3.86mol) propenal, drip 7h, in dropping process, described reaction flask is placed in to freezing tank, keep reaction flask temperature at 60 ℃~70 ℃; After propenal dropwises, continue reaction 1h, obtain reaction mixture;
By 180g deionized water wash three times of described reaction mixture, obtain 763g LYRAL crude product, described LYRAL is carried out to gas chromatographic analysis, wherein the content of LYRAL is 92.0%; Described crude product is carried out below vacuum tightness 2mmHg to rectifying, the cut between collecting 120 ℃~125 ℃, obtains 603g LYRAL.
Described LYRAL is carried out to gas chromatographic analysis, and when its main peak comes across 10.991min and 11.190min, total content is 99.31%.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. a preparation method for LYRAL, comprises the following steps:
A) myrcenol is warming up to 50 ℃~130 ℃; The stopper that contains 0.1wt%~0.3wt% in described myrcenol;
B) in the myrcenol obtaining to step a), drip propenal, in dropping process, controlling temperature is 50 ℃~130 ℃, dropwises rear continuation reaction, obtains LYRAL.
2. preparation method according to claim 1, is characterized in that, in described step b), the time for adding of described propenal is 6h~10h.
3. preparation method according to claim 1, is characterized in that, in described step b), the temperature of described reaction is 50 ℃~130 ℃.
4. preparation method according to claim 1, is characterized in that, in described step b), described in dropwise rear continuation reaction time be 1h~2h.
5. preparation method according to claim 1, is characterized in that, the mol ratio of described propenal and described myrcenol is 1.1~1.5:1.
6. preparation method according to claim 1, is characterized in that, described step b) specifically comprises the following steps:
B1) in the myrcenol obtaining to step a), drip propenal;
B2) by step b1) reaction mixture that obtains washs in deionized water, obtains LYRAL crude product;
B3) by described LYRAL crude product, in vacuum tightness, be below 2mm mercury column, to carry out rectifying, obtain LYRAL.
7. preparation method according to claim 1, is characterized in that, in described step b), contains the stopper of 0.1wt%~0.3wt% in described propenal.
8. according to the preparation method described in claim 1 or 7, it is characterized in that, described stopper is Resorcinol, 2,6 ditertiary butyl p cresol, 4,4-methylene-bis (2,6 di t butyl phenol) or N-phenyl-2-naphthylamine.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201010592887.XA CN102531858B (en) | 2010-12-16 | 2010-12-16 | Preparation method of lyral |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201010592887.XA CN102531858B (en) | 2010-12-16 | 2010-12-16 | Preparation method of lyral |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102531858A CN102531858A (en) | 2012-07-04 |
CN102531858B true CN102531858B (en) | 2014-04-16 |
Family
ID=46340047
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201010592887.XA Active CN102531858B (en) | 2010-12-16 | 2010-12-16 | Preparation method of lyral |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102531858B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109734568A (en) * | 2019-01-22 | 2019-05-10 | 武汉格源精细化学有限公司 | The preparation method of lyral |
CN110183319B (en) * | 2019-06-14 | 2021-11-09 | 江西省药品检验检测研究院 | Method for preparing lyral for cosmetic detection |
CN110187033B (en) * | 2019-06-14 | 2021-09-17 | 江西省药品检验检测研究院 | Preparation method of lyral and application of lyral in cosmetic detection |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2947780A (en) * | 1960-01-15 | 1960-08-02 | Int Flavors & Fragrances Inc | Cyclohexene and hexadiene carboxyaldehydes and derivatives thereof |
US3433839A (en) * | 1966-05-12 | 1969-03-18 | Takasago Perfumery Co Ltd | Process for the production of a mixture of alicyclic hydroxyaldehydes |
US3758590A (en) * | 1969-11-24 | 1973-09-11 | Scm Corp | Hydrolyzed diels-alder adducts of ocimenol |
US4007137A (en) * | 1975-10-07 | 1977-02-08 | International Flavors & Fragrances Inc. | Process for producing mixture containing 4-(4-methyl-4-hydroxyamyl)Δ3 -cyclohexenecarboxaldehyde, product produced, and its perfume uses |
US4266087A (en) * | 1978-11-13 | 1981-05-05 | Givaudan Corporation | Process for preparing a myrcenol, cis-ocimenol mixture substantially free of trans-ocimenol |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62141097A (en) * | 1985-12-13 | 1987-06-24 | 花王株式会社 | Purification of perfume base material |
-
2010
- 2010-12-16 CN CN201010592887.XA patent/CN102531858B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2947780A (en) * | 1960-01-15 | 1960-08-02 | Int Flavors & Fragrances Inc | Cyclohexene and hexadiene carboxyaldehydes and derivatives thereof |
US3433839A (en) * | 1966-05-12 | 1969-03-18 | Takasago Perfumery Co Ltd | Process for the production of a mixture of alicyclic hydroxyaldehydes |
US3758590A (en) * | 1969-11-24 | 1973-09-11 | Scm Corp | Hydrolyzed diels-alder adducts of ocimenol |
US4007137A (en) * | 1975-10-07 | 1977-02-08 | International Flavors & Fragrances Inc. | Process for producing mixture containing 4-(4-methyl-4-hydroxyamyl)Δ3 -cyclohexenecarboxaldehyde, product produced, and its perfume uses |
US4266087A (en) * | 1978-11-13 | 1981-05-05 | Givaudan Corporation | Process for preparing a myrcenol, cis-ocimenol mixture substantially free of trans-ocimenol |
Non-Patent Citations (5)
Title |
---|
JP特开昭62-141097A 1987.06.24 |
从月桂烯出发合成新铃兰醛;林晓等;《广州化学》;20020930;第27卷(第3期);42-48 * |
张国安.新铃兰醛香料的合成.《陕西化工》.1989,(第6期),21-23. |
新铃兰醛香料的合成;张国安;《陕西化工》;19891231(第6期);21-23 * |
林晓等.从月桂烯出发合成新铃兰醛.《广州化学》.2002,第27卷(第3期),42-48. |
Also Published As
Publication number | Publication date |
---|---|
CN102531858A (en) | 2012-07-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102531858B (en) | Preparation method of lyral | |
CN107056596B (en) | Preparation method of 2,6,11, 15-tetramethyl-2, 4,6,8,10,12, 14-hexadecaheptadien dialdehyde | |
CN102304024B (en) | Method for synthesizing difluoroethanol | |
CN104592030A (en) | Method for synthesizing phthalate compounds | |
CN101423475B (en) | Preparation method of 3-ethoxyl ethyl propionate | |
CN105503582A (en) | Continuous production method for trifluoro monochloro chrysanthemic acid | |
KR101679717B1 (en) | A Method for Preparation of Allyl alcohol and the Allyl alcohol Prepared by the Same | |
JP2012513983A (en) | Method for producing dichloropropanol using glycerol with improved selectivity for dichloropropanol | |
CN102167657B (en) | Hdrogenation synthesis method for preparing 2-methyl allyl alcohol by using recyclable catalyst | |
CN107986962B (en) | Method for recovering acetoacetates from acetoacetates distillation residues | |
JP7438391B2 (en) | How to synthesize oxetane compounds by microreactor | |
CN102040486A (en) | Preparation method of trimethylolpropane diallyl ether | |
CN106632161A (en) | Method used for preparing gamma-valerolactone via high-selectivity catalysis | |
CN108129352A (en) | A kind of preparation method of 3- allyloxys propionitrile | |
CN101774957B (en) | Process for synthesizing beta-carotene | |
CN103304536B (en) | Method for preparing high-content helional | |
CN209537352U (en) | Hexafluoropropylene dimmer prepares the device of perfluor isobutyl ether | |
CN103342688B (en) | Method for preparing furfural by one-step selective catalytic cracking | |
CN104271559A (en) | Method for producing alkanediol monoglycidyl ether (meth)acrylate | |
CN101182329B (en) | Method for hydrolyzing methyl phenyl siloxane | |
CN104059094B (en) | The dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane | |
CN106146302B (en) | The preparation method of propionic ester | |
CN101265186A (en) | Method for synthesizing allyl phenoxyacetate by ionic liquid | |
CN209537353U (en) | Hexafluoropropylene dimmer cracking prepares the device of perfluoropentyl ether | |
CN107892645A (en) | A kind of method of the high efficiency synthesis propane diols of 2 phenyl 1,3 |
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 | ||
C56 | Change in the name or address of the patentee |
Owner name: GLEE BIOTECHNOLOGY CO., LTD. Free format text: FORMER NAME: GELIN PERFUME CHEMISTRY CO LTD, HANGZHOU |
|
CP03 | Change of name, title or address |
Address after: 311600, Zhejiang City, Jiande Province town of plum peak - South Peak High-tech Industrial Park Patentee after: Green Biotechnology Co.,Ltd. Address before: 311600 No. 98 Xiang Xiang Road, Yangxi street, Jiande, Zhejiang Patentee before: Gelin Perfume Chemistry Co., Ltd., Hangzhou |