CN102531858A - Preparation method of lyral - Google Patents
Preparation method of lyral Download PDFInfo
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- CN102531858A CN102531858A CN201010592887XA CN201010592887A CN102531858A CN 102531858 A CN102531858 A CN 102531858A CN 201010592887X A CN201010592887X A CN 201010592887XA CN 201010592887 A CN201010592887 A CN 201010592887A CN 102531858 A CN102531858 A CN 102531858A
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- lyral
- myrcenol
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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 the biomass processing technical field, relate in particular to a kind of preparation method of LYRAL.
Background technology
LYRAL, English name are Lyral, chemical name be to ()-(4-hydroxy-4-methyl amyl group)-3-tetrahydrobenzene-1-formaldehyde, molecular formula is C
12H
22O
2, molecular weight is 210.32, structural formula is suc as formula shown in (I) or the formula (II).LYRAL is a kind of colorless viscous liquid, has light, the sweet root of Common Pecteilis fragrance of a flower, and lily of the valley note is preferably arranged, and fragrance is stable and lasting, can be used as the essence of daily chemical products such as preparation perfume, perfumed soap, washing composition, makeup.
Myrcenol is a kind of compound for preparing based on renewable resources; Its typical production is following: the turps separation obtains beta-pinene; Obtain myrcene after the beta-pinene cracking; Myrcene is converted into the myrcene sulfone under the protection of sulfurous gas, reheat is sloughed sulfurous gas after myrcene sulfone and the sulfuric acid hydration, can obtain myrcenol.The output of myrcenol does not receive the influence 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 the method that a kind of pressure sintering prepares LYRAL, mainly may further comprise the steps: myrcenol, propenal and Resorcinol are joined in the airtight autoclave, react 4.5h down at 150 ℃, obtain LYRAL.Because myrcenol and propenal are the very exothermic reaction, reaction system is sharply heated up cause propenal to volatilize, so reaction needed carries 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 equipped with the method for LYRAL; Mainly may further comprise the steps: myrcenol, lewis acid catalyst and organic solvent are mixed the back heat up; Add propenal then, obtain LYRAL behind reaction 1h～10h, wherein; Lewis acid catalyst is generally zinc chloride, zinc bromide, tin tetrachloride etc., and organic solvent is generally toluene.Though the Louis acid catalysis method can reduce temperature of reaction, need carry out aftertreatment to reaction product, as removing 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 that the present invention will solve 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 need not complicated last handling process.
The invention provides a kind of preparation method of LYRAL, may further comprise the steps:
A) myrcenol is warming up to 50 ℃～130 ℃;
B) in the myrcenol that step a) obtains, drip propenal, controlled temperature is 50 ℃～130 ℃ in the dropping process, dropwises the continued reaction, obtains LYRAL.
Preferably, in the said step b), the dropping time of said propenal is 6h～10h.
Preferably, in the said step b), the temperature of said reaction is 50 ℃～130 ℃.
Preferably, in the said step b), the said time that dropwises the continued reaction is 1h～2h.
Preferably, the mol ratio of said propenal and said myrcenol is 1.1～1.5: 1.
Preferably, said step b) specifically may further comprise the steps:
B1) in the myrcenol that step a) obtains, drip propenal;
B2) with step b1) reaction mixture that obtains washs in deionized water, obtains the LYRAL bullion;
B3) said LYRAL bullion is carried out high vacuum rectification, obtain LYRAL.
Preferably, said step b3) in, the vacuum tightness when carrying out high vacuum rectification is below the 2mm mercury column.
Preferably, in the said step b), contain the stopper of 0.1wt%～0.3wt% in the said propenal.
Preferably, in the said step a), contain the stopper of 0.1wt%～0.3wt% in the said myrcenol.
Preferably, said stopper is Resorcinol, DBPC 2,6 ditertiary butyl p cresol, 4,4-methylene-bis (2,6 di t butyl phenol) or N-phenyl-2-naphthylamines.
Compared with prior art, the present invention at first is warming up to 50 ℃～130 ℃ with myrcenol, and to wherein dripping propenal, controlled temperature is 50 ℃～130 ℃ in the dropping process then, dropwises the continued reaction, obtains LYRAL.The present invention at first is warming up to 50 ℃～130 ℃ with myrcenol, adds propenal with the dropping mode then, makes myrcenol and propenal continue to react, slowly heat release; In the process that drips propenal, temperature is controlled to be 50 ℃～130 ℃ all the time, avoid exothermic heat of reaction to cause temperature of reaction system to rise; Thereby avoid the propenal volatilization; After dropwising, continue reaction and make reaction more complete, can obtain all higher LYRAL of yield and purity.The present invention makes myrcenol and propenal need not at HTHP or under the condition of lewis acid catalyst and organic solvent the Diels-Alder reaction to take place through the adding mode and adding temperature of control propenal, and reaction conditions is gentle, and by product is less.Owing to need not HTHP, therefore conversion unit is required lowlyer, can not increase the cost of LYRAL; Owing to need not to add 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.
Description of drawings
The gas chromatogram of the LYRAL that Fig. 1 provides for the embodiment of the invention;
Fig. 2 is the gas chromatogram of the LYRAL standard model of American I FF company.
Embodiment
The invention provides a kind of preparation method of LYRAL, may further comprise the steps:
A) myrcenol is warming up to 50 ℃～130 ℃;
B) in the myrcenol that step a) obtains, drip propenal, controlled temperature is 50 ℃～130 ℃ in the dropping process, dropwises the continued reaction, obtains LYRAL.
The present invention at first is warming up to 50 ℃～130 ℃ with myrcenol; Promptly 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 said temperature is preferably 70 ℃～120 ℃, more preferably 100 ℃～110 ℃.
Myrcenol is the diene body with conjugated double bond, is easy to generate self-polymeric reaction, in order to prevent myrcenol generation self-polymeric reaction; Said myrcenol preferably contains stopper; Said stopper is preferably Resorcinol, DBPC 2,6 ditertiary butyl p cresol, 4,4-methylene-bis (2; The 6-DI-tert-butylphenol compounds) or N-phenyl-2-naphthylamines, more preferably Resorcinol.The quality optimization of said stopper is 0.1%～0.3% of a said myrcenol quality, more preferably 0.15%～0.25%.
Drip propenal in the myrcenol after heating up, controlled temperature is 50 ℃～130 ℃ in the dropping process, is preferably 70 ℃～120 ℃, more preferably 100 ℃～110 ℃.Owing in advance myrcenol is warming up to 50 ℃～130 ℃, so after dripping propenal, propenal can react with myrcenol immediately, continue to drip propenal, propenal promptly can continue to react with myrcenol.In the process that propenal and myrcenol continue to react, also can continue release reaction heat, the present invention is through the temperature of reaction system in the control dropping process, and the reaction heat of having avoided reaction to discharge causes system sharply to heat up.The present invention preferably places freezing tank to realize the purpose of controlled temperature reaction system.
Because the reaction of myrcenol and propenal is the very exothermic reaction, has only the dropping propenal, makes propenal and myrcenol sustained reaction can control the temperature of reaction system, avoids reaction system sharply to heat up; If myrcenol is directly mixed with propenal, moment reacts, and during a large amount of reaction heat of abrupt release, is difficult to the control reaction system and remains on 50 ℃～130 ℃.
In the process that drips, the Diels-Alder reaction takes place in propenal and myrcenol, obtains LYRAL, and reaction formula is following:
Propenal is a dienophile, and self-polymeric reaction takes place easily, for fear of propenal generation self-polymeric reaction; Contain stopper in the said propenal; Said stopper is preferably Resorcinol, DBPC 2,6 ditertiary butyl p cresol, 4,4-methylene-bis (2; The 6-DI-tert-butylphenol compounds) or N-phenyl-2-naphthylamines, more preferably Resorcinol.The quality optimization of said stopper is 0.1%～0.3% of a said propenal quality, more preferably 0.15%～0.25%.
Control more easily for the temperature that makes reaction system, the dropping time of said propenal is preferably 6h～10h, more preferably 8h～9h.The dropping time is long more, 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 that obtains and purity are higher.
After propenal dropwised, propenal and myrcenol continue reaction made reaction more abundant, obtains LYRAL.Temperature when continuing reaction is preferably 50 ℃～130 ℃, more preferably 70 ℃～120 ℃, most preferably is 100 ℃～110 ℃; Time is preferably 1h～2h.
In entire reaction, the mol ratio of said propenal and said myrcenol is preferably 1.1～1.5: 1, more preferably 1.1～1.2: 1.
After reaction finishes, after with deionized water reaction mixture being washed, can obtain the LYRAL bullion.The waste water that produces in the washing process can obtain propenal and water after distillation is handled, propenal can be used as raw material to be continued to use, and water can be used for the washing reaction mixture once more.
Said LYRAL bullion is carried out molecular distillation, can obtain the higher LYRAL of purity.When carrying out molecular distillation, said vacuum tightness is preferably below the 2mm mercury column, and after the molecular distillation, the cut between collecting 120 ℃～125 ℃ is LYRAL.
Said LYRAL is carried out gas chromatographic analysis, have essentially identical gas chromatogram, therefore, can access LYRAL through preparation method provided by the invention with the LYRAL standard model of American I FF company.Can know that by gas chromatogram the LYRAL purity that obtains through preparation method provided by the invention can reach more than 99%.
The present invention makes myrcenol and propenal need not at HTHP or under the condition of lewis acid catalyst and organic solvent the Diels-Alder reaction to take place through the adding mode and adding temperature of control propenal, and reaction conditions is gentle, and by product is less.Owing to need not HTHP, therefore conversion unit is required lowlyer, can not increase the cost of LYRAL; Owing to need not to add 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 specify the present invention, the preparation method of LYRAL provided by the invention is described in detail below in conjunction with embodiment.
Embodiment 1
In the 1000mL four-hole boiling flask that TM, mechanical stirring device and reflux exchanger are housed, add 539g (3.5mol) myrcenol and 0.539g Resorcinol, be heated to 110 ℃; In said myrcenol, drip 235g (4.2mol) propenal, drip 6h, in the dropping process, said reaction flask is placed freezing tank, keep the reaction flask temperature at 110 ℃～130 ℃; After propenal dropwises, continue reaction 1h, obtain reaction mixture;
Said reaction mixture with 200g deionized water wash three times, is obtained 770g LYRAL bullion, said LYRAL is carried out gas chromatographic analysis, wherein the content of LYRAL is 96.6%; Said bullion is carried out rectifying below vacuum tightness 2mmHg, the cut between collecting 120 ℃～125 ℃ obtains the 616g LYRAL.
Said LYRAL is carried out gas chromatographic analysis, and the result is referring to Fig. 1 and Fig. 2, the gas chromatogram of the LYRAL that Fig. 1 provides for the embodiment of the invention, and Fig. 2 is the gas chromatogram of the LYRAL standard model of American I FF company.
In Fig. 2, between two peaks that 10.924min and 11.123min occur are respectively-peak of (4-hydroxy-4-methyl amyl group)-3-tetrahydrobenzene-1-formaldehyde and right-(4-hydroxy-4-methyl amyl group)-3-tetrahydrobenzene-1-formaldehyde, its total content is 97.76%; And among Fig. 1; Two main peaks have appearred during respectively at 10.991min and 11.190min; These two main peaks be between-peak of (4-hydroxy-4-methyl amyl group)-3-tetrahydrobenzene-1-formaldehyde and right-(4-hydroxy-4-methyl amyl group)-3-tetrahydrobenzene-1-formaldehyde, its total content is 99.26%.
Can know by Fig. 1 and Fig. 2, prepare LYRAL, and the purity of the LYRAL that obtains is higher through method provided by the invention.
Embodiment 2
In the 1000mL four-hole boiling flask that TM, mechanical stirring device and reflux exchanger are housed, add 539g (3.5mol) myrcenol and 0.539g Resorcinol, be heated to 110 ℃; In said myrcenol, drip 216g (3.86mol) propenal, drip 6h, in the dropping process, said reaction flask is placed freezing tank, keep the reaction flask temperature at 110 ℃～130 ℃; After propenal dropwises, continue reaction 1h, obtain reaction mixture;
Said reaction mixture with 180g deionized water wash three times, is obtained 761g LYRAL bullion, said LYRAL is carried out gas chromatographic analysis, wherein the content of LYRAL is 95.2%; Said bullion is carried out rectifying below vacuum tightness 2mmHg, the cut between collecting 120 ℃～125 ℃ obtains the 605g LYRAL.
Said LYRAL is carried out gas chromatographic analysis, and when its main peak came across 10.990min and 11.191min, total content was 99.30%.
Embodiment 3
In the 1000mL four-hole boiling flask that TM, mechanical stirring device and reflux exchanger are housed, add 539g (3.5mol) myrcenol and 0.539g Resorcinol, be heated to 110 ℃; In said myrcenol, drip 196g (3.5mol) propenal, drip 6h, in the dropping process, said reaction flask is placed freezing tank, keep the reaction flask temperature at 110 ℃～130 ℃; After propenal dropwises, continue reaction 1h, obtain reaction mixture;
Said reaction mixture with 180g deionized water wash three times, is obtained 755g LYRAL bullion, said LYRAL is carried out gas chromatographic analysis, wherein the content of LYRAL is 87.4%; Said bullion is carried out rectifying below vacuum tightness 2mmHg, the cut between collecting 120 ℃～125 ℃ obtains the 516g LYRAL.
Said LYRAL is carried out gas chromatographic analysis, and when its main peak came across 10.991min and 11.190min, total content was 99.25%.
Embodiment 4
In the 1000mL four-hole boiling flask that TM, mechanical stirring device and reflux exchanger are housed, add 539g (3.5mol) myrcenol and 0.539g Resorcinol, be heated to 60 ℃; In said myrcenol, drip 235g (4.2mol) propenal, drip 7h, in the dropping process, said reaction flask is placed freezing tank, keep the reaction flask temperature at 60 ℃～70 ℃; After propenal dropwises, continue reaction 1h, obtain reaction mixture;
Said reaction mixture with 200g deionized water wash three times, is obtained 771g LYRAL bullion, said LYRAL is carried out gas chromatographic analysis, wherein the content of LYRAL is 93.1%; Said bullion is carried out rectifying below vacuum tightness 2mmHg, the cut between collecting 120 ℃～125 ℃ obtains the 612g LYRAL.
Said LYRAL is carried out gas chromatographic analysis, and when its main peak came across 10.991min and 11.190min, total content was 99.23%.
Embodiment 5
In the 1000mL four-hole boiling flask that TM, mechanical stirring device and reflux exchanger are housed, add 539g (3.5mol) myrcenol and 0.539g Resorcinol, be heated to 60 ℃; In said myrcenol, drip 216g (3.86mol) propenal, drip 7h, in the dropping process, said reaction flask is placed freezing tank, keep the reaction flask temperature at 60 ℃～70 ℃; After propenal dropwises, continue reaction 1h, obtain reaction mixture;
Said reaction mixture with 180g deionized water wash three times, is obtained 763g LYRAL bullion, said LYRAL is carried out gas chromatographic analysis, wherein the content of LYRAL is 92.0%; Said bullion is carried out rectifying below vacuum tightness 2mmHg, the cut between collecting 120 ℃～125 ℃ obtains the 603g LYRAL.
Said LYRAL is carried out gas chromatographic analysis, and when its main peak came across 10.991min and 11.190min, total content was 99.31%.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (10)
1. the preparation method of a LYRAL may further comprise the steps:
A) myrcenol is warming up to 50 ℃～130 ℃;
B) in the myrcenol that step a) obtains, drip propenal, controlled temperature is 50 ℃～130 ℃ in the dropping process, dropwises the continued reaction, obtains LYRAL.
2. preparation method according to claim 1 is characterized in that, in the said step b), the dropping time of said propenal is 6h～10h.
3. preparation method according to claim 1 is characterized in that, in the said step b), the temperature of said reaction is 50 ℃～130 ℃.
4. preparation method according to claim 1 is characterized in that, in the said step b), the said time that dropwises the continued reaction is 1h～2h.
5. preparation method according to claim 1 is characterized in that, the mol ratio of said propenal and said myrcenol is 1.1～1.5: 1.
6. preparation method according to claim 1 is characterized in that, said step b) specifically may further comprise the steps:
B1) in the myrcenol that step a) obtains, drip propenal;
B2) with step b1) reaction mixture that obtains washs in deionized water, obtains the LYRAL bullion;
B3) said LYRAL bullion is carried out high vacuum rectification, obtain LYRAL.
7. preparation method according to claim 6 is characterized in that, said step b3) in, the vacuum tightness when carrying out high vacuum rectification is below the 2mm mercury column.
8. preparation method according to claim 1 is characterized in that, in the said step b), contains the stopper of 0.1wt%～0.3wt% in the said propenal.
9. preparation method according to claim 1 is characterized in that, in the said step a), contains the stopper of 0.1wt%～0.3wt% in the said myrcenol.
10. according to Claim 8 or 9 described preparing methods, it is characterized in that said stopper is Resorcinol, DBPC 2,6 ditertiary butyl p cresol, 4,4-methylene-bis (2,6 di t butyl phenol) or N-phenyl-2-naphthylamines.
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Cited By (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 |
| CN110187033A (en) * | 2019-06-14 | 2019-08-30 | 江西省药品检验检测研究院 | The preparation method of lyral and its purposes in cosmetics detection |
| CN110183319A (en) * | 2019-06-14 | 2019-08-30 | 江西省药品检验检测研究院 | The method for preparing cosmetics detection lyral |
Citations (6)
| 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 |
| 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 (6)
| 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 |
| JPS62141097A (en) * | 1985-12-13 | 1987-06-24 | 花王株式会社 | Purification of perfume base material |
Non-Patent Citations (2)
| Title |
|---|
| 张国安: "新铃兰醛香料的合成", 《陕西化工》 * |
| 林晓等: "从月桂烯出发合成新铃兰醛", 《广州化学》 * |
Cited By (5)
| 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 |
| CN110187033A (en) * | 2019-06-14 | 2019-08-30 | 江西省药品检验检测研究院 | The preparation method of lyral and its purposes in cosmetics detection |
| CN110183319A (en) * | 2019-06-14 | 2019-08-30 | 江西省药品检验检测研究院 | The method for preparing cosmetics detection lyral |
| 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 |
| 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 |
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|---|---|---|---|
| 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 |
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| 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 |