CN115215725A - Method for preparing lavender acetate and lavender alcohol - Google Patents
Method for preparing lavender acetate and lavender alcohol Download PDFInfo
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- CN115215725A CN115215725A CN202110405232.5A CN202110405232A CN115215725A CN 115215725 A CN115215725 A CN 115215725A CN 202110405232 A CN202110405232 A CN 202110405232A CN 115215725 A CN115215725 A CN 115215725A
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- acetate
- lavender
- linalool
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- 244000178870 Lavandula angustifolia Species 0.000 title claims abstract description 84
- 235000010663 Lavandula angustifolia Nutrition 0.000 title claims abstract description 84
- 239000001102 lavandula vera Substances 0.000 title claims abstract description 84
- 235000018219 lavender Nutrition 0.000 title claims abstract description 84
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 title claims abstract description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 23
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 claims abstract description 40
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 claims abstract description 40
- 229930007744 linalool Natural products 0.000 claims abstract description 40
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 13
- 230000032050 esterification Effects 0.000 claims abstract description 12
- 238000005886 esterification reaction Methods 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 11
- 239000010970 precious metal Substances 0.000 claims abstract 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 89
- UWKAYLJWKGQEPM-LBPRGKRZSA-N linalyl acetate Chemical compound CC(C)=CCC[C@](C)(C=C)OC(C)=O UWKAYLJWKGQEPM-LBPRGKRZSA-N 0.000 claims description 48
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 46
- UWKAYLJWKGQEPM-UHFFFAOYSA-N linalool acetate Natural products CC(C)=CCCC(C)(C=C)OC(C)=O UWKAYLJWKGQEPM-UHFFFAOYSA-N 0.000 claims description 24
- 239000012074 organic phase Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- CZVXBFUKBZRMKR-UHFFFAOYSA-N lavandulol Chemical compound CC(C)=CCC(CO)C(C)=C CZVXBFUKBZRMKR-UHFFFAOYSA-N 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 15
- 239000012295 chemical reaction liquid Substances 0.000 claims description 13
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 229910000510 noble metal Inorganic materials 0.000 claims description 11
- 150000007530 organic bases Chemical class 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- CZVXBFUKBZRMKR-JTQLQIEISA-N (R)-lavandulol Natural products CC(C)=CC[C@@H](CO)C(C)=C CZVXBFUKBZRMKR-JTQLQIEISA-N 0.000 claims description 7
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 6
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 6
- 229960004011 methenamine Drugs 0.000 claims description 6
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims description 5
- XGZKYPXTXBKQTM-UHFFFAOYSA-N 42949-24-6 Chemical compound C1C(C2)CC3C(=O)C1CN2C3 XGZKYPXTXBKQTM-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 238000000066 reactive distillation Methods 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 101150003085 Pdcl gene Proteins 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000002941 palladium compounds Chemical class 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 241001529749 Lavandula Species 0.000 claims 2
- 235000002997 Lavandula Nutrition 0.000 claims 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 150000003212 purines Chemical class 0.000 claims 1
- 150000003222 pyridines Chemical class 0.000 claims 1
- 239000000341 volatile oil Substances 0.000 abstract description 6
- 239000003205 fragrance Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000012216 screening Methods 0.000 abstract 1
- HIGQPQRQIQDZMP-UHFFFAOYSA-N geranil acetate Natural products CC(C)=CCCC(C)=CCOC(C)=O HIGQPQRQIQDZMP-UHFFFAOYSA-N 0.000 description 24
- HIGQPQRQIQDZMP-DHZHZOJOSA-N geranyl acetate Chemical compound CC(C)=CCC\C(C)=C\COC(C)=O HIGQPQRQIQDZMP-DHZHZOJOSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 19
- HIGQPQRQIQDZMP-FLIBITNWSA-N neryl acetate Chemical compound CC(C)=CCC\C(C)=C/COC(C)=O HIGQPQRQIQDZMP-FLIBITNWSA-N 0.000 description 13
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- -1 methyl Grignard reagent Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- JRTBBCBDKSRRCY-UHFFFAOYSA-N 3,7-dimethyloct-6-en-3-ol Chemical compound CCC(C)(O)CCC=C(C)C JRTBBCBDKSRRCY-UHFFFAOYSA-N 0.000 description 2
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 2
- 239000005792 Geraniol Substances 0.000 description 2
- GLZPCOQZEFWAFX-JXMROGBWSA-N Nerol Natural products CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229940113087 geraniol Drugs 0.000 description 2
- 239000000171 lavandula angustifolia l. flower oil Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- DONSTYDPUORSDN-UHFFFAOYSA-N 2,6-dimethylhepta-1,5-diene Chemical compound CC(C)=CCCC(C)=C DONSTYDPUORSDN-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 238000010478 Prins reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- JPTOCTSNXXKSSN-UHFFFAOYSA-N methylheptenone Chemical compound CCCC=CC(=O)CC JPTOCTSNXXKSSN-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- 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
- Y02P20/10—Process efficiency
Abstract
The invention provides a method for preparing lavender acetate and lavender alcohol. Screening a high-steric-hindrance organic alkaline and precious metal compound system to catalyze the esterification isomerization reaction of linalool to obtain high-quality lavender acetate, and then carrying out hydrolysis reaction on the lavender acetate to obtain the lavender alcohol. The lavender acetate and the lavender alcohol have excellent fragrance, and are particularly suitable for being applied to the field of blending of essential oil.
Description
Technical Field
The invention relates to a method for preparing lavender acetate and lavender alcohol. The directional conversion of the raw materials is realized by adding organic base with large steric hindrance and noble metal compounds, and finally high-quality lavender acetate and lavender alcohol products are obtained.
Background
The lavender acetate and the lavender alcohol are naturally contained in the lavender oil, the miscellaneous lavender oil, the lavender spica oil and some natural essential oils, and are index components of the lavender essential oil. Yang Shaoyu in the literature "extraction and ingredient identification of lavender essential oil" reports that the content of lavender alcohol and the content of lavender ester in essential oil extracted from lavender whole grass are 5.44% and 10.80%, respectively. The lavender acetate and the lavender alcohol are used for blending daily chemical essence, and have elegant lavender fragrance.
Lavender alcohol Chinese name: the 2-isopropenyl-5-methyl-4-hexenol can separate the lavandulol from the natural oil, but the lavandulol is expensive and is generally prepared by chemical synthesis, and the method for synthesizing the lavandulol mainly comprises the following steps:
(1) Dehydrating a reaction product of methylheptenone and a methyl Grignard reagent to obtain 2,6-dimethyl-1,5-heptadiene, and then carrying out Prins reaction to obtain the compound;
(2) The ester generated by the reaction of the 3-methyl-2-butyryl chloride and the 2-methyl-1-butene-2-ol is rearranged to obtain the lavender acid and then reduced to obtain the lavender acid.
The synthesis method of the lavender acetate is to acetylate the lavender alcohol. Firstly, the lavender alcohol is obtained when the lavender acetate is synthesized, and the synthesis process of the lavender alcohol is complex and the post-treatment is complicated.
Disclosure of Invention
Aiming at the problem of complicated synthesis of the lavender acetate and the lavender alcohol in the prior art, the invention adopts the following technical scheme:
a method for preparing lavender acetate and lavender alcohol comprises the following steps:
(1) The method comprises the steps of preparing lavender acetate by using linalool and acetic anhydride as raw materials and using a high-steric-hindrance organic basic catalyst and a noble metal compound in a reactive distillation mode, controlling the reaction pressure to ensure that the temperature of a distillation tower kettle is not higher than 130 ℃, and purifying a reaction liquid to obtain the lavender acetate with the purity of more than 90%;
(2) And (3) carrying out hydrolysis reaction on the purified lavender acetate to prepare the lavender alcohol, wherein the hydrolysis reaction can use an acid or alkali aqueous solution, separating an organic phase after the reaction is finished, and refining the organic phase to obtain the high-purity lavender alcohol.
Further, the step (1) comprises: the Lavender acetate is prepared by using organic base with large steric hindrance and noble metal compound to catalyze linalool to react with acetic anhydride. The sterically bulky organic base is used to have a sterically bulky structure, such as an azabridged ring compound, a purine compound, a pyridine compound, etc., preferably 1,5,7 triazabicyclo [4,4,0]Deca-5-ene, 5-azaadamantan-2-one, hexamethylene tetramine and purine. The noble metal compound is preferably a ruthenium, rhodium, palladium compound, for example ruthenium acetylacetonate Ru (acac) 3 Dodecacarbonyltetrarhodium Rh 4 (CO) 12 Palladium chloride PdCl 2 。
Further, the molar ratio of acetic anhydride to linalool in the step (1) is 1 to 10, preferably 1.05. The molar ratio of the sterically hindered organic base to linalool is in the range of 1 to 100, preferably 1 to 50 to 1. The noble metal is calculated by the amount of metal atom substances in the noble metal compound, and the dosage of the metal compound is 0.01 per mill to 0.5 per mill of the molar dosage of linalool.
Linalool and acetic anhydride are subjected to esterification isomerization reaction under the action of organic alkalinity with large steric hindrance, acetic acid is generated in the esterification process of linalool and acetic anhydride, the combination of acetic acid and the organic alkalinity with large steric hindrance is weaker, and the esterification isomerization reaction of linalool is catalyzed by acid and alkali in a system.
Further, the temperature range of the linalool esterification and isomerization reaction in the step (1) is 80 to 130 ℃, and preferably 90 to 120 ℃. The reaction time is 1 to 48h, preferably 4 to 24h.
Further, acetic acid is generated in the linalool esterification and isomerization reaction tower kettle reaction in the step (1), in order to ensure the catalytic effect, the content of the acetic acid in the reaction process needs to be ensured in a lower range, the content of the acetic acid is generally lower than 1.5%, so that the acetic acid needs to be continuously extracted from the tower top in a reactive distillation mode, a certain vacuum degree is needed for a system to be rectified and separated to generate the acetic acid, and the vacuum degree (absolute pressure) range of the system is 0.1 to 55 kPa, preferably 1.0 to 30 kPa.
Further, the linalool esterification isomerization reaction rectifying tower in the step (1) has 15 to 80 theoretical plates and a reflux ratio of 1 to 50. In a preferred scheme, the rectifying tower has 25 to 80 theoretical plates, and the reflux ratio is 5 to 1. After the reaction is finished, acetic acid and most of acetic anhydride are separated out from the tower top.
Further, after the linalool esterification and isomerization reaction in the step (1) is finished, the tower kettle contains acetic anhydride, mainly lavender acetate, linalyl acetate, organic base and other components. The lavender acetate product with the purity of more than 90 percent can be separated by a vacuum rectification mode.
Further, the purified lavender acetate is subjected to hydrolysis reaction in the step (2) to prepare the lavender alcohol, the purified lavender acetate is subjected to purification treatment in the patent to obtain the lavender acetate with the purity of more than 90%, so that the high-purity lavender alcohol can be obtained after hydrolysis, the tower bottom liquid obtained after esterification and isomerization reaction of linalool in the step (1) can be directly subjected to hydrolysis reaction, and the high-purity lavender alcohol is obtained after purification treatment.
Further, in the step (2), an aqueous solution of acid or alkali can be used for the hydrolysis reaction, an organic phase is separated after the reaction is finished, and the high-purity lavandulol is obtained after the organic phase is refined. Wherein an acid or base can be used, acid or base systems known in the art can be used, such as hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide, potassium hydroxide, calcium hydroxide, and the like.
Further, after hydrolysis reaction in the step (2), obtaining an organic phase rich in the lavender alcohol in a liquid separation mode, and rectifying or drying the organic phase to obtain the high-purity lavender alcohol.
The invention has the advantages that:
according to the method, the high-purity lavender acetate and the high-purity lavender alcohol are obtained in a simple and efficient manner by adding the high-steric-hindrance organic base into the system, the industrial operability is greatly improved after the synthetic route is optimized, the obtained lavender acetate and the lavender alcohol have excellent fragrance, and the method has advantages in essential oil blending and application.
Detailed Description
The following examples will further illustrate the process provided by the present invention but the present invention is not limited to the examples listed but also includes any other known variations within the scope of the claimed invention.
The analysis method comprises the following steps:
gas chromatograph: agilent7820A, column HP-5 (30 m.times.320. Mu.m.times.0.25 μm), injection port temperature: 150. DEG C; the flow splitting ratio is 50; carrier gas flow rate: 1.5 ml/min; temperature rising procedure: keeping at 50 deg.C for 1min, heating to 90 deg.C at 10 deg.C/min for 0min, heating to 180 deg.C at 5 deg.C/min for 0min, heating to 280 deg.C at 30 deg.C/min for 6min. Detector temperature: 280 ℃.
Example 1
244.8g of acetic anhydride, 308.2g of linalool, 13.9g of 1,5, 7-triazabicyclo [4,4,0] dec-5-ene and 15.92mg of ruthenium acetylacetonate are added into the bottom of the rectifying tower, and the internal temperature of the tower kettle is 90 to 95 ℃ for reaction under the vacuum degree of 20 kPa. The theoretical plate number of the rectifying tower is 25, and the reflux ratio is 10. The reaction time is 12h, 139.4g of acetic acid and acetic anhydride mixture are taken out from the top of the tower. Sampling meteorological chromatography to detect tower bottom composition, reaction liquid composition: 4.961% by mass of acetic anhydride, 0.014% by mass of linalool, 4.909% by mass of linalyl acetate, 0.356% by mass of linalyl dihydroacetate, 0.124% by mass of geranyl acetate, 0.225% by mass of neryl acetate, 85.478% by mass of lavender acetate, 1,5,7 triazabicyclo [4,4,0] dec-5-ene, 3.253% by mass of other 0.681%.
Adding 200g of linalyl acetate reaction liquid to the bottom of a rectifying tower, and carrying out vacuum rectification at the temperature of 108-112 ℃ in a tower kettle under the vacuum degree of 1 kPa. The theoretical plate number of the rectifying tower is 75, and the reflux ratio is 10. Collecting components at the top of the tower, collecting 179 g lavender acetate at the top of the tower, detecting the components by a gas chromatography, and preparing a product linalyl acetate: 0.003 percent of linalool, 3238 percent of linalyl acetate, 3238 percent of zxft 3238 percent of linalyl dihydrogen acetate, 0.210 percent of geranyl acetate, 0.035 percent of neryl acetate, 0.097 percent of neryl acetate and 3262 percent of lavanyl acetate.
Taking 50g of rectified lavender acetate, adding 100g of pure water and 25g of sodium hydroxide, heating for 8 hours under an inert atmosphere, cooling, and separating out an organic phase. The organic phase was washed with a saturated sodium chloride solution and then with pure water. Drying the washed organic phase by using magnesium sulfate, and detecting the composition of the dried organic phase by using a gas chromatography: the weight content of linalool is 4.074%, the weight content of dihydrolinalool is 0.211%, the weight content of geraniol is 0.034%, the weight content of nerol is 0.095%, and the weight content of lavender alcohol is 95.586%.
Example 2
Adding 306.1g of acetic anhydride, 308.2g of linalool, 6.05g of 5-azaadamantan-2-one and 14.95mg of dodecacarbonyl tetrarhodium into the bottom of a rectifying tower, and reacting at the internal temperature of the tower kettle of 85 to 90 ℃ under the vacuum degree of 10 kPa. The theoretical plate number of the rectifying tower is 25, and the reflux ratio is 15. The reaction time is 18h, and 212.24g of acetic acid and acetic anhydride mixture is collected from the top of the column. Sampling meteorological chromatography detection tower bottom composition, reaction liquid composition: 2.402 percent of acetic anhydride, 0.010 percent of linalool, 3.703 percent of linalyl acetate, 0.373 percent of linalyl dihydroacetate, 0.091 percent of geranyl acetate, 0.201 percent of neryl acetate, 91.044 percent of lavender acetate, 1.483 percent of 5-azaadamantane-2-one and 0.694 percent of the rest.
Adding 200g of linalyl acetate reaction liquid to the bottom of a rectifying tower, and carrying out vacuum rectification at the temperature of 108-112 ℃ in a tower kettle under the vacuum degree of 1 kPa. The theoretical plate number of the rectifying tower is 75, and the reflux ratio is 10. Collecting the components at the top of the tower, collecting 182 g lavender acetate at the top of the tower, and detecting the components by using a gas chromatography, wherein the product linalyl acetate comprises the following components: 0.003 percent of linalool, 3238 percent of linalyl acetate, 3238 percent of zxft 3238 percent of linalyl dihydroacetate, 0.197 percent of geranyl acetate, 0.029 percent of neryl acetate, 0.091 percent of neryl acetate and 3262 percent of zxft 3262 percent of lavender acetate.
Taking 50g of rectified lavender acetate, adding 100g of pure water and 25g of potassium hydroxide, heating for 8 hours under an inert atmosphere, cooling, and separating out an organic phase. The organic phase was washed with a saturated sodium chloride solution and then with pure water. Drying the washed organic phase by using magnesium sulfate, and detecting the composition of the dried organic phase by using a gas chromatography: 3.412 percent of linalool, 0.195 percent of dihydrolinalool, 0.028 percent of geraniol, 0.089 percent of nerol and 96.276 percent of lavender alcohol.
Example 3
Adding 306.1g of acetic anhydride, 308.2g of linalool, 28.04g of hexamethylene tetramine and 177.33mg of palladium chloride into the bottom of a rectifying tower, and reacting at the internal temperature of a tower kettle of 75 to 80 ℃ under the vacuum degree of 1.0 kPa. The theoretical plate number of the rectifying tower is 25, and the reflux ratio is 20. The reaction time is 24h, and 118.01g of acetic acid is collected from the top of the tower. Sampling meteorological chromatography to detect tower bottom composition, reaction liquid composition: 0.491% of acetic acid, 1.263% of acetic anhydride, 0.365% of linalool, 2.963% of linalyl acetate, 0.348% of linalyl dihydrogen acetate, 0.168% of geranyl acetate, 0.440% of neryl acetate, 86.657% of lavender acetate, 6.558% of hexamethylene tetramine and 0.746% of the rest.
Adding 200g of linalyl acetate reaction liquid to the bottom of a rectification tower, and carrying out rectification under reduced pressure at the temperature of 108-112 ℃ in a tower kettle under the vacuum degree of 1 kPa. The theoretical plate number of the rectifying tower is 75, and the reflux ratio is 10. Collecting the components at the top of the tower, collecting 165 g lavender acetate at the top of the tower, and detecting the components by using a gas chromatography, wherein the product linalyl acetate comprises the following components: linalool mass content of 0.135%, linalyl acetate mass content of 2.951%, linalyl dihydrogen acetate mass content of 0.200%, geranyl acetate mass content of 0.091%, neryl acetate mass content of 0.205%, and lavender acetate mass content of 96.418%.
Example 4
408.1g of acetic anhydride, 308.2g of linalool, 5.61g of hexamethylene tetramine and 7.97mg of ruthenium acetylacetonate are added to the bottom of the rectifying tower, and the reaction is carried out at the internal temperature of the tower kettle of 110 to 120 ℃ under the vacuum degree of 30 kPa. The number of theoretical plates of the rectifying tower is 25, and the reflux ratio is 5:1. The reaction time is 8h, and 118.01g of acetic acid and acetic anhydride mixture is collected from the top of the column. Sampling meteorological chromatography detection tower bottom composition, reaction liquid composition: 7.597% by mass of acetic anhydride, 0.002% by mass of linalool, 4.372% by mass of linalyl acetate, 0.355% by mass of linalyl dihydroacetate, 0.072% by mass of geranyl acetate, 0.181% by mass of neryl acetate, 85.460% by mass of lavender acetate, 1.303% by mass of hexamethylene tetramine, and 0.657% by mass of the rest.
Adding 200g of linalyl acetate reaction liquid to the bottom of a rectifying tower, and carrying out vacuum rectification at the temperature of 108-112 ℃ in a tower kettle under the vacuum degree of 1 kPa. The theoretical plate number of the rectifying tower is 75, and the reflux ratio is 10. Collecting components at the top of the tower, collecting 177 g lavender acetate at the top of the tower, detecting the components by a gas chromatography, and preparing the product linalyl acetate: linalyl acetate 4.183%, linalyl dihydrogen acetate 0.203%, geranyl acetate 0.023%, neryl acetate 0.075%, and lavender acetate 95.516%.
Example 5
265.3g of acetic anhydride, 308.2g of linalool, 9.28g of 1,5, 7-triazabicyclo [4,4,0] dec-5-ene and 29.91mg of tetracarbonyl-tetrarhodium are added into the bottom of a rectifying tower, and the reaction is carried out at the internal temperature of the tower kettle of 85 to 90 ℃ under the vacuum degree of 10 kPa. The theoretical plate number of the rectifying tower is 25, and the reflux ratio is 10. The reaction time is 4h, and 171.44g of acetic acid and acetic anhydride mixture is collected from the top of the column. Sampling meteorological chromatography to detect tower bottom composition, reaction liquid composition: 2.300 percent of acetic anhydride, 0.0052 percent of linalool, 2.258 percent of linalyl acetate, 0.353 percent of linalyl dihydroacetate, 0.067 percent of geranyl acetate, 0.174 percent of neryl acetate, 89.978 percent of lavender acetate, 2.156 percent of 1,5,7 triazabicyclo [4,4,0] dec-5-ene and 0.263 percent of the rest.
Adding 200g of linalyl acetate reaction liquid to the bottom of a rectification tower, and carrying out rectification under reduced pressure at the temperature of 108-112 ℃ in a tower kettle under the vacuum degree of 1 kPa. The theoretical plate number of the rectifying tower is 75, and the reflux ratio is 10. Collecting the components at the top of the tower, collecting 188 g lavender acetate at the top of the tower, and detecting the components by using a gas chromatography, wherein the product linalyl acetate comprises the following components: linalyl acetate 2.090%, linalyl dihydrogen acetate 0.201%, geranyl acetate 0.021%, neryl acetate 0.070%, and lavender acetate 97.618%.
Comparative example 1
244.8g of acetic anhydride and 308.2g of linalool are added to the bottom of the rectifying tower, and the reaction is carried out at the temperature of 90 to 95 ℃ in the tower kettle under the vacuum degree of 20 kPa. The theoretical plate number of the rectifying tower is 25, and the reflux ratio is 10. The reaction time is 24h, and 177.93g of acetic acid and acetic anhydride mixture is collected from the top of the column. Sampling meteorological chromatography detection tower bottom composition, reaction liquid composition: 6.031% of acetic anhydride, 38.878% of linalool, 53.448% of linalyl acetate, 0.211% of linalyl dihydrogen acetate, 0.331% of geranyl acetate, 0.459% of neryl acetate, 0.336% of lavender acetate and 0.307% of the rest.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A method for preparing high quality linalyl acetate, comprising the steps of:
(1) The method comprises the steps of preparing lavender acetate by using linalool and acetic anhydride as raw materials and using a high-steric-hindrance organic alkali and noble metal compound system catalyst in a reactive distillation mode, controlling the reaction pressure to ensure that the temperature of a distillation tower kettle is not higher than 130 ℃, and purifying reaction liquid to obtain the lavender acetate with the purity of more than 90%;
(2) And (3) carrying out hydrolysis reaction on the purified lavender acetate to prepare the lavender alcohol, wherein the hydrolysis reaction can use an acid or alkali aqueous solution, separating an organic phase after the reaction is finished, and refining the organic phase to obtain the high-purity lavender alcohol.
2. The method of claim 1, wherein step (1) comprises: the preparation method of Lavandula acetate is characterized in that the reaction of linalool and acetic anhydride is catalyzed by using organic bases with large steric hindrance and precious metal compound systems to prepare Lavandula acetate, and the organic bases with large steric hindrance, such as aza-bridged ring compounds, purine compounds, pyridine compounds and the like, are preferably 1,5,7 triazabicyclo [4,4,0]Deca-5-ene, 5-azaadamantan-2-one, hexamethylene tetramine, purine; the noble metal compound is preferably a ruthenium, rhodium, palladium compound, for example ruthenium acetylacetonate Ru (acac) 3 Dodecacarbonyltetrarhodium Rh 4 (CO) 12 PdCl, palladium chloride 2 。
3. The method of claims 1-2, step (1) comprising: the molar ratio of acetic anhydride to linalool is 1 to 10, preferably 1.05; the molar ratio of the sterically hindered organic base to the linalool is 1 to 100, preferably 1 to 50 to 1; the noble metal compound is calculated by the amount of metal atom substances in the noble metal compound, and the dosage of the noble metal compound is 0.01 per mill to 0.5 per mill of the molar dosage of linalool.
4. The method of any one of claims 1-3, step (1) comprising: the temperature range of the linalool esterification isomerization reaction is 80 to 130 ℃, and preferably 90 to 120 ℃; the reaction time is 1 to 48h, preferably 4 to 24h.
5. The method according to claims 1-4, wherein the linalool in the step (1) is esterified and isomerized to produce acetic acid, the acetic acid is extracted from the top of the tower by means of reactive distillation, and the vacuum degree (absolute pressure) of the system is 0.1 to 55 kPa, preferably 1.0 to 30 kPa.
6. The method according to any one of claims 1 to 5, wherein the linalool esterification isomerization reaction rectifying tower in the step (1) has 15 to 80 theoretical plates and a reflux ratio of 1 to 50; in a preferred scheme, the rectifying tower has 25 to 80 theoretical plates, and the reflux ratio is 5 to 1.
7. The method according to any one of claims 1-6, wherein after the linalool esterification and isomerization reaction in step (1) is finished, the tower still contains acetic anhydride, mainly lavender acetate, linalyl acetate, organic base and other components; the lavender acetate product with the purity of more than 90 percent can be separated by a vacuum rectification mode.
8. The method according to any one of claims 1-7, wherein in step (2), the hydrolysis reaction is carried out by using an aqueous solution of acid or alkali, an organic phase is separated after the reaction is finished, and the organic phase is refined to obtain the high-purity lavandulol; wherein an acid or base can be used, acid or base systems known in the art can be used, such as hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide, potassium hydroxide, calcium hydroxide, and the like.
9. The method according to any one of claims 1-8, wherein the organic phase rich in lavandulol is obtained by liquid separation after the hydrolysis reaction in step (2), and the organic phase is rectified or dried to obtain high purity lavandulol.
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