CN115557838A - Method for synthesizing linalyl acetate - Google Patents
Method for synthesizing linalyl acetate Download PDFInfo
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- CN115557838A CN115557838A CN202110749205.XA CN202110749205A CN115557838A CN 115557838 A CN115557838 A CN 115557838A CN 202110749205 A CN202110749205 A CN 202110749205A CN 115557838 A CN115557838 A CN 115557838A
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- linalyl acetate
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- linalool
- acetic acid
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- UWKAYLJWKGQEPM-LBPRGKRZSA-N linalyl acetate Chemical compound CC(C)=CCC[C@](C)(C=C)OC(C)=O UWKAYLJWKGQEPM-LBPRGKRZSA-N 0.000 title claims abstract description 128
- UWKAYLJWKGQEPM-UHFFFAOYSA-N linalool acetate Natural products CC(C)=CCCC(C)(C=C)OC(C)=O UWKAYLJWKGQEPM-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 46
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 81
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 claims abstract description 29
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 claims abstract description 29
- 229930007744 linalool Natural products 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- 150000004679 hydroxides Chemical class 0.000 claims description 4
- 235000021317 phosphate Nutrition 0.000 claims description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 239000011964 heteropoly acid Substances 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
- 238000004817 gas chromatography Methods 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 238000009776 industrial production Methods 0.000 description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- QWOJMRHUQHTCJG-UHFFFAOYSA-N CC([CH2-])=O Chemical compound CC([CH2-])=O QWOJMRHUQHTCJG-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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- 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
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for synthesizing linalyl acetate, which takes linalool and acetic acid as raw materials, only water is generated in the preparation process, byproducts such as acetic acid and the like are not generated, three wastes are greatly reduced, meanwhile, a catalyst is also added in the preparation process, the reaction can be carried out at a lower temperature due to the addition of the catalyst, the conversion rate of reactants, the yield and the purity of products can be further improved by adding the catalyst, the catalyst can be recovered only by filtering, the post-treatment is simple, the activity of the recovered catalyst is not obviously reduced, and the production cost is greatly reduced.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for synthesizing linalyl acetate.
Background
Linalyl acetate (structural formula shown in Scheme 1), chemical name: 3, 7-dimethyl-1, 6-octadien-3-ol acetate, colorless to pale yellow liquid, has flower fragrance and fruity odor, and compared with linalool, linalyl acetate has more elegant fragrance. Linalyl acetate is used mainly as perfume, and may be used widely in compounding essential oil of different fragrance types, cosmetics, perfume, shampoo, soap and other daily use articles. With the improvement of the living standard of human beings, the demand of the market for linalyl acetate will be greatly increased, however, the linalyl acetate contained in natural plants is difficult to extract, and the yield of the obtained linalyl acetate is low, which is far from meeting the market demand. Therefore, how to improve the synthesis process of linalyl acetate is a technical problem to be solved urgently to prepare high-purity linalyl acetate.
At present, the reports of preparing linalyl acetate from linalool reported at home and abroad mainly comprise the following steps:
in 2002, linalool and acetic anhydride are used as raw materials and anhydrous potassium carbonate is used as an alkaline catalyst in the front of the remainder of the Hunan light industry research institute, acetic acid is continuously removed in vacuum by a thermal reaction method, a reaction crude product is washed by saline water and alkaline water, and then the reaction crude product is purified by rectification under reduced pressure to obtain linalyl acetate, wherein the molar yield is more than 95.2%. But the complex post-treatment process greatly increases the production cost. (Synthesis of Pre-Shelken, zhou Chang, li Jian. Linalyl acetate [ J ] Fine chemical intermediate, 2002,32 (6): 15-16.)
In 2013, the Turkey march of Jiangxi light industry research institute and the like synthesizes linalyl acetate by using linalool and acetic anhydride as raw materials and 4-Dimethylaminopyridine (DMAP) as a catalyst through a reaction-distillation process, and the molar yield is more than 96%. However, the catalyst is expensive and difficult to recover, which greatly increases the production cost. (guan pacejun, zhao Li Xia, li Xiang Min et al. Linalyl acetate synthesis process improvement [ J ] light industry Standard and quality, 2013,4
In 2000, US6156926 reported a linalool and a process for the preparation of linalyl acetate by thermal cleavage of acetic acid to produce the acylating agent, ketene. When zinc acetate is used as a catalyst, the dosage of the catalyst is only 1 percent of linalool, the reaction temperature is controlled to be 80-95 ℃, linalyl acetate is obtained after the reaction time is 143min, and the molar yield reaches 98.45 percent. However, the toxicity of the acetonide is high, the preparation is difficult, and the industrial production is difficult to realize.
In 1995, nasser Irapoor reported a process for the preparation of linalyl acetate with a molar yield of 87% using linalool and acetic anhydride as starting materials and 2,3-dichloro-5, 6-dicyan-p-benzoquinone (DDQ) as a catalyst. Although the yield is high, the dosage of DDQ is large, the price is high, and the method is not suitable for industrial production. (Nasser Iranpoor. Alcohols and Alcohols of alcoholic and catalytic Alcohols Catalyzed by 2, 3-dichoro-5, 6-Dicyanobenzoquinone [ J ] Synth Commun,1995,25
In 2016, M.J. da Silva reported a formulation of Fe (NO) from linalool and acetic anhydride as starting materials 2 ) 3 As a catalyst, linalyl acetate can be prepared by reacting at 60 ℃ for about 1h, and the conversion rate is as high as 90%, but the selectivity is poor.
The reports on the preparation of linalyl acetate from linalool show that the processes require more catalyst, longer reaction time, difficult catalyst recovery and difficult application, and the post-treatment process is complex, and generates more three wastes, so that the production cost is greatly increased, and the economy, environmental protection and safety are further improved, therefore, how to obtain the high-yield, high-quality and environment-friendly linalyl acetate preparation process is still worth exploring.
Disclosure of Invention
Based on the above technical background, the present inventors have made a keen search and, as a result, have found that: the linalyl acetate with higher purity can be prepared by taking acetic acid and linalyl acetate as raw materials under the catalysis condition of a supported catalyst, meanwhile, the reaction temperature is lower and the reaction condition is milder due to the addition of the supported catalyst, the process method does not generate acetic acid and other byproducts, the reaction selectivity is high, the post-treatment is simple, the catalyst can be recycled and reused only by filtration, and the preparation process is safe, environment-friendly and high in yield, so that the invention is completed.
In a first aspect, the present invention provides a method for synthesizing linalyl acetate, which comprises the following steps:
and 3, after the reaction is finished, performing post-treatment to obtain the linalyl acetate.
In a second aspect, the present invention provides linalyl acetate prepared by the method according to the first aspect of the present invention.
The method for synthesizing linalyl acetate and the linalyl acetate prepared by the method have the following advantages:
(1) The process method disclosed by the invention is simple to operate, low in reaction temperature, mild in reaction condition, less in three wastes generated in the preparation process, green and environment-friendly, and suitable for industrial production;
(2) The process method has simple post-treatment, the catalyst can be recycled, and the production cost is low;
(3) The linalyl acetate prepared by the method has higher purity and yield.
Drawings
FIG. 1 shows a gas chromatogram of linalyl acetate obtained according to example 1 of the present invention.
Detailed Description
The present invention will be described in detail below, and features and advantages of the present invention will become more apparent and apparent as the description proceeds.
The first aspect of the present invention is to provide a method for synthesizing linalyl acetate, which uses linalool and acetic acid as raw materials.
In the prior art, the linalool acetate is prepared by the reaction of acetic anhydride and linalool, acetic acid is generated in the production process, and the acetic acid has the defect of difficult removal, so that the post-treatment is complex and the cost is high.
According to a preferred embodiment of the invention, a supported catalyst is also added during the synthesis.
The supported catalyst refers to a catalyst in which an active component and a cocatalyst are uniformly dispersed and supported on a specially selected carrier. The carrier provides an effective surface and a suitable pore structure for supporting the active ingredient.
The temperature required by the selected supported catalyst is lower, the reaction temperature is reduced by adding the supported catalyst, so that the reaction is milder and safer, the energy consumption can be greatly reduced by reducing the reaction temperature particularly in industrial production, the reaction selectivity of the catalyst is high, and tests show that the purity and the yield of the prepared linalyl acetate are effectively improved after the catalyst is added in the reaction process.
Specifically, the method comprises the following steps:
and 3, after the reaction is finished, carrying out post-treatment to obtain the linalyl acetate.
This step is specifically described and illustrated below.
The reaction kettle is a reaction kettle with a rectifying column, and after the reaction is finished, the reaction product linalyl acetate can be obtained by directly rectifying.
In the invention, the carrier of the supported catalyst is selected from one or more of inorganic oxides, carbon materials, zeolite, molecular sieves and heteropoly acid, preferably selected from one or more of titanium oxide, aluminum oxide, silicon dioxide, zirconium oxide, zeolite, HZSM-5, hollow graphite, carbon nano tube and graphene, and more preferably selected from one or more of titanium oxide, zirconium oxide, zeolite, HZSM-5 and graphene.
The active component is selected from one or more of oxides, hydroxides, carbonates and phosphates of transition metals, preferably from one or more of oxides, hydroxides, carbonates and phosphates of scandium, titanium, francium, manganese, iron, cobalt, nickel, zirconium, niobium, molybdenum, ruthenium, rhodium, iridium, rhenium and neodymium, more preferably from one or more of oxides, hydroxides, carbonates and phosphates of zirconium, niobium, molybdenum, ruthenium and neodymium,
according to a preferred embodiment of the present invention, the supported catalyst is selected from ZrO 2 /HZSM-5、ZrO 2 /γ-Al 2 O 3 、ZrO 2 /TiO 2 、NbO/SiO 2 、MoO 3 HZSM-5 and Zr (OH) 2 One or more kinds of zeolite, preferably ZrO 2 /HZSM-5、ZrO 2 /γ-Al 2 O 3 And NbO/SiO 2 One or more of them.
Tests show that the supported catalyst can be used for reaction at a lower reaction temperature after being added into a reaction system, has high selectivity, and can greatly improve the conversion rate of reaction raw materials and the yield of prepared products.
In the present invention, the toluene is used as a reaction solvent, linalool and acetic acid are reacted in the toluene solvent, and the amount of toluene added is not limited.
The reaction equation of the reaction is described by formula (1):
the mass ratio of the linalool to the acetic acid to the catalyst is (450-1000) to (200-500): 1, the preferred mass ratio is (470-950) to (210-450): 1, more preferably the mass ratio of (490-940): (220-400): 1.
the mass ratio of linalool to acetic acid affects the conversion rate of the prepared reaction raw materials and the yield and purity of the product, a small amount of added acetic acid causes the conversion rate of linalool and the yield and purity of linalyl acetate to be low, and a large amount of added acetic acid causes excessive acetic acid not to react completely, thereby increasing the post-treatment process.
The addition of a proper amount of catalyst can reduce the reaction temperature, greatly reduce the energy consumption and ensure that the reaction is milder and safer in industrial production, and experiments show that the purity and the yield of the product are continuously improved along with the increase of the addition amount of the catalyst, but if the addition amount of the catalyst is continuously increased, the improvement of the purity and the yield of the product is not obvious, and the inventor finds that when the addition amounts of the reaction raw materials and the catalyst are in the range, the purity and the yield of the prepared product are higher.
And 2, reducing the pressure to negative pressure, and then heating for reaction.
The pressure is reduced to-0.10 to 0MPa, preferably-0.1 to-0.05 MPa, more preferably-0.1 to-0.08 MPa, and the water generated in the reaction can be taken away to the maximum extent when the pressure is reduced to the range of-0.1 to-0.08 MPa, so that the conversion rate of the linalool is improved, and the side reaction is reduced.
The temperature is raised to 50 to 100 ℃, preferably to 50 to 80 ℃, more preferably to 60 to 70 ℃.
The invention uses the load catalyst to carry out catalytic reaction, so that the reaction can be carried out at lower temperature, and the reaction condition is milder. The linalyl acetate prepared at the temperature has higher purity and the conversion rate of reaction raw materials is higher.
The reaction time is 5 to 15 hours, preferably 7 to 12 hours, and more preferably 8 to 10 hours.
If the reaction time is too short, the conversion of the raw materials is incomplete, the yield and the purity of the product are lower, if the reaction time is too long, the preparation efficiency is reduced, if the reaction time is 5 to 15 hours, the reaction is more complete, and the yield and the purity of the prepared reaction product linalyl acetate are higher.
And 3, after the reaction is finished, performing post-treatment to obtain the linalyl acetate.
The post-treatment comprises filtration and rectification, after the reaction temperature is reduced to room temperature, stirring is stopped, the catalyst is filtered and recovered, the activity of the filtered catalyst is not obviously reduced, the catalyst can be reused in the next preparation, and the catalyst can be recovered for more than 10 times, preferably 10-20 times.
And rectifying the filtrate to obtain high-purity linalyl acetate. The rectification is preferably vacuum rectification, so that the temperature in a reaction kettle during rectification is reduced, linalool is prevented from being dehydrated to form olefin, and the rectification efficiency is improved.
According to a preferred embodiment of the present invention, the specific operation process of the vacuum distillation is as follows: adding negative pressure to 0.5-2 mmHg, the kettle temperature is 90-120 ℃, the air temperature is 90-110 ℃, and the time of decompression rectification is 15-25 h.
The process method has the advantages of high conversion rate of the raw materials, 90-99 percent of conversion rate, high selectivity of 95-99.9 percent, purity of the prepared linalyl acetate of 99-99.9 percent and comprehensive yield of 90-97.6 percent.
In a second aspect, the present invention provides linalyl acetate prepared by the method according to the first aspect of the present invention.
The linalyl acetate has high purity of 99-99.9%.
The invention has the following beneficial effects:
(1) The invention takes linalool and acetic acid as raw materials and adopts ZrO 2 The HZSM-5 is used as a catalyst for preparing the linalyl acetate by catalysis, the conversion rate of the raw materials is up to 98.14 percent, the selectivity is up to more than 95 percent, the product purity is up to more than 99 percent, the comprehensive yield is up to 97.6 percent, and the preparation process is simple and easy to implement and is suitable for industrial production;
(2) The temperature required by the adopted supported catalyst is lower and is only 50-100 ℃, meanwhile, the post-treatment is simple, and the catalyst can be recycled and reused only by filtration;
(3) The supported catalyst adopted by the invention can be recycled for more than 10 times, the activity of the catalyst is not obviously reduced, and the production cost is greatly reduced;
(4) The process method of the invention has no byproducts such as acetic acid and the like, high reaction selectivity, only water in the preparation process and great reduction of three wastes.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting to the scope of the invention.
Example 1
A clean 2L reactor equipped with a rectifying column was charged with 462.60g of linalool (3.0 mol), 198.17g of acetic acid (3.3 mol), 414.63g of toluene (4.5 mol) and 0.93g of ZrO 2 HZSM-5, sealing, keeping pressure, detecting, setting the stirring speed at 1000rpm, increasing the negative pressure to-0.10 MPa, heating to 65 ℃, collecting the fraction when the reflux is stable, continuously extracting for 9h,after the reaction is finished, after the reaction temperature is reduced to room temperature, stopping stirring, filtering and recovering the solid supported catalyst, drying the solid supported catalyst, sealing and storing the dried solid supported catalyst by using nitrogen, detecting the obtained filtrate by GC to obtain 98.14% of conversion rate and 99.37% of selectivity, and obtaining linalyl acetate with the purity of 99.50% by vacuum rectification (the specific operation process of vacuum rectification, namely adding negative pressure to 1mmHg, heating the kettle at 100-110 ℃, keeping the temperature at 95-100 ℃ and carrying out vacuum rectification for 20 hours), wherein the total amount is 573.74g, the yield is 97.52%, and the gas chromatogram of the linalyl acetate is shown in figure 1.
Example 2
The preparation of linalyl acetate was carried out in a similar manner to that of example 1, except that: the catalyst being ZrO 2 /γ-Al 2 O 3 。
The conversion rate of the filtrate is 96.33 percent and the selectivity is 97.26 percent through GC detection, and linalyl acetate with the purity of 99.24 percent can be obtained through reduced pressure distillation, the total amount is 550.76g, and the yield is 93.69 percent.
Example 3
The preparation of linalyl acetate was carried out in a similar manner to that of example 1, except that: the catalyst is NbO/SiO 2 。
The conversion rate of the filtrate is 95.76 percent and the selectivity is 95.27 percent through GC detection, and linalyl acetate with the purity of 99.22 percent can be obtained through reduced pressure distillation, the total amount is 510.86g, and the yield is 91.23 percent.
Example 4
The preparation of linalyl acetate was carried out in a similar manner to that of example 1, with the only difference that: the reaction temperature was 70 ℃.
GC detection of the filtrate can obtain 98.76% of conversion rate and 98.39% of selectivity, and reduced pressure distillation can obtain 99.37% of linalyl acetate, wherein the total amount is 574.33g, and the yield is 97.17%.
Example 5
The preparation of linalyl acetate was carried out in a similar manner to that of example 1, except that: to a clean 2L reactor equipped with a rectifying column were charged 462.60g of linalool (3.0 mol), 198.17g of acetic acid (3.3 mol), 414.63g of toluene (4.5 mol) and 0.50g of ZrO 2 /HZSM-5。
GC detection of the filtrate can obtain 91.28 percent of conversion rate and 99.44 percent of selectivity, and reduced pressure distillation can obtain 99.24 percent of linalyl acetate, wherein the total amount is 527.71g, and the yield is 90.77 percent.
Comparative example
Comparative example 1
The preparation of linalyl acetate was carried out in a similar manner to example 1, with the only difference that: a clean 2L reactor equipped with a rectifying column was charged with 462.60g of linalool (3.0 mol), 198.17g of acetic acid (3.3 mol) and 414.63g of toluene (4.5 mol).
The conversion rate of the filtrate is 53.22 percent and the selectivity is 90.33 percent by GC detection, and linalyl acetate with the purity of 99.12 percent can be obtained by reduced pressure distillation, the total amount is 282.58g, and the yield is 48.07 percent.
Comparative example 2
The preparation of linalyl acetate was carried out in a similar manner to example 1, with the only difference that: to a clean 2L reactor equipped with a rectifying column were charged 462.60g of linalool (3.0 mol), 198.17g of acetic acid (3.3 mol), 414.63g of toluene (4.5 mol) and 0.93g of phosphoric acid.
The conversion rate of the filtrate is 66.98 percent and the selectivity is 89.99 percent through GC detection, and linalyl acetate with the purity of 99.11 percent can be obtained through reduced pressure distillation, the total amount is 354.35g, and the yield is 60.28 percent.
Examples of the experiments
Experimental example 1 gas chromatography test
The product obtained in example 1 was analyzed by Gas Chromatography (GC) using a Thermo scientific TRACE1300 gas chromatograph using a gas capillary column (30 mm. Times.0.25 mm. Times.1.4 μm). The detection conditions are as follows: the sample injection amount is 0.2 mu L, the flow rate of carrier gas is 1mL/min, the split ratio is 50. Temperature rising procedure: the initial temperature is 40 deg.C, and the temperature is maintained for 5min, and the temperature is raised to 250 deg.C at the rate of 20 deg.C/min, and the temperature is maintained for 5min. The test results are shown in table 1.
TABLE 1
As can be seen from Table 1, the reaction conversion and linalyl acetate yield can be greatly improved by using the catalyst of the present invention compared to comparative examples 1 and 2.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to limit the invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A method for synthesizing linalyl acetate, which is characterized in that linalool and acetic acid are used as raw materials.
2. The method of claim 1, wherein a supported catalyst is also added during the synthesis.
3. Method according to claim 2, characterized in that it comprises the following steps:
step 1, adding linalool, acetic acid, toluene and a supported catalyst into a reaction kettle, and then sealing;
step 2, reducing the pressure to negative pressure, and then heating for reaction;
and 3, after the reaction is finished, carrying out post-treatment to obtain the linalyl acetate.
4. The method according to claim 3, wherein, in step 1,
the carrier of the supported catalyst is selected from one or more of inorganic oxide, carbon material, zeolite, molecular sieve and heteropoly acid;
the active component is selected from one or more of transition metal oxides, hydroxides, carbonates and phosphates.
5. The method according to claim 3, wherein, in step 1,
the mass ratio of the linalool to the acetic acid to the catalyst is (450-1000): (200-500): 1.
6. the method according to claim 3, wherein in the step 2, the pressure is reduced to-0.10 to 0MPa.
7. The method of claim 3, wherein the temperature is raised to 50-100 ℃ in step 2, and the reaction time is 5-15 hours.
8. The method according to claim 3, wherein, in step 3,
the post-treatment comprises filtration and rectification, and the catalyst is recovered by filtration, can be recycled in the next preparation, and can be recycled for 10-20 times.
9. The method according to claim 8, wherein, in step 3,
the method has the advantages that the conversion rate of the raw materials is 90-99%, the purity of the linalyl acetate is 99-99.9%, and the yield is 90-97.6%.
10. Linalyl acetate characterized in that it is obtained by a process according to one of claims 1 to 9.
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| MA´RCIO J. DA SILVA，等: "Fe(SO4)3-Catalyzed Synthesis of Terpenic Alcohols Esters: A Simple and Bifunctional Reusable Solid Catalyst", CHEMISTRYSELECT, vol. 3, 31 December 2018 (2018-12-31) * |
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