CN116462587A - Synthesis method of high-purity storax acetate - Google Patents
Synthesis method of high-purity storax acetate Download PDFInfo
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- CN116462587A CN116462587A CN202310304616.7A CN202310304616A CN116462587A CN 116462587 A CN116462587 A CN 116462587A CN 202310304616 A CN202310304616 A CN 202310304616A CN 116462587 A CN116462587 A CN 116462587A
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- 241001060310 Styracaceae Species 0.000 title claims abstract description 62
- 235000001361 Styrax officinalis Nutrition 0.000 title claims abstract description 62
- 235000019382 gum benzoic Nutrition 0.000 title claims abstract description 62
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 title claims abstract description 28
- 238000001308 synthesis method Methods 0.000 title claims abstract description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 51
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 36
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 150000007524 organic acids Chemical class 0.000 claims description 13
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- 239000007868 Raney catalyst Substances 0.000 claims description 6
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 6
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- UNXHWFMMPAWVPI-QWWZWVQMSA-N D-threitol Chemical compound OC[C@@H](O)[C@H](O)CO UNXHWFMMPAWVPI-QWWZWVQMSA-N 0.000 claims description 5
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 5
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims 2
- 238000005886 esterification reaction Methods 0.000 abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 8
- FMFHUEMLVAIBFI-BQYQJAHWSA-N [(e)-2-phenylethenyl] acetate Chemical compound CC(=O)O\C=C\C1=CC=CC=C1 FMFHUEMLVAIBFI-BQYQJAHWSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000011403 purification operation Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 239000000543 intermediate Substances 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007701 flash-distillation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- MNNZINNZIQVULG-UHFFFAOYSA-N 2-chloroethylbenzene Chemical compound ClCCC1=CC=CC=C1 MNNZINNZIQVULG-UHFFFAOYSA-N 0.000 description 2
- 244000099147 Ananas comosus Species 0.000 description 2
- 235000007119 Ananas comosus Nutrition 0.000 description 2
- 244000111489 Gardenia augusta Species 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- CRRUGYDDEMGVDY-UHFFFAOYSA-N 1-bromoethylbenzene Chemical compound CC(Br)C1=CC=CC=C1 CRRUGYDDEMGVDY-UHFFFAOYSA-N 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 235000003261 Artemisia vulgaris Nutrition 0.000 description 1
- 240000006891 Artemisia vulgaris Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001632576 Hyacinthus Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000010254 Jasminum officinale Nutrition 0.000 description 1
- 240000005385 Jasminum sambac Species 0.000 description 1
- 241000218378 Magnolia Species 0.000 description 1
- 244000070406 Malus silvestris Species 0.000 description 1
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 1
- 244000014047 Polianthes tuberosa Species 0.000 description 1
- 235000016067 Polianthes tuberosa Nutrition 0.000 description 1
- 244000018633 Prunus armeniaca Species 0.000 description 1
- 235000009827 Prunus armeniaca Nutrition 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 244000297179 Syringa vulgaris Species 0.000 description 1
- 235000004338 Syringa vulgaris Nutrition 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- -1 methyl phenyl methyl Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 235000021018 plums Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing high-purity storax acetate, which relates to the technical field of organic synthesis, and comprises the steps of synthesizing storax alcohol through hydrogenation reaction of acetophenone, and synthesizing storax acetate through esterification reaction of the storax alcohol and acetic anhydride; according to the synthesis method provided by the invention, morpholine is added to inhibit the activity of the hydrogenation catalyst, the selectivity of Gao Jiaqing is improved, the yield of the intermediate styrol reaches more than 95%, the purification operation of the intermediate styrol is omitted, the esterification reaction is directly carried out, and the yield of the product styryl acetate is improved.
Description
Technical field:
the invention relates to the technical field of organic synthesis, in particular to a method for synthesizing high-purity storax acetate.
The background technology is as follows:
storax acetate, also called gardenia alcohol II, is known as methyl phenyl methyl acetate, and is transparent colorless to pale yellow viscous liquid, and has a molecular formula of C 10 H 12 O 2 The relative molecular weight is 164.20, the boiling point is 214 ℃, and the product belongs to carboxylic ester synthetic perfume. The ester spice has the most wide application in food essence, and can be used for preparing edible essence such as apples, pineapple, apricots, peaches, pineapples, plums and the like, so that the aroma of various foods such as cakes, beverages and the like is more abundant. The storax acetate has strong diffusivity, and can be used for preparing daily use essence of hyacinth, lilac, jasmine, mugwort, magnolia and the like, and daily use essence of gardenia and tuberose.
The current synthetic route of storax acetate mainly comprises the following steps:
(1) The ethyl benzene is chlorinated by chlorine to produce alpha-chlorobenzene, and then reacts with sodium acetate to synthesize storax acetate. The reaction route is as follows:
the method has the defects that a large amount of hydrogen chloride gas is generated in the halogenation stage and the substitution stage, the potential safety hazard is large, the reaction is not easy to control, and various halogenated mixtures can be generated.
(2) The ethyl benzene and N-bromosuccinimide (NBS) are subjected to substitution reaction at the benzyl position to generate alpha-bromoethylbenzene, and then are reacted with silver acetate and acetic acid to generate styryl acetate. The reaction route is as follows:
the method is only suitable for small-batch preparation, has poor atom economy and is not suitable for mass production.
(3) Styrene and hydrogen chloride are subjected to addition reaction to generate alpha-chloroethylbenzene, and then the alpha-chloroethylbenzene and sodium acetate are reacted to generate styryl acetate. The reaction route is as follows:
the method also uses hydrogen chloride gas, which brings inconvenience to large-scale production, and styrene is easy to polymerize under the condition of strong acid.
In summary, the synthesis process of storax acetate in the prior art has the disadvantages of high toxicity of raw materials, high potential safety hazard in the reaction process and low yield. Therefore, there is still an urgent need to develop a new, safe and efficient synthetic route for storax acetate, which can synthesize storax acetate simply, efficiently and under mild conditions.
The invention comprises the following steps:
the invention aims to provide a method for synthesizing storax acetate, which takes acetophenone and acetic anhydride as reaction raw materials, and synthesizes the storax acetate through two steps of reactions, so that the yield of the storax acetate reaches more than 89% and the GC purity reaches more than 99% without purifying intermediates.
The technical problems to be solved by the invention are realized by adopting the following technical scheme:
a process for synthesizing high-purity storax acetate includes such steps as hydrogenation reaction of acetophenone to obtain storax alcohol, esterifying reaction of storax alcohol with acetic anhydride to obtain storax acetate, and high-purity storax acetate.
The reaction route is as follows:
the beneficial effects of the invention are as follows:
(1) The synthesis method provided by the invention adopts acetophenone and acetic anhydride as reaction raw materials, has the advantages of low-cost and easily-obtained raw materials, short synthesis route, simple and convenient operation, no byproduct hydrogen chloride gas generation, high yield and good purity of the product styryl acetate, easy amplification and good application prospect.
(2) The synthesis method provided by the invention adopts the organic acid as the esterification catalyst, so that the organic acid has good solubility in the storax and no precipitation risk; the dosage is small, and the catalytic efficiency is high; meanwhile, the organic acid can be recycled, so that the cost and the environmental pollution are reduced.
(3) According to the synthesis method provided by the invention, morpholine is added to inhibit the activity of the hydrogenation catalyst, the selectivity of Gao Jiaqing is improved, the yield of the intermediate styrol reaches more than 95%, the purification operation of the intermediate styrol is omitted, the esterification reaction is directly carried out, and the yield of the product styryl acetate is improved.
(4) The synthesis method provided by the invention can be used for recovering the byproduct acetic acid, so that the esterification reaction process can be accelerated, and the conversion rate of the intermediate storax and the yield of the product storax acetate are improved; but also can enhance the environmental protection of the process, reduce the waste liquid generation amount and improve the economic benefit.
Description of the drawings:
FIG. 1 is a GC diagram of the synthesized storax of example 1;
FIG. 2 is a GC diagram of the storax acetate synthesized in example 1;
FIG. 3 is a GC diagram of the synthesized storax in the comparative example.
The specific embodiment is as follows:
the invention is further described below with reference to specific embodiments and illustrations in order to make the technical means, the creation features, the achievement of the purpose and the effect of the implementation of the invention easy to understand.
The invention provides a method for synthesizing high-purity storax acetate, which comprises the steps of synthesizing storax alcohol through acetophenone through hydrogenation reaction, and synthesizing the storax acetate through esterification reaction of the storax alcohol and acetic anhydride.
The reaction route is as follows:
preferably, the catalyst of the hydrogenation reaction is at least one of palladium carbon, ruthenium carbon and Raney nickel. Other noble metal hydrogenation catalysts commonly used in the art or supported hydrogenation catalysts with noble metal elements as the active component may also be employed.
Preferably, the catalyst is used in an amount of 1 to 5% by mass of acetophenone. The catalyst consumption is reduced as much as possible while the catalytic effect is ensured, and the catalyst cost is reduced.
Preferably, the temperature of the hydrogenation reaction is 80-120 ℃ and the pressure is 8-15 Bar. The synthesis of the storax by acetophenone hydrogenation is realized by controlling the reaction temperature and the hydrogen pressure.
Preferably, the inhibitor of the hydrogenation reaction is morpholine. The activity of the hydrogenation catalyst is inhibited by adding morpholine, the selectivity of Gao Jiaqing is improved, and the yield and purity of the intermediate threitol are improved.
Preferably, the morpholine is used in an amount of 1-3% of the acetophenone mass. The dosage of morpholine needs to be controlled, the activity of a hydrogenation catalyst is ensured, and the high-efficiency synthesis of the intermediate threitol is realized.
Preferably, the catalyst for the esterification reaction is an organic acid. Organic acid is used as catalyst for esterification reaction to reduce corrosion to equipment and to reduce pollution of waste liquid by recovering organic acid.
Preferably, the organic acid is at least one of methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid.
Preferably, the organic acid is used in an amount of 0.3 to 0.6% by mass of the storax. The dosage of the organic acid needs to be controlled, the catalytic activity is ensured, meanwhile, the acidity of a reaction system is reduced, and the recovery energy consumption and time investment of the organic acid are reduced.
Preferably, the molar ratio of the storax to the acetic anhydride is 1 (1-1.5). The excessive acetic anhydride can make the storax participate in the process as completely as possible, and the conversion rate of the storax is improved.
The following describes the technical scheme of the present invention in detail through specific embodiments:
example 1
1. Synthesis of storax by acetophenone hydrogenation
200g of acetophenone, 2g of morpholine and 4g of ruthenium carbon are added into a hydrogenation kettle together, and hydrogenation reaction is carried out for 8 hours at the temperature of 100 ℃ under the pressure of 12 Bar. After the completion of the hydrogenation, ruthenium carbon was filtered off (recovered) to obtain 196g of intermediate storax. GC analysis: the raw material remained 0.52%, impurity peak 3.22%, product 95.40%, as shown in fig. 1.
2. Synthesis of storax acetate by esterification of storax alcohol and acetic anhydride
120g of storax and 120g of acetic anhydride are added into a three-mouth bottle, 0.6g of benzenesulfonic acid is added, the reaction is carried out for 2 hours at 100 ℃, unreacted acetic acid is removed by flash evaporation at 60 ℃ after the reaction is finished, the flash evaporation is carried out at 100 ℃ to obtain a front distillation and a crude product, and the front distillation of the two flash distillation is combined to obtain a recovery material. The product is washed with 20g of 5% sodium carbonate solution, and the upper organic phase is separated into layers to make the acid value less than or equal to 2. The organic phase was flashed at 100deg.C to give 142g of the product with a GC purity of 99.50% as shown in FIG. 2.
Example 2
1. Synthesis of storax by acetophenone hydrogenation
200g of acetophenone, 2g of morpholine and 4g of Raney nickel are added into a hydrogenation kettle together, and hydrogenation reaction is carried out for 6 hours at the temperature of 100 ℃ under the pressure of 12 Bar. At the end of the hydrogenation, raney nickel was filtered off (recovered) to give 194g of intermediate storax. GC analysis: the residue of the raw material is 0.41%, the impurity peak is 2.39%, and the product is 95.87%.
2. Synthesis of storax acetate by esterification of storax alcohol and acetic anhydride
120g of storax and 120g of acetic anhydride are added into a three-mouth bottle, 0.6g of p-toluenesulfonic acid is added, the reaction is carried out for 1h at 100 ℃, unreacted acetic acid is removed by flash evaporation at 60 ℃ after the reaction is finished, the flash evaporation is carried out at 100 ℃ to obtain a front distillation and a crude product, and the front distillation of the two flash distillation is combined to obtain a recovery material. The product is washed with 20g of 5% sodium carbonate solution, and the upper organic phase is separated into layers to make the acid value less than or equal to 2. The organic phase was flashed at 100℃to give 141g of product with a GC purity of 99.98%.
Example 3
1. Synthesis of storax by acetophenone hydrogenation
200g of acetophenone, 2g of morpholine and 4g of palladium-carbon are added into a hydrogenation kettle together, and hydrogenation reaction is carried out for 6 hours at the temperature of 100 ℃ under the pressure of 12 Bar. After the completion of the hydrogenation, palladium on carbon was filtered off (recovered) to obtain 192g of intermediate storax. GC analysis: the raw material remained 0.21%, the impurity peak 3.32%, and the product 96.19%.
2. Synthesis of storax acetate by esterification of storax alcohol and acetic anhydride
120g of storax and 120g of acetic anhydride are added into a three-mouth bottle, 0.6g of 0.5wt% of methanesulfonic acid is added for reaction for 1h at 80 ℃, unreacted acetic acid is removed by flash evaporation at 60 ℃ after the reaction is finished, the flash evaporation is carried out at 100 ℃ to obtain a front distillation and a crude product, and the front distillation of the two flash distillation is combined to obtain a recovered material. The product is washed with 20g of 5% sodium carbonate solution, and the upper organic phase is separated into layers to make the acid value less than or equal to 2. The organic phase was flash distilled at 100℃to give 138g of product with a GC purity of 99.95%.
Example 4
1. Synthesis of storax by acetophenone hydrogenation
300g of acetophenone, 3g of morpholine and 6g of Raney nickel are added into a hydrogenation kettle together, and hydrogenation reaction is carried out for 12 hours at the temperature of 100 ℃ under the pressure of 10 Bar. At the end of the hydrogenation, raney nickel was filtered off (recovered) to give 280g of intermediate storax. GC analysis: the raw material remained 0.15%, impurity peak 3.62%, product 93.01%.
2. Synthesis of storax acetate by esterification of storax alcohol and acetic anhydride
240g of storax and 240g of acetic anhydride are added into a three-necked flask, 1.2g of 0.5wt% of methanesulfonic acid is added for reaction for 1h at 80 ℃, unreacted acetic acid is removed by flash evaporation at 60 ℃ after the reaction is finished, a pre-distillation product and a crude product are obtained by flash evaporation at 100 ℃, and the pre-distillation of the two flashes is combined to obtain a recovered material. The product is washed with 40g of 5% sodium carbonate solution, and the upper organic phase is separated into layers to make the acid value less than or equal to 2. The organic phase was flashed at 100deg.C to give product 2793 g with a GC purity of 99.65%.
Comparative example
The comparative example differs from example 1 only in that morpholine was not added as a catalyst in the hydrogenation reaction, and the remaining preparation conditions were the same as in example 1.
GC analysis: the starting material remained 1.07%, impurity peak 63.47%, product 34.14%, as shown in fig. 3.
In conclusion, the addition of morpholine in the hydrogenation reaction can obviously improve the hydrogenation selectivity, further improve the yield and purity of the intermediate threitol, avoid the purification operation of the intermediate threitol, and can directly carry out the next esterification reaction.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A method for synthesizing high-purity storax acetate is characterized by comprising the following steps of: the method comprises the steps of synthesizing the storax through the hydrogenation reaction of acetophenone, and then synthesizing the storax acetate through the condensation reaction of the storax and acetic anhydride.
2. The synthesis method according to claim 1, wherein: the catalyst for the hydrogenation reaction is at least one of palladium carbon, ruthenium carbon and Raney nickel.
3. The synthesis method according to claim 2, characterized in that: the dosage of the catalyst is 1-5% of the acetophenone by mass.
4. The synthesis method according to claim 1, wherein: the temperature of the hydrogenation reaction is 80-120 ℃ and the pressure is 8-15 Bar.
5. The synthesis method according to claim 1, wherein: the inhibitor of the hydrogenation reaction is morpholine.
6. The method of synthesis according to claim 5, wherein: the dosage of the morpholine is 1-3% of the acetophenone.
7. The synthesis method according to claim 1, wherein: the catalyst of the condensation reaction is an organic acid.
8. The method of synthesis according to claim 7, wherein: the organic acid is at least one selected from methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid.
9. The method of synthesis according to claim 7, wherein: the dosage of the organic acid is 0.3 to 0.6 percent of the mass of the threitol.
10. The synthesis method according to claim 1, wherein: the molar use ratio of the storax to the acetic anhydride is 1 (1-1.5).
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