CN112961121B - Synthesis process of cooling agent intermediate 1, 2-epoxy-3-L-menthoxypropane - Google Patents
Synthesis process of cooling agent intermediate 1, 2-epoxy-3-L-menthoxypropane Download PDFInfo
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- CN112961121B CN112961121B CN202110150705.1A CN202110150705A CN112961121B CN 112961121 B CN112961121 B CN 112961121B CN 202110150705 A CN202110150705 A CN 202110150705A CN 112961121 B CN112961121 B CN 112961121B
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- QSPXTBSJQJHAPF-UHFFFAOYSA-N 2-[(1-methyl-4-propan-2-ylcyclohexyl)oxymethyl]oxirane Chemical compound C1CC(C(C)C)CCC1(C)OCC1OC1 QSPXTBSJQJHAPF-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000002826 coolant Substances 0.000 title claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 claims abstract description 31
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229940041616 menthol Drugs 0.000 claims abstract description 31
- 238000009835 boiling Methods 0.000 claims abstract description 28
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000003208 petroleum Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000006276 transfer reaction Methods 0.000 claims description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- -1 alkyl hydrocarbon Chemical class 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 239000003444 phase transfer catalyst Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 2
- 239000011261 inert gas Substances 0.000 abstract description 8
- 238000004821 distillation Methods 0.000 abstract description 6
- 239000012046 mixed solvent Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000013076 target substance Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- IMVMIMWLBYHMBW-UHFFFAOYSA-N 1-chloro-3-(1-methyl-4-propan-2-ylcyclohexyl)oxypropan-2-ol Chemical compound CC(C)C1CCC(C)(OCC(O)CCl)CC1 IMVMIMWLBYHMBW-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 235000019504 cigarettes Nutrition 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- MDVYIGJINBYKOM-UHFFFAOYSA-N 3-[[5-Methyl-2-(1-methylethyl)cyclohexyl]oxy]-1,2-propanediol Chemical compound CC(C)C1CCC(C)CC1OCC(O)CO MDVYIGJINBYKOM-UHFFFAOYSA-N 0.000 description 1
- 235000006679 Mentha X verticillata Nutrition 0.000 description 1
- 235000002899 Mentha suaveolens Nutrition 0.000 description 1
- 235000001636 Mentha x rotundifolia Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019658 bitter taste Nutrition 0.000 description 1
- 229940112822 chewing gum Drugs 0.000 description 1
- 235000015218 chewing gum Nutrition 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 235000015094 jam Nutrition 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 235000013622 meat product Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000019640 taste Nutrition 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
-
- 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
Abstract
The invention discloses a synthesis process of a cooling agent intermediate 1, 2-epoxy-3-L-menthoxypropane, which adopts raw materials such as menthol, epoxy chloropropane, tetrabutylammonium bromide and the like, abandons inert gas, does not need a pressure-bearing reaction kettle, synthesizes 1, 2-epoxy-3-L-menthoxypropane through one-pot operation, has short reaction time, does not have byproducts, completely converts menthol raw materials into target substances, reduces purification steps, does not need to adopt low temperature, reduces energy consumption, adopts a linear boiling difference mixed solvent external circulation technology to replace inert gas, and then obtains the 1, 2-epoxy-3-L-menthoxypropane with the purity of more than 99 percent through simple reduced pressure distillation, and has the one-time yield of more than 98.5 percent, and the process is environment-friendly and safe.
Description
Technical Field
The invention relates to the technical field of cooling agents, and in particular belongs to a synthesis process of a cooling agent intermediate 1, 2-epoxy-3-L-menthoxypropane.
Background
Natural menthol has important application as a cooling agent in daily chemical industry, food, medicine and cigarette products, but because of high volatility and irritation of menthol, the cooling effect is short and strong, even the menthol is harmful to human skin and eyes, and the special mint smell limits the wide application of menthol in daily chemical products. The novel water-soluble cooling agent ws-10 (3-L-menthoxypropane-1, 2-diol) has the characteristics of strong water solubility, clear and pleasant taste, durability, freshness, no pungency and no bitter taste. Can be widely used for chewing gum, toothpaste, candy, jelly, jam, starch food, meat products, cigarettes, medicines and other products, so that the synthesis research of the 1, 2-epoxy-3-L-menthoxypropane as the WS-10 intermediate is of great practical significance.
The 1, 2-epoxy-3-L-menthoxypropane is obtained by using menthol, 1, 2-epoxy-3-chloropropane and a phase transfer catalyst, but the existing reaction is carried out in two steps under the protection of inert gas, the menthol and the 1, 2-epoxy-3-chloropropane in the first step respectively carry out ring opening reaction on anhydrous aluminum trichloride or zinc chloride, the 1-chloro-3-L-menthoxy-2-propanol is obtained by distillation, and the 1-chloro-3-L-menthoxy-2-propanol is obtained by distillation through the phase transfer reaction. Firstly, carrying out ring opening reaction, namely, carrying out distillation on anhydrous aluminum trichloride or zinc chloride under the condition of inert gas, separating unreacted menthol to obtain 1-chloro-3-L-menthoxy-2-propanol, wherein the 1, 2-epoxy-3-chloropropane is easy to carry out decomposition reaction in the ring opening process, so that byproducts are generated, the subsequent purification difficulty is high, and the yield is low; in the second step, under the condition of strict inert gas, the oxygen content is controlled, the influence of air on the phase transfer reaction is reduced, the requirement on a phase transfer catalyst is strict, incomplete phase transfer is easy to occur, the yield is reduced, excessive waste liquid is caused, the cost is gradually increased, the profit margin is reduced, and the current environmental protection and economic harmony development are not facilitated.
Disclosure of Invention
The invention aims to provide a synthesis process of a cooling agent intermediate 1, 2-epoxy-3-L-menthoxypropane, which overcomes the defects that the traditional synthesis process method has incomplete menthol reaction, overlong reaction time and more byproducts, the post-treatment needs distillation to purify and remove part of the byproducts, and meanwhile, a pressure-bearing reaction kettle is adopted to introduce inert gas, so that the reaction condition is harsh, and the industrial production is not facilitated.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the synthesis process of the cooling agent intermediate 1, 2-epoxy-3-L-menthoxypropane comprises the following steps:
s1, adding menthol, toluene, an organic reagent with a boiling range of 30-60 ℃, tetrahydrofuran, ethyl acetate and cyclohexane into a reaction kettle, heating and stirring until menthol is completely dissolved, then adding aluminum trichloride to enable the temperature in the reaction kettle to rise to 45-50 ℃, stirring, performing condensation reflux reaction, stopping condensation, enabling part of solvent to be heated and evaporated out of the reaction kettle, then continuing the condensation reflux reaction, simultaneously dropwise adding a mixed solution into a reaction system, and continuing heating and heat preservation after dropwise adding is completed to enable menthol to be completely converted;
s2, dropwise adding deionized water into a reaction system after menthol is completely converted, stirring, standing for layering, separating out lower water in a reaction kettle, and then adding alkali liquor and a phase transfer catalyst into the reaction kettle for phase transfer reaction;
s3, heating is started, part of the solvent is heated and evaporated out of the reaction kettle, and then condensation reflux reaction is carried out until the phase transfer reaction is finished;
s4, adding deionized water into the reaction kettle after the phase transfer reaction is finished until turbidity disappears in the reaction kettle, stirring and standing, separating a lower layer water layer, and then recovering a solvent in the reaction kettle to obtain the 1, 2-epoxy-3-L-menthoxypropane.
Preferably, the mass ratio of menthol, toluene, organic reagent with boiling range of 30-60 ℃, tetrahydrofuran, ethyl acetate and cyclohexane is 500:192:20:15:5:5.
Preferably, the organic reagent with the boiling range of 30-60 ℃ is petroleum ether with the boiling range of 30-60 ℃.
Preferably, the mixed solution is a mixture of epichlorohydrin and alkyl hydrocarbon.
Preferably, the mass ratio of the epichlorohydrin to the alkyl hydrocarbon is 412:5.
Preferably, the alkyl hydrocarbon is petroleum ether having a boiling range of 60-90 ℃.
Preferably, the lye is 41.2wt% sodium hydroxide aqueous solution.
Preferably, the phase transfer catalyst is tetrabutylammonium bromide.
Preferably, the time for evaporating part of the solvent out of the reaction kettle under heating is 10min.
Compared with the prior art, the invention has the following implementation effects:
1. the synthesis technology adopts menthol and 1, 2-epoxy-3-chloropropane, tetrabutylammonium bromide and other raw materials, abandons inert gas, does not need a pressure-bearing reaction kettle, synthesizes 1, 2-epoxy-3-L-menthoxypropane through one-pot operation, has short reaction time, does not have byproducts, completely converts menthol raw materials into target substances, reduces purification steps, does not need to adopt low temperature, reduces energy consumption, adopts a linear boiling difference mixed solvent technology to replace inert gas, and then obtains the 1, 2-epoxy-3-L-menthoxypropane with the purity of more than 99 percent through simple reduced pressure distillation, wherein the one-time yield can reach more than 98.5 percent, and is relatively environment-friendly and safe.
2. According to the invention, a linear boiling difference mixed solvent consisting of toluene, petroleum ether with the boiling range of 30-60 ℃, tetrahydrofuran, ethyl acetate and cyclohexane is used, when the solvent is heated and evaporated, the low-boiling point solvent can discharge most of air in the reaction kettle, so that the space of the reaction kettle is filled with solvent gas, the dropped epichlorohydrin is kept from being decomposed, part of petroleum ether with the boiling range of 60-90 ℃ is added into the mixed solution, and the petroleum ether with the boiling range of 60-90 ℃ is insoluble with the epichlorohydrin, so that the petroleum ether with the boiling range of 60-90 ℃ can seal the contact between the epichlorohydrin and the air on the upper layer, the product yield is greatly improved, the product quality is unchanged, the operation is simple, and the economic type is good.
3. The process method finally adds deionized water to make the solution become turbid, so that tetrabutylammonium bromide is completely dissolved, and the solvent is favorable for recovery.
4. The process method is convenient to operate, the 1, 2-epoxy-3-L-menthoxypropane product with higher purity is easy to obtain, the risk of industrial production is reduced, and the method has double significance of economy and environmental protection.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Firstly, installing a tower section and a condenser on a 2000L reaction kettle to form an external circulation channel, then weighing 500kg of menthol into the reaction kettle, adding 192kg of toluene, 20kg of petroleum ether with the boiling range of 30-60 ℃, 15kg of tetrahydrofuran, 5kg of ethyl acetate and 5kg of cyclohexane to form a series of mixed solvents with linear boiling points, starting stirring, and starting heating to ensure that the menthol is completely dissolved at the internal temperature of 41 ℃; then adding 0.15kg of aluminum trichloride, automatically raising the internal temperature of the reaction kettle to 49 ℃, stirring for 30min, opening an external circulation channel outwards, allowing part of evaporated solvent liquid to flow out of the whole reaction system for 10min, closing an external circulation outwards channel to enable circulating liquid to flow back into the reaction kettle, pumping 412kg of epichlorohydrin and 5kg of petroleum ether with the boiling range of 60-90 ℃ into a high-level tank to form semi-mixed liquid, and allowing most of petroleum ether with the boiling range of 60-90 ℃ to be at the upper layer; the heating temperature of the reaction kettle is controlled at 45 ℃, the mixed solution is dripped, and the dripping speed is controlled at about 10L/min; after the dripping is finished, heating and preserving heat for 1 hour, after the menthol is completely converted and preserving heat is finished, dripping 100kg of deionized water into the kettle, and continuously stirring for 30 minutes; stopping stirring, standing, and separating out lower water;
then 750kg of 41.2% sodium hydroxide aqueous solution is pumped into the kettle, 0.3kg of tetrabutylammonium bromide is added, stirring is started for 30min, and phase transfer reaction occurs; heating is started, an external circulation channel is opened outwards, part of liquid flows out of the whole reaction system for 10min, then the external circulation external channel is closed, so that circulating liquid flows back into the kettle, and the temperature in the kettle is controlled at 77 ℃; preserving the temperature for 2.5 hours, after the phase transfer is completed, pumping 300kg of deionized water into the reaction kettle, and eliminating turbidity in the reaction kettle; stirring for 10min, standing, and discharging lower water; vacuumizing the reaction kettle to-0.098 Mpa, recovering the solvent under reduced pressure, and stopping heating until the temperature in the kettle reaches 87 ℃ to obtain 671kg of 1, 2-epoxy-3-L-menthoxypropane with the purity of 99.3% and the one-time yield of 98.75%.
Example 2
Firstly, installing a tower section and a condenser on a 2000L reaction kettle to form an external circulation channel, then weighing 500kg of menthol into the reaction kettle, adding 192kg of toluene, 20kg of petroleum ether with the boiling range of 30-60 ℃, 15kg of tetrahydrofuran, 5kg of ethyl acetate and 5kg of cyclohexane to form a series of mixed solvents with linear boiling points, starting stirring, and starting heating to ensure that the menthol is completely dissolved at the internal temperature of 45 ℃; then adding 0.15kg of aluminum trichloride, automatically raising the internal temperature of the reaction kettle to 50 ℃, stirring for 30min, opening an external circulation channel outwards, allowing part of evaporated solvent liquid to flow out of the whole reaction system for 10min, closing an external circulation outwards channel to enable circulating liquid to flow back into the reaction kettle, pumping 412kg of epichlorohydrin and 5kg of petroleum ether with the boiling range of 60-90 ℃ into a high-level tank to form semi-mixed liquid, and allowing most of petroleum ether with the boiling range of 60-90 ℃ to be at the upper layer; the heating temperature of the reaction kettle is controlled at 54 ℃, the mixed solution is dripped, and the dripping speed is controlled at about 10L/min; after the dripping is finished, heating and preserving heat for 1 hour, after the menthol is completely converted and preserving heat is finished, dripping 100kg of deionized water into the kettle, and continuously stirring for 30 minutes; stopping stirring, standing, and separating out lower water;
then 750kg of 41.2% sodium hydroxide aqueous solution is pumped into the kettle, 0.3kg of tetrabutylammonium bromide is added, stirring is started for 30min, and phase transfer reaction occurs; heating is started, an external circulation channel is opened outwards, part of liquid flows out of the whole reaction system for 10min, then the external circulation external channel is closed, so that circulating liquid flows back into the kettle, and the temperature in the kettle is controlled at 78 ℃; preserving the temperature for 2.5 hours, after the phase transfer is completed, pumping 300kg of deionized water into the reaction kettle, and eliminating turbidity in the reaction kettle; stirring for 10min, standing, and discharging lower water; vacuumizing the reaction kettle to-0.098 Mpa, recovering the solvent under reduced pressure, and stopping heating until the temperature in the kettle reaches 87 ℃ to obtain 669.1kg of 1, 2-epoxy-3-L-menthoxypropane with the purity of 99.6% and the disposable yield of 98.47%.
Example 3
Firstly, installing a tower section and a condenser on a 2000L reaction kettle to form an external circulation channel, then weighing 500kg of menthol into the reaction kettle, adding 192kg of toluene, 20kg of petroleum ether with the boiling range of 30-60 ℃, 15kg of tetrahydrofuran, 5kg of ethyl acetate and 5kg of cyclohexane to form a series of mixed solvents with linear boiling points, starting stirring, and starting heating to ensure that the menthol is completely dissolved at the internal temperature of 45 ℃; then adding 0.15kg of aluminum trichloride, automatically raising the internal temperature of the reaction kettle to 47 ℃, stirring for 30min, opening an external circulation channel outwards, allowing part of evaporated solvent liquid to flow out of the whole reaction system for 10min, closing an external circulation outwards channel to enable circulating liquid to flow back into the reaction kettle, pumping 412kg of epichlorohydrin and 5kg of petroleum ether with the boiling range of 60-90 ℃ into a high-level tank to form semi-mixed liquid, and allowing most of petroleum ether with the boiling range of 60-90 ℃ to be at the upper layer; the heating temperature of the reaction kettle is controlled at 53 ℃, the mixed solution is dripped, and the dripping speed is controlled at about 10L/min; after the dripping is finished, heating and preserving heat for 1 hour, after the menthol is completely converted and preserving heat is finished, dripping 100kg of deionized water into the kettle, and continuously stirring for 30 minutes; stopping stirring, standing, and separating out lower water;
then 750kg of 41.2% sodium hydroxide aqueous solution is pumped into the kettle, 0.3kg of tetrabutylammonium bromide is added, stirring is started for 30min, and phase transfer reaction occurs; heating is started, an external circulation channel is opened outwards, part of liquid flows out of the whole reaction system for 10min, then the external circulation external channel is closed, so that circulating liquid flows back into the kettle, and the temperature in the kettle is controlled at 85 ℃; preserving the temperature for 2.5 hours, after the phase transfer is completed, pumping 300kg of deionized water into the reaction kettle, and eliminating turbidity in the reaction kettle; stirring for 10min, standing, and discharging lower water; vacuumizing the reaction kettle to-0.098 Mpa, recovering the solvent under reduced pressure, and stopping heating until the temperature in the kettle reaches 89 ℃ to obtain 670.0kg of 1, 2-epoxy-3-L-menthoxypropane with the purity of 99.70% and the disposable yield of 98.60%.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (3)
1. The synthesis process of the cooling agent intermediate 1, 2-epoxy-3-L-menthoxypropane is characterized by comprising the following steps of: the method comprises the following steps:
s1, adding menthol, toluene, petroleum ether with the boiling range of 30-60 ℃, tetrahydrofuran, ethyl acetate and cyclohexane into a reaction kettle, heating and stirring until menthol is completely dissolved, then adding aluminum trichloride to enable the temperature in the reaction kettle to rise to 45-50 ℃, stirring, performing condensation reflux reaction, stopping condensation, enabling part of solvent to be heated and evaporated out of the reaction kettle, then continuing the condensation reflux reaction, simultaneously dropwise adding a mixed solution into the reaction system, and continuing heating and heat preservation after dropwise adding is completed, so that menthol is completely converted;
s2, dropwise adding deionized water into a reaction system after menthol is completely converted, stirring, standing for layering, separating out lower water in a reaction kettle, and then adding alkali liquor and a phase transfer catalyst into the reaction kettle for phase transfer reaction;
s3, heating is started, part of the solvent is heated and evaporated out of the reaction kettle, and then condensation reflux reaction is carried out until the phase transfer reaction is finished;
s4, adding deionized water into the reaction kettle after the phase transfer reaction is finished until turbidity disappears in the reaction kettle, stirring and standing, separating a lower layer of water layer, and then recovering a solvent in the reaction kettle to obtain 1, 2-epoxy-3-L-menthoxypropane;
the mass ratio of menthol, toluene, petroleum ether with the boiling range of 30-60 ℃, tetrahydrofuran, ethyl acetate and cyclohexane is 500:192:20:15:5:5;
the mixed solution is a mixture of epoxy chloropropane and alkyl hydrocarbon;
the mass ratio of the epichlorohydrin to the alkyl hydrocarbon is 412:5;
the alkyl hydrocarbon is petroleum ether with the boiling range of 60-90 ℃;
the phase transfer catalyst is tetrabutylammonium bromide.
2. The process for synthesizing the cooling agent intermediate 1, 2-epoxy-3-L-menthoxypropane according to claim 1, which is characterized in that: the alkali liquor is 41.2wt% sodium hydroxide aqueous solution.
3. The process for synthesizing the cooling agent intermediate 1, 2-epoxy-3-L-menthoxypropane according to claim 1, which is characterized in that: the time for evaporating part of the solvent out of the reaction kettle by heating is 10min.
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