CN112341318A - Method for preparing thick vanilline from sassafras oil - Google Patents
Method for preparing thick vanilline from sassafras oil Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000010672 sassafras oil Substances 0.000 title claims abstract description 29
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- BJIOGJUNALELMI-ONEGZZNKSA-N Isoeugenol Natural products COC1=CC(\C=C\C)=CC=C1O BJIOGJUNALELMI-ONEGZZNKSA-N 0.000 claims abstract description 18
- BJIOGJUNALELMI-ARJAWSKDSA-N cis-isoeugenol Chemical compound COC1=CC(\C=C/C)=CC=C1O BJIOGJUNALELMI-ARJAWSKDSA-N 0.000 claims abstract description 18
- BJIOGJUNALELMI-UHFFFAOYSA-N trans-isoeugenol Natural products COC1=CC(C=CC)=CC=C1O BJIOGJUNALELMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940008406 diethyl sulfate Drugs 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 66
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- RADIRXJQODWKGQ-HWKANZROSA-N 2-Ethoxy-5-(1-propenyl)phenol Chemical compound CCOC1=CC=C(\C=C\C)C=C1O RADIRXJQODWKGQ-HWKANZROSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 24
- 238000010992 reflux Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- -1 methoxy isoeugenol potassium salt Chemical compound 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 239000001103 potassium chloride Substances 0.000 claims description 6
- 235000011164 potassium chloride Nutrition 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- CBOQJANXLMLOSS-UHFFFAOYSA-N ethyl vanillin Chemical compound CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 abstract description 16
- 239000006227 byproduct Substances 0.000 abstract description 10
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 abstract description 9
- 235000012141 vanillin Nutrition 0.000 abstract description 9
- 229940073505 ethyl vanillin Drugs 0.000 abstract description 8
- 239000000047 product Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 238000007142 ring opening reaction Methods 0.000 abstract description 6
- 238000006200 ethylation reaction Methods 0.000 abstract description 5
- 230000006203 ethylation Effects 0.000 abstract description 3
- 238000006317 isomerization reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 235000008671 Calycanthus floridus Nutrition 0.000 abstract 1
- 235000008670 Calycanthus occidentalis Nutrition 0.000 abstract 1
- 244000148992 Lindera benzoin Species 0.000 abstract 1
- 235000004520 Lindera benzoin Nutrition 0.000 abstract 1
- 235000008262 Lindera benzoin var. benzoin Nutrition 0.000 abstract 1
- ZMQAAUBTXCXRIC-UHFFFAOYSA-N safrole Chemical compound C=CCC1=CC=C2OCOC2=C1 ZMQAAUBTXCXRIC-UHFFFAOYSA-N 0.000 description 20
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 10
- BXOCHUWSGYYSFW-HVWOQQCMSA-N spilanthol Chemical compound C\C=C\C=C/CC\C=C\C(=O)NCC(C)C BXOCHUWSGYYSFW-HVWOQQCMSA-N 0.000 description 10
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 6
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 5
- 239000005770 Eugenol Substances 0.000 description 5
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 5
- BXOCHUWSGYYSFW-UHFFFAOYSA-N all-trans spilanthol Natural products CC=CC=CCCC=CC(=O)NCC(C)C BXOCHUWSGYYSFW-UHFFFAOYSA-N 0.000 description 5
- 229960002217 eugenol Drugs 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 239000003205 fragrance Substances 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- NPHBPWBHHFJTHW-UHFFFAOYSA-N C(C)[Na].S(O)(O)(=O)=O Chemical compound C(C)[Na].S(O)(O)(=O)=O NPHBPWBHHFJTHW-UHFFFAOYSA-N 0.000 description 3
- AOSKXPFBGRLCEG-UHFFFAOYSA-N 1-ethoxy-2-methoxy-4-prop-1-enylbenzene Chemical compound CCOC1=CC=C(C=CC)C=C1OC AOSKXPFBGRLCEG-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 238000010520 demethylation reaction Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003444 phase transfer catalyst 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
- 238000002360 preparation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 241000628997 Flos Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 244000227633 Ocotea pretiosa Species 0.000 description 1
- 235000004263 Ocotea pretiosa Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 244000263375 Vanilla tahitensis Species 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention discloses a method for preparing fragrant spicebush from sassafras oil, which adopts sassafras oil as a raw material, adjusts the dosage of KOH and methanol during ring opening isomerization of the sassafras oil, adopts a method of distilling methanol with water to carry out ring opening, has milder and controllable reaction, does not acidify a ring opening product, and then directly uses diethyl sulfate to carry out ethylation, greatly reduces the reaction temperature, has simple process and high yield; meanwhile, the ethyl vanillin is synthesized from a byproduct iso-eugenol generated in the production process through an oxidation reaction, so that the treatment process and the cost of the byproduct are reduced, the cost is further reduced by selling the byproduct ethyl vanillin, and the method is an ideal route for industrially preparing the strong vanillin.
Description
Technical Field
The invention relates to the technical field of organic chemical synthesis, in particular to a method for preparing fragrant spilanthol from sassafras oil.
Background
The thick vanilline, the chemical name of which is 2-ethoxy-5- (1-propenyl) phenol, is a white flaky crystal, has the melting point of 85-87 ℃, is slightly soluble in water, is dissolved in ethanol by 10 percent and is dissolved in benzyl alcohol by 20 percent. It has strong and lasting fragrance of flos Caryophylli and vanilla, fragrance intensity 16-25 times of vanillin, and can be used in food essence formula such as ice cream, candy, chocolate, etc., or used in soap and cosmetics, and can be used as antioxidant and synergist.
The strong fragrance vanillin is developed successfully as early as 20 th century, the initial synthetic route is to take safrole as a raw material, carry out hot-pressing reaction on the safrole and an alcoholic solution of potassium hydroxide to open a ring, carry out hydroxyl ethylation on the ring by adopting ethyl sodium sulfate, and finally hydrolyze the ring in an alcoholic solution by adopting sulfuric acid to obtain the strong fragrance vanillin. However, the method has poor aroma purity, so that the method is rarely applied to practical application. In the 50 s of the 20 th century, a synthetic route for preparing the concentrated vanilline from eugenol is developed to realize industrial production, and a common preparation method is to synthesize eugenol ethyl ether by taking eugenol as a raw material, then taking diethyl carbonate as an ethylation reagent and catalyzing by potassium carbonate; then adopts KOH and Phase Transfer Catalyst (PTC) polyethylene glycol to isomerize the eugenol ethyl ether into isoeugenol ethyl ether; finally, aluminum trichloride is used as a catalyst to catalyze the demethylation of isoeugenol ethyl ether to generate the vanitropane, but the demethylation reaction yield of the last step of the process route is too low and is only about 38%. The aroma chemist of the Soviet Union before the 60 th century in the 20 th century successfully developed a synthetic route using more cheap and easily available catechol as a raw material, and the catechol was monoalkylated by allyl chloride, and the yield was 75%; then carrying out rearrangement reaction, wherein the yield is 35-38%; then, the ethyl sodium sulfate is used for mono-ethylation, and the yield is 82%; finally, potassium hydroxide is used for isomerization to obtain the thick vanilline, the yield is 84%, the melting point of a crude product after recrystallization is 85.5-86 ℃, the raw materials are cheap and easy to obtain in the route, but the process route is long and the yield is very low.
In the synthetic route of the fragrant spilanthol, the fragrant spilanthol is synthesized by a eugenol route, and the problems of low yield, few and expensive raw material sources, high manufacturing cost and the like exist. The synthesis process using catechol as raw material has the disadvantages of long route and low yield (only 20%). The prior art for synthesizing the thick fragrant vanillin by the safrole has potential safety hazard in the reaction when the safrole is subjected to ring opening or is subjected to hot-pressing reaction with an alcohol-alkali solution or is subjected to normal-pressure reaction with metallic sodium, and meanwhile, the ethyl sodium sulfate is adopted in the ethylation reaction, the reaction temperature is about 150 ℃, and the temperature is too high.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide the method for preparing the fragrant vanillin from the sassafras oil, which has the advantages of simple process, milder and controllable reaction conditions and high product purity and yield.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing fragrant spilanthol from sassafras oil, which comprises the following steps:
s1, adding the sassafras oil, the methanol and the potassium hydroxide into a reaction kettle simultaneously, stirring, controlling the reaction temperature at 130-;
s2, stopping the reaction after the reaction is finished, cooling, adding a proper amount of water while stirring, standing for layering, and collecting the upper-layer methoxy isoeugenol sylvite solution;
s3, adding the methoxy isoeugenol potassium salt solution collected in the step S2 and diethyl sulfate into another reaction kettle, stirring, raising the temperature to 80-100 ℃, keeping the temperature for reaction for 2-3 hours, after the reaction is finished, sequentially adding a proper amount of water and toluene while stirring, standing for layering, and collecting an upper methylbenzene phase;
s4, carrying out rotary evaporation on the toluene phase obtained in the step S3 to recover toluene, then carrying out reduced pressure distillation, and collecting mixed ether fractions;
s5, sequentially adding the mixed ether fraction obtained in the step S4, alcohol, water and concentrated sulfuric acid into a reaction container, heating to a reflux temperature, carrying out reflux reaction for 2-3 hours, cooling and standing after the reaction is finished, crystallizing and separating out the vanitrope, and filtering to obtain a crude vanitrope and an alcohol aqueous solution containing isoeugenol;
s6, recrystallizing the crude vanitrope prepared in the step S5 to obtain the finished vanitrope.
Preferably, in the step S1, the mass ratio of the safrole oil, the methanol and the potassium hydroxide is (1-2) to (1-2): (2-6).
Preferably, in the step S2, the mixed solution in the reaction kettle is sampled, and when the content of safrole in the mixed solution is less than 1%, the reaction is determined to be finished.
Preferably, in step S3, the mass ratio of the methoxy isoeugenol potassium salt solution to diethyl sulfate is (2-6): (1-2).
Preferably, in step S5, the mass ratio of the mixed ether fraction, the alcohol, the water, and the concentrated sulfuric acid is (1-3): (2-8): (2-8): (0.01-0.05).
Preferably, in step S2, the temperature is reduced to 90 ℃ or lower.
Preferably, in the step S6, an aqueous alcohol solution is used to recrystallize the crude vanitrope, and the alcohol concentration in the aqueous alcohol solution is 10% to 30%.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, sassafras oil is used as a raw material, the dosage of KOH and methanol is adjusted during ring opening isomerization of sassafras, and ring opening is carried out by adopting a method of distilling methanol with water, so that the reaction is milder and controllable, the ring-opened product is not acidified, and then the ethyl reaction is directly carried out by using diethyl sulfate, the reaction temperature is greatly reduced, the process is simple, and the yield is high; meanwhile, the ethyl vanillin is synthesized from a byproduct iso-eugenol generated in the production process through an oxidation reaction, so that the treatment process and the cost of the byproduct are reduced, the cost is further reduced by selling the byproduct ethyl vanillin, and the method is an ideal route for industrially preparing the strong vanillin.
Drawings
The invention is described in further detail below with reference to specific embodiments and with reference to the following drawings.
FIG. 1 is a process flow diagram of the preparation of vanilline from sassafras oil according to the present invention.
Detailed Description
Example 1
A method for preparing vanilline from sassafras oil comprises the following steps:
s1, adding 100g of sassafras oil, 100g of methanol and 100g of potassium hydroxide into a reaction kettle at the same time, stirring, controlling the reaction temperature at 130 ℃, carrying out reflux reaction for 60min, then carrying out normal pressure distillation, raising the temperature to 160 ℃ to distill out the methanol, and continuing the reaction for 4-8 h;
s2, sampling the mixed solution in the reaction kettle, judging that the reaction is finished when the content of safrole in the mixed solution is less than 1%, stopping the reaction after the reaction is finished, cooling to below 100 ℃, adding a proper amount of water while stirring, standing for layering, and collecting the upper-layer methoxy isoeugenol sylvite solution;
s3, adding 320g of methoxy isoeugenol potassium salt solution collected in the step S2 and 108g of diethyl sulfate into another reaction kettle, stirring, raising the temperature to 80 ℃, keeping the temperature for reaction for 2-3 hours, after the reaction is finished, sequentially adding a proper amount of water and toluene while stirring, standing for layering, and collecting an upper methylbenzene phase;
s4, carrying out rotary evaporation on the toluene phase obtained in the step S3 to recover toluene, then carrying out reduced pressure distillation, and collecting mixed ether fractions;
s5, sequentially adding 101g of mixed ether fraction obtained in the step S4, 500g of alcohol, 500g of water and 1.5g of concentrated sulfuric acid into a reaction container, heating to a reflux temperature, carrying out reflux reaction for 2-3h, cooling and standing after the reaction is finished, crystallizing and separating out vanitrope, and filtering to obtain crude vanitrope and an alcohol aqueous solution containing isoeugenol;
s6, recrystallizing the crude vanitrope prepared in the step S5 by using an alcohol aqueous solution to obtain a finished product vanitrope, wherein the alcohol concentration in the alcohol aqueous solution is 10% -30%; and the byproduct isoeugenol is synthesized into ethyl vanillin through oxidation reaction.
Finally, 30g of the finished product of the fragrant spilanthol is obtained through recrystallization, and the purity is 98.2%.
Example 2
A method for preparing vanilline from sassafras oil comprises the following steps:
s1, adding 150g of sassafras oil, 150g of methanol and 400g of potassium hydroxide into a reaction kettle at the same time, stirring, controlling the reaction temperature at 125 ℃, carrying out reflux reaction for 120min, then carrying out normal pressure distillation, raising the temperature to 130-140 ℃, distilling out the methanol, and continuing the reaction for 4-8 h;
s2, sampling the mixed solution in the reaction kettle, judging that the reaction is finished when the content of safrole in the mixed solution is less than 1%, stopping the reaction after the reaction is finished, cooling to below 90 ℃, adding a proper amount of water while stirring, standing for layering, and collecting the upper-layer methoxy isoeugenol sylvite solution;
s3, adding 320g of methoxy isoeugenol potassium salt solution and 320g of diethyl sulfate collected in the step S2 into another reaction kettle, stirring, raising the temperature to 100 ℃, keeping the temperature for reaction for 2-3 hours, after the reaction is finished, sequentially adding a proper amount of water and toluene while stirring, standing for layering, and collecting an upper methylbenzene phase;
s4, carrying out rotary evaporation on the toluene phase obtained in the step S3 to recover toluene, then carrying out reduced pressure distillation, and collecting mixed ether fractions;
s5, sequentially adding 100g of mixed ether fraction obtained in the step S4, 800g of alcohol, 800g of water and 5g of concentrated sulfuric acid into a reaction container, heating to a reflux temperature, carrying out reflux reaction for 2-3h, cooling and standing after the reaction is finished, crystallizing and separating out the vanitrope, and filtering to obtain crude vanitrope and an alcohol aqueous solution containing isoeugenol;
s6, recrystallizing the crude vanitrope prepared in the step S5 by adopting an alcohol aqueous solution, wherein the alcohol concentration in the alcohol aqueous solution is 10-30%; and the byproduct isoeugenol is synthesized into ethyl vanillin through oxidation reaction.
Finally, 35g of the finished product of the fragrant vanillin is obtained through recrystallization, and the purity of the fragrant vanillin is 96.8%.
Example 3
A method for preparing vanilline from sassafras oil comprises the following steps:
s1, adding 100g of sassafras oil, 200g of methanol and 600g of potassium hydroxide into a reaction kettle at the same time, stirring and controlling the reaction temperature at 110 ℃, carrying out reflux reaction for 100min, then carrying out normal pressure distillation and raising the temperature to 160-180 ℃ so as to distill out the methanol, and continuing the reaction for 4-8 h;
s2, sampling the mixed solution in the reaction kettle, judging that the reaction is finished when the content of safrole in the mixed solution is less than 1%, stopping the reaction after the reaction is finished, cooling to below 90 ℃, adding a proper amount of water while stirring, standing for layering, and collecting the upper-layer methoxy isoeugenol sylvite solution;
s3, adding 320g of methoxy isoeugenol potassium salt solution collected in the step S2 and 80g of diethyl sulfate into another reaction kettle, stirring, raising the temperature to 90 ℃, keeping the temperature for reaction for 2-3 hours, after the reaction is finished, sequentially adding a proper amount of water and toluene while stirring, standing for layering, and collecting an upper methylbenzene phase;
s4, carrying out rotary evaporation on the toluene phase obtained in the step S3 to recover toluene, then carrying out reduced pressure distillation, and collecting mixed ether fractions;
s5, sequentially adding 100g of mixed ether fraction, 100g of alcohol, 100g of water and 3g of concentrated sulfuric acid obtained in the step S4 into a reaction container, heating to a reflux temperature, carrying out reflux reaction for 2-3h, cooling and standing after the reaction is finished, crystallizing and separating out the vanitrope, and filtering to obtain crude vanitrope and an alcohol aqueous solution containing isoeugenol;
s6, recrystallizing the crude vanitrope prepared in the step S5 by adopting an alcohol aqueous solution, wherein the alcohol concentration in the alcohol aqueous solution is 10-30%; and the byproduct isoeugenol is synthesized into ethyl vanillin through oxidation reaction.
27g of the finished product of the vanilline after recrystallization is finally obtained, and the purity is 97.5 percent.
Example 4
A method for preparing vanilline from sassafras oil comprises the following steps:
s1, adding 200g of sassafras oil, 100g of methanol and 200g of potassium hydroxide into a reaction kettle at the same time, stirring, controlling the reaction temperature at 130 ℃, carrying out reflux reaction for 120min, then carrying out normal pressure distillation, raising the temperature to 160 ℃ to distill out the methanol, and continuing the reaction for 4-8 h;
s2, sampling the mixed solution in the reaction kettle, judging that the reaction is finished when the content of safrole in the mixed solution is less than 1%, stopping the reaction after the reaction is finished, cooling to below 90 ℃, adding a proper amount of water while stirring, standing for layering, and collecting the upper-layer methoxy isoeugenol sylvite solution;
s3, adding 360g of the methoxy isoeugenol potassium salt solution collected in the step S2 and 60g of diethyl sulfate into another reaction kettle, stirring, raising the temperature to 80 ℃, keeping the temperature for reaction for 2-3 hours, after the reaction is finished, sequentially adding a proper amount of water and toluene while stirring, standing for layering, and collecting an upper methylbenzene phase;
s4, carrying out rotary evaporation on the toluene phase obtained in the step S3 to recover toluene, then carrying out reduced pressure distillation, and collecting mixed ether fractions;
s5, sequentially adding 100g of mixed ether fraction obtained in the step S4, 66.7g of alcohol, 66.7g of water and 0.33g of concentrated sulfuric acid into a reaction container, heating to a reflux temperature, carrying out reflux reaction for 2-3h, cooling and standing after the reaction is finished, crystallizing and separating out vanitrope, and filtering to obtain crude vanitrope and an alcohol aqueous solution containing isoeugenol;
s6, recrystallizing the crude vanitrope prepared in the step S5 by adopting an alcohol aqueous solution, wherein the alcohol concentration in the alcohol aqueous solution is 10-30%; and the byproduct isoeugenol is synthesized into ethyl vanillin through oxidation reaction.
31g of the finished product of the vanilline after recrystallization is finally obtained, and the purity is 97.1%.
The present invention has been described in terms of specific examples, which are provided to aid understanding of the invention and are not intended to be limiting. For a person skilled in the art to which the invention pertains, several simple deductions, modifications or substitutions may be made according to the idea of the invention.
Claims (7)
1. A method for preparing vanilline from sassafras oil is characterized by comprising the following steps:
s1, adding the sassafras oil, the methanol and the potassium hydroxide into a reaction kettle simultaneously, stirring, controlling the reaction temperature at 130-;
s2, stopping the reaction after the reaction is finished, cooling, adding a proper amount of water while stirring, standing for layering, and collecting the upper-layer methoxy isoeugenol sylvite solution;
s3, adding the methoxy isoeugenol potassium salt solution collected in the step S2 and diethyl sulfate into another reaction kettle, stirring, raising the temperature to 80-100 ℃, keeping the temperature for reaction for 2-3 hours, after the reaction is finished, sequentially adding a proper amount of water and toluene while stirring, standing for layering, and collecting an upper methylbenzene phase;
s4, carrying out rotary evaporation on the toluene phase obtained in the step S3 to recover toluene, then carrying out reduced pressure distillation, and collecting mixed ether fractions;
s5, sequentially adding the mixed ether fraction obtained in the step S4, alcohol, water and concentrated sulfuric acid into a reaction container, heating to a reflux temperature, carrying out reflux reaction for 2-3 hours, cooling and standing after the reaction is finished, crystallizing and separating out the vanitrope, and filtering to obtain a crude vanitrope and an alcohol aqueous solution containing isoeugenol;
s6, recrystallizing the crude vanitrope prepared in the step S5 to obtain the finished vanitrope.
2. The method for preparing vanitrope from sassafras oil according to claim 1, wherein in the step S1, the mass ratio of sassafras oil, methanol and potassium hydroxide is (1-2) to (1-2): (2-6).
3. The method for preparing vanitrope from sassafras oil according to claim 1 or 2, wherein in step S2, the mixed solution in the reaction kettle is sampled, and when the content of the sassafras oil in the mixed solution is less than 1%, the reaction is judged to be finished.
4. The method for preparing vanitrope from sassafras oil according to claim 3, wherein in the step S3, the mass ratio of the methoxy isoeugenol potassium salt solution to diethyl sulfate is (2-6): (1-2).
5. The method for preparing vanitrope from sassafras oil according to claim 4, wherein in the step S5, the mass ratio of the mixed ether fraction, the alcohol, the water and the concentrated sulfuric acid is (1-3): (2-8): (2-8): (0.01-0.05).
6. The method for preparing vanitrope from sassafras oil according to claim 1, wherein in step S2, the temperature is reduced to 90 ℃ or below.
7. The method for preparing vanitrope from sassafras oil according to claim 1, wherein in step S6, an aqueous alcohol solution is used for recrystallizing crude vanitrope, and the alcohol concentration in the aqueous alcohol solution is 10% -30%.
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| 孙凌峰等: "黄樟素的天然来源及其在合成香料中的利用", 《香料香精化妆品》 * |
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