CN112390710A - Preparation method of anisic aldehyde - Google Patents
Preparation method of anisic aldehyde Download PDFInfo
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- CN112390710A CN112390710A CN201910748268.6A CN201910748268A CN112390710A CN 112390710 A CN112390710 A CN 112390710A CN 201910748268 A CN201910748268 A CN 201910748268A CN 112390710 A CN112390710 A CN 112390710A
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- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 24
- RUVINXPYWBROJD-ONEGZZNKSA-N trans-anethole Chemical compound COC1=CC=C(\C=C\C)C=C1 RUVINXPYWBROJD-ONEGZZNKSA-N 0.000 claims abstract description 24
- 239000012071 phase Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- RUVINXPYWBROJD-UHFFFAOYSA-N para-methoxyphenyl Natural products COC1=CC=C(C=CC)C=C1 RUVINXPYWBROJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 239000012074 organic phase Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 10
- 238000004821 distillation Methods 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000006722 reduction reaction Methods 0.000 claims abstract description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 229940011037 anethole Drugs 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000009776 industrial production Methods 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 description 26
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 239000002351 wastewater Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 238000005191 phase separation Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- MIDXCONKKJTLDX-UHFFFAOYSA-N 3,5-dimethylcyclopentane-1,2-dione Chemical compound CC1CC(C)C(=O)C1=O MIDXCONKKJTLDX-UHFFFAOYSA-N 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000006927 Foeniculum vulgare Species 0.000 description 1
- 235000004204 Foeniculum vulgare Nutrition 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-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
- 244000018633 Prunus armeniaca Species 0.000 description 1
- 235000009827 Prunus armeniaca Nutrition 0.000 description 1
- 235000011034 Rubus glaucus Nutrition 0.000 description 1
- 244000235659 Rubus idaeus Species 0.000 description 1
- 235000009122 Rubus idaeus Nutrition 0.000 description 1
- 244000299461 Theobroma cacao Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 244000290333 Vanilla fragrans Species 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000001387 anti-histamine Effects 0.000 description 1
- 239000000739 antihistaminic agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 235000013736 caramel Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 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
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/40—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with ozone; by ozonolysis
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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 preparation method of anisaldehyde, which comprises the following steps: s1, adding natural anise camphor and water into a bubble reactor, introducing ozone at the temperature of 15-27 ℃ to perform ozone oxidation reaction for 200-300 min, standing reaction liquid for phase splitting after the reaction is finished, and separating to remove a water phase to obtain an organic phase to be used; s2, adding a reducing agent aqueous solution into the organic phase obtained in the step S1, carrying out reduction reaction at the temperature of 70-80 ℃ for 40-60 min, and adding alkali liquor for neutralization to obtain a crude anisaldehyde product; s3, carrying out reduced pressure distillation on the crude anisic aldehyde obtained in the step S2, and collecting fractions with the pressure of 120-220 Pa and the temperature of 120-170 ℃ to obtain the finished anisic aldehyde. The method has the advantages of simple process, mild reaction conditions, high yield, high utilization rate of raw materials, total yield of 68-75%, meeting the process requirements of environmental protection and being beneficial to realizing industrial production.
Description
Technical Field
The invention relates to the technical field of anisaldehyde preparation methods, and particularly relates to a preparation method of anisaldehyde.
Background
Anisic aldehyde, also called anisic aldehyde, p-anisic aldehyde, the chemical name is: 4-methoxybenzaldehyde, the chemical structural formula is: the chemical formula is: c8H8O2Molecular weight 136.15, colorless or pale yellow liquid. Anisic aldehyde is mainly used in the following aspects: 1. used for preparing essence, is an allowable spice in China GB2760-86,is mainly used for preparing vanilla, spice, apricot, cream, fennel, caramel, cherry, chocolate, walnut, raspberry, strawberry, mint and other types of essence; 2. important intermediates for preparing hydroxyaminobenzylpenicillin, antihistaminic drugs and the like; 3. used as brightening agent for plating metal; 4. compounds with functional groups of nitrogen atoms were followed as developers.
The methods currently used for preparing anisaldehyde are mainly the following methods:
1. the traditional chemical oxidation method comprises the following steps: the method adopts potassium permanganate, manganese dioxide, sulfuric acid and the like as oxidants, consumes a large amount of heavy metal salts such as chromium, manganese and the like and a large amount of acid and alkali in the reaction process, generates a large amount of manganese salt waste residues, chromium residues and wastewater, has the problem of difficult treatment of three-waste pollution, causes great pollution to the environment, causes serious corrosion to production equipment in the presence of acid, and has the yield of the prepared anisaldehyde of only about 50 percent.
2. Electrochemical oxidation method: the electrochemical oxidation method is that graphite or titanium base is used as anode, stainless steel is used as cathode, 80% -90% ethanol water solution is used as solvent, 0.25mol/L H2SO4As an electrolyte, the concentration of natural anethole is not more than 0.15mol/L, and the yield of the obtained anisic aldehyde is about 60 percent; compared with the traditional chemical oxidation method, the yield of anisic aldehyde is greatly improved, but the method has high power consumption, and the product is difficult to separate after reaction, so that the method can not meet the requirement of industrial production.
3. An ozone oxidation method: the ozone oxidation method is a method which is researched more in recent 30 years, ozone has the characteristics of strong oxidizing power, good selectivity, high reaction speed and the like, anethole is unsaturated olefin with benzene ring, ozone can oxidize double bonds and cannot attack the benzene ring, but a large amount of organic solvent is needed in the process of preparing the anisaldehyde by the ozone oxidation method, on one hand, the organic solvent is difficult to recover and consume, the product purification difficulty is high, on the other hand, the ozone oxidation reaction has high potential safety hazard, such as explosion accident, and the industrial production is difficult to realize.
Disclosure of Invention
The invention aims to overcome the defects and provides a preparation method of anisic aldehyde, wherein the anisic aldehyde can be prepared by taking natural anethole as an initial raw material through three steps of processes, the process is simple, the reaction conditions are mild, the yield is high, the utilization rate of the raw material is high, the total yield is 68-75%, and the obtained anisic aldehyde has pure fragrance, high purity and high naturalness, meets the process requirements of environmental protection and is beneficial to realizing industrial production.
In order to realize the aim, the invention provides the following technical scheme that the preparation method of anisaldehyde comprises the following steps:
s1, adding natural anise camphor and water into a bubble reactor, introducing ozone at the temperature of 15-27 ℃ to perform ozone oxidation reaction for 200-360 min, standing reaction liquid for phase splitting after the reaction is finished, and separating to remove a water phase to obtain an organic phase to be used;
s2, adding a reducing agent aqueous solution into the organic phase obtained in the step S1, carrying out reduction reaction at the temperature of 70-80 ℃ for 40-60 min, and adding alkali liquor for neutralization to obtain a crude product of natural anisic aldehyde;
s3, carrying out reduced pressure distillation on the crude anisic aldehyde obtained in the step S2, and collecting fractions with the pressure of 120-220 Pa and the temperature of 120-170 ℃ to obtain the finished anisic aldehyde.
Through determination, the finished anisic aldehyde prepared by the method is colorless or light yellow liquid, is solidified when meeting cold, has the relative density of 1.119-1.123, the refractive index of 1.5710-1.5750, the boiling point of 246-248 ℃, the melting point of 1-2.5 ℃, the flash point of over 100 ℃ and the solubility of 0.3% in water, is dissolved in most organic solvents and is slightly soluble in propylene glycol and glycerol; when dissolved in ethanol with the volume fraction of 50%, the mass ratio of the ethanol with the volume fraction of 50% to the anisic aldehyde prepared by the invention is 1: 7; when dissolved in ethanol with the volume fraction of 60%, the mass ratio of the ethanol with the volume fraction of 60% to the anisic aldehyde prepared by the invention is 1: 2; can be dissolved with oil perfume, and has an acid value less than 6.0.
The total yield of anisic aldehyde prepared by the method is 68-75%.
The method for preparing the anisic aldehyde has the advantages that the acid and alkali consumption is low, organic solvents are not required to be added, and unreacted ozone is automatically decomposed into oxygen, so that the method for preparing the anisic aldehyde has small wastewater yield, is easy to treat, does not generate organic waste gas and dust, and is high in material collection, high in purity and high in naturalness, and convenient for realizing industrial production.
Preferably, the mass ratio of the natural anise camphor to the water in the step S1 is 1: 1.
preferably, the mass ratio of the natural anise camphor to the water is 1: 6.
preferably, the reaction temperature of the ozone oxidation reaction in the step S1 is 25 ℃, and the reaction time is 40-60 min.
Preferably, the reaction solution in step S1 is allowed to stand for phase separation in a phase separation tank.
Preferably, the mass ratio of the organic phase to the reducing agent in the step S2 is 2: 1-1: 5.
preferably, the reducing agent in step S2 is selected from any one or more of sodium sulfite, sodium bisulfite and sodium metabisulfite, and the alkali liquor in step S2 is 30% sodium hydroxide solution by mass fraction.
Preferably, the vacuum distillation in step S2 adopts a metal corrugated packed tower.
Preferably, the pH value of the alkaline solution after neutralization in step S2 is 7.
Preferably, the step S3 is to collect the fraction with the pressure of 150-220 Pa and the temperature of 120-170 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of anisic aldehyde can prepare anisic aldehyde by using natural anethole as an initial raw material through three steps of processes, and has the advantages of simple process, mild reaction conditions, low power consumption, high yield, high raw material utilization rate, total yield of 68-75%, pure fragrance, high purity and high naturalness of the obtained anisic aldehyde.
2. Heavy metal substances are not used in the reaction process, the using amount of acid and alkali is small, the generated wastewater is small in amount and easy to treat, the ozone which does not participate in the reaction is automatically decomposed to be changed into oxygen, other organic waste gas and dust are not discharged, the production cost is reduced, and meanwhile, the process requirement of environmental protection is met;
3. the method for preparing the anisaldehyde avoids the key problems of environmental pollution, equipment corrosion and other industrial production caused by using potassium permanganate, potassium dichromate, manganese dioxide and the like, has wide raw material sources, low equipment cost and production cost, high raw material conversion rate, high product yield and low yield of three wastes in the reaction process, and is beneficial to realizing industrial production.
Drawings
FIG. 1 is a process flow diagram of a method for preparing anisaldehyde of the present invention.
Detailed Description
In order to make the technical means, the characteristics, the purposes and the functions of the invention easy to understand, the invention is further described with reference to the specific drawings.
Example 1
Referring to fig. 1, a preparation method of anisaldehyde comprises the following steps:
(1) and (3) carrying out ozone oxidation reaction: mixing 100mL of natural anise camphor with water according to the weight ratio of the natural anise camphor: water 2:1, putting the mixture into a bubbling reactor, keeping the temperature at 23 ℃, introducing ozone for oxidation reaction, and stopping introducing ozone after reacting for 240 min;
(2) standing and phase splitting: transferring the reaction system to a separating funnel, standing for 30min, and then carrying out phase separation, wherein the upper layer of light yellow transparent liquid is an aqueous phase (the aqueous phase is subjected to wastewater removal treatment), and the lower layer of yellow liquid is an organic phase;
(3) and reduction reaction: adding 32.4g of 15% sodium bisulfite aqueous solution into the organic phase, reacting at 80 ℃ for 40min, transferring into a separating funnel, standing for 30min, and separating phases, wherein the upper layer of light yellow transparent liquid is water phase (water phase is subjected to wastewater removal treatment), and the lower layer of yellow liquid is crude anisaldehyde;
(4) and (3) neutralization reaction: adding 30% liquid alkali into the crude product of anisic aldehyde to perform a neutralization reaction to enable the pH value to reach 6-7, transferring the product into a separating funnel, standing for 30min, and then performing phase separation, wherein the upper layer of light yellow transparent liquid is a water phase (the water phase is subjected to wastewater removal treatment), and the lower layer of yellow liquid is the crude product of anisic aldehyde;
(5) and reduced pressure distillation: and putting the neutralized crude anisaldehyde into a 150mL three-neck flask with a filler column, carrying out reduced pressure distillation under 220Pa, and collecting fractions at the temperature of 118-146 ℃, wherein the obtained substance is the finished anisaldehyde product. The total mass yield is 68.29%, and the content of anisic aldehyde is 99.67%.
The obtained anisic aldehyde finished product is colorless or light yellow liquid, is solidified when meeting cold, has the relative density of 1.119-1.123, the refractive index of 1.5710-1.5750, the boiling point of 246-248 ℃, the melting point of 1-2.5 ℃, the flash point of over 100 ℃, the solubility of 0.3 percent in water, is dissolved in most organic solvents and is slightly soluble in propylene glycol and glycerol.
Example 2
Referring to fig. 1, a preparation method of anisaldehyde comprises the following steps:
(1) and (3) carrying out ozone oxidation reaction: mixing 100mL of natural anise camphor with water according to the weight ratio of the natural anise camphor: water 1: 3, putting the materials into a bubbling reactor in proportion, keeping the temperature at 15 ℃, introducing ozone for oxidation reaction, and stopping introducing ozone after reacting for 360 min;
(2) standing and phase splitting: transferring the reaction system to a separating funnel, standing for 30min, and then carrying out phase separation, wherein the upper layer of light yellow transparent liquid is an aqueous phase (the aqueous phase is subjected to wastewater removal treatment), and the lower layer of yellow liquid is an organic phase;
(3) and reduction reaction: adding 31.8g of 15% sodium sulfite aqueous solution into the organic phase, reacting at 70 ℃ for 60min, transferring into a separating funnel, standing for 30min, and then separating phases, wherein the upper layer of light yellow transparent liquid is an aqueous phase (the aqueous phase is subjected to wastewater removal treatment), and the lower layer of yellow liquid is a crude product of anisaldehyde;
(4) and (3) neutralization reaction: adding 30% liquid alkali into the crude product of anisic aldehyde to perform a neutralization reaction to enable the pH value to reach 6-7, transferring the product into a separating funnel, standing for 30min, and then performing phase separation, wherein the upper layer of light yellow transparent liquid is a water phase (the water phase is subjected to wastewater removal treatment), and the lower layer of yellow liquid is the crude product of anisic aldehyde;
(5) and reduced pressure distillation: and putting the neutralized crude anisaldehyde into a 150mL three-neck flask with a filler column, carrying out reduced pressure distillation under 220Pa, and collecting fractions at the temperature of 118-146 ℃, wherein the obtained substance is the finished anisaldehyde product. The total mass yield is 74.87%, and the content of anisic aldehyde is 99.04%.
The obtained anisic aldehyde finished product is colorless or light yellow liquid, is solidified when meeting cold, has the relative density of 1.119-1.123, the refractive index of 1.5710-1.5750, the boiling point of 246-248 ℃, the melting point of 1-2.5 ℃, the flash point of over 100 ℃, the solubility of 0.3 percent in water, is dissolved in most organic solvents and is slightly soluble in propylene glycol and glycerol.
Example 3
Referring to fig. 1, a preparation method of anisaldehyde comprises the following steps:
(1) and (3) carrying out ozone oxidation reaction: mixing 100mL of natural anise camphor with water according to the weight ratio of the natural anise camphor: water 1: 10, putting the materials into a bubbling reactor, keeping the temperature at 27 ℃, introducing ozone for oxidation reaction, and stopping introducing ozone after reacting for 200 min;
(2) standing and phase splitting: transferring the reaction system to a separating funnel, standing for 30min, and then carrying out phase separation, wherein the upper layer of light yellow transparent liquid is an aqueous phase (the aqueous phase is subjected to wastewater removal treatment), and the lower layer of yellow liquid is an organic phase;
(3) and reduction reaction: adding 22.4g of 20% sodium metabisulfite aqueous solution into the organic phase, reacting at 70 ℃ for 40min, transferring into a separating funnel, standing for 30min, separating phases, wherein the upper layer of light yellow transparent liquid is water phase (water phase is subjected to wastewater removal treatment), and the lower layer of yellow liquid is crude anisaldehyde;
(4) and (3) neutralization reaction: adding 30% liquid alkali into the crude product of anisic aldehyde to perform a neutralization reaction to enable the pH value to reach 6-7, transferring the product into a separating funnel, standing for 30min, and then performing phase separation, wherein the upper layer of light yellow transparent liquid is a water phase (the water phase is subjected to wastewater removal treatment), and the lower layer of yellow liquid is the crude product of anisic aldehyde;
(5) and reduced pressure distillation: and putting the neutralized crude anisaldehyde into a 150mL three-neck flask with a filler column, carrying out reduced pressure distillation under 220Pa, and collecting fractions at the temperature of 115-155 ℃ to obtain the material, namely the finished anisaldehyde. The total mass yield is 71.1 percent, and the content of anisic aldehyde is 99.2 percent.
The obtained anisic aldehyde finished product is colorless or light yellow liquid, is solidified when meeting cold, has the relative density of 1.119-1.123, the refractive index of 1.5710-1.5750, the boiling point of 246-248 ℃, the melting point of 1-2.5 ℃, the flash point of over 100 ℃, the solubility of 0.3 percent in water, is dissolved in most organic solvents and is slightly soluble in propylene glycol and glycerol.
In conclusion, the natural anise camphor is used as an initial raw material, the anisic aldehyde can be prepared through three steps of processes, the process is simple, the reaction conditions are mild, the yield is high, the utilization rate of the raw materials is high, the total yield is 68-75%, and meanwhile, the obtained anisic aldehyde is pure in fragrance, high in purity and high in natural degree, meets the process requirements of environmental protection, and is beneficial to realization of industrial production.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The preparation method of anisaldehyde is characterized by comprising the following steps:
s1, adding natural anise camphor and water into a bubble reactor, introducing ozone at the temperature of 15-27 ℃ for oxidation reaction for 200-360 min, standing reaction liquid for phase splitting after the reaction is finished, and separating to remove a water phase to obtain an organic phase for later use;
s2, adding a reducing agent aqueous solution into the organic phase obtained in the step S1, carrying out reduction reaction at the temperature of 70-80 ℃ for 40-60 min, and adding alkali liquor for neutralization to obtain a crude anisaldehyde product;
s3, carrying out reduced pressure distillation on the crude anisic aldehyde obtained in the step S2, and collecting fractions with the pressure of 120-220 Pa and the temperature of 120-170 ℃ to obtain the finished anisic aldehyde.
2. The method for preparing anisaldehyde according to claim 1, wherein the mass ratio of the natural anethole to water in step S1 is 2: 1-1: 20.
3. The method for preparing anisaldehyde according to claim 2, wherein the mass ratio of the natural anethole to water is 1: 6.
4. the method for preparing anisaldehyde of claim 1, wherein the ozone oxidation reaction in step S1 is carried out at a temperature of 25 ℃ for a time of 270-300 min.
5. The method for preparing anisaldehyde according to claim 1, wherein the mass ratio of the organic phase to the reducing agent in step S2 is 2:1 to 1: 5.
6. The method of claim 1, wherein the reducing agent in step S2 is selected from the group consisting of sodium sulfite, sodium bisulfite and sodium metabisulfite, and the lye in step S2 is 30% by weight sodium hydroxide solution.
7. The process for producing anisaldehyde of claim 1 wherein the vacuum distillation in step S2 employs a metal corrugated packed tower.
8. The method for producing anisaldehyde of claim 1 wherein the pH of the neutralized solution in step S2 is 7.
9. The method according to claim 1, wherein the step S3 is performed by collecting a fraction having a pressure of 150 to 220Pa and a temperature of 120 to 170 ℃.
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