CN104292088B - A kind of preparation method of anisic aldehyde - Google Patents
A kind of preparation method of anisic aldehyde Download PDFInfo
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- CN104292088B CN104292088B CN201310302581.XA CN201310302581A CN104292088B CN 104292088 B CN104292088 B CN 104292088B CN 201310302581 A CN201310302581 A CN 201310302581A CN 104292088 B CN104292088 B CN 104292088B
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Abstract
The invention discloses a kind of preparation method of anisic aldehyde, comprise the following steps: 1, in reactor, first add N, dinethylformamide and pyridine, the triphosgene that then drips at low temperatures chloroform dissolving is reacted, and triphosgene drips and finishes rear insulation continuation reaction 0.2～1h; 2, keep low temperature that alchlor is joined in above-mentioned reactant liquor in batches, alchlor adds rear insulation 0.2～1h; 3, the chloroform in still is steamed, and make still temperature reach 60～100 DEG C, keep the slow methyl phenyl ethers anisole that drips at this temperature; 4, methyl phenyl ethers anisole dropwises rear continuation and at 60～100 DEG C, adds thermal agitation 6～10h; 5, reaction finish after by the cancellation of reactant liquor liquid caustic soda solution, wash, extract, after precipitation, rectifying, obtain end product anisic aldehyde. That the inventive method has is easy, be easy to control and the feature of suitability for industrialized production; The anisic aldehyde safety and stability of producing, has improved production efficiency.
Description
Technical field
The present invention relates to a kind of preparation method of organic intermediate, be specifically related to a kind of preparation method of anisic aldehyde, belong to spices and essence chemical technology field.
Background technology
Anisic aldehyde (p-Anisaldehyde; Anisicaldehyde) sterling is colourless or weak yellow liquid, and with strong May bloom fragrance, fragrance is lasting, has stronger antioxygenic property. Anisaldehyde is the raw material of synthetic anise alcohol and ester type compound, anisic acid and ester type compound thereof, anisonitrile, is also important synthetic perfume, is widely used in allotment daily chemical essence and flavoring essence. In May bloom, sunflower, lilac essence, make main body fragrant material; In muguet compound, make pastil; In osmanthus flower fragrance, make dressing agent, also can be used for daily essence and food flavor. Gai Pinshi China GB2760-86 is defined as the flavorant that temporary transient permission is used, mainly in order to prepare the type essence such as vanilla, spice, apricot, cream, fennel, caramel, cherry, chocolate, English walnut, raspberry, strawberry, peppermint. Coordinate with the essential oil of tangerine etc., effect is fine.
The most ancient method of synthetic anisic aldehyde is to be oxidized and to obtain being present in anethole in fennel oil, ennel oil, oil of badian. But unstable due to the deficiency of natural essential oil and output, this method is eliminated in industrial production. Tang Xinjun is at " Chemical Industry in Guangzhou " 2009,37(7) in introduced several method and the route of at present synthetic anisic aldehyde. One, taking phenol as raw material, obtain chloromethylbenzene methyl ether, then will react with methenamine chloromethylbenzene methyl ether, hydrolysis makes product. This method step is more, and route is oversize, and reaction is not easy to control, and " three wastes " are many, is difficult for processing. Two, utilize MnO2Make product Deng oxidation p-methyl anisole, or be oxidized with oxygen by the method for catalytic oxidation. But this oxidation can only not rest on this step of aldehyde, but have quite a few P-methoxybenzoic acid produce. Three, parahydroxyben-zaldehyde and dimethyl suflfate carry out alkylated reaction and make product. The advantages such as that the method has is easy to operate, safety, reaction condition gentleness, but raw material sources are limited, are difficult to suitability for industrialized production. Four,, taking p-cresol as raw material, first methylate synthetic to methoxy toluene, and then oxidation obtains product. The crucial of this route is still being oxidized this step. In addition, adopt POCl3Carrying out VShi formylation reaction with N-methyl formyl aniline and methyl phenyl ethers anisole is also one of method of preparing anisic aldehyde, but this method can be brought a large amount of phosphorus-containing wastewaters.
Consider all limitation of said method aspect synthetic anisic aldehyde, we adopt new route directly to carry out formylated to methyl phenyl ethers anisole, have saved step and time, also can obtain higher yield simultaneously.
Summary of the invention
The present invention is directed to the problems referred to above a kind of preparation method of anisic aldehyde is provided, its object is: a kind of method that can prepare high-quality anisic aldehyde is provided, saves preparation time, enhance productivity.
The technology of the present invention solution:
A preparation method for anisic aldehyde, is characterized in that: comprise the following steps:
Step 1), in reactor, first add DMF and pyridine, the triphosgene that then drips at low temperatures chloroform dissolving is reacted, and triphosgene drips and finishes rear insulation continuation reaction 0.2～1h;
Step 2), keep low temperature that alchlor is joined in above-mentioned reactant liquor in batches, alchlor adds rear insulation 0.2～1h;
Step 3), the chloroform in still is steamed, and make still temperature reach 60～100 DEG C, keep the slow methyl phenyl ethers anisole that drips at this temperature;
Step 4), methyl phenyl ethers anisole dropwises rear continuation and at 60～100 DEG C, adds thermal agitation 6～10h;
Step 5), after reaction finishes, by liquid caustic soda solution cancellation for reactant liquor, wash, extract, after precipitation, rectifying, obtain end product anisic aldehyde.
In step 1 of the present invention, in reactor, add the pyridines of DMF and different amounts, drip at a certain temperature triphosgene that chloroform dissolves and react and obtain VShi reagent, triphosgene drips and finishes rear insulation and continue to react 0.2～1h.
OrganicReactions, 49(1) in the synthetic method of VShi reagent introduced, often adopt POCl3、COCl2Or P2O3Cl4React and make with DMF. The people such as Heaney are at Tetrahedron, 1993,49(19) in utilize POCl3Or P2O3Cl4React with DMF and make VShi reagent, and methyl phenyl ethers anisole has been carried out to formylation reaction. In addition patent FR2824555 has also reported and has utilized COCl2React with DMF and make VShi reagent, and methyl phenyl ethers anisole is carried out to formylated. But the inventor finds, utilizes the triphosgene of safety and stability to substitute COCl2、POCl3Or P2O3Cl4Equally also can realize the preparation of VShi reagent. But need to, with pyridine as catalyst, carry out catalytic decomposition to triphosgene.
Particularly, adopt the solvent of chloroform as VShi reaction, and adopt dropping mode that triphosgene is added in the reaction system of DMF and pyridine composition.
According to technical scheme of the present invention, in step 1, the addition of pyridine is 3～11% of triphosgene weight, preferably 4～8%, more preferably 5～6%.
In reaction system of the present invention, in order to make reaction temperature and to carry out, avoid the too more accessory substance of violent generation of reaction, should suitably control the reaction temperature of this step. According to the present invention, this step reaction temperature is 0～10 DEG C, preferably 0～5 DEG C.
Triphosgene addition is excessive a little for DMF, and the molar feed ratio of DMF and triphosgene is 1:1.01～1.20, preferably 1:1.02～1.15, more preferably 1:1.03～1.10, most preferably 1:1.04～1.06. The time for adding of triphosgene is controlled at 3～8 hours, and preferably 4～7 hours, more preferably 5～6 hours.
Carry out in order to react fully, triphosgene also will be proceeded reaction after dripping and finishing, and in the situation that reaction temperature remains unchanged, is incubated a period of time, for example, be incubated 0.2～1h, preferably 0.3～0.9h, and more preferably 0.5～0.6h, thus reaction is carried out completely.
In step 2 of the present invention, add alchlor to make the VShi reagent that itself and step 1 obtain carry out complexing. The people such as Zollinger are at Helv.Chim.Acta, 1959(177) in confirm that alchlor can carry out complexing with VShi reagent, and can be characterized by IR.
Find after deliberation, alchlor joins in the reactant liquor of step 1 can emit amount of heat, and still temperature is sharply raise. In reaction system of the present invention, be unlikely to make still temperature sharply to raise to destroy VShi reagent in order to make alchlor add fashionable liberated heat. The joining day of alchlor is 0.1～0.8 hour, preferably 0.2～0.7 hour, and more preferably 0.5～0.6 hour. Adding the temperature after alchlor is 20～60 DEG C, preferably 20～40 DEG C, and more preferably 20～30 DEG C.
In technical scheme of the present invention, the molar feed ratio of triphosgene and alchlor is 1:1.01～1.20, preferably 1:1.03～1.16, more preferably 1:1.04～1.14, most preferably 1:1.05～1.06.
In reaction system of the present invention, the object of insulation is for can be by alchlor and the complete complexing of VShi reagent. Therefore temperature retention time is 0.2～1h, is preferably 0.3～0.9h, more preferably 0.5～0.6h.
In step 3 of the present invention, chloroform is steamed from reaction system, make still temperature reach certain temperature, then at this temperature, slowly drip methyl phenyl ethers anisole. Drip in the process of methyl phenyl ethers anisole, can emit a large amount of HCl gas.
In the present invention program, the molar feed ratio of methyl phenyl ethers anisole and DMF is 1:1.01～1.30, preferably 1:1.10～1.25, more preferably 1:1.15～1.20, most preferably 1:1.16～1.18.
In reaction system of the present invention, the reaction temperature that methyl phenyl ethers anisole drips is 60～100 DEG C, preferably 70～90 DEG C, and more preferably 75～80 DEG C. The time for adding of methyl phenyl ethers anisole is 1～5 hour, preferably 2～4 hours, and more preferably 3～3.5 hours.
In step 4 of the present invention, the reactant liquor that step 3 is obtained at high temperature continues to add thermal agitation and reacts. Step 4 is final steps of whole reaction, and product mainly generates in this step.
Find after deliberation, the too high and too low yield that all can affect reaction of reaction temperature, the length in reaction time also can obviously affect the generation of impurity in reaction.
In this reaction system, reaction temperature is 60～100 DEG C, preferably 70～90 DEG C, and more preferably 80～85 DEG C. Reaction time is 6～10h, is preferably 7～9h, more preferably 7～8h.
In step 5 of the present invention, reactant liquor, through the cancellation of liquid caustic soda solution, is washed, extracted, after precipitation, rectifying, obtain end product anisic aldehyde.
According to the present invention, reaction finishes to exist in rear reaction system unreacted raw material, solvent and product, now by obtaining product anisic aldehyde crude product after desolvation, add and in rectifying still, carry out rectifying, by gas-chromatography (GC) sample analysis, determine and obtain qualified products. Solvent after precipitation can continue to apply mechanically to extract.
The anisic aldehyde of above-mentioned embodiment gained is light yellow transparent liquid, index of refraction (nd20) between 1.571～1.574, proportion (25 DEG C, mg/mL) is between 1.119～1.123; , GC content (area normalization method): o-anisic aldehyde<2.0%, p-anisic aldehyde>=97.0%, o-anisic aldehyde+p-anisic aldehyde>=98.0%; Moisture≤0.25%.
Beneficial effect of the present invention:
(1), the VShi stage of reaction, select triphosgene react with DMF. Avoided the use of traditional phosphorus-containing compound, and the safety and stability of triphosgene is also brought certain security;
(2), adopt alchlor complexing VShi reagent, avoid VShi reagent in the pyroreaction in later stage, to decompose destruction;
(3), by the adjustment of end reaction time and temperature, can obtain the anisic aldehyde of high conversion;
(4), thick product is carried out to rectifying, can obtain the pure qualified products of fragrance.
The present invention has explored the scheme of utilizing VShi formylation reaction to prepare anisic aldehyde, and has obtained good effect. In addition the inventive method also has easy, to be easy to control and suitability for industrialized production feature.
Detailed description of the invention
Further explain and describe by the following examples content of the present invention.
Embodiment 1:
In the glass reactor of 500 milliliters, remain on and when temperature is 0～10 DEG C, add 44.11gDMF and 3.16g pyridine. Then the 59.35g triphosgene that slowly adds 300g chloroform to dissolve within 6h. After all triphosgenes add, insulation 1h.
75.2 grams of alchlors are joined in above-mentioned reactant liquor within 0.5h in batches, while adding alchlor, maintain the temperature at 20～30 DEG C. After all alchlors add, insulation 0.5h.
Then the chloroform in above-mentioned reaction system is steamed, reach 80 DEG C to still temperature. And in 3h, add gradually 52.5 grams of methyl phenyl ethers anisoles. After methyl phenyl ethers anisole adds, continue at 80～85 DEG C, to keep 6 hours, keep stirring simultaneously.
Reaction finishes the rear aqueous solution with NaOH reactant liquor is hydrolyzed. After undue water, washing, extraction, desolvation, obtains anisic aldehyde crude product, and this crude product is carried out to rectifying, obtains end product anisic aldehyde, is light yellow transparent liquid, index of refraction (nd20) be 1.572, proportion (25 DEG C, mg/mL) is 1.119; , GC content (area normalization method): o-anisic aldehyde is that 2.0%, p-anisic aldehyde is 97.0%, and moisture is 0.22%.
Embodiment 2:
In the glass reactor of 500 milliliters, remain on and when temperature is 0～5 DEG C, add 44.11gDMF and 4.26g pyridine. Then the 61.47g triphosgene that slowly adds 300g chloroform to dissolve within 4h. After all triphosgenes add, insulation 0.2h.
75.2 grams of alchlors are joined in above-mentioned reactant liquor within 0.5h in batches, while adding alchlor, maintain the temperature at 20～30 DEG C. After all alchlors add, insulation 0.5h.
Then the chloroform in above-mentioned reaction system is steamed, reach 60 DEG C to still temperature. And in 2h, add gradually 52.5 grams of methyl phenyl ethers anisoles. After methyl phenyl ethers anisole adds, continue at 80～85 DEG C, to keep 7 hours, keep stirring simultaneously.
Reaction finishes the rear aqueous solution with NaOH reactant liquor is hydrolyzed. After undue water, washing extraction, desolvation, obtains anisic aldehyde crude product, and this crude product is carried out to rectifying, obtains end product anisic aldehyde, is light yellow transparent liquid, index of refraction (nd20) be 1.574, proportion (25 DEG C, mg/mL) is 1.120; , GC content (area normalization method): o-anisic aldehyde is that 1.1%, p-anisic aldehyde is 98.0%, and moisture is 0.21%.
Embodiment 3:
In the glass reactor of 500 milliliters, remain on and when temperature is 0～5 DEG C, add 44.11gDMF and 3.16g pyridine. Then the 59.35g triphosgene that slowly adds 300g chloroform to dissolve within 7h. After all triphosgenes add, insulation 0.5h.
80 grams of alchlors are joined in above-mentioned reactant liquor within 0.3h in batches, while adding alchlor, maintain the temperature at 30～40 DEG C. After all alchlors add, insulation 0.5h.
Then the chloroform in above-mentioned reaction system is steamed, reach 80 DEG C to still temperature. And in 3h, add gradually 53.5 grams of methyl phenyl ethers anisoles. After methyl phenyl ethers anisole adds, continue at 80～85 DEG C, to keep 10 hours, keep stirring simultaneously.
Reaction finishes the rear aqueous solution with NaOH reactant liquor is hydrolyzed. After undue water, washing extraction, desolvation, obtains anisic aldehyde crude product, and this crude product is carried out to rectifying, obtains end product anisic aldehyde, is light yellow transparent liquid, index of refraction (nd20) be 1.571, proportion (25 DEG C, mg/mL) is 1.121; , GC content (area normalization method): o-anisic aldehyde is that 1.5%, p-anisic aldehyde is 97.7%, and moisture is 0.23%.
Embodiment 4:
In the glass reactor of 500 milliliters, remain on and when temperature is 0～5 DEG C, add 44.11gDMF and 5.74g pyridine. Then the 59.35g triphosgene that slowly adds 300g chloroform to dissolve within 3h. After all triphosgenes add, insulation 1h.
75.2 grams of alchlors are joined in above-mentioned reactant liquor within 0.5h in batches, while adding alchlor, maintain the temperature at 40～50 DEG C. After all alchlors add, insulation 1h
Then the chloroform in above-mentioned reaction system is steamed, reach 70 DEG C to still temperature. And in 3h, add gradually 52.5 grams of methyl phenyl ethers anisoles. After methyl phenyl ethers anisole adds, continue at 80～85 DEG C, to keep 9 hours, keep stirring simultaneously.
Reaction finishes the rear aqueous solution with NaOH reactant liquor is hydrolyzed. After undue water, washing extraction, desolvation, obtains anisic aldehyde crude product, and this crude product is carried out to rectifying, obtains end product anisic aldehyde, is light yellow transparent liquid, index of refraction (nd20) be 1.572, proportion (25 DEG C, mg/mL) is 1.123; , GC content (area normalization method): o-anisic aldehyde is that 1.5%, p-anisic aldehyde is 98.0%, and moisture is 0.22%.
Embodiment 5:
In the glass reactor of 500 milliliters, remain on and when temperature is 0～5 DEG C, add 44.11gDMF and 4.56g pyridine. Then the 61.47g triphosgene that slowly adds 300g chloroform to dissolve within 6h. After all triphosgenes add, insulation 0.5h.
80 grams of alchlors are joined in above-mentioned reactant liquor within 0.7h in batches, while adding alchlor, maintain the temperature at 20～30 DEG C. After all alchlors add, insulation 0.5h.
Then the chloroform in above-mentioned reaction system is steamed, reach 80 DEG C to still temperature. And in 4h, add gradually 55.5 grams of methyl phenyl ethers anisoles. After methyl phenyl ethers anisole adds, continue at 80～85 DEG C, to keep 8 hours, keep stirring simultaneously.
Reaction finishes the rear aqueous solution with NaOH reactant liquor is hydrolyzed. After undue water, washing extraction, desolvation, obtains anisic aldehyde crude product, and this crude product is carried out to rectifying, obtains end product anisic aldehyde, is light yellow transparent liquid, index of refraction (nd20) be 1.571, proportion (25 DEG C, mg/mL) is 1.122; , GC content (area normalization method): o-anisic aldehyde is that 1.7%, p-anisic aldehyde is 98.2%, and moisture is 0.22%.
Should be appreciated that, although the present invention has been described in detail in conjunction with example, above-mentioned explanation is intended to illustrate, and limits never in any form its summary of the invention. Concerning art technology people, the explanation based on herein can farthest utilize the present invention, and can carry out multiple amendment or modification not departing from claim scope of the present invention or spirit. Each bibliography that the application quotes, which is hereby incorporated by reference.
Claims (14)
1. a preparation method for anisic aldehyde, is characterized in that: comprise the following steps:
Step 1 first adds DMF and pyridine in reactor, then the triphosgene that drips at low temperatures chloroform dissolving is reacted, triphosgene drips and finishes rear insulation continuation reaction 0.2～1h, and wherein, the addition of pyridine is 3～11% of triphosgene weight;
Step 2, keeps low temperature that alchlor is joined in above-mentioned reactant liquor in batches, and alchlor adds rear insulation 0.2～1h;
Step 3, steams the chloroform in still, and makes still temperature reach 60～100 DEG C, keeps the slow methyl phenyl ethers anisole that drips at this temperature;
Step 4, methyl phenyl ethers anisole dropwises rear continuation and at 60～100 DEG C, adds thermal agitation 6～10h;
Step 5, by liquid caustic soda solution cancellation for reactant liquor, washs, extracts after reaction finishes, and obtains end product anisic aldehyde after precipitation, rectifying;
In step 1, the temperature that drips triphosgene is 0～10 DEG C; In step 2, add the temperature after alchlor to remain between 20～60 DEG C; In step 3, the temperature while dripping methyl phenyl ethers anisole is controlled between 60～100 DEG C.
2. a kind of preparation method of anisic aldehyde according to claim 1, is characterized in that: in step 1, the addition of pyridine is 4～8% of triphosgene weight.
3. a kind of preparation method of anisic aldehyde according to claim 1, is characterized in that: in step 1, the addition of pyridine is 5～6% of triphosgene weight.
4. according to the arbitrary described preparation method of claims 1 to 3, it is characterized in that: in step 1, the temperature that drips triphosgene is 0～5 DEG C; In step 2, add the temperature after alchlor to remain between 20～40 DEG C; In step 3, the temperature while dripping methyl phenyl ethers anisole is controlled between 70～90 DEG C; In step 4, methyl phenyl ethers anisole dropwises rear temperature and is controlled between 70～90 DEG C.
5. according to the arbitrary described preparation method of claims 1 to 3, it is characterized in that: in step 2, add the temperature after alchlor to remain between 20～30 DEG C; In step 3, the temperature while dripping methyl phenyl ethers anisole is controlled between 75～80 DEG C; In step 4, methyl phenyl ethers anisole dropwises rear temperature and is controlled between 80～85 DEG C.
6. according to the preparation method one of claims 1 to 3 Suo Shu, it is characterized in that: in step 1, it is 0.3～0.8h that triphosgene dropping finishes rear temperature retention time; In step 2, adding the temperature retention time after alchlor is 0.3～0.9h.
7. according to the preparation method one of claims 1 to 3 Suo Shu, it is characterized in that: in step 1, it is 0.5～0.6h that triphosgene dropping finishes rear temperature retention time; In step 2, adding the temperature retention time after alchlor is 0.5～0.6h.
8. according to the preparation method one of claims 1 to 3 Suo Shu, it is characterized in that: in step 1, the molar feed ratio of DMF and triphosgene is 1:1.01～1.20; The time for adding of triphosgene is 3～8 hours; In step 2, the molar feed ratio of triphosgene and alchlor is 1:1.01～1.20; Joining day is controlled between 0.1～0.8h alchlor in batches; In step 3, the molar feed ratio of methyl phenyl ethers anisole and DMF is 1:1.01～1.30.
9. according to the preparation method one of claims 1 to 3 Suo Shu, it is characterized in that: in step 1, the molar feed ratio of DMF and triphosgene is 1:1.02～1.15; The time for adding of triphosgene is 4～7h; In step 2, the molar feed ratio of triphosgene and alchlor is 1:1.03～1.16; Joining day is controlled between 0.2～0.7h alchlor in batches; In step 3, the molar feed ratio of methyl phenyl ethers anisole and DMF is 1:1.10～1.25.
10. according to the preparation method one of claims 1 to 3 Suo Shu, it is characterized in that: in step 1, the molar feed ratio of DMF and triphosgene is 1:1.03～1.10; The time for adding of triphosgene is 5～6h; In step 2, the molar feed ratio of triphosgene and alchlor is 1:1.04～1.14; Joining day is controlled between 0.2～0.7h alchlor in batches; In step 3, the molar feed ratio of methyl phenyl ethers anisole and DMF is 1:1.15～1.20.
11. according to the preparation method one of claims 1 to 3 Suo Shu, it is characterized in that: in step 1, the molar feed ratio of DMF and triphosgene is 1:1.04～1.06; In step 2, the molar feed ratio of triphosgene and alchlor is 1:1.05～1.06; In step 3, the molar feed ratio of methyl phenyl ethers anisole and DMF is 1:1.16～1.18.
12. according to the preparation method one of claims 1 to 3 Suo Shu, it is characterized in that: in step 3, the time for adding of methyl phenyl ethers anisole is 1～5h; In step 4, the reaction time is 6～10h.
13. according to the preparation method one of claims 1 to 3 Suo Shu, it is characterized in that: in step 3, the time for adding of methyl phenyl ethers anisole is 2～4h; In step 4, the reaction time is 7～9h.
14. according to the preparation method one of claims 1 to 3 Suo Shu, it is characterized in that: in step 3, the time for adding of methyl phenyl ethers anisole is 3～3.5h; In step 4, the reaction time is 7～8h.
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| FR2824555A1 (en) * | 2001-05-11 | 2002-11-15 | Poudres & Explosifs Ste Nale | Synthesis of a para-alkoxybenzaldehyde by formylation of a phenylethyl ether using a complex of a Vilsmeier salt with aluminium trichloride, useful in the preparation of medicaments and perfumes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2824555A1 (en) * | 2001-05-11 | 2002-11-15 | Poudres & Explosifs Ste Nale | Synthesis of a para-alkoxybenzaldehyde by formylation of a phenylethyl ether using a complex of a Vilsmeier salt with aluminium trichloride, useful in the preparation of medicaments and perfumes |
Non-Patent Citations (2)
| Title |
|---|
| "VILSMEIER-HAACK SYNTHESIS OF AROMATIC ALDEHYDES USING bis-(TRICHLOROMETHYL) CARBONATE AND DIMETHYLFORMAMIDE";W.G.Shan, et al.;《Organic Preparations and Procedures International: The New Journal for Organic Synthesis》;20041231;第36卷(第4期);337-340 * |
| "三光气的反应机理和应用";季宝;《科技情报开发与经济》;20091231;第19卷(第10期);136-137 * |
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