CN101570473A - Method for synthesizing 3-methoxybenzaldehyde - Google Patents
Method for synthesizing 3-methoxybenzaldehyde Download PDFInfo
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- CN101570473A CN101570473A CNA2009100692035A CN200910069203A CN101570473A CN 101570473 A CN101570473 A CN 101570473A CN A2009100692035 A CNA2009100692035 A CN A2009100692035A CN 200910069203 A CN200910069203 A CN 200910069203A CN 101570473 A CN101570473 A CN 101570473A
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- nitric acid
- methoxybenzaldehyde
- water
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- methoxybenzyl alcohol
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Abstract
The invention relates to a method for synthesizing 3-methoxybenzaldehyde. M-methoxybenzyl alcohol is used as a raw material; at room temperature, 3-methoxybenzaldehyde is obtained by taking water as a dissolvent and using nitric acid for direct oxidation; and the use level of the nitric acid is 1 to 2 times as that of the m-methoxybenzyl alcohol on a molar basis and the use level of water is 0.8 to 1.5 times that of the m-methoxybenzyl alcohol on a mass basis. The method adopts water as the dissolvent and the nitric acid as an oxidizer to efficiently oxidize the m-methoxybenzyl alcohol into corresponding aldehyde, and has the advantages of simple operation, cheap and easily accessible raw materials, low requirement on equipments, environmental protection, low toxicity, easy post treatment and the like; and furthermore, the cost of the dissolvent is nearly zero. The method meets the requirement of environment-friendly industrial production; therefore, the application prospect of the method is considerably broad.
Description
Technical field
The invention belongs to the technical field of the preparation and the application of fine chemical product, is a kind of synthetic method of 3-methoxybenzaldehyde specifically.
Background technology
3-methoxybenzaldehyde/NSC 43794/meta-anisaldehyde 99, English name: 3-methoxybenzaldehyde/m-methoxybenzaldehyde/m-anisaldehy de, colourless or pale yellow oily liquid body, density: 1.119, boiling point: 143 ℃ (50mmHg), specific refractory power: 1.55-1.554, flash-point: 110 ℃, solvability: water insoluble, dissolve in alcohol, ether, benzene.CAS:591-31-1, molecular formula: C
8H
8O
2Molecular weight: 136.15, be widely used in chemical field as medicinal chemicals and organic intermediate and spices etc.The synthetic method of 3-methoxybenzaldehyde as claimed in claim belongs to this patent of invention.Compound of the present invention is the necessary raw material of synthetic isoquinoline 99.9 and derivative thereof, isoquinoline 99.9 and derivative thereof are the important intermediate of synthetic drugs and dyestuff, and has good biological activity, be to synthesize some at the pharmaceutical intermediate that the better curative effect effect is arranged aspect the treatment human diseases, such as: with the 3-methoxybenzaldehyde is that starting raw material synthetic 6-methoxyl group-5-Cyanoisoquinoline compounds is the important source material of synthesis of natural alkaloid Yohimbine, Yohimbine is not only obvious in the effect of treatment male sexual disorder, and tangible effect is also arranged at the aspects such as treatment heart disease and fat-reducing that bring high blood pressure down, Yohimbine can also be as instrument medicines such as diuretic(s) and antagonists simultaneously, and this compounds is used more and more widely aspect human disease treatment.
Based on this compounds at medical field, the importance of dyestuff manufacture field and chemical field, so NSC 43794 has very high practical value, but the method and the condition of synthetic this compound are limited at present, document introduction at present be that the method for the synthetic NSC 43794 of raw material is mostly utilized catalyzer with the meta-methoxy phenylcarbinol, such as being catalyzer with TEMPO/Cu (II), under airtight pressurization alkaline condition, arrive aldehyde (Adv.Synth.Catal.2007 with dioxygen oxidation alcohol, 349,1173-1179); With Na
4[W
10O
32]/ZrO
2For catalyzer in acetonitrile with dioxygen oxidation alcohol to aldehyde (Journal of Molecular Catalysis A:Chemical 277 (2007) 47-52) and microwave reaction as with KIO
4/ Et
4NBr is that catalyzer is oxidized to corresponding aldehyde with oxygen with alcohol under microwave condition.(SynthesisCommunications，36：2563-2568，2006)。Aforesaid method has all used catalyzer, and compressive reaction in enclosed system, therefore to the requirement of plant and instrument than higher, and the catalyzer price is expensive, is not easy to obtain, and uses acetonitrile to make solvent in microwave reaction, price is much higher with respect to the water of zero cost almost, simultaneously human body and environment are had harm, and water all is friendly to human body and environment, the aftertreatment of above-mentioned reaction is than complexity of the present invention.And microwave reaction and compressive reaction are big to the instrument loss, cost is high, economic benefit is low, is not suitable for suitability for industrialized production.The method of pertinent literature with the nitric acid direct oxidation also arranged, such as using HNO simultaneously
3/ CH
2Cl
2(Eur.J.Org.Chem.2003,526_536) system direct oxidation alcohol obtains corresponding aldehyde, but adopted methylene dichloride to make solvent in the document, and the consumption of nitric acid is three times of alcohol, and the present invention uses water as solvent, and the consumption of nitric acid is more than a times of alcohol, and simultaneously productive rate is low than the present invention, from cost consideration, this method is not as economy of the present invention.In addition, pertinent literature reports that a kind of method of synthetic NSC 43794 is: utilize m-hydroxybenzaldehyde to be raw material, methylating with methyl-sulfate obtains product.It is simple that this method seems, but the relative meta-methoxy phenylcarbinol of stock yard hydroxy benzaldehyde is expensive, and adopted high toxicity (show as photophobia during calomel poisoning, shed tears, conjunctival congestion, cough, expectoration, uncomfortable in chest, show as obvious cough, expectoration during moderate intoxication, out of breath, with cyanosis uncomfortable in chest and slight, then cough up a large amount of whites or pink frothy sputum during severe intoxication, obviously have difficulty in breathing cyanosis, occur together and suffocate, pneumothorax, mediastinal emphesema, subcutaneous emphysema.The adult respiratory distress syndrome appears in severe patient) methyl-sulfate as methylating reagent, from hazardness, economy and environmental friendliness aspect, not as method of the present invention superior.
Summary of the invention
The object of the present invention is to provide a kind of not only efficient but also economic method that meets the synthetic 3-methoxybenzaldehyde that green synthetic is suitable for producing in enormous quantities.
The preparation method of 3-methoxybenzaldehyde of the present invention, with the meta-methoxy phenylcarbinol is raw material, under the condition of room temperature, obtains with the nitric acid direct oxidation with water as solvent, the molar weight of nitric acid and meta-methoxy phenylcarbinol than be 1～2,0.8～1.5 of the quality of water and meta-methoxy phenylcarbinol.
The concentration of described nitric acid is 10%-50%.
Temperature of reaction is preferably 10-18 ℃.
The concentration of nitric acid is for being preferably 25%-35%.
The present invention adopts water to make solvent, nitric acid is as oxygenant, the meta-methoxy phenylcarbinol is oxidized to corresponding aldehyde efficiently, and this method is easy and simple to handle, and raw material is cheap and easy to get, simple to equipment requirements, environmentally friendly, advantage such as low toxicity and aftertreatment are simple, and solvent near-zero cost, meet the suitability for industrialized production requirement of environmental protection, therefore application prospect of the present invention is very wide.
The present invention has these points advantage: 1. the present invention adopts the meta-methoxy phenylcarbinol as starting raw material, and raw material is cheap and easy to get.2. the present invention adopts nitric acid as oxygenant, does not almost directly use nitric acid that the meta-methoxy benzyl alcohol oxidation is become corresponding aldehyde in document in the past, and relative other oxygenant cheapnesss of nitric acid.3. the present invention adopts the water as solvent that cost is almost equal to zero, the organic solvent cheapness that adopts in the relative additive method, environmental protection.4. the present invention is the oxidizing reaction of carrying out at ambient temperature, and some reacting by heating have further reduced production cost relatively.5. termination reaction of the present invention is convenient, and the thin-layer chromatography detection reaction finishes the back and stops to stir layering, reaction terminating at once.The aftertreatment of reaction is simple, and waste treatment is easy, makees solvent with water, the productive rate that room temperature just can reach more than 90% in seven hours, so the present invention has very high superiority in industrial production.
Description of drawings
Fig. 1 is the reaction process of water as solvent with nitric acid direct oxidation synthesizing methoxy phenyl aldehyde
Embodiment
Synthesizing methoxy method of benzaldehyde of the present invention is as follows:
The oxidation of meta-methoxy phenylcarbinol
Embodiment 1
Nitric acid is 1.5 with the molar weight ratio of meta-methoxy phenylcarbinol, and the mass ratio of water and meta-methoxy phenylcarbinol is 1;
With two-mouth bottle reduce to 5 the degree below add the meta-methoxy phenylcarbinol then, start stirring, then add the salpeter solution for preparing in advance, finish, system is returned to room temperature, TLC and liquid phase monitoring reaction, after about seven hours, in system, add the sodium hydroxide solution neutralization, use dichloromethane extraction, water and saturated common salt water washing, anhydrous magnesium sulfate drying.The decompression precipitation obtains product.Yield: 94%.
1HNMR(300M，CDCl
3)δ(ppm)9.87(s，1H，CHO)，3.73(s，3H，CH
3)，7.05(d，1H，ArH)，7.32-7.37(m，3H，ArH).
Embodiment 2
Nitric acid is 1 with the molar weight ratio of meta-methoxy phenylcarbinol, and the mass ratio of water and meta-methoxy phenylcarbinol is 0.8～1.5; Step is identical with embodiment 1, yield: 71%.
Embodiment 3
Nitric acid is 2 with the molar weight ratio of meta-methoxy phenylcarbinol, and the mass ratio of water and meta-methoxy phenylcarbinol is 1.5; Step is identical with embodiment 1, yield: 73%.
Claims (4)
1. the preparation method of a 3-methoxybenzaldehyde, it is characterized in that with the meta-methoxy phenylcarbinol be raw material, under the condition of room temperature, obtain with the nitric acid direct oxidation with water as solvent, nitric acid is 1～2 with the molar weight ratio of meta-methoxy phenylcarbinol, and the mass ratio of water and meta-methoxy phenylcarbinol is 0.8～1.5.
2. the preparation method of 3-methoxybenzaldehyde as claimed in claim 1 is characterized in that, the concentration of nitric acid is 10%-50%.
3. the preparation method of 3-methoxybenzaldehyde as claimed in claim 1 is characterized in that, temperature of reaction is 10-18 ℃.
4. the preparation method of 3-methoxybenzaldehyde as claimed in claim 2 is characterized in that, the concentration of nitric acid is 25%-35%.
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|---|---|---|---|
| CN2009100692035A CN101570473B (en) | 2009-06-10 | 2009-06-10 | Method for synthesizing 3-methoxybenzaldehyde |
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|---|---|---|---|
| CN2009100692035A CN101570473B (en) | 2009-06-10 | 2009-06-10 | Method for synthesizing 3-methoxybenzaldehyde |
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| CN101570473B CN101570473B (en) | 2011-11-09 |
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| CN2009100692035A Expired - Fee Related CN101570473B (en) | 2009-06-10 | 2009-06-10 | Method for synthesizing 3-methoxybenzaldehyde |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483166A (en) * | 2013-09-16 | 2014-01-01 | 台州职业技术学院 | Method for preparing m-anisaldehyde |
-
2009
- 2009-06-10 CN CN2009100692035A patent/CN101570473B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483166A (en) * | 2013-09-16 | 2014-01-01 | 台州职业技术学院 | Method for preparing m-anisaldehyde |
| CN103483166B (en) * | 2013-09-16 | 2015-06-24 | 台州职业技术学院 | Method for preparing m-anisaldehyde |
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| CN101570473B (en) | 2011-11-09 |
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