CN104418717B - A kind of preparation method of P-methoxybenzal-dehyde - Google Patents
A kind of preparation method of P-methoxybenzal-dehyde Download PDFInfo
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Abstract
The present invention relates to the preparation method of a kind of P-methoxybenzal-dehyde, its step is as follows: methyl phenyl ethers anisole, formaldehyde, organic solvent are pressed certain mol proportion mixing, and at ambient pressure, 0 20 DEG C, with under stirring condition, lead to hydrogen chloride gas in reactant liquor and react；Then by reactant liquor stratification, separate organic layer, then add water, alkaline aqueous solution washing, normal pressure desolventizing, methoxyl group benzyl chloride will be steamed by decompression；Methoxyl group benzyl chloride, hexamethylenamine will be pressed certain mol proportion mixing, add ethanol and water as solvent back flow reaction, continue back flow reaction after then adjusting pH to 36 until raw material reaction is complete；Normal pressure takes off ethanol, has taken off stratification after ethanol, and product P-methoxybenzal-dehyde is steamed by upper organic layer decompression.The crude yield of the present invention is 90 95%, and o-methoxybenzaldehyde is 96 99% with the purity of P-methoxybenzal-dehyde, o-methoxybenzaldehyde: P-methoxybenzal-dehyde mol ratio is less than 20%, such as=2:9.
Description
Technical field
The present invention relates to the preparation method of a kind of organic intermediate, in particular to right
The preparation method of methoxybenzaldehyde, belongs to spices and essence chemical technology field.
Background technology
P-methoxybenzal-dehyde (p-methoxybenzaldehyde), in organic synthesis
Mesosome, as middle taste type spice, is widely used in preparation bouquet type composition；For medicine,
Food and daily chemical industry.P-methoxybenzal-dehyde is also used as preparation to methoxy
Base benzyl alcohol and the raw material of some sunscreen products.
The method disclosing multiple synthesis P-methoxybenzal-dehyde at present, such as:
A kind of method preparing P-methoxybenzal-dehyde is with paracresol as raw material, at alkali
Under the conditions of property, with the compounding catalysis of the catalyst such as cobalt salt, mantoquita, logical dioxygen oxidation generates
Hydroxy benzaldehyde, then generates P-methoxybenzal-dehyde with dimethyl sulfate methylation of ester,
Two step yields are about 66-70%.
The major defect of this method is mainly reflected in two aspects: on the one hand, aoxidizes at PHB
In step, produce substantial amounts of waste water, mainly the para hydroxybenzene first containing over oxidation
Acid and other by-products, the ether compound such as generated；On the other hand, raw material
The source of paracresol is relatively difficult, either separates or toluene sulfonation alkali from tar-acids
Melt method, between being of gained, paracresol mixture, owing to both boiling points are the poorest
0.3-0.4 DEG C, therefore generally can not get pure paracresol by rectificating method.External logical
Cross urea complexation or isobutene. alkylation method separates, cause the pure paracresol of gained
Expensive.
It is being former to methoxy toluene that another kind prepares the method for P-methoxybenzal-dehyde
Material, by acid condition, adds the compounding logical dioxygen oxidation of the catalyst such as cobalt salt and generates
P-methoxybenzal-dehyde.The shortcoming of this method is also mainly reflected in two aspects: on the one hand meeting
Produce substantial amounts of waste water, on the other hand can produce substantial amounts of p-Methoxybenzoic acid, by
Cheap in this side-product, thus cause and on cost, have certain pressure.
Therefore, how to avoid the raw material that use cost is higher, reduce life the most as far as possible
During product produce waste water thus reduce environmental protection pressure, and as the highest yield,
It is urgently to be resolved hurrily that high yield acquisition target product is always commercial production methoxybenzaldehyde
Problem.
Summary of the invention
Therefore, it is an object of the invention to provide a kind of technique simple, eco-friendly
Low cost prepares the method for P-methoxybenzal-dehyde.
The present inventor finds through research, and can select methyl phenyl ethers anisole is raw material, to benzene first
After ether adds solvent and formalin, it is passed through hydrogen chloride gas while stirring and carries out
Chloromethylation, obtains methoxyl group benzyl chloride, then to adding second in methoxyl group benzyl chloride
Alcohol and hexamethylenamine, thus aoxidize the P-methoxybenzal-dehyde of preparation high-quality, two steps
Overall yield of reaction is generally 70-80%, wherein o-methoxybenzaldehyde with to methoxybenzene
The mol ratio of formaldehyde is generally below 20%, for example, 2:9.
Therefore, the technique of the synthesis P-methoxybenzal-dehyde that the present invention provides includes as follows
Step:
Step 1), by (the most nonpolar organic molten to methyl phenyl ethers anisole, formaldehyde, organic solvent
Agent) mix for 1:1.0-1.5:1-5 in molar ratio, at ambient pressure, 0-20 DEG C and stir
Under the conditions of mixing, logical hydrogen chloride gas in reactant liquor, methyl phenyl ethers anisole and hydrogen chloride gas
Mol ratio is 1:4-6, reacts 1-10h；
Step 2), by reactant liquor stratification, separate organic layer, then add water, carbon
Acid sodium or sodium hydrate aqueous solution washing, normal pressure desolventizing, decompression will be to methoxyl group chlorine
Benzyl steams；
Step 3), methoxyl group benzyl chloride, hexamethylenamine 1:1-2 in molar ratio will be mixed,
Add ethanol and water as solvent back flow reaction, then add concentrated hydrochloric acid and adjust pH to 3-6 follow-up
Continuous back flow reaction is until raw material reaction is complete；
Step 4), normal pressure takes off ethanol, has taken off stratification after ethanol, upper organic layer
Product P-methoxybenzal-dehyde is steamed by decompression.
The chemical reaction skeleton symbol of the present invention is expressed as:
According to the present invention, in step 1, the methyl phenyl ethers anisole that alternative costs are cheap is as former
Material, uses formaldehyde to carry out chloromethylation.Described formaldehyde is the aqueous solution form of formaldehyde,
Its concentration is 30～50%, and preferred concentration is the formalin of 33～45%, more excellent
The formalin (also referred to as formalin) selecting concentration to be 35～40%, such as its
Concentration can be 38～39%.
Methyl phenyl ethers anisole is 1:1.0-1.5, preferably methyl phenyl ethers anisole and formaldehyde with the mol ratio of formaldehyde
Mol ratio be 1:1.01-1.2, more preferably 1:1.01-1.1.Formaldehyde excess be in order to
Methyl phenyl ethers anisole is made fully to react.
According to the present invention, in chloromethylation step, the solvent used is organic molten
Agent, preferably non-polar organic solvent, its effect is to be beneficial to be layered, and forms water layer
And organic solvent layer, described non-polar organic solvent can be inert to chloromethylation
Any organic solvent, such as normal hexane, hexamethylene, petroleum ether, benzene, toluene,
Carbon tetrachloride and Carbon bisulfide etc., preferably normal hexane, hexamethylene, petroleum ether, toluene,
More preferably normal hexane, hexamethylene, petroleum ether, especially hexamethylene and petroleum ether.
Methyl phenyl ethers anisole is 1:1-5, preferably 1:1-3 with the mol ratio of organic solvent, more excellent
Select 1:1-2, most preferably 1:1-1.5.
Therefore, in step 1, methyl phenyl ethers anisole, formaldehyde, organic solvent can by mole
Mix than 1:1.0-1.5:1-5, preferably methyl phenyl ethers anisole, formaldehyde, organic solvent
Mol ratio is 1:1.01-1.2:1-3, more preferably 1:1.01-1.1:1-2.
According to the present invention, methyl phenyl ethers anisole can be 1:4-6 with the mol ratio of hydrogen chloride gas,
Preferably 1:4-5, most preferably 1:4-4.5.
Logical with the reactant liquor of organic solvent formation to above-mentioned methyl phenyl ethers anisole, formalin
After hydrogen chloride gas, chloromethylation is carried out the most under agitation, instead
Answering temperature to be 0-20 DEG C, the reaction temperature preferably controlling chloromethylation is 5-15 DEG C, more
It is preferably controlled in 8-12 DEG C.Carry out at relatively low temperature, be to make chloromethane
Glycosylation reaction is steadily carried out, it is to avoid temperature is too high causes by-product to increase.
Chloromethylation carries out 1-10h, preferably carries out 1.5-8h, more preferably react into
Row 2-5h.
According to the present invention, the chloromethylation carried out under these conditions can realize benzene
The conversion completely of methyl ether, then by reactant liquor stratification, separates organic layer, then
Add water, aqueous sodium carbonate or sodium hydrate aqueous solution washing, washable repeatedly, excellent
Selecting washable 3 times, then normal pressure desolventizing, decompression (such as uses oil pump to obtain true
Dummy status, such as pressure reach 1mmHg) methoxyl group benzyl chloride will be steamed, Qi Zhonghan
There is a small amount of O-methoxy benzyl chlorine.
According to the present invention, the O-methoxy benzyl chlorine obtained and the choosing of p-methoxybenzyl chloride
Selecting property reaches 85-95%, and separation yield reaches 80-90%, dichloromethyl by-product
Seldom, generally less than 5%.
According to the present invention, in step 3, hexamethylenamine is used to aoxidize with to methoxy
Base benzyl chlorine is main benzyl chloride.Hexamethylenamine is also referred to as hexamethylenetetramine, six methines
Tetramine, is a multi-ring heterocyclic compound similar with adamantane structure, and molecular formula is
C6H12N4。
According to the present invention, will be to methoxyl group benzyl chloride, hexamethylenamine 1:1-2 in molar ratio
Mixing, mol ratio is preferably 1:1-1.5, more preferably 1:1-1.2.
Then in the mixed solution of gained, add second alcohol and water as solvent, ethanol and
Water can be to add the most respectively, it is also possible to directly adds the aqueous solution of ethanol,
The ratio that wherein ethanol accounts for can be 40% or more than, preferably 40-95%, more preferably
For 50-80%, particularly preferred 55-75%.Under reflux conditions carry out oxidation reaction,
Then add concentrated hydrochloric acid and adjust pH to 3-6, preferably 3-5, more preferably 3-4, then continue
Continuous back flow reaction, until raw material reaction is complete.
According to the present invention, by selection ethanol as solvent, and concentrated hydrochloric acid regulation and control pH
Value, it is possible to achieve benzyl chlorine complete oxidation is converted into aldehyde, and then normal pressure takes off ethanol, has taken off
Rear stratification, upper organic layer decompression (such as use oil pump to obtain vacuum state,
Such as pressure reaches 1mmHg) product P-methoxybenzal-dehyde is steamed, due to wherein
Containing a small amount of o-methoxybenzaldehyde, the most actually o-methoxybenzaldehyde and to first
Epoxide benzaldehyde steams in the lump.
According to the present invention, the selectivity of the methoxybenzaldehyde obtained reach 95% with
On, yield reaches 90-95%, and product of distillation (comprises o-methoxybenzaldehyde and right
Methoxybenzaldehyde) purity reach 96-99%, o-methoxybenzaldehyde accounts for adjacent first
Epoxide benzaldehyde is generally below 20% with the ratio of P-methoxybenzal-dehyde mixture, example
As less than 18.2%.Other by-products are little.
The beneficial effects are mainly as follows the following aspects:
1, in chloromethylation step, by select suitable non-polar organic solvent with
And the intake of the reaction temperature of conservative control chloromethylation, hydrogen chloride gas, formaldehyde
The process conditions such as the inventory of aqueous solution, it is achieved that the conversion completely of methyl phenyl ethers anisole, a first
The selectivity of epoxide benzyl chlorine and p-methoxybenzyl chloride reaches 85-95%, and separation yield reaches
To 80-90%, dichloromethyl by-product is generally less than 5%.
2, in hexamethylenamine oxidation step, by selecting ethanol or ethanol water to make
For solvent and Reasonable Regulation And Control pH value, it is achieved that methoxybenzyl chlorine complete oxidation converts
For methoxybenzaldehyde, it is achieved that 100% conversion of methoxybenzyl chlorine, methoxybenzene
The selectivity of formaldehyde reaches more than 95%, and yield reaches 90-95%, product of distillation
Purity reaches (adjacent+to) 96-99%, and adjacency pair reaches 2/9 for ratio.
The raw material that the inventive method is used is easy to get, and technique is simple, and the response time is short,
Yield is high, and reaction only needs extracting and demixing, decompression distillation and rectification i.e. to can get high-quality
Product, yield 70-80%.Crude yield 90-95%, product purity is 96-99%,
Wherein P-methoxybenzal-dehyde ratio is the highest, such as o-methoxybenzaldehyde: to methoxy
Benzaldehyde can reach 2:9.
Detailed description of the invention
Present invention is further explained and described below by way of detailed description of the invention, but
Embodiment is not to be construed as limiting the scope of the invention.
Embodiment 1
Throw methyl phenyl ethers anisole 100g (0.926mol), 40% formalin 76.4g (1.02mol, 1.1eq)
With petroleum ether 100g, temperature control 8-12 DEG C, it is passed through hydrogen chloride gas 5.0eq(while stirring relative
In methyl phenyl ethers anisole).Response time 3h, during logical hydrogen chloride gas, first has white in reactant liquor
Color solid separates out, then re-dissolved.
After reaction terminates, reactant liquor stratification, upper organic layer is successively with 100g water, 100g
10% sodium hydrate aqueous solution washing, oil phase normal pressure removing petroleum ether, oil pump is decompressed to 1mmHg
Steam benzyl chloride, the crude product 130.5g that must reduce pressure (O-methoxy benzyl chlorine+p-methoxybenzyl chloride, content
96.2%, O-methoxy benzyl chlorine/p-methoxybenzyl chloride mol ratio=2/9), yield 86.6%.
130.5g distillation crude product after chloromethylation adds 134.7g (0.962mol, 1.2eq)
Hexamethylenamine and 120g water and 100g ethanol, stirring and dissolving, be heated to reflux 1h, then use
37% concentrated hydrochloric acid adjusts reactant liquor pH to 3, continues back flow reaction 4h, until methoxybenzyl chloro
The complete stopped reaction of this reaction.
Normal pressure takes off ethanol, has taken off direct layering after ethanol, upper organic layer oil pump decompression distillation (example
As at 1mmHg) steam product 105.6g (o-methoxybenzaldehyde+P-methoxybenzal-dehyde,
Content 98.2%, o-methoxybenzaldehyde/P-methoxybenzal-dehyde mol ratio=1/4.4), yield
95.1%。
Embodiment 2
Throw methyl phenyl ethers anisole 100g (0.926mol), 40% formalin 76.4g (1.02mol, 1.1eq)
With hexamethylene 100g, temperature control 15-20 DEG C, it is passed through hydrogen chloride gas 6.0eq(while stirring relative
In methyl phenyl ethers anisole).Response time 3h, during logical hydrogen chloride gas, first has white in reactant liquor
Color solid separates out, then re-dissolved.
After reaction terminates, reactant liquor stratification, upper organic layer is successively with 100g water, 100g
10% sodium hydrate aqueous solution washing, oil phase normal pressure removing hexamethylene, oil pump is decompressed to 1mmHg
Steam benzyl chloride, the crude product 120.4g that must reduce pressure (O-methoxy benzyl chlorine+p-methoxybenzyl chloride, content
94.3%, O-methoxy benzyl chlorine/p-methoxybenzyl chloride mol ratio mol ratio=1/4.3), yield
78.3%。
120g distillation crude product after chloromethylation adds 121.8g (0.87mol, 1.2eq) crow
Lip river tropine and 100g water and 100g ethanol, stirring and dissolving, be heated to reflux 1h, then with 37%
Concentrated hydrochloric acid adjusts reactant liquor pH to 3, continues back flow reaction 4h, until methoxybenzyl benzyl chloride is basic
React stopped reaction.
Normal pressure takes off ethanol, and ethanol has taken off rear stratification, and upper organic layer oil pump is decompressed to 1mmHg
Steam product, obtain product 97g (o-methoxybenzaldehyde+P-methoxybenzal-dehyde, content
95.3%, o-methoxybenzaldehyde/P-methoxybenzal-dehyde mol ratio=1/4.15), yield 93.8%.
Embodiment 3
Throw methyl phenyl ethers anisole 100g (0.926mol), 40% formalin 76.4g (1.02mol, 1.1eq)
With petroleum ether 100g, temperature control 15-20 DEG C, it is passed through hydrogen chloride gas 5.0eq(while stirring relative
In methyl phenyl ethers anisole).Response time 3h, during logical hydrogen chloride gas, first has white in reactant liquor
Color solid separates out, then re-dissolved.
After reaction terminates, reactant liquor stratification, upper organic layer is successively with 100g water, 100g
10% sodium hydrate aqueous solution washing, oil phase normal pressure removing hexamethylene, oil pump is decompressed to 1mmHg
Steam benzyl chloride, the crude product 122.8g that must reduce pressure (O-methoxy benzyl chlorine+p-methoxybenzyl chloride, content
95.2%, O-methoxy benzyl chlorine/p-methoxybenzyl chloride mol ratio=2/9), yield 80.6%.
122.8g distillation crude product after chloromethylation adds 125.3g (0.895mol, 1.2eq)
Hexamethylenamine and 100g water and 100g ethanol, stirring and dissolving, be heated to reflux 1h, then use
37% concentrated hydrochloric acid adjusts reactant liquor pH to 3, continues back flow reaction 4h, until methoxyl group chlorobenzyl
The complete stopped reaction of this reaction.
Normal pressure takes off ethanol, and ethanol has taken off rear stratification, and upper organic layer oil pump is decompressed to 1mmHg
Steaming product, (o-methoxybenzaldehyde+P-methoxybenzal-dehyde, contains to obtain product 98.3g
Amount 97.3%, o-methoxybenzaldehyde/P-methoxybenzal-dehyde mol ratio=1/4.4), yield 94.3%.
Embodiment 4
Throw methyl phenyl ethers anisole 100g (0.926mol), 40% formalin 76.4g (1.02mol, 1.1eq)
And normal hexane 50g and hexamethylene 50g, temperature control 8-12 DEG C, it is passed through hydrogen chloride gas while stirring
Body 5.0eq(is relative to methyl phenyl ethers anisole).Response time 3h, during logical hydrogen chloride gas,
Reactant liquor first there is white solid separate out, then re-dissolved.
After reaction terminates, reactant liquor stratification, upper organic layer is successively with 100g water, 100g
10% sodium hydrate aqueous solution washing, oil phase normal pressure removing hexamethylene, oil pump is decompressed to 1mmHg
Steam benzyl chloride, the crude product 113.9g that must reduce pressure (O-methoxy benzyl chlorine+p-methoxybenzyl chloride, content
93.2%, O-methoxy benzyl chlorine/O-methoxy benzyl chlorine=1/3.9), yield 73.2%.
113.9g distillation crude product after chloromethylation adds 114g (0.81mol, 1.2eq) crow
Lip river tropine and 100g water and 100g ethanol, stirring and dissolving, be heated to reflux 1h, then with 37%
Concentrated hydrochloric acid adjusts reactant liquor pH to 3, continues back flow reaction 4h, until methoxyl group benzyl chloride is the most anti-
Answer stopped reaction.
Normal pressure takes off ethanol, and ethanol has taken off rear stratification, and upper organic layer oil pump is decompressed to 1mmHg
Steaming product, (o-methoxybenzaldehyde+P-methoxybenzal-dehyde, contains to obtain product 86.8g
Amount 97.3%, o-methoxybenzaldehyde/P-methoxybenzal-dehyde mol ratio=1/4), yield 91.6%.
Should be appreciated that, although the present invention combines example and has been described in detail, but on
State and bright be intended to illustrate, and limit its summary of the invention never in any form.To this
For art people, can farthest utilize the present invention based on explanation herein,
And multiple amendment can be carried out in without departing from scope of the presently claimed invention or spirit
Or modify.Each list of references cited in the application, is incorporated herein in its entirety as ginseng
Examine.
Claims (12)
1. the synthetic method of a P-methoxybenzal-dehyde, it is characterised in that the method
Comprise the steps:
1) it is, 1 in molar ratio by methyl phenyl ethers anisole, formaldehyde, non-polar organic solvent:
1.01-1.2:1-3 mixes, at ambient pressure, under 5-15 DEG C and stirring condition, to reaction
Being passed through hydrogen chloride gas in liquid, methyl phenyl ethers anisole is 1:4-5 with the mol ratio of hydrogen chloride gas,
Reaction 1.5-8h, described formaldehyde be concentration be the formalin of 30～50%, non-pole
Property organic solvent selected from normal hexane, hexamethylene, petroleum ether；
2), by reactant liquor stratification, separate organic layer, then add water, sodium carbonate
Aqueous solution or sodium hydrate aqueous solution washing, normal pressure desolventizing, decompression will be to methoxyl group
Benzyl chloride steams；
3), methoxyl group benzyl chloride, hexamethylenamine 1:1-1.5 in molar ratio will be mixed,
Add ethanol and water as solvent back flow reaction, the ratio that wherein ethanol accounts for be 40% or more than,
Then add after concentrated hydrochloric acid adjusts pH to 3-6 and continue back flow reaction until raw material reaction is complete；
4), normal pressure takes off ethanol, has taken off stratification after ethanol, and upper organic layer reduces pressure
Product P-methoxybenzal-dehyde is steamed.
Method the most according to claim 1, it is characterised in that: in step 1,
Described formaldehyde be concentration be the formalin of 33～45%, methyl phenyl ethers anisole rubs with formaldehyde
That ratio is 1:1.01-1.1.
Method the most according to claim 1, it is characterised in that: in step 1,
Described non-polar organic solvent is selected from hexamethylene and petroleum ether, methyl phenyl ethers anisole and organic solvent
Mol ratio be 1:1-2.
Method the most according to claim 1, it is characterised in that: in step 1,
Methyl phenyl ethers anisole is 1:4-4.5 with the mol ratio of hydrogen chloride gas.
Method the most according to claim 1, it is characterised in that: in step 1,
The reaction temperature of chloromethylation is 8-12 DEG C.
Method the most according to claim 1, it is characterised in that: in step 1,
Chloromethylation carries out 2-5h.
7. according to the method one of claim 1 to 6 Suo Shu, it is characterised in that: step
In rapid 2, by reactant liquor stratification, separate organic layer, then add water, sodium carbonate
Aqueous solution or sodium hydrate aqueous solution washing, then normal pressure desolventizing, use oil pump to subtract
Methoxyl group benzyl chloride will be steamed by pressure.
8. according to the method one of claim 1 to 6 Suo Shu, it is characterised in that: step
In rapid 3, the mol ratio to methoxyl group benzyl chloride Yu hexamethylenamine is 1:1-1.2, uses
Second alcohol and water is 40-95% as solvent, the ratio that wherein ethanol accounts for.
Method the most according to claim 8, it is characterised in that: wherein ethanol accounts for
Ratio be 50-80%.
Method the most according to claim 9, it is characterised in that: wherein ethanol
The ratio accounted for is 55-75%.
11. according to the method one of claim 1 to 6 Suo Shu, it is characterised in that:
In step 3, add concentrated hydrochloric acid and adjust pH value to be 3-5.
12. methods according to claim 11, it is characterised in that: step 3
In, add concentrated hydrochloric acid and adjust pH value to be 3-4.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1491930A (en) * | 2002-10-25 | 2004-04-28 | 大化集团有限责任公司研究院 | Synthetic process for p-methoxy benzaldehyde |
| WO2008023836A1 (en) * | 2006-08-23 | 2008-02-28 | Ube Industries, Ltd. | Process for production of benzaldehyde compound |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1491930A (en) * | 2002-10-25 | 2004-04-28 | 大化集团有限责任公司研究院 | Synthetic process for p-methoxy benzaldehyde |
| WO2008023836A1 (en) * | 2006-08-23 | 2008-02-28 | Ube Industries, Ltd. | Process for production of benzaldehyde compound |
Non-Patent Citations (1)
| Title |
|---|
| 对甲氧基苯乙腈的合成研究;严少平;《浙江大学硕士学位论文》;20101018;第12-16页 * |
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