CN103159635A - Method for preparing 4-methoxy-N-4-methylphenyl amine - Google Patents
Method for preparing 4-methoxy-N-4-methylphenyl amine Download PDFInfo
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- CN103159635A CN103159635A CN 201110416609 CN201110416609A CN103159635A CN 103159635 A CN103159635 A CN 103159635A CN 201110416609 CN201110416609 CN 201110416609 CN 201110416609 A CN201110416609 A CN 201110416609A CN 103159635 A CN103159635 A CN 103159635A
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Abstract
The invention relates to a method for preparing 4-methoxy-N-4-methylphenyl phenylaniline, comprising the steps of: (1) an acylation step: anisidine is subjected to an acylation reaction in the action of an organic acid to form N-acyl-4-methoxyaniline; (2) a condensation step: acylated products of the first step and p-halotoluene are subjected to a condensation reaction in the presence of an alkali, a composite catalyst, and ligand tri-tert-butylphosphine to form a condensation solution of N-acyl-4-methoxydiphenylamine; (3) an acyl alcoholysis step: in the system of potassium hydroxide and methanol, the deacylation step is performed to give a crude product solution of 4-methoxy-N-4-methylphenyl phenylaniline; and (4) a purification step: the finished product of 4-methoxy-N-4-methylphenyl phenylaniline is obtained through the distillation and crystallization of the crude product solution of 4-methoxy-N-4-methylphenyl phenylaniline. The method of the present invention is mild in reaction conditions, high in conversion rate and selectivity, and cheap and available in raw materials, thereby being suitable for industrial production.
Description
Technical field
The invention relates to the preparation method of organic synthesis intermediate 4-methoxyl group-N-4-tolyl aniline, belong to the organic synthesis intermediate technology of preparing.
Technical background
4-methoxyl group-N-4-tolyl aniline is the intermediate of synthetic electroluminescent organic material (OLED), also is used for the synthetic of medicine.
There is patent (CN101570490A) to mention with N-(p-methylphenyl) ethanamide with to methoxyl group iodobenzene synthetic this product under catalyzer and part existence.Wherein expensive to the methoxyl group iodobenzene as the reactant main body, make the finished product price high, affects downstream user and use.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of reaction conditions gentleness, transformation efficiency and selectivity is high, raw material is cheap and easy to get, be suitable for the preparation method that large-scale industrial is produced.
In order to solve the problems of the technologies described above, the invention provides the synthetic method of a kind of 4-methoxyl group-N-4-tolyl aniline, comprise the following steps:
(1) acidylate step: P-nethoxyaniline carries out acylation reaction under the organic acid effect, generates N-acyl group-4-anisidine;
(2) condensation step: go up the acylate of step and toluene halide is carried out condensation reaction in the presence of alkali, composite catalyst and part tri-tert phosphorus, generating the condensated liquid of N-acyl group-4-methoxyl group-N-4-tolyl aniline;
(3) acyl group alcoholysis step: go the acyl group step in potassium hydroxide and methanol system, obtain 4-methoxyl group-N-4-tolyl aniline crude product solution;
(4) purification step: form 4-methoxyl group-N-4-tolyl aniline finished product by 4-methoxyl group-N-4-tolyl aniline crude product distillation is added crystallization.
In wherein said step (1), organic acid is formic acid, acetic acid or diacetyl oxide.
Be para-bromo toluene or parachlorotoluene to toluene halide in wherein said step (2).
Wherein said step is also used as reaction solvent toluene halide in (2).
In wherein said step (2), composite catalyst is palladium and cuprous iodide composite catalyst, palladium and cuprous bromide composite catalyst, wherein palladium: the ratio of cuprous iodide or cuprous bromide is 1: 1～15 (mol).
The input amount of wherein said step (2) composite catalyst in reaction system is 100ppm～1%.
In wherein said step (2), alkali is potassium tert.-butoxide, sodium tert-butoxide, cesium carbonate, potassium hydroxide, sodium carbonate, Tripotassium phosphate, sodium amide and sodium hydride.
In wherein said step (2), part is tri-butyl phosphine.
Positive progressive effect of the present invention is: the present invention has optimized reaction conditions, provides that a kind of reaction conditions is gentle, transformation efficiency and selectivity is high, raw material is cheap and easy to get, be suitable for the preparation method that large-scale industrial is produced.
Embodiment
Embodiment 1. preparation 4-methoxyl group-N-4-tolyl aniline comprise the following steps:
1), acidylate step: add formic acid (88%) 26.1g (0.5mol) in the 100ml reaction flask; slowly add P-nethoxyaniline 12.3g (0.1mol) under stirring; finish; stir and slowly be warming up to backflow after 20 minutes; be incubated 1 hour, cooling, decompression steams water and excessive formic acid; get N-(p-methoxyphenyl) methane amide 14.6g, yield 96%.
2), condensation step: add 250ml dry upper step gained N-(p-methoxyphenyl) methane amide, in the four-hole reaction flask that nitrogen replacement is crossed, add successively 51.3g (0.3mol) para-bromo toluene, 10.57g (0.11mol) sodium tert-butoxide, 0.202g (10mmol) tri-butyl phosphine, the composite catalyst that fully adds again 0.112g (0.5mmol) palladium and 0.475g (2.5mmol) cuprous iodide to form after stirring and dissolving, be heated to return stirring reaction 12 hours under nitrogen protection, be down to room temperature, add 30ml toluene and stir fully dissolving, organic phase water (30ml * 3) is washed till neutrality, concentrated, steam except reclaiming toluene and as the para-bromo toluene of reaction solvent, in still, residue is condensation product.
3), acyl group alcoholysis step: upper step condensation product is put in the 100ml reaction flask; add methyl alcohol 60ml; potassium hydroxide 8.4g (0.15mol), reflux 2 hours changes water distilling apparatus; add toluene after reclaiming methyl alcohol; stir fully dissolving, organic phase water (30ml * 3) is washed till neutrality, concentrated organic phase; steam recovery toluene, in still, residue is 4-methoxyl group-N-4-tolyl aniline crude product.
4), purification step: 4-methoxyl group-N-4-tolyl aniline crude product is put in the 50ml still kettle, carry out molecular distillation, effluent liquid is obtained 4-methoxyl group-N-4-tolyl aniline finished product white squamous crystallization 15.1g with the sherwood oil recrystallization, purity 99.2% (HPLC), mp82～84 ℃, product yield 71% (in P-nethoxyaniline).
Embodiment 2～5:
Change the following reaction conditions in embodiment 1: organic acid step 1); Step 2) in to toluene halide; Composite catalyst and alkali, all the other parameters are all constant, obtain embodiment 2～5, thereby obtain the product yield of corresponding 4-methoxyl group-N-4-tolyl aniline.Particular content and data results see Table 1.
Table 1
Claims (8)
1. method for preparing 4-methoxyl group-N-4-tolyl aniline is characterized in that comprising the following steps:
(1) acidylate step: P-nethoxyaniline carries out acylation reaction under the organic acid effect, generates N-acyl group-4-anisidine;
(2) condensation step: go up the acylate of step and toluene halide is carried out condensation reaction in the presence of alkali, composite catalyst and part tri-tert phosphorus, generating the condensated liquid of N-acyl group-4-methoxyl group-N-4-tolyl aniline;
(3) acyl group alcoholysis step: go the acyl group step in potassium hydroxide and methanol system, obtain 4-methoxyl group-N-4-tolyl aniline crude product solution;
(4) purification step: by the distillation of 4-methoxy diphenylamine crude product, crystallization are formed 4-methoxy diphenylamine finished product.
2. the method for preparing 4-methoxyl group-N-4-tolyl aniline according to claim 1 is characterized in that: in described step (1), organic acid is formic acid, acetic acid or diacetyl oxide.
3. the method for preparing 4-methoxyl group-N-4-tolyl aniline according to claim 1, is characterized in that: be para-bromo toluene or parachlorotoluene to toluene halide in described step (2).
4. the method for preparing 4-methoxyl group-N-4-tolyl aniline according to claim 3, it is characterized in that: described step is also used as reaction solvent toluene halide in (2).
5. the method for preparing 4-methoxyl group-N-4-tolyl aniline according to claim 1, it is characterized in that: in described step (2), composite catalyst is palladium and cuprous iodide composite catalyst, palladium and cuprous bromide composite catalyst, wherein palladium: the ratio of cuprous iodide or cuprous bromide is 1: 1～15 (mol).
6. the method for preparing 4-methoxyl group-N-4-tolyl aniline according to claim 5, it is characterized in that: the input amount of described step (2) composite catalyst in reaction system is 100ppm～1%.
7. the method for preparing 4-methoxyl group-N-4-tolyl aniline according to claim 1 is characterized in that: in described step (2), alkali is potassium tert.-butoxide, sodium tert-butoxide, cesium carbonate, potassium hydroxide, sodium carbonate, Tripotassium phosphate, sodium amide and sodium hydride.
8. the method for preparing 4-methoxyl group-N-4-tolyl aniline according to claim 1 is characterized in that: in described step (2), part is tri-butyl phosphine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110416609 CN103159635A (en) | 2011-12-14 | 2011-12-14 | Method for preparing 4-methoxy-N-4-methylphenyl amine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110416609 CN103159635A (en) | 2011-12-14 | 2011-12-14 | Method for preparing 4-methoxy-N-4-methylphenyl amine |
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Application publication date: 20130619 |