CN104003898A - Method for synthesizing o-methoxy-m-acetyl amino-N,N-diallyl phenylamine by utilizing 2,4-dinitrobenzene methyl ether - Google Patents
Method for synthesizing o-methoxy-m-acetyl amino-N,N-diallyl phenylamine by utilizing 2,4-dinitrobenzene methyl ether Download PDFInfo
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- CN104003898A CN104003898A CN201410246470.6A CN201410246470A CN104003898A CN 104003898 A CN104003898 A CN 104003898A CN 201410246470 A CN201410246470 A CN 201410246470A CN 104003898 A CN104003898 A CN 104003898A
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Abstract
The invention relates to the field of chemical industry and in particular relates to a method for synthesizing o-methoxy-m-acetyl amino-N,N-diallyl phenylamine by utilizing 2,4-dinitrobenzene methyl ether. Overall, the method for synthesizing the o-methoxy-m-acetyl amino-N,N-diallyl phenylamine by utilizing the 2,4-dinitrobenzene methyl ether has the advantages that steps are simplified, nor separation or purification is needed in an intermediate process, a one-pot method can be adopted for production, and finally the o-methoxy-m-acetyl amino-N,N-diallyl phenylamine product is separated; zero discharge of three wastes is realized, conversion rate of each step is high, and excessive chloropropene and solvent are recycled together. The method for firstly synthesizing the o-methoxy-m-acetyl amino-N,N-diallyl phenylamine by utilizing the 2,4-dinitrobenzene methyl ether comprises the following steps: firstly, hydrogenating and then sedimenting or filtering by adopting a rotary plate for removing a catalyst, directly carrying out location acylation, wherein the conversion rate is more than 99%, HPLC (high performance liquid chromatography) main peak content is more than 99%; secondly, realizing a location acylation catalysis technology, wherein single acylation control can be 97%, and purity of a market product in the prior art is completely realized; thirdly, carrying out stable allylation in DMF (dimethyl formamide), wherein yield is high, and no acid-binding agent or phase transfer catalyst is needed to be added; after a reaction is finished, DMF and residual chloropropene and water are recycled by adopting a scraper evaporator; the chloropropene and water are recycled in the three step, and DMF is returned to the first step for hydrogenation; a material discharged from the scraper evaporator is naturally cooled, smashed and packaged into the o-methoxy-m-acetyl amino-N,N-diallyl phenylamine finished product, and no emission of three wastes exists.
Description
Technical field
The present invention relates to a kind of chemical field, refer to especially from the synthetic O-methoxy-m-acetamino-N of 2,4-dinitroanisol, the method for N-diallyl aniline.
Background technology
Reaction formula now:
The problem of shortcoming and existence:
Start to prepare subject matter step from p-Nitromethoxybenzene many, the three wastes are many, and cost is high, and yield is low, and energy consumption is large, is specially:
1, prepare Para-Anisidine from p-Nitromethoxybenzene reduction, because the intrinsic purity of p-Nitromethoxybenzene is low, necessary rectification process after reduction, overall yield only has 90%, if with a large amount of organic waste water of sodium polysulphide reduction meeting generation, wherein contain a large amount of Sulfothiorine;
2, prepared amide group methyl-phenoxide by Para-Anisidine, yield, purity are very high, but need very high temperature of reaction, produce a large amount of dilute acetic acid simultaneously, need comprehensive utilization;
3, the 3rd step nitrifying process, front product is many, and 2-nitro-4-acetyl-anisidine per ton need consume 2.5-3 ton 98% sulfuric acid, and these sulfuric acid all become the dilute sulphuric acid of 30%-40% containing organic waste, cannot utilize, the more than 100 tons water of ton product needed is washed simultaneously at all;
4, the existing technique of the 4th step is used iron powder reducing substantially, has a large amount of iron mud to produce, even if there are indivedual producers to use hydrogenating reduction, is also to make a certain amount of moisture 2-nitro-4-acetyl-anisidine;
5, water react is slow, and propenyl chloride easily decomposes, and excessive propenyl chloride remains in product, makes in the packing of product, transport, use procedure smell very large, has a large amount of waste water to produce simultaneously, in reaction, will use a large amount of acid binding agents.In waste water, be difficult to, biochemical propenyl chloride and organism, to also have a large amount of muriates except containing.Product also need finish to use a large amount of liquid caustic soda to adjust medium PH to make product crystallization in reaction.
Summary of the invention
In order to overcome the above problems, the invention provides that a kind of step is simple, productive rate is high, without any the three wastes from the synthetic O-methoxy-m-acetamino-N of 2,4-dinitroanisol, the method for N-diallyl aniline.
From the synthetic O-methoxy-m-acetamino-N of 2,4-dinitroanisol, the method for N-diallyl aniline, reaction scheme carries out successively by reaction formula (1)-(3):
From the synthetic O-methoxy-m-acetamino-N of 2,4-dinitroanisol, the method for N-diallyl aniline, comprises following reactions steps:
1) in preparation still, add dimethyl formyl (acetyl) amine, add quantitative 2.4-dinitroanisol, heat up and confirm to dissolve completely, airtight preparation still, nitrogen replacement air is stand-by;
2) in hydrogenation still, add a certain amount of dimethyl formyl (acetyl) amine, Pd/C/Ni catalyzer, nitrogen, hydrogen exchange hydrogenation still and all inlet and outlet pipings.Stir lower keep certain hydrogen pressure and temperature, with high-pressure diaphragm pump, 2.4-dinitroanisol solution quantitative timing in preparation still is carried and added in hydrogenation still, after adding, continue to keep certain temperature and hydrogen pressure 1-2 hour, confirm that reaction end arrives;
3) hydrogenation liquid is filtered out to catalyzer under nitrogen protection, directly squeezes in acidylate still, add compound location catalyzer, at a certain temperature from aceticanhydride scale tank drip aceticanhydride, terminal to after transfer in propenyl reactor;
4) in propenyl still, vacuum sucks propenyl chloride, closed reactor, slowly system is heated up, keep back heating up in a steamer state 2-3 hour and be warmed up to 80 DEG C, keep heating up in a steamer for 80 ± 5 DEG C times reaction 7-9 hour, the monosubstituted content of terminal control (HPLC) < 2%, main content >=96%.
5) terminal arrives, will return to heat up in a steamer to change recovery into, and cut recovery in 100 DEG C, 100 DEG C keep 1-2 hour, then material are pressed in scraper evaporator, and vacuum reclaims DMF to 120 DEG C/100pa, and in tower reactor, material scraper goes out natural air cooledly, pulverizes, and packaging is finished product.
Preferably, described step 1) in, purity >=99.5% of 2,4-dinitroanisol, the volume ratio of the weight of 2,4-dinitroanisol and dimethyl formamide or N,N-DIMETHYLACETAMIDE is 1:2～3, temperature is controlled at 60-80 DEG C.
Preferably, described step 2) in, in hydrogenation still, add amount and the step 1 of dimethyl formamide or N,N-DIMETHYLACETAMIDE) in 2,4-dinitroanisol V/D=1～2/1; The amount of Ni catalyzer is the 3-7% of 2,4-dinitroanisol weight, wherein the content 40-60% of Ni; Pd/C catalyzer is 5%Pd/C, and its consumption is the 0.3-0.5% of 2,4-dinitroanisol weight; Hydrogenation hydrogen pressure 8-25kg/cm2, temperature 30-70 DEG C, the main content of hydrogenation terminal is greater than 99%.
Preferably, described step 3) middle filtrator: sedimentation filtration method+bag filter for Ni catalyzer, Pd/C rotating plate strainer; Compound location catalyzer is Na2CO3, NaOH, MgO, CaO, NaAC, the compound compound of one or more of NaH2PO4; Acidylate temperature-5-10 DEG C, the mol ratio of aceticanhydride consumption and 2,4-dinitroanisol is 1:0.98～1.02, reaction end: amino substance≤0.5%, single acyl thing >=97%, two acyl 2-3%.
Preferably, step 3) in solvent can be dimethyl formamide or ethanamide, the consumption of propenyl chloride is by 2,4-dinitroanisol meter mol ratio is 1.9-1.96:1, the temperature 60-90 DEG C of reaction, reaction times 6-10 hour, product and separated from solvent, the recovery of residual raw materials is used scraper evaporator.
The present invention totally says, step simplification, and pilot process does not need to carry out any separation and purification, can use the method for the treatment of different things alike to produce, product separation the most at last.Zero emission, respectively walks transformation efficiency high, and excessive propenyl chloride is recycled together with solvent.
After the first step hydrogenation, sedimentation or rotating plate filter out catalyzer, directly position acidylate, transformation efficiency > 99%, HPLC main peak content > 99%;
Second step location acidylate catalysis technique, single acidylate control can reach 97%, reaches the purity of prior art commercially available product completely;
In the 3rd DMF, propenylization is steady, and productive rate is high, does not need to add acid binding agent, phase-transfer catalyst again.Reaction finishes, scraper plate evaporation recovery DMF and residual nitrogen propylene, water.Propenyl chloride, water are applied mechanically in the 3rd step, and DMF gets back in the first step for hydrogenation.In scraper evaporator, discharge material naturally cooling, pulverize, packaging is finished product, without any three waste discharge.
Embodiment
Embodiment 1
In 5000L enamel preparation still, add DMF4500 liter, under stirring, add 99.5%2.4-dinitroanisol 1800kg, be warmed up to 60-80 DEG C, stir and within 1-2 hour, confirm to dissolve, airtight preparation still, nitrogen replacement three times, guarantees system no oxygen (sampling detects);
In hydrogenation still, add DMF2700 liter, 55 kilograms of Ni catalyzer, the each displacement of nitrogen hydrogen three times, sampling oxygen determination gas surplus is qualified, system in hydrogenation still is warmed up to 30-40 DEG C, pass into 12atm pressure hydrogen, rise and quantitatively the DMF solution of 2.4-dinitroanisol is added in hydrogenation still simultaneously with high-pressure diaphragm pump 1200-1500 per hour, hierarchy of control temperature is no more than 60 DEG C, add and keep hydrogen pressure 12-16atm, temperature 60-70 DEG C of 1-2 hour, sampling, the main content of terminal is more than or equal to 99%.Terminal arrives, and reduces the temperature to 40 DEG C, and static 1-2 hour is pressed into feed liquid acidylate still by a bag filter with nitrogen from certain altitude discharge port, in acidylate still, falls air in advance with nitrogen replacement;
Material in acidylate still is cooled to 0 DEG C, keeps 0 ± 5 DEG C, add location composite catalyst 240kg, drip aceticanhydride 840kg, terminal control (HPLC) amino substance≤0.5%, two acyl≤2%, main content 96-97%;
Acidylate material is a collection of, be pressed in propenyl still, airtight propenyl still, vacuum sucks propenyl chloride 1250kg, open back and heat up in a steamer condenser, heat up, system has back the generation of heating up in a steamer in the time of 68-70 DEG C, maintain certain quantity of reflux to heat with steam jacket, within 2-3 hour, be warmed up to 80 ± 5 DEG C, keep control in 80 ± 5 DEG C of samplings in 7-9 hour, monosubstituted < 2%, main content >=96%, change back and heat up in a steamer for reclaiming, while being recovered to 100 DEG C, keep 1-2 hour, stop reclaiming, material is pressed in scraper evaporator, vacuum reclaims DMF to 120 DEG C/100pa, DMF is for hydrogenation reaction, material scrapes through naturally cooling, pulverize, packaging, obtain the finished product 1850kg of >=96% purity.
Embodiment 2:
Preparation still operates with example 1, adds 2700 liters of DMF in hydrogenation still, adds the fresh Ni catalyzer of 5kg, controls with the same terms in example 1, and hydrogenation, to terminal, is transferred to hydrogenation liquid in acidylate still;
Material is cooled to 0 DEG C in acidylate still, adds location composite catalyst 264kg, keep 0 ± 5 DEG C, drip aceticanhydride 935kg, control (HPLC) amino substance≤0.5%, two acyl≤2%, main content 96-97%;
Acylate is transferred in propenyl still, airtight propenyl still, vacuum sucks propenyl chloride 1375kg, open back and heat up in a steamer condenser, heat up, system has back the generation of heating up in a steamer in the time of 68-70 DEG C, maintain certain quantity of reflux to heat with steam jacket, within 2-3 hour, be warmed up to 80 ± 5 DEG C, keep control in 80 ± 5 DEG C of samplings in 7-9 hour, monosubstituted < 2%, main content >=96%, change back and heat up in a steamer for reclaiming, while being recovered to 100 DEG C, keep 1-2 hour, stop reclaiming, material is pressed in scraper evaporator, vacuum reclaims DMF to 120 DEG C/100pa, DMF is for hydrogenation reaction, material scrapes through naturally cooling, pulverize, packaging, obtain the finished product 2035kg of >=96% purity.
Finally, it is also to be noted that, what more than enumerate is only specific embodiments of the invention.Obviously, the invention is not restricted to above examples of implementation, can also have many distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (3)
1. synthesize O-methoxy-m-acetamino-N from 2,4-dinitroanisol, the method for N-diallyl aniline, reaction scheme carries out successively by reaction formula (1)-(3):
2. from the synthetic O-methoxy-m-acetamino-N of 2,4-dinitroanisol, the method for N-diallyl aniline, is characterized in that: comprise following reactions steps:
1) in preparation still, add dimethyl formamide or N,N-DIMETHYLACETAMIDE, add 2.4-dinitroanisol, heat up and confirm to dissolve completely, airtight preparation still, nitrogen replacement air is stand-by;
2) in hydrogenation still, add dimethyl formamide or N,N-DIMETHYLACETAMIDE, Pd/C/Ni catalyzer, nitrogen, hydrogen exchange hydrogenation still and all inlet and outlet pipings; Stir lower keep hydrogen pressure and temperature, with high-pressure diaphragm pump, 2.4-dinitroanisol solution quantitative timing in preparation still is carried and added in hydrogenation still, after adding, continue to keep temperature and hydrogen pressure 1-2 hour, confirm that reaction end arrives;
3) hydrogenation liquid is filtered out to catalyzer by strainer under nitrogen protection, directly squeezes in acidylate still, add compound location catalyzer, from aceticanhydride scale tank drip aceticanhydride, terminal to after transfer in propenyl reactor;
4), in propenyl still, vacuum sucks propenyl chloride, closed reactor, slowly system is heated up, keep back heating up in a steamer state 2-3 hour and be warmed up to 80 DEG C, keep heating up in a steamer for 80 ± 5 DEG C times reaction 7-9 hour, the monosubstituted content < 2% of terminal control, main content >=96%.
5) terminal arrives, will return to heat up in a steamer to change recovery into, and cut recovery in 100 DEG C, 100 DEG C keep 1-2 hour, then material are pressed in scraper evaporator, and vacuum reclaims DMF to 120 DEG C/100pa, and in tower reactor, material scraper goes out natural air cooledly, pulverizes, and packaging is finished product.
3. according to claim 2 from 2,4-dinitroanisol synthesizes O-methoxy-m-acetamino-N, the method of N-diallyl aniline, it is characterized in that: step 3) in solvent can be dimethyl formamide or ethanamide, the consumption of propenyl chloride by 2,4-dinitroanisol meter mol ratio be 1.9-1.96:1, the temperature 60-90 DEG C of reaction, reaction times 6-10 hour, product and separated from solvent, the recovery of residual raw materials is used scraper evaporator.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437091A (en) * | 2019-07-31 | 2019-11-12 | 中北大学 | A kind of method and apparatus of 2,4- diamino anisole selectively acylating synthesis 2- amino -4- acetamido methyl phenyl ethers anisole |
| CN111153828A (en) * | 2020-01-22 | 2020-05-15 | 浙江迪邦化工有限公司 | Continuous production method and system of 3- (N, N-diallyl) amino-4-methoxyacetanilide |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437091A (en) * | 2019-07-31 | 2019-11-12 | 中北大学 | A kind of method and apparatus of 2,4- diamino anisole selectively acylating synthesis 2- amino -4- acetamido methyl phenyl ethers anisole |
| CN111153828A (en) * | 2020-01-22 | 2020-05-15 | 浙江迪邦化工有限公司 | Continuous production method and system of 3- (N, N-diallyl) amino-4-methoxyacetanilide |
| CN111153828B (en) * | 2020-01-22 | 2022-11-22 | 浙江迪邦化工有限公司 | Continuous production method and system of 3- (N, N-diallyl) amino-4-methoxyacetanilide |
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Application publication date: 20140827 |