CN1869003A - Preparation method of 4-aminobenzoyl-N-(4-aminobenzoyl) amine - Google Patents
Preparation method of 4-aminobenzoyl-N-(4-aminobenzoyl) amine Download PDFInfo
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- CN1869003A CN1869003A CN 200610052267 CN200610052267A CN1869003A CN 1869003 A CN1869003 A CN 1869003A CN 200610052267 CN200610052267 CN 200610052267 CN 200610052267 A CN200610052267 A CN 200610052267A CN 1869003 A CN1869003 A CN 1869003A
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Abstract
A process for preparing 4-aminobenzoyl-N-(4-aminobenzoyl) amine includes such steps as dissolving nitrobenzoyl chloride in organic solvent, adding it to ammonia water, ammonolysis reaction to obtain p-nitrobenzoylamine, iron powder reducing reaction or hydrocatalytic nitro reducing reaction in alcohol-water solution to obtain p-amino benzoylamine, condensating reaction on p-nitrobenzoyl chloride in organic solvent under existence of acid binding agent to obtain 4-nitrobenzoyl-N-(4-aminobenzoyl) amine, and iron powder reducing reaction of hydrocatalytic nitro reducing reaction in solvent.
Description
Technical field
The invention belongs to the compounds process for production thereof technical field, be specially the preparation method of 4-aminobenzoyl-N-(4-aminobenzoyl) amine.
Background technology
4-aminobenzoyl-N-(4-aminobenzoyl) amine is a kind of pigment dyestuff intermediate, and main application is the yellow C.I 181#. of synthetic organic pigment.The yellow C.I 181# of pigment dyestuff is a high-grade pigment dyestuff that various performances are very good, and of paramount importance a kind of raw material was exactly amino this formyl of 4--N-(amino this formyl of 4-) amine during it was synthetic.Up to the present, in the world also just a few countries such as Germany, the U.S. this product is had suitability for industrialized production, and up to the present China do not have the manufacturing enterprise of this product as yet, our country still depends on external import to the use of this product.In investigation, find relevant enterprise, the difficulty of producing the yellow C.I 181# of pigment dyestuff mainly concentrates on its intermediate 4-aminobenzoyl-N-(4-aminobenzoyl) amine synthetic, the subject matter here is first: the synthetic intermediate is difficult to reach the synthetic required specification of quality of the finished product; Second: the manufacturing cost of this intermediate is too high, makes the finished product be difficult to satisfy the demand of market competition.Pertinent literature is reported seldom 4-aminobenzoyl-N-(4-aminobenzoyl) amine synthetic, only included the synthetic document of one piece of yellow 181# of relevant pigment dyestuff of DE2.845.947 in the U.S. chemical abstract, and be that one piece of relevant report (Synth.Commun is only arranged equally among the Beil.; EN32,8 2002), the synthetic method that is adopted wherein, though reached gratifying result on yield and quality product, the catalyst cupport hydrogenation that he adopted makes process complications, the also corresponding increase of cost.
Summary of the invention
The invention belongs to the above-mentioned problems in the prior art, design provides the preparation method's of 4-aminobenzoyl-N-that a kind of technology is simple, production cost is low (4-aminobenzoyl) amine technical scheme.
The preparation method of described 4-aminobenzoyl-N-(4-aminobenzoyl) amine is characterized in that in turn including the following steps:
1) paranitrobenzoyl chloride is dissolved in organic solvent, joins then in the ammoniacal liquor, carry out ammonolysis reaction and make the p-nitrophenyl methane amide;
2) in ethanol-aqueous medium, the p-nitrophenyl methane amide adopts iron powder reducing or shortening to carry out nitro-reduction reaction, obtains Para Amino Benzamide;
3) carry out condensation reaction under the condition that Para Amino Benzamide and paranitrobenzoyl chloride have acid binding agent to exist in organic solvent, make 4-oil of mirbane formyl-N-(4-aminobenzoyl) amine;
4) in solvent, adopt iron powder reducing or shortening to carry out nitro-reduction reaction 4-oil of mirbane formyl-N-(4-aminobenzoyl) amine, make 4-aminobenzoyl-N-(4-aminobenzoyl) amine.
The preparation method of described 4-aminobenzoyl-N-(4-aminobenzoyl) amine, it is characterized in that in the step 3), setting-up point is 20-100 ℃, preferred 56-60 ℃, used organic solvent is polyoxyethylene glycol series, benzene, toluene, dioxane, acetone or sherwood oil, and acid binding agent is organic bases or inorganic salt.
The preparation method of described 4-aminobenzoyl-N-(4-aminobenzoyl) amine is characterized in that in the step 4) that the catalytic hydrogenating reduction temperature of reaction is 80-150 ℃, preferred 110-130 ℃; Solvent for use is ethanol-water, DMF-H
2O or DMSO-H
2O; Catalyst system therefor is a Ruan Shi nickel, and consumption is the 0.5-5.0% of 4-oil of mirbane formyl-N-(4-aminobenzoyl) amine weight, preferred 1.0-3.0%; Hydrogen pressure is 1.0-10.0atm, preferred 3.0-5.0atm.
The preparation method of described 4-aminobenzoyl-N-(4-aminobenzoyl) amine is characterized in that in the step 4), and iron powder adopts hydrochloric acid, sulfuric acid or Glacial acetic acid to activate, and reduction reaction temperature is 80-150 ℃, preferred 95-100 ℃; Solvent for use is DMF-H
2O or DMSO-H
2O.
The preparation method of described 4-aminobenzoyl-N-(4-aminobenzoyl) amine is characterized in that described organic bases is pyridine or triethylamine, and inorganic salt are inorganic carbonate or supercarbonate.
The preparation method of described 4-aminobenzoyl-N-(4-aminobenzoyl) amine is characterized in that DMF concentration is 20-100%, preferred 50%.
The preparation method of above-mentioned 4-aminobenzoyl-N-(4-aminobenzoyl) amine, technology is simple, the yield height, good product quality, and production cost is low.
Embodiment
The invention will be further described below to provide specific embodiment.
1) paranitrobenzoyl chloride ammonolysis reaction, preparation p-nitrophenyl methane amide
Be equipped with in the 1000ml four-hole bottle of stirring, reflux exchanger, thermometer, heating in water bath one, be sequentially added into 218g, 25% ammoniacal liquor (3.20mol), 135g water, begin to stir, then to wherein adding 1.0g (70%) phase-transfer catalyst---palmityl trimethyl ammonium chloride, build bottle stopper, with the method for water-bath by indirect heating system slowly is heated to 55-60 ℃, this moment, catalyzer dissolved fully, system is homogeneous phase, and insulated and stirred is standby;
In addition a 500ml there-necked flask is installed stirring, thermometer, heated water bath, then to wherein adding 265g toluene, start stirring, under agitation condition, slowly to wherein adding 200g, the paranitrobenzoyl chloride of 99% (1.07mol), finish, open outside heating in water bath system, system slowly is heated to 50-55 ℃, this moment, system was dissolved fully, stop to stir, the paranitrobenzoyl chloride toluene solution that dissolving is good is poured into to a 500ml dropping funnel, under agitation condition, in about 2.5h, be added drop-wise in the above-mentioned ammoniacal liquor system, because exothermic heat of reaction, the ammoniacal liquor system temperature can raise to some extent, whole dropping process reaction maintains 55-60 ℃, after dropwising, under this temperature, continue insulation reaction 3.0h, insulation finishes, and the intensification toluene distillation is the mixture of toluene and water because of system, so toluene and water steam azeotropic, when the system internal temperature reached 100 ℃, toluene had been distilled fully, was cooled to 20 ℃, filter the product that generates, drain a spot of water washing in back, the ammonium chloride that mother liquid obtained concentrated recovery generates is dried to constant weight under the product infrared lamp, obtain p-nitrophenyl formyl ammonia 178g, liquid chromatography area normalization purity 98.5%, yield 98.7%, m.p200-201.5 ℃.
2) p-nitrophenyl formyl ammonia reduction preparation p-benzoyl ammonia
2.1) hydrogenating reduction of p-nitrophenyl formyl ammonia, preparation p-benzoyl ammonia
In the autoclave of 500ml cleaning, add 300ml, 85% ethanol, the 0.5g raney nickel catalyst, 35.1g, 98.5% (0.208mol) p-nitrophenyl formyl ammonia finishes, and builds kettle cover, with the air among nitrogen and the repeatedly displacement system of hydrogen difference, displacement finishes, and system is fed the hydrogen of 5atm, open and stir water coolant, open stirring, then system slowly is warming up to 110 ℃, and maintain under this temperature, pressure condition and react 5h, reaction finishes, cool to about 75 ℃, stop to stir, bleed off hydrogen pressure, open kettle cover, leave standstill about 10min, filtered while hot, catalyst recovery is applied mechanically, product liquid naturally cooling is separated out product, filter, oven dry makes p-benzoyl ammonia 27.1g, liquid chromatography area normalization purity 99%, m.p.181-182 ℃, yield 94.8%.
2.2) iron powder reducing of p-nitrophenyl formyl ammonia, preparation p-benzoyl ammonia
The 500ml four-hole bottle is installed stirring, the backflow condenser, thermometer, then to wherein adding 300g, 85% ethanol, start stirring, under agitation condition to wherein adding 86g iron powder and 3.2g, 30% hydrochloric acid, finish, build bottle cap, open condenser cooling water, pass through indirect heating then, system is warming up to backflow, and keep reflux state to activate 30 minutes, after activation finishes, beginning intermittently add the p-nitrophenyl methane amide to system, amount to and add 36.3g (0.215mol), whole reinforced process approximately needs 3.0 hours, temperature maintains back the slide state all the time during this time, behind reinforced the finishing, it is complete to raw material reaction to continue insulation reaction 3.0 hours, cools to 70 ℃, be neutralized to PH=7 with yellow soda ash, again be warmed up to 80 ℃ then, stop to stir, be incubated static 20 minutes, B with a prior preheating in 90 ℃ of water filters then, mother liquor cooling back product is separated out, and product is filtered a small amount of washing, oven dry, the heavy 24.5g of product, m.p.181-182 ℃, liquid chromatography area normalization purity 99.2%; Above-mentioned filtration is mother liquid obtained from newly returning the 500ml four-hole bottle, to filter iron mud simultaneously and together return wherein, install stirring, thermometer, condenser, then under agitation condition with system from newly being warmed up to 80 ℃, stirred 10 minutes, stop to stir, be incubated static 20 minutes, filter as mentioned above, product is separated out, must reclaim product 2.3g, m.p.180.3-181.5 ℃, liquid chromatography area normalization purity 98.8%; Merge the p-benzoyl ammonia that makes for twice, gross weight 27.8g, yield 93.7%.
3) p-benzoyl ammonia and paranitrobenzoyl chloride condensation reaction, preparation 4-oil of mirbane formyl-N-(4-aminobenzoyl) amine
In a 1000ml four-hole bottle that installs stirring, reflux exchanger, thermometer, dropping funnel, the p-benzoyl ammonia that adds 34.0g (0.247mol), and then to benzene that wherein adds 337g and 23.4g (0.220mol) yellow soda ash, finish, start stirring, under agitation condition, slowly system is heated to 55 ℃ with water-bath;
Have stirring at a 250ml in addition, in the there-necked flask of thermometer, add 150g benzene, the paranitrobenzoyl chloride of 47.3g (0.252mol) finishes, start stirring, slowly system is heated to 50 ℃ with water-bath under agitation condition, the paranitrobenzoyl chloride in the system stops to stir with dissolving fully at this moment, solution is poured in the dropping funnel of an above-mentioned 250ml, and under agitation condition, after reflux state was added drop-wise in the benzole soln of above-mentioned p-benzoyl ammonia, dropwises in 4.5 hours, insulation continues reaction 6 hours, insulation finishes, and solvent distillation benzene is when steaming about 300g, system is cooled to 70 ℃, to wherein adding 350ml water,, remaining benzene distillation is come out then with the method for component distillation from new intensification, to effluent liquid not till oil droplet is arranged, cool to below 25 ℃, filter, washing, draining the back dries under infrared lamp, make 4-oil of mirbane formyl-N-(4-aminobenzoyl) amine 67.3g, liquid chromatography area normalization purity 98.1%, yield 93.8%.
4) 4-oil of mirbane formyl-N-(4-aminobenzoyl) amine carries out nitro-reduction reaction, preparation 4-aminobenzoyl-N-(4-aminobenzoyl) amine
4.1) 4-oil of mirbane formyl-N-(4-aminobenzoyl) amine adopts shortening to carry out nitro-reduction reaction, preparation 4-aminobenzoyl-N-(4-aminobenzoyl) amine
In the 500ml autoclave, add 120gDMF, 120g water, 0.5g raney nickel catalyst, 25.2g, 4-aminobenzoyl-N-of 98.1% (0.0867mol) (4-oil of mirbane formyl) amine, finish, build kettle cover, with the nitrogen replacement reaction system repeatedly, and then under the 4atm condition, replace three times with hydrogen, displacement finishes, the system hydrogen pressure is controlled at 4atm, open the stirring water coolant, open and stir, system slowly is warmed up to 120 ℃ under agitation condition, and keeps under this condition and react 6.0h, after reaction finishes, cool to 95-100 ℃, bleed off the still internal pressure, open the reactor kettle cover, filtered while hot goes out the catalyzer Raney Ni, product liquid is transferred in the 500ml there-necked flask, install and stir, thermometer, condenser, dropping funnel receiving flasks etc. are used about the method distilling off solvent 200g of underpressure distillation again, and still-process control vacuum tightness is at 0.90-0.95atm, distillation finishes, stop heating, under agitation condition, drip 250ml distilled water then, cool to room temperature to system, after continuing to stir 20min, stop to stir, filtering product washes filter cake with water after draining, drain, dry to constant weight under the infrared lamp, make 4-aminobenzoyl-N-(4-aminobenzoyl) amine 20.4g, product appearance: canescence crystalline powder, liquid chromatography area normalization purity: 99.1%, yield: 91.4%.
4.2) reaction of 4-oil of mirbane formyl-N-(4-aminobenzoyl) amine employing iron powder reducing, preparation 4-aminobenzoyl-N-(4-aminobenzoyl) amine
One 250ml four-hole bottle is installed stirring, reflux exchanger, thermometer, and heating system, after installing, to wherein adding 40g DMF, 40g water, finish, open and stir, under agitation condition sequentially to wherein adding 16g (0.286mol) iron powder, 0.5g, 36% hydrochloric acid, add the back and open heating system and reflux exchanger water coolant, by indirect heating system is heated up, when reaching 95 ℃, system begins to calculate soaking time, insulation activation 30min in 95-100 ℃ of scope, then in batches to wherein adding 4-aminobenzoyl-N-(4-oil of mirbane formyl) amine, amount to add-on 8.5g (0.0295mol), whole reinforced process 3.0h, finish, keep 95-100 ℃ and continue to react 3.0 hours to reacting completely, during this time at any time the detection architecture iron ion have a situation, if there is not iron ion to exist, can solve by the method for adding hydrochloric acid, after reaction finishes, reaction mixture is cooled to 90 ℃, stir down with the yellow soda ash PH=7 that neutralizes, again be warmed up to more than 95 ℃ then, stop to stir, be incubated static 30min, filter, iron mud returns four-hole bottle,, filters at 80-90 ℃ of agitator treating with 100gDMF, merge mother liquor and washing lotion, join and carry out underpressure distillation in the 250ml there-necked flask, control vacuum tightness is within 0.9-0.95atm, when separating out appears in system, stop distillation, to wherein dripping 100ml distilled water, cool to room temperature while hot, continue to stir 30min, filter, washing, drain the back and dry to constant weight under infrared lamp, make 4-aminobenzoyl-N-(4-aminobenzoyl) amine 6.6g, outward appearance is the canescence crystalline powder, liquid chromatography area normalization purity: 99.0%, yield: 87.0%.
Claims (6)
1, the preparation method of 4-aminobenzoyl-N-(4-aminobenzoyl) amine is characterized in that in turn including the following steps:
1) paranitrobenzoyl chloride is dissolved in organic solvent, joins then in the ammoniacal liquor, carry out ammonolysis reaction and make the p-nitrophenyl methane amide;
2) in ethanol-aqueous medium, the p-nitrophenyl methane amide adopts iron powder reducing or shortening to carry out nitro-reduction reaction, obtains Para Amino Benzamide;
3) carry out condensation reaction under the condition that Para Amino Benzamide and paranitrobenzoyl chloride have acid binding agent to exist in organic solvent, make 4-oil of mirbane formyl-N-(4-aminobenzoyl) amine;
4) in solvent, adopt iron powder reducing or shortening to carry out nitro-reduction reaction 4-oil of mirbane formyl-N-(4-aminobenzoyl) amine, make 4-aminobenzoyl-N-(4-aminobenzoyl) amine.
2, the preparation method of 4-aminobenzoyl-N-as claimed in claim 1 (4-aminobenzoyl) amine, it is characterized in that in the step 3), setting-up point is 20-100 ℃, preferred 56-60 ℃, used organic solvent is polyoxyethylene glycol series, benzene, toluene, dioxane, acetone or sherwood oil, and acid binding agent is organic bases or inorganic salt.
3, the preparation method of 4-aminobenzoyl-N-as claimed in claim 1 (4-aminobenzoyl) amine is characterized in that in the step 4) that the catalytic hydrogenating reduction temperature of reaction is 80-150 ℃, preferred 110-130 ℃; Solvent for use is ethanol-water, DMF-H
2O or DMSO-H
2O; Catalyst system therefor is a Ruan Shi nickel, and consumption is the 0.5-5.0% of 4-oil of mirbane formyl-N-(4-aminobenzoyl) amine weight, preferred 1.0-3.0%; Hydrogen pressure is 1.0-10.0atm, preferred 3.0-5.0atm.
4, the preparation method of 4-aminobenzoyl-N-as claimed in claim 1 (4-aminobenzoyl) amine is characterized in that in the step 4), and iron powder adopts hydrochloric acid, sulfuric acid or Glacial acetic acid to activate, and reduction reaction temperature is 80-150 ℃, preferred 95-100 ℃; Solvent for use is DMF-H
2O or DMSO-H
2O.
5, the preparation method of 4-aminobenzoyl-N-as claimed in claim 2 (4-aminobenzoyl) amine is characterized in that described organic bases is pyridine or triethylamine, and inorganic salt are inorganic carbonate or supercarbonate.
6, as the preparation method of claim 3 or 4 described 4-aminobenzoyl-N-(4-aminobenzoyl) amine, it is characterized in that DMF concentration is 20-100%, preferred 50%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870664A (en) * | 2010-06-18 | 2010-10-27 | 淄博圣马化工厂 | Preparation method of 4-amino-benzoyl formic-N-(4-amino-benzoyl formic) amine |
| CN102911115A (en) * | 2012-11-19 | 2013-02-06 | 江苏扬农化工股份有限公司 | Method for preparing fluazinam intermediate 2-amino-3-chloro-5-trifluoromethyl pyridine |
| CN106946726A (en) * | 2017-03-24 | 2017-07-14 | 连云港恒贸化工有限公司 | A kind of method for synthesizing Para Amino Benzamide |
| CN115594603A (en) * | 2022-10-09 | 2023-01-13 | 湖北师范大学（Cn） | Method for preparing N-tert-butyl-4-aminobenzamide by using microchannel reactor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2845947A1 (en) * | 1978-10-21 | 1980-04-30 | Hoechst Ag | AZO COMPOUNDS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| CN1116276C (en) * | 1999-09-23 | 2003-07-30 | 浙江新农化工有限公司 | Process for synthesizing N-(3'-isopropoxyphenyl)-2-methyl benzoylamine |
-
2006
- 2006-07-03 CN CNB2006100522670A patent/CN100358864C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870664A (en) * | 2010-06-18 | 2010-10-27 | 淄博圣马化工厂 | Preparation method of 4-amino-benzoyl formic-N-(4-amino-benzoyl formic) amine |
| CN101870664B (en) * | 2010-06-18 | 2014-04-16 | 淄博圣马化工厂 | Preparation method of 4-amino-benzoyl formic-N-(4-amino-benzoyl formic) amine |
| CN102911115A (en) * | 2012-11-19 | 2013-02-06 | 江苏扬农化工股份有限公司 | Method for preparing fluazinam intermediate 2-amino-3-chloro-5-trifluoromethyl pyridine |
| CN106946726A (en) * | 2017-03-24 | 2017-07-14 | 连云港恒贸化工有限公司 | A kind of method for synthesizing Para Amino Benzamide |
| CN115594603A (en) * | 2022-10-09 | 2023-01-13 | 湖北师范大学（Cn） | Method for preparing N-tert-butyl-4-aminobenzamide by using microchannel reactor |
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Granted publication date: 20080102 Termination date: 20180703 |