N-(3-Amino-4-methoxyphenyl)acetamide

General procedure: In conjunction with the drawings, a continuous flow reactor with a solid-liquid separator is connected with a constant-current pressure pump and a nitrogen gas cylinder, respectively. First, nitrogen gas is introduced to replace the air in the reaction system, Then the first section of the reactor with an oil bath heated to a certain temperature, through the back pressure valve, The first reactor pressure is adjusted to the desired pressure. 2, 4-dinitroanisole andCatalyst (Pd / C, 1percent, particle size less than 100 microns)Added to the methanol solution, with a metering pump inlet 1, After preheating into the tubular continuous flow reactor, At the same time through the gas flow meter inlet 2 into the hydrogen, Into the tubular continuous flow reactor, at a certain temperature andUnder pressure for a certain period of time, into the gas-liquid solid separator, Recycled catalyst recycling, the liquid directly through the feed port 3 leads to the second reactor, while the second reactor feed port 4, 5 metering pumps were added to tie acid and acetic anhydride, into the reactor and add Hydrogen mixed, at a certain temperature after the reaction time into the post-treatment tank, filtered, distilled methanol recovery, washing, Obtained after recrystallization, the highest yield of 99percent, Product purity 99.9percent (Example 11).Weighing 140g2, 4-diamino benzene methyl ether, the HPLC purity of 99.3percent (embodiment 6 by preparing), adding 54g sodium carbonate, 84g methanol, cooled to -5 °C, adding 118.2g acetic anhydride, is omitted, the temperature is increased to 5 °C and thermal insulation to the reaction to complete. Boil off some methanol, adding water to the residue, the cooling crystallization, filtration, to obtain 179.5g (99.6percent) 2-amino-4-acetamido anisole (IV), 2, 4-di-acetaminoanisole generation amount in 1percent the following (measured by HPLC), the yield is 98.6percent.In a reaction flask with a reflux condenser were added sequentially 2, 4-dinitroanisole 100kg, 50percent by mass of hydrazine hydrate 50kg, Iron acetylacetonate 10kg, Methanol 500kg, the reaction temperature was controlled at 65 4h, Filtering and recovering magnetic Fe3O4 powder to obtain 2, 4-diaminoanisole-methanol mixture; Then will get it 2, 4-diaminoanisole-methanol mixing Liquid placed in the reaction flask, Ice bath (0 ~ 5 ) under the conditions of stirring while dropping 75kg of acetic anhydride, Control within 40min drip finished, And kept in an ice bath for 30 minutes while stirring, Vacuum distillation recovery of methanol, and then filtered, After drying, 89.5 kg of 2-amino-4-acetamidoanisole was obtained (content: 99.7percent, yield: 98.5percent).Step 3: Add 0.25 mol of 2, 4-diaminoanisole to the vessel.50 ml of acetic acid and 0.1 mol of catalyst, Stirring was carried out, cooled to 0 to 5 ° C with an ice bath, and 0.25 mol of acetic anhydride was added dropwise over 2 hours.After the addition is completed, continue to keep warm for 30 minutes.Then, 125 ml of ice water was added, stirred for 15 minutes, filtered, and the filter cake was washed once with an aqueous solution of sodium dithionite.Drying under reduced pressure gave 2-amino-4-acetamidoanisole.Under a nitrogen atmosphere, 40 g of 2, 4-aminoanisole and 74 ml of dichloromethane were placed in a 250 ml four-necked flask equipped with a mechanical stirring device and a thermometer.18 g of sodium carbonate, stirred and dissolved, cooled in an ice water bath, the temperature was 2 ° C, and 31 ml of acetic anhydride was added dropwise, the dropping time was 2 h, the temperature was kept at 1 ° C for 5 h, and separated by 137 ml of n-hexane, and suction filtered.The filter cake was washed with water and dried in vacuo to give 47.2 g of the desired product, yield: 90.5percent, purity 99.2percent.Take 800g 4-acetamido-2-nitroanisole (IV) was dissolved in 2.5kg methanol solution, Followed by addition of Pd / C catalyst was hydrogenated 32g catalytic reduction reaction, The pressure of the reduction reaction is 0.6Mpa, Temperature is 50 , Reaction time 25min, The reaction is over, After the filter to remove the catalyst, The filtrate was distilled off to remove 2.2 kg of methanol, followed by 1: 1 with waterThe volume of mixing, cooling crystallization, suction filtration, That is to say73.6 g of 2-amino-4-acetamidoanisole (V) (HPLC purity99.5percent), yield 98.1percent.1000 kg of 2-nitro-4-acetamidoanisole, 20 kg of a three-way catalyst Ni_Mo_B (in which the weight percentages of Ni, Mo, and B are 95.0percent, 3.0percent, and 2.0percent, respectively, and the carrier is modified alumina), 1000L of methanol was added to catalytic hydrogenationIn the kettle, pass nitrogen gas into the reactor and empty the air.Repeat five times to thoroughly remove the air from the reactor and then introduce hydrogen gas.Keep the pressure in the kettle at 1.50 MPa, raise the temperature to 60 °C, and start the stirrer.Catalytic hydrogenation reaction.During the reaction, sampling was continuously performed. When the purity of the target product was greater than 99percent, the hydrogen vent valve was closed and the hydrogen flow was stopped.After the end of the reaction, the catalyst is filtered while still hot, and the liquid is filtered. The liquid is then discharged into a de-alcoholic tank for distillation. The methanol and water distilled out then enter the methanol recovery column, and the distilled methanol is recycled.The de-alcoholized material was placed in a cooling pot for cooling and crystallization. After cooling and crystallization, the resulting product was centrifuged to obtain 2-amino-4-acetylaminoanisole with a yield of 96.52percent and a purity of 99.8percent (GC).(5) Add 1000 kg of 2-nitro-4-acetanisole and 1000 L of methanol to a catalytic hydrogenation reactor and add20kg catalyst Ni-Mo-B(The weight percentages of Ni, Mo, and B are 95.0percent, 3.0percent, and 2.0percent, respectively.The carrier is modified alumina).After the hydrogenation tank is purged with nitrogen, hydrogen is added proportionately.Control the temperature at 80 °C, Pressure at 1.0MPaFor hydrogenationAfter the reaction is completed, it is pressed into the catalyst sedimentation tank.Recovery of catalyst sedimentation, The supernatant of the sedimentation tank enters the filtration system.After filtering, the liquid enters the de-alcoholization tank for distillation.Distilled methanol and water enter methanol to recover the distillation tower.Distilled methanol recycling;The dealcoholized material is placed in a cooling pot for cooling and crystallization.After cooling and crystallization, Centrifuge to obtain 2-amino-4-acetamidoanisole by centrifugation.Yield 96.52percent, Purity 99.8percent (GC).A 500 mL dry flask was charged with 50 g of 2-nitro-4-acetamidoanisole, 200 g of recovered methanol (recovered in Example 11), 3.0 g of 10percent palladium on carbon and nitrogen three times. Hydrogen gas Pressure 0.05-0.2MPa, the reaction automatically exothermic, control the temperature 30-40 ° C. Hydrogenation time 3-4 hours. HPLC to p-nitroanisole less than 0.1percent of the reaction end. 0.1 g of antioxidant sodium metabisulfite was added and the solution was filtered off under nitrogen pressure to obtain 40.1 g of 2-methoxy-5-acetamidoaniline, yield 94.7percent. Product purity 98.6percent.15.4 kg of 2-nitro-4-aminophenol having a purity of 99.8percent in the same manner as in was mixed with 40 kg of a 10percent liquid base at a concentration of 10percent, and 12.6 kg of dimethyl sulfate was added to obtain 15.8 Kg of 2-nitro -4-aminoanisole. 15.8 Kg 2-nitro-4-aminoanisole was mixed with 95 Kg of methanol, 10.1 Kg of acetic anhydride, and 5.5 Kg of sodium carbonate to give 19.2 Kg of 2-nitro-4-acetylaminoanisole. 19.2Kg 2-nitro-4-acetylaminoanisole was mixed with 70 Kg of methanol, 10 Kg of water and 1.0 Kg of FeCl3.6H2O and mixed with 6.3 Kg of hydrazine hydrate to give 16.8 Kg of 2-amino-4-acetylaminoanisole.

Used in the production of disperse blue 79# and other dye intermediates

Molecular Weight:180.20
XLogP3:0.5
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:2
Exact Mass:180.089877630
Monoisotopic Mass:180.089877630
Topological Polar Surface Area:64.4
Heavy Atom Count:13
Complexity:185
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes