2,5-Diaminobenzonitrile

Step 1: Add 3 kg of 2-cyano-4-nitroaniline, 15 L of ethanol, 80 g of 3percent Pt / C catalyst and 300 mL of ammonia (chemically pure) to a 20 L autoclave, replace with nitrogen, replace with hydrogen, warm to 50 ° C, The pressure is kept at 1.6MPa, the reaction is not to absorb hydrogen, and then the reaction material after the reaction is filtered to obtain filtrate; Step 2, the filtrate described in step 1 is precipitated and crystallized at a temperature of -10 ° C for 18 hours to obtain a solid-liquid mixture; Step 3, solid-liquid separation of the solid-liquid mixture in the second step is carried out under the protection of nitrogen to obtain the solid and the filtrate, and then the solid is dried in a vacuum drying box, and then the solid is dried at 130 ° C ~ 136 ° C under vacuum distillation, to be white 2, 5-diaminobenzonitrile;  Step 4: The filtrate described in step 3 is concentrated in vacuum at 45 ° C to 1/5 of the volume of the filtrate.The reduced filtrate was repeated in steps 2 and 3 and combined with 2, 5-diaminobenzonitrile in step 3 to afford 2.4 kg of product 2. 5-diaminobenzonitrile. The mass purity of 2, 5-diaminobenzonitrile prepared in this example was not less than 99.5percent and the yield was 98.0percent.General procedure: Hydrazine hydrate was chosen as the hydrogen donor for the low emission of pollutants. In a typical procedure, hydrazine hydrate (4 equiv) was added into the reactor which containing fresh prepared catalyst as described above. Then the reactor was put into a preheated oil bath with a stirring speed of 500 rpm, and the substrate (1 mmol)dissolved in 1 mL ethanol was added drop-wisely under argon. The reactions were monitored by TLC. After the reaction, the reaction mixture was vacuum filtered through a pad of silica on a glass-fritted funnel and an additional 15 mL of ethyl acetate (5 mL portions) was used to rinse the product from the silica, the filtrate was concentrated in vacuum and analyzed by GC. Products were purified by column chromatography and identified by 1H NMR and 13C NMR.General procedure: To an oven-dried reaction flask with Teflon coated stir bar purgedwith argon, Pd(OAc)2 0.01 mmol, IL4 0.08 mmol, KOH (or K2CO3)0.30 mmol, nitroarene 1 1.0 mmol and degassed HPLC grade water1.5 mL were added, and the mixture was stirred for 5 min under argonat room temperature. Then, 0.5 mL of hydrazine hydrate aqueous solution(~5.0 mmol) was syringed into the flask at the same temperature.After stirring for additional 5 min, the reaction was heat to 50 °C, and stirring for 8 h under argon. After completion, the reaction mixturewas extracted by methyl tertiary butyl ether (MTBE) (3 × 2 mL), andthe organic layer was collected and filtered through a bed of silica gellayered over Celite. The volatiles were removed in vacuo to afford theproduct 2. In some cases, further column chromatography on silica gelwas required to afford the pure desired products.A mixture of 5-nitroanthranilonitrile (200 mg, 1.23 mmol) and palladium/ charcoal (10 mg, 10 wt percent) in methanol (3 ml) was stirred at room temperature under hydrogen atmosphere overnight and then filtered through a celite pad. The resulting filtrate was concentrated under reduced pressure. The resulting residue was purified with silica gel column chromatography (n-hexane/ethyl acetate=1/2) to give 160.3 mg of the titled compound as a pale yellow solid. [0551] 100 parts by weight of methanol as a hydrocarbon solvent was placed in a 1 liter pressure reactor equipped with a condenser and a thermometer, and 50 parts by weight of the nitroaniline compound represented by the following formula (1) was added to the hydrocarbon solvent while stirring, 0.25 parts by weight of a 5% Pd / C catalyst was subjected to a hydrogenation reaction at a reaction temperature of 120 C and a hydrogen pressure of 20 bar to prepare a phenyleneamine compound represented by the following formula (2).

Molecular Weight:133.15
XLogP3:0.8
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:3
Exact Mass:133.063997236
Monoisotopic Mass:133.063997236
Topological Polar Surface Area:75.8
Heavy Atom Count:10
Complexity:158
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes