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| CAS No. : | 836-30-6 |
| Formula : | C12H10N2O2 |
| M.W : | 214.22 |
| SMILES Code : | O=[N+](C1=CC=C(C=C1)NC2=CC=CC=C2)[O-] |
| English Name : | 4-Nitro-N-phenylaniline |
| MDL No. : | MFCD00007301 |
| InChI Key : | XXYMSQQCBUKFHE-UHFFFAOYSA-N |
| Pubchem ID : | 13271 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With nitric acid; acetic acid |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 96% | With water; ammonium chloride; zinc In tetrahydrofuran at 20℃; | Ammonium chloride (48 mg, 9 mmol) in water (1 mL) was added to a stirred solution of (4-nitro-phenyl)-phenyl-amine (200 mg, 0.9 mmol) in THF (4 mL). Zinc powder (48 mg, 7.4 mmol) was then added portion wise and the resulting mixture was stirred at room temperature for 2 hours then filtered over celite. The filtrate was extracted with ethyl acetate and the ethyl acetate was washed with brine solution, dried over Na2SO4 and concentrated to 160 mg (96%) of N-phenyl-benzene-1,4-diamine. LCMS: 185.1 (M+1)+, 93.9%, 1H NMR: (DMSO-d6): 67.2 (t, 2H), 7.0 (d, 2H), 6.8 (m, 2H), 6.7 (d, 2H). |
| 96% | With palladium-carbon; hydrogen for 14h; Milling; | |
| 39% | With hydrogen; C45H56BN5OPRh(2+)*2F6Sb(1-) In toluene at 80℃; for 15h; Glovebox; chemoselective reaction; |
| With acetic acid; zinc | ||
| durch elektrolytische Reduktion; | ||
| With nickel Hydrogenation; | ||
| With ethanol; ammonium chloride; zinc | ||
| With hydrazine hydrate Heating; | ||
| With hydrogen | ||
| 1 Use of Prepared Catalyst (1) Reduction of p-nitrodiphenylamine to p-aminodiphenylamine catalyzed by the Pd+2 polymer catalyst. STR12 | ||
| With hydrogen In ethanol at 20℃; for 5 - 6h; | 1.i A mixture of 4-fluoronitrobenzene (0.02 mol), anilines (0.022 mol), and potassium carbonate (0.022 mol) in 40 ml of anhydrous DMF was heated to 1500C with stirring for overnight. After cooling to room temperature, the reaction mixture was poured into 500 ml of ice water and stirred for 30 min. The precipitates formed were collected by filtration, washed with water and dried in vacuo to give the intermediate. This crude intermediate was dissolved in 100-200 ml of ethanol, and l-2g 10%Pd-C was added. The compound was hydrogenated under ambient pressure at room temperature for 5-6 hours. Then the catalyst was removed by filtration, and the filtrate was concentrated to dryness to give a mixture of crude anilines, which was used for the next step with further purification. | |
| With hydrogen at 50 - 120℃; for 2.5h; | 1.3 hydrogenation step The above-mentioned organic phase ( condensation fluid ) and phase quality 5 wt % of the Raney nickel catalyst into 500 ml stainless steel high-pressure reactor, nitrogen are used, hydrogen replacement three times, in order to ensure that air does not exist in the reaction device. Opening stirring and heating, setting the reaction temperature is 50 °C, the pressure of the hydrogen gas in the reactor to 1.5 MPa, when the reaction temperature reaches 60 °C time, start timing reaction. When the hydrogen pressure in the reactor is less than 1.0 MPa, the, in the cauldron makes up adding hydrogen to the reaction required to 1.5 MPa, so repeatedly hydrogen added to the system. The reaction temperature is kept at 80-120 °C reaction 2h, when the observed when the hydrogen pressure is constant, and then to continue reaction 30 min to stop the reaction. Sampling analysis, control azobenzol content is less than 0.05%. Cooling the pressure relief discharge, filtering and recycling Raney nickel catalyst, to continue to apply to all the next batch of material in the hydrogenation step. From the organic phase (also stock solution) to obtain the target product in 4-aminodiphenylamine (4-ADPA), gas phase chromatography (GC) analysis, delete solvent peak, its content is 98.5%, 4-nitro-diphenylamine and 4-nitrosodi diphenylammonium conversion is 100%. |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 93% | With potassium hydroxide In tetrahydrofuran; methanol; water at 0 - 70℃; for 12h; | p-Nitro-N,N-diphenylamine (4) A portion of p-nitro-N,N-diphenylbenzamide intermediate (172 mg, 0.54 mmol) was dissolved in anhydrous THF (5 mL), treated with 6 M Claisen’s base (KOH in MeOH/H2O, 5 mL) and then stirred at 70 °C for 12 h. The reaction mixture was then cooled to 0 °C, neutralized with 10% HCl solution, then diluted and extracted with EtOAc (3 × 10 mL), washed with brine (15 mL) dried with Na2SO4, and concentrated under reduced pressure. After workup, the crude mixture was passed through a plug of silica gel (neutralized with 1% Et3N) packed on a fritted funnel and eluted with 5% EtOAc in hexanes with 1% Et3N to remove byproducts, followed by 10-70% gradient of EtOAc in hexanes with 1% Et3N, to afford p-nitro-N,N-diphenylamine 4 as a yellow solid ( 107 mg, 93%). |
| With sodium hydroxide |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 100% | Stage #1: 4-chlorobenzonitrile; aniline With bis-triphenylphosphine-palladium(II) chloride at 20℃; for 0.166667h; Stage #2: With potassium carbonate for 16h; Reflux; | |
| 98% | With C50H72ClPPd; 2,6-bis(2,4,6-triisopropylphenyl)phenyldicyclohexylphosphine; potassium carbonate In <i>tert</i>-butyl alcohol at 100℃; for 6h; | |
| 97% | With PEPPSI-IPr; caesium carbonate In 1,2-dimethoxyethane at 80℃; for 24h; Inert atmosphere; |
| 97% | With dichloro(3-chloropyridinyl)(1,3-(diisopropylphenyl)-4,5-bis(dimethylamino)imidazol-2-ylidene)palladium(II); caesium carbonate In 1,2-dimethoxyethane at 80℃; for 24h; Schlenk technique; Sealed tube; Inert atmosphere; | |
| 96% | With potassium hydroxide; bis(tri-tert-butylphosphine)palladium(0); cetyltrimethylammonim bromide In water; toluene at 90℃; for 1h; | |
| 96% | With [(2,6-bis(2,4,6-triisopropylphenyl)phenyl-dicyclohexylphosphine)(allyl)PdCl]; potassium hydrogencarbonate In <i>tert</i>-butyl alcohol at 100℃; for 12h; Inert atmosphere; Sealed tube; | 48-51 Examples 48-68. General procedure: In the pressure tube, under a nitrogen atmosphere, the aryl halide (1.0 mmol), amine (1.2 mmol), Bicarbonate (1.3mmol), 0.5 mmol% [(TPhos)Pd(all)Cl] and 75 uL of dodecane (As an internal standard for GC analysis) dissolved in 2.0 mL solvent. The tube was sealed and placed at 100°C to react for 12 hours. Add dichloromethane and diatomaceous earth to aid filtration, Analyze by gas chromatography, The product was separated by (petroleum ether/ethyl acetate) column chromatography. |
| 95% | With potassium phosphate; 1,2,3,4,5-pentaphenyl-1'-(di-tert-butylphosphino)ferrocene; bis(dibenzylideneacetone)-palladium(0) In 1,2-dimethoxyethane at 100℃; for 20h; | |
| 95% | With potassium phosphate In 1,2-dimethoxyethane | 70 4-nitro-diphenylamine (Table 9, Entry 6) Example 70 4-nitro-diphenylamine (Table 9, Entry 6) According to the general procedure B, 4-chloronitrobenzene (80 mg, 0.51 mmol) reacted with aniline (57 mg, 0.60 mmol) using 1 mol % of Pd(dba)2, 2 mol % of Ph5FcP(t-Bu)2, and K3PO4 (254 mg, 1.21 mmol) in DME at 100° C. to give the title compound (102 mg, 95%) as a yellow solid: 1H-NMR (400 MHz, CDCl3): δ 8.12 (d, 2H, J=7.2 Hz), 7.40 (t, 2H, J=7.2 and 8.8 Hz), 6.96 (d, 2H, J=7.2 Hz), 7.24-7.18 (m, 3H), 6.48 (bs, 1H). 13C{1H}-NMR (125 MHz, CDCl3): δ 150.26, 139.51, 139.44, 129.64, 126.18, 124.54, 121.83, 113.59. GC/MS(EI): m/z 214 (M+). Anal. Calcd for C12H10N2O2: C, 67.28; H, 4.71; N, 13.08. Found: C, 67.45; H, 4.75; N, 13.02. |
| 88% | With carbonyl(pentamethylcyclopentadienyl)cobalt diiodide; copper diacetate In neat (no solvent) at 100℃; for 4h; | |
| 87% | With potassium hydroxide In N,N-dimethyl-formamide at 100℃; for 5h; | 2.3 General Procedure for the O-arylationand N-arylation with Aryl Halides General procedure: A mixture of phenol or amine (1.0 mmol), aryliodide (1.5 mmol), KOH (2 mmol) and BNPs (at) SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0) (0.05 g catalyst equal 0.0725 mmol/g pd) in DMF (2 mL) was stirred at 100 °C. The reaction progress was monitored by TLC. After the completion of the reaction, the catalyst was filtered,washed with ethanol and dried. The reaction mixture was extracted with ethyl acetate (3 × 5) and the organic layer was dried over magnesium sulfate (MgSO4). Then pure products were obtained from recrystallization in n-hexane. |
| 87.9% | With C36H45Cl3N4Pd; caesium carbonate In 1,2-dimethoxyethane at 80℃; for 24h; Inert atmosphere; | 15 Example 15: Buchwald-Hartwig coupling reaction test of 4-nitrochlorobenzene and aniline Add N-(4-indolyl) azacyclic carbene palladium complex (4mol%), 4-nitrochlorobenzene (1mmol), Cs2CO3 (3mmol), aniline into the reaction tube equipped with a magnetic stir bar. (1.5mmol) and DME (1mL). After argon replacement, the reaction mixture was heated at 80°C for 24h. The reaction solution was diluted with ethyl acetate (2 mL), filtered through Celite, and washed with ethyl acetate. The filtrate was washed with water, the aqueous phase (4 mL) was extracted with ethyl acetate, extracted twice, the organic layers were combined, dried over Na2SO4, filtered, concentrated and purified by silica gel column chromatography (PE:EA=5:1) to obtain the corresponding product. |
| 83% | With copper diacetate at 110℃; for 6h; | |
| 80% | With caesium carbonate at 170℃; for 12h; | 22 1.06 g (6.7 mmol) of p-chloronitrobenzene, 1.4 g (10.1 mmol) of caesium carbonate and 300 mg (0.7 mmol) of the catalyst from example 1 are stirred in 2 ml of aniline under an argon atmosphere at 170° C. for 12 h. The GC analysis of the crude product indicates the selective formation of the monoarylated compound and 83% conversion; triarylamine is not detected. After workup by column chromatography, 1.14 g (80%) of product are obtained. [0160] GC-MS/EI: 214 (M) |
| 76% | With potassium acetate; 1-butyl-3-methylimidazolium Tetrafluoroborate for 90h; microwave irradiation; | |
| 75% | at 170℃; for 12h; | 27 [0148] 1.06 g (6.7 mmol) of p-chloronitrobenzene, 1.4 g (10.1 mmol) of caesium carbonate and 500 mg (0.7 mmol) of the catalyst from Example 1 are stirred in 2 ml of aniline under an argon atmosphere at 170° C. for 12 h. The GC analysis of the crude product indicates the selective formation of the monoarylated compound and 83% conversion; triarylamine is not detected. After workup by column chromatography, 1.07 g (75%) of product are obtained. [0149] GC-MS/EI: 214 (M) |
| 74% | With potassium <i>tert</i>-butylate In toluene at 90℃; for 12h; Sealed tube; Inert atmosphere; | |
| 68% | With potassium hydroxide In dimethyl sulfoxide at 130℃; for 10h; | |
| 63% | at 170℃; for 12h; | 33 [0155] 1.06 g (6.7 mmol) of p-chloronitrobenzene, 1.4 g (10.1 mmol) of caesium carbonate and 490 mg (0.7 mmol) of the catalyst from Example 2 are stirred in 2 ml of aniline under an argon atmosphere at 170° C. for 12 h. The GC analysis of the crude product indicates the selective formation of the monoarylated compound and 63% conversion; triarylamine is not detected. |
| 61% | With potassium hydroxide In water at 20℃; for 6h; Green chemistry; | |
| 55% | With potassium carbonate In dimethyl sulfoxide for 12h; Reflux; Inert atmosphere; | 2.3 General procedure for the N-arylation of aryl amines with aryl halides General procedure: In a 25ml round bottom flask a mixture of 4:1 methanol/water, aryl halide (1mmol), Resin-CuNPs (0.2g), K2CO3 (3mmol) and aryl amine (1.2mmol) were taken and heated at reflux temperature for 12-24h in an oil bath under inert conditions. Resin beads were filtered off at the end of reaction while the solution was still hot. After a work up with dichloromethane and water, the organic layer was separated, dried over anhydrous Na2SO4. The crude products obtained after removal of solvent (Scheme 1) were purified by column chromatography (ethyl acetate: hexane) and identified by mass or 1H NMR spectroscopy (see ESI). |
| 49% | With oxalic acid hydrazide; trihydrate phosphoric acid; tetrabutylammomium bromide; 2,5-hexadione; copper(II) oxide In water at 120℃; for 24h; | |
| 46% | With cerium(IV) oxide; potassium hydroxide In dimethyl sulfoxide at 110℃; for 6h; Air atmosphere; | General procedure for the O-alkylation with 4-nitrochlorobenzene: General procedure: In a 25 mL round bottomed flask was taken a mixture of phenol/amine/thiophenol (1.2 mmol, 0.112 g), 4-nitrochlorobenzene (1 mmol, 0.157 g), base KOH (1.2 mmol, 0.08 g) and 1 mL DMSO was added. Further 2.5 mol % catalyst (4.5 mg) was added to the reaction mixture. The reaction mixture was heated to 110 °C for appropriate time. Reaction is monitored on TLC. After completion of the reaction the catalyst was separated by centrifugation and subsequently washed with dichloromethane. The reaction mixture was diluted with water and the product was extracted by dichoromethane (3 × 10 cm3). The organic layer was dried over anhydrous sodium sulfate and was evaporated under reduced pressure to give the product. The product was purified by column chromatography by using pet ether and ethyl acetate solvent system. The purified product was then confirmed by its spectral analysis after analyzing by IR, 1H NMR, and mass spectra. |
| 41% | With copper diacetate; manganese(II) acetate at 100℃; for 12h; Sealed tube; Green chemistry; | Coupling Products 1-23; General Procedure General procedure: A clean and oven-dried tube was charged with the appropriateprimary or secondary amine (1 mmol) and chloro(het)arenederivative (1 mmol). Mn(OAc)2 (5 mol%), Cu(OAc)2 (0.5 mmol),and PAMAM (40 mol%) were added, and the tube was sealed.The mixture was heated at 100 °C for 12 h while the reactionwas periodically monitored by TLC. The mixture was thencooled to r.t. and H2O (45 mL) and EtOAc (70 mL) were added.The organic layer was extracted (3×) then dried (Na2SO4) andconcentrated under reduced pressure. Finally, the crude productwas purified by column chromatography (silica gel, EtOAc-hexane). |
| 8% | With dicyclohexylamino[(2,6-dimethyl)morpholin-4-yl]phenylphosphine; potassium <i>tert</i>-butylate; palladium dichloride In toluene for 48h; Reflux; | |
| With copper(l) iodide; potassium carbonate | ||
| With copper; potassium carbonate In N,N-dimethyl-formamide at 186 - 194℃; for 4h; | ||
| 99 % Chromat. | With potassium phosphite; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl Heating; | |
| With caesium carbonate at 170℃; for 12h; | 24 1.06 g (6.7 mmol) of p-chloronitrobenzene, 1.4 g (10.1 mmol) of caesium carbonate and 360 mg (0.7 mmol) of the catalyst from example 2 are stirred in 2 ml of aniline under an argon atmosphere at 170° C. for 12 h. The GC analysis of the crude product indicates the selective formation of the monoarylated compound (comparison with GC-MS/EI of 1101-7) and 91% conversion; triarylamine is not detected. | |
| 21 %Chromat. | With C31H37ClN3NiO2(1-)*Li(1+); Lithium 1,1,1,3,3,3-hexamethyldisilazide In dimethyl sulfoxide at 110℃; for 3h; Inert atmosphere; Sealed tube; | 2.4 General Amination Procedure of Aryl Halides Using Different Amines General procedure: A representative amination method using chlorobenzene,pentylamine, and KOtBuin DMSO is described here. Allother amination reactions including different aryl halides,primary (1°) and secondary (2°) amines, solvents and baseswere performed using a similar method. A 4mL reactionvial containing a magnetic stir bar was charged with 1.4mLof anhydrous DMSO. The reaction vial, after being sealed with a septum and parafilm, was purged with Ar for 10min.Chlorobenzene [0.4mL, 3.9mmol, 2.25 equivalent (eq.)],pentylamine (0.21mL, 1.8mmol, 1.0eq.), anhydrous powderedKOtBu(70mg, 0.63mmol, 0.3eq.), and 2 (2mg,0.2mol%) were added sequentially. The reaction mixturewas stirred for 5min while continually purging with Ar. Thevial was then sealed with a Teflon screw cap. The reactionmixture was stirred for 3h at 110°C in a preheated oil bath,then allowed to cool to room temperature and filtered bypassing through Celite to remove the base and the catalyst.30L of the solution was then dissolved in 1mL absolute ethanol, and 10μL of decane was added as an internalstandard. Turn over number (TON) was determined usingGC-MS. |
| 80 % | With copper(l) iodide; sodium carbonate; N-(9H-carbazol-9-yl)-1H-pyrrole-2-carboxamide In ethylene glycol at 60℃; Sealed tube; | 13 Example 13: Synthesis of 4-nitro-N-phenylaniline 158mg (1mmol) 4-chloronitrobenzene, 121mg (1.3mmol) aniline, 10mg (0.05mmol) cuprous iodide, 28mg (0.1mmol) N-carbazolyl-1H-pyrrole-2-carboxamide, 276mg (2mmol) sodium carbonate, 2mL ethylene glycol, added to a 10mL reaction tube, sealed, reaction temperature 60 °C for 36h. After the reaction stops, add water, extract with ethyl acetate, wash with water, wash with saturated saline, dry anhydrous sodium sulfate, filter, filtrate distillation under reduced pressure, and separate and purify by silica gel column column chromatography to obtain 4-nitro-N-phenylaniline 171mg with a yield of 80% |
| 14% | With dichlorodipyridine nickel(II); sodium t-butanolate; 1,3-bis[2,6-diisopropylphenyl]imidazolium chloride In o-xylene at 150℃; Sealed tube; Inert atmosphere; |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 100% | In acetonitrile at 100℃; for 50h; | |
| 95.8% | With triethylamine In N,N-dimethyl-formamide at 30℃; for 72h; | |
| 87% | With toluene-4-sulfonic acid at 165℃; for 0.666667h; Ionic liquid; Microwave irradiation; | 4.1 General procedure for the MW-assisted C-N cross coupling General procedure: In a new sealed pressure regulation 10-mL pressurized vial were placed aryl halide (1 mmol), p-toluenesulfonic acid (1 mmol, 0.172 g), [DBU][HOAc] (1.5 mL), N-nucleophile (2 mmol), and a Teflon-coated magnetic stir bar. The vessel was closed with a snap-on cap, stirred at room temperature for 5 min and then placed into the MW cavity. Microwave irradiation of 100 W at a set temperature of 165°C was used and the reaction mixture was held under these conditions for the specified time. After completion of the reaction (monitored through TLC), the mixture was cooled to room temperature and was poured to a vessel containing distilled water. This was extracted with ethyl acetate (3*10 mL) and the combined organic phase was washed with brine (2*10 mL), dried over Na2SO4, and was concentrated under rotary vacuum evaporator. The crude product was purified by column chromatography using a mixture of ethyl acetate/n-hexane as eluent. |
| 62% | With potassium fluoride supported on Clinoptilolite In dimethyl sulfoxide at 110 - 115℃; for 2h; | |
| 7% | In tetrahydrofuran at 50℃; for 50h; | |
| With water; magnesium oxide at 200℃; | ||
| With potassium carbonate In N,N-dimethyl-formamide at 150℃; | 1.i A mixture of 4-fluoronitrobenzene (0.02 mol), anilines (0.022 mol), and potassium carbonate (0.022 mol) in 40 ml of anhydrous DMF was heated to 1500C with stirring for overnight. After cooling to room temperature, the reaction mixture was poured into 500 ml of ice water and stirred for 30 min. The precipitates formed were collected by filtration, washed with water and dried in vacuo to give the intermediate. This crude intermediate was dissolved in 100-200 ml of ethanol, and l-2g 10%Pd-C was added. The compound was hydrogenated under ambient pressure at room temperature for 5-6 hours. Then the catalyst was removed by filtration, and the filtrate was concentrated to dryness to give a mixture of crude anilines, which was used for the next step with further purification. | |
| With potassium carbonate In N,N-dimethyl-formamide |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With platinum on activated charcoal; isopropyl alcohol at 50 - 150℃; Hydrogenation; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With nickel at 60 - 100℃; Hydrogenation; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| at 0 - 5℃; weitere Produkte: Benzoldiazoniumnitrat, Phenol, Diphenyl, Kohlendioxyd, Stickstoff, Stickoxyd und salpetrige Saeure; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 1: 86.9% 2: 8.5% 3: 3.7% 4: 0.7% | In water at 70 - 75℃; for 3.5h; | 18 Example 18 Influence of different molar ratios of organic and inorganic hydroxides to betaine on the condensation of aniline with nitrobenzene and, simultaneously, influence of betaine and tetramethylammonium hydroxide (TMAH) on aniline methylation to N-methylaniline (N-MAn) is obvious from the results in Table 10. Example 18 Influence of different molar ratios of organic and inorganic hydroxides to betaine on the condensation of aniline with nitrobenzene and, simultaneously, influence of betaine and tetramethylammonium hydroxide (TMAH) on aniline methylation to N-methylaniline (N-MAn) is obvious from the results in Table 10. Seven-fold molar excess of aniline was added to a prepared aqueous solution of individual components of the reaction system, consisting of TMAH, betaine and potassium hydroxide. After azeotropic distilling off the water, 0.95 mol of nitrobenzene were added to the reaction mixture at 70° C. and at a pressure of 7.3 kPa during 1.5 h. The reaction was completed after further 2 h. Yield (Table 10) of the components in the reaction product has been calculated in relation to the introduced nitrobenzene. N-methylaniline (N-MAn) was expressed in mole per cent, related to the introduced TMAH. |
| 1: 65% 2: 13.2% 3: 15.7% 4: 1.3% | at 80℃; for 6h; | 12 Example 12 Influence of a Crown Ether as the Phase Transfer Agent on the Conversion and Yield of the Reaction. Example 12 Influence of a Crown Ether as the Phase Transfer Agent on the Conversion and Yield of the Reaction. Experimental Conditions: Mole ratio of aniline: nitrobenzene: betaine-KOH: 18 dibenzocrown-6-ether=7:1:1.1:0.1; the reaction took place in an inert atmosphere at 80° C. and at a pressure of 7.3 kPa during the overall reaction time of 6 h (Table 6). |
| 1: 65.8% 2: 7.1% 3: 17.2% 4: 1.3% | In water; isopropyl alcohol at 80℃; for 6h; | 15 Example 15 Influence of Polarity of Auxiliary Solvents, Forming Azeotropic Mixtures with Water, on the Course of the Reaction of Nitrobenzene with Aniline Under Anaerobic Conditions. Example 15 Influence of Polarity of Auxiliary Solvents, Forming Azeotropic Mixtures with Water, on the Course of the Reaction of Nitrobenzene with Aniline Under Anaerobic Conditions. 0.078 mol of nitrobenzene were dosed into a reaction mixture, consisting of 0.09 mol of KOH (84.0% concentration), 0.09 mol of betaine hydrate, 4 ml of water, 0.51 mol of aniline and 15 ml of an auxiliary solvent, at 80° C. during 1.5 h. Completing the reaction required further 4.5 h, while water was continuously removed from the reaction medium as an azeotrope with the auxiliary solvent. In an experiment with 2-propanol, the azeotrope was distilled off through a short column under an atmospheric pressure. In an experiment with pyridine, the azeotrope distilled at a reduced pressure of 13.3 to 9.3 kPa. In an experiment with cyclohexane water was continuously removed as an azeotrope by means of an azeotropic attachment. The results are given in the following Table 7. |
| 1: 62.2% 2: 21.9% 3: 14% 4: 1.9% | In pyridine; water at 80℃; for 6h; | 15 Example 15 Influence of Polarity of Auxiliary Solvents, Forming Azeotropic Mixtures with Water, on the Course of the Reaction of Nitrobenzene with Aniline Under Anaerobic Conditions. Example 15 Influence of Polarity of Auxiliary Solvents, Forming Azeotropic Mixtures with Water, on the Course of the Reaction of Nitrobenzene with Aniline Under Anaerobic Conditions. 0.078 mol of nitrobenzene were dosed into a reaction mixture, consisting of 0.09 mol of KOH (84.0% concentration), 0.09 mol of betaine hydrate, 4 ml of water, 0.51 mol of aniline and 15 ml of an auxiliary solvent, at 80° C. during 1.5 h. Completing the reaction required further 4.5 h, while water was continuously removed from the reaction medium as an azeotrope with the auxiliary solvent. In an experiment with 2-propanol, the azeotrope was distilled off through a short column under an atmospheric pressure. In an experiment with pyridine, the azeotrope distilled at a reduced pressure of 13.3 to 9.3 kPa. In an experiment with cyclohexane water was continuously removed as an azeotrope by means of an azeotropic attachment. The results are given in the following Table 7. |
| 1: 56.9% 2: 8.1% 3: 1% 4: 0.13% | In water at 70 - 75℃; for 3.5h; | 18 Example 18 Influence of different molar ratios of organic and inorganic hydroxides to betaine on the condensation of aniline with nitrobenzene and, simultaneously, influence of betaine and tetramethylammonium hydroxide (TMAH) on aniline methylation to N-methylaniline (N-MAn) is obvious from the results in Table 10. Example 18 Influence of different molar ratios of organic and inorganic hydroxides to betaine on the condensation of aniline with nitrobenzene and, simultaneously, influence of betaine and tetramethylammonium hydroxide (TMAH) on aniline methylation to N-methylaniline (N-MAn) is obvious from the results in Table 10. Seven-fold molar excess of aniline was added to a prepared aqueous solution of individual components of the reaction system, consisting of TMAH, betaine and potassium hydroxide. After azeotropic distilling off the water, 0.95 mol of nitrobenzene were added to the reaction mixture at 70° C. and at a pressure of 7.3 kPa during 1.5 h. The reaction was completed after further 2 h. Yield (Table 10) of the components in the reaction product has been calculated in relation to the introduced nitrobenzene. N-methylaniline (N-MAn) was expressed in mole per cent, related to the introduced TMAH. |
| 1: 53% 2: 24% 3: 11.4% 4: 1% | In cyclohexane; water at 80℃; for 6h; | 15 Example 15 Influence of Polarity of Auxiliary Solvents, Forming Azeotropic Mixtures with Water, on the Course of the Reaction of Nitrobenzene with Aniline Under Anaerobic Conditions. Example 15 Influence of Polarity of Auxiliary Solvents, Forming Azeotropic Mixtures with Water, on the Course of the Reaction of Nitrobenzene with Aniline Under Anaerobic Conditions. 0.078 mol of nitrobenzene were dosed into a reaction mixture, consisting of 0.09 mol of KOH (84.0% concentration), 0.09 mol of betaine hydrate, 4 ml of water, 0.51 mol of aniline and 15 ml of an auxiliary solvent, at 80° C. during 1.5 h. Completing the reaction required further 4.5 h, while water was continuously removed from the reaction medium as an azeotrope with the auxiliary solvent. In an experiment with 2-propanol, the azeotrope was distilled off through a short column under an atmospheric pressure. In an experiment with pyridine, the azeotrope distilled at a reduced pressure of 13.3 to 9.3 kPa. In an experiment with cyclohexane water was continuously removed as an azeotrope by means of an azeotropic attachment. The results are given in the following Table 7. |
| 1: 46% 2: 8.8% 3: 11.5% 4: 0.7% | In water at 50 - 80℃; for 3.5 - 6h; | 7,17,18 Example 7 Reaction of Aniline with Nitrobenzene Under the Conditions, where Water (reaction water and water, introduced as a solvent) is Continually Removed from the Reaction Medium, Particularly by Distillation in the Form of an Azeotrope Water-aniline, while Vacuum in the System is Gradually Decreased. Example 7 Reaction of Aniline with Nitrobenzene Under the Conditions, where Water (reaction water and water, introduced as a solvent) is Continually Removed from the Reaction Medium, Particularly by Distillation in the Form of an Azeotrope Water-aniline, while Vacuum in the System is Gradually Decreased. 114.0 g (0.131 mol) of 20% solution of an equimolar amount of betaine and potassium hydroxide were introduced into a 500 ml three-neck flask, and after heating up to 50° C. water was distilled off under vacuum, until crystalline slurry remained in the flask. 72.3 g of aniline (0.776 mol) were added, and 13.5 g (0.1097 mol) of nitrobenzene were dosed to the reaction mixture during 1.5 h at 80° C. in nitrogen atmosphere under intensive stirring. In the course of aniline adding a pressure of 26 kPa was maintained in the flask, while an azeotrope water-aniline distilled. During the final stage of the reaction in which the reaction mixture was stirred for further 4.5 h, the pressure in the apparatus was gradually reduced from the starting 26 kPa down to 4 kPa at the end of the reaction. After cooling down the reaction mixture was analyzed. A 100% conversion of nitrobenzene was achieved with the following yields (in %) of individual reaction components (calculated in relation to the introduced nitrobenzene): 4-NODFA 82.1%; 4-NO2DFA 11.7%; azobenzene 11.6%; phenazine 1.4%. Example 17 Effect of Water Content on the Reaction of Aniline with Nitrobenzene. A reaction mixture, consisting of aniline, nitrobenzene, potassium hydroxide, betaine and water with mutual molar ratios, given in Table 9, was let to react under intensive stirring at 80° C. at an atmospheric pressure under nitrogen during 6 h. After cooling down and diluting with methanol the obtained solution was analyzed, and the results were expressed in nitrobenzene conversion and yields, related to the charged nitrobenzene. Water in the reaction mixture is a sum of the reaction water, dissolving water and water, introduced by raw material, and it is expressed in mol per 1 mol of nitrobenzene. Example 18 Influence of different molar ratios of organic and inorganic hydroxides to betaine on the condensation of aniline with nitrobenzene and, simultaneously, influence of betaine and tetramethylammonium hydroxide (TMAH) on aniline methylation to N-methylaniline (N-MAn) is obvious from the results in Table 10. Seven-fold molar excess of aniline was added to a prepared aqueous solution of individual components of the reaction system, consisting of TMAH, betaine and potassium hydroxide. After azeotropic distilling off the water, 0.95 mol of nitrobenzene were added to the reaction mixture at 70° C. and at a pressure of 7.3 kPa during 1.5 h. The reaction was completed after further 2 h. Yield (Table 10) of the components in the reaction product has been calculated in relation to the introduced nitrobenzene. N-methylaniline (N-MAn) was expressed in mole per cent, related to the introduced TMAH. |
| 1: 39.1% 2: 17.6% 3: 10.8% 4: 9.8% | at 70℃; | 2 Example 2 Results of the Reaction of Aniline with Nitrobenzene, when Using Lithium, sodium, Potassium and Cesium Hydroxide in a Reaction System, Containing Betaine-hydroxide. Example 2 Results of the Reaction of Aniline with Nitrobenzene, when Using Lithium, sodium, Potassium and Cesium Hydroxide in a Reaction System, Containing Betaine-hydroxide. The reaction systems were prepared by the reaction of betaine monohydrate with alkali hydroxides. According to the procedure, described in Example 1, 3 identical reactions were performed at a temperature of 70° C. with various cations of alkali metals, given in Table 2. |
| 1: 24.7% 2: 31.1% 3: 31.6% 4: 10.9% | at 70℃; | 2 Example 2 Results of the Reaction of Aniline with Nitrobenzene, when Using Lithium, sodium, Potassium and Cesium Hydroxide in a Reaction System, Containing Betaine-hydroxide. Example 2 Results of the Reaction of Aniline with Nitrobenzene, when Using Lithium, sodium, Potassium and Cesium Hydroxide in a Reaction System, Containing Betaine-hydroxide. The reaction systems were prepared by the reaction of betaine monohydrate with alkali hydroxides. According to the procedure, described in Example 1, 3 identical reactions were performed at a temperature of 70° C. with various cations of alkali metals, given in Table 2. |
| 1: 89 % Chromat. 2: 4 % Chromat. 3: 3.5 % Chromat. 4: 3.5 % Chromat. | With tetramethyl ammoniumhydroxide at 50℃; | |
| 1: 22.2 - 40.3 %Chromat. 2: 18.7 - 23.1 %Chromat. 3: 7.3 - 44.1 %Chromat. 4: 1.4 - 9.3 %Chromat. | In methanol at 50 - 130℃; for 4.5h; | 1 Example 1 Results of the Reaction of Aniline with Nitrobenzene Under Anaerobic Conditions, when the Reaction System is a Solution of Betaine and Potassium Hydroxide in Methanol at Different Temperatures in the Range of 55 to 130° C. Example 1 Results of the Reaction of Aniline with Nitrobenzene Under Anaerobic Conditions, when the Reaction System is a Solution of Betaine and Potassium Hydroxide in Methanol at Different Temperatures in the Range of 55 to 130° C. For the reaction an apparatus was used which consisted of a 100 ml 3-neck flask with a magnetic stirrer, a thermometer, a dropping funnel and an azeotropic attachment, and was joined with a water-jet pump. 3,5 g (84.02%) of potassium hydroxide (0.052 mol) were dissolved in 6 g of methanol. 6.1 g of betaine (0.052 mol) were added and, after heating up to 50° C., 37.0 g of aniline (0.49 mol) were added. Air in the apparatus was replaced by nitrogen and after heating up to the reaction temperature at first methanol was distilled off at a pressure of 5.2 kPa, and then nitrobenzene, 6.4 g (0.052 mol) on the whole, was dosed under intensive stirring during 1.5 h. The reaction mixture was left to react for further 3 hours, then it was cooled down, diluted by methanol, and analyzed by the method of highly effective liquid chromatography. The yield of reaction components was calculated relative to the amount of nitrobenzene, introduced into the reaction. Further reaction conditions and results achieved are given in Table 1. |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 1: 63 mmol 2: 19.7 mmol 3: 3.3 mmol 4: 3.1 mmol 5: 1.1 mmol | With dihydrogen peroxide In dimethyl sulfoxide for 24h; also N-methylaniline; |