N,N′-Diphenyl-N,N-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine

solid

3.0 g (30 mmol) of sodium tert-butoxide, 217 mg (0.5 mmol) of IPr-HCl (compound No. 1), 45 mg (0.2 mmol) of palladium(II) acetate, 3.67 g (20 mmol) of 3-methyldiphenylamine, 3.2 g (10 mmol) of 4, 4'-dibromobiphenyl and 30 ml of toluene were put into a 50-ml three-neck flask equipped with a stirrer, a condenser tube, a thermometer and a gas-introducing duct, in an argon current at room temperature, and reacted under reflux in an oil bath controlled at a temperature of 130°C for 7 hours. The reaction liquid was cooled to room temperature, then left overnight at room temperature, and 150 ml of methylene chloride was added thereto. The insoluble matter was removed by filtration, and the filtrate was washed twice with 50 ml of water. This was dewatered and dried with 30 g of anhydrous sodium sulfate, and the solvent was evaporated away to give a residue. The residue was purified through column chromatography (carrier, Fuji Silicia's NH silica gel 150 g; eluent, cyclohexane) to give 4.4 g of N, N'-diphenyl-N, N'-di(m-tolyl)benzidine (TPD) (yield 85.2percent).In a 100 ml flask purged with a nitrogen atmosphere, 30 g of xylene, 7.33 g (40 mmol) of N- (3-methylphenyl) aniline, 0.96 g (40 mmol) of sodium hydride, 7.36 g (40 mmol) of magnesium bromide was charged, The reaction solution was heated to 140 ° C. while stirring.After aging for 2 hours at the same temperature, 0.063 g (0.5 mmol) of iron (II) chloride, 3.12 g (10 mmol) of 4, 4'-dibromobiphenyl was added, Further aging was carried out for 14 hours at the same temperature. After completion of the reaction, After cooling, water was added to dissolve the salt and liquid separation was carried out. After separating the organic layer, As a result of analysis by GC using the internal standard method, Bis (3-methylphenylphenylamino) biphenyl as a target product was produced in a yield of 51percent.Charge a dry, nitrogen filled flask with 4.9 g (0.07 mol of zinc powder), 3.4 g (0.01 mol) of triphenylphosphine. 0.4 g (0.002 mol) of 2, 2'-bipyridyl, 0.3 g (0.002 mol) of anhydrous NiCl2, 30 mL of dry, deoxygenated DMF, and 2 g of activated 3A molecular sieves. The mixture is heated under nitrogen to 65° C. until the gray color changed to dark brown (about 10-15 minutes). Maintaining a pot temperature of 60° C., a solution of (4-chloro-phenyl)-phenyl-m-tolyl amine (13.4 g, 0.04 mol) in 40 mL of DMF is added dropwise. After addition is over, the reaction is stirred between 60-65° C. for 2-5 hours, until TLC analysis revealed complete consumption of starting aryl chloride. The reaction is diluted with dichloromethane, filtered to remove excess zinc and solids. The filtrate washed four times with water. The dichloromethane layer is dried over sodium sulfate, filtered and concentrated to a reduced volume. The dichloromethane solution is treated with silica gel, filtered, and solution is treated with neutral alumina until the solution is pale yellow. The product is crystallized twice to afford 8.7 g (80percent) of N4, N4'-diphenyl-N4, N4'-di-m-tolyl-biphenyl-4, 4'- diamine as a white solid. An analytical sample can be obtained by chromatography using a slow gradient of 0-5percent ethyl acetate in hexane.(Synthetic Example 1) N, N'-diphenyl-N, N'-bis(3-tolyl)-4, 4'-diaminobiphenyl (3, 3-TPD) was synthesized as follows. 1.0g (2.46mmol) of 4, 4'-diiodobiphenyl and 20 ml of o-dichlorobenzene were added to a 100 ml four-necked flask made of glass. Furthermore 1.08g (5.90mmol) of m-methyldiphenylamine, 0.104g of poly(ethylene glycol) PEG-6000 as a reaction accelerator that was available from Wako Pure Chemical Industries, Ltd., 2.73g (0.0198mol) of potassium carbonate and 0.635g (9.87mmol) of powdered copper were added thereto. It was determined for tracing by the high-speed liquid chromatography. And it was stirred and refluxed for 22 hours until no peaks of starting materials and intermediates were determined. It was filtrated at the hot temperature. The product was washed with dichloromethane until color of the filtrate was to be light. The solvent was distilled under reduced pressure. Residual product was purified by silica gel column chromatography to obtain 3, 3-TPD that is represented by Compound Example 1.3.0 g (30 mmol) of sodium tert-butoxide, 217 mg (0.5 mmol) of IPr-HCl (compound No. 1), 45 mg (0.2 mmol) of palladium(II) acetate, 3.67 g (20 mmol) of 3-methyldiphenylamine, 3.2 g (10 mmol) of 4, 4'-dibromobiphenyl and 30 ml of toluene were put into a 50-ml three-neck flask equipped with a stirrer, a condenser tube, a thermometer and a gas-introducing duct, in an argon current at room temperature, and reacted under reflux in an oil bath controlled at a temperature of 130°C for 7 hours. The reaction liquid was cooled to room temperature, then left overnight at room temperature, and 150 ml of methylene chloride was added thereto. The insoluble matter was removed by filtration, and the filtrate was washed twice with 50 ml of water. This was dewatered and dried with 30 g of anhydrous sodium sulfate, and the solvent was evaporated away to give a residue. The residue was purified through column chromatography (carrier, Fuji Silicia's NH silica gel 150 g; eluent, cyclohexane) to give 4.4 g of N, N'-diphenyl-N, N'-di(m-tolyl)benzidine (TPD) (yield 85.2percent).In a 100 ml flask purged with a nitrogen atmosphere, 30 g of xylene, 7.33 g (40 mmol) of N- (3-methylphenyl) aniline, 0.96 g (40 mmol) of sodium hydride, 7.36 g (40 mmol) of magnesium bromide was charged, The reaction solution was heated to 140 ° C. while stirring.After aging for 2 hours at the same temperature, 0.063 g (0.5 mmol) of iron (II) chloride, 3.12 g (10 mmol) of 4, 4'-dibromobiphenyl was added, Further aging was carried out for 14 hours at the same temperature. After completion of the reaction, After cooling, water was added to dissolve the salt and liquid separation was carried out. After separating the organic layer, As a result of analysis by GC using the internal standard method, Bis (3-methylphenylphenylamino) biphenyl as a target product was produced in a yield of 51percent.In the reactor with a thermometer and reflux device, 3.61 kg (5.97 mol) of intermediate 3a was added.0.08 kg (0.56 mol) of copper(I) oxide, 0.03 kg (0.26 mol) of TMEDA, 3.55 kg (35.85 mol) of NMP, and reacted at 200 ° C for 4 h.After the reaction, the NMP solvent was distilled off, and 1.5 L of water was added thereto to be uniformly mixed, and filtered to obtain a crude black product.The crude black product was recrystallized from cyclohexane to give white crystals of N, N'-bis(3-methylphenyl)-N, N'-diphenyl-1, 1'-biphenyl-4, 4'-diamine. (4a) 2.88kg, The purity was 99.6percent and the yield was 93.5percent. Compound 4a was characterized as in Example 1.Synthesis of TPD-crosslinking group compound 1) Synthesis of TPD-CHO [0052] At 0°C, under nitrogen protection, POCl3 (6.0g) is added to DMF (2.8g), followed by the addition of TPD (12.5g) in 120ml 1, 2-dichloroethane and the mixture heated to 70°C for 3h. After cooling, the mixture is added into 500 ml water, and extracted with ethyl acetate. The organic layer is neutralized with aqueous NaCO3 solution. Finally isolation is conducted by silica gel chromatography using a petroleum ether/ethyl acetate (with a volume ratio of 8:1) mixed solvent as the developing solvent, to give TPD-CHO, and the yield is 50percent.

Hole transport material for electrophotographic photoconductor in xerography.

Molecular Weight:516.7
XLogP3:10.8
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:7
Exact Mass:516.256549029
Monoisotopic Mass:516.256549029
Topological Polar Surface Area:6.5
Heavy Atom Count:40
Complexity:660
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes