Structure of 65181-78-4
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CAS No. : | 65181-78-4 |
Formula : | C38H32N2 |
M.W : | 516.67 |
SMILES Code : | CC1=CC(N(C2=CC=CC=C2)C3=CC=C(C=C3)C4=CC=C(C=C4)N(C5=CC=CC(C)=C5)C6=CC=CC=C6)=CC=C1 |
MDL No. : | MFCD00144965 |
InChI Key : | OGGKVJMNFFSDEV-UHFFFAOYSA-N |
Pubchem ID : | 103315 |
GHS Pictogram: |
![]() ![]() |
Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335-H351-H361 |
Precautionary Statements: | P261-P305+P351+P338 |
Num. heavy atoms | 40 |
Num. arom. heavy atoms | 36 |
Fraction Csp3 | 0.05 |
Num. rotatable bonds | 7 |
Num. H-bond acceptors | 0.0 |
Num. H-bond donors | 0.0 |
Molar Refractivity | 171.18 |
TPSA ? Topological Polar Surface Area: Calculated from |
6.48 Ų |
Log Po/w (iLOGP)? iLOGP: in-house physics-based method implemented from |
5.94 |
Log Po/w (XLOGP3)? XLOGP3: Atomistic and knowledge-based method calculated by |
10.75 |
Log Po/w (WLOGP)? WLOGP: Atomistic method implemented from |
10.91 |
Log Po/w (MLOGP)? MLOGP: Topological method implemented from |
8.14 |
Log Po/w (SILICOS-IT)? SILICOS-IT: Hybrid fragmental/topological method calculated by |
8.05 |
Consensus Log Po/w? Consensus Log Po/w: Average of all five predictions |
8.76 |
Log S (ESOL):? ESOL: Topological method implemented from |
-10.02 |
Solubility | 0.0000000494 mg/ml ; 0.0000000001 mol/l |
Class? Solubility class: Log S scale |
Insoluble |
Log S (Ali)? Ali: Topological method implemented from |
-10.84 |
Solubility | 0.0000000074 mg/ml ; 0.0 mol/l |
Class? Solubility class: Log S scale |
Insoluble |
Log S (SILICOS-IT)? SILICOS-IT: Fragmental method calculated by |
-14.23 |
Solubility | 0.0 mg/ml ; 0.0 mol/l |
Class? Solubility class: Log S scale |
Insoluble |
GI absorption? Gatrointestinal absorption: according to the white of the BOILED-Egg |
Low |
BBB permeant? BBB permeation: according to the yolk of the BOILED-Egg |
No |
P-gp substrate? P-glycoprotein substrate: SVM model built on 1033 molecules (training set) |
Yes |
CYP1A2 inhibitor? Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set) |
No |
CYP2C19 inhibitor? Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set) |
Yes |
CYP2C9 inhibitor? Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set) |
No |
CYP2D6 inhibitor? Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set) |
No |
CYP3A4 inhibitor? Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set) |
No |
Log Kp (skin permeation)? Skin permeation: QSPR model implemented from |
-1.82 cm/s |
Lipinski? Lipinski (Pfizer) filter: implemented from |
2.0 |
Ghose? Ghose filter: implemented from |
None |
Veber? Veber (GSK) filter: implemented from |
0.0 |
Egan? Egan (Pharmacia) filter: implemented from |
1.0 |
Muegge? Muegge (Bayer) filter: implemented from |
1.0 |
Bioavailability Score? Abbott Bioavailability Score: Probability of F > 10% in rat |
0.17 |
PAINS? Pan Assay Interference Structures: implemented from |
0.0 alert |
Brenk? Structural Alert: implemented from |
0.0 alert: heavy_metal |
Leadlikeness? Leadlikeness: implemented from |
No; 1 violation:MW<2.0 |
Synthetic accessibility? Synthetic accessibility score: from 1 (very easy) to 10 (very difficult) |
3.45 |
* 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 |
---|---|---|
85.2% | With sodium t-butanolate;palladium diacetate; 1,3-bis[2,6-diisopropylphenyl]imidazolium chloride; In toluene; at 20 - 130℃;Inert atmosphere; | 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). |
51% | 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. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With copper; potassium carbonate;PEG-6000; In 1,2-dichloro-benzene; for 22h;Heating / reflux; | (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. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With 3 A molecular sieve;[2,2]bipyridinyl; triphenylphosphine; nickel dichloride; zinc; In N,N-dimethyl-formamide; at 60 - 65℃; for 2.16667 - 5.25h; | 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. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
(Synthetic Example 3) The mixture of 3,3-TPD, 4,4-TPD and N,N'-diphenyl-N-(3-tolyl)-N'-(4-tolyl)-4,4'-diaminobiphenyl (3,4-TPD) that is represented by Compound Example 3 was synthesized as follows. Mixture of 438g (2.43mol) of 3-methyldiphenylamine and 49g (0.27mol) of 4-methyldiphenylamine whose mol ratio is 90: 10 were added to a 5000 ml four-necked flask made of glass. Further 28g (4.4mol) of powdered copper was added thereto. It was heated at 30 degrees Centigrade. 450g (1.1mol) of 4,4'-diiodobiphenyl and 47g of poly(ethylene glycol) PEG-6000 that was available from Wako Pure Chemical Industries, Ltd. were added thereto. It was heated at 100 degrees Centigrade, and then 307g (2.2mol) of powdered potassium carbonate was added thereto. It was heated at 205 degrees Centigrade, and stirred for 14 hours. After cooling, DMF was added thereto, and stirred at 130 degrees Centigrade for 1 hour. After cooling till 90 degrees Centigrade, hot water was added thereto. It was stirred for 2 hours. After filtration, filtrated cake was washed with hot water to obtain brown solid. The obtained brown solid was dispersed and stirred into DMF for 1 hour, filtrated and washed with DMF and methanol. The obtained solid was refluxed with activated carbon in xylene for 1 hour. After cooling till 70 degrees Centigrade, it was filtrated. The filtrate was passed through a column packing adsorbent to obtain colorless solution. The solvent was distilled under reduced pressure. Precipitated crystals were filtrated out and dried to obtain 455g of mixture of TPD. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium hydroxide; copper; In Soltrol/70; at 165℃; for 7h;Product distribution / selectivity; | A 5 L tri-neck round bottom flask (equipped with a mechanical stirrer, a thermal controller, and a condensing tube) was communicated with a nitrogen source and contained 500 g of dibromobiphenyl (1.6 moles), 620 g of 3-methyldiphenylamine (3.4 moles), 50 g of diphenylamine (0.3 mole), 168 g of potassium hydroxide (3 moles), 122 g of copper powder (1.76 moles) and 224 ml of Soltrol/70.(R). (fatty mixture of C13-C15 purchased from Phillips Chemical Company). The mixture solution was heated to 165° C. for 7 hours and then 2.5 L Soltrol/70.(R). was added. The temperature of the mixture solution was lowered to 154° C. to filter inorganic solids and to obtain a filtering liquid. 2 L of methanol was added to the filtering liquid to accelerate crystallization of the benzidine compounds. Then, the filtering liquid was filtered again to obtain a yellow solid, which is a crude mixture of three types of benzidine compounds. Moreover, 2 L of methanol dissolved the crude mixture of benzidine compounds and filtered by 1.2 Kg of Woelm neutral alumina to obtain a light-yellow solid. Lastly, n-octane was used to dissolve the light-yellow solid and to re-crystallize the benzidine compounds in the form of white crystal. The white crystal weighed 500 g, has a melting point range of 168-170° C., and is a final mixture of the benzidine compounds having high purity. | |
tris-(dibenzylideneacetone)dipalladium(0); 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; at 139℃; for 6.5h;Product distribution / selectivity; | A 5 L tri-neck round bottom flask (equipped with a mechanical stirrer, a thermal controller, a condensing tube, and a Dean-Stark device) was communicated with a nitrogen source and accommodated 500 g of dibromobiphenyl (1.6 moles), 620 g of 3-methyldiphenylamine (3.4 moles), 50 g of diphenylamine (0.3 mole), 2.4 L of 10-crown-6-ether, 7.36 g of Pd2(dba)3 (0.008 mole) and 5.0 g 2,2'-bis(diphenylphosphino-1,1'-(binaphthyl) (0.008 mole). The mixture solution was stirred for 30 minutes and heated to a reflux temperature of 139° C. The mixture solution was further stirred to react for 6 hours and had further added thereto 1 L of m-xylene and 1 L of deionized water. The mixture solution was held at 65° C. and poured into an extracting bottle to place for 10 minutes until layers of the mixture solution separated. An organic layer, i.e. an m-xylene solution, was removed from the mixture solution, washed with 2 L of deionized water twice and kept at 55° C. The m-xylene solution was filtered by 600 g of Woelm neutral alumina to obtain a filtering liquid. Then, the filtering liquid was dried to obtain 630 g of a crude mixture of benzidine compounds in the form of a yellow solid. Lastly, n-octane was used to dissolve the crude mixture and to re-crystallize the benzidine compounds in the form of pure white crystal. The pure white crystal weighed 595 g, has a melting point range of 169-170° C., and is a final mixture of the benzidine compounds having high purity. | |
With calcium carbonate; zinc;1,10-Phenanthroline; copper diacetate; In xylene; at 120℃; for 10.5h;Product distribution / selectivity; | A 5 L tri-neck round bottom flask (equipped with a mechanical stirrer, a thermal controller, and a condensing tube) was communicated with a nitrogen source and contained 500 g of dibromobiphenyl (1.6 moles), 620 g of 3-methyldiphenylamine (3.4 moles), 50 g of diphenylamine (0.3 mole), 2.4 L of xylene, 27 g of 1,10-phenanthroline (0.14 mole), 420 g of cuprous acetate-monohydrate (2.1 moles), 140 g of zinc (2.1 moles) and 552 g of calcium carbonate (4 moles). The mixture solution was stirred for 30 minutes and heated to 120° C. The mixture solution was further stirred to react for 10 hours and had further added thereto 500 ml of xylene, 500 ml of deionized water and 350 g of acetic acid to neutralize calcium carbonate. The mixture solution was held at 65° C. and poured into an extracting bottle to place for 10 minutes until layers of the mixture solution separated. An organic layer, i.e. a xylene solution, was removed from the mixture solution, washed with 1.5 L of deionized water twice and kept at 55° C. The xylene solution was filtered by 500 g of Woelm neutral alumina to obtain a filtering liquid. Then, 1 L of methanol was added to the filtering liquid to accelerate crystallization of benzidine compounds to obtain 595 g crude mixture of benzidine compounds in the form of a white solid. Lastly, n-octane was used to dissolve the crude mixture and to re-crystallize the benzidine compounds in the form of pure white crystal. The pure white crystal weighed 545 g, has a melting point range of 169-170° C., and is a final mixture of the benzidine compounds having high purity |
With potassium hydroxide;1,10-Phenanthroline; copper dichloride; In toluene; at 125℃; for 6.5h;Product distribution / selectivity; | A 5 L tri-neck round bottom flask (equipped with a mechanical stirrer, a thermal controller, and a condensing tube) was communicated with a nitrogen source and contained 500 g of dibromobiphenyl (1.6 moles), 620 g of 3-methyldiphenylamine (3.4 moles), 50 g of diphenylamine (0.3 mole), 24 L of toluene, 27 g of 1,10-phenanthroline (0.14 mole), 16 g of cuprous chloride (0.14 mole) and 168 g potassium hydroxide (3 moles). The mixture solution was stirred for 30 minutes and heated to 125° C. The mixture solution was further stirred to react for 6 hours and had added thereto 500 ml of toluene, 500 ml of deionized water and 400 g of acetic acid to neutralize the potassium hydroxide. The mixture solution was held at 70° C. and then poured into an extracting bottle to place for 10 minutes until layers of the mixture solution separated. An organic layer, i.e. a toluene solution, was removed from the mixture solution, washed with 1 L of deionized water twice and kept at 60° C. The toluene solution was filtered by 500 g of Woelm neutral alumina to obtain a filtering liquid. Then, the filtering liquid was dried to obtain 605 g of a crude mixture of benzidine compounds in the form of a white solid. Lastly, n-octane was used to dissolve the crude mixture and to re-crystallize the benzidine compounds in the form of pure white crystal. The pure white crystal weighed 500 g, has a melting point range of 169-170° C., and is a final mixture of the benzidine compounds having high purity. | |
With potassium hydroxide;1,10-Phenanthroline; copper dichloride; In m-xylene; at 139℃; for 7.5h;Heating / reflux;Product distribution / selectivity; | A 5 L tri-neck round bottom flask (equipped with a mechanical stirrer, a thermal controller, a condensing tube, and a Dean-Stark device) was communicated with a nitrogen source and accommodated 500 g of dibromobiphenyl (1.6 moles), 620 g of 3-methyldiphenylamine (3.4 moles), 50 g of diphenylamine (0.3 mole), 2.4 L of m-xylene, 27 g of 1,10-phenanthroline (0.14 mole), 16 g of cuprous chloride (0.14 mole) and 168 g potassium hydroxide (3 moles). The mixture solution was stirred for 30 minutes and heated to a reflux temperature of 139° C. The mixture solution was further stirred to react for 7 hours and had further added thereto 1 L of m-xylene, 1 L of deionized water and 400 g of acetic acid to neutralize the potassium hydroxide. The mixture solution was held at 65° C. and poured into an extracting bottle to place for 10 minutes until layers of the mixture solution separated. An organic layer, i.e. an m-xylene solution, was removed from the mixture solution, washed with 2 L of deionized water twice and kept at 55° C. The m-xylene solution was filtered by 600 g of Woelm neutral alumina to obtain a filtering liquid. Then, the filtering liquid was dried to obtain 610 g of a crude mixture of benzidine compounds in the form of a Elite solid. Lastly, n-octane was used to dissolve the crude mixture and to re-crystallize the benzidine compounds in the form of pure white crystal. The pure white crystal weighed 585 g, has a melting point range of 169-170° C., and is a final mixture of the benzidine compounds having high purity. | |
With potassium hydroxide;1,10-Phenanthroline; copper dichloride; In xylene; at 145℃; for 7.5h;Heating / reflux;Product distribution / selectivity; | A 5 L tri-neck round bottom flask (equipped with a mechanical stirrer, a thermal controller, a condensing tube, and a Dean-Stark device) was communicated with a nitrogen source and accommodated 500 g of dibromobiphenyl (1.6 moles), 620 g of 3-methyldiphenylamine (3.4 moles), 50 g of diphenylamine (0.3 mole), 2.4 L of xylene, 27 g of 1,10-phenanthroline (0.14 mole), 16 g of cuprous chloride (0.14 mole) and 168 g of potassium hydroxide (3 moles). The mixture solution was stirred for 30 minutes and heated to a reflux temperature of 145° C. The mixture solution was further stirred to react for 7 hours and had further added thereto 1 L of o-xylene, 1 L of deionized water and 400 g of acetic acid to neutralize the potassium so hydroxide. The mixture solution was held at 100° C. and poured into an extracting bottle to place for 10 minutes until layers of the mixture solution separated. An organic layer, i.e. an o-xylene solution, was removed from the mixture solution, washed with 1.5 L of deionized water twice and kept at 70° C. The o-xylene solution was filtered by 20 g of Alcoa-C neutral alumina to obtain a filtering liquid. Then, the filtering liquid was dried to obtain 615 g of a crude mixture of benzidine compounds in the form of a white solid. Lastly, n-octane was used to dissolve the crude mixture and to re-crystallize the benzidine compounds in the form of pure white crystal. The pure white crystal weighed 600 g, has a melting point range of 168-170° C., and is a final mixture of the benzidine compounds having high purity. | |
With potassium hydroxide; 18-crown-6 ether; copper; In m-xylene; at 139℃; for 10.5h;Product distribution / selectivity; | A 5 L tri-neck round bottom flask (equipped with a mechanical stirrer, a thermal controller, and a condensing tube) was communicated with a nitrogen source and contained 500 g of dibromobiphenyl (1.6 moles), 620 g of 3-methyldiphenylamine (3.4 moles), 50 g of diphenylamine (0.3 mole), 2.4 L of m-xylene (0.14 mole), 150 g of copper powder (2.4 moles), 168 g potassium hydroxide (3 moles) and 35 g of 18-crown-6-ether. The mixture solution was stirred for 30 minutes and heated to a reflux temperature of 139° C. The mixture solution was further stirred to react for 10 hours and had further added thereto 1 L of m-xylene, 1 L of deionized water and 400 g of acetic acid to neutralize the potassium hydroxide. The mixture solution was held at 65° C. and poured into an extracting bottle to place for 10 minutes until layers of the mixture solution separated. An organic layer, i.e. an m-xylene solution, was removed from the mixture solution, washed with 2 L of deionized water twice and kept at 55° C. The m-xylene solution was filtered by 600 g of Woelm neutral alumina to obtain a filtering liquid. Then, the filtering liquid was dried to obtain 620 g of a crude mixture of benzidine compounds in the form of a white solid. Lastly, n-octane was used to dissolve the crude mixture and to re-crystallize the benzidine compounds in the form of pure white crystal. The pure white crystal weighed 600 g, has a melting point range of 169-170° C., and is a final mixture of the benzidine compounds having high purity. | |
With potassium hydroxide; copper; In Soltrol/170; at 190℃; for 10.5h;Product distribution / selectivity; | A 5 L tri-neck round bottom flask (equipped with a mechanical stirrer, a thermal controller, and a condensing tube) was communicated with a nitrogen source and accommodated 500 g of dibromobiphenyl (1.6 moles), 620 g of 3-methyldiphenylamine (3.4 moles), 50 g of diphenylamine (0.3 mole), 2 L of Soltrol.(R)./170, 150 g of copper powder (2.4 moles) and 168 g potassium hydroxide (3 moles). The mixture solution was stirred for 30 minutes and heated to 190° C. The mixture solution was further stirred to react for 10 hours and had further added thereto 1 L of toluene, 1.5 L of deionized water and 400 g of acetic acid to neutralize the potassium hydroxide. The mixture solution was held at 65° C. and poured into an extracting bottle to place for 10 minutes until layers of the mixture solution separated. An organic layer, i.e. a toluene solution, was removed from the mixture solution, washed with 2 L of deionized water twice and kept at 55° C. The toluene solution was filtered by 500 g of Woelm neutral alumina to obtain a filtering liquid. Then, the filtering liquid was dried to obtain 630 g of a crude mixture of benzidine compounds in the form of a white solid. Lastly, n-octane was used to dissolve the crude mixture and to re-crystallize the benzidine compounds in the form of pure white crystal. The pure white crystal weighed 600 g, has a melting point range of 167-170° C., and is a final mixture of the benzidine compounds having high purity. | |
With sodium t-butanolate;palladium diacetate; tri-tert-butyl phosphine; In xylene; at 125℃; for 5.5h;Product distribution / selectivity; | A 5 L tri-neck round bottom flask (equipped with a mechanical stirrer, a thermal controller, a condensing tube, and a Dean-Stark device) was communicated with a nitrogen source and accommodated 500 g of dibromobiphenyl (1.6 moles), 620 g of 3-methyldiphenylamine (3.4 moles), 50 g of diphenylamine (0.3 mole), 2.5 L of xylene, 0.183 g of Pd(OAc)2 (0.051 mole), 0.14 g of P(t-Bu)3 (0.043 mole) and 350 g NaO-(t-Bu) (3.64 mole). The mixture solution was stirred for 30 minutes and heated to a reflux temperature of 125° C. The mixture solution was further stirred to react for 5 hours and had further added thereto 500 ml of o-xylene and 500 ml of deionized water. The mixture solution was held at 65° C. and poured into an extracting bottle to place for 10 minutes until layers of the mixture solution separated. An organic layer, i.e. an o-xylene solution, was removed from the mixture solution, washed with 1 L of deionized water twice and kept at 55° C. The o-xylene solution was filtered by 500 g of Woelm neutral alumina to obtain a filtering liquid. Then, the filtering liquid was dried to obtain 660 g of a crude mixture of benzidine compounds in the form of a white solid. Lastly, n-octane was used to dissolve the crude mixture and to re-crystallize the benzidine compounds in the form of pure white crystal. The pure white crystal weighed 580 g, has a melting point range of 168-170° C., and is a final mixture of the benzidine compounds having high purity. | |
With sodium t-butanolate;tris-(dibenzylideneacetone)dipalladium(0); In toluene; at 110℃; for 5.5h;Product distribution / selectivity; | A 5 L tri-neck round bottom flask (equipped with a mechanical stirrer, a thermal controller, a condensing tube, and a Dean-Stark device) was communicated with a nitrogen source and accommodated 500 g of dibromobiphenyl (1.6 moles), 620 g of 3-methyldiphenylamine (3.4 moles), 50 g of diphenylamine (0.3 mole), 2.4 L of toluene, 7.36 g of Pd2(dba)3 (0.008 mole) (prepared according to J. Org. Chem. 2000,65,p.5330) and 350 g NaO-(t-Bu) (3.64 mole). The mixture solution was stirred for 30 minutes and heated to a reflux temperature of 110° C. The mixture solution was further stirred to react for 5 hours and had further added thereto 500 ml of toluene and 500 ml of deionized water. The mixture solution was held at 55° C. and poured into an extracting bottle to place for 10 minutes until layers of the mixture solution separated. An organic layer, i.e. a toluene solution, was removed from the mixture solution, washed with 2 L of deionized water twice and kept at 55° C. The toluene solution was filtered by using 500 g of Woelm neutral alumina to obtain a filtering liquid. Then, the filtering liquid was dried to obtain 650 g of a crude mixture of benzidine compounds in the form of a yellow solid. Lastly, n-octane was used to dissolve the crude mixture and to re-crystallize the benzidine compounds in the form of pure white crystal. The pure white crystal weighed 550 g, has a melting point range of 169-170° C., and is a final mixture of the benzidine compounds having high purity. |
Yield | Reaction Conditions | Operation in experiment |
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82% | With tri-tert-butyl phosphine; 5%-palladium/activated carbon; sodium t-butanolate; In o-xylene; at 110℃; for 2h;Inert atmosphere; | General procedure: A cooling tube, round bottom flask 50mL equipped with athermometer, at room temperature, bromobenzene 1.4g in a nitrogen atmosphere(9.0 mmol), 3- methyl-diphenylamine 1.1 g (6.0 mmol), palladium supported materialB 0 .13g (palladium atom 0.12mmol), was mixed with sodium -tert- butoxide 0.86g(9.0mmol) and o- xylene 6.0g. After nitrogen is a flow of about 20 minutes, tri(tert- butyl) phosphine (hereinafter, "P- (tBu) 3" and also indicate)36.4 mg (0.18 mmol) was dissolved o- xylene ( 150 uL) was added and undernormal pressure, pressurized to 110 ° C.It was raised and the mixture was stirred for 2 hours after.Incidentally, the yield by gas chromatography, was calculated by internalstandard method with an internal standard substance n- eicosane. The resultsare shown in Table 1. |
Procedures for Fabrication of Organic Light-Emitting Devices (OLEDs) Chemicals ISB was prepared according to the following procedure: A round bottom flask was charged with Na-t-butoxicle (4.25 g), Pd2dba3 (0.22 g), DPPF (diphenylphosphinoferrocene 0.33 g), and 50 ml anhydrous toluene. The reaction mixture was stirred under argon at 90° C. for 15 minutes. Then dibromobiphenyl (3.12 g) and iminostilbene (4.25 g) were added, and the reaction was stirred for 8 hours until the amine could not be detected by mass spectroscopy. The solvent was then stripped from the reaction mixture and the crude residue was dried under vacuum. The dried residue was then subjected to a gradient sublimation under reduced pressure (10-4 torr). The sublimation yielded 2.06 g of pure material, 36percent of the theoretical reaction yield. IDB was prepared according to the following procedure: 51 mmol (10.000 g) iminodibenzyl was reacted with 17 mmol (6.94 g) 4,4'-diiodobiphenyl. The reaction product was added to a round bottom flask fitted with a condenser, along with 34 mmol (2.16 g) copper powder, 68 mmol (9.398 g) potassium carbonate, 2 mmol (0.530 g) 18-crown-6 ether, and 20 ml o-dichlorobenzene. The flask was heated to 185° C. and then refluxed under argon for 24 hours. The reaction mixture was filtered hot and the filtrate was put under vacuum to remove the solvent. The residue was then passed through a short column of silica gel in toluene. The solvent was then removed from the column filtrate and the solid left behind was sublimed at 220° C. under a vacuum of 0.01 Torr. for purification. The electron transporting material Alq3, as well as the TPD and NPD, were synthesised according to literature procedure. All organic materials were sublimed before use. The fluorene bridged materials were prepared according to the following general procedure: A round bottomed flask was charged with Pd2dba3 (0.030 eq), dppf (0.045 eq), and Na-t-butoxide (3.0 eq) in a nitrogen glove box. | ||
(ii) Low molecular weight compounds:...1,1-bis (p-diethylaminophenyl)-4,4-diphenyl-1,3-butadiene,N,N,N',N'-tetraphenylbenzidine,N,N'-diphenyl-N,N'-bis (3-methylphenyl)benzidine,N,N'-di-2-naphthyl-N,N'-bis(3-methyphenyl)-benzidine,... |
EXAMPLE I N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine can be prepared in the following manner. A 500 milliliter 3-neck round bottom flask equipped with a mechanical stirrer, reflux condenser, and argon inlet was purged with argon and then charged with the following reagents in the indicated order, all under an argon blanket: Under an inert atmosphere of argon, the reaction mixture was quickly heated over a period of 30 minutes to the temperature of reflux (125°) and allowed to proceed at that temperature until chromatographic analysis by high performance liquid chromatography indicated that the reaction was complete after approximately 5 hours. 150 Milliliters of toluene and 150 milliliters of deionized water were then added, and finally 17.7 grams of acetic acid were also added to neutralize the KOH. The resulting warm, 60° C., two phase mixture was transferred to a separatory funnel, and the layers separated. The organic phase was washed with two 100 milliliter portions of deionized water and treated while warm, approximately 45° C., and under argon with 2.0 grams of Alcoa CG-20 alumina. The crude N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine was isolated by filtering off the alumina and distilling toluene. A total of 100 milliliters of toluene was removed in this manner and replaced by 100 milliliters of ISOPAR M.(TM).. Slow cooling of the solution under argon afforded the high purity crude product in 92 percent yield after vacuum filtration and drying. The crude purity was 95 percent as evidenced by high performance liquid chromatography. | ||
EXAMPLE I N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1 '-biphenyl-4,4'-diamine can be prepared in the following manner. A 500 milliliter 3-neck round bottom flask equipped with a mechanical stirrer, reflux condenser, and argon inlet was purged with argon and then charged with the following reagents in the indicated order, all under an argon blanket: Under an inert atmosphere of argon, the reaction mixture was quickly heated over a period of 30 minutes to the temperature of reflux (125°) and allowed to proceed at that temperature until chromatographic analysis by high performance liquid chromatography indicated that the reaction was complete after approximately 5 hours. 150 Milliliters of toluene and 150 milliliters of deionized water were then added, and finally 17.7 grams of acetic acid were also added to neutralize the KOH. The resulting warm, 60° C., two phase mixture was transferred to a separatory funnel, and the layers separated. The organic phase was washed with two 100 milliliter portions of deionized water and treated while warm, approximately 45° C., and under argon with 2.0 grams of Alcoa CG-20 alumina. The crude N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl- 4,4'-diamine was isolated by filtering off the alumina and distilling toluene. A total of 100 milliliters of toluene was removed in this manner and replaced by 100 milliliters of ISOPAR M.(TM). Slow cooling of the solution under argon afforded the high purity crude product in 92 percent yield after vacuum filtration and drying. The crude purity was 95 percent as evidenced by high performance liquid chromatography. |
Yield | Reaction Conditions | Operation in experiment |
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With potassium hydroxide; | EXAMPLE V Preparation of N,N'-diphenyl-N,N'-bis-(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine in the absence of the aliphatic hydrocarbon solvent. A 500 milliliter 3 necked round bottom flask equipped with an argon purge, a condenser and an overhead mechanical stirrer was charged with 81.2 grams (0.2 mole) of 4,4'-diiodobiphenyl, 146.4 grams (0.8 mole) of 3-methyl-diphenylamine, 89.6 grams (1.6 moles) of KOH flake and 80 grams (1.0 mole) of copper powder. The flask was immersed in a 165° C. oil bath and the two-phase melt was stirred for 3 hours. Hot (140° C.) Soltrol.(R). 170 was added and the inorganic solid separated by vacuum filtration. On cooling, the product crystallized from the filtrate and was isolated in 89percent yield by filtration. Purification was accomplished by slurrying the product with neutral alumina (10 grams) in 1 liter of Soltrol.(R). 170 at 150° C. for six hours, the alumina was removed by filtration and the purified product crystallized from the filtration on cooling. Isolation by filtration was accomplished with a 95percent recovery of the product. |
Yield | Reaction Conditions | Operation in experiment |
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Comparative Example 1 Thin films were deposited as in Example 6 except that the compound of Example 1 was replaced by compound (1): N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diamino-1,1'-biphenyl (mp: 171.2°C, Tg: 61.3°C) or compound (2): 1,1'-bis(4-di-p-tolylaminophenyl)cyclohexane (mp: 187.8°C, Tg: 79.9°C). The thin films were allowed to stand in a constant temperature chamber at 30°C/RH 100percent. Although the films were allowed to stand in a milder temperature environment than in Examples 6 to 8, crystallization started on the third day in the film of compound (1) and on the 30th day in the film of compound (2). As in Example 6, the films of compounds (1) and (2) were measured for ionization potential. Both had an Ip of 5.40 eV. |
Yield | Reaction Conditions | Operation in experiment |
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In acetonitrile; for 1.5h;Reflux; Inert atmosphere; | Alternatively both steps of the process can be performed in a single reaction vessel without isolation of the imidazolium intermediate. A 5 L round bottom flask equipped with mechanical stirring was flame-dried and cooled under Ar. Acetonitrile (800 mL), imidazole (79 g, 115 mmol), N,N'-diphenyl-N,N'-bis(3-methylphenyl)benzidine (mTBD) (100 g, 192 mmol), and trifluoroacetic anhydride (323 mL, 233 mmol) were combined and the mixture was heated to reflux and monitored by HPLC. The reaction was complete in less than 1.5 h to form the tetrasubstituted imidazoline product. The reaction mixture was removed from the oil bath and THF (1.6 L) and HCl (2 M aq, 800 mL) was added. The mixture was returned to the heating bath and stirred at 90 C for 16 h. No starting material remained with the tetrasubstituted imidazoline compound fully hydrolyzed to the tetraformyl product. The mixture was cooled to room temperature, diluted with MeOH (500 mL, drop-wise) and slowly poured into 4 L of water. This mixture was filtered to obtained a rust-coloured solid which contained byproducts. The mixture was dissolved in THF (1.2 L) and added drop-wise to a mixture of MeOH/water (5 L, 1:1). The resulting yellow solid was collected by filtration (144 g as wet solid). The sample was further purified by dissolving in toluene and filtering through a celite plug. All pure material was eluted from the plug by subsequent elution with THF. The product was obtained as adducts of toluene and THF. Taking into account the mass of included solvent in the purified product the total mass obtained was 85 g. |
Yield | Reaction Conditions | Operation in experiment |
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50% | With trichlorophosphate; In 1,2-dichloro-ethane; at 0 - 70℃; for 3h;Inert atmosphere; | Example 3: 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. |
Yield | Reaction Conditions | Operation in experiment |
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93.5% | With copper(I) oxide; N,N,N,N,-tetramethylethylenediamine; at 200℃; for 4h;Large scale; | 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. |