* 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.
Reference:
[1] Journal of Physical Chemistry B, 1999, vol. 103, # 49, p. 10741 - 10745
2
[ 603-34-9 ]
[ 81090-53-1 ]
Yield
Reaction Conditions
Operation in experiment
99%
With N-Bromosuccinimide In ethyl acetate at 20℃; for 24 h;
Step 1: Synthesis of 4,4'-dibromotriphenylamine] [0479]A synthetic scheme of 4,4'-dibromotriphenylamine in Step 1 is shown in the following (K-I). [0480][0481]After 12 g (50 mmol) of triphenylamine was dissolved in a mixture solvent of 250 mL of ethyl acetate in a 500-mL conical flask, 18 g (100 mmol) of λT-bromo succinimide (abbreviation: NBS) was added to this solution. After that, this mixture was stirred at room temperature for 24 hours. After completion of the reaction, this mixture solution was washed with water, and magnesium sulfate was added thereto to remove moisture. This mixture solution was filtrated and the obtained filtrate was concentrated and dried to obtain 20 g of an objective white solid at a yield of 99 percent
99%
With N-Bromosuccinimide In ethyl acetate at 20℃; for 24 h;
After 12 g (50 mmol) of triphenylamine was dissolved in 250 mL of ethyl acetate in a 500-mL conical flask, 18 g (100 mmol) of iV-Bromosuccinimide (abbreviation: NBS) was added to this solution. After that, this mixture was stirred at room temperature for 24 hours to be reacted. After completion of the reaction, this mixture solution was washed with water, and magnesium sulfate was added thereto to remove moisture. This mixture solution was filtrated, and the obtained filtrate was concentrated and dried to obtain 20 g of an objective white solid at a yield of 99 percent. A synthesis scheme of Step 1 is shown in (b-4) given below.
Reference:
[1] Patent: WO2009/72587, 2009, A1, . Location in patent: Page/Page column 191
[2] Patent: WO2009/139358, 2009, A1, . Location in patent: Page/Page column 90
[3] Journal of Materials Chemistry C, 2016, vol. 4, # 13, p. 2579 - 2586
[4] Journal of Materials Chemistry C, 2016, vol. 4, # 43, p. 10301 - 10308
[5] Journal of Materials Chemistry, 2012, vol. 22, # 23, p. 11629 - 11635
[6] New Journal of Chemistry, 2016, vol. 40, # 11, p. 9725 - 9738
[7] RSC Advances, 2016, vol. 6, # 3, p. 2191 - 2201
[8] Journal of Materials Chemistry C, 2018, vol. 6, # 41, p. 11111 - 11117
[9] Journal of the American Chemical Society, 2016, vol. 138, # 34, p. 10742 - 10745
[10] Journal of Materials Chemistry, 2012, vol. 22, # 16, p. 7945 - 7953
[11] Physical Chemistry Chemical Physics, 2018, vol. 20, # 44, p. 28279 - 28286
[12] Journal of Physical Chemistry B, 1999, vol. 103, # 49, p. 10741 - 10745
[13] Patent: US2006/208235, 2006, A1, . Location in patent: Page/Page column 8-9
[14] Dyes and Pigments, 2014, vol. 106, p. 58 - 70
[15] Journal of the American Chemical Society, 2017, vol. 139, # 32, p. 11073 - 11080
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[ 589-87-7 ]
[ 62-53-3 ]
[ 81090-53-1 ]
Reference:
[1] RSC Advances, 2015, vol. 5, # 37, p. 28879 - 28884
[2] RSC Advances, 2014, vol. 4, # 32, p. 16385 - 16390
[3] New Journal of Chemistry, 2018, vol. 42, # 22, p. 18448 - 18457
[4] Journal of Organometallic Chemistry, 2009, vol. 694, # 12, p. 1818 - 1825
[5] Organic and Biomolecular Chemistry, 2016, vol. 14, # 10, p. 2961 - 2968
[6] Patent: WO2006/114921, 2006, A1, . Location in patent: Page/Page column 74-77
[7] Dyes and Pigments, 2014, vol. 104, p. 1 - 7
[8] Ultrasonics Sonochemistry, 2015, vol. 22, p. 365 - 370
4
[ 66-71-7 ]
[ 591-50-4 ]
[ 16292-17-4 ]
[ 81090-53-1 ]
Reference:
[1] Patent: US2006/83945, 2006, A1,
5
[ 16292-17-4 ]
[ 104-15-4 ]
[ 637-88-7 ]
[ 81090-53-1 ]
Reference:
[1] Patent: US6300502, 2001, B1,
6
[ 16292-17-4 ]
[ 637-88-7 ]
[ 81090-53-1 ]
Reference:
[1] Bulletin of the Chemical Society of Japan, 1986, vol. 59, # 3, p. 803 - 808
[2] RSC Advances, 2014, vol. 4, # 65, p. 34332 - 34342
7
[ 591-50-4 ]
[ 16292-17-4 ]
[ 81090-53-1 ]
Reference:
[1] Journal of Materials Chemistry B, 2017, vol. 5, # 43, p. 8525 - 8531
8
[ 4051-56-3 ]
[ 81090-53-1 ]
Reference:
[1] Bulletin of the Chemical Society of Japan, 1986, vol. 59, # 3, p. 803 - 808
9
[ 99234-92-1 ]
[ 81090-53-1 ]
Reference:
[1] Bulletin of the Chemical Society of Japan, 1986, vol. 59, # 3, p. 803 - 808
10
[ 603-35-0 ]
[ 81090-53-1 ]
Reference:
[1] New Journal of Chemistry, 2016, vol. 40, # 12, p. 10246 - 10258
With potassium hydroxide;copper(l) chloride; In toluene;
Example 10 4,4'-dibromotriphenylamine In an oxygen-free glovebox, a 250 mL flask was charged with 4,4'-dibromodiphenylamine (15.0 g, 45.8 mmol), iodobenzene (18.7 g, 91.7 mmol), 1,10-phenanthroline (0.827 g, 4.59 mmol), CuCl (0.454 g, 4.59 mmol), KOH (15.4 g, 275 mmol), and toluene (125 mL). The flask was sealed and removed from the glovebox and heated to 130 C. and stirred for 24 hr. The flask was then removed from the oil bath and allowed to cool to room temperature. The solids were filtered off and the solvent was removed to yield a bluish oily substance, which was passed through silica gel column using toluene as the eluant. The fractions were collected and the solvent was removed followed by vacuum distillation at 160 C. for 30 min to remove the remaining iodobenzene to afford a blue solid. This solid was further purified by a second silica plug column using hexanes as the eluant. The colorless clear fractions were combined and the solvent removed to yield the desired product. Purity: 99+%.
(4) Synthesis of 4,4'-dibromotriphenylamine Charged under Ar atmosphere were bromoiodobenzene 62.2 g, aniline 9.31 g, copper iodide 1.90 g, N,N'-dimethylethylenediamine 1.76 g, sodium t-butoxide 28.8 g and xylene 200 ml, and the mixture was refluxed for 24 hours under heating. After cooled down to room temperature, the mixture was extracted with toluene, and the insoluble matter was filtered. The filtrate was concentrated, and then the concentrate was refined by silica gel chromatography to obtain 20.1 g of a white solid matter of 4,4'-dibromotriphenylamine.
In a 100-mL three-neck flask, 6.0 g (15 mmol) of 4,4'-dibromotriphenylamine which was synthesised in Step 1, 5.2 g (30 mmol) of 1-naphthaleneboronic acid, 2.0 mg (0.01 mmol) of palladium(II) acetate, and 6.0 mg (0.02 mmol) of tri(o-tolyl)phosphine were put, and 20 mL of toluene, 5 mL of ethanol, and 20 mL of a potassium carbonate aqueous solution (2 mol/L) were added to this mixture. This mixture was deaerated while being stirred under low pressure. After the deaeration, the mixture was stirred under a nitrogen atmosphere at 90 C. for 4.5 hours to be reacted. After the reaction, 150 mL of toluene was added to this reaction mixture, and this suspension was filtrated through Florisil and then Celite. The obtained filtrate was washed with water, and magnesium sulfate was added thereto to remove moisture. This suspension was filtrated through Florisil, alumina, silica gel, and then Celite to obtain filtrate. The obtained filtrate was concentrated, methanol was added thereto, ultrasonic waves were applied thereto, and then recrystallization thereof was performed to obtain 6.4 g of an objective white solid at a yield of 86%. A synthetic scheme of Step 2 is shown in (c-4) given below. An Rf value of the objective substance by a silica gel thin layer chromatography (TLC) (developing solvent, ethyl acetate: hexane=1:10) was 0.53 and that of 4,4'-dibromotriphenylamine was 0.69. The molecular weight of the white solid which was obtained in Step 2 was measured by a TOF-MS detector (Waters Micromass LCT Premier, manufactured by Waters). A mixture solution containing acetonitrile and 0.1% of a formic acid solution (mixture rate of acetonitrile and the forminc acid solution, 80/20 vol/vol) was used as a solvent. Accordingly, a main peak with a molecular weight of 498.22 (mode is ES+) was detected and it was confirmed that objective alphaNBB1P was obtained.
5
[ 81090-53-1 ]
4-[N,N-bis(4-bromophenyl)amino]benzenesulfonic acid[ No CAS ]
7,12-diphenylbenzo[k]fluorantheno-3-boric acid[ No CAS ]
[ 81090-53-1 ]
C82H51N[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In 50 cm3 of dimethoxyethane were dissolved 2 g (4.5 mmol) of the boric acid prepared above and 0.56 g (1.4 mmol) of bis-p-dibromotriphenylamine. The solution was heated at 80C, to which 50 cm3 of distilled water and 10 g of sodium carbonate were admitted. Finally, 0.2 g of tetrakistriphenylphosphine palladium (0) was admitted to the solution. After 3 hours, the precipitated end compound was recovered. It was purified by silica gel chromatography, obtaining 1 g of yellow crystals. The compound thus obtained was identified by mass spectroscopy, infrared absorption spectroscopy and NMR. Mass spectrum m/e = 1050 (M+1)+
4,4'-dibromotriphenylamine: A mixture of 4,4'-dibromodiphenylamine (7.3 g. 22 mmol), cyclohexane-1,4-dione (2.5 g., 23.3 mole), para-toluenesulfonic acid (0.1 g.) and toluene (100 ml) was kept at reflux with a Dean-Stark phase separator containing 4A molecular sieves. After 18 hours at reflux, the reaction was diluted with toluene, and the toluene solution was washed with water, dried and concentrated. The residue was dissolved in hexanes, and the hexanes solution was passed through a column of silica gel to afford 4,4'-dibromotriphenylamine as a colorless glass, 5.04 g., 67% yield. Mass Spec (m/z): 401, 403, 405 (M+).
Bis(4-(7-benzothiazol-2-yl-9,9-diethylfluoren-2-yl)phenyl)phenylamine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
56%
With sodium carbonate;palladium; In ethanol;
Bis(4-(7-benzothiazol-2-yl-9,9-diethylfluoren-2-yl)phenyl)phenylamine: A mixture of 4,4'-dibromotriphenylamine (2.06 g., 5 mmol.), 9,9-diethyl-7-(2-benzothiazolyl)-2-fluorene boronic acid (6.24 g., 15.6 mmol.), ethanol (40 ml), and N-methyl-2-pyrrolidinone (100 ml) was heated under nitrogen to 120 C., and cooled. To the mixture, sodium carbonate (5.2 g., 50 mmol.) and 5% palladium on carbon (1.6 g.) were added and the reaction mixture was kept at 110 C. for 42 hours. The cooled reaction mixture was poured into 750 ml water, and the separated green solids containing the chromophore were collected. These were transferred to a column of alumina and eluted with heptane to obtain 2.65 g., 56% yield of the product, m.p. 256.7-261.9 C. Recrystallization from toluene-heptane (3:1) raised the m.p. to 259.6-263 C. Mass spec (m/z): 951 (M+). Anal. Calcd. for C66H53N3S2: C, 83.25; H, 5.61; N, 4.41; S, 6.72. Found: C, 83.10; H, 5.35; N, 4.24; S, 6.50.
With tert.-butyl lithium; In tetrahydrofuran; pentane; at -78 - 20℃; for 4h;
The synthetic route to amino-benzaldhyde (11) is presented in scheme V. 4,4'-dibromotriphenylamine was synthesized according to the method reported in Lee, H. J.; Sohn, J.; Hwang, J.; Park, S. Y.; Choi, H.; Cha, M. Chem. Mater. 2004, 16, 456. The solution containing 4,4'-dibromotriphenylamine (1.9 g, 4.7 mmol) and an excess of dry 1,6-dibromohexane (11.5 g, 47 mmol) in 50 mL of dry THF was cooled down to -78 C. 8.3 mL (3 eq.) of t-butyl lithium (in pentane, 1.7 M) was added dropwise and the reaction mixture was gradually allowed to reach room temperature for 4 hrs. The resulting solution was quenched with water, evaporated under reduced pressure, and extracted with methylene chloride. The organic phase was dried over magnesium sulfate and concentrated. Non-reacted 1,6-dibromohexane was removed by vacuum distillation and the pure bis[4-(6'-bromohexyl)phenyl]phenylamine was obtained by column chromatography (methylene chloride/hexane=1:10) in a colorless oil (1.7 g, 63%). The 100 mL flask containing 20 mL of dry DMF was cooled down to 0 C. Phosphorous oxychloride (0.75 g, 4.9 mmol) was added dropwise maintaining the temperature below 5 C. The reaction mixture was stirred for 30 min. 0.93 g (1.62 mmol) of bis[4-(6'-bromohexyl)phenyl]phenylamine in 10 mL of dry DMF was added to the above solution and the temperature was slowly increased to 90 C. After the solution was heated overnight, it was cooled down to room temperature and poured into cold water. The pH of the solution was adjusted to around 7 with aqueous NaOH solution. The product was extracted with methylene chloride, dried over magnesium sulfate, and purified by silica gel column chromatography (ethyl acetate/hexane=1:10). The product yield was 0.65 g (78%). 1H-NMR (200 MHz, CDCl3): delta 9.78 (s, 1H, -CHO), 7.65 (d, 2H, J=8.8 Hz), 7.15 (d, 4H, J=8.6 Hz), 7.08 (d, 4H, J=8.8 Hz), 6.95 (d, 2H, J=8.8 Hz), 3.55 (t, 4H, -CH2Cl, J=6.7 Hz), 2.61 (t, 4H, ArCH2-, J=7.7 Hz), 1.80 (m, 4H), 1.65 (m, 4H), 1.44 (m, 8H). 13C-NMR (100 MHz, CDCl3): delta 190.5, 131.5, 129.8, 126.5, 126.2, 118.4, 45.3, 35.5, 32.7, 31.4, 28.7, 26.9. HRMS (EI): m/z=509.2253 (M+), Delta=0.1 ppm.
With copper(l) iodide; 1,10-Phenanthroline; sodium t-butanolate; In toluene; at 115℃; for 18h;Inert atmosphere;
1-bromo-4-iodobenzene (41.7g, 0.148mol) and aniline (5.5g, 0.059mol) were dissolved in 100mLTo anhydrous toluene, then add sodium tert-butoxide (22.7g, 0.236mol), CuI (2.3g, 0.012mol) and 1,10-phenanthroline (4.3g, 0.023mol),Heat to 115 C under a nitrogen atmosphere for 18 hours, and then cool to concentrate and remove toluene.Deionized water and dichloromethane were added for extraction, and the organic layer obtained after separation was dried over anhydrous magnesium sulfate, suction filtered, and distilled under reduced pressure, and then purified by column chromatography using petroleum ether as a developing agent to obtain a thick paste product,The yield is about 85% (20.2 g);
With copper(I) iodide; 1,7-phenanthroline; potassium hydroxide; In toluene;Inert atmosphere; Reflux;
General procedure: In a two-necked flask a mixture of aniline (3mmol), iodobenzene (7.5mmol), CuI nanoparticles (3%mol), 1,10-phenanthroline (3%mol), potassium hydroxide (1.29g, 0.024mmol) and 20mL of toluene was stirred under nitrogen atmosphere at reflux for a suitable time. The completion of the reaction was monitored by TLC with hexane as the eluent. At the end of reaction, the mixture was then cooled to room temperature and poured into distilled water. The products were extracted by CH2Cl2 and the organic layer was dried over anhydrous sodium sulfate (Na2SO4). Then the solvent was evaporated in vacuo, the products were purified by silica column chromatography using normal hexane as an eluent.
With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 90℃; for 4.5h;
Step 1: Synthesis of 4,4'-di(2-naphthyl)-triphenylamine][0776]A synthetic scheme of 4,4'-di(2-naphthyl)-triphenylamine in Step 1 is shown in the following (U-I). [0777] <n="256"/>[0778] in a 300-mL three-neck flask, 6.0 g (15 mmol) of 4,4'-dibromotriphenylamine, 6.2g (36 mmol) of 2-naphthaleneboronic acid, 16 mg (0.1 mmol) of palladium(II) acetate, and 21 mg (0.1 mmol) of tri(o-tolyl)phosphine were put, and 50 mL of toluene, 20 mL of ethanol, and 20 mL of a potassium carbonate solution (2 mol/L) were added to this mixture. This mixture was deaerated while being stirred under low pressure. After the deaeration, the mixture was stirred under a nitrogen atmosphere at 90 0C for4.5 hours to be reacted. [0779]After the reaction, 150 mL of toluene was added to this reaction mixture, and this suspension was filtrated through Florisil, silica gel, and then Celite. The obtained filtrate was washed with water. Then, magnesium sulfate was added to remove moisture. This suspension was filtrated through Florisil, alumina, silica gel, and then Celite to obtain filtrate. The obtained filtrate was concentrated, and hexane was added thereto. The mixture was irradiated with supersonic and then recrystallized to obtain5.6 g of an objective white powder at a yield of 75 %.
75%
With potassium carbonate; tris-(o-tolyl)phosphine;palladium diacetate; In ethanol; water; toluene; at 90℃; for 4.5h;Inert atmosphere;
In a 300-mL three-neck flask, 6.0 g (15 mmol) of 4,4'-dibromotriphenylamine which was synthesized in Step 1, 6.2g (36 mmol) of 2-naphthaleneboronic acid, 16 mg(0.1 mmol) of palladium(II) acetate, and 21 mg (0.1 mmol) of tri(°-tolyl)phosphine were put, and 50 mL of toluene, 20 mL of ethanol, and 20 mL of a potassium carbonate <n="97"/>aqueous solution (2 mol/L) were added to this mixture. This mixture was deaerated while being stirred under low pressure. After the deaeration, the mixture was stirred under a nitrogen atmosphere at 90 0C for 4.5 hours to be reacted. After the reaction, 150 mL of toluene was added to this reaction mixture, and this suspension was filtrated through Florisil, silica gel, and then Celite. The obtained filtrate was washed with water, and magnesium sulfate was added thereto to remove moisture. This suspension was filtrated through Florisil, alumina, silica gel, and then Celite to obtain filtrate. The obtained filtrate was concentrated, hexane was added thereto, ultrasonic waves were applied thereto, and then recrystallization thereof was performed to obtain 5.6 g of an objective white powder at a yield of 75 %. A synthetic scheme of Step 2 is shown in (c-6) given below. [0265] [0266] An Rf value of the objective substance by a silica gel thin layer chromatography (TLC) (developing solvent, ethyl acetate: hexane = 1:10) was 0.53 and that of 4,4'-dibromotriphenylamme was 0.78. [0267]The molecular weight of the white powder which was obtained in Step 2 was measured by a TOF-MS detector (Waters Micromass LCT Premier, manufactured by Waters). A mixture solution containing acetonitrile and 0.1 % of a formic acid solution (mixture rate of acetonitrile and the forminc acid solution, 80/20 vol/vol) was used as a solvent. Accordingly, a main peak with a molecular weight of 498.22 (mode is ES+) was detected and it was confirmed that objective betaNBBlP was obtained.
75%
With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; sodium hydroxide; In water; toluene; at 80℃; for 12h;Inert atmosphere;
Intermediate 17 synthesis: under the environment of nitrogen, will (20.2 g, 50 mmol) of compound 15 and (17.2 g, 100 mmol) of compound 16, (3.5 g, 3 mmol) four (triphenyl phosphate) palladium, (8.1 g, 25 mmol) tetrabutyl ammonium bromide, (4 g, 100 mmol) sodium hydroxide, (20 ml) and water (150 ml) toluene by adding 300 ml three-opening in the bottle, heating 80 C stirring for 12 hours, the end of the reaction, the reaction liquid rotary evaporate most of the solvent, dichloromethane is used for dissolving water washing 3 times, to collect organic the fluid mixes silica gel column purification, yield 75%.
75%
With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; sodium hydroxide; In water; toluene; at 80℃; for 12h;Inert atmosphere;
Under a nitrogen atmosphere, (20.2 g, 50 mmol) of compound 20 and (17.2 g, 100 mmol) of compound 21, (3.5 g, 3 mmol) tetrakis(triphenylphosphonium)palladium, (8.1 g, 25 mmol) tetrabutylammonium bromide, (4g, 100mmol) sodium hydroxide, (20mL) water and (150mL) toluene were added to a 300mL three-necked flask, heated at 80 C with stirring for 12 hours, and the reaction was ended. Part of the solvent was washed 3 times with dichloromethane and washed with water. The organic liquid was collected and purified by passing through a column with silica gel. The yield was 75%.
With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 90℃; for 4.5h;
Step 2: Synthesis of 4,4'-di(l-naphthyl)triphenylamine] [0483]A synthetic scheme of 4,4'-di(l-naphthyl)triphenylamine in Step 2 is shown in the following (K-2). [0484][0485] <n="193"/>In a 100-mL three-neck flask, 6.0 g (15 mmol) of 4,4'-dibromotriphenylamine,5.2 g (30 mmol) of 1-naphthaleneboronic acid, 2.0 mg (0.01 mmol) of palladium(II) acetate, and 6.0 mg (0.02 mmol) of tri(o-tolyl)phosphine were put, and 20 mL of toluene, 5 mL of ethanol, and 20 mL of a potassium carbonate solution (2 mol/L) were added to this mixture. This mixture was deaerated while being stirred under low pressure. After the deaeration, the mixture was stirred under a nitrogen atmosphere at90 0C for 4.5 hours to be reacted.[0486]After the reaction, 150 mL of toluene was added to this reaction mixture, and on this suspension was filtrated through Florisil and then Celite. The obtained filtrate was washed with water. Then, magnesium sulfate was added to remove moisture.This suspension was filtrated through Florisil, alumina, silica gel, and then Celite to obtain filtrate. The obtained filtrate was concentrated, and methanol was added thereto.The mixture was irradiated with supersonic and then recrystallized to obtain 6.4 g of an objective white powder at a yield of 86 %.
86%
With potassium carbonate; tris-(o-tolyl)phosphine;palladium diacetate; In water; toluene; at 90℃; for 4.5h;Inert atmosphere;
In a 100-mL three-neck flask, 6.0 g (15 mmol) of 4,4'-dibromotriphenylamine which was synthesized in Step 1, 5.2 g (30 mmol) of 1-naphthaleneboronic acid, 2.0 mg (0.01 mmol) of palladium(II) acetate, and 6.0 mg (0.02 mmol) of tri(o-tolyl)phosphine were put, and 20 mL of toluene, 5 mL of ethanol, and 20 mL of a potassium carbonate aqueous solution (2 mol/L) were added to this mixture. This mixture was deaerated while being stirred under low pressure. After the deaeration, the mixture was stirred under a nitrogen atmosphere at 90 0C for 4.5 hours to be reacted. After the reaction, 150 mL of toluene was added to this reaction mixture, and this suspension was filtrated through Florisil and then Celite. The obtained filtrate was washed with water, and magnesium sulfate was added thereto to remove moisture. This suspension was filtrated through Florisil, alumina, silica gel, and then Celite to obtain filtrate. The obtained filtrate was concentrated, methanol was added thereto, ultrasonic waves were applied thereto, and then recrystallization thereof was performed to obtain 6.4 g of an objective white solid at a yield of 86 %. A synthetic scheme of Step 2 is shown in (c-4) given below. [0246] [0247]An Rf value of the objective substance by a silica gel thin layer chromatography (TLC) (developing solvent, ethyl acetate: hexane = 1:10) was 0.53 and that of 4,4'-dibromotriphenylamine was 0.69. [0248]The molecular weight of the white solid which was obtained in Step 2 was measured by a TOF-MS detector (Waters Micromass LCT Premier, manufactured by Waters). A mixture solution containing acetonitrile and 0.1 % of a formic acid solution <n="93"/>(mixture rate of acetonitrile and the forminc acid solution, 80/20 vol/vol) was used as a solvent. Accordingly, a main peak with a molecular weight of 498.22 (mode is ES+) was detected and it was confirmed that objective alphaNBBlP was obtained.
With potassium iodate; potassium iodide; In acetic acid;Inert atmosphere; Reflux;
General procedure: A 5mL acetic acid solution of triarylamine (3a-c) (2.0mmol), potassium iodide (0.34g, 2.1mmol) and potassium iodate (0.62g, 3.08mmol) in a two-necked round bottom flask was stirred in 3-5h under nitrogen atmosphere at reflux. After the completion of the reaction (followed by TLC), the mixture was cooled to room temperature and poured into 50mL of distilled water. The precipitate was filtered and dissolved in dichloromethane, then washed with aqueous Na2S2O3 and dried over anhydrous Na2SO4. The residue after evaporation of the solvent, was recrystallized in acetone and obtained pure iodo phenyl diarylamine (4a-c).
With tetrakis(triphenylphosphine) palladium(0); lithium tert-butoxide; In 1,4-dioxane; at 120℃; for 21h;Sealed tube;
Preparation of compound 5bPy [0114] A mixture of bis-bromotriphenylamine 3b (426 mg, 1 mmol, 1 equiv.), 5-pyridyloxazole (386 mg, 2.6 mmol, 2.5 equiv.), lithium tert-butoxide (338 mg, 4.2 mmol, 4 equiv.), tetrakis(triphenylphosphine)palladium(0) (122 mg, 0.1 mmol, 0.10 equiv.) in dry dioxane (10 mL) was stirred for 21 h at 120C in a sealed tube. Ethyl acetate and water were added. After decantation, the resulting organic layer was washed with brine, dried over MgSO4, filtered and concentrated to dryness. The crude residue was purified by column chromatography (dichloromethane/methanol = 100/0 to 90/10), dissolved in a minimal amount of dichloromethane and precipitated with a small quantity of diethyl ether and a large quantity of pentane to afford the desired compound 5bPy in 26 % yield (147 mg, 0.27 mmol) as a bright yellow solid. 1H NMR (300 MHz, CDCl3) delta 8.66 (d, J = 5. 4, 4H), 8. 00 (d, J = 8.7, 4H), 7.63 (s, 2H), 7.54 (d, J = 5.4, 4H), 7.41 - 7.30 (m, 2H), 7.25 - 7.13 (m, 7H) 13C NMR (75 MHz, CDCl3) delta 162.6, 150.5, 149.6, 148.4, 146.3, 135.1, 130.0, 128.0, 127.2, 126.3, 125.3, 123.5, 121.2, 118.0 MS (ES+) m/z 534.2
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,2-dimethoxyethane; water; for 20h;Inert atmosphere; Reflux;
To a mixture of 4,4'-dibromotriphenylamine (5.0 g; 0.0124 mole), 1- thianthrenylboronic acid (7.1 g; 0.0273 mole), tetrakis(triphenyl phosphine) palladium (1.4 g; 0.0012 mole) in ethyleneglycoldimethyl ether (60 ml) was added potassium carbonate (17.2 g; 0.124 mole) in water (40 ml). The reaction mixture was magnetically stirred and refluxed under a nitrogen atmosphere for 20 hours, allowed to cool and the solvent was removed under reduced pressure. The residue was dissolved in dichloromethane and extracted with water. The organic phase was dried over anhydrous magnesium sulphate and solvent removed to give a light green residue which was again dissolved in dichloromethane, adsorbed onto silica gel and then subjected to flash column chromatography over silica gel eluting with dichloromethane. The fractions containing the product were collected together and solvent removed using a rotary evaporator to give a residue which was triturated with methanol and addition of small amounts of petroleum ether. Cooling in an ice water bath gave a pale yellow solid which was dried under vacuum at 80C, yield 7.4g (88 %). It was further purified twice by sublimation to give a light yellow glassy solid, 2.4 g (33 %), showing light bluish fluorescence under UV. DSC did not show any melting peak, but it showed a Tg at 122 C. Found: C 74.76, H 4.12, N 2.03, S 19.04 %. C42H27NS4, requires C 74.85, H 4.04, N 2.08, S 19.03 %. UV: max(CH2Cl2)/nm (epsilon/dm3 mol"1 cm"1) 328 (37,515) 261(68,620) and 232(sh)(40,368). ^(Thin film)/nm: 336, 266 and 199 nm. Optical band gap:3.24 eV. FL: max/nm(CH2Cl2)em: 418; ex/nm: 330; maX/nm(Powder)em: 419, ex/nm: 330; Xmax /nm(Thin film)em: 409, ex/nm: 330. TGA/ C (% weight loss): 420 (1) and 466(5).
5,5’-(4,4’-(phenylazanediyl)bis(4,1-phenylene))dithiophene-2-carbaldehyde[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
56%
With potassium phosphate; palladium diacetate; XPhos; In tetrahydrofuran; water; at 60℃; for 24h;
A mixture of compound 1 (<strong>[81090-53-1]4-bromo-N-(4-bromophenyl)-N-phenylaniline</strong>) (347 mg, 0.86 mmol),5-formyl-2-thiophene-boronic acid (322 mg, 2.06 mmol), Pd(OAc)2 (9.3 mg, 0.04 mmol), x-phos (23.6 mg,0.05 mmol), and K3PO4 (1.49 g, 7.0 mmol) in THF (12 mL) and H2O (4 mL) were stirred at 60C for 24 h.After cooled to room temperature, the reaction mixture was poured into saturated NH4Cl solution, and thenextracted with CH2Cl2. The combined organic phases were washed with water and brine, and dried overanhydrous sodium sulfate. The crude product was purified by column chromatography on silica gel usingCH2Cl2/hexane (4:1, v/v) as eluent to give a yellow powder (225 mg, 56 %).
With tetrakis(triphenylphosphine) palladium(0); sodium t-butanolate; In 2-methoxy-ethanol; for 20h;Reflux; Inert atmosphere;
(a) To a slurry of 4,4'-dibromotriphenylamine (5.3 g; 0.013 mole) in 2- methoxyethanol (50 ml) was added tetrakis(triphenylphosphine) palladium (0.76 g; 0.00066 mole) followed by 1-thianthrenylboronic acid (3.42g; 0.013 mole) in 2- methoxy ethanol(30 ml). Then sodium tert-butoxide (2.4 g; 0.025 mole) was added followed by 2-methoxy ethanol (20 ml). The reaction mixture was refluxed under nitrogen for 20 hrs. The solution at the beginning became homogeneous then cloudy finally dark green in colour. The solvent removed under reduced pressure using the rotary evaporator and the residue extracted with dichloromethane. The dichloromethane solution was washed with brine and water then dried over anhydrous magnesium sulphate. The solvent after filtration of magnesium sulphate was evaporated in a rotary evaporator to give dark green solid. The solid was purified by column chromatography using petroleum ether- dichloromethane (3:2) to give a colourless solid, 3.4 g (48 %).
4,4'-bis(4-n-hexyloxyphenyl)triphenylamine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
90%
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium carbonate; In tetrahydrofuran; for 24h;Reflux;
In a round bottom flask, 6.0 g (14.9 mmol) dibromo-triphenylamine, 8.9 g (38.2 mmol) <strong>[121219-08-7]4-n-hexyloxybenzeneboronic acid</strong> and 0.2 g (0.25mmol) dichloro-bis(diphenylphosphino) ferrocene palladium (II) was combined in 50 ml. THF and 30 ml. 10% Na2C03. The batch was held at reflux for 24 h and HPLC showed complete reaction. Mixture was poured into a beaker with 300 ml. water and the product was filtered off, washed with water, and dried. Crude product was dissolved in methylene chloride then passed through a plug of silica gel and washed through with dichloromethane. The solvent was removed and replaced with acetonitrile. (0120) The resulting solid was filtered off, washed with acetonitrile and dried, yielding 8 g tan solid (90% yield). UV/Vis max 325nm, LCMS m/z = 598.4