Abstract: NIR dyes have become popular for many applications, including biosensing and imaging. For this reason, the mol. switch mechanism of the xanthene dyes makes them useful for in vivo detection and imaging of bioanalytes. Our group has been designing NIR xanthene-based dyes by the donor-acceptor-donor approach; however, the equilibrium between their opened and closed forms varies depending on the donors and spacer. We synthesized donor-acceptor-donor NIR xanthene-based dyes with an alkyne spacer via the Sonogashira coupling reaction to investigate the effects of the alkyne spacer and the donors on the maximum absorption wavelength and the mol. switching (ring opening) process of the dyes. We evaluated the strength and nature of the donors and the presence and absence of the alkyne spacer on the properties of the dyes. It was shown that the alkyne spacer extended the conjugation of the dyes, leading to absorption wavelengths of longer values compared with the dyes without the alkyne group. In addition, strong charge transfer donors shifted the absorption wavelength towards the NIR region, while donors with strong π-donation resulted in xanthene dyes with a smaller equilibrium constant DFT/TDDFT calculations corroborated the exptl. data in most of the cases. Dye 2 containing the N,N-dimethylaniline group gave contrary results and is being further investigated.
* 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.
With tetrabutyl ammonium fluoride In tetrahydrofuran at 20℃; for 5 h;
1.0 g (2.93 mmol) of Intermediate 6(1) was dissolved in 10.0 mL of THF, and 14.64 mL (14.64 mmol) of a 1.0 M tetrabutylammonium fluoride solution in THF was gradually added thereto at room temperature, and then the mixture was stirred at room temperature for 5 hours. After the reaction was terminated, 50 mL of distilled water was added thereto, and the resultant was subjected to extraction three times with 50 mL of methylene chloride to obtain an organic layer. The organic layer was collected and dried with magnesium sulfate to evaporate the solvent. The residue was separately purified using silica gel column chromatography to obtain 730 mg (2.78 mmol) of Intermediate 6(2) (Yield: 93percent). The produced compound was identified using LC-MS. [0137] C20H15N: M+270.12
93%
With tetrabutyl ammonium fluoride In tetrahydrofuran at 20℃; for 5 h;
B. Synthesis of Intermediate 6(2)[0129] 1.0 g (2.93 mmol) of Intermediate 6(1) was dissolved in 10.0 mL of THF, and 14.64 mL (14.64 mmol) of a 1.0M tetrabutylammonium fluoride solution in THF was gradually added thereto at room temperature, and then the mixturewas stirred at room temperature for 5 hours. After the reaction was terminated, 50 mL of distilled water was addedthereto, and the resultant was subjected to extraction three times with 50 mL of methylene chloride to obtain an organiclayer. The organic layer was collected and dried with magnesium sulfate to evaporate the solvent. The residue wasseparately purified using silica gel column chromatography to obtain 730 mg (2.78 mmol) of Intermediate 6(2) (Yield:93 percent). The produced compound was identified using LC-MS.C20H15N : M+ 270.12
93%
With potassium carbonate In methanol; dichloromethane at 20℃; for 3 h; Inert atmosphere
To a mixture of 4-bromotriphenylamine (0.401 g, 1.24 mmol), PdCl2(PPh3)2 (42.1 mg, 0.06 mmol) and CuI (9.5 mg, 0.05 mmol) was dissolved in toluene (10 mL) by stirring with a magnetic bar in a sealed tube. 1,8-Diazabicycloundec-7-ene (DBU 2.0 mL) was added, followed by trimethylsilyl acetylene (1.6 mL, 1.5 g, 15 mmol) under N2 atmosphere. The reaction mixture was stirred at 70 °C. After 3 h, the reaction mixture was then filtered and the solid was washed with EtOAc (3 x 15 mL) and the filtrate was evaporated under reduced pressure. The residue was dissolved in a minimal amount of dichloromethane and eluted through a silica gel column with hexane to afford the desired product after solvent removal as light yellow oil (0.398 g, 94percent yield); δH (400 MHz, CDCl3) 7.32-7.24 (6H, m, Ph), 7.09-7.05 (6H, m, Ph), 6.95 (2H, d, J 8.0 Hz, Ph), 0.24 (9H, s, Si-Me). Next, the TMS protect compound (0.395 g,1.16 mmol) and K2CO3 (2.013 g) were dissolved in dichloromethane(15 mL) and methanol (15 mL) under N2 gas by stirring with a magnetic bar in a round-bottom flask at room temperature for 3 h. Then, the reaction was filtered and the solid was washed with dichloromethane (15 mL) and the filtrate was evaporated under reduced pressure. The residue was dissolved in a minimal amount of dichloromethane and eluted through a silica gel column with gradient solvents starting from pure hexane to hexane/dichloromethane (4/1) to afford the desired product after solvent removal (0.290 mg, 93percent yield) as a brown solid, m.p. 112-113 C; δH (400 MHz, CDCl3) 7.33 (2H, d, J 8.0 Hz, Ph), 7.26-7.29 (4H, m,Ph), 7.11-7.04 (6H, m, Ph), 6.96 (2H, d, J 8.0 Hz, Ph), 3.02 (1H, s, Csp-H).
91%
With tetrabutyl-ammonium chloride In tetrahydrofuran for 0.5 h;
8 g of Intermediate 1-a was dissolved in 100 ml of THF,And 60 ml of tetrabutylammonium chloride in THF was added dropwise thereto(1.0 M) solution and stirred for about 30 minutes.100 ml of water was added to the reaction solution, and the resultant was extracted three times with 100 ml of ether each time. The organic layer was collected and dried over magnesium sulfate and the solvent was evaporated. The residue was separated and purified by silica gel column chromatography to obtain 5.6 g (91percent yield) of Intermediate 1-b.
86%
With potassium carbonate In methanol at 20℃; for 3 h;
General procedure: 9-[4-{2-(Trimethylsilyl)ethynyl}phenyl]carbazole (4a, 0.68g, 2.7mmol), potassium carbonate (0.42g, 3.0mmol), and methanol (4.0mL) were placed in a flask, and the suspension was stirred at room temperature. After stirring for 3h, the precipitate that was insoluble in the solvent was separated by atmospheric filtration, and the filtrate was poured into saturated aqueous NH4Cl solution (20mL). The crude product was extracted with AcOEt (20mL) three times and the combined organic layer was washed with brine (once). The organic layer was collected and dried over anhydrous Na2SO4, which was separated by filtration. The filtrate was evaporated in vacuo and subjected to silica-gel column chromatography (eluent: hexane/CH2Cl2=5/1) to obtain the deprotection product 5a in 99percent yield (0.53g, 2.0mmol) as a white solid.
78%
With methanol; potassium hydroxide In tetrahydrofuran at 20℃; for 1 h;
A solution of KOH / MeOH (0.164 g / 2 ml) was added to a THF solution prepared by dissolving N, N-diphenyl-4 - [(trimethylsilyl) ethynyl] aniline (1 g, 2.94 mmol) The mixture was slowly added using a dropping funnel and stirred at room temperature for 1 hour. The solvent was concentrated under reduced pressure to obtain a black solid product, N, N-diphenyl-4-ethynylaniline (0.65 g, yield: 78percent).
0.5 g
With methanol; sodium hydroxide In tetrahydrofuran at 25℃; for 2 h;
A 100 mL three-necked round bottomed flask, equipped with a magnetic stir bar and condenser, was charged with ligand (4-bromophenyl)diphenylamine (leftmost compound of the above scheme) (1 g, 3.08mmol), trimethylsilylacetylene (0.6mL, 4.62mmol), bis(triphenylphosphine) palladium dichloride (0.1 1 g, 0.3mmol), copper iodide (0.03g, 0.15mmol) and 40 mL of degassed THF/triethylamine (v:v= 3: 1 ). The mixture was stirred at 80°C for 20 hours, and then concentrated under reduced pressure. The product was dissolved in dichloromethane solvent. The hydrophobic solvent solution was then sequentially washed with saturated ammonium chloride solution, brine and water. The combined hydrophobic phase was dried over MgS04 and filtered through a filter paper. The product was then purified using flash chromatography through silica using 4percent ethyl acetate in hexane as eluent. After removal of eluent solvent under reduced pressure, the resulting white solid was dissolved in 10 mL of tetrahydrofuran solvent and treated with sodium hydroxide in methanol (20 mL of a 2.0 M solution). After stirring for 2 hour, the resulting mixture was concentrated under reduced pressure. After extraction with dichloromethane, the hydrophobic solution was dried over MgS04, filtered and the solvent was removed under reduced pressure to give the product (4-ethynylphenyl)diphenylamine ("Ph2NPhCCH") (middle compound of Scheme for Example 2) as a white solid (0.5g, 60percent). Yield 60percent.
Reference：
[1] Tetrahedron Letters, 2010, vol. 51, # 6, p. 917 - 920
[2] Tetrahedron, 2010, vol. 66, # 29, p. 5479 - 5485
[3] RSC Advances, 2013, vol. 3, # 39, p. 17914 - 17917
[4] Organic Letters, 2012, vol. 14, # 15, p. 3970 - 3973
[5] Patent: US2013/292653, 2013, A1, . Location in patent: Paragraph 0136-0137
[6] Patent: EP2666768, 2013, A2, . Location in patent: Paragraph 0127; 0129
[7] Tetrahedron, 2017, vol. 73, # 17, p. 2483 - 2487
[8] Patent: CN103570742, 2018, B, . Location in patent: Paragraph 0221-0224; 0227; 0228
[9] Journal of Materials Chemistry A, 2015, vol. 3, # 21, p. 11607 - 11614
[10] Journal of Fluorine Chemistry, 2017, vol. 202, p. 54 - 64
[11] Journal of Materials Chemistry, 2012, vol. 22, # 12, p. 5319 - 5329
[12] Heteroatom Chemistry, 2016, vol. 27, # 5, p. 306 - 315
[13] Patent: KR101521483, 2015, B1, . Location in patent: Paragraph 0079-0081
[14] European Journal of Inorganic Chemistry, 2010, # 29, p. 4683 - 4696
[15] Patent: EP1170273, 2002, A1, . Location in patent: Page 10
[16] Journal of Organic Chemistry, 2005, vol. 70, # 4, p. 1134 - 1146
[17] Bulletin of the Korean Chemical Society, 2014, vol. 35, # 4, p. 1247 - 1250
[18] Chemical Communications, 2014, vol. 50, # 71, p. 10251 - 10254
[19] Patent: WO2014/138912, 2014, A1, . Location in patent: Page/Page column 43; 44
[20] Chinese Journal of Chemistry, 2018, vol. 36, # 2, p. 134 - 138
2
[ 4181-05-9 ]
[ 1034-49-7 ]
[ 205877-26-5 ]
Yield
Reaction Conditions
Operation in experiment
77%
Stage #1: With potassium <i>tert</i>-butylate In tetrahydrofuran at -78℃; for 2 h; Inert atmosphere Stage #2: at -78 - 20℃; for 21 h; Inert atmosphere
t-BuOK (4 equiv) was allowed to dissolve in dried THF (2 ml/mmol) under argon and the solution was cooled to 78 C. After 20 min, 1.6 equiv of (bromomethyl)triphenylphosphonium bromide was added portionwise and stirring under argon continued for 2 h. Then a solution of aldehyde 8 (2.47 mmol) or 9 (0.74 mmol) in dried THF (2 ml/mmol) was slowly added dropwise and stirring continued for 1 h at 78 C and 20 h at rt. The solution was mixed with the same volume of NH4Cl (aq), acidified with 2 M HCl (aq) and extracted with ethyl acetate (350 ml). The organic layer was dried over Na2SO4, filtered and the solvent was evaporated in vacuo. Purification of the residue by chromatography on a SiO2 column (20percent CHCl3 in hexanes) gave the title compound 7a (510 mg), 77percent, (yellow solid) or 7b (80 mg, 41percent, light-yellow crystalline solid; after chromatography the semi-solid oil was dissolved in hot hexanes, the solution was allowed to reach RT, filtered and concentrated under vacuum).
Reference：
[1] Tetrahedron, 2016, vol. 72, # 44, p. 7081 - 7092
[2] Journal of Organic Chemistry, 2010, vol. 75, # 9, p. 3053 - 3068
[3] Journal of Organic Chemistry, 2011, vol. 76, # 21, p. 8726 - 8736
3
[ 1223510-91-5 ]
[ 205877-26-5 ]
Reference：
[1] Journal of Organic Chemistry, 2010, vol. 75, # 21, p. 7273 - 7278
[2] European Journal of Inorganic Chemistry, 2012, # 1, p. 65 - 75
[3] Journal of Organic Chemistry, 2010, vol. 75, # 9, p. 3053 - 3068
4
[ 36809-26-4 ]
[ 205877-26-5 ]
Reference：
[1] Journal of Organic Chemistry, 2005, vol. 70, # 4, p. 1134 - 1146
[2] European Journal of Inorganic Chemistry, 2010, # 29, p. 4683 - 4696
[3] Organic Letters, 2012, vol. 14, # 15, p. 3970 - 3973
[4] Journal of Materials Chemistry A, 2013, vol. 1, # 23, p. 6949 - 6960
[5] Patent: US2013/292653, 2013, A1,
[6] Patent: EP2666768, 2013, A2,
[7] Inorganic Chemistry, 2014, vol. 53, # 14, p. 7188 - 7196
[8] Patent: WO2014/138912, 2014, A1,
[9] Journal of Materials Chemistry C, 2015, vol. 3, # 9, p. 2016 - 2023
[10] Journal of Materials Chemistry A, 2015, vol. 3, # 21, p. 11607 - 11614
[11] Heteroatom Chemistry, 2016, vol. 27, # 5, p. 306 - 315
[12] Tetrahedron, 2017, vol. 73, # 17, p. 2483 - 2487
[13] Journal of Fluorine Chemistry, 2017, vol. 202, p. 54 - 64
[14] Patent: CN103570742, 2018, B,
5
[ 36809-26-4 ]
[ 1066-54-2 ]
[ 205877-26-5 ]
Reference：
[1] Advanced Functional Materials, 2014, vol. 24, # 46, p. 7257 - 7271
[2] European Journal of Organic Chemistry, 2009, # 32, p. 5587 - 5593
[3] Journal of Materials Chemistry, 2012, vol. 22, # 33, p. 16781 - 16790
6
[ 1440427-03-1 ]
[ 205877-26-5 ]
Reference：
[1] Journal of Materials Chemistry A, 2013, vol. 1, # 23, p. 6949 - 6960
7
[ 4181-05-9 ]
[ 90965-06-3 ]
[ 205877-26-5 ]
Reference：
[1] New Journal of Chemistry, 2015, vol. 39, # 12, p. 9700 - 9713
[2] Synlett, 2009, # 18, p. 2977 - 2981
8
[ 247145-25-1 ]
[ 205877-26-5 ]
Reference：
[1] Inorganic Chemistry, 2014, vol. 53, # 14, p. 7188 - 7196
[2] Journal of Physical Chemistry A, 2010, vol. 114, # 13, p. 4542 - 4549
[3] Tetrahedron, 2010, vol. 66, # 51, p. 9641 - 9649
[4] Journal of Materials Chemistry C, 2015, vol. 3, # 9, p. 2016 - 2023
9
[ 122-39-4 ]
[ 205877-26-5 ]
Reference：
[1] Dalton Transactions, 2006, # 30, p. 3693 - 3698
[2] Journal of Organic Chemistry, 2005, vol. 70, # 4, p. 1134 - 1146
10
[ 603-34-9 ]
[ 205877-26-5 ]
Reference：
[1] European Journal of Inorganic Chemistry, 2010, # 29, p. 4683 - 4696
[2] Journal of Organic Chemistry, 2011, vol. 76, # 21, p. 8726 - 8736
[3] Chemical Communications, 2014, vol. 50, # 71, p. 10251 - 10254
[4] Journal of Materials Chemistry C, 2015, vol. 3, # 9, p. 2016 - 2023
[5] New Journal of Chemistry, 2015, vol. 39, # 12, p. 9700 - 9713
11
[ 38257-52-2 ]
[ 205877-26-5 ]
Reference：
[1] RSC Advances, 2013, vol. 3, # 39, p. 17914 - 17917
[2] Bulletin of the Korean Chemical Society, 2014, vol. 35, # 4, p. 1247 - 1250
[3] Chemical Communications, 2014, vol. 50, # 71, p. 10251 - 10254
[4] Patent: KR101521483, 2015, B1,
12
[ 38257-52-2 ]
[ 1066-54-2 ]
[ 205877-26-5 ]
Reference：
[1] Molecular Crystals and Liquid Crystals Science and Technology, Section A: Molecular Crystals and Liquid Crystals, 2001, vol. 370, p. 207 - 210
[2] Dyes and Pigments, 2017, vol. 140, p. 203 - 211
With tetrabutyl ammonium fluoride; In tetrahydrofuran; at 20℃; for 5h;
1.0 g (2.93 mmol) of Intermediate 6(1) was dissolved in 10.0 mL of THF, and 14.64 mL (14.64 mmol) of a 1.0 M tetrabutylammonium fluoride solution in THF was gradually added thereto at room temperature, and then the mixture was stirred at room temperature for 5 hours. After the reaction was terminated, 50 mL of distilled water was added thereto, and the resultant was subjected to extraction three times with 50 mL of methylene chloride to obtain an organic layer. The organic layer was collected and dried with magnesium sulfate to evaporate the solvent. The residue was separately purified using silica gel column chromatography to obtain 730 mg (2.78 mmol) of Intermediate 6(2) (Yield: 93%). The produced compound was identified using LC-MS. [0137] C20H15N: M+270.12
93%
With tetrabutyl ammonium fluoride; In tetrahydrofuran; at 20℃; for 5h;
B. Synthesis of Intermediate 6(2)[0129] 1.0 g (2.93 mmol) of Intermediate 6(1) was dissolved in 10.0 mL of THF, and 14.64 mL (14.64 mmol) of a 1.0M tetrabutylammonium fluoride solution in THF was gradually added thereto at room temperature, and then the mixturewas stirred at room temperature for 5 hours. After the reaction was terminated, 50 mL of distilled water was addedthereto, and the resultant was subjected to extraction three times with 50 mL of methylene chloride to obtain an organiclayer. The organic layer was collected and dried with magnesium sulfate to evaporate the solvent. The residue wasseparately purified using silica gel column chromatography to obtain 730 mg (2.78 mmol) of Intermediate 6(2) (Yield:93 %). The produced compound was identified using LC-MS.C20H15N : M+ 270.12
93%
With potassium carbonate; In methanol; dichloromethane; at 20℃; for 3h;Inert atmosphere;
To a mixture of 4-bromotriphenylamine (0.401 g, 1.24 mmol), PdCl2(PPh3)2 (42.1 mg, 0.06 mmol) and CuI (9.5 mg, 0.05 mmol) was dissolved in toluene (10 mL) by stirring with a magnetic bar in a sealed tube. 1,8-Diazabicycloundec-7-ene (DBU 2.0 mL) was added, followed by trimethylsilyl acetylene (1.6 mL, 1.5 g, 15 mmol) under N2 atmosphere. The reaction mixture was stirred at 70 C. After 3 h, the reaction mixture was then filtered and the solid was washed with EtOAc (3 x 15 mL) and the filtrate was evaporated under reduced pressure. The residue was dissolved in a minimal amount of dichloromethane and eluted through a silica gel column with hexane to afford the desired product after solvent removal as light yellow oil (0.398 g, 94% yield); deltaH (400 MHz, CDCl3) 7.32-7.24 (6H, m, Ph), 7.09-7.05 (6H, m, Ph), 6.95 (2H, d, J 8.0 Hz, Ph), 0.24 (9H, s, Si-Me). Next, the TMS protect compound (0.395 g,1.16 mmol) and K2CO3 (2.013 g) were dissolved in dichloromethane(15 mL) and methanol (15 mL) under N2 gas by stirring with a magnetic bar in a round-bottom flask at room temperature for 3 h. Then, the reaction was filtered and the solid was washed with dichloromethane (15 mL) and the filtrate was evaporated under reduced pressure. The residue was dissolved in a minimal amount of dichloromethane and eluted through a silica gel column with gradient solvents starting from pure hexane to hexane/dichloromethane (4/1) to afford the desired product after solvent removal (0.290 mg, 93% yield) as a brown solid, m.p. 112-113 C; deltaH (400 MHz, CDCl3) 7.33 (2H, d, J 8.0 Hz, Ph), 7.26-7.29 (4H, m,Ph), 7.11-7.04 (6H, m, Ph), 6.96 (2H, d, J 8.0 Hz, Ph), 3.02 (1H, s, Csp-H).
91%
With tetrabutyl-ammonium chloride; In tetrahydrofuran; for 0.5h;
8 g of Intermediate 1-a was dissolved in 100 ml of THF,And 60 ml of tetrabutylammonium chloride in THF was added dropwise thereto(1.0 M) solution and stirred for about 30 minutes.100 ml of water was added to the reaction solution, and the resultant was extracted three times with 100 ml of ether each time. The organic layer was collected and dried over magnesium sulfate and the solvent was evaporated. The residue was separated and purified by silica gel column chromatography to obtain 5.6 g (91% yield) of Intermediate 1-b.
90%
With potassium carbonate; In methanol; at 20℃; for 3h;
The compound represented by the formula (1-c) was synthesized by the following reaction scheme [3].60 g (176 mmol) of the compound represented by the formula (1-b) obtained from the above-mentioned scheme 2 and 72.8 g (527 mmol) of K2CO3 were dissolved in 600 ml / 100 ml of methanol / dimethyl chloride in a 1 L 3- After the reaction is completed, the reaction solution is filtered through a Buchner funnel filled with 30 g of celite, and then the solvent of the filtered solution is removed to obtain yellow oil. (43 g, 90% yield)
86%
With potassium carbonate; In methanol; at 20℃; for 3h;
General procedure: 9-[4-{2-(Trimethylsilyl)ethynyl}phenyl]carbazole (4a, 0.68g, 2.7mmol), potassium carbonate (0.42g, 3.0mmol), and methanol (4.0mL) were placed in a flask, and the suspension was stirred at room temperature. After stirring for 3h, the precipitate that was insoluble in the solvent was separated by atmospheric filtration, and the filtrate was poured into saturated aqueous NH4Cl solution (20mL). The crude product was extracted with AcOEt (20mL) three times and the combined organic layer was washed with brine (once). The organic layer was collected and dried over anhydrous Na2SO4, which was separated by filtration. The filtrate was evaporated in vacuo and subjected to silica-gel column chromatography (eluent: hexane/CH2Cl2=5/1) to obtain the deprotection product 5a in 99% yield (0.53g, 2.0mmol) as a white solid.
78%
With methanol; potassium hydroxide; In tetrahydrofuran; at 20℃; for 1h;
A solution of KOH / MeOH (0.164 g / 2 ml) was added to a THF solution prepared by dissolving N, N-diphenyl-4 - [(trimethylsilyl) ethynyl] aniline (1 g, 2.94 mmol) The mixture was slowly added using a dropping funnel and stirred at room temperature for 1 hour. The solvent was concentrated under reduced pressure to obtain a black solid product, N, N-diphenyl-4-ethynylaniline (0.65 g, yield: 78%).
78%
With methanol; potassium hydroxide; In tetrahydrofuran; at 20℃; for 1h;
Compound 3b1 g (2.94 mmol)Potassium hydroside / methanol in this dissolved tetrahydrofuran solution0.164g / 2ml solution droping funnelThe mixture was slowly added with stirring at room temperature for 1 hour.After concentration of the solvent under reduced pressure, it is a black solid product.4-ethynyl-N, N-diphenylaniline (4b)0.65 g (yield: 78%) was obtained
0.5 g
With methanol; sodium hydroxide; In tetrahydrofuran; at 25℃; for 2h;
A 100 mL three-necked round bottomed flask, equipped with a magnetic stir bar and condenser, was charged with ligand (4-bromophenyl)diphenylamine (leftmost compound of the above scheme) (1 g, 3.08mmol), trimethylsilylacetylene (0.6mL, 4.62mmol), bis(triphenylphosphine) palladium dichloride (0.1 1 g, 0.3mmol), copper iodide (0.03g, 0.15mmol) and 40 mL of degassed THF/triethylamine (v:v= 3: 1 ). The mixture was stirred at 80C for 20 hours, and then concentrated under reduced pressure. The product was dissolved in dichloromethane solvent. The hydrophobic solvent solution was then sequentially washed with saturated ammonium chloride solution, brine and water. The combined hydrophobic phase was dried over MgS04 and filtered through a filter paper. The product was then purified using flash chromatography through silica using 4% ethyl acetate in hexane as eluent. After removal of eluent solvent under reduced pressure, the resulting white solid was dissolved in 10 mL of tetrahydrofuran solvent and treated with sodium hydroxide in methanol (20 mL of a 2.0 M solution). After stirring for 2 hour, the resulting mixture was concentrated under reduced pressure. After extraction with dichloromethane, the hydrophobic solution was dried over MgS04, filtered and the solvent was removed under reduced pressure to give the product (4-ethynylphenyl)diphenylamine ("Ph2NPhCCH") (middle compound of Scheme for Example 2) as a white solid (0.5g, 60%). Yield 60%.
N,N'-bis-(2,6-diisopropylphenyl)-1,7-dibromoperylene-3,4:9,10-tetracarboxydiimide[ No CAS ]
[ 205877-26-5 ]
C88H68N4O4[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
89%
With N-ethyl-N,N-diisopropylamine;copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; at 80℃; for 24h;
EXAMPLE b To a solution of 1,7-dibromo-N,N'-di((2,5-diisopropyl)phenyl)-3, 4:9, 10-perylenebis(dicarboximide) (0.61 g, 0.70 mmol) in 50 ml 1:1 mixture of THF and ethyldiisopropylamine degassed with nitrogen, were added tetrakis(triphenylphosphino)palladium(0) (73 mg, 63 mumol), copper(I) iodide (0.182 g, 0.96 mmol) and (4-diphenylaminophenyl)acetylene (0.45 g, 1.67 mmol). The reaction mixture was heated at 80 C. under nitrogen for 24 hours. After cooling to room temperature, the mixture was extracted with dichloromethane over 100 ml 2 M HCl solution. The organic solution was dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was taken up with silica gel and purified by flash chromatography eluting with 1:1 dichloromethane/hexane. 0.78 g (89%) of a dark solid was obtained. 1H NMR (300 MHz, CDCl3), delta (ppm): 10.21 (d, J=8.4 Hz, 2H), 8.97 (s, 2H), 8.77 (d, J=8.4 Hz, 2H), 7.49 (d, J=9.0 Hz, 6H), 7.32 (m, 12H), 7.11 (m, 14H), 2.76 (m, J=6.7 Hz, 4H), 1.18 (d, J=6.6 Hz, 24H). MS (FAB): m/z calc. for C89H68N4O4 1244.5241; found 1244.5276. Elemental analysis: calcd. for C89H68N4O4, C, 84.86; H, 5.50; N, 4.50. found C, 85.21; H, 5.52; N, 4.46.
With tris-(dibenzylideneacetone)dipalladium(0); triethylamine; Tetra(tert-butyl)phosphonium-tetrafluoroborat; In tetrahydrofuran; at 20℃; for 20h;Inert atmosphere;
To a 50 mL flask Tris(dibenzylideneacetone)dipalladium(0) (1.02 g, 1 .1 1 mmol), Tri-fe/f-butylphosphonium tetrafluoroborate (0.32 g, 1.11 mmol) 4-ethynyl-N,N-diphenyl-aniline (1.50 g, 5.57 mmol), 2-bromoethynyl(trimethyl)silane (0.98g, 5.57 mmol), triethylamine (15 mL), and anhydrous tetrahydrofuran (15 mL) were added under nitrogen. The reaction mixture was stirred for 20 h at room temperature. The reaction mixture extracted with ethylacetate (30 mL) and washed with water (10 mL) and brine solution (10 mL). Organic layer was dried over anhydrous sodium sulfate and concentrated. The crude product was purified using column chromatography on silica gel (0 to 5 % ethylacetate in hexanes) to obtain N,N-diphenyl-4-(4- trimethylsilylbuta-1 ,3-diynyl)aniline (1.60 g). LCMS m/z = 366.
t-BuOK (4 equiv) was allowed to dissolve in dried THF (2 ml/mmol) under argon and the solution was cooled to 78 C. After 20 min, 1.6 equiv of (bromomethyl)triphenylphosphonium bromide was added portionwise and stirring under argon continued for 2 h. Then a solution of aldehyde 8 (2.47 mmol) or 9 (0.74 mmol) in dried THF (2 ml/mmol) was slowly added dropwise and stirring continued for 1 h at 78 C and 20 h at rt. The solution was mixed with the same volume of NH4Cl (aq), acidified with 2 M HCl (aq) and extracted with ethyl acetate (350 ml). The organic layer was dried over Na2SO4, filtered and the solvent was evaporated in vacuo. Purification of the residue by chromatography on a SiO2 column (20% CHCl3 in hexanes) gave the title compound 7a (510 mg), 77%, (yellow solid) or 7b (80 mg, 41%, light-yellow crystalline solid; after chromatography the semi-solid oil was dissolved in hot hexanes, the solution was allowed to reach RT, filtered and concentrated under vacuum).
2,5-diiodo-1,4-bis[(3,7-dimethyloctyl)oxy]benzene[ No CAS ]
[ 205877-26-5 ]
C46H58INO2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); diisopropylamine; In toluene; at 25℃; for 12h;Inert atmosphere;
(1) Under nitrogen protection, 2.7 g of compound a and 12.8g 1,4-bis(3,7-dimethyloctyl,-ODMO)-2,5-diiodobenzene After mixing, it is dissolved in 100 ml of toluene-diisopropylamine solution. Add 0.6g Pd(PPh3)4) and 0.1g Cul at the same time, Fully reacted at room temperature (room temperature generally means 25 C, the same below) for 12 h, Add saturated ammonium chloride solution, Extracted with methylene chloride, Washed with saturated sodium chloride solution, Dry with anhydrous sodium sulfate, Filter, remove the solvent, Column chromatography to obtain compound b;
The general procedure was followed. The reaction was carried out with tert-butylisonitrile (171 muL, 1.5 mmol), cyclohexylamine (95 mg, 1 mmol), 4-ethynyl-N,N-diphenylaniline (269 mg, 1 mmol), and 2 (32.4 mg, 0.1 mmol) in toluene (2 mL) and was heated for 24 h at 100 C. After completion of the reaction the pressure tube was cooled to room temperature. Then the same pressure tube was charged with hydroxylamine hydrochloride (83 mg, 1.2 mmol) and absolute ethanol (2 mL) and stirred at room temperature for 16 h. After completion of the reaction, solvents were removed under reduced pressure, and the crude product was dissolved in CH2Cl2 (20 mL) and washed with water (50 mL). Purification was accomplished by column chromatography on neutral alumina. The eluent was hexanes/ethyl acetate 9.5:0.5, which afforded the desired compound (143 mg, 48%) as a white solid. Mp: 144-146 C. 1H NMR (CDCl3, 500 MHz) 6.97-6.99 (2H, t, 7 Hz, Ar-H), 7.02-7.05 (6H, m, Ar-H), 7.18-7.22 (4H, m, Ar-H), 7.25-7.27 (2H. d, 9 Hz, Ar-H) 8.44 (1H, s, 3-CH isoxazole), 8.54 (1H, s, 5-CH isoxazole). 13C{1H} NMR (CDCl3, 125 MHz): 121.1, 122.1, 123.3, 123.7, 124.6, 127.2, 129.4, 147.4, 147.8, 147.9, 152.7. MS(EI): m/z 312 (M+). Elemental Analysis: found: %C, 80.82; %H, 5.24; %N, 8.82; expected: %C, 80.75; %H, 5.16; %N, 8.97.
With copper(ll) sulfate pentahydrate; sodium hydrogencarbonate; ascorbic acid; In tetrahydrofuran; water; for 8h;Inert atmosphere;
General procedure: In a 50 mL of flask, a mixture of the terminal alkynes (2-4) (1.05 equiv.), organic azide (1) (1.0 equiv.), NaHCO3 (0.05 equiv.) and ascorbic acid (0.05 equiv.) were dissolved in the solution of THF and H2O (V/V=5/1), and then an aqueous solution of CuSO4·5H2O (0.05 equiv.) was added to it. After stirring for 8h under an argon atmosphere, the mixture was extracted with ether (10 mL × 3). The organic phase was dried over anhydrous Na2SO4. Then the solvent was removed and the residue was purified by a silica gel column eluted with toluene/methanol (V/V=10/1) to give the target dyes. 2.2.1 2-cyano-3-(3,4?,5'-tris(9-hexyl-9H-carbazol-3-yl)-2,2'-bithiophen-5-yl)acrylic acid (DH-1) [19]. (0006) Yellow powder, Yield: 85%. 1H NMR (300MHz, d6-DMSO): delta 8.87 (s, 1H), 8.32 (s, 1H), 7.93 (s, 1H), 7.83 (d, J=8.1Hz, 2H), 7.50 (s, 1H), 7.35 (t, J=7.5Hz, 4H), 7.10-7.04 (m, 8H), 4.10 (t, J=7.5Hz, 2H), 4.05 (t, J=7.2Hz, 2H), 1.75-1.69 (m, 4H), 1.42-1.19 (m, 12H), 0.86-0.75 (m, 6H). 13C NMR (75MHz, CDCl3): delta 164.9, 151.4, 146.9, 146.7, 146.0, 142.8, 142.2, 128.9, 127.9, 126.93, 125.9, 123.8, 122.9, 122.7, 122.1, 121.3, 118.2, 113.1, 111.8, 108.0, 69.0, 68.7, 31.1, 30.7, 28.3, 28.2, 25.0, 24.8, 21.8, 13.5. MS (ESI-MS): m/Z=683.6. C42H45N5O4 (Mw=683.84): Calcd. C, 73.77; H, 6.63; N, 10.24; Found C, 73.83; H, 7.04; N, 10.67.
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine; In tetrahydrofuran; at 20℃; for 20h;
1.0 g (3.52 mmol) of <strong>[265981-13-3]2-bromo-3-iodopyridine</strong> was dissolved in 10.0 mL of THF, and 1.1 g (3.87 mmol) of Intermediate 6(2), 200 mg (0.18 mmol) of tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4), 20 mg (0.18 mmol) of copper iodide (CuI), and 1.47 mL (10.57 mmol) of triethylamine (TEA) were added thereto, and then the mixture was stirred at room temperature for 20 hours. After the reaction was terminated, 20 mL of distilled water was added thereto, and the resultant was subjected to extraction three times with 30 mL of methylene chloride to obtain an organic layer. The organic layer was collected and dried with magnesium sulfate to evaporate the solvent. The residue was separately purified using silica gel column chromatography to obtain 1.47 g (3.46 mmol) of Intermediate 6(3) (Yield: 98%). The produced compound was identified using LC-MS. [0139] C25H17BrN2: M+425.06
98%
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine; In tetrahydrofuran; at 20℃; for 20h;
C. Synthesis of Intermediate 6(3)[0130] 1.0 g (3.52 mmol) of <strong>[265981-13-3]2-bromo-3-iodopyridine</strong> was dissolved in 10.0 mL of THF, and 1.1 g (3.87 mmol) ofIntermediate 6(2), 200 mg (0.18 mmol) of tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4), 20 mg (0.18 mmol) ofcopper iodide (Cul), and 1.47 mL (10.57 mmol) of triethylamine (TEA) were added thereto, and then the mixture wasstirred at room temperature for 20 hours. After the reaction was terminated, 20 mL of distilled water was added thereto,and the resultant was subjected to extraction three times with 30 mL of methylene chloride to obtain an organic layer.The organic layer was collected and dried with magnesium sulfate to evaporate the solvent. The residue was separatelypurified using silica gel column chromatography to obtain 1.47 g (3.46 mmol) of Intermediate 6(3) (Yield: 98 %). Theproduced compound was identified using LC-MS.C25H17BrN2: M+ 425.06
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; N-ethyl-N,N-diisopropylamine; triphenylphosphine; In toluene; at 70℃; for 4h;Inert atmosphere;
A mixture of 4-bromobenzaldehyde (98.8 mg, 0.54 mmol), PdCl2(PPh3)2 (14.0 mg, 0.02 mmol), CuI (3.8 mg, 0.02 mmol), 4-ethynyl-N,N-diphenylaniline (1) (145.3 mg, 0.54 mmol) and PPh3 (5.2 mg, 0.02 mmol) in toluene (15 mL) was added to diisopropylamine (DIPA) (10 mL) under N2 gas and the mixture was stirredat 70 C. After 4 h, the reaction mixture was then filtered and the solid was washed with EtOAC (3 x 15 ml). The residue was evaporated under reduced pressure and the residue was eluted through a silica gel column with pure hexane to hexane/dichloromethane (2/1 (v/v)) as an eluent to afford 2 (163.2 mg, 81% yield) as a yellow solid, m.p. 154-155 C; deltaH (400 MHz, CDCl3) 10.01 (1H, s, O=CH),7.85 (2H, d, J 8.0 Hz, Ph), 7.64 (2H, d, J 8.0 Hz, Ph), 7.39 (2H, d, J8.0 Hz, 2H), 7.31-7.27 (4H, m, Ph), 7.14-7.07 (6H, m, Ph), 7.01 (2H, d,J 8.0 Hz, Ph).
N,N-diphenyl-4-(1-benzyl-1H-1,2,3-triazol-4-yl)aniline[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
72%
With tetrakis(actonitrile)copper(I) hexafluorophosphate; N-ethyl-N,N-diisopropylamine; tris[(1-benzyl-1H-1,2,3-triazol-4yl)methyl]amine; In dichloromethane; at 25℃;Schlenk technique; Inert atmosphere;
To a 50 mL Schlenk flask equipped with a magnetic stir bar was added (4-ethynylphenyl)diphenylamine (0.5g, 1.86mmol), benzyl azide (0.29g, 2.21 mmol), diisopropylethylamine (0.475g, 3.68mmol), tris[(1-benzyl-1 -/-1 ,2,3-triazol-4-yl)methyl]amine (1 mol %) and 30 mL of dichloromethane. The resulting solution was bubbled with nitrogen gas for 20 minutes. [Cu(CH3CN)4]PF6 (1 mol %) was added as a catalyst. The resulting mixture was stirred overnight, after which the solvent was removed under reduced pressure. The crude product was dissolved in dichloromethane. The solution was washed with saturated ammonium chloride solution, brine and water. Following isolation, the non-aqueous phase was dried over MgS04 and filtered through a filter paper. The product was then purified using flash chromatography through silica (1 :1 hexanes:ethyl acetate as eluent) to afford 0.54 g N,N-diphenyl-4-(1 -benzyl-1 H-1 ,2,3-triazol-4-yl) aniline as white solid (72% yield). 1H NMR (300 MHz, CDCI3) delta 7.68 (d, J = 8.8 Hz, 2H), 7.60 (s, 1 H), 7.45-7.36 (m, 3H), 7.35-7.20 (m, 6H), 7.19-6.98 (m, 8H), 5.59 (s, 2H).
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In tetrahydrofuran; at 70℃; for 15h;Inert atmosphere;
General procedure: To a stirred solution of the respective alkyne (10/11) (0.40 mmol), and bromo-BT 2 (0.30 mmol)in THF, and TEA (1:1, v/v) were added [PdCl2(PPh3)2] (10 mg, 0.014 mmol) and CuI (2 mg,0.01 mmol) under an argon flow at room temperature. The reaction mixture was stirred for 15 hat 70 C, and then cooled to room temperature. The solvent was then evaporated under reducedpressure, and the mixture was purified by SiO2 chromatography with DCM/hexane (2:2, v/v),followed by recrystallization in DCM:hexane (1:3) to obtain 3/4 as colored solids.
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine; In toluene; at 45℃;Inert atmosphere; Schlenk technique;
General procedure: Dibromothienoisoindigo 1 (100 mg, 152.2 mmol, 1 eq), alkyne compound 2 or 3 (319.6 mmol, 2.1 eq), copper (I) iodide (0.29 mg, 1.52 mmol, 0.01 eq) and tetrakis-(triphenylphosphine) palladium (0) (8.79 mg, 7.61 mmol, 0.05 eq) were combined in a Schlenk flask. Then 20 mL of a freshly distillated and degassed solution of triethylamine: toluene (1:1) was added to the flask and the reaction mixture was stirred overnight at 45 C. The solution was then poured into 150 mL of brine and extracted with diethyl ether (2 × 100mL). The organic layers were combined, washed with brine, dried over anhydrous MgSO4 and concentrated under vacuum. The crude product was finally purified by column chromatography (dichloromethane/pentane 3:7) to afford the desired dark green compound. TII-TPA: (75 mg, 47.7% yield) 1H NMR (300 MHz, CDCl3, ppm): delta: 7.30 (m, 14H), 7.11 (m, 12H), 7.00 (d, J=8.7Hz, 4H), 6.85 (s, 2H), 3.66 (d, J=7.2Hz, 4H), 1.83 (s, 2H), 1.35-1.21 (m, 16H), 0.92-0.81 (m, 12H). 13C NMR (75 MHz, CDCl3, ppm) delta: 170.80, 150.71, 148.44, 146.91, 132.37, 131.72, 129.46, 125.28, 123.89, 121.71, 120.13, 115.58, 114.87, 114.21, 99.31, 83.91, 45.77, 38.44, 30.53, 28.64, 23.88, 23.03, 14.05, 10.49. ESI HRMS: calculated for C68H64N4O2S2 1032.4471, found 1032.4467. IR (neat): upsilon = 1676cm-1 (C]O).
1-bromo-[4-(N,N-diphenylamino)-2-phenyl]ethynyl}benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
85%
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine; at 20℃; for 1h;Inert atmosphere;
[Chemical Formula 1-d] was synthesized by the following Reaction Scheme 4. 40 g (148 mmol) of the compound represented by the formula 1-c obtained from the above-mentioned scheme 3 was added dropwise to 35 g (124 mmol) of 1- bromo-2-iodobenzene as a dropping funnel under nitrogen,And 1.2 g (6 mmol) of copper iodine,Pd (PPh3) 4, 2.8 g (2 mmol) is slowly added to a 1 L 3-neck round-bottom flask dissolved in 150 mL of triethylamine. After stirring for 1 hour at room temperature, add 500 mL of normal hexane to dilute. The reaction solution is filtered through a Buchner vacuum funnel filled with 200 g of silica gel to remove the catalyst, and then washed with 1 L of n-hexane. The solvent of the filtered solution is all removed to obtain a compound represented by the formula [1-d]. (45 g, 85% yield)
55%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In tetrahydrofuran; at 20℃; for 2h;Inert atmosphere;
7.5g (1.2eq) of 2-bromoiodobenzene,780 mg (0.05 eq) of bis(chloro(triphenylphosphine))palladium (PdCl2(PPh3)2) and 250 mg (0.06 eq) of CuI were mixed together in a flask.Then supply nitrogen under vacuum,Then 70 mL of THF was added to the mixture and stirred.13 mL (8 eq) of triethylamine and 6 g (1 eq) of intermediate 1-3 were slowly added dropwise thereto,And then stirred for about 2 hours at room temperature under N2 pressure.The resulting product was evaporated using a rotary evaporator to remove the solvent.After adding 50mL of water,The reaction solution was extracted three times with 50 mL of diethyl ether.The organic layer was collected and dried using magnesium sulfate to evaporate the solvent.The residue was separated and purified using silica gel column chromatography.5 g of intermediate 1-a were obtained (yield: 55%).This compound was identified using LC-MS.
With copper(II) acetate monohydrate; 2-amino-phenol; In acetonitrile; at 20℃; for 0.5h;Inert atmosphere;
General procedure: Method A:7 Mesyl azide (363.3 mg, 3.0 mmol), (p-dimethylaminophenyl)acetylene (435.6 mg, 3.0 mmol), Cu(OAc)2·H2O (10 mol %, 60.0 mg), 2-aminophenol (5 mol %, 16.4 mg), and acetonitrile (3.0 mL) were added to a 4 mL-vial equipped with a stirrer bar. The reaction mixture was stirred at room temperature for 30 min. The solution was passed through a pad of celite and eluted with AcOEt (15 mL). The filtrate was washed with NH4Cl aq. (50 mL). The aqueous layer was extracted with AcOEt (20 mL x 3). The combined organic layer was washed with brine (50 mL) and dried over MgSO4. The solvent was removed under reduced pressure. The residue was purified by silica-gel column chromatography (Hex/AcOEt 5:1 to 1:1) to give the triazole 7a (631.0 mg, 79%) as a yellowish solid.
Stage #1: 4-(4-bromophenyl)-2,6-diphenylpyridine; 4-diphenylaminophenylacetylene In tetrahydrofuran; triethylamine for 0.5h; Inert atmosphere;
Stage #2: With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide for 36h; Reflux; Inert atmosphere;
2.3. Synthesis
General procedure: General procedure for the preparation of compounds 2-6:Equal amount of 1 and substituted ethynylbenzenes were dissolved in triethylamine/tetrahydrofuran (1:1, v/v). The solution was purged for 30 min with bubbling nitrogen followed by addition of Pd(PPh3)2Cl2 (0.03 equiv.) and CuI (0.06 equiv.). Afterwards, there action mixture was purged another 20 min and then refluxed for 36 h. After filtration, the solvent was removed under reduced pressure. Purification of the residue on silica gel (hexane/ethyl acetate:4/1) gave the solid product as yellow powder.
With copper(l) iodide; triethylamine; In dichloromethane; at 20℃; for 3h;Inert atmosphere; Schlenk technique;
The alkynylgold(III) complex was prepared according to a literature procedure [4,5]. To a mixture of [Au{C^N(COOEt)^C}Cl] (267 mg, 0.50 mmol), 4-ethynyltriphenylamine (202 mg, 0.75 mmol) and a catalytic amount of copper(I) iodide (10 mg, 0.05 mmol) was added dichloromethane (35 mL). Triethylamine (2 mL) was added to the resulting suspension. After stirring under an inert atmosphere at room temperature for 3 h, the solvent was removed in vacuo. The resulting residue was purified by column chromatography on silica gel with dichloromethane. The complex was then recrystallized by slowly diffusing diethyl ether vapor into the concentrated dichloromethane solution to give orange-yellow crystals. Yield: 172 mg (45%). 1H NMR (300 MHz, CDCl3, 298 K)/ppm: delta 1.46 (t, 3H, J 7.1 Hz, -CH3), 4.51 (q, 2H, -OmicronCH2-), 7.01 (d, 4H, J 6.2 Hz, -C^CC6H4-), 7.12 (m, 4H, -N(C6H5)2), 7.29 (m, 6H, -N(C6H5)2), 7.39 (t, 2H, J 7.4 Hz, phenyl of C^N^C), 7.49 (d, 2H, J 7.4 Hz, phenyl of C^N^C), 7.63 (d, 2H, J 7.4 Hz, phenyl of C^N^C),7.98 (s, 2H, pyridine of C^N^C), 8.07 (d, 2H, J 7.4 Hz, phenyl of C^N^C). Positive FAB-MS: m/z 767 [M]. IR (KBr): 2147 cm-1 (n(C^C)). Elemental analyses calcd for C40H29AuN2O21/2CH2Cl2 (found): C, 60.12 (59.75); H, 3.74 (3.64); N, 3.46 (3.45).
General procedure: Arylacetylide compound (0.1mmol) and KOH (11.2mg, 0.2mmol, 2.0equiv.) were dissolved in MeOH (20mL) under stirring at room temperature for 30min. Then complex 2 (57.4mg, 0.1mmol, 1.0equiv.) and CuI (1.2mg, 0.06mmol, 0.6equiv.) were added. The mixture was purged under N2 for 30min, and then stirred at room temperature for 18h. After the reaction, the reaction mixture was concentrated, and ether was added. The precipitants were separated by filtration. The solid was dissolved in 20mL MeOH, then 20mL saturated aqueous solution of NH4PF6 was added at room temperature. The mixture was stirred at room temperature for 3h, then the solid was filtered, washed with ether and CH2Cl2 to give the desired product.
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); diisopropylamine; In toluene; at 20℃; for 20h;Inert atmosphere;
The suspension of 2-bromo-3-iodonaphthalene (5 mmol), <strong>[205877-26-5]4-(N,N-diphenylamino)phenylacetylene</strong> (5.25 mmol), Pd(PPh3)4 (0.10 mmol), CuI (0.10 mmol), toluene (10 mL), and i-Pr2NH (5 mL) was stirred at room temperature for 20 hours. Then, inorganic salts were removed by filtration, and all the volatiles were evaporated under reduced pressure. The reaction product was subjected to silica gel chromatography (eluent: hexane/CH2Cl2=4/1), and then the resulting crude product was purified by recrystallization from MeOH to yield synthetic intermediate M8b as white powders in 96% yield.
1,2-diphenyl-3-[4-(N,N-diphenylamino)phenyl]ethynyl}benzo[b]phosphole P-oxide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
94%
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine; In tetrahydrofuran; at 80℃; for 18h;Inert atmosphere;
General procedure: To a solution of 4 (0.192 g,0.503mmol) in a mixed solvent of toluene (10 mL) and water(2.5 mL) was added 4-(N,N-diphenylamino)phenylboronic acid(0.160 g, 0.553mmol), [Pd2(dba)3]*CHCl3 (13.9 mg, 0.0134mmol), S-Phos (10.1 mg, 0.0246mmol) and K3PO4 (0.161 g,0.758mmol). The mixture was heated at 80 C with stirring for44 h and then extracted with chloroform. The combined organiclayer was washed with brine, dried over anhydrous Na2SO4,and filtered. After removing solvents under reduced pressure,the yellow solid was subjected to silica gel column chromatography (CHCl3/AcOEt 8:1, Rf = 0.30) to afford 0.186 g(0.340mmol, 68% yield) of 2a as yellow solids.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; N-ethyl-N,N-diisopropylamine; In tetrahydrofuran; at 50℃;Schlenk technique; Inert atmosphere;
Iodinated squaraine dye (2) (48.0 mg, 0.061 mmol), compound 1c (30.0 mg, 0.111 mmol), Pd(PPh3)2Cl2 (3.91 mg, 0.0056 mmol), CuI (1.06 mg, 0.0056 mmol), 0.37 mL of diisopropylamine and 0.53 mL of THF were added to a flask. Under nitrogen atmosphere, the reaction mixture was heated overnight at 50 C. After the solvent was evaporated, the reaction mixture was subjected to the column chromatography (hexane/CHCl3, 1:10) to obtain a deep blue fraction. The targeted compound was recrystallized from a solution of hexane/chloroform as a deep green solid (38 mg, 67%).
A mixture of DPP-Br2 (100mg, 0.146mmoles), Ethynyl benzoic acid (20.3mg, 0.138mmoles) and N-(4-ethynylphenyl)-N-phenylbenzenamine (35.6mg, 0.138mmoles) in dry THF (15mL) and NEt3 (3mL) was degassed with dinitrogen for 20min, Then Pd2(dba)3 (80.10mg, 0.087mmol) and AsPh3 (178mg, 0.584mmole) were added to the mixture. The solution was refluxed for 12h under dinitrogen. The solvent was removed in vacuum. The residue was purified on a column chromatograph (silica gel) using CHCl3 /methanol=95/05as eluent to afford DPP1 Yield: 15.0%. 1H NMR (400MHz, CD2Cl2) delta 8.53-8.52 (d, J=7.2Hz, 2H), 7.24-7.23 (d, J=2.1Hz, 4H), 7.22 (t, J=2.3Hz, 4H), 7.20 (d, J=1.4Hz, 2H), 7.18 (d, J=4.0Hz 2H), 7.01 (d, J=2.0Hz, 4H), 7.00 (d, J=6.3, 4H), 3.84 (t, J=7.5Hz, 4H), 1.26-1.14 (m, 16H), 0.82-0.76 (m, 14H). MALDI-TOF MS Calcd. for936.2; Found 937.51. HRMS C59H57N3O4S2 calcd. for 936.03889 found 936.3823. Anal. Calcd. For C59H57N3O4S2% (936.23): C, 75.69; H, 6.14; N, 4.49. Found: C, 75.65; H, 6.13; N, 4.50.
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine; In tetrahydrofuran; at 20℃; for 2h;Inert atmosphere;
General procedure: 5 g (1 eq) of Intermediate 75a, 2.26 g (0.15 eq) of Pd(PPh3)4, and 740 mg (0.30 eq) of CuI were put into a flask in a vacuum, which was then supplied with N2 gas. After 100 mL of THF was added into the flask and then stirred, 58.2 mL (4.5 eq) of triethylamine and 7.7 g (2.2 eq) of Compound E were slowly dropwise added thereto, and then stirred at room temperature for about 2 hours in a N2 atmosphere. After removing the solvent using a rotary evaporator, 100 mL of water was added to the resulting reaction solution, which was then extracted three times each with 100 mL of ethylether. An organic layer was collected and then dried using magnesium sulfate to evaporate the solvent. The residue was separated and purified using silica gel column chromatography to obtain 6.24 g of Intermediate 75b (Yield: 63%). This compound was identified using LC-MS. C44H28Br2N2O1: M+760.05
With bis-triphenylphosphine-palladium(II) chloride; triethylamine; copper dichloride; In tetrahydrofuran; at 70℃; for 24h;
D2 Compound M2 (244mg, 0.2mmol), 4- (N, N- diphenylamino) phenylacetylene i.e., when Q represents C?C (134mg, 0.5mmol), bis (triphenylphosphine) dichloride palladium (4mg, 0.005mmol) and cuprous iodide (2mg, 0.01mmol) was dissolved in tetrahydrofuran (20 mL) and triethylamine (15mL) mixed solution, 70 refluxed for 24 hours.After the reaction mixture was cooled to room temperature, poured into 50mL of deionized water and extracted with dichloromethane, and the combined organic phase was dried over anhydrous sodium sulfate.After the organic solvent was removed by rotary evaporation, the crude product with petroleum ether / methylene chloride (v: v, 5: 2) as eluent to give the desired product is purified by column chromatography as an orange-red solid in 56% yield.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In tetrahydrofuran; at 70℃; for 24h;
The present embodiment discloses a specific synthesis process of the organic small molecule donor material F3, which comprises the following steps:A mixture of compound A (147 mg, 0.2 mmol), 4- (N, N-diphenylamino) phenylacetylene, i.e. Q,(134 mg, 0.5 mmol), bis (triphenylphosphine) palladium dichloride (4 mg, 0.005 mmol) and iodinationCopper (2 mg, 0.01 mmol) was dissolved in a mixed solution of 20 mL of tetrahydrofuran and 15 mL of triethylamine at 70 CRefluxed for 24 hours. The reaction solution cooled to room temperature was poured into 50 mL of deionized water, extracted with dichloromethane, and combinedAnd the organic phase was dried over anhydrous sodium sulfate. The organic solvent was removed by rotary evaporation, and the crude product was recrystallized from petroleum ether / methylene chloride (v: v,5: 1) as a developing solvent, which was purified by column chromatography to give the object product as an orange solid in 45% yield..
N,N-diphenyl-{4-[4-(5,5-dimethyl-[1,3]-dioxan-2-yl)-phenylethynyl]aniline[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
58%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In tetrahydrofuran; at 45℃; for 8h;
CuI (0.0251 g, 0.135 mmol) and Pd(PPh3) 2Cl2 (0.15 mmol) were added to a THF / TEA (1: 1) solution prepared by dissolving N, N-diphenyl-4-ethynylaniline (0.094 g, 0.135 mmol) was added followed by 2- (4-iodo-phenyl) -5,5-dimethyl- [1,3] dioxane (0.86 g, 45 CThe mixture was stirred for 8 hours while maintaining the temperature. After stirring, the reaction mixture was separated and purified by chromatography (n-hexane: dichloromethane = 4: 1 (v / v)) to obtain a dark green solid product N, N-diphenyl- {4- [4- (5,5- - [1,3] dioxan-2-yl) -phenylethynyl] phenyl} aniline (0.99 g, yield: 58%).
4,4'-((4,6-dibromo-1,3-phenylene)bis(ethyne-2,1-diyl))bis(N,N-diphenylaniline)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
60%
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine; In tetrahydrofuran; at 20℃; for 2h;Inert atmosphere;
3.46 g (0.48 eq) of 1,5-dibromo-2,4-diiodo-benzene, 1.2 g (0.07 eq) of Pd (PPh3) 4 and 400 mg(0.14 eq) of CuI was placed in a reaction vessel, which was then supplied with N2 gas under vacuum. Next, 50 ml of THF was added to the reaction vessel, followed by stirring. Then, 4.5 ml (2.2 eq) of triethylamine and 4 g (1 eq) of Intermediate 1-b were slowly dropped thereto, and then stirred in a N 2 atmosphere at room temperature for about 2 hours. After the solvent was removed using a rotary evaporator, 50 ml of water was added to the reaction solution, and the resultant was extracted three times with 50 ml each of ether. The organic layer was collected and dried over magnesium sulfate and the solvent was evaporated. The residue was separated and purified using silica gel column chromatography to obtain 6.6 g (60% yield) of Intermediate 1-c.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In tetrahydrofuran; at 40℃; for 12h;Inert atmosphere; Schlenk technique;
A mixture of compound A (143 mg, 0.20 mmol), CuI (2 mg,0.01 mmol), Pd(PPh3)2Cl2 (4 mg, 0.005 mmol) and compound D2(135 mg, 0.5 mmol) in 20 mL THF and 15 mL Et3N was refluxed at70 C for 12 h. The solvent was evaporated and the residue waspurified by column chromatography on silica gel column elutingwith PE: DCM (4: 1, v/v) to give a red solid (164 mg, yield: 75%),M.p.: 60e62 C. 1H NMR (400 MHz, CDCl3, ppm): d 8.52 (d,J 4.0 Hz, 2H), 7.39 (d, J 8.8 Hz, 4H), 7.34 (d, J 4.0 Hz, 2H), 7.29(t, J 7.8 Hz, 8H), 7.13 (d, J 7.6 Hz, 8H), 7.08 (t, J 7.4 Hz, 4H), 7.02(d, J 8.8 Hz, 4H), 4.14 (t, J 7.0 Hz, 4H), 1.99e1.95 (m, 4H),1.29e1.49 (m, 20H), 0.88 (t, J 6.6 Hz, 6H). 13C NMR(100 MHz,CDCl3, ppm): d 151.93, 150.73, 148.11, 147.15, 135.28,132.39, 131.36, 130.89, 129.43, 125.35, 125.09, 123.66, 122.16, 117.34,115.74, 95.33, 82.42, 74.59, 31.83, 30.32, 29.50, 29.31, 25.97, 22.68,14.11. HRMS (MALDI-TOF): 1090.4269 [M] (calcd forC70H66N4O2S3: 1090.4348).
2-(3,5-bis(trifluoromethyl)phenyl)-4,7-dibromo-2H-benzo[d][1,2,3]triazole[ No CAS ]
[ 205877-26-5 ]
4,4'-((2-(3,5-bis(trifluoromethyl)phenyl)-2H-benzo[d][1,2,3]triazole-4,7-diyl)bis(ethyne-2,1-diyl))bis(N,N-diphenylaniline)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
87%
With copper(l) iodide; 1,8-diazabicyclo[5.4.0]undec-7-ene; In acetonitrile; at 130℃; for 0.333333h;Inert atmosphere; Microwave irradiation;
General procedure: General procedure: A mixture of 2-(3,5-bis(trifluoromethyl)phenyl)-4,7-dibromo-2Hbenzo[d][1,2,3]triazole (3) (0.100 g,0.2 mmol), the corresponding acetylene derivative (4) (0.4 mmol),DBU (0.061 g, 0.40 mmol), CuI (0.002 g, 0.01 mmol) and Pd-EncatTM TPP30 (0.018 g, 0.007 mmol) was charged under argonto a dried microwave vessel. CH3CN (1 mL) was added. The vesselwas closed and irradiated at 130 C for 20 min. The crude reactionproduct was purified by chromatography, eluting with hexane/ethyl acetate to give analytically pure products 1.
2-(4-(diphenylamino)phenyl)benzofuran-6-carbaldehyde[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
1.08 g
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In acetonitrile; at 50℃; for 3h;Inert atmosphere;
[0134] To a 50 mL flask was added 4-ethynyltriphenylamine (1.01 g), 3-hydroxy-4- iodobenzaldehyde (0.77 g), bis(triphenylphosphine)palladium dichloride (0.066 g), and copper(l) iodide (0.054 g). The flask was purged with nitrogen for 20 minutes. A solution of triethylamine (2.18 mL) in anhydrous acetonitrile (15.6 mL) was degassed by bubbling nitrogen through for 20 minutes. The triethylamine solution was added to the reaction and the reaction then heated to 50 C for 3 hours. The reaction was cooled to room temperature and water (25 mL) added. The aqueous layer was extracted with ethyl acetate (3x30 mL) and the combined organic fractions washed with brine and dried over sodium sulfate. The organic layer was filtered and concentrated. The residue was purified via chromatography on silica gel (elution with 0 to 13% ethyl acetate in hexanes) to afford 2-(4-(diphenylamino)phenyl)benzofuran-6-carbaldehyde (1.08 g). 1 H-NMR (400 MHz, DMSO-d6): delta 10.04 (s, 1 H), 8.1 1 (d, 1 H), 7.86 (d, 2H), 7.80 (s, 2H), 7.42-7.34 (m, 5H), 7.17-7.10 (m, 6H), 7.03 (d, 2H).
1.08 g
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In acetonitrile; at 50℃; for 3h;Inert atmosphere;
To a 50 mL flask was added 4-ethynyltriphenylamine (1.01 g), 3-hydroxy- 4-iodobenzaldehyde (0.77 g), bis(triphenylphosphine)palladium dichloride (0.066 g), and copper(l) iodide (0.054 g). The flask was purged with nitrogen for 20 minutes. A solution of triethylamine (2.18 mL) in anhydrous acetonitrile (15.6 mL) was degassed by bubbling nitrogen through for 20 minutes. The triethylamine solution was added to the reaction and the reaction then heated to 50 C for 3 hours. The reaction was cooled to room temperature and water (25 mL) added. The aqueous layer was extracted with ethyl acetate (3x30 mL) and the combined organic fractions washed with brine and dried over sodium sulfate. The organic layer was filtered and concentrated. The residue was purified via chromatography on silica gel (elution with 0 to 13% ethyl acetate in hexanes) to afford 2-(4-(diphenylamino)phenyl)benzofuran-6-carbaldehyde (1.08 g). 1H-NMR (400 MHz, DMSO-d6): delta 10.04 (s, 1H), 8.1 1 (d, 1H), 7.86 (d, 2H), 7.80 (s, 2H), 7.42-7.34 (m, 5H), 7.17-7.10 (m, 6H), 7.03 (d, 2H).
2-(4-(diphenylamino)phenyl)-benzofuran-5-carbaldehyde[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
0.24 g
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; N-ethyl-N,N-diisopropylamine; In 1,4-dioxane; at 80℃; for 2h;
[0160] To a nitrogen filled flask was added 4-ethynyl-N,N-diphenylaniline (0.49 g), 3- bromo-4-hydroxybenzaldehyde (0.30 g), bis(triphenylphosphine)palladium dichloride (0.032 g), and copper(l) iodide (0.026 g) and the flask was purged with nitrogen for 20 minutes. Degassed 1 ,4-dioxane (7.5 ml_) and N,N-diisopropylethylamine (1.3 ml_) were added to the reaction and the reaction heated to 80 C for 2 hours. The reaction temperature was increased to 100 C for 22 hours. The reaction mixture was cooled to room temperature and water (10 ml_) and brine (10 ml_) were added. The aqueous layer was extracted with ethyl acetate (3x 30 ml_) and the combined organic layers dried over magnesium sulfate, filtered, and concentrated. The residue was purified via chromatography on silica gel (elution with 0 to 10% ethyl acetate in hexanes) to afford 2-(4-(diphenylamino)phenyl)benzofuran-5-carbaldehyde (0.24 g). 1H NMR (400 MHz, Chloroform-d) delta 10.04 (s, 1 H), 7.98 (s, 1 H), 7.78 - 7.71 (m, 3H), 7.64 (d, 2H), 7.33 - 7.27 (m, 4H), 7.18 - 7.06 (m, 7H), 6.94 (d, 1 H).
0.24 g
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; N-ethyl-N,N-diisopropylamine; In 1,4-dioxane; at 80 - 100℃; for 24h;Inert atmosphere;
To a nitrogen filled flask was added 4-ethynyl-N,N-diphenylaniline (0.49 g), 3-bromo-4-hydroxybenzaldehyde (0.30 g), bis(triphenylphosphine)palladium dichloride (0.032 g), and copper(l) iodide (0.026 g) and the flask was purged with nitrogen for 20 minutes. Degassed 1,4-dioxane (7.5 mL) and N,N-diisopropylethylamine (1.3 mL) were added to the reaction and the reaction heated to 80 C for 2 hours. The reaction temperature was increased to 100 C for 22 hours. The reaction mixture was cooled to room temperature and water (10 mL) and brine (10 mL) were added. The aqueous layer was extracted with ethyl acetate (3x 30 mL) and the combined organic layers dried over magnesium sulfate, filtered, and concentrated. The residue was purified via chromatography on silica gel (elution with 0 to 10% ethyl acetate in hexanes) to afford 2-(4-(diphenylamino)phenyl)benzofuran-5-carbaldehyde (0.24 g). 1H NMR (400 MHz, Chloroform-d) delta 10.04 (s, 1H), 7.98 (s, 1H), 7.78 - 7.71 (m, 3H), 7.64 (d, 2H), 7.33 - 7.27 (m, 4H), 7.18 - 7.06 (m, 7H), 6.94 (d, 1H).
N-(4-(2-(4-(2-(trimethylsilyl)ethynyl)phenyl)ethynyl)phenyl)-N-phenylbenzenamine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
49%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine; at 100℃; for 15h;
General procedure: N-(4-(Ethynyl)phenyl)carbazole (5a, 0.53g, 2.0mmol), 4-{2-(trimethylsilyl)ethynyl}-1-bromobenzene (0.76g, 3.0mmol), Cl2Pd(PPh3)2 (0.084g, 0.12mmol), PPh3 (0.052g, 0.20mmol), CuI (0.038g, 0.20mmol), and Et3N (20mL) were placed in a flask, and the mixture was stirred at 100C for 15h. After stirring, the resulting precipitate was separated by atmospheric filtration, and the filtrate was poured into saturated aqueous NH4Cl solution (20mL). The crude product was extracted with AcOEt (20mL) three times and the combined organic layer was washed with brine (once). The organic layer was collected and dried over anhydrous Na2SO4, which was separated by filtration. The filtrate was evaporated in vacuo and subjected to silica-gel column chromatography (eluent: hexane/CH2Cl2=5/1) to obtain the coupling product 6a in 55% yield (0.48g, 1.1mmol) as a white solid.
ethyl 5-((4-(diphenylamino)phenyl)ethynyl)-4-methylthiazole-2-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
50%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In N,N-dimethyl-formamide; for 18h;Inert atmosphere; Reflux;
Ethyl 5-bromo-4-methylthiazole-2-carboxylate (0.183 g, 0.738 mmol) was dissolved in deaerated mixture of DMF (5.0 mL) and NEt3 (5.0 mL). To the solution was added 4-ethynyl-N,N-diphenylaniline3 (0.235 g, 0.874 mmol), Pd(PPh3)2Cl2 (25.6 mg, 0.0364 mmol), and CuI (28.0 mg, 0.147 mmol). The mixture was stirred for 18 h under refluxing conditions. After being cooled to room temperature, the reaction mixture was filtered with pads of Celite and Florizil. To the filtrate was added EtOAc (15 mL), and the solution was washed with H2O (10 mL × 4) and brine (15 mL). The organic layer was dried with MgSO4. After filtration and evaporation, the residue was subject to column chromatography on SiO2 (hexane : EtOAc = 3 : 1) to give ethyl 5-((4-(diphenylamino)phenyl)ethynyl)-4-methylthiazole-2-carboxylate (0.1613 g, 0.368 mmol, 50%) as yellow solid. Recrystallization from CHCl3 and hexane gave yellow powder: m.p. = 118 C; 1H NMR (300 MHz, CDCl3) delta 1.44 (t, J = 7.1 Hz, 3H), 2.61 (s, 3H), 4.47 (q, J = 7.1 Hz, 2H), 7.00 (d, J = 8.5 Hz, 2H), 7.09 (t, J = 7.4 Hz, 2H), 7.12 (d, J = 7.6 Hz, 4H), 7.30 (t, J = 7.5 Hz, 4H), 7.36 (d, J = 8.5 Hz, 2H); 13C NMR (75 MHz, CDCl3) delta 14.2, 16.4, 62.6, 78.3, 100.3, 114.1, 120.9, 121.6, 124.0, 125.3, 129.5, 132.5, 146.8, 148.8, 154.7, 158.3, 159.7; IR (KBr disk) 3432, 2198, 1590, 1490, 1283, 1094, 697 cm-1. HRMS (ESI) m/z: [M+H]+ Calcd for C27H23N2O2S 439.1475; Found 439.1472.
methyl 3,5-dicyano-4-((4-(diphenylamino)phenyl)ethynyl)benzoate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
89%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In tetrahydrofuran; at 60℃; for 20h;Inert atmosphere;
A solution of methyl 3,5-dicyano-4-iodobenzoate (39.7 mg, 0.121 mmol) and 4-ethynyl-N,N-diphenylaniline (39.7 mg, 0.121 mmol) in THF (1 mL) and NEt3 (1 mL) was bubbled with Ar to exclude O2. To that solution was added Pd(PPh3)2Cl2 (3.7 mg, 0.0053 mmol), CuI (10.0 mg, 0.0525 mmol). The mixture was stirred at 60 C for 20 h. After being cooled to room temperature, the reaction mixture was filtered with pads of Celite and Florizil, and the filtrate was evaporated. The residue was dissolved with CHCl3 (10 mL), and the solution was washed with H2O (10 mL × 2) and brine (10 mL). The organic layer was dried with Na2SO4. After filtration and evaporation, the residue was subject to column chromatography on SiO2 (hexane : EtOAc = 3 : 1) to give methyl 3,5-dicyano-4-((4-(diphenylamino)phenyl)ethynyl)benzoate (1) (40.5 mg, 0.0893 mmol, 89%) as yellow solid. Recrystallization from CHCl3 and hexane gave yellow powder: m.p. = 228-229 C; 1H NMR (300 MHz, CDCl3) delta 3.99 (s, 3H), 6.99 (d, J = 8.8 Hz, 2H), 7.14 (t, J = 8.8 Hz, 2H), 7.15 (d, J = 7.8 Hz, 4H), 7.32 (t, J = 8.7 Hz, 4H), 7.53 (d, J = 8.9 Hz, 2H), 8.45 (s, 2H); 13C NMR (75 MHz, CDCl3) delta 53.2, 83.3, 108.8, 111.7, 115.5, 115.9, 120.5, 124.6, 125.8, 129.2, 129.6, 134.1, 134.7, 136.7, 146.4, 150.4, 163.2; IR (KBr disk) 3078, 3034, 2196, 1726, 1583, 1512, 1491, 1323, 1299, 1220, 1147, 755, 697 cm-1. HRMS (ESI) m/z: [M+H]+ Calcd for C30H20N3O2 454.1550; Found 454.1550.
With piperidine; copper(l) iodide; In 1,4-dioxane; at 90℃; for 12h;Inert atmosphere;
General procedure: The appropriate mono-, di- or tri-acetylene TPA derivative(200 mg) and 4-iodopyridine were dissolved in a mixture ofdioxane/piperidine (25 mL, 4/1). Ar was bubbled through themixture for 10 min and [Pd(PPh3)4] and CuI were added. The reactionmixture was stirred at 90 C for 12 h. The cooled reactionmixture was diluted with H2O (50 mL) and extracted with CH2Cl2(2 50 mL). The combined organic extracts were thenwashed withsaturated NH4Cl solution, brine, and dried. Finally, the solventswere evaporated under vacuum and the crude productwas purifiedby column chromatography (SiO2, appropriate eluent). Chromophore 4. The title compound was synthesized from 4-ethynyltriphenylamine (200 mg, 0.743 mmol), 4-iodopyridine(167 mg, 0.817 mmol), [Pd(PPh3)4] (17.16 mg, 0.015 mmol) andCuI (2.83 mg, 0.015 mmol) following the general procedure forSonogashira cross-coupling. Yellow solid. Yield: 231 mg (90%). Rf:0.6 (SiO2, CHCl3/EtOAc 1/1). Mp: 196-197 C. 1H NMR (500 MHz,CDCl3): delta (ppm) 7.00 (d, 2H, 3J 8.5 Hz, CHAr), 7.08 (t, 2H, 3J 7.5 Hz,CHAr), 7.12 (d, 4H, 3J 7.5 Hz, CHAr), 7.28 (t, 4H, 3J 7.5 Hz, CHAr),7.33 (d, 2H, 3J 5.5 Hz, CHPy), 7.37 (d, 2H, 3J 8.5 Hz, CHAr), 8.56 (d,2H, 3J 5.5 Hz, CHPy). 13C NMR (125 MHz, CDCl3): delta (ppm) 86.2,94.9, 114.4, 121.8, 124.1, 125.4, 125.5, 129.7, 132.0, 133.1, 147.1, 148.9,149.9. HR-MALDI-MS (DHB): calcd for C25H18N2 (M) 346.1465,found 346.1473.
With silver nitrate; In toluene; acetonitrile; at 50℃; for 48h;Inert atmosphere;
Decaborane (291 mg, 2.39 mmol) was dissolved in CH3CN (2 mL) at roomtemperature under Ar atmosphere. The mixture was stirred for 1 h at 50 C, and then,dry toluene (20 mL), AgNO3 (25.8 mg, 0.152 mmol) and 4-ethynyltriphenylamine (533mg, 1.98 mmol) were added. The mixture was refluxed for 2 d. After cooling to roomtemperature, the solvent was evaporated, and the residue was subjected to silica gelcolumn chromatography with hexane/CH2Cl2 (v/v = 9/1) as an eluent. Recrystallizationfrom chloroform and methanol (good and poor solvent, respectively) to give 1B as ayellow solid (54.4 mg, 6%).
1-bromo-2-(4-diphenylaminophenylethynyl)naphthalene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
44%
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); diisopropylamine; In toluene; at 40℃; for 16h;
[In the formula,OTf represents a trifluoromethanesulfonyloxy group.Ph represents a phenyl group. The same applies to the following. ]1-Bromonaphthalen-2-yl triflate (3.55 g, 10.0 mmol),4- (N, N-diphenylamino) phenylacetylene (2.96 g, 11.0 mmol),Toluene (20 mL),And diisopropylamine (iPr 2 NH; 10 mL)Degassed by bubbling for 20 minutes.Tetrakis (triphenylphosphine) palladium (0)(Pd (PPh 3) 4; 0.578 g, 0.50 mmol),And CuI (0.095 g, 0.50 mmol) were added,The mixture was stirred at 40 C. for 16 h. Filter to remove inorganic salts,Wash with toluene (30 mL) and evaporate all volatiles under reduced pressure.The mixture was isolated by silica gel column chromatography (5/1 hexane / CH 2 Cl 2, R f = 0.48)The resulting crude product was purified by recrystallization from ethanol (20 mL)Compound 2-1 (1-bromo-2- (4-N, N-diphenylaminophenylethynyl) naphthalene) was obtained as a pale yellow powder(2.11 g, 4.45 mmol, 44%).
Compound 2 (50.00 mg, 0.13 mmol),4-ethynyl-N,N-diphenylaniline 27 (32.00 mg, 0.13 mmol),Pd(PPh3)2Cl2 (7.54 mg, 0.01 mmol), CuI (2.38 mg, 0.01mmol) were dissolved in 2.00 mL toluene and 2.00 mL THF and the resulting mixture was stirred for 10 min. After this,TEA (0.05 mL, 0.38 mmol) was added and the resulting mixture was stirred under N2 atmosphere for 5 h. The reaction mixture was extracted with DCM and organic layer was dried over anhydrous Na2SO4. The organic layer was evaporated under reduced pressure to provide a yellow solid. The crude product was purified by silica column chromatography and eluted with 40% DCM/petroleum ether to provide crude solid (29.60 mg, Yield: 42%); M.p.: 251.6C; IR(neat, cm-1): 2918.00, 2849.00, 2211.00, 1624.00, 1595.00,1513.00, 1492.50, 1464.00, 1451.00, 1314.00, 1268.50,1208.00, 1128.00, 1050.50, 1046.00, 908.50; 1H NMR (500MHz, CDCl3, delta ppm): 8.29 (s, 1H), 7.56 (m, 3H), 7.33 (m,8H) 7.06 (m, 8H), 6.59 (s, 2H), 3.90 (s, 3H); 13C NMR(125 MHz, CDCl3, delta ppm): 160.77, 148.30, 147.13, 139.26,138.75, 133.48, 132.65, 132.55, 129.43, 125.12, 123.71,123.38, 122.11, 114.07, 111.18, 96.14, 87.55, 56.00, 33.82,31.93, 31.63, 29.62, 29.51, 29.16, 28.97, 22.69, 14.10; ESIMS:C34H25BFN2O+2[M-F]+: calcdm/z 523.19, foundm/z523.59.
methyl 2-(4-(diphenylamino)phenyl)benzofuran-6-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
1.5 g
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In acetonitrile; at 40℃; for 2.5h;Inert atmosphere;
To a 100 mL flask was added methyl 2-hydroxy-3-iodobenzoate (1.1 g), 4-ethynyltriphenylamine (1.28 g), bis(triphenylphosphine)palladium dichloride (0.083 g), and copper(l) iodide (0.068 g). The flask was purged with nitrogen for 20 minutes. A solution of triethylamine (2.76 mL) in anhydrous acetonitrile (19.8 mL) was degassed by bubbling nitrogen through for 20 minutes. The triethylamine solution was added to the reaction flask and the reaction heated to 40 C for 2.5 hours. The mixture was cooled to room temperature and water (15 mL) and brine (15 mL) added. The mixture was stirred at room temperature for 1 hour. The layers were then separated and the aqueous layer extracted with ethyl acetate (3x 25 mL). The combined organic fractions were washed with 1 M HCI and brine, dried over magnesium sulfate, filtered and concentrated. The residue was purified via chromatography on silica gel (elution with 0 to 8% ethyl acetate in hexanes) to afford methyl 2-(4-(diphenylamino)phenyl)benzofuran-6-carboxylate (1.5 g). 1 H NMR (400 MHz, Chloroform-d) delta 8.17 (s, 1H), 7.93 (dd, 1H), 7.72 (d, 2H), 7.56 (d, 1H), 7.29 (dd, 5H), 7.19 - 7.05 (m, 7H), 6.91 (d, 1H), 3.94 (s, 3H).
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine; In tetrahydrofuran; at 80℃; for 24h;Inert atmosphere;
Add 1.71 mmol of 4-ethynyltriphenylamine (460 mg) and 0.81 mmol of dendritic group to a 50 mL two-necked flask.Substituted 1,4-diiodobenzene (965 mg), 0.17 mmol of tetrakis(triphenylphosphine)palladium (94 mg), cuprous iodide (15 mg, 0.17 mmol),The system was charged with N2 three times, and then degassed 20 mL of tetrahydrofuran and 10 mL of triethylamine were added under nitrogen to react and mix.After refluxing at 80 C for 24 h, the system was cooled to room temperature, and the filtrate was filtered through celite, dried, and purified by column chromatography.810 mg of an orange solid of the formula II-2, yield: 68%.
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine; In tetrahydrofuran; at 80℃; for 24h;Inert atmosphere;
Add 1.71 mmol of 4-ethynyltriphenylamine (460 mg), 2,5-bis(4-tert-butylbenzyl) to a 50 mL two-necked flask.Oxy)-1,4-diiodobenzene (530 mg, 0.81 mmol), 0.17 mmol of tetrakis(triphenylphosphine)palladium (94 mg),0.17mmol cuprous iodide (15mg),The system was charged with N2 three times, then degassed 20 mL of tetrahydrofuran and 10 mL of triethylamine were added under nitrogen.After refluxing at 80 C for 24 h, the system was cooled to room temperature.The filtrate was filtered through celite, dried, and separated by column chromatography.505 mg of a yellow solid of the formula II-1 were obtained, yield: 67%.
With copper(l) iodide; triethylamine; In methanol; at 50℃; for 8h;Inert atmosphere;
1.0 mmol of the complex precursor and 1.0 mmol of organic monodentate ligand and0.1 mmol of cuprous iodide and 30.0 mmol of triethylamine were placed in a reaction vessel, and 15 mL of methanol was added thereto under a nitrogen atmosphere, and the mixture was heated to 50 C for 8 hours, and then cooled to room temperature to cause precipitation. The precipitate was obtained by suction filtration and washed several times with deionized water, methanol and methyl t-butyl ether.After drying the solvent, a high-purity organometallic platinum complex phosphorescent material Pt2 was obtained in a yield of 68.3%.
9,10-Bis{2-[4-(N,N-diphenylamino)phenyl]ethynyl}anthracene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
1.45 g
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine; In N,N-dimethyl-formamide; at 80℃; for 0.5h;Inert atmosphere;
This embodiment discloses a conjugated alkynyl fluorene derivative, and the synthesis method thereof is as follows:Weigh 9,10-dibromoindole (1.01 g, 3 mmol),Cuprous iodide (28.5 mg, 0.15 mmol),Triphenylphosphine (39.3 mg, 0.15 mmol),Di(triphenylphosphine)palladium dichloride (21.1 mg, 0.01 mmol),Add to a 100 ml three-necked flask equipped with a magnet and a thermometer.20 ml of DMF and 15 ml of TEA were added to dissolve.4-Ethynyltriphenylamine (2.02 g, 7.5 mmol) was weighed.Dissolve in 10 ml DMF and transfer to a constant pressure dropping funnel.After vacuuming under nitrogen for three times, the temperature was raised to 80 C at 5 C / min.A solution of 4-ethynyltriphenylamine in DMF was added dropwise after stirring for half an hour.TCL monitors the 9,10-dibromofluorene raw material and stops heating after the reaction is completed.The reaction solution was cooled to room temperature and solid precipitated, and dried by filtration.The crude product was recrystallized from chloroform to give a yellow powder(1.45g, conversion rate 68%),
2,7-di-tert-butyl-9,17-diphenyl-11-methoxy-12-bromo-dibenzo[de,qr]tetracene[ No CAS ]
[ 205877-26-5 ]
4-((2,7-di-tert-butyl-9,17-diphenyl-11-methoxy)-9,17-diphenyldibenzo[de,qr]tetracene-12-yl)ethynyl-N,N-diphenylamine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With copper(l) iodide; trans-bis(triphenylphosphine)palladium dichloride; triethylamine; triphenylphosphine; In tetrahydrofuran; at 80℃; for 24h;Inert atmosphere;
Under nitrogen protection, 613 mg of 2,7-di-tert-butyl-9,17-diphenyl-11-methoxy-12-bromo-dibenzo[de,qr]tetracene and 205 mg of 4-ethynyltriphenylamine were reacted. Further, 18 mL of tetrahydrofuran and 15 mL of triethylamine were added, and 14 mg of cuprous iodide, 15 mg of triphenylphosphine and 22 mg of bistriphenylphosphorous palladium dichloride were added. Then, the temperature was raised to 80 C, and the reaction was carried out at a temperature of 80 C for 24 h, then cooled to room temperature, saturated brine was added, and the organic phase was extracted with dichloromethane. The solvent was evaporated under reduced pressure and purified by silica gel chromatography. The eluent is a petroleum ether/dichloromethane mixture, the petroleum ether/dichloromethane mixture is a mixture of petroleum ether and dichloromethane, and the volume ratio of petroleum ether to dichloromethane is 8:1. 4-((2,7-di-tert-butyl-9,17-diphenyl-11-methoxy)-9,17-diphenyldibenzo[de,qr]tetracene-12-yl)ethynyl-N,N-diphenylamine.
1-bromo-2-(4-diphenylaminophenylethynyl)naphthalene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
70%
With tetrakis(triphenylphosphine) palladium(0); triethylamine; at 20℃; for 1h;
[Chemical Formula 1-h] was synthesized by the following Reaction Scheme 8.20 g (74 mmol) of the compound represented by the formula (1-c) obtained from the above-mentioned scheme 3 was added to 20 g (60 mmol) of 1-bromo-2- iodonaphthalene, 0.6 g (3 mmol), Pd (PPh3) 4, 1.4 g (1 mmol) was slowly added to a 1 L 3-necked round-bottom flask dissolved in 150 mL of triethylamine. 1 After stirring at room temperature for one hour, 500 mL of normal hexane was added to dilute the solution. The reaction solution was filtered through a Buchner vacuum funnel filled with 200 g of silica gel to remove the catalyst and washed with 1 L of n-hexane. After removing all of the solvent of the filtered solution, a compound represented by the formula (1-h) was obtained. (20 g, 70% yield)
5-((4-(diphenylamino)phenyl)ethynyl)picolinaldehyde[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
67%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In tetrahydrofuran; for 24h;Inert atmosphere; Reflux;
General procedure: The appropriate ethynyl-derivatives (5.1 mmol), 5-bromopicolinaldehyde (1.26 g, 6.8 mmol), Pd(PPh3)2Cl2 (0.21 g, mixture of triethylamine (10 mL) and distilled THF (30 mL) under N2atmosphere. The mixed solution was refluxed for 24 h, and then extractedwith CH2Cl2 solvent and washed by ammonium chloride solution.The resulting solution was evaporated under reduced pressure.The products were purified by column chromatography (EtOAc:PE=1:5).5-(p-tolylethynyl)picolinaldehyde (1)
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In tetrahydrofuran; at 45℃; for 8h;
Compound 4b 1 g (3.73 mmol) CuI in dissolved tetrahydrofuran / triethylamine (1: 1) solution0.0251g (0.135mmol) and Pd (PPh3) 2Cl2 0.094g (0.135mmol)After adding the compound 0.86 g (3.74 mmol) of 4-Iodobenzaldehyde was added and stirred for 8 hours while maintaining the temperature at 45 C. Chromatography after stirring(n-hexane: dichloromethane = 4: 1 (v / v)) separated and purified to give a dark green solid productof (4-Ethynyl-N, N-diphenylaniline) -benzaldehyde (5b) 0.99 g (yield: 58%) was obtained
4,4'-bis(4-diphenylaminophenylethynyl)-6,6'-dimethyl-2,2'-bipyridine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
49.5%
4,4'-Dibromo-6,6'-dimethyl-2,2'-bipyridine (100 mg, 292 mumol, 1.0 eq), Pd(dppf)Cl2 (12.8 mg, 17.5 mumol, 6 mol%), CuI (5.56 mg, 29.2 mumol, 10 mol%), 4-ethynyl-N,N-diphenylaniline (181 mg, 672 mumol, 2.3 eq) and PPh3 (7.66 mg, 29.2 mumol, 10 mol%) were loaded into a heat-dried microwave vial, previously degassed and purged with N2 three times. After 15 min of N2 purging, Et3N (583 muL) was added to the reaction mixture, which was then stirred at 80 C overnight. After cooling to room temperature, the reaction mixture was poured into water (10 mL) and extracted with CH2Cl2 (3 x 10 mL). The organic layers were combined and washed with brine (10 mL). After back-extraction of theaqueous phase, the organic layers were dried over MgSO4 and then dried under reduced pressure. The product was recrystallized from a mixture of EtOH and CHCl3 and isolated as a dark orange powder (104 mg, 145 mumol, 49.5%). 1H NMR (500 MHz, CDCl3): delta/ppm 8.28 (s, 2H, HA3), 7.40 (d, J = 8.7 Hz,4H, HB2), 7.29 (m, 4H, HC3), 7.25 (s, 2H, HA5), 7.13 (d, J = 7.5 Hz, 8H, HC2), 7.09 (t, J = 7.4 Hz, 4H, HC4),7.01 (d, J = 8.9 Hz, 4H, HB3), 2.64 (s, 6H, HMe). 13C{1H} NMR (126 MHz, CDCl3): delta/ppm 158.0 (CA6),148.9 (CB4), 147.0 (CC1), 132.9 (CB2), 129.5 (CC3), 125.2 (CC2), 124.8 (CA5), 123.9 (CC4), 121.8 (CB3), 114.8(CB1), 94.0 (Cb), 86.8 (Ca), 24.7 (CMe); CA2, CA4 not resolved in HMBC. UV-VIS (CHCl3, 2.2 x 10-5 moldm-3) lambda/nm 302 (epsilon/dm3 mol-1 cm-1 41,600), 380 (63,750), 468 (3300). HR EIS-MS m/z 719.3162 [M + H]+(calc. 719.3169). IR spectrum: see Figure S4 in the Supporting Information.
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