* 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 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane at 100℃; for 8 h;
After introducing 2-(4-bromophenyl)-benzoxazole (5 g, 18.2 mmol), bis(pinacolato)diboron (5.1 g, 20.1 mmol) and potassium acetate (5.4 g, 54.7 mmol) in 1,4-dioxane (182 ml, 0.1 M) and suspension stirring the result, Pd(dppf) Cl2 (260 mg, 0.36 mmol) was added thereto, and the result was heated and stirred for 8 hours at 1000 C. After the reaction solution was cooled to room temperature, H20 (100 ml) was added thereto, the result was stirred for 10 minutes and then extracted using THF. The water layer was removed, and the organic layer was treated with magnesium sulfate (Mg504) and then concentrated. The result was crystallized with ethanol (150 ml) and then filtered to obtain a compound of Chemical Formula A (5.3 g, yield 90percent). MS: [M+H]=322
81%
With potassium acetate In 1,4-dioxane at 85℃; for 48 h; Inert atmosphere
[0106] 2-(4-(4,4,5,5-tetramethyl-l ,3,2-dioxaborolan-2- yl)phenyl)benzo[d]oxazole (Compound 28): A mixture of 10 (4.45 g, 16 mmol), bis(pinacolate)diborane (4.09 g, 16.1 mmol), anhydrous potassium acetate (3.14 g, 32 mmol) and Pd(dppf)Cl2 (0.48 g, 0.66 mmol) in anhydrous 1,4-dioxane (80 mL) was degassed and the resulting mixture was heated at about 85 °C for about 48 hours under argon. After cooling to room temperature, the mixture was poured into ethyl acetate (-200 mL) and filtered. The filtrate was absorbed on silica gel and purified by column chromatography (hexanes/ethyl acetate, 4:1) to give a white solid (Compound 28) (4.15 g, in 81percent yield).
2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[d]oxazole (Compound 28): A mixture of 10 (4.45 g, 16 mmol), bis(pinacolate)diborane (4.09 g, 16.1 mmol), anhydrous potassium acetate (3.14 g, 32 mmol) and Pd(dppf)Cl2 (0.48 g, 0.66 mmol) in anhydrous 1,4-dioxane (80 mL) was degassed and the resulting mixture was heated at about 85° C. for about 48 hours under argon. After cooling to room temperature, the mixture was poured into ethyl acetate (~200 mL) and filtered. The filtrate was absorbed on silica gel and purified by column chromatography (hexanes/ethyl acetate, 4:1) to give a white solid (Compound 28) (4.15 g, in 81percent yield).
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In toluene; for 4.0h;Reflux; Inert atmosphere;
2-(4-Bromophenyl)benzo[d]azole (10 parts), bis(pinacol)diboron (10.8 parts), potassium acetate (6.9 parts) and [1,1'-double ( Diphenylphosphino)ferrocene]palladium(II) chloride dichloride adduct (1.0 part) was mixed in toluene (500 parts), and stirred at reflux temperature for 4 hours under a nitrogen atmosphere.After the obtained reaction liquid was cooled to room temperature, 20 parts of tannin was added, and the mixture was stirred for 5 minutes.Then, by separating the solid fraction by filtration, and removing the solvent under reduced pressure,2-(Benzo[d]oxazol-2-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane pentane (11.4 parts, yield 99%).
90%
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 100.0℃; for 8.0h;
After introducing 2-(4-bromophenyl)-benzoxazole (5 g, 18.2 mmol), bis(pinacolato)diboron (5.1 g, 20.1 mmol) and potassium acetate (5.4 g, 54.7 mmol) in 1,4-dioxane (182 ml, 0.1 M) and suspension stirring the result, Pd(dppf) Cl2 (260 mg, 0.36 mmol) was added thereto, and the result was heated and stirred for 8 hours at 1000 C. After the reaction solution was cooled to room temperature, H20 (100 ml) was added thereto, the result was stirred for 10 minutes and then extracted using THF. The water layer was removed, and the organic layer was treated with magnesium sulfate (Mg504) and then concentrated. The result was crystallized with ethanol (150 ml) and then filtered to obtain a compound of Chemical Formula A (5.3 g, yield 90%). MS: [M+H]=322
81%
With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 85.0℃; for 48.0h;Inert atmosphere;
[0106] 2-(4-(4,4,5,5-tetramethyl-l ,3,2-dioxaborolan-2- yl)phenyl)benzo[d]oxazole (Compound 28): A mixture of 10 (4.45 g, 16 mmol), bis(pinacolate)diborane (4.09 g, 16.1 mmol), anhydrous potassium acetate (3.14 g, 32 mmol) and Pd(dppf)Cl2 (0.48 g, 0.66 mmol) in anhydrous 1,4-dioxane (80 mL) was degassed and the resulting mixture was heated at about 85 C for about 48 hours under argon. After cooling to room temperature, the mixture was poured into ethyl acetate (-200 mL) and filtered. The filtrate was absorbed on silica gel and purified by column chromatography (hexanes/ethyl acetate, 4:1) to give a white solid (Compound 28) (4.15 g, in 81% yield).
With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 100.0℃;
Intermediate 10 2-[4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3-benzoxazole <n="29"/>Intermediate 9 (0.8 g), potassium acetate (0.86 g), bis(pinacolato)diboron (1.1 g) and PdCI2(dppf) (160 mg) were dissolved in anhydrous dioxane (16 ml_) and were heated at 1000C overnight. The reaction mixture was evaporated to dryness and the residue partitioned between water and DCM. The aqueous phase was separated and extracted twice with DCM. The combined organic phases were dried using a hydrophobic frit and evaporated to dryness. This was purified by ISCO Companion silica chromatography eluting with a gradient of ethyl acetate in cyclohexane to give the title compound. MS calcd for (C19H20BNO3 + H)+ : 322 MS found (electrospray) : (M+H)+ = 322
With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; for 48.0h;Inert atmosphere;
[0084] 2-(4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2- yl)phenyl)benzo[d]oxazole (11): A mixture of 10 (4.45 g, 16 mmol), bis(pinacolate)diborane (4.09 g, 16.1 mmol), anhydrous potassium acetate (3.14 g, 32 mmol) and Pd(dppf)Cl2 (0.48 g, 0.66 mmol) in anhydrous 1,4-dioxane (80 mL) was degassed and heated at about 85 C for about 48 hours under argon. After cooling to room temperature, the mixture was poured into ethyl acetate (-200 mL) and filtered. The filtrate was absorbed on silica gel and purified by column chromatography (hexanes/ethyl acetate, 4: 1) to give a white solid (4.15 g, in 81% yield).
methyl 5-bromo-2-[[(trans-4-methylcyclohexyl)carbonyl](1-methylethyl)amino]-3-thiophenecarboxylate[ No CAS ]
[ 439090-73-0 ]
methyl 5-[4-(1,3-benzoxazol-2-yl)phenyl]-2-[[(trans-4-methylcyclohexyl)carbonyl](1-methylethyl)amino]-3-thiophenecarboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; N,N-dimethyl-formamide; at 100.0℃; for 5.0h;
Intermediate 13Methyl 5-[4-(1 ,3-benzoxazol-2-yl)phenyl]-2-[[(frans-4-methylcyclohexyl)carbonyl](1 - methylethyl)amino]-3-thiophenecarboxylateIntermediate 3 (150 mg), Intermediate 10 (167 mg), Pd(PPh3)4 (58 mg) and Na2CO3 (158 mg in aqueous solution) were dissolved in DMF (14 mL) and were heated at 1000C for 5 h.The reaction mixture was evaporated to dryness and the residue partitioned between water and DCM. The aqueous phase was separated and extracted twice more with DCM. The combined organic phases were dried using a hydrophobic frit and evaporated to dryness.This was purified by ISCO Companion silica chromatography eluting with a gradient of ethyl acetate in cyclohexane to give the title compound.MS calcd for (C30H32N2O4S + H)+ : 517 MS found (electrospray) : (M+H)+ = 517
With potassium acetate;Pd(dppf)Cl2; In 1,4-dioxane;
2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[d]oxazole (Compound 28): A mixture of 10 (4.45 g, 16 mmol), bis(pinacolate)diborane (4.09 g, 16.1 mmol), anhydrous potassium acetate (3.14 g, 32 mmol) and Pd(dppf)Cl2 (0.48 g, 0.66 mmol) in anhydrous 1,4-dioxane (80 mL) was degassed and the resulting mixture was heated at about 85 C. for about 48 hours under argon. After cooling to room temperature, the mixture was poured into ethyl acetate (~200 mL) and filtered. The filtrate was absorbed on silica gel and purified by column chromatography (hexanes/ethyl acetate, 4:1) to give a white solid (Compound 28) (4.15 g, in 81% yield).
With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water;Inert atmosphere; Reflux;
[0114] Compound 36: A mixture of 35 (1.40 g, 3.5 mmol), Compound 28(1.52 g, 3.85 mmol), Na2CO3 (1.32g, 12.5 mmol) and Pd(PPh3)4 (121 mg, 0.105 mmol) in THF/H2O (21 mL/12.5 mL) was degassed and the resulting mixture was heated at reflux overnight under argon atmosphere. After cooling to room temperature, the resulting mixture was poured into dichloromethane (150 mL), then washed with water (150 mL) and brine (150 mL). The organic phase was dried over Na2SO4, absorbed on silica gel, and purified with flash column chromatography (hexane/ethyl acetate 5:1 to 2:1, then dichoromethane as eluent). The product was collected and recrystallized from acetone/hexanes to give a solid (1.69g). It was recrystallized again in dichoromethane/ethyl acetate to give a solid (Compound 36) (1.4 g, 68% yield).
With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 80.0℃;Inert atmosphere;
[0107] Compound 29: A mixture of Compound 28 (0.66 g, 2.05 mmol), Compound 22 (0.80 g, 1.87 mmol), Na2CO3 (0.708 g, 6.68 mmol) and Pd(PPh3)4 (0.065 g, 56.1 mmol) in THF/H2O (10 mL/6 mL) was degassed and the resulting mixture was heated at about 80 0C overnight under argon atmosphere. After cooling, the resulting mixture was poured into dichloromethane (100 mL) and washed with water (2x 200 mL) and brine (100 mL). The organic phase was collected, dried over Na2SO4, then purified by flash chromoatography (silica gel, hexanes/ethyl acetate 40: 1 to 9: 1) to give a solid (Compound 29) (0.936 g, in 93% yield).
With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 85.0℃;Inert atmosphere;
[0109] Compound 31: A mixture of 9-(4'-bromobiphenyl-4-yl)-9H-carbazole (Compound 30) (1.6 g, 4.03 mmol), Compound 28 (1.42 g, 4.43 mmol), Na2CO3 (1.53 g, 14.39 mmol) and Pd(PPh3)4 (0.14 g, 0.121 mmol) in THF/H2O (24 mL/14 mL) was degassed and the resulting mixture was heated to about 85 0C overnight under argon atmosphere. After cooling, the resulting mixture was poured into dichloromethane (200 mL), and washed with water (2x 150 mL) and brine (150 mL). The organic phase was collected and dried over Na2SO4, and concentrated to form a grey precipitate. Filtration gave a filtrate (A) and solid, which was redissolved in chloroform (550 niL) and filter off suspended particles, the clear filtrate (B) was kept at -15 C overnight to form a white solid (1.19g). The filtrate (C) was combined with the Filtrate A and absorbed on silica gel, purified by flash chromatography (dichloromethane) give an additional 0.52 g solid. Both solids were combined and washed with hot ethyl acetate, and filtered to yield the product (Compound 31)(1.66g, 81% yield).
With KF; potassium acetate;Pd(dppf)Cl2; In 1,4-dioxane; dichloromethane; chloroform; ethyl acetate; N,N-dimethyl-formamide;
2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[d]oxazole (11): A mixture of 10 (4.45 g, 16 mmol), bis(pinacolate)diborane (4.09 g, 16.1 mmol), anhydrous potassium acetate (3.14 g, 32 mmol) and Pd(dppf)Cl2 (0.48 g, 0.66 mmol) in anhydrous 1,4-dioxane (80 mL) was degassed and heated at about 85 C. for about 48 hours under argon. After cooling to room temperature, the mixture was poured into ethyl acetate (~200 mL) and filtered. The filtrate was absorbed on silica gel and purified by column chromatography (hexanes/ethyl acetate, 4:1) to give a white solid (4.15 g, in 81% yield). Host-4 (12): A mixture of 3,6-dibromo-9-p-tolyl-9H-carbazole (2.62 g, 6.35 mmol), 10 (4.08 g, 12.7 mmol), Pd(dppf)Cl2 and KF (2.21 g, 38 mmol) in DMF (100 mL) was heated at about 120 C. under argon overnight. After the mixture was cooled to room temperature, it was poured into water (~200 mL) and filtered. The solid was collected and redissolved in chloroform (~200 mL). After the water was removed the chloroform solution was dried over Na2SO4. The chloroform solution was absorbed on silica gel, purified by column chromatography (with gradient of dichloromethane to dichloromethane/ethyl acetate 20:1), and recrystallized in dichloromethane to give a pale yellow crystalline solid (1.5 g, in 37% yield).
With potassium fluoride;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,2-dimethoxyethane;Inert atmosphere;
[0085] Host-4 (12): A mixture of 3,6-dibromo-9-p-tolyl-9H-carbazole (2.62 g, 6.35 mmol), 10 (4.08 g, 12.7 mmol), Pd(dppf)Cl2 and KF (2.21 g, 38 mmol) in DMF (100 mL) was heated at about 120 C under argon overnight. After the mixture was cooled to room temperature, it was poured into water (-200 mL) and filtered. The solid was collected and redissolved in chloroform (-200 mL). After the water was removed the chloroform solution was dried over Na2S04. The chloroform solution was absorbed on silica gel, purified by column chromatography (with gradient of dichloromethane to dichloromethane/ethyl acetate 20: 1), and recrystallized in dichloromethane to give a pale yellow crystalline solid (1.5 g, in 37% yield).
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; at 90.0℃; for 12.0h;
18.0 g (38.6 mmol) of the intermediate product (N), 14.9 g (46.4 mmol) of <strong>[439090-73-0]2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-phenyl)benzooxazole</strong>, and 1.3 g (1.2 mmol) of tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] were dissolved in 360 ml of a tetrahydrofuran (THF) solvent. A solution in which 21.4 g (154.5 mmol) of potassium carbonate (K2CO3) was dissolved in 180 ml of water was added thereto, and then they were reacted at 90 C. for 12 hours. The solvent was removed under a reduced pressure, and the reaction product was rinsed with water and methanol. The residues were recrystallized with toluene, precipitated crystals were separated by a filter, rinsed with toluene, and dried to provide a white solid of a compound in 21.0 g (yield: 87%). (calculation value: 624.73, measurement value: MS[M+1] 625.03)
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 95.0℃; for 48.0h;
6 (3 g, 6.9 mmol), 1-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole (3.3 g, 10.36 mmol), Palladium tetrakis triphenylphoshine (1.2 g) and 30 mL of a 1M potassium carbonate solution in water were introduced in a flask together with 100 mL toluene. This mixture is stirred at 95 C. during 48 hours before being let cooled to room temperature and filtered with a paper filter. The solid is then washed with toluene, and the obtain grey solid is dissolved in 500 ml of hot (150 C.) xylene, this suspension is filtered over a celite pad and the volatiles are then removed by rotary evaporation. The obtained solid is then dried in a vacuum oven. Yield: 2.4 g (65%).HPLC: >98%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; toluene;Reflux;
A 500 mL flask was charged with 5.0 g (0.011 mol) of intermediate (3)Int.22 3.5 g (0.011 mol) of Pd (PPh3) 4, 0.4 g (0.323 mmol) of Pd (PPh3) 4 and 200 mL of toluene were added to the solution. 100 mL of ethanol and 100 mL of K2CO3 2.2 (0.016 mol) And the mixture was stirred for 7 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, followed by extraction with DCM. The organic phase was dried over anhydrous MgSO4, The residue was purified by silica gel column chromatography to obtain 3.0 g (yield: 48%) of Compound 4-68 (WS15-30-266) as a white solid.
48%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; for 7.0h;Reflux;
A 500 mL flask was charged with 5.0 g (0.011 mol) of intermediate (3) Int.22 3.5 g (0.011 mol),0.4 g (0.323 mmol) of Pd (PPh3) 4,toluene (200 mL), stir with 100 mL of ethanol,100 mL of K2CO3 2.2 (0.016 mol) / H2O was added,And the mixture was stirred under reflux for 7 hours.After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, followed by extraction with DCM. The organic phase was dried over anhydrous MgSO4,The residue was purified by silica gel column chromatography to obtain 3.0 g (yield: 48%) of Compound 4-68 (WS15-30-266) as a white solid.
4-([1,1'-biphenyl]-4-yl)-6-(2-bromophenyl)-2-phenylpyrimidine[ No CAS ]
[ 439090-73-0 ]
C41H27N3O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
46.9%
With palladium diacetate; potassium carbonate; In water; toluene; at 90.0℃; for 12.0h;
4.0 g (8.63 mmol) of Intermediate (8) and 3.05 g (9.50 mmol) of Int.22,Pd (OAc) 2 194 mg (864) and2 N aq. To 56 mL (112.2 mmol) of K2CO3 was added 86 mL of toluene and the mixture was stirred at 90 DEG C for 12 hours.After the temperature of the reaction mixture was lowered to room temperature, 150 mL of dichloromethane and 60 mL of water were added to separate the organic layer, and the organic layer was washed with water and concentrated under reduced pressure.The resulting reaction mixture was purified by silica gel column chromatography to obtain 2.34 g (yield: 46.9%) of a white solid compound 4-117 (WS15-30-265).
4-([1,1′-biphenyl]-4-yl)-6-(4-bromophenyl)-2-phenylpyrimidine[ No CAS ]
[ 439090-73-0 ]
C41H27N3O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
46.9%
With palladium diacetate; potassium carbonate; In water; toluene; at 90.0℃; for 12.0h;
4.0 g (8.63 mmol) of intermediate (2) andInt. 22 3.05 g (9.50 mmol) of 194 mg (864) of Pd (OAc) 2 and 2 N aq. To 56 mL (112.2 mmol) of K2CO3 was added 86 mL of toluene and the mixture was stirred at 90 for 12 hours.After the temperature of the reaction mixture was lowered to room temperature,After separation by adding 150 mL of dichloromethane and 60 mL of water, the organic layer was washed with water and concentrated under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography to obtain 2.34 g (yield: 46.9%) of a white solid compound 4-142 (WS15-30-269).
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 8.0h;Reflux;
After the compound of Chemical Formula A (10 g, 31.1 mmol) and 1-bromo-3,5-diphenylbenzene (9.6 g, 31.1 mmol) were suspension stirred in THF (310 ml), K2C03 (8.6 g, 62.3 mmol) dissolved in H20 (100 ml), and then tetrakis (triphenylphosphine) palladium(0) (720 mg, 0.62 mmol) were added thereto, and the result was refluxed for 8 hours. Afier the reaction was complete, the temperature was lowered to room temperature, the water layer was removed, and the organic layer was treated with magnesium sulfate (Mg504) and then filtered. The solution was vacuum concentrated under reduced pressure, and colunm purified with a ratio of THF/Hexane=1/3 to obtain a compound of Chemical Formula 1-4 (10 g, yield: 76%). MS: [M+H]=424
2,4‐bis([1,1'‐biphenyl]‐4‐yl})‐6‐chloro‐1,3,5‐triazine[ No CAS ]
[ 439090-73-0 ]
C40H26N4O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 8.0h;Reflux;
General procedure: After the compound of Chemical Formula A (10 g, 31.1 mmol) and 1-bromo-3,5-diphenylbenzene (9.6 g, 31.1 mmol) were suspension stirred in THF (310 ml), K2C03 (8.6 g, 62.3 mmol) dissolved in H20 (100 ml), and then tetrakis (triphenylphosphine) palladium(0) (720 mg, 0.62 mmol) were added thereto, and the result was refluxed for 8 hours. Afier the reaction was complete, the temperature was lowered to room temperature, the water layer was removed, and the organic layer was treated with magnesium sulfate (Mg504) and then filtered. The solution was vacuum concentrated under reduced pressure, and colunm purified with a ratio of THF/Hexane=1/3 to obtain a compound of Chemical Formula 1-4 (10 g, yield: 76%). MS: [M+H]=424
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 8.0h;Reflux;
After the compound of Chemical Formula A (10 g,31.1 mmol) and 2,6-dibromo-N-(2-naphthyl)carbazole (7.0 g, 15.6 mmol) were suspension stirred in THF (310 ml), K2C03 (8.6 g, 62.3 mmol) dissolved in H20 (100 ml), and then tetrakis(triphenylphosphine) palladium(0) (720 mg, 0.62 mmol) were added thereto, and the result was refluxed for 8 hours. After the reaction was complete, the temperature was lowered to room temperature, the water layer was removed, and the organic layer was treated with magnesium sulfate (MgSO4) and then filtered. The solution was vacuum concentrated under reduced pressure, and column purified with a ratio of THF/Hexane=1/2 to obtain a compound of Chemical Formula 1-51 (8.7 g, yield: 80%).MS: [M+H]=680
2,7-bis(4-(benzo[d]oxazol-2-yl)phenyl)[1]benzothieno[3,2-b][1]benzothiophene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
57%
With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In water; N,N-dimethyl-formamide; at 80.0℃; for 5.0h;Inert atmosphere;
Water (11 parts), 2,7-diiodo[1]benzothieno[3,2-b][1]benzothiophene (4.9 parts) synthesized by the method described in Japanese Patent No. 4945757,2-(Benzo[d]oxazol-2-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane pentane (8.0 parts) obtained in Step ),Tripotassium phosphate (34 parts) and hydrazine (triphenylphosphine) palladium (0.8 parts) were mixed in DMF (430 parts), and stirred at 80 C for 5 hours under a nitrogen atmosphere.After cooling the obtained reaction liquid to room temperature, water (430 parts) was added, and the solid fraction was separated by filtration.By purifying the obtained solid fraction with acetone and purifying it after sublimation,The compound (3.6 parts, yield 57%) represented by No. 30 of the above specific example was obtained.
With potassium phosphate; palladium diacetate; In N,N-dimethyl-formamide; at 150.0℃;Inert atmosphere;
In a 250 mL three-necked flask, nitrogen gas was introduced, and 0.01 mol of intermediate E1, 150 ml of DMF, and 0.015 mol were added.Body B1, 0.0001 mol of palladium acetate, stirred, then added 0.01 mol of K3PO4 aqueous solution, heated to 150 C, refluxed for 24 hours, sampled the plate, and the reaction was completed.It is naturally cooled, extracted with 200 ml of dichloromethane, and the layers are separated. The extract is dried over anhydrous sodium sulfate, filtered, and the filtrate is evaporated to silicaThe HPLC purity was 99.3%, and the yield was 58.7%.
With potassium phosphate; palladium diacetate; In water; N,N-dimethyl-formamide; at 150.0℃; for 24.0h;Inert atmosphere;
In a 250mL three-neck bottle,Passing nitrogen,Add 0.01 mol of intermediate A1,150ml of DMF, 0.03molRaw material B1,0.0002 mol of palladium acetate, stirred, then added 0.02 mol of K3PO4 aqueous solution, heated to 150 C, refluxed for 24 hours, sampling the plate, the reaction was complete. It is naturally cooled, extracted with 200 ml of dichloromethane, and the layers are separated. The extract is dried over anhydrous sodium sulfate, filtered, and the filtrate is evaporated to dryness.The HPLC purity was 99.2%, and the yield was 53.6%.
With potassium phosphate; palladium diacetate; In water; N,N-dimethyl-formamide; at 150.0℃; for 24.0h;Inert atmosphere;
In a 250 mL three-necked flask, nitrogen gas was introduced, 0.01 mol of intermediate A12, 150 ml of DMF, 0.012 mol of raw material B1, 0.0001 mol of palladium acetate, and stirred, and then 0.012 mol of K3PO4 aqueous solution was added thereto, and the mixture was heated to 150 C, and refluxed for 24 hours.When the plate is sampled, the reaction is complete. Naturally cooled, extracted with 200 ml of dichloromethane, layered, and the extract was dried over anhydrous sodium sulfateDrying, filtration, and rotary evaporation of the filtrate were purified by silica gel column to give the desired product. The HPLC purity was 99.4% and the yield was 60.8%.
With potassium phosphate; palladium diacetate; In N,N-dimethyl-formamide; at 150.0℃; for 24.0h;Inert atmosphere;
In a 250 mL three-necked flask, nitrogen gas was introduced, 0.01 mol of intermediate A2, 150 ml of DMF, 0.03 mol of intermediate B1, 0.0002 mol of palladium acetate were added, stirred, and then 0.02 mol of K3PO4 aqueous solution was added, heated to 150 C, refluxed for 24 hours, and sampled. Point plate, the reaction is complete. It is naturally cooled, extracted with 200 ml of dichloromethane, and the layers are separated. The extract is dried over anhydrous sodium sulfate, filtered, and the filtrate is evaporated to silicaThe HPLC purity was 99.1%, and the yield was 67.2%.
With potassium phosphate; palladium diacetate; In N,N-dimethyl-formamide; at 150.0℃; for 24.0h;Inert atmosphere;
In a 250 mL three-necked flask, nitrogen gas was introduced, 0.01 mol of intermediate A1, 150 ml of DMF, 0.03 mol of intermediate B1, 0.0002 mol of palladium acetate were added, stirred, and then 0.02 mol of K3PO4 aqueous solution was added, heated to 150 C, refluxed for 24 hours, and sampled. Point plate, the reaction is complete. It is naturally cooled, extracted with 200 ml of dichloromethane, and the layers are separated. The extract is dried over anhydrous sodium sulfate, filtered, and the filtrate is evaporated to silicaThe HPLC purity was 99.4%, and the yield was 64.7%
With potassium phosphate; palladium diacetate; In N,N-dimethyl-formamide; at 150.0℃; for 24.0h;Inert atmosphere;
In a 250 mL three-necked flask, nitrogen gas was introduced, 0.01 mol of intermediate A13, 150 ml of DMF, 0.03 mol of intermediate B1, 0.0002 mol of palladium acetate were added, stirred, and then 0.02 mol of K3PO4 aqueous solution was added, heated to 150 C, refluxed for 24 hours, and sampled. Point plate, the reaction is complete. It is naturally cooled, extracted with 200 ml of dichloromethane, and the layers are separated. The extract is dried over anhydrous sodium sulfate, filtered, and the filtrate is evaporated to silicaThe HPLC purity was 99.3%, and the yield was 65.4%.
With anhydrous potassium acetate; Palladium(0) bis(dibenzylideneacetone); tricyclohexylphosphine In 1,4-dioxane Inert atmosphere; Reflux;
1 Synthesis of intermediate C2:
In a 500 mL three-mouth bottle, nitrogen was added, 0.03 mol of raw material 2-(4-chlorophenyl)benzo[d][1,3] oxazide azetidyl, 0.05 mol of divaleryl diboron, 0.0015 potassium acetate (KOAc), 300 ml of 1,4-dioxane, under the condition of reflux stirring, 0.00068mol of dibenzylpropione palladium (Pd(dba)2) and 0.00023mol tricyclohexylphosphine (PCy3), stirred to the end of the reaction. Water and chloroform were added at room temperature for extraction, dried and distilled after layering, and recrystallized, naturally cooled, water was added, the mixture was filtered and dried in a vacuum drying box, and the resulting residue was purified by the silica gel column to give compound intermediate C1; HPLC purity was 99.7, yield 85%.
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
For Research Only
110K+ Compounds
Competitive Price
1-2 Day Shipping
