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CAS No. : | 6165-69-1 |
Formula : | C4H5BO2S |
M.W : | 127.96 |
SMILES Code : | OB(C1=CSC=C1)O |
MDL No. : | MFCD00151851 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Ethyl 5-bromo-1-benzothiophene-2-carboxylate (2.0 g), 3-thiopheneboronic acid (0.99 g), 1 M potassium carbonate aqueous solution (15 mL) and ethanol (15 mL) were added to toluene (50 mL), and stirred for 30 minutes at room temperature in an argon atmosphere. Tetrakis triphenylphosphine palladium (0.24 g) was added and refluxed for 8 hours. The mixture was extracted with ethyl acetate, the organic layer was washed with water and sodium chloride solution and dried over magnesium sulfate, and the solvent was evaporated. The residue was purified by silica gel column chromatography (elution solvent: ethyl acetate/hexane) to obtain ethyl 5-(3-thienyl)-1-benzothiophene-2-carboxylate (1.9 g) as colorless crystals. 1H-NMR (300MHz, CDCl3) δ 1.43 (3H, t, J = 7.2 Hz), 4.42 (2H, q, J = 7.2 Hz), 7.39-7.49 (2H, m), 7.51-7.52 (1H, m) 7.71(1 H, dd, J = 1.5, 8.5Hz,) 7.88 (1H, d, J = 8.5 Hz), 8.07 (1H, d, J = 1.5 Hz) 8.08 (1H, s) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
(ff) 6-(3-thienyl)-1H-indazole (237 mg, 71%); from 6-iodo-1H-indazole (403.5 mg, 1.65 mmol) and 3-thiopheneboronic acid (236.5 mg, 1.8 mmol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 100℃;Inert atmosphere; | Step 1: synthesis of methyl 3-(thiophen-3-yl)benzoate (82)Nitrogen (gas) was bubbled through the solution of <strong>[618-89-3]methyl 3-bromobenzoate</strong> (50 mg, 0.233 mmol), potassium carbonate (96 mg, 0.698 mmol) and 3-thiopheneboronic acid (59.5 mg, 0.465 mmol) in dioxane (2 mL) and Water (0.2 mL) for 5 minutes.tetrakis(triphenylphosphine)palladium(0) (26.9 mg, 0.023 mmol) was added and again nitrogen was bubbled through the solution for 5 minutes. The reaction mixture was heated overnight at 100C and concentrated to dryness. Purified by chromatography (20% EtOAc in heptane) gave compound methyl 3-(thiophen-3-yl)benzoate 82 (50 mg, 99%). (m/z) = 219 (M+H)+. |
99% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 100℃;Inert atmosphere; | Step 1: synthesis of methyl 3-(thiophen-3-yl)benzoate (82) Nitrogen (gas) was bubbled through the solution of <strong>[618-89-3]methyl 3-bromobenzoate</strong> (50 mg, 0.233 mmol), potassium carbonate (96 mg, 0.698 mmol) and 3-thiopheneboronic acid (59.5 mg, 0.465 mmol) in dioxane (2 mL) and Water (0.2 mL) for 5 minutes. tetrakis(triphenylphosphine)palladium(0) (26.9 mg, 0.023 mmol) was added and again nitrogen was bubbled through the solution for 5 minutes. The reaction mixture was heated overnight at 100 C. and concentrated to dryness. Purified by chromatography (20% EtOAc in heptane) gave compound methyl 3-(thiophen-3-yl)benzoate 82 (50 mg, 99%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87.4% | 2-(thiophen-3-yl)isonicotinaldehyde was prepared using the general boronic acid coupling procedure for 2-bromoisonicotinaldehyde and thiophen-3-ylboronic acid (89 mg, 101.8 mg theoretical, 87.4percent). LC-MS m/z 190.2 (M+1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79.3% | 3-fluoro-6-(thiophen-3-yl)picolinaldehyde was prepared using the general boronic acid coupling procedure for <strong>[885267-36-7]6-bromo-3-fluoropicolinaldehyde</strong> and thiophen-3-ylboronic acid (80.5 mg, 101.5 mg theoretical, 79.3%). LC-MS m/z 208.2 (M+1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; at 80℃; for 12h;Inert atmosphere; | General procedure: The compound TP was prepared by a palladium-catalyzed cross-coupling reaction from 3-bromo-1,10- phenanthroline. First, <strong>[66127-01-3]<strong>[66127-01-3]3-bromo-1,10-phenanthrolin</strong>e</strong> (2.6 g, 10 m ml) in methylbenzene (80 m ml) was stirred in N2 atmosphere. Second, Na2CO3 solution (10 ml, 20 m mol), the mixtures of thiophen-3-yl-3-boronic acid (1.54 g, 12 m mol), methylbenzene (50 m ml) and ethanol (5 ml) were carefully added in turn. Then, the new suspension was left to react for 12 h at 80 C by constant refluxing. The reaction mixture was rotating-evaporated, and was then purified by dissolving with CH2Cl2, water washing, drying with Na2SO4, filtration, concentration and column chromatography (silica gel, CHCl3). Finally, the white solid product (yield, 85%) was obtained after drying in vacuo. FT-IR(KBr, numax/cm-1): 3061 (Ar-H), 2958 (CH), 2918 (CH)], 2850 (CH), 1590, 1559, 1501 (Phen), 731 (CH). 1H NMR (300 MHz, CDCl3): deltaH = 9.40(1H, s, phen), 9.15(1H, s, phen), 8.28(1H, s,phen), 8.16-8.19 (1H, d, phen), 7.75(2H, s, phen), 7.69(1H, s, phen), 7.52(2H, s, thienyl), 7.47(1H, s, thienyl), 7.28(1H, s, CDCl3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | With tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene;Inert atmosphere; Reflux; | <strong>[1075-34-9]5-bromo-2-methyl-1H-indole</strong> (0.5 g, 2.38 mmol) was dissolved in anhydrous toluene (50 mL) and Pd(PPh3)4 (0.12 g, 0.11 mmol) was added. The resulting solution was allowed to stir for 30 min under nitrogen flow. 3-Thiopheneboronic acid (0.45 g, 3.57 mmol) was dissolved in 15 mL absolute ethanol and added to the reaction, followed by saturated 25 mL aqueous NaHCO3. The reaction mixture was heated to reflux overnight. The solvent was evaporated and the residue was dissolved in water and ethyl acetate. The organic portion was dried (MgSO4) and the solvent was removed under reduced pressure. The residue was purified by flash chromatography on silica gel (isooctane/ethyl acetate, gradient) to give the title compound in 84percent yield (0.42 g, 1.96 mmol). MS m/z (relative intensity, 70 eV) 213 (M+, bp), 212 (73),167 (9),139 (4),106(8). 1H NMR (CDCl3, 300 MHz) delta: 2.38 (s, 3H), 6.21 (s, 1H), 7.22 (d,J = 8.23 Hz, 1H), 7.35 (dd, J = 6.30, 0.76, 2H), 7.38-7.46 (m, 1H), 7.72(s, 2H). 13C NMR (CDCl3, 75 MHz) delta: 13.65, 100.70, 110.38, 117.47,118.53, 120.18, 125.61, 126.79, 127.96, 129.52, 135.45, 135.77, 143.81. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; silver trifluoroacetate; In methanol; at 100℃;Schlenk technique; Inert atmosphere; | General procedure: A mixture of N-pyrimidyl indoles 1 (0.20 mmol, 1.0 equiv.), arylboronicacids 2 (0.40 mmol, 2.0 equiv.),AgOOCF3 (0.80 mmol, 4.0 equiv.), and [RhCp*Cl2]2(0.002 mmol, 0.01 equiv.) were combined in MeOH (1.0 mL) in a dried Schlenk tubeunder a argon atmosphere. The resulting mixture was stirred at 60 C andmonitored by TLC. Uponcompletion or no further improvement of reaction, the reaction mixture wascooled to room temperature and added with Et3N (1 mL). Then themixture was filtered through a pad of silica gel eluting with 25 mL of CH2Cl2.The solvent was removed under reduced pressure and the residue was purified byflash chromatography on silica gel to afford the desired products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | With bis(acetylacetonato)palladium(II); 18-crown-6 ether; potassium phosphate tribasic trihydrate; 2-(2,6-dimethylphenyl)-5-(2,4,6-triisopropylphenyl)imidazo[1,5-a]pyridin-2-ium chloride; In 1,4-dioxane; at 130℃; for 48h;Sealed tube; Inert atmosphere; | In a nitrogen atmosphere, 94 mg of the above nitroaromatic hydrocarbon, 115 mg of the above phenylboronic acid, 9.2 mg of Pd(acac) 2, 28 mg of imidazolium salt L5, 480 mg of tripotassium phosphate trihydrate, 7.9 were added to the dried sealed tube. Mg 18-crown-6 and 3 mL dioxane, then tighten the capped screw cap and react at 130 C for 48 h. After the reaction, it was filtered through celite.Concentration and passing through a silica gel column gave product 55 mg (yield: 48%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With palladium bis[bis(diphenylphosphino)ferrocene] dichloride; potassium carbonate; In 1,4-dioxane; water; at 110℃; for 2h;Inert atmosphere; | Compound 15 (10 g), Thiophene boronic acid and K2CO3 were taken in Dioxane (120 ml): Wa- ter(15ml) mixture in a two neck RB flask equipped with Nitrogen balloon and reflux condenser. Reaction mass was degassed for 20 min. Palladium catalyst was added and reaction mass was again degassed for 3 min. Reaction mixture was refluxed at 110C for 2 hrs under Nitrogen. Re- action progress was monitor by TLC. After completion of the reaction, the mixture was filtered through a bed of celite. Filtrate was diluted with ethyl acetate. Ethyl acetate layer was washed with water and brine and concentrated. Crude material was taken in 80 ml methanol and stirred for 45 min at RT. Solid obtained is filtered and wash with cold methanol to get 8.4 g white solid product. (0863) 1H NMR (300 MHz, DMSO-d6) delta 8.50 (s, 1H), 8.40 (s, 1H), 8.22- 8.08 (m, 2H), 7.98 (d, J = 8.3 Hz, 2H), 7.82 (d, J = 8.7 Hz, 1H), 7.70 (d, J = 1.8 Hz, 2H), 7.41 (d, J = 8.2 Hz, 2H), 2.31 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In toluene; at 110.0℃; for 3.0h; | General procedure: To an argon degassed solution of 6-halogeno-2,4-dichloropyrido[2,3-d]pyrimidine 6 or 7 (0.5 mmol) in toluene (6mL) the desired (Het)aryl boronic acid was added then (1.5 equiv)potassium carbonate and (0.05 equiv) Pd(PPh3)4 were also added.The reaction was stirred at 110C for the desired time. After completion of the reaction, 10 mL of water was added, and then extracted with dichloromethane (3 10 mL), the organic layers were combined and dried using magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained material was purified on silica gel by column chromatography (CH2Cl2/PE: 90/10)to afford compounds 8-12. 2,4-Dichloro-6-(4-methoxyphenyl)pyrido[2,3-d]pyrimidine (8) (C14H9Cl2N3O): Compound 8 was obtained from 2,4,6-trichloropyrido[2,3-d]pyrimidine 6 using 4-methoxyphenyl boronic acid (1.05 equiv), as a white solid in 83%yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With palladium diacetate; potassium carbonate; triphenylphosphine; In water; N,N-dimethyl-formamide; at 100℃; for 3h;Microwave irradiation; Inert atmosphere; Sealed tube; | <strong>[16870-28-3]2-hydroxy-4-iodobenzoic acid</strong> (50 mg, 0.189 mmol), 3-thienylboronic acid (29.0 mg, 0.227 mmol), PPh3 (7.4 mg, 0.028 mmol), K2CO3 (91.4 mg, 0.662 mmol), Pd(AcO)2 (2.12 mg, 0.0095 mmol), 1:1 DMF: H2O (2 ml) were used. In this case, prior to chromatographic purification, the residue from evaporating the filtrate was resuspended in acetonitrile. The precipitate was separated from the liquid phase and the latter was discarded. The solid was then purified by flash chromatography (elution with AcOEt: CH3CN:H2O:CH3OH 70:10:5:5 mixture). 87 was obtained in the form of a brown solid. Yield after purification: 87 % (36 mg). 1H NMR (500 MHz, methanol-d4) delta 7.78 (dd, J = 8.4, 4.0 Hz, 1H), 7.61 (dd, J = 2.9, 1.4 Hz, 1H), 7.37 (qd, J = 5.1, 2.2 Hz, 2H), 7.09-7.03 (m, 2H). 13C NMR (126 MHz, methanol-d4) delta 161.82, 141.51, 141.16, 130.82, 126.08, 125.71, 121.53, 116.41, 113.53. HRMS (TOF, ES-): Calculated for C11H7O3S (M-H)-: m/z 219.0116. 219.0122 found (deviation 2.7 ppm). m.p. (C) > 300. |