Structure of 100590-43-0
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CAS No. : | 100590-43-0 |
Formula : | C10H8O2S |
M.W : | 192.23 |
SMILES Code : | COC(=O)C1=CC=CC2=C1C=CS2 |
MDL No. : | MFCD20527696 |
InChI Key : | LJEKEROHNAFUGD-UHFFFAOYSA-N |
Pubchem ID : | 13448678 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302 |
Precautionary Statements: | P261-P280-P305+P351+P338-P304+P340 |
* 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 |
---|---|---|
84% | With triethylamine;1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; In dimethyl sulfoxide; at 80℃; for 24h; | EXAMPLE 192-[2-(3-piperazin-1-ylpropylamino)-pyrimidin-4-yl]-benzo[b]thiophene-4-carboxylic acid cyclopropylamide tri-hydrochloride(A). Preparation of benzo[b]thiophene-4-carboxylic acid methyl ester; A mixture of 4-bromobenzo[b]thiophene (20.0 g, 93.8 mmol), Pd(OAc)2 (4.26 g, 19.0 mmol), 1,1'-bis(diphenylphosphino)ferrocene (15.4 g, 27.8 mmol) and triethylamine (72.0 mL, 520 mmol) in MeOH (422 mL)/dimethylsulfoxide (DMSO) (638 mL) is introduced to a 1 i high pressure reaction vessel. The vessel is pressurized with 100 psi carbon monoxide (CO) gas, then the mixture is heated at 80 C. for 24 hours. The dark reaction mixture is concentrated to evaporate off MeOH before it is poured onto 2.4 L ice water with stirring to form a suspension. After filtration, the solid is taken up in dichloromethane and the filtrate is extracted with dichloromethane. The combined dichloromethane solution is concentrated to give a dark gum, it is dissolved in dichloromethane (50 mL) and subjected to chromatography on silica gel, eluting with dichloromethane in hexanes 50-100%, to give the title compound as a tan oil (15.2 g, 84% yield). |
44% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; triethylamine; at 120℃;Inert atmosphere; | [196] Into a 30-mL pressure tank reactor (60 atm) purged and maintained with an inert atmosphere of CO, was placed 4-bromo-l-benzothiophene (3 g, 14.08 mmol, 1.00 equiv), PdidppQCh'Q bC (5.8 g, 0.50 equiv), TEA (7.2 g, 71.15 mmol, 5.00 equiv), methanol (15 mL). The resulting solution was stirred overnight at 120 C. The resulting mixture was cooled to room temperature and concentrated under vacuum. The residue was applied onto a silica gel column and eluted with ethyl acetate/petroleum ether (1/10). The collected fraction was concentrated to give 1.18 g (44%) of methyl benzo[b]thiophene-4- carboxylate as a yellow solid. MS (ES, m/z): [M+H]+ : 193 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | (B). Preparation of 2-(2-chloropyrimidin-4-yl)-<strong>[100590-43-0]benzo[b]thiophene-4-carboxylic acid methyl ester</strong>; Lithium diisopropylamide (5.70 mL, 2 M in THF) is added dropwise to a stirred solution of <strong>[100590-43-0]benzo[b]thiophene-4-carboxylic acid methyl ester</strong> (2.00 g, 10.4 mmol) and triisopropyl borate (2.63 mL, 11.4 mmol) in anhydrous THF (20 mL) at -78 C. under nitrogen. Upon the completion of the addition, the mixture is allowed to warm slowly over 1 hour to ambient temperature where it is stirred for another 1 hour. Aqueous Na2CO3 solution (2 M, 15.6 mL) is added to the mixture, followed by the addition of 1,1'-bis(diphenylphosphino)ferrocene (318 mg, 0.570 mmol), palladium(II) acetate (129 mg, 0.570 mmol) and 2,4-dichloropyrimidine (1.46 g, 10.4 mmol). The reaction mixture is heated to reflux for 16 hours. At ambient temperature THF is evaporated off, the aqueous layer is extracted with CHCl3 (100 mL×2) and the combined layers are concentrated to give a dark solid. The solid is dissolved in dichloromethane and purified by chromatography on silica gel, eluting with dichloromethane in hexanes 50-100%, to give the title compound as a yellowish solid (1.60 g, 51% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | [198] Into a 100-mL 3 -necked round-bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed methyl 1 -benzothiophene-4-carboxylate (31 1 mg, 1.62 mmol, 1.00 equiv), tetrahydrofuran (10 mL). The mixture was cooled to -78 C, Then LDA (0.9 mL, 1.10 equiv 2mol/l) was added with dropwise at -78 C. The mixture was stirred for 30 min at -78 C, then Mel was added (253 mg, 1.10 equiv). The resulting solution was stirred overnight at room temperature. The reaction was then quenched by the addition of water/ice (10 mL). The resulting solution was extracted with ethyl acetate (50ml x2), dried over anhydrous sodium sulfate and concentrated under vacuum. The crude product was purified by Prep-TLC with ethyl acetate/petroleum ether (1/1). The collected fraction was concentrated to give 200 mg (60%) of methyl 2-methylbenzo[b]thiophene-4-carboxylate as a yellow solid. MS (ES, m/z): [M+H]+: 207. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
5.8 g | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; triethylamine; In N,N-dimethyl-formamide; at 80℃; under 2585.81 Torr; for 16h; | General procedure: Compound 3b (24.00 g, 102.99 mmol) was dissolved in methanol (300 mL), then N,N-dimethylformamide (100 mL), triethylamine (100 mL) was addedAnd [l,l-bis(diphenylphosphino)ferrocene]dichloropalladium (12.62 g, 15.45 mmol).Reaction solution at 80CAfter stirring for 16 hours under a carbon monoxide atmosphere (50 psi),The reaction solution was filtered, concentrated under reduced pressure, and extracted with ethyl acetate (500 mL×2). The organic phases were combined, dried, concentrated to dryness under reduced pressure and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100-0%) to compound 3c (11.00 g). |
5.80 g | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; triethylamine; In N,N-dimethyl-formamide; at 80℃; under 2585.81 Torr; for 16h; | General procedure: Compound 33b (24.00 g, 102.99 mmol) was dissolved in methanol (300 mL), and N,N-dimethylformamide (100 mL), triethylamine (100 mL), and [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium (12.62g, 15.45 mmol) were added successively. The reaction mixture was stirred under a carbon monoxide atmosphere (50 psi) for 16 hr at 80 C, filtered, concentrated under reduced pressure to dryness, diluted with 100 mL of water, and extracted with ethyl acetate (500 mL×2). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure to dryness, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100-0%) to give Compound 33c (11.00 g). 1H NMR (400 MHz, CDCl3) δ3.95(s, 3H), 3.97(s, 3H), 7.20-7.24 (m, 1H), 8.21-8.23 (m, 1H), 8.63-8.65 (m, 1H). MS-ESI calculated value [M+ H]+ 213, measured value 213. |
5.8 g | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; triethylamine; In N,N-dimethyl-formamide; at 80℃; under 2585.81 Torr; for 16h; | General procedure: Compound 46b (24.00 g, 102.99 mmol) was dissolved in methanol (300 mL), and N,N-dimethylformamide (100 mL), triethylamine (100 mL), and [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium (12.62g, 15.45 mmol) were added. The reaction mixture was stirred under a carbon monoxide atmosphere (50 psi) for 16 hr at 80 C, filtered, concentrated under reduced pressure, and extracted with ethyl acetate (500 mL×2). The organic phases were combined, dried, concentrated under reduced pressure to dryness, and purified by silica gel column chromatography (petroleum ether/ethyl acetate=100-0%), to give Compound 46c (11.00 g). 1H NMR (400 Hz, CDCl3) δ 3.95(s, 3H), 3.97(s, 3H), 7.20-7.24 (m, 1H), 8.21-8.23 (m, 1H), 8.63-8.65 (m, 1H). MS-ESI calculated value [M+ H]+ 213, measured value 213. |
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