Structure of 24410-55-7
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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
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CAS No. : | 24410-55-7 |
Formula : | C8H5ClO |
M.W : | 152.58 |
SMILES Code : | ClC1=C(OC=C2)C2=CC=C1 |
MDL No. : | MFCD18207570 |
InChI Key : | AROWSPBDKGWJNQ-UHFFFAOYSA-N |
Pubchem ID : | 90491 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P280-P301+P312-P302+P352-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 |
---|---|---|
75% | With tin-exchanged H-b zeolite (Sn-b); for 4h;Reflux; | General procedure: A 25 mL round-bottomed flask was charged with 2-aryloxyacetaldehyde diethyl acetals (1 mmol), Sn-b (0.1 g), andtrifluorotoluene (10 mL). The mixture was stirred under refluxingcondition and monitored by GC. Upon completion, the mixture wascooled to room temperature, and the catalyst Sn-b was filtrate off.The filter cake was washed with trifluorotoluene (10 mL3). Thecombined filtratewas concentrated under vacuum. The residuewaspurified by flash column chromatography on SiO2 (petroleumether/ethyl acetate) to afford the desired 2,3-unsubstituted benzo[b]furans. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
A mixture of 2 g (13 mmol) 7-chloro-1 -benzofuran in dry THF (100 mL) was cooled to -78C. 7.9 ml (19.7 mmol) of a solution of n-butyllithium in hexane was added and the resulting mixture was stirred for 1 h at -78C. 5.3 mL (19.7 mmol) of tributyltin chloride was added. The reaction was stirred at room temperature over night. Methanol was carefully added and the solvent evaporated. The obtained residue was purified by flash chromatography to yield 6.2 g of crude product of the corresponding 2-stannylbenzofurane, which was used without further purification in step 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
To diisopropylamine (0.280 mL, 1.966 mmol) in THF (4.0 mL) at -78 C wasadded 1.6 N n-BuLi in hexanes (1.229 mL, 1.966 mmol). The reaction mixture wasstirred at -78 C for 0.5 h. 7-Chlorobenzofuran (200 mg, 1.3 11 mmol) in THF (1.0 mL)was added, The reaction mixture was stirred at -78 C for 0.5 h. Iodine (665 mg, 2.62mmol) in THF (1.0 mL) was added dropwise until the brown color persisted (ca 1.3 eq.)The reaction mixture was stirred at -78 C for 0.5 h, then at room temperature for 0.5 h.The reaction mixture was diluted with EtOAc, quenched with saturated ammoniumchloride (5.0 mL) and 10% Na25203 (5.0 mL). After stirring at room temperature for 10 mm, the organic layer was washed with brine, dried over sodium sulfate. After evaporation of solvent, the crude product Intermediate 37A (360 mg, 1.189 mmol, 91 % yield) was obtained as a slightly brown oil. It was used for the next step without furtherpurification. ‘H NMR (400MHz, chloroform-d) 7.40 (dd, J7.7, 1.3 Hz, 1H), 7.24-7.20 (m, 1H), 7.17-7.11 (m, 1H), 6.99 (s, 1H). LC-MS: method H, 2 to 98% B. RT = 1.07mm, MS (ESI) m/z: MW not observed (M+H)t |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | With dirhodium tetraacetate; In 1,2-dichloro-ethane; at 85℃; for 5h;Inert atmosphere; | To a solution of <strong>[24410-55-7]7-chlorobenzofuran</strong> (0.39 niL, 3.28 mmol) in 1 ,2-dichloroethane (5 mL) was added rhodium (II) acetate dimer (72 mg, 0.160 mmol) under nitrogen. The mixture was heated to 85 C and a solution of ethyl diazoacetate (2.0 mL, 16.4 mmol) in 1,2- dichloroethane (5 mL) was added via a syringe pump over 3 hours. The reaction was stirred at 85 C for 2 hours then overnight at 20C. The mixture was concentrated, diluted with water and extracted with ethyl acetate. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and concentrated. The residue was purified by flash column chromatography (0- 100% DCM in hexanes, 50 g S1O2 column) to give rac-( lR,laR,6bS)-ethyl 3-chloro-la,6b- dihydro-lH-cyclopropa[b]benzofuran-l-carboxylate (387 mg, 1.62 mmol, 49% yield). NMR (500 MHz, CDCb) 5 7.28 (dd, J = 7.4, 1.0 Hz, 1H), 7.17 (dd, J = 8.1, 1.2 Hz, 1H), 6.90 - 6.86 (m, 1H), 5.16 (dd, J = 5.4, 1.1 Hz, 1H), 4.21 - 4.12 (m, 2H), 3.31 (dd, J = 5.4, 3.2 Hz, 1H), 1.35 (dd, J = 3.2, 1.1 Hz, 1H), 1.30 - 1.26 (m, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bromine; potassium acetate; In dichloromethane; for 2.68333h;Reflux; | To a mixture of <strong>[24410-55-7]7-chlorobenzofuran</strong> (26.7 g, 175 mmol) and potassium acetate (1.72 g, 17.5 mmol) in DCM (250 mL) was added bromine (9.9 mL, 190 mmol) over 1 min. The mixture was heated at reflux for 2 hrs 40 min, then allowed to cool slowly to room temperature over 50 min. The reaction mixture was diluted with water (100 mL), the layers were separated and the aqueous was extracted with DCM (50 mL). The combined organic extracts were washed with saturated NaHCO3(aq) (100 mL) and brine (100 mL), filtered through a phase separator cartridge and concentrated in vacuo to provide crude 2-bromo-<strong>[24410-55-7]7-chlorobenzofuran</strong> (1) (54.8 g, assumed 175 mmol, 100% yield), which was used without further purification. |
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