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CAS No. : | 881189-74-8 | MDL No. : | MFCD14654077 |
Formula : | C9H6BrFO | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | FVPXVDTWEBFLLE-UHFFFAOYSA-N |
M.W : | 229.05 | Pubchem ID : | 50989426 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | |
Hazard Statements: | H302 | Packing Group: | |
GHS Pictogram: |
* 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 |
---|---|---|
With triethylsilane; trifluoroacetic acid; at 20℃; | To a solution of 6-bromo-4-fluoroindan-l-one (57 mg, 0.26 mmol) in trifluoroacetic acid (1.1 mL) was added triethylsilane (103 ih, 0.65 mmol), and the mixture was stirred at room temperature overnight. The reaction solution was poured into ice water, and the mixture was extracted with ethyl acetate three times. The organic layer was combined, washed with saturated aqueous sodium hydrogen carbonate solution, and the organic layer was filtered through Phase-separator (Varian Inc.), and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate = 100:0) to give a crude 6-bromo-4-fluoroindane (61 mg) as a yellow oil. The resultant was used in the next step without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With copper(l) iodide; caesium carbonate; N,N`-dimethylethylenediamine; In 1,4-dioxane; at 85℃; for 3h;Inert atmosphere; | Alternative Preparation of (R)-3-[6-(2-Cyclopropyl-ethoxy)-pyridin-3-yloxv]-1-(7-fluoro-3-oxo-indan-5-yl)-pyrrolidin-2-one (Example 1-08) A mixture of (R)-3-[6-(2-cyclopropyl-ethoxy)-pyridin-3-yloxy]-pyrrolidin-2-one (100 mg), <strong>[881189-74-8]6-bromo-4-fluoro-2,3-dihydro-1H-inden-1-one</strong> (87 mg) and 1,4-dioxane (2 mL) was purged with argon. N,N'-Dimethyl-ethylene-diamine (336 mg), cesium carbonate (248 mg) and copper(I) iodide (7 mg) were added. The mixture was heated to 85 C. for 3 hours. After cooling to r.t. the mixture was filtered and the filtrate purified by preparative HPLC to provide Example 1-08. 1H-NMR (400 MHz, DMSO) 67.99 (1H, dd, J=11.3, 1.8 Hz), 7.97 (1H, d, J=3.1 Hz), 7.77 (1H, d, J=1.8 Hz), 7.53 (1H, dd, J=9.0, 3.1 Hz), 6.77 (1H, d, J=9.0 Hz), 5.22 (1H, dd, J=8.3, 8.3 Hz), 4.24 (2H, t, J=6.8 Hz), 3.96 (1H, m), 3.86 (1H, m), 3.10 (2H, m), 2.72 (2H, m), 2.69 (1H, m), 2.14 (1H, m), 1.60 (2H, dt, J=6.8, 6.8 Hz), 0.80 (1H, m), 0.42 (2H, m), 0.10 (2H, m). | |
With copper(l) iodide; caesium carbonate; N,N`-dimethylethylenediamine; In 1,4-dioxane; at 85℃; for 3h;Inert atmosphere; | A mixture of (R)-3-[6-(2-cyclopropyl-ethoxy)-pyridin-3-yloxy]-pyrrolidin-2-one (100 mg), 6-bromo-4-fluoro-2,3-dihydro-1 H-inden-1 -one (87 mg) and 1 ,4-dioxane (2 mL) was purged with argon. Lambda/,Lambda/'-Dimethyl-ethylene-diamine (336 mg), cesium carbonate (248 mg) and copper(l) iodide (7 mg) were added. The mixture was heated to 85C for 3 hours. After cooling to r.t. the mixture was filtered and the filtrate purified by preparative HPLC to provide Example 1 -08. 1H-NMR (400 MHz, DMSO) 5 7.99 (1 H, dd, J = 1 1 .3, 1 .8 Hz), 7.97 (1 H, d, J = 3.1 Hz), 7.77 (1 H, d, J= 1 .8 Hz), 7.53 (1 H, dd, J= 9.0, 3.1 Hz), 6.77 (1 H, d, J = 9.0 Hz), 5.22 (1 H, dd, J = 8.3, 8.3 Hz), 4.24 (2H, t, J = 6.8 Hz), 3.96 (1 H, m), 3.86 (1 H, m), 3.10 (2H, m), 2.72 (2H, m), 2.69 (1 H, m), 2.14 (1 H, m), 1 .60 (2H, dt, J = 6.8, 6.8 Hz), 0.80 (1 H, m), 0.42 (2H, m), 0.10 (2H, m). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With copper(l) iodide; caesium carbonate; N,N`-dimethylethylenediamine; In 1,4-dioxane; at 100℃; for 1.5h;Inert atmosphere; | Alternative Preparation of (R)-3-(6-Ethoxy-pyridin-3-yloxy)-1-(7-fluoro-3-oxo-indan-5-yl)-pyrrolidin-2-one (Example 2-08) To a mixture of (R)-1-(7-fluoro-3-oxo-indan-5-yl)-3-(6-hydroxy-pyridin-3-yloxy)-pyrrolidin-2-one (60 mg), ethanol (23 mg) and solvent (THF/DCM/NMP 4:4:1, 5 mL) under argon was added triphenylphosphine (polymer, 0.4 mmol). After 5 minutes DIAD (51 mg) was added. The mixture was shaken at 40 C. for 12 hours. The mixture was filtered and the filtrate was concentrated. The residue was purified by preparative HPLC to provide Example 2-08. In a further alternative preparation a mixture of (R)-3-((6-ethoxypyridin-3-yl)oxy)pyrrolidin-2-one (2.00 g), <strong>[881189-74-8]6-bromo-4-fluoro-2,3-dihydro-1H-inden-1-one</strong> (2.30 g), N,N'-dimethyl-ethylene-diamine (10 mL) and 1,4-dioxane (20 mL) was purged with argon and cesium carbonate (3.8 g) and copper(I) iodide (100 mg) were added. The mixture was heated to 100 C. for 1.5 hours. After cooling to r.t. the mixture was diluted with EA and washed with water (5 times) and brine. The organic layer was dried (Na2SO4) and concentrated. The residue was purified by SGC (eluent: heptane with 0 to 70% EA) to provide Example 2-08. 1H-NMR (400 MHz, DMSO) delta 7.99 (1H, dd, J=11.3, 1.8 Hz), 7.97 (1H, d, J=3.1 Hz), 7.77 (1H, d, J=1.8 Hz), 7.53 (1H, dd, J=8.9, 3.1 Hz), 6.76 (1H, d, J=8.9 Hz), 5.22 (1H, dd, J=8.3, 8.3 Hz), 4.24 (2H, q, J=7.0 Hz), 3.96 (1H, m), 3.86 (1H, m), 3.11 (2H, m), 2.72 (2H, m), 2.69 (1H, m), 2.13 (1H, m), 1.30 (3H, t, J=7.0 Hz). | |
With copper(l) iodide; caesium carbonate; N,N`-dimethylethylenediamine; In 1,4-dioxane; at 100℃; for 1.5h;Inert atmosphere; | In a further alternative preparation a mixture of (R)-3-((6-ethoxypyridin-3- yl)oxy)pyrrolidin-2-one (2.00 g), 6-bromo-4-fluoro-2,3-dihydro-1 H-inden-1 -one (2.30 g), Lambda/,Lambda/'-dimethyl-ethylene-diamine (10 mL) and 1 ,4-dioxane (20 mL) was purged with argon and cesium carbonate (3.8 g) and copper(l) iodide (100 mg) were added. The mixture was heated to 100C for 1 .5 hours. After cooling to r.t. the mixture was diluted with EA and washed with water (5 times) and brine. The organic layer was dried (Na2SO4) and concentrated. The residue was purified by SGC (eluent: heptane with 0 to 70% EA) to provide Example 2-08. 1H-NMR (400 MHz, DMSO) delta 7.99 (1 H, dd, J = 1 1 .3, 1 .8 Hz), 7.97 (1 H, d, J = 3.1 Hz), 7.77 (1 H, d, J = 1 .8 Hz), 7.53 (1 H, dd, J = 8.9, 3.1 Hz), 6.76 (1 H, d, J = 8.9 Hz), 5.22 (1 H, dd, J = 8.3, 8.3 Hz), 4.24 (2H, q, J = 7.0 Hz), 3.96 (1 H, m), 3.86 (1 H, m), 3.1 1 (2H, m), 2.72 (2H, m), 2.69 (1 H, m), 2.13 (1 H, m), 1 .30 (3H, t, J = 7.0 Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With copper(l) iodide; caesium carbonate; N,N`-dimethylethylenediamine; In 1,4-dioxane; at 80℃; for 4h;Inert atmosphere; | Alternative Preparation of (R)-3-(6-Cyclopropylmethoxy-pyridin-3-yloxy)-1-(7-fluoro-3-oxo-indan-5-yl)-pyrrolidin-2-one (Example 1-11) A mixture of (R)-3-[6-(2-cyclopropyl-methoxy)-pyridin-3-yloxy]-pyrrolidin-2-one (100 mg), <strong>[881189-74-8]6-bromo-4-fluoro-2,3-dihydro-1H-inden-1-one</strong> (92 mg) and 1,4-dioxane (2 mL) was purged with argon. N,N'-Dimethyl-ethylene-diamine (355 mg), cesium carbonate (263 mg) and copper(I) iodide (8 mg) were added. The mixture was heated to 80 C. for 4 hours. After cooling to r.t. the mixture was filtered and the filtrate purified by preparative HPLC to provide Example 1-11. 1H-NMR (400 MHz, DMSO) delta 7.99 (1H, dd, J=11.2, 1.8 Hz), 7.95 (1H, d, J=3.1 Hz), 7.77 (1H, d, J=1.8 Hz), 7.53 (1H, dd, J=9.0, 3.1 Hz), 6.79 (1H, d, J=9.0 Hz), 5.22 (1H, dd, J=8.3, 8.3 Hz), 4.03 (2H, d, J=7.1 Hz), 3.96 (1H, m), 3.86 (1H, m), 3.10 (2H, m), 2.72 (2H, m), 2.68 (1H, m), 2.13 (1H, m), 1.22 (1H, m), 0.54 (2H, m), 0.30 (2H, m). | |
With copper(l) iodide; caesium carbonate; N,N`-dimethylethylenediamine; In 1,4-dioxane; at 80℃; for 4h;Inert atmosphere; | A mixture of (R)-3-[6-(2-cyclopropyl-methoxy)-pyridin-3-yloxy]-pyrrolidin-2-one (100 mg), 6-bromo-4-fluoro-2,3-dihydro-1 H-inden-1 -one (92 mg) and 1 ,4-dioxane (2 mL) waspurged with argon. Lambda/,Lambda/'-Dinnethyl-ethylene-diannine (355 mg), cesium carbonate (263 mg) and copper(l) iodide (8 mg) were added. The mixture was heated to 80C for 4 hours. After cooling to r.t. the mixture was filtered and the filtrate purified by preparative HPLC to provide Example 1 -1 1 . 1 H-NMR (400 MHz, DMSO) 5 7.99 (1 H, dd, J = 1 1 .2, 1 .8 Hz), 7.95 (1 H, d, J = 3.1 Hz), 7.77 (1 H, d, J = 1 .8 Hz), 7.53 (1 H, dd, J = 9.0, 3.1 Hz), 6.79 (1 H, d, J = 9.0 Hz), 5.22 (1 H, dd, J = 8.3, 8.3 Hz), 4.03 (2H, d, J = 7.1 Hz), 3.96 (1 H, m), 3.86 (1 H, m), 3.10 (2H, m), 2.72 (2H, m), 2.68 (1 H, m), 2.13 (1 H, m), 1 .22 (1 H, m), 0.54 (2H, m), 0.30 (2H, m). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With copper(l) iodide; caesium carbonate; N,N`-dimethylethylenediamine; In 1,4-dioxane; at 80℃; for 3h;Inert atmosphere; | (S)-1-(7-Fluoro-3-oxo-indan-5-yl)-3-hydroxy-pyrrolidin-2-one A mixture of <strong>[881189-74-8]6-bromo-4-fluoro-indan-1-one</strong> (Enamine, 453 mg), (S)-3-hydroxy-pyrrolidin-2-one (200 mg) and 1,4-dioxane (3 mL) was purged with argon. Cesium carbonate (645 mg), N,N'-dimethyl-ethylene-diamine (2.24 mL) and copper(I) iodide (38 mg) were added and the mixture was heated to 80° C. for 3 hours. After cooling to r.t. the mixture was filtered and the filtrate evaporated. The residue was purified by SGC (eluent: heptane/EA 1:1 with 0 to 20percent MeOH) to provide the title compound. MS ESI+: m/z=250 [M+H]+. | |
With copper(l) iodide; caesium carbonate; N,N`-dimethylethylenediamine; In 1,4-dioxane; at 80℃; for 3h;Inert atmosphere; | A mixture of 6-bromo-4-fluoro-indan-1 -one (Enamine, 453 mg), (S)-3-hydroxy-pyrrolidin- 2-one (200 mg) and 1 ,4-dioxane (3 mL) was purged with argon. Cesium carbonate (645 mg), Lambda/,Lambda/'-dimethyl-ethylene-diamine (2.24 mL) and copper(l) iodide (38 mg) were added and the mixture was heated to 80°C for 3 hours. After cooling to r.t. the mixture was filtered and the filtrate evaporated. The residue was purified by SGC (eluent: heptane/EA 1 :1 with 0 to 20percent MeOH) to provide the title compound. MS ESI+: m/z = 250 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Methyl 2-(6-bromo-4-fluoro-1 -oxo-2,3-dihydro-1 H-inden-2-yl)acetate To a mixture of diisopropylamine (1 .4 mL) and THF (25 mL) was added n-BuLi (3.4 mL, 2.6 M in toluene) at -78C. After 30 minutes a solution of 6-bromo-4-fluoro-2,3-dihydro- 1 H-inden-1 -one (2.0 g) in THF (10 mL) was added dropwise. After 30 minutes methyl 2- bromoacetate (1 .34 g) was added dropwise. The mixture was allowed to warm to RT with stirring for 2 hours. The mixture was poured into an ammonium chloride solution (10%, aqueous) and then extracted with EA (100 ml_ x 3). The organic phase was washed with brine and then dried over Na2SO4. The solvent was removed by evaporation under reduced pressure and the residue was purified by SGC (heptane to EA/heptane = 4:1 ) to provide the title compound. MS ESI+: m/z = 301 [M+H]+. As a second product (6-bromo-4-fluoro-2-methoxycarbonylmethyl-1 -oxo-indan-2-yl)-acetic acid methyl ester was isolated. MS ESI+: m/z = 373 [M+H]+. |