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CAS No. : | 64169-34-2 |
Formula : | C8H5BrO2 |
M.W : | 213.03 |
SMILES Code : | O=C1OCC2=C1C=CC(Br)=C2 |
MDL No. : | MFCD01797360 |
InChI Key : | IUSPXLCLQIZFHL-UHFFFAOYSA-N |
Pubchem ID : | 603144 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | 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 |
---|---|---|
In water; | Example 3 A mixture of 5-bromo-3H-isobenzofuran-1-one (4.2 g, 0.02 mol) and Cu(CN)2 (2.3 g, 0.02 mol) in NMP (60 mL) were stirred at 140° C. for 3hrs. Then solvent was removed by distilation under reduced pressure and the residue was refluxed in water (150 mL) for 10 minutes and allowed to cool to room temperature. Filtration and followed by drying in vacuo give the crude 5-cyano-3H-isobenzofuran-1-one (2.1 g) (HPLC 97percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
tetrakis(triphenylphosphine)palladium (0); In N,N-dimethyl-formamide; | Example 1 A mixture of Zn(CN)2 (2.4 g, 0.02 mol) and 5-bromo-3H-isobenzofuran-1-one (4.2 g, 0.02 mol) in DMF (80 mL) were stirred at room temperature under an atmosphere of argon for 30 minutes. Then dissolved oxygen was removed by bubbling argon through the reaction mixture for 10 minutes before the addition of tetrakis(triphenylphosphine)palladium (0) (1.2 g, 0.00096 mol,). Then the reaction was heated at 75° C. for 3 hrs, and then the solvent was removed under reduce pressure and the residue poured into water (150 mL). Filtration and followed by drying in vacuo give the crude 5-cyano-3H-isobenzofuran-1-one (2.8 g) (HPLC 95percent). | |
With NaCN;tetrakis(triphenylphosphine)palladium (0); In N,N-dimethyl-formamide; | Example 2 A mixture of Zn(CN)2 (0.3 g, 0.00256 mol), NaCN (1 g, 0,02 mol) and 5-bromo-3H-isobenzofuran-1-one (4.2 g, 0.02 mol) in DMF (80 mL) were stirred at room temperature under an atmosphere of argon for 30 minutes. Then dissolved oxygen was removed by bubbling argon through the reaction mixture for 10 minutes before the addition of tetrakis(triphenylphosphine)palladium (0) (1.2 g, 0.00096 mol). Then the reaction was heated at 75° C. for 3 hrs, and then the solvent was removed under reduce pressure and the residue poured into water (150 mL). Filtration and followed by drying in vacuo give the crude 5-cyano-3H-isobenzofuran-1-one (2.7 g) (HPLC 94percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With potassium carbonate; acetylacetone; copper(I) bromide; In N,N-dimethyl-formamide; at 90℃;Inert atmosphere; | Add phenol (20.4g, 0.22mol) and DMF 50mL to the reaction flask and start stirring.5-Bromoisobenzofuran-1(3H)-one (34.0 g, 0.16 mmol), acetylacetone (3.2 g, 0.03 mol), cuprous bromide (3.6 g, 0.03 mol), potassium carbonate (at room temperature) 30.8g, 0.22mol), three times of nitrogen replacement, heating to 90 C, stirring reaction overnight, adding 1000 mL of purified water to the reaction solution, suction filtration, the filter cake was dissolved in 800 mL of dichloromethane, and the organic phase was washed with 800 mL of 1N hydrochloric acid solution, with purified water. 1000 mL washing, drying the organic phase, and concentrating to dryness under reduced pressure to give a yellow solid.The title compound 2b (22.5 g, 63%) was obtained. |
72.22 g | With 2,2,6,6-tetramethylheptane-3,5-dione; caesium carbonate; copper(l) chloride; In 1-methyl-pyrrolidin-2-one; at 130℃; for 64h; | A mixture of 5-bromo-3H-isobenzofuran- 1 -one (75.9 g, 0.36 mol) (Sigma-Aldrich), phenol (67.1 g, 0.713 mol), CuCl (17.6 g, 0.178 mol), 2,2,6,6-tetramethyl-heptane-3,5-dione (TMHD, 7.33 mL) and cesium carbonate (232.3 g, 0.713 mol) in NMP (200 mL) was heated at 130 C for 64 h. After cooled, reaction mixture was poured into ice/2M HCl mixture (1 L). The mixture was then refluxed for 1 h. After cooled, the solid was collected, rinsed with water and dried in vacuo to provide the title compound (72.22 g, 0.32 mol). lH NMR in DMSO-d6, delta in ppm: 7.82 (dd, 1 H, J = 1.6 Hz, 7.6 Hz), 7.51-7.40 (m, 2 H), 7.3-7.1 (m, 5 H), 5.31 (s, 2 H). |
With potassium carbonate; copper(I) bromide; In N,N-dimethyl-formamide; acetylacetone; at 85℃; | j0234j A reactor was charged with DMF (68 Kg), and stirring was initiated. The reactor was then charged with phenol (51 Kg), acetylacetone (8 Kg), 5-bromophthalide (85 Kg), copper bromide (9 Kg), and potassium carbonate (77 Kg). The mixture was heated above 85 C and maintained until reactioncompletion and then cooled. Water was added. Solid was filtered and washed with water. Solid was dissolved in dichloromethane, and washed with aqueous HC1 and then with water. Solvent was removed under pressure and methanol was added. The mixture was stirred and filtered. Solid was washed with methanol and dried in an oven giving 5-phenoxyphthalide (Yield: 72%, HPLC: 99.6%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tris-(dibenzylideneacetone)dipalladium(0); N-ethyl-N,N-diisopropylamine; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; In 1,4-dioxane;Inert atmosphere; Reflux; | Step C: tert-Butyl 4-[(l-Oxo-l,3-dihydro-2-benzofuran-5-yl)sulfanyllpiperidine-l-carboxylate A solution of tert-butyl 4-sulfanylpiperidine-l-carboxylate (490 mg, 2.3 mmol) in 20 mL of anhydrous 1,4-dioxane was added 5-bromo-2-benzofuran-l(3H)-one (500 mg, 2.3 mmol), DIEA (596 mg, 4.62 mmol), tris(dibenzylideneacetone)dipalladium (0) (190 mg, 0.12 mmol) and Xantphos (67 mg, 0.12 mmol), and the mixture was heated at reflux under a nitrogen atmosphere overnight. The reaction mixture was concentrated under vacuum, and the resulting residue was purification by prep-TLC (Petrol ether/EtOAc = 2: 1) to provide tert-butyl 4-[(l-oxo-l,3-dihydro- 2-benzofuran-5-yl)sulfanyl]piperidine- 1 -carboxylate. 1H-NMR (400 MHz, CDC13) δ ppm 7.72 (d, J= 8.4 Hz, 1H), 7.60 -7.62 (m, 2H), 5.23 (s, 2H), 3.93-3.97 (m, 2H), 2.72-2.82 (m, 3H), 1.89-1.93 (m, 2H), 1.43-1.49 (m, 2H), 1.39 (s, 9H). | |
With tris-(dibenzylideneacetone)dipalladium(0); N-ethyl-N,N-diisopropylamine; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; In 1,4-dioxane;Inert atmosphere; Reflux; | [0142] A solution of <strong>[134464-79-2]tert-butyl 4-sulfanylpiperidine-1-carboxylate</strong> (490 mg, 2.3 mmol) in 20 mL of anhydrous 1,4-dioxanewas added 5-bromo-2-benzofuran-1(3H)-one (500 mg, 2.3 mmol), DIEA (596 mg, 4.62 mmol), tris(dibenzylideneacetone)dipalladium (0) (190 mg, 0.12 mmol) and Xantphos (67 mg, 0.12 mmol), and the mixture was heated at reflux undera nitrogen atmosphere overnight. The reaction mixture was concentrated under vacuum, and the resulting residue waspurification by prep-TLC (Petrol ether/EtOAc = 2:1) to provide tert-butyl 4-[(1-oxo-1,3-dihydro-2-benzofuran-5-yl)sulfanyl]piperidine-1-carboxylate.1H-NMR (400 MHz, CDCl3) δ ppm 7.72 (d, J= 8.4 Hz, 1H), 7.60 ∼7.62 (m, 2H), 5.23 (s, 2H), 3.93∼3.97 (m, 2H), 2.72∼2.82(m, 3H), 1.89∼1.93 (m, 2H), 1.43∼1.49 (m, 2H), 1.39 (s, 9H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66.7% | With palladium diacetate; potassium carbonate; catacxium A; In 1,4-dioxane; water; at 80℃; for 12h; | 5-Bromoisobenzofuran-1(3H)-one (2.5g, 11.8mmol), <strong>[27762-64-7](cyclohexylmethyl)boronic acid</strong>(2.00 g, 14.2 mmol), palladium acetate (0.13 g, 0.59 mmol), n-butylbis(1-adamantyl)phosphine (4.24 g, 1.18 mmol), potassium carbonate (3.3 g, 23.6 mmol), 1, 4-Dioxane (50 mL) and water (5 mL) were added to a reaction flask, and the mixture was warmed to 80 C for 12 h, and the reaction was monitored by TLC until the reaction was completed and the reaction was stopped. After cooling to room temperature, the solvent was evaporated under reduced pressure and the title compound was obtained by silica gel chromatography.72b (1.8g, 66.7%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Quinuclidine; (1,2-dimethoxyethane)dichloronickel(II); [4,4?-bis(1,1-dimethylethyl)-2,2?-bipyridine-N1,N1?]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate; potassium carbonate; 4,4'-di-tert-butyl-2,2'-bipyridine; In acetonitrile; at 20℃; for 22h;Irradiation; | Step 1. tert-butyl ((1S,2S)-2-((1-oxo-1,3-dihydroisobenzofuran-5-yl)oxy)cyclohexyl)carbamate (19-2a) To 5-bromoisobenzofuran-1(3H)-one (19-1a, 500 mg, 2.35 mmol), <strong>[121282-70-0]tert-butyl ((1S,2S)-2-hydroxycyclohexyl)carbamate</strong> (13-1a, 505 mg, 2.35 mmol), NiCl2(glyme) (26 mg, 0.12 mmol), dtbbpy (32 mg, 0.12 mmol), Ir[(dF(CF3)ppy)2dtbbpy]PF6 (26 mg, 0.023 mmol), quinuclidine (26 mg, 0.24 mmol) and K2CO3 (324 mg, 2.35 mmol) was added MeCN (30 mL) and the resulting mixture was stirred vigorously for 22 h under irradiation of blue LED light at room temperature. The reaction mixture was then concentrated to dryness and the crude material was purified by silica gel chromatography eluting with 0% to 100% EtOAc in heptane to afford 19-2a (732 mg, 1.93 mmol, 82% yield) as a white powder. MS [M-tBu+H]+=292.1. |