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CAS No. : | 216393-67-8 | MDL No. : | MFCD01318122 |
Formula : | C6H4ClFIN | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | SSNQXCONXNVTJN-UHFFFAOYSA-N |
M.W : | 271.46 | Pubchem ID : | 2773650 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | |
Hazard Statements: | H317-H319 | 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 |
---|---|---|
98% | With silver(II) sulfate; iodine; In ethanol; at 20℃; for 2h; | Step 1: synthesis of 4-chloro-2-fluoro-6-iodoaniline To a solution of 4-chloro-2-fluoroaniline (1.15 g, 7.9 mmol) in 125 mL of ethanol added silversulphate (1.7 g, 8.3 mmol), then followed by addition of ?2 (2.1 g, 8.3 mmol) in portions. Afterthe addition was completed, the mixture was stirred at RT for 2 hours. The mixture was filtered through celite and the filtration was evaporated to give dark oil which was dissolved in 125 mL of DCM. The solution was washed with 2M sodium hydroxide (40 mL x 2), saturated Na25203 (40 mL x 2) and water (40 mL x 2). The resulting solution was dried over Mg504 and thenevaporated to give the crude 4-chloro-2-fluoro-6-iodoaniline as dark oil (2.1 g, yield: 98%). |
87% | With iodine; silver sulfate; In ethanol; at 20℃; for 1.5h; | 4-Chloro-2-fluoroaniline (2.9 g, 20 mmol) was dissolved in ethanol (200 mL). Silver sulphate (6.22 g, 20 mmol) was added and then iodine (5.08 g, 20 mmol) was added in small portions. After the addition was complete the reaction mixture was stirred at ambient temperature for 90min. The reaction mixture was filtered through Celite and evaporated to leave a dark oil which was taken up in DCM (200 mL). and washed with 2M sodium hydroxide (2 x 50 mL), saturated sodium thiosulphate (2x50 mL) and water (2x50 mL). The solution was dried (MgSO4) and evaporated to leave the title compound as a dark oil (4.73g, 87%).1H NMR (400 MHz, DMSO-d6) delta 5.30 (2H, s), 7.25 - 7.29 (IH, m), 7.47 (IH, t) |
40% | With iodine; silver sulfate; In ethanol; at 20℃; for 2h; | To a solution of 4-chloro-2-fluoroaniline (2 g, 14 mmol) in EtOH (40 mL) was added Ag2S04 (12.9 g, 42 mmol), followed by the addition of I2 (10.5 g, 42 mmol). The reaction mixture was stirred at RT for 2 h and then filtered through Celite. The filtrate was evaporated to give a dark oil. The residue was dissolved in DCM (70 mL), washed with 2M NaOH (40 mL x 2), Na2S203 (40 mL x 2) and water (40 mL x 2). The resulting solution was dried over MgS04, filtered and concentrated. The residue was purified by column chromatography on silica gel (PE/EA = 5/1) to give 4-chloro-2-fluoro-6-iodoaniline (1.5 g, 40% yield) as a dark oil. 1H NMR (400 MHz, DMSO-i): d 7.47-7.46 (m, 1H), 7.28-7.25 (m, 1H), 5.31 (brs, 2H). |
With iodine; silver sulfate; In ethanol; at 20℃; for 2h; | Step 1: synthesis of 4-chloro-2-fluoro-6-iodoaniline To a solution of 4-chloro-2-fluoroaniline (1.15 g, 7.9 mmol) in 125 mL of ethanol added silver sulphate (1.7 g, 8.3 mmol), then followed by addition of I2 (2.1 g, 8.3 mmol) in portions. After the addition was completed, the mixture was stirred at RT for 2 hours. The mixture was filtered through celite and the filtration was evaporated to give dark oil which was dissolved in 125 mL of DCM. The solution was washed with 2M sodium hydroxide (40 mL*2), saturated Na2S2O3 (40 mL*2) and water (40 mL*2). The resulting solution was dried over MgSO4 and then evaporated to give the crude 4-chloro-2-fluoro-6-iodoaniline as dark oil (2.1 g, yield: 98%). | |
With iodine; silver sulfate; In ethanol; at 20℃; for 2h; | To a solution of 4-chloro-2-fluoroaniline (1.15 g, 7.9 mmol) in 125 mL of ethanol added silver sulphate (1.7 g, 8.3 mmol), then followed by addition of I2 (2.1 g, 8.3 mmol) in portions. After the addition was completed, the mixture was stirred at RT for 2 hours. The mixture was filtered through celite and the filtration was evaporated to give dark oil which was dissolved in 125 mL of DCM. The solution was washed with 2M sodium hydroxide (40 mL×2), saturated Na2S2O3 (40 mL×2) and water (40 mL×2). The resulting solution was dried over MgSO4 and then evaporated to give the crude 4-chloro-2-fluoro-6-iodoaniline as dark oil (2.1 g, yield: 98%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With 1,4-diaza-bicyclo[2.2.2]octane; palladium diacetate; In N,N-dimethyl-formamide; at 100℃; for 3h; | 4-Chloro-2-fluoro-6-iodoaniline (2.5 g, 9.2 mmol), pyruvic acid (2.5 g, 27 mmol) and DABCO (3.1 g, 27 mmol) were dissolved in DMF (15 mL). The solution was degassed and palladium acetate (500 mg) was added. The reaction mixture was heated at 100 C for 3 h, cooled to RT and then filtered. The filtrate was diluted with EA (90 mL), washed with 2M HC1 (20 mL x 3), water (40 mL) and brine (40 mL). The organic phase was dried over MgS04, filtered and evaporated to give 5-chloro-7-fluoro-lH-indole-2-carboxylic acid (1.9 g, 97% yield) as a dark solid. 1H NMR (400 MHz, DMSO^): d 13.06 (br s, 1H), 12.50 (s, 1H), 7.59 (s, 1H), 7.21 (d, = 1.2 Hz, 1H), 7.16-7.15 (t, 7= 3.2 Hz, 1H). |
85% | With 1,4-diaza-bicyclo[2.2.2]octane; palladium diacetate; In N,N-dimethyl-formamide; at 100℃; for 3h; | 4~Chloro-2-fluoro-6-iodoaniline (Intermediate 30, 1.35 g, 5 mmol), pyruvic acid (1.32 g,15 mmol) and DABCO (1.68 g,15 mmol) were dissolved in DMF(15 mL). The solution was degassed and palladium acetate (56 mg) was added. The mixture was then heated to 1000C for 3h., cooled to ambient and filtered. The filtrate was diluted with EtOAc (100 mL), washed with 2M HCl (2 x 2OmL), water (20 mL) and brine (20 mL), dried (MgSO4) and evaporated to leave the title compound as a dark solid (0.9g, 85% ). 1H NMR (400 MHz, DMSO-de) delta 7.16 (IH, t), 7.21 - 7.24 (IH, m), 7.59 (IH, d), 12.52 (IH, s), 13.27 (IH, s); MS m/z 212 (M-H)" |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With copper(l) iodide; triethylamine;bis-triphenylphosphine-palladium(II) chloride; for 1h;Reflux; | To a mixture of 3-ethynylpyridine (1.13 g, 11 mmol) and 2-fluoro^-chloro-6-iodoaniline (2.71 g, 10 mmol) in triethylamine (100 mL) is added PdCI2(PPh3)2 (175 mg, 0.25 mmol) and CuI (95 mg, 0.50 mmol) and the mixture is refluxed for 1 h. The solvent is removed in vacuo and the residue is purified by silica gel flash chromatography (dichloromethane- methanol, 1 :0 to 24:1 ) to give 4-chloro-2-fluoro-6-pyridin-3-ylethynyl-phenylamine. MS (ESI) m/z 247 (M+H)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
25% | With sodium carbonate; lithium chloride;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In N,N-dimethyl-formamide; at 100℃; | INTERMEDIATE 150 - PREPARATION of Lambda/-(2-(5-chloro-7-fluoro-2-(triethylsilyl)-1 H-indol- 3-yl)ethyl)-5-(2,5-difluorobenzyl)isoxazole-3-carboxamide; A mixture of <strong>[216393-67-8]4-chloro-2-fluoro-6-iodoaniline</strong> (0.100 g; 0.368 mmol), 5-(2,5-difluorobenzyl)- N-(4-(triethylsilyl)but-3-ynyl)isoxazole-3-carboxamide (0.150 g; 0.347 mmol), Bis(diphenylphosphino)ferrocene]palladium(ll) chloride (0.015 g; 0.018 mmol), lithium chloride (0.016 mg; 0.368 mmol), sodium carbonate (0.078 g; 0.737 mmol) in DMF (5 ml.) was stirred at 100 0C overnight. The solution was reparted between ethyl acetate and brine, washed with sodium thiosulphate, dried and concentrated under reduced pressure. The crude mixture was purified by flash chromatography on silica (eluent 2 to 60 % ethyl acetate in heptane) to yield 0.05 g (25%) of Lambda/-(2-(5-chloro-7-fluoro-2-(triethylsilyl)-1 H- indol-3-yl)ethyl)-5-(2,5-difluorobenzyl)isoxazole-3-carboxamide as a yellow oil. ESI/APCI(+): 549(M+H). |
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