Structure of 103362-07-8
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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. : | 103362-07-8 |
Formula : | C10H10FNO5 |
M.W : | 243.19 |
SMILES Code : | O=C(OCC)COC1=CC(F)=CC=C1[N+]([O-])=O |
* 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 acetic acid; ethyl acetate; | EXAMPLE 10 Production of the compound (X) from the compound (IX): Iron powder (36.42 g) was suspended in 5% aqueous acetic acid (69 ml) and heated to 80 C. To the suspension, a solution of ethyl 5-fluoro-2-nitrophenoxyacetate (15.86 g) in acetic acid (65 ml) and ethyl acetate (65 ml) was dropwise added, and the resultant mixture was heated at 60 to 80 C. under reflux for 3 hours. After removal of residue by filtration, the filtrate was extracted with ethyl acetate. The extract was washed with water and sodium bicarbonate solution, dried and concentrated to give 7-fluoro-2H-1,4-benzoxazin-3(4H)-one (6.82 g). m.p., 186.7 C. 1 H-NMR (CDCl3 +DMSO-D6) delta ppm: 4.2 (1H, broad), 4.51 (2H, s), 6.5-7.0 (3H, m). | |
In acetic acid; ethyl acetate; | A. Iron powder (36.42 g) is suspended in 5% aqueous acetic acid (69 ml) and heated to 80 C. To the suspension, a solution of ethyl 5-fluoro-2-nitrophenoxyacetate (15.86 g) in acetic acid (65 ml) and ethyl acetate (65 ml) is dropwise added, and the resulting mixture is heated at 60 to 80 C. under reflux for 3 hours. After removal of residue by filtration, the filtrate is extracted with ethyl acetate. The extract is washed with water and sodium bicarbonate solution, dried and concentrated to give 7-fluoro-3,4-dihydro-3-oxo-2H-1,4-benzoxazine. | |
In acetic acid; | Step B: 7-Fluoro-2H-1,4-benzoxazin-3(4H)-one A solution of the 49.0 grams (0.20 mole) of ethyl 2-(5-fluoro-2-nitrophenoxy)acetate in 100 ml of glacial acetic acid was added to a warm (60 C.), stirred mixture of iron powder (50.0 grams, 0.90 mole) in 300 ml of glacial acetic acid. The reaction temperature was allowed to reach 100 C., and the mixture was stirred for approximately three hours. This mixture was poured into water, forming a precipitate. The precipitate was collected by filtration and was recrystallized from ethanol to yield 25.0 grams of 7-fluoro-2H-1,4-benzoxazin-3(4H)-one; another sample of this compound prepared in a similar manner, and then purified further, had a melting point of 205-206 C. and an nmr spectrum which was consistent with the proposed structure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With iron; acetic acid; for 3h;Reflux; | Ethyl 2-nitro-5-fluorophenoxyacetate (50 mmol) was added to 50 mL of glacial acetic acid.Heat to reflux under stirring and iron powder (100 mmol) was added in three portions.After the addition was completed, the reaction was continued for 3 hours. After the reaction is completed, the iron powder is removed by filtration through diatomaceous earth while hot.The filtrate was cooled, poured into 200 mL of water and stirred vigorously for 30 min.The resulting solid was suction filtered, washed with water,After drying in vacuo, 7.18 g of a white solid was obtained.The yield was 86%. |
86% | With iron; acetic acid; for 3h;Reflux; | 2) Ethyl 2-nitro-5-fluorophenoxyacetate (50 mmol) was added to 50 mL of glacial acetic acid, heated to reflux with stirring, and iron powder (100 mmol) was added in three portions.After the addition was completed, the reaction was continued for 3 hours. After completion of the reaction, the iron powder was removed by filtration through celite, and the filtrate was cooled, poured into 200 mL of water, and stirred vigorously for 30 min.The resulting solid was filtered off with suction, washed with water, and dried in vacuo to give a white solid, yield 86% |
70.7% | With iron; acetic acid; In ethyl acetate; at 70℃; for 1.75h; | [00065] A solution of 5% acetic acid (340 mL) and iron powder (172.5 gm) was stirred and heated to 70C. A mixture of acetic acid (300 mL), ethyl-2-(2-nitro-5-fluorophenoxy) acetate (75 gm, 0.308 mol) and ethyl acetate (300 mL) were added drop wise to the above solution at 70C over a period of 45 mm and the reaction mixture was allowed to stir for 1 h. The reaction was monitored by HPLC. After completion of reaction, the reaction mixture was diluted with water (50 ml) and extracted with ethyl acetate (3 x 50 mL) at 40C and allowed to stir for 30 mins.Organic layer was washed with brine (50 mL), dried over anhydrous sodium sulfate and solvent was removed under reduced pressure to afford crude product which was purified by preparative HPLC to give pure product as white solid, 7-fluoro-2H-1,4- benzoxazin-3 (4H)-one.Drywt. :36.5gmYield 70.7%HPLC Purity : 99.2% |
With iron; ammonium chloride; In methanol; water; at 80℃; for 2h; | Intermediate 33: 7-fluoro-2H-1 ,4-benzoxazin-3(4H)-oneTo a suspension of ethyl [(5-fluoro-2-nitrophenyl)oxy]acetate (intermediate 32, 7.6 g, 31 .3 mmol) in methanol (40 mL) / water (40 mL) was added ammonium chloride (16.72 g, 313 mmol) followed by iron (10.47 g, 188 mmol) powder and the mixture was heated at 80 C for 2hr. The reaction mixture was filtered through celite, the filtrate was evaporated under vacuo, and the residue was extracted with EtOAc (4x40 mL). The organic phases were washed with brine and dried over IS^SC^. The mixture was filtered through a phase separator filter tube and the mixture was removed in vacuo to give the title product; m/z (ES): 168.10 [M+H]+; 1 H NMR (500 MHz, DMSO-d6) delta ppm 4.59 (s, 2 H) 6.77 - 6.83 (m, 1 H) 6.85 - 6.91 (m, 2 H) 10.68 - 10.74 (m, 1 H). | |
2.75 g | With iron; ammonium chloride; In methanol; water; at 80℃; for 2h; | Ammonium chloride (1 1 g, 205.58 mmol) was added to stirred suspension of step 1 intermediate (5.0 g, 20.558 mmol), methanol (30 ml) and water (80 ml) followed by addition of iron powder (6.8 g, 123.306), the reaction mixture was stirred at 80 C for 2 h. The reaction mixture was filtered through celite. The filtrate was concentrated under reduced pressure to obtain residue. To the residue, water (150 ml) and ethyl acetate (150 ml) was added and stirred for 15 min. the organic layer was separated and washed with brine (100 ml). The mixture was dried (Na2S04) and concentrated under reduced pressure. The product was purified by column chromatography to yield 2.75 g of product as an off-white solid; 1H NMR (300 MHz, DMSO-J6) delta 4.58 (s, 2H), 6.77-6.89 (m, 3H), 10.72 (br s, 1H); APCI-MS (m/z) 166.24 (M-H)". |
Tags: 103362-07-8 synthesis path| 103362-07-8 SDS| 103362-07-8 COA| 103362-07-8 purity| 103362-07-8 application| 103362-07-8 NMR| 103362-07-8 COA| 103362-07-8 structure
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