Structure of 103361-67-7
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CAS No. : | 103361-67-7 |
Formula : | C8H5FN2O4 |
M.W : | 212.13 |
SMILES Code : | O=C1COC2=CC(F)=C([N+]([O-])=O)C=C2N1 |
MDL No. : | MFCD22056242 |
* 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 |
---|---|---|
92% | With sulfuric acid; nitric acid; at -10℃; for 0.166667h; | To a solution of <strong>[103361-99-5]7-fluoro-4H-benzo[1,4]oxazin-3-one</strong> (3.00 g, 17.95 mmol) in concentrated H2SO4 (12 mL) at -10 C. was added a mixture of fuming nitric acid (1.131 g, 17.95 mmol, 0.75 mL) and concentrated H2SO4 (0.75 mL) dropwise, keeping the internal temperature below 0 C. After addition, the reaction mixture was stirred at -10 C. for 10 min. The reaction mixture was poured onto crushed ice (200 g) with care. The precipitate was collected by filtration, washed with water (50 mL) and dried in vacuo to give 7-fluoro-6-nitro-4H-benzo[1,4]oxazin-3-one as a light yellow solid (3.5 g, 92%). 1H NMR (DMSO-d6, 400 MHz): delta 11.02 (s, 1H), 7.61 (d, J=7.6 Hz, 1H), 7.23 (d, J=12.0 Hz, 1H), 4.77 (s, 2H). |
92% | With sulfuric acid; nitric acid; at -15℃; for 0.5h; | Add 7-fluoro-2H-benzo[b][1,4]oxazine-3(4H)one (20 mmol) to 40 mL of 80% by weight concentrated sulfuric acid, And cooled to -15 C. A mixture of 22 mmol of concentrated nitric acid (65% by weight) and 2.2 mL of 80% by weight of concentrated sulfuric acid was slowly added dropwise with stirring. After the dropwise addition was completed, the reaction was further stirred for 30 minutes. After the reaction was completed, the reaction solution was poured into 100 g of ice water and stirred vigorously for 15 min. The obtained solid is suction filtered, washed with water,After drying in vacuo, a pale yellow solid 3.9 g was obtained. The yield was 92%. |
92% | With sulfuric acid; nitric acid; at -15℃; for 0.5h; | 3) 7-Fluoro-2H-benzo[b][1,4]oxazin-3(4H)one (20 mmol) was added to 40 mL of 80% concentrated sulfuric acid and cooled to -15 C. A mixture of 22 mmol of concentrated nitric acid (65%) and 2.2 mL of 80% concentrated sulfuric acid was slowly added dropwise with stirring.After the dropwise addition was completed, the reaction was further stirred for 30 min. After the reaction was completed, the reaction solution was poured into 100 g of ice water and stirred vigorously for 15 min. The resulting solid was filtered off with suction, washed with water, and dried in vacuo to give a pale yellow solid, yield 92% |
With nitric acid; In sulfuric acid; | EXAMPLE 9 Production of the compound (III) from the compound (X): A solution of <strong>[103361-99-5]7-fluoro-2H-1,4-benzoxazin-3(4H)-one</strong> (2.0 g) in 80% aqueous sulfuric acid (30 ml) was cooled to 0 to 5 C., and 60% nitric acid (1.6 g) was gradually added thereto at 0 to 5 C. The resultant mixture was stirred at the same temperature for 30 minutes and poured onto ice water. The precipitated crystals were collected by filtration, washed with water and dried to give 7-fluoro-6-nitro-2H-1,4-benzoxazin-3(4H)-one (2.1 g) as pale brown crystals. m.p., 205.9 C. 1 H-NMR (CDCl3 +DMSO-D6) delta ppm: 3.2 (1H, broad), 4.62 (2H, s), 6.76 (1H, d, J=10 Hz), 7.6 (1H, d, J=6 Hz). | |
With nitric acid; In (2S)-N-methyl-1-phenylpropan-2-amine hydrate; sulfuric acid; ethyl acetate; | Step B: Preparation of 7-fluoro-6-nitro-2 H -1,4-benzoxazin-3(4 H)-one To a stirred solution of the title compound of Step A (10 g, 59 mmol) in concentrated sulfuric acid (35 mL) was added a mixture of concentrated nitric acid (7 mL) and concentrated sulfuric acid (7 mL) at 0 to 5 C over a period of 30 minutes. After the addition was finished, the reaction mixture was stirred for another 30 minutes. The solution was poured into 1 L of ice water. After the product precipitated, it was isolated by filtration and was then dissolved in ethyl acetate (500 mL). The organic layer was separated, dried and concentrated under reduced pressure to afford the title compound of Step B as a colorless solid melting at 185-189 C (10.5 g, 84%). 1H NMR ((CD3)2SO): delta 7.62 (d, 1H), 7.24 (d, 1H), 4.78 (s, 2H), 3.52 (s, 3H). 1.39 (d, 6H). | |
With nitric acid; In sulfuric acid; | B. A solution of <strong>[103361-99-5]7-fluoro-3,4-dihydro-3-oxo-2H-1,4-benzoxazine</strong> (2.0 gram) in 80% aqueous sulfuric acid (30 ml) is cooled to 0 to 5 C., and 60% nitric acid (1.6 g) is gradually added thereto at 0 to 5 C. The resultant mixture is stirred at the same temperature for 30 minutes and poured onto ice water. The precipitated crystals are collected by filtration, washed with water and dried to give 7-fluoro-3,4-dihydro-3-oxo-6-nitro-2H-1,4-benzoxazine. | |
60 | With sulfuric acid; nitric acid; at 20℃; for 0.75h; | To compound 21A (5 g, 30 mmol) in concentrated H2SO4 (17 mL) was added a 1:1 mixture of fuming HNO3 and conc. H2SO4 (7 mL) over 15 min. The mixture was stirred for additional 30 min at RT and was slowly poured into ice water (500 mL). The mixture was filtered to collect solid and washed with water (4×). The solid was placed under high vacuum in an 80 C. oil bath for 5 h to provide 21B (3.82 g, 60%). |
2.6 g | With sulfuric acid; nitric acid; at 0℃; for 0.5h;Inert atmosphere; | To a stirred solution of step 2 intermediate (2.7 g, 16.157 mmol) in sulphuric acid (3 ml) a mixture of nitric acid (69 %, 0.72 ml, 16.157 mmol) and concentrated sulphuric acid (2 ml) was drop wise added at 0 C under nitrogen atmosphere. The reaction mixture was stirred at 0 C for 30 min. The reaction mixture was quenched with ice-cooled water and solid was precipitated. The precipitated solid was dissolved in ethyl acetate (30 ml) and washed with aqueous saturated solution of sodium bicarbonate (150 ml). The ethyl acetate layer was dried and filtered and dried (Na2S04) and concentrated to yield 2.6 g of product as yellow solid. 1H NMR (300 MHz, DMSO-d6) delta 4.79 (s, 2H), 7.26 (d, J = 12.0 Hz, 1H), 7.63 (d, / = 7.2 Hz, 1H), 1 1.03 (br s, 1H). |
With sulfuric acid; nitric acid; at 0℃; | 100066] A mixture of <strong>[103361-99-5]7-fluoro-2H-1,4-benzoxazin-3(4H)-one</strong> (35 gm, 0.209 mol)and 80% sulphuric acid (525 mL) was cooled to 0C. 70% nitric acid was addeddropwise to the above mixture for over a period of 45-60 mins. The reaction mixturewas stirred for 1 hr at 0C and monitored by HPLC. After completion of reaction, thereaction mixture was slowly quenched with water at 0-5C and stirred well till densesolid appeared. The reaction mixture was then filtered and washed with water. Thesolid 6-nitro-7-fluoro-2H- 1 ,4-benoxazin-3(4H)-one obtained was dried under vacuumat 55-60C for 8 h at 500 mm of Hg.Drywt. :36gmYield : 81%HPLC Purity : 92.5% | |
With sulfuric acid; nitric acid; at 50℃; for 2.5h; | A certain amount of concentrated sulfuric acid is put into the nitration tank and the temperature is controlled to be less than 50C.Add a certain amount of intermediate 2 slowly and stir for 30 min; control the reactor temperature below 50C,A certain amount of 70% nitric acid was added dropwise to the mixture and dripped for about 60 minutes; the addition was completed.Incubate and stir for 60 minutes under 50C, sample material <0.5% qualified;The above materials are slowly dripped into the high water tank containing water to quench the phase, and the precipitated solids are stirred and filtered.The filter cake is beaten with a certain amount of water once, and a certain amount of sodium bicarbonate is added, filtered, and the filter cake is dried to obtain intermediate 3 . | |
A certain amount of concentrated sulfuric acid is put into the nitration tank, and the temperature is controlled to be less than 60C.Slowly add a certain amount of dichloroethane,<strong>[103361-99-5]7-fluoro-2H-1,4-benzoxazin-3(4H)-one</strong>,Stir for 30 min. A certain amount of acetic anhydride is added dropwise,Then add a certain amount of 60-98% nitric acid, about 1-2 hours, temperature 30-60 C.After the addition, the mixture is stirred at 30-60C for 1 hour.Sampling material <0.5% qualified. The above materials were slowly dropped into a reaction vessel containing water under stirring for quenching, and the solids were precipitated by stirring. After filtration, the filter cake is beaten with a certain amount of water and put in a certain amount of sodium bicarbonate.Filtration, filter cake drying to get the product.Among them, the product is C8H5FN2O4,Water H2O; C8H5FN2O4, water H2O mass ratio of 212:18;Among them, the <strong>[103361-99-5]7-fluoro-2H-1,4-benzoxazin-3(4H)-one</strong> (167),The mass ratio of concentrated nitric acid HNO3 (63) was 167:63.In step (1),The conversion rates of the nitration and hydrogenation reactions were all greater than 99.5%. |
Tags: 103361-67-7 synthesis path| 103361-67-7 SDS| 103361-67-7 COA| 103361-67-7 purity| 103361-67-7 application| 103361-67-7 NMR| 103361-67-7 COA| 103361-67-7 structure
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