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Chemical Structure| 81721-86-0 Chemical Structure| 81721-86-0

Structure of 81721-86-0

Chemical Structure| 81721-86-0

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Product Details of [ 81721-86-0 ]

CAS No. :81721-86-0
Formula : C8H6N2O4
M.W : 194.14
SMILES Code : [O-][N+](=O)C1=CC2=C(NC(=O)CO2)C=C1
MDL No. :MFCD00090355
InChI Key :YVGHCFMAEHXPBH-UHFFFAOYSA-N
Pubchem ID :2763830

Safety of [ 81721-86-0 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of [ 81721-86-0 ]

* 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.

  • Downstream synthetic route of [ 81721-86-0 ]

[ 81721-86-0 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 81721-86-0 ]
  • [ 26215-14-5 ]
YieldReaction ConditionsOperation in experiment
97% With hydrogen;palladium on activated charcoal; In tetrahydrofuran; at 20℃; Synthesis of 7-amino-2H-benzo[b][1,4]oxazin-3(4H)-one A 1000 mL round-bottom flask was purged, flushed and maintained with a hydrogen atmosphere, then, was added a solution of 7-nitro-2H-benzo[b][1,4]oxazin-3(4H)-one (16.5 g, 85.05 mmol, 1.00 equiv) in THF (500 mL). To the mixture was added Pd/C (10%, 4 g). The resulting solution was allowed to react, with stirring, overnight while the temperature was maintained at room temperature. The reaction progress was monitored by TLC (PE/EtOAc=1:1). A filtration was performed. The filtrate was concentrated by evaporation under vacuum using a rotary evaporator. This resulted in 13.5 g (97%) of 7-amino-2H-benzo[b][1,4]oxazin-3(4H)-one as a red solid.
91% With hydrogen;palladium 10% on activated carbon; In methanol; ethyl acetate; for 2h; INTERMEDIATE 11; 7-Amino-4H-benzori,41oxazin-3-one; 7-Nitro-4i/-benzo[l,4]oxazin-3-one (0.65 g, 3.3 mmol) and 10% palladium on carbon (0.13 g) were combined in EtOAc (15 mL) and MeOH (15 mL) and hydrogenated for 2 h at atmospheric pressure. The catalyst was removed by filtration through celite and the filtrate reduced in vacuo to yield the title compound as a colourless oil (0.50 g, 91%). δH (DMSO-d6) 4.42 (2H, s), 4.89 (2H, br s), 6.13-6.20 (2H, m), 6.56 (IH, d, J 8.1 Hz),10.27 (IH, br s).
68% With hydrogen;palladium 10% on activated carbon; In N,N-dimethyl-formamide; at 20℃; for 16h; The suspension of 7-nitro-2H-benzo[b][1,4]oxazin-3(4H)-one (61.9 mmol) and 10% palladium on carbon (5 g) in N,N-dimethylformamide (150 mL) was maintained under an atmosphere of hydrogen gas at rt for 16 h. The insoluble solids were removed by filtration and the filtrate was concentrated. The residue was diluted water and the precipitated solids were collected by filtration, washed with hexane, and dried to provide 7-amino-2H-benzo[b][1,4]oxazin-3(4H)-one in 68% yield as a yellow solid.
68% With hydrogen;palladium on activated charcoal; In N,N-dimethyl-formamide; at 20℃; Synthesis of 7-amino-2H-benzo[b][1,4]oxazin-3(4H)-one Into a 500 mL 3-necked round-bottom flask was added a solution of 7-nitro-2H-benzo[b][1,4]oxazin-3(4H)-one (12 g, 61.86 mmol) in DMF (150 mL). To the mixture was added Pd/C (5 g) followed by hydrogen. The resulting solution was allowed to react, with stirring, overnight while the temperature was maintained at room temperature. The reaction progress was monitored by TLC (PE/EA=1:1). A filtration was performed. The filtrate was concentrated by evaporation under vacuum using a rotary evaporator. The product was precipitated by the addition of H2O. A filtration was performed. The filter cake was washed 3 times with 300 mL of hexane. This resulted in 7.3 g (68%) of 7-amino-2H-benzo[b][1,4]oxazin-3(4H)-one as a yellow solid.
68% With hydrogen;palladium 10% on activated carbon; In N,N-dimethyl-formamide; at 20℃; for 16h; Intermediate 23: Synthesis of 3-oxo-3,4-dihydro-2H-benzo[b][1,4]oxazine-7-sulfonyl chloride; 1. Synthesis of 7-amino-2H-benzo[b][1,4]oxazin-3(4H)-one; The suspension of 7-nitro-2H-benzo[b][1,4]oxazin-3(4H)-one (61.9 mmol) and 10% palladium on carbon (5 g) in N,N-dimethylformamide (150 mL) was maintained under an atmosphere of hydrogen gas at rt for 16 h. The insoluble solids were removed by filtration and the filtrate was concentrated. The residue was diluted water and the precipitated solids were collected by filtration, washed with hexane, and dried to provide 7-amino-2H-benzo[b][1,4]oxazin-3(4H)-one in 68% yield as a yellow solid.
68% With hydrogen;palladium 10% on activated carbon; In N,N-dimethyl-formamide; at 20℃; for 16h; Intermediate 29: Synthesis of 3-oxo-3,4-dihydro-2H-benzo[b][l,4]oxazine-7-sulfonyl chloride.1. Synthesis of 7-amino-2H-benzo[bl[ 1 ,4]oxazin-3(4H)-one.The suspension of 7-nitro-2//-benzo[b][l,4]oxazin-3(4H)-one (61.9 mmol) and 10% palladium on carbon (5 g) in N,N-dimethylformamide (150 mL) was maintained under an atmosphere of hydrogen gas at rt for 16 h. The insoluble solids were removed by filtration and the filtrate was concentrated. The residue was diluted water and the precipitated solids were collected by filtration, washed with hexane, and dried to provide 7-amino-2H- benzo[b][l,4]oxazin-3(4H)-one in 68% yield as a yellow solid.
68% With hydrogen;palladium 10% on activated carbon; In N,N-dimethyl-formamide; at 20℃; for 16h; The suspension of 7-nitro-2H-benzo[b][1,4]oxazin-3(4H)-one (61.9 mmol) and 10% palladium on carbon (5 g) in N,N-dimethylformamide (150 mL) was maintained under an atmosphere of hydrogen gas at rt for 16 h. The insoluble solids were removed by filtration and the filtrate was concentrated. The residue was diluted water and the precipitated solids were collected by filtration, washed with hexane, and dried to provide 7-amino-2H-benzo[b][1,4]oxazin-3(4H)-one in 68% yield as a yellow solid.
68% With hydrogen;palladium 10% on activated carbon; In N,N-dimethyl-formamide; at 20℃; for 16h; Intermediate 29: Synthesis of 3-oxo-3,4-dihydro-2/7-benzo[b][l,4]oxazine-7-sulfonyl chloride. 1. Synthesis of 7-amino-2H-benzo[b][L4]oxazin-3(4H)-one.The suspension of 7-nitro-2H-benzo[b][l,4]oxazin-3(4H)-one (61.9 mmol) and 10% palladium on carbon (5 g) in N,7V-dimethylforrnamide (150 mL) was maintained under an atmosphere of hydrogen gas at rt for 16 h. The insoluble solids were removed by filtration and the filtrate was concentrated. The residue was diluted water and the precipitated solids were collected by filtration, washed with hexane, and dried to provide 7-amino-2H- benzo[b][l,4]oxazin-3(4H)-one in 68% yield as a yellow solid.
68% With hydrogen;palladium 10% on activated carbon; In N,N-dimethyl-formamide; at 20℃; for 16h; The suspension of 7-nitro-2H-benzo[b][1,4]oxazin-3(4H)-one (61.9 mmol) and 10% palladium on carbon (5 g) in N,N-dimethylformamide (150 mL) was maintained under an atmosphere of hydrogen gas at rt for 16 h. The insoluble solids were removed by filtration and the filtrate was concentrated. The residue was diluted water and the precipitated solids were collected by filtration, washed with hexane, and dried to provide 7-amino-2H-benzo[b][1,4]oxazin-3(4H)-one in 68% yield as a yellow solid.
68% With hydrogen;palladium over charcoal; In N,N-dimethyl-formamide; at 20℃; Into 500 mL 3-necked round bottom flask was added a solution of 7-nitro-2H- benzo[b][l,4]oxazin-3(4H)-one (12 g, 61.86 mmol) in DMF (150 mL). To the mixture was added Pd/C (5 g) followed by addition of hydrogen gas. The resulting solution was allowed to react, with stirring, overnight while the temperature was maintained at room temperature. The reaction progress was monitored by TLC (ethyl acetate/petroleum ether = 1:1). A filtration was performed. The filtrate was concentrated by evaporation under vacuum using a rotary evaporator. The product was precipitated by the addition of H2O. A filtration was performed. The filter cake was washed 3 times <n="144"/>with 300 mL of hexane. This resulted in 7.3 g (68%) of 7-amino-2H-benzo[b][l,4]oxazin-3(4H)-one as a yellow solid.
1.63 g (81%) palladium; In methanol; 7-Amino-2H-1,4-benzoxazine-3-one (2c) A suspension of 10% palladium on carbon (0.24 g) and 2b (2.39 g, 12.3 mmol) in methanol (65 ml) was shaken under 25 lbs H2 in a Parr hydrogenation apparatus. After 3 h, the catalyst was filtered and the filtrate evaporated to afford 1.63 g (81%) of compound 2c. An analytical sample was recrystallization from MeOH/hexane. Mp 216-7 C.
In methanol; EXAMPLE 2 7-amino-3-oxo-3,4-dihydro-(2H)-1,4-benzoxazine Under argon, 10% palladium on carbon (350 mg, 5% w/w) was added to a suspension of 7-nitro-3-oxo-3,4-dihydro-(2H)-1,4-benzoxazine (7 g, 39.3 mmol) in 50 ml of MeOH. The reaction mixture was hydrogenated at 40 psi for 16 hours. The reaction mixture was then diluted with THF (-200 mls) and the reaction was filtered through celite. The solvent was evaporated, leaving a brown solid as the residue. Product was recrystallized from THF/Hexane (1:5). Collected 4.2 g (72%) of a tan solid: m.p. 213-215, 'H NMR (300 M Hz, DMSO) δ 4.410 (S, 2H), 4.869 (S, 2H) 6.141 (d, 1H, J=2.44) 6.176 (dd, 1H, J=2.25, 4.69), 6.563 (d, 1H, J=8.19), 9.535 (brs, 1H); 13 C NMR (300 MHz, DMSO) δ 66.9496, 102.2081, 108.1369, 116.5779; 116.8982, 144.5502, 145.4287, 164.389; Mass spectrum M+ at m/z 164
With hydrogen;palladium 10% on activated carbon; In methanol; for 2h; E. To a solution of 5-nitro-4H benzo[1,4]oxazin-3-one (0.314 g, 1.62 mmol) in 7 mL of MeOH was added 10% palladium on charcoal (0.172 g, 0.162 mmol). The reaction mixture was hydrogenated under balloon pressure of H2 gas for 2 hours. The catalyst was removed by filtration, and the filtrate was concentrated under reduced pressure to provide 7-amino-4H-benzo[1,4]oxazin-3-one as light brown solid.
13.5 g With palladium 10% on activated carbon; hydrogen; In tetrahydrofuran; at 20℃; A 1000 mL round-bottom flask was purged, flushed and maintained with a hydrogen atmosphere, then was added a solution of compound 3 (R = H; 16.5 g, 85.05 mmol, 1.00 equiv) in THE (500 mL). To the mixture was added Pd/C (lOpercent, 4 g). The resulting solution was allowed to react, with stirring, overnightwhile the temperature was maintained at room temperature. The reaction progress was monitored by TLC (PE/EtOAc=1 :1). A filtration was performed. The filtrate was concentrated by evaporation under vacuum using a rotary evaporator. This resulted in 13.5 g (97%) of compound 4 a red solid. Compounds with R= OH and Cl were obtained by the same procedure.

 

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