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Chemical Structure| 125568-71-0

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Product Details of [ 125568-71-0 ]

CAS No. :125568-71-0
Formula : C8H5F2NO4
M.W : 217.13
SMILES Code : O=C(OC)C1=CC([N+]([O-])=O)=C(F)C=C1F
MDL No. :MFCD07779369
InChI Key :KLMBOVOUTOBMLS-UHFFFAOYSA-N
Pubchem ID :11447263

Safety of [ 125568-71-0 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H319
Precautionary Statements:P305+P351+P338

Application In Synthesis of [ 125568-71-0 ]

* 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 [ 125568-71-0 ]

[ 125568-71-0 ] Synthesis Path-Downstream   1~2

  • 2
  • [ 67-56-1 ]
  • [ 153775-33-8 ]
  • [ 125568-71-0 ]
YieldReaction ConditionsOperation in experiment
100% With hydrogenchloride; In 1,4-dioxane; for 16h;Heating / reflux; Step 1:To a solution of <strong>[153775-33-8]2,4-difluoro-5-nitrobenzoic acid</strong> (4.96 g, 24.4 mmol, 1 eq) in MeOH (100 mL), was added a solution of 4N HCI in 1 ,4-dioxane (9 ml_). The reaction mixture was heated to reflux for 16 h, then cooled to RT and the MeOH was evaporated under vacuum. The residue was dissolved in EtOAc (50 mL) and the organic phase was washed with aqueous saturated NaHCO3 (25 mL) and brine (25 mL), then dried over MgSO4, filtered and concentrated. A quantitative yield of the ester 3a was obtained as a yellow solid (5.30 g, 24.4 mmol).
93% With sulfuric acid; at 65℃; for 40h; <strong>[153775-33-8]2,4-difluoro-5-nitrobenzoic acid</strong> (25.00 g, 123 mmol) was dissolved in MeOH (300 mL). Sulfuric acid (0.7 mL, 12.3 mmol, 0.1 eq) was added dropwise. The reaction was heated to 65 C for 40 h. The reaction mixture was cooled and concentrated under reduced pressure. The residue was taken up into DCM (100 mL) and washed with water (50 mL), aqueous saturated NaHC03solution (50 mL) and brine (50 mL). The aqueous layer was back-extracted with DCM (2 x 50 mL). The combined organic phases were dried over Na2S04, filtered and concentrated under reduced pressure to afford 25.21g of the desired product as a light brown solid. Yield: 93% in 99% purity.
92% With sulfuric acid; for 15h;Heating / reflux; Preparation of methyl 2,4-difluoro-5-nitrobenzoate (Chem. Abstr. Reg. No. 125568-71-0); <strong>[153775-33-8]2,4-Difluoro-5-nitrobenzoic acid</strong> (33.0 g, 162 mmol) was dissolved in 400 mL anhydrous methanol under an argon atmosphere, added 4 mL concentrated sulfuric acid, then heated to reflux for 15 hours. The solution was cooled and concentrated in vacuo. Redissolved in 400 mL diethyl ether, washed with sat. sodium bicarbonate (3 x 200 mL), brine, dried with magnesium sulfate, filtered and concentrated to yield title compound. (32.6 g, 92%) APCI" 217.0; Anal. HPLC Retention time = 15.7 minutes (>99% pure).
85% With sulfuric acid; for 18h;Heating / reflux; Sulfuric acid (3 mL) was added to a solution of 2,4-diotafluoro-5-niotatrobenzoiotac acid intermediate 17(100 g, 049 mol, 1 equiv) in methanol (700 mL) and the reaction heated to reflux for 18 h The reaction mixture was concentrated and the residue taken up in water and brought to pH 8 by addition of 1N NaOH The product was extracted into ethyl acetate, dried over Na2SO4, filtered and concentrated The residue was purified by silica gel flash column chromatography (0 ? 25% EtOAc Hexanes) to give intermediate 18 (90 g, 85% yield) as a tan solid1H NMR (400 MHz, DMSO-cfe) delta ppm 8 56 - 8 64 (m, 1 H), 7 83 - 7 94 (m, 1 H), 3 85 - 3 92 (m, 3 H)
85% sulfuric acid; for 18h;Heating / reflux; Intermediate 17; methyl 2,4-difluoro-5-nitrobenzoate; <n="24"/>Sulfuric acid (3 mL) was added to a solution of 2,4-difluoro-5-nitrobe?zoic acid intermediate 16 (100 g, 0.49 mol, 1 equiv) in methanol (700 mL) and the reaction heated to reflux for 18 h. The reaction mixture was concentrated and the residue taken up in water and brought to pH 8 by addition of 1 N NaOH. The product was extracted into ethyl acetate, dried over Na2SO4, filtered and concentrated. The residue was purified by silica gel flash column chromatography (0 ? 25% EtOAc: Hexanes) to give intermediate. 7 (90 g, 85% yield) as a tan solid. 1H NMR (400 MHz, DMSO-cfe) delta ppm 8.56 - 8.64 (m, 1 H), 7.83 - 7.94 (m, 1 H), 3.85 - 3.92 (m, 3 H).
85% sulfuric acid; for 18h;Heating / reflux; Intermediate 2; methyl 2,4-difluoro-5-nitrobenzoate; <n="13"/>Sulfuric acid (3 mL) was added to a solution of <strong>[153775-33-8]2,4-difluoro-5-nitrobenzoic acid</strong> intermediate 1 (100 g, 0.49 mol, 1 equiv) in methanol (700 mL) and the reaction heated to reflux for 18 h. The reaction mixture was concentrated and the residue taken up in water and brought to pH 8 by addition of 1N NaOH. The product was extracted into ethyl acetate, dried over Na2SO4, filtered and concentrated. The residue was purified by silica gel flash column chromatography (0 ? 25% EtOAc: Hexanes) to give intermediate 2 (90 g, 85% yield) as a tan solid.1H NMR (400 MHz, DMSO-Cf6) delta ppm 8.56 - 8.64 (m, 1 H), 7.83 - 7.94 (m, 1 H), 3.85 - 3.92 (m, 3 H).
With thionyl chloride; at 0 - 50℃; To a methanol solution of the benzoic acid cooled to 0 C. using an ice bath, would be added thionyl chloride dropwise. The reaction mixture would then be heated at 50 C. for 5 h. The solvent would be evaporated, and ethyl acetate and saturated aqueous sodium bicarbonate would be added. The phases would be separated, and the aqueous phase would be extracted twice with ethyl acetate. The combined organics would be dried over sodium sulfate and then filtered. The solvent would be evaporated to give the pure methyl ester; 2,4-Difluoro-5-nitro-benzoic acid methyl ester (440 mg) was prepared by following General Procedure K starting from <strong>[153775-33-8]2,4-difluoro-5-nitro-benzoic acid</strong> (500 mg) and thionyl chloride (233 uL).

 

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