2-Fluoro-4-nitrobenzaldehyde

Add borane-tetrahydrofuran complex (16.21 [ML, ] [1] M) to a mixture of 2-fluoro-4- nitro-benzoic acid (1.2 g) and tetrahydrofuran (10 [ML)] at [0°C.] Heat at [80°C] for 3 hours. Cool at room temperature and add 1 N aqueous hydrochloric acid (20 mL) and extract with ethyl acetate. Wash with saturated aqueous sodium bicarbonate and dry the remaining organic phase over sodium sulfate and concentrate under reduced pressure to provide (0.91 g, 83percent) of an oil. Add (2-fluoro-4-nitro-phenyl) -methanol (0.91 g) to a mixture of dioxide manganese (1.1 g) in 20 ml of dichloromethane. Stir at room temperature overnight and filter over [CELITECOMMAT;. ] Concentrate under reduced pressure to provide (0.27 g, 30percent) of the title compound as an oil.Add borane-tetrahydrofuran complex (16.21 [ML, ] [1] M) to a mixture of 2-fluoro-4- nitro-benzoic acid (1.2 g) and tetrahydrofuran (10 [ML)] at [0°C.] Heat at [80°C] for 3 hours. Cool at room temperature and add 1 N aqueous hydrochloric acid (20 mL) and extract with ethyl acetate. Wash with saturated aqueous sodium bicarbonate and dry the remaining organic phase over sodium sulfate and concentrate under reduced pressure to provide (0.91 g, 83percent) of an oil. Add (2-fluoro-4-nitro-phenyl) -methanol (0.91 g) to a mixture of dioxide manganese (1.1 g) in 20 ml of dichloromethane. Stir at room temperature overnight and filter over [CELITECOMMAT;. ] Concentrate under reduced pressure to provide (0.27 g, 30percent) of the title compound as an oil.Compound 14a (860 mg) was dissolved in tetrahydrofuran (10.0 ml), and the reaction mixture was ice-cooled. [2-FLUORO-4-NITROBENZALDEHYDE-BIS-ACETATE (FROM STEP 1, (6.9 G, 25.4 MMOL) ), ETOH (15] mL, water (15 mL) and concentrated sulfuric acid (1.4 [ML)] are mixed together and heated to reflux for 40 minutes. The reaction mixture is filtered through Solka-flok and is cooled to [0°C.] The white solid precipitate is isolated by filtration, washed with cold water and dried (20 Torr, 70°C) to give 3.2 g (49percent) of the desired aldehyde :1H NMR (400 MHz, [CDC13)] [810.] 5, 8. 16, 8. 09.Ethyl 2-(triphenylphosphoranylidene)acetate (4.12 g, 11.83 mmol) was added to a solution of 2-fluoro-4- nitrobenzaldehyde (1.00 g, 5.91 mmol) in THF (11.83 ml) and this was heated for 5h. The solvent was removed and the residue diluted in toluene and purified on a short pad of Si02 Hx-EA (9-1). This was then treated with 5% mol of iodine in 50 ml of toluene at 100 C overnight. The solvent was removed to give 1.25g of the title compound. 1H NMR (400 MHz, CDCI3of) delta ppm 1.37 (t, J=7.24 Hz, 3 H) 4.31 (q, J=7.17 Hz, 2 H) 6.68 (d, J=16.43 Hz, 1 H) 7.68 - 7.76 (m, 1 H) 7.69 - 7.76 (m, 1 H) 8.00 (dd, J=9.98, 2.15 Hz, 1 H) 8.07 (dd, J=8.41 , 2.15 Hz, 1 H).General procedure: To a stirred solution of compound 1a-1n (9.90 mmol) in DMF (20 mL) were added methyl thioglycolate (10.9 mmol) and potassium carbonate (39.6 mmol). The resulting mixture was stirred at 60 C for 15 h. The DMF was removed under reduced pressure, water (50 mL) was added and the mixture was extracted with ethylacetate (2 x 40 mL). The combined organic layers were dried withsodium sulfate, filtered, and the solvents were removed under reduced pressure to afford the title compound 2a-2n [31, 34].

Molecular Weight:169.11
XLogP3:1.3
Hydrogen Bond Acceptor Count:4
Rotatable Bond Count:1
Exact Mass:169.01752115
Monoisotopic Mass:169.01752115
Topological Polar Surface Area:62.9
Heavy Atom Count:12
Complexity:192
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes