3-Hydroxybenzamide

General procedure: Aldehyde (0.5mmol), NHExample 49; 3-Hydroxybenzamide (49a). 3-Cyanophenol (295 mg, 2.48 mmol, 100 mol-percent) and NaBOTo a solution of 3-hydroxybenzoic acid (1) (10.0 g, 72.41 mmol) in toluene (80 mL) at room temperature was slowly added thionyl chloride (7.71 mL, 108.62 mmol). The resulting solution was heated to reflux for 4.5 h and concentrated in vacuo to give crudeproduct of 3-hydroxybenzoyl chloride (2). The crude product was dissolved in THF (30 mL) in an ice-methanol bath and concentrated aqueous ammonia (28 mL) was dropwise added.The resulting reaction mixture was warmed slowly to room temperature and stirredfor 18 h at the same temperature. After concentrating in vacuo, the residue was suspended in water (20 mL) and filtered. The collected solid was washed with water (3 × 15 mL) and then dried in vacuo to give 3-hydroxybenzamide (3) (7.03g, 70.8percent) as anoff-white crystals. mp 160–163 °C, TLC RTo a solution of 3-hydroxybenzoic acid (1) (5.0 g, 36.21mmol) in toluene (40 mL) at room temperature was slowly added thionyl chloride (3.86 mL, 54.38 mmol). The reaction solution was heated to reflux for 4.5 h and concentrated invacuo to give 3-hydroxybenzoyl chloride (2). The crude product 2 was dissolved in THF (15 mL) in an ice bath and aqueous ammonia (14 mL) was dropwise added. The resulting mixture was slowly warmed to room temperature and stirred for 18 h at the same temperature. After concentrating in vacuo, the residue was suspended in water (10 mL) and filtered. The collected solid was washed with water (3 x10mL) and then dried in vacuo to give 3-hydroxybenzamide (3)(7.03 g, 70.8percent) as an off-white solid. mp 160–163°C, TLC R. Example 25 Synthesis of 3-hydroxybenzamideTo a reactor was charged methyl 3-hydroxybenzoate (160 mg) and 7N ammonia in methanol (4 ml). The reactor was then sealed, heated to 50 °C, and stirred for 16 hours. The reaction mixture was cooled to ambient temperature then reduced by rotary evaporation to yield an oil. This was purified by flashchromatography, eluting with n-hexane and ethyl acetate. Appropriate fractions were collected for the product peak and were reduced by rotary evaporation to obtain the desired product as yellow oil (15 mg, 10percent). The structure was confirmed as 3-hydroxybenzamide by 1H NMR.Using 1-methyl-3-cyanoquinoline salt as photosensitizer, cobalt oxime complex 2 as cobalt catalyst and 5mL of acetonitrile, 2.69mg (1 × 10-2mmol) photosensitizer and 2.80mg ) Cobalt catalyst, the atmosphere was replaced with Ar atmosphere, Then 0.2 mmol of benzamide (R1 is CONH2, R2, R3, R4 are independently H) and 2 mmol H2O. Room temperature, high pressure mercury lamp irradiation 5h. After completion of the reaction, H2 production was detected by GC (TCD), benzene conversion by GC (FID) was detected, and then column separation was performed. Nuclear magnetic hydrogenSpectroscopy and mass spectrometry identified products as 2-hydroxybenzamide, 3-hydroxybenzamide, 4-hydroxybenzamide and Ν- (3-carbamoylphenyl) benzamide. The conversion of benzamide was 63percent, the yields of 2-hydroxybenzamide, 3-hydroxybenzamide and 4-hydroxybenzamide were 35percent, 8percent, 11percentThe yield of N- (2-carbamoylphenyl) benzamide was 9percent and the yield of H2 was 58percent.General procedure: Aldehyde (0.5mmol), NH2OH·HCl (0.6mmol) and Cs2CO3 (0.6mmol) were stirred at 125C for 48h in a 3:1 mixture of DMSO-H2O (2mL) under air. The progress of the reaction was monitored by TLC using ethyl acetate and hexane as eluent. After completion, the reaction mixture was cooled to room temperature and treated with water (1mL). The resulting mixture was extracted with ethyl acetate (3×5mL). Drying (Na2SO4) and evaporation of the solvent gave a residue that was purified on silica gel column chromatography using ethyl acetate and hexane. The purified products were identified by 1H NMR spectra and the melting points comparison with the literature data.General procedure: 1 mmol of benzoic acid, 3 ml of 25-28% aqueous ammonia, and cesium carbonate were added to a microwave reactor.0.2 mmol and 0.01 mmolTetrabutylammonium bromide was reacted at a microwave power of 120 W for 20 min.Extracted with ethyl acetate, concentrated under reduced pressure, and the product was recrystallized from ethanol.A white solid was obtained in 97% yield.b

Molecular Weight:137.14
XLogP3:0.4
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:1
Exact Mass:137.047678466
Monoisotopic Mass:137.047678466
Topological Polar Surface Area:63.3
Heavy Atom Count:10
Complexity:136
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes