Methyl3-(4-hydroxyphenyl)propionate

white transparent low melting mass

Methyl 3-(4-hydroxyphenyl)propionate is a methyl ester resulting from the formal condensation of the carboxy group of phloretic acid with methanol. It is a nitrification inhibitor and a plant growth regulator. It has a role as a nitrification inhibitor and a plant growth regulator. It is a member of phenols and a methyl ester. It derives from a phloretic acid.

Methyl 3-(4-hydroxyphenyl)propanoate (0413) (0414) To a solution of (E)-methyl 3-(4-hydroxyphenyl)acrylate (1.0 g, 5.6 mmol) in EtOH (20 mL), Pd/C (0.1 g) was added. The reaction mixture was vigorously stirred under hydrogen atmosphere (1 bar) at room temperature for 21 h. The suspension was filtered through a Celite pad and evaporated to dryness under vacuum to afford 1.0 g (5.6 mmol, 99percent yield) of an oil identified as methyl 3-(4-hydroxyphenyl)propanoate. (0415) General procedure: To a suspension of 3(4-hydroxyphenyl)propanoic acid 1 (0.05 mmol) in TMCS (0.1 mmol), the appropriate alcohol (1.0 mL) was added and the reaction mixture was stirred at 25°C. After 24 h, the reaction was stopped and evaporated under reduced pressure to afford 1a–d in quantitative yield without the need of purification: 3-(4-Hydroxyphenyl)propionic acid methyl ester(1a) Oil; To a solution of3-(4-hydroxyphenyl)propanoic acid (2.50g, 15.04 mmol) in methanol(40 mL) were added dropwise 5.35 mL acetyl chloride (5.0eq, 75.20 mmol) at 0 °C. The reaction mixture was stirred over 1.5 h at0 °C. After completion of the reaction, the mixture was concentratedin vacuo and ethyl acetate was added. The organic layer waswashed with NaHCO3 (3 x 50 mL) and concentrated in vacuo to givemethyl 3-(4-hydroxyphenyl)propanoate 38 (2.70 g, 100percent) as acolorless oil. UPLC-MS: 1.62 min, 100percent. 1H NMR (300 MHz, CD3OD) δ (ppm) 7.08-6.94 (m, 2H), 6.80-6.64 (m, 2H), 3.69-3.49 (m, 3H), 2.87-2.70 (m, 2H), 2.60-2.45 (m, 2H). 13C NMR (75 MHz, CD3OD) δ (ppm) 174.4, 155.8, 131.8, 129.3, 115.3, 51.1, 36.1, 30.2. MS (ES) m/z181.7 (M + H)+. HRMS calculated for C10H12O3: 203.0679; found:203.0679 (M + Na)+.[355] Preparation 3-(4-hydroxy-phenyl)-propionic acid methyl ester[356] After 3-(4-hydroxy-phenyl)propionic acid (3 g, 18 mmol) was added with MeOH(6 mL), 4M HCl/dioxane solution (18 mL, 72 mmol) was added thereto, and themixture was stirred at room temperature for 3 hours. The reactant wasconcentrated, added with EtOAc, and then washed with NaCl aqueous solution. Theorganic layer was separated, dried with MgSO4.61 g p-hydroxyphenpropionic acid, 50 ml methanol and 0.5 ml concentrated HIntermediate 10: Methyl p-hydroxyphenpropionate General procedure: According to a literature protocol.[1] Propanoic acid derivative (10 g) was dissolved inmethanol (80 ml) and H2SO4 (700μl, 6 mmol) added. The resulting solution was refluxed for16 h and then allowed to cool to room temperature. The reaction mixture was reduced todryness and re-dissolved in ethyl acetate (20 ml). The organic phase was washed withsaturated aqueous sodium hydrogen carbonate (10 ml), brine (10 ml) and dried over MgSO4.Removal of the solvent gave the desired methyl ester. (Note: column chromatography is oftennot required for the methyl ester starting materials). Methyl 3-(4-hydroxyphenyl)propanoate (1a) Synthesized according to general procedure A (98percent); 1H NMR (500 MHz, d4-MeOH): δ 6.98(d, J = 8.4 Hz, 2H), 6.66 (d, J = 8.4 Hz, 2H), 3.60 (s, 3H), 2.78 (t, J = 7.6 Hz, 2H), 2.53 (t, J= 7.6 Hz, 2H); 13C NMR (125 MHz, d4-MeOH): 172.8, 155.6, 130.6, 129.1, 115.1, 51.2, 35.4, 29.5; HRMS (EI) calculated for C10H12O3 [M]+: 180.078643; found: 180.078803.20 g of p-hydroxyphenylpropionic acid was added to 300 ml of anhydrous methanol and2 ml of concentrated sulfuric acid, heated to reflux for 10 h, the solvent was evaporated under reduced pressure, then dissolved with ethyl acetate and washed sequentially with sodium hydrogen carbonate and water.Polyester, organic layer dried over anhydrous magnesium sulfate, The solvent was evaporated to give 21.2 g (yield: 98.2percent).15 g (0.09 mol, 1 eq) of 3-(4-hydroxyphenyl)propanoic acid are dissolved in 50 ml of methanol and 4 drops of sulfuric acid are added. The reaction mixture is stirred for 16 hours at room temperature. The reaction is stopped by addition of 50 mL of saturated sodium hydrogen carbonate solution and then extracted with ethyl acetate. The organic phases are combined and dried over sodium sulfate. The solvents are evaporated off and the residue is then chromatographed on silica gel (70/30 heptane/ethyl acetate). 14.9 g of methyl 3-(4-hydroxyphenyl)propanoate are obtained. Yield = 92 percentTo a solution of 3-(4-hydroxyphenyl)propanoic acid (3 g, 18.1 mmol) in 50 mL MeOH was added ΒΡ0. 8g 4-hydroxy cinnamic acid in 40 ml methanol and 10 drops HCl were refluxed for 12 hours. Workup as above gave 0.6g oil, 68percent yield. NMR CDC13 7.02, 6.75 (4H, Abq, J=8.6 Hz), 3.66 (3H, s), 2.86 (2H, t, J=7.4 Hz), 2.60 (2H, t, J=7. 4 Hz).AV 32 [ CNHISNOG] Mol. Wt.: 209.24 A. 0.8 gr 4-hydroxy cinnamic acid in 40 [ML METHANOL] and 10 drops HCI were [REFLUXED] for 12 hours. Workup as above gave 0.6 gr oil, 68percent yield. NMR CDCl3 7.02, 6.75 (4H, Abq, J=8.6 Hz), 3.66 (3H, s), 2.86 (2H, t, J=7.4 [HZ), ] 2.60 (2H, t, J=7. 4 Hz). B. 0.6 gr, 3.3 mM, ester from step A and 0.26 gr, 4.2 mM, ethanol amine were heated at 100 for 3 hours in an open vessel. Chromatography gave 0.3 gr recovered ester followed by amide. The viscous oil was triturated with acetone-methylene chloride and filtered to give 160 mg white solid, 23percent yield, mp-102. NMR acetone d6 8.10 (1H, s, OH), 7. [03, ] 6.74 (4H, Abq, J=8. [8 HZ), ] 3.90 (1H, t, J=5.2 Hz, NH), 3.54 (2H, q, J=7.1 Hz), 3.28 (2H, t, J=7.1 [HZ), ] 2.80 (2H, t, J=8.2 Hz), 2.41 (2H, t, J=8.2 Hz).0. 8g 4-hydroxy cinnamic acid in 40 ml methanol and 10 drops HCl were refluxed for 12 hours. Workup as above gave 0.6g oil, 68percent yield. NMR CDC13 7.02, 6.75 (4H, Abq, J=8.6 Hz), 3.66 (3H, s), 2.86 (2H, t, J=7.4 Hz), 2.60 (2H, t, J=7. 4 Hz).General procedure: After dissolving the carboxylic acid in the alcohol, three drops of HTo a solution of 3-(4-hydroxyphenyl)propionic acid (20 mg, 120 mmol) in MeOH (300 mL) was added SOCl2L three-mouth bottle, is provided with a stirring, thermometer and a condenser. Adding 340.0g the hydroxy phenylpropanoic acid, 3.4g concentrated sulfuric acid and 1500 ml methanol, heating reflux for 7 hours. Cooling to room temperature, using NaHCO Intermediate 2: Methyl 3-(4-hydroxyphenyl) propanoateTo a 1000 mL RB flask fitted with magnetic stirrer was charged 250 mL of DMF, 3-(4- Hydroxy-phenyl)-propanoic acid (25.0 g, 150.43 mmol) and K(a) Methyl 3-(4-Hydroxyphenyl)propionate

Molecular Weight:180.20
XLogP3:2
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:4
Exact Mass:180.078644241
Monoisotopic Mass:180.078644241
Topological Polar Surface Area:46.5
Heavy Atom Count:13
Complexity:160
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes