ChemicalBook CAS DataBase List 3-ETHYNYL-BENZOIC ACID METHYL ESTER

3-ETHYNYL-BENZOIC ACID METHYL ESTER synthesis

10synthesis methods

Product Name:3-ETHYNYL-BENZOIC ACID METHYL ESTER
CAS Number:10602-06-9
Molecular formula:C10H8O2
Molecular Weight:160.17

67-56-1

914943-91-2

10602-06-9

Tert-butyl 3-ethynylbenzoate (117) (1.50 g, 9.37 mmol) was dissolved in anhydrous dichloromethane (DCM) (70 mL) and trifluoroacetic acid (TFA) (35.9 mL, 488 mmol) was added slowly. The reaction mixture was stirred at room temperature for 3 hours and then concentrated under vacuum. Toluene was then added and concentrated again under vacuum to give a light yellow solid. The solid was dissolved in methanol (50 mL) and concentrated again. Concentrated sulfuric acid (about 1 mL) was added and the resulting solution was stirred at 85°C for 20 hours. After completion of the reaction, it was cooled to room temperature and the volatiles were removed under vacuum. The residue was diluted with ethyl acetate (EtOAc) (200 mL) and slowly neutralized with saturated aqueous sodium bicarbonate (NaHCO3) (100 mL). The organic and aqueous layers were separated and the aqueous layer was further extracted with ethyl acetate (200 mL). The organic layers were combined, washed sequentially with water (100 mL) and brine (100 mL), dried over anhydrous magnesium sulfate (MgSO4), filtered and concentrated in vacuo to afford methyl 3-alkynylbenzoate (131) (1.136 g, 96% overall yield in two steps) as a pale yellow solid. The product was confirmed by 1H NMR (400 MHz, CDCl3): δ 8.17 (t, J = 1.5 Hz, 1H), 8.03-8.00 (m, 1H), 7.66 (dt, J = 7.7, 1.4 Hz, 1H), 7.41 (td, J = 7.8, 0.4 Hz, 1H), 3.93 (s, 3H), 3.12 (s, 1H) . the LCMS analysis method C showed a retention time of 5.84 min.

67-56-1 Synthesis

67-56-1
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914943-91-2 Synthesis

914943-91-2
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10602-06-9
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Yield: 96%

Reaction Conditions:

Stage #1:tert-butyl 3-ethynylbenzoate with trifluoroacetic acid in dichloromethane at 20; for 3 h;
Stage #2:methanol with sulfuric acid at 65; for 20 h;

Steps:

7.a Methyl 3-ethynylbenzoate (131)
terf-Butyl 3-ethynylbenzoate (117) (1.50 g, 9.37 mmoi) was dissolved in dry DCM (70 mL) and TFA (35.9 mL, 488 mmoi) was added carefully. The reaction was stirred at room temperature for 3 hours, concentrated in vacuo and toluene was added and then removed in vacuo to give a pale yellow solid. This material was dissolved in methanol (50 mL) and cone. H₂S0₄ (-1 mL) was added and the resulting solution was stirred at 85 °C for 20 hours. Upon cooling to room temperature, the volatiies were removed in vacuo and the residue was diluted with EtOAc (200 mL) and sat. aq. NaHCO₃ (100 mL) was added slowly. The layers were separated and the aqueous layer was extracted with EtOAc (200 mL), the organic layers were combined and washed with water (100 mL), brine (100 mL), dried ( gS0₄), filtered and concentrated in vacuo to give the title compound (131) (1.136 g, 96% yield over 2 steps) as a pale yellow solid; ¹H NMR (400 MHz, CDCI₃) δ 8.17 (t, J = 1.5 Hz, 1 H), 8.03 - 8.00 (m, 1 H), 7.66 (dt, J = 7.7, 1.4 Hz, 1 H), 7.41 (td, J = 7.8, 0.4 Hz, 1 H), 3.93 (s, 3H), 3.12 (s, 1 H). LCMS Method C: rt 5.84 min.

References:

CANCER THERAPEUTICS CRC PTY LTD;DEVLIN, Mark Graeme;STREET, Ian Philip;TONG, Warwick Bonner WO2014/27199, 2014, A1 Location in patent:Page/Page column 75

77123-59-2 Synthesis