Triethylamine → HCID 12470809, compound

Triethylamine (1.49 mL, 10.7 mmol, 1.50 equiv) was added to a solution of 3-chloropropiophenone (1.20 g, 7.12 mmol, 1 equiv) in dichloromethane (100 mL) at 23° C. Thioacetic acid (602 μL, 8.54 mmol, 1.20 equiv) was then added dropwise to the solution. After 1 h, the reaction mixture was concentrated in vacuo. The crude residue was dissolved in tetrahydrofuran (50 mL) and aqueous hydrochloric acid (6 N, 50 mL) was added to the solution. Thee reaction mixture was then heated to reflux. After 36 h, the reaction was diluted with ethyl acetate (200 mL) and washed with saturated aqueous sodium bicarbonate solution (400 mL). The aqueous layer was extracted with ethyl acetate (3×200 mL), and the combined organic layers were dried over sodium sulfate, were filtered, and were concentrated under reduced pressure. The crude reaction mixture was purified by flash column chromatography on silica gel (eluent: 20% ethyl acetate in hexanes) to afford 3-mercaptopropiophenone (E2-30, 703 mg, 59.4%) as a colorless oil. 1H NMR (500 MHz, CDCl3, 20° C.): δ 7.93 (d, J=7.5, 2H, COPh-o-H), 7.55 (t, J=7.5, 1H, COPh-p-H), 7.45 (app-t, J=7.5, 2H, COPh-m-H), 3.31 (t, J=7, 2H, CH2CH2SH, 2.89 (dt, J=8.5, 6.0, 2H, CH2CH2SH), 1.74 (t, J=8.5, 1H, SH). 13C NMR (125.8 MHz, CDCl3, 20° C.): δ 198.2 (C═O), 136.8 (COPh-ipso-C), 133.6 (COPh-p-C), 128.9 (COPh-m-C), 128.2 (COPh-o-C), 42.7 (CH2CH2SH), 19.1 (CH2CH2SH). FTIR (thin film) cm−1: 3061 (w), 2941 (w), 1683 (s), 1597 (m), 1580 (m) 1448 (m). HRMS (ESI) (m/z): calc'd for C9H11OS [M+H]+: 167.0525. found 167.0526. TLC (20% ethyl acetate in hexanes), Rf: 0.28 (UV, CAM).

1. concentrationthe reaction mixture was concentrated in vacuo
2. dissolutionThe crude residue was dissolved in tetrahydrofuran (50 mL)
3. additionaqueous hydrochloric acid (6 N, 50 mL) was added to the solution
4. temperatureThee reaction mixture was then heated to reflux
5. waitAfter 36 h
6. additionthe reaction was diluted with ethyl acetate (200 mL)
7. washwashed with saturated aqueous sodium bicarbonate solution (400 mL)
8. extractionThe aqueous layer was extracted with ethyl acetate (3×200 mL)
9. dry with materialthe combined organic layers were dried over sodium sulfate
10. filtrationwere filtered
11. concentrationwere concentrated under reduced pressure
12. customThe crude reaction mixture
13. customwas purified by flash column chromatography on silica gel (eluent: 20% ethyl acetate in hexanes)

ORD record

ord-735fd9ff35aa46c4b344fd677e602b52

Source dataset

uspto-grants-2016_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09353150B2