반응 #80655

반응 방정식

2,2,4,4-tetramethyl-6-ethynylthiochroman

Compound 35

2,2,4,4-tetramethyl-6-ethynylthiochroman

ethyl 6-chloro-nicotinate

Compound 29

ethyl 6-chloro-nicotinate

→

title compound

Ethyl 6-[(2,2,4,4-tetramethyl-thiochroman-6-yl)ethynyl]nicotinate

용매

triethylamine

반응 조건

후처리

1. 1
   기타degassed
2. 2
   기타The mixture was degassed again
3. 3
   기타the tube was sealed
4. 4
   온도cooled to room temperature
5. 5
   workup.ADDITIONThe mixture was treated with water and ether
6. 6
   기타the organic layer was separated
7. 7
   추출The aqueous layer was extracted with ether
8. 8
   세척washed with saturated NaCl solution
9. 9
   건조dried (MgSO4)
10. 10
    기타The solvent was removed in vacuo
11. 11
    기타the resultant residue was purified by flash chromatograhy (silica; 10% ethyl acetate in hexanes)

실험 절차

A solution of 232 mg (1.01 mmol) of 2,2,4,4-tetramethyl-6-ethynylthiochroman (Compound 35) and 190 mg (1.03 mmol) of ethyl 6-chloro-nicotinate (Compound 29) in 2 ml of triethylamine was placed in a heavy-walled glass tube, degassed, placed under argon and then treated with a powdered mixture of 53 mg (0.28 mmol) of cuprous iodide and 84 mg (0.12 mmol) of bis(triphenylphosphine) palladium (II) chloride. The mixture was degassed again, placed under argon and the tube was sealed. The reaction mixture was heated at 55 degrees C. for 60 h and then cooled to room temperature. The mixture was treated with water and ether and the organic layer was separated. The aqueous layer was extracted with ether, the organic layers were then combined and washed with saturated NaCl solution and then dried (MgSO4). The solvent was removed in vacuo and the resultant residue was purified by flash chromatograhy (silica; 10% ethyl acetate in hexanes) to give the title compound as a dark yellow oil. PMR (CDCl3): & 1.32-1.43 (15H, m), 1.92 (2H, s), 4.38 (2H, q, J-7.1 Hz), 7.28 (1H, dd, J-8.3 Hz, 1.8 Hz), 7.32-7.38 (2H, m), 7.53 (1H, d, J-8.3 Hz), 8.24 (1H, dd, J-8.2 Hz, 2.2 Hz), 9.16 (1H, d, J-2.2 Hz). MS exact mass, m/e 379.1594 (calcd. for C23H25NO2S, 379.1606).

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