반응 #706808

ord-a708faf232f145f8bae8e831f9a04b84

반응 방정식

CCOC(=O)c1ccc(C#Cc2ccc3c(c2)C(OS(=O)(=O)C(F)(F)F)=CC(C)(C)S3)cc1
ethyl 4-[(2,2-dimethyl-4-trifluoromethanesulfonyloxy-(2H)-thiochromen-6-yl)ethynyl]-benzoate
CCOC(=O)c1ccc(C#Cc2ccc3c(c2)C(OS(=O)(=O)C(F)(F)F)=CC(C)(C)S3)cc1
ethyl 4-(2,2-dimethyl-4-trifluoromethanesulfonyloxy-(2H)-thiochromen-6-ylethynyl)-benzoate
CCOC(=O)c1ccc(C#Cc2ccc3c(c2)C(OS(=O)(=O)C(F)(F)F)=CC(C)(C)S3)cc1
Compound 224
CCOC(=O)c1ccc(C#Cc2ccc3c(c2)C(OS(=O)(=O)C(F)(F)F)=CC(C)(C)S3)cc1
ethyl 4-(2,2-dimethyl-4-trifluoromethanesulfonyloxy-(2H)-thiochromen-6-ylethynyl)-benzoate
CCc1cccs1
2-ethylthiophene
[Li][CH2]CCC
n-butyllithium
CCOC(=O)c1ccc(C#Cc2ccc3c(c2)C(C2(CC)CC=CS2)=CC(C)(C)S3)cc1
title compound
CCOC(=O)c1ccc(C#Cc2ccc3c(c2)C(C2(CC)CC=CS2)=CC(C)(C)S3)cc1
Ethyl 4-[[4-(2-ethyl-thiophen-2-yl)-2,2-dimethyl-(2H)-thiochromen-6-yl]-ethynyl]-benzoate

반응 조건

온도
0°CELSIUS
상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    온도The resulting solution was warmed to room temperature
  2. 2
    온도This solution was heated to 50° C. for 2 hours
  3. 3
    온도cooled to room temperature
  4. 4
    기타the reaction quenched by the addition of saturated aqueous NH4Cl
  5. 5
    추출The solution was extracted with EtOAc
  6. 6
    세척the combined organic layers were washed with H2O and saturated aqueous NaCl
  7. 7
    건조before being dried (MgSO4)
  8. 8
    농축concentrated under reduced pressure

실험 절차

A solution of 2-ethylthiophene (112.0 mg, 1.00 mmol) in 2.0 mL of THF was cooled to -78° C. and n-butyllithium (64.0 mg, 1.00 mmol, 0.63 ml of a 1.6M solution in hexanes) was added and the solution warmed to 0° C. during 1.5 hours. A solution of ZnCl2 (218.0 mg, 1.60 mmol) in 3.0 mL THF was slowly added via cannula. The resulting solution was warmed to room temperature, stirred for 40 minutes, and transferred via cannula to a solution of ethyl 4-[(2,2-dimethyl-4-trifluoromethanesulfonyloxy-(2H)-thiochromen-6-yl)ethynyl]-benzoate (Compound 224, 200.0 mg, 0.40 mmol) and tetrakis(triphenylphosphine) palladium(0) (24.0 mg, 0.02 mmol) in 2.0 mL THF. This solution was heated to 50° C. for 2 hours, cooled to room temperature, and the reaction quenched by the addition of saturated aqueous NH4Cl. The solution was extracted with EtOAc and the combined organic layers were washed with H2O and saturated aqueous NaCl before being dried (MgSO4) and concentrated under reduced pressure. The title compound, 29.0 mg (16%), was isolated by HPLC (1.25% EtOAc/hexanes) as a pale-yellow solid. 1H NMR (300 MHz, CDCl3) δ: 8.01 (2H, d, J=8.4 Hz), 7.65 (1H, s), 7.55 (2H, d, J=8.4 Hz), 7.35 (2H, s), 6.84 (1H, d, J=3.5 Hz), 6.77 (1H, m), 6.02 (1H, s), 4.39 (2H, q, J=7.1 Hz), 2.88 (2H, q, J=7.6 Hz), 1.46 (6H, s), 1.41 (2H, t, J=7.1 Hz), 1.35 (2H, t, J=7.6 Hz),

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US05958954uspto-grants-1999_09