2-tert-Butylthiophene → Ethyl 4-[[4-(5-tert-butyl-thiophen-2-yl)-2,2-dimethyl-(2H)-thiochromen-6-yl]-ethynyl]-benzoate

HRID 619627ノート

反応式

HRID 619627 の反応式
[C:1]([C:5]1[S:6][CH:7]=[CH:8][CH:9]=1)([CH3:4])([CH3:3])[CH3:2].C([Li])CCC.[CH3:15][C:16]1([CH3:47])[CH:25]=[C:24](OS(C(F)(F)F)(=O)=O)[C:23]2[C:18](=[CH:19][CH:20]=[C:21]([C:34]#[C:35][C:36]3[CH:46]=[CH:45][C:39]([C:40]([O:42][CH2:43][CH3:44])=[O:41])=[CH:38][CH:37]=3)[CH:22]=2)[S:17]1>C1COCC1.[Cl-].[Cl-].[Zn+2].[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:1]([C:5]1[S:6][C:7]([C:24]2[C:23]3[C:18](=[CH:19][CH:20]=[C:21]([C:34]#[C:35][C:36]4[CH:46]=[CH:45][C:39]([C:40]([O:42][CH2:43][CH3:44])=[O:41])=[CH:38][CH:37]=4)[CH:22]=3)[S:17][C:16]([CH3:15])([CH3:47])[CH:25]=2)=[CH:8][CH:9]=1)([CH3:4])([CH3:3])[CH3:2]

参加物

7

反応物 3

HCID 155282-tert-ButylthiopheneHCID 10051511ethyl 4-(2,2-dimethyl-4-trifluoromethanesulfonyloxy-(2H)-thio-chromen-6-ylethynyl)-benzoate2 回HCID 178418339Butyllithium

生成物 1

HCID 21846655Ethyl 4-[[4-(5-tert-butyl-thiophen-2-yl)-2,2-dimethyl-(2H)-thiochromen-6-yl]-ethynyl]-benzoate

試薬・触媒・溶媒 3

HCID 3007855Zincchloride触媒HCID 11979704Tetrakis(triphenylphosphine)palladium触媒HCID 8028Tetrahydrofuran溶媒3 回

反応条件

温度
0 °C

実験手順

A solution of 2-tert-butylthiophene (105.0 mg, 0.75 mmol) in 2.0 mL of THF was cooled to -78° C. and n-butyllithium (48.1 mg, 0.75 mmol, 0.47 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 (163.2 mg, 1.20 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) (20.0 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, 110.0 mg (76%), was isolated by column chromatography (5% EtOAc/hexanes) as a colorless solid. 1H NMR (300 MHz, CDCl3) δ: 8.01 (2H, d, J=8.3 Hz), 7.68 (1H, s), 7.56 (2H, d, J 8.3 Hz), 7.36 (2H, m), 6.82 (2H, m), 6.04 (1H, s), 4.39 (2H, q, J=7.1 Hz), 1.46 (6H, s), 1.43 (9H, s), 1.41 (2H, t, J=7.1 Hz).

後処理

  1. temperatureThe resulting solution was warmed to room temperature
  2. temperatureThis solution was heated to 50° C. for 2 hours
  3. temperaturecooled to room temperature
  4. customthe reaction quenched by the addition of saturated aqueous NH4Cl
  5. extractionThe solution was extracted with EtOAc
  6. washthe combined organic layers were washed with H2O and saturated aqueous NaCl
  7. dry with materialbefore being dried (MgSO4)
  8. concentrationconcentrated under reduced pressure

出典と根拠

ORDレコード
ord-6e7853432d594eb4ba231c4214e78b3e
出典データセット
uspto-grants-1999_09
特許番号
US05958954

反応ノート

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