4-Bromotoluene → HCID 21846645, 화합물

HRID 619651노트

반응식

HRID 619651 반응식
[CH3:1][C:2]1[CH:7]=[CH:6][C:5](Br)=[CH:4][CH:3]=1.C([Li])(C)(C)C.[CH3:14][C:15]1([CH3:46])[CH:24]=[C:23](OS(C(F)(F)F)(=O)=O)[C:22]2[C:17](=[CH:18][CH:19]=[C:20]([C:33]#[C:34][C:35]3[CH:45]=[CH:44][C:38]([C:39]([O:41][CH2:42][CH3:43])=[O:40])=[CH:37][CH:36]=3)[CH:21]=2)[O:16]1>C1COCC1.CCCCC.[Cl-].[Cl-].[Zn+2].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([C:23]2[C:22]3[C:17](=[CH:18][CH:19]=[C:20]([C:33]#[C:34][C:35]4[CH:45]=[CH:44][C:38]([C:39]([O:41][CH2:42][CH3:43])=[O:40])=[CH:37][CH:36]=4)[CH:21]=3)[O:16][C:15]([CH3:14])([CH3:46])[CH:24]=2)=[CH:4][CH:3]=1

참가 물질

8

반응물 3

HCID 78054-BromotolueneHCID 21846667HCID 21846667, 화합물2회HCID 178418306HCID 178418306, 화합물

생성물 1

HCID 21846645HCID 21846645, 화합물

시약·촉매·용매 4

HCID 3007855Zincchloride촉매HCID 178418397HCID 178418397, 화합물촉매HCID 8003Pentane용매HCID 8028Tetrahydrofuran용매3회

실험 절차

A solution of 4-methylbromobenzene (237.0 mg, 1.38 mmol) in 3.0 mL of THF was cooled to -78° C. and tert-butyllithium (177.5 mg, 2.77 mmol, 1.6 ml of a 1.7M solution in pentane) was added to give a yellow solution. After 30 minutes a solution of ZnCl2 (377.0 mg, 2.77 mmol) in 5.0 mL THF was slowly added via cannula. The resulting solution was warmed to room temperature and transferred via cannula to a solution of ethyl 4-(2,2-dimethyl-4-trifluoromethanesulfonyloxy-(2H)-chromen-6-ylethynyl)-benzoate (Compound 264, 150.0 mg, 0.31 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. This 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, 120.0 mg (92%), was isolated by column chromatography (2.5% EtOAc/hexanes) as a colorless solid. 1H NMR (300 MHz, CDCl3) δ: 7.98 (2H, d, J=8.5 Hz), 7.50 (2H, d, J=8.5 Hz), 7.34 (1H, dd, J=2.1, 8.3 Hz), 7.25-7.21 (5H, m), 6.85 (1H, d, J=8.3 Hz), 5.62 (1H, s), 4.36 (2H, q, J=7.1 Hz), 2.41 (3H, s), 1.49 (6H, s), 1.39 (3H, t, J=7.1 Hz).

후처리

  1. customto give a yellow solution
  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. extractionThis 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

출처 및 근거

ORD 기록
ord-a1279b369f4944eaa6a9b8d25e4566dc
출처 데이터셋
uspto-grants-1999_09
특허 번호
US05958954

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