3-Butyn-1-OL → tert-Butyl 4-(4-hydroxybut-1-yn-1-yl)benzoate

HRID 1675667노트

반응식

HRID 1675667 반응식
I[C:2]1[CH:14]=[CH:13][C:5]([C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7])=[CH:4][CH:3]=1.[CH2:15]([OH:19])[CH2:16][C:17]#[CH:18]>C(N(CC)CC)C.ClCCl.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.[Cu]I>[OH:19][CH2:15][CH2:16][C:17]#[C:18][C:2]1[CH:14]=[CH:13][C:5]([C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7])=[CH:4][CH:3]=1

참가 물질

7

반응물 2

HCID 135663-Butyn-1-OLHCID 11130493Tert-butyl 4-iodobenzoate

생성물 1

HCID 58024754tert-Butyl 4-(4-hydroxybut-1-yn-1-yl)benzoate수율 145.8%

시약·촉매·용매 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 6102075Dichlorobis(triphenylphosphine)palladium촉매HCID 6344Dichloromethane용매HCID 8471Triethylamine용매

실험 절차

A mixture of 1,1-dimethylethyl 4-iodobenzoate (1.1 g, 3.62 mmol, e.g. which can be preparable e.g. according to E. C. Taylor, J. Org. Chem., 1995, 60(24), 7947), 3-butyn-1-ol (0.36 ml, 4.70 mmol, 1.3 equivalents), bis(triphenylphosphine)palladium(II)dichloride [(PPh3)2PdCl2] (0.13 g, 018 mmol, 5 mol %) and copper(I)iodide (0.014 g, 0.07 mmol, 2 mol %) in triethylamine (5 ml) was stirred at room temperature for 18 hours. The mixture was diluted with dichloromethane (50 ml) and washed with water (50 ml). The organic phase was collected by passing through a hydrophobic frit and evaporated to give a dark brown oil (1.3 g). This was purified by flash chromatography on silica gel (100 g silica cartridge, FlashMaster II), eluting with a gradient of 0 to 100% ethyl acetate in cyclohexane over 20 minutes. Fractions containing product (obtained from 4:1 cyclohexane:ethyl acetate eluant) were pooled and evaporated to dryness to give the title compound as a brown gummy oil (0.9 g). 1H NMR (400 MHz, chloroform-d) δ (delta) ppm 1.60 (9H, s), 1.85 (1H, t, J=6.27 Hz), 2.73 (2H, t, J=6.27 Hz), 3.85 (2H, q, J=6.27 Hz), 7.45 (2H, d, J=8.53 Hz), 7.92 (2H, d, J=8.53 Hz).

후처리

  1. washwashed with water (50 ml)
  2. customThe organic phase was collected
  3. customevaporated

출처 및 근거

ORD 기록
ord-e2370b2109f84b45903ecc27bbc0b3d1
출처 데이터셋
uspto-grants-2011_08
특허 번호
US08003663B2

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