三乙胺 → (E)-2-(Phenylmethylidene)deca-3,9-diyn-1-al

HRID 1936912

反应方程式

HRID 1936912 反应方程式
Br[C:2](=[CH:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[CH:3]=[O:4].[CH:12]#[C:13][CH2:14][CH2:15][CH2:16][CH2:17][C:18]#[CH:19].C(N(CC)CC)C.[Al]>C1COCC1.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.[Cu]I>[C:6]1(/[CH:5]=[C:2](\[C:12]#[C:13][CH2:14][CH2:15][CH2:16][CH2:17][C:18]#[CH:19])/[CH:3]=[O:4])[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1

参与物

8

反应物 4

HCID 8471三乙胺HCID 21585alpha-溴代肉桂醛HCID 700991，7-辛二炔HCID 5359268铝

产物 1

HCID 11817217(E)-2-(Phenylmethylidene)deca-3,9-diyn-1-al收率 91%

试剂、催化剂与溶剂 3

HCID 24350碘化亚铜催化剂HCID 178418397HCID 178418397，化合物催化剂HCID 8028四氢呋喃溶剂2 次

实验过程

To a solution of Pd(PPh3)4 (0.55 g, 0.24 mmol) and α-bromocinnamaldehyde Compound 1 (2.08 g, 4.74 mmol) in degassed THF (170 mL) cooled in an ice-water bath was added a solution of 1,7-octadiyne (2.23 g, 9.48 mmol), triethylamine (15 mL), and CuI (0.36 g, 0.95 mmol) in degassed THF (30 mL) via a syringe under a nitrogen atmosphere. The reaction flask was then covered by a sheet of aluminum foil. After stirring at room temperature for 8 hours the reaction was quenched with saturated aqueous NH4Cl (50 mL) and diluted with EtOAc (100 mL). The organic layer was washed with brine, dried over anhydrous MgSO4, filtered, and concentrated in vacuo. The residue was purified by flash column chromatography (silica gel, 10 percent EtOAc in hexane) to give 2.13 g (91 percent) of Compound 2: yellow oil; Rf=0.50 (15 percent EtOAc in hexane); IR (neat) 3294, 2944, 2230, 2116, 1692, 1598, 1450, 1324, 1180 cm−1; 1H NMR (300 MHz, CDCl3) δ9.56 (s, 1H), 8.11-8.07 (m, 2H), 7.48-7.43 (m, 3H), 7.43 (s, 1H), 2.60 (t, J=6.65 Hz, 2H), 2.27 (td, J=6.78, 2.64 Hz, 2H), 1.97 (t, J=2.64 Hz, 1H), 1.86-1.69 (m, 4H); 13C NMR (75 MHz, CDCl3) δ192.4, 151.8, 134.9, 132.0, 131.1, 129.4, 124.1, 103.4, 84.6, 75.4, 69.4, 28.2, 28.0, 20.3, 18.7; MS (+FAB) m/z (relative intensity) 237 (M+H+, 100).

后处理

  1. customwas quenched with saturated aqueous NH4Cl (50 mL)
  2. additiondiluted with EtOAc (100 mL)
  3. washThe organic layer was washed with brine
  4. dry with materialdried over anhydrous MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by flash column chromatography (silica gel, 10 percent EtOAc in hexane)

来源与证据

ORD记录
ord-8fb6b7587d844f3dafa0ba2b8d918ef6
来源数据集
uspto-grants-2002_05
专利号
US06391916B1

关联笔记

加载中…