Trimethylsilylacetylene → Silane, trimethyl[[4-[(tetrahydro-2H-pyran-2-yl)oxy]phenyl]ethynyl]-

HRID 10476ノート

反応式

HRID 10476 の反応式
I[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH:9]2[CH2:14][CH2:13][CH2:12][CH2:11][O:10]2)=[CH:4][CH:3]=1.[CH3:15][Si:16]([C:19]#[CH:20])([CH3:18])[CH3:17]>C(NC(C)C)(C)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[O:10]1[CH2:11][CH2:12][CH2:13][CH2:14][CH:9]1[O:8][C:5]1[CH:6]=[CH:7][C:2]([C:20]#[C:19][Si:16]([CH3:18])([CH3:17])[CH3:15])=[CH:3][CH:4]=1

参加物

6

反応物 2

HCID 66111TrimethylsilylacetyleneHCID 29168032H-Pyran, tetrahydro-2-(4-iodophenoxy)-

生成物 1

HCID 10540306Silane, trimethyl[[4-[(tetrahydro-2H-pyran-2-yl)oxy]phenyl]ethynyl]-

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418476HCID 178418476、化合物触媒HCID 7912Diisopropylamine溶媒

実験手順

To a degassed solution of compound 1 (9.12 g, 30 mmol) in diisopropylamine (180 ml) under nitrogen, Pd(PPh3)2Cl2 (140 mg, 0.2 mmol) and CuI (78 mg, 0.4 mmol) were added. Then trimethylsilyl acetylene (3.3 g, 33 mmol) was added dropwise to this clear solution. The reaction mixture was stirred for 2 hours at room temperature. The salt formed during the reaction procedure was filtered off and washed well with ethyl acetate. The filtrate was evaporated to dryness and hydrolyzed with concentrated hydrochloric acid (5 ml), water (25 ml) and crushed ice (10 g), then extracted with ethyl acetate. The combined organic paste was washed with brine and dried with MgSO4. The solvent was removed in vacuo and the residue was purified by column chromatography (petroleum ether-ethyl acetate=9:1) to give a yellow oil of 2. Yield 7.9 g (96%); δH(CDCl3; 300 MHz): 7.39(d, J=8.7, 2H, Ar—H, 6.97(d, J=8.6, 2H, Ar—H), 5.41(t, J=3.1, 1H, OCHO), 3.84(m, 1H, THP), 3.59(m, 1H, THP), 1.86˜1.61(m, 6H, THP), 0.23(s, 9H, 3 CH3).

後処理

  1. customThe salt formed during the reaction procedure
  2. filtrationwas filtered off
  3. washwashed well with ethyl acetate
  4. customThe filtrate was evaporated to dryness and hydrolyzed with concentrated hydrochloric acid (5 ml), water (25 ml)
  5. customcrushed ice (10 g)
  6. extractionextracted with ethyl acetate
  7. washThe combined organic paste was washed with brine
  8. dry with materialdried with MgSO4
  9. customThe solvent was removed in vacuo
  10. customthe residue was purified by column chromatography (petroleum ether-ethyl acetate=9:1)
  11. customto give a yellow oil of 2

出典と根拠

ORDレコード
ord-eeefb2a199d048a9aeec94c9f646f6f9
出典データセット
uspto-grants-2006_08
特許番号
US07094809B2

反応ノート

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