Dibromodifluoromethane → Silane, [(4-bromo-4,4-difluoro-2-butynyl)oxy](1,1-dimethylethyl)dimethyl-

HRID 1363291ノート

反応式

HRID 1363291 の反応式
[C:1]([Si:5]([CH3:11])([CH3:10])[O:6][CH2:7][C:8]#[CH:9])([CH3:4])([CH3:3])[CH3:2].[Li]CCCC.[C:17](Br)([Br:20])([F:19])[F:18]>C1COCC1>[Br:20][C:17]([F:19])([F:18])[C:9]#[C:8][CH2:7][O:6][Si:5]([C:1]([CH3:3])([CH3:4])[CH3:2])([CH3:10])[CH3:11]

参加物

5

反応物 3

HCID 6382DibromodifluoromethaneHCID 3445622Propargyloxy-t-butyldimethylsilaneHCID 178418339Butyllithium

生成物 1

HCID 11961725Silane, [(4-bromo-4,4-difluoro-2-butynyl)oxy](1,1-dimethylethyl)dimethyl-収率 759.1%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

To a solution of tert-butyl-dimethyl-prop-2-ynyloxy-silane (11.6 g, 6.78 mmol) in dry THF (190 mL) was added nBuLi (46.6 mL, 1.6 M solution in hexanes) dropwise (via an addition funnel) over 30 min at 0° C. under N2. The reaction mixture was stirred at rt for 1.5 h before being cooled to −78° C. Then, CF2Br2 (18.8 mL, 20.3 mmol) was added dropwise over 30 min. After stirring for 2.5 h at −78° C., the reaction mixture was quenched with a saturated solution of NH4Cl and was extracted with ether. The combined organic extracts were washed with brine, dried over anhydrous Na2SO4, filtered, and concentrated. Vacuum distillation (0.35-0.7 Torr) provided (4-bromo-4,4-difluoro-but-2-ynyloxy)-tert-butyl-dimethyl-silane (15.4 g, 76% yield) as a yellow liquid (55-70° C.): 1H NMR (400 MHz, CDCl3) δ0.15 (s, 6H), 0.93 (s, 9H), 4.46 (t, J=4.08 Hz, 2H); 19F NMR (376.19 MHz, CDCl3) δ −33.01 (t, J=4.1 Hz, 2F).

後処理

  1. temperaturebefore being cooled to −78° C
  2. stirringAfter stirring for 2.5 h at −78° C.
  3. customthe reaction mixture was quenched with a saturated solution of NH4Cl
  4. extractionwas extracted with ether
  5. washThe combined organic extracts were washed with brine
  6. dry with materialdried over anhydrous Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. distillationVacuum distillation (0.35-0.7 Torr)

出典と根拠

ORDレコード
ord-27e89d829fbb42d4af0a5d47a051dcd5
出典データセット
uspto-grants-2011_02
特許番号
US07884124B2

反応ノート

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