Tetrahydrofuran → 6'-Bromospiro[cyclobutane-1,2'-inden]-1'(3'H)-one

HRID 539286

反応式

HRID 539286 の反応式
[Br:1][C:2]1[CH:14]=[CH:13][C:5]([CH2:6][C:7]2([C:11]#N)[CH2:10][CH2:9][CH2:8]2)=[C:4](I)[CH:3]=1.C([Li])(C)(C)C.C1C[O:24]CC1>>[Br:1][C:2]1[CH:14]=[C:13]2[C:5]([CH2:6][C:7]3([CH2:10][CH2:9][CH2:8]3)[C:11]2=[O:24])=[CH:4][CH:3]=1

参加物

4

反応物 3

HCID 8028TetrahydrofuranHCID 679794311-(4-Bromo-2-iodobenzyl)cyclobutanecarbonitrile2 回HCID 178418306HCID 178418306、化合物

生成物 1

HCID 679796166'-Bromospiro[cyclobutane-1,2'-inden]-1'(3'H)-one収率 63%

反応条件

温度
-78 °C

実験手順

A dried flask charged with 1-(4-bromo-2-iodobenzyl)cyclobutanecarbonitrile (Intermediate 37, 2.60 g, 6.91 mmol), was dissolved in dry THF (100 mL) under an argon atmosphere. The resulting mixture was cooled to −78° C. and then was tert-butyllithium (1.7 M in pentane, 8.13 mL, 13.83 mmol), added dropwise. The reaction was stirred for 1.5 h at −78° C. and then the reaction was quenched with MeOH (0.5 mL), followed by aq. hydrochloric acid (2M, 10 mL). The resulting solution was concentrated to remove the organic solvent and then partitioned between DCM and water. The organic phase was dried over MgSO4 and concentrated to give a crude product which was purified by flash chromatography (eluent: heptane/EtOAc20:1-15:1-10:1) to afford the title compound (1.1 g, 63% yield): 1H NMR (500 MHz, CDCl3) δ ppm 1.97-2.13 (m, 3 H), 2.13-2.24 (m, 1 H), 2.45-2.60 (m, 2 H), 3.24 (s, 2 H), 7.31 (d, 1 H), 7.67 (dd, 1 H), 7.88 (d, 1 H); GC MS (EI) m/z 250 M+.

後処理

  1. additionadded dropwise
  2. customthe reaction was quenched with MeOH (0.5 mL)
  3. concentrationThe resulting solution was concentrated
  4. customto remove the organic solvent
  5. custompartitioned between DCM and water
  6. dry with materialThe organic phase was dried over MgSO4
  7. concentrationconcentrated
  8. customto give a crude product which
  9. customwas purified by flash chromatography (eluent: heptane/EtOAc20:1-15:1-10:1)

出典と根拠

ORDレコード
ord-30ee14740c3748e0a041cd63a9c76ef4
出典データセット
uspto-grants-2014_10
特許番号
US08865911B2

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