N,N,N',N'-Tetramethylethylenediamine → Spiro[cyclohexane-1,3'-indolin]-2'-one

HRID 9311

反応式

HRID 9311 の反応式
[NH:1]1[C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[CH2:3][C:2]1=[O:10].C([Li])CCC.CN(C)CCN(C)C.I[CH2:25][CH2:26][CH2:27][CH2:28][CH2:29]I.[Cl-].[NH4+]>O1CCCC1.CCOC(C)=O>[NH:1]1[C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[C:3]2([CH2:29][CH2:28][CH2:27][CH2:26][CH2:25]2)[C:2]1=[O:10]

参加物

8

反応物 5

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 123541,5-DiiodopentaneHCID 25517Ammonium ChlorideHCID 321710OxindoleHCID 178418339Butyllithium

生成物 1

HCID 12888301Spiro[cyclohexane-1,3'-indolin]-2'-one収率 69.6%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

実験手順

A solution of oxindole (25 g, 0.19 mol) in anhydrous tetrahydrofuran (800 cm3) was cooled to −20° C., then n-butyllithium (2.5M in hexanes, 152 cm3, 0.38 mol) was added slowly followed by N,N,N′,N′-tetramethylethylenediamine (51 cm3, 0.38 mol,). After 15 min. 1,5-diiodopentane (174 g, 0.54 mol) was added slowly and the mixture was allowed to warm to room temperature. After stirring for 16 h. saturated aqueous ammonium chloride solution (1 L) and EtOAc (1 L) were added. After 15 min., the layers were separated and the aqueous phase was extracted with EtOAc (×2). The combined organic layers were extracted with hydrochloric acid (1N), then washed with brine (500 cm3), dried (MgSO4), and concentrated to obtain an oil. The oil was triturated with hexane (200 cm3) and benzene (20 cm3). The precipitate was collected and dried in vacuo to obtain the subtitled compound (26.3 g, 69.6%) as colorless crystals: mp 110–114° C.; 1H NMR (DMSO-d6) δ 1.67 (m, 10H), 6.84 (d, 1H, J=8 Hz), 6.94 (t, 1H, J=8 Hz), 7.17 (t, 1H, J=8 Hz), 7.44 (d, 1H, J=8 Hz), 10.3 (s, 1H).

後処理

  1. additionwere added
  2. waitAfter 15 min.
  3. customthe layers were separated
  4. extractionthe aqueous phase was extracted with EtOAc (×2)
  5. extractionThe combined organic layers were extracted with hydrochloric acid (1N)
  6. washwashed with brine (500 cm3)
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated
  9. customto obtain an oil
  10. customThe oil was triturated with hexane (200 cm3) and benzene (20 cm3)
  11. customThe precipitate was collected
  12. customdried in vacuo

出典と根拠

ORDレコード
ord-36a01d141f4a4baca50a7e0cdac2419d
出典データセット
uspto-grants-2006_08
特許番号
US07091234B2

関連ノート

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