Triphenylphosphine → 3-amino-1'-(4-methoxybenzyl)spiro[furo[3,2-f][1,2]benzisoxazole-5,3'-indol]-2'(1'H)-one

HRID 1965811ノート

反応式

HRID 1965811 の反応式
O[N:2]=[C:3]([C:5]1[C:6]([OH:32])=[CH:7][C:8]2[O:31][CH2:30][C:11]3([C:19]4[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=4)[N:13]([CH2:20][C:21]4[CH:26]=[CH:25][C:24]([O:27][CH3:28])=[CH:23][CH:22]=4)[C:12]3=[O:29])[C:9]=2[CH:10]=1)[NH2:4].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O.[OH-].[Na+]>O1CCCC1>[NH2:4][C:3]1[C:5]2[CH:10]=[C:9]3[C:11]4([C:19]5[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=5)[N:13]([CH2:20][C:21]5[CH:26]=[CH:25][C:24]([O:27][CH3:28])=[CH:23][CH:22]=5)[C:12]4=[O:29])[CH2:30][O:31][C:8]3=[CH:7][C:6]=2[O:32][N:2]=1

参加物

6

反応物 4

HCID 11776TriphenylphosphineHCID 14798Sodium HydroxideHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 136348351N',6-dihydroxy-1'-(4-methoxybenzyl)-2'-oxo-1',2'-dihydrospiro[1-benzofuran-3,3'-indole]-5-carboximidamide

生成物 1

HCID 593522673-amino-1'-(4-methoxybenzyl)spiro[furo[3,2-f][1,2]benzisoxazole-5,3'-indol]-2'(1'H)-one収率 19%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

To a solution of N′,6-dihydroxy-1′-(4-methoxybenzyl)-2′-oxo-1′,2′-dihydrospiro[1-benzofuran-3,3′-indole]-5-carboximidamide (0.90 g, 2.1 mmol) and triphenylphosphine (0.71 g, 2.7 mmol) in tetrahydrofuran (30 mL) was added diethyl azodicarboxylate (0.43 mL, 2.7 mmol) at 0° C. The reaction mixture was allowed to warm to ambient temperature and was stirred for 16 h. 10% w/v aqueous sodium hydroxide (10 mL) was added and the mixture was stirred for 3 h. Most of the tetrahydrofuran was removed in vacuo and the resultant mixture was extracted with ethyl acetate (3×50 mL). The combined organic extracts were washed with water and brine, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated in vacuo. The residue was purified by column chromatography to afford 3-amino-1′-(4-methoxybenzyl)spiro[furo[3,2-f][1,2]benzisoxazole-5,3′-indol]-2′(1′H)-one (0.16 g, 19%): mp 214-216° C.; 1H NMR (300 MHz, DMSO-d6) δ 7.29-7.20 (m, 5H), 7.14-7.12 (m, 1H), 7.05 (s, 1H), 7.02-6.98 (m, 2H), 6.90-6.87 (m, 2H), 6.29 (s, 1H), 4.92-4.69 (m, 4H), 3.69 (s, 3H); 13C NMR (75 MHz, DMSO-d6) δ 177.3, 162.8, 159.1, 155.3, 148.8, 142.6, 138.1, 132.5, 129.1, 128.7, 124.5, 124.1, 123.4, 114.5, 109.9, 109.2, 93.0, 79.9, 57.9, 55.5, 42.9; MS (ES+) m/z 413.9 (M+1).

後処理

  1. additionwas added
  2. stirringthe mixture was stirred for 3 h
  3. customMost of the tetrahydrofuran was removed in vacuo
  4. extractionthe resultant mixture was extracted with ethyl acetate (3×50 mL)
  5. washThe combined organic extracts were washed with water and brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationThe filtrate was concentrated in vacuo
  9. customThe residue was purified by column chromatography

出典と根拠

ORDレコード
ord-4de61cbd40c244c582bada229737cc62
出典データセット
uspto-grants-2013_04
特許番号
US08415370B2

反応ノート

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