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

HRID 1965811노트

반응식

HRID 1965811 반응식
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

참가 물질

6

반응물 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

생성물 1

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

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-4de61cbd40c244c582bada229737cc62
출처 데이터셋
uspto-grants-2013_04
특허 번호
US08415370B2

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