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

HRID 2385571Notes

Reaction equation

HRID 2385571 reaction equation
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

Participants

6

Reactant 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

Product 1

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

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

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).

Workup

  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

Sources & evidence

ORD record
ord-2932d0cdd6c741089884578b2a49e2b4
Source dataset
uspto-grants-2012_09
Patent number
US08263606B2

Reaction notes

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