Acetic Anhydride → HCID 14758613, compound

HRID 260387Notes

Reaction equation

HRID 260387 reaction equation
[CH:1]1[C:14]2[C:13]3[CH2:12][CH2:11][CH2:10][CH2:9][C:8]=3[CH:7]=[N+:6]([O-])[C:5]=2[CH:4]=[CH:3][CH:2]=1.[C:16]([O:19]C(=O)C)(=[O:18])[CH3:17]>>[C:16]([O:19][CH:12]1[C:13]2[C:8](=[CH:7][N:6]=[C:5]3[C:14]=2[CH:1]=[CH:2][CH:3]=[CH:4]3)[CH2:9][CH2:10][CH2:11]1)(=[O:18])[CH3:17]

Participants

3

Reactant 2

HCID 7918Acetic AnhydrideHCID 14758612HCID 14758612, compound2×

Product 1

HCID 14758613HCID 14758613, compoundYield 77%

Procedure

A solution of 7,8,9,10-tetrahydrophenanthridine N-oxide (Compound 4a) (1.23 g, 6.18 mmol) in acetic anhydride (50 mL) was heated to 100° C. for 20 hours, evaporated to dryness, dissolved in dichloromethane (50 mL) and washed with saturated sodium bicarbonate solution (50 mL). The aqueous layer was extracted with dichloromethane (2×50 mL), the combined organic layers were dried (Na2SO4), evaporated in vacuo, and the residue was purified by flash chromatography on silica eluting with Et2O to give pure Compound 5 (1.15 g, 77 percent) as a white crystalline solid: Rf =0.33 (ether); mp=128°-129° C. (from ether); IR (CDCl3) νmax 2970, 1728, 1241 cm-1 ; 1H NMR (500 MHz, CDCl3): δ 8.70 (s, 1 H, H-6), 8.08 (d, J=9.5 Hz, 1 H, H-4), 7.76 (d, J= 9.5 Hz, 1 H, H-1), 7.63 (t, J=7.2 Hz, 1 H, H-2 or H-3), 7.52 (t, J=7.2 Hz, 1 H, H-2 or H-3), 6.57 (bs, 1 H, CH--OAc), 3.02 (bd, J=17.5 Hz, 1 H, H-7), 2.88-2.80 (m, 1 H, H-7), 2.27 (bd, J=13.8 Hz, 1 H, H-9), 2.05 (s, 3 H, 0Ac), 2.01-1.88 (m, 3 H); 13C NMR (125 MHz, CDCl3): δ 170.2, 152.3, 147.5, 137.8, 131.8, 130.1, 127.9, 127.0, 126.8, 122.2, 64.5, 29.1, 27.8, 21.7, 18.4; MS (FAB+) m/e (relative intensity) 242 (M+H, 100), 182 (23); HRMS calcd. for C15H16NO2 (M+H) 242.1181, found 242.1181; Anal. calcd. for C15H15NO2 ; C, 74.67; H, 6.27; N, 5.80. Found: C, 74.59; H, 6.31; N, 5.82.

Workup

  1. customevaporated to dryness
  2. dissolutiondissolved in dichloromethane (50 mL)
  3. washwashed with saturated sodium bicarbonate solution (50 mL)
  4. extractionThe aqueous layer was extracted with dichloromethane (2×50 mL)
  5. dry with materialthe combined organic layers were dried (Na2SO4)
  6. customevaporated in vacuo
  7. customthe residue was purified by flash chromatography on silica eluting with Et2O

Sources & evidence

ORD record
ord-ccadfe4f70a34840a68aecfab83aa1e2
Source dataset
uspto-grants-1996_06
Patent number
US05527805

Reaction notes

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