Acetic Anhydride → HCID 71311757, compound

HRID 1175109Notes

Reaction equation

HRID 1175109 reaction equation
[N:1]([CH2:4][C:5]([NH:7][C@H:8]1[C@@H:14]([OH:15])[C@H:13]([OH:16])[C@@H:12]([CH2:17][OH:18])[O:11][CH:9]1[OH:10])=[O:6])=[N+:2]=[N-:3].C(O[C:23](=[O:25])[CH3:24])(=O)C>N1C=CC=CC=1.CN(C1C=CN=CC=1)C.C(Cl)Cl>[C:5]([O:10][CH:9]1[O:11][C@H:12]([CH2:17][O:18][C:23](=[O:25])[CH3:24])[C@@H:13]([O:16][C:12](=[O:11])[CH3:13])[C@H:14]([O:15][C:9](=[O:10])[CH3:8])[C@@H:8]1[NH:7][C:5](=[O:6])[CH2:4][N:1]=[N+:2]=[N-:3])(=[O:6])[CH3:4]

Participants

6

Reactant 2

HCID 7918Acetic AnhydrideHCID 42612215HCID 42612215, compound

Product 1

HCID 71311757HCID 71311757, compoundYield 190.8%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1049PyridineSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 20 (25 mg, 0.095 mmol) in pyridine (2 mL) was cooled to 0° C. To this solution was added acetic anhydride (1.0 mL, 11 mmol) and a catalytic amount of DMAP. The reaction mixture was stirred overnight and allowed to warm to rt. The resulting light yellow solution was diluted with CH2Cl2 (100 mL) and washed with 1 N HCl (3×50 mL), sat. NaHCO3 (1×50 mL), water (1×50 mL) and sat. NaCl (1×50 mL). The combined aqueous layers were back extracted with 50 mL of CH2Cl2. The combined organic layers were dried over Na2SO4 and concentrated. The crude product was purified by silica gel chromatography eluting with a gradient of 1:10 to 1:2 EtOAc/hexanes to afford 39 mg (95%) of a light yellow oil. IR (thin film): 3317, 2106, 1744, 1677, 1529 cm−1. 1H NMR (500 MHz, CDCl3): δ 2.05 (app s, 6H), 2.10 (s, 3H), 2.12 (s, 3H), 3.82 (ddd, 1H, J=2.4, 4.5, 9.6), 3.93 (s, 2H), 4.13 (dd, 1H, J=2.4, 12.6), 4.29 (dd, 1H, J=4.5, 12.6), 5.15 (app t, 1H, J=9.6), 5.21 (app t, 1H, J=5.7), 5.78 (app t, 1H, J=4.5), 6.37 (d, 1H, J=5.7). 13C NMR (125 MHz, CDCl3): δ 20.5, 20.5, 20.6, 20.6, 20.6, 20.8, 20.8, 51.2, 52.4, 52.5, 53.2, 61.4, 61.5, 67.4, 67.6, 69.8, 70.3, 72.0, 72.1, 72.9, 90.2, 92.1, 166.9, 168.6, 169.1, 169.2, 170.6, 170.8, 171.5. HRMS (FAB) m/z 437.1496 (MLi+C16H22LiN4O10 requires 437.1496).

Workup

  1. washwashed with 1 N HCl (3×50 mL), sat. NaHCO3 (1×50 mL), water (1×50 mL) and sat. NaCl (1×50 mL)
  2. extractionThe combined aqueous layers were back extracted with 50 mL of CH2Cl2
  3. dry with materialThe combined organic layers were dried over Na2SO4
  4. concentrationconcentrated
  5. customThe crude product was purified by silica gel chromatography
  6. washeluting with a gradient of 1:10 to 1:2 EtOAc/hexanes

Sources & evidence

ORD record
ord-0a8bd5ac5a1b408382e019858cfbdfa9
Source dataset
uspto-grants-2010_11
Patent number
US07838665B2

Reaction notes

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