Acetic Anhydride → HCID 67003569, compound

HRID 1970789Notes

Reaction equation

HRID 1970789 reaction equation
[CH2:1]([C:8]1[C:9]([NH:21][C:22](=[O:31])[CH2:23][C:24]2[CH:29]=[CH:28][C:27]([OH:30])=[CH:26][CH:25]=2)=[N:10][CH:11]=[C:12]([C:14]2[CH:19]=[CH:18][C:17]([OH:20])=[CH:16][CH:15]=2)[N:13]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:32](OC(=O)C)(=[O:34])[CH3:33].C(=O)(O)[O-].[Na+].[C:44](OCC)(=[O:46])[CH3:45]>N1C=CC=CC=1>[C:32]([O:20][C:17]1[CH:18]=[CH:19][C:14]([C:12]2[N:13]=[C:8]([CH2:1][C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)[C:9]([NH:21][C:22](=[O:31])[CH2:23][C:24]3[CH:25]=[CH:26][C:27]([O:30][C:44](=[O:46])[CH3:45])=[CH:28][CH:29]=3)=[N:10][CH:11]=2)=[CH:15][CH:16]=1)(=[O:34])[CH3:33]

Participants

6

Reactant 4

HCID 7918Acetic AnhydrideHCID 8857Ethyl AcetateHCID 448487CoelenteramideHCID 516892Sodium Bicarbonate

Product 1

HCID 67003569HCID 67003569, compoundYield 60.7%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Conditions

Temperature
0 °C

Procedure

Under an argon atmosphere, 3-benzyl-5-(4-hydroxyphenyl)-2-[(4-hydroxyphenyl)acetylamino]pyrazine (coelenteramide) (c-4) (prepared by the method described in Inouye, S. & Hosoya, T., Biochem. Biophys. Res. Commun., 386, 617-622 (2009)) (410 mg, 997 μmol) was dissolved in pyridine (11 mL) and cooled to 0° C. To this was added acetic anhydride (475 μL, 5.02 mmol) and stirred for 22 h after warming to room temperature. To this were added saturated aqueous solution of sodium bicarbonate and ethyl acetate to stop the reaction, and after separating the aqueous layer and organic layer, the organic layer was washed twice with water and once with saturated brine. The precipitate in the organic layer was collected by filtration and dried in vacuo to give 5-(4-acetoxyphenyl)-2-(4-acetoxyphenyl)acetylamino-3-benzylpyrazine (c-29) as a colorless solid (300 mg, 60.7%). Rf=0.28 (n-hexane/ethyl acetate=1/1). Mp. 225-227° C. UV (MeOH, 0.3% DMSO) λmax (log ε) 318 (4.14), 290 (4.12), 259 (4.19). 1H NMR (400 MHz, DMSO-d6) δ 2.26 (s, 3H), 2.29 (s, 3H), 3.71 (s, 2H), 4.11 (s, 2H), 7.08 (t, J=8.6 Hz, 4H), 7.15 (t, J=7.8 Hz, 1H), 7.21 (t, J=7.8 Hz, 2H), 7.24-7.29 (AA′BB′, 2H), 7.34-7.40 (AA′BB′, 2H), 8.08-8.14 (AA′BB′, 2H), 8.95 (s, 1H), 10.67 (s, 1H). 13C NMR (75.5 MHz, DMSO-d6) δ 20.89, 20.92, 41.6, 121.8 (2C), 122.5 (2C), 126.3, 127.8 (2C), 128.3 (2C), 128.9 (2C), 130.3 (2C), 132.9, 133.2, 137.9, 138.1, 144.4, 147.5, 149.3, 150.6, 151.7, 169.1, 169.3, 169.9 (one carbon at benzyl position was unobservable due to overlapping with the septet peak of DMSO). IR (KBr, cm−1) 515, 590, 654, 704, 854, 918, 1016, 1157, 1190, 1211, 1238, 1346, 1371, 1418, 1449, 1493, 1543, 1672, 1751, 3287. HRMS (FAB+) m/z 496.1863 (M+H, C29H26N3O5 requires 496.1872).

Workup

  1. temperatureafter warming to room temperature
  2. customthe reaction
  3. customafter separating the aqueous layer and organic layer
  4. washthe organic layer was washed twice with water and once with saturated brine
  5. filtrationThe precipitate in the organic layer was collected by filtration
  6. customdried in vacuo

Sources & evidence

ORD record
ord-f5a380024ef64705a8639461c2ac5382
Source dataset
uspto-grants-2013_04
Patent number
US08431525B2

Reaction notes

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