Acetic Anhydride → 5-(4-Acetoxyphenyl)-2-amino-3-benzylpyrazine

HRID 1970785

Reaktionsgleichung

Reaktionsgleichung von HRID 1970785
[NH2:1][C:2]1[C:7]([CH2:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[N:6][C:5]([C:15]2[CH:20]=[CH:19][C:18]([OH:21])=[CH:17][CH:16]=2)=[CH:4][N:3]=1.[C:22](OC(=O)C)(=[O:24])[CH3:23].C(=O)(O)[O-].[Na+].C(OCC)(=O)C>N1C=CC=CC=1>[C:22]([O:21][C:18]1[CH:17]=[CH:16][C:15]([C:5]2[N:6]=[C:7]([CH2:8][C:9]3[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=3)[C:2]([NH2:1])=[N:3][CH:4]=2)=[CH:20][CH:19]=1)(=[O:24])[CH3:23]

Komponenten

6

Edukt 4

HCID 7918Acetic AnhydrideHCID 8857Ethyl AcetateHCID 1937434-(5-Amino-6-(phenylmethyl)-2-pyrazinyl)phenolHCID 516892Sodium Bicarbonate

Produkt 1

HCID 670035525-(4-Acetoxyphenyl)-2-amino-3-benzylpyrazineAusbeute 96,7 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1049PyridineLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

Under an argon atmosphere, 2-amino-3-benzyl-5-(4-hydroxyphenyl)pyrazine (coelenteramine) (c-5) (prepared by the method described in Adamczyk, M. et al., Org. Prep. Proced. Int., 33, 477-485 (2001)) (303 mg, 1.09 mmol) was dissolved in pyridine (2 mL) and cooled to 0° C. To this was added acetic anhydride (133 μL, 1.40 mmol) and stirred for an hour after warming to room temperature. To the mixture was added saturated aqueous solution of sodium bicarbonate and ethyl acetate to stop the reaction. After separating the aqueous layer and organic layer, it was extracted 3 times with ethyl acetate. The organic layer was washed 3 times with water and once with saturated brine, and then dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the filtrate was concentrated under reduced pressure with a rotary evaporator. The residue was purified by column chromatography (50 g, n-hexane/ethyl acetate=1/1) to give 5-(4-acetoxyphenyl)-2-amino-3-benzylpyrazine (c-19) as a pale yellow solid (337 mg, 96.7%). Rf=0.31 (n-hexane/ethyl acetate=3/2). Mp. 183.5-185.5° C. 1H NMR (400 MHz, DMSO-d6) δ 2.27 (s, 3H), 4.07 (s, 2H), 6.42 (s, 2H), 7.12-7.17 (AA′BB′, 2H), 7.19 (d, J=7.2 Hz, 1H), 7.27 (t, J=7.5 Hz, 2H), 7.33 (d, J=7.0 Hz, 2H), 7.90-7.95 (AA′BB′, 2H), 8.41 (s, 1H). IR (KBr, cm−1) 513, 596, 640, 654, 710, 746, 851, 910, 1016, 1136, 1167, 1198, 1217, 1373, 1423, 1452, 1466, 1493, 1508, 1535, 1630, 1746, 3148, 3289.

Aufarbeitung

  1. temperatureafter warming to room temperature
  2. customthe reaction
  3. customAfter separating the aqueous layer and organic layer, it
  4. extractionwas extracted 3 times with ethyl acetate
  5. washThe organic layer was washed 3 times with water
  6. dry with materialonce with saturated brine, and then dried over anhydrous sodium sulfate
  7. customAfter removing anhydrous sodium sulfate
  8. filtrationby filtration
  9. concentrationthe filtrate was concentrated under reduced pressure with a rotary evaporator
  10. customThe residue was purified by column chromatography (50 g, n-hexane/ethyl acetate=1/1)

Quellen und Nachweise

ORD-Eintrag
ord-6c2faddbd92b478ab08feb3f6db004b6
Quelldatensatz
uspto-grants-2013_04
Patentnummer
US08431525B2

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