Hydrochloric Acid → 5-(4-Acetoxyphenyl)-3-benzyl-2-bis(benzylsulfonyl)aminopyrazine

HRID 1970786

反応式

HRID 1970786 の反応式
[C:1]([O:4][C:5]1[CH:10]=[CH:9][C:8]([C:11]2[N:12]=[C:13]([CH2:18][C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[C:14]([NH2:17])=[N:15][CH:16]=2)=[CH:7][CH:6]=1)(=[O:3])[CH3:2].C(N([CH2:30][CH3:31])CC)C.[CH2:32]([S:39](Cl)(=[O:41])=[O:40])[C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1.Cl>ClCCl>[C:1]([O:4][C:5]1[CH:6]=[CH:7][C:8]([C:11]2[N:12]=[C:13]([CH2:18][C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[C:14]([N:17]([S:39]([CH2:32][C:31]3[CH:30]=[CH:35][CH:34]=[CH:33][CH:38]=3)(=[O:41])=[O:40])[S:39]([CH2:32][C:33]3[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=3)(=[O:41])=[O:40])=[N:15][CH:16]=2)=[CH:9][CH:10]=1)(=[O:3])[CH3:2]

参加物

6

反応物 4

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 74740Phenylmethanesulfonyl chloride2 回HCID 670035525-(4-Acetoxyphenyl)-2-amino-3-benzylpyrazine

生成物 1

HCID 468661695-(4-Acetoxyphenyl)-3-benzyl-2-bis(benzylsulfonyl)aminopyrazine

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

反応条件

温度
0 °C

実験手順

Under an argon atmosphere, 5-(4-acetoxyphenyl)-2-amino-3-benzylpyrazine (c-19) (367 mg, 1.15 mmol) was dissolved in anhydrous dichloromethane (9 mL) and to this was added triethylamine (480 μL, 3.44 mmol), and cooled to 0° C. To this was added benzylsulfonyl chloride (658 mg, 3.45 mmol) and stirred for 4.5 h after warming to room temperature. To this was further added benzylsulfonyl chloride (658 mg, 3.45 mmol) and the mixture was stirred for 1.5 h. To this was added 2 M hydrochloric acid to stop the reaction and after separating the aqueous layer and organic layer, the organic layer was washed once 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 silica gel column chromatography (23 g, n-hexane/ethyl acetate=4/1→7/3) to give 5-(4-acetoxyphenyl)-3-benzyl-2-bis(benzylsulfonyl)aminopyrazine (c-20) as a yellow amorphous (487 mg, 67.4%). Rf=0.53 (n-hexane/ethyl acetate=3/2). Mp. 84-86.5° C. UV (MeOH) λmax (log ε) 307 (4.26), 293.5 (4.21), 259.5 (4.19). UV (pH 7.4 PB) λmax (log ε) 320 (4.30), 298.5 (4.25), 265 (4.29). 1H NMR (400 MHz, DMSO-d6) δ 2.29 (s, 3H), 3.90 (s, 2H), 5.00 (s, 1H), 5.03 (s, 1H), 5.18 (s, 1H), 5.22 (s, 1H), 7.13-7.17 (m, 2H), 7.18-7.23 (m, 1H), 7.25-7.33 (m, 4H), 7.39-7.45 (m, 10H), 8.09-8.14 (AA′BB′, 2H), 9.21 (s, 1H). 13C NMR (75.5 MHz, DMSO-d6) δ 20.9, 37.4, 61.0 (1C×2), 122.7 (2C), 126.4, 126.8 (1C×2), 128.2 (2C), 128.5 (2C), 128.8 (2C×2), 129.3, 129.6 (2C), 131.6 (2C×2), 132.1, 137.5, 139.2, 141.0, 151.3, 152.5, 155.6, 169.0. IR (KBr, cm−1) 509, 534, 611, 696, 777, 876, 912, 1144, 1163, 1198, 1354, 1375, 1416, 1433, 1757. HRMS (FAB+) m/z 628.1582 (M+H, C33H30N3O6S2 requires 628.1576).

後処理

  1. temperatureafter warming to room temperature
  2. stirringthe mixture was stirred for 1.5 h
  3. customthe reaction
  4. customafter separating the aqueous layer and organic layer
  5. washthe organic layer was washed once with water and once with saturated brine
  6. dry with materialdried 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 silica gel column chromatography (23 g, n-hexane/ethyl acetate=4/1→7/3)

出典と根拠

ORDレコード
ord-ee2fd804721b4776846ae0ab7f045f3a
出典データセット
uspto-grants-2013_04
特許番号
US08431525B2

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