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

HRID 1970796

반응식

HRID 1970796 반응식
[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(CC)CC)C.[CH3:32][S:33](Cl)(=[O:35])=[O:34].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:33]([CH3:32])(=[O:35])=[O:34])[S:33]([CH3:32])(=[O:35])=[O:34])=[N:15][CH:16]=2)=[CH:9][CH:10]=1)(=[O:3])[CH3:2]

참가 물질

6

반응물 4

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 670035525-(4-Acetoxyphenyl)-2-amino-3-benzylpyrazine

생성물 1

HCID 468661705-(4-Acetoxyphenyl)-3-benzyl-2-bis(methanesulfonyl)aminopyrazine

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

Under an argon atmosphere, 5-(4-acetoxyphenyl)-2-amino-3-benzylpyrazine (c-19) (337 mg, 1.05 mmol) was dissolved in anhydrous dichloromethane (9 mL), and to this was added triethylamine (220 μL, 1.58 mmol) and stirred at room temperature. To this was added methanesulfonyl chloride (245 μL, 3.16 mmol) and stirred for 1.5 h at the same temperature. 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 with saturated aqueous solution of sodium sulfate and 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 (28 g, n-hexane/ethyl acetate=3/1→3/2) to give 5-(4-acetoxyphenyl)-3-benzyl-2-bis(methanesulfonyl)aminopyrazine (c-39) as a yellow amorphous (241 mg, 48.3%). Rf=0.32 (n-hexane/ethyl acetate=3/2). Mp. 165.5-167° C. UV (MeOH) λmax (log ε) 306 (4.29), 293 (4.25), 259 (4.21). UV (pH PB) λmax (log ε) 336.5 (4.19), 264 (4.09). 1H NMR (400 MHz, DMSO-d6) δ 2.29 (s, 3H), 3.59 (s, 6H), 4.36 (s, 2H), 7.20-7.26 (m, 1H), 7.26-7.35 (m, 6H), 8.11-8.17 (AA′BB′, 2H), 9.14 (s, 1H). 13C NMR (75.5 MHz, DMSO-d6) δ 20.9, 38.5, 43.1 (1C×2), 122.7 (2C), 126.6, 128.3 (2C), 128.6 (2C), 129.5 (2C), 132.1, 137.6, 139.2, 141.5, 151.4, 152.5, 155.6, 169.0. IR (KBr, cm−1) 509, 523, 706, 756, 766, 912, 974, 1015, 1163, 1200, 1321, 1368, 1418, 1435, 1528, 1603, 1755, 3032. HRMS (FAB+) m/z 476.0936 (M+H, C21H22N3O6S2 requires 476.0950).

후처리

  1. stirringstirred for 1.5 h at the same temperature
  2. customthe reaction
  3. customafter separating the aqueous layer and organic layer
  4. washthe organic layer was washed with saturated aqueous solution of sodium sulfate
  5. dry with materialdried over anhydrous sodium sulfate
  6. customAfter removing anhydrous sodium sulfate
  7. filtrationby filtration
  8. concentrationthe filtrate was concentrated under reduced pressure with a rotary evaporator
  9. customThe residue was purified by silica gel column chromatography (28 g, n-hexane/ethyl acetate=3/1→3/2)

출처 및 근거

ORD 기록
ord-f1a91e066de64c72a457d0d42f326764
출처 데이터셋
uspto-grants-2013_04
특허 번호
US08431525B2

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