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Diisopropylethylamine → 5-[4-(3,5-di-tert-butyl-4-hydroxy-phenylsulfanyl)-piperidine-1-sulfonyl]-1-methyl-1H-pyrrole-2-carboxylic acid methyl ester

HRID 599474
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HRID 599474 반응식
[C:1]([C:5]1[CH:10]=[C:9]([S:11][CH:12]2[CH2:17][CH2:16][NH:15][CH2:14][CH2:13]2)[CH:8]=[C:7]([C:18]([CH3:21])([CH3:20])[CH3:19])[C:6]=1[OH:22])([CH3:4])([CH3:3])[CH3:2].C(N(C(C)C)CC)(C)C.[CH3:32][O:33][C:34]([C:36]1[N:37]([CH3:45])[C:38]([S:41](Cl)(=[O:43])=[O:42])=[CH:39][CH:40]=1)=[O:35]>C1COCC1.C(OCC)(=O)C.O>[CH3:32][O:33][C:34]([C:36]1[N:37]([CH3:45])[C:38]([S:41]([N:15]2[CH2:16][CH2:17][CH:12]([S:11][C:9]3[CH:8]=[C:7]([C:18]([CH3:21])([CH3:20])[CH3:19])[C:6]([OH:22])=[C:5]([C:1]([CH3:4])([CH3:3])[CH3:2])[CH:10]=3)[CH2:13][CH2:14]2)(=[O:43])=[O:42])=[CH:39][CH:40]=1)=[O:35]
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참가 물질

7

반응물 3

HCID 81531DiisopropylethylamineHCID 2736899Methyl 5-(chlorosulfonyl)-1-methyl-1H-pyrrole-2-carboxylateHCID 86635428HCID 86635428, 화합물

생성물 1

HCID 866354305-[4-(3,5-di-tert-butyl-4-hydroxy-phenylsulfanyl)-piperidine-1-sulfonyl]-1-methyl-1H-pyrrole-2-carboxylic acid methyl ester수율 98.8%

시약·촉매·용매 3

HCID 962
Water
용매
HCID 8028Tetrahydrofuran용매
HCID 8857Ethyl Acetate용매

실험 절차

Alternatively, to a solution of 2,6-di-tert-butyl-4-(piperidin-4-ylsulfanyl)-phenol (Ex. 3d, 48.0 g, 0.15 moles) in THF (1000 mL) was added diisopropylethyl amine (39.0 mL, 0.22 moles) and methyl-5-(chlorosulfonyl)-1-methyl-1H-pyrrole-2-carboxylate (35.5 g, 0.15 moles) and the resulting solution was stirred at room temperature for 5 hours. Upon completion, as determined by HPLC, the reaction was diluted with ethyl acetate (500 mL) and water (500 mL). The layers were cut and the organic layer was washed with 1N HCl (500 mL) and 6% brine (2×500 mL), and concentrated under reduced pressure to afford 77.2 g (98.8%) of 5-[4-(3,5-di-tert-butyl-4-hydroxy-phenylsulfanyl)-piperidine-1-sulfonyl]-1-methyl-1H-pyrrole-2-carboxylic acid methyl ester as a white solid, mp 185-187° C. 1H-NMR (400 MHz, CDCl3): δ 7.23 (s, 2H), 7.17 (d, 1H, J=1.6 Hz), 7.09 (d, 1H, J=2.0 Hz), 5.29 (s, 1H), 3.96 (s, 3H), 3.84 (s, 3H), 3.57 (m, 2H), 2.79 (m, 1H), 2.50 (m, 2H), 1.99 (m, 2H), 1.70 (m, 2H), 1.42 (s, 18H). HRMS (ESI) Calcd. for C26H38N2O5S2, 522.2222 (M+). Found: 522.2228. Anal. Calcd. for C26H38N2O5S2: C, 59.74; H, 7.33; N, 5.36; S, 12.27. Found: C, 59.48; H, 7.50; N, 5.22; S, 12.05.

후처리

  1. washthe organic layer was washed with 1N HCl (500 mL) and 6% brine (2×500 mL)
  2. concentrationconcentrated under reduced pressure

출처 및 근거

ORD 기록
ord-d40585d96c60429b9fd181f3d30fbb3e
출처 데이터셋
uspto-grants-2011_03
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US07897776B2

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