Diisopropylethylamine → 5-Bromo-N-methyl-N-(2,2,6,6-tetramethylpiperidin-4-yl)-1,3,4-thiadiazol-2-amine

HRID 579309노트

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HRID 579309 반응식
[Br:1][C:2]1[S:3][C:4](Br)=[N:5][N:6]=1.[CH3:8][NH:9][CH:10]1[CH2:15][C:14]([CH3:17])([CH3:16])[NH:13][C:12]([CH3:19])([CH3:18])[CH2:11]1.CCN(C(C)C)C(C)C>O1CCOCC1>[Br:1][C:2]1[S:3][C:4]([N:9]([CH3:8])[CH:10]2[CH2:11][C:12]([CH3:18])([CH3:19])[NH:13][C:14]([CH3:17])([CH3:16])[CH2:15]2)=[N:5][N:6]=1

참가 물질

5

반응물 3

HCID 81531DiisopropylethylamineHCID 30925302,5-Dibromo-1,3,4-thiadiazoleHCID 13657792N,2,2,6,6-Pentamethylpiperidin-4-amine

생성물 1

HCID 867271295-Bromo-N-methyl-N-(2,2,6,6-tetramethylpiperidin-4-yl)-1,3,4-thiadiazol-2-amine수율 72%

시약·촉매·용매 1

HCID 312751,4-Dioxane용매

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온도
120 °C

실험 절차

To a stirred solution of 2,5-dibromo-1,3,4-thiadiazole (2.975 g, 12.2 mmol) and N,2,2,6,6-pentamethylpiperidin-4-amine (2.493 g, 14.64 mmol) in dioxane (40 mL) was added DIPEA (10.65 mL, 61 mmol) and the resulting mixture refluxed at 120° C. for 16 hours. The reaction mixture was cooled to room temperature then filtered under vacuum, rinsed with dioxane, and the filtrate concentrated in vacuo to afford the crude product as a pink/red oil. The crude material was purified by flash chromatography using 3% [7M NH3 in MeOH]/DCM as the eluent to afford the title compound as a pink/red solid (2.924 g, 72% yield). LC-MS: Rt 0.70 min; MS m/z 335.2 [M+2H]+ [Method A]. 1H NMR (400 MHz, DMSO-d6) δ ppm 4.13-4.03 (m, 1H), 2.92 (s, 3H), 1.57 (dd, J=12.13, 3.54 Hz, 2H), 1.39 (t, J=12.13 Hz, 2H), 1.26 (br. s., 1H), 1.16 (s, 6H), 1.06 (s, 6H). LC-MS: Rt 1.12 min; MS m/z 335.2 [M+H]+ [Method B].

후처리

  1. temperatureThe reaction mixture was cooled to room temperature
  2. filtrationthen filtered under vacuum
  3. washrinsed with dioxane
  4. concentrationthe filtrate concentrated in vacuo
  5. customto afford the crude product as a pink/red oil
  6. customThe crude material was purified by flash chromatography

출처 및 근거

ORD 기록
ord-29f8cd7043c74086980a58b9355d0ce2
출처 데이터셋
uspto-grants-2015_05
특허 번호
US09040712B2

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