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

HRID 579309ノート

反応式

HRID 579309 の反応式
[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

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 312751,4-Dioxane溶媒

反応条件

温度
120 °C

実験手順

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].

後処理

  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

出典と根拠

ORDレコード
ord-29f8cd7043c74086980a58b9355d0ce2
出典データセット
uspto-grants-2015_05
特許番号
US09040712B2

反応ノート

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