Triethylamine → tert-Butyl 4-(5-bromo-2,3-dihydro-1H-inden-2-yl)piperazine-1-carboxylate

HRID 1519504ノート

反応式

HRID 1519504 の反応式
[CH2:1]([N:4]([CH2:12][CH:13]=C)[C:5](=[O:11])[O:6][C:7]([CH3:10])([CH3:9])[CH3:8])[CH:2]=C.[Br:15][C:16]1[CH:17]=[C:18]2[C:22](=[CH:23][CH:24]=1)[CH2:21][CH:20]([NH2:25])[CH2:19]2.C(N(CC)CC)C.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClCCl.O>[Br:15][C:16]1[CH:17]=[C:18]2[C:22](=[CH:23][CH:24]=1)[CH2:21][CH:20]([N:25]1[CH2:2][CH2:1][N:4]([C:5]([O:6][C:7]([CH3:8])([CH3:9])[CH3:10])=[O:11])[CH2:12][CH2:13]1)[CH2:19]2

参加物

7

反応物 4

HCID 8471TriethylamineHCID 5049666Sodium triacetoxyborohydrideHCID 5107724tert-Butyl N,N-diallylcarbamateHCID 112987955-bromo-2,3-dihydro-1H-inden-2-amine

生成物 1

HCID 86694442tert-Butyl 4-(5-bromo-2,3-dihydro-1H-inden-2-yl)piperazine-1-carboxylate

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6344Dichloromethane溶媒

反応条件

温度
-78 °C

実験手順

In a 100 mL round bottom flask, tert-butyl di(prop-2-en-1-yl)carbamate (0.74 mL, 3.4 mmol) was dissolved in dichloromethane (10 mL). The solution was cooled to −78° C. To above solution was bubbled ozone for 15 min. The solution turned into light blue and the color stayed. To above solution was bubbled nitrogen to remove excess ozone until the solution turned into colorless. To above solution was added (5-bromo-2,3-dihydro-1H-inden-2-amine (1.0 g, 3.4 mmol), triethylamine (0.48 mL, 3.4 mmol) followed by sodium triacetoxyborohydride (4.3 g, 20 mmol). The reaction was allowed to warm up to room temperature and stirred at this temperature overnight. HPLC-MS showed product was formed as major peak. To above solution was added water (5 mL), extracted with dichloromethane (10 mL×3). The organic phase was dried over MgSO4, filtered and concentrated. The product was obtained as white solid after purification by flash column chromatography. LC-MS (IE, m/z): 381.2 [M+1]+. 1H NMR (500 MHz, CDCl3, δ in ppm): 7.30 (1H, s), 7.25 (d, J=8.0 Hz, 1H), 7.03 (d, J=8.0 Hz, 1H), 2.0-4.0 (m, 13H), 1.5 (s, 9H).

後処理

  1. customTo above solution was bubbled ozone for 15 min
  2. customTo above solution was bubbled nitrogen
  3. customto remove excess ozone until the solution
  4. temperatureto warm up to room temperature
  5. customwas formed as major peak
  6. extractionextracted with dichloromethane (10 mL×3)
  7. dry with materialThe organic phase was dried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe product was obtained as white solid
  11. customafter purification by flash column chromatography

出典と根拠

ORDレコード
ord-685f5d67e3c948f8ad9d6a6e356f980b
出典データセット
uspto-grants-2015_07
特許番号
US09073882B2

反応ノート

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