Nitrogen → Isopropyl 4-(3-bromopyrazolo[1,5-a]pyrimidin-5-yl)piperazine-1-carboxylate

HRID 1478265ノート

反応式

HRID 1478265 の反応式
N#N.[Br:3][C:4]1[CH:5]=[N:6][N:7]2[CH:12]=[CH:11][C:10]([N:13]3[CH2:18][CH2:17][NH:16][CH2:15][CH2:14]3)=[N:9][C:8]=12.CCN(C(C)C)C(C)C.Cl[C:29]([O:31][CH:32]([CH3:34])[CH3:33])=[O:30]>C(OCC)(=O)C.C1(C)C=CC=CC=1>[CH:32]([O:31][C:29]([N:16]1[CH2:17][CH2:18][N:13]([C:10]2[CH:11]=[CH:12][N:7]3[N:6]=[CH:5][C:4]([Br:3])=[C:8]3[N:9]=2)[CH2:14][CH2:15]1)=[O:30])([CH3:34])[CH3:33]

参加物

7

反応物 4

HCID 947NitrogenHCID 7917Isopropyl chloroformateHCID 81531DiisopropylethylamineHCID 866974343-Bromo-5-(piperazin-1-yl)pyrazolo[1,5-a]pyrimidine

生成物 1

HCID 86697433Isopropyl 4-(3-bromopyrazolo[1,5-a]pyrimidin-5-yl)piperazine-1-carboxylate

試薬・触媒・溶媒 2

HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
0 °C

実験手順

To a rapidly stirred, 0° C., N2 blanketed, solution of 3-bromo-5-piperazin-1-yl-pyrazolo[1,5-a]pyrimidine (15.8 g, 56.0 mmol) and Hunig's base [7087-68-5] (20.0 mL, 114.8 mmol) in ethyl acetate (280 mL) was steadily added a 1.0M solution of isopropyl chloroformate in toluene (67.0 mL) over the course of 10 minutes. The reaction was allowed to stir and warm to ambient temperature over night at which time it was washed with brine, dried (MgSO4), preloaded onto silica gel, chromatographed (Silica gel, eluted with 100% ethyl acetate) and crystallized from ethyl acetate/heptane to afford 13.2 g of white powder, mp. 78-79° C. 1H NMR (400 MHz, DMSO-d6) δ ppm 1.22 (d, J=6.32 Hz, 6 H) 3.44-3.54 (m, 4 H) 3.67-3.79 (m, 4 H) 4.82 (spt, J=6.23 Hz, 1 H) 6.77 (d, J=7.83 Hz, 1 H) 7.97 (s, 1 H) 8.69 (d, J=7.83 Hz, 1 H). 13C NMR (100 MHz, DMSO-d6) δ ppm 21.94, 42.80, 43.87, 68.17, 77.32, 97.66, 136.47, 143.87, 144.40, 154.29, 155.64. LRMS (ESI) m/z 368.0/370.0 [(M+H)]+, calc'd for C14H18BrN5O2: 368.24.

後処理

  1. stirringto stir
  2. temperaturewarm to ambient temperature over night at which time it
  3. washwas washed with brine
  4. dry with materialdried (MgSO4)
  5. customchromatographed
  6. wash(Silica gel, eluted with 100% ethyl acetate)
  7. customcrystallized from ethyl acetate/heptane

出典と根拠

ORDレコード
ord-ba3012f927ce44469c851b2c43f0dbdf
出典データセット
uspto-grants-2016_08
特許番号
US09403832B2

反応ノート

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