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

HRID 1478265노트

반응식

HRID 1478265 반응식
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]

참가 물질

7

반응물 4

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

생성물 1

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

시약·촉매·용매 2

HCID 1140Toluene용매HCID 8857Ethyl Acetate용매

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온도
0 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-ba3012f927ce44469c851b2c43f0dbdf
출처 데이터셋
uspto-grants-2016_08
특허 번호
US09403832B2

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