Triethylamine → 3'-chloro-4-(1-ethyl-5-methyl-1H-pyrazol-4-ylmethyl)-3,4,5,6-tetrahydro-2H-[1,2']bipyrazinyl

HRID 220553노트

반응식

HRID 220553 반응식
[CH2:1]([N:3]1[C:7]([CH3:8])=[C:6]([CH:9]=O)[CH:5]=[N:4]1)[CH3:2].Cl.Cl.[Cl:13][C:14]1[C:15]([N:20]2[CH2:25][CH2:24][NH:23][CH2:22][CH2:21]2)=[N:16][CH:17]=[CH:18][N:19]=1.C(N(CC)CC)C.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClCCCl.C(O)(=O)C>[Cl:13][C:14]1[C:15]([N:20]2[CH2:21][CH2:22][N:23]([CH2:9][C:6]3[CH:5]=[N:4][N:3]([CH2:1][CH3:2])[C:7]=3[CH3:8])[CH2:24][CH2:25]2)=[N:16][CH:17]=[CH:18][N:19]=1

참가 물질

7

반응물 4

HCID 8471TriethylamineHCID 5732041-Ethyl-5-methyl-1H-pyrazole-4-carbaldehydeHCID 5049666Sodium triacetoxyborohydrideHCID 866416583'-chloro-3,4,5,6-tetrahydro-2H-[1,2']bipyrazinyl dihydrochloride

생성물 1

HCID 866416643'-chloro-4-(1-ethyl-5-methyl-1H-pyrazol-4-ylmethyl)-3,4,5,6-tetrahydro-2H-[1,2']bipyrazinyl수율 88.6%

시약·촉매·용매 2

HCID 111,2-Dichloroethane용매HCID 176Acetic Acid용매

실험 절차

Dissolve 1-ethyl-5-methyl-1H-pyrazole-4-carbaldehyde (2.92 g, 21.1 mmol) in 1,2-dichloroethane (184 mL). Add 3′-chloro-3,4,5,6-tetrahydro-2H-[1,2′]bipyrazinyl dihydrochloride (4.97 g, 18.3 mmol), triethylamine (5.9 mL, 42.3 mmol), sodium triacetoxyborohydride (6.72 g, 31.7 mmol) and acetic acid (1.98 mL) and stir at room temperature for 18 hr. Add aq. saturated sodium bicarbonate and extract four times with DCM. Dry combined organic layers (magnesium sulfate), filter, concentrate, and purify (silica gel chromatography, eluting with 50:50 to 100:0 ethyl acetate:hexanes then 10:90 to 20:80 methanol:ethyl acetate) to give 3′-chloro-4-(1-ethyl-5-methyl-1H-pyrazol-4-ylmethyl)-3,4,5,6-tetrahydro-2H-[1,2′]bipyrazinyl (5.2 g, 88%). MS (ES): m/z=321 [M+H]+.

후처리

  1. extractionAdd aq. saturated sodium bicarbonate and extract four times with DCM
  2. customDry
  3. filtrationfilter
  4. concentrationconcentrate
  5. custompurify (silica gel chromatography
  6. washeluting with 50:50 to 100:0 ethyl acetate

출처 및 근거

ORD 기록
ord-8001cda7f8dd4de2aa89f2d9acdb9526
출처 데이터셋
uspto-grants-2012_06
특허 번호
US08202873B2

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