Chloroacetone → 6-Bromo-2-methylpyridin-3-amine

HRID 1257065

반응식

HRID 1257065 반응식
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[C:6](=[CH:8][N:9]([CH2:11][C:12](=[O:14])[CH3:13])[N:10]=2)[N:7]=1.ClCC(=O)C.C(=O)([O-])[O-].[K+].[K+].[Br:26][C:27]1[N:32]=[C:31]2[CH:33]=[N:34][NH:35][C:30]2=[CH:29][CH:28]=1.[NH2:36]C1C(C)=NC(Br)=CC=1.[Br:45][C:46]1[N:51]=[C:50]([CH3:52])[C:49]([N+:53]([O-])=O)=[CH:48][CH:47]=1>CC(=O)OCC.CCCCCCC>[NH2:36][C:12]([CH3:13])([CH2:11][N:9]1[CH:8]=[C:6]2[N:7]=[C:2]([Br:1])[CH:3]=[CH:4][C:5]2=[N:10]1)[C:31]#[N:32].[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[C:6](=[CH:8][N:9]([CH2:11][C:12](=[O:14])[CH3:13])[N:10]=2)[N:7]=1.[Br:26][C:27]1[N:32]=[C:31]2[CH:33]=[N:34][NH:35][C:30]2=[CH:29][CH:28]=1.[NH2:53][C:49]1[C:50]([CH3:52])=[N:51][C:46]([Br:45])=[CH:47][CH:48]=1

참가 물질

11

반응물 6

HCID 6571ChloroacetoneHCID 11430Potassium CarbonateHCID 144180456-Bromo-2-methylpyridin-3-amineHCID 247280146-Bromo-2-methyl-3-nitropyridineHCID 713076205-bromo-1H-pyrazolo[4,3-b]pyridineHCID 866418361-(5-Bromo-2H-pyrazolo[4,3-b]pyridin-2-yl)propan-2-one

생성물 4

HCID 144180456-Bromo-2-methylpyridin-3-amine수율 93%HCID 713076205-bromo-1H-pyrazolo[4,3-b]pyridine수율 24%HCID 866418352-Amino-3-(5-bromo-2H-pyrazolo[4,3-b]pyridin-2-yl)-2-methylpropionitrile수율 73%HCID 866418361-(5-Bromo-2H-pyrazolo[4,3-b]pyridin-2-yl)propan-2-one수율 12%

시약·촉매·용매 1

HCID 21899848Ethylacetate heptane용매

실험 절차

Using a procedure similar to that described in Example 1, except using 2-amino-3-(5-bromo-2H-pyrazolo[4,3-b]pyridin-2-yl)-2-methylpropionitrile (33 mg), the title compound was isolated as a white solid (46 mg, 84%). Rf=0.4 (1:1 EA/heptane). MS (ES): M/Z [M+H]=468. 1H NMR: (400 MHz, DMSO-d6): 1.69 (s, 3H), 5.06-5.24 (m, 2H), 7.44 (d, J=9.0 Hz, 1H), 7.53 (d, J=8.1 Hz, 2H), 7.97 (d, J=8.8 Hz, 2H), 8.12 (d, J=9.0 Hz, 1H), 8.69 (s, 1H) and 8.96 (s, 1H). 19F NMR (376 MHz, DMSO-d6): −57.1 (s, 3F). 2-Amino-3-(5-bromo-2H-pyrazolo[4,3-b]pyridin-2-yl)-2-methylpropionitrile [40 mg, 73%; Rf=0.35 (EA)] was prepared using a procedure similar to that described in Example 1, part b, except starting from 1-(5-bromo-2H-pyrazolo[4,3-b]pyridin-2-yl)propan-2-one (50 mg). 1-(5-Bromo-2H-pyrazolo[4,3-b]pyridin-2-yl)propan-2-one [80 mg, 12%; Rf=0.25 (2:1 EA/heptane)] was prepared using a procedure similar to that described in Example 182 part g using chloroacetone and potassium carbonate except starting from 5-bromo-1H-pyrazolo[4,3-b]pyridine (0.5 g). 5-Bromo-1H-pyrazolo[4,3-b]pyridine (0.5 g, 24%) was prepared using a procedure similar to that described in Example 182 part f except starting from 3-amino-6-bromo-2-methylpyridine (2 g). 3-Amino-6-bromo-2-methylpyridine [3.2 g, 93%; Rf=0.75 (1:1 EA/heptane)] was prepared using a procedure similar to that described in Example 182 part e except starting from 6-bromo-2-methyl-3-nitropyridine (4 g).

출처 및 근거

ORD 기록
ord-6e08628b746c4943b7a04c8e33109941
출처 데이터셋
uspto-grants-2013_06
특허 번호
US08461176B2

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