Iodine → 2-Amino-3-(6-bromo-2H-pyrazolo[4,3-b]pyridin-2-yl)-2-methylpropionitrile

HRID 71004

반응식

HRID 71004 반응식
[Br:1][C:2]1[CH:7]=[N:6][C:5]2=[CH:8][N:9]([CH2:11][C:12](=O)[CH3:13])[N:10]=[C:4]2[CH:3]=1.[Si]([O:22][CH:23]([CH3:35])[CH2:24][N:25]1[CH:34]=[C:28]2[N:29]=[CH:30][C:31]([Br:33])=[CH:32][C:27]2=[N:26]1)([C:18](C)(C)[CH3:19])(C)C.[Br:36][C:37]1[CH:38]=[C:39]([N+:45]([O-:47])=[O:46])[C:40]([CH:43]=[O:44])=[N:41][CH:42]=1.N[C:49]1[C:54]([N+:55]([O-:57])=[O:56])=[CH:53][C:52]([Br:58])=[CH:51][N:50]=1.II.BrC1C=C([N+]([O-])=O)C(I)=NC=1.I([O-])(=O)(=O)=O.[Na+]>O.C1COCC1.[Cu](Br)Br.[Os](=O)(=O)(=O)=O>[NH2:41][C:12]([CH3:13])([CH2:11][N:9]1[CH:8]=[C:5]2[N:6]=[CH:7][C:2]([Br:1])=[CH:3][C:4]2=[N:10]1)[C:24]#[N:25].[Br:33][C:31]1[CH:30]=[N:29][C:28]2=[CH:34][N:25]([CH2:24][C:23](=[O:22])[CH3:35])[N:26]=[C:27]2[CH:32]=1.[Br:36][C:37]1[CH:38]=[C:39]([N+:45]([O-:47])=[O:46])[C:40]([CH:43]=[O:44])=[N:41][CH:42]=1.[Br:58][C:52]1[CH:53]=[C:54]([N+:55]([O-:57])=[O:56])[C:49]([CH:18]=[CH2:19])=[N:50][CH:51]=1

참가 물질

15

반응물 7

HCID 807IodineHCID 1388782-Amino-5-bromo-3-nitropyridineHCID 23667635Sodium periodateHCID 573723425-Bromo-2-iodo-3-nitropyridineHCID 574158695-Bromo-3-nitropyridine-2-carbaldehydeHCID 666199941-(6-Bromo-2H-pyrazolo[4,3-b]pyridin-2-yl)propan-2-oneHCID 666203832-[2-(tert-butyldimethylsilanyloxy)propyl]-6-bromo-2H-pyrazolo[4,3-b]pyridine

생성물 4

HCID 574158695-Bromo-3-nitropyridine-2-carbaldehyde수율 62%HCID 666199941-(6-Bromo-2H-pyrazolo[4,3-b]pyridin-2-yl)propan-2-oneHCID 666201262-Amino-3-(6-bromo-2H-pyrazolo[4,3-b]pyridin-2-yl)-2-methylpropionitrile수율 80%HCID 666206915-Bromo-2-ethenyl-3-nitropyridine

시약·촉매·용매 4

HCID 24611Copper bromide (CuBr2)촉매HCID 30318Osmium Tetroxide촉매HCID 962Water용매2회HCID 8028Tetrahydrofuran용매

실험 절차

2-Amino-3-(6-bromo-2H-pyrazolo[4,3-b]pyridin-2-yl)-2-methylpropionitrile (416 mg, 80%) was prepared using a procedure similar to that described in Example 1, part b, except starting from 1-(6-bromo-2H-pyrazolo[4,3-b]pyridin-2-yl)propan-2-one (471 mg). 1-(6-Bromo-2H-pyrazolo[4,3-b]pyridin-2-yl)propan-2-one was prepared using a procedure similar to that described in Example 105 part c and d except starting from 2-[2-(tert-butyldimethylsilanyloxy)propyl]-6-bromo-2H-pyrazolo[4,3-b]pyridine (289 mg, 39%) that was prepared using a procedure similar to that described in Example 155 except starting from 5-bromo-3-nitropyridine-2-carboxaldehyde (462 mg). 5-Bromo-3-nitropyridine-2-carboxaldehyde was prepared using a procedure similar to that described in Example 136 part a to c except starting from 2-amino-5-bromo-3-nitropyridine (50 g) and using iodine (69.9 g) in part a instead of copper bromide to generate 5-bromo-2-iodo-3-nitropyridine as a yellow solid (27.4 g, 36%). Oxidative cleavage using a 4% solution of osmium tetroxide in water (4 mL) and sodium periodate (6.7 g) was carried out in a mixture of THF and water (10:1, 390 mL) in part c instead of ozonolysis following a procedure similar to that described in Example 61 to afford 5-bromo-3-nitropyridine-2-carboxaldehyde as a tan solid (3.8 g, 62%) from 5-bromo-3-nitro-2-vinylpyridine (6 g).

후처리

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  2. custom5-Bromo-3-nitropyridine-2-carboxaldehyde was prepared

출처 및 근거

ORD 기록
ord-66d4abf65856467594060c2ed7b017f3
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08822689B2

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