Iodine → 5-Bromo-4-methyl-3-nitropyridine-2-carboxaldehyde

HRID 70998

Reaktionsgleichung

Reaktionsgleichung von HRID 70998
N[C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[C:6]([CH3:11])[C:5]([Br:12])=[CH:4][N:3]=1.II.[Br:15][C:16]1[C:17]([CH3:26])=[C:18]([N+:23]([O-:25])=[O:24])[C:19](I)=[N:20][CH:21]=1.I([O-])(=O)(=O)=O.[Na+].[OH2:33]>C1COCC1.[Cu](Br)Br.[Os](=O)(=O)(=O)=O>[Br:12][C:5]1[C:6]([CH3:11])=[C:7]([N+:8]([O-:10])=[O:9])[C:2]([CH:16]=[O:33])=[N:3][CH:4]=1.[Br:15][C:16]1[C:17]([CH3:26])=[C:18]([N+:23]([O-:25])=[O:24])[C:19]([CH:2]=[CH2:7])=[N:20][CH:21]=1

Komponenten

10

Edukt 5

HCID 807IodineHCID 962Water2×HCID 72132072-Amino-5-bromo-4-methyl-3-nitropyridineHCID 23667635Sodium periodateHCID 866255945-Bromo-2-iodo-4-methyl-3-nitropyridine

Produkt 2

HCID 666209635-Bromo-4-methyl-3-nitro-2-vinylpyridineHCID 866255935-Bromo-4-methyl-3-nitropyridine-2-carboxaldehydeAusbeute 59 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24611Copper bromide (CuBr2)KatalysatorHCID 30318Osmium TetroxideKatalysatorHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

2-Amino-3-(6-bromo-3-methoxy-7-methyl-2H-pyrazolo[4,3-b]pyridin-2-yl)-2-methylpropionitrile (20 mg) was prepared using a procedure similar to that described in Example 1, part b, except starting from 1-(6-bromo-3-methoxy-7-methyl-2H-pyrazolo[4,3-b]pyridin-2-yl)propan-2-one (117 mg). 1-(6-Bromo-3-methoxy-7-methyl-2H-pyrazolo[4,3-b]pyridin-2-yl)propan-2-one was prepared using a procedure similar to that described in Example 105 part a to d except using 5-bromo-4-methyl-3-nitropyridine-2-carboxaldehyde (5.5 g) in part a to yield [2-(tert-butyldimethylsilanyloxy)propyl]-(5-bromo-4-methyl-3-nitropyridin-2-yl-methyl)amine (6 g, 67%). 5-Bromo-4-methyl-3-nitro-pyridine-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-4-methyl-3-nitropyridine (58.6 g) and using iodine (64 g) in part a instead of copper bromide to generate 5-bromo-2-iodo-4-methyl-3-nitropyridine (28.7 g, 33%). Oxidative cleavage using a 4% solution of osmium tetroxide in water (3 mL) and sodium periodate (23.1 g) was carried out in a mixture of THF and water (10:1, 330 mL) in part c instead of ozonolysis following a procedure similar to that described in Example 61 to afford 5-bromo-4-methyl-3-nitropyridine-2-carboxaldehyde (11.7 g, 59%) from 5-bromo-4-methyl-3-nitro-2-vinylpyridine (18.8 g). 2-Amino-5-bromo-4-methyl-3-nitropyridine (120.2 g, 85%) was prepared using a procedure similar to that described in Example 38 part a except starting from 2-amino-4-methyl-3-nitropyridine (101.5 g).

Aufarbeitung

  1. custom5-Bromo-4-methyl-3-nitro-pyridine-2-carboxaldehyde was prepared

Quellen und Nachweise

ORD-Eintrag
ord-36051ea289fc4cfc99d26aac560692b9
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08822689B2

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