Chloroacetone → HCID 87378571, compound

HRID 1257063Notes

Reaction equation

HRID 1257063 reaction equation
[Br:1][C:2]1[C:3]([Br:15])=[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.Cl[CH2:17]C(=O)C.C(=O)([O-])[O-].[K+].[K+].[Br:27][C:28]1[N:33]=[C:32]2[CH:34]=[N:35][NH:36][C:31]2=[CH:30][C:29]=1[Br:37].[NH2:38][C:39]1[C:40]([CH3:47])=[N:41][C:42]([Br:46])=[C:43]([Br:45])[CH:44]=1.NC1C(C)=NC=C(Br)C=1.BrN1C(=O)CCC1=O>C(#N)C.C1(C)C=CC=CC=1>[NH2:7][C:6]([CH3:17])([CH2:5][N:35]1[CH:34]=[C:32]2[N:33]=[C:28]([Br:27])[C:29]([Br:37])=[CH:30][C:31]2=[N:36]1)[C:8]#[N:9].[Br:1][C:2]1[C:3]([Br:15])=[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:1][C:2]1[N:7]=[C:6]2[CH:8]=[N:9][NH:10][C:5]2=[CH:4][C:3]=1[Br:15].[NH2:38][C:39]1[C:40]([CH3:47])=[N:41][C:42]([Br:46])=[C:43]([Br:45])[CH:44]=1

Participants

13

Reactant 7

HCID 6571ChloroacetoneHCID 11430Potassium CarbonateHCID 67184N-bromobutanimideHCID 219640965-Bromo-2-methylpyridin-3-amineHCID 76847112HCID 76847112, compoundHCID 87378571HCID 87378571, compoundHCID 87544091HCID 87544091, compound

Product 4

HCID 76847112HCID 76847112, compoundYield 75%HCID 86641834HCID 86641834, compoundYield 86%HCID 87378571HCID 87378571, compoundYield 89%HCID 87544091HCID 87544091, compound

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6342AcetonitrileSolvent

Procedure

Using a procedure similar to that described in Example 1, except using 2-amino-3-(5,6-dibromo-2H-pyrazolo[4,3-b]pyridin-2-yl)-2-methylpropionitrile (60 mg), the title compound was isolated as a white solid (51 mg, 56%). MS (ES): M/Z [M+H]=546. 1H NMR: (400 MHz, DMSO-d6): 1.68 (s, 3H), 5.15 (d, J=13.6 Hz, 1H), 5.16 (d, J=13.6 Hz, 1H), 7.53 (d, J=8.4 Hz, 2H), 7.97 (d, J=8.8 Hz, 2H), 8.74 (s, 1H), 8.78 (s, 1H) and 8.96 (s, 1H). 19F NMR (376 MHz, DMSO-d6): −57.1 (s, 3F). 2-Amino-3-(5,6-dibromo-2H-pyrazolo[4,3-b]pyridin-2-yl)-2-methylpropionitrile (260 mg, 86%; MS (ES): M/Z [M+H]=360) was prepared using a procedure similar to that described in Example 1, part b, except starting from 1-(5,6-dibromo-2H-pyrazolo[4,3-b]pyridin-2-yl)propan-2-one (280 mg). 1-(5,6-Dibromo-2H-pyrazolo[4,3-b]pyridin-2-yl)propan-2-one (300 mg) was prepared using a procedure similar to that described in Example 182 part g using chloroacetone and potassium carbonate except starting from 5,6-dibromo-1H-pyrazolo[4,3-b]pyridine (1.18 g). 5,6-Dibromo-1H-pyrazolo[4,3-b]pyridine (1.18 g, 75%) was prepared using a procedure similar to that described in Example 182 part f except starting from 3-amino-5,6-dibromo-2-methylpyridine (1.5 g) and using toluene instead of chloroform. 3-Amino-5,6-dibromo-2-methylpyridine (2.53 g, 89%) was prepared by bromination of 3-amino-5-bromo-2-methylpyridine (2 g, described in Example 182) with N-bromosuccinimide (2.1 g) in acetonitrile (80 mL) at 50° C.

Sources & evidence

ORD record
ord-750182962efe4dc2b2fafa8c648b1718
Source dataset
uspto-grants-2013_06
Patent number
US08461176B2

Reaction notes

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