Oxalyl chloride → Ethyl 4-chloro-1,6-diethyl-1H-pyrazolo[3,4-b]pyridine-5-carboxylate

HRID 1675654Notes

Reaction equation

HRID 1675654 reaction equation
[CH2:1]([N:3]1[C:7]2=[N:8][C:9]([CH2:18][CH3:19])=[C:10]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[C:11](O)=[C:6]2[CH:5]=[N:4]1)[CH3:2].C(Cl)(=O)C([Cl:23])=O>ClCCl.C1(C)C=CC=CC=1>[Cl:23][C:11]1[C:10]([C:13]([O:15][CH2:16][CH3:17])=[O:14])=[C:9]([CH2:18][CH3:19])[N:8]=[C:7]2[N:3]([CH2:1][CH3:2])[N:4]=[CH:5][C:6]=12

Participants

5

Reactant 2

HCID 65578Oxalyl chlorideHCID 178468995Ethyl 1,6-diethyl-4-hydroxy-1H-pyrazolo[3,4-b]pyridine-5-carboxylate2×

Product 1

HCID 59683218Ethyl 4-chloro-1,6-diethyl-1H-pyrazolo[3,4-b]pyridine-5-carboxylateYield 80.3%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Procedure

Ethyl 1,6-diethyl-4-hydroxy-1H-pyrazolo[3,4-b]pyridine-5-carboxylate (0.10 g, 0.38 mmol, 1 equivalent, e.g. which can be as prepared in Intermediate 2C) was dissolved in dichloromethane (1.5 ml). Oxalyl chloride (0.07 ml, 0.10 g, 0.76 mmol, 2.0 equivalents) was added in one portion to the stirred solution. The reaction mixture, a solution, was stirred at room temperature for 2 hours, then was heated to 39° C. and stirred for 22.5 hours at this temperature, and then allowed to cool. The reaction mixture was diluted with toluene and then the solvent was removed in vacuo to give a brown oil which solidified on standing at room temperature to yield the title compound as a brown solid (0.086 g, about 80% theory yield). HPLC (5 min generic solvent gradient): TRET about 3.43. Mass Spectrum: Found: MH+ 282.1.

Workup

  1. temperaturewas heated to 39° C.
  2. stirringstirred for 22.5 hours at this temperature
  3. temperatureto cool
  4. customthe solvent was removed in vacuo
  5. customto give a brown oil which
  6. customon standing at room temperature

Sources & evidence

ORD record
ord-5cd512dcac7b4c2a91cd25f4832eeeb4
Source dataset
uspto-grants-2011_08
Patent number
US08003663B2

Reaction notes

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