Hydrochloric Acid → HCID 20161367, compound

HRID 247045Notes

Reaction equation

HRID 247045 reaction equation
[CH2:1]([N:4]1[CH2:8][C:7]([NH:9][C:10]2[N:14]([CH2:15][CH2:16][Cl:17])[N:13]=[CH:12][C:11]=2[C:18]#[N:19])=[CH:6][C:5]1=[O:20])[CH:2]=[CH2:3].C[Al](C)C.Cl>ClCCl.CCCCCC.[OH-].[Na+]>[NH2:19][C:18]1[C:6]2[C:5](=[O:20])[N:4]([CH2:1][CH:2]=[CH2:3])[CH2:8][C:7]=2[N:9]=[C:10]2[N:14]([CH2:15][CH2:16][Cl:17])[N:13]=[CH:12][C:11]=12

Participants

7

Reactant 3

HCID 313Hydrochloric AcidHCID 16682925TrimethylaluminumHCID 20161351HCID 20161351, compound

Product 1

HCID 20161367HCID 20161367, compound

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolvent2×HCID 8058HexaneSolventHCID 14798Sodium HydroxideSolvent

Procedure

A suspension of 5-[N-(2-propenyl)-2-oxo-3-pyrrolin-4-yl]amino-1-(2-chloroethyl)-4-cyanopyrazole (19.60 g.) in dry dichloromethane (200 ml.) was cooled to 0° under nitrogen with stirring, while a solution of trimethylaluminium in hexane (57 ml. of 25 wt. % solution) was added dropwise. Gas evolved. The resulting clear yellow solution was warmed to room temperature and allowed to stir under nitrogen for three days. After cooling to 0° and introducing a vigorous stream of nitrogen, 3N aqueous HCl was added cautiously until gas evolution ceased. The mixture was then diluted with aqueous NaOH (400 ml. of 20% w/v solution) and dichloromethane (500 ml.) and the phases were separated. The aqueous layer was further extracted twice with dichloromethane (250 ml. each time) and the organic extracts were combined. These were washed with aqueous NaOH (250 ml. of 10% w/v solution), and then with brine (400 ml.), and finally dried (Na2SO4) Evaporation gave a yellow solid which was recrystallized from a minimum of EtOAc to give 4-amino-1-(2-chloroethyl)-6,7-dihydro-6-(2-propenyl)pyrazolo[3,4-b]pyrrolo[3,4-e]pyridin-5(1H)-one as a light yellow powder, 15.71 g.: m.p. 197.5°-199°.

Workup

  1. temperaturewas cooled to 0° under nitrogen
  2. additionwas added dropwise
  3. temperatureAfter cooling to 0°
  4. additionwas added cautiously until gas evolution
  5. customthe phases were separated
  6. extractionThe aqueous layer was further extracted twice with dichloromethane (250 ml
  7. washThese were washed with aqueous NaOH (250 ml. of 10% w/v solution)
  8. dry with materialwith brine (400 ml.), and finally dried
  9. custom(Na2SO4) Evaporation
  10. customgave a yellow solid which
  11. customwas recrystallized from a minimum of EtOAc

Sources & evidence

ORD record
ord-9f99bfac0513497c8efa337d3899069b
Source dataset
uspto-grants-1987_11
Patent number
US04705793

Reaction notes

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