Hydrochloric Acid → HCID 20161347, compound

HRID 247043Notes

Reaction equation

HRID 247043 reaction equation
[O:1]=[C:2]1[CH:7]=[C:6]([NH:8][C:9]2[N:13]([CH2:14][CH2:15][Cl:16])[N:12]=[CH:11][C:10]=2[C:17]#[N:18])[CH2:5][CH2:4][NH:3]1.C[Al](C)C.Cl.[OH-].[Na+]>C(Cl)Cl.CCCCCCC.CCOC(C)=O>[NH2:18][C:17]1[C:7]2[C:2](=[O:1])[NH:3][CH2:4][CH2:5][C:6]=2[N:8]=[C:9]2[N:13]([CH2:14][CH2:15][Cl:16])[N:12]=[CH:11][C:10]=12

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 16682925TrimethylaluminumHCID 20161354HCID 20161354, compound

Product 1

HCID 20161347HCID 20161347, compoundYield 72%

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolventHCID 8900HeptaneSolvent

Procedure

To a mechanically stirred suspension of 5-[N-(2-oxo-1,2,5,6-tetrahydropyridin-4-yl)]amino-1-(2-chloroethyl)-4-cyanopyrazole (12.31 g.) in dry methylene chloride (100 ml.) under a nitrogen atmosphere at 0° was added slowly trimethylaluminum (68.64 ml. of a 1.35 M solution in heptane). There was a vigorous gas evolution. The resulting yellowish sludge was warmed to room temperature and stirred for one hour. EtOAc was added, the yellow solution was cooled to 0° , and enough 10% v/v aqueous hydrochloric acid was cautiously added to bring the pH to 4 (about 15 ml.). The reaction mixture was stirred overnight (17 hours). 10% w/v Aqueous sodium hydroxide solution (500 ml.) was added and the mixture stirred for three hours, followed by extraction several times into EtOAc/MeOH (9:1 v/v). The extracts were washed with brine, dried over magnesium sulfate, filtered through diatomaceous earth and concentrated to an off-white solid. Chromatography using silica gel with acetone/ methylene chloride (1:1 v/v) as eluant gave 4-amino-1-(2-chloroethyl)-7,8-dihydro-1H-pyrazolo[3,4-b][1,6]-napthyridin -5(6H)-one as a white solid (8.89 g.) (72% yield).

Workup

  1. temperaturethe yellow solution was cooled to 0°
  2. stirringThe reaction mixture was stirred overnight (17 hours)
  3. additionwas added
  4. stirringthe mixture stirred for three hours
  5. extractionfollowed by extraction several times into EtOAc/MeOH (9:1 v/v)
  6. washThe extracts were washed with brine
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered through diatomaceous earth
  9. concentrationconcentrated to an off-white solid

Sources & evidence

ORD record
ord-ca9c501c184a480faa400c01973f4a61
Source dataset
uspto-grants-1987_11
Patent number
US04705793

Reaction notes

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