Hydrochloric Acid → HCID 178462993, compound

HRID 542567Notes

Reaction equation

HRID 542567 reaction equation
[Li]CCCC.Br[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][N:8]=1.[CH2:13]([N:15]1[C:19]2=[N:20][CH:21]=[C:22](C=O)[C:23]([O:24][N:25]=[C:26]([CH3:28])[CH3:27])=[C:18]2[CH:17]=[N:16]1)[CH3:14].Cl.C[CH2:33][O:34]CC>C1COCC1>[CH2:13]([N:15]1[C:19]2=[N:20][CH:21]=[CH:22][C:23]([CH:33]([C:7]3[CH:12]=[CH:11][CH:10]=[CH:9][N:8]=3)[OH:34])([O:24][N:25]=[C:26]([CH3:27])[CH3:28])[C:18]2=[CH:17][NH:16]1)[CH3:14]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 3283Diethyl Ether2×HCID 79732-BromopyridineHCID 13732608HCID 13732608, compoundHCID 178418339Butyllithium

Product 1

HCID 178462993HCID 178462993, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Twenty-five ml of 1.44M n-BuLi was dissolved in 100 ml of anhydrous ether and chilled to -65°. 2-Bromopyridine (5.70 g) was then added dropwise and stirring was continued for 30 minutes. This solution was then added under nitrogen pressure through a catheter to 8.30 g of 1-ethyl-5-formyl-4-isopropylidenaminoxy-1H-pyrazolo[3,4-b]pyridine in 100 ml of THF at ice bath temperature. This reaction mixture was stirred for additional 30 minutes and then distributed between 5% hydrochloric acid and ether. The aqueous phase was washed well with ether and then made basic by pouring it over solid sodium bicarbonate. The product was extracted with dichloromethane and purified by preparative HPLC (5% methanol-dichloromethane, 200 ml/minute) to give 6.20 g of product, mp 131°-133° C. Recrystallization from dichloromethane-hexane raised the mp to 134°-135° C.

Workup

  1. temperaturechilled to -65°
  2. stirringThis reaction mixture was stirred for additional 30 minutes
  3. washThe aqueous phase was washed well with ether
  4. additionby pouring it over solid sodium bicarbonate
  5. extractionThe product was extracted with dichloromethane
  6. custompurified by preparative HPLC (5% methanol-dichloromethane, 200 ml/minute)

Sources & evidence

ORD record
ord-b9bc9aa858574160ae250ab05109ba62
Source dataset
uspto-grants-1987_04
Patent number
US04658029

Reaction notes

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