2,2'-Bipyridine → HCID 20031095, compound

HRID 232148Notes

Reaction equation

HRID 232148 reaction equation
[C:1]1([N:7]2[C:11]3[CH2:12][CH2:13][CH2:14][C:10]=3[C:9]([CH2:15][OH:16])=[N:8]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C([Li])CCC.N1C=CC=C[C:23]=1C1C=CC=CN=1.BrC[C:36]([O:38]CC)=[O:37].[OH-].[Na+]>C1COCC1.CO>[C:1]1([N:7]2[C:11]3[CH2:12][CH2:13][CH2:14][C:10]=3[C:9]([CH:15]([O:16][CH3:23])[C:36]([OH:38])=[O:37])=[N:8]2)[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

8

Reactant 5

HCID 14742,2'-BipyridineHCID 7748Ethyl bromoacetateHCID 14798Sodium HydroxideHCID 14576149HCID 14576149, compoundHCID 178418339Butyllithium

Product 1

HCID 20031095HCID 20031095, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 1-phenyl-1,4,5,6-tetrahydro-3-cyclopentapyrazolemethanol (2.14 g, 10 mmol) in THF (40 ml) was cooled to -10° C. and treated with 1.6M n-butyl lithium (6.2 ml, 10 mmol) using bipyridyl indicator. After 20 minutes, ethyl bromoacetate (1.9 g, 1.26 ml, 11.4 mmol) was added, reached at -20° C. for 45 minutes, then at ambient temperature for 18 hours. The solution was poured into ice water, acidified, and the products extracted into ethyl acetate. Drying and evaporation of solvent gave a residue containing unreacted methanol starting material. The residue was soaponified in methanol (150 ml) with 2N sodium hydroxide (25 ml) for 2 hours. The solution was concentrated to 50 ml, diluted to 300 ml with water, and neutral products extracted into ethyl acetate. The alkaline solution was acidified and extracted with ethyl acetate to yield crude title compound. Purification on CC-4 silica gel (100 g) with 1:1 ethyl acetate-Skelly B eluent gave pure title compound. Crystallization from ethyl acetate provided title compound (0.50 g), m.p. 106°-107° C.

Workup

  1. waitreached at -20° C. for 45 minutes
  2. waitat ambient temperature for 18 hours
  3. extractionthe products extracted into ethyl acetate
  4. customDrying
  5. customevaporation of solvent
  6. customgave a residue
  7. concentrationThe solution was concentrated to 50 ml
  8. additiondiluted to 300 ml with water, and neutral products
  9. extractionextracted into ethyl acetate
  10. extractionextracted with ethyl acetate
  11. customto yield crude title compound
  12. customPurification on CC-4 silica gel (100 g) with 1:1 ethyl acetate-Skelly B eluent

Sources & evidence

ORD record
ord-d29b9eed446b40e59f5c601eb81036f3
Source dataset
uspto-grants-1989_07
Patent number
US04851425

Reaction notes

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