Formic Acid → HCID 86680742, compound

HRID 868814Notes

Reaction equation

HRID 868814 reaction equation
[Br:1][C:2]1[N:7]=[CH:6][C:5]([N:8]2[C:12](=[O:13])[CH2:11][C:10]([CH3:15])([CH3:14])[NH:9]2)=[CH:4][CH:3]=1.[CH:16](O)=O.C=O.[OH-].[Na+]>O>[Br:1][C:2]1[N:7]=[CH:6][C:5]([N:8]2[C:12](=[O:13])[CH2:11][C:10]([CH3:15])([CH3:14])[N:9]2[CH3:16])=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 284Formic AcidHCID 712FormaldehydeHCID 14798Sodium HydroxideHCID 86680743HCID 86680743, compound

Product 1

HCID 86680742HCID 86680742, compoundYield 45.2%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
100 °C

Procedure

A suspension of 2-(6-bromo-pyridin-3-yl)-5,5-dimethyl-pyrazolidin-3-one (Example 12, step 1) (800 mg, 2.96 mmol) and formic acid (0.57 ml, 14.8 mmol, 5 equiv.) in water (8 ml) was heated to 100° C. At this temperature formaldehyde (36% in water) (1.13 ml, 14.8 mmol, 5 equiv.) was added drop wise. The mixture was stirred overnight at 100° C. The reaction mixture was cooled and basified carefully with 2N NaOH and extracted two times with a small amount of dichloromethane. The organic layers were loaded directly on a silica gel column and the crude product was purified by flash chromatography eluting with a heptane:ethyl acetate gradient 100:0 to 0:100. The desired 2-(6-bromo-pyridin-3-yl)-1,5,5-trimethyl-pyrazolidin-3-one (380 mg, 45% yield) was obtained as a colorless oil, MS: m/e=284.3/286.3 (M+H+).

Workup

  1. temperatureThe reaction mixture was cooled
  2. extractionextracted two times with a small amount of dichloromethane
  3. customthe crude product was purified by flash chromatography
  4. washeluting with a heptane

Sources & evidence

ORD record
ord-a7b20db4b1ed4043b5b9352d48f62d0b
Source dataset
uspto-grants-2015_03
Patent number
US08969338B2

Reaction notes

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