Water → HCID 53668106, compound

HRID 1739653Notes

Reaction equation

HRID 1739653 reaction equation
[Cl:1][C:2]1[C:3]([Cl:11])=[N:4][CH:5]=[C:6]([CH:10]=1)[C:7]([OH:9])=[O:8].C(N1C=CN=C1)(N1C=CN=C1)=O.[CH3:24][C:25](O)([C:27]#[CH:28])[CH3:26].O>O1CCCC1>[Cl:1][C:2]1[C:3]([Cl:11])=[N:4][CH:5]=[C:6]([CH:10]=1)[C:7]([O:9][C:25]([CH3:26])([CH3:24])[C:27]#[CH:28])=[O:8]

Participants

6

Reactant 4

HCID 962WaterHCID 82582-Methyl-3-butyn-2-olHCID 682631,1'-CarbonyldiimidazoleHCID 2479875,6-Dichloronicotinic acid

Product 1

HCID 53668106HCID 53668106, compoundYield 19.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
40 °C

Procedure

5,6-Dichloronicotinic acid (1.92 g, 10.0 mmol) was slurried in 10 mL tetrahydrofuran to which carbonyldiimidazole (CDI) (1.78 g, 11.0 mmol) was added. The mixture was stirred at 40° C. for one hour to a uniform solution. 2-Methyl-3-butyn-2-ol (1.01 g, 12.0 mmol) was added via pipette and the solution refluxed overnight. The solution was poured into 4-5 volumes of water and extracted with Et2O (2×100 mL). The organics were washed with 2.0 N NaOH, dried over MgSO4, and concentrated to 1.2 g pale yellow oil. Crude product was chromatographed on medium column using silica gel (23-400 mesh) with descending solvent gradient from 100% petroleum ether to 50/50 pet. ether/ethyl acetate as the mobile phase. Elution and concentration gave (dimethyl)propargyl 5,6-dichloronicotinate (0.50 g) as a colorless oil.

Workup

  1. additionwas added
  2. temperaturethe solution refluxed overnight
  3. extractionextracted with Et2O (2×100 mL)
  4. washThe organics were washed with 2.0 N NaOH
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated to 1.2 g pale yellow oil
  7. customCrude product was chromatographed on medium column
  8. washElution and concentration

Sources & evidence

ORD record
ord-4db625d6fd2441cf9076ba3bf254ba36
Source dataset
uspto-grants-1999_10
Patent number
US05968875

Reaction notes

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