Furfurylamine → N-(2-Furanylmethyl)-alpha-methyl-alpha-(phenylmethyl)-2-pyridineethanimidothioic acid, methyl ester

HRID 440305Notes

Reaction equation

HRID 440305 reaction equation
[CH3:1][CH:2]([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][N:11]=1)[CH2:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[CH2:16]([Li])CCC.CCCCCC.[O:27]1[CH:31]=[CH:30][CH:29]=[C:28]1[CH2:32][N:33]=[C:34]=[S:35].O1C=CC=C1CN.CI>O1CCCC1.C(Cl)(Cl)Cl>[O:27]1[CH:31]=[CH:30][CH:29]=[C:28]1[CH2:32][N:33]=[C:34]([S:35][CH3:16])[C:2]([CH3:1])([CH2:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][N:11]=1

Participants

8

Reactant 5

HCID 3438FurfurylamineHCID 6328Methyl iodideHCID 783802-(Isothiocyanatomethyl)furanHCID 153424762-(1-Methyl-2-phenylethyl)pyridineHCID 178418244HCID 178418244, compound

Product 1

HCID 86748377N-(2-Furanylmethyl)-alpha-methyl-alpha-(phenylmethyl)-2-pyridineethanimidothioic acid, methyl esterYield 89%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
25 °C

Procedure

A solution of 2-(1-methyl-2-phenylethyl)pyridine (6.12 g, 31 mmol) in 60 mL of anhydrous tetrahydrofuran under nitrogen at -35° C. was treated (via syringe) with 2.50N n-butyllithium/hexane (30 mmol), and stirred at -25° (±5) C. for 30 minutes. The mixture was transferred via a cannula over a 15-minute period into a cooled (-70° C.) solution of 2-furanylmethyl isothiocyanate (prepared in 89% yield from 2-furanylmethylamine by the procedure of J. C. Joehims and A. Seeliger, Angew. Chem. Int. Ed. Engl. 6, 174-175 (1967) (4.45 g, 32 mmol) in 25 mL of anhydrous tetrahydrofuran under nitrogen. The solution was warmed to 25° C. over one hour, maintained at room temperature for 30 minutes, cooled (0° C.), and treated (via syringe) with methyl iodide (4.68 g, 2.05 mL, 33 mmol). After 30 minutes at room temperature, the cooled (0° C.) solution was poured into a stirred mixture of 300 mL of chloroform and 150 mL of ice water. The organic layer was separated, and the aqueous solution was extracted with 150 mL of chloroform. The combined organic extracts were washed with 150 mL of brine, dried (Na2SO4) and concentrated in vacuo to afford the crude intermediate used below without further purification.

Workup

  1. waitThe mixture was transferred via a cannula over a 15-minute period
  2. temperaturemaintained at room temperature for 30 minutes
  3. temperaturecooled (0° C.)
  4. waitAfter 30 minutes at room temperature
  5. temperaturethe cooled (0° C.) solution
  6. customThe organic layer was separated
  7. extractionthe aqueous solution was extracted with 150 mL of chloroform
  8. washThe combined organic extracts were washed with 150 mL of brine
  9. dry with materialdried (Na2SO4)
  10. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-37fe38eb1a0d43f0a13a86ee45a5e873
Source dataset
uspto-grants-1996_05
Patent number
US05519037

Reaction notes

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