Dichloromethane → 1-Methylsulfinyl-1-methylthio-2-amino-5,5-dimethoxy-1-pentene

HRID 1606257Notes

Reaction equation

HRID 1606257 reaction equation
[CH3:1][S:2][CH2:3][S:4]([CH3:6])=[O:5].[H-].[Na+].[CH3:9][O:10][CH:11]([O:16][CH3:17])[CH2:12][CH2:13][C:14]#[N:15].C(Cl)Cl>C1COCC1.O>[CH3:6][S:4]([C:3]([S:2][CH3:1])=[C:14]([NH2:15])[CH2:13][CH2:12][CH:11]([O:16][CH3:17])[O:10][CH3:9])=[O:5]

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 24758Sodium hydrideHCID 845584,4-DimethoxybutyronitrileHCID 99129Methyl (methylsulfinyl)methyl sulfide

Product 1

HCID 737940341-Methylsulfinyl-1-methylthio-2-amino-5,5-dimethoxy-1-penteneYield 76.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

2.370 Grams of methyl methylthiomethyl sulfoxide was dissolved in 20 ml of anhydrous THF, and to which 475 mg of sodium hydride was added under cooling with ice, followed by 50 minutes' stirring at 0°C. and additional 50 minutes' stirring at room temperature. Again icecooling the system, 3.73 ml of 4,4-dimethoxybutyronitrile was added dropwise, followed by 18 hours' stirring and further 23 hours' stirring at 50° - 55°C. The reaction liquid was again cooled with ice while 30 ml of methylene chloride and 1 ml of water were added thereto, and after a little while the temperature was returned to the normal level, followed by 3 hours' stirring. After an overnight's drying with Glauber's salt, the reaction mixture was filtered, and the solvent was evaporated off under reduced pressure. The residue was parted by a column chromatography (Florisil, methylene chloride, ethyl acetate and methanol), to allow the recovery of 457 mg of methyl methylthiomethyl sulfoxide and 4.332 g of a crystalline product. The crystals were dissolved in hot methylene chloride, and the insoluble matter was removed by filtration. The filtrate was concentrated under a reduced pressure to leave 3.70 g of 1-methylsulfinyl-1-methylthio-2-amino-5,5-dimethoxy-1-pentene in light yellow, crystalline form. The yield was 76.5%, and the conversion yield was 94.8%.

Workup

  1. temperatureunder cooling with ice
  2. stirringstirring at room temperature
  3. additionwas added dropwise
  4. waitfollowed by 18 hours
  5. stirring' stirring and further 23 hours'
  6. stirringstirring at 50° - 55°C
  7. customThe reaction liquid
  8. additionwere added
  9. waitfollowed by 3 hours
  10. stirring' stirring
  11. dry with materialAfter an overnight's drying with Glauber's salt
  12. filtrationthe reaction mixture was filtered
  13. customthe solvent was evaporated off under reduced pressure
  14. dissolutionThe crystals were dissolved in hot methylene chloride
  15. customthe insoluble matter was removed by filtration
  16. concentrationThe filtrate was concentrated under a reduced pressure

Sources & evidence

ORD record
ord-1f7030aa68c24634977163f674dff00d
Source dataset
uspto-grants-1976_04
Patent number
US03952044

Reaction notes

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