Methane → HCID 22164933, compound

HRID 1032712Notes

Reaction equation

HRID 1032712 reaction equation
C([Li])CCC.C(NC(C)C)(C)C.[C:13]1([CH:19]2[CH2:23][CH2:22][CH2:21][S:20]2)[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.[CH3:24][N:25]=[C:26]=[S:27].C>CCCCCC.C(O)C.C(OCC)(=O)C.O.O1CCCC1.CN(C)P(=O)(N(C)C)N(C)C>[CH3:24][NH:25][C:26]([C:19]1([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH2:23][CH2:22][CH2:21][S:20]1)=[S:27]

Participants

12

Reactant 5

HCID 297Methane2×HCID 7912DiisopropylamineHCID 11167Methyl isothiocyanateHCID 5962882-PhenylthiolaneHCID 178418339Butyllithium

Product 1

HCID 22164933HCID 22164933, compound

Reagents, catalysts & solvents 6

HCID 702EthanolSolvent2×HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolventHCID 12679HexamethylphosphoramideSolvent3×

Procedure

To 135 cc of a 1.6M solution of n-butyllithium in hexane maintained in an atmosphere of argon at a temperature of about -60° C., add, dropwise, over 10 minutes, a solution of 22 g of di-isopropylamine in 125 cc of a mixture of anhydrous hexamethylphosphoric triamide and anhydrous tetrahydrofuran (47:53 v/v) and stir the mixture for 5 minutes. Then add, dropwise, over 20 minutes, a solution of 28 g of 2-phenyltetrahydrothiophene in 125 cc of the mixture of anhydrous hexamethylphosphoric triamide and anhydrous tetrahydrofuran (47:53 v/v) and stir the mixture for 10 minutes. Then add, dropwise, over 15 minutes, a solution of 18.3 of methyl isothiocyanate in 62 cc of the mixture of anhydrous hexamethylphosphoric triamide and anhydrous tetrahydrofuran (47:53 v/v), stirring the mixture at the same temperature initially for 45 minutes, then for 1 hour, allowing the temperature to increase progressively to +15° C. Lastly, add 600 cc of distilled water and 600 cc of ethyl acetate. After separation, the organic phase is washed successively with 600 cc of distilled water, 250 cc of an aqueous solution of N hydrochloric acid, twice with 600 cc (1200 cc in total) of distilled water, then dried over anhydrous sodium sulphate, filtered and concentrated to dryness under reduced pressure (15 mm Hg; 2 kPa) at 45° C. The product obtained (37.5 g) is dissolved in 100 cc of boiling ethanol and activated charcoal is added to the solution thus obtained; the solution is then filtered, cooled and set aside for 2 hours at a temperature of about 20° C. The crystals formed are separated by filtration, washed with 15 cc of ethanol, then twice with 20 cc (40 cc in total) of di-isopropyl oxide and dried under reduced pressure (15 mm Hg; 2 kPa) at 20° C. The product obtained (17.7 g) is mixed with 1.3 g of the same product prepared beforehand under the same conditions, then dissolved in 70 cc of boiling ethanol. Activated charcoal is added to the solution thus obtained; the solution is then filtered while hot, cooled and set aside for 1 hour at a temperature of about 5° C. The crystals formed are separated by filtration, washed with 10 cc of ethanol and twice with 10 cc (20 cc in total) of di-isopropyl oxide and dried under reduced pressure (1 mm Hg; 0.13 kPa) at 53° C. 15.5 g of N-methyl-2-phenyltetrahydrothiophene-2-carbothioamide, with a melting point of 113° C, is thus obtained.

Workup

  1. additionadd
  2. additionThen add
  3. waitdropwise, over 20 minutes
  4. additionThen add
  5. waitdropwise, over 15 minutes
  6. waitfor 1 hour
  7. temperatureto increase progressively to +15° C
  8. customAfter separation
  9. washthe organic phase is washed successively with 600 cc of distilled water, 250 cc of an aqueous solution of N hydrochloric acid, twice with 600 cc (1200 cc in total) of distilled water
  10. dry with materialdried over anhydrous sodium sulphate
  11. filtrationfiltered
  12. concentrationconcentrated to dryness under reduced pressure (15 mm Hg; 2 kPa) at 45° C
  13. customThe product obtained (37.5 g)
  14. customthus obtained
  15. filtrationthe solution is then filtered
  16. temperaturecooled
  17. waitset aside for 2 hours at a temperature of about 20° C
  18. customThe crystals formed
  19. customare separated by filtration
  20. washwashed with 15 cc of ethanol
  21. dry with materialtwice with 20 cc (40 cc in total) of di-isopropyl oxide and dried under reduced pressure (15 mm Hg; 2 kPa) at 20° C
  22. customThe product obtained (17.7 g)
  23. customprepared
  24. customthus obtained
  25. filtrationthe solution is then filtered while hot,
  26. temperaturecooled
  27. waitset aside for 1 hour at a temperature of about 5° C
  28. customThe crystals formed
  29. customare separated by filtration
  30. washwashed with 10 cc of ethanol and twice with 10 cc (20 cc in total) of di-isopropyl oxide
  31. customdried under reduced pressure (1 mm Hg; 0.13 kPa) at 53° C

Sources & evidence

ORD record
ord-aef527b339d74757ad43ba3eca6c2f35
Source dataset
uspto-grants-1990_09
Patent number
US04959385

Reaction notes

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