Methane → HCID 22164932, compound

HRID 1032713Notes

Reaction equation

HRID 1032713 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=[O:24])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.[CH3:25][N:26]=[C:27]=[S:28].C>CCCCCC.C(O)C.C(OCC)(=O)C.O.O1CCCC1.CN(C)P(=O)(N(C)C)N(C)C>[CH3:25][NH:26][C:27]([C:19]1([C:13]2[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=2)[CH2:23][CH2:22][CH2:21][S:20]1=[O:24])=[S:28]

Participants

12

Reactant 5

HCID 297MethaneHCID 7912DiisopropylamineHCID 11167Methyl isothiocyanateHCID 22164934HCID 22164934, compoundHCID 178418339Butyllithium

Product 1

HCID 22164932HCID 22164932, compoundYield 47.4%

Reagents, catalysts & solvents 6

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

Conditions

Temperature
20 °C

Procedure

To 97.5 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 15 minutes, a solution of 16 g of di-isopropylamine in 90 cc of a 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 22.5 g of 2-phenyltetrahydrothiophene-1-oxide in 90 cc of the mixture of anhydrous hexamethylphosphoric triamide and anhydrous tetrahydrofuran (47:53 v/v) and continue to stir the mixture for 20 minutes. Then add, dropwise, over 15 minutes, a solution of 13.6 g of methyl isothiocyanate in 55 cc of the mixture of anhydrous hexamethylphosphoric triamide and anhydrous tetrahydrofuran (47:53 v/v) and continue to stir the mixture for 2 hours, allowing the temperature to increase progressively to 20° C. The reaction mixture is taken up with 450 cc of distilled water and 225 cc of ethyl acetate. The crystals formed are separated by filtration, washed twice with 30 cc (60 cc in total) of ethyl acetate, with 30 cc of di-isopropyl oxide and dried under reduced pressure (15 mm Hg; 2 kPa) at 20° C. A first batch of 16.3 g is thus obtained. The filtrate is separated and the organic phase is washed three times with 50 cc (150 cc in total) of distilled water, dried over anhydrous sodium sulphate, filtered and concentrated to dryness under reduced pressure (15 mm Hg; 2kPa) at 50° C. 30 cc of ethyl acetate is added to the product obtained and the crystals formed are separated by filtration, washed twice with 5 cc (10 cc in total) of di-isopropyl oxide and dried under reduced pressure (15 mm Hg; 2 kPa) at 20° C. A second batch of 1 g is thus obtained. Both batches (17.3 g) are mixed with 0.7 g of the same product, prepared beforehand under the same conditions and dissolved in 500 cc of boiling ethanol. Activated charcoal is added to the solution thus obtained; the solution is filtered while hot, cooled, then set aside for 15 hours at a temperature of about 5° C. The crystals formed are separated by filtration, washed with 20 cc of ethanol, then twice with 25 cc (50 cc in total) of di-isopropyl oxide and dried under reduced pressure (1 mm Hg; 0.13 kPa) at 50° C. 15 g of N-methyl-2-phenyltetrahydrothiophene-2-carbothioamide-1-oxide, with a melting point of 236° C., is thus obtained.

Workup

  1. additionadd
  2. additionThen add
  3. waitdropwise, over 15 minutes
  4. additionThen add
  5. waitdropwise, over 15 minutes
  6. stirringto stir the mixture for 2 hours
  7. customThe crystals formed
  8. customare separated by filtration
  9. washwashed twice with 30 cc (60 cc in total) of ethyl acetate, with 30 cc of di-isopropyl oxide
  10. customdried under reduced pressure (15 mm Hg; 2 kPa) at 20° C
  11. customA first batch of 16.3 g is thus obtained
  12. customThe filtrate is separated
  13. washthe organic phase is washed three times with 50 cc (150 cc in total) of distilled water
  14. dry with materialdried over anhydrous sodium sulphate
  15. filtrationfiltered
  16. concentrationconcentrated to dryness under reduced pressure (15 mm Hg; 2kPa) at 50° C
  17. addition30 cc of ethyl acetate is added to the product
  18. customobtained
  19. customthe crystals formed
  20. customare separated by filtration
  21. washwashed twice with 5 cc (10 cc in total) of di-isopropyl oxide
  22. customdried under reduced pressure (15 mm Hg; 2 kPa) at 20° C
  23. customA second batch of 1 g is thus obtained
  24. customprepared beforehand under the same conditions
  25. customthus obtained
  26. filtrationthe solution is filtered while hot,
  27. temperaturecooled
  28. waitset aside for 15 hours at a temperature of about 5° C
  29. customThe crystals formed
  30. customare separated by filtration
  31. washwashed with 20 cc of ethanol
  32. dry with materialtwice with 25 cc (50 cc in total) of di-isopropyl oxide and dried under reduced pressure (1 mm Hg; 0.13 kPa) at 50° C

Sources & evidence

ORD record
ord-d2a933b572c14277b5ceb7b460b15b40
Source dataset
uspto-grants-1990_09
Patent number
US04959385

Reaction notes

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