Methane → HCID 20192965, compound

HRID 2118722Notes

Reaction equation

HRID 2118722 reaction equation
[CH3:1][NH:2][C:3]([C:5]1([C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([CH3:18])[N:13]=2)[CH2:10][CH2:9][CH2:8][CH2:7][S:6]1=O)=[S:4].P12(SP3(SP(SP(S3)(S1)=S)(=S)S2)=S)=S.C(OCC)(=O)C.C>C(Cl)Cl>[CH3:1][NH:2][C:3]([C:5]1([C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([CH3:18])[N:13]=2)[CH2:10][CH2:9][CH2:8][CH2:7][S:6]1)=[S:4]

Participants

6

Reactant 4

HCID 297MethaneHCID 8857Ethyl AcetateHCID 14817Phosphorus sulfide (P2S5)HCID 20192967HCID 20192967, compound

Product 1

HCID 20192965HCID 20192965, compoundYield 99.7%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
25 °C

Procedure

To a solution of N-methyl-2-(6-methyl-2-pyridyl)-2-tetrahydrothiopyrancarbothioamide 1-oxide (72.4 g) in methylene chloride (1.4 liters), phosphorus pentasulphide (28.5 g) is added at a temperature below 28° C. and in the course of 50 minutes. The reaction mixture is stirred for 1 hour 45 minutes at a temperature in the region of 25° C. and distilled water (250 cc) is then added. The organic phase is decanted and washed 3 times with distilled water (750 cc in total) and dried over anhydrous magnesium sulphate, decolorising charcoal is added and the mixture is kept for 15 hours at a temperature in the region of 5° C. After filtration, the solution is poured onto neutral silica gel (1.6 kg; 0.063-0.200 mm) contained in a column 8 cm in diameter. The column is eluted with methylene chloride, collecting one fraction (3.9 liters) and 13 fractions (900 cc). The column is then eluted with a mixture of cyclohexane and ethyl acetate (60:40 by volume), collecting 5 fractions (900 cc). Fractions 6 to 13 and 15 to 18 are combined and concentrated to dryness under reduced pressure (0.5 mm Hg; 0.06 kPa) at 45° C. To the product obtained (49.6 g) there is added some product (41.2 g) prepared under the same conditions in a previous operation, and the combined product is dissolved in boiling ethyl acetate (600 cc); decolorising charcoal (10 g) is added to the solution, which is filtered hot and then kept, after being cooled, for 4 hours at 0° C. The crystals which appear are separated by filtration, washed twice with ethyl acetate (30 cc in total) and 4 times with isopropyl ether (160 cc in total), and then dried under reduced pressure (0.2 mm Hg; 0.026 kPa) at 55° C. N-Methyl-2-(6-methyl-2-pyridyl)-2-tetrahydrothiopyrancarbothioamide (68.1 g), m.p. 139° C., is thereby obtained.

Workup

  1. distillationdistilled water (250 cc)
  2. additionis then added
  3. customThe organic phase is decanted
  4. washwashed 3 times with distilled water (750 cc in total)
  5. dry with materialdried over anhydrous magnesium sulphate
  6. additionis added
  7. waitthe mixture is kept for 15 hours at a temperature in the region of 5° C
  8. filtrationAfter filtration
  9. additionthe solution is poured onto neutral silica gel (1.6 kg; 0.063-0.200 mm)
  10. washThe column is eluted with methylene chloride
  11. customcollecting one fraction (3.9 liters) and 13 fractions (900 cc)
  12. washThe column is then eluted with a mixture of cyclohexane and ethyl acetate (60:40 by volume)
  13. customcollecting 5 fractions (900 cc)
  14. concentrationconcentrated to dryness under reduced pressure (0.5 mm Hg; 0.06 kPa) at 45° C
  15. customTo the product obtained (49.6 g) there
  16. customprepared under the same conditions in a previous operation
  17. dissolutionthe combined product is dissolved
  18. filtrationis filtered hot
  19. temperatureafter being cooled, for 4 hours at 0° C
  20. customThe crystals which appear are separated by filtration
  21. washwashed twice with ethyl acetate (30 cc in total) and 4 times with isopropyl ether (160 cc in total)
  22. customdried under reduced pressure (0.2 mm Hg; 0.026 kPa) at 55° C

Sources & evidence

ORD record
ord-2ee5bd5241624f8a94e20885b5caebc7
Source dataset
uspto-grants-1987_07
Patent number
US04680303

Reaction notes

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