Methane → HCID 13043963, compound

HRID 1701884Notes

Reaction equation

HRID 1701884 reaction equation
CN.[N:3]1[CH:8]=[CH:7][C:6]([C:9]2([C:14]([S:16]C)=S)[CH2:13][CH2:12][CH2:11][S:10]2)=[CH:5][CH:4]=1.C.[C:19](#[N:21])C>C(O)C>[CH3:19][NH:21][C:14]([C:9]1([C:6]2[CH:7]=[CH:8][N:3]=[CH:4][CH:5]=2)[CH2:13][CH2:12][CH2:11][S:10]1)=[S:16]

Participants

6

Reactant 4

HCID 297Methane3×HCID 6329MethylamineHCID 6342AcetonitrileHCID 13043958HCID 13043958, compound

Product 1

HCID 13043963HCID 13043963, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent4×

Conditions

Temperature
20 °C

Procedure

A 33% (weight/volume) solution of methylamine in ethanol (12 cc) is added dropwise, in the course of 15 minutes, to a solution of methyl 2-(pyrid-4-yl)-tetrahydrothiophen-2-carbodithioate (16 g) in ethanol (35 cc), kept at 20° C. The solution is subsequently stirred for 1 hour at a temperature of about 20° C. and is then cooled to 0° C. The resulting crystals are filtered off, washed twice with ethanol (30 cc in total) and dried under reduced pressure (20 mm Hg; 2.7 kPa) at a temperature of about 20° C. A crystalline crude product (11 g) is thus obtained, which is redissolved in boiling ethanol (100 cc); decolourising charcoal (0.3 g) is added to the solution obtained, which is filtered hot, and the filtrate is then cooled for one hour at 0° C. The resulting crystals are filtered off, washed twice with ethanol (20 cc in total) and dried under reduced pressure (20 mm Hg; 2.7 kPa) at a temperature of about 20° C. The product thus obtained (9 g) is chromatographed on neutral silica gel (20 g) contained in a column of diameter 1.7 cm. Elution is carried out with methylene chloride (1000 cc) and then with a methylene chloride/ethanol mixture (90/10 by volume; 250 cc), 250 cc fractions being collected. Fractions 1 to 5 are combined and concentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 50° C. The product thus obtained (8 g) is dissolved in boiling ethanol (94 cc); decolourising charcoal (0.4 g) is added to the solution, which is filtered hot, and the filtrate is then cooled for 15 hours at a temperature of about 5° C. The resulting crystals are filtered off, washed twice with ethanol (14 cc in total) and dried under reduced pressure (20 mm Hg; 2.7 kPa) at a temperature of about 20° C. The product thus obtained (6.9 g) is dissolved in boiling acetonitrile (75 cc) and the solution, to which decolourising charcoal (0.2 g) is added, is filtered hot and the filtrate is then cooled for 1 hour at 0° C. The resulting crystals are filtered off, washed with acetonitrile (7 cc) and dried under reduced pressure (1 mm Hg; 0.13 kPa) at 60° C. N-Methyl-2-(pyrid-4-yl)-tetrahydrothiophen-2-carbothioamide (5.9 g), melting at 178° C., is thus obtained.

Workup

  1. customkept at 20° C
  2. temperatureis then cooled to 0° C
  3. filtrationThe resulting crystals are filtered off
  4. washwashed twice with ethanol (30 cc in total)
  5. customdried under reduced pressure (20 mm Hg; 2.7 kPa) at a temperature of about 20° C
  6. customA crystalline crude product (11 g) is thus obtained
  7. dissolutionwhich is redissolved
  8. customobtained
  9. filtrationwhich is filtered hot
  10. temperaturethe filtrate is then cooled for one hour at 0° C
  11. filtrationThe resulting crystals are filtered off
  12. washwashed twice with ethanol (20 cc in total)
  13. customdried under reduced pressure (20 mm Hg; 2.7 kPa) at a temperature of about 20° C
  14. customThe product thus obtained (9 g)
  15. customis chromatographed on neutral silica gel (20 g)
  16. washElution
  17. customwith a methylene chloride/ethanol mixture (90/10 by volume; 250 cc), 250 cc fractions being collected
  18. concentrationconcentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 50° C
  19. customThe product thus obtained (8 g)
  20. dissolutionis dissolved
  21. filtrationis filtered hot
  22. temperaturethe filtrate is then cooled for 15 hours at a temperature of about 5° C
  23. filtrationThe resulting crystals are filtered off
  24. washwashed twice with ethanol (14 cc in total)
  25. customdried under reduced pressure (20 mm Hg; 2.7 kPa) at a temperature of about 20° C
  26. customThe product thus obtained (6.9 g)
  27. dissolutionis dissolved
  28. additionis added
  29. filtrationis filtered hot
  30. temperaturethe filtrate is then cooled for 1 hour at 0° C
  31. filtrationThe resulting crystals are filtered off
  32. washwashed with acetonitrile (7 cc)
  33. customdried under reduced pressure (1 mm Hg; 0.13 kPa) at 60° C

Sources & evidence

ORD record
ord-6a60cb21c0904c1bab745cf223320e0d
Source dataset
uspto-grants-1983_04
Patent number
US04379154

Reaction notes

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