Methane → HCID 20135506, compound

HRID 579988Notes

Reaction equation

HRID 579988 reaction equation
[CH2:1]([NH2:3])[CH3:2].[N:4]1[CH:9]=[CH:8][CH:7]=[C:6]([C:10]2([C:17](SC)=[S:18])[CH2:15][CH2:14][CH2:13][CH2:12][S:11]2=[O:16])[CH:5]=1.C>C(O)C.C(C(C)=O)C.C(OC(C)C)(C)C>[CH2:1]([NH:3][C:17]([C:10]1([C:6]2[CH:5]=[N:4][CH:9]=[CH:8][CH:7]=2)[CH2:15][CH2:14][CH2:13][CH2:12][S:11]1=[O:16])=[S:18])[CH3:2]

Participants

7

Reactant 3

HCID 297MethaneHCID 6341EthylamineHCID 11011568HCID 11011568, compound

Product 1

HCID 20135506HCID 20135506, compoundYield 28.3%

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 6569Methyl Ethyl KetoneSolvent2×HCID 7914Diisopropyl EtherSolvent

Procedure

Ethylamine (34 g) is added dropwise, in the course of 5 minutes, to a solution of methyl 2-(pyridin-3-yl)tetrahydrothiopyran-2-carbodithioate 1-oxide (10.7 g) in ethanol (120 cc), kept at between 20° and 25° C. The solution is then stirred for 1 hour 30 minutes at the same temperature and then concentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 50° C. The product obtained (12 g) is chromatographed on neutral silica gel (0.040-0.063 mm; 145 g) contained in a column of diameter 4 cm, under a pressure of 40 kPa. The column is eluted with a mixture of ethyl acetate and methanol (90/10 by volume), one 300 cc fraction and thirty-two 120 cc fractions being collected. Fractions 16 to 33 are combined and concentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 40° C. The product obtained (4 g) is dissolved in a boiling mixture of methyl ethyl ketone (9 cc) and diisopropyl ether (2 cc); after cooling, the solution is kept at a temperature of about 0° C. for 2 hours. The resulting crystals are filtered off, washed with methyl ethyl ketone (3 cc) and with diisopropyl ether (0.5 cc) and dried under reduced pressure (20 mm Hg; 2.7 kPa) at a temperature of about 20° C. The product obtained (2.6 g), to which 1.2 g prepared under the same condtions in an earlier operation have been added, is dissolved in boiling methyl ethyl ketone (25 cc); the solution is treated with decolourising charcoal (0.2 g) and filtered hot and the filtrate is cooled and kept at a temperature of about 0° C. for 1 hour 30 minutes. The resulting crystals are filtered off, washed with methyl ethyl ketone (6 cc) and dried under reduced pressure (1 mm Hg; 0.13 kPa) at 60° C. This gives the A form of N-ethyl-2-(pyridin-3-yl)tetrahydrothiopyran-2-carbothioamide 1-oxide (3 g) melting initially at about 169° C. and then, after resolidification, at 183° C. [Rf=0.32; chromatography on a thin layer of silica gel; solvent: ethyl acetate/methanol (80/20 by volume)].

Workup

  1. customkept at between 20° and 25° C
  2. concentrationconcentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 50° C
  3. customThe product obtained (12 g)
  4. customis chromatographed on neutral silica gel (0.040-0.063 mm; 145 g)
  5. washThe column is eluted with a mixture of ethyl acetate and methanol (90/10 by volume), one 300 cc fraction and thirty-two 120 cc fractions
  6. custombeing collected
  7. concentrationconcentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 40° C
  8. customThe product obtained (4 g)
  9. temperatureafter cooling
  10. waitthe solution is kept at a temperature of about 0° C. for 2 hours
  11. filtrationThe resulting crystals are filtered off
  12. washwashed with methyl ethyl ketone (3 cc) and with diisopropyl ether (0.5 cc)
  13. customdried under reduced pressure (20 mm Hg; 2.7 kPa) at a temperature of about 20° C
  14. customThe product obtained (2.6 g)
  15. customto which 1.2 g prepared under the same condtions in an earlier operation
  16. additionhave been added
  17. dissolutionis dissolved
  18. filtrationfiltered hot
  19. temperaturethe filtrate is cooled
  20. waitkept at a temperature of about 0° C. for 1 hour 30 minutes
  21. filtrationThe resulting crystals are filtered off
  22. washwashed with methyl ethyl ketone (6 cc)
  23. customdried under reduced pressure (1 mm Hg; 0.13 kPa) at 60° C

Sources & evidence

ORD record
ord-1e5f5dc9692f43fa99e49396bad01c3b
Source dataset
uspto-grants-1988_06
Patent number
US04751234

Reaction notes

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