Methane → HCID 13043970, compound

HRID 1701904Notes

Reaction equation

HRID 1701904 reaction equation
C([Li])CCC.[N:6]1[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=1[CH:12]1[CH2:16][CH2:15][CH2:14][O:13]1.[CH3:17][N:18]=[C:19]=[S:20].C(OC(C)C)(C)C.C>CCCCCC.C(O)C.C(OCC)(=O)C.O.O1CCCC1.CN(P(N(C)C)(N(C)C)=O)C>[CH3:17][NH:18][C:19]([C:12]1([C:7]2[CH:8]=[CH:9][CH:10]=[CH:11][N:6]=2)[CH2:16][CH2:15][CH2:14][O:13]1)=[S:20]

Participants

12

Reactant 5

HCID 297Methane2×HCID 7914Diisopropyl EtherHCID 11167Methyl isothiocyanateHCID 13720637HCID 13720637, compoundHCID 178418339Butyllithium

Product 1

HCID 13043970HCID 13043970, compoundYield 26.8%

Reagents, catalysts & solvents 6

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

Conditions

Temperature
0 °C

Procedure

A mixture of anhydrous hexamethylphosphorotriamide and anhydrous tetrahydrofuran (47/53 by volume; 80 cc) is added dropwise and in the course of 15 minutes to a 1.6 M solution of n-butyllithium in hexane (75 cc), kept under a nitrogen atomosphere and at a temperature of about -60° C. A solution of 2-(pyrid-2-yl)-tetrahydrofuran (15 g) in a mixture of anhydrous hexamethylphosphorotriamide and anhydrous tetrahydrofuran (47/53 by volume; 80 cc) is then added in the course of 20 minutes. After stirring for 30 minutes at the same temperature, a solution of methyl isothiocyanate (8.8 g) in a mixture of anhydrous hexamethylphosphorotriamide and anhydrous tetrahydrofuran (47/53 by volume; 80 cc) is added in the course of 20 minutes. The reaction mixture is subsequently stirred for 45 minutes at about -60° C. and then for 1 hour whilst allowing the temperature to rise gradually to about 20° C. It is then run into a mixture of distilled water (600 cc) and ethyl acetate (400 cc). After decantation, the aqueous solution is extracted twice with ethyl acetate (800 cc in total). The organic extracts are combined, washed three times with distilled water (1500 cc in total), dried over anhydrous sodium sulphate and filtered and the filtrate is concentrated under reduced pressure (20 mm Hg; 2.7 kPa) at 45° C. The product obtained (6.6 g) is dissolved in boiling diisopropyl ether (350 cc); decolourising charcoal (0.5 g) is added to the solution, which is filtered hot, and the filtrate is then cooled for 30 minutes at 0° C. The resulting crystals are filtered off, washed twice with diisopropyl ether (10 cc in total) and dried under reduced pressure (20 mm Hg; 2.7 kPa) at a temperature of about 20° C. The product obtained (7.7 g) is combined with a product (0.8 g) prepared under the same conditions, and the combined product is dissolved in boiling ethanol (30 cc); decolourising charcoal (0.2 g) is added to the solution, which is filtered hot, and the filtrate is then cooled for 1 hour at 0° C. The resulting crystals are filtered off, washed twice with ethanol (10 cc in total) and dried under reduced pressure (1 mm Hg; 0.13 kPa) at 45° C. N-Methyl-2-(pyrid-2-yl)-tetrahydrofuran-2-carbothioamide (6 g), melting at 115° C., is thus obtained.

Workup

  1. customat a temperature of about -60° C
  2. additionis then added in the course of 20 minutes
  3. additionis added in the course of 20 minutes
  4. stirringThe reaction mixture is subsequently stirred for 45 minutes at about -60° C.
  5. waitfor 1 hour whilst allowing
  6. customto rise gradually to about 20° C
  7. extractionAfter decantation, the aqueous solution is extracted twice with ethyl acetate (800 cc in total)
  8. washwashed three times with distilled water (1500 cc in total)
  9. dry with materialdried over anhydrous sodium sulphate
  10. filtrationfiltered
  11. concentrationthe filtrate is concentrated under reduced pressure (20 mm Hg; 2.7 kPa) at 45° C
  12. customThe product obtained (6.6 g)
  13. dissolutionis dissolved
  14. filtrationis filtered hot
  15. filtrationThe resulting crystals are filtered off
  16. washwashed twice with diisopropyl ether (10 cc in total)
  17. customdried under reduced pressure (20 mm Hg; 2.7 kPa) at a temperature of about 20° C
  18. customThe product obtained (7.7 g)
  19. customprepared under the same conditions
  20. dissolutionthe combined product is dissolved
  21. filtrationis filtered hot
  22. temperaturethe filtrate is then cooled for 1 hour at 0° C
  23. filtrationThe resulting crystals are filtered off
  24. washwashed twice with ethanol (10 cc in total)
  25. customdried under reduced pressure (1 mm Hg; 0.13 kPa) at 45° C

Sources & evidence

ORD record
ord-95e38f1f82b14f7a96fc3ce84de820c3
Source dataset
uspto-grants-1983_04
Patent number
US04379154

Reaction notes

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