Methane → HCID 13043959, compound

HRID 1701889Notes

Reaction equation

HRID 1701889 reaction equation
C([Li])CCC.[N:6]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH:9]=[CH:8][C:7]=1[CH:16]1[CH2:20][CH2:19][CH2:18][S:17]1.[CH3:21]I.C(OC(C)C)(C)C.C.[C:31](=[S:33])=[S:32]>CCCCCC.C(OCC)(=O)C.O.O1CCCC1.CN(P(N(C)C)(N(C)C)=O)C>[N:6]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH:9]=[CH:8][C:7]=1[C:16]1([C:31]([S:33][CH3:21])=[S:32])[CH2:20][CH2:19][CH2:18][S:17]1

Participants

12

Reactant 6

HCID 297MethaneHCID 6328Methyl iodideHCID 6348Carbon DisulfideHCID 7914Diisopropyl EtherHCID 13043972HCID 13043972, compoundHCID 178418339Butyllithium

Product 1

HCID 13043959HCID 13043959, compoundYield 20.2%

Reagents, catalysts & solvents 5

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent4×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolventHCID 12679HexamethylphosphoramideSolvent4×

Conditions

Temperature
5 °C

Procedure

A mixture of anhydrous hexamethylphosphorotriamide and anhydrous tetrahydrofuran (47/53 by volume; 100 cc) is added dropwise and in the course of 10 minutes to a 1.6 M solution of n-butyllithium in hexane (138 cc), kept under an argon atmosphere and at a temperature of about -60° C. A solution of 2-(quinol-2-yl)-tetrahydrothiophen (31 g) in a mixture of anhydrous hexamethylphosphorotriamide and anhydrous tetrahydrofuran (47/53 by volume; 100 cc) is then added in the course of 15 minutes. After stirring for 5 minutes, a solution of carbon disulphide (17 g) in a mixture of anhydrous hexamethylphosphorotriamide and anhydrous tetrahydrofuran (47/53 by volume; 100 cc) is added dropwise in the course of 15 minutes and at the same temperature. After stirring for 5 minutes, a solution of methyl iodide (32 g) in a mixture of anhydrous hexamethylphosphorotriamide and anhydrous tetrahydrofuran (47/53 by volume; 100 cc) is added dropwise and in the course of 25 minutes. The reaction mixture is subsequently stirred for 45 minutes at - 65° C. and then for 45 minutes, whilst allowing the temperature to rise gradually to about 20° C. It is then run into a mixture of distilled water (750 cc) and ethyl acetate (450 cc). After decantation, the aqueous phase is extracted with ethyl acetate (250 cc). The organic extracts are combined, washed three times with distilled water (2250 cc in total), dried over anhydrous sodium sulphate and filtered and the filtrate is concentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 70° C. The product obtained (57 g) is chromatographed on neutral silica gel (550 g) contained in a column of diameter 5.2 cm; the column is then eluted with a cyclohexane/ethyl acetate mixture (95/5 by volume; 1000 cc) and with a cyclohexane/ethyl acetate mixture (90/10 by volume; 1000 cc), 500 cc fractions being collected. Fractions 1 to 3 are combined and concentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 50° C.; a crude product (36.6 g) is thus obtained. 14 g thereof are dissolved in boiling diisopropyl ether (70 cc); decolourising charcoal (0.3 g) is added to the solution, which is filtered hot, and the filtrate is then cooled for 2 hours at a temperature of about 5° C. The resulting crystals are filtered off, washed with diisopropyl ether (7 cc) and then twice with petroleum ether (30 cc in total). After drying under reduced pressure (1 mm Hg; 0.13 kPa) at 45° C., methyl 2-(quinol-2-yl)-tetrahydrothiophen-2-carbodithioate (8.9 g), melting at 72° C., is obtained.

Workup

  1. customkept under an argon atmosphere and at a temperature of about -60° C
  2. additionis then added in the course of 15 minutes
  3. additionis added dropwise in the course of 15 minutes and at the same temperature
  4. stirringAfter stirring for 5 minutes
  5. additionis added dropwise and in the course of 25 minutes
  6. stirringThe reaction mixture is subsequently stirred for 45 minutes at - 65° C.
  7. waitfor 45 minutes
  8. customto rise gradually to about 20° C
  9. extractionAfter decantation, the aqueous phase is extracted with ethyl acetate (250 cc)
  10. washwashed three times with distilled water (2250 cc in total)
  11. dry with materialdried over anhydrous sodium sulphate
  12. filtrationfiltered
  13. concentrationthe filtrate is concentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 70° C
  14. customThe product obtained (57 g)
  15. customis chromatographed on neutral silica gel (550 g)
  16. washthe column is then eluted with a cyclohexane/ethyl acetate mixture (95/5 by volume; 1000 cc) and with a cyclohexane/ethyl acetate mixture (90/10 by volume; 1000 cc), 500 cc fractions
  17. custombeing collected
  18. concentrationconcentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 50° C.
  19. customa crude product (36.6 g) is thus obtained
  20. dissolution14 g thereof are dissolved
  21. filtrationis filtered hot
  22. filtrationThe resulting crystals are filtered off
  23. washwashed with diisopropyl ether (7 cc)
  24. customAfter drying under reduced pressure (1 mm Hg; 0.13 kPa) at 45° C.

Sources & evidence

ORD record
ord-e6a15c82317d44418ca172ac11385a4c
Source dataset
uspto-grants-1983_04
Patent number
US04379154

Reaction notes

Loading…