Methyl iodide → HCID 13043961, compound

HRID 1701896Notes

Reaction equation

HRID 1701896 reaction equation
C([Li])CCC.[N:6]1[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=1[CH:12]1[S:17][CH2:16][CH2:15][CH2:14][S:13]1.[C:18](=[S:20])=[S:19].[CH3:21]I>CCCCCC.CN(P(N(C)C)(N(C)C)=O)C.O1CCCC1.C(O)C>[N:6]1[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=1[C:12]1([C:18]([S:20][CH3:21])=[S:19])[S:13][CH2:14][CH2:15][CH2:16][S:17]1

Participants

9

Reactant 4

HCID 6328Methyl iodideHCID 6348Carbon DisulfideHCID 13720638HCID 13720638, compoundHCID 178418339Butyllithium

Product 1

HCID 13043961HCID 13043961, compoundYield 14.7%

Reagents, catalysts & solvents 4

HCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent4×HCID 8058HexaneSolventHCID 12679HexamethylphosphoramideSolvent4×

Conditions

Temperature
-60 °C

Procedure

A mixture of anhydrous hexamethylphosphorotriamide and anhydrous tetrahydrofuran (47/53 by volume; 140 cc) is added dropwise and in the course of 10 minutes to a 1.6 M solution of n-butyllithium in hexane (140 cc), kept under a nitrogen atmosphere and cooled to -60° C. A solution of 2-(pyrid-2-yl)-1,3-dithiane (36 g) in a mixture of anhydrous hexamethylphosphorotriamide and anhydrous tetrahydrofuran (47/53 by volume; 140 cc) is then added in the course of 20 minutes and at the same temperature. After stirring for 15 minutes, a solution of carbon disulphide (17 g) in a mixture of anhydrous hexamethylphosphorotriamide and anhydrous tetrahydrofuran (47/53 by volume; 70 cc) is added in the course of 10 minutes. After stirring for 5 minutes at -60° C., a solution of methyl iodide (32 g) in anhydrous hexamethylphosphorotriamide and anhydrous tetrahydrofuran (70 cc) is added in the course of 10 minutes. After stirring for 1 hour 30 minutes at a temperature of about -40° C., distilled water (500 cc) is added; the mixture is then extracted four times with ethyl acetate (1100 cc in total). The organic extracts are combined, washed three times with distilled water (1200 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 40° C. The product obtained (57 g) is chromatographed on neutral alumina (1080 g) contained in a column of diameter 5.2 cm. Elution is carried out with cyclohexane (6000 cc), 1000 cc fractions being collected, and then with a cyclohexane/ethyl acetate mixture (99/1 by volume; 2500 cc), 500 cc fractions being collected. Fractions 7 to 11 are combined and concentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 40° C. The product obtained (15 g) is dissolved in boiling ethanol (30 cc) and the solution is cooled for 1 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. Methyl 2-(pyrid-2-yl)-1,3-dithiane-2-carbodithioate (7.7 g), melting at 91° C., is thus obtained.

Workup

  1. additionis then added in the course of 20 minutes and at the same temperature
  2. additionis added in the course of 10 minutes
  3. stirringAfter stirring for 5 minutes at -60° C.
  4. stirringAfter stirring for 1 hour 30 minutes at a temperature of about -40° C.
  5. distillationdistilled water (500 cc)
  6. additionis added
  7. extractionthe mixture is then extracted four times with ethyl acetate (1100 cc in total)
  8. washwashed three times with distilled water (1200 cc in total)
  9. dry with materialdried over anhydrous sodium sulphate
  10. filtrationfiltered
  11. concentrationthe filtrate is concentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 40° C
  12. customThe product obtained (57 g)
  13. customis chromatographed on neutral alumina (1080 g)
  14. washElution
  15. custombeing collected
  16. customwith a cyclohexane/ethyl acetate mixture (99/1 by volume; 2500 cc), 500 cc fractions being collected
  17. concentrationconcentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 40° C
  18. customThe product obtained (15 g)
  19. dissolutionis dissolved
  20. temperaturethe solution is cooled for 1 hour at 0° C
  21. filtrationThe resulting crystals are filtered off
  22. washwashed twice with ethanol (20 cc in total)
  23. customdried under reduced pressure (20 mm Hg; 2.7 kPa) at a temperature of about 20° C

Sources & evidence

ORD record
ord-6df46821bb644bd3a00696473b4e15b5
Source dataset
uspto-grants-1983_04
Patent number
US04379154

Reaction notes

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