Water → HCID 21250999, compound

HRID 1531837Notes

Reaction equation

HRID 1531837 reaction equation
[C:1]1([N:7]2[C:11]3[CH2:12][CH2:13][CH2:14][CH2:15][C:10]=3[N:9]=[CH:8]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C([Li])CCC.[CH3:21][S:22]SC.O>CCCCCC.O1CCCC1.C(OCC)(=O)C>[C:1]1([N:7]2[C:11]3[CH2:12][CH2:13][CH2:14][CH2:15][C:10]=3[N:9]=[C:8]2[S:22][CH3:21])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

8

Reactant 4

HCID 962WaterHCID 12232Dimethyl DisulfideHCID 212510184,5,6,7-Tetrahydro-1-phenyl-1H-benzimidazoleHCID 178418339Butyllithium

Product 1

HCID 21250999HCID 21250999, compoundYield 74%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

2.36 g (12 mmol) of 1-phenyl-4,5,6,7-tetrahydro-1H-benzimidazole are placed in a 100-ml three-necked flask under nitrogen, 20 ml of tetrahydrofuran are added and then the mixture is cooled to −78° C. 9 ml (14.3 mmol) of a 1.6 N butyllithium solution in hexane are then slowly added. The mixture is stirred at −80° C. for 5 minutes and then the temperature is allowed to rise to −20° C. and the mixture is stirred for a further 45 minutes at this temperature. The reaction medium is then cooled to −80° C. and a solution of 2.24 g (24 mmol) of dimethyl disulphide diluted in 10 ml of tetrahydrofuran is introduced into it dropwise. When the addition is complete, the medium is allowed to return to room temperature. It is then cooled to 0° C. before gently introducing 15 ml of water and then 15 ml of ethyl acetate. The phases are separated and then the aqueous phase is extracted twice with 10 ml of ethyl acetate. The combined organic phases are washed twice with 10 ml of water, once with 5 ml of brine and then dried over MgSO4 and concentrated under vacuum. The crude reaction product is purified on a silica gel using, as eluting solution, a methanol gradient from 1 to 2% in dichloromethane. 2.17 g of 1-phenyl-2-methylthio-4,5,6,7-tetrahydrobenzimidazole are obtained. Yield=74% (m.p.=112° C.).

Workup

  1. customto rise to −20° C.
  2. stirringthe mixture is stirred for a further 45 minutes at this temperature
  3. temperatureThe reaction medium is then cooled to −80° C.
  4. additionis introduced into it dropwise
  5. additionWhen the addition
  6. customto return to room temperature
  7. temperatureIt is then cooled to 0° C.
  8. customThe phases are separated
  9. extractionthe aqueous phase is extracted twice with 10 ml of ethyl acetate
  10. washThe combined organic phases are washed twice with 10 ml of water, once with 5 ml of brine
  11. dry with materialdried over MgSO4
  12. concentrationconcentrated under vacuum
  13. customThe crude reaction product
  14. customis purified on a silica gel using
  15. washas eluting solution

Sources & evidence

ORD record
ord-b3fbbf7318f848839282cf4ddf4e873b
Source dataset
uspto-grants-2001_03
Patent number
US06200991B1

Reaction notes

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