Methane → HCID 70056502, compound

HRID 1030501Notes

Reaction equation

HRID 1030501 reaction equation
I.CS[C:4]1[NH:8][C@@H:7]2[CH2:9][CH2:10][CH2:11][CH2:12][C@H:6]2[N:5]=1.[C:13]1([CH:19]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[CH2:20][CH2:21][NH2:22])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C.[ClH:30]>CO.[OH-].[Na+].C(Cl)Cl>[ClH:30].[C:23]1([CH:19]([C:13]2[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=2)[CH2:20][CH2:21][NH:22][C:4]2[NH:8][C@@H:7]3[CH2:9][CH2:10][CH2:11][CH2:12][C@H:6]3[N:5]=2)[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=1

Participants

8

Reactant 4

HCID 297Methane2×HCID 313Hydrochloric AcidHCID 796983,3-DiphenylpropylamineHCID 22843607HCID 22843607, compound

Product 1

HCID 70056502HCID 70056502, compound

Reagents, catalysts & solvents 3

HCID 887MethanolSolvent2×HCID 6344DichloromethaneSolventHCID 14798Sodium HydroxideSolvent

Conditions

Temperature
0 °C

Procedure

A flask containing 2-methylthio-trans-3a,4,5,6,7,7a-hexahydro-1H-benzimidazole hydroiodide (3.00 g, 1.01×10-2 mole) and 3,3-diphenylpropylamine (2.13 g, 1.01×10-2 mole) was immersed in an oil bath which had been preheated to ca. 155° C. The reaction was stirred at between 150°-160° C. for 1 hour. The resulting yellow glass was dissolved in methanol. The solution was treated with charcoal which was subsequently removed by filtration through a pad of celite. The filtrate was evaporated at reduced pressure affording a foam which was dissolved in a stirred, two phase mixture of 5 molar aqueous NaOH (70 ml) and CH2Cl2 (65 ml). After stirring over the weekend, the CH2Cl2 layer was separated. The aqueous alkaline layer was extracted with CH2Cl2 (2×). The CH2Cl2 layers were combined, washed with H2O (2×), washed with saturated aqueous NaCl, and dried over anhydrous Na2SO4. The drying agent was removed by filtration and the filtrate was evaporated at reduced pressure leaving an oil which was dissolved in methanol (43 ml). This solution was cooled to 0° C. before being treated with a methanolic solution of HCl. This solution was treated with charcoal which was subsequently removed by filtration through a pad of celite. The filtrate was evaporated on the steam bath and 2-butanone was added periodically until the temperature approached 80° C. The solution was then placed in the freezer. After ca. 3 days, a solid was collected by filtration. This material was recrystallized two times from methanol/2-butanone affording 2-(3,3-diphenylpropylamino)-trans-3a,4,5,6,7,7a-hexahydro-1H-benzimidazole hydrochloride as a colorless solid: 1.18 g (32%), m.p. 155°-157° C.

Workup

  1. customwas immersed in an oil bath
  2. customhad been preheated to ca. 155° C
  3. customwas subsequently removed by filtration through a pad of celite
  4. customThe filtrate was evaporated at reduced pressure
  5. customaffording a foam which
  6. stirringAfter stirring over the weekend
  7. customthe CH2Cl2 layer was separated
  8. extractionThe aqueous alkaline layer was extracted with CH2Cl2 (2×)
  9. washwashed with H2O (2×)
  10. washwashed with saturated aqueous NaCl
  11. dry with materialdried over anhydrous Na2SO4
  12. customThe drying agent was removed by filtration
  13. customthe filtrate was evaporated at reduced pressure
  14. customleaving an oil which
  15. customwas subsequently removed by filtration through a pad of celite
  16. customThe filtrate was evaporated on the steam bath and 2-butanone
  17. additionwas added periodically until the temperature
  18. customapproached 80° C
  19. waitAfter ca. 3 days
  20. filtrationa solid was collected by filtration
  21. customThis material was recrystallized two times from methanol/2-butanone

Sources & evidence

ORD record
ord-c3317abd393247e3bbf1210d205bf089
Source dataset
uspto-grants-1992_04
Patent number
US05106845

Reaction notes

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