Tin atom → HCID 24956501, compound

HRID 1095568Notes

Reaction equation

HRID 1095568 reaction equation
Cl.[CH3:2][N:3]([CH3:32])[C:4]1([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH2:9][CH2:8][C:7]([C:10]2[NH:11][C:12]3[C:17]([C:18]=2[CH2:19][CH:20]2[CH2:25][CH2:24][CH2:23][CH2:22][CH2:21]2)=[CH:16][CH:15]=[CH:14][CH:13]=3)=[CH:6][CH2:5]1.[Sn]>Br.O>[CH2:19]([C:18]1[C:17]2[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=2)[NH:11][C:10]=1[CH:7]1[CH2:6][CH2:5][C:4]([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)([N:3]([CH3:2])[CH3:32])[CH2:9][CH2:8]1)[C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1

Participants

5

Reactant 2

HCID 5352426Tin atomHCID 66783294HCID 66783294, compound

Product 1

HCID 24956501HCID 24956501, compound

Reagents, catalysts & solvents 2

HCID 260Hydrogen BromideSolventHCID 962WaterSolvent

Procedure

Ex. 41 (768 mg, 1.733 mmol) was dissolved in hydrogen bromide/glacial acetic acid (33% HBr, 40 ml). Tin powder (2.060 g, 17.353 mmol) was then added to the mixture in portions at room temperature in the course of 40 min and the mixture was stirred for a further 20 min. The mixture was then diluted with water (100 ml). The mixture was stirred at 5° C. for 1 h. The product precipitated out as the hydrobromide. This was filtered off and washed with water (2×5 ml). 1 N NaOH (50 ml) was added to the beige-coloured moist solid (4.3 g). The mixture was extracted with methylene chloride (3×30 ml). The combined organic phases were dried with Na2SO4 and then filtered. The volatile constituents were removed completely in vacuo. An oil (619 mg) remained. After separation of this mixture by chromatography [silica gel 60 (80 g); ethyl acetate (500 ml), ethyl acetate/methanol 20:1 (525 ml), ethyl acetate/methanol 5:1 (600 ml), ethyl acetate/methanol 2:1 (600 ml)], 4-(3-benzyl-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine (less polar diastereoisomer) (186 mg, 26%, m.p.: 194-199° C.) and the more polar diastereoisomer (241 mg, 34%, m.p.: 205-209° C.) were obtained as beige-coloured solids.

Workup

  1. stirringThe mixture was stirred at 5° C. for 1 h
  2. customThe product precipitated out as the hydrobromide
  3. filtrationThis was filtered off
  4. washwashed with water (2×5 ml)
  5. addition1 N NaOH (50 ml) was added to the beige-coloured moist solid (4.3 g)
  6. extractionThe mixture was extracted with methylene chloride (3×30 ml)
  7. dry with materialThe combined organic phases were dried with Na2SO4
  8. filtrationfiltered
  9. customThe volatile constituents were removed completely in vacuo
  10. customAfter separation of this mixture by chromatography [silica gel 60 (80 g); ethyl acetate (500 ml), ethyl acetate/methanol 20:1 (525 ml), ethyl acetate/methanol 5:1 (600 ml), ethyl acetate/methanol 2:1 (600 ml)], 4-(3-benzyl-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine (less polar diastereoisomer) (186 mg, 26%, m.p.: 194-199° C.)
  11. customthe more polar diastereoisomer (241 mg, 34%, m.p.: 205-209° C.) were obtained as beige-coloured solids

Sources & evidence

ORD record
ord-db947eec8dba41a7b4fa524fc22e64ce
Source dataset
uspto-grants-2012_03
Patent number
US08138187B2

Reaction notes

Loading…