Tin atom → HCID 13376759, compound

HRID 1979815Notes

Reaction equation

HRID 1979815 reaction equation
[Sn].[CH3:2][C:3]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[N:5]2[CH2:12][CH2:13][CH2:14][C:15](=[O:16])[C:4]=12.[Br-:17].[Br-].[Br-].C[N+](C)(C)C1C=CC=CC=1.C[N+](C1C=CC=CC=1)(C)C.C[N+](C1C=CC=CC=1)(C)C>C(Cl)Cl>[Br:17][CH:14]1[CH2:13][CH2:12][N:5]2[C:6]3[C:11]([C:3]([CH3:2])=[C:4]2[C:15]1=[O:16])=[CH:10][CH:9]=[CH:8][CH:7]=3

Participants

5

Reactant 3

HCID 5352426Tin atomHCID 10899625HCID 10899625, compoundHCID 17977687Phenyltrimethylammonium bromide dibromide

Product 1

HCID 13376759HCID 13376759, compoundYield 86.8%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
10 °C

Procedure

The reaction was performed in the dark (the flask wrapped in a tin-foil), and with the provision for maintaining a nitrogen atmosphere. To a solution of 10-methyl-6,7,8,9-tetrahydropyrido[1,2-a]indol-9-one (described in Example 7, 49.75 g) in methylene chloride (250 mL) was added a solution of trimethylphenylammonium tribromide (94 g) in methylene chloride (1200 mL) as fast as possible (over 2 min); the inside temperature was maintained at 10° C. The reaction mixture was stirred at room temperature for 30 hr, evaporated in vacuo, and the solid residue was partitioned between water (600 mL) and benzene-diethyl ether 1:1 (800 mL, v/v). The separated organic layer was dried (MgSO4), filtered, and the filtrate was evaporated. The crude product was dissolved in chloroform (55 mL), and diethyl ether (600 mL) was added at once, whereby a voluminous, dark-green material precipitated. It was quickly removed by filtration (without suction), and the filtrate was chilled to 0° C. The crystals which formed were collected by filtration; 38 g, mp 126°-128° C. This material was recrystallized from chloroform-diethyl ether (1:8, v/v) to give 35 g of the title compound, mp 131°-133° C.; IR (CHCl3) 1665-1660, and 1535 cm-1 ; UV max (MeOH) 246 and 327 nm, (ε16000) and (18200) respectively; NMR (CDCl3) δ 2.67 (br s, 3H), overlapping with 2.65 (m, 2H), 4.29 (dd, J1 =7.5 Hz, J2 =4.5 Hz, 2H), 4.67 (t, J=4 Hz, 1H), 7.25-7.7 (m, 4H); Anal. Calcd for C13H12BrNO: C, 56.12% H, 4.35% N, 5.03% and Found: C, 56.20% H, 4.32% N, 5.05%.

Workup

  1. temperaturefor maintaining a nitrogen atmosphere
  2. customevaporated in vacuo
  3. customthe solid residue was partitioned between water (600 mL) and benzene-diethyl ether 1:1 (800 mL, v/v)
  4. dry with materialThe separated organic layer was dried (MgSO4)
  5. filtrationfiltered
  6. customthe filtrate was evaporated
  7. dissolutionThe crude product was dissolved in chloroform (55 mL)
  8. additiondiethyl ether (600 mL) was added at once, whereby a voluminous, dark-green material
  9. customprecipitated
  10. customIt was quickly removed by filtration (without suction)
  11. temperaturethe filtrate was chilled to 0° C
  12. customThe crystals which formed
  13. filtrationwere collected by filtration
  14. customThis material was recrystallized from chloroform-diethyl ether (1:8, v/v)

Sources & evidence

ORD record
ord-71f6498d8e354940bd4abfa96a88fd9e
Source dataset
uspto-grants-1984_11
Patent number
US04482714

Reaction notes

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