Water → HCID 13732936, compound

HRID 1731827Notes

Reaction equation

HRID 1731827 reaction equation
[ClH:1].[CH3:2][N:3]([CH3:22])[CH2:4][CH2:5][CH2:6][CH:7]1[C:11]2([CH2:17][CH2:16][CH2:15][CH2:14][CH2:13][CH2:12]2)[O:10][C:9]2[CH:18]=[CH:19][CH:20]=[CH:21][C:8]1=2.[Br:23]N1C(=O)CCC1=O.O.C(=O)(O)[O-].[Na+]>CO>[ClH:1].[Br:23][C:20]1[CH:19]=[CH:18][C:9]2[O:10][C:11]3([CH2:17][CH2:16][CH2:15][CH2:14][CH2:13][CH2:12]3)[CH:7]([CH2:6][CH2:5][CH2:4][N:3]([CH3:2])[CH3:22])[C:8]=2[CH:21]=1

Participants

6

Reactant 4

HCID 962WaterHCID 67184N-bromobutanimideHCID 516892Sodium BicarbonateHCID 13732934HCID 13732934, compound

Product 1

HCID 13732936HCID 13732936, compoundYield 93.4%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a stirred solution of 3.89 g of 3-(3-dimethylaminopropyl)-spiro[benzofuran-2(3H),1'-cycloheptane] hydrochloride in 35 ml of methanol at room temperature under nitrogen was added 2.24 g of N-bromosuccinimide. All solid dissolved rapidly as the pot temperature rose to 33° C. A TLC analysis after 20 minutes showed a complete reaction. The mixture was poured into water (175 ml), and 250 ml of saturated sodium bicarbonate solution was added with stirring. The mixture was then extracted with ether (2×250 ml). The combined organic extracts were washed with water (100 ml) and saturated sodium chloride solution (100 ml), dried briefly over anhydrous sodium sulfate, filtered and concentrated in vacuo to an oil. This material was dissolved in 100 ml of ether and the solution was stirred and treated with hydrogen chloride-saturated ether solution until the liquid phase was acidic to a pH paper. After a few minutes, the salt was filtered off, washed with ether and dried to afford 4.52 g of a solid, m.p. 169°-172° C. This crude salt was combined with two other batches of previously prepared crude salt and recrystallized by dissolving the solids in 20 ml of absolute ethanol, filtering by gravity, and treating the stirred filtrate dropwise with ether (140 ml). After stirring for 30 minutes the recrystallized salt was filtered, triturated and washed with ethanol/ether (1:7) solution, then ether and finally hexane. Drying in vacuo afforded 5.08 g of crystalline solid, m.p. 174°-176° C.

Workup

  1. dissolutionAll solid dissolved rapidly as the pot temperature
  2. customrose to 33° C
  3. customa complete reaction
  4. additionwas added
  5. extractionThe mixture was then extracted with ether (2×250 ml)
  6. washThe combined organic extracts were washed with water (100 ml) and saturated sodium chloride solution (100 ml)
  7. dry with materialdried briefly over anhydrous sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo to an oil
  10. dissolutionThis material was dissolved in 100 ml of ether
  11. stirringthe solution was stirred
  12. additiontreated with hydrogen chloride-saturated ether solution until the liquid phase
  13. waitAfter a few minutes
  14. filtrationthe salt was filtered off
  15. washwashed with ether
  16. customdried

Sources & evidence

ORD record
ord-8ccb029a5e994ccf9029a46b7a79ffd9
Source dataset
uspto-grants-1986_11
Patent number
US04623657

Reaction notes

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