1,2-Dibromoethane → HCID 13732942, compound

HRID 1731825Notes

Reaction equation

HRID 1731825 reaction equation
[Mg].BrCCBr.[CH3:6][N:7]([CH3:12])[CH2:8][CH2:9][CH2:10]Cl.[Br:13][C:14]1[CH:15]=[CH:16][C:17]2[O:27][C:20]3([CH2:26][CH2:25][CH2:24][CH2:23][CH2:22][CH2:21]3)[C:19](=[O:28])[C:18]=2[CH:29]=1.[Cl-].[NH4+]>C(OCC)C.C1C=CC=CC=1>[Br:13][C:14]1[CH:15]=[CH:16][C:17]2[O:27][C:20]3([CH2:26][CH2:25][CH2:24][CH2:23][CH2:22][CH2:21]3)[C:19]([CH2:10][CH2:9][CH2:8][N:7]([CH3:12])[CH3:6])([OH:28])[C:18]=2[CH:29]=1

Participants

8

Reactant 5

HCID 78391,2-DibromoethaneHCID 25517Ammonium ChlorideHCID 669603-Chloro-N,N-dimethyl-1-propanamineHCID 5462224MagnesiumHCID 13732929HCID 13732929, compound

Product 1

HCID 13732942HCID 13732942, compound

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 3283Diethyl EtherSolvent3×

Procedure

A stirred mixture of 2.72 g of magnesium turnings in 32 ml of diethyl ether containing about 0.5 ml of 1,2-dibromoethane was treated with a solution of 13.62 g of freshly distilled 3-dimethylaminopropyl chloride in 32 ml of ether at a rate sufficient to produce and maintain reflux. After the addition, a solution of 16.53 g of 5-bromo-spiro[benzofuran-2(3H),1'-cycloheptan]-3-one in 65 ml of benzene was added, followed by an additional 32 ml of ether and the mixture was refluxed overnight under nitrogen. After 14.5 hours of reflux, the mixture was cooled in ice water and treated cautiously with 140 ml of saturated aqueous ammonium chloride solution. The mixture was then poured into a separatory funnel, the flask was rinsed with a few hundred ml's of distilled water, and the combined mixture was extracted with ether (2×400 ml). The combined organic extracts were washed with water (250 ml) and saturated sodium chloride solution (250 ml), dried over anhydrous sodium sulfate, filtered and concentrated in vacuo to an oil which crystallized to a solid. This material was triturated with petroleum ether and filtered to afford 8.74 g of crude product. Preparative HPLC purification of this material was performed using two columns and 5% methanol/dichloromethane as a solvent. The purest fractions containing the desired material were combined and concentrated in vacuo to a solid. This material was triturated with hexane, filtered and dried to afford 4.16 g of a solid, m.p. 126°-128° C.

Workup

  1. customto produce
  2. temperaturemaintain
  3. temperaturereflux
  4. additionAfter the addition
  5. temperaturethe mixture was refluxed overnight under nitrogen
  6. temperatureAfter 14.5 hours of reflux
  7. additionThe mixture was then poured into a separatory funnel
  8. washthe flask was rinsed with a few hundred ml's of distilled water
  9. extractionthe combined mixture was extracted with ether (2×400 ml)
  10. washThe combined organic extracts were washed with water (250 ml) and saturated sodium chloride solution (250 ml)
  11. dry with materialdried over anhydrous sodium sulfate
  12. filtrationfiltered
  13. concentrationconcentrated in vacuo to an oil which
  14. customcrystallized to a solid
  15. customThis material was triturated with petroleum ether
  16. filtrationfiltered
  17. customto afford 8.74 g of crude product
  18. customPreparative HPLC purification of this material
  19. additionThe purest fractions containing the desired material
  20. concentrationconcentrated in vacuo to a solid
  21. customThis material was triturated with hexane
  22. filtrationfiltered
  23. customdried

Sources & evidence

ORD record
ord-1085458bcc794be98d1732b406159232
Source dataset
uspto-grants-1986_11
Patent number
US04623657

Reaction notes

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