Methyl iodide → HCID 67417624, compound

HRID 1920611Notes

Reaction equation

HRID 1920611 reaction equation
[H-].[Na+].[Br:3][CH:4]1[CH:17]=[CH:16][C:15]2[C:14]3[C:9](=[CH:10][C:11]([Br:18])=[CH:12][CH:13]=3)[C:8](=[O:19])[C:7]([CH2:21][CH:22]([CH2:27][CH3:28])[CH2:23][CH2:24][CH2:25][CH3:26])([OH:20])[C:6]=2[CH2:5]1.[CH3:29]I.[NH4+].[OH-]>CS(C)=O.CO>[Br:3][CH:4]1[CH:17]=[CH:16][C:15]2[C:14]3[C:9](=[CH:10][C:11]([Br:18])=[CH:12][CH:13]=3)[C:8](=[O:19])[C:7]([CH2:21][CH:22]([CH2:27][CH3:28])[CH2:23][CH2:24][CH2:25][CH3:26])([O:20][CH3:29])[C:6]=2[CH2:5]1

Participants

7

Reactant 4

HCID 6328Methyl iodideHCID 14923Ammonium HydroxideHCID 24758Sodium hydrideHCID 67418309HCID 67418309, compound

Product 1

HCID 67417624HCID 67417624, compound

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolvent2×HCID 887MethanolSolvent

Procedure

3.3 g (81.5 mmol) of NaH (60% dispersion in mineral oil) in 30 ml of DMSO were introduced into a 500 ml four-necked flask with mechanical stirrer, condenser, thermometer and dropping funnel which had been dried by heating. 21.6 g (54.3 mmol) of 2,7-dibromo-9-keto-10-(2-ethylhexyl)-10-hydroxydihydrophenanthrene in 60 ml of DMSO were slowly added dropwise, and the mixture was stirred at room temperature for 30 min. 5.1 ml (81.5 mmol) of methyl iodide were then added dropwise over the course of 1 h with ice cooling. The mixture was stirred at room temperature for 2-days, then cooled to 5° C., 90 ml of semi-conc. NH4OH were added dropwise, 100 ml of MeOH were added dropwise, the mixture was stirred in an ice bath for 30 min, and the product was filtered off with suction, washed with MeOH and dried at 60° C. in a vacuum drying cabinet. The crude product was recrystallised a number of times from methanol. The total yield was 17.3 g (65% of theory) with a purity of >99.8%. 1H-NMR (CDCl3): [ppm]=8.16 (d, 4JHH=2.3 Hz, 1H), 7.78 (m, 4H), 7.56 (dd, 3JHH=8.7 Hz, 4JHH=2.3 Hz, 2H), 3.17 (s, 3H), 1.71 (m, 2H), 1.26 (m, 1H), 1.06 (m, 8H), 0.77 (m, 3H), 0.59 (m, 3H).

Workup

  1. customhad been dried
  2. temperatureby heating
  3. stirringThe mixture was stirred at room temperature for 2-days
  4. temperaturecooled to 5° C.
  5. stirringthe mixture was stirred in an ice bath for 30 min
  6. filtrationthe product was filtered off with suction
  7. washwashed with MeOH
  8. customdried at 60° C. in a vacuum
  9. customdrying cabinet
  10. customThe crude product was recrystallised a number of times from methanol

Sources & evidence

ORD record
ord-423143eb6115409d9e01ab016b6e5d57
Source dataset
uspto-grants-2012_05
Patent number
US08173276B2

Reaction notes

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