HCID 22179298, compound → HCID 13706801, compound

HRID 928641Notes

Reaction equation

HRID 928641 reaction equation
[Li]CCCC.Br[CH2:7][C:8]1[CH:18]=[CH:17][CH:16]=[C:10]2[C:11]([NH:13][C:14](=[O:15])[C:9]=12)=[O:12]>COCCOC>[CH2:7]=[C:8]1[CH:18]=[CH:17][CH:16]=[C:10]2[C:11]([NH:13][C:14](=[O:15])[CH:9]12)=[O:12]

Participants

4

Reactant 2

HCID 22179298HCID 22179298, compoundHCID 178418339Butyllithium

Product 1

HCID 13706801HCID 13706801, compoundYield 105.5%

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent2×

Conditions

Temperature
-33 °C

Procedure

The starting carborane, 1-C6H5-1,2-C2B10H11 1.00 g (4.53 mmol) dried in vacuum, was dissolved in DME (40 ml) in Schlenk-type flask under argon, and the resulting solution was cooled down to −33° C. and BuLi (2.5 M in hexane, Aldrich, 2.0 ml, 5.0 mmol) was added under stirring from a syringe through septum. The reaction slurry was stirred for 15 min. and then left to warm up to room temperature. The reaction mixture was again cooled down and bromomethyl phtalimide 1.20 g (Aldrich, 5.0 mmol) dissolved in v 15 ml of DME was added dropwise from a syringe. The reaction mixture was stirred for 15 min. −33° C. at and then left slowly to warm up to room temperature over 4 h period. After standing overnight, the solids were filtered off under argon, and washed under argon with two portions of DME (10 ml). Diluted acetic acid (3 M, 0.5 ml) was added to the combined DME extracts and volatiles were removed under reduced pressure. A solid residue was dissolved in benzene and poured atop of a silica gel column (3×25 cm). Elution with benzene led to isolation of the starting 1-Ph-carborane (240 mg), continued elution using benzene-CH3CN (4:1, b.v.) solvent mixture afforded the methylene-phtalimide substituted intermediate carborane 0.85 g (49%).

Workup

  1. stirringThe reaction slurry was stirred for 15 min.
  2. waitleft
  3. temperatureto warm up to room temperature
  4. temperatureThe reaction mixture was again cooled down
  5. additionwas added dropwise from a syringe
  6. stirringThe reaction mixture was stirred for 15 min. −33° C. at and
  7. waitthen left slowly
  8. temperatureto warm up to room temperature over 4 h period
  9. filtrationthe solids were filtered off under argon
  10. washwashed under argon with two portions of DME (10 ml)
  11. additionDiluted acetic acid (3 M, 0.5 ml) was added to the combined DME extracts and volatiles
  12. customwere removed under reduced pressure
  13. dissolutionA solid residue was dissolved in benzene
  14. additionpoured atop of a silica gel column (3×25 cm)
  15. washElution with benzene
  16. washelution

Sources & evidence

ORD record
ord-648285d9d59e480caacb019bc1026894
Source dataset
uspto-grants-2016_03
Patent number
US09290529B2

Reaction notes

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