KBS11-6 - Azidation of 1-bromoadamantane

[KlementineJBS]

Link to HIRAC, original method and master page.

HIRAC doc file: KBS11 Azidation of 1-adamantane.docx

Reaction Scheme

Outcome

N/A - crude product appeared to be desired compound, but was lost in purification

Notes

Need to optimise purification techniques.

[KlementineJBS]

04.05.22

1-bromoadamantane (103.6 mg, 0.482 mmol) was placed in a flask under nitrogen by solution transfer (MeCN, 5 mL). SnCl4 (0.14 mL, 1 M in heptane, 0.3 equiv.) and TMSN3 (0.15 mL, 1.14 mmol, 2.3 equiv.) were added and the reaction was left to reflux at 80 C from 1 pm.

[KlementineJBS]

05.05.22

TLC at 11 am indicated reaction completion. Took an aliquot of crude reaction mixture to analyse via NMR.

[KlementineJBS]

10.05.22

The reaction was quenched with water (15 mL) and then extracted with ethyl acetate (3 x 10 mL) and washed with brine (30 mL). After being dried over MgSO4, solvent was removed by rotary evaporation to give a crystalline yellowish solid.

Vial (empty): 15.8003 g Vial (product): 15.8825 g Product: 82.2 mg

Image of solid obtained after rotary evaporation

NMR

NMR analysis seems to indicate some azidoadamantane present, though the peak at 2.15 is largely obscured by acetonitrile (peak at 2.17).

KBS11-6 crude_1.zip

Reaction mixture (red) overlaid with known sample KBS 11-1 (blue)

[KlementineJBS]

14.06.22

1. Columned KBS11-6 but failed to find any product in fractions. (100% pet. benz. for 5 CV, 0 - 15% EtOAc in pet. benz. for 8 CV)

2. Tried columning again and still saw no product. (25% EtOAc in pet. benz. for 10 CV)

Have retained column but unlikely to be able to recover much pure product.