KBS11-4 - Azidation of 1-bromoadamantane - Githubissues

KlementineJBS / USYD_PhD_ELN

This repository forms the electronic laboratory notebook (ELN)for Klementine Burrell-Sander's PhD's

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KBS11-4 - Azidation of 1-bromoadamantane #7

Closed KlementineJBS closed 2 years ago

KlementineJBS commented 2 years ago

Link to HIRAC, original method and master page.

KBS11 Azidation of 1-adamantane.docx

Reaction Scheme

Bromoadamantane to azidoadamantane (ELN)

Outcome

N/A

Notes

No evidence of product in NMR. Abandoned.

KlementineJBS commented 2 years ago

19.04.22

Monitor closely and consider adding extra TMSN3
Attempt alternative purification?

KlementineJBS commented 2 years ago

20.04.22

496.8 mg (2.31 mmol) 1-bromoadamantane added to oven-dried flask under positive pressure
9 mL dry THF added
0.6 mL (4.56 mmol, 2equiv.) TMSN3 added
0.7 mL (0.3 equiv.) SnCl4 added at 10.15 am
heated to reflux and left
TLC'd at 4.30 pm (20:80 EtOAc:hexane)

TLC plate

added more TMSN3 (0.3 mL, 2.28 mmol, 1 equiv.)

KlementineJBS commented 2 years ago

21.04.22

TLC'd at 9.45 am

TLC

TLC'd again at 4.30 pm (10% EtOAc in hexane)

TLC

confused by spots

KlementineJBS commented 2 years ago

22.04.22

TLC'd at 9.30 am (10:90 EtOAc:hexane)

TLC

decided to quench reaction anyway - added 50 mL water dropwise
extracted with ethyl acetate (3 X 40 mL) and washed with brine (100 mL)
dried over mag sulphate
vial (empty) = 15.4911 g

KlementineJBS commented 2 years ago

26.04.22

NMR of crude product

KBS11-4 cr_1.zip

KBS11-4 crude

KBS11-1 clean over KBS11-4 crude

tried to column crude product
initially ran on ethyl acetate by mistake for ~1.5 CV
then ran on 100% pet. benzine

$TLC of fractions$

KlementineJBS commented 2 years ago

29.04.22

Ran a second column (gradient from 0 - 40% ethyl acetate in hexane). Product only evident in fractions 10 and 11.

$fractions 1-16$ $fractions 8 - 12$

Unfortunately, NMR indicated little or no desired product was present.

KBS11-4 columned_1.zip

KBS11-4 columned