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KlementineJBS / USYD_PhD_ELN

This repository forms the electronic laboratory notebook (ELN)for Klementine Burrell-Sander's PhD's
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KBS16-4 - Azidation of ferrocenylmethanol #17

Closed KlementineJBS closed 1 year ago

KlementineJBS commented 2 years ago

Link to HIRAC, original method and master page.

KBS16 Ferrocenylmethanol to azidomethylferrocene DPPA.docx

Next attempt is #27.

Reaction Scheme

Bromoadamantane to azidoadamantane (ELN)

Outcome

236 mg (0.978 mmol), 64%

Notes

KlementineJBS commented 2 years ago

23.06.22

  1. Set up a dry 50 mL 2-neck flask under N2
  2. Added 331.8 mg (1.54 mmol) via solution transfer (10 mL dry THF)
  3. Added DPPA (0.4 mL, 1.85 mmol, 1.2 equiv.) and DBU (0.28 mL, 1.85 mmol, 1.2 equiv.)
  4. Stirred from 10.15 am to 11.15 am (1 hr)
  5. Heated to reflux at 11.15 am
  6. Added NaN3 (116.9 mg, 1.69 mmol, 1.1 equiv.) at 1.15 pm
  7. Left stirring at reflux
  8. TLC at 4.30 pm indicated reaction was not yet complete
KlementineJBS commented 2 years ago

24.06.22

  1. TLC at 9.45 am indicated reaction was still not complete.

Strangely, the order of spots is reversed as compared with previous attempt #10 . The azide is expected to appear further up the plate than the alcohol, as in #10, so unsure what is causing this. There also appears to be a second product in the SM - the SM used was from KBS15-3 (made in 2021) so this may be a decomposition product?

  1. Added more DPPA (0.26 mL, 1.23 mmol, 0.8 equiv.) and DBU (0.18 mL, 1.23 mmol, 0.8 equiv.) at 10 am

  2. TLC at 4pm indicated completion - used a fresher sample of SM (from NMR sample of 15-4).

  1. Quenched with water (40 mL) and extracted with toluene (3 x 60 mL)
  2. Washed with brine, dried over MgSO4 and rotovapped
KlementineJBS commented 2 years ago

27.06.22

Vial (empty) = 15.7808 Vial (full) = 16.5859 Mass = 0.8051 mg

NMR

1H NMR (300 MHz, CDCl3) δ 4.23, 4.20, 4.17, 4.12.

NMR indicates product formation but has lots of junk - probably ethyl acetate, DBU and DPPA.

KBS16-4 cr_1.zip KBS16-4 cr processed.pdf

KBS16-4 cr

Will try to column before carrying through.

KlementineJBS commented 2 years ago

28.06.22

Ran a column with a gradient of ethyl acetate in hexanes, 0 - 10%. Fractions had 2 products by TLC -- first product largely in fractions 1 - 14 and second largely in fractions 16 - 30 (didn't check more closely).

PXL_20220628_065001126.MP.jpg

Product

Vial (empty) = 15.9410 Vial (full) = 16.1768 Mass = 235.8 mg

0.978 mmol

Side product

Vial (empty) = 15.9786 Vial (full) = 16.0726

KlementineJBS commented 2 years ago

29.06.22

NMR

Product

1H NMR (300 MHz, Chloroform-d) δ 4.24 (s, 2H), 4.20 (s, 2H), 4.17 (s, 5H), 4.12 (s, 2H).

KBS16-4_1.zip KBS16-4 processed.pdf

Mostly product, with some traces of ethyl acetate and water.

Side product

KBS16-4 SP_1.zip KBS16-4 SP processed.pdf

Possibly some unreacted SM but largely grease/solvent impurities.

IR

KBS16-4.0.zip KBS16-4.pdf

KlementineJBS commented 2 years ago

01.07.22

LRMS

20220701_KBS16-4.d.zip KBS16-4.pdf