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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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KBS48-1 - Mitsunobu reaction with KBS28 and KBS43 #180

Closed KlementineJBS closed 2 months ago

KlementineJBS commented 5 months ago

Link to HIRAC and master page #174.

HIRAC KBS48 Mitsunobu reaction on linear amines.docx

Reaction scheme

KBS48 - Mitsunobu on linear amines

Outcome

147.9 mg (0.164 mmol, 82%)

KlementineJBS commented 5 months ago
  1. Added SM KBS43-3 (97.2 mg, 0.200 mmol), KBS28 (116 mg, 0.515 mmol, 2.6 equiv.) and PPh3 (182.6 mg, 0.696 mmol, 3.5 equiv.) to a dry flask
  2. Evacuated and backfilled x 5. Noted a small bubble of liquid on first vac, so left vac on for ~10 minutes in last go.
  3. Added dry THF (4 mL). Vac was still on at first so some solvent might have been lost.
  4. Cooled to 0 C
  5. Added DIAD (1.4 mL, 1.442 mg, 7.13 mmol, 36 equiv.) dropwise
  6. Left stirring at rt from 2.15 pm
KlementineJBS commented 5 months ago

LRMS of reaction mixture

Some evidence of mono-product, not sure what peaks at 313.19+, 777.23+, 856.94 (3+) 1133.90 (4+) or 975.20- mean.

856.94/3 = 285.65, 1133.90/4 = 283.48,

triphenylphosphine oxide = 278.29 (+Cl = 313 but this would be negative)

KBS48-1 RM.pdf KBS48-1 RM.d.zip

KlementineJBS commented 5 months ago

TLC's from yesterday afternoon and this morning indicate some formation of new compound, but little consumption of either SM. (SM used in TLC is KBS43).

  1. Added more PPh3 (103.1 mg, 0.393 mmol, 2 equiv.). Realised that the amount of DIAD added was too large by a factor of 10.
KlementineJBS commented 5 months ago

LRMS

KBS48-1 RM 23-01-24.pdf KBS48-1 RM 23-01-2400000.d.zip

KlementineJBS commented 5 months ago

Column b

image
Fractions Tare (g) Mass (mg) Substance
8-10 15.5673 11 junk
11-14 not isolated
15-45 15.6767 159.8 mono product
61-105 15.6561 190.7 bis:mono 1:4
W1 15.6763 147.9 bis product
W2 15.6191 75.2 mg unknown - thought was azide but has no 2200 peak on IR

Note these masses are far too large - presumably still contain solvent.

TLC
KlementineJBS commented 5 months ago

H NMR

KBS48-1b.pdf KBS48-1b F61-105_1.zip KBS48-1b F8-10_1.zip KBS48-1b F15-45_1.zip KBS48-1b W2_1.zip

Product

KBS48-1b W1 triturated.pdf

KBS48-1b W1_1.zip KBS48-1b W1 triturated_1.zip

KlementineJBS commented 4 months ago

Realised that if bis product is present in F61-105, that is probably the dominant species in W1. Lower spot believed to be PPh3O - tried to remove by tritutation with ether but product is still slightly impure. Need to measure mass.