search

KlementineJBS / USYD_PhD_ELN

This repository forms the electronic laboratory notebook (ELN)for Klementine Burrell-Sander's PhD's
2 stars 0 forks source link

KBS17-6 - Propargylation of 1,6-diaminohexane #28

Closed KlementineJBS closed 1 year ago

KlementineJBS commented 1 year ago

Link to HIRAC, original method and master page.

Last attempts are #19 and #23.

KBS17 Generic propargylation of 1,n-diamine.docx

Reaction Scheme

KBS17 hexadiamine

KlementineJBS commented 1 year ago

09.08.22

  1. Dissolved KBS3 (1.00 g, 3.17 mmol) in dry DMF (20 mL)
  2. Added NaH (1.748 g, 26.9 mmol, 8.5 equiv.)
  3. Added propargyl bromide (1.00 mL, 10.6 equiv.)

Reaction immediately went a dirty brown dishwater colour.

Within a few minutes, reaction was completely black.

KlementineJBS commented 1 year ago

10.08.22

TLC at 11 am indicated reaction was complete.

  1. Quenched with NH4Cl (40 mL). Make sure to do this DROPWISE
  2. Diluted with water (60 mL)
  3. Extracted with toluene (3 x 125 mL)
  4. Washed with water (5 x 200 mL)
KlementineJBS commented 1 year ago

11.08.22

Empty vial: 16.0985 Full vial: 17.2010 Mass: 1.1025 g

KlementineJBS commented 1 year ago

12.08.22

Second extraction

Empty vial: 15.8755 Full vial: 16.4060 Mass: 530.5 mg

KlementineJBS commented 1 year ago

15.08.22

LRMS

For both:

KBS17-6 cr.pdf KBS17-6 cr.d.zip

KBS17-6 cr 2nd extract.pdf KBS17-6 cr 2nd extract.d.zip

KlementineJBS commented 1 year ago

25.08.22

Fractions Empty vial Full vial Mass (mg) Moles % Species
1-12 15.8657 15.8807 15 0.038 - -
13-18 16.2209 16.2943 73.4 0.187 - -
19-27 15.9732 15.9892 16 0.041 - -
28-47 16.0098 16.0273 17.5 0.045 - -
Column runoff 16.1856 16.1994 13.8 0.035 - -

NMR

KBS17-6 column (2nd extract).zip KBS17-6 column (2nd extract).pdf

None of these seem to have any product. Will try flushing column with 100% ethyl acetate.

KlementineJBS commented 1 year ago

26.08.22

Flushed with 100% ethyl acetate (2nd flush, 30-100 over 3 CV, 100 for 9 CV). NMR unclear, but mass spec indicates only SM present (339 is [M+Na]).

KBS17-6 2nd flush.zip KBS17-6 2nd flush processed.pdf

Mass spec

KBS17-6 2nd flush.pdf KBS17-6 2nd flush.d.zip

KlementineJBS commented 1 year ago

01.09.22

Manual column

~ 15 cm silica

Starting with 200 mL of 5:95 EtOac:hexanes 100 mL 10:90 as above 100 mL 50:50 150 mL straight ethyl acetate 100 mL 10:90 MeOH:DCM

Fractions Action Empty vial Full vial Mass (mg) Moles % Yield
3-15 Mono and bis product 16.0363 16.6931 656.8 1.67 53
16-19 Unknown 15.9959 15.9993 3.4 0.0087 0.3
20-28 Unknown 16.0607 16.0638 3.1 0.0079 0.2
29 onwards SM 15.8642 15.9108 46.9 0.119 4

Vial after loading sample: 16.1523