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30th May 2013 @ 18:19

 

375 mg of 4-fluorophenyl azide (2 mmol) and 127 mg of methyl propynyloxyacetate (1 mmol) were dissolved in DCM:H2O (3ml:2ml) and stirred overnight with copper sulfate (12 mg) and sodium ascorbate (20 mg). The mixture was diluted with DCM and the organic layer washed with water, dried over magnesium sulfate and concentrated in vacuo to give 272 mg of yellow solid which was purified by dry column vacuum chromatography (40% ethyl acetate in heptane, followed by 100% ethyl acetate after 20 fractions) to give 4 products:

 

 

C1, 8.6 mg orange waxy solid. Inconsistent mass spec data.

PT-1-14-C1 1H.pdf
PT-1-14-C1 13C.pdf
PT-1-14-C1 DEPT135.pdf
PT-1-14-C1 DEPT90.pdf

 

 

C2, 42.3 mg (15%) white solid ESI-Nom 302 (M+Na)+, 581 (2M+Na) HRMS consistent

PT-1-14-C2 1H.pdf
PT-1-14-C2 13C.pdf
PT-1-14-C2 DEPT135.pdf
PT-1-14-C2 DEPT90.pdf
PT-1-14-C2 ESI-MS.jpg
PT-1-14-C2 HRMS.pdf

 

 

C3, desired product, white solid, 44.7 mg (17%) ESI-Nom 288 (M+Na+), 553 (2M+Na) HRMS consistent

PT-1-14-C3 1H.pdf
PT-1-14-C3 13C.pdf
PT-1-14-C3 DEPT135.pdf
PT-1-14-C3 DEPT90.pdf
PT-1-14-C3 ESI-MS.jpg
PT-1-14-C3 HRMS.pdf

 

 

C4, 18.6 mg (4%) white solid ESI-Nom 449 (M+Na+), 875 (2M+Na) HRMS consistent

PT-1-14-C4 1H.pdf
PT-1-14-C4 13C.pdf
PT-1-14-C4 DEPT135.pdf
PT-1-14-C4 DEPT90.pdf
PT-1-14-C4 ESI-MS.jpg
PT-1-14-C4 HRMS.pdf

 

Results and discussion.

C1, C3, and C4 seemingly correspond to the three possible products of the previous reaction and are present due to insufficient purification of PT-1-13 shown here:

Products.png

 C2 has apparently been produced by trans-esterification with ethanol even though no ethanol was used at any point.

The Mass Spectroscopy evidence for C1 is extremely unreliable, but the NMR evidence fits extremely well with analagous chemical shifts for CH2 groups in similar environments in product C4 (triazole-CH2-ester) and methyl bromoacetate (Br-CH2-ester). DEPT is consistent but there isn't enough sample to identify all the quaternary carbons - requires further study if it's a compound of interest.

C1-C4 have all been sent for antimalarial screening.

 

 

Linked Posts
Attached Files
PT-1-14-C1 1H.pdf
PT-1-14-C2 1H.pdf
PT-1-14-C3 1H.pdf
PT-1-14-C4 1H.pdf
Experiment 14.png
Products.png
PT-1-14-C3 DEPT90.pdf
PT-1-14-C3 DEPT135.pdf
PT-1-14-C3 13C.pdf
PT-1-14-C2 ESI-MS.jpg
PT-1-14-C3 ESI-MS.jpg
PT-1-14-C4 ESI-MS.jpg
PT-1-14-C2 13C.pdf
PT-1-14-C1 DEPT90.pdf
PT-1-14-C1 DEPT135.pdf
PT-1-14-C4 DEPT90.pdf
PT-1-14-C1 13C.pdf
PT-1-14-C4 DEPT135.pdf
PT-1-14-C4 13C.pdf
PT-1-14-C2 DEPT90.pdf
PT-1-14-C2 DEPT135.pdf
PT-1-14-C3 HRMS.pdf
PT-1-14-C2 HRMS.pdf
PT-1-14-C4 HRMS.pdf
PT-1-14-C4 NMR raw data.zip
PT-1-14-C3 NMR raw data.zip
PT-1-14-C2 NMR raw data.zip
PT-1-14-C1 NMR raw data.zip