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9th April 2014 @ 02:38

Synthesis of a variation of JU 2. Key starting material for JU 8-1.

Reaction Scheme

Procedure

Started 12:30pm

JU 1-5 (crude, 2.509 g, 17.3 mmol) was stirred into a solution of AcOH (1 mL) and MeCN (30 mL). 4-chlorobenzaldehyde (1.950 g, 13.84 mmol, 0.8 equiv) was added and the reaction was stirred at room temperature for 1 h. Analysis by TLC showed the reaction was incomplete.

TLC JU 7-1 30:70 EtOAc:Hex 1 h.jpg

The reaction was stirred for a further 4 hours. Analysis by TLC showed the reaction was complete due to the disappearance of JU 1-5. The product spot appeared smeared, this may be due to hydrolysis on the TLC plate.

TLC JU 7-1 10:90 EtOAc:Hex 5 h.jpg

The solvent was removed by rotary evaporation and the crude product dried in vacuo to yield a pale yellow solid (3.885 g, 14.54 mmol). The crude product was analysed by 1H NMR.

1H NMR, crude, DMSO, 200 MHz

JU 7-1 crude DMSO 200 MHz.pdf
JU 7-1 crude DMSO.zip

1H NMR, 4-chlorobenzaldehyde, CDCl3, 200 MHz

4-chlorobenzaldehyde CDCl3 200 MHz.pdf
4-chlorobenzaldehyde CDCl3.zip


09/05/2014

1.571 g (5.881 mmol) of JU 7-1 was purified using the Biotage Isolera instrument (see report below). The red fractions (fractions 15-51) were collected as were the yellow ones (fractions 11-14) as they showed the product spot in a TLC.

JU 7-1_arch.pdf

The solvent from the two fractions was removed by rotary evaporation and the product dried in vacuo to yield pale yellow crystals for each. Each fraction was analysed by proton NMR.

1H NMR, pure (red frac), DMSO, 300 MHz

JU 7-1 pure DMSO 300 MHz.pdf
JU 7-1 pure red frac DMSO.zip

1H NMR, impure (yellow frac), DMSO, 300 MHz

JU 7-1 yellow impure frac DMSO 300 MHz.pdf
JU 7-1 yellow frac DMSO.zip

13/05/2014

The remaining 1.207 g (4.519 mmol) of JU 7-1 was purified using the Biotage Isolera instrument (see report below).

JU 7-1 2_arch.pdf

The solvent from the two fractions was removed by rotary evaporation and the product dried in vacuo to yield pale yellow crystals for each. Each fraction was analysed by proton NMR.

1H NMR, pure, DMSO, 300 MHz

JU 7-1 pure 2 DMSO 300 MHz.pdf
JU 7-1 pure 2 DMSO.zip

1H NMR, impure, DMSO, 300 MHz

JU 7-1 2 impure frac DMSO 300 MHz.pdf
JU 7-1 impure 2 DMSO.zip

19/05/14

The impure fraction from the first purification batch and both fractions from the second batch were combined and a second purification was attempted due to impurities present in all 3 samples. See run report below.

JU 7-1 3_arch.pdf

1H NMR, pure, DMSO, 300 MHz

JU 7-1 3 pure DMSO 300 MHz.pdf
JU 7-1 3 pure DMSO.zip

1H NMR, impure, DMSO, 300 MHz

JU 7-1 3 impure frac DMSO 300 MHz.pdf
JU 7-1 3 impure DMSO.zip


IR data

JU 7-1.pdf

13C NMR, DMSO, 300 MHz

JU 7-1 carbon 300 MHz.pdf
JU 7-1C.zip


HIRAC

HIRAC JU 7-1.pdf

InChI strings

InChI=1S/C4H5ClN4/c5-3-1-7-2-4(8-3)9-6/h1-2H,6H2,(H,8,9)

and

InChI=1S/C7H5ClO/c8-7-3-1-6(5-9)2-4-7/h1-5H

to

InChI=1S/C12H8ClN5/c13-11-7-15-8-12(17-11)18-16-6-10-3-1-9(5-14)2-4-10/h1-4,6-8H,(H,17,18)/b16-6+

SMILES

ClC1=CN=CC(NN)=N1

and

[H]C(C1=CC=C(Cl)C=C1)=O

to

ClC1=CN=CC(N/N=C/C2=CC=C(C#N)C=C2)=N1

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Attached Files
Reaction Scheme JU 7-1.png
HIRAC JU 7-1.pdf
TLC JU 7-1 10:90 EtOAc:Hex 5 h.jpg
TLC JU 7-1 30:70 EtOAc:Hex 1 h.jpg
JU 7-1 crude DMSO 200 MHz.pdf
JU 7-1 crude DMSO.zip
4-chlorobenzaldehyde CDCl3 200 MHz.pdf
4-chlorobenzaldehyde CDCl3.zip
JU 7-1 pure DMSO 300 MHz.pdf
JU 7-1_arch.pdf
JU 7-1 pure red frac DMSO.zip
JU 7-1 yellow impure frac DMSO 300 MHz.pdf
JU 7-1 yellow frac DMSO.zip
JU 7-1 3_arch.pdf
JU 7-1 3 impure DMSO.zip
JU 7-1 3 pure DMSO.zip
JU 7-1 3 impure frac DMSO 300 MHz.pdf
JU 7-1 3 pure DMSO 300 MHz.pdf
JU 7-1 impure 2 DMSO.zip
JU 7-1 2 impure frac DMSO 300 MHz.pdf
JU 7-1 pure 2 DMSO 300 MHz.pdf
JU 7-1 pure 2 DMSO.zip
JU 7-1 2_arch.pdf
JU 7-1.pdf
JU 7-1C.zip
JU 7-1 carbon 300 MHz.pdf