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23rd March 2014 @ 22:38

Conclusions: 1H NMR showed no trace of the product and only the alcohol. It is likely that the combination of high temperature and base caused JU 3-6 to break down.

This reaction is a model reaction to test if previously trialled conditions in JU 4-1 will work on the triazolopyrazine.

Literature reference: 10.1021/jo901707x

GitHub link: #165

Reaction Scheme

Procedure

Started 11am

Phenethyl alcohol (0.06 mL, 60 mg, 0.5 mmol, 1.2 equiv) was added to 1 mL toluene along with JU 3-6 (100 mg, 0.4 mmol, 1 equiv), potassium hydroxide (93 mg, 1.66 mmol, 4 equiv) and 18-crown-6 (15 mg, 0.06 mmol, 0.15 equiv). The mixture turned dark red brown and was heated at reflux for 1 h 20 (bath tempertaure 110oC). Analysis by TLC was unlcear and the reaction was left for a further 3 h 40.

TLC JU 6-1 EtOAc:Hex 50:50 1.3h.jpg

Analysis by TLC using a more polar solvent system showed the reaction was complete as JU 3-6 had all disappeared.

TLC JU 6-1 EtOAc:Hex 75:25 5h.jpg
TLC JU 6-1 EtOAc:Hex 75:25 5h vanillin.jpg

The sample was cooled to room temperature and diluted with 4 mL of water. The mixture was extracted with EtOAc (4 x 3 mL). The combined organic layer was washed with water (2 x 4 mL) until the aqueous layer became neutral followed by brine (3 mL) and dried over Na2SO4. This was filtered and dried under reduced pressure and in vacuo to yield a pale orange oil (102 mg, 75% crude yield) that was analysed by 1H NMR.

1H NMR, crude, DMSO, 200 MHz

JU 6-1 crude DMSO 200 MHz.pdf
JU 6-1 crude DMSO.zip

 

HIRAC

HIRAC JU 6-1.pdf

InChI strings

InChI=1S/C12H6ClN5/c13-10-6-15-7-11-16-17-12(18(10)11)9-3-1-8(5-14)2-4-9/h1-4,6-7H

and

InChI=1S/C8H10O/c9-7-6-8-4-2-1-3-5-8/h1-5,9H,6-7H2

to

InChI=1S/C20H15N5O/c21-12-16-6-8-17(9-7-16)20-24-23-18-13-22-14-19(25(18)20)26-11-10-15-4-2-1-3-5-15/h1-9,13-14H,10-11H2

SMILES

N#CC(C=C1)=CC=C1C2=NN=C3C=NC=C(Cl)N32

and

OCCC1=CC=CC=C1

to

N#CC(C=C1)=CC=C1C2=NN=C3C=NC=C(OCCC4=CC=CC=C4)N32

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Attached Files
Reaction Scheme JU 6-1.png
HIRAC JU 6-1.pdf
TLC JU 6-1 EtOAc:Hex 75:25 5h vanillin.jpg
TLC JU 6-1 EtOAc:Hex 50:50 1.3h.jpg
TLC JU 6-1 EtOAc:Hex 75:25 5h.jpg
JU 6-1 crude DMSO 200 MHz.pdf
JU 6-1 crude DMSO.zip