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16th August 2016 @ 07:16

Procedure:

For details of synthesis of hydrazinylpyrazine, see Synthesis of 2-Chloro-6-hydrazinylpyrazine (AEW 85-7)

Hydrazinylpyrazine can also be purchased commercially.

Hydrazinylpyrazine (8.00g, 55.3mmol, 1 equiv.), triethyl orthoformate (16.40g 18.4 ml, 111 mmol, 2 equiv.), and tosylic acid (1.9g, 11.1mmol, 0.2 equiv.) were dissolved in toluene (158ml, 0.35 M with respect to Hydrazinylpyrazine) and heated at reflux for about 24 hours

Volatiles were removed under reduced pressure, remaining orthoester was blown off under a gentle stream of nitrogen.

NMR of the crude showed that purification is needed. TLC showed that 6 fractions were spotted. The reaction mixture was dissolved in ethyl acetate and mixed with slica. The solvent (ethyl acetate) was evaporated under reduced pressure. Purified by column chromatography (30 to 100% ethyl acetate in hexanes). All fractions are yellow solid.

Strings:

ClC1=CN=CC(NN)=N1

and

CCOC(OCC)([H])OCC

to

ClC1=CN=CC2=NN=CN21

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

and  

InChI=1S/C7H16O3/c1-4-8-7(9-5-2)10-6-3/h7H,4-6H2,1-3H3  

to  

InChI=1S/C5H3ClN4/c6-4-1-7-2-5-9-8-3-10(4)5/h1-3H

HIRAC
See Synthesis of 5-chloro-[1,2,4]triazolo[4,3-a]pyrazine (HM 1-3)
 
Log
 
16th Aug
The reaction started at 4:30pm. Hydrazinylpyrazine was place in the flask then toluene was added while stirring.  Triethyl orthoformate was then added to the mixture and heat to 90℃ to get a clear wine red solution. At 5:30pm, tosylic acid was added.
 
17th Aug
 
No sticky solid formed.TLC was performed, showing product was formed and there was only small amout of by product. Reaction was switched off at 11:00am.
 
NMR data
Crude NMR:
HM 1-5.png
HM 1-5 crude.zip
Attached Files
IMG_2758.JPG
HM 1-5.png
HM 1-5 crude.zip