2-Amino-6-chloro-5-chloromethyl-3-cyanopyrazine

Amino-6-chloro-5-chloromethyl-3-cyanopyrazine with sodium acetate in dimethylformamide afforded 2-acetoxymethyl-5-amino-3-chIoro-6-cyanopyrazine (874), and 2-amino-5-chloromethyl-3-cyanopyrazine with potassium acetate in 2-propanol gave 5-acetoxymethyl-2-amino-3[Pg.165]

The synthesis of 2-amino-5-chloromethyl-3-cyanopyrazine 1-oxide (529) from aminomalononitrile and chloromethyl hydroxyiminomethyl ketone, and of 2-amino-6-chloromethyl(and chloroalkyl)-3-cyanopyrazine 1-oxide (534) from aminomalononitrile and -chloro-a-hydroxyiminopropionaldehyde (prepared from the addition of nitrosyl chloride to acrolein) has been described in Section III.l. 

Chloro-3-dichloromethylpyrazine with sodium methanethiolate has been claimed to give a mixture of products analogous to those obtained from its reaction with sodium methoxide (688). 2-Amino-5-chloromethyl-3-cyanopyrazine with... 

Amino-5-chloromethyl-3-cyanopyrazine 1-oxide with triphenylphosphine in dimethylformamide at 80-90° gave 2-amino-3-cyano-5-(triphenylphosphonio)-methylpyrazine 1-oxide chloride (97) (520) and the 5-bromomethyl analogue reacted similarly with triphenylphosphine in propan-2-ol (542). Compound (97) on hydrolysis with 30% aqueous ethanol containing a small amount of triethylamine gave 2-amino-3-cyano-5-methylpyrazine 1-oxide and thus enabled removal of the chloro substituent from the chloromethylpyrazine (529) compound (97) with triethylamine and acetaldehyde (and other aldehydes) in chloroform at room temperature gave 2-amino-3-cyano-5-(prop-l -enyl)pyrazine 1-oxide (and other alkenyl analogues) (529). 

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