Science of Synthesis

Gilchrist, T. L., Science of Synthesis, (2005) 18, 1010.

Carbonimidic dichlorides ‌33‌ can be produced by the addition of electrophilic reagents to cyanogen chloride. The addition of acyl chlorides to cyanogen chloride does not require a catalyst; for example, benzoyl chloride and chloroacetyl chloride react with cyanogen chloride at 50°C under pressure to give the carbonimidic dichlorides ‌33‌ (R1 = Bz) (in 20% yield) and ‌33‌ (R1 = COCH2Cl) (in 64% yield).[‌71‌] (‌Scheme 12‌). The addition reactions of haloalkanes can be catalyzed by Lewis acids such as iron(III) chloride, in which case the carbonimidic dichlorides are isolated as complexes with the Lewis acid.[‌72‌] Inorganic electrophiles such as chlorine and sulfur dichloride also add to cyanogen chloride.[‌8‌] The addition of chlorine is carried out in an autoclave with activated carbon as a catalyst, giving N-chlorocarbonimidic dichloride ‌33‌ (R1 = Cl) in 77% yield.[‌73‌] Cyanogen chloride reacts with chlorine in the presence of monosubstituted alkenes to give carbonimidic dichlorides ‌34‌ in moderate yield (‌Scheme 12‌) (the corresponding 1,2-dichloroalkanes being the major products); analogous addition reactions are also reported with disubstituted alkenes, including cyclohexene.[‌74‌] Similar reactions with vinyl chloride and with 2-chloropropene give the corresponding carbonimidic dichlorides in good yield.[‌75‌] In these reactions the electrophile is probably the carbocation; it is generated by addition of the chlorinium ion to the alkene.

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References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) M 8, 8888.
• 8.Meeeee-Meee, (8888) M 8, 888.
• 8.Meeeee-Meee, (8888) M 8, 888.
• 8.Meeeee-Meee, (8888) M 8, 888.