With classic Reimer-Tiemann reaction a variation is also given in my lecture notes which use carbon tetrachloride instead of chloroform. But to me, it seems like it would be just a substitution reaction rather than Reimer-Tiemann which proceeds through carbene. Given slow hydrolysis of $\ce{CCl4}$ how such a substitution reaction could be useful, even if we use $\ce{OH-}$ ? Or is there something else going on here?

  • $\begingroup$ You're right, as far as I know the $\ce{CCl4}$ reaction first occurs by the phenol (or phenoxide) acting as a nucleophile and substituting one of the chlorine atoms. The remaining three chlorine atoms are hydrolyzed and salicylic acid is formed $\endgroup$
    – TRC
    Commented Jul 12, 2021 at 9:23
  • $\begingroup$ Will not the hydroxide be better-attacking species than phenoxide due to steric factors, if so we should expect a phosgene type intermediate. $\endgroup$ Commented Jul 12, 2021 at 9:36
  • $\begingroup$ That never occurred to me... I'm sorry, I'm not knowledgeable enough to provide a satisfying explanation. $\endgroup$
    – TRC
    Commented Jul 12, 2021 at 9:50
  • $\begingroup$ Are you asking about abnormal RT reaction? chemistry.stackexchange.com/questions/152344/… $\endgroup$ Commented Jul 12, 2021 at 10:57
  • $\begingroup$ @NilayGhosh the A V Gaonkar paper just point to the original German paper. I doubt that mechanisms in CCl4 and CHCL3 are different. How will CCl4 form the carbene ? $\endgroup$ Commented Jul 12, 2021 at 11:21


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