Density functional theory-based molecular modeling was used to study the mechanism of 2,5-dichloro phenoxide carboxylation with CO2 for the synthesis of 3,6-dichloro salicylic acid by Kolbe–Schmitt reaction, and the in situ Fourier transform infrared (FTIR) spectroscopy technology under reaction conditions was employed to confirm the validity of the calculated mechanism. The reaction route was optimized using B3LYP/6-311+G (d, p), showing a path including an electrophilic attack by CO2, and then followed by a proton transfer. The chlorine atoms substituted on the benzene ring as electron-attracting groups cause higher activation energy barriers for electrophilic attack than in the case of the corresponding unsubstituted phenol. The comparison between calculated vibrational spectra and experimental spectra showed good agreement. The results revealed the forming path of carboxyl, by showing a carboxyl stretching vibration absorption band at 1,739 cm−1, which then splits into two bands at 1,584 and 1,472 cm−1 assigned to the carbonate as the final product, giving hypostatic evidence for the reliability of the calculated 3-intermediates and 3-transition states mechanism for the Kolbe–Schmitt reaction.
Research on Chemical Intermediates – Springer Journals
Published: Mar 19, 2013
It’s your single place to instantly
discover and read the research
that matters to you.
Enjoy affordable access to
over 18 million articles from more than
15,000 peer-reviewed journals.
All for just $49/month
Query the DeepDyve database, plus search all of PubMed and Google Scholar seamlessly
Save any article or search result from DeepDyve, PubMed, and Google Scholar... all in one place.
Get unlimited, online access to over 18 million full-text articles from more than 15,000 scientific journals.
Read from thousands of the leading scholarly journals from SpringerNature, Elsevier, Wiley-Blackwell, Oxford University Press and more.
All the latest content is available, no embargo periods.
“Hi guys, I cannot tell you how much I love this resource. Incredible. I really believe you've hit the nail on the head with this site in regards to solving the research-purchase issue.”Daniel C.
“Whoa! It’s like Spotify but for academic articles.”@Phil_Robichaud
“I must say, @deepdyve is a fabulous solution to the independent researcher's problem of #access to #information.”@deepthiw
“My last article couldn't be possible without the platform @deepdyve that makes journal papers cheaper.”@JoseServera