One-electron oxidation of 2-alkyl-1,4-dimethoxybenzenes 1a-f (2-alkyl=Me, Et, i-Pr, cy-C3H5CH2, PhCH2 and t-Bu) by 4-nitrobenzoyl peroxide 2 and pentaflurobenzoyl peroxide 3 was proved by the observation of great acceleration of decomposition of the peroxides at room temperature, the detection of the corresponding radical cations 1 +• a-f and product analysis. The product studies have disclosed that under the conditions employed (in acetonitrile at 40°C), the reaction pathways of the radical cations are greatly dependent on the nature of 2-alkyl substituents: Ring-4-nitrobenzoloxylation product at C 5 and C 6 were obtained exclusively in the reactions of the donors with aliphatic 2-alkyl substituents bearing at least one α-hydrogen atom, such as 1a, 1b, 1c and 1d; whereas in the case of 1e (with 2-benzyl group), both ring-substitution at C 5 (4e) and C 6 (5e) and deprotonation/4-nitrobenzoloxylation products 8e were isolated; from the donor without α-hydrogen atom, 1f, de-t-butylation products 12 and t-butyl 4-nitrobenzoate 13 were incorporated with ring-substitution at C 5 (4f) and C 6 (5f). Furthermore, the product distribution (4 over 5) is also affected by the bulkiness of 2-alkyl group. For all the electron-transfer reactions, large amounts of the benzoic acid (4-NO2-C6H4COOH or C6F5COOH) were generated and trace amounts of de-methylation product (2-alkyl-1,4-benzoqinones 6) were also detected by 1H NMR.
Research on Chemical Intermediates – Springer Journals
Published: Jul 7, 2009
It’s your single place to instantly
discover and read the research
that matters to you.
Enjoy affordable access to
over 12 million articles from more than
10,000 peer-reviewed journals.
All for just $49/month
Read as many articles as you need. Full articles with original layout, charts and figures. Read online, from anywhere.
Keep up with your field with Personalized Recommendations and Follow Journals to get automatic updates.
It’s easy to organize your research with our built-in tools.
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