Pyridine-Imidazlolium Salts: Oxidatively Cleavage of N-C Bond via Nitration

Round 1

Reviewer 1 Report

This communication by Mangalagiu and co-workers reports the oxidative cleavage of an imidazolium bromide, under nitration conditions. The adducts yields are not reported. The unexpected transformation was nicely characterized. However, control reactions are missing. Nonetheless, I recommend publication after minor revision as follows:

Add the yields of both adducts. Add references to both adducts in the material and methods sections. So, readers can compare your characterization data with known data. Since, both compounds are known compounds. Run control reactions using only HNO3, only H2SO4, and not acids, and report the outcomes, using the same time and temperature. Adding a table is optional, a sentence will be enough. What happened to the methylene? In other words, what is the third by-product?

Author Response

Ms. Ref. No.: molbank-650959

Title: Pyridine-imidazlolium salts: oxidatively cleavage of N-C bond via nitration

Iasi,  November 20, 2019

 

                        Dear Editor,

 

            Many thanks for the opportunity to publish our work to Molbank. According with the referee advices, we have carried out all the requested corrections. The answers for reviewer 1 are listed bellow, market with yellow.

 

Answers to Rw1

 

This communication by Mangalagiu and co-workers reports the oxidative cleavage of an imidazolium bromide, under nitration conditions. The adducts yields are not reported. The unexpected transformation was nicely characterized. However, control reactions are missing. Nonetheless, I recommend publication after minor revision as follows:

Add the yields of both adducts. Add references to both adducts in the material and methods sections. So, readers can compare your characterization data with known data. Since, both compounds are known compounds. Run control reactions using only HNO3, only H2SO4, and not acids, and report the outcomes, using the same time and temperature. Adding a table is optional, a sentence will be enough. What happened to the methylene? In other words, what is the third by-product?

 

Answers.

Add the yields of both adducts.

We added the yields, page 2, on lines 71 and 75.

 

Add references to both adducts in the material and methods sections.

We did it page 2 (on lines 53-57) and on page 4, on lines 140-144, as follow:

Page 2:

2,6-Bis((1H-imidazol-1-yl)methyl)pyridine 2, was initially synthetised by Garrison and Co [22], and on the supporting information of the paper could be founded all the data concerning compound, for comparison.

4-Nitrobenzoic acid 3, is a commercially available compound and relevant data could be founded for instance to Sigma-Aldrich catalog [23].

Page 4:

Garrison, J.C.; Simons, R.S.; Talley, J.M.; Wesdemiotis, C.; Tessier, C.A.; Youngs, W.J. Synthesis and Structural Characterization of an Imidazolium-Linked Cyclophane and the Silver Complex of an N-Heterocyclic Carbene-Linked Cyclophane. Organometallics 2001, 20, 1276-1278.

23.https://www.sigmaaldrich.com/catalog/product/sial/72910?lang=en&region=RO&gclid=EAIaIQobChMI2Lbo_oP55QIVE-R3Ch1CQwsMEAAYASAAEgIiTfD_BwE

 

What happened to the methylene? In other words, what is the third by-product?

We presume that in the oxidation process the metylene is transformed to CO2 or maybe CH3-NO2, but we did not have proves in this respect and, this is why we prefer to say nothing about this.

 

Run control reactions using only HNO3, only H2SO4, and not acids, and report the outcomes, using the same time and temperature. Adding a table is optional, a sentence will be enough.

The purpose of this thematically issue is about side products and reactions. And this is what we presented. The suggestion of reviewer is very interesting but we belive that will not bring significant value for this paper, having in view this thematically issue. Anyhow, we wish to thank to reviewer  for suggestion, and we will take it into consideration in a future work.

 

Yours,

Lecture dr. Violeta Mangalagiu

Author Response File: Author Response.docx

Reviewer 2 Report

Pyridine‐imidazlolium salts: oxidatively cleavage of 2 N‐C bond via nitration
Dumitrela Cucu (Diaconu)and Violeta Mangalagiu

This manuscript focuses on the synthesis of the 2,6‐bis((1H‐imidazol‐1‐yl) methyl)pyridine by nitration of 1,1ʹ‐(pyridine‐2,6‐diylbis(methylene))bis(3‐(2‐(4‐ nitrophenyl)‐2‐oxoethyl)‐1H‐ imidazol ‐3‐ium) bromide with an unexpec-ted oxidative cleavage N-C bond between imidazolium ring and methylene group.

The structures of compounds were proven by spectroscopic analysis: 1H‐NMR, 13C‐NMR, and two‐dimensional experiments 2D‐ COSY, 37 2D‐HMQC, 2D‐HMBC.

Author Response

The reviewer 2 was for the publication, with no requests.