2-(2,5-Dimethoxyphenoxy)isoindoline-1,3-dione
Round 1
Reviewer 1 Report
The manuscript numbered molbank-2046532 by S.A. Paveliev et al. describes the optimization of a simple synthesis of an uncomplicated new compound. I found similar structures in the Reaxys and SciFinder databases. I appreciate that the Authors have included a MOL file, which makes it easier to search for the compound discussed. The obtained compound is pure, as confirmed by NMR spectra, especially the proton spectrum. An elemental analysis would be useful. I don't think chemical shifts of the solvent (CDCl3) were used to calibrate the spectrum. Please check it out. The spectra end at zero ppm, so I cannot assess whether TMS was used. I suggest explaining the abbreviations used for fluorinated alcohols. Self-citations account for a quarter of all citations (13 out of 53). In the sentence (l. 31-33) "A number of processes are known in which the resulting PINO radical enters into reactions of C-H functionalization [20-30] or selective difunctionalization of multiple bonds [31-48]." too many references are given focusing on own papers.
Author Response
Point 1: An elemental analysis would be useful.
Response 1: At the suggestion of the Reviewer, the result of elemental analysis was added to the manuscript.
Point 2: I don't think chemical shifts of the solvent (CDCl3) were used to calibrate the spectrum. Please check it out. The spectra end at zero ppm, so I cannot assess whether TMS was used.
Response 2: The provided NMR specta were re-cheked to ensure calibration using solvent chemical shifts (in case of CDCl3 - 7.26 ppm for 1H NMR and 77.16 ppm for 13C NMR).
Point 3: I suggest explaining the abbreviations used for fluorinated alcohols.
Response 3: The suggested explanations were provided in the appropriate place in manuscript.
Point 4: Self-citations account for a quarter of all citations (13 out of 53). In the sentence (l. 31-33) "A number of processes are known in which the resulting PINO radical enters into reactions of C-H functionalization [20-30] or selective difunctionalization of multiple bonds [31-48]." too many references are given focusing on own papers.
Response 4: In accordance with the Reviewer's requirement, we have reduced the number of cited paper (38 in total), including self-citations (7 in total), leaving only the essential references.
Author Response File: 
Author Response.pdf
Reviewer 2 Report
Terent’ev group describes N-hydroxyphthalimide (NHPI)-catalyzed a radical type ortho-oxidation of 1,4-dimethoxybenzne to produce the corresponding title compound. Although Molbank criteria is “One-compound-per-paper short note,” the reviewer suggests derivatisation to 2-hydroxy1,4-dimethoxybenzne via N-O bond cleavage in view of a significant utility. In addition, analogous reactions using 1,2- dimethoxybenzne and 1,3- dimethoxybenzne may be encouraged, in which probably regioselective isomers will be produced.
Compared with the present short content, this manuscript contains too many references [1]-[53] including 9 self-citations. The authors should integrate really relevant reviews. Moreover, pertinent reviews such as (i) Y. Ishii, et al., Avd. Synth. Catal. 2001, 343, 393, (ii) F. Recupero, C. Punta, Chem Rev. 2007, 107, 3800, (iii) L. Melon, C. Punta, Beil. J. Org. Chem. 2013, 9, 1296 should be included.
The reviewer basically recommends the publication in Molbank after the major revision commented below: There are a number of improper descriptions and the authors should carefully revise this issue.
<Comments and suggestions>
1. Abstract; “electron-rich arenes” This manuscript provides only one arene, 1,4-dimethoxybenzne.
2. Abstract; proceeds → proceeded, conditions, a commercially → conditions, in which a commercially, is → was
3. Abstract, line 11; is → will be a prommising
4. Abstract; “potentially” should be deleted (too exaggeration)
5. P. 1, line 35; Citation(s) is required at this stage.
6. P. 2, line 45; TFE → tetrafuluoroethylene (TFE)
7. P. 2, line 47; HFIP → hexafluoroisopropyl alcohol (HFIP)
8. P. 2, line 47; according to NMR. → determined by NMR analysis.
9. P. 2, line 50; were promoting → promoted
10. Table 1; Meaning of the parenthesis of entry 5 should be addressed in the footnote.
11. Conclusions; Previous unknown → A novel was obtained → produced
12. References; page numbers are not consistent. All numbers should be ###-###.
Author Response
Point 1: Although Molbank criteria is “One-compound-per-paper short note,” the reviewer suggests derivatisation to 2-hydroxy1,4-dimethoxybenzne via N-O bond cleavage in view of a significant utility. In addition, analogous reactions using 1,2-dimethoxybenzne and 1,3-dimethoxybenzne may be encouraged, in which probably regioselective isomers will be produced.
Response 1: We thank the Reviewer for his interest in the discovered transformation and fully share the desire to expand its applicability. In this work, we aimed at the rapid publication of the obtained result, taking into account its scientific novelty. In this regard we chose the type of publication "Short Note", that implies a report of one substance, which was rightly noted by the Reviewer. We plan to expand the scope of the developed method, as well as to study the synthetic transformations of the obtained products withing the framework of a full article.
Point 2: Compared with the present short content, this manuscript contains too many references [1]-[53] including 9 self-citations. The authors should integrate really relevant reviews. Moreover, pertinent reviews such as (i) Y. Ishii, et al., Avd. Synth. Catal. 2001, 343, 393, (ii) F. Recupero, C. Punta, Chem Rev. 2007, 107, 3800, (iii) L. Melon, C. Punta, Beil. J. Org. Chem. 2013, 9, 1296 should be included.
Response 2: In accordance with the Reviewer's requirement, we reduced the number of cited paper (38 in total), including self-citations (7 in total), leaving only the essential references.
Point 3: <Comments and suggestions>
- Abstract; “electron-rich arenes” This manuscript provides only one arene, 1,4-dimethoxybenzne.
- Abstract; proceeds → proceeded, conditions, a commercially → conditions, in which a commercially, is → was
- Abstract, line 11; is → will be a prommising
- Abstract; “potentially” should be deleted (too exaggeration)
- P. 1, line 35; Citation(s) is required at this stage.
- P. 2, line 45; TFE → tetrafuluoroethylene (TFE)
- P. 2, line 47; HFIP → hexafluoroisopropyl alcohol (HFIP)
- P. 2, line 47; according to NMR. → determined by NMR analysis.
- P. 2, line 50; were promoting → promoted
- Table 1; Meaning of the parenthesis of entry 5 should be addressed in the footnote.
- Conclusions; Previous unknown → A novel was obtained → produced
- References; page numbers are not consistent. All numbers should be ###-###.
Response 3: All the suggested corrections were made.
Author Response File: Author Response.pdf
Reviewer 3 Report
In this contribution, the authors displayed novel direct aromatic C-H oxidation reaction using NHPI as the oxygen-introducing reagent.
The reaction protocol is very simple, and the obtained oxygenated aromatic compounds should be useful for various applications.
However, before the acceptance, the authors are strongly encouraged to investigate the following points.
1)
The substrate scope is quite limited...only one compound (1,4-dimethoxybenzene).
This reaction is expected to apply to other electron-rich (or neutral) aromatic compounds, such as phenol, anisole and aniline derivatives as well as poly alkylated benzenes (e.g., xylenes).
The authors should investigate the scope of this interesting and useful reaction.
2)
Reaction mechanisms should be further investigated.
In the introductory section, the authors suggested the reaction proceeds via radical intermediates (i.e., PINO), which should be confirmed experimentally. Addition of radical scavengers and use of radical clock reactions may be helpful.
Author Response
Point 1: The substrate scope is quite limited...only one compound (1,4-dimethoxybenzene).
This reaction is expected to apply to other electron-rich (or neutral) aromatic compounds, such as phenol, anisole and aniline derivatives as well as poly alkylated benzenes (e.g., xylenes).
The authors should investigate the scope of this interesting and useful reaction.
Response 1: We thank the Reviewer for his interest in the discovered transformation and fully share the desire to expand its applicability. In this work, we aimed at the rapid publication of the obtained result, taking into account its scientific novelty. In this regard we chose the type of publication "Short Note", that implies a report of one substance. We plan to expand the scope of the developed method, as well as to study the synthetic transformations of the obtained products withing the framework of a full article.
Point 2: Reaction mechanisms should be further investigated.
In the introductory section, the authors suggested the reaction proceeds via radical intermediates (i.e., PINO), which should be confirmed experimentally. Addition of radical scavengers and use of radical clock reactions may be helpful.
Response 2: In accordance with the request of the Reviewer and in order to confirm the radical nature of the discovered process, we perfomed a control experiment in optimal conditions with the addition of TEMPO (2 equiv. per mol of starting 1,4-dimethyoxybenzene) as a radical scavenger. In this case, we did not observed a formation of the target product 3, that confirms the radical nature of the process. We were unable to isolate any adducts with TEMPO.
Author Response File: Author Response.pdf
Round 2
Reviewer 2 Report
A little more decrease of the citations including self-citations will be encouraged.
Author Response
Point 1: A little more decrease of the citations including self-citations will be encouraged.
Response 1: In accordance with the Reviewer's suggestion, we additionally reduced the number of citations to 21 (including 5 self-citations).
Reviewer 3 Report
The authors have carried out additional experiments in order to elucidate the mechanism. Reaction in the presence of TEMPO did not proceed at all, clearly showing the free radical nature of this interesting reaction.
Although the reaction scope remains quite limited, this result should has a merit of publication. The reviewer strongly expects the authors expand the reaction and report in the near future.
Author Response
Point 1: The authors have carried out additional experiments in order to elucidate the mechanism. Reaction in the presence of TEMPO did not proceed at all, clearly showing the free radical nature of this interesting reaction.
Although the reaction scope remains quite limited, this result should has a merit of publication. The reviewer strongly expects the authors expand the reaction and report in the near future.
Response 1: We would like to once again thank the Reviewer for his interest in the discovered transformation. We plan to expand the scope of this reaction and to prepare a full article based on these results as soon as possible.
