One-Pot Synthesis of Dioxime Oxalates

Round 1

Reviewer 1 Report

The authors report a a one-pot method for the synthesis of cyclic and acyclic dioxime oxalates, starting from ketones in good to excellent yields. The work is clearly presented and the experimental procedures are carefully detailed and the conclusions are reasonably supported by the data. The characterization of the substrates is exhaustive, including an x-Ray structure, so nothing to object with that fine work.

There are however some minor issues to be addressed:

The authors state “to our knowledge, compounds (2c), (2d), and (2e) were not reported until now”. However compound 2c is described in the literature while compound 2a is not reported so far.

Scheme 3, the C=N bonds should be corrected.

Table 2 can be moved to supporting info

It appears that carbon NMR is made with H decoupling, so the right form to give NMR is “¹³C NMR {¹H} (101 MHz, CDCl₃)”

“ν” is the right symbol for FTIR

Solvents used for crystallization should be provided in melting points.

Line 226: “¹³C NMR”, 13 is superscript

The intensity of the spectra in the ESI should be increased. Also, the quality of the image can be improved.

Overall, I think they authors provide a nice contribution to the synthesis of dioxime oxalates that will be of interest for organic chemists and, consequently I support the publication of the manuscript in MolBank after the comments above have been taken into account.

Author Response

Please see the attachment

Author Response File: Author Response.pdf

Reviewer 2 Report

This work deals with the synthesis of dioxime oxalates in One-pot. Synthesis of  dioxime oxalates is interesting, nevertheless, the experimental is a beat confusing according to my personal opinion. The authors claim that they describe one-pot method for synthesizing dioxime oxalates, starting from the corresponding ketones. Is this one pot? Or they mean from the corresponding oxime. In addition, the authors describe in line 61 that experiment was car ried out by adding dropwise 2 equiv. of oxalyl chloride but in line 180-181 they claim that To a solution of 1.5 mmol ketoxime in 5 mL of anhydrous dichloromethane is added the Et3N (1.65 mmol). Then, oxalyl chloride (1.8 mmol) was added dropwise at room temperature under stirring and a nitrogen atmosphere. Which of the two is true? Eitherway, it seems more suitable to use 2 equiv of the oxime. Can they comment on this?

In line 72 they claim that 2c is a new compound. Do they mean 2b?

In the nomenclature, since the title of the manuscript is about dioxime oxalates, in my opinion is more suitable to name the compounds as dioxime oxalates. As an example cyclohexanone dioxime oxalate etc

Finally, some minors:

11)      dioxime oxalates have long lives: please rephrase

22)      line 131 KMnO4 subscript

33)      line 131 CDCl3 subscript

4)       

5)       

Author Response

Please see the attachment

Author Response File: Author Response.pdf

Reviewer 3 Report

Dear Editor and Reviewers,

Thank you for the opportunity to review the manuscript.

The manuscript “One-pot synthesis of dioxime oxalates” is devoted to synthesis of dioxime oxalates from Ketone and hydroxylamine through ketoximes. Compared with the previously described methods, the proposed method doesn’t need low temperatures, and it is applicable for acyclic and cyclic ketoximes. As a result several dioxime oxalates were afforded in moderate to good yields. Three oxolates have never been known before. X-ray crystal data of the cyclopentanone dioxime oxalate is also reported.

The paper may be puplished after some issues are addressed:

1.    It is not clear why the method is a One-Pot approach. According to Materials and Methods, preparation of ketoximes and preparation of dioxime oxalates it is separate stages, the ketoximes are isolated with flash chromatography. It should be clarified or the term “one-pot” should be excluded from the title and text.

2.    If it remains one-pot approach, One-Pot approaches should be mentioned in introduction part.

3.    Inert nitrogen atmosphere is used for reaction. It should be noted on Scheme 3 and Table 1.

4.    The description of TLC control may be described more thoroughly. Which solvents did you use?

5.    Please, explain HRMS results of 2c. HRMS (ESI): Calculated for C15H25N2O5 (M+ CH3OH+H) 313.1758; found, 313.1758.
How CH3OH is formed in reaction condition or purification?

6.    In 13C spectra of 1a you have 8 carbons and 6 signals. Consider revision of NMR DATA and presentation of it as follows:
156.2, 136.5, 129.4 (2C), 128.7 (2C), 126.1, 12.5
instead of 156.2, 136.5, 129.4, 128.7, 126.1, 12.5.
The same for other compounds.

Author Response

Please see the attachment

Author Response File: Author Response.pdf

Round 2

Reviewer 2 Report

The authors have sufficiently replied to all of my concerns