Hemiacetal Ester Exchanges, Study of Reaction Conditions and Mechanistic Pathway
and Claire Negrell 1,*Round 1
Reviewer 1 Report
The manuscript submitted by Boucher et al. details on the analysis of reaction conditions and mechanistic pathway focused on hemiacetal ester exchanges. The manuscript is not suitable for the publication in Reaction in the present way for several raisons. The manuscript is not well written. Moreover, data, results and conclusion are not well defined and supported by a discussion. Bibliography is very poor and outdated.
-English language is incorrect, just as an example the sentences in paragraph 2.7 reported: In an…..was added 200 mg of….instead of were added.. In the same paragraph, the last sentence makes no sense in the present way.
-The aims of the work are illustrated in only two rows at the end of the introduction paragraph
-The experiments and data analysis are not well detailed.
Author Response
The manuscript submitted by Boucher et al. details on the analysis of reaction conditions and mechanistic pathway focused on hemiacetal ester exchanges. The manuscript is not suitable for the publication in Reaction in the present way for several raisons. The manuscript is not well written. Moreover, data, results and conclusion are not well defined and supported by a discussion. Bibliography is very poor and outdated.
Answer: The bibliography has been updated and the article was modified to strengthen the weaker parts mentionned by this reviewer.
-English language is incorrect, just as an example the sentences in paragraph 2.7 reported: In an…..was added 200 mg of….instead of were added.. In the same paragraph, the last sentence makes no sense in the present way.
Answer: We have proofread the manuscript again, and corrected a few mistakes. We have also of course corrected the error mentionned by the reviewer. The last sentence of paragraph 2.7 was also modified.
-The aims of the work are illustrated in only two rows at the end of the introduction paragraph.
Answer: Indeed, the aim of the article is illustrated in the last 2 lines of the introduction. We respectfully do not see what the problem is with this. The objectives are clearly stated and do not need to be further explained. However, an outline of the article was added at the end of the introduction.
-The experiments and data analysis are not well detailed.
Answer: The experimental section has been modified., more details on the compound characterisation have been provided.
Reviewer 2 Report
See attachment
Comments for author File: 
Comments.pdf
Author Response
The work presented to me for review ”Hemiacetal ester exchanges, study of reaction conditions and mechanistic pathway” is quite interesting and well written. The publication deals with a very interesting topic of the synthesis of hemiacetal esters. The authors carefully planned the synthesis and investigation of obtained compounds.
They discussed the obtained results in detail referring to previously published investigation of hemiacetal esters. They undertook to explain the mechanism of exchange in the studied compounds.
I would accept the paper in the present form, after correcting editing errors, such as figure numbers or determination of symbols, such as pKa (pKa or pKa).
Answer: The figure numbers have been corrected as well as the way pKa was written throughout the manuscript.
Moreover, I think that in the expression: In addition, the detergent-like behavior of the catalyst may also help the solubilization of the diacids, more suitable term will be surfactant-like behavior than detergent-like behavior.
Answer: The word detergent has been replaced by the word surfactant.
Reviewer 3 Report
The ms of Negrell et al is sound. However, the following problems should be treated before further consideration.
– This Referee does not like the phrase “hemiacetal ester”. This is rather an acylated hemiacetal”. The same should be applied to the bis derivative.
– “mono-dodecyl phosphate” is again not a good name. It is rather the monododecyl ester of phosphoric acid.
– It is surprising that the compound characterization is completely missing. This is a serious shortage.
– In subchapter 3.2, the acid strength of the carboxylic acids should be somehow given (characterized).
– Authors should include the importance of the ester exchange reactions.
In summary, the ms can be accepted after a major revision.
Author Response
The ms of Negrell et al is sound. However, the following problems should be treated before further consideration.
– This Referee does not like the phrase “hemiacetal ester”. This is rather an acylated hemiacetal”. The same should be applied to the bis derivative.
Answer: We understand the opinion of this reviewer. However, these acylated hemiacetals are commonly named hemiacetal ester in the vast majority of articles published so far. We thus decided to keep this accepted nomenclature. Nevertheless we mentioned the other name in the introduction an conclusion of the article.
– “mono-dodecyl phosphate” is again not a good name. It is rather the monododecyl ester of phosphoric acid.
Answer: Mono-n-dodecyl phosphate may not be the IUPAC name, but it is the name of the compound that one can purchase from a reseller. We therefore decided to keep mention of this nomenclature in the Materials section. In the rest of the manuscript the catalyst is now designated as n-dodecyl dihydrogen phosphate (the IUPAC recommended name).
– It is surprising that the compound characterization is completely missing. This is a serious shortage.
Answer: NMR characterization and chemical shift of each compound synthesized were provided in supporting information. These data are now also in the experimental part of the main manuscript.
– In subchapter 3.2, the acid strength of the carboxylic acids should be somehow given (characterized).
Answer: The pKa of the acids are now given in Table 1. However, since the strength of the acid is not the determining factor in the exchange mechanism, it would be misleading to put emphasis on these values.
– Authors should include the importance of the ester exchange reactions.
Answer: We do not fully understand this comment, as there are no ester exchange reaction. Nevertheless, we added a sentence referring to the reactivity of the hemiacetal esters with water and alcohols in the conclusion. We also expanded the conclusion to explain how this novel exchnage reaction may have impact in materials science.
Round 2
Reviewer 1 Report
The manuscript is now suitable for publication in the journal.
Reviewer 3 Report
Although, au-s were not fully understanding, the ms can be accepted for Reactions.
