2-[Difluoro(phenylselenyl)methyl]benzo-1,3-thiazole

Round 1

Reviewer 1 Report

line 55: synthesis 

 

The article is well written and includes all required analytical and experimental data. The justification of research is well described in the introduction section.  The procedures are clear and should be easily reproducible by the other researchers. Therefore, I recommend the publication of the article without any changes.

Author Response

Response to Reviewer 1 Comments

 

Point : line 55: synthesis

 

Response : lines 55 & 64 have been correct "syhthesis" to "Synthesis"

Reviewer 2 Report

In the present manuscript, the authors describe a new method for the synthesis of 2-[difluoro(phenylselenyl)methyl]benzo-1,3-thiazole (2) from 2-aminobenzenethiol. The method features a highly concise two-step protocol using the condensation reaction of 2-aminobenzenethiol, a commercially available raw material, with bromodifluoroacetic acid (5 equiv) followed by the copper-mediated phenylselenylation of the resultant 2-bromodifluoromethyl benzo-1,3-thiazole (1). While the metal-mediated substitution of 2-bromodifluoromethyl benzo-1,3-oxazole and thiazole with various reactants is known for accessing diflurorinated derivatives and only limited example is shown in the present study, the copper-mediated phenylselenylation process is unique. The spectroscopic and analytical data of the compounds are adequate, supporting their assigned chemical structures. The text is concisely written and the artworks are appropriate.

In my opinion, the present manuscript may be acceptable for publication after the following corrections/modifications have been made.

1) The title; ‘difluoro(phenylselanyl)methyl’ should be corrected to ‘difluoro(phenylselenyl)methyl’.

2) Page 2, line 57; 375 mg should read 37.5 mg.

3) Page 2, line 60; the quantity of compound 1 should be indicated.

4) The whole text should be carefully edited by professional proofreading services.

Author Response

Response to Reviewer 2 Comments

 

Point 1: The title; ‘difluoro(phenylselanyl)methyl’ should be corrected to ‘difluoro(phenylselenyl)methyl’.

 

Response 1: The title and abstract: ‘difluoro(phenylselanyl)methyl’ has been corrected to ‘difluoro(phenylselenyl)methyl’

 

Point 2: Page 2, line 57; 375 mg should read 37.5 mg

 

Response 2: Page 2, line 57; 375 mg has been corrected to 37.5 mg

 

Point 3: Page 2, line 60; the quantity of compound 1 should be indicated

 

Response 3: Page 2, line 60; the quantity of compound 1 have been indicated in the revised manuscript

 

Point 4: The whole text should be carefully edited by professional proofreading services

 

Response 4: The grammar of the whole manuscript has been improved and presented in the revised manuscript

Reviewer 3 Report

2-[Difluoro(phenylselanyl)methyl]benzo-1,3-thiazole:

This manuscript focuses on the synthesis of  2-[difluoro(phenylselanyl)methyl]benzo-1,3-thiazole.The compound 2 was  synthesized from 2-aminobenzenethiol in two steps.

The purity, composition and structure of the compounds were determined using a variety of techniques, NMR, FTIR spectroscopy and ESI-MS. The preparations and characterisations (H-, F- and C-NMR) are described.  This is acceptable for organic compounds.

The Chapter Results and Discussion is of good scientific quality and the rich and instructive graphic realizes the understanding of the obtained results and of their significance. The experimental data is described appropriately and the manuscript needs no language and grammar corrections. The manuscript is written straight forward.

The study is a meaningful suppliment  to the series of publications regarding the heterocyclic comp-ounds (with P, S, N atoms) related to natural products: synthesis, structural analysis and investigation of their biological activity, that  have been extensively studied because their important properties and applications, especially in biological activities, such as, anti-microbial, anti-proliferative (prostate cancer cells),  anti-cancer , anti-influenza  and with antioxidant activity. In Introduction the autors did not reflect any other field of another heterocyclic with the important applications as chiral ligands for metal catalyst or receptors especially in biological activities.

I believe that you should describe in the introduction more generally to the use of  heterocyclic derivatives with biological activity. Therefore, you should cite more special topics. It is of interest for synthetic chemists.

The authors well have also to present in the introduction part the data about the other heterocyclic derivatives, heterocyclic phosphorous compounds with antioxidant and cytostatic activity . Examples of relevant publications are given below. It is recommended to the authors to cite these papers in their introduction a wider base.              

The medicinal chemistry of gold complexes as anticancer drugs, Ott, I. On,  Coord. Chem. Rev. 2009, 253, 1670–1681;

1.3-Dimethyl-l,3-diaza-2-R-5,6-benzo-2 λ³-phosphorinan-4-ones (R = F, Me₂N, 2-Methylpiperidino, MeC(:O)NH-) as Ligands in Transition-Metal Complexes; Synthesis and Structure of Dichloro-Platinum(II)- and Tetracarbonyl-Metal(0) Coordination Compounds (Metal = Cr, Mo and W), Plinta H.-J., Neda I.,Schmutzler R., Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, 1994, 49,100; 

Organometallic anticancer compounds, Gasser G., Ott, I.; Metzler-Nolte, N. J. Med. Chem. 2011, 54, 3–25;

N-Heterocyclic carbenes derived from imidazo-[1,5-a]pyridines related to natural products: synthesis, structure and potential biological activity of some corresponding gold(I) and silver(I) complexes,  Mihorianu, M.; Franz, M.H.; Jones, P.G.; Freytag, M.; Kelter, G.; Fiebig, H.H.; Tamm, M.; Neda, I., Appl. Organomet. Chem. 2016, 30, 581–589;

Synthesis, structure, and reactivity of tetrakis(o,o-phosphorus)-bridged calix[4]resorcinols and their derivatives, Vollbrecht A., Neda I.,Thonnessen H._, Jones P.G., Harris R.K., Crowe L.A., Schmutzler R._, Chemische Berichte, 1997, 130, 1715 – 1720.

Some references should be inserted.

In conclusion of my review,

I recommend this manuscript for publication with minor revisions!

Author Response

Response to Reviewer 3 Comments

 

Point 1: The authors well have also to present in the introduction part the data about the other heterocyclic derivatives, heterocyclic phosphorous compounds with antioxidant and cytostatic activity . Examples of relevant publications are given below. It is recommended to the authors to cite these papers in their introduction a wider base.              

The medicinal chemistry of gold complexes as anticancer drugs, Ott, I. On,  Coord. Chem. Rev. 2009, 253, 1670–1681;

1.3-Dimethyl-l,3-diaza-2-R-5,6-benzo-2 λ³-phosphorinan-4-ones (R = F, Me₂N, 2-Methylpiperidino, MeC(:O)NH-) as Ligands in Transition-Metal Complexes; Synthesis and Structure of Dichloro-Platinum(II)- and Tetracarbonyl-Metal(0) Coordination Compounds (Metal = Cr, Mo and W), Plinta H.-J., Neda I.,Schmutzler R., Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, 1994, 49,100; 

Organometallic anticancer compounds, Gasser G., Ott, I.; Metzler-Nolte, N. J. Med. Chem. 2011, 54, 3–25;

N-Heterocyclic carbenes derived from imidazo-[1,5-a]pyridines related to natural products: synthesis, structure and potential biological activity of some corresponding gold(I) and silver(I) complexes,  Mihorianu, M.; Franz, M.H.; Jones, P.G.; Freytag, M.; Kelter, G.; Fiebig, H.H.; Tamm, M.; Neda, I., Appl. Organomet. Chem. 2016, 30, 581–589;

Synthesis, structure, and reactivity of tetrakis(o,o-phosphorus)-bridged calix[4]resorcinols and their derivatives, Vollbrecht A., Neda I.,Thonnessen H._, Jones P.G., Harris R.K., Crowe L.A., Schmutzler R._, Chemische Berichte, 1997, 130, 1715 – 1720

 

Response : We has added the  introduction of important properties and applications of heterocyclic compounds (with P, S, N atoms) related to natural products in revised manuscript, and cited these relevant papers in references 4.

Reviewer 4 Report

The following minor corrections should be made:

·         line 29 – compound name to "2-(Bromodifluoromethyl)benzo-1,3-thiazole" (parentheses, no space, capital letter in place of the first letter of the sentence, even if preceded by numbers and punctuation marks)

·         lines 32, 33-34, and 55 –compound name to "2-(bromodifluoromethyl)benzo-1,3-thiazole" (parentheses, no space)

·         line 57 – "0.3 mmol" to "3.0 mmol" 

·         line 86 – "pape" to "paper"

·         line 95 – "GABAA" to "GABA_A"

·         line 105 – third author from "Xu, W." to "Lu, W."

·         lines 105, 109, and 115 – prefix "gem" to italics

·         line 111 – "facile" to "Facile" (capitalized first letter)

·         Both in the chapter "Materials and Methods" and in the supplement, it would be desirable to add what method was used to the information on the measurement of IR spectra.

Furthermore, I consider it suitable to always use the abbreviations of journal names according to CAS Source Index. This means in addition the following corrections:

·         line 102 – abbreviated journal title from "Acta Chim. Sinica" to "Huaxue Xuebao"

·         line 104 – extension of the abbreviated journal title to "ARKIVOC (Gainesville, FL, U.S.)"

·         line 107 – extension of the abbreviated journal title to "Chem. Commun. (Cambridge, U. K.)"

·         line 110 – insertion of a hyphen in the abbreviated journal name in the form "Chem. – Eur. J."

Author Response

Response to Reviewer 4 Comments

 

Point :

 line 29 – compound name to "2-(Bromodifluoromethyl)benzo-1,3-thiazole" (parentheses, no space, capital letter in place of the first letter of the sentence, even if preceded by numbers and punctuation marks)

• lines 32, 33-34, and 55 –compound name to "2-(bromodifluoromethyl)benzo-1,3-thiazole" (parentheses, no space)
• line 57 – "0.3 mmol" to "3.0 mmol" 
• line 86 – "pape" to "paper"
• line 95 – "GABAA" to "GABA_A"
• line 105 – third author from "Xu, W." to "Lu, W."
• lines 105, 109, and 115 – prefix "gem" to italics
• line 111 – "facile" to "Facile" (capitalized first letter)
• Both in the chapter "Materials and Methods" and in the supplement, it would be desirable to add what method was used to the information on the measurement of IR spectra.

Furthermore, I consider it suitable to always use the abbreviations of journal names according to CAS Source Index. This means in addition the following corrections:

• line 102 – abbreviated journal title from "Acta Chim. Sinica" to "Huaxue Xuebao"
• line 104 – extension of the abbreviated journal title to "ARKIVOC (Gainesville, FL, U.S.)"
• line 107 – extension of the abbreviated journal title to "Chem. Commun. (Cambridge, U. K.)"
• line 110 – insertion of a hyphen in the abbreviated journal name in the form "Chem. – Eur. J."

Response : All modification suggestions have been adopted and presented in the revised manuscript.  the line 57  was "0.3 mmol" , not "3.0 mmol"