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Solvent-assisted monomeric molecular structure of the phosphate diester and the synthesis of menthol-based phosphate diesters

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Abstract

Phosphate diesters are well known to form intermolecular H-bonded dimeric structures in their solid-state. Recently, we reported 2,6-(CHPh)2-4-iPr-phenyl substituted phosphate diester exists as H-bonded monomeric molecular structure along with water dimer in the solid-state. Herein we report 2,6-(CHPh)2-4-iPr-phenyl substituted phosphate diester forms a monomeric molecular structure in the solid-state upon co-crystallization with dimethylformamide, DMF (Me2NCHO). The -CHO group of DMF simultaneously acts as an H-bond acceptor to P-OH and an H-bond donor to P=O moieties. We also used the alcohols, ROH (R = Me, Et, iPr, and tBu), for crystallisation of 2,6-(CHPh)2-4-iPr-phenyl substituted phosphate diester. In these instances, solvent-incorporated dimeric structures are found in the solid-state. We also report the syntheses and molecular structures of anionic phosphate diesters of 2,6-(CHPh)2-4-iPr-phenyl substituted phosphate diester possessing various counter cations. Moreover, we also report the syntheses and molecular structures of phosphate diesters based on (−)-menthol, (+)-menthol and (+)/(−)-menthol. These exist as H-bonded dimers in the solid-state.

Graphic abstract

Herein we report 2,6-(CHPh)2-4-iPr-phenyl substituted phosphate diester forms a monomeric molecular structure in the solid-state upon co-crystallization with dimethylformamide, DMF (Me2NCHO). The -CHO group of DMF simultaneously acts as an H-bond acceptor to P-OH and an H-bond donor to P=O moieties.

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Acknowledgements

This work is supported by the TIFR Centre for Interdisciplinary Science Hyderabad, Hyderabad, India. V. G. acknowledges financial support from the Science and Engineering Research Board (SERB-NPDF) (Project No. PDF/2017/001902), Government of India. VC is thankful to the Department of Science and Technology, New Delhi, India, for National J. C. Bose fellowships.

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Authors and Affiliations

  1. Tata Institute of Fundamental Research Hyderabad, Gopanpally, Hyderabad, 500 107, Telangana, India

    Debdeep Mandal, Vivek Gupta, Biswajit Santra, Avijit Maiti, Abhisek Kar,  Suman, Anku Guha, Pallavi Thakur, Ramakirushnan Suriya Narayanan, Vadapalli Chandrasekhar & Anukul Jana

  2. Institut für Biochemie, Universität Greifswald, Felix-Hausdorff-Straße 4, 17487, Greifswald, Germany

    Nicolas Chrysochos & Carola Schulzke

  3. Department of Chemistry, Indian Institute of Science Education and Research (IISER)-Bhopal, Bhopal, 462 066, Madhya Pradesh, India

    Vivek W Bhoyare & Nitin T Patil

  4. Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208 016, Uttar Pradesh, India

    Vadapalli Chandrasekhar

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  1. Debdeep Mandal
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Mandal, D., Gupta, V., Santra, B. et al. Solvent-assisted monomeric molecular structure of the phosphate diester and the synthesis of menthol-based phosphate diesters. J Chem Sci 131, 121 (2019). https://doi.org/10.1007/s12039-019-1712-8

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