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Faezeh Makari
Mostafa Gholizadehcorresponding author
Seyed Reza Nokhbeh


Thermal properties and spectroscopic characterization of new synthesized 1,3-propanediylbis (triphenylphosphonium) peroxydisulfate as a member of phosphonium persulfates were studied. 1H, 13C, 31P NMR and FT-IR were used to structural characterization of the title salt. To study the thermal behavior of the salt DSC, TG and DTA methods were used. Specific heat capacity of the salt was determined by DSC method in comparison of sapphire disk. Theoretical DFT computations such as structural optimization, energy, charge distribution, HOMO-LUMO energy levels and thermochemical parameters were performed with the Gaussian 09 package software using B3LYP/6-31+G* level of theory. Oxidation of several benzylic alcohols was performed by the persulfate salt in water as a mild oxidative agent.

thermal properties, phosphonium peroxydisulfate, specific heat capacity, oxidizing agent, Density Function Theory computations

Article Details

Supporting Agencies
Ferdowsi University of Mashhad
How to Cite
Makari, F., Gholizadeh, M., & Nokhbeh, S. (2020). Synthesis, thermal properties, spectroscopic characterization and DFT computations of 1,3-propanediylbis (triphenylphosphonium) peroxydisulfate as a new oxidative agent. Chemical Reports, 2(1), 144-155.


  1. Ghandi K. Green and sustainable chemistry. Green and Sustainable Chemistry, 2014, 4(1): 44-53.
  2. Chiappe C. Ionic Liquids in Synthesis, 2008, 265-568.
  3. M. A. B. Zahoor Ullah, Zakaria Man and Amir Sada Khan ARPN Journal of Engineering and Applied Sciences,3,11,1653-1659,( 2016 )
  4. Castillo J, Coll MT, Fortuny A, et al. Cu(II) extraction using quaternary ammonium and quaternary phosphonium based ionic liquid. Hydrometallurgy, 2014, 141: 89-96.
  5. Ma K, Li S and Weiss RG. Stereoselective Bromination Reactions Using Tridecylmethylphosphonium Tribromide in a “Stacked” Reactor. Organic letters, 2008, 10(19): 4155- 4158.
  6. Esch GJ. Flame retardants: tris (2-butoxyethyl) phosphate, tris (2-ethylhexyl) phosphate, tetrakis (hydroxymethyl) phosphonium salts. World Health Organization and International Programme on Chemical Safety. 2000.
  7. Rzelewska M, Janiszewska M, Regel-Rosocka M, et al. Trihexyl(tetradecyl)phosphonium bromide as extractant for Rh(III), Ru(III) and Pt(IV) from chloride solutions. Chemical Papers, 2016, 70(4): 515-520.
  8. Ovcharov VI, Okhtina OV and Golovko DA. Phosphonium Salts as Inorganic Filler Modifiers. International Polymer Science and Technology, 2002, 29(10): 17-20.
  9. Bachowska B, Kazmierczak-Baranska J, Cieslak M, et al. High Cytotoxic Activity of Phosphonium Salts and Their Complementary Selectivity towards HeLa and K562 Cancer Cells: Identification of Trinbutylnhexadecylphosphonium bromide as a Highly Potent AntiHeLa Phosphonium Salt. ChemistryOpen, 2012, 1(1): 33-38.
  10. Xue Y, Pan Y, Xiao H, et al. Novel quaternary phosphoniumtype cationic polyacrylamide and elucidation of dualfunctional antibacterial/antiviral activity. RSC Advances, 2014, 87(4): 46887-46895.
  11. Khasiyatullina NR, Vazykhova AM, Mironov VF, et al. Phosphonium salts with a dihydroxynaphthyl substituent: versatile synthesis and evaluation of antimicrobial activity. Mendeleev Communications, 2017, 27(2): 134-136.
  12. Kumar V and Malhotra SV. Study on the potential anticancer activity of phosphonium and ammonium-based ionic liquids. Bioorganic and Medicinal Chemistry Letters, 2009, 19(16): 4643-4646.
  13. Selva M, Perosa A and No M. Phosphonium salts and Pylides. Organophosphorus Chemistry, 2016, 45: 132-169.
  14. Dey RR and Dhar SS. Synthesis and Characterization of 2-Carboxyethyltriphenyl Phosphonium Tribromide and Its Application as Catalyst in Silylation of Alcohols and Thiols Under Solvent-Free Condition. Synthetic Communications, 2014, 44(16): 2355-2363.
  15. Liu SY, Kumatabara Y and Shirakawa S. Chiral quaternary phosphonium salts as phase-transfer catalysts for environmentally benign asymmetric transformations. Green Chemistry, 2016, 18(2): 331-341.
  16. Werner T. Phosphonium Salt Organocatalysis. Advanced synthesis and catalysis, 2009, 351(10): 1469-1481.
  17. Starks CM. Phase-transfer catalysis. I. Heterogeneous reactions involving anion transfer by quaternary ammonium and phosphonium salts. Journal of the American Chemical Society, 1971, 93(1): 195-199.
  18. Macarie L, Simulescu V and Ilia G. PhosphoniumBased Ionic Liquids Used as Reagents or Catalysts. ChemistrySelect, 2019, 4(32): 9285-9299.
  19. Chaudhuri MK, Khan AT, Patel BK, et al. An environmentally benign synthesis of organic ammonium tribromides (OATB) and bromination of selected organic substrates by tetrabutylammonium tribromide (TBATB). Tetrahedron letters, 1998, 39(44): 8163-8166.
  20. Cristiano R, Ma K, Pottanat G, et al. Tetraalkylphosphonium Trihalides. Room Temperature Ionic Liquids As Halogenation Reagents. The Journal of Organic Chemistry, 2009, 74(23): 9027-9033.
  21. Badri R and Mostoufi A. The Synthesis and Application of 3,6-Bis(triphenylphosphonium) Cyclohexene Dichromate: An Efficient Oxidizing Agent. Phosphorus, Sulfur, and Silicon, 2006, 181(7): 1513-1519.
  22. Cristau HJ, Torreilles E, Morand P, et al. Bichromates de phosphonium: Reactifs d’oxydation. Tetrahedron letters, 1986, 27(16): 1775-1776.
  23. Gholizadeh M, Ebrahimpour M, Hojati S, et al. Oxidation of benzylic and some aliphatic alcohols 1,2-ethylenebis (triphenylphosphonium) chlorochromate (EBTPPCC): As a new, an efficient and mild oxidant. Arabian Journal of Chemistry,2014, 7(3): 267-271.
  24. Tajbakhsh M, Lakouraj MM, Yadollahzadeh K, et al. Conversion of sulfides to sulfoxides and thiols to disulfides with o-xylylenebis (triphenylphosphonium tribromide). Journal of Chemical Research, 2005, 2005(12): 796-799.
  25. Firouzabadi H and Adibi M. Methyltriphenylphosphonium tetrahydroborate (meph3pbh4). A stable, selective and versatile reducing agent. Phosphorus, Sulfur, and Silicon and the Related Elements, 1998, 142(1): 125-147.
  26. Mariani A, Nuvoli D, Alzari V, et al. Phosphonium-Based Ionic Liquids as a New Class of Radical Initiators and Their Use in Gas-Free Frontal Polymerization. Macromolecules, 2008, 41(14): 5191-5196.
  27. Dauben WG, Lorber ME and Fullerton DS. Allylic oxidation of olefins with chromium trioxide pyridine complex. The Journal of Organic Chemistry, 1969, 34(11): 3587- 3592.
  28. Lou JD and Xu ZN. Selective oxidation of primary alcohols with chromium trioxide under solvent free conditions. Tetrahedron Letters, 2002, 43(35): 6095-6097.
  29. Trahanovsky WS and Young LB. Controlled Oxidation of Organic Compounds with Cerium(IV). II. The Oxidation of Toluenes. The Journal of Organic Chemistry, 1966, 31(6): 2033-2035.
  30. Noureldin NA, Zhao D and Lee DG. Heterogeneous Permanganate Oxidations. 7. The Oxidation of Aliphatic Side Chains. The Journal of Organic Chemistry, 1997, 62(25): 8767-8772.
  31. Waitkins GR and ClarkCW. Selenium Dioxide: Preparation, Properties, and Use as Oxidizing Agent. Chemical Reviews, 1945, 36(3): 235-289.
  32. Anderson JM and Kochi JK. Silver(I)-catalyzed oxidative decarboxylation of acids by peroxydisulfate. Role of silver( II). Journal of the American Chemical Society, 1970, 92(6): 1651-1659.
  33. Walling C, Camaioni DM and Kim SS. Aromatic hydroxylation by peroxydisulfate. Journal of the American Chemical Society, 1978, 100(15): 4814-4818.
  34. Walling C and Camaioni DM. Role of silver(II) in silvercatalyzed oxidations by peroxydisulfate. The Journal of Organic Chemistry, 1978, 43(17): 3266-3271.
  35. Mohammadpoor-Baltork I, Hajipour AR and Haddadi R. n-Butyltriphenylphosphonium Peroxodisulfate (BunPPh3)2S2O8: an Efficient and Inexpensive Reagent for the Cleavage of CarbonNitrogen Double Bonds under Non-aqueous and Aprotic Conditions. Journal of Chemical Research, 1999, 23(2): 102-103.
  36. Perumal PT. Oxidation of Alkenes by Peroxydisulphatecopper Sulphate. Synthetic Communications, 1990, 20(9): 1353-1356.
  37. Badri R, Shalbaf H and Heidary MA. 3,6-Bis (triphenylphosphonium)- cyclohexene peroxodisulfate: a highly efficient oxidant for the selective oxidation of benzylic alcohols. Synthetic Communications, 2001, 31(22): 3473-3479.
  38. Shigekazu Y and Yasuyuki Y. Nickel-Catalyzed Oxidation of Allylic Alcohols with K2S2O8. Chemistry Letters, 1998, 18(8): 1361-1364.
  39. Shigekazu Y and Yasuyuki Y. Nickel-Catalyzed Dehydrogenation of Amines to Nitriles. Bulletin of the Chemical Society of Japan, 1990, 63(1): 301-303.
  40. Snook ME and Hamilton GA. Oxidation and fragmentation of some phenyl-substituted alcohols and ethers by peroxydisulfate and Fenton’s reagent. Journal of the American Chemical Society, 1974, 96(3): 860-869.
  41. Badri R and Soleymani M. 3,6-Bis(triphenylphosphonium) cyclohexene peroxodisulfate as an efficient and mild oxidizing agent for conversion of alkylbenzenes to corresponding carbonyl compounds. Synthetic communications, 2002, 32(15): 2385-2389.
  42. Badri R, Adlu M and Mohammadi MK. Synthesis and application of 1,4-bis(triphenyl phosphonium)butane peroxodisulfate for conversion of alkyl benzenes to their corresponding acylbenzenes. Arabian Journal of Chemistry, 2015, 8(1): 62-65.
  43. Yang SG, Hwang JP, Park MY, et al. Highly efficient epoxidation of electron-deficient olefins with tetrabutylammonium peroxydisulfate. Tetrahedron, 2007, 63(24): 5184- 5188.
  44. Chen F, Wan J, Guan C, Yang J, et al. Tetrabutylammonium Peroxydisulfate in Organic Synthesis; III1. An Efficient Procedure for the Selective Oxidation of Sulfides to Sulfoxides by Tetrabutylammonium Peroxydisulfate. Synthetic communications, 1996, 26(2): 253-260.
  45. Park MY, Yang SG, Jadhav V, et al. Practical and regioselective brominations of aromatic compounds using tetrabutylammonium peroxydisulfate. Tetrahedron letters, 2004, 45(25): 4887-4890.
  46. Hajipoura A, Zahmatkesha S and Ruohob A. Methyl triphenylphosphonium peroxydisulfate (MTPPP): A mild and inexpensive reagent for the cleavage of oximes, penylhydrazones and 2,4-dinitro phenylhydrazones to the corresponding carbonyl compounds under non-aqueous conditions. Journal of the Iranian Chemical Society, 2008, 5(1): S54-S58.
  47. Hajipour AR and Ruoho A. Methyltriphenylphosphonium peroxydisulfate and iodine as mild reagents for the iodination of activated aromatic compounds. Organic preparations and procedures international, 2005, 37(3): 279-283.
  48. Badri R and Soleymani M. Selective Oxidation of Benzylic Substrates to Their Corresponding Carbonyl Compounds with 3,6- Bis (Triphenylphosphonium)cyclohexene Peroxodisulfate. Synthetic communications, 2003, 33(8): 1325- 1332.
  49. Mohammadpoor-Baltork I, Hajipour AR and Mohammadi H. Benzyltriphenylphosphonium Peroxodisulfate (PhCH2PPh3)2S2O8: a Mild and Inexpensive Reagent for Efficient Oxidation of Organic Compounds under Nonaqueous and Aprotic Conditions. Bulletin of the Chemical Society of Japan, 1998, 71(7): 1649-1653.
  50. Fieser LF, Fieser M, Hershberg EB, et al. Carcinogenic Activity of the Cholanthrenes and of other 1:2Benzanthracene Derivatives. American Journal of Cancer, 1937, 29(2): 260- 268.
  51. Nokhbeh SR, Gholizadeh M, Salimi A, et al. Synthesis, crystal structure, Hirshfeld surface analysis, DFT calculations and characterization of 1,3-propanediylbis (triphenylphosphonium) monotribromide as brominating agent of double bonds and phenolic rings. Journal of Molecular Structure, 2020, 1206: 127700.
  52. Nilchi M, Ghiasi R and Mohammadi Nasab E. Pseudo- JahnTeller effect in Si4X4 (X=F, Cl, Br, I) molecules: a theoretical investigation. Molecular Physics, 2019, 117(5): 567-574.
  53. Zandiyeh Z and Ghiasi R. A Theoretical Approach towards Identification of External Electric Field Effect on ( 5-C5H5)Me2Ta( 2-C6H4). Russian Journal of Physical Chemistry A, 2019, 93(3): 482-487.
  54. Nasrolahi M, Ghiasi R and Shafiee F. Stability, Electronic, and Structural Features of the Conformers of 2-Methyl- 1,3,2-Diheterophosphinane 2-Oxide (Heteroatom = O, S, Se): DFT and NBO Investigations. Journal of Structural Chemistry, 2019, 60(5): 746-754.
  55. Hajhoseinzadeh K, Ghiasi R and Marjani A. A computational investigation on the stability and properties of the various isomers of [B7]- anion. Eurasian Chemical Communications, 2020, 2(1): 78-86.
  56. Esmaeili A, Fazaeli R and Mohammadi Nasab E. Quantum chemical study of the Jahn Teller effect on the distortions of XO2 (X = O, S, Se, Te) systems. Eurasian Chemical Communications, 2020, 2(7): 739-749.
  57. Ansari ES, Ghiasi R and Forghaniha A. Thermodynamic and kinetic studies of the retro-Diels-Alder reaction of 1,4- cyclohexadiene, 4H-pyran 4H-thiopyran, 1,4-dioxine, and 1,4-dithiine: a theoretical investigation. Structural Chemistry, 2019, 30(3): 877-885.
  58. Ghiasi R and Amini E. Substituent and solvent effects on geometric and electronic structure of C5H5Ir(PH3)3 iridabenzene: A theoretical insight. Journal of Structural Chemistry, 2015, 56(8): 1483-1494.
  59. Ghiasi R and Ahmadi R. The Study of Substituent Effect on Osmabenzene Complexes. International Journal of New Chemistry, 2014, 1(1): 30-40
  60. Ghiasi R and Mokaram EE. Natural Bond Orbital (NBO) Population Analysis of Iridabenzene (C5H5Ir)(PH3)3. Journal of Applied Chemical Research, 2012, 6(1): 7-13.
  61. Dewar MJS. Molecular orbital theory of organic chemistry, 1969: 152-190.
  62. Carey FA and Sundberg RJ. Advanced organic chemistry: part A: structure and mechanisms, 2007.
  63. Johnson BG, Gill PM and Pople JA. The performance of a family of density functional methods. The Journal of chemical physics, 1993, 98(7): 5612-5626.
  64. Hehre WJ, Ditchfield R, Radom L, et al. Molecular orbital theory of the electronic structure of organic compounds. V. Molecular theory of bond separation. Journal of the American Chemical Society, 1970, 92(16): 1765-1771.
  65. Mukhina OA, Cronk WC, Kumar NNB, et al. Intramolecular Cycloadditions of Photogenerated Azaxylylenes: An Experimental and Theoretical Study. Journal of Physical Chemistry A, 2014, 118(45): 10487-10496.
  66. Tirado-Rives J and Jorgensen JX. Performance of B3LYP Density Functional Methods for a Large Set of Organic Molecules. Journal of Chemical Theory and Computation, 2008, 4(2): 297-306.
  67. Chen ZY and Yang ZL. The B3LYP hybrid density functional study on solids. Frontiers of Physics in China, 2006, 1(3): 339-343.
  68. Jensen F. Atomic orbital basis sets. Wiley Interdisciplinary Reviews: Computational Molecular Science, 2013, 3(3): 273-295.
  69. Davidson ER and Feller D. Basis set selection for molecular calculations. Chemical Reviews,1986, 86(4): 681-696.
  70. Dunning Jr TH. Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen. The Journal of chemical physics, 19892, 90(2): 1007-1023.
  71. Wolinski K, Hinton JF and Pulay P. Efficient implementation of the gauge-independent atomic orbital method for NMR chemical shift calculations. Journal of the American Chemical Society, 1990, 112(23): 8251-8260.