SpringerLink
Log in

Characterization and Structure of Trans, Trans, Trans-1,3,5,7-Tetrakis(3ʹ,3ʹ,3ʹ-Trifluoropropyl)-1,3,5,7-Tetramethylcyclotetrasiloxane, and Structure of Trans-1,3,5-(3ʹ,3ʹ,3ʹ-Trifluoropropyl)-1,3,5-Trimethylcyclotrisiloxane

  • Research
  • Published:
Silicon Aims and scope Submit manuscript

Abstract

One of four possible stereoisomers of a methyl(trifluoropropyl)siloxane cyclic tetramer was isolated from low molecular weight volatiles, formed in a reaction mixture during ring-opening/equilibration polymerization of methyl(3,3,3-trifluoropropyl)cyclotrisiloxane (D3F). The crystalline solid was recognized as resembling a previously isolated cyclic siloxane with undetermined stereochemistry, assigned as a cyclotetrasiloxane by IR spectroscopy, and then further characterized by multinuclear (1H, 13C, 19F, and 29Si) NMR spectroscopy as a relatively high symmetry species with respect to the potential cis–trans relationships of the methyl and 3,3,3-trifluoropropyl substituents at Si. Unambiguous characterization and assignment of the stereochemistry was accomplished by a single crystal X-ray diffraction study, which revealed the compound was the trans, trans, trans-isomer, one species in these equilibration polymerization mixtures. The single crystal X-ray structure of the related, commercially important trans-D3F cyclotrisiloxane has also been determined. The structures of the two cyclic fluorinated siloxanes are discussed with respect to each other, and in the context of prototypical structures for these common Si3O3 and Si4O4 ring systems.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

Data Availability

The data generated and/or analyzed during the current study are available from the corresponding author on reasonable request, but please read the supplementary information of this article prior to any request. Crystallographic data for 1 and 2 in this article have been deposited at the Cambridge Crystallographic Data Centre, under numbers CCDC 2296541 (1) and 2296540 (2). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All other data generated and analyzed during this study, which include experimental and spectroscopic data, are included in this article and its supplementary information.

References

  1. Tarrant P, Dyckes DW, Dunmire R, Butler GB (1957) The preparation of some fluoroalkylmethyldichlorosilanes and their hydrolysis products. J Am Chem Soc 79:6536–6540

    Article  CAS  Google Scholar 

  2. Pasquet C, Longuet C, Hamdani-Devarennes S, Ameduri B, Ganachaud F (2012) Comparison of surface and bulk properties of pendant and hybrid fluorosilicones. In Silicone Surface Science, Springer, 115–178

  3. Owen MJ (2000) Surface properties and applications. In Silicone-containing polymers, the science and technology of their synthesis and applications, Springer, 213–231

  4. Boutevin B, Guida-Pietrasanta F, Ratsimihety A (2000) Side group modified polysiloxanes. In Silicon-containing polymers, the science and technology of their synthesis and applications, Springer, 79–112

  5. Breunig S, Chardon J, Guennouni N, Mignani G, Olier P, Derspuy AV, Vergelati C (2005) Poly‐functionalization of polysiloxanes — New industrial opportunities. In Organosilicon chemistry set: From molecules to materials, Wiley 645–658

  6. Pierce OR, Holbrook GW, Johannson OK, Saylor JC, Brown ED (1960) Fluorosilicone Rubber. Ind Eng Chem 52:783–784

    Article  CAS  Google Scholar 

  7. Midland Silicones Ltd. (1960) GB Patent No. 832,487

  8. Pierce OR, Holbrook GW (1961) US Patent No. 2,979,519 assigned to Dow-Corning

  9. Klebanskii AL, Yuzhelevski YA, Kogan EV, Kagan EG (1962) The isomerism of 1,3,5-tris(3,3,3-trifluoropropyl)-1,3,5-trimethylcyclotrisiloxane. Russ J Gen Chem (Engl Transl) 32:320

    Google Scholar 

  10. Burshtein LL, Yuzhelevski YA, Kogan EV, Klebanskii AL (1963) The structure of isomers of 1,3,5-tris(3,3,3-trifluoropropyl)-1,3,5-trimethylcyclotrisiloxane. Russ J Gen Chem (Engl Transl) 33:2716

    Google Scholar 

  11. Yuzhelevski YA, Kogan EV, Klebanskii AL, Larionova ON (1964) The isomerism of 3,3,3-trifluoropropylmethylcyclosiloxanes. Russ J Gen Chem (Engl Transl) 34:1794–1795

    Google Scholar 

  12. Kuo C-M, Saam JC, Taylor RB (1994) Stereoregularity of poly[methyl(3,3,3-trifluoropropylsiloxane. Polym Int 33:187–195

    Article  CAS  Google Scholar 

  13. Collins WT, Kuo C-M, Saam JC (1995) US Patent No. 5,401,822 assigned to Dow-Corning

  14. For convenience, we adopt here the “General Electric” shorthand nomenclature commonly used in the silicone industry, where “Dx” represents a difunctional -[(CH3)2SiO]x- moiety, and by analogy, “DxF” represents a -[CF3C2H4(CH3)SiO]x- repeat unit. For details see Wilcock DF (1947) Liquid methylpolysiloxane systems. J Am Chem Soc 69:477-486

  15. Battjes KP, Kuo CM, Miller RL, Saam JC (1995) Strain-induced crystallization in poly[methyl(3,3,3-trifluoropropyl)siloxane] networks. Macromolecules 28:790–792

    Article  ADS  CAS  Google Scholar 

  16. Kuo CM, Battjes KP, Miller RL, Saam JC (1997) Strain induced crystallization in stereoregular poly methyl(3,3,3-trifluoropropyl) siloxane networks. Rubber Chem Technol 70:769–780

    Article  CAS  Google Scholar 

  17. Owen MJ (2014) Poly[methyl(3,3,3-trifluoropropyl)siloxane]. Handbook of Fluoropolymer Science and Technology, 183–200. https://doi.org/10.1002/9781118850220

  18. Yang Z, Bai Y, Meng L, Wang Y, Pang A, Guo X, **ao J, Li W (2022) A review of poly[(3,3,3-trifluoropropyl)methylsiloxane]: Synthesis, properties and applications. Eur Polymer J 163:110903. https://doi.org/10.1016/j.eurpolymj.2021.110903

    Article  CAS  Google Scholar 

  19. Nakamura K, Refojo MF, Crabtree DV, Leong F-L (1990) Analysis and fractionation of silicone and fluorosilicone oils for intraocular use. Invest Ophthalmol Vis Sci 31:2059–2069

    PubMed  CAS  Google Scholar 

  20. McLachlan MS, Kierkegaard A, Radke M, Sobek A, Malmvärn A, Alsberg T, Arnot JA, Brown TN, Wania F, Breivik K, Xu S (2014) Using model-based screening to help discover unknown environmental contaminants. Environ Sci Technol 48:7264–7271

    Article  ADS  PubMed  CAS  Google Scholar 

  21. Zhi L, Xu L, Qu Y, Zhang C, Cao D, Cai Y (2018) Identification and elimination of fluorinated methylsiloxanes in environmental matrices near a manufacturing plant in eastern China. Environ Sci Technol 52:12235–12243. https://doi.org/10.1021/acs.est.8b02508

    Article  ADS  PubMed  CAS  Google Scholar 

  22. Huang Z, **ang X, Xu L, Cai Y (2020) Phenylmethylsiloxanes and trifluoropropylmethylsiloxanes in municipal sludges from wastewater treatment plants in China: Their distribution, degradation and risk assessment. Water Res 185:116224

    Article  PubMed  CAS  Google Scholar 

  23. Zhi L, Sun H, Xu L, Cai Y (2021) Distribution and elimination of trifluoropropylmethylsiloxane oligomers in both biosolid-amended soils and earthworms. Environ Sci Technol 55:985–993. https://doi.org/10.1021/acs.est.0c05443

    Article  ADS  PubMed  CAS  Google Scholar 

  24. In the context of environmental contaminants with multiple isomeric forms, the presence or absence of which (as well as their relative distributions) may be source or process dependent, it is desirable to have more definitive identification of specific stereoisomers. In this way, the ultimate source of the pollution, and perhaps even different rates/mechanisms of degradation of the isomers, may be more readily identified

  25. Fulmer GR, Miller AJM, Sherden NH, Gottlieb HE, Nudelman A, Stoltz BM, Bercaw JE, Goldberg KI (2010) NMR chemical shifts of trace impurities: Common laboratory solvents, organics, and gases in deuterated solvents relevant to the organometallic chemist. Organometallics 29:2176–2179

    Article  CAS  Google Scholar 

  26. Bruno TJ, Svoronos PDN (2011) Handbook of Basic Tables for Chemical Analysis, 3rd edn. CRC Press, New York, pp 553–555

    Google Scholar 

  27. Dolomanov OV, Bourhis LJ, Gildea RJ, Howard JAK, Puschmann H (2009) OLEX2: a complete structure solution, refinement and analysis program. J Appl Cryst 42:339–341

    Article  CAS  Google Scholar 

  28. Sheldrick GM (2015) SHELXT – Integrated space-group and crystal structure determination. Acta Cryst A71:3–8

    Google Scholar 

  29. Sheldrick GM (2015) Crystal structure refinement with SHELXL. Acta Cryst C71:3–8

    Google Scholar 

  30. Brown ED, Carmichael JB (1965) Cyclics distribution in 3,3,3-trifluoropropylmethylsiloxane polymers. J Poly Sci B Polymer Lett 3:473–482

    Article  CAS  Google Scholar 

  31. Wright N, Hunter MJ (1947) Organosilicon polymers. III. Infrared spectra of the methylpolysiloxanes. J Am Chem Soc 69:803–809

    Article  PubMed  CAS  Google Scholar 

  32. Young CW, Servais PC, Currie CC, Hunter MJ (1948) Organosilicon polymers. IV. Infrared studies on cyclic disubstituted siloxanes. J Am Chem Soc 70:3758–3764

    Article  PubMed  CAS  Google Scholar 

  33. The original literature (Ref 25) gave these distinctive band ranges as 1010–1020 cm-1 for diorgano-substituted cyclotrisiloxanes and 1081–1093 cm-1 for diorgano-substituted cyclotetrasiloxanes. Compound 1, with the corresponding strongest IR band appearing at 1030 cm-1, falls between these two reported ranges, but in fact is closer to the higher end of the wavenumber range associated with cyclotrisiloxanes. The assignment of Compound 1 as a cyclotetrasiloxane by IR spectroscopy was therefore somewhat indeterminant until further (this current) work was done. Resolution of this anomaly with the historical literature was accomplished by comparison to spectra acquired on our lab instrumentation, using genuine D3F, D3, and D4 as reference materials. See the Supplementary Material for more details

  34. Lewis RN (1948) Methylphenylpolysiloxanes. J Am Chem Soc 70:1115–1117

    Article  CAS  Google Scholar 

  35. Ahn HW, Clarson SJ (2002) Synthesis and characterization of cis and trans trimethyltriphenylcyclotrisiloxane. J Inorg Organomet Polymers 11:203–216

    Article  Google Scholar 

  36. Jiang K, Ni Y, Qiu H, Li M, Jiang J, Lai G (2006) Separation of the isomers of oligomethylphenyl-cyclosiloxanes and determination of their structures by capillary GC-MS. Chromatographia 64:689–694

    Article  CAS  Google Scholar 

  37. The GC-MS ion chromatogram is found in Figure S1 of the Supplementary Information addendum for Ref 14. GC retention times with labeled structural drawings for each assigned isomer are in Table S1 in the Supplementary Information for Ref 16

  38. Pestunovich VA, Larin MF, Voronkov MG, Engelhardt G, Jancke H, Mileshkevich VP, Yuzhelevskii YA (1977) 29Si NMR spectroscopy of cyclosiloxanes. Journal of Structural Chemistry (English translation) 18:463–470

    Article  Google Scholar 

  39. Belyakova NR, Mileshkevich VP (1990) Identification of stereoisomeric siloxanes from the signals of methyl groups in the PMR spectra. Russ J Gen Chem (Engl Transl) 60:2045–2048

    Google Scholar 

  40. Lin D, Willson TR, Haque ME, Vu AD, Dao K-LD, Tshita MM, Davis JM, Honeychuck RV (2000) Fluorinated siloxane amine oligomers. J Appl Poly Sci 78:1315–1320

    Article  CAS  Google Scholar 

  41. Kälig H, Zoellner P, Mayer-Helm BX (2009) Characterization of degradation products of poly [(3,3,3-trifluoropropyl) methylsiloxane] by nuclear magnetic resonance spectroscopy, mass spectrometry and gas chromatography. Polym Degrad Stab 94:1254–1260

    Article  Google Scholar 

  42. Zhang G-D, Hu Y-Q, Wu J-R, Li J-Y, Lai G-Q, Zhong M-Q (2016) Improved synthesis and properties of hydroxyl-terminated liquid fluorosilicone. J Appl Poly Sci 133:43220. https://doi.org/10.1002/APP.43220

    Article  Google Scholar 

  43. These spectra were also taken in the same acetone-d6 solvent as in this work, so solvent effects are unlikely to be the cause of the lack of correspondence in chemical shift

  44. It should be noted that in the 29Si NMR experimental data cited, the spectra were measured on a low-field (100 MHz 1H-resonance frequency, ≈ 2.35 Tesla field strength) instrument, which may have limited resolution of all the isomers present. The spectra were also acquired in CCl4, which might obviate direct comparison of chemical shift data with this work (in acetone-d6) due to solvent-effects

  45. In reality, symmetry inequivalent atoms in a structure may not be present in sufficiently different magnetic environments to be resolved in the NMR spectrum as observable chemical shift differences or specific spin-spin splittings dictated by that inequivalence. As an example, the 75 MHz 29Si-NMR spectrum of the commercial cis- and trans-D3F mixture, with three different Si-methyl or 3,3,3-trifluoropropyl group environments, was not resolvable into distinct resonances for the two isomeric forms, much less distinguishing the two equivalent ring sub-units from the third one in the trans-isomer. See Ref. 33

  46. You Y, Chen J, Zheng A, Wei D, Xu X, Guan Y (2020) Effect of silanol on the thermal stability of poly[methyl(trifluoropropyl)siloxane]. J Appl Poly Sci 137:e49347. https://doi.org/10.1002/app.49347

    Article  CAS  Google Scholar 

  47. Steinfink H, Post B, Fankuchen I (1955) The crystal structure of octamethyl cyclotetrasiloxane. Acta Cryst 8:420–424

    Article  CAS  Google Scholar 

  48. Couzijn EPA, Lutz M, Spek AL, Lammertsma K (2009) 2,2,6,6-Tetrakis(biphenyl-2-yl)-4,4,8,8-tetramethylcyclotetrasiloxane. Acta Cryst E65:o2182–o2183

    Google Scholar 

  49. Malinovskii ST, Vallina AT, Stoeckli-Evans H (2007) X-ray diffraction investigation of siloxanes. III. Structure and configuration of cyclic tetra- and pentasiloxanes bearing different organic substituents at silicon atoms. J Struct Chem 48:128–136. Multiple methyl-methoxyphenyl derivatized cyclic tetrasiloxanes were reported

  50. Shklover VE, Kalinin AE, Gusev AI, Bokii NG, Struchkov YuT, Andrianov KA, Petrova IM (1973) Crystalline structures of cyclic siloxanes: 1,1,2,2-Tetramethyl-3,3,4,4-tetraphenylcyclotetrasiloxane. Zh Strukt Khim 14:692–699

    CAS  Google Scholar 

  51. Hensen K, Gebhardt F, Kettner M, Pickel P, Bolte M (1997) Two cyclotetrasiloxanes at 143K. Acta Cryst C53:1867–1869. Both the octaphenylcyclotetrasiloxane and an unusual tetraspiro compound, cyclotetrasiloxane-2,4,6,8-tetraspiro-tetrakis(cyclopentane) [(C4H8)SiO]4, were reported

  52. Beckers H, Brauer DJ, Biirger H, Gielen R, Moritz P (1996) Siloxanes and silylamines with fluoromethyl-methylsilicon groups: X-ray study of [CH2F(CH3)SiO]4. J Organomet Chem 511:293–298

    Article  CAS  Google Scholar 

  53. Abe Y, Suyama K-I, Gunji T (2006) Synthesis and Structure of cis-trans-cis-1,3,5,7-tetraisocyanato-1,3,5,7 tetramethylcyclotetrasiloxane. Chem Lett 35:114–115

    Article  CAS  Google Scholar 

  54. Egert E, Haase M, Klingebiel U, Lensch C, Schmidt D, Sheldrick G (1986) Unusual conformations of isoelectronic (SiO)4, (SiOSiN)2 and (SiN)4 rings. J Organomet Chem 315:19–25

    Article  CAS  Google Scholar 

  55. Büschen T, Dietz W, Klingebiel U, Noltemeyer M, Schwerdtfeger Y (2007) Synthesis of fluorosilylenolates, aminosilylenolates, -ethers, and aldol condensates. Z Naturforsch 62b:1358–1370

    Article  Google Scholar 

  56. Braga D, Zanotti G (1980) The room-temperature structure of octaphenylcyclotetra(siloxane) (OPCTS). Acta Cryst B 36:950–953

    Article  Google Scholar 

  57. Hossain MA, Hursthouse MB, Malik KMA (1979) Octaphenylcyclotetrasiloxane: The monoclinic form. Acta Cryst B35:522–524

    Article  CAS  Google Scholar 

  58. Grey IE, Hardie MJ, Ness TJ, Raston CL (1999) Octaphenylcyclotetrasiloxane confinement of C60 into double columnar arrays. Chem Commun 1139–1140. https://doi.org/10.1039/a901719d

  59. Albright A, Gawley RE (2011) NHC-catalyzed dehydrogenative self-coupling of diphenylsilane: A facile synthesis of octaphenylcyclotetra(siloxane). Tet Lett 52:6130. https://doi.org/10.1016/j.tetlet.2011.09.028

    Article  CAS  Google Scholar 

  60. Nataro C, Cleaver WM, Allen CW (2009) 1-Methyl-1-vinyl-3,3,5,5-tetraphenylcyclotrisiloxane: An organofunctional cyclotrisiloxane. J Inorg Organomet Polym 19:566–569

    Article  CAS  Google Scholar 

  61. Aggarwal EH, Bauer SH (1950) The structure of hexamethylcyclotrisiloxane as determined by diffraction of electrons on the vapor. J Chem Phys 18:42–50

    Article  ADS  Google Scholar 

  62. Peyronel G (1954) Struttura cristallina dell’Esametilciclotrisilossano, Nota III. Rendiconti Accademia Nazionale Dei Lincei Classe di Scienze Fisiche. Matematiche e Naturali 16:231–236

    CAS  Google Scholar 

Download references

Acknowledgements

The NSF is gratefully acknowledged for support of the acquisition of an X-ray diffractometer (Award Number 2117596) through the Major Research Instrumentation program.

Funding

The authors declare that no funds, grants, or other support were received during the preparation of this manuscript.

Author information

Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, Rensselaer Polytechnic Institute, Troy, NY, 12108, USA

    John T. Leman, James Gibson & Peter J. Bonitatibus Jr

Authors
  1. John T. Leman
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. James Gibson
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Peter J. Bonitatibus Jr
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

The original concept of this paper was proposed by Dr. Leman. Synthesis, isolation and partial characterization of 1 was performed by Dr. Leman. Dr. Gibson performed all NMR characterization; Dr. Bonitatibus collected X-ray crystallographic data and refined the structures. The co-authors shared writing activities. All authors consent to publication of the work in its current form.

Corresponding author

Correspondence to Peter J. Bonitatibus Jr.

Ethics declarations

Ethics Approval

The authors declare that there were no ethical issues during this research.

Consent to Participate

All the authors consent to participate in this research.

Consent to Publication

All the authors consent to the publication of this research.

Competing Interests

The authors declare no competing interests.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 571 KB)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Leman, J.T., Gibson, J. & Bonitatibus, P.J. Characterization and Structure of Trans, Trans, Trans-1,3,5,7-Tetrakis(3ʹ,3ʹ,3ʹ-Trifluoropropyl)-1,3,5,7-Tetramethylcyclotetrasiloxane, and Structure of Trans-1,3,5-(3ʹ,3ʹ,3ʹ-Trifluoropropyl)-1,3,5-Trimethylcyclotrisiloxane. Silicon 16, 1491–1500 (2024). https://doi.org/10.1007/s12633-023-02768-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12633-023-02768-x

Keywords

Search

Navigation