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ANHYDROUS FLUORIDE SALTS and REAGENTS and METHODS for THEIR PRODUCTION Stephen G University of Nebraska - Lincoln DigitalCommons@University of Nebraska - Lincoln Faculty Publications -- Chemistry Department Published Research - Department of Chemistry 2009 ANHYDROUS FLUORIDE SALTS AND REAGENTS AND METHODS FOR THEIR PRODUCTION Stephen G. DiMagno Lincoln, NE, [email protected] Haoran Sun Lincoln, NE Follow this and additional works at: https://digitalcommons.unl.edu/chemfacpub Part of the Analytical Chemistry Commons, Medicinal-Pharmaceutical Chemistry Commons, and the Other Chemistry Commons DiMagno, Stephen G. and Sun, Haoran, "ANHYDROUS FLUORIDE SALTS AND REAGENTS AND METHODS FOR THEIR PRODUCTION" (2009). Faculty Publications -- Chemistry Department. 185. https://digitalcommons.unl.edu/chemfacpub/185 This Article is brought to you for free and open access by the Published Research - Department of Chemistry at DigitalCommons@University of Nebraska - Lincoln. It has been accepted for inclusion in Faculty Publications -- Chemistry Department by an authorized administrator of DigitalCommons@University of Nebraska - Lincoln. US007592486B2 (12) United States Patent (10) Patent No.: US 7,592.486 B2 DiMagno et al. (45) Date of Patent: Sep. 22, 2009 (54) ANHYDROUS FLUORIDE SALTS AND 6,794,401 B2 9/2004 Nag REAGENTS AND METHODS FOR THEIR PRODUCTION FOREIGN PATENT DOCUMENTS CA 2035561 11, 1991 (75) Inventors: Stephen G. DiMagno, Lincoln, NE OTHER PUBLICATIONS (US); Haoran Sun, Lincoln, NE (US) CheMBioChemSpecial Issue: Fluorine in the Life Sciences 2004, 5, (73) Assignee:rsr rr l Regent oths laterily of Christe,557726. K.O., et al., J. Am. Chem. Soc. 1990, 112, 7619-25. eDraska, L1ncoln, Gnann, R.Z., et al., J. Am. Chem. Soc. 1997, 119, 112-115. (*) Notice: Subject to any disclaimer, the term of this JyK th,1990, A., et al.y ...."I . Chem. 2003, 42,2894-2901. patent is extended or adjusted under 35 J. AmChemSoc., Bennett, B.K. et al., 1994, 116, 11165-11166. U.S.C. 154(b) by 312 days. JACS, 1997, 119, 112-115. Inorg. Chem., 2003, 42,2894-2901. (21) Appl. No.: 11/226,277 Cox, D.P. et al., J. Org. Chem. 1984, 49, 3216-19. Shannn, R.K., et al., J. Org. Chem. 1983, 48, 2112-14. (22) Filed: Sep.15, 2005 Pilcher, et al. J. Am. Chem. Soc. 1995, 117. 5166-5167. Akiyama, Y, et al., S. Synlett 2003, 1530-1532. (65) Prior Publication Data Primary Examiner Shailendra Kumar US 2006/008.9514 A1 Apr. 27, 2006 (74) Attorney, Agent, or Firm Thompson Coburn LLP: Steven M. Ritchey, Esq. Related U.S. Application Data (57) ABSTRACT (60) Provisional application No. 60/610,412, filed on Sep. 16, 2004. Anhydrous organic fluoride salts and reagents prepared by a method comprising the nucleophilic Substitution of a fluori (51) Int. Cl. nated aromatic or fluorinated unsaturated organic compound CD7C 2 II/63 (2006.01) with a salt having the formula: (52) U.S. Cl. ........ grgrrr. 564/281: 568/9 Q, MA (58) Field of Classification Search ................. 56. in an inert polar, aprotic solvent; wherein M is an atom See application file for complete search history. capable of supporting a formal positive char2C, then groups Q are independently varied organic moieties, n is an integer (56) References Cited such that the QM carries at least one formal positive charge, X is an integer defining the number of formal positive U.S. PATENT DOCUMENTS charge(s), +, carried by the Q.M., A is an anionic nucleo 5,369,212 A 11/1994 Christe phile capable of substituting for F in the fluorinated com 5,854,084 A 12/1998 Drukier pound and F represents fluorine or a radioisotope thereof. 6,156,812 A 12/2000 Lau 6,451,921 B2 9, 2002 Weisse 16 Claims, 10 Drawing Sheets U.S. Patent Sep. 22, 2009 Sheet 1 of 10 US 7,592.486 B2 U.S. Patent Sep. 22, 2009 Sheet 2 of 10 US 7,592.486 B2 d --------------------------rror--r-er-re-rrrrrrrrrr 50 -80 O -80 -90 -100 -110 -120 -130 ppm Fig. 2 U.S. Patent Sep. 22, 2009 Sheet 3 of 10 US 7,592.486 B2 -66 -68 -70 -72 -74. -6 -78 ppm Fig. 3 U.S. Patent Sep. 22, 2009 Sheet 4 of 10 US 7,592.486 B2 YX64 - N e YX -- d Yx64 -1N C Y* -1N b -66 -68 -70 -72 -74 6 -78 ppm Fig. 4 U.S. Patent Sep. 22, 2009 Sheet 5 of 10 US 7,592.486 B2 h 2 hours 9 92 min f 75 min 8 53 min d 38 min C 29 min b 13 min 3. before addition of water .70 -80 -90 -100 -110 120 -130 -140 ppm Fig. 5 U.S. Patent Sep. 22, 2009 Sheet 6 of 10 US 7,592.486 B2 h 2 hours ---T—9 92 min f 75 min -- - eI - 53 Tmin - d A 38 min C A 29 min b 13 min before addition of water Fig. 6 U.S. Patent Sep. 22, 2009 Sheet 7 of 10 US 7,592.486 B2 f l 97 min e l 77 min d l 55 min C 40 min b 25 min al before addition of Water re-ret Trrrrrrrrrrrrrrrrrrrrty-fir - r-T-Y Titt tri-r-, rrrrrrrrrrr. It frt Trrrrrrrrrrrrr, 7 16 15 14 13 12 11 10 9 8 7 6 5 ppm Fig. 7 U.S. Patent Sep. 22, 2009 Sheet 8 of 10 US 7,592.486 B2 9 4.5 hours f 68 min e 62 min d 44 min C 30 min b 14 min 3. before addition of Water -70 -80 -90 -100 -110 -120 -130 -140 ppm Fig. 8 U.S. Patent Sep. 22, 2009 Sheet 9 of 10 US 7,592.486 B2 DF2 68 min 66 min A 62 min 44 min 30 min HF2 14 min -------TH---- -:42.6 -142.8 -143.0 -143.2 -143.4 -143.6 -143.8 ppm Fig. 9 U.S. Patent Sep. 22, 2009 Sheet 10 of 10 US 7,592.486 B2 e 79 in d 58 min C 39 min b 17 min 8. before addition of Water 7 16 15 14 13 12 11 O 9 8 7 6 5 ppm Fig. 10 US 7,592.486 B2 1. 2 ANHYDROUS FLUORIDE SALTS AND parative methods for synthesizing these individual salts are REAGENTS AND METHODS FOR THEIR not applicable for the preparation of a wide variety of fluoride PRODUCTION salts. Anhydrous fluoride salts with alkyl groups capable of beta-elimination (ethyl, propyl, butyl, isopropyl, pentyl, This application claims benefit of 60/610,412, filed Sep. 5 isobutyl, etc.) in particular are not accessible by current meth 16, 2004. ods. FIELD OF THE INVENTION Generally, then, these compounds are commonly prepared in a hydrated State and are Subsequently dried by heating The invention relates to novel organic fluorides and meth- 10 under dynamic vacuum or by azeotropic distillation. How ods for their production. ever, the conditions used to dry these salts are often incom patible with a variety of desirable cations. For example, dried BACKGROUND OF THE INVENTION tetrabutylammonium fluoride. (TBAF) Cox, D. P. et al., J. Fluorine substitution is a powerful tool to improve the 1s Org. Chem. 1984, 49, 3216-19 is reported to decompose by bioavailability of pharmaceuticals and agrochemicals. Thus, Hofmann elimination at room temperature. The salt isolated an expansive set of nucleophilic and electrophilic reagents after dehydration is contaminated with copious amounts of have been developed to replace various C—X functional bifluoride ion (HF) and tributylamine Shannn, R.K., etal, J. groups with C F. Org. Chem. 1983, 48, 2112-14. These considerations and Che MBioChem Special Issue. Fluorine In the Life Sciences 20 findings have led to the belief among those skilled in the art 2004, 5,557726. Simplest among the nucleophilic fluori that “it is very unlikely that pure, anhydrous tetraalkylammo nating reagents are “anhydrous” or “naked’ organic fluo nium fluoride salts have ever, in fact, been produced in the ride salts, represented by tetramethylammonium fluoride case of ammonium ions susceptible to E2 eliminations' (TMAF) Christe, K.O. etal, J. Am. Chem. Soc. 1990, 112, Sharma et al. Supra. 7619-25, 1-methylhexamethylenetetramine fluoride 25 It is an object of the present invention to provide a novel (MHAF) Gnann, R.Z., etal, J. Am. Chem. Soc. 1997, 119, method of producing truly anhydrous organic fluoride Salts 112-115 and tetramethylphosphonium fluoride (TMPF) and reagents. Kornath, A, et al. Inorg. Chem. 2003, 42, 2894-2901. Highly soluble anhydrous fluoride salts possessing a wide It is a further object of the invention to provide novel variety of alkyl groups are desirable for synthetic purposes, 30 anhydrous organic fluoride salts and reagents. but these compounds cannot be prepared according to cur rent methodologies. SUMMARY OF THE INVENTION Typical of prior art methods for preparing Such salts are those described in U.S. Pat. No. 5,369,212 and Canadian The above and other objects are realized by the present patent no. 2035561. 35 invention one embodiment of which relates to a method of The preparation of absolutely anhydrous fluoride salts synthesizing an anhydrous fluoride Salt having the formula: whose cations are substituted with alkyl groups possessing beta-hydrogenatoms has proved to be a significant challenge. QM'F. Approximately 20 years ago, the first claims for “anhydrous tetrabutylammonium fluoride appeared. The compounds 40 comprising the nucleophilic Substitution of a fluorinated aro were prepared by physical drying of the hydrated salt, i.e., matic or fluorinated unsaturated organic compound with a salt dynamic high vacuum (<0.1 mmHg) to remove water for at having the formula: least 48 hours from TBAF.3H2O at 40-45° C. (JOC, 1984, 49, 3216-3219). However, there was still 0.1 to 0.3 equiv of Q, MA water in this “anhydrous TBAF and copius quantities of the 45 in an inert polar, aprotic solvent; wherein M is an atom elimination products (tributylamine, bifluoride ion, and capable of supporting a formal positive charge, then groups Q butane) as a result of this process.
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    HEXACHLOROBENZENE 317 9. REFERENCES Abd-Allah AMA. 1999. Organochlorine contaminants in microlayer and subsurface water of Alexandria Coast, Egypt. J AOAC Int 82(2):391-398. Abraham K, Hille A, Ende M, et al. 1994. Intake and fecal excretion of PCDDs, PCDFs, HCB and PCBs (138,153,180) in a breast-fed and a formula-fed infant. Chemosphere 29(9-11):2279-2286. Abraham K, Papke O, Wahn U, et al. 2000. POP accumulation in infants during breast feeding. Organohalogen Compounds 48:25-26. ACGIH. 2014. Hexachlorobenzene. In: TLVs and BEIs based on the documentation of the threshold limit values for chemical substances and physical agents and biological exposure indices. Cincinnati, OH: American Conference of Governmental Industrial Hygienists, 33, 72-77. Ackerman LK, Schwindt AR, Simonich SL, et al. 2008. Atmospherically deposited PBDEs, pesticides, PCBs, and PAHs in Western U.S. National Park fish: Concentrations and consumption guidelines. Environ Sci Technol 42(7):2334-2341. Addae C, Cheng H, Martinez-Ceballos E. 2013. Effect of the environmental pollutant hexachlorobenzene (HCB) on the neuronal differentiation of mouse embryonic stem cells. Int J Environ Res Public Health 10(10):5244-5256. Adjarov DG. 1990. Decreased activity of liver coproporphyrinogen oxidase in hexachlorobenzene­ induced porphyria. Exp Pathol 40:117-122. *Adjarov DJ, Elder GH. 1986. Accumulation of uroporphyrin does not provoke further inhibition of liver uroporphyrinogen decarboxylase activity in hexachlorobenzene-induced porphyria. In: Hexachlorobenzene: Proceedings of an international symposium. IARC Sci Publ 77:467-469. Adjarov D, Ivanov E, Keremidchiev D. 1982. Gamma-glutamyl transferase: A sensitive marker in experimental hexachlorobenzene intoxication. Toxicology 23:73-77.
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  • Gamma Irradiation of Hexafluorobenzene1 R
    JOURNAL OF RESEARCH of the National Bureau of Standards-A. Physics and Chemi stry Vol. 64A, No. 4, July- August 1960 Gamma Irradiation of Hexafluorobenzene1 R. E. Florin, 1. A. Wall, and D. W. Brown r, (March 27, 1960) Mi xtures of hexafluorobenze ne a,nd benzene were irradi ated in li quid phase by means of a C060 cram ma ource at 20° a nd a t '2 18° C. P crfiuorohep tane a nd vari ous binar.v mixt ures involvi~ g perfluorohepta nc, hexaflu or obe ll ze ne, be nze ne, and cyclo hexane were a lso in'adi­ ated at 20° C. H exafluorobenzene rese mbled benzene very closely in its behavior upon r adio\ysis. Generall y t he fluorocarbon-hydrocarbon mixt ures evolved much mo rc SiF4 (indicatin g the formation of J-IF, which r eacts with the glass vessel) than the pure flu oro­ carbon components. The polymer from hexaflu o robenzene-benzrne mixtures was p r oba~ly rich in cyclohexadiene and cyclohexene un its, I' csembiing t hat from pu re benzene, a nd Its co mposition ratio exhibited a strong "altern atin g" tendency. The res ults a re discussed in terms of free-radical and excited-state mechanisms. r\ t 218 0 C hexaflu orobenzene a nd a lso its mixtures with benze ne showed qualitative difl'erences from their behavior a t 20° C, a ltho ugh t he G va lues for SiF4 and polymer rema ined moderate. 1. Introduction more resistant than hydrocarbons to heat, and also ftromatic compounds more resistant than aliphatic.
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