Delocalized Lipophilic Cations as a Source of Naked Fluoride and Phase-Transfer Catalysts

Efficient Preparations of Fluorine Compounds

Volumn , Issue , 2012, Pages 220-226

  Kalinovich, Nataliya ^a   Kazakova, Olesya ^a   Röschenthaler, Gerd Volker ^a  

^a JACOBS UNIVERSITY BREMEN   (Germany)

Author keywords

(TMAF) or salt TDAE2+ 2F (TDAE, tetrakis(dimethylamino)ethylene); Delocalized lipophilic cations, of naked fluoride phase transfer catalysts; HMGF synthesis; Hypervalent fluorosilicon or tin onium derivative synthesis; Route to thermally stable salts stable, fluorides for "Halex" process

Indexed keywords

EID: 84886355795     PISSN: None     EISSN: None     Source Type: Book    
DOI: 10.1002/9781118409466.ch31     Document Type: Chapter

References (39)

1. Christe KO, Wilson WW, Wilson RD, Bau R, Feng J. Syntheses, properties, and structures of anhydrous tetramethylammonium fluoride and its 1:1 adduct with trans-3-amino-2- butenenitrile. J Am Chem Soc 1990;112:7619-7625.
2. Seppelt K. Gibt es das nackte F-Ion? Angew Chem 1992;104:299-300; Does the naked fluoride ion exist? Angew Chem, Int Ed 1992;31:292-293.
3. Seppelt K. Does the naked fluoride ion exist? Angew Chem Int Ed 1992;31:292-293.
4. Adams DJ, Clark JH. Nucleophilic routes to selectively fluorinated aromatics. Chem Soc Rev 1999;28:225-231.
5. Kolomeitsev AA, Seifert FU, Roeschenthaler G-V. Simple preparation of difluorophosphoranes using anhydrous zinc and tetramethylammonium fluorides. J Fluorine Chem 1995;71:47-49.
6. Chambers RD, Gray WK, Sandford G, Vaughan JFS. 'Naked fluoride ion' from elemental fluorine. J Fluorine Chem 1999;94:213-215.
7. Middleton WJ Homopolymers of polyfluorinated vinyl isocyanates. US19750624975,. Du Pont, 1976, 22 Jun.
8. Gingras M. Tetrabutylammonium difluorotripheylstannate as a new anhydrous synthetic equivalent to TBAF. Tetrahedron Lett 1991;32:7381-7384.
9. Hatanaka Y, Goda K, Okahara Y, Hiyama T. Highly selective cross-coupling reactions of aryl(halo)silanes with aryl halides: a general and practical route to functionalized biaryls. Tetrahedron 1994;50:8301-8316.
10. Pilcher PS, Ammon HL, DeShong P. Utilization of tetrabutylammonium triphenylsilyldifluoride as a fluoride source for nucleophilic fluorination. J Am Chem Soc 1995;117:5166-5167.
11. Brescia M-R, DeShong P. Stereoselective phenylation of allylic alcohol derivatives by palladium-catalyzed cross-coupling with hypervalent silicon complexes. J Org Chem 1998;63:3156-3157.
12. Smart BE, Middleton WJ, FarnhamWB. Stable perfluoroalkyl carbanion salts. J AmChem Soc 1986;108:4905-4907.
13. Delyagina NI, Igumnov SM, Snegirev VF, Knunyants IL. α-Fluoroalkylamides, a new source of nonhydrated fluoride Ion. 3.19F NMR spectra of perfluoro carbanions generated by Means of N,N,N',N',-tetramethylformamidinium bifluoride Bull Acad Sci USSR, Div Chem Sci 1981;30:1836-1839.
14. Kolomeitsev AA, Bissky G, Kirsch P, Röschenthaler G-V. A simple route to hexamethylguanidinium fluoride. J Fluorine Chem 2000;103:159-161.
15. Bis(dimethylamino)difluoromethane was prepared according to the procedure presented by Kolomeitsev and Roeschenthaler [13]. To a stirred solution of 17.1 g (100 mmol) tetramethylchloroform amidinium chloride in CH2Cl2 (50 mL) held at 0 ?C, 23.3 g (250 mmol) tetramethylammonium fluoride was added over 5 min. The cold mixture was stirred for additional 5 h, the precipitate filtered off, and washed twice with 25 mL pentane. The resulting solution was distilled using a 30-cm Vigreux column. Yield 13.1 g (95%). Purity 96-97% (1H NMR); bp 99-100 ?C. 19F NMR: -97.0 (s) ppm [16].
16. Igumnov SM, Delyagina NI, Knunyants IL. α-Fluoroalkylamines, a new source of unhydrated fluoride ion. Communication 6. Hexamethylguanidinium fluoride. Bull Acad Sci USSR, Div Chem Sci 1986;35:1191-1193.
17. Fawcett FS, Tullock CW, Coffman DD. The chemistry of carbonyl fluoride. I. The fluorination of organic compounds. J Am Chem Soc 1962;84:4275-4285.
18. Albanese D, Landini D, Maia A, Penso M. Key role of water for nucleophilic substitutions in phase-transfer-catalyzed processes: a mini-review Ind. Eng Chem Res 2001;40:2396-2401.
19. Albanese D, Landini D, Maia A, Penso M. Phase transfer catalysis: some recent applications in organic synthesis. J Mol Catal A:Chem 1999;150:113-131.
20. Makosza M, Bujok R. Cocatalysis by tetravalent tin compounds in phase-transfer catalyzed fluorination of alkyl halides and sulfonates. Tetrahedron Lett 2002;43:2761-2763.
21. Dehmlow EV, Knufinke V. J Chem Res (S) 1989;224-225.
22. Fantin VR, Berardi MJ, Scorrano L, Korsmeyer SJ, Leder P. Anovel mitochondriotoxic small molecule that selectively inhibits tumor cell growth. Cancer Cell 2002;2:29-42.
23. Modica-Napolitano JS, Aprille JR. Delocalized lipophilic cations selectively target the mitochondria of carcinoma cells. Adv Drug Delivery Rev 2001;49:63.
24. Langlois B, Gilbert L, Forat G. A new family of delocalized lipophilic cations. In: Desmurs J-R, Ratton S, editors. Industrial Chemistry Library. Amsterdam: Elsevier; 1996. Vol. 8, p 244.
25. Clark HJ, Wails D, Bastock TW. Aromatic Fluorination. New York: CRC Press; 1996.
26. Sasson Y, Negussie S, Royz M, Mushkin N. Tetramethylammonium chloride as a selective and robust phase transfer catalyst in a solid-liquid halex reaction: the role of water. J Chem Soc, Chem Commun 1996;297-298.
27. Issleib K, Lischewski M. Dimethylamino-Iminophosphorane. Synth Inorg Met Org Chem 1973;3:255-264.
28. Koidan GN, Marchenko P, Kudryavtsev AA, Pinchuk AM. J Gen Chem USSR 1982;52:1779-1787.
29. Marchenko P, Koidan GN, Povolotskii MI, Pinchuk AM. J Gen Chem USSR 1983;53:1364-1368.
30. Pazenok SV, Kolomeitsev AA, inventors. Process for preparing fluorine-containing compounds. HOECHST RES & TECH GMBH & CO [DE]; KOLOMEITSEV ALEXANDER [UA]; PASENOK SERGEJ [DE] Patent WO 9805610. 1998 12 Feb; Chem Abstr 1998;128, 252250a.
31. Kolomeitsev AA, Yagupolskii YL, Yagupolskii LM, Pazenok SV, Appel WK, Pfirmann R, Wessel T. 12th European Symposium on Fluorine Chemistry; Berlin, Germany; 1998, Abstract PII-83.
32. Kolomeitsev AA, Kirij NV, Pazenok SV, Appel WK, Röschenthaler G-V. 14th Winter Fluorine Conference; St. Petersburg, Florida; 1999, Abstract 37, p 26.
33. Henrich M, Marhold A, Kolomeitsev AA, Röschenthaler G-V, inventors; Bayer AG, assignee. Process for preparing nuclear-fluorinated aromatics. DE 10129057/EP 1266904, 2002 Dec 18.
34. Simultaneously to this patent application, the use of symmetrical and nonsymmetrical diphosphazenium salts as highly effective PT catalysts for halogen exchange aromatic fluorination has been claimed: Schanen V, Cristau H-J, Taillefer M, WO 02092226, 2002.
35. Marchenko AP, Koidan GN, Pinchuk AM. J Gen Chem USSR 1983;53:583-589.
36. Schwesinger R, Link R, Thiele G, Rotter H, Honnert D, Limbach HH, Männle F. Stabile phosphazenium-ionen in der synthese - ein leicht zugängliches, extrem reaktives "nacktes" Fluoridsalz. Angew Chem 1991;103:1376-1378; Stable phosphazenium ions in synthesis-an easily accessible, extremely reactive "naked" fluoride salt. Angew Chem, Int Ed 1991;30:1372-1375.
37. Schwesinger R, Link R, Thiele G, Rotter H, Honnert D, Limbach HH, Männle F. Stable phosphazenium ions in synthesis-an easily accessible extremely reactive "naked" fluoride salt. Angew Chem Int Ed 1991;30:1372-1375.
38. Hamed A, Mueller E, Jochims JC. The reaction of 2,4,6-tris(trimethylsiloxy)-1,3,5-triazine with chlorocarbenium ions: a new access to 1-oxa-3-azabutatrienium and 2-azaallenium salts. Tetrahedron 1986;42:6645-6656.
39. Henrich M, Marhold A, Kolomeitsev AA, Kalinovich N, Röschenthaler G-V. Anewfamily of delocalized lipophilic cations. Tetrahedron Lett 2003;44:5795-5798.