Syntheses of Mono-And Di-Pyrenyl Per Uoroalkanes: David Wiedenfeld, Sandip Niyogi, Debasis Chakrabarti
Syntheses of Mono-And Di-Pyrenyl Per Uoroalkanes: David Wiedenfeld, Sandip Niyogi, Debasis Chakrabarti
Syntheses of Mono-And Di-Pyrenyl Per Uoroalkanes: David Wiedenfeld, Sandip Niyogi, Debasis Chakrabarti
Abstract The syntheses of a series of uorophores of the general formula: pyrene-(CF2)n-pyrene (n3, 4 and 6) and pyrene-(CF2)n-F (n4 and 6) are reported using two different methodologies. Copper catalyzed coupling of 1-bromopyrene and the corresponding mono- and di-iodoperuoroalkanes are used in most cases. All the compounds have been characterized by 1H, 13C, 19F NMR and mass spectroscopies. # 2000 Elsevier Science S.A. All rights reserved.
Keywords: Fluorophores; Excimers; Pyrene; Conformational dynamics
1. Introduction The use of uorocarbon materials as high temperatureresistant lubricants [1] and insulators [2] highlight the importance of these molecules. These properties of uorocarbons are thought to be due in part to the rotational barrier of the CC bonds [3]. We are systematically studying the exibility of uorocarbon chains using emission and nuclear magnetic resonance (NMR) spectroscopies. For this purpose, we synthesized a series of uorophores of the general formula: pyrene(CF2)npyrene, (1, n3, 4 and 6). We primarily intend to study the emission properties of this class of uorocarbons as a function of chain length, temperature and solvent; steady-state and time-resolved light-emission measurements on the excimers of these dipyrenyl systems will allow us to infer the barriers to rotation in the uorocarbon chains. NMR studies on our molecules will also reveal information about the conformational properties of uorocarbons. Fluorocarbon monomers (3), and the corresponding hydrocarbon analogs (2) and (4), will be utilized as control compounds: Pyr-(CF2)n-Pyr (1), Pyr(CH2)n-Pyr (2), Pyr-(CF2)n-F (3), Pyr-(CH2)n-H (4), where n3, 4, 6. The 1-pyrenyl system was selected as the uorophore due to its favorable uorescence [4,5] lifetime. 1-Pyrenyl hydrocarbon excimers have previously been studied to obtain conformational information about the exibility of hydrocarbon-chains [5]. The effect of a uorocarbon chain on pyreneexcimer formation was also previously studied
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[4] with a mixed hydrocarbonuorocarbon species in between pyrene units; the pyrene units were attached via ester linkages. Comparison of the temperature-dependent kinetics, obtained from single photon counting lifetime measurements, demonstrated that the rate constant is signicantly slower and kinetic barrier higher for end-to-end cyclization for the partially uorinated molecules than the hydrocarbon analog. Our study differs in that it features a series of homologous peruoro-n-alkanes whose members do not contain the ester and hydrocarbon portions that were present in the earlier study. We wish to report herein the syntheses of the uorocarbons of general formula (1) where n3, 4 and 6 and (3) where n4 and 6.
2. Results and discussion One of the earliest known methods to prepare uoroalkylsubstituted aromatic compounds is uorination of uoroalkyl aryl ketones with sulfur tetrauorides [6]. The earliest known direct introduction of a uoroalkyl group in aromatic compounds was thermolysis or peroxide-promoted thermo-
Corresponding author.
0022-1139/00/$ see front matter # 2000 Elsevier Science S.A. All rights reserved. PII: S 0 0 2 2 - 1 1 3 9 ( 0 0 ) 0 0 2 6 2 - 1
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Scheme 1
lysis of peruoroalkyl iodides [79]. Photolysis of peruoroalkyl iodide [10], hexauoroacetone or peruoroalkylsulfonyl halides [1116] and also nickel carbonyl-promoted thermolysis of peruoroacyl chlorides [17] were later developments. The main disadvantage of these processes lies in the usage of vigorous conditions. Coe and Milner [18] reported a direct route to peruoroalkyl benzenes under mild conditions using hexauoropropylcopper species as reagents. From synthetic viewpoint, this also has some drawbacks: (i) the usage of excess copper to generate organometallic reagent; (ii) a large stoichiometric excess of substrate to drive the reaction; and (iii) very low yields (530%). We decided to follow the direct method of preparation of the uorocarbons (1) by a coupling reaction of 1-bromopyrene and the corresponding di-iodoperuoroalkanes in the presence of copper bronze as shown in Scheme 1. Although in previous reports [19,20], the aryl iodides were preferred in the coupling reactions, our reactions worked equally well with the more readily available 1-bromopyrene. The reactions proceed in moderate yields in DMSO at 1208C over 72 h. The coupling reaction also worked in pyridine (at 808C) and with HMPA as an additive or in DMSO at harsher
(>1808C) conditions, although at temperatures >1508C thermal decomposition of uoroalkylcopper occurs quite rapidly with the deposition of copper. The results are tabulated in Table 1. The coupling, although moderate in pyridine at 808C, is bromopyrene were comparable to that from 1-iodopyrene. 1,3-Di-iodohexauoropropane, the starting material for the synthesis of 1 (n3) was not available commercially and, hence, we had to adopt an alternate strategy for its synthesis. A novel 1,o-peruoroalkylation of aromatic systems (phenyl, tolyl, p-uorophenyl) via bis-decarboxylation of peruorodicarboxylic acids with XeF2 was reported by Brel et al. [21]. Initial attempts of synthesizing 1,3 diiodohexauoropropane using conditions analogous to those reported in Ref. [21] failed, although 1,2-dibromo and 1,2dichloro derivatives were reportedly synthesized. Direct decarboxylative alkylation of hexauoroglutaric acid in presence of pyrene was successful and afforded 1 (n3) in 65% yield as shown in Scheme 2. Coupling mono-iodoperuoro alkanes with 1-iodo or 1bromopyrene in the presence of copper bronze was employed for the syntheses of the uorocarbons 3 as shown in Scheme 3.
Scheme 3
Scheme 2
Table 1 Pyrene fluoroalkylation reactions Entry 1 Starting material I-(CF2)6-I Product Pyr-(CF2)6-Pyr Method A Solvents/condition Pyridine/808C DMSO/1208C DMSO/1808C Pyridine/808C DMSO/1208C DMSO/1808C Pyridine/HMPA/808C DMSO/1208C DMSO/1808C Pyridine/808C DMSO/1208C DMSO/1808C CH2Cl2/08C Yieldsa (%) 61 55 50 41 15 63 46 25 55 60 20 65 Recovery of 5 (%) 35 35 10 40 25 8 45 25 10 60 10 15
I-(CF2)6-F
Pyr-(CF2)6-F
I-(CF2)4-I
Pyr-(CF2)4-Pyr
4 5
a
I-(CF2)4-F HOOC-(CF2)3-COOH
Pyr-(CF2)4-F Pyr-(CF2)3-Pyr
A B
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3. Experimental details The 1H and 13C NMR spectra were recorded at 200 and 50.4 MHz, respectively, on a Varian Gemini 200 MHz Fourier transform spectrometer (chemical shifts are relative to TMS) and the 19F spectra were recorded on a Varian 300 MHz spectrometer, scan frequency 282 MHz, (chemical shifts are relative to CFCl3). The HREI mass spectra were obtained from the Nebraska Center for Mass Spectrometry, University of Nebraska, Lincoln, NE. The solvents pyridine and DMSO were dried by standard procedures from KOH and CaH2, respectively. Copper bronze was activated by treatment with iodine followed by washing with HCl in acetone and, nally, acetone alone, according to a reported [22] procedure. All yields were unoptimized. 1Iodopyrene (5) was synthesized by a FriedelCraft reaction [23] of pyrene with cyanogen iodide in the presence of AlCl3. 3.1. Method A: involving copper bronze The mono and di-iodoperuoroalkanes were obtained from Aldrich or Lancaster. Reactions involving either 1iodopyrene or 1-bromopyrene and mono- and di-iodoperuoroalkanes were carried out in a ame-dried three-necked 25 ml round-bottomed ask tted with a reux condenser. Copper bronze was freshly activated by a known procedure [22] and dried over CaCl2 in a desiccator. The reagents were transferred and the apparatus sealed from the glove box before use. Although the experimental details outline the usage of 1-iodopyrene as starting material and pyridine as solvent, 1-bromopyrene and DMSO were also used in every case. All the solvents and the conditions employed are tabulated in Table 1. The yields were calculated based on the recovery of either 1-bromopyrene or 1-iodopyrene. The iodoperuoroalkane starting material is usually decomposed at the end of the reaction. 3.1.1. 1-(1,1,2,2,3,3,4,4,5,5,6,6,6Tridecafluorohexyl)pyrene (6) A mixture of 1-iodopyrene (5 [23], 500 mg, 1.5 mmol), copper bronze (63 mg, 1 mmol), and 1-iodoperuorohexane (0.12 ml, 2.47 mmol) in pyridine (1 ml) was heated for 72 h at 808C under a positive pressure of nitrogen. It was then ltered through a short pad of celite and the resulting dark solution was chromatographed with chloroform. The fastest moving fraction was collected and was rechromatographed using a precoated TLC plate (silica gel HLO 20 cm20 cm, 500 microns). Elution with 10% ethyl acetate in hexanes yielded yellow crystals of 6 (240 mg, 31%). Crystals of 5 (200 mg, 40%) were recovered after the reaction and the yield corrected for this SM recovery was 50%. H NMR (CDCl3, d ppm): 7.858.20 (m, 7H), 8.40 8.50 (br d, J8.14 Hz, 2H).
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C NMR (CDCl3, d ppm): 96.22, 124.88, 125.34, 125.69, 125.79, 125.83, 126.33, 126.96, 127.32, 127.86, 129.25, 130.87, 131.07, 131.26, 136.69. 19 F NMR (CDCl 3 , d ppm): 81.34, 103.38, 120.51, 121.99, 123.28, 126.71. Mass (M/z): (HREI): M520.0496; calculated for C22H9F13 (520.0496). 3.1.2. 1-(1,1,2,2,3,3,4,4,4-nonafluorobutyl)pyrene (7) Synthesis of 7 was carried out as described for 6 using 1iodopyrene (5, 200 mg, 0.6 mmol), 1-iodononauorobutane (210 mg, 0.6 mmol) and copper bronze (63 mg, 1 mmol) in DMSO (1 ml) and a reaction time of 72 h. The yield of 7 was 37% (95 mg); 5 (80 mg, 40%) was recovered after the reaction and the yield corrected for this SM recovery was 60%: H NMR (CDCl3, d ppm): 7.98.1 (m, 7H), 8.38.55 (br d, J10.4 Hz, 2H). 19 F NMR(CDCl3, d ppm): 93.7, 111.5, 118.5, 131.8. Mass (M/z): (HREI): M420.0567; calculated for C20H9F9 (420.0560). 3.1.3. 1-[1,1,2,2,3,3,4,4,5,5,6,6-Dodecafluoro-6(1-pyrenyl) hexyl]pyrene (8) Synthesis of 8 was carried out as described for 6 using 1iodopyrene (5, 500 mg, 1.5 mmol), 1,6-di-iodoperuorohexane (456 mg, 0.82 mmol) and copper bronze (292 mg, 4.59 mmol) in DMSO (1 ml) and a reaction time of 72 h. The yield was 40% (200 mg). 5 (175 mg, 35%) was recovered after the reaction and the yield corrected for this SM recovery was 61%: H NMR (CDCl3, d ppm): 7.958.30 (m, 14 H), 8.458.50 (br d, J10.4 Hz, 4H) 19 F NMR (CDCl3, d ppm): 103.02, 120.12, 121.28. Mass (M/z): (HREI): Found M702.1207 calculated for C38H18F12 (702.1217). 3.1.4. 1-[1,1,2,2,3,3,4,4-Octafluoro-4(1-pyrenyl)butyl]pyrene (9) Synthesis of 9 was carried out as described for 6 using 1bromopyrene (500 mg, 1.77 mmol), l,4-di-iodoctauorobutane (226 mg, 0.5 mmol) and copper bronze (126 mg, 2 mmol) in either pyridine or DMSO (1 ml) and a reaction time of 72 h. The yield was 35% (105 mg). 1-bromopyrene (225 mg, 45%) was recovered after the reaction and the yield corrected for this SM recovery was 63%: H NMR (CDCl3, d ppm): 7.98.3 (m, 14H), 8.38.4 (d, J8.4 Hz, 4H). 19 F NMR (CDCl3, d ppm): 100.717, 113.577. Mass (M/z): (LREI): Found M602.3; calculated for C36H18F8 (602.1281).
1 1 1
13
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D. Wiedenfeld et al. / Journal of Fluorine Chemistry 104 (2000) 303306 [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] R.C. Bowers, W.A. Bisman, Ind. Chem. Prod. Res. 13 (1974) 115. E.L. Pace, J.G. Aston, J Am. Chem. Soc. 70 (1948) 566. F.D. Eaton, B.E. Smart, J Am. Chem. Soc. 112 (1990) 2821. Th. Forster, K. Kasper, Z. Phys. Chem. (Neue Folge) 1 (1954) 275. W.R. Hasek, W.C. Smith, V.A. Engelhardt, J. Am. Chem. Soc. 82 (1960) 543. G.V.D. Tiers, J Am. Chem. Soc. 82 (1960) 5513. E.S. Huyser, E. Bedard, J. Org Chem. 29 (1964) 1588. A.B. Cowell, C. Tamborski, J Fluorine Chem. 17 (1981) 345. N.O. Brace, U.S. Pat. 3,271,441 CA., (1981) 66, 2388y. J.M. Birchall, G.P. Irvin, R.A. Boysen, J. Chem. Soc. Perkin Trans. II (1975) 435. Y. Kobyashi, I. Kumadaki, A. Ohsawa, S. Murakami, T. Nakano, Chem Pharm Bull. 26 (1978) 1247. S.W. Charles, E. Whittle, Chem. Soc. Faraday Trans. I 56 (1960) 794. S.W. Charles, J.T. Pearson, E. Whittle, Chem. Soc. Faraday Trans. I 57 (1961) 1356. J.L. Holms, K.O. Kutsche, Chem. Soc. Faraday Trans. I 58 (1962) 333. J.R. Mattson, U.S. Pat. 3,326,928 CA., (1969), 68, P59357h. D.D. Coffmann, J.J. Drysdale, J. Am. Chem. Soc. 82 (1960) 5111. P.L. Coe, N.E. Milner, J. Fluorine Chem. 2 (1972/73) 167. V.C.R. McLoughlin, J. Thrower, Tetrahedron 25 (1969) 5921. J Sepliok, R.L. Soulen, J. Fluorine Chem. 24 (1984) 61. V.K. Brel, V.I. Uvarov, N.S. Zefirov, P.S. Stang, R. Caple, J Org. Chem. 58 (1993) 6922. Vogel's Textbook of Practical Organic Chemistry, 5th Edition, Longman Scientific & Technical, Wiley, New York, 1994, 426 pp. F. Radner, Acta Chem. Scand. 43 (1989) 481.
3.2. Method B: involving XeF2 3.2.1. 1-[1,1,2,2,3,3-Hexafluoro-3(1-pyrenyl)propyl)pyrene (10) To a solution of hexauoroglutaric acid (500 mg, 2.11 mmol) and pyrene (1.8 g, 9 mmol) in dry dichloromethane (20 ml) was added XeF2, (360 mg, 2.11 mmol). The mixture was stirred at 10208C for 3.5 h and treated with aqueous bicarbonate solution. Concentration and ash chromatography gave 10 (754 mg, 65%). H NMR (CDCl3, d ppm): 8.08.30 (m, 14H), 8.32 8.42 (br d, J10.2 Hz, 4H). 19 F NMR (CDCl3, d ppm): 123.305 and 124.289. Mass (M/z): (HREI): Found M552.1310 calculated for C35H18F6 (552.1313). Acknowledgements We thank the Robert A. Welch Foundation (Grant B1415) for nancial support. References
[1] Teflon PFA Fluorocarbon Resin-Wear and Frictional Data, APD#2, bulletin, E.I. DuPont de Nemours & Co., Wilmington, DE., 1973.
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