Sonogashira Coupling Reaction in Water Using a Polymer-Supported Terpyridine–Palladium Complex Under Aerobic Conditions

Trans. Mat. Res. Soc. Japan 40[2] 103-106 (2015)

Sonogashira Coupling Reaction in Water Using a Polymer-Supported Terpyridine–Palladium Complex under Aerobic Conditions

Toshimasa Suzuka,* Mika Adachi, and Kazuhito Ogihara Department of Chemistry, Biology and Marine Science, University of the Ryukyus, Nishihara Okinawa 903-0213, Japan Fax: 81-098-895-8531, e-mail: [email protected]

The palladium-catalyzed coupling reaction between an aryl halide and a terminal alkyne, the so-called Sonogashira coupling reaction, was found to occur in water under copper-free conditions using an amphiphilic polystyrene–poly(ethylene glycol) (PS-PEG) resin-supported palladium–terpyridine complex, giving the corresponding aryl-substituted alkyne in high yield. The PS-PEG resin-supported palladium–terpyridine catalyst was recovered simply by filtering the product mixture under air and could be reused three times with only slightly decreased catalytic activity after each use. Key words: Sonogashira, palladium, terpyridine, water, cross-coupling

1. INTRODUCTION organic solvent or metal-contaminated wastes are The palladium-catalyzed coupling reaction produced; and (2) the presence of oxygen and between an aryl halide and a terminal alkyne, the moisture do not negatively affect the reaction. so-called Sonogashira reaction [1], is recognized These benefits therefore allow the Sonogashira as being the most successful method for forming coupling reaction to be performed meeting the an sp2 carbon–sp3 carbon bond. Since its requirements of “green chemistry”. discovery by Sonogashira and co-workers in 1975, a vast amount of research has been performed cat 1. ( 5mol% Pd) into its synthetic applications and on improving X + R1 R1 the reaction efficiency [2]. However, one of the Et3N, in H2O 100 °C, 12 h, air 2 3 4 major problems with using the Sonogashira (without Cu) reaction lies in the reaction conditions that are required. The use of a homogeneous mixture of a palladium catalyst and a copper reagent PEG 3000 N O (co-catalyst) is frequently required to promote the PS O N C N Pd+Cl n H reaction, and this leads to the coupling products Cl- n = 60~74 N being contaminated with considerable amounts of 1 metal residues. We have recently developed a copper-free Sonogashira coupling reaction using Scheme 1. Sonogashira reaction in water using a polymer-supported palladium catalyst in water the PS-PEG–terpyridine–Pd complex 1 under an inert gas atmosphere [3]. The polymeric catalyst consists of a polymer, a linkage moiety, 2. EXPERIMENTAL SECTION and a catalytic center prepared from a transition 2.1 General methods metal and a phosphine-based ligand. Therefore, All of the procedures were carried out under the catalytic reactions are carried out under aerobic conditions. Water was deionized using a nitrogen atmosphere to avoid the phosphine Millipore Milli-Q Gradient A10 system. NMR ligands being oxidized [4,5]. spectra were recorded using a Bruker AVANCE 1 We recently developed an amphiphilic spectrometer (500 MHz for H and 125 MHz for 13 polystyrene–poly(ethylene glycol) (PS-PEG) C), a Bruker AV400N spectrometer (400 MHz 1 13 resin-supported terpyridine–metal complex. We for H and 100 MHz for C), and a Hitachi 1 have found that it is an effective catalyst for R1900 spectrometer (90 MHz for H and 22 MHz 13 1 13 coupling reactions in water under heterogeneous for C). H and C NMR spectra were recorded and aerobic conditions, and that it is highly at 25 °C, with the compound for analysis recyclable when used in that way [6]. As an dissolved in CDCl3 or dimethyl sulfoxide-d6 13 extension to that study, we investigated the (DMSO-d6). The C chemical shifts are given ability of a PS-PEG-supported relative to the CDCl3 and DMSO-d6 internal terpyridine–palladium(II) complex standards (δ 77.0 ppm and 39.7 ppm, (PS-PEG–terpyridine–Pd) to catalyze the respectively). Mass spectra were measured using Sonogashira coupling reaction in water. Herein, a JEOL JMS-T100GCv MS (gas we report the results of this investigation, and chromatography–mass spectrometry) instrument show that the complex effectively catalyzes the or a JEOL JMS-T100LP MS (liquid Sonogashira coupling reactions between various chromatography–mass spectrometry) instrument, aryl halides and alkynes in water under aerobic and the base peak of a mass spectrum is labeled conditions (Scheme 1). This catalyst system “bp.” Gas chromatography and infra-red offers two benefits over other systems: (1) no spectroscopy analyses were performed using a

103 104 Sonogashira Coupling Reaction in Water Using a Polymer-Supported Terpyridine-Palladium Complex under Aerobic Conditions

Shimadzu GC-2014 instrument and a Jasco 33.1 Hz, 1 C), 128.8, 128.4, 126.4 (q, J = 272 Hz, 129.5, 128.5, 128.4, 128.3, 124.9, 122.7, 90.5, iodobenzene derivatives 2e, 2f, and 2g (which FTIR-410 instrument, respectively. Inductively 1 C), 125.2 (q, J = 272 Hz, 1 C), 122.5, 91.7, 87.8. MS (EI): m/z (rel %) 212 (bp, M+), 176 (46), each have methyl substituents at the meta- or coupled plasma–atomic emission (ICP–AES) 87.9. MS (EI): m/z (rel %) 246 (73, M+), 176 (43), 151 (13). IR (ATR): v (cm−1) 3055, 1490. CAS ortho-positions) gave spectra were acquired using a Shimadzu 98 (bp), 75 (49), 51 (46). IR (ATR): v (cm−1) registry number: 51624-34-1. 1-phenyl-2-(o-tolyl)acetylene (4e) in 57% yield, ICPE-9000 instrument. 3080, 2219, 1508. CAS registry number: 1-phenyl-2-(m-tolyl)acetylene (4f) in 71% yield, 370-99-0. 3. RESULTS AND DISCUSSION and 1-(1-naphthyl)-2-phenylacetylene (4g) in 2.2 Materials We developed a Sonogashira coupling reaction 79% yield, respectively (runs 5–7). The PS-PEG–terpyridine–Pd (1) was prepared 1-(p-Methoxycarbonylphenyl)-2-phenylacetylene for aryl iodides and bromides using the polymeric Bromobenzene 2j was reacted with 3 using a 1 from a PS-PEG-NH2 resin (Tenta Gel S NH2, with (4d): H NMR (CDCl3) δ 8.02 (d, J = 8.5 Hz, 2 H), catalyst 1 in water. The polymeric catalyst was longer reaction time (24 h) than was used for the an average diameter of 90 µm, 1% divinylbenzene 7.59 (d, J = 8.5 Hz, 2 H), 7.57–7.53 (m, 2 H), readily prepared from other reactions, and this reaction gave the cross-links, and an amino residue loading value 7.38–7.36 (m, 3 H), 3.93 (s, 3 H). 13C NMR 4-methoxycarbonylbenzaldehyde, corresponding acetylene derivative 4a in 1.6% of 0.31 mmol/g, purchased from Rapp Polymer), a (CDCl3) δ 166.5, 131.7, 131.4, 129.5, 129.4, 2-acetylpyridine, NH4OH, PS-PEG-NH2 resin, yield (run 11). polymeric terpyridine ligand, and 128.7, 128.4, 127.9, 122.6, 92.4, 88.6, 52.9. MS and (C6H5CN)2PdCl2 following the procedures + (C6H5CN)2PdCl2 following a procedure that has (EI): m/z (rel %) 236 (80, M ), 205 (bp), 176 (91), described elsewhere [6,7]. Table I. Effects of different bases on the been reported previously [6]. The Pd loading 151 (34). IR (ATR): v (cm−1) 2949, 2217, 1718, The polymeric catalyst 1 exhibited a high Sonogashira coupling reaction between level in the polymeric catalyst 1 was 0.26 1606, 1508, 1455, 1374, 1280. CAS registry catalytic activity for the Sonogashira coupling iodobenzene and phenylacetylene using polymeric mmol/g. number: 42497-80-3. reaction. Iodobenzene (2a) and phenylacetylene 3 catalyst 1 in watera PS-PEG-terpyridine-Pd 1 were coupled in water using catalyst 1 (5 mol% 5 mol% I + 2.3 Sonogashira coupling reaction 1 Pd) in the presence of 3 equiv. of base at 100 °C base, 100 °C, 12 h The procedure used to obtain the Sonogashira 1-Phenyl-2-(o-tolyl)acetylene (4e): H NMR for 12 h. The reaction mixture was filtered and air, in H2O coupling reaction product 4a is described here. (CDCl3) δ 7.44-7.39 (m, 3 H), 7.25–7.21 (m, 3 H), the recovered resin beads were rinsed with a 2a 3 4a The Sonogashira coupling reaction products 4b–i 7.12–7.10 (m, 2 H), 7.08–7.04 (m, 1 H), 2.41 (s, 3 small portion of water and then extracted with 13 Run Base Yield were obtained using this procedure with slight H). C NMR (CDCl3) δ 166.5, 131.7, 131.4, EtOAc to give diphenylacetylene (4a). modifications. Iodobenzene (2a; 81.6 mg, 0.40 129.5, 129.4, 128.7, 128.4, 127.9, 122.6, 92.4, We used different bases in the Sonogashira + 1 32 88.6, 52.9. MS (EI): m/z (rel %) 192 (bp, M ), Li2CO3 mmol) was added to a mixture of the polymeric −1 coupling reaction using catalyst 1 in water to catalyst 1 (80 mg, 0.020 mmol), the base Et N 165 (27), 115 (11).IR (ATR): v (cm ) 3055, 2919, identify which bases were most suitable for use in 3 2 Na CO 28 (121 mg, 1.2 mmol), and phenylacetylene (3; 81.7 1600, 1492. CAS registry number: 14309-60-5. the reaction (Table I). The reaction efficiencies 2 3 mg, 0.80 mmol) in H2O (3.0 mL). The reaction were very different for different bases. Lithium 3 K CO 45 mixture was shaken at 100 °C for 12 h and then carbonate, sodium carbonate, potassium carbonate, 2 3 1-Phenyl-2-(m-tolyl)acetylene (4f): 1H NMR filtered. The resin beads that were recovered were and cesium carbonate gave 4a in 32%, 28%, 45%, (CDCl ) δ 7.51 ( d, J = 5.8 Hz, 2 H), 7.35–7.28 4 47 rinsed with H O and extracted three times with 3 and 47% yields, respectively (runs 1–4). Sodium Cs2CO3 2 (m, 5 H), 7.21 (t, J = 7.5 Hz, 1 H), 7.12 (d, J = EtOAc (6 mL). The EtOAc layer and the aqueous hydroxide, potassium hydroxide, and cesium 7.5 Hz, 1 H), 2.33 (s, 3 H). 13C NMR (CDCl ) δ 5 44 layer were separated and the aqueous layer was 3 hydroxide gave 4a in 44%, 40%, and 50% yields, NaOH 137.9, 132.1, 131.5, 129.3, 128.6, 128.2, 128.2, extracted with more EtOAc (3 mL). The respectively (runs 5–7). 128.1, 123.3, 122.9, 89.5, 89.0, 21.1. MS (EI): 6 40 combined EtOAc extracts were washed with brine Organic amines were found to smoothly KOH m/z (rel %) 192 (bp, M+), 165 (13), 115 (5). IR (2 mL), dried over MgSO , and concentrated in promote the Sonogashira coupling reaction in 4 (ATR): v (cm−1) 3003, 2919, 1492. CAS registry 7 50 vacuo. The resulting residue was passed through a water. Using the base CsOH number: 14635-91-7. silica gel chromatography column eluted with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) gave 8 73 hexane to give 58.8 mg (a yield of 82%) of 4a in 73% yield (run 8) under the same reaction DBU diphenylacetylene (4a). 1-(1-Naphthyl)-2-phenylacetylene (4g): 1H NMR conditions as were used in all of the tests using 9 Et3N 82 (CDCl3) δ 8.44 (d, J = 8.3 Hz, 1 H), 7.83 (ddd, J different bases. The most effective base was Et3N, 2.4 Spectral and analytical data for the acetylene = 13.2, 13.2, 4.9 Hz, 2 H), 7.75 (d, J = 7.1 Hz, 1 and using this base gave 4a in an impressive 82% a All reactions were carried out using iodobenzene (2a; compounds yield (run 9). 0.4 mmol), phenylacetylene (3; 0.8 mmol), and the 1 H), 7.64 (d, J = 7.3 Hz, 2 H), 7.58 (t, J = 7.3 Hz, Diphenylacetylene (4a): H NMR (CDCl3) δ The scope of aryl halides that were suitable for selected base (1.2 mmol) in the presence of the 13 1 H), 7.52 (t, J = 7.3 Hz, 1 H), 7.44 (t, J = 7.6 Hz, 7.55–7.51 (m, 4 H), 7.36–7.29 (m, 6 H). C NMR 1 H), 7.39–7.34 (m, 3 H). 13C NMR (CDCl ) δ use in the Sonogashira coupling reaction with polymeric catalyst 1 in 3.0 mL of H2O at 100 °C for 12 3 h under aerobic conditions. (CDCl3) δ 131.5, 128.3, 128.2, 123.2, 89.4. MS 133.1, 131.7, 131.6, 130.3, 128.7, 128.4, 128.3, phenylacetylene using catalyst 1 in water was + (EI): m/z (rel %) 178 (bp, M ), 152 (24). IR 128.2, 128.2, 126.7, 126.4, 126.1, 125.2, 125.2, also examined (Table II). The general procedure −1 We examined the recyclability of catalyst 1 (ATR): v (cm ) 3062, 1598, 1491. CAS registry 94.3, 87.5. MS (EI): m/z (rel %) 228 (bp, M+), that was used was to perform the reaction of an used for the Sonogashira coupling reaction number: 64666-02-0. 202 (6), 113 (13). IR (ATR): v (cm−1) 3055, 1488, aryl halide with phenylacetylene in the presence between iodobenzene (2a) and phenylacetylene 1396. CAS registry number: 4044-57-9. of Et3N (3 equiv.) and catalyst 1 (5 mol% Pd) in 1-Phenyl-2-(p-tolyl)acetylene (4b): 1H NMR water. The results obtained using different aryl (3) (Scheme 2). The first reaction, which gave diphenylacetylene (4a) in 82% yield, was (CDCl3) δ 7.52 (dd, J = 8.1, 1.9 Hz, 2 H), 7.43 (d, halides and phenylacetylene are described below. J = 8.1 Hz, 2 H), 7.38–7.30 (m, 3 H), 7.15 (d, J = 1-(o-Chlorophenyl)-2-phenylacetylene (4h): 1H The aryl halides 2a–k were reacted with performed, then the catalyst was recovered by 13 simply filtering the product mixture. The catalyst 7.8, 2 H), 2.36 (s, 3 H). C NMR (CDCl3) δ NMR (CDCl3) δ 7.57-7.55 ( m, 3 H), 7.53–7.50 phenylacetylene (3). Iodobenzene (2a) gave 138.3, 134.8, 131.5, 131.4, 129.1, 128.3, 128.0, (m, 1 H), 7.34–7.32 (m, 3 H), 7.22–7.18 (m, 2 H). diphenylacetylene (4a) in 82% yield (run 1). The was then washed with H2O, dried under vacuum, 13 and reused four times under the same reaction 127.7, 120.1, 89.5, 21.5. MS (EI): m/z (rel %) 192 C NMR (CDCl3) δ 135.9, 133.2, 131.7, 129.2, iodobenzene derivatives 2b, 2c, and 2d (which (bp, M+), 165 (27), 39 (21). IR (ATR): v (cm−1) 128.6, 128.3, 126.4, 123.1, 122.8, 94.5, 86.2. MS each have electron-donating or conditions. Diphenylacetylene (4a) was obtained 3052, 3029, 2215, 1594, 1509, 1441, 1380. CAS (EI): m/z (rel %) 212 (bp, M+), 176 (38), 151 (11). electron-withdrawing substituents at their in 72%, 76%, 51%, and 42% yields when the registry number: 185817-85-0. IR (ATR): v (cm−1) 3057, 1491, 1468. CAS para-positions) gave catalyst was reused the first, second, third, and registry number: 10271-57-5. 1-phenyl-2-(p-tolyl)acetylene (4b) in 70% yield, fourth times, respectively. Importantly, ICP-AES 1-Phenyl-2-(p-trifluoromethylphenyl)acetylene 1-phenyl-2-(p-trifluoromethylphenyl)acetylene analysis showed that slightly detectable 1 1 concentrations of palladium residues were present (4c): H NMR (CDCl3) δ 7.62 (dd, J =14.1, 8.2 1-(m-Chlorophenyl)-2-phenylacetylene (4i): H (4c) in 77% yield, and 13 in aqueous solution [8]. Hz, 4 H), 7.56–7.54 (m, 2 H), 7.37 (m, 3 H). C NMR (CDCl3) δ 7.46-7.43 ( m, 3 H), 7.34–7.32 1-(p-methoxycarbonylphenyl)-2-phenylacetylene

NMR (CDCl3) δ 132.5, 131.8, 131.7, 129.8 (q, J = (m, 1 H), 7.29–7.27 (m, 3 H), 7.23–7.16 (m, 2 H). (4d) in 76% yield, respectively (runs 2–4). The 13 C NMR (CDCl3) δ 134.1, 131.6, 131.4, 129.6,

Toshimasa Suzuka et al. Trans. Mat. Res. Soc. Japan 40[2] 103-106 (2015) 105

129.5, 128.5, 128.4, 128.3, 124.9, 122.7, 90.5, iodobenzene derivatives 2e, 2f, and 2g (which 87.8. MS (EI): m/z (rel %) 212 (bp, M+), 176 (46), each have methyl substituents at the meta- or 151 (13). IR (ATR): v (cm−1) 3055, 1490. CAS ortho-positions) gave registry number: 51624-34-1. 1-phenyl-2-(o-tolyl)acetylene (4e) in 57% yield, 1-phenyl-2-(m-tolyl)acetylene (4f) in 71% yield, 3. RESULTS AND DISCUSSION and 1-(1-naphthyl)-2-phenylacetylene (4g) in We developed a Sonogashira coupling reaction 79% yield, respectively (runs 5–7). for aryl iodides and bromides using the polymeric Bromobenzene 2j was reacted with 3 using a catalyst 1 in water. The polymeric catalyst was longer reaction time (24 h) than was used for the readily prepared from other reactions, and this reaction gave the 4-methoxycarbonylbenzaldehyde, corresponding acetylene derivative 4a in 1.6% 2-acetylpyridine, NH4OH, PS-PEG-NH2 resin, yield (run 11). and (C6H5CN)2PdCl2 following the procedures described elsewhere [6,7]. Table I. Effects of different bases on the The polymeric catalyst 1 exhibited a high Sonogashira coupling reaction between catalytic activity for the Sonogashira coupling iodobenzene and phenylacetylene using polymeric reaction. Iodobenzene (2a) and phenylacetylene 3 catalyst 1 in watera PS-PEG-terpyridine-Pd 1 were coupled in water using catalyst 1 (5 mol% 5 mol% I + Pd) in the presence of 3 equiv. of base at 100 °C base, 100 °C, 12 h for 12 h. The reaction mixture was filtered and air, in H2O the recovered resin beads were rinsed with a 2a 3 4a small portion of water and then extracted with Run Base Yield EtOAc to give diphenylacetylene (4a). We used different bases in the Sonogashira 1 Li CO 32 coupling reaction using catalyst 1 in water to 2 3 identify which bases were most suitable for use in 2 Na CO 28 the reaction (Table I). The reaction efficiencies 2 3 were very different for different bases. Lithium 3 K CO 45 carbonate, sodium carbonate, potassium carbonate, 2 3 and cesium carbonate gave 4a in 32%, 28%, 45%, 4 47 and 47% yields, respectively (runs 1–4). Sodium Cs2CO3 hydroxide, potassium hydroxide, and cesium 5 44 hydroxide gave 4a in 44%, 40%, and 50% yields, NaOH respectively (runs 5–7). 6 40 Organic amines were found to smoothly KOH promote the Sonogashira coupling reaction in 7 50 water. Using the base CsOH 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) gave 8 73 4a in 73% yield (run 8) under the same reaction DBU conditions as were used in all of the tests using 9 Et N 82 different bases. The most effective base was Et3N, 3 and using this base gave 4a in an impressive 82% a All reactions were carried out using iodobenzene (2a; yield (run 9). 0.4 mmol), phenylacetylene (3; 0.8 mmol), and the The scope of aryl halides that were suitable for selected base (1.2 mmol) in the presence of the use in the Sonogashira coupling reaction with polymeric catalyst 1 in 3.0 mL of H2O at 100 °C for 12 phenylacetylene using catalyst 1 in water was h under aerobic conditions. also examined (Table II). The general procedure that was used was to perform the reaction of an We examined the recyclability of catalyst 1 aryl halide with phenylacetylene in the presence used for the Sonogashira coupling reaction between iodobenzene (2a) and phenylacetylene of Et3N (3 equiv.) and catalyst 1 (5 mol% Pd) in water. The results obtained using different aryl (3) (Scheme 2). The first reaction, which gave halides and phenylacetylene are described below. diphenylacetylene (4a) in 82% yield, was The aryl halides 2a–k were reacted with performed, then the catalyst was recovered by phenylacetylene (3). Iodobenzene (2a) gave simply filtering the product mixture. The catalyst diphenylacetylene (4a) in 82% yield (run 1). The was then washed with H2O, dried under vacuum, iodobenzene derivatives 2b, 2c, and 2d (which and reused four times under the same reaction each have electron-donating or conditions. Diphenylacetylene (4a) was obtained electron-withdrawing substituents at their in 72%, 76%, 51%, and 42% yields when the para-positions) gave catalyst was reused the first, second, third, and 1-phenyl-2-(p-tolyl)acetylene (4b) in 70% yield, fourth times, respectively. Importantly, ICP-AES 1-phenyl-2-(p-trifluoromethylphenyl)acetylene analysis showed that slightly detectable (4c) in 77% yield, and concentrations of palladium residues were present 1-(p-methoxycarbonylphenyl)-2-phenylacetylene in aqueous solution [8]. (4d) in 76% yield, respectively (runs 2–4). The

106 Sonogashira Coupling Reaction in Water Using a Polymer-Supported Terpyridine-Palladium Complex under Aerobic Conditions

PS-PEG-terpyridine-Pd 1 5 mol% compound in water under aerobic conditions to I + Synthesis and Magnetic Properties of Phthalocyanine Et3N, 100 °C, 12 h give the corresponding diarylacetylene in high to air, in H2O excellent yield. The catalyst can be recovered and Based Carbon Materials 2a 3 4 reused several times with only a slight decrease recycling experiments 1st reuse 72% yield in catalytic activity after each use. We are 2nd reuse 76% yield 3rd reuse 51% yield continuing to investigate the scope of the 4th reuse 42% yield 1* 1 2 2 1 Sonogashira coupling reaction and possible Yuta Muto , Shun Sato , Masayuki Hagiwara , Takanori Kida , Masamichi Sakai , Scheme 2. Catalyst recycling experiments applications of the catalyst in other organic 1 1 1 Takeshi Fukuda , Norihiko Kamata , and Zentaro Honda transformations. Table II. Sonogashira coupling reactions between 1 Saitama Univ., 225 Shimo-Ohkubo, Sakura-ku, Saitama 338-8570, Japan

aryl halides and phenylacetylene using the 2 AHMF, Osaka Univ., 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan ACKNOWLEDGEMENTS polymeric catalyst 1 in water a [email protected] We are grateful for financial support from the PS-PEG-terpyridine-Pd 1 5 mol% X + International Research Hub project of the Faculty Et3N, 100 °C, 12 h of Science University of the Ryukyus, Joint Study  R1 R1 air, in H2O Program of the Institute for Molecular Science. 2 3 4 A magnetic phthalocyanine based carbon material has been successfully synthesized by using Run ArX Product Yield REFERENCES [1] K. Sonogashira, Y. Tohda, Tetrahedron Lett., a low energy process that employs highly chlorinated iron-phthalocyanine as building blocks and I an alkali metal as a coupling reagent. The X-ray diffraction patterns and XPS spectrum for the 1 82 16, 4467-4470 (1975). Sonogashira, K. J. 2a 4a Organomet. Chem. 653, 46-49 (2002). reaction products suggest that they consist of amorphouscarbon material that contains uniformly [2] For reviews, see: (a) R. Chinchilla, C. dispersed iron ions. The iron phthalocyanine based carbon material exhibits ferromagnetic I CH3 CH3 Nájera, Chem. Rev., 107, 874-922 (2007). (b) K. properties at room temperature and the ferromagnetic phase transition occurs at T =490 K. 2 70 C 2b 4b Sonogashira, In Metal-Catalyzed Reactions; Key words: ferromagnetism, carbon material, high Curie temperature, phthalocyanine Diederich, F., Stang, P. J., Eds.; Wiley-VCH: I CF3 CF3 New York, 1998. 1. INTRODUCTION and the magnetic characterization of the resulting 3 77 [3] T. Suzuka, Y. Okada, K. Ooshiro, Y. Uozumi, 2c 4c The transition metal phthalocyanine is one example of samples indicates the presence of ferromagnetic Tetrahedron 66, 1064-1069 (2010). magnetic organometallic molecules that contain metal behavior well above room temperature.

I CO CH CO CH [4] For a review, see R. A. Sheldon, I. Arends, U. 2 3 2 3 ions with local magnetic moments [1]. Since manganese 4 76 Hanefeld, Green Chemistry and Catalysis; Wiley–VCH, 2d 4d phthalocyanine was first reported as an organometallic 2. EXPERIMENTAL Weinheim (2007). ferromagnet, magnetic properties of transition metal The synthesis of the iron PBCM samples was H C H3C 3 [5] For recent studies on the copper-free Sonogashira phthalocyanines have attracted much attention [2, 3]. performed by the following methods using 5 I 57 coupling under heterogeneous conditions, see: (a) N. Lu, The Curie temperatures TC of typical phthalocyanines hexadecachlorophthalocyanine iron (II) (abbreviated as 2e 4e Y. –C. Chen, T. –L. Chen, S. –J. Wu, J. Organomet. are very low (e.g., β-phase MnPc: T =8.3 K) and the Cl FePc), sodium, and potassium as purchased from Chem., 694, 278-284 (2009) (fluorous biphasic system). C 16 CH3 CH3 magnetic susceptibility obeys a paramagnetic Aldrich Chemical Company Inc. In a typical procedure, (b) A. Komáromi, Z. Novák, Chem. Commun., I Curie-Weiss law in a wide temperature range because of 0.1 mmol of Cl FePc powder was pressed into a pellet. 6 71 16 4968-4970, (2008) (palladium on charcoal). (c) K. very weak exchange interaction between phthalocyanine The pellet and 0.8mmol (alkali metal/Cl FePc molar 2f 4f 16 Komura, H. Nakamura, Y. Sugi, J. Mol. Cat. A., 293, molecules. ratio x=8), 1.2 mmol (x=12), 1.6 mmol (x=16), 2.0 mmol 72-78 (2008) (palladium supported on MCM-41) (d) P. I One of the attempts to increase the TC of transition (x=20), or 2.4 mmol (x=24) of alkali metal (sodium or G. De Lima, O. A. Antunes, 49, 2505-2509 (2008). (e) metal phthalocyanine is the use of ferromagnetic potassium) chunks were placed in a Pyrex glass tube that 7 79 J. –H. Kim, D. –H. Lee, B. –H. Jun, Y. –S. Lee, surfaces as substrates, and several advances using this was subsequently sealed under vacuum (1x10-2 Pa). The 2g 4g Tetrahedron Lett., 48, 7079-7084 (2007) approach have been realized [4-6]. In addition, such sealed tube was placed in a conventional box furnace Cl Cl (polymer-support). (f) A. Cwik, Z. Hell, F. Figueras, organometallic molecules, which contain metal ions and maintained at 300, 350, 400, or 450 °C for 24 h 8 I 77 Tetrahedron Lett., 47, 3023-3026 (2006). (h) E. Tyrrell, with local magnetic moments, are important building before being allowed to cool naturally to room 2h 4h A. Al-Saardi, J. Millet, Synlett 487-488 (2005). (g) L. blocks for constructing metal containing magnetic temperature to provide products that will be called Djakovitch, P. Rollet, Adv. Synth. Catal., 346, Cl Cl carbon materials. as-prepared samples. The resultant black reaction 1782-1792 (2004) (zeolite). (h) L. Djakovitch, P. I Recently, various carbon materials (carbon onions, product was washed with distilled water to remove the 9 77 Rollet, Tetrahedron Lett., 45, 1367-1370 (2004) (zeolite). 2i 4i rods, and nanographite) have been successfully residual alkali metal and byproducts such as alkali metal (i) T. Fukuyama, M. Shinmen, S. Nishitani, M. Sato, I. synthesized by using a low energy process that employs chlorides. Finally, the resultant black powder was dried Ryu, Org. Lett. 4, 1691-1694 (2002) (ionic liquid). (j) T. Br highly chlorinated organic precursors (e.g., in air overnight. 10 1.4 Suzuka, K. Kimura, T. Nagamine, Polymer, 3, 621-639, 2j 4a hexachlorobenzene) as building blocks and an alkali The crystal structure of the reaction products was (2011). (k) Y. S. Feng, X. Y. Lin, J. Hao, H. –J. Xu, metal as a coupling reagent [7, 8]. Therefore, magnetic analyzed by standard powder X-ray diffraction (XRD) Tetrahedron, 34, 5249-5253 (2014). Br b carbon materials containing a transition metal can be methods by using the RIGAKU Ultima-III X-ray 11 1.6 [6] (a) T. Suzuka, K. Ooshiro, K. Kina Heterocycles 81, synthesized using highly chlorinated transition metal diffractmeter with Cu Kα monochromatic radiation. The 2j 4a 601-610 (2010); (b) T. Suzuka, T. Ngamine, K. Ogihara, a phthalocyanine molecules as the building blocks. The XPS studies were performed on a Kratos AXIS ULTRA All reactions were carried out using ArX (2; 0.4 mmol), M. Higa, Catal. Lett., 139, 85-89 (2010). resulting hybrid materials are expected to exhibit high X-ray photoelectron spectrometer, using Al Kα X-ray as phenylacetylene (3; 0.8 mmol), and Et3N (1.2 mmol) in the [7] For a review of terpyridine–metal complexes, see I. TC magnetic ordering in such phthalocyanine based an excitation source. Charge neutralization using low presence of the polymeric catalyst 1 in 3.0 mL of H2O at Eryazici, N. Moorefield, and R. Newkome, Chem. Rev., b carbon material (PBCM) involving local magnetic energy electrons provided for charge compensation. All 100 °C for 12 h under aerobic conditions. The reaction time 108, 1834-1895 (2008) and references therein. was 24 h. moments on the central metal ions which interact via the spectra were charge referenced to the graphite [8] After recycling experiments, ICP–AES analysis delocalized π electrons. From the point of view of carbon at 284.6 eV. Transmission electron microscopy showed that leaching of Pd to the aqueous solution was 4. SUMMARY technological applications for spintronic devices, it is (TEM) images were collected using a microscope (FEI 1.5 ppm (4.5 µg /3 mL). 0.21% of Pd catalysis (use of We developed a novel polymer-supported interesting to investigate the magnetism in PBCM [9, Tecnai G2 20) operated at 200 kV. Finally, the DC Pd: 0.020 mmol, 2.1 mg) eluted it to water. terpyridine–palladium complex that efficiently 10].In this paper, we report the synthesis of iron PBCM magnetization of a powder sample was measured with a catalyzes the Sonogashira coupling reaction by the reaction of highly chlorinated iron phthalocyanine SQUID magnetometer (Quantum Design MPMS-XL7) between an aryl halide and an acetylene (Received January 14, 2015; Accepted February 04, 2015) building blocks with an alkali metal coupling reagent, with a sample-space oven. The magnetization was