Pentafluorosulfanyl (SF5) in dyes: C3-Regioselective synthesis of α-mono-substituted subphthalocyanine with SF5-phenyl group

Accepted Manuscript Title: Pentafluorosulfanyl (SF5 ) in dyes: C3 -Regioselective synthesis of ␣-mono-substituted subphthalocyanine with SF5 -phenyl group Author: Norihito Iida Etsuko Tokunaga Norimichi Saito Norio Shibata PII: DOI: Reference:

S0022-1139(14)00243-7 http://dx.doi.org/doi:10.1016/j.jfluchem.2014.08.016 FLUOR 8408

To appear in:

FLUOR

Received date: Revised date: Accepted date:

3-8-2014 23-8-2014 25-8-2014

Please cite this article as: N. Iida, E. Tokunaga, N. Saito, N. Shibata, Pentafluorosulfanyl (SF5 ) in dyes: C3 -Regioselective synthesis of rmalphamono-substituted subphthalocyanine with SF5 -phenyl group, Journal of Fluorine Chemistry (2014), http://dx.doi.org/10.1016/j.jfluchem.2014.08.016 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

1

Journal of Fluorine Chemistry

Short communication

ip t

Pentafluorosulfanyl (SF5) in dyes: C3-Regioselective synthesis of α-mono-substituted subphthalocyanine with SF5-phenyl group Norihito Iida,1 Etsuko Tokunaga,2 Norimichi Saito3 and Norio Shibata1,2*

Department of Frontier Materials, 2Department of Nanopharmaceutical Sciences, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan, and 3Pharmaceutical Division, UBE INDUSTRIES LTD. Seavans North Bldg., 1-2-1 Shibaura, Minato-ku, Tokyo 105-8449, Japan

cr

1

us

*corresponding author: Norio Shibata, TEL +81-527357543; FAX +81-527357543; e-mail: [email protected]

an

Abstract: Pentafluorosulfanyl (SF5) is a unique fluorinated functional group. It has high lipophilicity and electronegativity, and is chemically and thermally stable. In addition, the steric hindrance of SF5 is larger than that of the trifluoromethyl (CF3) group. Therefore the introduction of SF5 group into functional dyes such as phthalocyanines and subphthalocyanines should be an attractive strategy to improve their robustness and alter their optical property. We attempted the C3-regioselective cyclotrimerization of aryl-substituted phthalonitriles 3 to provide subphthalocyanines (SubPcs) 1. α-Mono-substituted SubPc 1a was C3-regioselectively synthesized by introducing a bis(SF5)Ph group on the α-peripheral position providing 1a as a single isomer. The effect of the SF5 group on the synthesis and optical property of SubPcs were investigated by comparing with the H and CF3 analogues, 1b and 1c.

M

© 2014 Elsevier Science. All rights reserved

1. Introduction

d

Key words: fluorine; pentafluorosulfanyl; subphthalocyanine; aggregation; trifluoromethyl; regioselective

Ac ce p

te

Subphthalocyanines (SubPcs) are trimers of phthalonitrile with a singular conical structure [1]. These macrocycles have a three dimensional 14-π electron system which produces unique optical properties. Indeed, SubPcs have been considered as chromophores with potential applications in optical data storage, nonlinear optics, energy and electron transfer systems, among others [2]. These properties are highly dependent on the nature of 1) the axial functional groups and 2) the peripheral functional groups on the SubPc-rings, as well as their positions [1,2]. Functionalization of the axial moiety of SubPcs is wellstudied [3], while research of peripherally functionalized SubPcs is rather limited, especially phenyl group [1,4]. This fact is surprizing since examples of peripherally functionalized phenyl phthalocyanines (Pcs), tetramers of phthalonitrile, have been examined [5]. Recently, we have reported the first synthesis of trifluoroethoxy-coated SubPc and revealed its outstanding axial reactivity on the boron centre towards oxygen nucleophiles [6]. Thus, a variety of derivatives of trifluoroethoxy-coated SubPc can be easily accessed by the direct nucleophilic axial substitution reaction under very mild conditions. As part of our research on Pcs and SubPcs [6,7], we have focused on C3symmetrical SubPcs 1 having a phenyl group on their αperipheral positions (Figure 1). One of the defects of SubPcs is chemical instability [1,2]. SubPcs are often labile in the presence of a nucleophile under high temperature

conditions and decompose via ring-opening [1]. We envisaged that introduction of a pentafluorosulfanyl (SF5) functionalized phenyl ring into the α-peripheral positions of SubPcs should make their framework more robust. SF5substituted aryl compounds were first reported in the 1960 [8], but research on organic compounds having SF5 group was not so active until recent years [9]. The great success of trifluormethyl (CF3) organic compounds in pharmaceuticals, agrochemicals and material sciences [10] indicates the powerful potential of SF5 molecules in the future market of drugs and functional materials for improving and/or altering their original properties [9]. The SF5 group is considered to be a “super-trifluoromethyl (CF3) group”. The size, lipophilicity and electronegativity of the SF5 group are larger than those of CF3. More importantly, SF5 is thermally stable at temperatures exceeding 300 ºC, and is inert to a wide range of transformations such as hydrolysis under alkaline conditions [11]. In addition to the robust character of the SF5-aryl group, the 14-π space of SubPcs over the boron atom should be covered with a fluorophilic atmosphere, which renders the SubPcs as attractive functional molecules as molecular flasks and molecular capsules [12]. The potential of the biphenyl-like orientation of the SF5-aryl group to a SubPc skeleton might generate a chiral π space in the cleft of SubPc. We disclose herein the design and regioselective synthesis of novel SubPcs 1a having 3,5bis(SF5)Ph at α-peripheral positions. The bis(CF3)Ph and phenyl analogues 1b and 1c were also respectively synthesized for comparison (Figure 1). Complete

Page 1 of 7

2

Journal of Fluorine Chemistry

R

R R

N

N B

R R

R

N

Cl

N

R N

R

N

N 1a: R=SF5 1b: R=CF3 1c: R=H

N Cl

R

N

N

R

C3 symmetry

N B

2b: R=CF3 2c: R=H

R

cr

N

R

spectra. Pyridine inhibits aggregation by coordination on central metal of SubPc. If SubPc is aggregated, spectra is changed by addtion of a drop of pryridine. Therefore, all SubPcs 1a—c are free from aggregation in solution. The Qbands of 1a and 1b appeared at the same position of 578 nm, while the Q-band of 1c was red-shifted to 586 nm. These results indicate that the phenyl group of 1c should conjugate to the SubPc framework. On the other hand, due to the bulkiness of SF5 and CF3, the rotation of dihedral angles of the 3,5-bis(SF5)Ph group in 1a and the 3,5(CF3)Ph group in 1b is likely to be far from straight.

ip t

regioselectivity was achieved, providing 1a with a C3symmetry, while 1b and 1c were obtained as a mixture of C3-regioisomers 1b,c and C1-regioisomers 2b,c. To fortify the discussion, UV/Vis spectra of 1 were also taken.

C1 symmetry

us

Figure 1. Regioisomers of SubPcs 1 with α-peripheral aryl groups.

Ac ce p

te

d

M

The synthesis of 1 was achieved as follows. The cyclotrimerization of 3’,5’-bis-pentafluorosulfanylbiphenyl-2,3-dicarbonitrile 3a [7f] to 1a required a solution of trichloroborane in 1.0 M of p-xylene under reflux. SubPc 1a, having 3,5-bis(SF5)Ph, was obtained in 15% yield (Table 1, entry 1). Generally, a mono-substituted SubPc is generated as a mixture of C3 and C1 regioisomers. The 1H NMR spectrum of 1a showed simple peaks which was indicated that 1a is a single isomer. On the other hand, the CF3 analogue 1b and unsubstituted 1c were produced as mixtures of regioisomers 2b,c by the trimerization reaction of 3b,c. Their 1H NMR spectra were complicated (entries 2 and 3). The regioselectivity observed for the cyclotrimerization to 1a can be explained by the steric hindrance of the SF5 group.

an

2. Results and Discussion

Table 1. Cyclotrimerization of 3 to SubPcs 1. R

R

BCl3 (3.6 eq.)

CN

p-xylene, reflux

1a-c

+

C 3 symmetry

2a-c

C 1 symmetry

CN

3a-c

entry 1 2 3 a b

3

R

Product

Yield (%)

3a 3b 3c

SF5 CF3 H

1a 1b+2ba 1c+2cb

15 47 12

1b and 2b can be separated by silica-gel column chromatography. 1c and 2c are difficult to separate by silica-gel column

chromatography.

The UV/Vis spectra of SubPcs 1 were analyzed to investigate the effect of fluorine functional groups (Figure 2). The spectra of 1c were taken as a mixtue with 2c. The positions of Q-bands in different concentrations, even in the presence of one drop of pyridine (approximately 100fold excess relative to SubPc), appeared the same in all

Figure 2. a) UV/Vis spectra of 1a (blue: 1.0 × 10-4 M, pink: 1.0 × 105

M, green: 1.0 × 10-6 M, purple: 1.0 × 10-4 M + one drop of pyridine)

Page 2 of 7

3

Journal of Fluorine Chemistry in dichloromethane. b) UV/Vis spectra of 1b as a mixture with 2b (blue: 1.0 × 10-4 M, pink: 1.0 × 10-5 M, green: 1.0 × 10-6 M, purple: 1.0 × 10-4 M + one drop of pyridine) in dichloromethane. c) UV/Vis spectra of 1c as a mixture with 2c (blue: 1.0 × 10-4 M, pink: 1.0 ×

bis(SF5)Ph group is 40º. Hence, the SubPc and the 3,5bis(SF5)Ph conjugate to each other with difficulty, which supports the expected structure from the results of the UV/Vis spectra of 1a and 4 (Figure 4).

10-5 M, green: 1.0 × 10-6 M, purple: 1.0 × 10-4 M + one drop of pyridine) in dichloromethane. d) UV/Vis spectra of 1a (blue: 1.0 ×10-4 M), 1b (green: 1.0 × 10-4 M), and 1c (pink: 1.0 × 10-4 M) in

F5 S

cr us

Finally, the β-substituted bis(SF5)Ph analogue, SubPc 4 was synthesized to investigate the effect of the substituted position. 3',5'-Bis-pentafluorosulfanyl-biphenyl-3,4dicarbonitrile 5 [7f] was trimerized with BCl3 in p-xylene solution in 15% yield as a mixture of two regioisomers. The solubility of 4 was pretty high but poorer than that of 1a.

ip t

dichloromethane.

Figure 4. Estimated 3D structures of 1a generated by computation. Left: Top view; Right: Side view.

SF5

3. Conclusion SF5

N CN

F5 S

CN

BCl3 (3.6 eq.)

N

pxylene, reflux

F5 S

N B

N N

N

SF5

15% yield SF5

Scheme 1. Synthesis subphthalocyanine 10.

of

SF5

4

β-substituted

M

5

We report on the design and synthesis of SF5-aryl substituted subphthalocyanine 1. C3-Regioselective synthesis of 1 was successful by introducing a bis(SF5)Ph group to the α-position on the parent SubPc. In the case of the bis(CF3)Ph group and the phenyl group, the regioselectivity for the cyclization to 1 is lost. Investigation of the UV/Vis spectra of 1 and β-substituted analogue 4 reveals that the conjugation between peripheral phenyl groups with a parent SubPc π-system is prevented due to the steric hindrance of SF5 and CF3groups. Further study of the effect of SF5 group in dyes is under investigation [13].

an

Cl

3,5-bis(SF5)Ph

Ac ce p

te

d

The UV/Vis spectra of 4 in dichloromethane solution at different concentrations were next investigated (Figure 3). The Q-bands appeared at the same position regardless of the differences in concentration. Hence, SubPc 4 does not aggregate in solution. The Q-bands of 4 and 1a are almost the same (4: 575 nm, 1a: 578 nm). This result supports the notion that bis(SF5)Ph and the isoindoline unit of the SubPc framework in 1a are not in the same plane and that the phenyl group does not conjugate with π-electrons of the parent SubPc.

Figure 3. UV/Vis spectra of SubPc 4 as a mixture of regioisomer (blue: 1.0 × 10-4 M , pink: 1.0 × 10-5 M, green: 1.0 × 10-6 M , purple: 1.0 × 10-4 M + one drop of Pyridine) in dichloromethane.

An estimated 3D molecular structure of 1a generated by computation (DFT/B3LYP/6-31G*) shows that the dihedral angle of the phenyl plane of SubPc having a bulky 3,5-

Experimental General procedure for synthesis of subphthalocyanine BCl3 (0.789 mmol, 1.0 M solution in p-xylene) was added to phthalonitrile (0.219 mmol) under an argon atmosphere. The reaction mixture was stirred under reflux for 6 h. The purple solution was then flushed with argon. Water was added to the reaction mixture and was extracted with AcOEt three times. The organic layer was washed with brine and dried over Na2SO4. The solvent was evaporated and the resultant purple solid was purified by silica-gel column chromatography (eluent: 1a Hex / AcOEt = 90 / 10, 1b Hex / AcOEt = 70 / 30, 1c Hex / AcOEt = 80 / 20, 4 Hex / AcOEt = 90 / 10) to furnish 1a (15% yield), 1b (47% yield), 1c (12% yield), 4 (15% yield). Chloro-[1,8,15-tris(3',5'-Bis-pentafluorosulfanylphenyl)-subphthalocyaninato]boron (III) (1a) 1 H NMR (300 MHz, CDCl3): δ = 7.96 (d, 3H, J = 6.9 Hz), 8.05(t, 3H, J = 7.5 Hz), 8.47 (s, 3H), 8.61 (d, 3H, J = 8.4 Hz), 8.80 (s, 6H) 19 F NMR (282 MHz, CDCl3): δ = -148.2 (quintet, 6F, SF, J = 150 Hz), -167.11 (d, 24F, SF4, J = 150 Hz) IR (KBr): 3853, 3734, 3410, 3120, 2973, 2881, 1653, 1558, 1447, 1256, 1196, 1138, 1101, 850, 761, 661, 574 cm-1 MALDI-TOF MASS: m/z = 1415.6―1418.6 ([M]+, isotopic pattern)

Page 3 of 7

4

Journal of Fluorine Chemistry

Rf = 0.5 (Hex / AcOEt =9 / 1)

[4]

[5]

Ac ce p

te

d

Chloro-[2(3),9(10),16(17)-tris(3',5'-Bispentafluorosulfanyl-phenyl)subphthalocyaninato]boron (III) (4) 1 H NMR (300 MHz, CDCl3): δ = 7.92―8.04 (m, 6H), 8.08―8.22 (m, 6H) 8.27 (s, 2H), 8.37―8.38 (m, 2H), 9.07―9.09 (m, 1H), 9.15 (s, 1H) 19 F NMR (282 MHz, CDCl3): δ = -148.5―150.9 (m, 6F, SF), -167.1―-167.6 (m, 24F, SF4) IR (KBr): 3853, 3735, 2649, 3446, 3116, 2933, 2873, 1717, 1654, 1558, 1457, 1558, 1457, 1185, 1139, 811, 730, 660, 597 cm-1 MALDI-TOF MASS: m/z = 1412.8―1416.8 ([M]+, isotopic pattern) Rf = 0.4 (Hex / AcOEt = 9 /1)

[6]

[7]

Acknowledgements

This research was financially supported in part by the Platform for Drug Discovery, Informatics, and Structural Life Science, and Scientific Research (B) (25288045) from MEXT Japan, Exploratory Research (25670055). References and Notes [1]

[2]

a) N. Kobayashi, in The Porphyrin Handbook, Vol. 15 (Eds.: K. M. Kadish, K. M. Smith, R. Guilard), Academic Press, San Diego, (2003) pp. 161―262. b) C. G. Claessens, D. González-Rodríguez, T. Torres, Chem. Rev. 102 (2002) 835―853. c) C. G. Claessens, D. González-Rodríguez, M. S. Rodríguez-Morgade, A. Medina, T. Torres, Chem. Rev. 114 (2014) 2192―2277. a) A. Sastre, T. Torres, M. A. Díaz-García, F. AgullóLópez, C. Dhenaut, S. Brasselet, I. Ledoux, J. Zyss, J. Am. Chem. Soc. 118 (1996) 2746―2747. b) B. del Rey, U.

cr

us

an

[3]

M

Chloro-[1(4),8(11),15(18)-tris-phenylsubphthalocyaninato]boron (III) (1c) 1 H NMR (300 MHz, CDCl3): δ = 7.29―7.37 (m, 5H), 7.66―7.76 (m, 5H), 7.82―7.99 (m, 5H), 8.15―8.21 (m, 3H), 8.37―8.45 (m, 3H), 8.84―8.93 (m, 3H) IR (KBr): 3734, 3056, 3025, 2956, 2666, 1455, 1427, 1244, 1192, 1133, 963, 814, 750, 699, 581 cm-1 MALDI-TOF MASS: m/z = 658.7―663.0 ([M] +, isotopic pattern) Rf = 0.4 (Hex /AcOEt = 8 / 2)

ip t

Chloro-[1(4),8(11),15(18)-tris(3',5'-Bis-trifluoromethylphenyl)-subphthalocyaninato]boron (III) (1b) 1 H NMR (300 MHz, CDCl3): δ = 7.76―7.83 (m, 3H), 7.98―8.12 (m, 6H) 8.15―8.23 (m, 3H), 8.62―8.67 (m, 3H), 9.01―9.08 (m, 3H) 19 F NMR (282 MHz, CDCl3): δ = -62.87 (s, 10F), -62.88 (s, 4F), -63.15 (s, 4F) IR (KBr): 3853, 3649, 3080, 2965, 2877, 1623, 1457, 1380, 1281, 1176, 1133, 899, 786, 706, 583 cm-1 MALDI-TOF MASS: m/z = 1065.7―1072.1 ([M]+, isotopic pattern) Rf = 0.4 (Hex /AcOEt = 7 / 3)

Keller, T. Torres, G. Rojo, F. Agulló-López, S. Nonell, C. Martí, S. Brasselet, I. Ledoux, J. Zyss, J. Am. Chem. Soc. 120 (1998) 12808―12817. c) G. Martín, G. Rojo, F. Agulló-López, V. R. Ferro, J. M. G. de la Vega, M. V. Martínez-Díaz, T. Torres, I. Ledoux, J. Zyss, J. Phys. Chem. B. 106 (2002) 13139―13145. d) C. G. Claessens, D. González-Rodríguez, T. Torres, G. Martín, F. AgullóLópez, I. Ledoux, J. Zyss, V. R. Ferro, J. M. G. de la Vega, J. Phys. Chem. B 109 (2005) 3800―3806. e) G. Bottari, G. de la Torre, D. M. Guldi, T. Torres, Chem. Rev. 110 (2010) 6768―6816. f) J-Y. Liu, H.-S. Yeung, W. Xu, X. Li, D. K. P. Ng, Org. Lett. 10 (2008) 5421―5424. g) F. Camerel, G. Ulrich, P. Retailleau, R. Ziessel, Angew. Chem. Int. Ed. 47 (2008) 8876―8880 h) Raymond Ziessel, G. Ulrich, K. J. Elliott, A. Harriman, Chem. Eur. J. 15 (2009) 4980―4984. i) M. E. El-Khouly, D. K. Ju, K.-Y. Kay, F. D’Souza, S. Fukuzumi, Chem. Eur. J. 16 (2010) 6193―6202. a) T. Kato, F. S. Tham, P. D. W. Boyd, C. A. Reed. Heteroatom.Chem. 17 (2006) 209―216. b) J. Guilleme, D. González-Rodríguez, T. Torres, Angew. Chem. Int. Ed. 50 (2011) 3506―3509. c) M. V. Fulford, D. Jaidka, A. S. Paton, G. E. Morse, E. R. L. Brisson, A. J. Lough, T. P. Bender J. Chem. Eng. Data 57 (2012) 2756―2765. d) G. E. Morse, T. P. Bender, Inorg. Chem. 51 (2012) 6460―6467. a) D. González-Rodríguez T. Torres, Eur. J. Org. Chem. (2009), 1871―1879. b) D. Dini, S. Vagin, M. Hanack, V. Amendolab, M. Meneghetti, Chem. Commun. (2005) 3796―3798. a) T. Sugimori, S. Okamoto, N. Kotoh, M. Handa, K. Kasuga, Chem. Lett. (2000) 1200―1201. b) V. Aranyos, A. M. Castaño, H. Grennberg, Acta Chemica Scand. 53 (1999) 714―720. c) N. Kobayashi, T. Fukuda, K. Ueno, H. Ogino, J. Am. Chem. Soc. 123 (2001) 10740―10741. d) G. A. Selivanova, E. V. Amosov, L. I. Goryunov, S. V. Balina, V. G. Vasil’ev, G. E. Sal’nikov, E. A. Luk’yanets, and V. D. Shteingarts, Russian J. Org. Chem. 47 (2011) 1240―1246. a) B. Das, E. Tokunaga, N. Shibata, N. Kobayashi, J. Fluorine Chem. 131 (2010) 652―654. b) N. Shibata, B. Das, E. Tokunaga, M. Shiro, N. Kobayashi, Chem. Eur. J. 16 (2010) 7554―7562. a) M. Ramesh Reddy, N. Shibata, Y. Kondo, S. Nakamura, T. Toru, Angew. Chem. Int. Ed. 45 (2006) 8163―8166. b) H. Yoshiyama, N. Shibata, T. Sato, S. Nakamura, T. Toru, Chem. Commun. (2008) 1977―1979. c) H. Yoshiyama, N. Shibata, T. Sato, S. Nakamura, T. Toru, Org. Biomol. Chem. 7 (2009) 2265―2269. d) B. Das, M. Umeda, E. Tokunaga, T. Toru, N. Shibata, Chem. Lett. 39 (2010), 337―339. e) N. Shibata, S. Mori, M. Hayashi, M. Umeda, E. Tokunaga, M. Shiro, H. Sato, T. Hoshi, N. Kobayashi, Chem. Commun. 50 (2014) 3040―3043. f) N. Iida, E. Tokunaga, N. Saito, N. Shibata, J. Fluorine Chem. submitted. G. A. Silvey, G. H. Cady, J. Am. Chem. Soc. (1950) 3624―3626. S. Altomonte, M. Zanda, J. Fluorine Chem. 143 (2012) 57―93. a) K. Muller, C. Faeh, F. Diederch, Science 317 (2007) 1881―1886. b) T. Furuya, A. S. Kamlet, T. Ritter, Nature, 473 (2011) 470―477. c) T. Liang, C. N. Neumann, T. Ritter, Angew. Chem. Int. Ed. 52 (2013) 8214―8264. d) V. V. Grushin, Acc. Chem. Res. 43 (2010) 160―171. a) W. A. Sheppard, J. Am. Chem. Soc. 84 (1962) 3072―3076. b) R. D. Bowden, P. J. Comina, M. P. Greenhall, B. M. Kariuki, A. Loveday, D. Philp, Tetrahedron 56 (2000) 3399―3408. c) P. Kirsch, M.

[8] [9] [10]

[11]

Page 4 of 7

5

Journal of Fluorine Chemistry [12]

[13]

a) A. Szumna, Chem. Soc. Rev. 39 (2010) 4274―4285. b) C. G. Claessens, T. Torres, J. Am. Chem. Soc. 124 (2002) 14522―14523. c) C. G. Claessens, T. Torres, Chem. Commu. (2004) 1298―1299. This paper is a series of our works of “SF5 in Dyes”. The part 1 has been submitted. See reference 7f.

Ac ce p

te

d

M

an

us

cr

ip t

Bremer, M. Heckmeier, K. Tarumi, Angew. Chem. Int. Ed. 38 (1999) 1989―1992. d) A. M. Sipyagin, V. S. Enshov, S. A. Kashtanov, C. P. Bateman, B. D. Mullen, Y.-T. Tan, J. S. Thrasher, J. Fluorine Chem. 125 (2004) 1305―1316. e) T. Moa, X. Mi, E. E. Milner, G. S. Dowc, P. Wipf, Tetrahedron Lett. 51 (2010) 5137―5140.

Page 5 of 7

6

Journal of Fluorine Chemistry

Graphical Abstract Pentafluorosulfanyl (SF5) in dyes: C3Regioselective synthesis of α-monosubstituted subphthalocyanine with SF5phenyl group

R

3

N

R

N

N B

Cl

N

R N

N B

N Cl

R

N

N

R

C3 symmetry

R

N

N 1a: R=SF5 1b: R=CF3 1c: R=H

R R

R

N

R

2b: R=CF3 2c: R=H

C1 symmetry

Ac ce p

te

d

M

an

us

Norihito Iida, Etsuko Tokunaga, Norimichi Saito and Norio Shibata1,2 The pentafluorosulfanyl (SF5) group is one of the most attractive, but unexploited fluorinated functional groups. We disclose the regioselective synthesis of α-mono-substituted subphthalocyanine with bis(SF5)Ph on the α-position. The effect of the SF5 moiety was investigated by comparison with CF3 and H analogues.

ip t

2

cr

1

R

R

Page 6 of 7

7

Journal of Fluorine Chemistry Highlights

Subphthalocyanine having Ph(SF5)2 group on αposition was synthesized.

ip t

The effect of SF5 on subphthalocyanine was investigated by comparison with CF3. The SF5 moiety enables regioselective synthesis, while CF3 cannot.

Ac ce p

te

d

M

an

us

cr

Bulky SF5 group controls dihedral angle of the phenyl plane of subphthalocyanine.

Page 7 of 7