Release and catch catalysis by tungstate species for the oxidative cleavage of olefins

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1 Electronic Supplementry Mteril (ESI) for Ctlysis Science & Technology. This journl is The Royl Society of Chemistry 2017 Electronic supplementry informtion (ESI) for Relese nd ctch ctlysis by tungstte species for the oxidtive clevge of olefins Yu Yoshimur, Yoshiyuki gswr,* Kosuke Suzuki, Kzuy Ymguchi* nd Noritk Mizuno* Deprtment of Applied Chemistry, School of Engineering, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo , Jpn. E-mil: Dt of oxidized products 6-xo-heptnoic cid (2) (CAS No ) S1,S2 CH GC (InertCp FFAP cpillry column, 0.25 mm 30 m, GL Science Inc.): initil column temp. (80 C, 2 min), finl column temp. (250 C, 6 min), progress rte (10 C min 1 ), injection temperture (250 C), detection temperture (250 C), retention time (18.6 min). MS (EI): (%): 144 (1) [M + ], 126 (35), 111 (10), 101 (32), 98 (26), 84 (25), 83 (25), 73 (30), 71 (16), 69 (14), 59 (21), 58 (97), 57 (10), 56 (25), 55 (100). 1 H NMR (500 MHz, CDCl 3, TMS): (m, 4H), 2.16 (s, 3H), (m, 2H), (m, 2H), (brs, 1H). 13 C { 1 H} NMR (125 MHz, CDCl 3, TMS): 23.1, 24.1, 30.0, 33.8, 43.3, 179.2, Methyl-1,2-cyclohexnediol (4) (CAS No ) S1,S3 H H GC (InertCp FFAP cpillry column, 0.25 mm 30 m, GL Science Inc.): initil column temp. (80 C, 2 min), finl column temp. (250 C, 6 min), progress rte (10 C min 1 ), injection temperture (250 C), detection temperture (250 C), retention time (12.7 min). MS (EI): (%): 130 (7) [M + ], 112 (22), 97 (26), 84 (16), 83 (12), 71 (100), 70 (47), 69 (23), 68 (10), 58 (43), 57 (26), 56 (12), 55 (24). Adipic cid (2b) (CAS No ) S1,S4 HC CH GC (InertCp FFAP cpillry column, 0.25 mm 30 m, GL Science Inc.): initil column temp. (40 C, 3 min), finl column temp. (250 C, 20 min), progress rte (10 C min 1 ), injection temperture (250 C), detection S1

2 temperture (250 C), retention time (34.2 min). MS (EI): (%): 128 (5), 100 (100), 87 (30), 82 (13), 73 (25), 69 (34), 60 (39), 58 (11), 56 (11), 55 (56), 54 (14). Benzoic cid (2c) (CAS No ) S1,S4,S5 CH (250 C), retention time (17.7 min). MS (EI): (%): 122 (84) [M + ], 105 (100), 77 (76), 51 (34), 50 (20). Benzldehyde (CAS No ) S1,S4,S6 CH (250 C), retention time (8.2 min). MS (EI): (%): 106 (98) [M + ], 105 (95), 78 (17), 77 (100), 52 (12), 51 (47), 50 (26). 1-Phenylethne-1,2-diol (CAS No ) S1,S4,S6 H H (250 C), retention time (18.7 min). MS (EI): (%): 138 (2) [M + ], 120 (21), 107 (37), 106 (30), 105 (35), 104 (12), 92 (26), 91 (100), 79 (32), 78 (16), 77 (60), 65 (25), 63 (12), 51 (34), 50 (18). Acetophenone (2d) (CAS No ) S1,S4,S7 GC (InertCp 5 cpillry column, 0.25 mm 30 m, GL Science Inc.): initil column temp. (80 C, 2 min), finl column temp. (280 C, 8 min), progress rte (10 C min 1 ), injection temperture (280 C), detection temperture (280 C), retention time (5.6 min). MS (EI): (%): 120 (34) [M + ], 105 (100), 77 (79), 51 (28), 50 (11). S2

3 2-Phenylpropionldehyde (CAS No ) S1,S4,S8 CH GC (InertCp 5 cpillry column, 0.25 mm 30 m, GL Science Inc.): initil column temp. (80 C, 2 min), finl column temp. (280 C, 8 min), progress rte (10 C min 1 ), injection temperture (280 C), detection temperture (280 C), retention time (6.1 min). MS (EI): (%): 134 (12) [M + ], 106 (11), 105 (100), 103 (15), 79 (23), 77 (21), 51 (10). Heptnoic cid (2e) (CAS No ) S1,S4,S9 CH (250 C), retention time (12.9 min). MS (EI): (%): 130 (0.2) [M + ], 101 (7), 87 (24), 73 (50), 71 (33), 70 (17), 61 (12), 60 (100), 55 (29). Heptnl (CAS No ) S1,S4,S10 CH (250 C), retention time (3.8 min). MS (EI): (%): 114 (1) [M + ], 96 (14), 86 (18), 81 (28), 72 (12), 71 (30), 70 (100), 68 (19), 67 (11), 57 (55), 55 (64). Hexnoic cid (2f) (CAS No ) S1,S4,S11 CH (250 C), retention time (11.8 min). MS (EI): (%): 87 (15), 73 (49), 61 (10), 60 (100), 57 (10), 56 (11), 55 (15). Hexnl (CAS No ) S1,S4,S12 CH S3

4 (250 C), retention time (2.9 min). MS (EI): (%): 100 (0.5) [M + ], 82 (21), 72 (27), 71 (11), 67 (15), 58 (12), 57 (66), 56 (100), 55 (22). Phenylcetic cid (CAS No ) S1,S13 CH (250 C), retention time (18.7 min). MS (EI): (%): 136 (35) [M + ], 92 (21), 91 (100), 65 (18). Phthlic cid (2h) (CAS No ) CH CH HPLC (Inertsil DS-3 column, 4.6 mm 250 mm, GL Science Inc.): eluent (CH 3 H/H 2, 9/1 v/v, 0.4 ml min 1 ), oven temp. (40 C), retention time (7.7 min). 1,4-Nphthoquinone (CAS No ) HPLC (Inertsil DS-3 column, 4.6 mm 250 mm, GL Science Inc.): eluent (CH 3 H/H 2, 9/1 v/v, 0.4 ml min 1 ), oven temp. (40 C), retention time (9.3 min). 2,3-Nphthlenedicrboxylic cid (2i) (CAS No ) CH CH HPLC (Inertsil DS-3 column, 4.6 mm 250 mm, GL Science Inc.): eluent (CH 3 H/H 2, 9/1 v/v, 0.4 ml min 1 ), oven temp. (40 C), retention time (25.6 min). S4

5 Anthrquinone (CAS No ) S1,S4,S14 GC (InertCp 5 cpillry column, 0.25 mm 30 m, GL Science Inc.): initil column temp. (80 C, 2 min), finl column temp. (280 C, 8 min), progress rte (10 C min 1 ), injection temperture (280 C), detection temperture (280 C), retention time (20.1 min). MS (EI): (%): 209 (17), 208 (96) [M + ], 207 (13), 181 (13), 180 (90), 153 (12), 152 (100), 151 (47), 150 (24), 126 (14), 77 (11), 76 (52), 75 (22), 74 (18), 63 (13), 50 (33). Additionl references S1 Spectrl dt were obtined from Wiley Subscription Services, Inc. (US). S2 F. Foubelo, F. Lloret nd M. Yus, Tetrhedron, 1992, 48, S3 C. Döbler, G. M. Mehltretter, U. Sundermeier nd M. Beller, J. Am. Chem. Soc., 2000, 122, S4 SDBSWeb, (Ntionl Institute of Advnced Industril Science nd Technology, ccessed Jnury 2017). S5 N. Td, K. Httori, T. Nobut, T. Miur nd A. Itoh, Green Chem., 2011, 13, S6 A. Wng nd H. Jing, J. rg. Chem., 2010, 75, S7 P. B. Brondni, H. M. Dudek, C. Mrtinoli, A. Mttevi nd M. W. Frije, J. Am. Chem. Soc., 2014, 136, S8 Y.-D. Du, C.-W. Tse, Z.-J. Xu, Y. Liu nd C.-M. Che, Chem. Commun., 2014, 50, S9 S. Bernhrdt, A. Metzger nd P. Knochel, Synthesis, 2010, S10 M. E. González-Núñez, R. Mello, A. lmos, R. Acerete nd G. Asensio, J. rg. Chem., 2006, 71, S11 A. Boteztu, B. S. Kemp nd G. J. Pickering, Molecules, 2016, 21, S12 J. K. Ptr, G. Ds nd K.-H. Bek, Molecules, 2015, 20, S13 M. S. Gchet,. Kunert, M. Kiser, R. Brun, R. A. Muñoz, R. Buer nd W. Schühly, J. Nt. Prod., 2010, 73, 553. S14 K. S. Jng, H. Y. Shin nd D. Y. Chi, Tetrhedron, 2008, 64, S5

6 (b) [H 3 W 4 ( 2 )] [H 5 W 5 ( 2 )] [H 3 W 3 ( 2 ) 2 ] [HW 2 ( 2 ) 2 ] [HW( 2 ) 3 ] [HW 2 3 ( 2 ) 4 ] [W 2 2 ( 2 ) 4 t Bu] [HW 3 4 ( 2 ) 6 ] [HW 4 5 ( 2 ) 8 ] Fig. S1 CSI-mss spectr (negtive-ion mode) of the rection filtrtes nd their ssignments. Rection conditions: t BuH (1.5 ml), 30% queous H 2 2 (2.5 mmol), 80 C, 1 h, W 3 (50 µmol), nd (b) W/Zn Sn 2 (100 mg). The signl sets t 280.9, 282.9, 296.9, 298.9, 300.9, 544.9, 600.9, 808.8, nd were ssignble to [HW 2 ( 2 ) 2 ], [H 3 W 4 ( 2 )], [HW( 2 ) 3 ], [H 3 W 3 ( 2 ) 2 ], [H 5 W 5 ( 2 )], [HW 2 3 ( 2 ) 4 ], [W 2 2 ( 2 ) 4 t Bu], [HW 3 4 ( 2 ) 6 ], nd [HW 4 5 ( 2 ) 8 ], respectively. S6

7 Rmn Shift (cm 1 ) Fig. S2 Rmn spectrum of the precipitte obtined fter the rection in Fig. 1 (see Fig. 1c). [HW 6 19 ] Fig. S3 CSI-mss spectrum (negtive-ion mode) of the filtrte of the solution fter the rection for entry 2, Tble 1. The signl set t ws ssignble to [HW 6 19 ]. S7

8 (b) Sn 2 (JCPDS ) (c) (d) Si 2 (JCPDS ) W 3 (JCPDS ) (degree) Fig. S4 XRD ptterns of W/Sn 2, (b) Sn 2, nd (c) W/Si 2 nd (d) Si 2. (b) (c) (d) Rmn Shift (cm 1 ) Fig. S5 Rmn spectr of W/Sn 2, (b) Sn 2, nd (c) W/Si 2 nd (d) Si 2. S8

9 (b) (c) Sn 2 (JCPDS ) W 3 (JCPDS ) (degree) Fig. S6 XRD ptterns of W/Zn Sn 2, (b) Zn Sn 2, nd (c) Sn 2. (b) (c) Rmn Shift (cm 1 ) Fig. S7 Rmn spectr of W/Zn Sn 2, (b) Zn Sn 2, nd (c) Sn 2. The spectrum of Zn Sn 2 hs signl t 1050 cm 1 which is ssignble to the (N 3 ) vibrtion derived from Zn(N 3 ) 6H 2. S9

10 W/Zn Sn H 2, H 2 2 t BuH, 80 C CH H CH : Yield of 3 : Yield of 2 : Yield of 4 : Yield of 5 : Yield of 6 Yield (%) Time (h) Fig. S8 Rection profile for the W/Zn Sn 2 -ctlyzed oxidtive clevge of 3 into 2 using H 2 2 s the oxidnt. Rection conditions: 3 (0.5 mmol), W/Zn Sn 2 (100 mg, W: 10 mol% with respect to 3), 30% queous H 2 2 (2.0 mmol), t BuH (1.5 ml), H 2 (2.2 mmol), nd 80 C. Yields were determined by GC nlysis using o- dichlorobenzene s n internl stndrd. H W/Zn Sn 2, H H t BuH, 80 C 2 CH : Yield of 4 : Yield of 2 Yield (%) Time (h) Fig. S9 Rection profile for the W/Zn Sn 2 -ctlyzed oxidtive clevge of 4 into 2 using H 2 2 s the oxidnt. Rection conditions: 4 (0.5 mmol), W/Zn Sn 2 (100 mg, W: 10 mol% with respect to 3), 30% queous H 2 2 (2.0 mmol), t BuH (1.5 ml), H 2 (2.2 mmol), nd 80 C. Yields were determined by GC nlysis using o- dichlorobenzene s n internl stndrd. S10

11 6 W/Zn Sn 2, H 2 2 t BuH, 80 C 2 CH : Yield of 6 : Yield of 2 +: Yield of 7 Yield (%) Time (h) Fig. S10 Rection profile for the W/Zn Sn 2 -ctlyzed oxidtive clevge of 6 into 2 using H 2 2 s the oxidnt. Rection conditions: 2 (0.5 mmol), W/Zn Sn 2 (100 mg, W: 10 mol% with respect to 3), 30% queous H 2 2 (2.0 mmol), t BuH (1.5 ml), H 2 (2.2 mmol), nd 80 C. Yields were determined by GC nlysis using o- dichlorobenzene s n internl stndrd. S11

12 Tble S1 Decomposition of H 2 2 in the presence of vrious supports Entry Support Decomposition of H 2 2 (%) 1 Sn Si Al Zr 2 >99 5 Ti 2 >99 6 Zn >99 7 Mg >99 Rection conditions: Support (100 mg), 30% queous H 2 2 (2.5 mmol), t BuH (1.5 ml), 80 C, 1 h. The mounts of remining H 2 2 were determined by Ce 3+/4+ titrtion. Tble S2 Effect of rection tempertures on the W/Zn Sn 2 -ctlyzed oxidtive clevge of 1 with H 2 2 W/Zn Sn 2 1 H 2 2, t BuH 2 CH Entry Temperture ( C) Yield (%) Tungsten leching (%) < <1 Rection conditions: 1 (0.5 mmol), W/Zn Sn 2 (W: 9.1 wt%, Zn: 0.7 wt%, 125 mg), 30% queous H 2 2 (2.5 mmol), t BuH (1.5 ml), 24 h. Yields were determined by GC nlysis using o-dichlorobenzene s n internl stndrd. Tungsten leching ws determined by ICP-AES nlysis. S12

13 Tble S3 Effect of solvents on the W/Zn Sn 2 -ctlyzed oxidtive clevge of 1 with H W/Zn Sn 2 H 2 2, 80 C 2 CH Entry Solvent Yield (%) Tungsten leching (%) 1 t BuH 83 <1 2 CH 3 CN EtAc 47 <1 4 DMC 35 <1 5 H Rection conditions: 1 (0.5 mmol), W/Zn Sn 2 (W: 9.1 wt%, Zn: 0.7 wt%, 125 mg), 30% queous H 2 2 (2.5 mmol), solvent (1.5 ml), 80 C, 24 h. Yields were determined by GC nlysis using o-dichlorobenzene s n internl stndrd. Tungsten leching ws determined by ICP-AES nlysis. Tble S4 Effect of the mounts of supported zinc species on the W/Zn Sn 2 -ctlyzed oxidtive clevge of 1 with H W/Zn Sn 2 H 2 2, t BuH 80 C 2 CH Entry Zn loding (wt%) Yield (%) Tungsten leching (%) < < < < < <1 Rection conditions: 1 (0.5 mmol), W/Zn Sn 2 (W: 9.1 wt%, 125 mg), 30% queous H 2 2 (2.5 mmol), t BuH (1.5 ml), 80 C, 24 h. Yields were determined by GC nlysis using o-dichlorobenzene s n internl stndrd. Tungsten leching ws determined by ICP-AES nlysis. S13

14 Tble S5 Effect of the mounts of supported tungsten species on the W/Zn Sn 2 -ctlyzed oxidtive clevge of 1 with H W/Zn Sn 2 H 2 2, t BuH 80 C 2 CH Entry W loding (wt%) Yield (%) Tungsten leching (%) 1 0 < < < < < Rection conditions: 1 (0.5 mmol), W/Zn Sn 2 (Zn: 0.9 wt%, 125 mg), 30% queous H 2 2 (2.5 mmol), t BuH (1.5 ml), 80 C, 24 h. Yields were determined by GC nlysis using o-dichlorobenzene s n internl stndrd. Tungsten leching ws determined by ICP-AES nlysis. Tble S6 Effect of the mounts of W/Zn Sn 2 on the oxidtive clevge of 1 with H W/Zn Sn 2 H 2 2, t BuH 80 C 2 CH Entry Amount of the ctlyst (mg) Yield (%) Tungsten leching (%) 1 0 < < < <1 Rection conditions: 1 (0.5 mmol), W/Zn Sn 2 (W: 9.1 wt%, Zn: 0.9 wt%), 30% queous H 2 2 (2.5 mmol), t BuH (1.5 ml), 80 C, 24 h. Yields were determined by GC nlysis using o-dichlorobenzene s n internl stndrd. Tungsten leching ws determined by ICP-AES nlysis. S14

15 Tble S7 Detiled comprison of W/Sn 2 nd W/Zn Sn 2 for the oxidtive clevge rection of 1 into 2 Entry 1 Ct. Ct., H 2 2 t BuH, 80 C Time (h) H CH H CH Conv. Yield (%) (%) W/Sn 2 4 >99 36 < >99 64 <1 10 < W/Zn Sn 2 4 >99 44 < >99 92 <1 3 <1 < TBHP (mmol) Rection conditions: 1 (0.5 mmol), Ctlyst (100 mg, W: 10 mol% with respect to 1), 30% queous H 2 2 (2.5 mmol), t BuH (1.5 ml), 80 C. Yields were determined by GC nlysis using o-dichlorobenzene s n internl stndrd. S15