Supplementary Material
Synthesis of titanium containing helical silicates for catalytic oxidation of alkenes
Xiaoyong Li1 · Benhua Huang1 · Le Li1 · Zhen Niu2 · Yu Li1 · Donghua Zhang2 · Yang Sun1
Yang Sun (Corresponding author) [email protected]
Tel.: + 86 29 82663914; fax: +86 29 82668559.
1 Department of Applied Chemistry, School of Science, Xi’an Jiaotong University, No. 28,
Xianning West Road, Xi’an 710049, P.R. China
2 School of Materials & Chemical Engineering, Xi’an Technological University, No. 2, Xuefu
Road, Xi’an 710021, P.R. China
Contents
1. Synthesis of BMImNO3 (1-n-butyl-3-methylimidazolium nitrate) 2. FT-IR of TiSi0 (Fig. S1) 3. UV-vis of TiSi0 (Fig. S2) 4. Nitrogen adsorption-desorption isotherms and pore size distributions of TiSi0 and TiSi5 (Fig. S3) 5. Low-angle XRD of TiSi0 (Fig. S4) 6. Surface and bulk contents of titanium for titanosilicates (Table S1) 7. Enantioselective adsorption of chiral valine over TiSi1 (a), TiSi2 (b), TiSi3 (c), TiSi4 (d) and TiSi5 (e) (Fig. S5) 8. Leaching percentage of Ti ions during recycling (Table S2) 9. GC-MS examples for oxidations of R-(+)-limonene (Fig. S6-S18) 10. GC-MS and HPLC examples for oxidations of (-)-α-pinene (Fig. S19-S29) 11. GC-MS and HPLC examples for oxidations of styrene (Fig. S30-S36) References
1 1. Synthesis of BMImNO3 (1-n-butyl-3-methylimidazolium nitrate) [a]
BMImCl (17.4 g, 0.1 mol) was dissolved in distilled water (60 mL), then AgNO 3 (16.9 g, 0.1 mol) was added. After stirring at 60 oC for 1 h, this mixture was filtered under reduced pressure, and filtrate was concentrated by rotary evaporation. The light yellow oil was dried at 70 oC in air,
1 obtained in 96% yield (19.3 g). H NMR (400 MHz, d6-DMSO) δ: 9.43 (s, 1H), 7.87 (s, 1H), 7.78
(s, 1H), 4.18 (t, J = 8.0 Hz, 2H), 3.86 (s, 3H), 1.71 (m, 2H), 1.21 (m, 2H), 0.83 (t, J = 7.2 Hz, 3H).
(Notes: The BMImNO3 is water-soluble. A small drop of preparative BMImNO3 could be
dissolved into 20 mL of distilled water, then AgNO3 (50 mg) was added under magnetic stirring. If no turbid was observed, it would be clear that Cl- anions were completely exchanged.).
2. FT-IR of TiSi0
Fig. S1 FT-IR of TiSi0
3. UV-vis of TiSi0
2 Fig. S2 UV-vis spectrum of TiSi0
4. Nitrogen adsorption-desorption isotherms and pore size distributions of TiSi0 and TiSi5
Fig. S3 Nitrogen adsorption-desorption isotherms and pore size distributions of TiSi0 (a and a’)
and TiSi5 (b and b’)
5. Low-angle XRD of TiSi0
3 Fig. S4 Low-angle XRD of powdered TiSi0
6. Surface and bulk contents of titanium for titanosilicates
Table S1 Surface and bulk contents of titanium for titanosilicates
Sample Ti content from XPS (wt.%) a Ti content from ICP (wt.%) b TiSi1 0.98 1.61 TiSi2 1.04 1.90 TiSi3 1.43 2.02 TiSi4 1.89 2.65 TiSi5 3.39 4.69 a Mass percentage determined by at% from XPS data in Table 2 b o -1 Sample (100 mg) was incinerated at 1000 C and dissolved in H2SO4 (3.0 mol L , 2 mL), then diluted to pH = 4.9 at volumetric flask (1000 mL) with NaOH (1 mol L -1), measured by ICP-AES on ICPE-9000
7. Enantioselective adsorption of chiral valine over TiSi1 (a), TiSi2 (b), TiSi3 (c), TiSi4 (d) and
TiSi5 (e)
4 Fig. S5 Enantioselective adsorption of chiral valine over TiSi1 (a), TiSi2 (b), TiSi3 (c), TiSi4 (d)
and TiSi5 (e)
8. Leaching percentage of Ti ions during recycling
Table S2 Leaching percentage of Ti ions from TiSi2 during recycling
Runa Leaching of Ti (%)b Cycle fresh of Entry 5, Table 3 1.1 Cycle 2 of Entry 5, Table 3 0.5 a According to profile of entry 5 of Table 3 b Leaching percent, based on original Ti content; After TiSi2 were filtered, the filtrate was completely concentrated
-1 by rotary evaporation, then treated with a few drops of H2SO4 (3 mol L ). The solution was diluted to pH = 4.3 in volumetric flask (1000 mL), then measured by ICP-AES on ICPE-9000, using the standard working curve method
9. GC-MS examples for oxidations of R-(+)-limonene a. Equipment information
5 GC-MS were performed according to Section 2.2 of manuscript.
b. Representative GC-MS chromatographs
(1) Entry 11, Table 3
Fig. S6 GC-MS chromatograph of Entry 11, Table 3
From left to right, the first peak (integrated in red) is R-(+)-limonene (starting material), which had been tested by MS:
Fig. S7 MS image of R-(+)-limonene
(Note: the upper MS referred to real MS, while the following referred the reference in MS
library.) GC-MS: calcd. for C10H16 136, found 136 (C10H16).
The second peak is iodobenzene:
6 Fig. S8 MS image of iodobenzene
GC-MS: calcd. for C6H5I 204, found 204 (C6H5I).
The third peak is product A or A’, Table 3:
Fig. S9 MS image of product A or A’, Table 3
GC-MS: calcd. for C10H16O – CH3 137, found 137 (C10H16O – CH3).
The forth peak is product A or A’, Table 3:
Fig. S10 MS image of product A or A’, Table 3
GC-MS: calcd. for C10H16O – CH3 137, found 137 (C10H16O – CH3).
7 The fifth peak is product B, Table 3:
Fig. S11 MS image of product B, Table 3
GC-MS: calcd. for C10H16O – CH3 137, found 137 (C10H16O – CH3).
The sixth peak is product C, Table 3:
Fig. S12 MS image of product C, Table 3
GC-MS: calcd. for C10H14O 150, found 150 (C10H14O).
The seventh peak is product D, Table 3:
Fig. S13 MS image of product D, Table 3
GC-MS: calcd. for C10H16O2 – 2O 136, found 137 (C10H16O2 – 2O + H).
8 The eighth peak is product E, Table 3:
Fig. S14 MS image of product E, Table 3
GC-MS: calcd. for C10H18O2 – H2O 152, found 152 (C10H18O2 – H2O).
(2) Cycle fresh, Entry 5, Table 3
Fig. S15 GC-MS chromatograph of Cycle fresh, Entry 5, Table 3
From left to right (marked in red):
Peak 1: R-(+)-limonene; Peak 2: iodobenzene; Peaks 3 and 4: Products A and A’, Table 3; Peak
5: B, Table 3; Peak 6: C, Table 3; Peak 7: D, Table 3.
(3) Cycle 2, Entry 5, Table 3
9 Fig. S16 GC-MS chromatograph of Cycle 2, Entry 5, Table 3
From left to right (marked in red):
Peak 1: R-(+)-limonene; Peak 2: iodobenzene; Peaks 3 and 4: Products A and A’, Table 3; Peak
5: B, Table 3; Peak 6: C, Table 3; Peak 7: D, Table 3.
(4) Cycle fresh, Entry 9, Table 3
Fig. S17 GC-MS chromatograph of Cycle fresh, Entry 9, Table 3
From left to right (marked in red):
Peak 1: R-(+)-limonene; Peak 2: iodobenzene; Peaks 3 and 4: Products A and A’, Table 3; Peak
5: B, Table 3; Peak 6: C, Table 3.
(5) Cycle 2, Entry 9, Table 3
Fig. S18 GC-MS chromatograph of Cycle 2, Entry 9, Table 3
Peak 1: R-(+)-limonene; Peak 2: iodobenzene; Peaks 3 and 4: Products A and A’, Table 3; Peak
10 5: B, Table 3; Peak 6: C, Table 3; Peak 7: E, Table 3.
10. GC-MS and HPLC examples for oxidations of (-)-α-pinene a. Equipment information
GC-MS and chiral HPLC were performed according to Section 2.2 of manuscript.
b. Representative GC-MS chromatographs
(1) Entry 12, Table 4
Fig. S19 GC-MS chromatograph of Entry 12, Table 4
Peak 1 (marked in red):
Fig. S20 MS of (-)-α-pinene, Entry 12, Table 4
GC-MS: calcd. for C10H16 136, found 136 (C10H16).
Peak 2: iodobenzene (abbreviated)
11 Peak 3:
Fig. S21 MS of product A, Entry 12, Table 4
GC-MS: calcd. for C10H16O 152, found 137 (C10H16O - methyl).
Peak 4:
Fig. S22 MS of product B and B’, Entry 12, Table 4
GC-MS: calcd. for C10H16O 152, found 137 (C10H16O - methyl).
Peak 5:
Fig. S23 MS of product A (diastereoisomer), Entry 12, Table 4
GC-MS: calcd. for C10H16O 152, found 137 (C10H16O - methyl).
12 Peak 6:
Fig. S24 MS of product A (another diastereoisomer), Entry 12, Table 4
GC-MS: calcd. for C10H16O 152, found 137 (C10H16O - methyl).
Peak 7:
Fig. S25 MS of product D, Entry 12, Table 4
GC-MS: calcd. for C10H14O 150, found 135 (C10H14O - methyl).
Peak 8:
Fig. S26 MS of product E, Entry 12, Table 4
Analysis was performed according to MS library.
13 (2) Entry 13, Table 4
Fig. S27 GC-MS chromatograph of Entry 13, Table 4
Recognition of peaks was performed by comparison with GC-MS chromatograph of Entry 12,
Table 4 as above.
c. Representative chiral HPLC chromatographs
(1) Entry 12, Table 4
Fig. S28 Chiral HPLC chromatograph for B and B’ of Entry 12, Table 4
Retention time Area (min) (μV·s) 3.836 3320838 4.067 982906 de = 54 %
(2) Entry 13, Table 4
14 Fig. S29 Chiral HPLC chromatograph for B and B’ of Entry 13, Table 4
Retention time Area (min) (μV·s) 3.846 1530610 de = 100 %
11. GC-MS and HPLC examples for oxidations of styrene a. Equipment information
GC-MS and chiral HPLC were performed according to Section 2.2 of manuscript.
b. Representative GC-MS chromatographs
(1) Entry 17, Table 5
Fig. S30 GC-MS chromatograph of Entry 17, Table 5
From left to right (marked in red):
Peak 1:
15 Fig. S31 MS chromatograph of styrene in Entry 17, Table 5
GC-MS: calcd. for C8H8 104, found 104 (C8H8).
Peak 2:
Fig. S32 MS chromatograph of A in Entry 17, Table 5
GC-MS: calcd. for C7H6O 106, found 106 (C7H6O).
Peak 3:
Fig. S33 MS chromatograph of iodobenzene in Entry 17, Table 5
Peak 4:
16 Fig. S34 MS chromatograph of B and B’ in Entry 17, Table 5
GC-MS: calcd. for C8H8O 120, found 119 and 120 (C8H8O – H and C8H8O).
(2) Entry 14, Table 5
Fig. S35 GC-MS chromatograph of Entry 14, Table 5
From left to right (marked in red):
Peak 1, styrene; Peak 2, benzaldehyde (A); Peak 3, iodobenzene; Peak 4, styrene oxide (B +
B’).
c. Representative chiral HPLC chromatograph
(1) Entry 14, Table 5
17 Fig. S36 Chiral HPLC chromatograph for B and B’ of Entry 14, Table 5
Retention time Area (min) (μV·s) 2.424 393719 2.776 52189 ee = 60 % (R)
Major configuration was determined by comparison of elution order of styrene oxide enantiomers with those in literature [b]. Meanwhile, an authentic (R)-styrene oxide (CAS: 20780-
53-4) was tested on the same condition to confirm the major configuration.
References
[a] Li L, Li Y, Pang D, Liu F, Zheng A, Zhang G, Sun Y (2015) Tetrahedron 71:8096-8103
[b] Li X, Shen Q, Zhang G, Zhang D, Zheng A, Guan F, Sun Y (2013) Catal Commun 41:126-131
18