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Green Chemistry
C17H30O3N3 ([Ph(OCH2CH2)3TMG]+): 324.2282; m/z = 368.2535, calcd. respectively, with intense stirring. After 15 min,VtiehweArrtieclaecOtniloinne
for C19H34O4N3 ([Ph(OCH2CH2)4TMG]+): 368.2544; m/z = 412.2795, was terminated by placing the autoclave in an ice bath. Upon
DOI: 10.1039/C9GC00679F
calcd. for C21H38O5N3 ([Ph(OCH2CH2)5 TMG]+): 412.2806; m/z = 60releasing the gas, the solution was submitted to GC analysis.
456.3053, calcd. for C23H42O6N3 ([Ph(OCH2CH2)6TMG]+): 456.3068;
5
m/z = 500.3312, calcd. for C25H46O7N3 ([Ph(OCH2CH2)7TMG]+):
Conflicts of interest
There are no conflicts of interest to declare.
500.3330; HRMS (Q−ToF MS, ES−): m/z = 368.0453 (z = 2), calcd. for
C39H30O7P2S2: 368.0460; m/z
= 737.0977 (z = 1), calcd. for
C39H31O7P2S2: 737.0992.
Preparation of [Ph(EO)16TMG]2[Xantphos-(SO3)2] (3d) and its
Acknowledgements
10characterization. Under Ar atmosphere, 2,7- bis(SO3Na)Xantphos
(1.0 g, 1.3 mmol), 1d [Ph(EO)16TMG][OMs] (2.5 g, 2.5 mmol) and
acetonitrile (25 mL) were added to a 100 mL Schlenk flask, and the
mixture was stirred at room temperature for 72h. The reaction was
terminated when 1H NMR analysis indicated that residual CH3SO3Na
15in products was <5%. The mixture was filtered and then acetonitrile
was evaporated under reduced pressure to give 3d as a yellow solid
We gratefully acknowledge the financial support from the
65National Natural Science Foundation of China (No.21576144),
the Natural Science Foundation of Shandong Province (No.
ZR2014BM009), Taishan Scholars Projects of Shandong (No.
ts201511033), and the National Natural Science Foundation of
China (No.21878164).
1
at room temperature. Yield: 2.7 g (85%). Characterization: H NMR
(500.0 MHz, D2O): δ = 7.99 (s, 2H), 7.15–6.83(m, 32H), 3.99–3.23 (m,
124H, OCH2CH2), 2.82 (s, 24H), 1.61 (s, 6H); 13C NMR (150.9 MHz,
20CD3OD): δ = 163.97, 160.30, 154.50, 142.30, 137.91, 135.14, 131.00,
130.56, 129.87, 129.57, 127.98, 125.88, 121.93, 115.69, 74.70-71.32,
70.86, 70.53, 68.52, 45.93, 40.25, 36.10, 31.93; 31P NMR (202.4 MHz,
D2O): δ = −17.46; HRMS (Q−ToF MS, ES+): m/z = 808.5155, calcd. for
C39H74O14N3 ([Ph(OCH2CH2)14TMG]+): 808.5165; m/z = 852.5418,
25calcd. for C41H78O15N3 ([Ph(OCH2CH2)15TMG]+): 852.5427; m/z =
896.5680, calcd. for C43H82O16N3 ([Ph(OCH2CH2)16TMG]+): 896.5690;
m/z = 940.5940, calcd. for C45H86O17N3 ([Ph(OCH2CH2)17TMG]+):
940.5952; HRMS (Q−ToF MS, ES−): m/z = 368.0452 (z = 2), calcd. for
70Notes and references
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C39H30O7P2S2: 368.0460; m/z
30C39H31O7P2S2: 737.0992.
= 737.0980 (z = 1), calcd. for
80
General procedure for evaluating the catalyst activity and
selectivity of hydroformylation of C8-C14 1-alkenes in the HCBS
system using Rh-RTP-PolyGILs catalysts. Under Ar atmosphere, a 60
mL autoclave was loaded with Rh(acac)(CO)2 (1.0 mg, 3.88 103
35mmol), 10 equivalents of 2 (3.88 102 mmol, 55 mg for 2a, 116 mg
for 2b, 62 mg for 2c, 124 mg for 2d) or 5 equivalents of 3 (1.94 102
mmol, 26 mg for 3a, 47 mg for 3b, 28 mg for 3c, 49 mg for 3d), and
solvent (MeOH or EtOH, see Table 1 for the volumes). Subsequently,
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40octene, 14.5 mL for 1-decene, 17.0 mL for 1-dodecene, 19.5 mL for
1-tetradecene) was added along with the internal standard (see
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brought to 100 °C and 7.0 MPa, respectively, with intense stirring.
After 30 min (for 2) or 2 h (for 3), the reaction was terminated by
45placing the autoclave in an ice bath. Upon releasing the syngas, the
solution was submitted to GC analysis.
General procedure for evaluating the catalyst activity and
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system using Rh-2b catalyst. Under Ar atmosphere, a 60 mL
50autoclave was loaded with RhCl3·3H2O (1.0 mg, 3.8 103
mmol), 10 equivalents of 2b (114 mg, 3.8 102 mmol), and
solvent (MeOH or EtOH, see Table 3 for the volumes).
Subsequently, 1 103 equivalents of C8–C14 1-alkene (3.8 mmol,
0.6 mL for 1-octene, 0.7 mL for 1-decene, 0.85 mL for 1-
55dodecene, 1.0 mL for 1-tetradecene) was added along with the
internal standard (see Table 3), and the reaction temperature
and H2 pressure were brought to 80 °C and 6.0 MPa,
85
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