Dalton Transactions
ARTICLE
DOI: 10.1039/C5DT02 7A
Dalton Transac19tions
removed under reduced pressure and the residue was dissolved 1.91 ꢀ 1.83 (m, 2H), 1.75 ꢀ 1.66 (m, 4H), 1.56 ꢀ 1.48 (m, 4H), 1.18 ꢀ
1
3
in dichloromethane, washed with aqueous ammonia solution 1.11 (m, 2H), 0.99 ꢀ 0.89 (m, 2H), 0,84 ꢀ 0.74 (m, 2H); C NMR
10%, 3 x 10mL), brine, then dried over magnesium sulfate and (100,61 MHz, CDCl ) δ 140.47 (d, J = 132.1 Hz), 133.13 (d, J =
(
3
the solvent was evaporated under reduced pressure. The 40.3 Hz), 132.23 (d, J = 2.9 Hz), 131.94 (d, J = 2.8 Hz), 131.79 (d, J
product was isolated as specified below.
= 10 Hz), 131.56 (d, J = 11 Hz), 130.20 (d, J = 21.9 Hz), 128.62 (d,
J = 12.6 Hz), 128.40 (d, J = 13,0 Hz), 34.27 (s), 59.71 (s), 32.35 (s),
4
,4’-bis(diphenylphosphinoxy)-1,1’-dibenzyl-5,5’-bis-1,2,3-
31
2
1
5.39 (s), 25.22 (s), 24.89 (s); P NMR (161.97 MHz, CDCl ) δ
3
triazole dioxide (8.1). The compound was isolated as a white solid
after recrystallization from ethanol; Yield: 49%; H NMR (400,13
MHz, CDCl ) δ 8.13 ꢀ 7.97 (m, 4H), 7.65 ꢀ 7.41 (m, 10H), 7.39 ꢀ
+
7,07 (s); HRMS (EI): m/z Calcd. for C H N O P [M+H] :701.28;
40
42
6
2 2
1
Found: 701.2908; mp: 282.4ꢀ283.0 °C.
3
7
.08 (m, 12H), 6.91 ꢀ 6.77 (m, 4H), 5.51 (d, J = ꢀ14.7 Hz, 2H), 4.70 4,4’-bis(diphenylphosphinoxy)-1,1’-bis(benzyloxyacetyl)-5,5’-bis-
1
3
(d, J = ꢀ14.7 Hz, 2H); C NMR (100,61 MHz, CDCl ) δ 141.18 (d, J 1,2,3-triazole dioxide (8.5). The compound was isolated as a white
3
=
130.4 Hz), 132.88 (s), 132.36 (d, J = 2.8 Hz), 132.04 (d, J = 2.8 solid after purification by a chromatography column on silica gel
Hz), 131.65 (d, J = 10.0 Hz), 131.39 (dd, J = 55.3 Hz, J = 109.07 with as eluent a mixture of dichloromethaneꢀisopropanol (98/2);
1
Hz), 131.23 (d, J = 10.9 Hz), 130.85 (d, J = 241.7 Hz), 128.92(s), Yield: 28%; H NMR (400,13 MHz, CDCl ) δ 7.97 ꢀ 7.89 (m, 4H),
3
1
28.83 (s), 128.62 (d, J = 12.6 Hz), 128.54 (d, J = 12.8 Hz), 128.15 7,59 ꢀ 7,52 (m, 2H), 7.51 ꢀ 7.39 (m, 8H), 7.34 ꢀ 7.28 (m, 8H), 7.25 ꢀ
31
(s), 53.13 (s); P NMR (161.97 MHz, CDCl ) δ 16.80 (s); HRMS 7.19 (m, 4H), 7.17 ꢀ 7.09 (m, 4H), 5.40 (d, J = ꢀ17.8 Hz, 2H), 5.18
3
+
(EI): m/z Calcd. for C H N O P [M+H] :717.22; Found: (d, J = ꢀ17.8 Hz, 2H), 5.05 (d, J = ꢀ12.1 Hz, 2H), 4.99 (d, J = ꢀ12.1
4
2
34
6
2 2
13
7
17.2306; mp: 224.5ꢀ227.4°C.
Hz, 2H); C NMR (100,61 MHz, CDCl ) δ 165.89 (s), 141.10 (d, J
3
=
129.7 Hz), 134.58 (s), 132.54 (d, J = 2.7 Hz), 132.3 (dd, J = 20.8
Hz, J = 110.9 Hz), 132.19 (d, J = 2.7 Hz), 131.83 (d, J = 10.2 Hz),
31.82 (d, J = 21.7 Hz), 131.21 (d, J = 10.9 Hz), 128,77 (d, J = 12.6
Hz), 128.75 (s), 128,72 (s), 128.55 (s), 128.5 (d, J = 13.0 Hz), 68.04
4
,4’-bis(diphenylphosphinoxy)-1,1-dibutyl-5,5’-bis-1,2,3-triazole
dioxide (8.2). The compound was isolated as a white solid after
purification by a chromatography column on silica gel with as eluent
a mixture of dichloromethaneꢀisopropanol (98/2); Yield: 42%; H
NMR (400,13 MHz, CDCl ) δ7. 96 (dd, J = 7.6 Hz, J = 12.1 Hz,
4
4
1
1
1
31
(s), 50.11 (s); P NMR (161.97 MHz, CDCl ) δ 17,36 (s); HRMS
3
+
3
(EI): m/z Calcd. for C H N O P [M+H] :833.23; Found:
46
38
6
6 2
H), 7.61 ꢀ 7.35(m, 10H), 7.33 ꢀ 7.21 (m, 2H), 7.20 ꢀ 7.08 (m, 4H),
.23 ꢀ 4.40 (m, 2H), 4.13 ꢀ 4.01 (m, 2H), 1.92ꢀ1.78(m, 2H), 1.77 ꢀ
8
33.2400; mp: 157.4ꢀ157.9 °C.
13
.64 (m, 2H), 1.22 ꢀ 1.08 (m, 4H), 0.78 (t, J = 7.4 Hz, 6H); C NMR 4,4’-bis(diphenylphosphinoxy)-1,1’-bis(methoxyacetyl) -5,5’-bis-
(
100,61 MHz, CDCl ) δ140.82 (d, J = 130,0 Hz), 133.27 (d, J = 2.7 1,2,3-triazole dioxide (8.6). The compound was isolated as a white
3
Hz), 131.98 (d, J = 2.7 Hz), 131.66 (d, J = 10,0 Hz), 131.57 (dd, J = solid after purification by a chromatography column on silica gel
9 Hz, J = 110.3 Hz), 131.27 (d, J = 10.9 Hz), 130.42 (d, J = 21.9 with as eluent a mixture of dichloromethaneꢀisopropanol (98/2);
2
1
Hz), 129,57 (d, J = 12.7 Hz), 129.47 (d, J = 13,0 Hz), 49.40 (s), Yield: 20%; H NMR (400,13 MHz, CDCl ) δ 7.92 ꢀ 7.84 (m, 4H),
3
δ16,52 (s); HRMS (EI): m/z Calcd. for C H N O P
2 2
3
3
1
1.07 (s), 19.84 (s), 13.31 (s); P NMR (161.97 MHz, CDCl3) 7.50 ꢀ 7.32 (m, 10H), 7.24 ꢀ 7.18 (m, 2H), 7.09 ꢀ 7.03 (m, 4H), 5.29
13
(d, J = ꢀ17.8 Hz, 2H), 5.06 (d, J = ꢀ17.8 Hz, 2H), 3.58 (s, 6H);
NMR (100,61 MHz, CDCl ) δ 166.45 (s), 147.07 (d, J = 129.0 Hz),
C
36
38
6
+
[
M+H] :649.25; Found: 649.2607; mp: 172.2ꢀ172.7 °C.
3
1
32.57 (d, J = 2.78 Hz), 132.19 (d, J = 2.8 Hz), 131.82 (d, J = 10.9
Hz), 131.6 (dd, J = 23.4 Hz, J = 110.81 Hz), 131.17 (d, J = 10.9 Hz),
30.93 5 (s), 128,78 (d, J = 12.8 Hz), 128.5 (d, J = 13,0 Hz), 52.99
4
,4’-bis(diphenylphosphinoxy)-1,1’-diisobutyl-5,5’-bis-1,2,3-
triazole dioxide (8.3). The compound was isolated as a white solid
after purification by a chromatography column on silica gel with as
1
31
(s), 49.89 (s); P NMR (161.97 MHz, CDCl ) δ 17.22 (s); HRMS
3
eluent a mixture of dichloromethaneꢀisopropanol (98/2); Yield: 23%;
+
(EI): m/z Calcd. for C H N O P [M+H] :681.17; Found:
34
30
6
6 2
1
H NMR (400,13 MHz, CDCl ) δ 8.05 ꢀ 7.92 (m, 4H), 7.61 ꢀ 7.44
3
6
81.1790; mp: 211.7ꢀ212.1°C.
(m, 10H), 7.38 ꢀ 7.27 (m, 2H), 7.23 ꢀ 7.14 (m, 4H), 4.20 (dd, J = 7.5
Hz, J = ꢀ13.9 Hz, 2H), 3.88 (dd, J = 7.4 Hz, J = ꢀ13.9 Hz, 2H), 2.10 4,4’-bis(diphenylphosphinoxy)-1,1’-bis(benzyloxymethyl)-5,5’-
ht, J = 6.87 Hz, J = 6.87 Hz, 2H), 0.81 (d, J = 6.7 Hz, 6H), 0.73 (d, bis-1,2,3-triazole dioxide (8.7). The compound was isolated as a
(
13
J = 6.6 Hz, 6H); C NMR (100,61 MHz, CDCl ) δ 140.87 (d, J = white solid after purification by a chromatography column on silica
3
1
31.2 Hz), 133.26 (d, J = 41.9 Hz), 132.27 (d, J = 2.7 Hz), 132.00 gel with as eluent a mixture of dichloromethaneꢀisopropanol (98/2);
1
(d, J = 2.8 Hz), 131.71 (d, J = 10.0 Hz), 131.22 (d, J = 10.8 Hz), Yield: 12%; H NMR (400,13 MHz, CDCl ) δ 8.04ꢀ7.89 (m, 4H),
3
1
30.67 (d, J = 22 Hz), 128.58 (d, J = 12.6 Hz), 128.08 (d, J = 13.0 7.64 ꢀ 7.40 (m, 10H), 7.37 ꢀ 7.11 (m, 16H), 5.87 (d, J = ꢀ11.2 Hz,
3
1
13
Hz), 56.97 (s), 28.02 (s), 20.16 (s), 20.03 (s); P NMR (161.97 2H), 5.75 (d, J = ꢀ11.2 Hz, 2H), 4.42 (s, 4H); C NMR (100,61
MHz, CDCl ) δ 16.5 (s); HRMS (EI): m/z Calcd. for C H N O P
MHz, CDCl ) δ 141.51 (d, J = 129.5 Hz), 135.72 (s), 132.43 (d, J =
2.6 Hz), 132.07 (d, J = 2.7 Hz), 131.84 (dd, J = 31.1 Hz, J = 111
Hz), 131.78 (d, J = 10.2 Hz), 131.22 (d, J = 10.9 Hz), 130.84 (dd, J
3
36 38
6
2
2
3
+
[
M+H] :649.25; Found: 649.2618; mp: 237.1ꢀ238.0 °C.
4
,4’-bis(diphenylphosphinoxy)-1,1’-dicyclohexyl-5,5’-bis-1,2,3-
=
21.3 Hz), 128.64 (d, J = 12.8 Hz), 128.50 (s), 128.42 (d, J = 12.9
triazole dioxide (8.4). The compound was isolated as a white solid
31
Hz), 128.36 (s), 128.26 (s), 76.79 (s), 71.29 (s); P NMR (161.97
1
after sublimation; Yield: 6%; H NMR (400,13 MHz, CDCl ) δ7.95
3
MHz, CDCl ) δ 17,34 (s); HRMS (EI): m/z Calcd. for C H N O P
2 2
3
36 38
6
ꢀ
7.89 (qt, 3H), 7.51 ꢀ 7.38 (m, 11H), 7.27 ꢀ 7.21 (m, 6H), 3.70 (tt, J
+
[
M+H] :777.24; Found: 777.25183; mp: 154.0ꢀ154.8 °C.
=
11.74 Hz,3.70 Hz, 2H), 2.53 ꢀ 2.56 (m, 2H), 2.11 ꢀ 2.02 (m, 2H),
4
| Dalton Trans., 2015, 00, 1-3
This journal is © The Royal Society of Chemistry 2015