catalyst–free synthesis of cycloalkenyl phosphonates · 2014-03-12 · 1 supplementary...
TRANSCRIPT
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Supplementary Information for
Catalyst–free synthesis of cycloalkenyl phosphonates
Xunfu Xu,a Hu Chen,*ab Yulei Wang,a Yuxing Gao,a Guo Tang*a and Yufen Zhaoa
a College of Chemistry and Chemical Engineering and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiamen 361005, P. R. China. [email protected]; b Department of Chemistry and Chemical Engineering, Hefei Normal University, Hefei 230601, China. [email protected] Table of Contents Page 2 - 3 Analysis of byproduct 3aa Page 3 31P NMR spectra for the synthesis of 3k Page 4 – 12 Spectral Data
Page 13 – 31 1H NMR , 13C NMR and 31P NMR Spectra of all compounds
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2014
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Analysis of byproduct 3aa
[M+Na] m/z : 393.0
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301.6
371.5393.1
459.1
erhuanwuerxi-linque-D-A-0412.d: +MS
277.1
315.0
343.0
371.0
erhuanwuerxi-linque-D-A-0412-2.d: +MS2(371.4)
248.9 277.0
314.9
342.9
erhuanwuerxi -linque-D-A-0412-3.d: +MS3(371.4->343.0)
166.9
232.9
248.9
296.9
314.9
erhuanwuerxi-linque-D-A-0412-4.d: +MS4(371.4->343.0->314.9)
0
2
4
4x10Intens.
0
1
2
3
4x10
0
2000
4000
6000
8000
0
500
1000
1500
31P NMR spectra for the synthesis of 3k. The yield of the crude product 3k was determined by 31P NMR spectrum after reaction at 120 °C for 48 h. The conversion of alkynyl phosphonate was almost quantitative.
-70-60-50-40-30-20-1070 60 50 40 30 20 10 0 ppm
-0.50
14.91
1.13
98.87
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Spectral Data
Diethyl 3-phenylbicyclo[2.2.1]hepta-2,5-dien-2-ylphosphonate(3a)
Yellow oil;1H NMR (400 MHz, CDCl3) δ 7.61 – 7.49 (m, 2H), 7.43 – 7.23 (m, 3H), 6.96 (m, 2H), 4.14 –
4.05 (m, 1H), 4.05 – 3.72 (m, 5H), 2.27 (dt, J = 6.6, 1.4 Hz, 1H), 2.06 (dq, J = 6.6, 1.5 Hz, 1H), 1.17 (td,
7.0, 0.4 Hz, 3H), 1.12 (td, 7.2, 0.3 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 170.6 (d, JPC = 14.3 Hz),
143.5, 140.9 (d, JPC = 2.1 Hz), 135.6 (d, JPC = 3.5 Hz), 134.5 (d, JPC = 201.9 Hz), 128.7, 127.9, 127.5 (d,
JPC = 1.6 Hz), 71.4 (d, JPC = 6.2 Hz), 61.5 (d, JPC = 5.5 Hz), 61.3 (d, JPC = 5.4 Hz), 58.4 (d, JPC = 16.3 Hz),
55.2 (d, JPC = 12.2 Hz), 16.1 (d, JPC = 7.2 Hz), 16.0 (d, JPC = 7.3 Hz). 31P NMR (160 MHz, CDCl3) δ 17.6.
IR (film): 3062, 2982, 2937, 2905, 2869, 1591, 1557, 1492, 1445, 1391, 1293, 1245, 1162, 1095, 1052,
1025, 965, 795, 766, 724, 698, 661, 604, 577, 546, 508 cm-1. HRMS (ESI) calcd for C17H22NaO3P,
328.1204; found 328.1209.
Dimethyl 3-phenylbicyclo[2.2.1]hepta-2,5-dien-2-ylphosphonate(3b)
Yellow oil;1H NMR (400 MHz, CDCl3) δ 7.61 – 7.44 (m, 2H), 7.35 (m, 3H), 7.04 – 6.86 (m, 2H), 4.17 –
4.02 (m, 1H), 3.95 (d, J = 1.4 Hz, 1H), 3.57 (d, J = 11.2 Hz, 3H), 3.47 (d, J = 11.4 Hz, 3H), 2.32 – 2.20
(m, 1H), 2.08-2.05 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 171.7 (d, JPC = 14.7 Hz), 143.5, 140.9 (d, JPC
= 2.3 Hz), 135.3(d, JPC = 3.8 Hz), 133.4(d, JPC = 201.6 Hz), 128.9, 128.0, 127.3 (d, JPC = 1.7 Hz), 71.4 (d,
JPC = 6.2 Hz), 58.5 (d, JPC = 16.4 Hz), 55.2 (d, JPC = 12.1 Hz), 52.1 (d, JPC = 5.5 Hz), 51.8 (d, JPC = 5.5
Hz). 31P NMR (160 MHz, CDCl3) δ 20.6. IR (film): 3062, 2988, 2950, 2849, 1590, 1492, 1447, 1293,
1247, 1183, 1052, 1028, 930, 825, 795, 767, 725, 698, 661, 602, 575, 545 cm-1. HRMS (ESI) calcd for
C15H17NaO3P, 299.0813; found 299.0800.
Diisopropyl (3-phenylbicyclo[2.2.1]hepta-2,5-dien-2-yl)phosphonate(3c)
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Brown oil; 1H NMR (400 MHz, CDCl3) δ 7.58 – 7.55 (m, 2H), 7.37– 7.27 (m, 3H), 6.96 (dd, J = 4.8, 3.1
Hz, 1H), 6.90 (dd, J = 4.8, 3.2 Hz, 1H), 4.58 – 4.45 (m, 5H), 4.09 (d, J = 1.2 Hz, 1H), 3.93 - 3.92(m, 1H),
2.24 - 2.22 (m, 1H), 2.04 - 2.01 (m, 1H), 1.26 (d, J = 6.2 Hz, 3H), 1.21 (d, J = 6.2 Hz, 3H), 1.11 (d, J =
6.2 Hz, 3H), 1.07 (d, J = 6.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 169.2 (d, JPC = 15.0 Hz), 143.5 (d,
JPC = 1.3 Hz), 140.6 (d, JPC = 2.0 Hz), 135.8 (d, JPC = 201.7 Hz), 135.7 (d, JPC = 3.8 Hz), 128.4, 127.8,
127.7 (d, JPC = 1.5 Hz), 71.2 (d, JPC = 6.0 Hz), 70.1 (d, JPC = 5.7 Hz), 70.0 (d, JPC = 5.5 Hz), 58.4 (d, JPC
= 16.3 Hz), 55.5 (d, JPC = 12.3 Hz), 24.0 (d, JPC = 4.0 Hz), 23.9 (d, JPC = 4.2 Hz), 23.7 (d, JPC = 4.9 Hz),
23.5 (d, JPC = 5.1 Hz). 31P NMR (160 MHz, CDCl3) δ 15.0. IR (film): 3060, 2978, 2935, 2871, 1721,
1657, 1594, 1492, 1466, 1448, 1385, 1374, 1242, 1177, 1141, 1105, 986, 896, 766, 722, 697, 660, 605,
579, 549 cm-1. HRMS (ESI) calcd for C19H25NaO3P, 355.1439; found 355.1440.
Dibutyl 3-phenylbicyclo[2.2.1]hepta-2,5-dien-2-ylphosphonate(3d)
Yellow oil;1H NMR (400 MHz, CDCl3) δ 7.58 – 7.50 (m, 2H), 7.41 – 7.25 (m, 3H), 6.98 – 6.91 (m, 2H),
4.10 (s, 1H), 4.09-3.73 (m, 5H), 2.26 (dt, J = 6.6, 1.4 Hz, 1H), 2.10 – 1.98 (m, 1H), 1.56 – 1.35 (m, 4H),
1.35 – 1.16 (m, 4H), 0.85 (dt, J = 14.5, 7.4 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 170.5 (d, JPC = 14.4
Hz), 143.5, 140.9(d, JPC = 2.1 Hz), 135.6(d, JPC = 3.7 Hz), 134.5(d, JPC = 201.9 Hz), 128.6, 127.9, 127.5
(d, JPC = 1.6 Hz), 71.4 (d, JPC = 6.2 Hz), 65.2 (d, JPC = 5.8 Hz), 64.9 (d, JPC = 5.6 Hz), 58.4 (d, JPC = 16.2
Hz), 55.3 (d, JPC = 12.1 Hz), 32.3 (d, JPC = 6.8 Hz), 32.2 (d, JPC = 7.0 Hz), 18.7 (d, JPC = 6.6 Hz), 13.6 (d,
JPC = 3.2 Hz). 31P NMR (160 MHz, CDCl3) δ 17.7. IR (film): 3063, 2960, 2933, 2872, 1591, 1492, 1461,
1295, 1247, 1065, 1023, 980, 902, 765, 723, 697, 605, 579, 548 cm-1. HRMS (ESI) calcd for C21H30O3P,
361.1927; found 361.1925.
Diphenyl 3-phenylbicyclo[2.2.1]hepta-2,5-dien-2-ylphosphine oxide(3e)
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White solid, m.p. 85-87 °C ; 1H NMR (400 MHz, CDCl3) δ 7.70 – 7.61 (m, 2H), 7.53 – 7.38 (m, 5H),
7.38 – 7.27 (m, 3H), 7.21 (m, 2H), 7.11 – 7.05 (m, 3H), 7.01 (dd, J = 4.9, 3.2 Hz, 1H), 6.73 (dd, J = 4.7,
3.0 Hz, 1H), 4.03 – 3.93 (m, 1H), 3.71 – 3.60 (m, 1H), 2.39 (dt, J = 6.6, 1.4 Hz, 1H), 2.02 (dd, J = 6.6, 1.1
Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 172.1 (d, J = 9.1 Hz), 143.1, 141.0(d, JPC = 2.1 Hz), 138.2(d, JPC
= 108.6 Hz), 135.5(d, JPC = 3.1Hz), 133.3(d, JPC = 108.9 Hz), 132.0 (d, JPC = 106.4 Hz), 131.4(d, JPC =
9.8 Hz),131.3 (d, JPC = 3.1 Hz), 131.2(d, JPC = 9.6 Hz), 131.1(d, JPC = 3.0 Hz), 128.4(d, JPC = 11.7Hz),
128.3, 128.0(d, JPC = 12.3 Hz), 127.6, 127.4 (d, JPC = 1.3 Hz), 71.3 (d, JPC = 5.1 Hz), 59.2 (d, JPC = 11.6
Hz), 55.8 (d, JPC = 11.9 Hz). 31P NMR (160 MHz, CDCl3) δ 22.8. IR (film): 3057, 2967, 2939, 2869,
1717, 1586, 1556, 1489, 1438, 1296, 1261, 1182, 1115, 1025, 927, 808, 754, 721, 698, 661, 591, 573, 545,
523 cm-1. HRMS (ESI) calcd for C25H21NaOP, 391.1222; found 391.1230.
Diethyl 3-o-tolylbicyclo[2.2.1]hepta-2,5-dien-2-ylphosphonate(3f)
Yellow oil;1H NMR (400 MHz, CDCl3) δ 7.24 – 7.11 (m, 3H), 7.00 (dd, J = 5.1, 3.0 Hz, 2H), 6.88 (dd, J
= 4.9, 3.2 Hz, 1H), 4.07 (s, 1H), 3.94 – 3.68 (m, 5H), 2.38 (d, J = 6.5 Hz, 1H), 2.23 (s, 3H), 2.12 – 1.99
(m, 1H), 1.08 (dt, J = 19.3, 7.1 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 171.6 (d, JPC = 14.1 Hz), 143.6,
141.1 (d, JPC = 2.4 Hz), 137.2 (d, JPC = 3.5 Hz), 137.0(d, JPC = 204.0 Hz), 135.1 (d, JPC = 2.0
Hz),129.7,127.9,127.4,125.3, 72.6 (d, JPC = 6.0 Hz), 61.4 (d, JPC = 6.1 Hz), 61.3 (d, JPC = 6.8 Hz), 59.1 (d,
JPC = 16.5 Hz), 53.8 (d, JPC = 13.3 Hz), 20.2, 16.1 (d, JPC = 6.8 Hz), 16.0 (d, JPC = 7.0 Hz). 31P NMR (160
MHz, CDCl3) δ 17.1. IR (film): 3065, 2982, 2935, 2900, 2868, 1620, 1596, 1558, 1482, 1453, 1391,
1296, 1244, 1199, 1162, 1095, 1052, 1027, 964, 868, 795, 755, 728, 654, 609, 582, 560 cm-1. HRMS (ESI)
calcd for C18H23NaO3P, 341.1277; found 341.1276.
Diethyl (3-(p-tolyl)bicyclo[2.2.1]hepta-2,5-dien-2-yl)phosphonate(3g)
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Yellow oil;1H NMR (400 MHz, CDCl3) δ 7.43 (dd, J = 6.4, 1.7 Hz, 2H), 6.15 (d, J = 7.9 Hz, 2H), 6.93 –
6.87 (m, 2H),4.04 – 3.76 (m, 6H), 2.33 (s, 3H), 2.22 – 2.20 (m, 1H), 2.01 – 1.99 (m, 1H), 1.13 (dt, J =
21.8, 7.0 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 170.6 (d, JPC = 14.1 Hz), 143.4, 140.7 (d, JPC = 2.1 Hz),
138.7, 133.1 (d, JPC = 200.7 Hz), 132.5 (d, JPC = 3.8 Hz), 128.5, 127.4 (d, JPC = 1.4 Hz), 71.1 (d, JPC = 6.3
Hz), 61.3 (d, JPC = 5.2 Hz), 61.1 (d, JPC = 5.3 Hz), 58.3 (d, JPC = 16.5 Hz), 55.1 (d, JPC = 12.1 Hz), 21.2,
16.1 (d, JPC = 6.6 Hz), 16.0 (d, JPC = 7.2 Hz). 31P NMR (160 MHz, CDCl3) δ 17.1. IR (film): 2982, 2935,
1508, 1443, 1391, 1290, 1231, 1163, 1095, 1052, 1024, 967, 820, 603, 573, 537 cm-1. HRMS (ESI) calcd
for C18H23NaO3P, 341.1283; found 341.1278.
Diethyl 3-(4-fluorophenyl)bicyclo[2.2.1]hepta-2,5-dien-2-ylphosphonate(3h)
Yellow oil;1H NMR (400 MHz, CDCl3) δ 7.61 – 7.47 (m, 2H), 7.13 – 7.00 (m, 2H), 6.99 – 6.85 (m, 2H),
4.07 (d, J = 0.9 Hz, 1H), 4.03 – 3.69 (m, 5H), 2.25 (dd, J = 6.6, 1.4 Hz, 1H), 2.05 (dd, J = 6.6, 1.5 Hz,
1H), 1.25 – 1.18 (m, 3H), 1.17 – 1.09 (m, 3H). 13C NMR (100 MHz, CDCl3) δ 169.5 (d, JPC = 14.2 Hz),
164.2, 161.7, 143.6 (d, JPC = 1.0 Hz),, 140.6 (d, JPC = 2.3 Hz), 133.4(d, JPC = 201.0 Hz), 131.6, 129.5 (d,
JPC = 1.7 Hz), 129.4 (d, JPC = 1.6 Hz), 114.9 (d, JPC = 21.6 Hz), 71.4 (d, JPC = 6.2 Hz), 61.5 (d, JPC = 5.4
Hz), 61.3 (d, JPC = 5.3 Hz), 58.5 (d, JPC = 16.2 Hz), 55.3 (d, JPC = 11.9 Hz), 16.2 (d, JPC = 6.7 Hz), 16.1 (d,
JPC = 6.9 Hz). 31P NMR (160 MHz, CDCl3) δ 17.3. IR (film): 3068, 2983, 2938, 2906, 2871, 1717, 1666,
1600, 1506, 1445, 1392, 1293, 1235, 1162, 1097, 1052, 1025, 966, 840, 794, 732, 603, 575, 539 cm-1.
HRMS (ESI) calcd for C17H20FNaO3P, 345.1026; found 345.1026.
Diethyl 3-(3-chlorophenyl)bicyclo[2.2.1]hepta-2,5-dien-2-ylphosphonate(3i)
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Yellow oil;1H NMR (400 MHz, CDCl3) δ 7.52 – 7.48 (m, 1H), 7.48 – 7.41 (m, 1H), 7.33 – 7.25 (m, 2H),
6.95 (ddt, J = 8.0, 7.4, 3.8 Hz, 2H), 4.13 – 4.06 (m, 1H), 4.05 – 3.79 (m, 5H), 2.26 (dt, J = 6.7, 1.5 Hz,
1H), 2.06 (dt, J = 6.7, 1.5 Hz, 1H), 1.24 – 1.09 (m, 6H). 13C NMR (100 MHz, CDCl3) δ 168.8 (d, JPC =
13.9 Hz), 143.6, 140.8 (d, JPC = 2.3 Hz), 137.4 (d, JPC = 5.2 Hz), 136.5(d, JPC = 201.0 Hz), 133.8, 129.2,
128.5, 127.3 (d, JPC = 1.7 Hz), 125.9, 71.6 (d, JPC = 6.2 Hz), 61.6 (d, JPC = 5.7 Hz), 61.4 (d, JPC = 5.5 Hz),
58.4 (d, JPC = 16.0 Hz), 55.4 (d, JPC = 12.0 Hz), 16.2 (d, JPC = 4.7 Hz), 16.1 (d, JPC = 4.8 Hz). 31P NMR
(160 MHz, CDCl3) δ 16.7. IR (film): 3067, 2982, 2937, 2906, 2869, 1586, 1559, 1474, 1392, 1296, 1246,
1162, 1096, 1052, 1025, 965, 790, 713, 696, 611, 580 cm-1. HRMS (ESI) calcd for C17H20ClNaO3P,
361.0731; found 361.0739.
Diethyl (3-(4-bromophenyl)bicyclo[2.2.1]hepta-2,5-dien-2-yl)phosphonate(3j)
Brown oil; 1H NMR (400 MHz, CDCl3) δ 7.48 – 7.46 (m, 2H), 7.41 – 7.39 (m, 2H), 6.94 – 6.89(m, 2H),
4.06 – 3.76 (m, 6H), 2.23 (d, J = 6.6 , 1H), 2.03 (dd, J = 6.7, 1.3 Hz, 1H), 1.21 – 1.17 (m, 3H), 1.15 –
1.11 (m, 3H). 13C NMR (100 MHz, CDCl3) δ 169.3 (d, JPC = 14.3 Hz), 143.5, 140.7 (d, JPC = 2.2 Hz),
135.5 (d, JPC = 200.2 Hz), 134.3 (d, JPC = 4.1 Hz), 131.0, 129.1 (d, JPC = 1.3 Hz), 122.8, 71.4 (d, JPC = 6.2
Hz), 61.5 (d, JPC = 5.4 Hz), 61.4 (d, JPC = 5.4 Hz), 58.3 (d, JPC = 16.1 Hz), 55.3 (d, JPC = 11.9 Hz), 16.2 (d,
JPC = 7.1 Hz), 16.1 (d, JPC = 7.8 Hz). 31P NMR (160 MHz, CDCl3) δ 17.0. IR (film): 2981, 2934, 1584,
1485, 1443, 1394, 1287, 1244, 1163, 1024, 971, 827, 796, 730, 602, 577, 553 cm-1. HRMS (ESI) calcd
for C17H20BrNaO3P, 405.0231; found 405.0240.
Diethyl (3-(4-cyanophenyl)bicyclo[2.2.1]hepta-2,5-dien-2-yl)phosphonate(3k)
Deep yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.63 (s, 4H), 6.96 – 6.92 (m, 2H), 4.08 – 3.79 (m, 6H) ,
2.26 – 2.24 (m, 1H), 2.09 – 2.07 (m, 1H), 1.17 (dt, J = 32.9, 7.1 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ
178.3 (d, JPC = 13.9 Hz), 143.5 (d, JPC = 1.5 Hz), 140.7 (d, JPC = 2.2 Hz), 140.0 (d, JPC = 3.9 Hz), 138.9 (d,
JPC = 199.7 Hz), 131.6, 128.1 (d, JPC = 1.4 Hz), 118.7, 111.9, 71.7 (d, JPC = 6.1 Hz), 61.7 (d, JPC = 5.5
Hz), 61.6 (d, JPC = 5.6 Hz), 58.2 (d, JPC = 15.8 Hz), 55.6 (d, JPC = 11.4 Hz), 16.2 (d, JPC = 6.7 Hz), 16.1 (d,
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JPC = 6.6 Hz). 31P NMR (160 MHz, CDCl3) δ 15.8. IR (film): 2983, 2937, 2869, 2226, 1605, 1500, 1391,
1290, 1246, 1163, 1095, 1054, 1025, 965, 842, 797, 719, 603, 573, 551, 518 cm-1. HRMS (ESI) calcd for
C18H20NNaO3P, 352.1078; found 352.1081.
Diethyl (3-(thiophen-2-yl)bicyclo[2.2.1]hepta-2,5-dien-2-yl)phosphonate(3l)
Pale yellow oil;1H NMR (400 MHz, CDCl3) δ 7.83 (d, J = 3.7 Hz, 1H), 7.39 (d, J = 4.6 Hz, 1H), 7.09 (dd,
J = 5.0, 3.8 Hz, 1H), 6.91 – 6.90 (m, 1H), 6.84 – 6.83 (m, 1H), 4.11 –3.86 (m, 6H), 2.20 (d, J = 6.7 Hz,
1H), 2.01 (dd, J = 6.7, 1.4 Hz, 1H), 1.25 (dt, J = 16.6, 7.1Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 162.2
(d, JPC = 14.1 Hz), 143.6, 139.8 (d, JPC = 2.0 Hz), 137.9 (d, JPC = 4.7 Hz), 130.3 (d, JPC = 201.9 Hz),
129.3, 128.2, 127.9,70.1 (d, JPC = 6.0 Hz), 61.5 (d, JPC = 5.0 Hz), 61.4 (d, JPC = 5.1Hz), 59.0 (d, JPC =
11.4 Hz), 55.8 (d, JPC = 11.4 Hz), 16.2 (d, JPC = 6.5 Hz), 16.2 (d, JPC = 6.7 Hz). 31P NMR (160 MHz,
CDCl3) δ 17.1. IR (film): 2963, 2934, 2870, 1729, 1616, 1452, 1384, 1374, 1260, 1177, 1105, 1018, 981,
799, 595 cm-1. HRMS (ESI) calcd for C15H19NaO3PS, 333.0690; found 333.0691.
Ethyl methyl 3-butylbicyclo[2.2.1]hepta-2,5-dien-2-ylphosphonate(3m)
Yellow oil;1H NMR (400 MHz, CDCl3) δ 6.81 (dd, J = 4.8, 3.1Hz, 1H), 6.69 (dd, J = 4.8, 3.1Hz 1H),
4.08 - 3.84 (m, 4H), 3.79 (s, 1H), 3.56 (s, 1H), 2.70 - 2.57 (m, 2H), 2.01 (d, J = 6.3 Hz, 1H), 1.93 (dd, J =
6.4, 1.2 Hz, 1H), 1.51 - 1.25 (m,10H), 0.91 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 177.0 (d,
JPC = 17.8 Hz), 143.3, 140.8, 132.4 (d, JPC = 202.5 Hz), 71.8 (d, JPC = 6.0 Hz), 61.0, 60.9, 56.0 (d, JPC =
17.7 Hz), 53.0 (d, JPC =13.1 Hz), 30.1 (d, JPC = 2.7 Hz), 29.2 (d, JPC = 2.1 Hz), 22.5, 16.3 (d, JPC = 5.7
Hz), 16.3 (d, JPC = 6.3Hz), 13.9. 31P NMR (160 MHz, CDCl3) δ 18.7. IR (film): 3070, 2980, 2936, 2903,
2868, 1573, 1556, 1477, 1443, 1419, 1390, 1364, 1298, 1276, 1246,1193, 1163, 1095, 1050, 1024, 961,
863, 847, 792, 720, 673, 635, 597, 579, 535, 506 cm-1. HRMS (ESI) calcd for C15H17NaO3P, 299.0808;
found 299.0800.
Diisopropyl (3-(3-chloropropyl)bicyclo[2.2.1]hepta-2,5-dien-2-yl)phosphonate(3n)
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Yellow oil;1H NMR (400 MHz, CDCl3) δ 6.82 (dd, J = 5.0, 3.0Hz, 1H), 6.68 (dd, J = 4.9, 3.2Hz 1H),
4.66-4.43 (m, 2H), 3.76 (s, 1H), 3.53 (s, 1H), 3.51 – 3.43 (m, 2H), 2.88 – 2.80 (m, 1H), 2.78 – 2.70 (m,
1H), 2.00 – 1.82 (m, 4H), 1.33(d, J = 6.2Hz, 3H), 1.30 (d, J = 6.2Hz, 3H), 1.27 (d, J = 6.2Hz, 3H), 1.19 (d,
J = 6.2Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 173.0 (d, JPC = 17.4 Hz), 143.5, 140.4 (d, JPC = 2.1 Hz),
135.6 (d, JPC = 203.4 Hz), 71.9 (d, JPC = 5.9 Hz), 69.7, 69.6, 56.0 (d, JPC = 17.5 Hz), 53.1 (d, JPC =12.4
Hz), 44.3, 30.4 (d, JPC = 2.0 Hz), 27.9 (d, JPC = 2.7 Hz), 24.1 (d, JPC = 3.7 Hz), 24.1 (d, JPC = 3.5 Hz),
24.0 (d, JPC = 4.4 Hz), 23.9 (d, JPC = 4.4 Hz). 31P NMR (160 MHz, CDCl3) δ 15.2. IR (film): 3067, 2976,
2935, 2869, 1726, 1616, 1557, 1451, 1373, 1385, 1302, 1283, 1240, 1178, 1140, 1107, 1042, 979, 849,
882, 798, 772, 723, 649, 596, 523 cm-1. HRMS (ESI) calcd for C16H26ClNaO3P, 355.1206; found
355.1212.
Diethyl (3-(hydroxymethyl)bicyclo[2.2.1]hepta-2,5-dien-2-yl)phosphonate(3o)
Brown oil; 1H NMR (400 MHz, CDCl3) δ 6.81 (dd, J = 5.0,3.0Hz, 1H), 6.69 (dd, J = 4.9,3.3Hz 1H), 5.52
(s, 1H), 4.63 (dd, J = 17.8,3.5Hz 1H), 6.69 (dd, J = 17.8,4.0Hz 1H), 4.13 – 3.78 (m, 4H), 3.75 (s, 1H),
3.50 (s, 1H), 2.03 (d, J = 6.6 Hz, 1H), 1.91 (dd, J = 6.6,1.1 Hz, 1H), 1.31 (t, J = 7.1 Hz, 3H), 1.23 (t, J =
7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 177.5 (d, JPC = 18.2 Hz), 143.3, 140.5 (d, JPC = 2.3 Hz),
132.2 (d, JPC = 201.1 Hz), 71.6 (d, JPC = 5.8 Hz), 62.5 (d, JPC = 4.2 Hz), 61.8 (d, JPC = 5.1 Hz), 61.7 (d,
JPC =5.1 Hz), 55.5 (d, JPC = 16.6 Hz), 53.5 (d, JPC = 11.3 Hz), 16.2(d, JPC = 6.4 Hz), 16.1 (d, JPC = 6.7Hz). 31P NMR (160 MHz, CDCl3) δ 19.7. IR (film): 2983, 2938, 2870, 1725, 1669, 1392, 1281, 1226, 1164,
1095, 1024, 971, 796, 587 cm-1. HRMS (ESI) calcd for C12H19NaO4P, 281.0919; found 281.0925.
Diethyl (3-(thiophen-2-yl)bicyclo[2.2.1]hepta-2,5-dien-2-yl)phosphonate(3p)
-
11
Yellow oil;1H NMR (400 MHz, CDCl3) δ 9.95 (s, 1H), 7.36 -7.19 (m,5H), 6.89 (dd, J = 4.1, 4.1Hz, 1H),
6.879 (dd, J = 4.8, 3.2Hz, 1H), 4.71 - 4.63 (m, 1H), 4.55 - 4.45 (m, 2H), 4.44 - 4.34 (m, 2H), 3.93 (s, 1H),
2.06 (d, J = 6.8 Hz, 1H), 1.94 (d, J = 6.8Hz, 1H), 1.36 (d, J = 6.2Hz, 3H), 1.30 (d, J = 6.2Hz, 3H), 1.26 (d,
J = 6.2Hz, 3H), 1.11 (d, J = 6.2Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 164.2 (d, JPC = 15.4 Hz), 163.0 (d,
JPC = 4.6 Hz), 143.7 (d, JPC = 194.2 Hz), 142.6 (d, JPC = 2.4 Hz), 141.6 (d, JPC = 1.3 Hz), 138.9, 128.4,
127.9, 127.0, 71.5 (d, JPC = 6.9 Hz), 71.4 (d, JPC = 9.5 Hz), 56.3 (d, JPC = 9.3 Hz), 54.8 (d, JPC =15.8 Hz),
43.7, 24.0 (d, JPC = 3.8 Hz), 23.9 (d, JPC = 4.3 Hz), 23.8 (d, JPC =4.2 Hz), 23.7 (d, JPC = 5.2 Hz). 31P NMR
(160 MHz, CDCl3) δ 13.9. IR (film): 3064, 2979, 2935, 1657, 1538, 1497, 1453, 1386, 1375, 1232, 1177,
1142, 1103, 988, 897, 700, 585 cm-1. HRMS (ESI) calcd for C21H28NNaO4P, 412.1654; found412.1654.
Diethyl (3-(thiophen-2-yl)bicyclo[2.2.1]hepta-2,5-dien-2-yl)phosphonate(3q)
Pale yellow oil;1H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 7.4 Hz, 2H), 7.57 (dd, J = 7.4, 7.4 Hz, 1H),
7.45 (dd, J = 7.7, 7.7 Hz, 2H), 4.86 - 4.84 (m, 1H), 6.74 - 4.72 (m, 1H), 5.49 (dd, J = 13.7, 2.4 Hz, 1H),
5.30 (dd, J = 13.7, 2.8 Hz, 1H), 4.72 - 4.53 (m, 2H), 3.86 (s, 1H), 3.77 (s, 1H), 2.10 (d, J = 6.5 Hz, 1H),
1.98 (d, J = 6.4Hz, 1H), 1.36(d, J = 6.2Hz, 3H), 1.33 (d, J = 6.2Hz, 3H), 1.30 (d, J = 6.2 Hz, 3H), 1.21 (d,
J = 6.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 167.3 (d, JPC= 15.5 Hz), 166.2, 143.0 (d, JPC = 1.4 Hz),
141.1 (d, JPC = 2.3 Hz), 139.9 (d, JPC = 200.5 Hz), 133.0, 130.1, 129.7, 128.4, 72.2 (d, JPC = 5.8 Hz), 70.3
(d, JPC = 5.3Hz), 70.2 (d, JPC = 5.3Hz), 61.5 (d, JPC = 2.2 Hz), 54.1 (d, JPC = 16.2 Hz), 53.5 (d, JPC =11.6
Hz), 24.1 (d, JPC = 1.9 Hz), 24.1 (d, JPC = 1.4 Hz), 24.0 (d, JPC = 3.0 Hz), 23.9 (d, JPC = 3.6 Hz). 31P NMR
(160 MHz, CDCl3) δ 13.5. IR (film): 2977, 2935, 1722, 1451, 1385, 1269, 1176, 1106, 1069, 1045, 1021,
979, 712,594 cm-1. HRMS (ESI) calcd for C21H27NaO5P, 413.1494; found 413.1493.
Diethyl [1,1'-biphenyl]-2-ylphosphonate(3r)
Pale yellow oil;1H NMR (400 MHz, CDCl3) δ 8.04 (dd, J = 14.2,7.7Hz, 1H), 7.55 (dd, J = 7.1,7.1Hz 1H),
7.44-7.31 (m, 7H), 3.97-3.78 (m, 4H), 1.12 (t, J = 6.9 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 146.0 (d,
JPC = 9.7 Hz), 141.4 (d, JPC = 4.2 Hz), 133.8 (d, JPC = 9.8 Hz), 131.9 (d, JPC = 3.0 Hz), 131.3 (d, JPC =
-
12
14.1 Hz) ,129.3, 127.5, 127.4, 127.0 (d, JPC = 187.3 Hz), 126.8 (d, JPC = 14.7 Hz), 61.8 (d, JPC = 6.0 Hz),
16.0 (d, JPC =6.9Hz). 31P NMR (160 MHz, CDCl3) δ 18.2. IR (film): 3056, 2981, 2929, 1467, 1444, 1390,
1242, 1163, 1139, 1094, 1056, 1024, 965, 777, 756, 701, 569, 552, 523 cm-1. HRMS (ESI) calcd for
C16H19NaO3P, 313.0970; found 313.0978.
Diethyl (4,5-dimethyl-3,6-dihydro-[1,1'-biphenyl]-2-yl)phosphonate(3s)
Pale yellow oil;1H NMR (400 MHz, CDCl3) δ 7.34 – 7.23 (m, 5H), 3.90 – 3.81 (m, 2H), 3.77 – 3.68 (m,
2H), 3.03 (d, J = 5.8 Hz, 2H), 2.93 (d, J = 6.8 Hz, 2H), 1.71 (s, 3 H), 1.64 (s, 3 H), 1.10 (t, J =7.0 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 150.1 (d, JPC = 8.6 Hz), 142.3 (d, JPC = 8.2 Hz), 127.8, 127.3 (d, JPC = 1.4
Hz), 122.7 (d, JPC = 11.0 Hz), 121.8(d, JPC = 1.8Hz), 121.5 (d, JPC = 183.6 Hz), 61.1 (d, JPC = 6.1 Hz),
42.3 (d, JPC = 16.1 Hz), 35.4 (d, JPC = 10.9 Hz), 17.8 (d, JPC = 8.6 Hz), 16.0 (d, JPC = 6.7 Hz). 31P NMR
(160 MHz, CDCl3) δ 18.8. IR (film): 3055, 2980, 2927, 2862, 1601, 1479, 1443, 1390, 1367, 1287, 1239,
1166, 1137, 1096, 1026, 966, 887, 781, 767, 751, 723, 700, 651, 635, 582, 571, 527 cm-1. HRMS (ESI)
calcd for C18H25NaO3P, 343.1439; found 343.1444.
-
13
1H , 13C and 31P NMR spectra of all compounds 3a
10 9 8 7 6 5 4 3 2 1 0 ppm
1.09
801.
1155
1.13
311.
1339
1.15
141.
1689
1.16
971.
1865
1.18
722.
0467
2.05
062.
0632
2.06
712.
2597
2.27
623.
8183
3.82
333.
8362
3.83
743.
8415
3.85
533.
8598
3.87
323.
8909
3.89
323.
9109
3.92
873.
9337
3.93
853.
9408
3.95
173.
9697
4.08
924.
0913
4.09
346.
9402
6.94
746.
9575
6.95
896.
9659
7.28
377.
3192
7.33
327.
3368
7.35
337.
3567
7.36
777.
3717
7.38
917.
5295
7.53
267.
5366
7.54
977.
5537
6.00
1.02
1.02
5.01
1.00
1.97
3.16
2.00
PO
O
O
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.0
116
.09
16.1
6
55.2
055
.32
58.3
958
.56
61.2
061
.26
61.4
461
.50
71.3
571
.41
76.7
377
.05
77.3
7
127.
4912
7.51
127.
8812
8.66
133.
5213
5.53
135.
5914
0.87
140.
8914
3.54
170.
5417
0.68
PO
O
O
-80-60-40-20120 100 80 60 40 20 0 ppm
17.5
7
PO
O
O
-
14
3b
10 9 8 7 6 5 4 3 2 1 0 ppm
2.05
202.
0558
2.05
972.
0636
2.06
862.
0725
2.07
632.
0802
2.26
362.
2673
2.27
702.
2803
2.28
373.
4592
3.48
753.
5558
3.58
393.
9454
3.94
894.
0754
4.07
714.
0796
6.93
496.
9461
6.95
326.
9565
6.95
916.
9660
6.97
757.
2835
7.30
817.
3114
7.31
487.
3210
7.32
977.
3365
7.34
347.
3471
7.35
117.
3590
7.36
257.
3735
7.37
747.
3898
7.39
447.
3991
7.51
577.
5219
7.52
507.
5291
1.02
1.02
2.94
3.00
1.01
1.02
1.97
3.10
2.02
P
O O
O
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
51.7
951
.84
52.0
752
.13
55.1
355
.25
58.4
458
.60
71.4
271
.48
76.7
677
.07
77.3
9
127.
3612
7.38
127.
9612
8.85
132.
3513
4.36
135.
3213
5.35
140.
9414
0.97
143.
51
171.
6817
1.82
P
O O
O
-80-70-60-50-40-30-20-10120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
20.5
6
P
O O
O
-
15
3c
10 9 8 7 6 5 4 3 2 1 0 ppm
1.06
671.
0822
1.10
821.
1237
1.20
291.
2183
1.24
981.
2573
1.26
522.
0135
2.01
722.
0209
2.02
982.
0336
2.22
002.
2364
3.92
273.
9244
3.92
654.
0861
4.08
894.
4825
4.48
674.
4979
4.50
224.
5097
4.51
764.
5252
4.52
924.
5447
6.89
426.
9024
6.90
656.
9142
6.94
826.
9556
6.95
996.
9681
7.27
157.
2899
7.30
447.
3077
7.31
117.
3297
7.33
287.
3445
7.34
857.
3660
7.36
957.
5549
7.55
737.
5609
7.56
977.
5748
7.57
86
3.08
3.01
3.03
3.12
1.10
1.03
1.03
1.05
2.03
1.01
1.00
3.13
2.04
POO
O
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
23.5
323
.58
23.6
723
.72
23.8
823
.92
23.9
724
.01
55.4
555
.58
58.3
158
.47
70.0
270
.07
70.1
370
.18
71.1
771
.23
127.
6512
7.76
128.
4413
4.82
135.
7313
6.83
140.
5814
3.55
169.
1216
9.27
POO
O
-80-60-40-20120 100 80 60 40 20 0 ppm
14.9
8
POO
O
-
16
3d
10 9 8 7 6 5 4 3 2 1 0 ppm
0.81
260.
8310
0.84
880.
8664
0.88
481.
2098
1.22
781.
2470
1.25
931.
2662
1.27
741.
2965
1.31
551.
4089
1.42
991.
4462
1.47
341.
4940
1.51
022.
0417
2.04
552.
0582
2.06
202.
2536
2.27
013.
7307
3.74
733.
7642
3.78
083.
8192
3.83
673.
8696
3.88
623.
9279
3.93
143.
9349
4.08
914.
0908
6.93
556.
9372
6.94
456.
9517
6.95
327.
3123
7.32
987.
3447
7.34
817.
3591
7.36
317.
3804
7.53
387.
5368
7.54
097.
5539
7.55
79
6.00
4.33
4.09
1.06
1.00
5.02
0.99
1.95
3.10
1.99
PO
OnBu
OnBu
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.5
613
.59
18.6
518
.71
32.2
032
.27
32.2
832
.35
55.2
755
.38
58.3
458
.50
64.9
164
.96
65.1
865
.24
71.3
471
.40
76.7
477
.06
77.3
7
127.
4812
7.49
127.
8912
8.63
133.
5313
5.53
135.
5913
5.62
140.
8714
0.90
143.
55
170.
4417
0.58
PO
OnBu
OnBu
-80-70-60-50-40-30-20-10120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
17.7
0
PO
OnBu
OnBu
-
17
3e
10 9 8 7 6 5 4 3 2 1 0 ppm
2.02
482.
0276
2.38
372.
4003
3.99
023.
9923
3.99
536.
7278
7.00
237.
0102
7.01
457.
0701
7.07
327.
0753
7.07
907.
0825
7.08
647.
2035
7.20
677.
2109
7.22
267.
2300
7.28
397.
3051
7.33
687.
3400
7.34
267.
3460
7.34
987.
3544
7.35
657.
3609
7.41
027.
4140
7.41
757.
4213
7.42
857.
4358
7.45
007.
4531
7.45
597.
4707
7.47
407.
4802
7.48
377.
5010
7.50
417.
6281
7.63
217.
6490
7.65
227.
6581
7.66
227.
6788
7.68
22
1.00
1.29
1.01
1.00
0.97
1.03
2.95
2.00
3.26
5.16
2.02
PO
Ph
Ph
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
55.8
355
.95
59.1
559
.27
71.2
971
.34
76.7
377
.04
77.3
6
127.
4012
7.60
127.
9512
8.07
128.
3212
8.44
131.
1213
1.14
131.
1713
1.21
131.
3113
1.36
131.
4113
2.51
132.
8113
3.87
135.
4813
5.52
137.
6413
8.72
141.
0214
3.10
171.
9717
2.06
PO
Ph
Ph
-80-60-40-20120 100 80 60 40 20 0 ppm
22.7
5
PO
Ph
Ph
-
18
3f
10 9 8 7 6 5 4 3 2 1 0 ppm
1.03
611.
0538
1.07
141.
0843
1.10
191.
1196
2.07
232.
0759
2.08
862.
0921
2.23
042.
3674
2.38
373.
7135
3.72
103.
7317
3.73
833.
7452
3.75
023.
7568
3.76
353.
7753
3.78
183.
8006
3.83
253.
8432
3.85
023.
8578
3.86
103.
8681
3.87
533.
8788
3.88
603.
8929
3.90
404.
0662
6.86
876.
8769
6.88
116.
8890
6.99
397.
0006
7.00
587.
0143
7.12
627.
1429
7.14
827.
1614
7.16
717.
1824
7.18
687.
1897
7.20
317.
2062
7.28
38
3.01
2.97
1.07
3.00
1.04
5.01
1.00
0.99
1.94
3.00
PO
O
O
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
15.9
716
.03
16.0
616
.13
20.2
0
53.7
653
.89
58.9
859
.14
61.2
561
.32
61.3
872
.53
72.5
976
.74
77.0
677
.38
125.
2712
7.44
127.
8912
9.74
135.
0613
6.00
137.
1713
7.20
138.
0314
1.14
141.
1614
3.60
171.
5317
1.67
PO
O
O
-80-70-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm
17.0
5
PO
O
O
-
19
3g
10 9 8 7 6 5 4 3 2 1 0 ppm
1.08
171.
0992
1.11
671.
1355
1.13
621.
1531
1.15
381.
1714
1.99
601.
9998
2.01
252.
0163
2.19
982.
2031
2.20
652.
2160
2.21
952.
3314
3.78
403.
7920
3.80
173.
8034
3.81
023.
8211
3.82
833.
8355
3.84
593.
8478
3.85
323.
8709
3.87
323.
8838
3.89
093.
8935
3.90
703.
9250
3.93
213.
9431
3.95
044.
0391
4.04
176.
8743
6.88
596.
8933
6.90
976.
9168
6.92
086.
9285
7.13
577.
1554
7.25
997.
4171
7.42
157.
4333
7.43
75
6.02
1.01
1.03
3.02
6.06
2.00
2.01
2.00
PO OO
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
15.9
516
.02
16.0
921
.23
55.0
555
.17
58.2
358
.39
61.0
661
.11
61.3
061
.35
71.0
571
.12
76.6
877
.00
77.3
2
127.
4312
7.44
128.
4913
2.14
132.
5213
2.56
134.
1313
8.65
140.
6714
0.69
143.
41
170.
6317
0.77
PO OO
-100-80-60-40-20120 100 80 60 40 20 0 ppm
17.9
2
PO OO
-
20
3h
10 9 8 7 6 5 4 3 2 1 0 ppm
1.12
261.
1402
1.15
781.
1903
1.20
791.
2259
2.04
112.
0449
2.05
772.
0616
2.24
052.
2571
3.81
983.
8261
3.83
763.
8391
3.84
473.
8569
3.86
263.
8899
3.89
263.
8977
3.89
993.
9039
3.90
743.
9097
3.91
513.
9328
3.93
523.
9529
3.96
063.
9789
3.99
694.
0719
4.07
416.
9214
6.92
876.
9459
6.95
326.
9572
7.03
447.
0513
7.05
637.
0612
7.07
287.
0782
7.28
357.
5407
7.54
627.
5542
7.55
967.
5629
7.57
097.
5764
3.06
3.00
1.04
1.04
5.04
0.99
2.01
2.01
2.01
F
PO
O
O
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.0
616
.13
16.1
516
.21
55.2
255
.33
58.3
758
.53
61.2
661
.31
61.4
561
.51
71.3
171
.37
76.7
277
.04
77.3
5
114.
7811
4.99
129.
4812
9.55
129.
5613
1.61
133.
3613
5.36
140.
6214
0.64
143.
5714
3.58
161.
7016
4.17
169.
4616
9.60
F
PO
O
O
-80-60-40-20120 100 80 60 40 20 0 ppm
17.3
2
F
PO
O
O
-
21
3i
10 9 8 7 6 5 4 3 2 1 0 ppm
1.14
321.
1440
1.16
071.
1616
1.17
901.
1965
1.19
731.
2148
2.05
042.
0542
2.06
702.
0709
2.24
782.
2645
3.86
063.
8782
3.88
023.
8923
3.89
593.
8968
3.90
243.
9146
3.91
723.
9198
3.93
763.
9566
3.97
453.
9929
4.09
024.
0923
4.09
424.
0962
6.93
466.
9418
6.95
376.
9550
6.96
126.
9621
7.28
417.
2860
7.28
917.
2937
7.29
837.
3004
7.30
227.
4339
7.43
827.
4479
7.45
117.
4876
7.49
097.
4937
7.49
607.
4978
6.00
1.05
1.03
5.02
1.01
1.96
2.00
0.99
0.96
10 9 8 7 6 5 4 3 2 1 0 ppm
1.14
321.
1440
1.16
071.
1616
1.17
901.
1965
1.19
731.
2148
2.05
042.
0542
2.06
702.
0709
2.24
782.
2645
3.86
063.
8782
3.88
023.
8923
3.89
593.
8968
3.90
243.
9146
3.91
723.
9198
3.93
763.
9566
3.97
453.
9929
4.09
024.
0923
4.09
424.
0962
6.93
466.
9418
6.95
376.
9550
6.96
126.
9621
7.28
417.
2860
7.28
917.
2937
7.29
837.
3004
7.30
227.
4339
7.43
827.
4479
7.45
117.
4876
7.49
097.
4937
7.49
607.
4978
6.00
1.05
1.03
5.02
1.01
1.96
2.00
0.99
0.96
10 9 8 7 6 5 4 3 2 1 0 ppm
1.14
321.
1440
1.16
071.
1616
1.17
901.
1965
1.19
731.
2148
2.05
042.
0542
2.06
702.
0709
2.24
782.
2645
3.86
063.
8782
3.88
023.
8923
3.89
593.
8968
3.90
243.
9146
3.91
723.
9198
3.93
763.
9566
3.97
453.
9929
4.09
024.
0923
4.09
424.
0962
6.93
466.
9418
6.95
376.
9550
6.96
126.
9621
7.28
417.
2860
7.28
917.
2937
7.29
837.
3004
7.30
227.
4339
7.43
827.
4479
7.45
117.
4876
7.49
097.
4937
7.49
607.
4978
6.00
1.05
1.03
5.02
1.01
1.96
2.00
0.99
0.96
PO
O
OCl
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.0
716
.12
16.1
9
29.6
7
55.3
055
.42
58.2
958
.45
61.3
861
.43
61.5
861
.63
71.5
971
.65
76.7
377
.05
77.3
7
125.
8712
7.33
127.
3412
8.50
129.
1513
3.78
135.
5213
7.35
137.
3913
7.52
140.
7914
0.81
143.
56
168.
7716
8.91
PO
O
OCl
-80-70-60-50-40-30-20-10120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.6
7
PO
O
OCl
-
22
3j
10 9 8 7 6 5 4 3 2 1 0 ppm
1.14
821.
1777
1.19
531.
2130
2.02
492.
0282
2.04
162.
0448
2.21
932.
2359
3.76
283.
7805
3.78
803.
8001
3.80
583.
8181
3.82
503.
8364
3.84
293.
8546
3.86
173.
8720
3.89
663.
9017
3.91
453.
9217
3.93
193.
9396
3.94
463.
9520
3.96
323.
9698
3.98
113.
9883
3.99
904.
0064
4.02
424.
0552
6.88
726.
8996
6.90
716.
9239
6.93
126.
9436
7.26
007.
3976
7.41
907.
4633
7.48
47
3.00
3.06
1.02
1.00
6.06
2.00
2.02
2.00
Br
PO O
O
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.0
516
.13
16.2
0
55.2
955
.41
58.2
258
.38
61.3
361
.38
61.5
161
.57
71.4
071
.46
76.6
877
.00
77.3
2
122.
8212
9.13
129.
1513
1.03
134.
3313
4.37
134.
5013
6.49
140.
6714
0.69
143.
49
169.
2616
9.40
Br
PO O
O
-100-80-60-40-20100 80 60 40 20 0 ppm
16.9
7
Br
PO O
O
-
23
3k
10 9 8 7 6 5 4 3 2 1 0 ppm
1.21
401.
2316
2.06
612.
0698
2.08
312.
0867
2.24
522.
2621
3.79
023.
7978
3.81
103.
8155
3.82
923.
8332
3.83
493.
8476
3.85
313.
8658
3.87
133.
8842
3.89
863.
9157
3.92
343.
9336
3.93
613.
9411
3.95
403.
9589
3.96
133.
9768
3.97
833.
9952
4.00
194.
0132
4.02
024.
0311
4.03
854.
0565
4.08
356.
9176
6.92
986.
9370
6.94
516.
9523
6.96
457.
2600
7.62
79
6.04
0.98
1.00
6.02
1.95
3.91
PO
OO
NC
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.0
716
.14
16.1
716
.24
55.5
255
.63
58.1
658
.31
61.5
361
.58
61.6
661
.72
71.6
571
.71
76.6
977
.00
77.3
2
111.
8811
8.72
128.
1312
8.14
131.
6213
7.87
139.
8613
9.97
140.
0114
0.74
143.
54
168.
2216
8.36
PO
OO
NC
-100-80-60-40-20120 100 80 60 40 20 0 ppm
15.7
7
PO
OO
NC
-
24
3l
10 9 8 7 6 5 4 3 2 1 0 ppm
1.21
51.
233
1.25
11.
257
1.27
51.
292
1.99
51.
999
2.01
22.
015
2.18
92.
206
3.87
33.
891
3.89
33.
898
3.91
13.
916
3.91
83.
936
3.95
33.
966
3.97
13.
978
3.98
33.
990
3.99
64.
004
4.00
94.
012
4.02
94.
032
4.05
14.
058
4.06
14.
069
4.08
64.
094
6.82
66.
836
6.84
46.
896
6.90
36.
907
6.91
47.
075
7.08
57.
088
7.09
77.
260
7.38
77.
399
7.40
07.
825
7.83
5
6.14
1.01
1.01
6.07
1.00
1.04
1.05
1.00
0.99
S
PO
O O
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.1
416
.21
16.2
8
55.3
255
.44
58.8
859
.04
61.3
661
.41
61.4
561
.50
70.1
270
.18
76.6
977
.00
77.3
2
127.
8912
8.21
129.
3213
1.33
137.
8613
7.91
139.
8313
9.85
143.
65
162.
1016
2.24
S
PO
O O
-100-80-60-40-20120 100 80 60 40 20 0 ppm
17.3
9
S
PO
O O
-
25
3m
10 9 8 7 6 5 4 3 2 1 0 ppm
-0.0
001
0.89
510.
9129
0.93
081.
2542
1.27
191.
2896
1.30
121.
3091
1.31
881.
3364
1.36
211.
3832
1.40
121.
4554
1.47
061.
9233
1.93
912.
0002
2.01
612.
6033
2.60
942.
6245
2.63
182.
6383
2.64
802.
6545
2.66
052.
6705
3.55
793.
7892
3.86
493.
8707
3.88
993.
9079
3.95
113.
9690
3.97
633.
9870
3.99
434.
0050
4.01
204.
0225
4.02
454.
0381
4.04
244.
0559
6.67
616.
6876
6.69
636.
8029
6.81
046.
8146
6.82
287.
2770
3.09
10.3
0
1.04
1.04
2.05
1.01
1.02
4.01
1.00
1.01
P OO
O
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.9
116
.29
16.3
616
.41
22.5
129
.23
29.2
530
.13
30.1
5
52.9
253
.04
55.9
856
.16
60.9
861
.03
71.6
871
.74
76.7
277
.04
77.3
5
131.
4213
3.43
140.
7814
0.81
143.
28
176.
8917
7.07
P OO
O
-80-60-40-20120 100 80 60 40 20 0 ppm
18.6
5
P OO
O
-
26
3n
10 9 8 7 6 5 4 3 2 1 0 ppm
1.18
091.
1964
1.25
981.
2753
1.29
271.
3081
1.32
271.
3382
1.81
671.
8387
1.85
571.
8604
1.87
371.
8774
1.89
551.
9127
1.92
221.
9255
1.92
951.
9376
1.94
101.
9511
1.98
752.
0035
2.75
542.
8196
2.83
623.
4582
3.46
763.
4756
3.48
543.
4931
3.50
333.
5300
3.75
804.
4616
4.47
714.
4814
4.49
264.
4969
4.51
244.
5787
4.59
424.
5989
4.60
974.
6144
4.62
996.
6730
6.68
526.
6932
6.80
966.
8171
6.82
216.
8297
7.26
01
3.04
3.09
3.00
3.06
4.06
1.09
1.10
2.02
1.08
1.04
2.06
1.00
1.00
P O
OOCl
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
23.9
624
.01
24.0
624
.09
24.1
327
.89
27.9
230
.44
44.3
153
.04
53.1
755
.88
56.0
569
.66
69.7
171
.90
71.9
676
.68
77.0
077
.32
134.
6113
6.63
140.
3514
0.38
143.
54
172.
8917
3.07
P O
OOCl
-80-60-40-20120 100 80 60 40 20 0 ppm
15.2
4
P O
OOCl
-
27
3o
10 9 8 7 6 5 4 3 2 1 0 ppm
1.21
041.
2281
1.24
581.
2991
1.31
681.
3345
1.89
731.
9001
1.91
371.
9165
2.02
242.
0388
3.49
813.
5009
3.74
963.
7998
3.80
733.
8197
3.82
513.
8379
3.84
343.
8446
3.86
303.
9168
3.93
473.
9527
3.96
003.
9707
3.97
803.
9887
3.99
604.
0284
4.03
604.
0536
4.07
134.
0910
4.10
874.
1147
4.12
634.
1338
4.39
304.
4030
4.43
764.
4476
4.60
064.
6094
4.64
514.
6540
6.68
586.
6980
6.70
636.
7931
6.80
066.
8055
6.81
32
3.00
2.97
1.05
1.05
1.02
1.06
4.08
1.01
1.05
0.97
1.02
1.03
PO
OO
OH
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.1
116
.18
16.2
116
.27
53.4
453
.55
55.4
155
.58
61.7
161
.77
61.8
262
.52
62.5
671
.53
71.5
976
.68
77.0
077
.32
131.
2413
3.24
140.
5014
0.52
143.
32
177.
3717
7.55
PO
OO
OH
-100-80-60-40-20120 100 80 60 40 20 0 ppm
19.7
4
PO
OO
OH
-
28
3p
11 10 9 8 7 6 5 4 3 2 1 0 ppm
1.10
441.
1198
1.25
441.
2698
1.29
621.
3117
1.35
401.
3695
1.67
981.
9352
1.95
222.
0526
2.06
973.
9343
4.33
754.
3523
4.37
134.
3825
4.40
184.
4175
4.43
324.
4503
4.46
484.
4874
4.50
034.
5131
4.53
524.
5501
4.62
734.
6428
4.65
844.
6612
4.67
704.
6927
4.70
826.
7841
6.79
616.
8040
6.88
456.
8933
6.90
497.
1944
7.21
267.
2303
7.26
547.
2858
7.30
417.
3425
7.36
079.
9458
3.00
3.02
3.03
3.04
1.09
1.10
1.04
2.01
2.09
1.08
1.00
1.00
5.05
1.03
NH
CO P O
OO
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
23.7
323
.78
23.8
623
.90
23.9
523
.99
43.6
7
54.7
254
.88
56.2
256
.31
71.4
071
.44
71.4
976
.70
77.0
177
.33
126.
9612
7.94
128.
3813
8.90
141.
5914
2.58
142.
6014
2.71
144.
64
163.
0216
3.06
164.
0716
4.23
NH
CO P O
OO
-120-100-80-60-40-20120 100 80 60 40 20 0 ppm
13.8
7
NH
CO P O
OO
-
29
3q
11 10 9 8 7 6 5 4 3 2 1 0 ppm
1.20
601.
2214
1.25
501.
2719
1.29
671.
3122
1.32
401.
3394
1.35
221.
3676
1.97
511.
9911
2.09
112.
1073
3.76
903.
8594
4.53
204.
5475
4.56
314.
5667
4.58
244.
5979
4.61
354.
6409
4.65
644.
6719
4.67
594.
6876
4.69
174.
7072
4.72
275.
2749
5.28
215.
3091
5.31
635.
4694
5.47
555.
5036
5.50
976.
7249
6.73
656.
7446
6.83
886.
8462
6.85
046.
8583
7.26
027.
4321
7.45
107.
4704
7.55
517.
5736
7.59
218.
0421
8.06
05
3.00
9.08
0.99
0.98
1.00
0.99
2.05
1.01
1.01
0.99
0.98
1.99
1.00
2.03
CO
O PO
OO
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
23.9
223
.96
23.9
724
.00
24.1
124
.13
24.1
553
.41
53.5
253
.98
54.1
461
.49
61.5
270
.20
70.2
670
.29
70.3
472
.19
72.2
576
.68
77.0
077
.32
128.
4012
9.65
130.
1013
3.02
138.
8714
0.87
141.
0714
1.10
143.
00
166.
1916
7.18
167.
33
CO
O PO
OO
-140-120-100-80-60-40-20120 100 80 60 40 20 0 ppm
13.5
1
CO
O PO
OO
-
30
3r
10 9 8 7 6 5 4 3 2 1 0 ppm
1.10
381.
1212
1.13
85
3.77
973.
7982
3.82
093.
8399
3.85
823.
8763
3.89
443.
9123
3.93
093.
9350
3.95
373.
9715
7.26
007.
3077
7.32
477.
3397
7.37
027.
3869
7.39
977.
4271
7.44
007.
5346
7.55
317.
5703
8.01
218.
0313
8.04
778.
0669
6.00
4.09
7.05
1.01
0.99
PO
O
O
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
15.9
816
.05
61.7
361
.79
76.6
877
.00
77.3
2
126.
0612
6.76
126.
9012
7.39
127.
4412
7.92
129.
3213
1.26
131.
4013
1.90
133.
7313
3.83
141.
4214
1.47
145.
9914
6.08
PO
O
O
-70-60-50-40-30-20-10100 90 80 70 60 50 40 30 20 10 0 ppm
18.2
0
POO
O
-
31
3s
10 9 8 7 6 5 4 3 2 1 0 ppm
1.07
371.
0913
1.10
891.
6384
1.70
702.
9236
2.94
073.
0181
3.03
273.
6763
3.69
423.
7012
3.71
323.
7190
3.73
133.
7380
3.74
923.
7562
3.77
403.
8071
3.82
483.
8320
3.84
243.
8497
3.86
023.
8675
3.87
793.
8852
3.90
307.
2350
7.25
167.
2554
7.26
817.
2809
7.28
437.
3061
7.32
467.
3412
6.01
3.03
3.00
2.06
2.07
2.03
2.03
5.07
PO O
O
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.0
116
.08
17.7
817
.86
35.3
635
.47
42.1
842
.34
61.0
561
.12
76.6
877
.00
77.3
2
120.
6112
1.83
121.
8412
2.43
122.
6412
2.75
127.
2212
7.28
127.
2912
7.76
142.
2514
2.33
150.
0215
0.10
PO O
O
-100-80-60-40-20120 100 80 60 40 20 0 ppm
18.7
7
PO O
O