Molecules 2016, 21, 936
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824; 622.Elemental analysis: Calcd. for C35H26NO3P: C, 77.91; H, 4.86; N, 2.60. Found: C, 77.76, H,
4.86, N, 2.79.
Diphenyl N-(4-methoxyphenyl)amino(pyren-1-yl)methylphosphonate (3b). Y = 0.3 g (52%), yellow solid, m.p.
161 ˝C. 1H-NMR (CDCl3):
δ
8.49 (d, 3JHH = 9.2 Hz, Hpyr, 1H); 8.34 (dd, 3JHH = 7.7 and 4JHH = 1.9 Hz,
Hpyr, 1H); 8.24-8.21 (m, Hpyr, 3H); 8.14 (d, Hpyr, 3JHH = 8.1 Hz, 1H); 8.08 (d, 3JHH = 8.9 Hz, Hpyr, 1H);
8.04 (d, 3JHH = 7.7 Hz, Hpyr, 1H); 8.02–8.01 (m, Hpyr, 2H); 7.31–7.28 (m, HPh, 2H); 7.19–7.16 (m, HPh, 3H);
6.95–6.92 (m, HPh, 2H); 6.89–6.87 (m, HPh, 1H); 6.62–6.58 (m, HPh, p-C6H4, 6H); 6.23 (d, 2JPH = 24.4 Hz,
CHP, 1H); 3.61 (s, CH3, 3H). 13C-NMR (CDCl3):
δ
153.2 (d, 2JCP = 5.4 Hz, Cpara); 150.7 (d, 2JCP = 9.9 Hz,
C
POC); 150.3 (d, 2JCP = 9.7 Hz, CPOC); 131.5 (Cpyr); 131.2 (d, 4JCP = 3.2 Hz, Cpyr); 130.8 (Cpyr); 130.0 (CPh);
129.7 (Cpyr); 129.6 (d, 3JCP = 7.2 Hz, Cpyr); 129.5 (CPh); 128.8 (Cpyr); 128.6 (Cpyr); 127.9 (Cpyr); 127.7
(Cpyr); 126.3 (CPh); 125.8 (CPh); 125.6 (Cpyr); 125.6 (Cpyr); 125.5 (Cpyr); 125.2 (d, 4JCP = 1.8 Hz, Cpyr);
125.0 (Cpyr); 124.9 (Cpyr); 122.2 (Cpyr); 121.0 (d, 3JCP = 4.2 Hz, CPh); 120.0 (d, 4JCP = 4.4 Hz, CPh); 115.7
(d, 4JCP = 9.7 Hz, CPh); 115.1 (Cpara); 55.7 (CAr-OC); 53.0 (d, 1JCP = 154.3 Hz, PC). 31P-NMR (CDCl3):
δ 16.32. IR (KBr): 3383 (νNH); 3294 (νCH); 3037; 2958 (CH3); 1591, 1511, 1486; 1451 (C=C); 1245 (P=O);
1211; 1068; 1024 (P-O); 941; 834; 815; 618. Elemental analysis: Calcd. for C36H28NO4P: C, 75.91; H, 4.95;
N, 2.46. Found: C, 75.76, H, 5.06, N, 2.54.
Diphenyl N-(4-methylphenyl)amino(pyren-1-yl)methylphosphonate (3c). Y = 0.44 g (79%), yellow solid,
˝
1
3 HH
3 HH
m.p. 181–182 C. H-NMR (CDCl3):
δ
8.51 (d, J
= 9.3 Hz, Hpyr, 1H); 8.34 (dd, J
= 8.2
4
and JHH = 2.5 Hz, Hpyr, 1H); 8.25-8.21 (m, Hpyr, 3H); 8.13 (d, Hpyr
(d, 3JHH = 8.9 Hz, Hpyr, 1H); 8.04 (t, J
,
3JHH = 8.2 Hz, 1H); 8.08
3 HH
3 HH
= 7.6 Hz, Hpyr, 1H); 8.01 (d, J
= 8.8 Hz, Hpyr, 2H);
7.31–7.29 (m, HPh, 2H); 7.20–7.15 (m, HPh, 3H); 7.05–7.02 (m, HPh, 2H); 6.94–6.91 (m, HPh, 2H); 6.88-6.86
(m, HPh, 1H); 6.68-6.64 (m, HPh, 3H); 6.58–6.57 (m, HPh, 2H); 6.31 (d, 2JPH = 24.6 Hz, CHP, 1H). 13C-NMR
(CDCl3):
δ
150.7 (d, 2JCP = 9.8 Hz, CPOC); 150.3 (d, 2JCP = 9.7 Hz, CPOC); 143.7 (d, 2JCP = 15.9 Hz, Cpara);
131.6 (Cpyr); 131.2 (d, 4JCP = 3.2 Hz, Cpyr); 130.8 (Cpyr); 130.0 (CPh); 129.8 (Cpyr); 129.6 (d, 3JCP = 7.3 Hz,
4
Cpyr); 129.5 (Cpara); 128.8 (d, JCP = 2.1 Hz, Cpyr); 128.6 (Cpyr); 128.3 (Cpyr); 127.8 (Cpara); 127.7
(d, 4JCP = 1.6 Hz, Cpyr); 126.3 (Cpyr); 125.8 (Cpyr); 125.6 (CPh); 125.5 (d, 4JCP = 2.3 Hz, Cpyr); 125.5 (CPh);
125.2 (d, 4JCP = 1.9 Hz, Cpyr); 125.0 (Cpyr); 124.9 (Cpyr); 122.2 (Cpyr); 121.0 (d, 3JCP = 4.0 Hz, CPh); 120.0
(d, 3JCP = 4.4 Hz, CPh); 114.3 (Cpara); 52.5 (d, 1JCP = 155.1 Hz, PC); 20.5 (CAr-OC). 31P-NMR (CDCl3):
δ 15.23. IR (KBr): 3303 (νCH); 2923 (CH3); 1591, 1489, 1458 (C=C); 1268 (P=O); 1024 (P-O); 926, 840;
770; 688. Elemental analysis: Calcd. for C36H28NO3P: C, 78.11; H, 5.10; N, 2.53. Found: C, 77.86;
H, 5.31; N, 2.47.
Diphenyl˝ N-benzylamino(pyren-1-yl)methylphosphonate (3d). Y = 0.43 g (77%), yellow solid, m.p.
118–119 C. 1H-NMR (CDCl3):
δ
8.51–8.49 (m, Hpyr, 1H); 8.26 (d, 3JHH = 8.0 Hz, Hpyr, 1H); 8.24–8.21
3 HH
(m, Hpyr, 3H); 8.13–8.09 (m, Hpyr, 3H); 8.04 (t, J
= 7.6 Hz, Hpyr, 1H); 7.29–7.25 (m, HPh, 5H);
7.20–7.19 (m, HPh, 2H); 7.15–7.13 (m, HPh, 3H); 7.02–7.00 (m, HPh, 2H); 6.93 (app. t, 3JHH = 7.4 Hz,
HPh, 1H); 6.73 (app. d, 3JHH = 8.2 Hz, HPh, 2H); 5.58 (d, JPH = 20.8 Hz, CHP, 1H); 3.93
2
(d, 3JHH = 13.3 Hz, NCH2, 1H); 3.66 (d, J
= 13.3 Hz, NCH2, 1H). 13C-NMR (CDCl3):
C
δ
151.0
3 HH
(d, 2JCP = 9.9 Hz, CPOC); 150.5 (d, 2JCP = 9.7 Hz,
POC); 139.1 (CPh); 131.6 (Cpyr); 131.4 (d, 4JCP = 3.0 Hz,
Cpyr); 130.8 (Cpyr); 130.4 (Cpyr); 130.3 (Cpyr) 130.0 (Cpyr); 129.9 (Cpyr); 129.8 (CPh); 129.5 (CPh); 128.8
(CPh); 128.6 (CPh); 128.2 (Cpyr); 128.0 (Cpyr); 127.7 (d, 4JCP = 1.5 Hz, Cpyr); 127.5 (Cpyr); 126.3 (Cpyr);
125.7 (CPh); 125.5 (d, 4JCP = 2.8 Hz, Cpyr); 125.4 (CPh); 125.2 (Cpyr); 125.0 (Cpyr); 122.7 (Cpyr); 120.8
(d, 3JCP = 4.3 Hz, CPh); 120.3 (d, 3JCP = 4.3 Hz, CPh); 51.6 (d, 3JCP = 17.8 Hz, PCNC). 31P-NMR (CDCl3):
δ
16.22. IR (KBr): 3386 (νNH); 3041, 2917 (CH3); 1616, 1587, 1518, 1451 (C=C); 1245 (P=O); 1066; 1024
(P-O); 941, 843; 777; 618. Elemental analysis: Calcd. for C36H28NO3P: C, 78.11; H, 5.10; N, 2.53. Found:
C, 77.81; H, 5.24; N, 2.40.
3.1.2. Dimethyl N-(R)-α-Methylbenzylamino(pyren-1-yl)methylphosphonate (4)
The reaction was carried out as it is described above, but the post-reaction mixture was dissolved
in dichloromethane and washed three times with a saturated aqueous sodium bicarbonate solution. The