2570 J . Org. Chem., Vol. 62, No. 8, 1997
Reynolds et al.
1300, 1176, 993, 742, 708; UV-vis (CH2Cl2) 232, 276; mp 138-
140 °C. Anal. Calcd for C39H47N3BP: C, 78.12; H, 7.90; N,
7.01. Found: C, 77.85; H, 7.87; N, 7.42.
Hz), 136.7 (dd, 3J CF ) 8.2 Hz, 3J PC ) 23.3 Hz), 131.4 (d, 3J CF
)
2 2
8.1 Hz), 125.0, 118.5 (d, J CF ) 21.4 Hz), 114.8 (d, J CF ) 22.3
3
Hz), 109.5 (1J PC ) 162.0 Hz), 36.5 (d, J PC ) 3.8 Hz).
3k ‚BPh4: 1H NMR (CD3CN, δ) 7.50-7.47 (m, 3H), 7.36 (dd,
J HH ) 17.7 Hz, J PH ) 22.5 Hz, 1H), 7.26 (br s, 9H), 6.98 (t, J
) 7.5 Hz, 8H), 6.82 (t, J ) 7.2 Hz, 4H), 6.61 (dd, J HH ) 17.7
3d ‚Cl: 1H NMR (D2O, δ) 7.48 (dd, J PH ) 23.7 Hz, J HH ) 17.7
Hz, 1 H), 7.01 (s, 2H), 6.24 (dd, J PH ) 24.6 Hz, J HH ) 18.0 Hz,
1 H), 2.81 (d, J PH ) 9.9 Hz, 18 H), 2.29 (s, 6H), 2.27 (s, 3H);
13C NMR (D2O, δ) 150.8 (d, 2J PC ) 5.2 Hz), 140.2, 137.1, 131.7
3
Hz, J PH ) 21.3 Hz, 1H), 2.74 (d, J PH ) 10.2 Hz); 31P NMR
(CH3CN, δ) 51.4; IR (KBr, cm-1) 3053, 3001, 2984, 2949, 2912,
1579, 1481, 1448, 1302, 1178, 995, 742, 708; UV-vis (CH2Cl2)
232, 268; mp 170-173 °C dec. Anal. Calcd for C38H44N3BFP:
C, 75.62; H, 7.35; N, 6.96. Found: C, 75.88; H, 7.23; N, 7.12.
3l‚BPh4: 1H NMR (CD3CN, δ) 8.28 (d, J ) 8.7 Hz, 2H), 7.88
(d, J ) 9Hz, 2H), 7.45 (dd, J PH ) 22.5, J HH ) 17.9, 1 H), 7.25
3
1
(d, J PC ) 21.0 Hz), 129.6, 113.9 (d, J PC ) 156.1 Hz), 36.6 (d,
2J PC ) 3.8 Hz), 20.7, 20.6; 31P NMR (D2O, δ) 50.0; UV-vis (H2O)
200, 214, 274. 3d ‚BPh4: IR (KBr, cm-1) 3055, 2970, 2860,
1612, 1482, 1303, 1202, 995, 700; mp 171-173 °C.
3e‚Cl: 1H NMR (D2O, δ) 7.63 (d, J HH ) 8.7 Hz, 1H), 7.30
(dd, J PH ) 22.7 Hz, J HH ) 17.4 Hz, 1H), 7.02 (d, J HH ) 9.0 Hz,
1H), 6.46 (dd, J PH ) 21.5 Hz, J HH ) 17.4 Hz, 1H), 3.83 (s, 3H),
(br s, 8H), 6.97 (t, J ) 7.2 Hz, 8H), 6.84-6.69 (m, 5H), 2.74 (d,
1
3J PH ) 10.2 Hz, 18 H); 13C NMR (CD3CN, δ) 164.2 (q, J BC
)
3
2.73 (d, J PH ) 9.61 Hz, 18H); 13C NMR (D2O, δ) 161.9, 151.3
2
3
2
1
49.2 Hz), 149.5, 149.0 (d, J PC ) 6.6 Hz), 140.5 (d, J PC ) 22.9
(d, J PC ) 6.4 Hz), 130.7, 128.1, 115.0, 104.7 (d, J PC ) 164.3
1
Hz), 56.0, 36.5 (d, J PC ) 3.5 Hz). 3e‚BPh4: 31P NMR (CH3-
2
Hz), 136.1, 129.8, 126.1, 124.5, 122.3, 112.9 (d, J PC ) 160.7
Hz), 36.4 (d, 2J PC ) 3.9 Hz); 31P NMR (CD3CN, δ) 50.7; IR (KBr,
cm-1) 3053, 2964, 2908, 1591, 1520, 1481, 1342, 1302, 1176,
995, 850, 708; UV-vis (CH2Cl2) 234, 276 (sh), 294; mp 202-
203 °C. Anal. Calcd for C38H44N4BO2P: C, 72.38; H, 7.03; N,
8.89. Found: C, 71.90; H, 7.06; N, 8.85.
CN, δ) 52.5; IR (KBr, cm-1) 3054, 3005, 2944, 1601, 1512, 1479,
1302, 1261, 1177, 993, 735, 708; UV-vis (CH2Cl2) 234, 312; mp
206-221 °C.
3f‚BPh4: 1H NMR (CDCl3, δ) 7.43 (br s, 8H), 7.03 (t, J )
3
7.2 Hz, 8H), 6.94-6.86 (m, 5H), 6.69 (s, 2H), 5.97 (dd, J PH
)
21.2 Hz, J HH ) 17.6 Hz, 1H), 4.16 (s, 3H), 3.82 (s, 6H), 2.46 (d,
3m ‚BPh4: 1H NMR (CD3CN, δ) 7.67 (s, 1H), 7.21-7.12 (br
s and partial dd from vinyl H, 9H), 6.98 (t, J ) 7.5 Hz, 8H),
3J PH ) 9.9 Hz, 18 H); 13C NMR (CD3CN, δ) 164.2 (q, J BC
)
1
3
49.4 Hz), 154.1, 151.9 (d, 2J PC ) 6.9 Hz), 136.19, 136.16, 130.0
6.88-6.81 (m, 5H), 6.60 (br s, 1H), 6.27 (J HH ) 17.2 Hz, J PH
(d, J PC ) 23.0 Hz), 126.0, 122.2, 106.6, 106.4 (d, J PC ) 162.9
) 21.6 Hz, 1H), 2.71 (d, J PH ) 9.9 Hz, 18H); 13C NMR (CD3-
3
1
3
2
1
3
Hz), 60.5, 56.4, 36.6 (d, J PC ) 4.5 Hz); 31P NMR (CD3CN, δ)
CN, δ) 164.3 (q, J BC ) 49.3 Hz), 150.8 (d, J PC ) 25.4 Hz),
146.9, 137.9 (d, 2J PC ) 7.9 Hz), 136.2, 126.0, 122.2, 117.5, 113.4,
103.7 (d, 1J PC ) 167.2), 36.5 (d, 2J PC ) 3.9 Hz); 31P NMR (CH3-
CN, δ) 51.9; IR (KBr, cm-1) 3051, 2999, 2906, 1616, 1479, 1302,
1167, 991, 860, 741, 706; UV-vis (CH2Cl2) 234, 304; mp
decomposed to brown solid at 120 °C. Anal. Calcd for
C36H43N3BOP: C, 75.13; H, 7.53; N, 7.30. Found: C, 74.96;
H, 7.72; N, 7.15.
52.6; IR (KBr, cm-1) 3054, 2997, 2937, 1579, 1481, 1333, 1302,
1128, 991, 708; UV-vis (CH2Cl2) 232, 316; mp 190-192 °C.
3g‚Cl: 1H NMR (D2O, δ) 7.34 (d, J ) 8.7 Hz, 1H), 7.269 (dd,
J PH ) 23.1 Hz, J HH ) 17.7 Hz, 1 H), 6.77 (d, J ) 9.0 Hz, 1H),
6.44 (dd, J PH ) 22.4 Hz, J HH ) 17.7 Hz, 1 H), 3.72 (s, 3H),
3.71 (s, 3H), 3.68 (s, 3H), 2.61 (d, J PH ) 9.6 Hz, 18 H); 13C
3
2
NMR (D2O, δ) 156.1, 152.3, 145.4 (d, J PC ) 7.3 Hz), 141.8,
124.26, 121.4 (d, 3J PC ) 30.3 Hz), 109.3, 106.7 (d, 1J PC ) 162.7
3n ‚Cl: 1H NMR (D2O, δ) 7.68-7.21 (m, 8H), 6.18 (dd, J PH
)
Hz), 62.4, 61.5, 56.5, 36.4 (d, J PC ) 3.2 Hz). 3g‚BPh4: 31P
22.5 Hz, J HH ) 17.7 Hz, 1H), 2.55 (d, J PH ) 10.2 Hz, 18 H);
2
NMR (CH3CN, δ) 52.6; IR (KBr, cm-1) 3055, 2999, 2937, 1618,
1491, 1300, 1176, 1096, 993, 735, 707; UV-vis (CH2Cl2) 234,
312; mp 178-180 °C. Anal. Calcd for C41H51N3BO3P: C,
72.88; H, 7.61; N, 6.22. Found: C, 72.45; H, 7.50; N, 6.32.
3h ‚Cl: 1H NMR (D2O, δ) 7.41 (dd, J PH ) 26.4 Hz, J HH ) 17.7
Hz, 1 H), 6.65 (dd, J PH ) 26.9 Hz, J HH ) 17.7 Hz, 1 H), 6.02 (s,
13C NMR (D2O, δ) 147.8 (d, 2J PC ) 5.4 Hz), 133.6, 131.8, 131.1
3
(d, J PC ) 21.9 Hz), 130.8, 129.2, 129.0, 128.0, 127.1, 126.2,
1
2
122.9, 110.6 (d, J PC ) 161.2 Hz), 36.5 (d, J PC ) 2.5 Hz); 31P
NMR (CH3CN, δ) 51.1. 3n ‚BPh4: IR (KBr, cm-1) 3051, 2999,
2947, 2908, 1579, 1479, 1300, 1174, 1064, 993, 743, 708; UV-
vis (CH2Cl2) 230, 244, 328; mp 160-162 °C. Anal. Calcd for
C42H47N3BP: C, 79.36; H, 7.45; N, 6.61. Found: C, 79.12; H,
7.24; N, 6.99.
3
2H), 3.76 (s, 6H), 3.74 (s, 3H), 2.69 (d, J PH ) 9.6 Hz, 18 H);
13C NMR (D2O, δ) 163.9, 161.4, 141.6 (d, 2J PC ) 9.0 Hz), 105.2
(d, 3J PC ) 21.5 Hz), 105.1 (d, 1J PC ) 159.6 Hz), 91.1, 56.3, 55.9,
3o‚BPh4: 1H NMR (CD3CN, δ) 8.16 (s, 1H), 7.97-7.82 (m,
4H), 7.60-7.47 (m, 3H, naphthalene aromatics and one vinyl
proton), 7.25 (br s, 8H), 6.97 (t, J ) 7.2 Hz, 8H), 6.82 (t, J )
36.6 (d, J PC ) 3.0 Hz). 3h ‚BPh4: 31P NMR (CD3CN, δ) 53.6;
2
IR (KBr, cm-1) 3054, 2999, 2940, 2858, 1505, 1488, 1298, 1207,
1159, 1120, 991, 734, 707; UV-vis (CH2Cl2) 234, 318; mp 160-
163 °C. Anal. Calcd for C41H51N3BO3P: C, 72.88; H, 7.61; N,
6.22. Found: C, 73.03; H, 7.55; N, 6.00.
7.2 Hz, 4H), 6.68 (dd, J HH ) 17.7 Hz, J PH ) 21.6, 1H), 2.77 (d,
1
3J PH ) 9.9 Hz, 18 H); 13C NMR (CD3CN, δ) 164.2 (q, J BC
)
2
49.6 Hz), 151.9 (d, J PC ) 6.5 Hz), 136.1, 134.9, 133.5, 132.3,
3i‚Cl: 1H NMR (D2O, δ) 7. 56 (d, J ) 8.7 Hz, 2H), 7.21 (dd,
131.2, 129.3, 129.2, 128.4, 128.2, 127.6, 126.0, 123.9, 122.2,
1
2
2J PH ) 22.5 Hz, J HH ) 17.4, 1H), 6.85 (d, J ) 8.7 Hz, 2H), 6.26
107.7 (d, J PC ) 162.4 Hz), 36.5 (d, J PC ) 4.1 Hz); 31P NMR
(CH3
1481, 1300, 1177, 993, 735, 708; UV-vis (CH2Cl2) 234, 270, 310,
H47N3BP: C,
CN, δ) 51.9; IR (KBr, cm-1) 3053, 2999, 2949, 1608, 1481,
3
(dd, J PH ) 21.7 Hz, J HH ) 17.6 Hz, 1H), 2.95 (s, 6H), 2.72 (d,
3J PH ) 10.2, 18H). 3i‚BPh4: 1H NMR (CDCl3, d) 7.43 (br s,
8H), 7.35 (d, J ) 9 Hz, 2H), 7.04 (t, J ) 7.2 Hz, 8H), 6.96-
354 (sh); mp 222-227 °C. Anal. Calcd for C42
3
79.36; H, 7.45; N, 6.61. Found: C, 79.64; H, 7.28; N, 6.49.
6.86 (m, 3H), 5.66 (dd, J PH ) 22.1, J HH ) 17.3, 1H), 3.05 (s,
6H), 2.49 (d, 3J PH ) 9.6 Hz, 18 H); 13C NMR (CD3CN, δ) 164.2
(q, 1J BC ) 49 Hz), 136.2, 126.1, 112.1, 39.8, 36.6; 31P NMR
(CH3CN, δ) 53.6; IR (KBr, cm-1) 3053, 2997, 2908, 1608, 1523,
1479, 1182, 993, 742, 706; UV-vis (CH2Cl2) 234, 322, 378; mp
193-195 °C. Anal. Calcd for C38H46N4BP: C, 76.43; H, 8.02;
N, 8.91. Found: C, 76.56; H, 7.90; N, 8.76.
1
3p ‚Cl: H NMR (D2O, δ) 7.71-7.19 (m, 7H), 7.01-6.93 (m,
3H), 5.82 (dd, J PH ) 22.2 Hz, J HH ) 17.4 Hz, 1 H), 2.48 (d,
3J PH ) 9.9 Hz, 18 H); 13C NMR (D2O, δ) 148.1 (d, J PC ) 6.0
2
Hz), 130.8, 130.7, 130.2 (d, 3J PC ) 22.0 Hz), 130.0, 129.7, 129.1,
128.3, 127.9, 127.6, 127.4, 127.2, 124.0, 123.0, 122.4, 111.1 (d,
1J PC ) 161.3 Hz), 36.3 (d, J PC ) 3.6 Hz). 3p ‚BPh4: 31P NMR
2
3j‚BPh4: 1H NMR (CDCl3, δ) 7.67 (d, J ) 8.4 Hz, 2H), 7.48
(d, J ) 8.7 Hz, 2H), 7.74 (dd, J HH ) 17.7 Hz, J PH ) 19.5 Hz,
1H), 7.25 (br s, 8H), 6.97 (t, J ) 7.2 Hz, 8H), 6.82, (t, J ) 7.2
(CD3CN, δ) 49.9; IR (KBr, cm-1) 3053, 2999, 2906, 1601, 1579,
1479, 1302, 1174, 991, 744, 708; UV-vis (CH2Cl2) 248, 334; mp
204-208 °C. Anal. Calcd for C46H49N3BP: C, 80.58; H, 7.20;
N, 6.13. Found: C, 80.06; H, 7.19; N, 6.46.
Hz, 4 H), 6.56 (dd, J HH ) 17.6 Hz, J PH ) 21.2 Hz, 1H), 2.73 (d,
3J PH ) 9.9 Hz, 18 H); 13C NMR (CD3CN, δ) 164.2 (q, J BC
)
1
3q‚BPh4: 1H NMR (CD3CN, δ) 7.56 (d, J ) 7.5 Hz, 2H),
7.41-6.82 (aromatics and vinyls; overlapping peaks, 28 H),
2
49.2 Hz), 150.4 (d, J PC ) 6.6 Hz), 136.2, 130.4, 129.6, 126.0,
122.2, 108.6 (d, J PC ) 162.3 Hz), 36.5 (d, J PC ) 3.1 Hz); 31P
NMR (CH3CN, δ) 51.6; IR (KBr, cm-1) 3053, 2999, 2909, 1608,
1481, 1302, 1177, 995, 735, 708; UV-vis (CH2Cl2) 230, 276; mp
189-192 °C. Anal. Calcd for C38H44N3BClP: C, 73.61; H, 7.15;
N, 6.78. Found: C, 73.18; H, 7.04; N, 7.10.
1
2
6.12-5.99 (m, 1H), 2.70 (d, J PH ) 9.9 Hz, 18 H); 13C NMR
3
(CD3CN, δ) 164.2 (q, 1J BC ) 49.4 Hz), 152.0 (d, 2J PC ) 5.9 Hz),
2
142.9, 136.2, 130.2, 129.5, 128.3, 127.9, 127.0 (d, J PC ) 13.1
Hz), 126.0, 122.2, 109.8 (d, J PC ) 162.8 Hz); 31P NMR (CH3-
1
CN, δ) 51.2; IR (KBr, cm-1) 3055, 2999, 2951-2822, 1622,
1597, 1479, 1300, 1176, 993, 747, 708; UV-vis (CH2Cl2) 232,
316; mp 229-232 °C. Anal. Calcd for C40H47N3BP‚1/2H2O: C,
78.55; H, 7.75; N, 6.87. Found: C, 78.61; H, 7.67; N, 7.10.
3k ‚Cl: 1H NMR (D2O, δ) 7.52-7.23 (m, 5H), 6.70 (dd, J HH
17.7 Hz, J PH ) 21.0 Hz, 1H), 2.78 (d, 3J PH ) 9.9 Hz, 18 H); 13
)
C
NMR (D2O, δ) 163.2 (d, 1J CF ) 244.1 Hz), 150.4 (d, 2J PC ) 20.4