1,2,4ꢀOxzaphosphinanes
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 8, August, 2013
1889
3
3
1 H, H(12), JHH = 7.6 Hz); 7.81 (br.dd, H(10), JPCCH
=
= 7.2 Hz, 5JPCCCCC(18) = 2.7 Hz); 128.23 (dm (d), C(16), 1JHC(16)
=
= 12.1Hz, 3JHH = 7.5Hz). 13C NMR (DMSOꢀd6), : 57.79 (ddt (d)*,
C(3), JHC(3) = 139.7 Hz, JPC(3) = 96.2 Hz, JHC(16)CC(3)
= 4.1 Hz); 117.18 (dd (s), C(5), 1JHC(5) = 159.3 Hz, 3JHC(7)CC(5)
= 160.0 Hz, JPCCC(16) = 5.0 Hz); 128.31 (dm (d), C(17),
3
1
1
3
4
=
=
1JHC(17) = 160.0 Hz, JPCCCC(17) = 2.2 Hz); 128.90 (ddd (d),
C(11), 1JHC(11) = 162.5 Hz, 3JPCCC(11) = 13.1 Hz, 3JHC(13)CC(11)
=
1
1
= 8.5 Hz); 121.39 (br.dd (d), C(7), JHC(7) = 162.5 Hz,
= 7.2 Hz); 129.21 (br.dt (d), C(9), JPC(9) = 132.8 Hz,
3JHC(5)CC(7) = 8.6Hz, JPOCCC(7) = 1.3); 119.67 (br.ddd (d),
3JHC(11)CC(9) = 7.2 Hz); 131.45 (ddddd (d), C(10), JHC(10)
=
4
1
C(8), 1JHC(8) = 161.3 Hz, 3JHC(6)CC(8) = 6.5—7.0 Hz, 3JPOCC(8)
=
=
= 162.4 Hz, JPCC(10) = 10.3 Hz, JHC(12)CC(10) = 7.2 Hz,
2
3
2
1
2
= 6.3 Hz, JHC(7)C(8) = 2.8 Hz); 124.39 (dd (s), C(6), JHC(6)
3JHC(14)CC(10) = 7.2 Hz, JHCC(10) = 1.8 Hz); 133.29 (dtdt (d),
C(12), 1JHC(12) = 162.6 Hz, 3JHC(10)CC(12) = 7.2 Hz, 4JPCCCC(12)
3
= 162.1 Hz, JHC(8)CC(6) = 8.7 Hz); 128.57 (br.dt (d), C(18),
=
1JHC(18) = 160.8 Hz, JHC(16)CC(18) = 7.2 Hz, JPCCCCC(18)
=
= 2.8 Hz, JHCC(12) = 1.2 Hz); 134.72 (m (d), C(15),
2JHC(17)CC(15) = 7.8 Hz, 2JPCC(15) = 6.2 Hz, 2JH(3)C(15) = 4.5 Hz);
135.87 (m (d), C(4a), 3JPCNC(4a) = 4.3 Hz); 139.88 (br.dddd (d),
3
5
2
1
= 3.7 Hz); 127.58 (dddd (d), C(16), JHC(16) = 159.7 Hz,
3JHC(20)CC(16) = 5.5—6.0 Hz, JHC(18)CC(16) = 5.5—6.0 Hz,
3
3JPCCC(16) = 5.1 Hz); 128.67 (br.ddd (d), C(17), 1JHC(17) = 160.8 Hz,
3JHC(19)CC(17) = 7.2 Hz, 4JPCCCC(17) = 2.6 Hz); 128.08 (br.dddm (d),
C(8a), 3JHC(7)CC(8a) = 13.8 Hz, 3JHC(5)CC(8a) = 10.7 Hz, 2JPOC(8a)
=
= 7.2 Hz, JHC(8)C(8a) = 3.9 Hz). 31Pꢀ{1H} NMR (161.9 MHz,
2
C(11), 1JHC(11) = 161.1 Hz, 3JPCCC(11) = 13.6 Hz, 3JHC(13)CC(11)
=
CDCl3) : 32.1. 31P NMR (DMSOꢀd6), : 29.0 (m, JHNCP
= 27.0 Hz, 3JHCCP = 15.5—16.0 Hz, 3JHCCP = 12.0 Hz, 4JHCCCP
= 4.0 Hz).
=
=
3
2
2
= 7.7 Hz, JHCC(11) = 3.8 Hz, JHCC(11) = 3.5 Hz); 126.72
1
3
(br.dt (d), C(9), JPC(9) = 139.0 Hz, JHC(11)CC(9) = 7.7 Hz);
133.03 (br.dddd (d), C(10), 1JHC(10) = 164.4 Hz, 2JPCC(10) = 9.2 Hz,
3JHC(12)CC(10) = 7.6 Hz, JHC(14)CC(10) = 7.4—7.6 Hz); 133.11
(dtd (d), C(12), JHC(12) = 163.8 Hz, JHC(10)CC(12) = 7.5 Hz,
4JPCCCC(12) = 2.8 Hz); 133.23 (br.tdd (d), C(15), 3JHC(17)CC(15)
= 7.0—7.2 Hz, JPCC(15) = 6.2 Hz, JH(3)C(15) = 5.5—5.8 Hz);
134.61 (m (d), C(4a), 3JPCNC(4a) = 2.6 Hz); 139.88 (m (d), C(8a),
2JPOC(8a) = 8.4 Hz). 31Pꢀ{1H} NMR, : 24.9 (CDCl3), 24.9
(CF3COOH).
Diastereomer 5(d2) (from the mixture of 5(d2) : 5(d1) =
= 11 : 1). 1H NMR (CDCl3), : 3.96 (v.br.s, 1 H, NH); 4.66 (d, 1 H,
H(3), JPCH(3) = 15.0 Hz); 6.90 (dd, 1 H, H(5), JH(6)H(5)
= 7.8 Hz, 4JH(7)H(5) = 1.6 Hz); 6.97 (dddd, 1 H, H(7), 3JH(8)H(7)
3ꢀ(4ꢀMethoxy)phenylꢀ2ꢀoxoꢀ2ꢀphenylꢀ5,6ꢀbenzoꢀ1,4,2ꢀoxꢀ
azaphosphinane (6) was obtained similarly to 5. The total yield of
compound 6 was 79%. Diastereomer 6(d1) was isolated in the
individual state, m.p. 184—185 C (from acetonitrile, pale yelꢀ
low crystals). Diastereomer 6(d2) was characterized using a sample
of the light brown oil from the eluate fraction with the ratio
6(d2) : 6(d1) = 6 : 1. Found (%): C, 68.02; H, 4.91; N, 4.34;
P, 9.11. C20H18NO3P. Calculated (%): C, 68.38; H, 5.13;
3
1
3
=
2
2
+
N, 3.99; P, 8.83. MS, m/z (Irel (%)): 351 (7.9) M •, 274 (10.5)
[M – C6H5]+, 226 (27.8) [M – PH(O)C6H5]+, 217 (7.4) [M –
– NHCC6H4OCH3]+, 138 (19.2) [CH2P(O)C6H5]+, 121 (100.0)
[CH2C6H4OCH3]+, 77 (18.5) [C6H5]+.
2
3
=
=
=
=
3
4
5
= 8.0 Hz, JH(6)H(7) = 7.5 Hz, JH(5)H(7) = 1.6 Hz, JPH(7)
= 1.1 Hz); 7.06 (ddd, 1 H, H(6), 3JH(5)H(6) = 7.8 Hz, 3JH(7)H(6)
Diastereomer 6(d1). 1H NMR (CDCl3), : 3.77 (s, 3 H,
2
H(21)); 4.58 (d, 1 H, H(3), JPCH(3) = 3.5 Hz); 6.78 (dd, 1 H,
4
= 7.5—7.6 Hz, JH(8)H(6) = 1.5 Hz); 7.11 (dm, 2 H, H(16),
3JH(17)H(16) = 7.4 Hz, 4JHH(16) = 2.2 Hz, 4JHH(16) = 1.7—1.8 Hz);
7.20 (m, 3 H, H(17) and H(8)); 7.21 (dd, H(8), 3JH(7)H(8) = 8.0 Hz,
4JH(6)H(8) = 1.5 Hz); 7.25 (tdt, 1 H, H(18), 3JH(17)H(18) = 7.3 Hz,
H(5), 3JHH = 7.9 Hz, 4JHH = 1.5 Hz); 6.80 (m, 2 H, H(17), 3JHH
=
= 8.7 Hz); 6.83 (dddd, 1 H, H(7), 3JHH = 8.0 Hz, 3JHH = 7.4 Hz,
5
3
4JHH = 1.5 Hz, JPH = 1.2 Hz); 6.97 (ddd, 1 H, H(6), JHH
=
= 7.9 Hz, 3JHH = 7.4 Hz, JHH = 1.5 Hz); 7.07 (dd, 1 H, H(8),
3JHH = 8.0 Hz, 4JHH = 1.4 Hz); 7.25 (m, 2 H, H(16), 3JHH = 8.7 Hz,
4
4JH(16)H(18) = 1.7 Hz, JPH(7) = 1.6 Hz); 7.29 (br.ddd, 2 H,
6
H(11), JHH(11) =8.3 Hz, 3JHH(11) = 7.6 Hz, JPH(11) = 4.4 Hz);
4JHH = 2.0 Hz); 7.44 (br.ddd, 2 H, H(11), 3JHH = 8.3 Hz, 3JHH
=
3
4
7.41 (br.ddd, 2 H, H(10), 3JPCCH(10) = 11.9 Hz, 3JHH(10) = 8.3 Hz,
= 7.5 Hz, 4JPH = 3.8 Hz); 7.58 (tdt, 1 H, H(12), 3JHH = 7.5 Hz,
4JHH(10) = 1.4 Hz); 7.51 (tdt, 1 H, H(12), JH(11)H(12) = 7.4 Hz,
4JHH = 1.4 Hz, 5JPH = 1.4 Hz); 7.73 (ddm, 2 H, H(10), 3JPH
=
3
5JPH(12) = 1.4 Hz, 4JH(10)H(12) = 1.4 Hz). 1H NMR (DMSOꢀd6),
= 12.1 Hz, 3JHH = 8.3 Hz, 4JHH = 1.4 Hz). 1H NMR (DMSOꢀd6),
: 3.72 (s, 3 H, H(21)); 5.06 (dd, 1 H, H(3), 2JPCH(3) = 7.8 Hz,
2
: 4.74 (d, 1 H, H(3), JPCH(3) = 15.9 Hz); 6.70 (d, 1 H, NH,
3JPCNH = 26.8 Hz); 6.84 (br.dd, 1 H, H(7), 3JH(8)H(7) = 8.2 Hz,
3JHNCH(3) = 2.5 Hz); 6.71 (ddd, 1 H, H(7), JHH = 8.1 Hz,
3
3JH(6)H(7) = 7.8 Hz); 7.02 (ddd, 1 H, H(6), JH(5)H(6) = 8.3 Hz,
3JHH = 8.0 Hz, 4JHH = 1.8 Hz); 6.80 (dd, 1 H, NH, 3JPH = 21.9 Hz,
3JHH = 2.5 Hz); 6.87 (m, 2 H, H(17), 3JHH = 8.7 Hz); 6.90 (dd, 1 H,
3
3JH(7)H(6) = 7.8 Hz, 4JH(8)H(6) = 1.2 Hz); 7.08 (m, 2 H, H(16), 1 H,
3
4
3
4
H(5)); 7.12 (dd, 1 H, H(8), JH(7)H(8) = 8.2 Hz, JH(6)H(8)
= 1.2 Hz); 7.21—7.23 (m, 3 H, H(17), H(18)); 7.28 (m, 2 H,
=
H(5), JHH = 8.0 Hz, JHH = 1.8 Hz); 6.94 (ddd, 1 H, H(6),
3
4
3JHH = 8.1 Hz, JHH = 8.0 Hz, JHH = 1.4 Hz); 7.01 (dd, 1 H,
3
3
4
3
4
H(10), JPCCH(10) = 11.4 Hz, JHH(10) = 8.2 Hz, JHH(10)
= 1.3 Hz); 7.38 (br.ddd, 2 H, H(11), 3JHH(11) = 8.4 Hz, 3JHH(11)
= 7.5 Hz, 4JPH(11) = 3.9 Hz); 7.57 (tdt, 1 H, H(12), 3JH(11)H(12)
=
=
=
H(8), JHH = 8.0 Hz, JHH = 1.3 Hz), 7.24 (m, 2 H, H(16),
3JHH = 8.7 Hz, JHH = 2.0 Hz); 7.54 (br.ddd, 2 H, H(11),
4
3JHH = 8.3 Hz, 3JHH = 7.4 Hz, 4JPH = 3.7 Hz); 7.65 (tdt, 1 H, H(12),
3JHH = 7.4 Hz, 4JHH = 1.4 Hz, 5JPH = 1.4 Hz); 7.77 (ddm, 2 H,
= 7.5 Hz, JPH(12) = 1.2 Hz, JH(10)H(12) = 1.2 Hz). 13C NMR
5
4
1
1
3
3
4
(CDCl3), : 53.69 (ddt (d), C(3), JHC(3) = 140.0 Hz, JPC(3)
= 92.2 Hz, JH,C(16)CC(3) = 3.6—3.7 Hz); 116.37 (dd (s), C(5),
1JHC(5) = 159.8 Hz, JHC(7)CC(5) = 8.5 Hz); 118.49 (br.dd (d),
=
H(10), JPH = 12.1 Hz, JHH = 8.3 Hz, JHH = 1.4 Hz).
13C NMR (CDCl3), : 55.34 (q (s), C(21), 1JHC(21) = 144.0 Hz);
56.37 (ddt (d), C(3), JHC(3) = 138.2 Hz, JPC(3) = 95.6 Hz,
3JHC(16)CC(3) = 4.1 Hz); 114.30 (br.ddd (d), C(17), JHC(17)
=
= 160.0 Hz, JHC(19)CC(17) = 5.0 Hz, JPCCCC(17) = 2.1 Hz);
116.94 (dm (s), C(5), 1JHC(5) = 161.1 Hz, 3JHC(7)CC(5) = 8.7 Hz);
120.20 (br.ddd (d), C(7), 1JHC(7) = 162.4 Hz, 3JHC(5)CC(7) = 8.7 Hz,
4JPOCCC(7) = 1.4 Hz); 119.56 (ddddd (d), C(8), 1JHC(8) = 161.6 Hz,
3JHC(6)CC(8) = 8.7 Hz, 3JPOCC(8) = 6.3 Hz, 2JHC(7)C(8) = 2.4 Hz,
4JHC(5)CCC(8) = 1.1 Hz); 124.52 (dm (s), C(6), 1JHC(6) = 160.9 Hz,
3JHC(8)CC(6) = 8.5 Hz); 159.86 (tqd (d), C(18), JHC(16)CC(18)
3
3
1
1
1
3
4
1
C(7), JHC(7) = 164.0 Hz, JHC(5)CC(7) = 8.9 Hz, JPOCCC(7)
=
1
3
4
= 1.2 Hz); 118.85 (br.ddd (d), C(8), JHC(8) = 160.3 Hz,
3JHC(6)CC(8) = 7.8 Hz, JPOCC(8) = 5.9 Hz); 124.54 (ddd (s),
3
C(6), 1JHC(6) = 161.5 Hz, 3JHC(8)CC(6) = 8.5 Hz, 2JHCC(6) = 1.8 Hz);
1
3
127.89 (br.dt (d), C(18), JHC(18) = 160.5 Hz, JHC(16)CC(18)
=
* Here and further the splitting in the 13Cꢀ{1H} NMR spectra is
given in parentheses.
3
=