, 2005, 15(3), 101–103
C(10)
C(13)
Cl(7)
C(14)
C(9)
C(11)
C(8b)
C(8)
C(7)
C(15)
Cl(2)
C(12)
C(16)
C(8a)
C(6)
O
NH
H2N
C(12a)
C(4b)
C(12b)
O
P(2)
P
O(2)
O(1)
C(5)
C(4a)
C(4)
Ph
Cl(3)
Cl
C(3)
C(17)
4
2
C(18)
C(22)
C(21)
Cl(5)
C(19)
Cl(4)
O
OH
C(20)
O
H2O
P
Figure 1 Molecular structure of the solvate of compound 2 with CDCl3.
Selected bond lengths (Å): Cl(2)–P(2) 2.010(2), Cl(7)–C(7) 1.719(4),
P(2)–O(1) 1.586(3), P(2)–O(2) 1.471(3), P(2)–C(3) 1.740(5), O(1)–C(12b)
1.398(4), C(3)–C(4) 1.353(5), C(4b)–C(4a) 1.451(5), C(4a)–C(12b) 1.370(6);
selected bond angles (°): Cl(2)–P(2)–O(1) 103.2(1), Cl(2)–P(2)–O(2)
112.1(2), Cl(2)–P(2)–C(3) 108.5(2), O(1)–P(2)–O(2) 110.6(2), O(1)–P(2)–
C(3) 101.9(2), O(2)–P(2)–C(3) 119.0(2), P(2)–O(1)–C(12b) 120.9(3),
P(2)–C(3)–C(4) 117.6(3), C(4a)–C(4b)–C(5) 122.3(4), C(3)–C(4)–C(4a)
121.6(4), O(1)–C(12b)–C(4a) 118.7(4), O(1)–C(12b)–C(12a) 116.6(3),
C(4a)–C(12b)–C(12a) 124.8(3); selected torsion angles (°): Cl(2)–P(2)–
O(1)–C(12b) –65.0(3), O(2)–P(2)–O(1)–C(12b) 174.9(3), C(3)–P(2)–
O(1)–C(12b) 47.5(3), Cl(2)–P(2)–C(3)–C(4) 81.6(4), O(1)–P(2)–C(3)–
C(4) –26.8(4), O(2)–P(2)–C(3)–C(4) –148.7(3), P(2)–O(1)–C(12b)–C(4a)
–31.9(5), P(2)–O(1)–C(12b)–C(12a) 149(3), P(2)–C(3)–C(4)–C(4a) –6.9(6),
C(5)–C(4b)–C(4a)–C(12b) –169.1(4), C(3)–C(4)–C(4a)–C(12b) 30.0(6),
C(17)–C(4)–C(4a)–C(12b) –145.2(4), C(3)–C(4)–C(17)–C(18) –135.6(4),
C(3)–C(4)–C(17)–C(22) 40.0(6).
Ph
Cl
5
H2O
OH
O
P
OH
OH
Ph
Cl
The phenyl group at the 4-position is turned along the P(2)C(3)–
C(4)C(4a) plane on an angle of 40.0(6)° [C(3)C(4)C(17)C(22)].
The chrysene system is twisted to some extent, and a dihedral
angle between the C(4b)C(5)C(6)C(7)C(8)C(8a) benzo fragment
[which is planar within 0.011(5) Å] and the C(8b)C(9)C(10)–
C(11)C(13)C(14)C(15)C(16)C(12) naphtho fragment [which is
planar within 0.024(5) Å] is equal to 7.3(2)°.
6
§
7-Chloro-2-isopropylamino-2-oxo-4-phenylbenzo[o]-1,2-oxaphospha-
triphenylene 4. The mixture of 0.65 ml of isopropylamine and 10 ml of
benzene was added to 2 (1.5 g in 30 ml of dry benzene) and allowed to
stand for 2 days. The precipitate obtained after 2 days was filtered off,
washed with alkaline water (pH 8) and dried in air. Amide 4 was
obtained as white powder (1.26 g, 80%) with mp 299 °C. 1H NMR
Amide 4§ was obtained by the isopropylamine treatment of
1
compound 2. Its cyclic nature was established using H NMR
(400 MHz, [2H6]DMSO, 40 °C) d: 9.86 [ddd, H(16), JH(15)CCH(16) 6.2–
3
spectra [the 2JPOC(12b) and 3JPCCC(4a) 16.6 Hz coupling constants,
indicating two PC(3)C(4)C(4a) and POC(12b)C(4a) pathways
for the spin–spin interaction]. The full interpretation of the
13C-{1H} spectrum of amide 4 was made taking into account
both the signals multiplicity caused by the carbon–proton and
carbon–phosphorus coupling constants in 13C NMR spectrum
and published data.1–4
6.3 Hz, 4JH(14)CCCH(16) 3.3 Hz, 5JH(13)CCCCH(16) 0.7 Hz], 8.93 [br. dd, H(8),
4JH(6)CCCH(8) 1.5 Hz, 5JH(8)CCCCH(9) 1.1 Hz], 8.92 [br. dd, H(9), 3JH(10)CCH(9)
3
9.0 Hz], 8.27 [br. d, H(10), JH(9)CCH(10) 9.0 Hz], 8.19 [br. dd, H(13),
3JH(14)CCH(13) 6.0 Hz], 7.76–7.77 [m, H(14), H(15)], 7.31 [d, H(5), B-part
3
of AB-spectrum, JH(6)CCH(5) 8.8 Hz], 7.27 [br. dd, H(6), A-part of AB-
spectrum, 3JH(5)CCH(6) 8.8 Hz, 4JH(8)CCCH(6) 1.5 Hz], 7.27 and 7.40 (br. m,
Ph), 6.64 [d, H(3), 2JPCH 22.0 Hz], 5.68 (br. m, PNH), 3.58 (br. m, NCH),
1.21 and 1.22 (2d, Me, 3JHCCH 6.5 Hz). 13C NMR (the view of signal in
13C-{1H} NMR spectrum is given in parentheses) (100.6 MHz, [2H6]DMSO,
70 °C) d: 119.28 [dd (d), C(3), 1JPC 163.0 Hz, 1JHC 163.5 Hz], 152.24 [m
3
(br. s), C(4)], 115.49 [m (d), C(4a), JPCCC 16.6 Hz], 128.48 and 128.78
[2m (2s) C(4b), C(12)], 128.88 [d (s), C(5), 1JHC 163.9 Hz], 125.54 [dd
PCl3
O
O
1
3
O
(s), C(6), JHC 168.2 Hz, JHC(8)CC(6) 5.8 Hz], 130.09 [ddd (s), C(7),
2
2
3JHC(5)CC(7) 11.0 Hz, JHCC 6.0 Hz, JHCC 4.1 Hz], 122.93 [dd (s), C(8),
PCl3
1JHC 164.9 Hz, 3JHC(6)CC(8) 3.8 Hz], 127.05 [br. dd (s), C(8a), 3JHC(5)CC(8a)
O
3
3
7.7 Hz, JHC(9)CC(8a) 6.3 Hz], 130.54 [m (s), C(8b), JHC(10)CC(8b) 9.0 Hz,
3JHC(8)CC(8b) 3.0 Hz, 2JHC(9)C(8b) 1.4 Hz], 120.91 [d (s), C(9), 1JHC 157.5 Hz],
128.49 [is superimposed on C(19), (s), C(10)], 132.95 [m (s), C(11)],
1
3
3
2
120.68 [m (d), C(12a), JPOCC 4.9 Hz], 149.36 [d (d), C(12b), JPOC
1
3
9.9 Hz], 127.59 [br. dm (s), C(13), JHC 164.0 Hz, JHCCC 3.7–4.0 Hz,
Ph
C
CH – HCl
3JHCCC 3.2–3.5 Hz], 126.66 and 126.69 [2dd (2s), C(14), C(15), JHC
1
160.0 Hz and JHCCC 7.3 Hz, 1JHC 159.0 Hz and 3JHCCC 7.4 Hz], 130.29
3
14
[dd (s), C(16), 1JHC 162.0 Hz, 3JHC(14)CC(16) 5.7 Hz], 141.63 [m (d), C(17),
3JPCCC 18.2 Hz], 126.96 [br. dm (s), C(18), 1JHC 159.3–160.2 Hz, 3JHCCC
13
15
11
16
10
3
1
6.5–7.0 Hz, JHCCC 6.5–7.0 Hz], 128.49 [br. dd (s), C(19), JHC 159.0–
12
1
O
3
1
3
12a
160.0 Hz, JHCCC 7.3 Hz], 128.32 [dt (s), C(20), JHC 161.0 Hz, JHCCC
O
2
9
7.9 Hz], 42.65 [dm (s), NCH, JHC 137.6 Hz, 2JPNC 0 Hz, JHNC 4.9 Hz,
1
2
P
Cl
8b
8a
12b
2JHCC 3.7 Hz], 24.80 and 24.51 [2br. qm (2d), Me, JHC 125.0 Hz and
1
4a
3
8
3JPNCC 4.0 Hz, 1JHC 122.4 Hz and 3JPNCC 6.1 Hz]. 31P NMR (162.0 MHz,
[2H6]DMSO) dP: 12.5. IR (n/cm–1): 3158 (NH), 1618, 1589, 1565, 1542,
1515, 1399, 1303, 1244, 1231, 1200, 1180, 1161, 1133, 1106, 1078,
1048, 994, 954, 906, 864, 847, 825, 792, 762, 745, 714, 701, 681, 652,
619, 582, 572, 549, 521, 505, 477, 430. Found (%): C, 72.18; H, 4.77;
P, 6.51. Calc. for C29H22ClNO2P (%): C, 72.12; H, 4.56; P, 6.42.
4b
5
4
17
7
18
19
Cl
6
20
2
102 Mendeleev Commun. 2005