124
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 1, January, 2009
Matveeva et al.
Diethyl [4ꢀpyridyl(2ꢀpyridylamino)methyl]phosphonate (7).
M.p. 108—110 °C. Found (%): C, 56.26; Н, 6.32; N, 13.25.
1240 (Р=О); 1470 (C=N arom.); 1580, 1610 (C=C arom.);
3300 (N—Н).
C15Н20N3О3P. Calculated (%): C, 56.07; Н, 6.27; N, 13.08.
Diethyl {[1ꢀ(2ꢀcyanoethyl)ꢀ1Hꢀindolꢀ3ꢀyl](2ꢀpyridylamino)ꢀ
methyl}phosphonate (10). M.p. 147—149 °C. Found (%):
C, 61.27; H, 6.11; N, 13.65. C21H25N4O3P. Calculated (%):
C, 61.16; H, 6.11; N, 13.58. 1H NMR, δ: 1.10, 1.22 (both t, 6 Н,
2 Me, 3JH,H = 7.1 Hz); 2.66 (t, 2 Н, CН2CН2CN, 3JH,H = 6.8 Hz);
3.82—3.92, 3.39—4.16 (both m, 1 Н, 2 H, 2 ОCН2); 4.18—4.29
(m, 3 Н, CН2CН2CN, 2 ОCН2); 5.48—5.50 (m, 1 Н, NH); 6.12
3
1H NMR, δ: 1.15, 1.22 (both t, 6 Н, 2 Me, JH,H = 7.0 Hz,
3JH,H = 7.1 Hz); 3.82—3.92, 3.97—4.18 (both m, 1 Н, 3 H,
2 ОCН2); 5.64 (dd, 1 Н, CН, 2JH,P = 23.8 Hz, 3JH,H = 8.8 Hz);
5.79—5.83 (m, 1 Н, NН); 6.49 (d, 1 Н, H(3)NHPy, 3JH,H = 8.3 Hz);
6.58 (t, 1 Н, H(5)NHPy, 3JH,H = 6.0 Hz); 7.36 (t, 1 Н, H(4)NHPy
,
3JH,H = 7.7 Hz); 7.44—7.46 (m, 2 Н, H(3)Py, H(5)Py); 8.02 (d,
3
1 Н, H(6)NHPy, JH,H = 5.3 Hz); 8.53 (d, 2 Н, H(2)Py, H(6)Py
,
(dd, 1 Н, 2JH,P = 18.4 Hz, 2JH,H = 9.2 Hz); 6.45 (d, 1 Н, H(3)Py
,
3JH,H = 5.8 Hz). 31P NMR, δ: 21.51. 13C NMR, δ: 16.17, 16.34
3JH,H = 8.3 Hz); 6.57 (t, 1 Н, H(5)Py, JH,H = 5.9 Hz); 7.13 (t,
1 Н, H(5)ind or H(6)ind
3
3
3
(both d, Me, JC,P = 5.1 Hz, JC,P = 5.9 Hz); 51.77 (d, CН,
,
3JH,H = 7.4 Hz); 7.20—7.23 (m, 2 Н,
1JC,P = 150.0 Hz); 63.27, 63.51 (both d, OCH2, 2JC,P = 6.6 Hz);
H(7)ind, H(6)ind or H(5)ind); 7.32 (t, 1 Н, H(4)Py, 3JH,H = 7.7 Hz);
108.90 (C(3)HNHPy); 114.29 (C(5)HNHPy); 122.96 (d, C(3)HPy
,
7.46 (d, 1 Н, H(2)ind, ,
4JH,P = 1.8 Hz); 7.82 (d, 1 Н, H(4)ind
3
C(5)HPy JC,P = 5.1 Hz); 137.43 (C(4)HNHPy); 145.96 (C(4)Py);
147.85 (C(6)HNHPy); 149.75 (C(2)HPy, C(6)HPy); 156.56 (d,
C(2)NHPy, 3JC,P = 11.0 Hz). IR, ν/cm–1: 1040, 1060 (Р—О—C);
1240 (Р=О); 1470 (C=N arom.); 1520, 1600 (C=C arom.);
3300 (N—H).
3JH,H = 7.8 Hz); 8.15 (d, 1 Н(6)Py, 3JH,H = 5.1 Hz). 31P NMR,
δ: 23.40. 13C NMR, δ: 16.28, 16.43 (both d, Me, 3JC,P = 5.2 Hz,
3JC,P = 5.9 Hz); 18.89 (CН2CН2CN); 41.94 (CН2CН2CN);
1
44.61 (d, CН, JC,P = 161.0 Hz); 62.88, 63.21 (both d, ОCН2,
2JC,P = 6.6 Hz); 108.77, 108.83 (C(3)HPy, C(7)Hind); 111.66
Diethyl [(1ꢀmethylꢀ1Hꢀindolꢀ2ꢀyl)(2ꢀpyridylamino)methyl]ꢀ
phosphonate (8). M.p. 138—140 °C. Found (%): C, 61.11;
Н, 6.57; N, 11.26. C19Н24N3О3P. Calculated (%): C, 61.12;
Н, 6.48; N, 11.25. 1H NMR, δ: 1.13, 1.23 (both t, 6 Н, 2 Me,
(C(3)ind); 113.62 (C(5)HPy); 117.13 (CN); 120.24, 120.42,
122.63 (C(4)Hind,, C(5)Hind, C(6)Hind); 127.04 (d, C(2)H
,
3JC,P = 5.8 Hz); 127.59 (d, C(9)ind
,
3JC,P = 8.0 Hz); 135i.n6d0
(C(8)ind); 137.29 (C(4)HPy); 147.77 (C(6)HPy); 157.10 (d,
3
POEt, JH,H = 7.1 Hz); 3.84—3.91, 4.05—4.23 (both m, 1 Н,
C(2)Py
,
3JC,P = 7.3 Hz). IR, ν/cm–1: 1030, 1070 (Р—О—C);
3 H, 2 ОCН2); 3.86 (s, 3 Н, NMe); 5.51—5.53 (m, 1 Н, NH);
6.14 (dd, 1 Н, CН, 2JH,P = 22.4 Hz, 3JH,H = 9.4 Hz); 6.54 (d, 1 Н,
H(3)Py, 3JH,H = 8.3 Hz); 6.61 (t, 1 Н, H(5)Py, 3JH,H = 6.0 Hz);
1220 (Р=О); 1470 (C=N arom.); 1580, 1600 (C=C arom.);
2260 (C≡N); 3300 (N—Н).
Diethyl [hydroxy(phenyl)methyl]phosphonate (11) was isolated
as a side product in the synthesis of αꢀaminophosphonate 6.
M.p. 82—83 °C (cf. Ref. 25: m.p. 82—83 °C). 1H NMR, δ: 1.22,
6.85 (s, 1 Н, H(3)ind); 7.09, 7.21 (both t, 1 Н each, H(5)ind
H(6)ind, 3JH,H = 7.4 Hz); 7.31 (d, 1 Н, H(7)ind, 3JH,H = 8.3 Hz);
7.37 (t, 1 Н, H(4)Py
3JH,H = 8.0 Hz); 7.56 (d, 1 Н, H(4)ind
3JH,H = 7.9 Hz); 8.13 (d, 1 Н, H(6)Py 3JH,H = 5.0 Hz).
31P NMR, δ: 21.65. 13C NMR, δ: 16.26, 16.41 (both d, Me,
,
3
,
,
1.27 (both t, 6 Н, 2 Me, JH,H = 7.0 Hz); 3.94—4.10 (m, 4 Н,
,
2 ОCН2); 4.39 (br.s, 1 Н, ОН); 5.03 (d, 1 Н, CН, 2JH,P = 11 Hz);
7.37—7.50 (m, 5 Н, Py). 31P NMR, δ: 21.58. IR, ν/cm–1: 1040,
1065 (Р—О—C); 1240 (Р=О); 1600 (C=C arom.); 3280 (ОН).
Diethyl [hydroxy(1ꢀmethylꢀ1Hꢀindolꢀ2ꢀyl)methyl]phosphoꢀ
nate (12) was isolated as the major product in the reaction of
Nꢀmethylindoleꢀ2ꢀcarbaldehyde, 2ꢀaminopyridine, and diethyl
phosphite according to the general procedure. M.p. 131—132 °C.
Found (%): C, 56.60; Н, 6.85; N, 4.77. C14Н20NО4P. Calculated
(%): C, 56.56; Н, 6.78; N, 4.71. 1H NMR, δ: 1.22, 1.26 (both t,
3
3
POEt, JC,P = 5.1 Hz, JC,P = 5.9 Hz); 30.15 (Me, NMe);
1
44.58 (d, CН, JC,P = 162.5 Hz); 63.19, 63.44 (both d, ОCН2,
2JC,P = 7.3 Hz); 101.92 (d, C(3)Hind 3JC,P = 4.4 Hz); 109.26,
,
109.30 (C(3)HPy, C(7)Hind); 113.99 (C(5)HPy); 119.48, 120.69,
121.66 (C(4)Hind, C(5)Hind, C(6)Hind); 127.50 (C(9)ind); 135.46
(d, C(2)ind, 3JC,P = 6.6 Hz); 137.34 (C(4)HPy); 137.52 (C(8)ind);
147.67 (C(6)HPy); 156.54 (d, C(2)Py,
3JC,P = 8.1 Hz). IR,
ν/cm–1: 1030, 1060 (Р—О—C); 1240 (Р=О); 1480 (C=N arom.);
1530, 1610 (C=C arom.); 3290 (N—Н).
6 Н, 2 Me, POEt, JH,H = 7.1 Hz); 3.78 (s, 3 Н, NMe);
3
4.00—4.16 (m, 4 Н, ОCН2); 4.70 (br.s, 1 Н, ОН); 5.18 (d, 1 Н,
Diethyl [(1Hꢀindolꢀ3ꢀyl)(2ꢀpyridylamino)methyl]phosphonate
(9). M.p. 140—141 °C. Found (%): C, 59.81; H, 5.85; N, 11.50.
C18H22N3O3P. Calculated (%): C, 60.16; H, 6.17; N, 11.69.
CН, 2JH,P = 13.9 Hz); 6.78 (s, 1 Н, H(3)ind); 7.11, 7.24 (both t,
3
1 Н each, H(5)ind, H(6)ind
,
3JH,H = 7.8 Hz, JH,H = 8.1 Hz);
7.31 (d, 1 Н, H(7)ind, ,
3JH,H = 8.3 Hz); 7.60 (d, 1 Н, H(4)ind
3
1H NMR, δ: 1.05, 1.23 (both t, 6 Н, 2 Me, JH,H = 7.1 Hz);
3JH,H = 7.9 Hz). 31P NMR, δ: 20.19. 13C NMR, δ: 16.35, 16.41
3
3.75—3.85, 3.94—4.04, 4.08—4.25 (all m, 1 Н, 1 Н, 2 H,
(both d, Me, POEt, JC,P = 5.9 Hz); 30.29 (Me, NMe);
2
1
2 ОCН2 JН ,Нb = 10.1 Hz, 3JН,Me = 7.07 Hz); 5.22—5.24 (m, 1
64.20 (d, CН, JC,P = 162.5 Hz); 63.37, 63.50 (both d, ОCН2,
а
2
3
Н, NH); 6.05 (dd, 1 Н, CН, JH,P = 20.6 Hz, JH,H = 9.1 Hz);
2JC,P = 7.3 Hz); 102.33 (d, C(3)ind 3JC,P = 4.4 Hz); 109.24
,
6.39 (d, 1 Н, H(3)Py
,
3JH,H = 8.0 Hz); 6.57 (t, 1 Н, H(5)Py
,
,
,
(C(7)ind); 119.57, 120.95, 122.04, (C(4)Hind,, C(5)Hind, C(6)Hind);
3JH,H = 6.1 Hz); 7.09, 715 (both t, 1 Н each, H(5)ind, H(6)ind
127.22 (C(9)ind); 134.80 (d, C(2)ind,
3JC,P = 5.1 Hz); 137.98
3JH,H = 7.5 Hz, JH,H = 7.6 Hz); 7.27—7.33 (m, 3 Н, H(2)ind
(C(8)ind). IR, ν/cm–1: 1030, 1065 (Р—О—C); 1240 (Р=О);
1530, 1610 (C=C arom.); 3280 (ОН).
3
H(7)ind, H(4)Py); 7.76 (d, 1 Н, H(4)ind
,
3JH,H = 7.8 Hz); 8.14
(d, 1 Н, H(6)Py
,
3JH,H = 5.0 Hz); 9.15 (br.s, 1 Н, NHind).
Diethyl [(1Hꢀindolꢀ3ꢀyl)(4ꢀpyridylamino)methyl]phosphonate
(13). M.p. 126—127 °C. Found (%): C, 60.13; Н, 6.32; N, 11.50.
C18Н22N3О3P. Calculated (%): C, 60.16; Н, 6.17; N, 11.69.
31P NMR, δ: 23.93. 13C NMR, δ: 16.19, 16.40 (both d, Me,
3JC,P = 5.1 Hz, JC,P = 5.8 Hz); 44.43 (d, CН, JC,P = 161.7
3
1
2
3
Hz); 62.93, 63.17 (both d, ОCН2, JC,P = 7.3 Hz); 108.56
1H NMR, δ: 1.08, 1.24 (both t, 6 Н, 2 Me, JH,H = 7.1 Hz);
(C(3)HPy); 110.42 (C(3)ind); 111.51 (C(7)ind); 113.70 (C(5)HPy);
119.39, 119.58, 122.06 (C(4)Hind, C(5)Hind, C(6)Hind); 124.30
(d, C(2)Hind, 3JC,P = 5.8 Hz); 126.52 (d, C(9)ind, 3JC,P = 8.0 Hz);
136.29 (C(8)ind); 137.31 (C(4)HPy); 147.79 (C(6)HPy); 157.21
(d, C(2)Py, 3JC,P = 8.8 Hz). IR, ν/cm–1: 1040, 1070 (Р—О—C);
3.76—3.86, 3.93—4.01, 4.06—4.19 (all m, 1 Н, 1 Н, 2 Н, 2 ОCН2);
2
5.36 (d, 1 Н, CН, JH,P = 20.8 Hz); 6.77 (d, 2 Н, H(3)Py
,
,
,
3
H(5)Py, JH,H = 6.5 Hz); 7.06, 7.14 (both t, 1 Н each, H(5)ind
H(6)ind, 3JH,H = 7.7 Hz, 3JH,H = 7.6 Hz); 7.38 (d, 1 Н, H(7)ind
3JH,H = 8.1 Hz); 7.47 (d, 1 Н, H(2)ind
,
4JH,P = 2.5 Hz); 7.71