238 Chaikovskaya et al.
Yield 85%. mp 140–142◦C. 31P NMR (DMSO-d6): δ
14.7. 1H NMR (DMSO-d6): δ 3.11 (br s, 8H, O CH2),
3.57 (br s, 8H, N CH2), 7.20 (m, 3H, Ar), 7.34 (br s,
1H, Ar), 7.69 (br s, 1H, Ar), 7.86 (br s, 1H, Ar), 7.93
(m, 2H, Ar), 8.02 (d, 1H, JHP = 15.0 Hz, Ar), 11.97
(br s, 1H, NH). 13C NMR (DMSO-d6): δ 44.89 (s,
O C), 66.29 (s, N C), 99.34, 97.87 (d, JCP = 185.0 Hz,
C3), 113.79 s, 115.67 (d, JCP = 18.5 Hz), 119.52 s,
120.63 (d, JCP = 12.5 Hz), 122.05 s, 125.59 s, 127.53
(d, JCP = 11.5 Hz), 129.27 (d, JCP = 25.0 Hz), 131.09 s,
135.15 (d, JCP = 18.5 Hz), 137.37 (d, JCP = 14.0 Hz),
141.22 s, 148.60 (d, JCP = 16.0 Hz). m/z 457 [M]+.
Anal. Calcd. for C22H28N5O4P (457): C 57.76, H 6.17,
P 6.77. Found: C 57.74, H 6.15, P 6.75.
1H-Indol-3-yl[di(4-morpholyl)]phosphine
Sulfide 6
To a solution of compound 4 (0.01 mol) in benzene
(50 mL), elementary sulfur (0.01 mol) was added, fol-
lowed by 0.5 h of boiling and evaporation of the re-
action mixture. The residue was recrystallized from
acetonitrile. Yield 85%. mp 129–130◦C. 31P NMR
(DMSO): δ 69.0. 1H NMR (DMSO-d6): δ 2.99 (m, 8H,
O CH2), 3.56 (m, 8H, N CH2), 7.13 (m, 2H, Ar), 7.47
(d, 1H, JHH = 7.5 Hz, Ar), 7.80 (br s, 1H, Ar), 7.92 (d,
1H, JHH = 9.0 Hz, Ar), 11.84 (br s, 1H, NH). 13C NMR
(DMSO-d6): δ 47.53 (d, JCP = 18.0 Hz, O C), 67.28 (d,
JCP = 25.0 Hz, N C), 95.00, 100.82 (d, JCP = 133.5 Hz,
C3), 113.25 s, 121.08 s, 122.09 s, 122.86 s, 125.82
(d, JCP = 25.0 Hz), 142.38 (d, JCP = 46.5 Hz), 142.83
(d, JCP = 25.0 Hz). m/z 351 [M]+. Anal. Calcd. for
C16H22N3O2PS (351): C 54.69, H 6.31, P 8.81. Found:
C 54.65, H 6.30, P 8.79.
1-Acetyl-1H-indol-3-yl[di(4-morpholyl)]-
phosphine Oxide 9
To a stirred solution of compound 7 (0.01 mol)
in DMF (10 mL), a 60% mineral oil suspension of
sodium hydride (0.012 mol) was added, followed
by stirring the reaction mixture at room tempera-
ture for 12 h. After the addition of acetyl chloride
(0.01 mol), the mixture was stirred at 40◦C for an-
other 8 h, poured into water, and extracted with
dichloromethane (3 × 20 mL). The organic layer was
separated and dried over sodium sulfate, and the
solvent was evaporated in vacuo. The residue was
recrystallized from acetonitrile. Yield 80%. mp 200–
201◦C. 31P NMR (DMSO-d6): δ 19.7. 1H NMR (DMSO-
d6): δ 2.67 (s, 3H, CH3), 3.17 (m, 8H, O CH2), 3.65 (m,
8H, N CH2) 7.26 (br s, 1H, H2), 7.67 (m, 2H, Ar), 8.04
(d, 1H, JHH = 5.4 Hz, Ar), 8.50 (d, JHP = 8.1 Hz 1H, Ar).
13C NMR (DMSO-d6): δ 24.65 (s, CH3), 44.91 (s, O C),
67.20 (s, N C), 106.45, 100.86 (d, JCP = 222.0 Hz, C3),
111.70 s, 124.57 (d, JCP = 10.0 Hz), 125.08 s, 125.60 s,
126.21 (d, JCP = 8.0 Hz), 134.13 (d, JCP = 16.0 Hz),
139.50 (d, JCP = 8.0 Hz), 166.42 s. m/z 378 [M]+. Anal.
Calcd. for C18H24N3O4P (377): C 57.29, H 6.41, P 8.21.
Found: C 57.25, H 6.38, P 8.20.
1H-Indol-3-yl[di(4-morpholyl)]phosphine
Oxide 7
To a stirred solution of compound 4 (0.01 mol)
in benzene (30 mL), hexachloroethane (0.01 mol)
was added at room temperature, followed by stir-
ring the reaction mixture for 3 h. The resulting pre-
cipitate was filtered off, dissolved in dichloroethane
(30 mL), and treated with a 10% aqueous solution
of sodium hydrogen carbonate (30 mL). The or-
ganic layer was separated and evaporated, and the
residue was recrystallized from diethyl ether. Yield
90%. mp 203–205◦C. 31P NMR (DMSO): δ 22.9. H
1
NMR (DMSO-d6): δ 3.01 (br s, 8H, O CH2), 3.52
(br s, 8H, N CH2), 7.07 (t, 1H, JHP = 7.5 Hz, Ar), 7.14
(t, 1H, JHP = 7.5 Hz, Ar), 7.44 (d, 1H, JHP = 8.0 Hz,
Ar), 7.66 (br s, 1H, H2), 7.75 (d, 1H, JHP = 8.0 Hz,
Ar), 11.76 (br s, 1H, NH). 13C NMR (DMSO-d6): δ
43.97 (s, O C), 66.35 (s, N C), 101.79, 100.36 (d,
JCP = 180.0 Hz, C3), 111.7 s, 119.88 (d, JCP = 29.0 Hz),
121.49 s, 127.49 (d, JCP = 11.0 Hz), 127.99 s, 133.92
(d, JCP = 20.0 Hz), 137.16 (d, JCP = 12.5 Hz). m/z 335
[M]+. Anal. Calcd. for C16H22N3O3P (335): C 57.31, H
6.61, P 9.24. Found: C 57.0, H 6.60, P 9.20.
REFERENCES
[1] Hoffman, A.; Heim, R.; Brack A. Helv Chim Acta
1959, 42, 1557–1570.
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3240.
[3] Musabekova, Z. R.; Razumov, A. I.; Aleksandrova,
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[4] Gurevich, P. A.; Razumov, A. I.; Komina T. V.;
Klimentova, G. Y.; Zykova, T. V. Zh Obshch Khim
1985, 55, 1257–1262.
1H-Indol-3-yl[di(4-morpholyl)](N-phenyl)-
phosphine Imide 8
To a stirred solution of compound 4 (0.01 mol) in
benzene (30 mL), m-nitrophenyl azide (0.01 mol)
was added at room temperature, followed by stir-
ring the reaction mixture for 12 h (δP = 37.14 ppm).
Then, the mixture was boiled for 5 h and evapo-
rated; the residue was recrystallized from methanol.
Heteroatom Chemistry DOI 10.1002/hc