140 Kiss et al.
2
80%; 31P NMR (CDCl3) δ: –5.7 (d, J = 17.1), 60.0
(CDCl3) δ: 1.61 (s, 6H, C3–CH3), 2.15–2.37 (m, 2H,
PCH2), 2.76–2.93 (m, 2H, PCH2), 4.47–4.65 (m, 2H,
NCH2), 6.98–7.21, 7.33–7.64, and 7.71–7.87 (m,
(d, 2J = 17.1); 13C NMR (CDCl3) δ: 13.7 (CH2CH3),
3
16.5 (d, J = 15.9, C3–CH3), 20.1 (CH2CH3), 33.2
15H, Ar); [M + H]+
= 436.1598, C25H28NO2P2
(NCH2CH2), 39.5 (1J = 83.1, C2), 45.8 (NCH2),
found
3
2
requires 436.1595.
ꢁ
ꢁ
120.3 (d, J = 4.8, C2 ), 125.5 (C4 ), 127.3 ( J =
2
1
Diethylphosphoryl-1-n-butylamino-3-methyl-2,5-
dihydro-1H-phosphole 1-Oxide (11b). Yield: 29%;
31P NMR (CDCl3) δ: 3.8 (d, 2J = 16.4), 65.5 (d,
2J = 16.4); 13C NMR (CDCl3) δ: 13.7 (CH2CH3),
ꢁ
ꢁ
12.7, C4), 129.8 (C3 ), 150.2 (d, J = 7.0, C1 ); H
NMR (CDCl3) δ: 0.94 (t, 3JH,H = 7.4, 3H, CH2CH3),
1.30–1.44 (m, 2H, CH2), 1.69 (s, 6H, C3–CH3),
1.72–1.87 (m, 2H, CH2), 2.33–2.50 (m, 2H, PCH2),
2.71–2.90 (m, 2H, PCH2), 3.48–3.66 (m, 2H, NCH2),
3
16.0 (d, J = 7.2, OCH2CH3), 20.0 (CH2CH3), 20.5
3
(d, J = 12.9, C3–CH3), 33.2 (NCH2CH2), 34.6 (1J
7.11–7.41 (m, 10H, Ar); [M + H]+
= 434.1653,
found
= 81.7, C5), 37.2 (1J = 85.4, C2), 45.2 (NCH2),
63.0 (d, 2J = 5.4, OCH2), 120.1 (2J = 10.5, C4),
C22H30NO4P2 requires: 434.1650.
1
136.1 (2J = 16.6, C3); H NMR (CDCl3) δ: 0.92 (t,
Theoretical Calculations
3JH,H = 7.4, 3H, CH2CH2CH3), 1.26–1.36 (m, 8H,
CH2, CH3), 1.62–1.72 (m, 2H, CH2), 1.82 (s, 3H,
C3–CH3), 2.32–2.60 (m, 2H, PCH2), 2.78–2.92 (m,
2H, PCH2), 3.26–3.38 (m, 2H, NCH2), 4.03–4.17
Quantum chemical investigations were carried out
with electronic structure computations, using the
B3LYP [16] method, employing the 6–31G(d,p) basis
set for all atoms, using the Gaussian09 (G09) pro-
gram package [17].
3
(m, 4H, OCH2), 5.55 (d, JP,H = 36.2, 1H, CH= );
[M + H]+
= 324.1497, C13H28NO4P2 requires
found
324.1494.
Diethylphosphoryl-1-benzylamino-3-methyl-2,5-
dihydro-1H-phosphole 1-Oxide (11c). Yield: 32%;
31P NMR (CDCl3) δ: 3.1 (d, 2J = 15.9), 66.3 (d,
REFERENCES
[1] Quin, L. D. The Heterocyclic Chemistry of Phospho-
rus: System Based on the Phosphorus–Carbon Bond;
Wiley: New York, 1981; p. 30.
[2] Quin, L. D. A Guide to Organophosphorus Chemistry;
Wiley: New York, 2000; p. 249.
[3] Mathey, F. (Ed.): Phosphorus-Carbon Heterocyclic
Chemistry: The Rise of a New Domain; Pergamon:
Amsterdam, The Netherlands, 2001; p. 195.
[4] Quin, L. D. In Comprehensive Heterocyclic Chem-
istry II; Katritzky, A. R.; Rees, C. W.; Scriven, E. F.
V.; Bird, C. W. (Eds.); Pergamon/Elsevier: Oxford,
UK, 1996; Vol. 2, Ch. 2.15, p. 826.
[5] Keglevich, G. In Topics in Heterocyclic Chemistry;
Gupta, R. R.; Bansal, R. K. (Eds.); Springer: Dor-
drecht, The Netherlands, 2009; Vol. 20, pp. 65–98.
[6] Keglevich, G. Curr Org Chem 2006, 10, 93–111.
[7] Keglevich, G. Synthesis 1993, 10, 931–942.
[8] Keglevich, G.; Kiss, N. Z.; Mucsi, Z.; Ko¨rtve´lyesi, T.
Org Biomol Chem 2012, 10, 2011–2018.
3
2J = 15.9); 13C NMR (CDCl3) δ: 15.8 (d, J = 7.4,
3
OCH2CH3), 20.5 (d, J = 13.0, C3–CH3), 34.6 (1J =
81.3, C5), 37.2 (1J = 85.0, C2), 47.6 (NCH2), 63.1 (d,
2
2
ꢁ
J = 5.4, OCH2), 120.2 ( J = 10.7, C4), 127.4 (C1 ),
2
1
ꢁ
ꢁ
ꢁ
128.3 (C2 , C3 ), 136.1 ( J = 16.7, C3), 138.4 (C4 ); H
NMR (CDCl3) δ: 1.19 (m, 6H, CH2CH3), 1.79 (s, 3H,
C3–CH3), 2.36–2.58 (m, 2H, PCH2), 2.77–2.92 (m,
2H, PCH2), 3.73–3.86 (m, 2H, OCH2), 3.96–4.06
(m, 2H, OCH2), 4.56–4.63 (m, 2H, NCH2), 5.54 (d,
3JP,H = 36.4, 1H, CH= ), 7.22–7.46 (m, 5H, Ar);
[M + H]+
= 358.1340, C16H26NO4P2 requires
found
358.1337.
Diphenylphosphoryl-1-n-butylamino-3-methyl-2,5-
dihydro-1H-phosphole 1-Oxide (12b). Yield: 68%;
2
31P NMR (CDCl3) δ: –5.81 (d, J = 17.9), 66.6 (d,
2J = 17.9); 13C NMR (CDCl3) δ: 13.7 (CH2CH3),
[9] Kiss, N. Z.; Bo¨ttger, E.; Drahos, L.; Keglevich, G.
´
3
Heteroatom Chem 2013, 24, 283–288.
[10] Keglevich, G.; Kiss, N. Z.; Drahos, L.; Ko¨rtve´lyesi, T.
Tetrahedron Lett 2013, 54, 466–469.
[11] Keglevich, G.; Kiss, N. Z.; Ko¨rtve´lyesi, T. Heteroatom
Chem 2013, 24, 91–99.
20.1 (CH2CH3), 20.5 (d, J = 13.2, C3–CH3), 33.1
(NCH2CH2), 34.9 (1J = 80.7, C5), 37.4 (1J = 84.5,
C2), 45.7 (NCH2), 120.1 (2J ࣈ
10.7, C4) overlapped
3
3
ꢁ
by 120.2 ( J = 4.6) and 120.3 ( J = 4.6) C2 , 125.5
(C4 ), 129.8 (C3 ), 136.1 (d, 2J = 16.9, C3), 150.1
[12] Keglevich, G.; Kova´cs, A.; To˝ke, L.; Ujsza´szy, K.; Ar-
´
ꢁ
ꢁ
2
2
1
gay, G.; Czugler, M.; Ka´lma´n, A. Heteroatom Chem
1993, 4, 329–335.
[13] Keglevich, G.; Dvorszki, J.; Ujj, V.; Luda´nyi, K.
Heteroatom Chem 2010, 21, 271–277.
[14] Kiss, N. Z.; Simon, A.; Drahos, L.; Huben, K.;
Jankovski, S.; Keglevich, G. Synthesis 2013, 45, 199–
204.
[15] Kenn, M.; Jansen, W.; Schmitz-DuMont, O. Z Anorg
Allg Chem 1979, 452, 176–192.
ꢁ
(d, J = 7.1) and 150.2 (d, J = 7.2) C1 ; H NMR
(CDCl3) δ: 0.95 (t, 3JH,H = 7.3, 3H, CH2CH3), 1.29–
1.46 (m, 2H, CH2), 1.73–1.87 (m, CH2), overlapped
by 1.77 (s, C3–CH3) total intensity 5H, 2.26–2.56
(m, 2H, PCH2), 2.64–2.86 (m, 2H, PCH2), 3.48–3.68
3
(m, 2H, NCH2), 5.52 (d, JP,H = 35.5, 1H, CH= ),
7.15–7.40 (m, 10H, Ar); [M + H]+
= 420.1497,
found
C21H28NO4P2 requires 420.1494.
[16] Becke, A. D. J Chem Phys 1993, 98, 5648–5652.
[17] Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria,
G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.;
Diphenylphosphoryl-1-n-butylamino-3,4-dimethyl-
2,5-dihydro-1H-phosphole 1-Oxide (13b). Yield:
Heteroatom Chemistry DOI 10.1002/hc