148
PANARINA et al.
the amount of I) of CuCl in 3 ml of absolute methanol
in a sealed ampule. The ampules were kept at 100
110 C for 10 30 h. The reaction progress was moni-
Diethyl N-tert-butylaminophenylethenephospho-
nate IIc. Yield 65%, bp 166 170 C (0.1 mm Hg). IR
1
spectrum (KBr), , cm : 2986, 1593 (C=C), 1253
1
(P=O), 1026. 1H NMR spectrum (CDCl3), , ppm:
tored by H NMR spectroscopy until the initial al-
kynephosphonate was consumed completely. The sol-
vent was removed in a vacuum, and the residue was
distilled in a deep vacuum. -Enaminophosphonates
are yellow oily liquids. In the course of distillation
the compounds partially decompose, and the yield sig-
nificantly decreases.
1.09 s (9H, CH3, t-Bu), 1.24 t (6H, CH3), 3.93 d (1H,
2
CH-Z, JHP 14.09 Hz), 4.05 q (4H, CH2 O), 4.37 d
2
(1H, CH-E, JHP 10.08 Hz), 7.29 7.45 m (5H, arom.).
13C NMR spectrum (CDCl3), C, ppm: 16.11 (CH3),
29.49 (CH3, t-Bu-E), 31.84 (CH3, t-Bu-Z), 51.66 (C,
t-Bu-E), 53.39 (C, t-Bu-Z), 61.81 (CH2 O, E), 62.41
Diethyl N-tert-butylaminopropenephosphonate
IIa. Yield 57%, bp 152 155 C (0.4 mm Hg). IR spec-
1
(CH2 O, Z), 77.7 d (CH-E, JPC 216.84 Hz), 84.4 d
1
(CH-Z, JPC 188.3 Hz), 127.38 127.7 (CH arom., E),
1
trum (KBr), , cm : 2970, 1587 (C=C), 1200 (P=O),
128.39 128.83 (CH arom., Z), 138.76 d (Cipso arom.,
1
1013. H NMR spectrum (CDCl3), , ppm: 1.18 t (6H,
3
3
E, JPC 2.76 Hz), 140.7 d (Cipso arom., Z, JPC
CH3), 1.28 m (9H, CH3, t-Bu), 1.99 s (3H, CH3-E),
2
19.9 Hz), 155.42 d (=C N, Z, JPC 16.59 Hz),
2
2.01 s (3H, CH3-Z), 3.41 d (1H, CH-Z, JHP 13.4 Hz),
164.46 d (=C N, E, 2JPC 6.08 Hz). 31P NMR spectrum
(CDCl3), P, ppm: 23.57 (Z), 24.2 (E).
2
3.9 d (1H, CH-E, JHP 10.6 Hz), 3.95 q (4H, CH2 O).
13C NMR spectrum (CDCl3), C, ppm: 16.08 (CH3),
3
3
The IR spectra were taken on a Specord IR-75 in-
strument from thin layers on KBr. The NMR spectra
were registered on a Tesla BS-497 instrument (100 Mz)
21.35 d (CH3-E, JPC 5.0 Hz), 22.86 d (CH3-Z, JPC
22.14 Hz), 28.41 (CH3, t-Bu-E), 30.87 (CH3, t-Bu-Z),
50.98 (C, t-Bu-E), 51.4 (C, t-Bu-Z), 60.36 (CH2 O,
E), 62.17 (CH2 O, Z), 72.63 d (CH-Z, 1JPC 192.3 Hz),
1
using H {31P} NMDR technique, with HMDS as
1
external reference. The H, 31P, and 13C NMR spectra
1
74.80 d (CH-E, JPC 210.0 Hz), 156.1 d (=C N, E,
were registered on a Bruker AC-200 instrument, with
85% H3PO4 as external reference and CDCl3 as inter-
nal reference.
2
2JPC 19.32 Hz), 163.57 d (=C N, Z, JPC 5.79 Hz).
31P NMR spectrum (CDCl3), P, ppm: 25.51 (E),
26.13 (Z).
REFERENCES
Diethyl N-tert-butylaminobutenephosphonate
IIb. Yield 55%, bp 162 164 C (0.4 mm Hg). IR spec-
1. Lee, S.-L., Hepburn, T.W., Swartz, W.H., Ammon, H.L.,
Mariano, P.S., and Dunaway-Mariano, D., J. Am. Chem.
Soc., 1992, vol. 114, pp. 7346 7354.
1
trum (KBr), , cm : 2974, 1580 (C=C), 1200 (P=O),
1
1013. H NMR spectrum (CDCl3), , ppm: 1.08 t (3H,
2. Walker, B.J. Organophosphorus Reagents in Organic
Synthesis, Cadogan, J.G.G., Ed., Academic, 1979,
issue 4, pp. 155 206.
CH3), 1.25 t (6H, CH3), 1.27 m (9H, CH3, t-Bu),
2.37 q (2H, CH2-E), 2.57 q (2H, CH2-Z), 3.53 d (1H,
2
CH-Z, JHP 12.6 Hz), 3.91 d (1H, CH-E, 2JHP 9.6 Hz),
3.95 q (4H, CH2 O). 13C NMR spectrum (CDCl3),
C, ppm: 13.51 (CH3, Et), 16.07 (CH3), 27.17 d (CH2,
3. Palacios, F., Garcia, J., Ochoa de Retana, A., and Oyar-
zabal, J., Heterocycles, 1995, vol. 41, p. 1915.
4. Lopez, F., Pelaez, E., Palacios, F., Barluenga, J.,
Garcia, S., Tejerina, B., and Garcia, A., J. Org. Chem.,
1994, vol. 59, p. 1984.
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1996, vol. 52, no. 28, pp. 9609 9628.
6. Palacios, F., Ochoa de Retana, A.M., and Oyarzabal, J.,
3
Et-Z, JPC 20.97 Hz), 28.03 d (CH2, Et-E, 3JPC 6.7 Hz),
28.46 (CH3, t-Bu-E), 31.05 (CH3, t-Bu-Z), 50.76 (C,
t-Bu-E), 51.52 (C, t-Bu-Z), 60.44 (CH2 O, E), 62.31
1
(CH2 O, Z), 71.57 (CH-Z, JPC 193.9 Hz), 74.06 d
1
2
(CH-E, JPC 215.45 Hz), 161.83 d (=C N, E, JPC
2
19.22 Hz), 169.92 d (=C N, Z, JPC 6.2 Hz).
Tetrahedron, 1999, vol. 55, pp. 3091 3104.
7. Duncan, M. and Gallagher, M.J., Org. Magn. Reson.,
31P NMR spectrum (CDCl3), P, ppm: 26.53 (E),
27.47 (Z).
1981, vol. 15, no. 1, pp. 37 42.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 1 2001