1202
ONYS’KO et al.
1
2
Diethyl N-cyclopentyltrifluoroacetimidoylphos-
7 Hz), 118.1 q.d (CF3CO, JC4F 278, JCP 3.5 Hz),
1
phonate (Ik). A mixture of 0.01 mol of imidoyl chlo-
ride IIf and 0.012 mol of triethyl phosphite was ref-
luxed for 3 h at 145 150 C. Vacuum distillation gave
phosphonate Ik, yield 34%, bp 73 75 C
(0.05 mm Hg), n2D0 1.4630. 1H NMR spectrum
122.5 q.d (CF3CH=, JCH 280, JCP 7 Hz), 156.7 q.d
(C=N, JCF 39.5, JCP 10.6 Hz). 19F NMR spectrum
(CDCl3), F, ppm: 72.45 br.s (3F, CF3CH=N);
67.95 t (3F, CF3CHP, JFH
NMR spectrum (CDCl3), P, ppm: 7.9. Found, %: N
4.09; P 9.56. C10H16F6NO3P. Calculated, %: N 4.08;
P 9.02.
2
3
3JPF 7.8 Hz). 31P
3
3
(CDCl3), , ppm: 1.38 t (6H, Me, JHH 6.9 Hz), 1.6
2.0 m (8H, CH2), 4.2 m (4H, CH2O), 4.8 m (1H, CH).
19F NMR spectrum (CDCl3), , ppm: 69.6 s. 31P
NMR spectrum (CDCl3):
2.9 ppm. Found, %: N
REFERENCES
4.68; P 10.54. C11H19F3NOP3P. Calculated, %: N 4.65;
P 10.28.
1. Onys’ko, P.P., Kim, T.V., Kiseleva, E.I., and Sini-
tsa, A.D., Zh. Obshch. Khim., 2004, vol. 74, no. 12,
p. 1981.
Diethyl [1-(2,2,2-trifluoroethylideneamino)-2,2,
2-trifluoroethyl]phosphonate (IVe). A solution of
0.003 mol of imidoyl chloride IId and 0.003 mol of
triethyl phosphite in 3 ml of anhydrous toluene was
heated in the sealed ampule at 120 C for 2.5 h. Accor-
ding to 19F and 31P NMR data, the reaction mixture
contains a mixture of prototropic isomers IVe/Ie
( 5:1). Imidoylphosphonate Id: F, ppm: 72.2 t
(CF3CH2); 70.1 [CF3C=N (Z)]; 65.0 [CF3C=N (E)];
P, ppm: 4.5 (Z), 4.4 (E), Z/E 10:1. Triethylamine,
5 ml, was added. After 30 min, signals of imidoyl-
phosphonate completely disappeared. The resulting
solution was filtered, evaporated, and the residue was
distilled in a vacuum. Yield of phosphonate IVd 33%,
2. Onys’ko, P.P., Kim, T.V., Kiseleva, E.I., and Sini-
tsa, A.D., Zh. Obshch. Khim., 2004, vol. 74, no. 9,
p. 1447.
3. Flynn, G.A., Beight, D.W., and Boehme, E.H.W.,
Tetrahedron Lett., 1985, vol. 26, no. 3, p. 285;
Aminophosphonic and Aminophosphinic Acids.
Chemistry and Biological Activity, Kukhar, V.P. and
Hudson, H.R., New York: Wiley, 2000; Kafarski, P.
and Lejczak, B., Phosphorus, Sulfur Silicon, 1991,
vol. 63, p. 193; Kukhar, V.P., Soloshonok, V.A., and
Solodenko, V.A., Phosphorus, Sulfur Silicon, 1994,
vol. 92, p. 239.
bp 76 C (6 mm Hg), nD20 1.3758. H NMR spectrum
1
(CDCl3), , ppm: 1.38 m (6H, Me), 4.22 m (5H,
4. Sinitsa, A.D., Onys’ko, P.P., Kim, T.V., Kiseleva, E.I.,
and Pirozhenko, V.V., Zh. Obshch. Khim., 1986,
vol. 56, no. 12, p. 2681.
3
CH2O + CHP), 7.87 d.q (1H, CH=, JHF
4JHP
3.5 Hz). 19F NMR spectrum (CDCl3), F, ppm:
72.43 br.s (3F, CF3CH=), 68.25 t (3F, CF3CHP,
3JFH 4JFP 7.6 Hz). 31P NMR spectrum, P, ppm:
9.8. Found.%: P 9.88. C8H12F6NO3P. Calculated, %:
P 9.83.
5. Onys’ko, P.P., Kim, T.V., Kiseleva, E.I., Sinitsa, A.D.,
and Kornilov, M.Yu., Zh. Obshch. Khim., 1990,
vol. 60, no. 6, p. 1304.
6. Asensio, A., Bravo, P., Crucianelli, M., Farina, A.,
Fustero, S., Soler, J.G., Meille, S.V., Panzeri, W.,
Viani, F., Volonterio, A., and Zanda, M., Eur. J. Org.
Chem., 2001, no. 8, p. 1449.
Diisopropyl [1-(2,2,2-trifluoroethylideneamino)-
2,2,2-trifluoroethyl]phosphonate (IVg). A solution
of 0.007 mol of imidoyl chloride IId and 0.007 mol
of triisopropyl phosphite in 6 ml of anhydrous toluene
was heated in a sealed ampule at 120 C for 4 h. Ac-
7. Onys’ko, P.P., Kim, T.V., Kiseleva, E.I., and Sini-
tsa, A.D., Phosphorus, Sulfur Silicon, 1990, vols. 49
50, nos. 1 4, p. 73.
1
cording to F and 31P NMR data, the ratio of proto-
tropic isomers IVg and Ig was 5:1. Imidoylphos-
phonate Ig: F, ppm: 72.2 t (CF3CH2); 69.7 [CF3C=
8. Onys’ko, P.P., Kim, T.V., Kiseleva, E.I., Prokopen-
ko, V.P., and Sinitsa, A.D., Zh. Obshch. Khim., 1997,
vol. 67, no. 5, p. 749.
N (Z)], 65.0 [CF3C=N (E)];
6.8 ppm (Z),
P
1.1 ppm (E), Z/E 7:1. Triethylamine, 0.2 g, was
added. After a day, the solvent was evaporated, and
the residue was distilled in a vacuum. Yield 33%, bp
9. Xiao, J., Zhang, X., and Yuan, C., Heteroatom. Chem.,
87 90 C (6 mm Hg), nD20 1.3810. H NMR spectrum
1
2000, vol. 11, no. 7, p. 536.
(CDCl3), , ppm: 1.34 m (12H, Me), 4.25 d.q (1H,
10. Onys’ko, P.P., Kim, T.V., Kiseleva, E.I., Prokopen-
ko, V.P., and Sinitsa, A.D., Zh. Obshch. Khim., 1996,
vol. 66, no. 8, p. 1283.
2
3
CHP, JHP 18.8, JHF3 8.2 Hz), 4.83 m (2H, CHO),
7.86 d.q (1H, CH=, JHF 4JHP 4 Hz). 13C NMR
3
spectrum (CDCl3), C, ppm: 23.5 (CH3, JCP 4 Hz),
11. Rassukana, Yu.V., Davydova, K.O., Onys’ko, P.P.,
and Sinitsa, A.D., J. Fluorine Chem., 2002, vol. 117,
no. 2, p. 107.
3
1
1
23.9 (CH3, JCP 5 Hz), 68.3 d.q (CHP, JCP 146, JCF
2
2
30 Hz), 73.7 d (CHO, JCP 7 Hz), 74.1 d (CHO, JCP
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 8 2005