REACTION OF TRICHLORO(o-PHENYLENEDIOXY)PHOSPHORANE
341
reaction can be regarded as a new selective procedure
for preparation of alkyl 1,2-alkadienylchlorophos-
phonates.
We failed to separate mixtures VI/IX by vacuum
distillation.
Reaction of phosphorane I with 3-methyl-1,2-
butadienylphosphonic dichloride (Xb). Dichloride
Xb, 0.01 mol, was added to a solution of 0.01 mol
of phosphorane I in 15 ml of benzene, and the mixture
was heated for 15 h at 80 90 C. Subsequent vacuum
distillation gave colorless needles of chlorophosphate
IV, yield 0.6 g (32%), mp 62 C. Fractional distilation
of the residue gave 0.45 g (20%) of phosphonic di-
EXPERIMENTAL
The IR spectra (films) were recorded on a UR-20
spectrometer. The NMR spectra were obtained on
Varian-60 (1H, 60 MHz) and Bruker CXP instruments
(31P, 36.47 MHz) using CCl4 or C6H6 as solvent.
The chemical shifts were measured relative to TMS
(1H) or H3PO4 (31P). All operations were performed
under argon.
chloride XI, bp 51 53 C (0.5 mm), n2D0 1.5160; pub-
lished data [12]: bp 65 67 C (1 mm), n2D0 1.5179.
Reaction of trichloro(o-phenylenedioxy)phos-
phorane (I) with dialkyl 1,2-propadienyl- and
ACKNOWLEDGMENTS
3-methyl-1,2-butadienylphosphonates
IIa IIc,
This study was performed in the framework of
the Program Universities of Russia Fundamental
Research and the Program for financial support of
leading scientific schools of the Russian Federation
(project no. 00-15-97424).
Va, and Vb. Dialkyl 1,2-alkadienylphosphonate IIa
IIc, Va, or Vb, 0.01 mol, was added dropwise to
a solution of 0.01 mol of phosphorane I in 10 ml of
carbon tetrachloride or benzene; the mixture warmed
up by 14 15 C. After a day, the mixture was distilled
in vacuo, a fraction boiling in the range 58 80 C
(0.4 mm) being collected. Colorless needles of
o-phenylene chlorophosphate (IV) separated from
the distillate on storage. Yield 1.2 1.3 g (64 70%),
REFERENCES
1. Gloede, J., Z. Chem., 1982, vol. 22, no. 4, pp. 126
mp 59 61 C. 31P NMR spectrum:
18 19 ppm.
134.
P
2. Mironov, V.F., Konovalov, A.I., Litvinov, I.A.,
Gubaidullin, A.T., Petrov, R.R., Shtyrlina, A.A.,
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and Il’yasov, A.V., Zh. Obshch. Khim., 1998,
vol. 68, no. 9, pp. 1482 1509.
Published data [13]: mp 61 63 C, P 19 ppm.
Fractional distillation of the liquid part of the
distillate gave alkyl propadienylchlorophosphonates
IIIa IIIc.
Methyl propadienylchlorophosphonate (IIIa).
3. Mironov, V.F., Shtyrlina, A.A., Azancheev, N.M.,
and Konovalov, A.I., Zh. Obshch. Khim., 2000,
vol. 70, no. 1, pp. 160 161.
Yield 0.76 g (50%), bp 67 70 C (0.03 mm). 31P NMR
spectrum:
34 ppm. Found, %: C 31.58; H 3.85;
P
P 20.49. C4H6ClO2P. Calculated, %: C 31.47; H 3.93;
P 20.32.
4. Khusainova, N.G., Mironov, V.F., and Cherka-
sov, R.A., Zh. Obshch. Khim., 1995, vol. 65, no. 9,
pp. 1578 1579.
Ethyl propadienylchlorophosphonate (IIIb).
Yield 1 g (61%), bp 63 65 C (0.5 mm), n2D0 1.4760;
5. Khusainova, N.G., Reshetkova, G.R., and Cherka-
sov, R.A., Zh. Obshch. Khim., 1998, vol. 68, no. 3,
pp. 396 398.
published data [14]: bp 72 74 C (2 mm), n2D0 1.4781.
31P NMR spectrum:
32 ppm. Found, %: C 36.14;
H 4.94; P 18.47. C5H8PClO2P. Calculated, %: C 36.03;
H 4.80; P 18.62.
6. Khusainova, N.G. and Pudovik, A.N., Usp. Khim.,
1987, vol. 56, no. 6, pp. 975 1003.
Propyl propadienylchlorophosphonate (IIIc).
Yield 1.2 g (66%), bp 74 77 C (0.6 mm), n2D0 1.4772;
published data [14]: bp 96 97 C (1.5 mm), nD20
7. Mikhailova, T.S., Angelov, Kh.M., Ignat’ev, V.M.,
Dogadina, A.V., Zakharov, V.I., Ionin, B.I., and
Petrov, A.A., Zh. Obshch. Khim., 1977, vol. 47,
no. 12, pp. 2701 2707.
1.4790. 31P NMR spectrum:
31 ppm. Found, %:
P
C 40.03; H 5.64; P 17.32. C6H10ClO2P. Calculated,
%: C 39.89; H 5.53; P 17.17.
8. Mikhailova, T.S., Zakharov, V.I., Ignat’ev, V.M.,
Ionin, B.I., and Petrov, A.A., Zh. Obshch. Khim.,
1980, vol. 50, no. 8, pp. 1690 1702.
In the reactions of phosphorane I with 1,2-butadi-
enylphosphonates Va and Vb, products VIa, VIb,
IXa, and IXb were identified by NMR and IR spec-
troscopy in the liquid part of the distillate obtained
after separation of crystalline chlorophosphate IV.
9. Mikhailova, T.S., Ignat’ev, V.M., Ionin, B.I., and
Petrov, A.A., Zh. Obshch. Khim., 1978, vol. 48,
no. 3, p. 701.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 3 2001