Interaction of 1,2-alkadienephosphonic dialkyl esters with sulfenyl-and selenenylbromides

Article abstract of DOI:10.1002/hc.20083

The reactivity of dialkyl esters of 1, 2-alkadienephosphonic acids towards sulfenyl-and selenenyl-bromides was investigated. The reactions of 3,5 with phenylsulfenyl and phenylselenenyl-bromides were performed in polar solvent at low temperature and argon

Full text of DOI:10.1002/hc.20083

Heteroatom Chemistry
Volume 16, Number 2, 2005
Interaction of 1,2-Alkadienephosphonic
Dialkyl Esters with Sulfenyl-
and Selenenylbromides
Dobromir D. Enchev
Department of Organic Chemistry and Technology, Faculty of Natural Sciences, “Konstantin
Preslavsky” University, 9712, Shumen, Bulgaria
Received 15 November 2004
phenylsulfenyl- and phenylselenenyl-bromides. The
ABSTRACT: The reactivity of dialkyl esters of 1,
mentioned reagents were chosen because of their
similarity to sulfenyl- and selenenyl-chlorides, as
2-alkadienephosphonic acids toward sulfenyl- and
ꢀ
C
selenenyl-bromides has been investigated.
2005
well as because of some differences between them
of course, i.e.: (1) Energy and bond length of the
S Cl (255 kJ/mol, 207 nm) and S Br (217 kJ/mol,
227 nm) [19], (2) the higher dealkylation rate (Arbu-
zov reaction) in case of bromide anion as compared
to chloride anion [20], (3) the degree of stabiliza-
tion of quasiphosphonium intermediate, in general,
is more significant in the case of bromide than in the
case of chloride anion [21].
As starting compounds in our investigation, we
synthesized dichlorides of 1,2-alkadienephosphonic
acids 2 following the procedure described earlier
[18]. The nucleophilic displacement of the two chlo-
rine atoms at phosphorus with alkoxy-groups leads
to the titled compounds, 3, 5 in very good yields
(Scheme 1).
Wiley Periodicals, Inc. Heteroatom Chem 16:156–158,
2005; Published online in Wiley InterScience (www.inter-
science.wiley.com). DOI 10.1002/hc.20083
INTRODUCTION
The phosphorylated 1,2-alkadienes provide an
unusual system of centers of unsaturation. Their
preparation as well as their reactions attracts per-
manent interest [1–4]. An increasing number of
reactions involving phosphorylated 1,2-alkadienes
as well as concepts of their reactivity are noticed
[5–18].
RESULTS AND DISCUSSION
The reactions of 3, 5 with phenylsulfenyl- and
phenylselenenyl-bromides were performed in polar
solvent, at low temperature and argon atmosphere
(see Scheme 2).
The study of the reactivity of these compounds, as
well as the creation of methods for their preparation,
is one of the topics in our investigations for more
than 20 years [8–14].
In this paper, we wish to report our results
from the investigations of the interaction of di-
alkyl esters of 1,2-alkadienephosphonic acids with
Obtaining of the 2,5-dihydro-1,2-oxaphosphole
1
derivatives 4,6 and 7,8 was confirmed by their H,
31P NMR, and IR spectra as well as by elemental anal-
ysis (see Experimental). Very good yields of these
compounds and the absence of other products are
probably due to the combined influence of the fac-
tors mentioned above, especially to the increased sta-
bility of the quasiphosphonium intermediate of the
Correspondence to: Dobromir D. Enchev; e-mail: enchev@shu-
bg.net.
c
ꢀ
2005 Wiley Periodicals, Inc.
156

Interaction of 1,2-Alkadienephosphonic Dialkyl Esters with Sulfenyl- and Selenenylbromides 157
TABLE 1 R and R1 for Compounds 3, 4, 7
reaction:
R
R1
a
b
c
d
e
f
g
h
i
Me
Et
Me
Me
Me
Me
Me
Me
Me
Me
Et
Prn
Pri
Bun
But
The literature data and the results we reported
PhCH2
Ph(CH2)2
Me
here confirm the direction of the reaction of dialkyl
esters of 3,3-disubstituted 1,2-alkadienephosphonic
acids with sulfenyl- and selenenyl-halogenides, i.e.
irrespective to the kind of the reagent in all cases
oxaphospholic derivatives were isolated.
j
k
l
Et
Et
Et
Prn
Pri
Bun
Et
Et
Et
Et
Et
m
n
o
p
q
r
s
t
u
v
w
x
But
EXPERIMENTAL
PhCH2
Ph(CH2)2
1H and 31P NMR spectra were determined on Jeol
PX 10 and FX-90 Q spectrometers in normal tem-
perature as solution in CDCl3 with TMS as internal
standard. The IR-spectra were recorded on a spec-
trophotometer IR-72 (Carl Zeiss Jena).
The phenylsulfenyl- and phenylselenenyl-bro-
mides were prepared from diphenyl disulfide and
diphenyl diselenide, commercially available, and
bromine in nonpolar media.
Me
Et
Pri
Pri
Pri
Pri
Pri
Pri
Pri
Pri
Prn
Pri
Bun
But
PhCH2
Ph(CH2)2
Preparation of 4-Phenylthio-2-alkoxy-2,5-
dihydro-1,2-oxaphosphol-2-oxides 4a–x, 6a–h
the solvent was evaporated and the residue was dis-
tilled in vacuum.
4a: Yield 85%; found P, 12.94; S, 13.42; formula
General Procedure. To the solution of 0.05 mol
of 3a–x, 5a–h in 50 mL dry methylene chloride under
argon atmosphere and stirring, at −10 to −8◦C, a so-
lution of 0.05 mol of phenylsulfenyl bromide in the
same solvent was added dropwise in 30 min. Then
1
C12H15OPS; calcd. P, 12.99; S, 13.46. H NMR 6.36
(d 2JHP 7.0 Hz), 1.46, 1.51, 7.8 m; 31P 33.09, IR 1590
ꢀ(C C), 1256 ꢀ(P O), 930 ꢀ(P O C) cm−1.
4i: Yield 82%; found P, 12.24; S, 12.68; formula
1
C13H17OPS; calcd. P, 12.27; S, 12.71; H NMR 6.38
(d 2JHP 7.1 Hz), 1.51, 0.92, 1.89, 7.8 m, 31P 33; IR 1588
ꢀ(C C), 1259 ꢀ(P O), 930 ꢀ(P O C) cm−1.
6a: Yield; 86%; found P, 11.10; S, 11.49; formula
1
C15H19OPS; calcd. P, 11.13; S, 11.52; H NMR 6.40
(d 2JHP 7.0 Hz), 1.68, 7.9 m, 31P 32.9; IR 1582 ꢀ(C C),
1257 ꢀ(P O), 930 ꢀ(P O C) cm−1.
TABLE 2 R for Compounds 5, 6, 8
R
a
b
c
d
e
f
Me
Et
Prn
3a–x, 5a–h
Pri
Bun
i = Pyr., Pyr. HCl
ii = 2 ROH, 2 Pyr.
3 R2 = Me
5 R1 + R2 = (CH2)5
for R1 see Tables 1, 2
But
g
h
PhCH2
Ph(CH2)2
SCHEME 1

158 Enchev
iii = PhSBr or PhSeBr −10 to −8◦C, CH2Cl2
for R and R1 see Tables 1,2
SCHEME 2
[4] Angelov, Ch. M.; Vachkov, K. V.; Ionin, B. I.; Kirilov,
M. Zh Obshch Khim 1979, 49, 2438.
[5] Alabugin, I. V.; Brel, V. K.; Zefirov, N. S. Zh Obshch
Khim 1993, 63, 2387.
[6] Chekhlov, A. N.; Alabugin, I. V.; Brel, V. K.; Zefirov,
N. S. Proc Russ Acad Sci 1994, 335, 753.
[7] Alabugin, I. V.; Brel, V. K.; Chekhlov, A. N.; Zefirov,
N. S.; Stang, P. J. Tetrahedron Lett 1994, 35, 8275.
[8] Angelov, Ch. M.; Vachkov, K. V.; Ionin, B. I.; Kirilov,
M. Proc Bulg Acad Sci 1979, 32, 611.
[9] Khusainova, N. G.; Naumova, L. V.; Berdnikov, E. A.;
Pudovik, A. N.; Zh Obshch Khim 1984, 54, 1452.
[10] Angelov, Ch. M.; Tancheva, Ch. Zh Obshch Khim
1985, 55, 53.
[11] Angelov, Ch. M.; Christov, Ch. Zh. Zh Obshch Khim
1980, 50, 1891.
[12] Angelov, Ch. M.; Enchev, D. D.; Kirilov, M. Phospho-
rus Sulfur 1988, 20, 35.
[13] Tancheva, T. N.; Angelov, Ch. M.; Mondeshka, D. M.
Heterocycles 1985, 22, 843.
Preparation of 4-Phenylseleno-2-alkoxy-2,
5-dihydro-1,2-oxaphosphol-2-oxides 7a–x, 8a–h
General Procedure. To the solution of 0.05 mol
of 3a–x, 5a–h in 50 mL dry methylene chloride un-
der argon atmosphere and stirring, at −10 to −8◦C,
a solution of 0.05 mol of phenylselenenyl bromide
in the same solvent was added dropwise in 30 min.
Then the solvent was evaporated and the residue was
distilled in vacuum.
7a: Yield 85%; found P, 10.82; formula
1
C12H15OPSe; calcd. P, 10.86; H NMR 6.36 (d 2JHP
7.0 Hz), 1.57, 1.53, 7.7 m, 31P 32; IR 1594 ꢀ(C C),
1257 ꢀ(P O), 930 ꢀ(P O C) cm−1.
7i: Yield 84%; cryst. found P, 10.31; formula
C13H17OPSe; calcd. P, 10.35; 1H NMR 6.38 (d2JHP
7.1 Hz), 1.50, 0.90, 1.88, 7.9 m, 31P 33; IR 1589
ꢀ(C C), 1260 ꢀ(P O), 930 ꢀ(P O C) cm−1.
8a: Yield 87%; found P, 9.50; formula
C15H19OPSe; calcd. P, 9.52; 1H NMR 6.40 (d 2JHP
7.0 Hz), 1.68, 7.8 m, 31P 31.9; IR 1584 ꢀ(C C), 1258
ꢀ(P O), 930 ꢀ(P O C) cm−1.
[14] Angelov, Ch. M.; Kirilov, M.; Vachkov, K. V.; Spassov,
S. L. Tetrahedron Lett 1980, 21, 3507.
[15] Khusainova, N. G.; Sippel, I. Ja.; Berdnikov, E. A.;
Pudovik, A. N. Zh Obshch Khim 1984, 54, 2796.
[16] Khusainova, N. G.; Sippel, I. Ja.; Cherkasov, R. A.;
Berdnikov, E. A.; Pudovik, A. N. Zh Obshch Khim
1980, 55, 701.
[17] Alabugin, I. V.; Brel, V. K. Usp Khim 1997, 66, 3.
[18] Mikhailova, T. S.; Zaharov, V. I.; Ignatiev, V. M.; Ionin,
B. I.; Petrov, A. A. Zh Obshch Khim 1980, 50, 1690.
[19] Huheey, J. E.; Keiter, E. A.; Keiter, R. L. Inorganic
Chemistry: Principles of Structure and Reactivity, 4th
ed.; Harper & Row: New York, 1997.
REFERENCES
[1] Angelov, Ch. M.; Vachkov, K. V.; Kirilov, M. Zh Obshch
Khim 1984, 52, 538.
[2] Angelov, Ch. M.; Vachkov, K. V. Phosphorus Sulfur
1984, 21, 237.
[20] Kirby, A. J.; Warren, S. G. Organic Chemistry of Phos-
phorus; Elsevier, New York, 1967.
[3] Alabugin, I. V.; Brel, V. K. Zh Obshch Khim 1995, 65,
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[21] Comprehensive Organic Chemistry; Pergamon Press:
Elmsford, NY, 1979, Russ. Transl., 1985, 32, 638.