4-Phenylsulfenyl- and 4-phenylselenenyl-2,5-dihydro-1,2-oxaphosphole-2- oxides by the reaction of 1,2-alkadienephosphonic amidoesters with sulphenyl- and selenenylbromides

Article abstract of DOI:10.1080/10426500801968011

The reactivity of 1,2-alkadienephosphonic amidoesters towards sulphenyl- and seleneneylbromides has been investigated. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/10426500801968011

This article was downloaded by: [University of California Santa Cruz]
On: 27 October 2014, At: 15:38
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,
UK
Phosphorus, Sulfur, and Silicon
and the Related Elements
Publication details, including instructions for
authors and subscription information:
http://www.tandfonline.com/loi/gpss20
4-Phenylsulfenyl- and
4-Phenylselenenyl-2,5-
dihydro-1,2-oxaphosphole-2-
oxides by the Reaction of
1,2-Alkadienephosphonic
Amidoesters with Sulphenyl-
and Selenenylbromides
D. D. Enchev a
a Department of Organic Chemistry and Technology,
Faculty of Natural Sciences , Konstantin Preslavsky
University of Shumen , Shumen, Bulgaria
Published online: 10 Oct 2008.
To cite this article: D. D. Enchev (2008) 4-Phenylsulfenyl- and 4-Phenylselenenyl-2,5-
dihydro-1,2-oxaphosphole-2-oxides by the Reaction of 1,2-Alkadienephosphonic
Amidoesters with Sulphenyl- and Selenenylbromides, Phosphorus, Sulfur, and Silicon
and the Related Elements, 183:11, 2649-2654
To link to this article: http://dx.doi.org/10.1080/10426500801968011
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the
information (the “Content”) contained in the publications on our platform.
However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness,
or suitability for any purpose of the Content. Any opinions and views
expressed in this publication are the opinions and views of the authors, and

are not the views of or endorsed by Taylor & Francis. The accuracy of the
Content should not be relied upon and should be independently verified with
primary sources of information. Taylor and Francis shall not be liable for any
losses, actions, claims, proceedings, demands, costs, expenses, damages,
and other liabilities whatsoever or howsoever caused arising directly or
indirectly in connection with, in relation to or arising out of the use of the
Content.
This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan,
sub-licensing, systematic supply, or distribution in any form to anyone is
expressly forbidden. Terms & Conditions of access and use can be found at
http://www.tandfonline.com/page/terms-and-conditions

Phosphorus, Sulfur, and Silicon, 183:2649–2654, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500801968011
4-Phenylsulfenyl- and 4-Phenylselenenyl-2,5-dihydro-1,2-
oxaphosphole-2-oxides by the Reaction of
1,2-Alkadienephosphonic Amidoesters with Sulphenyl-
and Selenenylbromides
D. D. Enchev
Department of Organic Chemistry and Technology, Faculty of Natural
Sciences, Konstantin Preslavsky University of Shumen, Shumen,
Bulgaria
The reactivity of 1,2-alkadienephosphonic amidoesters towards sulphenyl- and se-
leneneylbromides has been investigated.
Keywords 1,2-Alkadienephosphonates; electrophilic reagents
INTRODUCTION
Phosphorylated 1,2-alkadienes provide an unusual system of reaction
centers. Their syntheses as well as their reactions are subject of current
interest.1−4 There is an increasing number of publications concerning
the reactivity of phosphorylated 1,2-alkadienes, as well as theoretical
studies in this area.5−18
In continuation of our studies on phosphorus-substituted hete-
rocycles, we now report a straight forward synthesis with high
yields of 4-phenylsulphenyl- and 4-phenylselenenyl-2,5-dihydro-1,2-
oxaphosphole-2-oxides.
RESULTS AND DISCUSSION
As starting compounds for our investigations we synthesized the dichlo-
rides of 1,2-alkadienephosphonic acids following the procedure de-
scribed earlier.18 The nucleophilic displacement of the two chlorine
Received 4 February 2008; accepted 6 February 2008.
The authors are indebted to Prof. S. Simova and to all the staff of the National Centre
of NMR Spectroscopy, Bulgarian Academy of Sciences.
Address correspondence to D. D. Enchev, Department of Organic Chemistry and
Technology, Faculty of Natural Sciences, Konstantin Preslavsky University of Shumen,
Shumen 9700, Bulgaria. E-mail: enchev@shu-bg.net
2649

2650
D. D. Enchev
atoms at phosphorus with an alkoxy- and a dialkylamino group leads
to the amidoesters of 1,2-alkadienephosphonic acids 3a−d in very good
yields.19
SCHEME 1
The reactions of 3a−d with phenylsulphenyl and phenylselenenyl
bromide were performed in a polar solvent at low temperature and
under argon atmosphere.
SCHEME 2
The composition and structure of the 2,5-dihydro-1,2-oxaphosphole
derivatives 4a−d and 5a−d was confirmed by their 1H, 31P NMR
and IR spectra, as well as by elemental analyses (see EXPERIMEN-
TAL). The results here reported confirm the direction of the reaction

4-Phenylsulfenyl- and 4-Phenylselenenyl-2,5-dihydro-1,2-oxaphosphole-2-oxides 2651
of amidoesters of 3,3-disubstituted-1,2-alkadienephosphonic acids with
sulphenyl- and selenenyl halides: regardless of the kind of the reagent
in all cases 2,5-dihydro-1,2-oxaphosphole derivatives were isolated. The
driving force of the reaction is the formation of the intermediate A,
stabilized by two methyl groups (4a,b and 5a,b) or by cyclohexyl ring
(4c,d and 5c,d), which facilitates its intramolecular interaction with
the phosphoryl group, acting as a nucleophile. The dealkylation of the
resulting phosphonium intermediate B leads to the 2,5-dihydro-1,2-
oxaphosphole derivatives:
SCHEME 3
EXPERIMENTAL
The 1H NMR and 31P NMR spectra were measured in CDCl3 solution at
ambient temperature on a Bruker Avance DRX 250 MHz spectrometer
using TMS (1H) and 85% H3PO4 (31P) as external standards. Chemical
shifts are given in ppm and are positively downfield from the standard.
The IR spectra were run on an IR-72 spectrophotometer (Carl Zeiss
Jena). Elemental analyses were carried out by the University of Shu-
men Microanalytical Service Laboratory.
Phenylselenenyl bromide is commercially available. Phenylsulfenyl
bromide was synthesized according to the procedure described.20 Com-
pounds 3a−d was synthesized according to the procedure described.19
The solvents were purified by standard methods. All reactions were
carried out in oven-dried glassware under an argon atmosphere and
exclusion of moisture. All compounds were checked for their purity on
TLC plates.

2652
D. D. Enchev
Preparation of Compounds 4a−d and 5a−d—General
Procedure
To a solution of 0.005 mol of 3a−d in 50 mL of dry methylene chloride
under argon atmosphere and stirring at –10◦C to –8◦C a solution of
0.005 mol of phenylsuphenyl bromide (0.094 g) or phenylselenenyl bro-
mide (0.118 g) in 10 mL of the same solvent was added dropwise during
30 min. Then the solvent was evaporated and the residue was purified
by column chromatography hexane/benzene 1:1.
(5,5-Dimethyl-2-oxo-4-phenylsulphenyl-2,5-dihydro-2 λ5-
[1,2]oxaphosphol-2-yl)diethylamine (4a)
Pale yellow oil, yield 1.32 g (85%); C15H21O2NPS; calcd.: P, 9.98; N,
4.51; S 10.33%, Found: P, 9.95; N, 4.49; S, 10.29%; IR, ν(cm−1): 1590
1
(C C), 1256 (P O). H NMR (CDCl3): δ = 7.56−7.23 (m, 5H, arom-
H), 6.36 (dd, 2 J = 27.8 Hz, 3 J = 3.8 Hz, 1H, H C=); 2.59 (m,
PH
HH
4H, CH3CH N)), 1.46 (s, 3H, CCH ), 1.51 (s, 3H, CCH ), 1.02 (m, 6H,
2
3
CH CH2N). 31P NMR (CDCl3): δ =333.1.
3
(5,5-Dimethyl-2-oxo-4-phenylsulphenyl-2,5-dihydro-2λ5-
[1,2]oxaphosphol-2-yl)-dipropylamine (4b)
Pale yellow oil, yield 1.37 g (81%); C17H26NO2PS; calcd.: P, 9.12; N,
4.12; S, 9.44%, Found: P, 9.08; N, 4.09; S, 9.40%; IR, ν(cm−1): 1592
1
(C C), 1259 (P O), 1000 (P O C), H NMR (CDCl3); δ = 7.56−7.46
(m, 2H, arom-H), 7.29−7.23 (m, 3H, arom-H), 5.35 (dd, 2 J = 27.8 Hz,
PH
3 J = 3.8 Hz, 1H, H C=), 2.54−2.48 (m, 4H, CH3CH2CH N), 1.46
HH
2
(s, 3H, CCH ), 1.51 (s, 3H, CCH ); 1.28−1.19 (m, 4H, CH3CH CH2N),
3
3
2
0.91-0.89 (m, 6H, CH CH2CH2N). 31P NMR (CDCl3): δ = 29.0.
3
4-(2-Oxo-4-phenylsulphenyl-1-oxo-2λ5-phospha-spiro[4,5]dec-
3-en-2-yl)-diethylamine (4c)
Yellow oil, yield 1.28 g (71%); C18H26NO2PS; calcd.: P, 8.81; N, 3.98;
S, 9.12%; Found: P, 8.79; N, 3.95; S, 9.10%; IR ν(cm−1): 1589 (C C),
1
1237 (P O). H NMR (CDCl3): δ = 7.56 − 7.46 (m, 2H, arom-H); 7.29
2
3
− 7.23 (m, 3H, arom-H); 5.35 (dd, J = 27.8 Hz, J = 3.8 Hz, 1H,
PH
HH
H C=), 2.59 (m, 4H, CH3CH N), 1.90-1.43 (m, 10H, (CH2)5), 1.02 (m,
2
6H, CH CH2N). 31P (CDCl3): δ = 28.9.
3
4-(2-Oxo-4-phenylsulphenyl-1-oxo-2λ5-phospha-spiro[4,5]dec-
3-en-2-yl)-dipropylamine (4d)
Yellow oil, yield 1.33 g (70%); C20H30NO2PS; calcd.: P, 8.16; N,
3.69; S, 8.45%; Found: P, 8.12; N, 3.66; S, 8.41; IR, ν(cm−1): 1590
1
(C C), 1253 (P O); H NMR (CDCl3): δ =7.56-7.46 (m, 2H, arom-H);

4-Phenylsulfenyl- and 4-Phenylselenenyl-2,5-dihydro-1,2-oxaphosphole-2-oxides 2653
7.29−7.23 (m, 3H, arom-H); 5.35 (dd, 2 J = 27.8 Hz, 3 J = 3.8 Hz, 1H,
PH
HH
H C=), 2.54−2.48 (m, 4H, CH3CH2CH N), 1.90−1.43 (m, 10H, (CH2)5);
2
1.28−1.19 (m, 4H, CH3CH CH2N), 0.91-0.89 (m, 6H, CH CH2CH2N).
2
3
31P NMR (CDCl3): δ = 28.9.
(5,5-Dimethyl-2-oxo-4-phenylselenenyl-2,5-dihydro-2λ5-
[1,2]oxaphosphol-2-yl)diethylamine (5a)
Pale yellow oil, yield 1.46 g (82%); C15H21O2NPSe; calcd.: P, 8.67; N,
3.92%, Found: P, 8.64; N, 3.89%; IR, ν(cm−1): 1589 (C C), 1258 (P O).
1H NMR (CDCl3): δ = 7.56−7.23 (m, 5H arom-H), 6.36 (dd, 2 J
=
PH
27.8 Hz, 3 J = 3.8 Hz, 1H, H C=), 2.59 (m, 4H, CH3CH N), 1.46
HH
2
(s, 3H, CCH ), 1.51 (s, 3H, CCH ), 1.02 (m, 6H, CH CH2N). 31P NMR
3
3
(CDCl3): δ = 333.1.
(5,5-Dimethyl-2-oxo-4-phenylselenenyl-2,5-dihydro-2λ5-
[1,2]oxaphosphol-2-yl)-dipropylamine (5b)
Pale yellow oil, yield 1.54 g (80%); C17H26NO2PSe; calcd.: P, 8.02;
N, 3.62%, Found: P, 8.00; N, 3.59%; IR, ν(cm−1): 1592 (C C), 1259
(P O), 1000 (P O C). 1H NMR (CDCl3): δ = 7.56−7.46 (m, 2H, arom-
H), 7.29−7.23 (m, 3H, arom-H), 5.35 (dd, 2 J = 27.8 Hz, 3 J = 3.8
PH
HH
Hz, 1H, H C=), 2.54−2.48 (m, 4H, CH3CH2CH N), 1.46 (s, 3H, CCH ),
2
3
1.51 (s, 3H, CCH ), 1.28−1.19 (m, 4H, CH3CH CH2N), 0.91-0.89 (m,
3
2
6H, CH CH2CH2N). 31P NMR (CDCl3): δ = 29.0.
3
4-(2-Oxo-4-phenylselenenyl-1-oxo-2λ5-phospha-spiro[4,5]dec-
3-en-2-yl)-diethylamine (5c)
Yellow oil, yield 1.43 g (72%); C18H26NO2PSe; calcd.: P, 7.77; N,
3.51%; Found: P, 7.74; N, 3.47%; IR, ν(cm−1): 1593 (C C), 1245 (P O).
1H NMR (CDCl3): δ =7.56 − 7.46 (m, 2H, arom-H), 7.29−7.23 (m, 3H,
arom-H), 5.35 (dd, 2 J = 27.8 Hz, 3 J = 3.8 Hz, 1H, H C=), 2.59 (q,
PH
HH
4H, CH3CH N), 1.90-1.43 (m, 10H, (CH2)5), 1.02 (m, 6H, CH CH2N).
2
3
31P NMR (CDCl3)δ = 28.9.
4-(2-Oxo-4-phenylselenenyl-1-oxo-2λ5-phospha-spiro[4,5]dec-
3-en-2-yl)-dipropylamine (5d)
Yellow oil, yield 1.57 g (74%); C20H30NO2PSe; calcd.: P, 7.26; N,
3.28%; Found: P, 7.22; N, 3.23%; IR, ν(cm−1): 1589 (C C), 1237 (P O).
1H NMR (CDCl3): δ = 7.56 − 7.46 (m, 2H, arom-H), 7.29−7.23 (m,
3H, arom-H), 5.35 (dd, 2 J = 27.8 Hz, 3 J = 3.8 Hz, 1H, H C=
PH
HH
), 2.54−2.48 (m, 4H, CH3CH2CH N), 1.90−1.43 (m, 10H, (CH2)5),
2
1.28−1.19 (m, 4H, CH3CH CH2N), 0.91−0.89 (m, 6H, CH CH2CH2N).
2
3
31P NMR (CDCl3): δ = 28.9.

2654
D. D. Enchev
REFERENCES
[1] Ch. M. Angelov, K. V. Vachkov, and M. Kirilov, Zh. Obshch. Khim., 52, 538 (1984).
[2] Ch. M. Angelov and K. V. Vachkov, Phosphorus, Sulfur, 21, 237 (1984).
[3] I. V. Alabugin and V. K. Brel, Zh. Obshch. Khim., 65, 1670 (1995).
[4] Ch. M. Angelov, K. V. Vachkov, B. I. Ionin, and M. Kirilov, Zh. Obshch. Khim., 49,
2438 (1979).
[5] I. V. Alabugin, V. K. Brel, and N. S. Zefirov, Zh. Obshch. Khim., 63, 2387 (1993).
[6] A. N. Chekhlov, I. V. Alabugin, V. K. Brel, and N. S. Zefirov, Proc. Rus. Acad. Sci.,
335, 753 (1994).
[7] I. V. Alabugin, V. K. Brel, A. N. Chekhlov, N. S. Zefirov, and P. J. Stang, Tetrahedron
Lett., 35, 8275 (1994).
[8] Ch. M. Angelov, K. V. Vachkov, B. I. Ionin, and M. Kirilov, Proc. Bulg. Acad. Sci., 32,
611 (1979).
[9] N. G. Khusainova, L. V. Naumova, E. A. Berdnikov, and A. N. Pudovik, Zh. Obshch.
Khim., 54, 1452 (1984).
[10] Ch. M. Angelov and Ch. Tancheva, Zh. Obshch. Khim., 55, 53 (1985).
[11] Ch. M. Angelov and Ch. Zh. Christov, Zh. Obshch. Khim., 50, 1891 (1980).
[12] Ch. M. Angelov, D. D. Enchev, and M. Kirilov, Phosphorus, Sulfur, and Silicon, 35,
35 (1988).
[13] T. N. Tancheva, Ch. M. Angelov, and D. M. Mondeshka, Heterocycles, 22, 843 (1985).
[14] Ch. M. Angelov, K. V. Vachkov, and M. Kirilov, Tetrahedron Lett., 21, 3507 (1983).
[15] N. G. Khusainova, I. Ya. Sipel, E. A. Berdnikov, and A. N. Pudovik, Zh. Obshch.
Khim., 54, 2796 (1984).
[16] N. G. Khusainova, I. Ya. Sipel, R. A. Cherkasov, E. A. Berdnikov, and A. N. Pudovik,
Zh. Obshch. Khim., 55, 701 (1980).
[17] I. V. Alabugin and V. K Brel, Usp. Khim., 66, 3 (1997).
[18] T. S. Mikhailova, V. I. Zaharov, V. M. Ignatiev, B. I. Ionin, and A. A. Petrov, Zh.
Obshch. Khim., 50, 1690 (1980).
[19] Ch. M. Angelov and D. D. Enchev, Phosphorus, Sulfur, and Silicon, 34, 163 (1987).
[20] M. P. Simonin, M. J. Pauet, J. M. Gence, and C. Paumier, Org. Magn. Reson., 8, 508
(1976).