Reaction of 2,2,2-trichloro-1,2,3-dioxaphospholo[4,5-b]pyridine with 4-bromophenylacetylene

Full text of DOI:10.1134/S1070363210100336

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 10, pp. 2067–2069. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © E.N. Varaksina, V.F. Mironov, 2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 10, pp. 1747–1749.
LETTERS
TO THE EDITOR
Reaction of 2,2,2-trichloro-1,2,3-dioxaphospholo[4,5-b]pyridine
with 4-Bromophenylacetylene
E. N. Varaksina and V. F. Mironov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Centre,
Russian Academy of Sciences, ul. Arbuzova 8, Kazan, 420088 Russia
e-mail: mironov@iopc.ru
Received January 14, 2010
DOI: 10.1134/S1070363210100336
A simple transformation of dioxaphospholene fragment
into the oxaphosphorinine we found earlier studying
the reaction of 2,2,2-trihalogenobenzo[d]-1,3,2-dioxa-
phosphols with arylacetylenes [1] opens a way to pre-
paration of phosphorus-containing analogs of coumarins,
benzo[e]-1,2-oxaphosphorinine derivatives [2–4].
dihydroxypyridine II in several stages: a silylation
using hexamethyldisilazane to form compound III, the
reaction of the latter with phosphorus trichloride to
give phosphol IV, and chlorination of the latter. The
selected way to phosphol I allows maximally to avoid
possible complexation processes of the base nitrogen
with phosphorus atom or hydrogen chloride in the
intermediate synthesis stages. However phosphorane I
proper is in the equilibrium with hexacoordinated form
V (δР –160.7 ppm).
In this work 2,2,2-trichloro-1,3,2-dioxaphospholo-
[4,5-b]pyridine I was brought into the reaction with
acetylene. Compound I was obtained starting from 2,3-
Me3SiNHSiMe3
OH
OSiMe3
OSiMe3
O
PCl3
ClSiMe3
PCl
−ClSiMe3
−NH3, −HCl
O
N
OH
N
N
II
III
IV
O
O
O
O
Cl2, CH2Cl2
−30oC
PCl3
PCl3
N
N
n
V
I
The reaction of trichlorophosphorane I with 4-
bromophenylacetylene in the presence of equimolar
amount of hexene, which was used to bind the released
hydrogen chloride, under mild conditions (CH2Cl2, 20°С)
proceeds also to the formation of oxaphosphorinane
derivatives. The 31Р NMR spectrum of the reaction
mixture contains characteristic doublet of the main
compound VI at δР 16.6 ppm (2JPCH 23.1 Hz) and the
signal of the starting phosphorus derivative as the ate-
complex V, which precipitates due to the poor
solubility. The removal of compound V and the
solvent followed by evacuating the residue (150°С,
15 mm Hg) to remove hexene and styrenes results in a
glassy substance, which was dissolved in chloroform,
treated with water, and crystallized to obtain
phosphonic acid VII. The structure of the latter was
proved by the 13С, 13С–{1Н} NMR spectra. The
observed signal multiplicity for the nuclei C8a (d.d) and
C4a (d.d) and the coupling constants values are in
accordance with the ipso-substitution of the oxygen
atom in the meta-position relative to the nitrogen atom
and with the chlorination into the position 6 of the
2067

2068
VARAKSINA, MIRONOV
heterocycle. The formation of 2,3,5-trisubstituted
pyridine is also in good agreement with the Н NMR
spectrum, where the protons H5 and H7 resonate as
singlets.
1
8a
N
O
O
P
7
6
Cl
N
OH
O
P
4a
3
Cl
4
H2O
OH
OH
4-BrC6H4C
BuCH
CH, CH2Cl2
, 20oC
5
9
I
10
11
Cl
−HCl
CH2
C6H4Br
−BuCHClCH3
12
Br
VII
VI
Thus, the reaction of phospholopyridine I with 4-
bromophenylacetylene proceeds to form exclusively
compounds of the phosphirine nature. The reaction
makes it possible to extend the synthesis method of
oxaphosphorinine heterocycle to the derivatives, in
which the latter is fused with pyridine that opens
prospects for using other hydroxy substituted N-
heterocycles, including alkaloids.
CH2Cl2 (20 ml) was added a solution of 3.6 g of 4-
bromophenylacetylene and 5 ml of hexene in 15 ml of
CH2Cl2. We observed HCl release and dissolution of
the phosphorane precipitate. After 24 h the solvent was
removed and the reaction mixture was kept in a
vacuum (15 mm Hg) for 2 h at 120°С (the external
heating temperature). The obtained glassy brown
residue containing predominantly compound VI was
washed with anhydrous hexane (2×20 ml) to remove
the formed styrenes and dissolved in 15 ml of
chloroform. The solution was treated with 1 ml of
water. The formed white precipitate was filtered off,
washed with acetone, and dried in air. Yield of
phosphonate VII 1.03 g (12.6%), bp 190–191°С. IR
spectrum, ν, cm–1: 3447, 3232, 3069, 2955, 2925,
2855, 2289, 1634, 1614, 1548, 1488, 1455, 1378,
1313, 1204, 1132, 1077, 1007, 933, 868, 803, 787,
761, 666, 510. 1H NMR spectrum, δ, ppm: 6.28 d (1Н,
2,3-Bis(trimethylsiloxy)pyridine (III). A mixture
of 10 g of 2,3-dihydroxypyridine II, 39 ml of hexa-
methyldisilazane, and some drops of trimethyl-
chlorosilane was refluxed for 4 h. Then the hexa-
methyldisilazane excess was removed by distillation.
The residual colorless clear liquid was distilled in a
vacuum. Yield 19.1 g (68.6%), bp 119°C (25 mm Hg),
nD20 1.512. IR spectrum, ν, cm–1: 412, 579, 597, 624,
695, 739, 766, 795, 847, 906, 933, 1063, 1107, 1201,
1251, 1284, 1305, 1372, 1462, 1584, 1623, 1655,
1872, 1959, 2555, 2901, 2959, 3058, 3462.
2
4
H3, JРCH 13.0 Hz), 7.46 d (1Н, H5, JHCCCH 2.9 Hz),
4
3
7.63 d (1Н, H7, JHCCCH 2.9 Hz), 7.26 d (H10, JНСCH
8.6 Hz), 7.53 d (H11, JНСCH 8.6 Hz). 13С NMR
3
2-Chloro-1,3,2-dioxaphospholo[4,5-b]pyridine (IV).
A mixture of 45.9 g (0.18 mol) of compound III and
26 ml (0.30 mol) of phosphorus trichloride was heated
to boiling. The residue was distilled. Yield 13.1 g
(41.4%), bp 90–100°С (15 mm Hg), colorless clear
liquid. 31Р–{1Н} NMR spectrum (162.0 MHz, CDCl3),
δР 171.2 ppm.
spectrum, δ, ppm (the signal multiplicity in the 13С–
{1H} spectrum is given in the brackets): 123.21 d.d (d)
1
1
(С3, JPC 182.1, JНC 150.3 Hz), 148.75 m (d) (С4,
3
3
JPCCC 4.6, JНCC 2.2 Hz), 124.12 d.d (d) (С4a, JPCCC
3
2
3
4
4
4а
3
4а
1
15.2, JНCCC 9.5 Hz), 131.35 d.d (s) (С5, JHC 184.1,
5
3
1
3
6
7
5
JНССC 3.7 Hz), 110.68 br.s (s) (С ), 141.09 d.d (s) (С ,
JHC 167.0, JHCCC 5.3 Hz), 159.31 d.d.d (d) (С8а,
3
7
7
2,2,2-Trichloro-1,3,2-dioxaphospholo[4,5-b]pyri-
dine (I). To a solution of 3.7 g (0.055 mol) of
phosphite IV in 10 ml of methylene chloride was
added 1.5 g (0.058 mol) of chlorine in 30 ml of CH2Cl2
at –30°С (the bath temperature). 31Р–{1Н} NMR
spectrum (СН2Сl2): δР –40 ppm. The obtained
compound was used without further purification.
3
3
8а
8а
8а
JНCCC 8.6, JНCCC 7.3, JРCССC 1.0 Hz), 138.73 d.d.d
(d) (С9, JPCCCС 20.8, JНCCС 7.0, JНCCС 7.0 Hz),
3
3
3
9
9
9
121.94 d.d (s) (С10, JHC 161.1, JНCCС 7.0 Hz),
1
3
10
10
128.44 d.d (s) (С11, JHC3 166.9, JНССC 5.7 Hz),
1
3
11
11
121.94 d.d.d.d (s) (С12, JН3С1СC 11.2, JНССC 11.2,
3
12
12
3
3
1
12
12
JНССC 3.0, JНССC 3.0 Hz). Р–{ H} NMR spectrum:
δР 10.0 ppm.
Reaction of compound (I) with 4-bromophenyl-
acetylene. To a suspension of phosphorane I in
1
The H and 31Р NMR spectra were recorded on
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 10 2010

REACTION OF 2,2,2-TRICHLORO-1,2,3-DIOXAPHOSPHOLO[4,5-b]PYRIDINE
2069
1
Bruker Avance-400 (400 MHz, Н; 100.6 MHz, 13С)
REFERENCES
and Bruker CXP-100 (36.48 MHz, 31Р) spectrometers
in DMSO-d6 relative to the solvent or external
reference (H3PO4) signal. The IR spectra were re-
gistered on a Bruker Vector-22 instrument (mineral oil,
KBr).
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Gubaidullin, A.T., Petrov, R.R., Shtyrlina, A.A.,
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p. 1482.
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ACKNOWLEDGMENTS
3. Borges, F., Roleira, F., Milhazes, N., Santana, L., and
Uriarte, E., Curr. Med. Chem., 2005, vol. 12, no. 8,
p. 887.
4. Grazul, M. and Budzisz, E., Coord. Chem. Rev., 2009,
vol. 253, p. 2588.
This work was financially supported by the Russian
Foundation for Basic Research (grant no. 07-03-
00180).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 10 2010