Cyclic p(III)-phosphorylated derivatives of pamoic acid. the reaction of 4,4′-methylene-bis(2-phenylnaphtho[2,3-d]-1,3,2-dioxaphosphorin-4-one) with chloral

Full text of DOI:10.1134/S107036321003028X

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 3, pp. 536–537. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © L.M. Abdrakhmanova, V.F. Mironov, L.A. Burnaeva, I.V. Konovalova, 2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80,
No. 3, pp. 508–509.
LETTERS
TO THE EDITOR
Cyclic P(III)-Phosphorylated Derivatives of Pamoic Acid.
The Reaction of 4,4'-Methylene-bis(2-phenylnaphtho[2,3-d]-
1,3,2-dioxaphosphorin-4-one) with Chloral
L. M. Abdrakhmanovaa, V. F. Mironova,b, L. A. Burnaevab, and I. V. Konovalovab
a Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
e-mail: mironov@iopc.knc.ru
b Ulyanov-Lenin Kazan State University, Kazan, Tatarstan, Russia
Received October 5, 2009
DOI: 10.1134/S107036321003028X
The mixed cyclic anhydride derivatives of natural
hydroxycarbocylic acids, as well as of phosphorous or
phosphonous acids are convenient reagents for the
synthesis of heterocycles with predefined structure.
Such acids react with activated unsaturated compounds
under mild conditions, readily cleaving the macroergic
RO–C(O) fragment and forming the products of cyclic
and acyclic structures [1–3]. Recently, by an example
of hexafluoroacetone we demonstrated the possibility
to involve also more complex objects in such
processes, the P(III)-cyclic derivatives derived from
the natural substance, 4,4'-methylene-bis(3,2-hydroxy-
naphthoic) (pamoic) acid (I) [4], interesting due to
their biological properties [5–7]. In this paper we
attempted to prepare the products of expansion of a
six-membered ring to a seven-membered one by an
example of reaction of chloral with a phosphorylated
derivative of the pamoic acid containing phosphorus–
carbon bond, 4,4'-methylene-bis(2-phenylnaphtho[2,3-d]-
1,3,2-dioxaphosphorin-4-one) (II). Direct phospho-
ylation of acid I with PCl3 did not give an unam-
biguous result [8], so we synthesized compound II in
two steps: The silylation of acid I with hexa-
methyldisilazane followed by the reaction of the acid I
O-trimethylsilyl derivative with dichlorophenylphos-
phine.
O
O
O4
*
2P
7
6
5a
11
6a
COOH
5
8
9
1C2 Cl3
_
O
P
3
Ph13 16
*
10a
17
OH
O
O
Ph
Ph
O
10
(1) 2(Me3Si)2NH
CCl3CHO
1
O
O
(2) 2PhPCl2
*
O
OH
P
Ph
CCl3
P
O
*
O
COOH
O
O
I
II
III
Compound II reacts with the prochiral chloral
under mild conditions with the formation of six
stereoisomeric bis(naphtho-1,4,2-dioxaphosphepines)
(III) (δP 33.6, 32.5, 31.6, 31.2, 29.3, 28.7 ppm) in the
ratio 4:5:5:33:4:9. This reaction gives rise to four
chiral center resulting in the formation of a mixture of
diastereomers. However, one of them (δP 31.2 ppm)
dominates. In a similar reaction of the cycle expansion
of 2-phenylnaphtho[d]1,3,2-dioxaphosphepine at the
action of chloral [9] the stereoselectivity is very high:
of the two possible 2-phenyl-2,5-dioxo-3-(trichloro-
methyl)naphtho[2,3-e]1,4,2-dioxaphosphepine
dia-
536

537
4.0–5.0, 3JHC CC 4.0–5.0), 121.04 br.s (s) (C5а), 135.32
CYCLIC P(III)-PHOSPHORYLATED DERIVATIVES OF PAMOIC ACID
6
5
stereomers only one is formed. The difference in the
solubility in methylene chloride of the diastereomers
obtained provided a possibility to separate the domi-
nating one. The remaining isomers were isolated as
mixtures by reprecipitation of the reaction mixture
from methylene chloride to pentane. Structure of
individual diastereoisomers of compound III is pro-
ved by spectral methods.
1
3
d.d (s) (C6, JHC 166.6, JHC CC 5.1), 131.35 m (s)
6
7
6
1
3
(C6а), 130.62 br. d.d. d (br. s) (C7, JHC 163.0, JHC CC
7
9
7
3
1
8
8.5, JHC CC 5.0–6.0), 130.62 d.d (s) (C8, JHC 163.6,
6
7
1
3
3JHC
8.1), 130.23 d.d (s) (C9, JHC 163.6, JHC CC
1 3
10 8 10
10CC8
9
7
9
7.3), 123.92 d.d (s) (C10, JHC 161.8, JHC CC 7.3),
134.43 m (s) (C10а), 128.40 m (d) (C11, JРОCC 4.8),
3
11
141.46 m (d) (C11а, JРОC 9.2), 94.40 d (d) (C12,
2
11a
JРCC 6.2), 127.92 d.m (d) (C13, JРC 128.7, JHC
2
1
3
12
13
15CC13
Compound II. a. To a solution of pamoic acid
(8.25 g, 21.3 mmol) was added hexamethyldisilazane
(18.0 g, 11.0 mmol). The reaction mixture was heated
at 120°C for 30 h until the ammonia liberation ceased.
The resulting orange precipitate of methylene-bis(2-
trimethylsiloxycarbonyl-3-trimethylsiloxynaphthalene)
was filtered off, dried in a vacuum (0.1 mm Hg at 60°C),
and used further without additional purification, yield
97%.
7.3), 131.86 d.d.d.d (d) (C14, JHC 165.8, JРCC 10.3,
1
2
14
14
3JHC
7.7, JHC
7.7), 129.40 d.d.d (d) (C15,
3
14'CC14
16CC14
1
3
3
15'CC15
15
15
JHC 165.1, JРCCC 13.6, JHC
7.7), 134.21 br.d.t
(br.s) (C16, 1JHC 164.5, 3JHC
7.7), 22.66 t (s) (C17,
16
14CC16
JHC 130.7). The 31Р–{1H} NMR spectrum (DMSO-
1
17
d6): δР 31.2 ppm (s).
The NMR spectra were recorded on a Bruker
Avance-400 instrument (1H, 400 MHz, 13C, 100.6 MHz,
31P, 162.0 MHz). The IR spectrum was recorded on a
Bruker Vector-22 instrument from a suspension of the
substance in mineral oil.
b. A mixture of methylene-bis(2-trimethylsiloxy-
carbonyl-3-trimethylsiloxynaphthalene) (12.49 g,
20.1 mmol), CH2Cl2 (30 ml) and phenyldichloro-
phosphine (7.2 g, 40.2 mmol) was maintained at 20°C
for 5 days, then the volatile compounds were removed
by a vacuum distillation (12 mm Hg). The residue was
dried in a vacuum (0.1 mm Hg, 60–70°C). Compound
II was obtained as a dense vitreous substance of light-
cream color, which was used further without additional
purification. 31Р-{1H} NMR spectrum (CDCl3): δP
158.5 ppm (δ1), 157.7 ppm (δ2).
REFERENCES
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Compound (III). A mixture of phosphonite II
(2.28 g, 3.8 mmol), CH2Cl2 (10 ml), and chloral (1.51 g,
10.2 mmol) was maintained at 20°C for 4 days. During
this period occurred a partial formation of compound
III, which was filtered off, washed with diethyl ether,
and dried in a vacuum (12 mm Hg). Yield 20%, mp
243-245°C. Found, %: C 51.97, H 2.49, Р 7.11.
C39H24Cl6O8P2. Calculated, %: C 52.29, H 2.68, Р
6.93. IR spectrum, cm–1: 3435, 3057, 2894, 1742,
1623, 1594, 1504, 1448, 1440, 1369, 1344, 1285,
1257, 1206, 1160, 1143, 1122, 1077, 1056, 999, 932,
897, 875, 837, 821, 809, 783, 750, 690, 661, 644, 615,
536. The 1H NMR spectrum (DMF-d7, δ , ppm, J, Hz):
8.58 с (H6), 8.14 br.d (H7, 3JH CCH 8.4), 7.84–7.92 and
8
7
7.68, two m (H14–16), 7.79 br.d (H10, 3JH CCH 8.6), 7.64
9
10
2
m (H9), 7.56 m (H8), 6.80 d (H3, JРCH 4.1), 3.66 m
3
(H17). The 13C NMR spectrum (in parentheses is shown
the multiplicity of the signal in 13C–{1H} NMR
spectrum) (DMF-d7, δC, ppm, J, Hz): 79.98 d.d (d) (C3,
1
1
3
JHC 151.1, JPC 96.1), 165.08 d.d (s) (C5, JHC ОC
3
3
3
5
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 3 2010