Reaction of hexafluoroacetone with 2,7-diethoxybenzo-[1,2-d:4,5-d′] bis[1,3,2]dioxaphosphinine-4,9-dione derived from 2,5-dihydroxyterephthalic acid

Full text of DOI:10.1134/S1070428007070251

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 7, pp. 1090–1091. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © L.M. Abdrakhmanova, V.F. Mironov, T.A. Baronova, R.Z. Musin, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43,
No. 7, pp. 1095–1096.
SHORT
COMMUNICATIONS
Reaction of Hexafluoroacetone with 2,7-Diethoxybenzo-
[1,2-d:4,5-d′]bis[1,3,2]dioxaphosphinine-4,9-dione Derived
from 2,5-Dihydroxyterephthalic Acid
L. M. Abdrakhmanova, V. F. Mironov, T. A. Baronova, and R. Z. Musin
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
Received October 30, 2006
DOI: 10.1134/S1070428007070251
Reactions of cyclic phosphorylated derivatives of
salicylic and hydroxynicotinic acids with carbonyl
compounds offer a simple and convenient synthetic ap-
proach to seven-membered heterocycles such as 1,3,2-
and 1,4,2-benzodioxaphosphepines [1–4]; some of
these compounds may be used in the synthesis of
fluorinated ketones [5]. We made an attempt to extend
the above approach to more complex bis-phosphoryl-
ated derivatives of 2,5-dihydroxyterephthalic acid
(III), namely 2,7-diethoxybenzo[1,2-d:4,5-d′]bis-
[1,3,2]dioxaphosphinine-4,9-dione (I) which was pre-
pared by reaction of tetrakis(trimethylsilyl) derivative
II of acid III with dichloro(ethoxy)phosphine in al-
most quantitative yield. Compound II was synthesized
by treatment of 2,5-dihydroxyterephthtalic acid (III)
with hexamethyldisilazane.
acetone to give a new heterocyclic system, 2,8-di-
ethoxy-4,4,10,10-tetrakis(trifluoromethyl)benzo-
[1,2-d:4,5-d′]bis[1,3,2λ5-dioxaphosphepine)-5,11-di-
one 2,8-dioxide (IV). The latter was formed as a mix-
ture of two diastereoisomers at a ratio of 1:1 (CDCl3,
δP –11.8 and –12.1 ppm, dl and meso; overall yield
>90%). One diastereoisomer of IV gradually crys-
tallized from methylene chloride and was isolated
(δP –11.8 ppm). Its structure was proved by the 1H, 19F,
and 13C NMR, IR, and electron impact mass spectra.
Thus we have shown that complex bis-phospho-
rylated derivatives of 2,5-dihydroxyterephthalic acid
like I are capable of reacting with hexafluoroacetone to
give products of expansion of the six-membered heter-
orings to seven-membered. It seems promising to
extend the proposed procedure to other phosphorus-
containing cyclic derivatives of natural hydroxy acids.
Benzodiphosphinine I (CH2Cl2, δP 124.9 and
125.5 ppm, a mixture of d,l and meso forms at a ratio
of 1:1) readily reacted with 2 equiv of hexafluoro-
2,7-Diethoxybenzo[1,2-d:4,5-d′]bis[1,3,2]dioxa-
phosphinine-4,9-dione (I) was synthesized by heating
O
O
HO
Me3SiO
OSiMe3
OH
(Me3Si)2NH
–NH3
HO
Me3SiO
OSiMe3
OH
O
O
III
II
O
O
O
P
F3C
F3C
10
12
OEt
CF3
O
O
OEt
11
10
9
1
1
2
O8
P7
2P
3O
EtOPCl2
CF3COCF3
O 9
3 O
6
O
P8
4
–Me3SiCl
4
7
O
5
EtO
EtO
5
6
CF3
O
O
O
I
IV
1090

REACTION OF HEXAFLUOROACETONE WITH 2,7-DIETHOXYBENZO-...
1091
3
a mixture of 6.0 g of trimethylsilyl derivative II and
4.0 g of dichloro(ethoxy)phosphine at 40–50°C under
reduced pressure (100 mm); the product was isolated
as a thick light yellow liquid which was freed from
volatile impurities by evacuation at a residual pressure
of 12 mm and was then used without additional
purification.
1JCF = 289.3, JPC = 5.3 Hz), 68.83 t.d.q (d) (CH2,
1JCH = 151.2, 2JPC = 6.6, 2JCH = 4.5 Hz), 15.89 q.d.t (d)
(CH3, 1JCH = 128.0, 3JPC = 5.6, 2JCH = 3.0 Hz).
The IR spectrum was measured on a Bruker Vector-
22 instrument from a sample dispersed in mineral oil.
The NMR spectra were recorded on Bruker MSL-400
(31P, 162.0 MHz), Bruker Avance-600 (1H, 600 MHz;
13C, 13C–{1H}, DEPT, 150.9 MHz), and Varian Unity-
300 spectrometers (19F, 287.2 MHz) from solutions in
CDCl3 using HMDS (1H), C6F6 (19F), or solvent signal
(13C) as internal reference and H3PO4 (31P) as external
reference. The mass spectrum (electron impact, 70 eV)
was obtained on a Trace MS Finnigan MAT mass
spectrometer with direct sample admission into the ion
source (ion source temperature 200°C). The batch-inlet
system was heated in a programmed mode (from 35 to
150°C at a rate of 35 deg/min).
2,8-Diethoxy-4,4,10,10-tetrakis(trifluoromethyl)-
benzo[1,2-d:4,5-d′]bis[1,3,2λ5-dioxaphosphepine]-
5,11-dione 2,8-dioxide (IV). Compound I, 4.0 g, was
dissolved in a mixture of 10 ml of methylene chloride
and 30 ml of carbon tetrachloride, and 4.30 g of hexa-
fluoroacetone was recondensed thereto at –40°C. The
mixture was allowed to slowly warm up to 20°C and
was held for 7 days at that temperature. A crystalline
material separated and was filtered off, washed with
diethyl ether, and dried. Yield 37%, mp 161°C. Mass
spectrum: m/z 678 [M]+. IR spectrum, ν, cm–1: 3030,
1726, 1488, 1409, 1315, 1297, 1235, 1184, 1147,
1080, 1023, 984, 955, 908, 905, 786, 739, 711, 691,
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608, 576, 529, 510, 447. H NMR spectrum, δ, ppm:
3
4
1.51 t.d (6H, CH3, JHH = 7.2, JPH = 0.5 Hz), 4.53 q.d
3
3
(4H, OCH2, JHH = 7.2, JPH = 9.4 Hz), 7.61 d (2H,
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4
4
ppm: –72.31 q and –73.09 q (CF3, JFF = 9.2 Hz).
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3.0 Hz), 83.05 sept.d (sept.d) (C4, C10, JFC = 30.6,
2
2JPC = 5.1 Hz), 183.36 br.d (s) (C5, C11, 3JCH = 4.5 Hz),
145.19 d.d.d (d) (C6a, C12a, JCH = 9.2, JPC = 6.1,
3
2
2JCH = 5.2 Hz), 124.86 d.d (d) (C6, C12, JCH = 171.7,
1
3JPC = 9.3 Hz), 119.45 br.q.d (br.q.d) (CF3, JCF
=
1
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3
289.4, JPC = 8.3 Hz), 119.50 br.q.d (br.q.d) (CF3,
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 7 2007