Reaction of 2′,2′,2′,2″,2″,2″- Hexabromo-1,4-di(benzo-1,3,2-dioxaphosphol-5-yl)benzene with phenylacetyleneom

Full text of DOI:10.1134/S1070428013050278

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 5, pp. 768−770. © Pleiades Publishing, Ltd., 2013.
Original English Text © A.S. Aniskin, A.V. Nemtarev, V.F. Mironov, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 5, pp. 784−786.
SHORT
COMMUNICATIONS
Reaction of 2',2',2',2'',2'',2''-Hexabromo-1,4-di(benzo-1,3,2-
dioxaphosphol-5-yl)benzene with Phenylacetyleneom
A. S. Aniskin, A. V. Nemtarev, and V. F. Mironov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences,
Kazan, 420088 Russia
e-mail: nemtarev@iopc.ru
Received November 14, 2012
DOI: 10.1134/S1070428013050278
Terphenyl (diphenylbenzene) derivatives are widely
used in various fields of physics and chemistry [1–4], biol-
ogy, and medicine [5, 6]. The derivatives of m-terphenyl
are widely spread as spatially bulky ligands for the ef-
ficien stabilization of organic compounds of the elements
of the main groups and of transition metals in the low
coordination states [7–9]. m-Isomers of terphenyl are
used sometimes for the stabilization of compounds with
multiple bonds between phosphorus and elements [10].
The reaction of 2,2,2-trihaloareno-1,3,2-dioxaphos-
phols with acetylenes leads to the formation of areno[e]-
1,2-oxaphosphorines [11, 12], that attract growing interest
because of their possible applications in various fields
of chemistry and medicine [13]. It was previously estab-
lished that the halogenation of the arene fragment occurs
the most selectively in the reactions of 2,2,2-tribromoben-
OSiMe3
OH
3
3'
2'
5''
2
6''
1''
4 Me3SiCl, 4 NEt3
_4 NHEt3Cl
4''
Me3SiO
Me3SiO
OSiMe3
HO
OH
4
4'
1'
1
3''
5'
6'
2''
6
5
HO
III
I
_ 4Me3SiBr
2 PBr3
3''
O
2P'' Br3
O
PBr
3
3a''
2
7'
6'
4''
6''
2 Br2
4
7a'
5''
1
O1''
1O'
Br3P
O
O
5'
7a''
CH2Cl2
4'
7''
3a'
BrP
O
IV
2'
II
O3'
_
2
Ph
PhCBr=CHBr
O
O
O
P
Br
O
P OH
8a'
3
2
8'
3'
Ph
Ph
1
4
2 H2O
_2HBr
4'
9'
4a'
7'
10'
11'
6'
5'
Ph
Br
P
O
HO
P O
V
VI
O
12'
O
768

REACTION OF 2',2',2',2'',2'',2''-HEXABROMO-1,4-DI(BENZO-1,3,2-DIOXAPHOSPHOL-5-YL)BENZENE
769
To a slurry of compound IV in 30 ml of CH2Cl2 was
added dropwise at vigorous stirring a solution of 0.66 ml
(13 mmol) of bromine in 5 ml of CH2Cl2 (–40°C). The re-
action mixture was stirred gradually worming to the room
temperature thus obtaining the solution of compound II.
zo-1,3,2-dioxaphosphols with terminal acetylenes [14].
In this study we carried out for the first time the phos-
phorylation of the p-terphenyl derivative, 3,4,3'',4''-tet-
rahydroxy-1,1':4',1''-terphenyl (I) with PBr3 followed by
the bromination and the reaction was investigated of the
obtained bis(phosphorane) II with phenylacetylene. To
improve the selectivity of the phosphorylation compound
I was first converted into tetrakis(trimethylsilyl) ether III
by treating with trimethylchlorosilane and triethylamine.
On adding compound III to excess PBr3 2',2''-dibromo-
1,4-di(benzo-1,3,2-λ3-dioxaphosphol-5-yl)benzene (IV)
formed quantitatively, that was characterized by a singlet
in the 31P NMR spectrum at δ 198 ppm. The Me3SiBr
formed at this stage and excess PBr3 are easily removed
in a vacuum.
To a solution of diphosphol II was added dropwise at
stirring a solution of 2.6 ml (24 mmol) of phenylacetylene
in 5 ml of CH2Cl2 (–10 × 0°C). Therewith compound V
was obtained. 31P-{1H} NMR spectrum (31P) (CH2Cl2),
δ, ppm: 9.4 s , 9.3 br.d ( 2JPC H 26.4 Hz).
3
From the solution of compound V the solvent and
volatile products were removed in a vacuum, the residue
was kept in air for 4 h, washed with hexane, dissolved in
acetone, and precipitated by ethanol. The formed light-
brown precipitate was filtered off, washed with a little
acetone and ether, and dried in a vacuum. After several
crystallizations from ethanol we isolated 1.77 g (63%)
of compound VI, mp >350°C. IR spectrum, cm–1: 3435,
2346, 2029, 1976, 1959, 1655, 1638, 1616, 1588, 1572,
1537, 1445, 1394, 1343, 1313, 1243, 1197, 1181, 1166,
1119, 1076, 1006, 966, 929, 880, 862, 820, 761, 748, 701,
668, 629, 601, 588, 570, 537, 511, 434. 1H NMR spectrum
(DMSO-d6), δ, ppm: 6.28 d (H3', 2JPCH 17.5 Hz), 7.19 d
(H5', 3JHCCH 8.2 Hz), 7.66 d (H8', 4JHCCCH 1.8 Hz), 7.55 d.d
(H6', 3JHCCH 8.2, 4JHCCCH 1.8 Hz), 7.88 s (H2,3,5,6), 7.40–
7.54 m (C4'Ph). 13C NMR spectrum (DMSO-d6), δ, ppm:
115.88 d.d (d) (C3', 1JPC 169.8, 1JHC 165.1 Hz), 151.65 m
The bromination of diphosphol IV with bromine was
carried out in CH2Cl2 solution (–10...–15°C). As a result
we obtained 2',2',2',2'',2'',2''-hexabromo-1,4-di(benzo-
1,3,2-λ5-dioxaphosphol-5-yl)benzene (II), which due to
its instability against hydrolysis was brought into the re-
action with phenylacetylene without further purification.
The reaction afforded a single product, 2',2''-dibromo-
2',2''-dioxo-4',4''-diphenyl-1,4-di(benzo[e]-1,2-oxa-
phosphorin-7-yl)-benzene (V) in the form of two diaste-
reomers in approximately equal ratio. Their appearance is
due to the presence in the molecule of two asymmetrical
phosphorus atoms.
3
(s) (C4'), 121.29 m (d) (C4a', JPCCC 16.0 Hz), 129.26 d
The high selectivity should be stressed of the process
of the ipso-substitution of the oxygen atoms in both dioxa-
phosphol fragments in the para-position to the 1,4-phen-
ylene substituents. No bromine is introduced in the annu-
lated phenylene fragment of diphosphorine V in contrast
to the reactions of the unsubstituted benzodioxaphosphols
[15]. After the hydrolysis 2',2''-dihydroxy-2',2''-dioxo-
4',4''-diphenyl-1,4-di(benzo[e]-1,2-oxaphosphorin-7-yl)
benzene (VI) was isolated whose structure was estab-
lished by spectral methods.
(s) (C5', 1JPC 161.4 Hz), 121.50 d.d (s) (C6', 1JHC 162.4,
3JHCCC 6.8 Hz), 141.98 m (s) (C7'), 117.02 br.d.d.d (d)
(C8', 1JHC 162.4, 3JHCCC 6.8, 3JPOCC 5.6 Hz), 151.97 m (d)
(C8a', 2JPOC 5.9 Hz), 138.57 m (d) (C9', 3JPCCC 18.7 Hz),
128.47 br.d.d.d (s) (C10', 1JHC 160.7, 3JHCCC 6.6, 3JHCCC
5.5 Hz), 128.87 d.d (s) (C11', 1JHC 162.0, 3JHCCC 7.5 Hz),
129.04 d.t (s) (C12', 1JHC 161.2, 3JHCCC 7.5 Hz), 138.17
3
3
m (s) (C13', JHCCC 4.5, JHCCC 3.5 Hz), 127.57 br.d (s)
(C14',15', JHC 160.3 Hz). 31P NMR spectrum (DMSO),
1
δ, ppm: 5.53 br.d (2JPCH 17.5 Hz). Found, %: C 68.80;
H 4.23; P 10.64. C34H24O6P2. Calculated, %: C 69.16;
H 4.10; P 10.49.
2',2''-Dihydroxy-2',2''-dioxo-4',4''-diphenyl-1,4-
di(benzo[e]-1,2-oxaphosphorin-7-yl)benzene (VI). To
11.4 ml (120 mmol) pf phosphorus tribromide was added
dropwise under dry argon atmosphere while stirring a so-
lution of 2.77 g (4.8 mmol) of silyl ether III [16] in 15 ml
of benzene.After 24 h benzene and volatile products were
distilled off from the reaction mixture at the atmospheric
pressure and then in a vacuum (12 mm Hg) excess PBr3
was removed. As a residue a light-yellow thick oily sub-
stance was obtained, compound IV. 31P NMR spectrum
(CH2Cl2): δ 198.3 ppm
Compounds I and III were obtained by procedures
[16, 17]. 1H, 13C, 13C-{1H}, 31P, 31P-{1H} NMR spectra
were registered on a spectrometer Bruker Avance-400
[400 (1H), 162.0 (31P), 100.6 MHz (13C)] using as internal
reference the signals of the residual protons or carbon
atoms of the solvent, and as external reference, H3PO4.
IR spectrum was recorded on an instrument Bruker Vec-
tor-22 from mull in mineral oil.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 5 2013

ANISKIN et al.
9. Clyburne, J.A.C. and McMullen, N., Coord. Chem. Rev.,
770
ACKNOWLEDGMENTS
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11. Mironov, V.F., Konovalov, A.I., Litvinov, I.A., Gubaidul-
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The study was carried out under the financial support
of the Russian Foundation for Basic Research (grant
no. 10-03-00525a).
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