Reaction of 1,6-bis(diphenylphosphino)hexane with 6-bromo-1,2- naphthoquinone

Full text of DOI:10.1134/S1070363212050222

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 5, pp. 936–938. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © N.R. Khasiyatullina, V.F. Mironov, 2012, published in Zhurnal Obshchei Khimii, 2012, Vol. 82, No. 5, pp. 866–868.
LETTERS
TO THE EDITOR
Reaction of 1,6-Bis(diphenylphosphino)hexane
with 6-Bromo-1,2-naphthoquinone
N. R. Khasiyatullina and V. F. Mironov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre, Russian Academy of Sciences,
ul. Akad. Arbuzova, 8, Kazan, Tatarstan, 420088 Russia
e-mail: mironov@iopc.ru
Received December 5, 2011
DOI: 10.1134/S1070363212050222
The phosphonium salts with a wide range of
practically useful properties are of a considerable
interest [1]. Among them biologically active com-
pounds were found capable of the preferential accu-
mulation in mitochondria that causes inhibiting tumor
cell growth owing to antioxidant effect [2], anti-
bacterial substances [3], ionic liquids [4], phase-trans-
fer catalysts [5] and organocatalysts [6]. Previously,
we developed a new synthetic approach to phos-
phonium salts on the basis of the reaction of
triphenylphosphine with 6-bromo-1,2-naphthoquinone
I, in which the phosphorylation of naphthalene
fragment occurs in the position 4 to form phosphorus
ylide followed by its treating with hydrogen halides
[7]. An attempt to extend this approach to 1,2-bis
(diphenylphosphino)ethane led to the formation of
phosphonium salts with only one phosphorus atom [8].
It may probably be due to steric hindrances to the
double phosphorylation of the naphthalene ring. In this
report we show that lengthening the spacer connecting
two phosphine centers in 1,6-bis(diphenylphosphino)
hexane II makes it possible to obtain the bis-phos-
phorylated derivative III in almost the quantitative
yield in the reaction with quinone I.
O
O
5
4
4a
8a
OH
O
6
3
2
Ph P(CH ) PPh
+
2
2 6
2
1
7
Br
Br
8
I
II
PhP
(CH2)6
PPh2
9
Br
10
11
12
OH
O
III
OH
O
OH
O
2Br−
Ph2P+ (CH2)6
2Br−
Ph2P+ (CH2)6
Br
Br
4Br2
−4HBr
HBr
+
+
PPh2
PPh2
Br
Br
HO
O
OH
O
IV
V
936

REACTION OF 1,6-BIS(DIPHENYLPHOSPHINO)HEXANE
937
The reaction of bis-ylide III with dry hydrogen
bromide results in a more stable bis(1,2-dihydroxy-
naphthylphosphonium) salt IV.
3JРССС 3.3), the signal of С14 was not identified due to
the overlapping with the DMF signal. 31Р–{1H} (31Р)
NMR spectrum (DMF-d7, 162.0 MHz): δP 20.3 ppm
[s (m)]. Found, %: С 64.31; Н 4.41; Br 17.41; Р 6.37.
C50H42Br2O4P2. Calculated, %: С 64.65; Н 4.52; Br
17.24; Р 6.68.
In the 13C NMR spectra of compound IV the signal
of C1 is shifted upfield (from 122.55 in III to 97.90 ppm)
that indicates a change in the electron density on the
phosphorus atom and the salt formation from ylide III.
The signals of carbons C3 and C4 are observed in the
stronger field at δС 140.68 and 146.86 ppm in
comparison with the signals of ylide III (δС 143.89 and
164.30 ppm). The broad absorption band in the region
of 3458 cm–1 in the IR spectrum of bisphosphonium
salt IV corresponds to the stretching vibrations of
hydroxy groups.
1,6-Bis-(6-bromo-1,2-dihydroxynaphth-4-yldi-
phenylphosphoniumbromido)hexane (IV). Through
a suspension of 0.50 g (0.54 mmol) of compound III
in 15 ml of СHCl3 was passed hydrogen bromide until
the solution became pale yellow. After 2 h the reaction
mixture was evaporated to dryness under vacuum
(14 mm Hg). The dry glassy residue was triturated
with 15 ml of anhydrous diethyl ether. The resulting
white precipitate was filtered off, washed with 5 ml of
diethyl ether, and dried in a vacuum (12 mm Hg).
Yield 0.50 g (85%), mp 186°С. IR spectrum, ν, cm–1:
3458 (OH), 1620, 1592, 1563, 1339, 1318, 1211, 1162,
The bis-phosphonium salt IV is oxidized with
bromine under the mild conditions (20°C) to give the
corresponding phosphorus diquinone in high yield.
The reaction progress was monitored by the
disappearance of a broad absorption band of hydroxy
groups at of 3458 cm–1 and the appearance of a narrow
intense absorption band at 1671 cm–1 belonging to the
ortho-quinone moiety in the IR spectrum of the
resulting salt.
1
1111, 1079, 979, 961, 818, 744, 722, 691. Н NMR
3
spectrum (CDCl3), δ, ppm (J, Hz): 8.59 d (Н2, JРССН
5
3
16.4, JНССССН 0.5), 7.44 d.d (Н5, JНССН 8.9–9.1,
5JРССССН 1.1–1.3), 8.17 d.d (Н6, JНССН 8.7, JНСССН
3
4
1.2), 7.28 br.s (Н8, JНССССН 0.6), 7.74 m (Н10, Н11),
5
3.34 br. d. t (Н13, JРСН 11.9, JНССН 3.7), 1.65–1.75 m
(Н14, Н15). 13С NMR spectrum (CDCl3), δС, ppm
(J, Hz) (the signal form in the 13С–{1H} NMR
spectrum is given in parentheses): 97.90 d (d) (С1, 1JРС
2
3
1,6-Bis-(diphenylphosphonium 6-bromo-2-hyd-
roxynaphth-4-yl-1-ate)hexane (III). To a boiling
suspen-sion of 0.62 g (2.62 mmol) of naphthoquinone
I in 15 ml of benzene was added dropwise 0.59 g
(1.30 mmol) of diphosphine II under argon atom-
sphere. The reaction mixture became black, and the
light green precipitate was formed. After 10 min the
color of reaction mixture was changed to brown-green.
The precipitate was filtered off, washed with 10 ml of
diethyl ether, and dried in a vacuum (12 mm Hg).
Yield 0.98 g (81%), mp 190–191°С (decomp.). IR
spectrum, ν, cm–1: 1596, 1536, 1343, 1284, 1222,
92.8), 129.33 d.d (d) (С2, JНС 161.2, JРСС 12.1,
1
2
overlapped with the signal of С8а), 140.68 d.d (d) (С3,
3JРССС 17.9, JНСС 3.3), 146.86 d (d) (С4, JРСССС 2.2),
2
4
124.75 m (d) (С4а, JРССС 11.7, overlapped with the
3
signal of С5), 125.39 d (s) (С5, JНС 166.9), 129.07 d.d
1
(s) (С6, 1JНС 169.1, 3JНССС 5.1–5.5, overlapped with the
signal of С8а), 120.22 d.d (s) (С7, JНССС 12.8, JНСС
3
2
5.1), 126.54 d.d. (d) (С8, 1JНС 161.7, 3JРССС 5.9, 3JНССС
4.8), 129.98 m (d) (С8а, JРСС 8.1, overlapped with the
2
signals of С2 and С6), 119.11 d.t (d) (С9, JРС 85.1,
1
1
1154, 1110, 1072, 966, 817, 722, 689, 478. Н NMR
3JНССС 7.3–7.7), 133.05 d.d.d (d) (С10, 1JНС 163.9, 2JРСС
9.9, 3JНССС 7.3), 130.50 d.d (d) (С11, 1JНС 165.8, 3JРССС
spectrum (DMF-d7), δ, ppm (J, Hz): 7.18 d (Н2, 3JРССН
3
4
14.9), 7.22 d (Н5, JНССН 8.9–9.1, JРСССН 1.3–1.5),
12.5), 134.77 br.d.d (d) (С12, JНС 163.2, JНССС 7.3,
1
3
8.36 d.d (Н6, JНССН 8.6, JНСССН 1.0), 7.31 br.s (Н8),
3
4
4JРСССС 2.2), 25.42 t.d (d) (С13, JНС 131.6, JРС 53.6,
1
1
7.86 m (Н10, Н12), 7.74 d.d (Н11, JНССН 7.5, JРССССН
3
5
3JНССС 3.7), 29.15 br.t.d (d) (С14, JНС 129.6, JРСС
1
2
2.8), 3.40 m (Н13), 1.54 m (Н14, Н15). С–{1H}/DEPT
13
17.2), 22.53 t. d (d) (С15, JНС 128.4, JРССС 3.3). 31Р–
{1H} (31Р) NMR spectrum (DMF-d7, 162.0 MHz): δP
21.6 ppm [s (m)]. Found, %: С 55.01; Н 4.09; Br
29.65; Р 5.15. C50H44Br4O4P2. Calculated, %: С 55.04;
Н 4.03; Br 29.35; Р 5.68.
1
3
NMR spectrum (DMF-d7), δС, ppm (J, Hz): 122.55 d
(С1, 1JРС 85.5), 128.74 d (С2, 2JРСС 11.4), 143.89 d (С3,
3JРССС 20.2), 164.30 br.s (С4), 123.98 br.s (С4а,
overlapped with the signal of С5), 123.98 br.s (С5),
3
128.39 s (С6), 119.24 s (С7), 125.99 d (С8, JРССС 6.2),
2
1
127.65 d (С8а, JРСС 12.1), 122.55 d (С9, JРС 85.5),
1,6-Bis-(6-bromo-1,2-dioxonaphth-4-yldiphenyl-
phosphoniumbromido)hexane (V). To a solution of
0.3 g (0.27 mmol) of compound IV in 20 ml of
2
3
133.19 d (С10, JРСС 9.9), 130.09 d (С11, JРССС 12.1),
134.02 br.s (С12), 23.83 d (С13, 1JРС 54.3), 22.79 d (С15,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 5 2012

938
KHASIYATULLINA, MIRONOV
trichloromethane was added dropwise 0.06 ml
(1.08 mmol) of bromine. The dark red reaction mixture
was poured into 30 ml of hot (70°C) water. The red
precipitate was filtered off, washed with 10 ml of
diethyl ether, and dried in a vacuum (12 mm Hg) at
room temperature. Yield 0.25 g (86%), mp 180–182°С.
IR spectrum, ν, cm–1: 1671 (С=О), 1620, 1580, 1341,
1310, 1273, 1161, 1110, 108, 963, 932, 746, 723, 692,
515, 488. 1Н NMR spectrum (400 MHz, DMSO-d6), δ,
ppm (J, Hz): 7.44 m (Н2, Н11), 7.69 d.d (Н5, 3JНССН 8.2,
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4JРСССН 1.7), 7.92 d (Н6, JНССН 8.2), 7.23 s (Н8), 7.65
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1
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1
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ACKOWLEDGMENTS
8. Khasiyatullina, N.R., Bogdanov, A.V., and Mironov, V.F.,
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This work was supported by the Ministry of
Education and Science (contract no 02.740.11.0633).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 5 2012