Features of 6-bromo-1,2-naphthoquinone reaction with 1,2- bis(diphenylphosphino)ethane

Full text of DOI:10.1134/S1070428009020284

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 2, pp. 304−305. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © N.R. Khasiyatullina, A.V. Bogdanov, V.F. Mironov, 2009, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 2,
pp. 307−308.
SHORT
COMMUNICATIONS
Features of 6-Bromo-1,2-naphthoquinone Reaction
with 1,2-Bis(diphenylphosphino)ethane
N. R. Khasiyatullina,A. V. Bogdanov, and V. F. Mironov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Science,
Kazan, 420088 Russia
e-mail: mironov@iopc.knc.ru
Received May 6, 2009
DOI: 10.1134/S1070428009020284
The intense development of the chemistry of quinones
and related compounds is due to the wide spread of these
compounds in the nature and their versatile biological
activity; they play the key part in many biological
processes, like respiration or photosynthesis. The
presence of a reactive system of multiple bonds C=C
and C=O leads to their extensive employment in the
organic synthesis as precursors of various heterocyclic
and spiro compounds, and the presence in the o-qionones
of a chelate-forming 1,2-diketone fragment easily
transformed into dioxyvinyl moiety makes it possible to
use the latter for preparation of a large number of metal
complexes [1–7].
quinone and its halo derivatives were capable to react
with hexaethyltriamidophosphite via regioselective
phosphorylation of the position 4 of the naphthalene
skeleton with the formation of phosphobetaines containing
a bond phosphorus-carbon [10, 11]; reactions with tributyl-
[12, 13] and triphenylphosphines proceeded similarly [13,
14].
We extended in this study the discovered approach to
more complex phosphorus(III) derivatives, tertiary
diphosphines. It turned out that the reaction of 6-bromo-
1,2-naphthoquinone (I) with 1,2-bis-(diphenylphosphino)-
ethane (II) in the ratio 1:1 resulted in phosphobetaine
III, product of the reaction involving only one phosphorus
atom. In the 31P−{1H} NMR spectrum it possesses two
signals at δ 19.8 and –12.0 ppm, belonging to phosphorus
atoms in coordination P(IV) and P(III) (3JPCCP 48.1 Hz).
By treating with bromine in the presence of air moisture
phosphobetaine III was converted into a more stable
derivative, phosphinoxidophosphonium salt IV whose
o-Quinones fairly easily react with P(III) derivatives
giving as a rule phosphoranes [8, 9]. At the same time
the phosphorylation of 1,2-naphthoquinone was described
in rare publications; it was for instance shown that they
reacted with trialkyl phosphites also forming phos-
phoranes [9]. We showed recently that 1,2-naphtho-
_
O
H
O
OH
5
8
O
OH
O
Br2
6
+ Ph2PCH2CH2PPh2
H2O
2
Br_
O
II
Br
Br
Br
I
18
Ph2P+
P+
PPh2
Ph
P
17
Ph
III
14
10
11
15
16
12
IV
304

FEATURES OF 6-BROMO-1,2-NAPHTHOQUINONE REACTION
305
1
structure was proved by H, 31P−{1H}NMR spectra.
Program no. 1 of the Department of chemistry and
material science of the Russian Academy of Sciences
“Theoretical and experimental investigation of the nature
of the chemical bond and the mechanisms of the most
important chemical reactions and processes”.
(7-Bromo-3,4-dihydroxy-1-naphthyl)[2-
(diphenyl-phosphoryl)ethyl]diphenylphosphonium
bromide (IV). To a dispersion of 0.59 g (2.50 mmol) of
quinone I in 5 ml of CH2Cl2 at bubbling argon was added
dropwise a solution of 0.5 g (1.25 mmol) of 1,2-bis-
(diphenylphosphino)ethane (II) in 10 ml of CH2Cl2. The
reaction mixture turned dark, and a green fine crystalline
precipitate separated that within 24 h completely dissolved.
The obtained solution of compound III [δ 19.8 d (P+,
3JPCCP 46.2 Hz),–12.0 d (PIII, 3JPCCP 48.1 Hz)] was treated
with 0.13 ml (2.50 mmol) of bromine. According to the
31P NMR spectrum the content of compound IV in the
reaction mixture corresponded to the quantitative yield.
After 10 days from the solution separated a light-gray
precipitate that was filtered off and dried in a vacuum
(12 mm Hg). Yield 0.2 g (19%), mp 175–179°C. IR
spectrum, ν, cm–1: 3584–3563 (OH), 1712, 1618, 1593,
1559, 1462, 1441, 1377, 1341, 1269 (P=O), 1212, 1177,
1156, 1124, 1106, 1076, 1027, 984, 880, 727, 694, 540, 482.
1H NMR spectrum, δ, ppm: 7.59 d (H2, 3JPCCH 16.5 Hz),
8.20 d.d (H5, 3JHCCH 9.2, 5JPCCCCH 1.8 Hz), 7.58 d.d (H6,
3JHCCH 9.1, 4JHCCCH 1.8 Hz), 7.29 br.s (H8), 7.83 d.d (H10,
3JPCCH 12.8, 3JHCCH 7.8 Hz), 7.72 d.d.d (H11, 3JHCCH 8.1,
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4
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The study was carried out in the framework of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 2 2010