Unusual aryl-aryl coupling of 6-bromo-1,2-naphthoquinone to 6,6'-dibromo-1,1',2,2'-tetrahydroxy-4,4'-binaphthyl in the presence of trialkylphosphine and water

Article abstract of DOI:10.1016/j.mencom.2009.01.016

The reaction of 6-bromo-1,2-naphthoquinone with tri(2-cyanoethyl)phosphine or tricyclohexylphosphine leads to the unusual formation of 6,6'-dibromo-1,1',2,2'-tetrahydroxy-4,4'-binaphthyl; its structure was confirmed by NMR spectroscopy and single crystal

Full text of DOI:10.1016/j.mencom.2009.01.016

Mendeleev
Communications
Mendeleev Commun., 2009, 19, 39–41
Unusual aryl–aryl coupling of 6-bromo-1,2-naphthoquinone
to 6,6'-dibromo-1,1',2,2'-tetrahydroxy-4,4'-binaphthyl
in the presence of trialkylphosphine and water
Andrei V. Bogdanov, Nadezhda R. Khasiyatullina, Vladimir F. Mironov,*
Dmitry B. Krivolapov, Igor A. Litvinov and Alexander I. Konovalov
A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre of the Russian Academy
of Sciences, 420088 Kazan, Russian Federation. Fax: +7 8432 75 5322; e-mail: mironov@iopc.knc.ru
DOI: 10.1016/j.mencom.2009.01.016
The reaction of 6-bromo-1,2-naphthoquinone with tri(2-cyanoethyl)phosphine or tricyclohexylphosphine leads to the unusual
formation of 6,6'-dibromo-1,1',2,2'-tetrahydroxy-4,4'-binaphthyl; its structure was confirmed by NMR spectroscopy and single
crystal X-ray diffraction analysis.
Considerable attention has been devoted to the chemistry of
ortho-quinones and their derivatives because not only com-
pounds of this type occur in nature and possess many kinds of
biological activity but also they find use in syntheses of metal
complexes, enantioselective syntheses and syntheses of nitrogen-
and oxygen-containing heterocycles.1–6
2 with a characteristic chemical shift (dP –17 ppm) in the
31P-{1H} NMR spectrum. Mild hydrolysis of this compound
results in 3-bromo-1,2-dihydroxynaphthalene 3† in a nearly
quantitative yield (Scheme 1).
The reaction of 6-bromo-substituted 1,2-naphthoquinone 4
with tri(2-cyanoethyl)phosphine unexpectedly follows a different
route, namely, formation of tri(2-cyanoethyl)phosphine oxide
and tetrahydroxy-4,4'-binaphthyl derivative 5,‡ with one water
molecule participating as a reagent (Scheme 2).
The mechanism of the reaction is unclear. It can be proposed
that the phosphine molecule is a reducing agent, and the quinone
molecule is an oxidant. Water is likely a protons source for a
quinone moiety and an oxygen source for the phosphine oxide
formation. Taking into account the full oxidation of the used
phosphine, the additional participation of oxygen as an oxidizing
Trivalent phosphorus compounds are generally used to obtain
pentacoordinate phosphorus derivatives, such as phosphoranes,
or tetracoordinate derivatives, such as quasi-phosphonium salts
of betaine nature incorporating a P+–OC– bond.7,8 Of ortho-
quinones, 1,2-naphthoquinones have been studied least thoroughly
in reactions with PIII derivatives; they were shown to react with
phosphites to give phosphoranes.9 1,2-Naphthoquinone10 and
its halo-substituted derivatives11–13 are regioselectively phos-
phorylated at the 4-position on treatment with triphenylphosphine,
hexaethyltriamidophosphite and tri(n-butyl)phosphine under mild
conditions to give the corresponding phosphobetaines incorporating
a phosphorus–carbon bond. Many derivatives of 1,2-naphtho-
quinones, particularly 4-substituted 1,2-naphthoquinones, display
various types of biological activity and can serve as models of
binding of polycyclic carcinogenic hydrocarbons with amino
acids.14
The synthetic result of the reaction of 1,2-naphthoquinone
derivatives depends considerably not only on the nature of the
original tertiary phosphine but also on the positions of the sub-
stituents in 1,2-naphthoquinone. The reaction with tri(2-cyano-
ethyl)phosphine containing electron-withdrawing substituents
at the phosphorus atom occurs as the classical addition of the
PIII derivative to 3-bromo-1,2-naphthoquinone 1 in dichloro-
methane (20 °C) to give hydrolytically unstable phosphorane
†
3-Bromo-1,2-dihydroxynaphthalene 3. A suspension of tri(2-cyano-
ethyl)phosphine (0.83 g, 4.3 mmol) in 20 ml of dichloromethane was
added dropwise to a suspension of quinone 1 (1 g, 4.3 mmol) in 10 ml of
the same solvent with bubbling dry argon. During the addition, the reaction
mixture turned black. After 24 h, the solution produced a gray crystalline
precipitate of tri(2-cyanoethyl)phosphine oxide, which was filtered off
and dried in vacuo (12 Torr). Yield 0.82 g (92 %), mp 149–150 °C.
31P-{1H} NMR (36.48 MHz, CDCl3) dP: 43.1. 1H NMR (600 MHz,
2
3
[2H6]DMSO) d: 2.20 (dt, PCH2, JPCH 3.3 Hz, JHCCH 7.8–8.1 Hz), 2.73
(dt, CH2CN, JPCCH 2.5 Hz, JHCCH 7.8 Hz). 13C NMR (100.9 MHz,
[2H6]DMSO) (here and further a multiplicity of the signal in 13C-{1H}
spectrum is given in brackets) d: 22.84 [dtt (d), PCH2, 1JPC 64.2 Hz, 1JHC
130.7 Hz, 2JHCC 4.5 Hz], 9.56 [dtt (d), CH2, 2JPCC 1.7 Hz, 1JHC 137.7 Hz,
3JHCCC 3.7–4.6 Hz], 120.03 [m (d), CN, JPCCC 15.7 Hz, JHCC 5.2 Hz].
MS, m/z: 209 [M]+ (C9H12N3OP).
3
3
3
2
·
A filtrate was evaporated in a vacuum (12 Torr) to dryness to form
compound 3 as a brown solid. Yield 0.82 g (80%), mp 120 °C. IR (Nujol,
n/cm–1): 3514–3319 (OH), 1628, 1598, 1506, 1393, 1377, 1355, 1299,
1254, 1222, 1147, 1090, 1022, 973, 954, 890, 830, 743, 578, 555,
447. 1H NMR (600 MHz, [2H6]DMSO) d: 7.70 (s, H4), 7.71 (d, H5,
P(CH2CH2CN)3
O
O
O
O
P(CH2CH2CN)3
3
4
3JHCCH 8.4 Hz), 7.42 (dt, H6, JHCCH 6.8 Hz, JHCCCH 1.1 Hz), 7.31 (dt,
Br
Br
H7, JHCCH 6.8 Hz, JHCCCH 1.0 Hz), 8.04 (d, H8, JHCCH 8.4 Hz), 9.40,
9.19 (2br. s, 2OH). 13C NMR (100.9 MHz, [2H6]DMSO) d: 139.62 [d (s),
C1, 3JHCCC 3.7 Hz], 137.96 [d (s), C2, 3JHCCC 8.2 Hz], 113.82 [d (s), C3,
2JHCC 4.0 Hz], 121.91 [dd (s), C4, 1JHC 166.8 Hz, 3JHCCC 6.6 Hz], 128.85
[dd (s), C4a, 3JHCCC 6.6 Hz, 3JHCCH 6.6 Hz], 126.60 [dt (s), C5, 1JHC 154.8 Hz,
3
4
3
1
2
OH
OH
Br
H2O
– O=P(CH2CH2CN)3
3JHCCC 5.4–6.5 Hz], 125.98 [dd (s), C6, JHC 160.3 Hz, JHCCC 8.5 Hz],
1
3
121.15 [dd (s), C7, JHC 161.3 Hz, JHCCC 6.9 Hz], 124.18 [dd (s), C8,
1
3
3
1JHC 160.6 Hz, JHCCH 8.5 Hz], 125.17 [ddd (s), C8a, JHCCC 7.2 Hz,
3
3
3JHCCC 6.9 Hz, 3JHCCH 9.2 Hz]. MS, m/z: 238.0 (C10H7BrO2).
Scheme 1
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© 2009 Mendeleev Communications. All rights reserved.

Mendeleev Commun., 2009, 19, 39–41
OH
O(2B)
O(1B)
OH
C(2B)
C(3B)
C(1B)
Br
O
C(8C)
C(4C)
C(8B)
C(7B)
C(4B)
C(4)
Br
O
P(CH2CH2CN)3
C(3)
C(2)
C(5B)
H2O
C(6B)
Br(2)
HO
Br
– O=P(CH2CH2CN)3
C(22)
C(20)
C(4A)
O(2)
4
OH
C(5)
5
C(8A)
C(8)
Scheme 2
C(1)
C(21)
agent should be assumed as well (the possible reaction schemes
are given in the Online Supplementary Materials).
The structure of this compound was confirmed by H and
O(1)
C(6)
C(7)
Br(1)
O(20)
1
13C NMR spectra.‡ The carbon signals in the 13C and 13C-{1H}
NMR spectra of binaphthyl 5 do not have any additional multi-
plicity due to coupling with phosphorus. The weak-field region
displays four groups of signals of carbon atoms bound with
protons and six groups of signals of carbon atoms lacking C–H
bonds. The characteristic multiplicity of the signals of C(4) (dd,
Figure 1 Molecular geometry of compound 5 in a crystal (solvate with
acetone). Selected bond lengths (Å): Br(1)–C(6B) 1.904(4), Br(2)–C(6)
1.901(4), C(2)–O(2) 1.379(4), C(1)–O(1) 1.366(4), O(2B)–C(2B) 1.376(4),
O(1B)–C(1B) 1.370(4), C(4)–C(4B) 1.495(5).
d(H···O) 2.38(5) Å, d(O···O) 2.744(5) Å, Ð 112(4)°; O(1B)–
H(1B)···O(2B) d(O–H) 0.79(4) Å, d(H···O) 2.24(4) Å, d(O···O)
2.703(4) Å, Ð 118(3)°.
3
3
3JH5CCC 4.1 Hz, JH3'CCC 4.1 Hz), C(8a) (dd, JH5CCC 6.8 Hz,
3
2
JH CCC 6.8 Hz) and C2 atoms (d, JHCC 2.0 Hz) shows that
7
A lot of the intermolecular hydrogen bonds of O–H···O-type
between the molecules of 1,1',2,2'-tetrahydroxy-6,6'-dibromo-
4,4'-binaphthyl and acetone are revealed in the crystal of com-
pound 5. As a result, infinite hydrogen bonded chains are formed
along the 0b crystal axis. The hydrogen bond parameters are
O(1B)–H(1B)···O(2B') (1 – x, –y, –z) d(O–H) 0.79(4) Å, d(H···O')
2.07(4) Å, d(O···O') 2.739(4) Å, Ð 142(3)°; O(2B)–H(2B)···O(2')
(1 – x, –y, –z) d(O–H) 0.86(5) Å, d(H···O') 1.89(5) Å, d(O···O')
2.743(4) Å, Ð 169(6)°; O(1)–H(11)···O(1B'') (x, 1 + y, z) d(O–H)
0.74(5) Å, d(H···O'') 2.19(5) Å, d(O···O'') 2.858(4) Å Ð 151(5)°;
O(2)–H(10)···O(20''') (1/2 + x, 1/2 + y, z) d(O–H) 0.77(4) Å,
d(H···O''') 1.95(4) Å, d(O···O''') 2.707(5) Å, Ð 168(4)°.
coupling of the two naphthalene rings occurs at the C(4) atoms.
The presence of hydroxy groups follows from the intense
characteristic absorption in the IR spectrum around 3313 cm–1.
The reaction of quinone 4 with electron-donating tricyclo-
hexylphosphine§ occurs similarly to give binaphthyl derivative
5. This compound was isolated and crystals suitable for X-ray
diffraction analysis¶ were obtained after recrystallization from
acetone. The molecule of compound 5 forms a solvate with acetone
(Figure 1). The planes of the naphthalene rings are rotated with
respect to each other by an angle C(4A)C(4)C(4B)C(4C) of
76.6(4)°.
The following intramolecular hydrogen bonds of O–H···O-type
are realized in a crystal: O(1)–H(11)···O(2) d(O–H) 0.74(5) Å,
‡
6,6'-Dibromo-1,1',2,2'-tetrahydroxy-4,4'-binaphthyl 5. A suspension
of tri(2-cyanoethyl)phosphine (0.83 g, 4.3 mmol) in 10 ml of dichloro-
methane was added dropwise to a suspension of quinone 4 (1 g, 4.3 mmol)
in 5 ml of the same solvent at 35 °C with bubbling dry argon. Reaction
mixture turned deep brown immediately and gray tri(2-cyanoethyl)-
phosphine oxide precipitated, which after 15 min was filtered off. After
24 h, compound 5 precipitated from the filtrate was filtered off and dried
in a vacuum (12 Torr) to give a white powder. Yield 0.70 g (71%),
mp 122–124 °C. IR (Nujol, n/cm–1): 3313 (OH), 1624, 1592, 1500, 1330,
1297, 1246, 1156, 1068, 1013, 961, 904, 815, 736, 587, 519, 430. 1H NMR
4
(600 MHz, [2H6]DMSO) d: 7.12 (s, H3), 7.20 (d, H5, JHCCCH 1.9 Hz),
7.48 (dd, H7, 3JHCCH 9.0 Hz, 4JHCCCH 1.9 Hz), 8.08 (d, H8, 3JHCCH 9.0 Hz),
9.67, 9.31 (2br. s, 2OH). 13C NMR (100.9 MHz, [2H6]DMSO) d: 137.88
[dd (s), C1, 3JHCCC 15.6 Hz, 3JHCCC 4.2 Hz], 140.04 [d (s), C2, 2JHCC 2.0 Hz],
Figure 2 Hydrogen bonds in the molecule of compound 5.
¶
Crystal data. The X-ray diffraction data for compound 5 were collected
1
3
121.64 [d (s), C3, JHC 157.7 Hz], 127.02 [dd (s), C4, JH5CCC 4.1 Hz,
at 293 K on a Bruker Smart Apex II CCD diffractometer using graphite mono-
chromated MoKα (0.71073 Å) radiation. Crystals of 5 (C20H12Br2O4·C3H6O,
Mr = 534.19) are monoclinic, a = 21.824(2), b = 11.9881(9) and c =
= 16.859(1) Å, b = 100.186(1)°, V = 4341.2(6) Å3, dcalc = 1.635 g cm–3,
Z = 8, space group C2/c. Cell parameters and intensities of 4265 independent
reflections, from which 2682 with I ³ 2s (Rint = 0.0502), were measured
in the w-scan mode, 1.95° £ q £ 26.00°. Data were corrected for absorp-
tion using the SADABS program15 [m(MoKα) = 3.766 mm–1]. The structures
were solved by direct method using the SHELXS program16 and refined
by the full matrix least-squares using SHELXL97 program17 on all F2
data. All non-hydrogen atoms were refined anisotropically. The hydrogen
atoms were calculated and refined as riding atoms except H(1B), H(2B),
H(10), H(11) which were located on difference map and refined isotropically.
The final residuals were Rob = 0.0433, Rwob = 0.0801. Data collection:
images were indexed, integrated, and scaled using the APEX2 data reduc-
tion package.18 Figures was made using the program PLATON.19
3
3
3JH3'
4.1 Hz], 128.61 [dd (s), C4a, JHCCC 7.4 Hz, JHCCC 7.3 Hz],
CCC
126.84 [dd (s), C5, JHC 164.4 Hz, JHCCC 5.1 Hz], 116.41 [ddd (s), C6,
3JHCCC 12.4 Hz, 2JHCC 2.8–3.1 Hz, 2JHCC 2.8–3.0 Hz], 127.53 [dd (s), C7,
1JHC 167.6 Hz, 3JHCCC 5.9 Hz], 123.90 [d (s), C8, 1JHC 163.8 Hz], 124.34
[dd (s), C8a, 3JHCCC 6.8 Hz, 3JHCCC 6.8 Hz]. MS, m/z: 476 (C20H12Br2O4).
1
3
§
Reaction of 6-bromo-1,2-naphthoquinone with tricyclohexylphosphine.
To a solution of quinone 4 (0.93 g, 3.9 mmol) in 10 ml of dichloromethane
tricyclohexylphosphine (1.10 g, 3.9 mmol) was added dropwise with intense
bubbling dry argon. Reaction mixture turned black immediately and
slight exothermic effect occurred. After 10 h, the reaction mixture became
yellow and solution gradually produced yellow precipitate, which was
filtered off and dried in a vacuum (12 Torr). Filtrate was evaporated under
reduced pressure in an atmosphere of dry argon. Yellow residue obtained
was treated with 10 ml of dry acetone, which gradually produced light
brown precipitate, which was filtered off and recrystallized from acetone
to give colourless 6,6'-dibromo-1,1',2,2'-tetrahydroxy-4,4'-binaphthyl 5
as a solvate with acetone, mp 158–160 °C (decomp.). Yield 0.51 g (55%).
All data of compound 5 (mp, mass, IR and NMR spectra) were identical
to the above except for acetone signals.
CCDC 713876 contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
For details, see ‘Notice to Authors’, Mendeleev Commun., Issue 1, 2009.
– 40 –

Mendeleev Commun., 2009, 19, 39–41
9
(a) A. A. Kutyrev and V. V. Moskva, Usp. Khim., 1987, 56, 1798 (Russ.
Chem. Rev., 1987, 56, 1028); (b) F. H. Osman and F. A. El-Samahy,
Chem. Rev., 2002, 102, 629.
Thus, the reaction of 6-bromo-1,2-naphthoquinone 4 with
tri(2-cyanoethyl)phosphine or tricyclohexylphosphine is a con-
venient synthetic route to tetrahydroxybinaphthyls 5, and it can
serve as a new facile method of aryl–aryl coupling.
10 (a) B. Tapodi, G. Speier, M. Giorgi, M. Reglier, T. Funabiki, L. Korecz
and A. Rockenbauer, Inorg. Chem. Commun., 2006, 9, 367; (b) A. V.
Bogdanov, V. F. Mironov, N. R. Khasiyatullina, D. B. Krivolapov, I. A.
Litvinov and A. I. Konovalov, Phosphorus Sulfur Silicon Relat. Elem.,
2008, 183, 571.
11 A. V. Bogdanov, N. R. Khasiyatullina, V. F. Mironov, A. I. Konovalov,
A. A. Balandina and Sh. K. Latypov, Zh. Org. Khim., 2005, 41, 1879
(Russ. J. Org. Chem., 2005, 41, 1845).
12 A. V. Bogdanov, V. F. Mironov, N. R. Khasiyatullina, D. B. Krivolapov,
I. A. Litvinov and A. I. Konovalov, Mendeleev Commun., 2007, 17, 183.
13 A. V. Bogdanov, V. F. Mironov, N. R. Khasiyatullina and A. I. Konovalov,
Izv. Akad. Nauk, Ser. Khim., 2007, 534 (Russ. Chem. Bull., Int. Ed.,
2007, 56, 555).
This work was supported by the join programme of CRDF
and the Ministry of Education of the Russian Federation ‘Basic
Research and High Education’ (REC-007) and by the Council
on Grants of the President of the Russian Federation (grant
no. MK-2444.2007.3).
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.mencom.2009.01.016.
14 (a) F. J. Bullock, J. F. Tweedie, D. D. McRitchie and M. A. Tucker,
J. Med. Chem., 1970, 13, 97; (b) E. F. Elslager, L. M. Werbel and D. F.
Worth, J. Med. Chem., 1970, 13, 104; (c) C. Cavallotti, F. Orsini
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S. K. Kang, S. S. Kim, H. G. Cheon, S.-D. Yang and J.-K. Choi, Bioorg.
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– 41 –