Bromination regiochemistry of 4-Phenyl-2,7-dichloro-2H- chryseno-[6,5-e][1,2]phosphinine 2-oxide

Article abstract of DOI:10.1134/S1070428013110109

Regioselective bromination of 4-phenyl-2,7-dichloro-2H-chryseno[6,5-e][1,2] phosphinine 2-oxide proceeded in the position 3 with the formation of 3-bromo-4-phenyl-2,7-dichloro-2H-chryseno[6,5-e][1,2] phosphinine 2-oxide; the structure of its 2-tert-butyla

Full text of DOI:10.1134/S1070428013110109

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 11, pp. 1623−1627. © Pleiades Publishing, Ltd., 2013.
Original English Text © A.V. Bogdanov, V.F. Mironov, A.B. Dobrynin, O.I. Gnezdilov, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 11,
pp. 1644−1647.
Bromination Regiochemistry of 4-Phenyl-2,7-dichloro-2Н-
chryseno-[6,5-e][1,2]phosphinine 2-Oxide
A. V. Bogdanova, V. F. Mironova, A. B. Dobrynina, and O. I. Gnezdilovb
aArbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences
Kazan, 420088 Russia
e-mail: abogdanov@inbox.ru
bZavoiskii Kazan Physico-Technical Institute, Kazan Research Center,
Russian Academy of Sciences, Kazan, Russia
Received April 23, 2013
Abstract—Regioselective bromination of 4-phenyl-2,7-dichloro-2Н-chryseno[6,5-e][1,2]phosphinine 2-oxide
proceeded in the position 3 with the formation of 3-bromo-4-phenyl-2,7-dichloro-2Н-chryseno[6,5-e][1,2]
phosphinine 2-oxide; the structure of its 2-tert-butylamino derivative was established by XRD analysis and
correlation spectroscopy.
DOI: 10.1134/S1070428013110109
Halogenation of aromatic compounds, including the
polyfused arenes, is widely used in the organic synthesis.
Haloarenes are successfully utilized in versatile research,
particularly in cross-coupling reactions, as show the nu-
merous publications concerning this topic. However the
problem of the halogenation regioselectivity still remains
urgent, and it is especially complex for polycyclic systems
like chrysene and its derivatives whose properties [1–7]
and biological activity [8–11] are subjected to intense
investigation.
formation of the dibromination product at a slight reduc-
tion of the monobrominated compound yield [13–15].At
the same time the use of the two-fold or greater excess of
bromine in sym-tetrachloroethane [16], acetic acid [17],
carbon disulfide [18], or nitrobenzene [19, 20] at the boil-
ing temperature of the solvent made it possible to obtain
6,12-dibromochrysene in a pure state.
We studied the bromination of 4-phenyl-2,7-dichloro-
2Н-chryseno[6,5-e][1,2]phosphinine 2-oxide (II), the
product of the cascade reaction of chrysenequinone (I)
with phosphorus trichloride in the presence of phenyl-
acetylene [23]. Compound II contains a chrysene frag-
ment fused to oxaphosphinine heterocycle; its reaction
with a slight excess of bromine in chloroform at room
temperature afforded solely product III of the regiose-
lective bromination in the position 3 of the heterocycle
Nowadays several publications concern the chrysene
bromination; the commonly used reagents are N-bromo-
succinimide [12] or bromine [13–21]. The application to
the synthesis of dibromo derivatives of a system alumi-
num oxide–CuBr2 was also described [22].All these data
indicate two possible reaction paths: monohalogenation
into position 6 or at once into positions 6 and 12. This fact
may be explained if the chrysene would be represented
as two fused naphthalene fragments with two activated
peri-positions (Scheme 1).
Scheme 1.
The regioselectivity of chrysene bromination depends
both on tthe solvent and on the reaction conditions: The
reaction of chrysene with bromine in nitrobenzene at
room temperature leads to the formation of 6-bromoch-
rysene in 84% yield and of trace amounts of the dibromo
derivative [21]; the replacement of the solvent for more
polar carbon disulfide and heating at 40°С excludes the
12
Br
Br2
6
Br
1623

BOGDANOV et al.
1624
(Scheme 2).As a result of this conversion the signal of the
phosphorus atom in the 31Р NMR spectrum of the initial
heterocycle II (δ, 16.4 ppm, 2JРСН 28.0 Hz) transforms
into a singlet (11.4 ppm). The arylene fragment does not
undergo the halogenation.
3-Bromo-4-phenyl-2,7-dichloro-2Н-chryseno[6,5-e]
[1,2]phosphinine 2-oxide (III) by reaction with tert-
butylamine was converted into the corresponding cyclic
amide IV that after keeping in air in dioxane solution
suffered a partial hydrolysis at the P–N bond retaining
the heterocycle and forming salt V (Scheme 3).
The structure of compound IV was established from
1Н and 31Р NMR spectra and also by XRD analysis of
a single crystal obtained by slow evaporation of the sol-
vent from the dioxane solution of substance IV (see the
figure). The conformation of the heterocycle is a distorted
boat, fragments O1C12bC4aC4 and P2C3C4C4a are coplanar
in the limits of 0.052(4), 0.001(3), 0.023(4) Å, atoms С3,
Р2 and О1, С12b deviate from the plane to the same side,
but to different distances. The dihedral angle between the
planes is 17.9(2)°. The phosphoryl group is situated in
the axial position, the amino group, the equatorial. The
phenyl substituent at the atom С4 is inclined to the double
С3=С4 bond by an angle 60.8(5)°. The chrysene fragment
is slightly twisted, the dihedral angle between flat benzo
fragments and flat naphtho fragment is 7.3(2)°. The pres-
ence of the bromine atom in the position 3 does not affect
the torsion of the chrysene part which practically does not
differ from that found in the structure II [23].
The geometry of the molecule of compound IV in the crystal
and numeration of atoms (one of the two independent molecules
is shown). Selected bond lengths, bond and torsion angles
are as follows: Br3–C3 1.890(3), P2–O2 1.455(3), P2–O1
1.607(2), P2–N2 1.614(3), P2–C3 1.776(4), Cl7–C7 1.735(4),
O1–C12b 1.371(4), N2–C23 1.486(4), C4а–С12b 1.377(5), C4а–C4b
1.443(5), C4а–C4 1.491(5), C8b–C12a 1.407(5), C8b–C9 1.430(5),
C8a–C8b 1.450(5), C12a–C12b 1.434(5), C8a–C4b 1.414(5), C8a–C8
1.427(5), C8–C7 1.362(5), C12a–C12 1.466(5), C4b–C5 1.409(5)
Å; O2P2O1 115.2(1), O2P2N2 115.6(2), O1P2N2 101.3(2), O2P2C3
115.2(2), O1P2C3 97.8(2), N2P2C3 109.6(2), O2P2N2C23 6.7(4),
O1P2C3Br3 –148.1(2), O1P2C3C4 28.0(3), O2P2C3Br3 89.2(2),
O2P2C3C4 –94.7(3), C3C4C4aC4b 158.4(3) deg.
and 1H–13C HMBC made it possible to perform the com-
plete interpretation of the carbon spectra.
The structure of the product of hydrolysis of cyclic
amide IV, ammonium salt V, was established from 1H,
13C, 13C–{1H} NMR spectra. The parameters of the car-
bon spectra are listed in the table. The application of the
methods of the correlation spectroscopy 1H–13C HSQC
Hence the bromination of a complex polycyclic
phosphorus heterocycle, 4-phenyl-2,7-dichloro-2Н-
chryseno[6,5-e][1,2]phosphinine 2-oxide, proceeds regi-
oselectively in the position 3 of the heterocycle though
Scheme 2.
14
13
11
15
16
10
9
12
12
12a
1
O
O
O
2
P
b
O
O
O
PCl3
PhC
Br2
P
8b
Cl
Br
Cl
4a
8a
CHCl3
3
CH
8
7
4b
4
17
5
18
19
Cl
Cl
6
20
I
II
III
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

BROMINATION REGIOCHEMISTRY
1625
Scheme 3.
O
O
O
O
O
O
t-BuNH2
H2O
1,4-dioxane
+
O_
H3N
P
P
P
N
Cl
Br
H
Br
Br
Cl
Cl
Cl
III
IV
V
in the arylene fragment activated positions 6 and 12 are
present.
H), 1600 (C=C), 1228 (P=O). 1Н NMR spectrum, δ, ppm
(J, Hz): 1.23 s (9H, СН3), 7.15 d.d (1H, H6, 3JHССH 9.2,
4JHСССH 1.9), 7.19–7.21 m (2H, H18), 7.31–7.34 m (3H,
H19, H20), 7.39 d (1H, H5, 3JHССH 9.2), 7.70–7.77 m (2H,
H14, H15), 8.08 br.s (3H, N+H3), 8.13–8.15 m (1H, H13),
8.19 d (1H, H10, 3JHССH 9.2), 8.85 d (1H, H9, 3JHССH 9.2),
8.86 d (1H, H8, 4JHСССH 2.2), 9.97 m (1H, H16). 31PNMR
spectrum, δ, ppm: –7.7 (s). Found, %: C 60.49; H 4.30;
N 2.25. C30H26BrClNO3P. Calculated, %: C 60.57;
H 4.41; N 2.35.
EXPERIMENTAL
IR spectra were recorded on a spectrometer Bruker
1
Vector-22 from mulls of compounds in mineral oil. H
and 13C NMR spectra were registered on a spectrom-
eter Bruker Avance-400 [400 (1Н), 100.6 МHz (13C)],
31P NMR spectra, on a spectrometer Bruker CXP-100
(36.48 МHz) in DMSO-d6. The chemical shifts are report-
ed with respect to the residual signals of the deuterated
solvent. The solvents before use were purified an dried
by standard procedures. Melting points were measured
on an instrument SMP10 Stuart, elemental analysis was
carried out on an analyzer CHNS-3. Chrysene quinone
(I) was obtained by method [24].
N-tert-Butyl-3-bromo-4-phenyl-2,7-dichloro-2Н-
chryseno[6,5-e][1,2]phosphinin-2-amine 2-oxide (IV)
was obtained as light-yellow crystals after keeping for
two days the filtrate after the separation of compound
V. Yield 0.46 g (55%), mp 287–290°С. IR spectrum,
ν, cm–1: 2923–3200 (N–H), 1614 (C=C), 1231 (P=O).
1Н NMR spectrum, δ, ppm (J, Hz): 1.28 s (3H, CН3),
5.97 d (1H, NH, 2JPNH 12.2), 7.21 d.d (1H, 3JHССH 9.5,
4JHСССH 2.2), 7.26 m (2H), 7.41 m (4H), 7.77–7.81 m
(2H), 8.20 d.d (1H, 3JHССH 9.5, 4JHСССH 2.3), 8.28 d (1H,
3JHССH 9.0), 8.92 d (1H, 3JHССH 9.5), 8.93 s (1H), 9.80 d
(1H, 3JHССH 8.1). 13С NMR spectrum was not recorded be-
cause of the low solubility of compound IV in organic sol-
vents. 31P NMR spectrum, δ, ppm: 5.1 d (2JPNH 12.2 Hz).
Found, %: С 62.30; Н 4.09; N 2.38. С30H24BrClNO2P.
Calculated, %: С 62.46; Н 4.19; N 2.43.
tert-Butylammonium 3-bromo-4-phenyl-2,7-
dichloro-2Н-chryseno[6,5-e][1,2]phosphinin-2-ola-
te 2-oxide (V). To a slurry of 0.63 g (1.40 mmol) of
compound II in 15 mL of dry chloroform at 25°С was
added dropwise in an atmosphere of dry argon 0.08 mL
(1.50 mmol) of bromine; hydrogen bromide liberated,
the precipitate dissolved. On the completion of bromine
addition the reaction mixture was left standing at room
temperature for 8 h. Through the solution argon was
bubbled for 30 min to remove the residue of hydrogen
bromide, 0.44 mL (4.20 mmol) of tert-butylamine was
added, and the reaction mixture was heated at boiling
for 2 h. On cooling the separated tert-butylammonium
chloride was filtered off, the filtrate was evaporated in a
vacuum (12 mm Hg). The white powder was treated with
5 mLof dioxane, the precipitate was filtered off and dried
in a vacuum (12 mm Hg). Yield 0.3 g (40%), light brown
powder, mp 243–245°С. IR spectrum, ν, cm–1: 3177 (N–
XRD analysis was carried out on a diffractometer
Smart Apex II CCD (λMoKα 0.71073 Å). The structure
was solved by the direct method using SIR program [25]
and was refined first in isotropic and then in anisotropic
approximation along software SHELXL97 [26] and
WinGX [27].
Compound IV. C30H24BrClNO2P. М 576.82. Crystals
triclinic, space group P-1, a 12.7470(13), b 12.8340(13),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

BOGDANOV et al.
1626
Parameters of 13С NMR spectraа of tert-butylammonium 3-bromo-4-phenyl-2,7-dichloro-2Н-chryseno[6,5-e]-[1,2]phosphinin-
2-olate 2-oxide (V) in DMSO-d6
Cross-peaks in spec- Cross-peaks in spec-
Atom
δ, ppm (J, Hz)b
trum HMBC
trum HSQC
С3 121.89 d (d) (1JPC 180.5)
–
–
С4 142.69 br.d.t (d) (2JPСC 8.4, 2JHCСC 3.6–4.0)
С4a 119.30 d.d (d) (3JPCCC 12.5, 3JHCCC 3.3)
H18
H5
–
–
С4b 128.41 br.d.d (s) (3JHC CC 7.2 , 3JHC CC 7.2)
H6, H5, H8
H6
–
6
8
С5 128.99 d (s) (1JНC 165.8)
H5
H6
–
С6 126.16 d.d (s) (1JНC 167.0, 3JHCCC 5.3)
H5, H8
H6, H5, H8
H6
С7 130.35 d.d.d (s) (3JHC CC 8.0, 2JHCC 2.7-3.1, 2JHCC 1.6–2.0)
5
С8 123.51 d.d (s) (1JНC 163.7, 3JHCCC 4.8)
H8
–
С8a 128.89 d.d (s) (3JHC CC 7.2, 3JHC CC 3.3)
H5, H9
5
9
С8b 129.83 m (s) (the signal overlapped with components of signals С18
and С16)
С9 121.31 d (s) (1JНC 162.2)
H10, H8
H10
–
H9
С10 130.32 br.d.d (s) (1JНC 161.9, 3JHC CC 5.6)
H13, H9
H14, H13, H10, H9, H16
H10
–
13
С11 133.66 br.d.d.d (s) (3JHC CC 7.3–7.5, 3JHC CC 7.3–7.5, JHC
9
14
3
16
CC
6.0–6.3)
С12 129.98 m (s)
H16, H13, H10, H15
H16, H9
–
С12a 122.12 m (s) (3JPOCC 3.7)
С12b 150.75 br.d (d) (2JPOC 8.4)
–
H9
–
С13 129.03 br.d.d (s) (1JНC 161.0, 3JHC CC 7.2)
H10, H15, H14
H16, H13
H13
H14
15
С14 127.31 d.d (s) (1JНC 161.6, 3JHC CC 8.7)
16
С15 127.35 d.d (s) (1JНC 160.6, 3JHC CC 9.0)
H16, H13
H14, H15
H15
H16
13
С16 129.03 d.d (s) (the signal overlapped with components of signals С18
andC19)
С17 140.88 d.t (d), (3JPССC 11.0, 3JHC CC 7.0–8.0)
H18, H19
H22, H20
H21
H17
H18
H19
H20
19
С18 130.18 d.d.d (s) (1JНC 160.1, 3JHCCC 6.0–7.0, 3JHCCC 6.0–7.0)
С19 128.62 br.d.d (s) (3JHCCC 6.9)
С20 128.23 d.t (s), (1JНC 161.3, 3JHCCC 7.4)
H18, H22
а
Of the anion part of the molecule. Cation fragment [(СH3)3СNH3]+: 27.54 q.sept (s) (СH3, 1JHC 126.8, 3JHCCC 4.1 Hz), 51.41 m (s) [С(СH3)3].
b The form of the signal in the 13С–{1H} NMR spectrum is given in parentheses.
c17.6330(18) Å; α104.216(1), β109.921(1), γ91.217(1)°;
V 2611.5(5) Å3, Z 4; 23(2)°C, F(000) 1176, 2θmax 54.000°,
wR(F2) 0.13426 (for 11268 reflections), R 0.0472 [for
6182 reflections with I2 ≥ 2σ (I)]. Crystallographic data
are deposited into the Cambridge Crystallographic Data
Center, CCDC 801243.
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