The rotameric (R*,S*)- and (R*,R*)-biaryl-3,3′-diphthalides of polyphenylene series

Article abstract of DOI:10.1016/j.tet.2019.01.043

A wide range of diastereomeric pairs of biaryl-3,3′-diphthalides with aromatic (heteroaromatic) substituents of polyphenylene series (including halogen substituted) was synthesized. All of them were separated and characterized by the methods of X-ray analysis, HPLC, IR-, 1H and 13C NMR spectroscopy. It was determined that solubility, tendency to adsorption and related to it retention times, chemical shifts of equivalent hydrogen and carbon atoms of biaryl-3,3′-diphthalides diastereoisomers are determined firstly by the stereo-electronic effects of two adjacent strongly polar phthalide groups. It was shown that both in crystalline phase and in solution all the diphthalides, regardless of the chemical structure of their substituents, are existing as stable rotamers with cis or synperiplanar (chiral forms) and trans or antiperiplanar (meso-forms) conformation.

Full text of DOI:10.1016/j.tet.2019.01.043

Accepted Manuscript
The rotameric (R*,S*)- and (R*,R*)-biaryl-3,3′-diphthalides of polyphenylene series
Tagir A. Yangirov, Akhnef A. Fatykhov, Elvira A. Sedova, Leonard M. Khalilov,
Ekaterina S. Meshcheryakova, Sergey P. Ivanov, Sergey N. Salazkin, Vladimir A.
Kraikin
PII:
S0040-4020(19)30082-1
https://doi.org/10.1016/j.tet.2019.01.043
TET 30095
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 28 November 2018
Revised Date: 16 January 2019
Accepted Date: 17 January 2019
Please cite this article as: Yangirov TA, Fatykhov AA, Sedova EA, Khalilov LM, Meshcheryakova ES,
Ivanov SP, Salazkin SN, Kraikin VA, The rotameric (R*,S*)- and (R*,R*)-biaryl-3,3′-diphthalides of
polyphenylene series, Tetrahedron (2019), doi: https://doi.org/10.1016/j.tet.2019.01.043.
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ACCEPTED MANUSCRIPT
O
Ar
Ar
Cis
Trans
Ar =
Ar
O
O
O
O
(R*,R*)
Ar
O
O
O
O
O
Ar
Ar
Cis
Trans
Ar
O
O
O
O
O
(R*,S*)
Ar
O
O
O
Electroctatic repulsion

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The rotameric (R*,S*)- and (R*,R*)-biaryl-3,3′-diphthalides of
polyphenylene series
Tagir A. Yangirova, Akhnef A. Fatykhova, Elvira A. Sedovaa, Leonard M. Khalilovb,
Ekaterina S. Meshcheryakovab, Sergey P. Ivanova, Sergey N. Salazkinc, Vladimir A.
Kraikina,*
aUfa Institute of Chemistry – Subdivision of the Ufa Federal Research Centre of the Russian
academy of Sciences (UIC UFRC RAS), prospekt Oktyabrya 69, Ufa 450054, Russia.
bInstitute Petrochemistry and Catalysis UFRC RAS, Ufa, Russia.
cA.N.Nesmeyanov Institute of Organoelement Compounds of the Russian academy of
Sciences, Moscow, Russia.
ABSTRACT
A wide range of diastereomeric pairs of biaryl-3,3′-diphthalides with aromatic
(heteroaromatic) substituents of polyphenylene series (including halogen substituted)
was synthesized. All of them were separated and characterized by the methods of X-ray
analysis, HPLC, IR-, 1H and 13C NMR spectroscopy. It was determined that solubility,
tendency to adsorption and related to it retention times, chemical shifts of equivalent
hydrogen and carbon atoms of biaryl-3,3′-diphthalides diastereoisomers are determined
firstly by the stereo-electronic effects of two adjacent strongly polar phthalide groups. It
was shown that both in crystalline phase and in solution all the diphthalides, regardless
of the chemical structure of their substituents, are existing as stable rotamers with cis or
synperiplanar (chiral forms) and trans or antiperiplanar (meso-forms) conformation.
Key words: biaryl-3,3′-diphthalides, meso- and chiral diastereomers, cis and
trans rotamers, X-ray analysis, 1H and 13C NMR.
Introduction
The compounds of the class of diphthalides have been known for more than 120
years starting with the work of Ulman1, who first obtained biphenyl-3,3′-diphthalide. But
despite of the long history, a relatively small number of diphthalides with mononuclear
substitutes have been synthesized to date. Most of them are compounds obtained on
*Corresponding author. Tel. +7 347 2356096. E-mail address: kraikin@anrb.ru (V.A. Kraikin, Head of
Laboratory of Synthesis of the Functional Polymers).
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the basis of commercially available and well soluble derivatives of o-benzoylbenzoic
acid and its substituted analogs (o-(p-nitrobenzoyl)-benzoic, o-(p-methylbenzoyl)-
benzoic etc.). Practically all ways of obtaining biphenyl-3,3′-diphthalides are based on
the dimerization of intermediates (cation, radical) formed by heterolysis or homolysis of
C–X bond, where C represents a sp3-hybridised carbon atom of phthalide group, and X
is a hydrogen atom or heteroatom O, S, N, Cl. The pioneering biaryl-3,3′-diphthalides
were produced by the reduction of benzoylbenzoic acids and their esters by various
metals in the acidic media: Zn/acetic acid2,3, Al/sulfuric acid4,5. Another early methods of
synthesizing the diphthalides involve dimerization of 3-arylphthalides in the presence of
6
7
the halogens Br2 and I2 . The well known Bhatt’s method suggests the dimerization of
benzoylbenzoic pseudoacid chlorides by treatment with sodium or potassium iodides8,9.
Applying these reductants leads to 3,3′-diphthalides with high yields in mild conditions8-
10. Later the diphthalides were obtained by carbonylation of β-iodoenones11,
photopinacolisation-lactonisation of o-benzoylbenzoic acid and photolysis of amides12,
as well by photoreduction of alkylbenzoates13-15. Also, the formation of biaryl-3,3′-
diphthalides during the photochemical transformation of S-aryl 2-benzoylbenzothioates
was described16. And just recently, there was a report dealing with the microwave
assisted synthesis of 3-amine dithiocarbamyl phthalides and their further transformation
to dihydro-3,3′-diphthalides17.
With all diversity of the synthetic methods, the structural investigations were
performed just for a small amount of 3,3′-diphthalides. Using the X-ray analysis, the
molecular structures of biphenyl-3,3′-diphthalide, bis-(4-chlorophenyl)-3,3′-diphthalide
and bis-(4-bromophenyl)-3,3′-diphthalide were investigated18-21. It’s shown that meso-
forms of the diphthalides always exist in the staggered configuration, while there is no
reliable information concerning configurational structure of the chiral isomers. Besides
the X-ray analysis, nowadays there are no general physical methods for precise
distinguishing between (R*,S*)- and (R*,R*)-isomers of diphthalides18. In the Pfau’s
work12 the 13C NMR spectra of both isomers of biphenyl-3,3′-diphthalide are presented,
however, without assignment of each spectrum to individual diastereomeric form.
The present report reveals the synthesis and the structure of 8 diastereomeric
pairs of new biaryl-3,3′-diphthalides, with substituents of polyphenylene series, that we
succeeded to separate, to characterize with various physical-chemical methods and to
determine their relative configuration and the preferred conformation. The compounds
of this type could find application as monomers for producing the polyheteroarylenes
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with diphthalide groups in polymeric chain22 by the reactions of dehalogenation23-25 or
Friedel-Crafts electrophilic substitution26,27
.
Results and discussion
At first, the phthalic anhydride was condensed with commercially available
aromatic (heteroaromatic) hydrocarbons by the Friedel-Crafts reaction to synthesize the
starting o-aroylbenzoic acids that were transformed to corresponding pseudo acids
chlorides 1а-g by refluxing in thionyl chloride (Scheme 1).
Scheme 1. Preparation of o-aroylbenzoic pseudo acids chlorides 1a-g.
The further coupling of 1а-g with NaI in acetone media at room temperature led
to diastereoisomeric pairs of biaryl-3,3′-diphthalides 2a-g/2’a-g which were not
described before our investigations (Table 1).
Table 1. Synthesis of biaryl-3,3'-diphtalides 2a-g/2’a-g.
Yielda
(%)
Entry
1
Ar
Product
Form
2a
(R*,S*)
97
2'a
2b
(R*,R*)
(R*,S*)
2
3
80
4
5
6
7
2'b
2c
(R*,R*)
(R*,S*)
(R*,R*)
(R*,S*)
80
95
2'c
2d
3

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8
9
2'd
(R*,R*)
(R*,S*)
2e
80
10
11
2'e
(R*,R*)
(R*,S*)
2f
95
94
12
2'f
(R*,R*)
13
14
2g
(R*,S*)
(R*,R*)
2'g
a General yield for both diastereomers. The molar ratio (R*,S*)/ (R*,R*) is 1:1.
In all cases the dimerization was followed by precipitation of the produced 3,3′-
diphthalides, whereas the dimerization of poor soluble pseudo acids chlorides 1a-b, 1e-
g proceeded heterogeneously from the very beginning. Nevertheless, conducting the
dehalogenation in heterophase conditions didn’t affect the efficiency and selectivity of
the process.
In addition to homo coupling of 1а-g, in the present work we carried out the joint
coupling of pseudo acids chlorides of diphenyloxide (1c) and diphenylsulphide (1d)
type. Separation of the resulting mixture by HPLC gave the individual diphthalides 2с-
d/2’с-d, and moreover, the unsymmetrical diastereometric diphthalides 3 and 3’ were
first isolated (Scheme 2).
Scheme 2. Joint dimerization of pseudo acids chlorides 1c and 1d.
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The molar ratio of 2c, 2’с, 3, 3’, 2d, 2’d in the products mixture, according to the 13C
NMR data, amounted to 1: 1: 2: 2: 1: 1 correspondingly.
The significant differences in solubility of (R*,S*)- and (R*,R*)-biaryl-3,3′-
diphthalides (the chiral forms posses higher solubility) made it possible to separate most
part of the synthesized diastereomeric pairs. Meso-isomers with conjugated
polyphenylene substituents 2a, 2b, 2e-g, which are characterized by extremely low
solubility, were quite easily freed from corresponding racemates 2’a, 2′b, 2’e-g by
extracting the initial diastereomeric mixture with hot toluene. A diastereomeric pair of
more soluble diphthalides with heteroaromatic substituent 2d/2’d was split by fractional
crystallization from toluene. For separating the diastereomers of diphenyloxide type
2c/2’c, which crystallized out jointly from all the used solvents, as well as for isolating
the unsymmetrical diphthalides 3 and 3’, the semi-preparative HPLC was applied.
All the diastereoisomers were characterized by the methods of 1H, 13C NMR, IR-
and mass-spectroscopy. The crystallized compounds were investigated by X-ray
analysis (Figure 1).
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Figure 1. Molecular structures of biaryl-3,3′-diphthalides. Atoms are represented by
thermal displacement ellipsoids at the 30% probability level.
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In accordance with X-ray analysis data, all the investigated diphthalides,
depending on their diastereomeric form, crystallize out as two stable conformers
(rotamers) whose stability is determined by their configurational structure and by
stereoelectronic effects of two adjacent strongly polar phthalide groups. The
electrostatic repulsion of oxygen atoms (both ether and carbonyl) of phthalide groups
and consequent retardation of С3–С3′ bond twisting lead to the fact that chiral
diastereoisomers in crystalline phase exist in cis or synperiplanar conformation, and
meso-isomers exist in trans or antiperiplanar one (Figure 2).
Figure 2. Favorable rotameric conformation of biaryl-3,3′-diphthalides diastereoisomers.
In both rotamers the electronegative oxygen atoms of adjacent phthalide groups keep
away from each other at maximum. By the results of X-ray analysis, it was figured out
that optimal value of a dihedral angle Ar–С3–С3′–Ar′ in (R*,R*)-isomers amounts to the
range from ~40°( 2’a) to ~52° (2’f), and in meso-isomers always amounts to 180° (Table
2).
Table 2. Structural characteristics of biaryl-3,3'-diphtalides 2a-d/2’a-f from the X-ray
analyses data.
Space Anglea
Product
Unit cell
group
Pbca
I41/a
P21/n
I2/a
(°)
2a
2'a
2b
2'b
2c
orthorhombic
tetragonal
monoclinic
monoclinic
triclinic
180.0
39.9
180
50.9
180.0
43.5
P-1
2'c
triclinic
P-1
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2d
2'd
2e
2'e
2f
triclinic
P-1
P21/n
-
180.0
47.7
-
monoclinic
-
monoclinic
-
P21/n
-
42.4
-
2'f
triclinic
P-1
51.8
a Dihedral angle Ar-С3-С3′-Ar′
Most of obtained biaryl-3,3'-diphtalides form the crystal systems of triclinic (2c,
2’c, 2d, 2’f) and monoclinic (2’b, 2’d, 2’e) syngony, diastereomer 2a is of orthorhombic
system and 2’a is of tetragonal one. The diphthalide crystals of monoclinic
crystallographic system posses a platy structure. This fact was confirmed on the
example of 2’d compound in which a classical image of a plastic slip deformation typical
for the plate-like crystals was observed in polarized light (Figure 3).
Figure 3. Plastic deformation of a platy crystal of (R*,R*)-3,3'-bis[4-(phenylthio)phenyl]-
3,3'-diphthalide observed in polarized light.
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In Figure 4, which displays a molecular packing of (R*,S*)- and (R*,R*)-diastereomers of
biaryl-3,3′-diphthalides 2a-d/2’a-d along the crystallographic axes, one can see that
formation of the crystals occurs via stacking-interaction.
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Figure 4. Molecular packing along the crystallographic axes for (R*,S*)- and (R*,R*)-
biaryl-3,3'-diphthalide crystals 2a/2’a, 2b/2’b, 2c/2’c and 2d/2’d.
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Cisoid form of (R*,R*)-diastereomers and transoid form of (R*,S*)-diastereomers
of biaryl-3,3'-diphthalides keep up in a solution as well. This conclusion was made on
the basis of HPLC data, according to which the meso-isomers are characterized by
smaller retention times and always eluted first, and chiral diphthalides eluted second
(Figure 5).
Figure 5. HPLC of the mixture of biaryl-3,3'-diphtalides 2c, 2’c, 2d, 2’d, 3, 3’.
By analogy with literature data on adsorption of diastereoisomers of other classes28-38
,
differences in chromatographic behavior of the diastereomeric diphthalides can be
explained by a different mechanism of their adsorption, which in its turn is determined
by configurational structure and preferred conformation of these compounds. It is
considered, that compounds adsorbed on an adsorbent’s surface posses the same
conformation as in a solution28-30. In case of cisoid rotamers, a two-point adsorption is
realized by means of two adsorption centres (polyphenylene substitutents) which are
located on one side of the skeletal С3-С3' bond. In case of transoid rotamers of meso-
diphthalides, a single-point adsorption is most probable (Figure 6).
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Figure 6. Schematic representation of a single- and two-point adsorption of meso- (a)
and chiral (b) rotamers of biaryl-3,3'-diphthalides on a hydrophobic stationary phase.
Collating the results of X-ray analysis with 1H and 13C NMR spectra revealed the
fact that determination of diastereomeric configuration of one-type biaryl-3,3'-
diphthalides might be done only on the basis of spectral data. A correlation of relative
configuration and conformation of the diphthalides with characteristic signals of protons
and carbons of the phthalide groups allows us to do it (Table 3).
Table 3. Spectral characteristics of biaryl-3,3′-diphthalides 2a-g/2’a-g.
NMR (CDCl3, ppm.)
IR, cm-1
Entry Prod.
Form
(νС=О
)
H5
C3
C1
2a
2'a
(R*,S*) 8.43
(R*,R*) 8.00
90.24 168.85 1772.66
90.99 169.37 1768.80
1
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2b
2'b
(R*,S*) 8.41
(R*,R*) 7.98
90.11 168.74 1780.37
90.83 169.27 1776.52
2
3
4
2c
2'c
(R*,S*)
(R*,R*)
1774.59
1770.73
8.31
7.95
90.18 168.65
90.82 169.10
2d
2'd
(R*,S*)
1782.30
8.28
89.88 168.45
(R*,R*) 7.93
90.57 168.92 1778.44
2e
2'e
(R*,S*)
(R*,R*) 8.02
1772.66
91.56 169.57 1778.44
8.45
90.74 168.93
5
6
7
2f
2'f
(R*,S*)
(R*,R*) 8.08
1764.94
90.62 168.81
91.46 169.42 1775.55
8.51
2g
2'g
(R*,S*)
(R*,R*) 8.02
1781.34
90.26 168.85
90.99 169.38 1776.52
8.44
In 1H NMR spectra, the most characteristic and informative signals represent staying
apart doublets of the protons at C5, which in case of meso-stereomers are always
widened and registered at higher resonance frequencies ( 8.4 ppm) than those of chiral
isomers ( 8.0 ppm). The diastereomeric effect ∆δ = δmeso – δrac is rather significant and
definitely characterize each of the diastereoisomers. Backwards, in 13C NMR spectra,
the most characteristic signals of sp3-hybridized carbons C3 and carbonyl carbons C1,
which resonate in fields 90 and 169 ppm correspondingly, for (R*,S*)-diphthalides are
registered at lower frequencies as compared with (R*,R*)-isomers. The distinctions
between diastereomers, apparent in 1H and 13C NMR spectra, are illustrated in Figures
7 and 8 respectively on the example of compounds 2c/2’c. The 1H and 13C NMR
spectra of all obtained biaryl-3,3′-diphthalides 2a-g/2’a-g, 3/3’ are available in
supplementary materials.
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Figure 7. 1H NMR spectra of (R*,S*)- (a) and (R*,R*)- (b) 3,3'-bis(4-phenoxyphenyl)-
3,3'-diphthalide.
Figure 8. 13C NMR spectra of (R*,S*)- (a) and (R*,R*)- (b) 3,3'-bis(4-phenoxyphenyl)-
3,3'-diphthalide.
Differences between the diastereomers appear in IR-spectra as well.
Characteristic frequencies of carbonyl group’s valence vibrations, for meso-isomers with
substituents of linear polyphenylene series, are 5-7 cm-1 less than for chiral
stereoisomers (Table 3). For diastereomeric pairs with coplanar disposition of
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phenylene rings in fluorene (Table 3, Entry 5) and dibenzofurane (Table 3, Entry 6)
substituents, the relation is inverse. The characteristic band in the field 975 cm-1, which
had been sighted in spectrum of racemic 3,3′-diphthalides earlier8, is also observed in
case of all new diphthalides of analogous structure 2’a-g, 3’.
Conclusion
On the basis of the results of the conducted work we can summarize that a
strong repulsion of the electronegative oxygen atoms in adjacent phthalide groups of
biaryl-3,3′-diphthalides leads to retardation of С3–С3′ bond twisting and consequently
causes the formation of stable conformers (rotamers) of these compounds. In case of
chiral diastereomers, these are conformers with erythroid disposition of phthalide
groups (cis or synperiplanar rotamers), in which a dihedral angle Ar–С3–С3′–Ar′ has a
value from ~40° to ~52°, and in case of meso-diphthalides these are threoyd
conformers (trans or antiperiplanar rotamers) with the dihedral angle equal to 180°(for
all meso-diastereoisomers). Distinguishing between (R*,S*)- and (R*,R*)-diphthalides
may be done very precisely by means of the 1H NMR spectroscopy, since the
characteristic signals of the protons at C5, which are registered at ~8.4 ppm for meso-
forms and at ~8.0 ppm for chiral forms, allow us to clearly attribute each spectrum to
definite diastereoisomer.
Experimental
Measurements
The IR-spectroscopy was performed on a Shimadzu IR Prestige-21 instrument.
The 1H and 13C NMR spectra were recorded on a Bruker Avance III 500 MHz
spectrometer, at 500 and 126 MHz correspondingly, in CDCl3. The HPLC was carried
on a Waters Breeze liquid chromatograph equipped with spectrophotometric detector (λ
215 nm) and Luna C18 column (10×250 mm, particle size 10 ꢀm) at 25°С. Eluent
(acetonitrile-water, 83:17) was fed with a flow rate of 4 mL min-1. Mass spectra were
obtained using Thermo Finnigan MAT 95 XP (EI, 70 eV) and Shimadzu LCMS-2010EV
(CI) instruments. Elemental analyses were carried on Euro EA 3000 CHNS-analyzer.
X-ray analysis
The X-ray diffraction analysis of 2a, 2’a, 2b, 2’b, 2c, 2’c, 2d, 2’d, 2’e and 2’f was
carried out on a XCalibur Eos automated four-circle diffractometer (graphite
monochromator, MoKα radiation, λ = 0.71073 Å, ω-scanning, 2θmax = 62°). The data
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were collected and processed using a CrysAlisPro Oxford Diffraction Ltd program39.
The structures were solved by direct methods and refined by full-matrix least-squares
method in the anisotropic approximation for non-hydrogen atoms. All hydrogen atoms
are generated using the proper HFIX command and refined isotropically using the riding
model. The calculations were performed using the SHELX40 program package. The
molecular plots were drawn using Mercury41.
CCDC 1876560, 1409636, 1876841, 1876843, 1409641, 1876849, 1876571,
1876566, 1876848, 1876839 contain the supplementary crystallographic data for the
structures 2a, 2’a, 2b, 2’b, 2c, 2’c, 2d, 2’d, 2’e and 2’f accordingly. This data can be
obtained free of charge from the Cambridge Crystallographic Data Centre via
http://www.ccdc.cam.ac.uk/datarequest/cif.
Materials
Commercially available starting reactants were used as received unless
otherwise indicated. Acetone was stirred over dry K2CO3 overnight, then distilled and
stored over 4-A molecular sieves. NaI was dried by heating. Pseudo acids chlorides 1а-
g were obtained by AlCl3-promoted acylation of the corresponding aromatic compounds
with phthalic anhydride followed by treatment of produced o-keto carboxylic acids with
thionyl chloride in accordance with the procedures described in literature.42-46
Biaryl-3,3'-diphthalides 2a-g/2’a-g.
Biaryl-3,3'-diphthalides 2a-g/2’a-g were synthesized via dimerization of pseudo
monoacids chlorides 1а-g by treatment with sodium iodide in acetone according to the
published method.8
(R*,S*)-3,3'-bis(diphenyl-4-yl)-3,3'-diphthalide (2a). Colorless crystals, mp 285.0-
286.0°С (dec). IR, cm-1: 1772.66, 1488.15, 1366.62, 1284.65, 1241.25, 1216.17,
1069.57, 1022.32, 1009.78, 993.38, 765.77, 759.02, 736.84, 717.55, 701.15. 1H NMR,
δ (ppm): 7.32 (t, 2H, J = 7.7 Hz), 7.37 (d, 4H J = 8.5 Hz), 7.38 (t, 4H, J = 7.8 Hz), 7.43
(t, 2H, 7.6 J = Hz), 7.47 (d, 4H, J = 7.8 Hz), 7.62 (d, 2H, J = 7.6 Hz), 7.71 (d, 4H, J = 8.5
Hz), 7.77 (t, 2H, J = 7.7 Hz), 8.43 (d, 2H, J = 7.7 Hz); 13C NMR, δ (ppm): 90.24,
125.16, 125.81, 126.30, 126.47, 127.02, 127.40, 127.74, 128.86, 129.91, 134.06,
134.39, 139.85, 141.18, 149.16, 168.85.
(R*,R*)-3,3'-bis(diphenyl-4-yl)-3,3'-diphthalide (2’a). Colorless crystals, mp 295.0-
300.0°С (dec). IR, cm-1: 1768.80, 1489.11, 1449.57, 1286.58, 1246.07, 1230.64,
1084.04, 993.38, 975.06, 823.64, 758.06, 735.87, 697.30. 1H NMR, δ (ppm): 7.32 (t,
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2H, J = 7.7 Hz), 7.37 (t, 2H, J = 7.7 Hz), 7.40 (t, 4H, J = 7.8 Hz), 7.48 (d, 4H, J = 8.5
Hz), 7.52 (d, 4H, J = 8.5 Hz), 7.60 (t, 2H, J = 7.8 Hz), 7.65 (d, 2H, J = 7.7 Hz), 7.83 (d,
4H, J = 8.5 Hz), 8.00 (d, 2H, J = 7.8 Hz); 13C NMR, δ (ppm): 90.99, 124.56, 125.81,
126.84, 126.97, 127.03, 127.06, 127.66, 128.85, 129.92, 134.79, 135.67, 140.06,
141.16, 149.11, 169.37. Found, %: С 84.05; Н 4.35. М+ 570.1826 (EI). Anal. Calcd for
С40Н26О4, %: С 84.19; Н 4.59. М 570.1826.
(R*,S*)-3,3'-bis[4-(p-bromophenyl)phenyl]-3,3'-diphthalide (2b). Colorless crystals,
mp 315.0-320.0°C (dec). IR, cm -1: 1780.37, 1593.17, 1481.95, 1287.80, 1248.00,
1074.40, 1001.10, 807.24, 747.45. 1H NMR, δ (ppm): 7.32 (d, 4H, J = 8.2 Hz), 7.33 (d,
4H, J = 8.1 Hz), 7.45 (t, 2H, J = 7.5 Hz), 7.51 (d, 4H, J = 8.4 Hz), 7.63 (d, 2H, J = 7.6
Hz), 7.71 (d, 4H, J = 8.5 Hz), 7.78 (t, 2H, J = 7.6 Hz), 8.41 (d, 2H, J = 7.6 Hz); 13C
NMR, δ (ppm): 90.11, 122.09, 125.10, 125.86, 126.22, 126.30, 127.52, 128.60, 130.01,
131.98, 134.48, 138.72, 140.03, 149.05, 168.74.
(R*,R*)-3,3'-bis[4-(p-bromophenyl)phenyl]-3,3'-diphthalide (2’b). Colorless crystals,
mp 280.0-285.0°C (dec). IR, cm -1: 1776.52, 1592.00, 1483.32, 1286.58, 1246.07,
1226.78, 1102.37, 1080.18, 1002.06, 995.31, 976.02, 811.10, 733.95, 685.72. 1H NMR,
δ (ppm): 7.36 (t, 2H, J = 7.2 Hz), 7.37 (d, 4H, J = 8.5 Hz), 7.44 (d, 4H, J = 8.6 Hz), 7.52
(d, 4H, J = 8.5 Hz), 7.60 (t, 2H, J = 7.7 Hz), 7.65 (d, 2H, J = 8.6 Hz), 7.84 (d, 4H, J = 8.6
Hz), 7.98 (d, 2H, J = 7.8 Hz); 13C NMR, δ (ppm): 90.83, 122.01, 124.49, 125.66,
128.86, 126.69, 127.02, 128.61, 130.01, 131.97, 134.86, 136.17, 138.89, 139.94,
148.97, 169.27. Found, %: C 65.70; H 3.25; Br 21.93. [М/2]+ 363.0021 (EI); [M+H]+ 727
(CI). Anal. Calcd for С40Н24О4Br2, %: C 65.95; H 3.32; Br 21.94. М 726.0036.
(R*,S*)-3,3'-bis(4-phenoxyphenyl)-3,3'-diphthalide (2c). Colorless crystals, mp 220.5-
221.0°C. IR, cm -1: 1774.59, 1587.48, 1505.51, 1489.11, 1456.32, 1288.50, 1241.25,
1202.67, 1167.95, 1098.51, 1073.47, 1022.32, 1003.03, 994.35, 869.93, 742.63. 1H
NMR, δ (ppm): 6.75 (d, 4H, J = 8.8 Hz), 6.83 (d, 4H, J = 8.1 Hz), 7.09 (t, 2H, J = 7.4
Hz), 7.29 (t, 4H, J = 7.8 Hz), 7.48 (t, 2H, J = 7.5 Hz), 7.56 (d, 4H, J = 8.8 Hz), 7.68(d,
2H, J = 7.6 Hz), 7.75 (t, 2H, J = 7.6 Hz), 8.31 (d, 2H, J = 7.6 Hz); 13C NMR, δ (ppm):
90.18, 117.86, 119.12, 123.73, 125.12, 125.70, 126.39, 128.52, 129.52, 129.82, 134.35,
149.15, 156.50, 157.50, 168.65.
(R*,R*)-3,3'-bis(4-phenoxyphenyl)-3,3'-diphthalide (2’c). Colorless crystals, mp
211.0-212.0°C. IR, cm -1: 1770.73, 1587.48, 1505.51, 1487.18, 1366.62, 1332.87,
1307.79, 1287.54, 1248.96, 1202.67, 1169.88, 1102.37, 1079.22, 1067.65, 1021.35,
1003.03, 996.28, 973.13, 738.77. 1H NMR, δ (ppm): 6.88 (d, 4H, J = 8.9 Hz), 6.92 (d,
4H, J = 7.8 Hz), 7.11 (t, 2H, J = 7.4 Hz), 7.31 (t, 4H, J = 7.7 Hz), 7.36 (t, 2H, J = 7.5 Hz),
17

ACCEPTED MANUSCRIPT
7.58 (t, 2H, J = 7.8 Hz), 7.63 (d, 2H, J = 7.7 Hz), 7.65 (d, 4H, J = 8.9 Hz), 7.95 (d, 2H, J
= 7.8 Hz); 13C NMR, δ (ppm): 90.82, 118.19, 119.09, 123.65, 124.37, 125.86, 125.93,
128.27, 129.77, 129.78, 129.89, 134.70, 149.40, 156.70, 157.53, 169.10. Found, %: С
79.63; Н 4.26. М+ 602.1684 (EI). Anal. Calcd for С40Н26О6, %: С 79.72; Н 4.35. М
602.1724.
(R*,S*)-3,3'-bis[4-(phenylthio)phenyl]-3,3'-diphthalide (2d). Colorless crystals, mp
227.0-227.5°C. IR, cm -1: 1782.30, 1580.81, 1477.54, 1244.14, 1069.57, 1020.39,
1008.81, 745.52, 701.15. 1H NMR, δ (ppm): 7.02 (d, 4H, J = 8.6 Hz), 7.19 (d, 4H, J =
7.5 Hz), 7.25-7.30 (m, 6H), 7.47 (t, 2H, J = 7.6 Hz), 7.50 (d, 4H, J = 8.6 Hz), 7.66 (d, 2H,
J = 7.6 Hz), 7.73 (t, 2H, J = 7.5 Hz), 8.28 (d, 2H, J = 7.8 Hz); 13C NMR, δ (ppm): 89.88,
125.02, 125.34, 125.73, 126.22, 127.56, 127.64, 129.32, 129.94, 131.78, 133.27,
134.27, 134.42, 137.51, 148.73, 168.45.
(R*,R*)-3,3'-bis[4-(phenylthio)phenyl]-3,3'-diphthalide (2’d). Colorless crystals, mp
166.0-166.5°C. IR, cm -1: 1778.44, 1594.3, 1492.27, 1477.54, 1286.58, 1247.03,
1244.85, 1039.69, 1084.04, 1020.39, 1003.99, 993.38, 927.16, 812.07, 753.23, 722.37,
691.51. 1H NMR, δ (ppm): 7.16 (d, 4H, J = 8.6 Hz), 7.25-7.30 (m, 10H), 7.34 (t, 2H, J =
7.5 Hz), 7.56 (t, 2H, J = 7.5 Hz), 7.62 (d, 2H, J = 7.6 Hz), 7.63 (d, 4H, J = 8.6 Hz), 7.93
(d, 2H, J = 7.8 Hz); 13C NMR, δ (ppm): 90.57, 124.36, 125.76, 125.80, 127.22, 127.62,
129.38, 129.73, 129.96, 131.75, 134.48, 134.76, 135.02, 137.28, 148.49, 168.92.
Found, %: C 75.80; H 3.91; S 10.00. М+ 634.1267 (EI). Anal. Calcd for С40Н26О4S2, %:
C 75.69; H 4.13; S 10.10. М 634.1263.
(R*,S*)-3,3'-bis(fluoren-2-yl)-3,3'-diphthalide (2e). Yellowish powder, mp 276.0-
280.0°C (dec). IR, cm -1: 1772.66, 1595.07, 1455.35, 1403.27, 1284.65, 1235.46,
1103.33, 1072.47, 1018.46, 993.38, 752.27, 741.66, 732.02. 1H NMR, δ (ppm): 3.68 (d,
2H, J = 21.8 Hz), 3.82 (d, 2H, J = 21.8 Hz), 7.30 (t, 2H, J = 7.4 Hz), 7.34 (t, 2H, J = 7.2
Hz), 7.39 (t, 2H, J = 7.5 Hz), 7.50 (d, 2H, J = 7.3 Hz), 7.54 (d, 2H, J = 8.4 Hz), 7.55 (d,
2H, J = 8.4 Hz), 7.68 (d, 4H, J = 7.8 Hz), 7.76 (t, 2H, J = 7.9 Hz), 7.82 (s, 2H), 8.45 (d,
2H, J = 7.5 Hz); 13C NMR, δ (ppm): 36.92, 90.74, 119.20, 120.27, 123.75, 125.14,
125.29, 125.73, 128.79, 126.37, 126.90, 127.25, 129.76, 133.48, 134.17, 140.81,
141.91, 142.79, 143.65, 149.40, 168.93.
(R*,R*)-3,3'-bis(fluoren-2-yl)-3,3'-diphthalide (2’e). Yellowish crystals, mp 288.0-
290.0°C (dec). IR, cm -1: 1778.44, 1591.96, 1465.32, 1284.65, 1248.96, 1223.89,
1103.33, 1096.58, 1006.89, 983.74, 761.91, 736.84, 685.43. 1H NMR, δ (ppm): 3.74 (d,
2H, J = 21.8 Hz), 3.81 (d, 2H, J = 21.8 Hz), 7.27 (t, 2H, J = 8.2 Hz), 7.32 (t, 2H, J = 7.3
Hz), 7.36 (t, 2H, J = 7.3 Hz), 7.48 (d, 2H, J = 7.4 Hz), 7.59(d, 2H, J = 7.9 Hz), 7.60 (t,
18

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2H, J = 7.2 Hz), 7.66 (d, 2H, J = 7.6 Hz), 7.68 (d, 2H, J = 7.5 Hz), 7.77 (d, 2H, J = 8.3
Hz), 7.92 (s, 2H), 8.02 (d, 2H, J = 7.9 Hz); 13C NMR, δ (ppm): 37.03, 91.56, 119.53,
120.18, 123.11, 124.72, 125.07, 125.29, 125.75, 125.77, 126.81, 127.10, 129.82,
134.71, 135.12, 140.88, 141.92, 143.12, 143.59, 149.44, 169.57. Found, %: C 84.00; H
4.07. М+ 594.1832 (EI). Anal. Calcd for С42Н26О4, %: C 84.83; H 4.41. М 594.1826.
(R*,S*)-3,3'-bis(dibenzofuran-2-yl)-3,3'-diphthalide (2f). White powder, mp 336.0-
338.0°C (dec). IR, cm -1: 1764.94, 1595.12, 1450.03, 1273.17, 1242.21, 1201.70,
1077.29, 999.17, 744.55, 723.34. 1H NMR, δ (ppm): 7.35 (t, 2H, J = 6.8 Hz), 7.37 (d,
2H, J = 8.5 Hz), 7.39 (t, 2H, J = 6.8 Hz), 7.45 (t, 2H, J = 8.2 Hz), 7.51 (d, 2H, J = 8.2
Hz), 7.55 (d, 2H, J = 7.5 Hz), 7.78 (t, 2H, J = 8.2 Hz), 7.84 (d, 2H, J = 8.8 Hz), 7.90 (d,
2H, J = 7.4 Hz), 8.21 (s, 2H), 8.51 (d, 2H, J = 7.6 Hz); 13C NMR, δ (ppm): 90.62,
111.11, 111.81, 119.65, 120.81, 123.08, 123.82, 123.95, 125.15, 125.89, 125.98,
126.24, 127.66, 129.89, 129.98, 134.40, 149.43, 155.81, 156.60, 168.81.
(R*,R*)-3,3'-bis(dibenzofuran-2-yl)-3,3'-diphthalide (2’f). Colorless crystals, mp
285.0-290.0°C (dec). IR, cm -1: 1775.55, 1592.20, 1447.64, 1279.82, 1247.03, 1203.63,
1104.29, 1008.81, 999.17, 980.84, 753.23, 747.45, 728.16. 1H NMR, δ (ppm): 7.29 (t,
2H, J = 8.2 Hz), 7.38 (t, 2H, J = 7.3 Hz), 7.39 (t, 2H, J = 7.4 Hz), 7.40 (d, 2H, J = 8.8
Hz), 7.45 (d, 2H, J = 8.2 Hz), 7.63 (t, 2H, J = 7.6 Hz), 7.68 (d, 2H, J = 7.6 Hz), 7.89 (d,
2H, J = 7.7 Hz), 7.99 (d, 2H, J = 8.8 Hz), 8.08 (d, 2H, J = 7.8 Hz), 8.30 (s, 2H); 13C
NMR, δ (ppm): 91.46, 111.47, 111.69, 118.83, 120.87, 122.92, 123.83, 124.18, 124.70,
125.58, 125.65, 125.86, 127.51, 129.93, 131.48, 134.82, 149.49, 155.79, 156.52,
169.42. Found, %: C 80.95; H 3.34. М+ 598.1417 (EI). Anal. Calcd for С40Н22О6, %: C
80.26; H 3.70. М 598.1411.
(R*,S*)-3,3'-bis(terphenyl-4-yl)-3,3'-diphthalide (2g). White powder, mp 290.0-
294.0°C (dec). IR, cm -1: 1781.34, 1594.32, 1485.58, 1247.12, 1074.40, 1003.03,
816.89, 765.77, 745.52, 700.19. 1H NMR, δ (ppm): 7.37 (t, 2H, J = 7.2 Hz), 7.43-7.47
(m, 10H), 7.56 (d, 4H, J = 8.2 Hz), 7.61-7.65 (m, 10H), 7.74 (d, 4H, J = 8.4 Hz), 7.79 (t,
2H, J = 7.6 Hz), 8.44 (d, 2H, J = 7.1 Hz); 13C NMR, δ (ppm): 90.26, 125.17, 126.34,
127.10, 127.36, 127.47, 127.53, 127.59, 128.91, 129.00, 129.94, 134.13, 134.42,
138.67, 140.58, 140.63, 149.15, 168.85.
(R*,R*)-3,3'-bis(terphenyl-4-yl)-3,3'-diphthalide (2’g). White powder, mp 309.0-
312.0°C (dec). IR, cm -1: 1776.52, 1595.20, 1484.29, 1366.62, 1285.61, 1247.03,
1098.51, 1077.29, 1003.03, 993.38, 972.16, 815.92, 763.84, 745.52, 697.30. 1H NMR,
δ (ppm): 7.35-7.40 (m, 4H), 7.46 (t, 4H, J = 7.6 Hz), 7.55 (d, 4H, J = 8.5 Hz), 7.60-7.68
(m, 16H), 7.87 (d, 4H, J = 8.5 Hz), 8.02 (d, 4H, J = 7.8 Hz); 13C NMR, δ (ppm): 90.99,
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124.56, 125.79, 125.83, 126.71, 127.04, 127.09, 127.40, 127.49, 127.58, 128.89,
129.95, 134.82, 135.73, 138.89, 140.52, 140.61, 149.08, 169.38. Found, %: С 86.65; Н
4.45. [М+H]+ 723 (CI). Anal. Calcd for C52H34O4, %: C 86.41; H 4.74. М 722.2452.
3-(4-phenoxyphenyl)-3'-[4-(phenylthio)phenyl]-3,3'-diphthalides (3/3’).
A solution of 25.0 g sodium iodide (0.17 mol) in dry acetone (100 mL) was added to a
stirred solution of mixture of 15.0 g o-[p-(phenylthio)-benzoyl]-benzoic pseudo acid
chloride (42.5 mmol) and 14.3 g o-(p-phenoxybenzoyl)-benzoic pseudo acid chloride
(42.5 mmol) in acetone (200 mL). Stirring was continued for 4h, then reaction mixture
was poured into solution of Na2S2O3ꢁ5H2O (90 g) in water (450 ml) to remove the
liberated iodine. Insoluble solid was filtered off and washed with water. The solid was
stirred in 10 % KOH solution (500 mL) for 1 h, then washed with water until neutral, and
then dried. General yield 23.7 g (90%). Isolation of individual diphthalides 3 and 3’ was
performed using semi-preparative HPLC.
(R*,S*)-3-(4-phenoxyphenyl)-3'-[4-(phenylthio)phenyl]-3,3'-diphthalide
(3).
Colorless crystals, mp 215-216°C. IR, cm -1: 1782.30, 1580.10, 1490.07, 1466.93,
1377.23, 1286.58, 1231.60, 1168.91, 1067.65, 1007.85, 860.60, 759.02, 745.52,
710.80. 1H NMR, δ (ppm): 6.73 (d, 2H, J = 8.8 Hz), 6.83 (d, 2H, J = 8.2 Hz), 7.03 (d,
2H, J = 8.5 Hz), 7.09 (t, 1H, J = 7.4 Hz), 7.19 (d, 2H, J = 7.4 Hz), 7.30-7.26 (m, 6H),
7.47 (t, 2H, J = 7.5 Hz), 7.53 (t, 4H, J = 8.8 Hz), 7.67 (d, 2H, J = 7.6 Hz), 7.74 (t, 2H, J =
7.6 Hz), 8.30 (d, 2H, J = 7.6 Hz); 13C NMR, δ (ppm): 90.03, 90.06, 123.76, 125.09,
125.72, 125.77, 126.29, 126.32, 127.57, 127.63, 128.56, 129.35, 129.42, 129.84,
129.89, 129.93, 131.78, 133.45, 134.37, 134.40, 134.42, 137.43, 148.89, 149.02,
156.44, 157.52, 168.57, 168.63.
(R*,R*)-3-(4-phenoxyphenyl)-3'-[4-(phenylthio)phenyl]-3,3'-diphthalides
(3’).
Colorless crystals, mp 180-181°C. 1H NMR, δ (ppm): 6.87 (d, 2H, J = 8.8 Hz), 6.92 (d,
2H, J = 8.5 Hz), 7.12 (t, 1H, J = 7.4 Hz), 7.17 (d, 2H, J = 8.5 Hz), 7.26-7.29 (m, 5H),
7.31 (t, 2H, J = 7.4 Hz), 7.35 (t, 2H, J = 7.4 Hz), 7.57 (t, 2H, J = 7.7 Hz), 7.65-7.59 (m,
6h), 7.93 (d, 1H, J = 7.7 Hz), 7.94 (d, 1H, J = 7.7 Hz); 13C NMR, δ (ppm): 90.70, 90.74,
123.74, 124.37, 124.39, 125.85, 127.33, 127.61, 128.18, 129.35, 129.40, 129.85,
129.90, 129.93, 129.98, 131.05, 131.70, 134.62, 134.78, 134.80, 135.18, 137.18,
148.59, 148.78, 156.62, 157.53, 169.06, 169.11. Found, %: С 77.46; Н 4.01; S 5.00.
[М+H]+ 619 (CI). Anal. Calcd for С40Н26О5S, %: C 77.65; H 4.24; S 5.18. М 618.1495.
Acknowledgements
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Authors are grateful to Dr Yu.A.Lebedev of IMCP UFRC RAS for kindly making
the microscopic image of the crystal of (R*,R*)-3,3'-bis[4-(phenylthio)phenyl]-3,3'-
diphthalide in polarized light.
The IR-, NMR-analyses and HPLC were performed on equipment at the Centre
for the Collective Use “Chemistry” of UIC UFRC RAS. The X-ray analyses were carried
out on equipment at the Centre for the Collective Use “Agidel” of IPC UFRC RAS.
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Table 1. Synthesis of biaryl-3,3'-diphtalides 2a-g/2’a-g.
Table 2. Structural characteristics of biaryl-3,3'-diphtalides 2a-d/2’a-f from the X-ray
analyses data.
Table 3. Spectral characteristics of biaryl-3,3′-diphthalides 2a-g/2’a-g.
Figure 1. Molecular structures of biaryl-3,3′-diphthalides. Atoms are represented by
thermal displacement ellipsoids at the 30% probability level.
Figure 2. Favorable rotameric conformation of biaryl-3,3′-diphthalides diastereoisomers.
Figure 3. Plastic deformation of a platy crystal of (R*,R*)-3,3'-bis[4-(phenylthio)phenyl]-
3,3'-diphthalide observed in polarized light.
Figure 4. Molecular packing along the crystallographic axes for (R*,S*)- and (R*,R*)-
biaryl-3,3'-diphthalide crystals 2a/2’a, 2b/2’b, 2c/2’c and 2d/2’d.
Figure 5. HPLC of the mixture of biaryl-3,3'-diphtalides 2c, 2’c, 2d, 2’d, 3, 3’.
Figure 6. Schematic representation of a single- and two-point adsorption of meso- (a)
and chiral (b) rotamers of biaryl-3,3'-diphthalides on a hydrophobic stationary phase.
Figure 7. 1H NMR spectra of (R*,S*)- (a) and (R*,R*)- (b) 3,3'-bis(4-phenoxyphenyl)-
3,3'-diphthalide.
Figure 8. 13C NMR spectra of (R*,S*)- (a) and (R*,R*)- (b) 3,3'-bis(4-phenoxyphenyl)-
3,3'-diphthalide.
Scheme 1. Preparation of o-aroylbenzoic pseudo acids chlorides 1a-g.
Scheme 2. Joint dimerization of pseudo acids chlorides 1c and 1d.
24