Synthesis and crystal structure of chiral (1R,5R)-3-arylidenopinones

Article abstract of DOI:10.14233/ajchem.2013.14949

Three (1R,5R)-(-)3-arylideneopinones (2a, 2b and 2c) were first synthesized and characterized by IR, MS, NMR, elemental analysis and single-crystal X-ray diffraction method. The structure indicates that the compound 2a belongs to orthorhombic, space group P212121 with a = 1.0378 (5) nm, b = 1.1156 (6) nm, c = 1.2775 (7) nm, b = 90. V = 1.4791 (13) nm3, Z = 4, r = 1.223 g cm-3, μ = 0.083 mm-1, F (000) = 584 and final R1 = 0.0327, wR2 = 0.0876. The compound 2b belongs to trigonal, space group P32 with a = 0.93024(1₂) nm, b = 0.93024(1₂) nm, c = 1.3215(4) nm, b = 90.0. V = 0.9903(3) nm3, Z = 3, r = 1.219 g cm-3, μ = 0.079 mm-1, F(000) = 390 and final R1 = 0.0350, wR2 = 0.0912. The compound 2c belongs to monoclinic, space group P21 with a = 1.20252 (15) nm, b = 0.99228(1₂) nm, c = 2.3905(3) nm, b = 92.769( ₂). V = 2.8491(6) nm3, Z = 8, r = 1.216 g cm-3, μ = 0.254 mm-1, F(000) = 1104 and final R1 =0.0440, wR2 = 0.1069.

Full text of DOI:10.14233/ajchem.2013.14949

Asian Journal of Chemistry; Vol. 25, No. 13 (2013), 7490-7494
http://dx.doi.org/10.14233/ajchem.2013.14949
Synthesis and Crystal Structure of Chiral (1R,5R)-3-Arylidenopinones
1
2
1
1,2,*
YI-QIN YANG , HAI-JUN XU , LAN LAN and SHI-FA WANG
1Institute of Light Industry Science and Engineering, Institute of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, P.R. China
2Jiangsu Key Lab of Biomass-based green Fuels and Chemicals, College of Chemical Engineering, Nanjing Forestry University, Nanjing
210037, P.R. China
*Corresponding author: Fax: +86 25 85418873; Tel: +25 85427812; E-mail: wsfyyq@njfu.com.cn; xuhaijun@njfu.edu.cn
(Received: 10 December 2012;
Accepted: 1 July 2013)
AJC-13735
Three (1R,5R)-(-)3-arylideneopinones (2a, 2b and 2c) were first synthesized and characterized by IR, MS, NMR, elemental analysis and
single-crystal X-ray diffraction method. The structure indicates that the compound 2a belongs to orthorhombic, space group P212121 with
a = 1.0378 (5) nm, b = 1.1156 (6) nm, c = 1.2775 (7) nm, β = 90º. V = 1.4791 (13) nm3, Z = 4, ρ = 1.223 g cm-3, µ = 0.083 mm-1, F (000) =
584 and final R1 = 0.0327, wR2 = 0.0876. The compound 2b belongs to trigonal, space group P32 with a = 0.93024(12) nm, b = 0.93024(12)
nm, c = 1.3215(4) nm, β = 90.0º. V = 0.9903(3) nm3, Z = 3, ρ = 1.219 g cm-3, µ = 0.079 mm-1, F(000) = 390 and final R1 = 0.0350, wR2 =
0.0912. The compound 2c belongs to monoclinic, space group P21 with a = 1.20252 (15) nm, b = 0.99228(12) nm, c = 2.3905(3) nm, β =
92.769(2)º. V = 2.8491(6) nm3, Z = 8, ρ = 1.216 g cm-3, µ = 0.254 mm-1, F(000) = 1104 and final R1 =0.0440, wR2 = 0.1069.
Key Words: (1S,5S)-(-)-β-pinene, (1R,5S)-(+)-nopinone, (1R,5R)-(-)-3-arylideneno-pinones, Crystal structure, Synthesis.
13C, respectively. The chemical shifts were expressed in ppm
INTRODUCTION
(δ scale) relative to the reference compound tetramethylsilane
It is a well-known fact that an over exposure to solar ultra-
(TMS). Electronic impact (EI) gas chromatography-mass
violet radiation is harmful to human health, the major acute
spectrometry (GC-MS) was conducted on an Agilent 6890 N
effects on normal human skin comprise sunburn cells, tanning,
GC coupled to anAgilent Technologies 5973 inert mass selec-
premature skin aging and an increased risk for skin cancers1-3.
tive detector using a 30 m × 0.25 mm i.d., 0.25 µm file thickness
The steady increase in the incidence of melanoma, non-melanoma
HP-5MS capillary column (Agilent Technologies, Wilmington,
cutaneous neoplasia and preneoplasic disorders has contributed
DE) with helium as carrier gas (36 cm/s, 80 ºC for 2 min and
to the demand for more effective protection from the sun4-6.
then programmed to 280 ºC at 15 ºC/min and held for 20 min).
Terpenoid derivatives, such as benzylidene camphor, p-
A 70 eV electron beam was employed for sample ionization.
methylbenzylidene camphor, benzylidene camphor sulfonic
GC analyses were performed on anAgilent 6890 GC equipped
acid, are widely used as UV filters in cosmetics because of their
with a flame ionization detector (FID) using a 30 m × 0.32
stable storage, no irritation to skin, no photosensitization, low
mm i.d., 0.25 µm file thickness HP-5 capillary column with
toxicity, good stability and chemical inertness and low absor-
nitrogen as carrier gas (38 cm/s, 80 ºC for 2 min and then
ption to skin7,8. However, natural camphor is expensive and the
programmed to 280 ºC at 10 ºC/min and held for 20 min) in
synthesized camphor exist several disadvantages including a
the split mode and the split ratio was 50:1. Fourier-transform
long process of synthesis routes and severe environmental
infrared (FT-IR) spectra of samples were recorded from pota-
pollution. The crystal structure of such compounds are interesting
ssium bromide disks prepared with each crystalline sample
and have seldom been reported. Herein, we report the synthesis
on a Nicolet 380 FT-IR spectrophotometer in the scan range
and structural characterization of a chiral (1R, 5R)-3-arylideno-
pinones (2a-2c) which had good ultraviolet absorption charac-
of 4000-400 cm-1. Melting points and specific rotation were
measured using X-6 microscopic melting point apparatus and
teristics by using a low cost and abundant renewable resource
Shanghai Spoif W22-2S automatic polarimeter. The raw
β-pinene as the raw material.
material β-pinene with a purity of 98.1 % (GC) and [α]D25 -21.1º
EXPERIMENTAL
(c = 1.0, CHCl3) was purchased from Deqing Forest Chemical
Plant of China. Flash column chromatography was carried out
on silica gel 60 (230-400 mesh).All reactions were performed
NMR spectra were recorded in CDCl3 solution on a Bruker
AV 400 spectrometer at 400 MHz for H and 100 MHz for
1

Vol. 25, No. 13 (2013)
Synthesis and Crystal Structure of Chiral (1R,5R)-3-Arylidenopinones 7491
under a nitrogen atmosphere with magnetic stirring and the
syntheses of 3-arylidenenopinones from β-pinene were shown
in Scheme-I.
30.95, 39.49, 55.82, 55.91, 113.61, 114.66, 124.84, 128.29,
130.16, 135.90, 203.58; FT-IR (KBr, νmax, cm-1): 3238 ν(O-H),
2966-2901 ν(C-H), 1674 ν(C=O), 1593-1440 (C6H3-, νas C=C),
1307-1130 ν(O-CH3), 856-619 τ(C-H); EI-MS m/z (%): 272
(M+, 100), 257 (19), 229 (18), 203 (30), 162 (26), 137 (24),
115 (21), 91 (20), 83 (16), 55 (33), 41 (19).
CH3 CH3
3CH CH3
CH3 CH3
Ar CHO
catalyst
Ar
oxidant
H
H
H
(1R,5R)-(-)-3-(4-hydroxybenzylidene) nopinone (2b):
A 100 mL dried flask equippedd with a agitator, thermometer
and condensor was charged with (+)-nopinone (1.380 g, 0.01
mol), p-hydroxybenzaldehyde (1.83 g, 0.015 mol) and 3.0 g
of powderd potassium tert-butoxide in 30 mL of tert-butanol
under a nitrogen atmosphere and the resulting mixture was
refluxed for 7~8 h until the conversion ratio of nopinone
reached over 95 % (monitored with GC) and then 10 mL of
water was added. The mixture was extracted with ethyl acetate
(3 × 10 mL) and the combined organic layers were washed
with water and saturated brine to neutrality, dried over Na2SO4
and concentrated to afford the yellow crude product, which
was purified by recrystallization in 10 mL of acetone for 3
days at room temperature to provide 1.88 g (7.76 mmol, 77.6 %
isolated yield, purity of 97.4 %) of compound 2b as a colourless
transparent crystal, m.p. 199.6-200.6 ºC, [α]D25 -56.3º (c = 0.6,
O
CH2
(1S,5S)-(-)-beta-pinene
O
H
H
H
(1R,5R)-(-)-3-arylidene-nopinone
(1R,5S)-(+)-nopinone e
2a-2c
1
CH3 CH3
CH3 CH3
CH3 CH3
Cl
OH
OMe
OH
H
H
H
O
H
O
O
H
H
(1R,5R)-(-)-3-(4'-chloro-
benzylidene)-nopinone (2c
(1R,5R)-(-)-3-(4'-hydroxy-3'-methoxy (1R,5R)-(-)-3-(4'-hydroxy-
)
-benzylidene)-nopinone (2a
)
benzylidene)-nopinone (2b)
Scheme-I
Synthesis
(+)-Nopinone (1): Nopinone was prepared by β-pinene
oxidation using acidic potassium permanganate. A 500 mL
dried three-necked flask equipped with a thermometer, con-
denser and stirrer was charged with acetone 100 mL, 2 mol/L
H2SO4 15 mL and β-pinene 50 g and cooled with ice bath to
about 15 ºC. 87 g of KMnO4 fully crashed was added in por-
tions within 1~1.5 h. The ice bath was removed after com-
plete addition of KMnO4 and the reaction was kept at room
temperature for another 5-6 h. The reaction was monitored by
GC until the peak of β-pinene was disappeared. The resulting
mixture was filted with a sand-core funnel to remove the solid
MnO2 and was washed with acetone (2 × 40 mL). The filtrate
was concentrated by a rotor evaporator to recover acetone and
the bottom residue was diluted with 100 mL of hexane. The
diluted residue was washed with saturated brine to neutral and
the organic layer was dried over Na2SO4 and then was distilled
to collect the fraction at 100~102 ºC/266 kPa, a colourless
oily liquid with a yield over 83.9 %, purity 95.04 % (GC),
specific rotation [α]D25 + 27.3º (c = 1.0, CHCl3).
1
CHCl3). H NMR (400 MHz, CDCl3): δ (ppm) 0.929-1.378
(d, 6H, -CH3), 1.496-1.531 (d, 1H, -CH2), 2.374-2.384 (m,
1H, -CH2), 2.587-2.641 (m, 1H, -CH), 2.661-2.730 (t, 1H,
-CH), 2.948-2.956 (s, 2H -CH2), 7.690 (s, 1H, C=CH-C),
6.908(m, 1H, -OH), 7.312-7.601 (m, 2H, CH), 7.573-7.601
(d, 2H, CH); 13C NMR (100 MHz, CDCl3): δ (ppm) 21.63,
26.19, 27.59, 29.69, 31.00, 39.47, 55.86, 115.78, 128.14,
129.84, 132.96, 136.23, 157.17, 204.92; FT-IR (KBr, νmax, cm-1):
3378 ν(O-H), 2962-2911 ν(C-H), 1669 ν(C=O), 1607~1469
(C6H4-, νas C=C), 987-647 (C6H4-, τC-H); EI-MS m/z (%): 242
(M+, 100), 227 (M+-15, 31), 199 (227-C2H4, 42), 186 (22),
171 (47), 132 (56), 107 (54), 83 (35), 55 (53), 41(34).
(1R, 5R)-(-)-3-(4-chlorobenzyliene) nopinone (2c): A
100 mL dried flask fitted with a agitator, thermometer and
condensor was charged with (+)-nopinone (1.38 g, 0.01 mol),
p-chlorobenzaldehyde (1.68 g, 0.012 mol) and 3 g of powderd
sodium mehoxide in 30 mL of tertiary butanol under a nitrogen
atmosphere and the resulting mixture was refluxed for 5-8 h
until the conversion ratio of nopinone reached 100 % and 15
mL of water was added and then extracted with ethyl acetate
for three times (3 × 15 mL). The combined organic layer was
washed with water and brine to neutrality, dried over Na2SO4
and concentrated to afford the deep yellow crude product,
which was purified by recrystallization in mixed solvent conta-
ining 10 mL of acetone and 0.5 mL of ethanol for several days
at room temperature to afford 2.223 g (8.55 mmol, 85.5 %
isolated yield, purity 97.8 %) of compound 2c as a colourless
(1R, 5R)-(-)-3-(4-hydroxy-3-methoxybenzylidene)
nopinone (2a): A 100 mL dried flask fitted with a agitator,
thermometer and condensor was charged with (+)-nopinone
(1.38 g, 0.01 mol), vanillin (1.824 g, 0.012 mol) and 3 g of
powderd potassium tert-butoxide in 30 mL of toluene under a
nitrogen atmosphere and the resulting mixture was refluxed
for 10~12 h until the main product reached 70~75 % and the
byproduct was controlled within 10~15 % (monitored with
GC) and then 15 mL of water was added. The mixture was
separated into two layers and the organic layer was washed
with water and brine to neutrality, dried over Na2SO4 and
concentrated to afford the yellow crude product, which was
purified by recrystallization in mixed solvent containing 10
mL of acetone and 0.5 mL of ethanol for several days at room
temperature to afford 1.044 g (3.84 mmol, 38.4 % isolated
yield, purity 95.3 %) of compound 2a as a colourless trans-
parent crystal, m.p. 173.5-174.2 ºC, [α] -44.7º (c = 0.32,
25
transparent crystal, m.p. 109.7-110.7 ºC, [α]D -22.88º (c =
0.31, CCl3). 1H NMR (400 MHz, CDCl3): δ (ppm) 0.921-1.381
(d, 6H, -CH3), 1.484-1.505 (d, 1H, -CH2), 2.356-2.374 (m,
1H, -CH2), 2.618-2.651 (m, 1H, -CH), 2.694-2.717 (t, 1H,
-CH), 2.930-2.941 (t, 2H, -CH2), 7.636-7.645 (t, 1H, C=CH-
C), 7.362-7.384 (t, 2H, CH), 7.499-7.516 (t, 2H, CH); 13C NMR
(100 MHz, CDCl3): δ (ppm) 21.55, 26.12, 27.36, 30.78, 39.29,
40.82, 55.78, 128.73, 131.78, 133.10, 134.10, 134.18, 134.74,
202.91; FT-IR (KBr, νmax, cm-1): 2984-2874 ν(C-H), 1686
1
CHCl3). H NMR (400 MHz, CDCl3): δ (ppm) 0.929-1.379
(d, 6H, -CH3), 1.500-1.520 (d, 1H, -CH2), 2.368-2.379 (m,
1H, -CH2), 2.609-2.633 (m, 1H, -CH), 2.681-2.704 (t, 1H,
-CH), 2.951-2.972 (s, 2H, -CH2), 7.644-7.653 (s, 1H, C=CH-
C), 3.921 (s, 3H,-OCH3), 6.056 (s, 1H, -OH), 6,955-6.972 (d,
1H, CH), 7.095-7.099 (s, 1H, CH), 7.189-7.209 (d, 1H, CH);
13C NMR (100 MHz, CDCl3): δ (ppm) 21.58, 26.18, 27.56,

7492 Yang et al.
Asian J. Chem.
TABLE-1
CRYSTALLOGRAPHIC DATA AND STRUCTURE REFINEMENT RESULTS FOR 2a-2c
Compound
2a
2b
2c
Empirical formula
Formular weight
Temperature [K]
Wavelength (Å)
Crystal system
space group
Unit cell dimension
a(Å)
C17H20O3
272.33
296(2)
0.71073
Orthorhombic
P212121
C16H18O2
242.30
296(2) K
0.71073
Trigonal
P32
C16H17OCl
260.75
296(2)
0.71073
Monoclinic
P21
10.378(5)
11.156(6)
12.775(7)
90
1479.1(13)
4
1.223
0.083
9.3024(12)
9.3024(12)
13.215(4)
90
990.3(3)
3
1.219
0.079
12.0252(15)
9.9228(12)
23.905(3)
92.769(2)
2849.1(6)
8
1.216
0.254
1104
b(Å)
c(Å)
β(º)
Volume [Å3]
z
ρ (calc)(g/cm3)
Absorption Coefficient
F(000)
584
390
Crystal size (mm)
Limiting indices
0.20 × 0.20 × 0.10
-12 <= h <= 12
-13 <= k <= 12
-15 <= l <= 15
10742/2825 [R(int) = 0.0312]
0.984 and 0.992
Full-matrix least-squares on F2
2825/0/182
0.15 × 0.15 × 0.10
-11 <= h <= 11
-11 <= k <= 11
-16 <= l <= 15
7385/1288 [R(int) = 0.0254]
0.988 and 0.992
Full-matrix least-squares on F2
1288/1/167
0.20 × 0.15 × 0.10
-14 <= h <= 13
-11 <= k <= 12
-29 <= l <= 29
Reflections collected/ unique
Max. and min. transmission
Refinement method
21132/9917 [R(int) = 0.0273]
0.955 and 0.975
Full-matrix least-squares on F2
9917/1/649
Data/restraints/parameters
Goodness-of-fit on F2
1.013
1.094
1.026
R1 = 0.0327, wR2 = 0.0876
R1 = 0.0365, wR2 = 0.0906
0.2 (10)
R1 = 0.0350, wR2 = 0.0912
R1 = 0.0359, wR2 = 0.0918
0.2(15)
R1 = 0.0440, wR2 = 0.1069
R1 = 0.0718, wR2 = 0.1178
-0.03(5)
Final R indices [I > 2 σ (I)]
R indices (all data)
Absolute structure parameter
ν(C=O), 1686-1407 (C6H4-, νas C=C), 979-686 (C6H4-, τC-H);
EI-MS m/z (%): 260 (M+, 97), 245 (54), 217 (54), 204 (21),
189 (39), 165 (31), 150 (48), 141 (47), 125 (48), 115 (100),
83 (78), 55 (89).
Crystal structure determination: Crystallographic data
of 2a-2c were collected at 292 K on a Bruker SMART APEX
CCD diffractometer with graphite-monochromatized MoKα
radiation (λ = 0.071073 nm). An empirical absorption correc-
tion was applied. The structures were solved by the direct
method and refined using the SHELXL-97 software9. All
nonhydrogen atoms were refined by full-matrix least-squares
method on F2 with anisotropy thermal parameters, while all
hydrogen atoms were refined in calculated positions, assigned
isotropic thermal parameters and allowed to ride their parent
atoms. Crystallographic data and structure refinement results
are summarized in Table-1.
Fig. 1. Molecular structure of the compound 2a
configuration of C11 and C13 was established as R. The
selected bond lengths and bond angles are listed in Table-2. The
C-C bond lengths within the phenyl ring are normal in the range
from 0.1380(2) to 0.1409(2) nm with normal angles close to 120º
with the exception of the the angle (C2-C1-C6, 117.61(13). The
cyclohexanone ring in the bicyclic ring system adopts a flattened
half chair conformation that is constrained by the dimethyl substi-
tuted cyclobutane ring. The dihedral angle between the plane
consisting of C9-C10-C11-C13-C14 and the phenyl ring is 5.04
(0.10)º, which indicates the two planes are nearly coplanar. In
addition, the aromatic ring bonded to the C8 is coplanar around
the C8-C9 bond with a torsion angle C6-C1-C8-C9 of 2.6 (3)º,
which suggests a conjugation with the remaining part of the
system of C8-C9-C10-O2. The bond length of C8-C9 and C10-
O3 are 0.1348(2) and 0.12248(17) nm respectively which indi-
cates a doule-bond character, but they are slight longer than that
of lack conjugation of the double bond10. However, the C1-C8
(0.1463(2) is shorter than the normal C-C single bond, suggest-
ing a big conjugation system exists in the double bond and phenyl
ring and the electronic transfer occurs from the aromatic ring the
RESULTS AND DISCUSSION
The compounds 2a-2c are light yellow crystals and stable
in air at room temperature. The 1H NMR, MS and elemental
analysis for these three compounds are all in good agreement
with the assumed structure. In order to obtain a definitive struc-
tural proof of the 3-arylideneopinones and stereochemical
information, the single crystal X-ray diffraction study was
undertaken.
The compound 2a crystallizes in the orthorhombic space
group P212121. The molecular structure of the compound 2a is
shown in Fig. 1, which displays the E conformataion with
respect to the C=C double bond mainly due to the intramolecular
repulsive interaction between O3 and H6A. The absolute

Vol. 25, No. 13 (2013)
Synthesis and Crystal Structure of Chiral (1R,5R)-3-Arylidenopinones 7493
TABLE-2
SELECTED BOND LENGTHS (Å) AND BOND ANGLES (º) FOR THE COMPOUND 2a
Bond
C1-C2
C2-C3
C3-C4
C4-C5
C5-C6
C1-C6
C1-C8
Distance (Å)
1.409(2)
1.385(2)
1.402(2)
1.380(2)
1.389(2)
1.401(2)
1.463(2)
Bond
C9-C10
C9-C14
C10-C11
C11-C12
C11-C15
C12-C13
C13-C14
Distance (Å)
1.501(2)
1.522(2)
1.505(2)
1.558(2)
1.565(2)
1.527(3)
1.528(2)
Bond
C13-C15
C15-C17
O1-C3
O1-C7
O2-C4
Distance (Å)
1.566(2)
1.542(2)
1.3708(19)
1.426(2)
1.3621(18)
1.2248(17)
–
O3-C10
–
C8-C9
1.348(2)
C15-C16
1.520(3)
–
–
Angle
(º)
Angle
(º)
Angle
(º)
C3-C2-C1
C2-C3-C4
C5-C4-C3
C4-C5-C6
C5-C6-C1
C6-C1-C2
C6-C1-C8
C2-C1-C8
C9-C8-C1
121.69(14)
119.62(14)
119.22(13)
121.34(15)
120.51(15)
117.61(13)
125.35(13)
116.99(13)
132.17(14)
O2-C4-C5
O1-C3-C2
C3-O1-C7
O3-C10-C9
C8-C9-C10
C9-C10-C11
C10-C11-C12
C10-C11-C15
C14-C13-C12
118.57(14)
125.92(14)
117.89(13)
124.09(13)
117.42(13)
115.14(12)
107.25(12)
109.66(12)
109.33(15)
C14-C13-C15
C9-C14-C13
C10-C9-C14
C17-C15-C11
C11-C15-C13
C16-C15-C17
C16-C15-C13
C9-C14-C13
C17-C15-C13
111.09(13)
111.53(13)
116.07(13)
110.86(15)
85.05(12)
109.00(16)
119.20(16)
111.53(13)
112.33(15)
TABLE-3
O=C-C=C system. The other bond lengths and angels for the
bicyclic ring fragments are consistent with those previously
reported values10.A srong O-H···O intermolecular hydrogen-bond
interaction is observed in the molecule structure, which forms an
infinite one dimension zigzag chain structure (Table-3, Fig. 2).
The compound 2b crystallizes in the orthorhombic space
group P32. The molecular structure of the compound 2b is
shown in Fig. 3. The selected bond lengths and bond angles
are listed in Table-4. Bond lengths and angles observed in 2b
HYDROGEN BOND LENGTHS (Å) AND BOND
ANGLES (º) FOR THE COMPOUND 2a
D-H···A
d(D-H)
0.82
D(H···A)
1.95
D(D···A)
2.7189(19)
∠DHA
155.1
O2-H2A···O3i
Symmetry codes: (i) x + 1/2, -y-1/2, -z-2
Fig. 3. Molecular structure of the compound 2b
are in normal ranges and similar to the corresponding values
in 2a. However, the phenyl ring is oriented with the respect to
the plane consisting of C8-C9-C10-C12-C3 at a dihedral angle
of 42.94(0.07)º. In addition, a torsion angle of C6-C1-C7-C8
Fig. 2. Molecular one-dimensional chain hydrogen-bond structure of the
compound 2a
TABLE-4
SELECTED BOND LENGTHS (Å) AND BOND ANGLES (º) FOR THE COMPOUND 2b
Bond
C1 C2
C2-C3
C3-C4
C4-C5
C5-C6
C1-C6
C7-C1
Angle
Distance (Å)
1.399(3)
1.370(3)
1.390(3)
1.388(3)
1.374(3)
1.400(3)
1.459(3)
(º)
Bond
C7-C8
O1-C4
O2-C9
C8-C9
C9-C10
C10-C11
C10-C14
Angle
Distance (Å)
1.342(3)
1.361(3)
1.230(3)
1.494(3)
1.495(3)
1.551(3)
1.568(3)
(º)
Bond
C11-C12
C12-C14
C13-C12
C8-C13
C16-C14
C14-C15
–
Distance (Å)
1.533(4)
1.563(3)
1.522(3)
1.515(3)
1.510(4)
1.538(4)
–
Angle
(º)
C3-C2-C1
C2-C3-C4
C5-C4-C3
C6-C5-C4
C5-C6-C1
C2-C1-C6
C8-C7-C1
O1-C4-C3
121.9(2)
120.2(2)
119.0(2)
120.5(2)
121.45(19)
116.9(2)
129.19(19)
123.0(2)
C7-C8-C9
C8-C9-C10
C9-C10-C11
C9-C10-C14
C13-C12-C11
C13-C12-C14
C12-C14-C10
C11-C12-C14
117.41(18)
115.44(17)
106.91(19)
110.16(19)
110.0(2)
110.92(19)
85.11(18)
87.94(19)
C8-C13-C12
C9-C8-C13
C16-C14-C10
C16-C14-C12
C15-C14-C10
C16-C14-C15
O2-C9-C8
–
111.30(18)
115.78(18)
118.0(2)
119.2(2)
111.2(2)
109.8(2)
121.6(2)
–

7494 Yang et al.
Asian J. Chem.
TABLE-6
SELECTED BOND LENGTHS (Å) AND BOND ANGLES (º) FOR THE COMPOUND 2c
Bond
C1-C2
C2-C3
C3-C4
C4-C5
C5-C6
C1-C6
C7-C1
Cl1-C4
Cl3-C36
C18-C19
C22-C21
C23-C24
C26-C27
C28-C29
C29-C31
C56-C55
Angle
Distance (Å)
1.395(4)
1.372(4)
1.362(4)
1.361(4)
1.374(4)
1.385(4)
1.460(4)
1.740(3)
1.740(3)
1.380(4)
1.374(4)
1.344(4)
1.532(4)
1.554(4)
1.524(5)
1.344(3)
(º)
Bond
C7-C8
C8-C9
Distance (Å)
1.338(4)
1.495(4)
1.484(4)
1.551(5)
1.554(4)
1.523(4)
1.549(5)
1.743(3)
1.736(3)
1.374(4)
1.389(4)
1.514(4)
1.544(4)
1.485(4)
1.503(4)
–
Bond
C12-C14
C13-C15
C13-C16
C8-C14
O1-C9
O2-C30
O3-C46
O4-C57
C17-C18
C20-C21
C23-C17
C26-C25
C26-C29
C29-C32
C39-C40
–
Distance (Å)
1.512(4)
1.548(5)
1.521(5)
1.526(4)
1.209(3)
1.217(3)
1.213(3)
1.218(3)
1.394(4)
1.371(4)
1.461(4)
1.517(3)
1.548(4)
1.532(4)
1.340(3)
–
C9-C10
C10-C11
C10-C13
C11-C12
C13-C12
Cl2-C20
Cl4-C52
C20-C19
C22-C17
C24-C25
C28-C27
C30-C28
C24-C30
–
Angle
(º)
Angle
(º)
C1-C2-C3
C2-C3-C4
C3-C4-C5
C4-C5-C6
C5-C6-C1
C6-C1-C2
C6-C1-C7
O2-C30-C24
C35-C36-Cl3
121.3(3)
119.9(3)
120.5(3)
119.9(3)
121.5(3)
116.9(3)
124.4(3)
123.1(3)
119.9(2)
C8-C7-C1
C7-C8-C9
C10-C9-C8
C9-C10-C11
C9-C10-C13
C12-C11-C10
C12-C13-C10
C19-C20-Cl2
O4-C57-C56
130.3(3)
118.1(2)
115.2(3)
107.3(3)
110.6(2)
86.5(3)
85.5(2)
119.2(3)
123.5(2)
C16-C13-C15
C15-C13-C10
C16-C13-C12
C12-C14-C8
C9-C8-C14
O1-C9-C8
C3-C4-Cl1
O3-C46-C40
C51-C52-Cl4
110.1(3)
115.9(3)
112.7(4)
110.7(2)
115.9(2)
122.9(3)
119.9(3)
123.1(2)
120.0(2)
is -31.92(1)º. All these parameters indicate that there is lack
of conjugation in the system of C7-C8-C9-O2. However, there
is also a strong intermolecular O-H···O hydrogen bond (Table-5)
between the carbonyl and hydroxy groups which link the
molecules into a two-dimesional network, in which they may
be effective in the stabilization of the structure.
Conclusion
Three (1R, 5R)-(-)3-arylideneopinone derivatives (2a, 2b
and 2c) were successfully synthesized and characterized by
single-crystal X-ray diffraction method. These compounds
crystallize on three different space group belongs P212121, P32
and P21 respectively. There is also a strong intermolecular
O–H···O hydrogen bond between the carbonyl and hydroxy
groups in 2a and 2b, but there are lack of inetermolecular
hydrogen in 2c.
TABLE-5
HYDROGEN BOND LENGTHS (Å) AND BOND
ANGLES (º) FOR THE COMPOUND 2b
ACKNOWLEDGEMENTS
D-H···A
d(D-H)
0.88(5)
D(H···A) D(D···A)
1.91(5) 2.775(2)
∠DHA
169(4)
O1-H1A···O2i
The authors acknowledged the financial support received
from Forestry Public Sector Research Fund of State Forestry
Administration of China (Grant No. 201104015) and from the
Committee of National Natural Science Foundation of China
(Grant No. 30972316 and No. 31170538), and a project funded
by the Priority Academic Program Development of Jiangsu
Higher Education institutions. Thanks are also due to Mr. Lai
Jie who provided the starting material.
Symmetry code: (i) –x + y + 1/2, -x + 1, z-2/3
The compound 2c crystallizes in the orthorhombic space
group P21. The molecular structure of the compound 2c is
shown in Fig. 4. There are four crystallographically indepen-
dent molecules in the asymmetric unit different from 2a and
2b. The selected bond lengths and bond angles are listed in
Table-6. The C-Cl bond distances are in the range of 1.736(3)-
1.743(3) Å. There are lack of inetermolecular hydrogen and
π-π stacking interactions, the molecular strucuture is is
stablilized by van der Waals forces.
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