Supporting information for
synthesis and spatial structure of new chiral dopants from allobetuline series for
cholesteric liquid-crystal compositions
Nikolay L. Babaka  Oleg V. Shishkina,c  Svitlana V. Shishkinaa,c  Ivan M. Gellaa,c 
Vladimir I. Musatova  Nataliya B. Novikovaa Victoria V. Lipsona-c@
a
State Scientific Institution “Institute for Single Crystals” of the National Academy of Sciences
of Ukraine, 61001, Kharkov, Ukraine.
b
Medicinal Chemistry Department, State Institution “V.Ya. Danilevsky Institute for Endocrine
Pathology Problems” of the National Academy of Medical Sciences of Ukraine, Artema St., 10,
61002 Kharkov, Ukraine, *E-mail: lipson@ukr.net
c
V. N. Karazin Kharkiv National University, 4 Svobody sq., Kharkiv 61122, Ukraine
Table of contents
Spectroscopic and analytical data……………………………………………………………S2
General methods ……………………………………………………………………………...S2
Synthetic procedure and characterization data for compounds 4 …………………….….S2
Synthetic procedure and characterization data for compounds 5 …………….…….…....S4
Synthetic procedures and characterization data for compounds 6 …………...……….….S6
Synthetic procedures and characterization data for compounds 7, 8...……...…………....S8
S1
Spectroscopic and analytical data
General methods
All commercially available reagents and solvents were purchased from Sigma Aldrich and used
without further purification. 1H NMR and 13C NMR spectra were recorded on a Varian Mercury200 spectrometer 200 MHz and Varian Mercury-400 spectrometer 100 MHz, respectively, with
TMS as an internal reference and CDCl3 as a solvent. The IR spectra were performed between
4,000 and 400 cm-1 on a Perkin Elmer Spectrum One FT-IR spectrometer using the KBr pellets.
Elemental analyses were carried out on an EA 3000 Eurovector elemental analyzer. Melting
points were determined on a Kofler hot bench. The progress of reactions and also the purity of
the obtained compounds were monitored by TCL on Alugram® Xtra SIL G/UV254 plates with
hexane - ethylacetate (10:1) as an eluent.
General procedure for the synthesis of (E)-2-(4-chlorobenzylidene)allobetulone (4)
A mixture of 1 g (2.3 mmol) of allobetulon (3) and 0.35 g (2.5 mmol) 4-chlorbezaldehyde in
30 mL 2-methoxyethanol, containing a catalytic amount of potassium hydroxide was refluxed
for 8 h. The solvent was evaporated under reduced pressure to a volume of 10 mL, the residue
was cooled, and the white amorphous precipitate was filtered off.
(E)-2-(4-chlorobenzylidene)allobetulone (4)
White solid, yield 78%, 1 g, mp 173-174 °C.1H NMR (400 MHz, CDCl3) δ 7.40 (s, 1H, CHvinil),
7.33 s (s, 4H, Ar-H), 3.75 (s,1H, 28-CHB), 3.52 (s, 1H, 19-CH), 3.42 (s, 1H, 28-CHA), 3.01 (d, J
= 16.1 Hz, 1H, 1-CHe), 2.19 (d, J = 15.1 Hz, 1H, 1-CHa), 1.13, 1.10, 0.99, 0.94, 0.91, 0.78 (all
s, 21H, 7×CH3).
S2
Cl
O
O
C NMR (101 MHz, CDCl3) δ 208.19, 136.19, 135.09, 134.71, 134.61, 131.73, 128.96, 88.18,
13
71.56, 53.29, 49.31, 47.08, 45.52, 44.93, 41.77, 41.10, 40.75, 37.03, 36.86, 36.58, 34.59, 32.99,
29.75, 29.11, 26.84, 26.70, 26.54, 24.85, 22.64, 22.09, 20.61, 16.41, 15.54, 13.73.
Cl
O
O
S3
Cl
O
O
General procedure for the synthesis of (E)-2-(4-chlorophenylmethylidene)allobetuline (5)
To suspension of 0.5 g (0.9 mmol) of α,β-unsaturated ketone (4) in 10 mL of propan-2-ol 0.1g
(2.7 mmol) of NaBH4 were added under stirring. The reaction mixture was stirred under room
temperature (RT) for 16 h and than was diluted by water (20 mL) and stirred for 1 h. The white
amorphous precipitate was filtered off.
(E)-2-(4-chlorophenylmethylidene)allobetuline (5)
White solid, yield 0.5 g ( 99 %), mp 233-235 °C.1H NMR (400 MHz, CDCl3) δ 7.25 (d, J = 8.3
Hz, 2H, Ar-H), 7.11 (d, J = 8.2 Hz, 2H, Ar-H), 6.64 (s, 1H, CHvinil), 3.83 (s, 1H, 3-CHa), 3.73 (d,
S4
J = 7.8 Hz, 1H, 28-CHB), 3.48 (s, 1H, 19-CH), 3.41 (d, J = 7.7 Hz, 1H, 28-CHA), 2.93 (d, J =
12.7 Hz, 1H, 1-CHe), 1.10, 0.90, 0.76, 0.71, 0.66 (all s, 21H, 7×CH3).
Cl
O
O
C NMR (101 MHz, CDCl3) δ 141.48, 136.77, 131.92, 130.35, 128.51, 121.84, 88.15, 81.22,
13
71.44, 64.60, 56.27, 50.59, 47.02, 42.32, 41.82, 41.65, 41.04, 40.98, 40.64, 36.95, 36.46, 34.34,
33.97, 32.90, 29.02, 28.73, 26.65, 26.54, 26.45, 25.56, 24.75, 21.38, 18.58, 16.74, 15.79, 13.69.
Cl
O
O
S5
Cl
O
O
General procedure for the synthesis of (2R,3R)-3-(4´-chlorophenyl)-2,2´-spirooxyronoallobetuline (6)
To solution of 0.3 g (0.53 mmol) of allobetuline derivative (5) in dichloromethane (5 mL) 0.1 g
(0.59 mmol) of m-chloroperoxybenzoic acid (m-ClPBA) was added (Scheme 3) and reaction
mixture was stirred for 14 h under RT. At the end of reaction mixture was washed with the 10 %
solution of NaHCO3 in water (3×10 mL). The organic phase was dried over anhydrous
magnesium sulfate, and the solvent was removed in vacuo.
(2R,3R)-3-(4´-chlorophenyl)-2,2´-spirooxyronoallobetuline (6)
White solid, yield 0.3 g ( 97 %), mp 244-246 ºC 1H NMR (400 MHz, CDCl3) δ 7.25 (d, J = 8.0
Hz, 2H, Ar-H), 7.14 (d, J = 8.2 Hz, 2H, Ar-H), 4.35 (s, 1H, 3´-CH), 3.64 (d, J = 7.3 Hz, 1H, 28CHB), 3.53 (s, 1H, 3-CHa), 3.39 (s, 1H, 19-CH), 3.34 (d, J = 7.0 Hz, 1H, 28-CHA), 2.05 (s, 1H,
OH), 1.04, 0.82, 0.76, 0.70, 0.29 (all s, 21H, 7×CH3).
S6
Cl
O
O
O
C NMR (101 MHz, CDCl3) δ 134.74, 133.36, 128.35, 128.15, 128.03, 87.84, 78.46, 71.14,
13
66.21, 59.97, 55.69, 50.57, 46.71, 41.35, 40.70, 40.63, 39.77, 39.49, 36.66, 36.17, 33.89, 33.59,
32.60, 28.74, 28.63, 26.24, 26.13, 24.48, 20.85, 17.73, 16.58, 16.47, 15.51, 13.37.
Cl
O
O
O
S7
Cl
O
O
O
General procedure for the synthesis of (1S,2S)-,(1R,2R)-1- (4´-chlorophenyl)-2,2´spirocyclopropylallobetulone (7, 8)
A mixture of 0.08 g (1.8 mmol) 50 % sodium hydride and 0.43 g (1.95 mmol) of trimethylsulfoxonium iodide in dry DMF (15 mL) was stirred until hydrogen evolution (Scheme 4). Than
to mixture heated until 60 °С 0.5 g (0.9 mmol) of α,β-unsaturated ketone (4) was added. After
0.5 h this reaction mixture was diluted by water (50 mL) and white amorphous precipitate was
filtered off. The precipitate was dried at 50 °С and a mixture of isomers was divided by column
chromatography with silica gel and dichloromethane as eluent.
(1S,2S)-1- (4´-chlorophenyl)-2,2´-spirocyclopropylallobetulone (7)
White solid, yield 69 %, 0.35g, mp 252-253 ºC 1H NMR (400 MHz, CDCl3) δ 7.23 (d, J = 6.0
Hz, 2H,Ar-H), 6.97 (d, J = 8.1 Hz, 2H, Ar-H), 3.70 (d, J = 7.4 Hz, 1H, 28-CHB), 3.45 (s, 1H, 19CH), 3.39 (d, J = 7.6 Hz, 1H, 28-CHA), 2.90 (t, J = 8.2 Hz, 1H, 2´-CH), 1.10, 1.05, 0.89,
0.87,0.85, 0.74, 0.53 (all s, 21H, 7×CH3).
S8
Cl
O
O
C NMR (101 MHz, CDCl3) δ 217.36, 135.26, 132.44, 130.43, 128.07, 87.79, 71.17, 54.24,
13
48.30, 46.68, 45.92, 41.36, 40.66, 40.49, 40.28, 37.05, 36.78, 36.67, 36.18, 34.16, 32.82, 32.63,
32.14, 29.62, 28.75, 26.35, 26.27, 26.18, 24.46, 22.98, 22.85, 21.22, 19.97, 15.39, 14.60,
Cl
O
O
S9
Cl
O
O
(1R,2R)-1- (4´-chlorophenyl)-2,2´-spirocyclopropylallobetulone (8)
White solid, yield 29 %, 0.15g, mp 115-116 ºC 1H NMR (400 MHz, CDCl3) δ 7.25 (d, J = 7.8
Hz, 1H, Ar-H), 7.03 (d, J = 7.8 Hz, 1H, Ar-H), 3.73 (d, J = 7.3 Hz, 1H, 28-CHB), 3.47 (s, 1H,
19- CH), 3.41 (d, J = 7.8 Hz, 1H, 28-CHA), 2.71 (d, J = 7.7 Hz, 1H, 2´-CH ), 1.10, 1.06, 0.98,
0.94, 0.89, 0.83, 0.73 (all s, 21H, 7×CH3).
Cl
O
O
C NMR (101 MHz, CDCl3) δ 216.96, 135.80, 132.31, 130.75, 129.57, 128.40, 127.68, 87.80,
13
S10
71.21, 54.29, 48.30, 46.68, 46.05, 44.58, 41.38, 40.73, 40.31, 37.54, 36.66, 36.21, 34.14, 33.73,
32.78, 32.63, 31.31, 29.42, 28.74, 27.46, 26.29, 26.18, 24.46, 22.80, 21.38, 20.19, 15.43, 15.40,
13.33.
S11
Cl
O
O
Cl
O
O
S12