Synthesis of Molecular Glasses
1247
rate of 10K=min under nitrogen atmosphere. The glass tran-
sition temperatures (Tg) were determined from the second
heating. The XRD analysis was performed using diffractome-
ter DRON-UM2. Diffraction patterns were recorded at 30 kV
and 20 mA in 1ꢂsecꢁ1 detector’s movement speed, intensity
was measured every 2ꢂ ¼ 0.02ꢂ. A flat diffracted beam pyro-
litic graphite monochromator was used to remove fluorescent
X-rays. Compound 1 was made according to Ref. [17].
layer was dried over anhydrous MgSO4, filtered, and ethyl
acetate was removed. The residue was dissolved in 40cm3
methanol and, after keeping at 5ꢂC, crystals formed. The
crystalline product was filtered off, washed with 2-propanol,
and recrystallized from methanol. Yield 6 g (45%); mp 198–
200ꢂC; IR (KBr): ꢃꢀ¼ 3371 (OH), 3036 (CHarom), 2896, 2666
(CHaliph), 1653 (CHO), 1604, 1555, 1491 (C¼C, C–N), 943,
822, 791, 768, 702 (CH¼CH of mono- and 1,2,4-trisubstituted
1
benzenes) cmꢁ1; H NMR (CDCl3, 300 MHz): ꢀ ¼ 9.61 (s,
CHO), 7.57–7.22 (m, 7H, Ar), 6.52 (d, J7,8 ¼ 8.6 Hz, H-8
of Ht), 4.43–4.33 (m, CH), 3.83–3.56 (m, NCH2), 3.16 (dd,
1H, JAB ¼ 16.2, JAX ¼ 4.1 Hz, HA of CH2CH), 2.93 (dd, 1H,
JAB ¼ 16.2, JBX ¼ 5.3 Hz, HB of CH2CH), 2.87–2.78 (m, OH)
ppm; APCI-MS: m=z (%) ¼ 254 [Mþ H]þ (100).
rac-3-Acetyl-6-(1,3-dioxoindan-2-ylmethylene)-1-phenyl-
1,2,3,4-tetrahydroquinoline (2, C27H21NO4)
Compound rac-1 (20 g, 0.06 mol) and 9.5 g 1,3-indandione
(0.06 mol) were stirred in 170 cm3 ethanol at room tempera-
ture overnight. The crystalline product that had been formed
was filtered off, washed with diethyl ether:n-hexane¼ 1:2 and
recrystallized from toluene. Yield 20.6 g (75%); mp 237–
239ꢂC; IR (KBr): ꢃꢀ¼ 3060 (CHarom), 2995, 2754 (CHaliph),
1727 (OC¼O, C¼O), 1667 (C¼O), 1613, 1594, 1567, 1464
(C¼C, C–N), 937, 834, 779, 736, 704, 677 (CH¼CH of
u=l-3-Oxiranylmethoxy-1-phenyl-1,2,3,4-tetrahydro-
quinoline-6-carboxaldehyde (5)
To 27cm3 epichlorohydrin (0.34 mol) 6 g rac-4 (0.02 mol)
were added and stirred vigorously at 35–40ꢂC. During
the reaction 7.6 g 85% KOH (0.12 mol) and 2.7 g Na2SO4
(0.02 mol) were added in 5 equal portions every hour with
prior cooling to 30ꢂC. The reaction mixture was stirred at
35–40ꢂC overnight. After termination of the reaction (control
with TLC, diethyl ether:n-hexane¼ 2:1), the mixture was
extracted with ethyl acetate. The organic layer was dried over
anhydrous MgSO4, filtered, and ethyl acetate was removed
to give 6 g of crude product u=l-5, which could be used in
the further synthesis of u=l-6 without purification.
mono-, 1,2-di- and 1,2,4-trisubstituted benzenes) cmꢁ1 1H
;
NMR (CDCl3, 300 MHz): ꢀ ¼ 8.49 (s, CH of methine), 8.09
(dd, J7,8 ¼ 8.8, J7,5 ¼ 1.6 Hz, H-7 of Ht), 7.94–7.21 (m, 10H,
Ar), 6.57 (d, J7,8 ¼ 8.8Hz, H-8 of Ht), 5.45–5.37 (m, CH),
3.96–3.73 (m, NCH2), 3.26 (dd, 1H, JAB ¼ 16.5, JAX ¼ 4.3 Hz,
HA of CH2CH), 3.18 (dd, 1H, JBX ¼ 4.7 Hz, HB of CH2CH),
2.05 (s, CH3) ppm; APCI-MS: m=z (%) ¼ 424 [M þ H]þ
(100), 364 [Mþ H–COOCH3]þ (20).
rac-3-Hydroxy-6-(1,3-dioxoindan-2-ylmethylene)-1-phenyl-
1,2,3,4-tetrahydroquinoline (3, C25H19NO3)
u=l-3-Oxiranylmethoxy-6-(1,3-dioxoindan-2-ylmethylene)-1-
phenyl-1,2,3,4-tetrahydroquinoline (6, C28H23NO4)
Compound rac-2 (20.6 g, 0.05 mol) was dissolved in 40cm3
dioxane by heating. The solution was cooled to room tem-
perature, and 40 cm3 37% hydrochloric acid were added.
The reaction mixture was refluxed for 3.5 h. After termination
the mixture was stored at room temperature overnight. The
crystalline product was filtered off, washed with water until
neutral, and and then with 2-propanol. The product was recrys-
tallized from toluene. Yield 13.8g (74%); mp 198–200ꢂC; IR
(KBr): ꢃꢀ¼ 3412 (OH), 3051 (CHarom), 2891, 2641 (CHaliph),
1714, 1668 (C¼O), 1614, 1540, 1565, 1439 (C¼C, C–N),
934, 828, 734, 698, 677 (CH¼CH of mono-, 1,2- and 1,2,4-
Compound u=l-5 (6g, 0.02mol) was dissolved in 15cm3
methanol by heating. The mixture was cooled to room tem-
perature, and 2.9 g 1,3-indandione (0.02 mol) were added. The
reaction mixture was stirred at room temperature for 3 days.
At the end of the reaction (control with TLC, diethyl ether:n-
hexane¼ 2:1) the crystalline product was filtered off, washed
with 2-propanol, and recrystallized from 2-propanol:ethyl
acetate ¼ 2:1. Yield 7 g (82%); mp 164–166ꢂC; IR (KBr):
ꢃꢀ¼ 3362 (CHarom), 2999, 2894 (CHaliph), 1714, 1670 (C¼O),
1617, 1539, 1509, 1440 (C¼C, C–N), 903, 824, 732, 703, 697,
676 (CH¼CH of mono-, 1,2-di-, and 1,2,4-trisubstituted ben-
1
trisubstituted benzenes) cmꢁ1; H NMR (CDCl3, a few drops
1
zenes) cmꢁ1; H NMR (CDCl3, 300MHz): ꢀ ¼ 8.54 (s, 0.5H
of DMSO, 300 MHz): ꢀ ¼ 8.38 (s, CH of methine), 8.06 (dd,
J7,8 ¼ 8.9, J7,5 ¼ 1.7 Hz, H-7 of Ht), 7.87–7.25 (m, 10H, Ar),
6.47 (d, J7,8 ¼ 8.9 Hz, H-8 of Ht), 5.10 (d, J ¼ 3.7Hz, OH),
4.37–4.27 (m, CH), 3.80 (dd, 1H, JAB ¼ 12.2 Hz,
JAX ¼ 2.1 Hz, HA of NCH2), 3.62 (dd, 1H, JBX ¼ 5.6 Hz, HB
of NCH2), 3.14 (dd, 1H, JAB ¼ 15.9, JAX ¼ 4.0 Hz, HA of
CH2CH), 2.94 (dd, 1H, JBX ¼ 6.4 Hz, HB of CH2CH) ppm;
APCI-MS: m=z (%) ¼ 382 [Mþ H]þ (100).
CH of methine of one diastereomer), 8.52 (s, 0.5H CH of
methine of other diastereomer) 8.09–8.00 (m, H-7 of Ht),
7.94–7.25 (m, 10H, Ar), 6.56 (d, 0.5H, J7,8 ¼ 8.8 Hz, H-8 of
one diastereomer), 6.53 (d, 0.5H, J7,8 ¼ 8.8 Hz, H-8 of other
diastereomer), 4.18–4.08 (m, 1H, NCH2CHO), 3.99–3.40 (m,
4H, NCH2, OCH2), 3.29–2.99 (m, 3H, CH2CHO of epoxy gr.),
2.82–2.75 (m, 1H, one H of PhCH2CH), 2.64–2.56 (m, 1H,
another H of PhCH2CH) ppm; APCI-MS: m=z (%) ¼ 438
[Mþ H]þ (100), 364 [Mþ H ꢁ OCH2CHCH2O]þ (16).
rac-3-Hydroxy-1-phenyl-1,2,3,4-tetrahydroquinoline-6-
carbaldehyde (4, C16H15NO2)
Compound rac-1 (22 g, 0.07mol) was dissolved in 40cm3
methanol by heating. A solution of 4.7 g 85% KOH
(0.07 mol) in 7 cm3 H2O was added to the mixture. The reac-
tion mixture was refluxed for 35 min. When the reaction was
over, the mixture was extracted with ethyl acetate. The organic
u=l-1,3-Bis-{3-hydroxy-4-[6-(1,3-dioxoindan-2-ylmethylene)-
1-phenyl-1,2,3,4-tetrahydroquinolin-3-yloxy]-1-thiabuthyl}-
benzene (7a, C62H52N2O8S2)
Compound u=l-6 (3g, 7 mmol) and 25cm3 MEK were
refluxed for 10 min. The mixture was cooled to room temper-