References and Notes
<A NAME="RG00810ST-1">1</A>
Kula P.
Dąbrowski R.
Tykarska M.
Phase Transitions
2007,
80:
771
<A NAME="RG00810ST-2">2</A>
Lagerwall ST.
Dahlgren A.
Jägemalm P.
Rudquist P.
Dhavé K.
Pauwels H.
Dąbrowski R.
Drzewiński W.
Adv. Funct. Mater.
2001,
11:
87
<A NAME="RG00810ST-3">3</A>
Dąbrowski R.
Gąsowska J.
Otón J.
Piecek W.
Przedmojski J.
Tykarska M.
Displays
2004,
25:
9
<A NAME="RG00810ST-4">4</A>
Kula P.
Dąbrowski R.
Kenig K.
Chyczewska D.
Ferroelectrics
2006,
343:
19
<A NAME="RG00810ST-5">5</A>
Havens SJ.
Hergenrother PM.
J. Org. Chem.
1985,
50:
1763
<A NAME="RG00810ST-6">6</A>
Synthesis of 4-Benzyloxy-4′-ethynylbiphenyl (3)
4-Benzyloxy-4-bromobiphenyl
(128.8 g, 0.38 mol), Et3N (57.6 g, 0.57 mol), DBU (29
g, 0.19 mol), PdCl2
(PPh3)2 (2
g, 2.85 mmol), CuI (1 g, 5.27 mmol), and THF (400 mL) have been
added in a 1 L nitrogen-filled flask. The mixture were heated(boiling)
for 5 min, and 2-methyl-3-butyn-2-ol (38.3 g, 0.456 mol) has been
dropped in slowly. After 4 h of stirring the GC-MS analysis was
performed. To complete the reaction, 25% of the initial
amount of 2-methyl-3-butyn-2-ol and 0.5g of PdCl2
(PPh3)2 were
added and stirred for additional 8 h. Then the reaction mixture
was poured onto H2O and the solid was filtered off, dried
and washed using CH2Cl2 (0.5 L). The obtained
4-[4′-(benzyloxy)biphenyl-4-yl]-2-methylbut-3-yn-2-ol
(112 g, 0.33 mol), NaH (1.1 g, 46 mmol) and dry toluene (1 L) have
been placed in a flask equipped with column and distillation head
to distill off the emerging acetone. When the distillate temperature
reached the bp of toluene, the reaction mixture was cooled down
and poured onto the H2O. The organic layer was separated
and poured through active carbon pad and dried over anhyd MgSO4.
The toluene solution was concentrated and the final product crystallized
in freezer. 4-Benzyloxy-4′-ethynyl-biphenyl (3) was obtained in 57% yield (61.5
g, 0.217 mol).
MS (EI 70eV): m/z = 284 [M+
],
193, 165, 139, 91, 65. IR (neat): 3282, 3061, 3036, 2861, 2359,
2340, 1600, 1488, 1454, 1380, 1284, 1246, 1026, 1008, 812, 738,
619. ¹H NMR (200 MHz, CDCl3): δ = 7.53
(m, 2 H, ArH), 7.51 (m, 5 H, ArH), 7.43 (m, 2 H, ArH), 7.39 (m,
2 H, ArH), 7.03 (m, 2 H, ArH), 5.10 (s, CH2), 3.11 (s,
1 H CºCH). ¹³C NMR (50 MHz, CDCl3): δ = 158.89
(1 C), 141.31 (1 C), 137.04 (1 C), 133.15 (1 C), 132.74 (2 CH),
128.84 (2 CH), 128.32 (2 CH), 128.25 (2 CH), 127.69 (1 CH), 126.70
(2 CH), 120.49 (1 C), 115.44 (2 CH), 83.87 (1 C), 77.87 (1 CH),
70.28 (1 CH2). Mp 156.7-157.2 ˚C
(dec.).
<A NAME="RG00810ST-7">7</A>
1-[(
S
)-4-(1-Methylheptyloxycarbonyl)phenyl]-2-[4′-(2,2,3,3,4,4,4-heptafluorobutoxyhexyloxy)biphenyl-4-yl]ethane
(6.6)
MS (EI 70eV): 712 [M+
],
465, 183, 55. MS (ESI+, MeOH-H2O):
735 [M + Na+], 615.
IR (neat): 2934, 2856, 1710, 1608, 1499, 1354, 1222, 1103, 810,
736 cm-¹. ¹³C
NMR (50 MHz, CDCl3): δ = 166.29
(1 COO), 158.55 (1 CO), 146.94 (1 CEt), 139.63 (1 CEt), 138.69 (1
C), 133.38 (1 C), 129.67 (2 CH), 128.83 (2 CH), 128.75 (1 CCOO),
128.48 (2 CH), 127.95 (2 CH), 126.67 (2 CH), 114.74 (2 CH), 73.13
(1 COOC), 71.59 (1 CH2O), 67.88 (1 CH2O),
37.87 (1 CH2Ar), 37.12 (1 CH2Ar), 36.11 (1
CH2), 31.77 (1 CH2), 29.41 (1 CH2),
29.19 (2 CH2), 25.82 (1 CH2), 25.60 (1 CH2),
25.43 (1 CH2), 22.61 (1 CH2), 20.11 (CH3),
14.08 (CH3).
<A NAME="RG00810ST-8">8</A>
1-[(
S
)-3-Fluoro-4-(1-methylheptyloxycarbonyl)phenyl]-2-[4′-(2,2,3,3,4,4,4-heptafluorobutoxybutoxy)biphenyl-4-yl]ethane
(12.4)
MS (EI, 70eV): m/z = 702 [M+
],
465, 183, 55. MS (ESI+, MeOH-H2O): m/z = 725 [M + Na+],
605. IR (neat): 2950, 2859, 1699, 1622, 1499, 1354, 1219, 1117,
971, 817, 734.
<A NAME="RG00810ST-9">9</A>
Drzewiński W.
Dąbrowski R.
Czupryński K.
Pol. J. Chem.
2002,
76:
273
<A NAME="RG00810ST-10">10</A>
Żurowska M.
Dąbrowski R.
Dziaduszek J.
Czupryński K.
Skrzypek K.
Filipowicz M.
Mol. Cryst. Liq. Cryst.
2008,
495:
145
