AAV 12: Hydrosilylierung

In einer Argonatmosphäre werden das entsprechende Olefin (1 Äqu.) und das Hydrosiloxan/-carbosilan (1-2 Äqu.) in absolutem Toluol (3 ml pro 1 mmol Olefin) gelöst und mit 1 Tr.

Karstedt’s Katalysator versetzt. Die Reaktionsmischung wird dann 24 h bei Raumtemperatur gerührt. Der Reaktionsverlauf wird dünnschichtchromatographisch verfolgt. Nach vollständiger Umsetzung wird das Reaktionsgemisch unter vermindertem Druck eingeengt.

Das Rohprodukt wird chromatograpisch gereinigt.

7.2. Synthese der 3’-[4-(4-Alkoxybenzoyloxy)benzoyloxy]-4-{4-[11-(1,1,3,3,5,5,5-heptamethyltrisiloxan-1-yl)undec-1-yloxy])benzoyloxy}biphenyle Si3-11Bn

Die im Folgenden beschriebenen Verbindungen wurden mittels einer Hydrosilylierungs-reaktion nach der allgemeinen Arbeitsvorschrift AAV 12 dargestellt.

7.2.1. 3’-[4-(4-Methoxybenzoyloxy)benzoyloxy]-4-{4-[11-(1,1,3,3,5,5,5-heptamethyl-trisiloxan-1-yl)undec-1-yloxy])benzoyloxy}biphenyl Si3-11B1

O

Ansatzgröße:

3’-[4-(4-Methoxybenzoyloxy)benzoyloxy]- 0.25 g (0.35 mmol) 4-(undec-10-enyloxy)benzoyloxybiphenyl

O O

O O

Me Me Me O

O OMe

(CH₂)₁₁ O Si

OSi Si

Me Me Me

Me

1,1,1,3,3,5,5-Heptamethyltrisiloxan 0.094 g (0.42 mmol)

Karstedt-Katalysator 1 Tr.

Toluol 5 ml

Das Rohprodukt wurde mittels fliehkraftvermittelter präparativer Dünnschichtchromato-graphie (Eluent CHCl3;Rf = 0.19) gereinigt.

Ausbeute: 0.146 g (45 % d. Th.), farbloser Feststoff Smp.: 130 °C

C52H66O10Si3 M = 935.34 g/mol

berechnet: C, 66.78; H, 7.11 gefunden: C, 67.2; H, 7.15

1H-NMR (400 MHz, CDCl3): δ 8.29 (d, ³J = 8.9 Hz, 2H, Ar-H), 8.15 (m, 4H, Ar-H), 7.63 (d,

3J = 8.7 Hz, 2H, Ar-H), 7.49 (d, ³J = 4.9 Hz, 2H, Ar-H), 7.43 (m, 1H, Ar-H), 7.36 (d, ³J = 8.9 Hz, 2H, Ar-H), 7.27 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.21 (m, 1H, Ar-H), 6.98 (m, 4H, Ar-H), 4.03 (m, 4H, OCH2), 3.90 (s, 3H, OCH3), 1.83 (m, 2H, OCH2CH2), 1.47 (m, 2H, OCH2CH2CH2), 1.27 (m, 14H, CH2), 0.49 (m, 2H, SiCH2), 0.07 [s, 9H, Si-(CH3)3], 0.04 [s, 6H, Si-(CH3)2], 0.005 [s, 6H, Si-(CH3)2].

13C-NMR (125 MHz, CDCl3): δ 164.75, 164.31, 164.11, 164.07, 163.48, 155.29, 151.24, 150.78, 142.08, 137.66, 132.35, 132.21 (4C), 131.74 (2C), 129.74, 128.14 (2C), 126.86, 124.59, 122.10 (2C), 122.10 (2C), 122.02, 121.45, 120.47, 120.34, 120.33, 114.28 (2C), 113.93, 68.37, 55.57, 33.50, 29.69, 29.64, 29.63, 29.45 (2C), 29.19, 26.07, 23.31, 18.39, 1.92 (3C), 1.38 (2C), 0.32 (2C).

29Si-NMR (99.3 MHz, CDCl3): δ 7.48, 7.03, -21.06.

7.2.2. 3’-[4-(4-Butyloxybenzoyloxy)benzoyloxy]-4-{4-[11-(1,1,3,3,5,5,5-heptamethyl-trisiloxan-1-yl)undec-1-yloxy])benzoyloxy}biphenyl Si3-11B4

O O

O

O O

OC₄H₉ O

(CH₂)₁₁ O O Si

OSi Si

Me

Me Me

Me Me Me

Ansatzgröße: Me

3’-[4-(4-Butyloxybenzoyloxy)benzoyloxy]- 0.18 g (0.24 mmol) 4-(undec-10-enyloxy)benzoyloxybiphenyl

1,1,1,3,3,5,5-Heptamethyltrisiloxan 0.05 g (0.24 mmol)

Karstedt-Katalysator 1 Tr.

Toluol 3 ml

Das Rohprodukt wurde mittels Säulenchromatographie (Eluent CHCl3 Rf = 0.21) gereinigt.

Ausbeute: 0.172 g (72 % d. Th.), farbloser Feststoff

Phasenumwandlungstemperaturen/°C (-enthalpien/kJ mol^-1) Cr 93 (10.9) SmCPF[*^] 113 (17.1) Iso

C55H72O10Si3 M =977.42 g/mol

berechnet: C, 67.59; H, 7.42 gefunden: C, 65.65; H, 7.76

1H-NMR (400 MHz, CDCl3): δ 8.29 (d, ³J = 8.9 Hz, 2H, Ar-H), 8.15 (d, ³J = 8.7 Hz, 4H, Ar-H), 7.65 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.49 (d, ³J = 4.9 Hz, 2H, Ar-H), 7.43 (m, 1H, Ar-H), 7.37 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.27 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.21 (m, 1H, Ar-H), 6.97 (d, ³J = 8.7 Hz, 2H, Ar-H), 6.96 (d, 2H, ³J = 8.7 Hz, Ar-H), 4.04 (m, 4H, OCH2), 1.82 (m, 4H, OCH2CH2), 1.49 (m, 4H, OCH2CH2CH2), 1.27 (m, 12H, CH2), 0.99 (t, ³J = 6.5 Hz, 3H, CH3),

0.51 (m, 2H, SiCH2), 0.07 [s, 9H, Si-(CH3)3], 0.04 [s, 6H, Si-(CH3)2], 0.004 [s, 6H, Si-(CH3)2].

13C-NMR (125 MHz, CDCl3): δ 164.73, 164.29, 164.13, 163.68, 163.45, 155.29, 151.21, 150.75, 142.05, 137.64, 132.31 (4C), 132.20 (2C), 131.72 (2C), 129.72, 128.13 (2C), 126.79, 124.57, 122.08 (2C), 122.02 (2C), 121.42, 120.93, 120.45, 120.33, 114.36 (2C), 114.26, 68.36, 68.08, 33.50, 31.20, 29.69, 29.65, 29.63, 29.46 (2C), 29.19, 26.08, 25.99, 23.32, 22.64, 19.28, 18.40, 13.90, 1.94 (3C), 1.40 (2C), 0.34 (2C).

29Si-NMR (99.3 MHz, CDCl3): δ 7.48, 7.04, -21.06.

7.2.3. 3’-[4-(4-Hexyloxybenzoyloxy)benzoyloxy]-4-{4-[11-(1,1,3,3,5,5,5-heptamethyl-trisiloxan-1-yl)undec-1-yloxy])benzoyloxy}biphenyl Si3-11B6

O O

O

O O

OC₆H₁₃ O

(CH₂)₁₁ O OSi

OSi Si

Me

Me Me

Me Me Me

Ansatzgröße: Me

3’-[4-(4-Hexyloxybenzoyloxy)benzoyloxy]-4-(undec- 0.3 g (0.38 mmol) 10-enyloxy)benzoyloxybiphenyl

1,1,1,3,3,5,5-Heptamethyltrisiloxan 0.085 g (0.38 mmol)

Karstedt-Katalysator 1 Tr.

Toluol 5 ml

Das Rohprodukt wurde mittels Säulenchromatographie (Eluent CHCl3, Rf = 0.08) und anschließende Kristallisation aus Essigsäureethylester gereinigt.

Ausbeute: 0.145 g (38 % d. Th.), farbloser Feststoff

Phasenumwandlungstemperaturen/°C (-enthalpien/kJ mol^-1) Cr 100 (31.59) SmCPF[*^] 118 (20.90) Iso

C57H76O10Si3 M = 1005.48 g/mol

berechnet: C, 68.09; H, 7.62 gefunden: C, 67.97; H, 7.64

1H-NMR (400 MHz, CDCl3): δ 8.28 (d, ³J = 8.7 Hz, 2H, Ar-H), 8.14 (d, ³J = 8.9 Hz, 4H, Ar-H), 7.63 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.49 (d, ³J = 5.2 Hz, 2H, Ar-H), 7.44 (s, 1H, Ar-H), 7.36 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.27 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.21 (m, 1H, Ar-H), 6.97 (d, ³J = 8.9 Hz, 2H, Ar-H), 6.96 (d, ³J = 8.9 Hz, 2H, Ar-H), 4.03 (m, 4H, OCH2), 1.79 (m, 4H, OCH2CH2), 1.44 (m, 4H, CH2), 1.31 (m, 1H, CH2), 0.90 (t, ³J = 7.2 Hz, 3H, CH3), 0.50 (m, 2H, SiCH2), 0.07 [s, 9H, Si-(CH3)3], 0.05 [s, 6H, Si-(CH3)2], 0.005 [s, 6H, Si-(CH3)2].

13C-NMR (125 MHz, CDCl3): δ 164.90, 164.45, 164.29, 163.80, 163.57, 155.40, 151.30, 150.83, 142.14, 137.73, 132.39, 132.28, 131.80, 129.81, 128.21, 126.84, 124.65, 122.15, 122.09, 121.43, 120.94, 120.51, 120.39, 114.40, 114.29, 68.36, 68.32, 33.41, 31.50, 29.59, 29.55, 29.53, 29.35, 29.08, 29.02, 25.96, 25.62, 23.19, 22.54, 18.26, 13.98, 1.78, 1.24, 0.17.

29Si-NMR (99.3 MHz, CDCl3): δ 7.48, 7.03, -21.06.

7.2.4. 3’-[4-(4-Octyloxybenzoyloxy)benzoyloxy]-4-{4-[11-(1,1,3,3,5,5,5-heptamethyl-trisiloxan-1-yl)undec-1-yloxy])benzoyloxy}biphenyl Si3-11B8

O O

O

O O

OC₈H₁₇ O

(CH₂)₁₁ O OSi

OSi Si

Me

Me Me

Me Me Me

Ansatzgröße: Me

3’-[4-(4-Octyloxybenzoyloxy)benzoyloxy]- 0.3 g (0.37 mmol) 4-(undec-10-enyloxy)benzoyloxybiphenyl

1,1,1,3,3,5,5-Heptamethyltrisiloxan 0.082 g (0.37 mmol)

Karstedt-Katalysator 1 Tr.

Toluol 5 ml

Das Rohprodukt wurde mittels Säulenchromatographie (Eluent CHCl3, Rf = 0.29) gereinigt.

Ausbeute: 0.12 g (31 % d. Th.), farbloser Feststoff

Phasenumwandlungstemperaturen/°C (-enthalpien/kJ mol^-1) Cr 94 (20.3) SmCPF[*^] 117 (18.3) Iso

C59H80O10Si3 M = 1033.54 g/mol

berechnet: C, 68.57; H, 7.8 gefunden: C, 68.50; H, 8.30

1H-NMR (400 MHz, CDCl3): δ 8.29 (d, ³J = 8.7 Hz, 2H, Ar-H), 8.14 (d, ³J = 8.9 Hz, 4H, Ar-H), 7.63 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.49 (d, ³J = 4.9 Hz, 2H, Ar-H), 7.43 (s, 1H, Ar-H), 7.37 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.27 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.21 (m, 1H, Ar-H), 6.97 (d, 2H,

3J = 8.8 Hz, Ar-H), 6.96 (d, 2H, ³J = 8.7 Hz, Ar-H), 4.03 (m, 4H, OCH2), 1.81 (m, 4H, OCH2CH2), 1.48 (m, 4H, OCH2CH2CH2), 1.25 (m, 20H, CH2), 0.87 (t, ³J = 6.5 Hz, 3H, CH3), 0.51 (m, 2H, SiCH2), 0.07 [s, 9H, Si-(CH3)3], 0.04 [s, 6H, Si-(CH3)2], 0.003 [s, 6H,

Si-(CH3)2].

13C-NMR (125 MHz, CDCl3): δ 164.93, 164.48, 164.33, 163.83, 163.60, 155.43, 151.33, 150.86, 142.17, 137.76, 132.42 (4C), 132.31 (2C), 131.83 (2C), 129.84, 128.24 (2C), 126.87, 124.68, 122.18 (2C), 122.13 (2C), 121.46, 120.96, 120.54, 120.42, 114.43 (2C), 114.32, 68.39, 68.35, 33.43, 31.78, 29.62, 29.56, 29.55, 29.37, 29.31, 29.20, 29.10, 29.08, 25.99, 25.97 (2C), 23.22, 22.64, 18.28, 14.08, 1.80 (3C), 1.26 (2C), 0.19 (2C).

29Si-NMR (99.3 MHz, CDCl3): δ 7.48, 7.04, -21.06.

7.2.5. 3’-[4-(4-Decyloxybenzoyloxy)benzoyloxy]-4-{4-[11-(1,1,3,3,5,5,5-heptamethyl-trisiloxan-1-yl)undec-1-yloxy])benzoyloxy}biphenyl Si3-11B10

O O

O

O O

OC₁₀H₂₁ O

(CH₂)₁₁ O OSi

OSi Si

Me

Me Me

Me Me Me

Ansatzgröße: Me

3’-[4-(4-Decyloxybenzoyloxy)benzoyloxy]- 0.2 g (0.24 mmol) 4-(undec-10-enyloxy)benzoyloxybiphenyl

1,1,1,3,3,5,5-Heptamethyltrisiloxan 0.056 g (0.25 mmol)

Karstedt-Katalysator 1 Tr.

Toluol 3 ml

Das Rohprodukt wurde mittels Säulenchromatographie (Eluent CHCl3, Rf = 0.37) gereinigt.

Ausbeute: 0.117 g (46 % d. Th.), farbloser Feststoff

Phasenumwandlungstemperaturen/°C (-enthalpien/kJ mol^-1) Cr 61 (12.5) SmCPF[*^] 117 (22.3) Iso

C61H84O10Si3 M = 1061.59 g/mol

berechnet: C, 69.02; H, 7.98 gefunden: C, 69.1; H, 7.85

1H-NMR (400 MHz, CDCl3): δ 8.28 (d, ³J = 8.9 Hz, 2H, Ar-H), 8.14 (d, ³J = 8.9 Hz, 4H, Ar-H), 7.63 (d, ³J = 8.5 Hz, 2H, Ar-H), 7.49 (d, ³J = 5.4 Hz, 2H, Ar-H), 7.44 (s, 1H, Ar-H), 7.36 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.27 (d, ³J = 8.5 Hz, 2H, Ar-H), 7.19 (m, 1H, Ar-H), 6.97 (d, ³J = 8.9 Hz, 2H, Ar-H), 6.96 (d, ³J = 9.1 Hz, 2H, Ar-H), 4.04 (m, 4H, OCH2), 1.81 (m, 4H, OCH2CH2), 1.48 (m, 8H, CH2), 1.25 (m, 22H, CH2), 0.87 (t, ³J = 6.5 Hz, 3H, CH3), 0.51 (m, 2H, SiCH2), 0.07 [s, 9H, Si-(CH3)3], 0.04 [s, 6H, Si-(CH3)2], 0.004 [s, 6H, Si-(CH3)2].

13C-NMR (125 MHz, CDCl3): δ 164.73, 164.28, 164.13, 163.64, 163.40, 155.23, 151.13, 150.66, 141.97, 137.56, 132.22, 132.11, 131.63, 129.64, 128.04, 126.68, 124.48, 121.97, 121.91, 121.26, 120.77, 120.34, 120.22, 114.23, 114.12, 68.20, 68.15, 33.23, 31.68, 29.37, 29.35, 29.18, 29.15, 29.10, 28.91, 28.88, 25.79, 25.77, 23.02, 22.47, 18.09, 13.89, 1.60, 1.07, 0.00.

29Si-NMR (99.3 MHz, CDCl3): δ 7.49, 7.03, -21.06.

7.2.6. 3’-[4-(4-Undecyloxybenzoyloxy)benzoyloxy]-4-{4-[11-(1,1,3,3,5,5,5-heptamethyl-trisiloxan-1-yl)undec-1-yloxy])benzoyloxy}biphenyl Si3-11B11

O O

O

O O

OC₁₁H₂₅ O

(CH₂)₁₁ O OSi

OSi Si

Me

Me Me

Me Me Me

Ansatzgröße: Me

3’-[4-(4-Undecyloxybenzoyloxy)benzoyloxy]- 0.2 g (0.23 mmol) 4-(undec-10-enyloxy)benzoyloxybiphenyl

1,1,1,3,3,5,5-Heptamethyltrisiloxan 0.055 g (0.24 mmol)

Karstedt-Katalysator 1 Tr.

Toluol 3 ml

Das Rohprodukt wurde mittels Säulenchromatographie (Eluent CHCl3, Rf = 0.33) gereinigt.

Ausbeute: 0.11 g (44 % d. Th.), farbloser Feststoff

Phasenumwandlungstemperaturen/°C (-enthalpien/kJ mol^-1) Cr 63 (12.5) SmCPF[*^] 113 (22.2) Iso

C62H86O10Si3 M = 1075.61 g/mol

berechnet: C, 69.23; H, 8.06 gefunden: C, 69.41; H, 8.40

1H-NMR (400 MHz, CDCl3): δ 8.28 (d, ³J = 8.9 Hz, 2H, Ar-H), 8.14 (d, ³J = 8.9 Hz, 4H, Ar-H), 7.63 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.49 (d, ³J = 5.3 Hz, 2H, Ar-H), 7.43 (s, 1H, Ar-H), 7.36 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.27 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.19 (m, 1H, Ar-H), 6.97 (d, ³J = 8.9 Hz, 2H, Ar-H), 6.96 (d, ³J = 8.9 Hz, 2H, Ar-H), 4.03 (m, 4H, OCH2), 1.81 (m, 4H, OCH2CH2), 1.47 (m, 4H, CH2), 1.25 (m, 28H, CH2), 0.87 (t, ³J = 6.9 Hz, 3H, CH3), 0.49 (m, 2H, SiCH2), 0.07 [s, 9H, Si-(CH3)3], 0.05 [s, 6H, Si-(CH3)2], 0.01 [s, 6H, Si-(CH3)2].

13C-NMR (125 MHz, CDCl3): δ 164.73, 164.29, 164.13, 163.64, 163.41, 155.23, 151.13, 150.66, 141.98, 137.56, 132.22, 132.11, 131.63, 129.64, 128.04, 126.68, 124.49, 121.98,

121.92, 121.27, 120.77, 120.34, 120.22, 114.23, 114.12, 68.20, 68.16, 33.24, 31.70, 29.40, 29.38, 29.34, 29.19, 29.15, 29.13, 28.88, 25.77, 23.02, 22.48, 18.09, 13.90, 1.60, 1.07, 0.00.

29Si-NMR (99.3 MHz, CDCl3): δ 7.49, 7.03, -21.07.

7.2.7. 3’-[4-(4-Tetradecyloxybenzoyloxy)benzoyloxy]-4-{4-[11-(1,1,3,3,5,5,5-heptamethyl-trisiloxan-1-yl)undec-1-yloxy])benzoyloxy}biphenyl Si3-11B14

Ansatzgröße:

3’-[4-(4-Tetradecyloxybenzoyloxy)benzoyloxy]- 0.3 g (0.34 mmol) 4-(undec-10-enyloxy)benzoyloxybiphenyl

1,1,1,3,3,5,5-Heptamethyltrisiloxan 0.07 g (0.34 mmol)

Karstedt-Katalysator 1 Tr.

Toluol 5 ml

Das Rohprodukt wurde mittels Säulenchromatographie (Eluent CHCl3, R_f = 0.31) gereinigt.

Ausbeute: 0.198 g (52 % d. Th.), farbloser Feststoff

Phasenumwandlungstemperaturen/°C (-enthalpien/kJ mol^-1) Cr 61 (22.6) [SmX^[*^] 60 (11.4)] SmCPF[*^] 113 (20.4) Iso

C65H92O10Si3 M = 1117.6923 g/mol

berechnet: C, 69.85; H, 8.29 gefunden: C, 70.17; H, 8.04

1H-NMR (400 MHz, CDCl3): δ 8.29 (d, ³J = 8.7 Hz, 2H, Ar-H), 8.14 (d, ³J = 8.9 Hz, 4H, Ar-H), 7.63 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.49 (d, ³J = 4.9 Hz, 2H, Ar-H), 7.44 (m, 1H, Ar-H), 7.37 (d, ³J = 8.9 Hz, 2H, Ar-H), 7.27 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.21 (m, 1H, Ar-H), 6.97 (d, ³J = 8.9 Hz, 2H, Ar-H), 6.96 (d, ³J = 8.9 Hz, 2H, Ar-H), 4.03 (m, 4H, OCH2), 1.81 (m, 4H, OCH2CH2), 1.47 (m, 4H, OCH2CH2CH2), 1.26 (m, 34H, CH2), 0.87 (t, ³J = 6.9 Hz, 3H, CH3), 0.51 (m, 2H, SiCH2), 0.07 [s, 9H, Si-(CH3)3], 0.05 [s, 6H, Si-(CH3)2], 0.01 [s, 6H, Si-(CH3)2].

13C-NMR (125 MHz, CDCl3): δ 164.93, 164.49, 164.33, 163.84, 163.61, 155.44, 151.33, 150.86, 142.18, 137.77, 132.42 (4C), 132.32 (2C), 131.84 (2C), 129.85, 128.25 (2C), 126.88, 124.69, 122.18 (2C), 122.12 (2C), 121.47, 120.97, 120.55, 120.42, 114.43 (2C), 114.33, 68.40, 68.36, 33.44, 31.92, 29.68, 29.67 (2C), 29.65 (2C), 29.62, 29.58 (2C), 29.56, 29.55, 29.38, 29.35(2C), 29.11, 29.09, 25.99, 25.97, 23.23, 22.68, 18.29, 14.11, 1.81 (3C), 1.27 (2C),

0.20 (2C).

29Si-NMR (99.3 MHz, CDCl3): δ 7.48, 7.04, -21.06.

7.2.8. 3’-[4-(4-Hexadecyloxybenzoyloxy)benzoyloxy]-4-{4-[11-(1,1,3,3,5,5,5-heptamethyl-trisiloxan-1-yl)undec-1-yloxy])benzoyloxy}biphenyl Si3-11B16

O O

O

O O

OC₁₄H₂₉ O

(CH₂)₁₁ O O Si

OSi Si

Me

Me Me

Me Me Me

Me

O O

O

O O

OC₁₆H₃₃ O

(CH₂)₁₁ O O Si

OSi Si

Me

Me Me

Me Me Me

Ansatzgröße: Me

3’-[4-(4-Hexadecyloxybenzoyloxy)benzoyloxy]- 0.25 g (0.27 mmol) 4-(undec-10-enyloxy)-benzoyloxybiphenyl

1,1,1,3,3,5,5-Heptamethyltrisiloxan 0.06 g (0.27 mmol)

Karstedt-Katalysator 1 Tr.

Toluol 5 ml

Das Rohprodukt wurde mittels fliehkraftvermittelter präparativer Dünnschichtchromato-graphie (Eluent CHCl3, Rf = 0.22) gereinigt.

Ausbeute: 0.166 g (54 % d. Th.), farbloser Feststoff

Phasenumwandlungstemperaturen/°C (-enthalpien/kJ mol^-1) Cr 70 (23.9) SmCPF[*^] 111 (22.9) Iso

C67H96O10Si3 M = 1145.75 g/mol

berechnet: C, 70.24; H, 8.45 gefunden: C, 70.27; H, 8.16

1H-NMR (400 MHz, CDCl3): δ 8.29 (d, ³J = 8.9 Hz, 2H, Ar-H), 8.14 (d, ³J = 8.9 Hz, 4H, Ar-H), 7.63 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.49 (d, ³J = 4.9 Hz, 2H, Ar-H), 7.43 (m, 1H, Ar-H), 7.36 (d, ³J = 8.9 Hz, 2H, Ar-H), 7.27 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.21 (m, 1H, Ar-H), 6.97 (d, 2H,

3J = 8.9 Hz, Ar-H), 6.96 (d, 2H, ³J = 8.8 Hz, Ar-H), 4.03 (m, 4H, OCH2), 1.81 (m, 4H, OCH2CH2), 1.45 (m, 4H, OCH2CH2CH2), 1.25 (m, 38H, CH2), 0.87 (t, ³J = 6.8 Hz, 3H, CH3), 0.51 (m, 2H, SiCH2), 0.07 [s, 9H, Si-(CH3)3], 0.05 [s, 6H, Si-(CH3)2], 0.01 [s, 6H, Si-(CH3)2].

13C-NMR (125 MHz, CDCl3): δ 164.91, 164.47, 164.31, 163.83, 163.59, 155.42, 151.32, 150.85, 142.16, 137.74, 132.41 (4C), 132.29 (2C), 131.82 (2C), 129.83, 128.23 (2C), 126.86, 122.17 (2C), 122.10 (2C), 121.45, 120.96, 120.53, 120.41, 114.41 (2C), 114.31 (2C), 68.38, 68.33, 33.43, 31.91, 29.68 (4C), 29.66 (2C), 29.64 (2C), 29.61 (2C), 29.57, 29.54, 29.36 (2C), 29.34, 29.09, 29.07, 25.98, 25.96, 23.21, 22.67, 18.28, 14.09, 1.79 (3C), 1.26 (2C), 0.19 (2C).

29Si-NMR (99.3 MHz, CDCl3): δ 7.48, 7.04, -21.06.

7.2.9. 3’-[4-(4-Octadecyloxybenzoyloxy)benzoyloxy]-4-{4-[11-(1,1,3,3,5,5,5-heptamethyl-trisiloxan-1-yl)undec-1-yloxy])benzoyloxy}biphenyl Si3-11B18

O O

O

O O

OC₁₈H₃₇ O

(CH₂)₁₁ O O Si

OSi Si

Me

Me Me

Me Me Me

Ansatzgröße: Me

3’-[4-(4-Octadecyloxybenzoyloxy)benzoyloxy]- 0.3 g (0.32 mmol) 4-(undec-10-enyloxy)-benzoyloxybiphenyl

1,1,1,3,3,5,5-Heptamethyltrisiloxan 0.07 g (0.32 mmol)

Karstedt-Katalysator 1 Tr.

Toluol 5 ml

Das Rohprodukt wurde mittels fliehkraftvermittelter präparativer Dünnschichtchromato-graphie (Eluent: CHCl3, Rf = 0.46) gereinigt.

Ausbeute: 0.168 g (45 % d. Th.), farbloser Feststoff

Phasenumwandlungstemperaturen/°C (-enthalpien/kJ mol^-1)

Cr 87 (23.9) USmCsPF’ 96 (1.8) USmCsPF 109 (16.3) Iso

C69H100O10Si3 M = 1173.80 g/mol

berechnet: C, 70.60; H, 7.50 gefunden: C, 70.64; H, 8.19

1H-NMR (400 MHz, CDCl3): δ 8.28 (d, ³J = 8.7 Hz, 2H, Ar-H), 8.13 (d, ³J = 8.9 Hz, 4H, Ar-H), 7.63 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.49 (d, ³J = 4.9 Hz, 2H, Ar-H), 7.43 (s, 1H, Ar-H), 7.37

(d, ³J = 8.9 Hz, 2H, Ar-H), 7.27 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.21 (m, 1H, Ar-H), 6.97 (d, ³J = 8.9 Hz, 2H Ar-H), 6.96 (d, ³J = 9.1 Hz, 2H Ar-H), 4.04 (m, 4H, OCH2), 1.81 (m, 4H, OCH2CH2), 1.45 (m, 4H, OCH2CH2CH2), 1.25 (m, 42H, CH2), 0.87 (t, ³J = 6.8 Hz, 3H, CH3), 0.51 (m, 2H, SiCH2), 0.07 [s, 9H, Si-(CH3)3], 0.05 [s, 6H, Si-(CH3)2], 0.01 [s, 6H, Si-(CH3)2].

13C-NMR (125 MHz, CDCl3) δ 164.94, 164.49, 164.34, 163.61, 155.43, 151.33, 150.86, 142.18, 137.77, 132.43 (4C), 132.31 (2C), 131.84 (2C), 129.85, 128.25 (2C), 126.87, 124.32, 122.18 (2C), 122.12 (2C), 121.46, 120.97, 120.42, 114.43 (2C), 114.33 (2C), 68.40, 68.36, 33.44, 31.92, 30.91, 29.69 (6C), 29.65 (4C), 29.62 (2C), 29.58(2C), 29.39 (2C), 29.35 (2C), 29.09, 25.98, 23.23, 22.68, 18.29, 14.11, 1.81 (3C), 1.27 (2C), 0.20 (2C).

29Si-NMR (99.3 MHz, CDCl3): δ 7.48, 7.04, -21.06.

7.2.10. 3’-[4-(4-Icosyloxybenzoyloxy)benzoyloxy]-4-{4-[11-(1,1,3,3,5,5,5-heptamethyl-trisiloxan-1-yl)undec-1-yloxy])benzoyloxy}biphenyl Si3-11B20

O O

O

O O

OC₂₀H₄₁ O

(CH₂)₁₁ O OSi

OSi Si

Me

Me Me

Me Me Me

Ansatzgröße: Me

3’-[4-(4-Icosyloxybenzoyloxy)benzoyloxy]- 0.20 g (0.2 mmol) 4-(undec-10-enyloxy)benzoyloxybiphenyl

1,1,1,3,3,5,5-Heptamethyltrisiloxan 0.045 g (0.2 mmol)

Karstedt-Katalysator 1 Tr.

Toluol 3 ml

Das Rohprodukt wurde mittels Säulenchromatographie (Eluent CHCl3 Rf = 0.24) gereinigt.

Ausbeute: 0.15 g (62 % d. Th.), farbloser Feststoff

Phasenumwandlungstemperaturen/°C (-enthalpien/kJ mol^-1)

Cr 83 (22.4) USmCsPF 96 (-) ColobPA 100 (17.3) Iso

C71H104O10Si3 M = 1201.85 g/mol

berechnet: C, 70.96; H, 8.72 gefunden: C, 70.77; H, 8.77

1H-NMR (400 MHz, CDCl3): δ 8.29 (d, ³J = 8.7 Hz, 2H, Ar-H), 8.14 (d, ³J = 8.9 Hz, 4H, Ar-H), 7.63 (d, ³J = 8.5 Hz, 2H, Ar-H), 7.49 (d, ³J = 4.8 Hz, 2H, Ar-H), 7.44 (s, 1H, Ar-H), 7.37 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.27 (d, ³J = 8.5 Hz, 2H, Ar-H), 7.21 (m, 1H, Ar-H), 6.97 (d, ³J = 8.9 Hz, 2H Ar-H), 6.96 (d, ³J = 8.9 Hz, 2H Ar-H), 4.04 (m, 4H, OCH2), 1.79 (m, 4H, OCH2CH2), 1.47 (m, 4H, OCH2CH2CH2), 1.26 (m, 46H, CH2), 0.87 (t, ³J = 6.8 Hz, 3H, CH3), 0.52 (t, ³J = 7.8 Hz, 2H, SiCH2), 0.07 [s, 9H, Si-(CH3)3], 0.05 [s, 6H, Si-(CH3)2], 0.01 [s, 6H,

Si-(CH3)2].

13C-NMR (100 MHz, CDCl3) δ 164.75, 164.32, 164.16, 163.74, 163.50, 155.36, 151.29150.82, 142.11, 137.69, 132.34, 132.22, 131.74, 129.74, 128.16, 126.87, 124.60, 122.10, 122.03, 121.51, 121.01, 120.47, 120.37, 120.54, 120.41, 114.42, 114.32, 68.42, 68.33, 33.52, 32.02, 29.79, 29.75, 29.72, 29.68, 29.48, 29.45, 29.23, 26.11, 23.35, 22.79, 18.44,

14.19, 1.95, 1.41, 0.36.

29Si-NMR (99.3 MHz, CDCl3): δ 7.47, 7.02, -21.07.

7.2.11. 3’-[4-(4-Docosyloxybenzoyloxy)benzoyloxy]-4-{4-[11-(1,1,3,3,5,5,5-heptamethyl-trisiloxan-1-yl)undec-1-yloxy])benzoyloxy}biphenyl Si3-11B22

O O

O

O O

OC₂₂H₄₅ O

(CH₂)₁₁ O OSi

OSi Si

Me

Me Me

Me Me Me

Ansatzgröße: Me

3’-[4-(4-Docosyloxybenzoyloxy)benzoyloxy]- 0.20 g (0.2 mmol) 4-(undec-10-enyloxy)benzoyloxybiphenyl

1,1,1,3,3,5,5-Heptamethyltrisiloxan 0.044g (0.2 mmol)

Karstedt-Katalysator 1 Tr.

Toluol 3 ml

Das Rohprodukt wurde mittels Säulenchromatographie (Eluent CHCl3 Rf = 0.33) gereinigt.

Ausbeute: 0.146 g (59 % d. Th.), farbloser Feststoff

Phasenumwandlungstemperaturen/°C (-enthalpien/kJ mol^-1) Cr 88 (28.8) ColobPA 98 (13.1) Iso

C73H108O10Si3 M = 1229.91 g/mol

berechnet: C, 71.29; H, 8.85 gefunden: C, 71.56; H, 8.93

1H-NMR (400 MHz, CDCl3): δ 8.29 (d, ³J = 8.7 Hz, 2H, Ar-H), 8.14 (d, ³J = 8.7 Hz, 4H, Ar-H), 7.64 (d, ³J = 8.5 Hz, 2H, Ar-H), 7.49 (d, ³J = 4.8 Hz, 2H, Ar-H), 7.44 (s, 1H, Ar-H), 7.37 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.27 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.21 (m, 1H, Ar-H), 6.97 (d, ³J = 8.9 Hz, 2H Ar-H), 6.96 (d, ³J = 8.7 Hz, 2H Ar-H), 4.04 (m, 4H, OCH2), 1.82 (m, 4H, OCH2CH2), 1.46 (m, 4H, OCH2CH2CH2), 1.28 (m, 50H, CH2), 0.87 (t, ³J = 6.7 Hz, 3H, CH3), 0.52 (m, 2H, SiCH2), 0.08 [s, 9H, Si-(CH3)3], 0.05 [s, 6H, Si-(CH3)2], 0.01 [s, 6H, Si-(CH3)2].

13C-NMR (125 MHz, CDCl3) δ 164.90, 164.46, 164.30, 163.83, 163.60, 155.43, 151.33, 150.87, 142.16, 137.75, 132.41, 132.30, 131.82, 129.83, 129.01, 128.23, 126.86, 125.50, 125.28, 124.67, 122.17, 122.11, 121.47, 120.97, 120.54, 120.41, 114.42, 114.31, 68.38, 68.33, 33.43, 31.92, 30.31, 29.69, 29.65, 29.62, 29.57, 29.55, 29.37, 29.35, 29.10, 29.08, 25.99, 25.97, 23.22, 22.68, 18.29, 14.10, 1.80, 1.77, 1.56, 1.26, 1.13, 1.04, 0.97, 0.20.

29Si-NMR (99.3 MHz, CDCl3): δ 7.48, 7.03, -21.07.

7.3. Synthese der 3’-[4-(4-Dodecyloxybenzoyloxy)benzoyloxy]-4-{4-[ω-(1,1,3,3,5,5,5-heptamethyltrisiloxan-1-yl)alkan-1-yloxy])benzoyloxy}biphenyle Si3-mB12

7.3.1. 3’-[4-(4-Dodecyloxybenzoyloxy)benzoyloxy]-4-{5-[11-(1,1,3,3,5,5,5-heptamethyl-trisiloxan-1-yl)pent-1-yloxy])benzoyloxy}biphenyl Si3-5B12

O O

O

O O

OC₁₂H₂₅ O

(CH₂)₅ O OSi

OSi Si

Me

Me Me

Me Me Me

Ansatzgröße: Me

3’-[4-(4-Dodecyloxybenzoyloxy)benzoyloxy]- 0.2 g (0.26 mmol) 4-(hex-5-enyloxy)benzoyloxybiphenyl

1,1,1,3,3,5,5-Heptamethyltrisiloxan 0.057 g (0.26 mmol)

Karstedt-Katalysator 1 Tr.

Toluol 3 ml

Das Rohprodukt wurde mittels Säulenchromatographie (Eluent CHCl3, Rf = 0.15) gereinigt.

Ausbeute: 0.13 g (50 % d. Th.), farbloser Feststoff

Phasenumwandlungstemperaturen/°C(-enthalpien/kJ mol^-1) Cr 105 [SmCsPF[*^/°^] 83 (53.2)] Iso

C57H76O10Si3 M = 1005.49 g/mol

berechnet: C, 68.09; H, 7.62 gefunden: C, 67.98; H, 7.65

1H-NMR (400 MHz, CDCl3): δ 8.28 (d, ³J = 8.7 Hz, 2H, Ar-H), 8.14 (d, ³J = 8.9 Hz, 4H, Ar-H), 7.64 (d, ³J = 8.5 Hz, 2H, Ar-H), 7.49 (d, ³J = 4.9 Hz, 2H, Ar-H), 7.43 (m, 1H, Ar-H), 7.36 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.27 (d, ³J = 8.5 Hz, 2H, Ar-H), 7.21 (m, 1H, Ar-H), 6.98 (d, ³J = 8.9 Hz, 2H, Ar-H), 6.96 (d, ³J = 8.9 Hz, 2H, Ar-H), 4.04 (m, 4H, OCH2), 1.82 (m, 4H, OCH2CH2), 1.45 (m, 4H, CH2), 1.25 (m, 18H, CH2), 0.87 (t, ³J = 6.9 Hz, 3H, CH3), 0.57 (m, 2H, SiCH2), 0.08 [s, 9H, Si-(CH3)3], 0.07 [s, 6H, Si-(CH3)2], 0.01 [s, 6H, Si-(CH3)2].

13C-NMR (125 MHz, CDCl3): δ 164.93, 164.49, 164.33, 163.84, 163.60, 155.43, 151.33, 150.86, 142.17, 137.76, 132.42, 132.31, 131.83, 129.84, 128.24, 126.87, 124.69, 122.18, 122.12, 121.46, 120.97, 120.54, 120.42, 114.43, 114.32, 68.40, 68.31, 31.91, 29.65, 29.62, 29.58, 29.54, 29.34, 29.34, 29.08, 28.85, 25.97, 23.05, 22.68, 18.21, 14.10, 1.82, 1.28, 0.20.

29Si-NMR (99.3 MHz, CDCl3): δ 7.29, 7.12, -20.92.

7.3.2. 3’-[4-(4-Dodecyloxybenzoyloxy)benzoyloxy]-4-{4-[6-(1,1,3,3,5,5,5-heptamethyl-trisiloxan-1-yl)hex-1-yloxy])benzoyloxy}biphenyl Si3-6B12

O O

O

O O

OC₁₂H₂₅ O

(CH₂)₆ O OSi OSi Si

Me

Me Me

Me Me Me

Ansatzgröße: Me

3’-[4-(4-Dodecyloxybenzoyloxy)benzoyloxy]- 0.2 g (0.25 mmol) 4-(hex-5-enyloxy)benzoyloxybiphenyl

1,1,1,3,3,5,5-Heptamethyltrisiloxan 0.056 g (0.25 mmol)

Karstedt-Katalysator 1 Tr.

Toluol 3 ml

Das Rohprodukt wurde mittels Säulenchromatographie (Eluent CHCl3, Rf = 0.14) gereinigt.

Ausbeute: 0.14 g (52 % d. Th.), farbloser Feststoff

Phasenumwandlungstemperaturen/°C (-enthalpien/kJ mol^-1) Cr 86 (18.1) SmCsPF [*^/°^] 93 (14.8) Iso

C58H78O10Si3 M = 1019.50 g/mol

berechnet: C, 68.3; H, 7.7 gefunden: C, 68.49; H, 7.8

1H-NMR (400 MHz, CDCl3): δ 8.28 (d, ³J = 8.9 Hz, 2H, Ar-H), 8.14 (d, ³J = 8.9 Hz, 4H, Ar-H), 7.63 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.49 (d, ³J = 4.9 Hz, 2H, Ar-H), 7.43 (m, 1H, Ar-H), 7.36 (d, ³J = 8.9 Hz, 2H, Ar-H), 7.27 (d, ³J = 8.5 Hz, 2H, Ar-H), 7.20 (m, 1H, Ar-H), 6.97 (d, ³J = 9.1 Hz, 2H, Ar-H), 6.96 (d, ³J = 9.1 Hz, 2H, Ar-H), 4.04 (m, 4H, OCH2), 1.81 (m, 4H, OCH2CH2), 1.43-1.24 (m, 24H, CH2), 0.87 (t, ³J = 6.8 Hz, 3H, CH3), 0.54 (m, 2H, SiCH2), 0.08 [s, 9H, Si-(CH3)3], 0.06 [s, 6H, Si-(CH3)2], 0.01 [s, 6H, Si-(CH3)2].

13C-NMR (125 MHz, CDCl3): δ 164.93, 164.49, 164.33, 163.85, 163.61, 155.44, 151.34,

150.88, 142.18, 137.77, 132.43, 132.31, 131.84, 129.85, 128.25, 126.89, 124.69, 122.18, 122.12, 121.48, 120.98, 120.55, 120.43, 114.44, 114.33, 68.41, 68.36, 33.09, 31.9229.69, 29.65, 29.63, 29.58, 29.55, 29.35, 29.09, 29.05, 25.98, 25.71, 23.17, 22.68, 18.23, 14.11, 1.82,

1.28, 0.20.

29Si-NMR (99.3 MHz, CDCl3): δ 7.48, 7.07, -21.06.

7.3.3. 3’-[4-(4-Dodecyloxybenzoyloxy)benzoyloxy]-4-{4-[7-(1,1,3,3,5,5,5-heptamethyl-trisiloxan-1-yl)hept-1-yloxy])benzoyloxy}biphenyl Si3-7B12

O O

O

O O

OC₁₂H₂₅ O

(CH₂)₇ O OSi

OSi Si

Me

Me Me

Me Me Me

Ansatzgröße: Me

3’-[4-(4-Dodecyloxybenzoyloxy)benzoyloxy]- 0.2 g (0.25 mmol) 4-(hept-6-enyloxy)benzoyloxybiphenyl

1,1,1,3,3,5,5-Heptamethyltrisiloxan 0.055 g (0.25 mmol)

Karstedt-Katalysator 1 Tr.

Toluol 3 ml

Das Rohprodukt wurde mittels Säulenchromatographie (Eluent CHCl3, Rf = 0.14) gereinigt.

Ausbeute: 0.16 g (62 % d. Th.), farbloser Feststoff

Phasenumwandlungstemperaturen/°C (-enthalpien/kJ mol^-1) Cr 75 (21.3) SmCsPF[*^/°^] 104 (20.6) Iso

C59H80O10Si3 M = 1033.53 g/mol

berechnet: C, 68.56; H, 7.80 gefunden: C, 68.21; H, 7.90

1H-NMR (400 MHz, CDCl3): δ 8.28 (d, ³J = 8.7 Hz, 2H, Ar-H), 8.14 (d, ³J = 8.9 Hz, 4H, Ar-H), 7.63 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.49 (d, ³J = 5.1 Hz, 2H, Ar-H), 7.44 (s, 1H, Ar-H), 7.36 (d, ³J = 8.9 Hz, 2H, Ar-H), 7.27 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.21 (m, 1H, Ar-H), 6.97 (d, ³J = 8.9 Hz, 2H, Ar-H), 6.96 (d, ³J = 8.7 Hz, 2H, Ar-H), 4.04 (m, 4H, OCH2), 1.81 (m, 4H, OCH2CH2), 1.47 (m, 4H, CH2), 1.29 (m, 22H, CH2), 0.87 (t, ³J = 6.8 Hz, 3H, CH3), 0.53 (m, 2H, SiCH2), 0.07 [s, 9H, Si-(CH3)3], 0.05 [s, 6H, Si-(CH3)2], 0.01 [s, 6H, Si-(CH3)2].

13C-NMR (125 MHz, CDCl3): δ 164.92, 164.49, 164.33, 163.84, 163.60, 155.44, 151.34, 150.87, 142.18, 137.76, 132.42, 132.31, 131.84, 129.84, 128.24, 126.88, 124.69, 122.18, 122.12, 121.47, 120.97, 120.55, 120.42, 114.43, 114.32, 68.40, 68.34, 33.30, 31.91, 29.65, 29.63, 29.58, 29.55, 29.35, 29.34, 29.14, 29.09, 25.97, 25.92, 23.16, 22.68, 18.27, 14.11, 1.81,

1.28, 0.20.

29Si-NMR (99.3 MHz, CDCl3): δ 7.41, 7.05, -21.03.

7.3.4. 3’-[4-(4-Dodecyloxybenzoyloxy)benzoyloxy]-4-{4-[8-(1,1,3,3,5,5,5-heptamethyl-trisiloxan-1-yl)oct-1-yloxy])benzoyloxy}biphenyl Si3-8B12

Ansatzgröße:

3’-[4-(4-Dodecyloxybenzoyloxy)benzoyloxy]- 0.2 g (0.24 mmol) 4-(oct-7-enyloxy)benzoyloxybiphenyl

1,1,1,3,3,5,5-Heptamethyltrisiloxan 0.061 g (0.27 mmol)

Karstedt-Katalysator 1 Tr.

Toluol 3 ml

Das Rohprodukt wurde mittels Säulenchromatographie (Eluent CHCl3, Rf = 0.08) gereinigt.

Ausbeute: 0.12 g (48 % d. Th.), farbloser Feststoff

Phasenumwandlungstemperaturen/°C (-enthalpien/kJ mol^-1)

Cr 71 (21.8) SmCsPF[*^/°^] 102 (16.3) Iso C60H82O10Si3 M = 1047.56 g/mol

berechnet: C, 68.79; H, 7.89 gefunden: C, 68.58; H, 8.08

1H-NMR (400 MHz, CDCl3): δ 8.28 (d, ³J = 8.5 Hz, 2H, Ar-H), 8.14 (d, ³J = 8.9 Hz, 4H, Ar-H), 7.63 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.49 (d, ³J = 5.1 Hz, 2H, Ar-H), 7.43 (m, 1H, Ar-H), 7.36 (d, ³J = 8.9 Hz, 2H, Ar-H), 7.27 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.19 (m, 1H, Ar-H), 6.97 (d, ³J = 8.9 Hz, 2H, Ar-H), 6.96 (d, ³J = 8.7 Hz, 2H, Ar-H), 4.04 (m, 4H, OCH2), 1.81 (m, 4H, OCH2CH2), 1.52-1.26 (m, 28H, CH2), 0.87 (t, ³J = 6.8 Hz, 3H, CH3), 0.52 (m, 2H, SiCH2), 0.07 [s, 9H, Si-(CH3)3], 0.05 [s, 6H, Si-(CH3)2], 0.01 [s, 6H, Si-(CH3)2].

13C-NMR (125 MHz, CDCl3): δ 164.92, 164.47, 164.31, 163.83, 163.60, 155.43, 151.32, 150.86, 142.16, 137.75, 132.41, 132.30, 131.83, 129.83, 128.23, 126.87, 124.67, 122.17, 122.11, 121.46, 120.96, 120.41, 114.42, 114.32, 68.39, 68.34, 68.26, 33.33, 31.90, 29.64, 9.62, 29.57, 29.54, 29.34, 29.33, 29.29, 29.27, 29.10, 29.08, 26.01, 25.96, 25.47, 23.20, 22.68,

18.27, 14.10, 1.81, 1.27, 0.20.

29Si-NMR (99.3 MHz, CDCl3): δ 7.45, 7.05, -21.03.

7.3.5. 3’-[4-(4-Dodecyloxybenzoyloxy)benzoyloxy]-4-{4-[9-(1,1,3,3,5,5,5-heptamethyl-trisiloxan-1-yl)non-1-yloxy])benzoyloxy}biphenyl Si3-9B12

O O

O

O O

OC₁₂H₂₅ O

(CH₂)₈ O OSi OSi Si

Me

Me Me

Me Me Me

Me

O O

O

O O

OC₁₂H₂₅ O

(CH₂)₉ O OSi OSi Si

Me

Me Me

Me Me Me

Ansatzgröße: Me

3’-[4-(4-Dodecyloxybenzoyloxy)benzoyloxy]- 0.2 g (0.24 mmol) 4-(non-8-enyloxy)benzoyloxybiphenyl

1,1,1,3,3,5,5-Heptamethyltrisiloxan 0.058 g (0.26 mmol)

Karstedt-Katalysator 1 Tr.

Toluol 3 ml

Das Rohprodukt wurde mittels Säulenchromatographie (Eluent CHCl3, Rf = 0.25) gereinigt.

Ausbeute: 0.17 g (67 % d. Th.), farbloser Feststoff

Phasenumwandlungstemperaturen/°C (-enthalpien/kJ mol^-1)

Cr1 58 Cr2 68 [SmX^[*^] 61 (11.9)] SmCsPF [*^] 108 (21.1) Iso

C61H84O10Si3 M = 1061.59 g/mol

berechnet: C, 69.02; H, 7.98 gefunden: C, 69.22; H, 8.03

1H-NMR (400 MHz, CDCl3): δ 8.28 (d, ³J = 8.7 Hz, 2H, Ar-H), 8.14 (d, ³J = 8.7 Hz, 4H, Ar-H), 7.63 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.49 (d, ³J = 5.4 Hz, 2H, Ar-H), 7.43 (s, 1H, Ar-H), 7.36 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.27 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.21 (m, 1H, Ar-H), 6.97 (d, ³J = 8.9 Hz, 2H, Ar-H), 6.96 (d, ³J = 8.9 Hz, 2H, Ar-H), 4.04 (m, 4H, OCH2), 1.81 (m, 4H, OCH2CH2), 1.47-1.26 (m, 30H, CH2), 0.87 (t, ³J = 6.9 Hz, 3H, CH3), 0.52 (m, 2H, SiCH2), 0.07 [s, 9H, Si-(CH3)3], 0.05 [s, 6H, Si-(CH3)2], 0.006 [s, 6H, Si-(CH3)2].

13C-NMR (125 MHz, CDCl3): δ 164.73, 164.29, 164.13, 163.64, 163.41, 155.23, 151.13, 150.66, 141.97, 137.56, 132.22, 132.11, 131.63, 129.64, 128.04, 126.67, 121.98, 121.92, 121.26, 120.76, 120.34, 120.22, 114.23, 114.12, 68.20, 68.15, 33.20, 31.71, 29.45, 29.42, 29.38, 29.35, 29.29, 29.20, 29.14, 29.11, 28.91, 28.88, 25.77, 23.02, 22.48, 18.09, 13.90, 1.61,

1.07, 0.00.

29Si-NMR (99.3 MHz, CDCl3): δ 7.46, 7.04, -21.03.

7.3.6. 3’-[4-(4-Dodecyloxybenzoyloxy)benzoyloxy]-4-{4-[10-(1,1,3,3,5,5,5-heptamethyl-trisiloxan-1-yl)dec-1-yloxy])benzoyloxy}biphenyl Si3-9B12

O O

O

O O

OC₁₂H₂₅ O

(CH₂)₁₀ O O Si

OSi Si

Me

Me Me

Me Me Me

Ansatzgröße: Me

3’-[4-(4-Dodecyloxybenzoyloxy)benzoyloxy]- 0.25 g (0.30 mmol) 4-(dec-9-enyloxy)benzoyloxybiphenyl

1,1,1,3,3,5,5-Heptamethyltrisiloxan 0.066 g (0.30 mmol)

Karstedt-Katalysator 1 Tr.

Toluol 5 ml

Das Rohprodukt wurde mittels Säulenchromatographie (Eluent CHCl3,Rf = 0.18) gereinigt.

Ausbeute: 0.15 g (46 % d. Th.), farbloser Feststoff

Phasenumwandlungstemperaturen/°C (-enthalpien/kJ mol^-1) Cr 63 (39.2) SmCsPF [*^] 115 (22.3) Iso

C62H86O10Si3 M = 1075.61 g/mol

berechnet: C, 69.23; H, 8.06 gefunden: C, 69.42; H, 8.10

1H-NMR (400 MHz, CDCl3): δ 8.28 (d, ³J = 8.7 Hz, 2H, Ar-H), 8.14 (d, ³J = 8.9 Hz, 4H, Ar-H), 7.63 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.49 (d, ³J = 4.9 Hz, 2H, Ar-H), 7.44 (m, 1H, Ar-H), 7.36 (d, ³J = 8.9 Hz, 2H, Ar-H), 7.27 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.21 (m, 1H, Ar-H), 6.97 (d, 2H,

3J = 8.9 Hz, Ar-H), 6.96 (d, 2H, ³J = 8.9 Hz, Ar-H), 4.04 (m, 4H, OCH2), 1.81 (m, 4H, OCH2CH2), 1.48 (m, 4H, OCH2CH2CH2), 1.26 (m, 28H, CH2), 0.87 (t, ³J = 6.9 Hz, 3H, CH3), 0.52 (m, 2H, SiCH2), 0.07 [s, 9H, Si-(CH3)3], 0.05 [s, 6H, Si-(CH3)2], 0.01 [s, 6H, Si-(CH3)2].

13C-NMR (125 MHz, CDCl3): δ 164.92, 164.48, 164.32, 163.84, 163.60, 155.43, 151.33, 150.86, 142.17, 137.76, 132.42, 132.31, 131.83, 129.84, 128.24, 126.87, 124.68, 122.18, 122.12, 121.47, 120.97, 120.55, 120.42, 114.43, 114.32, 68.40, 68.35, 33.42, 31.91, 29.64,

29.62, 29.59, 29.54, 29.52, 29.37, 29.35, 29.11, 29.08, 25.99, 25.97, 23.22, 22.68, 18.29,

14.10, 1.81, 1.27, 0.20.

29Si-NMR (99.3 MHz, CDCl3): δ 7.47, 7.04, -21.06.

7.4. Synthese von 3’-[4-(4-Tetradecyloxybenzoyloxy)benzoyloxy]-4-{4-[6-(1,1,3,3,5,5,5-heptamethyltrisiloxan-1-yl)hex-1-yloxy])benzoyloxy}biphenyl Si3-6B14

O O

O

O O

OC₁₄H₂₉ O

(CH₂)₆ O O Si

OSi Si

Me

Me Me

Me Me Me

Ansatzgröße: Me

3’-[4-(4-Tetradecyloxybenzoyloxy)benzoyloxy]- 0.2 g (0.24 mmol) 4-(hex-5-enyloxy)benzoyloxybiphenyl

1,1,1,3,3,5,5-Heptamethyltrisiloxan 0.054 g (0.24 mmol)

Karstedt-Katalysator 1 Tr.

Toluol 5 ml

Das Rohprodukt wurde mittels Säulenchromatographie (Eluent: CHCl3, R_f = 0.23) gereinigt.

Ausbeute: 0.082 g (33 % d. Th.), farbloser Feststoff

Phasenumwandlungstemperaturen/°C (-enthalpien/kJ mol^-1)

Cr 92 (31.7) [Col 87 (15.3)] Iso

C60H82O10Si3 M = 1047.56 g/mol

berechnet: C, 68.80; H, 7.89 gefunden: C, 69.30; H, 7.88

1H-NMR (400 MHz, CDCl3): δ 8.28 (d, ³J = 8.9 Hz, 2H, Ar-H), 8.14 (d, ³J = 8.9 Hz, 4H, Ar-H), 7.63 (d, ³J = 8.5 Hz, 2H, Ar-H), 7.49 (d, ³J = 5.4 Hz, 2H, Ar-H), 7.43 (s, 1H, Ar-H), 7.36 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.26 (d, ³J = 8.8 Hz, 2H, Ar-H), 7.19 (m, 1H, Ar-H), 6.97 (d, ³J = 8.9 Hz, 2H Ar-H), 6.96 (d, ³J = 9.1 Hz, 2H Ar-H), 4.04 (m, 4H, OCH2), 1.81 (m, 4H, OCH2CH2), 1.45-1.25 (m, 28H, CH2), 0.87 (t, ³J = 6.8 Hz, 3H, CH3), 0.53 (m, 2H, SiCH2), 0.07 [s, 9H, Si-(CH3)3], 0.05 [s, 6H, Si-(CH3)2], 0.01 [s, 6H, Si-(CH3)2].

13C-NMR (125 MHz, CDCl3): δ 164.90, 164.45, 164.29, 163.80, 163.57, 155.40, 151.30, 150.83, 142.14, 137.73, 132.39, 132.28, 131.0, 129.81, 128.21, 126.84, 124.65, 122.14, 122.08, 121.43, 120.94, 120.51, 120.39, 114.39, 114.29, 68.37, 68.32, 33.05, 31.88, 29.65, 29.63, 29.61, 29.55, 29.51, 29.31, 29.05, 29.01, 25.94, 25.67, 23.12, 22.65, 18.18, 14.07, 1.78,

1.24, 0.16.

29Si-NMR (99.3 MHz, CDCl3): δ 7.37, 7.08, -20.99.

7.5. Synthese von 3’-[4-(4-Octadecyloxybenzoyloxy)benzoyloxy]-4-{4-[6-(1,1,3,3,5,5,5-heptamethyltrisiloxan-1-yl)hex-1-yloxy])benzoyloxy}biphenyl Si3-6B18

O O

O

O O

OC₁₈H₃₇ O

(CH₂)₆ O OSi OSi Si

Me

Me Me

Me Me Me

Ansatzgröße: Me

3’-[4-(4-Octadecyloxybenzoyloxy)benzoyloxy]- 0.17 g (0.19 mmol) 4-(Hex-5-enyloxy)benzoyloxybiphenyl

1,1,1,3,3,5,5-Heptamethyltrisiloxan 0.043 g (0.19 mmol)

Karstedt-Katalysator 1 Tr.

Toluol 3 ml

Das Rohprodukt wurde mittels Säulenchromatographie (Eluent CHCl3/MeOH 10:0.05, Rf = 0.45) gereinigt.

Ausbeute: 0.14 g (68 % d. Th.), farbloser Feststoff

Phasenumwandlungstemperaturen/°C (-enthalpien/kJ mol^-1) Cr 98 (48.4) [Col 90 (17.40)] Iso

C64H90O10Si3 M = 1103.67 g/mol

berechnet: C, 69.65; H, 8.22 gefunden: C, 69.90; H, 8.10

1H-NMR (400 MHz, CDCl3): δ 8.28 (d, ³J = 8.7 Hz, 2H, Ar-H), 8.14 (d, ³J = 8.9 Hz, 4H, Ar-H), 7.63 (d, ³J = 8.5 Hz, 2H, Ar-H), 7.49 (d, ³J = 4.9 Hz, 2H, Ar-H), 7.43 (m, 1H, Ar-H), 7.36 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.27 (d, ³J = 8.7 Hz, 2H, Ar-H), 7.24 (m, 1H, Ar-H), 6.97 (d, ³J = 9.1 Hz, 2H, Ar-H), 6.96 (d, ³J = 9.1 Hz, 2H, Ar-H), 4.04 (m, 4H, OCH2), 1.81 (m, 4H, OCH2CH2), 1.45 (m, 4H, CH2), 1.34 (m, 32H, CH2), 0.86 (t, ³J = 6.9 Hz, 3H, CH3), 0.54 (m, 2H, SiCH2), 0.08 [s, 9H, Si-(CH3)3], 0.06 [s, 6H, Si-(CH3)2], 0.01 [s, 6H, Si-(CH3)2].

13C-NMR (125 MHz, CDCl3): δ 164.93, 164.49, 164.33,163.84, 163.60, 155.44, 151.33, 150.87, 142.17, 137.76, 132.42, 132.31, 131.83, 129.84, 128.24, 126.87, 124.69, 122.18, 122.12, 121.47, 120.97, 120.55, 120.42, 114.29, 114.32, 68.40, 68.36, 33.09, 31.92, 31.54, 29.69, 29.67, 29.65, 29.58, 29.55, 29.6, 29.09, 29.05, 28.81, 25.98, 25.71, 25.66, 23.16, 22.68,

18.22, 14.11, 14.01, 1.82, 1.30, 1.01, 0.20.

29Si-NMR (99.3 MHz, CDCl3): δ 7.48, 7.07, -21.06.

Im Dokument Flüssigkristalldesign mit Organosiliziumeinheiten - Synthese und Charakterisierung neuartiger bent-core Mesogene (Seite 134-148)