Syntheses and Properties of Four-ring Liquid Crystals with Ethylene and Internal Alkyne Bridge†

doi:10.7503/cjcu20131233

Abstract

Abstract:

Ten four-ring liquid crystals with ethylene and internal alkyne bridge were synthesized via Grignard reaction, Huang Minglong reduction, iodination, “one-pot” Sonogashira cross-coupling reaction with trans-4-alkyl-cyclohexane-carboxylic-acid as the starting substrate. The structures of the compounds were confirmed by infrared spectrometry(IR), nuclear magnetic resonance(NMR) and mass spectra(MS). The differential scanning calorimetry(DSC), polarising optical microscopy(POM) and Abbe refractometer were used to measure their properties. The results show that the compounds possess high clearing point(220—240 ℃), broad nematic phase(59.6—99.6 ℃) and high birefringence(Δn>0.3). These properties match the requirement of liquid crystal optics.

Key words: High clearing point, Alkyne-bridge, Birefringence, Terahertz

CLC Number:

O625

TrendMD:

CHEN Ran, AN Zhongwei, CHEN Xinbing, CHEN Pei. Syntheses and Properties of Four-ring Liquid Crystals with Ethylene and Internal Alkyne Bridge^†[J]. Chem. J. Chinese Universities, 2014, 35(7): 1433.

Figures/Tables 8

References 23

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Compd.	m. p./℃	Yield(%)	Appearance	MS, m/z(RI, %)
2-F	82.7—83.3	65	Light yellow solid	298(M⁺, 9), 283(100), 155(28), 115(11), 55(8)
3-F	87.1—88.2	70	Light yellow solid	312(M⁺, 13), 297(100), 159(15)
4-F	81.4—82.7	68	Light yellow solid	326(M⁺, 10), 311(100), 159(24), 155(43), 115(15)
5-F	79.3—79.8	72	Light yellow solid	340(M⁺, 11), 325(100), 155(40), 115(12), 55(7)
2-2	159.3—161.5	45	White solid	454(M⁺, 100), 329(66), 204(21)
3-2	150.1—152.3	43	White solid	468(M⁺, 100), 343(27), 329(32), 204(17)
4-2	133.8—136.1	45	White solid	482(M⁺, 100), 357(19), 329(29), 204(16)
5-2	127.5—130.0	36	White solid	496(M⁺, 100), 371(9), 357(9), 343(13), 329(16), 204(14)
3-3	139.1—141.7	40	White solid	482(M⁺, 65), 371(30), 343(100), 204(41)
4-3	150.8—153.4	40	White solid	496(M⁺, 100), 357(21), 343(29), 204(14)
5-3	139.5—142.1	40	White solid	510(M⁺, 100), 371(14), 343(27), 204(13)
4-4	154.6—156.8	40	White solid	510(M⁺, 100), 357(50), 204(24)
5-4	143.7—146.1	38	White solid	524(M⁺, 100), 371(23), 357(22), 204(17)
5-5	143.2—145.6	43	White solid	538(M⁺, 100), 371(29), 204(11)

Compd.	m. p./℃	Yield(%)	Appearance	MS, m/z(RI, %)
2-F	82.7—83.3	65	Light yellow solid	298(M⁺, 9), 283(100), 155(28), 115(11), 55(8)
3-F	87.1—88.2	70	Light yellow solid	312(M⁺, 13), 297(100), 159(15)
4-F	81.4—82.7	68	Light yellow solid	326(M⁺, 10), 311(100), 159(24), 155(43), 115(15)
5-F	79.3—79.8	72	Light yellow solid	340(M⁺, 11), 325(100), 155(40), 115(12), 55(7)
2-2	159.3—161.5	45	White solid	454(M⁺, 100), 329(66), 204(21)
3-2	150.1—152.3	43	White solid	468(M⁺, 100), 343(27), 329(32), 204(17)
4-2	133.8—136.1	45	White solid	482(M⁺, 100), 357(19), 329(29), 204(16)
5-2	127.5—130.0	36	White solid	496(M⁺, 100), 371(9), 357(9), 343(13), 329(16), 204(14)
3-3	139.1—141.7	40	White solid	482(M⁺, 65), 371(30), 343(100), 204(41)
4-3	150.8—153.4	40	White solid	496(M⁺, 100), 357(21), 343(29), 204(14)
5-3	139.5—142.1	40	White solid	510(M⁺, 100), 371(14), 343(27), 204(13)
4-4	154.6—156.8	40	White solid	510(M⁺, 100), 357(50), 204(24)
5-4	143.7—146.1	38	White solid	524(M⁺, 100), 371(23), 357(22), 204(17)
5-5	143.2—145.6	43	White solid	538(M⁺, 100), 371(29), 204(11)

Compd.	¹H NMR(CDCl₃, 300 MHz), δ	¹³C NMR(CDCl₃, 75 MHz), δ
2-F	0.81—0.93(m, 7H), 1.11—1.27(m, 4H), 1.43—1.50(m, 2H), 1.60(s, 6H), 1.70—1.80(m, 4H), 2.51—2.63(m, 2H), 7.08(d, J=8.0 Hz, 2H), 7.31(d, J=8.1 Hz, 2H)	11.5, 30.0, 31.6, 32.8, 32.8, 33.3, 33.3, 33.3, 37.5, 39.0, 39.6, 65.6, 82.3, 93.2, 119.9, 128.3, 131.6, 143.6
3-F	0.84—0.98(m, 7H), 1.10—1.18(m, 4H), 1.25—1.34(m, 2H), 1.42—1.48(m, 2H), 1.60(s, 6H), 1.69—1.78(m, 4H), 2.54—2.63(m, 2H), 7.08(d, J=8.0 Hz, 2H), 7.31(d, J=8.0 Hz, 2H)	14.4, 20.0, 31.6, 33.3, 33.3, 33.3, 37.5, 37.5, 39.1, 39.8, 65.6, 82.3, 93.2, 119.9, 128.3, 131.6, 143.6
4-F	0.80—0.96(m, 7H), 1.09—1.19(m, 4H), 1.23—1.32(m, 4H), 1.42—1.50(m, 2H), 1.60(s, 6H), 1.69—1.80(m, 4H), 2.53—2.62(m, 2H), 7.07(d, J=8.0 Hz, 2H), 7.31(d, J=8.1 Hz, 2H)	14.2, 23.2, 29.3, 31.6, 33.3, 33.3, 33.3, 37.2, 37.5, 37.8, 39.1, 65.6, 82.3, 93.3, 119.9, 128.3, 131.6, 143.6
5-F	0.82—0.99(m, 7H), 1.07—1.20(m, 4H), 1.21—1.32(m, 6H), 1.45—1.54(m, 2H), 1.61(s, 6H), 1.69—1.79(m, 4H), 2.53—2.65(m, 2H), 7.10(d, J=8.0 Hz, 2H), 7.32(d, J=8.0 Hz, 2H)	14.1, 22.7, 26.7, 31.6, 32.2, 33.3, 33.3, 33.3, 37.5, 37.5, 37.8, 39.0, 65.6, 82.3, 93.2, 119.9, 128.3, 131.6, 143.6
2-2	0.74—0.85(m, 14H), 1.07—1.17(m, 8H), 1.38—1.44(m, 4H), 1.65—1.73(m, 8H), 2.51—2.57(m, 4H), 7.05(d, J=7.8 Hz, 4H), 7.34(d, J=7.9 Hz, 4H)	11.5, 30.0, 32.8, 32.8, 33.3, 33.3, 33.3, 37.5, 39.1, 39.6, 99.0, 120.6, 128.4, 131.5, 143.5
3-2	0.76—0.93(m, 14H), 1.03—1.10(m, 4H), 1.12—1.21(m, 4H), 1.21—1.28(m, 2H), 1.38—1.46(m, 4H), 1.62—1.75(m, 8H), 2.49—2.60(m, 4H), 7.06(d, J=7.9 Hz, 4H), 7.34(d, J=8.0 Hz, 4H)	11.5, 14.4, 20.0, 30.0, 32.8, 32.8, 33.3, 33.3, 33.3, 37.5, 37.6, 39.1, 39.6, 39.8, 99.0, 120.6, 128.4, 131.5, 143.5
4-2	0.84—0.99(m, 14H), 1.12—1.21(m, 6H), 1.21—1.24(m, 2H), 1.25—1.31(m, 4H), 1.45—1.53(m, 4H), 1.69—1.83(m, 8H), 2.55—2.68(m, 4H), 7.13(d, J=8.0 Hz, 4H), 7.41(d, J=8.0 Hz, 4H)	11.5, 14.1, 23.0, 29.3, 30.0, 32.8, 32.8, 33.3, 33.3, 33.3, 37.2, 37.5, 37.8, 39.1, 39.6, 99.0, 120.6, 128.4, 131.5, 143.5
5-2	0.83—0.96(m, 14H), 1.12—1.22(m, 8H), 1.23—1.30(m, 6H), 1.46—1.54(m, 4H), 1.70—1.83(m, 8H), 2.57—2.72(m, 4H), 7.13(d, J=7.4 Hz, 4H), 7.42(d, J=7.5 Hz, 4H)	11.5, 14.1, 22.7, 26.7, 30.0, 32.3, 32.8, 32.8, 33.3, 33.3, 33.3, 37.5, 37.5, 37.9, 39.1, 39.6, 99.0, 120.6, 128.4, 131.5, 143.5
3-3	0.70—0.92(m, 14H), 1.01—1.16(m, 8H), 1.18—1.30(m, 4H), 1.36—1.47(m, 4H), 1.55—1.79(m, 8H), 2.44—2.65(m, 4H), 7.05(d, J=8.0 Hz, 4H), 7.34(d, J=8.0 Hz, 4H)	14.4, 20.0, 33.3, 33.3, 33.3, 37.5, 37.6, 39.1, 39.8, 99.0, 120.6, 128.4, 131.5, 143.5
4-3	0.72—0.93(m, 14H), 0.98—1.14(m, 8H), 1.16—1.29(m, 6H), 1.36—1.47(m, 4H), 1.59—1.83(m, 8H), 2.43—2.64(m, 4H), 7.06(d, J=8.0 Hz, 4H), 7.34(d, J=8.0 Hz, 4H)	14.1, 14.4, 20.0, 23.0, 29.3, 33.3, 33.3, 33.3, 37.2, 37.5, 37.9, 39.1, 39.8, 99.0, 120.6, 128.4, 131.5, 143.5
5-3	0.77—0.94(m, 14H), 1.05—1.11(m, 8H), 1.16—1.23(m, 8H), 1.38—1.44(m, 4H), 1.63—1.72(m, 8H), 2.50—2.57(m, 4H), 7.06(d, J=7.8 Hz, 4H), 7.34(d, J=7.9 Hz, 4H)	14.1, 14.4, 20.0, 22.7, 26.7, 32.3, 33.3, 33.3, 33.3, 37.5, 37.5, 37.9, 39.1, 39.8, 99.0, 120.6, 128.4, 131.5, 143.5
4-4	0.84—0.95(m, 14H), 0.98—1.13(m, 8H), 1.15—1.28(m, 8H), 1.37—1.46(m, 4H), 1.58—1.79(m, 8H), 2.36—2.69(m, 4H), 7.06(d, J=7.8 Hz, 4H), 7.34(d, J=7.8 Hz, 4H)	14.1, 23.0, 29.3, 33.3, 33.3, 33.3, 37.2, 37.5, 37.8, 39.1, 99.0, 120.6, 128.4, 131.5, 143.5
5-4	0.74—0.93(m, 14H), 1.02—1.12(m, 8H), 1.15—1.26(m, 10H), 1.35—1.47(m, 6H), 1.62—1.73(m, 8H), 2.48—2.60(m, 4H), 7.05(d, J=7.2 Hz, 4H), 7.34(d, J=7.0 Hz, 4H)	14.1, 22.7, 23.0, 26.7, 29.3, 32.3, 33.3, 33.3, 33.3, 37.2, 37.5, 37.5, 37.9, 39.1, 99.0, 120.6, 128.4, 131.5, 143.5
5-5	0.82—1.00(m, 14H), 1.10—1.19(m, 8H), 1.20—1.33(m, 12H), 1.45—1.53(m, 4H), 1.68—1.84(m, 8H), 2.52—2.71(m, 4H), 7.13(d, J=8.0 Hz, 4H), 7.42(d, J=8.0 Hz, 4H)	14.1, 22.7, 26.7, 32.2, 33.3, 33.3, 33.3, 37.5, 37.5, 37.9, 39.1, 99.0, 120.6, 128.4, 131.5, 143.5

Compd.	¹H NMR(CDCl₃, 300 MHz), δ	¹³C NMR(CDCl₃, 75 MHz), δ
2-F	0.81—0.93(m, 7H), 1.11—1.27(m, 4H), 1.43—1.50(m, 2H), 1.60(s, 6H), 1.70—1.80(m, 4H), 2.51—2.63(m, 2H), 7.08(d, J=8.0 Hz, 2H), 7.31(d, J=8.1 Hz, 2H)	11.5, 30.0, 31.6, 32.8, 32.8, 33.3, 33.3, 33.3, 37.5, 39.0, 39.6, 65.6, 82.3, 93.2, 119.9, 128.3, 131.6, 143.6
3-F	0.84—0.98(m, 7H), 1.10—1.18(m, 4H), 1.25—1.34(m, 2H), 1.42—1.48(m, 2H), 1.60(s, 6H), 1.69—1.78(m, 4H), 2.54—2.63(m, 2H), 7.08(d, J=8.0 Hz, 2H), 7.31(d, J=8.0 Hz, 2H)	14.4, 20.0, 31.6, 33.3, 33.3, 33.3, 37.5, 37.5, 39.1, 39.8, 65.6, 82.3, 93.2, 119.9, 128.3, 131.6, 143.6
4-F	0.80—0.96(m, 7H), 1.09—1.19(m, 4H), 1.23—1.32(m, 4H), 1.42—1.50(m, 2H), 1.60(s, 6H), 1.69—1.80(m, 4H), 2.53—2.62(m, 2H), 7.07(d, J=8.0 Hz, 2H), 7.31(d, J=8.1 Hz, 2H)	14.2, 23.2, 29.3, 31.6, 33.3, 33.3, 33.3, 37.2, 37.5, 37.8, 39.1, 65.6, 82.3, 93.3, 119.9, 128.3, 131.6, 143.6
5-F	0.82—0.99(m, 7H), 1.07—1.20(m, 4H), 1.21—1.32(m, 6H), 1.45—1.54(m, 2H), 1.61(s, 6H), 1.69—1.79(m, 4H), 2.53—2.65(m, 2H), 7.10(d, J=8.0 Hz, 2H), 7.32(d, J=8.0 Hz, 2H)	14.1, 22.7, 26.7, 31.6, 32.2, 33.3, 33.3, 33.3, 37.5, 37.5, 37.8, 39.0, 65.6, 82.3, 93.2, 119.9, 128.3, 131.6, 143.6
2-2	0.74—0.85(m, 14H), 1.07—1.17(m, 8H), 1.38—1.44(m, 4H), 1.65—1.73(m, 8H), 2.51—2.57(m, 4H), 7.05(d, J=7.8 Hz, 4H), 7.34(d, J=7.9 Hz, 4H)	11.5, 30.0, 32.8, 32.8, 33.3, 33.3, 33.3, 37.5, 39.1, 39.6, 99.0, 120.6, 128.4, 131.5, 143.5
3-2	0.76—0.93(m, 14H), 1.03—1.10(m, 4H), 1.12—1.21(m, 4H), 1.21—1.28(m, 2H), 1.38—1.46(m, 4H), 1.62—1.75(m, 8H), 2.49—2.60(m, 4H), 7.06(d, J=7.9 Hz, 4H), 7.34(d, J=8.0 Hz, 4H)	11.5, 14.4, 20.0, 30.0, 32.8, 32.8, 33.3, 33.3, 33.3, 37.5, 37.6, 39.1, 39.6, 39.8, 99.0, 120.6, 128.4, 131.5, 143.5
4-2	0.84—0.99(m, 14H), 1.12—1.21(m, 6H), 1.21—1.24(m, 2H), 1.25—1.31(m, 4H), 1.45—1.53(m, 4H), 1.69—1.83(m, 8H), 2.55—2.68(m, 4H), 7.13(d, J=8.0 Hz, 4H), 7.41(d, J=8.0 Hz, 4H)	11.5, 14.1, 23.0, 29.3, 30.0, 32.8, 32.8, 33.3, 33.3, 33.3, 37.2, 37.5, 37.8, 39.1, 39.6, 99.0, 120.6, 128.4, 131.5, 143.5
5-2	0.83—0.96(m, 14H), 1.12—1.22(m, 8H), 1.23—1.30(m, 6H), 1.46—1.54(m, 4H), 1.70—1.83(m, 8H), 2.57—2.72(m, 4H), 7.13(d, J=7.4 Hz, 4H), 7.42(d, J=7.5 Hz, 4H)	11.5, 14.1, 22.7, 26.7, 30.0, 32.3, 32.8, 32.8, 33.3, 33.3, 33.3, 37.5, 37.5, 37.9, 39.1, 39.6, 99.0, 120.6, 128.4, 131.5, 143.5
3-3	0.70—0.92(m, 14H), 1.01—1.16(m, 8H), 1.18—1.30(m, 4H), 1.36—1.47(m, 4H), 1.55—1.79(m, 8H), 2.44—2.65(m, 4H), 7.05(d, J=8.0 Hz, 4H), 7.34(d, J=8.0 Hz, 4H)	14.4, 20.0, 33.3, 33.3, 33.3, 37.5, 37.6, 39.1, 39.8, 99.0, 120.6, 128.4, 131.5, 143.5
4-3	0.72—0.93(m, 14H), 0.98—1.14(m, 8H), 1.16—1.29(m, 6H), 1.36—1.47(m, 4H), 1.59—1.83(m, 8H), 2.43—2.64(m, 4H), 7.06(d, J=8.0 Hz, 4H), 7.34(d, J=8.0 Hz, 4H)	14.1, 14.4, 20.0, 23.0, 29.3, 33.3, 33.3, 33.3, 37.2, 37.5, 37.9, 39.1, 39.8, 99.0, 120.6, 128.4, 131.5, 143.5
5-3	0.77—0.94(m, 14H), 1.05—1.11(m, 8H), 1.16—1.23(m, 8H), 1.38—1.44(m, 4H), 1.63—1.72(m, 8H), 2.50—2.57(m, 4H), 7.06(d, J=7.8 Hz, 4H), 7.34(d, J=7.9 Hz, 4H)	14.1, 14.4, 20.0, 22.7, 26.7, 32.3, 33.3, 33.3, 33.3, 37.5, 37.5, 37.9, 39.1, 39.8, 99.0, 120.6, 128.4, 131.5, 143.5
4-4	0.84—0.95(m, 14H), 0.98—1.13(m, 8H), 1.15—1.28(m, 8H), 1.37—1.46(m, 4H), 1.58—1.79(m, 8H), 2.36—2.69(m, 4H), 7.06(d, J=7.8 Hz, 4H), 7.34(d, J=7.8 Hz, 4H)	14.1, 23.0, 29.3, 33.3, 33.3, 33.3, 37.2, 37.5, 37.8, 39.1, 99.0, 120.6, 128.4, 131.5, 143.5
5-4	0.74—0.93(m, 14H), 1.02—1.12(m, 8H), 1.15—1.26(m, 10H), 1.35—1.47(m, 6H), 1.62—1.73(m, 8H), 2.48—2.60(m, 4H), 7.05(d, J=7.2 Hz, 4H), 7.34(d, J=7.0 Hz, 4H)	14.1, 22.7, 23.0, 26.7, 29.3, 32.3, 33.3, 33.3, 33.3, 37.2, 37.5, 37.5, 37.9, 39.1, 99.0, 120.6, 128.4, 131.5, 143.5
5-5	0.82—1.00(m, 14H), 1.10—1.19(m, 8H), 1.20—1.33(m, 12H), 1.45—1.53(m, 4H), 1.68—1.84(m, 8H), 2.52—2.71(m, 4H), 7.13(d, J=8.0 Hz, 4H), 7.42(d, J=8.0 Hz, 4H)	14.1, 22.7, 26.7, 32.2, 33.3, 33.3, 33.3, 37.5, 37.5, 37.9, 39.1, 99.0, 120.6, 128.4, 131.5, 143.5

n	m	Transition temperature /℃[Enthalpy change/(kJ·mol^-1)]
		Heating process^a				Cooling process^b
		Cr	S_A	N	I	I	N	S_A	Cr
2	2	69.9(10.7)		160.8(23.2)	220.4(4.0)	219.9(-3.8)			159.4(-20.5)
3	2	50.7(1.9)		151.4(20.1)	233.5(6.2)	232.4(-5.1)			149.0(-15.9)
4	2	73.1(2.6)		135.2(16.1)	229.0(5.6)	227.4(-5.3)			132.3(-15.6)
5	2	78.4(24.7)		128.3(10.0)	225.8(4.6)	225.2(-4.4)			127.2(-9.4)
3	3	89.4(13.0)		140.5(10.4)	240.1(1.7)	239.6(-2.1)			138.4(-10.4)
4	3	58.5(14.6)		152.2(17.1)	240.4(5.1)	239.9(-4.6)			150.9(-16.5)
5	3	88.0(24.0)		140.2(12.0)	239.3(4.4)	238.8(-4.9)			138.9(-10.1)
4	4	66.8(17.5)		155.4(6.6)	235.7(3.9)	235.3(-3.8)			154.3(-16.1)
5	4	79.5(22.1)	144.9(0.6)	146.4(7.9)	234.8(4.5)	234.3(-4.3)	146.0(-4.2)	144.3(-8.9)	40.9(-18.5)
5	5	117.6(32.6)	144.5(8.9)	156.8(5.1)	234.0(5.0)	233.8(-4.9)	156.5(-4.9)	141.8(-9.7)	95.0(-29.5)