TWI229122B - Acetylene derivatives having three 1,4-phenylene rings, and liquid crystal composition and liquid crystal display device each comprising the same - Google Patents

Abstract

The present invention provides an acetylene derivative liquid crystalline compounds, represented by formula (I), wherein G1 is -CnH2n+1 or -OCnH2n+1, in which n is an integer of from 1 to 20; G2 is -CmH2m+1 or -OCmH2m+1, in which m is an integer of from 1 to 20; n is not equal to m; and R1, R2 and R3 independently represent H or C1-3 alkyl, wherein at least one of R1, R2, and R3 is not H. The present liquid crystalline compounds provide lower Tm and higher Tc, so is suitable to be used in liquid crystal display device.

Description

1229122 V. Description of the invention (1) The present invention relates to a triphenylbisacetylene compound, in particular to a phenyl group at both ends connected to a different alkyl or alkoxy group, and at least three of the benzene rings A triphenylbisacetylene compound having a pendant substituent. This radical diacetyl compound is suitable as one of the components of a liquid crystal mixture required for a liquid crystal display. The liquid crystal mixture 'required for a super-twisted nematic (STN) liquid crystal display needs to have a high optical anisotropy (Δη value is 0.15 to 0.20), and it needs a low melting point and a high clarification temperature to It has a wider temperature range of nematic liquid crystal phase. Generally speaking, the longer the resonance length of the liquid crystal core structure, the larger its A η value. Republic of China Patent No. 3 1 2702 discloses a liquid crystal monomer composed of diacetylene and two benzene rings. The Republic of China Patent No. 28804 has disclosed a triphenylbisacetylene liquid crystal monomer having an alkenyl group at its terminal.

Pugh et al. Disclosed a triphenylbisacetylene compound with a symmetrical alkoxy group on the terminal phenyl group, which can be used as a liquid crystal material (journal 〇f Polymer Science: Part A: Polymer Chemistry, Vol. 28, 1 1 0 1- 1 1 26 (1 990)). Although Pugh's triphenylbisacetylene compound has a high value of △ η, it has an excessively high melting point and a narrow nematic liquid crystal temperature range due to the alkoxy symmetrical structure, and it has a smectic liquid crystal phase, so it is not suitable for As a liquid crystal component required for a twist nematic (TN), super twist nematic (STN), and thin film transistor (TFT) liquid crystal display, it has no practical value. Therefore, the object of the present invention is to provide a solution

Page 4 1229122 V. Description of the invention (2) In addition to having a high value, it can also widen the range of its low melting point and relatively clear clarification industry, so it can be used as a grade The temperature of the liquid crystal is-, in particular: combined with the device: the required liquid crystal composition of the film-type transistor-type crystal display 扭转? Twisted nematic type, and one of the ingredients to achieve the purpose of the invention. Dibis-block compound, at both ends:! : Is to provide a novel triphenyl or alkoxy group, and three benzene rings are respectively connected with different alkyl groups. The triphenyl bis, one of the present invention has a pendant substituent. The basic diacetylene compound is shown in Chemical Formula ⑴ ...

-C ^ c- ^ •. Corpse 2 R, Ο) -g2 where G is -CnH2n + 1 or one μ ^ is an integer from 1 to 10, more particularly θ η, η is an integer from 1 to 20, especially -0C nine +1, m is an integer of 1 to 20 and f 6. "Heart is entrapped" or! To an integer of 6 ton, only a whole dagger, especially an integer of 1 to 10, more particularly, 2 3 is independently Η or a carbon number of 1 to 3 is a feature of the present invention In the formula, η is not equal to ra, so = an alkyl or alkoxy group having the same Gd% substituent at the terminal of the two-dried hydrazone. The terminal phenyl group in the process has a special group that is different from the present invention. Or ethoxy: In addition to the substituents of the above-mentioned gag2, that is, at least one of the R radicals has at least one of R1, R2, and r3 other than H. 1229122 ____ V. Description of the invention (3) ^ " ~ The compound of the present invention is mainly a triphenylbisacetylene structure, so it has a high Δη value, and the two ends of the triphenylbisacetylene compound of the present invention are clumsy. There are different alkyl or alkoxy groups on the base, because the length of the alkyl or alkyl groups at both ends is different, the attraction between the ends of the liquid crystal molecules is reduced. Furthermore, because there are side substituents on the benzene ring in the backbone center, The lateral forces of the liquid crystal molecules can be destroyed, so the dazzle point can be reduced, and the nematic phase temperature can be widened. As mentioned above, 'Because the present invention has a wide nematic liquid crystal temperature range, it is one of the crystal components, and is particularly suitable for nematic and thin film transistor liquid crystals. The base diacetyl compound has a wide range and can be used as The liquid required for a liquid crystal display is a liquid crystal component required for a twisted nematic, super twisted nematic display. The triphenylbisacetylene compound of the present invention can be added to any crystal as one of the liquid crystal compositions. Ingredients. The so-called liquid is generally known as a mixed substance with a liquid crystal phase composed of multiple ingredients. ° The liquid crystal composition of the present invention includes the present invention: a compound: and a liquid crystal. The best content is 〇〇2 2nd hair: the second benzyl diacetylene compound, and 50 to 99 99 wt ° two; the more preferred content of the triphenylbisacetylene compound of the invention is a liquid-forming liquid crystal composition 'Can be used according to the conventional technology to construct the following specific examples and cooperate with the drawings to explain the present invention in more detail.

1229122

^,, Features and advantages, but not to limit the present invention, the scope of the present invention should be based on the scope of the attached patent application. Brief description of the figure: Figure 1 is the first stage synthetic step of the triphenylbisacetylene compound of the present invention. Fig. 2 is a second stage synthetic step of the triphenylbisacetylene compound of the present invention. Figure 3 shows the relationship between the phase transition temperature and the number of m of PTPCCHdTP-nm series compounds (n = 1). Figure 4 shows the relationship between the phase transition temperature and the number of m of PTP (CH3) TP-nm series compounds (n = 3). Figure 5 shows the relationship between PTP (CH3) TP —nm series compounds (m temperature and the number of η. Phase transfer Figure 6 shows the increase in the Δη value of the triphenylbisacetylated human obtained in Example 7 of the present invention for the E63 liquid crystal Effect σ For the synthesis steps of the following Examples 1 to 6, please refer to the flowchart in Figure 1. For the synthesis steps of Example 7, please refer to the flowchart in Figure 2. Example 1: Synthesis of Compounds 1 a to 1 f Take compound la (n = 6) (l-hexyl-4-iodobenzene) as an example:

Dissolve 4-hexylaniline (10g, 56.5 mmole) in 30ml of thF 'cool to 0 ~ 5 ° C, slowly add 22ml of concentrated hydrochloric acid, stir the resulting solution in an ice bath for 5 ~ 10 minutes, and then quickly add 23ml Of the aqueous sodium nitrite aqueous solution (1 g / 3 m 1) 'was immediately poured into a 100 ml aqueous solution of potassium moth (0.56 mol) in an ice bath and dropped at the same temperature.

Page 7 1229122 V. Description of the invention (5) 2 ~ 3 hours. The product was diluted with n-hexane, and then washed with a saturated sodium thiosulfate aqueous solution, water and saturated brine, dried over anhydrous magnesium sulfate, concentrated, and separated by a silica gel column (using n-hexane as the eluent). A transparent colorless oily liquid was obtained with a yield of 94.7%. In a similar manner, compound lb (n = 5) (l-pentyl-4-iodobenzene) can be obtained with a yield of 95%: Example 2: Synthesis of compounds 2a to 2f with compound 2a (n = 6) (2- methyl-4- (4-hexylphenyl) -3-butyn-2-〇l) 2

Synthesis as an example: Compound la (14.4g, 50mmol) and 2-methyl-3-butyn-2-〇1 (6.3g, 7 5_〇1) were dissolved in 150 nil triethylamine, and each was added under nitrogen. Triphenylphosphine (l.00g, 3.75mmol) -bis (tripheny phosphine) palladium (II) chloride (0.35

g, 0.5 mmol) and cracked copper (0.38 g, 2 mmol), and the resulting solution was heated under reflux for one day. After cooling, the excess solvent was removed, diluted with diethyl ether, and then washed with a saturated aqueous solution of chloride, water and saturated brine, dried over anhydrous magnesium sulfate, concentrated, and separated on a silica gel column (using ethyl acetate: n-hexane = 1 : 4 is the extract solution). A brown oily liquid 2a was obtained in a yield of 95 ° / 0. In a similar manner, compound 2b (n = 5) (2-methyl-4- (4-pentylphenyl) -3-butyn-2 ~ ol) was obtained with a yield of 87%; compound 2c (n = 4) (2- methyl-4- (4-butylphenyl) -3-butyn-2-〇l),

Page 8 1229122 V. Description of the invention (6) Yield 88%; Compound 2d (n = 3) (2-methyl-4- (4-propylphenyl) -3-butyn-2-ol), Yield 96%; Compound 2e (n = 2) (2-methyl-4- (4-ethylphenyl) -3-butyn-2-〇1), yield ~ 100%; compound 2f (n = l) (2-methyl-4- (4 -methylphenyl) -3-butyn-2-〇1) with a yield of ~ 100%. Example 3: Synthesis of Compounds 3a to 3f Taking Compound 3a (n = 6) [l- (l-ethynyl) -4-hexylbenzene] as an example: Compound 2a (7.7 g, 31.6 mmol) and 100 ml of 1, 4-Dioxane (1,4-dioxane) was placed in a round-bottomed bottle, and 1.3 g of potassium hydroxide was added thereto, and heated to 100 ° C under a gas atmosphere. Collected by a dean-stark trap. The obtained product was cooled, added with water, and extracted with n-hexane, dried over anhydrous magnesium sulfate, concentrated, and separated by a silica gel column (n-hexane was used as an eluent). A transparent colorless oily liquid 3a was obtained in a yield of 97%. In a similar manner, compound 3b (n = 5) [l- (1-ethynyl) -4-pentylbenzene] was obtained in a yield of 83%; compound 3c (n = 4) [l- (l-ethynyl) -4-butylbenzene], yield 86%; compound 3d (n = 3) [l- (l-ethynyl) -4-propylbenzene], yield 93%; compound 3e (n = 2) [l- (l-ethynyl) -4-ethylbenzene], yield 81%, compound 3f (n = l) [l- (1-ethynyl) -4-methylbenzene], yield 78% .

Page 9 1229122 V. Description of the invention ⑻--Washed with L water and saturated brine, dried over anhydrous magnesium sulfate, concentrated, and separated on a silica gel column (with ethyl acetate: n-hexane = 1 ·· 4 as the extraction Liquid) to give a brown solid (5a) in 95% yield. In a similar manner, compound * 5b (n = 1, methyl in ortho position) can be obtained, yield 76%; compound 5c (n = 2, methyl in meta position), yield 86%. Example 6: Synthesis of compound 6a ~ 6c Take the synthesis of compound 6a (n = 3, methyl is in the ortho position) as an example: Compound 5a (7.25g, 29mmol) was dissolved in i5ml of THF. After cooling, Pour into an ice nitrite solution made up of 16m 1 concentrated hydrochloric acid and 17.5m 1 sodium nitrite. The resulting mixture is added to iced 6M potassium iodide aqueous solution (50ml), and stirred at the same temperature for 2 ~ 3 Hours later, a saturated aqueous sodium thiosulfate solution was added and extracted with n-hexane. The resulting organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, concentrated, and separated on a silica gel column (using n-hexane as the extract solution) 'A white crystalline solid (6a) was obtained in 6% yield. In a similar manner, compound 6b (n = 1, methyl in ortho position) can be obtained, yield 54%; compound 6c (n = 1, fluorenyl group in meta position) can be obtained, yield 27%. Example 7: Synthesis of triphenylbisacetylene compound [pTP (CH3) Tp —nm] Please refer to the flowchart in FIG. 2. Take the synthesis of compound PTP (CH3) TP-36 (n = 3, m = 6) as an example: First, compound 6a (3g, 8.3mmol), compound 3a (2.8g, 1 5 in in ο 1) > Gu Add 3 5 ml of diethylamine 'into a round-bottomed bottle, and under nitrogen, add two base plates (0.17 g, 0.65 μm η 1), bis (triphenylphosphine) palladium (II) chloride (60 mg, 0.083 mmol) and copper moth (60 mg, 0.31 mmol), the resulting solution was heated back

Page 11 1229122 V. Description of the invention (9) After flowing for one day, after cooling down, 'extract the extra Han Tian 丨 t ^ ^ W, the mixture, diluted with n-hexane, and then saturated aqueous ammonia gas solution, water and saturated food. , Raw, soil ^ ^ t _ & S washed with water β, dried over anhydrous magnesium sulfate, concentrated, and separated on a silica gel column (with i ρ,, and at as the eluent) to obtain a white crystalline solid [PTP ( CH3) TP-36] with a yield of 2i 5%. In a similar manner, a series of dibenzylbisacetylene compounds can be supplied. The yield and spectral data are shown in Table 1. In addition, the melting point (Tm), clear temperature (Tc), and enthalpy (ΔΗ) were measured with a micro difference scanning card. The results are shown in Table 2.

Page 121229122 V. Description of the invention (10) Table 1. Yield and chemical shift of compound PTP (CH3) TP-nm Compound yield (° / 〇) 300 MHz NMR (CDCl3,6, ppm) PTP (CH3) TP- 36 21.5% 0.86 ~ 0.95 (m, 6H), 1.24 ~; L27 (br, 6H), 1.57-1.67 (m, 4H), 2.48 (s, 3H), 2.55-2.62 (m, 4H), 7.1 2-7.16 (m, 4H), 7.29 ~ 7.45 (Γη, 7ΙΙ) 13C 13.74, 14.06, 20.56, 22.60, 24.29, 28.92, 31.23, 31.69, 35.89, 37.93, 87.52, 88.77, 90.93, 95.21, 120.33, 120.41, 122.98, 123.06, 128.48, 128.72, 131.39, 131.48, 161.60, 132.36, 139.99, 143.20, 143.52 PTP (CH3) TP- 35 28.6 ° / 〇.87-0.97 (m, 6H), 1.3 2 (br, 4H) , 1.61-1.68 (m, 4H), 2.49 (s, 3H), 2.57-2.63 (m, 4H), 7.14 ~ 7.17 (d, 4H), 7.30 ~ 7.33 (d, lH), 7.40 ~ 7.46 (m, 6H) 13C 13.74, 14.00, 20.94, 22.52, 24.32, 30.94, 31.40, 35.86, 37.96, 87.52, 88.74, 90.93, 95.21, 120.30, 120.41, 122.98, 123.07, 128.48, 128.71, 131.40, 131.49, 131.63, 132.36 , 143.26, 143.55 PTP (CH3) TP- 34 36.5% iH 0.88-0.93 (m, 6H), 1.3 0 ~ 1.36 (m, 2H), 1.54-1.64 (m, 4H), 2.47 (s, 3H), 2 52-2.60 (m, 4H), 7.1 0 ~ 7.1 3 (m, 4H), 7.28 ~ 7.30 (d, lH), 7.37 ~ 7.43 (m, 6H) 13C 13.71, 13.89, 20.53, 22.28, 24.26, 13.35, 35.57, 37.93, 87.52, 88.80, 90.96, 95.24, 120.36 , 120.44, 123.01, 123.07, 128.46, 128.72, 131.40, 131.47, 131.60, 132.33, 139.99, 143.17, 143.43

I.ϋ Page 13 1229122 V. Description of Invention (11) Continued Table 1 PTP (CH3) TP-33 31.0% 0.91-0.96 (t, 6H), 2.49 (s, 3H), 7. 13 ~ 7.16 (m, 4H), • 40 ~ 7.45 (m, 6H) 1.60 ~ 1.67 (m, 4H), 2.56 ~ 2.61 (t, 4H), 7.30 ~ 7.32 (d, lH),

13C 13.72, 20.53, 24.32, 37.93, 87.49, 88.74, 90.93, 95.18, 120.30, 120.44, 122.95, 123.04, 128.51, 128.69, 131.37, 131.46, 131.60, 131.75, 132.33, 140.02, 143.26_ PTP (CH3) TP32 21.0%

iH 0.91 ~ 0.96 (t, 3H), 1.21 ~ 1.27 (t, 3H), 0.61 ~ 1.68 (m, 2H), 2.46 (s, lH), 0.57 ~ 2.70 (m, 4H), 7.14 ~ 7.20 (m, 4l0, 0.30 to 7.33 (< A, 1: Η), 7.39 to 7.47 (Γη, 6Ιί)

13C 3.77, 15.38, 20.59, 24.32, 28.87, 37.99, 87.52, 88.77, 90.96, 95.21, 120.36, 120.50, 123.04, 123.09, 127.96, 128.54, 128.75, 131.52, 131.66, 132.39, 140.08, 143.29, CH3.86 P13.86TP TP- 16 69.2% 0.86-0.90 (t, 3H), 1.29-1.30 (br, 6H), 1.58 ~ 1.62 (m, 2H), 2.35 (s, 3H), 2.49 (s, 3H), 2.5 8-2 63 (t, 2H), .13 ~ 7.17 (m, 4H), 7.30 ~ 7.32 (d, lH), 7.39 ~ 7.45 (m, 6H)

13C 14.07, 20.56, 21.50, 22.57, 28.89, 31.27, 31.69, 35.92, 87.49, 88.74, 90.90, 95.21, 120.06, 120.41 122.94, 123.09, 128.48, 128.68 129.09, 131.40, 131.48, 131.63 132.60, PT. 138.45, 138.45, 138.45, 138.14 (CH3) TP- 15 79.3%

iH 0.89 ~ 0.91 (t, 3H), 1.31-1.34 (m, 4H), 1.59 ~ 1.63 (m, 2H), 2.36 (s, 3H), 2.49 (s, 3H), 2.58 ~ 2.63 (t, 2H) , 7.13 ~ 7.17 (m, 4H), 7_29 ~ 7.32 (d, lH), • 39 ~ 7.46 (m, 6H) _

Page 14 1229122 V. Description of Invention (12) Continued Table 1

13C 14.01, 20.56, 21.49, 22.48, 30.90, 31.40, 35.85, 87.48, 88.71, 90.86, 95.21, 120.06, 120.41, 122.95, 123.06, 128.39, 128.68, 129.09, 13 1.39, 131.45, 13 1.60, 132.36, 138.44, 140.02 , 143.54_ PTP (CH3) TP-14

iH 0.89-0. 94 (t, 3H), 1.30 ~ 1 · 3 8 (m, 2H), .56 ~ 1.61 (m, 2H), 2.34 (s, 3H), 2.48 (s, 3H), 2.5 8 ~ 2.63 (t, 2H), .12 ~ 7.16 (m, 4H), 7.29 ~ 7.32 (d, lH), 7.38 ~ 7.45 (m, 6H)

13C 13.91, 20.56, 21.49, 22.31, 33.38, 35.59, 87.51, 88.74, 90.89, 95.24, 120.09, 120.44, 122.97, 123.09, 128.51, 128.71, 129.12, 131.42, 13 1.48, 131.63, 132.36, 138.47, 140.05, 143.51

PTP (CH3) TP-13 90% Ή 0 ~ 91 ~ 0.96 (t, 3H), 1.60 ~ 1.65 (m, 2H), 2.35 (s, 3H), 2.49 (s, 3H), 2. 56-2.61 ( t, 2H), 7.1 3 ~ 7.1 6 (m, 4H), 7.30 ~ 7.32 (d, lH) 3 7.39 ~ 7.45 (m? 6H) PTP (CH3) TP-12 70.2%

iH PTP (CH3) TP-62 73.8% 13.74, 20.56, 21.49, 24.32, 37.95, 87.48, 88.71, 90.89, 95.21, 120.06, 120.47, 122.94, 123.06, 128.39, 128.68, 129.09, 131.39, 131.45, 131.63, 132.36, 138.44, 140.02, 143.28 1.20 ~ 1.25 (t, 3H), 2.48 (s, 3H), 7. 12 ~ 7.18 (m, 4H), 7.38 ~ 7.45 (m, 6H) 2-35 (s, 3H), 2.64 ~ 2.69 (m, 2H), 7.28 ~ 7.31 (d, lH),

lH 0.85 ~ 0.89 (t, 3H), 1.56-1.61 (m, 2H), 2.56 ~ 2.68 (m, 4H), 7.28 ~ 7.31 (d, lH), 1.20 ~ 1.31 (m, 8H), 2.48 (s, 3H), 7. 12 ~ 7.20 (m, 4H), 7.37 ~ 7.45 (m, 6H)

Page 15 1229122 V. Description of Invention (13) Continued Table 13C 4.06, 15.31, 20.53, 22.57, 28.80, 28.89, 31.16, 31.66, 35.88, 87.48, 88.74, 90.95, 95.18, 120.26, 120.47, 123.00, 123.06, 127.93 , 128.33, 128.42, 128.71, 131.48, 131.60, 132.36, 140.02, 143.49, 144.77 PTP (CH3) TP- 52 85.8% ΐΗ 0.84 ~ 0.89 (t, 3H), 1 · 61 ~ 1 · 28 (m, 6H), 1.53 ~ 1.5 8 (m, 2H), 2.45 (s, 3H), 2.51 ~ 2.62 (m, 4H), 7.07 ~ 7.12 (m, 4H), 7.26 ~ 7.29 (d, lH), 7.35 ~ 7.42 (m, 6H) 13C 13.97, 15.23, 20.47, 22.45, 28.75, 30.81, 31.40, 35.77, 87.48, 88.77, 90.98, 95.21, 120.26, 120.44, 122.97, 127.84, 128.36, 128.68, 131.42, 131.54, 132.27, 139.90, 143.34, 143.34 PTP (CH3) TP- 42 7 5 · 70 / 〇iH 0.90 ~ 0.95 (t, 3H), 1.22 ~ 1.27 (t, 3H), 1.30 ~ 1.36 (m, 2H), 1.55 ~ 1.60 (m, 2H), 2.49 (s, 3H), 2.5 9 ~ 2.67 (m, 4H), 7.14 ~ 7.20 (m, 4H), 7.30 ~ 7.33 (d, lHL 7.40-7.47 (m, 6H) 13C 13.90, 15.38, 20.56, 22.31 , 28.84, 33.38, 35.59, 87.49, 88.74, 90.96, 95.18, 120.27, 120.44, 123.01, 123.06, 127.96, 128.48, 128.71, 131.48, 131.63, 131.77, 132.39, 14〇 · 05, 143.52, 144.83 PTP (CH3) TP- 22 26% iH 1.22 ~ 1.27 (t, 6H), 2.50 (s, 3H), 2.63 ~ 2.67 (q, 4H), 7.16 ~ 7.20 (m, 4H), 7.30 ~ 7.33 (d, 1H), 7.43 ~ 7.47 (m, 6H) 13C 15.31, 15.37, 20.56, 28.83, 87.48, 88.71, 90.92, 95''8, 120.29, 120.44, 122.97, 123.06, 127.93, 128.71 , 131.48, 131.57, 13 1.63, 132.36, 140.05, 144.83

Η Page 16 1229122 V. Description of the invention (14) Table 2 PTP (CH,) TP-nm T 丄 τη τ. ΔΗ n = l, m = 2 143.2 192.4 Ί3Ί n = l, m = 3 139.1 187.4 6.64 n = l, m = 4 120.2 184.6 5.34 n = l, m = 5 111.3 185.7 5.38 n = l, m = 6 78.1 162.7 5.07 n = 2, m = l 136.5 189.6 7.12 n = 2, m = 2 144.5 186.4 6.33 n = 3, m = 2 115.3 190.0 5.38 n = 4, m = 2 72.2 177.4 4.19 n = 5, m = 2 61.6 173.5 3.54 n = 6, m = 2 61.0 165.1 5.80 n = 3, m = 3 123.4 200.4 5.03 n = 3, m = 4 98.5 191.2 5.27 n = 3, m = 5 86.2 182.8 3.61 n = 3, m = 6 ΊΊ. 9 170.0 3.75 n = 2, m = 5 97.8 179.9 4.52 n = 2, m = 6 Ί3 .9 166.5 5.17 n = 2, «1 = 6 * 133.6 191.1 3.61 n = 6, m = 3 57.3 168.7 3.28

* Without side substituents PTP (CH3) TP-nm series compounds (n = 1) phase transition temperature (ie, Tm and Tc) is plotted against the number of m. The results are shown in Figure 3. The area above Tc is the I area (isotropic; isotropic area), and the area between Tc * Tm is the N area (nematic;

Page 17

Claims (1)

Announcement 1229122 Thai VI. Patent application Sh 1. A triphenylbisacetylene compound, as shown by chemical formula (I) G -C ^ c Where Gi is -CnH2n + 1 or -OCnH2n + 1, η is an integer from 1 to 20, G2 is -CnH2m + 1 or -0 (^ 2111 + 1, m is an integer from 1 to 20, η is not equal to m, d , R2, and R3 are independently fluorene or an alkyl group having 1 to 3 carbon atoms, and at least one of dagger, R2 and dagger is not fluorene. 2. Triphenylbisacetylene as described in item 1 of the scope of patent application Compound where Gj is -CnH2n + 1, η is an integer from 1 to 10, G2 is -CmH2m + 1, and m is an integer from 1 to 10, as described in Article 3. Triphenylbisacetylene as described in item 2 of the scope of patent application Compound n and m are integers from 1 to 6. Compound 4. The triphenylbisacetylene compound as described in item 1 of the patent application range, wherein Gi is -OCnH2n + 1, η is an integer from 1 to 10, and G2 is- OCmH2m + 1, m is an integer from 1 to 10, 5. The triphenylbisacetylene compound as described in item 4 of the scope of the patent application, where n and m are integers from 1 to 6. 6. As the first scope of the patent application Triphenylbisacetylene compound Page 19 1229122, where both dagger and dagger are H, and R2 is an alkyl group having 1 to 3 carbon atoms. 7. The triphenylbisacetylene compound described in item 6 of the patent application, wherein R2 is fluorenyl. 8. A type of liquid crystal composition, including 0.01 to 50% by weight of the tribenzyl bisacetylene compound as described in the first item of the patent application 1, and 50 to 99.99 liquid crystals. Three to 9 • The liquid crystal composition according to item 8 of the scope of application for a patent, wherein the content of the bis-diethyl compound is 1 to 30 wt%. The liquid crystal is the liquid crystal composition described in item 8 of the scope of the patent application, wherein the liquid crystal composition is a TN liquid crystal, a super-twisted nematic (STN) liquid crystal, or a TFT liquid crystal. To be described ^ A liquid crystal display device composed of a crystal composition as described in item 8 of the scope of patent application.