GB2189785A - Tolan-type nematic liquid crystalline compounds - Google Patents

Tolan-type nematic liquid crystalline compounds Download PDF

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GB2189785A
GB2189785A GB08709632A GB8709632A GB2189785A GB 2189785 A GB2189785 A GB 2189785A GB 08709632 A GB08709632 A GB 08709632A GB 8709632 A GB8709632 A GB 8709632A GB 2189785 A GB2189785 A GB 2189785A
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Takatsu Haruyoshi
Sasaki Makoto
Tanaka Yasuyuki
Sato Hisato
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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Priority claimed from JP851984A external-priority patent/JPS60152427A/en
Priority claimed from JP1065884A external-priority patent/JPS60155142A/en
Priority claimed from JP5958984A external-priority patent/JPS60204734A/en
Priority claimed from JP5958884A external-priority patent/JPS60204731A/en
Priority claimed from JP59261413A external-priority patent/JPS61140579A/en
Priority claimed from GB08501733A external-priority patent/GB2155465B/en
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Abstract

A liquid crystalline compound which is a tolan derivative of the general formula <IMAGE> wherein <IMAGE> represents <IMAGE> or <IMAGE> R and R', independently from each other, represent a linear alkyl group having 1 to 10 carbon atoms, an alkoxymethylene group whose alkoxy moiety has 1 to 10 carbon atoms, a cyano group or a halogen atom, and n and m, independently from each other, represent 0 or 1, is useful as an electro-optical display material in a liquid crystal display cell.

Description

SPECIFICATION Tolan-type nematic liquid crystalline compounds This invention relates to novel tolan derivatives useful as an electrooptical display material. The novel tolan derivatives provided by this invention are compounds of the general formula
independently from each other, represent a linear alkyl group having 1 to 10 carbon atoms, an alkoxymethylene group whose alkoxy moiety has 1 to 10 carbon atoms, a cyano group or a halogen atom, and n and m, independently from each other, represent 0 or 1, and are referred to hereinafter as the compounds of formula (I).
Typical liquid crystal display cells include a field effect mode cell proposed by M. Schadt et al. [APPLIED PHYSICS LETTERS, 18, 127-128(1971], a dynamic scattering mode cell proposed by G. H. Heilmeier et al.
[PROCEEDINGS OF THE I.E.E.E., 56, 1 162-1171 (1968)1, and and a guest-host mode cell proposed by G. H.
Heilmeier et al. [APPLIED PHYSICS LETTERS, 13,91(1968)] or D. L. White et al. [JOURNAL OF APPLIED PHYSICS, 45,4718(1974)].
Among these liquid crystalline cells, a TN-type cell, a kind of the field effect mode cell, is now most prevailing. As reported by G. Bauer in Mol. Cryst. Liq. Cryst., 6345 (1981),the the product of the thickness in micrometers) of the TN-type cell multiplied by the anisotropy (An) of the refractive index of a liquid crystalline material filled in the cell should be preset at a specified value in order to prevent the occurrence of interference fringes on the cell surface which impair the appearance of the cell. In liquid crystalline cells now in practical use, the Anxd value is set at one of 0.5, 1.0, 1.6 and 2.2. Hence the d value can be decreased if a liquid crystalline material having a large An value is used.If the d value becomes smaller, the response time (T) becomes shorter in accordance with the weil-known expression and2. Accordingly, liquid crystalline materials having large An values are very important for the production of liquid crystal display cells having a high response speed and being free from an interference fringes.
The response time (T) is proportional to the viscosity (TI) of a liquid crsytalline material (namely, Tab). In other words, liquid crystalline materials having large An values and low viscosities are very important for the production of fast-responsive liquid crystal display cells.
The compounds represented by the formula
(wherein Rand R' represent a linear alkyl group) described in U. S. Patent No. 4,130,502 are especially good viscosity reducing agents for use in the production of fast-responsive liquid crystal display cells. These compounds can reduce the viscosity of mixed liquid crystals, but have the defect of decreasing their An values.
Many of practical liquid crystalline materials are prepared by mixing compounds having a nematic phase at room temperature or in its vicinity with compounds having a nematic phase at temperatures higher than room temperature. Many mixed liquid crystals of the above type now in practical use are required to have a nematic phase at least over the entire range of -30 C to +65"C. As the range of application of liquid crystal display cells has become wider, it has been desired to obtain liquid crystalline materials having a nematic liquid crystalline temperature range broadened to still higher temperatures.For this reason, a particular need has arisen recently for nematic liquid crystalline compounds having a high nematic phase-isotropic liquid phase transition temperature (this temperature is referred to as the N-l point). U. S. Patents Nos. 4,229,315 and 4,331,552 and West German Laid-Open Patent Publication No. 3233641 describe typical nematic liquid crystalline compounds having high N-l points which, however, have low An values.
The compounds of formula (I) in accordance with his invention are novel tolan derivatives all of which commonly have large An values, some of which have high N-l points, and some of which have an excellent ability to reduce viscosity.
Most of the compounds of formula (I) are nematic liquid crystalline compounds. Some of them are not liquid-crystalline, but are useful as viscosity reducing agents for liquid crystals. Accordingly, practical mixed liquid crystalline materials having a large An value, a high N-l point and a low viscosity can be prepared by mixing various matrix liquid crystals with the compounds of formula (I).
The compounds of formula (I) can be produced by the following process. This process, however, is not applicable to the production of compounds of general formula (I) in which
is
and compounds of general formula (I) in which R or R' is an alkoxymethylene group.
(i) First step }ClCOCH2Dw7Rl tii) RHCOCH2MmR. (iii) Second step } R-f /7 /1 /I Rm)Hc,H-cH2M)7R' (iv) OH Third step Rx & cH=cHD)7RI (v) Fourth step } s R%Th&num;cH-cHH7R' (vi) Br Br Fifth step R4DQcEc)7R' (I) First step The compound of formula (i) is reacted with the compound of formula (ii) and anhydrous aluminum chloride in carbon disulfide or nitrobenzene to produce the compound of formula (iii).
Second step The compound of formula (iii) produced in the first step is reacted with a reducing agent such as lithium aluminum hydride in anhydrous ether or anhydrous tetrahydrofuran to produce the compound of formula (iv).
Third step A dehydrating agent such as potassium hydrogen sulfate is added to the compound of formula (iv) produced in the second step, and the mixture is heated to perform dehydration and to produce the compound of formula (v).
Fourth step The compound offormula (v) produced in the third step is reacted with bromine in a solvent such as carbon tetrachloride, chloroform or 1,1,2-trichloroethane to produce the compound of formula (vi).
Fifth step The compound of formula (vi) produced in the fourth step is reacted with a base such as 1,5diazabicyclo[5.4.0]undecene-5 in a solvent such as N,N-dimethylformamide to produce the compound of formula (I).
The compound of formula (I) in which R or R' is CN can also be produced by first preparing the compound of formula (I) in which R or R' is Br and reacting the resulting compound with cuprous cyanide in a solvent such as N,N-dimethylformamide.
The compounds of formula (I) in which
is
can be produced by the following process.
In the first step, the compound of formula (vii) is reacted with p-iodobenzaldehyde in a solvent such as toluene to produce the compound of formula (viii). In the second step, the compound of formula (viii) produced in the first step is reacted with the compound of formula (ix) in a solvent such as N,Ndimethylformamide in the presence of a catalyst such as bis(triphenylphosphine) palladium (II) chloride to give the compound of formula (I).
The compounds of general formula (I) in which R or R' is an alkoxymethylene group can be produced by the following process.
In the first step, the compound of formula (x) is reacted with iodine in a mixed solvent of acetic acid and water to produce the compound of formula (xi). in the second step, the compound of formula (xi) produced in the first step is reacted with the compound of formula (xii) in a solvent such as N,N-dimethylformamide in the presence of a catalyst such as bis(triphenylphosphine)palladium (II) chloride to give the compound of formula (I).
Table 1 summarizes the transition temperatures of the compounds of formula (I) produced as above. In Table 1, all cyclohexane rings have a trans(equatorial-equatorial) configuration, and C, N, and I stand for a crystalline phase, a nematic phase and an isotropic liquid phase, respectively.
Table 1
No. R # m R' Transition temperature ( C) 1 n-C3H7- - 0 C2H5 51 (C # I) 2 n-C3H7- - 0 n-C3H7- 73 (C # I) 3 n-C3H7- - 0 n-C4H9- 22 (C # I) 15 (I # N) 4 n-C4H9 - 0 n-C4H9 41 (C # I) 5 n-C4H9 - 0 n-C5H11 26 (C # I) 21 (I # N) 6 F # 0 C2H5- 159 (C # N) 193 (N # I) 7 F # 0 n-C3H7- 162 (C # N) 202 (N # I) 8 F # 0 n-C5H11- 165 (C # N) 204 (N # I) 9 Cl # 0 n-C3H7- 188 (C # N) 230 (N # I) 10 C2H5- # 0 F 150 (C # N) 196 (N # I) 11 n-C3H7- # 0 F 154 (C # N) 207 (N # I) 12 n-C3H7- # 0 -Br 155 (C # N) 221 (N # I) 13 n-C3H7- # 0 -CN 153 (C # N) 265 (N # I) 14 n-C3H7- # 0 -Cl 141 (C # N) 219 (N # I) Table 1 (continued)
No. R # m R' Transition temperature ( C) 15 n-C3H7- # 0 -F 90 (C # N) 189 (N # I) 16 C2H5 # 0 -CN 135 (C # N) 250 (N # I) 17 C2H5 # 0 -Br 136 (C # N) 209 (N # I) 18 C2H5 # 0 -Cl 124 (C # N) 207 (N # I) 19 C2H5 # 0 -F 78 (C # N) 179 (N # I) 20 C2H5- # 0 n-C3H7- 86 (C # N) 189 (N # I) 21 n-C3H7- # 0 n-C3H7- 96 (C # N) 213 (N # I) 22 n-C3H7- # 0 n-C4H9- 87 (C # N) 201 (N # I) 23 n-C3H7- # 0 n-C5H11- 98 (C # N) 209 (N # I) 24 n-C4H9- # 0 n-C3H7- 89 (C # N) 207 (N # I) 25 n-C4H11- # 0 C2H5- 91 (C # N) 192 (N # I) 26 C2H5- # 0 n-C3H7- 163 (C # N) 221 (N # I) 27 n-C3H7- # 0 n-C3H7- 164 (C # N) 230 (N # I) 28 n-C5H11- # 0 n-C3H7- 160 (C # N) 211 (N # I) 29 n-C5H11- # 0 C2H5- 157 (C # N) 206 (N # I) - to be continued - Table 1 (continued)
No. R # m R' Transition temperature ( C) 30 C2H5- # 1 n-C3H7- 194 (C # N) above 300 (N # I) 31 C2H5- # 1 n-C5H11- 210 (C # N) above 300 (N # I) 32 n-C3H7- # 1 n-C3H7- 185 (C # N) above 300 (N # I) 33 n-C3H7- # 1 n-C5H11- 202 (C # N) above 300 (N # I) 34 n-C3H7 # 0 n-C4H9 83 (C # N) 195 (N # I) 35 n-C3H7 # 0 F 118 (C # N) 178 (N # I) 36 n-C6H13 # 0 n-C4H9 85 (C # N) 176 (N # I) 37 n-C6H13 # 0 F 113 (C # N) 174 (N # I) 38 n-C4H9 # 0 -CH2OCH3 -25 (C # I) 39 n-C5H11 # 0 -CH2OCH3 39 (C # I) 9 (I # N) 40 n-C4H9 # 0 -CH2OCH3 108 (C # S) 112 (S # N) 196 (N # I) All of the compounds of formula (I) in accordance with this invention show weak negative dielectric anisotropy. Most of them are nematic liquid crystalline compounds, and some of them are compounds similar to liquid crystals. Accordingly, they can be used, for example in the form of a mixture with other nematic liquid crystalline compounds having negative or weakly positive dielectric anisotropy, as a material for dynamic scattering mode display cells. Furthermore, as a mixture with other nematic liquid crystalline compounds having strong positive dielectric anistropy, they can be used as a material for field effect mode display cells.
Typical examples of preferred nematic liquid crystalline compounds which can be used as mixtures with the compounds of general formula (I) include 4,4'-substituted benzoates, phenyl 4,4'-substituted cyclohexanecarboxylates, bi phenyl 4,4'-su bstituted cyclohexaneca rboxylates, 4'-substituted phenyl 4-(4-substituted cyclohexanecarbonyloxy)benzoates, 4'-su bstituted phenyl 4-(4-su bstituted cyclohexyl )benzoates, 4'-su bstituted cyclohexyl 4-(4-substituted cyclohexyl)benzoates, 4,4'-substituted biphenyls, 4,4'-substituted phenylcyclohexanes, 4,4'-substituted terphenyls, 4,4'-biphenylcyclohexane, and 2-(4'-substituted phenyl)-5-substituted pyrimidines.
Table 2 summarizes the viscosities and An values (anisotropy of refractive index) measured of mixed crystals prepared from 75% by weight of matrix liquid crystals (A) now in widespread use as a nematic liquid crystalline material and 25% by weight of the compound Nos. 1 to 5 of formula (I) respectively, and for comparison, of the matrix liquid crystals (A) themselves.
The matrix liquid crystals (A) are composed of 40% by weight of n-C3H7 30% by weight of n--CSH11 30% by weight of n--C7HIS
TABLE 2 Viscosityat20 C An (c.p.) (-) (A) 22.0 0.118 (A)+No. 1 17.6 0.132 (A)+No. 2 17.7 0.133 (A)+No.3 18.1 0.131 (A)+No.4 18.4 0.129 (A)+No.5 18.3 0.129 From the data presented in Table 2, it can be understood that the compounds Nos. 1 to 5 of formula (I) shown in Table 1 can reduce the viscosity of the matrix liquid crystals (A), and increase their refractive index anistotropy (An).
The characteristic properties of these compounds can also be demonstrated by the following experiment.
A compound of the following formula
which is known to be an especially superior viscosity reducing agent for the production of fast-responsive liquid crystal display cells was mixed in varying proportions with the matrix liquid crystals (A) described above.
Likewise, compound No. 1 of this invention having the following formula
was mixed in varying proportions with the matrix liquid crystals (A).
The viscosities and An values of the resulting mixed liquid crystals were measured.
Figure 1 of the accompanying drawings is a graph drawn on the basis of the results of measurement and showing the relation between the viscosities and An values.
The results will demonstrate that while the known superior viscosity reducing agent reduces An, the compounds of formula (I) in accordance with this invention (Nos. 1 to 5 shown in Table 1) reduce the viscosity of liquid crystals and at the same time increase their An and thereby can greatly improve the response speed of the liquid crystals.
Table 3 summarizes the N-l points and An values (anisotropy of refractive index) of mixed liquid crystals composed of 90% by weight of matrix liquid crystals (B) shown below with 10% by weight of compounds Nos.
6 to 40 shown in Table 1 and for comparison, of the matrix liquid crystals (B). The matrix liquid crystals (B) are
composed of HQ 20% by weight of n-C3H7CN, 16% by weight ofn--C,HCN, 16% by weight of n-C7H15CN, 8% byweightofnC3H7}COO XOC2H5, 8% by weight of nC3H7eF O-n-C4H9, 8% by weight of n-C4H9 COO OCH3, 8% by weight of n-C4H9 -( H > COO OC2H5, and 8% by weight of n-C5H11 zCOO OCH3, ]A COOOCH3, 8% by weight of n-C5H11 COO OC2H5.
TABLE3 Mixed N-l point dn crystals ("C) (A) 54.0 0.0917 (A)+No.6 67.4 0.119 (A)+No.7 68.2 0.118 (A)+No.8 68.3 0.118 (A)+No.9 71.0 0.121 (A)+No.10 67.7 0.118 (A)+No.11 68.5 0.118 (A)+No.12 74.9 0.116 (A)+No.13 70.4 0.115 (A)+No.14 70.2 0.114 (A)+No.15 67.1 0.111 (A)+No.16 73.2 0.116 (A)+No.17 69.1 0.115 (A)+No.18 68.9 0.113 (A)+No.19 66.2 0.110 (A)+No.20 66.3 0.110 (A)+No.21 68.7 0.112 (A)+No.22 67.5 0.109 (A)+No.23 68.5 0.109 (A)+No.24 68.1 0.109 (A)+No.25 66.8 0.110 (A)+No.26 69.3 0.120 (A)+No.27 69.5 0.121 (A)+No. 28 68.4 0.120 (A)+No.29 68.1 0.120 (A)+No.30 82.0 0.111 (A)+No.31 81.8 0.109 (A)+No.32 82.1 0.111 (A)+No.33 81.9 0.110 (A)+No.34 67.3 0.118 (A)+No.35 65.0 0.119 (A)+No.36 64.2 0.118 (A)+No.37 63.6 0.120 (A)+No.38 - 0.104 (A)+No.39 - 0.103 (A)+No.40 - 0.110 The data presented in Table 3 demonstrate that the compounds Nos. 6 to 40 shown in Table 1 increase the N-I point of the matrix liquid crystals (B) to a level sufficient for practical purposes and also greatly increase their An.
The characteristic properties of these compounds will also be demonstrated by the following comparative experiment.
Known compounds of the following formulae (b) to (e) which are similar in chemical structure to the compounds of formula (I) in accordance with this invention and are used to increase the N-l points of mixed liquid crystals were each mixed in various proportions with the matrix liquid crystals (B).
On the other hand, compounds of this invention structurally similar to the four known compounds shown above (Nos. 7, 13,21 and 33) were each mixed in various proportions with the matrix liquid crystals (B).
The N-l points and An values of the resulting mixed liquid crystals were measured.
Figures 2, 4, 6 and 8 of the accompanying drawings are graphs drawn on the basis of the results of measurement and showing the relation between the N-l points and the amounts added.
Figures 3, 5, 7 and 9 of the accompanying drawings are graphs drawn on the basis of the results of measurement and showing the relation betwen An and the amounts added.
A comparative study of these graphs will show that as compared with the known compounds of formulae (b), (c), (d) and (e), the compounds of this invention Nos. 7, 13,21 and 33 can greatly increase the N-l points and An values of the matrix liquid crystals.
The following Examples illustrate the present invention more specifically.
Example 1 Anhydrous aluminum chloride (16 g; 0.120 mole) was added to 200 ml of carbon disulfide, and while heating the solution under reflux, a mixture of 10.6 g (0.100 mole) of ethylbenzene and 19.7 g (0.100 mole) of 4-n-propylphenyl-acetyl chloride was added dropwise to the solution. The mixture was headed under reflux for 1 hour, and carbon disulfide was evaporated. The product was added to ice water, and the mixture was stirred at 60"C for 1 hour. After cooling, the product was extracted with toluene, washed with water and dried.
Toluene was evaporated, and the residue was recrystallized from methanol to give 20 g (0.0752 mole) of a compound of the following formula.
The compound was dissolved in 50 ml of anhydrous tetrahydrofuran (THF), and the solution was added dropwise to a mixed solution of 3.2 g (0.0840 mole) of lithium aluminum hydride and 120 ml of anhydrous THF to perform reaction at room temperature for 1 hour. To the solution were added 200 ml of 9% HCI and 200 ml of water. The product was extracted with toluene, washed with water and dried. Toluene was evaporated fron the extract and the residue was dissolved in 300 ml of toluene. Potassium hydrogen sulfate (3 g; 0.0220 mole) was added to the solution, and the mixture was heated under reflux for 1 hour while removing water. After the reaction, the inorganic materials were separated by filtration and toluene was evaporated. Subsequent recrystallization from ethanol gave 15 g (0.0600 mole) of a compound of the following formula.
The resulting compound was dissolved in 200 ml of 1,1,2-trichloroethane, and at room temperature 9.6 g (0.0600 mole) of bromine was added dropwise to the solution to perform reaction for 1 hour. Methanol (150 ml) was added to the reaction solution, and the mixture was cooled. The precipitated crystals were collected by filtration, washed with methanol, and dried. The resulting compound was dissolved in 100 ml of N,N-dimethylformamide, and 14 g (0.0921 mole) of 1,5-diazabicyclo[5.4.0]undecene-5 was added. The mixture was heated under reflux for 2 hour. After cooling, dilute hydrochloric acid was added to render the reaction mixture acidic. It was then extracted with ethyl acetate, washed with water and dried, and the solvent was evaporated. Subsequent recrystallization from methanol gave 8.70 g (0.0351 mole) of a compound of the following formula.
Yield: 46.7% Transition temperature: 51 C (C < l) Example 2 A compound of the following formula was produced in the same way as in Example 1.
Yield: 43.5% Transition temperature: 73 C (C < l) Example 3 A compound of the following formula was producd in the same way as in Example 1.
Yield: 45.3% Transition temperature: 22 C (C~l) 15 C (I#N) Example 4 A compound of the following formula was produced in the same way as in Example 1.
Yield: 45.1% Transition temperature: 41 C (C~l) Example 5 A compound of the following formula was producd in the same way as in Example 1.
Yield: 45.4% Transition temperature: 26 C (C~l) 21 C (I < N) Example 6 Anhydrous aluminum chloride (16.0 g; 0.120 mole) was added to 150 ml of carbon disulfide, and while heating the solution under reflux, a mixture of 17.2 g (0.100 mole) of fluorobiphenyl and 19.7 g (0.100 mole) of 4-n-propylphenylacetyl chloride was added dropwise to the solution. The mixture was headed under reflux for 1 hour, and carbon disulfide was evaporated. The product was added to ice water, and stirred at 60 C for 1 hour. After cooling, the product was extracted with toluene, washed with water and dried. Toluene was evaporated, and subsequent recrystallization from ethanol-acetone gave 27 g (0.0813 mole) of a compound of the following formula.
The resulting compound as crystals was gradually added to a mixed solution of 3.10 g (0.813 mole) of aluminum lithium hydride and 100 ml of anhydrous THFto perform reaction at room temperature for 1 hour.
Furthermore, 300 ml of 9% HCI and 300 ml of water were added. The mixture was then extracted with toluene, washed with water and dried. Toluene was evaporated from the extract, and the resulting crystals were dissolved in 300 ml of toluene. Furthermore, 2.7 g (0.0198 mole) of potassium hydrogen sulfate was added to the solution. The mixture was heated under reflux for 1 hour while removing water. After the reaction, the product was washed with water and dried. Toiuene was evaporated, and the residue was recrystallized from ethanol-acetone to give 22 g (0.0701 mole) of a compound of the following formula.
The resulting compound was dissolved in 250 ml of 1,1 ,2-trichloroethane, and while 11.2 g (0.0701 mole) of bromine was added dropwise to the solution at room temperature, the reaction was carried out for 1 hour. The precipitated crystals were collected by filtration, washed with methanol, and dried. The resulting compound was dissolved in 200 ml of N,N-dimethylformamide. To the solution was further added 20 g (0.132 mole) of 1 ,5-diazabicyclo[5.4.0]undecene-5, and the mixture was heated under reflux for 5 hours. After cooling, the product was extracted with toluene, washed with water and dried. Subsequent recrystallization from ethanol-acetone gave 10 g(0.0316 mole) of a compound of the following formula.
Yield: 31.6% Transition temperature: 162"C (CN) 202"C (N~l) Example 7 A compound of the following formula was produced in the same way as in Example 6.
Yield: 30.7% Transition temperature: 159"C (C < N) 193"C (N < l) Example 8 A compound of the following formula was produced in the same way as in Example 6.
Yield: 32.2% Transition temperature: 165"C (C~N) 204 C (N#I) Example 9 A compound of the following formula was produced in the same way as in Example 6.
Yield: 31.4% Transition temperature: 188 C (C~N) 230 C (N#I) Example 10 A compound of the following formula was produced in the same way as in Example 6.
Yield: 34.3% Transition temperature: 1500C (CN) 196do (Nfl) Example 11 Acompound ofthefollowing formula was produced in the same way as in Example 6.
Yield: 32.8% Transition temperature: 150"C (N) 207"C (N2l) Example 12 Anhydrous aluminum chloride (24.0 g; 0.180 mole) was added to 250 ml of carbon disulfide, and while heating the solution under reflux, a mixture of 30.3 g (0.15 mole) of trans-4-propyl-1-phenylcyclohexane and 35 g (0.15 mole) of 4-bromo-phenylacetyl chloride was added dropwise. The mixture was heated under reflux for 1 hour, and carbon disulfide was evaporated. The residue was added to ice water, and then stirred at 60"C for 1 hour. After cooling, the product was extracted with toluene, washed with water, and dried.Toluene was evaporated, and the residue was recrystallized from ethanol-toluene (2:1) to give 35 g (0.088 mole) of a compound of the following formula.
The resulting compound was dissolved in anhydrous THF, and the solution was added dropwise to a mixed solution of 4.00 g (0.105 mole) of aluminum lithium hydroxide and 150 ml of anhydrous THF. The reaction was carried out at room temperature for 2 hours. Then, 200 ml of 9% HCI and 200 ml of water were added, and the reaction mixture was extracted with toluene, washed with water and dried. Toluene was evaporated. The resulting crystals were dissolved in 300 ml of toluene, and 2.80 g (0.0206 mole) of potassium hydrogen sulfate was added. While water was removed by a decanter, the mixture was heated under reflux for 1 hour. After the reaction, the inorganic materials were separated by filtration. The filtrate containing the product was recrystallized to give 26.8 g (0.07 mole) of a compound of the following formula.
The resulting compound was dissolved in 150 ml of 1,1 ,2trichloroethane, and reacted for 1.5 hours while adding dropwise 12.3 g (0.077 mole) of bromine at room temperature. The precipitated crystals were collected by filtration, washed with methanol, and dried. The resulting compound was dissolved in 250 ml of N,N-dimethylformamide, and 11.7 g (0.077 mole) of 1 ,5-azabicyclo[5.4.0]undecene-5 was added. The mixture was heated under reflux for 4 hours. After cooling, water was added. The precipitated crystals were collected by filtration, washed with methanol, and dried to give 18.9 g (0.0496 mole) of a compound of the following formula.
Yield: 33.1% Transition temperature: 1 55"C (CN) 211"C (Nvl) Example 13 3.81 g (0.0100 mole) of the tolan derivative obtained in Example 12 was dissolved in 70 ml of N,Ndimethylformamide, and 1.35 g (0.015 mole) of cuprous cyanide was added. The mixture was heated under reflux for 12 hours. After cooling, a hydrochloric acid solution of ferric chloride was added, and the mixture was stirred for 0.5 hour. The reaction mixture was extracted with ether, washed with water, and dried.
Subsequent recrystallization from ethanol-toluene (1 :2) gave 2.30 9 (0.00703 mole) of a compound of the following formula.
Yield: 23.3% Transition temperature: 153 C (CN) 265 C (N#I) Example 14 A compound of the following formula was produced in the same was as in Example 12.
Yield: 34.2% Transition temperature: 141 'C (C#N) 219 C (N#I) Example 15 A compound of the following formula was produced in the same way as in Example 12.
Yield: 32.7% Transition temperature: 90 C (C < N) 189 C (N#I) Example 16 A compound of the following formula was produced in the same way as in Example 12.
Yield: 22.7% Transition temperature: 1350C (C~N) 250 C (N#I) Example 17 A compound of the following formula was produced in the same way as in Example 12.
Yield:33.8% Transition temperature: 136 C (C#N) 209 C ((N#I) Example 18 A compound of the following formula was produced in the same way as in Example 12.
Yield: 34.7% Transition temperature: 124 C (C#N) 207 C (N#I) Example 19 A compound of the following formula was produced in the same way as in Example 12.
Yield: 32.2% Transition temperature: C (C < N)179 C (N
Example 20 Anhydrous aluminum chloride (24.0 g; 0.180 mole) was added to 200 ml of carbon disulfide, and while heating the solution under reflux, a solution composed of 28.2 g (0.150 mole) of trans-4-ethyl-1 phenylcyclohexane, 29.5 g (0.150 mole) of 4-n-propylphenylacetyl chloride and 50 ml of carbon disulfide was gradually added dropwise. After the addition, the mixture was refluxed for 1 hour. The reaction mixture was cooled, added to ice water and stirred at 60"C for 1 hour. Carbon disulfide was evaporated, and the residue was extracted with toluene, washed with water, and dried over anhydrous sodium sulfate.Toluene was evaporated, and the residue was recrystallized from ethanol-toluene (2:1) to give 38.1 g (0.109 mole) of a compound of the following formula.
The resulting compound was dissolved in anhydrous THF, and the solution was added dropwise to a mixed solution composed of 4.96 g (0.131 mole) of aluminum lithium hydride and 150 ml of anhydrous THF. The mixture was refluxed for 2 hours, and 250 ml of 9% hydrochloric acid and 250 ml of water were added dropwise. The reaction mixture was extracted with toluene, washed with water, and dried over anhydrous sodium sulfate. The solvent was evaporated to give a crude product of the following formula.
The crude product was dissolved in 300 ml of toluene, and 3.56 g (0.0262 mole) of potassium hydrogen sulfate was added. With refluxing, the dehydration reaction was carried out, and water was removed by a decanter. After the reaction, the reaction product was washed with water and dried. Toluene was evaporated, and the residue was recrystallized from ethanol-toluene (1 :2) to give 27.5 g (0.0828 mole) of a compound with the following formula.
The resulting compound was dissolved in 200 ml of 1,1,2-trichloroethane, and with stirring at 10"C, 14.6 g (0.0913 mole) of bromine was added dropwise, and the reaction was carried out for 2 hours. The reaction mixture was cooled. The precipitated crystals were collected by filtration, washed with methanol, and dried.
The resulting compound was dissolved in 250 ml of N,N-dimethylformamide, and 13.8 g (0.0908 mole) of 1,5-diazabicyclo[5.4.0]undecene-5 was added. The mixture was refluxed for 5 hours. After the reaction, the reaction mixture was cooled, and water was added. The precipitated crystals were collected by filtration, washed with methanol, and dried. The product was recrystallized from ethanol-toluene (1:2) to give 17.3 g (0.0524 mole) of a compound of the following formula.
Yield: 34.5% Transition temperature: 86 C (C < N) 189"C (Nfl) Example 21 A compound of the following formula was produced in the same way as in Example 20.
Yield: 35.8% Transition temperature: 96 C (C~N) 213C (Noi) Example 22 A compound of the following formula was produced in the same way as in Example 20.
Yield: 35.1% Transition temperature: 87 C (C#N) 201 C (N#I) Example 23 A compound of the following formula was produced in the same way as in Example 20.
Yield: 36.4% Transition temperature: 98 C (C#N) 209 C (N#I) Example 24 A compound of the following formula was produced in the same way as in Example 20.
Yield: 34.0% Transition temperature: 89 C (CN) 207 C (N#I) Example 25 A compound of the following formula was produced in the same way as in Example 20.
Yield: 32.7% Transition temperature: 91 C (C#N) 192 C (N#I) Example 26 A compound of the following formula was produced in the same way as in Example 20.
Yield: 36.9% Transition temperature: 163 C (C#N) 221 C (N#I) Example 27 A compound of the following formula was produced in the same way as in Example 20.
Yield: 37.4% Transition temperature: 164 C (C~N) 230 C (N#I) Example 28 A compound of the following formula was produced in the same way as in Example 20.
Yield: 37.1% Transition temperature: 160"C (CeN) 211 C (N#I) Example 29 A compound of the following formula was produced in the same way as in Example 20.
Yield: 36.6% Transition temperature: 157"C (CoN) 206 C (N#I) Example 30 To 100 mi of carbon disulfide was added 9 g (0.0680 mole) of anhydrous aluminum chloride, and while heating the solution under reflux, a mixture of 9.4 g (0.0500 mole) of trans-4-ethyl-1 -phenylcyclohexane and 14 g (0.0500 mole) of trans-4-n-propyicyclohexylphenylacetyl chloride was added dropwise to the solution.
The mixture was heated under reflux for 1 hour, and carbon disulfide was evaporated. The product was added to ice water, and stirred at 60"C for 1 hour. After cooling, the reaction product was extracted with toluene, washed with water and dried. Toluene was evaporated, and the residue was recrystallized from ethanol to give 18 g (0.0420 mole) of a compound of the following formula.
The resulting compound as crystals was gradually added to a mixture of 1.6 g (0.0420 mole) of aluminum lithium hydride and 80 ml of anhydrous THF, and the reaction was carried out at room temperature for 1 hour.
To the reaction solution were added 150 ml and 9% HCI and 150 ml of water. The mixture was extracted with toluene, washed with water, and dried. Toluene was evaporated from the extract. The resulting crystals were dissolved in 300 ml of toluene, and 1.5 g (0.0110 mole) of potassium hydrogen sulfate was added to the solution. While removing water, the mixture was heated under reflux for 1 hour. After the reaction, the inorganic materials were separated by filtration, and the residue was recrystallized to give 14.4 g (0.0350 mole) of a compound of the following formula.
The resulting compound was dissolved in 250 ml of 1,1,2-trichioroethane, and 5.6 g (0.0350 mole) of bromine was added dropwise at room temperature. The reaction was thus carried out for 1 hour. The precipitated crystals were collected by filtration, washed with methanol, and dried. The resulting compound was dissolved in 120 ml of N,N-dimethylformamide. To the solution was further added 14 g (0.0921 mole) of 1,5-diazabicyclo[5.4.0]undecene-5, and the micture was heated under reflux for 3 hours. After cooling, the reaction product was extracted with toluene, washed with water, and dried. Subsequent recrystallization from ethanol-acetone gave 8 g (0.0200 mole) of a compound of the following compound.
Yield: 40.0% Transition temperature: 194"C (C#N) above 300"C (N > l) Example 31 A compound of the following formula was produced in the same way as in Example 30.
Yield: 37.5% Transition temperature: 210"C (C < N) above 300"C (Nfl) Example 32 A compound of the following formula was produced in the same way as in Example 30.
Yield: 34.7% Transition temperature: 185 C (C#N) above 300 C (N#I) Example 33 A compound of the following formula was produced in the same way as in Example 30.
Yield: 36.4% Transition temperature: 202 C (CN) above 300 C (N#I) Example 34 A mixture of 5.4 g (0.048 mole) of 2-n-propyl-1 3-propanediol and 11.2 g (0.048 mole) of p-iodobenzaldehyde was dissolved in 100 ml of toluene, and a catalytic amount of p-toluenesulfonic acid was added. The mixture was heated under reflux for 2 hours. After the reaction, the toluene layer was washed with water and dried.
Toluene was evaporated under reduced pressure, and the residue was recrystallized from methanol to give 13 g (0.039 mole) of a compound of the following formula.
3.3 g (0.010 mole) of this compound was dissolved in 30 ml of N,N-dimethylformamide, and 3.3 mg (0.0047 mole) of bis(triphenylphosphine) palladium (II) chloride, 17 mg (0.088 mole) of cuprous iodide and 0.7 g (0.091 mole) of diethylamine were added. With stirring, 1.6 g (0.010 mole) of 4-n-butylphenylacetylene was further added. The reaction as carried out at room temperature for 1 hour. After the reaction, 30 ml of 9% hydrochloric acid was added, and the reaction product was extracted with toluene. The extract was washed with water, and dried, and toluene was evaporated under reduced pressure. The product was recrystallized from ethanol to give 2.6 g (0.0072 mole) of a compound of the following formula.
Yield: 72% Transition temperature: 83 C (CN) 195 C (N#I) Example 35 A compound of the following formula was produced in the same way as in Example 34.
Yield: 64% Transition temperature: 1 180C (C < N) 178 C (N#I) Example 36 A compound of the following formula was produced in the same way as in Example 34.
Yield: 68% Transition temperature: 85 C (C~N) 176 C (N#I) Example 37 A compound of the following formula was produced in the same way as in Example 34.
Yield: 61% Transition temperature: 113 C (C#N) 174 C (N#I) Example 38 Periodic acid (7.1 g; 0.0310 mole) and 33.7 g (0.138 mole) of iodine were dissolved in a mixed solvent composed of 122 ml of acetic acid, 23 ml of water and 15 ml of carbon tetrachloride, and 32.3 g (0.265 mole) of methyl benzyl ether was added. The mixture was heated under reflux for 20 hours. After the reaction, a solution of 32 g (0.300 mole) of sodium hydrogen sulfite in 200 ml of water was added. The reaction product was extracted with ether. The extract was washed with water and dried. Ether was evaporated, and the residue was distilled under reduced pressure to give 45 g (0.182 mole) of a compound of the following formula.
A portion (7.5 g; 0.0300 mole) of the resulting compound was dissolved in 50 ml of N,N-dimethylformamide, and 10 mg (0.0142 mmole) of bis(triphenylphosphine) palladium (II) chloride, 50 mg (0.263 mmole) of cuprous iodide and 2 g (0.274 mole) of diethylamine were added to the solution. With stirring, 5.2 g (0.0300 mole) of 4-n-pentylphenylacetylene was added, and the reaction was carried out at room temperature for 1 hour. After the reaction, 50 ml of 9% hydrochloric acid was added, and the reaction product was extracted with toluene.
The extract was washed with water and dried. Toluene was evaporated, and the residue was recrystallized from methanol to give 4 g of a compound of the following formula.
Yield: 46% Transition temperature: 39 C (C < l) 9 C (I#N) Example 39 A compound of the following formula was produced in the same way as in Example 38.
Yield: 42% Transition temperature: -25 C (C#I) Example 40 A compound of the following formula was produced in the same way as in Example 38.
Yield: 40% Transition temperature: 108 C (CoS) 112 C (S#N) 196 C (N#I)

Claims (10)

1. A compound of the general formula
wherein
represents
R and R', which may be the same or different, each represent a linear alkyl group having 1 to 10 carbon atoms, an alkoxymethylene group whose alkoxy moiety has 1 to 10 carbon atoms, a cyano group or a halogen atom, and n and m, which may be the same or different, each represent 0 or 1.
2. A compound according to claim 1 which is of the general formula
wherein R and R', which may be the same or different, each represent a linear alkyl group having 1 to 10 carbon atoms.
3. A compound according to claim 1 which is of the general formula
wherein one of the R1 and R2 represents a linear alkyl group having 1 to 10 carbon atoms, and the other represents a halogen atom.
4. A compound according to claim 1 which is of the general formula
wherein R represents a linear alkyl group having 1 to 10 carbon atoms, and R' represents a cyano group or a halogen atom.
5. A compound according to claim 1 which is of the general formula
wherein R and R', which may be the same or different, each represent a linear alkyl group having 1 to 10 carbon atoms
represents
or
and the cyclohexane ring has a trans(equatorialequatorial) configuration.
6. A compound according to claim 1 which is of the general formula
wherein R and R', which may be the same or different, each represent a linear alkyl group having 1 to 10 carbon atoms.
7. A compound according to claim 1 which is of the general formula
wherein R represents a linear alkyl group having 1 to 10 carbon atoms, R' represents a halogen atom or a linear alkyl group having 1 to 10 atoms, and the dioxane ring has a trans configuration.
8. A compound according to claim 1 which is of the general formula
wherein R and R', which may be the same or different, each represent a linear alkyl group having 1 to 10 carbon atoms, n isO or 1, and the cyclohexane ring has a trans(equatorial-equatorial) configuration.
9. A compound according to claim 1 substantially as described with reference to any one of Examples 1 to 10.
10. Use as an electro-optical display material in a liquid crystal display cell of a compound as claimed in any one of the preceding claims.
GB08709632A 1984-01-23 1987-04-24 Tolan-type nematic liquid crystalline compounds Expired GB2189785B (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP851984A JPS60152427A (en) 1984-01-23 1984-01-23 Novel trans-nematic liquid crystal compound
JP1065884A JPS60155142A (en) 1984-01-24 1984-01-24 Novel trans-type nematic liquid crystal compound
JP5958984A JPS60204734A (en) 1984-03-29 1984-03-29 Novel tolan based nematic liquid crystal compound
JP5958884A JPS60204731A (en) 1984-03-29 1984-03-29 Novel tolan nematic liquid crystal compound
JP59261413A JPS61140579A (en) 1984-12-11 1984-12-11 Novel tolan-type nematic liquid crystal compound
GB08501733A GB2155465B (en) 1984-01-23 1985-01-23 Tolan-type nematic liquid crystalline compounds

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4874543A (en) * 1986-11-14 1989-10-17 Casio Computer Co., Ltd. Liquid crystal composition
EP0393443A2 (en) * 1989-04-19 1990-10-24 MERCK PATENT GmbH Supertwist liquid crystal display
GB2240544A (en) * 1990-01-29 1991-08-07 Merck Patent Gmbh Liquid crystalline chloro tolanes
CN108822869A (en) * 2018-08-17 2018-11-16 西安近代化学研究所 A kind of liquid-crystal compounds containing chlorine and combinations thereof and high frequency assembly comprising it

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1166912A (en) * 1966-01-21 1969-10-15 Geigy Ag J R Improvements in the production of diphenyl acetylenes
GB1344040A (en) * 1971-11-19 1974-01-16 Anvar Disubstituted tolans and preparation thereof
GB1469818A (en) * 1973-04-21 1977-04-06 Hoechst Ag Process for preparation of acetylenes
GB2005296A (en) * 1977-09-12 1979-04-19 Secr Defence Liquid crystal materials and devices containing them

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1166912A (en) * 1966-01-21 1969-10-15 Geigy Ag J R Improvements in the production of diphenyl acetylenes
GB1344040A (en) * 1971-11-19 1974-01-16 Anvar Disubstituted tolans and preparation thereof
GB1469818A (en) * 1973-04-21 1977-04-06 Hoechst Ag Process for preparation of acetylenes
GB2005296A (en) * 1977-09-12 1979-04-19 Secr Defence Liquid crystal materials and devices containing them

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4874543A (en) * 1986-11-14 1989-10-17 Casio Computer Co., Ltd. Liquid crystal composition
EP0393443A2 (en) * 1989-04-19 1990-10-24 MERCK PATENT GmbH Supertwist liquid crystal display
EP0393443A3 (en) * 1989-04-19 1991-07-03 MERCK PATENT GmbH Supertwist liquid crystal display
GB2240544A (en) * 1990-01-29 1991-08-07 Merck Patent Gmbh Liquid crystalline chloro tolanes
GB2240544B (en) * 1990-01-29 1993-08-18 Merck Patent Gmbh Liquid crystalline fluorinated chloro tolans
CN108822869A (en) * 2018-08-17 2018-11-16 西安近代化学研究所 A kind of liquid-crystal compounds containing chlorine and combinations thereof and high frequency assembly comprising it
CN108822869B (en) * 2018-08-17 2022-10-25 西安近代化学研究所 Chlorine-containing liquid crystal compound, composition thereof and high-frequency assembly comprising chlorine-containing liquid crystal compound

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