JP2767299B2 - Tolan compounds - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to compounds of formula I below and to the use of these compounds as components of liquid crystal phases: C _m H _{2m + 1} -Q ¹ -C during ^{_{n H 2n -Q 2 -Ph 1 -C≡C}} -Ph 2 -Q 3 -C o H 2o + 1 I [ wherein, Ph ¹ and Ph ² are each, independently of one another, unsubstituted or 1,4-phenylene having one or two fluorine atoms as a substituent, Q ¹ is —CH ＝ CH—, Q ² is a single bond, and Q ³ is —O
-Or a single bond, m is 0-8, n is 2-5, and o is 1-12].

For simplicity, in the following description, Phe is an unsubstituted 1,4-phenylene group and PheX is a 1,4-phenylene group having one or two fluorine atoms as a substituent.

The compounds of the formula I are especially useful in twisted cells (SBE, ST
N, OMI, etc.), the liquid crystal phase for displays based on the guest-host effect, the effect of deformation of the ordered phase, or the effect of dynamic scattering. Can be used as a component. It is suitable to be used as a compound of the formula I or a component of a liquid crystal phase for a display based on the ECB effect.

Prior Art Compounds of similar structure are described in U.S. Pat. No. 3,925,482. However, these compounds do not contain an alkenyl group or a branched alkyl group or an alkoxy group in the side chain.

[Object and Utility of the Invention] An object of the present invention is to find a novel and stable liquid crystal or mesogen compound suitable as a component of a liquid crystal phase. This object has been achieved by providing compounds of the formula I.

It has been found that the compounds of the formula I are particularly suitable as components of the liquid crystal phase. In particular, by using these compounds, a stable liquid crystal phase having very high optical anisotropy and particularly preferable elasticity can be prepared. Thus, on the one hand, the substances of the formula I
It is particularly suitable for use in mixtures for effects and, on the other hand, for mixtures for TN cells with relatively large torsion angles.

BACKGROUND ART The ECB effect (the effect of electrically controlled birefringence) or the DAP effect (the effect of deformation of the ordered phase) was first reported in 1971 [Deformation of MFShieckel and K. Fahrenschon. nematic liquid crystals with
vertical orientation in electrical fields ", Appl.Ph
ys. Lett. 19 (1971) 3912]. Subsequently, JF Kahn [Appl. Phys. Lett. 20 (1972), p. 1193] and G. Labr
unie and J. Robert [J. Appl. Phys. 44 (1973), 4
869] A study has been published.

A paper by J. Robert and F. Clerc [SID 80 Digest T
echn.Papers (1980), 30], a paper by J. Duchene [Disp.
lays 7 (1986), 3] and a paper by H. Schad [SID 82
Digest Techn. Papers (1982), 244] states that a liquid crystal phase has a high elastic constant ratio value K ₃ / K ₁ , a high optical anisotropy value Δn, and a negative It is required to have a dielectric anisotropy value Δε of

An electro-optic display element based on the ECB effect has a homeotropic orientation. That is, the liquid crystal phase has negative dielectric anisotropy.

Cells with relatively large torsion angles are, for example, C.
Proc. Soc. Inf. Disp by M. Walters et al. (New York, 198
5) (3rd Intern.Display Conference, Kobe, Japan); DE
-OS 35 03 259; Ap by TJ Scheffer and J. Nehring
pl.Phys. Lett. 45 (1984), 1021; M. Schadt and F. Leenh
Outs Appl. Phys. Lett. 50 (1987), 236; EP-OS 0,2
46,842; and SID 87 Digest 391 by K. Kawasaki et al.
(20.6).

The corresponding mixture must carefully optimize the elastic materials (eg K ₃ / K ₁ and K ₃ / K ₂ ) that are critical for the particular cell type, especially for the determination of the optical properties As the compound, a compound having a high proportion of double bonds is advantageous.

For industrial use in electro-optical display devices, an LC phase is required that must meet many requirements. Here, moisture, air and physical effects such as heat,
Of particular importance is chemical stability, such as in the infrared, visible and ultraviolet radiations, as well as AC and DC electric fields. The LC phase which can be used industrially is also required to have a liquid crystal mesophase in a suitable temperature range and a low viscosity, especially at low temperatures.

DISCLOSURE OF THE INVENTION It has been surprisingly found that the addition of the compounds of the formula I results in a liquid-crystalline phase which meets the above-mentioned essential requirements in a particular way.

The compounds according to the invention are distinguished by a particularly favorable combination of the parameters of the materials in question in comparison with the known compounds.

Furthermore, by providing the compounds of the formula I, the scope of the liquid crystal materials suitable for the preparation of nematic mixtures is very generally extended from various technical points of view.

The compounds of the formula I have a wide range of applications. These compounds can be used as a base material mainly constituting a liquid crystal phase by selecting a substituent. However, the compounds of the formula I can also be added to liquid crystal substrates from other types of compounds, for example to optimize the dielectric and / or optical anisotropy of the corresponding dielectric. . The compounds of the formula I are furthermore suitable as intermediates for producing other substances which can be used as components of the liquid crystal phase.

The compounds of the formula I are colorless in pure form and form liquid-crystalline mesophases in a temperature range which is favorable for electro-optical applications. These compounds are chemicals,
It is sufficiently stable to heat and light.

The invention therefore relates to the compounds of the formula I and to the use of these compounds as components of the liquid-crystalline phase. The present invention still further relates to a liquid crystal phase containing at least one compound represented by the formula I and a liquid crystal display device containing such a phase, particularly an electro-optical display device. Throughout this ^{specification, Phe, Phex, Ph 1,} P
h ² , Q ¹ , Q ² , Q ³ , m, n and o have the above-mentioned meanings unless otherwise specified.

Binuclear like tolans having a vinylene group in the side chain (subformula _{I b) C m H 2m +} 1 -CH = CH-C n H 2n -Ph 1 -C≡C-Ph 2 -Q 3 -C o H _{2o + 1} Ib.

As subexpression I b are preferred include compounds represented by the following _{formula: C m H 2m + 1 -CH} = CH-C n H 2n -Phe-C≡C-Phe-Q 3 -C o H 2o ₊₁ I ba C _m H _{2m + 1} -CH = CH-C _n H _2n -Phe-C≡C-PheX-Q ³ -C _o H _{2o + 1 Ibb} C _m H _{2m + 1} -CH = CH- C _n H _2n -PheX-C≡C-Phe-Q ³ -C _o H _{2o + 1 Ibc} C _m H _{2m + 1} -CH = CH-C _n H _2n -PheX-C≡C-PheX-Q ³ -C _o H _{2o + 1} I bd among these compounds, partial formula I ba, I bb and I bc
Are particularly preferred, and in particular the compounds of the partial formula Iba are preferred.

Q ² and Q ³ are a single bond or an ether group -O-,
In the case of compounds I aa~I ad is, Q ² and Q ³ independently of one another can be different. However, preferably, only one of the two groups Q ² or Q ³ are an -O- ether group.

Preferred compounds of formula Ib are those of formula I
baa, I bab, I bba, I bbb, includes compounds represented by I bca and _{I bcc: C m H 2m +} 1 -CH = CH-C n H 2n -Phe-C≡C-Phe-C o H _{2o + 1} I baa C _m H _{2m + 1} -CH = CH-C _n H _2n -Phe-C≡C-Phe-O-C _o H _{2o + 1} I bab C _m H _{2m + 1} -CH = CH -C _n H _2n -PheX-C≡C-Phe-C _o H _{2o + 1} I bba C _m H _{2m + 1} -CH = CH-C _n H _2n -PheX-C≡C-Phe-O-C _o H _{2o + 1} I bbb C _m H _{2m + 1} -CH = CH-C _n H _2n -Phe-C≡C-PheX-C _o H _{2o + 1} I bca C _m H _{2m + 1} -CH = CH-C _{n H 2n -Phe-C≡C-PheX} -O-C o H 2o + 1 I bcb among these, compounds I bab, I bbb and I bcb are particularly preferred. Group C _m H _{2m + 1} and C _n H _2n -Phe for vinylene group (for m ≠ 0) cis - or trans - can be arranged, trans isomers are preferred. Subexpression
Corresponding compounds where m = 0 at Ib are also preferred.

The group C _m H _{2m + 1} and the group C present in the compounds of the formula I
_n H _2n may be linear or branched but is preferably linear.

When the compound of formula I contains a vinylene group in the side chain (subformula Ib), m0m8 and n2
n5. Thus, C _m H _{2m + 1} is preferably an H atom or a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl group, and C _n H _2n is preferably ethylene, Propylene, butylene or pentylene.

The alkyl group C _o H _{2o + 1} present in the compounds of the formula I
Can be linear or branched. This group is preferably straight-chain and o can be 1-12. Thus, C _O H _{2o + 1} is preferably a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl group. Ethyl, propyl and pentyl and also methyl are particularly preferred.

Compounds of the formula I having branched alkyl groups C _m H _{2m + 1} or C _o H _{2o + 1} in the side chains also have good solubility in conventional liquid-crystal substrates, since they have good solubility. , Especially when they are optically active, as chiral doping substances,
It can be important because it can be used.

Such branched groups generally do not have more than one chain branch. Preferred branched groups are isopropyl, 2-butyl (= 1-methylpropyl), isobutyl (= 2-methylpropyl), 2-methylbutyl, isopentyl in consideration of the numerical ranges of the groups relating to m and o. (=
3-methylbutyl), 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, 2-octyl, 4-methylhexyl, 2-nonyl,
2-decyl or 2-dodecyl. In the case of compounds having a branched terminal substituent, Formula I includes both optical antipodes and racemates, as well as mixtures thereof.

Among the compounds of the formula I and its sub-formulas, preference is given to those compounds in which at least one of the groups present in the molecule has one of the preferred meanings mentioned above.

Furthermore, preferred tolan compounds of the formula I are those in which Q ¹ present in the molecule is a vinylene group, Q ² is a single bond and Q ³ is an ether group, wherein The groups C _m H _{2m + 1} and C _n H _2n are in trans configuration, especially with respect to the double bond of the vinylene group (when m ≠ 0): Among these compounds, in subformula IV, n = 2,
4 or狹have the following group of a corresponding compound is 6 are particularly _{preferred: C m H 2m + 1 -CH} = CH-C 2 H 4 -Phe-C≡C-Phe-O-C o H 2o + ₁ C _m H _{2m + 1} -CH = CH-C ₄ H ₈ -Phe-C≡C-Phe-O-C _o H _{2o + 1} C _m H _{2m + 1} -CH = CH-C ₆ H ₁₂ -Phe _{-C≡C-Phe-O-C o} H 2o + 1 Furthermore, Trang compound represented by formula I preferred anti, Q ¹ present in the molecule is a vinylene group, Q ² is a single bond, And Q ³ is an ether group, the phenylene group in this compound is particularly unsubstituted, and m is particularly preferably 0 and n is the corresponding compound wherein 2, 4 or 6 is: CH = _{CH-C 2 H 4 -Phe-} C≡C-Phe-O-C o H 2o + 1 CH = CH-C 4 H 8 -Phe-C≡C-Phe-O-C o H 2o + 1 CH = _{CH-C 6 H 12 -Phe-} C≡C-Phe-O-C o H 2o + 1 ( in each formula, a 1o12).

Compounds of the formula I are described, for example, in the literature [eg Ho
Methoden der Organischen Chemie by uben-weyl (G
eorg-Thieme publisher, Stuttgart), according to conventional methods, especially under reaction conditions selected from known reaction conditions suitable for the reactions mentioned. Can be manufactured. In these reactions, variants which are known per se and which are not described in detail here can also be used.

If desired, the starting materials can also be produced in situ, such that they are directly reacted further, without isolation from the reaction mixture, to produce a compound of formula I.

Thus, compounds of formula I can be prepared by brominating the corresponding stilbene compound and then dehydrohalogenating the product. For this purpose, variants which are known per se and which are not described in detail here can also be used.

Stilbene compounds are 4-substituted benzaldehydes
It can be produced by reacting with the corresponding phosphoylide by the ig reaction, or by reacting the 4-substituted phenylethylene with the corresponding bromobenzene derivative by the Heck reaction.

Another way in which a CC triple bond can be created corresponds to formula I, but instead of a -C≡C- bond -CH
A compound having ₂ -CO- group, is reacted with an inorganic acid chloride, and then the generated group -CH ₂ -CCl ₂ - or dehydrohalogenation in the presence of a base, or reacting with semicarbazide and selenium dioxide It consists of a way to make The triple bond is then introduced with heating in the presence of methyllithium.

Another possible method is to convert the corresponding benzyl derivative to tran by reaction with hydrazine and then with HgO.

Compounds of formula I are also described by AOKing, E. Negishi,
Chem. 43 , 358 by FJ Villani and A. Silveira.
(1978), in a manner similar to that described in
It can also be prepared by coupling an alkynyl-zinc compound with an aryl halide.

Compounds of formula I are also described by Fritsch-Buttenberg
The 1,1-diaryl-2-halogeno-ethylene compound is rearranged in the presence of a strong base by the Wiechell rearrangement (Ann. 279, p. 319, p. 327, p. 332, 1984) to form a diarylacetylene compound Alternatively, it can be manufactured.

The compounds of the formula I can also be used in the presence of 4-substituted phenylacetylene compounds and aryl halides in the presence of palladium catalysts such as bis (triphenylphosphine) -palladium (II) chloride and copper (I) iodide. Can be manufactured from [This is Synthesi
s (1980) p. 627 or Tetrahedron Letters 27 (1986)
P. 1171].

The starting materials are in most cases known and can be prepared by processes known per se.

The liquid-crystal phases according to the invention comprise, in addition to one or more compounds of the formula I, preferably 2 to 40, in particular 4
Contains up to 30 components. These liquid crystal phases particularly preferably consist of 7 to 25 components and one or more of the compounds of the formula I. These additional components are preferably nematic or nematogenic (mono- or isotropic) materials, especially azoxybenzene compounds, benzylideneaniline compounds, biphenyl compounds, terphenyl compounds, phenyl or cyclohexylbenzoate compounds, phenyl or cyclohexylcyclohexanecarboxylate compounds. , Phenyl or cyclohexylcyclohexyl benzoate compound, phenyl or cyclohexyl cyclohexyl cyclohexane carboxylate compound, cyclohexyl phenyl benzoate compound, cyclohexyl phenyl cyclohexane carboxylate compound, cyclohexyl phenyl cyclohexyl cyclohexane carboxylate compound, phenyl cyclohexane compound, cyclohexyl biphenyl Phenylcyclohexylcyclohexane compound, cyclohexylcyclohexane compound, cyclohexylcyclohexene compound, cyclohexylsylcyclohexylcyclohexene compound, 1,4-bis-cyclohexylbenzene compound, 4,4′-bis-cyclohexylbiphenyl compound, phenyl or Cyclohexylpyridine compound, phenyl or cyclohexylpyridine compound, phenyl or cyclohexyldioxane compound,
Phenyl- or cyclohexyl-1,3-dithiane compound, 1,2-diphenylethane compound, 1,2-dicyclohexylethane compound, 1-phenyl-2-cyclohexylethane compound, 1-cyclohexyl-2- (4-phenyl-cyclohexyl) -Ethane compound, 1-cyclohexyl-2-biphenylethane compound, 1-phenyl-2
Selected from the group consisting of cyclohexyl-phenylethane compounds, optionally halogenated stilbene compounds, benzylphenylether compounds, tolan compounds and substituted cinnamic acid compounds.

The 1,4-phenylene groups present in these compounds may be fluorinated.

The most important compounds that can be used as components of the liquid crystal phase according to the present invention can have the characteristics represented by the following formulas 1, 2, 3, 4 and 5.

R'-L-U-R " 1 R'-L-COO-U-R" 2 R'-L-OOC-U-R "3 R'-L-CH 2 CH 2 -U-R" 4 R '-LC-C-U-R "5 In Formula 1, Formula 2, Formula 3, Formula 4 and Formula 5, L and U can each be the same or different, and independently of each other, -Phe-, -Cyc-, -Phe-Phe
-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-,
-G-Phe- and -G-Cyc- and a divalent group selected from the group consisting of their mirror image groups, in which Phe is 1,4-phenylene, and this group is unsubstituted. Cyc is trans-1,4-cyclohexylene or 1,4-cyclohexenylene, and Pyr is pyrimidine-2,5-diyl or pyridine-2,5-diyl. Dio is 1,3-dioxane-2,5-diyl, and G is 2- (trans-1,4
-Cyclohexyl) -ethyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl or 1,3-dioxane-2,
5-diyl.

Preferably, one of the groups L and U is Cyc, Phe
Or Pyr. U is preferably Cyc, Phe or Phe
-Represents Cyc. The liquid crystal phases according to the invention are preferably those in formulas 1, 2, 3, 4 and 5 where L and U are Cyc, P
It contains one or more components selected from the corresponding compounds meaning he and Pyr, and this liquid crystal phase further comprises, in formulas 1, 2, 3, 4 and 5, One represents Cyc, Phe and Pyr, and the other one of these groups is -Phe-Phe-, -Phe-Cyc
-, -Cyc-Cyc- and -G-Cyc- simultaneously contain one or more components selected from the corresponding compounds selected from the group consisting of -C-Cyc- and -G-Cyc-. In addition to this, this liquid crystal phase
Optionally a corresponding compound of formulas 1, 2, 3, 4 and 5 wherein L and U are selected from the group consisting of -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc And one or more components selected from the group consisting of:

In a narrow group of compounds of the formulas 1, 2, 3, 4 and 5 (subgroup 1), R ′ and R ″ independently of one another are alkyl, alkenyl having up to 8 carbon atoms, Alkoxy, alkenoxy In most of these compounds, R 'and R "are different from each other and one of these groups is usually alkyl or alkenyl. In another preferred narrow group of compounds of formulas 1, 2, 3, 4 and 5 (subgroup 2):
R ″ represents —CN, —CF ₃ , —F, —Cl or —NCS;
R ′ has the same meaning as described in the subgroup 1, preferably alkyl or alkenyl. In the compounds of formulas 1, 2, 3, 4, and 5, the various other substituents included are also conventional. Many such materials are commercially available. All of these substances are obtained by methods known from the literature or by analogous methods.

The liquid-crystal phases according to the invention preferably also contain, in addition to the components selected from sub-group 1, the components of sub-group 2, the proportions of these components being: sub-group 1: 20-90% Subgroup 2: 10 to 50%, especially 10 to 50% In these liquid-crystalline phases, the proportions of the compounds according to the invention and the compounds of subgroups 1 and 2 are both 100% Can be a percentage.

The phases according to the invention preferably contain 1 to 40%, in particular 5 to 30%, of a compound according to the invention. Phases which contain the compounds according to the invention in amounts of more than 40%, in particular in amounts of 45 to 90%, are also preferred. The phases according to the invention preferably contain three, four or five of the compounds according to the invention.

The liquid-crystal phases according to the invention are prepared in a manner customary per se. In general, the components are dissolved with one another, preferably at an elevated temperature. The liquid crystal phases according to the invention can be modified by using suitable additives so that they can be used in all liquid crystal display devices of the type disclosed hitherto. Such additives are known to those skilled in the art and are described in the literature (Handbook of Liq by H. Kelker / R. Hatz).
uid Crystals, Verlag Chemie, Weinheim, 1980). For example, a polychromatic dye can be added to create a colored guest-host system, or a substance can be added to alter the dielectric anisotropy, viscosity, and / or orientation of the nematic phase.

The following examples are intended to illustrate the invention without limiting it. Throughout this specification, percentages are percentages by weight. All temperatures are given in degrees Celsius.

The term "finish in the usual way" has the following meaning: water is added, the mixture is extracted with methylene chloride, the organic phase is separated off, dried and then evaporated, the product is then crystallized and ( Or) Purify by chromatography.

Example 1 15 mmol of 4-bromobut-1-ene and Mg 0.015
0.01 mol of 4-butoxy-4'-bromo-tolan (this compound is prepared from butoxybenzene and 4-bromo-phenyl-acetyl chloride according to GB 2,155,465) from 50 mol of a Grignard reagent prepared in 50 ml of ether from To a mixture of 50 ml of diethyl ether and 0.2 mmol of Dppf.PdCl ₂ (1,1-bis (diphenylphosphino) -ferrocene-palladium (II) dichloride) is added dropwise at room temperature. The mixture is stirred at room temperature for 24 hours, then hydrolyzed with water and the product is worked up in the usual way.

4-Butoxy-4 '-(3-butenyl) -tolan is obtained.

Similarly, the following compound is prepared: 4-butoxy-4 '-(4-pentenyl) -tolan 4-butoxy-4'-(3-pentenyl) -tolan 4-butoxy-4 '-(5-hexenyl ) -Tran 4-butoxy-4 '-(3-hexenyl) -tolan 4-butoxy-4'-(6-heptenyl) -tolan 4-butoxy-4 '-(3-heptenyl) -tolan 4-pentoxy-4 '-(3-Butenyl) -tolan 4-pentoxy-4'-(4-pentenyl) -tolan 4-pentoxy-4 '-(3-pentenyl) -tolan 4-pentoxy-4'-(5-hexenyl)- Tolan 4-pentoxy-4 '-(3-hexenyl) -tolan 4-pentoxy-4'-(6-heptenyl) -tolan 4-pentoxy-4 '-(3-heptenyl) -tolan 4-hexo Cy-4 '-(3-butenyl) -tran 4-hexoxy-4'-(4-pentenyl) -tolan 4-hexoxy-4 '-(3-pentenyl) -tolan 4-hexoxy-4'-(5- Hexenyl) -tran 4-hexoxy-4 '-(4-hexenyl) -tran 4-hexoxy-4'-(6-heptenyl) -tran 4-hexoxy-4 '-(3-heptenyl) -tran 4-heptoxy- 4 '-(3-butenyl) -tran 4-heptoxy-4'-(4-pentenyl) -tran 4-heptoxy-4 '-(3-pentenyl) -tran 4-heptoxy-4'-(5-hexenyl) -Tran 4-heptoxy-4 '-(3-hexenyl) -tolan 4-Heptoxy-4'-(6-heptenyl) -tolan 4-Heptoxy-4 '-(3-heptenyl) -tolan -Methoxy-4 '-(3-butenyl) -tolan 4-methoxy-4'-(4-pentenyl) -tolan 4-methoxy-4 '-(3-pentenyl) -tolan 4-methoxy-4'-(5 -Hexenyl) -tolan 4-methoxy-4 '-(3-hexenyl) -tolan 4-methoxy-4'-(6-heptenyl) -tolan 4-methoxy-4 '-(3-heptenyl) -tolan 4-ethoxy -4 '-(3-Butenyl) -tolan 4-ethoxy-4'-(4-pentenyl) -tolan 4-ethoxy-4 '-(3-pentenyl) -tolan 4-ethoxy-4'-(5-hexenyl ) -Tran 4-ethoxy-4 '-(3-hexenyl) -tolan 4-ethoxy-4'-(6-heptenyl) -tolan 4-ethoxy-4 '-(3-heptenyl) -tolan 4-propoxy-4 '-(3-Butenyl) -tolan 4-propoxy-4'-(4-pentenyl) -tolan 4-propoxy-4 '-(3-pentenyl) -tolan 4-propoxy-4'-(5-hexenyl)- Tolan 4-propoxy-4 '-(3-hexenyl) -tolan 4-propoxy-4'-(6-heptenyl) -tolan 4-propoxy-4 '-(3-heptenyl) -tolan 2,3 difluoro-4- Ethoxy-4 '-(3-butenyl) -tolan 2-fluoro-4-propoxy-4'-(4-pentenyl) -tolan 4-methoxy-3'-fluoro-4 '-(3-hexenyl) -tolan 4 -Hexoxy-2 ', 3'-difluoro-4'-(3
-Heptenyl) -tolan 4-ethyl-4 '-(3-butenyl) -tolan 4-ethyl-4'-(4-pentenyl) -tolan 4-ethyl-4 '-(3-pentenyl) -tolan 4-ethyl -4 '-(5-Hexenyl) -tolan 4-ethyl-4'-(3-hexenyl) -tolan 4-ethyl-4 '-(6-heptenyl) -tolan 4-ethyl-4'-(3-heptenyl ) -Tran 4-propyl-4 '-(3-butenyl) -tolan 4-propyl-4'-(4-pentenyl) -tolan 4-propyl-4 '-(3-pentenyl) -tolan 4-propyl-4 '-(5-Hexenyl) -tran 4-propyl-4'-(3-hexenyl) -tran 4-propyl-4 '-(6-heptenyl) -tolan 4-propyl-4'-(3-heptenyl)- Trang 4-buty -4 '-(3-Butenyl) -tolan 4-butyl-4'-(4-pentenyl) -tolan 4-butyl-4 '-(3-pentenyl) -tolan 4-butyl-4'-(5-hexenyl ) -Tran 4-butyl-4 '-(3-hexenyl) -tolan 4-butyl-4'-(6-heptenyl) -tolan 4-butyl-4 '-(3-heptenyl) -tolan 4-pentyl-4 '-(3-Butenyl) -tolan 4-pentyl-4'-(4-pentenyl) -tolan 4-pentyl-4 '-(3-pentenyl) -tolan 4-pentyl-4'-(5-hexenyl)- Tolan 4-pentyl-4 '-(3-hexenyl) -tolan 4-pentyl-4'-(6-heptenyl) -tolan 4-pentyl-4 '-(3-heptenyl) -tolan 4-hexyl-4'- (3-butenyl) -to Run 4-hexyl-4 '-(4-pentenyl) -tolan 4-hexyl-4'-(3-pentenyl) -tolan 4-hexyl-4 '-(5-hexenyl) -tolan 4-hexyl-4'- (3-hexenyl) -tolan 4-hexyl-4 '-(6-heptenyl) -tolan 4-hexyl-4'-(3-heptenyl) -tolan 4-heptyl-4 '-(3-butenyl) -tolan 4 -Heptyl-4 '-(4-pentenyl) -tolan 4-heptyl-4'-(3-pentenyl) -tolan 4-heptyl-4 '-(5-hexenyl) -tolan 4-heptyl-4'-(3 - hexenyl) - Tran 4-heptyl-4 '- (6-heptenyl) - Tran 4-heptyl-4' - (3-heptenyl) - Br ₂ to a mixture of Tran example 2 a) Mg 100 mmol and diethyl ether 50ml Add a drop. A solution of 150 mmol of 4-bromo-1- (3-methyl) -butoxybenzene in 50 ml of diethyl ether is then added. The mixture is stirred for about 30 minutes and then added to the Grignard reagent at 20-25 ° C.
A mixture of 150 mmol of 4-acetylpentylbenzene and 25 ml of diethyl ether is added. The mixture was stirred for 2 hours, poured over 500 ml of H ₂ O, acidified with concentrated HCl and then t
Extract with ert-butyl methyl ether (MTB ether). The organic phase was concentrated, the 20% H ₂ SO ₄ 120ml was added, 1 hour and the mixture is heated to reflux. 1- (p-pentylphenyl) 1- (p- (3-methyl) -butoxyphenyl)-
Ethene is obtained.

b) 1- (p-pentylphenyl) -1- (p- (3
-Methyl) -butoxyphenyl) -ethene in a mixture of 10 mmol and 50 ml of diethyl ether at room temperature with Br ₂ 0.01
Mole is added dropwise. The reaction mixture was evaporated, 0.03 mol of potassium tert-butyrate and 10% of tert-butanol.
0 ml are added and the mixture is heated to the boil under reflux for 4 hours. Pour the reaction mixture over ₂₀₀ ml of H ₂ O, then
Extract with MTB. The product is obtained by evaporation and crystallization. Thus, 4-pentyl-4 '-(3-
Methylbutoxy) tolan is obtained.

Similarly, the following compound is prepared: 4- (2-methylbutoxy) -4'-pentyltran 4- (2-methylpentoxy) -4'-pentyltran 4- (3-methylpentoxy)- 4'-pentyltolan 4- (4-methylpentoxy) -4'-pentyltolan 4- (2-methylpentoxy) -4'-pentyltolan 4- (3-methylhexoxy) -4'-pentyltolan 4- (4-methylhexoxy) -4'-pentyltran 4- (5-methylhexoxy) -4'-pentyltran 4- (5-methylheptoxy) -4'-pentyltran 4- (6-methylheptoxy) -4'-pentyltran 2,3-difluoro-4- (3-methylbutoxy)-
4'-heptyltran 2-fluoro-4- (4-methylpentoxy) -4 '
-Octyltran 3-fluoro-4- (5-methylhexoxy) -4 '
-Nonyltran 2,3-difluoro-4- (6-methylheptoxy)-
4'-decyltran 4- (3-methylbutoxy) -4'-nonyltran 4- (3-methylbutoxy) -4'-decyltran 4- (3-methylbutoxy) -4'-undecyltran 4- (3- Methylbutoxy) -4'-dodecyltran 4- (4-methylpentoxy) -4'-nonyltran 4- (4-methylpentoxy) -4'-decyltran 4- (4-methylpentoxy) -4'- Undecyltran 4- (4-methylpentoxy) -4'-dodecyltran 4- (5-methylhexoxy) -4'-nonyltran 4- (5-methylhexoxy) -4'-decyltran 4- (5-methylhexoxy)- 4'-undecyltran 4- (5-methylhexoxy) -4'-dodecyltran 2-fluoro-4- (4-methylhexoxy) -4'-
Propyltran 2-fluoro-4- (4-methylheptoxy) -4 '
-Butyltolan 4- (3-methylnonoxy) -2 ', 3'-difluoro-4'-pentyltolan 4- (4-methyldecoxy) -2'-fluoro-4'
-Pentyltolan 4- (5-methylundecoxy) -3'-fluoro-
4'-Pentyltran 4- (6-methyldecoxy) -2 ', 3'-difluoro-4'-pentyltran Example 3 In the same manner as in Example 1, 4-butoxy-4'-bromotran was converted to a Grignard reagent (this was Addition of a solution of 1-bromo-3-methylbutane and Mg in ether) followed by hydrolysis affords the reaction product 4-butoxy-4 '-(3-methylbutyl) -tolane. .

Similarly, the following compound is prepared: 4-butoxy-4 '-(4-methylpentyl) -tolan 4-butoxy-4'-(5-methylhexyl) -tolan 4-butoxy-4 '-(6 -Methylheptyl) -tolan 4-hexoxy-4 '-(3-methylbutyl) -tolan 4-hexoxy-4'-(4-methylpentyl) -tolan 4-hexoxy-4 '-(5-methylhexyl) -tolan 4-hexoxy-4 '-(6-methylheptyl) -tolan 4-octoxy-4'-(3-methylbutyl) -tolan 4-octoxy-4 '-(4-methylpentyl) -tolan 4-octoxy-4' -(5-methylhexyl) -tolan 4-octoxy-4 '-(6-methylheptyl) -tolan 4-propyl-4'-(3-methylbutyl) -tolan 4-propyl -4 '-(4-methylpentyl) -tolan 4-propyl-4'-(5-methylhexyl) -tolan 4-propyl-4 '-(6-methylheptyl) -tolan 4-butyl-4'-( 3-Methylbutyl) -tolan 4-butyl-4 '-(4-methylpentyl) -tolan 4-butyl-4'-(5-methylhexyl) -tolan 4-butyl-4 '-(6-methylheptyl)- Tolan 4-hexyl-4 '-(3-methylbutyl) -tolan 4-hexyl-4'-(4-methylpentyl) -tolan 4-hexyl-4 '-(5-methylhexyl) -tolan 4-hexyl-4 '-(6-Methylheptyl) -tolan 4-octyl-4'-(3-methylbutyl) -tolan 4-octyl-4 '-(4-methylpentyl) -tolan 4-octyl-4'-(5-methyl Xyl) -tolan 4-octyl-4 '-(6-methylheptyl) -tolan 2,3-difluoro-4-hexyl-4'-(3-methylbutyl) -tolan 4-hexyl-2'-fluoro-4 ' -(5-Methylpentyl) -tolan mixture example Ar-1-cyano-cis-4- (trans-4-propylcyclohexyl) -1-propylcyclohexane 14
%, 1- (trans-4-propylcyclohexyl) -2
-(2'-fluoro-4'-ethylbiphenyl-4-yl) -ethane 20%, 1- (trans-4-propylcyclohexyl) -2
-(2'-Fluoro-4'-pentylbiphenyl-4-
Yl) -ethane 19%, 1- (trans-4-pentylcyclohexyl) -2
-(2'-fluoro-4'-ethylbiphenyl-4-yl) -ethane 17%, 2-fluoro-4,4'-bis- (trans-4-propylcyclohexyl) -biphenyl 4%, 2-fluoro-4 -(Trans-4-pentylcyclohexyl) -4 '-(trans-4-propylcyclohexyl) -biphenyl 5%, 4-pentyl-4'-butoxytran 7%, 4-hexyl-4'-butoxytran 7%, And 4-butoxy-4 '-(3-butenyl) -tolan 7
% Of a liquid crystal phase is prepared.

Mixture example Br-1-cyano-cis-4- (trans-4-propylcyclohexyl) -1-pentylcyclohexane 11
%, Trans-1-p-methoxyphenyl-4-propylcyclohexane 10%, 2-fluoro-4,4'-bis- (trans-4-propylcyclohexyl) -biphenyl 4%, 2-fluoro-4- ( Trans-4-pentylcyclohexyl) -4 '-(trans-4-propylcyclohexyl) -biphenyl 5%, 4-propyl-4'-butyl-tolan 15%, 4-propyl-4'-pentyl-tolan 13%, 4-butyl-4'-pentyl-tolan 13%, 4-methyl-4'-ethoxy-tolan 5%, 4-ethyl-4'-methoxy-tolan 6%, 4-methylthio-4 '-(trans-4 -Propylcyclohexyl) -tolan 6%, 4- (4-methylpentoxy) -4'-nonyltolan 4%, 4-butoxy-4 '-(3-butenyl) -tolan 3
%, And 4-butoxy-4 '-(5-hexenyl) -tolan
A liquid crystal phase consisting of 11% is prepared.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09K 19/54 C09K 19/54 Z G02F 1/13 500 G02F 1/13 500 (72) Inventor Joachim Klaze D- 6100 Darmshitter Tut, Frankfurter, Schutlase 250 (72) Inventor Herbert Prague D-6100 Darmshitter Tut, Frankfurter, Schutlase 250 (56) References JP 62-298545 (JP, A) ( 58) Field surveyed (Int.Cl. ⁶ , DB name) C07C 15/54 C07C 25/24 C07C 43/215 C07C 43/225 C09K 19/54

Claims (7)

(57) [Claims] 1. A formula _{I C m H 2m + 1 -Q} 1 -C n H 2n -Q 2 -Ph 1 -C≡C-Ph 2 -Q 3 -C o H 2o + 1 I [ wherein, Ph ¹ and Ph ² are each independently 1,4-phenylene, unsubstituted or having one or two fluorine atoms as substituents, Q ¹ is -CH = CH- Yes, Q ² is a single bond, and Q ³ is -O-
Or a single bond, m is 0-8, and n is 2
-5, and o is 1-12]. (2) The tolan compound according to claim 1, which is represented by: 3. The tolan compound according to claim 2, wherein n is 2, 4 or 6. 4. The method according to claim 2, wherein m is 0.
4. The tolan compound according to at least one of 3. 5. A liquid crystal medium containing at least two liquid crystal compounds, characterized in that it contains at least one compound represented by the formula I according to claim 1. 6. A liquid crystal composition containing at least two kinds of liquid crystal compounds, characterized by containing at least one of the compounds represented by formula I according to claim 1. 7. An electro-optical display device comprising the liquid crystal medium according to claim 5 as a liquid crystal dielectric.