TWI254704B - Benzoic acid esters, and liquid-crystalline medium - Google Patents

Abstract

The invention relates to benzoic acid esters of the formula I, in which R1, X1, X2, X3, Y, Z and formula are as defined above. Benzoic acid esters of the formula I, in which R is H, an alkyl radical having 1-12 carbon atoms which is unsubstituted or at least monosubstituted by halogen or CN and in which, in addition, one or more CH2 groups may each, independently of one another, be replaced by -O-, -C=C- or -CH=CH- in such a way that heteroatoms are not connected directly, Z is -C=C- or a single bond, Y is H or F, and X1, X2, X3, X4 and X5, independently of one another, are H or F, with the proviso that, in the compounds of the formula I in which Y is F, and (a) R1 is an alkyl, oxaalkyl or alkoxy having 1 to 10 carbon atoms in which one or more CH2 groups have been replaced by -C=C- or (b) Z is -C=C-.

Description

1254704 A7 B7 Plant— _____-— I V. INSTRUCTION DESCRIPTION (i) The present invention relates to novel benzoate of formula I

| φ ! R1 is fluorene, an alkyl group having 1 to 12 carbon atoms and which is unsubstituted or at least monosubstituted with halogen or C Ν, and further, and one or more of the CH 2 groups may be Each of them is independently substituted by one, one C ^ C or one CH = C Η - and the other is that the heteroatoms are not directly connected, 8 - IH - - - - , I nnnn (please read the note on the back and then fill out this page) Department of Economics, Intellectual Property Office, Staff Consumer Cooperative, Print Y as Η or F., and X 1 , X 2, X 3, X 4 and X 5, Independently, Η or F, the restriction is; in the compound of formula I, X4

X5 Υ means F, line! ^ Hu -las ϋ iKl i Bas i

Ζ is a CEC—or single button. This paper scale applies to the Chinese National Standard (CNS) A4 specification (2]0 x 297 mm) -4- Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1254704 A7 B7 --- — — — — I V. INSTRUCTION DESCRIPTION (2) AND/OR R 1 is a hospital base, an oxygen-based hospital or an oxy group, and one to one carbon atom, one or more C Η 2 The group has been replaced by a C 3 C and / or | ζ is - c c c -. The present invention also relates to the use of a compound of the formula I as a liquid crystal medium.

I I component, and a liquid crystal and electro-optical display element containing the liquid crystal medium according to the present invention. I. The compound of formula I frequently has a highly positive enthalpy of dielectric anisotropy, with medium to high optical anisotropy Δη and a relatively low viscosity and can be used as a component of a liquid crystal medium, especially as a display. The system is based on the following principles: the effect of the torsion chamber, the guest-host effect, the deformation of the alignment phase (DA Ρ ) or the effect of electrical control birefringence (EC Β ) or the effect of dynamic scattering. All materials used to date for this purpose have particular disadvantages, such as insufficient stability to heat, light or electric fields, or unsuitable elastic and/or dielectric properties. The object of the present invention is to find novel, stable, liquid crystalline or meso-compounding compounds, especially having both high positive dielectric anisotropy and medium to high optical anisotropy, and low viscosity suitable for use as a component of a liquid crystal medium. , Pew | It is suitable for TN, TFT and STN displays. The compounds of Formula I have been found to be excellent as a component of liquid crystal media. It can be used to obtain a stable liquid crystal medium, especially for T F T or S tn displays. The excellence of this novel compound is especially applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) on this paper scale -------- order--------- line! (Please read the notes on the back and fill out this page.) Turtle-5-1254704. A. ______________ B7 V. INSTRUCTIONS (3) High thermal stability, which is beneficial to high "holding ratio" and shows suitable The point of transparency. The compound of the formula I is very broadly and broadly expanded in the range of liquid crystal materials, and is suitable for preparing a liquid crystal mixture from the viewpoint of various applications. The compounds of formula I have a wide range of uses. Depending on the choice of substituents, such compounds can serve as a binder in which the liquid crystal medium is predominantly contained, however, the compound of formula I can be added to the liquid crystal matrix by other grades of compounds, for example to improve this type of dielectric. The dielectric and/or optical anisotropy of the body, and/or to optimize the voltage at the opposite end and/or its viscosity. The addition of a compound of formula I to a liquid crystal dielectric allows Δη値 and Δε値 of the medium to be significantly affected. The meaning of Formula I encompasses all isotopes of the chemical elements incorporated in the compounds of Formula I. In the pure form or in a modified form of the mirror image isomer, the compound of formula I is also suitable as a dopant for the palm of the hand and is generally required to prepare a mesophase in the palm of the hand. Printed by the Consumer Intellectual Property Office of the Ministry of Economic Affairs in the Pure State, the compound of Formula I is colorless and forms a liquid phase in the liquid phase, which is advantageous in electro-optical applications. He is stable to chemistry, heat and light. The present invention is therefore directed to compounds of formula I, and to the use of such compounds as components of liquid crystal media. Further, the present invention relates to a liquid crystal medium comprising at least one compound of the formula I, and to a liquid crystal display element, particularly an electro-optical display element, which contains a medium of this type. Unless otherwise specified, above and below, R 1 , X 1 , Χ 2 paper waf is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -6- 1254704 λ7 _Β7____ V. Description of invention ( 4), Χ3, Χ4, Χ5, Υ and one (^) are defined as above. The following compound groups of the formula I Α to IX represent the best examples of the present invention (please read the back note and then fill out this page) -I ------- order----- ---1 Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printed This paper scale applies China National Standard (CNS) A4 specification (210 X 297 mm) 1254704 V. Invention description (5)

R

F 〇 0<0 〇

N C

IB

N C

1C (Please read the notes on the back and fill out this page) -m

F F 〇

N C line! Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative, printing

IE This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -8- 1254704 A7 B7

1254704 l·5' invention description (7)

F

F

1254704 V. Description of invention (8)

R

Is

F

R 〇 0^0

F 〇 >/\

F

IT

Nc

Lu (please read the notes on the back and fill out this page) m

IV

» 1 I I I

R 〇 /\o

F

F w 〇

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F

F Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing

R 〇 o<o

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I —31- ΜΜΚ0 31 I Fg-fc B— 3α efs BSB I

F ιγ

Nc Paper & Weekly Chinese National Standard (CNS) A4 Specification (2] 0 X 297 mm) -11 - 1254704 A7 B7 V. Invention Description (9

R 〇Ί, 〇 ΙΖ

λ λ-CN

F

R 〇 〇/, 〇 ο

Ν C

R

Β Β (Please read the notes on the back and fill out this page)

R

Ν C 8

F

R

Ν C

D D order --------- line!

F Ministry of Economic Affairs Intellectual Property Bureau Η Consumer Cooperative Print Γ 4

Ν C

/' R 040 〇 Ε Ε

F

F F

Ν C 4 A s Ν c quasi-drift home | PCT 2 1254704 A7 B7 V. Description of invention (1〇)

Wherein R 1 is as defined above, from R 2 being an alkyl, oxaalkyl or alkoxy group having from 1 to 10 carbon atoms and wherein one or more C Η 2 groups have been substituted C three C one. If R 1 is an alkyl group in the above formulas and below, this may be straight-chain or branched. More preferably linear, having 2, 3, 4, 5, 6, or 7 carbon atoms and, preferably, ethyl, propyl, butyl, pentyl, hexyl or heptyl, There are methyl, octyl, decyl, decyl, eleven carbon, 12, tridecyl, tetradecyl or pentadecyl. If R 1 is an alkyl group and one of the CH 2 groups has been substituted with -〇, this may be straight-chain or branched. Preferably, it is linear and has from 1 to 1 carbon atoms. Preferably, the first c Η 2 group of the alkyl group has been substituted with -〇-, and the group R 1 is converted to a oxy group and preferably a methoxy group, an ethoxy group, a propoxy group. , butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy or decyloxy. In addition, a C Η 2 group elsewhere may also be substituted for a 2-oxopropyl (=methoxymethyl) '2-ethoxyl group which is preferably linear in the group R 1 . Methyl) or 3-oxobutyl (di-2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2 —, 3 —, 4 —, 5 — or 6 —oxaheptyl, (please read the notes on the back and fill out this page)

1^ 1 ΛβΜβ ϋ n ϋ=-口 V ϋ ·ϋ n -I nn II Ministry of Economic Affairs Intellectual Property Bureau Η Consumer Cooperatives Print « -13- 1254704 B7 V...Invention Description 2 —, 3 4 I, 5 -, 6 - Or 7-oxaoctane 2 3 4 6 7- or 8-oxaindenyl, or 2 4 -, 5 7 8 - or 9-oxadecyl-propyl-2-yl, if R 1 is an alkenyl group This can be straight or branched. It is preferably and has 2 to 10 carbon atoms. Accordingly, it is especially a vinyl- 1 - or - 2 - alkenyl group, a butyl group, a 1-2, or a 1-3 group, a pentyl group, a 1-2 group, a 1-3 group, or a 1-4 alkyl group. — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — —, — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — - Aene or please read the back of the precautions and then fill in this page -4 6 7 - 8 - or a 9 - storage base R 1 is particularly preferred as a storage group:

A Η b

2 Η C Η c

CH 2 Η / Line Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 14.· Once Η C, la ¥

3 Η C 3 3ή Η C/ C *

C , 3 3 Η \ 5

3 Η C λ- Η , c Η , c

PCT -14- 1254704 A7 B7 V. Description of invention (12) CH,

CH 3 If R1 is an alkenyloxy group, this may be straight-chain or branched. It is preferably linear and has 2 to 10 carbon atoms. Particularly preferred is a group selected from the group consisting of: —Ο -0 CH. —Ο

CH 2 CH, CH, CH, —Ο :CH. -〇 CH, 一〇 〇

•CH 〇 3

-CH \\ -〇

3 CH CH, 3 h3c- -o CH, one 〇 —0

CK CH.

CH 3 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed — 2 — or 2 — alkynyl 1 If R 1 is an alkyl group and at least monosubstituted with a halogen, the group is preferably linear. Halogen is preferably F or C 1 . When more substituted, the halogen is better. The resulting group also includes perfluorinated groups. When monosubstituted, the fluoro or chloro substituent may be at any desired position, but preferably in the ^ position. If R 1 or R 2 is an alkynyl group, this may be straight-chain or branched. Preferably, it is linear and has 2 to 10 carbon atoms. According to this, 'particularly ethynyl, C-paper standard applies China National Standard (CNS) A4 specification (210 X 297 mm) -15- 1254704 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7_ V. Invention description ( 13) 3 - fast base, pentyl 1 - 1, 2 -, 3 - or 4 - fast radical 'hex-1', 1 2 -, - 3 -, - 4 - or -5 - alkynyl, g —1 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一One or a 7-alkynyl group, 壬-1, 2, 3, 4, 5, 6, 6 or 7 alkynyl, or 癸-1, — 2 —, — 3-, — 4 —, — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — R 1 is particularly preferably a group selected from the group consisting of: C = C Η ' - C Η 2 - C = CH λ - C = C - C Η 3 , one C ^ C - one, one GH 2 - CH 2 I, -CH2 - C^C - CHa n - CH2 - CH2 - c = c~ CH, 3 and -CH2 - CH2 - CeC - c2h5. If R 1 or R 2 is an oxaalkyl or alkoxy group wherein one CH 2 group has been substituted with - C ξ C -, this may be straight-chain or branched. Preferably, it is linear and has 2 to 10 carbon atoms. In particular, it may be a group selected from the group consisting of: -〇-ΟΗ2-ϋΞΞ〇Η ' - 0- CH2-C^CC Η 3 , one 〇 C Η 2 — C Η 2 — C Ξ C Η , one 〇一 C Η 2 — CH2 — C^C — CH: 3 , — 〇 — CH 2 — CH 2 — C ^ C — C 2 H 5 , C C C C CH 2 — — 〇 CH CH 3 , C C C I (please read the precautions on the back page again) _ Line · This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -16- 1254704 A7 ____B7_ V. Description of invention (14)

CH2 — OCsHs or a CeC — CHsCHs — O — CH Ο (Please read the notes on the back and then on this page) The compounds of formula I containing the branched group R 1 may occasionally be of importance, as they are The liquid crystal binder has better solubility, but especially as a dopant for palms, if it is optically active. This type of lipid liquid crystal compound is suitable as a component of a ferroelectric material. This type of branching group -_ generally contains no more than one chain branch. Preferred branched groups R1 are isopropyl, 2-butyl (=1-methylpropyl), isobutyl (di-2-methylpropyl), 2-methylbutyl, isopentyl (=3 monomethylbutyl), 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, isopropoxy, 2-methylpropoxy, 2 —methylbutoxy, 3-methylbutoxy, 2-methyl-pentyloxy, 3-methylpentyloxy, 2-ethylhexyloxy, 1-methylhexyloxy or 1 Monomethyl-heptyloxy. Formula I encompasses such compounds as racemates and optical versus palms, and mixtures thereof. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives. In the compounds and sub-formulas of the formula I, preference is given to those groups which exhibit at least one of them and which have a preferred meaning as indicated. Other preferred compounds of formula I are described below: a compound of formula I and the R 1 group is an alkyl, oxaalkyl or anthoxy group with from 1 to 10 carbon atoms and one or more of them The c η 2 group has been replaced by a C ^ c one. -17- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1254704 A7 _B7_ V. Description of invention (15) Compound of formula I wherein one of the two groups X 1 and X 2 is Η And the other is F, or wherein the :: group is also F.

A compound of formula I wherein the groups X 1 and X 1 are both F 化合物 a compound of formula I wherein Υ is F. a compound of formula I wherein ring one is

The Intellectual Property Office of the Ministry of Economic Affairs, the employee consumption cooperative, prints the compound of formula I, and the one is a single bond. Some very particularly preferred minor groups of the compounds of formula I are those of I 1 to I 2 1 : - 18 - This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1254704 A7 B7 V. Description of invention (16)

F Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing

(Please read the precautions on the back page again) Line · This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -19- 1254704 A7 __B7 V. Invention description (17) \

/\/\rI FVAV

F 0<0

F

N C

N C /\yx\

F

, F (please read the notes on the back and then on this page) Install \ I fvavv

F 0<0 Αν

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F Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing

N c

F

丨线 2 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -20- 1254704 A7 __B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -21 - V. Invention description (18) 1254704 A7 __B7 V. Invention description (19)

F

R 0^0

F

F

N C

R 0<0

F

N C

R 0^0

N. C 2 (Please read the notes on the back and then this page)

N C 12

F

N C 24 丨 line · Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing

N C

R 2

F

F ΟΛΧΟ

F F 6

N C This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -22- [254704 A7 B7 V. Invention description (20.

F

CN 〇 127

F 0 -

CN 128

FT 〇 F F 〇一

CN 129 〇 Ί\ 〇·

F

CN 130

CN X 131 Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumption Cooperative, Printed

F

CN 〇 •丫' 〇 I32

FT I33

\ rcN (please read the notes on the back and then on this page)

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -23 - Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1254704 A7 ___ B7____ V. Invention description (21) where X~ and X 1 Same as defined above. R 3 is an alkyl group having 1 to; [0 carbon atoms, preferably an IE-alkyl group having 1 to 7 carbon atoms. R 1 is fluorenyl or alkyl or oxaalkyl and has 1 to 7 carbon atoms, preferably n-alkyl and 1 to 5 carbon atoms, very preferably 1 to 3 One carbon atom. R 5 is an alkyl group or an alkenyl group and has 2 to 7 carbon atoms. 11 is an integer from 1 to 7, preferably 1, 2, 3, 4 or 5. Very particularly preferred compounds of this group are those of formulas I 2, 13, 16, 18, 112, 113 and 114. Further preferred are compounds of the formulae 122, 123, 124, 125, 126, I27 and I28. The compounds of formula I are prepared by methods known per se, as described in the literature (for example in standard work such as Houben-Weyl, Methoden der Organise hen Chemie), Georg-Thieme-Verlag, Stuttgart ), under known reaction conditions, and suitable for the reaction. The system in which the variables can be used is known per se, but will not be described in detail herein. If required, the starting material can also be formed in situ without separating from the reaction mixture, but will be replaced immediately. Further conversion of the compound of the formula I. The compounds according to the invention can be prepared, for example, as shown in the following reaction scheme: (Please read the notes on the back and then ___ this page) .. ; Line - This paper scale applies to the Chinese National Standard (CNS) A4 specification (21 〇x 297 mm) -24- 1254704 A7 B7 V. Description of invention (22) Illustration 1 X1 Br

CN X1

Ra-

CN X2 (Please read the note on the back and then the page) 1 - R a = alkyl line · Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) ) -25- [254704 V. Inventions (23) Illustration 2

Ra-Br + Mg + 1/2 ZnCI2 A7 B7

F F F F

CN X2 F F Rc

(Please read the notes on the back and then the page) R : 1 = alkyl IB horn

Br

Rd F F 1. BuLi 2. CO,

F

Pd(PPh3)4, base

F X' Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing

R ; 1 dialkyl

F F

Rd

F 〇 X1 CNX2 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -26- [254704 V. Invention description (24) Illustration 4 A7 B7

F

Br

R —= Pd(PPh3)2CI2/Cul

Rd

F

R = alkyl diagram 5

Rd

Br

ZnCI -►

Rd (please read the notes on the back and then on this page)

Pd(DPPF)2CI2

X

X . · R a = alkyl Figure Corner Army -- Line · Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1. BuLi or

R h = alkyl This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -27-

[254704 V. Description of invention (25) Illustration 7 F corpse 1. BuLik〇-tBu 2. Rb-I A7 B7

& F 1.BuLi/KO-tBu 2.CO,Π \> —i_►

F F

CN R b dialkyl diagram 8

R—X A 1. 巳 uLi 2. CO,

R

OH (please read the notes on the back and then on this page).-

F HO—(\ /)-CN M ——R DCC / DMAP 1-<5>

〇 F jj

〇/>- CN F 丨线· Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperative Printed This paper scale applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -28- 1254704 A7 ________Β7 V. Invention Description ( 26) WjM 9—

Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives. °_X °-\^CN F The esters of the formula I can also be obtained from the corresponding esterification of carboxylic acids (or their reactive derivatives) using alcohols or phenols ( Or its reactive derivative) or via the DCC method (DCC = dicyclohexylcarbonyldiimine). The corresponding carboxylic acids and alcohols or phenols are known or can be prepared by methods analogous to known methods. Suitable reactive derivatives of the carboxylic acid are, in particular, hydrazine halides; in particular chlorides and bromides, in addition to anhydrides, azides or esters, especially alkyl esters, which have from 1 to 4 in the alkyl group. One carbon atom. Suitable reactive derivatives of such alcohols and phenols are, in particular, the corresponding metal alkoxides and metal phenol oxides, respectively. Preferred metals are alkali metals such as N a or K. The esterification reaction is advantageously carried out in the presence of an inert solvent. Particularly suitable solvents are ethers such as diethyl ether, di-n-butyl ether, THF, dioxins or anisole, ketones such as acetone, methyl ethyl ketone or cyclohexane. Ketones, guanamines such as DMF _ hexamethylammonium phosphate, hydrocarbons such as benzene, toluene or xylene, halogenated diameter stomachs such as carbon tetrachloride or tetrachloroethylene, and sub-classes such as dimethyl Subcode or ring _ This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the back note on this page first). · Line - 1254704 A7 B7 V. Invention description (27) alkyl. A solvent which is incompatible with water can be advantageously used at the same time, and water formed during the esterification reaction is removed via azeotropic distillation. Occasionally, it is also possible to use an excess of an organic base such as pyridine, porphyrin or triethylamine as a solvent for the esterification reaction. The esterification reaction can also be carried out in the absence of a solvent, for example by simply heating the components in the presence of sodium acetate. The reaction temperature is usually between -50 and +250, preferably between one and two. And between + 80 °. At such temperatures, the esterification reaction is generally complete after 15 to 48 hours. In detail, the reaction conditions of the esterification reaction are substantially dependent on the nature of the starting materials used. The reaction of the 'free carboxylic acid with a free alcohol or phenol is generally carried out in the presence of a strong acid such as a mineral acid such as hydrochloric acid or sulfuric acid. A preferred reaction procedure is the reaction of an anhydride or especially ruthenium chloride with an alcohol, preferably in an alkaline medium, an important base, especially an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, a base. a metal carbonate or a hydrogen carbonate such as sodium carbonate, sodium hydrogencarbonate, potassium carbonate or potassium hydrogencarbonate, an alkali metal acetate such as sodium or potassium acetate, an alkaline earth metal hydroxide such as calcium hydroxide, or an organic base, Such as triethylamine, pyridine, lutidine, collidine or quinoline. Another preferred embodiment of the present invention esterification reaction comprises first converting an alcohol or a phenol to a sodium or potassium alkoxide or phenol oxide, for example, by treating a solution of sodium hydroxide or potassium hydroxide with ethanol, and separating The product is reacted with an anhydride or especially ruthenium chloride. Nitriles can be obtained by replacing the halogen with copper cyanide or alkali metal cyanide.

In another method for preparing a compound of the formula I, wherein the R paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -30 - (please read the notes on the back and then I. I — On this page. . Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1254704 A7 ____B7___ V. Description of the invention (28) is an alkenyl group, reacting an aryl halide with an olefin and in the presence of a third amine in the presence of a palladium catalyst (RF Heck, Acc. Chem. Res. 1 2 (1 979) 1 46 ). Examples of suitable aryl halides are chlorides, bromides and iodides, especially bromides and iodides. The third-amines must be capable of facilitating a coupling reaction, such as triethylamine, and are also suitable as solvents. Suitable examples of palladium catalysts are their salts, especially Pd(()) acetate, and organic phosphorus (HI). a compound such as a triarylphosphine. The method can be carried out in the presence of an inert solvent or in the absence of an inert solvent, and the temperature is between about 0 ° C and 150 ° C, preferably between 20 ° C and 100 ° C. Suitable solvents are, for example, nitrites such as acetonitrile or hydrocarbons such as benzene or toluene. The aryl halides and olefins as starting materials are frequently commercially available and can be prepared by methods known from the literature, for example by halogenating the corresponding parent compound or by eliminating the corresponding alcohol or halide. . Obtaining an ether of formula I, by etherification of the corresponding hydroxy compound, preferably the corresponding phenol 'this hydroxy compound can advantageously be first converted to the corresponding metal derivative, for example to convert the corresponding alkali metal alkoxide Or an alkali metal phenol oxide, via treatment with N a Η, N a N Η 2, Ν a〇Η, Κ〇Η, Ν a 2 C〇3 or Κ 2 C〇3. The metal derivative can then be reacted with a suitable alkyl halide, alkyl sulfonate or dialkyl sulfate, advantageously in an inert solvent such as acetone, 1,4-dimethoxyethane, DMF or dimethyl azide, or alternatively an excess of water-soluble or water-soluble-alcoholic N a 〇Η or Κ〇Η ' and a temperature between about 2Ot and 100t. In order to prepare a compound of formula 1 which is later substituted with fluorine or chlorine, the Chinese National Standard (CNS) A4 specification (21〇x 297 mm)-31 - (Please read the back note first. ) _ Line · Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1254704 Α7 Β7 V. Invention Description (29) The aniline derivative can react with sodium nitrite and with tetrafluoroboric acid (for the introduction of F atom) or The copper (I) chloride (in order to introduce a chlorine atom) is reacted to form a diazonium salt salt, and then thermally decomposed at a temperature of 1 〇 0 - 1 40 Torr. Preparation of an organometallic compound, for example, via a metal-halogen exchange between a corresponding halogen compound and an organolithium compound (eg, according to an organic reaction, 3 3 9 - 3 6 6 (1 9 5 1 )), eg, Preferably, the third - butyl lithium or lithium naphthalene, or by conversion with magnesium. The aliphatic group R 1 is bonded to the aromatic ring, preferably via a Fnedel-Crafts alkylation reaction or a deuteration reaction, by catalytic reaction with Lewis acid using a corresponding aromatic compound. Examples of suitable Lewis acids are S nC 1, ZnC 12 and especially A 1 C 13 and T 1 C 1 , ι. Further, the preparation of the compound of the formula I can be carried out by substituting the formula I by reducing it to contain one or more reducible groups and/or C-C bond compounds instead of the ruthenium atom. Suitable reducible groups are preferred carbonyl groups, especially keto groups, and further, for example, free or esterified hydroxyl groups or aromatic bonded halogen atoms. A preferred reduction starting material is a compound of formula I, but contains a CH=CH- group instead of a -CH2CH2 group and/7 or a C〇- group instead of a C Η 2 group. The group and/or white are free or functionally derived (for example in the form of their p-toluene sulfonate) in place of the ruthenium atom. This reduction can be performed via, for example, catalytic hydrogenation' and the temperature is within the paper scale applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -32 - (please read the notes on the back again -- This page) Line · Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Ministry of Printing and Economy Ministry Intellectual Property Bureau Staff Consumer Cooperatives Printed 1254074 A7 _____B7____ V. Invention Description (3Q) Between 0 ° and about 200 ° and pressure is in the middle Between about 1 and 200 bar (bar), in an inert solvent such as an alcohol such as methanol, ethanol or isopropanol, an ether such as tetrahydrofuran (THF) or dioxane, an ester such as ethyl acetate, a carboxylic acid Such as acetic acid, or a hydrocarbon such as cyclohexane. A suitable catalyst is advantageously a precious metal, such as Pt or Pd, which may be used in the form of an oxide (for example Pt〇2 or Pd〇) on a support (for example Pd in carbon, aging or On cesium carbonate) or in a finely dispersed form. The ketone may also be reduced to form the corresponding compound of formula I which contains an alkyl group and/or a C Η 2 C Η 2 -bond bridge via the Clemmensen process (using zinc, zinc mixtures) Or tin and hydrochloric acid, advantageously in a water-soluble-alcoholic solution or in a heterogeneous phase of water/toluene, at a temperature between about 80 and 120 ° C) or Wuqi (Wolf- Kishner's method (using hydrazine, advantageously in the presence of a base such as K 〇Η or Na 〇Η , in a high boiling solvent such as diethylene glycol or triethylene glycol, and the temperature is between about 1000 and Between 2 0 0 °C). In addition, it is possible to use a complex hydride system for reduction. For example, the arylsulfonyloxy group can be removed by reduction using L 1 A 1 H i , especially the p-toluenesulfonyloxymethyl group can be reduced to a methyl group, advantageously in an inert solvent. Among them, such as diethyl ether or THF, and the temperature is between about 〇 and l ° ° C. The hydrogenation of the double bond can be carried out using Na a Β Η 4 or a tributyl tin hydride in methanol. The starting material is known or can be prepared from a compound similar to known compounds. The liquid crystal medium according to the present invention preferably contains 2 to 40 components, in particular (please read the back note on this page) - line 'this Paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) - 33- 1254704 A7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed B7_5, invention description (31) In 4 to 30 kinds of ingredients, As other components than - or more depending on the compound of the present invention. Such media are very particularly suitable for containing from 7 to 25 components, in addition to one or more compounds according to the invention. Such other components are preferably selected from nematic or monomorphic (singly variable or isotropic) materials, especially one type of material and the other from azobenzene, benzylidene aniline, biphenyl. , a third-phenyl group, phenyl benzoate or cyclohexyl benzoate, a phenyl ester or a cyclohexyl ester of cyclohexanecarboxylic acid, a phenyl ester or a cyclohexyl ester of cyclohexylbenzoic acid, a cyclohexyl ring. a phenyl ester or a cyclohexyl ester of hexanecarboxylic acid, a cyclohexylphenyl ester of benzoic acid, a cyclohexylphenyl ester of cyclohexanecarboxylic acid or a cyclohexylphenyl ester of cyclohexylcyclohexanecarboxylic acid , phenylcyclohexane, cyclohexylbiphenyl, phenylcyclohexylcyclohexane, cyclohexylcyclohexane, cyclohexylcyclohexylcyclohexene, 1,4-cyclohexylbenzene, 4,4 '-dicyclohexyl Biphenyl, phenyl- or cyclohexyl-density [precipitated, phenyl- or cyclohexyl fluorene, phenyl- or cyclohexyl di-chew, phenyl- or cyclohexyl-1,3-dithiane, 1 , 2-biphenylethane, 1,2-dicyclohexylethane, 1-phenyl-2-cyclohexylethane, 1-cyclohexyl-2-(4-phenylcyclohexyl)ethane, 1 A cyclohexyl-2 - biphenyl ethane, 1-phenyl-2 - cyclohexyl phenyl optionally halogenated ethane Di, benzyl phenyl ethers, tolans and substituted cinnamic acids. The 1,4-phenylene group in such compounds may also be fluorinated. The most important compounds suitable as the other components of the medium according to the present invention are classified into the molecular formulas 1, 2, 3, 4 and 5: (Please read the back note on this page first) - Female--- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -34- 1254704 A7 B7_ V. Invention description (32) R, - L - E - R,, 1 R ' - L - C 〇 〇一E - — R ” 2 R′ a] L 〇〇 C E E — R” 3 R′ L L — CH 2 CH 2 — — E — R 4 4 R ' 一 L 三 C C C E E — R, 5 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives are printed in Molecular Formulas 1, 2, 3, 4 and 5, L and E, which may be the same or different, and in each case, each independently is a divalent group. Formed from a Ph 6 -1, a C yc - , a Ph 6 -P h 6 -, -Phe - Cyc -, a Cyc - Cyc - , a Pyr - , a Dio -, - G - Phe - and - G — Cyc — and its mirror image, where P he is unsubstituted or fluoro-substituted. 1,4 is a phenyl group, Cyc is a trans-1,4 ring-extension hexyl group or a 1,4-cyclohexylene group, P yr is卩 D D - 2,5 - diyl or 吼 steep one 2,5 - diyl, D 1 〇 is 1, 3 dioxane - 2,5 - diyl and G is 2 - (re - 1 , 4 A ring of cli) ethyl, 卩 卩 一 2 2,5 - a * base, 吼卩 一 2, 5 - a base or 1, 3 - ... 卩 一 a 2,5 - a base. Group L Preferably, one of E and C is Cyc, Phe or Pyr. E is preferably C y c., P he or P he — C yc. The medium according to the present invention preferably comprises one or more components selected from the group consisting of Compounds of formula 1, 2, 3, 4 and 5 wherein L and E are selected from the group consisting of C yc , P he and P yr , and one or more components are selected from the formula 1 a compound of 2, 3, 4, and 5 wherein one of the groups L and E is selected from the group of - and the group is Cyc, (please read the back note on the page first) m. _ line_ This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -35- 1254704 A7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed B7_5, invention description (33) P he and P yr And other groups and one selected from the group The group consists of -P he - P he -, - P he - C yc -, a Cyc - Cy c -, - G - Phe - and a G - Cyc - and optionally - or more a component selected from the group consisting of compounds of formula 1, 2, 3, 4 and 5 wherein the groups L and E are selected from the group consisting of -P he - C yc -, a C yc - C yc -, One G - Phe - and one G - C yc - are composed. Among the smaller subgroups of the compounds of the formulae 1, 2, 3, 4 and 5, R' and R" are each independently an alkyl group, an alkenyl group, an alkoxy group, an alkoxyalkyl group, an olefinic oxygen group. a group or an alkoxy group having up to 8 carbon atoms. The smaller subgroup below is referred to as a group A, and the compound is represented by the subgroups 1 a, 2 a, 3 a, 4 a and 5 a represents. In most of such compounds, R 'and R ' are different from each other, and one of such groups is usually an alkyl group, an alkenyl group, an alkoxy group or an alkoxyalkyl group. Among the smaller subgroups of the other compound of the formulae 1, 2, 3, 4 and 5, it is referred to as a group B, and R" is -F, a C1, -NCS or a (〇) ) C Η 3 ( u)F k C 1 !, where 1 is 〇 or 1 and k and 1 are 1, 2 or 3; wherein R's compound with this meaning is from sub-formula 1 b, 2 b , 3 b, 4 b and 5 b are represented. Specific preference is given to compounds of the & sub-formulas lb, 2b, 3b, 4b and 5b, where R" is -F, -C1, -NCS, a CF3, a CIi F2 or a CF 3. In the compounds of the sub-formulas 1 b, 2 1], 3 b, 4 b and 5 b, R 'is defined as in the compound of the sub-formula 1 a - 5 a (please read the back first) Precautions again ___ This page) . • Line · This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) - 36- 1254704 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative prints V. DESCRIPTION OF THE INVENTION (34) Preferred are a group, an alkenyl group, an alkoxy group or an alkoxyalkyl group. Among other minor subgroups of the compounds of the formulae 1, 2, 3, 4 and 5, R "为-CN; the following group is called a group 〇' and the compounds of this group are correspondingly described in the sub-formulas 1 c, 2c, 3c., 4c and 5 c. ΰ in the sub-formula ic, 2c In the compounds of 3c, 4c and 5c, R' is as defined in the compound of the sub-formula ia-5a and is preferably an alkyl group, an alkoxy group or an alkenyl group. In addition to the preferred compounds of the groups A, B and C, other variants of the formulae 1, 2, 3, 4 and 5 having the other substituents as set forth above are also conventional. All such materials are available from a number of methods and are known from the literature or the like. In addition to the compounds of the formula I according to the invention, the medium according to the invention preferably comprises one or more compounds selected from the group A and/or the group B and/or the group C. In the medium according to the invention, the weight ratio of the compound derived from such a group is preferably: Group A: 〇 to 90%, preferably 20% to 90%, especially 3〇 to 9 0 % group B: 〇 to 80%, preferably 10 to 80%, especially 1 to 6 5 %, group C: 〇 to 80%, preferably 5 to 80%, especially 5 to 5 % by weight in a particular medium according to the invention, the sum of the weight ratios of the groups A and / or b and / or C compound is preferably between 5% and 90%, and especially at 1% to 90%. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -37 - (Please read the back note first - ___ this page) - Line · 1254704 A7 ______Β7__ V. Invention description (35) ( Please read the following notes on the back side. The medium according to the invention preferably comprises from 1 to 40%, particularly preferably from 5 to 30%, of the compound according to the invention. Preferred media for the further steps are those which comprise more than 40%, especially from 4 5 to 90%, in accordance with the invention. This medium preferably contains three, four or five compounds according to the invention. The medium according to the invention can be prepared in a manner which is conventional in its own right. In general, the ingredients are compatible, advantageously at elevated temperatures. The liquid crystal phase can be modified in accordance with the present invention by suitable additives which can be used in all of the liquid crystal display elements of the type disclosed so far. Additives of this type are known to those skilled in the art and are described in detail in the literature (Η · K e 1 ke i7 R . H at ζ, Liquid Crystal Handbook, V er 1 ag C hem 1 e, Weinheim, 1 980). For example, a multi-colored dye can be added to prepare an additive color-host system, or a substance can be added to improve dielectric anisotropy, viscosity, and/or alignment of the nematic phase. - The following examples are intended to illustrate the invention and are not intended to be limiting. Above and below, the percentage is by weight. All temperatures are in degrees Celsius. m · P · means melting point, c 1 · p · = transparent point, T g two glass turn Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed shift temperature. Further, C is in a crystalline state, N = nematic phase, S m dilipid liquid crystal phase and I = isotropic phase. The number between such symbols means that the transition temperature ◦ Δ η means optical anisotropy (589 nm, 20t: ) and Δ ε means dielectric anisotropy (lkHz, 20t). The Δη and D s値 of the compound according to the invention are obtained from a mixture of extrapolated liquid crystals and are 100% specific according to the invention. The liquid crystal ZLI 4 7 9 2 (M erck) , D armstadt ). This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -38 - 1254704 A7 B7 36 V. INSTRUCTIONS (Viscosity (mm 2 / sec) is measured at 20 °C." Customary completion "Work-up" means that if water is required to be added, the mixture is extracted with dichloromethane, diethyl ether or toluene to separate the phases, the organic phase is dried and volatilized, and the product is purified by J i 1 i 1 analysis. Use the following enthalpy T Η F Tetrahydrofuran K 〇t BU No. - R Μ Room temperature Μ B Ether methyl DCCNND Μ AP 4 Monobutyl sulphate Third - Butyl ether - Dicyclohexylcarbonylmethylaminopyridinium Imine (please read the notes on the back and then on this page)

Br-< 〇

2 CH, -- Line · Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1 1 . 4 g of 1 and at 10 t: and in stirring + 4 iodine benzene (1 ) and 3 - T acetylene 100 ml of triethylamine, 6 0 · 2 g of 1-bromo-3-fluoroindole 0 ml of triethylamine was added to the resulting mixture. Next, a mixture of 2 · 8 g of P d ( Π ) catalyst and 0.4 g of Cul was added. The reaction mixture was stirred overnight at room temperature and charged with the usual completion of work to give one. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -39 - 1254704 A7 B7 V. Invention Description (37) Example 2

First, 7.5 g of propyne was fed into 100 g of 1-bromo-3-fluoro-4-isoiodobenzene (1) at 3 ° C in 3 1 5 ml of triethylamine at 1 ° C. 2 3 5 ml of a solution of THF, and after the cooling device has been removed, 2 · 2 16 g of bis(phenylphosphine) P d ( Π ) is added. After the mixture has been stirred overnight, it will be collected as usual. (Please read the notes on the back first - ___ this page. .- Example 3

Line· Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed at room temperature and pressure at 3. lba r in 4.6 ml of hexane in the presence of 4 · 6 g of P t / C (10 %) 4 5 . 8 g of _a_ is hydrogenated and obtained by routine completion. Example 4 The paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) - 40- Ϊ254704 A7 V. Description of invention (38)

4

5 A solution of 832 ml of butyllithium in the hospital was added dropwise to a solution of 3 2 · 0 g of main _ in 270 ml of T H F at a temperature of 7 °C. After the mixture was stirred for 3 minutes, excess carbon dioxide was introduced into the solution so that the temperature did not rise to a temperature of 55. (: above. Then remove the cooling device, and take this mixture as a routine completion to get j__. Implement gl 5

CN —► H3C/

(Please read the notes on the back and then - I. On this page, . ' 'Is the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Cooperatives, Print 5 6 7 Add 3 · 40 g of i - to a solution and the solution is 30 ml The toluene is dissolved in 2 · 40g of [, 3 · 40g of DCC and 〇 · 400g of DMAP, which is added so that the temperature does not rise above 40 ° C. After stirring the mixture overnight, 〇·40 g of oxalic acid dihydrate was added to the reaction mixture. The mixture was stirred for 1 hour and then filtered. The filtrate was subjected to customary completion to give 7 (e 6 〇I) ° Example 6 - 4. Winter paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -41 - — 1254704 A7 B7 V. Description of invention (39: h3c-

Βγ ΗΧ

3 8 at 65t:, a solution of 53·〇8 ml of 15% butyllithium in the hospital was added dropwise to a solution which had a concentration of 18.60 g at 112 ml. In THF. Excess carbon dioxide is then passed into the solution and the temperature is not raised to a level of 5 Torr. (: Above. Then remove the cooling device and collect the mixture as usual. Obtain the example (please read the back note first.

CN Ministry of Economics, Intellectual Property Bureau, Staff Consumer Cooperative, printed 2,500 g of _ (available from hydrogenation as described in Example 3) was added to a solution and the solution was 2.17 g and _ , 2.89 g of DCC and 〇· 3 4 2 g of DMAP dissolved in 3〇

ML is added to the toluene, and this is added so that the temperature does not rise above 40 °C. After the mixture was stirred overnight, 0. 3 3 3 g of oxalic acid dihydrate was added to the reaction mixture. The mixture was stirred for 1 hour and then filtered. The filtrate is routinely collected to obtain 10 (C paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -42-254704 V. Invention description (4Q) 7 0 I ) ° A7 B7 Example 8

8

11

H0-< 0 y-CN

12 a mixture of 1 · 0 0 g of i, 0.73 3 g of 11,1 · 17 g of DCC and 〇.1 1 5 g of DMAP dissolved in 11 ml of toluene at room temperature Stir for 2 days. After the addition of 0.136 g, the reaction mixture was stirred for 30 minutes and then filtered. This filter is routinely collected to obtain 12 (C 140 Ν ( 8 5.1) I ). Example 9

(Please read the notes on the back and then this page) · Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative

Br^ 〇 / *- F 13

Stir a mixture of 4, 3 〇 5 g of 1-hexyne, 5 · 9 8 g of tetrakis (phenylphosphine) palladium and 300 ml of pyrrolidine at room temperature 2 hours. The reaction mixture was routinely recovered to give 14. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -43- 1254704 A7 B7 V. Description of invention (41 Example 1〇

14 15 At a temperature of 70 ° C, 59.72 ml of a 15% solution of butyllithium in hexane was added dropwise to a solution of 1 · 10 ml of THF dissolved in 19 · 10 g of 14 . This mixture was stirred for 30 minutes. Excess carbon dioxide is then passed into the solution and the temperature is not raised above 55 °C. The cooling unit was then removed' and the mixture was routinely collected to obtain 15. Example

H.C

15 6

CN (Please read the notes on the back and then the ® page) .- • Line · Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed at room temperature, 9.48 g of DCC in 30 ml of dichloro The solution in methane is added dropwise to a mixture of 7·3 〇g of -15,4.99 g of 2,6-difluoro-4-hydroxyphenyl nitrile (U and 〇. 7 4 9 g of D Μ AP dissolved in a mixture of 70 ml of dichloromethane was added to the reaction mixture for stirring. After mixing overnight, 1.93 g of oxalic acid dihydrate was added. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 x 297 mm) -44- [254704 V. Description of the invention (42) hours and then filtration. This (C 4 7 I , △ 6 A7 B7 liquid The usual completion of the charge, get 丄 59.6, Δη = 〇.141 Example 1 2

17

18 At room temperature, a solution of 75.52 ml of 15% butyllithium in hexane was added dropwise to a solution which was dissolved in 17.76 g of zinc chloride. In 260 ml of THF. After adding 3 · 4 6 8 g of P cl C 1 2 - d p p f, the mixture was heated to boiling, and 5 0 g of 1 0 was added dropwise. The reaction mixture was refluxed overnight and received the usual completion of work to give 18. (Please read the notes on the back and then the page) I. • Line · Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing Example 1

19 6

F F

CN 20 according to Example 1 Example 1 〇) and 2,6 to generate 2 0 (C 5 8 will be 19 (available from . fluoro-4-hydroxyphenyl nitrile 1, Δ = 3 9 . 0 similar to the implementation i) reaction Apply Δ η = this paper scale to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -45- [254704 V. Inventive Note (43) 0.0 8 9 ) 〇 The following examples can be prepared in a manner similar to A7 B7 Example 1 4 - 1 7 2 R -Λ a

〇 X1

R1 〇—(π )—CN X2 X1 X2 (Please read the notes on the back page again) (14) Methyl (15) Ethyl (16) n-propyl (17) n-Butyl (18) n-pentyl Base (19) n-hexyl-b-

Η H

Η H

F H

F H - line ·

F

F H

FH Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed on this paper scale Applicable to China National Standard (CNS) A4 Specification (210 X 297 mm) -46- 1254704 A7 B7 V. Invention Description (44, (20) Positive-Heptyl (21) n-propyloxy (22) n-butyloxy (23) n-pentyloxy (24) 1-propynyl (25) 1-butynyl (26) 1-pentynyl (27 1-hexynyl (28) 1-heptyl (29) 3-butynyl (30) 3-pentynyl (31) 3-hexynyl (32) 3-heptynyl (33) -3-butene (34) anti-3-pentene F preparation F each F Η F Η (please read the back note before this page) 丨 line · Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing clothing F Η

•F

Wide.

F

F. ,Η备-b--b-

F H (C 140 N (85) I)

F H

F H

F H

F H

F H

F H

F H

F H

F H

FH This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) - 47 - 1254704 A7 B7 45, V. Description of invention (35) Trans-4-pentenyl (36) anti-3- Hexyl (37) anti-heptenyl (38) trans-5-heptenyl (39) methyl (4 〇) ethyl F Η F Η F Η f F .

F F

F

F F (Please read the following notes on the back page) (41) (42) (43) (44) (45) n-propyl n-butyl n-pentyl n-hexyl n-heptyl

-5- F-V F (C 70 I) . -丨线· Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative

F F

F F

F F

F F (46) n-propyloxy (47) n-butyloxy (48) n-pentyloxy (49) 1-propynyl

F

F

F F

F F

FF p This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) (C 60 I, Δε = 36.8, △n = 0.1102) -48 - 1254704 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative 5, invention description (46) (50) 1-butynyl (51) 1-pentynyl (52) 1-hexynyl (53) 1-heptynyl (54) 3-butynyl (55 3-pentynyl (56) 3-hexynyl (57) 3-heptynyl (58) trans-3-butenyl (59) trans-3-pentyl (60) anti-4-pentyl Alkenyl (61) trans-3-hexenyl (62) trans-3-heptenyl (63) trans-5-heptenyl

-fc- F-b-F b F F_lFF-b-F F

Prepare

F

F F

F

F

F

F

F

F

F

F

F

F F

F F

FF (please read the precautions on the back and then the page) -• Line · This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -49- 1254704 A7 B7 V. Description of invention (64 ) methyl (65) ethyl (66) n-propyl (67) n-butyl 47

F F

Η Η F F\ 尸 Η Η

F F

F Η F, F Η (C 47 I, Δε = 30.9, Δη = 0.110)

F (68) (69) (70) (71) n-pentyl. n-hexyl n-heptyl n-propyloxy

Fy/F F H (C 42 I, Δε = 65.0, Δη = 0.130) F F F h Good F F F h Good F F F H

(Please read the notes on the back and then the page) 1 - - 丨 line · (72) n-Butyloxy

F F F

F H Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed (73) n-Pentyloxy (74) 1-propynyl (75) 1-butynyl

F F F

F F F

F H

F H

FH This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) - 50- [254704 A7 B7 48 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description ((76) 1-pentyne (77) 1-hexynyl (78) 1-heptynyl (79) 3-butynyl (80) 3-pentynyl (81) 3-hexynyl ginseng (82) 3-heptyne Base (83) anti-butenyl (84) trans-3-pentenyl (85) trans-4-pentenyl (86) trans-3-hexenyl

F F

F Η

F F F

F F F

F F F

F F F

F F F

F F F

F F F

F F F

F F

F F

F F Η

F H

F H

F H

F H

F H

F H

F H

F H

FH This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -51 - (Please read the back note before this page) . ' | Line · 1254704 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau staff consumption Co-operative printing 5, invention description (9: (87) trans-3-heptenyl (88) anti-5_heptenyl (89) methyl (9 〇) ethyl (91) n-propyl (92) n-Butyl (93) n-Butyl (94) n-pentyl (95) n-heptyl (96) n-propyloxy (97) n-butyloxy (98) n-pentyloxy

F F

F Η

F F F

F F F

F F

F F

F F

F F

F F F

F F

F F F

F F

F F F

V F F Η

F F

F F (C 109 I, Δε Δη = 0.100) 177 F F (C 95 I) F F (C 50 I, Δε = 44) F F (C 56 I, Δε = 38)

F F

F F

F F

F F

FF This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the note on the back page again) (C 38 I, Δε Δη = 0.100) 103, Line _ -52- 1254704 A7 B7 50 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed V. Inventories (99) 1-propynyl (100) 1-butynyl (101) 1-pentynyl (102) 1-hexynyl (103) 丨_heptynyl·(104) 3-butynyl ginseng (1〇5) 3-pentynyl (1〇6) 3-hexynyl (107) 3-heptynyl (108) anti Each butyl group (109) trans-3-pentenyl

F F

F F

F F

F F F F F _

F F F Pu F F F, Pu

F F

F F F

F F F

F F

F F

F F F \~L F

F

F F

F F

F F

F F

F F

F F

F F

FF This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -53- (Please read the back note first on this page) Ϊ线· 1254704 Α7 Β7 V. Invention Description (Ministry of Economics Intellectual Property) Bureau employee consumption cooperative printed 51 (110) trans-4-pentenyl I good FFF (111) anti-3-hexenyl FF general FFF (112) anti-3-heptenyl FFF \ FF (113) 1 -propynyl~0r Η ·· · H (114) 1-butynyl I Η H (115) 1-propynyl FH (C 129 I) φ (116) 1-butynyl·FH (117) 1-pentynyl FH (C 55 I, Δε = Δn = 0.1645) 49.3, (118) 1-hexynyl FH (C 49 I, Δε = Δη = 0.1957) 44.6 (119) Buhneynyl FH ( C 46 I, Δε = Δη = 0.1937) 42.7 (120) 3-methoxy-prop-1-ynyl^^ FH (C 105 I) (121) 3-pentynyl FH (122) 3-hexyne Base (123) 3-heptynyl (please read the precautions on the back page again). Good F Η F Η This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -54 - 1254704 A7 B7 V. Description of invention (52)

(124) I-propynyl FF (C 127 I) (125) 1-butynyl-6- FF (126) 1-pentynyl FF (C 52 I, Δε = Δπ = 0.1896) 64.8, (127 ) 1-hexynyl F F (C 39 I, Δε = 57.5 VV Δη = 0.1715) (128) 1-heptynyl ancient F ··'· F (C 39 I, Δε = Δη = 0.1737) 54.8 ( 129) 3-butynyl ♦ * : 6~ FF (130) 3-pentynyl-6- FF (131) 3-methoxy-propenyl alkynyl. 'Good FF (C 98 I) (132) 3-heptynyl FFF (please read the notes on the back before this page). Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative

(133) Propynyl (134) 1-butynyl (135) 1-propynyl (136) 1-butyne basic paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) - 55- [254704 A7 B7 V. Description of the invention ( 53, (137) 1-pentynyl

F

F H (C 59 I) (138) 1-hexynyl

F F

F H (C 39 丨, Δε = 44.8, Δη II 0.160) (139) 1-heptynyl

F F

F

F H (C 31 I, Δε = 42.2, Δn = 0.1.606) (14〇) 3-butynyl

/F F

H (Please read the notes on the back and then I. Ipage: (141) Pentynyl

Fragrance.· F F

F H (142) 3-hexynyl

F F

F H (143) 3-heptynyl

F F

F H - 丨 line · (144) 1-propynyl group

F F

F F Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed (145) 1-butyne·1-pentynyl (147) hexynyl

F F

F F

F F

FFF (C 100 I) FF (C 67 I, Δε = 56.6, Δη = 0.1626) FF (C 47 I, Δε = 59.6, Δη = 0.1406) This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297) PCT) -56- 1254704 A7 B7 V. INSTRUCTIONS (148) 1-Heptynyl 54

♦ F

FF (C 33 I, Δε Δη = 0.1351) 54.8, (149) 3-butynyl (150) 3-pentynyl (151) 3-hexynyl (152) 3-heptynyl (153) n-propyl Base (154) n-butyl^(155) 1-propynyl (156) 1-butynyl (157) n-pentyl (158) n-hexyl (159) n-heptyl (160) 3-butyne (161) 3-pentynyl (162) 3-hexynyl (163) 3-heptynyl (164) n-propyl

F F (please read the note on the back and then the page) «- -丨线_ Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative, printing

F

F >>>>>>>>>> λ

F F

F

F F

H H F F F F F F F F F F

H H H H H H H H H H H

FF This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 x 297 mm) _ 57 - [254704 V. Description of invention (165) 1-butynyl (166) n-pentyl (167) 1_hex Alkynyl (168) 1-heptynyl (169) n-butyl (170) 3-pentynyl (171) 3-hexynyl (172) 3-heptynyl Example 1 7 A7 B7 55 >>

F F F F (C 31 I, Δε = 39.6, An = 0.0855) F F F F F F «Λ F F F F F F (Please read the back note before this page) 1 8 〇 Y x1

R1

X1 Y . -_线_ Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed (173) Methyl (174) Ethyl (175) n-propyl fluorene 76) n-pentyl (177) anti-butenyl (178) 1-propynyl (179) n-pentyl HFHFHF Η F (C 48 N 54 I, Δε = 24) \=/

W

H F

HFFF (C 38 I, Δε = 24) This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -58- [254704 Α7 Β7 56 V. Description of invention (180) n-propyloxy (181) n-pentyl (182) 1-propynyl Example 1 8 3 — 1 ε R1

F F

Fy_f F F (C 37 I, Δε - Δη = 0.090)

F F 30,

〇FF:)~, 〇—(CN 'potential ^ . FF (please read the note on the back and then on this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed R1 (183) Methyl (184) Ethyl ^ ( 185) n-propyl (186) n-butyl (187) n-pentyl (188) n-hexyl (189) n-heptyl (190) 1-propynyl (191) trans-3-pentene yl: (192) trans-3-butenyl: (C 72 I, Δε = 23) . _ line - -b-

F

This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -59- [254704 A7 B7 V. Inventive Note (57, Example 3 -233

(193) Methyl· Η Η Printed by the Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative (194) Ethyl (195) n-propyl (196) n-butyl (197) n-pentyl « (198) n-hexyl (199 n-Heptyl (200) n-propyloxy (201) n-butyloxy (202) n-pentyloxy (203) propynyl (204) 1-butynyl

F

F

-b--V

今Η Η •:·· ^ FF (Δε = 58.9, Δη 0.1969) F Η FF (Δε = 52.4, Δη 0.1875) F Η F Η F Η F Η F Η F Η F Η (Please read the notes on the back first (page) · -- Line · This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -60- [254704 A7 B7 V. Description of invention (58) (205) 1-pentynyl group (206) 1-hexynyl~4r(207) 1-heptynyl^6-(208) 3-J-fast (209) 3-pentynyl-b-(210) 3-hexynyl (211) Y-heptynyl group (212) anti-single salty base ^ factory F -〇c Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing (213) anti_3_pentyl Ί γ| (214) anti-4-pentenyl iy (215) trans-3-hexenyl y| (216) anti-heptenyl iyl (217) n-propyl (218) methyl (219) ethyl (220) n-propyl

FF Η F Η F Η F Η 乂, F Η ./·, ., ··· F Η F Η F Η F Η F Η F Η F Η FH (C 50 I, Δε = 28.6, Δη = 0.1215) FFFFFF ( Δε = 36.2, Δη = 0.0965) (Please read the notes on the back page again) This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -61 - Ministry of Economic Affairs Intellectual Property Office staff consumption Co-operative printing and printing [254704 V. Inventive Note (59) (221) n-Butyl (222) n-pentyl (223) n-hexyl (224) n-heptyl (225) n-propyloxy (226) Butyloxy (227) n-pentyloxy (228) propynyl (229) butynyl (23 〇) I-pentynyl (231) 1-hexynyl 1 (232) 1-g Alkynyl (233) 3-butynyl A7 B7

FFFFFFFFFF,,·, FFFFFFFFFFFFFFFF (please read the precautions on the back page again) . -·Line - This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -62- 1254704 A7 B7 V. Description of the invention (Example 2 3 4 60 2

Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, Printed (235) 1-Pentynyl (236) 1-butynyl (237) 1-pentynyl (238) 1-hexynyl (239) I-heptynyl (240) 2-propynyl (241) 3-butynyl (242) 4-pentynyl (243) 3 · methoxy-propenyl alkynyl (244) 1-propynyl (245) 1-pentynyl (246) 1-butynyl (247) 1-pentynyl (248) 1-hexynyl (249) 1-heptynyl F Η F Η

F F F F F

H H H H H

F H F H

F F F F

F F F F

FFFF This paper size is applicable to China National Standard (CNS) A4 specification (210 x 297 mm) (please read the note on the back and then this page) Order · -_ Line - (C 134 I) 63 1254704 A7 __B7 V. Invention Description (61) (250) 2-propynyl FF (251) 3-butynyl FF (252) 4-pentynyl-fluorene FF (253) 3-methoxy-propan-fluorene FF -1- Alkynyl group (please read the precautions on the back page again) The Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives, Printed Paper Scale Applicable to China National Standard (CNS) A4 Specification (210 X 297 mm) -64-

Claims (1)

1254704 ABCD VI. Scope of Application for Patent 7 Attachment 2(a): Patent Application No. 89 1 2804 No. 1 Replacement of Chinese Patent Application. Amendment of March 11, 1993. 1 · A benzoate of formula I Wherein R1 is hydrazine or an alkyl group having from 1 to 12 carbon atoms, the alkyl group being unsubstituted or at least monosubstituted by halogen or c ,, wherein one or more CH 2 groups may be independently - CeC or -CH = ^- (Please read the notes on the back and fill out this page) Order · Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives print C Η an alternative; and the alternative way is to make the hetero atom Directly connected, Ζ is a C = c—or a single bond, Y is Η or F, and X1, X2, X3, X4, and X5 are each independently F or F, and the limitation is: the paper size of the compound of formula I is applicable. China National Economic Rate (CNS) Α4 Specifications (210X297 public! " 4. 1254704 Α8 Β8 C8 D8 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 々, the patent application range is -4 or its Y is F, and a) R1 is an alkyl, oxaalkyl or alkoxy group having 1 to 1 carbon atoms, wherein one or more CH2 groups The group has been replaced by a C C C — or b) Z is —CeC —. 2. The benzoate of claim 1, wherein R 1 is an alkyl, oxaalkyl or alkoxy group having from 1 to 10 carbon atoms, and wherein one or more CH 2 The group has been replaced by a C C C. 3. The benzoate of claim 1, wherein one of the groups X 1 and X 2 is deuterium and the other is F or both of the groups are simultaneously F 〇 4 . The benzoate of the first item, wherein the groups X 1 and X 4 are both F. 5 · For example, the benzoate in the first paragraph of the patent application, wherein For ’ or . 6. The benzoate of claim 1, wherein γ is f 〇7 · benzoate according to claim 1 of the patent scope, which is of the formula I 1 to 112 and 117 to 123 Applicable to China National Standard (CNS) A4 Specification (210X297 mm) jmp Pack---fl· 丨----- (Please read the note on the back and fill out this page) 1254704 A8 B8 C8 D8 VI. Apply for a patent Scope F Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing Loading—: (Please read the notes on the back and fill out this page.) This paper size applies to the Chinese National Standard (CNS) A4 specification (2) 0X 297 mm) -3 - Order 1254704 ABCD N c 19 (Please read the note on the back and fill out this page) F fvh Λ V F 0<0 F N c F CN F Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Print This paper scale applies to China National Standard (CNS) A4 specification (21〇X 297 mm) -4 - 1254704 A8 B8 C8 D8 Patent application scope F F 〇 FT Ο—(x />-CN F F CN F F R, 〇 F F 〇-(\ /)— CN 117 118 119 (Please read the notes on the back and fill out this page) F R, 1/ 〇 F F < 120 〇 (\ /) a CN R' CN 121 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing CN CN I22 I23 wherein R3 is an alkyl group having 1 to 1 carbon atoms, R4 is H or the paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -5 - 1254704 A8 B8 C8 ______ D8 6. A patent or an alkyl or oxaalkyl group having 1 to 7 carbon atoms, and R5 is an alkyl or alkenyl group having 2 to 7 carbon atoms. 8. The benzoic acid ester of any one of claims 1 to 7 is used as a component of a liquid crystal medium. A liquid crystal medium having at least two liquid crystal compositions, characterized by comprising at least one compound of the formula I as defined in the first aspect of the patent application. 1 0 · Liquid crystal medium as claimed in item 9 of the patent application is used for liquid crystal display elements. 1 1 · A liquid crystal medium as claimed in claim 9 is used for an electro-optical display element. (Please read the precautions on the back and fill out this page) -Installation ·L--Ordering the Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Print this paper scale Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ), (3: