# US 8,273,264 B2 · Liquid-crystal compounds and LC media

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- Number: US 8,273,264 B2
- Document ID: US8273264B2
- Status: Granted
- Kind: B2
- Application number: 12/687,973
- Filed: 2010-01-15
- Published: 2010-07-22
- Granted: 2012-09-25
- Earliest claimed: 2009-01-20
- Assignees: Merck Patent GmbH
- Inventors: Axel Jansen; Detlef Pauluth; Bernd Fiebranz; Bernhard Rieger
- Web page: https://patentgrep.com/patent/US8273264B2

## CPC

- C09K 19/3003: {Compounds containing at least two rings in which the different rings are directly linked (covalent bond)}
- C09K 19/42: Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K 19/44: containing compounds with benzene rings directly linked
- C09K 2019/0444: {characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group}
- C09K 2019/301: {Cy-Cy-Ph}
- C09K 2019/3012: {Cy-Cy-Cy-Ph, or more Cy rings}
- C09K 2323/00: Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE

## Abstract

Disclosed are novel liquid-crystal compounds, processes and intermediates for the preparation thereof, the use thereof for optical, electro-optical and electronic purposes, in particular in liquid-crystal (LC) media and LC displays, and to LC media and LC displays containing the same.

## Claims

### Claim 1

A compound of formula I
in which
R1 denotes H, F, Cl, Br, —CN, —SCN, —NCS, SF5 or straight-chain or branched alkyl having 1 to 12 C atoms, in which, in addition, one or more non-adjacent CH2 groups may each be replaced, independently of one another, by —C≡C—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a way that O and/or S atoms are not linked directly to one another, and in which, in addition, one or more H atoms may be replaced by F, Cl or Br, or P-Sp-,
R2 denotes H or an unsubstituted alkyl having 1 to 5 C atoms,
P denotes a polymerizable group,
Sp denotes a spacer group or a single bond,
A1 on each occurrence, identically or differently, denotes phenylene-1,4-diyl, in which, in addition, one or two CH groups may be replaced by N and one or more H atoms may be replaced by halogen, CN, CH3, CHF2, CH2F, OCH3, OCHF2 or OCF3,
cyclohexane-1,4-diyl, in which, in addition, one or two non-adjacent CH2 groups may be replaced, independently of one another, by O and/or S, and one or more H atoms may be replaced by F,
cyclohexene-1,4-diyl, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl,
Z1 and Z2 each, independently of one another, denote —CF2O—, —OCF2—, —CH2O—, —OCH2—, —C2H4—, —C2F4—, —CF2CH2—, —CH2CF2—, —CFHCFH—, —CFHCH2—, —CH2CFH—, —CF2CFH—, —CFHCF2—, —CH═CH—, —CF═CH—, —CH═CF—, —CF═CF—, —C≡C— or a single bond, and
m denotes 0, 1, 2 or 3.

### Claim 2 (depends on 1)

A compound according to claim 1, wherein m denotes 0 or 1.

### Claim 3 (depends on 1)

A compound according to claim 1, wherein A1 is

### Claim 4 (depends on 1)

A compound according to claim 1, wherein Z1 and Z2 denote a single bond.

### Claim 5 (depends on 1)

A compound according to claim 1, wherein R1 denotes alkyl having 1 to 5 C atoms, and R2 denotes an unsubstituted alkyl having 1 to 5 C atoms.

### Claim 6 (depends on 1)

A compound according to claim 1, which is a compound of formula Ia
in which
R1 denotes H, F, Cl, Br, —CN, —SCN, —NCS, SF5 or straight-chain or branched alkyl having 1 to 12 C atoms, in which, in addition, one or more non-adjacent CH2 groups may each be replaced, independently of one another, by —C≡C—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a way that O and/or S atoms are not linked directly to one another, and in which, in addition, one or more H atoms may be replaced by F, Cl or Br, or P-Sp-, and
R2 denotes H or an unsubstituted alkyl having 1 to 5 C atoms.

### Claim 7 (depends on 1)

A liquid crystal medium comprising one or more compounds according to claim 1, and at least one further liquid crystalline compound that is not of formula I.

### Claim 8 (depends on 7)

A liquid crystal medium according to claim 7, comprising one or more compounds of formulae II and/or III:
in which
A denotes 1,4-phenylene or trans-1,4-cyclohexylene,
a is 0 or 1,
R3 denotes alkenyl having 2 to 9 C atoms, and
R4 denotes alkyl having 1 to 12 C atoms, where, in addition, one or two non-adjacent CH2 groups may be replaced by —O—, —CH═CH—, —CO—, —OCO— or —COO— in such a way that O atoms are not linked directly to one another.

### Claim 9 (depends on 7)

A liquid crystal medium according to claim 7, comprising one or more compounds of the following formulae:
in which
R0 denotes an alkyl or alkoxy radical having 1 to 15 C atoms, in which, in addition, one or more CH2 groups may each be replaced, independently of one another, by —C≡C—, —CF2O—, —CH═CH—,
—O—, —CO—O— or —O—CO— in such a way that O atoms are not linked directly to one another, and in which, in addition, one or more H atoms may be replaced by halogen,
X0 denotes F, Cl, CN, SF5, SCN, NCS, a halogenated alkyl radical, halogenated alkenyl radical, halogenated alkoxy radical or halogenated alkenyloxy radical, each having up to 6 C atoms,
Y1-6 each, independently of one another, denote H or F,
Z0 denotes —C2H4—, —(CH2)4—, —CH═CH—, —CF═CF—, —C2F4—, —CH2CF2—, —CF2CH2—, —CH2O—, —OCH2—, —COO—, —CF2O— or —OCF2—, and in the formulae V and VI also a single bond, and
b and c each, independently of one another, denote 0 or 1.

### Claim 10 (depends on 1)

A liquid crystal display containing one or more compounds according to claim 1.

### Claim 11 (depends on 10)

A liquid crystal display according to claim 10, which is an MLC, TN, STN or IPS display.

### Claim 12 (depends on 1)

A process for preparing a compound according to claim 1, comprising
a) metallating 1,4-dihalobenzene in one halogen position,
b) adding the organometallic compound obtained in a) onto a ketone of the following formula:
wherein R1, A1, Z1 and m have the meanings indicated for the compound of formula I,
c) eliminating water from the alcohol obtained in b),
d) hydrogenating the alkene obtained in c),
e) optionally isomerizing the mixture obtained in d) to give the trans-trans isomer of the bicyclohexyl group of the following formula:
wherein R1, A1, Z1 and m have the meanings indicated for the compound of formula I, and Hal is halogen,
f1) Sonogashira coupling the halogen compound obtained in e) to an alkyne of formula HC≡C—Z2—R2, in which R2 and Z2 have the meanings indicated for the compound of formula I,
or
f2) Sonogashira coupling the halogen compound obtained in e) to
trialkylsilylacetylene,
g2) desilylating the acetylene obtained in f2),
h2) deprotonating the terminal acetylene obtained in g2) by a base,
i2) alkylating the acetylide obtained in h2) by an alkylating agent, optionally by an alkyl iodide of formula R2—I,
or
i3) reacting the acetylide obtained in h2) with a haloalkane in a Kumada-Corriu reaction.

### Claim 13 (depends on 1)

A compound according to claim 1, wherein R2 denotes methyl.

### Claim 14 (depends on 6)

A compound according to claim 6, wherein R2 denotes methyl.

### Claim 15 (depends on 1)

A compound according to claim 1, which is a compound of formula Ia, Ib or Ic
in which
R1 denotes H, F, Cl, Br, —CN, —SCN, —NCS, SF5 or straight-chain or branched alkyl having 1 to 12 C atoms, in which, in addition, one or more non-adjacent CH2 groups may each be replaced, independently of one another, by —CH═CH—, —C≡C—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a way that O and/or S atoms are not linked directly to one another, and in which, in addition, one or more H atoms may be replaced by F, Cl or Br, or P-Sp-, and
R2 denotes H or an unsubstituted alkyl having 1 to 5 C atoms.

### Claim 16 (depends on 15)

A compound according to claim 15, wherein R2 denotes methyl.

### Claim 17 (depends on 1)

A compound according to claim 1, wherein R1 denotes alkyl.

### Claim 18 (depends on 1)

A compound according to claim 1, wherein R1 denotes F, Cl, Br, —CN, —SCN, —NCS, or SF5.

### Claim 19 (depends on 1)

A compound according to claim 1, wherein R2 denotes straight-chain methyl, ethyl, propyl, butyl or pentyl.

### Claim 20 (depends on 17)

A compound according to claim 17, wherein R2 denotes straight-chain methyl, ethyl, propyl, butyl or pentyl.

### Claim 21 (depends on 1)

A compound according to claim 1, wherein
Z2 denotes —CF2O—, —OCF2—, —CH2O—, —OCH2—, —C2F4—, —CF2CH2—, —CH2CF2—, —CFHCFH—, —CFHCH2—, —CH2CFH—, —CF2CFH—, —CFHCF2—, —CH═CH—, —CF═CH—, —CH═CF—, —CF═CF—, —C≡C— or a single bond.