Bimesogenic compounds and mesogenic media

Patent metadata

Field	Value
Publication number	US-9914876-B2
Application number	US-201314413011-A
Country	US
Kind code	B2
Filing date	Jun 14, 2013
Priority date	Jul 6, 2012
Publication date	Mar 13, 2018
Grant date	Mar 13, 2018

Abstract

The invention relates to bimesogenic compounds of formula I

wherein R 11 , R 12 , MG 11 , MG 12 , X 11 , X 12 and Sp 1 have the meaning given in claim 1 , to the use of bimesogenic compounds of formula I in liquid crystal media and particular to flexoelectric liquid crystal devices comprising a liquid crystal medium according to the present invention.

First claim

The invention claimed is:

1. A bimesogenic compound of formula I

wherein
R 11 is CF 3 ,
R 12 is OCF 3 , CF 3 , H, F, Cl, CN, NCS or a straight-chain or branched alkyl group with 2 to 25 C atoms which may be unsubstituted, mono- or polysubstituted by halogen or CN, wherein one or more non-adjacent CH 2 groups are each optionally replaced, in each occurrence independently from one another, by —O—, —S—, —NH—, —N(CH 3 )—, —CO—, —COO—, —OCO—, —O—CO—O—, —S—CO—, —CO—S—, —CH═CH—, —CH═CF—, —CF═CF— or —C≡C— in such a manner that oxygen atoms are not linked directly to one another,
MG 11 and MG 12 are each independently a mesogenic group and
at least one of
MG 11 and MG 12 comprises one, two or more 6-atomic rings, and
Sp 1 is a spacer group comprising 1, 3 or 5 to 40 C atoms, wherein one or more non-adjacent and non-terminal CH 2 groups are each optionally replaced by —O—, —S—, —NH—, —N(CH 3 )—, —CO—, —O—CO—, —S—CO—, —O—COO—, —CO—S—, —CO—O—, —CH(halogen)-, —CH(CN)—, —CH═CH— or —C≡C—, however in such a way that no two O-atoms are adjacent to one another, no two —CH═CH— groups are adjacent to each other, and no two groups selected from —O—CO—, —S—CO—, —O—COO—, —CO—S—, —CO—O— and —CH═CH— are adjacent to each other,
X 11 and X 12 are independently from one another a linking group selected from —CO—O—, —O—CO—, —CH═CH—, —C≡C—, and —S—,
under the condition that in —X 11 -Sp 1 -X 12 — no two O atoms are adjacent to one another, no two —CH═CH— groups are adjacent to each other, and no two groups selected from —O—CO—, —S—CO—, —O—COO—, —CO—S—, —CO—O— and —CH═CH— are adjacent to each other.

2. A bimesogenic compound according to claim 1 , wherein MG 11 and MG 12 are independently of each other selected from partial formula II
-A 11 -(Z 11 -A 12 ) k -  II

wherein
Z 11 are, independently of each other in each occurrence, a single bond, —COO—, —OCO—, —O—CO—O—, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O—, —CH 2 CH 2 —, —(CH 2 ) 4 —, —CF 2 CF 2 —, —CH═CH—, —CF═CF—, —CH═CH—COO—, —OCO—CH═CH— or —C≡C—, optionally substituted with one or more of F, S and/or Si,
A 11 and A 12 are each independently in each occurrence 1,4-phenylene, wherein in addition one or more CH groups are each optionally replaced by N, trans-1,4-cyclo-hexylene in which, in addition, one or two non-adjacent CH 2 groups are each optionally replaced by O or S, 1,4-cyclohexenylene, 1,4-bicyclo-(2,2,2)-octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydro-naphthalene-2,6-diyl, 1,2,3,4-tetrahydro-naphthalene-2,6-diyl, cyclobutane-1,3-diyl, spiro[3.3]heptane-2,6-diyl or dispiro[3.1.3.1] decane-2,8-diyl, it being possible for all these groups to be unsubstituted, mono-, di-, tri- or tetrasubstituted with F, Cl, CN or alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl groups with 1 to 7 C atoms, wherein one or more H atoms are each optionally replaced by F or Cl, and
k is 0, 1, 2, 3 or 4.

3. A bimesogenic compound according to claim 2 , wherein MG 11 and MG 12 are independently of one another selected from the group of formulae II-1 to II-26
-Phe-Z-Phe-  II-1

-Phe-Z-Cyc-  II-2

-Cyc-Z-Cyc-  II-3

-Phe-Z-PheL-  II-4

-PheL-Z-Phe-  II-5

-PheL-Z-Cyc-  II-6

-PheL-Z-PheL-  II-7

-Phe-Z-Phe-Z-Phe-  II-8

-Phe-Z-Phe-Z-Cyc-  II-9

-Phe-Z-Cyc-Z-Phe-  II-10

-Cyc-Z-Phe-Z-Cyc-  II-11

-Phe-Z-Cyc-Z-Cyc-  II-12

-Cyc-Z-Cyc-Z-Cyc-  II-13

-Phe-Z-Phe-Z-PheL-  II-14

-Phe-Z-PheL-Z-Phe-  II-15

-PheL-Z-Phe-Z-Phe-  II-16

-PheL-Z-Phe-Z-PheL-  II-17

-PheL-Z-PheL-Z-Phe-  II-18

-PheL-Z-PheL-Z-PheL-  II-19

-Phe-Z-PheL-Z-Cyc-  II-29

-Phe-Z-Cyc-Z-PheL-  II-21

-Cyc-Z-Phe-Z-PheL-  II-22

-PheL-Z-Cyc-Z-PheL-  II-23

-PheL-Z-PheL-Z-Cyc-  II-24

-PheL-Z-Cyc-Z-Cyc-  II-25

-Cyc-Z-PheL-Z-Cyc-  II-26

wherein
Cyc is 1,4-cyclohexlene, preferably trans-1,4-cyclohexlene,
Phe is 1,4-phenylene,
PheL is 1,4-phenylene, which is substituted by one, two or three fluorine atoms, by one or two Cl atoms or by one Cl atom and one F atom, and
Z is a single bond, —COO—, —OCO—, —O—CO—O—, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O—, —CH 2 CH 2 —, —(CH 2 ) 4 —, —CF 2 CF 2 —, —CH═CH—, —CF═CF—, —CH═CH—COO—, —OCO—CH═CH— or —C≡C—, optionally substituted with one or more of F, S and/or Si.

4. A bimesogenic compound according claim 1 , wherein R 12 is OCF 3 , CF 3 , F, Cl or CN.

5. A bimesogenic compound according to claim 1 , wherein Sp 1 is —(CH 2 ) o — and o is 1, 3 or an integer from 5 to 15.

6. A liquid-crystalline medium comprising one or more bimesogenic compounds according to claim 1 .

7. The liquid-crystalline medium according to claim 6 , wherein said medium further comprises one or more compounds selected from formulae III
R 31 -MG 31 -X 31 -Sp 3 -X 32 -MG 32 -R 32   III

wherein
R 31 and R 32 are each independently H, F, Cl, CN, NCS or a straight-chain or branched alkyl group with 1 to 25 C atoms which may be unsubstituted, mono- or polysubstituted by halogen or CN, wherein one or more non-adjacent CH 2 groups are each optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —N(CH 3 )—, —CO—, —COO—, —OCO—, —O—CO—O—, —S—CO—, —CO—S—, —CH═CH—, —CH═CF—, —CF═CF— or —C≡C— in such a manner that oxygen atoms are not linked directly to one another,
MG 31 and MG 32 are each independently a mesogenic group,
Sp 3 is a spacer group comprising 5 to 40 C atoms, wherein one or more non-adjacent CH 2 groups are each optionally replaced by —O—, —S—, —NH—, —N(CH 3 )—, —CO—, —O—CO—, —S—CO—, —O—COO—, —CO—S—, —CO—O—, —CH(halogen)-, —CH(CN)—, —CH═CH— or —C≡C—, and
X 31 and X 32 are each independently —O—, —S—, —CO—, —COO—, —OCO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CH═CH—, —CH═CH—COO—, —OCO—CH═CH—, —C≡C— or a single bond, and

with the condition that compounds of formula I are excluded.

8. A liquid crystal device comprising a liquid crystalline medium comprising two or more components, one or more of which is a bimesogenic compound according to claim 1 .

9. The liquid crystal device according to claim 8 , wherein said device is a flexoelectric device.

10. A bimesogenic compound according claim 1 , wherein —X 11 -Sp 1 -X 12 — is —O—CO-Sp 1 -O—CO— or —C≡C-Sp 1 -C≡C—,
Sp 1 is —(CH 2 ) n —, and
n is 1, 3 or an integer from 5 to 15,
wherein one or more H atoms in —(CH 2 ) n — are each optionally be replaced by F or CH 3 .

11. A bimesogenic compound according claim 3 , wherein MG 11 and MG 12 are independently of one another selected from formulae II-1, II-4, II-5, II-7, II-8, II-14, II-15, II-16, II-17, II-18 and II-19.

12. A bimesogenic compound according claim 3 , wherein one of Z is —COO—, —OCO—, —CH 2 —O—, —O—CH 2 —, —CF 2 —O— or —O—CF 2 —, and the others of Z, if present, are each a single bond.

13. A bimesogenic compound according claim 2 , wherein MG 11 and MG 12 are independently of one another selected from the following formulae and their mirror images:

wherein
L is in each occurrence independently of each other F or Cl, and
r is in each occurrence independently of each other 0, 1, 2 or 3.

14. A bimesogenic compound according claim 1 , wherein R 12 is H, F, Cl, CN, NO 2 , OCH 3 , COCH 3 , COC 2 H 5 , COOCH 3 , COOC 2 H 5 , CF 3 , C 2 F 5 , OCF 3 , OCHF 2 , or OC 2 F 5 .

Assignees

• Merck Patent Gmbh

Inventors

• Adlem Kevin
• Parri Owain Llyr
• Tuffin Rachel
• Saxton Patricia Eileen
• Snow Benjamin
• Goulding Mark John
• Smith Nathan

Classifications

• C07C43/225

  containing halogen · CPC title

• C07C69/67

  of saturated acids · CPC title

• C07C255/50

  to carbon atoms of non-condensed six-membered aromatic rings · CPC title

• C09K19/2014 Primary

  containing additionally a linking group other than -COO- or -OCO-, e.g. -CH2-CH2-, -CH=CH-, -C=C-; containing at least one additional carbon atom in the chain containing -COO- or -OCO- groups, e.g. -(CH2)m-COO-(CH2)n- · CPC title

• C07C25/18

  Polycyclic aromatic halogenated hydrocarbons · CPC title