Liquid crystal compounds having a chiral fluorinated terminal portion

• US 6,309,561 B1
• Filed: 12/24/1997
• Issued: 10/30/2001
• Est. Priority Date: 12/24/1997
• Status: Expired due to Fees

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Spawn, Terence D., Hasegawa, Masakazu, Keyes, Michael P., Snustad, Daniel C., Savu, Patricia M., Radcliffe, Marc D.
• Primary Examiner(s): WU, SHEAN CHIU
• Application Number:
  US08/998,400
• Time in Patent Office: 1,406 Days
• Field of Search: 252/299.01, 252/299.61, 252/299.62, 252/299.63, 252/299.65, 252/299.66, 252/299.67, 544/303, 546/346, 549/324, 549/380, 548/215, 568/634, 568/649, 568/669, 570/128, 570/130, 570/131, 570/132, 570/144, 570/183, 570/188, 560/65
• US Class Current: 252/299.61
• CPC Class Codes: C07D 239/26 with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
• CPC Class Codes: C07D 239/34 One oxygen atom
• CPC Class Codes: C09K 19/3405 the heterocyclic ring being a five-membered ring
• CPC Class Codes: C09K 19/3463 Pyrimidine with a carbon chain containing at least one asymmetric carbon atom, i.e. optically active pyrimidines
• CPC Class Codes: C09K 19/3469 Pyrimidine with a specific end-group other than alkyl, alkoxy or -C*-
• CPC Class Codes: C09K 19/3491 having sulfur as hetero atom
• CPC Class Codes: C09K 19/3497 the heterocyclic ring containing sulfur and nitrogen atoms
• CPC Class Codes: C09K 2019/3408 Five-membered ring with oxygen(s) in fused, bridged or spiro ring systems

Abstract

Fluorine-containing, chiral liquid crystal compounds comprise (a) a chiral fluorochemical terminal portion comprising (i) at least one chiral center, which can optionally be heteroatom-substituted; (ii) a terminal fluoroalkyl, fluoroether, perfluoroalkyl, or perfluoroether group; and (iii) an alkylene or fluoroalkylene group optionally containing at least one catenary ether oxygen atom; (b) a chiral or achiral terminal portion consisting of a hydrocarbon or hydrocarbon ether group, and, when chiral, comprising at least one chiral center, which can optionally be heteroatom-substituted; and (c) a central core connecting the terminal portions; the alkylene or fluoroalkylene group of the chiral fluorochemical terminal portion having at least 3 in-chain atoms and being located between the chiral center of the chiral fluorochemical terminal portion and the central core. The compounds have smectic mesophases or latent smectic mesophases and are useful, for example, in liquid crystal display devices.

Claims

1. Fluorine-containing, chiral liquid crystal compounds having smectic mesophases or latent smectic mesophases, the compounds comprising (a) a chiral fluorochemical terminal portion comprising (i) at least one chiral center, which can optionally be heteroatom-substituted;

(ii) a terminal fluoroalkyl, fluoroether, perfluoroalkyl, or perfluoroether group, wherein the fluoroalkyl and perfluoroalkyl groups are represented by the formula —

C_qF_2qX′

, wherein q is at least about 5 and X′

is hydrogen or fluorine; and

(iii) an alkylene or fluoroalkylene group optionally containing at least one catenary ether oxygen atom;

(b) a chiral or achiral terminal portion consisting of a hydrocarbon or hydrocarbon ether group and, when chiral, comprising at least one chiral center, which can optionally be heteroatom-substituted; and

(c) a central core connecting said terminal portions;

said alkylene or fluoroalkylene group of said chiral fluorochemical terminal portion having at least 3 in-chain atoms and being located between said chiral center of said chiral fluorochemical terminal portion and said central core.

2. The compounds of claim 1 wherein said chiral fluorochemical terminal portion is represented by the formula —

D—

R*—

D—

R_f, where R* is a cyclic or acyclic chiral moiety containing at least one chiral center;

R_f is fluoroalkyl, perfluoroalkyl, fluoroether, or perfluoroether; and

each D is independently and non-directionally selected from the group consisting of a covalent bond, —

C(═

O)—

O—

C_rH_2r—

, —

O—

C_rH_2r—

, —

O—

(O═

)C—

C_rH_2r—

, —

C≡

C—

, —

CH═

CH—

, —

C(═

O)—

, —

O

C₅H_2sO

_tC_r′

H_2r—

, —

C_rH_2r—

,

C_sH_2sO

_tC_r′

H_2r′

—

, —

O—

, —

S—

,

and combinations thereof, where one or more hydrogen atoms can optionally be replaced with fluorine, and where r and r′

are independently integers of 0 to about 20, s is independently an integer of 1 to about 10 for each (C_sH_2sO), t is an integer of 1 to about 6, and p is an integer of 0 to about 4;

with the proviso that there are at least 3 in-chain atoms between said central core and at least one said chiral center of R*.

3. The compounds of claim 2 wherein said R_f is perfluoroalkyl or perfluoroether.

4. The compounds of claim 3 wherein said R_f is perfluoroether.

5. The compounds of claim 1 wherein said compounds are represented by the general formula (I):

where M, N, and P are each independently selected from the group consisting of

a, b, and c are each independently zero or an integer of from 1 to 3, with the proviso that the sum of a+b+c be at least 1;

each A and B are non-directionally and independently selected from the group consisting of a covalent bond, —

C(═

O)—

O—

, —

C(═

O)—

S—

, —

C(═

O)—

Se—

, —

C(═

O)—

Te—

, —

(CH₂CH₂)_k—

where k is 1 to 4, —

CH═

CH—

, —

C≡

C—

, —

CH═

N—

, —

CH₂—

O—

, —

C(═

O)—

, and —

O—

;

each X, Y, and Z are independently selected from the group consisting of —

H, —

Cl, —

F, —

Br, —

I, —

OH, —

OCH₃, —

CH₃, —

CF₃, —

OCF₃, —

CN, and —

NO₂;

each 1, m, and n are independently zero or an integer of 1 to 4;

each D is non-directionally and independently selected from the group consisting of a covalent bond,

where one or more hydrogen atoms can optionally be replaced with fluorine, and where r and r′

are independently integers of 0 to about 20, s is independently an integer of 1 to about 10 for each (C_sH_2sO), t is an integer of 1 to about 6, and p is an integer of 0 to about 4;

R is selected from the group consisting of

where each R′

is independently selected from the group consisting of —

Cl, —

F, —

CF₃, —

NO₂, —

CN, —

H, —

C_qH_2q+1,

—

O—

(O═

)C—

C_qH_2q+1, —

C(═

O)—

O—

C_qH_2q+1, —

Br, —

OH, and —

OC_qH_2q+1;

q′

is independently an integer of 1 to about 20 for each (C_q′

H_2q′

—

O);

q is an integer of 1 to about 20;

w is an integer of 0 to about 10;

v is an integer of 0 to about 2;

each v′

is independently an integer of 0 to about 2;

g is an integer of 1 to about 3;

each D is independently and non-directionally selected from the group set forth for D above, with the proviso that the ring containing D has from about 3 to about 10 ring atoms;

each W is independently selected from the group consisting of N, CR′

, and SiR′

; and

R can be chiral or achiral; and

R* is a cyclic or acyclic chiral moiety containing at least one chiral center; and

R_f is fluoroalkyl, perfluoroalkyl, fluoroether, or perfluoroether group, wherein the fluoroalkyl and perfluoroalkyl groups are represented by the formula —

C_qF_2qX′

, wherein q is at least about 5 and X′

is hydrogen or fluorine;

with the proviso that there are at least 3 in-chain atoms between said central core structure —

(M)_a—

A

N

_bB

P

_c— and

at least one said chiral center of R*.

6. The compounds of claim 5 wherein said R* is selected from the group consisting of

where each R′

is independently selected from the group consisting of —

Cl, —

F, —

CF₃, —

NO₂, —

CN, —

H, —

C_qH_2q+1, —

O—

(O═

)C—

C_qH_2q+1, —

C(═

O)—

O—

C_qH_2q+1, —

Br, —

OH, and —

OC_qH_2q+1;

q′

is independently an integer of 1 to about 20 for each (C_q′

H_2q′

—

O);

q is an integer of 1 to about 20;

w is an integer of 0 to about 10;

v is an integer of 0 to about 3;

each v′

is independently an integer of 0 to about 3;

g is an integer of 1 to about 3;

each D is independently and non-directionally selected from the group set forth for D in claim 5, with the proviso that the ring containing D has from about 3 to about 10 ring atoms;

each W is independently selected from the group consisting of N, CR′

, and SiR′

; and

with the proviso that R* is chiral.

7. The compounds of claim 6 wherein each said R′

of said R* is independently selected from the group consisting of —

H, —

F, —

CF₃, —

Br, —

OH, and —

OCH₃.

8. The compounds of claim 5 wherein said R_f is a perfluoroalkyl group represented by the formula —

C_qF_2qX′

wherein q is at least about 5 and X′

is hydrogen or fluorine or a perfluoroether group.

9. The compounds of claim 8 wherein said R_f is perfluoroether.

10. The compounds of claim 5 wherein said perfluoroalkyl is represented by the formula —

C_qF_2qX′

where q is at least about 5 and X′

is hydrogen or fluorine; and

said perfluoroether is represented by the formula —

(C_xF_2xO)_zC_yF_2y+1, where x is independently an integer of 1 to about 10 for each (C_xF_2xO), y is an integer of 1 to about 10, and z is an integer of 1 to about 10.

11. The compounds of claim 5 wherein said compounds are represented by the general formula (II):

12. The compounds of claim 11 wherein said s′

, said t′

, and said r″

are each an integer of 1.

14. mixture of liquid crystal compounds comprising at least one fluorine-containing liquid crystal compound of claim 1.

15. The mixture of claim 14 further comprising at least one other liquid crystal compound having at least one fluorinated terminal portion.

17. A liquid crystal device containing at least one fluorine-containing liquid crystal compound of claim 1.

18. The device of claim 17 further containing at least one other liquid crystal compound having at least one fluorinated terminal portion.

19. The device of claim 18 wherein said other liquid crystal compound is a chiral or achiral, perfluoroether group-containing liquid crystal compound.

20. Fluorine-containing, chiral liquid crystal compounds having smectic mesophases or latent smectic mesophases, the compounds comprising two fluorochemical terminal portions and being represented by the general formula VIII:

where n′

is an integer of 0 to about 10;

j is an integer of 0 or 1;

each R_f moiety is independently selected from the group consisting of fluoroalkyl, fluoroether, perfluoroalkyl, and perfluoroether; and

all other moieties are as defined in claim 5 above.

21. The compounds of claim 20 wherein said compounds are represented by the general formula IX:

22. The compounds of claim 21 wherein said s′

, said t′

, and said r″

are each an integer of 1.

13. Fluorine-containing, chiral liquid crystal compounds having smectic mesophases or latent smectic mesophases, the compounds comprising

(a) a chiral fluorochemical terminal portion represented by the formula —

D—

R*—

D—

R_f where R* is a cyclic or acyclic chiral, moiety containing at least one chiral center;

R_f is perfluoroether; and

each D is independently and non-directionally selected from the aroup consisting of a covalent bond,

and combinations thereof where one or more hydrogene atoms can optionally be replaced with fluorine and where r and r′

are independently integers of 0 to about 20, s is independently an integer of 1 to about 10 for each (C_sH_2sO, t is an integer of 1 to about 6, and p is an integer of 0 to about 4 with the proviso that there are at least 3 in-chain atoms between central core and at least one said chiral center of R*,

(b) a chiral or achiral terminal portion consisting of a hydrocarbon or hydrocarbon ether group, and, when chiral, comprising at least one chiral center, which can optionally be heteroatom-substituted; and

(c) a central core connecting said terminal portions.

16. The mixture of claim wherein said other liquid crystal compound is a chiral or achiral, perfluoroether group-containing liquid crystal compound.

23. Fluorine-containing, chiral liquid crystal compounds having smectic mesophases or latent smectic mesophases, the compounds comprising (a) a chiral fluorochemical terminal portion;

(b) a chiral or achiral terminal portion consisting of a hydrocarbon or hydrocarbon ether group and, when chiral, comprising at least one chiral center, which can optionally be heteroatom-substituted; and

(c) a central core connecting said terminal portions;

said alkylene or fluoroalkylene group of said chiral fluorochemical terminal portion having at least 3 in-chain atoms and being located between said chiral center of said chiral fluorochemical terminal portion and said central core;

wherein said chiral fluorochemical terminal portion is represented by the formula —

D—

R*—

D—

R_f, where R* is a cyclic or acyclic chiral moiety containing at least one chiral center;

R_f is perfluoroalkyl or perfluoroether; and

each D is independently and non-directionally selected from the group consisting of a covalent bond, —

C(═

O)—

O—

C_rH_2r—

, —

O—

C_rH_2r—

, —

O—

(O═

)C—

C_rH_2r—

, —

C≡

C—

, —

CH═

CH—

, —

C(═

O)—

, —

O

C_sH_2sO

_tC_r′

H_2r′

—

, —

C_rH_2r—

, 

C_sH_2sO

_tC_r′

H_2r′

—

, —

O—

, —

S—

,

and combinations thereof, where one or more hydrogen atoms can optionally be replaced with fluorine, and where r and r′

are independently integers of 0 to about 20, s is independently an integer of 1 to about 10 for each (C_sH_2sO), t is an integer of 1 to about 6, and p is an integer of 0 to about 4;

with the proviso that there are at least 3 in-chain atoms between said central core and at least one said chiral center of R*.

24. Fluorine-containing, chiral liquid crystal compounds having smectic mesophases or latent smectic mesophases, the compounds comprising (a) a chiral fluorochemical terminal portion;

(b) a chiral or achiral terminal portion consisting of a hydrocarbon or hydrocarbon ether group and, when chiral, comprising at least one chiral center, which can optionally be heteroatom-substituted; and

(c) a central core connecting said terminal portions;

said alkylene or fluoroalkylene group of said chiral fluorochemical terminal portion having at least 3 in-chain atoms and being located between said chiral center of said chiral fluorochemical terminal portion and said central core;

wherein said compounds are represented by the general formula (I);

where M, N and P are each independently selected from the group consisting of

a, b, and c are each independently zero or an integer of from 1 to 3, with the proviso that the sum of a+b+c be at least 1;

each A and B are non-directionally and independently selected from the group consisting of a covalent bond, —

C(═

O)—

O—

, —

C(═

O)—

S—

, —

C(═

O)—

Se—

, —

C(═

O)—

Te—

, —

(CH₂CH₂)_k—

where k is 1 to 4, —

CH═

CH—

, —

C≡

C—

, —

CH═

N—

, —

CH₂—

O—

, —

C(═

O)—

, and —

O—

;

each X, Y, and Z are independently selected from the group consisting of —

H, —

Cl, —

F, —

Br, —

I, —

OH, —

OCH₃, —

CH₃, —

CF₃, —

OCF₃, —

CN, and —

NO₂;

each 1, m, and n are independently zero or an integer of 1 to 4;

each D is non-directionally and independently selected from the group consisting of a covalent bond,

—

C(═

O)—

O—

C_rH_2r—

, —

O—

C_rH_2r—

, —

O—

(O═

)C—

C_rH_2r—

, —

C≡

C—

, —

CH═

CH—

, —

C(═

O)—

, —

O

C_sH_2sO

_tC_rH_2r—

, —

C_r′

H_2r′

—

, 

C_sH_2sO

_tC_r′

H_2r′

—

, —

O—

, —

S—

,

where one or more hydrogen atoms can optionally be replaced with fluorine, and where r and r′

are independently integers of 0 to about 20, s is independently an integer of 1 to about 10 for each (C_sH_2sO), t is an integer of 1 to about 6, and p is an integer of 0 to about 4;

R is selected from the group consisting of —

O—

((C_q′

H<sub>2q′

−

v′</sub>

—

(R′

)_v′

)—

O)_w—

C_qH<sub>2q+1−

v</sub>—

(R′

)_v, —

((C_q′

H<sub>2q′

−

v′</sub>

—

(R′

)_v′

)—

O)_w—

C_qH<sub>2q+1−

v</sub>—

(R′

)_v, —

C(═

O)—

O—

C_qH<sub>2q+1−

v</sub>—

(R′

)_v, —

O—

(O═

)C—

C_qH<sub>2q+1−

v</sub>—

(R′

)_v,

—

CR′

H—

(D)_g—

CR′

H—

C_qH<sub>2q+1−

v</sub>—

(R′

)_v,

where each R′

is independently selected from the group consisting of —

Cl, —

F, —

CF₃, —

NO₂, —

CN, —

H, —

C_qH_2q+1,

—

O—

(O═

)C—

C_qH_2q+1, —

C(═

O)—

O—

C_qH_2q+1, —

Br, —

OH, and —

OC_qH_2q+1;

q′

is independently an integer of 1 to about 20 for each (C_q′

H_2q′

—

O);

q is an integer of 1 to about 20;

w is an integer of 0 to about 10;

v is an integer of 0 to about 2;

each v′

is independently an integer of 0 to about 2;

g is an integer of 1 to about 3;

each D is independently and non-directionally selected from the group set forth for D above, with the proviso that the ring containing D has from about 3 to about 10 ring atoms;

each W is independently selected from the group consisting of N, CR′

, and SiR′

; and

R can be chiral or achiral; and

R* is a cyclic or acyclic chiral moiety containing at least one chiral center; and

R_f is perfluoroether;

with the proviso that there are at least 3 in-chain atoms between said central core structure —

(M)_a—

A

N

_bB

P

_c— and

at least one said chiral center of R*.

25. Fluorine-containing, chiral liquid crystal compounds having smectic mesophases or latent smectic mesophases, the compounds comprising (a) a chiral fluorochemical terminal portion;

(b) a chiral or achiral terminal portion consisting of a hydrocarbon or hydrocarbon ether group and, when chiral, comprising at least one chiral center, which can optionally be heteroatom-substituted; and

(c) a central core connecting said terminal portions;

said alkylene or fluoroalkylene group of said chiral fluorochemical terminal portion having at least 3 in-chain atoms and being located between said chiral center of said chiral fluorochemical terminal portion and said central core;

wherein said compounds are represented by the general formula (II);

29. The compounds of claim 25 wherein said s′

, said t′

, and said r″

are each an integer of 1.

26. A mixture of liquid crystal compounds comprising at least one fluorine-containing, chiral liquid crystal compound having a smectic mesophase or a latent smectic mesophase, the compound comprising (a) a chiral fluorochemical terminal portion comprising (i) at least one chiral center, which can optionally be heteroatom-substituted;

(ii) a terminal fluoroalkyl, fluoroether, perfluoroalkyl, or perfluoroether group; and

(iii) an alkylene or fluoroalkylene group optionally containing at least one catenary ether oxygen atom;

(b) a chiral or achiral terminal portion consisting of a hydrocarbon or hydrocarbon ether group and, when chiral, comprising at least one chiral center, which can optionally be heteroatom-substituted; and

(c) a central core connecting said terminal portions;

said alkylene or fluoroalkylene group of said chiral fluorochemical terminal portion having at least 3 in-chain atoms and being located between said chiral center of said chiral fluorochemical terminal portion and said central core; and

at least one other liquid crystal compound having at least one fluorinated terminal portion, wherein said other liquid crystal compound is a chiral or achiral, perfluoroether group-containing liquid crystal compound.

27. A liquid crystal device containing at least one fluorine-containing, chiral liquid crystal compound having a smectic mesophase or a latent smectic mesophase, the compound comprising (a) a chiral fluorochemical terminal portion comprising (i) at least one chiral center, which can optionally be heteroatom-substituted;

(ii) a terminal fluoroalkyl, fluoroether, perfluoroalkyl, or perfluoroether group; and

(iii) an alkylene or fluoroalkylene group optionally containing at least one catenary ether oxygen atom;

(b) a chiral or achiral terminal portion consisting of a hydrocarbon or hydrocarbon ether group and, when chiral, comprising at least one chiral center, which can optionally be heteroatom-substituted; and

(c) a central core connecting said terminal portions;

said alkylene or fluoroalkylene group of said chiral fluorochemical terminal portion having at least 3 in-chain atoms and being located between said chiral center of said chiral fluorochemical terminal portion and said central core; and

at least one other liquid crystal compound having at least one fluorinated terminal portion, wherein said other liquid crystal compound is a chiral or achiral, perfluoroether group-containing liquid crystal compound.

28. Chiral liquid crystal intermediate compounds represented by the following general formulas IV and VI:

where N and P are each independently selected from the group consisting of

b and c are each independently zero or an integer of from 1 to 3;

B is non-directionally selected from the group consisting of a covalent bond, —

C(═

O)—

O—

, —

C(═

O)—

S—

, —

C(═

O)—

Se—

, —

C(═

O)—

Te—

, —

(CH₂CH₂)_k—

where k is 1 to 4, —

CH═

CH—

, —

C≡

C—

, —

CH═

N—

, —

CH₂—

O—

, —

C(═

O)—

, and —

O—

;

each Y and Z are independently selected from the group consisting of —

H, —

Cl, —

F, —

Br, —

I, —

OH, —

OCH₃, —

CH₃, —

CF₃, —

OCF₃, —

CN, and —

NO₂;

each m and n are independently zero or an integer of 1 to 4;

each D is non-directionally and independently selected from the group consisting of a covalent bond, —

C(═

O)—

O—

C_rH_2r—

, —

O—

C_rH_2r—

, —

O—

(O═

)C—

C_rH_2r—

, —

C≡

C—

, —

CH═

CH—

, —

C(═

O)—

, —

O

C_sH_2sO

_tC_rH_2r—

, —

C_r′

H_2r′

—

, 

C_sH_2sO

_tC_r′

H_2r′

—

, —

O—

, —

S—

,

where one or more hydrogen atoms can optionally be replaced with fluorine, and where r and r′

are independently integers of 0 to about 20, s is independently an integer of 1 to about 10 for each (C_sH_2sO), t is an integer of 1 to about 6, and p is an integer of 0 to about 4;

R* is a cyclic or acyclic chiral moiety containing at least one chiral center and selected from the group consisting of —

O—

((C_q′

H<sub>2q′

−

v′</sub>

—

(R′

)_v′

)—

O)_w—

C_qH<sub>2q−

v</sub>—

(R′

)_v —

((C_q′

H<sub>2q′

−

v′</sub>

—

(R′

)_v′

)—

O)_w—

C_qH<sub>2q−

v</sub>—

(R′

)_v—

, —

C(═

O)—

O—

C_qH<sub>2q−

v</sub>—

(R′

)_v—

, —

O—

(O═

)C—

C_qH<sub>2q−

v</sub>—

(R′

)_v—

,

where each R′

is independently selected from the group consisting of —

Cl, —

F, —

CF₃, —

NO₂, —

CN, —

H, —

C_qH_2q+1, —

O—

(O═

)C—

C_qH_2q+1, —

C(═

O)—

O—

C_qH_2q+1, —

Br, —

OH, and —

OC_qH_2q+1;

q′

is independently an integer of 1 to about 20 for each (C_qH_2q′

—

O);

q is an integer of 1 to about 20;

w is an integer of 0 to about 10;

v is an integer of 0 to about 3;

each v′

is independently an integer of 0 to about 3;

g is an integer of 1 to about 3;

each D is independently and non-directionally selected from the group set forth for D above, with the proviso that the ring containing D has from about 3 to about 10 ring atoms;

each W is independently selected from the group consisting of N, CR′

, and SiR′

; and

with the proviso that R* is chiral;

R_f is perfluoroether;

with the proviso that there are at least 3 in-chain atoms between said central core structure

or

and at least one said chiral center of R*;

and A″ and

B″

are selected from the group consisting of —

H, —

Cl, —

Br, —

I, —

OH, —

COOH, —

CH(CH₂OH)₂, —

SH, —

SeH, —

TeH, —

NH₂, —

COCl, —

CHO,—

C≡

CH, dialkyl borane, —

CH═

CH₂, —

OSO₂R_f′

″

, —

OSO₂CH₃, —

OSO₂-cyclo(C₆H₄)—

CH₃, —

CH₂COOH, —

NH(C═

O)OC_qH_2q+1, —

NCO, and —

CH(C(O)O—

C_qH_2q+1)₂, where R_f′

″

is a perfluoroalkyl group having from 1 to about 10 carbon atoms and q is an integer of 0 to about 20.