4,6-difluorodibenzothiophene derivatives
4,6-difluorodibenzothiophene compounds of formula I the preparation thereof, the use thereof as components in liquid-crystalline media and electro-optical display elements which contain the liquid-crystalline media.
1. A compound of formula I:
in which
m and n, independently of one another, are each 0, 1 or 2,
R 1 and R 2 , independently of one another, denote an alkyl or alkoxy radical having 1 to 15 C atoms, in which one or more CH 2 groups are optionally replaced, independently of one another, by —C≡C—, —CF 2 O—, —OCF 2 —, —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 one or more H atoms are optionally replaced by halogen,
A 1 and A 2 , independently of one another, denote
a) 1,4-phenylene, in which one or two CH groups are optionally replaced by N and in which one or more H atoms are optionally replaced by L,
b) trans-1,4-cyclohexylene or 1,4-cyclohexenylene, in which one or more non-adjacent CH 2 groups are optionally replaced by —O— and/or —S— and in which one or more H atoms are optionally replaced by F or Cl, or
c) tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydrofuran-2,5-diyl, cyclobutane-1,3-diyl, piperidine-1,4-diyl, thiophene-2,5-diyl or selenophene-2,5-diyl, each of which is optionally mono- or polysubstituted by L,
L on each occurrence, independently, denotes F, Cl, CN, SCN, SF 5 or straight-chain or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, and
Z 1 and Z 2 , independently of one another, denote a single bond, —CF 2 O—, —OCF 2 —, —CH 2 O—, —OCH 2 —, —(CO)O—, —O(CO)—, —(CH 2 ) 4 —, —CH 2 CH 2 —, —CF 2 —CF 2 —, —CF 2 —CH 2 —, —CH 2 —CF 2 —, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —(CH 2 ) 3 O—, —O(CH 2 ) 3 —, —C≡C—, —O—, —CH 2 —, —(CH 2 ) 3 — or —CF 2 .
2. A compound according to claim 1 , wherein the sum m+n is 0 or 1.
3. A compound according to claim 1 , wherein
R 1 and R 2 , independently of one another, denote an unsubstituted alkyl radical or alkoxy radical having 1 to 15 carbon atoms or an alkenyl, alkenyloxy or alkynyl radical having 2 to 15 C atoms, which are in each case optionally mono- or polyhalogenated.
4. A compound according claim 1 , wherein m+n=0.
5. A compound according to claim 1 , which is one of formula IA to IC
in which
R 1 , R 2 , A 1 and Z 1 have the meanings as for the compound of formula I.
6. A compound according to claim 1 , which is one of formulae IA-1 to IA-10,
in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-7 C atoms, alkenyl and alkenyl* each, independently of one another, denote a straight-chain alkenyl radical having 2-7 C atoms, alkoxy and alkoxy* each, independently of one another, denote a straight-chain alkoxy radical having 1-7 C atoms.
7. A compound according to claim 1 , wherein
R 1 and R 2 , independently of one another, denote an alkoxy or alkyl radical having 1 to 7 carbon atoms or an alkenyl radical having 2 to 7 carbon atoms.
8. A compound according to claim 1 , wherein
R 1 and R 2 each denote an alkoxy group having 1 to 7 carbon atoms.
9. A compound according to claim 1 , wherein
m+n=1 or 2, and
the ring A 1 is in each case one of the following
10. A liquid-crystalline medium comprising at least two compounds, one of which is a compound according to claim 1 .
11. An electro-optical display element containing a liquid-crystalline medium according to claim 10 .
12. A process for preparing a compound of formula I according to claim 1 , comprising deprotonating a compound of formula (B) at position 3
in which Z 2 , A 2 , n and R 2 , independently, are defined as in the compound of formula I,
by a deprotonating reagent and converting into a compound of formula (C)
in which, independently,
X denotes B(OR) 2 , —C(OH)R 2 , —(CO)OH, —(CO)Cl, OH or
R, independently, denotes H or an alkyl radical having 1 to 14 C atoms, and
Z 2 , A 2 , n, R 1 and R 2 are defined as in the compound of formula I, and converting into a compound of formula I.
13. A compound according to claim 1 , which is
14. A compound according to claim 1 , which is one of the following compounds
wherein R 1 and R 2 are straight-chain unless indicated otherwise
R 1
R 2
—CH 3
—CH 3
—CH 3
—C 2 H 5
—CH 3
—C 3 H 7
—CH 3
—C 4 H 9
—CH 3
—C 5 H 11
—CH 3
—C 6 H 13
—C 2 H 5
—C 2 H 5
—C 2 H 5
—C 3 H 7
—C 2 H 5
—C 4 H 9
—C 2 H 5
—(CH 2 ) 2 CH═CH 2
—C 2 H 5
—(CH 2 ) 2 CH(CH 3 ) 2
—C 2 H 5
—C 5 H 11
—C 2 H 5
—C 6 H 13
—C 2 H 5
—C 7 H 15
—C 2 H 5
—(CH 2 ) 3 CH(CH 3 ) 2
—C 3 H 7
—C 3 H 7
—C 3 H 7
—C 4 H 9
—C 3 H 7
—C 5 H 11
—C 3 H 7
—C 6 H 13
—C 3 H 7
—C 7 H 15
—C 4 H 9
—C 4 H 9
—C 4 H 9
—C 5 H 11
—C 4 H 9
—(CH 2 ) 2 CH═CHCH 3 *)
—C 4 H 9
—C 6 H 13
—C 4 H 9
—C 7 H 15
—C 5 H 11
—C 5 H 11
—C 5 H 11
—C 6 H 13
—C 6 H 13
—C 6 H 13
wherein *) means trans isomer.
15. A compound according to claim 1 , which is one of the following compounds
wherein R 1 and R 2 are straight-chain unless indicated otherwise
R 1
R 2
—CH 3
—CH 3
—CH 3
—C 2 H 5
—CH 3
—C 3 H 7
—CH 3
—C 4 H 9
—CH 3
—C 5 H 11
—CH 3
—C 6 H 13
—C 2 H 5
—CH 3
—C 2 H 5
—C 2 H 5
—C 2 H 5
—C 3 H 7
—C 2 H 5
—C 4 H 9
—C 2 H 5
—CH 2 CH(CH 3 ) 2
—C 2 H 5
—(CH 2 ) 2 CH═CH 2
—C 2 H 5
—(CH 2 ) 2 CH(CH 3 ) 2
—C 2 H 5
—C 5 H 11
—C 2 H 5
—C 6 H 13
—C 2 H 5
—(CH 2 ) 3 CH(CH 3 ) 2
—C 3 H 7
—CH 3
—C 3 H 7
—C 2 H 5
—C 3 H 7
—C 3 H 7
—C 3 H 7
—C 4 H 9
—C 3 H 7
—(CH 2 ) 2 CH═CH 2
—C 3 H 7
—C 5 H 11
—C 3 H 7
—C 6 H 13
—C 4 H 9
—CH 3
—C 4 H 9
—C 2 H 5
—C 4 H 9
—C 3 H 7
—(CH 2 ) 2 CH═CH 2
—C 2 H 5
—C 4 H 9
—C 4 H 9
—C 4 H 9
—C 5 H 11
—C 4 H 9
—(CH 2 ) 2 CH═CHCH 3 *)
—C 4 H 9
—C 6 H 13
—C 5 H 11
—CH 3
—C 5 H 11
—C 2 H 5
—(CH 2 ) 2 CH═CHCH 3 *)
—C 2 H 5
—C 5 H 11
—C 3 H 7
—C 5 H 11
—C 4 H 9
—C 5 H 11
—(CH 2 ) 2 CH═CH 2
—C 5 H 11
—C 6 H 13
wherein *) means trans isomer.
16. A compound according to claim 1 , which is one of the following compounds
wherein R 1 and R 2 are straight-chain unless indicated otherwise
R 1
R 2
—CH 3
—CH 3
—CH 3
—C 2 H 5
—CH 3
—C 3 H 7
—CH 3
—C 4 H 9
—CH 3
—C 5 H 11
—CH 3
—C 6 H 13
—CH 3
—(CH 2 ) 2 CH═CH 2
—CH 3
—(CH 2 ) 2 CH═CHCH 3 *)
—C 2 H 5
—C 2 H 5
—C 2 H 5
—C 3 H 7
—C 2 H 5
—C 4 H 9
—C 2 H 5
—CH 2 CH(CH 3 ) 2
—C 2 H 5
—(CH 2 ) 2 CH═CH 2
—C 2 H 5
—(CH 2 ) 2 CH(CH 3 ) 2
—C 2 H 5
—C 5 H 11
—C 2 H 5
—C 6 H 13
—C 2 H 5
—(CH 2 ) 3 CH(CH 3 ) 2
—C 3 H 7
—C 3 H 7
—C 3 H 7
—C 4 H 9
—C 3 H 7
—(CH 2 ) 2 CH═CH 2
—C 3 H 7
—C 5 H 11
—C 3 H7
—C 6 H 13
—C 4 H 9
—C 4 H 9
—(CH 2 ) 2 —CH═CH 2
—(CH 2 ) 2 CH═CH 2
—C 4 H 9
—C 5 H 11
—C 4 H 9
—(CH 2 ) 2 CH═CHCH 3 *)
—C 4 H 9
—C 6 H 13
—C 5 H 11
—(CH 2 ) 2 CH═CH 2
—C 5 H 11
—C 6 H 13
wherein *) means trans isomer.
17. A compound according to claim 1 , which is one of the following compounds
18. A compound according to claim 1 , which is one of formulae IB-1 to IC-13,
in which alkyl, independently of one another, denotes a straight-chain alkyl radical having 1-7 C atoms, and alkyl(O) stands for alkyl or alkoxy having 1 to 7 C atoms.
19. A compound according to claim 1 , which is one of the following compounds
20. A compound according to claim 1 , which is one of the following compounds