Thiadiazoloquinoxaline derivatives
The present invention relates to thiadiazoloquinoxaline derivatives of the formula I, in which R 11 , R 12 , A 11 , A 12 , A 21 , A 22 , Z 11 , Z 12 , Z 21 , Z 22 , W, X 11 , X 12 , r and s have the meanings indicated in Claim 1, to processes and intermediates for the preparation thereof, to the use of the compounds of the formula I for optical, electro-optical and electronic purposes, in particular in liquid-crystal media and in devices for regulating the passage of energy from an outside space into an inside space, and to these LC media and the devices comprising these media.
1. A guest-host liquid crystalline medium comprising a dye component A) which comprises one or more compounds of the formula I and a liquid-crystalline component B) which comprises one or more mesogenic compounds
in which
W denotes S or Se,
X 11 , X 12 , identically or differently, denote H, alkyl having 1-6 C atoms, in which one or more H atoms may be replaced by F and one or more CH 2 groups may be replaced by —O— or —S— in such a way that no O or S atoms are adjacent, perfluoroalkyl having 1-6 C atoms, halogen, CN, SF 5 , an aryl or heteroaryl group, which may be substituted by one or more radicals L, and alternatively the groups X 11 and X 12 together also denote a straight-chain or branched alkylene group having 2 to 10 C atoms, in which one, several or all H atoms may be replaced by F,
R 11 , R 12 , identically or differently, denote F, straight-chain or branched alkyl having 1 to 25 C atoms, in which, in addition, one or more non-adjacent CH 2 groups may each be replaced, independently of one another, by —C(R z )═C(R z )—, —C≡C—, —N(R z )—, —O—, —S—, —C(O)—, —C(O)—O—, —O—C(O)— or —O—C(O)—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, Br, I or CN,
R z on each occurrence, identically or differently, denotes H, halogen, straight-chain, branched or cyclic alkyl having 1 to 25 C atoms, in which, in addition, one or more non-adjacent CH 2 groups may be replaced by —O—, —S—, —C(O)—, —C(O)—O—, —O—C(O)— or —O—C(O)—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 or Cl,
A 11 , A 12 each, independently of one another, denote an aryl or heteroaryl group, which may be substituted by one or more radicals L,
A 21 , A 22 are each, independently of one another, defined like A 11 or denote a cyclic alkyl group having 3 to 10 C atoms, in which 1 to 4 CH 2 groups may be replaced by O in such a way that no two O atoms are adjacent,
L on each occurrence, identically or differently, denotes OH, CH 2 OH, F, Cl, I, —CN, —NO 2 , SF 5 , —NCO, —NCS, —OCN, —SCN, —C(═O)N(R z ) 2 , —C(═O)R z , —N(R z ) 2 , optionally substituted silyl, optionally substituted aryl having 6 to 20 C atoms, or straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, in which, in addition, one or more H atoms may be replaced by F or Cl,
Z 11 , Z 12 on each occurrence, identically or differently, denote a single bond, —CR x1 ═CR x2 —, —C≡C— or —C(O)—,
Z 21 , Z 22 are on each occurrence, identically or differently, defined like Z 11 or denote —O—, —S—, —CR y1 R y2 —, —CF 2 O—, —OCF 2 —, —C(O)—O—, —O—C(O)—, —O—C(O)—O—, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 S—, —SCF 2 —, —(CH 2 ) n1 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —(CF 2 ) n1 —, —CH═CH—COO— or —OCO—CH═CH—,
R x1 , R x2 , independently of one another, denote H, F, Cl, CN or alkyl having 1-12 C atoms,
R y1 , R y2 each, independently of one another, denote H or alkyl having 1-12 C atoms,
r, s, independently of one another, denote 0, 1, 2 or 3,
n1 denotes 1, 2, 3 or 4,
with the proviso that the compound of the formula
is excluded.
2. A liquid crystalline medium according to claim 1 , wherein in formula I, if r and s are identical, at least one of the groups
A 11 and A 12 , or
R 11 and R 12 , or
A 21 and A 22 , or
Z 11 and Z 12 , or
Z 21 and Z 22 , or
X 11 and X 12
is different from one another, where the parameters have the meanings indicated in claim 1 .
3. A liquid crystalline medium according to claim 1 , wherein in formula I, r denotes 0, 1 or 2 and s denotes r+1.
4. A liquid crystalline medium according to claim 1 , wherein in formula I, W denotes —S—.
5. A liquid crystalline medium according to claim 1 , wherein in formula I, X 11 and X 12 each, independently of one another, denote H, CH 3 , C 2 H 5 , F, Cl, CF 3 , OCF 3 , CN or together denote 1,4-butylene, 1,3-hexafluoropropylidene or 1,4-octafluorobutylidene.
6. A liquid crystalline medium according to claim 1 , wherein in formula I, A 11 , A 12 , A 21 , A 22 are selected on each occurrence, identically or differently, from groups, optionally substituted by radicals L, derived from the parent substances benzene, fluorene, naphthalene, pyridine, pyrimidine, thiophene, thiazole, dihydrothienodioxin, benzothiophene, dibenzothiophene, benzodithiophene, cyclopentadithiophene, thienothiophene, indenothiophene, furan, benzofuran, dibenzofuran and quinoline, where L is selected from the groups F, Cl, CN, NO 2 , CH 3 , C 2 H 5 , OCH 3 , OC 2 H 5 , COCH 3 , COC 2 H 5 , COOCH 3 , COOC 2 H 5 , CF 3 , OCF 3 , OCHF 2 , OC 2 F 5 and phenyl.
7. A liquid crystalline medium according to claim 1 , wherein the compounds of formula I, are selected from the following sub-formulae:
in which
R 11 , R 12 , independently of one another, denote F, a straight-chain alkyl or alkoxy group having 1 to 15 C atoms or a branched alkyl or alkoxy group having 3 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F,
A 11 , A 12 ,
A 21 , A 22 each, independently of one another, denote 1,4-phenylene, 2,6-naphthylene, thiophene-2,5-diyl or thiazole-2,5-diyl,
Z 21 , Z 22 , independently of one another, denote —CH 2 CH 2 —, —CF 2 CF 2 —, —CH═CH—, —CF═CF—, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O— or a single bond,
L on each occurrence, identically or differently, denotes OH, CH 2 OH, F, Cl, I, —CN, —NO 2 , SF 5 , —NCO, —NCS, —OCN, —SCN, —C(═O)N(R z ) 2 , —C(═O)R z , —N(R z ) 2 , optionally substituted silyl, optionally substituted aryl having 6 to 20 C atoms, or straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, in which, in addition, one or more H atoms may be replaced by F or Cl,
a, independently of one another, denotes 0, 1, 2, 3 or 4,
b, independently of one another, denotes 0, 1 or 2,
c, independently of one another, denotes 0 or 1, and
d, independently of one another, denotes 1, 2, 3, 4, 5 or 6.
8. A liquid crystalline medium according to claim 1 , wherein in formula I, Z 21 and Z 22 denote a single bond.
9. A method which comprises including a liquid crystalline medium according to claim 1 in electro-optical displays, devices for regulating the passage of energy from an outside space into an inside space, electrical semiconductors, organic field-effect transistors (OFETs), printed circuits, radio frequency identification elements (RFIDs), organic light-emitting diodes (OLEDs), lighting elements, photovoltaic devices, optical sensors, effect pigments, decorative elements or as dye for colouring polymers.
10. A process wherein compounds of the formula III are converted into compounds of the formula I according to claim 1 ,
in which W, R 11 , R 12 , A 11 , A 12 , A 21 , A 22 , Z 11 , Z 12 , Z 21 , Z 22 , r and s have the meanings indicated for formula I in claim 1 .
11. A process for the preparation of the LC media according to claim 1 , wherein two or more mesogenic compounds are mixed with one another, and one or more dyes of the formula I are added in a further process step.
12. A device for regulating the passage of energy from an outside space into an inside space, where the device contains a switching layer comprising an LC medium according to claim 1 .
13. A window containing a device according to claim 12 .