Liquid crystal compounds

摘要

#CMT# #/CMT# Substituted polyphenyl compounds (I) are new. #CMT# : #/CMT# Substituted polyphenyl compounds of formula (I) are new. B1 : -CF 2O-, -CH 2O-, -CH 2-CH 2-, -CF 2CF 2-, -CH 2CF2-, -CH=CH-, -CF=CF-, -CF=CH-, -O?=C- or -(CO)O-; B2 : -CF 2O-; Z : F, Cl, SCN, NCS, CN, OCN, NCO, CF 3or OCF 3; X1-X4 : F, H (both preferred) or Cl; Y1-Y6 : H, F, Cl or T; L1-L6 : H or T; T : alkyl, alkoxy, alkenyl, alkenyloxy or alkynyl having up to 6C; R : unsubstituted 1-15C alkyl (in which one or more CH 2groups are replaced by -C?=C-, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -(CO)O-, -O(CO)-, -(CO)- or -O-, where the O-atoms are not directly linked to each other), F, Cl, Br, CN, CF 3, SCN, NCS or SF 5; m : 2-4; and n, o : 0-2, where the sum of m+n+o is 3 or 4. Independent claims are included for: (1) a liquid crystal medium comprising (I); (2) preparing the liquid crystal medium comprising mixing (I) with one or more substituted polyphenyl compounds of formula (II) and optionally with one or more further compounds and one or more additives; (3) a component for high frequency technique; and (4) a phase controlled antenna array. L11 : R11 or X11; L2 : R12 or X12; R11, R12 : non-fluorinated 1-17C (preferably 3-10C) alkyl or alkoxy, or 2-5C (preferably 3-10C) non-fluorinated alkenyl, alkenyloxy or alkoxyalkyl; X11, X12 : F, Cl, Br, -ON, -NCS, -SCN, -SF 5, fluorinated 1-7C alkyl or alkoxy, or 2-7C fluorinated alkenyloxy or alkoxyalkyl; Z11-Z13 : trans- -CH=CH-, trans- -CF=CF-, -C?=C- or single bond; rings A11-A14 : (a) 1,4-phenylene (where one or more, preferably one or two, CH-groups are replaced by N), (b) trans-1,4-cyclohexylene or cyclohexenylene (where one or two non-adjacent CH 2groups are replaced by -O- and/or -S- and H is replaced by F) or (c) 1,4-naphthylene, where in groups (a) and (b), one or more H atoms are replaced by Br, Cl, F, CN, -NCS, -SCN, SF 5, 1-10C alkyl, 3-6C cycloalkyl, 1-10C alkoxy or once or multiple times fluorinated 1-10C alkyl or alkoxy groups; and p : 0-1. #CMT#[Image]#/CMT# #CMT#[Image]#/CMT# #CMT#USE : #/CMT# (I) are useful in: a liquid crystalline medium; and a component for high frequency technique, where the component is one or more functionally connected phase shifter. The component is useful in a phase controlled antenna array (all claimed). #CMT#ADVANTAGE : #/CMT# (I): exhibit improved properties i.e. the loss in the microwave range is reduced and the material quality (eta ) is improved; improves the low temperature behavior of the components and storage capacity; and have relatively high clearing point, high dielectric anisotropy, high optical anisotropy and convenient, high rotational viscosity have about the longitudinal axis of the molecule. #CMT#ORGANIC CHEMISTRY : #/CMT# Preparation (Disclosed): Preparation of (I) comprises Suzuki coupling of corresponding substituted aryl halide compounds of formula (III) and boric acid derivatives of formula (IV) to give (I) (where X1-X4 is X and B2 is -CF 2O). Either R1 : 1-6C alkyl; or R1+R1 : optionally alkylated alkylene; and X : not defined. Preferred Composition: The liquid crystal medium comprises additionally one or more of (II), and comprises 5-95% of (I). #CMT#[Image]#/CMT# #CMT#DEFINITIONS : #/CMT# Preferred Definitions: B1 : -CF 2O-; m : 2; and n, o : 1. When n is 1, m is 2 and o is 0, then at least one of Y1-Y6 or L1-L6 is T. #CMT#SPECIFIC COMPOUNDS : #/CMT# 2 Compounds (I) are disclosed i.e. 4-((4'-((3,5-difluoro-4'-pentylbiphenyl-4-yl)difluoromethoxy)-2',3,5-trifluorobiphenyl-4-yl)difluoromethoxy)-2,3',4',5'-tetrafluorobiphenyl-4-((4'-((3,5-difluoro-4'-pentylbiphenyl-4-yl)difluoromethoxy)-2',3,5-trifluorobiphenyl-4-yl)difluoromethoxy)-2,3',4',5'-tetrafluorobiphenyl of formula (Ia) and 4-((4'-(difluoro(2,3',4',5'-tetrafluorobiphenyl-4-yloxy)methyl)-2,3',5'-trifluoro-2'-propylbiphenyl-4-yloxy)difluoromethyl)-3,5-difluoro-4'-pentylbiphenyl. #CMT#[Image]#/CMT# #CMT#EXAMPLE : #/CMT# 4'-[(4-Bromo-2,6-difluoro-phenyl)-difluoro-methoxy]-3,4,5,2'-tetrafluoro-biphenyl (75 g) was dissolved in dioxane (580 ml) and bis-(pinacolato)-diboron (49 g) was added. Subsequently, potassium acetate (43 g) and [1,1-bis(diphenylphosphino)ferrocene] dichloropalladium(II) (3.4 g) were added and the reaction mixture was heated at 100[deg] C for 6 hours. 2-Mercaptobenzothiazole (1000 ml) and water (300 ml) were added at room temperature and the reaction mixture was further worked up to give 2-{4-[difluoro-(2,3',4',5'-tetrafluoro-biphenyl-4-yloxy)-methyl]-3,5-difluoro-phenyl}-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (E1). Sodium metaborate-octahydrate (6 g) was added into water (15 ml) and mixed with tetrahydrofuran (THF, 30 ml), bis(triphenylphosphine)-palladium(II)-chloride (286 mg) and hydrazinium hydroxide (0.05 ml) and stirred for 5 minutes at room temperature. Subsequently, 4-[(4-bromo-3-fluoro-phenoxy)-difluoro-methyl]-3,5-difluoro-4'-pentyl-biphenyl (10 g) and (E1) (10.6 g) dissolved in THF (70 ml) were added. The reaction mixture was heated under reflux for 8 hours. The reaction mixture was further worked up to give 4-((4'-((3,5-difluoro-4'-pentylbiphenyl-4-yl)difluoromethoxy)-2',3,5-trifluorobiphenyl-4-yl)difluoromethoxy)-2,3',4',5'-tetrafluorobiphenyl-4-((4'-((3,5-difluoro-4'-pentylbiphenyl-4-yl)difluoromethoxy)-2',3,5-trifluorobiphenyl-4-yl)difluoromethoxy)-2,3',4',5'-tetrafluorobiphenyl.