| 摘要 |
#CMT# #/CMT# Chromane derivatives (A) and chromene derivatives (A1) are new. #CMT# : #/CMT# Chromane derivatives (A) of formulae (I and II) and chromene derivatives (A1) of formulae (III-VI) are new. R 1>a linear or branched 1-15C alkyl, 2-15C alkenyl (both optionally chiral, unsubstituted, substituted with CN, CF 3 or halo, where one or more CH 2-groups are replaced through -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF-, -C?=C- or -cyclicbutane-), H or halo (F, Cl, Br or I); R 2>alkyl- or alkoxy with 1-15C atoms, alkenyl- or alkenyloxy with 2-15C atoms (all optionally substituted with F), H, F, Cl, NCS, CN or SF 5; A 1>, A 2>trans-1,4-cyclohexylene (where one or more non-adjacent CH 2-groups are replaced by -O- and/or -S-), 1,4-phenylene (where one or two CH-groups are replaced by N and one or more H atoms by F), 1,4-bicyclo(2,2,2)-octylene, piperidin-1,4-diyl, naphthalin-2,6-diyl, decahydronaphthalin-2,6-diyl, 1,2,3,4-tetrahydronaphthalin-2,6-diyl or 1,4-cyclohexenylene; Z 1>, Z 2>-O-, -CH 2O-, -OCH 2-, -CO-O-, -O-CO-, -CF 2O-, -OCF 2-, -CF 2CF 2-, -CH 2CF 2-, -CF 2CH 2-, -CH 2CF 2O-, -OCF 2CH 2-, -CH 2CH 2-, -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF-, -CF=CF-CO-O-, -O-CO-CF=CF-, -C?=C- or a bond; L 1>-L 4>alkyl- or alkoxy with 1-15C, alkenyl- or alkenyloxy with 2-15C atoms (all optionally substituted with one or more F), H, F, Cl, NCS, CN, SF 5 (preferably H or F); m : 0-4 (preferably 0-2); and n : 1-4 (preferably 1-2). Provided that the sum of m and n is 1-4 (preferably 1-2). In formula (II): L 2>L 3>oxy-compounds of formula (a-f); and L 5>, L 6>H, F, Cl, CN or -(Z 2>-A 2>-) nR 2>. Provided that when L 5> and L 6> is H, F, Cl or CN, then m is 1-4 (preferably 1-2); and when L 5> and L 6> is -(Z 2>-A 2>-) nR 2>, then m and n is 0-4 and the sum of m and n is 1-4 (preferably 1-3). Independent claims are also included for: (1) liquid crystalline medium comprising at least two liquid crystalline components of (I-VI); (2) liquid crystal display element comprising liquid crystalline medium; and (3) electrooptical display element comprising liquid crystalline medium as dielectric. #CMT#[Image]#/CMT# #CMT#[Image]#/CMT# #CMT#[Image]#/CMT# #CMT#[Image]#/CMT# #CMT#USE : #/CMT# (A) are useful as components in liquid crystalline media and useful in liquid crystal display element or electrooptical display element (claimed). #CMT#ADVANTAGE : #/CMT# (A) exhibits high dielectric anisotropy and are thermally, chemically and photo chemically stable. (A) exhibits broad nematic phase and also outstanding with nematic based mixtures, preferably at low temperatures. The solubility of (A) is favourable, due to it is suitable for the increase of the very low-temperature stability of polar liquid crystal mixtures. #CMT#ORGANIC CHEMISTRY : #/CMT# Preparation: Preparation of (A) comprises ring end metathesis of substituted diene compound of formula (3) to chromene compound (III) (where L 3> is H), which is transferred by catalytic hydration to chromane compound (Ib). Preferred Components: (II) is a compound (T) with a ring in the mesogen groups of formula (R 1>(-A 1>-Z 1>) m-). (T) is of partial formulae (R 1>-A 2>-) (a), (R 1>-A 2>-Z 2>-), (R 1>-A 1>-A 2>-) (c), (R 1>-A 1>-A 2>-Z 2>-) (d), (R 1>-A 1>-Z 1>-A 2>-) (e), (R 1>-A 1>-Z 1>-A 2>-Z 2>-), (R 1>-A 1>-A 1>-A 2>-), (R 1>-A 1>-Z 1>A 1>-A 2>-), (R 1>-A 1>-A 1>-Z 1>-A 2>-), (R 1>-A 1>-A 1>-A 2>-Z 2>-), (R 1>-A 1>-Z 1>-A 1>-Z 1>-A 2>-), (R 1>-A 1>-Z 1>-A 1>-A 2>-Z 2>-), (R 1>-A 1>-A 1>-Z 1>-A 2>-Z 2>-) or (R 1>-A 1>-Z 1>-A 1>-Z 1>-A 2>-Z 2>-). In formulae (a, c, d): A 1>, A 2>1,4-cyclohexanyl, 1,4-tetrahydro-pyranyl, 1,4-[1,3]dioxanyl, 1,4-benzenyl, 3-fluoro-1,4-benzenyl or 3,6-difluoro-1,4-benzenyl; and Z 2>CF 2O-. In formula (e): Z 1>CF 2O-; A 1> = 1,4-cyclohexanyl, 1,4-tetrahydro-pyranyl, 1,4-benzenyl, 3-fluoro-1,4-benzenyl or 3,6-difluoro-1,4-benzenyl; and A 2>1,4-cyclohexanyl, 1,4-benzenyl, 3-fluoro-1,4-benzenyl or 3,6-difluoro-1,4-benzenyl. #CMT#[Image]#/CMT# #CMT#DEFINITIONS : #/CMT# Preferred Definitions: In formula (II): L 2>L 3>2,3-dihydro-furan or tetrahydro-furan; L 1>F or CF 3; R 2>, L 2>F or CF 3; and m : 1-3. The mesogen groups are attached at 2nd and 3rd positions of (I-VI). #CMT#EXAMPLE : #/CMT# 3,4-Difluoro-2-hydroxy-5-(4-pentyl-cyclohexyl)-benzaldehyde (3 g) was dissolved in acetone (30 ml) and heated after the addition of potassium carbonate (2.1 g) and allylbromide (2.5 ml) for 3 hours at 60[deg]C. The reaction mixture was worked up to give 2-allyloxy-3,4-difluoro-5-(4-pentyl-cyclohexyl)-benzaldehyde (i). Methyltriphenylphosphoniumbromide (3.66 g) in tetrahydrofuran (THF) (20 ml) and potassium-tert-butanolate (1.15 g) was under ice cooling. After 10 minutes, a solution of (i) in THF (15 ml) was added to the reaction mixture and worked up to give 2-allyloxy-3,4-difluoro-5-(4-pentyl-cyclohexyl)-1-vinyl-benzol (ii). The solution of (ii) (2.68 g) was dissolved under nitrogen in dichloromethane (40 ml) and stirred for 2 hours after the supplement of Grubbs catalysts (63 mg). The resultant mixture was worked up to give 7,8-difluoro-6-(4-pentyl-cyclohexyl)-2H-chromene (iii). A solution of (930 mg) in ethanol at palladium on carbon (5%) at 1 bar and moderate temperature was hydrated and worked up to give 7,8-difluoro-6-(4-trans-pentyl cyclohexyl)-chromane (680 mg; 79%). |
