CN111094513A - Dibenzofurane and dibenzothiophene derivatives - Google Patents

Dibenzofurane and dibenzothiophene derivatives Download PDF

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CN111094513A
CN111094513A CN201880059451.9A CN201880059451A CN111094513A CN 111094513 A CN111094513 A CN 111094513A CN 201880059451 A CN201880059451 A CN 201880059451A CN 111094513 A CN111094513 A CN 111094513A
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diyl
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CN111094513B (en
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D·乌斯哈科夫
H·哈斯
M·恩格尔
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
    • C09K2019/3408—Five-membered ring with oxygen(s) in fused, bridged or spiro ring systems

Abstract

The invention relates to derivatives of dibenzofurans and dibenzothiophenes of general formula (I), in which the radicals and parameters that appear have the meanings indicated in the claims, to their use in liquid-crystalline or mesogenic media, to liquid-crystalline or mesogenic media comprising these derivatives, and to electro-optical display elements comprising these liquid-crystalline or mesogenic media.

Description

Dibenzofurane and dibenzothiophene derivatives
The present invention relates to derivatives of dibenzofuran and dibenzothiophene, their use in liquid-crystalline or mesogenic media, liquid-crystalline or mesogenic media comprising these derivatives, and electro-optical display elements comprising these liquid-crystalline or mesogenic media.
Liquid crystals have been widely used since the first commercially available liquid crystal compounds were discovered about 30 years ago. Known fields of application are, in particular, displays for watches and pocket calculators, and large display panels for railway stations, airports and sports grounds. Other areas of application are displays for portable computers and navigation systems and video applications. Especially for the last-mentioned applications, high demands are made on the response time and the contrast of the image.
The spatial arrangement of molecules in a liquid crystal has many property-direction dependent effects. Of particular importance for use in liquid crystal displays are optical, dielectric and elasto-mechanical anisotropy. Depending on whether the molecules are perpendicular or parallel to their long axis to the two plates of the capacitor, the latter having different capacitances; in other words, the dielectric constant ε of the liquid-crystalline medium has different values in the two directions. The dielectric constant when the long axes of the molecules are oriented perpendicular to the capacitor plates is greater than when they are oriented parallel is called dielectrically positive. Most liquid crystals used in conventional displays fall into this category.
Both the polarizability of the molecules and the permanent dipole moment contribute to the dielectric anisotropy. When a voltage is applied to the display, the long axes of the molecules orient themselves in a manner that is effective for the larger dielectric constant. The strength of the interaction with the electric field depends on the difference between the two constants. A case with a small difference requires a higher switching voltage than a case with a large difference. By introducing suitable polar groups, such as nitrile groups or fluorine, into the liquid crystal molecules, a wide range of operating voltages can be achieved.
In the case where liquid crystal molecules are used in a conventional liquid crystal display, the dipole moment oriented along the long axes of the molecules is larger than the dipole moment oriented perpendicular to the long axes of the molecules. The orientation of the large dipole moment along the long axis of the molecules also determines the orientation of the molecules in the liquid crystal display in the field-free state. In the most widely used TN ("twisted nematic") liquid crystal cells, a liquid crystal layer having a thickness of only 5 to 10 μm is arranged between two flat glasses, each of which is vapor-deposited with a conductive, transparent tin oxide or indium tin oxide layer as an electrode. A likewise transparent alignment layer, usually consisting of plastic (e.g. polyimide), is located between these films and the liquid crystal layer. The alignment layer serves to bring the long axes of adjacent crystal molecules into a preferential direction by surface forces so that they are uniformly located inside the display surface in a flat manner with the same alignment or with the same small tilt angle in the voltage-free state. Two polarizing films that allow only linearly polarized light to enter and escape are adhesively bonded to the exterior of the display in some arrangement.
Very high performance displays have been developed by liquid crystals with large dipole moments aligned parallel to the long axes of the molecules. Here, in most cases, mixtures of 5 to 20 components are used in order to achieve a sufficiently wide temperature range and short response times of the mesophase and low threshold voltages. However, difficulties are still caused by the strong viewing angle dependence in liquid crystal displays used, for example, in portable computers. The best imaging quality can be achieved if the surface of the display is perpendicular to the viewing direction of the observer. If the display is tilted with respect to the viewing direction, the imaging quality may in some cases be drastically reduced. For greater comfort, attempts are made to make the angle at which the display can be tilted from the viewing direction of the observer as large as possible. Recently, attempts have been made to improve the viewing angle dependence using a liquid crystal compound having a dipole moment perpendicular to the long axis of the molecule larger than a dipole moment parallel to the long axis of the molecule. In the field-free state, these molecules are oriented perpendicular to the glass surface of the display. In this way, improvement in viewing angle dependence can be achieved. This type of display is known as a VA-TFT ("vertical orientation") display.
Also known are so-called IPS ("in-plane switching") displays, which comprise an LC layer between two substrates having an in-plane orientation, wherein two electrodes are arranged on only one of the two substrates, and preferably have an interleaved comb-like structure. Upon application of a voltage to the electrodes, an electric field having a significant component parallel to the LC layer is generated between the electrodes. This results in the LC molecules realigning in the plane of the layer. Furthermore, so-called FFS ("fringe field switching") displays have been reported (see, inter alia, s.h. jung et al, jpn.j.appl.phys., Volume 43, No.3,2004,1028) which comprise two electrodes on the same substrate, one of which is structured in a comb-like manner and the other of which is not structured. This produces a strong so-called "fringe field", i.e. a strong electric field close to the edges of the electrodes, and in the entire liquid crystal cell, an electric field having both a strong vertical and a strong horizontal component. FFS displays have a low viewing angle dependence of the contrast. FFS displays usually comprise an LC medium with a positive dielectric anisotropy and an alignment layer, usually of polyimide, which provides a planar alignment of the molecules of the LC medium.
Another type of FFS display has been disclosed which has a similar electrode design and layer thickness as FFS displays, but comprises a layer of LC medium with negative dielectric anisotropy instead of a layer of LC medium with positive dielectric anisotropy (see Leeet al, appl. phys. lett.73(20),1998, 2882-.
The following compounds having negative dielectric anisotropy are described in JP (A) H10-236992:
Figure BDA0002409873230000031
compounds such as the following are described in CN 106699710:
Figure BDA0002409873230000032
Figure BDA0002409873230000041
the development in the field of liquid crystal materials has not been completed. In order to improve the performance of liquid crystal display elements, attempts have been made to develop new compounds capable of optimizing such displays.
It is an object of the present invention to provide compounds for liquid-crystalline media which have advantageous properties.
According to the invention, this object is achieved by the compounds of the general formula (I).
Figure BDA0002409873230000042
Wherein
W represents O or S, and W represents O or S,
L1represents R1Or X1,
L2Represents R2Or X2,
R1,R2Independently of one another, each represents H, an alkyl or alkoxy radical having 1 to 15 carbon atoms, where, in addition, one or more CH groups in these radicals2The radicals may each, independently of one another, be substituted by-C.ident.C-, -CH-,
Figure BDA0002409873230000043
Figure BDA0002409873230000044
-O-,-S-,-CF2O-,-OCF2-, -CO-O-or-O-CO-is replaced in such a way that O-or S-are not directly linked to one another, and wherein, in addition, one or more H atoms may be replaced by CN or halogenThe substitution of the element(s) is carried out,
X1and X2Independently of one another, represents haloalkyl, haloalkoxy, haloalkenyl or haloalkenyloxy, each having up to 5C atoms, F, Cl, CN, SCN, SF5Preferably F, CH2F，CF2H，CF3，OCF2H，OCF3，-OCH＝CF2or-OCF ═ CF2Particularly preferred are F, CF3Or OCF3,
A1And A2Each independently of the others represents a group selected from:
a) trans-1, 4-cyclohexylene, 1, 4-cyclohexenylene, and decahydronaphthalene-2, 6-diyl, wherein one or more non-adjacent CH' s2The radicals may be replaced by-O-and/or-S-and one or more H atoms may be replaced by F,
b) from the group consisting of 1, 4-phenylene and 2, 6-naphthylene, in which one or two CH groups may be replaced by N and in which, in addition, one or more H atoms may be replaced by L,
c) from the group consisting of cyclopentane-1, 3-diyl, cyclopentane-2-ene-1, 3-diyl, 1, 3-dioxane-2, 5-diyl, tetrahydrofuran-2, 5-diyl, cyclobutane-1, 3-diyl, thiophene-2, 5-diyl, selenophene-2, 5-diyl and 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, each of which may be mono-or polysubstituted by L,
d) from the group consisting of bicyclo [1.1.1] pentane-1, 3-diyl, bicyclo [2.2.2] octane-1, 4-diyl and spiro [3.3] heptane-2, 6-diyl, in which one or more H atoms may be replaced by F,
l each, identically or differently, denotes halogen, cyano, alkyl having 1 to 7C atoms, alkoxy, alkylcarbonyl, alkoxycarbonyl, where one or more H atoms may be substituted by F or Cl,
Z1and Z2Independently of one another, represents a single bond, -CF2O-，-OCF2-，-CH2CH2-，-CF2CF2-，-C(O)O-，-OC(O)-，-CH2O-，-OCH2-, -CF ═ CH-, -CH ═ CF-, -CF ═ CF-, -CH ═ CH-or-C ≡ C-, preferably-CH ≡ C-2O-，-OCH2-，-CH2CH2-or a single bond, particularly preferably a single bond.
Y1,Y2,Y3And Y4Independently of one another, H, F, Cl, CN, CF3Or OCF3Preferably, the molar ratio of H or F,
m and n are each independently of the other 0,1 or 2, and m + n is 0,1 or 2,
provided that Y is1,Y2,Y3And Y4Is different from F and Y1,Y2,Y3And Y4Is different from H.
It is a further object of the present invention to provide liquid-crystalline media, in particular for VA, IPS or FFS displays.
According to the invention, this object is achieved by providing compounds of the formula I.
In formula I, W preferably represents O.
In another preferred embodiment, W in formula I represents S.
In a preferred embodiment, in formula I or its subformulae, Y1,Y2,Y3And Y4Represents H.
In a particularly preferred embodiment, in formula I or its subformulae, Y1Represents H, Y2,Y3And Y4Both represent F.
In another particularly preferred embodiment, in formula I or its subformulae, Y2Represents H, and Y1,Y3And Y4Both represent F.
In another particularly preferred embodiment, in formula I or its subformulae, Y3Represents H, and Y1,Y2And Y4Both represent F.
In another particularly preferred embodiment, in formula I or its subformulae, Y4Represents H, and Y1,Y2And Y3Both represent F.
In a preferred embodiment, in formula I or its subformulae, Y1,Y2,Y3And Y4Two of them represent H.
In a particularly preferred embodiment, in formula I or its subformulae, Y1And Y2All represent H and Y3And Y4Both represent F.
In a particularly preferred embodiment, in formula I or its subformulae, Y1And Y2Are all F and Y3And Y4All represent H.
In a particularly preferred embodiment, in formula I or its subformulae, Y1And Y4Are all F and Y2And Y3All represent H.
In a particularly preferred embodiment, in formula I or its subformulae, Y1And Y4All represent H and Y2And Y3Both represent F.
The compound of formula I is preferably selected from the group consisting of formula IA, IB, IC and ID
Figure BDA0002409873230000061
Figure BDA0002409873230000071
Wherein R is1,R2,A1,Z1,X2,Y1,Y2,Y3And Y4Have the meanings and preferences given above for the formula I
R1,R2Each independently of the others, represents a straight-chain alkyl, alkenyl or alkoxy radical having up to 7C atoms or cyclopropyl, cyclobutyl, cyclopentyl or cyclopent-1-enyl radical,
X2each independently of the other, represents F, CF3Or OCF3,
A1Represents a group selected from:
Figure BDA0002409873230000072
Z1represents-CH2O-,-OCH2-,-CH2CH2-or a single bond, particularly preferably-CH2O-or a single bond,
m is 0 or 1.
In a first preferred embodiment, the compound of formula I is selected from formula IA and IC.
In a second preferred embodiment, the compound of formula I is selected from formulae IB and ID.
Preferred compounds of formula IA are selected from the following sub-formulae IA-1 to IA-10:
Figure BDA0002409873230000081
Figure BDA0002409873230000091
wherein the content of the first and second substances,
R1,R2and Z1Have the meaning indicated above for formula IA.
Particularly preferred compounds of formulae IA-1 to IA-10 are compounds of formulae IA-1 and IA-3.
Preferred compounds of formula IA-1 are compounds of the formula:
Figure BDA0002409873230000092
Figure BDA0002409873230000101
wherein
R1And R2Have the meaning indicated above for formula IA.
Preferred compounds of formula IA-2 are compounds of the formula:
Figure BDA0002409873230000102
Figure BDA0002409873230000111
wherein the content of the first and second substances,
R1,R2and Z1Have the meaning indicated above for formula IA.
Preferred compounds of formula IA-3 are compounds of the formula:
Figure BDA0002409873230000112
Figure BDA0002409873230000121
wherein the content of the first and second substances,
R1,R2and Z1Has the meaning indicated above for formula IA and Z1Preferably represents-CH2O-。
Preferred compounds of formula IA-4 are compounds of the formula:
Figure BDA0002409873230000122
Figure BDA0002409873230000131
wherein the content of the first and second substances,
R1,R2and Z1Have the meaning indicated above for formula IA.
Preferred compounds of formula IA-5 are compounds of the formula:
Figure BDA0002409873230000141
wherein the content of the first and second substances,
R1,R2and Z1Have the meaning indicated above for formula IA.
Preferred compounds of formula IA-6 are compounds of the formula:
Figure BDA0002409873230000151
Figure BDA0002409873230000161
wherein the content of the first and second substances,
R1,R2and Z1Have the meaning indicated above for formula IA.
Preferred compounds of formula IA-7 are compounds of the formula:
Figure BDA0002409873230000162
Figure BDA0002409873230000171
wherein the content of the first and second substances,
R1,R2and Z1Have the meaning indicated above for formula IA.
Preferred compounds of formula IA-8 are compounds of the formula:
Figure BDA0002409873230000172
Figure BDA0002409873230000181
wherein the content of the first and second substances,
R1,R2and Z1Have the meaning indicated above for formula IA.
Preferred compounds of formula IA-9 are of the formula:
Figure BDA0002409873230000182
Figure BDA0002409873230000191
wherein the content of the first and second substances,
R1,R2and Z1Have the meaning indicated above for formula IA.
Preferred compounds of formula IA-10 are of the formula:
Figure BDA0002409873230000192
Figure BDA0002409873230000201
wherein the content of the first and second substances,
R1,R2and Z1Have the meaning indicated above for formula IA.
Preferred compounds of formula IB-1 are selected from the following sub-formulae IB-1 to IB-12
Figure BDA0002409873230000202
Figure BDA0002409873230000211
Figure BDA0002409873230000221
Wherein the content of the first and second substances,
R1,X2and Z1Have the meanings indicated above for formula IB.
Particularly preferred compounds of formulae IB-1 to IB-10 are compounds of formula IB-1.
Preferred compounds of formula IB-1 are compounds of the formula:
Figure BDA0002409873230000222
Figure BDA0002409873230000231
wherein the content of the first and second substances,
R1and X2Have the meanings indicated above for formula IB.
Preferred compounds of formula IB-2 are compounds of the formula:
Figure BDA0002409873230000232
Figure BDA0002409873230000241
wherein the content of the first and second substances,
R1,X2and Z1Have the meanings indicated above for formula IB.
Preferred compounds of formula IB-3 are compounds of the formula:
Figure BDA0002409873230000242
Figure BDA0002409873230000251
wherein the content of the first and second substances,
R1,X2and Z1Has the meaning indicated above for formula IB and Z1Preferably represents-CH2O-。
Preferred compounds of formula IB-4 are compounds of the formula:
Figure BDA0002409873230000252
Figure BDA0002409873230000261
wherein the content of the first and second substances,
R1,X2and Z1Have the meanings indicated above for formula IB.
Preferred compounds of formula IB-5 are compounds of the formula:
Figure BDA0002409873230000262
Figure BDA0002409873230000271
wherein the content of the first and second substances,
R1,X2and Z1Have the meanings indicated above for formula IB.
Preferred compounds of formula IB-6 are compounds of the formula:
Figure BDA0002409873230000281
wherein the content of the first and second substances,
R1,X2and Z1Have the meanings indicated above for formula IB.
Preferred compounds of formula IB-7 are compounds of the formula:
Figure BDA0002409873230000291
Figure BDA0002409873230000301
wherein the content of the first and second substances,
R1,X2and Z1Have the meanings indicated above for formula IB.
Preferred compounds of formula IB-8 are compounds of the formula:
Figure BDA0002409873230000302
Figure BDA0002409873230000311
wherein the content of the first and second substances,
R1,X2and Z1Have the meanings indicated above for formula IB.
Preferred compounds of formula IB-9 are compounds of the formula:
Figure BDA0002409873230000312
Figure BDA0002409873230000321
wherein the content of the first and second substances,
R1,X2and Z1Have the meanings indicated above for formula IB.
Preferred compounds of formula IB-10 are compounds of the formula:
Figure BDA0002409873230000322
Figure BDA0002409873230000331
wherein the content of the first and second substances,
R1,X2and Z1Have the meanings indicated above for formula IB.
Preferred compounds of formula IC-1 are selected from the following subformulae IC-1 to IC-10:
Figure BDA0002409873230000332
Figure BDA0002409873230000341
Figure BDA0002409873230000351
wherein the content of the first and second substances,
R1,R2and Z1Has the meaning as indicated above for formula IC.
Particularly preferred compounds of formulae IC-1 to IC-12 are compounds of formulae IC-1 and IC-3.
Preferred compounds of formula IC-1 are compounds of the formula:
Figure BDA0002409873230000352
Figure BDA0002409873230000361
wherein the content of the first and second substances,
R1and R2Has the meaning as indicated above for formula IC.
Preferred compounds of formula IC-2 are compounds of the formula:
Figure BDA0002409873230000362
Figure BDA0002409873230000371
wherein the content of the first and second substances,
R1,R2and Z1Has the meaning as indicated above for formula IC.
Preferred compounds of formula IC-3 are compounds of the formula:
Figure BDA0002409873230000372
Figure BDA0002409873230000381
wherein the content of the first and second substances,
R1,R2and Z1Has the meaning as indicated above for formula IC and Z1Preferably represents-CH2O-。
Preferred compounds of formula IC-4 are compounds of the formula:
Figure BDA0002409873230000382
Figure BDA0002409873230000391
wherein the content of the first and second substances,
R1,R2and Z1Has the meaning as indicated above for formula IC.
Preferred compounds of formula IC-5 are compounds of the formula:
Figure BDA0002409873230000392
Figure BDA0002409873230000401
wherein the content of the first and second substances,
R1,R2and Z1Has the meaning as indicated above for formula IC.
Preferred compounds of formula IC-6 are compounds of the formula:
Figure BDA0002409873230000402
Figure BDA0002409873230000411
wherein the content of the first and second substances,
R1,R2and Z1Has the meaning as indicated above for formula IC.
Preferred compounds of formula IC-7 are of the formula:
Figure BDA0002409873230000421
wherein the content of the first and second substances,
R1,R2and Z1Has the meaning as indicated above for formula IC.
Preferred compounds of formula IC-8 are of the formula:
Figure BDA0002409873230000431
Figure BDA0002409873230000441
wherein the content of the first and second substances,
R1,R2and Z1Has the meaning as indicated above for formula IC.
Preferred compounds of formula IC-9 are compounds of the formula:
Figure BDA0002409873230000442
Figure BDA0002409873230000451
wherein the content of the first and second substances,
R1,R2and Z1Has the meaning as indicated above for formula IC.
Preferred compounds of formula IC-10 are compounds of the formula:
Figure BDA0002409873230000452
Figure BDA0002409873230000461
wherein the content of the first and second substances,
R1,R2and Z1Has the meaning as indicated above for formula IC.
Preferred compounds of formula ID-1 are selected from the following subformulae ID-1 to ID-12:
Figure BDA0002409873230000462
Figure BDA0002409873230000471
wherein the content of the first and second substances,
R1,X2and Z1Have the meaning indicated above for formula ID.
Particularly preferred compounds of the formulae ID-1 to ID-10 are compounds of the formula ID-1.
Preferred compounds of formula ID-1 are of the formula:
Figure BDA0002409873230000481
wherein the content of the first and second substances,
R1and X2Have the meaning indicated above for formula ID.
Preferred compounds of formula ID-2 are of the formula:
Figure BDA0002409873230000491
Figure BDA0002409873230000501
wherein the content of the first and second substances,
R1,X2and Z1Have the meaning indicated above for formula ID.
Preferred compounds of formula ID-3 are of the formula:
Figure BDA0002409873230000502
Figure BDA0002409873230000511
wherein the content of the first and second substances,
R1,X2and Z1Has the meaning indicated above for formula ID and Z1Preferably represents-CH2O-。
Preferred compounds of formula ID-4 are of the formula:
Figure BDA0002409873230000512
Figure BDA0002409873230000521
wherein the content of the first and second substances,
R1,X2and Z1Have the meaning indicated above for formula ID.
Preferred compounds of formula ID-5 are of the formula:
Figure BDA0002409873230000522
Figure BDA0002409873230000531
wherein the content of the first and second substances,
R1,X2and Z1Have the meaning indicated above for formula ID.
Preferred compounds of formula ID-6 are of the formula:
Figure BDA0002409873230000532
Figure BDA0002409873230000541
wherein the content of the first and second substances,
R1,X2and Z1Have the meaning indicated above for formula ID.
Preferred compounds of formula ID-7 are of the formula:
Figure BDA0002409873230000542
Figure BDA0002409873230000551
wherein the content of the first and second substances,
R1,X2and Z1Have the meaning indicated above for formula ID.
Preferred compounds of formula ID-8 are of the formula:
Figure BDA0002409873230000561
wherein the content of the first and second substances,
R1,X2and Z1Have the meaning indicated above for formula ID.
Preferred compounds of formula ID-9 are of the formula:
Figure BDA0002409873230000571
Figure BDA0002409873230000581
wherein the content of the first and second substances,
R1,X2and Z1Have the meaning indicated above for formula ID.
Preferred compounds of formula ID-10 are of the formula:
Figure BDA0002409873230000582
Figure BDA0002409873230000591
wherein the content of the first and second substances,
R1,X2and Z1Have the meaning indicated above for formula ID.
The compounds according to the invention of the formulae IA and IC both have a negative △ ε and are therefore particularly suitable for use in VA-TFT displays and IPS-and FFS displays the compounds according to the invention preferably have a △ ε of < -2.5, preferably ≦ 5 and particularly preferably ≦ -8 of △ ε, they have good compatibility with customary substances in liquid-crystalline mixtures for displays.
The compounds of the formulae IB and ID according to the invention are distinguished by a high dielectric ratio (. epsilon.)⊥△ epsilon) and has dielectric properties which are particularly suitable for LC media for IPS or FFS displays.
With respect to the present invention, it is,
Figure BDA0002409873230000592
represents a trans-1, 4-cyclohexylene group,
Figure BDA0002409873230000601
represents a1, 4-phenylene group.
Halogen is F, Cl, Br and I.
If R is1Or R2Is an alkyl and/or alkoxy group, it may be straight or branched. Preferably straight-chain, having 2,3,4, 5,6 or 7 carbon atoms, and thus preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy, furthermore methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octoxy, nonoxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.
R1And R2May each, independently of one another, be an alkenyl radical having from 2 to 15 carbon atoms, which may be linear or branched. It is preferably straight-chain and has 2 to 7 carbon atoms. Thus, it is preferably vinyl, prop-1-yl or 2-enyl, but-1-, -2-or-3-enyl, pent-1-, -2-, -3-or-4-enyl, hex-1-, -2-, -3-, -4-or 5-enyl, or hept-1, -2-, -3-, -4-, -5-or-6-enyl.
R1And R2Can each, independently of one another, be an oxaalkyl radical, preferably a linear 2-oxapropyl (═ methoxymethyl), 2-oxabutyl (═ ethoxymethyl) or 3-oxabutyl (═ methoxyethyl), 2-, 3-or 4-oxapentyl, 2-, 3-, 4-or 5-oxahexyl, or 2-, 3-, 4-or 5-oxahexyl radical-, 3-, 4-, 5-or 6-oxaheptyl.
R1And R2May each, independently of one another, be an alkyl radical having from 1 to 15 carbon atoms, in which one CH is2The groups are replaced by-O-and one by-CO-, where these are preferably adjacent. Thus, it contains an acyloxy group CO-O-or an oxycarbonyl group O-CO-. It is preferably straight-chain and has 2 to 6 carbon atoms.
R1And R2May each, independently of one another, be an alkyl radical having from 1 to 15 carbon atoms, in which one CH is2The radicals being substituted by unsubstituted or substituted-CH ═ CH-, and adjacent CH2The groups are replaced by CO or CO-O or O-CO, where these may be straight-chain or branched. It is preferably straight-chain and has from 4 to 13 carbon atoms.
R1And R2May each, independently of one another, be an alkyl radical having from 1 to 15 carbon atoms or an alkenyl radical having from 2 to 15 carbon atoms, each of which is substituted by-CN or-CF3Monosubstituted, and preferably linear. -CN or-CF3Substitutions may be made at any desired position.
R1And R2May each, independently of one another, be alkyl, in which two or more CH groups2The radicals are replaced by-O-and/or-CO-O, where these may be straight-chain or branched. It is preferably branched and has from 3 to 12 carbon atoms.
R1And R2May each, independently of one another, be an alkyl radical having from 1 to 15 carbon atoms or an alkenyl radical having from 2 to 15 carbon atoms, each of which is at least monosubstituted, preferably monosubstituted, by halogen, where these radicals are preferably straight-chain and the halogen is preferably F or Cl. The resulting radicals not comprising perfluoro-groups, e.g. CF3. In the case of monosubstitution, the fluorine or chlorine substituent may be in any desired position, but is preferably in the ω -position.
R1And R2Can be alkyl or alkoxy having 1 to 15 carbon atoms, preferably 1 to 5, particularly preferably 1 carbon atom, where one or more of these radicals, preferably 1 CH2The radicals may each, independently of one another, be
Figure BDA0002409873230000611
Figure BDA0002409873230000612
And (4) replacing. R1Preferably cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclobutylmethyl, cyclopentylmethyl, cyclopent-1-enyl or cyclopent-1-enylmethyl.
At X1And X2In the case of representing, independently of one another, a haloalkyl, haloalkoxy, haloalkenyl or haloalkenyloxy each having up to 5 carbon atoms, it may be straight-chain or branched, preferably straight-chain. Preferably, halogen is Cl or F, particularly preferably F. Preferably, these groups are perfluorinated, e.g. CF3and-C2F5。
The compounds of the formula I are prepared by processes known per se, as described, for example, in the literature (for example, in standard works, such as Houben-Weyl, Methodendeder organischen Chemie [ Methods of Organic Chemistry ], Georg-Thieme-Verlag, Stuttgart), to be precise under reaction conditions which are known and suitable for the reaction in question. Variants known per se may be used here, but are not mentioned here in greater detail.
If desired, the starting materials can also be formed in situ by not isolating them from the reaction mixture, but immediately converting them further into compounds of the formula I.
Preferred synthetic routes for preparing the compounds of the invention are shown in the following schematic schemes and are further illustrated by the working examples. By selecting suitable starting materials, the synthesis can be adapted to the particular desired compound of the general formula I.
The compounds of formula I are preferably synthesized as shown in schemes 1 to 3. In the schemes, the groups present are as defined above for formula I, and alkyl represents a straight chain alkyl or (alkylcycloalkyl) alkyl group having up to 15C atoms, preferably (alkylcycloalkyl) methyl.
Bromobofluorobenzene derivative 1 can be ortho-metalated, for example with LDA, to give a phenyllithium intermediate which is then usedReaction of the ligand with iodine affords compound 2 (scheme 1). The appropriately substituted phenylboronic acid (3) is then selectively reacted with iodine in 2 in a Suzuki reaction, for example in Pd (PPh)3)2Cl2In the presence of and with NaBO2As a base. Can be in Pd2(dba)3Substitution of the bromine atom in 4 with thiophenol in the presence of Xathphos and KOtBu gave the thioether (5). The latter via Pd (OAc)2/2,6-Me2PhCOOH catalyzes a ring closure reaction to obtain dibenzothiophene 6.
Scheme 1:
Figure BDA0002409873230000621
phenol 7 can be obtained from bromide 4, for example by treatment with palladium-catalysed aqueous potassium hydroxide. These phenols (7, scheme 2) are prepared by treatment with bases, e.g. K in DMPU3PO4Processing to close ring to obtain dibenzofuran. Alternatively, phenol 7 can be treated to dibenzothiophene 6 via the corresponding triflate (TfO, 9) in analogy to the method described in EP3085753 a 1.
Schematic 2:
Figure BDA0002409873230000631
preferred compounds of formula I are prepared according to scheme 3, wherein commercially available 2-bromo-4-fluoro-5-nitro-phenol is first protected, for example by a benzylation reaction, and then reacted with difluorophenylboronic acid in a Suzuki coupling reaction to give nitrobiphenyl 13. The nitro group is reduced and the resulting aniline (14) is converted to phenol (15) by diazotization and nucleophilic hydroxylation reactions according to standard procedures. Alkylation of phenol 15 and subsequent deprotection affords phenol 17, which phenol 17 is converted to compounds of formula I (18, 19) according to the methods shown in schemes 1 and 2.
Scheme 3:
Figure BDA0002409873230000641
another subject of the invention are the compounds of formula II
Figure BDA0002409873230000642
Wherein the radicals and parameters present have the meanings indicated above for the formula I, and
RIIrepresents alkyl having 1 to 5 carbon atoms, preferably methyl, or phenyl in which one or two CH groups may be replaced by N and one or more H atoms may be replaced by halogen or alkyl having 1 to 10 carbon atoms,
and their use as intermediates in the synthesis of compounds of formula I.
The compounds of formula II can be reacted in intramolecular cyclization to compounds of formula I according to M.Tobisu et al, chem.Sci.,2016,7, 2587-.
Another object of the present invention is a process for the preparation of a compound of formula I by treating a compound of formula II with a palladium catalyst in a solvent, preferably at a temperature in the range of 100 ℃ to 150 ℃. The concentration of the catalyst is from 1 to 20 mol%, preferably from 5 to 15%, based on the amount of the compound of the formula II. Preferred catalysts are palladium salts, preferably palladium (II) acetate or palladium (II) chloride, preferably in the presence of a ligand, particularly preferably a carboxylic acid, very particularly preferably 2, 6-dimethylbenzoic acid.
Preferred solvents are benzene, toluene, xylene, mesitylene, and the like.
The reactions described in the above schemes should be considered exemplary only. Corresponding variations of the synthesis can be carried out by the person skilled in the art and other suitable synthetic routes can also be followed to obtain the compounds of formula I.
As already mentioned, the compounds of the formula I can be used in liquid-crystalline media.
The invention therefore also relates to a liquid-crystalline medium comprising two or more liquid-crystalline compounds comprising one or more compounds of the formula I.
The invention also relates to liquid-crystalline media which, in addition to one or more compounds of the formula I according to the invention, comprise from 2 to 40, preferably from 4 to 30, components as further constituents. These media particularly preferably comprise, in addition to one or more compounds according to the invention, from 7 to 25 components. These further components are preferably selected from nematic or nematic (unidirectional or isotropic) substances, in particular from the following: azoxybenzene, benzylideneaniline, biphenyl, terphenyl, phenyl or cyclohexylbenzoate, phenyl or cyclohexyl ester of cyclohexanecarboxylic acid, phenyl or cyclohexyl ester of cyclohexylbenzoic acid, phenyl or cyclohexyl ester of cyclohexylcyclohexanecarboxylic acid, benzoic acid, cyclohexylphenyl ester of cyclohexanecarboxylic acid or cyclohexylcyclohexanecarboxylic acid, phenyl-cyclohexane, cyclohexylbiphenyl, phenylcyclohexyl-cyclohexane, cyclohexyl-cyclohexene, 1, 4-dicyclohexylbenzene, 4', 4' -dicyclohexylbiphenyl, phenyl or cyclohexylpyrimidine, phenyl or cyclohexylpyridine, phenyl-or cyclohexyldioxane, phenyl or cyclohexyl-1, 3-disulfane, 1, 2-diphenylethane, 1, 2-dibutylcyclohexanethane, 1-phenyl-2-cyclohexylethane, 1-cyclohexyl-2- (4-phenyl-cyclohexyl) ethane, 1-cyclohexyl-2-diphenylethane, 1-phenyl-2-cyclohexylphenylethane, optionally halogenated diphenylethylene, benzylphenyl ether, toluene sulfonic acid and substituted cinnamic acid. The 1, 4-phenylene groups in these compounds may also be fluorinated.
The most important compounds which are suitable for the other constituents of the media according to the invention can be characterized by the formulae (1), (2), (3), (4) and (5):
R'-L-E-R” (1)
R'-L-COO-E-R” (2)
R'-L-OOC-E-R” (3)
R'-L-CH2CH2-E-R” (4)
R'-L-CF2O-E-R” (5)
in the formulae (1), (2), (3), (4) and (5), L and E are identical or different and each, independently of one another, denote a divalent radical from the group consisting of-Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe-and-G-Cyc-, and mirror images thereof, where Phe is unsubstituted or fluorine-substituted 1, 4-phenylene, Cyc is trans-1, 4-cyclohexylene or 1, 4-cyclohexenylene, Pyr is pyrimidine-2, 5-diyl or pyridine-2, 5-diyl, Dio is 1, 3-dioxane-2, 5-diyl, and G is 2- (trans-1, 4-cyclohexyl) ethyl.
One of the radicals L and E is preferably Cyc or Phe. E is preferably Cyc, Phe or Phe-Cyc. The media according to the invention preferably comprise one or more components selected from the group of compounds of the formulae (1), (2), (3), (4) and (5), wherein L and E are selected from Cyc and Phe and at the same time one or more components selected from the compounds of the formulae (1), (2), (3), (4) and (5), wherein one of the radicals L and E is selected from Cyc and Phe and the other radical is selected from-Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -G-Phe-and-G-Cyc-, and optionally one or more components selected from the group consisting of compounds of formulae (1), (2), (3), (4) and (5), wherein the radicals L and E are selected from the group consisting of-Phe-Cyc-, -Cyc-Cyc-, -G-Phe-and-G-Cyc-.
In a smaller subgroup of the compounds of formulae (1), (2), (3), (4) and (5), R 'and R' are each, independently of one another, alkyl, alkenyl, alkoxy, alkoxyalkyl, alkenyloxy or alkanoyloxy having up to 8 carbon atoms. This smaller subgroup is hereinafter referred to as group a, and these compounds are represented by sub-formulae (1a), (2a), (3a), (4a) and (5a), respectively. In most of these compounds, R 'and R' are different from each other, and one of these groups is usually alkyl, alkenyl, alkoxy or alkoxyalkyl.
In a further smaller subgroup of the compounds of the formulae (1), (2), (3), (4) and (5), designated as group B, E is
Figure BDA0002409873230000671
In the group B compounds represented by sub-formulae (1B), (2B), (3B), (4B) and (5B), R' and R "are as defined for sub-formulae (1a) to (5a) and are preferably alkyl, alkenyl, alkoxy or alkoxyalkyl.
In a further smaller subgroup of formulae (1b), (2b), (3b), (4b) and (5b), R' is-CN. This subgroup is referred to below as group C and the compounds of this subgroup are described correspondingly as sub-formulae (1C), (2C), (3C), (4C) and (5C). In the compounds of the sub-formulae (1c), (2c), (3c), (4c) and (5c), R' is as defined for the sub-formulae (1a) to (5a) and is preferably alkyl, alkenyl, alkoxy or alkoxyalkyl.
In addition to the preferred compounds of groups A, B and C, further compounds of the formulae (1), (2), (3), (4) and (5) having further variants of the proposed substituents are also customary. All these substances can be obtained by methods known in the literature or by analogous methods.
In addition to the compounds of the general formula I according to the invention, the media according to the invention preferably also comprise one or more compounds selected from the groups A, B and/or C. In the medium according to the invention, the proportions by weight of the compounds from these groups are:
group A: 0 to 90%, preferably 20 to 90%, in particular 30 to 90%
Group B: 0 to 80%, preferably 10 to 80%, in particular 10 to 70%
Group C: from 0 to 80%, preferably from 5 to 80%, in particular from 5 to 50%.
The media according to the invention preferably comprise from 1 to 40%, particularly preferably from 5 to 30%, of the compounds of the formula I according to the invention. Preference is furthermore given to media which comprise more than 40%, in particular from 45 to 90%, of the compounds of the formula I according to the invention. The medium preferably comprises three, four or five compounds of the formula I according to the invention.
Examples of compounds of formulae (1), (2), (3), (4) and (5) are the following compounds:
Figure BDA0002409873230000672
Figure BDA0002409873230000681
Figure BDA0002409873230000691
Figure BDA0002409873230000701
wherein R is1And R2Independently of one another are-CnH2n+1or-OCnH2n+1And n is 1 to 8, and L1And L2Independently of one another are-H and-F,
Figure BDA0002409873230000702
Figure BDA0002409873230000711
wherein m and n are independently of each other 1 to 8.
The media of the invention are prepared in a manner conventional per se. In general, the components dissolve in one another, advantageously at elevated temperature. By means of suitable additives, the liquid-crystalline phases of the present invention can be varied in such a way that they can be used in all types of liquid-crystal display elements disclosed hitherto. Additives of this type are known to the person skilled in the art and are described in detail in the literature (H.Kelker/R.Hatz, Handbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980). For example, pleochroic dyes can be used to prepare colored guest-host systems, or substances can be added to alter the dielectric anisotropy, viscosity and/or alignment of the nematic phase.
The invention also relates to an electro-optical liquid-crystal display element comprising a liquid-crystalline medium according to the invention.
The present invention is explained in more detail below with reference to working examples, but the present invention is not limited thereto.
In this context, △ n denotes the optical anisotropy (589nm, 20 ℃ C.) and △ ε the dielectric anisotropy (1kHz, 20 ℃ C.).
The values Δ ε and Δ n of the compounds according to the invention were obtained by extrapolation of a liquid-crystal mixture consisting of 10% of the corresponding compound according to the invention and 90% of the commercially available liquid-crystal mixture ZLI-2857 (for Δ ε) or ZLI-4792 (for Δ n) (Merck KGaA, Darmstadt). In case of limited solubility, the compound should be measured in a mixture containing only 5% of the compound, which can be expressed by adding (5%) after the problematic value.
Solubility was measured by quantitative HPTLC using HPTLC silica RP 18F 254 plates (commercial number 1.16225, 10x20cm, Merck KGaA, Darmstadt, Germany) and methanol/2-methyltetrahydrofuran 80/20(v/v) as eluents. The migration distance was 5cm and the peak was detected by UV radiation at a wavelength of 254nm using a TLC scanner (CamagChemie-Erzeugnisse und Dsorptostechnik AG & Co.GmbH). Quantitative measurements were made by integrating the peak intensities and comparing to a calibration curve.
For the calibration curve, a starting solution of about 6mg of sample in 20ml of 2-methyltetrahydrofuran was prepared and 1ml of this solution was diluted with 50ml of 2-methyltetrahydrofuran. 1,3, 6, 10, 15, 20, 25 and 30. mu.l of the standard solutions were applied to TLC plates, respectively, TLC was developed and the peak intensities were determined.
Two samples of 25mg of the compound to be analyzed, each in 0.5ml of a given solvent, were prepared by shaking at 25 ℃ and 600rpm for 24 h. If the solution is clear, more material is added until a saturated solution is obtained.
After cooling to room temperature, the sample was filtered through a syringe filter (pore size 0.2 μm). The solution was stored at room temperature in a glass vial for 7d, then its solubility was determined by HPTLC on that day and after another 7d again with 20, 23 and 25 μ l of solution as described for the standard solutions, respectively.
Abbreviations
BuLi n-butyl lithium
LDA lithium diisopropylamide
DIPA diisopropylamine
THF tetrahydrofuran
DMSO dimethyl sulfoxide
DIPA diisopropylamine
MTBE ether methyl tert-butyl ether
m.p. melting Point
Examples
Comparative example 1
Step 1: 1-bromo-5-butoxy-3, 4-difluoro-2-iodobenzene
Figure BDA0002409873230000731
A solution of 5-bromo-1-butoxy-2, 3-difluorobenzene (19.5g, 74mmol) in THF (40mL) was added dropwise to a freshly prepared LDA solution (12.4mL DIPA, 120mL THF and 55mLBuLi (15% in hexanes)) at-70 ℃. The reaction was allowed to warm to-45 ℃ and stirred for 2h, after which it was cooled again (-70 ℃) and treated with iodine (22.4g, 88.2mmol) in THF (40 mL). The reaction mixture was stirred at the same temperature for 1h, slowly warmed to 0 ℃, and then treated with water (50mL), 25% HCl (until pH 5-6) and ethyl acetate. The aqueous phase was separated and extracted with ethyl acetate. The combined organic phases are treated with NaHSO3(saturated) aqueous solution, NaCl (saturated) aqueous solution, and Na2SO4Dried and concentrated in vacuo. The residue was filtered through silica to give 1-bromo-5-butoxy-3, 4-difluoro-2-iodo-benzene as a colorless oil.
Step 2: 1-bromo-5-butoxy-2- (4-ethoxy-2, 3-difluoro-phenyl) -3, 4-difluorobenzene
Figure BDA0002409873230000732
A solution of 4-ethoxy-2, 3-difluoroboronic acid (11.4g, 56.4mmol) and 1-bromo-5-butoxy-3, 4-difluoro-2-iodo-benzene (22.1g, 56.4mmol) in THF (180mL) was treated with a solution of sodium metaborate (12.6g, 45mmol) in water (70mL) at room temperature. The resulting mixture was degassed and treated with Pd (PPh)3)2Cl2(0.84g,1.17mmol) and hydrazine hydroxide (0.08mL, 1.72 mmol). The reaction mixture was stirred at 70 ℃ overnight, the two phases were separated and the aqueous phase was extracted with methyl tert-butyl ether. The combined organic phases were washed with aqueous NaCl (saturated) and Na2SO4Dried and concentrated in vacuo. The residue (23g) was purified by flash chromatography (heptane/ethyl acetate) to give 1-bromo-5-butoxy-2- (4-ethoxy-2, 3-difluoro-phenyl) -3, 4-difluoro-benzene as colorless crystals.
And step 3: 1-butoxy-4- (4-ethoxy-2, 3-difluoro-phenyl) -2, 3-difluoro-5-thiophenylbenzene
Figure BDA0002409873230000741
A solution of thiophenol (1.2g, 10.7mmol), 1-bromo-5-butoxy-2- (4-ethoxy-2, 3-difluoro-phenyl) -3, 4-difluorobenzene (4.1g, 9.73mmol) and KOtBu (1.31g, 11.68mmol) in degassed toluene (40mL) at room temperature under an argon atmosphere with Pd2(dba)3(92mg,0.10mmol) and Xanphos (128mg,0.21mmol) in toluene (2 mL). The resulting mixture was stirred at 110 ℃ overnight, then diluted with ethyl acetate and NaHCO3(saturated) aqueous solution and water washed over Na2SO4Dried, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography (heptane/ethyl acetate) to give 1-butoxy-4- (4-ethoxy-2, 3-difluoro-phenyl) -2, 3-difluoro-5-thiophenylbenzene as a light yellow oil.
And 4, step 4: 3-butoxy-7-ethoxy-1, 2,8, 9-tetrafluoro-dibenzothiophene
Figure BDA0002409873230000751
Palladium acetate (170mg, 0.73mmol) and 2, 6-dimethylbenzoic acid (250mg, 2.20mmol) were added to a solution of 1-butoxy-4- (4-ethoxy-2, 3-difluoro-phenyl) -2, 3-difluoro-5-thiophenyl-benzene (2.2g, 4.88mmol) in degassed toluene (20mL) at room temperature. The resulting mixture was stirred at 110 ℃ overnight, then diluted with ethyl acetate and NaHCO3(saturated) aqueous solution and water washed over Na2SO4Dried, filtered and concentrated under reduced pressure. The residue was purified by chromatography and recrystallized from acetonitrile to give 3-butoxy-7-ethoxy-1, 2,8, 9-tetrafluoro-dibenzothiophene as colorless crystals, m.p.143 ℃.
1H NMR:1.01(app t,J＝7.4Hz,3H),1.61–1.48(m,7H),1.86(app dq,J＝8.6,6.6Hz,2H),4.11(app t,J＝6.5Hz,2H),4.18(app q,J＝7.0Hz,2H),7.06(dd,J＝6.6,2.2Hz,2H)；19FNMR:–161.5(m,2F),–132.1(m,2F)；EI-MS:372.0
Comparative example 2
In analogy to comparative example 1, the following compounds were prepared:
Figure BDA0002409873230000752
1H NMR:δ7.33(dd,J＝5.6,1.5Hz,1H),7.11(dd,J＝6.4,1.7Hz,1H),3.93(d,J＝6.4Hz,2H),2.79(td,J＝7.6,1.4Hz,2H),2.01–1.80(m,5H),1.74(h,J＝7.3Hz,2H),1.42–1.18(m,5H),1.13(qd,J＝12.8,3.3Hz,2H),1.05–0.87(m,8H).19F NMR:δ-131.14–-131.77(m),-133.45–-134.10(m),-147.67(dd,J＝19.0,5.6Hz),-161.63.EI-MS:452.1.
phase sequence K153I
Δε：-12.0
Δn:0.1592
Clp:118℃
γ1:1319mPa s
(all values are inferred from 5% solution)
Comparative example 3:
in analogy to comparative example 1, the following compounds were prepared:
Figure BDA0002409873230000761
1H NMR:δ7.34(dd,J＝5.5,1.5Hz,1H),7.12(dd,J＝6.4,1.7Hz,1H),4.15(t,J＝6.5Hz,2H),2.80(td,J＝7.7,1.4Hz,2H),1.96–1.85(m,2H),1.71(dq,J＝9.7,7.3Hz,2H),1.62–1.53(m,2H),1.39(h,J＝3.6Hz,4H),1.04(t,J＝7.4Hz,3H),0.94(td,J＝7.2,6.2,3.4Hz,3H).EI-MS:398.1
comparative example 4:
in analogy to comparative example 1, the following compounds were prepared:
Figure BDA0002409873230000762
examples
Example 1: 1,2, 9-trifluoro-7-pentyl-3-propoxy-dibenzothiophene
Figure BDA0002409873230000763
Step 1: 1-bromo-3, 4-difluoro-2-iodo-5-propoxybenzene
Figure BDA0002409873230000764
A solution of 5-bromo-1, 2-difluoro-3-propoxy-benzene (29.0g, 115.5mmol) in THF (60mL) was added dropwise to a freshly prepared LDA solution (19.5mL DIPA, 180mL THF and 87mL BuLi (15% in hexanes)) at-70 ℃. The reaction was allowed to warm to-45 ℃ and stirred for 2h, then cooled again (-70 ℃) and treated with iodine (35.2g, 138.6mmol) in THF (60 mL). The reaction mixture was stirred at the same temperature for 1h, slowly warmed to 0 ℃, and then treated with water (100mL), 25% HCl (until pH 5-6) and ethyl acetate. The aqueous phase was separated and extracted with ethyl acetate. The combined organic phases are treated with NaHSO3(saturated) aqueous solution, NaCl (saturated) aqueous solution, and Na2SO4Dried and concentrated in vacuo. The residue was filtered through silica to give 1-bromo-5-butoxy-3, 4-difluoro-2-iodo-benzene as a colorless oil.
Step 2: 1-bromo-3, 4-difluoro-2- (2-fluoro-4-pentyl-phenyl) -5-propoxy-benzene
Figure BDA0002409873230000771
A solution of (2-fluoro-4-pentyl-phenyl) boronic acid (10.5g, 50.0mmol) and 1-bromo-3, 4-difluoro-2-iodo-5-propoxy-benzene (18.8g, 50.0mmol) in THF (150mL) was treated with a solution of sodium metaborate (11.1g, 40mmol) in water (65mL) at room temperature. The resulting mixture was degassed and treated with Pd (PPh)3)2Cl2(0.74g,1.04mmol) and hydrazine hydroxide (0.07mL, 1.53 mmol). The reaction mixture was stirred at 70 ℃ overnight, the two phases were separated and the aqueous phase was extracted with methyl tert-butyl ether. The combined organic phases were washed with aqueous NaCl (saturated) and Na2SO4Dried and concentrated in vacuo. The residue was purified by flash chromatography (heptane/ethyl acetate) to give 1-bromo-3, 4-difluoro-2- (2-fluoro-4-pentyl-phenyl) -5-propoxy-benzene as colorless crystals.
And step 3: 3, 4-difluoro-2- (2-fluoro-4-pentyl-phenyl) -1-thiophenyl-5-propoxy-benzene
Figure BDA0002409873230000772
A solution of thiophenol (0.92g, 8.21mmol), 1-bromo-3, 4-difluoro-2- (2-fluoro-4-pentyl-phenyl) -5-propoxy-benzene (4.1g, 9.73mmol) and KOtBu (1.31g, 11.68mmol) in degassed toluene (36mL) at room temperature under an argon atmosphere with Pd2(dba)3(140mg,0.15mmol) and Xanphos (196mg,0.33mmol) in toluene (2 mL). The resulting mixture was stirred at 110 ℃ overnight, then diluted with ethyl acetate and with NaHCO3(saturated) aqueous solution and water washed over Na2SO4Dried, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography (heptane/ethyl acetate) to give 3, 4-difluoro-2- (2-fluoro-4-pentyl-phenyl) -1-thiophenyl-5-propoxy-benzene as a light yellow oil.
And 4, step 4: 1,2, 9-trifluoro-7-pentyl-3-propoxy-dibenzothiophene
Figure BDA0002409873230000781
Palladium acetate (1.3g, 5.54mmol) and 2, 6-dimethylbenzoic acid (1.9g, 16.6mmol) were added to a solution of 3, 4-difluoro-2- (2-fluoro-4-pentyl-phenyl) -1-phenylthio-5-propoxy-benzene (5.7g, 12.3mmol) in degassed toluene (60mL) at room temperature. The resulting mixture was stirred at 110 ℃ overnight, then diluted with ethyl acetate and NaHCO3(saturated) aqueous solution and water washed over Na2SO4Dried, filtered and concentrated under reduced pressure. The residue was purified by chromatography (heptane/chlorobutane) and recrystallized from acetonitrile to give 1,2, 9-trifluoro-7-pentyl-3-propoxy-dibenzothiophene as colorless crystals.
1H NMR:δ7.73(dd,J＝7.0,1.8Hz,1H),7.16(dd,J＝12.6,1.4Hz,1H),4.13(t,J＝6.6Hz,2H),3.31(s,2H),2.76–2.64(m,2H),2.51(p,J＝1.9Hz,3H),1.91–1.74(m,2H),1.64(p,J＝7.4Hz,2H),1.40–1.23(m,4H),1.02(t,J＝7.4Hz,3H),0.87(t,J＝6.9Hz,3H).19FNMR:δ-108.38(dd,J＝99.5,12.7Hz),-133.82(ddd,J＝99.5,19.5,1.8Hz),-162.49(dd,J＝19.7,6.9Hz).EI-MS:366.1
Phase sequence: K80I
Δε:-7.3
Δn:0.1513
Clp:6℃
γ1:188mPa s
Example 2: 1,2, 8-trifluoro-7-pentyloxy-3-propoxy-dibenzothiophene
Figure BDA0002409873230000782
Step 1: 1-bromo-2- (2, 5-difluoro-4-pentyloxy-phenyl) -3, 4-difluoro-5-propoxy-benzene
Figure BDA0002409873230000791
Sodium metaborate octahydrate (1.37g, 4.96mmol) in water (8mL) was added at room temperature to a stirred solution of 2- (2, 5-difluoro-4-pentoxy-phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane (2.0g, 6.13mmol) and 1-bromo-3, 4-difluoro-2-iodo-5-propoxy-benzene (2.3g, 6.13 mmol). The mixture was degassed for 20min and then treated with bis (triphenylphosphine) palladium (II) chloride (0.09g, 0.13mmol) and aqueous hydrazine water (0.01mL, 0.19 mmol). The reaction mixture was stirred at reflux for 4h, the aqueous phase was separated and extracted with methyl tert-butyl ether. The combined organic phases were washed with saturated NaCl solution and Na2SO4Dried, filtered and concentrated under reduced pressure. The residue was purified by chromatography (heptane/ethyl acetate) to give 1-bromo-2- (2, 5-difluoro-4-pentyloxy-phenyl) -3, 4-difluoro-5-propoxy-benzene as a colorless oil.
Step 2: 2- (2, 5-difluoro-4-pentyloxy-phenyl) -3, 4-difluoro-5-propoxy-phenol
Figure BDA0002409873230000792
A solution of potassium hydroxide (2.6g, 46.7mmol) in water (30mL) was added to a solution of 1-bromo-2- (2, 5-difluoro-4-pentyloxy-phenyl) -3, 4-difluoro-5-propoxy-benzene (14.0g, 23.3mmol) in 1, 4-dioxane (60mL) at room temperatureThe solution was stirred. The mixture was degassed for 30min and then treated with bis (dibenzylideneacetone) palladium (0.67g, 1.17mmol) and tert-BuxPhos (0.79g, 1.87 mmol). The reaction mixture was stirred at 90 ℃ for 6 hours and quenched with aqueous hydrochloric acid (2M). The aqueous phase was separated and extracted with ethyl acetate. The combined organic phases were washed with saturated NaCl solution and Na2SO4Dried, filtered and concentrated under reduced pressure. The residue was purified by chromatography (heptane/ethyl acetate) to give 2- (2, 5-difluoro-4-pentyloxy-phenyl) -3, 4-difluoro-5-propoxyphenol as a colorless oil.
And step 3: [2- (2, 5-difluoro-4-pentyloxy-phenyl) -3, 4-difluoro-5-propoxy-phenyl ] trifluoromethanesulfonate
Figure BDA0002409873230000801
Trifluoromethanesulfonic anhydride (2.9mL, 17.7mmol) was added dropwise to a stirred solution of 2- (2, 5-difluoro-4-pentyloxy-phenyl) -3, 4-difluoro-5-propoxy-phenol (5.7g, 14.7mmol), triethylamine (3.1mL, 22.0mmol) and 4- (dimethylamino) -pyridine (54mg, 0.44mmol) in dichloromethane (50mL) at 10 ℃. The resulting mixture was stirred at room temperature overnight, filtered through a short pad of silica (eluent: chlorobutane) and concentrated under reduced pressure. The residue was purified by chromatography (heptane/chlorobutane) to give [2- (2, 5-difluoro-4-pentyloxy-phenyl) -3, 4-difluoro-5-propoxy-phenyl ] trifluoromethanesulfonate as a colorless oil.
And 4, step 4: 1,2, 8-trifluoro-7-pentyloxy-3-propoxy-dibenzothiophene
Figure BDA0002409873230000802
N, N-diisopropylethylamine (3.0mL, 17.9mmol) was added to [2- (2, 5-difluoro-4-pentyloxy-phenyl) -3, 4-difluoro-5-propoxy-phenyl]A stirred solution of triflate (5.9g, 11.4mmol) and 2-ethyl-hexyl 3-mercaptopropionate (3.5mL, 14.9mmol) in toluene (30 mL). The mixture was degassed for 1 hour and then treated with tris (dibenzylideneacetone) dipalladium (0) (110mg, 0.11mmol) and (di-2, 1-phenylene oxide) bis (diphenyl oxide)Phosphine) (125mg, 0.23 mmol). The reaction mixture was stirred at 110 ℃ overnight and treated slowly with potassium tert-butoxide (2.67g, 23.7mmol) in THF (15 mL). The resulting mixture was stirred at 110 ℃ for two days, cooled to ambient temperature, and treated with methyl tert-butyl ether and water. The aqueous phase was separated and extracted with methyl tert-butyl ether. The combined organic phases were washed with saturated NaCl solution and Na2SO4Dried, filtered and concentrated under reduced pressure. The residue was purified by chromatography (heptane/chlorobutane) and recrystallized from acetonitrile to give 1,2, 8-trifluoro-7-pentyloxy-3-propoxy-dibenzothiophene as colorless crystals.1H NMR:δ7.89(d,J＝11.5Hz,1H),7.35–7.23(m,1H),7.07(dd,J＝6.2,1.8Hz,1H),4.07(dt,J＝11.7,6.6Hz,4H),1.98–1.80(m,4H),1.54–1.36(m,4H),1.08(t,J＝7.4Hz,3H),0.95(t,J＝7.1Hz,3H).19F NMR:δ-136.34(dd,J＝11.5,7.7Hz),-144.15(dd,J＝19.3,2.0Hz),-162.90(dd,J＝19.3,6.3Hz).EI-MS:382.0.
Phase sequence: K126I
Δε：-10.1
Δn:0.1455
Clp:13.8℃
γ1:342mPa s
(all values are extrapolated from a 5% solution)
Example 3:
in analogy to example 2, the following compounds were prepared:
Figure BDA0002409873230000811
1H NMR:δ7.88(d,J＝10.5Hz,1H),7.55(d,J＝6.6Hz,1H),7.11(dd,J＝6.3,1.8Hz,1H),4.08(t,J＝6.6Hz,2H),2.75(t,J＝7.6Hz,2H),2.01–1.81(m,2H),1.68(p,J＝7.3Hz,2H),1.37(h,J＝3.6Hz,4H),1.09(t,J＝7.4Hz,3H),0.95–0.84(m,3H).19F NMR:δ-122.25(dd,J＝10.6,6.6Hz),-143.02(d,J＝19.2Hz),-162.95(d,J＝25.2Hz).EI-MS:366.2
phase sequence: K107I
Δε：-6.5
Δn:0.1372
Clp:-19.8℃
γ1:188mPa s
(all values are extrapolated from a 5% solution)
Example 4:
in analogy to example 1, the following compounds were prepared:
Figure BDA0002409873230000821
1H NMR(Chloroform-d)δ7.33(s,1H),7.07(dd,J＝6.5,1.6Hz,1H),6.96(d,J＝12.1Hz,1H),3.89(d,J＝6.4Hz,2H),2.70(t,J＝7.7Hz,2H),1.94(dd,J＝13.3,3.4Hz,2H),1.83(ddd,J＝14.1,8.1,4.9Hz,3H),1.67(p,J＝7.3Hz,2H),1.41–0.81(m,19H).19F NMR:δ-107.49(dd,J＝102.1,12.1Hz),-132.18(dd,J＝102.0,18.3Hz),-161.84(dd,J＝18.6,6.5Hz).EI-MS:462.2
phase sequence: K123N (111) I
Δε：-7.4
Δn:0.1649
Clp:134.4℃
γ1:933mPa s
(all values are extrapolated from a 5% solution)
Example 5: 1,2, 8-trifluoro-7-pentyloxy-3-propoxy-dibenzofuran
This compound was prepared from the same intermediate as in example 2.
Figure BDA0002409873230000822
Potassium phosphate (2.1g, 9.4mmol) was added to a stirred solution of 2- (2, 5-difluoro-4-pentyloxy-phenyl) -3, 4-difluoro-5-propoxy-phenol (3.0g, 7.8mmol) in 1, 3-dimethyl-3, 4,5, 6-tetrahydro-2 (1H) -pyrimidinone (35 mL). The reaction mixture was stirred at 110 ℃ overnight and then treated with saturated NaCl solution and methyl tert-butyl ether. The aqueous phase was separated and extracted twice with methyl tert-butyl ether. The combined organic phases were washed with saturated NaCl solution and Na2SO4Dried, filtered and concentrated under reduced pressure. The residue is purified by chromatography (heptane/chlorobutane) andrecrystallization from ethanol gave 1,2, 8-trifluoro-7-pentyloxy-3-propoxy-dibenzofuran as colorless crystals.1H NMR:δ7.64(dd,J＝10.5,2.8Hz,1H),7.50(d,J＝6.8Hz,1H),7.35(d,J＝5.8Hz,1H),4.15(td,J＝6.4,3.8Hz,4H),1.79(dq,J＝10.0,6.8Hz,4H),1.51–1.29(m,4H),1.02(t,J＝7.3Hz,3H),0.91(t,J＝7.0Hz,3H).19FNMR:δ-138.55(dd,J＝10.3,7.0Hz),-144.62–-144.76(m),-166.41(dd,J＝21.1,5.9Hz).EI-MS:366.0.m.p.147℃.
Phase sequence: K147I.
Example 6:
the following compounds were prepared analogously to example 5.
Figure BDA0002409873230000831
1H NMR:7.30(d,J＝5.7Hz,1H),6.91(dd,J＝5.6,1.7Hz,1H),4.06(t,J＝6.5Hz,2H),2.75(td,J＝7.7,1.4Hz,2H),1.91(dtd,J＝13.9,7.4,6.4Hz,2H),1.74–1.61(m,2H),1.36(h,J＝3.5Hz,4H),1.09(t,J＝7.4Hz,3H),0.96–0.85(m,3H).EI-MS:350.2
Phase sequence: K88I
Δε：-4.8
Δn:0.1291
Clp:-49.6℃
γ1:103mPa s
(all values are extrapolated from a 5% solution)
Example 7
The following compounds were prepared analogously to example 5.
Figure BDA0002409873230000832
1H NMR(Chloroform-d)δ7.61(d,J＝10.3Hz,1H),7.11(d,J＝6.7Hz,1H),6.91(dd,J＝5.6,1.7Hz,1H),4.09(t,J＝6.6Hz,2H),3.88(d,J＝6.4Hz,2H),2.02–1.76(m,7H),1.63–1.47(m,5H),1.32–0.84(m,13H).19F NMR:δ-138.83(dd,J＝10.3,6.8Hz),-144.10(dd,J＝20.1,2.0Hz),-165.98(dd,J＝20.0,5.3Hz).EI-MS:434.204.
Phase sequence: K142I
The solubility of comparative examples 1,2 and example 1 was determined according to the procedure described above. The results are shown in Table 1.
TABLE 1
Figure BDA0002409873230000841
It can be seen that the compound of example 1 has excellent solubility in cyclohexane, in contrast to the very low solubility of the prior art compound.
The compounds according to the invention are characterized by a high dielectric anisotropy and a high solubility, which makes them very suitable for use in liquid-crystalline media for VA, IPS and FFS displays.

Claims (15)

1. A compound of formula I
Figure FDA0002409873220000011
Wherein
W represents O or S, and W represents O or S,
L1represents R1Or X1,
L2Represents R2Or X2,
R1,R2Each independently of the others, represents H, an alkyl or alkoxy group having 1 to 15 carbon atoms, wherein, in addition, one or more CH groups in these groups2The radicals may each, independently of one another, be substituted by-C.ident.C-, -CH-,
Figure FDA0002409873220000012
Figure FDA0002409873220000013
-CF2O-,-OCF2-, -O-, -S-, -CO-O-or-O-CO-in such a way that O-or S-are not linked directly to one another, and wherein, in addition, one or more H atoms may be replaced by CN or halogen,
X1and X2Each of which isIndependently of one another, represents haloalkyl, haloalkoxy, haloalkenyl or haloalkenyloxy having up to 5C atoms, F, Cl, CN, SCN, SF5，
A1And A2Each independently of the others represents a group selected from:
a) trans-1, 4-cyclohexylene, 1, 4-cyclohexenylene, and decahydronaphthalene-2, 6-diyl, wherein one or more non-adjacent CH' s2The radicals may be replaced by-O-and/or-S-and one or more H atoms may be replaced by F,
b) from the group consisting of 1, 4-phenylene and 2, 6-naphthylene, in which one or two CH groups may be replaced by N and in which, in addition, one or more H atoms may be replaced by L,
c) from the group consisting of cyclopentane-1, 3-diyl, cyclopentane-2-ene-1, 3-diyl, 1, 3-dioxane-2, 5-diyl, tetrahydrofuran-2, 5-diyl, cyclobutane-1, 3-diyl, thiophene-2, 5-diyl, selenophene-2, 5-diyl and 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, each of which may be mono-or polysubstituted by L,
d) from the group consisting of bicyclo [1.1.1] pentane-1, 3-diyl, bicyclo [2.2.2] octane-1, 4-diyl and spiro [3.3] heptane-2, 6-diyl, in which one or more H atoms may be replaced by F,
l each, identically or differently, denotes halogen, cyano, alkyl having 1 to 7C atoms, alkoxy, alkylcarbonyl, alkoxycarbonyl, in which one or more H atoms may be substituted by F or Cl,
Z1and Z2Independently of one another, represents a single bond, -CF2O-，-OCF2-，-CH2CH2-，-CF2CF2-，-C(O)O-，-OC(O)-，-CH2O-，-OCH2-, -CF-CH-, -CH-CF-, -CF-, -CH-or-C.ident.C-,
Y1,Y2,Y3and Y4Independently of one another, H, F, Cl, CN, CF3Or OCF3，
m and n are each independently of the other 0,1 or 2, and m + n is 0,1 or 2,
provided that Y is1,Y2,Y3And Y4Is different from F and Y1,Y2,Y3And Y4Is different from H.
2. A compound according to claim 1, wherein the compound is selected from compounds of sub-formula IA
Figure FDA0002409873220000021
Figure FDA0002409873220000031
Wherein the radicals and parameters are as defined in claim 1.
3. A compound according to claim 1 or 2, wherein
R1,R2Each independently of the others, represents a straight-chain alkyl, alkenyl or alkoxy radical having up to 7C atoms, or cyclopropyl, cyclobutyl, cyclopentyl or cyclopent-1-enyl,
X2denotes F, CF3Or OCF3，
A1Represents a group selected from:
Figure FDA0002409873220000032
Z1represents-CH2O-,-CH2CH2-or a single bond,
Y1，Y2，Y3and Y4Represents H or F, provided that Y is1，Y2，Y3And Y4Is H, and
m is 0 or 1.
4. The compound according to one or more of claims 1 to 3, wherein m is 1 and Z1Represents a single bond or-CH2O-。
5. A compound according to one or more of claims 1 to 3, wherein m is 0.
6. A compound according to one or more of claims 1 to 5, wherein Y1Represents H and Y2，Y3And Y4Both represent F.
7. A compound according to one or more of claims 1 to 5, wherein Y2Represents H and Y1，Y3And Y4Both represent F.
8. A compound according to one or more of claims 1 to 5, wherein Y3Represents H and Y1，Y2And Y4Both represent F.
9. A compound according to one or more of claims 1 to 5, wherein Y4Represents H and Y1，Y2And Y3Both represent F.
10. A compound according to one or more of claims 1 to 5, wherein Y1And Y4Are all F and Y2And Y3All represent H.
11. A compound of formula II
Figure FDA0002409873220000041
Wherein the radicals and parameters present have the meanings indicated above for the formula I, and
RIIdenotes alkyl having 1 to 5C atoms, or phenyl, wherein one or two ═ CH-groups can be replaced by ═ N-and one or more H atoms can be replaced by halogen or alkyl having 1 to 10C atoms.
12. A process for the preparation of compounds of the formula I according to one or more of claims 1 to 10, which comprises catalyzing the intramolecular reaction of compounds of the formula ii according to claim 11 with a palladium catalyst in an aprotic organic solvent.
13. Use of a compound according to one or more of claims 1 to 10 in a liquid-crystalline medium.
14. Liquid-crystalline medium, characterized in that it comprises one or more compounds of the formula I according to one or more of claims 1 to 10.
15. An electro-optical display element comprising a liquid-crystalline medium according to claim 14.
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