text:
|Publication number
|Publication type
|Application number
|PCT number
|Publication date
|Sep 28, 1993
|Filing date
|Feb 27, 1989
|Priority date
|Mar 10, 1988
|Fee status
|Publication number
|Volker Reiffenrath, Joachim Krause, Andreas Wachtler, Georg Weber, Thomas Geelhaar, David Coates, Ian C. Sage, Simon Greenfield
|Original Assignee
|Merck Patent Gesellschaft Mit Beschrankter Haftung
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (32), Referenced by (12), Classifications (31), Legal Events (3)
|External Links: USPTO, USPTO Assignment, Espacenet
This application is a continuation of application Ser. No. 07/362,435, filed May 15, 1989 now abandoned.
The invention relates to 2,3-difluorohydroquinone derivatives of the formula I ##STR2## in which
R1 and R2, in each case independently of one another, are alkyl having 1 to 15 C atoms or alkenyl having 3 to 15 C atoms which are unsubstituted, monosubstituted by cyano or at least monosubstituted by fluorine or chlorine, it also being possible for one CH2 group in these radicals to be replaced by --O--, --CO--, --CO--O--, --O--CO-- or --O--CO--O--,
A1, A2 and A3, in each case independently of one another, are
(a) trans-1,4-cyclohexylene, in which, in addition, one or two non-adjacent CH2 groups may be replaced by --O-- and/or --S--,
(b) 1,4-phenylene, in which, in addition, one or two CH groups may be replaced by N, or
(c) a radical from the group comprising piperidine-1,4-diyl, 1,4-bicylo-(2,2,2)octylene (sic), 1,3,4-thiadiazole-2,5-diyl, napththalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl,
it being possible for the radicals (a) and (b) to be monosubstituted or polysubstituted by F, Cl, CH3 or CN,
Z1 is --CO--O--, --O--CO--, --CH2 --CH2 --, --OCH2 --, --CH2 O--, --C.tbd.C-- or a single bond,
Q1 and Q2, in each case independently of one another, arc --CO-- or --CH2 --,
m and n are each 0, 1 or 2, and
(m+n) is 0, 1 or 2.
For reasons of simplicity, Cyc below is a 1,4-cyclohexylene group and PheF2 below is a group of the formula ##STR3##
The compounds of the formula I can be used as components of liquid-crystalline media, in particular for displays based on the principle of the twisted cell, the guest-host effect, the effect of deformation of aligned phases or the effect of dynamic scattering.
The compounds of the formula I are distinguished by a clearly negative anisotropy of the dielectric constant and, in an electrical field, are aligned with their longitudinal molecular axes perpendicular to the field direction.
This effect is known and is utilized to control the optical transparency in various liquid-crystal displays, for example in liquid-crystal cells of the light-scattering type (dynamic scattering), of the so-called DAP type (deformation of aligned phases) or ECB type (electrically controlled birefrigence) or of the guest/host type (guest/host interaction).
The compounds of the formula I are also suitable as components of nematic or chirally nematic liquid-crystalline media having a dielectric anisotropy which is positive overall. The purpose of the compounds of the formula I here is to increase ε195. The negative dielectric anisotropy of the compounds according to the invention is overcompensated here by addition of components which are highly positive dielectrically. Such media are used for TN displays having a 90� twist or, in particular, for more highly twisted TN cells since they result here in particularly steep characteristic lines.
In addition, compounds of the formula I are suitable as components of chiral tilted smectic media. Chiral tilted smectic liquid-crystalline media having ferroelectric properties can be prepared by adding a suitable chiral dope to base mixtures containing one or more tilted smectic media (L. A. Veresnev et al., Mol. Cryst. Liq. Cryst. 89, 327 (1982); H. R. Brand et al., J. Physique 44 (lett.), L-771 (1983). Such media can be used as dielectrics for rapidly switching displays based on the principle, described by Clark and Lagerwall, of SSFLC technology (N. A. Clark and S. T. Lagerwall, Appl. Phys. Lett. 36, 899 (1980); U.S. Pat. 4,367,924) on the basis of the ferroelectric properties of the chiral tilted medium.
A number of liquid-crystalline compounds having slightly negative dielectric anisotropy have hitherto already been synthesized. In contrast, only relatively few liquid-crystal components having a large negative anisotropy of the dielectric constant are known. In addition, the latter generally have disadvantages, such as, for example, poor solubility in mixtures, high viscosity, high melting points and chemical instability. There is therefore a demand for further compounds having negative dielectric anisotropy which permit the properties of mixtures to be further improved for a very wide variety of electrooptical applications.
Liquid-crystal compounds having a negative dielectric anisotropy and containing two or three rings linked via carboxyl groups or a covalent bond and containing one or more side groups, such as halogen, cyano or nitro groups, are known from DE 2,240,864, DE 2,613,293, DE 2,835,662, DE 2,836,086 and EP 023,728.
EP 084,194 gives a broad formula covering the compounds claimed here. However, no individual compounds of the formula according to the invention are mentioned. Those skilled in the art would thus be able neither to deduce in simple manner possible syntheses for the compounds claimed nor to recognize that the compounds according to the invention have mesophase regions which are predominantly in a favorable location and are distinguished by a large negative anisotropy of the dielectricity with at the same time low viscosity.
Neither is there any indication of the possibility of using the compounds according to the invention in the displays based on SSFLC technology, since the compounds claimed therein have low smectic tendencies.
Furthermore, dibenzoic acid esters of 2,3-dichlorohydroquinone are known (for example Bristol et al., J. Org. Chem. 39, 3138 (1974) or Clanderman et al., J. Am. Chem. Soc. 97, 1585 (1975)), but these are monotropic or have very small mesophase ranges. The esters of 4-hydroxy-2,3-dichlorobenzoic acid described by Eidenschink et al. (Angew. Chem. 89, 103 (1977)) likewise have only narrow mesophase ranges.
The 4-alkyl-2,3-dichlorophenyl-4'-alkylbicyclohexyl-4-carboxylic acid esters known from German Offenlegungsschrift 2,933,563 cannot be used industrially due to their high viscosity.
The invention had the object of indicating stable, liquid-crystalline or mesogenic compounds having a large negative anisotropy of the dielectricity and simultaneously low viscosity.
It has been found that the compounds of the formula I are preeminently suitable as components of liquid-crystalline media. They can be used, in particular, to prepare stable liquid-crystalline media having a broad mesophase range and comparatively low viscosity.
The compounds of the formula I are furthermore suitable as components of chiral tilted smectic liquid-crystalline media.
In addition, the provision of compounds of the formula I very generally considerably broadens the range of liquid-crystalline substances which are suitable, from various applicational points of view, for the purpose of preparing liquid-crystalline media.
The compounds of the formula I have a broad field of application. Depending on the choice of substituents, these compounds can be used as base materials from which liquid-crystalline media are predominantly composed; however, it is also possible to add liquid-crystalline base materials from other classes of compounds to the compounds of the formula I in order, for example, to vary the dielectric and/or optical anisotropy and/or viscosity and/or the spontaneous polarization and/or the phase ranges and/or the tilt angle and/or the pitch of a dielectric of this type.
The compounds of the formula I are furthermore suitable as intermediates for the preparation of other substances which can be used as components of liquid-crystalline media.
In the pure state, the compounds of the formula I are colorless and form liquid-crystalline mesophases in a temperature range in a favorable location for electrooptical use. They are very stable chemically, thermally and to light.
The invention thus relates to the compounds of the formula I and to a process for their preparation, characterized in that an appropriate carboxylic acid or hydroxyl compound or a reactive derivative thereof is reacted with an appropriate hydroxyl compound or a reactive derivative thereof.
The invention additionally relates to the use of the compounds of the formula I as components of liquid-crystalline media. The invention furthermore relates to liquid-crystalline media containing at least one compound of the formula I, and to liquid-crystal display elements containing such media. Media of this type have particularly advantageous elastic constants, and, due to their low Δε/ε.sub.⊥ values, are particularly suitable for TFT mixtures.
The invention furthermore relates to all novel intermediates for the preparation of the compounds according to the invention.
Above and below, R1, R2, A1, A2, A3, Z1, Q1, Q2, n and m are as defined, unless expressly stated otherwise.
The compounds of the formula I accordingly include preferred compounds having two rings, of the sub-formula Ia:
R1 --A2 --Q1 --O--PheF2 --O--Q2 --R2 1a
preferred compounds having three rings, of the sub-formulae Ib to Id:
R1 --A2 --Q1 --O--PheF2 --O--Q2 --A3 --R2 1b
R1 --A1 --A2 --Q1 --O--PheF2 --O--Q2 --R2 1c
R1 --A1 --Z1 --A2 --Q1 --O--PheF2 --O--Q2 --R2 Id
and preferred compounds having four rings, of the sub-formulae Ie and If:
R1 --A1 --A1 --A2 --Q1 --O--PheF2 O--Q2 --R2 Ie
R1 --A1 --A2 --Q1 --O--PheF2 --O--Q2 --A3 --R2 If
Of these, the compounds of the sub-formulae Ia, Ib and Ic are particularly preferred.
In the compounds of the formulae above and below, R1 and R2 are preferably alkyl or alkoxy.
Additionally preferred compounds are those of the formulae above and below in which one of the radicals R1 and R2 is alkenyl or oxaalkyl (for example alkoxymethyl).
In the formulae above and below, R1 and R2 preferably have 2-12 C atoms, in particular 3-10 C atoms. It is also possible for one or two CH2 groups in R1 and R2 to have been replaced. It is preferred that only one CH2 group has been replaced, by --O-- or --CH═CH--.
In the formulae above and below, R1 and R2 are preferably alkyl, alkoxy or another oxaalkyl group, furthermore also alkyl groups in which one or two CH2 groups may be replaced by --CH═CH--.
If R1 and R2 are alkyl radicals in which, in addition, one ("alkoxy" or "oxaalkyl") or two ("alkoxyalkoxy" or "dioxaalkyl") non-adjacent CH2 groups may be replaced by O atoms, they can be straight-chain or branched. They are preferably straight-chain, have 2,3,4,5,6 or 7 C atoms and are accordingly 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, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy.
Oxaalkyl is preferably straight-chain 2-oxypropyl (═methoxymethyl), 2-(═ethoxymethyl) or 3-oxabutyl (═2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl, 1,3-dioxabutyl (═methoxymethoxy), 1,3-, 1,4- or 2,4-dioxapentyl, 1,3-, 1,4-, 1,5-, 2,4-, 2,5- or 3,5-dioxahexyl, or 1,3-, 1,4-, 1,5-, 1,6-, 2,4-, 2,5-, 2,6-, 3,5-, 3,6- or 4,6-dioxaheptyl.
If R1 and R2 are an alkyl radical in which one CH2 group has been replaced by --CH═CH--, the trans form is preferred. This alkenyl radical can be straight-chain or branched. It is preferably straight-chain and has 2 to 10 C atoms. It is accordingly particularly vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or -5-enyl, hept-1-, -2-, -3-, -4-, -5- or -6-enyl, oct-1-, -2-, -3-, -4-, -5-, -6- or -7-enyl, non-1-, -2-, -3-, -4-, -5-, -6-, -7- or -8-enyl, or dec-1-, -2-, -3-, -4-, -5-, -6-, -7-, -8- or - 9-enyl.
If the radicals R1 and R2 are monosubstituted by cyano or at least monosubstituted by fluorine or chlorine, they are preferably ω-fluoro- or ω-cyano-n-alkyl having 1-12 C atoms, n-alkyl groups having 2-12 C atoms with substitution by fluorine, chlorine or cyano on a secondary C atom, or perfluoro-n-alkyl groups having 1-12 C atoms in which, in addition, one or more CF2 groups may be replaced by --O-- and/or --CH2 --.
Compounds of the formula I having branched wing groups R1 and/or R2 may occasionally be of importance due to better solubility in the customary liquid-crystalline base materials, but in particular as chiral dopes if they are optically active. Smectic compounds of this type are suitable as components for ferroelectric materials.
Branched groups of this type generally contain not more than one chain branch. Preferred branch radicals R1 and/or R2 are isopropyl, 2-butyl (═1-methylpropyl), isobutyl (═2-methylpropyl), 2-methylbutyl, isopentyl (═3-methylbutyl), 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, -2methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 1-methylhexoxy, 1-methylheptoxy, 2-oxa-3-methylbutyl, 3-oxa-4-methylpentyl, 4-methylhexyl, 2-nonyl, 2-decyl, 2-dodecyl and 6-methyloctoxy.
The formula I covers the racemates of these compounds and the optical antipodes, and mixtures thereof.
A1, A2 and A3, in each case independently of one another, are preferably trans-1,4-cyclohexylene, 1,4-phenylene, 2- or 3-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, pyrimidine-2,5-diyl or pyridine-2,5-diyl. The compounds according to the invention preferably contain only one 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, pyridine-2,5-diyl or pyrimidine-2,5-diyl group. Particularly preferred meanings for A1, A2 and A3 are trans-1,4-cyclohexylene and 1,4-phenylene.
m and n are each preferably 0 or 1. Z1 is preferably --CH2 CH2 -- or a single bond. Q1 is --CO-- or --CH2 -- in the case where A2 =radical (a) [i.e. for example, 1,4-cyclohexylene], --CH2 -- being preferred. In the case where A2 ═radical (b) [i.e. for example, 1,4-phenylene], Q1 is preferably --CO--.
Of the compounds of the formulae I and Ia to If, those are preferred in which at least one of the radicals present therein has one of the preferred meanings indicated.
Particularly preferred compounds are 2,3-difluorohydroquinone derivatives of the formula Ia': ##STR4## in which
R3 and R4, in each case independently of one another, are alkyl having 1 to 15 C atoms, and o, p and q are 0 or 1, and
2,3-difluorohydroquinone derivatives of the formula Ia" ##STR5## in which R1, R2 and Q1 have the meaning indicated in claim 1, m is 0 or 1, Z1 is --CH2 CH2 -- or a single bond, Al and A2 are each trans-1,4-cyclohexylene.
The compounds of the formula I are prepared by methods known per se, as described in the literature (for example in the standard works such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), to be precise under reaction conditions which are known and suitable for the reactions mentioned. Use can also be made here of variants which are known per se, but are not described in greater detail here.
If desired, the starting materials can also be formed in situ by not isolating them from the reaction mixture, but instead immediately converting them further into the compounds of the formula I.
The compounds of the formula I are accessible starting from 1,2-difluorobenzene. The latter is metallated by a process known per se (for example A. M. Roe et al., J. Chem. Soc. Chem. Comm., 22, 582 (1965)), and the metallation product is reacted with the appropriate electrophile. This reaction sequence can be carried out a second time using the 1-substituted 2,3-difluorobenzene obtained in this way, for example using tert.-butylhydroperoxide as the electrophile, and the 1-substituted 2,3-difluorophenols are thus obtained. 1,2-difluorobenzene or 1-substituted 2,3-difluorobenzene is reacted with phenyllithium, lithium tetramethylpiperidine, n-, sec- or tert-butyllithium at temperatures of from -100� C. to +50� C., preferably -78� C. to 0� C., in an inert solvent, such as diethyl ether, tetrahydrofuran, dimethoxyethane, tert-butyl methyl ether or dioxane, hydrocarbons, such as hexane, heptane, cyclohexane, benzene or toluene, or mixtures of these solvents, if appropriate with the addition of a complexing agent, such as tetramethylethylenediamine (TMEDA) or hexamethylphosphoric triamide.
The lithium-2,3-difluorophenyl compounds are reacted with the appropriate electrophiles at -100� C. to 0� C., preferably at -50� C. Suitable electrophiles are aldehydes, ketones, nitriles, epoxides, carboxylic acid derivatives, such as esters, anhydrides or halides, haloformic acid esters or carbon dioxide.
For reaction with aliphatic or aromatic halogen compounds, the lithium 2,3-difluorophenyl compounds are transmetallated and coupled with transition-metal catalysis. Zinc 2,3-difluorophenyl compounds (cf. German Offenlegungsschrift 3,632,410) or titanium 2,3-difluorophenyl compounds (cf. German Offenlegungsschrift 3,736,489) are particularly suitable for this purpose.
The compounds of the formula I can be prepared by esterification of appropriate carboxylic acids (or reactive derivatives thereof) using alcohols or phenols (or reactive derivatives thereof).
Suitable reactive derivatives of the carboxylic acids mentioned are, in particular, the acid halides, above all the chlorides and bromides, furthermore the anhydrides, for example also mixed anhydrides, azides or esters, in particular alkyl esters having 1-4 C atoms in the alkyl group.
Suitable reactive derivatives of the alcohols or phenols mentioned are, in particular, the corresponding metal alcoholates or phenolates, preferably of an alkali metal such as Na or K.
The esterification is advantageously carried out in the presence of an inert solvent. Highly suitable solvents are, in particular, ethers, such as diethyl ether, di-n-butyl ether, THF, dioxane or anisole, ketones, such as acetone, butanone or cyclohexanone, amides, such as DMF or hexamethylphosphoric triamide, hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons, such as carbon tetrachloride or tetrachloroethylene, and sulphoxides, such as dimethyl sulphoxide or sulpholane. Water-immiscible solvents can advantageously be used at the same time for removal of the water formed during the esterification by azeotropic distillation. An excess of an organic base, for example pyridine, quinoline or triethylamine, can occasionally also be used as the solvent for the esterification. The esterification can also be carried out in the absence of a solvent, for example by simply heating the components in the presence of sodium acetate. The reaction temperature is usually between -50� and +250�, preferably between -20� and +80�. At these temperatures, the esterification reaction is generally complete after 15 minutes to 48 hours.
In detail, the reaction conditions for the esterification depend substantially on the nature of the starting materials used. Thus, the reaction of a free carboxylic acid with a free alcohol or phenol is generally carried out in the presence of a strong acid, for example a mineral acid such as hydrochloric acid or sulphuric acid. A preferred reaction procedure is to react an acid anhydride or, in particular, an acyl chloride with an alcohol, preferably in a basic medium, important bases being, in particular, alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, alkali metal carbonates or hydrogen carbonates, such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate, alkali metal acetates, such as sodium acetate or potassium acetate, alkaline earth metal hydroxides, such as calcium hydroxide, or organic bases such as triethylamine, pyridine, lutidine, collidine or quinoline. A further preferred embodiment of esterification is to first convert the alcohol or the phenol, for example by treatment with ethanolic sodium hydroxide solution or potassium hydroxide solution, into the sodium alcoholate or phenolate or potassium alcoholate or phenolate, to isolate and suspend the latter with stirring in acetone or diethyl ether together with sodium hydrogen carbonate or potassium carbonate, and to add a solution of the acyl chloride or acid anhydride in diethyl ether, acetone or DMF to this suspension, expediently at temperatures between about -25� and +20�.
The methyl ethers of the formula I can be prepared by known etherification reactions, for example by reacting a compound of the formula R--1 --(A1 --Z1)m --A2 --Q1 --O--PheF2 --ZA or R2 --(A3)n --Q2 --O--PheF2 --ZA, in which ZA is OH or OMe, SH or SMe where Me is an equivalent of a metal cation, and Hal is a halogen atom, preferably chlorine or bromine (reactive derivative of the phenols), with a compound of the formula R2 -(A3)n --ZB or R1 --(A1 --Z1)m --A2 --ZB in which ZB is --CH2 --OH or --CH2 -Hal (reactive derivative) in the presence of a base. In these formulae, the radicals R1, R2, A1, A2, A3, Z1, m, n, Q1 and Q2 have the meanings indicated in the formula I. The reaction conditions for these ether syntheses are those customary for such reactions; the solvents used are polar, aprotic solvents, for example dimethyl sulphoxide, N,N-dimethylformamide or N-methypyrrolidone; the bases used are preferably alkali metal salts of weak acids, for example sodium acetate, potassium carbonate or sodium carbonate. The reactions can be carried out at temperatures between 0� C. and the boiling point of the lowest-boiling component of the reaction mixture; it has proven particularly advantageous to use temperatures between 60� and 120� C. Some of the starting materials are known, and some can be prepared analogously to known compounds by standard methods of synthetic organic chemistry.
An important novel intermediate in the synthesis of compounds according to the invention is 2,3-difluorohydroquinone. This novel compound, which is likewise subject-matter of the invention, can be obtained by oxidation of the known 2,3-difluorophenol in a manner known per se, for example by oxidation using potassium peroxodisulphate in alkaline, aqueous solution.
In addition to one or more compounds according to the invention, the liquid-crystalline media according to the invention preferably contain, as further components, 2 to 40, in particular 4 to 30, components. Besides one or more compounds according to the invention, these media very particularly preferably contain 7 to 25 components. These further components are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, in particular substances from the classes of the azoxybenzenes, benzylideneanilines, biphenyls, terphenyls, phenyl or cyclohexyl benzoates, phenyl or cyclohexyl cyclohexanecarboxylates, phenyl or cyclohexyl cyclohexylbenzoates, phenyl or cyclohexyl cyclohexylcyclohexanecarboxylates, cyclohexylphenyl benzoate, cyclohexanecarboxylate and cyclohexylcyclohexanecarboxylate, phenylcyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes, cyclohexylcyclohexanes, cyclohexylcyclohexenes, cyclohexylcyclohexylcyclohexenes, 1,4-bis-cyclohexylbenzenes, 4,4'-bis-cyclohexylbiphenyls, phenyl- or cyclohexylpyrimidines, phenyl- or cyclohexylpyridines, phenyl- or cyclohexyldioxanes, phenyl- or cyclohexyl1,3-dithianes, 1,2-diphenylethanes, 1,2-dicyclohexylethanes, 1-phenyl-2-cyclohexylethanes, 1-cyclohexyl-2-(4-phenylcyclohexyl)ethanes, 1-cyclohexyl-2-biphenylylethanes, 1-phenyl-2-cyclohexylphenylethanes, optionally halogenated stilbenes, benzyl phenyl ethers, tolans and substituted cinnamic acids. The 1,4-phenylene groups in these compounds may also be fluorinated.
The most important compounds which are suitable as further components of media according to the invention can be characterized by the formulae 1, 2, 3, 4 and 5:
R'--L--C.tbd.C--E--R" 5
In formulae 1, 2, 3, 4 and 5, L and E, which may be identical or different and are in each case independent of one another, are a bivalent radical from the group formed from --Phe--, --Cyc--, --Phe--Phe--, --Phe--Cyc--, --Cyc--Cyc--, --Pyr--, --Dio--, --G--Phe-- and --G--Cyc-- and the 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, pyrimidine-2,5-diyl, pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl.
One of the radicals L and E is preferably Cyc, Phe or Pyr. E is preferably Cyc, Phe or Phe-Cyc. The media according to the invention preferably contain one or more components selected from the compounds of the formulae 1, 2, 3, 4 and 5, in which L and E are selected from the group comprising Cyc, Phe and Pyr and simultaneously one or more components selected from the compounds of the formulae 1, 2, 3, 4 and 5 in which one of the radicals L and E is selected from the group comprising Cyc, Phe and Pyr and the other radical is selected from the group comprising --Phe--Phe--, --Phe--Cyc--, --Cyc--Cyc--, --G--Phe-- and --G--Cyc--, and, if appropriate, one or more components selected from the compounds of the formulae 1, 2, 3, 4 and 5 in which the radicals L and E are selected from the group comprising --Phe--Cyc--, --Cyc--Cyc--, --G--Phe-- and --G--Cyc--. In the compounds of the sub-formulae 1a, 2a, 3a, 4a and 5a, R' and R", in each case independently of one another, are alkyl, alkenyl, alkoxy, alkenyloxy or alkanoyloxy having up to 8 carbon atoms. In most of these compounds, R' and R" are different from one another, one of these radicals usually being alkyl or alkenyl. In the compounds of the sub-formulae 1b, 2b, 3b, 4b and 5b, R" is --CN, --CF3, F, Cl or --NCS; in these formulae, R has the meaning indicated in the case of the compounds of the sub-formulae la to 5a and is preferably alkyl or alkenyl. However, other variants of the proposed substituents in the compounds of the formulae 1, 2, 3, 4 and 5 are common. Many such substances and also mixtures thereof are commercially available. All these substances can be obtained by methods known from the literature or analogously thereto.
Besides components from the group comprising the compounds 1a, 2a, 3a, 4a and 5a (group 1), the media according to the invention preferably also contain components from the group comprising the compounds 1b, 2b, 3b, 4b and 5b (group 2), whose proportions are preferably as follows:
Group 1: 20 to 90%, in particular 30 to 90%,
Group 2: 10 to 80%, in particular 10 to 50%,
the sum of the proportions of the compounds according to the invention and of the compounds from groups 1 and 2 adding up to 100%.
The media according to the invention preferably contain 1 to 40%, in particular preferably 5 to 30%, of compounds according to the invention. Additionally preferred media are those which contain more than 40%, in particular 45 to 90%, of compounds according to the invention. The media preferably contain three, four or five compounds according to the invention.
The media according to the invention are prepared in a manner customary per se. In general, the components are dissolved in one another, expediently at elevated temperature. By means of suitable additives, the liquid-crystalline phases according to the invention can be modified in a manner such that they can be used in all types of liquid-crystal display elements disclosed hitherto. Additives of this type are known to those 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 added for the preparation of coloured guest/host systems, or substances can be added to modify the dielectric anisotropy, the viscosity and/or the orientation of the nematic phases.
The examples below are intended to illustrate the invention without representing a limitation. mp.=melting point, cp. clear point. Above and below, percentages are percent by weight; all temperatures are given in degrees Celsius. "Customary work-up" means that water is added, the mixture is extracted with methylene chloride, the organic phase is separated off, dried and evaporated, and the product is purified by crystallization and/or chromatography.
In addition, the abbreviations have the following meanings:
C: crystalline-solid state, S: smectic phase (the index characterizes the phase type), N: nematic state, Ch: cholesteric phase, I: isotropic phase. The number between two symbols indicates the conversion temperature in degrees Celsius.
0.1 mol of 2,3-difluoro-4-ethoxyphenol (preparable from 2,3-difluorophenol by alkylation using diethyl sulphate/potassium carbonate in dimethylformamide, lithiation at -70� to -80�, reaction with N-methylpiperidine and oxidation of the aldehyde by the Baeyer-Villiger method using performic acid) and 0.1 mol of pyridine were dissolved in 100 ml of toluene. 0.1 mol of trans-4-pentylcyclohexanecarbonyl chloride is added dropwise at 80�, and the mixture is stirred for a further 3 hours. The pyridine hydrochloride precipitated is filtered off with suction, the toluene is removed by distillation, and the 2,3-difluoro-4-ethoxyphenyl trans-4-pentylcyclohexanoate remaining is purified by crystallization from ethanol, mp. 48�, cp. 62.5�.
The following are prepared analogously:
2,3-difluoro-4-ethoxyphenyl trans-4-propylcyclohexanoate, mp. 50�, cp. 52�
2,3-difluoro-4-ethoxyphenyl trans-4-ethylcyclohexanoate
2,3-difluoro-4-ethoxyphenyl trans-4-butylcyclohexanoate, C 59� N (48�) I
2,3-difluoro-4-ethoxyphenyl trans-4-heptylcyclohexanoate, C 53� N 66� I
2,3-difluoro-4-methoxyphenyl trans-4-ethylcyclohexanoate
2,3-difluoro-4-methoxyphenyl trans-4-propylcyclohexanoate
2,3-difluoro-4-methoxyphenyl trans-4-butylcyclohexanoate
2,3-difluoro-4-methoxyphenyl trans-4-pentylcyclohexanoate
2,3-difluoro-4-methoxyphenyl trans-4-heptylcyclohexanoate
2,3-difluoro-4-propoxyphenyl trans-4-ethylcyclohexanoate
2,3-difluoro-4-propoxyphenyl trans-4-propylcyclohexanoate
2,3-difluoro-4-propoxyphenyl trans-4-butylcyclohexanoate
2,3-difluoro-4-propoxyphenyl trans-4-pentylcyclohexanoate
2,3-difluoro-4-propoxyphenyl trans-4-heptylcyclohexanoate
2,3-difluoro-4-butoxyphenyl trans-4-ethylcyclohexanoate
2,3-difluoro-4-butoxyphenyl trans-4-propylcyclohexanoate
2,3-difluoro-4-butoxyphenyl trans-4-butylcyclohexanoate
2,3-difluoro-4-butoxyphenyl trans-4-pentylcyclohexanoate
2,3-difluoro-4-butoxyphenyl trans-4-heptylcyclohexanoate
2,3-difluoro-4-hexoxyphenyl trans-4-ethylcyclohexanoate
2,3-difluoro-4-hexoxyphenyl trans-4-propylcyclohexanoate
2,3-difluoro-4-hexoxyphenyl trans-4-butylcyclohexanoate
2,3-difluoro-4-hexoxyphenyl trans-4-pentylcyclohexanoate
2,3-difluoro-4-hexoxyphenyl trans-4-heptylcyclohexanoate
2,3-difluoro-4-octoxyphenyl trans-4-ethylcyclohexanoate
2,3-difluoro-4-octoxyphenyl trans-4-propylcyclohexanoate
2,3-difluoro-4-octoxyphenyl trans-4-pentylcyclohexanoate
2,3-difluoro-4-octoxyphenyl trans-4-heptylcyclohexanoate, C 43� N 64� I.
2,3-difluoro-4-ethoxyphenyl trans-4-(trans-4propylcyclohexyl)cyclohexanoate, C 88� SA 100� N 223� I, is obtained analogously to Example 1 from the same phenol by reaction with 4-(trans-4-propylcyclohexyl)cyclohexanecarbonyl chloride.
The following are prepared analogously:
2,3-difluoro-4-ethoxyphenyl trans-4-(trans-4-ethylcyclohexyl)-cyclohexanoate
2,3-difluoro-4-ethoxyphenyl trans-4-(trans-4-butylcyclohexyl)-cyclohexanoate, C 91� SB 109� SA 128� N 217� I
2,3-difluoro-4-ethoxyphenyl trans-4-(trans-4-pentylcyclohexyl)-cyclohexanoate, C 95� SB 119� SA 143� N 220� I
2,3-difluoro-4-ethoxyphenyl trans-4-(trans-4-heptylcyclohexyl)-cyclohexanoate
2,3-difluoro-4-methoxyphenyl trans-4-(trans-4-ethylcyclohexyl)-cyclohexanoate
2,3-difluoro-4-methoxyphenyl trans-4-(trans-4-propylcyclohexyl)-cyclohexanoate
2,3-difluoro-4-methoxyphenyl trans-4-(trans-4-butylcyclohexyl)-cyclohexanoate
2,3-difluoro-4-methoxyphenyl trans-4-(trans-4-pentylcyclohexyl)-cyclohexanoate
2,3-difluoro-4-methoxyphenyl trans-4-(trans-4-heptylcyclohexyl)-cyclohexanoate
2,3-difluoro-4-propoxyphenyl trans-4-(trans-4-ethylcyclohexyl)-cyclohexanoate
2,3-difluoro-4-propoxyphenyl trans-4-(trans-4-propylcyclohexyl)-cyclohexanoate
2,3-difluoro-4-propoxyphenyl trans-4-(trans-4-butylcyclohexyl)-cyclohexanoate
2,3-difluoro-4-propoxyphenyl trans-4-(trans-4-pentylcyclohexyl)-cyclohexanoate
2,3-difluoro-4-propoxyphenyl trans-4-(trans-4-heptylcyclohexyl)-cyclohexanoate
2,3-difluoro-4-butoxyphenyl trans-4-(trans-4-ethylcyclohexyl)-cyclohexanoate
2,3-difluoro-4-butoxyphenyl trans-4-(trans-4-propylcyclohexyl)-cyclohexanoate
2,3-difluoro-4-butoxyphenyl trans-4-(trans-4-butylcyclohexyl)-cyclohexanoate
2,3-difluoro-4-butoxyphenyl trans-4-(trans-4-pentylcyclohexyl)-cyclohexanoate
2,3-difluoro-4-butoxyphenyl trans-4-(trans-4-heptylcyclohexyl)-cyclohexanoate
0.1 mol of 4-hexyloxybenzoic acid, 0.01 mol of dimethylaminopyridine and 0.1 mol of 2,3-difluoro-4octyloxyphenol (preparable from 2,3-difluorooctyloxybenzene by lithiation at -70� to -80� and dropwise addition of a solution of lithium t-butylperoxide in ether prepared from 0.12 mol of t-butyl hydroperoxide and 0.12 mol of butyllithium) are introduced into 150 ml of dichloromethane, a solution of 0.1 mol of dicyclohexylcarbodiimide in 30 ml of dichloromethane is added dropwise with stirring at 10o, and the mixture is subsequently stirred at room temperature for 15 hours. The mixture is filtered through silica gel, the solvent is evaporated, and 2,3-difluoro-4-octyloxyphenyl 4-hexyloxybenzoate is obtained as the residue.
The following are prepared analogously:
2,3-difluoro-4-octyloxyphenyl p-(4-heptyloxy-3-fluorophenyl)benzoate, C 69.3�, SC 146 SA 152.7� N 156� I
2,3-difluoro-4-octyloxyphenyl p-(4-octyloxy-3-fluorophenyl)benzoate
2,3-difluoro-4-octyloxyphenyl p-(4-nonyloxy-3-fluorophenyl)benzoate, C 71.7� SC 14 SA 149.8� N 150.2 I
2,3-difluoro-4-octyloxyphenyl p-(4-decyloxy-3-fluorophenyl)benzoate
2,3-difluoro-4-octyloxyphenyl p-(4-heptyl-3-fluorophenyl)benzoate, C 81� SC 121� SA 128.5N 148� I
4-heptyloxy-2,3-difluorophenyl p-hexylbenzoate
4-heptyloxy-2,3-difluorophenyl p-heptylbenzoate
4-heptyloxy-2,3-difluorophenyl p-octylbenzoate, mp 43.5�
4-heptyloxy 2,3-difluorophenyl p-decylbenzoate
4-heptyloxy-2,3-difluorophenyl p-hexyloxybenzoate
4-heptyloxy 2,3-difluorophenyl p-heptyloxybenzoate
4-heptyloxy 2,3-difluorophenyl p-octyloxybenzoate, C 53� (SC 39�) N 57� I
2,3-difluoro-4-heptyloxyphenyl p-(4-hexyl-3-fluorophenyl)benzoate
2,3-difluoro-4-heptyloxyphenyl p-(4-heptyl-3-fluorophenyl)benzoate
2,3-difluoro-4-heptyloxyphenyl p-(4-octyl-3-fluorophenyl)benzoate, C 60� SC 15 SA 155� N 157� I
2,3-difluoro-4-heptyloxyphenyl p-(4-hexylphenyl)benzoate,
2,3-difluoro-4-heptyloxyphenyl p-(4-heptylphenyl)benzoate
2,3-difluoro-4-heptyloxyphenyl p-(4-octylphenyl)benzoate, C 86� SC 12 SA 131� N 145� I
2,3-difluoro-4-heptyloxyphenyl p-(4-hexyloxyphenyl)benzoate
2,3-difluoro-4-heptyloxyphenyl p-(4-heptyloxyphenyl)benzoate
2,3-difluoro-4-heptyloxyphenyl p-(4-octyloxyphenyl)benzoate, C 94� SC 157� SA 166� N 174� I
4-octyloxy-2,3-difluorophenyl p-hexylbenzoate
4-octyloxy-2,3-difluorophenyl p-heptylbenzoate
4-octyloxy-2,3-difluorophenyl p-octylbenzoate
4-octyloxy-2,3-difluorophenyl p-nonylbenzoate
4-octyloxy-2,3-difluorophenyl p-hexyloxybenzoate
4-octyloxy-2,3-difluorophenyl p-heptyloxybenzoate, C 45� N 53� I
4-octyloxy-2,3-difluorophenyl p-octyloxybenzoate, C 53� SC (39�) N 59.8� I
4-octyloxy-2,3-difluorophenyl p-nonyloxybenzoate, C 53.6� SC (49�) N 59.3� I
4-octyloxy-2,3-difluorophenyl trans-4-pentylcyclohexylcarboxylate, C 30� N 60� I
4-octyloxy-2,3-difluorophenyl trans,trans-4'-pentylbicyclohexyl-4-ylcarboxylate, C 58� SC (38�) SA 167� N 182.5� I
4-octyloxy-2,3-difluorophenyl 4-(trans-4-pentylcyclohexyl)benzoate, C 62� SC 63� SA 100� N 152.2� I
2,3-difluoro-4-nonyloxyphenyl p-(4-heptyloxy-3-fluorophenyl)benzoate
2,3-difluoro-4-nonyloxyphenyl p-(4-octyloxy-3-fluorophenyl)benzoate
2,3-difluoro-4-nonyloxyphenyl p-(4-nonyloxy-3-fluorophenyl)benzoate
2,3-difluoro-4-nonyloxyphenyl p-(4-decyloxy-3-fluorophenyl)benzoate
2,3-difluoro-4-decyloxyphenyl p-(4-heptyloxy-3-fluorophenyl)benzoate
2,3-difluoro-4-decyloxyphenyl p-(4-octyloxy-3-fluorophenyl)benzoate
2,3-difluoro-4-decyloxyphenyl p-(4-nonyloxy-3-fluorophenyl)benzoate
2,3-difluoro-4-decyloxyphenyl p-(4-decyloxy-3-fluorophenyl)benzoate
1 mol of 2,3-difluorophenol is dissolved in 2 l of 10% sodium hydroxide solution, and a saturated aqueous solution of potassium peroxodisulphate is added dropwise at 20� over the course of 3-4 hours. After the solution has been left to stand overnight, it is slightly acidified (pH 3-4), and unreacted starting material is extracted with ether. The aqueous phase is neutralized using sodium hydrogen carbonate and evaporated to dryness in vacuo. 2,3-difluoro-4-hydroxyphenylpotassium sulphate is dissolved out of the residue using 90% ethanol, and the alcohol is evaporated.
14 g of benzyl chloride are added dropwise with stirring and refluxing to 25 g of the crude product (˜0.1 mol) in aqueous-alcoholic sodium hydroxide solution (7 g of NaOH in 100 ml of 50% alcohol). The reaction is left to continue for 2 hours, and the mixture is slightly acidified using hydrochloric acid and heated for a further 2 hours. After cooling, 4-benzyloxy-2,3-difluorophenol is extracted and distilled after the solvent has been stripped off.
Monoalkyl ethers of 2,3-difluorohydroquinone are obtained analogously by reacting 2,3-difluoro-4-hydroxyphenylpotassium sulphate with alkyl bromides and sulphates.
0.1 mol of 2,3-difluoro-4-benzyloxyphenol are esterified using 0.1 mol of pyridine and 0.1 mol of 4-ethoxybenzoyl chloride in toluene, the resultant ester is isolated, the benzyl ether is subsequently cleaved hydrogenolytically using palladium/charcoal as catalyst.
2,3-Difluoro-4-butyryloxyphenyl 4-ethoxybenzoate is obtained by esterification of the free hydroxyl group using butyric acid/dicyclohexylcarbodiimide.
2,3-Difluoro-4-octanoyloxyphenyl 2-fluoro-4-(5-hexylpyrimidin-2-yl)benzoate is obtained analogously to Example 4 by esterification of 2,3-difluoro-4-benzyloxyphenol using 2-fluoro-4-(5-hexylpyrimidin-2-yl)benzoic acid (prepared by hydrolysis of the nitrile via the imidoester) and dicyclohexylcarbodiimide, hydrogenolytic cleavage of the benzyl ether and reesterification using octanoic acid.
0.1 mol of 2,3-difluoro-4-(trans-4-pentylcyclohexyl)methoxyphenol, 0.11 mol of butyl bromide and 0.11 mol of potassium carbonate are heated for 16 hours at 100� in 100 ml of dimethylformamide (DMF). After cooling, the inorganic salts are filtered off with suction, the filtrate is concentrated, and water is added. 1-butyloxy-2,3-difluoro-4-(trans-4-pentylcyclohexyl)methoxybenzene is obtained by extraction with dichloromethane.
The following are prepared analogously:
1-ethoxy-2,3-difluoro-4-(trans-4-pentylcyclohexyl)methoxybenzene, C 38� N (0�) I
1-ethoxy-2,3-difluoro-4-[trans-4-(trans-4-propylcyclohexyl)-cyclohexyl]methoxybenzene, C 63� N 153� I.
1-[trans-4-(trans-4-propylcyclohexyl)cyclohexylmethoxy]-2,3-difluoro-4-(trans-4-pentylcyclohexylmethoxy)benzene is obtained by the procedure of Example 6 from 0.1 mol of 2,3-difluoro-4-(trans-4-pentylcyclohexyl)methoxyphenol, 0.1 mol of trans-4-(trans-4-propylcyclohexyl)cyclohexylmethyl iodide and 0.1 mol of potassium carbonate.
1 mol of 2,3-difluorophenol is dissolved in 1 l of 10% sodium hydroxide solution, and a saturated aqueous solution of 1.1 mol of potassium peroxodisulphate is added dropwise over the course of 4 hours with ice cooling. During this addition, the temperature must not exceed 20o The mixture is stirred overnight at room temperature and neutralized using hydrochloric acid, and unreacted starting material is extracted with ether. 3 1 of toluene and 2 mol of sodium sulphite are added to the aqueous phase, and the mixture is strongly acidified using 1 1 of concentrated hydrochloric acid and refluxed for 20 minutes. After cooling, the toluene layer is separated off, the aqueous phase is extracted with ether in a perforator, and 2,3-difluorohydroquinone is obtained by evaporating the combined toluene and ether extracts.
0.05 mol of 2,3-difluorohydroquinone and 0.1 mol of pyridine are dissolved in 100 ml of toluene. 0.1 mol of trans-4-butylcyclohexanecarbonyl chloride is added dropwise at 80�, and the mixture is stirred for a further 3 hours. Customary work-up gives 2,3-difluoro-1,4-bis(trans-4-butylcyclohexylcarbonyloxy)benzene.
The following are prepared analogously:
2,3-difluoro-1,4-bis-(trans-4-pentylcyclohexylcarbonyloxy)benzene, C 87� N 208� I
2,3-difluoro-1,4-bis-(trans-4-octylcyclohexylcarbonyloxy)benzene, C 80� SF 94� SI 105� SC 124� N 176� I
Analogously to Example 4, 2,3-difluoro-1-(trans-4-propylcyclohexanoyloxy)-4-(trans-4-pentylcyclohexanoyloxy)benzene is obtained by reaction of 2,3-difluoro-4-benzyloxyphenol with trans-4-propylcyclohexanecarbonyl chloride/pyridine, hydrogenolytic cleavage of the benzyl ether and re-esterification using trans-4-pentylcyclohexanecarboxylic acid/dicyclohexylcarbodiimide in the presence of 4-dimethylaminopyridine.
The following examples relate to liquid-crystalline phases containing at least one compound according to the invention:
A liquid-crystalline phase comprising
6% of 4-octyloxyphenyl 4-decyloxybenzoate,
9% of 4-nonyloxyphenyl 4-decyloxybenzoate,
14% of 4-decyloxyphenyl 4-decyloxybenzoate,
5% of 2,3-difluoro-4-octyloxyphenyl 4-octyloxybenzoate
7% of 2,3-difluoro-4-octyloxyphenyl 4-decyloxybenzoate
9% of 2,3-difluoro-4-decyloxyphenyl 4-decyloxybenzoate
4% of 2,3-difluoro-4-nonanoyloxyphenyl 4-octyloxybenzoate
10% of 4'-pentyloxybiphenyl-4-yl 4-octyloxybenzoate
8% of 4'-heptyloxybiphenyl-4-yl 4-octyloxybenzoate
17% of r-1-cyano-cis-4-(4'-octyloxybiphenyl-4-yl)-1-octylcyclohexane and
11% of chiral p-(5-heptylpyrimidin-2-yl)phenyl 2-chloro-3-methylbutyrate
exhibits Sc * 62 SA 68 Ch 81 I and a spontaneous polarization of 13 nC/cm2 at room temperature.
A liquid-crystalline phase comprising
8% of 2-p-octyloxyphenyl-5-octylpyrimidine
10% of 2-p-nonyloxyphenyl-5-octylpyrimidine
12% of 2-p-octyloxyphhase comprising imidine
20% of 2-p-nonyloxyphenyl-5-nonylpyrimidine
7% of 2,3-difluoro-4-decyloxyphenyl 4-decyloxybenzoate
7% of 2,3-difluoro-4-octyloxyphenyl 4-decyloxybenzoate
9% of 2-(p-heptylphenyl)-5-(p-hexyloxyphenyl)-1,3,4-thiadiazole
9% of 2-(p-heptylphenyl)-5-(p-octyloxyphenyl)-1,3,4-thiadiazole
8% of 2,3-difluoro-4-octanoyloxyphenyl 4-(5-hexylpyrimidin-2-yl)-2-fluorobenzoate and
10% of chiral isopropyl 2-[p-(p-decyloxyphenyl)phenoxy]propionate
exhibits Sc * 58 SA and a spontaneous polarization of 11 nC/cm2 at room temperature.
A nematic liquid-crystalline phase comprising
7% of 2-p-cyanophenyl-5-propyl-13-dioxane,
7% of 2-p-cyanophenyl-5-butyl-1,3-dioxane,
6% of 2-p-cyanophenyl-5-pentyl-1,3-dioxane,
10% of trans-1-p-propylphenyl-4-pentylcyclohexane
8% of 4-cyano-4'-(trans-4-pentylcyclohexyl)biphenyl,
6% of 4-ethyl-4'-(trans-4-pentylcyclohexyl)biphenyl,
4% of 4-ethyl-4'-(trans-4-propylcyclohexyl)biphenyl,
5% of 2-p-pentyloxyphenyl-5-hexylpyrimidine,
6% of 2-p-heptyloxyphenyl-5-hexylpyrimidine,
5% of 2-p-methoxyphenyl-5-hexylpyrimidine,
8% of 2-p-heptyloxyphenyl-5-heptylpyrimidine,
8% of 2-p-nonyloxyphenyl-5-heptylpyrimidine,
4% of p-methoxyphenyl trans-4-propylcyclohexanecarboxylate
7% of 2,3-difluoro-4-ethoxyphenyl trans-4-pentylcyclohexanoate,
5% of 2,3-difluoro-4-ethoxyphenyl trans-4-(trans-4-propylcyclohexyl)cyclohexanoate and
4% of p-trans-4-propylcyclohexyphenyl butyrate is distinguished by good multiplex properties.
A liquid-crystalline phase comprising 12.5% of 4-heptyloxy-2,3-difluorophenyl 4'-octyloxybiphenyl- 4-ylcarboxylate
14.2% of 4-heptyloxy-2,3-difluorophenyl 4-octyloxybenzoate
12.5% of 4-heptyl-2-fluorophenyl 4'-heptyloxybiphenyl-4-ylcarboxylate
12.5% of 4-heptyl-2-fluorophenyl 4'-heptyloxy-2'-fluorobiphenyl-4-ylcarboxylate
14.2% of 4-octyloxy-3-fluorophenyl 4-octyloxybenzoate
12.34% of 4-pentyl-2-fluorophenyl 4-octyloxybenzoate
14.24% of 4-octyloxy-3-fluorophenyl 4-heptyloxybenzoate
5.04% of chiral 4-(2-methylbutyl)-phenyl 4'-octylbiphenyl-4-ylcarboxylate and
2.48% of chiral 1-cyano-2-methylpropyl 4'-octyloxybiphenyl-4-ylcarboxylate
exhibits SC * 66.4� SA 73� Ch 97.2� I and a spontaneous polarization of 9 nC/cm2 at 30� C.
A liquid-crystalline phase comprising
16.87% of 4-heptyl-2-fluorophenyl 4'-heptyloxybiphenyl-4-ylcarboxylate
16.87% of 4-heptyl-2-fluorophenyl 4,-heptyloxy-2'-fluorobiphenyl-4-ylcarboxylate
16.87% of 4-octyl-2-fluorophenyl 4,-octyloxy-2',3'-difluorobiphenyl-4-ylcarboxylate
14% of 4-octyloxy-3-fluorophenyl 4-octyloxybenzoate
14% of 4-hexyloxy-3-fluorophenyl 4-octyloxybenzoate
10% of 4-octyloxy-2-fluorophenyl 4-pentylbenzoate
9% of 4-heptyl-3-fluorophenyl 4'-octyloxy-2',3'-difluorobiphenyl-4-ylcarboxylate and
2.4% of chiral 1-cyano-2-methylpropyl 4'-octyloxy-biphenyl-4-ylcarboxylate
exhibits SC * 71.8� SA 81� Ch 103.8� I and a high spontaneous polarization.
|Cited Patent
|Filing date
|Publication date
|Sep 12, 1979
|Jul 21, 1981
|Chisso Corporation
|Liquid crystal 2,3-dicyano-hydroquinone derivatives
|Sep 30, 1980
|Dec 28, 1982
|Bch Chemicals Limited
|Intermediates useful in the production of liquid crystal compounds
|Jun 30, 1980
|Jan 11, 1983
|Bbc, Brown, Boveri & Company, Ltd.
|Anisotropic compounds with negative or positive DC-anisotropy and low optical anisotropy
|Nov 10, 1981
|Nov 15, 1983
|Merck Patent Gesellschaft Mit Beschrankter Haftung
|Liquid crystalline fluorine-containing cyclohexylbiphenyls and dielectrics and electro-optical display elements based thereon
|Jan 25, 1983
|Apr 30, 1985
|Merck Patent Gesellschaft Mit Beschrankter Haftung
|Anisotropic compounds and liquid crystal mixtures
|Sep 21, 1983
|Oct 8, 1985
|Merck Patent Gesellschaft Mit Beschrankter Haftung
|Liquid crystalline fluorine-containing cyclohexylbiphenyls and dielectrics and electro-optical display elements based thereon
|Mar 14, 1983
|Nov 5, 1985
|Merck Patent Gesellschaft Mit Beschrankter Haftung
|Polyhalogenoaromatic compounds for liquid crystal compositions
|May 11, 1984
|Jul 29, 1986
|The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland
|Disubstituted ethanes and their use in liquid crystal materials and devices
|May 14, 1984
|Aug 19, 1986
|Merck Patent Gesellschaft Mit Beschrankter Haftung
|Jun 26, 1985
|Nov 11, 1986
|Hoffmann-La Roche Inc.
|Novel liquid crystal mixtures
|Aug 6, 1984
|Jan 20, 1987
|Merck Patent Gesellschaft Mit Beschrankter Haftung
|Nematic compounds
|Jan 17, 1985
|Apr 21, 1987
|Merck Patent Gesellschaft Mit Beschrankter Haftung
|Ethane derivatives
|Nov 20, 1984
|May 12, 1987
|E. Merck
|Liquid crystal compounds
|Apr 13, 1985
|Dec 1, 1987
|Merck Patent Gesellschaft Mit Beschrankter Haftung
|Anisotropic compounds and liquid crystal mixtures therewith
|May 21, 1986
|Feb 9, 1988
|Merck Patent Gesellschaft Mit Beschrankter Haftung
|Aug 18, 1986
|Jun 28, 1988
|The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland
|Secondary alcohol derivatives for use in liquid crystal materials and devices
|Feb 24, 1986
|Oct 11, 1988
|Merck Patent Gesellschaft Mit Beschrankter Haftung
|Pyrimidine derivatives
|May 16, 1986
|Apr 11, 1989
|Merck Patent Gesellschaft Mit Beschrankter Haftung
|Nitrogen-containing heterocyclic esters
|Apr 23, 1986
|May 30, 1989
|Merck Patent Gesellschaft Mit Beschrankter Haftung
|Nitrogen-containing heterocycles
|Feb 3, 1988
|Oct 17, 1989
|Veb Werk Fuer Fernsehelektronik Im Veb Kombinat Mikroelektronik
|Ferroelectric liquid crystals
|Mar 9, 1989
|Jan 30, 1990
|Merck Patent Gesellschaft Mit Beschrankter Haftung
|2,3-difluorophenol derivatives
|Feb 22, 1987
|Mar 27, 1990
|The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland
|Alkylbyphenyloxyacetic acid esters and their use in smectic liquid crystal materials
|Dec 13, 1988
|May 15, 1990
|Hoffmann-La Roche Inc.
|Liquid crystalline esters
|Mar 9, 1989
|May 15, 1990
|Merck Patent Gesellschaft Mit Beschrankter Haftung
|Derivatives of 4-cyano-2,3-difluorophenol
|May 26, 1987
|Jan 22, 1991
|Merck Patent Gesellschaft Mit Beschrankter Haftung
|Cyclohexane derivatives
|Feb 27, 1989
|Feb 11, 1992
|Merck Patent Gesellschaft mit beschrankter Hafung
|Process for the preparation of 2,3-difluorobenzenes
|Jun 18, 1974
|Jan 23, 1975
|Werk Fernsehelektronik Veb
|Nematic liq. crystal substances for electro optical assemblies - modulation of transmitted or incident light using 4-n-alkylcyclohexanecarboxylic acid-4'-substd. phenyl esters
|Oct 1, 1979
|Apr 2, 1981
|Bbc Brown Boveri & Cie
|Anisotropic cpds. with three aromatic rings and polarising side gps. - have high negative dielectric constant anisotropy, useful in liquid crystal compsn.
|Oct 3, 1981
|May 19, 1982
|MERCK PATENT GmbH
|Cyclohexyl-biphenyl derivatives that contain fluor, dielectrics containing them and electro-optical indicating element
|Dec 16, 1982
|Jul 27, 1983
|MERCK PATENT GmbH
|Liquid crystal mixtures
|Jul 17, 1984
|Feb 27, 1985
|MERCK PATENT GmbH
|Nematic compounds
|Sep 9, 1987
|Mar 24, 1988
|MERCK Patent Gesellschaft mit beschr�nkter Haftung
|Liquid crystal phases for electro-optic display elements based on the ecb effect
|Citing Patent
|Filing date
|Publication date
|Nov 22, 1995
|Aug 11, 1998
|U.S. Philips Corporation
|Cholesteric polarizer and the manufacture thereof
|Jun 30, 1995
|Aug 25, 1998
|Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Gt. Britain & N. Ireland Of Defence Evaluation And Research Agency
|Liquid crystal compounds, mixtures and devices
|Mar 27, 1997
|Feb 20, 2001
|Chisso Corporation
|Liquid crystal compounds, liquid crystal compostions containing the compounds, and liquid crystal display devices made by using the compositions
|Mar 13, 1998
|Jun 19, 2001
|Merck Patent Gesellschaft Mit Beschrankter Haftung
|Electro-optical liquid-crystal display
|Jun 19, 2000
|Nov 20, 2001
|Chisso Corporation
|Liquid crystalline compound, liquid crystal composition comprising the liquid crystal-line compound, and liquid crystal display device using the liquid crystal composition
|Feb 27, 2006
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|Dainippon Ink And Chemicals, Inc.
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|Jun 20, 2003
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|Griffin Nigel Dennis
|Polycrystalline diamond partially depleted of catalyzing material
|Feb 27, 2006
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|Dainippon Ink And Chemicals, Inc.
|Difluorobenzene derivative and nematic liquid crystal composition using the same
|Mar 15, 2006
|Aug 13, 2009
|Dainippon Ink And Chemicals, Inc.
|Difluorobenzene derivative and nematic liquid crystal composition using the same
|Apr 26, 2004
|Nov 2, 2005
|AZ Electronic Materials (Germany) GmbH
|Chiral smectic liquid crystal mixture
|Apr 26, 2005
|Nov 3, 2005
|Az Electronic Materials (Germany) Gmbh
|Chiral smectic liquid crystal mixture
|U.S. Classification
|252/299.63, 252/299.67, 560/59, 568/645, 568/656, 560/63, 568/649, 560/62
|International Classification
|Cooperative Classification
|European Classification
|Mar 14, 1997
|Fee payment
Year of fee payment: 4
|Mar 8, 2001
|Fee payment
Year of fee payment: 8
|Mar 2, 2005
|Fee payment
Year of fee payment: 12


text:
Following the journey of a dachshund as it is shuffled from owner to owner, Todd Solondz's Wiener-Dog is one of his sharpest visions of futility.
Following the journey of a dachshund as it is shuffled from owner to owner, Todd Solondz's Wiener-Dog is one of his sharpest visions of futility.
It's just dull and hollow—a massive waste of time and money.
"The Ballad of Narayama" is a Japanese film of great beauty and elegant artifice, telling a story of startling cruelty. What a space it opens…
Patrice Leconte's "Monsieur Hire" is a tragedy about loneliness and erotomania, told about two solitary people who have nothing else in common. It involves a…
Ken Loach's "I, Daniel Blake" wins the Palme d'Or at the 69th Cannes Film Festival.
Barbara Scharres on the cats of Cannes 2016.
An article about Roger Ebert's reviews getting republished in the Chicago Sun-Times.
Chaz Ebert remembers the late Paul Cox and shares an article about Cox speaking with students at the 2009 Cannes Film Festival.
A report by FFC Seongyong Cho about Andrew Ahn's "Spa Night," which recently played the Jeonju International Film Festival.
FFC Gerardo Valero returns to "The Shawshank Redemption" to investigate how it remains the #1 film on IMDb.
A book review of "The Art & Making of Independence Day: Resurgence."
An interview with the directors of "Swiss Army Man."
Paul Devlin's "SlamNation" is a documentary about the 1996 National Poetry Slam, held in Portland, Ore., with 27 teams in the competition. The rules are simple: Four members to a team, every member must be a writer as well as a performer, no music, no props, no animal acts. There is a penalty for any poem that goes longer than three minutes. The judges are chosen from the audience. The performers are mostly dressed as if they're about to fix a leak in the basement.
Slams are nothing if not democratic. They are the only sport I'm aware of where the teams from Berwyn and San Francisco compete on the same field. (In 1996, Berwyn actually placed in the final four, led by its star, a slammer named Daniel Ferri, whose poem fiercely defends his baldness.) The documentary follows the New York team, which fielded four first-timers, including Saul Williams, who also stars in the fiction film "Slam," and Mums the Schemer, who plays the character Poet on the HBO prison drama "Oz." In evaluating the poetic content of the slams, one is tempted to take easy shots. (Poetry slams are to poetry as military music is to music?) Most of the material exists halfway between rap music and Vachel Lindsay. Slams are essentially performance art, not literary art, and there is a shot of a New York book editor, sighing at his stack of slam manuscripts and observing that sometimes the poems don't translate well to the printed page.
Maybe that's because "SlamNation," covering three semifinal rounds and the finals, inevitably focuses on the competition rather than the work. I have had one personal experience of slam-style poetry, and it was truly unforgettable.
Last April, at the annual meeting of the American Society of Newspaper Editors in Washington, D.C., the luncheon speaker was Secretary of State Madeleine Albright, who rattled off her speech as quickly as she could and hurried from the dais. Then the society's chairman called on a young woman to "give us one of your poems." This was Patricia Smith, a friend of mine from her Chicago days, then a columnist for the Boston Globe. She performed a poem about a visit to a grade school class at which she asked, "How many of you know some dead people?" Almost every hand went up, she said, because all of these inner-city children knew dead people--many of them dead from drugs and gunshots. At the end a little girl thanked her for saying it was all right to know dead people. The girl was speaking of her own murdered mother.
This summary fails to capture the impact of Smith's poem, which surprised me to tears. I looked around the room and thought I had rarely seen so few words have such a strong impact.
Pat Smith of course was soon to get publicity of a different sort, when her paper accepted her resignation after she confirmed that some details of her columns had been made up. Making things up is not what a journalist is supposed to do, but it is what a poet is supposed to do. Seeing Smith again in "SlamNation," as a member of the Boston team, I was reminded of the power of her words. She can see life and touch readers as few writers can. That is her vocation. Fiction and poetry exist to reach a different kind of truth. Maybe she had no business dealing with facts in the first place.
As for the other performers, I am prepared to believe that in context, uncut, seen as they should be, some of them have the same power. Others are basically soapbox orators with a new forum. In the cheerful anarchy of poetry slams, there is room for many styles. As a slammer named Jack McCarthy from Boston says, "You have to write one poem that everyone agrees is a poem. That qualifies you for your poetic license. After that, if you say it's a poem, it's a poem."
The new "Ghostbusters" film brings a battle between distorted nostalgia and the power of a child's imagination.
This message came to me from a reader named Peter Svensland. He and a fr...
FFC Gerardo Valero returns to "The Shawshank Redemption" to investigate how it remains the #1 film on IMDb.

subset: commoncrawl


text:
researcher using digital tablet in lab
Credit: CZQS2000 / STS
Creative #: 167903076
License type: Royalty-freeRoyalty-free pricing is based solely on the size of the product you need, not the specific use. You don't have to pay any additional royalties on a use-by-use basis. Once you license a royalty-free product, you may use it multiple times for multiple projects without paying additional fees. (Pornographic, defamatory, libelous or otherwise unlawful use of any image is, of course, prohibited.)
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Researcher Using Digital Tablet In Lab Stock Photo20-24 Years,Adult,Adults Only,Brown Hair,China - East Asia,Chinese Ethnicity,Color Image,Digital Tablet,Expertise,Eyeglasses,Holding,Horizontal,Indoors,Lab Coat,Laboratory,One Man Only,One Person,One Young Man Only,Only Men,People,Photography,Research,Science,Scientist,Selective Focus,Skill,Standing,Surgical Glove,Technology,Waist Up,Young AdultPhotographer CZQS2000 / STSCollection: Stockbyte ChuXiaolu


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Latest on retirement »
Government doctors in Odisha have raised objection to the Centre's decision to raise the retirement age of medical professionals to 65.
"As per plan, the complainant gave the officials the bribe money in packets with marked currency notes.
Lionel Messi's retirement from international football may have come as a shock to his many admirers but in hindsight there were plenty of clues that the Argentina superstar might call time on his career with the 'Albiceleste' sooner rather than later
Kruti, Priya and Asha recently retired after putting in over 20 years of service that included duty during communally sensitive rathyatra, bundobust during rioting and patrolling in rural areas in times of unrest.
Popat Sutreja was forcibly retired in 2014 from the post of deputy district manager in Gujarat State Civil Supply Corporation Ltd on the ground that he was not fit to work due to cancer.
Anandiben Patel has categorically said many times that she'd remain at the helm of the state government till her term is over in 2017, rumours of her chances of resigning continue to surface with regularity.
The retirement age of government doctors will be raised to 62 years, and that of the teaching faculty at Goa medical college (GMC) and hospital, Bambolim, to 65 years, chief minister Laxmikant Parsekar announced on Monday.
Here's why increasing the retirement age of doctors in govt service to 65 will help beat the shortage.
A septuagenarian woman died on Wednesday afternoon in a motor vehicle accident that occurred at Pulimoodu in the heart of the city.
Speed News
Justice C R Kumaraswamy,a senior judge of the Karnataka high court retired from service on Monday. In January, Justice Kumaraswmy was appointed as the special bench to hear the appeals filed by Tamil Nadu Chief Minister J Jayalalithaa and three others in relation to multi-crore disproportionate assets case. On May 11,2015, all the four were acquitted following a three month long hearing.
The state cabinet has approved the proposal to increase the retirement age of medical officers in the state to 60 years. Download the official TIMES NOW mobile app. Visit web.timesnowmobile.com or give a missed call on 1800 4190 300. Stay updated, stay ahead.
Kerala Chief Secretary E K Bharathbhooshan retires from service. Jiji Thomson IAS takes over as new chief secretary of the state. -
A group of 22 railway officials working with the Ranchi division retired on Friday.
Justice S Rajeswaran of the Madras high court retires from service on Friday. Farewell at 3.15pm on Friday.
Madras high court asks Villupuram division of State Transport Corporation to pay retirement benefits of conductor R Damodaran on July 30, a day before his retirement.
Andhra Pradesh legislature passed a bill to increase retirement age of government employees from 58 to 60 years. This will come into effect immediately.
Former world number one Dinara Safina, whose career was wrecked by a series of back injuries, formally announced her retirement in a ceremony at the Madrid Open on Sunday. Watch election news on TIMES NOW No.1 Eng News Channel of India. Do not miss it till Result Day May 16
Justice A Arumughaswamy of the Madras high court is to retire from service on Friday. His retirement will bring the number of judges in the court down to 44, as against the sanctioned vacancies of 60.
Madhya Pradesh Textile Mills Association (MPTMA) has opposed state government's move to increase retirement age of industrial workers to 60, as against the currently existing mark of 58. Association feels that it will stall chances of young aspirants from getting jobs in the industry. Apart from MPTMA, the Association has written to the state government in this connection. The state government's move has also been opposed by Dewas Industries Association and the MP unit of All India Manufacturing Association (AIMA).
Former Brazil and Barcelona star Rivaldo is officially retiring after a 24-year career that he says was built ``upon a miracle'' that allowed him to overcome financial challenges and disappointments.
The doctors who are retiring this month from the health service will get an extension of six months since the government is unable to fill up the vacancies. The government has decided to provide placements for all the candidates in the PSC list in the health service.
Devidas Thomre, a retired teacher, was robbed of his valuables worth Rs 1.67 lakhs, including cash Rs 5,000, while travelling in an auto-rickshaw along with wife on Tuesday. Thomre couple, native of Wardha district, had come to attend a marriage at their relative&rsquos place at Ishwar Nagar in Sakkardara.
Russian skating icon Yevgeny Plushenko dramatically announced his retirement on Thursday after withdrawing from the Winter Olympics with a back injury, leaving a nation stunned and questions asked over his original selection.
Justice H N Nagamohan Das, who served as a Judge of the Karnataka high court for nine years and four months, retired on Tuesday. Farewell functions were organized both by the high court as well Advocates Association of Bangalore for the retiring Judge.


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Gaurishankar Agrawal elected Speaker of Chhattisgarh Assembly
Raipur: BJP leader Gaurishankar Agrawal was elected as Speaker of the new Chhattisgarh Legislative Assembly, the first session of which began on Monday.
Agrawal, a two-time MLA, was the only candidate to file nomination for the post and was unanimously elected.
Chief Minister Raman Singh, Leader of Opposition T S Singhdeo and other legislators were administered oath by pro-tem Speaker Satyanarayan Sharma during the beginning of the opening day.
Later, the Speaker was elected.
In his first address to the House, Speaker Agarwal said with the help of each member of the Assembly, he would try to fulfil the expectations of 2.5 crore people of the state.
Immediately after his election to the post, Raman Singh and Singhdeo congratulated him. Singh also congratulated elected members of the House.
The Raman Singh-led BJP registered a victory for the third straight time by winning 49 of the 90 seats in the recently-concluded Chhattisgarh Assembly election.
The Congress on the other hand managed to win 39 seats. Rest of the two seats went to BSP and an independent each.
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Mic Handz, who appeared on DJ J-Ronin's Freestyle Files vol. 2 with the above track, shoots a video for the freestyle under the direction of The Last American B-Boy. For those who may be looking for a mixtape in similar vein to Tony Toca's classic 50 MC's / Power Cypha, look no further than Ronin's Freestyle Files vol. 2 and stop sleeping!
Mic Handz - Handz of Mischief (Video)
Vee Tha Rula - "Gang" f. Kid Ink (Video)
Tha Rula revisits From The Jump to put on for his crew.
RJ - "30 In The Middle" (Video)
Off the Cali spitter's OMMIO 3, out now.
Cam'ron – "Oh Yeah" f. Juelz Santana
Guess who's back.
Free Ackrite - "Jiggin" (Video)
Off Tha Committee re's self-titled project, out now.
Joey Purp - "Girls @" f. Chance the Rapper
Off the Chicago emcee's upcoming iiiDrops project.


text:
HAWKINS, Texas (AP) — A newly elected East Texas mayor has been accused of threatening to ticket and fine a woman $500 daily in a messy yard dispute.
Hawkins Mayor William Rogers was arrested Monday on a misdemeanor official oppression charge and freed on $1,000 bond.
Fire Marshal Eileen Frazier says the mayor is not authorized to write tickets or issue fines.
Rogers, who was elected in May, denied wrongdoing. He didn't immediately returned messages Tuesday.
An arrest affidavit says Rogers on July 10 stopped at a house and told a resident she must clean up her yard or he would ticket and fine her. Code enforcement officials later said the grass did not violate city rules.
Hawkins is a town of about 1,300, located 90 miles east of Dallas.
(© Copyright 2014 The Associated Press. All Rights Reserved. This material may not be published, broadcast, rewritten or redistributed.)
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Home →
→ Other Therapies
| Other Therapies
"Yawning Yoga: A Goodnight Book for a Good Night's Sleep" by Laurie Jordan helps children establish a bedtime routine that incorporates yoga poses while also allowing parents to positively interact and bond with their kids before bedtime.
Holding yoga poses helps both kids and parents increase the quality of sleep and helps them to relax because it transfers focus from the stresses of the day to focus on yoga postures, relaxation techniques and breathing.
The Greenwich-based author, who is also the director of kids programming at Kaia Yoga in Greenwich and Westport, created "Yawning Yoga" to help destress and destimulate children. The book provides explanations of each technique using Dr. Seuss-like prose that are accompanied by vibrant illustrations.
An excerpt from Yawning Yoga:
Squeeze your finger, your nose, your eyes, and your toes.HUG everything tight, tight, tight!Then let everything goand feel everything flowso your body feels light, light, light.
source: Yawning Yoga: A Goodnight Book for a Good Night's Sleep by Laurie Jordan
Learn more about Yawning Yoga at yawningyoga.com.
What is Applied Behavior Analysis?
Four-Legged Friends Aid Kids With Special Needs
How Do I Get My Picky Eater to Try New Foods?
Party Planning
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Camp Guide
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Family Health Guide
Special Needs Guide
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Relish in the opportunity to show off your clean and clutter-free home with these six tips for organizing and getting rid of the clutter in your home.
Let NY Kids Club help you plan your child's next birthday party.
Copyright 2016 | All Rights
Reserved | Davler Media
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Written on: 05/07/2013
Been looking for cars on Gumtree (amongst others)and not for the first time found that browsing the page proved impossible - jumps and jerks up and down and is so slow and then moves me from the page i'm on to something completely obscure. So i've given up with probably the worst site on the whole net. It's the people who post ads i feel sorry for though.
As rated by our community of reviewers
" Kept up to date " Read More
" I CANT SELL ON PRELOVED " Read More
" Pharme195 " Read More
" Easy to navigate and quite decent adverts, however many adverts wer... " Read More
" My child found this website and we thought the cell phone deals wer... " Read More
Written by MammaDiva3


text:
Listen to Orlando Benefit Song Featuring Kristen Bell, Lin-Manuel Miranda, Idina Menzel and More
- 08:33 PM, Jun 21
Eighteen year-old Helen Memel (Carla Juri) likes to skateboard, masturbate with vegetables and thinks that body hygiene is greatly overrated. Struggling with her parents divorce, she spends her time experimenting and breaking one social taboo after the other with her best friend, Corinna (Marlen Kruse). When a shaving accident lands her in the hospital, she sees it as a way to reconcile her parents and forms an unlikely bond with her male nurse, Robin (Christoph Letkowski). "Wetlands" is an unapologetically vulgar coming-of-age tale about divorce, first love and anal fissures.


text:
Today's Devotional
Always ThereDo you believe that the Lord is always with you?
Let's Make ItFacebook official!
Your Enemy is Real Part 3 Video 2 of 2
Embed ccfou 3038 views 2008-03-17T00:00:00 The Book Of Revelation--->>>Your Enemy is Real Part 3 Video 2 of 2
Pastor: Tom Sigley
Pastor: Tom Sigley


text:
Northern Territory
Tourists pitch tents in cemetery to save cash
Tight-fisted tourists have been using a cemetery as their campground in a desperate bid to save cash.
A Northern Territory town's cemetery is now sporting an unusual feature among its headstones and flowers – "no camping" signs, the Northern Territory News reports.
While Darwin has been struggling with its usual backpacker brigade blocking up space by popular beach locales, Katherine has been copping irreverent campers setting up in the local cemetery.
It has had to take the unusual step of erecting the signs to officially confirm it's not OK to pull up in your caravan and have a wash.
Katherine mayor Anne Shepherd said there had been a few tourists camping there during the dry season.
"They camp in an area where the ablution block is," she said.
The bemused mayor said she wasn't sure why people would choose to sleep there to save money.
Thrifty campers take note: Katherine Town Council can fine you $50 for ignoring the signs and setting up for the night.
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text:
School Bus Retrofits 'Can Cut Emissions Up To 90%'
For between $9,000 and $15,000 each, older school buses can be fitted with tailpipe and crankcase filters that reduce soot emissions by up to 90 percent, according to an Environmental Defense Fund report.
This makes the old buses as clean as new ones for a fraction of the cost — a new bus costs between $75,000 and $80,000, EDF says.
In its new report, Review of Texas' Clean School Bus Programs: How Far Have We Come and What Is Still Left to Do?, EDF recommends solutions for lower diesel-emitting buses that can be applied to fleets across the US.
Diesel engines power most of the 480,000 buses that carry 24 million American children to school every day, EDF reports. According to the California Air Resource Board, school bus trips can increase children's daily exposure to black carbon up to 34 percent compared to passenger cars, and particle matter (PM) levels inside a school bus can be five to 10 times the levels outside the bus.
As of the 2010-2011 school year, about two-thirds of Texas's school buses were over six years old, emitting at least 10 times as much PM as newer buses. (Editor's note: EDF actually wrote that buses over six years old emit at least 10 times as much PM as "older buses," which we assume is an error. UPDATE, Nov. 28, 10:24 CST: EDF has now confirmed this should read "newer.")
This affects more than 700,000 children.
Texas has made progress with clean bus programs, however. Through the end of the 2011 calendar year, 7,068 buses were retrofitted, 700 buses were replaced and more than $38 million was spent on clean-fuel and idle-reduction projects, the report says.
In addition to replacing or retrofitting old buses, turning off engines when waiting can lower diesel emissions and save "countless" gallons of gas, EDF reports. When a bus remains idles for more than three minutes, emissions from the bus can increase more than 65 percent. By reducing idling, a 25-strong bus fleet can save thousands of dollars a year in fuel costs.
Under the Texas Clean School Bus Program, the Texas Commission on Environmental Quality is accepting applications for grants through Nov. 30. All public school districts and charter schools in Texas are eligible to apply for this grant, intended to reduce diesel emissions.
Additionally, EPA has launched a new rebate funding opportunity for school bus replacements under the Diesel Emissions Reduction Act. Applications will be accepted until Dec. 14.
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text:
The Power of Chanel - Fei Fei Sun dons Chanel Haute Couture for the dazzling June cover shoot from Harper's Bazaar Singapore. Taking to the Shanghai streets at night, Fei Fei poses for Gan's lens in the elegant stylings of fashion editor Kenneth Goh. … [Read more...]
Harper's Bazaar Singapore June 2011 Cover | Fei Fei Sun by Gan
Fei Fei Sun by Gan for Harper's Bazaar Singapore June 2011 … [Read more...]
Li Bing Bing for Harper's Bazaar Singapore October 2010 by Gan
Photographed by Gan, Chinese actress Li Bing Bing, covers the October edition of Harper's Bazaar Singapore wearing Dior and a smoldering gaze. Inside the magazine, Li dons a perfect mix of masculine and feminine looks styled by Kenneth Goh. … [Read more...]
Harper's Bazaar Singapore August 2010 | Song Kyunga by Gan
South Korean model, Song Kyunga, brings a sense of dark glamour to the August edition of Harper's Bazaar Singapore. Lensed by Gan and styled by Kenneth Goh, Song dons an array of ruffles, satin and lace from the likes of Dolce & Gabbana and KTZ in the multi-colored Dye Heart. … [Read more...]
Carmen Kass for Harper's Bazaar Singapore July 2010 by Gan
After a stunning cover for Harper's Bazaar Singapore July, Carmen Kass continues to strike gold with the luxe main editorial photographed by Gan. Inside the magazine, Carmen opens up about being one of the industry's top models and what really makes her happy. Styled by Windy Aulia in glam ensembles, the Estonian beauty dazzles in From Pawn to Queen. … [Read more...]


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"Such businesses gain a competitive edge by paying illegal alien workers low wages or otherwise exploiting them. These inspections are one of the most powerful tools the federal government has to ensure that businesses are complying with US employment ...more »
When law enforcement officers can't recognize signs of mental illness, it can lead to brutality and tragedy, say Southern California criminal defense lawyers of Lessem & Newstat, LLP. Ventura County criminal defense lawyer Joshua E. Newstat When ...more »
25 in a decision from Administrative Law Judge Gregory Z. Meyerson in Washington, DC Meyerson ordered the Texas-based operator of the hotel to stop doing certain things, including pressuring workers to decertify the union and suspending or disciplining ...more »
Visibly annoyed, Florida Department of Law Enforcement Commissioner Gerald Bailey told reporters Thursday that he is "offended" by critics' suggestions that his department's investigation of the governor's ...more »
The Complaint asserts violations of the federal securities laws against Jiangbo and its officers and directors for issuing false and misleading information to investors about the financial and business condition of the Company and its lack of internal ...more »
Law enforcement agencies and banking regulators acknowledge that there's no way to know how much money is being moved undetected across US borders through the cards — that's the point of money laundering, after all. But in a report late last year on ...more »


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Olympus SH-21
Billed as the ideal point-and-shoot camera for travellers, the Olympus SH-21 is designed for versatility: it's just about small enough to fit into your jacket or trouser pocket, features a 12.5x optical zoom equivalent to a 24-300mm lens, can record 1080p HD video and comes with a touchscreen that (theoretically, at least) boosts user-friendliness. It even charges via USB.
We've always been a little wary of touchscreens on cameras – there's the potential for changing settings by mistake – but the SH-21 pulls it off well. First, the screen isn't over-sensitive, and it takes a fairly firm touch to register. Second, the touch function is only used to tweak camera settings in iAuto mode, and then only if you open up the "live guide" option. The rest of the time, it fulfils a "touch to focus" role. Tap something on the screen, and the camera focuses on it, or focuses and automatically takes a shot if "touch shooting" is turned on.
A nice touch
The focus setting is useful, particularly if you want to lock on to a subject that isn't in the centre of the frame. It also combines with AF tracking so if you tap on a subject, which then moves, the camera will attempt to keep it in focus as long as it's in the frame.
Live Guide is a newbie-friendly way to change the brightness, colour saturation and colour tone of a shot using touch-controlled sliders. You get to watch the shot change through the screen's live view, which gives you a preview of the final photo. It's a valuable feature.
Aside from the touchy stuff, the SH-21 features a range of other shooting modes, including program for those who want control over settings, and "handheld starlight" for taking sharper photos in dim conditions. And, naturally, there's a full range of scene modes that optimise settings for shooting fireworks, sunsets, sporting events and other situations.
Picture quality
So on to image quality. While there's nothing awful about the 16-megapixel shots the SH-21 turns out, there's nothing particularly wow-worthy about them either.
Look closely at photos, even those at lower ISO settings, and there's greater visible noise compared to some rival cameras. This graininess isn't especially noticeable when photos are viewed on Facebook or similar – but if you're planning on blowing them up for large prints it's worth noting. You can also take automatic HDR shots, with the camera combining several exposures to show detail in both light and dark areas of an image - but these come off looking quite flat and unrealistic.
HD video quality is clear and sharp, and you can use the 12.5x zoom while filming, but despite the built-in anti-shake it doesn't look great when you pan quickly. A steady hand is an asset here.
The Olympus SH-21 is a versatile compact camera that combines a usefully large zoom range with a wide selection of shooting modes. The camera's touchscreen doesn't come off as a gimmick, and is genuinely useful at times.
However, if you're looking for a point-and-shoot that delivers squeaky clean shots, this isn't the camera for you: while snaps are acceptable at smaller sizes, there's too much grainy noise when compared to similarly priced cameras from the likes of Canon.
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Today's Devotional
John's QuestionWhat steps can you take to seek God's perspective in a current challenging situation?
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I am 18 years old wuz a pastors kid but not since my dad became songservice leader for my church. im a little worn out but god gives me the strength to continue living i love rock and rap and i Love JESUS!!!
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MMAWeekly Radio's May the 4th Be With You edition features interviews with Jake Ellenberger, and Tachi Palace fighters Efrain Escudero and Ian McCall.
Also listen to the top of the show for your chance to win a UFC 129 official program with Georges St-Pierre and Jake Shields.
Click here to continue reading MMAWeekly while listening to this podcast
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Tune in Wednesday, April 1, at 6 p.m. EST, for Knockout Radio LIVE! with UFC middleweight challenger Michael Bisping and Ian McCall, as well as the week in MMA news! read news >>
Check out Knockout Radio's podcast featuring UFC fighters Michael Bisping and Ian McCall, as well as remembering MMAWeekly co-founder Ryan Bennett. read news >>


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Gov. Snyder signs $28M in aid for Flint
He says the funding will provide immediate resources in Flint but is not the end of state assistance.
He says the funding will provide immediate resources in Flint but is not the end of state assistance.
Below are some alkaline food and beverage recipes can help your body to return your pH to normal and fight off disease.
One thing he's not lacking is confidence. In the interview, he said "none of the other guys will win."
There were no arrests, and it's not clear if Manziel has yet been questioned.
Cruz brushed off the fuss. "I will apologize to nobody for using every tool we can to encourage Iowa voters to come out and vote," he said.
A cold front setting up just to our west will approach the state this afternoon.
There is no word yet on her condition.
The victim was transported to Sidney & Lois Eskenazi Hospital in good condition.
Currently, police do not have a description of the suspect or suspects involved in the shooting.
Police are continuing to investigate the shooting.


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For flower delivery to Cordova, you can even look to Memphis florists, flower shops in Collierville, or florists in Germantown because our shops are real neighborhood florists. You can count on Bartlett florists and Millington flower shops to deliver fresh flowers right to the recipient's door.
Can we conceive what humanity would be if it did not know the flowers?- Maurice Maeterlinck
flowers really do intoxicate me.- Vita Sackville-West
Let me show youSweet smell of a delicate whisperBehind the vision of gardensGo and read of your lifeTiny ripping at the heartDrunk from a rose- Erica Caitlin Lee
Flowers... are a proud assertion that a ray of beauty outvalues all the utilities of the world. - Ralph Waldo Emerson
Find florists from nearby cities:
Summer is
You make Me Smile
Your Local florist will create a unique gift, floral arrangement or basket. Artfully designed, hand created and delivered! That's the local florist difference.
901-327-4433 | view map460 McLemore Ave Memphis, TN 38106-3008
Been Serving Our Floral Community For Over 20+ Yrs. In The Same Location!Head/ Stepping Stones/Flowers For Any Occasion
888-901-6744 |
store hours | view map2435 Whitten Rd Memphis, TN 38133-4715
Free Delivery And Express Deli Available! Satisfaction Guaranteed!
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