DE4029165A1 - 4-Fluoro-pyrimidine cpds. used as components of liq. crystal mixts. - Google Patents
4-Fluoro-pyrimidine cpds. used as components of liq. crystal mixts.Info
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- DE4029165A1 DE4029165A1 DE19904029165 DE4029165A DE4029165A1 DE 4029165 A1 DE4029165 A1 DE 4029165A1 DE 19904029165 DE19904029165 DE 19904029165 DE 4029165 A DE4029165 A DE 4029165A DE 4029165 A1 DE4029165 A1 DE 4029165A1
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- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
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- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/32—One oxygen, sulfur or nitrogen atom
- C07D239/34—One oxygen atom
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- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
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- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
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- 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
- C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
- C09K19/345—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing two nitrogen atoms
- C09K19/3458—Uncondensed pyrimidines
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- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
- C09K19/345—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing two nitrogen atoms
- C09K19/3458—Uncondensed pyrimidines
- C09K19/3466—Pyrimidine with at least another heterocycle in the chain
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- 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
- C09K19/40—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals
- C09K19/406—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals containing silicon
Abstract
Description
Die ungewöhnliche Kombination von anisotropem und fluidem Verhalten der Flüssigkristalle hat zu ihrer Verwendung in einer Vielzahl verschiedener elektro-optischer Schalt- und Anzeigevorrichtungen geführt. Dabei können ihre elektrischen, magnetischen, elastischen und/oder thermischen Eigenschaften zu Orientierungsänderungen genutzt werden. Optische Effekte lassen sich beispielsweise mit Hilfe der Doppelbrechung, der Einlagerung dichroitisch absorbierender Farbstoffmoleküle ("guest-host mode") oder der Lichtstreuung erzielen.The unusual combination of anisotropic and fluid Behavior of liquid crystals has to their use in a variety of different electro-optical switching and Display devices led. Your electrical, magnetic, elastic and / or thermal properties be used to change orientation. Optical effects can be, for example, with the help of birefringence, the Storage of dichroic absorbing dye molecules ("guest-host mode") or the light scatter.
Zur Erfüllung der ständig steigenden Praxisanforderungen auf den verschiedenen Anwendungsgebieten besteht laufend ein Bedarf an neuen verbesserten Flüssigkristall("liquid crystal")-Mischungen und somit auch an einer Vielzahl mesogener Verbindungen unterschiedlicher Struktur. Dies gilt sowohl für die Gebiete, bei denen nematische LC-Phasen verwendet werden, als auch für solche mit smektischen LC-Phasen.To meet the ever increasing practice requirements the various areas of application are continuously updated Need for new improved liquid crystal ("liquid crystal ") - mixtures and thus also on a large number mesogenic compounds of different structure. this applies both for the areas where nematic LC phases be used, as well as for those with smectic LC phases.
Auf besonderes Interesse sind in den letzten Jahren ferroelektrische flüssigkristalline Mischungen (FLC- Mischungen) gestoßen (siehe z. B. Lagerall et al. "Ferroelectric Liquid Crystals for Display", SID Symposium, October Meeting 1985, San Diego, Ca. USA). Für die praktische Verwendung von ferroelektrischen Flüssigkristallen in elektrooptischen Anzeigen werden chirale, geneigt-smektische Phasen wie z. B. Sc-Phasen benötigt [siehe R. B. Meyer, L. Lieb´rt, L. Strzelecki und P. Keller, J. Physique 36, L-69 (1975)], die über einen großen Temperaturbereich stabil sind. Dieses Ziel kann man mit Verbindungen erreichen, die selbst solche Phasen, z. B. Sc-Phasen, ausbilden oder aber, indem man nicht chirale geneigt-smektische Phasen ausbildende Verbindungen mit optisch aktiven Verbindungen dotiert [siehe M. Brunet, Cl. Williams, Ann. Phys. 3, 237 (1978)].Ferroelectric liquid crystalline mixtures (FLC mixtures) have been of particular interest in recent years (see, for example, Lagerall et al. "Ferroelectric Liquid Crystals for Display", SID Symposium, October Meeting 1985, San Diego, Ca. USA). For the practical use of ferroelectric liquid crystals in electro-optical displays, chiral, inclined-smectic phases such as e.g. B. S c phases are required [see RB Meyer, L. Lieb´rt, L. Strzelecki and P. Keller, J. Physique 36, L-69 (1975)], which are stable over a wide temperature range. This goal can be achieved with compounds that themselves have such phases, e.g. B. S c phases, or by doping non-chiral inclined smectic phases with optically active compounds [see M. Brunet, Cl. Williams, Ann. Phys. 3, 237 (1978)].
Da der flüssigkristalline Temperaturbereich der meisten ferroelektrischen Flüssigkristallsysteme zu klein ist, besteht laufend ein Bedarf an neuen Komponenten und neuen Flüssigkristallmischungen, die eine Sc-Phase nahe Raumtemperatur ausbilden.Since the liquid crystalline temperature range of most ferroelectric liquid crystal systems is too small, there is an ongoing need for new components and new liquid crystal mixtures which form an S c phase close to room temperature.
In EP-B 01 58 137 werden 4-Fluorprimidine als Verbindungen und als Mischungskomponenten allgemein beschrieben. Sie weisen jedoch keine oder nur eine geringe Tendenz zur Ausbildung smektischer Phasen auf.In EP-B 01 58 137 4-fluorprimidines are used as compounds and generally described as blend components. they however have no or only a slight tendency to Training smectic phases.
Die vorliegende Erfindung betrifft die Verwendung eines speziellen 4-Fluorpyrimidin-Derivates als Komponente für eine Flüssigkristallmischung, wobei man mindestens ein 4-Fluorpyrimidin der allgemeinen Formel (I) als Komponente in einer ferroelektrischen Flüssigkristallmischung bestehend aus 2 bis 20, vorzugsweise 2 bis 15, Komponenten einsetzt.The present invention relates to the use of a special 4-fluoropyrimidine derivative as a component for a liquid crystal mixture, wherein at least one 4-fluoropyrimidine of the general formula (I) as a component in a ferroelectric liquid crystal mixture consisting of 2 to 20, preferably 2 to 15, components starts.
Die Symbole haben hierbei folgende Bedeutung:The symbols have the following meaning:
R¹, R² unabhängig voneinander geradkettiges oder verzweigtes Alkyl mit 1 bis 16 C-Atomen, wobei ein oder zwei nicht benachbarte -CH₂-Gruppen durch -O-, -S-, -CO-, -CO-O-, -O-CO-, -CH=CH-, -OC(O)O-, -C≡C-R¹, R² independently of one another straight-chain or branched Alkyl with 1 to 16 carbon atoms, one or two not adjacent -CH₂ groups by -O-, -S-, -CO-, -CO-O-, -O-CO-, -CH = CH-, -OC (O) O-, -C≡C-
oder -Si(CH₃)₂- ersetzt sein können, oder eine der folgenden Gruppen: or -Si (CH₃) ₂- can be replaced, or one of the following groups:
R³, R⁴ unabhängig voneinander H oder Alkyl mit 1 bis 16
oder Alkenyl mit 2 bis 16 C-Atomen, oder R³ und
R⁴ zusammen -(CH₂)₄- oder -(CH₂)₅-
-M¹- -CO-O-, -O-CO-, -CH₂-O-, -O-CH₂-, -C≡C-, -CH=CH-,
-CH₂-CH₂-, -CH₂CH₂CH₂CH₂-, -CH₂CH₂CH₂O-R³, R⁴ independently of one another are H or alkyl having 1 to 16 or alkenyl having 2 to 16 C atoms, or R³ and R⁴ together - (CH₂) ₄- or - (CH₂) ₅-
-M¹- -CO-O-, -O-CO-, -CH₂-O-, -O-CH₂-, -C≡C-, -CH = CH-, -CH₂-CH₂-, -CH₂CH₂CH₂CH₂-, - CH₂CH₂CH₂O-
a, b unabhängig voneinander Null oder Eins, unter der Bedingung, daß a Null ist, wenn b Null ist,a, b independently of one another zero or one below which Condition that a is zero when b is zero,
In einer bevorzugten Ausführungsform haben die Symbole in Formel (I) folgende Bedeutung:In a preferred embodiment, the symbols in Formula (I) has the following meaning:
R¹, R² unabhängig voneinander Alkyl mit 1 bis 16 C-Atomen, wobei eine -CH₂-Gruppe durch -O-, -CO-O-, -O-CO-,R¹, R² independently of one another alkyl having 1 to 16 carbon atoms, where a -CH₂ group by -O-, -CO-O-, -O-CO-,
oder -Si(CH₃)₂- ersetzt sein kann, oderor -Si (CH₃) ₂- can be replaced, or
-M¹- -CO-O-, -O-CO-, -CH₂O- oder -OCH₂-
-M²- -CO-O-, -CH₂O--M¹- -CO-O-, -O-CO-, -CH₂O- or -OCH₂-
-M²- -CO-O-, -CH₂O-
R³, R⁴ beide H oder C₁-C₅-Alkyl oder R³ und R⁴ zusammen
-(CH₂)₅-
a, b unabhängig voneinander Null oder Eins, unter der
Bedingung, daß a Null ist, wenn b Null ist.R³, R⁴ both H or C₁-C₅-alkyl or R³ and R⁴ together - (CH₂) ₅-
a, b are independently zero or one, provided that a is zero when b is zero.
Besonders bevorzugt bedeutenMean particularly preferred
R¹, R² unabhängig voneinander Alkyl mit 5 bis 12 C-Atomen, wobei eine -CH₂-Gruppe durch -O- und eine weitere -CH₂-Gruppe durchR¹, R² independently Alkyl with 5 to 12 carbon atoms, with a -CH₂ group through -O- and another -CH₂ group through
ersetzt sein kann, oderto be replaced can, or
-M¹- CO-O oder O-CO,-M¹- CO-O or O-CO,
R³, R⁴ beide gleich H oder C₁-C₅-Alkyl oder R³ und R⁴
zusammen -(CH₂)₅- und
a=b Null oder Eins.R³, R⁴ are both H or C₁-C₅-alkyl or R³ and R⁴ together - (CH₂) ₅- and
a = b zero or one.
Die Erfindung betrifft ferner eine ferroelektrische Flüssigkristallmischung bestehend aus 2 bis 20 Komponenten, die als eine Komponente mindestens ein 4-Fluor-pyrimidin der allgemeinen Formel (I) enthält.The invention further relates to a ferroelectric Liquid crystal mixture consisting of 2 to 20 components, which as a component at least one 4-fluoropyrimidine contains the general formula (I).
Diese FLC-Mischung enthält im allgemeinen 0,1 bis 80, vorzugsweise 1 bis 60, insbesondere 1 bis 20 Mol-% der Verbindung der Formel (I). Sind mehrere der Verbindungen in der Mischung enthalten, so liegt der Gesamtgehalt bei 0,1 bis 80 Mol-%, vorzugsweise bei 1 bis 60 Mol-%.This FLC mixture generally contains 0.1 to 80, preferably 1 to 60, in particular 1 to 20 mol% of the Compound of formula (I). Are several of the connections contained in the mixture, the total content is 0.1 to 80 mol%, preferably 1 to 60 mol%.
Die anderen Bestandteile der Mischungen werden vorzugsweise ausgewählt aus den bekannten Verbindungen mit nematischen, cholesterischen und/oder geneigt/smektischen Phasen, dazu gehören beispielsweise Schiffsche Basen, Biphenyle, Terphenyle, Phenylcyclohexane, Cyclohexylbiphenyle, Pyrimidine, Zimtsäureester, Cholesterinester oder verschieden überbrückte Ester von p-Alkylbenzoesäuren.The other components of the mixtures are preferred selected from the known compounds with nematic, cholesteric and / or inclined / smectic phases include, for example, Schiff bases, biphenyls, Terphenyls, phenylcyclohexanes, cyclohexylbiphenyls, Pyrimidines, cinnamic acid esters, cholesterol esters or various bridged esters of p-alkylbenzoic acids.
Die beschreibenen Flüssigkristallmischungen lassen sich in elektrooptischen Schalt- und Anzeigevorrichtungen (FLC-Lichtventilen bzw. Displays) vorteilhaft einsetzen. Diese weisen u. a. folgende Bestandteile auf: eine flüssigkristalline Mischung (enthaltend ein 4-Fluorpyrimidin), Trägerplatten (z. B. aus Glas oder Kunststoff), beschichtet mit transparenten Elektroden (zwei Elektroden), mindestens eine Orientierungsschicht, Abstandhalter, Kleberahmen, Polarisatoren, sowie für Farbdisplays dünne Farbfilterschichten. Weiter mögliche Komponenten sind Antireflex-, Passivierungs-, Ausgleichs- und Sperrschichten sowie elektrisch nichtlineare Elemente, wie z. B. Dünnschichttransistoren (TFT) und Metall-Isolator- Metall(MIM)-Elemente. Im Detail ist der allgemeine Aufbau von Flüssigkristalldisplays bereits in einschlägigen Monographien beschrieben (z. B. E. Kaneko, "Liquid Crystal Displays", KTK, Scientific Publishers, 1987, Seiten 12-30 und 163-172).The liquid crystal mixtures described can be in electro-optical switching and display devices (FLC light valves or displays) can be used advantageously. These have u. a. the following components: a liquid crystalline mixture (containing a 4-fluoropyrimidine), carrier plates (e.g. made of glass or Plastic), coated with transparent electrodes (two electrodes), at least one orientation layer, Spacers, adhesive frames, polarizers, as well as for Color displays thin layers of color filters. Other possible Components are anti-reflective, passivation, compensation and barrier layers as well as electrically non-linear elements, such as B. thin film transistors (TFT) and metal insulator Metal (MIM) elements. The general structure is in detail of liquid crystal displays already in relevant Monographs described (e.g. E. Kaneko, "Liquid Crystal Displays ", KTK, Scientific Publishers, 1987, pages 12-30 and 163-172).
Die 4-Fluor-pyrimidine der Formel (I) sind chemisch, photochemisch und thermisch stabil; sie weisen vorzugsweise sowohl Sc-Phasen als auch nematische Phasen auf. Besonders bevorzugt sind dabei die 5-Alkyloxy-2-(4-alkyloxy)phenyl-4- fluor-pyrimidine, die neben der Sc-Phase auch noch niedrigere Schmelzpunkte als ihre nicht fluorierten Analogen aufweisen. Vorzugsweise unterdrückt die Fluor-Substitution ferner die Bildung von höhergeordneten Phasen.The 4-fluoropyrimidines of the formula (I) are chemically, photochemically and thermally stable; they preferably have both S c phases and nematic phases. Particularly preferred are the 5-alkyloxy-2- (4-alkyloxy) phenyl-4-fluoropyrimidines, which in addition to the S c phase also have lower melting points than their non-fluorinated analogs. Preferably, the fluorine substitution also suppresses the formation of higher order phases.
Die Erfindung betrifft ein Verfahren zur Herstellung von 4-Fluor-pyrimidin-Derivaten, insbesondere solcher der Formel (I), wobei man Pyrimidin-4-on-Verbindungen der Formel (II) mit einem Aminofluorosulfuran der Formel (III) zur Reaktion bringt,The invention relates to a method for manufacturing of 4-fluoro-pyrimidine derivatives, especially those of Formula (I), wherein pyrimidin-4-one compounds of Formula (II) with an aminofluorosulfuran of the formula (III) react,
wobeiin which
R⁵ und R⁶ unabhängig voneinander C₁- bis C₁₉-Alkyl,
oder R⁵ und R⁶ zusammen (-CH₂)c(-O)d(-CH₂)e bedeuten, wobei
c=eine ganze Zahl von 1 bis 5,
d=Null oder 1 und
e=eine ganze Zahl von 1 bis 5 sind.R⁵ and R⁶ independently of one another are C₁ to C₁₉ alkyl, or R⁵ and R⁶ together are (-CH₂) c (-O) d (-CH₂) e , where
c = an integer from 1 to 5,
d = zero or 1 and
e = are an integer from 1 to 5.
Dabei wird eine Pyrimidin-4-on-Verbindung (II) - die Herstellung erfolgt in Analogie zu Boller et al., Z. Naturf. 33b (1978) - mit einem Fluorierungsreagenz direkt zu (I) umgesetzt. Gegenüber dem Verfahren der EP-B 01 58 137, Pyrimidin-4-on mit POCl₃ in die entsprechenden Chlorverbindungen zu überführen und diese dann mit einem fluorierenden Mittel zu den Fluorverbindungen umzusetzen, hat das erfindungsgemäße Verfahren den Vorteil, die Stufe der Chlorierung - die häufig mit Dunkelfärbungen und Bildung schwer abtrennbarer Verunreinigungen einhergeht - zu vermeiden. Prinzipiell ist das beschriebene Fluorierungsverfahren auf andere Pyrimidin-4-on-Verbindungen allgemein anwendbar.Doing so Pyrimidin-4-one compound (II) - the preparation takes place in analogy to Boller et al., Z. Naturf. 33b (1978) - converted directly to (I) with a fluorination reagent. Compared to the process of EP-B 01 58 137, pyrimidin-4-one with POCl₃ in the corresponding chlorine compounds and then transfer them with a fluorinating agent to implement the fluorine compounds has the invention Process the advantage, the level of chlorination - which is common with darkening and formation difficult to separate Contamination comes along - to avoid. In principle is the fluorination process described to others Pyrimidin-4-one compounds generally applicable.
Bevorzugt werden als Fluorierungsmittel Aminofluorosulfurane, bei denen in Formel (III) R⁵ und R⁶ C₁- bis C₃-Alkyl, oder R⁵ und R⁶ zusammen die Gruppe -(CH₂)₂-O-(CH₂)₂- bedeuten, (siehe z. B. M. Hudlicky in Org. Reactions 53, 513). Besonders bevorzugt werden Diethylaminoschwefeltrifluorid und Morpholinoschwefeltrifluorid eingesetzt.Preferred fluorinating agents are aminofluorosulfurans, in which in formula (III) R⁵ and R⁶ C₁- to C₃-alkyl, or R⁵ and R⁶ together represent the group - (CH₂) ₂-O- (CH₂) ₂-, (See e.g. M. Hudlicky in Org. Reactions 53, 513). Especially preferred are diethylaminosulfur trifluoride and Morpholinosulfur trifluoride used.
Die Erfindung wird durch die nachfolgenden Beispiele näher erläutert.The invention is illustrated by the following examples explained in more detail.
Eine Suspension von 2.1 g 5-Octyloxy-2-(4-octyloxy-phenyl)
pyrimidin-4-on (hergestellt z. B. nach Boller et al.,
Z. Naturf. 33b, 433 (1978)) in 30 ml Dichlormethan wird
bei 0°C binnen 10 Minuten mit einer Lösung von 0.7 ml
Diethylaminoschwefeltrifluorid (DAST) in 10 ml
Dichlormethan versetzt. Nach 8 h bei 40°C wird mit
wäßriger Natriumhydrogencarbonatlösung versetzt. Die
organische Phase liefert nach Chromatographie und
Umkristallisation aus Acetonitril 0.7 g farblose Kristalle.
Phasenfolge X 43,5 Sc 52 N 64,2 IA suspension of 2.1 g of 5-octyloxy-2- (4-octyloxy-phenyl) pyrimidin-4-one (prepared e.g. according to Boller et al., Z. Naturf. 33b, 433 (1978)) in 30 ml dichloromethane a solution of 0.7 ml of diethylaminosulfur trifluoride (DAST) in 10 ml of dichloromethane is added at 0 ° C. within 10 minutes. After 8 h at 40 ° C., aqueous sodium bicarbonate solution is added. After chromatography and recrystallization from acetonitrile, the organic phase gives 0.7 g of colorless crystals.
Phase sequence X 43.5 S c 52 N 64.2 I
Die unfluorierte Vergleichsverbindung weist mit 51°C einen Schmelzpunkt auf, der um 7°C höher liegt.The unfluorinated comparison compound has a temperature of 51 ° C Melting point, which is 7 ° C higher.
Analog werden erhalten:The following are obtained analogously:
4-Fluor-5-heptyl-2-(4-octyloxy-phenyl)pyrimidin
Phasenfolge X 40 N 43,8 I4-fluoro-5-heptyl-2- (4-octyloxy-phenyl) pyrimidine
Phase sequence X 40 N 43.8 I
4-Fluor-5-octyl-2-(4-octyloxy-phenyl)pyrimidin
Phasenfolge X 37 N 41,5 I4-fluoro-5-octyl-2- (4-octyloxyphenyl) pyrimidine
Phase sequence X 37 N 41.5 I
4-Fluor-5-nonyl-2-(4-octyloxy-phenyl)pyrimidin
Phasenfolge X 34 N 45 I4-fluoro-5-nonyl-2- (4-octyloxyphenyl) pyrimidine
Phase sequence X 34 N 45 I
5-Decyl-4-fluor-2-(4-octyloxy-phenyl)pyrimidin
Phasenfolge X 36 N 43 I5-decyl-4-fluoro-2- (4-octyloxyphenyl) pyrimidine
Phase sequence X 36 N 43 I
2-(4-Ethoxy-phenyl)-4-fluor-5-octyloxy-pyrimidin
Phasenfolge X 70,5 (N) 55 I
2- (4-ethoxyphenyl) -4-fluoro-5-octyloxypyrimidine
Phase sequence X 70.5 (N) 55 I
5-[4-(Butyldimethylsilyl)butyloxy]-4-fluor-2-(4-octyloxy-
phenyl)pyrimidin
Phasenfolge X 12.4 N 16 I5- [4- (Butyldimethylsilyl) butyloxy] -4-fluoro-2- (4-octyloxyphenyl) pyrimidine
Phase sequence X 12.4 N 16 I
4-Fluor-5-octyloxy-2-[4-(4-trans-pentyl-cyclohexyl)phenyl]pyrimidin
Phasenfolge X 71 (Sc) 61 N 148 I4-fluoro-5-octyloxy-2- [4- (4-trans-pentylcyclohexyl) phenyl] pyrimidine
Phase sequence X 71 (S c ) 61 N 148 I
Die unfluorierte Vergleichssubstanz weist bis 83°C eine höher geordnete smektische Phase auf. Offensichtlich führt die Fluorsubstitution zu einer Unterdrückung der höher geordneten smektischen Phase und damit zu einer Ausweitung der Sc-Phase nach tiefen Temperaturen.The unfluorinated reference substance has a higher order smectic phase up to 83 ° C. The fluorine substitution obviously leads to a suppression of the higher ordered smectic phase and thus to an expansion of the S c phase after low temperatures.
2-[4-(4-Cyclopropylbutyloxy)phenyl]-4-fluor-5-octyloxy-pyrimidin
Phasenfolge X (45 N) 62 I2- [4- (4-Cyclopropylbutyloxy) phenyl] -4-fluoro-5-octyloxypyrimidine
Phase sequence X (45 N) 62 I
2-[4-(8-Cyclopropyloctyloxy)phenyl]-4-fluor-5-octyloxy-pyrimidin
Phasenfolge X 51 (Sc 45 N 55) I2- [4- (8-Cyclopropyloctyloxy) phenyl] -4-fluoro-5-octyloxypyrimidine
Phase sequence X 51 (S c 45 N 55) I
Eine Lösung von 1,6 g 5-Octyloxy-2-[4-(4-trans-
pentylcyclohexylcarbonyloxy)phenyl]pyrimidin-4-on
(erhalten durch Umsetzung von 2-(4-Hydroxy-phenyl)-5-
octyloxy-pyrimidin-4-on - Herstellung nach Boller et al. -
mit trans-4-Pentylcyclohexancarbonsäure mittels
Dicyclohexylcarbodiimid) in 40 ml Dichlormethan wird mit
0,45 ml Diethylamino-schwefeltrifluorid versetzt und 16 h
bei 20°C gehalten. Nach Aufarbeitung wie in Beispiel 1 und
Umkristallisation aus n-Hexan werden 0,3 g farblose Kristalle
erhalten.
Phasenfolge X 80 Sc 87 N 173 I
Diese Sc-Phase ist bis zur Kristallisation bei 60 existent.A solution of 1.6 g of 5-octyloxy-2- [4- (4-transpentylcyclohexylcarbonyloxy) phenyl] pyrimidin-4-one (obtained by reacting 2- (4-hydroxyphenyl) -5-octyloxypyrimidine -4-one - preparation according to Boller et al. - with trans-4-pentylcyclohexane carboxylic acid using dicyclohexylcarbodiimide) in 40 ml dichloromethane, 0.45 ml diethylamino-sulfur trifluoride is added and the mixture is kept at 20 ° C. for 16 h. After working up as in Example 1 and recrystallization from n-hexane, 0.3 g of colorless crystals are obtained.
Phase sequence X 80 S c 87 N 173 I
This S c phase exists at 60 until crystallization.
Die unfluorierte Vergleichssubstanz weist hingegen bei 74°C eine höher geordnete smektische Phase auf, die offensichtlich durch die Fluorierung unterdrückt wird.The unfluorinated reference substance, however, shows at 74 ° C a higher order smectic phase that is obvious is suppressed by the fluorination.
Analog werden erhalten:The following are obtained analogously:
4-Fluor-5-octyl-2-[4-(4-trans-pentylcyclohexylcarbonyloxy)
phenyl]pyrimidin
Phasenfolge X 78 N 173 I4-fluoro-5-octyl-2- [4- (4-trans-pentylcyclohexylcarbonyloxy) phenyl] pyrimidine
Phase sequence X 78 N 173 I
(2R,3R)-3-Propyloxirancarbonsäure-[4-(4-fluor-5-octyloxy-
pyrimidin-2-yl)phenyl]ester
Drehwert [α] = -24.9° (c=2, 1,2-Dichlorethan)
Phasenfolge X 90 I(2R, 3R) -3-propyloxirane carboxylic acid [4- (4-fluoro-5-octyloxypyrimidin-2-yl) phenyl] ester
Rotation value [α] = -24.9 ° (c = 2, 1,2-dichloroethane)
Phase sequence X 90 I
Claims (7)
R¹, R² unabhängig voneinander geradkettiges oder verzweigtes Alkyl mit 1 bis 16 C-Atomen, wobei ein oder zwei nicht benachbarte -CH₂-Gruppen durch -O-, -S-, -CO-, -CO-O-, -O-CO-, -CH=CH-, -OC(O)O-, -C≡C-, oder -Si(CH₃)₂- ersetzt sein können, oder eine der folgenden Gruppen: R³, R⁴ unabhängig voneinander H oder Alkyl mit 1 bis 16 oder Alkenyl mit 2 bis 16 C-Atomen, oder R³ und R⁴ zusammen -(CH₂-)₄- oder -(CH₂)₅-
-M¹- -CO-O-, -O-CO-, -CH₂-O-, -O-CH₂-, -C≡C-, -CH=CH-, -CH₂-CH₂-, -CH₂CH₂CH₂CH₂-, -CH₂CH₂CH₂O- a, b unabhängig voneinander Null oder Eins, unter der Bedingung, daß a Null ist, wenn b Null ist, 1. Use of a fluoropyrimidine derivative as a component for liquid crystal mixtures, at least one 4-fluoropyrimidine of the general formula (I) being used as a component in a ferroelectric liquid crystal mixture consisting of 2 to 20 components, where the symbols have the following meaning:
R¹, R² independently of one another straight-chain or branched alkyl having 1 to 16 carbon atoms, one or two non-adjacent -CH₂ groups by -O-, -S-, -CO-, -CO-O-, -O-CO -, -CH = CH-, -OC (O) O-, -C≡C-, or -Si (CH₃) ₂- can be replaced, or one of the following groups: R³, R⁴ independently of one another are H or alkyl having 1 to 16 or alkenyl having 2 to 16 C atoms, or R³ and R⁴ together - (CH₂-) ₄- or - (CH₂) ₅-
-M¹- -CO-O-, -O-CO-, -CH₂-O-, -O-CH₂-, -C≡C-, -CH = CH-, -CH₂-CH₂-, -CH₂CH₂CH₂CH₂-, - CH₂CH₂CH₂O- a, b independently of one another zero or one, on the condition that a is zero when b is zero,
R¹, R² unabhängig voneinander Alkyl mit 1 bis 16 C-Atomen, wobei eine -CH₂-Gruppe durch -O-, -CO-O-, -O-CO-, oder -Si(CH₃)₂- ersetzt sein kann, oder -M¹- -CO-O, O-CO-, CH₂O oder -OCH₂-
-M²- -CO-O- oder -CH₂O- R³, R⁴ beide H oder C₁-C₅-Alkyl oder R³ und R⁴ zusammen -(CH₂)₅-
a, b unabhängig voneinander Null oder Eins, unter der Bedingung, daß a Null ist, wenn b Null ist.2. Use according to claim 1, characterized in that in formula (I) the symbols have the following meaning:
R¹, R² independently of one another alkyl having 1 to 16 carbon atoms, a -CH₂ group by -O-, -CO-O-, -O-CO-, or -Si (CH₃) ₂- can be replaced, or -M¹- -CO-O, O-CO-, CH₂O or -OCH₂-
-M²- -CO-O- or -CH₂O- R³, R⁴ both H or C₁-C₅-alkyl or R³ and R⁴ together - (CH₂) ₅-
a, b are independently zero or one, provided that a is zero when b is zero.
R¹, R² unabhängig voneinander Alkyl mit 5 bis 12 C-Atomen, wobei eine -CH₂-Gruppe durch -O- und eine weitere Gruppe durch ersetzt sein kann, oder -M¹- -CO-O- oder -O-CO-, R³, R⁴ beide gleich H oder C₁-C₅-Alkyl oder R³ und R⁴ zusammen -(CH₂)₅- und
a=b Null oder Eins.3. Use according to claim 1, characterized in that in formula (I) the symbols have the following meaning:
R¹, R² independently of one another alkyl having 5 to 12 carbon atoms, one -CH₂ group by -O- and another group by can be replaced, or -M¹- -CO-O- or -O-CO-, R³, R⁴ are both H or C₁-C₅-alkyl or R³ and R⁴ together - (CH₂) ₅- and
a = b zero or one.
R⁵ und R⁶ unabhängig voneinander C₁- bis C₁₀-Alkyl, oder R⁵ und R⁶ zusammen (-CH₂)c(-O)d(-CH₂)e bedeuten, wobei
c=eine ganze Zahl von 1 bis 5,
d=Null oder 1 und
e=eine ganze Zahl von 1 bis 5 sind
und die Substituenten R¹, M¹, R³, a, b, die in Anspruch 1 genannten Bedeutungen haben.6. A process for the preparation of 4-fluoropyrimidine derivatives of the formula (I) according to claim 1, characterized in that pyrimidin-4-one compounds of the formula (II) are reacted with an aminosulfurane of the formula (III) , in which
R⁵ and R⁶ independently of one another are C₁ to C₁₀ alkyl, or R⁵ and R⁶ together are (-CH₂) c (-O) d (-CH₂) e , where
c = an integer from 1 to 5,
d = zero or 1 and
e = are an integer from 1 to 5
and the substituents R¹, M¹, R³, a, b, have the meanings mentioned in claim 1.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19904029165 DE4029165A1 (en) | 1990-09-14 | 1990-09-14 | 4-Fluoro-pyrimidine cpds. used as components of liq. crystal mixts. |
| US07/758,633 US5344585A (en) | 1990-09-14 | 1991-09-12 | Use of 4-fluoropyrimidine derivatives as component for ferroelectric liquid crystal mixtures |
| JP3235117A JP3070992B2 (en) | 1990-09-14 | 1991-09-13 | Use of 4-fluoropyrimidine derivatives as components of ferroelectric liquid crystal mixtures |
| DE59109140T DE59109140D1 (en) | 1990-09-14 | 1991-09-13 | The use of 4-fluoropyrimidine derivatives as a component for ferroelectric liquid crystal mixtures and their preparation |
| KR1019910015957A KR920006479A (en) | 1990-09-14 | 1991-09-13 | Use of 4-fluoropyrimidine derivatives as ferroelectric liquid crystal mixture components |
| EP91115584A EP0475444B1 (en) | 1990-09-14 | 1991-09-13 | Use of 4-fluoro-pyrimidine derivatives as components for ferroelectric liquid crystal mixtures and process to prepare these compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19904029165 DE4029165A1 (en) | 1990-09-14 | 1990-09-14 | 4-Fluoro-pyrimidine cpds. used as components of liq. crystal mixts. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4029165A1 true DE4029165A1 (en) | 1992-03-19 |
Family
ID=6414230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19904029165 Withdrawn DE4029165A1 (en) | 1990-09-14 | 1990-09-14 | 4-Fluoro-pyrimidine cpds. used as components of liq. crystal mixts. |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE4029165A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0532916A1 (en) * | 1991-08-17 | 1993-03-24 | Hoechst Aktiengesellschaft | 2-Fluoropyrazines, process for their preparation, and their use in liquid crystalline mixtures |
| US5630962A (en) * | 1990-12-19 | 1997-05-20 | Hoechst Aktiengesellschaft | 2-Fluoropyridines, their preparation and their use in liquid crystal mixtures |
| DE19624590B4 (en) * | 1996-06-20 | 2007-07-12 | Merck Patent Gmbh | 2,2-Difluoro-1,3-dioxanes, liquid crystalline medium containing them, their use and intermediates (1,3-dioxane-2-thiones) |
-
1990
- 1990-09-14 DE DE19904029165 patent/DE4029165A1/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5630962A (en) * | 1990-12-19 | 1997-05-20 | Hoechst Aktiengesellschaft | 2-Fluoropyridines, their preparation and their use in liquid crystal mixtures |
| EP0532916A1 (en) * | 1991-08-17 | 1993-03-24 | Hoechst Aktiengesellschaft | 2-Fluoropyrazines, process for their preparation, and their use in liquid crystalline mixtures |
| US5562859A (en) * | 1991-08-17 | 1996-10-08 | Hoechst Aktiengesellschaft | 2-fluoropyrazines process for their preparation, and their use in liquid-crystalline mixtures |
| DE19624590B4 (en) * | 1996-06-20 | 2007-07-12 | Merck Patent Gmbh | 2,2-Difluoro-1,3-dioxanes, liquid crystalline medium containing them, their use and intermediates (1,3-dioxane-2-thiones) |
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| 8130 | Withdrawal | ||
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