DE19625441A1 - Chiral dopants for liquid crystalline media - Google Patents
Chiral dopants for liquid crystalline mediaInfo
- Publication number
- DE19625441A1 DE19625441A1 DE1996125441 DE19625441A DE19625441A1 DE 19625441 A1 DE19625441 A1 DE 19625441A1 DE 1996125441 DE1996125441 DE 1996125441 DE 19625441 A DE19625441 A DE 19625441A DE 19625441 A1 DE19625441 A1 DE 19625441A1
- Authority
- DE
- Germany
- Prior art keywords
- hydrogen
- alkyl
- compounds according
- ocoo
- oco
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000002019 doping agent Substances 0.000 title claims abstract description 6
- 239000007788 liquid Substances 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- -1 biphenylyl Chemical group 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000006850 spacer group Chemical group 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 5
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 5
- 125000001589 carboacyl group Chemical group 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 claims abstract description 3
- 239000004988 Nematic liquid crystal Substances 0.000 claims abstract description 3
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 239000000049 pigment Substances 0.000 claims abstract description 3
- 230000003098 cholesteric effect Effects 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Chemical group 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- 125000001651 cyanato group Chemical group [*]OC#N 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 2
- 235000021190 leftovers Nutrition 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 150000002431 hydrogen Chemical group 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 235000010355 mannitol Nutrition 0.000 description 5
- 229930195725 Mannitol Natural products 0.000 description 4
- 239000000594 mannitol Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002402 hexoses Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 101150092841 HAX1 gene Proteins 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 235000019256 formaldehyde Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000819038 Chichester Species 0.000 description 1
- WQZGKKKJIJFFOK-CBPJZXOFSA-N D-Gulose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O WQZGKKKJIJFFOK-CBPJZXOFSA-N 0.000 description 1
- WQZGKKKJIJFFOK-WHZQZERISA-N D-aldose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-WHZQZERISA-N 0.000 description 1
- WQZGKKKJIJFFOK-IVMDWMLBSA-N D-allopyranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@@H]1O WQZGKKKJIJFFOK-IVMDWMLBSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 206010012335 Dependence Diseases 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910002114 biscuit porcelain Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001841 cholesterols Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002983 circular dichroism Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002454 idoses Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000005907 ketalization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/58—Dopants or charge transfer agents
- C09K19/586—Optically active dopants; chiral dopants
- C09K19/588—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0098—Organic pigments exhibiting interference colours, e.g. nacrous pigments
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Wie für formanisotrope Moleküle bekannt, können beim Erwärmen flüssigkristalline Phasen, sogenannte Mesophasen, auftreten. Die einzelnen Phasen unterscheiden sich durch die räumliche Anordnung der Molekülschwerpunkte einerseits sowie durch die Molekülanord nung hinsichtlich der Längsachsen andererseits (G. W. Gray, P. A. Winsor, Liquid Crystals and Plastic Crystals, Ellis Horwood Limited, Chichester 1974). Die nematisch-flüssigkristalline Phase zeichnet sich dadurch aus, daß lediglich eine Orientierungsfern ordnung durch Parallellagerung der Moleküllängsachsen existiert. Unter der Voraussetzung, daß die die nematische Phase aufbauenden Moleküle chiral sind, entsteht eine sogenannte cholesterische Phase, bei der die Längsachsen der Moleküle eine zu ihnen senk rechte, helixartige Überstruktur ausbilden (H. Baessler, Festkör perprobleme XI, 1971) Der chirale Molekülteil kann im flüssig kristallinen Molekül selbst enthalten sein oder aber als Dotier stoff zur nematischen Phase gegeben werden. Durch Dotierung er zeugte Phasen werden als induziert cholesterische Phasen bezeich net. Dieses Phänomen wurde zuerst an Cholesterolderivaten unter sucht (H. Baessler, M. M. Labes, J. Chem. Phys. 52 (1970) 631; H. Baessler, T. M. Laronge, M. M. Labes. J. Chem. Phys. 51 (1969) 3213; H. Finkelmann, H. Stegemeyer, Z. Naturforschg. 28a (1973) 799). Später wurde die Induzierung cholesterischer Phasen auch durch Zusatz anderer chiraler Substanzen möglich, die selbst nicht flüssigkristallin sind (H. Stegemeyer, K. J. Mainusch, Na turwiss. 58 (1971) 599; H. Finkelmann, H. Stegemeyer, Ber. Bunsenges. Phys. Chem. 78 (1974) 869).As known for shape anisotropic molecules, when heated liquid-crystalline phases, so-called mesophases, occur. The individual phases differ in their spatial arrangement the molecular focus on the one hand and by the molecular arrangement on the other hand with regard to the longitudinal axes (G. W. Gray, P. A. Winsor, Liquid Crystals and Plastic Crystals, Ellis Horwood Limited, Chichester 1974). The nematic-liquid crystalline phase is characterized by the fact that only a distant orientation Order exists through parallel storage of the molecular axes. Provided that the building the nematic phase Molecules are chiral, a so-called cholesteric arises Phase in which the longitudinal axes of the molecules lower one towards them Form right, helical superstructure (H. Baessler, Solid perprobleme XI, 1971) The chiral part of the molecule can be liquid crystalline molecule itself or as a dopant can be added to the nematic phase. By doping it generated phases are referred to as induced cholesteric phases net. This phenomenon was first discovered on cholesterol derivatives addiction (H. Baessler, M. M. Labes, J. Chem. Phys. 52 (1970) 631; H. Baessler, T. M. Laronge, M. M. Labes. J. Chem. Phys. 51 (1969) 3213; H. Finkelmann, H. Stegemeyer, Z. Naturforschg. 28a (1973) 799). Later, the induction of cholesteric phases also possible by adding other chiral substances that themselves are not liquid crystalline (H. Stegemeyer, K. J. Mainusch, Na turwiss. 58 (1971) 599; H. Finkelmann, H. Stegemeyer, Ber. Bunsenges. Phys. Chem. 78 (1974) 869).
Die cholesterische Phase hat bemerkenswerte optische Eigenschaf ten: eine hohe optische Rotation sowie einen ausgeprägten Circu lardichroismus, der durch Selektivreflexion von circularpolari siertem Licht innerhalb der cholesterischen Schicht entsteht. Die je nach Blickwinkel zu beobachtenden unterschiedlichen Farben sind abhängig von der Ganghöhe der helicalen Überstruktur, die ihrerseits vom Verdrillungsvermögen der chiralen Komponente ab hängt. Dabei kann insbesondere durch Änderung der Konzentration eines chiralen Dotierstoffs die Ganghöhe und damit der Wellen längenbereich des selektiv-reflektierten Lichts einer cholesteri schen Schicht variiert werden (J. E. Adams, W. E. L. Haas, Mol. Cryst. Liq. Cryst. 16 (1972) 33). Solche cholesterischen Systeme bieten für eine praktische Anwendung interessante Möglichkeiten. So kann durch Einbau chiraler Molekülteile in mesogene Acryl säureester nach Orientierung in der cholesterischen Phase und Photovernetzung ein stabiles, farbiges Netzwerk hergestellt wer den, dessen Konzentration an chiraler Komponente aber nicht ver ändert werden kann (G. Galli, M. Laus, A. Angeloni, Makromol. Chem. 187 (1986) 289). Ferner kann durch Zumischen von nichtver netzbaren chiralen Verbindungen zu nematischen Acrylsäureestern nach Photovernetzung ein farbiges Polymer hergestellt werden (I. Heynderickx, D. J. Broer, Mol. Cryst. Liq. Cryst. 203 (1991) 113), das jedoch noch flüchtige Bestandteile enthält, die für eine Anwendung prohibitiv sind. Aus der Patentanmeldung P 43 42 280.2 sind schon chirale Verbindungen mit Zuckerresten bekannt.The cholesteric phase has remarkable optical properties ten: high optical rotation and a pronounced circu lardichroism by selective reflection from circularpolari generated light within the cholesteric layer. The different colors to be observed depending on the viewing angle depend on the pitch of the helical superstructure in turn depends on the twistability of the chiral component hangs. This can be done in particular by changing the concentration of a chiral dopant the pitch and thus the waves length range of the selectively reflected light of a cholesteri layer can be varied (J.E. Adams, W.E.L. Haas, Mol. Cryst. Liq. Cryst. 16 (1972) 33). Such cholesteric systems offer interesting possibilities for a practical application. For example, by incorporating chiral molecular parts into mesogenic acrylic acid esters after orientation in the cholesteric phase and Photo networking creates a stable, colored network the, whose concentration of chiral component does not ver can be changed (G. Galli, M. Laus, A. Angeloni, Makromol. Chem. 187 (1986) 289). Furthermore, by admixing non-ver wettable chiral compounds to nematic acrylic acid esters a colored polymer can be produced after photocrosslinking (I. Heynderickx, D. J. Broer, Mol. Cryst. Liq. Cryst. 203 (1991) 113), which however contains volatile components which are necessary for an application is prohibitive. From the patent application P 43 42 280.2 are already chiral compounds with sugar residues known.
Aufgabe der vorliegenden Erfindung war die Synthese neuer chiraler Verbindungen, die ein hohes Verdrillungsvermögen aufwei sen und die das Spektrum der verwendbaren Verbindungen erweitern.The object of the present invention was the synthesis of new ones chiral compounds that have a high twisting power sen and expand the range of compounds that can be used.
Die Erfindung betrifft Verbindungen der allgemeinen FormelThe invention relates to compounds of the general formula
in der die Reste
X unabhängig voneinander Bor, CH₂ oderin which the leftovers
X independently of one another boron, CH₂ or
B Wasserstoff, C₁- bis C₈-Alkyl, Phenyl, Diphenyl oder ein Rest der FormelB is hydrogen, C₁ to C₈ alkyl, phenyl, diphenyl or a Rest of the formula
A und A¹ Spacer
n 0, 1, 2 oder 3, m = 1 oder für X = CH₂ Null
M und M¹ gegebenenfalls durch Fluor, Chlor, Brom, Cyan, Hydroxy
oder Nitro substituierte ein- oder mehrkernige
aliphatische, aromatische, heteroaliphatische oder he
teroaromatische Ringsysteme, die Reste
Y unabhängig voneinander eine direkte Bindung,
O, S, COO, OCO, OCOO, CON(R) oder N(R)CO,
Z und Z¹ polymerisierbare Gruppen oder Wasserstoff,
R Wasserstoff oder C₁- bis C₄-Alkyl und
R¹ und R2 Wasserstoff, gegebenenfalls durch O, COO, OCO, OCOO
oder N(R) unterbrochenes C₁- bis C₃₀-Alkyl,
C₂- bis C₃₀-Alkenyl, C₁- bis C₃₀-Alkanoyl oder
C₃- bis C₃₀-Alkenoyl oder ein Rest der FormelA and A¹ spacers
n 0, 1, 2 or 3, m = 1 or for X = CH₂ zero
M and M¹ optionally substituted by fluorine, chlorine, bromine, cyano, hydroxy or nitro mono- or polynuclear aliphatic, aromatic, heteroaliphatic or he teroaromatic ring systems, the residues
Y independently of one another is a direct bond, O, S, COO, OCO, OCOO, CON (R) or N (R) CO,
Z and Z¹ polymerizable groups or hydrogen,
R is hydrogen or C₁ to C₄ alkyl and
R¹ and R 2 are hydrogen, optionally interrupted by O, COO, OCO, OCOO or N (R) C₁ to C₃₀ alkyl, C₂ to C₃₀ alkenyl, C₁ to C₃- alkanoyl or C₃ to C₃₀ alkenoyl or a Rest of the formula
sind,
wobei T eine direkte Bindung, CO, CH₂, CH=CH-CO, CH₂CH₂CO oder SO₂
ist und
A, M, n, y und Z die angegebene Bedeutung haben.are, wherein T is a direct bond, CO, CH₂, CH = CH-CO, CH₂CH₂CO or SO₂ and
A, M, n, y and Z have the meaning given.
Von besonderer Bedeutung sind Verbindungen mit:
X CH oder C-(C₁- bis-C₈-Alkyl),
n 1 oder 2,
M und M¹ einem aliphatischen oder aromatischen ein- oder mehr
kernigem Ringsystem,
Z und Z¹ Wasserstoff, Vinyl, Methylvinyl, Chlorvinyl, NCO, OCN
oderConnections with:
X is CH or C- (C₁- to C₈-alkyl),
n 1 or 2,
M and M¹ an aliphatic or aromatic mono- or multi-ring system,
Z and Z¹ are hydrogen, vinyl, methylvinyl, chlorovinyl, NCO, OCN or
R¹ und R² C₁- bis C₁₂-Alkyl- oder Alkanoyl, C₂- bis C₁₂-Alkenyl oder C₃- bis C₁₂-Alkenoyl, wobei die Reste noch durch O, COO, OCO oder OCOO unterbrochen sein können, oder ein Rest der FormelR¹ and R² are C₁ to C₁₂ alkyl or alkanoyl, C₂ to C₁₂ alkenyl or C₃- to C₁₂-alkenoyl, with the residues still through O, COO, OCO or OCOO can be interrupted, or a rest of the formula
Die Reste Y sind vorzugsweise eine direkte Bindung, O, COO, OCO oder OCOO.The radicals Y are preferably a direct bond, O, COO, OCO or OCOO.
Als Spacer A können alle für diesen Zweck bekannten Gruppen verwendet werden; üblicherweise sind die Spacer über Carbonat-, Ester- oder Ethergruppen oder eine direkte Bindung mit M, M¹, Z oder Z¹ verknüpft, d. h. die Reste Y entsprechen vorzugsweise einer direkten Bindung, O, COO, OCO oder OCOO. Die Spacer enthalten in der Regel 2 bis 30, vorzugsweise 2 bis 12 C-Atome und können in der Kette z. B. durch O, S, NH oder NCH₃ unterbrochen sein. Als Substituenten für die Spacerkette kommen dabei noch Fluor, Chlor, Brom, Cyan, Methyl oder Ethyl in Betracht.All groups known for this purpose can be used as spacers A. be used; The spacers are usually over carbonate, Ester or ether groups or a direct bond with M, M¹, Z or Z¹ linked, d. H. the radicals Y preferably correspond to one direct bond, O, COO, OCO or OCOO. The spacers contain in generally 2 to 30, preferably 2 to 12 carbon atoms and can in the chain z. B. be interrupted by O, S, NH or NCH₃. As Here, substituents for the spacer chain also contain fluorine, chlorine, Bromine, cyan, methyl or ethyl.
Repräsentative Spacer sind beispielsweise:
(CH₂)p, (CH₂CH₂O)qCH₂CH₂, CH₂CH₂SCH₂CH₂, CH₂CH₂NHCH₂CH₂,Representative spacers are for example:
(CH₂) p , (CH₂CH₂O) q CH₂CH₂, CH₂CH₂SCH₂CH₂, CH₂CH₂NHCH₂CH₂,
wobei
q 1 bis 3 und
p 1 bis 12 sind.in which
q 1 to 3 and
p are 1 to 12.
Die Reste M sind in der Regel nicht aromatisch oder aromatisch carbocyclische oder heterocyclische, gegebenenfalls durch Fluor, Chlor, Brom, Cyan, Hydroxy oder Nitro substituierte Ringsysteme, die z. B. folgenden Grundstrukturen entsprechen:The radicals M are generally not aromatic or aromatic carbocyclic or heterocyclic, optionally by fluorine, Chlorine, bromine, cyan, hydroxy or nitro substituted ring systems, the z. B. correspond to the following basic structures:
Besonders bevorzugt sind als Gruppen (M-Y)n oder (M¹-Y)n z.B.:Particularly preferred as groups are (MY) n or (M¹-Y) n, for example:
Die erfindungsgemäßen Einheiten Z-Y-A-(Y-M)n- oder Z¹-Y-A-(Y-M¹)n-, in denen Z, Z¹, Y, A, A¹, M und M¹ die oben ange gebene Bedeutung haben, sind durch allgemein bekannte Synthese verfahren, wie sie beispielsweise in der DE-A 39 17 196 beschrie ben sind, zugänglich.The units ZYA- (YM) n - or Z¹-YA- (Y-M¹) n -, in which Z, Z¹, Y, A, A¹, M and M¹ have the meaning given above, are by generally known synthesis procedure, as described for example in DE-A 39 17 196 ben accessible.
Die chiralen Molekülteile entstammen Hexosen, die käuflich erwor ben werden können und somit verfügbar sind. Die als Ausgangs material verwendeten optisch aktiven Hexaalkohole weisen die fol gende Grundstruktur auf:The chiral parts of the molecule come from hexoses, which can be purchased can be used and are therefore available. The as an exit optically active hexa alcohols used have the fol basic structure:
Diese Hexaalkohole sind die hydrierte Form der z. B. als Ausgangs substanzen genutzten Hexosen Allose, Altrose, Glucose, Mannose, Gulose, Idose, Galaktose und Talose. These hexa alcohols are the hydrogenated form of the z. B. as an output substances used hexoses allose, old rose, glucose, mannose, Gulose, idose, galactose and talose.
Die Herstellung der erfindungsgemäßen Verbindungen erfolgt in mehreren Schritten.The compounds according to the invention are prepared in several steps.
Zuerst wird, ausgehend von der Hexose durch Acetalisierung oder Ketalisierung mit Aldehyden bzw. Ketonen das gewünschte Bisacetal oder Bisketal hergestellt. In einem weiteren Reaktionsschritt werden dann die am Zuckerderivat verbliebenen OH-Gruppen z. B. mit entsprechenden Säuren verestert oder mit Halogenverbindungen verethert.First, starting from the hexose by acetalization or Ketalization with aldehydes or ketones is the desired bisacetal or bisque. In a further reaction step the OH groups remaining on the sugar derivative are then z. B. with corresponding acids esterified or with halogen compounds etherified.
Die Veresterung erfolgt nach der allgemein bekannten DCC-(Dicyclohexylcarbodiimid) Methode. Hierzu werden 0,01 mol des Zuckeracetals oder Zuckerketals sowie 0,022 mol der Carbonsäure in 100 ml Methylenchlorid gelöst oder suspendiert. Zu dieser Lösung oder Suspension werden bei 0°C 0,025 mol Dicyclohexylcarbo diimid sowie 0,0025 mol Dimethylaminopyridin (gelöst in CH₂Cl₂) gegeben. Die Reaktionsmischung rührt über Nacht. Zur Aufarbeitung wird das Reaktionsprodukt durch Eingießen in Wasser gefällt und anschließend säulenchromatographisch gereinigt.The esterification takes place according to the generally known DCC (dicyclohexylcarbodiimide) method. For this, 0.01 mol of Sugar acetals or sugar ketals and 0.022 mol of the carboxylic acid dissolved or suspended in 100 ml of methylene chloride. To this Solution or suspension are 0.025 mol dicyclohexylcarbo at 0 ° C diimide and 0.0025 mol dimethylaminopyridine (dissolved in CH₂Cl₂) given. The reaction mixture is stirred overnight. To work up the reaction product is precipitated by pouring it into water and then purified by column chromatography.
Verfahren zur Herstellung entsprechende Derivate sind z. B. in J. W. Goodby, J. Mater. Chem. 1 (1991)307; Organikum, 18. Auflage, Deutscher Verlag der Wissenschaften, Berlin 1990, S. 397; R. J. Ferrier, L. R. Hatton, Carbohydr. Res. 5(1967)132; T. B. Grind ley, V. Gulasekhram Carbohydr. Res. 74(1979)7; H. B. Sinclair, Car bohydr. Res. 12(1970)150; U. Peters W. Bankova, P. Welzel, Tetra hedron 43(1987)3803; F. E. Ziegler, G. D. Burger, Synth. Commun. 9(1979)539; B. Neises, W. Steglich, Angew. Chem. Intl. Ed 17(1978)522; E. H. Vickery, L. F. Pahler, E. J. Eisenbraun, J. Org. Chem 44(1979)4444; O. Mitsunobu, Synthesis(1981)1 und A. Hartwig, Dissertation, Universität Hamburg, 1994, beschrieben.Processes for the preparation of corresponding derivatives are e.g. B. in J. W. Goodby, J. Mater. Chem. 1 (1991) 307; Organic, 18th edition, German Publishing House of Sciences, Berlin 1990, p. 397; R.J. Ferrier, L.R. Hatton, Carbohydr. Res. 5 (1967) 132; T. B. Grind ley, V. Gulasekhram Carbohydr. Res. 74 (1979) 7; H. B. Sinclair, Car bohydr. Res. 12 (1970) 150; U. Peters W. Bankova, P. Welzel, Tetra hedron 43 (1987) 3803; F.E. Ziegler, G.D. Burger, Synth. Commun. 9 (1979) 539; B. Neises, W. Steglich, Angew. Chem. Intl. Ed 17 (1978) 522; E.H. Vickery, L.F. Pahler, E.J. Eisenbraun, J. Org. Chem 44 (1979) 4444; O. Mitsunobu, Synthesis (1981) 1 and A. Hartwig, Dissertation, University of Hamburg, 1994.
Die erfindungsgemäßen Verbindungen eignen sich insbesondere zur Verwendung in elektro-optischen Anzeigeelementen, als chiraler Dotierstoff für nematische oder cholesterische Flüssigkristalle zur Erzeugung farbig reflektierender Schichten oder zur Herstel lung von flüssigkristallin cholesterisch geordneten Pigmenten.The compounds according to the invention are particularly suitable for Use in electro-optical display elements, as chiral Dopant for nematic or cholesteric liquid crystals for producing colored reflective layers or for manufacturing development of liquid-crystalline cholesteric ordered pigments.
In einer Mischung aus 40 ml Benzaldehyd und 200 ml Dimethyl sulfoxid werden 20 g D-Mannitol gelöst. Dann werden in einem Zeitraum von etwa 20 Minuten 10 ml konzentrierte Schwefelsäure tropfenweise hinzugefügt, wobei sich die Mischung erwärmt. Nach 24 Stunden wird die Lösung in 3 l Eiswasser gegossen. Dabei scheidet sich ein Öl ab, das langsam fest wird. Der Feststoff wird abfiltriert und mit 200 ml Hexan gewaschen, dann mit 4-6 l Wasser bedeckt und zum Sieden erhitzt. Mit Natriumcarbonat wird der pH auf etwa 7-8 eingestellt. Beim Sieden der Lösung bleibt ein unlöslicher Rückstand zurück, der abfiltriert wird (wahr scheinlich Tri-O-(4-methoxybenzyliden)mannitol). Beim Abkühlen scheiden sich aus dem Filtrat Kristalle ab, durch Filtration erhält man 4,96 g 1,3; 4,6-Di-O-(4-methoxybenzyliden)-mannitol.In a mixture of 40 ml benzaldehyde and 200 ml dimethyl sulfoxide, 20 g of D-mannitol are dissolved. Then in one Period of about 20 minutes 10 ml of concentrated sulfuric acid added dropwise as the mixture warms. After The solution is poured into 3 l of ice water for 24 hours. Here separates an oil that slowly solidifies. The solid is filtered off and washed with 200 ml of hexane, then with 4-6 l Covered water and heated to boiling. With sodium carbonate the pH adjusted to about 7-8. When boiling the solution remains an insoluble residue that is filtered off (true apparently tri-O- (4-methoxybenzylidene) mannitol). When cooling down crystals separate out of the filtrate by filtration 4.96 g of 1.3 are obtained; 4,6-di-O- (4-methoxybenzylidene) mannitol.
4,81 g (0,01 Mol) des so erhaltenen Mannitols sowie 6,64 (0,022 Mol) der Verbindung der Formel4.81 g (0.01 mol) of the mannitol thus obtained and 6.64 (0.022 mol) of the compound of the formula
werden in 100 ml Methylenchlorid gelöst und dann bei 0°C mit 5,5 g (0,025 Mol) Dicyclohexylcarbodiimid und 0,31 g (0,025 Mol) 4-Dimethylaminopyridin versetzt. Nach dem Rühren über Nacht bei Raumtemperatur wird die Mischung in 500 ml Wasser gegossen und der ausfallende Niederschlag abgesaugt. Nach dem Chromatographie ren über Silicagel (Kieselgel 60; Laufmittel Toluol/Essigester 1 : 1) erhält man 5 g des 2,5-Bis-4-4′-heptylcyclohexyl)phenyl carbonyl-1,3; 4,6-di-O-(4-methoxybenzyliden)-D-mannitols der For melare dissolved in 100 ml of methylene chloride and then at 0 ° C with 5.5 g (0.025 mol) dicyclohexylcarbodiimide and 0.31 g (0.025 mol) 4-Dimethylaminopyridine added. After stirring overnight at The mixture is poured into 500 ml of water at room temperature the precipitate is suctioned off. After chromatography Ren over silica gel (silica gel 60; eluent toluene / ethyl acetate 1: 1) 5 g of 2,5-bis-4-4'-heptylcyclohexyl) phenyl are obtained carbonyl-1,3; 4,6-di-O- (4-methoxybenzylidene) -D-mannitol from For mel
Ausbeute: 49%
Phasenverhalten: K 202 (S 155) I
¹H-NMR (400 MHz, CDCl₃): 7,98 (d, 4H, H2′′, J = 8,14 Hz); 7,43
(d, 4H, H2′, J = 8,65 Hz); 7,32 (d, 4H, H3′, J = 8,14 Hz); 6,87
(d, 4H, H3′, J = 8,64 Hz); 5,54 (mc, 2H, H2, H5); 5,46
(s, 2H, Bz); 4,56 (dd, 2H, Heq1, Heq6, ²J = 10,68 Hz 3J = 5,59 Hz);
4,14 (d, 2H, H3, H4 J = 9,16 Hz); 3,8 (s, 6H, CH₃O); 3,72
(dd = t, 2H, Hax1, Hax6, J = 10,17 Hz); 2,56 (dd = t, 2H, H7′′,
J = 12,2 Hz); 1,91 (d, 8H, H8′′eq, J = 9,66 Hz);
1,52 (mc, 2H, H8′′ax); 1,13-0,86 (m, 36 H, Alkyl).Yield: 49%
Phase behavior: K 202 (S 155) I
1 H-NMR (400 MH z , CDCl₃): 7.98 (d, 4H, H2 ′ ′, J = 8.14 Hz); 7.43 (d, 4H, H2 ′, J = 8.65 Hz); 7.32 (d, 4H, H3 ′, J = 8.14 Hz); 6.87 (d, 4H, H3 ′, J = 8.64 Hz); 5.54 (mc, 2H, H2, H5); 5.46 (s, 2H, Bz); 4.56 (dd, 2H, Heq1, Heq6, ²J = 10.68 Hz 3J = 5.59 Hz); 4.14 (d, 2H, H3, H4 J = 9.16 Hz); 3.8 (s, 6H, CH₃O); 3.72 (dd = t, 2H, Hax1, Hax6, J = 10.17 Hz); 2.56 (dd = t, 2H, H7 ′ ′, J = 12.2 Hz); 1.91 (d, 8H, H8''eq, J = 9.66 Hz); 1.52 (mc, 2H, H8′′ax); 1.13-0.86 (m, 36H, alkyl).
Analog der angegebenen Arbeitsweise können auch die Verbindungen 3 der folgenden Beispiele hergestellt werden:The connections can also be carried out analogously to the specified mode of operation 3 of the following examples are prepared:
Ausbeute: 20%
Schmelzpunkt: 235°C
¹H-NMR (400 MHz, CDCl₃): 8,09 (d, 4H, H3′′, J = 8,14 Hz); 7,65
(d, 4H, H2′′, J = 8,14 Hz); 7,57 (d, 4H, H2′′′, J = 8,65 Hz);
7,42 (d, 4H, H2′, J = 8,65 Hz); 7,00 (d, 4H, H3′′′, J = 8,65 Hz);
6,93 (d, 4H, H3′′, J = 8,64 Hz); 5,60 (mc, 2H, H2); 5,49 (s, 2H,
Bz); 4,59 (dd, 2H, H1eq, H₆eq, ²J = 10,68 Hz, ³J = 5,6 Hz); 4,20
(d, 2H, H3, J = 9,15 Hz); 4,02 (t, 4H, CH₂O, J = 6,62 Hz); 3,78
(s, 6H, MeO); 3,77 (dd = t, 2H, H1ax, J = 10,43 Hz);
1,82 (mc, 4H, CH₂CH₂O); 1,54-1,26 (m, 16H, Alkyl);
0,90 (t, 6H, CH₃₁ J = 6,9 Hz)Yield: 20%
Melting point: 235 ° C
1 H-NMR (400 MH z , CDCl₃): 8.09 (d, 4H, H3 ′ ′, J = 8.14 Hz); 7.65 (d, 4H, H2 ′ ′, J = 8.14 Hz); 7.57 (d, 4H, H2 ′ ′ ′, J = 8.65 Hz); 7.42 (d, 4H, H2 ′, J = 8.65 Hz); 7.00 (d, 4H, H3 ′ ′ ′, J = 8.65 Hz); 6.93 (d, 4H, H3 ′ ′, J = 8.64 Hz); 5.60 (mc, 2H, H2); 5.49 (s, 2H, Bz); 4.59 (dd, 2H, H1eq, H₆eq, 2 J = 10.68 Hz, 3 J = 5.6 Hz); 4.20 (d, 2H, H3, J = 9.15 Hz); 4.02 (t, 4H, CH₂O, J = 6.62 Hz); 3.78 (s, 6H, MeO); 3.77 (dd = t, 2H, H1ax, J = 10.43 Hz); 1.82 (mc, 4H, CH₂CH₂O); 1.54-1.26 (m, 16H, alkyl); 0.90 (t, 6H, CH₃₁ J = 6.9 Hz)
Ausbeute: 35%
Schmelzpunkt: 219°C
¹H-NMR (400 MHz, CDCl₃): 8;01 (d, 2H, H3′′, J = 8,14 Hz);
7,58 (d, 2H, H2′′, J = 8,65 Hz), 7,55 (d, 2H, H3′′′,
J = 8,65 Hz); 7,45 (d, 2H, H2′, J = 8,65 Hz); 7,32
(d, 2H, H2′′′′, j = 8,65 Hz); 6,99 (d, 2H, H3′′′, J = 5,09 Hz);
6,90 (d, 2H, H3′, J = 9,15 Hz); 6,76 (d, 2H, H3′′′′,
J = 8,65 Hz); 5,61 (mc, 1H, H2); 5,57 (s, 1H, Bz); 5,37
(s, 1H, Bz); 4,59 (dd, 1H, H1eq, ²J = 10,68 Hz, ³J = 5,6 Hz); 4,43
(dd, 1H, H3, J = 2,54 Hz, J = 9,66 Hz); 4,31
(dd, 1H, ²J = 11,23 Hz, ³J = 5,09 Hz); 4,22 (mc, 1H, H5); 4,01
(t, 2H, CH₂O, J = 6,61 Hz); 3,87 (dd, 1H, H4, J = 2,29 Hz,
J = 9,16 HZ); 3,81 (s, 3H, MeO′); 3,83-3,78 (m, 1H, H1ax); 3,71
(s, 3H, MeO′′′), 3,59 (dd = t, H6ax, J = 10,17 Hz);
1,82 (mc, 2H, CH₂-CH₂-O); 1,50-1,08 (m, 8H, Alkyl); 0,90
(t, 3H, CH₃, J = 6,61 Hz).Yield: 35%
Melting point: 219 ° C
1 H-NMR (400 MH z , CDCl₃): 8; 01 (d, 2H, H3 ′ ′, J = 8.14 Hz); 7.58 (d, 2H, H2 ′ ′, J = 8.65 Hz), 7.55 (d, 2H, H3 ′ ′ ′, J = 8.65 Hz); 7.45 (d, 2H, H2 ′, J = 8.65 Hz); 7.32 (d, 2H, H2 ′ ′ ′ ′, j = 8.65 Hz); 6.99 (d, 2H, H3 ′ ′ ′, J = 5.09 Hz); 6.90 (d, 2H, H3 ′, J = 9.15 Hz); 6.76 (d, 2H, H3 ′ ′ ′ ′, J = 8.65 Hz); 5.61 (mc, 1H, H2); 5.57 (s, 1H, Bz); 5.37 (s, 1H, Bz); 4.59 (dd, 1H, H1eq, 2 J = 10.68 Hz, 3 J = 5.6 Hz); 4.43 (dd, 1H, H3, J = 2.54 Hz, J = 9.66 Hz); 4.31 (dd, 1H, ²J = 11.23 Hz, ³J = 5.09 Hz); 4.22 (mc, 1H, H5); 4.01 (t, 2H, CH₂O, J = 6.61 Hz); 3.87 (dd, 1H, H4, J = 2.29 Hz, J = 9.16 HZ); 3.81 (s, 3H, MeO ′); 3.83-3.78 (m, 1H, H1ax); 3.71 (s, 3H, MeO ′ ′ ′), 3.59 (dd = t, H6ax, J = 10.17 Hz); 1.82 (mc, 2H, CH₂-CH₂-O); 1.50-1.08 (m, 8H, alkyl); 0.90 (t, 3H, CH₃, J = 6.61 Hz).
Ausbeute: 16%
Schmelzpunkt: 183°C
¹H-NMR (400 MHz, CDCl₃): 7,99 (d, 4H, H3′′, J = 8,64 Hz); 7,42
(d, 4H, H2′; J = 8,65 Hz); 6,93 (d, 4H, H3′′, J = 8,64 Hz); 6,84
(d, 4H, H3′, J = 8,64 Hz); 5,52 (mc, 2H, H2, H5); 5,46
(s, 2H, Bz); 4,56 (dd, 2H, H1eq, H6eq, ²J = 10,68 Hz,
³J = 5,6 Hz); 4,15-4,09 (m, 6H, H3, CH₂-O); 3,8 (s, 6H, CH₃O);
3,72 (dd = t, 2H, H1ax, H6ax, J = 10,17 Hz); 1,46 (t, 6H, CH₃,
J = 7,13 Hz)
Yield: 16%
Melting point: 183 ° C
1 H-NMR (400 MH z , CDCl₃): 7.99 (d, 4H, H3 ′ ′, J = 8.64 Hz); 7.42 (d, 4H, H2 ′; J = 8.65 Hz); 6.93 (d, 4H, H3 ′ ′, J = 8.64 Hz); 6.84 (d, 4H, H3 ′, J = 8.64 Hz); 5.52 (mc, 2H, H2, H5); 5.46 (s, 2H, Bz); 4.56 (dd, 2H, H1eq, H6eq, 2 J = 10.68 Hz, 3 J = 5.6 Hz); 4.15-4.09 (m, 6H, H3, CH₂-O); 3.8 (s, 6H, CH₃O); 3.72 (dd = t, 2H, H1ax, H6ax, J = 10.17 Hz); 1.46 (t, 6H, CH₃, J = 7.13 Hz)
Ausbeute: 3%
Schmelzpunkt: 141,5°C
Verdrillungsvermögen: β = 34,8 µm-1 in ZLI 1840
¹H-NMR (400 MHz, CDCl₃): 7,98 (d, 4H, H2′′, J = 8,64 Hz); 7,42
(d, 4H, H2′, J = 8,64 Hz); 6,93 (d, 4H, H3′′, J = 9,16 Hz); 6,86
(d, 4H, H3′, J = 8,65 Hz); 5,50 (m, 2H, H2, H5); 5,46
(s, 2H, Bz); 4,56 (dd, 2H, Heq1, Heq6, ²J = 10,68 Hz,
³J = 5,6 Hz); 4,13 (d, 2H, H3, H4, J = 9,15 Hz); 4,03 (t, 4H,
-CH₂O, J = 6,61 Hz); 3,8 (s, 6H, CH₃O); 3,72 (dd = t, 2H,
Hax1, Hax6, J = 10,17 Hz); 1,80 (m, 4H, CH₂-CH₂O); 1,49-1,26
(m, 40H, Alkyl); 0,88 (t, 3H, -CH₃, J = 6,62)Yield: 3%
Melting point: 141.5 ° C
Twist: β = 34.8 µm -1 in ZLI 1840
1 H-NMR (400 MH z , CDCl₃): 7.98 (d, 4H, H2 ′ ′, J = 8.64 Hz); 7.42 (d, 4H, H2 ′, J = 8.64 Hz); 6.93 (d, 4H, H3 ′ ′, J = 9.16 Hz); 6.86 (d, 4H, H3 ′, J = 8.65 Hz); 5.50 (m, 2H, H2, H5); 5.46 (s, 2H, Bz); 4.56 (dd, 2H, Heq1, Heq6, ²J = 10.68 Hz, ³J = 5.6 Hz); 4.13 (d, 2H, H3, H4, J = 9.15 Hz); 4.03 (t, 4H, -CH₂O, J = 6.61 Hz); 3.8 (s, 6H, CH₃O); 3.72 (dd = t, 2H, Hax1, Hax6, J = 10.17 Hz); 1.80 (m, 4H, CH₂-CH₂O); 1.49-1.26 (m, 40H, alkyl); 0.88 (t, 3H, -CH₃, J = 6.62)
Claims (8)
X unabhängig voneinander Bor, CH₂ oder B Wasserstoff, C₁- bis C₈-Alkyl, Phenyl, Diphenyl oder ein Rest der Formel A und A¹ Spacer
n 0, 1, 2 oder 3, m = 1 oder für X = CH₂ Null
M und M¹ gegebenenfalls durch Fluor, Chlor, Brom, Cyan, Hydroxy oder Nitro substituierte ein- oder mehr kernige aliphatische, aromatische, heteroaliphati sche oder heteroaromatische Ringsysteme, die Reste
Y unabhängig voneinander eine direkte Bindung, O, S, COO, OCO, OCOO, CON(R) oder N(R)CO,
Z und Z¹ polymerisierbare Gruppen oder Wasserstoff,
R Wasserstoff oder C₁- bis C₄-Alkyl und
R¹ und R² Wasserstoff, gegebenenfalls durch O, COO, OCO, OCOO oder N(R) unterbrochenes C₁- bis C₃₀-Alkyl, C₂- bis C₃₀-Alkenyl, C₁- bis C₃₀-Alkanoyl oder C₃- bis C₃₀-Alkenoyl oder ein Rest der Formel sind,
wobei T eine direkte Bindung, CO, CH₂, CH=CH-CO, CH₂CH₂CO oder SO₂ ist und
A, M, n, y und Z die angegebene Bedeutung haben.1. Compounds of the general formula in which the leftovers
X independently of one another boron, CH₂ or B is hydrogen, C₁ to C₈ alkyl, phenyl, diphenyl or a radical of the formula A and A¹ spacers
n 0, 1, 2 or 3, m = 1 or for X = CH₂ zero
M and M¹ optionally substituted by fluorine, chlorine, bromine, cyano, hydroxy or nitro mono- or more nuclear aliphatic, aromatic, heteroaliphatic or heteroaromatic ring systems, the radicals
Y independently of one another is a direct bond, O, S, COO, OCO, OCOO, CON (R) or N (R) CO,
Z and Z¹ polymerizable groups or hydrogen,
R is hydrogen or C₁ to C₄ alkyl and
R¹ and R² are hydrogen, optionally interrupted by O, COO, OCO, OCOO or N (R) C₁ to C₃₀ alkyl, C₂ to C₃₀ alkenyl, C₁ to C₃₀ alkanoyl or C₃ to C₃₀ alkenoyl or a radical of the formula are,
where T is a direct bond, CO, CH₂, CH = CH-CO, CH₂CH₂CO or SO₂ and
A, M, n, y and Z have the meaning given.
X CH oder C-(C₁- bis-C₈-Alkyl) ist.2. Compounds according to claim 1 in which
X is CH or C- (C₁ to C₈ alkyl).
n 1 oder 2 ist.3. Compounds according to claim 1 in which
n is 1 or 2.
M und M¹ ein aliphatisches oder aromatisches ein- oder mehrkerniges Ringsystem sind.4. Compounds according to claim 1 in which
M and M¹ are an aliphatic or aromatic mono- or polynuclear ring system.
Z und Z¹ Wasserstoff, Vinyl, Methylvinyl, Chlorvinyl, NCO, OCN oder sind.5. Compounds according to claim 1 in which
Z and Z¹ are hydrogen, vinyl, methylvinyl, chlorovinyl, NCO, OCN or are.
Y eine direkte Bindung, O, COO, OCO oder OCOO sind.7. Compounds according to claim 1, in which the radicals
Y is a direct bond, O, COO, OCO or OCOO.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1996125441 DE19625441A1 (en) | 1996-06-25 | 1996-06-25 | Chiral dopants for liquid crystalline media |
| PCT/EP1997/003044 WO1997049694A1 (en) | 1996-06-25 | 1997-06-12 | Chiral doping agents for liquid crystalline media |
| AU31755/97A AU3175597A (en) | 1996-06-25 | 1997-06-12 | Chiral doping agents for liquid crystalline media |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1996125441 DE19625441A1 (en) | 1996-06-25 | 1996-06-25 | Chiral dopants for liquid crystalline media |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE19625441A1 true DE19625441A1 (en) | 1998-01-02 |
Family
ID=7797987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1996125441 Withdrawn DE19625441A1 (en) | 1996-06-25 | 1996-06-25 | Chiral dopants for liquid crystalline media |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU3175597A (en) |
| DE (1) | DE19625441A1 (en) |
| WO (1) | WO1997049694A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1136478A2 (en) * | 2000-03-20 | 2001-09-26 | Basf Aktiengesellschaft | Chiral 1,3-dioxane compounds |
| DE102012201962A1 (en) | 2011-10-13 | 2013-04-18 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Substituted amino alcohols as chiral dopants |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19940681A1 (en) | 1999-08-27 | 2001-03-01 | Basf Ag | Cholesteric layer material with improved color fastness and process for its production |
| DE19940682A1 (en) | 1999-08-27 | 2001-03-01 | Basf Ag | Cholesteric layer material with improved color impression and process for its production |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3405914A1 (en) * | 1984-02-18 | 1985-08-22 | Merck Patent Gmbh, 6100 Darmstadt | LIQUID CRYSTAL LINKS |
| GB9220189D0 (en) * | 1992-09-24 | 1992-11-04 | Central Research Lab Ltd | Dioxane derivatives |
| DE4342280A1 (en) * | 1993-12-11 | 1995-06-14 | Basf Ag | Polymerizable chiral compounds and their use |
| US5667721A (en) * | 1995-03-16 | 1997-09-16 | Rolic Ag | Liquid crystalline di-1,3-dioxane derivatives |
-
1996
- 1996-06-25 DE DE1996125441 patent/DE19625441A1/en not_active Withdrawn
-
1997
- 1997-06-12 AU AU31755/97A patent/AU3175597A/en not_active Withdrawn
- 1997-06-12 WO PCT/EP1997/003044 patent/WO1997049694A1/en active Application Filing
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1136478A2 (en) * | 2000-03-20 | 2001-09-26 | Basf Aktiengesellschaft | Chiral 1,3-dioxane compounds |
| EP1136478A3 (en) * | 2000-03-20 | 2003-01-22 | Basf Aktiengesellschaft | Chiral 1,3-dioxane compounds |
| US6616990B2 (en) | 2000-03-20 | 2003-09-09 | Basf Aktiengesellschaft | Chiral 1, 3-dioxane compounds |
| DE102012201962A1 (en) | 2011-10-13 | 2013-04-18 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Substituted amino alcohols as chiral dopants |
| WO2013053752A1 (en) | 2011-10-13 | 2013-04-18 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Substituted amino alcohols as chiral dopants |
| US9273247B2 (en) | 2011-10-13 | 2016-03-01 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Substituted amino alcohols as chiral dopants |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1997049694A1 (en) | 1997-12-31 |
| AU3175597A (en) | 1998-01-14 |
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