WO1996033251A1 - Liquid crystal compounds having a chiral fluorinated terminal portion - Google Patents

Liquid crystal compounds having a chiral fluorinated terminal portion Download PDF

Info

Publication number
WO1996033251A1
WO1996033251A1 PCT/US1996/002636 US9602636W WO9633251A1 WO 1996033251 A1 WO1996033251 A1 WO 1996033251A1 US 9602636 W US9602636 W US 9602636W WO 9633251 A1 WO9633251 A1 WO 9633251A1
Authority
WO
WIPO (PCT)
Prior art keywords
integer
group
independently
compounds
mmol
Prior art date
Application number
PCT/US1996/002636
Other languages
French (fr)
Inventor
Gilbert C. Johnson
Marc D. Radcliffe
Patricia M. Savu
Daniel C. Snustad
Terence D. Spawn
Original Assignee
Minnesota Mining And Manufacturing Company
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Minnesota Mining And Manufacturing Company filed Critical Minnesota Mining And Manufacturing Company
Priority to EP96908535A priority Critical patent/EP0821719B1/en
Priority to DE69625590T priority patent/DE69625590T2/en
Priority to JP8531712A priority patent/JPH11505212A/en
Publication of WO1996033251A1 publication Critical patent/WO1996033251A1/en

Links

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
    • C09K19/04—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • C07D239/26—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/18—Oxygen atoms
    • C07D263/20—Oxygen atoms attached in position 2
    • C07D263/24—Oxygen atoms attached in position 2 with hydrocarbon radicals, substituted by oxygen atoms, attached to other ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C09K19/126—Compounds containing at least one asymmetric carbon atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—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
    • C09K19/3463—Pyrimidine with a carbon chain containing at least one asymmetric carbon atom, i.e. optically active pyrimidines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/3483—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a non-aromatic ring

Definitions

  • This invention relates to fluorinated chiral smectic liquid crystal compounds, to a process for the preparation of such compounds (and to intermediates for use therein), and to liquid crystal compound mixtures and electrooptical display devices containing such compounds.
  • Liquid crystal displays have a number of unique characteristics, including low voltage and low power of operation, which make them the most promising of the non-emissive electrooptical display candidates currently available.
  • response time i.e., the time required for the device to switch from the on (light) state to the off (dark) state.
  • ⁇ the rotational viscosity
  • this invention provides fluorine-containing, chiral liquid crystal compounds having smectic mesophases or latent smectic mesophases. (Compounds having latent smectic
  • the chiral liquid crystal compounds of the invention comprise (a) a chiral fluorochemical terminal portion containing at least one methylene group and optionally containing at least one catenary, i.e., in-chain, ether oxygen atom; (b) a saturated, chiral or achiral, hydrocarbon terminal portion; and (c) a central core connecting the terminal portions.
  • R f group of the fluorochemical terminal portion is perfluoroalkyl or perfluoroether, it can contain small amounts of
  • R f is fluoroalkyl, fluoroether, or perfluoroether; more preferably, R f is perfluoroether, as the perfluoroether-containing compounds of the invention exhibit, e.g., a broad smectic C mesophase, good compatibility with other smectic C compounds, and advantageous layer spacing behavior.
  • D' is preferably a covalent bond.
  • the compounds of this invention have a central core comprised of at least one or two rings independently selected from the group consisting of aromatic, heteroaromatic, alicyclic, substituted aromatic, substituted heteroaromatic, and substituted alicyclic rings, the rings being connected one with another by a covalent bond or by chemical groups selected from the group consisting of -COO-, -COS-,
  • the rings can be fused or non-fused.
  • heteroaromatic rings comprise at least one atom
  • Non-adjacent ring carbon atoms in the alicyclic rings can be substituted by nitrogen, oxygen, or sulfur atoms.
  • the ring(s) are aromatic, heteroaromatic, substituted aromatic, or substituted heteroaromatic, the non-fused rings of the core are preferably no more than about two in number.
  • the chiral liquid crystal compounds of the invention provide exceptionally fast response times over broad temperature ranges.
  • the compounds exhibit surprisingly high polarization values (relative to comparable compounds having a chiral center located on the other side of the core, away from the fluorochemical terminal portion) and surprisingly low viscosities in view of their high polarizations.
  • many of the compounds have broad smectic C temperature ranges, making them useful alone, as well as in admixture with other chiral or achiral liquid crystal compounds (as dopants or as the major components), for electrooptical display applications.
  • the compounds of the invention have a number of desirable properties when used in admixture with other liquid crystal compounds, preferably compounds having fluorinated terminal portions such as those compounds disclosed, for example, in U.S. Pat. Nos. 4,886,619 (Janulis), 5,082,587 (Janulis), and 5,262,082 (Janulis et al.).
  • the compounds of the invention when admixed with such preferred liquid crystal compounds show excellent compatibility, show a beneficial effect or only a minimal negative effect on the smectic C temperature range of the resulting mixtures (even when present at high concentrations), and provide ferroelectric mixtures having fast
  • this invention also provides a mixture of liquid crystal compounds
  • liquid crystal compound of the invention comprising at least one liquid crystal compound of the invention, a liquid crystal display device containing at least one liquid crystal compound of the invention, liquid crystal intermediate compounds, and a process for preparing the liquid crystal compounds of the invention.
  • a class of the non-polymeric liquid crystal materials, i.e., liquid crystal compounds, of the present invention can be represented by the general formula I:
  • each X, Y, and Z are independently selected from the group consisting of -H, -Cl, -F, -Br, -I, -OH, -OCH 3 , -CH;., -CF 3 , -OCF 3 , -CN, and -NO 2 ; each l, m, and n are independently zero or an integer of 1 to 4;
  • D is non-directionally selected from the group
  • r and r' are independently integers of 0 to about 20, s is independently an integer of 1 to about 10 for each (C 5 H 2s O), t is an integer of 1 to about 6, and p is an integer of 0 to about 4;
  • R is selected from the group consisting of
  • q' is independently an integer of 1 to about 20 for each (C q ,H 2q ,-O); q is an integer of 1 to about 20;
  • w is an integer of 0 to about 10;
  • R f ' is -R*-D- (O) x -CH 2 -D' -R f , where R* is a cyclic or acyclic chiral moiety; D and D' are each independently and non-directionally selected from the group set forth for D above; x is an integer of 0 or 1; and R f is fluoroalkyl, perfluoroalkyl, fluoroether, or
  • R f is fluoroalkyl
  • R* is selected from the group consisting of
  • each R' is independently selected from the group consisting of -Cl, -F, -CF 3 , -NO 2 , -CN, -H, -C q H 2q+1 ,
  • q' is independently an integer of 1 to about 20 for each ((C q ,H 2q , -V' -(R') V ')-O); q is an integer of 1 to about 20; w is an integer of 0 to about 10; v is an integer of 0 to about 6; each v' is independently an integer of 0 to about 6; g is an integer of 1 to about 3; each D is independently and non-directionally selected from the group set forth for D above, with the proviso that the ring containing D has from about 3 to about 10 ring
  • fluoroalkyl and fluoroether groups are those which can be represented by the formula -R f ''-R h , where R f '' is a linear or branched, perfluorinated or partially- fluorinated alkylene group having from 1 to about 10 (preferably, from about 2 to about 6) carbon atoms and optionally containing one or more catenary, i.e., in- chain, ether oxygen atoms, and R h is a linear or branched alkyl group having from 1 to about 14
  • R f '' is perfluorinated, both R h and R f '' are linear, and at least one of the groups R h and R f '' contains at least one catenary ether oxygen atom. More preferably, R h or both R h and R f '' contains at least one catenary ether oxygen atom.
  • Particularly preferred perfluoroether groups are those which can be represented by the formula -(C x F 2x O) z C y F 2y+1 , where x is independently an integer of 1 to about 10 for each (C x F 2x O), y is an integer of 1 to about 10, and z is an integer of 1 to about 10.
  • the perfluoroether group is linear, x is independently an integer of 1 to about 6 for each
  • R'' is (R') v -C q H 2q+1-v , where q is an integer of 2 to about 10
  • each R' is independently selected from the group consisting of hydrogen, fluorine, chlorine, methyl, and perfluoromethyl
  • v is an integer of 1 to about 3
  • j is an integer of 0 or 1
  • G is selected from the group consisting of
  • R* is selected from the group consisting of
  • R' is -F
  • q is an integer of 1 to about 4
  • v is an integer of 1 to about 3
  • W is N or CH
  • s is an integer of 1 to about 6
  • t is an integer of 0 or 1
  • r' is an integer of 1 to about 3
  • Rf is selected from the group consisting of -C q F 2q X', -R f ''-R h , and - (C x F 2x O) z C y F 2y+1 , where q is an integer of 1 to about 6,
  • X' is fluorine
  • R f '' is a linear or branched, perfluorinated alkylene group having from about 2 to about 4 carbon atoms and
  • R h is a linear or branched alkyl group having from about 2 to about 7 carbon atoms and optionally containing one or more catenary ether oxygen atoms
  • x is independently an integer of 1 to about 10 for each (C x F 2x O)
  • y is an integer of 1 to about 8
  • z is an integer of 1 to about 5.
  • the fluorine-containing liquid crystal compounds of the invention can be prepared by a process comprising the steps of (a) mixing at least one
  • K with at least one compound represented by the formula where M, N, P, a, b, c, A, B, X, Y, Z, 1, m, n, D, R,
  • R*, R f , and R f ' are as defined above for formula I; x is an integer of 0 or 1; and each A', A'', B', and B' ' are independently selected from the group consisting of -H, -Cl, -Br, -I, -OH, -COOH, -CH(CH 2 OH) 2 , -SH, -SeH, -TeH, -NH 2 , -COCl, -CHO, -OSO 2 R f ''', -OSO 2 CH 3 ,
  • R f ''' is a perfluoroalkyl group having from 1 to about 10 carbon atoms and q is an integer of 0 to about 20, and with the proviso that (R*) x -A' can enter into an addition or condensation reaction with A'' and that (R*) x -B' can enter into an addition or condensation reaction with B''; and (b) allowing compounds III and IV, compounds V and VI, or compounds III and VII to react, optionally in the presence of suitable coupling agent (s), i.e., reagent (s) which effect coupling.
  • suitable coupling agent i.e., reagent (s) which effect coupling.
  • Most of the compounds of the present invention have enhanced smectic mesophases.
  • Mixtures of the compounds of the invention with other liquid crystal materials can be formulated to provide desired transition temperatures and broad mesophase temperature ranges.
  • Such mixtures preferably contain compounds having fluorinated terminal portions, such as those compounds described, for example, in U.S. Pat. Nos. 4,886,619 (Janulis), 5,082,587 (Janulis), and, most preferably, 5,262,082 (Janulis et al.).
  • the compounds of this invention in admixture with other chiral or achiral liquid crystal compounds may exhibit chiral smectic liquid crystal behavior.
  • many of the perfluoroether group- containing liquid crystal compounds of the invention when used alone or when mixed with other liquid crystal compounds of the invention or with achiral, fluorine- containing liquid crystal compounds preferably, the perfluoroether group-containing liquid crystal
  • transformations were comprised of acylation, esterification, etherification, alkylation, and
  • the p-toluene sulfonate derivative of the alcohol was prepared by the addition of 4-toluenesulfonyl chloride (120.6 mg, 0.63 mmol) to a solution of the alcohol (236 mg, 0.57 mmol), dimethylaminopyridine (DMAP, 2.8 mg, 0.02 mmol), and N,N'-diisopropylethylamine (0.2 ml, 1.14 mmol) in dichloromethane (2.0 ml). The resulting mixture was stirred for 8 hours at room temperature and was then coated onto 0.5 g of silica gel.
  • 4-toluenesulfonyl chloride (120.6 mg, 0.63 mmol)
  • DMAP dimethylaminopyridine
  • N,N'-diisopropylethylamine 0.2 ml, 1.14 mmol
  • dichloromethane 2.0 ml
  • pyrimidine (10.0 g, 29.3 mmol) (prepared essentially as described by Sakaguchi et al. in Ferroelectrics 114, 269 (1992)), 2,2-difluoro-2-[1,1,2,2-tetrafluoro-2- nonfluorobutoxy)ethanol] (15.2 g, 35.16 mmol), and tetrabutyl ammonium hydrogen sulfate (500 mg, 1.5 mmol) in tetrahydrofuran (20 ml) .
  • the resulting mixture was heated to reflux temperature for 23 hours, was diluted with water (100 ml), and was extracted with three 100 ml aliquots of ethyl acetate.
  • the resulting mixture was warmed to -30°C over a period of 2 hours, and then pyridine (3.3 g, 41.4 mmol) was added to the mixture.
  • the mixture was allowed to warm to ambient temperature and was stirred for 12 hours.
  • the mixture was then poured into a slurry of silica gel (40 g) in diethyl ether and was concentrated onto the silica gel under reduced pressure.
  • the product-coated silica was placed on top of 100 g of fresh silica gel and was eluted with a 10:1 hexanes/ethyl acetate solution.
  • Tetrabutylammonium bromide (416 mg, 1.29 mmol) was then added to the resulting mixture, and the mixture was allowed to warm to ambient temperature. The mixture was stirred at ambient temperature for 5 hours. The mixture was coated on to silica gel, and the resulting product was then purified by column chromatography
  • 5-Hexyloxy-2-(4-hydroxyphenyl)pyrimidine was prepared essentially by the procedure described by Zaschke et al., supra. The title compound was then prepared essentially as described in Example 8 by replacing 5-hexyl-2-(4-hydroxyphenyl)pyrimidine with 5- hexyloxy-2-(4-hydroxyphenyl)pyrimidine (0.54 g, 2.0 mmo1.
  • 5-Octyloxy-2-(4-hydroxyphenyl)pyrimidine was prepared essentially as described in Example 9 by substituting octanol for hexanol .
  • the title compound was then prepared essentially as described in Examples 3 and 4 by replacing (R)-5-octyl-2-[4-(2,3- oxiranylpropoxy)phenyl]pyrimidine with (S)-5-octyloxy- 2-[4-(2,3-oxiranylpropoxy)phenyl]pyrimidine (10.0 g, 28.0 mmol) and using 2-[2-(nonfluorobutoxy)- tetrafluoroethoxy]-2,2-difluoroethanol (13.3 g, 31 mmol).
  • the resulting (S)-hydroxy compound was treated with 2 equivalents of diethylaminosulfur trifluoride to produce the title compound.
  • the title compound was prepared essentially as described in Examples 3 and 4 by combining 5-butoxy- 2,2,3,3,4,4-hexafluoropentanol (3.1 g, 11.7 mmol, prepared essentially by the method described in U.S. Patent No. 5,399,291 (Janulis et al.)) with (S)-5- octyl-2-[4-(2,3-oxiranylpropoxy)phenyl] pyrimidine (2.0 g, 5.87 mmol) to produce 5-octyl-2-[4-((S)-2-hydroxy-3- (-5-butoxy-2,2,3,3,4,4- hexafluoropentoxy) propoxy) phenyl] pyrimidine.
  • This chiral (S)-hydroxy compound 2.0 g, 3.3 mmol
  • the title compound was prepared essentially as described in Examples 3 and 4 by combining 2-(N- (2,2,3,3,5,5,6,6-octafluoro)morpholino)-2,2- difluoroethanol (2.18 g, 7.0 mmol) with (S)-5-octyl-2- [4-(2,3-oxiranylpropoxy)phenyl]pyrimidine (2.0 g, 5.87 mmol) to produce 5-octyl-2-[4-((S)-2-hydroxy-3-(2-(N- (2,2,3,3,5,5,6,6-octafluoro)morpholino)-2,2- difluoroethoxy)propoxy)phenyl]pyrimidine.
  • This chiral (S)-hydroxy compound (3.0 g, 4.6 mmol) was treated with diethylaminosulfur trifluoride (1.5 g, 9.2 mmol) to produce the title compound.
  • the title compound was prepared essentially as described in Examples 3 and 4 by combining 2-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy) ethanol (3.3 g, 7.0 mmol) with (S)-5- octyl-2-[4-(2,3-oxiranylpropoxy)phenyl]pyrimidine (2.0 g, 5.87 mmol) to produce 5-octyl-2-[4-((S)-2-hydroxy-3- (2-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)ethoxy)propoxy)phenyl]pyrimidine.
  • This chiral (S)-hydroxy compound (1.6 g, 1.95 mmol) was treated with diethylaminosulfur trifluoride (0.63 g, 3.92 mmol) to produce the title compound.
  • the title compound was prepared essentially as described in Example 8 by combining 3-(2-[2- (nonfluorobutoxy)tetrafluoroethoxy]-2,2- difluoroethoxy)-(R)-2-fluoropropyl-1-p-toluenesulfonate (0.5 g, 0.75 mmol) with 2,3-difluoro-4-octyl-4'- hydroxybiphenyl (0.24 g, 0.75 mmol, prepared
  • Example 20 The title compound was prepared essentially as described in Example 18 using (S)-2-fluoro-decyl-p- toluenesulfonate (0.146 g, 0.44 mol) in place of (R) -2- fluoro-decyl-p-toluenesulfonate.
  • Triethylamine (230 mg, 1.76 mmol) was added to a solution of N-(4-hydroxy)phenyl-(S)-5-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy) 2,2-difluoroethoxy) methyl-2-oxazolidinone (500 mg, 0.88 mmol) and 4- octyloxybenzoyl chloride (220 mg, 0.88 mmol) in
  • a one liter flask was fitted with an addition funnel, a mechanical stirrer, a reflux condenser, and a thermometer and was charged with 1,3-dibromopropane (360 g, 1.78 mol), 2-(2- (nonafluorobutoxy)tetrafluoroethoxy) 2,2-difluoroethanol (150 g, 0.347 mol), and Adogen 464TM quaternary ammonium phase transfer catalyst (available from Aldrich
  • fluorochemical phase of the mixture was separated, and the upper phase was treated with ether (60 mL) and water (40 mL) and then washed with brine.
  • the cis (S,S) isomer of the product was isolated as a 4.9:1 ratio of the cis to trans, and the trans (S,R) isomer was isolated as a 7.3:1 ratio of the trans to cis isomers by liquid chromatography on silica gel using 4:1 hexanes/ethyl acetate as the eluent.
  • Example 23 was prepared essentially as described in Examples 3 and 4 by combination of
  • Example 24 trifluoride (0.6 g, 3.5 mmol) to produce Example 24.
  • Example 26 diethylaminosulfur trifluoride (6.6 g, 41 mmol) to produce Example 26.
  • the structures of the compounds are shown in Table 1.
  • Example 28 This chiral (S)-hydroxy compound (3 g, 3.4 mmol) was treated with diethylaminosulfur trifluoride (1.1 g, 6.8 mmol) to produce Example 28.
  • the structures of the compounds are shown in Table 1. Examples 29 and 30
  • Example 30 diethylaminosulfur trifluoride (5.8 g, 36 mmol) to produce Example 30.
  • the structures of the compounds are shown in Table 1.
  • 5-Octyl-2-(4-aminophenyl)pyrimidine was prepared by the following modification of the procedure described by Zaschke et al. in Z. Chem. 15, 441 (1975). Sodium methoxide (25% in methanol, 79.7 g, 3.07 eq) was added to a solution of 4-amino benzamidine
  • dichloromethane (2 ml) was then added dropwise to a 0°C solution of the amino alcohol (500 mg, 0.56 mmol) and pyridine (0.26 ml, 3.25 mmol) in dichloromethane (4 ml).
  • the resulting mixture was stirred for 1 hour at 0°C and then for 3 hours at ambient temperature.
  • the mixture was then coated onto silica gel and purified by chromatography on silica gel using 15:1
  • the title compound was prepared essentially as described in Examples 3 and 4 by combining 4- (2- (tridecafluorohexyloxy)tetrafluoroethoxy)-2,2,3,3,4,4- hexafluorobutanol (6.4 g, 10.1 mmol) with (S)-5-octyl- 2-[4-(2,3-oxiranylpropoxy)phenyl]pyrimidine (4.0 g, 11.8 mmol) .
  • the compounds of Table 1 were evaluated for transition temperatures by differential scanning calorimetry (DSC) and/or optical observation of DSC.
  • a device containing a chiral compound of this invention (Example 5) was prepared essentially as described in U.S. Patent No. 5,377,033 (Radcliffe) and filled with a mixture of 9.7 weight percent 5-octyl-2- [4-((R)-2-fluoro-3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 5),
  • the ITO-constituted electrodes of the device were connected to an arbitrary waveform generator with variable output voltage.
  • the device was driven by a voltage waveform consisting of bipolar, square pulses of ⁇ 10V/ ⁇ m amplitude, spaced 30 milliseconds apart by a train of square pulses having the same width and 3.3 V/ ⁇ m amplitude.
  • the device was heated to the
  • the electronic response time, ⁇ electric was derived from the displacement current of the ferroelectric liquid crystal device under an applied square voltage pulse. The current was viewed on a 100 megahertz bandwidth oscilloscope. The usual decaying exponential, associated with a dielectric filled capacitor, was followed by the spontaneous polarization (P S ) switching pulse. The time from the rising edge of the voltage pulse to the peak of the P S pulse was taken to be ⁇ electric .
  • phase transition temperatures of the achiral base material i.e., the above-described mixture without the chiral dopant
  • a device was prepared and evaluated essentially as described in Example 36 using a mixture of 5 weight percent 5-octyl-2-[(4-(S)-5-oxymethyl-3-(2- (2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)-2(3H)furanone)phenyl]pyrimidine
  • the resulting reaction mixture was heated at 100°C for three hours, cooled to room temperature, and diluted with water (75 mL) and perfluoro-N-methyl morpholine (153 g) in a separatory funnel.
  • the resulting lower fluorochemical phase was removed from the funnel, and the solvent was distilled at ambient pressure. The resulting residue was
  • a device was prepared and evaluated essentially as described in Example 36 using a mixture of 5 weight percent of the product (5-(6-(1,1- dihydroperfluoro (((2- methoxyethoxy)ethoxy)ethoxy)hexyloxy-2-(4-(dihydro-5-)
  • a device was prepared and evaluated essentially as described in Example 36 using a mixture of 5 weight percent 5-octyl-2-[4-((R)-2-hydroxy-3-(2- (2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 3) as the chiral dopant, 63.3 weight percent 5-octyl-2-[4- (6-(2-(nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6- decafluorohexyloxy)phenyl]
  • a device was prepared and evaluated essentially as described in Example 36 using a mixture of 20 weight percent 5-octyl-2-[4-((R)-2-hydroxy-3-(2- (2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 3) as the chiral dopant, 53.3 weight percent 5-octyl-2-[4- (6-(2-(nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy)phenyl]
  • Example 5 A device was prepared and evaluated essentially as described in Example 36 using 100 weight percent 5-octyl-2-[4-((R)-2-fluoro-3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 5).
  • the results given in Table 3 show very fast response times, high polarizations, and low viscosities. In addition, the response times are relatively
  • a device was prepared and evaluated essentially as described in Example 36 using a mixture of 50.1 weight percent 5-octyl-2-[(4-(S)-5-oxymethyl-3- (2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)-2(3H)furanone)phenyl]pyrimidine
  • phase transition temperatures of the achiral base material i.e., the above-described mixture without the chiral dopant
  • a device was prepared and evaluated essentially as described in Example 36 using a mixture of 10 weight percent 5-octyloxy-2-[4-((R)-2-fluoro-3- (2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 10) as the chiral dopant, 63.3 weight percent 5-octyl-2-[4- (6-(2-(nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6- decafluorohexyloxy)phenyl]
  • 2-(S)-fluorooctanol (3.0 g, 20.2 mmol; which can be prepared by the procedure described by H. Nohira et al. in Mol. Cryst. Liq. Cryst. 180B, 379-88 (1990)) was combined with toluene sulfonyl chloride (4.0 g, 21.2 mmol), ethyl diisopropyl amine (5.2 g, 40.4 mmol), and dimethylaminopyridine (123 mg, 1.0 mmol) in methylene chloride (50 mL). The resulting mixture was stirred at room temperature overnight. The resulting crude tosylate product was purified by flash chromatography on silica gel, eluting with 10 parts by volume of hexane and 1 part by volume of ethyl acetate.
  • a device was prepared and evaluated essentially as described in Example 36 using a mixture of 10 weight percent of the product (5-((S)-2- fluorooctyloxy)-2-[4-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)phenyl]pyrimidine, prepared essentially as described above), 63.3 weight percent 5-octyl-2- [4- (6-(2-(nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6- decafluorohexyloxy)phenyl]
  • Example 42 exhibits a much higher polarization than that of this Comparative Example (which effectively does not respond to an electric field) at similar concentrations of chiral dopant.
  • this data shows the importance of the position of the chiral moiety relative to the fluorochemical group.
  • Example 4 A device was prepared and evaluated essentially as described in Example 36 using 100 weight percent 5-octyl-2-[4-((S)-2-fluoro-3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 4).
  • the results given in Table 3 show very fast response times, high polarizations, and low viscosities. In addition, the response times are relatively
  • a device was prepared and evaluated essentially as described in Example 36 using 100 weight percent 5-hexyl-2-[4-((R)-2-fluoro-3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine
  • Example 8 The results given in Table 3 show very fast response times, high polarizations, and low viscosities. In addition, the response times are relatively temperature-independent .
  • Example 45 The results given in Table 3 show very fast response times, high polarizations, and low viscosities. In addition, the response times are relatively temperature-independent .
  • Example 10 A device was prepared and evaluated essentially as described in Example 36 using 100 weight percent 5-octyloxy-2-[4-((R)-2-fluoro-3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 10).
  • the results given in Table 3 show very fast response times, high polarizations, low viscosities, and a very broad smectic C temperature range. In addition, the response times are relatively temperature-independent.
  • Example 18 A device was prepared and evaluated essentially as described in Example 36 using 100 weight percent 5-((R)-2-fluorooctyloxy)-2-[4-((R)-2-fluoro-3- (2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 18).
  • the results given in Table 3 show very fast response times, high polarizations, and low viscosities.
  • Example 19 A device was prepared and evaluated essentially as described in Example 36 using 100 weight percent 5-((S)-2-fluorooctyloxy)-2-[4-((R)-2-fluoro-3- (2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 19).
  • the results given in Table 3 show very fast response times, high polarizations, and low viscosities.
  • a device was prepared and evaluated essentially as described in Example 36 using a mixture of 10.2 weight percent N-(4-octyloxy)phenyl-(S)-5-((2- (2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)methyl-2-oxazolidinone (Example 20), 59.9 weight percent 5-octyl-2-[4-(6-(2- (nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6- decafluorohexyloxy)phenyl]
  • Example 9 A device was prepared and evaluated essentially as described in Example 36 using 100 weight percent 5-hexyloxy-2-[4-((R)-2-fluoro-3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 9).
  • the results given in Table 3 show very fast response times, high polarizations, low viscosities, and a very broad smectic C temperature range. In addition, the response times are relatively temperature-independent.
  • a device was prepared and evaluated essentially as described in Example 36 using a mixture of 5 weight percent 5-octyl-2-[4-((R)-2-fluoro-3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 5) and 95 weight percent 5-heptyl-2-[4-(2-(2-(2-
  • Example 11 A device was prepared and evaluated essentially as described in Example 36 using 100 weight percent 5-octyl-2-[4-((R)-2-fluoro-3-(2-(2-(2- (trifluoromethoxy)tetrafluoroethoxy)tetrafluoroethoxy)- 2,2,-difluoroethoxy)propoxy)phenyl]pyrimidine (Example 11) .
  • the results given in Table 3 show very fast response times, high polarizations, and low
  • a device was prepared and evaluated essentially as described in Example 36 using 100 weight percent 5-octyl-2-[4-((R)-2-fluoro-3-(10-(2-
  • Example 13 The results given in Table 3 show a fast response time, a high polarization, and a low
  • a device was prepared and evaluated essentially as described in Example 36 using a mixture of 10 weight percent (S)-5-octyl-2-[4-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)methyl-2-oxazolidinone)phenyl]

Abstract

Fluorine-containing, chiral liquid crystal compounds comprise: (a) a chiral fluorochemical terminal portion containing at least one methylene group and optionally containing at least one catenary ether oxygen atom; (b) a saturated, chiral or achiral, hydrocarbon terminal portion; and (c) a central core connecting the terminal portions. The compounds have smectic mesophases or latent smectic mesophases and are useful, for example, in liquid crystal display devices.

Description

LIQUID CRYSTAL COMPOUNDS HAVING A CHIRAL FLUORINATED
TERMINAL PORTION
Field of the Invention
This invention relates to fluorinated chiral smectic liquid crystal compounds, to a process for the preparation of such compounds (and to intermediates for use therein), and to liquid crystal compound mixtures and electrooptical display devices containing such compounds.
Background of the Invention
Devices employing liquid crystals have found use in a variety of electrooptical applications, in particular those which require compact, energy- efficient, voltage-controlled light valves, e.g., watch and calculator displays, as well as the flat-panel displays found in portable computers and compact televisions. Liquid crystal displays have a number of unique characteristics, including low voltage and low power of operation, which make them the most promising of the non-emissive electrooptical display candidates currently available.
One of the most important characteristics of a liquid crystal display device is its response time, i.e., the time required for the device to switch from the on (light) state to the off (dark) state. In a ferroelectric or anti-ferroelectric device, response time (τ=η/PsE) is proportional to the rotational viscosity (η) of the liquid crystal compound (s) contained within the device and is inversely
proportional to their polarization (Ps) and to the applied electric field (E). Thus, response time can be reduced by using compound (s) having high polarizations or low viscosities, and such compounds are greatly desired in the art. In addition to fast response times, compounds should ideally possess broad smectic temperature ranges to enable operation of the device over a broad range of temperatures (or should be capable of combination with other liquid crystal compounds having different smectic temperature ranges without adversely affecting the smectic phase behavior of the base mixture). Surnmary of the Invention
Briefly, in one aspect, this invention provides fluorine-containing, chiral liquid crystal compounds having smectic mesophases or latent smectic mesophases. (Compounds having latent smectic
mesophases are those which by themselves do not exhibit a smectic mesophase, but which, when in admixture with compounds having smectic mesophases or with other compounds having latent smectic mesophases, develop smectic mesophases under appropriate conditions.) The chiral liquid crystal compounds of the invention comprise (a) a chiral fluorochemical terminal portion containing at least one methylene group and optionally containing at least one catenary, i.e., in-chain, ether oxygen atom; (b) a saturated, chiral or achiral, hydrocarbon terminal portion; and (c) a central core connecting the terminal portions. The chiral
fluorochemical terminal portion can be represented by the formula -D-R*-D-(O)x-CH2-D'-Rf, where R* is a cyclic or acyclic chiral moiety; x is an integer of 0 or 1; Rf is fluoroalkyl, perfluoroalkyl, fluoroether, or perfluoroether; and D' and each D are independently and non-directionally selected from the group consisting of a covalent bond, -C ( =O ) O-CrH2r , -O-CrH2r-, -O-(CsH2sO)tCr,H2r,-, -CrH2r-,
-( CsH2sO-)tCr ,H2r,-, -OSO2-, -SO2-, -SO2-CrH2r-,
Figure imgf000005_0001
and combinations thereof, where r and r' are
independently integers of 0 to about 20, s is
independently an integer of 1 to about 10 for each (CsH2sO), t is an integer of 1 to about 6, and p is an integer of 0 to about 4. When the Rf group of the fluorochemical terminal portion is perfluoroalkyl or perfluoroether, it can contain small amounts of
residual carbon-bonded hydrogen atoms but is preferably completely fluorinated. Preferably, Rf is fluoroalkyl, fluoroether, or perfluoroether; more preferably, Rf is perfluoroether, as the perfluoroether-containing compounds of the invention exhibit, e.g., a broad smectic C mesophase, good compatibility with other smectic C compounds, and advantageous layer spacing behavior. D' is preferably a covalent bond.
In general, the compounds of this invention have a central core comprised of at least one or two rings independently selected from the group consisting of aromatic, heteroaromatic, alicyclic, substituted aromatic, substituted heteroaromatic, and substituted alicyclic rings, the rings being connected one with another by a covalent bond or by chemical groups selected from the group consisting of -COO-, -COS-,
-HC=N-, -CH=CH-, -CsC-, and -COSe-. The rings can be fused or non-fused. The heteroatoms within the
heteroaromatic rings comprise at least one atom
selected from the group consisting of nitrogen, oxygen, and sulfur. Non-adjacent ring carbon atoms in the alicyclic rings can be substituted by nitrogen, oxygen, or sulfur atoms. When the ring(s) are aromatic, heteroaromatic, substituted aromatic, or substituted heteroaromatic, the non-fused rings of the core are preferably no more than about two in number.
When used in electrooptical display devices, the chiral liquid crystal compounds of the invention provide exceptionally fast response times over broad temperature ranges. The compounds exhibit surprisingly high polarization values (relative to comparable compounds having a chiral center located on the other side of the core, away from the fluorochemical terminal portion) and surprisingly low viscosities in view of their high polarizations. In addition, many of the compounds have broad smectic C temperature ranges, making them useful alone, as well as in admixture with other chiral or achiral liquid crystal compounds (as dopants or as the major components), for electrooptical display applications.
The compounds of the invention have a number of desirable properties when used in admixture with other liquid crystal compounds, preferably compounds having fluorinated terminal portions such as those compounds disclosed, for example, in U.S. Pat. Nos. 4,886,619 (Janulis), 5,082,587 (Janulis), and 5,262,082 (Janulis et al.). For example, the compounds of the invention when admixed with such preferred liquid crystal compounds show excellent compatibility, show a beneficial effect or only a minimal negative effect on the smectic C temperature range of the resulting mixtures (even when present at high concentrations), and provide ferroelectric mixtures having fast
electrical response times.
In other aspects, this invention also provides a mixture of liquid crystal compounds
comprising at least one liquid crystal compound of the invention, a liquid crystal display device containing at least one liquid crystal compound of the invention, liquid crystal intermediate compounds, and a process for preparing the liquid crystal compounds of the invention. Detailed Description of the Invention
A class of the non-polymeric liquid crystal materials, i.e., liquid crystal compounds, of the present invention can be represented by the general formula I:
Figure imgf000007_0001
where M, N, and P are each independently selected from the group consisting of
Figure imgf000008_0001
Figure imgf000009_0001
a, b, and c are each independently zero or an integer of from 1 to 3, with the proviso that the sum of a + b + c be at least 1 (and preferably no greater than 2); each A and B are non-directionally and independently selected from the group consisting of a covalent bond, -C(=O)-O-, -C(=O)-S-, -C(=O)-Se-,
-C(=O)-Te-, -(CH2CH2)k- where k is 1 to 4,
-CH=CH-, -C≡C-, -CH=N-, -CH2-O-, -C(=O)-, and -O- ; each X, Y, and Z are independently selected from the group consisting of -H, -Cl, -F, -Br, -I, -OH, -OCH3, -CH;., -CF3, -OCF3, -CN, and -NO2; each l, m, and n are independently zero or an integer of 1 to 4;
D is non-directionally selected from the group
consisting of a covalent bond, -C(=O)-O-CrH2r-, -O-CrH2r-, -O-(O=)C-CrH2r-, -C≡C-,
-CH=CH-, -C(=O)-,
-O-(CsH2sO-)-tCr,H2r,-, -CrH2r-,-(CsH2sO-)-tCr,H2r,-, -O-, -S-,
-OSO2-, -SO2-, -SO2-CrH2r-, O -N (CpH2p+1)-,
Figure imgf000010_0003
O -CH=N-, and combinations thereof, where
Figure imgf000010_0002
r and r' are independently integers of 0 to about 20, s is independently an integer of 1 to about 10 for each (C5H2sO), t is an integer of 1 to about 6, and p is an integer of 0 to about 4;
R is selected from the group consisting of
-O-((Cq,H2q,-v,-(R')v,)-O)w-CqH2q+1-v-(R')v ,
- ((Cq,H2q,-v,- (R')v') -O)w-CqH2q+1-v- (R')v,
-C (=O) -O-CqH2q+1-v- (R' )v , -O- (O=) C-CqH2q+1-v- (R')v ,
<
Figure imgf000010_0001
-CR' H- (D)g-CR'H-CqH2q+1-v- (R')v , where each R' is independently selected from the group consisting of -Cl, -F, -CF3, -NO2, -CN, -H, -CqH2q+1, -O- (O=)C-CqH2q+1, -C(=O)-O-CqH2q+1, -Br, -OH, and -OCqH2q+1 (preferably, -H or -F); q' is independently an integer of 1 to about 20 for each (Cq,H2q,-O); q is an integer of 1 to about 20; w is an integer of 0 to about 10; v is an integer of 0 to about 6; each v' is independently an integer of 0 to about 6; g is an integer of 1 to about 3; each D is independently and non-directionally selected from the group set forth for D above, with the proviso that the ring containing D has from about 3 to about 10 ring atoms; each W is independently selected from the group consisting of N, CR', and SiR'; and R can be chiral or achiral; and
Rf' is -R*-D- (O)x-CH2-D' -Rf, where R* is a cyclic or acyclic chiral moiety; D and D' are each independently and non-directionally selected from the group set forth for D above; x is an integer of 0 or 1; and Rf is fluoroalkyl, perfluoroalkyl, fluoroether, or
perfluoroether. Preferably, Rf is fluoroalkyl,
fluoroether, or perfluoroether; and
R* is selected from the group consisting of
-O-((Cq,H2q,-v,-(R')v,)-O)w-CqH2q-v-(R')v- ,
-((Cq,H2q,-v,-(R')v,)-O)w-CqH2q-v-(R,)v- ,
-C(=O)-O-CqH2q-v-(R')v- , -O-(O=)C-CqH2q-v-(R')v- ,
and -CR'H-(D)g-CR'H- ,
Figure imgf000011_0001
where each R' is independently selected from the group consisting of -Cl, -F, -CF3, -NO2, -CN, -H, -CqH2q+1,
-O- (O=)C-CqH2q+1, -C(=O)-O-CqH2q+1 , -Br, -OH, and -OCqH2q+1 (preferably, -H, -F, -CF3, -Br, -OH, or -OCH3; more preferably, -H, -F, or -CF3); q' is independently an integer of 1 to about 20 for each ((Cq,H2q,-V'-(R')V')-O); q is an integer of 1 to about 20; w is an integer of 0 to about 10; v is an integer of 0 to about 6; each v' is independently an integer of 0 to about 6; g is an integer of 1 to about 3; each D is independently and non-directionally selected from the group set forth for D above, with the proviso that the ring containing D has from about 3 to about 10 ring atoms; and each W is independently selected from the group consisting of N, CR', and SiR'. More preferably, Rf is perfluoroether. D' is preferably a covalent bond.
In defining Rf, particularly preferred perfluoroalkyl groups are those which can be
represented by the formula -CqF2qX', where q is as defined above (and, preferably, is at least about 5) and X' is hydrogen or fluorine. Particularly preferred fluoroalkyl and fluoroether groups are those which can be represented by the formula -Rf''-Rh, where Rf'' is a linear or branched, perfluorinated or partially- fluorinated alkylene group having from 1 to about 10 (preferably, from about 2 to about 6) carbon atoms and optionally containing one or more catenary, i.e., in- chain, ether oxygen atoms, and Rh is a linear or branched alkyl group having from 1 to about 14
(preferably, from about 3 to about 10) carbon atoms and optionally containing one or more catenary ether oxygen atoms. Preferably, Rf'' is perfluorinated, both Rh and Rf'' are linear, and at least one of the groups Rh and Rf'' contains at least one catenary ether oxygen atom. More preferably, Rh or both Rh and Rf'' contains at least one catenary ether oxygen atom.
Particularly preferred perfluoroether groups are those which can be represented by the formula -(CxF2xO)zCyF2y+1, where x is independently an integer of 1 to about 10 for each (CxF2xO), y is an integer of 1 to about 10, and z is an integer of 1 to about 10.
Preferably, the perfluoroether group is linear, x is independently an integer of 1 to about 6 for each
(CxF2xO), y is an integer of 1 to about 6, and z is an integer of 1 to about 6.
Preferred subclasses of the chiral compounds of the invention can be represented by the following formula:
R''-(O)j-G-(OCH2)j-R*-(CsH2sO)tCr,H2r,-Rf (II) where R'' is (R')v-CqH2q+1-v , where q is an integer of 2 to about 10, each R' is independently selected from the group consisting of hydrogen, fluorine, chlorine, methyl, and perfluoromethyl, and v is an integer of 1 to about 3; j is an integer of 0 or 1; G is selected from the group consisting of
Figure imgf000013_0001
R* is selected from the group consisting of
-CqH2q-v- (R')v- and
Figure imgf000014_0001
where R' is -F, q is an integer of 1 to about 4, v is an integer of 1 to about 3, W is N or CH, and D is -C(=O)-O- or -CH2-; s is an integer of 1 to about 6; t is an integer of 0 or 1; r' is an integer of 1 to about 3; and Rf is selected from the group consisting of -CqF2qX', -Rf''-Rh, and - (CxF2xO)zCyF2y+1, where q is an integer of 1 to about 6, X' is fluorine, Rf'' is a linear or branched, perfluorinated alkylene group having from about 2 to about 4 carbon atoms and
optionally containing one or more catenary ether oxygen atoms, Rh is a linear or branched alkyl group having from about 2 to about 7 carbon atoms and optionally containing one or more catenary ether oxygen atoms, x is independently an integer of 1 to about 10 for each (CxF2xO), y is an integer of 1 to about 8, and z is an integer of 1 to about 5.
The fluorine-containing liquid crystal compounds of the invention can be prepared by a process comprising the steps of (a) mixing at least one
compound represented by the formula
Figure imgf000014_0002
with at least one compound represented by the formula
Figure imgf000015_0001
or mixing at least one compound represented by the formula
Figure imgf000015_0002
with at least one compound represented by the formula
Figure imgf000015_0003
or mixing at least one compound represented by the formula
K
Figure imgf000016_0001
with at least one compound represented by the formula
Figure imgf000016_0002
where M, N, P, a, b, c, A, B, X, Y, Z, 1, m, n, D, R,
R*, Rf, and Rf' are as defined above for formula I; x is an integer of 0 or 1; and each A', A'', B', and B' ' are independently selected from the group consisting of -H, -Cl, -Br, -I, -OH, -COOH, -CH(CH2OH)2, -SH, -SeH, -TeH, -NH2, -COCl, -CHO, -OSO2Rf''', -OSO2CH3,
-NH(C=O)OCqH2q+1, -NCO, -OSO2-cyclo (C6H4 ) -CH3, -CH2COOH, and -CH (C (O) O-CqH2q+1)2, where Rf''' is a perfluoroalkyl group having from 1 to about 10 carbon atoms and q is an integer of 0 to about 20, and with the proviso that (R*)x-A' can enter into an addition or condensation reaction with A'' and that (R*)x-B' can enter into an addition or condensation reaction with B''; and (b) allowing compounds III and IV, compounds V and VI, or compounds III and VII to react, optionally in the presence of suitable coupling agent (s), i.e., reagent (s) which effect coupling.
Most of the compounds of the present invention have enhanced smectic mesophases. Mixtures of the compounds of the invention with other liquid crystal materials can be formulated to provide desired transition temperatures and broad mesophase temperature ranges. Such mixtures preferably contain compounds having fluorinated terminal portions, such as those compounds described, for example, in U.S. Pat. Nos. 4,886,619 (Janulis), 5,082,587 (Janulis), and, most preferably, 5,262,082 (Janulis et al.).
The compounds of this invention in admixture with other chiral or achiral liquid crystal compounds may exhibit chiral smectic liquid crystal behavior. Furthermore, many of the perfluoroether group- containing liquid crystal compounds of the invention when used alone or when mixed with other liquid crystal compounds of the invention or with achiral, fluorine- containing liquid crystal compounds (preferably, the perfluoroether group-containing liquid crystal
compounds described in U.S. Pat. No. 5,262,082 (Janulis et al.)) exhibit a reduced temperature dependence of the smectic interlayer spacing. This property provides for the spontaneous generation of a bookshelf type layer structure, which is ideal for a ferroelectric liquid crystal device.
Another advantage of using the materials of this invention in the formulation of liquid crystal mixtures is the low birefringence which can be
obtained. The low birefringence of the liquid crystal compounds of the invention (relative to their non- fluorine-containing analoques) allows the fabrication of devices with larger device spacings. Light
transmission through, e.g., a surface-stabilized ferroelectric device (as described in U.S. Patent No. 4,367,924) with two polarizers is represented by the following equation: I = I0 ( sin2 ( 4Θ) ) ( sin2 (πΔnd/λ) ) where I0 = transmission through parallel polarizers
Θ = material tilt angle
Δn = liquid crystal birefringence
d = device spacing
λ = wavelength of light used To maximize the transmission, both sin2(4Θ) and
sin' (πΔnd/λ) must be at maximum. This occurs when each term equals one. The first term is a maximum when the tilt angle equals 22.5°. This is a function of the liquid crystal and is constant for a given material at a given temperature. The second term is maximum when Δnd =λ/2. This demonstrates the criticality of the low birefringence of the materials of this invention. Low birefringence allows a larger device thickness, d, for a given wavelength of light. Thus, a larger device spacing is possible while still maximizing
transmission, allowing easier device construction.
Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and
details, should not be construed to unduly limit this invention.
In the following examples, all temperatures are in degrees Celsius and all parts and percentages are by weight unless indicated otherwise. Commercially available materials were chemically transformed by reaction pathways well-known to those skilled in the art and detailed in the examples. Chemical
transformations were comprised of acylation, esterification, etherification, alkylation, and
combinations thereof using fluorine-containing and non- fluorine-containing reactants to provide the precursor compounds, which, in turn, were caused to react
together to yield the chiral, fluorine-containing liquid crystal compounds of this invention.
Compounds prepared in the various examples of this invention were characterized by their melting or boiling point, and structures were confirmed by using at least one of the following methods of analysis:
chromatography; 13C-, 1H-, and 19F-NMR; and infrared and mass spectroscopies.
EXAMPLES
The 5-alkyl-2-(4-hydroxyphenyl) pyrimidines used in the examples were prepared essentially as described by Zaschke and Stolle in "Synthese
niedrigschmelzender Kristallin-Flussiger Heterocyclen; 5-n-Alkyl-2-[4-n-alkanoyloxy-phenyl]pyrimidine,"
Z.Chem. 15, 441-3 (1975). (S)- and (R)-2-fluoro-decyl- p-toluenesulfonate were prepared essentially as
described by Nohira et al. in Mol . Cryst. Liq. Cryst. 180B, 379 (1990). Fluorinated alcohols were prepared essentially as described in U.S. Patent No. 5,262,082 (Janulis et al.) by sodium borohydride reduction of the corresponding perfluorinated acids (or derivatives), which had been prepared by electrochemical fluorination (ECF) or by direct fluorination (using elemental fluorine) of the corresponding hydrocarbon acids (or derivatives). See, e.g., the description of ECF given in U.S. Patent No. 2,519,983 (Simons). Direct
fluorination is described, e.g., in U.S. Patent No.
5,362,919 (Costello et al.). Examples 1-35 describe procedures for preparing liquid crystal compounds and liquid crystal intermediate compounds of this invention. The chemical structure of each compound is given in Table 1.
Example 1
Preparation of 5-Octyl-2-[4-((R)-2-fluoro- 5,5,6,6,7,7,8,8,9,9,10,10,10- tridecafluorodecyloxy)phenyl]pyrimidine
Dry nitrogen was bubbled through a solution of (S)-1,2-O-isopropylidine-3-butene-1,2-diol (1.0 g, 7.8 mmol) (prepared essentially by the procedure of Jajer et al. described in Synthesis 1990, 556) and 1- iodo-perfluorohexane (3.48 g, 7.8 mmol) for 10 minutes. Tetrakis (triphenylphosphine) palladium (0) (90 mg, 0.078 mmol) was added to the resulting mixture, and the mixture was stirred at room temperature for 10 hours. Tributyl tin hydride (2.1 ml, 7.8 mmol) was then added by syringe, and the mixture was stirred for an
additional 10 hours. The resulting product was
distilled (44ºC , 0.4 mm Hg) from the mixture to give 2.5 g of (S)-1,2-O-isopropylidene-3-(perfluorohexyl)- butane diol as a clear liquid. The dioxolane
protecting group was then hydrolyzed to the diol by stirring the product in a solution of aqueous acidic tetrahydrofuran for 4 hours. The resulting product was distilled under reduced pressure (80-85°C, 0.4 mm Hg) to give 2.1 g of (S)-2-hydroxy- 5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluoro-1-decanol . The primary alcohol was protected with trityl chloride (triphenylmethyl chloride) essentially as described by Chaudhary et al. in Tetrahedron Letters 1979, 95, and the resulting secondary alcohol was subsequently treated with diethylaminosulfur ttifluoride (essentially as described by Middleton in J. Org. Chem. 40, 574 (1975)) to give triphenylmethoxy-(R)-2-fluoro- 5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluorodecane. The trityl protecting group was then removed with aqueous acidic tetrahydrofuran to give (R)-2-fluoro-
5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluoro-1-decanol. The p-toluene sulfonate derivative of the alcohol was prepared by the addition of 4-toluenesulfonyl chloride (120.6 mg, 0.63 mmol) to a solution of the alcohol (236 mg, 0.57 mmol), dimethylaminopyridine (DMAP, 2.8 mg, 0.02 mmol), and N,N'-diisopropylethylamine (0.2 ml, 1.14 mmol) in dichloromethane (2.0 ml). The resulting mixture was stirred for 8 hours at room temperature and was then coated onto 0.5 g of silica gel. The
resulting product was then purified by eluting with
10:1 hexanes/ethyl acetate on silica to give 280 mg of the sulfonate.
Sodium hydride (30 mg, 60 weight percent in oil, 6.6 mmol) was added to a stirred solution of 5- octyl-2-(4-hyd(oxyphenyl)pyrimidine (169 mg, 0.59 mmol) and dimethyl formamide (2.0 ml). The resulting mixture was stirred for 15 minutes under a nitrogen atmosphere, and then a solution of the above-described sulfonate (280 mg, 0.496 mmol) in 2 ml of dimethyl formamide was added by syringe. The mixture was heated to 60°C for 4 hours and then cooled to ambient temperature. The mixture was diluted with water (5 ml) and extracted with three 10 ml aliquots of diethyl ether. The organic extract were collected, dried (over MgSO4), filtered, and concentrated to give product in the form of a brown paste which solidified upon standing. The product was then purified by column chromatography on silica gel (eluting with 10:1 hexanes/ethyl acetate) to give 233 mg of the title compound (having the structure shown in Table 1) as a white solid. Example 2
Preparation of 5-Octyl-2-[4-((R)-2-fluoro-3- (2,2,3,3,4,4,5,5,6,6,6- undecafluorohexyloxy)propoxy)phenyl]pyrimidine
(S)-2-hydroxy-3-(2,2,3,3,4,4,5,5,6,6,6- undecafluorohexyloxy)-propanol was prepared by the following modification of a procedure described in U.S. Patent No. 3,470,258 (Teroso et al.). (R)-glycidol (5.0 g, 67.5 mmol) was added dropwise to a 120°C solution of 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexanol (30 g, 101 mmol) and N,N' -diisopropylethylamine (0.47 ml, 2.7 mmol). The resulting mixture was then stirred for one hour. The resulting product was distilled (79- 81ºC at 0.4 mm Hg) from the mixture to give 14.7 g of (S)-2-hydroxy-3-(2,2,3,3,4,4,5,5,6,6,6- undecafluorohexyloxy)-1-propanol as a clear liquid.
(R)-2-fluoro-3-(2,2,3,3,4,4,5,5,6,6,6- undecafluorohexane-1-p-toluenesulfonate was then prepared using essentially the procedure described in Example 1.
Sodium hydride (0.223 g, 9.3 mmol) was added to a stirred solution of the sulfonate (3.00 g, 5.65 mmol) and 5-octyl-2-(4-hydroxyphenyl)pyrimidine (1.77 g, 6.2 mmoles) using essentially the procedure
described in Example 1 to give the title compound.
Example 3
Preparation of 5-Octyl-2-[4-((R)-2-hydroxy-3-(2-(2-
(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine
A solution of potassium hydroxide (1.97 g, 35 mmol) in water (1.97 ml) was added to a solution of (R)-5-octyl-2-[4-(2,3-oxiranylpropoxy)phenyl]
pyrimidine (10.0 g, 29.3 mmol) (prepared essentially as described by Sakaguchi et al. in Ferroelectrics 114, 269 (1992)), 2,2-difluoro-2-[1,1,2,2-tetrafluoro-2- nonfluorobutoxy)ethanol] (15.2 g, 35.16 mmol), and tetrabutyl ammonium hydrogen sulfate (500 mg, 1.5 mmol) in tetrahydrofuran (20 ml) . The resulting mixture was heated to reflux temperature for 23 hours, was diluted with water (100 ml), and was extracted with three 100 ml aliquots of ethyl acetate. The organic extracts were concentrated under reduced pressure, and the resulting product was recrystallized from acetonitrile (150 ml) to give -2-[4-((R)-2-hydroxy-3-(2-(2- (nonafluorobutoxy) 1,1,2,2-tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]-5-octyl-pyrimidine as a white solid.
Example 4
Preparation of 5-Octyl-2-[4-((S)-2-fluoro-3-(2-(2- (nonafluorobutoxy) tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine
A solution of 5-octyl-2-[4-((R)-2-hydroxy-3- (2-(2-(nonafluorobutoxy) tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (prepared essentially as in Example 3, 8.0 g, 10.35 mmol) in dry tetrahydrofuran (50 ml) was added dropwise to a -70°C solution of diethylaminosulfur trifluoride (3.3 g, 20.7 mmol) in tetrahydrofuran (50 ml). The resulting mixture was warmed to -30°C over a period of 2 hours, and then pyridine (3.3 g, 41.4 mmol) was added to the mixture. The mixture was allowed to warm to ambient temperature and was stirred for 12 hours. The mixture was then poured into a slurry of silica gel (40 g) in diethyl ether and was concentrated onto the silica gel under reduced pressure. The product-coated silica was placed on top of 100 g of fresh silica gel and was eluted with a 10:1 hexanes/ethyl acetate solution.
Fractions collected containing the product were
concentrated under reduced pressure. The product was then recrystallized from methanol to give 4.9 g of the title compound as a white solid.
Example 5
Preparation of 5-Octyl-2-[4-((R)-2-fluoro-3-(2-(2- (nonafluorobutoxy) tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine
The title compound was prepared essentially as described in Example 4 using 5-octyl-2-[4-((S)-2- hydroxy-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)- 2,2,-difluoroethoxy(propoxy)phenyl]pyrimidine
in place of 5-octyl-2-[4-((R)-2-hydroxy-3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine.
Example 6
Preparation of 5-Octyl-2-[4-((S)-2-bromo-3-(2-(2-
(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine
Perfluorobutanesulfonyl fluoride (389 mg,
1.29 mmol) was added dropwise to a -20°C solution of 5- octyl-2-[4-((R)-2-hydroxy-3-(2-(2-
(nonafluorobutoxy)tetrafluoroethoxy)-2 ,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 4, 1.0 g, 1.29 mmol) and diisopropyl ethylamine (334 mg, 2.58 mmol) in tetrahydrofuran (2 ml).
Tetrabutylammonium bromide (416 mg, 1.29 mmol) was then added to the resulting mixture, and the mixture was allowed to warm to ambient temperature. The mixture was stirred at ambient temperature for 5 hours. The mixture was coated on to silica gel, and the resulting product was then purified by column chromatography
(eluting with 10:1 hexanes/ethyl acetate) followed by recrystallization from methanol.
Example 7
Preparation of 5-Octyl-2-[4-((R)-2-methoxγ-3-(2-(2-
(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine
Methyl iodide (1.1 g, 7.76 mmol) was added to a solution of 5-octyl-2-[4-((R)-2-hydroxy-3-(2-(2-
(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 4, 1.5 g, 1.94 mmol) and sodium hydride (116 mg, 60 weight percent in oil, 2.91 mmol) in dimethyl formamide (10 ml) . The resulting mixture was stirred at room
temperature for 10 hours, was diluted with 50 ml of water, and was extracted with three 50 ml aliquots of diethyl ether. The organic extracts were dried (over MgSO4), filtered, and concentrated. The resulting product was then recrystallized from methanol at -30°C to give a white smectic material.
Example 8
Preparation of 5-Hexyl-2-[4-((R)-2-fluoro-3-(2-(2-
(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine
A solution of 5-hexyl-2-(4- hydroxyphenyl) pyrimidine (1.0 g, 4.08 mmol), 3-(2-[2- (nonafluorobutoxy)tetrafluoroethoxy]-2,2- difluoroethoxy)-(R)-2-fluoropropyl-1-p-toluenesulfonate (2.7 g, 4.08 mmol, prepared essentially as described in Example 2 by replacing 2,2,3,3,4,4,5,5,6,6,6- undecafluorohexanol with 2-[2-(nonafluorobutoxy)- tetrafluoroethoxy]-2,2-difluoro-1-ethanol), and
potassium carbonate (0.62 g, 4.5 mmol) in acetonitrile (30 ml) was heated to reflux temperature and maintained at that temperature for 16 hours. The resulting mixture was then coated onto silica gel, and the resulting product was purified by column chromatography and subsequent recrystallization from methanol. Example 9
Preparation of 5-Hexyloxy-2-[4-((R)-2-fluoro-3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine
2-Hexyloxyacetaldehyde diethylacetal was prepared as follows:
Hexanol (200 g, 1.96 mol) and toluene (600 ml) were added to a 3 liter flask fitted with a mechanical stirrer and a reflux condenser. Sodium hydride (51.6 g, 2.15 mol) was added slowly to the resulting mixture, and then bromoacetaldehyde diethylacetal (385.7 g, 1.96 mol) was added dropwise. The mixture was heated to reflux temperature and maintained at that temperature for 6 hours. The mixture was then cooled to ambient temperature and was filtered to remove the resulting solids. Toluene was removed from the filtrate under reduced pressure, and the resulting product was
distilled (85-88°C) to give 189.4 g of 2- hexyloxyacetaldehyde diethylacetal .
5-Hexyloxy-2-(4-hydroxyphenyl)pyrimidine was prepared essentially by the procedure described by Zaschke et al., supra. The title compound was then prepared essentially as described in Example 8 by replacing 5-hexyl-2-(4-hydroxyphenyl)pyrimidine with 5- hexyloxy-2-(4-hydroxyphenyl)pyrimidine (0.54 g, 2.0 mmo1.
Example 10
Preparation of 5-Octyloxy-2-[4-((R)-2-fluoro-3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine
5-Octyloxy-2-(4-hydroxyphenyl)pyrimidine was prepared essentially as described in Example 9 by substituting octanol for hexanol . The title compound was then prepared essentially as described in Examples 3 and 4 by replacing (R)-5-octyl-2-[4-(2,3- oxiranylpropoxy)phenyl]pyrimidine with (S)-5-octyloxy- 2-[4-(2,3-oxiranylpropoxy)phenyl]pyrimidine (10.0 g, 28.0 mmol) and using 2-[2-(nonfluorobutoxy)- tetrafluoroethoxy]-2,2-difluoroethanol (13.3 g, 31 mmol). The resulting (S)-hydroxy compound was treated with 2 equivalents of diethylaminosulfur trifluoride to produce the title compound.
Example 11
Preparation of 5-Octyl-2-[4-((R)-2-fluoro-3-(2-(2-(2- (trifluoromethoxy)tetrafluoroethoxy)tetrafluoroethoxy)- 2,2,-difluoroethoxy)propoxy)phenyl]pyrimidine
The title compound was prepared essentially as described in Examples 3 and 4 by combining 2-(2-(2- (trifluoromethoxy)tetrafluoroethoxy)tetrafluoroethoxy)- 2,2-difluoro-1-ethanol (2.8 g, 7.0 mmol) with (S)-5- octyl-2-[4-(2,3-oxiranylpropoxy) phenyl]pyrimidine (2.0 g, 5.87 mmol) to produce 5-octyl-2-[4-((S)-2-hydroxy-3- (2-(2-(2-
(trifluoromethoxy)tetrafluoroethoxy)tetrafluoroethoxy)- 2,2,-difluoroethoxy)propoxy)phenyl]pyrimidine. This chiral (S)-hydroxy compound (2.95 g, 4.0 mmol) was treated with diethylaminosulfur trifluoride (1.29 g, 8.0 mmol) to produce the title compound.
Example 12
Preparation of 5-Octyl-2-[4-((S)-2-fluoro-3-(4- (nonafluorobutoxy)-2,2,3,3,4,4- hexafluorobutoxy)propoxy)phenyl]pyrimidine
(R)-Benzylglycidyl ether (2.0 g, 12.2 mmol, prepared essentially as described by Byun et al. in Tet. Lett. 30, 2751 (1989)) was added dropwise to a 120°C solution of potassium carbonate (0.17 g, 1.2 mmol) in 4-nonafluorobutoxy-2,2,3,3,4,4-hexafluoro-1- butanol (5.1 g, 12.2mmol). The resulting mixture was stirred for 3 hours at 120°C and was then cooled to ambient temperature and distilled (0.6 torr, 110-130°C) to give 6.25 g of 1-benzyloxy-(R)-2-hydroxy-3-(4- (nonafluorobutoxy)-2,2,3,3,4,4- hexafluorobutoxy)propane.
This product was then converted to 1-benzyloxy-(S)-2- fluoro-3-( 4-nonafluorobutoxy-2,2,3,3,4,4- hexafluorobutoxy)propane by essentially the procedure described in Example 4. Removal of the benzyl
protecting group was effected by hydrogenation (3100 torr (60 psi) H2 and a catalytic amount of 10% Pd on carbon in tetrahydrofuran) to give (S)-2-fluoro-3-(4- nonafluorobutoxy-2,2,3,3,4,4-hexafluorobutoxy)-1- propanol.
(S)-2-fluoro-3-(4-(nonafluorobutoxy)- 2,2,3,3,4,4-hexafluorobutoxy)propyl-1-p- toluenesulfonate was prepared essentially as described in Example 1. The title compound was then prepared essentially as described in Example 8 using 5-octyl-2- (4-hydroxyphenyl) pyrimidine (1.5 g, 5.28 mmol) and (S)- 2-fluoro-3-(4-(nonafluorobutoxy)-2,2,3,3,4,4- hexafluorobutoxy) propyl-1-p-toluenesulfonate (3.1 g, 4.8 mmol).
Example 13
Preparation of 5-Octyl-2-[4-((R)-2-fluoro-3-(10-(2-
(nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10- octadecafluorodecyloxy)propoxy)phenyl]pyrimidine
The title compound was prepared essentially as described in Examples 3 and 4 by combining 10- (2-
(nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-octadecafluoro-1- decanol (5.8 g, 7.0 mmol) with (S)-5-octyl-2-[4-(2,3- oxiranylpropoxy)phenyl]pyrimidine (2.0 g, 5.87 mmol) to produce 5-octyl-2-[4-((S)-2-hydroxy-3-(10-(2-
(nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10- octadecafluorodecyloxy)propoxy)phenyl]pyrimidine. This chiral (S)-hydroxy compound (3.6 g, 3.1 mmol) was treated with diethylaminosulfur trifluoride (1.0 g, 6.2 mmol) to produce the title compound. Example 14
Preparation of 5-Octyl-2-[4-((R)-2-fluoro-3-(5-butoxy-
2,2,3,3,4,4-hexafluoropentoxy)propoxy)phenyl]pyrimidine
The title compound was prepared essentially as described in Examples 3 and 4 by combining 5-butoxy- 2,2,3,3,4,4-hexafluoropentanol (3.1 g, 11.7 mmol, prepared essentially by the method described in U.S. Patent No. 5,399,291 (Janulis et al.)) with (S)-5- octyl-2-[4-(2,3-oxiranylpropoxy)phenyl] pyrimidine (2.0 g, 5.87 mmol) to produce 5-octyl-2-[4-((S)-2-hydroxy-3- (-5-butoxy-2,2,3,3,4,4- hexafluoropentoxy) propoxy) phenyl] pyrimidine. This chiral (S)-hydroxy compound (2.0 g, 3.3 mmol) was treated with diethylaminosulfur trifluoride (1.06 g, 6.6 mmol) to produce the title compound.
Example 15
Preparation of 5-Octyl-2-[4-((R)-2-fluoro-3-(2-(N- (2,2,3,3,5,5,6,6-octafluoro)morpholino)-2,2- difluoroethoxy)propoxy)phenyl]pyrimidine
The title compound was prepared essentially as described in Examples 3 and 4 by combining 2-(N- (2,2,3,3,5,5,6,6-octafluoro)morpholino)-2,2- difluoroethanol (2.18 g, 7.0 mmol) with (S)-5-octyl-2- [4-(2,3-oxiranylpropoxy)phenyl]pyrimidine (2.0 g, 5.87 mmol) to produce 5-octyl-2-[4-((S)-2-hydroxy-3-(2-(N- (2,2,3,3,5,5,6,6-octafluoro)morpholino)-2,2- difluoroethoxy)propoxy)phenyl]pyrimidine. This chiral (S)-hydroxy compound (3.0 g, 4.6 mmol) was treated with diethylaminosulfur trifluoride (1.5 g, 9.2 mmol) to produce the title compound.
Example 16 Preparation of 5-Octyl-2-[4-((R)-2-fluoro-3-(2-(2-(2-
(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)ethoxy)propoxy)phenyl]pyrimidine
The title compound was prepared essentially as described in Examples 3 and 4 by combining 2-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy) ethanol (3.3 g, 7.0 mmol) with (S)-5- octyl-2-[4-(2,3-oxiranylpropoxy)phenyl]pyrimidine (2.0 g, 5.87 mmol) to produce 5-octyl-2-[4-((S)-2-hydroxy-3- (2-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)ethoxy)propoxy)phenyl]pyrimidine. This chiral (S)-hydroxy compound (1.6 g, 1.95 mmol) was treated with diethylaminosulfur trifluoride (0.63 g, 3.92 mmol) to produce the title compound.
Example 17
Preparation of (R)-2,3-Difluoro-4-octyl-4'-(2-fluoro-3- (2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)1,1'-biphenyl
The title compound was prepared essentially as described in Example 8 by combining 3-(2-[2- (nonfluorobutoxy)tetrafluoroethoxy]-2,2- difluoroethoxy)-(R)-2-fluoropropyl-1-p-toluenesulfonate (0.5 g, 0.75 mmol) with 2,3-difluoro-4-octyl-4'- hydroxybiphenyl (0.24 g, 0.75 mmol, prepared
essentially as described by Gray et al. in J. Chem.
Soc, Perkin Trans. II 1989, 2041).
Example 18
Preparation of 5-((R)-2-Fluorodecyloxy)-2-[4-((R)-2- fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)- 2,2,-difluoroethoxy)propoxy)phenyl]pyrimidine
5-Benzyloxy-2-(4-hydroxy)phenyl]pyrimidine was prepared essentially as described in Example 9 by replacing benzyl alcohol for hexanol.
5-Benzyloxy-2-(4-((R)-2-fluoro-3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)propoxy)phenyl]pyrimidine was prepared essentially as described in Example 8 using 5- benzyloxy-2-(4-hydroxy)phenyl]pyrimidine (0.97 g, 3.47 mmol) in place of 5-hexyl-2-(4- hydroxyphenyl) pyrimidine. The benzyl protecting group was removed by hydrogenation using 10% Pd on carbon in tetrahydrofuran under 3100 torr (60 psi) hydrogen pressure until the reaction was shown to be complete by thin layer chromatography. The Pd catalyst was removed by filtration, and the solvent was removed under reduced pressure to give 5-hydroxy-2-(4-((R)-2-fluoro- 3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)propoxy)phenyl]pyrimidine as a white solid. This hydroxyphenylpyrimidine (760 mg, 1.12 mmol), (R)-2-fluoro-decyl-p-toluenesulfonate (370 mg, 1.12 mmol), and potassium carbonate (150 mg, 1.12 mmol) in acetonitrile (30 ml) were stirred at reflux
temperature until the reaction was shown to be complete by gas chromatography. The resulting product was then coated onto silica gel (2 g) and was purified by column chromatography (eluting with 15:1 hexane/ethyl acetate) to give 695 mg of the title compound as a white solid. The solid was further purified by recrystallization from methanol. Example 19
Preparation of 5-((S)-2-Fluorodecyloxy)-2-[4-((R)-2- fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)- 2,2,-difluoroethoxy)propoxy)phenyl]pyrimidine
The title compound was prepared essentially as described in Example 18 using (S)-2-fluoro-decyl-p- toluenesulfonate (0.146 g, 0.44 mol) in place of (R) -2- fluoro-decyl-p-toluenesulfonate. Example 20
Preparation of N-(4-Octyloxy)phenyl-(S)-5-((2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)methyl-2-oxazolidinone
A one liter flask, equipped with a dropping addition funnel, a mechanical stirrer, a thermometer, and a reflux condenser was charged with (R)- epichlorohydrin (5 g, 0.54 mol) under positive nitrogen pressure and was heated to 75°C. A mixture of 2-(2- (nonafluorobutoxy)tetrafluoroethoxy) 2,2-difluoroethanol (22.8 g, 53 mmol) and potassium-t-butoxide (53 mL of 1M in t-butanol) was added to the flask over a period of 1.5 hours, with stirring. The flask was then cooled to ambient temperature and the contents distilled to yield (S)-2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethyl-glycidyl ether (8.8 g, b.p. 65°C at 0.3 torr) .
A solution of N-(4-benzyloxy)phenylethyl urethane (1.0 g, 3.68 mmol, prepared essentially as described by Iwakura et al. in J. Org. Chem. 29, 379 (1964)), (S)-2-(2-(nonafluorobutoxy)tetrafluoroethoxy)- 2,2-difluoroethyl-glycidyl eteer (1.8 g, 3.68 mmol), and triethyl amine (370 mg, 3.68 mmol) in
tetrahydrofuran (5 ml) was heated to reflux temperature for 48 hours. The resulting product was coated onto silica gel and was purified by column chromatography (eluting with 20:1 toluene/ethyl acetate) to give 1.6 g of a tan solid. The solid was dissolved in
tetrahydrofuran (10 ml), and the resulting solution was stirred for 24 hours in the presence of 10% Pd on carbon (100 mg) under 3100 torr (60 psi) of hydrogen. The Pd catalyst was removed by filtration, and the filtrate was concentrated under reduced pressure to give 1.25 g of N-(4-hydroxy)phenyl-(S)-5-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy) methyl-2-oxazolidinone as a white solid.
A solution of of this oxazolidinone (250 mg, 0.4 mmol), 1-bromooctane (116 mg, 0.6 mmol), and potassium carbonate (83 mg, 0.6 mmol) in acetonitrile (20 ml) was stirred at reflux temperature for 18 hours. The resulting product was coated on to silica gel (2 g) and was purified by column chromatography to give 370 mg of the title compound. The compound was further purified by recrystallization from methanol.
Example 21
Preparation of N-(4-Octyloxybenzoyl)phenyl-(S)-5-(2-(2-
(nonafluorobutoxy)tetrafluoroethoxy)2,2- difluoroethoxy)methyl-2-oxazolidinone
Triethylamine (230 mg, 1.76 mmol) was added to a solution of N-(4-hydroxy)phenyl-(S)-5-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy) 2,2-difluoroethoxy) methyl-2-oxazolidinone (500 mg, 0.88 mmol) and 4- octyloxybenzoyl chloride (220 mg, 0.88 mmol) in
dichloromethane (10 ml) . The resulting mixture was stirred at ambient temperature for 4 hours and was then coated onto silica gel and the resulting product purified by column chromatography. The product was further purified by recrystallization from methanol to give 533 mg of the product as a white solid. Example 22
Preparation of 5-Octyl-2-[(4-(S)-5-oxymethyl-3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)-2(3H) furanone)phenyl]pyrimidine
A one liter flask was fitted with an addition funnel, a mechanical stirrer, a reflux condenser, and a thermometer and was charged with 1,3-dibromopropane (360 g, 1.78 mol), 2-(2- (nonafluorobutoxy)tetrafluoroethoxy) 2,2-difluoroethanol (150 g, 0.347 mol), and Adogen 464™ quaternary ammonium phase transfer catalyst (available from Aldrich
Chemical, 30 g). The resulting mixture was heated to 70°C, and the mixture was maintained at 70-90°C while potassium hydroxide (84 g, 1.5 mol, dissolved in 50 mL water) was added dropwise with stirring. After
complete addition, the mixture was maintained at 70-80°C for one hour, was cooled, and then water (300 mL) was added. The resulting upper aqueous layer of the mixture was discarded, and perfluorohexane was added to the remainder. Excess dibromopropane was decanted from the resulting mixture, and the remaining volatile components of the mixture were removed under reduced pressure. The resulting product, 3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)-1-bromopropane, was purified by
distillation on a six-plate Snyder column (b.p. 48-52°C at 0.05 torr) .
A flask was then charged with dry dimethyl formamide and sodium hydride (1.3 g, 43.3 mmol, 80 weight percent dispersion in oil) under positive nitrogen pressure, followed by dropwise addition of diethyl malonate (7.1 g, 44 mmol) with stirring. When gas evolution ceased, C4F9OC2F40CF2CH2OC3H6Br (25 g, 40.6 mmol) was added to the flask, and the resulting mixture was heated to 85°C and then stirred at ambient
temperature overnight. The resulting lower
fluorochemical phase of the mixture was separated, and the upper phase was treated with ether (60 mL) and water (40 mL) and then washed with brine. The
resulting ether phase was added to the fluorochemical phase. The volatile components of this combined fluorochemical phase were removed under reduced
pressure at 40°C, and then the product,
C4F9OC2F40CF2CH2OC3H6CH(CO2C2H5)2 , was purified by
distillation (b.p. 86-90°C at 0.05 torr).
A flask was then charged with the malonate product (4 g, 6.3 mmol), 5-octyl-2-((4-oxymethyl-(S)-2- oxiranyl) phenyl) pyrimidine (2.2 g, 6.8 mmol),
potassium-t-butoxide (6.8 mL of 1M), and t-butanol (15 mL) and was then heated at 83-87°C for 4 hours with stirring. The resulting mixture was acidified with 4.5% aqueous HCl and was stirred at 0°C for 30 minutes. The resulting yellow, gummy solid product was removed by filtration and was air-dried. The product was further purified by recrystallization from methanol. The cis (S,S) isomer of the product was isolated as a 4.9:1 ratio of the cis to trans, and the trans (S,R) isomer was isolated as a 7.3:1 ratio of the trans to cis isomers by liquid chromatography on silica gel using 4:1 hexanes/ethyl acetate as the eluent.
Examples 23 and 24
Preparation of 5-Octyl-2-[4-((S)-2-hydroxy-3-(4-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy) 2,2- difluoroethoxy)phenyl)propoxy)phenyl]pyrimidine and 5- Octyl-2-[4-((R)-2-fluoro-3-(4-(2-(2-
(nonafluorobutoxy)tetrafluoroethoxy) 2,2- difluoroethoxy)phenyl)propoxy)phenyl]pyrimidine
Example 23 was prepared essentially as described in Examples 3 and 4 by combination of
4-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy) phenol (1.4 g, 2.9 mmol, prepared essentially as described in U.S. Patent No. 5,262,082 (Janulis et al.)) with (S)-5-octyl-2-[4-(2,3- oxiranylpropoxy) phenyl]pyrimidine (1.0 g, 2.9 mmol) to produce 5-octyl-2-[4-((S)-2-hydroxy-3-(4-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)2,2- difluoroethoxy)phenyl)propoxy)phenyl]pyrimidine
(Example 23). This chiral (S)-hydroxy compound (1.5 g, 1.7 mmol) was treated with diethylaminosulfur
trifluoride (0.6 g, 3.5 mmol) to produce Example 24.
Examples 25 and 26
Preparation of 5-Octyl-2-[4-((S)-2-hydroxy-3-(6-(2- (nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6- decafluorohexylyloxy)propoxy)phenyl]pyrimidine
and 5-Octyl-2-[4-((R)-2-fluoro-3-(6-(2- (nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6- decafluorohexylyloxy)propoxy)phenyl]pyrimidine
The title compounds were prepared essentially as described in Examples 3 and 4 by combining 6-(2- (nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6--ecafluoro-1-hexanol (22.2 g, 35 mmol) with (S)-5-octyl-2-[4-(2,3- oxiranylpropoxy)phenyl]pyrimidine (10.0 g, 29.4 mmol) to produce 5-octyl-2-[4-((S)-2-hydroxy-3-(6-(2- (nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy)propoxy)phenyl] pyrimidine (Example 25). This chiral (S)-hydroxy compound (20 g, 21 mmol) was treated with
diethylaminosulfur trifluoride (6.6 g, 41 mmol) to produce Example 26. The structures of the compounds are shown in Table 1.
Examples 27 and 28
Preparation of 5-Octyl-2-[4-((S)-2-hydroxy-3-(4-(2-
(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4 - hexafluorobutyloxy)propoxy)phenyl]pyrimidine
and 5-Octyl-2-[4-((R)-2-fluoro-3-(4-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4 - hexafluorobutyloxy)propoxy)phenyl]pyrimidine
The title compounds were prepared essentially as described in Examples 3 and 4 by combining 4-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4- hexafluoro-1-butanol (3.7 g, 7 mmol) with (S)-5-octyl- 2-[4-(2,3-oxiranylpropoxy)phenyl] pyrimidine (2.0 g, 5.87 mmol) to produce 5-octyl-2-[4-((S)-2-hydroxy-3-(4- (2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4- hexafluorobutyloxy)propoxy)phenyl] pyrimidine (Example 27). This chiral (S)-hydroxy compound (3 g, 3.4 mmol) was treated with diethylaminosulfur trifluoride (1.1 g, 6.8 mmol) to produce Example 28. The structures of the compounds are shown in Table 1. Examples 29 and 30
Preparation of 5-Octyl-2-[6-((S)-2-hydroxy-3-(6-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6 -decafluorohexyloxy)propoxy)phenyl] pyrimidine and 5-Octyl-2-[6-((R)-2-fluoro-3-(6-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6 -decafluorohexyloxy)propoxy)phenyl] pyrimidine
The title compounds were prepared essentially as described in Examples 3 and 4 by combining 6-(2-(2- (nonafluorobutoxy) tetrafluoroethoxy) tetrafluoroethoxy- 2,2,3,3,4,4,5,5,6,6-decafluoro-1-hexanol (11.5 g, 15.4 mmol) with (S)-5-octyl-2-[4-(2,3- oxiranylpropoxy) phenyl]pyrimidine (5.0 g, 15.34 mmol) to produce 5-octyl-2-[4-((S)-2-hydroxy-3-(6-(2-(2-
(nonafluorobutoxy)tetrafluoroethoxy)tetrafluoroethoxy- 2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy)propoxy)phenyl] pyrimidine (Example 29). This chiral (S)-hydroxy compound (10.0 g, 9.2 mmol) was treated with
diethylaminosulfur trifluoride (5.8 g, 36 mmol) to produce Example 30. The structures of the compounds are shown in Table 1.
Examples 31 and 32
Preparation of 5-Octyl-2-[4-((S)-2-hydroxy-3-(2,2,2- trifluoroethoxy)propoxy)phenyl]pyrimidine and 5-Octyl- 2-[4-((R)-2-fluoro-3-(2,2,2- trifluoroethoxy)propoxy)phenyl]pyrimidine
The title compounds were prepared essentially as described in Examples 3 and 4 by combining 2,2,2- trifluoroethanol (1.1 g, 11.2 mmol) with (S)-5-octyl-2- [4-(2,3-oxiranylpropoxy)phenyl]pyrimodine (2.0 g, 5.6 mmol) to produce 5-octyl-2-[4-((S)-2-hydroxy-3-(2,2,2- trifluoroethoxy)propoxy)phenyl]pyrimidine (Example 31). This chiral (S)-hydroxy compound (2.0 g, 4.5 mmol) was treated with diethylaminosulfur trifluoride (1.46 g, 9.0 mmol) to produce Example 32. The structures of the compounds are shown in Table 1.
Example 33
Preparation of (S)-5-Octyl-2-[4-(2-(2-
(nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)methyl-2-oxazolidinone)phenyl]
pyrimidine
5-Octyl-2-(4-aminophenyl)pyrimidine was prepared by the following modification of the procedure described by Zaschke et al. in Z. Chem. 15, 441 (1975). Sodium methoxide (25% in methanol, 79.7 g, 3.07 eq) was added to a solution of 4-amino benzamidine
hydrochloride (25 g) and 2-octyl-3-dimethylamino acrolein (25.7 g, 1.0 eq) in methanol (400 ml). The resulting mixture was heated to reflux temperature for 18 hours and was then cooled to ambient temperature. The mixture was acidified with concentrated HCl and was then filtered. The filtrate was diluted with 400 ml of water and was extracted with three 200 ml aliquots of toluene. The combined extracts were concentrated, dissolved in 400 ml of methanol, filtered, and made strongly acidic by saturation with gaseous HCl.
Removal of the solvent provided a red oil which was treated with 250 ml of hot acetone and allowed to cool. Filtration gave 7.5 g of the crude HCl salt. The salt (1 g) was neutralized with 5 equivalents of
triethylamine in tetrahydrofuran (10 ml), and the resulting free amine was purified by liquid
chromatography on silica gel using 20:1
dichloromethane/ethyl acetate as the eluent.
A solution of the free amine (5-octyl-2-(4- aminophenyl) pyrimidine, 0.37 g, 1.31 mmol) in acetonitrile (2 ml) was added dropwise to a solution of magnesium perchlorate (0.29 g, 1.31 mmol) and 2-(2- (nonafluorobutoxy) tetrafluoroethoxy) ethyl-glycidyl ether (0.64 g, 1.31 mmol) in acetonitrile (1 ml). The resulting mixture was stirred under a nitrogen
atmosphere for 18 hours, during which time a white precipitate formed. The precipitate was isolated by filtration to give 0.88 g of crude amino alcohol (5- octyl-2-(4-(3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy-2-hydroxypropyl)aminophenyl)pyrimidine). A solution of triphosgene (96 mg, 0.33 mmol) in
dichloromethane (2 ml) was then added dropwise to a 0°C solution of the amino alcohol (500 mg, 0.56 mmol) and pyridine (0.26 ml, 3.25 mmol) in dichloromethane (4 ml). The resulting mixture was stirred for 1 hour at 0°C and then for 3 hours at ambient temperature. The mixture was then coated onto silica gel and purified by chromatography on silica gel using 15:1
dichloromethane/ethyl acetate as the eluent. The resulting product was further purified by
recrystallization from hexane.
Example 34
Preparation of 5-Octyl-2-[4-((S)-2-hydroxy-3-(8-(2-
(nonafluorobutoxy)tetrafluoroethoxy)-
2,2,3,3,4,4,5,5,6,6,7,7,8,8- tetradecafluorooctyloxy)propoxy)phenyl]pyrimidine
The title compound was prepared essentially as described in Examples 3 and 4 by combining 8-(2-
(nonafluorobutoxy)tetrafluoroethoxy)-
2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluoro-1-octanol
(6.4 g, 8.8 mmol) with (S)-5-octyl-2-[4-(2,3- oxiranylpropoxy)phenyl]pyrimidine (2.5 g, 7.35 mmol). Example 35
Preparation of 5-Octyl-2-[4-((S)-2-hydroxy-3-(4-(2- (tridecafluorohexyloxy)tetrafluoroethoxy)-2,2,3,3,4,4- hexafluorobutyloxy)propoxy)phenyl]pyrimidine
The title compound was prepared essentially as described in Examples 3 and 4 by combining 4- (2- (tridecafluorohexyloxy)tetrafluoroethoxy)-2,2,3,3,4,4- hexafluorobutanol (6.4 g, 10.1 mmol) with (S)-5-octyl- 2-[4-(2,3-oxiranylpropoxy)phenyl]pyrimidine (4.0 g, 11.8 mmol) .
Comparative Example 1
Preparation of 5-Octyl-2-[4-((R)-2-fluoro-3-(2-(2- butoxyethoxy)ethoxy)propoxy)phenyl]pyrimidine
Boron trifluoride etherate (1.3 ml, 10.8 mmol) was added dropwise to a 0°C solution of 2-(2- butoxyethoxy) ethanol (35 g, 216 mmol) and (S)- epichlorohydrin (10 g, 108 mmol). The resulting mixture was warmed slowly to ambient temperature and was stirred for 18 hours at ambient temperature. 1- chloro-3-(2-(2-butoxyethoxy)ethoxy)-2-propanol was distilled from the mixture (105-110°C at 0.3 torr) .
Potassium carbonate (2.1 g, 15.7 mmol) was added to a solution of 5-octyl-2-(4- hydroxyphenyl) pyrimidine (3.0 g, 10.5 mmol) and 1- chloro-3-(2-(2-butoxyethoxy)ethoxy)-2-propanol (2.7 g, 10.5 mmol) in N,N-dimethylformamide (100 ml). The resulting mixture was stirred at reflux temperature for 18 hours and then cooled to ambient temperature. The mixture was diluted with water (100 ml) and was
extracted with three 100 ml aliquots of diethyl ether. The extracts were dried (over MgSO4), filtered, and concentrated to give crude product as an oil. 5-Octyl- 2-[4-((S)-2-hydroxy-3-(2-(2- (butoxy)ethoxy)ethoxy)propoxy)phenyl]pyrimidine was then isolated by chromatography. The chiral (S)- hydroxy compound (3.5 g, 7.5 mmol) was treated with diethylaminosulfur trifluoride (5.3 g, 15 mmol) to produce Comparative Example 1.
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
The compounds of Table 1 were evaluated for transition temperatures by differential scanning calorimetry (DSC) and/or optical observation of
material phase changes using a Linkham TMH600 hot stage and a polarizing microscope. The transition
temperatures (°C) were obtained upon cooling through the isotropic state (I) to the smectic A mesophase (SA), the smectic C mesophase (SC), and higher order
mesophases (M1 and M2) and are set forth in Table 2 below.
Figure imgf000049_0001
Figure imgf000050_0001
The data in Table 2 shows that most of the compounds of the invention exhibit smectic mesophases and that many of the compounds exhibit a broad smectic C mesophase, which makes the compounds well-suited for use in liquid crystal display devices. As a result of the breadth of the smectic C mesophase, the compounds are useful in admixture with themselves or with other liquid crystal compounds, even at high concentration. In contrast with Example 5 which shows a broad smectic C mesophase. Comparative Example 1 shows no liquid crystal behavior above 20°C. Examples 36-53 describe liquid crystal compound
mixtures and/or liquid crystal display devices of the invention.
Example 36
A device containing a chiral compound of this invention (Example 5) was prepared essentially as described in U.S. Patent No. 5,377,033 (Radcliffe) and filled with a mixture of 9.7 weight percent 5-octyl-2- [4-((R)-2-fluoro-3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 5),
11.5 weight percent 5-octyloxy-2-[4-(2-(2-
(nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)phenyl]pyrimidine (prepared essentially as described in U.S. Patent No. 5,262,082 (Janulis et al.)), 11.6 weight percent 5-decyloxy-2-[4-(4- (nonafluorobutoxy)octafluorobutoxy)-2,2,3,3,4,4- hexafluorobutoxy)phenyl]pyrimidine, 12.6 weight percent 5-decyloxy-2-[2-(2- (tridecafluorohexyloxy)tetrafluoroethoxy)-2,2 - difluoroethoxy)phenyl]pyrimidine, 6.6 weight percent 5- octyl-2-[4-(3-(4-(2-(2-
(nonafluorobutoxy)tetrafluoroethoxy)2,2- difluoroethoxy)phenyl)phenyl]pyrimidine, 13.4 weight percent 5-octyl-2-[4-(4-
(nonafluorobutoxy)octafluorobutoxy)-2,2,3,3,4,4- hexafluorobutoxy)phenyl]pyrimidine, and
34.7 weight percent 5-decyl-2-[4-(4- (nonafluorobutoxy)octafluorobutoxy)-2,2,3,3,4,4- hexafluorobutoxy)phenyl]pyrimidine.
The ITO-constituted electrodes of the device were connected to an arbitrary waveform generator with variable output voltage. The device was driven by a voltage waveform consisting of bipolar, square pulses of ±10V/μm amplitude, spaced 30 milliseconds apart by a train of square pulses having the same width and 3.3 V/μm amplitude. The device was heated to the
temperatures noted in Table 3 (below) and the
polarization (nC/cm2), the τelectric, the smectic
viscosity, and the tilt angle φt were determined as described below:
The polarization of the device was determined
essentially as described by Miyasato et al . in Jap. J. Appl. Phys. 22, 661 (1983). The electronic response time, τelectric, was derived from the displacement current of the ferroelectric liquid crystal device under an applied square voltage pulse. The current was viewed on a 100 megahertz bandwidth oscilloscope. The usual decaying exponential, associated with a dielectric filled capacitor, was followed by the spontaneous polarization (PS) switching pulse. The time from the rising edge of the voltage pulse to the peak of the PS pulse was taken to be τelectric. The rotational viscosity (smectic viscosity, η) was calculated as shown below : η(10-3 kg / m • s) = 0.01 • Ps • E • telectric , where the units of PS, E, and telectric are
respectively nC/cm2 , V/μm, and μs. The tilt angle φt of the mixture was taken to be half the angle
separating the extinction points of the driven states. The results given in Table 3 show fast response times over a wide temperature range. In addition, the phase transition
temperatures of the mixture were measured essentially as described above and were found to be: I to A =
105.8°C, A to C = 12 .1°C, and C to M = -9.0°C. The phase transition temperatures of the achiral base material (i.e., the above-described mixture without the chiral dopant) were also measured and were found to be:
I to A = 106.2°C, A to C = 70.5°C, and C to M = -5.6°C. Thus, the smectic C temperature range of the mixture was essentially the same as that of the achiral base.
Comparative Example 2
A mixture was prepared essentially as
described in Example 36 using the same achiral base mixture and 9.7 weight percent 5-octyl-2-[4-((R)-2- fluoro-3-(2-(2- butoxyethoxy)ethoxy)propoxy)phenyl]pyrimidine
as chiral dopant (instead of Example 5). The phase transition temperatures of the resulting mixture were found to be: I to A = 99.5°C, A to C = 31.6°C, and C to M = 22.8°C. This data shows a severe loss of the smectic C mesophase range relative to Example 36, which loss effectively prevents the use of this comparative mixture in liquid crystal display devices.
Examples 37-52
Other devices were constructed using commercially available polyimides (such as RN-305, RN- 741, or RN-763 available from Nissan Chemical
Industries, Japan) in place of nylon 6/6, or using commercially available cells (such as a DisplayTech cell, available from DisplayTech in Boulder, CO, or an EHC cell, available from EHC Ltd., Japan). Since the properties measured to characterize the present invention are largely independent of cell type, a variety of cells could be utilized. Polarization, viscosity, response time, and tilt angle are
effectively independent of the alignment system in a cell, although there are minor differences in some properties (such as better alignment in nylon cells).
Example 37
A device was prepared and evaluated essentially as described in Example 36 using a mixture of 5 weight percent 5-octyl-2-[(4-(S)-5-oxymethyl-3-(2- (2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)-2(3H)furanone)phenyl]pyrimidine
(Example 22) as the chiral dopant, 63.3 weight percent 5-octyl-2-[4-(6-(2-
(nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6- decafluorohexyloxy)phenyl]
pyrimidine, and 31.6 weight percent 5-octyl-2-[4-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)phenyl]pyrimidine. The results are shown in Table 3 below.
In addition, the phase transition
temperatures of the mixture were measured essentially as described above and were found to be: I to A = 99.7°C, A to C = 54.1°C, and C to K = -16.1°C.
Comparative Example 3
Into a flask fitted with a stirrer, a thermometer, and a reflux condenser was charged KOH (24.6 g, 373 mmol, dissolved in 25 mL water), 1,1- dihydroperfluoromethoxyethoxyethoxyethanol (50 g, 125.6 mmol; prepared by sodium borohydride reduction of the corresponding methyl ester, essentially as described in Example 3 of U.S. Pat. No. 5,262,082 (Janulis et al.)), tetrabutylammonium hydrogen sulfate (3.0 g, 8.8 mmol), and 1,6-dibromohexane (150 g). The resulting reaction mixture was heated at 100°C for three hours, cooled to room temperature, and diluted with water (75 mL) and perfluoro-N-methyl morpholine (153 g) in a separatory funnel. The resulting lower fluorochemical phase was removed from the funnel, and the solvent was distilled at ambient pressure. The resulting residue was
distilled, and the fraction boiling at 83-97°C at 0.3 torr was collected. GC/MS analysis of this fraction showed that it contained 12 area % dibromohexane, 71 area % desired 6-(1,1- dihydroperfluoro (methoxyethoxyethoxyethoxy))-1- bromohexane (CF3O (CF2CF2O) 2CF2CH2O (CH2)6Br), and 7 area % CF3O (CF2CF2O) 2CF2CH2O (CH2)6OCH2CF2 (OCF2CF2)2OCF3.
Using essentially the procedure of Example 8, 5- hydroxy-2-(4-(dihydro-5-(R)-oxymethyl-3-(R)-hexyl- 2 (3H)-furanone)phenyl)pyrimidine (0.20 g, 0.54 mmol) was combined with potassium carbonate (0.09 g, 0.65 mmol) and 6-(1,1- dihydroperfluoro(methoxyethoxyethoxyethoxy))-1- bromohexane (0.30 g, 0.54 mmol) in acetonitrile (20 mL) to yield 0.18 g of product, a 90:10 mixture of
cis/trans dihydrofuranone isomers (as determined by 1H nuclear magnetic resonance spectroscopy) .
A device was prepared and evaluated essentially as described in Example 36 using a mixture of 5 weight percent of the product (5-(6-(1,1- dihydroperfluoro (((2- methoxyethoxy)ethoxy)ethoxy)hexyloxy-2-(4-(dihydro-5-
(R)-oxymethyl-3-(R)-hexyl-2-(3H)- furanone)phenyl)pyrimidine, prepared as described above), 63.3 weight percent 5-octyl-2-[4-(6-(2-
(nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6- decafluorohexyloxy)phenyl] pyrimidine, and 31.6 weight percent 5-octyl-2-[4-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)phenyl]pyrimidine. The results shown in Table 3 indicate that Example 37 exhibits a much higher polarization than that of this Comparative Example at similar concentrations of chiral dopant. Thus, this data shows the importance of the position of the chiral moiety relative to the fluorochemical group.
In addition, the phase transition
temperatures of the mixture were measured essentially as described above and were found to be: I to A =
100.6°C, A to C = 51.5°C, and C to K = < -10°C.
Example 38
A device was prepared and evaluated essentially as described in Example 36 using a mixture of 5 weight percent 5-octyl-2-[4-((R)-2-hydroxy-3-(2- (2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 3) as the chiral dopant, 63.3 weight percent 5-octyl-2-[4- (6-(2-(nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6- decafluorohexyloxy)phenyl]
pyrimidine, and 31.6 weight percent 5-octyl-2-[4-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)phenyl]pyrimidine. The results given in Table 3 show a low viscosity for the mixture, which provides a fast response time in spite of the low polarization exhibited.
In addition, the phase transition
temperatures of the mixture were measured essentially as described above and were found to be: I to A = 101.1°C, A to C = 54.5°C, and C to K = below room temperature. Example 39
A device was prepared and evaluated essentially as described in Example 36 using a mixture of 20 weight percent 5-octyl-2-[4-((R)-2-hydroxy-3-(2- (2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 3) as the chiral dopant, 53.3 weight percent 5-octyl-2-[4- (6-(2-(nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy)phenyl]
pyrimidine (prepared essentially by the methods
described in U.S. Patent No. 5,262,082 (Janulis et al.)), and 26.6 weight percent 5-octyl-2-[4-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)phenyl]pyrimidine. The results given in Table 3 show a low viscosity for the mixture, which provides a fast response time in spite of the low polarization exhibited.
In addition, the phase transition
temperatures of the mixture were measured essentially as described above and were found to be: I to A =
96.8°C, A to C = 54.3°C, and C to K = below room temperature.
Example 40
A device was prepared and evaluated essentially as described in Example 36 using 100 weight percent 5-octyl-2-[4-((R)-2-fluoro-3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 5). The results given in Table 3 show very fast response times, high polarizations, and low viscosities. In addition, the response times are relatively
temperature-independent . Example 41
A device was prepared and evaluated essentially as described in Example 36 using a mixture of 50.1 weight percent 5-octyl-2-[(4-(S)-5-oxymethyl-3- (2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)-2(3H)furanone)phenyl]pyrimidine
(Example 22) as the chiral dopant, 33.3 weight percent 5-octyl-2-[4-(6-(2- (nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6- decafluorohexyloxy) phenyl]
pyrimidine (prepared essentially by the methods
described in U.S. Patent No. 5,262,082 (Janulis et al.)), and 16.6 weight percent 5-octyl-2-[4-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)phenyl]pyrimidine (prepared essentially as described in U.S. Patent No. 5,262,082). The results given in Table 3 show very fast response times and high polarization.
In addition, the phase transition
temperatures of the mixture were measured essentially as described above and were found to be: I to A -
96.6°C, A to C = 51.5°C, and C to K = 21.4°C. The phase transition temperatures of the achiral base material (i.e., the above-described mixture without the chiral dopant) were also measured and were found to be:
I to A = 99.5°C, A to C = 53.8°C, and C to K = < -10°C. Thus, the use of this chiral compound of the invention (Example 22) at high concentration in an achiral base mixture provides minimal suppression of the smectic C mesophase. Example 42
A device was prepared and evaluated essentially as described in Example 36 using a mixture of 10 weight percent 5-octyloxy-2-[4-((R)-2-fluoro-3- (2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 10) as the chiral dopant, 63.3 weight percent 5-octyl-2-[4- (6-(2-(nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6- decafluorohexyloxy)phenyl]
pyrimidine, and 31.6 weight percent 5-octyl-2-[4-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)phenyl]pyrimidine. The results are shown in Table 3 below.
In addition, the phase transition
temperatures of the mixture were measured essentially as described above and were found to be: I to A =
106.5°C, A to C = 60.5°C, and C to K = < -10°C.
Comparative Example 4
2-(S)-fluorooctanol (3.0 g, 20.2 mmol; which can be prepared by the procedure described by H. Nohira et al. in Mol. Cryst. Liq. Cryst. 180B, 379-88 (1990)) was combined with toluene sulfonyl chloride (4.0 g, 21.2 mmol), ethyl diisopropyl amine (5.2 g, 40.4 mmol), and dimethylaminopyridine (123 mg, 1.0 mmol) in methylene chloride (50 mL). The resulting mixture was stirred at room temperature overnight. The resulting crude tosylate product was purified by flash chromatography on silica gel, eluting with 10 parts by volume of hexane and 1 part by volume of ethyl acetate.
A three-necked flask equipped with a magnetic stir bar, a condenser, and a nitrogen inlet was charged with potassium carbonate (380 mg, 2.74 mmol) and
acetonitrile (20 mL). With stirring, 5-hydroxy-2-(4- (1,1-dihydr-perfluoro-2- (butoxyethoxy)ethoxy)phenyl)pyrimidine (1.5 g, 2.49 mmol; prepared essentially as in Example 18 above with substitution of C4F9OC2F4OCF2CH2OSO2CF3 (4.86 g, 8.6 mmol) for 3-(2-[2-(nonafluorobutoxy)tetrafluoroethoxy]- 2,2-difluoroethoxy)-(R)-2-fluoropropyl-1-p- toluenesulfonate) was slowly added to the resulting mixture. The mixture was stirred at room temperature for 30 minutes. 1-p-toluenesulfonoxy-2-(S)- fluorooctane (0.75 g, 2.49 mmol) was then added to the stirred mixture. The mixture was heated to reflux overnight and then poured into a separatory funnel containing water (~ 20 mL). The resulting layers were separated, and the aqueous phase was extracted with diethyl ether and purified by chromatography
(essentially as in Example 8 above), eluting with 10 parts by volume of hexane and 1 part by volume of ethyl acetate. The yield of desired product was 1.4 g. The structure of the product was confirmed by 1H and 19F nuclear magnetic resonance spectroscopy.
A device was prepared and evaluated essentially as described in Example 36 using a mixture of 10 weight percent of the product (5-((S)-2- fluorooctyloxy)-2-[4-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)phenyl]pyrimidine, prepared essentially as described above), 63.3 weight percent 5-octyl-2- [4- (6-(2-(nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6- decafluorohexyloxy)phenyl]
pyrimidine, and 31.6 weight percent 5-octyl-2-[4-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)phenyl]pyrimidine. The results shown in Table 3 indicate that Example 42 exhibits a much higher polarization than that of this Comparative Example (which effectively does not respond to an electric field) at similar concentrations of chiral dopant. Thus, this data shows the importance of the position of the chiral moiety relative to the fluorochemical group.
In addition, the phase transition
temperatures of the mixture were measured essentially as described above and were found to be: I to A =
101°C, A to C = 56.5°C, and C to K = 0.1°C.
Example 43
A device was prepared and evaluated essentially as described in Example 36 using 100 weight percent 5-octyl-2-[4-((S)-2-fluoro-3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 4). The results given in Table 3 show very fast response times, high polarizations, and low viscosities. In addition, the response times are relatively
temperature-independent .
Example 44
A device was prepared and evaluated essentially as described in Example 36 using 100 weight percent 5-hexyl-2-[4-((R)-2-fluoro-3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine
(Example 8). The results given in Table 3 show very fast response times, high polarizations, and low viscosities. In addition, the response times are relatively temperature-independent . Example 45
A device was prepared and evaluated essentially as described in Example 36 using 100 weight percent 5-octyloxy-2-[4-((R)-2-fluoro-3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 10). The results given in Table 3 show very fast response times, high polarizations, low viscosities, and a very broad smectic C temperature range. In addition, the response times are relatively temperature-independent.
Example 46
A device was prepared and evaluated essentially as described in Example 36 using 100 weight percent 5-((R)-2-fluorooctyloxy)-2-[4-((R)-2-fluoro-3- (2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 18). The results given in Table 3 show very fast response times, high polarizations, and low viscosities. Example 47
A device was prepared and evaluated essentially as described in Example 36 using 100 weight percent 5-((S)-2-fluorooctyloxy)-2-[4-((R)-2-fluoro-3- (2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 19). The results given in Table 3 show very fast response times, high polarizations, and low viscosities.
Example 48
A device was prepared and evaluated essentially as described in Example 36 using a mixture of 10.2 weight percent N-(4-octyloxy)phenyl-(S)-5-((2- (2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)methyl-2-oxazolidinone (Example 20), 59.9 weight percent 5-octyl-2-[4-(6-(2- (nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6- decafluorohexyloxy)phenyl]
pyrimidine, and 29.9 weight percent 5-octyl-2-[4-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)phenyl]pyrimidine. The results given in Table 3 show high polarizations at low chiral dopant concentration.
In addition, the phase transition
temperatures of the mixture were measured essentially as described above and were found to be: I to A =
93.7°C, A to C = 41.9°C, and C to K = < -10°C.
Example 49
A device was prepared and evaluated essentially as described in Example 36 using 100 weight percent 5-hexyloxy-2-[4-((R)-2-fluoro-3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 9). The results given in Table 3 show very fast response times, high polarizations, low viscosities, and a very broad smectic C temperature range. In addition, the response times are relatively temperature-independent.
Example 50
A device was prepared and evaluated essentially as described in Example 36 using a mixture of 5 weight percent 5-octyl-2-[4-((R)-2-fluoro-3-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)propoxy)phenyl]pyrimidine (Example 5) and 95 weight percent 5-heptyl-2-[4-(2-(2-
(pentaafluoroethoxy)tetrafluoroethoxy)-2,2,- difluoroethoxy)phenyl]pyrimidine (prepared essentially as described in U.S. Patent No. 5,262,082 (Janulis et al.)). The results given in Table 3 show a low
viscosity for the mixture, which provides a very fast response time in spite of the low polarization
exhibited.
In addition, the phase transition
temperatures of the mixture were measured essentially as described above and were found to be: I to A = 84 . 2°C , A to C = 53 . 0°C , C to K = 8 . 4°C , and K to C = 29 . 1°C .
Example 51
A device was prepared and evaluated essentially as described in Example 36 using 100 weight percent 5-octyl-2-[4-((R)-2-fluoro-3-(2-(2-(2- (trifluoromethoxy)tetrafluoroethoxy)tetrafluoroethoxy)- 2,2,-difluoroethoxy)propoxy)phenyl]pyrimidine (Example 11) . The results given in Table 3 show very fast response times, high polarizations, and low
viscosities.
Example 52
A device was prepared and evaluated essentially as described in Example 36 using 100 weight percent 5-octyl-2-[4-((R)-2-fluoro-3-(10-(2-
(nonafluorobutoxy)tetrafluoroethoxy)-
2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10- octadecafluorodecyloxy)propoxy)phenyl]pyrimidine
(Example 13). The results given in Table 3 show a fast response time, a high polarization, and a low
viscosity. Example 53
A device was prepared and evaluated essentially as described in Example 36 using a mixture of 10 weight percent (S)-5-octyl-2-[4-(2-(2- (nonafluorobutoxy)tetrafluoroethoxy)-2,2- difluoroethoxy)methyl-2-oxazolidinone)phenyl]
pyrimidine (Example 33), 60 weight percent 5-octyl-2- [4-(6-(2-(nonafluorobutoxy)tetrafluoroethoxy)- 2,2,3,3,4,4,5,5,6,6- decafluorohexyloxy)phenyl]
pyrimidine, and 30 weight percent 5-octyl-2-[4-(2-(2- (nonafluorobutoxy)tetrafluoroet(oxy)-2,2- difluoroethoxy) phenyl] pyrimidine. The results given in Table 3 show high polarizations at low chiral dopant concentration.
In addition, the phase transition
temperatures of the mixture were measured essentially as described above and were found to be: I to A =
105.5°C, A to C = 57.3°C, and C to K = 16.4°C.
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention.

Claims

WHAT IS CLAIMED IS:
1. Fluorine-containing, chiral liquid crystal compounds having smectic mesophases or latent smectic mesophases, the compounds comprising (a) a chiral fluorochemical terminal portion containing at least one methylene group and optionally containing at least one catenary ether oxygen atom; (b) a saturated, chiral or achiral, hydrocarbon terminal portion; and (c) a central core connecting said terminal portions.
2. The compounds of Claim 1 wherein said chiral fluorochemical terminal portion is represented by the formula -D-R*-D- (O)x-CH2-D' -Rf , where R* is a cyclic or acyclic chiral moiety; x is an integer of 0 or 1; Rf is fluoroalkyl, perfluoroalkyl, fluoroether, or perfluoroether; and D' and each D are independently and non-directionally selected from the group consisting of a covalent bond,
-C ( =O) -O-CrH2r- , -O-CrH2r-, -O(C3H2sO)-tCr,H2r,-, -CrH2r-,
-(CsH2sO-)tCr ,H2r.-, -OSO2-, -SO2-, -SO2-CrH2r-,
- O
Figure imgf000070_0001
-C ( =O) - , -O- ( O= ) C-CrH2r-, -CH-N-, -O-,
Figure imgf000070_0002
-S-, -N (CpH2p+ 1 ) -, and combinations thereof, where r and r' are
independently integers of 0 to about 20, s is
independently an integer of 1 to about 10 for each (CsH2sO), t is an integer of 1 to about 6, and p is an integer of 0 to about 4.
3. The compounds of Claim 1 wherein said compounds are represented by the general formula (I) :
Figure imgf000071_0001
where M, N, and P are each independently selected from the group consisting of
Figure imgf000072_0001
Figure imgf000073_0001
a, b, and c are each independently zero or an integer of from 1 to 3, with the proviso that the sum of a + b + c be at least 1; each A and B are non-directionally and independently selected from the group consisting of a covalent bond, -C(=O)-O-, -C(=O)-S-, -C(=O)-Se-,
-C(=O)-Te-, -(CH2CH2)k- where k is 1 to 4,
-CH=CH-, -C≡C-, -CH=N-, -CH2-O-, -C(=O)-, and -O- ; each X, Y, and Z are independently selected from the group consisting of -H, -Cl, -F, -Br, -I, -OH, -OCH3, -CH3, -CF3, -OCF3, -CN, and -NO2; each 1, m, and n are independently zero or an integer of 1 to 4;
D is non-directionally selected from the group
consisting of a covalent bond, -C(=O)-O-CrH2r-, -O-CrH2r-, -O-(O=)C-CrH2r-, -C≡C-,
-CH=CH-, -C(=O)-,
-0-(C3H2sO-)-tCr,H2r ,-, -CrH2r-, -(CsH2sO-)-tCr,H2r,-, -O-, -S-,
-OSO2-, -SO2-, -SO2-CrH2r-, -N (CpH2p+1)-,
Figure imgf000074_0001
Cp p 1 -CH=N-, and combinations thereof, where
Figure imgf000074_0002
+1
r and r' are independently integers of 0 to about 20, s is independently an integer of 1 to about 10 for each (CsH2sO), t is an integer of 1 to about 6, and p is an integer of 0 to about 4;
R is selected from the group consisting of
-O-((Cq,H2q,.v.-(R')v,)-O)w-CqH2q+1-v-(R')v ,
- ((Cq'H2q,-v'-(R')v')-O)w-CqH2q+1-v- (R')v ,
-C (=O) -O-CqH2q-1-v- (R')v , -O- (O=) C-CqH2q+1-v- (R')v ,
Figure imgf000074_0003
-CR' H- (D)g-CR' H-CqH2q+1-v- (R')v , where each R' is independently selected from the group consisting of -Cl, -F, -CF3, -NO2, -CN, -H, -CqH2q+1, -O- (O= ) C-CqH2q+ 1 , -C (=O) -O-CqH2q+ 1 , -Br , -OH, and -OCqH2q+ 1 ; q' is independently an integer of 1 to about 20 for each (Cq,H2q,-O); q is an integer of 1 to about 20; w is an integer of 0 to about 10; v is an integer of 0 to about 6; each v' is independently an integer of 0 to about 6; g is an integer of 1 to about 3; each D is independently and non-directionally selected from the group set forth for D above, with the proviso that the ring containing D has from about 3 to about 10 ring atoms; each W is independently selected from the group consisting of N, CR', and SiR'; and R is chiral or achiral; and
Rf' is -R*-D- (O)x-CH2-D'-Rf , where R* is a cyclic or acyclic chiral moiety; D and D' are each independently and non-directionally selected from the group set forth for D above; x is an integer of 0 or 1; and Rf is fluoroalkyl, perfluoroalkyl, fluoroether, or
perfluoroether.
4. The compounds of Claim 3 wherein said R* is selected from the group consisting of
-0-((Cq,H2q,-v,-(R')v)-O)w-CqH2q-v-(R,)v- ,
- ( (Cq,H2q,-v,- (R')v,)-O)w-CqH2q-v- (R )v- ,
-C(=O)-O-CqH2q-v-(R')v- , -O-(O=)C-CqH2q-v-(R')v- ,
and -CR'H- (D)g-CR'H- ,
Figure imgf000075_0001
where each R' is independently selected from the group consisting of -Cl, -F, -CF3, -NO2, -CN, -H, -CqH2q+1 , -O- (O=)C-CqH2q+1, -C(=O)-O-CqH2q+1, -Br, -OH, and -OCqH2q+1; q' is independently an integer of 1 to about 20 for each (Cq,H2q,-O); q is an integer of 1 to about 20; w is an integer of 0 to about 10; v is an integer of 0 to about 6; each v' is independently an integer of 0 to about 6; g is an integer of 1 to about 3; each D is independently and non-directionally selected from the group set forth for D in Claim 3, with the proviso that the ring containing D has from about 3 to about 10 ring atoms; each W is independently selected from the group consisting of N, CR', and SiR'; and with the proviso that R* is chiral.
5. The compounds of Claim 3 wherein said perfluoroalkyl is represented by the formula -CqF2qX', where q is as defined in Claim 3 and X' is hydrogen or fluorine; said fluoroalkyl and fluoroether are
represented by the formula -Rf''-Rh' where Rf'' is a linear or branched, perfluorinated or partially- fluorinated alkylene group having from 1 to about 10 carbon atoms and optionally containing one or more catenary ether oxygen atoms, and Rh is a linear or branched alkyl group having from 1 to about 14 carbon atoms and optionally containing one or more catenary ether oxygen atoms; and said perfluoroether is
represented by the formula - (CxF2xO)zCyF2y+1, where x is independently an integer of 1 to about 10 for each (CxF2xO), y is an integer of 1 to about 10, and z is an integer of 1 to about 10.
6. The compounds of Claim 3 wherein said compounds are represented by the general formula (II) :
R''- (O)j-G-(OCH2)j-R*-(CsH2sO)tCr,H2r,-Rf (II) where R'' is (R')v-CqH2q+1-v , where q is an integer of 2 to about 10, each R' is independently selected from the group consisting of hydrogen, fluorine, chlorine, methyl, and perfluoromethyl, and v is an integer of 1 to about 3; j is an integer of 0 or 1; G is selected from the group consisting of
Figure imgf000077_0001
R* is selected from the group consisting of
-CqH2q-v- (R')v- and
Figure imgf000078_0001
where R' is -F, q is an integer of 1 to about 4, v is an integer of 1 to about 3, W is N or CH, and D is -C(=O)-O- or -CH2-; s is an integer of 1 to about 6; t is an integer of 0 or 1; r' is an integer of 1 to about 3; and Rf is selected from the group consisting of
-CqF2qX', -Rf''-Rh, and - (CxF2xO)zCyF2y+1, where q is an integer of 1 to about 6, X' is fluorine, Rf'' is a linear or branched, perfluorinated alkylene group having from about 2 to about 4 carbon atoms and
optionally containing one or more catenary ether oxygen atoms, Rh is a linear or branched alkyl group having from about 2 to about 7 carbon atoms and optionally containing one or more catenary ether oxygen atoms, x is independently an integer of 1 to about 10 for each (CxF2xO), y is an integer of 1 to about 8, and z is an integer of 1 to about 5.
7. A mixture of liquid crystal compounds comprising at least one fluorine-containing liquid crystal compound of Claim 1.
8. A liquid crystal display device containing at least one fluorine-containing liquid crystal compound of Claim 1.
9. A process for preparing fluorine- containing, chiral liquid crystal compounds comprising the steps of (a) mixing at least one compound
represented by the formula
Figure imgf000079_0001
with at least one compound represented by the formula
Figure imgf000079_0002
or mixing at least one compound represented by the formula
Figure imgf000079_0003
with at least one compound represented by the formula
Figure imgf000079_0004
or mixing at least one compound represented by the formula
Figure imgf000079_0005
with at least one compound represented by the formula
Figure imgf000080_0001
where M, N, P, a, b, c. A, B, X, Y, Z, l, m, n, D, R, R*, Rf, and Rf' are as defined in Claim 3; x is an integer of 0 or 1; and each A', A'', B', and B'' are independently selected from the group consisting of -H, -Cl, -Br, -I, -OH, -COOH, -CH(CH2OH)2, -SH, -SeH, -TeH, -NH2, -COCl, -CHO, -OSO2Rf"', -OSO2CH3,
-NH(C=O)OCqH2q+1 , -NCO, -OSO2-cyclo (C6H4)-CH3, -CH2COOH, and -CH (C (O)O-CqH2q+1) 2, where Rf"' is a perfluoroalkyl group having from 1 to about 10 carbon atoms and q is an integer of 0 to about 20, and with the proviso that (R*)x-A' can enter into an addition or condensation reaction with A" and that (R*)x-B' can enter into an addition or condensation reaction with B''; and (b) allowing compounds III and IV, compounds V and VI, or compounds III and VII to react.
10. Chiral liquid crystal intermediate compounds represented by the following general formulas IV, VI, and VII:
Figure imgf000080_0002
Figure imgf000081_0001
where N, P, b, c, B, Y, Z, m, n, D, Rf, and Rf' are as defined in Claim 3; and A'' and B'' are selected from the group consisting of -H, -Cl, -Br, -I, -OH, -COOH, -CH(CH2OH)2, -SH, -SeH, -TeH, -NH2, -COCl, -CHO,
-OSO2Rf''', -OSO2CH3, -OSO2-cyclo (C6H4) -CH3, -CH2COOH, -NH(C=O)OCqH2q+1 , -NCO, and -CH (C (O) O-CqH2q+1)2, where Rf'" is a perfluoroalkyl group having from 1 to about 10 carbon atoms and q is an integer of 0 to about 20; with the proviso that, for compound VII, B'' is
-CH(C(O)O-CqH2q+1)2.
PCT/US1996/002636 1995-04-19 1996-03-11 Liquid crystal compounds having a chiral fluorinated terminal portion WO1996033251A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP96908535A EP0821719B1 (en) 1995-04-19 1996-03-11 Liquid crystal compounds having a chiral fluorinated terminal portion
DE69625590T DE69625590T2 (en) 1995-04-19 1996-03-11 LIQUID CRYSTAL CONNECTIONS CONTAINING A CHIRAL, FLUORINATED END GROUP
JP8531712A JPH11505212A (en) 1995-04-19 1996-03-11 Liquid crystal compounds having chiral fluorinated terminal moieties

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/424,892 US5702637A (en) 1995-04-19 1995-04-19 Liquid crystal compounds having a chiral fluorinated terminal portion
US08/424,892 1995-04-19

Publications (1)

Publication Number Publication Date
WO1996033251A1 true WO1996033251A1 (en) 1996-10-24

Family

ID=23684304

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/002636 WO1996033251A1 (en) 1995-04-19 1996-03-11 Liquid crystal compounds having a chiral fluorinated terminal portion

Country Status (9)

Country Link
US (2) US5702637A (en)
EP (1) EP0821719B1 (en)
JP (1) JPH11505212A (en)
KR (1) KR100417356B1 (en)
CA (1) CA2217608A1 (en)
DE (1) DE69625590T2 (en)
MY (1) MY117239A (en)
TW (1) TW445292B (en)
WO (1) WO1996033251A1 (en)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998029559A1 (en) * 1996-12-25 1998-07-09 Hoechst Marion Roussel Ltd. Process for preparing purified dimer of bone-derived factor
WO1998046697A1 (en) * 1997-04-11 1998-10-22 Minnesota Mining And Manufacturing Company Compounds and process for controlling cone tilt angle in mixtures of smectic liquid crystal compounds
WO1999033814A1 (en) * 1997-12-24 1999-07-08 Minnesota Mining And Manufacturing Company Liquid crystal compounds having a chiral fluorinated terminal portion
WO2000009627A1 (en) * 1998-08-10 2000-02-24 Minnesota Mining And Manufacturing Company Tristable liquid crystal display device
EP0982386A1 (en) * 1997-02-24 2000-03-01 Chisso Corporation Liquid crystal compound having negative dielectric anisotropy, liquid crystal composition containing said liquid crystal compound and liquid crystal display device using said composition
US6417828B1 (en) 1999-02-18 2002-07-09 Canon Kabushiki Kaisha Liquid crystal composition, liquid crystal device, driving method thereof and liquid crystal apparatus
US6828460B2 (en) 1999-03-22 2004-12-07 Pfizer Inc. Resorcinol derivatives
WO2008046463A1 (en) * 2006-10-18 2008-04-24 Bayer Schering Pharma Aktiengesellschaft Metal chelates having a perfluorinated peg group, method for the production thereof, and use thereof
US7767677B2 (en) 2004-09-20 2010-08-03 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as stearoyl-CoA desaturase inhibitors
US7777036B2 (en) 2004-09-20 2010-08-17 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as therapeutic agents
US7829712B2 (en) 2004-09-20 2010-11-09 Xenon Pharmaceuticals Inc. Pyridazine derivatives for inhibiting human stearoyl-CoA-desaturase
US7919496B2 (en) 2004-09-20 2011-04-05 Xenon Pharmaceuticals Inc. Heterocyclic derivatives for the treatment of diseases mediated by stearoyl-CoA desaturase enzymes
US7951805B2 (en) 2004-09-20 2011-05-31 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as mediators of stearoyl-CoA desaturase
US8026360B2 (en) 2004-09-20 2011-09-27 Xenon Pharmaceuticals Inc. Substituted pyridazines as stearoyl-CoA desaturase inhibitors
US8071603B2 (en) 2004-09-20 2011-12-06 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as stearoyl-CoA desaturase inhibitors
US8541457B2 (en) 2005-06-03 2013-09-24 Xenon Pharmaceuticals Inc. Aminothiazole derivatives as human stearoyl-CoA desaturase inhibitors
US10125130B2 (en) 2014-04-30 2018-11-13 Pfizer Inc. Cycloalkyl-linked diheterocycle derivatives

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5702637A (en) * 1995-04-19 1997-12-30 Minnesota Mining And Manufacturing Company Liquid crystal compounds having a chiral fluorinated terminal portion
JPH10204036A (en) * 1997-01-27 1998-08-04 Mitsubishi Gas Chem Co Inc Antiferroelectric liquid crystal composition
US6084649A (en) * 1998-08-10 2000-07-04 3M Innovative Properties Company Tristable liquid crystal display device
US6248889B1 (en) 1998-11-20 2001-06-19 3M Innovative Properties Company Process for converting an alcohol to the corresponding fluoride
US6139924A (en) * 1998-11-20 2000-10-31 3M Innovative Properties Company Chiral liquid crystal compounds having a fluorinated terminal portion
US6413448B1 (en) * 1999-04-26 2002-07-02 Displaytech, Inc. Cyclohexyl- and cyclohexenyl-substituted liquid crystals with low birefringence
US6221543B1 (en) 1999-05-14 2001-04-24 3M Innovatives Properties Process for making active substrates for color displays
US6870163B1 (en) 1999-09-01 2005-03-22 Displaytech, Inc. Ferroelectric liquid crystal devices using materials with a de Vries smectic A phase
EP1299335B1 (en) * 2000-07-13 2007-09-05 MERCK PATENT GmbH Chiral compounds ii
US7083832B2 (en) 2000-09-01 2006-08-01 Displaytech, Inc. Partially fluorinated liquid crystal material
US7195719B1 (en) 2001-01-03 2007-03-27 Displaytech, Inc. High polarization ferroelectric liquid crystal compositions
US6703082B1 (en) 2001-06-20 2004-03-09 Displaytech, Inc. Bookshelf liquid crystal materials and devices
US6838128B1 (en) 2002-02-05 2005-01-04 Displaytech, Inc. High polarization dopants for ferroelectric liquid crystal compositions
TWI249225B (en) * 2004-03-10 2006-02-11 Taiwan Semiconductor Mfg Interconnection routing method
US7977359B2 (en) * 2005-11-04 2011-07-12 Amira Pharmaceuticals, Inc. 5-lipdxygenase-activating protein (FLAP) inhibitors
US8399666B2 (en) * 2005-11-04 2013-03-19 Panmira Pharmaceuticals, Llc 5-lipoxygenase-activating protein (FLAP) inhibitors
GB2431927B (en) * 2005-11-04 2010-03-17 Amira Pharmaceuticals Inc 5-Lipoxygenase-activating protein (FLAP) inhibitors
WO2007123844A1 (en) * 2006-04-17 2007-11-01 Dow Corning Corporation Bistable ferroelectric liquid crystal devices
EP2215188B1 (en) * 2007-10-19 2012-04-04 Dow Corning Corporation Oligosiloxane-modified liquid crystal formulations and devices using same
TW200920369A (en) * 2007-10-26 2009-05-16 Amira Pharmaceuticals Inc 5-lipoxygenase activating protein (flap) inhibitor
EP2217680B1 (en) * 2007-10-26 2011-11-30 Dow Corning Corporation Oligosiloxane modified liquid crystal formulations and devices using same
AU2009325091A1 (en) * 2008-05-23 2010-06-17 Panmira Pharmaceuticals, Llc 5-lipoxygenase-activating protein inhibitor
US8546431B2 (en) 2008-10-01 2013-10-01 Panmira Pharmaceuticals, Llc 5-lipoxygenase-activating protein (FLAP) inhibitors
EP2451796B1 (en) 2009-07-08 2013-04-17 Dermira (Canada), Inc. Tofa analogs useful in treating dermatological disorders or conditions
US9067914B1 (en) 2013-12-10 2015-06-30 Genzyme Corporation Tropomyosin-related kinase (TRK) inhibitors
NZ733825A (en) 2014-12-18 2022-02-25 Genzyme Corp Pharmaceutical formulations of tropomyosin related kinase (trk) inhibitors
DE102017010942A1 (en) * 2016-12-08 2018-06-14 Merck Patent Gmbh Additives for liquid crystal mixtures

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0255236A2 (en) * 1986-06-30 1988-02-03 Minnesota Mining And Manufacturing Company Fluorine-containing chiral smectic liquid crystals
EP0331367A2 (en) * 1988-02-29 1989-09-06 Showa Shell Sekiyu Kabushiki Kaisha Liquid crystal compounds having fluoroalkyl radical
US5141669A (en) * 1989-06-30 1992-08-25 Polaroid Corporation Liquid crystal compounds having chiral ester head groups
DE4308028A1 (en) * 1993-03-13 1994-09-15 Merck Patent Gmbh 1,2,2,2-tetrafluoroethyl ether and liquid crystalline medium
EP0641850A1 (en) * 1993-09-06 1995-03-08 Canon Kabushiki Kaisha Mesomorphic compound, liquid crystal composition containing the compound, liquid crystal device using the composition, liquid crystal apparatus and display method
DE4444701A1 (en) * 1993-12-15 1995-06-22 Hoechst Ag Aryl (hetero)-aryloxy-tetra:fluoro-propionates useful in liquid crystal mixt. esp. for electro-optical switch or display
EP0667384A1 (en) * 1994-02-14 1995-08-16 Sumitomo Chemical Company Limited Fluorine-containing optically active compound, process for preparing the same and liquid crystal mixture and liquid crystal element comprising the same

Family Cites Families (59)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2519983A (en) * 1948-11-29 1950-08-22 Minnesota Mining & Mfg Electrochemical process of making fluorine-containing carbon compounds
US3470258A (en) * 1967-04-19 1969-09-30 Stevens & Co Inc J P Fluorinated alcohols-glycidol addition products
US4001137A (en) * 1971-08-07 1977-01-04 Merck Patent Gesellschaft Mit Beschrankter Haftung Nematic compounds and mixtures
US4011173A (en) * 1972-08-03 1977-03-08 Merck Patent Gesellschaft Mit Beschrankter Haftung Modified nematic mixtures with positive dielectric anisotropy
US4113647A (en) * 1976-08-13 1978-09-12 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Liquid crystalline materials
GB1601601A (en) * 1978-01-18 1981-11-04 Standard Telephones Cables Ltd Liquid crystal display cells
JPS5941983B2 (en) * 1978-02-17 1984-10-11 大日本インキ化学工業株式会社 trans(equatorial↓-equatorial)1,4↓-disubstituted cyclohexane derivative
DE2937911A1 (en) * 1978-09-19 1980-03-27 Daikin Ind Ltd FLUORINE-CONTAINING PHENYLBENZOATE COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE
FR2439765A1 (en) * 1978-10-27 1980-05-23 Thomson Csf MESOMORPHIC ORGANIC COMPOUND HAVING A CHEMICAL FORMULA DERIVED FROM A TETRAFLUOROBENZOIC ACID, AND LIQUID CRYSTAL DEVICE USING SUCH A COMPOUND
DE2927277A1 (en) * 1979-07-06 1981-01-08 Merck Patent Gmbh CYCLOHEXYLBIPHENYLE, METHOD FOR THE PRODUCTION THEREOF, THESE DIELECTRICS AND ELECTRO-OPTICAL DISPLAY ELEMENT
US4367924A (en) * 1980-01-08 1983-01-11 Clark Noel A Chiral smectic C or H liquid crystal electro-optical device
GB2067811B (en) * 1980-01-16 1983-08-10 Standard Telephones Cables Ltd Co-ordinate addressing of smetic display cells
US4370486A (en) * 1980-09-02 1983-01-25 Bayer Aktiengesellschaft Biphenyl compounds, a process for their preparation and their use as intermediate products for optical brighteners, dyestuffs, plastics and medicaments
DE3040632A1 (en) * 1980-10-29 1982-05-27 Merck Patent Gmbh, 6100 Darmstadt CYCLOHEXYLPHENYL DERIVATIVES, THESE DIELECTRICS AND ELECTROOPTIC DISPLAY ELEMENT
DE3201721A1 (en) * 1981-01-30 1982-08-19 F. Hoffmann-La Roche & Co. AG, 4002 Basel DISUBSTITUTED AETHANE
EP0058981B1 (en) * 1981-02-25 1986-01-22 Hitachi, Ltd. Colorless liquid crystalline compounds
JPS57165334A (en) * 1981-04-02 1982-10-12 Chisso Corp Halogenobenzene derivative having optical active 2- methylbutyloxyphenyl group
DE3151367A1 (en) * 1981-12-24 1983-07-07 Merck Patent Gmbh, 6100 Darmstadt ACETONITRILE, METHOD FOR THEIR PRODUCTION, THESE DIELECTRICS AND ELECTRO-OPTICAL DISPLAY ELEMENT
DE3206269A1 (en) * 1982-02-20 1983-09-01 Merck Patent Gmbh, 6100 Darmstadt BICYCLOHEXYL DERIVATIVES
US4613209A (en) * 1982-03-23 1986-09-23 At&T Bell Laboratories Smectic liquid crystals
EP0110299B2 (en) * 1982-11-26 1993-06-09 Hitachi, Ltd. Smectic liquid crystal compounds and liquid crystal compositions
DE3332692A1 (en) * 1983-09-10 1985-03-28 Merck Patent Gmbh, 6100 Darmstadt ANISOTROPE COMPOUNDS AND LIQUID CRYSTAL MIXTURES
FR2561250B1 (en) * 1984-03-16 1987-03-06 Thomson Csf ORGANIC COMPOUND HAVING A SMECTIC PHASE A, MIXTURE COMPRISING THE SAME AND MANUFACTURING METHOD
JPS60218358A (en) * 1984-04-13 1985-11-01 Ajinomoto Co Inc Liquid crystal
EP0163229A3 (en) * 1984-05-23 1988-08-17 Hitachi, Ltd. Ferroelectric liquid crystal composition
GB2162515B (en) * 1984-07-04 1988-05-18 Secr Defence Liquid crystal esters
DE3524489A1 (en) * 1984-07-12 1986-01-23 Kabushiki Kaisha Suwa Seikosha, Tokio/Tokyo 2-PHENYLPYRIDINE DERIVATIVES AND METHOD FOR THE PRODUCTION THEREOF
JPH0662476B2 (en) * 1984-09-04 1994-08-17 チッソ株式会社 Liquid crystalline compound having methyleneoxy group and composition thereof
DE3441937A1 (en) * 1984-11-16 1986-05-28 Bayer Ag, 5090 Leverkusen LIQUID CRYSTAL MATERIAL
JPS61210056A (en) * 1985-03-14 1986-09-18 Chisso Corp Halogen-containing optically active liquid crystal compound and liquid crystal composition
FR2579591B1 (en) * 1985-03-29 1988-10-14 Rhone Poulenc Spec Chim PROCESS FOR THE PREPARATION OF PENTAFLUOROETHOXY AND PENTAFLUOROETHYLTHIOBENZENIQUE DERIVATIVES
FR2579594B1 (en) * 1985-03-29 1987-06-05 Rhone Poulenc Spec Chim PROCESS FOR THE PREPARATION OF TRIFLUOROETHOXY OR TRIFLUOROETHYLTHIOBENZENES
DE3629446A1 (en) * 1985-09-04 1987-03-12 Canon Kk OPTICALLY ACTIVE THIOLES AND THEIR MESOMORPHA ESTER DERIVATIVES
DE3766260D1 (en) * 1986-01-31 1991-01-03 Dainippon Ink & Chemicals OPTICALLY ACTIVE CARBONIC ACID DERIVATIVES AND LIQUID CRYSTALLINE COMPOSITIONS CONTAINING THEM.
US4816178A (en) * 1986-04-30 1989-03-28 Canon Kabushiki Kaisha Optically active compound and liquid crystal composition containing same
US4886619A (en) * 1986-06-30 1989-12-12 Minnesota Mining And Manufacturing Company Fluorine-containing chiral smectic liquid crystals
DE3638026A1 (en) * 1986-11-07 1988-05-11 Merck Patent Gmbh CHIRAL CONNECTIONS
GB2201687B (en) * 1987-01-30 1991-01-02 Merck Patent Gmbh Perfluoroalkylene additives for liquid crystalline mixtures
DE3714043A1 (en) * 1987-04-28 1988-11-17 Merck Patent Gmbh ELECTROOPTIC LIQUID CRYSTAL DISPLAY ELEMENT
JPH01104031A (en) * 1987-07-03 1989-04-21 Ajinomoto Co Inc Fluorine compound and liquid crystal composition
EP0330491B1 (en) * 1988-02-26 1993-04-28 Showa Shell Sekiyu Kabushiki Kaisha Novel liquid crystal compounds
DE3807802A1 (en) * 1988-03-10 1989-09-21 Merck Patent Gmbh CHIRAL DERIVATIVES OF 1,2-DIFLUORBENZENE
JPH0269443A (en) * 1988-09-02 1990-03-08 Sharp Corp Fluoroalkyl based compound and liquid crystal composition
US5082587A (en) * 1988-09-23 1992-01-21 Janulis Eugene P Achiral fluorine-containing liquid crystals
US5362919A (en) * 1988-12-02 1994-11-08 Minnesota Mining And Manufacturing Company Direct fluorination process for making perfluorinated organic substances
US5167859A (en) * 1988-12-22 1992-12-01 Merck Patent Gesellschaft Mit Beschraenkter Haftung 2,5-disubstituted heterocycle and liquid-crystalline phase
DE4006743A1 (en) * 1989-07-11 1991-01-24 Merck Patent Gmbh CHIRAL OR ACHIRREL RING LINKS
US5062691A (en) * 1989-10-27 1991-11-05 Minnesota Mining And Manufacturing Company Liquid crystal device with grey scale
KR0182253B1 (en) * 1990-01-27 1999-05-15 위르겐 호이만, 라인하르트 슈틀러 Partially fluorinated compounds
DE4034123A1 (en) * 1990-10-26 1992-04-30 Merck Patent Gmbh Partially fluorinated alkane derivs. - useful as components of liq. crystal media for electro=optical displays
EP0770662B1 (en) * 1991-11-22 2003-03-05 Canon Kabushiki Kaisha Liquid crystal composition, liquid crystal device and display apparatus
US5262082A (en) * 1992-04-28 1993-11-16 Minnesota Mining And Manufacturing Company Ferroelectric liquid crystal compounds having perfluoroether terminal portions
US5252695A (en) * 1992-06-03 1993-10-12 The United States Of America As Represented By The Secretary Of The Navy Fast switching ferroelectric liquid crystalline polymers
CA2099437A1 (en) * 1992-07-17 1994-01-18 Marc D. Radcliffe Liquid crystal display device
US5399291A (en) * 1993-09-30 1995-03-21 Minnesota Mining And Manufacturing Company Liquid crystal compounds having a fluoroether terminal portion
US5474705A (en) * 1993-12-22 1995-12-12 Minnesota Mining And Manufacturing Company Chiral liquid crystal compounds having a perfluoroether terminal portion
US5417883A (en) * 1994-04-11 1995-05-23 Minnesota Mining And Manufacturing Company Process for controlling layer spacing in mixtures of smectic liquid crystal compounds
US5702637A (en) * 1995-04-19 1997-12-30 Minnesota Mining And Manufacturing Company Liquid crystal compounds having a chiral fluorinated terminal portion
US5658491A (en) * 1995-10-12 1997-08-19 Minnesota Mining And Manufacturing Company Process for controlling cone tilt angle in mixtures of smectic liquid crystal compounds

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0255236A2 (en) * 1986-06-30 1988-02-03 Minnesota Mining And Manufacturing Company Fluorine-containing chiral smectic liquid crystals
EP0331367A2 (en) * 1988-02-29 1989-09-06 Showa Shell Sekiyu Kabushiki Kaisha Liquid crystal compounds having fluoroalkyl radical
US5141669A (en) * 1989-06-30 1992-08-25 Polaroid Corporation Liquid crystal compounds having chiral ester head groups
DE4308028A1 (en) * 1993-03-13 1994-09-15 Merck Patent Gmbh 1,2,2,2-tetrafluoroethyl ether and liquid crystalline medium
EP0641850A1 (en) * 1993-09-06 1995-03-08 Canon Kabushiki Kaisha Mesomorphic compound, liquid crystal composition containing the compound, liquid crystal device using the composition, liquid crystal apparatus and display method
DE4444701A1 (en) * 1993-12-15 1995-06-22 Hoechst Ag Aryl (hetero)-aryloxy-tetra:fluoro-propionates useful in liquid crystal mixt. esp. for electro-optical switch or display
EP0667384A1 (en) * 1994-02-14 1995-08-16 Sumitomo Chemical Company Limited Fluorine-containing optically active compound, process for preparing the same and liquid crystal mixture and liquid crystal element comprising the same

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998029559A1 (en) * 1996-12-25 1998-07-09 Hoechst Marion Roussel Ltd. Process for preparing purified dimer of bone-derived factor
US6551801B1 (en) 1996-12-25 2003-04-22 Biopharm Gesellschaft Zur Biotechnologischen Entwicklung Von Pharmaka Gmbh Process for preparing purified dimer of bone-derived factor
EP0982386A1 (en) * 1997-02-24 2000-03-01 Chisso Corporation Liquid crystal compound having negative dielectric anisotropy, liquid crystal composition containing said liquid crystal compound and liquid crystal display device using said composition
WO1998046697A1 (en) * 1997-04-11 1998-10-22 Minnesota Mining And Manufacturing Company Compounds and process for controlling cone tilt angle in mixtures of smectic liquid crystal compounds
KR100537054B1 (en) * 1997-04-11 2005-12-16 미네소타 마이닝 앤드 매뉴팩춰링 캄파니 Compounds and process for controlling cone tilt angle in mixtures of smectic liquid crystal compounds
US6309561B1 (en) 1997-12-24 2001-10-30 3M Innovative Properties Company Liquid crystal compounds having a chiral fluorinated terminal portion
WO1999033814A1 (en) * 1997-12-24 1999-07-08 Minnesota Mining And Manufacturing Company Liquid crystal compounds having a chiral fluorinated terminal portion
WO2000009627A1 (en) * 1998-08-10 2000-02-24 Minnesota Mining And Manufacturing Company Tristable liquid crystal display device
US6417828B1 (en) 1999-02-18 2002-07-09 Canon Kabushiki Kaisha Liquid crystal composition, liquid crystal device, driving method thereof and liquid crystal apparatus
US6828460B2 (en) 1999-03-22 2004-12-07 Pfizer Inc. Resorcinol derivatives
US6933319B2 (en) 1999-03-22 2005-08-23 Pfizer Inc. Resorcinol derivatives
US7829712B2 (en) 2004-09-20 2010-11-09 Xenon Pharmaceuticals Inc. Pyridazine derivatives for inhibiting human stearoyl-CoA-desaturase
US7767677B2 (en) 2004-09-20 2010-08-03 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as stearoyl-CoA desaturase inhibitors
US7777036B2 (en) 2004-09-20 2010-08-17 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as therapeutic agents
US7919496B2 (en) 2004-09-20 2011-04-05 Xenon Pharmaceuticals Inc. Heterocyclic derivatives for the treatment of diseases mediated by stearoyl-CoA desaturase enzymes
US7951805B2 (en) 2004-09-20 2011-05-31 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as mediators of stearoyl-CoA desaturase
US8026360B2 (en) 2004-09-20 2011-09-27 Xenon Pharmaceuticals Inc. Substituted pyridazines as stearoyl-CoA desaturase inhibitors
US8071603B2 (en) 2004-09-20 2011-12-06 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as stearoyl-CoA desaturase inhibitors
US8541457B2 (en) 2005-06-03 2013-09-24 Xenon Pharmaceuticals Inc. Aminothiazole derivatives as human stearoyl-CoA desaturase inhibitors
WO2008046463A1 (en) * 2006-10-18 2008-04-24 Bayer Schering Pharma Aktiengesellschaft Metal chelates having a perfluorinated peg group, method for the production thereof, and use thereof
US8263040B2 (en) 2006-10-18 2012-09-11 Bayer Schering Pharma Ag Metal chelates having a perfluorinated PEG radical, processes for their preparation, and their use
US10125130B2 (en) 2014-04-30 2018-11-13 Pfizer Inc. Cycloalkyl-linked diheterocycle derivatives
US10676471B2 (en) 2014-04-30 2020-06-09 Pfizer Inc. Cycloalkyl-linked diheterocycle derivatives

Also Published As

Publication number Publication date
MY117239A (en) 2004-06-30
US5972241A (en) 1999-10-26
CA2217608A1 (en) 1996-10-24
US5702637A (en) 1997-12-30
EP0821719A1 (en) 1998-02-04
DE69625590T2 (en) 2003-11-20
KR100417356B1 (en) 2004-03-19
KR19990007844A (en) 1999-01-25
DE69625590D1 (en) 2003-02-06
TW445292B (en) 2001-07-11
EP0821719B1 (en) 2003-01-02
JPH11505212A (en) 1999-05-18

Similar Documents

Publication Publication Date Title
EP0821719B1 (en) Liquid crystal compounds having a chiral fluorinated terminal portion
US5437812A (en) Liquid crystal compounds having perfluoroether terminal portions
EP0868501B1 (en) Process for controlling cone tilt angle in mixtures of smectic liquid crystal compounds
EP0646636B1 (en) Liquid crystal compounds having a fluoroether terminal portion
US6309561B1 (en) Liquid crystal compounds having a chiral fluorinated terminal portion
WO1996015092A1 (en) Liquid crystal compounds having perfluoroether terminal portions
EP0540648B1 (en) Ferroelectric liquid crystal compositions containing chiral haloalkoxy tail units
AU690944B2 (en) Chiral liquid crystal compounds having a perfluoroether terminal portion
EP0973844B1 (en) Compounds and process for controlling cone tilt angle in mixtures of smectic liquid crystal compounds
EP0388960B1 (en) Optically active compounds and their preparation and use
US20030003245A1 (en) Liquid crystal compounds having a silane tail with a perfluoroalkyl terminal portion
EP0351782B1 (en) Optically active compounds liquid crystal composition containing said compound, and liquid crystal optical modulator using said composition

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA JP KR

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2217608

Country of ref document: CA

Kind code of ref document: A

Ref document number: 2217608

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 1996 531712

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1996908535

Country of ref document: EP

Ref document number: 1019970707367

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 1996908535

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1019970707367

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 1996908535

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1019970707367

Country of ref document: KR