WO1996006061A2 - Laterally substituted chloroarenes, their manufacture and mixtures containing them - Google Patents

Laterally substituted chloroarenes, their manufacture and mixtures containing them Download PDF

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WO1996006061A2
WO1996006061A2 PCT/PL1995/000017 PL9500017W WO9606061A2 WO 1996006061 A2 WO1996006061 A2 WO 1996006061A2 PL 9500017 W PL9500017 W PL 9500017W WO 9606061 A2 WO9606061 A2 WO 9606061A2
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denote
group
single bond
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atom
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WO1996006061A3 (en
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Vladimir Bezborodov
Roman Dabrowski
Dimitri Trokhimets
Jerzy Dziaduszek
Genadi Sasnovski
Valery Lapinik
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Wojskowa Akademia Techniczna
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Priority claimed from PL94304749A external-priority patent/PL177052B1/en
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Publication of WO1996006061A2 publication Critical patent/WO1996006061A2/en
Publication of WO1996006061A3 publication Critical patent/WO1996006061A3/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3098—Unsaturated non-aromatic rings, e.g. cyclohexene rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/18—Preparation of halogenated hydrocarbons by replacement by halogens of oxygen atoms of carbonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
    • C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/657—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/657—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings
    • C07C49/683—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings having unsaturation outside the aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/687—Unsaturated compounds containing a keto groups being part of a ring containing halogen
    • C07C49/697—Unsaturated compounds containing a keto groups being part of a ring containing halogen containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/753—Unsaturated compounds containing a keto groups being part of a ring containing ether groups, groups, groups, or groups
    • 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
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • 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
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3028—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon single bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • This invention relates to a novel and simple method for manufacturing laterally sub ⁇ stituted chloroderivatives, their use as components of mixtures useful in the field of liquid crystal display technology.
  • This invention relates also to a new method of manufacturing inter ⁇ mediates being 3,6-disubstituted cyclohex-2-en-1-ones.
  • Liquid crystal compounds containing fluorine atoms in the lateral position of the ben ⁇ zene ring have gain in importance as a components of a liquid crystal mixture because of their low viscosity and high chemical stability.
  • the evidence of this give the following patent specifications: DE 4032579, DE 4030392, EP 460436, JP 92:255793, DE 4106345, DE 4027315, DE 4034508, DE 4100288, DE 4010447, DE 4110018, DE 4016130, DE 4013297, DE 4108705, DE 4012764, DE 4107120, DE 4108398, DE 4013083, DE 4012403, DE 4107389, DE 4012014, DE 4111015, DE 4037519, DE 4113053, DE 4123539, DE 4111991, DE 4104183, DE 4112024, GB 2240778, WO 92:05230, WO 91:05209, WO 92:06748, WO 91 :12233, WO
  • Fluoroderivatives are characterized by low value of viscosity, low value of optical indices, and high chemical stability. For some applications, especially in the field of non-linear optics or STN displays, compounds with high values of birefringence, optical ordinary index n 0 , and perpendicular component of dielectric constant ⁇ , and low ⁇ / ⁇ x ratio are desired. Such properties can be revealed by compounds in which fluorine atom is replaced with chlorine.
  • the known methods for the production of laterally substituted chloro- and fluoroderivatives are com ⁇ plicated and multistage. They have to be performed at low temperatures and using inert-atmo- sphere-lithation procedures, palladium catalyzed coupling of aryl boronic acids, or Grignard coupling.
  • the present invention removes these difficulties by giving a simple and effective method for preparing laterally substituted chloroderivatives and their intermediates.
  • This invention relates to a simple one-stage method for preparation of some 1 ,4-disub- stituted 2-chlorobenzenes by direct transformation of 3,6-disubstituted cyclohex-2-en-1-ones, and also to a new method for preparing these intermediates.
  • DE 3827675A Derivatives of 3,6-cyclohex-2-en-1-one are known from DE 3827675A. These compounds were obtained by joining smaller molecules containing cyclohex-2-en-1-one ring, for example by coupling 4-octyloxybromobenzene with cyclohex-2-en-1-one in the presence of catalyzer which was the complex of palladium salt and triphenylphosphine.
  • a method for preparing two-ring cyclohex-2-en-1-ones by a Michael-type reaction using the hydrochloride of aryl ⁇ -dialkylaminoalkyl ketones and ⁇ -ketoesters or ⁇ -diketons is also known. This reaction was carried in the presence of alcoholates such as potassium tert-but- oxide, sodium ethoxide or propoxide (J.Am.Chem.Soc, 75, 1330 (1952)).
  • Y is an H, F, Cl atom, or CN, OCF 3 , CF 3 , or COOC n H 2
  • Y is an H, F, Cl atom, or CN, OCF 3 , CF 3 , or COOC n H 2
  • Y is an H, F, Cl atom, or CN, OCF 3 , CF 3 , or COOC n H 2
  • Y is an H, F, Cl atom, or CN
  • the compounds of the present invention are produced by heating, advantageously at temperature above 50°C, the compounds of the general formula 11 (scheme 1), where the symbols are the same as in the case of formula 1 , in the excess of PCI 5 in hydrocarbon or chlorohydrocarbon solvent. Hexane, benzene, CCI 4 chlorobenzene, toluene or xylene are recommended as solvent.
  • liquid crystal compounds of the present invention are useful as components of a liquid crystalline mixture. They make it possible to increase the optical anisotropy ( ⁇ n) of mixture and to adjust the value of the ⁇ / ⁇ ratio.
  • the mixtures containing the compounds according to the present invention are also the subject of the present invention.
  • the mixtures of the present invention contain at least two compounds and at least one of them is a compound of the formula 1.
  • the mixtures may be composed exclusively of compounds of formula 1 , or they may contain apart from compounds of formula 1 other known liquid crystalline compounds and other
  • SUBSTITUTE SHEET substances such as solvents, optically active compounds, dichroic dyes or polymers.
  • Compounds of formulae 1a-g are advantageous components of the mixtures of the present invention, wherein R 1 and R 2 are an alkyl or alkoxy group..
  • the invention concerns also a liquid crystalline display composed of two plane parallel support plates, at least one of them is transparent, on which there are electrodes, orienting layers and/or isolating layers, and/or color filters between which a liquid crystalline medium is placed.
  • this medium is the liquid crystalline mixture of the present invention.
  • the invention provides also intermediates for obtaining laterally substituted chloro- arenes of the general formula 1.
  • the process (scheme 2) consists in heating acetoacetate acid esters of formula 15, where A 2 denotes a single bond or one of the fragments given by formulae 2-10; R 2 denotes a Y-(CH 2 ) n -(0) m -(C 2 ) k -(0) CHJ p - or Y-(CH 2 ) n -CH---CH-(CH 2 ) p - group, where Y denotes an H, F, or Cl atom, or a terminal group such as CN, OCF 3 , CF 3 , COOC n H 2n+1 ; R 3 denotes an alkyl group containing from 1 to 10 carbon atoms, advantageously 2, with the
  • the reaction is carried in organic solvents such as alcohols or ethers in the presence of inorganic base or alkaline metals salts, advan ⁇ tageously NaOH or KOH, Na 2 CO 3 or K 2 CO 3 .
  • organic base such as trialkylamine or 1 ,8-diazobicyclo[5.4.0]undec-7-ene (DBU).
  • DBU 1,8-diazobicyclo[5.4.0]undec-7-ene
  • the addition of a small amount of tetraamonium salt sometimes results in the increased yield.
  • the product of condensation is treated with an aqueous solution of an acid, advantageously sulfuric acid, then it is separated out of the reaction mixtures using known methods, advantageously the extraction.
  • Unsaturated cyclic ketones which are the subject of the invention as intermediates, often reveal nematic and/or smectic properties. They can be used as the components of liquid crystalline mixtures, especially as dopants for ferroelectric liquid crystal mixtures, but their chemical stability is not high, especially when the cyclohexenone ring is located in such a way that a system of conjugated bonds is created. That is why the unsaturated cyclic ketones of the present invention are more important as intermediates for the synthesis of liquid crystalline compounds of higher chemical and photochemical stability being the subject of the present invention (formula 1) and others descriebed in our concurrent aplication as well as aromatic compounds of formula 12, 13 and 14 as shown in scheme 1.
  • the compound of formula 12 (scheme 1) is obtained by treating the compound of formula 11 with the Grignard reagent, then with a diluted acid to form diene, which is heated in high boiling hydrocarbons, advantageously in xylene in the presence of 10% palladium on carbon.
  • the compound of the formula 13 (scheme 1) is prepared by treating the compound of formula 11 with sodium borohydride in alcohols at room temperature or above, advantageously at 50° C, to obtain a diene, which is heated in the presence of Pd/C in an aromatic-hydrocarbon solvent.
  • the compound of the formula 14 (scheme 1) is obtained by treating the compound of formula 11 in the presence of palladium on active carbon in an aromatic-hydrocarbon solvent, advantageously in xylene, at temperature 200-220° C.
  • 3,6-Disubstituted cyclohex-2-en-1-ones are also useful for the preparation of many other classes of compounds, for example derivatives of 2,5-disubstituted cyclohexanones, which are starting materials for the synthesis of liquid crystalline derivatives of cyclohexane or cyclohexene, what was shown in scheme 4.
  • the notation used in scheme 4 is the same as described above, except for Z ⁇ and Z A , which denote a single bond or a CH 2 CH 2 , CH 2 O or OCH 2 group.
  • Carbon tetrachloride was distilled off and the crude product was purified by column chromatography (silica gel, hexane) and then recrystaliized from a hexane: ethanol (2:1) solution. The colorless crystalline solid was obtained. Yield 60.9 % (1.5g); transition temperatures: Cr 81.5 N 220.5 I; mass spectrum: 494 and 492 (M * ), 394 and 392, 327 and 325 (C 3 H 7 -C ⁇ H 10 -Ph-PhCI-CH 2 ) * , 291, 227 and 225, 205, 165.
  • Mixtures B, C, D, E, and F have the following parameters:
  • Mixture G of the following composition was prepared :
  • mixture G 10 % wt of 4-(trans-4-pentylcyclohexylethyl-2)-3-chloro-4'-(trans-4-propylcyclohexyl)biphenyl was added to mixture G to obtain mixture H which has the following parameters: T N , 72°C ⁇ /20° 17.8 mPa*s
  • alkaline medium such as NaOH or KOH the following compounds were prepared.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention relates to a novel and simple method for manufacturing laterally substituted chloroderivatives of formula (1) and 3,6-disubstituted cyclohex-2-en-1-ones being intermediates for their manufacturing. The chloroderivatives of the present invention are useful as components of liquid crystalline mixtures used in the field of liquid crystal display technology.

Description

Laterally substituted chloroarenes, their manufacture and mixtures containing them
This invention relates to a novel and simple method for manufacturing laterally sub¬ stituted chloroderivatives, their use as components of mixtures useful in the field of liquid crystal display technology. This invention relates also to a new method of manufacturing inter¬ mediates being 3,6-disubstituted cyclohex-2-en-1-ones.
Liquid crystal compounds containing fluorine atoms in the lateral position of the ben¬ zene ring have gain in importance as a components of a liquid crystal mixture because of their low viscosity and high chemical stability. The evidence of this give the following patent specifications: DE 4032579, DE 4030392, EP 460436, JP 92:255793, DE 4106345, DE 4027315, DE 4034508, DE 4100288, DE 4010447, DE 4110018, DE 4016130, DE 4013297, DE 4108705, DE 4012764, DE 4107120, DE 4108398, DE 4013083, DE 4012403, DE 4107389, DE 4012014, DE 4111015, DE 4037519, DE 4113053, DE 4123539, DE 4111991, DE 4104183, DE 4112024, GB 2240778, WO 92:05230, WO 91:05209, WO 92:06748, WO 91 :12233, WO 91 :15555, JP 91:203987, JP 92:54138, JP 93:58928, JP 92:91056, EP 492668, EP 502407, EP 507094.
Fluoroderivatives are characterized by low value of viscosity, low value of optical indices, and high chemical stability. For some applications, especially in the field of non-linear optics or STN displays, compounds with high values of birefringence, optical ordinary index n0, and perpendicular component of dielectric constant ε , and low Δε/εx ratio are desired. Such properties can be revealed by compounds in which fluorine atom is replaced with chlorine. The known methods for the production of laterally substituted chloro- and fluoroderivatives are com¬ plicated and multistage. They have to be performed at low temperatures and using inert-atmo- sphere-lithation procedures, palladium catalyzed coupling of aryl boronic acids, or Grignard coupling.
The present invention removes these difficulties by giving a simple and effective method for preparing laterally substituted chloroderivatives and their intermediates.
This invention relates to a simple one-stage method for preparation of some 1 ,4-disub- stituted 2-chlorobenzenes by direct transformation of 3,6-disubstituted cyclohex-2-en-1-ones, and also to a new method for preparing these intermediates.
These latter compounds are interesting for preparing many other liquid crystal structures with aromatic, saturated or unsaturated rings which can be used for information displays, some of them are themselves new mesogenic compounds.
Disubstituted 3,6-diaryl- or arylalkylcyclohex-2-en-1-ones are known from JP 88:203634, 87:185036, 86:268646, 92:193844 and Brettle et al., Proceedings of the Fourth International Ferroelectric Liquid Crystals Conference, Tokyo 1993, Japan, p. 231. They are used for obtaining saturated cyclohexanones used as dopants for ferroelectric (JP 92:193844) or nematic (JP 87:185036, DE 3.510434, 86:268646) mixtures or for obtaining liquid crystalline compounds containing laterally unsubstituted cyclohexane ring (JP 88:203634). These compounds were obtained condensing chloroethylketones with acetoacetate derivatives (JP 87:185036, Brettle et al., Chem. Lett., p. 1663 (1993)).
Derivatives of 3,6-cyclohex-2-en-1-one are known from DE 3827675A. These compounds were obtained by joining smaller molecules containing cyclohex-2-en-1-one ring, for example by coupling 4-octyloxybromobenzene with cyclohex-2-en-1-one in the presence of catalyzer which was the complex of palladium salt and triphenylphosphine.
A method for preparing two-ring cyclohex-2-en-1-ones by a Michael-type reaction using the hydrochloride of aryl β-dialkylaminoalkyl ketones and β-ketoesters or β-diketons is also known. This reaction was carried in the presence of alcoholates such as potassium tert-but- oxide, sodium ethoxide or propoxide (J.Am.Chem.Soc, 75, 1330 (1952)).
The present invention provides a method using simple and more efficient alkaline coupling agents. These agents enable also the production of a novel type of 3,6-disubstituted cyclohex-2-en-1-ones with a HC=CH bridge group directly coupled with π electron systems of cyclohex-2-en-1-one ring.
The present invention relates to the compounds of the general formula 1, in which R, and R2 are the same or different and denote Y-(CH2)n-(O)m-(CH2)k-(O)l-(CH2)p- or Y-(CH2)n- CH=CH-(CH2)P-, where Y is an H, F, Cl atom, or CN, OCF3, CF3, or COOCnH2„*ι, n, p and k are integers from 0 to 7, m and I denote 0 or 1 ; s and t denote independently 0 or 1 with the condition that s+t≥1 ; Z, and Z2 are the same or different and denote a CH=CH, C≡C or CH2-CH2 group and also a single bond when s and t is not equal to 0; , and A2 denote independently a single bond or one of the fragments represented by the formulae 2-10, where X,, X2, X3 and X4 are independent and denote an H or F atom; B and B, denote independently a single bond or a bridge group such as CH2CH2, CsC, CH=CH, OCH2, CH2O.
The compounds of the present invention are produced by heating, advantageously at temperature above 50°C, the compounds of the general formula 11 (scheme 1), where the symbols are the same as in the case of formula 1 , in the excess of PCI5 in hydrocarbon or chlorohydrocarbon solvent. Hexane, benzene, CCI4 chlorobenzene, toluene or xylene are recommended as solvent.
The liquid crystal compounds of the present invention are useful as components of a liquid crystalline mixture. They make it possible to increase the optical anisotropy (Δn) of mixture and to adjust the value of the Δε/ε ratio. The mixtures containing the compounds according to the present invention are also the subject of the present invention.
The mixtures of the present invention contain at least two compounds and at least one of them is a compound of the formula 1.
The mixtures may be composed exclusively of compounds of formula 1 , or they may contain apart from compounds of formula 1 other known liquid crystalline compounds and other
SUBSTITUTE SHEET substances such as solvents, optically active compounds, dichroic dyes or polymers. Compounds of formulae 1a-g are advantageous components of the mixtures of the present invention, wherein R1 and R2 are an alkyl or alkoxy group..
The mixture containing two- and three-ring compounds show moderate clearing points. The presence of compounds of formulae 1d-g brings about mesophase ranges of the mixtures wider than 150°C.
The invention concerns also a liquid crystalline display composed of two plane parallel support plates, at least one of them is transparent, on which there are electrodes, orienting layers and/or isolating layers, and/or color filters between which a liquid crystalline medium is placed. According to the present invention this medium is the liquid crystalline mixture of the present invention.
The invention provides also intermediates for obtaining laterally substituted chloro- arenes of the general formula 1. The intermediates are compounds of formula 11 , where s and t denotes an integer 1 or 0 with the condition that s+t;>1, R, and R2 are the same, when s=t, and the same or different when s≠t, and denote a Y-(CH2)n-(O)m-(CH2)k-(O)r(CH2)p- or Y-(CH2)n- CH=CH-(CH2)P- group, where Y denotes an H, F, or Cl atom, or a CN, OCF3, CF3, or COOCnH2n+1 group, n, p and k are integers from the range of 0+7, m and I denote 0 or 1 ; Z, and Z2 are the same or different and denote a CH=CH or C≡C group; when s+t>1 Z, denotes also a single bond or a CH2-CH2 group ; A, and A2 denote independently a single bond or one of the fragments given by formulae 2-10, where X,, X2, X3 and X denote independently an H, or F atom; B and B1 denote independently a single bond or a bridge group such as CH2CH2, C≡C, CH=CH, OCH2, CH2O.
The present invention provides a convenient synthetic route for the preparation of intermediates of the general formula 11, where R1 and R2 are the same or different and denote a terminal group: V CHd O)m-(CHMP)r(p Jp- or Y-(CH2)n-CH=CH-(CH2)p-, where Y denotes an H, F, or Cl atom, or a terminal group such as CN, OCF3, CF3, COOCnH2n+1, n, p and k are from the range of 0+7, m and I denote 0 or 1 ; Z, and Z2 are the same or different and denote a single bond, CH=CH, C≡C or CH2-CH2 group; A, and A2 denote independently a single bond or one of the fragments given by formulae 2-10, where X,, X2, X3 and X denote independently an H or F atom; B and B1 denote independently a single bond or a bridge group such as CH2CH2, C≡C, CH=CH, OCH2, CH2O; s and t denote independently 0 or 1 with the condition that s+t≥1.
When s=0 and t=1 , the process (scheme 2) consists in heating acetoacetate acid esters of formula 15, where A2 denotes a single bond or one of the fragments given by formulae 2-10; R2 denotes a Y-(CH2)n-(0)m-(C 2)k-(0) CHJp- or Y-(CH2)n-CH---CH-(CH2)p- group, where Y denotes an H, F, or Cl atom, or a terminal group such as CN, OCF3, CF3, COOCnH2n+1; R3 denotes an alkyl group containing from 1 to 10 carbon atoms, advantageously 2, with the
SUBSTITUTE SHEET compound of formula 16, where R, denotes a Y-fCHj ^CHj fOHCHj ,,- or Y-(CH2)n- CH=CH-(CH2)P- group, where Y denotes an H, F, or Cl atom, or a terminal group such as CN, OCF3, CF3, COOCnHjn.,; A, denotes a single bond or one of the fragments given by formulae 2-10; Z2 denotes a single bond or a CH=CH, C≥C or CH2-CH2 group; and X denotes a pipe- rydyl, pirolidyl, morfonylyl or dialkylamine group, containing from 1 to 15 carbon atoms, advantageously a methyl, ethyl or propyl group. The reaction is carried in organic solvents such as alcohols or ethers in the presence of inorganic base or alkaline metals salts, advan¬ tageously NaOH or KOH, Na2CO3 or K2CO3. Very good results are obtained when inorganic base or alkaline metals salts are combined with organic base such as trialkylamine or 1 ,8-diazobicyclo[5.4.0]undec-7-ene (DBU). The addition of a small amount of tetraamonium salt sometimes results in the increased yield. Thereafter the product of condensation is treated with an aqueous solution of an acid, advantageously sulfuric acid, then it is separated out of the reaction mixtures using known methods, advantageously the extraction.
When s=1 and t=1 the process (scheme 3) consists in heating acetoacetate acid esters of formula 15, with the compound of formula 17 in the same conditions as described above (when s=0). Symbols Z1 t A1 ( Z2, and X in formula 17 have the same meaning as in formula 11 and 16.
The character of both reactions shown in scheme 2 and 3 is the same. The difference between compound 16 and compound 17 is that: compound 16 is a monofunctional compound (contains one group, which is a precursor for vinyl group) and the condensation reaction leads to the creation of a molecule with one cyclohex-2-en-1-one ring as it is shown in scheme 2; compound 17 is bifunctional compound and its use leads to the creation of a molecule contain¬ ing two cyclohex-2-en-1-one rings, as it is shown in scheme 3. The notation used in schemes 2 and 3 are the same as described above.
The formulae from 11.1 to 11.51 represent structures of compounds which can easily be produced by the described method. They were chosen for presentation because of their importance as intermediates for liquid crystalline structures, which are the subject of the invention.
Unsaturated cyclic ketones, which are the subject of the invention as intermediates, often reveal nematic and/or smectic properties. They can be used as the components of liquid crystalline mixtures, especially as dopants for ferroelectric liquid crystal mixtures, but their chemical stability is not high, especially when the cyclohexenone ring is located in such a way that a system of conjugated bonds is created. That is why the unsaturated cyclic ketones of the present invention are more important as intermediates for the synthesis of liquid crystalline compounds of higher chemical and photochemical stability being the subject of the present invention (formula 1) and others descriebed in our concurrent aplication as well as aromatic compounds of formula 12, 13 and 14 as shown in scheme 1.
SUBSTITUTE SHEET The compound of formula 12 (scheme 1) is obtained by treating the compound of formula 11 with the Grignard reagent, then with a diluted acid to form diene, which is heated in high boiling hydrocarbons, advantageously in xylene in the presence of 10% palladium on carbon.
The compound of the formula 13 (scheme 1) is prepared by treating the compound of formula 11 with sodium borohydride in alcohols at room temperature or above, advantageously at 50° C, to obtain a diene, which is heated in the presence of Pd/C in an aromatic-hydrocarbon solvent.
The compound of the formula 14 (scheme 1) is obtained by treating the compound of formula 11 in the presence of palladium on active carbon in an aromatic-hydrocarbon solvent, advantageously in xylene, at temperature 200-220° C.
The above mentioned methods are convenient for the synthesis of laterally substituted terphenyl and quaterphenyl derivatives, the synthesis of which by other methods is a complex and multistage process (LK.M.Chen, Mol.Cryst.Liq.Cryst., 123, 185 (1985)).
3,6-Disubstituted cyclohex-2-en-1-ones are also useful for the preparation of many other classes of compounds, for example derivatives of 2,5-disubstituted cyclohexanones, which are starting materials for the synthesis of liquid crystalline derivatives of cyclohexane or cyclohexene, what was shown in scheme 4. The notation used in scheme 4 is the same as described above, except for Z^ and ZA, which denote a single bond or a CH2CH2, CH2O or OCH2 group.
The present invention will be described in more detail by the following examples. However, these examples do not limit the scope of the present invention.
Example 1
Synthesis of 3,4-difluoro-3'-chloro-4 trans-4-pentylcyclohexylethyl-2)biphenyl
The mixture consisting of 0.1 mol of 3-(3,4-difluorophenyl)-6-(trans-4-pentylcyclohexylethyl- 2)cyclohex-2-one-1, 0.2 mol PCI5, and 100 cm3 benzene was refluxed for 8 hours. Then it was cooled and poured into water. The layers were separated and the organic layer was washed with a solution of K2CO3 until it was neutral, then it was dried over K2CO3 and filtrated. Subse¬ quently, benzene was distilled off and the residue was dissolved in hexane and the obtained solution was filtrated through a silica gel layer, then the solvent was distilled off by an evapo¬ rator. The remaining oily substance was dissolved in ethanol and the solution was cooled to obtain crystals. The yield was 40% and the obtained compound had the following parameters: phase transitions Cr 13 N 45 I, refraction indices at 20°C: n0=1.513, ne=1.620, Δn=0.107;
SUBSTITUTE SHEET viscosity at 40°, 30° and 20°: 48, 76 and 142 mPa-s, respectively, dielectric constants at 20°: ε,=5.4, εx=3.8, Δε=1.6.
In an analogous manner the following compound was obtained:
2-fluoro-4-methoxy-3'-chloro-4'-(trans-4-butylcyclohexylethyl-2)biphenyl which has the following parameters:
Cr 45.2 N 97 I
Δn=0.140, n0=1.517, n,=1.657
Δε=-0.25, ε =4.32, ε,=4.57
Example 2
Synthesis of 4-(trans-4-pentylcyclohexylethyl-2)-3-chloro-4'-(trans-4-propylcyclohexyl)biphenyl
A mixture of 2.9 g (0.005 mol) of 3-(4-(trans-4-propylcyclohexyl)phenyl)-6-(trans-4-pentyl- cyclohexylethyl-2)cyclohex-2-en-1-on, PCI5 (1.3 g, 0.006 mol) and CCI4 (50 cm3) was heated under reflux for 6 hours. The mixture was cooled and poured onto water with ice. The organic layer was separated and washed with a solution of sodium hydroxide, then water, and dried over MgSO4. Carbon tetrachloride was distilled off and the crude product was purified by column chromatography (silica gel, hexane) and then recrystaliized from a hexane: ethanol (2:1) solution. The colorless crystalline solid was obtained. Yield 60.9 % (1.5g); transition temperatures: Cr 81.5 N 220.5 I; mass spectrum: 494 and 492 (M*), 394 and 392, 327 and 325 (C3H7-CβH10-Ph-PhCI-CH2)*, 291, 227 and 225, 205, 165.
In an analogous manner the following compounds were obtained: 4-(trans-4-butylcyclohexylethyl-2)-3-chloro-4' -(trans-4'-propyl- cyclohexylethyl-2)biphenyl Cr 63.3 N 191 I
4-(trans-4-propylcyclohexylethyl-2)-3'-chloro-4"-methoxyteφhenyl Cr 92.6 N 232 I
4-(trans-4-pentylcyclohexyl)-3'-chloro-4"-mθthoxyteφhenyl Cr 90 N 273 I
4-(trans-4-pentylcyclohexyl)-3'-chloro-4"-ethoxyterphenyl Cr 102 N 275 I
4-(trans-4-pentylcyclohexyl)-3'-chloro-4"-fluoroteφhenyl Cr 105 N 210 I
4-pentyl-3,"-chloro-4,",-methoxyquateφhenyl Cr 115 SA 141 N 298 I
SUBSTITUTE SHEET Example 3
Mixture A of the following composition was prepared:
4-(trans-4-propylcyclohexyl)benzeneisothiocyanate 40 % wt
4-(trans-4-hexylcyclohexyl)benzeneisothiocyanate 42 % wt
4-(trans-4-octylcyclohexyl)benzeneisothiocyanate 18 % wt Mixture A was characterized by the following parameters:
TN-I 42°C
V10 20° 1.69V
Vsc/200 1.95V
Figure imgf000009_0001
Δn/20° 0.1680 η/20° 12.9 mPa -s
10% wt of S^-difluoro^'-ttrans^-pentylcyclohexylethyl-ΣJ-S'-chlorobiphenyl was introduced to mixture A to obtain mixture B.
10% wt of 4-(trans-4-pentylcyclohexylethyl-2)-3-chloro-4'-(trans-4-propylcyclohexyl)biphenyl was introduced to mixture A to obtain mixture C.
10% wt of 4-(trans-4-pentylcyclohexyl)-3'-chloro-4"-methoxyteφhenyl was introduced to mixture
A to obtain mixture D.
10% wt of 4-(trans-4-pentylcyclohexyl)-3'-chloro-4"-fluoroteφhenyl was introduced to mixture A to obtain mixture E.
10% wt of 4-pentyl-3'"-chloro-4""-methoxyquateφhenyl was introduced to mixture A to obtain mixture F.
Mixtures B, C, D, E, and F have the following parameters:
B C D E F
' /S 41.5 61.5 61 54 45 η, 20°C 15.2 15.5 16.5 17.9 15.6
Δn, 20°C 0.156 0.176 0.178 0.165 0.182
Δn', 20°C 0.32 0.32 0.12 0.38
Δn - estimated for the single compound
SUBSTITUTE SHEET Example 4
Mixture G of the following composition was prepared :
4-(trans-4-propylcyclohexyl)benzeneisothiocyanate 35.0 % wt
4-(trans-4-pentylcyclohexyl)benzeneisothiocyanate 9.0 % wt
4-(trans-4-heptylcyclohexyl)benzeneisothiocyanate 16.0 % wt
4-methoxyphenyl-4-trans~pentylcyclohexanecarboxylate 10.0 % wt
4-(trans-4-ethylcyclohexyl)nonylbenzene 5.0 % wt
1-(4-(trans-4-ethylcyclohexyl)phenyl)-2-(trans-4-propylcyclohexyl)ethane 25.0 % wt
It has the following parameters: TN, 42°C η/20° 14.5mPa -s
Δn/20° 0.1408
10 % wt of 4-(trans-4-pentylcyclohexylethyl-2)-3-chloro-4'-(trans-4-propylcyclohexyl)biphenyl was added to mixture G to obtain mixture H which has the following parameters: TN, 72°C η/20° 17.8 mPa*s
Δn/20° 0.1445
Example 5
3-(4-ethoxystyryl)-6-pentylcyclohex-2-en-1-one
A mixture composed of hydrochloride of 2-(dimethylamino)ethyl 4-ethoxystyryl ketone (0.1 mol), ethyl 2-pentylacetoacetate (0.11 mol), sodium isopropylate (0.12 mol) i 200 ml anhydrous isopropanol was refluxed for 6 hours. Thereafter the mixture was cooled and acidified with 20% solution of H2SO4. The oily substance from the mixture was extracted with diethyl ether. The extract was washed with water, dried over anhydrous Na2SO4 and filtrated. The residue obtained after the evaporation of the solvent was purified by crystallization from isopropanol, yield of 14.4 g (45 %) of 3-(4-ethoxystyryl)-6-pentylcyclohex-2-en-1-one having the following phase transition temperatures: Cr 98.5-99.3 SA 120.4-126.3 I was obtained. When KOH in the same mole ratio was used instead of sodium isopropylate the yield of the compound increased to 63%.
Using alkaline medium such as NaOH or KOH the following compounds were prepared.
SUBSTITUTE SHEET Table 1
Figure imgf000011_0001
Example 6
3-(3,4-difluorophenyl)-6-(trans-4-pentylcyclohexylethyl-2)cyclohex-2-en-1-one
A mixture composed of hydrochloride of β-(dimethylamino)ethyl-3,4-difluoropropiophenone (0.1 mol), ethyl 2-(trans-4-pentylcyclohexylethyl-2)acetoacetate (0.11 mol), sodium isopropylate (0.12 mol) and 150 ml of anhydrous isopropanol was refluxed for 6 hours. Thereafter the mixture was cooled and acidified with 20% solution of H2SO4. The oily substance from the mixture was extracted with diethyl ether. The extract was washed with water, dried over anhydrous Na2S04 and filtrated. The residue obtained after the evaporation of the solvent was purified by crystal¬ lization from isopropanol, where upon 20 g (52 %) 3-(3,4-difluorophenyl)-6-(trans-4-pentylcyclo- hexylethyl-2)cyclohex-2-en-1-one having the following phase transition temperatures: Cr 95.0-96.6 (N 84) I was obtained.
When 0.1 mol of KOH and 0.2 mol of DBU was used instead of sodium isopropylate the yield of the compound increased to 70%.
In an analogues way the following compounds were obtained:
3-(4-(trans-4-propylcyclohexyl)phenyl)-6-(trans-4-pentylcyclohexylethyl-2)cyclohex-2-en-1-one, Cr <20 SB 175 SA 248 l;
3-(4-(trans-4-propylcyclohexyl)phenyl)-6-(trans-4-butylcyclohexylethyl-2)cyclohex-2-en-1-one, Cr <20 SB 174 SA 243 N 252 l; 3-(4-pentylbiphenyl-4'-yl)-6-(2-cyanoethyl)cyclohex-2-en-1-one, Cr 92.0 N 159 I;
SUBSTITUTE SHEET 3-(4-(trans-4-propyicyclohexylethyl-2)phenyl)-6-(trans-4-butylcyclohexylethyl-2)cyclohex-2-en-1- one, Cr <20 Sθ 161 SA 222 I;
3-(4-(trans-4-butylcyclohexylethyl-2)phenyl)-6-(trans-4-butylcyclohexylethyl-2)cyclohex-2-en-1- one, Cr 71 SB 187 SA 226 I.
Example 7
3-(4-(trans-4-propylcyclohexyl)phenyl)-6-pentylcyclohex-2-en-1-one
A mixture composed of hydrochloride of 2-(dimethylamino)ethyl 4-(trans-4-propylcyclohexyl)- phenyl ketone (0.1 mol), ethyl 2-pentylacetoacetate (0.12 mol), potassium hydroxide (0.12 mol) and 150 ml of dioxane was refluxed for 8 hours. Thereafter the mixture was cooled, acidified with 20% solution of H2SO4. The oily substance from the mixture was extracted with diethyl ether. The extract was washed with water, dried over anhydrous Na2SO4 and filtrated. The residue obtained after the evaporation of the solvent was purified by crystallization from isopro¬ panol, and.27.5 g (75 %) of 3-(4-(trans-4-propylcyclohexyl)phenyl)-6-pentylcyclohex-2-en-1-one having the following phase transition temperatures: Cr 77 SA 149 N 157 I was obtained.
The compounds shown in Table 2 were obtained in an analogues way.
Table 2
Figure imgf000012_0001
SUBSTITUTE SHEET 103-(4-butoxyphenyl)-6-methylcyclohex-2-en-1-one 71 *
11 3-(4-butoxyphenyl)-6-propylcyclohex-2-en-1-one * 67 * 97 * 12 3-(4-butoxyphenyl)-6-butylcyclohex-2-en-1-one » 67 * 96 *
13 3-(4-butoxyphenyl)-6-pentylcyclohex-2-en-1-one * 41 * 109 *
14 3-(4-pentoxyphenyl)-6-propylcyclohex-2-en-1-one * 55 * 96 *
15 3-(4-pentoxyphenyl)-6-pentylcyclohex-2-en-1-one » 53 * 110 *
16 3-(4-hexyloxyphenyl)-6-pentylcyclohex-2-en-1-one * 56 * 109 * 17 3-(4-nonyloxyphenyl)-6-pentylcyclohex-2-en-1-one * 59 * 109 * 18 3-(4-decyloxyphenyl)-6-pentylcyclohex-2-en-1-one 60 * 113 *
19 3-(4-hexyloxyphenyl)-6-butylcyclohex-2-en-1-one 75 20 3-(4-hexylphenyl)-6-pentylcyclohex-2-en-1-one r 90 21 3-(4-trifluoromethoxyphenyl)-6-pentylcyclohex-2-en-1-one 31 22 3-(biphenyl-4-yl)-6-propylcyclohex-2-en-1-one * 119 * (104) 23 3-(biphenyl-4-yl)-6-butylcyclohex-2-en-1-one I* 110 * 116' 24 3-(biphenyl-4-yl)-6-pentylcyclohex-2-en-1-one 101 * 120' 25 3-(4'-fluorobiphenyl-4-yl)-6-pentylcyclohex-2-en-1-one r 89 114 * 141
26 3-(4'-bromobiphenyl-4-yl)-6-pentylcyclohex-2-en-1-one 91 114 * 219* 27 3-(4'-methylbiphenyl-4-yl)-6-pentylcyclohex-2-en-1-one 117 * 179* 28 3-(4'-ethylbiphenyl-4-yl)-6-pentylcyclohex-2-en-1-one 83 * 171 29 3-(4'-ethylbiphenyl-4-yl)-6-hexylcyclohex-2-en-1-one 94 * 191
30 3-(4'-pentylbiphenyl-4-yl)-6-ethylcyclohex-2-en-1-one r 93 157 31 3-(4-(4-phenylethyl-2)phenyl)-6-pentylcyclohex-2-en-1-one 66 * (54)
32 3-(4-ethoxyphenyl)-6-allilcyclohex-2-en-1-one 71 33 3-(4-(trans-4-butylcyclohexyl)phenyl)-6-(4-hexyl- 126 * 150 phenyl)cyclohexen-2-en-1-one
SUBSTITUTE SHEET
Figure imgf000014_0001
SUBSTITUTE SHEET

Claims

Claims
1. Laterally substituted chloroarenes of the general formula 1 , in which R1 and R2 are the same or different and denote Y-tCH^O CHj HCHj)-- or Y-(CH2)n-CH=CH-(CH2)p-, where Y is an H, F or Cl atom, or CN, OCF3, CF3, or COOCnH2n , n, p and k are integers from 0 to 7, m and I denote 0 or 1; s and t denote independently 0 or 1 with the condition that s+t≥1; Z, and Z2 are the same or different and denote a CH=CH, C≡C or CH2-CH2 group and also a single bond when s and t is not equal to 0; A1 and A2 denote independently a single bond or one of the fragments represented by the formulae 2-10, where X1 f X2, X3 and X4 are independent and denote an H or F atom; B and B, denote independently a single bond or a bridge group such as CH2CH2, C≡C, CH=CH, OCH2, CH2O.
2. The method for synthesis of laterally substituted chloro arenes of general formula 1 , in which R, and R2 are the same or different and denote Y-(CH2)n-(O)m-(CH2)k-(O)r(CH2)p- or Y-(CH2)n-CH=CH-(CH2)p-, where Y is an H, F, Cl atom, or CN, OCF3, CF3, or COOC-^,, n, p and k are integers from 0 to 7, m and I denote 0 or 1 ; s and t denote independently 0 or 1 with the condition that s+t≥1; Z1 and 2 are the same or different and denote a CH=CH, C≡C or CH2-CH2 group and also a single bond when s and t is not equal to 0; A1 and A2 denote independently a single bond or one of the fragments represented by the formulae 2-10, where X1 t X2, X3 and X4 are independent and denote an H or F atom; B and B1 denote independently single bond or bridge group such as CH2CH2, C≡C, CH=CH, OCH2, CH2O which consist in heating, advantageously at temperature above 50°C, the compounds of general formula 11 (scheme 1), where the symbols are the same as in the case of formula 1 , in the excess of PCI5 in hydrocarbon or chlorohydrocarbon solvent.
3. A liquid crystalline mixtures containing at least two compounds and at least one of them is a compound of the formula 1 , in which R, and R2 are the same or different and denote Y-(CH2)n-(O)m-(CH2)k-(0),-(CH2)p- or
Figure imgf000015_0001
where Y is an H, F, Cl atom, or CN, OCF3, CF3, or COOCnH2n+1, n, p and k are integers from 0 to 7, m and I denote 0 or 1; s and t denote independently 0 or 1 with the condition that s+t≥1 ; Z1 and Z are the same or different and denote a CH=CH, C≡C or CH2-CH2 group and also a single bond when s and t is not equal to 0; A, and A2 denote independently a single bond or one of the fragments repre¬ sented by the formulae 2-10, where X,, X2, X3 and X4 are independent and denote an H or F atom; B and B, denote independently single bond or bridge group such as CH2CH2, C≡C, CH=CH, OCH2, CH2O.
4. A liquid crystalline display composed of two plane parallel support plates, at least one of
SUBSTITUTE SHEET them is transparent, on which there are electrodes, orienting layers and/or isolating layers, and/or color filters between which liquid crystalline medium is placed, characterized by the fact that the said medium is a liquid crystalline mixtures containing at least two compounds and at least one of them is a compound of the fomiula 1, in which R, and R2 are the same or different and denote Y-(CH2)n-(O)m-(CH2)k-(O)l-(CH2)p- or Y-(CH2)n-CH=CH-(CH2)p-, where Y is an H, F, Cl atom, or CN, OCF3, CF3, or COOC„H2n l, n, p and k are integers from 0 to 7, m and I denote 0 or 1; s and t denote independently 0 or 1 with the condition that s+t≥1 ; Z, and Z2 are the same or different and denote a CH=CH, C≡C or CH2-CH2 group and also a single bond when s and t is not equal to 0; A, and A2 denote independently a single bond or one of the fragments represented by the formulae 2-10, where X,, X2, X3 and X4 are independent and denote an H or F atom; B and B, denote independently single bond or bridge group such as CH2CH2, C≡C, CH=CH, OCH2, CH20.
5. The intremediates for obtaining laterally substituted chloroarenes of the general formula 1 being compounds of formula 11 , where s and t denotes an integer 1 or 0 with the condition that s+t>1 , R, and R2 are the same, when s=t, and the same or different when s≠t, and denote a Y-(CH2)n-(O)m-(CH2)k-(O),-(CH2)p- or
Figure imgf000016_0001
group, where Y denotes an H, F, or Cl atom, or a CN, OCF3, CF3, or COOC.H^, group, n, p and k are integers from the range of 0+7, m and I denote 0 or 1; Z1 and Z2 are the same or different and denote a CH=CH or C≡C group; when s+t>1 Z, denotes also a single bond or a CH2-CH2 group ; A1 and A2 denote independently a single bond or one of the fragments given by formulae 2-10, where X,, X2, X3 and X4 denote independently an H, or F atom; and B and B, denote independently a single bond or a bridge group such as CH2CH2, C≡C, CH=CH, OCH2, CH20.
6 The method for synthesis of intermediates of the general formula 11 , where R, and R2 are the same or different and denote a terminal group:
Figure imgf000016_0002
or Y-(CH2)n-CH=CH-(CH2)p-, where Y denotes an H, F, or Cl atom, or a terminal group such as -CN, -OCF3, -CF3, -COOCnH2n+1, n, p and k are from the range of 0+7, m and I denotes 0 or 1 ; Z, and Z2 are the same or different and denote a single bond, CH=CH, C≡C or CH2-CH2 group; A1 and A2 denote independently a single bond or one of the fragments given by formulae 2-10, where X,, X2, X3 and X4 denote independently an H or F atom; B and B, denote independently a single bond or a bridge group such as CH2CH2, C≡C, CH=CH, OCH2, CH2O; s=0 and t=1, the process (scheme 2) consists in heating, in an organic solvent such as alcohol or ether in the presence of inorganic base or alkaline metals salts, advantageously NaOH or KOH, Na2CO3 or K2CO3, acetoacetate acid esters of formula 15, where A2 denotes a single bond or one of the fragments given by formulae 2-10; R2 denotes a Y-(CH2)n-(O)m-
SUBSTITUTE SHEET (CH2)k-(0)r(CH2)p- or Y-(CH2)n-CH=CH-(CH2)p- group, where Y denotes an H, F, or Cl atom, or a terminal group such as CN, OCF3, CF3, COOCnH2r ; R3 denotes an alkyl group containing from 1 to 10 carbon atoms, advantageously 2, with the compound of formula 16, where R, denotes a Y-(CH2)n-(0)m-(CH2)k-(0)r(CH2)p- or Y-(CH2)„-CH=CH-(CH2)P- group, where Y denotes an H, F, or Cl atom, or a terminal group such as CN, OCF3, CF3, COOC.H^,; A, denotes a single bond or one of the fragments given by formulae 2-10; Z2 denotes a single bond or a CH=CH, C≡C or CH2-CH2 group; and X denotes a piperydyl, pirolidyl, morfonylyl or dialkylamine group, containing from 1 to 15 carbon atoms, advanta¬ geously a methyl, ethyl or propyl group followed by treating the product of condensation with an aqueous solution of an acid, advantageously sulfuric acid and separating out the product from the reaction mixtures using known methods, advantageously the extraction.
7. The method for synthesis of intermediates of the general formula 11 , where R, and R2 are the same and denote a terminal group: Y-(CH2)n-(O)m-(CH2)k-(O),-(CH2)p- or Y-(CH2)n-CH=CH- (CH2)p-, where Y denotes an H, F, or Cl atom, or a terminal group such as CN, OCF3, CF3, COOCnH2n 1, n, p and k are from the range of 0+7, m and I denotes 0 or 1 ; Z and Z2 are the same or different and denote a single bond, CH=CH, C≡C or CH2-CH2 group; A, and A2 denote independently a single bond or one of the fragments given by formulae 2-10, where X,, X2, X3 and X4 denote independently an H or F atom; B and B, denote independently a single bond or a bridge group such as CH2CH2, C≡C, CH=CH, OCH2, CH2O; s=1 and t=1 , the process (scheme 3) consists in heating, in an organic solvent such as alcohol or ether in the presence of inorganic base or alkaline metals salts, advantageously NaOH or KOH, Na2CO3 or K2C03, acetoacetate acid esters of formula 15, where A2 denotes a single bond or one of the fragments given by formulae 2-10; R2 denotes a Y-fCH^.- OJn CH^OMCH;,)-,- or Y-(CH2)n-CH=CH-(CH2)p- group, where Y denotes an H, F, or Cl atom, or a terminal group such as CN, OCF3, CF3, COOCnH2n+1; R3 denotes an alkyl group containing from 1 to 10 carbon atoms, advantageously 2, with the compound of formula 17, where A, denotes a single bond or one of the fragments given by formulae 2-10; Z, and Z2 are the same or different and denote a single bond or a CH=CH, C≡C or CH2-CH2 group; and X denotes a piperydyl, pirolidyl, morfonylyl or dialkylamine group, containing from 1 to 15 carbon atoms, advantageously a methyl, ethyl or propyl group followed by treating the product of conden¬ sation with an aqueous solution of an acid, advantageously sulfuric acid and separating out the product from the reaction mixtures using known methods, advantageously the extraction.
SUBSTITUTE SHEET
PCT/PL1995/000017 1994-08-18 1995-08-18 Laterally substituted chloroarenes, their manufacture and mixtures containing them WO1996006061A2 (en)

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