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GB2280181A - Preparation of diarylene compounds - Google Patents

Preparation of diarylene compounds Download PDF

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Publication number
GB2280181A
GB2280181A GB9314237A GB9314237A GB2280181A GB 2280181 A GB2280181 A GB 2280181A GB 9314237 A GB9314237 A GB 9314237A GB 9314237 A GB9314237 A GB 9314237A GB 2280181 A GB2280181 A GB 2280181A
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Prior art keywords
diyl
alkyl
group
alkenyl
chlorine
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GB9314237D0 (en
Inventor
Richard Buchecker
Guy Marck
Alois Villiger
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F Hoffmann La Roche AG
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F Hoffmann La Roche AG
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Priority to CH821/92A priority Critical patent/CH683522A5/en
Priority to DE4307243A priority patent/DE4307243A1/en
Priority to JP5076440A priority patent/JPH06219971A/en
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Priority to GB9314237A priority patent/GB2280181A/en
Publication of GB9314237D0 publication Critical patent/GB9314237D0/en
Publication of GB2280181A publication Critical patent/GB2280181A/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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/04—Substitution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/05—Cyclic compounds having at least one ring containing boron but no carbon in the ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Pyridine Compounds (AREA)

Description

1 2280181 The present invention is concerned with a novel process for the
manufacture of diaryl derivatives.
Processes for the direct coupling of arylenes containing a suitable leaving group with organoboron compounds and with aromatic boronic acids or aromatic boronic acid derivatives are known. For example, such metalcatalyzed couplings with organic boron compounds are described in EP 354 434. Pall'adium-catalyzed couplings of aromatic boronic acids with corresponding aryl halides have also been described (Synth. Comm. (1981) JLL 513). Common to the previously known couplings is the fact that the metal catalyst was always present in the form of a metal complex or was used at least in the presence of ligands.
It has now surprisingly been found that the palladium-catalyzed coupling of aryl or heteroaryl halides or of aryl or heteroaryl fluoroalkylsulphonates with aromatic boronic acids or with their derivatives proceeds successfully in the presence of bases without any addition of ligands, i.e. that palladium on a carrier material - e.g. in the form of a hydrogenation catalyst - can be used for the coupling. In this manner there is provided an extraordinarily simple method for the manufacture of diarylenes, especially for the manufacture of intermediates for the synthesis of liquid crystalline compounds and for the manufacture of liquid crystalline compounds themselves.
The object of the present invention is accordingly a novel process for the manufacture of diarylenes by coupling an aryl or heteroaryl halide or an aryl. or heteroaryl fluoroalkylsulphonate with an aromatic boronic acid or with an aromatic boronic acid derivative in the presence of a base. This process comprises carrying out the coupling in the presence of palladium on a carrier material.
Although the process in accordance with the invention can be used generally for the synthesis of diaryl derivatives, it is especially of interest for the manufacture of diarylenes of the general formula 2 xl R' A R2 (2 I This is effected in accordance with the invention by coupling an aryl or heteroaryl halide or an aryl or heteroaryl fluoroalkylsulphonate of the general formula R' -&Z II with an aromatic boronic acid, its anhydride or an aromatic boronic acid derivative of the general formula xl R30 1% B - R2 III or d -C"' - R4d \ i J 1 X2 E B-R "B-E B-d E in the presence of a base and in the presence of palladium on a carrier material.
The symbols in formulae I - III and III-1 have the following significances:
R13, R2: independently of one another hydrogen, straight-chain or branched (optionally chiral) alkyl or alkenyl with 1 to 12 carbon atoms, in which optionally one or more methylene groups can be replaced by -0-, - COO-, -OOC-, -CO-, -CHYand/or -CY2-; or alkynyl, halogen, cyano, -OH, -Q- CHO, -Q-CH(OR5XOR6), or a group a group izi Z2 M -R7 IVY izi -Z2-C)=D n V or 3 a group Y: ring A:
Z: R3, R4:
E:
Q: R5, R6:
p: Z1, Z2:
OR5 U z _Z2-CKOR6 VI fluorine, chlorine, -CN, methyl or -CF3; 1,4-phenylene, which is unsubstituted or mono- or multiplysubstituted, pyridine-2,5-diyl, pdine-2, 5-diyl, pyrazine3,5-diyI, pyridazine-3,6-diyl, naphthalene-2,6-diyl, tetralin2,6-diyI, thiophene-2,5-diyl, 1,3,4-oxadiazole-2,5-diyl, 1,3, 4thiodiazole-2,5-diyl; Xl, X2: independently of one another hydrogen, fluorine, chlorine, -CN, -N02. -NH2 or lower alkyl; a leaving group; hydrogen or lower alkyl; X1 -(,-R2 I X2 a single bond or an alkylene group; lower alkyl or R5 and R6 together an alkylenediyl group of the formula -(CH2)p-; the number 2 or 3; independently of one another a single bond, -CI-12-CH2-COO-, -OOC-, -CH2-0-, -0-CH2-, -CH=CH-, -C-=C-, -(CH2)4-P -(CH2)30-p -O(CH2)3-, the trans form of -CH=CH-(CH2)2-, (CH2)2-CH=CH-, -0-CH2-CH=CH- or -CH=CH-CH20; rings B, C: independently of one another 1,4-phenylene, which is unsubstituted or mono- or multiply-substituted, pyridine2,5-diyl, pyfimidine-2,5-diyl, pyrazine-3,5-diyl, pyridazine3,6-diyl, naphthalene-2, 6-diyl, tetralin-2,6-diyl, thiophene2,5-diyl, 1,3,4-oxadiazole-2,5-diyl, 1,3,4-thiodiazole-2,5-diyl; trans-1,4-cyclohexylene, trans-1,3-dioxane-2, 5-diyl, trans1,3-dithiane-2,5-diyl, trans-decalin-2,6-diyl or bicyclo[2,2, 2]octane-1,4-diyI; independently of one another a number 0 or 1; straightchain or branched (optionally chiral) alkyl or alkenyl with 1 to 12 carbon atoms, in which optionally one or more methylene groups can be replaced by -0-, -COO-, -OOC-, -CO-, -CHY- and/or -CY2-; or alkenyl, -Q- CHO or -Q-CH(OR5)(OR6); and oxygen, CHOCH3, CHQ-CHO or CHQ-CH(OR5)(OR6).
n,m: R7:
D:
4 In the scope of the pregent invention palladium signifies metallic palladium on a carrier material or a palladium salt on a carrier material.
Malogen" signifies in connection with R1 and R2 fluorine, chlorine or bromine.
-CF3.
The term "1,4-phenylene, which is unsubstituted or mono- or multiplysubstituted" signifies' in the scope of the present invention 1, 4phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2, 6difluoro-1,4-phenylene, 2-chloro-1,4-phenylene, 2,3-dichloro-1, 4phenylene, 2,6-dichloro-1,4-phenylene, 2-cyano-1,4-phenylene, 2,3dicyano1,4-phenylene, 2-bromo-1,4-phenylene, 2-methyl-1,4-phenylene and the like. 1,4-Phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4phenylene or 2,6difluoro-1,4-phenylene is especially preferred.
The term "straight-chain or branched (optionally chiral) alkyl or alkenyl with 1 to 12 carbon atoms, in which optionally one or more methylene groups can be replaced by -0-, -COO-, -OOC-, -CO-, -CHYand/or -CY2-" embraces in the scope of the present invention groups such as, for example, alkyl, alkoxy, alkoxyalkyl, fluoroalkyl, fluoroalkoxy, alkanoyloxy, alkoxycarbonyl, alkanoyl, alkanoylalkyl and the like as well as, for example, (C2-C12)-1-alkenyI, M3-C10-2-alkenyl, M4-C10-3-alkenyl, (C5-C12)-4-alkenYI or (C3-C12)-alkenyl having a terminal double bond, W3C10-2-alkenyloxy, M4-C10-3-alkenyloxy, alkenyloxy having a terminal double bond, alkenyloxyalkyl, alkoxyalkenyl and the like.
Y signifies in this connection fluorine, chlorine, -CN, methyl or Examples of preferred alkyl residues are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, 2-butyl, 2- pentyl, 2-hexyl, 2-heptyl, 2-octyl, 2-nonyl, 2-decyl, 2-undecyl, 2- dodecyl, isopropyl, isobutyl, tert. butyl, 2-methyl-pentyl, 2-methyl- hexyl, 2-methylheptyl, 2-methyl-octyl, 2-methyl-nonyl, 2-methyl-decyl, 2- methylundecyl, 3-methyl-pentyl, 3-methyl-hexyl, 3-methyl-heptyl, 3-methyloctyl, 3-methyl-nonyl, 3-methyl-decyl, 3-methyl-undecyl and the like.
Examples of preferred alkoxy residues are methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, 2-butyloxy, 2-pentyloxy, 2-hexyloxy, 2heptyloxy, 2-octyloxy, 2-nonyloxy, 2-decyloxy, 2-undecyloxy, 2-dodecyloxy, 2methylbutyloxy, 4-methylhexyloxy, 5-methylheptyloxy, 6methy1heptyloxy and the like.
Examples of alkyloxyalkyl residues are methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, propyloxymethyl, propyloxyethyl, propyloxypropyl, propyloxybutyl and the like.
Examples of preferred fluoroalkyl residues are difluoromethyl, trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perflucrohexyl, 2-fluorohexyl, 3-fluoropropyl, 5fluoropentyl and the like.
Examples of preferred fluoroalkoxy residues are difluoromethoxy, trifluoromethoxy, perfluoroethoxy, perfluoropropyloxy, 2-fluorohexyloxy, 2-fluoroheptyloxy, 2-fluorooctyloxy, 2-fluorohexanoyloxy, 2fluoroheptanoyloxy and the like.
Examples of preferred alkanoyloxy residues are acetyl, propanoyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy and the like.
Examples of preferred alkoxycarbonyl residues are methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl, butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl and the Eke.
Examples of preferred alkenyl residues are vinyl, 1E-propenyl, IEbutenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 1E-octenyl, allyl, 2- 6 butenyl, 2-pentenyl, 2-hexenyl, 2-heptenyl, 2-octenyl, 3-butenyl, 3Epentenyl, 3E-hexenyl, 3E-heptenyl, 3E-octenyl, 4-pentenyl, 4Z-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl, 7-octenyl and the like.
Examples of preferred W3-C12)-2-alkenyloxy, (C4-CIO-3-alkenyloxy and alkenyloxy residues having a terminal double bond are allyloxy, 2Ebutenyloxy, 2E-pentenyloxy, 2E-hexenyloxy, 2E-heptenyloxy, 3butenyloxy, V-pentenyloxy, 3Z-hexenyloxy, 3Z-heptenyloxy, 4pentenyloxy, 5-hexenyloxy, 6-heptenyloxy, allyloxymethyl and the like.
E and Z in each case indicate the configuration of the double bond.
The term "alkynyl" signifies in the scope of the present invention branched and straight-chain, preferably straight-chain, alkynyl residues with 2-12 carbon atoms in which the triple bond is situated in the Iposition or in the 3-position. Examples of such preferred residues are ethynyl, 1-propynyl, 1-butynyl, 1-pentynyl and the like.
The term 1eaving group" signifies in the scope of the present invention halogen such as, for example, chlorine, bromine or iodine or a fluoroalkylsulphonate group of the formula -OSO2CqF2q+1. wherein q is a whole number 1 to 4, such as, for example, trifluoromethylsulphonate and the like.
The term 1ower alkyl" signifies in the scope of the present invention straight-chain alkyl groups with 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl, but especially methyl and ethyl.
The term "alkylene" signifies in the scope of the present invention methylene, ethane-1,2-diyl, propane-1,3-diyl or butane-1,4-diyl.
The process in accordance with the invention provides a costeflective and synthetically problem-free access to liquid crystalline compounds and primarily also to a wide range of intermediates for the synthesis of liquid crystalline compounds.
This process is of particular interest for the manufacture of intermediates and compounds of the general formula xl Re- cx 1= / 1 / R9 1 1 X3 X2 The symbols in general formula I-a have the following significances:
R8:
Pa, bromine, chlorine, straight-chain or branched (optionally chiral) alkyl or alkenyl with 1 to 12 carbon atoms, in which optionally one or more methylene groups can be replaced by -0-, -COO-, -OOC-, -CO-, -CHYand/or -CY2-; or -Q-CHO, -Q-CH(OR5)(OR6), or group R7_---&Z1- VII, group D==0-Z2- VIII or group R50 ' R6 01Z2- IX Xl, X2, X3: independently of one another hydrogen, fluorine, chlorine or methyl; R9: alkyl, alkoxy, difluoromethoxy, trifluoromethyl, trifluoromethoxy, fluorine, chlorine or -CN; Q a single bond or -CH2-CH2-; Z1, Z2: a single bond, -CH2-CH2-, -COO-, -OOC-, -CH2-0-, -0-CH2-9 -CH=CH- or -C=-C--, ring B: 1,4-phenylene, which is unsubstituted or mono- or multiplysubstituted, pyridine-2,5-diyl, pyrimidine-2,5-diyl, trans-1,4- cyclohexylene or trans-1,3-dioxane-2,5-diyl.
Y, R5, R6, R7 and D: the significances given above.
In an especially preferred embodiment, the process in accordance with the invention is used for the synthesis of intermediates and compounds of the following general formulae 8 xl R10-01---C\ -R9 2 xl R's -O-Zl- C\ R9 2 xl D-O-Z2 -0- - - R9 X2 xl RSOU - - R6 O>D-Z2-- R9 2 The symbols in formulae I-b to Pe have the following significances:
I-b PC I-d Pe.
chlorine, bromine, straight-chain or branched (optionally chiral) alkyl or alkenyl with 1 to 12 carbon atoms, in which optionally one or more methylene groups can be replaced by -0-, -COO-, -OOC-, -CO-, -CHY- and/or -CY2-; or -Q-CHO or -Q-dioxolane; R15: alkyl, alkenyl, -Q-CHO or -Q-dioxolane; Z1, Z2, Q: independently of one another a single bond or -CH2-CH2-; Xly X2: hydrogen or fluorine; D: oxygen, CHOCH3) CHQ-CHO or CHQ-dioxolane; and R9, Y: the definition given above.
Examples of such especially preferred intermediates for the synthesis of liquid crystalline compounds, which can be manufactured by the process in accordance with the invention, are set forth hereinafter:
9 Xl OHC-0-, -C xl CH30---'/ xl 1 W' 0HC-/ xl co - Rll 0/-CY xl 0 Rll co W-O-C - xl 0HC-0-Z1-C)-O-Rll Xl C CH3-0 xl OHC--/"--ZI -C)-O-Rll Xl Z1 W' co J-0- -C)-0- xl 0 Z1-0-0-Rll cc Xl 0 Z2 -0-C Rll C - 0 P1 1-2 P3 1-4 1-5 P6 1-7 P8 1-9 I-10 I-11 The symbols in formulae I-1 to I-11 have the following significances:
xl:
R11:
Z1, Z2:
hydrogen or fluorine; fluorine, chlorine, -CN, alkyl, alkoxy, difluoromethoxy, trifluoromethyl or trifluormethoxy; the significances given above.
Examples of such especially preferred liquid crystalline compounds which can be manufactured by the process in accordance with the invention are set forth hereinafter:
xl R12-0-0-F xl R12 -0-0-Cl xl R12 M xl R12-0-6-RI3 xl R12-0-Z1-C)-O-F xl R12 -O-Z1-, cl xl R12 -O-ZI- CN xl R12 -0-Z1 --0-0-R13 significances:
1-12 1-13 1-14 1-15 1-16 1-17 1-18 1-19 The symbols in formulae 1-12 to 1-19 have the following xl PZ1:
R12: R13:
the definition given above; alkyl, alkenyl or alkoxyalkyl; and alkyl, alkoxy, difluoromethoxy, trifluoromethyl or trifluoromethoxy.
For the coupling there are preferably used starting materials of formula II which -carry as R1 either a further fimctional group such as, for example, halogen, -OH, -Q-CHO, -Q-CH(OR5)(OR6) or a group of formula V or VI which is suitable for the synthesis of intermediates for liquid crystalline compounds or which already carry a side chain which is usual in the field of liquid crystal chemistry.
Especially preferred starting materials are those of the formula _z 11 X (3 c II-a wherein R8 and X3 have the significances given above and Z signifies chlorine, bromine, iodine or trffluoromethylsulphonate, but especially bromine, iodine or trifluoromethylsulphonate.
The aforementioned starting materials of formula II and especially of formula II-a are coupled with aromatic boronic acids of formula Ha, their anhydrides, for example of formula II1Pb, or aromatic boronic acid esters of formula III-c:
xl HO... B-10-Rg Hd X2 E1 \ B-0 1 % 0 B-El % 1 B-0 E1 III-a III-b 12 xl R3C -- C\ -R9 WC( )(2 III-C wherein Xl, X2, R3, R4 and R9 have the significances given above c xl and E l signifies a group -q2 R9 In an especially preferred embodiment the boronic acids of formula III-a are used for the coupling in accordance with the invention.
As mentioned hereinbefore, the coupling in accordance with the invention for the manufacture of diarylenes is carried out in the presence of palladium on a carrier material.
As carrier materials there come into consideration carriers which are usual for hydrogenation catalysts such as, for example, charcoal, aluminium oxide, calcium carbonate, strontium carbonate and the like.
As palladium catalysts there can be used not only metallic palladium, but also non-reduced Pd compounds, for example Pd(II) salts such as Pd(II) chloride or Pd(H) acetate and the like. Palladiumon-charcoal is preferably used as the catalyst, for example in the form of a hydrogenation catalyst.
The amount of catalyst used usually amounts to about 0.1 mol equivalent, preferably up to about 0.04 mol equivalent, but especially up to about 0. 01 mol equivalent, with respect to the amount of educt of formula II which is used.
The coupling is carried out in the presence of a base. To this end, there are suitable for such couplings usual inorganic or organic bases, such as alkali metal carbonates or alkali metal hydrogen carbonates such as, for example, sodium carbonate, sodium hydrogen carbonate, 13 lithium carbonate and the like or lower alkylamines such as e.g. diisopropylamine, triethylamine and the like. The alkali carbonates can be used in aqueous solution or in solid form. The amount of base which is used is not critica:4 but it must be at least 1 equivalent with respect to the boronic acid or the corresponding boronic acid derivative.
The reaction can be carried out in various solvents which are inert under the reaction conditions. As solvents there come into consideration lower alcohols such as, for example, methanol, ethanol or propanol; ethers such as, for example, dimethoxyethane, tetrahydrofuran, diglyme or triglyme and the like; amides such as, for example, dimethy1formamide or Nmethylpyrrolidone and the like; aromatic hydrocarbons such as, for example, benzene, toluene or Xylene, and the like. Solvent mixtures such as, for example, alcohol/water, aromatic hydrocarbon/water, ether/ water, amide/water, amidelalcohol and the like are also suitable.
Dimethoxyethane, ethanol, dimethoxyformamide, dimethoxyethane/water or toluene/water are especially preferred, particularly ethanol or dimethoxyethane/water.
The pressure and the temperature in the process in accordance with the invention have no critical limits. The reaction can be carried out at normal pressure and at temperatures of 500C to 1500C. The reaction is preferably carried out at the reflux temperature.
The process in accordance with the invention provides a simple and costeffective access to liquid crystalline diarylenes or to intermediates which lead to such liquid crystalline diarylenes. This process is especially interesting in that known palladium hydrogenation catalysts which are readily obtainable commercially can be used in place of the expensive catalysts mentioned hereinbefore.
The following Examples illustrate, but do not limit, the invention.
14 ExamDle 1 A mixture of 370 mg (2 mmol) of p-bromobenzaldehyde, 308 mg (2.2 mmol) of p-fluorophenylboronic acid, 43 mg of 5% palladium-oncharcoal (DEGUSSA E 101NAD), 10 mI of benzene, 5 ml of ethanol and 10 mI of 2M sodium carbonate solution was heated to boiling for 3 hours, the catalyst was filtered off and the aqueous phase was separated. The organic phase was washed with 1N sodium hydroxide solution, saturated sodium hydrogen carbonate solution and water, dried over sodium sulphate, filtered and concentrated. The resulting, colourless, solid crude product (373 mg, 93. 2% of theory) contained according to gas chromatography 95.1% of 4'fiuoro-4-biphenylcarboxaldehyde and 3.1% of p-brornobenzaldehyde; this was used for the synthesis of a liquid crystalline 1,3-dioxane without further purification.
ExamDle 2 A mixture of 185 mg of p-bromobenzaldehyde, 154 mg of pfluorophenylboronic acid, 21.5 mg of 5% palladium-on-charcoal (DEGUSSA E 101 N/D), 18 mI of ethanol, 2 ml of water and 0.5 mI of triethylamine was heated to boiling for 5 hours, the catalyst was filtered off and the filtrate was concentrated. The residue was taken up in diethyl ether and water. The organic phase was washed with 1N sodium hydroxide solution, saturated sodium hydrogen carbonate solution and water, dried over sodium sulphate, filtered and the filtrate was concentrated. The yellowish residue (176 mg, 88% of theory) contained according to gas chromatography 95.1% of 4'-fiuoro-4-biphenylcarboxaldehyde and 3.0% of pbromobenzaldehyde.
ExaMle 3 A mixture of 500 mg (1.43 mmol) of 4-(trans-4-propylcyclohexyl)phenyl trifluoromethylsulphonate, 208 mg (1.71 mmol) of phenylbornic acid, 90 mg (0.03 mmol) of 5% palladiurn-on-charcoal (DEGUSSA E 101 R/D), 302 g of solid sodium carbonate and 5 ml of dimethylformamide was stirred at 900C for 15 hours. A further 45 mg of palladium-on-charcoal were added to the reaction mixture and the reaction was continued for a further 15 hours. Thereupon, the cooled is reaction mixture was taken up in hexane, filtered over Celite and the clear solution was washed several times with water. After drying over magnesium sulphate and evaporation of the solvent there were obtained 360 mg of crude 4-(trans-4-propylcyclohexyl)biphenyl which still contained 17. 4% educt.
ExarWIle 4 A mixture of 588 mg (3.18 mmol) of 1-bromo-4-ethylbenzene, 666 mg (3.8 mmol) of 3-fluore-4-chlorophenylboronic acid, 135 mg (0.04 1) of 10% palladium-on-charcoal (DEGUSSA E 10 HID), 2.5 mI of 2M aqueous sodium carbonate solution and 5 mI of dimethyloxyethane was stirred at 800 for 2 hours, treated with a further 60 mg of palladium-oncharcoal and the reaction was continued for 19 hours. Gas-chromatographic analysis of the reaction mixture gave a content of 94.5% of 3fluoro-4-chloro-4'ethylbiphenyl.
Examble 5 A mixture of 1.05 g (5.28 mmol) of 1-bromo-4-propylbenzene, 1 g (6.33 mmol) of 3,5-difluorophenylboronic acid, 168 mg (0.16 mmol) of 10% panadium-on-charcoal (DEGUSSA E 10 NID), 1.12 g (10.55 mmol) of solid sodium carbonate and 10 mI of 95% ethanol was heated to 800C for 15 hours while stirring. Thereafter, the reaction mixture was cooled, diluted with ether, filtered over Celite and the filtrate was partitioned between water and ether. The combined ether phases were washed twice with saturated sodium chloride solution, dried over magnesium sulphate, filtered over Celite and the filtrate was evaporated completely on a rotary evaporator. Chromatography of the residue (1.49 g) on 75 g of silica gel with hexane gave 3,5-difluoro-4'-propylbiphenyl (4.65 mol) as a colourless liquid.
16

Claims (6)

Claims
1. A process for the manufacture of diarylenes by coupling an aryl or heteroaryl halide or an aryl or heteroaryl fluoroalkylsulphonate with an aromatic boronic acid or with an aromatic boronic acid derivative in the presence of a base, which process comprises carrying out the coupling in the presence of palladium on a carrier material.
2. A process in accordance with claim 1 for the manufacture of diarylenes of the general formula xl R' A R2 -.(D- - 1 / 1 2 by coupling an aryl or heteroaryl halide or an aryl or heteroaryl fluoroalkylsulphonate of the general formula W-&Z I II with an aromatic boronic acid, its anhydride or an aromatic boronic acid derivative of the general formula Xi R30" B__C _R2 III or R4C( X2 E B-Ct B_0 4P E in the presence of a base, which process comprises carrying out the coupling in the presence of palladium on a carrier material, wherein in formulae I to III and III-1 the symbols have the following significances:
R1, R2: independently of one another hydrogen, straight-chain or branched (optionally chiral) alkyl or alkenyl with 1 to 12 carbon atoms, in which optionally one or more methylene groups can be replaced by -0-, -COO-, OOC-, -CO-, -CHY- 17 d/or -CY2-; or alkynyl, halogen, cyano, -OH-, -Q-CHO, -Q-CH(OR5)(OR6), or a group a group a group Y:
Z:
zi _Z2 R7 IV) n M __z1_<j>_Z2-C)=D n 4ZI n Z2 _OR5 ORC' n V or VI fluorine, chlorine, -CN, methyl or -CF3; ring A: 1,4-phenylene, which is unsubstituted or mono- or multiply substituted, pyridine-2,5-diyl, pdine-2,5-diyl, pyrazine 3,5-diyl, pyridazine-3,6-diyl, naphthalene-2,6-diyl, tetralin 2,6-diyl, thiophene-2,5-diyl, 1,3,4-oxadiazole-2,5-diyl or 1,3,4 thiodiazole-2,5-diyl; Xl, X2: independently of one another hydrogen, fluorine, chlorine, -CN, -N02, -NH2 or lower alkyl; a leaving group; R3, R4: hydrogen or lower alkyl; xl -Cl-R2 1 X2 E:
Q: a single bond or an alkylene group; R5, R6: lower alkyl or R5 and R6 together an alkylenediyl. group of the formula -(CH2)p-; P: a number 2 or 3; Z1, Z2: independently of one another a single bond, -CH2-CH2-COO-, OOC-, -CH2-0-, -0-CH2-, -CH=CH-, -C-=C-, -(CH2)4-, -(CH2)30-, -O(CH2)3-, the trans form of -CH=CH-(CH2)2-, -(CH2)2-CH=CH-, -0-CH2-CH=CH- or -CH=CHCH20-; rings B, C: independently of one another 1,4-phenylene, which is unsubstituted or mono- or multiply-substituted, pyridine2,5-diyl, pyrimidine-2,5-diyl, pyrazine-3,5-diyl, pyridazine3,6-diyl, naphthalene-2, 6-diyl, tetralin-2,6-diyl, thiophene2,5-diyl, 1,3,4-oxadiazole-2,5-diyl, 1,3,4-thiodiazole-2,5-diyl; trans-1,4-cyclohexylene, trans- 1,3-dioxane-2, 5-diyl, trans- 18 n,m: R7:
D:
1,3-dithiane-2,5-diyl, trans-decalin-2,6-diyl or bicyclo[2,2,21octane-1,4-diyI; independently of one another a number 0 or 1; straight-chain or branched (optionally chiral) alkyl or alkenyl with 1 to 12 carbon atoms, in which optionally one or more methylene groups can be replaced by -0-, COO-, -OOC-, -CO-, -CHY- and/or -CY2-; or alkenyl, -Q-CHO or -QCH(OR5)(OR6); and oxygen, CHOCH& CHQ-CHO or CHQ-CH(OR5)(OR6).
0
3. A process in accordance with claim 1 or 2 for the manufacture of intermediates and compounds of the general formula xl R R9 )(3 X2 wherein the symbols have the following significances:
1t8:
Pa bromine, chlorine, straight-chain or branched (optionally chiral) alkyl or alkenyl with 1 to 12 carbon atoms, in which optionally one or more methylene groups can be replaced by -0-, -COO-, -OOC-, -CO-, -CHY- and/or -CY2-; or -Q-CHO, -Q-CH(OR5XOR6), or group R7_.&Z1- VII, group D=O-Z2VIII or group R500 _Z2- )o IX R 0 Xl, X2, X3: independently of one another hydrogen, fluorine, chlorine or methyl; R9:
Q:
alkyl, alkoxy, difluoromethoxy, trifluoromethyl, trifluoromethoxy, fluorine, chlorine or -CN; a single bond or -CH2-CH2-; 19 Z1, Z2: a single bond, -CH2-CH2-, -COO-, -OOC-, -CH2-0-, -0-CH2-, -CH=CH- or -C=-C--, ring B: 1,4-phenylene which is unsubstituted or mono- or multiplysubstituted, pyridine-2,5-dil, pyrimidine-2,5-diyl, trans-1, 4cyclohexylene or trans1,3-dioxane-2,5-diyl.
4. A process in accordance with any one of claims 1 to 3 for the manufacture of intermediates and compounds of the general formulae:
xl R10 -G--Q-Rg 2 xl R15 -O-Zl-o,-- - R9 2 xl D-O-Z2 R9 X2 xl R50 R6 be-Z2 -G- R9 o X2 wherein the symbols have the following significances:
Pb PC I-d Pe R10: chlorine, bromine, straight-chain or branched (optionally chiral) alkyl or alkenyl with 1 to 12 carbon atoms, in which optionally one or more methylene groups can be replaced by -0-, -COO-, -OOC-, -CO-, -CHY- and/or -CY2-; or -Q-CHO or -Q-dioxolane; R15: alkyl, alkenyl, -Q-CHO or - Q-dioxolane; Z1, Z2, Q: independently of one another a single bond or - CH2-CH2-; X1v X2: hydrogen or fluorine; D: oxygen, CHOCH3, CHQ-CHO or CHQ- dioxolane.
5. A process in accordance with any one claims 1 to 4 for the manufacture of intermediates for the synthesis of liquid crystalline compounds, of the formulae:
xl OHC-O-O-Rll xl RII CH30-" X1 R11 OHC-/ xi CO R11 0 xi 0 R11 C 0 Xl OHC-"Zl--., R11 xl C3-0 -Z2 H C xl OHC_/-Z1-0-0-Rll xl coo-0-zl-o- RII xl Z1-J/r \ xi, RI1 c 0 0 I-1 1-2 1-3 P4 P5 P6 P7 P8 P9 I-10 1 21 xl -,/---&Z2 -0- R11 CO 0 wherein R11 signifies fluorine, chlorine, -CN, alkyl, alkoxy, difluoromethoxy, trifluoromethyl or trifluoromethoxy.
I-11
6. A process in accordance with any one of claims 1 to 4 for the manufacture of liquid crystalline compounds of the general formulae:
Xl R'2-0-, -F xl R12 -C)-0-CI xl R12 -C) M Xl R12 -0-0-R13 Xl R12-0-Z1-0-., -F Xl R'2---Z1-, Cl xl R12 -&ZI- CN xl R12 -0-zi-C)-O-R13 wherein R12 represents alkyl, alkenyl or alkoxyalkyl; and R13 signifies alkyl, alkoxy, difluoromethoxy, trifluoromethyl or trifluoromethoxy.
1-12 1-13 1-14 1-15 1-16 1-17 1-18 1-19
GB9314237A 1992-03-13 1993-07-09 Preparation of diarylene compounds Withdrawn GB2280181A (en)

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CH821/92A CH683522A5 (en) 1992-03-13 1992-03-13 Process for the preparation of diaryls.
DE4307243A DE4307243A1 (en) 1992-03-13 1993-03-08 Prepn. of di:aryl cpds. useful for producing liquid crystal cpds. - involves coupling of aryl halide(s) with aromatic boron acid derivs. using palladium catalyst
JP5076440A JPH06219971A (en) 1992-03-13 1993-03-11 Method for producing diaryl derivative
GB9314237A GB2280181A (en) 1992-03-13 1993-07-09 Preparation of diarylene compounds

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CH821/92A CH683522A5 (en) 1992-03-13 1992-03-13 Process for the preparation of diaryls.
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