WO2001040154A1 - Method for producing 4'-alkyl-4-hydroxy-biphenyl derivatives - Google Patents

Method for producing 4'-alkyl-4-hydroxy-biphenyl derivatives Download PDF

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WO2001040154A1
WO2001040154A1 PCT/EP2000/012123 EP0012123W WO0140154A1 WO 2001040154 A1 WO2001040154 A1 WO 2001040154A1 EP 0012123 W EP0012123 W EP 0012123W WO 0140154 A1 WO0140154 A1 WO 0140154A1
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formula
alkyl
atoms
groups
compound
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PCT/EP2000/012123
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German (de)
French (fr)
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Andreas WÄCHTLER
Ulrich Fechtel
Karl-Heinz Wembacher
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Merck Patent Gmbh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol

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  • the invention relates to a method for producing 4 ! -Alkyl-4-hydroxy-biphenyl derivatives of the formula I.
  • a alkyl with 1 -10 C atoms, where one or two CH 2 groups can be replaced by O atoms or by -CH CH groups, by reacting a compound of the formula II
  • a 'alkyl with 1-8 C atoms, where one or two CH 2 groups can be replaced by O atoms or by -CH CH groups, means in a Grignard reaction with a compound of the formula III
  • A has the meaning given and L is Cl, Br, I, OH or a reactive esterified OH group, to a compound of formula IV
  • the invention relates in particular to a process as indicated for the preparation of non-racemic 4 '- (2-methylbutyl) -4-hydroxybiphenyl.
  • this also means lower solvent and energy consumption.
  • alkyl preferably has 1, 2, 3,
  • a ' has 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms and is preferably methyl, ethyl, propyl or butyl, but very particularly preferably methyl.
  • L preferably denotes Cl, Br, I or a reactively modified OH group such as alkylsulfonyloxy with 1-6 C atoms (preferably methylsulfonyloxy, trifluoromethylsulfonyloxy or nonafluorobutylsulfonyloxy) or arylsulfonyloxy with 6-10 C atoms (preferably phenyl - or p-tolylsulfonyloxy) or fluorosulfonyloxy.
  • a reactively modified OH group such as alkylsulfonyloxy with 1-6 C atoms (preferably methylsulfonyloxy, trifluoromethylsulfonyloxy or nonafluorobutylsulfonyloxy) or arylsulfonyloxy with 6-10 C atoms (preferably phenyl - or p-tolylsulfonyloxy) or fluorosulfonyloxy.
  • the compounds of the formula II and III are either known or are otherwise prepared by methods known per se, as described in the literature (for example in the standard works such as Houben-Weyl, methods of organic chemistry, Georg-Thieme-Verlag, Stuttgart) are.
  • the Grignard reaction is otherwise carried out by methods known per se, as described in the literature (for example in the standard works such as Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart), under reaction conditions, who are known and suitable for the implementations mentioned. Use can also be made of variants which are known per se and are not mentioned here in detail.
  • the Grignard reaction is carried out under precious metal halide catalysis.
  • Cu, Co or Ni are preferably suitable as metals.
  • Cu (I) chloride is very particularly preferred.
  • the reaction is preferably carried out in THF.
  • the reaction time is between a few minutes and 14 days, the reaction temperature is between about 0 ° and 150 °, preferably between 30 ° and 120 °.
  • the reaction time is very particularly preferably between 30 minutes and 20 hours and the temperature between 30 and 80 °.
  • the ether cleavage can be carried out in a manner known per se (Houben-Weyl, volume
  • alcoholates preferably potassium ethylate
  • dipolar aprotic solvents such as dimethylpropylene urea (DMPU), dimethylethylene urea (DMEU), dimethylformamide (DMF) , (N-methylpyrrolidone) NMP and others, or with KOH in glycol under reflux temperature.
  • Ether cleavage with alkali alcoholates in NMP, DMF, DMPU or DMEU is preferred.
  • Ether cleavage with potassium tert-butoxide in NMP is very particularly preferred.
  • Thiophenols and thio alcoholates are also suitable.
  • the ether cleavage can be carried out by boiling in HBr / glacial acetic acid or by treatment with aluminum chloride or boron trichloride.
  • the processing takes place according to known methods, e.g. by filtration, removal of the solvent, extraction and / or crystallization. All temperatures are in ° C.
  • the corresponding benzenesulfonate is first prepared from non-racemic (R- or S) -2-methylbutanol.
  • the corresponding Grignard compound is made from 109.2 g of 4-bromo-4'methoxybiphenyl and 11.1 g of magnesium in THF (300 ml)
  • reaction mixture is hydrolyzed with hydrochloric acid (approx. 20%).
  • hydrochloric acid approximately 20%.
  • the product is extracted from the aqueous phase with toluene.
  • the toluene phase is with a carbonate solution and then several times with

Abstract

The invention relates to a method for producing 4'-alkyl-4-hydroxy-biphenyl derivatives of the formula (I), wherein A represents an alkyl with 1-10 C atoms, wherein one or two CH2 groups may be substituted by O atoms or -CH=CH groups, by reacting, by means of a Grignard reaction, a compound of the formula (II), wherein Hal represents Cl, Br or I and A' represents an alkyl with 1-8 C atoms, wherein one or two CH2 groups may be substituted by O atoms or -CH=CH, with a compound of the formula (III): A-L, wherein A has the meaning indicated above and L represents Cl, Br, I, OH or a reactive esterified OH group, to give a compound of the formula (IV), wherein A and A' have the meanings indicated above, and subsequent ether cleavage.

Description

Verfahren zur Herstellung von 4'-Alkyl-4-hydroxy-biphenylderivaten Process for the preparation of 4'-alkyl-4-hydroxy-biphenyl derivatives
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von 4!-Alkyl-4- Hydroxy-biphenylderivaten der Formel IThe invention relates to a method for producing 4 ! -Alkyl-4-hydroxy-biphenyl derivatives of the formula I.
Figure imgf000003_0001
worin
Figure imgf000003_0001
wherein
A Alkyl mit 1 -10 C-Atomen, wobei eine oder zwei CH2-Gruppen durch O-Atome oder durch -CH=CH-Gruppen ersetzt sein können, bedeutet, durch Umsetzung einer Verbindung der Formel IIA alkyl with 1 -10 C atoms, where one or two CH 2 groups can be replaced by O atoms or by -CH = CH groups, by reacting a compound of the formula II
Figure imgf000003_0002
worin
Figure imgf000003_0002
wherein
Hai Cl, Br oder I undHai Cl, Br or I and
A ' Alkyl mit 1-8 C-Atomen, wobei eine oder zwei CH2-Gruppen durch O-Atome oder durch -CH=CH-Gruppen ersetzt sein können, bedeutet, in einer Grignard-Reaktion mit einer Verbindung der Formel IIIA 'alkyl with 1-8 C atoms, where one or two CH 2 groups can be replaced by O atoms or by -CH = CH groups, means in a Grignard reaction with a compound of the formula III
A-LA-L
worin A die angegebene Bedeutung hat und L Cl, Br, I, OH oder eine reaktionsfähig veresterte OH-Gruppe bedeutet, zu einer Verbindung der Formel IVwherein A has the meaning given and L is Cl, Br, I, OH or a reactive esterified OH group, to a compound of formula IV
Figure imgf000003_0003
worin A und A' die angegebenen Bedeutungen haben, und anschließender Etherspaltung.
Figure imgf000003_0003
wherein A and A 'have the meanings given, and subsequent ether cleavage.
Gegenstand der Erfindung ist insbesondere ein Verfahren wie angegeben zur Herstellung von nicht-racemischem 4'-(2-Methylbutyl)-4-hydroxy- biphenyl.The invention relates in particular to a process as indicated for the preparation of non-racemic 4 '- (2-methylbutyl) -4-hydroxybiphenyl.
Die Herstellung von Hydroxybiphenylderivaten durch Oxidation von Acylbiphenylen mit Peroxiden in Wasser ist beschrieben von Y. Ogawa et al. in JP 08157406.The preparation of hydroxybiphenyl derivatives by oxidation of acylbiphenylene with peroxides in water is described by Y. Ogawa et al. in JP 08157406.
S.N. Singh et al. beschreiben die Herstellung von 4-Methyl-4'- Hydroxybiphenyl durch Umsetzung von Phenol mit Benzylalkohol. Von V. Macho et al. kennt man die Herstellung von 4-lsopropyl-4'- hydroxybiphenyl durch Arylalkylierung von Phenol aus CS 250861.S.N. Singh et al. describe the preparation of 4-methyl-4'-hydroxybiphenyl by reacting phenol with benzyl alcohol. By V. Macho et al. one knows the preparation of 4-isopropyl-4'-hydroxybiphenyl by arylalkylation of phenol from CS 250861.
Verbindungen der Formel I stellen wichtige Zwischenprodukte im Rahmen der Chemie der reaktiven Mesogene sowie der cholesterischen Flüssigkristalle dar.Compounds of the formula I are important intermediates in the chemistry of reactive mesogens and cholesteric liquid crystals.
Überraschenderweise zeigte sich, daß die Verbindungen der Formel I, insbesondere 4'-(2-Methylbutyl)-4-hydroxybiphenyl in vorteilhafter Weise hergestellt werden können. Dabei ist die einfache durchzuführende Reaktion sowie eine dadurch bedingt einfache Produktisolierung zu nennen.Surprisingly, it was found that the compounds of the formula I, in particular 4 '- (2-methylbutyl) -4-hydroxybiphenyl, can be prepared in an advantageous manner. The simple reaction to be carried out and the resultant simple product isolation should be mentioned.
Das bedeutet in der Konsequenz auch einen geringeren Lösungsmittel- und Energieverbrauch.As a consequence, this also means lower solvent and energy consumption.
In den Verbindungen der Formeln I und III hat Alkyl vorzugsweise 1 , 2, 3,In the compounds of the formulas I and III, alkyl preferably has 1, 2, 3,
4, 5, 6, 7, 8, 9 oder 10 C-Atome, vorzugsweise 1 , 2, 3, 4, 5 oder4, 5, 6, 7, 8, 9 or 10 carbon atoms, preferably 1, 2, 3, 4, 5 or
10 C-Atome und bedeutet vorzugsweise Methyl, Ethyl oder Propyl, weiterhin bevorzugt Isopropyl, Butyl, Isobutyl, sek.-Butyl oder tert.-Butyl, aber auch n-Pentyl, neo-Pentyl oder Isopentyl, Hexyl, Heptyl oder Octyl oder optisch nicht-racemisches 3,7-Dimethyloctyl.10 carbon atoms and is preferably methyl, ethyl or propyl, further preferably isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, but also n-pentyl, neopentyl or isopentyl, hexyl, heptyl or octyl or optically non-racemic 3,7-dimethyloctyl.
A bedeutet ganz besonders bevorzugt 2-Methylbutyl. Besonders bevorzugt sind solche Alkylreste, die in der Kette verzweigt sind, insbesondere wenn durch die Verzweigung eine Chiralität erzeugt wird.A very particularly preferably denotes 2-methylbutyl. Particularly preferred are those alkyl residues that are branched in the chain, especially if the branching creates chirality.
In den Verbindungen der Formel II hat A' 1 , 2, 3, 4, 5, 6, 7 oder 8 C-Atome und bedeutet vorzugsweise Methyl, Ethyl, Propyl oder Butyl, ganz besonders bevorzugt jedoch Methyl.In the compounds of the formula II, A 'has 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms and is preferably methyl, ethyl, propyl or butyl, but very particularly preferably methyl.
In den Verbindungen der Formel III bedeutet L vorzugsweise Cl, Br, I oder eine reaktionsfähig abgewandelte OH-Gruppe wie Alkylsulfonyloxy mit 1-6 C-Atomen (bevorzugt Methylsulfonyloxy, Trifluormethylsulfonyloxy oder Nonafluorbutylsulfonyloxy) oder Arylsulfonyloxy mit 6-10 C-Atomen (bevorzugt Phenyl- oder p-Tolylsulfonyloxy) oder auch Fluorsulfonyloxy.In the compounds of the formula III, L preferably denotes Cl, Br, I or a reactively modified OH group such as alkylsulfonyloxy with 1-6 C atoms (preferably methylsulfonyloxy, trifluoromethylsulfonyloxy or nonafluorobutylsulfonyloxy) or arylsulfonyloxy with 6-10 C atoms (preferably phenyl - or p-tolylsulfonyloxy) or fluorosulfonyloxy.
Die Verbindungen der Formel II und III sind entweder bekannt oder werden im übrigen nach an sich bekannten Methoden hergestellt, wie sie in der Literatur (z.B. in den Standardwerken wie Houben-Weyl, Methoden der organischen Chemie, Georg-Thieme-Verlag, Stuttgart) beschrieben sind.The compounds of the formula II and III are either known or are otherwise prepared by methods known per se, as described in the literature (for example in the standard works such as Houben-Weyl, methods of organic chemistry, Georg-Thieme-Verlag, Stuttgart) are.
Die Grignard-Reaktion wird im übrigen nach an sich bekannten Methoden durchgeführt, wie sie in der Literatur (z.B. in den Standardwerken wie Houben-Weyl, Methoden der organischen Chemie, Georg-Thieme-Verlag, Stuttgart) beschrieben ist, und zwar unter Reaktionsbedingungen, die für die genannten Umsetzungen bekannt und geeignet sind. Dabei kann man auch von an sich bekannten, hier nicht näher erwähnten Varianten Gebrauch machen.The Grignard reaction is otherwise carried out by methods known per se, as described in the literature (for example in the standard works such as Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart), under reaction conditions, who are known and suitable for the implementations mentioned. Use can also be made of variants which are known per se and are not mentioned here in detail.
Die Grignard-Reaktion wird unter Edelmetallhalogenid-Katalyse durchge- führt. Als Metalle eignen sich vorzugsweise Cu, Co oder Ni. Ganz besonders bevorzugt ist Cu(l)-chlorid.The Grignard reaction is carried out under precious metal halide catalysis. Cu, Co or Ni are preferably suitable as metals. Cu (I) chloride is very particularly preferred.
Die Reaktion wird vorzugsweise in THF durchgeführt. Die Reaktionszeit liegt je nach den angewendeten Bedingungen zwischen einigen Minuten und 14 Tagen, die Reaktionstemperatur zwischen etwa 0° und 150°, vorzugsweise zwischen 30° und 120°. Ganz besonders bevorzugt liegt die Reaktionszeit zwischen 30 Minuten und 20 Stunden und die Temperatur zwischen 30 und 80°.The reaction is preferably carried out in THF. Depending on the conditions used, the reaction time is between a few minutes and 14 days, the reaction temperature is between about 0 ° and 150 °, preferably between 30 ° and 120 °. The reaction time is very particularly preferably between 30 minutes and 20 hours and the temperature between 30 and 80 °.
Die Etherspaltung kann in an sich bekannter Weise (Houben-Weyl, BandThe ether cleavage can be carried out in a manner known per se (Houben-Weyl, volume
6, Teil 1c) durch Behandlung mit Alkoholaten, bevorzugt Kaliumethylat,6, part 1c) by treatment with alcoholates, preferably potassium ethylate,
Kaliummethylat, Kaliumpropylat, Kaliumisopropylat, Kaliumbutylat, Kalium- tert.-Butylat usw., bei höheren Temperaturen, vorzugsweise zwischen 60 und 220°C in dipolar aprotischen Lösungsmitteln, wie Dimethylpropylen- hamstoff (DMPU), Dimethylethylenhamstoff (DMEU), Dimethylformamid (DMF), (N-Methylpyrrolidon) NMP und anderen, oder mit KOH in Glykol unter Rückflußtemperatur erfolgen. Bevorzugt ist die Etherspaltung mit Alkalialkoholaten in NMP, DMF, DMPU oder DMEU. Ganz besonders bevorzugt ist die Etherspaltung mit Kalium- tert.-butylat in NMP.Potassium methylate, potassium propylate, potassium isopropylate, potassium butoxide, potassium tert-butoxide, etc., at higher temperatures, preferably between 60 and 220 ° C in dipolar aprotic solvents such as dimethylpropylene urea (DMPU), dimethylethylene urea (DMEU), dimethylformamide (DMF) , (N-methylpyrrolidone) NMP and others, or with KOH in glycol under reflux temperature. Ether cleavage with alkali alcoholates in NMP, DMF, DMPU or DMEU is preferred. Ether cleavage with potassium tert-butoxide in NMP is very particularly preferred.
Thiophenole und Thioalkoholate eignen sich ebenfalls. Sauer kann die Etherspaltung durch Kochen in HBr/Eisessig oder durch Behandlung mit Aluminiumchlorid, Bortrichlorid erfogen. Besonders günstig ist die Etherspaltung mit DMF und KBr oder mit Trimethylsilyljodid, das auch in situ aus Trimethylchlorsilan und KJ hergestellt werden kann.Thiophenols and thio alcoholates are also suitable. The ether cleavage can be carried out by boiling in HBr / glacial acetic acid or by treatment with aluminum chloride or boron trichloride. Ether cleavage with DMF and KBr or with trimethylsilyl iodide, which can also be prepared in situ from trimethylchlorosilane and KJ, is particularly favorable.
Die Aufarbeitung erfolgt nach an sich bekannten Methoden, z.B. durch Filtration, Entfernen des Lösungsmittels, Extraktion und/ oder Kristallisation. Alle Temperaturangaben sind in °C.The processing takes place according to known methods, e.g. by filtration, removal of the solvent, extraction and / or crystallization. All temperatures are in ° C.
Beispiel 1example 1
Herstellung von 4-Brom-4'methoxybiphenylPreparation of 4-bromo-4'methoxybiphenyl
In 100 ml Ethanol werden 4,4 g NaOH und 24,9 g 4-Brom-4'-hydroxy- biphenyl gegeben. Es wird gerührt, wobei eine Lösung entsteht. Bei 30°C werden 13,89 g Dimethylsulfat (gelöst in 25 ml Ethanol) so zugegeben, daß eine Innentemperatur von 40°C nicht überschritten wird. - -4.4 g of NaOH and 24.9 g of 4-bromo-4'-hydroxybiphenyl are added to 100 ml of ethanol. It is stirred, a solution being formed. At 30 ° C, 13.89 g of dimethyl sulfate (dissolved in 25 ml of ethanol) are added so that an internal temperature of 40 ° C is not exceeded. - -
Bei dieser Temperatur wird 8 Stunden lang gerührt. Dann gibt man das Reaktionsgemisch auf Eiswasser, man saugt die Kristalle ab und kristallisiert um.The mixture is stirred at this temperature for 8 hours. Then the reaction mixture is poured onto ice water, the crystals are filtered off and recrystallized.
Beispiel 2Example 2
Herstellung von 4-Methoxy-4'-(2-Methylbutyl)biphenyl (nicht racemisch)Preparation of 4-methoxy-4 '- (2-methylbutyl) biphenyl (non racemic)
in bekannter Weise bzw. in Analogie zu anderen Sulfonaten stellt man zunächst aus nicht racemischem (R- oder S)-2-Methylbutanol das entsprechende Benzolsulfonat her. In üblicher Weise wird aus 109,2 g 4-Brom-4'methoxybiphenyl und 11 ,1 g Magnesium in THF (300 ml) die entsprechende Grignard-Verbindung unterin a known manner or in analogy to other sulfonates, the corresponding benzenesulfonate is first prepared from non-racemic (R- or S) -2-methylbutanol. In a conventional manner, the corresponding Grignard compound is made from 109.2 g of 4-bromo-4'methoxybiphenyl and 11.1 g of magnesium in THF (300 ml)
Ausschluß von Luftsauerstoff und Feuchtigkeit hergestellt. Zu dieser Grignard-Lösung gibt man zunächst 2,1g Cu(l)Chlorid und dann langsam eine Lösung von 120,1 g des oben hergestellten Benzolsulfonats in 120 ml THF.Exclusion of atmospheric oxygen and moisture. To this Grignard solution are first added 2.1 g of Cu (I) chloride and then slowly a solution of 120.1 g of the benzenesulfonate prepared above in 120 ml of THF.
Ma dosiert die Zugabe so, daß ein kräftiger Rückfluß auftritt. Gegen Ende der Zugabe wird erhitzt und danach noch eine Stunde am Rückfluß gekocht.Ma doses the addition so that a strong reflux occurs. Towards the end of the addition, the mixture is heated and then refluxed for an hour.
Nach dem Abkühlen hydrolysiert man das Reaktionsgenisch mit Salzsäure (ca 20%). Man extrahiert das Produkt aus der wäßrigen Phase mit Toluol.After cooling, the reaction mixture is hydrolyzed with hydrochloric acid (approx. 20%). The product is extracted from the aqueous phase with toluene.
Die Toluolphase wird mit einer Carbonatlösung und dann mehrfach mitThe toluene phase is with a carbonate solution and then several times with
Wasser gewaschen.Washed water.
Die organische Phase wird zum Rückstand eingedampft.The organic phase is evaporated to the residue.
Beispiel 3Example 3
Herstellung von 4-Hydroxy-4'-(2-Methylbutyl)biphenyl (nicht racemisch)Preparation of 4-hydroxy-4 '- (2-methylbutyl) biphenyl (non-racemic)
Man erhitzt 28,74 g des erhaltenen 4'-(2-Methylbutyl)-4-methoxybiphenyls zusammen mit Kalium-tert.-Butylat (28,65 g) in 200 ml NMP so lange, bis das Reaktionsgemisch etwa 200°C erreicht hat. Den flüchtigen Anteilen gibt man dabei die Möglichkeit abzudampfen.28.74 g of the 4 '- (2-methylbutyl) -4-methoxybiphenyl obtained are heated together with potassium tert-butoxide (28.65 g) in 200 ml of NMP until the reaction mixture has reached about 200 ° C. The volatile components are given the opportunity to evaporate.
Dann wird abgekühlt und das Reaktionsgenisch mit 1 I Wasser hydrolysiert. Das ausgefallene Produkt wird abgesaugt und aus Petrolether umkristallisiert. It is then cooled and the reaction mixture is hydrolyzed with 1 liter of water. The precipitated product is filtered off and recrystallized from petroleum ether.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von 4'-Alkyl-4-hydroxy-biphenylderivaten der Formel I1. Process for the preparation of 4'-alkyl-4-hydroxy-biphenyl derivatives of the formula I.
Figure imgf000009_0001
Figure imgf000009_0001
worinwherein
A Alkyl mit 1-10 C-Atomen, wobei eine oder zwei CH2-Gruppen durch O-Atome oder durch -CH=CH-Gruppen ersetzt sein können, bedeutet, durch Umsetzung einer Verbindung der Formel IIA means alkyl with 1-10 C atoms, where one or two CH 2 groups can be replaced by O atoms or by -CH = CH groups, by reacting a compound of the formula II
Figure imgf000009_0002
Figure imgf000009_0002
worinwherein
Hai Cl, Br oder I undHai Cl, Br or I and
A ' Alkyl mit 1-8 C-Atomen, wobei eine oder zwei CH2-Gruppen durch O-Atome oder durch -CH=CH-Gruppen ersetzt sein können, bedeutet, in einer Grignard-Reaktion mit einer Verbindung der Formel IIIA 'alkyl with 1-8 C atoms, where one or two CH 2 groups can be replaced by O atoms or by -CH = CH groups, means in a Grignard reaction with a compound of the formula III
A-LA-L
worin A die angegebene Bedeutung hat und L Cl, Br, I, OH oder eine reaktionsfähig veresterte OH-Gruppe bedeutet, zu einer Verbindung der Formel IV
Figure imgf000010_0001
wherein A has the meaning given and L is Cl, Br, I, OH or a reactive esterified OH group, to a compound of formula IV
Figure imgf000010_0001
worin A und A' die angegebenen Bedeutungen haben, und anschließender Etherspaltung.wherein A and A 'have the meanings given, and subsequent ether cleavage.
2. Verfahren nach Anspruch 1 , wobei die Grignard-Reaktion unter Cu- Katalyse durchgeführt wird.2. The method according to claim 1, wherein the Grignard reaction is carried out under Cu catalysis.
3. Verfahren nach Anspruch 1 oder 2, wobei in der Verbindung der Formel II Hai Br bedeutet.3. The method according to claim 1 or 2, wherein in the compound of formula II Hai Br means.
4. Verfahren nach Anspruch 1 , 2 oder 3, wobei die Etherspaltung basisch mit einem Alkalialkoholat in einem organischen Lösungsmittel durchgeführt wird.4. The method of claim 1, 2 or 3, wherein the ether cleavage is carried out basic with an alkali alcoholate in an organic solvent.
5. Verfahren nach Anspruch 1 , 2 oder 3, wobei die Etherspaltung mit einem Alkalialkoholat in NMP, DMF, DMPU oder DMEU erfolgt.5. The method of claim 1, 2 or 3, wherein the ether cleavage is carried out with an alkali alcoholate in NMP, DMF, DMPU or DMEU.
6. Verfahren nach einem der vorangehenden Ansprüche, wobei A 2- Methylbutyl bedeutet. 6. The method according to any one of the preceding claims, wherein A is 2-methylbutyl.
PCT/EP2000/012123 1999-12-02 2000-12-01 Method for producing 4'-alkyl-4-hydroxy-biphenyl derivatives WO2001040154A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003055285A (en) * 2001-08-09 2003-02-26 Hokko Chem Ind Co Ltd 4-tert-BUTOXY-4'-HALOGENOBIPHENYL, METHOD FOR PRODUCING THE SAME AND METHOD FOR PRODUCING 4-HALOGENO-4'- HYDROXYBIPHENYL

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE58001C (en) * Dr. R. HIRSCH in Berlin W., Potsdamerstrafse 113 Process for the preparation of phenyl ether and oxydiphenyl, as well as their homologues
DE1016716B (en) * 1956-04-18 1957-10-03 Kalle & Co Ag Process for the preparation of aromatic hydroxyl compounds substituted in the p-position to the hydroxyl group
DE2450088A1 (en) * 1974-10-22 1976-04-29 Merck Patent Gmbh Liquid crystalline dielectrics for electronic components - contg biphenylyl carboxylic acid phenyl ester or benzoic acid biphenylyl ester components

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE58001C (en) * Dr. R. HIRSCH in Berlin W., Potsdamerstrafse 113 Process for the preparation of phenyl ether and oxydiphenyl, as well as their homologues
DE1016716B (en) * 1956-04-18 1957-10-03 Kalle & Co Ag Process for the preparation of aromatic hydroxyl compounds substituted in the p-position to the hydroxyl group
DE2450088A1 (en) * 1974-10-22 1976-04-29 Merck Patent Gmbh Liquid crystalline dielectrics for electronic components - contg biphenylyl carboxylic acid phenyl ester or benzoic acid biphenylyl ester components

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
H. SHIRAKAWA ET AL.: "Synthesis of Liquid Crystalline Polyacetylene Derivatives", MOLECULAR CRYSTALS AND LIQUID CRYSTALS SCIENCE AND TECHNOLOGY. SECTION A, vol. 255, 1994, Philadelphia, pages 213 - 219, XP000996142 *

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003055285A (en) * 2001-08-09 2003-02-26 Hokko Chem Ind Co Ltd 4-tert-BUTOXY-4'-HALOGENOBIPHENYL, METHOD FOR PRODUCING THE SAME AND METHOD FOR PRODUCING 4-HALOGENO-4'- HYDROXYBIPHENYL

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