WO1993014065A1 - Procede de preparation de 1,3,5- tris(4'-hydroxyphenyl)benzene et de ses derives - Google Patents

Procede de preparation de 1,3,5- tris(4'-hydroxyphenyl)benzene et de ses derives Download PDF

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WO1993014065A1
WO1993014065A1 PCT/US1992/011015 US9211015W WO9314065A1 WO 1993014065 A1 WO1993014065 A1 WO 1993014065A1 US 9211015 W US9211015 W US 9211015W WO 9314065 A1 WO9314065 A1 WO 9314065A1
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compound
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tris
benzene
alkyl
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Mohammad Aslam
Daniel Alfonso Aguilar
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Hoechst Celanese Corporation
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/017—Esters of hydroxy compounds having the esterified hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/13—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups
    • C07C205/20—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C07C205/21—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to carbon atoms of six-membered aromatic rings having nitro groups and hydroxy groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C205/22—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to carbon atoms of six-membered aromatic rings having nitro groups and hydroxy groups bound to carbon atoms of the same non-condensed six-membered aromatic ring having one nitro groups bound to the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/13—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups
    • C07C205/20—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C07C205/21—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to carbon atoms of six-membered aromatic rings having nitro groups and hydroxy groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C205/23—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to carbon atoms of six-membered aromatic rings having nitro groups and hydroxy groups bound to carbon atoms of the same non-condensed six-membered aromatic ring having two nitro groups bound to the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
    • C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C07C309/66—Methanesulfonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C07C37/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of SO3H groups or a derivative thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
    • C07C37/0555—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group being esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
    • 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

Definitions

  • This invention relates to derivatives of 1,3,5-tris (4'- hydroxyaryl) benzene, intermediate compounds and methods for making these compounds More specifically, the invention relates to novel 1,3,5-tris (4'-acyloxy-substitutedphenyl) benzenes, 1,3,5- tris [4'-0-(N,N'-disubstitutedthiocarbamoyl) -phenyl] benzenes and 1,3,5-tris (4'-substitutedsulfonoxyphenyl) benzenes and methods for making these compounds.
  • the corresponding acetophenones namely the 4- acyloxyacetophenones , the novel 4' - substitutedsulfonyloxyacetophenones and the 0-(4'- acetylphenyl)-N,N'-disubst itutedthiocarbamates, are trimerized under appropriate reaction conditions.
  • the electron withdrawing groups that is,
  • trimerizing 4-hydroxyacetophenone, a 4-hydroxyacetophenone derivative, or a 4-substitutedoxyacetophenone by contacting such a compound with a tetrahalosilane, for instance tetrachlorosilane, preferably in an alkyl alcohol, for example, a lower alkyl alcohol such as methanol, ethanol, propanol or the like.
  • 1,3,5-tris (4'-hydroxyphenyl) benzene falls into the class of compounds known as trisphenyls.
  • Trisphenyls have been recognized as useful intermediates in the preparation of more complex organic structures. For example, reacting trisphenyls with formaldehyde, acid anhydrides and more importantly with epichlorohydrin produces epoxide resins. Epoxide resins prepared from such compounds exhibit low shrinkage, extraordinary hardness, chemical inertness, outstanding mechanical strength, and a variety of beneficial features. See, for example, U.S. Patent No. 4,394,496; and, the commonly owned, concurrently filed application of Hilton, Serial No. 07/819,166, filed January 8, 1992, incorporated herein by reference.
  • 1,3,5-tris (4'-hydroxyaryl) benzene (THAB) molecules are particularly useful in their ability to stabilize polycarbonates. This is accomplished via a three site rigid D 3h crosslink.
  • THAB molecules may also be used as crosslinking agents in epoxy resins. See, for example, Chem. Abstracts, 66, 3004C.
  • the compositions obtained by the invention are useful for their epoxidation products which can be used to form epoxy resins and also can be used in the preparation of polycarbonates.
  • THPB was first reported in Beilstein, E II 6 , 1115
  • THPB was also reported in Chimia, 12, 143 (1958) as formed by the trimerization of 4-haloacetophenone, where the halogen is either bromine or chlorine, in the presence of potassium pyrosulfate and sulfuric acid. This reaction results in 1,3,5-tris (4'-halophenyl) benzenes. These halogen-containing trimers were treated with sodium hydroxide and converted to THPB.
  • Starnes et al. U.S. Patent No. 3,458,473, issued July 29, 1969 and Starnes et al. U.S. Patent No. 3,644,538, issued February 22, 1972 are directed to the preparation of various hindered trisphenols.
  • the hindered trisphenols of both Starnes references are prepared by the cyclotrimerization of an acetylphenol which is the precursor.
  • the acetylphenol precursors are combined with triethylorthoformate in a solvent and then treated with gaseous hydrogen chloride.
  • U.S. Patent No. 3,026,264 to Rocklin et al., issued March 20, 1962 is directed to polynuclear polyphenols and stabilized compositions containing such compounds.
  • the substituted benzenes of Rocklin are prepared by alkylation of a trialkylbenzene with 3,5-dialkyl-4-hydroxy-benzyl alcohol under alkylating conditions and in the presence of sulfuric acid or a Friedel-Crafts catalyst.
  • U.S. Patent No. 3,053,803 to Jaffe et al., issued September 11, 1962 concerns polynuclear phenols, including tri (hydroxybenzyl) benzenes.
  • the polynuclear phenols of Jaffe are taught to be useful as phenolic anti-oxidants for stabilized compositions.
  • the polynuclear phenols of Jaffe are prepared by reacting a mononuclear aryl compound having up to two hydroxyl substituents attached to ring carbon atoms and having at least two replaceable hydrogen atoms attached to ring carbon atoms, with 3,5-dialkyl-4- hydroxybenzyl alcohol, in an inert solvent containing a catalytic amount of a catalyst selected from the group consisting of sulfuric acid and Friedel-Crafts catalysts.
  • German Patent 258,929 to Zimmerman et al. issued August 10, 1988 is directed to methods for the production of 1,3,5-tris (triarylbenzene) compounds. These compounds are reacted by combining 2,4,6-triaryl pyrylium salts with carboxylic acid anhydride in the presence of a basic condensing agent. The reaction of Zimmerman utilizes triaryl pyrylium carboxylic anhydride.
  • trimerizing a hydroxyacetophenone such as 4-hydroxyacetophenone or a 4- hydroxyacetophenone derivative
  • a hydroxyacetophenone such as 4-hydroxyacetophenone or a 4- hydroxyacetophenone derivative
  • Elmorsy et al. because of the belief that the hydroxy group would interfere with the reaction, for example, react with the tetrachlorosilane. See, e.g., Sharin et al., supra, which illustrate why it was believed, before now, that direct trimerization of hydroxyacetophenone was not feasible. Accordingly, Elmorsy et al. fail to teach or suggest the present invention.
  • This invention relates to derivatives of 1,3,5-tris (4'- hydroxyphenyl) benzene, various intermediate compounds and methods for making these compounds.
  • R is an electron withdrawing group such as
  • each of R 2 and R 3 is a C 1 -C 20 alkyl, e.g., C 1 -C 5 lower alkyl such as methyl or ethyl, a substituted alkyl, e.g., alkyl substituted by one or more halogen and/or nitro, or an aromatic such as phenyl, or an aromatic substituted by an alkyl and/or halogen and/or nitro such as tolyl, cumenyl, xylyl, mesityl, or an aryl halide, for instance a halophenyl such as chlorophenyl, R 2 and R 3 being the same or different;
  • R 1 is hydrogen, an alkyl group such as an alkyl group having from 1 to about 12 carbon atoms, preferably a C 1 -C 5 lower alkyl, e.g., methyl or ethyl, a cycloalkyl of from about 3 to about 6 carbon atoms, phenyl
  • R, R 1 and x are defined as above.
  • the reaction involves the use of 4-hydroxyacetophenone derivatives (4-HAP derivative) to prepare 4- substitutedoxyacetophenones (4-HAP subs) such as 4- acyloxyacetophenones, 4-substitutedsulfonyloxyacetophenones and 0-(4'-acetylphenyl)-N,N'-disubstitutedthiocarbamates.
  • 4-HAP sub compounds prepared in the present invention have the general formula II:
  • R is an electron withdrawing group such as
  • the trimerization of the compounds of formula II results in the new 1,3,5-tris (4'-hydroxyphenyl) benzene derivatives such as 1,3,5-tris (4'-acetoxyphenyl) benzene, 1,3,5-tris (4'-methanesulfonoxyphenyl) benzene and 1,3,5- tris [4'-0-(N,N'-dimethylthiocarbamoyl)phenyhl]benzene.
  • These derivatives are not only useful for preparing THPB, but also, like THPB, they can be used to form more complex organic structures. Furthermore, they can be used in the preparation of polycarbonates.
  • a compound such as 4-acetoxyacetophenone or a derivative is trimerized with dimethoxyethane and triethyl orthoformate to form a new compound, 1,3,5-tris (4'- acetoxyphenyl) benzene or one of its derivatives.
  • the 1,3,5- tris (4'-acetoxyphenyl) benzene derivative is in turn hydrolyzed to a 1,3,5-tris (4'-hydroxyphenyl) benzene.
  • Another embodiment provides for the preparation of compounds such as 1 , 3 , 5 - t ris ( 4 ' - methanesulfonoxyphenyl) benzene and 1,3,5-tris (4'- hydroxyphenyl) benzene and their derivatives by trimerizing 4-methanesulfonyloxyacetophenone (4-HAP mesylate) or a derivative of the formula
  • a water scavenger such as methanesulfonyl chloride arid methanesulfonic acid catalyst to produce 1,3,5-tris (4'- methanesulfonoxyphenyl) benzene (or the corresponding derivative).
  • This new compound in turn is cleaved by hydrolysis to form 1,3,5-tris (4'-hydroxyphenyl) benzene or a derivative thereof.
  • the 4-HAP mesylate and its derivatives are formed by mesylating the corresponding 4-hydroxyacetophenone (4-HAP), for example, by contacting the 4-HAP compound with methanesulfonyl chloride.
  • an embodiment of the present invention includes a process for the preparation of a 1,3,5-tris (4'- hydroxyphenyl) benzene derivative, which comprises contacting a compound such as 0-(4'-acetylphenyl) -N,N'- dimethylthiocarbamate or one of its derivatives, with triethyl orthoformate and chloroform under reaction conditions which results in a new compound 1,3,5-tris [4'-0- (N,N-dimethylthiocarbamoyl)-phenyhl]benzene or a derivative which may in turn be hydrolyzed to produce 1,3,5-tris (4'- hydroxyphenyl) benzene or one of its corresponding derivatives.
  • a compound such as 0-(4'-acetylphenyl) -N,N'- dimethylthiocarbamate or one of its derivatives
  • a 4-HAP sub compound of formula II, or a 4-HAP derivative such as 4- hydroxyacetophenone is contacted with a halosilane, preferably a tetrahalosilane such as tetrachlorosilane, tetrabromosilane, tetrafluorosilane, tetraiodosilane, and the like, to yield the corresponding trimer.
  • a halosilane preferably a tetrahalosilane such as tetrachlorosilane, tetrabromosilane, tetrafluorosilane, tetraiodosilane, and the like
  • the halosilane is preferably present in at least an equimolar amount with respect to the a'cetophenone; and, the contacting is preferably performed in the presence of a solvent such as an alkyl alcohol, for instance, methanol, ethanol, propanol, or the like, more preferably an anhydrous solvent.
  • a solvent such as an alkyl alcohol, for instance, methanol, ethanol, propanol, or the like, more preferably an anhydrous solvent.
  • a solvent such as an alkyl alcohol, for instance, methanol, ethanol, propanol, or the like, more preferably an anhydrous solvent.
  • a solvent such as an alkyl alcohol, for instance, methanol, ethanol, propanol, or the like
  • an anhydrous solvent for example, tetrachlorosilane, dry anhydrous ethanol, and reaction conditions of about 15° to about 80°C, typically about room temperature (e.g., about 20° to about 25°
  • the 4-HAP derivative may be converted to a 4-HAP sub:
  • R 1 is hydrogen, an alkyl group (including mono- or poly-substituted alkyl, e.g., with halogen and/or nitro) such as an alkyl group having from 1 to about 12 carbon atoms, preferably a C 1 -C 5 lower alkyl, such as methyl or ethyl, a cycloalkyl of from about 3 to about 6 carbon atoms, phenyl (including mono- or poly- substituted phenyl, e.g., with halogen and/or nitro), halogen, such as Cl, Br, F or I, nitro, alkyl sulfonyl or aromatic sulfonyl in which the alkyl group preferably has 1 to about 12 carbon atoms, more preferably the alkyl group is a C 1 -C 5 lower alkyl or a substituted alkyl, e.g., a C 1 -C 5 lower alkyl substituted by one or more halogen and
  • R 2 and R 3 are the same or different and each is a C 1 - 20 alkyl, preferably a C 1 - 5 alkyl and more preferably methyl or ethyl or a substituted alkyl, for instance, an alkyl substituted by one or more nitro and/or halogen groups, e.g., a halo-substituted alkyl or a nitro substituted alkyl, or an aromatic or a substituted aromatic, e.g., an alkyl substituted aromatic such tolyl, cumenyl, xylyl or mesityl, or a halo-substituted or nitro-substituted aromatic; and X is a halogen, e.g., F, Cl, Br, I, preferably Cl.
  • the R P compounds of formulae VIA and VIIA can be symmetrical or mixed anhydrides. When the R P compounds of formulae VIA and VIIA are symmetrical anhydrides, they are
  • R P can be a symmetrical anhydride of the formula
  • alkyl anhydride such as acetic anhydride or a substituted alkyl anhydride, such as, a halo- substituted alkyl anhydride, for instance, trifluoroacetic anhydride, or trichloroacetic anhydride, or an aromatic anhydride such as benzoic anhydride.
  • alkyl anhydride such as acetic anhydride or a substituted alkyl anhydride, such as, a halo- substituted alkyl anhydride, for instance, trifluoroacetic anhydride, or trichloroacetic anhydride, or an aromatic anhydride such as benzoic anhydride.
  • R p can also be a sulfonyl halide of the formula
  • R which is preferably an alkyl sulfonyl halide, such as ethanesulfonyl chloride or methanesulfonyl chloride (mesyl chloride) or an aromatic sulfonyl halide, such as tosyl chloride.
  • alkyl sulfonyl halide such as ethanesulfonyl chloride or methanesulfonyl chloride (mesyl chloride) or an aromatic sulfonyl halide, such as tosyl chloride.
  • R p can be
  • R 2 and/or R 3 may also be aromatic or substituted aromatic, such as phenyl, tolyl, xylyl, mesityl, an aryl halide, or a nitro-substituted aromatic. Therefore, R will be
  • the 4- HAP derivative may be converted to a 4-HAP sub wherein R is
  • R p anhydride or R P halide e.g., chloride
  • suitable reaction conditions such as reflux under an inert atmosphere such as nitrogen for a suitable time such as about 2 to 20, preferably about 4 hours.
  • the acid (formed during the reaction) and any excess anhydride or acid halide, e.g., chloride corresponding to R are removed, for instance, distilled, preferably in vacuo, leaving a product.
  • the product is preferably then purified, to yield the 4-HAP sub in which R is R 2 CO- .
  • 4-HAP can be converted to 4-HAP sub where R is which is preferably a 4-substitutedsulfonyloxyacetophenone, by contacting the 4-HAP derivative with the corresponding R p halide or anhydride of formula VII or VIIA under conditions which do not cause excessive decomposition of reactants and/or products, and, which allow for a sufficient yield of desired product.
  • the 4-HAP derivative can be added to a solvent, for example, methylene chloride, and cooled to an appropriate temperature, for example, about -10 to 20°C, preferably about 0°-15°C, more preferably about 10°C.
  • a base, such as triethylamine is added and preferably the mixture is maintained at the cool temperature.
  • the base to 4-HAP derivative mole ratio is preferably about 2:1 to 1:2, and more preferably about 1:1.
  • the R p halide or anhydride of formula VII or VIIA in a solvent, such as methylene chloride, is then added, in a mole ratio relative to the 4-HAP of about 2:1 to about 1:2, preferably about 1:1, at such a rate that the reaction temperature preferably is maintained at the cool temperature.
  • the reaction mixture is then allowed to achieve room temperature and stirred or agitated at ambient temperature for about 1 to 24 hours, preferably about 10 to 16 hours, for example, overnight.
  • R p halide or anhydride of formula VII or VIIA for instance mesyl or tosyl chloride or anhydride, is added in an amount of, for example about 10 to 20%, preferably about 15 to 17% of the amount initially utilized.
  • the mixture is heated with agitation for about 0.5-2 hours, preferably about 1 hour at about 30°-50°C, preferably about 40°C.
  • the reaction mixture is then concentrated, for example, by vacuum, at about 25-35°C, preferably about 30°C. See also Finley et al., U.S. Patent No. 4,128,490, incorporated herein by reference.
  • the 4-HAP sub formed can be recovered, if desired.
  • the solids from the concentrated reaction mixture can be slurried in a sufficient quantity of ice water, filtered, and dried, to result in a solid of the 4-HAP sub in which R is R 2 SO 2 -.
  • the 4-HAP sub is preferably an 0-(4'-acetylphenyl)-N,N'- disubstitutedthiocarbamate
  • the 4-HAP derivative is contacted with the corresponding R p halide of formula VIII under conditions which will not result in significant deterioration of reactants and/or products.
  • Such conditions include forming a cooled solution of alkali hydroxide in alkyl alcohol, such as, KOH in CH 3 OH, adding 4-HAP derivative, and, adding the halide corresponding to R, to form a reaction mixture.
  • the reaction mixture is gradually allowed to warm to room temperature. After stirring at room temperature, water is added and the mixture cooled, thereby causing precipitation of a solid.
  • the solid is the 4-HAP sub with R being R 2 R 3 NCS-.
  • the solid can be collected, for example, by filtration, washed, for instance, with water, and dried, for example, in vacuo, to obtain the 4-HAP sub in which R is R 2 R 3 NCS . See U.S. Patent No. 4,749,205, which is hereby incorporated herein by reference.
  • the 4-HAP sub is trimerized in an acidic medium to form the corresponding 1,3,5-tris (4'-substitutedphenyl) benzene derivative, which can be isolated and used in that form or can be converted to the corresponding THPB derivative by hydrolysis.
  • the 4- HAP derivative or 4-HAP sub can also be trimerized in the presence of a halosilane. For instance, when R is
  • the 4-HAP sub which is preferably a 4-acyloxyacetophenone is exposed to an acid such as anhydrous HCl, in a
  • the 4- acyloxyacetophenone is mixed with 1, 2 dimethoxyethane and triethylorthoformate which is cooled, for instance, to about -20° to 20°C, preferably to about 0°C and anhydrous HCl is added until the temperature rises, for example, to about at least 20° to 40°C, preferably at least about 30°C, for about 1 to about 4 hours, typically about 2 hours.
  • the orthoformate to 4-HAP sub mole ratio is preferably about 1:2 to 2:1, typically about 1:1.
  • the remaining HCl is purged, for example, by bubbling an inert gas such as nitrogen into the mixture and the resulting 1,3,5- tris (4'-acyloxysubstitutedphenyl) benzene is recovered.
  • Recovery can include concentrating the reaction mixture, adding an excess of anhydride such as a two to five, preferably a three-fold. molar excess, adding about 0.05 to 0.3, preferably about 0.1 molar equivalents of the salt of the acid corresponding to the anhydride,
  • the trimer can then be recovered by hydrolysis'.
  • a suitable time for example, about 1 to 4 hours, preferably about two hours, and, precipitating the trimer by cooling.
  • the precipitate can then be filtered, washed and dried.
  • the 4-acyloxyacetophenone can be contacted with a suitable acid in liquid form, such as methanesulfonic acid at room temperature to form the 1,3,5-tris-(4'-acyloxysubstitutedphenyl)benzene.
  • the trimer can then be recovered by hydrolysis'.
  • 1,3,5-tris (4'- acyloxysubstitutedphenyl) benzene is conveniently
  • a THPB derivative in a basic alcoholic medium for example, an alkali hydroxide in alkyl
  • the number of moles of alkali hydroxide be in excess of, preferably a three to 15-fold excess of, the number of moles of trimer.
  • the THPB derivative can be recovered by washing the reaction mixture with an organic solvent such as methylene
  • the acyloxy trimer can be hydrolyzed under acidic conditions.
  • the acyloxy trimer can be contacted with .an acid catalyst such as HCl, H 2 SO 4 and the like, for instance, catalytic amounts of an acid catalyst to an excess of an acid catalyst (with respect to the moles of the trimer); the contacting is preferably in the presence of a solvent such as water or a water miscible organic such as a lower alkyl
  • alcohol e.g., methanol, ethanol and the like, and is preferably performed under temperatures and pressures of reflux, and for a time sufficient to effect hydrolysis such as 2 to 12 hours, e.g., 4 to 8 hours.
  • the 4-HAP sub which is preferably a 4- substitutedsulfonyloxyacetophenone, is also trimerized in the presence of an acid and the trimer hydrolyzed.
  • the 4- substitutedsulfonyloxyacetophenone is preferably
  • R 2 -sulfonyl halide contacted with a R 2 -sulfonyl halide and a corresponding R 2 -sulfonic acid.
  • R 2 -sulfonyl halide contacted with a R 2 -sulfonic acid.
  • 4-HAP mesylate is
  • the mole ratio of the R 2 -sulfonyl halide to the 4- substitutedsulfonyloxyacetophenone is about 1:2 to about 2:1, preferably about 1:1; and, the R 2 -sulfonic acid is present in a mole ratio (to amount of the 4-HAP sub) of about 0.05:1 to about 0.5:1, preferably about 0.1:1 to about 0.44:1.
  • Suitable reaction conditions include times of about 2 to about 100 hours and temperatures of about 25 to about 150°, e.g., 100°C for 40 hr. The resulting
  • 1,3,5-tris (4'-substitutedsulfonoxyphenyl) benzene can then be recovered from the reaction mixture.
  • the trimer can be recrystallized for further purification.
  • trimer if desired, is hydrolyzed to a THPB derivative in a suitable manner such as that described above in the hydrolysis of the 1,3,5-tris (4'- acyloxysubstitutedphenyl) benzene.
  • reaction conditions for hydrolysis can include times of, for example, about 1 to 24 hours, preferably about 10 to 16 hours and
  • the 4-HAP sub which is preferably an 0-(4'- acetylphenyl)-N,N'-disubstitutedthiocarbamate, is also conveniently trimerized by contacting it with acid under suitable reaction conditions.
  • the 0 -(4'- acetylphenyl)-N,N'-disubstitutedthiocarbamate can be dissolved into a solvent such as triethylorthoformate and chloroform, and contacted with anhydrous HCl at about 45 to 65°C, typically about 55°C.
  • the temperature is maintained at about 60° to 80°C, preferably between about 65 and 71°C, for about 1 to about 5, preferably about 2 hours.
  • the orthoformate to 4-HAP sub mole ratio in this instance is typically 1:2 to 2:1, preferably about 3:2.
  • the HCl is purged leaving the 4-HAP sub trimer, 1,3,5- tris [4'-0-(N,N'- disubstitutedthiocarbamoyl) phenyl] benzene which is recovered, for example, by evaporating the chloroform, dissolving the product in ethyl acetate, and washing with water.
  • the resultant organic layer is separated, dried, filtered, concentrated, and the product is recrystallized (e.g., with ethanol).
  • the resulting trimer can be hydrolyzed to the
  • THPB derivative in a suitable manner such as that described above in the hydrolysis of the 1,3,5- tris (4'-acyloxysubstitutedphenyl) benzene.
  • a 4-HAP sub compound of formula II, or a 4-HAP derivative such as 4-hydroxyacetophenone can be trimerized by contacting the acetophenone with a
  • the halosilane is preferably a
  • tetrahalosilane such as tetrachlorosilane
  • the halosilane is preferably present in at least an equimolar amount with respect to the acetophenone; and, the contacting is preferably performed in the presence of a solvent such as an alkyl alcohol, for instance, methanol, ethanol, propanol, or the like.
  • a solvent such as an alkyl alcohol, for instance, methanol, ethanol, propanol, or the like.
  • An anhydrous solvent such as dry ethanol is preferred.
  • the reaction conditions of this alternative embodiment are any conditions which will promote the formation of the product and will not cause significant deterioation of starting materials or
  • Typical conditions include temperatures of about 15°C to about 80°C, more preferably about room temperature (e.g., about 20° to about 25°C) and stirring for about 2 to about 100 hours, usually about 4 to about 72 hours, e.g., about 6 to about 48 hours.
  • room temperature e.g., about 20° to about 25°C
  • stirring for about 2 to about 100 hours usually about 4 to about 72 hours, e.g., about 6 to about 48 hours.
  • an equilmolar amount of tetrachlorosilane is added slowly.
  • the mixture is stirred for 72 hours at room temperature.
  • the trimer can then be recovered, for instance, by pouring the reaction mixture into water to afford the trimer.
  • the trimer can be purified, for example, by drying, filtering, concentrating and
  • R, R 1 , and x are as defined above.
  • 1,3,5-tris (4'-substitutedaryl) benzenes which can be prepared in accordance with the invention include:
  • 1,3,5-tris (4'-trifluoroacetoxyphenyl) benzene; 1,3,5-tris (4'-trichloroacetoxyphenyl) benzene; 1,3,5-tris (2'-alkyl 4'-acetoxyphenyl) benzene; 1,3,5-tris(2',3'-dialkyl, 4'- acetoxyphenyl)benzene;
  • 1,3,5-tris(4'-hydroxyaryl)benzenes which can be prepared in accordance with the invention include the products of hydrolyzing the above-listed 1,3,5-tris (4'-substitutedaryl) benzenes as well as:
  • 4-substituted acetophenones used in the reactions include the acetophenone precursors of the above-listed 1,3,5-tris(4'-substitutedaryl)benzenes, such as:
  • 2-alkyl 4-trichloroacetoxyacetophenone
  • 2-alkyl 4-trifluoroacetoxyacetophenone
  • 4-hydroxyacetophenones deriviatives used in the reactions include the acetophenone precursors of the above-listed 1,3,5-tris(4'-hydroxyaryl)benzenes, as well as:
  • 1,3,5-tris(4'-hydroxyaryl)benzene includes 1,3,5- tris(4'-hydroxyphenyl)benzene and substituted 1,3,5- tris(4'-hydroxyphenyl)benzenes.
  • the term "4- hydroxyacetophenone derivative” includes 4- hydroxyacetophenone and substituted 4- hydro-xyacetophenones (whereas "4-HAP substituted” or “4- HAP sub” refers to a 4-hydroxyacetophenone derivative wherein the H of the hydroxy group has been substituted by R).
  • TAPB 1,3,5-tris (4'- acetoxyphenyl) benzene
  • TAPB prepared as in step (a) was hydrolyzed in a saturated solution of ethonolic potassium hydroxide by contacting the TAPB with the solution and refluxing the reaction mixture for several hours. The reaction mixture was then cooled to room temperature and solids were removed via filtration. The organic layer was discarded and the aqueous layer acidified to a pH of about 4 to 5 to afford a solid (9.8 grams) of crude THPB.
  • the magnesium sulfate was removed via filtration.
  • TDMTCPB prepared as in step (a) (7.7 g, 0.0125 mol) was hydrolyzed by contacting it with a saturated solution of saturated methanolic potassium hydroxide (115 ml). The reaction mixture was refluxed for about 6 hours, cooled to room temperature and washed with
  • 4-Hydroxyacetophenone (4-HAP) (81.6; 0.60 mol) was added to 300 ml of methylene chloride and the mixture was cooled to 10°C.
  • Triethylamine (60.6 g; 0.60 mol) was then added and a solution of methanesulfonyl chloride (69.0 g; 0.60 mol) in 300 ml of methylene chloride was added to the mixture at such a rate that the reaction temperature was maintained at about 10°C.
  • the mixture was agitated overnight at ambient temperature, then additional methanesulfonyl chloride (12.0 g; 0.1 mol) was added and the reaction mixture was heated to 40°C with agitation for 1 hr.
  • 4-HAP mesylate trimer (18.0 g; .031 mol) prepared as in step (b) was contacted with and methanol (150 ml). While stirring the mixture, a solution of sodium hydroxide (18.0 g; 0.45 mol) in demineralized water (36 ml) was added. The mixture was heated at reflux overnight, then cooled to ambient temperature. The mixture was then acidified with concentrated HCl, to a pH of about 4 to 5 and concentrated in vacuo to afford a suspension (93 g). The suspension was cooled in an ice bath, diluted with demineralized water (50 ml), and the solids were isolated by filtration.
  • the isolated solids were washed with water (25 ml) and dried, resulting in 13.3 g of a purple solid (88% pure by normalized LC). To remove color, the solid (12.7 g) was digested in a 10% (w/w) aqueous solution of sodium hydroxide (100 ml to form a dark green solution which was washed with dimethyl ether (50 ml) and acidified to a pH of about 4.0 to 5.0 with concentrated HCl to produce a solid which
  • 4-HAP mesylate (9.6 g; 45 mmol) was contacted with methanesulfonyl chloride (5.8 g; 50 mmol) and methane sulfonic acid (0.5 g; 5 mmol). The mixture was heated at 95-105°C for about 18 hours. A sample of the resultant dark brown pasty suspension was tested and found to be 86% 4-HAP mesylate trimer (by normalized LC). The suspension was cooled, quenched in methanol (25 ml), transferred to a concentration flask with methylene chloride and concentrated to give a dark brown solid (26.9 g).
  • methanesulfonic acid (1.9 g; 20 mmol) was heated at 60°C for 7 days, cooled to room temperature and poured over ice (50 g). The reaction flask was rinsed with methylene chloride (25 ml) and the wash was added to the ice, to form an aqueous mixture. The pH of the aqueous mixture was adjusted to basic with sodium carbonate causing
  • THPB 1,3,5-tris(4'-hydroxyphenyl)benzene
  • Tetrachlorosilane (8.5 g; 0.05 mol; 6.0 ml) was then added dropwise with a syringe. The reaction mixture was stirred at room temperature for 72 hours and poured into water (200 ml) to afford a reddish brown solid (7.9 g). HPLC analysis of the crude product revealed it to be THPB (64.4% pure) (86% yield).

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Abstract

Composés de la formule (I) dans laquelle R1 représente hydrogène, alkyle, halogène, nitro ou sulfonyle d'alkyle ou sulfonyle aromatique, x représente un nombre entier compris entre 1 et 4, et lorsque x est supérieur à 1, les substituants de R1 dans l'une des positions 2, 3, 5 et 6 ou dans toutes ces positions peuvent être identiques ou différents, et R représente (III, IV ou V), R2 et R3 représentant chacun un groupe alkyle substitué, un groupe aromatique ou aromatique substitué, R2 et R3 pouvant être identiques ou différents. Des intermédiaires et des procédés de préparation de ces nouveaux composés sont également décrits et revendiqués, ainsi que des procédés permettant d'utiliser ces composés et des dérivés de 4-hydroxyacétophénone, pour produire des composés de 1,3,5-tris(4'-hydroxyphényl)benzène.
PCT/US1992/011015 1992-01-08 1992-12-18 Procede de preparation de 1,3,5- tris(4'-hydroxyphenyl)benzene et de ses derives WO1993014065A1 (fr)

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MX9300054A MX9300054A (es) 1992-01-08 1992-12-18 Procedimiento para la preparacion de 1,3,5-tris(4'-hidroxifenilbenceno y derivados de los mismos y compuestos intermediarios

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* Cited by examiner, † Cited by third party
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CN107011109A (zh) * 2017-03-24 2017-08-04 哈尔滨工业大学（威海） 一种1,3,5‑三苯基苯类化合物的制备方法

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US3458473A (en) * 1968-09-04 1969-07-29 Exxon Research Engineering Co Phenolic antioxidant composition for polyolefins

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US3458473A (en) * 1968-09-04 1969-07-29 Exxon Research Engineering Co Phenolic antioxidant composition for polyolefins

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CHIMIA, 1958, HOPFF et al., "Zur Kenntis des Triphenylbenzols und Seiner Derivative", pp. 143-145. *
J. ORG. CHEM., 1971, KARGER et al., "Mixed Sulfonic Carboxylic Anhydrides", pp. 540-544. *
PROTECTIVE GROUPS IN ORGANIC SYNTHESIS, 1991, GREENE et al., pgs 162-170; 300-301. *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107011109A (zh) * 2017-03-24 2017-08-04 哈尔滨工业大学（威海） 一种1,3,5‑三苯基苯类化合物的制备方法

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