CZ20004439A3 - Epoxidation process for aryl allyl ethers - Google Patents

Abstract

The present invention provides a process for preparing an aromatic glycidyl ether epoxide compounds by contacting allyl ether made from a hydroxy group of an aromatic compound containing a hydroxy group with inorganic or organic a hydroperoxide oxidizing agent in the presence a transition metal complex catalyst; at least a) allylether is conformationally restricted, or b) the transition metal complex catalyst contains at least one or more stable ligands bound to a transition metal. The method of the present invention allows epoxidation of high epoxidation allylaryl ethers yield (e.g., greater than 70 to 90%) and high hydroperoxide selectivity (e.g., greater than 70-90%).

Description

Technical field:

The present invention relates to a process for epoxidizing an allyl ether of an active hydrogen-containing compound, more particularly allylary ethers, by combining allylary ethers with an inorganic oxidizing agent, more specifically aqueous hydrogen peroxide, or with an organic oxidizing agent, more specifically an organic hydroperoxide such as alkyl hydroperoxide or aromatic hydroperoxide. which is capable of forming an epoxide from allylarylethers.

BACKGROUND OF THE INVENTION:

Arylglycidyl ethers, commercially known as epoxy resins, have been successfully manufactured on an industrial scale and used in various industrial and commercial areas. Two types of reactions have been known to date for the preparation of the epoxy moiety of aryl glycidyl ethers. The first type of reaction is the reaction of reactive hydrogen-containing molecules, such as phenols or polyphenols, alcohols or carboxylic acids, with epichlorohydrin under basic conditions in the presence of or without the catalyst (s) to form glycidyl ethers or glycidyl esters. Glycidyl ethers produced by this first reaction process may have a high content of organically bound chlorine, which may be considered undesirable in some applications, such as electronic applications.

In the second type of reaction, the oxidizing agent is used to directly epoxidize the allyl ether or allyl ester of the corresponding reactive hydrogen-containing organic compounds, such as alcohols, phenols or carboxylic acids. Some known oxidizing agents useful in this second type of reaction include, for example, peracetic acid, hydrogen peroxide, dimethyldioxiran, and peroxyimidic acid.

U.S. Pat. U.S. Patent No. 5,578,740 discloses known epoxidation methods for the epoxidation of allylarylethers. These reaction methods include reacting the allyl ethers with a peroxide compound such as peracetic acid and hydrogen peroxide in the presence of a catalytic system such as a NajWO-i / HaPOV quaternary ammonium salt, wherein the quaternary ammonium salt is e.g.

trioctylmethylammonium nitrate.

Because of the cost of the aforementioned known oxidants, epoxidation side reactions or the difficult purification process associated with the above-mentioned epoxidation processes of allyl ethers and / or allyl esters, none of these epoxidation processes using previously known oxidizing agents are commercially viable for the production of large volumes of basic chemicals.

Another known epoxide formation method uses organic oxidizing agents, such as organic hydroperoxide via the oxidation of propylene in the presence of a transition metal catalyst, to prepare propylene oxide. This reaction is limited to the epoxidation of activated or electron-rich aliphatic or cycloaliphatic alkenes such as propylene, cyclohexene and 1-octene. In this known process, which includes the process currently used to produce propylene oxide on a large industrial scale, the limiting amount of the reagent is an oxidizing agent and propylene is used in large excess. The total conversion of propylene to epoxide is low (e.g., less than 50%). Therefore, fractional distillation is used as a separation process to separate the propylene oxide product from unreacted propylene and the unreacted propylene is then recycled back to the reactor in which the epoxidation reaction takes place.

U.S. Pat. U.S. Patent No. 5,118,822 issued to Shum et al. discloses a process for epoxidizing olefins, including monomeric allylphenyl ether, to epoxide compounds by contacting olefins with organic hydroperoxides in the presence of a rhenium salt salt catalyst formed of rhenate anions and cations containing organic compounds of the Va group elements. Shum et al. do not disclose the use of a ligand-containing catalyst and do not report on the yield of phenylglycidyl ether. It is inappropriate to use this acidic rhenate anion of high oxidation state, since this rhenate anion may be a catalyst that promotes the hydrolysis of the epoxy ring.

U.S. Pat. U.S. Patent No. 5,319,114 discloses a process for the olefin epoxidation comprising allylphenyl ethers by reaction of an organic hydroperoxide in the presence of a heterogeneous carbon molecular sieve catalyst comprising a transition metal oxide such as molybdenum oxide. U.S. Pat. No. 5,319,114, the transition metal is captured by absorption on carbon and a stable chemical bond is not formed between the transition metal oxide and the carbon molecular sieve. Thus, the active form of the catalyst is molybdenum trioxide, which is ineffective in providing a high yield of allylphenyl ether epoxidation. U.S. Pat. No. 5,319,114, no yield is disclosed for allylphenyl ether.

U.S. Pat. U.S. Patent No. 5,633,391 issued to Fenelli SP discloses a process for the epoxidation of olefins, including monomeric allylphenyl ether, by mixing olefins with bis (trimethylsilyl) peroxide such as An oxidizing agent in the presence of rhenium oxide as a catalyst in an organic solvent. The conversion of allylphenyl ether to phenylglycidyl ether as described by Fenelli is low (36%) and bis (trimethylsilyl) peroxide is expensive and is not commercially available. In the absence of an organic base as an additive in the epoxidation process described in U.S. Pat. No. 5,633,391 using a rhenium catalyst, the phenylglycidyl ether epoxide will rapidly decompose and hydrolyze to a glycol.

In addition, it has been found that during epoxidation the catalysts disclosed in U.S. Pat. U.S. Patent Nos. 5,118,822; Nos. 5,319,114 and 5,633,391 achieve low yields and therefore would be difficult to apply the methods disclosed in these patents, since most allyl ether substrates and their epoxidation products of commercial importance are high boiling compounds. The use of the methods and catalyst systems disclosed in U.S. Pat. U.S. Patent Nos. 5,118,822; Nos. 5,319,114 and 5,633,391 are therefore limited because of the difficulty of separating the reactant from the product to allow recycling of the reactant.

GB Patent No. 2,309,655 discloses a process for preparing heterogeneous transition metal containing inorganic molecular sieves useful in the oxidation of alkenes, including epoxidation of alkenes, hydrogen peroxide or organic hydroperoxide. However, these heterogeneous catalysts claimed in GB 2,309,655 are not selective, resulting in low epoxidation yields and therefore requires an excess of olefin used. It is also known that the heterogeneous catalysts of GB 2,309,655 are very acidic and the use of such acidic catalysts results in hydrolysis and opening of the epoxy ring of the product to form undesirable glycol products. In addition, GB 2,309,655 provides no data for any epoxidation of allylarylethers.

Thus, it would be desirable to provide a process for epoxidizing allylarylethers lacking the disadvantages of prior art processes, thereby ensuring high conversion of allylarylethers and high yields of epoxidation with good selectivity of the organic oxidizing agent.

SUMMARY OF THE INVENTION:

The present invention is directed to a process for preparing an aromatic glycidyl ether epoxy compound by contacting an allyl ether made from a hydroxy group of an hydroxy-containing aromatic compound with an inorganic or organic hydroperoxide oxidizing agent in the presence of a transition metal catalyst complex. transition metal complex - comprises at least one or more stable transition metal ligands.

«Φ ····

It is an object of the present invention to prepare epoxy portions of aryl glycidyl ethers by epoxidizing allylarylethers with an inorganic or organic hydroperoxide oxidizing agent in the presence of a group of transition metal complexes selected to provide high allylarylether conversion and high epoxidation yield along with good hydroperoxide selectivity.

In general, the present invention is a method of epoxidizing an allyl ether of an active hydrogen-containing compound, more particularly a method of epoxidizing an allylarylether of an aromatic hydroxyl-containing compound prepared by allylating an oxygen atom by contacting the allylarylether with an inorganic or organic oxidizing agent such as aqueous hydrogen peroxide or organic hyperoxide such as alkylhydroperoxide. or an aromatic hydroperoxide, in the presence of a transition metal catalyst that is capable of forming an epoxide from allylarylethers, more specifically to form the epoxy portion of the arylglycidyl ethers.

The process of the present invention can generally be described by reaction according to the following Scheme I:

Scheme I (R ¹ ) x (R ² ) y Ar (OR ³ ) _Z catalyst oxidizing agent (R ¹ ) x (R ² ) y Ar (OR ⁴ ) _Z wherein the catalyst has the following general formula A:

[M ^{+ n} s O _t (Q) _u (L) _v (L ¹ ) v (L ² ) v (L ³ ) v (L ⁴ ) v ... (L ^p ) v] w (G ¹ ) v (G ² ) in (G ³ ) in (G ⁴ ) in ... (G ^p ) in (A)

The various elements of the above reaction equation in Scheme I and the above general formula of the transition metal complex catalyst A are described in more detail in the subchapters that follow.

In one embodiment of the present invention, the present invention relates to a process for the preparation of epoxy moieties of arylglycidyl ethers by epoxidizing allylarylethers, which may optionally be conformationally constrained, with an inorganic or organic oxidizing agent such as aqueous hydrogen peroxide or organic hydroperoxide in the presence of a transition metal complex of the above formula A, which optionally has one or more stable ligands. Thus, in the preparation of glycidyl ether epoxide compounds via allylaryl ethers as shown in Scheme I above, high yields of epoxidation with good oxidizing agent selectivity are achieved.

Allylarylethers

The process of the present invention is generally useful for epoxidizing allyl ether compounds. The method of the present invention is particularly useful for epoxidizing allylarylether compounds. The terms "allylarylether compounds" or "allylarylether" as used herein mean allyl ethers containing an allyl ether moiety attached directly to the aromatic ring; or allyl ethers which comprise an allyl ether moiety and an aromatic ring, but the allyl ether moiety is not directly attached to the aromatic ring, but instead of the allyl ether moiety is attached to the aromatic ring via a linking group such as a polyalkylene oxide group. Typically, the allylarylethers used in the present invention are made from aromatic compounds containing a hydroxyl group. The hydroxyl moiety of the hydroxyl-containing aromatic compound may be directly attached to the aromatic ring of the hydroxyl-containing compound, or the hydroxyl moiety may not necessarily be attached directly to the aromatic ring, but instead the hydroxyl moiety may be attached to the aromatic ring via a linking group such as polyalkylene oxide group.

The allylarylethers required in the present invention can be synthesized by reacting, for example, allyl chloride, methallyl chloride, allyl acetate or allyl carbonate with a hydroxyl-containing aromatic compound precursor in the presence or absence of a catalyst, in the presence of a base or free base as disclosed in e.g. U.S. Patent Nos. 5,578,740; 4,740,330 and 4,507,492.

The process of the present invention is particularly suitable for the epoxidation of aryl monoallyl ethers, aryldiallyl ethers or aryl polyfunctional allyl ethers. An example of an aryldiallyl ether useful in the present invention includes bisphenol-A diallyl ether.

In one embodiment of the present invention, the allylarylethers to be treated are conformationally restricted allylarylethers. The term "conformationally restricted allylarylethers" means that (a) the free rotation of the allylarylether aromatic ring (s) is limited due to the proximity of the atoms on the aromatic ring (s) adjacent to the allylarylether containing ring (s), atomic condensation that limits the mobility of the allylarylether structure, such as the condensation of atoms on adjacent aromatic rings that may be observed with bifenol; (b) the free rotation of the allylarylether aromatic rings is limited due to the presence of a rigid moiety (s) attached to the allylarylether aromatic ring (s) that restrict the mobility of the allylarylether structure, such as those rigid moieties that may be found in in the case of aromatic rings of stilbene and fluorene, or in the case where the aromatic rings are linked by groups such as amide groups or ester groups; or (c) the free rotation of the allylarylether group (s) on the aromatic ring (s) of the allylarylether structure (s) is restricted due to the presence of at least one or more substituents on the aromatic ring (s) ortho to the allylarylether (s) to the group (s), namely that the allylarylether group (s) is sterically hindered. Examples of such substituents include methyl, ethyl, isopropyl, tert-butyl, bromine and chlorine, and these groups may be partially or fully fluorinated.

There is a theory that when any of the conformationally restricted allylarylethers defined above are used, deactivation of the epoxidation catalyst is prevented or prevented. Further, there is a theory that the epoxidation catalyst is inactivated because the interaction between the epoxide from allylarylether and the transition metal will lead to hydrolysis of the epoxide ring to form a hydrolyzed glycol. Excess of such a glycol, which is a strong ligand for the transition metal, can reduce the activity of the catalyst by preventing the coordination of the hydroperoxide to the active metal center and / or preventing allylarylether access to the catalytic site, and thus the glycol will act as a catalyst deactivator. However, it is contemplated in the present invention that the use of a conformationally restricted aryl ether will prevent or prevent the formation of a hydrolyzed glycol arylglycidyl ether, which will prevent or prevent the deactivation of the epoxidation catalyst.

In one embodiment of the present invention, allylarylethers containing an alkyl, phenyl or halogen substituent on the aromatic rings at the ortho position to the allylarylethers are used in the epoxidation process described herein, which may provide a high conversion of allylarylether to epoxide (e.g., in the range of more than 70% to 90%). ) and high selectivity of the organic hydroperoxide oxidizing agent (e.g., in the range of more than 70% to 90%).

In another embodiment of the present invention, the allylarylethers useful in the present invention are represented, without limitation, by the structures of the following formulas (I) to (V). The following formula (I) represents a generally preferred group of allylarylethers used in the present invention:

(R ¹ ) x (R ² ) y Ar (OR ³ ) 2 (I)

In formula I, x is from 0 to 750, y is from 0 to 750, and z is from 1 to 150.

In Formula I, Ar is a single-core aromatic ring moiety, such as phenyl. Ar may also be a ring-containing aromatic ring moiety such as biphenyl, 2,2-diphenylpropane, bisphenylene oxide, tetrakis (1,1,2,2-phenyl) ethane, stilbene, phenol-formaldehyde resins, cresol-formaldehyde resins , phenol-dicyclopentadiene resins and hyperbranched aromatic phenol dendrimers. Ar may also be a portion containing condensed aromatic rings formed of many nuclei, such as naphthalene, anthracene, and naphthalene-formaldehyde resins. Ar may also be a moiety comprising condensed aromatic rings consisting of multiple nuclei with one or more heteroatoms, such as O, N, S, Si, B or P, or a combination of such heteroatoms, such as quinoxaline, thiophene and quinoline. Ar may also be a group comprising aromatic ring (s) formed by one or more cores fused to an aliphatic ring (s) such as indane, 1,2,3,4-tetrahydronaphthalene and fluorene. Ar may also be a group comprising aromatic ring (s) formed by one or more cores fused to an aliphatic ring (s) containing one or more heteroatoms such as O, N, S, Si, B or P, or a combination of these heteroatoms, e.g. chroman, indoline and thioindan. Ar as described above for Formula I may be partially or fully fluorinated.

In formula I, Ar may also be a moiety containing aryl groups in which each aryl group is attached to oligomers of an organosiloxane unit (eg, polymers with an average molecular weight of less than 5000) or an organosiloxane unit with a high molecular weight (eg, with medium relative molecular mass greater than 5000). Aryl groups are attached directly to the Si atoms of the organosiloxane units, or these aryl groups are attached to the Si atoms indirectly via an organic aliphatic moiety, an organic cycloaliphatic moiety, an organic aromatic moiety, or a combination thereof. The organic aliphatic, cycloaliphatic or aromatic moiety should not contain more than 20 carbon atoms. When the Ar moiety comprises such oligomeric organosiloxane units or high molecular weight organosiloxane units, z is preferably 1 to 150.

In one embodiment of the present invention, the Ar moiety of Formula I is conformationally constrained. By "conformationally constrained" is meant that (a) the free rotation of the aromatic ring (s) of the Ar moiety containing the allyl ether is limited due to the proximity of the atoms on the ring (s) of the Ar moiety containing the allyl ether group (s) and the aromatic ring (s) of the Ar moiety, which may or may not contain the allyl ether group (s), providing a condensation of the atoms that limits the mobility of the aromatic ring (s) of the Ar moiety containing the allyl ether, such as eg in the case of aromatic rings of bifenol; (b) the free rotation of the aromatic ring (s) of the Ar moiety containing the allyl ether is restricted due to the presence of rigid moiety (s) such as -CH = CR ⁵ -, amide groups and ester groups linking the aromatic the ring (s) containing the allyl ether with the other aromatic ring (s) of the Ar moiety, which may or may not contain the allyl ether group (s), which limits the mobility of the aromatic ring (s) of Ar allyl ether containing moieties; or c) the free rotation of the OR ³ group on the aromatic ring (s) of the Ar moiety is limited due to the presence of at least one or more bulky sterically hindering R ¹ groups other than hydrogen in the ortho position relative to the OR ³ group (s).

In formula I, R ^{1 is a} group that replaces a hydrogen atom at a position that is ortho to the OR ³ group (s) on the aromatic ring (s) of the Ar moiety. R ¹ is halogen such as bromine and chlorine; or a hydrocarbon radical such as an alkyl group, a cycloaliphatic group or an aromatic group. R ¹ is preferably an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl or isopropyl; a cycloaliphatic group having 3 to 20 carbon atoms, such as cyclopentyl and cyclohexyl; an aromatic group having 6 to 20 carbon atoms such as phenyl and naphthyl; or any combination thereof. The aforementioned hydrocarbon residues may also contain one or more heteroatoms such as O, N, S, Si, B or P, or any combination of these heteroatoms. An example of a hydrocarbon radical containing an O heteroatom is ^x methoxy, ethoxy or polyalkylene oxide derived from ethylene oxide, propylene oxide, butylene oxide and cyclohexenoxide. R ¹ of formula I as described above may also be partially or fully fluorinated.

In one preferred embodiment, there is at least one or more R ¹ substituents in the ortho position (s) relative to the OR ³ group (s) on the aromatic ring (s) of the Ar moiety because in such cases the allyl ether conversion, epoxidation yield and hydroperoxide selectivity are very high compared to an allyl ether having no R ¹ substituent (s) at ortho position (s) relative to the OR ³ group (s).

In formula I, R ^{2 is a} group that replaces a hydrogen atom in a position that is not ortho to the OR group (s) on the aromatic ring (s) of the Ar moiety. R is halogen such as bromine and chlorine; or a hydrocarbon radical such as an alkyl group, a cycloaliphatic group or an aromatic group. R ² is preferably an alkyl group having 1 to 20 carbon atoms, e.g., methyl, ethyl or propyl; a cycloaliphatic group having 3 to 20 carbon atoms, such as cyclopentyl and cyclohexyl; an aromatic group having 6 to 20 carbon atoms such as phenyl and naphthyl; or any combination thereof. The aforementioned hydrocarbon residues may also contain one or more heteroatoms such as O, N, S, Si, B or P, or any one of them. Fr * a combination of these heteroatoms. An example of a hydrocarbon radical containing an O heteroatom is a methoxy group, an ethoxy group or a polyalkylene oxide group derived from ethylene oxide, propylene oxide, butylene oxide and cyclohexenoxide. R ² of formula I as described above can also be partially or completely fluorinated.

In formula I, OR ^{3 is a} propenyl group-containing oxy group that replaces the hydrogen atom on the aromatic ring (s) of the Ar moiety, wherein R ³ is preferably a propenyl group-containing moiety selected from:

-C (R ⁵⁾ 2 CR ⁵ = C (R ⁵⁾ 2, -C (R ⁵⁾ ₂ C (R ⁵⁾ 2 CR ⁵ = C (R ⁵⁾ 2, and

wherein R ⁵ is hydrogen or an alkyl group, a cycloaliphatic group or an aromatic group and i is 0 to 6. R ⁵ is preferably an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl and propyl; a cycloaliphatic group having 3 to 20 carbon atoms, such as cyclopentyl and cyclohexyl; an aromatic group having 6 to 20 carbon atoms such as phenyl and naphthyl; or any combination thereof. Each R ⁵ may be the same or different from the others.

In the general formula I, R ³ may also be a monoalkylene oxide group or a polyalkylene oxide group derived from ethylene oxide, propylene oxide, butylene oxide or cyclohexenoxide, wherein each monoalkylene oxide or each polyalkylene oxide unit is terminated with a propenyl group selected from:

-C (R ⁵⁾ 2 CR ⁵ = C (R ⁵⁾ 2, -C (R ⁵⁾ ₂ C (R ⁵⁾ 2 CR ⁵ = C (R ⁵⁾ 2, and

wherein R ⁵ is the same group as described above.

In one embodiment, when R ³ in formula I above is -CH 2 C = CH 2, the ether is "allyl ether"

In another embodiment, when R ³ in formula I above is -CH 2 C (CH 3) = CH 2, the aryl ether is a "methallyl ether".

In yet another embodiment, wherein R ³ in the above formula (I) is an aryl ether "cyclohexen-3-yl ether".

More specific and preferred examples of allylarylethers useful in the present invention are represented by the following formulas II to V.

Examples of a single aromatic ring allylarylether useful in the present invention are represented by the following general formula II:

In formula II, R ¹ , R ² , OR ³ and R ^{3 have the} same meaning as described above for formula I. In formula II, x is from 0 to 4, y is from 0 to 3 and z is from 1 The allylarylethers of the formula II can be prepared from aromatic hydroxyl-containing precursors such as 2,6-dimethylphenol, 2,6-diisopropylphenol and 2,6-dibromophenol.

Other examples of allylarylethers useful in the present invention are the two aromatic ring allylarylethers represented by the following general formula ΙΠ.

X

(AB ³ ) _Z (ΙΠ)

In formula III, R ¹ , R ² , OR ³ and R ^{3 have the} same meaning as described above for formula I. In formula III, each x is from 0 to 3 and each x can be the same or different, each y is from 0 to 3 and each y can be the same or different, and each of is from 1 to 2 and each of can be the same or different.

In formula III, X can be nothing; or X may be a heteroatom with or without substituents on the heteroatom to complement its necessary valence; the heteroatom is selected from O, N, S, Si, B or P, or any combination of two or more of said heteroatoms; X may also be, for example, -C (O) -; -S (O 2) -; -C (O) NH-; -P (O) Ar-; an organic aliphatic moiety with or without heteroatoms such as oxydimethylene, methylene, 2,2-isopropylidene, isobutylene and -CR ⁵ = CH-, wherein R ⁵ is the same as defined above for Formula I; a cycloaliphatic group with or without heteroatoms, such as a cycloaliphatic ring of more than 3 carbon atoms; or an aromatic group with or without heteroatoms; or any combination thereof, preferably containing less than 60 carbon atoms, X, as described above for the general formula ΙΠ, may be partially or fully fluorinated, such as 2,2-perfluoroisopropylidene.

Prodrugs suitable for the preparation of allylarylethers of the general formula ΠΙ include, for example, 4,4'-dihydroxybiphenyl; 3,3,, 5,5 etr-tetramethyl-4,4--dihydroxybiphenyl; 3,3 ´, 5,5´-tetramethyl-2,2 ´, 6,6´-tetrabromo-4,4´-dihydroxybiphenyl; bis (4-hydroxyphenyl) methane; bis (4-hydroxyphenyl) sulfone; 4,4´-bis (2,6-dibromophenol) isopropylidene; 2,2´-bis (4-hydroxyphenyl) propane; bisphenol K; 9,9-bis (4-hydroxyphenyl) fluorene; 4,4´-dihydroxy-α-methylstilbene and 1,3-bis (4-hydroxyphenyl) adamantane.

Other examples of allylarylethers useful in the present invention are multi-aromatic ring allylarylethers represented by the following general formula IV:

In the general formula (IV), the groups R ¹ , R ² , OR ³ , R ³ and X have the same meaning as described above for the general formula ΙΠ. In formula IV, each x is from 0 to 3 and each x may be the same or different, each y is from 0 to 3 and each y may be the same or different, and each of is from 1 to 2 and each of may be the same or different. In formula IV, m is from 0.001 to 10.

Prodrugs suitable for the preparation of allylarylethers of formula IV include, for example, phenol-formaldehyde resins (more than 2 functional groups); o-cresol-formaldehyde resins (more than 2 functional groups); phenol-dicyclopentadienyl resin (more than 2 functional groups) and naphthol-formaldehyde resin (more than 2 functional groups).

Other examples of allylarylethers useful in the present invention are multi-aromatic ring allylarylethers which are represented by the following formula (V):

(IN)

In formula V, R ¹ , R ² , OR ³ and R ^{3 have the} same meaning as described above for formula I. In formula V, each x is from 0 to 3 and each x can be the same or different, each y is from 0 to 3 and each y can be the same or different, and each of is from 1 to 2 and each of can be the same or different.

In the general formula V, Y is an organic aliphatic moiety with heteroatoms such as O, N, S, Si, B or P, or any combination of two or more of said heteroatoms, or without heteroatoms having 1 to 20 carbon atoms, such as e.g. a methine group; a cycloaliphatic moiety with or without heteroatoms having 3 to 20 carbon atoms, such as a cyclohexanetriyl group; an aromatic moiety with or without heteroatoms, such as benzentriyl, naphthalentriyl, fluorentriyl; or any combination thereof with less than 20 carbon atoms. Y, as described above for formula V, may be partially or fully fluorinated, such as a fluoromethine group.

In formula V, m 'is generally 3 or 4. However, Y may also be an oligomeric organosiloxane unit (e.g., having an average molecular weight less than 5000) or a high molecular weight organosiloxane unit (e.g., having an average relative molecular weight greater than 5000). 5000). In this case, the aryl groups are attached to the Si atoms of the organosiloxane unit directly or through an organic aliphatic group, a cycloaliphatic group, an aromatic group or any combination thereof with less than 20 carbon atoms. When Y is an oligomeric organosiloxane unit or a high molecular weight organosiloxane unit, m 'in formula V is preferably 1 to 150.

Prodrugs suitable for the preparation of allylarylethers of formula V include, for example, tris (4-hydroxyphenyl) methane and 1,1 ', 2,2'-tetrakis (4-hydroxyphenyl) ethane.

In preferred embodiments of the present invention, there is at least one or more R ¹ substituents in the ortho position (s) relative to the OR ³ group (s) on the aromatic ring (s) of formulas II to V, since in such cases the conversion of allyl ethers, epoxidation yield and hydroperoxide selectivity very high compared to an allyl ether having no R ¹ substituent (s) at ortho position (s) over OR ³ group (s).

In other preferred embodiments of the present invention, in formulas (III) to (V), the proximity of the atoms on the aromatic ring (s) adjacent to the allylarylether containing ring (s) provides proximity of the atoms which limits the mobility of the allylarylether structure; or a rigid moiety (i) attached to the aromatic ring (s) of the allylarylether structure that limits the mobility of the allylarylether structure is present. In these cases, the conversion of allyl ethers, the yield of epoxidation and the selectivity of the hydroperoxide are very high compared to the case where the allylarylethers lack the effect of atomic thickening or the effect of the rigid moiety connecting the aromatic rings.

Oxidizing agents

The oxidizing agents useful in the present invention may be inorganic or organic hydroperoxides. Inorganic hydroperoxides used as oxidizing agents in the process of the present invention generally include, for example, hydrogen peroxide. In general, the hydrogen peroxide used is an aqueous hydrogen peroxide solution containing 3 to 80% by weight hydrogen peroxide.

Hydrogen peroxide is reduced to water during epoxidation. To prevent deactivation by the catalyst, it may be necessary to remove the resulting water during the reaction from the reactor. It is known that water is a ligand for some catalysts and therefore may slow the epoxidation reaction or may hydrolyze and decompose the transition metal complex catalyst. Co-distillation of solvent water by passage through a fractional distillation column will remove this water from the epoxidation reaction mixture.

The organic hydroperoxides used as oxidizing agents in the process of the present invention can generally be any organic compounds containing at least one hydroperoxide (-OOH). functional group. However, secondary and tertiary hydroperoxides are preferred because of their higher stability and greater safety compared to primary hydroperoxides. The organic hydroperoxide used in the present invention preferably has the following general formula 1:

R _a

R-C-OOH (1) ^R c wherein R a, R b and R c are the same or different and may be selected from hydrogen; an alkyl group such as methyl or ethyl; a cycloaliphatic group such as cyclohexyl; an aromatic group such as phenyl; or a combination thereof. The combination of two or more R _a , R b and R c may also be contained in the same structural unit as in the case of a pinanyl group.

Examples of organic hydroperoxides useful in the present invention include tert-butyl hydroperoxide (TBHP); tert-amyl hydroperoxide; cumene hydroperoxide; ethylbenzene hydroperoxide; cyclohexanhydroperoxide; methylcyclohexanhydroperoxide; pinanhydroperoxide; tetrahydronaphthalene hydroperoxide; isobutylbenzene hydroperoxide; isopropyl hydroperoxide; and ethylnaphthalene hydroperoxide. A preferred hydroperoxide is t-butyl hydroperoxide or t-amyl hydroperoxide. Mixtures of organic hydroperoxides may also be used in the present invention.

Organic hydroperoxides may be prepared by air oxidation of the corresponding alkane or aromatic hydrocarbon prior to use. Alternatively, the organic hydroperoxide may be formed in situ. A process for preparing the organic hydroperoxide in situ is possible, but is generally more difficult to control than the previously prepared organic hydroperoxide.

The hydroperoxide is reduced to alcohol during epoxidation. For example, tert-butyl hydroperoxide is reduced to tert-butanol. In order to prevent deactivation of the catalyst system, it may be necessary to remove the alcohol formed during the reaction from the reactor. It is known that alcohols are ligands for some catalysts and therefore may slow the epoxidation reaction. Codestillation of the alcohol with the solvent by passing through the fractional distillation column will remove the solvent, alcohol and organic hydroperoxide. The unused organic hydroperoxide can then be recycled back to the reactor.

The organic hydroperoxide may be present in water or an inert organic solvent which is the same or different from the solvent used in the epoxidation reaction, if the solvent is used. In some cases, the organic hydroperoxide may contain some of the water that is present in the organic peroxide prior to use. In cases where transition metal complexes such as Mo (CO) 6 are water sensitive, the water content of the organic hydroperoxide is preferably less than 5%, more preferably less than 0.5% and most preferably less than 0.05 %. If the water content of the organic hydroperoxide is greater than 0.05%, it is advantageous to remove the water by known methods before use. Water may be removed from the hydroperoxide prior to use, for example, by drying the organic hydroperoxide with molecular sieves having a cavity size of 0.4 µm. In another embodiment, water from the hydroperoxide can be removed prior to use of the hydroperoxide by azeotropic distillation of water with solvent (s). When aqueous hydroperoxide oxidizing agents are used, hydrolysis-stable or hydrophobic catalysts are usually selected.

In a preferred embodiment, the ratio of the inorganic or organic hydroperoxide used in the epoxidation of the aryl ether is preferably in the range of 0.6 mol to 20 mol of hydroperoxide to 1 equivalent of allylarylethers. More preferably, the ratio of hydroperoxide used in epoxidizing the aryl ether is in the range of 1 mole to 5 moles of hydroperoxide to 1 equivalent of allylarylethers. Most preferably, the ratio of hydroperoxide used in the epoxidation of the aryl ether is in the range of 1 mole to

2.5 mol of hydroperoxide to 1 equivalent of allylarylethers. One equivalent of hydroperoxide is theoretically needed to oxidize one equivalent of a monoallyl ether substrate, but in order to optimize conversion to epoxide, it may be desirable to use an excess of hydroperoxide oxidizing agent.

In carrying out the reaction of the present invention, the hydroperoxide oxidizing agent may be added to the rector in a single dose along with the allylarylether of formulas I to V. When a large amount of hydroperoxide oxidizing agent is used, it is preferable to add the oxidizing agent in portions. In another embodiment, the hydroperoxide oxidizing agent may be added to the reactor in a continuous manner concurrently with the allylary ether.

Catalysts and ligands

In general, the transition metal catalysts used in the present invention are represented by the following general formula A:

[M ^{+ n} with Ot (Q) _u (H) _v (L ¹ ) v (L ² ) _v (L ³ ) v (L ⁴ ) v ... (L ^p ) _v ] w (G ¹ ) v ( G ² ) v (G ³ ) v (G ⁴ ) v ... (G ^p ) v (A) where M is a transition metal; n is the oxidation degree of the metal M and n is 0 or an integer from 1 to 7; s is an integer from 1 to 5;

O is oxygen, which in the above formula A is bonded to metal M to form an oxometallic moiety having the following general structure:

M = O;

or O is oxygen, which in the above formula A connects the metal M with H, or M with the other M to form a μ-oxometallic moiety having one of the following general structures:

Μ -O-H or Μ-O-M;

or O is oxygen, which in the above formula A is bonded to metal M to form an anionic oxometallic moiety having the following general structure:

M-O ';

and t is an integer from 0 to 3.

Q is O ₂ , where O is oxygen and Q is the peroxy group attached in the above formula to metal M so as to form a three membered ring, one of which is a metal atom M and the other two are a peroxy group, as shown in the following general structure:

and u is an integer from 0 to 3.

In the above general formula A, H is a hydrogen atom that is attached to the metal atom M to form the following general structure:

M-H;

or H is hydrogen which is attached to the oxygen of the μ-oxometallic moiety having the following general structure.

M-O-H.

Each group of L ¹ , L ² , L ³ , L ⁴ ... L ^p in the above general formula A is a different ligand up to the maximum number of L ^p ligands; each group of G ¹ , G ² , G ³ , G ⁴ ... G ¹ * in the above general formula A is a different counterion to the M-O 'moiety up to the maximum number of cations ^Gp ; v is an integer from 0 to 10; and w is an integer from 1 to 10.

In the above general formula A, M is a transition metal. Preferably, M is a transition metal selected from d ° elements such as Ti, Zr, V, W, Mo, Re or Mn, or from δ elements such as La and Ac. Preferably, the transition metal M is selected from Group IIIa, Group IVa, Group Va, Group VIa and Group VIIa elements (former IUPAC notation of the Periodic Table of the Elements); or from group 3, group 4, group 5, group 6 and group 7 (new IUPAC notation of the periodic table of elements); more preferably, the transition metal M may be selected from the group of elements comprising V, Mo, W, Mn and Re. When s is greater than 1 and when w is greater than 1, or when s is equal to 1 and w is greater than 1, M may be the same transition metal, or it may be a combination of two or more different transition metals.

The oxidation state n of the metal M can be 0 to 7. The highest oxidation state M complies with the 18-electron rule for d ° transition elements. For example, for Mo (CO) 6 n is 0. If s is 1 and t is from 0 to 3, then the oxidation state n of the metal M can be 0 to 7. When the oxidation state n of the metal M is higher the oxidation state, ie n is 7, so the metal M comprises eg Re and Mn. When higher oxidation metals such as Re and Mn are used in the present invention, an equivalent or a slight excess (depending on the metal) of basic ligands such as pyridine is preferably used to reduce the acidity of such metal complex types and pyrazole, or buffering agents, so that the acidic nature of these metals does not degrade both the oxidizing agent and the resulting epoxy product.

In the above general formula A, the integer is from 0 to 10 for a single metal and v may be the same or different for H, any of L ¹ , L ² , L ³ , L ⁴ ... L ^p and any of the groups G ^1, G ^2, G ^3, G ⁴ ... G *

Total number of Ot, (Qk (H) _v , (L ') _v , (L ² ) v, (L ³ ) _v , (L ⁴ ) v ... (L ^p ) va (G \, (G ² ) _v , (G ³ ) v, (G ⁴ ) v ... (G ^p ) v satisfies the binding properties of transition metal M. For d ° metal element, the total number of electrons in orbital is less than or equal to 18.

In a preferred embodiment, the transition metal complex useful as a catalyst in the present invention may include, for example, single metal complexes or single metal oxocomplexes such as Mo (CO 6); MOO2Cl2; MoChiXyLMe ^; MOO2;

MoO ₃ ; Cp ₂ MoCl ₂ ; Cp * MoO ₂ Cl; Cp ₂ MoCl ₄ ; Cp2WCl ₂ ; Cp ₂ ReCl ₃ ; Cp ₂ 'MoOCl ₂ ; CpV (CO) ₄ ;

· «····· ·· ···· · · ·

CpíVCb; Cp ₂ * VOCl ₂ ; Cp ₂ V; V (CO) ₅ ; CH ₃ ReO ₃ and Cp * Re (CO) ₅ Cl; wherein Cp is a cyclopentadienyl ligand and Cp * is a pentamethylcyclopentadienyl ligand.

In another preferred embodiment, the transition metal complex useful as a catalyst in the present invention may include, for example, bimetallic complexes, polymetallic complexes, bimetallic oxocomplexes, polymetallic oxocomplexes, and metal clusters. In such an embodiment, the metal atoms may be linked to each other via metal-metal bonds, but such a bond is not a requirement. Alternatively, the metal atoms can be linked to each other via an oxygen atom, such as in the μ-oxometallic portion of MOM. The metal atoms may also be linked to one another via bidentate or multidentate ligands which contain, for example, sulfur atoms, nitrogen atoms or phosphorus atoms. Bimetallic complexes or clusters and heterobimetallic complexes or clusters that are useful in the epoxidation of allylarylethers with inorganic or organic hydroperoxides are complexes such as [CpMo (CO) ₂ ] ₂ ; [Cp * Mo (CO) ₂ ] ₂ ; [CpW (CO) ₂ ] ₂ and [Cp * W (CO) ₂ ] ₂ , wherein Cp is a cyclopentadienyl ligand and Cp * is a pentamethylcyclopentadienyl ligand.

In another preferred embodiment, the transition metal complex useful as a catalyst in the present invention may include transition metal complexes with peroxostructures such as peroxomolybdenum complexes, e.g., MoO (O ₂ ) L ₂ , wherein L is hexamethylphosphoric triamide or picolinic acid, ( LL) MoO (O ₂ ) 2, where LL is 2- (1-octyl-3-pyrazoyl) pyridine, and VO (O ₂ ) (L) (H ₂ O) ₂ , wherein L is picolinic acid; and diperoxomolybdenum oxocomplexes, e.g., MoO (O ₂ ) L, wherein L is endo, endo-3- (diphenylphosphoryl) -2-hydroxyboman. The structures of the peroxo and diperoxocomplexes of transition metals useful in the present invention are in no way limited by the above structures.

Mo, W and Re complexes are commercially available, e.g., from Aldrich Chemical Company, Inc. Commercially available Mo complexes can typically be used as catalysts without further chemical modification of their structure.

Each cation G ¹ , G ² , G ³ , G ⁴ ... G ^P in the above general formula A can be an inorganic cation of the Ia alkali metal group, such as Na ⁺ , K ⁺ or Cs ⁺ ; or from the Ha group of an alkaline earth metal such as Mg ²⁺ or Ca ²⁺ ; or from an Ulb metal group such as Al ³⁺ ; or a cation comprising an organic compound of an element of the Vb group, wherein the cation is formed by at least one element of the Vb group and at least one organic substituent bound to the element of the Vb group. The above groups are defined by the old IUPAC notation of the Periodic Table of the Elements.

Specifically, each group of G ¹ , G ² , G ³ , G ⁴ .G ^P in formula A above is a cationic moiety formed by at least one or more quaternary cationic centers selected from nitrogen, phosphorus, arsenic, antimony or bismuth, with one or more organic substituents attached to each quaternary cationic center. These organic substituents may be hydrocarbons having 1 to 20 carbon atoms selected from the group consisting of linear, branched or cyclic aliphatic or aromatic hydrocarbons with or without heteroatoms selected from the group consisting of N, P, S, O, Si or halides, such as F, Cl, Br and J, or combinations thereof. Examples of quaternary nitrogen-containing cationic centers having only one cationic center useful in the present invention are tetramethylammonium, tetraethylammonium, tetraisopropylammonium, tetra-n-butylammonium, tetraisobutylammonium, tetra-n-hexylammonium tetra-n-octylammonium, tetisooktylammonium, tetraisooktylammonium benzyltrimethylammonium, benzyltriethylammonium, benzyltrihexylamonium, benzyltri-n-oktylamonium, decyltrimethylamonium, tetradodecylamonium, hexadecyltrimethylammonium, hydroxyethyltrimethylamonium, hydroxyethyltriethylamonium, trimethoxysilylpropyltri-n-butylammonium, triethoxysilylpropyltri-n-butylammonium, trimethoxysilylpropyltrimethylamonium, trimethoxysilylpropyltriethylamonium, and n-oktadecyldimethyltrimethoxysilylpropylamonium tetradecyldimethyltrimethoxysilylpropylamonium.

Examples of quaternary nitrogen-containing cationic centers having more than one cationic center useful in the present invention are, for example, Ν, Ν, Ν, Ν, Ν, hexamethylethylenediammonium; Ν, Ν, Ν, Ν, Ν, hexaethylethylenediammonium; Ν, Ν, Ν, ’, N’, hex-hexamethylpropylene-1,3-diammonium; and Ν, Ν, Ν, ’, Ν, N--hexaethylpropylene-1,3-diammonium.

Examples of quaternary phosphorus-containing cationic centers having only one cationic center useful in the present invention are tetramethylphosphonium, tetraethylphosphonium, tetra-n-propylphosphonium, tetraisopropylphosphonium, tetra-n-butylphosphonium, tetraisobutylphosphonium, tetraheptylphosphonium, tetraheptylphosphonium, tetraheptylphosphonium, tetraheptylphosphonium, tetraheptylphosphonium, , ethyltritoluylphosphonium, cyclohexyltriphenylphosphonium, 2-chloroethyltriphenylphosphonium, 2-butyltriphenylphosphonium, tetrabenzylphosphonium, allyltrimethylphosphonium, allyltriphenylphosphonium and trimethylsilylethoxy ethyltriphenylphosphonium.

When the organic, inorganic or hybrid organic-inorganic oligomeric or polymeric structure comprises more than one hydrocarbon substituent selected from the group consisting of linear, branched, cyclic aliphatic or aromatic hydrocarbons having 1 to 20 carbon atoms with or without heteroatoms such as N, P, S, O, Si or halides such as F, Cl, Br and J, or combinations thereof; and when these hydrocarbon substituents are attached to an oligomeric or polymeric chain and attached to a quaternary cationic center, the organic, inorganic or hybrid organic-inorganic oligomeric or polymeric structure may be ionically bonded to more than one transition metal atom. In such a case, the transition metal complexes are anchored or bound to the organic, inorganic or hybrid organic-inorganic polymer chain via more than one hydrocarbon substituent containing a cationic center. An example of such a hydrocarbon substituent on a polymer chain containing a cationic center is the benzyltrimethylammonium group formed when the cross-linked polystyrene is first chloromethylated and then aminated with trimethylamine.

When the cationic center containing a trimethoxysilyl or triethoxysilyl group, such as e.g. trimethoxysilylpropyltri-n-butylammonium, triethoxysilylpropyltri-n-butylammonium, trimethoxysilylpropyltrimethylamonium, trimethoxysilylpropyltriethylamonium, oktadecyldimethyltrimethoxysilylpropylamonium, n-tetradecyldimethyltrimethoxysilylpropylamonium and trimethylsilylethoxyethyltrifenylfosfonium condensed with tetraethoxysilane, thereby forming a sol-gel, silicate or zeolite containing multiquartemic ammonium or quaternary phosphonium cationic centers. When these quaternary cationic centers form ionic bonds with the transition metal complex, the transition metal complex is anchored or bound to the sol-gel, silicate or zeolite. The silicate and zeolite solid phases useful in the present invention are, for example, those with a microporous crystalline structure having a pore size similar to a type 4A molecular sieve (0.4 μηι pore size), or such a mix-porous crystalline structure having pores larger than a molecular sieve Type 4A. Zeolites, silicates, aluminophosphates and silica aluminophosphates useful in the present invention are, for example, TS-1, TS-2, ZSM-5, ZSM-11, ZSM-12, ZSM-22, AZM-48, SAPO-5, SAPO-11 , zeolite X, zeolite Y, Linda type L, VPI-5, NCL-1, MCM-41 and MCM-48.

Each of the ligands L ¹ , L ² , L ³ , L ⁴ ... L ^P in the above general formula A can be either labile, weakly bound, neutral or basic unidentate ligand; a strongly bound, non-interchangeable, neutral or basic bidentate or multidentate ligand; or combinations thereof. When the ligand is a multidentate ligand, it may be bound to the same metal atom, or to two or more different metals. In addition, the ligands may be attached to an organic polymer chain, an inorganic polymer chain, or a hybrid organic-inorganic polymer chain. When the ligands are anchored in this manner, the transition metal catalyst is anchored or bound to the polymer chain.

When the ligands are not part of an organic or inorganic polymer, such as an organosiloxane or silicate, the total number of carbon atoms and heteroatoms in each ligand is generally between 1 and 100, and preferably between 5 and 100, excluding the hydrogen atom.

When the ligands are part of an organic or inorganic polymer, such as an organosiloxane or silicate, the total number of carbon atoms and heteroatoms in each ligand is generally in the range of 100 to 50,000, and preferably in the range of 100 to 25,000, excluding the hydrogen atom.

The ligands in formula (A) above may also contain heteroatoms such as O, N, S, Si, B and P, or any combination of two or more of these heteroatoms. The ligands in formula (A) above may also contain one or more asymmetric or chiral centers.

In yet another preferred embodiment of the present invention, the transition metal catalyst comprises at least one or more stable ligands attached to the transition metal. In particular, this type of catalyst is preferably used when the allylarylether is not conformationally constrained as defined above. By "stable ligand" is meant it is preferred that the ligand is strongly bound, eg, a coordinated or ion-bound, non-interchangeable monodentate, bidentate, or multidentate ligand, or a combination thereof, which is firmly bound to the metal center during epoxidation.

In addition, a "stable ligand" means that the ligand does not react with the oxidizing agent, the additives to the reaction, or the epoxidation product, and that it is not damaged by the temperature, time or other conditions of the reaction.

Stable ligand (s) on the catalyst is desirable because it has been found that certain glycidyl ethers, such as phenylglycidyl ether, which is the product of allylphenyl ether epoxidation, can function as metal ligands. This type of interaction between the epoxide from allylarylethers and the transition metal can lead to the hydrolysis of the epoxide ring to form a glycol. Excess of this glycol, which is a strong ligand for the transition metal, can reduce the activity of the catalyst by preventing the coordination of the hydroperoxide with the transition metal and / or by preventing allylarylethers from accessing the active site of the catalyst. Thus, excess glycol will act as a catalyst deactivator.

In addition, it has surprisingly been found that when different substituents are placed in the ortho positions on the aryl group relative to the allyl ether or methallyl ether group of allylarylethers, the size of these substituents dramatically affects allylarylether conversion, epoxidation rate, epoxidation selectivity and organic hydroperoxide efficacy. catalyst performance. In general, the larger the substituents on the aromatic ring are ortho positions to the allyl ether and methallyl ether groups, the better the yield of epoxidation. For example, when an isopropyl group or bromine is placed on an aryl group at both ortho positions to the methallyl ether (formula Π), more than 90% yield of methallyl ether epoxidation and TBHP selectivity is achieved.

In addition, it has been found that the dramatic effect on allylarylether conversion, epoxidation rate, epoxidation selectivity, and hydroperoxide efficiency is when the free rotation of the allyl ether or difunctional arylmethallyl ether-containing aromatic rings is limited due to the proximity of atoms on aromatic rings adjacent to the arylmethallyl ether ring. The proximity of the atoms on the aromatic rings adjacent to the arylmethallyl ether containing rings provides a densification of the atoms that limits the mobility of the arylmethallyl ether containing rings, e.g., such densification of the atoms on adjacent aromatic rings that may be observed for bifenol. Better allylarylether conversion results, epoxidation yield, reduced impurity formation in the epoxidation end product, and hydroperoxide efficiency indicate improved catalyst activity and performance.

Without wishing to be bound by theory, it is believed that epoxidized allylarylethers having large substituents on aromatic rings at ortho positions to glycidyl ether groups and / or those in which condensation of atoms on aromatic rings adjacent to aromatic rings containing a glycidylether group exists, both limit the mobility of glycidyl ether groups, they cannot function as metal ligands. That is, during the catalytic epoxidation process, glycidyl ethers cannot approach the transition metal atom and form coordinating ligands. Thus, if the glycidyl ether cannot advantageously form a coordinating ligand with the center of the transition metal atom, the epoxy rings cannot be hydrolyzed to form an excess of glycol. Excess of this glycol, which is a strong transition metal ligand, can reduce catalyst activity by preventing the coordination of the hydroperoxide to the active metal center and / or preventing allylarylether access to the catalytic site, thus acting as a catalyst deactivator.

Thus, it is postulated that the introduction of at least one stable ligand into the transition metal catalyst will create a conformational constraint in the form of a steric hindrance around the transition metal atom (s) and thereby prevent the hydrolyzed glycol derivatives from approaching the center (s) of the transition metal atom. bound ligands and thus catalyst deactivators.

• · · · ··· ·················

It is envisaged that the conformational constraint in the form of a steric hindrance can also be constructed around the transition metal atom (s) of the catalyst by binding the transition metal atom (s) to the stable ligand (s). At the same time, the electron property of the transition metal atom (s) of the catalyst can be altered by binding the transition metal atom (s) to the stable ligand (s) so as to increase the catalytic activity of the transition metal catalyst complex in the present invention. Variations in the steric and electron properties of stable ligands can be made based on the teachings of Crabtree R. in The Organometallic Chemistry of Transition Metals, 2nd Edition, John Wiley & Sons, N.Y. (1994); Yamamoty A. in Organotransition Metal Chemistry, John Wiley & Sons, N.Y. (1986) and Cotton F. and Wilkinson G. in Advanced Inorganic Chemistry, 4th Edition, John Wiley & Sons, N.Y. (1980).

Stable L ¹ , L ² , L ³ , L ⁴ ... L ^P ligands useful in the present invention for the construction of sterically hindered transition metal complexes include, for example, unchangeable, stable, neutral monodentate ligands, bidentate ligands, multidentate ligands or a combination thereof, or polymeric organic or inorganic multidentate ligands; non-interchangeable or strongly bound, anionic monodentate ligands, bidentate ligands, multidentate ligands or a combination thereof, or polymeric organic or inorganic multidentate ligands.

Although it is desirable to have one or more stable ligands attached to the transition metal because of the sterically hindered complexes, it is also preferred that one or more labile ligands or one or more free coordination sites exist on the transition metal to allow insertion of hydrogen peroxide or an organic hydroperoxide to a transition metal and thereby activating the hydroperoxide to the epoxidation process.

In one embodiment of the present invention, stable ligands useful in the present invention include, for example, oxygen-containing ligands, phosphorus-containing ligands, nitrogen-containing ligands, aromatic-containing ligands, organosilyl or organosilyloxy-containing ligands, or combinations thereof. These stable ligands may also contain one or more asymmetric or chiral centers. These stable ligands may also contain one or more hydrophilic moieties, such as, but not limited to, a sodium sulfonate containing moiety.

Ligands including stable ligands that may be useful in the present invention include, but are not limited to, the following representative ligands:

Oxygen-containing ligands

Mono-dentate, bidentate or polydentate oxygen-containing ligands useful in the present invention include, but are not limited to, aliphatic and cycloaliphatic alcohols and diols; phenolates; carboxylic acids; ketones or combinations of these oxygen-containing ligands. Partially or fully fluorinated oxygen-containing monodentate or polydentate ligands are also included as examples of ligands useful in the present invention.

Examples of oxygen-containing ligands useful in the present invention are alcohols and diols, such as ethanol, propanol, cyclohexanol, diethylene glycol monomethyl ether, propane-1,2-diol, cis- and Zra / z-cyclohexane-1,2- diol, 2,3-dimethylbutane-2,3-diol, octane-1,2-diol and diethylene glycol. Also included as examples of oxygen-containing ligands useful in the present invention are fluorinated alcohols such as trifluoroethanol, 1,3-difluoro-2-propanol; 2,2,3,3,3-pentafluoro-1-propanol and hexafluoroisopropanol. Examples of oxygen-containing ligands useful in the present invention are also carboxylic acids and hydroxyl-containing carboxylic acid esters such as lactic acid and ethyl lactate; ketones such as acetoacetate and acetoacetone; phenol or bisphenol ligands such as 2,6-dimethyl-, 2,6-di-tert-butyl- or 2,6-diisopropylphenol, 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2, 2'-ethylenebis (6-tert-butyl-4-methylphenol), 1,1'-binaphthyl-2,2'-diol, methylene-1,1'-binaphthyl-2,2'-diol and 2,2'- thiobis (6-tert-butyl-4-methylphenol); but the present invention is not limited by these ligand structures.

A strongly bound, unmistakable, neutral or basic bidentate or multidentate ligand is usually more stable than the monodentate ligand. Stable oxygen-containing ligands useful in the present invention include, for example, aliphatic and cycloaliphatic diols, bisphenolates, dicarboxylic acids, diketones, or a combination thereof. Such stable ligands useful in the present invention include, but are not limited to, propane-1,2-diol, cis- and Zraws-cyclohexane-1,2-diol, 2,3-dimethylbutane-2,3-diol, octane-1,2. -diol, diethylene glycol,

2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-ethylenebis (6-tert-butyl-4-methylphenol), 1,1'-binaphthyl-2,2'-diol, methylene-1,1'-binaphthyl-2,2'-diol, and 2,2'-thiobis (6-tert-butyl-4-methylphenol), tartaric acid, cis- and trans -cyclohexane-1,2- dicarboxylic, acetoacetate and acetoacetone.

The oxygen-containing ligands may also contain one or more asymmetric or chiral centers. Such asymmetric or chiral oxygen-containing ligands include, without limitation e.g. l- (5) -2- (7?) - (+) - or l- (7?) - 2- _(t ¹ S) - (-) - / trans-2-phenylcyclohexanol, (S) - (+) - or (R) - (-) - 3-hydroxytetrahydrofuran, (S) - (-) - or (A) - (+) - and - methyl 1-naphthalenyl methyl, (S) - (-) or (R) - (+) - α-methyl-2-naphthalenylmethanol, (S) - (+) - or (72) - (-) - propanediol, (5) - (+) - or (5) - (-) - 3-chloro-1 , 2-propanediol, (S) - (+) - or ¢5) - (-) - 1,3-butanediol, (25,35) - (+) - or (25,35) - (-) - 2 , 3-butanediol, (25,45) - (+) - or (25,45) - (-) - 2,4-pentanediol, (15,25,35,55) - (+) - or (15, 25,35,55) - (-) - pinanediol, (1S, 2S) -trans- or (15,25) -rans-1,2-cyclohexanediol, (1S, 2S) -trans- or (1S, 2S) -trans- 25) -Zrans-1,2-cyclopentanediol, D-xylose γ-lactone, D-ribose γ-lactone, L or D-xylose, L- or D-arabinose, L- or D-ribose, L- or D-threitol , L- or D-arabitol, L- or D-glucose, 2-deoxy-D-ribose, D-xylopyranoside, D-focose, 2-deoxy-D-glucose, 5-thio-D-glucose, L -glucose, methyl 5 - (+) - or 5 - (-) - lactate, diethyl L- or D-tartrate, diisopropyl L- or D-tartrate, 5 - (-) - or 5 - (+) -1,1'-bi-2-naphthol and 25,35 - (-) - or 25,35 - (+) - 1,4-dibenzyloxy-2,3-butanediol.

Also included as examples of ligands useful in the present invention are partially or fully fluorinated bidentate or polydentate oxygen containing ligands.

The stable oxygen-containing ligands described above are suitable for the construction of transition metal complexes for the epoxidation of allylarylethers.

Ligands containing phosphorus

Monodentate, bidentate or polydentate phosphorus-containing ligands useful in the present invention include, for example, inorganic or organic derivatives of phosphoric acid and phosphorous acid, aliphatic, cycloaliphatic or aromatic organophosphinyl ligands. Partially or fully fluorinated phosphorus-containing monodentate or polydentate ligands are also included as examples of ligands useful in the present invention.

Examples of phosphorus-containing monodentate, bidentate or polydentate ligands useful in the present invention include, but are not limited to, trimethylphosphine, triethylphosphine, triisopropylphosphine, triphenylphosphine, tricyclohexylphosphine, cyclopentadienylphenylphosphine, methyldiphenylphosphine, or any combination thereof. Also included as examples of phosphorus-containing ligands useful in the present invention are 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1- (1). 1'-diphenylphosphinopherocenyl) -1-dicyclohexylphosphinylethane, 2- (diphenylphosphinyl) cyclohexanol, 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl, 1,1'-bis (diphenylphosphino) ferrocene, 1,2-bis ( 2,5-dimethylphospholano) benzene, 1,2-bis (2,5-dimethylphospholano) ethane, 1,2-bis (2,5-diethylphospholano) ethane and camphor-based hydroxyphosphoryl ligands such as endo, endo-3 - (diphenylphosphoryl) -2-hydroxyboman. These examples of phosphorus-containing ligands useful in the present invention are not limited to those described above.

A strongly bound, unmistakable, neutral or basic bidentate or multidentate ligand is usually more stable than the monodentate ligand. Stable ligands comprising inorganic phosphoric and phosphorous acid derivatives and organic phosphoric and phosphorous acid derivatives useful in the present invention are bidentate and polydentate ligands such as e.g.

phenylphosphonate (PhPO ₃ ^'3) diphenylphosphine (Ph2PO2 ~ ²⁾ and -hydroxyphosphinol (HPO3' ^2). Stable ligands containing aliphatic, cycloaliphatic or aromatic organophosphinyl ligands which are useful in the present invention are bidentate or polydentate ligands such as, but not limited to, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,1-bis (diphenylphosphino) propane. 4-bis (diphenylphosphino) butane, 1- (r-diphenylphosphinopherocenyl) -1-dicyclohexylphosphinylethane, 2- (diphenylphosphinyl) cyclohexanol, 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl, 1,1 '- bis (diphenylphosphino) ferrocene, 1,2-bis (2,5-dimethylphospholano) benzene, 1,2-bis (2,5-dimethylphospholano) ethane, 1,2-bis (2,5-diethylphospholano) ethane and hydroxyphosphoryl ligands camphor-based such as endo, endo-3- (diphenylphosphoryl) -2-hydroxyboman.

Phosphorus-containing ligands may also contain one or more asymmetric or chiral centers. Such asymmetric or chiral phosphorus-containing ligands without limitation include (+) - neomentyldiphenylphosphine; chiral camphor derivatives, such as (1 R) - endo, endo-35 '- (diphenylphosphoryl) - (2 R) - hydroxyboman; (S) - (-) - or (R) - (+) - 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl, (S) - (-) - or (H) - (+ ) -2,2'-bis (di-p-tolylylphosphino) -1,1'-binaphthyl; and 25/35 - (-) - or 27 R, 37 R - (+) - bis (diphenylphosphino) butane.

The phosphorus-containing ligands may also contain one or more hydrophilic moieties. Such hydrophilic phosphorus-containing ligands include, but are not limited to, 3,3 ', 3'-phosphinidyl-tris (benzenesulfonate) trisodium.

Examples of ligands useful in the present invention also include partially or fully fluorinated phosphorus-containing monodentate or polydentate ligands.

Also useful in the present invention are oxidized phosphorus-containing monodentate or polydentate ligands, e.g., organophosphine oxides, such as triphenylphosphine oxide, tritolylphosphine oxide, tricyclohexylphosphine oxide and 1,2-bis (diphenylphosphine oxide) ethane.

The stable phosphorus-containing ligands described above are suitable for the construction of transition metal complexes for the epoxidation of allylarylethers.

Nitrogen-containing ligands

Nitrogen-containing ligands such as the monodentate or polydentate amino compounds, heterocyclic compounds, biheterocyclic compounds, or fused heterocyclic compounds, are ligands useful in the preparation of the transition metal complexes of the present invention. The nitrogen-containing ligands may comprise non-nitrogen heteroatoms such as O, S, Si, B or P, or any combination thereof. Examples of ligands useful in the present invention also include partially or fully fluorinated monodentate or polydentate nitrogen-containing ligands.

Monodentate and bidentate aminoligands useful in the present invention include, but are not limited to, aminoligands having the following general formulas', B 'and B':

HN (R ⁶ ) Ar ' (B) or HN (SiR ⁶ 3) Ar ' (B ’) or N (SiR ⁶ 3) ₂ Ar ' (B ”)

wherein R ⁶ is methyl, ethyl, isopropyl, tert-butyl, cyclohexyl and phenyl and R ⁶ may be partially or fully fluorinated and Ar 1 is an aryl group with or without substituents that are ortho to the nitrogen atom, such as e.g. 2,6-diisopropylphenyl; or aminoligands having the following general formula C:

Ar'N (R ⁶ ) (CH 2) _n ^and N (R ^e ) Ar '(C) wherein R ⁶ and Ar' are the same as those described above, and n 'is from 1 to 5; or oxygen-containing tridentate diamine ligands having the following general formula D:

[Ar'N (R ⁶ ) CH ₂ CH 2] ₂ O '(D) wherein R ⁶ and Ar' are the same groups as those described above.

Examples of the above aminoligands useful in the present invention include, but are not limited to, N, N-bis (2,6-diisopropylphenyl) amine, N-2,6-diisopropylphenyl-N-trimethylsilylamine, N-tert-butyl-N -3,5-dimethylphenylamine, N, N-di-trimethylsilylamine, N, N'-bis (trimethylsilyl) -1,2-diaminoethane, N, N'-bis (2,6-diisopropylphenyl) -1,3-diaminopropane , bis [2- (N-2,6-dimethylphenyl) aminoethyl] ether and bis [2- (N-2,6-diisopropylphenyl) aminoethyl] ether.

Also included as examples of aminoligands useful in the present invention are multiazaacyclic, cyclic and macrocyclic amines, such as e.g.

(2'-pyridyl) pentan-3-ol, bis [4- (diethylamino) tris [2- (N-trimethylsilyl) aminoethyl] amine, 1,3,5-trimethyl-1,3,5-triazacyclohexane, 1, 3,5-tert-butyl-1,3,5-triazacyclohexane, 1,3,5-tribenzyl-1,3,5-triazacyclohexane, 1,5,9-triazacyclododecane, cyclam- (1,4,8,11) -tetraazacyclododecane), cyclam- (1,4,7,10-tetraazacyclododecane), 1,2-cyclohexanediamine-N, N'-bis (3,3-di-tert-butylsylicylidene) known as Jacobsen Ligand, ethylenebis (salicylimine) known as Salen and 2,6-bis (imino) pyridyl ligands and related bis (imide) pyridyl ligands described by Gibson VC et al., Chem. Commun., Pp. 849-850 (1998) and Brookhart M. et al., J. Am. Chem. Soc. 120, 16, pp. 4049-4050 (1998).

Monodentate and multidentate nitrogen-containing monoheterocyclic and multiheterocyclic ligands useful in the present invention include, but are not limited to, monoheterocyclic pyridine ligands such as (2'-pyridyl) propan-2-ol, (2'-pyridyl) -2 4-dimethylpentan-3-ol, (2'-pyridyl) cyclohexanol,

9- (2-pyridyl) -9-fluorenol, bis (4-phenylphenyl) -2-pyridylmethanol, phenyl] -2-pyridylmethanol, 1- (2-pyridyl) dibenzosuberol, 2-cyano-6- (2-hydroxyphenyl) pyridine and 6- (2-hydroxyphenyl) pyridine-2-carboxylic acid.

Monodentate and multidentate monoheterocyclic and multiheterocyclic ligands useful in the present invention also include, but are not limited to, multiheterocyclic pyridine ligands such as tris (2'-pyridylaminodimethylsilyl) methane, tris (2 '- (4-methylpyridyl) aminodimethylsilyl) methane , tris (2 '- (4,6-dimethylpyridyl) aminodimethylsilyl) methane, 2,2'-bipyridine, dendridic bipyridine and 2,6-bis (2-pyridyl) pyridine.

Monodentate and multidentate monoheterocyclic and multiheterocyclic ligands useful in the present invention include, but are not limited to, eg, multiheterocyclic pyridine-oxazoline, pyridine-pyrazole and pyrazine-pyrazole ligands such as 2,6-bis [4-methyloxazolin-2-yl]. pyridine, 2,6-bis [4-isopropyloxazolin-2-yl] pyridine, 5-phenyl-4-hydroxymethyl-2- (2-pyridinyl) -4,5-dihydro [2,1-d] oxazole, 2- ( 5-methylpyrazol-3-yl) pyridine,

2- (5-phenyl-pyrazol-3-yl) pyridine, 2- (4-chloropyrazol-3-yl) pyridine, 2- (4-bromopyrazol-3-yl) pyridine, 2- (4-nitro-pyrazole- 3-yl) pyridine, 2- (5-methyl-1-octylpyrazol-3-yl) pyridine, 2- (1-octyl-5-phenylpyrazol-3-yl) pyridine, 2- (4-chloro-1-octylpyrazole) 3-yl) pyridine, 2- (5-methylpyrazol-3-yl) pyrazine and 2- (5-methyl-1-octylpyrazol-3-yl) pyrazine.

Nitrogen-containing ligands useful in the present invention include biheterocyclic quinoline and biheterocyclic oxazoline ligands such as, but not limited to, 2-methyl-8-hydroxyquinoline, 5,7-dibromo-2-methyl-8-hydroxyquinoline, 2,2 ' -methylenebis (oxazoline) and 2,2'-isopropylidenebis (oxazoline).

··· ··· ·············· · · ···

Nitrogen-containing ligands useful in the present invention also include boron-containing nitrogen-containing heterocyclic ligands such as, but not limited to, hydrotri (3,5-dimethyl-1-pyrazolyl) borate, hydrotris [5-methyl-3- ( 3-pyridyl) pyrazolyl] borate; and hydrotris [5-methyl-3- (5-α-picolyl) pyrazolyl] borate.

A strongly bound, unmistakable, neutral or basic bidentate or multidentate ligand is usually more stable than the monodentate ligand. Among the stable nitrogen-containing ligands useful in the present invention are such heterocyclic rings or fused heterocyclic rings such as, but not limited to, N, N-bis (2,6-diisopropylphenyl) amine, N-2,6-diisopropylphenyl-N -trimethylsilylamine, N-tert-butyl-N-3,5-dimethylphenylamine, N, N-di-trimethylsilylamine, N, N'-bis (trimethylsilyl) -1,2-diaminoethane, N, N'-bis (2, 6-diisopropylphenyl) -1,3-diaminopropane, bis [2- (N-2,6-dimethylphenyl) aminoethyl] ether, bis [2- (N-2,6-diisopropylphenyl) aminoethyl] ether, tris [2- ( N-trimethylsilyl) aminoethyl] amine, 1,3,5-trimethyl-1,3,5-triazacyclohexane, 1,3,5-tert-butyl-1,3,5-triazacyclohexane, 1,3,5-tribenzyl- 1,3,5-triazacyclohexane, 1,5,9-triazacyclododecane, cyclam- (1,4,8,11-tetraazacyclododecane), cyclam- (1,4,7,10-tetraazacyclododecane), 1,2-cyclohexanediamine- N, N'-bis (3,3-di-tert-butylsalicylidene), ethylenebis (salicylimine), 2,6-bis (imino) pyridyl ligands, (2'-pyridyl) propan-2-ol, (2-pyridyl) - 2,4-dimethylpentan-3-ol, (2'- pyridyl) cyclohexanol, (2'-pyridyl) pentan-3-ol, 9- (2'-pyridyl) -9-fluorenol, bis (4-phenylphenyl) -2-pyridylmethanol, bis [4- (diethylamino) phenyl] - 2-pyridylmethanol, 1- (2-pyridyl) dibenzosuberol, 2-cyano-6- (2-hydroxyphenyl) pyridine, 6- (2-hydroxyphenyl) pyridine-2-carboxylic acid, tri with (2'-pyridylaminodimethylsilyl) methane, tris (2 '- (4-methylpyridyl) aminodimethylsilyl) methane, tris (2' - (4,6-dimethylpyridyl) aminodimethylsilyl) methane, 2,2'-bipyridine, dendridic bipyridine, 2,6-bis (2- pyridyl) pyridine, 2,6-bis [4-methyloxazolin-2-yl] pyridine, 2,6-bis [4-isopropyloxazolin-2-yl] pyridine, 5-phenyl-4-hydroxymethyl-2- (2-pyridinyl) -4,5-dihydro [2,1-d] oxazole, 2- (5-methylpyrazol-3-yl) pyridine, 2- (5-phenylpyrazol-3-yl) pyridine, 2- (4-chloropyrazol-3) -yl) pyridine, 2- (4-bromopyrazol-3-yl) pyridine, 2- (4-nitropyrazol-3-yl) pyridine, 2- (5-methyl-1-octylpyrazol-3-yl) pyridine, 2- (1-octyl-5-phenylpyrazol-3-yl) pyridine, 2- (4-chloro-1-octylpyrazol-3-yl) pyridine, 2- (5-methylpyrazol-3-yl) pyrazine, 2- (5- methyl-1-octylpyr azol-3-yl) pyrazine, 2-methyl-8-hydroxyquinoline, 5,7-dibromo-2-methyl-8-hydroxyquinoline, 2,2'-methylenebis (oxazoline), 2,2'-isopropylidenebis (oxazoline), hydrotri (3,5-dimethyl-1-pyrazolyl) borate, hydrotris [5-methyl-3- (3-pyridyl) pyrazolyl] borate and hydrotris [5-methyl-3- (5-α-picolyl) pyrazolyl] borate.

The nitrogen-containing ligands may also contain one or more asymmetric or chiral centers. Such asymmetric or chiral nitrogen-containing ligands without limitation include (45,55) - (+) - 5-phenyl-4-hydroxymethyl -2- (2-pyridinyl) -4,5-dihydro [2,1-a] oxazole, S- or R- (2'-pyridyl) nonanol, S- or N- (2'-pyridyl) cyclohexanol.

Examples of ligands useful in the present invention also include partially or fully fluorinated monodentate or polydentate nitrogen-containing ligands.

Because of the basicity of nitrogen-containing ligands such as monodentate, monoheterocyclic and bidentate biheterocyclic ligands, these ligands can also be used for metals with a higher oxidation state, such as Re. However, some nitrogen-containing ligands are basic compounds which may also open the epoxy ring of glycidyl ethers and in particular may open the epoxy ring of arylglycidyl ethers.

The stable nitrogen-containing ligands described above are suitable for the construction of transition metal complexes for the epoxidation of allylarylethers.

Ligands containing an aromatic part

The following formulas VI to IX represent four types of partial structures of transition metal complexes that contain aromatic-containing ligands such as cyclopentadienyl (Cp), pentamethylcyclopentadienyl (Cp *), indenyl (In) or 9-fluorenyl (Fl) ligands that are useful in the hydroperoxide epoxidation process of the present invention.

The following general formula (VI) is a partial structure of the transition metal catalyst-complex shown in Scheme I above:

R ⁷ -M (VI) wherein R ⁷ is Cp, Cp *, In or Fl; and M is a transition metal such as Ti, Zr, Hf, V, Mo, W, Re, Mn, and La. The above general formula VI represents a half-shell transition metal complex.

Monodentate ligands containing Cp-, Cp * -, In- and Fl- are described by Hitchcock S. in Organometallics, 14, pp. 3732-3740 (1995). An example of such a "half-shell" transition metal complex is the generalized molybdenum complex shown below in Formula VIa:

(VIa) wherein R ⁸ is hydrogen, methyl, ethyl, isopropyl, cyclohexyl and phenyl, and is partially or fully fluorinated; L ¹ , L ² , L ³ and L ⁴ are ligands as defined above and include, for example, ligands selected from the group consisting of carbon monoxide, Cl, P (R ⁶ ) ₃ , -Si (R ⁶ ) 3; and R ⁶ is the same as defined above.

Mo complexes having one Cp ligand or a substituted analog thereof are a well known class of compounds. These complexes are typically electronically saturated with 18 valence electrons and contain one or more labile halide or carbonyl ligands such as Cp * MoCl (CO) ₃ ;

Cp '(CO) ₂ [(CH 3) 3 P] Mo-Si (C ₆ H ₅ XOH) ₂ ; Cp * (CO) ₂ [(CH ₃ ) ₃ P] W-Si (C ₆ H ₅ ) (OH) ₂ ;

Cp * (CO) ₂ [(CH ₃ ) ₃ P] Mo-Si (CH ₃ ) (OH) ₂ ;

Cp * (CO) ₂ [(CH ₃ ) ₃ P] W-Si (CH ₃ ) (OH) ₂ ;

Cp * (CO) ₂ t (CH ₃ ) 3 P] Mo-Si (Me) [OSi (CH 3) ₂ OH] ₂ ;

Cp * (CO) ₂ [(CH ₃ ) 3 P] Mo-Si (C ₆ H ₅ ) [OSi (CH ₃ ) ₂ OH] ₂ ; Cp (CO) ₂ [(CH ₃ ) ₃ P] Mo-Si (OH) ₃ ; Cp (COhKCHs-JW-SKOHh Cp (CO) ₂ [(CH3) ₃ P] Mo-Si [OSi (CH _{3) 2} H] _3;

Cp * (CO) ₂ [(CH3) ₃ P] W-Si (H) (CH _{3) 2} and Cp * (CO) _{2 [(CH3)} 3P), W-Si (H) (Cl) (CH ₃ ).

In these complexes, labile halide and carbonyl ligands may be replaced by more strongly bound ligands such as -SiMe3, -OSiMe ₃ or PMe ₃ . Methods for exchanging labile halide and carbonyl ligands with stronger ligands are described by Malisch W. in J. Chem. Soc., Chem. Commun., Pp. 1917-1919 (1995) and vlnorg. Chem., 32, 3, pp. 303-309 (1993).

Also included in formula VI above are electronically unsaturated transition metal complexes with a 16- or 17-electron configuration, such as Cp * MoCl [P (CH ₃ ) ₃ ] ₂ ; Cp * MoCl ₃ P (CH ₃ ) 3; Cp * MoCl [P (CH ₃ ) ₃ ] ₂ (CO); Cp * MoCl ₂ (dppe) and CpMoCl ₂ (dppe), wherein dppe is 1,2-bis (diphenylphosphino) ethane. Examples of such electronically unsaturated transition metal complexes are described by Field R. in Chem. Rev., 96, pp. 2135-2204 (1996); in Organometallics, 16, pp. 1581-1594 (1997); in J. Am. Chem. Soc., 118, pp. 3617-3625 (1996) and in J. Chem. Soc., Chem. Commun., Pp. 2317-2318 (1994).

Formula VII below is a partial structure of the transition metal catalyst-complex shown in Scheme I above:

^R7 -MR ⁷ (V) wherein R ⁷ and m are the same groups as those defined above in connection with the general formula VI wherein each R ⁷ group may be the same or different. The above formula VII represents a metallocene transition metal sandwich complex.

An example of such a transition metal metallocene complex useful in the present invention is the generalized molybdenum complex set forth below in Formula VIIa.

(VIIa) wherein R ⁸ is a group as defined above in relation to formula VI and L ¹ , L ² are ligands as defined above in relation to formula VIa.

Mo complexes having two Cp ligands or substituted analogs thereof are a well known class of compounds. These complexes are typically electron saturated with 18 valence electrons and contain one or more labile halide or carbonyl ligands. Examples of such complexes are (Cp MoCb; (Cp) ₂ 2MoBr; (Cp MoCb; (Cp *) ₂ Mobra _2; (In-Mocha; bis (2- (4-methoxyphenyl) -4,5,6,7 bis (2- (4-methylphenyl) -4,5,6,7-tetrahydroindenyl) MCl 2 and bis (2- (4-bromophenyl) -4,5,6,7-tetrahydroindenyl) MCl 2, wherein: Cp, Cp *, In and M are the same groups as previously defined Cl or Br ligands in these complexes may be exchanged for more strongly bound ligands such as -SiMe ₃ or -0SiMe3; 9 as described by Malisch W. vJ. Chem. Soc., Chem. Commun., Pp. 1917-1919 (1995) and Inorg. Chem., 32, 3, pp. 303-309 (1993).

Formula VIII below is a partial structure of the transition metal catalyst-complex shown in Scheme I above:

/ \ 7 / R ⁷ (vin)

M ^Z wherein R ⁷ and M are the same groups as defined above in connection with the general formula VII and wherein X 'is the bridging or linking R group moiety such that the structure R -X'-R becomes a bidentate ligand in which R ⁷ it may be the same or different group. X 'can be, for example, methylene, ethylene, isopropylidene, binaphthyldimethylene, dimethylsilylene and bis (dimethylsilyl) oxy. The above general formula (VIII) is an ansa circular transition metal complex.

The Mo complexes represented by the general formula (VIII) are a well known class of compounds. These complexes are typically electronically saturated with 18 valence electrons and contain one or more labile halide or carbonyl ligands. Such complexes can be synthesized as described by Hermann W. in Angew. Chem., Int. Ed. Engl., 33, 19, 1946-1949 (1994). The synthesis scheme published by Hermann is shown below for illustration and synthesis is not limited by this scheme:

In the above synthetic scheme, M and X defin are defined above in relation to Formula VIII.

In these complexes, labile halide ligands may be replaced by more strongly ligated ligands such as -SiMe3 or -OSiMe3. Methods for exchanging labile halide ligands with stronger ligands are described by Malisch W. in J. Chem. Soc., Chem. Commun., Pp. 1917-1919 (1995) and Inorg. Chem., 32, 3, pp. 303-309 (1993).

An example of a transition metal complex with a bidentate ansa ligand of Formula VIII is the molybdenum complex of Formula VIIIa below:

wherein R ⁸ is as defined above; L ¹ and L ² in the above specific molybdenum complex are ligands selected from the group consisting of carbon monoxide, Cl, P (R ⁶ ) 3, -Si (R ⁶ ) 3; and R ⁶ is the same as defined above. R ⁶ may be partially or fully fluorinated. X 'is a bridge linking together the Cp groups. Thus, Cp-X'-Cp becomes a bidentate ligand containing an "ansa" ring, X 'is methylene, ethylene, isopropylene, and dimethylsilylene. Such bidentate "ansa" ring containing ligands useful in the present invention include, but are not limited to, bis (4-tert-butyl-2-methylcyclopentadienyl) dimethylsilane; bis (cyclopentadienyl) dimethylsilane; bis (9-fluorenyl) dimethylsilane; bis (1-indenyl) dimethylsilane; bis (2-methyl-1-indenyl) dimethylsilane; cyclopentadienyl- (9-fluorenyl) diphenylmethane; cyclopentadienyl- (9-fluorenyl) dimethylsilane; 1,2-bis (1-indenyl) ethane; 1,2-bis (2'-methyl-1-indenyl) ethane; 1,2-bis (4 ', 5', 6 ', 7'-tetrahydro-1-indenyl) ethane; 2,2- (cyclopentadienyl) - (9-fluorenyl) propane and bis (1-benzoindenyl) dimethylsilane.

A strongly bound, unmistakable, neutral or basic bidentate or multidentate ligand is usually more stable than the monodentate ligand. Among the stable Cp, Cp *, In and Fl containing ligands that are useful in the present invention are, for example, such bidentate or multidentate ligands as shown above in formula VIII.

The following general formulas (IXA, IXB, IXC) represent "ansa" transition metal complexes in which one of the metal-ligand bonds is formed through an auxiliary group:

35 • · · · · • · · · · • · · • · · M <t AND Λ <4 AND R ^{7 '} X'r-A-M v (IXA) (IXB) (IXC)

wherein R ⁷ , X 'and M in formulas IXA, IXB and IXC are the same groups as those defined above in relation to formula IIIa. A is an auxiliary group attached to the R ⁷ or X 'group, provided that A is a moiety including, but not limited to, alkylamine, cycloalkylamine, an aromatic amine, or any combination thereof; an alkyl alcohol, a cycloalkyl alcohol, an aromatic alcohol, or any combination thereof; alkyl ether, cycloalkyl ether, aromatic ether, or any combination thereof; alkylorganophosphine, cycloalkylorganophosphine, aromatic organophosphine, or any combination thereof. Thus, the R ⁷ -A moiety is a bidentate ligand.

A strongly bound, unmistakable, neutral or basic bidentate or multidentate ligand is usually more stable than the monodentate ligand. Among the stable Cp, Cp *, In and Fl containing ligands that are useful in the present invention are, for example, such bidentate or multidentate ligands as shown above in the general formulas IXA, IXB and IXC.

The specific structure of the "ansa" of the molybdenum complex containing the stable Cp ligand with the auxiliary group is shown below as formula IXAa:

wherein R ⁶ , L ¹ and L ² are ligands and L ¹ , L ² and R ⁶ are the same groups as those defined above in connection with the general formula VIa. The substituent on the nitrogen atom in the above general formula (IXAa) may also be other than 2,6-diisopropylphenyl, e.g., isopropyl, tert-butyl, n-butyl, adamantyl,

2,6-dimethylphenyl, cyclohexyl and dodecanyl. Complexes of formula (IXAa) are described, for example, by Roesky H. in J. Chem. Soc., Dalton Trans., Pp. 4143-4146 (1996) and Organometallics, 15, pp. 3176-3181 (1996).

In such complexes containing the remaining labile ligands, such as halide or carbon monoxide, the remaining labile ligands may be replaced by ligands such as -SiMe3 or -OSiMe3. Methods for exchanging labile ligands with stronger ligands are described by Malisch W. vJ. Chem. Soc., Chem, Commun., Pp. 1917-1919 (1995) and Wavorg. Chem., 32, 3, pp. 303-309 (1993).

Other specific "ansa" ligands with an auxiliary group include, but are not limited to, bis (Cp *) (3-methoxy-1-propyl) methylsilane; bis (Cp *) (3-methoxy-1-pentyl) methylsilane; dimethyl (dimethylaminoethylcyclopentadienyl) (Cp *) silane; trimethyl (2-methoxyethylcyclopentadienyl) silane; trimethyl (2-isobomyloxyethylcyclopentadienyl) silane; trimethyl (2-menthylethyloxycyclopentadienyl) silane; trimethyl (2-phenchyloxyethylcyclopentadienyl) silane; N, N-dimethyl-2-aminoethylcyclopentadiene; N, N-dimethyl-3-aminopropyl-cyclopentadiene and (Cp) dimethyl (diphenylphosphinomethyl) silane.

A strongly bound, unmistakable, neutral or basic bidentate or multidentate ligand is usually more stable than the monodentate ligand. Among the stable ligands containing Cp, Cp *, In, and Fl which are useful in the present invention are those bidentate or multidentate ligands which are shown above in the general formulas IXA, IXB and IXC.

Ligands containing an organosilyl group and an organosilyloxy group

The incorporation of a silicon-derived functional group in the transition metal complexes of the present invention is important not only to provide a functional group for coupling the precious metal complex to solid supports, but also because the silicon-based ligands confer advantageous solubility and hydrolysis stability to the catalyst. Silicon-based ligands also impart hydrophobic properties to the catalyst, which may limit the hydrolysis of the epoxide to glycols.

Silicon-containing ligands can generally be divided into two groups, the organosilyl group-containing ligands and the organosilyloxy group.

In ligands containing an organosilyl group, the silicon atom is bonded directly to the transition metal atom. An example of an organosilyl group-containing monodentate ligand is -Si (R ⁶ ) _3, and an example of a bidentate or multidentate organosilyl group-containing ligand is -Si (R ⁶ ) 2 [-O-Si (R ⁶ ) 2] _m '-O-Si (R ⁶ ) 2, wherein R ⁶ is the same group as described above and m "is from 0 to 10.

Transition metal complexes with organosilyl group-containing ligands may be prepared by reacting an organosilyl salt of an alkali metal, wherein the alkali metal is lithium, sodium or potassium; or by reacting a transition metal chloride or bromide complex with organosilyl magnesium chloride. Thus, a transition metal-chloride or transition metal-bromide bond is exchanged for a transition metal-silicon bond. The method used to prepare these organosilyl ligands in which the silicon atom is directly bound to the transition metal is described, for example, by Malisch W. in Inorg. Chem., 34, 23, 5701-5702 (1995).

The organosilyl group-containing ligands may also be incorporated into the transition metal complex by indirectly attaching the organosilyl group-containing moiety to the transition metal via monodentate ligands, such as -L-Si (R ⁶ ) 3, where L is a ligand as defined above. An example of such an organosilyl group-containing monodentate ligand is γ-aminopropyltrimethoxysilane, wherein the amide moiety is attached to one end and the organosilyl moiety is attached to the other end of the ligands, as described, for example, in US Patent No. 5,620,938.

Ligands containing an organosilyloxy group may be monodentate ligands such as -O-Si (R ⁶ ) 3, or multidentate ligands such as -O-Si (R ⁶ ) 2 [-O-Si (R ⁶ ) 2] m " -O-Si (R ⁶ ) 2 -O-, wherein the silicon atom bound to the transition metal indirectly via an oxygen atom, wherein R ^{6 and} m 'are as defined above.

Organosilyloxy-containing ligands may be introduced into the transition metal complex by indirectly attaching the organosilyloxy-containing moiety to the transition metal via a monodentate ligand, such as -LO-Si (R ⁶ ) 3, where L is a ligand as defined above. One method of introducing organosilyloxy-containing ligands into a transition metal complex is described, for example, by Malisch W. in Inorg. Chem., 34, 23, 5701-5702 (1995). The synthesis scheme published by Malisch is shown below for illustration and the synthesis is not limited by this scheme:

If lithium salts of organosilane diols or trioles are used in the reaction with transition metal halides, transition metal complexes having the following general formulas (E) and (F) may be formed:

R6

R ⁶

O / ° h

o _{/ RE} e SL

Mo f / \\

O O

R ⁶ (E)

Mo (F) wherein the substituents R ⁶ are the same as described above.

When the transition metal complex with one, two or three organosilyl hydroxyl groups is condensed with a mono-, di-, tri- or tetramethoxysilane or mono-, di-, trine or tetraethoxysilane, a hybrid organic-inorganic material is formed. This hybrid is organic-inorganic. the material may be soluble or partially soluble in organic solvents. One method of preparing hybrid organic-inorganic materials useful in the present invention that is soluble or partially soluble in organic solvents is described by Shea K. J. et al. in Chem. Rev., 95, pp. 1431-1442 (1995). Another method for preparing hybrid organic-inorganic materials that are soluble or partially soluble in organic solvents employs dendrimers containing Si-OH and is described by Majorali J. P. et al. in Chem. Rev., 99, 845-880 (1999).

When the transition metals with ligands are bound one by one to sesquisiloxane, an organic solvent soluble metalosiloxane is formed, an example of which is shown in formula G below:

wherein the substituents R ⁶ are as defined above.

The above transition metal sesquisiloxane, which is soluble in organic solvents, can be anchored or bound on a solid silicon-based support to form a heterogeneous catalyst. If the transition metal is coupled to sesquvisiloxane via a multiple M-O-Si bond, it is bound very tightly as shown below in the general formula

H:

· · · · · · * · «* * * * * * * * * * * * * * * * * * wherein the substituents R ⁶ are as described above. Thus, when the M-O bond from the MO-Si moiety is dissociated during epoxidation by hydroperoxide insertions such as TBHP, the transition metal still remains bound to the sesquisiloxane structure via one or more MO-Si bonds. Thus, to a lesser extent, undesirable "leaching" of transition metals occurs.

A strongly bound, unmistakable bidentate or multidentate ligand is usually more stable than the monodentate ligand. Among the stable ligands that are useful in the present invention are the bidentate or multidentate ligands having the organosilyl moieties or organosilyloxy moieties described above.

The above-described stable ligands containing an organosilyl group or organosilyloxy group are suitable for the construction of transition metal complexes for the epoxidation of allylarylethers.

Homogeneous / heterogeneous catalytic systems

One embodiment of the present invention encompasses a process for preparing epoxides of aryl glycidyl ethers by epoxidizing allylary ethers which optionally utilizes a homogeneous or heterogeneous transition metal complex as a catalyst.

When certain ligands or combinations of ligands are selected in the preparation of the transition metal complex catalyst, the transition metal complex catalyst will be soluble in the reaction mixture during epoxidation. If the catalyst-transition metal complex is soluble, epoxidation efficiency is increased due to homogeneous mixing.

In the epoxidation process of the present invention using a homogeneous catalyst, the molar ratio of transition metal catalyst to allylarylether in the reaction mixture is from 1.10 ^-6 to 1 mol catalyst per mole of allylarylether, more preferably the molar ratio of transition metal catalyst to allylarylether in the reaction mixture is from 1.10 ⁶ to 1.10 ^'1 mole of catalyst per 1 mole allylaryletheru, most preferably the molar ratio of the transition metal catalyst to allylaryletheru in the reaction mixture from 10.1 to 10.1 ^{6' 2} moles of catalyst per 1 mole allylaryletheru.

Once the epoxidation has been carried out to the desired degree of conversion, the epoxy product can be separated and recovered from the reaction mixture by suitable techniques such as filtration, fractional distillation, extractive distillation, liquid-liquid extraction, liquid-solid extraction and crystallization, or a combination of these techniques. .

········································

In another embodiment of the present invention, the transition metal complex catalyst used is a heterogeneous catalyst. By heterogeneous catalyst is meant that the catalyst-transition metal complex is (i) insoluble in the reaction mixture during epoxidation; (ii) placed on or mounted on a solid support; or (iii) placed in a solid support by encapsulating it.

When the heterogeneous catalyst is formed by applying a transition metal catalyst of formula A to a solid support, the transition metal catalyst of formula A is dissolved in a solvent and the solution of the transition metal catalyst of formula A is then adsorbed onto the solid support and subsequently removed by any one of skill. known procedures.

The heterogeneous catalyst prepared by the process of applying the transition metal catalyst of general formula A to a solid support may be used directly, or the heterogeneous catalyst may be additionally calcined. When the process comprises calcination, the calcination temperature may be from 50 to 1000 ° C, more preferably from 100 to 700 ° C and even more preferably from 150 to 500 ° C. When calcination is carried out at these temperatures, the organic ligands bound to the transition metal may be completely exchanged by reactive groups on the support, such as hydroxyl groups of the silicate support. In such a case, the transition metal catalyst is firmly bonded to the silicate solid support via stable silyloxy bonds between the transition metal and the silicate solid support.

When the transition metal catalyst of formula (A) is applied to a solid support, the solid support may include, without limitation, for example, crosslinked polymers or ion exchange resins such as those based on styrene-co-divinylbenzene or vinylpyridine-codivinylbenzene; aromatic polyimides; organosolgels; activated carbon; coal; silicas; alumina; Ba ₂ SO ₄ ; MgO; clays; silicates; zeolites; phosphites; aluminates; or any combination thereof.

The zeolite or silicate solid supports useful in the present invention are those having a microporous crystalline structure with a pore size similar to a 4A molecular sieve (0.4 µm pore size) or one having a mesoporous crystalline structure with a pore size larger than type 4A molecular sieve. Zeolites, silicates, aluminophosphates and silica aluminophosphates useful in the present invention are, for example, TS-1, TS-2, ZSM-5, ZSM-11, ZSM-12, ZSM-22, AZM-48, SAPO-5, SAPO-11 , zeolite X, zeolite Y, Linda type L, VPI-5, NCL-1, MCM-41 and MCM-48.

· · · · T t t t t t t t t t t t t t t t t t t t t

The support materials for the heterogeneous catalysts of the present invention also include, for example, zeolites or silicates having a pore size greater than that described above that are modified to less acidic materials such as a low aluminate silicate, "zeolite beta" as described by Bekkum. H. et al. in Applied Catalysis, A: General, 167, pp. 331-342 (1998). The larger pore size zeolites or silicates described above that are modified to less acidic materials also include zeolites or silicates that are neutralized by ion exchange with alkali metal salts such as lithium acetate and sodium acetate.

Other examples of carriers modified to be less acidic and thus useful as carriers for the heterogeneous catalysts of the present invention include Ti-beta, Ti-MCM-41, Ti-silicalite-1 (TS-1), TS-2, Ti -ZSM-48, Ti-APSO-5, and Ti-HMS. It is known that solid carriers, which are acidic in nature and which are used as epoxy oxidation catalyst supports in the epoxidation of aliphatic alkenes, destroy the epoxy rings and form open by-products with a glycol structure. Because of the high yields of epoxidation, these acidic carrier materials are unsuitable for use in the present invention. The above-described zeolite and silicate carrier materials having lower acidity are preferably used in the present invention as carrier materials for heterogeneous epoxidation catalysts.

As mentioned above, heterogeneous catalysts may be formed by anchoring the transition metal catalyst of Formula A to a solid support. The anchoring of the transition metal catalyst of formula (A) to a solid support means that covalent chemical bonds or strong ionic bonds are formed between the transition metal catalyst and the solid support, and thus the transition metal catalyst is converted to a heterogeneous state.

The heterogeneous catalyst useful in the present invention can further be prepared by a process wherein the transition metal catalyst complex A is anchored on a solid support to form a strong, stable ligand-metal bond. In this method of preparing the heterogeneous catalyst, the ligand (s) are bound to the solid support components or form part of the solid support. The transition metal catalyst is anchored to the solid support via an exchange reaction in which a stronger, more stable ligand of the solid support displaces the weaker ligand on the transition metal complex to form a new transition metal complex in which the solid support is part of the ligand attached to the metal. An example of such a process for preparing a solid support anchored transition metal catalyst is described by Jiang J. et al. in J. Macromolecular Science, Part A: Chem., 35, 3, pp. 531-538 (1998) and Clark J. et al. in Chem. Commun., Pp. 853-860 (1998).

»A a a a a a a a a a a a a a a a a a a a a a a

The heterogeneous catalyst of the present invention can further be prepared by a method wherein the catalyst-transition metal complex of formula (A) is anchored on a solid support through a condensation reaction between a reactive group on a transition metal complex ligand and a reactive group on a solid support. An example of such a process for preparing a solid support anchored transition metal catalyst is described by Corma A. in J. Chem. Soc., Chem. Commun., Pp. 795-796 (1997). The transition metal complex of formula (A) may be anchored on a solid support, for example by means of a condensation reaction between Si-OH groups on the transition metal complex and Si-OH groups on a solid support. Transition metal catalysts that are soluble in organic solvents and which contain organosiloxane moieties, such as -Si-OH and -O-Si-OH, may be anchored or bound to highly crosslinked siloxane gels; or to dendrimers terminated by Si-OH groups, as described, for example, by Majorali J. P. et al. in Chem. Rev., 99, 845-880 (1999); or to silicates via Si-OH condensation reactions, to form a heterogeneous catalyst. In another embodiment, the transition metal catalyst with the -L-Si-OH moiety can also be anchored on a siloxane gel or silicate also through condensation of Si-OH groups as shown below in formula J, where L 1 and L 2 are the same ligands as those described above.

—Si-0 * —Si-O ^ Si-L —Si-0 \ ^ 0 r < ₀ (J)

-Si-0

-Si-O-Si-b-M1 -Si-O / O

An example of Si-OH condensation reactions used to form heterogeneous catalysts is described by Arai T. et al. in J. Polymer Sci., Part A: Polymer Chemistry, 36, pp. 421-428 (1998). Also included in the present invention are partially or fully fluorinated monodentate or polydentate silicon-containing ligands.

More specifically, the transition metal catalysts of formula (A) containing M-Si-OH or ML-Si-OH groups are anchored to sesquvisiloxane, primarily by the formation of a simple one. Binding to a metal-soluble siloxane soluble in the metalosiloxane organic solvents such as formula G below:

wherein the substituents R ⁶ are as defined above. Thus, the above-mentioned metalosesquvisiloxane of formula G is anchored to a solid silicon-based support to form a heterogeneous catalyst.

In addition, if the transition metal of the transition metal catalyst is bound via a multiple M-O-Si bond, it is very tightly bound to the sesquvisiloxane, as shown below in formula H:

Thus, when the M-0 bond from the MO-Si moiety is dissociated by inserting a hydroperoxide such as TBHP into the M-0 bond, the transition metal still remains bound to the sesquisiloxane structure. Via one or more of the remaining MO-Si parts. Thus, when the metalosesquvisiloxane is anchored to a solid support by condensation reactions between hydroxyl groups, transient metal leaching will occur to a lesser extent after repeated use of the heterogeneous catalyst and the heterogeneous metal complex catalyst can be reused.

More specifically, the heterogeneous catalysts of the present invention can be prepared by a method wherein the catalyst-transition metal complex A is anchored or bound to an oligomeric or polymeric solid support by ionic bonds between the transition metal complex and the cationic moiety that is attached or bound to the solid support. In the above general formula of Catalyst A, each of G ¹ , G ² , G ³ , G ⁴ ... G ¹⁵ moieties is a cationic moiety containing one or more quaternary cationic nitrogen, phosphorus, arsenic, antimony or bismuth centers with one or more organic substituents attached to each quaternary cationic center. When an organic, inorganic or hybrid organic-inorganic oligomeric or polymeric structure comprises a plurality of hydrocarbon substituents containing 1-20 carbon atoms that are selected from linear, branched, cyclic aliphatic or aromatic substituents with or without heteroatoms such as N, P, S , O, Si or halides such as F, Cl, Br and J, or a combination of these substituents, and when these substituents are attached to an oligomeric or polymer chain and bonded to a quaternary cationic center, this may be organic, inorganic or hybrid an organic-inorganic oligomer or polymeric structure attached to one or more transition metals. In such a case, the transition metal catalysts are anchored or bound to an organic, inorganic or hybrid organic-inorganic oligomer or polymer carrier. An example of such hydrocarbon substituents attached to an oligomeric or polymeric chain and attached to the quaternary cationic center is the benzyl portion of the benzyltrimethylammonium group formed when the crosslinked polystyrene is first chloromethylated and then aminated with trimethylamine.

In another embodiment of the present invention, quaternary ammonium or quaternary phosphonium cationic sol-gels, silicates or zeolites are formed when cationic centers containing a trimethoxysilyl group or a triethoxysilyl group, such as trimethoxysilylpropyltrin-n-butylammonium, triethoxysylammonium -butylammonium, trimethoxysilylpropyltrimethylammonium, trimethoxysilylpropyltriethylammonium, octadecyldimethyltrimethoxysilylpropylammonium, n-tetradecyldimethyltrimethoxysilylpropylammonium and trimethylsilylethoxyethyltriphenylphosphonethoxy, condensate; a Si-OH-containing dendrimer, such as those described by Majorali J. P. et al. in Chem. Rev., 99, p.

• ·

845-880 (1999); silicate or zeolite. When these quaternary cationic centers form ionic bonds with the transition metal complex, the transition metal complex is anchored or bound to the sol-gel, silicate, or zeolite.

Silicate and zeolite solid supports useful in the present invention are, for example, those with a microporous crystalline structure having a pore size similar to a 4A type molecular sieve (0.4 µm pore size), or such with a mesoporous crystalline structure having pores larger than a molecular sieve screen type 4A. Zeolites, silicates, aluminophosphates and silica aluminophosphates useful in the present invention are, for example, TS-1, TS-2, ZSM-5, ZSM-11, ZSM-12, ZSM-22, AZM-48, SAPO-5, SAPO-11 , zeolite X, zeolite Y, Linda type L, VPI-5, NCL-1, MCM-41 and MCM-48.

As mentioned above, the heterogeneous catalyst may also be formed by encapsulating the transition metal catalyst of Formula A in a solid support. The encapsulation process involves attaching a transition metal catalyst of formula A to the intrazeolite space of the support such that the transition metal catalyst of formula A, once arranged inside the zeolite, is too large to diffuse out of the zeolite. In this case, there is no covalent attachment of the transition metal complexes of the general formula A to the intrazeolite surface, so it can be expected that the complexes of the transition metal catalysts of the general formula A will be much more similar to their homogeneous analogs. Encapsulation of the transition metal catalyst of general formula A will simplify the separation of the transition metal catalyst from the final epoxidation product. An example of such an encapsulation technique is described by Bedioui F. in Coord. Chem. Rev., 144, 39 (1995).

In one embodiment of the heterogeneous catalysis method of the present invention, the weight ratio of the transition metal or transition metal complex in the catalyst to the total weight of the solid support is preferably in the range of 1.10 ^-6 to 1 part transition metal or transition metal complex per part solid support; more preferably, the weight ratio of the total weight of the transition metal or transition metal complex in the catalyst to the total weight of the solid support is in the range of 1.1 θ ⁶ to 1.10 ^-1 parts of transition metal or transition metal complex per part of solid support; and most preferably the weight ratio of the total weight of the transition metal or transition metal complex in the catalyst to the total weight of the solid support is in the range of 1.10 ^-6 to 1.10 ^-2 parts of transition metal or transition metal complex per part of solid support.

In another embodiment of the heterogeneous catalysis of the present invention, the weight ratio of the heterogeneous catalyst to the substrate allylarylether in the epoxidation reaction mixture is in the range of

1.10 ⁶ to 1.10 ^-6 parts of heterogeneous catalyst per part of allylarylethers; preferably, the weight ratio of the heterogeneous catalyst to the substrate allylarylethers in the epoxidation reaction mixture is in the range of 1.10 ³ to 1.10 ^-4 parts of heterogeneous catalyst per part of allylarylethers; and more preferably, the weight ratio of heterogeneous catalyst to substrate - allylarylethers - in the epoxidation reaction mixture is in the range of 1.10 ² to 1.10 ^-2 parts of heterogeneous catalyst per part of allylarylethers.

The heterogeneous catalysts of the present invention are useful again after each reaction, after washing with certain non-reactive solvents or dilute acid or dilute base. Once the epoxidation is carried out to the desired degree of conversion, the epoxy product can be separated and recovered from the reaction mixture by suitable techniques such as filtration, washing, fractional distillation, extractive distillation, liquid-liquid extraction, liquid-solid extraction and crystallization, or a combination of these methods.

Solvent

The reaction of the present invention may optionally be carried out in the presence of a solvent. Solvents that may be used in the reaction mixture of the present invention include solvents that do not react with the inorganic or organic hydroperoxide used in the reaction mixture of the present invention. Some solvents, such as dimethylsulfoxide, will react with an organic hydroperoxide, such as tert-butyl hydroperoxide (TBHP). Solvents that may be used in the present invention include, for example, aliphatic, cycloaliphatic or aromatic hydrocarbon solvents; partially or fully chlorinated, fluorinated or a combination of these halogenated aliphatic, cycloaliphatic or aromatic hydrocarbon solvents; aliphatic, cycloaliphatic or aromatic alcohols and nitriles; and partially or fully fluorinated aliphatic, cycloaliphatic or aromatic alcohols and nitriles.

The solvents used in the present invention are preferably chlorinated solvents such as dichloromethane, chloroform, carbon tetrachloride, chloroethane, dichloroethane, carbon tetrachloride, 1-chloropropane, 2-chloropropane and chlorobenzene; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; hydrocarbon solvents such as n-pentane, cyclopentane, methylcyclopentane, n-hexane, 2,5-dimethylhexane, 2,3-dimethylbutane, cyclohexane, methylcyclohexane, 1,3-dimethylcyclohexane, n-heptane, n-octane, isooctane , n-nonane and n-decane; aromatic solvents such as benzene, toluene, ethylbenzene, xylene and cumene; and low-boiling alcohols such as ethanol, propanol, isopropanol, n-butanol, sec-butanol, t-butanol, n-amyl alcohol, t-amyl alcohol, n-hexanol and cyclohexanol. The above list is not an exhaustive list and is intended only to represent solvents that are useful in the present invention.

Chlorinated solvents such as dichloromethane, dichloroethane, carbon tetrachloride and chlorobenzene are preferably used in the present invention.

In another embodiment of the present invention, solvents that can be used in the present invention are those that can be used under dense phase or supercritical conditions. Such solvents include, but are not limited to, carbon dioxide, ethane, and dimethyl ether.

Particularly useful solvents of the present invention are those that form azeotropic mixtures with water or alcohols, such as tert-butanol or tert-amyl alcohol, which are formed during epoxidation by reduction of hydroperoxide. The choice of such a solvent allows the continuous removal of water or alcohol formed in the epoxidation mixture and thus provides greater catalyst efficiency, since the water or alcohol formed can form strong bonds with the transition metal atom and thus reduce the activity of the catalyst.

Solvents that form azeotropic mixtures with water or an alcohol such as tert-butanol include, for example, cyclopentane, pentane, benzene, cyclohexane, methylcyclopentane, 2,3-dimethylbutane, hexane, heptane, ethylbenzene, 1,3-dimethylcyclohexane and 2-ol. 5-dimethylhexane.

Solvents that form azeotropic mixtures with water or an alcohol such as t-amyl alcohol include, for example, benzene, cyclohexane, methylcyclopentane, toluene, methylcyclohexane, heptane, ethylbenzene, 1,3-dimethylcyclohexane, 2,5-dimethylcyclohexane and octane.

Continuous removal of azeotropic mixtures can be carried out under ambient conditions, or under conditions below or above ambient conditions. The azeotropic mixtures may be separated and the solvent may be continuously returned to the reactor.

The solvent useful in the present invention is generally used in an amount of from 0 to 100 parts by weight of solvent per 1 part by weight of the substrate allylarylether. Preferably, the amount of solvent used is from 0 to 25 parts by weight of solvent per 1 part by weight of allylarylether substrate, and more preferably from 0 to 10 parts by weight of solvent per 1 part by weight of allylarylether substrate.

Ingredients

For example, the optional additive that may be used in the present invention may include a free radical inhibitor. These free radical inhibitors are preferably used to suppress non-epoxidation reactions and thus improve the selectivity of the hydroperoxide. Examples of free radical inhibitors that are useful in the present invention include, for example, 4-methyl-2,6-di-tert-butylphenol, 1,4-hydroquinone, 4-methoxyphenol, phenothiazine and the like.

4-tert-butylcatechol. The amount of these additives used in the present invention may be from 0 to less than 5% by weight of the total weight of the allylarylether substrate.

Another optional additive that may be used in the present invention may include, for example, an organic base or a buffering agent. The organic base or buffer is particularly useful in combination with a transition metal catalyst-complex in which the metal is in a higher oxidation state, such as the above-mentioned Mn and Re catalysts. The organic base or buffering agent is preferably used in the process of the present invention such that the epoxidation is carried out under neutral or slightly basic conditions. When the epoxidation is carried out under neutral or slightly basic conditions, unwanted opening of the epoxy ring of the product is avoided.

Organic bases useful in the present invention include, for example, organic pyridinyl derivatives such as pyridine and 3-cyanopyridine. The amount of this organic base used in the present invention may be from 0 to less than 20% by weight of the total weight of the allylarylether substrate. However, some organic bases, such as pyridine, function as epoxy ring opening catalysts of glycidyl ether. The aryl glycidyl ether epoxy ring (s) is particularly susceptible to opening by the action of organic bases. Thus, it is preferred to use an amount of organic base that is not detrimental to epoxidation, e.g., such amount of organic base may preferably be less than 5% by weight of the total weight of the substrate allylarylethers.

Reaction conditions

The reaction temperature of the present invention should be sufficient to achieve a solid conversion of the allylarylethers to the epoxide in a reasonably short time. In general, it is preferred to carry out the reaction so as to achieve the highest hydroperoxide conversion, preferably at least 50%, and more preferably at least 90%, in accordance with acceptable selectivity. The optimum reaction temperature will be influenced, inter alia, by catalyst activity, allylarylether reactivity, reactant concentration, and the type of solvent used. Typically, however, the reactions of the present invention are carried out at temperatures of from 0 to 120 ° C, preferably from 10 to 100 ° C, and more preferably from 20 to 80 ° C.

A suitable reaction time will typically be 10 minutes to 48 hours, depending on the above variables. The reaction time may preferably be in the range of 30 minutes to 24 hours.

The reaction pressure may be atmospheric, lower than atmospheric (e.g., from 666.6 to 1.01325.10 ⁵ Pa) or higher than atmospheric (from 1.01325.10 ⁵ to 1.01325.10 ⁷ Pa). It is preferred to carry out the reaction under an inert atmosphere such as nitrogen, helium or argon. In general, it will be preferable to maintain the reactants in a liquid mixture. However, the reaction may be carried out under conditions such that the water or alcohol formed during the epoxidation by reduction of the hydroperoxide is removed with the solvent as steam.

The process of the present invention may be carried out in a stirred batch, semi-continuous or continuous manner using any suitable type of screening vessel or apparatus. Thus, the reactants may be mixed together or sequentially. For example, the hydroperoxide may be added incrementally to the reaction. For example, when the hydroperoxide is used in excess, it is preferable to add it continuously to the mixture of allylarylethers and catalyst.

During the reaction, the reaction mixture may be analyzed by gas chromatography, high performance liquid chromatography or other known analytical methods.

After the epoxidation is complete, the reaction mixture is subjected to purification and separation using known methods, and the excess of unreacted organic oxidizing agent can be recycled. For example, once the epoxidation is brought to the desired degree of conversion, the desired epoxide product can be separated and isolated from the reaction mixture by suitable techniques such as filtration, fractional distillation, extractive distillation, liquid-liquid extraction, liquid-solid extraction or crystallization.

The by-product of the reaction will usually be the corresponding alcohol derived from the reduced organic hydroperoxide and can also be separated and recovered as a valuable product. For example, tert-butyl alcohol will be formed when TBHP is used as the oxidizing agent, while 1-phenylethanol is obtained using 1-phenylethyl hydroperoxide as the oxidizing agent. The alcohol product can be easily dehydrated to a useful olefin, such as isobutylene or styrene. Similarly, any unreacted olefin or organic hydroperoxide can be separated and recycled. After separation from the epoxidation reaction mixture, the obtained catalyst can be economically reused in further epoxidations.

Glycidyletherepoxidy

In general, the process of the present invention is useful in the production of arylglycidyl ether epoxides. A typical example of aryl glycidyl ethers produced by the process of the present invention includes 4,4'-bisphenol A diglycidyl ether.

In one embodiment of the present invention, arylglycidyl ethers produced by the method of the present invention are represented without limitation by the following general formula X:

(R ¹ ) x (R ² ) yAr (OR ⁴ ) z (X)

In formula X, x is from 0 to 750, y is from 0 to 750, and z is from 1 to 150.

Ar is a single core aromatic ring moiety such as phenyl. Ar may also be a ring-containing aromatic ring moiety such as biphenyl, 2,2-diphenylpropane, bisphenylene oxide, tetrakis (1,1,2,2-phenyl) ethane, stilbene. Also included are examples containing multi-core aromatic rings such as phenol-formaldehyde resins, cresol-formaldehyde resins, phenol-dicyclopentadiene resins and hyperbranched aromatic phenol dendrimers. Ar may also be a portion containing condensed aromatic rings formed of many nuclei, such as naphthalene, anthracene, and naphthalene-formaldehyde resins. Ar may also be a moiety comprising condensed aromatic rings consisting of multiple nuclei with one or more heteroatoms, such as O, N, S, Si, B or P, or a combination of such heteroatoms, such as quinoxaline, thiophene and quinoline. Ar may also be a moiety containing aromatic rings formed by one or more cores fused to the aliphatic (s) ring (s), such as indane, 1,2,3,4-tetrahydronaphthalene, and fluorene. Ar may also be a group containing aromatic rings formed by one or more nuclei fused to an aliphatic (s) ring (s) containing one or more heteroatoms, such as O, N, S, Si, B or P, or a combination of such heteroatoms, e.g. chromate, indoline and thioindane. Ar as described above in formula I may be partially or fully fluorinated.

In formula I, Ar may also be a moiety containing aryl groups in which each aryl group is attached to oligomers of an organosiloxane unit (eg, polymers with an average molecular weight of less than 5000) or an organosiloxane unit with a high molecular weight (eg, with medium relative molecular mass greater than 5000). Aryl groups are attached directly to the Si atoms of the organosiloxane units, or these aryl groups are attached to the Si atoms indirectly via an organic aliphatic moiety, an organic cycloaliphatic moiety, an organic aromatic moiety, or a combination thereof. The organic aliphatic, cycloaliphatic or aromatic moiety should not contain more than 20 carbon atoms. When the Ar moiety comprises such oligomeric organosiloxane units or high molecular weight organosiloxane units, z is preferably 1 to 150.

In one embodiment of the present invention, the aromatic ring of the Ar moiety containing the glycidyl ether of formula X is conformationally limited. The aromatic ring of the glycidyl ether-containing Ar moiety is conformationally limited because a) the free rotation of the aromatic ring (s) of the glycidyl ether-containing Ar moiety is limited due to the proximity of the atoms on the ring (s) of the glycidyl ether-containing Ar moiety (s) and adjacent aromatic ring (s) of the Ar moiety, which may or may not contain the glycidyl ether group (s), providing densification of the atoms that restrict the mobility of the aromatic ring (s) of the Ar moiety containing glycidyl ether and thus limits the mobility of the glycidyl ether group (s) OR ⁴ , such as when Ar is biphenyl; (b) the free rotation of the aromatic ring (s) of the Ar part containing the glycidyl ether is restricted due to the presence of rigid part (s) such as -CH = CR ⁵ -, amide groups and ester groups linking the aromatic the glycidyl ether ring (s) with the other aromatic ring (s) of the Ar moiety, which may or may not contain the glycidyl ether group (s), which limits the mobility of the aromatic ring (s) of Ar a glycidyl ether-containing moiety and thus limits the mobility of the OR ⁴ glycidyl ether moiety; or c) the free rotation of the OR ⁴ group on the aromatic ring (s) of the Ar moiety is limited due to the presence of at least one or more sterically hindered R ¹ groups other than hydrogen in the ortho position relative to the OR ⁴ group (s). In this case, the yield of glycidyl ether and the selectivity of the hydroperoxide are usually higher.

In formula X, R ^{1 is a} group that replaces a hydrogen atom at a position that is ortho to the OR ⁴ group (s) on the aromatic ring (s) of the Ar moiety. R ¹ is halogen such as bromine and chlorine; or a hydrocarbon radical such as an alkyl group, a cycloaliphatic group or an aromatic group. R ¹ is preferably an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl or isopropyl; a cycloaliphatic group having 3 to 20 carbon atoms, such as cyclopentyl and cyclohexyl; an aromatic group having 6 to 20 carbon atoms such as phenyl and naphthyl; or any combination thereof. The aforementioned hydrocarbon residues may also contain one or more heteroatoms such as O, N, S, Si, B or P, or any combination of these heteroatoms. An example of a hydrocarbon radical containing an O heteroatom is a methoxy, ethoxy or polyalkylene oxide group derived from ethylene oxide, propylene oxide, butylene oxide and cyclohexene oxide or the like. R ¹ of formula X as described above may also be partially or fully fluorinated.

In one preferred embodiment, there is at least one or more R ¹ substituents in the ortho position (s) relative to the OR ⁴ group (s) on the aromatic ring (s) of the Ar part. In such a preferred embodiment, the glycidyl ether (s) is conformationally limited because, due to the presence of at least one or more R ¹ groups, the free rotation of the OR ⁴ group on the aromatic ring (s) of the Ar moiety is limited due to the presence of at least one or more R ¹ groups in the ortho position (s) relative to the OR ⁴ group on the aromatic ring (s) of the Ar moiety. In such cases, the yield of glycidyl ether and the selectivity of the hydroperoxide are usually higher compared to a glycidyl ether having no R ¹ substituent (s) at the ortho position (s) relative to the OR ⁴ group (s).

In formula X, R ^{2 is a} group that replaces a hydrogen atom in a position that is not ortho to the OR ⁴ group (s) on the aromatic ring (s) of the Ar moiety. R ² is halogen such as bromine and chlorine; or a hydrocarbon radical such as an alkyl group, a cycloaliphatic group or an aromatic group. R ² is preferably an alkyl group having 1 to 20 carbon atoms, e.g., methyl, ethyl and propyl; a cycloaliphatic group having 3 to 20 carbon atoms, such as cyclopentyl and cyclohexyl; an aromatic group having 6 to 20 carbon atoms such as phenyl and naphthyl; or any combination thereof. The aforementioned hydrocarbon residues may also contain one or more heteroatoms such as O, N, S, Si, B or P, or any combination of these heteroatoms. An example of a hydrocarbon radical containing an O heteroatom is a methoxy, ethoxy or polyalkylene oxide group derived from ethylene oxide, propylene oxide, butylene oxide and cyclohexene oxide or the like. R ² of formula X as described above may also be partially or fully fluorinated.

In formula X, OR ^{4 is} an epoxy-containing oxy group that replaces the hydrogen atom on the aromatic ring (s) of the Ar moiety, wherein R ⁴ is the epoxy-moiety selected from:

/ ° \

C (R ⁵ ) 2 CR ⁵ -C (R ⁵ ) 2 / ° C

C (R ⁵⁾ 2 C (R ⁵⁾ 2 CR ⁵ -C (R ⁵⁾ ₂

wherein R ⁵ is hydrogen or an alkyl group, a cycloaliphatic group or an aromatic group and i is 0 to 6. R ⁵ is preferably an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl or propyl; a cycloaliphatic group having 3 to 20 carbon atoms, such as cyclopentyl and cyclohexyl; an aromatic group having 6 to 20 carbon atoms such as phenyl and naphthyl; or any combination thereof. Each R ⁵ may be the same or different from the others.

R ⁴ may also be a monoalkylene oxide group or a polyalkylene oxide group derived from ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide or the like, wherein each monoalkylene oxide group and each polyalkylene oxide unit is terminated with an epoxy moiety selected from:

/ ° \

C (R ⁵ ) 2 CR ⁵ -C (R ⁵ ) 2, -C (R ⁵ ) 2 C (R ⁵ ) 2 CR ⁵ -C (R ⁵ ) ₂ , and

wherein R ⁵ is the same group as described above.

In one embodiment, wherein R ⁴ in formula X is

Thus, the ether is "arylglycidyl ether".

In another embodiment, wherein R ⁴ in formula X is

O / \

-CH-C-CH ₂

CH, the ether is "aryl (methylglycidyl) ether". \

In yet another embodiment, wherein R ⁴ in formula X is

Thus, the ether is "aryl- (2,3-epoxycyclohexan-1-yl) ether".

More typical and preferred examples of aryl glycidyl ethers prepared by the process of the present invention are represented by the following formulas XI-XIV.

Examples of single-aromatic-core arylglycidyl ethers prepared by the process of the present invention are represented by the following general formula XI:

In formula XI, the groups R ¹ , R ² , OR ⁴ and R ^{4 have the} same meaning as described above in relation to formula X. In formula XI, x is from 0 to 4, y is from 0 to 3 and z is from 1 to 4.

Examples of "arylglycidyl ethers" and "aryl (methylglycidyl) ethers" represented by the general formula XI include, for example, 2,6-dimethylphenylglycidyl ether, 2,6-dimethylphenyl (methylglycidyl) ether, 4-methyl-2,6-dibromophenyl (methylglycidyl) ether and 1 , 4-, 1,5- or 2,6-naphthalenediglycidyl ethers.

Other examples of arylglycidyl ethers prepared by the process of the present invention are two-aromatic-core arylglycidyl ethers, which are represented by the following general formula XII:

(ΧΠ)

In formula XH, R ¹ , R ² , OR ⁴ and R ^{4 have the} same meaning as described above in relation to formula X. In formula XII, each x is from 0 to 3 and each x can be the same or different , each y is from 0 to 2 and each y may be the same or different, and each of is from 1 to 2 and each of may be the same or different.

In formula XII, X can be nothing; or X may be a heteroatom with or without substituents on the heteroatom to complement its necessary valence; the heteroatom is selected from O, N, S, Si, B or P, or any combination of two or more of said heteroatoms; X may also be, for example, -C (O) -; -S (O ₂ ) -; -C (O) NH-; -P (O) Ar-; an organic aliphatic moiety with or without heteroatoms such as oxydimethylene, methylene, 2,2-isopropylidene, isobutylene and -? R ⁵ = CH-, wherein R ⁵ is the same as defined above for formula X; a cycloaliphatic group with or without heteroatoms, such as a cycloaliphatic ring of more than 3 carbon atoms; or an aromatic group with or without heteroatoms; or any combination thereof, preferably containing less than 60 carbon atoms. X, as described above for formula XII, may be partially or fully fluorinated, such as 2,2-perfluoroisopropylidene.

Examples of "arylglycidyl ethers" and "aryl (methylglycidyl) ethers" represented by the general formula XII include, for example, 4,4'-bisphenol A diglycidyl ether; 4,4 '- (3,3', 5,5'-tetramethyl) bisphenol A diglycidyl ether; 4,4 '- (3,3', 5,5'-tetrabromo) bisphenol A diglycidyl ether; 4,4 '- (3,3', 5,5'-tetramethyl-2,2 ', 6,6'-tetrabromo) bisphenol A diglycidyl ether; 4,4 '- (3,3', 5,5'-tetramethyl) bisphenol F diglycidyl ether; 4,4´-bisphenol F diglycidylether; 4,4´-bisphenol sulfone diglycidyl ether; 4,4´-bisphenol K diglycidylether; 4,4 '- (3,3', 5,5'-tetramethyl-2,2 ', 6,6'-tetrabromobifenol) diglycidyl ether; 9,9-bis (4-glycidyloxyphenyl) fluorene; 4,4´-biphenol diglycidyl ether;

4,4 - - (3,3 5,5, 5,5 ’-tetramethylbiphenol) diglycidyl ether; (4,4'-dihydroxy-α-methylstilbene) diglycides 1ether; 1,3-bis (4-glycidyloxyphenyl) adamantane; 4,4´-bisphenol A dimethylglycidyl ether; 4,4 '- (3,3', 5,5'-tetramethyl) bisphenol A dimethylglycidyl ether; 4,4 '- (3,3', 5,5'-tetrabromo) bisphenol A dimethylglycidyl ether; 4,4 '- (3,3', 5,5'-tetramethyl-2,2 ', 6,6'-tetrabromo) bisphenol A dimethylglycidyl ether; 4,4 '- (3,3', 5,5'-tetramethyl) bisphenol F dimethylglycidyl ether; 4,4´-bisphenol F dimethylglycidyl ether; 4,4´-bisphenol sulfone dimethylglycidyl ether; 4,4´-bisphenol K dimethylglycidyl ether; 4,4 '- (3,3', 5,5'-tetramethyl-2,2 ', 6,6'-tetrabromobiphenol) dimethylglycidyl ether; 9,9-bis (4-methylglycidyloxyphenyl) fluorene; 4,4´-biphenol dimethyl glycidyl ether; 4,4 '- (3,3', 5,5'-tetramethylbifenol) dimethylglycidyl ether; (4,4'-dihydroxy-α-methylstilbene) dimethylglycidyl ether; 1,3-bis (4-methylglycidyloxyphenyl) adamantane.

Further examples of arylglycidyl ethers prepared by the process of the present invention are multi-aromatic-core arylglycidyl ethers which are represented by the following general formula (XIII):

(R ¹ ) _x (OR ⁴ ) _{Z (} α) (R ² ) y

In the general formula ΧΙΠ, the groups R ¹ , R ² , OR ⁴ , R ⁴ and X have the same meaning as described above in relation to the general formula ΧΠ. In formula XIII, each x is from 0 to 3 and each x may be the same or different, each y is from 0 to 3 and each y may be the same or different, and each of is from 1 to 2 and each of may be the same or different. In formula XIII, m is from 0.001 to 10.

Examples of "arylglycidyl ethers" and "aryl (methylglycidyl) ethers" represented by the general formula ΧΙΠ include eg glycidyl ether of o-cresol-formaldehyde resin (more than 2 functional groups), glycidyl ether of phenol-formaldehyde resin (more than 2 functional groups), glycidyl ether phenol- dicyclopentadienyl resins (more than 2 functional groups), naphthol-formaldehyde resin glycidyl ether (more than 2 functional groups), o-cresol-formaldehyde methyl glycidyl ether, phenol-formaldehyde resin methyl glycidyl ether, phenol-dicyclopentadienyl formaldehyde resin and methylglycidyl ether methyl ether.

Other examples of arylglycidyl ethers prepared by the process of the present invention are multi-aromatic-core arylglycidyl ethers which are represented by the following general formula XTV:

In the general formula XIV, the groups R ¹ , R ² , OR ⁴ and R ^{4 have the} same meaning as described above for the general formula vzorceΠΙ. In formula XIV, each x is from 0 to 3 and each x may be the same or different, each y is from 0 to 3 and each y may be the same or different, and each of is from 1 to 2 and each of may be the same or different.

In formula XIV, Y is an organic aliphatic moiety with heteroatoms such as O, N, S, Si, B or P, or any combination of two or more of said heteroatoms, or without heteroatoms having 1 to 20 carbon atoms, such as e.g. methine; a cycloaliphatic moiety with or without heteroatoms having 3 to 20 carbon atoms, such as a cyclohexanetriyl group; an aromatic moiety with or without heteroatoms, such as benzentriyl, naphthalentriyl, fluorentriyl; or any combination thereof with less than 20 carbon atoms. Y, as described above for formula XIV, may be partially or fully fluorinated, such as a fluoromethane group.

In formula XIV m is generally 3 or 4. However, Y may also be an oligomeric organosiloxane unit or a high molecular weight organosiloxane unit. In such a case, the aryl groups are attached to the Si atoms of the organosiloxane unit directly or indirectly through an organic aliphatic group, a cycloaliphatic group, an aromatic group, or any combination thereof with less than 20 carbon atoms. Thus, in formula XIV, m is from 1 to 150.

Examples of "arylglycidyl ethers" and "aryl (methylglycidyl) ethers" represented by the general formula XTV include, for example, tris (hydroxyphenyl) methane triglycidyl ether; tris (2,6-dimethylhydroxyphenyl) methane triglycidyl ether; 1,1,2,2-tetrakis (hydroxyphenyl) ethane tetraglycidyl ether; tris (hydroxyphenyl) methane trimethylglycidyl ether; tris (2,6-dimethylhydroxyphenyl) methane trimethylglycidyl ether and 1,1,2,2-tetrakis (hydroxyphenyl) ethane tetramethylglycidyl ether.

In another embodiment of the present invention, the glycidyl ethers of the above formulas XI-XIV are conformationally limited due to the presence of at least one or more R ¹ groups such as methyl, ethyl, isopropyl, phenyl, halogen, such as bromine, on aromatic rings in the ortho position (s) relative to OR ⁴ group (s). In such cases, the yield of glycidyl ether and the selectivity of hydroperoxide are very high compared to aryl glycidyl ethers without the R ¹ group (s) at ortho position (s) relative to the OR ⁴ group (s). Such steric hindrance can be observed, for example, in the case of 2,6-diisopropylphenylglycidyl ether.

In another preferred embodiment of the present invention, in the above formulas, ažΠ to XIV, either a small distance of atoms on the aromatic ring (s) adjacent to the aryl glycidyl ether containing ring (s) exists, which provides densification of the atoms which limits the mobility of the arylglycidyl ether group (s) (groups); or there is a rigid moiety linking the glycidyl ether containing aromatic ring (s) to another aromatic ring, which limits the mobility of the arylglycidyl ether structure. In both cases, the conversion of the allyl ether, the yield of epoxidation, and the selectivity of the hydroperoxide are very high compared to the allylarylethers which lack the effect of atomization or the effect of the rigid moiety connecting the aromatic rings.

It is believed that when such conformationally restricted aryl glycidyl ethers are formed, the interaction between the aryl glycidyl ether epoxide and the transition metal from the transition metal catalyst, which can lead to hydrolysis of the epoxy ring to form an undesired hydrolyzed glycol, is prevented.

The epoxy resins prepared by the process of the present invention are suitable for applications such as electrolytic coatings, powder coating, motor vehicle lacquers, industrial and construction coatings, plastic embedding of electrical components, compaction, molding, composites, laminates and adhesives.

The epoxy resins prepared by the process of the present invention based on aromatic compounds containing hydroxyl groups, e.g. based on cresol-formaldehyde resins, are particularly useful for preparing laminates for electrical engineering and plastic embedding of electrical components, cathodic electrolytic coatings and powder coatings because halogen atoms are undesirable components in the epoxy resins used in these applications.

From the foregoing description, one skilled in the art can readily recognize the essential features of the present invention and can, without departing from the spirit and scope of the present invention, make various changes and modifications to the present invention to adapt to various uses, conditions and embodiments.

The following examples further illustrate the method of the present invention, but are not intended to limit the invention in any way.

DETAILED DESCRIPTION OF THE INVENTION.

Examples 1 to 9

In Examples 1 to 9, the various aryl monoallyl ethers described in Table I below were epoxidized according to the following general procedure:

A mixture of allylarylether, tetrachloroethane solvent and t-butyl hydroperoxide (TBHP, 3 mol / l visooktan solution, anhydrous, water content less than 800 parts) was added to a four-necked glass reactor equipped with a condenser, thermometer, magnetic stirrer, nitrogen inlet, and temperature controller heater. water per million parts of solution). The catalyst Mo (CO) ₆ is added at room temperature under a nitrogen atmosphere. The amount of allylarylether used was 0.05 mol. The molar ratio of allylarylether to TBHP was 1: 1.1. The amount of Mo (CO) 6 catalyst used was 2.5 mol% of the molar amount of allylarylethers used. The amount of tetrachloroethane was 30 ml. The reaction was carried out at 65 ° C for 8 hours. After completion of the reaction, the reaction mixture was analyzed by GC / MS-gas chromatography coupled to a mass spectrometer to determine the amount of unreacted allylarylethers, the amount of glycidyl ether epoxide and the amount of hydrolyzed epoxide, i.e. glycol impurities.

Experimental results for Examples 1 to 9 are shown below in Table I, where "epoxidation yield,%" and "TBHP conversion,%" are based on the area of the peaks from the gas chromatogram. In Table I, "selectivity of TBHP,%" equals the ratio of "epoxidation yield,%" and "conversion of TBHP,%".

The R, R, and R groups listed in Table I correspond to the substituents of the following general equation:

Table I

Example The substituents R ^1, R ^2, R ³ Yield epoxidation,% Conversion TBHP,% Epoxidation yield,% * Example 1 R ¹ , R ² = H; R ³ = methyl 60 82 (74) Example 2 R ^1, R ³ = methyl; ^R2 = H 75 80 (93) > 90 Example 3 R ¹ = isopropyl; R ^J is methyl; ^R2 = H > 90 91 (> 98) > 95 Example 4 R ¹ = bromo; R ³ - methyl; ^R2 = H 85 88 (97) > 90 Example 5 R ^1, R ^2, R ³ = H 12 90 (12) Example 6 R ¹ = methyl; R ^2, R ³ = H 38 73 (52) Example 7 R ¹ = isopropyl; R ^2, R ³ = H 47 83 (57) Example 8 R ¹ = tert-butyl; R ^2, R ³ = H 27 Mar: 63 (42) Example 9 R ¹ = bromo; R ^2, R ³ = H 39 69 (56) In these experiments, after the initial amount of TBHP was consumed yes additional

the amount of TBHP to achieve a total molar ratio of TBHP to allylarylether used of up to 1.6: 1.

Comparison of the above results of Examples 2 to 4 with Example 1 and comparison of the above results of Examples 6 to 9 with Example 5 in Table I shows that glycidyl ethers that are conformationally constrained to prevent free rotation of the aromatic rings of glycidyl ethers due to different substituents in both ortho positions with respect to the OR ⁴ substituent, arise in higher yield with higher selectivity of TBHP. The substituent size has been found to dramatically affect the yield of epoxidation and the purity of the final "methylglycidyl ether" epoxide product in Examples 1-4 in Table I. For example, by introducing methyl, isopropyl and bromo groups at both ortho to OR ⁴ positions on the aromatic ring, achieves a 75 to 90% epoxidation yield and a TBHP selectivity of greater than 90% as shown in Table I of Examples 2-4. In Examples 2-4, the amount of impurity - hydrolyzed epoxy product - is less than 1 to 3%.

Improvements have also been observed in the yield of epoxidation of the final "glycidyl ether" epoxide product shown in Examples 6-9 in Table I. For example, by introducing methyl, isopropyl, tert-butyl and bromo groups at both positions on the aromatic ring that are ortho to OR ⁴ , achieves a 2 to 4-fold improvement in epoxidation yield and a 3 to 4-fold improvement in TBHP selectivity, as shown in Table I for Examples 5 to 9.

Similar results were also observed when the diglycidyl ethers of formula XII were synthesized as shown in Table Π. When conformationally limited diallyl ethers of bifenol (s) were used, such as in the examples in Table Π, not only did the epoxidation yield improve, but also the total amount of diglycidyl ether diepoxides increased.

Examples 10 to 18

Examples 10 to 18 in Table Π were performed in the same manner as Examples 1 to 9 except that aryl bis bisallyl ethers and bismethallyl ethers were used as substrates. The amount of aryl bis (meth) allyl ether used was 0.025 mol. The molar ratio of arylbis (meth) allyl ether to TBHP was 1: 2.2. The amount of Mo (CO) 6 catalyst used was 5 mol% of the molar amount of arylbis (meth) allyl ether used. The amount of tetrachloroethane was 50 ml. The reaction was carried out at 65 ° C for 6 to 20 hours, whereby two or more samples of the reaction mixture were analyzed after the time period shown in Table II. The reaction mixture was analyzed by high pressure liquid chromatography (HPLC) and the structure of the product was confirmed by GC / MS. In Examples 11-15 and Example 17, where the reaction rate was very slow, an additional amount of TBHP was added after the initial amount of TBHP was consumed to achieve a total molar ratio of TBHP to allylarylethers of up to 3.2: 1. Thereafter, the reaction was maintained until the reaction rate was again very slow.

The results of Examples 10-18 are shown in Table H, wherein the ratio of aryldi (methyl) glycidyl ether diepoxide ("Di-E,%") to arylmono (methyl) glycidyl ether monoepoxide ("Μθηο-Ε,%") to arylbis (meth) Allyl ether ("Bis-AE,%") is based on the ratio of peak areas measured by HPLC. The total epoxidation yield ("TEY,%") is calculated as follows:

TEY,% = [(2 x peak area Di-E) + peak area Mono-E] + 2 x [(peak area Di-E) + (peak area Mono-E) + (peak area Bis-AE)]

The reaction in these examples using the substrates listed in Table II is illustrated by the following general equation:

OCH

R1 ^R3

Table II

Example Substrate Response time, clock Di-E%; Mono-E% .Bis-AE% (TEY%) 10 R ^{1 =} H; R ^J is methyl; Z = isopropylidene 16 46:43:11 (69) 11 R ^{1 =} R ³ = methyl; Z = isopropylidene 16 58: 36: 6 20 ’ 74: 23: 3 12 R ^{1 =} H; R ^J is methyl; Z = nothing 8 29: 4: 22 16 ’ 56: 37: 6 13 R ³ = R ³ = methyl; Z = nothing 8 23:51:26 (47) 12 26:52:10 (51) 20 ’ 53: 40: 7 14 R = isopropyl; R = methyl; Z = nothing 6 38:47:15 (63) 12 ’ 72: 26: 2 15 Dec R / ^J R = H; Z = isopropylidene 8 6:36:58 (23) 16 ’ 9:39:51 (28) 16 R ^{1 =} methyl; R ³ = H; Z = isopropylidene 8 12:46:42 (34) 16 24:52:24 (49) 17 R ^{1 =} Br; R ^J = H; Z = isopropylidene 8 9:41:50 (31) 16 ’ 15:48:37 (38) 18 R '= isopropyl; R ^J = H; Z = isopropylidene 8 9:42:49 (29) 16 23:53:28 (47)

An additional amount of TBHP was added to achieve a total molar ratio of TBHP to arylbisallyl ether of up to 3.2: 1.

The above results from Table Π show that in cases where glycidyl ethers were conformationally constrained because the free rotation of the glycidyl ether aromatic rings was limited due to the proximity of the hydrogen atoms on the aromatic rings adjacent to the glycidyl ether containing aromatic rings, providing densification of the atoms structure, so that in these cases the yields were usually higher, as shown in Examples 11, 13, 14 and 16-18 of Table II above.

Examples 19 to 32

In Examples 19 to 32, various catalysts with different ligands, such as cyclopentadienyl (Cp) and DPPE (diphenylphosphinylethane), were used in the epoxidation of arylmethallyl ethers and the same general procedure as described in Examples 1 to 9, except that the amount was varied. of the catalyst and the reaction was carried out at different temperatures as indicated in Table ΙΠ. The results of Examples 19-32 are shown in Table ΙΠ.

The R ¹ , R ² and R ³ groups listed in Table III below correspond to the substituents of the following general equation:

⁽²⁾ Examples 22 to 24: R 1 is methyl; R ² = H; R ³ = methyl.

⁽³⁾ Examples 30 to 32: R ^{1 =} isopropyl; R ² = H; R ³ = methyl.

I.E

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<

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sr • c

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• · • and • * · »· · · to M <· _{Ί --ΛΑ-Μ-} ¹ * - * - * - * Ί

LU it with LU of- at. uj O ζλ it s © it 00 it -O it σχ it LA it -at £ it LU it it it 1— * / · “» to- > » it O z — h s © Example ? O K> of-*\ £ £ K> with O O O O\ £ O O K> O M + O ΪΛ > - * » O 5J Jr UJ with O O tsJ £ £ KJ O TO) Q κΤ I.E G O_ Cp (CO) (DPPE) MoCl 3 ►0 I.E w AND /-"WITH O O to '□' doopi with O O it Q tS " § O O ir KJ AND O O X — Z os Catalyst lu LA lu LA to-' lo LA k — o lo LA to-' lo LA to-* lo LA w- lo LA !_AT lo LA »- » lo LA ►— * “it Ol YEAH la lo LA 1,25 2.5 Catalyst, molar% 65 65 65 55 55 LA LA 55 55 55 65 65 40 1 60 65 Temperature, ° C 00 00 00 to-* O LA Ό 00 Ό 00 -at it 00 00 00 Response time, clock 77 82 00 to — ► 54 and 50 ZS 55 54 57 57 64 42 52 57 Yield epoxidation,% 80 85 99 -O to-* 00 77 00 -AT 80 75 75 82 49 Ϊ ⁷⁵ 82 TBHP Conversion % 96 95 00 LA -4 pers Ch it 68 65 68 76 -0 Os 78 00 Os 69 70 TBHP selectivity, %

Table HI «·« · ·

9 r · »» V V V V 9 9 9 9 »

9 9 9 99 9 9 9 9 9 · · ·

Comparative Examples A and B

In Comparative Examples A and B, aryl monoallyl ethers with the structures described in Table IV below were epoxidized according to the following procedure described in U.S. Patent No. 5,633,391:

To a four-necked glass reactor equipped with a condenser, thermometer, magnetic stirrer, nitrogen inlet, and temperature controller heater was added 8.8 g (0.06 mol) of bis (trimethylsilyl) peroxide, 50 g of t-amyl alcohol and 0.32 g of rhenium methyltrioxide. (MTO, 2.5 mol% of the molar amount of monoallyl ether used) and the mixture was stirred at room temperature under nitrogen atmosphere for 5 minutes. Then, 0.05 mol of monoallyl ether was added to the reactor. The molar ratio of allylarylether to oxidizing agent was 1: 1.2. The reaction was carried out at 25 ° C for 5-8 hours. After completion of the reaction, the reaction mixture was analyzed by GC / MS-gas chromatography coupled to a mass spectrometer to determine the amount of unreacted allylarylether, the amount of glycidyl ether epoxide and the amount of hydrolyzed epoxide, i.e. glycol impurities.

Experimental results for Comparative Examples A and B are shown below in Table IV, where "epoxidation yield,%" and "glycol impurity yield,%" are based on the area of the peaks from the gas chromatogram.

The R ¹ , R ² and R ³ groups listed in Table IV correspond to the substituents of the following general equation:

(CH3) ₃ SiOOSi (CH3) ₃

MTO t-amyl alcohol

Table IV

Comparative example The substituents R ^1, R ^2, R ³ Epoxidation yield,% Yield of glycol impurities,% Comparative example R ^1, R ³ = methyl; ^R2 = H 58 ’ 12 Comparative example R ^ R ^ R ^ H <1 9

y— - ..... — ............... I ..... .........-,., 1 ..

All epoxide decomposed within 3 days of standing at room temperature.

························································ 4 9

Comparative Examples A and B in Table IV show that the oxidant-catalyst system described in U.S. Pat. No. 5,633,391 had a detrimental effect on the yield of epoxidation and the purity of the final epoxy product - glycidyl ether.

In Comparative Example A, in which rhenium bis (trimethylsilyl) peroxide and methyltrioxide were used, the yield of epoxidation before final product treatment was only 58% and 12% was the yield of hydrolyzed glycol impurities. After finishing and standing at room temperature for three days, the reaction product of Comparative Example A decomposed and all epoxide disappeared. By way of comparison, Example 2 of Table I showed an epoxidation yield of 75% without significant amounts of glycol impurities and after finishing and standing at room temperature for several months there was no indication of decomposition of the epoxy product of Example 2. These two examples indicate that higher valency catalysts , such as rhenium methyltrioxide, are very acidic and cause epoxide hydrolysis both during epoxidation and after the epoxy product has been finished.

Similar results to those described for Comparative Example A and Example 2 were obtained when comparing Comparative Example B and Example 5.

Comparative Examples C to F

In the following Comparative Examples C to F, the following glycols were added to the epoxidation reaction mixture containing allylarylether and TBHP prior to starting the epoxidation. 12.5 mol% and 25 mol% 3-phenoxy-1,2-propanediol (Comparative Examples C and D) or 12.5 mol% and 25 mol% 1,2-propanediol (Comparative Examples E and F) (mole percent) are derived from allylphenyl ether as shown in Table V below. The following general procedure was used in Comparative Examples C to F:

To a four-necked glass reactor equipped with a condenser, a thermometer, a magnetic stirrer, a nitrogen inlet, and a temperature regulator heater, glycol (as shown in Table V below), 0.05 mol of 2,6-dimethylphenylmethallyl ether, was added at room temperature under nitrogen. , 10/25 ^'3 Mo (CO) 6 and 50 g tetrachloroethane. After stirring at 65 ° C for 30 min, the reaction mixture was cooled to room temperature and 0.06 mol of TBHP was added to the reactor. The molar ratio of arylmethallyl ether to oxidizing agent was 1: 1.2. The amount of Mo (CO) δ catalyst used was 2.5 mol% of the molar amount of methallyl ether used. The reaction was carried out at 65 ° C for 4 hours. After completion of the reaction, the reaction mixture was analyzed by GC / MS-gas chromatography coupled to a mass spectrometer. Experimental results for Comparative Examples C to F are shown in Table V below, where "epoxidation yield,%" is based on the area of the peaks from the gas chromatogram.

Table V

Example Glycol added to the epoxidation reaction mixture Epoxidation yield,% Example 2 none 60 Comparative Example 3-Phenoxy-1,2-propanediol <2 Comparative example 3-Phenoxy-1,2-propanediol <20 Comparative Example 1,2-propanediol <5 Comparative Example 1,2-propanediol <10

Comparative Examples C and D show that the addition of 3-phenoxy-1,2-propanediol to the epoxidation reaction mixture immediately caused inactivation of the molybdenum catalyst and low yield of glycidyl ethers. Comparative Examples E and F show a similar inactivating effect of glycol. When 1,2-propanediol was added to the epoxidation reaction mixture, the molybdenum catalyst was also deactivated and the yield of glycidyl ethers was also low.

The results of Comparative Examples C to F, as opposed to Example 2 of the present invention, illustrate the assumption that inactivation of the epoxidation catalyst was due to the formation of hydrolyzed glycol from arylglycidyl ethers during epoxidation. It is further believed that the formation of glycol is due to the interaction of arylglycidyl ethers with a transition metal catalyst and that the use of conformationally restricted allylarylethers prevents or prevents the formation of hydrolyzed glycol.

Industrial applicability.

The invention is useful in the production of aromatic glycidyl ether epoxide compounds by a method which uses a conformationally restricted allylary ether as the starting compound, a hydroperoxide oxidizing agent, and a transition metal catalyst comprising at least one or more stable ligands bound to the transition metal.

Claims (51)

PATENT CLAIMS A process for the preparation of an aromatic glycidyl ether epoxide compound, characterized in that allylarylether is contacted with a hydroperoxide oxidizing agent in the presence of a transition metal complex catalyst, wherein at least (a) allylarylether is conformationally restricted; or b) the transition metal complex catalyst comprises at least one or more stable transition metal ligands. Method according to claim 1, characterized in that an allylary ether is used which is conformationally limited: (ii) the presence of a rigid moiety linking the aromatic rings of which at least one is an allylarylether moiety which limits the mobility of the allylarylether structure; or (iii) the presence of at least one substituent on the aromatic ring of the allylarylethers ortho to the allyl ether group, which sterically prevents or restricts the free rotation of the allyl ether group. 3. A process for the preparation of a multifunctional aryl glycidyl ether epoxide compound, characterized in that the multifunctional allylarylether of arylphenol is contacted with a hydroperoxide oxidizing agent in the presence of a transition metal complex catalyst. A method according to claim 3, characterized in that at least (a) the multifunctional allylarylether is conformationally limited; or b) the transition metal complex catalyst comprises at least one or more stable transition metal ligands. The method of claim 1, wherein an allylary ether having the structure represented by the following formula (I) is used: (R ') _x (R ² ), Ar (OR ³ ), (I) wherein x is from 0 to 750, y is from 0 to 750 and z is from 1 to 150; Ar is a moiety containing aromatic rings; R ¹ is a group that replaces a hydrogen atom at positions ortho to the OR ³ group on the aromatic ring of the Ar moiety; R ² is a group that replaces a hydrogen atom at positions other than ortho to the OR ³ group on the aromatic ring of the Ar moiety; OR ³ is an oxy group containing a propenyl group that replaces the hydrogen atom on the aromatic ring of the Ar moiety; and R ³ is a propenyl group. The method of claim 5, wherein Ar is a moiety selected from the group consisting of a single core aromatic ring moiety; the ring-containing aromatic ring; a multi-core condensed aromatic ring moiety; a portion comprising condensed aromatic rings consisting of many nuclei with one or more heteroatoms; a ring-containing aromatic ring formed by a single ring condensed with a cycloaliphatic ring or a ring-containing aromatic ring formed by a plurality of rings condensed with a cycloaliphatic ring; a ring-containing aromatic ring formed with one ring fused to a cycloaliphatic ring containing one or more heteroatoms selected from O, N, S, Si, Β, P and combinations thereof or a ring-containing aromatic ring formed from many rings fused to cycloaliphatic rings containing one or more heteroatoms selected from O, N, S, Si, Β, P and combinations thereof; and a group of aryl moieties in which each aryl moiety is attached to an oligomeric or high molecular weight organosiloxane unit. A method according to claim 5, characterized in that an allylary ether having a structure represented by any of the following formulas Π to IV is used: <( ^{R 1} ) _X (Π) (R ² where x is from 0 to 4, y is from 0 to 3 and z is from 1 to 4; R ¹ is a group that replaces a hydrogen atom at positions ortho to the OR ³ group on the aromatic ring; R ² is a group that replaces a hydrogen atom at positions other than ortho to the OR ³ group on the aromatic ring; OR ³ is an oxy group containing a propenyl group which replaces the hydrogen atom on the aromatic ring; R ³ is a propenyl group containing portion; X is nothing; heteroatom; -WHAT)-; -S (O 2) -; -C (O) -NH-; -P (O) Ar-; an organic aliphatic moiety with or without heteroatoms; a cycloaliphatic group with or without heteroatoms; an aromatic group with or without heteroatoms; or any combination thereof; m is from 0.001 to 10; Y is an organic aliphatic moiety with or without heteroatoms having 1 to 20 carbon atoms; a cycloaliphatic moiety with or without heteroatoms having from 3 to 20 carbon atoms; an aromatic moiety with or without heteroatoms having less than 20 carbon atoms; or is Y an oligomer or a high molecular weight organosiloxane unit; and m 'is 3 or 4, or when Y is an oligomeric or high molecular weight organosiloxane unit, m is from 1 to 150. 8. A method according to claim 7, characterized in that R ¹ and R ² are selected from the group consisting of halogen; (C 1 -C 20) alkyl; C 3 -C 20 cycloaliphatic; an aromatic group having 6 to 20 carbon atoms; or any combination thereof; wherein R ¹ and R ² may be different or the same. The method of claim 8, wherein the alkyl group; a cycloaliphatic group; or the aromatic group contains one or more heteroatoms and these heteroatoms are selected from the group consisting of O, N, S, Si, B or P, or any combination of these heteroatoms with or without substituents on those heteroatoms necessary to complement the bonding of the heteroatoms. 10. The method according to claim 9, characterized in that R ¹ and R ² may be partially or completely fluorinated. 11. The method of claim 8 wherein R ¹ is selected from the group consisting of methyl, ethyl, isopropyl and halo. A method according to claim 7, characterized in that R ³ is selected from the group R k / - ( ^{R 5} ) i containing -C (R ⁵ ) 2 CR ⁵ = C (R ⁵ ) 2, -C (R ⁵ ) 2 C ( R ⁵ ) 2CR ⁵ = C (R ⁵ ) ₂ and ^{R 5 R 5} ; and a polyalkylene oxide group derived from ethylene oxide, propylene oxide, butylene oxide and cyclohexene oxide terminated by one of the structures selected from the group consisting of 1 to 20 carbon atoms; a cycloaliphatic group having 3 to 20 carbon atoms; or an aromatic group having 6 to 20 carbon atoms, wherein each individual R ⁵ may be the same or different from the others; and i is from 0 to 6. The method of claim 7, wherein the allylary ether is selected from the group consisting of 2,6-dimethylphenylallyl ether; 2,6-dimethylphenylmethallyl ether; 4-methyl-2,6-dibromophenylallyl ether; 4-methyl-2,6-dibromophenylmethallyl ether; 1,4-, 1,5- or 2,6-naphthalenediallyl ethers; 1,4-, 1,5- or 2,6-naphthalenedimethallyl ethers; 4,4´-bisphenol A diallyl ether; 4,4 '- (3,3', 5,5'-tetramethyl) bisphenol A diallyl ether; 4,4 '- (3,3', 5,5'-tetrabromo) bisphenol A diallyl ether; 4,4 '- (3,3', 5,5'-tetramethyl-2,2 ', 6,6'-tetrabromo) bisphenol A diallyl ether; 4,4 '- (3,3', 5,5'-tetramethyl) bisphenol F diallyl ether; 4,4´-bisphenol F diallylether; 4,4´-bisphenol sulfone diallyl ether; 4,4´-bisphenol K diallylether; 4,4 '- (3,3', 5,5 '- tetramethyl-2,2', 6,6 '- tetrabromobifenol) dially lether; 9,9-bis (4-allyloxyphenyl) fluorene; 4,4'-bifenoldially lether; 4,4 '- (3,3', 5,5'-tetramethylbiphenol) diallyl ether; 4,4´-diallyloxy-α-methylstiene; 1,3-bis (4-allyloxyphenyl) adamantane; 4,4´-bisphenol A dimethallyl ether; 4,4 '- (3,3', 5,5'-tetramethyl) bisphenol A dimethallyl ether; 4,4 '- (3,3', 5,5'-tetrabromo) bisphenol A dimethallylether; 4,4 '- (3,3', 5,5'-tetramethyl-2,2 ', 6,6'-tetrabromo) bisphenol A dimethallyl ether; 4,4 '- (3,3', 5,5'-tetramethyl) bisphenol F dimethallyl ether; 4,4´-bisphenol F dimethallylether; 4,4´-bisphenol sulfone dimethallyl ether; 4,4´-bisphenol K dimethallylether; 4,4 '- (3,3', 5,5'-tetramethyl-2,2 ', 6,6' -tetrabromobifenol) dimethallyl ether; 9,9-bis (4-methallyloxyphenyl) fluorene; 4,4´-bifenoldimethallylether; 4,4 '- (3,3', 5,5'-tetramethylbifenol) dimethallyl ether; 4,4´-dimethallyloxy-α-methylstilbene; 1,3-bis (4-methallyloxyphenyl) adamantane; allyl ether of o-cresol-formaldehyde resins with more than 2 functional groups; phenol-formaldehyde resin allyl ether with more than 2 functional groups; phenol-dicyclopentadienyl resin allyl ether with more than 2 functional groups; naphthol-formaldehyde resin allyl ether with more than 2 functional groups; o-cresol-formaldehyde methallyl ether with more than 2 functional groups; phenol-formaldehyde resin methallyl ether with more than 2 functional groups; phenol-dicyclopentadienyl resin methallyl ether with more than 2 functional groups; naphthol-formaldehyde methallyl ether resin with more than 2 functional groups; tris (hydroxyphenyl) methane triallyl ether; tris (2,6-dimethylhydroxyphenyl) methane triallyl ether; 1,1,2,2-tetrakis (hydroxyphenyl) ethane tetraallyl ether; tris (hydroxyphenyl) methane trimethallyl ether; tris (2,6-dimethylhydroxyphenyl) methane trimethallyl ether and 1,1,2,2-tetrakis (hydroxyphenyl) ethane tetramethallyl ether. 14. The process of claim 1 wherein the hydroperoxide oxidizing agent is aqueous hydrogen peroxide containing from about 3% to about 75% hydrogen peroxide. The method of claim 1, wherein the hydroperoxide oxidizing agent is an organic hydroperoxide having the following general formula 1: R _a R — C-OOH (2) R _c wherein R a, R b and R c are the same or different and are selected from the group consisting of hydrogen; an alkyl group; a cycloaliphatic group; an aromatic group; or a combination thereof; or a combination of two or more Ra, Rb and Rc may also be contained in the same structural unit. The method of claim 15, wherein an organic oxidizing agent selected from the group consisting of tert-butyl hydroperoxide, tert-amyl hydroperoxide; and optionally, the organic oxidizing agent is used in an inert organic solvent or aqueous solution, wherein the tert-butyl hydroperoxide and tert-amyl hydroperoxide solutions contain 3 to 75% by weight of the organic hydroperoxide. 17. The process of claim 1 wherein the transition metal complex having the following formula (A) is used as the catalyst: [M ⁿ with Ot (Q) u (HX (L ¹ ) v (L ² ) v (L ³ ) v (L ⁴ ) _v ... (L% (G \ (G ² ), · (G ³ ) v (G ⁴ ) v ... (0% (A) where M is d ° or f ° transition metal atom; n is the oxidation degree of the metal M and n is 0 or an integer from 1 to 7; s is an integer from 1 up to 5; O is the oxygen of the oxometallic moiety having the general structure M = O; or O is the oxygen of the μ-oxometallic moiety having the general structure M-O-H or M-O-M; t is an integer from 0 to 3; Q is O 2, where O is oxygen and Q is a peroxy group attached to the metal M to form a three-membered ring, one peak of which is the metal atom M and the other two peaks are the peroxy group, as is M /? Illustrated in the general structure ^0-0 ; is an integer from 0 to 3; H is a hydrogen atom which is attached to the metal atom M to form the general structure M-H; or H is hydrogen which is attached to the oxygen of the μ-oxometallic moiety having the general structure M-O-H; L, L ¹ , L ² , L ³ , L ⁴ and ^Lβ are ligands up to the maximum number of β ligands; G ¹ , G ² , G ³ , G ⁴ and G ^p are cations to M-O 'anions up to the maximum number of p cations; v is an integer from 0 to 10; and w is an integer from 1 to 10. The method of claim 17, wherein the transition metal M is selected from the group of elements IVa, Va, Via, and Vila. 19. The process of claim 18 wherein the transition metal M is selected from the group consisting of Ti, Zr, V, Mo, W, Re, and Mn. The method of claim 17, wherein each of the L ¹ , L ² , L ³ , L ⁴ ... L ^p ligands may be either a strongly bound, non-interchangeable, neutral or basic, monodentate or multidentate ligand; or a labile, weakly bound, neutral or basic, monodentate or multidentate ligand; or combinations thereof. 21. The method of claim 20 wherein the ligand is a multidentate ligand that is bound to the same metal atom or to two or more different metal atoms, or the ligands are bound to an organic polymer chain, an inorganic polymer chain, or a hybrid inorganic-organic polymer. string. The method of claim 17, wherein the ligands comprise heteroatoms selected from the group consisting of O, N, S, Si, Β, P, or any combination of these heteroatoms. 23. The method of claim 17, wherein the ligand is a monodentate or multidentate ligand selected from oxygen-containing ligands, phosphorus-containing ligands, nitrogen-containing ligands, aromatic-containing ligands, organosilyl-containing ligands, organosilyloxy-containing ligands, and combinations thereof. 24. The method of claim 17 wherein the ligands are partially or fully fluorinated, or ligand L comprises one or more asymmetric or chiral centers in its structure. 25. The method of claim 17 wherein each cation G ^1, G ^2, G ^3, G ⁴ ... G ^p is an inorganic cation of Group Ia alkali metals; or inorganic cations of the IIIa alkaline earth metal group; or inorganic cations of the Illb metal group; or a cation comprising an organic compound of a Vb group element, wherein the cation is formed by at least one Vb group element and at least one organic substituent bound to the Vb group element. 26. The method of claim 25, wherein each of the cations of la of the alkali metal group is Na ⁺ , K ^+, or Cs ⁺ ; or the inorganic cation of the Illb metal group is Al ³⁺ . The method of claim 25, wherein each of the inorganic cations of the IIIa alkaline earth metal group is Mg ²⁺ or Ca ²⁺ . 28. The method of claim 27, wherein the cation containing the organic compound of the Vb group element is formed by at least one or more quaternary cationic centers selected from the group consisting of nitrogen, phosphorus, arsenic, antimony, or bismuth. 29. The method of claim 27 wherein the organic substituents bound to the Vb group element are C1-C20 aliphatic hydrocarbons, aromatic hydrocarbons, heterocyclic aliphatic or aromatic hydrocarbons, and aliphatic or aromatic hydrocarbons containing halogen. 30. The method of claim 29, wherein the organic substituents bound to the Vb group element are attached to the backbone of an organic, inorganic or hybrid organic-inorganic oligomer or polymer structure. 31. The process of claim 1 wherein the catalyst is a homogeneous catalyst which is a transition metal complex. 32. The process of claim 1 wherein the catalyst is a heterogeneous transition metal catalyst. Process according to claim 31 or 32, characterized in that a catalyst is used which is a transition metal complex of Ti, Zr, V, Mo, W, Re or Mn, or any combination thereof. 34. The process of claim 31, wherein the catalyst is a transition metal complex anchored to the solid support via a condensation reaction between the reactive group on the transition metal complex ligands and the reactive group on the solid support. 35. The method of claim 31, wherein a transition metal complex is anchored to the solid support by forming a strong, stable metal-ligand bond, wherein the ligand is initially bound to or is part of a solid support. 36. The method of claim 31, wherein the catalyst is a transition metal complex deposited on, anchored to, or encapsulated in a carrier selected from the group consisting of crosslinked polymers based on styrene divinylbenzene copolymer; ion exchange resins; aromatic polyimides; organosolgels; activated carbon; coal; silicas; alumina; Ba ₂ SO ₄ ; MgO; clays; silicates; zeolites; phosphites; aluminates; or any combination thereof. 37. The process of claim 1, wherein an arylglycidyl ether having the structure represented by formula (X) is prepared: (R ¹ ) _x (R ² ), Ar (OR ⁴ ) z (X) wherein x is from 0 to 750, y is from 0 to 750 and z is from 1 to 150; Ar is a moiety containing aromatic rings; R ¹ is a group that replaces a hydrogen atom at positions ortho to the OR ⁴ group on the aromatic ring of the Ar moiety; R ² is a group that replaces a hydrogen atom at positions other than ortho to the OR ⁴ group on the aromatic ring of the Ar moiety; OR ⁴ is an epoxy-containing oxy group that replaces the hydrogen atom on the aromatic ring of the Ar moiety; and R ⁴ is an epoxy moiety. 38. The method of claim 37 wherein Ar is a moiety selected from the group consisting of an aromatic ring comprising a single core; the ring-containing aromatic ring; a multi-core condensed aromatic ring moiety; the condensed aromatic ring moiety consisting of many nuclei with one or more heteroatoms selected from O, N, S, Si, Β, P and combinations thereof; a ring-containing aromatic ring formed by a single ring condensed with a cycloaliphatic ring or a ring-containing aromatic ring formed by a plurality of rings condensed with a cycloaliphatic ring; a ring-containing aromatic ring comprising one nucleus fused to a cycloaliphatic ring containing one or more heteroatoms or a ring-containing aromatic ring consisting of many nuclei fused to cycloaliphatic rings containing one or more heteroatoms; and a group of aryl moieties in which each aryl moiety is attached to an oligomeric or high molecular weight organosiloxane unit. 39. The method of claim 37, wherein an aryl glycidyl ether having the structure represented by any one of formulas XI-XIV is prepared: wherein x is from 0 to 4, y is from 0 to 4 and z is from 1 to 4; R ¹ is a group that replaces a hydrogen atom at positions ortho to the OR ⁴ group on the aromatic ring; R ² is a group that replaces a hydrogen atom at positions other than ortho to the OR ⁴ group on the aromatic ring; OR ⁴ is an epoxy-containing oxy group that replaces the hydrogen atom on the aromatic ring; and R ⁴ is an epoxy moiety; X is nothing; heteroatom; -WHAT)-; -S (O 2) -; -C (O) -NH-; -P (O) Ar-; an organic aliphatic moiety with or without heteroatoms; a cycloaliphatic group with or without heteroatoms; an aromatic group with or without heteroatoms; or any combination thereof; wherein x is from 0 to 3, y is from 0 to 2 and z is from 1 to 2; m is from 0.001 to 10; Y is an organic aliphatic moiety with or without heteroatoms having 1 to 20 carbon atoms; a cycloaliphatic moiety with or without heteroatoms having from 3 to 20 carbon atoms; an aromatic moiety with or without heteroatoms having less than 20 carbon atoms; or Y is an oligomeric or high molecular weight organosiloxane unit; and m 'is from 3 to 4, or when Y is an oligomeric or high molecular weight organosiloxane unit, m is from 1 to 150. 40. The method of claim 39 wherein R &lt; ⁴ &gt; is selected from the group ^O / ^R &^lt; ^{5 &gt;} OO / \ / \ C (R ⁵⁾ 2 CR ⁵ -C (R ⁵⁾ second -C (R ⁵⁾ 2 C (R ⁵⁾ 2CRS- C ^(R5) ₂ ^(R5) and containing ^'a; '''And^a''' and a polyalkylene oxide group derived from ethylene oxide, propylene oxide, butylene oxide and _CR6 _ / \ _RS cyclohexene end a structure selected from L-RC (R) _second R ⁵ ₀ R ⁵ of ° \ -C (R 5) ₂ C (R 5) ₂ CRS-C (R ⁵ ) ₂ R ¹ - (R ⁵ ) 1, wherein R ⁵ is hydrogen; an alkyl group having 1 to 20 carbon atoms; a cycloaliphatic group having 3 to 20 carbon atoms; or an aromatic group having 6 to 20 carbon atoms, wherein each R ⁵ may be the same or different from the others; and i is 0 to 6. 41. The method of claim 40 wherein R ⁴ is AND -CH — CH — CH3 42. The method of claim 39, wherein the aryl glycidyl ether is selected from the group consisting of 2,6-dimethylphenylglycidyl ether; 2,6-dimethylphenyl (methylglycidyl) ether; 4-methyl-2,6-dibromophenylglycidyl ether; 4-methyl-2,6-dibromophenyl (methylglycidyl) ether; 1,4-, 1,5- or 2,6-naphthalenediglycidyl ethers; 4,4´-bisphenol A diglycidyl ether; 4,4 '- (3,3', 5,5'-tetramethyl) bisphenol A diglycidyl ether; 4,4 '- (3,3', 5,5'-tetrabromo) bisphenol A diglycidyl ether; 4,4 '- (3,3', 5,5'-tetramethyl2,2 ', 6,6'-tetrabromo) bisphenol A diglycidyl ether; 4,4 '- (3,3', 5,5'-tetramethyl) bisphenol F diglycidyl ether; 4,4´-bisphenol F diglycidylether; 4,4´-bisphenol sulfone diglycidyl ether; 4,4´-bisphenol K diglycidylether; 4,4 '- (3,3', 5,5'-tetramethyl-2,2 ', 6,6'-tetrabromobifenol) diglycidyl ether; 9,9-bis (4-glycidyloxy phenyl) fluorene; 4,4'-bifenoldiglycidylether; 4,4 '- (3,3', 5,5'-tetramethylbiphenol) diglycidyl ether; (4,4 &apos; -dihydroxy- <x-methylstilbene) diglycidyl ether; 1,3-bis (4-glycidyloxyphenyl) adamantane; 4,4´-bisphenol A dimethylglycidyl ether; 4,4 '- (3,3', 5,5'-tetramethyl) bisphenol A dimethylglycidyl ether; 4,4 '- (3,3', 5,5'-tetrabromo) bisphenol A dimethylglycidyl ether; 4,4 '- (3,3', 5,5'-tetramethyl-2,2 ', 6,6'-tetrabromo) bisphenol A dimethylglycidyl ether; 4,4 '- (3,3', 5,5'-tetramethyl) bisphenol F dimethylglycidyl ether; 4,4´-bisphenol F dimethylglycidyl ether; 4,4´-bisphenol sulfone dimethylglycidyl ether; 4,4´-bisphenol K dimethylglycidyl ether; 4,4 '- (3,3', 5,5'-tetramethyl-2,2 ', 6,6'-tetrabromobiphenol) dimethylglycidyl ether; 9,9-bis (4-methylglycidyloxyphenyl) fluorene; 4,4'-biphenoldimethylglycidyl ether; 4,4 '- (3,3', 5,5'-tetramethylbifenol) dimethylglycidyl ether; (4,4'-dihydroxy-α-methylstilbene) dimethylglycidyl ether; 1,3-bis (4-methylglycidyloxyphenyl) adamantane; glycidyl ether of o-cresol-formaldehyde resin with more than 2 functional groups; phenol-formaldehyde resin glycidyl ether with more than 2 functional groups; phenol-dicyclopentadienyl resin glycidyl ether with more than 2 functional groups; glycidyl ether of naphthol-formaldehyde resin with more than 2 functional groups; o-cresol-formaldehyde methyl glycidyl ether having more than 2 functional groups; phenol-formaldehyde resin methyl glycidyl ether with more than 2 functional groups; phenol-dicyclopentadienyl resin with more than 2 functional groups methyl glycidyl ether; naphthol-formaldehyde methyl glycidyl ether having more than 2 functional groups; tris (hydroxyphenyl) methane triglycidyl ether; tris (2,6-dimethylhydroxyphenyl) methane triglycidyl ether; 1,1,2,2-tetrakis (hydroxyphenyl) ethane tetraglycidyl ether; Tris (hydroxyphenyl) methane trimethylglycidyl ether; tris (2,6-dimethylhydroxyphenyl) methane trimethylglycidyl ether and 1,1,2,2-tetrakis (hydroxyphenyl) ethane tetramethylglycidyl ether. 43. The process of claim 1 wherein the reaction is carried out at a temperature of 0 to 120 ° C. 44. The process of claim 1, wherein the reaction is carried out at atmospheric pressure, a pressure below atmospheric pressure or a pressure above atmospheric pressure. 45. The process of claim 1 wherein the reaction mixture comprises a solvent selected from the group consisting of aliphatic, cycloaliphatic or aromatic hydrocarbon solvents; partially or fully halogenated aliphatic, cycloaliphatic or aromatic hydrocarbon solvents; aliphatic, cycloaliphatic or aromatic alcohols or nitriles; partially or fully fluorinated aliphatic, cycloaliphatic or aromatic alcohols; CO2 and their combinations. 46. The process of claim 1 wherein the mole ratio of catalyst to allylarylethers present in the reaction mixture is 1.10 ^-6 to 1 mole of catalyst per mole of allylarylethers. 47. The method of claim 34, wherein the total weight of metal in the catalyst complex to the total weight of the solid support is in the range of about 1.10 ^-6 to 1 part metal per 1 part solid support. 48. The method of claim 34, wherein the weight ratio of the heterogeneous catalyst to the allylarylether substrate is in the range of 10 to 100 parts heterogeneous catalyst to 1 part allylarylether. 49. The process of claim 15 wherein the molar ratio of oxidizing agent to allyl ether is 0.6 to 20 moles per mole of allylarylethers. 50. An article characterized in that it is produced by the method of claim 1. • · · «· ··· ······ · * ············· 51. A composition comprising a reaction mixture of: A) allylarylethers, B) a hydroperoxide oxidizing agent, and C) a catalyst, which is a transition metal complex, wherein at least (a) allylarylether is conformationally restricted; or b) a catalyst by which the transition metal complex comprises at least one or more stable ligands bound to the transition metal.