Peracid Promoters in the Iridium-Catalyzed Hydrosilylation Synthesis of Haloalkylorganosilanes

Abstract

The present invention is directed to a process for producing a compound of formula (I): (R 1 ) y (R 2 O) 3-y SiCH2CHR 3 CR 4 R 5 X (I) (a) Halogenated olefins; (b) alkoxysilanes; (c) a catalytically effective amount of an iridium-containing catalyst; and (d) reacting a reaction-promoting effective amount of peroxycarboxylic acid to produce the product of formula (I).

Description

[Technical Field]

[0001] The present invention relates to a process for making haloorganosilicon compounds. More particularly, the present invention relates to a process for preparing haloorganoalkoxysilanes, particularly chloropropyltriethoxysilane, via the hydrosilylation of haloalkenes with alkoxysilanes, compositions comprising one or more haloorganoalkoxysilanes, one or more iridium-containing compounds, and one or more perbenzoic acids, and uses of such compositions. [Background technology]

[0002] Haloalkylorganosilanes are important intermediates for the preparation of various functionalized organosilanes, such as amino-, mercapto-, and methacryloyloxyorganosilanes, which are used as silane coupling agents. For example, chloropropyltriethoxysilane is a key intermediate for the preparation of polysulfone-containing organoalkoxysilanes, which are used in the manufacture of silica-filled tires. As known in the art, chloropropyltriethoxysilane (CPTES) can be produced by transesterification of chloropropyltrimethoxysilane or by hydrosilylation of the corresponding haloalkene allyl chloride with triethoxysilane (TES).

[0003] The hydrosilylation of allyl chloride with triethoxysilane (TES) in the presence of platinum catalysts shows a large variability in the yield of the target product, chloropropyltriethoxysilane (CPTES), ranging from 14 to 70% (US 9556208 and cited references US 3795656, JP 11-199588, Belyakova et al., and Chernyshev et al.). The reason for the low yield is the tendency for propene to form as an undesired by-product. Rhodium- and palladium-based catalyst systems have the same drawbacks (US 9556208).

[0004] Dimeric halogenated olefin complexes of iridium(I) have been disclosed as effective catalysts for the synthesis of CPTES from TES and allyl chloride (US Pat. No. 4,658,050). Yields of up to 75% are reported for 100 ppm of catalyst.

[0005] US5616762 describes the synthesis of CPTES from TES and allyl chloride in the presence of iridium(III) chloride hydrate, where an excess of allyl chloride is used to obtain a yield of over 80%.

[0006] Although the above reactions can produce CPTES in high yields, the iridium-catalyzed reaction to produce CPTES suffers from a lack of reproducibility. Yields vary unpredictably, especially at low iridium concentrations. Therefore, there is a need for additives to stabilize and further increase the yield of the iridium-catalyzed hydrosilylation of allyl chloride with TES.

[0007] WO2017 / 154846A1 discloses a process for producing (3-chloropropyl)dimethoxymethylsilane in which allyl chloride is reacted with dimethoxymethylsilane in the presence of an iridium catalyst, and a composition obtained by this process.

[0008] Therein, WO2017 / 154846A1 appears to teach that iridium-catalyzed hydrosilylation of allylic species can be significantly accelerated when a binuclear complex of iridium bearing silyl groups is reacted with an allyl compound in a pretreatment step to form an iridium complex, but it does not disclose the presence of peroxycarboxylic acid in the hydrosilylation process or the presence of peroxycarboxylic acid and / or carboxylic acid in the composition obtained by this process.

[0009] US Pat. No. 6,015,920A discloses a process for producing (3-chloropropyl)trimethoxysilane by the iridium-catalyzed hydrosilylation of allyl chloride with trimethoxysilane.

[0010] Generally, US 6,015,920 A is directed to a hydrosilylation reaction process in which a portion of the reactor outlet product is continuously recycled to the reactor, and demonstrates the production of (3-chloropropyl)trimethoxysilane by the iridium-catalyzed hydrosilylation of allyl chloride with trimethoxysilane. However, it does not disclose the presence of peroxycarboxylic acid in the hydrosilylation process or the presence of peroxycarboxylic acid and / or carboxylic acid in the composition obtained by this process.

[0011] Organic peroxy compounds and oxygen are known to affect the hydrosilylation reaction.

[0012] US9556208 describes the use of hydroperoxides, dialkyl peroxides, and diacyl peroxides as promoters for the hydrosilylation of allyl chloride with alkoxysilanes in the presence of a ruthenium catalyst. Di-tert-butyl peroxide is used in the reaction of allyl chloride with TES.

[0013] m-Chloroperbenzoic acid has been described as a promoter for the reaction of 1-octene with triethylsilane in the presence of a rhodium-phosphine complex (Calhoun et al., Trans. Metal. Chem., 8(6), 365 (1983)).

[0014] DE 10133008 proposes peracids, particularly m-chloroperbenzoic acid, as promoters for the hydrosilylation of hydrosilanes or hydrosiloxanes with hydrocarbons, silanes, or siloxanes containing double or triple bonds. The catalysts are all known hydrosilylation catalysts, preferably based on platinum, ruthenium, rhodium, and palladium.

[0015] US5559264 describes the hydrosilylation of allyl chloride to trimethoxysilane (TMS) in the presence of a ruthenium-CO complex. By adding oxygen as a promoter, yields of over 80% can be achieved.

[0016] US6872845 discloses aromatic compounds as promoters for ruthenium-catalyzed hydrosilylation reactions to produce haloorganoalkoxysilanes. It also suggests adding oxygen to activate the outlined ruthenium-CO and ruthenium-phosphine catalysts. Generally, naturally occurring oxygen levels in the raw materials are sufficient. Further activation is possible by adding, for example, 3% O2 ​​to N2.

[0017] On the other hand, US Pat. No. 5,986,122 teaches that peroxides present in alkenyl polyethers inhibit the hydrosilylation reaction with SiH siloxanes in the presence of platinum catalysts.

[0018] Furthermore, US Pat. No. 8,580,994 describes the beneficial effect of reducing the oxygen content during the hydrosilylation of allyl chloride to dimethylethoxysilane in the presence of an iridium-diene complex catalyst.

[0019] From the prior art disclosures, it can be concluded that peroxy compounds and oxygen are advantageous in some hydrosilylation reactions.

[0020] However, these findings represent individual cases in nature, and in view of the wide variety of potential catalysts, unsaturated monomers, SiH-functional silanes, and peroxy compounds, no general rules for the advantageous use of peroxy compounds and oxygen can be derived from the prior art.

[0021] The situation is further complicated by the fact that the seemingly contradictory behavior of either peroxides or oxygen has been found to inhibit the desired hydrosilylation reaction.

[0022] Thus, although both academic and patent literature disclosures teach that iridium-based catalysts are advantageous for the hydrosilylation of allyl chloride with triethoxysilane, deficiencies remain in reproducibly obtaining the desired product selectivity, reaction rate, and reaction yield at cost-effective iridium concentrations. Summary of the Invention

[0023] These problems are addressed by the present invention, which provides a method for the iridium-catalyzed hydrosilylation of halogenated olefins with alkoxysilanes in the presence of a peroxycarboxylic acid promoter to produce products of formula (I), (R 1 ) y (R 2 O) 3-y The process of the present invention allows for the efficient synthesis of SiCH2CHR3CR4R5X(I). The desired compound is reproducibly obtained at cost-effective iridium concentrations with the desired selectivity, rate, and reaction stability.

[0024] In this process, the formation of by-products is reduced and desirable results are obtained for as-received solid catalysts as well as homogeneous catalyst solutions. The catalyst system consisting of an iridium-containing catalyst and peroxycarboxylic acid as a promoter is very tolerant to the use of as-received halogenated olefins, thus eliminating the need for additional purification of the olefin compounds.

[0025] The present invention, as described in detail below, is directed to a process for producing an organoalkoxysilane product, (a) Halogenated olefins; (b) alkoxysilanes; (c) a catalytically effective amount of an iridium-containing catalyst; and (d) reacting with an effective reaction-promoting amount of peroxycarboxylic acid to purify the organoalkoxysilane product.

[0026] In particular, the present invention relates to a process for producing a compound of formula (I): (R 1 ) y (R 2 O) 3-y SiCH2CHR 3 CR 4 R 5 X (I) (a) Formula H2C=CR 3 CR 4 R 5 (b) a halogenated olefin having the formula (R 1 ) y (R 2 O) 3-y (c) a catalytically effective amount of an iridium-containing catalyst; and (d) a reaction-promoting effective amount of a peroxycarboxylic acid to form a product of formula (I), (R 1 ) y (R 2 O) 3-y SiCH2CHR 3 CR 4 R 5 X (I) During the ceremony, R 1 and R 2 is an alkyl group of 1 to 6 carbon atoms; R 3 is an alkyl group of 1 to 6 carbon atoms or hydrogen; R 4 is an alkyl group of 1 to 6 carbon atoms, hydrogen, or halogen; R 5 is hydrogen or an alkyl group of 1 to 6 carbon atoms; X is a halogen; and y is 0, 1, or 2. DETAILED DESCRIPTION OF THE INVENTION

[0027] The process according to the invention is a process for preparing a compound of formula (I) (R 1 ) y (R 2 O) 3-y SiCH2CHR 3 CR 4 R 5 X (I) (a) Formula H2C=CR 3 CR 4 R 5 (b) a halogenated olefin having the formula (R 1 ) y (R 2 O) 3-y (c) a catalytically effective amount of an iridium-containing catalyst; and (d) a reaction-promoting effective amount of a peroxycarboxylic acid to form a product of formula (I), (R 1 ) y (R 2 O) 3-y SiCH2CHR 3 CR 4 R 5 X (I) During the ceremony, R 1 and R 2 is an alkyl group of 1 to 6 carbon atoms; R 3 is an alkyl group of 1 to 6 carbon atoms or hydrogen; R 4 is an alkyl group of 1 to 6 carbon atoms, hydrogen, or halogen; R 5 is hydrogen or an alkyl group of 1 to 6 carbon atoms; X is a halogen; and y is 0, 1, or 2.

[0028] This invention relates to a process for making haloorganosilicon compounds, and more particularly to a process for preparing products of formula (I) via the hydrosilylation of a haloalkene with an alkoxysilane in the presence of a peroxycarboxylic acid and an iridium-containing catalyst.

[0029] As used herein, "alkyl" is meant to include straight-chain, branched-chain, and cyclic alkyl groups. Specific non-limiting examples of alkyl include, but are not limited to, methyl, ethyl, propyl, and isobutyl.

[0030] As used herein, "substituted alkyl" refers to an alkyl group that contains one or more substituents that are inert under the process conditions to which the compound containing those groups is subjected. These substituents also do not substantially or detrimentally interfere with the process.

[0031] As used herein, "aryl" refers to a non-limiting group that is any aromatic hydrocarbon from which one hydrogen atom has been removed. Aryl may have one or more aromatic rings that may be fused or linked by single bonds or other groups. Specific non-limiting examples of aryl include, but are not limited to, tolyl, xylyl, phenyl, and naphthalenyl.

[0032] As used herein, "substituted aryl" refers to an aromatic group substituted as described above for "substituted alkyl." Similar to aryl, substituted aryl may have one or more aromatic rings, which may be fused or connected by single bonds or other groups; however, when the substituted aryl has a heteroaromatic ring, the free valence of the substituted aryl group may be to a heteroatom (e.g., nitrogen) of the heteroaromatic ring rather than to a carbon. Unless otherwise specified, the substituted aryl group of this application preferably contains from 1 to about 30 carbon atoms.

[0033] As used herein, "alkenyl" refers to any straight-chain, branched-chain, or cyclic alkenyl group containing one or more carbon-carbon double bonds, where substitution can be at either the carbon-carbon double bond or elsewhere in the group. Specific non-limiting examples of alkenyl include, but are not limited to, vinyl, propenyl, allyl, methallyl, and ethylidenylnorbornane.

[0034] As used herein, "alkynyl" refers to any straight, branched, or cyclic alkynyl group containing one or more carbon-carbon triple bonds, where substitution can be at either the carbon-carbon triple bond or elsewhere in the group.

[0035] "Unsaturated" means one or more double or triple bonds. In preferred embodiments, it refers to a carbon-carbon double or triple bond.

[0036] As used herein, "inert functional group" means a group other than hydrocarbyl or substituted hydrocarbyl that is inert under the process conditions to which the compound containing the group is subjected. Inert functional groups also do not substantially or detrimentally interfere with any of the processes described herein in which the compound containing them may be involved. Examples of inert functional groups include halo (fluoro, chloro, bromo, and iodo), -OR, -O ... 30 ethers such as 30 is a hydrocarbyl or substituted hydrocarbyl.

[0037] As used herein, "heteroatom" means any of the elements in Groups 13-17, excluding carbon, and can include, for example, oxygen, nitrogen, silicon, sulfur, phosphorus, fluorine, chlorine, bromine, and iodine.

[0038] As used herein, "olefin" means any aliphatic or aromatic hydrocarbon containing one or more additional carbon-carbon double bonds. Such olefins may be straight-chain, branched-chain, or cyclic, and may be substituted with heteroatoms as described above, provided that the substituents do not substantially or detrimentally interfere with the desired reaction sequence to produce the product.

[0039] As used herein, "peroxycarboxylic acid" refers to any compound containing a peroxycarboxylic acid moiety, i.e., a structure of the formula -RC(O)-OOH, where R can be any organyl group.

[0040] As used herein, "catalytically effective amount" means an amount effective to catalyze a hydrosilylation reaction.

[0041] As used herein, "a reaction-promoting effective amount" means an amount sufficient to promote a reaction, but not an amount that inhibits the reaction.

[0042] As used herein, "halogen" refers to any atom that is a member of Group VIIA of the Periodic Table (fluorine, chlorine, bromine, iodine, astatine). As used herein, the prefix "halo" when used with respect to a compound refers to a compound that contains a halogen atom.

[0043] In the process for producing the product of formula (I) of the present invention as described above, (R 1 ) y (R 2 O) 3-y SiCH2CHR 3 CR 4 R 5 X (I) The primary product of the hydrosilylation process of the present invention is a compound of general formula (I): (R 1 ) y (R 2 O) 3-y SiCH2CHR 3 CR 4 R 5 X (I) R in the formula 1 and R 2 is an alkyl group of 1 to 6 carbon atoms; R 3 is an alkyl group of 1 to 6 carbon atoms or hydrogen; R 4 is an alkyl group of 1 to 6 carbon atoms, hydrogen or halogen; R 5 is hydrogen or an alkyl group of 1 to 6 carbon atoms; X is a halogen; and y is 0, 1, or 2.

[0044] Specific examples of useful products of the process of the present invention include, but are not limited to, (CHO)Si(CH)Cl, (CHO)Si(CH)Cl, (CHO)SiCHCH(CH)CHBr, (CHO)SiCHCH(Cl)CH, CH(CHO)Si(CH)Cl, and (CHO)Si(CH)CH(Cl)CH.

[0045] During the hydrosilylation reaction, a by-product is formed having the general formula: (R 2 O)4Si, (R 1 )Si(R 2 O)3, (R 1 )SiH2(R 2 O), (R 2 O)3SiX, (R 1 is not hydrogen), (R 2 O)3SiCH2CHR 3 CR 4 R 5 H, (R 1 ) y X(R 2 O) 2-y SiCH2CHR 3 CR 4 R 5 X, CH2=CHR 3 CR 4 R 5 H, XCH2CHR 3 CR 4 R 5 H, and HX.

[0046] A one-step hydrosilylation reaction between a halogenated olefin and an alkoxysilane in the presence of an iridium-containing catalyst and a peroxycarboxylic acid to produce a product of formula (I): (R 1 ) y (R 2 O) 3-y SiCH2CHR 3 CR 4 R 5 X (I) Several factors have been found to be important in obtaining high yields of

[0047] According to an embodiment of the present invention, the most preferred product of formula (I) is chloropropyltriethoxysilane.

[0048] Halogenated Olefins The halogenated olefins used as starting materials in the process according to the invention have the general formula H2C=CR 3 CR 4 R 5 X wherein R 3 is an alkyl group of 1 to 6 carbon atoms or hydrogen; R 4 is an alkyl group of 1 to 6 carbon atoms, hydrogen or halogen; R 5 is hydrogen or an alkyl group of 1 to 6 carbon atoms; X is a halogen. X is a fluoro, chloro, bromo, or iodo substituent, preferably a bromo or chloro substituent, and most preferably a chloro substituent.

[0049] R 3 and R 5 are independently selected from the group consisting of straight-chain, branched-chain or cyclic C1-C6 alkyl groups or hydrogen, in particular selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, cyclopentyl, cyclohexyl or hydrogen, preferably selected from methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl or hydrogen, more preferably selected from methyl, ethyl, n-propyl, isopropyl or hydrogen, even more preferably selected from methyl, ethyl or hydrogen, and most preferably selected from R 3 and R 5 is hydrogen.

[0050] R 4are independently selected from the group consisting of straight-chain, branched-chain or cyclic C1-C6 alkyl groups or hydrogen, in particular selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, cyclopentyl, cyclohexyl, hydrogen or halogen, preferably selected from methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl or hydrogen, more preferably selected from methyl, ethyl, n-propyl, isopropyl or hydrogen, even more preferably selected from methyl, ethyl or hydrogen, and most preferably selected from R 4 is hydrogen.

[0051] R 4 is a halogen group independently selected from fluoro, chloro, bromo, and iodo substituents, R 4 is preferably a chloro substituent.

[0052] Preferably, R in the halogenated olefin 3 , R 4 and R 5 is a hydrogen substituent or a substituent R 3 , R 4 and R 5 two of the substituents are hydrogen substituents and the remaining substituent is a C1-C6 alkyl substituent, more preferably R 3 , R 4 and R 5 is a hydrogen substituent or a substituent R 3 , R 4 and R 5 two of the substituents are hydrogen substituents and the remaining substituent is an alkyl substituent selected from methyl, ethyl, and n-propyl, and even more preferably R 3 , R 4 and R 5 is a hydrogen substituent or a substituent R 3 , R 4 and R 5 two of the substituents are hydrogen substituents and the remaining substituent is a methyl substituent, most preferably R 3 , R 4 and R 5is a hydrogen substituent or a substituent R 3 and R 5 is a hydrogen substituent and R 4 The substituent is a methyl substituent.

[0053] Suitable halogenated olefin starting materials for the present invention include, among others, allyl chloride, methallyl chloride, 3-chloro-1-butene, 3,4-dichloro-1-butene, and others, of which allyl chloride, i.e., HC=CHCHCl, is preferred in embodiments.

[0054] According to an embodiment of the present invention, the halogenated olefins can be used in the as-received state with technical-grade purity, which means that the content of the respective halogenated olefin is ≧90 wt%, preferably ≧95 wt%, even more preferably ≧98 wt%, and most preferably ≧99 wt%. Rectification of the halogenated olefin starting material by evaporation and subsequent condensation can have a beneficial effect on the yield of the hydrosilylation reaction of the process of the present invention, but is not required to carry out the process of the present invention. The term "as-received" halogenated olefin means that the halogenated olefin is not subjected to a purification step, such as distillation or evaporation / condensation, before the hydrosilylation step is carried out.

[0055] Thus, because the process of the present invention does not require high grade halogenated olefins to operate in high yield, the purity of the technical grade halogenated olefins can be in the range of 95.0 to 99.5 wt %, more particularly in the range of 95.5 to 99.0 wt %, and even more particularly in the range of 96.0 to 98.0 wt %.

[0056] Therein the halogenated olefin of technical grade purity can be as received, or it can be a halogenated olefin that has previously been subjected to a purification process, such as a process based on evaporation and condensation.

[0057] Alkoxysilane The alkoxysilanes used as starting materials in the process according to the invention have the general formula (R 1 ) y (R 2 O)3- y SiH, where R 1 and R 2 is an alkyl group of 1 to 6 carbon atoms, and y is 0, 1, or 2.

[0058] Therefore, the general formula (R 1 ) y (R 2 O) 3-y Alkoxysilanes of SiH and the corresponding products of formula (I), (R 1 ) y (R 2 O) 3-y SiCH2CHR 3 CR 4 R 5 X (I) R in 1 and R 2 are independently selected from the group consisting of linear, branched or cyclic C1-C6 alkyl groups, in particular methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, tert-butyl, isopentyl, neo-pentyl, cyclopentyl or cyclohexyl, preferably selected from methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclopentyl or cyclohexyl, more preferably selected from methyl, ethyl, n-propyl, isopropyl, even more preferably selected from methyl and ethyl, and most preferably R 1 and R 2 is a methyl group.

[0059] Preferably, y is 0, i.e., the alkoxysilane (b) applied in the process for producing the product of formula (I) is preferably an alkoxysilane substituted with three alkoxy groups. In such an alkoxysilane bearing three alkoxy groups on the silicon atom, and in the corresponding product of formula (I), all R 2Preferably, the groups represent the same type of C1-C6 alkyl groups, more preferably alkyl groups selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, and cyclohexyl, even more preferably alkyl groups selected from methyl, ethyl, n-propyl, and isopropyl, and most preferably the alkoxysilanes and corresponding products of formula (I) carry three ethoxy groups on the silicon atom, i.e., y=0 and R 2 is ethyl.

[0060] Alkoxysilanes suitable as starting materials in the process of the present invention include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane, diethylethoxysilane, and others. Of these alkoxysilanes, trimethoxysilane and triethoxysilane are preferred in embodiments of the present invention.

[0061] Trialkoxysilanes useful in this process can be obtained via alcohol esterification of trihalosilanes, as disclosed, for example, in US Pat. Nos. 3,792,071 and 3,985,781. Trimethoxysilane and triethoxysilane can be obtained in distillation purities of 89-92 wt. %. Residual chlorine levels can be as high as 100 ppm. Impurities include H2Si(OR)2, HSi(OR)2Cl, Si(OR)4, and higher-boiling condensed silicates.

[0062] Alternatively, trialkoxysilanes useful in this process can be obtained via the direct reaction of alcohols with copper-activated silicon, as disclosed, for example, in US Pat. Nos. 7,652,164 and 7,429,672. Trimethoxysilane and triethoxysilane synthesized according to this process are chlorine-free and typically have a purity of about 89-99% by weight before distillation. The distillate product has a purity of about 99.0-99.9% by weight. Impurities include H2Si(OR)2, RSiH(OR)2, RSi(OR)3, Si(OR)4, and higher-boiling condensed silicates.

[0063] Peroxycarboxylic acid Peroxycarboxylic acids contain a -C(O)-O-OH moiety. They decompose under the influence of heat, acid, and certain metal compounds. Therefore, because the reactants in a hydrosilylation process are subjected to such influences during the reaction, product recovery, and recycling of unreacted starting materials and catalyst, a peroxide promoter must be selected to maintain stable hydrosilylation activity throughout a batch or continuous process.

[0064] Preferably, the concentration of peroxycarboxylic acid used in embodiments of the process of the present invention ranges from about 1 to about 2000 ppm, more preferably from about 2 to about 500 ppm, more preferably from about 3 to about 200 ppm, even more preferably from about 4 to about 100 ppm, even more preferably from about 5 to about 50 ppm, even more preferably from about 5 to about 25 ppm, and most preferably from about 5 to about 15 ppm, all based on the combined weight of halogenated olefin and alkoxysilane applied to the process. Preferred temperature and concentration ranges for different types of peroxycarboxylic acids are described below in the detailed description of specific embodiments of the present invention.

[0065] The half-life of peroxycarboxylic acid can be as short as about 30 minutes at the boiling point of allyl chloride (44-45°C) and thus may be shorter within the temperature range of about 70 to about 100°C where the hydrosilylation reaction is preferably carried out. Therefore, the concentration of peroxycarboxylic acid is not always adequate to promote and drive the hydrosilylation reaction to completion. Therefore, if peroxycarboxylic acid is not present at an effective reaction-promoting concentration, variable and inconsistent results may occur in laboratory experiments and commercial operations. The process of the present invention involves the presence of peroxycarboxylic acid at a level that will effect effective hydrosilylation. Peroxycarboxylic acid must be present in the hydrosilylation reaction zone along with the reactants and iridium-containing catalyst. It can be added directly to the reaction zone or, preferably, mixed with the olefin.

[0066] Generally, peroxycarboxylic acids, as defined herein, include all types of organic compounds containing one or more peroxycarboxylic acid moieties of the structure -C(O)-O-OH.

[0067] Preferred classes of peroxycarboxylic acids according to embodiments of the present invention are halogenated perbenzoic acids, unsubstituted peroxyalkanoic acids, and α-halogenated peroxyalkanoic acids, with halogenated perbenzoic acids comprising the most preferred class within the group of peroxycarboxylic acids just described.

[0068] Halogenated perbenzoic acids include mono-, di-, tri-, tetra-, and pentahalogenated perbenzoic acids, and are preferably selected from monohalogenated perbenzoic acids and dihalogenated perbenzoic acids.

[0069] It is further preferred that the halogenated perbenzoic acid bears at least one halogen substituent meta to the peroxycarboxylic acid group.

[0070] It is also preferred that at least one halogen substituent of the perbenzoic acid is a fluoro or chloro substituent, and even more preferably all halogen substituents are independently selected from fluoro and chloro substituents.

[0071] Examples of peroxycarboxylic acids selected from halogenated perbenzoic acids preferred for the process of the present invention are 2-bromo-5-chlorobenzoic acid, 3,5-difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 2,3,6-trifluoroperbenzoic acid, 2,4,5-trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, 2,3,4,5,6-pentafluorobenzoic acid, 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid, with particularly preferred halogenated perbenzoic acids being 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid.

[0072] The unsubstituted peroxyalkanoic acid is preferably selected from C2 to C12 peroxyalkanoic acids, wherein more preferably the peroxycarboxylic acid group is at the terminal position of a straight or branched chain alkyl group, and more preferably the alkyl residue is either a methyl group or a C2 to C11 n-alkyl group. Examples of peroxycarboxylic acids selected from the unsubstituted peroxyalkanoic acids preferred for the process of the present embodiment are peracetic acid, peroxypropionic acid, and peroxybutyric acid.

[0073] The α-halogenated peroxyalkanoic acid, i.e., a peroxyalkanoic acid bearing at least one halogen substituent α-positioned to the peroxycarboxylic acid group, is preferably selected from α-halogenated C2-C12 peroxyalkanoic acids, more preferably from linear α-halogenated C2-C12 peroxyalkanoic acids, wherein the halogen substituents are independently selected from chloro and fluoro substituents. Examples of preferred α-halogenated peroxyalkanoic acids are chloroperacetic acid, fluoroperacetic acid, dichloroperacetic acid, difluoroperacetic acid, trifluoroperacetic acid, and trichloroperacetic acid.

[0074] The presence of peroxycarboxylic acid allows for a reduction in the amount of iridium catalyst loading required to carry out the hydrosilylation in high yield and at reasonable reaction rates, and also allows for the reaction to be carried out using technical grade halogenated olefins without additional purification steps prior to the hydrosilylation reaction.

[0075] Furthermore, commercially available iridium catalysts, such as IrCl and H2IrCl6, can be successfully applied to hydrosilylation reactions in the presence of peroxycarboxylic acid promoters with low catalyst loadings and without purification of technical-grade halogenated olefin starting materials.

[0076] Iridium-containing catalyst Suitable iridium metal-containing catalysts can be selected from iridium metal or homogeneous and heterogeneous iridium metal-containing compounds and complexes, where iridium can be in any oxidation state from 0 to 8. Examples include the following iridium compounds: iridium clusters and particles ranging from about 1 nanometer to about 100 micrometers; iridium on solid supports, such as iron-supported iridium, alumina-supported iridium, carbon-supported iridium, and silica-supported iridium; iridium halides (IrX); n , X is a halogen atom and n is any value from 2 to 4), such as IrCl3 and IrBr3; M2IrCl6, especially H2IrCl6, MIrCl3, M2Ir5Cl 12 , M4Ir4Cl 12 (M=H or alkali metal); zinc and tin reduction products of iridium halides, e.g., ZnIrCl 12 and SnIr5Cl 12 ;IrO2, Ir3(CO) 12, [Ir(CO)3Cl2]2; cycloolefin complexes of iridium, such as Ir(COD)(COT), COD-IrCl2, [COD-IrCl2]2, where COD is cyclooctadiene and COT is cyclooctatriene; bis(6,6-dimethylcyclopentadienyl)iridium, bis(η5-2,4-dimethylpentadienyl)iridium, bis(1,3-dimethylcyclopentadienyl)iridium, Ir(AcAc)3, where AcAc is an acetylacetonate ligand; (π-arene)iridium complexes, such as (p-cymene)iridium(II) chloride dimer and (benzene)iridium(II) chloride dimer; ammine complexes of iridium, such as [Ir(NH3)6]X2 and [Ir(NH3)6]X3.

[0077] Preferred iridium-containing catalysts are iridium chloride compounds, with H2IrCl6 and hydrates of H2IrCl6, IrCl3, hydrates of IrCl3, and their zinc reduction products being most preferred. Catalyst used in one batch can be recycled to the next batch without significant loss of activity. Catalyst use levels can range from 1 to 300 ppm iridium metal, with 5 to 50 ppm being preferred, based on the total reactant charge.

[0078] The catalyst can be added to the hydrosilylation reaction in the form of a solid, a suspension in an organic solvent, or a solution. The iridium-containing catalyst can also be added in immobilized form, for example, tethered to a substrate material or adsorbed to a surface.

[0079] Hydrosilylation Process The hydrosilylation process according to the present invention is not limited to any particular protocol.

[0080] In a preferred protocol for the hydrosilylation reaction according to the present invention using a solid catalyst, a premix of halogenated olefin, alkoxysilane, and peroxycarboxylic acid is added to a mixture of alkoxysilane and iridium-based hydrosilylation catalyst. Preferably, the premix is ​​added stepwise, or more preferably, it is fed from a reactor to a mixture of alkoxysilane and iridium-based hydrosilylation catalyst fed from a reaction, mixing, or storage vessel. Preferably, the reactor in which the reactants are combined is equipped with a mixing device.

[0081] In another preferred protocol for the hydrosilylation reaction of the present invention using a catalyst solution, preferably for small-scale reactions, a peroxycarboxylic acid, a halogenated olefin, and an alkoxysilane are mixed, and then a solution or suspension of the catalyst in a solvent, preferably an organic solvent, is added to the mixture to carry out the hydrosilylation reaction. Preferably, a mixing device is used to form and maintain a homogeneous reaction mixture.

[0082] Furthermore, this process is advantageously carried out by slowly adding the halogenated olefin and peroxycarboxylic acid to a reaction medium containing the alkoxysilane, and the hydrosilylation is carried out in the presence of an iridium metal-containing catalyst in a semi-batch or continuous process. This addition sequence effectively maintains a minimum concentration of unreacted halogenated olefin relative to the alkoxysilane in the reaction medium, thus effectively establishing a very large molar excess of the alkoxysilane relative to the halogenated olefin in the reaction medium. In general practice, the maximum rate of addition of the halogenated olefin to the alkoxysilane is determined by the reaction rate, which, as will be understood by those skilled in the art, is determined in part by the reaction temperature, catalyst concentration, peroxycarboxylic acid concentration and temperature stability, as well as the heat transfer limitations and reactor size of the reaction equipment.

[0083] As noted above, the process of the present invention can be carried out in any equipment suitable for hydrosilylation reactions, including equipment designed for continuous or alternatively discontinuous reactions. The use of trimethoxysilane or triethoxysilane derived from silicon metal and the corresponding alkanol in the present process avoids the use of corrosive and hazardous hydridochlorosilanes and eliminates the generation of large amounts of chlorine-containing by-product waste inherent in the use of products derived from hydridochlorosilanes.

[0084] Reaction conditions include reaction temperatures of about 15°C to about 250°C, preferably about 30°C to about 180°C, more preferably about 50°C to about 130°C, with about 60°C to 80°C being even more preferred. Generally, the process is carried out at atmospheric or superatmospheric pressure, with atmospheric pressure being preferred. While the process of the present invention can provide high yields of the desired chloroalkylalkoxysilanes in batch systems, it will be recognized that it may be practiced in semi-batch or continuous processes as well. However, batch reactions are typically carried out at lower temperatures and consequently involve longer reaction times.

[0085] The process of the present invention converts halogenated olefins into the desired products of formula (I), (R 1 ) y (R 2 O) 3-y SiCH2CHR 3 CR 4 R 5Because the conversion to X(I) is nearly quantitative, particularly for the reaction of allyl chloride and triethoxysilane to produce chloropropyltriethoxysilane, the generation of undesirable by-products is significantly reduced. This reduces the amount of material that must be treated as waste, separated as a separate stream, i.e., by distillation, or vented from the reaction system. The process of the present invention is highly exothermic, and continuous external heating is typically not required, resulting in short reaction times. Generally, the only significant impurities that need to be removed from the reaction product are unreacted alkoxysilane, tetraalkoxysilane, catalyst, and peroxycarboxylic acid residues, or their decomposition products. Low levels of halide residues that may be present in the product can be neutralized by methods well known in the art. When the hydrosilylation product of the present invention is used as an intermediate for the production of other organofunctional silicon compounds, the purity of the as-received material may be sufficient. No additional purification steps are required. For example, when applied to the preparation of chloropropyltriethoxysilane, the process of the present invention provides a higher yield of the target product, calculated on a molar basis, than any other one- or two-step process described in the prior art. This is accomplished through the addition of an effective amount of peroxycarboxylic acid promoter in combination with an effective level of iridium-containing catalyst. Moreover, the process produces the target product at iridium levels significantly lower than those described in the prior art. The process also results in higher yields per unit volume of equipment used because it avoids the use of inert solvents and does not produce significant amounts of by-product impurities.

[0086] Although the process of the present invention does not require operation at pressures above atmospheric pressure, in embodiments, elevated pressures, for example up to 2 atmospheres, may be used to control the boiling point of the reaction mixture in a closed reactor. In alternative embodiments, subatmospheric pressures may be used when a reaction temperature below the atmospheric boiling point of the alkoxysilane is desired. The product of formula (I), (R 1 ) y (R 2 O)3-y SiCH2CHR 3 CR 4 R 5 X(I) may be purified by standard processes, ie, distillation, or may be used directly without intermediate purification.

[0087] In an embodiment according to the present invention, the halogenated olefin (a) is selected from the group consisting of allyl chloride, methallyl chloride, 3-chloro-1-butene, 3,4-dichloro-1-butene, and combinations thereof, preferably the halogenated olefin (a) is allyl chloride.

[0088] The halogenated olefin (a) used in the process according to this embodiment is preferably reacted with a trialkoxysilane, more preferably triethoxysilane. Most preferably, chloropropyltriethoxysilane is obtained by reacting allyl chloride with triethoxysilane in the presence of an iridium catalyst and a peroxycarboxylic acid as specified herein, preferably a halogenated perbenzoic acid, acting as a promoter.

[0089] In another embodiment according to the present invention, the alkoxysilane (b) is selected from the group consisting of trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane, diethylethoxysilane, and combinations thereof, preferably the alkoxysilane is triethoxysilane.

[0090] In yet another embodiment according to the present invention, the effective reaction-promoting amount of peroxycarboxylic acid (d) is in the range of from about 1 to about 2000 ppm, preferably from about 2 to about 500 ppm, more preferably from about 3 to about 200 ppm, even more preferably from about 4 to about 100 ppm, even more preferably from about 5 to about 50 ppm, even more preferably from about 5 to about 25 ppm, and most preferably from about 5 to about 15 ppm, based on the combined weight of the halogenated olefin (a) and alkoxysilane (b) starting materials.

[0091] Preferably, the starting materials (a) and (b) are allyl chloride and triethoxysilane, and the amount of peroxycarboxylic acid (d) is calculated based on the total amount of allyl chloride and triethoxysilane.

[0092] The ratio of the iridium-containing catalyst (c) to the hydrosilylation reaction-promoting peroxycarboxylic acid (d) is in the range of about 1:1 to about 1:40, preferably in the range of about 1:1.5 to about 1:25, more preferably in the range of about 1:2 to about 1:20, and most preferably in the range of about 1:2 to about 1:10.

[0093] The ratio of iridium-containing catalyst (c) to peroxycarboxylic acid (d) is based on the amount of each of components (c) and (d) given in "ppm," where the amount in ppm indicates the amount of each of components (c) or (d) relative to the combined mass of halogenated olefin (a) and alkoxysilane (b). In the case of iridium catalyst (c), the amount of iridium metal in component (c) is related to the combined mass of (a) and (b) to determine the amount of (c) in ppm.

[0094] In an embodiment according to the present invention, the peroxycarboxylic acid (d) is selected from the group of the halogenated perbenzoic acids, the group of the unsubstituted peroxyalkanoic acids, and the group of the α-halogenated peroxyalkanoic acids.

[0095] As defined herein, the term "peroxyalkanoic acid" refers to a peroxycarboxylic acid consisting of a peroxycarboxyl group and an alkyl residue, where the alkyl residue can be a primary n-alkyl group, a secondary alkyl group, or a tertiary alkyl group, with primary alkyl groups being preferred. The alkyl group can be a linear, branched, or cyclic alkyl group, with C1-C11 n-alkyl groups being preferred. The term "unsubstituted" indicates that the carbon atoms of the alkyl group do not carry any other substituents other than hydrogen atoms.

[0096] As defined herein, the term "α-halogenated peroxyalkanoic acid" indicates that the alkyl group of such compounds bears one or more halogen substituents on the carbon atom of the alkyl group that is attached to the carbon atom of the peroxycarboxyl group.

[0097] The group of halogenated perbenzoic acids is preferred and is advantageously applied in the process of the present invention catalyzed by an iridium catalyst, preferably IrCl3 or H2IrCl6, particularly the iridium-catalyzed hydrosilylation reaction of allyl chloride and triethoxysilane.

[0098] In another embodiment according to the invention, the peroxycarboxylic acid (d) is selected from the group of the monohalogenated perbenzoic acids, the group of the dihalogenated perbenzoic acids, and the group of the tri-, tetra- and pentahalogenated perbenzoic acids.

[0099] It should be noted that the nomenclature used herein for halogenated perbenzoic acid compounds is that the atom of the carbon ring bearing the peroxycarboxylic group is designated as position "1," and the positions of one or more halogen substituents on the phenyl ring are numbered relative to this position. For example, 3-bromo-perbenzoic acid denotes a perbenzoic acid bearing a bromo substituent meta to the peroxycarboxylic acid group.

[0100] Examples of monohalogenated perbenzoic acids according to this embodiment are 2-, 3-, or 4-chloroperbenzoic acid, of which 3-chloroperbenzoic acid is preferred, and 2-, 3-, or 4-fluoroperbenzoic acid, of which 3-fluoroperbenzoic acid is preferred.

[0101] Examples of dihalogenated perbenzoic acids are dichloroperbenzoic acids, such as 2,3-dichloroperbenzoic acid, 2,4-dichloroperbenzoic acid, 2,6-dichloroperbenzoic acid, 3,4-dichloroperbenzoic acid, 3,5-dichloroperbenzoic acid, of which 3,5-dichloroperbenzoic acid is preferred, and difluoroperbenzoic acids, such as 2,3-difluoroperbenzoic acid, 2,4-difluoroperbenzoic acid, 2,6-difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 3,5-difluoroperbenzoic acid, of which 3,5-difluoroperbenzoic acid is preferred, and Monochloro-monofluoroperbenzoic acids such as 2-chloro-4-fluoroperbenzoic acid, 2-chloro-5-fluoroperbenzoic acid, 3-chloro-2-fluoroperbenzoic acid, 3-chloro-5-fluoroperbenzoic acid, 4-chloro-2-fluoroperbenzoic acid, 5-chloro-2-fluoroperbenzoic acid, of which 3-chloro-5-fluoroperbenzoic acid is preferred, and monobromo-monochloroperbenzoic acids such as 2-bromo-5-chloroperbenzoic acid and 3-bromo-5-chloroperbenzoic acid, of which 3-bromo-5-chloroperbenzoic acid is preferred.

[0102] Preferred examples of tri-, tetra- and pentahalogenated perbenzoic acids are 2,3,6-trifluoroperbenzoic acid, 2,4,5-trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, and 2,3,4,5,6-pentafluoroperbenzoic acid.

[0103] In another embodiment according to the invention, the peroxycarboxylic acid (d) is selected from the group of halogenated perbenzoic acids bearing at least one halogen substituent in the meta position relative to the peroxycarboxylic group.

[0104] Preferred examples of halogenated perbenzoic acids bearing at least one halogen substituent meta to the peroxycarboxyl group are 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid.

[0105] In yet another embodiment according to the present invention, peroxycarboxylic acid (d) is selected from halogenated perbenzoic acids bearing a total of one, two, or three halogen substituents, wherein preferably at least one, and more preferably all, of the halogen substituents are independently selected from fluoro and chloro substituents, and most preferably either all halogen substituents are chloro substituents or all halogen substituents are fluoro substituents.

[0106] The most preferred halogenated perbenzoic acids according to this embodiment are 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, 3,5-difluoroperbenzoic acid, 3,5-dichloroperbenzoic acid, and 2,3,6-trifluoroperbenzoic acid.

[0107] In a preferred embodiment according to the present invention, the peroxycarboxylic acid (d) is selected from the group of perbenzoic acids consisting of 2-bromo-5-chloroperbenzoic acid, 3,5-difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 2,3,6-trifluoroperbenzoic acid, 2,4,5-trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, 2,3,4,5,6-pentafluoroperbenzoic acid, 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid.

[0108] Preferably, the peroxycarboxylic acid (d) is selected from 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid.

[0109] The halogenated perbenzoic acids according to this embodiment of the invention are either commercially available or readily available from the corresponding halogenated benzoic acids.

[0110] When these compounds are applied as promoters in the process of the present invention in an amount of about 3 to about 200 ppm based on the combined weight of the halogenated olefin (a) and the alkoxysilane (b), the catalyst loading of the iridium-based catalyst, preferably IrCl or HIrCl, can be in the range of about 1 to about 25 ppm of iridium based on the combined weight of the halogenated olefin (a) and the alkoxysilane (b).

[0111] In another embodiment according to the present invention, the peroxycarboxylic acid (d) is an α-halogenated peroxyalkanoic acid selected from the group of C2-C12 α-halogenated peroxyalkanoic acids bearing one or more halogen substituents independently selected from chloro and fluoro substituents, or the peroxycarboxylic acid (d) is an unsubstituted C2-C12 peroxyalkanoic acid.

[0112] Preferably, the peroxycarboxylic acid (d) is an α-halogenated alkanoic acid selected from chloroperacetic acid, fluoroperacetic acid, dichloroperacetic acid, difluoroperacetic acid, trifluoroperacetic acid, and trichloroperacetic acid.

[0113] In another embodiment according to the present invention, the iridium-containing catalyst (c) is selected from the group consisting of nanometer-sized and micrometer-sized iridium particles, iridium halides, zinc or tin reduction reaction products of iridium halides, cycloolefin complexes of iridium, amine complexes of iridium, phosphine complexes of iridium, CO complexes of iridium, and combinations thereof.

[0114] As defined herein, nanometer-sized particles are particles having an average diameter of 1 to 500 nm as determined by dynamic light scattering, and micrometer-sized particles are particles having an average diameter of 0.5 to 50 μm as determined by dynamic light scattering.

[0115] In yet another embodiment according to the present invention, the amount of iridium-containing catalyst (c) based on the combined weight of the starting materials halogenated olefin (a) and alkoxysilane (b) is in the range of from about 1 to about 100 ppm, preferably from about 1 to about 50 ppm, more preferably from about 1 to about 25 ppm, even more preferably from about 2 to about 25 ppm, and most preferably from about 3 to about 15 ppm.

[0116] In yet another embodiment according to the present invention, the iridium-containing catalyst (c) is selected from the group consisting of IrCl, IrBr, M2IrCl6, where M=H or an alkali metal; cycloolefin complexes of iridium, such as Ir2Cl2(COE)4, Crabtree's catalyst, [Ir(μ 2~C l) Ir(OCH)(COD) where COE is cyclooctene and COD is 1,5-cyclooctadiene; pentamethylcyclopentadienyl iridium dichloride dimer [Cp*IrCl]; (π-arene)iridium complexes, and combinations thereof.

[0117] In a preferred embodiment according to the present invention, the iridium-containing catalyst (c) is selected from IrCl3·xH2O or H2IrCl6.

[0118] The number of water molecules in "x" in IrCl3 hydrate can be any fraction from 0, i.e., anhydrous IrCl3, to 1. Because IrCl3 is highly hygroscopic, IrCl3 hydrate may absorb additional water beyond one molecule per iridium ion. HIrCl6 may also be applied as a hydrosilylation catalyst, either as an anhydrous reagent or as the corresponding hydrate. Both IrCl3 and HIrCl6 can be applied to the hydrosilylation reaction as solids or as pre-prepared stock solutions or suspensions. Such solutions or suspensions are preferably prepared using organic solvents with OH functionality, preferably alkanols with one, two, or three hydroxyl groups, such as methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerin, or polyglycols such as polyethylene glycol and polypropylene glycol.

[0119] Preferably, the amount of iridium-containing catalyst IrCl or H2IrCl6 in the process of this embodiment is in the range of about 1 to about 50 ppm, more preferably in the range of about 2 to about 25 ppm, and even more preferably in the range of about 3 to about 15 ppm, where the "ppm" designation indicates the mass content of iridium in IrCl or H2IrCl6 relative to the combined mass of the halogenated olefin (a) and the alkoxysilane (b). wherein the ratio (ppm to ppm) of the iridium-containing catalyst IrCl or HIrCl to the peroxycarboxylic acid promoter (d) according to this embodiment is preferably in the range of about 1:1.5 to about 1:25, more preferably in the range of about 1:2 to about 1:20, and most preferably in the range of about 1:2 to about 1:10, and the preferred peroxycarboxylic acid (d) according to this embodiment is a halogenated perbenzoic acid, more preferably selected from 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid. The "ppm" designation for the peroxycarboxylic acid (d) indicates the mass of the peroxycarboxylic acid relative to the combined mass of the halogenated olefin (a) and the alkoxysilane (b).

[0120] According to this embodiment, the conditions described above are preferably applied to the hydrosilylation of allyl chloride with triethoxysilane to give chloropropyltriethoxysilane.

[0121] In a further embodiment according to the invention, the iridium-containing catalyst (c) is added to the reaction as a solid or as a solution or suspension in an organic solvent, preferably from an OH-functionalized solvent, i.e., for example, OH-functionalized alkanols, diols and triols, such as ethanol, polyethers, preferably the catalyst (c) is added as a solid.

[0122] Examples of OH-functionalized solvents are methanol, ethanol, n-propanol, isobutanol, n-butanol, tert-butanol, pentanol, hexanol, cyclohexanol, and polyglycols such as polyethylene glycol and polypropylene glycol, glycol mono- and polyglycols such as the methyl and butyl ethers of ethylene glycol, diethylene glycol and triethylene glycol, and the methyl and butyl ethers of propylene glycol, dipropylene glycol and tripropylene glycol.

[0123] In another embodiment according to the present invention, the halogenated olefin (a) is a technical grade halogenated olefin, preferably technical grade allyl chloride.

[0124] As defined herein, the term "technical grade" refers to a halogenated olefin having a purity of ≧90 wt.%, preferably ≧95 wt.%, even more preferably ≧98 wt.%, and most preferably ≧99 wt.%.

[0125] Typically, commercially available halogenated olefins have a quality with respect to purity that can be characterized as "technical grade." However, in many cases, a higher degree of purity is required, which is associated with additional purification steps and higher costs.

[0126] The process of the present invention allows for the iridium-catalyzed hydrosilylation reaction to be carried out in high yields using technical-grade halogenated olefins (a) in the presence of percarboxylic acid (d). Thus, according to this embodiment, the halogenated olefins may have a purity ranging from about 95.0 wt. % to about 99.5 wt. %, more particularly from about 95.5 wt. % to about 99.0 wt. %, and even more particularly from about 96.0 wt. % to about 98.0 wt. %. The halogenated olefins may be used as received.

[0127] In embodiments according to the present invention, the molar ratio of halogenated olefin (a) to alkoxysilane (b) is in the range of from about 10:1 to about 1:10, preferably from about 5:1 to about 1:5, more preferably from about 2:1 to about 1:2, even more preferably from about 1.7:1 to about 1:1.7, even more preferably from about 1.5:1 to about 1:1.5, and most preferably from about 1.2:1 to about 1:1.2.

[0128] In another embodiment according to the present invention, the ratio of the iridium-containing catalyst (c) to the peroxycarboxylic acid (d) in ppm to ppm based on the total weight of the starting halogenated olefin (a) and alkoxysilane (b), respectively, is in the range of about 1:1 to about 1:40, preferably in the range of about 1:1.5 to about 1:25, more preferably in the range of about 1:2 to about 1:20, and most preferably in the range of about 1:2 to about 1:10.

[0129] To determine the ratio of iridium-containing catalyst (c) to peroxycarboxylic acid (d) in ppm to ppm, the mass of peroxycarboxylic acid (d) is divided by the combined mass of halogenated olefin (a) and alkoxysilane (b) and multiplied by 1,000,000; the mass of iridium contained in iridium-containing catalyst (c) is divided by the combined mass of halogenated olefin (a) and alkoxysilane (b) and multiplied by 1,000,000. Using this calculation, the amounts of iridium-containing catalyst (c) and peroxycarboxylic acid (d) according to the present invention are obtained in ppm. Thus, the ratio given in this embodiment indicates the ratio of the amounts of iridium-containing catalyst and peroxycarboxylic acid in "ppm" determined as described above.

[0130] In a preferred embodiment according to the present invention, the halogenated olefin (a) is allyl chloride, the alkoxysilane (b) is triethoxysilane, the iridium-containing catalyst (c) is IrCl or H2IrCl6, and the peroxycarboxylic acid (d) is 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, or 3,5-difluoroperbenzoic acid.

[0131] In a further preferred embodiment according to the present invention, the halogenated olefin (a) is allyl chloride, the alkoxysilane (b) is triethoxysilane, the amount of iridium-containing catalyst (c) ranges from about 5 to about 20 ppm, and the peroxycarboxylic acid (d) is one of the following: mCPBA present in an amount satisfying the requirement that the ratio of catalyst (c) to promoter (d) in [ppm / ppm] ranges from about 1:2.5 to about 1:20; or mFPBA present in an amount satisfying the proviso that the ratio of catalyst (c) to promoter (d) in [ppm / ppm] is in the range of about 1:2.5 to about 1:10; or dFPBA present in an amount satisfying the proviso that the ratio of catalyst (c) to promoter (d) in [ppm / ppm] is in the range of from about 1:2 to about 1:4.

[0132] Preferably, wherein the iridium-containing catalyst (c) is selected from IrCl3 and H2IrCl6.

[0133] The [ppm / ppm] ratio of the iridium-containing catalyst (c) to the promoter (d) is determined as described above.

[0134] The present invention also relates to compositions that can be obtained when the process according to the invention is carried out as detailed above with respect to the various embodiments.

[0135] The present invention particularly relates to one or more compounds of formula (I), (R 1 ) y (R 2 O) 3-y A composition comprising SiCH2CHR3CR4R5X(I), one or more iridium-containing compounds, and one or more compounds selected from i) peroxycarboxylic acids, and / or ii) carboxylic acids, R in the formula 1 and R 2 is an alkyl group of 1 to 6 carbon atoms; R 3 is an alkyl group of 1 to 6 carbon atoms or hydrogen; R 4 is an alkyl group of 1 to 6 carbon atoms, hydrogen, or halogen; R 5 is hydrogen or an alkyl group of 1 to 6 carbon atoms; X is a halogen; and y is 0, 1, or 2.

[0136] The iridium-containing compound of the composition according to the present invention is not restricted to any particular compound other than that it necessarily contains one or more iridium atoms or ions. Thus, the iridium-containing compound can be any iridium-containing catalyst or compound, or an iridium particle derived from an iridium-containing hydrosilylation catalyst described in the above description of the process of the present invention. Preferably, the iridium-containing compound is a compound formed from the catalyst used in the process of the present invention, i.e., an intermediate and active catalytic species in the catalytic cycle of the hydrosilylation reaction, such as iridium(0) nanoparticles or iridium(0) micrometer-sized particles.

[0137] As defined herein, nanoparticles are particles having an average particle size of 1 to 500 nm, and micrometer-sized particles are particles having an average particle size of 0.5 to 50 μm, as determined by dynamic light scattering. Additionally, the iridium-containing compound can be a compound derived by deactivation or decomposition from the iridium-containing catalyst of the process of the present invention.

[0138] Similarly, the peroxycarboxylic acids of the compositions of the present invention, as is true of the peroxycarboxylic acids of the processes of the present invention, are not restricted in any particular way other than necessarily containing a peroxycarboxyl group.

[0139] The carboxylic acids of the compositions of the present invention, as defined herein, are not restricted in any particular way other than necessarily containing a carboxyl group.

[0140] In particular, the peroxycarboxylic acid compounds described in the above description of the process of the present invention may be included in the composition of the present invention, and the same compounds as those preferably applied in the process of the present invention may be preferably included in the composition of the present invention. The carboxylic acids of the composition of the present invention are preferably compounds similar to the peroxycarboxylic acid compounds described in the above description of the process of the present invention, and carboxylic acids similar to the peroxycarboxylic acids preferably applied in the process of the present invention are more preferably included in the composition of the present invention. The term "similar," as defined herein with respect to peroxycarboxylic acids and carboxylic acids, means that the carboxylic acid corresponds to the peroxycarboxylic acid in that they are structurally identical except for having a carboxyl group instead of a peroxycarboxyl group.

[0141] The compound of formula (I) contained in the composition according to the present invention is preferably a product obtained by hydrosilylation of a halogenated olefin selected from the group consisting of allyl chloride, methallyl chloride, 3-chloro-1-butene, 3,4-dichloro-1-butene, and combinations thereof, wherein allyl chloride is preferred, and the alkoxysilane is selected from the group consisting of trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane, and diethylethoxysilane, wherein trimethoxysilane and triethoxysilane are preferred.

[0142] The most preferred compounds of formula (I) that may be included in the compositions of the present invention are chloropropyltrimethoxysilane and chloropropyltriethoxysilane.

[0143] In a preferred embodiment of the composition according to the invention, the compound of formula (I) is chloropropyltriethoxysilane.

[0144] In embodiments, the one or more compounds selected from i) peroxycarboxylic acids and / or ii) carboxylic acids are selected from halogenated perbenzoic acids, unsubstituted peroxyalkanoic acids, and α-halogenated peroxyalkanoic acids, and also from halogenated benzoic acids, unsubstituted alkanoic acids, and α-halogenated alkanoic acids.

[0145] The terms "peroxyalkanoic acid," "unsubstituted," and "α-halogenated peroxyalkanoic acid" have the same meanings as defined above. Correspondingly, the term "unsubstituted alkanoic acid" refers to a carboxylic acid consisting of a carboxyl group and an alkyl residue, in which the carbon atoms of the alkyl group bear no other substituents other than hydrogen atoms. The alkyl group may be a primary n-alkyl group, a secondary alkyl group, or a tertiary alkyl group, with primary alkyl groups being preferred, in which the alkyl group may be a linear, branched, or cyclic alkyl group, with C1-C11 n-alkyl groups being preferred. Similarly, the term "α-halogenated alkanoic acid" indicates that the alkyl group of such a compound bears one or more halogen substituents on the carbon atom of the alkyl group bonded to the carbon atom of the carboxyl group.

[0146] In a further embodiment, the one or more compounds selected from i) peroxycarboxylic acids and / or ii) carboxylic acids are selected from monohalogenated perbenzoic acids, dihalogenated perbenzoic acids, tri-, tetra- and pentahalogenated perbenzoic acids, and also from monohalogenated benzoic acids, dihalogenated benzoic acids, tri-, tetra- and pentahalogenated benzoic acids.

[0147] In still further embodiments, the one or more compounds selected from i) peroxycarboxylic acids and / or ii) carboxylic acids are selected from halogenated perbenzoic acids bearing at least one halogen substituent in the meta position relative to the peroxycarboxylic group, and from halogenated benzoic acids bearing at least one halogen substituent in the meta position relative to the carboxylic group.

[0148] In an embodiment according to the invention, the one or more compounds selected from i) peroxycarboxylic acids and / or ii) carboxylic acids are selected from the group of perbenzoic acids consisting of 2-bromo-5-chloroperbenzoic acid, 3,5-difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 2,3,6-trifluoroperbenzoic acid, 2,4,5-trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, 2,3,4,5,6-pentafluoroperbenzoic acid, 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid and 3,5-difluoroperbenzoic acid, preferably the perbenzoic acid is 3-chloroperbenzoic acid , 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid, and / or selected from the group of benzoic acids consisting of 2-bromo-5-chlorobenzoic acid, 3,5-difluorobenzoic acid, 3,4-difluorobenzoic acid, 2,3,6-trifluorobenzoic acid, 2,4,5-trifluorobenzoic acid, 2,3,4-trifluorobenzoic acid, 2,3,4,5,6-pentafluorobenzoic acid, 3-chlorobenzoic acid, 3-fluorobenzoic acid, and 3,5-difluorobenzoic acid, preferably the benzoic acid is selected from 3-chlorobenzoic acid, 3-fluorobenzoic acid, and 3,5-difluorobenzoic acid.

[0149] According to an embodiment, the one or more compounds selected from i) peroxycarboxylic acids and / or ii) carboxylic acids are selected from 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid, and preferably from 3-chlorobenzoic acid, 3-fluorobenzoic acid, and 3,5-difluorobenzoic acid.

[0150] In another embodiment according to the present invention, the one or more compounds selected from i) peroxycarboxylic acids and / or ii) carboxylic acids are selected from the group consisting of C2-C12 α-halogenated peroxyalkanoic acids carrying one or more halogen substituents independently selected from chloro and fluoro substituents, and unsubstituted C2-C12 peroxyalkanoic acids, and also from the group consisting of C2-C12 α-halogenated alkanoic acids carrying one or more halogen substituents independently selected from chloro and fluoro substituents, and unsubstituted C2-C12 alkanoic acids.

[0151] In a further embodiment of the present invention, the iridium-containing compound is selected from nano-sized and micrometer-sized iridium particles.

[0152] The nano-sized and micrometer-sized iridium particles are based on iridium(0) and are typically formed from the iridium-containing catalyst used in the hydrosilylation reaction of the process of the present invention.

[0153] In another embodiment of the present invention, the amount of iridium-containing compound included in the composition ranges from about 1 to about 100 ppm, preferably from about 1 to about 50 ppm, more preferably from about 1 to about 25 ppm, even more preferably from about 2 to about 25 ppm, and most preferably from about 3 to about 15 ppm, based on the total weight of the haloorganosilane of Formula (I).

[0154] Preferably, the amount of iridium-containing compound included in the composition is within the ranges set forth above, based on the total weight of chloropropyltriethoxysilane present as the compound of formula (I) in the composition.

[0155] In a further embodiment, the present invention relates to the use of the compositions described above and compositions obtained from the process of the present invention described above for the preparation of aminoorganosilanes, mercaptoorganosilanes, or methacryloyloxyorganosilanes.

[0156] As defined herein, the term "organosilane" includes organoalkoxysilanes, i.e., organosilanes bearing one, two, or three alkoxy groups on the silicon atom.

[0157] As defined herein, an aminoorganosilane is an organosilane containing a primary, secondary, or tertiary amino group in the organyl residue.

[0158] Preferably, the aminoorganosilane has a structure represented by formula (II): (R 1 ) y (R 2 O) 3-y SiCH2CHR 3 CR 4 R 5 Z 1 (II) R in the formula 1 , R 2 , R 3 , R 4 , R 5 and y is as defined above, Z 1 -NH2, -NHR 6 and NR 6 R 7 , [ka] R in the formula 6 are independently selected from the group consisting of C1-C12 alkyl groups and the following residues: [ka] Preferably R 6 -CH3, -CH2CH2NH2, [ka] R 7 are independently selected from the group consisting of C1 to C12 alkyl groups, preferably R 7is CH3, and more preferably R 6 and R 7 represent the same residue, most preferably R 6 and R 7 represents -CH3.

[0159] As defined herein, a mercaptoorganosilane is an organosilane bearing at least one residue selected from a thiol group, a disulfanyl group, a polysulfanyl group, a thioalkyl group, a dithioalkyl group, or a polythioalkyl group, bonded to the organyl residue of the organosilane via an -S- atom.

[0160] Preferably, the mercaptoorganosilane has a structure represented by formula (III): (R 1 ) y (R 2 O) 3-y SiCH2CHR 3 CR 4 R 5 Z 2 (III) R in the formula 1 , R 2 , R 3 , R 4 , R 5 and y is as defined above, Z 2 -SH, -S-SH, -S (u) -SH, -SR 8 , -S-SR 8 , -S (u) -SR 8 , where u is an integer from 2 to 8, preferably u is 2, 3 or 4, and R 8 is a C1-C12 alkyl group optionally containing a C=O group, preferably a C2 to C12 acyl group, i.e., a group and residue (R 1 ) y (R 2 O) 3-y SiCH2CHR3 CR 4 R 5 wherein R 1 , R 2 , R 3 , R 4 , R 5 and y is as defined above.

[0161] The term "derived from a carboxylic acid" when used in reference to an acyl group means that the acyl group R 8 This means that the carbonyl carbon atom is bonded to the S atom. 8 Compounds bearing the group can be formed by condensing a carboxylic acid with the terminal SH group of a precursor compound.

[0162] Therefore, preferred groups R according to this embodiment 8 is an acetyl group, a butanoyl group, a hexanoyl group, an octanoyl group, a decanoyl group, a dodecanoyl group, a neodecanoyl group, and a 2-ethylhexanoyl group.

[0163] As defined herein, a methacryloyloxyorganosilane is an organosilane bearing at least one methacryloyloxy group attached via an -O- atom to the organyl residue of the organosilane.

[0164] Preferably, the methacryloyloxyorganosilane has a structure represented by formula (IV): (R 1 ) y (R 2 O) 3-y SiCH2CHR 3 CR 4 R 5 Z 3 (IV) R in the formula 1 , R 2 , R 3 , R 4 , R 5 and y is as defined above, and Z 3 is -OC(O)C(CH2)CH3.

[0165] The compounds of formula (I) contained in the compositions according to the invention can be converted into the desired functionalized organosilanes by displacing the halide substituents in a nucleophilic reaction with amine reagents, sulfide, thiolate or polysulfide reagents or methacrylate reagents, e.g., methacrylate salts, respectively.

[0166] In an embodiment according to the present invention, the composition is used to prepare a polysulfane-containing organoalkoxysilane.

[0167] As defined herein, a polysulfane-containing organoalkoxysilane is a compound having the formula (R 1 ) y (R 2 O) 3-y SiCH2CHR 3 CR 4 R 5 Z 2 (III) is a mercaptoorganosilane having the structure R in the formula 1 , R 2 , R 3 , R 4 , R 5 and y is as defined above, and Z 2 -S-SH, -S (u) -SH, -S-SR 8 , -S (u) -SR 8 , where u is an integer from 2 to 8, preferably u is 2, 3, or 4, and R 8 is a C1 to C12 alkyl group optionally containing a C=O group, preferably a C2 to C12 acyl group, more preferably an acetyl group, a butanoyl group, a hexanoyl group, an octanoyl group, a decanoyl group, a dodecanoyl group, a neodecanoyl group, and a 2-ethylhexanoyl group, and a residue (R 1 ) y (R 2 O) 3-y SiCH2CHR 3 CR 4 R 5wherein R 1 , R 2 , R 3 , R 4 , R 5 and y is as defined above.

[0168] In a preferred embodiment, the composition is used for the preparation of polysulfane-containing organoalkoxysilanes, which are used in the manufacture of silica-filled tires.

[0169] In another embodiment of the present invention, the composition used to prepare the aminoorganosilane, mercaptosilane, or methacryloyloxyorganosilane comprises chloropropyltriethoxysilane.

[0170] According to an embodiment, the chloropropyltriethoxysilane contained in the composition is converted to aminopropyltriethoxysilane of formula (V) (EtO)3SiCH2CH2CH2Z 1 (V) Z in the formula 1 is as defined above, converted to a mercaptoorganosilane of formula (VI) (EtO)3SiCH2CH2CH2Z 2 (VI) Z in the formula 2 is as defined above, Or it is converted to methacryloyloxypropyltriethoxysilane.

[0171] Overview of the Preferred Embodiments of the Invention In the following, preferred embodiments of the present invention are outlined:

[0172] 1. A process for producing a compound of formula (I), comprising: (R 1 ) y (R 2 O) 3-y SiCH2CHR 3 CR 4 R 5X (I) (a) Formula H2C=CR 3 CR 4 R 5 (b) a halogenated olefin having the formula (R 1 ) y (R 2 O) 3-y (c) a catalytically effective amount of an iridium-containing catalyst; and (d) a reaction-promoting effective amount of a peroxycarboxylic acid to produce a product of formula (I), R 1 and R 2 is an alkyl group of 1 to 6 carbon atoms; R 3 is an alkyl group of 1 to 6 carbon atoms or hydrogen; R 4 is an alkyl group of 1 to 6 carbon atoms, hydrogen, or halogen; R 5 is hydrogen or an alkyl group of 1 to 6 carbon atoms; X is a halogen; and The process, where y is 0, 1, or 2.

[0173] 2. The process of embodiment 1, wherein the halogenated olefin (a) is selected from the group consisting of allyl chloride, methallyl chloride, 3-chloro-1-butene, 3,4-dichloro-1-butene, and combinations thereof; preferably, the halogenated olefin (a) is allyl chloride.

[0174] 3. The process of embodiment 1 or 2, wherein the alkoxysilane (b) is selected from the group consisting of trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane, diethylethoxysilane, and combinations thereof; preferably, the alkoxysilane is triethoxysilane.

[0175] 4. The process of any of embodiments 1 to 3, wherein the reaction-promoting effective amount of peroxycarboxylic acid (d) is in the range of from about 1 to about 2000 ppm, preferably from about 2 to about 500 ppm, more preferably from about 3 to about 200 ppm, even more preferably from about 4 to about 100 ppm, even more preferably from about 5 to about 50 ppm, even more preferably from about 5 to about 25 ppm, and most preferably from about 5 to about 15 ppm, based on the combined weight of the starting halogenated olefin (a) and alkoxysilane (b).

[0176] 5. The process of any of embodiments 1 to 4, wherein the peroxycarboxylic acid (d) is selected from the group of halogenated perbenzoic acids, the group of unsubstituted peroxyalkanoic acids, or the group of α-halogenated peroxyalkanoic acids.

[0177] 6. The process of any of embodiments 1 to 5, wherein the peroxycarboxylic acid (d) is selected from the group of monohalogenated perbenzoic acids, the group of dihalogenated perbenzoic acids, and the group of tri-, tetra-, and pentahalogenated perbenzoic acids.

[0178] 7. The process of any of embodiments 1 to 6, wherein the peroxycarboxylic acid (d) is selected from the group of halogenated perbenzoic acids bearing at least one halogen substituent in the meta position relative to the peroxycarboxylic group.

[0179] 8. The process of any of embodiments 1 to 7, wherein the peroxycarboxylic acid (d) is selected from halogenated perbenzoic acids bearing a total of one, two, or three halogen substituents, wherein preferably at least one, and more preferably all, of the halogen substituents are independently selected from fluoro and chloro substituents, and most preferably either all halogen substituents are chloro substituents or all halogen substituents are fluoro substituents.

[0180] 9. The process of any of embodiments 1 to 8, wherein the peroxycarboxylic acid (d) is selected from the group of perbenzoic acids consisting of 2-bromo-5-chloroperbenzoic acid, 3,5-difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 2,3,6-trifluoroperbenzoic acid, 2,4,5-trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, 2,3,4,5,6-pentafluoroperbenzoic acid, 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid.

[0181] 10. The process of any of embodiments 1 to 9, wherein the peroxycarboxylic acid (d) is selected from 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid.

[0182] 11. The process of any of embodiments 1 to 5, wherein the peroxycarboxylic acid (d) is an α-halogenated peroxyalkanoic acid selected from the group of C2 to C12 α-halogenated peroxyalkanoic acids bearing one or more halogen substituents independently selected from chloro and fluoro substituents, or the peroxycarboxylic acid (d) is an unsubstituted C2 to C12 peroxyalkanoic acid.

[0183] 12. The process of any of embodiments 1 to 5 or 11, wherein the peroxycarboxylic acid (d) is an α-halogenated alkanoic acid selected from chloroperacetic acid, fluoroperacetic acid, dichloroperacetic acid, difluoroperacetic acid, trifluoroperacetic acid, and trichloroperacetic acid.

[0184] 13. The process of any of embodiments 1 to 12, wherein the iridium-containing catalyst (c) is selected from the group consisting of nanometer-sized and micrometer-sized iridium particles, iridium halides, zinc or tin reduction reaction products of iridium halides, cycloolefin complexes of iridium, amine complexes of iridium, phosphine complexes of iridium, CO complexes of iridium, and combinations thereof.

[0185] 14. The process of any of embodiments 1 to 13, wherein the amount of iridium-containing catalyst (c), based on the combined weight of the starting halogenated olefin (a) and alkoxysilane (b), is in the range of from about 1 to about 100 ppm, preferably from about 1 to about 50 ppm, more preferably from about 1 to about 25 ppm, even more preferably from about 2 to about 25 ppm, and most preferably from about 3 to about 15 ppm.

[0186] 15. Iridium-containing catalysts (c) include IrCl3, IrBr3, M2IrCl6, where M = H or an alkali metal; cycloolefin complexes of iridium, e.g., Ir2Cl2(COE)4, Crabtree's catalyst, [Ir(μ 2~C 15. The process of any of embodiments 1 to 14, wherein the compound is selected from the group consisting of Ir(OCH)(COD), where COE is cyclooctene and COD is 1,5-cyclooctadiene; pentamethylcyclopentadienyl iridium dichloride dimer [Cp*IrCl]; (π-arene)iridium complexes, and combinations thereof.

[0187] 16. The process of any of embodiments 1 to 15, wherein the iridium-containing catalyst (c) is selected from IrCl3·xH2O or H2IrCl6.

[0188] 17. The process of any of embodiments 1 to 16, wherein the iridium-containing catalyst (c) is added to the reaction as a solid or as a solution or suspension in an organic solvent, preferably from an OH-functionalized solvent, i.e., for example, OH-functionalized alkanols, diols and triols, such as ethanol, polyethers, preferably catalyst (c) is added as a solid.

[0189] 18. The process of any of embodiments 1 to 17, wherein the halogenated olefin (a) is a technical grade halogenated olefin, preferably technical grade allyl chloride.

[0190] 19. The process of any of embodiments 1 to 18, wherein the molar ratio of halogenated olefin (a) to alkoxysilane (b) is in the range of from about 10:1 to about 1:10, preferably from about 5:1 to about 1:5, more preferably from about 2:1 to about 1:2, even more preferably from about 1.7:1 to about 1:1.7, even more preferably from about 1.5:1 to about 1:1.5, and most preferably from about 1.2:1 to about 1:1.2.

[0191] 20. The process of any of embodiments 1 to 19, wherein the ratio of iridium-containing catalyst (c) to peroxycarboxylic acid (d) in [ppm to ppm] based on the combined weight of the starting halogenated olefin (a) and alkoxysilane (b), respectively, is in the range of about 1:1 to about 1:40, preferably in the range of about 1:1.5 to about 1:25, more preferably in the range of about 1:2 to about 1:20, and most preferably in the range of about 1:2 to about 1:10.

[0192] 21. The process of any of embodiments 1 to 20, wherein the halogenated olefin (a) is allyl chloride, the alkoxysilane (b) is triethoxysilane, the iridium-containing catalyst (c) is IrCl3 or H2IrCl6, and the peroxycarboxylic acid (d) is 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, or 3,5-difluoroperbenzoic acid.

[0193] 22. The process of any of embodiments 1 to 21, wherein the halogenated olefin (a) is allyl chloride, the alkoxysilane (b) is triethoxysilane, the amount of iridium-containing catalyst (c) is in the range of about 5 to about 20 ppm, and the peroxycarboxylic acid (d) is one of the following: mCPBA present in an amount satisfying the requirement that the ratio of catalyst (c) to promoter (d) in [ppm / ppm] ranges from about 1:2.5 to about 1:20; or mFPBA present in an amount satisfying the proviso that the ratio of catalyst (c) to promoter (d) in [ppm / ppm] is in the range of about 1:2.5 to about 1:10; or dFPBA present in an amount satisfying the proviso that the ratio of catalyst (c) to promoter (d) in [ppm / ppm] is in the range of from about 1:2 to about 1:4.

[0194] 23. The process of any of the previous embodiments, wherein the iridium-containing catalyst is selected from IrCl3 and H2IrCl6.

[0195] 24. A composition obtainable by the process of any of embodiments 1 to 23.

[0196] 25. One or more compounds of formula (I), (R 1 ) y (R 2 O) 3-y 1. A composition comprising SiCH2CHR3CR4R5X(I), one or more iridium-containing compounds, and one or more compounds selected from i) peroxycarboxylic acids, and / or ii) carboxylic acids, R in the formula 1 and R 2 is an alkyl group of 1 to 6 carbon atoms; R 3 is an alkyl group of 1 to 6 carbon atoms or hydrogen; R 4 is an alkyl group of 1 to 6 carbon atoms, hydrogen, or halogen; R 5 is hydrogen or an alkyl group of 1 to 6 carbon atoms; X is a halogen; and The composition wherein y is 0, 1, or 2.

[0197] 26. The composition of embodiment 25, wherein the compound of formula (I) is chloropropyltriethoxysilane.

[0198] 27. The composition of embodiment 25 or 26, wherein the one or more compounds selected from i) peroxycarboxylic acids, and / or ii) carboxylic acids are selected from halogenated perbenzoic acids, unsubstituted peroxyalkanoic acids, or α-halogenated peroxyalkanoic acids, halogenated benzoic acids, unsubstituted alkanoic acids, or α-halogenated alkanoic acids.

[0199] 28. The composition of any of embodiments 25 to 27, wherein the one or more compounds selected from i) peroxycarboxylic acids, and / or ii) carboxylic acids are selected from monohalogenated perbenzoic acids, dihalogenated perbenzoic acids, and tri-, tetra-, and pentahalogenated perbenzoic acids, and from monohalogenated benzoic acids, dihalogenated benzoic acids, and tri-, tetra-, and pentahalogenated benzoic acids.

[0200] 29. The composition of any of embodiments 25 to 28, wherein the one or more compounds selected from i) peroxycarboxylic acids, and / or ii) carboxylic acids are selected from halogenated perbenzoic acids bearing at least one halogen substituent in the meta position relative to the peroxycarboxylic group, and from halogenated benzoic acids bearing at least one halogen substituent in the meta position relative to the carboxylic group.

[0201] 30. The one or more compounds selected from i) peroxycarboxylic acids and / or ii) carboxylic acids are 2-bromo-5-chloroperbenzoic acid, 3,5-difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 2,3,6-trifluoroperbenzoic acid, 2,4,5-trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, 2,3,4,5,6-pentafluoroperbenzoic acid, 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid. 30. The composition of any of embodiments 25 to 29, wherein the perfluorobenzoic acid is selected from the group of perfluorobenzoic acids consisting of 2-bromo-5-chlorobenzoic acid, 3,5-difluorobenzoic acid, 3,4-difluorobenzoic acid, 2,3,6-trifluorobenzoic acid, 2,4,5-trifluorobenzoic acid, 2,3,4-trifluorobenzoic acid, 2,3,4,5,6-pentafluorobenzoic acid, 3-chlorobenzoic acid, 3-fluorobenzoic acid, and 3,5-difluorobenzoic acid.

[0202] 31. The composition of any of embodiments 25 to 30, wherein the one or more compounds selected from i) peroxycarboxylic acids, and / or ii) carboxylic acids are selected from 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid, and also from 3-chlorobenzoic acid, 3-fluorobenzoic acid, and 3,5-difluorobenzoic acid.

[0203] 32. The composition of any of embodiments 25 to 31, wherein the one or more compounds selected from i) peroxycarboxylic acids, and / or ii) carboxylic acids are selected from the group consisting of C2 to C12 α-halogenated peroxyalkanoic acids, and unsubstituted C2 to C12 peroxyalkanoic acids, bearing one or more halogen substituents independently selected from chloro and fluoro substituents; and also selected from the group consisting of C2 to C12 α-halogenated alkanoic acids, and unsubstituted C2 to C12 alkanoic acids, bearing one or more halogen substituents independently selected from chloro and fluoro substituents.

[0204] 33. The composition of any of embodiments 25 to 32, wherein the iridium-containing compound is nanometer-sized and micrometer-sized iridium particles.

[0205] 34. The composition of any of embodiments 25 to 33, wherein the amount of iridium-containing compound is in the range of about 1 to about 100 ppm, preferably about 1 to about 50 ppm, more preferably about 1 to about 25 ppm, even more preferably about 2 to about 25 ppm, and most preferably about 3 to about 15 ppm, based on the total weight of the compounds of formula (I).

[0206] 35. Use of the composition of any of embodiments 24 to 34 for the preparation of aminoorganosilanes, mercaptoorganosilanes, or methacryloyloxyorganosilanes.

[0207] 36. The use of the composition of embodiment 35, wherein the composition is used for preparing a polysulfane-containing organoalkoxysilane.

[0208] 37. The use of the composition of embodiment 36, wherein the polysulfane-containing organoalkoxysilane is used for the manufacture of silica-filled tires.

[0209] 38. The use of the composition of any of embodiments 35 to 37, wherein the composition comprises chloropropyltriethoxysilane.

[0210] While the exact scope of the present invention is set forth in the claims, the following specific examples illustrate certain embodiments of the invention and, more particularly, point out various embodiments of methods for evaluating the invention. However, these examples are provided for illustrative purposes only and should not be construed as limitations on the invention.

[0211] Example The present invention is further illustrated by, but not limited to, the following examples.

[0212] General - Chemical Substances and Abbreviations IrCl3·xH2O: abcr; 99.99% CAS 14996-61-3; Iridium(III) chloride hydrate H2IrCl6: abcr; 99.90% CAS 110802-84-1; Hexachloroiridin(IV) acid hydrate Dry ethanol: analytical grade ethanol further dried over molecular sieves (3A) Allyl chloride: Momentive grade (batch RBT190731C), ≥ 99% by weight Hypercondensed allyl chloride: Hypercondensed allyl chloride was obtained by vacuum treatment of as-received allyl chloride.

[0213] The as-received allyl chloride was fed into a Schlenk flask connected by a glass bridge to a second Schlenk flask (cooled with dry ice / iPr). Compounds that did not evaporate at 20°C / 0.4 mbar remained in the first flask and were thus separated from the overcondensed allyl chloride. NMR and GC-TCD measurements showed no obvious change in the purity of the overcondensed allyl chloride compared to the as-received allyl chloride, but the non-volatile compounds formed a yellow liquid.

[0214] Triethoxysilane: Momentive grade (TES; Momentive grade synthesized from HSiCl), 89-92 wt% Di-tert-butyl peroxide (DtBP): Sigma-Aldrich; 98% tert-Butyl hydroperoxide (tBHP): Sigma-Aldrich; 5.5 moles in decane tert-Butyl perbenzoic acid (tBPB): Sigma-Aldrich; 98% m-Chloroperbenzoic acid or metachloroper(oxy)benzoic acid (mCPBA): Sigma-Aldrich; 77% activity CAS 937-14-4; the mCPBA purchased is a mixture of mCPBA, m-chlorobenzoic acid, and water (for stabilization), and the 77% activity, as determined by titration with NaSO according to the seller, is assumed to be equal to the amount of mCPBA in the mixture. m-Fluoroperbenzoic acid (mFPBA) and 3,5-difluoroperbenzoic acid (dFPBA) were synthesized according to the literature (Organic Synthesis, Coll. Vol. 6, p. 276 (1988); Vol. 50, p. 15 (1970) "m-Chloroperbenzoic Acid"), DOI: 10.15227 / orgsyn.050.0015.

[0215] Analysis details NMR NMR measurements were carried out using either a BRUKER DPX400 or a BRUKER AVANCEIII 500 MHz equipped with a 5 mm multinuclear probe head.

[0216] The table below shows the resonant frequencies of the nuclei investigated. TIFF2025542003000004.tif48155

[0217] The compounds under investigation were stored under an argon atmosphere. Therefore, 0.2 ml of compound was dissolved in 0.4 ml of solvent. In all cases, deuterated chloroform was used as the solvent, and 1% TMS was added as a standard. Thus, the TMS signal serves as the reference point for all chemical shifts, which are given in ppm. Where necessary, 100 μl of HMDSO was used as an internal standard to determine the mass fractions.

[0218] FT-IR Spectra were generated on a Nicolet 380 FT-IR using standard FT-IR ATR measurement procedures. The investigated peroxycarboxylic acid samples required no additional preparation prior to measurement.

[0219] Catalyst Preparation and Hydrosilylation All catalyst preparations and hydrosilylation reactions were carried out under an argon atmosphere using Schlenk techniques. The structure of the product is: 1 H-NMR, 13 The results were confirmed by C-NMR and FTIR spectroscopy.

[0220] Synthesis Example 1: Synthesis of m-fluoroperbenzoic acid (m-FPBA) [ka] 36 ml of DI water, 3.6 g of NaOH, 0.15 g of MgSO4·7H2O, and 45 ml of 1,4-dioxane were mixed in a 250 ml glass beaker and cooled to 10–15 °C. 9 ml of a 30% (wt%) H2O2 solution was added. After vigorous stirring, 4.76 g (30 mmol) of m-fluorobenzoyl chloride was slowly added. The mixture was stirred at ≤25 °C for 15 min. The mixture was then transferred to a separatory funnel. 90 ml of ice-cold 3.7 M H2SO4 was added. After phase separation, the aqueous phase was extracted four times with 20 ml of ice-cold dichloromethane. The organic phases were combined and dried over MgSO4. The dichloromethane was removed under reduced pressure using a rotary evaporator. The water bath was at 30° C. and the pressure was reduced in steps of 25 mbar from 200 mbar to 0 mbar. The desired product was obtained as a white solid. Yield: 1.81 g (39%). Purity: 100%. The structure of the product was: 1 H-NMR, 13 The results were confirmed by C-NMR and FTIR spectroscopy.

[0221] Synthesis Example 2: Synthesis of 3,5-difluoroperbenzoic acid (dFPBA) [ka] 36 ml of DI water, 3.6 g of NaOH, 0.15 g of MgSO4·7H2O, and 45 ml of 1,4-dioxane were mixed in a 250 ml glass beaker and cooled to 10–15°C. 9 ml of 30% active H2O2 solution was added. After vigorous stirring, 5.3 g (30 mmol) of 3,5-difluorobenzoyl chloride was slowly added. The mixture was stirred at <25°C for 15 minutes. The mixture was then transferred to a separatory funnel. 90 ml of ice-cold 3.7 M H2SO4 was added. After phase separation, the aqueous phase was extracted four times with 20 ml of ice-cold dichloromethane. The organic phases obtained by the extraction of the aqueous phase were combined and dried over MgSO4. The dichloromethane was removed under reduced pressure at room temperature using a rotary evaporator. The water bath was at 30°C and the pressure was reduced stepwise from 200 mbar to 0 mbar in 25 mbar increments. A white solid was obtained. Yield: 0.97 g (19%). Purity: 100%. The structure of the product shown above is: 1 H-NMR, 13 The results were confirmed by C-NMR and FTIR spectroscopy.

[0222] Synthesis Example 3: IrCl3·xH2O catalyst solution in dry ethanol 0.1 g of IrCl3·xH2O was placed in a Schlenk bottle under an argon atmosphere. 10 ml of dry ethanol was added. The mixture was stirred at 1200 rpm for 4 days. A clear, greenish solution was obtained, which could be used as a catalyst for approximately 2 days.

[0223] Synthesis Example 4: Solid catalyst IrCl3·xH2O Commercially available solid IrCl3·xH2O was used without further pretreatment for the hydrosilylation reaction.

[0224] Synthesis Example 5: H2IrCl6 catalyst solution in dry ethanol 1 g of H2IrCl6 was dissolved in 10 ml of dry ethanol. A black catalyst solution was obtained, which can be used as a catalyst for approximately 2 months.

[0225] Hydrosilylation Reaction Example 1: General Protocol for Hydrosilylation Using Catalyst Solution The reaction was carried out in a 50 ml Schlenk bottle equipped with a reflux condenser. A calculated amount of peracid (expressed in ppm based on the combined mass of the starting materials triethoxysilane and allyl chloride) was placed in the Schlenk bottle. Then, 33.5 g of a stock solution consisting of 10 g of purified (percondensed) allyl chloride and 23.5 g of TES (triethoxysilane) was added. A calculated amount of catalyst solution (catalyst content expressed in ppm based on the combined mass of the starting materials triethoxysilane and allyl chloride, where ppm indicates the amount of iridium metal contained in the catalyst compound) was added, and the mixture was heated to 80 °C while stirring using a magnetic stir bar at 300 rpm.

[0226] [ka]

[0227] Example 2: General protocol for hydrosilylation using solid catalysts The reaction was carried out in a 50 ml Schlenk bottle equipped with a reflux condenser. The calculated amount of solid catalyst and 2.35 g (10 mol % of the calculated amount) of TES were placed in the Schlenk bottle. The Schlenk bottle was heated to 80° C., and the mixture was stirred at 300 rpm. Separately, a mixture consisting of 10 g of allyl chloride (either as received or overcondensed), 21.15 g (90 mol % of the calculated amount) of TES, and the calculated amount of peracid was prepared and placed in a dropping funnel. This mixture was fed into the Schlenk bottle over 30 minutes. After the end of the feed, the reaction temperature was maintained at 80° C. for the indicated reaction time.

[0228] [Table 1]

[0229] The data in Table 1 show that at high iridium concentrations (100 ppm), moderate to good yields are achievable in the absence of a promoter or in the presence of a hydroperoxide or dialkyl peroxide (non-inventive comparative examples 3-6). The addition of a halogenated perbenzoic acid significantly increases the yield (example 7).

[0230] At low iridium concentrations (10 ppm and below), the presence of a halogenated perbenzoic acid derivative is essential to obtain high yields (Examples 4 and 9). mFPBA is the halogenated perbenzoic acid derivative that gives the best results (Examples 10 and 11).

[0231] The data presented in Table 1 demonstrate a synergistic effect between iridium and halogenated perbenzoic acids because the reaction requires iridium catalyst when halogenated perbenzoic acids are present in low amounts. At high iridium catalyst concentrations of 100 ppm, other peroxy compounds, such as tBHP, are less effective than mCPBA. DtBP has a detrimental effect on the yield of the target product (Examples 5 and 6).

[0232] [Table 2]

[0233] [Table 3]

[0234] [Table 4]

[0235] The data in Table 2 show that the presence of a 2.5 to 20-fold excess of promoter results in substantially increased yields of the desired compound (Examples 12, 9, 13, 14, 10, 15, and 16 compared to Example 4).

[0236] The data in Table 3 show that for as-received allyl chloride, the addition of halogenated perbenzoic acids is essential to achieve high yields at suitably low iridium concentrations (Examples 21 and 22). The use of peroxide ethers results in significantly lower yields when compared to analogous reactions using peroxycarboxylic acids in the process of the present invention as promoters (Example 23). It can be concluded that the presence of halogenated perbenzoic acids increases the tolerance of as-received solid IrCl3xH2O with low iridium concentrations to the presence of impurities in the as-received raw materials. The availability of as-received allyl chloride and as-received solid catalysts with low iridium concentrations are both prerequisites for a robust and economically attractive large-scale process.

[0237] The data in Table 4 show that at high iridium concentrations (100 ppm), H2IrCl6 solutions give reasonable yields of CPTES (Example 24).

[0238] At low iridium concentrations (10 ppm and below), the combination of H2IrCl6 solution with halogenated perbenzoic acids, such as mFPBA, is essential for high yields of CPTES (Comparative Examples 25 and 27).

[0239] The results of Example 28 show that H2IrCl6 is also applicable to processes based on easy-to-prepare catalyst solutions, low concentrations of iridium, and as-received allyl chloride. Comparative Example 29 shows that even at substantially higher catalyst concentrations, yields using H2IrCl6 solutions are only moderate compared to reactions carried out in the presence of halogenated perbenzoic acids.

Claims

1. A process for producing a compound of formula (I), comprising: () １ ) ｙ () ２ [] ３－ｙ SiCH ２ CHR ３ CR ４ - ５ X (I) (a) Formula H ２ C=CR ３ CR ４ R ５ a halogenated olefin having X; (b) Formula (R １ ) ｙ (R ２ O) ３－ｙ Alkoxysilanes containing SiH; (c) a catalytically effective amount of an iridium-containing catalyst; and (d) a reaction-accelerating effective amount of peroxycarboxylic acid to produce a product of formula (I), During the ceremony R １ and R ２ is an alkyl group of 1 to 6 carbon atoms; R ３ is an alkyl group of 1 to 6 carbon atoms or hydrogen; R ４ is an alkyl group of 1 to 6 carbon atoms, hydrogen or halogen; R ５ is hydrogen or an alkyl group of 1 to 6 carbon atoms; X is a halogen; and y is 0, 1 or 2; Preferably, the amount of iridium-containing catalyst (c) based on the combined weight of the starting halogenated olefin (a) and alkoxysilane (b) is in the range of from about 1 to about 100 ppm, preferably from about 1 to about 50 ppm, more preferably from about 1 to about 25 ppm, even more preferably from about 2 to about 25 ppm, and most preferably from about 3 to about 15 ppm.

2. 2. The process of claim 1, wherein the halogenated olefin (a) is selected from the group consisting of allyl chloride, methallyl chloride, 3-chloro-1-butene, 3,4-dichloro-1-butene, and combinations thereof, preferably the halogenated olefin (a) is allyl chloride.

3. 3. The process of claim 1 or 2, wherein the alkoxysilane (b) is selected from the group consisting of trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane, diethylethoxysilane, and combinations thereof; preferably, the alkoxysilane is triethoxysilane.

4. 4. The process according to any one of claims 1 to 3, wherein the peroxycarboxylic acid (d) is selected from the group of monohalogenated perbenzoic acids, the group of dihalogenated perbenzoic acids, and the group of tri-, tetra- and pentahalogenated perbenzoic acids, preferably the peroxycarboxylic acid (d) is selected from the group of halogenated benzoic acids bearing at least one halogen substituent in the meta position relative to the peroxycarboxyl group.

5. 5. The process according to any one of claims 1 to 4, wherein the peroxycarboxylic acid (d) is selected from the group of perbenzoic acids consisting of 2-bromo-5-chloroperbenzoic acid, 3,5-difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 2,3,6-trifluoroperbenzoic acid, 2,4,5-trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, 2,3,4,5,6-pentafluoroperbenzoic acid, 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid, preferably the peroxycarboxylic acid (d) is selected from 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid.

6. The iridium-containing catalyst (c) is selected from the group consisting of nanometer-sized and micrometer-sized iridium, iridium halides, zinc or tin reduction reaction products of iridium halides, cycloolefin complexes of iridium, amine complexes of iridium, phosphine complexes of iridium, CO complexes of iridium, and combinations thereof, or IrCl ３ , IrBr ３ , M ２ IrCl ６ where M=H, or an alkali metal; cycloolefin complexes of iridium, e.g., Ir ２ Cl ２ (COE) ４ , Crabtree catalyst, [Ir(μ ２～Ｃ l) (COD)] ２ and Ir ２ (OCH ３ ) ２ (COD) ２ where COE is cyclooctene and COD is 1,5-cyclooctadiene; pentamethylcyclopentadienyl iridium dichloride dimer [Cp*IrCl ２ ] ２ 6. The process according to any one of claims 1 to 5, wherein the compound is selected from the group consisting of: (π-arene)iridium complexes; (π-arene)iridium complexes; and combinations thereof.

7. 7. The process according to any one of claims 1 to 6, wherein the ratio of the iridium-containing catalyst (c) to the peroxycarboxylic acid (d) in ppm to ppm based on the combined weight of the starting halogenated olefin (a) and alkoxysilane (b), respectively, is in the range of about 1:1 to about 1:40, preferably in the range of about 1:1.5 to about 1:25, more preferably in the range of about 1:2 to about 1:20, and most preferably in the range of about 1:2 to about 1:

10.

8. The halogenated olefin (a) is allyl chloride, the alkoxysilane (b) is triethoxysilane, and the iridium-containing catalyst (c) is IrCl ３ or H ２ IrCl ６ and the peroxycarboxylic acid (d) is 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, or 3,5-difluoroperbenzoic acid.

9. one or more compounds of formula (I), (R １ ) ｙ (R ２ O) ３－ｙ SiCH ２ CHR ３ CR ４ R ５ A composition comprising X(I), one or more iridium-containing compounds, and one or more compounds selected from i) peroxycarboxylic acids, and / or ii) carboxylic acids, During the ceremony R １ and R ２ is an alkyl group of 1 to 6 carbon atoms; R ３ is an alkyl group of 1 to 6 carbon atoms or hydrogen; R ４ is an alkyl group of 1 to 6 carbon atoms, hydrogen or halogen; R ５ is hydrogen or an alkyl group of 1 to 6 carbon atoms; X is a halogen; and y is 0, 1 or 2; wherein the amount of iridium-containing compound, based on the total weight of the compounds of formula (I), is in the range of from about 1 to about 100 ppm, preferably from about 1 to about 50 ppm, more preferably from about 1 to about 25 ppm, even more preferably from about 2 to about 25 ppm, and most preferably from about 3 to about 15 ppm.

10. 10. The composition of claim 9, wherein the compound of formula (I) is chloropropyltriethoxysilane.

11. 11. The composition of claim 9 or 10, wherein the one or more compounds selected from i) peroxycarboxylic acids and / or ii) carboxylic acids are selected from monohalogenated perbenzoic acids, dihalogenated perbenzoic acids, tri-, tetra- and pentahalogenated perbenzoic acids, monohalogenated benzoic acids, dihalogenated benzoic acids, tri-, tetra- and pentahalogenated benzoic acids, preferably the one or more compounds selected from i) peroxycarboxylic acids and / or ii) carboxylic acids are selected from halogenated perbenzoic acids bearing at least one halogen substituent in the meta position relative to the peroxycarboxyl group and halogenated benzoic acids bearing at least one halogen substituent in the meta position relative to the carboxyl group.

12. The one or more compounds selected from i) peroxycarboxylic acids and / or ii) carboxylic acids are selected from the group of perbenzoic acids consisting of 2-bromo-5-chloroperbenzoic acid, 3,5-difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 2,3,6-trifluoroperbenzoic acid, 2,4,5-trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, 2,3,4,5,6-pentafluoroperbenzoic acid, 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid; 12. The composition of any one of claims 9 to 11, wherein the one or more compounds selected from the group of benzoic acids consisting of 6-trifluorobenzoic acid, 2,4,5-trifluorobenzoic acid, 2,3,4-trifluorobenzoic acid, 2,3,4,5,6-pentafluorobenzoic acid, 3-chlorobenzoic acid, 3-fluorobenzoic acid, and 3,5-difluorobenzoic acid, preferably the one or more compounds selected from i) peroxycarboxylic acids and / or ii) carboxylic acids are selected from 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid, and 3-chlorobenzoic acid, 3-fluorobenzoic acid, and 3,5-difluorobenzoic acid.

13. 13. The composition of any of claims 9 to 12, wherein the iridium-containing compound is selected from nanometer-sized and micrometer-sized iridium particles.

14. 14. Use of a composition according to any one of claims 9 to 13, preferably comprising chloropropyltriethoxysilane, for the preparation of an aminoorganosilane, a mercaptoorganosilane or a methacryloyloxyorganosilane.

15. 15. Use of the composition of claim 14, wherein the composition is used for the preparation of polysulfane-containing organoalkoxysilanes, and preferably the polysulfane-containing organoalkoxysilanes are used for the production of silica-filled tires.

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