Method for producing halogenoalkoxy(organo)silanes and -siloxanes and pseudohalogenoalkoxy(organo)silanes and -siloxanes

Abstract

The invention relates to a method for producing a compound of general formula (I), wherein m is 0 or an integer from 1 to 10; and n, at each occurrence, is 0 or 1; wherein at least one of the R1 groups is halogen or pseudohalogen, and wherein at least one of the R1 groups is a -O-R2 group. The method comprises reacting a compound of general formula (II) with a compound of general formula (III), wherein x is 0 or 1; and y, at each occurrence, is 0 or 1; wherein at least one of the R3 groups is halogen or pseudohalogen; in the presence of a catalyst, wherein the catalyst is an organophosphine.

Description

Description Process for the preparation of haloalkoxy(organo)silanes and -siloxanes and pseudohaloalkoxy(organo)silanes and -siloxanes

[0001] The invention relates to a process for the preparation of haloalkoxy(organo)silanes and -siloxanes and pseudohaloalkoxy(organo)silanes and -siloxanes.

[0002] Tetraalkoxysilanes are common byproducts of large-scale industrial reactions for the catalytic conversion of hydridoalkoxysilanes. The separation and purification of these tetraalkoxysilanes are cost-intensive processes. Direct sale of the resulting compounds is not economically viable due to the comparatively low demand. Likewise, the targeted conversion of tetraalkoxysilanes into more sought-after compounds presents a challenge due to their comparatively high chemical inertness.

[0003] The possibilities for obtaining haloalkoxy(organo)silanes and siloxanes can be divided into three basic concepts: alcoholysis, chlorination and ligand exchange reactions.

[0004] The best known and most widespread preparation is the alcoholysis of corresponding halogen(organo)silanes or -siloxanes. In general, halogen(organo)silanes or -siloxanes are reacted with an alcohol, yielding, depending on the stoichiometry, a product mixture of the corresponding (halo)alkoxy(organo)silanes or -siloxanes. This reaction, for example, has been widely investigated in the literature for tetrachlorosilane since the 1940s (Peppard et al., J. Am. Chem. Soc. 1946, 68, 1, 70-72), particularly with the aim of increasing the very low selectivity. Equation Pl shows the reaction of a halogenosilane with an alcohol, denoted as AlkOH, to form a halogen(trialkoxy)silane. Equation Pl The term “Alk” used in equation P-1 denotes an alkyl radical.

[0005] The chlorination of alkoxy(organo)silanes or -siloxanes to produce haloalkoxy(organo)silanes or -siloxanes is limited in the literature to the reaction using common chlorinating agents such as hydrogen chloride (Roberts et al., Ind. Eng. Chem. Res. 2016, 55, 1813-1818), acetyl chloride (Mirskov et al., Dokl. Chem., 2008, 421, 2, 194-196), trichloroisocyanuric acid (Varaprath et al., J. Organomet. Chem., 2007, 692, 1892-1897) and thionyl chloride in the presence of dimethylformamide (WO 2013 / 137904 Al; WO 2014 / 206876 Al). Equation P-2 The term “Alk” used in equation P-2 denotes an alkyl radical, the term “Me” denotes a methyl group.

[0006] A promising approach for the economical synthesis of haloalkoxy(organo)silanes and -siloxanes from tetraalkoxysilanes is the non-catalyzed or catalyzed ligand exchange with halogen-containing compounds.

[0007] Uncatalyzed ligand exchange, for example, between tetraalkoxysilanes and tetrahalosilanes, has been known since 1952 (Kumada et al.; J. Inst. Polytech. Osaka City Univ. Ser. C, 1952, 2, 139). Since then, attempts have been made to optimize the reaction parameters. Similarly, titanium tetrahalides have also been described as suitable (Kissin et al., J. Polym. Sci., Part A: Polym. Chem., 2010, 48, 4219-4229). Nevertheless, uncatalyzed ligand exchange remains economically unattractive due to its lower selectivity and high temperature and time requirements.

[0008] Catalyzed ligand exchange offers the possibility of overcoming these problems. In the literature, the reactions of tetraalkoxysilanes with tetrahalosilanes, benzyl chloride, and acetyl chloride in counter- Lewis acids such as aluminum chloride (Zdrakov et al., Russ. J. Appl. Chem., 2008, 81, 9, 1532-1537; WO 2017 / 136945), boron trichloride (Frazer et al., J. Chem. Soc., 1960, 4695-4712), and bismuth(III) chloride (Komata et al., Chem. Asian J., 2016, 11, 3225-3233) have been reported. The bismuth(III) chloride-catalyzed reaction of a tetraalkoxysilane with a tetrahalosilane to form the corresponding monohaloalkoxysilane (Komata et al., Chem. Asian J., 2016, 11, 3225-3233) is very selective.

[0009] However, to date, no synthetic routes based on Lewis base catalysts have been reported in the literature. Only the activating influence of Lewis bases on a variety of Si bonds is sufficiently known (Sturm et al., Chem. Eur. J., 2018, 24, 17796–17801). Furthermore, Lewis bases are known as potential promoters of alkoxy group transfer (US Pat. No. 4,762,939 A).

[0010] The object of the invention is to eliminate the disadvantages of the prior art. In particular, it is intended to provide a process that enables the preparation of haloalkoxy(organo)silanes and siloxanes and pseudohaloalkoxy(organo)silanes and siloxanes from alkoxy(organo)silanes. The haloalkoxy(organo)silanes and siloxanes and pseudohaloalkoxy(organo)silanes and siloxanes are to be obtained in as high yields and / or as short reaction times as possible.

[0011] This object is solved by the features of claim 1. Expedient embodiments of the inventions emerge from the features of the subclaims.

[0012] According to the invention, a process for preparing a compound of general formula I (Formula 1), provided, in which R 1 at each occurrence is selected from the group consisting of hydrogen, halogen, pseudohalogen and a group -OR 2 exists, whereby R 2 is selected at each occurrence from the group consisting of a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group, and a substituted or unsubstituted alkylaryl group; m is 0 or an integer from 1 to 10; and n is at each occurrence 0 or 1; with the proviso that at least one of the radicals R1 halogen or pseudohalogen and that at least one of the radicals R 1 a group -OR 2 wherein the process comprises reacting a compound of general formula II (Formula II), worm R 6 at each occurrence is selected from the group consisting of hydrogen, a group R 7 and a group -OR 7 exists, whereby R 7 at each occurrence is selected from the group consisting of a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group and a substituted or unsubstituted alkylaryl group; m and n have the meanings given in connection with the general formula I; with the proviso that at least one of the radicals R 6 a group -OR 7 with a compound of the general formula III wherein R 3 at each occurrence is selected from the group consisting of hydrogen, halogen, pseudohalogen and a radical R 4 consists; R 4 is selected at each occurrence from the group consisting of a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group, and a substituted or unsubstituted alkylaryl group; x is 0 or 1; and y is at each occurrence 0 or 1; with the proviso that at least one of the radicals R 3Halogen or pseudohalogen; in the presence of a catalyst, wherein the catalyst is an organophosphane. It can be provided that the compound of general formula I does not contain any pseudohalogen if it contains at least one halogen. It can be provided that the compound of general formula I does not contain any halogen if it contains at least one pseudohalogen.

[0013] In the compound of general formula I, the unit is by one unit of the general formula WA when n is 0, and by one unit of the formula WB when n is 1: Formula WA Formula WB A compound of the general formula I can contain at least one unit of the general formula WA as well as at least one unit of the general formula WB.

[0014] A compound of general formula I is a haloalkoxy(organo)silane or pseudohaloalkoxy(organo)silane if m is 0 or if m is an integer from 1 to 10 and n is 0 at each occurrence. A haloalkoxy(organo)silane or pseudohaloalkoxy(organo)silane has only units of general formula WA. A haloalkoxy(organo)silane or pseudohaloalkoxy(organo)silane is a compound of general formula IA: (Formula IA), where R 1 and m have the meanings given in connection with the general formula I. A compound of the general formula IA is a compound of the general formula I in which n is 0 at each occurrence. The compound of the general formula IA has at least one radical R 1 which is halogen or pseudohalogen, and at least one radical R 1 , which is a group -OR 2 is, on.

[0015] A compound of the general formula I is a halogenalkoxy(organo)siloxane or pseudohaloalkoxy(organo)siloxane if m is an integer from 1 to 10 and n is 1 at least once. In other words, this means that the compound of the general formula I contains at least one unit of the general Formula WB. However, it may additionally contain at least one unit of the general formula WA. An example of a haloalkoxy(organo)siloxane or pseudohalogenoalkoxy(organo)siloxane is a compound of the general formula IB: (Formula IB), where R 1 has the meanings given in connection with the general formula I and m is an integer from 1 to 10. A compound of the general formula IB is a compound of the general formula I in which m is an integer from 1 to 10 and n is 1 at each occurrence. The compound of the general formula IB has at least one radical R1 which is halogen or pseudohalogen, and at least one radical R 1 , which is a group -OR 2 A haloalkoxy(organo)silane or pseudohalogenalkoxy(organo)silane has only units of the general formula WA. The compound of the general formula IB has only units of the general formula WB.

[0016] Preferably, in the compound of general formula I R 1 at each occurrence is selected from the group consisting of hydrogen, halogen and a group -OR 2 exists, whereby R 2 at each occurrence is selected from the group consisting of a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group and a substituted or unsubstituted alkylaryl group, where R 2preferably at each occurrence is a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 6 carbon atoms, and particularly preferably at each occurrence is an unsubstituted, branched or unbranched alkyl group having 1 to 6 carbon atoms; m is 0 or an integer from 1 to 10; and n is 0 or 1 at each occurrence; with the proviso that at least one of the radicals R 1 halogen and that at least one of the radicals R 1 a group -OR 2 is.

[0017] The catalyst is a Lewis base. It enables ligand exchange between the compound of general formula II and the compound of general formula III, thereby yielding the compound of general formula I. The process according to the invention is based on a Lewis base-catalyzed ligand exchange.

[0018] According to the invention, the catalyst is an organophosphane. The catalyst can be a compound P(R 5 )3, where R 5 at each occurrence is selected from the group consisting of halogen, a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted alkylaryl group. Preferably, the catalyst is selected from the group consisting of triphenylphosphane, tri(ω-tolyl)phosphane, tri(o-tolyl)phosphane, tricyclohexylphosphane, tri(ω-butyl)phosphane, and trichlorophosphane. A particularly preferred catalyst is triphenylphosphane.

[0019] Compared to the prior art, the catalyst provided according to the invention shortens the required reaction time for the reaction of a compound of general formula II with a compound of general formula III to form a compound of general formula I. The reaction time required for the process according to the invention is preferably in a range from 0.5 to 2.5 hours, more preferably from 0.75 to 2.25 hours, and particularly preferably from 1 to 2 hours. However, it may also be advantageous to provide a longer reaction time in order to achieve higher yields. Reactions requiring a longer reaction time could not be realized with the catalysts known from the prior art, or only with extremely poor yields. The reaction time can therefore, in one embodiment of the process according to the invention, be in a range from 0.5 hours to 14 days, with 2 to 12 days being preferred, 4 to 10 days being more preferred, and 7 days being particularly preferred. The concentration of the catalyst is preferably in a range from 0.01 to 1 mol%, more preferably from 0.05 to 0.5 mol%, even more preferably from 0.075 to 0.25 mol% and particularly preferably 0.1 mol%, in each case based on the sum of the molar amount of the compound of the general formula II and the molar amount of the compound of the general formula III.

[0020] Scheme 1 illustrates the process according to the invention for preparing a compound of general formula I. (Scheme 1) According to the invention, the compound of general formula I has at least one radical R 1 which is halogen or pseudohalogen, and at least one radical R 1 on, the -OR 2 According to the invention, the compound of general formula II has at least one radical R 6 on, the -OR 7 is.

[0021] It can be provided that all residues R 1in the compound of general formula I are each independently selected from the group consisting of hydrogen, halogen, pseudohalogen and a group -OR 2 where R 2 is a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 12 carbon atoms. It may be provided that all radicals R 1 in the compound of general formula I are each independently selected from the group consisting of hydrogen, halogen and a group -OR 2 where R 2 is a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 12 carbon atoms. Preferably, R 2 a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 6 carbon atoms. It may be provided that in the compound of general formula I, m is 0 or 1.

[0022] According to the invention, the compound of general formula II (Formula II) residues R 6 which at each occurrence are each selected from the group consisting of hydrogen, a group R 7 and a group -OR 7 exists, whereby R 7 at each occurrence is selected from the group consisting of a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group and a substituted or unsubstituted alkylaryl group; m and n have the meanings given in connection with the general formula I; with the proviso that at least one of the radicals R 6 a group -OR 7 is.

[0023] The compound of general formula II corresponds to the compound of general formula I, except that at least one group R6 is replaced by a halogen or pseudohalogen.

[0024] In the compound of general formula I, the unit is by one unit of the general formula WA-2 when n is 0, and by one unit of the formula WB-2 when n is 1: Formula WA-2 Formula WB-2 A compound of general formula II may contain at least one unit of general formula WA-2 as well as at least one unit of general formula WB-2.

[0025] A compound of general formula II is an alkoxy(organo)silane if m is 0 or if m is an integer from 1 to 10 and n is 0 at each occurrence. An alkoxy(organo)silane has only units of general formula WA-2. An alkoxy(organo)silane is a compound of general formula II-A: (Formula II-A), where R 6and m have the meanings given in connection with the general formula II. A compound of the general formula II-A is a compound of the general formula II in which n is 0 at each occurrence. The compound of the general formula II-A has at least one radical R 6 , which is a group -OR 7 is, on.

[0026] A compound of general formula II is an alkoxy(organo)siloxane if m is an integer from 1 to 10 and n is 1 at least once. In other words, this means that the compound of general formula II has at least one unit of general formula WB-2. However, it may additionally have at least one unit of general formula WA-2. An example of an alkoxy(organo)siloxane is a compound of general formula II-B: where R 6has the meanings given in connection with the general formula II and m is an integer from 1 to 10. A compound of the general formula II-B is a compound of the general formula II in which m is an integer from 1 to 10 and n is 1 at each occurrence. The compound of the general formula II-B has at least one radical R 6 , which is a group -OR 7 An alkoxy(organo)silane has only units of the general formula WA-2. The compound of the general formula II-B has only units of the general formula WB-2.

[0027] Preferably, all residues R 6 Preferably, all radicals R 6 each one residue -OR 7 A preferred compound of general formula II is a compound of general formula II-C R i 7 O R 7 -O-Si-O-R 7 l O i R 7 (Formula II-C). The compound of general formula II-C is a compound of general formula II in which all radicals R 6 -OR 7 are.

[0028] Scheme 3 illustrates the process of the invention for preparing a compound of general formula IC using a compound of general formula II-C. ll-C III lC (Scheme 3) According to the invention, the compound of general formula IC has at least one radical R 1 which is halogen or pseudohalogen, and at least one radical R 1 on, the -OR 2 is.

[0029] It can be provided that all residues R 7 in the compound of general formula II or the compound of general formula II-C are each independently a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 12 carbon atoms. Preferably, all radicals R 7in the compound of general formula II or the compound of general formula II-C, independently of one another, each represents a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 6 carbon atoms.

[0030] The compound of general formula II is thus preferably a tetraalkoxysilane. Preferably, the compound of general formula II is selected from the group consisting of tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) and tetra-w-propoxysilane (T n POS).

[0031] One or more of the residues R 6 are replaced by a halogen or pseudohalogen derived from the compound of general formula III by catalytic ligand exchange. The other radicals R 6 remain unchanged during the ligand exchange. In the compound of general formula I, the radicals R 1which are not halogen or pseudohalogen, the residues R which remained unchanged during the catalytic ligand exchange 6 .

[0032] According to the invention, the compound of general formula III (Formula III) residues R 3 which at each occurrence are each selected from the group consisting of hydrogen, halogen, pseudohalogen and a radical R 4 exists, whereby R 4 is selected at each occurrence from the group consisting of a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group, and a substituted or unsubstituted alkylaryl group; x is 0 or 1; and y is at each occurrence 0 or 1; with the proviso that at least one of the radicals R 3Halogen or pseudohalogen. The compound of general formula III may be provided with no pseudohalogen if it contains at least one halogen. The compound of general formula III may be provided with no halogen if it contains at least one pseudohalogen.

[0033] The compound of general formula III necessarily contains a halogen atom or a pseudohalogen group. If the compound of general formula III contains a halogen atom, it is a halosilane or halosiloxane. If the compound of general formula III contains, in addition to a halogen atom, a radical R 4 it is a halogen(organo)silane or a halogen(organo)siloxane. If the compound of general formula III has a pseudohalogen group, it is a pseudohalogensilane or pseudohalogensiloxane. If the compound of general formula III has, in addition to a pseudohalogen group, a radical R 4it is a pseudohalogen(organo)silane or a pseudohalogen(organo)siloxane. A compound of general formula III may be a compound of general formula III-A or a compound of general formula III-B Formula III-A Formula III-B. In the compound of general formula III-A, R 3 the meanings given in connection with the general formula III, x is 0 or 1. The compound of the general formula III-A is a compound of the general formula III in which y is 0 at each occurrence. In the compound of the general formula III-B, R 3 the meanings given in connection with the general formula III, x is 1. The compound of the general formula III-B is a compound of the general formula III in which y is 1 at each occurrence.

[0034] It can be provided that all residues R 3are independently selected from the group consisting of hydrogen, halogen and pseudohalogen, with the proviso that at least one of the radicals R 3 halogen or pseudohalogen. It can be provided that all radicals R 3 are independently hydrogen or halogen, with the proviso that at least one of the radicals R 3 Halogen. Preferably, the halogen is chlorine. It can be provided that at least one of the radicals R 3 in the compound of the general formula III R 4 Preferably R 4 independently of one another, each represents a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 12 carbon atoms. More preferably, R 4 independently of one another, each represents a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 6 carbon atoms. R is particularly preferably 4 Methyl.

[0035] The compound of general formula III is preferably selected from the group consisting of dichlorosilane (HiSiCh), trichlorosilane (HSiCh), tetrachlorosilane (SiCE), hexachlorodisiloxane (O(SiCh)2), methyltrichlorosilane (CHsSiCh), methyl- dichlorosilane (HSiCHaCh) and dimethyldichlorosilane (CSiCh). Tetrachlorosilane is particularly preferred. Tetrachlorosilane is produced in very large quantities and with high purity as a byproduct of the Siemens process for producing high-purity silicon.

[0036] The present invention provides a cost-effective synthesis route in which, by means of a combination of organophosphanes and halogen-containing silane and siloxane compounds, i.e. compounds of the general formula III, industrially relevant haloalkoxy(organo)silanes and -siloxanes can be obtained in high yields from compounds of the general formula II, in particular tetraalkoxysilanes. In particular, it has been shown that tetraalkoxysilanes can be reacted with halo(organo)silanes or -siloxanes in the presence of 0.1 mol% (based on the amount of reactants) of phosphane compounds to form the corresponding haloalkoxy(organo)silanes or -siloxanes. In most cases, a reaction time of only 1 to 2 hours is necessary. In the same way, compounds of the general formula II, in particular tetraalkoxysilanes, can be reacted with pseudohalo(organo)silanes or-siloxanes in the presence of 0.1 mol% (based on the amount of reactants) of phosphine compounds can be reproducibly converted into the corresponding pseudohaloalkoxy(organo)silanes or -siloxanes. In most cases, a reaction time of only 1 to 2 hours is required. Longer reaction times may be required for reactions that were not feasible using state-of-the-art catalysts or only led to extremely poor conversions.

[0037] The process according to the invention can be carried out at ambient pressure and / or ambient temperature. For example, the process according to the invention can be carried out at room temperature. Room temperature can be understood as a temperature in a range from 10 to 30°C. The process according to the invention is preferably carried out under a protective gas. A preferred protective gas is argon.

[0038] A solvent is not required. The process according to the invention can therefore be a solvent-free process. However, it can be provided that the compound of the general formula III is provided in an aprotic organic solvent. The aprotic organic solvent can be, for example, toluene. The maximum concentration of the compound of the general formula III in the solvent can correspond to the saturation limit, but the concentration is preferably below this limit. In one embodiment, the compound of the general formula III can be present in the solvent in a concentration ranging from 1% by weight, based on the total weight of the solution, up to the saturation concentration. The compound of the general formula III can be present in the solvent, for example, in a concentration ranging from 1% by weight to 50% by weight, based in each case on the total weight of the solution.

[0039] The compound of general formula II and the compound of general formula III can, in one embodiment, be provided in a molar ratio of 4:1 to 1:4, more preferably of 3:1 to 1:3, even more preferably of 3:2 to 2:3 and particularly preferably of 2:1 to 1:2. The number of radicals R 7 which are replaced by halogen groups or pseudohalogen groups. Thus, the molar ratio can be selected depending on the desired target product. In one embodiment, the compound of formula II and the compound of formula III are provided in a stoichiometric ratio.

[0040] In the compound of general formula I, the halogen is selected at each occurrence from the group consisting of bromine, chlorine, fluorine, and iodine. In the compound of general formula III, the halogen is selected at each occurrence from the group consisting of bromine, chlorine, fluorine, and iodine.

[0041] In the compound of general formula I, the pseudohalogen at each occurrence is selected from the group consisting of -CN, -N3, -OCN, -NCO and -CNO. In the compound of general formula III, the pseudohalogen is at each occurrence selected from the group consisting of -CN, -N3, -OCN, -NCO and -CNO.

[0042] The term "alkyl," unless otherwise stated, refers in particular to a saturated aliphatic hydrocarbon group having a branched or unbranched carbon chain of 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. The alkyl group may optionally be substituted with one or more substituents, each substituent independently being alkyl, alkoxy, halogen, haloalkyl, cyano, nitro, or dialkylamino, unless specifically stated otherwise.

[0043] The term "aryl," unless otherwise stated, refers in particular to a monovalent cyclic aromatic hydrocarbon group which may comprise a mono-, bi-, or tricyclic aromatic ring. Examples of aryl groups are optionally substituted phenyl, naphthyl, phenanthryl, fluorenyl, indenyl, azulenyl, oxydiphenyl, biphenyl, methylenediphenyl, aminodiphenyl, diphenyl sulfidyl, diphenylsulfonyl, diphenylisopropylidenyl, benzodioxanyl, benzodioxylyl, benzoxazinyl, benzoxazinonyl, benzopiperadinyl, benzopiperazinyl, benzopyrrolidinyl, benzomorpholinyl, methylenedioxyphenyl, ethylenedioxyphenyl, and the like, although this list is not exhaustive. Preferably, aryl includes optionally substituted phenyl and optionally substituted naphthyl, with phenyl being particularly preferred.The aryl group may optionally be substituted with one or more substituents, each substituent independently being alkyl, alkoxy, halogen, haloalkyl, cyano, nitro or dialkylamino, unless specifically stated otherwise.

[0044] The term "alkylaryl" refers, unless otherwise stated, in particular to a monovalent aryl group bearing one or more alkyl groups, where the aryl group and the alkyl group are as defined above. Preferably, the aryl group is a phenyl group, where the alkyl group can be, for example, methyl, ethyl, n-propyl, n-propyl, n-butyl, n-isobutyl, n-butyl, or n-butyl. Preferably, the aryl group bears only one alkyl group. The alkylaryl group may optionally be substituted with one or more substituents, each substituent independently being alkyl, alkoxy, halogen, haloalkyl, cyano, nitro or dialkylamino, unless specifically stated otherwise.

[0045] The term "cycloalkyl," unless otherwise specified, refers specifically to saturated carbocyclic groups consisting of mono- or bicyclic rings. The cycloalkyl group may optionally be substituted with one or more substituents, each substituent independently being alkyl, alkoxy, halogen, haloalkyl, cyano, nitro, or dialkylamino, unless specifically stated otherwise. Examples of cycloalkyl moieties include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like, including partially unsaturated derivatives thereof, such as cyclohexenyl, cyclopentenyl, and the like.

[0046] The term “halogen” refers, unless otherwise stated, to chlorine, bromine or iodine.

[0047] The term “pseudohalogen” refers, unless otherwise stated, to -CN (cyanide), -N3 (nitrile), -OCN (cyanate), -NCO (isocyanate), -CNO (fulminate), -SCN (thiocyanate), -NCS (isothiocyanate) and -NR X -CN (cyanamide), where R x hydrogen or alkyl. Preferably, the pseudohalogen group is selected from the group consisting of -CN, -N3, and -NCO.

[0048] The invention is explained in more detail below using exemplary embodiments which are not intended to limit the invention.

[0049] The catalyst provided according to the invention can be a liquid compound or a solid compound at ambient temperature, in particular at room temperature. For example, triphenylphosphane is solid at room temperature. In contrast, tri(w-butyl)phosphane and trichlorophosphane are liquid at room temperature. In the case of a solid catalyst, the process according to the invention was carried out according to the first general synthesis route. In the case of a liquid catalyst, The process according to the invention was carried out according to the second general synthesis route. All reactions were carried out under an argon atmosphere using the SCHLENK technique. First general synthesis route

[0050] The process according to the invention was carried out in 50 ml Schlenk flasks. The calculated amount of solid catalyst was placed in the flask. The calculated amount of the compound of general formula II was added to the catalyst and stirred. Subsequently, the compound of general formula III was added in the specified molar ratio. The reaction mixture thus obtained was stirred at room temperature for the specified time. The stirring speed was 700 revolutions per minute (rpm). Second general synthesis route

[0051] The process according to the invention was carried out in 50 ml Schlenk flasks. The calculated amount of the compound of general formula II was initially charged into the flask. The compound of general formula III was then added in the specified molar ratio. The catalyst was then added. The reaction mixture thus obtained was stirred at room temperature for the specified time. The stirring speed was 700 rpm. Reagents used

[0052] The following reagents were used in the examples: Tetram ethoxy silane (TMOS): but; 98%; CAS 681-84-5 Tetraethoxy silane (TEOS): but; 99.9%; CAS 78-10-4 Tetra-w-propoxy silane (T"POS): TCI; 98%; CAS 682-01-9 Dichlorosilane: Linde; 3.0 g; CAS 4109-96-0; 25 wt% in toluene Trichlorosilane: Acros Organics; 99%; CAS 10025-78-2 Tetrachlorosilane: Acros Organics; 99%; CAS 10026-04-7 Hexachlorodisilane: Sigma-Aldrich; 96%; CAS 13465-77-5 Hexachl ordi sil oxan : but; 96%; CAS 14986-21-1 Methy Itri chl or sil an : Sigma-Aldrich; 99%; CAS 75-79-6 Methyldichlorosilane: Sigma-Aldrich; 97%; CAS 75-54-7 Dimethyldichlorosilane: Sigma-Aldrich; 99.5%; CAS 75-78-5 Tetrafluorosilane: in-situ synthesis from Na2[SiF6] (Sigma-Aldrich; CAS 16893-85-9) and 96% H2SO4 Tetrabromosilane: Sigma-Aldrich; 99%; CAS 7789-66-4 Tetraiodosilane: but; 99%; CAS 13465-84-4 Trimethylsilyl cyanide: but; 98%; CAS 7677-24-9 Trimethylsilyl isocyanate: but; 95%; CAS 1118-02-1 Trimethylsilyl azide: but; 95%; CAS 4648-54-8 Triphenylphosphine: but; 99%; CAS 603-35-0 T ri ( / ?-tolyl)phosphane: TCI; 96%; CAS 1038-95-5 Tri(o-tolyl)phosphane: TCI; 97%; CAS 6163-58-2 Tricyclohexylphosphane: but; 98%; CAS 2622-14-2 Tri(w-butyl)phosphane: Sigma-Aldrich; 93.5%; CAS 998-40-3 Trichl orphosphine: Sigma-Aldrich; 99%; CAS 7719-12-2 Bismuth(III) chloride: Sigma-Aldrich; 98%; CAS 7787-60-2 Triphenylamine: Sigma-Aldrich; 98%; CAS 603-34-9 Triethylamine: Sigma-Aldrich; 99%; CAS 121-44-8 Pyridine: Sigma-Aldrich; 99%; CAS 110-86-1 Measurement method The percentages of the target compounds given in Tables 1 to 8 were calculated using 29 Si NMR spectra. The amounts in “mol%” refer to the sum of all integrals, which reflect the molar amounts of the silicon species in the 29 Si NMR spectra. The molar percentages were determined from the integral area relative to the internal standard HMDSO. Examples 1 to 14

[0053] Examples 1 to 14 illustrate the reaction of tetraethoxysilane (TEOS) with a compound of general formula III using triphenylphosphine (PPU) as a catalyst. The reaction was carried out according to the first general synthesis route. Tetraethoxysilane (TEOS) is a compound of general formula II in which all four R radicals 2 ethyl. Example 1

[0054] Scheme Bl illustrates the reaction of tetraethoxysilane 1 with SiCh 2 in the presence of triphenylphosphine. PPh Si(OCH2CH3)4+ SiCI4 3 >> CISi(OCH2CH3)3+ CI2Si(OCH2CH3)2+ CI3Si(OCH2CH3) 1 2 3A 3B 3C (Scheme Bl) SiCE 2 is a compound of the general formula III, in which all radicals R 3 Chlorine and x is 0. Compounds 3A, 3B and 3C are compounds of the general formula I, wherein m is 0. In compound 3A, a radical R 1 Chlorine and the other residues R 1are each -OR 2 with R 2 is ethyl. In compound 3B, two radicals R 1 each chlorine and the other residues R 1 are each -OR 2 with R 2 is ethyl. In compound 3C, three radicals R 1 each chlorine and the remaining residue R 1 is -OR 2 with R 2 equals ethyl.

[0055] A stoichiometrically complete reaction of tetraethoxy silane 1 with SiCU 2 to compound 3A is shown in Scheme B2. (Scheme B2)

[0056] Using the first general synthesis route, tetraethoxysilane 1 was reacted with SiCh 2 in a molar ratio of 3 : 1. The reaction was carried out in the presence of triphenylphosphane. 0.1 mol% of triphenyl- phosphine, based on the sum of the molar amount of compound 1 and the molar amount of compound 2. The reaction time was 168 h.

[0057] Table 1 shows the percentage molar fractions of the target compounds 3A, 3B and 3C and the starting compounds 1 and 2 in the mixture obtained in the reaction. Example 2

[0058] Tetraethoxysilane 1 was reacted with SiCl 2 as described in Example 1, except that the reaction time was 2 h. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the resulting mixture are shown in Table 1. Example 3

[0059] Tetraethoxysilane 1 was reacted with SiCU 2 as described in Example 1, except that the reaction time was 1 h. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the reaction mixture are shown in Table 1. Example 4

[0060] Tetraethoxysilane 1 was reacted with SiCU 2 as described in Example 1, except that the reaction time was 1 h and the molar ratio of tetraethoxysilane to SiCU 2 was 1. The molar percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the mixture obtained in the reaction are shown in Table 1. Example 5

[0061] Tetraethoxysilane 1 was reacted with SiCU 2 as described in Example 1, except that the reaction time was 1 h and the molar ratio of tetraethoxysilane to SiCU was 1:1. The molar percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the mixture obtained in the reaction are shown in Table 1. Example 6

[0062] Tetraethoxysilane 1 was reacted with SiCU 2 as described in Example 1, except that the reaction time was 1 h and the molar ratio of tetraethoxysilane to SiCU was 1:2. The molar percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the mixture obtained in the reaction are shown in Table 1. Example 7

[0063] Tetraethoxysilane 1 was reacted with SiCU 2 as described in Example 1, except that the reaction time was 1 h and the molar ratio of tetraethoxysilane to SiCU was 1:3. The molar percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the mixture obtained in the reaction are shown in Table 1. Example 8

[0064] Scheme B8 illustrates the reaction of tetraethoxysilane 1 with HSiCh 4 in the presence of triphenylphosphine. (Scheme B8) HSiCh 4 is a compound of the general formula III, in which three radicals R 3 Chlorine and the remaining residue R 3 H and x is 0. HSiCh is a hydridohalosilane.

[0065] Using the first general synthesis route, tetraethoxysilane 1 was reacted with HSiCh 4 in a molar ratio of 3:1. The reaction was carried out in the presence of triphenylphosphine. 0.1 mol% of triphenylphosphine was used, based on the sum of the molar amounts of compound 1 and the molar amounts of compound 4. The reaction time was 168 h.

[0066] Table 1 shows the mole percentages of the target compounds 3A, 3B, and 3C and the starting compound 1 in the mixture obtained during the reaction. Additionally, the mixture contained 10 mol% HSiCl(OCH2CH3)2 and 5 mol% HSi(OCH2CH3)3. Example 9

[0067] Tetraethoxysilane 1 was reacted with HSiCh 4 as described in Example 8, except that the reaction time was 1 h. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compound 1 in the resulting mixture are shown in Table 1. In addition, the mixture contained 16 mol% HSiCl(OCH2CH3)2 and 7 mol% HSi(OCH2CH3)3. Example 10

[0068] Scheme B10 illustrates the reaction of tetraethoxy silane 1 with FbSiCh 5 in the presence of triphenylphosphine. PPh Si(OCH2CH3)4+ H2SiCI2 3 >> CISi(OCH2CH3)3+ CI2Si(OCH2CH3)2+ CI3Si(OCH2CH3) 1 5 3A 3B 3C (Scheme B10) FbSiCh 5 is a compound of the general formula III, in which two radicals R 3 Chlorine and the remaining residues R 3 H and x is 0. FbSiCh 5 is a hydridohalosilane.

[0069] Using the first general synthesis route, tetraethoxysilane 1 was reacted with H2SiCh 5 (25 wt. % solution in toluene) in a molar ratio of 2:1. The reaction was carried out in the presence of triphenylphosphine. 0.1 mol% of triphenylphosphine was used, based on the sum of the molar amounts of compound 1 and the molar amounts of compound 5. The reaction time was 168 h.

[0070] Table 1 shows the mole fractions of the target compounds 3A, 3B, and 3C and the starting compound 1 in the mixture obtained during the reaction. The mixture also contained 22 mol% FbSiCh. Example 11

[0071] Tetraethoxysilane 1 was reacted with FbSiCh 5 as described in Example 10, except that the reaction time was 1 h. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compound 1 in the resulting mixture are shown in Table 1. Additionally, the mixture contained 35 mol% of HiSiCh and 5 mol% of (Tol)SiH2Cl, where "Toi" denotes a benzyl group (-CH2-C5H6). Example 12

[0072] Scheme B12 illustrates the reaction of tetraethoxysilane 1 with ChSi-SiCh (also referred to as Si2CU) 6 in the presence of triphenylphosphine. PPh Si(OCH2CH3)4+ CI3Si-SiCI3 3 »> CISi(OCH2CH3)3+ CI2Si(OCH2CH3)2+ CI3Si(OCH2CH3) 1 6 3A 3B 3C (Scheme Bl 2) Si2Cl66 is a compound of general formula III, in which all radicals R 3 Chlorine, x is 1 and y is 0.

[0073] Using the first general synthesis route, tetraethoxysilane 1 was reacted with Si2Ch6 in a molar ratio of 3:2. The reaction was carried out in the presence of triphenylphosphane. 0.1 mol% of triphenylphosphane was used, based on the sum of the molar amounts of compound 1 and the molar amounts of compound 6. The reaction time was 168 h.

[0074] Table 1 shows the percentage amounts of the target compounds 3A, 3B and 3C and the starting compound 1 in the product obtained during the reaction obtained mixture. In addition, the mixture contained 69 mol% Si2Cl6, 6 mol% SiCl4, and 2 mol% O(Si(OCH2CH3)3)2. Example 13

[0075] Scheme B13 illustrates the reaction of tetraethoxysilane 1 with Cl3Si-O-SiCl3 (also referred to as O(SiCl3)2) 7 in the presence of triphenylphosphine. (Scheme Bl 3) Cl3Si-O-SiCl37 is a compound of general formula III, in which all radicals R 3 Chlorine, x is 1 and y is 0.

[0076] Using the first general synthesis route, tetraethoxysilane 1 was reacted with compound 7 in a molar ratio of 3:2. The reaction was carried out in the presence of triphenylphosphane. 0.1 mol% of triphenylphosphane was used, based on the sum of the molar amounts of compound 1 and the molar amounts of compound 7. The reaction time was 168 h.

[0077] Table 1 shows the mole fractions of the target compounds 3A, 3B, and 3C and the starting compound 1 in the mixture obtained during the reaction. The mixture also contained 34 mol% of mixed siloxanes. Example 14

[0078] Tetraethoxysilane 1 was reacted with Cl3Si-O-SiCl37 as described in Example 13, except that the reaction time was 1 h. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compound 1 in the resulting mixture are shown in Table 1. Additionally, the mixture contained 31 mol% of mixed siloxanes. Table 1 Examples 15 and 16

[0079] Examples 15 and 16 illustrate the reaction of tetramethoxysilane (TMOS) 8 with a compound of general formula III using triphenylphosphine (PPI13) as a catalyst. The reaction was carried out according to the first general synthesis route. Tetramethoxysilane (TMOS) is a compound of general formula II in which all four R radicals 2 Methyl. Example 15

[0080] Scheme B15 illustrates the reaction of tetramethoxysilane 8 with SiCU 2 in the presence of triphenylphosphine. PPh Si(OCH3)4+ SiCI4 3 »> CISi(OCH3)3+ CI2SiH(OCH3)2+CI3Si(OCH3) 8 2 9A 9B 9C (Scheme Bl 5) Compounds 9A, 9B and 9C are compounds of the general formula I, wherein m is 0. In compound 9A, a radical R 1 Chlorine and the other residues R 1 are each -0-R 2 with R 2 is methyl. In compound 9B, two radicals R 1 each chlorine and the other residues R 1 are each -OR 2 with R 2 is methyl. In compound 9C, three radicals R 1 each chlorine and the remaining residue R 1 is -OR 2 with R 2 equals methyl.

[0081] Using the first general synthesis route, tetramethoxysilane 9 was reacted with SiCU 2 in a molar ratio of 3:1. The reaction was carried out in the presence of triphenylphosphine. 0.1 mol% of triphenylphosphine was used, based on the sum of the molar amounts of compound 8 and the molar amounts of compound 2. The reaction time was 168 h.

[0082] Table 2 shows the percentage molar fractions of the target compounds 9A, 9B and 9C and the starting compounds 8 and 2 in the mixture obtained in the reaction. Example 16

[0083] Tetramethoxysilane 8 was reacted with SiCl 2 as described in Example 15, except that the reaction time was 1 h. The mole percentages of the target compounds 9A, 9B, and 9C and the starting compounds 8 and 2 in the reaction mixture are shown in Table 2. Table 2 Examples 17 and 18

[0084] Examples 17 and 18 illustrate the conversion of tetra-w-propoxysilane (T n POS) with a compound of general formula III using triphenylphosphine (PPI13) as catalyst. The reaction was carried out according to first general synthesis route. Tetra-«-propoxysilane (T n POS) is a compound of the general formula II, in which all four radicals R 2 «-propyl. Example 17

[0085] Scheme B17 illustrates the reaction of tetra-«-propoxysilane 10 with SiCU 2 in the presence of triphenylphosphine. PPh Si(OCH2CH2CH3)4+ SiCI4 3 >> CISi(OCH2CH2CH3)3+ CI2Si(OCH2CH2CH3)2+CI3Si(OCH2CH2CH3) 10 2 11A 11 B 11C (Scheme Bl 7) Compounds 11A, 11B and 11C are compounds of general formula I, wherein m is 0. In compound 11A, a radical R 1 Chlorine and the other residues R1 are each -OR 2 with R 2 equals «-propyl. In compound 11B, two radicals R 1 each chlorine and the other residues R 1 are each -OR 2 with R 2 equals «-propyl. In compound 11C, three radicals R 1 each chlorine and the remaining residue R 1 is -OR 2 with R 2 equals «-propyl.

[0086] Using the first general synthesis route, tetra-«-propoxysilane 10 was reacted with SiCl 2 in a molar ratio of 3:1. The reaction was carried out in the presence of triphenylphosphine. 0.1 mol% of triphenylphosphine was used, based on the sum of the molar amounts of compound 10 and the molar amounts of compound 2. The reaction time was 168 h.

[0087] Table 3 shows the molar fractions of the target compounds 11A, 11B and 11C and the starting compounds 10 and 2 in the mixture obtained in the reaction. Example 18

[0088] Tetra-«-propoxysilane 10 was reacted with SiCh 2 as described in Example 17, except that the reaction time was 1 h. The mole percentages of the target compounds 11A, 11B, and 11C and the starting compounds 10 and 2 in the reaction mixture are shown in Table 3. Table 3 Examples 19 to 28

[0089] Examples 19 to 28 illustrate the reaction of tetraethoxysilane (TEOS) with SiCU 2 using other organophosphanes as catalyst. Example 19

[0090] Scheme B 19 illustrates the reaction of tetraethoxysilane 1 with SiCU 2 in the presence of triphenylphosphine. plt Si(OCH2CH3)4+ SiCI4>» CISi(OCH2CH3)3+ CI2Si(OCH2CH3)2+ Cl3Si(OCH2CH3) 1 2 3A 3B 3C (Scheme Bl 9) The term “Cat.” in Scheme B 19 refers to an organophosphane catalyst.

[0091] Using the first general synthesis route, tetraethoxysilane 1 was reacted with SiCU 2 in a molar ratio of 3:1. The reaction was carried out in the presence of tri( / ?-tolyl)phosphane. 0.1 mol% of tri( / ?-tolyl)phosphane was used, based on the sum of the molar amounts of compound 1 and the molar amounts of compound 2. The reaction time was 168 h.

[0092] Table 4 shows the percentage molar fractions of the target compounds 3A, 3B and 3C and the starting compounds 1 and 2 in the mixture obtained in the reaction. Example 20

[0093] Tetraethoxysilane 1 was reacted with SiCl 2 as described in Example 19, except that the reaction time was 1 h. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the reaction mixture are shown in Table 4. Example 21

[0094] Tetraethoxysilane 1 was reacted with SiCl 2 as described in Example 19, except that tri(o-tolyl)phosphine was used instead of tri( / ?-tolyl)phosphine. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the reaction mixture are shown in Table 4. Example 22

[0095] Tetraethoxysilane 1 was reacted with SiCl 2 as described in Example 19, except that tri(o-tolyl)phosphine was used instead of tri(I-tolyl)phosphine and the reaction time was 1 h. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the resulting mixture are shown in Table 4. Example 23

[0096] Tetraethoxysilane 1 was reacted with SiCl 2 as described in Example 19, except that tri(cyclohexyl)phosphane was used instead of tri( / ?-tolyl)phosphane. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the reaction mixture are shown in Table 4. Example 24

[0097] Tetraethoxy silane 1 was reacted with SiCU 2 as described in Example 19, except that tri(cyclohexyl)phosphane was used instead of tri( / ?-tolyl)phosphane and the reaction time was 1 h. The mole fractions of the Target compounds 3A, 3B and 3C and the starting compounds 1 and 2 on the mixture obtained in the reaction are shown in Table 4. Example 25

[0098] Tetraethoxysilane 1 was reacted with SiCl 2 as described in Example 19, except that the second general synthesis route was used instead of the first general synthesis route, and tri(ω-butyl)phosphine was used instead of tri(ω-tolyl)phosphine. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the reaction mixture are shown in Table 4. Example 26

[0099] Tetraethoxysilane 1 was reacted with SiCl 2 as described in Example 19, except that the second general synthesis route was used instead of the first general synthesis route, tri(ω-butyl)phosphine was used instead of tri(ω-tolyl)phosphine, and the reaction time was 1 h. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the reaction mixture are shown in Table 4. Example 27

[0100] Tetraethoxysilane 1 was reacted with SiCl 2 as described in Example 19, except that the second general synthesis route was used instead of the first general synthesis route and trichlorophosphane was used instead of tri( / ?-tolyl)phosphane. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the mixture obtained in the reaction are shown in Table 4. Example 28

[0101] Tetraethoxysilane 1 was reacted with SiCU 2 as described in Example 19, except that the second general synthesis route was used instead of the first general synthesis route, trichlorophosphane was used instead of tri( / ?-tolyl)phosphane, and the reaction time was 1 h. The percentage molar fractions of the target compounds 3A, 3B and 3C and the starting compounds 1 and 2 on the mixture obtained in the reaction are shown in Table 4. Table 4 Examples 29 to 34

[0102] Examples 29 to 34 illustrate the reaction of tetraethoxysilane (TEOS) with a halo(organo)silane using triphenylphosphine as catalyst. Example 29

[0103] Scheme B29 illustrates the reaction of tetraethoxysilane 1 with methyltrichlorosilane 12 in the presence of triphenylphosphine. PPh Si(OCH2CH3)4+ CH3SiCI3 3>> CISi(OCH2CH3)3+ CI2Si(OCH2CH3)2+ CI3Si(OCH2CH3) 1 12 3A 3B 3C (Scheme B29) Methyltrichlorosilane 12 is a compound of the general formula III, in which three radicals R 3 Chlorine, the remaining residue R 3 is methyl and x is 0.

[0104] Using the first general synthesis route, tetraethoxysilane 1 was reacted with compound 12 in a molar ratio of 3:4. The reaction was carried out in the presence of triphenylphosphane. 0.1 mol% of triphenylphosphane was used, based on the sum of the molar amounts of compound 1 and the molar amounts of compound 12. The reaction time was 168 h.

[0105] Table 5 shows the mole fractions of the target compounds 3A, 3B, and 3C and the starting compound 1 in the mixture obtained during the reaction. Additionally, 51 mol% of CFFSiCl(OCIUCI), 9 mol% of CH3SiCl(OCH2CH3)2, and 2 mol% of CH3SiCl3 were obtained. Example 30

[0106] Tetraethoxysilane 1 was reacted with methyltrichlorosilane 12 as described in Example 29, except that the reaction time was 1 h. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compound 1 in the reaction mixture are shown in Table 5. In addition, 37 mol% of CH3SiCl2(OCH2CH3), 17 mol% of CH3SiCl3, and 5 mol% of CH3SiCl(OCH2CH3)2 were obtained. Example 31

[0107] Scheme B31 illustrates the reaction of tetraethoxysilane 1 with dimethyldichlorosilane 13 in the presence of triphenylphosphine. (Scheme B31) Dimethyldichlorosilane 13 is a compound of general formula III, in which two radicals R 3 Chlorine and the other two residues R 3 are methyl and x is 0.

[0108] Using the first general synthesis route, tetraethoxysilane 1 was reacted with compound 13 in a molar ratio of 1 : 2. The reaction was carried out in the presence of triphenylphosphane. 0.1 mol% Triphenylphosphane, based on the sum of the molar amounts of compound 1 and the molar amounts of compound 13, was used. The reaction time was 168 h.

[0109] Table 5 shows the mole fractions of the target compounds 3A, 3B, and 3C and the starting compound 1 in the mixture obtained during the reaction. Additionally, 40 mol% of (CHa^SiCh) and 35 mol% of (CH3)2SiCl(OCH2CH3) were obtained. Example 32

[0110] Tetraethoxysilane 1 was reacted with dimethyldichlorosilane 13 as described in Example 31, except that the reaction time was 1 h. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compound 1 in the reaction mixture are shown in Table 5. In addition, 52 mol% of (CHa^SiCh) and 24 mol% of (CH3)2SiCl(OCH2CHa) were obtained. Example 33

[0111] Scheme B33 illustrates the reaction of tetraethoxysilane 1 with methyldichlorosilane (HSiCHaCh) 14 in the presence of triphenylphosphine. PPh Si(OCH2CH3)4+ HSiCH3CI2 3 >> CISi(OCH2CH3)3+ CI2Si(OCH2CH3)2+ CI3SiH(OCH2CH3) 1 14 3A 3B 3C (Scheme B33) Methyldichlorosilane 14 is a compound of the general formula III, in which two radicals R 3 Chlorine, another residue R 3 Methyl and the remaining residue R 3 is hydrogen and x is 0.

[0112] Using the first general synthesis route, tetraethoxysilane 1 was reacted with compound 14 in a molar ratio of 1:2. The reaction was carried out in the presence of triphenylphosphine. 0.1 mol% of triphenylphosphine was used, based on the sum of the molar amounts of compound 1 and the molar amounts of compound 14. The reaction time was 168 h.

[0113] Table 5 shows the mole fractions of the target compounds 3A, 3B, and 3C and the starting compound 1 in the mixture obtained during the reaction. Additionally, 37 mol% of HSiCH3Cl(OCH2CH3) and 34 mol% of HSiCHaCh were obtained. Example 34

[0114] Tetraethoxysilane 1 was reacted with methyldichlorosilane 14 as described in Example 33, except that the reaction time was 1 h. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compound 1 in the reaction mixture are shown in Table 5. In addition, 43 mol% of HSiCH3Cl2 and 23 mol% of HSiCH3Cl(OCH2CH3) were obtained. Table 5 Comparative examples 35 to 46 For comparison purposes, tetraethoxysilane 1 was reacted with a compound of general formula III without the use of an organophosphane catalyst. Either no catalyst or no organophosphane catalyst was used. Comparison example 35

[0115] Tetraethoxysilane 1 was reacted with SiCl 2 as described in Example 1, except that no catalyst was used. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the resulting mixture are shown in Table 6. Comparison example 36

[0116] Tetraethoxysilane 1 was reacted with SiCh 2 as described in Example 1, except that BiCh was used instead of triphenylphosphine. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the reaction mixture are shown in Table 6. Comparison example 37

[0117] Tetraethoxysilane 1 was reacted with SiCh 2 as described in Example 1, except that BiCh was used instead of triphenylphosphine and the reaction time was 24 h. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the resulting mixture are shown in Table 6. Comparison example 38

[0118] Tetraethoxysilane 1 was reacted with SiCh 2 as described in Example 1, except that BiCh was used instead of triphenylphosphine and the reaction time was 1 h. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the resulting mixture are shown in Table 6. Comparison example 39

[0119] Tetraethoxysilane 1 was reacted with HSiCh 4 as described in Example 8, except that BiCh was used instead of triphenylphosphine and the reaction time was 120 h. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compound 1 in the reaction mixture are shown in Table 6. In addition, 4 mol% of HSi(OCH2CJh)3 was obtained. Comparison example 40

[0120] Tetraethoxy silane 1 was reacted with T SiCh 5 as described in Example 10, except that BiCh was used instead of triphenylphosphane, Tetraethoxy - silane 1 was reacted with T SiCh 5 (25 wt.% solution in toluene) in a molar ratio of 3:1 and the reaction time was 120 h. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compound 1 in the mixture obtained in the reaction are shown in Table 6. In addition, 17 mol% of (Tol)SiH2Cl and 7 mol% of (Tol)SiH(OCH2CH3)2 were obtained, where "Toi" denotes a benzyl group (-CH2-C5H6). Comparison example 41

[0121] Tetraethoxysilane 1 was reacted with SiCU 2 as described in Example 1, except that triphenylamine (NPI13) was used instead of triphenylphosphine. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the reaction mixture are shown in Table 6. Comparison example 42

[0122] Tetraethoxysilane 1 was reacted with SiCl 2 as described in Example 1, except that triphenylamine (NPI13) was used instead of triphenylphosphine and the reaction time was 1 h. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the resulting mixture are shown in Table 6. Comparison example 43

[0123] Tetraethoxysilane 1 was reacted with SiCl 2 as described in Example 1, except that pyridine was used instead of triphenylphosphine. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the resulting mixture are shown in Table 6. Comparison example 44

[0124] Tetraethoxysilane 1 was reacted with SiCl 2 as described in Example 1, except that pyridine was used instead of triphenylphosphine and the reaction time was 1 h. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the resulting mixture are shown in Table 6. Comparison example 45

[0125] Tetraethoxysilane 1 was reacted with SiCl 2 as described in Example 1, except that triethylamine was used instead of triphenylphosphine. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the mixture obtained in the reaction are shown in Table 6. Comparison example 46

[0126] Tetraethoxysilane 1 was reacted with SiCl 2 as described in Example 1, except that triethylamine was used instead of triphenylphosphine and the reaction time was 1 h. The mole percentages of the target compounds 3A, 3B, and 3C and the starting compounds 1 and 2 in the resulting mixture are shown in Table 6. Table 6 The term “VB” means “comparison example”. Examples 47 to 50

[0127] Examples 47 to 50 illustrate the reaction of tetraethoxysilane (TEOS) with other tetrahalosilanes of general formula III using triphenylphosphine (PPI13) as the catalyst. The reaction was carried out according to the first general synthesis route. Example 47

[0128] Scheme B47 illustrates the reaction of tetraethoxysilane 1 with SiF4 15 in the presence of triphenylphosphine. PPh Si(OCH2CH3)4+ Si F43 >» FSi(OCH2CH3)34- F2Si(OCH2CH3)2+ F3Si(OCH2CH3) 1 15 16A 16B 16C (Scheme B47) SiF4 15 is a compound of the general formula III, in which all radicals R 3 Fluorine and x is 0. Compounds 16A, 16B and 16C are compounds of general formula I, wherein m is 0. In compound 16A, a radical R 1 Fluorine and the other residues R 1 are each -OR 2 with R 2 is ethyl. In compound 16B, two radicals R 1 each fluorine and the other residues R 1 are each -OR 2 with R 2 is ethyl. In compound 16C, three radicals R 1 each fluorine and the remaining residue R 1 is -OR 2 with R 2 equals ethyl.

[0129] Using the first general synthesis route, tetraethoxysilane 1 was reacted with SiF4 15 in a molar ratio of 3:1. The reaction was carried out in the presence of triphenylphosphane. 0.1 mol% of triphenylphosphane was used, based on the sum of the molar amounts of compound 1 and the molar amounts of compound 15. The reaction time was 168 h.

[0130] Table 7 shows the mole percentages of the target compounds 16A, 16B, and 16C and the starting compounds 1 and 15 in the mixture obtained during the reaction. Additionally, 3 mol% of O(Si(OCH2CH3)3)2 was obtained. Example 48

[0131] Scheme B48 illustrates the reaction of tetraethoxysilane 1 with SiBn 17 in the presence of triphenylphosphine. PPh Si(OCH2CH3)4+ SiBr4 3 »> BrSi(OCH2CH3)3+ Br2Si(OCH2CH3)2+ Br3Si(OCH2CH3) 1 17 18A 18B 18C (Scheme B48) SiBn 17 is a compound of the general formula III, in which all radicals R 3 Bromine and x is 0. Compounds 18A, 18B and 18C are compounds of general formula I, wherein m is 0. In compound 18A, a radical R 1 Bromine and the other residues R 1 are each -OR 2 with R 2 is ethyl. In compound 18B, two radicals R 1 each bromine and the other residues R 1 are each -OR 2 with R 2 is ethyl. In compound 18C, three radicals R 1 each bromine and the remaining residue R 1 is -OR 2 with R 2 equals ethyl.

[0132] Using the first general synthesis route, tetraethoxysilane 1 was reacted with SiBr417 in a molar ratio of 3:1. The reaction was carried out in the presence of triphenylphosphine. 0.1 mol% of triphenylphosphine was used, based on the sum of the molar amounts of compound 1 and compound 17. The reaction time was 168 h.

[0133] Table 7 shows the percentage molar fractions of the target compounds 18A, 18B and 18C and the starting compounds 1 and 17 in the mixture obtained in the reaction. Example 49

[0134] Tetraethoxysilane 1 was reacted with SiBr417 as described in Example 48, except the reaction time was 1 h. The mole percentages of the target compounds 18A, 18B, and 18C and the starting compounds 1 and 17 in the reaction mixture are shown in Table 7. Example 50

[0135] Scheme B50 illustrates the reaction of tetraethoxysilane 1 with SiE 19 in the presence of triphenylphosphine. PPh Si(OCH2CH3)4+ Sil4 3 »> ISi(OCH2CH3)3+ l2Si(OCH2CH3)2+ l3Si(OCH2CH3) 1 19 20A 20B 20C (Scheme B50) SÜ4 19 is a compound of general formula III, in which all radicals R 3 iodine and x is 0. Compounds 20A, 20B and 20C are compounds of the general formula I, wherein m is 0. In compound 20A, a radical R 1 iodine and the other residues R 1 are each -OR 2 with R 2 is ethyl. In compound 20B, two radicals R 1 each iodide and the other residues R 1 are each -OR 2 with R 2 is ethyl. In compound 20C, three radicals R 1 each lod and the remaining residue R 1 is -OR 2 with R 2 equals ethyl.

[0136] Using the first general synthesis route, tetraethoxysilane 1 was reacted with SÜ4 19 in a molar ratio of 3:1. The reaction was carried out in the presence of triphenylphosphine. 0.1 mol% of triphenylphosphine was used, based on the sum of the molar amounts of compound 1 and the molar amounts of compound 19. The reaction time was 168 h.

[0137] Table 7 shows the mole fractions of the target compounds 20A, 20B, and 20C and the starting compounds 1 and 19 in the mixture obtained during the reaction. Additionally, 8 mol% of siloxanes were obtained. Table 7 Examples 51 to 53

[0138] Examples 51 to 53 illustrate the reaction of tetraethoxysilane (TEOS) with pseudohalosilanes of general formula III using triphenylphosphine (PPI13) as the catalyst. The reaction was carried out according to the first general synthesis route. Example 51

[0139] Scheme B51 illustrates the reaction of tetraethoxysilane 1 with trimethylsilyl cyanide ((CHa^SiCN) 21) in the presence of triphenylphosphine. PPh Si(OCH2CH3)4+ (CH3)3SiCN 3 >. (CN)Si(OCH2CH3)3+ (CN)2Si(OCH2CH3)2+ (CN)3Si(OCH2CH3) 1 21 22A 22B 22C (Scheme B51) (CHa^SiCN 21 is a compound of the general formula III, in which three radicals R 3 Methyl, the remaining residue R 3 -CN and x is 0. Compounds 22A, 22B and 22C are compounds of general formula I, wherein m is 0. In compound 22A, a radical R 1 -CN and the other residues R 1are each -OR 2 with R 2 is ethyl. In compound 22B, two radicals R 1 each -CN and the other residues R 1 are each -OR 2 with R 2 is ethyl. In compound 22C, three radicals R 1 each -CN and the remaining residue R 1 is -OR 2 with R 2 equals ethyl.

[0140] Using the first general synthesis route, tetraethoxysilane 1 was reacted with (CHa^SiCN 21) in a molar ratio of 1:2. The reaction was carried out in the presence of triphenylphosphane. 0.1 mol% of triphenylphosphane was used, based on the sum of the molar amount of compound 1 and the molar amount of compound 21. The reaction time was 168 h.

[0141] Table 8 shows the percentage molar fractions of the target compounds 22A, 22B and 22C and the starting compounds 1 and 21 in the mixture obtained in the reaction. Example 52

[0142] Scheme B52 illustrates the reaction of tetraethoxysilane 1 with trimethylsilyl isocyanate ((CHa^SiNCO) 23) in the presence of triphenylphosphine. (Scheme B52) (CH3)3 SiNCO 23 is a compound of general formula III, in which three radicals R 3 Methyl, the remaining residue R 3 -NCO and x is 0. Compounds 24A, 24B and 24C are compounds of general formula I, wherein m is 0. In compound 24A, a radical R 1 -NCO and the other residues R 1 are each -OR 2 with R 2 is ethyl. In compound 24B, two radicals R 1 each -NCO and the other residues R 1 are each -OR 2 with R 2 is ethyl. In compound 24C, three radicals R 1 each -NCO and the remaining residue R 1 is -OR 2 with R 2 equals ethyl.

[0143] Using the first general synthesis route, tetraethoxysilane 1 was reacted with (CHa^SiNCO 23) in a molar ratio of 1:1. The reaction takes place in the presence of triphenylphosphane. 0.1 mol% of triphenylphosphane was used, based on the sum of the molar amount of compound 1 and the molar amount of compound 23. The reaction time was 168 h.

[0144] Table 8 shows the mole percentages of the target compounds 24A, 24B, and 24C and the starting compounds 1 and 23 in the mixture obtained during the reaction. Additionally, 6 mol% of (CH3)3Si(OCH2CH3) was obtained. Example 53

[0145] Scheme B53 illustrates the reaction of tetraethoxysilane 1 with trimethylsilyl azide ((CHa^SiNs) 25) in the presence of triphenylphosphine. (Scheme B53) (CH3)3SiN3 25 is a compound of general formula III, in which three radicals R 3Methyl, the remaining residue R 3 -N3 and x is 0. Compounds 26A, 26B and 26C are compounds of general formula I, wherein m is 0. In compound 26A, a radical R 1 -N3 and the other residues R 1 are each -OR 2 with R 2 is ethyl. In compound 26B, two radicals R 1 each -N3 and the other residues R 1 are each -OR 2 with R 2 is ethyl. In compound 26C, three radicals R 1 each -N3 and the remaining residue R 1 is -OR 2 with R 2 equals ethyl.

[0146] Using the first general synthesis route, tetraethoxysilane 1 was reacted with (CEE^SiNs) 25 in a molar ratio of 1:1. The reaction was carried out in the presence of triphenylphosphine. 0.1 mol% of triphenylphosphine was used, based on the sum of the molar amount of compound 1 and the molar amount of compound 25. The reaction time was 168 h.

[0147] Table 8 shows the mole percentages of the target compounds 26A, 26B, and 26C and the starting compounds 1 and 25 in the mixture obtained during the reaction. In addition, 7 mol% of (O43)3 S^OCEECHa) was obtained. Table 8 Results

[0148] Examples 1 to 3 confirm that triphenylphosphine (PPlv) is a highly suitable catalyst for the chosen ligand exchange reaction. Compared to related examples using BiCl as the catalyst (see Comparative Examples 36 to 38), a significant reduction in the required reaction time to 1 h is achieved. In contrast to BiCl, the resulting product composition is also virtually constant.

[0149] Examples 4 to 7 demonstrate the dependence of the product composition on the ratio of starting materials used. This allows for controlling which substitution pattern is preferentially formed.

[0150] The ligand exchange reaction was also successful with hydridohalosilanes in the presence of triphenylphosphine (PPI13) (Examples 8 to 11), although the reaction only proceeded with the formation of byproducts. The selected halobosilane from Example 12 did not undergo any significant reaction. With the halosiloxane from Examples 13 and 14, however, the ligand exchange reaction was again observed, but also with the noticeable formation of byproducts.

[0151] The reaction was also successful with other homologues of tetraalkoxysilanes. For TMOS, the product composition obtained after 1 h is the same as after 168 h (Examples 15 and 16). For T n For POS, however, an increased reaction time is preferable, since the reaction is probably slower due to the steric demand.

[0152] A variety of aryl, alkyl, and halogen-containing phosphine compounds were tested as alternative catalysts to PPI13 (Examples 19 to 28). It was found that, with the exception of tri(cyclohexyl)phosphine (PCya) (Example 23), all tested compounds achieved a similarly good product composition of the desired haloalkoxysilanes as triphenylphosphine (PPI13) at a reaction time of 168 h (Examples 19, 21, 25, 27). However, reducing the reaction time to one hour resulted in almost all compounds (Examples 22, 24, 26, 28) showing hardly any catalytic activity. Only tri( / ?-tolyl)phosphine (P( / ?-Tol)3) (Example 20) continued to achieve a similar product composition to triphenylphosphine (PPI13). Thus, tri( / ?-tolyl)phosphane (P( / ?-Tol)3) can be considered an alternative to PPI13. However, triphenylphosphane (PPI13) is significantly cheaper.

[0153] Examples 29 to 34 show that the ligand exchange reaction with haloorganosilanes is still catalyzed by triphenylphosphine (PPI13). In addition to the typical haloalkoxysilanes, a variety of haloalkoxyorganosilanes are formed. The product composition thus becomes significantly more variable.

[0154] Comparative Example 35, the uncatalyzed reaction of TEOS and SiCL, demonstrated that a reaction occurred under the chosen reaction conditions. This also exhibited the typical substitution pattern, but was characterized by very low conversion even after 168 hours of reaction.

[0155] The reactions of the selected halosilanes with BiCL as Lewis acid catalyst (Examples 36 to 40) resulted in similar product compositions as the reactions with triphenylphosphine (PPI13) (see Examples 1, 3, 8 to 11). For di- and trichlorosilane (Examples 39 to 40), BiCl shows somewhat more selective reactions with higher conversions than triphenylphosphane (PPI13). However, the example of the reaction of TEOS with SiCl (Examples 36 to 38) shows that the BiCl3-catalyzed reaction requires significantly more reaction time. Thus, even after 24 hours, the conversion of the one-hour triphenylphosphane-catalyzed reaction (Example 3) is not yet achieved. Even typical representatives of nitrogen-based Lewis bases, such as triphenylamine (Examples 41 and 42) or pyridine (Examples 43 and 44), do not approach the conversion or selectivity of triphenylphosphane (PPI13), regardless of the reaction time. Only the reaction of TEOS and SiCL in the presence of BiCL is known in the literature (Komata et al., Chem. Asian J., 2016, 11, 3225-3233). Comparative examples for Lewis base catalysts, however, are not known in the literature.

Claims

Patent claims 1. Process for the preparation of a compound of general formula I (Formula I), wherein R 1 is selected at each occurrence from the group consisting of hydrogen, halogen, pseudohalogen, a group R 2 and a group -OR 2 exists, whereby R 2 is selected at each occurrence from the group consisting of a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group, and a substituted or unsubstituted alkylaryl group; m is 0 or an integer from 1 to 10; and n is at each occurrence 0 or 1; with the proviso that at least one of the radicals R 1 halogen or pseudohalogen and that at least one of the radicals R 1 a group -OR 2wherein the process comprises reacting a compound of general formula II (Formula II), where R 6 is selected at each occurrence from the group consisting of hydrogen, a group R 7 and a group -OR 7 exists, whereby R 7 is selected at each occurrence from the group consisting of a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group and a substituted or unsubstituted alkylaryl group; m and n have the meanings given in connection with the general formula I; with the proviso that at least one of the radicals R 6 a group -OR 7 with a compound of the general formula III wherein R 3is selected at each occurrence from the group consisting of hydrogen, halogen, pseudohalogen and a radical R 4 consists; R 4 is selected at each occurrence from the group consisting of a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group, and a substituted or unsubstituted alkylaryl group; x is 0 or 1; and y is at each occurrence 0 or 1; with the proviso that at least one of the radicals R 3 halogen or pseudohalogen; in the presence of a catalyst, wherein the catalyst is an organophosphane.

2. Process according to claim 1, characterized in that the catalyst is a Compound P(R 5 )3, where R 5 at each occurrence from the group selected from halogen, a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group and a substituted or unsubstituted alkylaryl group.

3. A process according to claim 1 or claim 2, characterized in that the catalyst is selected from the group consisting of triphenylphosphane, tri(I-tolyl)phosphane, tri(o-tolyl)phosphane, tricyclohexylphosphane, tri(z-butyl)phosphane and trichlorophosphane.

4. Process according to one of the preceding claims, characterized in that all radicals R 1 in the compound of general formula I are each independently selected from the group consisting of hydrogen, halogen, pseudohalogen and a group -OR 2 where R 2a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 12 carbon atoms.

5. Process according to one of the preceding claims, characterized in that in the compound of general formula I m is 0 or 1.

6. Process according to one of the preceding claims, characterized in that the compound of general formula I is a compound of general formula IA or a compound of general formula IB Formula IA Formula IB is where R 1 and m have the meanings given in connection with the general formula I.

7. Process according to one of the preceding claims, characterized in that in the compound of general formula II R 6 at each occurrence one group -OR 7 where R 7each represents a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 12 carbon atoms.

8. Process according to one of the preceding claims, characterized in that the compound of general formula II is selected from the group consisting of tetramethoxysilane, tetraethoxysilane and tetra-w-propoxysilane.

9. Process according to one of the preceding claims, characterized in that in the compound of general formula III R 4 at each occurrence is a substituted or unsubstituted, branched or unbranched alkyl group having 1 to 12 carbon atoms.

10. Process according to one of the preceding claims, characterized in that the compound of general formula III is a compound of general formula III-A or a compound of general formula III-B Formula III-A is Formula III-B, wherein in the compound of general formula III-A R 3 has the meanings given in connection with the general formula III and x is 0 or 1 and where in the compound of the general formula III-B R 3 has the meanings given in connection with the general formula III and x is 1.

11. Process according to one of the preceding claims, characterized in that in the compound of general formula I and / or in the compound of general formula III halogen is selected at each occurrence from the group consisting of bromine, chlorine, fluorine and iodine.

12. Process according to one of the preceding claims, characterized in that in the compound of general formula I and / or in the compound of general formula III, pseudohalogen is selected at each occurrence from the group consisting of -CN, -N3, -OCN, -NCO, -CNO, -SCN, -NCS and -NRX -CN, where R x is hydrogen or alkyl.

13. Process according to one of the preceding claims, characterized in that the compound of general formula III is selected from the group consisting of dichlorosilane (BSiCh), trichlorosilane (HSiCF), tetrachlorosilane (SiCl), hexachlorodisiloxane (( / »(SiClsjz), methyltrichlorosilane (CHaSiCF), methyldichlorosilane (HSiCHaCh) and dimethyldichlorosilane (CHaSiCh).

14. A process according to any one of the preceding claims, characterized in that it is carried out under protective gas.

15. Method according to one of the preceding claims, characterized in that the method is carried out at ambient pressure and / or ambient temperature.

16. A process according to any one of the preceding claims, characterized in that it is carried out at room temperature.

17. A process according to any one of the preceding claims, characterized in that it is a solvent-free process.

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