Preparation of organosilicon compounds containing aldehyde functional groups

Abstract

The process for preparing aldehyde-functional organosilicon compounds comprises 1) combining starting materials comprising: (A) a gas comprising hydrogen and carbon monoxide, (B) a vinyl-functional organosilicon compound, and (C) a rhodium / ligand complex catalyst under conditions to catalyze a hydroformylation reaction.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority to and the entire benefit of U.S. Provisional Patent Application No. 63 / 330,571, filed April 13, 2022, the contents of which are incorporated herein by reference.

[0002] FIELD OF THEINVENTION A process for preparing aldehyde-functional organosilicon compounds is disclosed. More specifically, the process for preparing aldehyde-functional organosilicon compounds uses a rhodium / ligand complex catalyst for the hydroformylation of vinyl-functional organosilicon compounds with carbon monoxide and hydrogen. [Background technology]

[0003] Aldehydes are important intermediates in the synthesis of other functionalized materials such as alcohols, carboxylic acids, and amines. The introduction of aldehyde functionality into organosilicon compounds such as silanes and siloxanes provides the opportunity to generate a wide variety of organically functionalized organosilicon compounds.

[0004] Existing methods for preparing aldehyde-functional organosilicon compounds (e.g., silanes and siloxanes) may have one or more drawbacks, such as requiring multiple chemical steps, harsh conditions, and / or high catalyst loadings, and such methods may also have slow reaction rates and / or produce undesirable by-products. US Patent No. 7,999,053 discloses one means for preparing aldehyde-functional siloxanes, which involves the reaction of a hydride-functional siloxane with an acetal containing an α-olefin group. After hydrosilylation is complete, the aldehyde is then liberated using an acid catalyst and water. This reaction is typically biphasic, produces significant amounts of waste by-products, and requires multiple steps to recover the desired product.

[0005] Ozonolysis is another route to aldehyde-functional siloxanes. This route involves exposing olefin-functional siloxanes to ozone to form silicone ozonides. The ozonides can be further reacted under acidic conditions to form aldehydes. This route also has multiple steps.

[0006] Grignard coupling of bromophenyldioxolanes with chlorosilanes and subsequent hydrosilylation with vinyl-functional siloxanes is another method for preparing aldehyde-functional siloxanes, which also has multiple steps and generates waste products.

[0007] Another possible route to aldehyde-functional silicones is the hydrosilylation of SiH-functional siloxanes with (non-silicon) aldehyde compounds that also contain other unsaturated carbon-carbon bonds. This route may suffer from the competing reaction of the addition of SiH across the aldehyde carbonyl group. Furthermore, the hydrosilylation route may also suffer from the formation of large amounts of undesirable branched isomers as by-products.

[0008] Hydroformylation of vinyl-functional silanes and vinyl-functional siloxanes has also been proposed. However, the previously proposed processes suffer from one or more of the following shortcomings: slow reaction rate, low selectivity to the desired linear isomer product, and high catalyst loading required for the reaction. A slow reaction rate leads to low productivity. The high catalyst loading required would lead to difficulties in catalyst recycling. Low linear selectivity would lead to product decomposition, since branched products tend to undergo the Brook rearrangement reaction. Summary of the Invention

[0009] A process for preparing aldehyde-functional organosilicon compounds is disclosed which comprises: 1) combining starting materials comprising: (A) a gas comprising hydrogen and carbon monoxide, (B) a vinyl-functional organosilicon compound, and (C) a rhodium / ligand complex catalyst under conditions to catalyze a hydroformylation reaction. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The hydroformylation process described herein employs starting materials comprising (A) a gas comprising hydrogen and carbon monoxide, (B) a vinyl-functional organosilicon compound, and (C) a rhodium / ligand complex catalyst. The starting materials may optionally further comprise (D) a solvent.

[0011] The gas starting material (A) used in the hydroformylation process includes carbon monoxide (CO) and hydrogen gas (H2). For example, the gas can be synthesis gas. As used herein, "syngas" (from synthesis gas) refers to a gas mixture containing various amounts of CO and H2. Production methods are well known and include, for example, (1) steam reforming and partial oxidation of natural gas or liquid hydrocarbons, and (2) gasification of coal and / or biomass. CO and H2 are typically the major components of synthesis gas, but synthesis gas can contain carbon dioxide and inert gases such as CH4, N2, and Ar. The molar ratio of H2 to CO (H2:CO molar ratio) varies widely but can range from 1:100 to 100:1, alternatively 1:10 to 10:1. Synthesis gas is commercially available and is often used as a fuel source or as an intermediate for producing other chemicals. Alternatively, CO and H2 from other sources (i.e., other than syngas) may be used as starting material (A) herein. Alternatively, the H2:CO molar ratio in starting material (A) for use herein may be 3:1 to 1:3, alternatively 2:1 to 1:2, alternatively 1:1.

[0012] The vinyl-functional organosilicon compound has at least one vinyl group covalently bonded to silicon per molecule. Alternatively, the vinyl-functional organosilicon compound can have two or more vinyl groups covalently bonded to silicon per molecule. The starting material (B) can be one vinyl-functional organosilicon compound. Alternatively, the starting material (B) can include two or more vinyl-functional organosilicon compounds that are different from each other. For example, the vinyl-functional organosilicon compound can include one or both of (B1) silane and (B2) polyorganosiloxane.

[0013] The starting material (B1), a vinyl-functional silane, has the formula (B1-1): R A x SiR 23 (4-x) (In the formula, each R A is a vinyl group, and each R 23 is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, an acyloxy group of 2 to 18 carbon atoms, and a hydrocarbyloxy functional group of 1 to 18 carbon atoms, and the subscript x is 1 to 4. Alternatively, the subscript x can be 1 or 2, alternatively 2, alternatively 1. Alternatively, each R 23 may be independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms, aryl groups of 6 to 18 carbon atoms, acyloxy groups of 1 to 18 carbon atoms, and hydrocarbyloxy functional groups of 1 to 18 carbon atoms. 23 may be independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms, aryl groups of 6 to 18 carbon atoms, and alkoxy functional groups of 1 to 18 carbon atoms. 23 may be independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms, aryl groups of 6 to 18 carbon atoms, and hydrocarbyloxy functional groups of 1 to 18 carbon atoms.

[0014] R 23Suitable alkyl groups for may be linear, branched, cyclic, or a combination of two or more thereof. The alkyl groups are exemplified by methyl, ethyl, propyl (including n-propyl and / or isopropyl), butyl (including n-butyl, tert-butyl, sec-butyl, and / or isobutyl), pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and branched isomers having 5 to 18 carbon atoms), and the alkyl groups are further exemplified by cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Alternatively, R 23 The alkyl group of R may be selected from the group consisting of methyl, ethyl, propyl, and butyl, alternatively methyl, ethyl, and propyl, alternatively methyl or ethyl. 23 The alkyl group in may be methyl.

[0015] R 23 Suitable aryl groups for may be monocyclic or polycyclic and may have pendant hydrocarbyl groups. For example, R 23 Aryl groups of R include phenyl, tolyl, xylyl, and naphthyl, as well as aralkyl groups such as benzyl, 1-phenylethyl, and 2-phenylethyl. 23 The aryl group of R may be monocyclic, such as phenyl, tolyl, or benzyl; alternatively, R 23 The aryl group can be phenyl.

[0016] R 23 Suitable hydrocarbyloxy functional groups for the compound are of the formula -OR 24 Or expression - OR 25 -OR 24 (In the formula, each R 25 is an independently selected divalent hydrocarbyl group of 1 to 18 carbon atoms, and each R 24 are independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms, which are 23 As described and exemplified above for R 25Examples of divalent hydrocarbyl groups include alkylene groups such as ethylene, propylene, butylene, or hexylene, arylene groups such as phenylene, or

[0017] [ka] or

[0018] [ka] Alternatively, R 25 may be an alkylene group such as ethylene. Alternatively, the hydrocarbyloxy functionality may be an alkoxy functionality such as methoxy, ethoxy, propoxy, or butoxy, alternatively methoxy or ethoxy, alternatively methoxy.

[0019] R 23 Suitable acyloxy groups for the formula

[0020] [ka] (In the formula, R 24 (wherein is as described above). Examples of suitable acyloxy groups include acetoxy. Vinyl-functional acyloxysilanes and methods for their preparation are known in the art, for example, U.S. Patent No. 5,387,706 to Rasmussen et al. and U.S. Patent No. 5,902,892 to Larson et al.

[0021] Suitable vinyl-functional silanes are exemplified by vinyl-functional trialkylsilanes such as vinyltrimethylsilane and vinyltriethylsilane, vinyl-functional trialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, and vinyltris(methoxyethoxy)silane, vinyl-functional dialkoxysilanes such as vinylphenyldiethoxysilane, vinylmethyldimethoxysilane, and vinylmethyldiethoxysilane, vinyl-functional monoalkoxysilanes such as trivinylmethoxysilane, vinyl-functional triacyloxysilanes such as vinyltriacetoxysilane, and vinyl-functional diacyloxysilanes such as vinylmethyldiacetoxysilane.All of these vinyl-functional silanes are commercially available from Gelest Inc. (Morrisville, Pennsylvania, USA).Furthermore, vinyl-functional silanes can be prepared by known methods such as those disclosed in U.S. Patent No. 4,898,961 to Baile et al. and U.S. Patent No. 5,756,796 to Davern et al.

[0022] Alternatively, (B) the vinyl-functional organosilicon compound may comprise (B2) a vinyl-functional polyorganosiloxane. The vinyl-functional polyorganosiloxane may be cyclic, linear, branched, resinous, or a combination of two or more thereof. The vinyl-functional polyorganosiloxane may have a unit formula (B2-1): (R 23 3SiO 1 / 2 ) a (R 23 2R A SiO 1 / 2 ) b (R 23 2SiO 2 / 2 ) c (R 23 R A SiO 2 / 2 ) d (R 23 SiO 3 / 2 ) e (R A SiO 3 / 2 ) f (SiO 4 / 2 ) g(ZO 1 / 2 ) h (In the formula, R A and R 23 is as defined above, and each Z is independently selected from a hydrogen atom and R 24 (In the formula, R 24 are as above), and the subscripts a, b, c, d, e, f, and g represent the number of each unit in formula (B2-1) and have values ​​such that subscript a≧0, subscript b≧0, subscript c≧0, subscript d≧0, subscript e≧0, subscript f≧0, and subscript g≧0, and have values ​​such that the quantity (a+b+c+d+e+f+g)≧2 and the quantity (b+d+f)≧1, and the subscript h has a value such that 0≦h / (e+f+g)≦1.5). At the same time, the quantity (a+b+c+d+e+f+g) can be ≦10,000. Alternatively, in formula (B-2-1), each R 23 may be independently selected from the group consisting of a hydrogen atom, an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, and a hydrocarbyloxy functional group of 1 to 18 carbon atoms. 23 may be independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms, aryl groups of 6 to 18 carbon atoms, and alkoxy functional groups of 1 to 18 carbon atoms. 23 may be independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms, and aryl groups of 6 to 18 carbon atoms. Alternatively, each Z may be hydrogen or an alkyl group of 1 to 6 carbon atoms. Alternatively, each Z may be hydrogen.

[0023] Alternatively, the vinyl-functional polyorganosiloxane (B2) may comprise a linear polydiorganosiloxane (B2-2) having at least one vinyl group per molecule, alternatively at least two vinyl groups (e.g., when subscripts e=f=g=0 in formula B2-1 above). For example, the polydiorganosiloxane may have the unit formula (B2-3): (R 23 3SiO 1 / 2 ) a (R A R 23 2SiO1 / 2 ) b (R 23 2SiO 2 / 2 ) c (R A R 23 SiO 2 / 2 ) d (In the formula, R A and R 23 is as above, subscript a may be 0, 1, or 2, subscript b may be 0, 1, or 2, subscript c > 0, subscript d > 0, with the proviso that the quantity (b+d) > 1, the quantity (a+b) = 2, and the quantity (a+b+c+d) > 2. Alternatively, in unit formula (B2-3), the quantity (a+b+c+d) may be at least 3, alternatively at least 4, alternatively > 50. At the same time, in unit formula (B2-3), the quantity (a+b+c+d) may be 10,000 or less, alternatively 4,000 or less, alternatively 2,000 or less, alternatively 1,000 or less, alternatively 500 or less, alternatively 250 or less. Alternatively, in unit formula (B2-3), each R 23 may be independently selected from the group consisting of alkyl and aryl, alternatively methyl and phenyl. Alternatively, each R in the unit formula (B2-3) 23 can be an alkyl group, alternatively, each R 23 can be methyl.

[0024] Alternatively, the polydiorganosiloxane of the unit formula (B2-3) may be a polydiorganosiloxane of the unit formula (B2-4): (R 23 2R A SiO 1 / 2 )2(R 23 2SiO 2 / 2 ) m (R 23 R A SiO 2 / 2 ) n , Unit formula (B2-5): (R 23 3SiO 1 / 2 )2(R 23 2SiO 2 / 2 ) o (R 23 R A SiO 2 / 2 ) por a combination of both (B2-4) and (B2-5).

[0025] In formulas (B2-4) and (B2-5), each R 23 and R A are as above. Subscript m may be 0 or a positive number. Alternatively, subscript m may be at least 2. Alternatively, subscript m may be from 2 to 2,000. Subscript n may be 0 or a positive number. Alternatively, subscript n may be from 0 to 2000. Subscript o may be 0 or a positive number. Alternatively, subscript o may be from 0 to 2000. Subscript p is at least 2. Alternatively, subscript p may be from 2 to 2000.

[0026] The starting material (B2) is a vinyl-functional polydiorganosiloxane, for example i) bis-dimethylvinylsiloxy terminated polydimethylsiloxane, ii) bis-dimethylvinylsiloxy terminated poly(dimethylsiloxane / methylvinylsiloxane), iii) bis-dimethylvinylsiloxy terminated polymethylvinylsiloxane, iv) bis-trimethylsiloxy terminated poly(dimethylsiloxane / methylvinylsiloxane), v) bis-trimethylsiloxy terminated polymethylvinylsiloxane, vi) bis-dimethylvinylsiloxy terminated poly(dimethylsiloxane / methylphenylsiloxane), The polydimethylsiloxanes may include bis-dimethylvinylsiloxy terminated poly(dimethylsiloxane / methylvinylsiloxane), vii) bis-dimethylvinylsiloxy terminated poly(dimethylsiloxane / methylphenylsiloxane), viii) bis-dimethylvinylsiloxy terminated poly(dimethylsiloxane / diphenylsiloxane), ix) bis-phenyl,methyl,vinyl-siloxy terminated polydimethylsiloxane, x) bis-dimethylvinylsiloxy terminated poly(dimethylsiloxane / methylhexenylsiloxane), and xi) a combination of two or more of i)-ix).

[0027] Methods for preparing the linear vinyl-functional polydiorganosiloxanes described above for starting material (B2), such as the hydrolysis and condensation of the corresponding organohalosilanes and oligomers, or the equilibration of cyclic polydiorganosiloxanes, are known in the art, see, for example, U.S. Pat. Nos. 3,284,406, 4,772,515, 5,169,920, 5,317,072, and 6,956,087, which disclose the preparation of linear polydiorganosiloxanes having vinyl groups. Examples of linear polydiorganosiloxanes having vinyl groups are commercially available, for example, under the trade names DMS-V00, DMS-V03, DMS-V05, DMS-V21, DMS-V22, DMS-V25, DMS-V-31, DMS-V33, DMS-V34, DMS-V35, DMS-V41, DMS-V42, DMS-V43, DMS-V46, DMS-V51, DMS-V52 from Gelest Inc., Morrisville, Pennsylvania, USA.

[0028] Alternatively, the (B2) vinyl-functional polyorganosiloxane may be cyclic, for example, where in the unit formula (B2-1), the subscripts a=b=c=e=f=g=h=0. Cyclic vinyl-functional polydiorganosiloxanes are represented by the unit formula (B2-7): (R 23 R A SiO 2 / 2 ) d (In the formula, R A and R 23is as above, and subscript d can be from 3 to 12, alternatively from 3 to 6, alternatively from 4 to 5. Examples of cyclic vinyl functional polydiorganosiloxanes include 2,4,6-trimethyl-2,4,6-trivinyl-cyclotrisiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl-cyclotetrasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8,10-pentavinyl-cyclopentasiloxane, and 2,4,6,8,10,12-hexamethyl-2,4,6,8,10,12-hexavinyl-cyclohexasiloxane. These cyclic vinyl functional polydiorganosiloxanes are known in the art and are commercially available, for example, from Sigma-Aldrich (St. Louis, Missouri, USA), Milliken (Spartanburg, South Carolina, USA), and other vendors.

[0029] Alternatively, the cyclic vinyl-functional polydiorganosiloxane may be represented by the unit formula (B2-8): (R 23 2SiO 2 / 2 ) c’ (R 23 R A SiO 2 / 2 ) d (In the formula, R 23 and R A is as above, and subscript c' is >0 to 6, and subscript d is 3 to 12. Alternatively, in formula (B2-8), c' can be 3 to 6, and d can be 3 to 6.

[0030] Alternatively, (B2) vinyl-functional polyorganosiloxane may be an oligomer, for example, where the quantity (a+b+c+d+e+f+g) in the above unit formula (B2-1) is ≦50, alternatively ≦40, alternatively ≦30, alternatively ≦25, alternatively ≦20, alternatively ≦10, alternatively ≦5, alternatively ≦4, alternatively ≦3. The oligomer may be cyclic, linear, branched, or a combination thereof. The cyclic oligomer is as described above as starting material (B2-6).

[0031] An example of a linear vinyl-functional polyorganosiloxane oligomer is represented by the formula (B2-10):

[0032] [ka] (In the formula, R 23 is as above, and each R 26 are independently 23 and R A with the proviso that at least one R 26 is R A where the subscript z is 0 to 48. Examples of linear vinyl-functional polyorganosiloxane oligomers can include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,1,1,3,3-pentamethyl-3-vinyl-disiloxane, 1,1,1,3,5,5,5-heptamethyl-3-vinyl-trisiloxane, all of which are commercially available, for example, from Gelest, Inc. (Morrisville, Pennsylvania, USA) or Sigma-Aldrich (St. Louis, Missouri, USA).

[0033] Alternatively, the vinyl-functional polyorganosiloxane oligomer can be branched. The branched oligomer has the general formula (B2-11): R A SiR 27 3 (wherein, R A is as above, and each R 27 is R 28 and -OSi(R 29 ) 3, each R 28 is a monovalent hydrocarbon group, and each R 29 is R 27 , -OSi(R 30 )3, and -[OSiR 28 2] ii OSiR 28 3 are selected, and each R 30 is R 27 , -OSi(R 31 )3, and -[OSiR 28 2]ii OSiR 28 3 are selected, and each R 31 is R 28 and -[OSiR 28 2] ii OSiR 28 3, where subscript ii has a value such that 0≦ii≦100. 27 At least two of -OSi(R 29 ) 3. Alternatively, R 27 All three of these are -OSi(R 29 )3.

[0034] Alternatively, in formula (B2-11), each R 27 -OSi(R 29 )3, then each R 29 The branched polyorganosiloxane oligomer has the following structure:

[0035] [ka] (In the formula, R A and R 30 is as described above) 30 ) 3 moieties. Alternatively, each R 30 As above, R 28 Each R 28 can be methyl.

[0036] Alternatively, in formula (B2-11), each R 27 -OSi(R 29 )3, then one R 29 is each R 27 -OSiR 28 (R 29 )2 for each -OSi(R 29 )3 in R 28 Alternatively, -OSiR 28 (R 29 )2 R's 29 each of which is a branched polyorganosiloxane oligomer having the following structure:

[0037] [ka] (In the formula, R A , R 28 , and R 30 is as described above) 30 ) 3 moieties. Alternatively, each R 30 is R 28 Each R 28 can be methyl.

[0038] Alternatively, in formula (B2-11), one R 27 is R 28 R 27 Two of them are -OSi(R 29 )3. R 27 Two of them are -OSi(R 29 )3, then one R 29 Each -OSi(R 29 )R in 3 28 and R 27 Two of them are -OSiR 28 (R 29 )2. Alternatively, -OSiR 28 (R 29 ) Each R in 2 29 The branched polyorganosiloxane oligomer has the following structure:

[0039] [ka] (In the formula, R A , R 28 , and R 30 is as described above) 30 ) 3. Alternatively, each R 30 is R 28 Each R 28can be methyl. Alternatively, the vinyl functional branched polyorganosiloxane can have 3 to 16 silicon atoms per molecule, alternatively 4 to 16 silicon atoms per molecule, alternatively 4 to 10 silicon atoms per molecule. Examples of vinyl functional branched polyorganosiloxane oligomers include those having the formula:

[0040] [ka] vinyl-tris(trimethylsiloxy)silane having the formula formula

[0041] [ka] (1,1,1,3,5,7,9,9,9-nonamethyl-3,7-bis((trimethylsilyl)oxy)-5-vinylpentasiloxane), and formula

[0042] [ka] (5-((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-1,1,1,3,7,9,9,9-octamethyl-3,7-bis((trimethylsilyl)oxy)-5-vinylpentasiloxane) having the formula: The branched vinyl-functional polyorganosiloxane oligomers can be prepared by known methods such as those disclosed in "Testing the Functional Tolerance of the Piers-Rubinsztajn Reaction: A new Strategy for Functional Silicones" by Grande et al., Supplementary Material (ESI) for Chemical Communications, (Copyright) The Royal Society of Chemistry 2010.

[0043] Alternatively, the vinyl-functional polyorganosiloxane (B2) may be branched, such as the branched oligomers described above, and / or branched vinyl-functional polyorganosiloxanes that may have, for example, more vinyl groups and / or more polymer units per molecule than the branched oligomers described above (e.g., in formula (B2-1), the quantity (a+b+c+d+e+f+g)>50). The branched vinyl-functional polyorganosiloxane may have a quantity (e+f+g) sufficient to provide the branched vinyl-functional polyorganosiloxane (in formula (B2-1)) with >0-5 mol% trifunctional and / or tetrafunctional units.

[0044] For example, the branched vinyl-functional polyorganosiloxane may be represented by the unit formula (B2-13): (R 23 3SiO 1 / 2 ) q (R 23 2R A SiO 1 / 2 ) r (R 23 2SiO 2 / 2 ) s (SiO 4 / 2 ) t (In the formula, R 23 and R A is as above, and the subscripts q, r, s, and t have average values ​​such that 2≧q≧0, 4≧r≧0, 995≧s≧4, t=1, (q+r)=4, and (q+r+s+t) has a value sufficient to impart to the branched polyorganosiloxane a viscosity of >170 mPa·s as measured by a rotational viscometer (described below along with the test method). Alternatively, the viscosity may be >170 mPa·s to 1000 mPa·s, alternatively >170 to 500 mPa·s, alternatively 180 mPa·s to 450 mPa·s, alternatively 190 mPa·s to 420 mPa·s. Q-type branched polyorganosiloxanes suitable for the starting material (B2-12) are known in the art and can be made by known methods, exemplified by those disclosed in U.S. Pat. No. 6,806,339 to Cray et al. and U.S. Patent Application Publication No. 2007 / 0289495 to Cray et al.

[0045] Alternatively, the branched vinyl-functional polyorganosiloxane may be represented by the formula (B2-14): [R A R 23 2Si-(O-SiR 23 2) x -O] (4-w) -Si-[O-(R 23 2SiO) v SiR 23 3] w (In the formula, R A and R 23 is as above, and subscripts v, w, and x may have values ​​such that 200≧v≧1, 2≧w≧0, and 200≧x≧1. Alternatively, in formula (B2-14), each R 23 is independently selected from the group consisting of methyl and phenyl; A is vinyl. Branched polyorganosiloxanes suitable for starting material (B2-14) can be prepared by known methods such as by heating a mixture containing a polyorganosilicate resin and a cyclic or linear polydiorganosiloxane in the presence of a catalyst such as an acid or a phosphazene base, followed by neutralization of the catalyst.

[0046] Alternatively, the branched vinyl-functional polyorganosiloxane for the starting material (B2-11) may have the unit formula (B2-15): (R 23 3SiO 1 / 2 ) aa (R A R 23 2SiO 1 / 2 ) bb (R 23 2SiO 2 / 2 ) cc (R A R 23 SiO 2 / 2 ) ee (R 23 SiO 3 / 2 ) dd (In the formula, R 23 and R Ais as above, subscript aa≧0, subscript bb>0, subscript cc is 15-995, subscript dd>0, and subscript ee≧0). Subscript aa can be 0-10. Alternatively, subscript aa can have a value such that 12≧aa≧0, alternatively 10≧aa≧0, alternatively 7≧aa≧0, alternatively 5≧aa≧0, alternatively 3≧aa≧0. Alternatively, subscript bb≧1. Alternatively, subscript bb≧3. Alternatively, subscript bb can have a value such that 12≧bb>0, alternatively 12≧bb≧3, alternatively 10≧bb>0, alternatively 7≧bb>1, alternatively 5≧bb≧2, alternatively 7≧bb≧3. Alternatively, the subscript cc may have a value such that 800≧cc≧15, alternatively 400≧cc≧15. Alternatively, the subscript ee may have a value such that 800≧ee≧0, 800≧ee≧15, alternatively 400≧ee≧15. Alternatively, the subscript ee may be 0. Alternatively, the quantity (cc+ee) may have a value such that 995≧(cc+ee)≧15. Alternatively, the subscript dd≧1. Alternatively, the subscript dd may be 1 to 10. Alternatively, the subscript dd may have a value such that 10≧dd>0, alternatively 5≧dd>0, alternatively dd=1. Alternatively, the subscript dd may be 1 to 10, alternatively the subscript dd may be 1 or 2. Alternatively, when subscript dd=1, subscript bb can be 3 and subscript cc can be 0. The value of subscript bb can be sufficient to provide a silsesquioxane of formula (B2-15) having a vinyl content of 0.1% to 1%, alternatively 0.2% to 0.6%, based on the weight of the silsesquioxane. Suitable T-branched polyorganosiloxanes (silsesquioxanes) for the starting material (B2-15) are exemplified by those disclosed in U.S. Patent No. 4,374,967 to Brown et al., U.S. Patent No. 6,001,943 to Enami et al., U.S. Patent No. 8,546,508 to Nabeta et al., and U.S. Patent No. 10,155,852 to Enami.

[0047] Alternatively, the (B2) vinyl-functional polyorganosiloxane may be represented by the formula R M 3SiO 1 / 2 and monofunctional units ("M" units) of formula SiO 4 / 2 wherein each R M are independently selected monovalent hydrocarbon radicals, and each R M are independently R as above 23 and R A Alternatively, each R M may be selected from the group consisting of alkyl, vinyl, and aryl. Alternatively, each R M may be selected from methyl, vinyl, and phenyl. Alternatively, R M At least one third, alternatively at least two thirds, of the groups are methyl groups. Alternatively, the M units are (MeSiO 1 / 2 ), (Me2PhSiO 1 / 2 ), and (Me2ViSiO 1 / 2 The polyorganosilicate resins are soluble in solvents such as those described herein as starting material (D), exemplified by liquid hydrocarbons such as benzene, ethylbenzene, toluene, xylene, and heptane, or in liquid non-functional organosilicon compounds such as low viscosity linear and cyclic polydiorganosiloxanes.

[0048] When prepared, the polyorganosilicate resin contains the M and Q units described above, and the polyorganosiloxane contains silicon-bonded hydroxyl groups, and / or the moieties (ZO) described above. 1 / 2 ) and further comprising units having hydrolyzable groups represented by the formula Si(OSiR M 3) may contain 4 neopentamers, where R M is as described above, for example, the neopentamer can be tetrakis(trimethylsiloxy)silane. 29 Si NMR and 13C NMR spectroscopy can be used to measure the hydroxyl and alkoxy content, as well as the molar ratio of M and Q units, expressed as {M(resin)} / {Q(resin)}, excluding the M and Q units from the neopentamer. The M / Q ratio represents the molar ratio of the total number of triorganosiloxy groups (M units) in the resinous portion of the polyorganosilicate resin to the total number of silicate groups (Q units) in the resinous portion. The M:Q ratio can be from 0.5 / 1 to 1.5 / 1, alternatively from 0.6 / 1 to 0.9 / 1.

[0049] The Mn of the polyorganosilicate resin is determined by the R M The Mn of the polyorganosilicate resins varies depending on a variety of factors including the type of hydrocarbon group represented by Mn=Mn+Mn. The Mn of the polyorganosilicate resins refers to the number average molecular weight measured using GPC when the peak representing the neopentamer is excluded from the measurement. The Mn of the polyorganosilicate resins may be 1,500-30,000, alternatively 1,500-15,000, alternatively >3,000-8,000 Da. Alternatively, the Mn of the polyorganosilicate resins may be 3,500-8,000 Da.

[0050] U.S. Patent No. 8,580,073, column 3, line 5 to column 4, line 31, and U.S. Patent Application Publication No. 2016 / 0376482, paragraphs

[0023] to

[0026] , are incorporated herein by reference to disclose MQ resins, which are suitable polyorganosilicate resins for use as starting material (B2). The polyorganosilicate resins can be prepared by any suitable method, such as cohydrolysis of the corresponding silanes or a silica hydrosol capping method. The polyorganosilicate resins can be prepared by a silica hydrogel capping process, such as those disclosed in U.S. Patent No. 2,676,182 to Daudt et al., U.S. Patent No. 4,611,042 to Rivers-Farrell et al., and U.S. Patent No. 4,774,310 to Butler et al. The method of Daudt et al., supra, involves reacting a silica hydrosol with a hydrolyzable triorganosilane, such as trimethylchlorosilane, a siloxane, such as hexamethyldisiloxane, or mixtures thereof, under acidic conditions, and recovering a copolymer having M and Q units. The resulting copolymer generally contains 2-5 weight percent hydroxyl groups.

[0051] The intermediates used to prepare the polyorganosilicate resins can be triorganosilanes and silanes or alkali metal silicates containing four hydrolyzable substituents. The triorganosilanes are represented by the formula R M 3SiX, where R M is as above, and X represents a hydroxyl group or a hydrolyzable substituent, for example of the formula OZ above. A silane having four hydrolyzable substituents has the formula SiX 2 4, wherein each X 2 is independently selected from the group consisting of halogen, alkoxy, and hydroxyl. Suitable alkali metal silicates include sodium silicate.

[0052] The polyorganosilicate resins prepared as described above typically have the formula, for example, HOSiO 3 / 2of silicon-bonded hydroxyl groups. The polyorganosilicate resin may contain up to 3.5% silicon-bonded hydroxyl groups as measured by FTIR spectroscopy and / or NMR spectroscopy as described above. In certain applications, it may be desirable for the amount of silicon-bonded hydroxyl groups to be less than 0.7%, alternatively less than 0.3%, alternatively less than 1%, alternatively between 0.3% and 0.8%. The silicon-bonded hydroxyl groups formed during the preparation of the polyorganosilicate resin can be converted to trihydrocarbon siloxane groups or different hydrolyzable groups by reacting the silicone resin with a silane, disiloxane or disilazane containing the appropriate end group. The silane containing the hydrolyzable group can be added in a molar excess over the amount required to react with the silicon-bonded hydroxyl groups in the polyorganosilicate resin.

[0053] Alternatively, the polyorganosilicate resin has no more than 2%, alternatively no more than 0.7%, alternatively no more than 0.3%, alternatively between 0.3% and 0.8% hydroxyl groups, e.g., of the formula XSiO 3 / 2 wherein R M is as above, and X represents a hydrolyzable substituent, such as OH. The concentration of silanol groups (wherein X=OH) present in the polyorganosilicate resin can be determined using FTIR spectroscopy and / or NMR, as described above.

[0054] For use herein, polyorganosilicate resins further comprise one or more terminal vinyl groups per molecule. Polyorganosilicate resins having terminal vinyl groups can be prepared by reacting the product of Daudt et al. with a sufficient amount of a vinyl-containing endblocking agent and an endblocking agent free of aliphatic unsaturation to provide 3 to 30 mole percent vinyl groups in the final product. Examples of endblocking agents include, but are not limited to, silazanes, siloxanes, and silanes. Suitable endblocking agents are known in the art and are exemplified in U.S. Pat. Nos. 4,584,355 to Blizzard et al., 4,591,622 to Blizzard et al., and 4,585,836 to Homan et al. A single endblocking agent or a mixture of such agents can be used to prepare such resins.

[0055] Alternatively, the polyorganosilicate resin may be represented by the unit formula (B2-17): (R 23 3SiO 1 / 2 ) mm (R 23 2R A SiO 1 / 2 ) nn (SiO 4 / 2 ) oo (ZO 1 / 2 ) h (In the formula, Z, R 23 , and R A , and subscript h are as above, and subscripts mm, nn, and oo may include (mm≧0, nn>0, oo>0, and having average values ​​such that 0.5≦(mm+nn) / oo≦4. Alternatively, 0.6≦(mm+nn) / oo≦4, alternatively, 0.7≦(mm+nn) / oo≦4, alternatively, 0.8≦(mm+nn) / oo≦4.

[0056] Alternatively, the vinyl-functional polyorganosiloxane (B2) may be a vinyl-functional silsesquioxane resin (B2-18), i.e., a polyorganosiloxane having the unit formula: (R 23 3SiO 1 / 2 ) a (R 23 2R A SiO 1 / 2 ) b(R 23 2SiO 2 / 2 ) c (R 23 R A SiO 2 / 2 ) d (R 23 SiO 3 / 2 ) e (R A SiO 3 / 2 ) f (ZO 1 / 2 ) h (wherein R 23 and R A are as described above, and the subscript f > 1, 2 < (e + f) < 10,000, 0 < (a + b) / (e + f) < 3, 0 < (c + d) / (e + f) < 3, and 0 < h / (e + f) < 1.5), and may include a resin containing trifunctional (T) units. Alternatively, the vinyl-functional silsesquioxane resin has the unit formula (B2-19): (R 23 SiO 3 / 2 ) e (R A SiO 3 / 2 ) f (ZO 1 / 2 ) h (wherein R 23 , R A , Z, and the subscripts h, e, and f are as described above). Alternatively, the vinyl-functional silsesquioxane resin may further include, in addition to the above T units, a difunctional (D) unit of the formula (R 23 2SiO 2 / 2 ) c (R 23 R A SiO 2 / 2 ) d , that is, a DT resin, wherein the subscripts c and d are as described above. Alternatively, the vinyl-functional silsesquioxane resin may further include a monofunctional (M) unit of the formula (R 23 3SiO 1 / 2 ) a (R 23 2R A SiO 1 / 2 ) b , that is, an MDT resin, wherein the subscripts a and b are as described above for the unit formula (B2-1).

[0057] Vinyl-functional silsesquioxane resins are commercially available, for example, as follows: 1 / 2 ) 25 (PhSiO 3 / 2 ) 75 RMS-310, which contains D units, is commercially available from Dow Silicones Corporation (Midland, Michigan, USA). Vinyl-functional silsesquioxane resins can be produced by hydrolysis and condensation of trialkoxysilanes or mixtures using methods such as those described in "Chemistry and Technology of Silicone" by Noll, Academic Press (1968), Chapter 5, pages 190-245. Alternatively, vinyl-functional silsesquioxane resins can be produced by hydrolysis and condensation of trichlorosilanes using methods described in U.S. Patent No. 6,281,285 to Becker et al. and U.S. Patent No. 5,010,159 to Bank et al. Vinyl-functional silsesquioxane resins containing D units can be prepared by known methods such as those disclosed in U.S. Patent Application No. 2020 / 0140619 and WO 2018 / 204068 to Swier et al.

[0058] Alternatively, the vinyl-functional organosilicon compound starting material (B) may include (B3) a vinyl-functional silazane. The vinyl-functional silazane has the formula (B3-1): [(R 32 (3-gg) R A gg Si) ff NH (3-ff) ] hh (In the formula, R A is as above, and each R 32 is independently selected from the group consisting of alkyl and aryl groups, each subscript ff is independently 1 or 2, and each subscript gg is independently 0, 1, or 2, with 1>hh>10. 32 For the alkyl and aryl groups, R 23The vinyl functional silazanes may be alkyl and aryl groups as described above for (VII) or (VII). Alternatively, the subscript hh may have a value such that 1>hh>6. Examples of vinyl functional silazanes include MePhViSiNH2, Me2ViSiNH2, (ViMe2Si)2NH, (MePhViSi)2NH. Vinyl functional silazanes may be prepared by known methods, such as by reacting a vinyl functional halosilane with ammonia under anhydrous or substantially anhydrous conditions, followed by distillation of the resulting reaction mixture to separate the cyclic and linear vinyl functional silazanes, such as those disclosed in U.S. Pat. No. 2,462,635 to Haber, U.S. Pat. No. 3,243,404 to Martellock, and WO 83 / 02948 to Dziark. Suitable vinyl-functional silazanes are commercially available, for example, 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane (MeViSiNH) is available from Sigma-Aldrich (St. Louis, MO, USA), sym-tetramethyldivinyldisilazane (ViMeSi)NH is available from Alfa Aesar, and 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisilazane (MePhViSi)NH is available from Gelest, Inc. (Morrisville, Pennsylvania, USA).

[0059] The starting material (B) can be any one of the vinyl-functional organosilicon compounds described above. Alternatively, the starting material (B) can include a mixture of two or more of the vinyl-functional organosilicon compounds.

[0060] The starting material (C) hydroformylation catalyst for use herein comprises an active complex of rhodium and a ligand. The ligand may be symmetric or asymmetric. Alternatively, the ligand may be symmetric. In one embodiment, the ligand comprises or is a bisphosphoramidite ligand. In another embodiment, the ligand comprises or is a tetraphosphoramidite ligand. In yet another embodiment, the ligand comprises or is a phosphine amine ligand. In yet another embodiment, the ligand comprises or is a phosphine ligand. In yet another embodiment, the ligand comprises or is a phosphine ligand. In yet another embodiment, the starting material (C) may comprise a blend of rhodium / ligand complexes comprising different types of ligands.

[0061] The ligand has the formula (C1), (C2), and / or (C3):

[0062] [ka] In the formula, R 1 ~R 22 are each independently selected from hydrogen, a hydrocarbyl group, a heteroaryl group, a halogen atom, or a heterocarbyl group; R 1 ~R 22 two or more of may optionally be joined together to provide one or more cyclic moieties, 1 ~X 4 is independently selected from O, CH, NH, NR, NSO2R, or NSO2A, where each R is an independently selected substituted or unsubstituted alkyl or aryl group, each A is an independently selected aryl or heteroaryl group, and Y 1 ~Y 8each is an independently selected nitrogen-containing heterocyclic moiety bonded to P through N, wherein each heterocyclic moiety is optionally substituted with one or more groups or atoms selected from alkyl, aryl, heteroaryl, alkoxy, acyl, carboxyl, carboxylate, cyano, -SOH, sulfonate, amino, trifluoromethyl, and halogen.

[0063] In one embodiment, the ligand has the formula (C1). In another embodiment, the ligand has the formula (C2). In yet another embodiment, the ligand has the formula (C3).

[0064] R 1 ~R 22Suitable hydrocarbyl groups of may be independently linear, branched, cyclic, or combinations thereof. Cyclic hydrocarbyl groups include aryl groups, and saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups may be monocyclic or polycyclic. Linear and branched hydrocarbyl groups may be independently saturated or unsaturated. An example of a combination of linear and cyclic hydrocarbyl groups is an aralkyl group. "Substituted" means that one or more hydrogen atoms may be replaced by an atom other than hydrogen (e.g., a halogen atom such as chlorine, fluorine, bromine, etc.). Suitable alkyl groups are exemplified by, but are not limited to, methyl, ethyl, propyl (e.g., iso-propyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, and branched saturated hydrocarbon groups of 6 carbon atoms. Suitable aryl groups are exemplified by, but are not limited to, phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, and cyclohexenyl. Suitable monovalent halogenated hydrocarbon groups include, but are not limited to, halogenated alkyl groups having 1-6 carbon atoms or halogenated aryl groups having 6-10 carbon atoms. Suitable halogenated alkyl groups are exemplified by, but are not limited to, the above-mentioned alkyl groups in which one or more hydrogen atoms are replaced with a halogen atom such as F or Cl.For example, fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl are examples of suitable halogenated alkyl groups.Suitable halogenated aryl groups are exemplified by, but not limited to, the above-mentioned aryl groups in which one or more hydrogen atoms are replaced with halogen atoms such as F or Cl.For example, chlorobenzyl and fluorobenzyl are suitable halogenated aryl groups. Suitable heterocarbyl groups include any of the hydrocarbyl groups described above, but containing one or more heteroatoms, such as oxygen, sulfur, nitrogen, etc. Suitable halogen atoms include F, Cl, Br, I, At, and Ts, alternatively F, Cl, and Br, alternatively Cl.

[0065] As mentioned above, R 1 ~R 22 Two or more of R may optionally be joined together to provide one or more cyclic moieties. 1 ~R 22 The cyclic moiety formed by any combination of may be aliphatic or aromatic and may be monocyclic, bicyclic, or polycyclic.

[0066] As an example, when the ligand has the formula (C1), R 1 , R 2 , R 7 , and R 8 are H and R 3 and R 4 forms an aliphatic cyclic ring, and R 5 and R 6 taken together to form an aliphatic cyclic ring, the ligand of formula (C1) is

[0067] [ka] (In the formula, X 1 , X 2 , and Y 1 ~Y 4 is defined above).

[0068] As another example, when the ligand has the formula (C1), R 1 , R 2 , R 7 , and R 8 are H and R 3 and R 4 forms an aromatic ring, and R 5 and R 6 taken together to form an aromatic cyclic ring, the ligand of formula (C1) is

[0069] [ka] (In the formula, X 1 , X 2 , and Y 1 ~Y 4 is defined above).

[0070] As yet another example, when the ligand has the formula (C1), R 3 , R 4 , R 5 , and R 6 are H and R 1 and R 2 forms a bicyclic aromatic ring structure, and R 7 and R 8 taken together to form a bicyclic aromatic structure, the ligand of formula (C1) is

[0071] [ka] (In the formula, X 1 , X 2 , and Y 1~Y 4 is defined above).

[0072] X 1 ~X 4 is independently selected from O, CH, NH, NR, NSO2R, or NSO2A, where each R is an independently selected substituted or unsubstituted alkyl or aryl group and each A is an independently selected aryl or heteroaryl group. 1 ~X 4 Each of is O.

[0073] Y 1 ~Y 8 Each of Y is an independently selected nitrogen-containing heterocyclic moiety bonded to P through N, where each heterocyclic moiety is optionally substituted with one or more groups or atoms selected from alkyl, aryl, heteroaryl, alkoxy, acyl, carboxyl, carboxylate, cyano, -SOH, sulfonate, amino, trifluoromethyl, and halogen. 1 ~Y 8 Each of may be independently monocyclic, bicyclic, and / or polycyclic. Illustrative examples of nitrogen-containing heterocyclic groups include indole, isoindole, pyrrole, carbazole, and imidazole groups. As noted above, any of the carbon atoms in these groups may be substituted with one or more groups or atoms selected from alkyl, aryl, heteroaryl, alkoxy, acyl, carboxyl, carboxylate, cyano, -SO3H, sulfonate, amino, trifluoromethyl, and halogen. In certain embodiments, Y 1 ~Y 8 At least one of Y is substituted with an alkoxy group having 1 to 8 carbon atoms. 1 ~Y 8 At least one of the is substituted with an alkyl group having 1 to 12 carbon atoms, such as a tert-butyl group.

[0074] In certain embodiments, the ligand has the formula (C1), where R 1 ~R8 , X 1 ~X 2 , and Y 1 ~Y 4 is a ligand of the following formula (wherein Me represents methyl and tBu represents t-butyl):

[0075] [ka]

[0076] [ka]

[0077] [ka] The ligand is selected to be a bisphosphoramidite ligand having one of the following structures: A method for preparing the first ligand structure above in this section for formula (C1) is disclosed in US Pat. No. 9,795,952 to Diebolt et al., which is incorporated herein by reference in its entirety.

[0078] In other embodiments, the ligand has the formula (C2), R 9 ~R 22 , X 1 ~X 2 , and Y 5 ~Y 8 is defined as a ligand having the formula:

[0079] [ka] The ligand is selected to be a bisphosphoramidite ligand having one of the following structures:

[0080] In yet other embodiments, the ligand has the formula (C3), R 1 ~R 6 , X 1 ~X 4 , and Y 1~Y 8 is defined as a ligand having the formula:

[0081] [ka] The ligand is selected to be a tetraphosphoramidite ligand having one of the following structures: Methods for preparing these ligand structures described above in this section for formula (C3) are disclosed in US Pat. No. 7,531,698 to Zhang et al., which is incorporated herein by reference in its entirety.

[0082] The starting material (C), the rhodium / ligand complex catalyst, may be prepared by methods known in the art, such as those disclosed in U.S. Patent No. 4,769,498 to Billig et al., column 20, line 50 to column 21, line 40, and U.S. Patent No. 10,023,516 to Brammer et al., column 11, line 35 to column 12, line 12, by varying the appropriate starting materials. For example, the rhodium / ligand complex catalyst may be prepared by a process comprising combining a rhodium precursor with the above-described ligand under conditions to form a complex, which may then be introduced into a hydroformylation reaction medium containing one or both of the above-described starting materials (A) and / or (B). Alternatively, the rhodium / ligand complex catalyst may be formed in situ by introducing a rhodium catalyst precursor to the reaction medium and a ligand to the reaction medium (e.g., before, during, and / or after the introduction of the rhodium catalyst precursor) for in situ formation of the rhodium / ligand complex catalyst. The rhodium / ligand complex catalyst may be activated by heating and / or exposure to starting material (A) to form (C) the rhodium / ligand complex catalyst. The rhodium catalyst precursor may be rhodium dicarbonyl acetylacetonate, Rh2O3, Rh4(CO) 12 , Rh6(CO) 16 Further methods for preparing certain ligands are described herein in the accompanying Examples.

[0083] The rhodium precursor, e.g., rhodium dicarbonyl acetylacetonate, optionally the starting material (D), the solvent, and the ligand may be combined by any convenient means, e.g., by mixing. The resulting rhodium / ligand complex catalyst may be introduced into the reactor, optionally with an excess of the ligand. Alternatively, the rhodium precursor, (D) the solvent, and the ligand may be combined with the starting materials (A) and / or (B), the vinyl-functional organosilicon compound, in the reactor, and the rhodium / ligand complex may be formed in situ. The relative amounts of the ligand and the rhodium precursor are sufficient to provide a molar ratio of ligand / Rh of 10 / 1 to 1 / 1, alternatively 5 / 1 to 1 / 1, alternatively 3 / 1 to 1 / 1, alternatively 2.5 / 1 to 1.5 / 1. In addition to the rhodium / ligand complex catalyst, an excess (e.g., uncomplexed) ligand may be present in the reaction mixture. The excess ligand may be the same as or different from the ligand in the rhodium / ligand complex catalyst.

[0084] The amount of (C) rhodium / ligand complex catalyst (catalyst) is sufficient to catalyze the hydroformylation of (B) vinyl-functional organosilicon compound. The exact amount of catalyst depends on various factors, including the type of vinyl-functional organosilicon compound selected for starting material (B), its exact vinyl content, and reaction conditions such as temperature and pressure of starting material (A). However, the amount of (C) catalyst may be sufficient to provide a rhodium metal concentration of at least 0.1 ppm, alternatively 0.15 ppm, alternatively 0.2 ppm, alternatively 0.25 ppm, alternatively 0.5 ppm, based on the weight of (B) vinyl-functional organosilicon compound. At the same time, the amount of (C) catalyst may be sufficient to provide a rhodium metal concentration of up to 300 ppm, alternatively up to 100 ppm, alternatively up to 20 ppm, alternatively up to 5 ppm, on the same basis. Alternatively, the amount of (C) catalyst may be sufficient to provide from 0.1 ppm to 300 ppm, alternatively from 0.2 ppm to 100 ppm, alternatively from 0.25 ppm to 20 ppm, alternatively from 0.5 ppm to 5 ppm, based on the weight of the (B) vinyl functional organosilicon compound.

[0085] The hydroformylation process reaction may be carried out without additional solvent. Alternatively, the hydroformylation process reaction may be carried out with a solvent to facilitate mixing and / or delivery of one or more of the above starting materials, such as (C) catalyst and / or starting material (B), when a solvent, such as vinyl-functional polyorganosilicate resin, is selected for starting material (B). Solvents are exemplified by aliphatic or aromatic hydrocarbons capable of dissolving the starting materials, such as toluene, xylene, benzene, hexane, heptane, decane, cyclohexane, or combinations of two or more of these. Additional solvents include THF, dibutyl ether, diglyme, and texanol. Without wishing to be bound by theory, it is believed that a solvent may be used to reduce the viscosity of the starting material. The amount of solvent is not critical, but if present, the amount of solvent may be 5% to 70% based on the weight of the vinyl-functional organosilicon compound, which is starting material (B).

[0086] In the process described herein, step 1) is carried out at a relatively low temperature. For example, step 1) can be carried out at a temperature of at least 30°C, alternatively at least 50°C, alternatively at least 70°C. At the same time, the temperature in step 1) can be up to 150°C, alternatively up to 100°C, alternatively up to 90°C, alternatively up to 80°C. Without wishing to be bound by theory, it is believed that lower temperatures, for example, 30°C-90°C, alternatively 40°C-90°C, alternatively 50°C-90°C, alternatively 60°C-90°C, alternatively 70°C-90°C, alternatively 80°C-90°C, alternatively 30°C-60°C, alternatively 50°C-60°C, may be desirable to obtain high selectivity and ligand stability.

[0087] In the process described herein, step 1) may be carried out at a pressure of at least 101 kPa (ambient pressure), alternatively at least 206 kPa (30 psi), alternatively at least 344 kPa (50 psi). At the same time, the pressure in step 1) may be up to 6,895 kPa (1,000 psi), alternatively up to 1,379 kPa (200 psi), alternatively up to 1000 kPa (145 psi), alternatively up to 689 kPa (100 psi). Alternatively, step 1) may be carried out at 101 kPa to 6,895 kPa, alternatively 344 kPa to 1,379 kPa, alternatively 101 kPa to 1000 kPa, alternatively 344 kPa to 689 kPa. Without wishing to be bound by theory, it is believed that it may be beneficial to use relatively low pressures in the processes herein, e.g., <-6,895 kPa, and the ligands described herein enable low pressure hydroformylation processes, which have the benefits of lower cost and better safety than high pressure hydroformylation processes.

[0088] The hydroformylation process may be carried out in batch, semi-batch, or continuous mode using one or more suitable reactors, such as fixed bed reactors, fluidized bed reactors, continuous stirred tank reactors (CSTRs), or slurry reactors. (B) The choice of vinyl-functional organosilicon compound, (C) the catalyst, and (D) whether a solvent is used may affect the size and type of reactor used. One reactor, or two or more different reactors may be used. The hydroformylation process may be carried out in one or more steps, which may be influenced by balancing capital costs, achieving high catalyst selectivity, activity, life, and ease of operation, as well as the reactivity of the particular starting materials and the reaction conditions selected, and the products desired.

[0089] Alternatively, the hydroformylation process can be carried out in a continuous manner. For example, the process used can be as described in U.S. Patent No. 10,023,516, except that the olefin feed stream and catalyst described therein are replaced with (B) the vinyl-functional organosilicon compound and (C) the rhodium / ligand complex catalyst described herein, respectively.

[0090] Step 1) of the hydroformylation process forms a reaction fluid containing an aldehyde-functional organosilicon compound. The reaction fluid may further include additional materials, such as those intentionally used during step 1) of the process or those formed in situ. Examples of such materials that may also be present include unreacted (B) vinyl-functional organosilicon compound, unreacted (A) carbon monoxide and hydrogen gas, and / or by-products formed in situ, such as ligand decomposition products and their adducts, and high-boiling liquid aldehyde condensation by-products, and (D) solvent, if used. The term "ligand decomposition products" includes, but is not limited to, any and all compounds resulting from one or more chemical transformations of at least one of the ligand molecules used in the process.

[0091] The hydroformylation process may further include one or more additional steps, such as 2) recovering (C) the rhodium / ligand complex catalyst from the reaction fluid containing the aldehyde-functional organosilicon compound. Recovering (C) the rhodium / ligand complex catalyst may be carried out by methods known in the art, including, but not limited to, adsorption and / or membrane separation (e.g., nanofiltration). Suitable recovery methods are described, for example, in U.S. Patent No. 5,681,473 to Miller et al., U.S. Patent No. 8,748,643 to Priske et al., and U.S. Patent No. 10,155,200 to Geilen et al.

[0092] However, one benefit of the process described herein is that it is not necessary to remove and reuse (C) catalyst.Due to the low level of Rh required, it may be more cost-effective not to recover and reuse (C) catalyst, and the aldehyde-functional organosilicon compound produced by the process may be stable even if catalyst is not removed.Therefore, alternatively, the above process may be carried out without step 2).

[0093] Alternatively, the hydroformylation process may further include 3) purification of the reaction product. For example, the aldehyde-functional organosilicon compound may be isolated from the additional materials described above by any convenient means, such as stripping and / or distillation, optionally using reduced pressure. EXAMPLES

[0094] These examples are provided to illustrate the invention to one of ordinary skill in the art and should not be construed as limiting the scope of the invention as set forth in the claims. The starting materials used herein are listed in Table 1 below.

[0095] The following examples are intended to illustrate the present invention and should not be construed as limiting the scope of the invention in any way.

[0096] The specific ingredients utilized in the examples are set forth in Table 1 below.

[0097] [Table 1-1]

[0098] [Table 1-2]

[0099] [Table 1-3]

[0100] [Table 1-4]

[0101] [Table 1-5]

[0102] [Table 1-6]

[0103] [Table 1-7]

[0104] The structure and composition of the product are 1 H, 13 C, and 29 This was confirmed by Si Nuclear Magnetic Resonance (NMR).

[0105] 1 H, 13 C, and 29 Si NMR spectra were recorded on a Varian 400-NMR spectrometer (400 MHz, 1 H). 1 H and 13 Chemical shifts (δ) for C spectra are referenced to internal solvent resonances and reported relative to tetramethylsilane. 1 H and 13 The predicted chemical shifts of the C spectrum were obtained.

[0106] Preparation example: Ligand synthesis Unless otherwise stated, all solvents and reagents were obtained from commercial suppliers and used as received. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by passage through activated alumina. Solvents used in experiments performed in a nitrogen-filled glove box were further dried by storage over activated 3 Å molecular sieves. Moisture-sensitive reaction glassware was dried overnight in an oven (120 °C) before use. NMR spectra were recorded on a Bruker 400-MHz spectrometer. LC-MS analyses were performed using a Waters e2695 separations module coupled with a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separations were performed on an XBridge C18 3.5 μm 2.1 × 50 mm column using a gradient of 5:95 to 100:0 acetonitrile to water with 0.1% formic acid as the ionization agent. HRMS analysis was performed using an Agilent 1290Infinity LC equipped with a Zorbax Eclipse Plus C18 1.8 μm 2.1×50 mm column coupled to an Agilent 6230TOF mass spectrometer with electrospray ionization. 1 H NMR data are reported as follows: chemical shifts (multiplicities (br=broadline, s=singlet, d=doublet, t=triplet, q=quartet, p=quintet, sex=sextet, sept=septet, and m=multiplet), integrals, and assignments). 1 Chemical shifts for 1 H NMR data are reported in ppm with deuterated solvent as the standard. 13 C NMR data is 1 H decoupling was used and chemical shifts are reported in ppm relative to tetramethylsilane (TMS, δ scale) using residual carbon in the deuterated solvent as the standard. 31 P NMR data chemical shifts are reported in ppm (referenced to H3PO4).

[0107] Preparation example 1: Ligand 2

[0108] [ka] A 2 L three-necked round bottom flask was charged with 25 g (155.3 mmol) of 1H-indole-6-boronic acid, 2.7 g (3.1 mmol) of precatalyst, and 500 mL of THF to give a mixture. The mixture was stirred at room temperature. After 5 minutes, 41.2 g (170.8 mmol) of 1-bromo-3,5-di-tert-butylbenzene was added to the mixture, followed by about 600 mL of aqueous potassium phosphate tribasic (99 g, 466 mmol in 600 mL of H2O) to give a reaction mixture. The reaction mixture was then stirred overnight at room temperature. The next morning, an aliquot was removed and analyzed by UP-LC, which indicated complete consumption of the starting material. Diethyl ether (400 mL) was added, and the mixture was then transferred to a separatory funnel. The organic layer was separated and the aqueous layer was washed with an additional 200 mL of diethyl ether (2x). The organic layers were combined and dried over anhydrous MgSO4. The solvent was removed under reduced pressure to give a brownish solid. This material was then dissolved in diethyl ether and treated with activated charcoal for decolorization. The product was filtered through a Celite™ pad and concentrated to give a brownish solid. The solid was purified by trituration procedure.

[0109] Trituration procedure: Hexane (300 mL, approximately 10 mL / g crude material) was added to the crude material (solid) formed above to obtain a mixture. The mixture was heated in a water bath (55° C.) for 15 minutes to dissolve non-polar impurities, and the mixture was quickly filtered through a fritted filter to recover the pure product. After the first trituration, 23.0 g of pure product was isolated as a white powder. The filtrate from the first trituration was concentrated on a rotary evaporator to obtain a solid residue, which was purified by silica gel column chromatography using hexane:ethyl acetate as the eluent to obtain the second batch of product (7.5 g) as a white solid. The product here was 6-(3,5-di-tert-butylphenyl)-1H-indole.

[0110] Next, bis(indolyl)chlorophosphine was prepared from 6-(3,5-di-tert-butylphenyl)-1H-indole:

[0111] [ka] Specifically, triethylamine (34 mL, 245.5 mmol) in toluene (50 mL) was placed in a 110 mL glass jar and cooled in a glove box refrigerator. PCl3 (3.6 mL, 41.1 mmol) was placed in a 1 L round bottom flask along with 50 mL of toluene and simultaneously placed in the glove box refrigerator. After 1 h, both solutions were removed from the refrigerator and the triethylamine solution was slowly added to the PCl3 solution. An additional 175 mL of chilled toluene was added to the flask to maintain the concentration at approximately 0.2 M (with respect to PCl3). 6-(3,5-di-tert-butyl)-1H-indole (25.0 g, 81.8 mmol) was weighed into a 110 mL glass jar and slowly added in portions to the chilled PCl3 / NEt3 solution over 0.5-1 h with vigorous stirring. A white precipitate began to form during the addition. The reaction mixture was allowed to warm to room temperature and stirred for an additional 12 h. The progress of the reaction was monitored by 31 The reaction mixture was monitored by P NMR. The next day, an aliquot of the reaction mixture was removed, filtered, and 31 The crude reaction mixture was analyzed by P NMR spectroscopy. The NMR indicates the formation of the desired mono-chlorophosphoramidite (δ 108.17 ppm) as the major product along with a small amount of tri(indolyl)phosphine (δ 70.95 ppm). The crude reaction mixture was passed through a Celite™ pad. The filtrate was transferred to a 1 L flask and concentrated to a volume of 200 mL using a glove box vacuum pump (vacuum trap cooled with liquid nitrogen). The crude reaction mixture was 31 It was sampled for P NMR and then used directly in the next step.

[0112] Next, ligand 2 was prepared from bis(indolyl)chlorophosphine:

[0113] [ka] Specifically, in a N2-purged glovebox, bis[6-(3,5-di-tert-butylphenyl)-1H-indolyl]chlorophosphine (27.75 g, 41.1 mmol) and toluene (200 mL) were charged to a 1 L round bottom flask and stored in the glovebox freezer for 1 h (-35 °C). A solution of 5,5',6,6',7,7',8,8'-octahydro-1,1'-bi-2-naphthol (5.5 g, 18.7 mmol) in 50 mL of toluene was slowly added. Triethylamine (15.5 mL, 112 mmol) was then added dropwise to the solution with stirring, resulting in the immediate formation of a white precipitate. The reaction mixture later turned cloudy and yellow. The mixture was stirred at room temperature. After 1 h, an aliquot of the reaction mixture was removed, filtered, and 31 Analysis by P NMR showed complete conversion to the bis(phosphordiamidite) product (ligand 2, δ 112.73 ppm) along with some cyclic phosphoramidite (<2% δ 130.53 ppm) and tri(indolyl)phosphine (<6%, δ 70.96 ppm) by-products. The reaction mixture was removed from the glovebox and passed through a Celite™ pad to remove all inorganic salts, and the filtrate volatiles were removed on a rotary evaporator to leave an orange foamy solid. This crude material was split into two batches (each batch was approximately 10-12 g crude material) for silica gel chromatography. Two 330 g columns were used to purify the material using hexane-DCM as the eluent. After purification of the two batches, the total product isolated was approximately 20 g of white powdery material in 68% yield and 98% purity.

[0114] Preparation example 2: Ligand 3

[0115] [ka] In a N2-purged glovebox, 2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-7,7'-diol (0.58 g, 2.3 mmol) was added to a cooled solution of bis-indolylchlorophosphine (5.6 mmol) in toluene (10 mL) in a 110 mL glass jar. Triethylamine (1.3 mL, 9.2 mmol) was added dropwise to the solution with stirring, resulting in the formation of a white precipitate. The reaction mixture was stirred at room temperature and allowed to warm slowly to room temperature overnight. The next morning, an aliquot of the reaction mixture was removed, filtered, and 31 The reaction was analyzed by P NMR spectroscopy; the reaction was very clean with only one major peak (δ 100.12 ppm) observed. The glass jar was removed from the glove box and the reaction mixture was passed through a Celite™ pad. The filtrate was concentrated and loaded directly onto a 330 g silica column using liquid injection. The product was purified utilizing a 330 g gold silica gel column (5-25% dichloromethane in hexanes), and after column purification, 0.9 g of pure bisphosphoramidite product (ligand 3) was obtained in 49% yield.

[0116] Preparation example 3: Ligand 4

[0117] [ka] In a N2-purged glovebox, 2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-7,7'-diol (0.275 g, 1.2 mmol) was added to a cooled solution of bis[6-(3,5-di-tert-butylphenyl)-1H-indolyl]chlorophosphine (2.8 mmol) in toluene (10 mL) in a 110 mL glass jar. Triethylamine (0.7 mL, 4.8 mmol) was added dropwise to the solution with stirring, resulting in the immediate formation of a white precipitate. The reaction mixture was stirred at room temperature and allowed to warm slowly to room temperature overnight. The next morning, an aliquot of the reaction mixture was removed, filtered, and 31The reaction was analyzed by P NMR spectroscopy; the reaction was very clean with only one major peak (δ 105.28 ppm) observed along with some minor products. The glass jar was removed from the glove box and the reaction mixture was passed through a Celite™ pad. The filtrate was concentrated and loaded directly onto a 330 g silica column using liquid injection. The silica gel column was necessary to remove all the accompanying by-products. A 330 g gold silica gel column (5-25% dichloromethane in hexanes) was utilized to purify the bis product along with the rest of the by-products. After column purification, 0.95 g of pure bisphosphoramidite product (ligand 4) was obtained in 51% yield.

[0118] Preparation example 4: Ligand 5

[0119] [ka] A 250 mL three-neck round bottom flask was charged with 2 g (12.4 mmol) of 1H-indole-6-boronic acid, 0.2 g (0.25 mmol) of precatalyst, and 80 mL of THF. The mixture was stirred at room temperature for 5 min. After 5 min, 2.5 g (13.7 mmol) of 4-bromoanisole was added to the solution, followed by about 50 mL of aqueous potassium phosphate tribasic (7.9 g, 38 mmol) in 25 mL of HO. The reaction mixture was then stirred overnight at room temperature. The next day, the reaction was monitored by LC-MS. Diethyl ether (80 mL) was added to the reaction mixture, and the mixture was then transferred to a separatory funnel. The organic layer was separated and the aqueous layer was further washed with 80 mL of diethyl ether (2×). The organic layers were combined and dried over MgSO and activated charcoal. The solvent was removed under reduced pressure to give a brownish solid. The solid was purified by ISCO silica gel chromatography to give 2.0 g (70%) of the product (6-(4-methoxyphenyl)-1H-indole).

[0120] Next, bis(indolyl)chlorophosphine was prepared from 6-(4-methoxyphenyl)-1H-indole:

[0121] [ka] Specifically, in a N2-purged glove box, phosphorus trichloride (0.3 mL, 3.2 mmol) and triethylamine (2.7 mL) were added to 20 mL of toluene in a 110 mL glass jar. The solution was placed in a glove box freezer (-35 °C) for 1 hour to cool. 6-(4-Methoxyphenyl)-1H-indole (1.45 g, 6.5 mmol) was weighed into a 50 mL glass jar and dissolved in 10 mL of toluene. The PCl3 / NEt3 solution was removed from the freezer and the indole solution was added dropwise (via an addition funnel) to the cold PCl3 / NEt3 solution with stirring. A large amount of white precipitate formed during the addition. The reaction mixture was allowed to warm to room temperature and stirred overnight. The next day, an aliquot of the reaction mixture was removed, filtered, and 31 The crude mixture was analyzed by P NMR spectroscopy. The NMR spectrum indicated the formation of the desired mono-chlorophosphoramidite (d 103.29 ppm) as the major product. The crude mixture was filtered through a Celite™ pad to remove inorganic salts, and the filtrate was further evaporated using a glove box vacuum pump (while maintaining liquid nitrogen in the trap) to leave 3.1 g of the desired mono-chlorophosphoramidite as a yellowish powder (yield >90%). The compound was used directly in the next step without further purification.

[0122] Next, ligand 5 was prepared from bis(indolyl)chlorophosphine:

[0123] [ka] Specifically, in a N2-purged glove box, 5,5',6,6',7,7',8,8'-octahydro-1,1'-bi-2-naphthol (0.4 g, 1.4 mmol) and bis[6-(4-methoxyphenyl)-1H-indolyl]chlorophosphine (1.5 g, 2.9 mmol) were weighed into a 110 mL glass jar and dissolved in 10 mL of THF to produce a reddish yellow solution that was kept in a freezer (-35 °C) for 1 hour. Triethylamine (1.2 mL) was added dropwise to the solution with stirring, resulting in the immediate formation of a white precipitate. The reaction mixture was stirred at room temperature and slowly warmed to 50 °C overnight. The next morning, an aliquot of the reaction mixture was removed, filtered, and 31 The product was analyzed by P NMR spectroscopy; complete conversion to the bisphosphoramidite product (δ 104.37 ppm) was observed. A two-step purification was required to remove all the associated by-products. In the first step, a 330 g gold silica gel column (5-20% dichloromethane in hexane) was utilized to purify the bis product along with the remaining by-products. In the second step, a 160 g neutral alumina column was utilized to further purify the bisphosphoramidite product from the indole by-product (5-20% dichloromethane in hexane). After column purification, 0.6 g of pure bisphosphoramidite product (ligand 5) was obtained in 35% yield.

[0124] Preparation example 5: Ligand 6

[0125] [ka] In a N2-purged glovebox, [1,1'-binaphthalene]-2,2'-diol (0.25 g, 0.9 mmol) was added to a cooled solution of bis[6-(3,5-di-tert-butylphenyl)-1H-indolyl]chlorophosphine (2.8 mmol) in toluene (5 mL) in a 110 mL glass jar. Triethylamine (0.5 mL, 3.6 mmol) was added dropwise to the solution with stirring, resulting in the immediate formation of a white precipitate. The reaction mixture was stirred at room temperature and allowed to warm slowly to room temperature overnight. The next morning, an aliquot of the reaction mixture was removed, filtered, and 31 The bis product was purified using a 330 g gold silica gel column (5-25% dichloromethane in hexanes). After column purification, 0.4 g of pure bisphosphoramidite product (ligand 6) was obtained in 29% yield.

[0126] Preparation Example 6: Ligand 7

[0127] [ka] In a N2-purged glove box, 4,4',5,5',6,6'-hexamethyl-[1,1'-biphenyl]-2,2'-diol (1.0 g, 3.7 mmol) and bis[6-(3,5-di-tert-butylphenyl)-1H-indolyl]chlorophosphine (6.2 g, 8.13 mmol) were weighed into a 220 mL glass jar and dissolved in 75 mL of THF to produce a reddish yellow solution that was kept in a freezer for 1 h (-35 °C). Triethylamine (1.6 mL, 11.1 mmol) was added dropwise to the solution with stirring, resulting in the immediate formation of a white precipitate. The reaction mixture was stirred at room temperature and slowly warmed to 50 °C overnight. The next morning, an aliquot of the reaction mixture was removed, filtered, and 31The product was analyzed by P NMR. A two-step purification was required to remove all the associated by-products. Specifically, in the first step, a 330 g gold silica gel column (5-20% dichloromethane in hexane) was used to purify the bis-product along with the remaining by-products. In the second step, a 160 g neutral alumina column was used to further purify the bis-phosphoramidite product (5-20% dichloromethane in hexane). After column purification, 1.2 g of pure bis-phosphoramidite product (ligand 7) was obtained in 28% yield.

[0128] Preparation Example 7: Ligand 8

[0129] [ka] A 250 mL three-necked round bottom flask was charged with 3.0 g (18.6 mmol) of 6-indole boronic acid, 0.3 g (0.4 mmol) of precatalyst, and 60 mL of THF. The mixture was stirred at room temperature for 5 min. After 5 min, 6.2 g (20.5 mmol) of 4-bromo-3,5-di-tert-butylanisole was added to the solution, followed by about 75 mL of an aqueous solution of potassium phosphate tribasic (12 g, 55 mmol) in 75 mL of H2O. The reaction mixture was then stirred overnight at room temperature. The next day, the reaction was monitored by LC-MS. Diethyl ether (80 mL) was added to the reaction mixture, and the mixture was then transferred to a separatory funnel. The organic layer was separated and the aqueous layer was further washed with 80 mL of diethyl ether (2x). The organic layers were combined and dried over MgSO4. The solvent was removed under reduced pressure to give a brownish solid. The solid was purified by ISCO silica gel chromatography to give 5.2 g (84% yield) of product (6-(3,5-di-tert-butyl-4-methoxyphenyl)-1H-indole).

[0130] Next, bis(indolyl)chlorophosphine was prepared using (6-(3,5-di-tert-butyl-4-methoxyphenyl)-1H-indole):

[0131] [ka] Specifically, in a N2-purged glove box, phosphorus trichloride (0.6 mL, 6.7 mmol) was added to 20 mL of toluene in a 110 mL glass jar. The solution was placed in the glove box freezer (-35 °C) for 1 h to cool. After 1 h, triethylamine (5.6 mL) was added to the PCl3 solution and placed back in the freezer to keep. 6-(3,5-di-tert-butyl-4-methoxyphenyl)-1H-indole (4.5 g, 13.5 mmol) was weighed into a 50 mL glass jar and dissolved in 20 mL of toluene. The PCl3 / NEt3 solution was removed from the freezer and the indole solution was added dropwise to the cold PCl3 / NEt3 solution with stirring. A white precipitate formed during the addition. The reaction mixture was allowed to warm to room temperature and stirred at room temperature for an additional 12 h. The next day, an aliquot of the reaction mixture was removed, filtered, and 31 The crude NMR was analyzed by P NMR spectroscopy. The NMR spectrum indicated the formation of the desired mono-chlorophosphoramidite (δ 108.56 ppm) as the major product. The crude NMR was clean enough to proceed to the next step without further purification.

[0132] Ligand 8 was then prepared using bis(indolyl)chlorophosphine:

[0133] [ka] In a N2-purged glovebox, 5,5',6,6',7,7',8,8'-octahydro-1,1'-bi-2-naphthol (0.8 g, 2.7 mmol) was added to a cooled solution of bis[4-(3,5-di-tert-butyl-4-methoxyphenyl)-1H-indolyl]chlorophosphine (6.7 mmol) in toluene (20 mL) in a 110 mL glass jar. Triethylamine (1.5 mL, 11 mmol) was added dropwise to the solution with stirring, resulting in the immediate formation of a white precipitate. The reaction mixture was stirred at room temperature and allowed to warm slowly to room temperature overnight. The next morning, an aliquot of the reaction mixture was removed, filtered, and 31 The reaction mixture was analyzed by P NMR spectroscopy; complete conversion to the bisphosphoramidite with some minor product was observed. The glass jar was removed from the glove box and the reaction mixture was passed through a Celite™ pad. The filtrate was concentrated and loaded directly onto a 330 g silica column using liquid injection. A 330 g gold silica gel column (5-60% dichloromethane in hexanes) was utilized to purify the product. After column purification, 1.8 g of pure bisphosphoramidite product (ligand 8) was obtained in 40% yield.

[0134] Examples 1 to 15: In the following Examples 1 to 15, the reaction conversion rate, selectivity, and position selectivity (N / I ratio) in C6D6 were measured. 1 The structure and composition of the product were determined by H NMR. 13 This was confirmed by C NMR.

[0135] The reaction mixture 1 H and 13 The hydroformylation of pure substrates involved either catalyst activation during an initial reaction period or catalyst preactivation in toluene prior to hydroformylation, followed by transfer of the activated catalyst to the specific substrate utilized. In addition to linear aldehydes as the main products, the hydroformylation produced several by-products, which were detected and analyzed by NMR. A. Branched aldehydes that determine the reaction regioselectivity (N / I or N / B is the molar ratio of normal aldehyde to branched aldehyde):

[0136] [ka] B. Brook rearrangement by-products formed from branched aldehydes at high temperatures

[0137] [ka] C. Olefin hydrogenation by-products that unproductively consume olefins

[0138] [ka]

[0139] Example 1 Catalyst precursor (25.8 mg, 0.1 mmol) and Ligand 1 (164.6 mg, 0.2 mmol) were dissolved in nitrogen-purged toluene (100 g) with stirring in a purge box. Pure substrate 1 (25 g, 1.67 mmol) was purged with nitrogen and rapidly introduced into a 150 mL open reactor under a nitrogen blanket. The reactor was sealed and purged with syngas three times, followed by slow stirring after each charge and venting after stirring was stopped, to obtain the Rh / Ligand 1 stock solution. The Rh / Ligand 1 stock solution in toluene (0.5 g, 0.58 mL) was then charged to the reactor by syringe. An initial syngas pressure of 40-60 psi was charged and the temperature was gradually increased to 70 °C with slow stirring. The syngas pressure was then adjusted to about 100 psig and stirring to about 400 rpm. The reaction was carried out at 70° C. and approximately 100 psig syngas. The conversion of substrate 1 reached 100% in 2 hours with N / B=74. The reaction parameters, conversion, and N / I ratio as measured by NMR are listed in Table 2 below.

[0140] Example 2: Example 2 followed the same process as Example 1, except that different concentrations of catalyst precursor were utilized, as listed in Table 2 below, which affected the time required to achieve 100% conversion of Substrate 1.

[0141] Example 3: Example 3 follows the same process as Example 1, using the Rh / Ligand 1 stock solution diluted 8-fold with toluene, but Example 3 was carried out at 90° C. instead of 70° C., which affected the time required to achieve 100% conversion of Substrate 1. After 8 hours, the conversion of Substrate 1 was 87% and the N / I ratio was 78, as measured by NMR, as listed in Table 2. The content of olefin hydrogenation by-products in Example 3 was 4.5%, and the content of Brook rearrangement by-products was 2.1%.

[0142] Example 4: Catalyst precursor (25.8 mg, 0.1 mmol) was dissolved in nitrogen-purged toluene (100 g). Ligand 1 (20.6 mg, 0.025 mmol) was dissolved in 12.5 g (14.4 mL) of this solution with stirring under nitrogen. This mixture was diluted 8-fold by adding 87.5 g (100.9 mL) of toluene. Approximately 30-50 mL of this solution was transferred to a 150 mL Parr reactor #1 and maintained at 70 °C under 100 psig syngas for 30 min. The reactor was then cooled to 30-40 °C. Pure substrate 1 (25 g, 1.67 mmol) was purged with nitrogen and rapidly introduced into a 150 mL open Parr reactor #2 under a nitrogen blanket. The reactor was sealed and purged with syngas three times, followed by stirring at low speed after each charge and venting after stirring was stopped. A portion of the activated Rh / Ligand 1 stock solution in toluene (0.5 g, 0.58 mL) was then charged from reactor #1 to reactor #2 via syringe. An initial syngas pressure of 40-60 psi was introduced and the temperature was gradually increased to 70°C with slow stirring. The syngas pressure was then adjusted to about 100 psig and the stirring to about 400 rpm. The reaction was run at 70°C and about 100 psig syngas. The conversion of substrate 1 reached 93% in 4 hours with N / B=82 (as shown in Table 2 below). The amount of olefin hydrogenation by-product was only 2.9% and no Brook rearrangement by-product was detected by NMR.

[0143] Examples 5 to 16: Examples 5-16 follow the same process as Example 1, except that different concentrations of catalyst precursor were utilized, as set forth in Table 2 below, and different ligands were utilized, also as set forth in Table 2, with the reaction parameters and results (measured by NMR) for Examples 5-16.

[0144] Example 17: Catalyst precursor (25.8 mg, 0.1 mmol) and Ligand 1 (164.6 mg, 0.2 mmol) were dissolved in nitrogen-purged toluene (100 g) with stirring in a purge box. Pure substrate 4 (25 g, 2.31 mmol) was purged with nitrogen and rapidly introduced into a 150 mL open reactor under a nitrogen blanket. The reactor was sealed and purged with syngas three times, followed by slow stirring after each charge and venting after stirring was stopped. Rh / Ligand 1 stock solution in toluene (0.5 g, 0.58 mL) was then charged into the reactor by syringe. An initial syngas pressure of 40-60 psi was introduced and the temperature was gradually increased to 70 °C with slow stirring. The syngas pressure was then adjusted to about 100 psig and stirring was at about 400 rpm. The reaction was carried out at 70 °C and about 100 psig of syngas. Conversion of substrate 4 reached >99% in 2 hours with N / B=57 as measured by NMR (Table 2 below).

[0145] Example 18: The catalyst precursor (25.8 mg, 0.1 mmol) and Ligand 1 (164.6 mg, 0.2 mmol) were dissolved in nitrogen-purged toluene (100 g) with stirring in a purge box. Pure substrate 2 (25 g, 35.5 mmol) was purged with nitrogen and rapidly introduced into an 80 mL open reactor under a nitrogen blanket. The reactor was sealed and purged with syngas three times, followed by slow stirring after each charge and venting after stirring was stopped. The Rh / Ligand 1 stock solution in toluene (2.5 g, 2.9 mL) prepared above was then charged into the reactor by syringe. An initial syngas pressure of 40-60 psi was charged and the temperature was gradually increased to 70 °C with slow stirring. The syngas pressure was then adjusted to about 100 psig and stirring was at about 400 rpm. The reaction was carried out at 70 °C and about 100 psig of syngas. As determined by NMR, the conversion of substrate 2 reached 100% in 2 hours with N / B=98 (as shown in Table 2 below).

[0146] Example 19: Catalyst precursor (25.8 mg, 0.1 mmol) and Ligand 1 (164.6 mg, 0.2 mmol) were dissolved in nitrogen-purged toluene (100 g) with stirring in a purge box. Substrate 3 (10 g) was mixed with hexane (15 g, 22.8 mL), purged with nitrogen, and introduced into a 150 mL open reactor under a nitrogen blanket. The reactor was sealed and purged with syngas three times, followed by slow stirring after each charge and venting after stirring was stopped. The Rh / Ligand 1 stock solution in toluene (0.5 g, 0.58 mL) prepared above was then charged into the reactor via syringe. An initial syngas pressure of 40-60 psi was introduced and the temperature was gradually increased to 70 °C with slow stirring. The syngas pressure was then adjusted to about 100 psig and stirring was increased to about 400 rpm. The reaction was carried out at 70° C. and approximately 100 psig syngas, and the conversion of substrate 3 reached 63% in 2 hours as measured by NMR (listed in Table 2 below).

[0147] Examples 20 and 21: Examples 20 and 21 follow the process of Example 19, except that Examples 20 and 21 use different concentrations of Rh (but the same Rh / ligand ratio). The reaction parameters and results (measured by NMR) for Examples 20 and 21 are shown in Table 2 below.

[0148] Example 22: Catalyst precursor (25.8 mg, 0.1 mmol) and Ligand 1 (164.6 mg, 0.2 mmol) were dissolved in nitrogen-purged toluene (100 g) with stirring in a purge box. Pure substrate 5 (25 g, 32.6 mmol) was purged with nitrogen and rapidly introduced into a 150 mL open reactor under a nitrogen blanket. The reactor was sealed and purged with syngas three times, followed by slow stirring after each charge and venting after stirring was stopped. Rh / Ligand 1 stock solution in toluene (5 g, 5.8 mL) was then charged into the reactor by syringe. An initial syngas pressure of 40-60 psi was introduced and the temperature was gradually increased to 70 °C with slow stirring. The syngas pressure was then adjusted to about 100 psig and stirring was at about 400 rpm. The reaction was carried out at 70 °C and about 100 psig of syngas. As measured by NMR, the conversion of substrate 5 reached 98% in 2 hours with N / B=63 (as shown in Table 2 below).

[0149] Example 23: Catalyst precursor (25.8 mg, 0.1 mmol) and Ligand 1 (164.6 mg, 0.2 mmol) were dissolved in nitrogen-purged toluene (100 g) with stirring in a purge box. Pure substrate 7 (25 g, 0.10 mol) was purged with nitrogen and rapidly introduced into a 150 mL open reactor under nitrogen blanket. The reactor was sealed and purged with syngas three times, followed by slow stirring after each charge and venting after stirring was stopped. Rh / Ligand 1 stock solution in toluene (2.5 g, 2.9 mL) was then charged into the reactor by syringe. An initial syngas pressure of 40-60 psi was charged and the temperature was gradually increased to 70 °C with slow stirring. The syngas pressure was then adjusted to about 100 psig and stirring was at about 400 rpm. The reaction was carried out at 70 °C and about 100 psig of syngas. Conversion of substrate 7 reached 100% in 2 hours with N / B=41 as determined by NMR (listed in Table 2 below).

[0150] Example 24 The catalyst precursor (25.8 mg, 0.1 mmol) and Ligand 1 (164.6 mg, 0.2 mmol) were dissolved in nitrogen-purged toluene (100 g) with stirring in a purge box. Pure substrate 6 (25 g, 0.134 mol) was purged with nitrogen and rapidly introduced into a 150 mL open reactor under a nitrogen blanket. The reactor was sealed and purged with syngas three times, followed by slow stirring after each charge and venting after stirring was stopped. The Rh / Ligand 1 stock solution in toluene (2.5 g, 2.9 mL) was then charged into the reactor by syringe. An initial syngas pressure of 40-60 psi was charged and the temperature was gradually increased to 70 °C with slow stirring. The syngas pressure was then adjusted to about 100 psig and stirring to about 400 rpm. The reaction was run at 70 °C and about 100 psig of syngas. As determined by NMR, conversion of substrate 6 reached 100% in 2 hours with N / B=46 (as shown in Table 2 below).

[0151] Example 25: The catalyst precursor (25.8 mg, 0.1 mmol) and ligand 10 (97.9 mg, 0.1 mmol) were dissolved in nitrogen-purged toluene (100 g) with stirring in a purge box. Pure substrate 6 (25 g, 0.134 mol) was purged with nitrogen and rapidly introduced into a 150 mL open reactor under a nitrogen blanket. The reactor was sealed and purged with syngas three times, followed by slow stirring after each charge and venting after stirring was stopped. The Rh / ligand 10 stock solution in toluene (2.5 g, 2.9 mL) was then charged into the reactor by syringe. An initial syngas pressure of 40-60 psi was charged and the temperature was gradually increased to 70 °C with slow stirring. The syngas pressure was then adjusted to about 100 psig and stirring was at about 400 rpm. The reaction was carried out at 70 °C and about 100 psig of syngas. As measured by NMR, the conversion of substrate 6 reached 100% in 6 hours with N / B=95 (as shown in Table 2 below).

[0152] Example 26: Catalyst precursor (25.8 mg, 0.1 mmol) and Ligand 1 (164.6 mg, 0.2 mmol) were dissolved in nitrogen-purged toluene (100 g) with stirring in a purge box. Substrate 8 (8.5 g, 0.085 mol) was mixed with toluene (8.5 g, 9.8 mL), purged with nitrogen, and rapidly introduced into a 150 mL open reactor under a nitrogen blanket. The reactor was sealed and purged with syngas three times, followed by slow stirring after each charge and venting after stirring was stopped. Rh / Ligand 1 stock solution in toluene (0.85 g, 0.98 mL) was then charged to the reactor by syringe. An initial syngas pressure of 40-60 psi was charged and the temperature was gradually increased to 70 °C with slow stirring. The syngas pressure was then adjusted to approximately 100 psig and stirring was increased to approximately 400 rpm. The reaction was carried out at 70° C. and approximately 100 psig syngas, and the conversion of substrate 8 reached 99% in 4 hours with N / B=147 as measured by NMR (listed in Table 2 below).

[0153] Example 27: Catalyst precursor (25.8 mg, 0.1 mmol) and Ligand 1 (164.6 mg, 0.2 mmol) were dissolved in nitrogen-purged toluene (100 g) with stirring in a purge box. Substrate 9 (11.25 g) was mixed with toluene (11.25 g, 13 mL), purged with nitrogen, and rapidly introduced into a 150 mL open reactor under a nitrogen blanket. The reactor was sealed and purged with syngas three times, followed by slow stirring after each charge and venting after stirring was stopped. Rh / Ligand 1 stock solution in toluene (2.5 g, 2.9 mL) was then charged to the reactor via syringe. An initial syngas pressure of 40-60 psi was charged and the temperature was gradually increased to 90 °C with slow stirring. The syngas pressure was then adjusted to approximately 100 psig and stirring was increased to approximately 400 rpm. The reaction was carried out at 90° C. and approximately 100 psig syngas. At 2 hours, there was only 1% conversion of substrate 9. The reaction mixture was cooled to room temperature and an additional amount of Rh / Ligand 1 stock solution in toluene (2.5 g, 2.9 mL) was introduced into the reactor via syringe. The reaction was continued at 90° C. and approximately 100 psig syngas, and at 4 hours, there was 100% conversion of substrate 9 as measured by NMR (listed in Table 2 below).

[0154] Example 28: Catalyst precursor (25.8 mg, 0.1 mmol) and Ligand 1 (164.6 mg, 0.2 mmol) were dissolved in nitrogen-purged toluene (100 g) with stirring in a purge box. Substrate 10 (25 g) was purged with nitrogen and rapidly introduced into a 150 mL open reactor under a nitrogen blanket. The reactor was sealed and purged with syngas three times, followed by slow stirring after each charge and venting after stirring was stopped. Rh / Ligand 1 stock solution in toluene (2.5 g, 2.9 mL) was then charged to the reactor via syringe. An initial syngas pressure of 40-60 psi was charged and the temperature was gradually increased to 90 °C with slow stirring. The syngas pressure was then adjusted to about 100 psig and stirring was at about 400 rpm. The reaction was run at 90 °C and about 100 psig of syngas. Conversion of substrate 10 reached 100% in 2 hours as measured by NMR (listed in Table 2 below).

[0155] Comparative Example 1 The catalyst precursor (25.8 mg, 0.1 mmol) and comparative ligand 1 (524.6 mg 2 mmol) were dissolved in nitrogen-purged toluene (200 g, 230.7 mL) with stirring in a purge box. Pure substrate 1 (25 g, 1.67 mmol) was purged with nitrogen and rapidly introduced into a 150 mL open reactor under a nitrogen blanket. The reactor was sealed and purged with syngas three times, followed by slow stirring after each charge and venting after stirring was stopped. The Rh / comparative ligand 1 catalyst stock solution in toluene (2.5 g, 2.88 mL) was then charged into the reactor by syringe. Under an initial syngas pressure of about 50 psi, the temperature was gradually increased to 90° C. with slow stirring. The syngas pressure was then adjusted to about 100 psig and stirring was at about 400 rpm. The reaction was carried out at 90° C. and about 100 psig syngas. As measured by NMR, conversion of Substrate 1 reached 96% at 1 hour and was 100% at 2 hours with N / B=2.6 (as shown in Table 2 below).

[0156] Comparative Example: 2 The catalyst precursor (25.8 mg, 0.1 mmol) and comparative ligand 2 (405 mg, 2 mmol) were dissolved in nitrogen-purged toluene (100 g, 115.3 mL) with stirring in a purge box. Pure substrate 1 (25 g, 1.67 mmol) was purged with nitrogen and rapidly introduced into a 150 mL open reactor under a nitrogen blanket. The reactor was sealed and purged with syngas three times, followed by slow stirring after each charge and venting after stirring was stopped. The Rh / comparative ligand 2 catalyst stock solution in toluene (2.5 g, 2.88 mL) was then charged into the reactor by syringe. Under an initial syngas pressure of about 50 psi, the temperature was gradually increased to 90° C. with slow stirring. The syngas pressure was then adjusted to about 100 psig and stirring was at about 400 rpm. The reaction was carried out at 90° C. and about 100 psig syngas. As measured by NMR, the conversion of Substrate 1 reached 100% in 2 hours with N / B=2.3 (as shown in Table 2 below).

[0157] Comparative Examples 3 and 4: Comparative Examples 3 and 4 follow the process of Comparative Example 2, except that Comparative Examples 3 and 4 use different concentrations of Rh (but the same Rh / ligand ratio). The reaction parameters and results (measured by NMR) for Comparative Examples 3 and 4 are shown in Table 2 below.

[0158] Comparative Example 5: The catalyst precursor (25.8 mg, 0.1 mmol) and comparative ligand 3 (167.8 mg, 0.2 mmol) were dissolved in nitrogen-purged toluene (100 g) with stirring in a purge box. Pure substrate 1 (25 g, 1.67 mmol) was purged with nitrogen and rapidly introduced into a 150 mL open reactor under a nitrogen blanket. The reactor was sealed and purged with syngas three times, followed by slow stirring after each charge and venting after stirring was stopped. Then, Rh / comparative ligand 2 stock solution in toluene (1.25 g, 1.44 mL) was charged into the reactor by syringe. Under an initial syngas pressure of about 40-60 psi, the temperature was gradually increased to 70 °C with slow stirring. The syngas pressure was then adjusted to about 100 psig and stirring was at about 400 rpm. The reaction was carried out at 70 °C and about 100 psig of syngas. Conversion reached 100% in 2 hours with N / B=17 as determined by NMR (reported in Table 2 below).

[0159] Comparative Examples 6 to 8: Comparative Examples 6-8 follow the process of Comparative Example 5, except that Comparative Examples 6-9 use different concentrations of Rh (but the same Rh / ligand ratio). The reaction parameters and results (measured by NMR) for Comparative Examples 6-9 are shown in Table 2 below.

[0160] In Table 2 below, CE indicates comparative example, CL indicates comparative ligand, L / Rh indicates the molar ratio of the specific ligand utilized relative to the Rh content in the catalyst precursor, and N / B is the ratio of the target linear aldehyde product to the branched aldehyde by-product.

[0161] [Table 2-1]

[0162] [Table 2-2] 1 The Rh / L catalyst was preactivated; 2 40% solution; 3 50% solution; 4 58% solution.

[0163] Example 29: Catalyst precursor (25.8 mg, 0.1 mmol) was dissolved in nitrogen-purged toluene (100 g) to obtain a solution. Ligand 1 (20.6 mg, 0.025 mmol) was dissolved in 12.5 g (14.4 mL) of this solution with stirring under nitrogen. This mixture was diluted 8-fold by adding 87.5 g (100.9 mL) of toluene. Approximately 30-50 mL of this solution was transferred to a 150 mL Parr reactor #1 and maintained at 70 °C under 100 psig syngas for 30 min. Pure substrate 1 (25 g, 1.67 mmol) was purged with nitrogen and rapidly introduced into a 150 mL open Parr reactor #2 under a nitrogen blanket. The reactor was sealed and purged with syngas three times, followed by stirring at low speed after each charge and venting after stirring was stopped. A portion of the activated Rh / Ligand 1 stock solution in toluene (0.5 g, 0.58 mL) was then charged from reactor #1 to reactor #2 via syringe. An initial syngas pressure of 40-60 psi was introduced and the temperature was gradually increased to 70° C. with slow stirring. The syngas pressure was then adjusted to about 100 psig and the stirring was at about 400 rpm. The reaction was run at 70° C. and about 100 psig syngas. The results are listed in Table 3 below.

[0164] Examples 30 to 33: Examples 30-33 follow the same process as Example 29, except that different ligands, as set forth in Table 3 below, were used, along with different concentrations of Rh utilized, different temperatures, and different reaction times, also set forth in Table 3 below.

[0165] [Table 3]

[0166] All amounts, ratios, and percentages are by weight unless otherwise specified. The Summary and Abstract are incorporated herein by reference. The transitional phrases "comprising," "consisting essentially of," and "consisting of" are used as set forth in Sections §2111.03 I., II., and III of the Manual of Patent Examining Procedure Ninth Edition, Revision 08.2017, Last Revised January 2018. Abbreviations used herein have the definitions in Table 4.

[0167] [Table 4]

[0168] Issues to be resolved The lack of a good catalytic system constitutes a significant challenge to the commercialization of hydroformylation processes for organosilicon compounds. Previously proposed processes suffer from one or more of the following shortcomings: slow reaction rate, low linear selectivity, and high catalyst loading. A slow reaction rate leads to low productivity. A high catalyst loading used would lead to difficulties in catalyst recycling. A low linear selectivity would ultimately lead to product decomposition, since branched products tend to undergo the Brook rearrangement reaction.

[0169] The present hydroformylation process offers one or more advantages over previously proposed processes, namely faster reaction rates, improved selectivity, and lower catalyst loadings to achieve these. As shown in the above examples, the hydroformylation process can produce a reaction product comprising a) a first organosilicon compound comprising linear aldehyde functional moieties, and b) a second organosilicon compound comprising branched aldehyde functional moieties, wherein the molar ratio of linear aldehyde functional moieties / branched aldehyde functional moieties (N / I ratio) is >25, alternatively >30.

Claims

1. A process for preparing an aldehyde-functional organosilicon compound, wherein the process comprises: Under conditions that catalyze the hydroformylation reaction, (A) A gas containing hydrogen and carbon monoxide, (B) A vinyl-functional organosilicon compound having at least one vinyl group covalently bonded to silicon, (C) A rhodium / ligand complex catalyst wherein the ligand is of formula (C1), (C2), and / or (C3): 【Chemistry 1】 (wherein, R １ ~R ２２ are each independently selected from hydrogen, a hydrocarbyl group, a heteroaryl group, a halogen atom, or a heterocarbyl group, and two or more of R １ ~R ２２ may optionally be joined together to provide one or more cyclic moieties, and each of X １ ~X ４ is independently selected from O, CH ２ , NH, NR, NSO ２ R, or NSO ２ A, wherein each R is an independently selected substituted or unsubstituted alkyl or aryl group, each A is an independently selected aryl or heteroaryl group, and each of Y １ ~Y ８ is an independently selected nitrogen-containing heterocyclic moiety bonded to P via N, wherein each heterocyclic moiety may be substituted with one or more groups or atoms selected from alkyl, aryl, heteroaryl, alkoxy, acyl, carboxyl, carboxylate, cyano, -SO ３ H, sulfonate, amino, trifluoromethyl, and halogen), and a starting material containing a rhodium / ligand complex catalyst, the process comprising combining the starting materials.)

2. The starting material (B) is given by formula (B1): R Ａ ｘ SiR ２３ （４－ｘ） (In the formula, each R Ａ It is a vinyl group, and each R ２３ The process according to claim 1, wherein the vinyl functionalized silane is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, an acyloxy group of 2 to 18 carbon atoms, and a hydrocarbon oxy functional group of 1 to 18 carbon atoms, wherein the subscript x is 1 to 4.

3. The vinyl-functional organosilicon compound has the unit formula (B2-1): (R ２３ ３ SiO １／２ ) ａ (R ２３ ２ R Ａ SiO １／２ ) ｂ (R ２３ ２ SiO ２／２ ) ｃ (R ２３ R Ａ SiO ２／２ ) ｄ (R ２３ SiO ３／２ ) ｅ (R Ａ SiO ３／２ ) ｆ (SiO ４／２ ) ｇ (ZO １／２ ) ｈ (In the formula, each R Ａ It is a vinyl group, and each R ２３ Each Z is independently selected from the group consisting of alkyl groups with 1 to 18 carbon atoms, aryl groups with 6 to 18 carbon atoms, acyloxy groups with 2 to 18 carbon atoms, and hydrocarbonoxy groups with 1 to 18 carbon atoms, and each Z is independently a hydrogen atom and R ２４ Selected from the group consisting of each R ２４ The process according to claim 1, wherein the polyorganosiloxane is independently selected from the group consisting of alkyl groups of 1 to 18 carbon atoms and aryl groups of 6 to 18 carbon atoms, and the subscripts a, b, c, d, e, f, and g represent the number of each unit in formula (B2-1), with values ​​such as a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, and g≧0, and the subscript h has values ​​such as 0≦h / (e+f+g)≦1.5, 10,000≧(a+b+c+d+e+f+g)≧2, and quantity(b+d+f)≧1.

4. The vinyl-functional polyorganosiloxane is cyclic and has the unit formula (R ２３ R Ａ SiO ２／２ ), ｄ where the subscript d is from 3 to 12, (R ２３ ２ SiO ２／２ ), ｃ’ (R ２３ R Ａ SiO ２／２ ), ｄ where c' is greater than 0 to 6 and d is from 3 to 12, and is selected from the group consisting of these combinations, or the vinyl-functional polyorganosiloxane is linear and has the unit formula (B3): (R ２３ ３ SiO １／２ ), ａ (R ２３ ２ R Ａ SiO １／２ ), ｂ (R ２３ ２ SiO ２／２ ), ｃ (R ２３ R Ａ SiO ２／２ ), ｄ where the amount (a + b) = 2, the amount (b + d) ≥ 1, and the amount (a + b + c + d) ≥ 2, or the vinyl-functional polyorganosiloxane has the unit formula: (R ２３ ３ SiO １／２ ), ｍｍ (R ２３ ２ R Ａ SiO １／２ ), ｎｎ (SiO ４／２ ), ｏｏ (ZO １／２ ), ｈ (wherein the subscripted letters mm, nn, and oo represent the molar percentages of each unit in the polyorganosilicate resin, and the subscripted letters mm, nn, and oo have average values such that mm ≥ 0, nn ≥ 0, oo > 0, and 0.5 ≤ (mm + nn) / oo ≤ 4), or the vinyl-functional polyorganosiloxane is of the unit formula: (R ２３ ３ SiO １／２ ) ａ (R ２３ ２ R Ａ SiO １／２ ) ｂ (R ２３ ２ SiO ２／２ ) ｃ (R ２３ R Ａ SiO ２／２ ) ｄ (R ２３ SiO ３／２ ) ｅ (R Ａ SiO ３／２ ) ｆ (ZO １／２ ) ｈ (wherein f > 1, 2 < (e + f) < 10,000, 0 < (a + b) / (e + f) < 3, 0 < (c + d) / (e + f) < 3, and 0 < h / (e + f) < 1.5), which is a vinyl-functional silsesquioxane resin, the process according to claim 3.)

5. Each R ２３ The process according to claim 3 or 4, wherein the following are independently selected from the group consisting of methyl and phenyl.

6. The process according to claim 1, wherein the vinyl-functionalized organosilicon compound comprises a vinyl-functionalized silazane.

7. The starting material (C) has the following structure: 【Chemistry 2】 【Transformation 3】 The process according to claim 1, comprising one of the following (wherein Me represents methyl and tBu represents t-butyl).

8. The process according to claim 1, wherein the starting material (C) has a ligand / Rh molar ratio of 1 / 1 to 10 / 1.

9. The above condition is, i) Temperatures between 30°C and 150°C, ii) Pressures from 101 kPa to 6,895 kPa, iii) The molar ratio of CO / H2 in synthesis gas 3 / 1 to 1 / 3, and The process according to claim 1, selected from the group consisting of two or more combinations of conditions i), ii), and iii).

10. The process according to claim 1, wherein the starting material (C) is formed by combining a rhodium precursor with the ligand to form a rhodium / ligand complex, and then combining the rhodium / ligand complex with the starting material (A) while heating.

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