Process for synthesizing organosilicon compounds from halosilanes

Abstract

Provided herein is a process for synthesizing organosilicon compounds. Also provided herein are novel organosilicon compounds prepared by the process. The process involves the reaction of a halosilane with an organofunctional alkyl halide in the presence of a metal catalyst, a promoter, and an optional cocatalyst. The process provides an efficient synthetic route to producing organosilicon compounds. The process also allows for the synthesis of organosilicon compounds with multiple different functional groups.

Description

[Technical Field]

[0001] Cross-reference to related applications This application claims priority and benefits of Provisional Application for Registration of Indian Patents No. 202021031933, filed on 25 July 2020, the entirety of which disclosures are incorporated herein by reference.

[0002] This invention relates to a process for synthesizing organosilicon compounds. In particular, this invention relates to a process for synthesizing organosilicon compounds by reacting halosilane with an organically functional alkyl halide. [Background technology]

[0003] Organosilicon compounds are a very important type of compound not only in organic chemistry but also in other fields of chemistry, such as materials science, medicinal chemistry, agricultural chemistry, and others. Two of the best-known processes for synthesizing organosilicon compounds are (i) hydrosilylation of olefins with silicon hydride, and (ii) cross-coupling (Grignard reaction) between organometallic compounds and silicon halides. Another process for synthesizing organosilicon compounds is (iii) cross-coupling with alkyl halides and silicon-metal complexes. Each of these processes has its own advantages, but at the same time, they also have disadvantages that limit the widespread use of these reactions on an industrial scale.

[0004] Hydrosilylation has been the most promising of the above processes for the synthesis of organosilicon compounds due to its atomic efficiency during the process. However, hydrosilylation has several limitations, including the formation of an internal carbon-carbon double bond as a result of olefin isomerization, partial hydrogenation, insufficient regioselectivity (1,2-addition or 1,4-addition), limited availability of various Si-H materials, and limitations on the functional groups that can be used because certain functional groups can interact with the catalyst and act as catalyst poisons. Organomagnesium (Grignard reagents) are well-known and widely used organonucleophiles for reaction with silicon electrophiles (e.g., chlorosilanes). However, due to their high reactivity, insufficient selectivity, and poor functional group tolerance, this process has not been adopted as the mainstream for specialized products on an industrial scale. Therefore, there is a need for a process for the synthesis of organosilicon compounds that overcomes the aforementioned shortcomings. [Overview of the project]

[0005] The following outline provides a summary of the disclosure to give a basic understanding of several embodiments. This outline is not intended to identify essential or important elements, nor to impose any limitations on the embodiments or claims. Furthermore, this outline may provide a simplified overview of some embodiments, which may be described in more detail in other parts of the disclosure.

[0006] Provided is a process for synthesizing organosilicon compounds. In one embodiment, this process provides an efficient synthetic route for producing organosilicon compounds using halosilane as a starting material. This process allows for the synthesis of organosilicon compounds with various organofunctional groups.

[0007] In one embodiment, provided is a process for synthesizing an organosilicon compound from the reaction of a halosilane and an organofunctional alkyl halide in the presence of a non-magnesium metal, an accelerator, and an optional catalyst.

[0008] In one embodiment, provided is an organosilicon compound of formula (1) [(R 1 )-(C(R 2 )(R 3 )) m p -Si(R 4 ) 4-n (X 1 ) n-p (1) by reacting a halosilane of formula (2) (X 1 ) n -Si(R 4 ) 4-n (2) with p moles of an organofunctional alkyl halide of formula (3): [(R 1 )-(C(R 2 )(R 3 )) m -X 2 (3) wherein R 1 is C1-C20 alkyl, -CR 5 =CR 6 2, -C≡CR 7 , -CN, -C(O)R 8 , -OC(O)R 9 , -C(O)OR [[ID=6M]]<00000M> 10 , -SR 11 , -S(O)2R 12 , -NR 13 2, -C(O)NR 14 2, -OC(O)-CR 15 =R 16 2, -CF3, -(CR 17 2)n-CF3, -NCO, -CS-OR 18 , -CSSR 19 , -NR 20 C(O)-CR 21 =CR 22 2, C6-C20 A functional group independently selected from aryl, aralkyl, or alkaryl, where R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 18 , R 19 , R 20 , R 21 , and R 22 Each of these is independently H, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C30 aryl, aralkyl, or alkaryl, and R 17 is H or C1-C10 alkyl; R 2 is H or C1-C20 alkyl; R 3 is H or C1-C20 alkyl; R 4 C1-C20 alkyl groups; X 1 is F, Cl, Br, or I; X 2 is F, Cl, Br, or I; m is an integer between 1 and 10; n is an integer in the range of 1 to 4; and p is an integer between 1 and 4, provided that p is ≤ n.

[0009] In one embodiment, R 1 C1-C20 alkyl, -CR 5 =CR 6 2. -C≡CR 7 -CN, -C(O)R 8 -OC(O)R 9 , -C(O)OR 10 , -SR 11 -S(O)2R 12 , -NR 13 2, -C(O)NR 14 2. -OC(O)-CR15 =R 16 2, -CF3, -(CR 17 2)n-CF3, -NCO, -CS-OR 18 , -CSSR 19 , -NR 20 C(O)-CR 21 =CR 22 2, C6-C 20 are independently selected from aryl, aralkyl, or alkaryl, where R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 18 , R 19 , R 20 , R 21 , and R 22 are each independently H, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C30 aryl, aralkyl, or alkaryl, and R 17 is H, C1-C10 alkyl, or F.

[0010] In one embodiment of the process of any of the above-described embodiments, the non-magnesium metal is selected from alkali metals, alkaline earth metals excluding magnesium, transition metals, post-transition metals, metalloids, lanthanoids, or combinations of two or more thereof.

[0011] In one embodiment of the process of any of the above-described embodiments, the non-magnesium metal is selected from Li, Na, K, Rb, Cs, Be, Ca, Sr, Ba, Fe, Co, Ni, Cu, Zn, B, Sb, Te, La, Ce, Sm, or combinations of two or more thereof. In one embodiment, the non-magnesium metal is Zn.

[0012] In one embodiment of the process of any of the embodiments described above, the molar ratio of the non-magnesium metal to the organic functional alkyl halide is in the range of 0.5:1 to 1:1.5.

[0013] In one embodiment of the process of any of the embodiments described above, the accelerator is a phosphorus-containing compound, a sulfur-containing compound, or a combination of two or more of these.

[0014] In one embodiment of the process of any of the embodiments described above, the accelerator is selected from phosphine oxide, phosphate, phosphate, phosphine, phosphoramide, or a combination of two or more of these.

[0015] In one embodiment of the process of any of the above embodiments, the phosphine oxide is of formula R 20 3P=O, and in the formula R 20 Each of these is independently a C4-C20 alkyl, C3-C20 cyclic alkyl, aralkyl, or alkaryl.

[0016] In one embodiment of the process of any of the embodiments described above, the accelerator is tributylphosphine oxide (TBPO), trioctylphosphine oxide (TOPO), hexamethylphosphoramide (HMPA), trimorpholinophosphine oxide, tripyrrolidinophosphine oxide, or a combination thereof.

[0017] In one embodiment of the process of any of the above embodiments, the accelerator is of formula (R 21 It is a phosphoramide of 2N)3P=O, and in the formula R 21 Each of these is independently a C1-C10 alkyl or a C3-C20 cyclic alkyl.

[0018] In one embodiment of the process of any of the above embodiments, the process further includes the use of a catalyst.

[0019] In one embodiment, the catalyst is a metal selected from metal halides, metal acetates, metal esters, metal amides, metal triflates, metal borates, metal nitrates, or two or more combinations thereof. In one embodiment, the metal halide includes a metal selected from alkali metals, alkaline earth metals excluding magnesium, transition metals, post-transition metals, metalloids, lanthanides, or two or more combinations thereof. In one embodiment, the catalyst is a metal iodide. In one embodiment, the catalyst is X 2 This is used when the value is Cl.

[0020] In one embodiment of the process of any of the embodiments described above, the halosilane is reacted with an alkyl halide at a temperature in the range of about 10°C to about 200°C. In one embodiment, the halosilane is reacted with an alkyl halide at a temperature in the range of about 70°C to about 100°C.

[0021] In one embodiment, the synthesis of organosilicon compounds having multiple functional groups is enabled. In one embodiment, the organosilicon compound contains at least two organic functional groups that are distinct from each other.

[0022] Another embodiment provides a process for synthesizing organosilicon compounds having at least two different organic functional groups: (i) Formula (X 1 ) n -Si(R 4 ) 4-n The formula for p moles of halosilane [(R 1 )-(C(R 2 )(R 3 )) m ]-X 2 The first organofunctional alkyl halide is reacted with the formula [(R 1 )-(C(R 2 )(R 3 )) m ] p -Si(R 4 ) 4-n (X1) n-p This produces the first organosilicon compound; and (ii) The first organosilicon compound [(R 1 )-(C(R 2 )(R 3 )) m ] p -Si(R 4 ) 4-n (X 1 ) n-p The formula for p' moles [(R 1’ )-(C(R 2’ )(R 3’ )) m’ ]-X 2’ Reacting with a second organofunctional alkyl halide, the formula ([(R 1 )-(C(R 2 )(R 3 )) m ] p )([(R 1’ )-(C(R 2’ )(R 3’ )) m’ ] p’ )(-Si(R 4 ) 4-n (X 1 ) n-p-p’ This includes generating a second organosilicon compound, R in the formula 1 and R 1’ Each of these is an independently independent organic functional group; R 2 and R 2’ Each is independently H or C1-C20 alkyl; R 3 and R 3’ Each is independently H or C1-C20 alkyl; R 4 C1-C20 alkyl groups; X 1 is F, Cl, Br, or I; X 2 and X 2’ These are F, Cl, Br, or I, respectively, independently. m and m' are each independently 1 to 10; n is 1 to 4; p is between 1 and 4, but p is ≤ n; Here R 1’is R 1 Unlike; R 2’ is R 2 It is either identical or different from; R 3’ is R 3 m' is either identical or different from m, m' is either identical or different from m, and p' is ≤(np).

[0023] One embodiment provides a compound of formula (1): [(R 1 )-(C(R 2 )(R 3 )) m ] p -Si(R 4 ) 4-n (X 1 ) n-p (1) R in the formula 1 is an organic functional group; R 2 is H or C1-C20 alkyl; R 3 is H or C1-C20 alkyl; R 4 C1-C20 alkyl groups; X 1 is F, Cl, Br, or I; m is an integer between 1 and 10; n is an integer in the range of 1 to 4; and p is an integer between 1 and 4, provided that p is ≤ n.

[0024] In one embodiment of this compound, m is an integer in the range of 3 to 10.

[0025] In one embodiment of this compound, p is an integer in the range of 2 to 4.

[0026] In one embodiment of this compound, p is 3.

[0027] In one embodiment of this compound, m is an integer in the range of 3 to 10, and p is an integer in the range of 2 to 4.

[0028] In one embodiment of this compound, R 1 C1-C20 alkyl, -CR 5 =CR 6 2. -C≡CR 7 -CN, -C(O)R 8 -OC(O)R 9 , -C(O)OR 10 , -SR 11 -S(O)2R 12 , -NR 13 2, -C(O)NR 14 2. -OC(O)-CR 15 =R 16 2, -CF3, -(CR 17 2) n-CF3, -NCO, -CS-OR 18 ,-CSSR 19 , -NR 20 C(O)-CR 21 =CR 22 2. C6-C 20 Selected independently from aryl, aralkyl, or alkaryl, where R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 18 , R 19 , R 20 , R 21 , and R 22 Each of these is independently H, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C30 aryl, aralkyl, or alkaryl, and R 17 is H, C1-C10 alkyl, or F.

[0029] In one embodiment of this compound, R 1 -C≡CR 7 , -C(O)R 8 , -C(O)OR 10 , -SR 11 , -CS-OR 18 ,-CSSR19 , -NR 20 C(O)-CR 21 =CR 22 2. C6-C 20 Selected independently from Aralquil, or Alkaliar, where R 7 , R 8 , R 10 , R 11 , R 18 , R 19 , R 20 , R 21 , and R 22 Each of these is independently H, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C30 aryl, aralkyl, or alkaryl, and R 17 is H, C1-C10 alkyl, or F.

[0030] In one embodiment of this compound, X in formula 1 It is Cl.

[0031] The following description is illustrative of various embodiments. Some improvements and novel aspects may be explicitly identified, while other aspects may be evident from the description and drawings. [Modes for carrying out the invention]

[0032] Referencing the following exemplary embodiments, examples are illustrated in the accompanying drawings. As will be understood, other embodiments may also be used, and structural and functional modifications may be made. Furthermore, features of various embodiments may be combined or modified. Thus, the following description is presented merely as an example and does not in any way limit the various alternatives or modifications that may be made to the exemplary embodiments. In this disclosure, several specific details will lead to a complete understanding of the disclosed subject matter. It should be understood that embodiments of this disclosure may be implemented in other embodiments that do not necessarily include all aspects described in this application or elsewhere.

[0033] As used in this application, the terms “example” and “illustration” mean examples or illustrations. The terms “example” and “illustration” do not indicate essential or preferred embodiments or forms. The term “or” is intended to be inclusive, not exclusive, unless the context suggests otherwise. For example, the statement “A uses B or C” includes any inclusive substitution (e.g., A uses B; A uses C; or A uses both B and C). Separately, the articles “one” and “a” are generally intended to mean “one or more,” unless the context suggests otherwise.

[0034] As used in this application, the term "alkyl" includes linear alkyl groups, branched alkyl groups, and cyclic alkyl groups. Specific and non-limiting examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, nonyl, decyl, and others. In embodiments, alkyl groups are selected from C1-C30 alkyl groups, C1-C18 alkyl groups, C2-C10 alkyl groups, and even C4-C6 alkyl groups. In embodiments, alkyl groups are selected from C1-C6 alkyl groups.

[0035] As used in this application, the term “substituted alkyl” refers to an alkyl group containing one or more substituents that are inert under the processing conditions imposed on the compound containing those groups. These substituents also do not substantially interfere with the processes described herein. In some embodiments, the substituted alkyl group is a C1-C18 substituted alkyl group. In other embodiments, it is a C1-C10 substituted alkyl group. Substituents of such alkyl groups include, but are not limited to, the inert functional groups described herein.

[0036] As used in this application, the term “aryl” refers to a non-limiting group of any aromatic hydrocarbons from which one hydrogen atom has been removed. Aryls may have one or more aromatic rings that are fused or connected by single bonds or other groups. Specific and non-limiting examples of aryls include, but are not limited to, tolyl, xylyl, phenyl, and naphthalenyl. In embodiments, the aryl group may be selected from C6-C30 aryls, C6-C20 aryls, and even C6-C10 aryls.

[0037] As used in this application, the term “substituted aryl” refers to an aromatic group containing one or more substituents that is inert under the processing conditions imposed on the substituent-containing compound. These substituents also do not substantially interfere with the processes described herein. Like aryls, substituted aryls may have one or more aromatic rings that are fused or connected by single bonds or other groups; however, if the substituted aryl has heteroaromatic rings, the free valence in the substituted aryl group may be for heteroatoms (such as nitrogen) of the heteroaromatic ring, rather than for carbon atoms. Unless otherwise specified, substituents of substituted aryl groups may contain 0 to about 30 carbon atoms, specifically 0 to 20 carbon atoms, and more specifically 0 to 10 carbon atoms. In one embodiment, the substituents are selected from the inert groups described herein.

[0038] As used in this application, the term “alkenyl” refers to any linear, branched, or cyclic alkenyl group containing one or more carbon-carbon double bonds, wherein the substitution site may be either a carbon-carbon double bond or another site within the group. Specific and non-limiting examples of alkenyls include, but are not limited to, vinyl, propenyl, allyl, methallyl, and ethylidenylnorbornane.

[0039] As used in this application, the term "alkaryl" refers to an aryl group containing one or more alkyl substituents. Non-limiting examples of alkaryl compounds include tolyl, xylyl, and others.

[0040] As used in this application, the term "aralkyl" refers to an alkyl group in which one or more hydrogen atoms are substituted by an equal number of aryl groups, the aryl groups being either identical or distinct from one another. Non-limiting examples of aralkyls include benzyl and phenylethyl.

[0041] As used in this application, the term “organosilicon compound” may be used interchangeably with the term “organofunctional silicon compound,” and includes silicon-based compounds having one or more organic functional groups bonded to a silicon atom. Organosilicon compounds may include organic functional silanes and organic functional siloxanes. Organosilicon compounds may contain multiple organic functional groups, which may be identical or different from each other.

[0042] This disclosure relates to a process for the synthesis of organosilicon compounds and a series of novel organosilicon compounds synthesized by this process. The terms “process” and “method” for synthesizing these compounds are used interchangeably below. The process involves the reaction of a halosilane with an organofunctional alkyl halide. The process provides a useful route for synthesizing a wide range of organosilicon compounds. The process provides an efficient route for synthesizing organosilicon compounds with multiple functional groups. The process also provides a route for synthesizing organosilicon compounds with multiple organic functional groups, wherein the organosilicon compound has at least two distinct organic functional groups.

[0043] This disclosure relates to organosilicon compounds of formula (1). [(R 1 )-(C(R 2 )(R 3 )) m ]p -Si(R 4 ) 4-n (X 1 ) n-p (1) The synthesis of the halosilane of formula (2) (X 1 ) n -Si(R 4 ) 4-n (2) And, p moles of the organic functional alkyl halide of formula (3): [(R 1 )-(C(R 2 )(R 3 )) m ]-X 2 (3) It provides a process that is carried out through a reaction with, where R 1 C1-C20 alkyl, -CR 5 =CR 6 2. -C≡CR 7 -CN, -C(O)R 8 -OC(O)R 9 , -C(O)OR 10 , -SR 11 -S(O)2R 12 , -NR 13 2, -C(O)NR 14 2. -OC(O)-CR 15 =R 16 2, -CF3, -(CR 17 2) n-CF3, -NCO, -CS-OR 18 ,-CSSR 19 , -NR 20 C(O)-CR 21 =CR 22 2. C6-C 20 A functional group independently selected from aryl, aralkyl, or alkaryl, where R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 18 , R19 , R 20 , R 21 , and R 22 Each of these is independently H, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C30 aryl, aralkyl, or alkaryl, and R 17 is H or C1-C10 alkyl; R 2 is H or C1-C20 alkyl; R 3 is H or C1-C20 alkyl; R 4 C1-C20 alkyl groups; X 1 is F, Cl, Br, or I; X 2 is F, Cl, Br, or I; m is an integer between 1 and 10; n is an integer in the range of 1 to 4; and p is an integer between 1 and 4, provided that p is ≤ n. Specifically, n and p may have the following integer values: n=1; p=1 n=2; p=1 n=2; p=2 n=3; p=1 n=3; p=2 n=3; p=3 n=4; p=1 n=4; p=2 n=4; p=3 n=4; p=4

[0044] In one embodiment, R 2 and R 3 is independently selected from H, C1-C20 alkyl, C2-C16 alkyl, C3-C10 alkyl, or C4-C6 alkyl. In one embodiment, R 2 and R 3 These are H, respectively. In one embodiment, R 2 and R 3Each of these is a C1-C4 alkyl group. In embodiments, m is an integer in the range of 1 to 10, 2 to 8, or 4 to 6. In one embodiment, m is an integer in the range of 1 to 4.

[0045] In one embodiment, R 4 is C1-20 alkyl, C2-C16 alkyl, C3-C10 alkyl, or C4-C6 alkyl. In one embodiment, R 4 It is -CH3.

[0046] As shown in the formula, X 1 and X 2 These can be F, Cl, Br, or I, respectively. 1 and X 2 They may be the same or different from each other. In one embodiment, X 1 and X 2 Both are the same halogen atom. In one embodiment, X 1 and X 2 These are both Cl.

[0047] The reaction between the halosilane of formula (2) and the alkylhalide of formula (3) is carried out in the presence of a non-magnesium metal, an optional catalyst, and an accelerator. This reaction may be carried out in a solvent.

[0048] This reaction is typically carried out in the presence of a non-magnesium metal. The non-magnesium metal may be in the form of a metal powder. Examples of non-magnesium metals that may be used include, but are not limited to, alkali metals, alkaline earth metals excluding magnesium, transition metals, post-transition metals, metalloids, lanthanides, or two or more combinations thereof. Suitable alkali metals include Li, Na, K, Rb, and / or Cs. Suitable alkaline earth metals include Be, Ca, Sr, and / or Ba. Suitable transition metals include, but are not limited to, Fe, Co, Ni, Cu, and / or Zn. Suitable metalloids include, but are not limited to, B, Sb, and / or Te. Suitable lanthanides and actinides include, but are not limited to, La, Ce, and / or Sm.

[0049] In one embodiment, the non-magnesium metal is metallic zinc. Advantageously, in one embodiment, the metallic zinc is in powder form.

[0050] In a reaction, the number of moles of non-magnesium metal used must be equal to or greater than the number of moles of organofunctional alkylhalides used in the reaction. For example, if it is desirable to add multiple organofunctional alkyl groups to a silane, the number of moles of the non-magnesium metal must be at least equal to the number of moles of organofunctional alkylhalides used. If, for example, two organofunctional alkyl groups are to be added to a halosilane having two or more halogen groups, then at least two moles of the non-magnesium metal will be used in the reaction.

[0051] In some embodiments of the process, the molar ratio of the non-magnesium metal to the organofunctional alkyl halide is in the range of 0.5:1 to 1:5. In some other embodiments of the process, the molar ratio of the non-magnesium metal to the organofunctional alkyl halide is in the range of 0.5:1 to 1:1.5. In one or more embodiments of the process, the molar ratio of the non-magnesium metal to the organofunctional alkyl halide is at least 1:1. In some other embodiments, the molar ratio of the non-magnesium metal to the organofunctional alkyl halide is 1:1.5.

[0052] In one embodiment, a catalyst is used in a method for forming organosilicon compounds. The catalyst is typically a metal salt. The metal salt is selected from metal halides, metal acetates, metal esters, metal amides, metal triflates, metal borates, metal nitrates, or two or more combinations thereof. The metal salt (catalyst) includes metals selected from alkali metals, alkaline earth metals excluding magnesium, transition metals, post-transition metals, metalloids, lanthanides, or two or more combinations thereof. Suitable alkali metals include Li, Na, K, Rb, and / or Cs. Suitable alkaline earth metals include Be, Ca, Sr, and / or Ba. Suitable transition metals include, but are not limited to, Fe, Co, Ni, Cu, and / or Zn. Suitable metalloids include, but are not limited to, B, Sb, and / or Te. Suitable lanthanides and actinides include, but are not limited to, La, Ce, and / or Sm.

[0053] In one embodiment, the catalyst is selected from metal halides such as alkali metal halides, alkaline earth metal halides, or transition metal halides. In one embodiment, the catalyst is a metal iodide. Some exemplary metal halides include, but are not limited to, ZnI2, LiBr, LiI, KI, NaI, ZnBr2, KBr, NaBr, and others.

[0054] In one embodiment, when alkylhalide (3) is an alkyl chloride (i.e., X 2 If (i.e., ) a catalyst is generally required and should be used in the reaction. In one embodiment, if alkylhalide (3) is alkyl bromide or alkyl iodide (i.e., X 2 The catalyst is optional (if Br or I).

[0055] When a catalyst is used in the reaction: approximately 0.01 mol% to approximately 100 mol%, approximately 0.1 mol% to approximately 90 mol%, approximately 1 mol% to approximately 80 mol%, approximately 5 mol% to approximately 75 mol%, approximately 10 mol% to approximately 60 mol%, approximately 20 mol% to approximately 50 mol%, or approximately 30 mol% to approximately 40 mol% relative to the number of moles of organic functional alkylhalides; approximately 0.01 mol% to approximately 100 mol%, approximately 0.1 mol% to approximately 90 mol%, and approximately 1 mol% to approximately 80 mol% relative to the number of moles of halosilane. It can be present in amounts of approximately 5 mol% to approximately 75 mol%, approximately 10 mol% to approximately 60 mol%, approximately 20 mol% to approximately 50 mol%, or approximately 30 mol% to approximately 40 mol% relative to the number of moles of non-magnesium metal; or approximately 0.01 mol% to approximately 100 mol%, approximately 0.1 mol% to approximately 90 mol%, approximately 1 mol% to approximately 80 mol%, approximately 5 mol% to approximately 75 mol%, approximately 10 mol% to approximately 60 mol%, approximately 20 mol% to approximately 50 mol%, or approximately 30 mol% to approximately 40 mol% relative to the number of moles of non-magnesium metal.

[0056] This process involves accelerators. In this application, the term "accelerator" refers to a compound that facilitates the reaction by removing metal-halide by-products through complex formation, thereby promoting the formation of the desired product.

[0057] The accelerator likely also helps stabilize the metal complex. Some of these accelerators are readily regenerative and recyclable. In some embodiments, the accelerator functions as a non-reactive solvent. In embodiments of this process, the accelerator is typically a phosphorus or sulfur-containing compound. Examples of suitable accelerators include, but are not limited to, phosphine oxides, phosphates, phosphites, phosphonium salts, phosphines, phosphoramides, or two or more combinations thereof.

[0058] In one embodiment, the accelerator is a phosphine oxide. An example of a suitable phosphine oxide is given by formula R 20 It has 3P=O, and in the formula R 20 Each of these is independently selected from C4-C20 alkyl, C3-C20 cyclic alkyl, aralkyl, and alkaryl. Suitable phosphine oxides as accelerators include, but are not limited to, tributylphosphine oxide (TBPO), trioctylphosphine oxide (TOPO), triphenylphosphine oxide (TPPO), and others.

[0059] In one embodiment, the accelerator is a phosphoramide. Examples of suitable phosphoramides include those of formula (R 21 It includes the form 2N)3P=O, and in the formula R 21 R is independently selected from C1-C10 alkyl and C3-C20 cyclic alkyl groups. In one embodiment, R 21 is a C2-8 alkyl, C3-C6 alkyl, or C4-C5 alkyl. In one embodiment, R 21The cyclic alkyl group is a C6 alkyl group. The cyclic alkyl group can be a monovalent (separate) group bonded to a nitrogen atom, or a divalent group that forms a ring with the nitrogen atom as part of the ring. The cyclic alkyl group (whether a separate group or a group that forms a ring with the nitrogen atom) can contain a heteroatom selected from N, O, and S in the ring. In one embodiment, the cyclic alkyl group contains an oxygen atom in the ring structure. Examples of phosphoramides suitable as accelerators include, but are not limited to, hexamethylphosphoramide (HMPA), trimorpholinophosphine oxide, or tripyrrolidinophosphine oxide.

[0060] The accelerator is generally: about 0.01 mol% to about 100 mol%, about 0.1 mol% to about 90 mol%, about 1 mol% to about 80 mol%, about 5 mol% to about 75 mol%, about 10 mol% to about 60 mol%, about 20 mol% to about 50 mol%, or about 30 mol% to about 40 mol% relative to the number of moles of organic functional alkyl halides; about 0.01 mol% to about 100 mol%, about 0.1 mol% to about 90 mol%, or about 1 mol% to about 80 mol% relative to the number of moles of halosilane. It is present in amounts of approximately 5 mol% to approximately 75 mol%, approximately 10 mol% to approximately 60 mol%, approximately 20 mol% to approximately 50 mol%, or approximately 30 mol% to approximately 40 mol% relative to the number of moles of non-magnesium metal; or approximately 0.01 mol% to approximately 100 mol%, approximately 0.1 mol% to approximately 90 mol%, approximately 1 mol% to approximately 80 mol%, approximately 5 mol% to approximately 75 mol%, approximately 10 mol% to approximately 60 mol%, approximately 20 mol% to approximately 50 mol%, or approximately 30 mol% to approximately 40 mol% relative to the number of moles of non-magnesium metal.

[0061] In one or more embodiments, the process is carried out in a solvent. The solvent for this process can be selected as desired and can be optionally selected from a variety of known different solvents. The solvent can be polar or nonpolar. The solvent can be selected from alkane solvents, cyclic alkane solvents, furan solvents, aromatic solvents, acetyl solvents, ester solvents, nitrile solvents, glycol solvents, ether solvents, sulfide solvents, sulfoxide solvents, cyclic amide solvents, formamide solvents, imidazole solvents, ketone solvents, or two or more combinations thereof. When multiple materials are used in the solvent, whether from the same material category (e.g., different alkane solvents) or different material categories, each material can be used in any suitable ratio as desired. A solvent used in smaller amounts than another solvent can be considered and referred to as a “co-solvent”.

[0062] Examples of alkane solvents include, but are not limited to, lower saturated alkanes with 3 to 20 carbon atoms, halogenated saturated alkanes with 4 to 10 carbon atoms, and aromatic hydrocarbons with 6 to 20 carbon atoms. Suitable examples of alkane solvents include, but are not limited to, propane, butane, pentane, heptane, hexane, nonane, decane, and dodecane.

[0063] Examples of cyclic alkane solvents include, but are not limited to, C3-C20 cyclic alkanes such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cyclooctane.

[0064] Suitable aromatic solvents include, but are not limited to, C6-C20 aromatic solvents or C6-C15 aromatic solvents. In one embodiment, the aromatic solvent is selected from toluene, xylene, naphthalene, naphthenic oil, alkylated naphthalene, diphenyl, polychlorinated biphenyl, polycyclic aromatic hydrocarbons, or any combination or mixture thereof.

[0065] Examples of suitable ether solvents include, but are not limited to, diisopropyl ether, diglyme, dimethoxyethane, and others.

[0066] Suitable ester solvents include, but are not limited to, ethyl acetate.

[0067] Examples of suitable nitrile solvents include, but are not limited to, acetonitrile.

[0068] Suitable glycol solvents include, but are not limited to, alkylene glycols, dialkylene glycols, mono and dialkyl ethers of trialkylene glycols, and others. Some examples of glycol solvents include, but are not limited to, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, hexylene glycol, ethylene glycol dimethyl ether, polyethylene glycol alkyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, tripropylene glycol methyl ether, propylene glycol methyl ether (PM), dipropylene glycol methyl ether (DPM), propylene glycol acetate methyl ether (PMA), dipropylene glycol acetate methyl ether (CPMA), propylene glycol n-butyl ether, dipropylene glycol monobutyl ether, ethylene glycol n-butyl ether and ethylene glycol n-propyl ether, and others.

[0069] Suitable sulfide solvents include, but are not limited to, dimethyl sulfide, diethyl sulfide, dipropyl sulfide, dibutyl sulfide, and others. Suitable sulfoxide solvents include, but are not limited to, dimethyl sulfoxide. Suitable cyclic amide solvents include, but are not limited to, N-methylpyrrolidone. Suitable formamide solvents include, but are not limited to, N,N-dimethylformamide and dimethylacetamide. Suitable imidazole solvents include, but are not limited to, methylimidazole, dimethylimidazole, and others. Suitable ketone solvents include, but are not limited to, acetone, methyl ethyl ketone, and others.

[0070] In some embodiments of this process, one or more nonreactive solvents are used. The term "nonreactive," as used in this application, refers to a solvent that does not react with Grignard-type complexes. Typical nonreactive solvents used in this process include, but are not limited to, toluene, xylene, diglyme, and cyclohexane. In a few examples, cyclic solvents, such as THF and dioxane, have been used, but processes using these solvents have not yielded the desired product (see, for example, Comparative Examples 1 to 9). It is thought that the cyclic solvents used in these examples react with the Zn complex formed in the process, rather than with the halosilane (reacting component). However, processes using toluene as the solvent do lead to the desired product. In some embodiments, the accelerators used in this process act additionally as solvents, as shown in Example 25.

[0071] This process can be carried out over a wide temperature range. In one embodiment, the process is carried out at temperatures ranging from 10°C to about 200°C. Advantageously, the process is carried out in the range of 20°C to about 175°C or 50°C to about 150°C, and more advantageously, in the range of 70°C to about 100°C.

[0072] In one embodiment, the process is carried out by (i) providing a mixture of a non-magnesium metal, an accelerator, and optionally a catalyst; (ii) adding a halosilane to the mixture in (i); and (iii) adding an organofunctional alkyl halide to the mixture in (ii) and heating to produce an organosilicon compound. This method can be carried out under an inert atmosphere such as a nitrogen atmosphere.

[0073] Organosilicon compounds can be obtained by any suitable method. In one embodiment, the final product of the organosilicon compound is optionally obtained by filtering the product obtained in step (iii) under an inert atmosphere and then isolating the product by vacuum distillation. Vacuum distillation may be carried out at a temperature in the range of 120°C to about 180°C and at a pressure of about 1 to about 5 mbar.

[0074] This process enables the synthesis of organosilicon compounds with multiple functional groups by using a halosilane containing multiple halogen atoms and controlling the molar ratio of the organofunctional halide to the halosilane. This may be used to functionalize organosilicon compounds with a specific type of organofunctional group. This process also enables the synthesis of organosilicon compounds with different organofunctional groups. To produce organosilicon compounds with at least two different organofunctional groups, this process includes (i) reacting a first organofunctional alkyl halide with a halosilane containing multiple halogen atoms to produce a first organosilicon compound containing a halogen functional group; and (ii) yielding a second organofunctional alkyl halide containing an organofunctional group different from the organofunctional group of the first organofunctional alkyl halide; and reacting the second organofunctional alkyl halide with the first organosilicon compound containing a halogen functional group to provide a second organosilicon compound containing organofunctional groups different from each other.

[0075] In one embodiment of the process, the organosilicon compound contains at least two non-identical organic functional groups. In some embodiments, this process involves formula (i) (X 1 ) n -Si(R 4 ) 4-n The formula for p moles of halosilane [(R 1 )-(C(R 2 )(R 3 )) m ]-X 2 The first organofunctional alkyl halide is reacted with the formula [(R 1 )-(C(R 2 )(R 3 )) m ] p -Si(R 4 ) 4-n (X1) n-p The first organosilicon compound is produced, and then (ii) formula [(R 1 )-(C(R 2 )(R 3 )) m ] p -Si(R 4 ) 4-n (X 1 ) n-p The first organosilicon compound is given by the formula [(R 1’ )-(C(R 2’ )(R 3’ )) m’ ]-X 2’ It reacts with a second organofunctional alkyl halide to form formula ([(R 1 )-(C(R 2 )(R 3 )) m ] p )([(R 1’ )-(C(R 2’ )(R 3’ )) m’ ] p’ )(-Si(R 4 ) 4-n (X 1 ) n-p-p’ This involves generating a second organosilicon compound, where R 1 and R 1’ Each is an independently independent organic functional group; R 2 and R2’ Each is independently H or C1-C20 alkyl; R 3 and R 3’ Each is independently H or C1-C20 alkyl; R 4 C1-C20 alkyl;X 1 is F, Cl, Br, or I;X 2 and X 2’ F, Cl, Br, or I are independent of each other; m and m' are independent of each other, 1-10; n is 1-4; p is 1-4, where p is ≤n; where R 1’ is R 1 Unlike; R 2’ is R 2 It is either identical or different from; R 3’ is R 3 m' is either identical or different from m, m' is either identical or different from m, and p' is ≤(np).

[0076] A process for synthesizing organosilicon compounds having different organic functional groups can be described as follows in one embodiment: (i)(X 1 ) n -Si(R 4 ) 4-n + p[(R 1 )-(C(R 2 )(R 3 )) m ]-X 2 → [(R 1 )-(C(R 2 )(R 3 )) m ] p -Si(R 4 ) 4-n (X 1 ) n-p Here, p is less than n; (ii)[(R 1 )-(C(R 2 )(R 3 )) m ] p -Si(R 4 ) 4-n (X 1 ) n-p + p'[(R1’ )-(C(R 2’ )(R 3’ )) m’ ]-X 2’ ↓ ([(R 1 )-(C(R 2 )(R 3 )) m ] p )([(R 1’ )-(C(R 2’ )(R 3’ )) m’ ] p’ )(-Si(R 4 ) 4-n (X 1 ) n-p-p’ Here R 1’ is R 1 Unlike; R 2’ is R 2 It is either identical or different from; R 3’ is R 3 m' is either identical or different from m, m' is either identical or different from m, and p' is ≤(np).

[0077] In the synthesis of organosilicon compounds having mutually different functional groups, various steps may be performed as desired or necessary to produce the desired product. In embodiments, this process may require the isolation of a first organosilicon compound, followed by the reaction of the first organosilicon compound (supported with a halogen functional group) with a second organosilicon compound. Isolation of the first organosilicon compound may include, but are not limited to, various steps or treatments as needed, including, removing the solvent, collecting, drying, and / or purifying the product. In another embodiment, the process for producing organosilicon compounds having at least two different organofunctional groups may be a continuous, semi-continuous, or batch process, in which the process includes reacting a first organofunctional alkylhalide with a halosilane to produce a solution containing a first organosilicon compound containing a halogen functional group, and then adding a second organosilicon compound to the solution to produce a second organosilicon compound. In another embodiment, this process is a one-pot reaction, where all reactants may be added to a single reaction vessel, and the product may also be obtained from the same vessel. In one or more embodiments, the first organosilicon compound and the second organosilicon compound are obtained with selectivity exceeding 99%. As understood, the step of reacting the second organofunctional alkyl halide with the first organosilicon compound in the presence of a non-magnesium metal may optionally include additional catalysts, solvents, and / or co-catalysts.

[0078] In addition, as will be appreciated, the process for synthesizing organosilicon compounds with multiple different functional groups is not limited to the synthesis of organosilicon compounds with only two different organic functional groups. This process can be used to synthesize organosilicon compounds with two, three, or four different organic functional groups. The developed process presented herein not only generates various mono-functional / multi-functional halosilanes, but also allows the use of organo-functional halosilanes as intermediates to synthesize functionalized alkoxysilanes, functionalized cyclic and linear silicones. A simplified scheme representing an exemplary embodiment for manufacturing such compounds is shown below. [Chemical formula] [Chemical formula] [Chemical formula]

[0079] In one or more embodiments, the compound of formula (1) is made using the process of this specification. The compound of formula (1) is: [(R 1 [[ID=二十六]])-(C(R 2 )(R 3 )) m p -Si(R 4 ) 4-n (X 1 ) n-p (1) wherein in formula (1), R 1 is an organic functional group; R 2 is H or C1-C20 alkyl; R 3 is H or C1-C20 alkyl; R 4 is C1-C20 alkyl; X 1 is F, Cl, Br, or I; m is an integer in the range of 1 to 10; n is an integer in the range of 1 to 4; and p is an integer in the range of 1 to 4, provided that p ≤ n.

[0080] ​ In one or more embodiments of the compound of formula (1), m is an integer equal to or greater than 3. In some embodiments, m in formula (1) is an integer in the range of 3 to 10. In some embodiments, m in formula (1) is an integer in the range of 4 to 9. In some embodiments, m in formula (1) is an integer in the range of 5 to 8. In some other embodiments, m in formula (1) is an integer in the range of 6 to 7.

[0081] In one or more embodiments of the compound of formula (1), p is an integer in the range of 2 to 4. In some embodiments, p in formula (1) is an integer in the range of 1 to 3. In one embodiment, p in formula (1) is an integer 1. In one embodiment, p in formula (1) is an integer 2. In one embodiment, p in formula (1) is an integer 3. In one embodiment, p in formula (1) is an integer 4.

[0082] In one or more embodiments of the compound of formula (1), m is an integer in the range of 3 to 10, and / or p is an integer in the range of 2 to 4. In some embodiments of the compound of formula (1), m is an integer in the range of 3 to 10, and p is an integer in the range of 2 to 4. In some embodiments of the compound of formula (1), m is an integer in the range of 3 to 10, and p is an integer 3.

[0083] In one or more exemplary embodiments, when m=3, p=4, and n=4, the compound of structure (1) is structure Si(R 1 )4 is Organosilan.

[0084] In one or more exemplary embodiments, when m=3, p=1, and n=4, the compound of structure (1) is structure Si(R 4 )(X 1 )3 organotrihalosilane, and in another exemplary embodiment, when m=3, p=1, and n=3, the compound of structure (1) has structure Si(R 4 )(R 1 )(X 1This is organo dihalosylan (2).

[0085] In one example, when p=3, m=3, and n=4 in equation (1), the compound of structure (1) is: [ka] And in the formula R 1 and X 1 This is as stated above.

[0086] In another example, when p=2, m=3, and n=3 in equation (1), the compound of structure (1) is: [ka] And in the formula R 1 , R 4 and X 1 This is as stated above.

[0087] In another example, when p=2, m=3, and n=2 in equation (1), the compound of structure (1) is: [ka] And in the formula R 1 and R 4 This is as stated above.

[0088] In another example, when p=1, m=3, and n=2 in equation (1), the compound of structure (1) is: [ka] And in the formula R 1 , R 4 and X 1 This is as stated above.

[0089] In another example, when p=3, m=3, and n=3 in equation (1), the compound of structure (1) is: [ka] And in the formula R 1 and R 4 This is as stated above.

[0090] In one or more embodiments of the compound of formula (1), R 1 C1-C20 alkyl, -CR 5 =CR 6 2. -C≡CR 7 -CN, -C(O)R 8 -OC(O)R 9 , -C(O)OR 10 , -SR 11 -S(O)2R 12 , -NR 13 2, -C(O)NR 14 2. -OC(O)-CR 15 =R 16 2, -CF3, -(CR 17 2) n -CF3, -NCO, -CS-OR 18 ,-CSSR 19 , -NR 20 C(O)-CR 21 =CR 22 2. C6-C 20 Selected independently from aryl, aralkyl, or alkaryl, where R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 18 , R 19 , R 20 , R 21 , and R 22 Each is independently H, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C30 aryl, aralkyl, or alkaryl, and R 17 is H, C1-C10 alkyl, or F.

[0091] In one or more embodiments of the compound of formula (1), R 1 is -C≡CR 7 、-C(O)R 8 、-C(O)OR 10 、-SR 11 、-CS-OR 18 、-CSSR 19 、-NR 20 C(O)-CR 21 =CR 22 2, C6-C20 aralkyl, or arylalkyl, independently selected, where R 7 、R 8 、R 10 、R 11 、R 18 、R 19 、R 20 、R 21 、and R 22 is each independently H, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C30 aryl, aralkyl, or arylalkyl, and R 17 is H, C1-C10 alkyl, or F. In some of such embodiments, p is from 1 to 3. In one of such embodiments, p is 2. In one of such embodiments, p is 1.

[0092] In one or more embodiments of the compound of formula (1), X 1 is Cl.

[0093] In one embodiment of the compound of formula (1), m = 3, p = 1, and n = 2, and R 1 is -C≡CR 7 、-C(O)R 8 、-C(O)OR 10 、-SR 11 、-CS-OR 18 、-CSSR 19 、-NR 20 C(O)-CR 21 =CR 22 2, C6-C20 aralkyl, or arylalkyl, independently selected, where R 7, R 8 , R 10 , R 11 , R 18 , R 19 , R 20 , R 21 , and R 22 Each of these is independently H, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C30 aryl, aralkyl, or alkaryl, and R 17 is H, C1-C10 alkyl, or F.

[0094] The organosilicon compounds of formula (1) may include organically functional substituted silanes, organically functional substituted halosilanes, organically functional substituted alkylhalosilanes, organically functional substituted alkylsilanes, halosilanes, or combinations thereof. Some non-limiting examples of organosilicon compounds of formula (1) synthesized by this process are: [ka] [ka] [ka] [ka] [ka] [ka] That is the case.

[0095] Embodiments and examples of the process for forming organosilicon compounds can be better understood with reference to the following examples. These examples are for illustrative purposes only and are not intended to limit the present invention to such embodiments and examples. [Examples]

[0096] Example 1: Reaction of chloropropylmethanesulfone with dimethyldichlorosilane in the presence of Zn / ZnI2 and HMPA [ka]

[0097] In a flask equipped with a condenser and a dropping funnel, Zn powder (4.6 g, 0.07 mol) and zinc iodide (1 g, 0.003 mol) were added to a mixture of hexamethylphosphoramide (23 mL) and toluene (27 mL) under an N2 atmosphere. Dimethyldichlorosilane (DMDCS) (12 g, 0.1 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. Chloropropylmethanesulfone (10 g, 0.6 mol) was added over a period of 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. Complete conversion from DMDCS to functionalized chlorosilane was observed. 1 This was confirmed by 1H NMR. The product was isolated by filtration under an N2 atmosphere followed by vacuum distillation at 130°C and a pressure of 2 mbar.

[0098] Comparative Example 1: Reaction of chloropropylmethanesulfone and dimethyldichlorosilane in THF in the presence of Mg [ka]

[0099] In a flask equipped with a condenser and a dropping funnel, shaved Mg (1.6 g, 0.07 mol) was added to anhydrous THF (50 mL) under an N2 atmosphere. After adding 1 mL of dibromoethane and iodine crystals, chloropropylmethanesulfone (10 g, 0.6 mol) was added dropwise to the magnesium. This mixture was heated at 50°C for 3 hours until most of the Mg was dissolved. Dimethyldichlorosilane (DMDCS) (12 g, 0.1 mol) was added to the reaction mixture via a dropping funnel with stirring at 50°C, and then heated at 75°C for 24 hours. At this stage, no solid precipitate of MgCl2 was observed. 1 HNMR analysis confirmed that no functionalized chlorosilane product was formed.

[0100] Comparative Example 2: Reaction of chloropropylmethanesulfone and dimethyldichlorosilane in 1,4-dioxane in the presence of Mg

[0101] [ka]

[0102] A reaction similar to that in Comparative Example 1 was carried out in anhydrous 1,4-dioxane at 100°C, but no product was formed.

[0103] Comparative Example 3: Reaction of chloropropylmethanesulfone and dimethyldichlorosilane in 1,4-dioxane in the presence of Mg / LiCl

[0104] [ka]

[0105] An experiment similar to Comparative Example 1 was carried out in anhydrous 1,4-dioxane at 100°C in the presence of LiCl as an accelerator. No products were formed or isolated.

[0106] Comparative Example 4: Reaction of chloropropylmethanesulfone with dimethyldichlorosilane in the presence of Mg and HMPA

[0107] [ka]

[0108] An experiment similar to Comparative Example 1 was carried out at 100°C in a mixture of anhydrous 1,4-dioxane (27 ml) and HMPA (23 ml). No products were formed or isolated.

[0109] Comparative Example 5: Reaction of chloropropylmethanesulfone and dimethyldichlorosilane in HMPA in the presence of Mg / LiCl

[0110] [ka]

[0111] An experiment similar to Comparative Example 1 was carried out at 100°C in a mixture of anhydrous 1,4-dioxane (27 ml) and HMPA (23 ml) in the presence of LiCl as a catalyst. However, no product was formed or isolated.

[0112] Comparative Example 6: Reaction of chloropropylmethanesulfone and dimethyldichlorosilane in THF in the presence of Zn [ka]

[0113] An experiment similar to Example 1 was carried out in an anhydrous THF mixture at 75°C in the presence of zinc and in the absence of a halide catalyst. However, no products were formed or isolated.

[0114] Comparative Example 7: Reaction of chloropropylmethanesulfone and dimethyldichlorosilane in 1,4-dioxane in the presence of zinc [ka]

[0115] An experiment similar to Comparative Example 1 was carried out in anhydrous 1,4-dioxane (50 ml) at 100°C in the presence of zinc. However, no products were formed or isolated.

[0116] Comparative Example 8: Reaction of chloropropylmethanesulfone and dimethyldichlorosilane in 1,4-dioxane in the presence of Zn / ZnI2 [ka]

[0117] An experiment similar to Comparative Example 1 was carried out in a mixture of anhydrous 1,4-dioxane (50 ml) at 100°C in the presence of Zn / ZnI2. However, no product was formed or isolated.

[0118] Comparative Example 9: Reaction of chloropropylmethanesulfone and dimethyldichlorosilane in dioxane / HMPA in the presence of Zn / ZnI2 [ka]

[0119] An experiment similar to Example 1 was carried out in a mixture of anhydrous 1,4-dioxane (27 ml) and HMPA (23 ml) at 100°C in the presence of Zn / ZnI2. However, no product was formed or isolated.

[0120] Comparative Example 10: Reaction of chloropropylmethanesulfone with dimethyldichlorosilane in the presence of Zn and HMPA [ka]

[0121] An experiment similar to Example 1 was carried out in a mixture of toluene (27 ml) and HMPA (23 mL) at 100°C in the presence of zinc and in the absence of a halide accelerator. However, no products were formed or isolated.

[0122] Comparative Example 11: Reaction of chloropropylmethanesulfone and dimethyldichlorosilane in the presence of Zn / ZnCl2 and in the absence of HMPA [ka]

[0123] An experiment similar to Example 1 was carried out in a mixture of anhydrous toluene (50 ml) in the presence of Zn / ZnCl2. The reaction was carried out in the absence of HMPA. No products were formed or isolated.

[0124] Comparative Example 12: Reaction of chloropropylmethanesulfone and dimethyldichlorosilane in the presence of Zn / ZnI2 and DMI (dimethylimidazolidinone) [ka]

[0125] An experiment similar to Example 1 was carried out in the presence of DMI (50 ml) and Zn / ZnI2. However, no products were formed or isolated.

[0126] Example 2: Synthesis of bis-(methanesulfonylpropyl)-dimethylsilane [ka]

[0127] In a flask equipped with a condenser and a dropping funnel, Zn powder (4.3 g, 0.07 mol) and zinc iodide (1 g, 0.003 mol) were added to a mixture of hexamethylphosphoramide (23 mL) and toluene (27 mL) under an N2 atmosphere. Dimethyldichlorosilane (DMDCS) (4 g, 0.03 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. Chloropropylmethanesulfone (10 g, 0.06 mol) was added over a period of 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. Complete conversion from DMDCS to functionalized chlorosilane was observed. 1 This was confirmed by 1H NMR. The product was isolated by filtration under an N2 atmosphere followed by vacuum distillation at 160°C and a pressure of 2 mbar.

[0128] Example 3: Synthesis of (methanesulfonylpropyl)-methyldichlorosilane [ka]

[0129] In a flask equipped with a condenser and a dropping funnel, Zn powder (4.3 g, 0.07 mol) and zinc iodide (1 g, 0.003 mol) were added to a mixture of hexamethylphosphoramide (23 mL) and toluene (27 mL) under an N2 atmosphere. Methyltrichlorosilane (MTCS) (10 g, 0.06 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. Chloropropylmethanesulfone (10 g, 0.06 mol) was added over a period of 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. Complete conversion from MTCS to functionalized chlorosilane was observed. 1 This was confirmed by 1H NMR. The product was isolated by filtration under an N2 atmosphere followed by vacuum distillation.

[0130] Example 4: Synthesis of bis-(methanesulfonylpropyl)-methylchlorosilane [ka]

[0131] In a flask equipped with a condenser and a dropping funnel, Zn powder (4.3 g, 0.07 mol) and zinc iodide (1 g, 0.003 mol) were added to a mixture of hexamethylphosphoramide (23 mL) and toluene (27 mL) under an N2 atmosphere. Methyltrichlorosilane (MTCS) (5 g, 0.03 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. Chloropropylmethanesulfone (10 g, 0.06 mol) was added over a period of 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. Complete conversion from MTCS to bifunctionalized chlorosilane was observed. 1 This was confirmed by 1H NMR. The product was isolated by filtration under an N2 atmosphere followed by vacuum distillation.

[0132] Example 5: Synthesis of Tris-(Methanesulfonylpropyl)-methylsilane [ka]

[0133] In a flask equipped with a condenser and a dropping funnel, Zn powder (6.9 g, 0.11 mol) and zinc iodide (1.5 g, 0.005 mol) were added to a mixture of hexamethylphosphoramide (33 mL) and toluene (27 mL) under an N2 atmosphere. Methyltrichlorosilane (MTCS) (4 g, 0.03 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. Chloropropylmethanesulfone (10 g, 0.06 mol) was added over a period of 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. Complete conversion of MTCS to trifunctionalized silane was observed. 1 This was confirmed by 1H NMR. The product was isolated by filtration under an N2 atmosphere followed by vacuum distillation.

[0134] Example 6: Synthesis of nitrilopropyl-dimethylchlorosilane [ka]

[0135] In a flask equipped with a condenser and dropping funnel, Zn powder (6.4 g, 0.1 mol) and zinc iodide (1.6 g, 0.005 mol) were added to a mixture of hexamethylphosphoramide (34 mL) and toluene (41 mL) under an N2 atmosphere. DMDCS (12 g, 0.1 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. Chloropropyl nitrile (10 g, 0.1 mol) was added over 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. Complete conversion from DMDCS to functionalized chlorosilane was observed. 1 This was confirmed by 1H NMR. The product was isolated by filtration under an N2 atmosphere followed by vacuum distillation.

[0136] Example 7: Synthesis of nitrilopropyl-methanesulfonylpropyl-dimethylsilane [ka]

[0137] In a flask equipped with a condenser and a dropping funnel, Zn powder (6.4 g, 0.1 mol) and zinc iodide (1.6 g, 0.005 mol) were added to a mixture of hexamethylphosphoramide (34 mL) and toluene (41 mL) under an N2 atmosphere. Methanesulfonylpropyl-dimethylchlorosilane (21 g, 0.1 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. Chloropropyl nitrile (10 g, 0.1 mol) was added over a period of 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. Complete conversion from chlorosilane to functionalized chlorosilane was observed. 1 This was confirmed by 1H NMR. The product was isolated by filtration under an N2 atmosphere followed by vacuum distillation.

[0138] Example 8: Reaction of chloropropylmethanesulfone with dimethyldichlorosilane in the presence of Zn / ZnI2 and TPPO [ka]

[0139] In a flask equipped with a condenser and a dropping funnel, Zn powder (4.3 g, 0.07 mol) and zinc iodide (1 g, 0.003 mol) were added to a mixture of triphenylphosphine oxide (36.5 g) and toluene (27 mL) under an N2 atmosphere. Dimethyldichlorosilane (DMDCS) (12 g, 0.1 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. Chloropropylmethanesulfone (10 g, 0.06 mol) was added over a period of 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. Complete conversion from DMDCS to functionalized chlorosilane was observed. 1 This was confirmed by 1H NMR. The product was isolated by filtration under an N2 atmosphere followed by vacuum distillation.

[0140] Example 9: Reaction of chloropropylmethanesulfone with dimethyldichlorosilane in the presence of Zn / ZnI2 and TOPO [ka]

[0141] In a flask equipped with a condenser and a dropping funnel, Zn powder (4.3 g, 0.07 mol) and zinc iodide (1 g, 0.003 mol) were added to a mixture of trioctylphosphine oxide (60 g) and toluene (27 mL) under an N2 atmosphere. Dimethyldichlorosilane (DMDCS) (12 g, 0.1 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. Chloropropylmethanesulfone (10 g, 0.06 mol) was added over a period of 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. Complete conversion from DMDCS to functionalized chlorosilane was observed. 1 This was confirmed by 1H NMR. The product was isolated by filtration under an N2 atmosphere followed by vacuum distillation.

[0142] Example 10: Reaction of chloropropylmethanesulfone with dimethyldichlorosilane in the presence of Zn / LiI and HMPA [ka]

[0143] In a flask equipped with a condenser and a dropping funnel, Zn powder (4.6 g, 0.07 mol) and lithium iodide (0.9 g, 0.006 mol) were added to a mixture of hexamethylphosphoramide (23 mL) and toluene (27 mL) under an N2 atmosphere. Dimethyldichlorosilane (DMDCS) (12 g, 0.1 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. Chloropropylmethanesulfone (10 g, 0.06 mol) was added over a period of 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. Complete conversion of DMDCS to functionalized chlorosilane was observed. 1 Confirmed by HNMR.

[0144] Example 11: Reaction of chloropropylmethanesulfone with dimethyldichlorosilane in the presence of Zn / KI and HMPA [ka]

[0145] In a flask equipped with a condenser and a dropping funnel, Zn powder (4.6 g, 0.07 mol) and potassium iodide (1.1 g, 0.006 mol) were added to a mixture of hexamethylphosphoramide (23 mL) and toluene (27 mL) under an N2 atmosphere. Dimethyldichlorosilane (DMDCS) (12 g, 0.1 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. Chloropropylmethanesulfone (10 g, 0.06 mol) was added over a period of 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. Complete conversion of DMDCS to functionalized chlorosilane was observed. 1 Confirmed by HNMR.

[0146] Example 12: Reaction of chloropropylmethanesulfone with dimethyldichlorosilane in the presence of Zn / NaI and HMPA [ka]

[0147] In a flask equipped with a condenser and a dropping funnel, Zn powder (4.6 g, 0.07 mol) and sodium iodide (1.0 g, 0.006 mol) were added to a mixture of hexamethylphosphoramide (23 mL) and toluene (27 mL) under an N2 atmosphere. Dimethyldichlorosilane (DMDCS) (12 g, 0.1 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. Chloropropylmethanesulfone (10 g, 0.06 mol) was added over a period of 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. Complete conversion of DMDCS to functionalized chlorosilane was observed. 1 Confirmed by HNMR.

[0148] Example 13: Synthesis of Methoxypropyl-Dimethylchlorosilane [ka]

[0149] In a flask equipped with a condenser and dropping funnel, Zn powder (6.0 g, 0.09 mol) and zinc iodide (0.3 g, 0.001 mol) were added to a mixture of hexamethylphosphoramide (32 mL) and toluene (68 mL) under an N2 atmosphere. DMDCS (18 g, 0.14 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. 1-Chloro-3-methoxypropane (10 g, 0.09 mol) was added over 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. Complete conversion from DMDCS to functionalized chlorosilane was observed. 1 Confirmed by HNMR.

[0150] Example 14: Synthesis of 3-acetoxypropyldimethylchlorosilane [ka]

[0151] In a flask equipped with a condenser and a dropping funnel, Zn powder (4.8 g, 0.07 mol) and zinc iodide (0.2 g, 0.001 mol) were added to a mixture of hexamethylphosphoramide (25 mL) and toluene (75 mL) under an N2 atmosphere. DMDCS (14 g, 0.11 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. 3-chloropropyl acetate (10 g, 0.07 mol) was added over 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. Complete conversion from DMDCS to functionalized chlorosilane was observed. 1 Confirmed by HNMR.

[0152] Example 15: Synthesis of phenylpropyl-dimethylchlorosilane [ka]

[0153] In a flask equipped with a condenser and dropping funnel, Zn powder (4.2 g, 0.06 mol) and zinc iodide (0.2 g, 0.001 mol) were added to a mixture of hexamethylphosphoramide (23 mL) and toluene (77 mL) under an N2 atmosphere. DMDCS (13 g, 0.10 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. Phenylpropyl chloride (10 g, 0.06 mol) was added over a period of 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. Complete conversion from DMDCS to functionalized chlorosilane was observed. 1 Confirmed by HNMR.

[0154] Example 16: Synthesis of pentynyl-dimethylchlorosilane [ka]

[0155] In a flask equipped with a condenser and dropping funnel, Zn powder (6.4 g, 0.1 mol) and zinc iodide (0.3 g, 0.001 mol) were added to a mixture of hexamethylphosphoramide (34 mL) and toluene (66 mL) under an N2 atmosphere. DMDCS (19 g, 0.15 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. 5-chloro-1-pentine (10 g, 0.1 mol) was added over 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. Complete conversion from DMDCS to functionalized chlorosilane was observed. 1 Confirmed by HNMR.

[0156] Example 17: Synthesis of 3-(chlorodimethylsilyl)propylthioacetate [ka]

[0157] In a flask equipped with a condenser and a dropping funnel, Zn powder (4.3 g, 0.07 mol) and zinc iodide (0.2 g, 0.001 mol) were added to a mixture of hexamethylphosphoramide (23 mL) and toluene (77 mL) under an N2 atmosphere. DMDCS (13 g, 0.10 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. 3-chloropropylthioacetate (10 g, 0.07 mol) was added over a period of 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. Complete conversion from DMDCS to functionalized chlorosilane was observed. 1 Confirmed by HNMR.

[0158] Example 18: Synthesis of 3-(methylsulfanyl)propyldimethylchlorosilane [ka]

[0159] In a flask equipped with a condenser and dropping funnel, Zn powder (5.3 g, 0.08 mol) and zinc iodide (0.3 g, 0.001 mol) were added to a mixture of hexamethylphosphoramide (28 mL) and toluene (72 mL) under an N2 atmosphere. DMDCS (16 g, 0.12 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. 3-chloropropylmethylsulfan (10 g, 0.08 mol) was added over 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. Complete conversion from DMDCS to functionalized chlorosilane was observed. 1 Confirmed by HNMR.

[0160] Example 19: Synthesis of 5-chloropropyldimethylchlorosilane [ka]

[0161] In a flask equipped with a condenser and dropping funnel, Zn powder (3.5 g, 0.05 mol) and zinc iodide (0.2 g, 0.001 mol) were added to a mixture of hexamethylphosphoramide (19 mL) and toluene (50 mL) under an N2 atmosphere. DMDCS (10 g, 0.08 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. 1-Bromo-3-chloropropane (10 g, 0.05 mol) was added over 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnBr2 was formed as a by-product. Complete conversion from DMDCS to functionalized chlorosilane was observed. 1 Confirmed by HNMR.

[0162] Example 20: Synthesis of Methoxypropyl-Nitrilopropyl-Dimethylsilane [ka]

[0163] In a flask equipped with a condenser and a dropping funnel, Zn powder (6.3 g, 0.1 mol) and zinc iodide (0.3 g, 0.001 mol) were added to a mixture of hexamethylphosphoramide (34 mL) and toluene (50 mL) under an N2 atmosphere. DMDCS (19 g, 0.15 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. Chloromethoxypropane (10.5 g, 0.1 mol) was added over 5 minutes at 70°C, and then the mixture was heated at 100°C for 24 hours. The reaction was then cooled. Another batch of Zn powder (6.3 g, 0.1 mol) and zinc iodide (0.3 g, 0.001 mol) was added together with hexamethylphosphoramide (34 mL) and toluene (50 mL) under an N2 atmosphere. This reaction mixture was then slowly heated to 70°C. 4-chlorobutyronitrile (10 g, 0.10 mol) was added over a period of 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. The formation of a bifunctionalized silane was observed. 1 Confirmed by HNMR.

[0164] Example 21: Synthesis of pentinyl-3-(methylsulfanyl)propyldimethylsilane [ka]

[0165] In a flask equipped with a condenser and a dropping funnel, Zn powder (6.4 g, 0.1 mol) and zinc iodide (0.3 g, 0.001 mol) were added to a mixture of hexamethylphosphoramide (35 mL) and toluene (50 mL) under an N2 atmosphere. DMDCS (19 g, 0.15 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. 5-chloropentine (10 g, 0.10 mol) was added over 5 minutes at 70°C, and then the mixture was heated at 100°C for 24 hours. The reaction was then cooled. Another batch of Zn powder (6.4 g, 0.1 mol) and zinc iodide (0.3 g, 0.001 mol) was added together with hexamethylphosphoramide (35 mL) and toluene (50 mL) under an N2 atmosphere. This reaction mixture was then slowly heated to 70°C. Chloropropylmethylsulfan (12.1 g, 0.1 mol) was added at 70°C over a period of 5 minutes, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. The formation of a bifunctionalized silane was observed. 1 Confirmed by HNMR.

[0166] Example 22: Synthesis of 3-acetoxypropyl 3-methoxypropyldimethylsilane [ka]

[0167] In a flask equipped with a condenser and a dropping funnel, Zn powder (4.8 g, 0.07 mol) and zinc iodide (0.25 g, 0.001 mol) were added to a mixture of hexamethylphosphoramide (26 mL) and toluene (50 mL) under an N2 atmosphere. DMDCS (14 g, 0.11 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. Chloropropyl acetate (10 g, 0.07 mol) was added over 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The reaction was then cooled. Another batch of Zn powder (4.8 g, 0.07 mol) and zinc iodide (0.25 g, 0.001 mol) was added together with hexamethylphosphoramide (26 mL) and toluene (50 mL) under an N2 atmosphere. The reaction mixture was then slowly heated to 70°C. 1-Chloro-3-methoxypropane (7.9 g, 0.07 mol) was added over 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. The formation of a bifunctionalized silane was observed. 1 Confirmed by HNMR and GCMS.

[0168] Example 23: Synthesis of 3-phenylpropyl 3-(methylsulfonyl)propyldimethylsilane [ka]

[0169] In a flask equipped with a condenser and a dropping funnel, Zn powder (4.3 g, 0.06 mol) and zinc iodide (0.2 g, 0.001 mol) were added to a mixture of hexamethylphosphoramide (23 mL) and toluene (50 mL) under an N2 atmosphere. DMDCS (19 g, 0.15 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. Chloropropylmethylsulfone (10.1 g, 0.06 mol) was added over 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The reaction was then cooled. Another batch of Zn powder (4.3 g, 0.06 mol) and zinc iodide (0.2 g, 0.001 mol) was added together with hexamethylphosphoramide (23 mL) and toluene (50 mL) under an N2 atmosphere. The reaction mixture was then slowly heated to 70°C. Phenylpropyl chloride (10 g, 0.06 mol) was added over 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. The formation of a bifunctionalized silane was observed. 1 Confirmed by HNMR and GCMS.

[0170] Example 24: Synthesis of 3-phenylpropyldi(methoxypropyl)methylsilane [ka]

[0171] In a flask equipped with a condenser and a dropping funnel, Zn powder (8.5 g, 0.13 mol) and zinc iodide (0.4 g, 0.002 mol) were added to a mixture of hexamethylphosphoramide (45 mL) and toluene (50 mL) under an N2 atmosphere. Trichloromethylsilane (11 g, 0.07 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. 1-Chloro-3-methoxypropane (14 g, 0.13 mol) was added over 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The reaction was then cooled. A separate batch of Zn powder (4.3 g, 0.06 mol) and zinc iodide (0.2 g, 0.001 mol) was added together with hexamethylphosphoramide (23 mL) and toluene (50 mL) under an N2 atmosphere. The reaction mixture was then slowly heated to 70°C. Phenylpropyl chloride (10 g, 0.06 mol) was added over 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. The formation of a trifunctionalized silane was observed. 1 Confirmed by HNMR and GCMS.

[0172] Example 25: Reaction of chloropropylmethanesulfone with dimethyldichlorosilane in the presence of Zn / ZnI2 and HMPA (without additional solvent) [ka]

[0173] In a flask equipped with a condenser and a dropping funnel, Zn powder (4.6 g, 0.07 mol) and zinc iodide (1 g, 0.003 mol) were mixed with hexamethylphosphoramide (50 mL) under an N2 atmosphere. Dimethyldichlorosilane (DMDCS) (12 g, 0.1 mol) was added to the reaction mixture via a dropping funnel with stirring at room temperature, and then slowly heated to 70°C. Chloropropylmethanesulfone (10 g, 0.6 mol) was added over 5 minutes at 70°C, and the mixture was then heated at 100°C for 24 hours. The formation of a large amount of salt was observed, indicating that ZnCl2 was formed as a by-product. Complete conversion from DMDCS to functionalized chlorosilane was observed. 1 This was confirmed by 1H NMR. The product was isolated by filtration under an N2 atmosphere followed by vacuum distillation at 130°C at a pressure of 2 mbar. In this example, only HMPA was used, which acted not only as a solvent but also as an accelerator, and the desired product was successfully formed. Thus, it is clear from this example that accelerators can also be used as non-reactive solvents for this process.

[0174] Table 1 shows examples of reactions for forming organically functionalized silanes. Examples marked with "C" are comparative examples. [Table 1]

[0175] From the results shown in Table 1 and the examples above (Comparative Examples 1 to 11), it is very clear that conventional known processes using Mg as the metal do not yield the desired product, especially when functional groups such as -CN, -COR, -COOR, -CSR, -CSSR, -CSOR, -CSO2R, -CONR2, and others are present in one of the reactants. Surprisingly, it was observed that non-Mg metals (e.g., Zn) lead to the formation of the desired organosilicon compounds.

[0176] Furthermore, the table above clearly shows that the specific combinations of reactive components, accelerators, and metal halide catalysts play important roles in the synthesis of the desired compounds. In some examples of this process, accelerators containing P=O (e.g., HMPA, TOPO, TPPO) are expected to promote the reaction to produce the desired organosilicon compound (product). These accelerators are presumed to stabilize the Zn complex while simultaneously allowing the removal of Zn halide by-products as the complex [ZnX2(HMPA)2], thereby promoting the reaction to form the desired product. One advantage of this process is that the accelerators can be easily regenerated (by simple acid treatment of the complex [ZnX2(HMPA)2]) and recycled. Also, from Example 25, it is clear that accelerators can act as non-reactive solvents. In this example, HMPA functions as both an accelerator and a solvent, leading to the successful formation of the desired product.

[0177] This disclosure provides a process that is a viable alternative to conventional hydrosilylation for the synthesis of organosilicon compounds. Moving away from the conventional wisdom of using magnesium metals for the reaction of halosilanes and alkylhalides, this process remarkably achieves high selectivity (>99%) for the conversion of alkylhalides and halosilanes to organosilicon compounds by using non-magnesium metals in the presence of reaction accelerators. This disclosure also yields novel organosilicon compounds.

[0178] Within the scope of the present invention, several obvious variations of the process are also considered. For example, when the reactant "alkyl halide" is selected as an alkyl iodide, the specific requirement for a metal iodide catalyst for the process can be avoided. In this process, a metal iodide (LiI, NaI, KI, ZnI2, etc.) is used to in-situ convert the reactant, which is an alkyl chloride, to an alkyl iodide, which further helps to accelerate the formation of the Zn complex [ZnX2(HMPA)2] and promote the reaction to the desired product.

[0179] Furthermore, the degree to which organic functional alkyl groups are inserted (substituted) onto the halosilane depends on the ratio of metallic Zn of the alkyl halide to the halosilane. Thus, this process provides those skilled in the art with the flexibility to incorporate mono- / di- / tri- / tetra-substituted organosilicon compounds by modifying the reaction components as required.

[0180] Furthermore, those skilled in the art can use one-pot sequential addition of different functionalized alkyl halides to prepare polyfunctional organosilicon compounds.

[0181] The provisions described above include examples of this specification. Of course, for the purposes of making this specification, it is impossible to describe all recognizable combinations of components or methodologies, and those skilled in the art will recognize that many further combinations and substitutions of this specification are possible. This specification is therefore intended to encompass all such changes, modifications and variations that are included in the idea and scope of the appended claims. Furthermore, wherever the term “includes” is used in the detailed description or claims, such term is intended to be as comprehensive as “includes,” as is the case when “includes” is used as a substitute in the claims.

[0182] The above description illustrates various non-limiting embodiments of a method for producing organically functional silicones from organically functional alkyl halides and halosilanes. Modifications may be conceived by those skilled in the art and those who create and use the present invention. The disclosed embodiments are for illustrative purposes only and are not intended to limit the scope of the invention or subject matter described in the claims.

Claims

1. A process for the synthesis of the organosilicon compound of formula (1), [(R １ )-(C(R ２ )(R ３ )) ｍ ] ｐ -Si(R ４ ) ４－ｎ (X １ ) ｎ－ｐ (1) (i) Halosilane of formula (2) (X １ ) ｎ -Si(R ４ ) ４－ｎ (2) (ii) p moles of the organic functional alkyl halide of formula (3) per mole of halosilane of formula (2) [(R １ )-(C(R ２ )(R ３ )) ｍ ]-X ２ (3) (iii) a non-magnesium metal selected from Zn, (iv) an accelerator selected from phosphorus-containing compounds, and (v) a metal salt selected from metal halides, metal acetates, metal esters, metal amides, metal triflates, metal borates, metal nitrates, or combinations of two or more of these, This includes reacting in the presence of: In the formula R １ Each of these is independently C1-C20 alkyl, -CR ５ =CR ６ ２ -C≡CR ７ -CN, -C(O)R ８ , -OC(O)R ９ , -C(O)OR １０ , -SR １１ , -S(O) ２ R １２ , -NR １３ ２ , -C(O)NR １４ ２ -OC(O)-CR １５ = R １６ ２ , -CF ３ ,-(CR １７ ２ )n-CF ３ , -NCO, -CS-OR １８ , -CSSR １９ , -NR ２０ C(O)-CR ２１ =CR ２２ ２ , independently selected from C6-C20 aryl, aralkyl, or alkaryl, where R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １８ , R １９ , R ２０ , R ２１ , and R ２２ Each of these is independently H, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C30 aryl, aralkyl, or alkaryl, and R １７ is an organic functional group selected from H, C1-C10 alkyl, or F; R ２ is H or C1-C20 alkyl; R ３ is H or C1-C20 alkyl; R ４ is C1-C20 alkyl; X １ is F, Cl, Br, or I; X ２ is F, Cl, Br, or I; m is an integer in the range of 1 to 10; n is an integer in the range of 1 to 4; and p is an integer between 1 and 4, but p is ≤ n, in this process.

2. The process according to claim 1, wherein the molar ratio of the non-magnesium metal to the organically functional alkyl halide is in the range of 0.5:1 to 1:

5.

3. The process of claim 1 or 2, wherein the accelerator is selected from phosphine oxide, phosphate, phosphate, phosphine, phosphoramide, or a combination of two or more of these.

4. Phosphine oxide is given by formula R ２０ ３ P = O or formula (R ２１ ２ N) ３ P = O, and in the formula R ２０ Each of them is independently a C4-C20 alkyl, C3-C20 cyclic alkyl, aralkyl, or alkaryl, where R ２１ The process of claim 3, wherein is independently selected from C1-C10 alkyl and C3-C20 cyclic alkyl.

5. The process of claim 4, wherein the accelerator is tributylphosphine oxide (TBPO), trioctylphosphine oxide (TOPO), hexamethylphosphoramide (HMPA), trimorpholinophosphine oxide or tripyrrolidinophosphine oxide, or a combination thereof.

6. The process of claim 1, wherein the metal salt comprises a metal selected from alkali metals, alkaline earth metals excluding magnesium, transition metals, post-transition metals, metalloids, lanthanides, or combinations of two or more of these.

7. The process of claim 1 or 6, wherein the catalyst is a metal halide.

8. The process according to any one of claims 1 to 7, wherein the catalyst is a metal iodide.

9. X ２ A process of any one of claims 1 to 8, wherein is Cl.

10. The process according to any one of claims 1 to 9, wherein the halosilane is reacted with an alkyl halide at a temperature in the range of 10°C to 200°C.

11. The process of claim 1, wherein the organosilicon compound has at least two non-identical organic functional groups.

12. The process is: (i) The halosilane of formula (X １ ) ｎ -Si(R ４ ) ４－ｎ is reacted with p moles of the first organofunctional alkyl halide of formula [(R １ )-(C(R ２ )(R ３ )) ｍ -X ２ to produce the first organosilicon compound of formula [(R １ )-(C(R ２ )(R ３ )) ｍ ) ｐ -Si(R ４ ) ４－ｎ (X1) ｎ－ｐ ; and then (ii) The first organosilicon compound of the formula [(R １ )-(C(R ２ )(R ３ )) ｍ ｐ -Si(R ４ ) ４－ｎ (X １ ) ｎ－ｐ is reacted with p'moles of the second organic functional alkyl halide of the formula [(R １’ )-(C(R ２’ )(R ３’ )) ｍ’ -X ２’ to produce a second organosilicon compound of the formula ([(R １ )-(C(R ２ )(R ３ )) ｍ ｐ )([(R １’ [[ID= forty]])-(C(R ２’ )(R ３’ )) ｍ’ ｐ’ )(-Si(R ４ ) ４－ｎ (X １ ) ｎ－ｐ－ｐ’ including,​​​ In the formula R １ and R １’ Each of these is an independently independent organic functional group; R ２ and R ２’ Each is independently H or C1-C20 alkyl; R ３ and R ３’ Each is independently H or C1-C20 alkyl; R ４ is C1-C20 alkyl; X １ is F, Cl, Br, or I; X ２ and X ２’ Each is independently F, Cl, Br, or I; m and m' are each independently between 1 and 10; n is 1 to 4; p is between 1 and 4, but p is ≤ n; Here R １’ is R １ Unlike; R ２’ is R ２ Identical to or different from; R ３’ is R ３ The process of claim 11, wherein m' is the same as or different from m, m' is the same as or different from m, and p' is ≤(n-p).

13. The process according to claim 12, wherein the process is a one-pot process.

14. The process of claim 12, wherein the first organosilicon compound and the second organosilicon compound are obtained with a selectivity of more than 99%.

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