Selective non-precious metal-catalyzed mono-hydrosilylation polyunsaturated compounds
Disclosed herein is the selective synthesis of mono-hydrosilylated derivatives of polyunsaturated compounds, such as trivinylcyclohexane using non-precious metal based pyridinediimine and terpyridine complex as selective hydrosilylation catalysts.
1. A process for selectively producing a monosilylated product from a composition containing a silyl hydride and a polyunsaturated compound comprising contacting the composition with a complex of Formula (I), Formula (II) or Formula (III) to cause the silyl hydride to react with the polyunsaturated compound such that hydrosilylation occurs selectively at one unsaturated group of the unsaturated compound thereby producing the mono-hydrosilylated product, wherein the polyunsaturated compound is represented by Formula (IV) or Formula (V)
E 1 [(CH 2 ) β CR 1 ═CH 2 ] α (Formula IV)
R 2 γ E 2 [(CH 2 ) β CR 1 ═CH 2 ] α (Formula V)
wherein
E 1 is a divalent or polyvalent aliphatic or aromatic cyclic hydrocarbon group containing from 3 to 25 carbon atoms, or a divalent or polyvalent aliphatic or aromatic heterocyclic hydrocarbon containing from 3 to 25 carbon atoms, wherein the heteroatom is selected from the group consisting of oxygen, nitrogen, silicon and sulfur;
E 2 is a divalent or polyvalent cyclic silicone group containing from 3 to 8 silicon atoms and from 3 to 8 oxygen atoms;
each occurrence of R 1 and R 2 is independently a hydrogen or a hydrocarbon group containing from 1 to 8 carbon atoms; and
each occurrence of α, β and γ is independently an integer, wherein α is 2 to 6; β is 0 to 6; and γ is 0 to 4;
wherein Formula (I), Formula (II) and Formula (III) are:
wherein:
G is Mn, Fe, Ni, or Co;
each occurrence of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 19 , and R 20 is independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert functional group, wherein R 1 to R 9 , R 19 , R 20 , other than hydrogen, optionally contain at least one heteroatom;
each occurrence R 23 is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R 23 optionally contains at least one heteroatom; and
optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 19 , R 20 , and R 23 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure;
each of L 1 and L 2 is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, C2-C18 alkenyl, C2-C18 alkynyl, or L 1 -L 2 together is one of the following
wherein each occurrence of R 10 , R 11 , R 13 , R 14 , R 15 and R 16 is independently hydrogen, C1-C18 alkyl, C2-C18 alkenyl, or C2-C18 alkynyl, wherein R 10 , R 11 , R 13 , R 14 , R 15 and R 16 , other than hydrogen, optionally contain at least one heteroatom, and R 10 , R 11 , R 13 , R 14 , R 15 and R 16 , other than hydrogen, are optionally substituted;
each occurrence of R 12 is independently C1-C18 alkyl, C1-C18 substituted alkyl, C2-C18 alkenyl, C2-C18 substituted alkenyl, C2-C18 alkynyl, C2-C18 substituted alkynyl, aryl, substituted aryl, wherein R 12 optionally contains at least one heteroatom;
optionally any two of R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 taken together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure;
each occurrence of R 17 and R 18 is independently alkyl, substituted alkyl, aryl, or substituted aryl, wherein each of R 17 and R 18 optionally contains at least one heteroatom, and wherein R 17 and R 18 taken together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure;
each occurrence of R 19 and R 20 is independently a covalent bond that connects Si and C, an alkyl, substituted alkyl, or a heteroatom, wherein R 19 , and R 20 optionally contain at least one heteroatom; wherein L 1 -L 2 bonds with G through unsaturated sites S 1 and S 2 ;
each X is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, wherein X optionally contains at least one heteroatom; and
wherein the molar ratio of the Si—H functional groups in the silyl hydride to the alkenyl functional groups in the unsaturated compound is between about (0.5:α) and about (1.1:α).
2. The process of claim 1 wherein the molar ratio of the Si—H functional groups in the silyl hydride to the alkenyl functional groups in the unsaturated compound is about 1:α.
3. The process of claim 1 wherein the unsaturated compound is selected from the group consisting of trivinylcyclohexanes, trivinylbenzenes, tetravinylcyclobutane, trivinyltrimethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, triallylcyanurate, and triallylisocyanurate.
4. The process of claim 1 wherein the unsaturated compound is trivinylcyclohexane.
5. The process of claim 1 , wherein the silyl hydride is selected from the group consisting of R a SiH 4-a , (RO) a SiH 4-a , HSiR a (OR) 3-a , R 3 Si(CH 2 ) f (SiR 2 O) e SiR 2 H, (RO) 3 Si(CH 2 ) f (SiR 2 O) e SiR 2 H, Q u T v T p H D w D H x M H y M z , and combinations thereof, wherein Q is SiO 4/2 , T is R′SiO 3/2 , T H is HSiO 3/2 , D is R′ 2 SiO 2/2 , D H is R′HSiO 2/2 , M H is H g R′ 3-g SiO 1/2 , M is R′ 3 SiO 1/2 , each occurrence of R and R′ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, wherein R and R′ optionally contain at least one heteroatom, each occurrence of a independently has a value from 1 to 3, f has a value of from 1 to 8, e has a value of from 1 to 11, g has a value of from 1 to 3, p is from 0 to 20, u is from 0 to 20, v is from 0 to 20, w is from 0 to 1000, x is from 0 to 1000, y is from 0 to 20, and z is from 0 to 20, provided that p+x+y equals 1 to 3000, and the valences of the all the elements in the silyl hydride are satisfied.
6. The process of claim 1 wherein the silyl hydride has one of the following structures: R 3 3 SiH (Formula VI), HSi(OR 4 ) 3 (Formula VII),
wherein each occurrence of R 3 , R 4 , R 7 , R 8 , and R 9 is independently a C1-C20 alkyl or an aryl group; R 6 is hydrogen, a C1-C20 alkyl or an aryl group; and x and w are independently greater than or equal to 0.
7. The process of claim 5 wherein the silyl hydride is selected from the group consisting of (CH 3 O) 3 SiH, (C 2 H 5 O) 3 SiH, (CH 3 ) 3 SiOSi(CH 3 ) 2 H, [(CH 3 ) 3 SiO] 2 SiH(CH 3 ), [(CH 3 ) 2 SiO] 3 OSiH(CH 3 ), and [(CH 3 ) 2 SiO] 4 OSiH(CH 3 ).
8. The process of claim 5 wherein the complex has a structural Formula (I), and wherein
R 23 is
wherein R 1 and R 2 are both methyl, ethyl, propyl or isopropyl groups, and R 4 , R 5 , and R 6 are as defined in claim 1 .
9. The process of claim 1 wherein the complex is immobilized on a support.
10. A process for selectively producing a mono-hydrosilylated product from 1,2,4-trivinylcyclohexane and a silyl hydride comprising reacting trivinylcyclohexane with the silyl hydride in the presence of a complex of Formula (I), Formula (II) or Formula (III),
wherein Formula (I), Formula (II) and Formula (III) are as defined in claim 1 ;
wherein the molar ratio of the Si—H functional groups in the silyl hydride to the alkenyl functional groups in the 1,2,4-trivinylcyclohexane is between about (0.5:3) and about (1.1:3); and
wherein the silyl group from the silyl hydride is selectively added to the 4 position of the 1,2,4-trivinylcyclohexane.
11. The process of claim 10 wherein the silyl hydride is triethoxysilane.
12. The process of claim 11 wherein the silyl hydride is bis(trimethylsiloxy)methylsilane.
13. The process of claim 10 wherein the trivinylcyclohexane is a mixture of trivinylcyclohexane stereoisomers.
14. The process of claim 10 wherein the 1,2,4-trivinylcyclohexane is 1,2,4-trivinylcyclohexane isomer A of Formula (XVI) and/or 1,2,4-trivinylcyclohexane isomer B of Formula (XVII)