Organic metal-free catalysts with electrophilic and nucleophilic dual-functions, preparation methods of making the same, and uses thereof
AssigneeZhejiang University
InventorsGuangpeng Wu, Guanwen Yang, Yaoyao Zhang
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Abstract
The present invention relates to a kind of organic metal-free catalysts containing both electrophilic and nucleophilic dual-functions, preparation methods of making the same, and uses thereof. The organic metal-free catalysts in the present invention have the chemical structure shown in formula (I): Compared with the metal-free organic polymerization catalytic systems that have been reported before, the organic metal-free catalysts in this invention have the combined advantages of simple preparation, high reactivity, easy operation, low cost, wide applicability, easy for industrial production.
Claims20
An organic metal-free catalyst with electrophilic and nucleophilic dual-functions, which has the chemical structures shown in the formula (I)
- wherein each set of the substituents of Y1˜Y3 were independently selected from the following structural formulas 1˜5:
- wherein each D1˜D6 is represented independently as
- wherein B represents boron atom, N represents nitrogen atom, P represents phosphorus atom, and represents connecting point;
- each a and b is independently selected from the integers of 0˜20, but cannot be equal to 0 at the same time;
- each c, d, and e is independently selected from the integers of 0˜20;
- b cannot be equal to 0, when a=0;
- e cannot be equal to 0, when b=0;
- each set of the substituents of Z1˜Z4, R1˜R2, E1˜E4 are independently selected from the group containing substituted and unsubstituted C1-C30 alkyl, C3-C30 alkenyl, C3-C30 alkynyl, C6-C30 aryl, and C5-C30 heteroaryl, any of which may be heteroatom (O, S, N, Si, and P)-containing;
- any two or more of the substituents of Z1˜Z4, R1˜R2, E1˜E4 may from bonds or rings;
- but the proviso is that Z1 cannot be the aromatic group of C6 when a=1;
- Z2 cannot be the aromatic group of C6 when c=1;
- Z3 cannot be the aromatic group of C6 when d=1;
- Z1, Z2, Z3, Z4, R1, and R2 cannot be the substituted or non-substituted aromatic groups at the same time;
- each set of D1˜D3 and D4˜D6 cannot be substituted or non-substituted aromatic groups of C6-C10 at the same time;
- each X⊖ represents a negative ion;
- each X⊖ exists independently in the form of a single negative ion, or each X⊖ is connected with one or more of D1˜D6 in the form of covalent bond.
A preparation method for an organic metal-free catalyst with electrophilic and nucleophilic dual-functions, characterized in that the catalyst is obtained by the hydroboration of a raw material W1 containing at least one unsaturated bond and a second raw material W2 containing contains at least one boron-hydrogen bond, wherein
- the structural formula of is represented by one or more of the following:
- wherein
- each f is an independently selected integer from 0 to 3, but cannot be equal to 0 in a structure;
- g is an independently selected integer from 3 to 20;
- each p is an independently selected integer from 0 to 3, each j is an independently selected integer from 0 to 2, however the p and j cannot be equal to 0 in a structure;
- each h is an independently selected integer from 0 to 3, but cannot equal to be 0 in a structure;
- each set of K1 is independently selected from the group containing substituted and unsubstituted C1-C30 alkyl, C3-C30 alkenyl, C3-C30 alkynyl, C7-C30 aryl, and C5-C30 heteroaryl, or the group containing one or more of O, S, N, Si and P atoms;
- wherein any two or more of the substituents of K1 may form bond or ring;
- each set of the substituents of R3˜R6, R3′˜R6′, K2˜K4, and K1′˜K3′ are independently selected from the group containing substituted and unsubstituted C1-C30 alkyl, C3-C30 alkenyl, C3-C30 alkynyl, C6-C30 aryl, and C5-C30 heteroaryl, or the group containing one or more of O, S, N, Si and P atoms;
- wherein
- any two or more of the substituents of K1˜K4, K1′˜K3′, R3˜R6, R3′˜R6′ may form bond or ring;
- but the proviso is that R3˜R5 cannot be equal to an aryl group or a heteroaryl group in a structure;
- A is selected from N or P atoms;
- each independently represents carbon-carbon double bond or carbon-carbon triple bond;
- each X⊖ represents a negative ion, which exists independently in the form of a single negative ion;
- W2 has the structure of
- wherein G1 and G2 are independently selected from the group containing H, halogen, and substituted and unsubstituted C1-C30 alkyl, C3-C30 alkenyl, C3-C30 alkynyl, C6-C30 aryl, and C5-C30 heteroaryl, or the group containing one or more of O, S, N, Si and P atoms;
- wherein any two or more of the substituents of G1 and G2 may form bond or ring.
Dependencies are inferred from the claim text.