Method for preparing conjugated diene phosphonate compounds
It is provided a method for preparing conjugated diene phosphonate compounds with high reactivity, which can be used to prepare a variety of phosphonate-bearing conjugated dienes. Some of those dienes will become reactive monomers to make polymers and co-polymers. The said method comprises the step of reacting α, β- or β, γ-unsaturated ketones or aldehydes with phosphorus acid or its derivates optionally in a mixture of acetic anhydride and/or acetic acid, to obtain a conjugated diene phosphonate compound having the formula (III)
1. A method for preparing conjugated diene phosphonate compounds from α,β- or β,γ-unsaturated ketones or aldehydes, which comprises, reacting an α,β- or β,γ-unsaturated ketone or aldehyde having the formula I or II,
with a phosphorus acid or its derivatives having the structure,
to obtain a conjugated diene phosphonate compound having the formula III,
wherein,
R 1 , R 2 , R 3 , R 4 , and R 5 represent, independently, hydrogen, alkyl, aryl, alkaryl, aralkyl, cycloalkyl, heterocycloalkyl, or alkenyl groups;
R 6 and R 7 represent, independently, hydrogen, alkyl, aryl, alkaryl, aralkyl, cycloalkyl, alkenyl groups, or metals selected from the group consisting of Na, Li, and Ca; and
said reaction is optionally carried out in a mixture of acetic anhydride and/or acetic acid.
2. The method of claim 1 , wherein the said alkyl, alkenyl comprise from 1˜24 carbon atoms, said aryl comprises from 6˜24 carbon atoms, said alkaryl, aralkyl comprise from 7˜24 carbon atoms, and said cycloalkyl, heterocycloalkyl comprise from 3˜24 carbon atoms.
3. The method of claim 1 , wherein the said alkyl, alkenyl comprise from 1˜18 carbon atoms, said aryl comprises from 6˜18 carbon atoms, said alkaryl, aralkyl comprise from 7˜18 carbon atoms, and said cycloalkyl, heterocycloalkyl comprise from 3˜18 carbon atoms.
4. The method of claim 1 , wherein R 1 and/or R 2 represent hydrogen.
5. The method of claim 1 , wherein any two of R 1 , R 2 , R 3 , R 4 and R 5 are together formed into a cycloalkyl, or heterocycloalkyl group.
6. The method of claim 5 , wherein said cycloalkyl or heterocycloalkyl group is selected from 5, 6, 7 and 8 membered rings.
7. The method of claim 1 , wherein R 6 and R 7 are together formed into a cycloalkyl, or heterocycloalkyl group.
8. The method of claim 7 , wherein said cycloalkyl or heterocycloalkyl group is selected from 5, 6, 7 and 8 membered rings.
9. The method according to claim 1 , wherein R 1 , R 2 and R 4 , represent hydrogen.
10. The method according to claim 1 , wherein R 3 and R 5 represent methyl.
11. The method according to claim 1 , wherein R 1 , R 2 , and R 4 represent hydrogen and R 3 and R 5 represent methyl.
12. The method according to claim 1 , wherein R 6 , and R 7 represent hydrogen.
13. The method according to claim 1 , wherein said compound I or II is added in the molar ratio of (1˜1.5):1 relative to said phosphorus acid or its derivates.
14. The method according to claim 13 , wherein said compound I or II is added in the molar ratio of (1˜1.2):1 relative to said phosphorus acid or its derivate.
15. The method according to claim 1 , wherein the reaction time remains 4˜24 hours.
16. The method according to claim 15 , wherein the reaction time remains 4˜8 hours.
17. The method according to claim 1 , wherein the reaction temperature remains 0˜100° C.
18. The method according to claim 17 , wherein the reaction temperature remains 20˜60° C.