Low pressure carbonylation of heterocycles
Heterocycles, e.g., epoxides, are carbonylated at low pressure with high percentage conversion to cyclic, ring expanded products using the catalyst where L is tetrahydrofuran (THF).
1. A process for carbonylation of a compound having the formula:
where R 1 , R 2 , R 3 and R 4 are the same or different and are each selected from the group consisting of a hydrogen atom, a halogen atom, a carbon-containing group, a fluorine containing group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, and two or more of these can be bonded to each other to form a ring or rings;
said process comprising the steps of reacting compound (I) with carbon monoxide under a pressure up to 125 psi, in the presence of a catalytically effective amount of a catalyst (D), described below, to yield a beta-lactone
where the catalyst (D) has the formula:
where R 7 and R 16 are each a hydrogen atom, a carbon-containing group containing 1-30 carbon atoms, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, or a silicon-containing group;
where R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 are the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, a carbon-containing group containing 1 to 30 carbon atoms, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, and two or more of R 7 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 can be bonded to each other to form a ring or rings; and
where L is a Lewis base, which can be absent, and if present, each L is the same or different and is selected from the group consisting of ethers, thioethers, esters, amines, pyridines, phosphines, phosphites, nitriles and carbenes.
2. The process of claim 1 were the catalyst (D) has the structural formula:
where L is tetrahydrofuran.
3. The process of claim 2 where the reaction is carried out in glassware.
4. The process of claim 2 where the carbon monoxide is at a pressure of 100 psig.
5. The process of claim 2 where the reaction is carried out at atmospheric pressure.
6. The process of claim 1 where R 1 , R 2 , R 3 and R 4 are the same or different and are each selected from the group consisting of a hydrogen atom and a carbon-containing group with from 1 to 20 carbons.
7. The process of claim 1 where R 1 , R 2 , R 3 and R 4 are the same or different and are each selected from the group consisting of a hydrogen atom and an oxygen-containing group with from 1 to 20 carbons.
8. The process of claim 1 where R 1 , R 2 , R 3 and R 4 are the same or different and are each selected from the group consisting of a hydrogen atom and a nitrogen-containing group with from 1 to 20 carbons.
9. The process of claim 1 where R 1 , R 2 , R 3 and R 4 are the same or different and are each selected from the group consisting of a hydrogen atom and a sulfur-containing group with from 1 to 20 carbons.
10. The process of claim 1 where R 2 and R 4 are hydrogen atoms.
11. The process of claim 10 where R 1 and R 3 are methyl.
12. The process of claim 1 where R 2 , R 3 and R 4 are hydrogen atoms.
13. The process of claim 12 where R 1 is selected form the group consisting of:
14. The process of claim 1 where R 1 , R 2 , R 3 and R 4 are each hydrogen and the product is propiolactone.
15. The process of claim 1 where R 1 is methyl, R 2 , R 3 and R 4 are each hydrogen and the product is beta-butyrolactone.
16. The process of claim 1 where R 2 and R 4 are hydrogen and R 1 and R 3 taken together with the atoms to which they are attached form a ring.
17. The process of claim 16 where (I) is cyclohexene oxide.
18. The process of claim 16 where (I) is
19. The process of claim 1 where R 7 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 are each a hydrogen atom or a carbon-containing group containing 1-30 carbon atoms.
20. The process of claim 1 where at least one L is tetrahydrofuran.
21. The process of claim 1 where the reaction is carried out in glassware.
22. The process of claim 1 where the carbon monoxide is at 100 psig.
23. The process of claim 1 where the reaction is carried out at atmospheric pressure.
24. The process of claim 1 where the mole ratio of (I) charged into the reaction to catalyst (D) charged is in the range of 1:1 to 10,000:1.
25. The process of claim 1 where the mole ratio of (I) charged into the reaction to catalyst (D) charged is in the range of 25:1 to 150:1.
26. The process of claim 1 where the reaction is carried out in a solvent selected from the group consisting of dimethoxyethane, diglyme, triglyme, tetrahydrofuran and toluene.
27. The process of claim 1 where the reaction is carried out in dimethoxyethane.