Process for the manufacture of a 1,2-epoxide
View Patent ↗The invention relates to a process for the manufacture of a 1,2-epoxide by catalytic oxidation of a terminal olefin with hydrogen peroxide wherein the catalytic oxidation is performed in a biphasic system comprising an organic phase and an aqueous reaction medium, wherein a water-soluble manganese complex is used as oxidation catalyst, wherein a terminal olefin is used with a solubility at 20° C. of at least 0.01 to 100 g in 1 liter water, and wherein the molar ratio of terminal olefin to hydrogen peroxide is in the range of from 1:0.1 to 1:2.
1. A process for the manufacture of a 1,2-epoxide, comprising:
reacting a terminal olefin with an oxidant in the presence of a catalyst, in a biphasic system comprising an organic phase and an aqueous reaction medium, wherein the catalyst comprises a water-soluble manganese complex and the terminal olefin has a solubility at 20° C. of at least 0.01 to 100 g in 1 liter water, and wherein the molar ratio of the terminal olefin to the oxidant is in the range of from 1:0.1 to 1:1, wherein the water-soluble manganese complex comprises a mononuclear manganese complex of the formula (I):
[LMnX 3 ]Y (I)
or a binuclear manganese complex of the formula (II):
[LMn(μ−X) 3 MnL]Y 2 (II)
wherein Mn is a manganese; L or each L independently is a polydentate ligand; each X independently is a coordinating species and each μ−X independently is a bridging coordinating species, selected from the group consisting of: RO − , Cl − , Br − , I − , F − , NCS − , N 3 − , I 3 − , NH 3 , NR 3 , RCOO − , RSO 3 − , RSO 4 − , OH − , O 2− , HOO − , H 2 O, SH − , CN − , OCN − , and S 4 2− and combinations thereof, wherein R is a C 1 -C 20 radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl and combinations thereof, and Y is an oxidatively-stable counterion.
2. The process of claim 1 , wherein each polydentate ligand is independently selected from acyclic compounds having at least 7 atoms in the backbone or cyclic compounds having at least 9 atoms in the ring, wherein each polydentate ligand having 3 nitrogen atoms with the nitrogen atoms separated by at least two carbon atoms.
3. The process of claim 1 , wherein a binuclear water-soluble manganese complex is used as the catalyst.
4. The process of claim 1 , wherein the catalyst is used in a molar ratio of the catalyst (Mn) to the terminal olefin of from 1:10 to 1:10,000,000.
5. The process of claim 1 , wherein the aqueous reaction medium is a water phase.
6. The process of claim 1 , wherein the aqueous reaction medium further comprises a buffer system and a pH in the range of from 2.5 to 7.
7. The process of claim 1 , wherein the reaction is carried out at temperatures in the range from −5° C. and 30° C.
8. The process of claim 1 , wherein the biphasic system is created by adding the terminal olefin in an amount greater than what dissolves in the reaction medium, by conversion of the terminal olefin into the corresponding 1,2-epoxide, or combinations thereof.
9. The process of claim 1 , wherein the terminal olefin is one or more olefins having a solubility from 0.01 to 50 g/L.
10. The process of claim 9 , wherein the terminal olefin is one or more olefins selected from the group of halogenated olefins having from 3 to 8 carbon atoms in the molecule, hydroxyl-substituted olefins having 4 to 6 carbon atoms in the molecule, carbonyl-substituted olefins having 3 to 6 carbon atoms in the molecule, alkoxy-substituted olefins having 3 to 8 carbon atoms in the molecule, alkenoic acids having 7 to 8 carbon atoms and esters of alkenoic acids having in total 4 to 8 carbon atoms, and allyl esters of alkanoic acids having 3 to 8 carbon atoms.
11. The process of claim 9 , wherein the terminal olefin is selected from the group consisting of allyl bromide, allyl chloride, allyl propionate and allyl acetate.
12. The process of claim 1 , wherein the oxidant comprises hydrogen peroxide and is used as an aqueous solution in a concentration of from 15% to 98%.
13. The process of claim 1 , wherein the oxidant comprises hydrogen peroxide at a molar ratio of the terminal olefin to the hydrogen peroxide in the range of from 1:0.1 to 1.2:1.
14. The process of claim 1 , wherein the oxidant is added to the aqueous reaction medium at a rate about equal to the reaction rate.
15. The process of claim 1 , wherein the reaction is performed in a batch process, in a continuous process or in a semi-continuous process.
16. The process of claim 9 , wherein the terminal olefin is an allyl ester of an alkanoic acid having in total 3 to 8 carbon atoms.
17. The process of claim 9 , wherein the terminal olefin is a diolefin.
18. The process of claim 9 , wherein the terminal olefin is selected from the group consisting of allyl deconoate, allyl salicylate, diallyl phthalate, and combinations thereof.
19. The process of claim 1 , wherein the aqueous reaction medium comprises a 100% aqueous medium excluding any dissolved epoxide and terminal olefin.
20. The process of claim 6 , wherein the aqueous reaction medium further comprises a pH in the range of from 2.5 to 6.5.
21. The process of claim 6 , wherein the buffer system comprises an acid-salt combination.
22. The process of claim 21 , wherein the acid-salt combination comprises oxalic acid-oxalate salt.
23. The process of claim 1 , wherein Y is an oxidatively-stable counterion selected from the group consisting of RO − , Cl − , Br − , I − , F − , SO 4 2− , RCOO − , PF 6 − , acetate, tosylate, triflate (CF 3 SO 3 − ) and a combination thereof.
24. The process of claim 1 , wherein the terminal olefin comprises one or more terminal olefins selected from the group of halogenated terminal olefins having from 3 to 8 carbon atoms in the molecule, alkenoic acids having 7 to 8 carbon atoms and esters of alkenoic acids having in total 4 to 8 carbon atoms, and allyl esters of alkenoic acids having 3 to 8 carbon atoms.
25. The process of claim 1 , wherein the catalyst comprises a mononuclear manganese complex of the formula (I):
[LMnX 3 ]Y (I)
or a binuclear manganese complex of the formula (II):
[LMn(μ−X) 3 MnL]Y 2 (II)
wherein Mn is a manganese; L or each L independently is a polydentate ligand; each X independently is a coordinating species and each μ−X independently is a bridging coordinating species, selected from the group consisting of: RO − , Cl − , Br − , I, F − , NCS − , N 3 − , I 3 − , NH 3 , NR 3 , RCOO − , RSO 3 − , RSO 4 − , OH − , O 2− , O 2 2− , HOO − , H 2 O, SH − , CN − , OCN − , and S 4 2− and combinations thereof, wherein R is a C 1 -C 20 radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl and combinations thereof, and Y is an oxidatively-stable counterion;
wherein the aqueous reaction medium further comprises a buffer system with a pH range from 2.5 to 7; and
wherein the molar ratio of the terminal olefin to the hydrogen peroxide in the range of from 1:0.1 to 1.2:1.