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 hydrogen peroxide in the presence of a catalyst, in a biphasic system comprising an organic phase and an aqueous reaction medium, and wherein the molar ratio of the terminal olefin to the hydrogen peroxide is in the range of from 1:0.1 to 1:1, and wherein the catalyst comprises a water-soluble manganese complex of 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 atom; L or each L independently is a polydentate ligand of triazacyclononane or 1,4,7-trimethyl-1,4,7,-triazacyclononane; each X independently is a 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 selected from the group consisting of C 1 -C 20 alkyl, C 1 -C 20 cycloalkyl, C 1 -C 20 aryl, benzyl and combinations thereof and each μ-X independently is a bridging coordinating species selected from the group consisting of: RO − , Cl − , Br − , F − , 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 selected from the group consisting of C 1 -C 20 alkyl, C r C 20 cycloalkyl, C 1 -C 20 aryl, benzyl and combinations thereof, and Y is an anion counterion is 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, wherein R is selected from the group consisting of C 1 -C 20 alkyl, C 1 -C 20 cycloalkyl, C 1 -C 20 aryl, benzyl and combinations thereof, wherein the aqueous reaction medium further comprises a buffer system to stabilize a pH, and the aqueous reaction medium has a pH range from 3 to 6.5.
2. The process of claim 1 , further comprising stirring the biphasic system.
3. The process of claim 2 , wherein the stirring the biphasic system comprises stirring the system with a stirrer at between 100 rpms and 650 rpm.
4. The process of claim 1 , wherein the aqueous reaction medium further comprises a buffer system at a buffer to catalyst ratio from 10:1 to 100:1.
5. The process of claim 4 , wherein the buffer system comprises an acid-salt combination.
6. The process of claim 1 , wherein the catalyst is present in a concentration from 0.01 mmol/L to 10 mmol/L.
7. 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.
8. The process of claim 1 , wherein the terminal olefin is one or more terminal olefins having a solubility in the range of from 0.1 to 50 g/L.
9. 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.
10. The process of claim 1 , wherein the biphasic system further includes a phase transfer agent, a surfactant, or both.
11. The process of claim 1 , wherein the catalyst comprises
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 of triazacyclononane or 1,4,7-trimethyl-1,4,7,-triazacyclononane; each μ-X independently is a bridging coordinating species of: O 2− , RCOO − , RSO 3 − , RSO 4 − , wherein R is selected from the group consisting of C 1 -C 20 alkyl, C 1 -C 20 cycloalkyl, C 1 -C 20 aryl, benzyl and combinations thereof, and Y is selected from the group consisting of SO 4 2− , PF 6 − , acetate, and combinations thereof.
12. The process of claim 1 , wherein the molar ratio of the terminal olefin to the hydrogen peroxide in the range of from 1:0.1 to 1.2:1.
13. The process of claim 1 , wherein the reaction is performed in a batch process, in a continuous process or in a semi-continuous process.
14. The process of claim 1 , wherein the aqueous reaction medium comprises a 100% aqueous medium excluding any dissolved epoxide and terminal olefin.
15. The process of claim 8 , wherein the aqueous reaction medium comprises a pH in the range of from 3 to 4.2.
16. The process of claim 1 , wherein the catalyst comprises
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 of triazacyclononane or 1,4,7-trimethyl-1,4,7,-triazacyclononane; each μ-X independently is a bridging coordinating species of: O 2− , RCOO − , RSO 3 − , RSO 4 − , wherein R is selected from the group consisting of C 1 -C 20 alkyl, C 1 -C 20 cycloalkyl, C 1 -C 20 aryl, benzyl and combinations thereof, and Y is selected from the group consisting of SO 4 2− , PF 6 − , acetate, and a combination thereof;
wherein the aqueous reaction medium further comprises a buffer system with a pH range from 3.0 to 4.2; 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.
17. The process of claim 1 , wherein the terminal olefin is 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.
18. The process of claim 17 , wherein the terminal olefin is selected from the group of allyl bromide, allyl chloride, allyl acetate, allyl propionate, allyl butanoate, allyl hexanoate, allyl octanoate, allyl decanoate, allyl stearate, allyl palmitate, allyl salicylate, allyl lactate, allyl succinate, diallyl glutarate, diallyl adipate, diallyl pimelate, diallyl oxalate, diallyl maleate, diallyl phthalate, and diallyl isophthalate.
19. The process of claim 17 , wherein the terminal olefin is 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 alkanoic acids having 3 to 8 carbon atoms.
20. The process of claim 5 , wherein the acid-salt combination comprises oxalic acid-oxalate salt.