CONVERSION OF MUCONOLACTONE TO BETA-KETOADIPATES AND METHODS THEREFOR
Described herein are materials and methods to generate beta-ketoadipates cost-efficiently and with reduced environmental impact from muconolactone. Advantageously, the described beta-ketoadipates, including dimethyl beta-ketoadipates, are more stable than traditional βKA and can be produced with a reduction in the amount of salt byproducts, by as much as half.
1 . A method comprising:
providing methyl muconolactone; and
reacting the methyl muconolactone in the presence of a base and an alcohol, thereby generating a β-ketoadipate.
2 . The method of claim 1 , wherein the β-ketoadipate is dimethyl β-ketoadipate.
3 . The method of claim 1 , wherein the step of reacting is performed in the presence of a catalyst.
4 . The method of claim 3 , wherein the catalyst is a heterogenous catalyst comprising copper oxide and calcium oxide.
5 . The method of claim 3 , wherein the catalyst comprises K 2 CO 3 , NaCO 3 or a combination thereof.
6 . The method of claim 1 further comprising:
providing muconolactone; and
reacting muconolactone in the presence of an acid and methanol, thereby generating the methyl muconolactone.
7 . The method of claim 6 , wherein the acid is H 2 SO 4 .
8 . The method of claim 1 , wherein the base is NEt 3 , pyridine, piperidine, N,N-dimethylamine, 1,5,7-triazabicyclo 4.4.0 dec-5-ene or a combination thereof.
9 . The method of claim 1 , wherein the alcohol is methanol.
10 . The method of claim 1 , wherein the step of reacting methyl muconolactone further comprises reacting in the presence of a solvent.
11 . The method of claim 10 , wherein the solvent is a polar solvent.
12 . The method of claim 10 , wherein the solvent is acetone, dichloromethane, tetrahydrofuran, or a combination thereof.
13 . A catalyst comprising:
a copper oxide dispersed on a calcium oxide support.
14 . The catalyst of claim 13 , wherein the catalyst has a weight percentage of copper selected from the range of 1 wt % to 18 wt %.
15 . The catalyst of claim 13 , wherein the catalyst promotes the conversion of methyl muconolactone to muconic acid at a conversion efficiency greater than or equal to 75%.
16 . The catalyst of claim 13 , wherein the catalyst promotes the conversion of methyl muconolactone to β-ketoadipate at a conversion efficiency greater than or equal to 50%.
17 . A method comprising:
providing a calcium hydroxide support;
dispersing copper nitrate trihydrate on the calcium hydroxide support via incipient wetness impregnation;
calcinating the copper nitrate trihydrate and calcium hydroxide support, thereby generating a copper oxide catalyst on a calcium oxide support.
18 . The method of claim 17 , wherein the step of calcinating is performed at a temperature of about 500° C. for about 4 hours.
19 . The method of claim 17 , wherein the copper oxide catalyst has a weight percentage of copper selected from the range of 1 wt % to 18 wt %.