Methods of producing alkylfurans
Provided herein are methods of producing dialkylfurans, such as 2,5-dimethylfuran, and other alkyl furans, such as 2-methylfuran. For example, 2,5-dimethylfuran may be produced by reducing (5-methylfuran-2-yl)methanol or 2-(chloromethyl)-5-methylfuran.
1. A method of producing a compound of formula (I′):
wherein:
R 1′ is C m alkyl, wherein m is an integer between 1 and 5; and
R 2′ is C n alkyl, wherein n is an integer between 1 and 5, the method comprising converting a compound of formula (A) to the compound of formula (I′) in the presence of (1) hydrogen and (2) a solid-supported metal catalyst, wherein:
the compound of formula (A) is:
wherein:
R 1a is C m alkyl, (CH 2 ) m Y, (CH 2 ) m-1 CH(O) or —(CH 2 ) m OH wherein:
m is as defined for formula (I′); and
Y is halo; and
R 2a is —(CH 2 ) n-1 CH(O), —(CH 2 ) n OH, or —(CH 2 ) n X, wherein:
n is as defined for formula (I′); and
X is halo; and
wherein the solid-supported metal catalyst is Pd+Pt/MgO; Pd+Au/MgO; or Pd/MgO, or a combination thereof.
2. A composition, comprising:
a compound of formula (A):
wherein:
R 1a is C m alkyl, —(CH 2 ) m Y, —(CH 2 ) m-1 CH(O) or —(CH 2 ) m OH wherein:
m is an integer between 1 and 5; and
Y is halo; and
R 2a is —(CH 2 ) n-1 CH(O), —(CH 2 ) n OH, or —(CH 2 ) n X, wherein:
n is an integer between 1 and 5; and
X is halo;
hydrogen; and
a solid-supported metal catalyst, wherein the solid-supported metal catalyst is Pd+Pt/MgO; Pd+Au/MgO; or Pd/MgO, or a combination thereof.
3. The method of claim 1 , further comprising isolating the compound of formula (I′).
4. The method of claim 1 , wherein the converting the compound of formula (A) to the compound of formula (I′) in the presence of (1) hydrogen and (2) the solid-supported metal catalyst produces a residual solid-supported metal catalyst, and the method further comprises isolating the residual solid-supported metal catalyst.
5. The method of claim 1 , wherein the converting the compound of formula (A″) to the compound of formula (I′) in the presence of (1) hydrogen and (2) the solid-supported metal catalyst produces a residual solid-supported metal catalyst, and the method further comprises:
regenerating the residual solid-supported metal catalyst to produce a regenerated solid-supported metal catalyst; and
combining the regenerated solid-supported metal catalyst with additional compound of formula (A) in the presence of additional hydrogen and optionally additional amide reagent, urea reagent, or a combination thereof, to produce additional compound of formula (I′).
6. The method of claim 1 , wherein R 1a is C m alkyl.
7. The method of claim 1 , wherein R 1a is —(CH 2 ) m Y.
8. The method of claim 1 , wherein R 1a is —(CH 2 ) m-1 CH(O).
9. The method of claim 1 , wherein R 1a is —(CH 2 ) m OH.
10. The method of claim 1 , wherein R 2a is —(CH 2 ) n-1 CH(O).
11. The method of claim 1 , wherein R 2a is —(CH 2 ) n OH.
12. The method of claim 1 , wherein R 2a is —(CH 2 ) n X.
13. The method of claim 1 , wherein m is 1.
14. The method of claim 1 , wherein n is 1.
15. The method of claim 1 , wherein the compound of formula (I′) is
and the compound of formula (A) is
16. The composition of claim 2 , wherein R 1a is C m alkyl.
17. The composition of claim 2 , wherein R 1a is —(CH 2 ) m Y.
18. The composition of claim 2 , wherein R 1a is —(CH 2 ) m-1 CH(O).
19. The composition of claim 2 , wherein R 1a is —(CH 2 ) m OH.
20. The composition of claim 2 , wherein R 2a is —(CH 2 ) n-1 CH(O).
21. The composition of claim 2 , wherein R 2a is —(CH 2 ) n OH.
22. The composition of claim 2 , wherein R 2a is —(CH 2 ) n X.
23. The composition of claim 2 , wherein m is 1.
24. The composition of claim 2 , wherein n is 1.
25. The composition of claim 2 , wherein the compound of formula (A) is
26. A composition comprising:
a compound of formula (A):
wherein:
R 1a is C m alkyl, —(CH 2 ) m Y, —(CH 2 ) m-1 CH(O) or —(CH 2 ) m OH wherein:
m is an integer between 1 and 5; and
Y is halo; and
R 2a is —(CH 2 ) n-1 CH(O), —(CH 2 ) n OH, or —(CH 2 ) n X, wherein:
n is an integer between 1 and 5; and
X is halo:
hydrogen;
a solid-supported metal catalyst, wherein the solid-supported metal catalyst is Pd+Pt/MgO; Pd+Au/MgO; or Pd/MgO, or a combination thereof; and
a compound of formula (I′),
wherein:
R 1′ is C m alkyl, wherein m is an integer between 1 and 5; and
R 2′ is C n alkyl, wherein n is an integer between 1 and 5.
27. The composition of claim 26 , wherein the compound of formula (A) is
and the compound of formula (I′) is