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 hydrogenation of (5-methylfuran-2-yl) methanol or 2-(chloromethyl)-5-methylfuran in the presence of a solid supported metal catalyst having an excess of either basic or acidic sites (as determined by chemisorption of CO2 or NH3). The process could further include a urea reagent (TMU, DMPU, TMI) and an alkyl benzene.
1. A method of producing a compound of formula (I′):
wherein:
R 1′ is C m alkyl, wherein m is an integer greater than or equal to 0, provided that when m is 0, R 1′ is H; and
R 2′ is C n alkyl, wherein n is an integer greater than or equal to 1,
the method comprising converting a compound of formula (A) to the compound of formula (I′) in the presence of (1) hydrogen, (2) a solid-supported metal catalyst comprising a metal component and an acidic solid support, and (3) a urea reagent,
wherein:
the compound of formula (A) is:
wherein:
R 1a is —(CH 2 ) m-1 CH(O) or —(CH 2 ) m OH, wherein:
m is as defined for formula (I′), provided that when m is 0, R 1a is H; 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
the acidic solid support is a solid support that (i) has more acidic sites than basic sites, and (ii) chemisorbs at least 0.001 g ammonia/g solid support.
2. The method of claim 1 , wherein the acidic solid support comprises zeolite, an acidic metal oxide, or an acidic mixed metal oxide, or any combination thereof.
3. The method of claim 1 , wherein the acidic solid support comprises SiO 2 , ZnO, CdO, Al 2 O 3 , CeO 2 , ThO 2 , TiO 2 , ZrO 2 , SnO 2 , PbO, As 2 O 3 , Bi 2 O 3 , Sb 2 O 5 , V 2 O 5 , Cr 2 O 3 , MoO 3 , WO 3 , SiO 2 —Al 2 O 3 , SiO 2 —TiO 2 , SiO 2 —SnO 2 , SiO 2 —ZrO 2 , SiO 2 —BeO, SiO 2 —MgO, SiO 2 —CaO, SiO 2 —SrO, SiO 2 —ZnO, SiO 2 —Ga 2 O 3 , SiO 2 —YrO 3 , Si—O 2 —La 2 O 3 , SiO 2 —MoO 3 , SiO 2 —WO 3 , SiO 2 —V 2 O 5 , SiO 2 —ThO 2 , Al 2 O 3 —MgO, Al 2 O 3 —ZnO, Al 2 O 3 —CdO, Al 2 O 3 —B 2 O 3 , Al 2 O 3 —ThO 2 , Al 2 O 3 —TiO 2 , Al 2 O 3 —ZrO 2 , Al 2 O 3 —V 2 O 5 , Al 2 O 3 —MoO 3 , Al 2 O 3 —WO 3 , Al 2 O 3 —Cr 2 O 3 , Al 2 O 3 —Mn 2 O 3 , Al 2 O 3 —Fe 2 O 3 , Al 2 O 3 —Co 3 O 4 , Al 2 O 3 —NiO, TiO 2 —CuO, TiO 2 —MgO, TiO 2 —ZnO, TiO 2 —CdO, TiO 2 —ZrO 2 , TiO 2 —SnO 2 , TiO 2 —Bi 2 O 3 , TiO 2 —Sb 2 O 5 , TiO 2 —V 2 O 5 , TiO 2 —Cr 2 O 3 , TiO 2 —MoO 3 , TiO 2 —WO 3 , TiO 2 —Mn 2 O 3 , TiO 2 —Fe 2 O 3 , TiO 2 —Co 3 O 4 , TiO 2 —NiO, ZrO 2 —CdO, ZnO—MgO, ZnO—Fe 2 O 3 , MoO 3 —CoO—Al 2 O 3 , MoO 3 —NiO—Al 2 O 3 , TiO 2 —SiO 2 —MgO, MoO 3 —Al 2 O 3 —MgO, ZSM5, or Beta zeolite, or any combination thereof.
4. The method of claim 3 , wherein the acidic solid support comprises Al 2 O 3 , or SiO 2 , or any combination thereof.
5. The method of claim 1 , wherein the solid-supported metal catalyst is:
Pd/Al 2 O 3 ;
Pd/ZSM5;
Pd/Beta zeolite;
Pd+Au/Al 2 O 3 ;
Pd+Ag/Al 2 O 3 ; and
Pd+Cu/Al 2 O 3 ,
or any combination thereof.
6. The method of claim 5 , wherein the solid-supported metal catalyst is Pd/Al 2 O 3 .
7. The method of claim 1 , wherein the compound of formula (A) is converted to the compound of formula (I′) in the presence of (1) hydrogen, (2) the solid-supported metal catalyst, (3) a urea reagent, and (4) an aromatic reagent.
8. A method of producing a compound of formula (I′):
wherein:
R 1′ is C m alkyl, wherein m is an integer greater than or equal to 0, provided that when m is 0, R 1′ is H; and
R 2′ is C n alkyl, wherein n is an integer greater than or equal to 1,
the method comprising converting a compound of formula (A) to the compound of formula (I′) in the presence of (1) hydrogen, (2) a solid-supported metal catalyst comprising a metal component and a solid support, and (3) a urea reagent under acidic conditions,
wherein:
the compound of formula (A) is:
wherein:
R 1a is —(CH 2 ) m-1 CH(O) or —(CH 2 ) m OH, wherein:
m is as defined for formula (I′), provided that when m is 0, R 1a is H; 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.
9. The method of claim 8 , wherein the compound of formula (A) is converted to the compound of formula (I′) in the presence of (1) hydrogen, (2) the solid-supported metal catalyst, (3) the urea reagent, and (4) an aromatic reagent.
10. The method of claim 8 , wherein the solid support is an acidic support.
11. The method of claim 8 , wherein the solid support is a neutral support, and wherein the compound of formula (A) is converted to the compound of formula (I′) in the presence of (1) hydrogen, (2) the solid-supported metal catalyst, (3) the urea reagent, and (4) an acid.
12. The method of claim 11 , wherein the neutral support comprises carbon.
13. The method of claim 11 , wherein the solid support is a neutral support, and wherein the compound of formula (A) is converted to the compound of formula (I′) in the presence of (1) hydrogen, (2) the solid-supported metal catalyst, (3) the urea reagent, (4) the acid, and (5) an aromatic reagent.
14. A method of producing a compound of formula (I′):
wherein:
R 1′ is C m alkyl, wherein m is an integer greater than or equal to 0, provided that when m is 0, R 1′ is H; and
R 2′ is C n alkyl, wherein n is an integer greater than or equal to 1,
the method comprising converting a compound of formula (A) to the compound of formula (I′) in the presence of (1) hydrogen, (2) a solid-supported metal catalyst comprising a metal component and a solid support, (3) a urea reagent, and (4) an acid, wherein:
the compound of formula (A) is:
wherein:
R 1a is —(CH 2 ) m-1 CH(O) or —(CH 2 ) m OH, wherein:
m is as defined for formula (I′), provided that when m is 0, R 1a is H; 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;
the solid support is:
an acidic support that (i) has more acidic sites than basic sites, and (ii) chemisorbs at least 0.001 g ammonia/g solid support, or
a neutral support.
15. The method of claim 11 , wherein the acid is:
(i) generated in situ;
(ii) a Bronsted acid;
(iii) H—X or H—Y, wherein X and Y are as defined for formula (A) above; or
(iv) hydrochloric acid or sulfonic acid.
16. The method of claim 14 , wherein the compound of formula (A) is converted to the compound of formula (I′) in the presence of (1) hydrogen, (2) the solid-supported metal catalyst, (3) the urea reagent, (4) the acid, and (5) an aromatic reagent.
17. The method of claim 7 , wherein the urea reagent and the aromatic reagent are present in a mass ratio of between 1:10 and 10:1.
18. The method of claim 1 , wherein the compound of formula (I′) is produced at a yield of at least 25%; and a selectivity of at least 25%.
19. The method of claim 1 , wherein the compound of formula (A) and the hydrogen are present in a mass ratio between 1:2.9 and 1:3.8.
20. The method of claim 1 , wherein the compound of formula (A) is converted to the compound of formula (I′) at a temperature of less than 50° C.
21. The method of claim 1 , wherein the metal component is impregnated, deposited, precipitated, or any combination thereof, onto the solid support.
22. The method of claim 1 , wherein the metal component comprises:
(i) at least one metal;
(ii) at least two metals;
(iii) one metal, two metals, or three metals;
(iv) at least one Group 10 metal; or
(v) at least one Group 10 metal, and at least one Group 11 metal.
23. The method of claim 1 , wherein the metal component comprises:
(i) palladium, or platinum, or a combination thereof; and
(ii) gold, silver, or copper, or any combination thereof.
24. The method of claim 1 , wherein the metal component comprises palladium and at least one additional metal, wherein the palladium and the least one additional metal are present in the catalyst in a weight ratio of 0.1 to 20.
25. The method of claim 1 , wherein the metal component comprises:
(i) palladium;
(ii) palladium and platinum;
(iii) palladium and gold;
(iv) palladium and copper;
(v) palladium and silver;
(vi) platinum;
(vii) platinum and gold;
(viii) platinum and copper; or
(ix) platinum and silver.
26. The method of claim 1 , wherein the catalyst has a total metal loading between 0.1% to 20% by weight.
27. The method of claim 1 , wherein the urea reagent is a reagent of formula (ii):
wherein:
(A) each R a , R b , R c and R d is independently H, aliphatic, aryl or heteroaryl; or
(B) R a and R b are taken together with the nitrogen atoms to which they are connected to form a cyclic moiety having at least 3 ring atoms; and each R c and R d is independently H, aliphatic, aryl or heteroaryl; or
(C) each R a and R b is independently H, aliphatic, aryl or heteroaryl; and R c and R d are taken together with the nitrogen atoms to which they are connected to form a cyclic moiety having at least 3 ring atoms; or
(D) R a and R b are taken together with the nitrogen atoms to which they are connected to form a cyclic moiety having at least 3 ring atoms; and R c and R d are taken together with the nitrogen atoms to which they are connected to form a cyclic moiety having at least 3 ring atoms; or
(E) each R a and R c is independently H, aliphatic, aryl or heteroaryl; and R b and R d are taken together with the nitrogen atoms to which they are connected to form a cyclic moiety having at least 5 ring atoms; or
(F) each R b and R d is independently H, aliphatic, aryl or heteroaryl; and R a and R c are taken together with the nitrogen atoms to which they are connected to form a cyclic moiety having at least 5 ring atoms.
28. The method of claim 1 , wherein the urea reagent is a cyclic urea reagent.
29. The method of claim 1 , wherein the urea reagent is a reagent of formula (iii):
wherein:
each R a and R c is independently H, aliphatic, aryl or heteroaryl; and
t is an integer greater than or equal to 0.
30. The method of claim 1 , wherein the urea reagent is
or a combination thereof.
31. The method of claim 7 , wherein the aromatic reagent comprises:
(i) at least one mono-aryl compound, at least one di-aryl compound, or at least one tri-aryl compound, or any mixtures thereof;
(ii) an alkyl benzene;
(iii) a linear alkyl benzene; or
(iv) toluene, benzene, xylene, or mesitylene, or any combination thereof.
32. The method of claim 1 , wherein:
(i) m is 0 or 1;
(ii) n is 1; or
both (i) and (ii).
33. A method of producing a compound of formula (J):
wherein:
R 1′ is C m alkyl, wherein m is an integer greater than or equal to 0, provided that when m is 0, R 1′ is H; and
R 2′ is C n alkyl, wherein n is an integer greater than or equal to 1,
the method comprising:
combining a compound of formula (I′) produced according to the method of claim 1 , and ethylene to produce the compound of formula (J).
34. A composition, comprising:
a compound of formula (A):
wherein:
R 1a is —(CH 2 ) m-1 CH(O) or —(CH 2 ) m OH, wherein:
m is an integer greater than or equal to 0, provided that when m is 0, R 1a is H; 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 greater than or equal to 1; and
X is halo;
hydrogen;
a catalyst comprising a metal component and an acidic solid support, wherein the acidic solid support is a solid support that (i) has more acidic sites than basic sites, and (ii) chemisorbs at least 0.001 g ammonia/g solid support; and
a urea reagent.
35. A composition, comprising:
a compound of formula (A):
wherein:
R 1a is —(CH 2 ) m-1 CH(O) or —(CH 2 ) m OH, wherein:
m is an integer greater than or equal to 0, provided that when m is 0, R 1a is H; 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 greater than or equal to 1; and
X is halo;
hydrogen;
a catalyst comprising a metal component and a solid support, wherein the solid support is:
an acidic solid support (i) having more acidic sites than basic sites, and (ii) chemisorbs at least 0.001 g ammonia/g solid support, or
a neutral support;
a urea reagent; and
an acid.
36. The composition of claim 34 , further comprising an aromatic reagent.