# US 2012/0083609 A1 · Methods for the conversion of a substituted furan to a substituted pyrrole

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- Number: US 2012/0083609 A1
- Document ID: US20120083609A1
- Status: Published application
- Kind: A1
- Application number: 12/895,945
- Filed: 2010-10-01
- Published: 2012-04-05
- Earliest claimed: 2010-10-01
- Assignees: Chevron Phillips Chemical Company LP
- Inventors: Bruce E. Kreischer; Orson L. Sydora; Steven Hutchinson; Eduardo J. Baralt; Ron D. Knudsen
- Web page: https://patentgrep.com/patent/US20120083609A1

## CPC

- C07D 207/323: with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atoms
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## Abstract

The present invention discloses processes for producing substituted pyrrole compounds, such as 2,5-disubstituted pyrroles. Synthetic processes which directly convert substituted furan compounds to substituted pyrrole compounds, via a reaction of the substituted furan compound with ammonia and/or an ammonium salt in the presence of a catalyst, also are described.

## Claims

### Claim 1

(canceled)

### Claim 2 (depends on 24)

The process of claim 24, wherein the substituted pyrrole compound has the formula:
wherein:
R2p, R3p, R4p, and R5p independently are a hydrogen atom, a C1-C30 organyl group, or a C3-C60 silyl group, and
at least one of R2p, R3p, R4p, and R5p is not a hydrogen atom.

### Claim 3 (depends on 2)

The process of claim 2, wherein R2p, R3p, R4p, and R5p independently are a hydrogen atom or a C1-C18 hydrocarbyl group, and
at least one of R2p, R3p, R4p, and R5p is not a hydrogen atom.

### Claim 4 (depends on 2)

The process of claim 2, wherein R2p and R5p independently are a C1-C18 hydrocarbyl group, and R3p and R4p are hydrogen.

### Claim 5 (depends on 2)

The process of claim 2, wherein R2p and R5p independently are a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a t-butyl group, a phenyl group, a benzyl group, a tolyl group, or a xylyl group.

### Claim 6 (depends on 2)

The process of claim 2, wherein at least one of R2p and R5p is a hydrogen atom.

### Claim 7 (depends on 24)

The process of claim 24, wherein the substituted pyrrole compound comprises a compound having formula P2, P3, P4 or P5:
wherein R12p, R13p, R14p, R22p, R24p, R33p, R34, R42, and R45 independently are a C1-C18 hydrocarbyl group.

### Claim 8 (depends on 24)

The process of claim 24, wherein the substituted pyrrole compound comprises 2,5-dimethylpyrrole, 2-methyl-5-ethylpyrrole, 2,5-diethylpyrrole, 2-ethyl-5-methylpyrrole, 2-ethyl-5-n-propylpyrrole, 2,5-di-n-propylpyrrole, 2,5-diisopropylpyrrole, 2,5-di-n-butylpyrrole, 2,5-di-n-pentylpyrrole, 2,5-di-n-hexylpyrrole, 2,5-di-n-heptylpyrrole, 2,5-di-n-octylpyrrole, 2,3,5-triethylpyrrole, 2,3,5-tri-n-butylpyrrole, 2,3,5-tri-n-pentylpyrrole, 2,3,5-tri-n-hexylpyrrole, 2,3,5-tri-n-heptylpyrrole, 2,3,5-tri-n-octylpyrrole, 2,3,4,5-tetraethylpyrrole, 2,3,4,5-tetra-n-butylpyrrole, 2,3,4,5-tetra-n-hexylpyrrole, 2,5-dibenzylpyrrole, 2,4-dimethylpyrrole, 2-methyl-4-isopropylpyrrole, 2,4-dimethyl-3-ethylpyrrole, 2,4-diethylpyrrole, 2-ethyl-4-isopropylpyrrole, 2-methyl-4-sec-butylpyrrole, 2-ethyl-4-sec-butylpyrrole, 2-methyl-4-isobutylpyrrole, 2-ethyl-4-isobutylpyrrole, 2-methyl-4-t-butylpyrrole, 2-ethyl-4-t-butylpyrrole, 2-methyl-4-neopentylpyrrole, 2-ethyl-4-neopentylpyrrole, 3,4-dimethylpyrrole, 3,4-diethylpyrrole, 3,4-diisopropylpyrrole, 3,4-di-sec-butylpyrrole, 3,4-diisobutylpyrrole, 3,4-di-t-butylpyrrole, 3,4-di-neopentylpyrrole, or any combination thereof.

### Claim 9 (depends on 24)

The process of claim 24, wherein the substituted pyrrole compound comprises 2,5-dimethylpyrrole.

### Claim 10 (depends on 24)

The process of claim 24, wherein ammonia is contacted with the substituted furan compound and the catalyst.

### Claim 11 (depends on 24)

The process of claim 24, wherein the ammonium salt is contacted with the substituted furan compound and the catalyst, and wherein the ammonium salt comprises ammonium acetate, ammonium carbonate, ammonium bicarbonate, ammonium chloride, ammonium hydroxide, ammonium nitrate, ammonium phosphate, ammonium sulfate, or any combination thereof.

### Claim at position 12

12-14. (canceled)

### Claim 15 (depends on 23)

The process of claim 23, wherein the treated solid oxide comprises fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof.

### Claim 16 (depends on 24)

The process of claim 24, wherein the acidic resin comprises an AMBERLYST® catalyst resin, a NAFION® catalyst resin, or a combination thereof.

### Claim at position 15

17-18. (canceled)

### Claim 19 (depends on 24)

The process of claim 24, wherein an equivalent ratio of the ammonia, the ammonium salt, or a combination thereof, to the substituted furan compound is in a range from 0.975:1 to 50:1.

### Claim 20 (depends on 24)

The process of claim 24, wherein the substituted pyrrole compound is formed:
at a pressure in a range from 25 psig to 3500 psig;
at a temperature in a range from 50° C. to 400° C.;
at a weight hourly space velocity in a range from 0.05 to 50;
in the presence of added water;
in the presence of an organic solvent;
in a continuous reactor; or
any combination thereof.

### Claim 21 (depends on 24)

The process of claim 24, wherein the substituted pyrrole compound is formed:
in the substantial absence of added water;
in the presence of a water scavenger; or
both.

### Claim 22 (depends on 24)

The process of claim 24, wherein step 1 and step 2 are conducted in a single reactor.

### Claim 23

A process for producing a substituted pyrrole compound, the process comprising:
1) contacting
a) a substituted furan compound;
b) ammonia, an ammonium salt, or a combination thereof; and
c) a catalyst comprising a treated solid oxide; and
2) forming the substituted pyrrole compound;
wherein the treated solid oxide comprises a solid oxide treated with an electron-withdrawing anion, wherein:
the solid oxide comprises silica, alumina, titania, zirconia, magnesia, boria, zinc oxide, silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminum phosphate, aluminophosphate, aluminophosphate-silica, titania-zirconia, or any combination thereof; and
the electron-withdrawing anion comprises sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phospho-tungstate, or any combination thereof.

### Claim 24

A process for producing a substituted pyrrole compound, the process comprising:
1) contacting
a) a substituted furan compound;
b) ammonia, an ammonium salt, or a combination thereof; and
c) a catalyst comprising an acidic resin; and
2) forming the substituted pyrrole compound.

### Claim 25

(canceled)

### Claim 26 (depends on 24)

The process of claim 24, wherein the acidic resin comprises a styrene-divinylbenzene resin, a 4-vinylpyridine divinylbenzene resin, an ionomer resin, a tetrafluoroethylene resin modified with perfluorovinyl ether groups terminated with sulfonate groups, or any combination thereof.

### Claim 27 (depends on 23)

The process of claim 23, wherein the treated solid oxide comprises fluorided alumina, chlorided alumina, bromided alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, or any combination thereof.

### Claim 28 (depends on 23)

The process of claim 23, wherein the treated solid oxide comprises sulfated alumina, sulfated silica-alumina, sulfated silica-zirconia, sulfated silica-coated alumina, or any combination thereof.

### Claim 29 (depends on 23)

The process of claim 23, wherein the substituted pyrrole compound comprises 2,5-dimethylpyrrole.