# US 8,148,545 B2 · Processes for the synthesis of γ nitrocarbonyl and γ dicarbonyl compounds and their pyrrole derivatives

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- Number: US 8,148,545 B2
- Document ID: US8148545B2
- Status: Granted
- Kind: B2
- Application number: 12/418,661
- Filed: 2009-04-06
- Published: 2010-10-07
- Granted: 2012-04-03
- Earliest claimed: 2009-04-06
- Assignees: Chevron Phillips Chemical Company LP
- Inventors: Hu Yang; Eduardo J. Baralt
- Web page: https://patentgrep.com/patent/US8148545B2

## CPC

- C07C 201/12: by reactions not involving the formation of nitro groups
- C07C 45/294: {with hydrogen peroxide}
- C07D 207/32: with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## Abstract

The present invention discloses processes for producing γ-nitrocarbonyl and γ-dicarbonyl compounds, which can be precursors in the synthesis of pyrrole compounds. A process for producing pyrroles such as 2,5-dimethylpyrrole, and structurally similar pyrrole compounds, is also disclosed.

## Claims

### Claim 1

A process for producing a γ-dicarbonyl compound comprising:
a) contacting a primary nitro compound, an α,β-unsaturated carbonyl compound, a base, and water to produce a γ-nitrocarbonyl compound; and
b) contacting a peroxide compound with the γ-nitrocarbonyl compound at a molar ratio of the peroxide compound to the γ-nitrocarbonyl compound in a range from about 1:1 to about 15:1 to produce the γ-dicarbonyl compound; wherein:
the primary nitro compound has the formula:
the α,β-unsaturated carbonyl compound has the formula:
the γ-dicarbonyl compound has the formula:
wherein:
R, R1, R2, R3, and R4 independently are a hydrogen atom, a C1-C30 organyl group, a C1-C30 organyl group consisting of inert functional groups, or a C1-C30 hydrocarbyl group.

### Claim 2 (depends on 1)

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

### Claim 3 (depends on 1)

The process of claim 1, wherein the γ-nitrocarbonyl compound is produced in a yield of at least about 75 mole %.

### Claim 4 (depends on 1)

The process of claim 1, wherein the γ-dicarbonyl compound is produced in an overall yield of at least about 70 mole %.

### Claim 5 (depends on 1)

The process of claim 1, wherein an initial effective concentration of the primary nitro compound in step a) is greater than about 1 molar, the molar ratio of the primary nitro compound to the α,β-unsaturated carbonyl compound is greater than about 1.05:1, and the molar ratio of the peroxide compound to the γ-nitrocarbonyl compound is in a range from about 1:1 to about 10:1.

### Claim 6 (depends on 1)

The process of claim 1, wherein step a) and step b) are conducted in a time period of from about 10 minutes to about 10 hours.

### Claim 7 (depends on 1)

The process of claim 1, wherein R and R1 independently are a C1-C18 hydrocarbyl group, and R2, R3, and R4 are hydrogen.

### Claim 8 (depends on 1)

The process of claim 1, wherein R and R1 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 9 (depends on 1)

The process of claim 1, further comprising isolating the γ-dicarbonyl compound, wherein the isolating comprises an extraction of the γ-dicarbonyl compound with an organic solvent.

### Claim 10 (depends on 1)

The process of claim 1, wherein the molar ratio of the peroxide compound to the γ-nitrocarbonyl compound is in a range from about 1:1 to about 10:1.

### Claim 11 (depends on 1)

The process of claim 1, wherein an initial effective concentration of the γ-nitrocarbonyl compound in step b) is greater than about 0.25 molar.

### Claim 12 (depends on 1)

The process of claim 1, wherein the base is potassium carbonate.

### Claim 13 (depends on 1)

The process of claim 1, wherein the peroxide compound is hydrogen peroxide.

### Claim 14 (depends on 1)

The process of claim 1, wherein the contacting of the γ-nitrocarbonyl compound, the peroxide compound, the base, and water is initiated at a temperature in a range from about 20° C. to about 30° C., and an exotherm results in a temperature in a range from about 40° C. to about 100° C.

### Claim 15 (depends on 1)

The process of claim 1, wherein the γ-nitrocarbonyl compound has the formula:
wherein R and R1 independently are a C1-C18 hydrocarbyl group, and R2, R3, and R4 are hydrogen.

### Claim 16 (depends on 1)

The process of claim 1, further comprising contacting the γ-dicarbonyl compound with ammonia or an ammonium salt to produce a pyrrole compound.

### Claim 17 (depends on 16)

The process of claim 16, wherein the ammonium salt is ammonium carbonate, ammonium acetate, or a combination thereof.

### Claim 18 (depends on 6)

The process of claim 6, wherein step a) is conducted in a time period of from about 1 minute to about 2 hours.

### Claim 19 (depends on 9)

The process of claim 9, wherein the organic solvent is a C1 to C10 halogenated organic solvent.

### Claim 20 (depends on 19)

The process of claim 19, wherein the halogenated organic solvent is dichloromethane.

### Claim 21

A process for producing a γ-dicarbonyl compound comprising:
a) contacting a primary nitro compound, an α,β-unsaturated carbonyl compound, a base, and water to produce a γ-nitrocarbonyl compound; and
b) contacting a peroxide compound with the γ-nitrocarbonyl compound at a molar ratio of the peroxide compound to the γ-nitrocarbonyl compound in a range from about 1:1 to about 15:1 to produce the γ-dicarbonyl compound; wherein:
step b) is conducted at a temperature in a range from about 40° C. to about 100° C.;
the base is an alkali metal carbonate;
the primary nitro compound has the formula:
the α,β-unsaturated carbonyl compound has the formula:
the γ-dicarbonyl compound has the formula:
wherein:
R, R1, R2, R3, and R4 independently are a hydrogen atom, a C1-C30 organyl group, a C1-C30 organyl group consisting of inert functional groups, or a C1-C30 hydrocarbyl group.

### Claim 22 (depends on 21)

The process of claim 21, wherein R and R1 independently are a C1-C18 hydrocarbyl group, and R2, R3, and R4 are hydrogen.

### Claim 23 (depends on 22)

The process of claim 22, wherein:
the γ-nitrocarbonyl compound is produced in a yield of at least about 75 mole %; and
the γ-dicarbonyl compound is produced in an overall yield of at least about 70 mole %.

### Claim 24 (depends on 23)

The process of claim 23, wherein:
step a) is conducted in a time period of from about 1 minute to about 2 hours; and
step a) and step b) are conducted in a time period of from about 10 minutes to about 10 hours.

### Claim 25 (depends on 24)

The process of claim 24, wherein:
the alkali metal carbonate is potassium carbonate; and
the peroxide compound is hydrogen peroxide.