Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...
Reexamination Certificate
2003-03-24
2004-06-01
Desai, Rita (Department: 1626)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Having -c-, wherein x is chalcogen, bonded directly to...
C548S543000
Reexamination Certificate
active
06743819
ABSTRACT:
FIELD OF INVENTION
This invention relates to a process for producing 5-methyl-N-aryl-2-pyrrolidone and 5-methyl-N-cycloalkyl-2-pyrrolidone by reductive amination of levulinic acid or its derivatives amine salts with aryl amines, ammonia or ammonium hydroxide utilizing a metal catalyst, which is optionally supported.
BACKGROUND OF THE INVENTION
Levulinic acid is a well-known product of hexose acid hydrolysis, and can be inexpensively obtained from cellulose feedstocks. Consequently, it is an attractive starting material in producing many useful 5-carbon compounds and their derivatives. For example, N-cyclohexyl-2-pyrrolidone is used as a solvent or intermediate in many industrial applications, including the electronics industry (photo-resist stripping solutions), industrial cleaners, oil gas well maintenance, and fiber dyeing.
U.S. Pat. No. 3,337,585 discloses a process for preparing 5-methyl-1-alkyl-2-pyrrolidone utilizing levulinic acid and a primary alkyl amine at a temperature of 50° C. to 350° C. under carbon monoxide at a pressure of 1.0 to 101 MPa. Additional potential primary amines include alkylene diamines, aryl amines and cycloalkyl amines. In U.S. Pat. No. 3,235,562 a vapor phase process is used for the production of lactams by reductive amination of oxo carboxylic acid compounds. Alkyl or aryl volatile primary amines may be used. Candeloro and Bowie (
Aust. J. Chem
., 1978, 31:2031-2037) describe a process for producing 5-methyl-2,3-dihydro-1-H-benzazepin-2-one and 5-(2-methyl-5-oxo-1-phenylpyrrolidin-2-yl)-4-oxo-N-phenylpentanamide by reacting levulinic acid with aniline under a nitrogen atmosphere.
An efficient and low cost process for the production of aryl, alkyl and cycloalkyl pyrrolidones would be advantageous.
SUMMARY OF THE INVENTION
The present invention is a novel, one-step process for converting levulinic acid or its amine salts and aryl amines, ammonia or ammonium hydroxide to aryl and cycloalkyl pyrrolidones as set forth in greater detail below in the presence of catalysts. Specifically, the present invention relates to a process for preparing 5-methyl-N-aryl-2-pyrrolidone (III), 5-methyl-N-cycloalkyl-2-pyrrolidone (IV), or a mixture thereof, which comprises the step of contacting the compound levulinic acid (I) with an aryl amine (II) in the presence of a catalyst and hydrogen gas;
wherein R
1
is an aromatic group having from 6 to 30 carbons and R
2
is a fully or partially reduced derivative of R
1
, and wherein 5-methyl-N-aryl-2-pyrrolidone (III), 5-methyl-N-cycloalkyl-2-pyrrolidone (IV), or a mixture thereof, may comprise 100% by weight of the total products formed, or wherein additional products may be produced.
The catalyst useful in the process of the invention is selected from metals from the group consisting of palladium, ruthenium, rhenium, rhodium, iridium, platinum, nickel, cobalt, copper, iron, osmium; compounds thereof; and combinations thereof.
The present invention also relates to a process for preparing 5-methyl-N-aryl-2-pyrrolidone (VII), 5-methyl-N-cycloalkyl-2-pyrrolidone (VIII), or a mixture thereof, which comprises the step of contacting an ammonium salt of levulinic acid (V) with an aryl amine (VI) in the presence of a catalyst and hydrogen gas;
wherein R
1
is an aromatic group having from 6 to 30 carbons and R
2
is a fully or partially reduced derivative of R
1
, and wherein 5-methyl-N-aryl-2-pyrrolidone (VII), 5-methyl-N-cycloalkyl-2-pyrrolidone (VIII), or a mixture thereof, may comprise 100% by weight of the total products formed, or wherein additional products may be produced.
The catalyst useful in this process of the invention is selected from metals from the group consisting of palladium, ruthenium, rhenium, rhodium, iridium, platinum, nickel, cobalt, copper, iron, osmium; compounds thereof; and combinations thereof.
The present invention also relates to a process for preparing 5-methyl-N-aryl-2-pyrrolidone (XI), 5-methyl-N-cycloalkyl-2-pyrrolidone (XII), or a mixture thereof, which comprises the step of contacting an R
3
-ammonium salt of levulinic acid (IX) with ammonia or ammonium hydroxide (X) in the presence of a catalyst and hydrogen gas;
wherein R
3
is an aromatic group having from 6 to 30 carbons, R
2
is a fully or partially reduced derivative of R
3
, and A is hydrogen or hydronium ion (H
3
O
+
), and wherein 5-methyl-N-aryl-2-pyrrolidone (XI), 5-methyl-N-cycloalkyl-2-pyrrolidone (XII), or a mixture thereof, may comprise 100% by weight of the total products formed, or wherein additional products may be produced.
The catalyst useful in this process of the invention is selected from metals from the group consisting of palladium, ruthenium, rhenium, rhodium, iridium, platinum, nickel, cobalt copper, iron, osmium; compounds thereof; and combinations thereof.
DETAILED DESCRIPTION OF THE INVENTION
By “levulinic acid” is meant the compound having the following formula:
By “R
3
-ammonium salt of levulinic acid” is meant the compound having the following formula wherein R
3
is an aromatic group having from 6 to 30 carbons:
By “aryl amine” is meant the compound having the formula R—NH
2
wherein R is an aromatic group. An “aromatic group” is benzene or compounds that resemble benzene in chemical behavior.
By “5-methyl-N-aryl-2-pyrrolidone” is meant the compound having the general formula below wherein R
1
is an aryl group having from 6 to 30 carbons:
By “5-methyl-N-cycloalkyl-2-pyrrolidone” is meant the compound having the general formula below wherein R
2
is a cycloalkyl group having from 6 to 30 carbons:
By “catalyst” is meant a substance that affects the rate of the reaction but not the reaction equilibrium, and emerges from the process chemically unchanged.
By “metal catalyst” is meant a catalyst that is comprised of at least one metal, at least one Raney metal, compounds thereof or combinations thereof.
By “promoter” is meant an element of the Periodic Table that is added to enhance the physical or chemical function of the catalyst. The promoter can also be added to retard undesirable side reactions and/or affect the rate of the reaction.
By “metal promoter” is meant a metallic compound that is added to enhance the physical or chemical function of a catalyst. The metal promoter can also be added to retard undesirable side reactions and/or affect the rate of the reaction.
By “fully or partially reduced derivative” of an aryl compound is meant a compound that can be derived from the parent compound by saturating or reducing one or more of the unsaturated bonds in the aromatic ring. Unsaturated compounds are compounds that contain one or more carbon to carbon double or triple bonds. For example, a fully reduced derivative of a phenyl group is a cyclohexyl group.
This invention relates to the synthesis of 5-methyl-N-aryl-2-pyrrolidone (III), 5-methyl-N-cycloalkyl-2-pyrrolidone (IV) or a mixture thereof, from a reaction between levulinic acid (I) and an aryl amine (II) in the presence of a catalyst and hydrogen gas;
wherein R
1
is an aromatic group having from 6 to 30 carbons and R
2
is a fully or partially reduced derivative of R
1
, and wherein 5-methyl-N-aryl-2-pyrrolidone (III), 5-methyl-N-cycloalkyl-2-pyrrolidone (IV), or a mixture thereof, may comprise 100% by weight of the total products formed, or wherein additional products may be produced.
In addition, this invention relates to the synthesis of 5-methyl-N-aryl-2-pyrrolidone (VII), 5-methyl-N-cycloalkyl-2-pyrrolidone (VIII) or a mixture thereof, from a reaction between an ammonium salt of levulinic acid (V) and an aryl amine (VI) in the presence of a catalyst and hydrogen gas;
wherein R
1
is an aromatic group having from 6 to 30 carbons and R
2
is a fully or partially reduced derivative of R
1
, and wherein 5-methyl-N-aryl-2-pyrrolidone (VII), 5-methyl-N-cycloalkyl-2-pyrrolidone (VIII), or a mixture thereof, may comprise 100% by weight of the total products formed, or wherein additional products may be produced.
In addition, this invention relates to the synthesis of 5-methyl-N-aryl-2-pyrrolidone (XI), 5-methyl-N-cycloalkyl-2-pyrrolidone
Desai Rita
E. I. du Ponte de Nemours and Company
Shiao Robert
LandOfFree
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