Method for manufacturing industrial chemical agents

Abstract

"METHOD FOR MANUFACTURING INDUSTRIAL CHEMICAL AGENTS". The present invention relates to a process for producing industrially important chemical agents from renewable sources. This 'biobase' process employs readily available, renewable sources, comprising fatty acids instead of exploiting fossil sources, such as coal or oil. In a modality of the 1-octene process, together with methyl-9-decenoate and butadiene, it is produced from linoleic acid through an enzyme-mediated isomerization reaction, followed by a metathesis reaction with ethylene. Linoleic acid can be isolated from vegetable oils, such as soybean oil.

Description

Descriptive Report of the Invention Patent for "METHOD "FOR THE MANUFACTURE OF INDUSTRIAL CHEMICAL AGENTS". CROSS-REFERENCE ON RELATED REQUEST This application claims the benefit of provisional patent application U.S. No. 60 / 439,959 filed January 13, 2003, which is incorporated herein by reference. FIELD The present invention relates to a process for producing industrial organic chemical agents, with one embodiment comprising isomerization of unsaturation sites, such as through enzyme-mediated isomerization of olefins, particularly fatty acids or fatty acid derivatives, in combination with metathesis chemistry. BACKGROUND Organic chemical agents used to produce various industrial products, such as paints, solvents, synthetic fibers, and plastics, are currently synthesized primarily from petroleum-based products. Furthermore, the major portion of pharmaceutical and good chemical agents is manufactured from petroleum-derived organic chemical agents. In fact, of the more than one hundred thousand tons of good, special, intermediate, and convenience chemical agents produced annually in the United States, only ten percent of these chemical agents are bio-based, that is, produced from renewable sources. (Committee on Biobased Industrial Products, Biobased Industrial Products: Research and Commercialization Priorities, National Academic Press: Washington, DC, 1999, 25 pp. 17, 18). There is a great need to replace petroleum-derived chemical agents with chemical agents derived from renewable sources. Unsaturated compounds, such as alkenes (which are also referred to here as olefins), are particularly important chemical inputs for the production of various products, including polyethylene, polypropylene, and polybutylene polymers. The properties of such polymers are modified by copolymerization with different unsaturated chemical agents. For example, linear low-density polyethylene (LLDPE) is produced through Ethylene-1-octene copolymerization. Known processes for producing 1-octene from petroleum-based sources, such as Fischer-Tropsch processes or SHOP-type ethylene oligomerization processes, are inefficient and result in mixtures of oligomerization products that are produced in statistical proportions. Thus, large quantities of unwanted materials are produced. As a result, there is currently a shortage of 1-octene, and LLDPE production is restricted by the limited supply of 1-octene. An additional disadvantage associated with current processes is that pollutants are released during the extraction and processing of coal and oil, presenting several potential hazards to the environment and human health. Therefore, in addition to economic influences, significant environmental and health concerns provide impetus for the development of bio-based products from renewable sources to replace petroleum-based products. A potential method for the formation of unsaturated industrial chemical agents is metathesis chemistry. Metathesis often involves the reaction of two different compounds through the exchange of atoms or groups of atoms between two molecules. The olefin metathesis reaction can be thought of as a reaction where carbon-carbon double bonds in an olefin are broken and rearranged in a statistical manner. An example of alkene metathesis is illustrated in Scheme 1. SCHEME I In recent years, with the development of catalysts for Novel, well-defined, functional group-tolerant metatheses, metathesis chemistry has been applied to polymer chemistry and complex total synthesis. See, for example, Fürstner, A. Olefin Metathesis and Beyond. Angew. Chem., Int. Ed. Engl. 2000, 39, 3012-3043. Newman et al., publication number PCT WO 02 / 076920 (Newman) describes a process for metathesis of unsaturated fatty acid esters or unsaturated fatty acids with short-chain olefins. Newman describes "contact of an unsaturated fatty acid ester or an unsaturated fatty acid... with ethylene in the presence of a metathesis catalyst..." Newman, page 5, lines 22-24. Newman states that in a "more preferred embodiment related thereto, the unsaturated fatty acid is oleic acid; the lower olefin is ethylene; and the olefinic metathesis products include 1-decenoic and 9-decenoic acid." Newman, page 5, line 32, page 6, line 2. Newman does not, however, describe any method for isomerization of fatty acids or fatty acid derivatives, nor does Newman teach conjugated linoleic acid or a method for its production. Newman also does not describe the manufacture of 1-octene. Therefore, for the reasons mentioned above, new methods for converting renewable sources into industrial chemical agents, such as 1-octene, are desired. SUMMARY According to the embodiments described in the present process, industrially important unsaturated hydrocarbons are produced from renewable sources. In particular embodiments, the renewable sources are fatty acids or fatty acid derivatives. Fatty acids having at least one unsaturation site are readily available from vegetable oils including, without limitation, soybean, castor, dried castor bean, corn, cucumber, poppy seed, safflower, flaxseed, rapeseed, linseed, grapeseed, sunflower, walnut, pumpkin, cottonseed, meadowfoam, mustard seed / peanut oils, perilla, tallow oil, tung and sesame. In certain embodiments, processed oils, such as blown oils, are the source of fatty acids.Although vegetable oils are preferred sources of fatty acids for the embodiments described in the present process, fatty acids are also available from animal fats including, without limitation, lard and fish oils, such as sardine oil and herring oil, and the like. As mentioned above, in certain embodiments a fatty acid or... The desired fatty acid precursor is produced by plants or animals found in nature. However, particular fatty acids or fatty acid precursors are advantageously available from genetically modified organisms, such as a genetically modified plant. Such genetically modified organisms are designed to produce a desired fatty acid or fatty acid precursor biosynthetically or to produce larger quantities of such compounds. One described embodiment of the present process comprises providing an unsaturated compound, such as a conjugated linoleic acid (e.g., 9,11-octadecadienoic acid), and contacting the compound with a metathesis catalyst to produce a desired lower olefin. Alternatively, the described embodiments comprise providing an unsaturated compound, such as a fatty acid or fatty acid derivative, isomerizing an unsaturation site in the fatty acid or fatty acid derivative to produce an isomerized fatty acid or fatty acid derivative, and then contacting the isomerized fatty acid or fatty acid ester with a lower olefin or alkyne in the presence of a metathesis catalyst. As used herein, "lower" typically refers to compounds having 20 or fewer carbon atoms, and more typically from 1 to about 10 carbon atoms.For the metathesis reaction, the contact step is carried out under conditions that provide at least one unsaturated product, the unsaturated product being an alkene, an alkyne, or both. Typically in this embodiment, the unsaturated fatty acid derivative undergoing metathesis is a diene; however, monounsaturated fatty acids as well as fatty acids having two or more unsaturation sites can also be used. -- One aspect of the method is that monounsaturated fatty acids are produced from polyunsaturated fatty acids. Isomerized fatty acids or fatty acid esters can be produced through isomerization of a fatty acid or fatty acid ester with or without subsequent esterification or transesterification. Isomerization can be catalyzed by biochemical or chemical techniques. For example, an isomerase enzyme, such as linoleate isomerase, can be used. This process is used to isomerize linoleic acid from the c / s 9, cis 12 isomer to the cis 9, trans 11 isomer. This isomerization process is stereospecific; however, non-stereospecific processes can be used because both cis and trans isomers are suitable for metathesis. For example, an alternative process employing a chemical isomerization catalyst, such as an acid or base catalyst, can be used to isomerize an unsaturated fatty acid or fatty acid derivative having an unsaturation site at one location in the molecule into an isomerized unsaturated fatty acid or fatty acid derivative having an unsaturation site at a different location in the molecule. Metal or organometallic catalysts can also be used to isomerize an unsaturated fatty acid or fatty acid derivative. For example, nickel catalysts are known to catalyze positional isomerization of unsaturated sites in fatty acid derivatives.Similarly, esterification, transesterification, reduction, oxidation, and / or other modifications of the starting compound or products, such as fatty acids or fatty acid derivatives, can be catalyzed by biochemical or chemical techniques. For example, a fatty acid or fatty acid derivative can be modified by a lipase, esterase, reductase, or other enzyme before or after isomerization. In a particular embodiment described involving the conversion of linoleic acid, or a linoleic acid derivative, to the cis 9, trans 11 isomer, using linoleate isomerase, the c / s 9, trans 11 isomer is then subjected to metathesis conditions in the presence of ethylene. The resulting metathesis reaction gives industrially useful products, including 1,3-butadiene, 1-octene and 9-decenoic acid or their derivatives. Particular derivatives include 9-decenoate esters, such as 9-decenoate esters, lower alkyl. In another described embodiment of the method, an enzyme, such as an isomerase, is used in an immobilized reactor so that a metathesis substrate can be produced continuously. In one working embodiment, linoleate isomerase is bound to a solid support and an immobilized enzyme reactor is constructed using isolated, bound linoleate isomerase. In yet another embodiment described of the present method, an immobilized metathesis catalyst is used. Immobilization of the metathesis catalyst allows flow conditions to be used for the metathesis process and can aid in catalyst recycling. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a graph of percentage conversion versus time (hours) illustrating the passage of time of the conversion of 9,11-octadecadienoic acid to 9-methyldecenoate via ethenolysis in the presence of various metathesis catalysts. Figure 2 is a graph of percentage conversion versus time (hours) illustrating the passage of time of the conversion of 9,11-octadecadienoic acid to 1-octene via ethenolysis in the presence of various metathesis catalysts. DETAILED DESCRIPTION According to the described embodiments of the present process, industrial chemical agents can be produced from renewable sources, and agricultural crops can be used as chemical suppliers for the production of such industrial chemical agents. Although the present method is not limited to the use of fatty acids as a precursor for the production of industrial chemical agents, particular embodiments described of the process use fatty acids and fatty acid derivatives that are available from renewable sources. As used herein, the term "fatty acid" generally refers to any carboxylic acid derived from fats through hydrolysis, especially those found in animal and vegetable oils. Typically, but not necessarily, fatty acids are straight-chain hydrocarbons having from about 3 to about 20 carbon atoms.It is also understood that certain compounds are equivalent to fatty acids, for example, fatty acids and the corresponding salts and esters can be readily interconverted. In general, ester derivatives employed in the method are lower alkyl esters, including but not limited to methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec-butyl, so-butyl and the like. Also, fatty acid derivatives, which include... Any compound or portion of a compound that is derived from, or is theoretically derived from, a fatty acid, including, without limitation, esterified, dehydrated, reduced, and oxidized fatty acid derivatives. For example, fatty acids may be reduced at the carboxylate or at a site of unsaturation to provide fatty acid derivatives that are useful for the production of industrial chemical agents according to the method described. According to embodiments of the process described, a fatty acid precursor is isolated, and the fatty acid is modified to give a fatty acid derivative. The fatty acid derivative is then converted into one or more industrial chemical agents by means of at least one metathesis reaction. In certain aspects of the process, a fatty acid is directly subjected to metathesis conditions without any chemical modification. The products of such a direct metathesis process may optionally be chemically modified to produce desired derivatives. Embodiments of each step of the present process are described in more detail below. I. Renewable Sources Raw materials for the production of biobased industrial chemical agents include oils, such as vegetable oils and animal fats. Some currently important industrial chemical agents can be made directly through metathesis of such raw materials with an alkene or allyne. To solve this problem, embodiments of the present process provide a method for producing industrial chemical agents from these raw materials through isomerization of the raw material prior to metathesis. For example, there is currently a shortage of 1-octene, but 1-octene is not directly available through metathesis of any common fatty acid. According to a particular embodiment of the present method, 1-octene can be produced from renewable sources through a combination of an isomerization process and a metathesis process. For example, linoleic acid can be isomerized to conjugated linoleic acid (CLA). CLA is a generic term that refers to various conjugated isomers of linoleic acid. Any CLA having olefins (c / s or trans) in the Positions 9 and 11 are useful for the production of the industrially useful chemical agents 1-octene, butadiene and 9-decenoic acid. Historically, conjugated linoleic acid has been produced by heating linoleic acid in the presence of a strongly basic material, such as hydroxide. This procedure provides a mixture of conjugated positional isomers, as well as mixtures of c / se trans double bonds. One embodiment of the present process exploits the selectivity of an enzymatic transformation, which produces CLA having olefins at positions 9 and 11 substantially free of other CLA isomers. Unsaturated fatty acids are referred to here either by their common name, systematic name, or shorthand by the number of carbons, followed by the number and position of any double bonds, as numbered from the carboxylate carbon. For example, structure 8 (Scheme 2), having the common name linoleic acid, has eighteen carbon atoms and two double bonds, the first between the ninth and tenth carbons and the second between the twelfth and thirteenth carbons. Thus, linoleic acid 8 is systematically called A9,12-octadecadienoic acid, where "octadeca" indicates that there are 18 carbon atoms, "diene" indicates that there are two double bonds, and A9,12- indicates the alkene carbons. The suffix "oic" indicates that the compound is the free carboxylic acid, rather than an esterified carboxylic acid.The shorthand system for naming linoleic acid 8 is 18:2 A9,12, where 18 indicates the number of carbons, 2 indicates the number of double bonds, and A9,12 indicates the position of the two double bonds in the carbon chain. With reference to Scheme 2, A9,12-octadecadienoic acid 8 is exomerized to A9,11-octadienoic acid 10 in the presence of an enzyme, linoleate isomerase. In another embodiment of the process, a monoene fatty acid, such as an isomer of vaccenic acid having a C-11 olefin, is produced through an isomerization reaction, a hydrogenation reaction, or both. For example, in one aspect of the method, a diene having a C-11 olefin and another olefin is selectively enzymatically reduced to provide A11-octadecenoic acid. This transformation is This process is carried out, for example, by rumen microorganisms. See Kelly et al., / Nutr., 1998, 128, 881-885, which is incorporated here by reference. Such vaccenic acid isomers are useful intermediates for the production of 1-octene via metathesis. SCHEME 2 According to the described embodiments of the present process using an enzyme to isomerize unsaturation sites, the enzyme may be an isolated enzyme or may be used as a whole-cell preparation. "Isolated" refers to a partially or substantially completely purified enzyme. Enzyme isolation can increase enzyme activity. Examples of isolated enzymes include crude extracts, membrane-bound enzymes, soluble enzymes, recombinantly produced enzymes, solubilized enzymes, and the like. In particular embodiments, enzymes may be solubilized or stabilized through complexation with lipids, proteins, artificial membranes, and combinations thereof. In embodiments using linoleate isomerase, the enzyme can be isolated or used in a whole cell according to the procedure described by Rosson et al. in PCT Publication WO 99 / 32604. Certain embodiments can use whole cells to produce 9,11-octadecadienoic acid according to the fermentation protocol described by Pariza and Yang in U.S. Patent 6,060,304. PCT Publication WO 99 / 32604 and U.S. Patent 6,060,304 are incorporated herein by reference. In certain methods, the enzyme or the cell containing the enzyme can be immobilized. For example, enzymes can be immobilized through... A selected technique from the group consists of matrix trapping, microencapsulation, adsorption, and covalent binding. Cells expressing the enzyme can be immobilized by crosslinking with a surface using a bifunctional or multifunctional crosslinking agent, or they can be bound to a surface through a non-covalent interaction, such as a protein-ligand interaction. In such embodiments, a flow reactor can be used to carry out the isomerization reaction. An alternative route to compound 10 employs an A9-octadecenoic acid (not shown) and exploits an A11-desaturase enzyme to produce compound 10. Alternatively, another route employs the saturated starting material, octadecenoic acid, and an A11-desaturase enzyme to produce A11-octadecenoic acid (not shown), which is commonly known as vaccenic acid. Such a route may also use an A9-desaturase enzyme to produce compound 10. A11-octadecenoic acid is a useful intermediate for the production of 1-octene, and this fatty acid can also be produced by isomerization of readily available A9,12-octadecadienoic acid to A9,11-octadecadienoic acid, followed by selective, enzymatic reduction of the A9 double bond. II. Metathesis Any known or future developed metathesis catalyst may be used, alone or in combination with one or more additional catalysts, according to embodiments of the present method. Typical metathesis catalysts used for the described embodiments include metal carbene catalysts based on transition metals, such as ruthenium. Exemplary ruthenium-based metathesis catalysts include those commercially available represented by structures 12 (generally referred to as Grubb catalyst), 14 and 16. ciJ Cy3 p h PCy3 Month- Cl, I Ru— Cl**' PCy3 N-Mes Ph 12 14 16 Structures 18-28, illustrated below, represent catalyzed- Additional useful ruthenium-based metathesis catalysts. Techniques for using catalysts 12-28, as well as additional related metathesis catalysts, are described in PCT publications numbers WO 99 / 26949, WO 00 / 71554, WO 02 / 14376 and in US patent application publication number 2002 / 0177710. Each of these patent publications is incorporated herein by reference in its entirety. Ck ' J JRu=-Cl x ' PCp3 py 20 22 Mes— N-Mes Cl Ph 26 28 Additional metathesis catalysts include, without limitation, metal carbene complexes selected from the group consisting of molybdenum, osmium, chromium, rhenium, tungsten, and tungsten carbene complexes. The term "complex" refers to a metal atom, such as a transition metal atom, with at least one ligand or complexing agent coordinated or bonded to it. Such a ligand is typically a Lewis base in metal carbene complexes useful for alkene, alkyne, or alkene metathesis. Typical examples of such ligands include phosphines, halides, and stabilized carbenes. Some metathesis catalysts employ plural metal or metal co-catalysts. For example, German patent publication number A1-282594, which is incorporated herein by reference, describes a catalyst comprising a tungsten halide, a tetraalkyltin compound, and an organoaluminum compound. An immobilized catalyst can be used for the metathesis process. See, for example, Blechert, et al., Synthesis and Application of a Permanently Immobilized Olefin Metathesis Catalyst. Angew. Chem. Int. Ed. Engl. 2000, 39, 3898-3901, incorporated herein by reference. Catalysts Immobilized catalysts can be used in a flow process, as is known to a person skilled in the art. An immobilized catalyst can simplify product purification and catalyst recovery, making catalyst recycling convenient. The metathesis process for the production of industrial chemical agents can be carried out under any conditions suitable for producing the desired metathesis product or products. For example, stoichiometry, atmosphere, solvent, temperature, and pressure can be selected to produce a desired product and to minimize undesirable byproducts. The metathesis process is typically carried out under an inert atmosphere. Similarly, if an olefin or alkyne reagent is supplied as a gas, an inert gaseous diluent can be used. The inert atmosphere or inert gaseous diluent is typically an inert gas, meaning that the gas does not interact with the metathesis catalyst to substantially impede catalysis. For example, particular inert gases are selected from the group consisting of helium, neon, argon, nitrogen, and their combinations. In certain embodiments, a lower unsaturated gaseous reagent is employed.In such modalities, the lower unsaturated reagent can be used with or without a gaseous diluent. Similarly, if a solvent is used, the solvent chosen is typically substantially inert with respect to the metathesis catalyst. For example, substantially inert solvents include, without limitation, aromatic hydrocarbons such as benzene, toluene, xylene and the like; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; aliphatic solvents including pentanhexane, heptane, cyclohexane and the like; and chlorinated alkanes such as dichloromethane, chloroform, dichloroethane and the like. In certain embodiments, a ligand is added to the metathesis reaction mixture. Typically, the ligand is a molecule that stabilizes the catalyst, thereby providing a greater total change for the catalyst. In some cases, the ligand can alter the selectivity of the reaction and product distribution. Examples of ligands that can be used These include Lewis base ligands, such as, without limitation, trialkylphosphines, for example, tricyclohexylphosphine and tributylphosphine; triarylphosphines, such as triphenylphosphine; diarylalkylphosphines, such as diphenylcyclohexylphosphine; pyridines, for example, 2,6-dimethylpyridine, 2,4,6-trimethylpyridine; as well as other Lewis basic ligands, such as phosphine oxides and phosphinites. Using currently known catalysts, the metathesis processing temperature is a highly rate-dependent variable where the temperature is selected to provide a desired product at an acceptable production rate. The selected temperature is typically greater than about -40°C, typically greater than about -20°C, more typically greater than about 0°C, and most typically greater than about 20°C. Generally, the process temperature is less than about 150°C, and preferably less than about 120°C. Thus, a currently preferred temperature range for the metathesis reaction is from more than about 20°C to about 120°C. Lower temperatures may be used, for example, to minimize the production of unwanted impurities or to favor a particular reaction course.Examples of using temperature to control reaction rate and to vary reaction products are described in PCT publication number WO 02 / 094748, which is incorporated herein by reference. The metathesis process can be carried out under any pressure of alkene, alkyne, and / or gaseous diluent. The total pressure is generally greater than about 30 kPa, and more typically is greater than about 100 kPa. In general, the total pressure is less than about 7,000 kPa, and more typically is less than about 3,000 kPa. Thus, a pressure range likely useful for the metathesis process carried out under pressure is from about 100 kPa to about 3,000 kPa. Any useful quantity of the selected metathesis catalyst can be used in the current process. If the catalyst has a relatively high total change number, the molar ratio of the metathesis process precursor, such as a fatty acid or unsaturated fatty acid derivative, to the catalyst can be as high as about 10,000,000 to 1, but The ratio is typically less than about 500,000 to 1. The molar ratio of the fatty acid or unsaturated fatty acid derivative to the catalyst is typically greater than about 5 to 1, and preferably greater than about 50 to 1, and most preferably greater than about 100 to 1. Several working examples have used a substrate-to-catalyst molar ratio of 25 to 1. III. Production of Industrial Chemical Agents Industrial chemical agents are typically derived from petroleum sources. Using the present process, a desired industrial chemical agent can be produced from renewable sources by selecting an appropriate unsaturated precursor fatty acid and an appropriate unsaturated reagent. This process is illustrated retrosynthetically in Scheme 3. Rf Rt R 32 R R SCHEME 3 With reference to Scheme 3, structure 36 represents a desired compound and structures 32 and 34 represent the precursors for 36. Compounds having structures 32 and 34 can be converted into a compound having structure 36 through a metathesis reaction. Structure 32 can be obtained from renewable source 30 using an isomerization reaction. In preferred embodiments, more than one industrially useful product is produced. As retrosynthetically illustrated in Scheme 4, two product compounds represented by structures 36 and 38 can be formed. Rx Rf 36r R- Rf Rf R R SCHEME 4 Alternatively, three or more products may be produced. For example, polyunsaturated fatty acids having two or more unsaturated sites give three or more products according to the embodiments of the present invention. Method 5. See Diagram 5 below. Rl— \= SCHEME 5 The embodiments of the present process as illustrated by Schemes 3-5 are particularly useful for the production of chemical agents that are not directly available from readily available renewable sources through a metathesis reaction. A particularly valuable class of industrial chemical agents comprises α-olefins. α-olefins are terminal alkenes and are mainly used as comonomers as a second olefin for the production of polyolefins. A particularly useful process for the production of α-olefins includes ethylene as a starting material. For example, with reference to Schemes 3-5, α-olefins are used as a starting material. Above, R3 is hydrogen and compound 34 is ethylene. With reference to Schemes 3-5, described embodiments of the present process generally employ an olefin reagent, such as the compound represented by structure 34 in Schemes 3-5. However, in particular embodiments, an alkyne reagent may replace the olefin reagent. In such embodiments, a 1,3-diene derivative is formed through Alkene-alkyne (enin) metathesis. The olefin or allyne reagent reacts with a fatty acid to give at least one desired chemical agent. In preferred embodiments of the present process, the olefin or alkyne is a lower unsaturated reagent, such as a lower olefin or alkyne. By definition, the lower unsaturated reagent has at least one carbon-carbon double or triple bond, and may have multiple carbon-carbon double or triple bonds. The lower olefin may contain an internal double or triple bond, a terminal double or triple bond, or both. Double bonds may be tetra-, tri-, di-, or monosubstituted. Suitable substituents for the lower unsaturated reagent may include, without limitation, aliphatic, aromatic, hydroxyl, ether, keto, aldehyde, and halogen functional groups. Preferably, aliphatic substituents are lower alkyl substituents. Preferred lower olefins include ethylene, propylene, butene, butadiene, pentene, hexene, and their isomers. Preferred lower alkynes include acetylene and propyne. Yields for the described embodiments of the present process are defined as mole percent with respect to the fatty acid precursor. Typically, the yield of at least one saturated product from the metathesis process is greater than about 35 mole percent, and more typically greater than about 50 mole percent. With reference to Scheme 6, 1-octene is produced according to an embodiment of the present process starting with a conjugated linoleate, such as a methyl linoleate derivative 48. Compound 48 can be prepared by isomerization of linoleic acid (18:2 A9,12) to the conjugated linoleic acid isomer 10 (18:2 A9,11) as shown in Scheme 2. Esterification of 10 with methanol gives 48. Conjugated methyl linoleate derivative 48 is then contacted with a metathesis catalyst in the presence of ethylene to give 1-octene 50, methyl 9-decenoate 52 and butadiene 54. Alternatively, the conjugated linoleic acid isomer 10 can be used directly in the metathesis reaction, without prior esterification, to produce 50, 54 and 9-decenoic acid (not shown). Met 18:2 A9,11 H2C=CH2 THE + 50 catalyst Mei SCHEME 6 All three products illustrated 50, 52, and 54 in Scheme 6 are industrially useful chemical agents. For example, 1-octene 50 is used industrially as a comonomer with ethylene to produce LLDPE. Methyl 9-decenoate 52 can be used to produce azelaic acid, decanol, decanoic acid, aminodecanoic acid, and other industrially useful compounds. These compounds are used industrially to produce nylon and thermosetting resins as well as other products. Butadiene 54 is used industrially in the production of rubber and latex polymers. Diagram 7 illustrates an alternative method for production. Vaccenic acid derivative 56 (18:1 A11) of linoleic acid derivative 48 (18:2 A9,11) via regioselective reduction reaction. Subsequent metathesis with ethylene gives 1-octene 50 and methyl 11-dodecenoate 58. As in Scheme 6, an alternative embodiment employs linoleic acid isomer 10 in place of methyl ester 48. In this embodiment, the corresponding free acids of compounds 56 and 58 are produced. .Mei 18:2 A9,11 THE Me 18:1 1 A11 H2C=CH2 SCHEME 7 Mei catalyst Scheme 8 illustrates an embodiment of the described method suitable for producing the useful industrial chemical agent methyl 9-decenoate. In this embodiment, oleic acid derivative 62 is produced from linoleic acid derivative 60 (18:2 A9,12) via a regioselective enzymatic reduction process. Subsequent metathesis with ethylene gives 1-deceno 64 and methyl-9-decenoate 66. As in other examples of the method, the corresponding fatty acid of compound 60 can be used directly to give 9-decenoic acid. SCHEME 8 EXAMPLES The following examples are provided to illustrate certain particular modalities of the description. It should be understood that additional modalities, not limited to these particular characteristics described, are consistent with the examples that follow. EXAMPLE 1 This example describes a method for producing conjugated linoleic acid A9,11 10 (CLA) from linoleic acid. The cells used here, Lactobacillus reuteri PYR8 (ATCC Accession No. 55739, deposited February 15, 1996 with the American Type Culture Collection (ATCC), 10801 University Boulevard, Manassas, VA 20110, USA) are grown in Lactobacillus MRS Broth (BBL) in closed containers with limited headspace. Large-scale cultures were grown (1-2% (inoculum) in 2 L bottles without agitation at 37°C for about 36 to about 40 hours, harvested by centrifugation, washed once with 0.1 M bis-tris, 0.9% NaCl buffer pH 6.0 and are immediately used or stored at around -80°C. Lactobacillus reuteri cells (or another organism carrying the linoleate isomerase gene) are cultured in modified AV medium with 40 g / L yeast extract, 20 g / L Hy soybean, and 40 g / L glucose to a cell density of approximately 3–4 g / L dry cell weight. When the cells reach the stationary phase, they are harvested and resuspended in breakdown buffer at a concentration between 5 and 20 g dry cell weight per liter. Biotransformation is preferably carried out at a temperature between 4 o C and 8 oC to maintain optimal enzyme activity. Linoleic acid can be added, for example, as a purified material having a purity of about 99%, or as a component of another oil, such as soybean oil, which has a concentration of about 50% linoleic acid. Alternatively, linoleic acid can be dissolved in a co-solvent, such as propylene glycol. Typically, linoleic acid is added at a concentration between about 0.5 and 4 g / L by adding several aliquots of smaller amounts of linoleic acid. Higher CLA product concentrations can be obtained by adding cells in successive steps as the reaction proceeds. Under such conditions using the linoleic acid concentrations described, conversion of linoleic acid to CLA is between 80% and 100% within from about 2 to about 8 hours. Methyl 9,11-octadecadienoate, as well as other esters, can be prepared from compound 10, which is produced as described above. In one method for preparing such esters, compound 10 is esterified with methanol under Dean-Stark conditions in the presence of 1% sulfuric acid to give the corresponding methyl ester. After no more water is released, the excess methanol is distilled, leaving methyl 9,11-octadecadienoate. EXAMPLE 2 This example describes a procedure for fatty acid analysis to determine the conversion of linoleic acid to α9,11-CLA. From the reaction mixture described in Example 1, fatty acids are extracted from about 1 mL to about 2.5 mL of aqueous samples with 0.5 mL of 5M NaCl added. The samples were shaken with 5 mL of a 2:1 chloroform / methanol mixture in a screw-top glass tube with a Teflon-lined cap. The two phases are separated, and about 1 to 2 mL of the chloroform layer is removed. The organic layer is dried with Na2SÜ4 and concentrated. Concentrated fatty acids are converted into the corresponding methyl esters using the following procedure adapted from Chin et al., J. Food Composition, 1992, 5, 185-192: Approximately 6 mL of 4% HCl in methanol preheated to 60°C are added to the glass tube containing the fatty acid sample.The tube is sealed with a lined Teflon cap and incubated in a tube heater at 60°C for 20 minutes, cooled to room temperature, and 2 mL of water and 3 mL of hexane are added. After shaking, the organic layer is separated, dried with Na2SO4, and analyzed by gas chromatography. EXAMPLE 3 This example describes the production of industrial chemical agents from methyl-9,11-octadecenoate via ethenolysis. In a glove box under an inert atmosphere, methyl-9,11-octadecenoate produced according to Example 1 (2.95 g; 0.01 mol) was dissolved in dichloromethane to prepare 100 mL of a 0.1 M stock solution. Additionally, a 0.1 M solution of 20 (60 mg; 0.1 mmol) was also prepared in dichloromethane. A solution of conjugated methyl linoleate (25 mt) was then loaded into a Fisher-Porter bottle fitted with a stirring bar. Catalyst solution 20 (100 µl) was added via a microsyringe, and the top of a Fisher-Porter bottle fitted with a pressure gauge and a dip tube was fitted onto the bottle. The system was sealed and removed from the glove box to an ethylene line. The container was then purged with ethylene (3 times), pressurized to 1034 kPa. (150 psi) of ethylene and placed in an oil bath at 30°C. The reaction was monitored by collecting samples using a dip tube at different reaction times and quenching each sample by adding a tris-hydroxymethyl phosphine solution. The samples were then heated for at least 1 hour at 60°C, washed with distilled water, extracted with hexanes, and analyzed by gas chromatography (GC). During the reaction, the following ethenolysis products were observable by GC: 1-octene (C8 Scheme 6, compound 50); 1,3-decadiene (C10); methyl 9-decenoate (Scheme 6, compound 52); 7-tetradecene (C14); methyl 9,11-dodecadienoate (C12); and 1,18-dimethyl 9-octadecenedioate (C18). The percentages (%) of these products in the reaction mixture over time are recorded in Table 1. Table 1 Time (hour) 50 C10 52 C12 C14 C18 48 Impurities 0.0 0.0 0.0 0.0 0.0 0.0 0.0 98.4 1.6 0.5 14.3 22.8 35.6 5.3 0.7 0.0 16.9 4.4 2.0 8.5 22.1 37.4 5.5 0.6 0.0 16.7 9.2 6.75 13.2 23.7 36.7 8.2 NI 0.0 16.2 2.0 17.45 13.4 21.6 35.2 7.4 NI 0.0 15.6 6.8 NI = Non-integrated Example 4 This example describes the production of industrial chemical agents through ethenolysis using catalyst 12. Using the general procedure and conditions described in Example 2, the ethenolysis of conjugated dermethylinoleate catalyzed by catalyst 12 was monitored over time. The percentages (%) of ethenolysis products in the reaction mixture over time are recorded in Table 2. Table 2 Time (h) 50 C10 52 C12 C14 C13 48 Impurities 0.0 0.0 0.0 0.0 0.0 0.0 0.0 98.4 1.6 0.5 12.9 20.2 32.1 7.4 0.7 0.0 19.1 7.6 2.0 17.6 21.5 42.2 6.8 0.4 0.0 7.3 4.2 6.75 17.8 23.2 43.7 6.9 0.5 0.0 5.9 2.0 17.45 19.2 20.2 43.9 5.5 0.6 0.0 6.3 4.3 Example 5 This example describes the production of industrial chemical agents through ethenolysis using catalyst 16. Using the general procedure and conditions described in Example 2, the ethenolysis of conjugated methyl linoleate catalyzed by catalyst 16 was monitored over time. The percentages (%) of ethenolysis products in the reaction mixture over time are described in Table 3. Table 3 Time (h) 50 C10 52 C12 C14 C18 48 Impurities 0.0 0.0 0.0 0.0 0.0 0.0 0.0 98.4 1.6 0.5 11.2 20.9 29.1 8.3 0.0 0.0 27.8 2.7 2.0 16.6 23.2 39.4 7.7 0.0 0.0 9.6 3.5 7.0 17.2 23.6 42.6 7.4 0.0 0.0 7.2 2.0 17.50 15.6 22.5 41.6 7.0 0.0 0.0 6.8 6.5 Example 6 This example describes the production of industrial chemical agents. Trials via ethenolysis using catalyst 18. Using the general procedure and the same conditions as those described in Example 2, the ethenolysis of conjugated methyl linoleate catalyzed by catalyst 18 was monitored over time. The percentages (%) of ethenolysis products in the reaction mixture over time are described in Table 4. Table 4 Time (h) 50 C10 52 C12 C14 C18 48 Impurities 0.0 0.0 0.0 0.0 0.0 0.0 0.0 98.4 1.6 0.5 4.3 18.6 22.7 6.4 0.0 0.0 44.8 3.2 2.0 9.0 23.5 29.8 7.3 0.0 0.0 26.8 3.6 7.0 7.3 23.6 30.6 7.9 0.0 0.0 29.4 1.2 17.50 5.1 23.4 30.0 7.7 0.0 0.0 28.0 5.8 Example 7 This example describes the production of industrial chemical agents via ethenolysis using catalyst 14. Using the general procedure 5 and conditions described in Example 3, the ethenolysis of conjugated methyl linoleate catalyzed by catalyst 14 was monitored over time. The percentages (%) of ethenolysis products in the reaction mixture over time are recorded in Table 5. Table 5 Time (h) 50 C10 52 C12 C14 C18 48 Impurities 0.0 0.0 0.0 0.0 0.0 0.0 0.0 98.4 1.6 0.5 0.4 0.7 2.0 0.5 0.7 5.8 59.7 30.2 2.0 1.7 1.5 4.4 0.8 0.7 5.8 55.2 29.9 7.0 2.4 1.6 4.7 0.9 1.0 5.9 54.5 29.0 17.50 1.6 1.6 5.0 1.5 0.7 5.4 53.0 31.2 Example 8 This example describes the production of industrial chemical agents through ethenolysis using catalyst 26. Using the same procedure and conditions as those described in Example 3, the ethenolysis of conjugated methyl linoleate catalyzed by catalyst 26 was monitored over time. The percentages (%) of ethenolysis products in the reaction mixture over time are recorded in Table 6. Table 6 Time (h) 50 C10 52 C12 C14 C18 48 Impurities 0.0 0.0 0.0 0.0 0.0 0.0 0.0 98.4 1.6 0.5 2.5 3.2 7.4 2.0 0.0 2.0 48.4 34.5 2.0 5.0 5.0 10.6 1.1 0.0 2.8 49.1 26.4 6.75 5.9 5.3 10.0 1.5 0.0 3.5 47.1 26.7 17.45 5.6 4.4 10.4 1.2 0.0 3.9 48.7 25.8 Example 9 This example describes the production of industrial chemical agents via ethenolysis using catalyst 28. Using the general procedure and conditions described in Example 3, the ethenolysis of conjugated methyl linoleate catalyzed by 28 was monitored over time. The percentages (%) of ethenolysis products in the reaction mixture over time are recorded in Table 7. Table 7 Time (h) 50 C10 52 C12 C14 C18 48 Impurities 0.0 0.0 0.0 0.0 0.0 0.0 0.0 98.4 1.6 0.5 7.4 8.6 18.8 3.3 1.0 0.0 50.3 10.6 2.0 8.8 9.2 19.7 4.6 1.0 1.1 51.0 4.6 6.75 9.0 9.5 19.4 4.8 0.0 1.7 49.4 6.2 17.45 10.2 8.6 18.6 4.0 0.0 1.3 49.5 7.8 Example 10 This example describes the production of industrial chemical agents. Trials via ethenolysis using catalyst 24. Using the general procedure and conditions described in Example 3, the ethenolysis of conjugated methyl linoleate catalyzed by 24 was monitored over time. The percentages (%) of ethenolysis products in the reaction mixture over time are recorded in Table 8. Table 8 Time (h) 50 C10 52 C12 C14 C18 48 Impurities 0.0 0.0 0.0 0.0 0.0 0.0 0.0 98.4 1.6 0.5 0.6 1.0 2.6 1.0 1.3 6.8 51.2 35.5 2.0 0.6 1.0 2.7 0.8 1.3 6.8 50.2 36.6 7.0 0.9 1.0 2.5 0.6 1.4 7.0 52.2 34.4 17.50 0.0 1.0 2.9 0.9 1.0 6.5 50.4 37.3 Example 11 Using a high-pressure Parr reactor, reactions of etheno- The lysis of methyl 9,11-octadecenoate (Scheme 6, compound 48) was carried out at room temperature (24°C) as in Examples 3-10, except that the ethylene pressure was increased to 5517 kPa (800 psi). The samples were analyzed as previously described. The percentages (%) of ethenolysis products observed in the reaction mixture at 2 hours with different catalysts are recorded in Table 9. Table 9 Time (h) 50 C10 52 C12 C14 C18 48 Impurities 601 5.4 16.6 19.3 7.1 0.0 0.0 49.1 2.5 823 5.9 18.4 20.9 7.9 0.0 0.0 41.1 5.8 712 4.8 6.6 8.2 3.6 0.1 2.8 60.2 13.8 933 1.2 2.1 2.6 0.7 0.2 3.0 67.9 22.5 It will become apparent to those versed in the technique that several modifications Variations can be made to the present method without departing from the scope or spirit of the description. Other embodiments of the method will become apparent to those skilled in the art from consideration of the descriptive report and practice of the procedures described herein. It is intended that the report and examples be considered as exemplary only, with the true scope and spirit of the invention being indicated by the claims that follow.

Claims

CLAIMS 1- Process for the production of an industrial chemical agent comprising: provision of an isomerization precursor; isomerization of an unsaturation site in the precursor to produce an isomerized derivative; and Reaction of the isomerized derivative with an unsaturated compound in the presence of a metathesis catalyst to produce at least one desired industrial chemical agent. 2- Process according to claim 1, wherein the isomerization precursor is an unsaturated fatty acid or fatty acid derivative. 3- Process according to claim 2, wherein the fatty acid or fatty acid derivative is a polyunsaturated fatty acid. 4- Process according to claim 1, wherein the metathesis catalyst is a ruthenium-based catalyst. 5- Process according to claim 2, wherein the isomerization of the fatty acid or fatty acid derivative includes contact of the fatty acid or fatty acid derivative with an enzyme. 6- Process according to claim 1, wherein the isomerization produces a conjugated diene derivative. 7- Process according to claim 6, wherein the conjugated diene derivative is a conjugated linoleic acid. 8- Process according to claim 7, wherein the conjugated linoleic acid is 18:2 linoleic acid A9.

11. 9- Process according to claim 1, wherein the reaction of the isomerized derivative produces at least a compound selected from the group consisting of butadiene, 1-octene, 9-decenoic acid, their derivatives and combinations thereof. 10- Process according to claim 2, wherein the reaction of the fatty acid or fatty acid derivative with an unsaturated compound produces at least one compound selected from the group consisting of butadiene, 1-octene, 9-decenoic acid, their derivatives and combinations thereof. 11- Process according to claim 10, wherein the reaction of the fatty acid or fatty acid derivative with an unsaturated compound produces 1-octene. 12- Process for the production of 1-octene comprising: provision of linoleic acid or a derivative thereof; Enzymatic isomerization of an unsaturation site in linoleic acid or its derivative to produce an isomerized linoleic acid or isomerized lower ester of linoleic acid; and The reaction of isomerized linoleic acid or isomerized lower ester of linoleic acid with a metathesis catalyst in the presence of ethylene, thereby producing 1-octene. 13- Process according to claim 12, wherein the isomerized linoleic acid is α9,11-octadecadienoic acid. 14- Process according to claim 13, wherein 9,11-octadecadienoic acid is esterified to provide a lower alkyl ester before reaction with ethylene in the presence of a metathesis catalyst. 15- Process according to claim 12, wherein the metathesis catalyst is a ruthenium-based catalyst. 16- Process according to claim 15, wherein the metathesis catalyst is: there c 2z ph PCy3 17- Process according to claim 12, wherein linoleic acid is derived from soybean oil. 18- Process for the production of 1-octene comprising: provision of linoleic acid from soybean oil; linoleic acid comes into contact with a linoleate isomerase to produce α9,11-octadecadienoic acid; esterification of 9,11-octadecadienoic acid to produce a lower alkyl ester; and contact of the ester with a metathesis catalyst in the presence of ethylene, thereby producing 1-octene. 19- Process according to claim 18, wherein contact of the ester with a metathesis catalyst in the presence of ethylene produces a 9-decenoate ester. 20- Process according to claim 18, wherein the catalyst is a ruthenium-based catalyst. 21- Process according to claim 20, where the catalyst The trainer is selected from the group consisting of 22- Process for the production of 1-octene comprising: provision of a fatty acid diene or an ester thereof; conversion of the fatty acid diene or its ester into vaccine- Nico or one of its esters; and Contact of vaccenic acid or one of its esters with a metathesis catalyst in the presence of ethylene, thereby producing 1-octene. 23- Method for manufacturing 1-octene comprising: provision of 9,11-octadecadienoic acid or a derivative thereof; and Contact of 9,11-octadecadienoic acid or its derivative with a metathesis catalyst in the presence of ethylene, thereby producing 1-octene. 24- Method according to claim 23, wherein 9,11-octadecadienoic acid or a derivative thereof is provided as an ester or a salt of 9,11-octadecadienoic acid. 25- Method according to claim 24, wherein the provision comprises a lower alkyl ester of octadecadienoic acid. 26- Method according to claim 25, wherein the ester is a methyl ester. 27- Method according to claim 23, wherein the method yields 9-decenoic acid. 28- Method according to claim 23, wherein the metathesis catalyst is a ruthenium-based catalyst. 29- Method according to claim 23, wherein the catalyst Metastatic pain is selected from the group consisting of