BR112012020146A2 - metathesis catalyst and processes for its use. - Google Patents

Abstract

METATHESIS CATALYST AND PROCESSES FOR THE SAME USE. This invention relates to a catalyst compound for the olefin metathesis represented by formula (1): where M is a Group 8 metal; X and X 'are anionic ligands; L is a neutral, two-electron donor; L 'is N, O, P, or S, preferably N or O; R is a Cj to C30 hydrocarbyl or a Cj to C30 hydrocarbyl substituted; G * is selected from the group consisting of hydrogen, a Cj to C30 hydrocarbyl, and a Cj to C30 hydrocarbyl substituted; R 'is selected from the group consisting of hydrogen, a Cj to C30 hydrocarbyl, and a Cj to C30 hydrocarbyl substituted; and G is independently selected from the group consisting of substituted hydrogen, halogen, Cj to C30 hydrocarbyl and Cj to C30 hydrocarbyl. This invention further relates to the process for producing alpha olefins comprising contacting an olefin, such as ethylene, with a feed oil containing a triacylglyceride (typically a fatty acid ester (such as methyl oleate)) with the described catalyst compound. above. The fatty acid ester can be a fatty acid methyl ester derived from biodiesel.

Description

| Doo 1/59 Invention Patent Descriptive Report for "CATALYSIS-: METATHESIS PAIN AND PROCESSES FOR THE SAME USE".

PRIORITY CLAIM This application claims priority and benefit from USSN 12 // 05.136, filed on February 12, 2010, and EP 10159428.1, filed on April 8, 2010, the disclosures of which are incorporated herein by reference in their totalities. DECLARATION OF RELATED ORDERS 'This invention relates to USSN 12 / 939,063, filed on November 3, 2010 and claiming priority of USSN 61 / 259,521, filed on November 9, 2009. This invention also refers to USSN 12 / 9390,054, filed on November 3, 2010 and claiming priority of USSN 61 / 259,514, filed on November 9, 2009.

FIELD OF THE INVENTION This invention relates to the olefin metathesis, more particularly! metathesis catalyst compounds and processes for their use.

BACKGROUND OF THE INVENTION Cross-metathesis of two reagent olefins, each olefin agent comprising at least one unsaturation site, to produce new olefins that are different from reagent olefins is of significant commercial importance. The metathesis cross-reaction is usually catalyzed by one or more catalytic metals, usually one or more transition metals.

One such commercially significant application is the cross-metathesis of ethylene and internal olefins to produce alpha-olefins, which is generally referred to as ethenolysis. In particular, ethylene cross-metathesis and an internal olefin to produce linear alpha-olefins (LAOS) is of particular commercial importance. LAOS are useful as monomers or co-monomers in certain (co) polymers (polyalphaolefins or PAOs) and / or as intermediates in the production of epoxides, amines, oxo alcohols, lubricants | synthetic, synthetic fatty acids and alkylated aromatics. Converted Olefins

2/59 sion Technologyº, based on the Phillips Triolefin Process, is an example of 'an ethenolysis reaction that converts ethylene and 2-butene to propylene. These processes use heterogeneous catalysts, such as tungsten and rhenium oxides, which have not shown effectiveness for internal olefins containing functional groups such as cis-methyl oleate, a fatty acid methyl ester.

Methods for the production of polyalphaolefins are typically multi-step processes that generally create unwanted by-products and waste from reactants and energy. Linear full-range plant alpha-olefins are based on oil, are inefficient and result in mixtures of oligomerization products that typically generate Schulz-Flory distributions producing large amounts of undesirable materials. In recent years, new technologies have been implemented to produce linear alpha-olefins for purposes such as 1-hexene and 1-octene through selective ethylene trimerization based on chromium or tetramerization catalyst. Alternatively, 1-octene was produced by telomerization of butadiene and methanol. Similar strategies are not currently available ”for the production of 1-decene.

1-Decene is a co-product typically produced in the cross-metathesis of ethylene and methyl oleate. Alkylate oleates are esters of acids — fatty acids that can be the main components in biodiesel! produced by transesterification of alcohol and vegetable oils. Vegetable oils containing at least one place of unsaturation include canola, soy, palm, peanuts, mustard, sunflower, tung, pinewood, perilla, grape seed, rapeseed, flaxseed, safflower, pumpkin, corn and many other oils extracted from plant seeds . Alkyl erucates similarly are esters of fatty acids that can be the main components in biodiesel. Useful biodiesel compositions are those that typically have high concentrations of oleate and erucate ethers. These fatty acid esters preferably have an unsaturation site so that ethylene cross-metathesis generates 1-decene as a co-product.

Biodiesel is a fuel prepared from renewable sources, such as plant oils or animal fats. To produce biodiesel,

| | flight 3/59 | triacylglycerides ("TAG"), the main compound in plant oils and animal fats, are converted to the alkyl esters of fatty acid ("FAAE," that is, biodiesel) and glycerol by reaction with an alcohol in the presence of a base, acid, or enzyme catalyst.

Biodiesel fuel can be | use diesel engines, alone or in a mixture with diesel based on petroleum, or can be further modified to produce other chemical products.

Cross-metathesis catalysts reported so far for methyl oleate ethenolysis are typically ruthenium-based catalysts containing phosphine or carbene binders.

Dow researchers in 2004 achieved approximately | 15,000 using the first generation of Grubb catalyst, bis (tricyclo | hexylphosphino) benzylidene ruthenium (IV) dichloride, (Organometallics 2004, 23, | 2027). Researchers at Materia, Inc. reported transformation numbers | 15 tion up to 35,000 using a ruthenium catalyst containing an α carbene amino cyclic alkyl binder, (WO 2008/010961). These transformers were obtained with a catalyst reportedly very expensive for industrial consideration due to the high costs associated with the catalysts being derived from a low yield synthesis (See Final Technical Report entitled "Platform Chemicals from an Oilseed Biorefinery" concession number DE-FG36-04GO14016 granted by the Department of Energy). In addition, the introduction of isopropoxybenzylidene ligands gave ruthenium catalysts improved activities for metathesis reactions (J.

Am.

Chem.

Soc. 1999, 121, 791). However, these alkylene rhenium catalysts are generally prepared by reacting ruthenium species with diazo compounds.

Concerns associated with industrial-scale reactions comprising diazo compounds have led to increased efforts to prepare ruthenium alkylidenes via alternative synthetic routes, such as using terminal alkynes or propargyl alcohol.

The synthesis of RuCl (PCy3)> (3-phenylindenylene) has been shown to be useful in providing an easy pathway for ruthenium alkylidenes that avoids costly diazo preparations (Platinum Metals Rev. 2005, 49, 33). Furstner et

| : '4/59 al. prepared (N, N "-bis (mesiti) imidazol-2-ylidene) RuCl> (3-phenylindenylene).: However, these types of complexes do not prove efficacy in e-tenolysis reactions. To obtain an economically viable process for the production of -decene through cross-metathesis of ethylene and biodiesel (such as animal or vegetable oils), greater activity catalysts must be discovered, so there is a need for greater activity processes that produce desired products and co-products in commercial proportions- desirable.

There remains a need for the catalyst we gave | high activity and selectivity in cross-reaction metathesis, including | ethenolysis, which are capable of being synthesized in both synthetic routes | soft and accessible. The metathesis catalyst compounds of the present invention both provide a mild and commercial "atomic-economic" pathway. 15 economically effective for desirable olefins, in particular alpha-olefins, which in turn can be useful in the preparation of PAOs. More particularly, the metathesis catalyst compounds of the present invention improved the activity and selectivity for ethylene products in ethylene metathesis cross-reactions.

SUMMARY OF THE INVENTION This invention relates to a metathesis catalyst compound represented by the formula: | wr P | and NÉ / O R

RL G G

G o to the OCuimaA Bad Metal 0: VA I saw no EDasanteas mana NA. OL A's 5/59

EN à ador of two neutral electrons; L 'is N, O, P, or S, preferably N or O; : G * is selected from the group consisting of hydrogen, a C; hydroxy C39, and a C, substituted hydrocarbyl Cao; R is a C, the Cao hydrocarbyl or a C, the substituted Cao hydrocarbyl; R 'is selected from the group consisting of hydrogen, C; hydrocarbyl Cao, and a C, substituted hydrocarbyl C39; and G is independently selected from the group consisting of hydrogen, halogen, C, C39 hydrocarbitla and C, C3z9 hydrocarbyl subs- | replaced. This invention further relates to a process for producing alpha olefin (preferably 1-decene) comprising contacting the metathesis catalyst described above with an olefin (preferably ethylene), and one or more triacylglycerides as fatty acid esters (preferably methyl esters) fatty acid, preferably methyl oleate). In a preferred embodiment, this refers to an alpha olefin production process (preferably 1-decene) comprising contacting the metathesis catalyst described above with an olefin (preferably ethylene), and one or more triacylglycerides with acid esters fatty (preferably fatty acid methyl esters, preferably methyl oleate) derived from biodiesel.

BRIEF DESCRIPTION OF THE FIGURE Figure 1 is a representation of the molecular structure of (P-Ph3) ClzRu (3-pentafluorfenyl-6,8-diisopropoxyinden-1-ylidene) (J) designed with 30% thermal ellipsoids.

DETAILED DESCRIPTION The present invention comprises a new metathesis catalyst compound useful for cross-olefin metathesis, and processes for using it. More particularly, the present invention comprises a new metathesis catalyst compound comprising an indenilinate chelating group. Even more particularly, the present invention comprises a new - metathesis catalyst compound that demonstrates the improved activity and selectivity for ethylene products in cross-methane ethylene reactions.

: '6/59 This invention also relates to a process which comprises: contacting a feed oil or oil derivative (and optional alkene) with an olefin metathesis catalyst under conditions that generate an alpha-olefin. Typically, the feed oil is esterified or transesterified with an alcohol before contacting the olefin metathesis catalyst.

This invention further relates to a process comprising contacting a triacylglyceride or a derivative thereof with an optional alkene (such as ethylene) and an olefin metathesis catalyst under conditions that generate an alpha-olefin, typically generating a linear alpha-olefin. | (such as 1-decene, 1-heptene, and / or 1-butene) and an ester or acid functionalized olefin.

This invention also relates to a process for the production of alpha-olefins (preferably linear alpha-olefins) comprising contacting a triacylglyceride with an alcohol! (such as methanol) to produce an alkyl fatty acid ester and then contact the fatty acid alkyl ester - with an olefin metathesis catalyst (and optional alkene, such as ethylene) under conditions that generate an alpha-olefin (preferably alpha - linear olefin, preferably 1-decene, 1-heptene, and / or 1-butene) and an olefin functionalized with ester or acid.

This invention further relates to a process for producing alpha-olefins (preferably linear alpha-olefins) comprising contacting a triacylglyceride with water or an alkaline reactive (such as sodium hydroxide) to produce a fatty acid and then contacting the fatty acid with an olefin metathesis catalyst (and something optional, such as ethylene) under conditions that generate an alpha-olefin (preferably a linear alpha-olefin, preferably 1-decene, 1-heptene, and / or 1-butene) and a functionalized olefin with ester or acid.

This invention also relates to the contact of unsaturated fatty acid with an alkene (such as ethylene) in the presence of an olefin catalyst catalyst under conditions that generate an alpha-olefin (preferably a linear alpha-olefin, preferably 1-decene, 1-heptene, and / or

: ': 7/59 1-butene) and an ester or acid functionalized olefin. ] This invention also relates to the contact of unsaturated fatty acid ester with an alkene (such as ethylene) in the presence of an olefin metathesis catalyst under conditions that generate an alpha-olefin (preferably a linear alpha-olefin, preferably 1-decene, 1-heptene, and / or 1-butene) and an ester or acid functionalized olefin.

This invention also relates to the contact of an unsaturated fatty acid alkyl ester with an alkene (such as ethylene) in the presence of an olefin metathesis catalyst under conditions that generate an alpha-olefin | 10 (preferably a linear alpha-olefin, preferably 1-decene, 1-heptene, and / or 1-butene) and an ester or acid functionalized olefin.

This invention further relates to a process for producing alpha olefin (preferably linear alpha olefin, preferably 1-decene, 1-heptene and / or 1-butene) comprising contacting a methane catalyst with an alkene (preferably ethylene), and one or more fatty acid esters (preferably fatty acid methyl esters, preferably methyl oleate). In a preferred embodiment, this refers to a process for producing alpha olefin (preferably linear alpha olefin, preferably 1-decene, 1-heptene and / or 1-butene) comprising contacting a metathesis catalyst with an alkene ( preferably ethylene), and one or more fatty acid esters (preferably fatty acid methyl esters, preferably methyl oleate) derived from biodiesel.

In a preferred embodiment, the olefin metathesis catalyst described here can be combined directly with food oils | , triacylglycerides, biodiesel, fatty acids, fatty acid esters and / or alkyl esters of fatty acids to produce alpha-olefins, preferably linear alpha-olefins, preferably C, to Co, alpha-olefins, preferably alpha- linear olefins, such as 1-decene, 1-heptene and / or 1- butene.

In a preferred embodiment, a mixture of one or more biodiesels, triacylglycerides, fatty acids, fatty acid esters and / or

P '8/59 alkyl fatty acid esters are used to produce alpha-olefins, preferably linear alpha-olefins, preferably Ca, to Ca, alpha-olefins, preferably | preferably C, to C7, linear alpha-olefins. In a preferred embodiment a mixture of alpha olefins, preferably linear alpha olefins, preferably 1-decene, 1-heptene and / or 1-butene is produced. Process In a preferred embodiment, the metathesis catalysts described here can be combined directly with feed oils, seed oils, biodiesel, triacylglycerides, fatty acids, fatty acid esters and / or alkyl fatty acid esters ("fatty acid materials"). feed ") to produce alpha-olefins, preferably linear alpha-olefins, preferably C, to C>, alpha-olefins, preferably C, to Co, alpha-olefins | linear, such as preferably 1-decene, 1-heptene and / or 1-butene.

Typically, the molar ratio of alkene to unsaturated feed material (such as unsaturated fatty acid or fatty acid ester) is greater than about 0.8 / 1.0, preferably greater than about - 0.9 / 1.0. Typically, the molar ratio of alkene to the feed material (such as unsaturated fatty acid or fatty acid ester) is less than about 3.0 / 1.0, preferably less than about 2.0 / 1 , 0. Depending on the specific reagents, other molar ratios may still be appropriate. With ethylene, for example, a significantly higher molar ratio can be used, because the auto-metathesis of ethylene produces only ethylene again; no by-products of undesirable olefins are formed. Thus, the molar ratio of ethylene to feed material (such as fatty acid or fatty acid ester) can range from greater than about 0.8 / 1 to typically less than about 20/1.

The amount of metathesis catalyst that is employed in the process of this invention is any amount that provides an operable metathesis reaction. Preferably, the ratio of moles of feed material (preferably fatty acid ester and / or alkyl fatty acid ester) to moles of metathesis catalyst is typically greater than about 10: 1, preferably greater than about 100: 1, preferably

o | . '9/59 greater than about 1000: 1, preferably greater than about 10,000: 1, preferably greater than about 25,000: 1, preferably greater than about 50,000: 1, preferably greater than than about 100,000: 1. Alternatively, the molar ratio of feed material (preferably fatty acid ester and / or alkyl fatty acid ester) to the metathesis catalyst is typically less than about

10,000,000: 1, preferably less than about 1,000,000: 1, and more preferably less than about 500,000: 1. The contact time of the reagents and catalyst in a delote reactor can be of any duration, as long as the desired olefin metathesis products are obtained. Generally, the contact time in a reactor is greater than about 5 minutes, and preferably greater than about 10 minutes. Generally, the contact time in a reactor is less! than about 25 hours, preferably less than about 15 hours, and more preferably less than about 10 hours. In a preferred embodiment, the reactives (for example, catalyst, metathesis; food materials; something optional, optional alcohol, optional water, etc.) are combined in a reaction vessel at a temperature of 20 to 300ºC ( preferably 20 to 200 ° C, preferably 30 to 100 ° C, preferably 40 to 60 ° C) and an alkene (such as ethylene) at a pressure of 0.7 kPa to 6.9 MPa (0.1 to 1000 psi) 0.14 MPa to 2.8MPa (preferably 20 to 400 psi), 0.34 MPa to 1.7MPa (preferably 50 to 250 psi), if alkene is present, for a residence time of 0.5 second to 48 hours (preferably 0.25 to 5 hours, preferably 30 minutes2 hours).

In certain embodiments, where the alkene is a gaseous olefin, the pressure of the olefin is greater than about 34.5 kPa (5 psig), preferably greater than about 68.9 kPa (10 psig), and more preferably greater than about 310 kPa (45 psig). When a diluent is used with the alkaline gas, the pressure ranges mentioned above can still be appropriately used as the total pressure of olefin and diluent. Likewise, when a liquid alkene is used and the process is

% '10/59 conducted under an atmosphere of inert gas, so the pressure ranges mentioned above can be appropriately used for inert gas pressure.

In a preferred embodiment, from about 0.005 nmol to about 500 nmoles, preferably from about 0.1 to about 250 nmols, and more preferably from about 1 to about 50 nmoles of the metathesis catalyst they are charged to the reactor by 3 mmoles of feed material (such as triacylglycerides, biodiesel, fatty acids, fatty acid esters and / or alkyl esters of fatty acids or mixtures thereof, preferably fatty acid esters).

In a preferred embodiment, the alkene and an ester of unsaturated fatty acid or unsaturated fatty acid are co-metatized to form a first and a second olefin product, preferably a first reduced-chain alpha-olefin product and a second re-chain product - alpha-olefin terminal derivative functionalized with ester or acid. As a preferred example, metathesis of methyl oleate with ethylene will generate - co-metathesis products of 1-decene and methyl-9-decenoate. Both products are alpha-olefins; the decenoate still ends in an ester fraction at the opposite end of the carbon-carbon double bond chain. In addition to the desired products, methyl oleate can self-metatize to produce small amounts of 9-octadecene, a less desirable product, and dimethyl-9-octadecene-1,18-dioate, CH3OC (O0) (CH); CH = CH (CH2); C (0) OCH ;, a second less desirable product.

In the process of this invention, the conversion of feed material (preferably fatty acid ester and / or alkyl fatty acid ester) can vary widely depending on the specific reactive olefins, the specific catalyst, and specific process conditions employed. For the purpose of this invention, "conversion" is defined as the mole percentage of the feed material that is converted or reacted to the cross-metathesis alpha-olefin products. Typically, the conversion of feed material (preferably fatty acid ester and / or alkyl fatty acid ester) is greater than about 50 mole percent, preferably

oils 11/59 are greater than about 60 mole percent, and more preferably i greater than about 70 mole percent.

In the process of this invention, the yields of the first olefin product and ester or acid functionalized olefin product may still | 5 vary depending on the specific reagent olefins, catalyst, and process conditions employed. For the purpose of this invention, "yield" will be defined as the percentage in mol cross-metastasizing alpha-olefin olefin product formed in relation to the initial moles of the feed material (such as fatty acid ester and / or alkyl fatty acid ester ) in the food. Typically, the yield of alpha-olefin will be greater than about 35 mole percent, preferably greater than about 50 mole percent. Typically, the yield of ester or acid functionalized alpha-olefin will be greater than about 35 mole percent, preferably greater than about 50 mole percent.

In a preferred embodiment, the process is typically a solution process, although this may be a volume or high pressure BR process. Homogeneous processes are preferred. (A homogeneous process is defined as a process where at least 90% by weight of the product is soluble in the reaction medium.) A homogeneous process in volume is particularly preferred. (A volume process is defined as a process where the concentration of the reactant in all foods in the reactor is 70% by volume or more.) Alternatively no solvent or diluent is present in the reaction medium, (except for parts - small quantities used as a carrier for the catalyst or other additives, or quantities typically found with reactants (for example, propane in propylene). Diluents / solvents appropriate for the process include inert non-coordinating liquids. Examples include straight or branched chain hydrocarbons such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof as can be found

s' 12/59 traded commercially (Isoparº); perhalogenated hydrocarbons such as' perfluorinated C4.15 alkanes, chlorobenzene, and substituted aromatics and alkyl compounds like benzene, toluene, mesitylene, and xylene. Suitable diluents / solvents further include aromatic hydrocarbons, such as toluene or xylenes, and chlorinated solvents, such as dichloromethane. In a preferred embodiment, the feed concentration for the process is 60% by volume of solvent or less, preferably 40% by volume or less, preferably 20% by volume or less.

The process can be batch, semi-batch or continuous. As used here, the term continuous means a system that operates without interruption or cessation. For example, a continuous process to produce a metathesis product could be one where the reactants are continuously introduced into one or more reactors and the alpha- | olefin is continuously withdrawn.

Useful reaction vessels include reactors (including reactors in continuous agitation tanks, batch reactors, reactive extruders, R tubing or pump). The processes can be conducted in reaction type equipment coated with glass, stainless steel or similar. Useful reaction vessels include reactors (including continuous stirring reactors, batch reactors, reactive extruders, tubing or pump, continuous flow fixed bed reactors, slurry reactors, fluidized bed reactors, and distillation reactors catalytic). The reaction zone can be adjusted with one or more internal and / or external heat exchangers to control temperature fluctuations, or to prevent "fugitive" reaction temperatures.

If the process is conducted in a continuous flow reactor, then the hourly mass space velocity, given in units of grams of feed material (preferably fatty acid ester and / or alkyl fatty acid ester) per gram of catalyst per hour (h ”), will determine the relative amounts of feed material to the employed catalyst, as well as the residence time in the reactor of the unsaturated starting compound. In a flow reactor, the hourly mass space velocity of the material

. ! 13/59 unsaturated feed material (preferably fatty acid ester and / or fatty acid alkyl ester) is typically greater than about 0.04 g feed material (preferably fatty acid ester and / or al ester) - kil fatty acid) per g of catalyst per hour (h ”), and preferably — greater than about 0.1 h". In a flow reactor, at the hourly mass space velocity of the feed material (preferably acid ester) - of the fatty and / or fatty acid alkyl ester) is typically less than about 100 h ”, and preferably less than about 20 h”. In certain embodiments, reactions using the catalytic complexes of the present invention can be carried out in a biphasic mixture of solvents, in an emulsion or suspension, or in a lipid or bilayer vesicle.

The feed material is typically supplied as a liquid phase, preferably pure. In particular embodiments, the feed material is supplied in a liquid phase, preferably pure; while the alkene is supplied as a gas that is dissolved in the liquid phase. gives. In certain embodiments, the feed material is an ester of unsaturated fatty acid or unsaturated fatty acid and is supplied in a liquid phase, preferably pure; while the alkene is a gaseous alpha-olefin, such as ethylene, which is dissolved in the liquid phase.

Generally, the feed material is an ester of unsaturated fatty acid or unsaturated fatty acid and is supplied as a liquid at the process temperature, and is generally preferred to be used neat, that is, without a diluent or solvent. The use of a solvent generally increases recycling requirements and increases costs. Optionally, however, if desired, a solvent can be used with the alkene and / or the feed material. A solvent may be desirable, for example, where a liquid feed material and alkene are not fully miscible, and both can be solubilized in an appropriate solvent.

In a preferred embodiment, the productivity of the process is at least 200 g of linear alpha-olefin (such as decene-1) per mmol of catalyst per hour, preferably at least 5000 g / mmol / hour, preferably

: 14/59 at least 10,000 g / mmol / h, preferably at least 1 300,000 g / mmol / h.

For the purposes of this invention, "productivity" is defined as the amount in grams of linear alpha-olefin produced per mmol of catalyst introduced into the reactor, per hour. | | 5 For the purpose of this invention, selectivity is a measure of | conversion of alkene and feed material to alpha- cross-metathesis | olefin product, and is defined by the percentage of molten ol of olefin product formed in relation to the initial moles of someone or food material.

In a preferred embodiment, the selectivity of the process is at least 20% by linear alpha-olefin weight, based on the weight of the material exiting the reactor, preferably at least 25%, preferably at least 30%, preferably at least 35%. For the purpose of this invention, catalyst transformation number (TON) is a measure of how active the catalyst compound is and is defined as the number of moles of cross-methane alpha-olefin product formed per mole of catalyst compound.

In a preferred embodiment, the (TON) of the process is at least 10,000, preferably at least 50,000, preferably at least 100,000, preferably at least 1,000,000. In a preferred embodiment, the yield of alpha olefin (when converting unsaturated fatty acids, esters of unsaturated fatty acid, alkyl esters of unsaturated fatty acid or mixtures thereof), defined as the molar percentage of cross-linked alpha-olefin product formed by mole of unsaturated fatty acids, esters of unsaturated fatty acid, alkyl esters of unsaturated fatty acid or mixtures thereof introduced into the reactor, is 30% or more, preferably 40% or more, preferably 45% or more, preferably 50% or more, preferably 55% or more, preferably 60% or more.

In a preferred embodiment, the yield for the reactions (when converting triacylglycerides as represented in the formula below), is defined as the moles of alpha olefin formed divided by (the moles of unsaturated Rº + moles of unsaturated Rº + moles of unsaturated Rº) intro -

. '15/59 | in the reactor is 30% or more, preferably 40% or more, preferably 45% or more, preferably 50% or more, preferably 55% or more, preferably 60% or more,

HC - o - E & Rº o nc — o — d — rR | o HC - O - & - Rº where R ?, Rº and Rº each, independently, represents a chain of | 5 —saturated or unsaturated hydrocarbon (preferably Rº, Rº and Rº each | independently, are a C12 to C> 3 alkyl or alkene, preferably C15 to C> 7 alkyl or alkene). | Alkenes] In addition to the feed materials, the BR 10 metathesis process of this invention can use someone as a reactive. The term "alkene" must mean an organic compound containing at least one carbon-carbon double bond. Alkenes useful here typically have less than about 10 carbon atoms. The alkene may have an unsaturated carbon-carbon bond, or alternatively, two or more unsaturated carbon-carbon bonds. Since the metathesis reaction can occur on any double bond, alkenes containing more than one double bond will produce more metathesis products. Thus, in some embodiments, it is preferable to employ an alkene containing only a carbon-carbon double bond. The double bond can be, among others, a terminal double bond or an internal double bond. The alkene can also be replaced at any position along the carbon chain with one or more substitutes, provided that one or more substituents are essentially inert with respect to the metathesis process. Suitable substituents include, but are not limited to, alkyl, preferably C1, alkyl; cycloalkyl, preferably C3z; 5cycloalkyl; as well as hydroxy, ether, keto, villager

| | flight 16/59 gone, and halogen.

Non-limiting examples of suitable alkenes include ethylene, propylene, butene, butadiene, pentene, hexene, the various isomers thereof, as well as larger homologues thereof.

Preferably- | te, the alkene is a C> .8 alkene.

Most preferably the someone is a C2.6 - alkene, even more preferably a C2., 4 alkene, and more preferably ethylene.

Useful alkenes include those represented by the formula: R * - HC = CH-R *, where each R * is independently, hydrogen or a C, hydrocarbyl Co, preferably hydrogen or a C, hydrocarbyl Cs, preferably hydrogen, methyl, ethyl, propyl or butyl, more preferably R * is hydrogen.

In a preferred embodiment, both R * are the same, preferably both R * are hydrogen.

Ethylene, propylene, butene, pentene, hexene, octene and nonene (preferably ethylene) are useful alkenes here.

For the purposes of this invention and its claims, the term lower olefin means an alkene represented by the formula: R * -: HC = CH-R *, where each R * is independently, hydrogen or a C; hydrocarbyl Cs, preferably hydrogen or a C; hydrocarbyl C3z, preferably hydrogen, methyl, ethyl, propyl or butyl, more preferably R * is hydrogen.

In a preferred embodiment, both R * are the same, preferably both R * are hydrogen.

Ethylene, propylene, butene, pentene, hexene, and octene (preferably ethylene) are lower olefins useful here.

Triacylglycerides Triacylglycerides (TAGs), also called triglycerides, are a naturally occurring ester of three fatty acids and glycerol which is the main constituent of natural fats and oils.

The three fatty acids can all be different, all of the same, or just two of the same, they can be saturated or unsaturated fatty acids, and saturated fatty acids can have one or multiple unsaturations.

The chain lengths of fatty acids in naturally occurring triacylglycerides can be of varying lengths, but 16, 18 and 20 carbons are the most common.

Acid

. '17/59 of the natural fats found in plants and animals are typically made up of' odd numbers of carbon atoms only because of the way in which they are biosynthesized. Most natural fats contain a complex mixture of individual triglycerides and because of this, they melt in a wide range of temperatures.

Biodiesel is a monoalkyl ester derived from the processing of vegetable or animal oils and alcohols. Processing is typically conducted by an esterification reaction mechanism, and is typically performed in an excess of alcohol to maximize conversion. Esterification can refer to direct esterification, such as between a free fatty acid and an alcohol, as well as transesterification, such as between an ester and an alcohol. While vegetable oils and alcohols are commonly used as reactives in esterification reactions, a source of fatty acid free fatty acids, | soaps, esters, glycerides (mono-, di-), phospholipids, lusophospholipids, or amidase a source of monohydric alcohol, such as an alcohol or an ester, 1] can be esterified. In addition, various combinations of these reagents - can be used in an esterification reaction. Vegetable and animal oils include triglycerides and neutral fats, such as triacylglycerides, the main form of energy storage in animals and plants. These typically have the chemical structure: 'HC - O - C - R? | o HC —Oo —— R NS, HC - O - C— Rº where Rº, Rº and Rº each, independently, represents a saturated or unsaturated hydrocarbon chain (preferably Rº, Rº and Rº each, independently , are a C12 to C>; 6 alkyl or alkene, preferably C16 to C22 alkyl or alkene). Different vegetable oils have different fatty acid profiles, with the same or different fatty acids

: '18/59 occurring in a single glycerol.

For example, an oil can have linoleic, oleic and stearic acids attached to the same glycerol, with each of Rº, Re Rº representing one of these three fatty acids.

In another example, there may be two oleic acids and one stearic acid joined to the same glycerol, | —Every Rº, Rº and Rºrepresenting one of these fatty acids.

A triglice- | Particularly useful video consists of three fatty acids (for example, saturated fatty acids of general structure of CH3 (CH2)). COOH, where n is typically an integer from 4 to 28 or greater) joined to a glycerol (CaHs ( OH); 3) | by ester bonds.

In the esterification process, vegetable oils and short-chain alcohols are reacted to form mono-alkyl esters of fatty acid and glycerol (also called glycerin). When the alcohol used is methanol (CH3OH), a methyl ester is created with the general form CH3 (CH2), COOCH; 3 for saturated fatty acids.

Typically, but not always, the length of the carbon chain structure is 12 to 24 carbon atoms.

The esterification process can be catalyzed or not catalyzed.

Catalyzed processes are categorized into processes based on. chemical or enzyme.

Chemical catalytic methods can employ an acid and / or base catalyst mechanism.

Catalysts can be homogeneous and / or heterogeneous catalysts.

Homogeneous catalysts are typically liquid phase mixtures, while heterogeneous catalysts are solid phase catalysts mixed with liquid phase reactants, Oils and alcohols.

The fatty acid-rich material useful in the processes described here can be derived from plant, animal, microbial, or other sources (feed oil). Preferred feed oils include vegetable oils such as corn, soy, rapeseed, canola, sunflower, palm and other oils that are readily available, however, any vegetable oil or animal fat can be used.

Crude or unrefined oil can be used in certain modalities; however, filtered and refined oils are typically preferred.

The use of degummed and filtered raw material minimizes the potential for emulsification and blocking in the reactors.

The raw material with high water content can be dried before basic catalyst processing.

Bad-

. . 19/59 o. | raw material with high fatty acid content can be passed through a process | 'esterification to reduce the free fatty acid content prior to the esterification process to convert fatty acid glycerides into monoalkyl esters. The reduction of free fatty acids and the conversion of fatty acid glycerides can still be in the same processing step. Matter- | raw materials containing other organic compounds (such as hexane, heptane, isohexane, etc.) can typically be processed without significant changes to the reactor. Other materials containing fatty acid glycerides or others | fatty acid esters can also be used, including phospholipids, lysophospholipids, and fatty acid wax esters. The material rich in | fatty acid useful in the processes described here typically includes a mixture of fatty acids. For example, fatty acid profiles of various raw materials | Useful raw materials are shown in Table 1. Feed oil used as a raw material can also include a mixture of fatty acid glycerides from different sources. The free fatty acid content of useful vegetable oils is preferably about 0.1% by weight or less when used in. a homogenous catalyst esterification reaction. Higher levels can be used as well, and levels up to about 3% by weight, or even as high as 15% by weight or more can typically be tolerated. TABLE 1 fatty palm soy (also called Alto Oleico) | Yellow o, o,

EEPAPANEIENIA o, o,

. '20/59 Fatty Acid Profile of Various Typical Feed Oils: Acid | Oleode | Oil Rape Alto Oleico Fatty grease palm soy (also called Alto Oleico) | Yellow% 0% 2% by weight | by weight by weight 44% 7% 23% C16: 0 4% by weight by weight | by weight by weight 5% 5% 13% C18: 0 1% by weight by weight | by weight by weight V Y 44% in Soh by weight by weight | by weight by weight 109% y / T% oo Weight pre-weight | by weight by weight o, o, 1% at 1st weight in weight | by weight by weight 0% 0% 0% 'by weight | by weight by weight% 0% 0%. by weight | by weight by weight 1% 8% 9% by weight | by weight by weight 100% 100% 100% too by weight by weight | by weight by weight Alcohol! (also called Alcanóis)

The alcohol used here can be any monohydric, dihydric or polyhydric alcohol that is able to condense with the food material (such as unsaturated fatty acid) to form the corresponding unsaturated ester (such as the acid ester) fat). Typically, alcohol contains at least one carbon atom.

Typically, alcohol contains less than about 20 carbon atoms, preferably less than about 12 carbon atoms, and more preferably less than about 8 carbon atoms.

Carbon atoms can be organized in a straight or branched chain structure, and can be replaced with a variety of substituents, such as those previously disclosed in relation to

o a '21/59 tion with fatty acid, including the aforementioned alkyl, cycloalkyl,' aromatic monocyclic, arylalkyl, alkylaryl, hydroxyl, halogen, ether, ester, aldehyde and keto substituents.

Preferably, the alcohol is a straight or branched C1-12 alkanol.

A preferred alcohol is glycerol alcohol! trihydric, the fatty acid esters of which are known as "glycerides." Other preferred alcohols include methane! and ethanol.

Preferably, the alcohol used in the esterification and / or transesterification reactions is preferably a low molecular weight monohydric alcohol such as methanol, ethanol, 1-propanol, 2-propanol, 1- butanol, 2-butanol, or t -butanol.

The alcohol is preferably anhydrous; however, a small amount of water in the alcohol may be present (for example, less than about 2% by weight, preferably less than about 1% by weight, and more preferably less than about 0 , 5% by weight; however, in certain embodiments larger quantities may be tolerated). Acid esterification reactions are more tolerant of the presence of small amounts of water in alcohol than in reactions. basic transesterification processes.

While specific monohydric alcohols are discussed here with respect to certain modalities and examples, the preferred modalities are not limited to said specific monohydric alcohols.

Other suitable monohydric alcohols can also be used in the preferred modes.

Transesterification / Esterification Reactions Conversion of TAGs to alkyl fatty acid esters ("FA-AE") via TAG transesterification typically involves the formation of a reactive stream, which includes TAG (for example, at least about 75% by weight), alkanol (for example, about 5% by weight to 20% by weight), a transesterification catalyst (for example, about 0.05% by weight to 1% by weight), and optionally, glycerol ( typically up to about 10% by weight). Suitable alkanols may include C1-C6 alkanols and commonly may include methanol, ethanol, or mixtures thereof.

Appropriate transesterification catalysts may include alkali metal alkoxides containing 1 to 6 carbon atoms and commonly may include metals.

| 22/59 alkali metal oxide, such as sodium methoxide and / or potassium methoxide.

The basic catalyst is desirably selected so that the alkali metal alkoxide may suitably contain an alkoxide group which is the counterpart of the alkanol used in the reaction stream (for example, a combination of methanol and an alkali metal methoxy such as methoxy - sodium and / or potassium methoxide). The reactive stream may suitably include about 0.05 wt% to 0.3 wt% sodium methoxide | at least about 75% by weight of triacylglyceride, about 1% by weight to 7% by weight glycerol, and at least about 10% by weight methanol. | 10 In some embodiments, the reactive current may desirably include | about 0.05% by weight to 0.25% by weight of sodium methoxide, at least about 75% by weight triacylglyceride, about 2% by weight to 5% by weight glycerol, and about 10% by weight to 15% by weight methanol.

The rate and extent of the reaction for esterification of fatty acid glycerides or other fatty acid derivatives with monohydric alcohol in the presence of a catalyst depends on factors including, among others. other, the concentration of reagents, the concentration and type of catalyst and the conditions of temperature and pressure, and reaction time.

The reaction generally occurs at temperatures above about 50 ° C, preferably at temperatures above 65 ° C; however, the selected catalyst or the amount of catalyst used can affect this temperature to some extent.

Higher temperatures generally result in higher reaction rates.

However, the use of very high temperatures, such as those in excess of about 300ºC, or even those in excess of 250ºC, can lead to increased generation of side products, which can be undesirable depending on their presence can increase the costs of downstream purification.

Higher temperatures can be advantageously employed, however, for example, in situations where side products are not an issue.

The reaction temperature can be achieved by preheating one or more of the feed materials or by heating a mixture of the feed materials.

Heating can be achieved using appliances

. '23/59

They are known in the art, for example, heat exchangers, filled containers, submerged rollers, and the like. While specific temperatures and methods of obtaining specific temperatures are discussed here with respect to certain modalities and examples, the preferred modalities are not limited to said temperatures and specific methods of obtaining specific temperatures. Other temperatures and methods of obtaining temperatures can also be used in the modalities | preferred shares.

The amount of alcohol used in the reaction is preferentially in excess of the amount of fatty acid present in a molar base. The fatty acid can be free or combined, such as alcohol, glycol or glycerol, with up to three fractions of fatty acids being added to a glycerol. Additional amounts of alcohol above stoichiometric provide the advantage of assisting in directing the reaction balance to produce more of the fatty acid ester product. However, greater excesses of alcohol can result in higher processing costs and a greater investment of BR capital for the higher volumes of reagents used in the process, as well as higher energy costs associated with the recovery, purification and recycling of this process. excess alcohol. Thus, it is generally preferable to employ an amount of alcohol that generates a molar ratio of alcohol to fatty acid from about 15: 1 to about 1: 1 (stoichiometric), and more preferably from about 4: 1 to about 2 :1; however, the process can operate a much wider range of ratios from alcohol to fatty acid, with unreacted materials undergoing recycling or other processing steps. Generally, lower relative levels of alcohol to fatty acid result in reduced income and higher relative levels of alcohol to fatty acid levels result in increased capital and operating expenses. Some cases of operation in alcohol to fatty acid ratios above a wider range include when first starting the process or ending the process, when balancing the reactor's output to other processing steps or other processing facilities, such as those that produce alcohol or use a chain

. : 24/59 lateral, or when process disturbance occurs. When a 2: 1 methanol to fatty acid ratio is employed and a sodium hydroxide concentration of about 0.5% by weight of the total reaction mixture is used, the sodium hydroxide to methanol ratio is used. about 2% by weight entering the reactor and about 4% by weight at the outlet due to about half of the alcohol being consumed in the esterification reaction.

Similarly, larger amounts generally result in faster reactions. However, larger amounts of catalyst can lead to higher downstream separation costs and a different profile of reaction side products. The amount of homogeneous catalyst is preferably from about 0.2% by weight to about 1.0% by weight of the reaction mixture when the catalyst is sodium hydroxide; in a typical concentration of 0.5% by weight when a 2: 1 molar ratio of methanol to fatty acid is used; however, in certain embodiments, greater or lesser amounts may be employed. The amount of catalyst used can also vary depending on the nature of the catalyst, supply materials, operating conditions and other factors. Specifically, the temperature, pressure, free fatty acid content of the feeder, and degree of mixing can change the amount of catalyst preferentially employed. While quantities of specific catalysts are discussed here with respect to certain modalities and examples, the preferred modalities are not limited to said specific quantities of catalysts. Other amounts of suitable catalysts can also be employed in the preferred embodiments.

The esterification reaction can be carried out batchwise, as in a stirred tank, or it can be carried out continuously, as in a continuously stirred tank reactor (CSTR) or a plug flow reactor (PFR ). When operated in a continuous mode, a series of continuous reactors (including CSTRs, PFRs, or combinations thereof) can advantageously operate in series. Alternatively, batch reactors can be organized in parallel and / or series.

When the reactor is operated in a continuous mode, one or more

| . '25/59 of the feed materials is preferably measured in the process. Various measurement techniques can be employed (for example, metering pumps, positive displacement pumps, control valves, flow meters, and the like). While types of specific reactors are discussed here with respect to certain modalities and examples, the preferred modalities are not limited to said specific reactors. Other types of suitable reactors can also be used in the preferred modalities.

Fatty acids and fatty acid esters Fatty acids are carboxylic acids with sa- aliphatic tails | cloudy or unsaturated fats that are found naturally in many different | different oils and fats. Any unsaturated fatty acid can be appropriately employed in the process of this invention, as long as the unsaturated fatty acid can be metatized as shown herein. An unsaturated fatty acid comprises a long carbon chain containing at least one carbon-carbon double bond and ending in a carboxylic acid group. Typically, the unsaturated fatty acid will contain more than about 8 carbon atoms, preferably more than about 10 carbon atoms, and more preferably more than about 12 carbon atoms. Typically, the unsaturated fatty acid will contain less than about 50 carbon atoms, preferably less than about 35 carbon atoms, and more preferably less than about carbon atoms. At least one carbon-carbon double bond is present along with the carbon chain, this double bond generally occurring in about half of the chain, but not necessarily. The carbon-carbon double bond can still occur at any other internal location along the chain. A terminal carbon-carbon double bond, at the opposite end of the carbon chain from the carboxylic acid terminal group, is still appropriately employed, although the terminal carbon-carbon double bond occurs less commonly in fatty acids. Unsaturated fatty acids containing terminal carboxylic acid functionality and two or more carbon-carbon double bonds

. 26/59 may be suitably employed in the process of this invention. Since U metathesis can occur on any of the carbon-carbon double bonds, a fatty acid containing more than one double bond can produce a variety of metathesis products. Unsaturated fatty acid - can be linear or branched and substituted along the fatty acid chain with one or more substituents, provided that the one or more substituents are | substantially inert with respect to the metathesis process. Examples | non-limiting suitable substituents include alkyl fractions, preferably C1., 09 alkyl fractions, including, for example, methyl, ethyl, propyl, butyl, and the like; cycloalkyl fractions, preferably Ca.g cycloalkyl, including, for example, cyclopentyl and cyclohexyl; aromatic monocyclic fractions, preferably aromatic Ck fractions, that is, phenyl; arylalkyl fractions, preferably C; .16 arylalkyl fractions, including, for example, benzyl; and alkylaryl fractions, preferably C 7.16 alkylaryl fractions, including, for example, tolyl, ethylphenyl, xylyl, and the like; as well as: hydroxyl, ether, keto, aldehyde, and halide, preferably chlorine and bromine, fun-. tionalities.

Non-limiting examples of suitable unsaturated fatty acids include 3-hexenoic (hydrosorbic), trans-2-heptenoic, 2-octe- "- noic, 2-nonenoic, cis- and trans-4-decenoic, 9-decenoic acids ( caproleic), 10-undeceneic (undecylenic), trans-3-dodeceneic (linderic), trideceneic, cis-9-tetradeceonic (myristoleic), pentadeceneic, cis-9-hexadecenoic (cis-9-palmitoelic), trans-9-hexadecene (trans-9-palmitoleic), 9-heptadekenoic, cis-6-octadecenoic (petroselinic), trans-S-octadecenoic (petrose-laidico), cis-9-octadecenoic (oleic), trans-9-octadecenoic (elaidic ), cis-11-octadecenoic, trans-11-octadecenoic (vaccenic), cis-5-eicosenoic, cis-9-eicosenoic (gadoleic), cis-11-docosenoic (ketoleic), cis-13-docoseenoic (erucic ), trans-13-docosenoic (brasshydric), cis-15-tetracosenoic (selacoleic), cis-17-hexacosenoic (ximenic), and cis-21-triacontenoic (lu-mequeic), as well as 2,4-hexadiene acids (sorbic), cis-9-cis-12-octa-decadienoic (linole ico), cis-9-cis-12-cis-15-octadecatrienoic (linolenic), eleostearic, 12-hydroxy-cis-9-octadecenoic (ricinoleic), and the like.

Roo 27/59 Oleic acid is the most preferred.

Unsaturated fatty acids can be obtained commercially or synthesized by saponification of fatty acid esters, this method being known in the art.

Fatty acid esters are formed by condensation of a fatty acid and an alcohol.

Alkyl esters of fatty acids are fatty acids where the hydrogen of -OH of the acid group is replaced by a hydro-carbyl group, typically a C group, to Ca, alkyl, preferably a C; a | Cao alkyl.

Alkyl esters of fatty acids are fatty acids where the hydrogen-OH of the acid group is replaced by an alkyl group.

Alkyl esters of fatty acids useful here are typically represented by the formula: R * -C (0) -O-R *, where R 'is a C group; to C199 hydrocarbyl, preferably a group Cs to C> 7, preferably a group CÊ to C14 1-someone, and R * is an alkyl group, preferably a group C; a Cao alkyl, preferably methyl, ethyl, butyl, pentyl and hexyl.

Preferred fatty acid alkyl esters useful here are typically represented by the formula: R * -: CH2 = CH7-R * -C (0) -O-R *, where each R 'is independently a C group; C104 alkyl, preferably a Cs to Cao, preferably a Cs to C6 alkyl group, preferably a C14 group and R * is an alkyl group, preferably a C group; to C>, 5 alkyl, preferably methyl, ethyl, butyl, pentyl and hexyl.

Particularly preferred alkyl esters of fatty acids useful here are typically represented by the formula: CH3- (CH2) nC = C- (CH2) MC (0) -OR *, where e R * is an alkyl group, preferably a group C1 to C20 alkyl, preferably methyl, ethyl, butyl pentyl and hexyl, men are, independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 , 15 or 16, preferably 5, 7,9 or 11, preferably 7. Fatty acid methyl esters are fatty acids where the hydrogen of the -OH of the acid group is replaced by a methyl group.

Fatty acid methyl esters useful here are typically represented by the formula: R $ -C (O) - O-CH3, where R 'is a C group; to C1099 hydrocarbyl, preferably an A to A o to A DA AM (4% to Ps ES.

+ 'Preferred fatty acid useful here are typically represented by the' formula: R-CH2 = CH2-R * -C (0) -O-CH; 3, where each R 'is independently a C group; to C1905 alkyl, preferably a Cs to Cao, preferably a group Cg to Ci, alkyl, preferably a group Co. Particularly preferred fatty acid methyl esters useful here are represented by the formula: CH3- (CH2) nC = C- ( CH2) MC (0) -O-CH3, where men are, independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, preferably 5, 7,9 or 11, preferably 7. Preferred fatty acid methyl esters include methyl palmitoleate, methyl oleate, methyl gadoleate, methyl erucate, methyl linoleate, | methyl linolenate, methyl siate, and mixtures of methyl esters derived from oil | soy, beef tallow, pine oil, animal fats, residual oils | Igraxas, rapeseed oil, seaweed oil, Canola oil, palm oil, jatropha oil, soy oil rich in oleic oil (eg 75 mol% or more, preferably 85 mol% or more, preferably 90 mol% or more), safflower oil rich in oleic (eg 75% mol or more, preferably 85% mol or more, preferably 90% mol or more), sunflower oil rich in oleic (eg example 75% by mol or more, preferably 85% by mol or more, preferably 90% by —molourmais), and other sources derived from plants or animals containing fatty acids.

A preferred source of fatty acid methyl esters for use here includes sources of TAG and biodiesel. As described above, biodiesel refers to a transesterified vegetable oil or animal fat based on diesel fuel containing long-chain alkyl esters (typically methyl, propyl, or ethyl). Biodiesel is typically prepared by lipids that react chemically (like vegetable oil) with an alcohol. Biodiesel, TAG and derivatives thereof can be used in the processes described here. Likewise, preferred fatty acid methyl esters useful here can be obtained by reacting canola oil, corn oil, soybean oil, beef tallow, pine oil, animal fats, residual / grease oils, rapeseed oil, oil seaweed, canola oil, palm oil, jatropha oil,

. '29/59 oleic-rich soybean oil, oleic-rich safflower oil, sunflower oil' rich in oleic or mixtures of animal and / or vegetable fats and oils with one or more alcohols (as described above), preferably methanol.

Vegetable oils useful here preferably contain at least | 5 an unsaturation site and include, among others, canola, soy, palm, peanut, mustard, sunflower, tung, pine, perilla, grape seed, rapeseed, flax, safflower, pumpkin, corn and other oils extracted from plant seeds tas.

For the purposes of this invention and the claims of the same term "feed oil" refers to one or more plant, animal or microbial oil, including, but not limited to, canola oil, corn oil, soybean oil, fish, beef tallow, pine oil, animal fats, residual oils / greases, rapeseed oil, seaweed oil, peanut oil, mustard oil, sunflower oil, tung oil, perilla oil, dry oil grape mind, linseed oil, safflower oil, pumpkin oil, palm oil, jatropha oil, high oleic soybean oil, safflower oil. rich in oleic, sunflower oil rich in oleic, mixtures of animal and / or vegetable fats and oils, castor bean oil, dehydrated castor bean oil, cucumber oil, poppy seed oil, flaxseed oil , keratin oil, walnut oil, cottonseed oil, magnet seed oil, tuna oil, and sesame oils.

In a preferred embodiment, a combination of oils is used here. Preferred combinations include two (three or four) or more of pine oil, palm oil, tallow, residual grease, rapeseed oil, canola oil, soybean oil and seaweed oil. Alternative useful combinations include two (three or four) or more soy oil, canola oil, rapeseed oil, seaweed oil, and tallow.

In certain embodiments, processed oils, such as burnt oils, are the useful fatty acid sources here. While vegetable oils are preferred sources of fatty acids to practice revealed modalities of the present process, fatty acids are still available from animal fats including, among others, lard and fish oil,

O . 30/59 such as sardine oil and herring oil, and the like. As noted Ú above, in certain embodiments a desired fatty acid or fatty acid precursor is produced by a plant or animal source found in nature. However, particular fatty acids or fatty acid precursors are advantageously available from genetically modified organisms, such as genetically modified plants, particularly genetically modified algae. Said genetically modified organisms are designed to produce a desired fatty acid or fatty acid precursor biosynthetically to produce increased amounts of said compounds.

Alkyl oleates and alkyl erucates are fatty acid esters that are generally major components in the biodiesel produced by transesterification of alcohol and vegetable oils (preferably the alkis are a group C; a C39 alkyl, alternatively a group C; a C29 alkyl) . Biodiesel compositions that are particularly useful in this invention are those that have higher concentrations of alkyl oleate esters and alkyl eructe. These fatty acid esters preferably have an unsaturation site so that metathesis crossed with ethylene generates 1-decene as the co-product. The biodiesel compositions that are particularly useful are those produced from vegetable oils such as canola, rapeseed oil, palm oil, and other oils rich in oleate, oils rich in erucate. Particularly preferred vegetable oils include those containing at least 50% (on a molar basis) combined in oleic and erucic fatty acid chains of all fatty acid chains, preferably 60%, preferably 70%, preferably 80%, preferably 90%.

In another embodiment, useful fatty acid esters containing mixtures include those containing at least 50% (on a molar basis) fatty acid alkyl oleate ester, preferably 60% fatty acid alkyl oleate ester, preferably 70% alkyl ester fatty acid oleate, preferably 80% alkyl ester fatty acid oleate, preferably 90% alkyl ester! fatty acid oleate.

In another embodiment, useful fatty acid ester containing

| + '31/59 ras include those containing at least 50% (on a molar basis) fatty acid alkyl erucate ester, preferably 60% fatty acid alkyl erucate ester, preferably 70% fatty acid alkyl erucate ester, preferably 80 % fatty acid alkyl ester erucate, pre- | 5 preferably 90% fatty acid alkyl erucate ester.

In another embodiment, useful fatty acid esters containing mixtures include those containing at least 50% (on a molar basis) combined oleic and erucic fatty acid esters of all fatty acid ester chains, preferably 60%, preferably 70%, preferably 80%, preferably 90%. Isomerization In another embodiment, the feed material is first isomerized, then combined with a metathesis catalyst as described here. For example, the processes disclosed here may comprise providing a feed material (typically a fatty acid or fatty acid-derived), isomerization of an unsaturation site in the material: feed (typically a fatty acid or acid derivative) fatty) to produce an isomerized feed material (typically a fatty acid or fatty acid derivative), and then contact the isomerized material with an alkene in the presence of a metathesis catalyst. The isomerized material can be produced by isomerization with or without subsequent esterification or transesterification. Isomerization can be catalyzed by known biochemical or chemical techniques. For example, an isomerase enzyme, such as a linoleate isomerase, can be used to i - somerize linoleic acid from cis 9, cis 12 isomers to 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 basic catalyst, can be used to isomerize an unsaturated feed material (typically a fatty acid or fatty acid derivative) containing an unsaturation site in a site on the molecule in an e. 32/59 isomerized feed material (typically a fatty acid or a fatty acid derivative) containing an unsaturation site at a different location in the molecule.

Metal or organometallic catalysts can also be used to isomerize an unsaturated feed material (typically a fatty acid or a fatty acid derivative). For example, nickel catalysts are known to catalyze position isomerization of unsaturated sites in fatty acid derivatives.

Similarly, esterification, transesterification, reduction, oxidation and / or other modifications of the initial compound or products, such as a fatty acid or a fatty acid derivative, 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 another embodiment, the isomerization described above can be practiced with any triacylglyceride, biodiesel, fatty acids, fatty acid esters and / or alkyl fatty acid esters described here, typically before contacting the metathesis catalyst.

Metathesis Catalyst Compounds In a preferred embodiment, the metathesis catalyst compound is represented by the formula (1): xqax pl O Rº G: G GS Formula (|) where: M is a Group 8 metal, preferably Ru or Os , preferably Ru;

Ns mr sS3: ÍSSOSSAPS E ni = Am EE “Oo9m! M) + AIIIISBIí <í“ ”“ í3AÔt5os in li so, À -. 33/59 XeX! ' are, independently, any anionic binder, preferably a halide (preferably CI), an alkoxide, aryloxide, or an alkyl sulfonate, or X and X * can be joined to form a dianionic group and can form single rings of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms; L is a neutral two electron donor, preferably a phosphine or an N-heterocyclic carbene or an amino cyclic carbene; L 'is a heteroatom selected from the group consisting of N, O, P, or S, preferably N or O; . L and X can be joined to form a monoanionic group | multidentate and can form a single ring of up to 30 non-hydrogen atoms; or a multinuclear ring system of up to 30 non-hydrogen atoms; R and a C ,; to C39 hydrocarbyl or a C; the substituted hydrocarbyl C39; G * is selected from the group consisting of hydrogen, C; a C3 hydrocarbyl, and a C, a substituted hydrocarbon C39, preferably: an alkyl or substituted alkyl or hydrogen, preferably fluorinated alkyls or hydrogen; 'R' is selected from the group consisting of hydrogen, a C, aCzhydrocarbila, and a C; the substituted hydrocarbyl C39, preferably methoxy-substituted by phenyl, preferably 3,5- substituted by phenyl, preferably 3,5-dimethoxyphenyl; and each G is independently selected from the group consisting of hydrogen, halogen, a C; a C39 hydrocarbyl, and a C, Cao — hydrogen substituted hydrocarbyl, (preferably a C, Cao alkyl or a C; substituted C3.9 alkyl, or a Cs to Ca9 aryl or a C5 to C39 substituted aryl ). For the purposes of this invention and claims to it, a "Group 8 metal" is an element of Group 8 of the Periodic Table, as referenced by IUPAC in Nomencliature of Inorganic Chemistry: Recommendations 1990, GJ Leigh, Editor, Blackwell Scientific Publications,

nineteen ninety.

"'34/59 For the purposes of this invention and claims thereon a' substituted hydrocarbyl is a radical made of carbon and hydrogen where at least one hydrogen is replaced by a heteroatom.

For the purposes of this invention and claims, a substituted alkyl or aryl group is a radical made up of carbon and hydrogen where at least one hydrogen is replaced by a straight, branched, heteroatom or hydrocarbyl group | or substituted or unsubstituted cyclic containing 1 to 30 carbon atoms | at the.

For the purposes of this invention and claims thereon, "alkoxides" include those where the alkyl group is a C; hydrocarbyl Cio.

The alkyl group can be a straight or branched chain.

Preferred alkoxides include a group at C; C10 alkyl, preferably methyl, ethyl, propyl, butyl, or isopropyl.

Preferred alkoxides include those where the alkyl group is a phenol, substituted phenol (where phenol can be substituted with up to 1,2,3,4or5 group C; to C127 hydrocarbyl) or a C; C10 is hydrocarbon, preferably a C group; C 1-6 alkyl, preferably methyl,. ethyl, propyl, butyl, or phenyl.

Preferred alkyl sulfonates are represented by the formula (Il): R2? 0 = the 4 Formula (1) where R 'is a C group; to Ca, hydrocarbyl, fluoro-substituted carbyl group, chloro-substituted carbyl group, aryl group, or substituted aryl group, preferably a C group; the C172 alkyd or aryl, preferably trifluoromethyl, methyl, phenyl, para-methyl-phenyl.

For the purposes of this invention and claims therein, "ari- —loxides" include those where the aryl group is a phenol or naphthalene, or substituted phenol or substituted naphthalene, where the phenol or naphthalene can be substituted '35/59 with a or more substituents. (Replaced meaning that a 'hydrogen group is replaced by a linear, branched or cyclic heteroatom or hydrocarbyl group containing 1 to 30 carbon atoms.) Appropriate substitutes are independently selected and may comprise halogen, C groups; to C 2 hydrocarbyl, groups C, to C 2 hydrocarbyl substituted, preferably halogen, trifluoromethyl, amino, alkyl, alkoxy, alkylcarbonyl, cyano, carbamoyl, alkoxycarbamoyl, methylendioxy, carboxyl, alkoxycarbonyl, aminocarbonyl, some-alkylaminocarbonyl, n-alkylaminocarbonyl, dialkylaminocarbonyl, n-alkylaminocarbonyl, dialkylamine , nitro and the like, more preferably phenyl, chlorophenyl, trifluormethylphenyl, chlorofluorphenyl, aminophenyl, methylcarbonylphenyl, methoxyphenyl, methylendioxiphenyl, 1-naphthyl and 2-naphthyl.

For the purposes of this invention and claims to it, "phosphines" can be represented by the formula PR3, where R is independently selected from the group comprising hydrogen, groups C; hydrocarbyl C12, groups C; to C12 hydrocarbyl substituted, and halides. 'For the purposes of this invention and claims to it, "N-heterocyclic carbons." (NHCs) are represented by the formula (Ill): R $ /

Huh

GC

N Wa Formula (! Il) in which ring A is a 4-, 5-, 6-, or 7-membered ring, and Q is a large | group comprising one to four apex atoms selected selectively - dosdo of the group comprising C, O, N, B, Al, P, S and Si with available valences optionally occupied by hydrogen, oxo or R-substituents, where R is independently selected from the group comprising C groups; C12 hydrocarbyl, C groups, substituted C12 hydrocarbyl, and halides, and

", 36/59 each Rº is independently a hydrocarbyl group or substituted hydrocarbyl group Ú containing 1 to 40 carbon atoms, preferably methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclo- hexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclododyl, mesity, adamantyl, phenyl, benzyl, tolulyl, chlorophenyl, phenol, or substituted phenol.

Some particularly useful N-heterocyclic carbenes can be represented by the formula (IV) and (V): Rº Rº i gx go Ly IL 5 N 5 NR No R No Formula (IV) or Formula (V) in which - each Rº is independently a hydrocarbyl group or substituted hydrocarbyl group containing 1 to 40 carbon atoms, preferably methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl , decila, cyclodecila, - dodecila, cyclododecita, mesitila, adamantila, phenyl, benzyl, tolulil, chlorophenilla, phenol, hay! substituted, or CHXC (CH3) 3; and each Ró is independently hydrogen, halogen, a group C, C12 hydrocarbyl, or a group C; a substituted hydrocarbyl Ci2, preferably hydrogen, bromine, chlorine, methyl, ethyl, propyl, butyl, or aryl In other useful modalities, one of the N groups linked to the carbon in Formulas (IV) or (V) is replaced with another hetero atoms , preferably S, O or P, preferably a heteroatom S.

Other useful N-heterocyclic carbons include the compounds described in Hermann, WA Chem.

Eur.

J. 1996, 2,772 and 1627; Enders, D. et al., Angew.

Chem.

Int.

Ed. 1995, 34, 1021; Alder R.

W., Angew.

Chem.

Int.

Ed. 1996, 35, 1121;

. , 37/59 and Bertrand, G. et al., Chem. Rev. 2000, 100, 39. 'For the purposes of this invention and claims to it, "cyclic carbon amino alkyl" (CAACs) are represented by the formula (VI):

RÍ / o Rº Formula (VI) in which ring A is a 4-, 5-, 6-, or 7-membered ring, and Q is a large | group comprising from one to four apexed atoms selected from the group comprising C, O, N, B, AI, P, S and Si with available valences optionally occupied by hydrogen, oxo or R-substituents, where R is independently selected from the group comprising groups C, C12 hydrocarbyl , substituted C, C12 hydrocarbyl groups, and halides, and - 10 each Rº is independently a substituted hydrocarbyl group or hydrocarbyl group containing 1 to 40 carbon atoms, preferably methyl, ethyl, propyl, butyl (including isobutyl and n-butyl ), pentyl, cyclopentyl, hexyl, cyclohexite, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclododyl, mesityl, adamantyl, phenyl, benzyl, tolulyl, chlorophenyl, phenol, or substituted phenol. Some particularly useful CAACs include: Other useful CAACs include the compounds described in U.S.

7,312,331 and Bertrand et al., Angew. Chem. Int. Ed. 2005, 44, 7236-7239. Some preferred metathesis catalyst compounds include:

. , 38/59 | 7 to o Ck FR EF Co o

2. PII Cc! 1 b [Dr É O Yi "* - + P 1º 1º R F ck o” CA, and PISAOS to PISA OS-r o. Ft AS x

O and A - Ne el RF Ru TIDAS +

VS x Although the catalyst compounds are described herein in connection with cross-metathesis, one skilled in the art will appreciate that the catalyst compounds of this invention may be suitable for any metathesis reaction, including but not limited to closed-ring, thesisenino, acyclic dieno metathesis, and so on.

In certain embodiments, the catalyst compound employed in the process of the invention can be attached to or deposited on a solid catalyst support. The solid catalyst support will generate the heterogeneous catalyst compound, which will simplify the recovery of the catalyst. In addition,

it's the. 39/59: so, the catalyst support can increase the catalyst strength and frictional resistance.

Suitable catalyst supports include, but are not limited to, silicas, aluminas, silica-aluminins, aluminosilicates, including zeolites and other porous crystalline aluminosilicates; as well as titaniums, zirconia, magnesium oxide, carbon, and crosslinked, reticular polymeric resins, such as functionalized crosslinked polystyrenes, for example, chloromethyl functionalized crosslinked polystyrenes.

The catalyst compound can be deposited on the support by any method known to those skilled in the art, including, for example, impregnation, ion exchange, precipitation deposition, and vapor deposition.

Alternatively, the catalyst compound can be chemically attached to the support via one or more covalent chemical bonds, for example, the catalyst compound can be immobilized by one or more covalent bonds with one or more of the indenylene linker substitutes.

If a catalyst support is used, the catalyst compound 'can be loaded onto the catalyst support in any amount provided that the metathesis process of this invention proceeds with the desired metathesis products.

Generally, the catalyst compound is loaded onto the support in an amount that is greater than about 0.01% by weight of Group 8 metal, and preferably greater than about 0.05% by weight of Group 8. Group 8 metal, based on the total weight of the catalyst compound plus the support.

Generally, the catalyst compound is loaded onto the support in an amount that is less than about 20% by weight of Group 8 metal, and preferably less than about 10% by weight of Group 8 metal, based on total weight of the catalyst compound and support.

Synthesis of Metathesis Catalyst Compounds The catalyst compounds described herein can be synthesized by any method known to those skilled in the art.

Representative methods of synthesis of catalyst compounds | Group 8 of the type described here include, for example, treating a solution of the binder complex in an appropriate solvent, such as THF, with a complex

- '40/59 reactive of a Group 8 metal, such as dichloro-bis- (triphenylphosphino) ruthenium (II) and acetyl chloride.

The mixture can be heated, for example, to reflux, for an appropriate period of time to generate the desired chelating indene catalyst compound.

Typically, the removal of volatiles generates the Group 8 chelating indenylene catalyst compound, which can optionally be purified by appropriate chromatographic methods, as known in the art.

A phosphine binder, such as tricyclohexylphosphine can then be added, if desired.

Reaction conditions typically include a Group 8 reactive catalyst compound and the preferred phosphine binder in an appropriate solvent, such as benzene, for a time sufficient to effect the phosphine binder exchange, at a typically appropriate temperature. environment.

Copper chloride (1) is then added in excess and removal of the volatiles from the resulting slurry typically generates the Group 8 chelating indenylene catalyst compound comprising the most preferred phosphine binder. . While the present invention describes a variety of transition metal complexes useful in catalytic metathesis reactions, it should be noted that said complexes can be formed in situ.

Thus, additional binders can be added to a reaction solution as separate compounds, or they can be complexed into the central metal to form a metal binder complex prior to introduction to the reaction.

Alpha-olefin Metathesis Products In a preferred embodiment, the processes described here produce an alpha-olefin, preferably a linear alpha-olefin, which contains at least one more carbon than the alkene used in the reaction to produce the alpha-olefin .

In another embodiment, the processes described here produce a mixture of an alpha olefin and an alpha olefin functionalized with an ester.

Generally, a mixture of alpha olefins containing non-ester will be produced due to the presence of unsubstituted mono-, di-, and tri-fatty acid chains.

The main alpha olefin products are typically 1-decene,

:. 41/59 1-heptene, and 1-butene. The main alpha olefin product containing ester is typically methyl 9-decenoate.

In a preferred embodiment, the alpha olefin produced here is 1-decene. Typically the 1-decene co-product is an ester.

In a preferred embodiment, the major alpha olefin produced here is 1-decene. Typically the 1-decene co-product is an ester.

In a preferred embodiment, ethylene and methyl oleate are combined with the metathesis catalysts described here (such as triphenyl-phosphinodichloretorutene (3- (3,5-dimethoxyphenyl) -6,8-dimethoxyinden-1-ylidene); tri-phenylphosphinodichloroethane ( 3-pentafluorfenyl-6,8-diisopropoxyinden-1-ylidene); and / or tricyclohexylphosphinodichloretorutene (3-pentafluorfenyl-6,8-di-isopropoxy-inden-1-ylidene)) to produce 1-decene and methyl 9-decenoate.

The separation of 1-olefin (such as 1-decene) from the ester can typically be known in the art as distillation or filtration. ] The cross-linked linear alpha-olefin product (such as 1-decene or a mixture of Cg, Cio, C12 linear alpha-olefin) is then separated from any ester present and preferably used to produce poly-alpha-olefins (PAOs). Specifically, PAOs can be produced by polymerizing feed olefin in the presence of a catalyst such as AICl3, BF3, or BF3 complexes. Processes for producing PAOs are disclosed, for example, in the following patents: US patents 3,149,178;

3,382,291; 3,742,082; 3,769,363; 3,780,128; 4,172,855; and 4,956,122, which are fully incorporated by reference. PAOs are further discussed in Wil, JG. Lubrication Fundamentals, Marcel Dekker: New York,

1980. Certain high viscosity indices of PAO can still be conveniently prepared by polymerizing an alpha-olefin in the presence of polymerization catalysts such as Friedel-Crafts catalysts. These include, for example, aluminum trichloride, boron trifluoride, aluminum trichloride or boron trifluoride promoted with water, with alcohols such as ethanol, propanol, or butanol, with carboxylic acids, or with esters such as ethyl acetate or ethyl propionate or ether such as diethyl ether, diisopropyl o 42/59 ether, etc., see, for example, the methods disclosed by US Patents 4,149,178; 3,382.29; 3,742,082; 3,769,363 (Brennan); 3,876,720; 4,239,930;

4,367,352; 4,413,156; 4,434,408, 4,910,355; 4,956,122; 5,068,487;

4,827,073; 4,827,064; 4,967,032; 4,926,004; and 4,914,254. PAO can also be prepared using various metallocene catalyst systems. Examples include US patents 6,706,828; 5,688,887; 6,043,401; 6,548,724; 5,087,788;

6,414,090; 6,414,091; 4,704,491; 6,133,209; 6,713,438; WO 96/23751; WO 03/020856; and EP 0 613 873. PAOs are generally used as additives and base stocks for lubricants, among other things. Additional information on the use of PAOs in formulations of fully synthetic, semi-synthetic or partially synthetic lubricants or functional fluids can be found in "Synthetic Lubricants and High-Performance Functional Fluids", 2nd Ed. L. Rudnick, etc. Marcel Dekker, Inc., N.Y. (1999). Additional information on additives used in the formulation of the product can be found in 'Lubricants and Lubrications, Ed. By T. Mang and W. Dresel, by Wiley-VCH' GmbH, Weinheim 2001. In another embodiment this invention relates to :

1. A metathesis catalyst compound represented by the formula: x q Ss

MK A xD Rº G: G

G where M is a Group 8 metal; X and X 'are anionic ligands; L is a neutral two-electron donor; L 'is N, O, P, or S, preferably N or O; R

| «'43/59 is a C; hydrocarbyl Ca9 or a C, hydrocarbyl substituted Ca9; G * is B selected from the group consisting of hydrogen, a C; to hydrocarbyl C39, and a C; Ca, substituted hydrocarbyl; R 'is selected from the group consisting of hydrogen, a C ;, a C39 hydrocarbyl, and a C ;, a substituted hydrocarbyl C39; and G is independently selected from the group consisting of hydrogen, halogen, C; to Cao hidrocarbila and C, to Cao hidrocarbila substituted, preferably the compound comprises one or more of: triphenyl-phosphinodichloretorutene (3- (3,5-dimethoxyphenyl) - 6,8-dimethoxyinden-1-ylidene); tri-phenylphosphinodichloretorutene (3-pentafluorfenyl-6,8-diisopropoxyinden-1-ylidene); tricyclohexylphosphinodichloretorutene (3-pentafluorfenyl-6,8-diisopropoxyinden-1-ylidene); or mixtures thereof.

2. The catalyst compound in paragraph 1, where M is Ru.

3. The catalyst compound of paragraph 1 or 2, where X and X * are, independently, a halogen, an alkoxide, aryloxide, or a sulfonatoalkyl. '4. The catalyst compound of any of paragraphs 1 to 3,' wherein at least X and X 'is chloride, preferably both X and X * are chloride.

5. The catalyst compound of any one of paragraphs 1 to 4, in which it is NORO.

6. The catalyst compound of any of paragraphs 1 to 5, wherein L is selected from the group consisting of a phosphine, an N-heterocyclic carbene, and an amino cyclic carbene.

7. The catalyst compound in any of paragraphs 1 to 6, where (G * is selected from the group consisting of hydrogen, an alkyl, and substituted alkyl.

8. The catalyst compound of any of paragraphs 1 to 7, wherein each G is independently a C; substituted or unsubstituted C39 alkyl, or C, Ca; 9 substituted or unsubstituted aryl.

9. The catalyst compound of any one of paragraphs 1 to 8, where R 'is a methoxy substituted by phenyl.

10. The catalyst compound in any of paragraphs 1 to

| S . 44/59 | 9, in which L and X are joined to form a multi-multiply monoanonic group or a dianionic group and can form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms.

11. A process for producing alpha-olefin comprising con- | contact a feed material (such as a feed oil) with the | catalyst compound of any of paragraphs 1 to 10.

12. The process of paragraph 11, in which the feed material is selected from the group consisting of canola oil, corn oil, soybean oil, rapeseed oil, seaweed oil, peanut oil, mos oil - tarda, sunflower oil, tung oil, perilla oil, grape seed oil, linseed oil, safflower oil, pumpkin oil, palm oil, jatropha oil, soybean oil rich in oleic oil oil-rich safflower, oil-rich sunflower oil, mixtures of animal and vegetable fats and oils, castor bean oil, dehydrated castor oil, cucumber oil, poppy seed oil, flaxseed oil , lesquerella oil, oil. walnut oil, cottonseed oil, limante seed oil, tuna oil, sesame oils and mixtures thereof.

13. The process of paragraph 11, in which the feed material is selected from the group consisting of palm oil and seaweed oil.

14. A process for producing alpha-olefin comprising contacting a triacylglyceride with an alkene and the catalyst compound of any one of paragraphs 1 to 10, preferably wherein the alpha-olefin produced has at least one carbon atom a more than the alkene.

15. The process of paragraph 14, in which the triacylglyceride is contacted with alcohol and converted to a fatty acid ester or alkyl fatty acid ester before contacting the catalyst compound in any of paragraphs 1 to 10.

16. The process in paragraph 14, in which the triacylglyceride is contacted with water or an alkaline reagent and converted to a fatty acid or before contacting the catalyst compound in any of paragraphs 1a to 10.

-. 45/59

17. A process for producing alpha-olefin comprising con- | tactile an unsaturated fatty acid with an alkene and the catalyst compound of any of paragraphs 1 to 10, preferably where the alpha oil produced has at least one carbon atom more than the alkene.

18. A process for producing alpha-olefin comprising contacting a triacylglyceride with the catalyst compound of any one of paragraphs 1 to 10, preferably wherein the alpha-olefin produced has at least one more carbon atom than the alkene.

19. A process for producing alpha-olefin comprising contacting an unsaturated fatty acid ester and / or an unsaturated fatty acid alkyl ester with an alkene and the catalyst compound of any of paragraphs 1 to 10, preferably where the alpha The olefin produced has at least one carbon atom more than the alkene.

20. The process of any of paragraphs 11 to 19, wherein 'alpha olefin is a linear alpha olefin containing 4 to 24 carbon atoms. BR 21. The process of any one of paragraphs 11 to 20, wherein the alkene is ethylene, propylene, butene, hexene or octene.

22. The process of any one of paragraphs 19 to 21, where the fatty acid ester is a methyl fatty acid ester.

23. The process of any one of paragraphs 14 to 22, wherein the triacylglyceride, fatty acid, fatty acid alkyl ester, fatty acid ester is derived from biodiesel.

24. The process of any of paragraphs 11 to 23, wherein the alpha-olefin is butene-1, decene-1 and / or heptene-1.

25. The process of any of paragraphs 11 to 24, wherein the process productivity is at least 200 g of linear alpha-olefin per mmol of catalyst per hour.

26. The process of any of paragraphs 11 to 25, wherein the selectivity of the process is at least 20% linear alpha-olefin weight, based on the weight of the material leaving the reactor.

27. The process under any of paragraphs 11 through 26, where

| . . 46/59 the transformation number, defined as the moles of alpha olefin formed per mole of catalyst, of the process is at least 10,000.

28. The process of any of paragraphs 11 to 27, wherein the yield, when converting unsaturated fatty acids, unsaturated fatty acid esters, alkyl esters of unsaturated fatty acid or mixtures thereof, is 30% or more, said yield being defined as moles of alpha olefin formed by moles of unsaturated fatty acids, esters of unsaturated fatty acid, alkyl esters of unsaturated fatty acid or mixtures of the same introduced into the reactor.

29. The process of any of paragraphs 11 to 27, in which the yield, when converting TAGs as represented in the formula below, is 30% or more, said yield being defined as the moles of alpha olefin formed divided by (moles of Unsaturated rº + moles of unsaturated Rº + moles of unsaturated Rº) introduced in the reactor,: HC —O— ER. TE 'HC - O - C— R | o H, C - O - & Rº emqueRº?, Rº and Rº each, independently, represents a saturated or unsaturated hydrocarbon chain.

30. The process in paragraph 28, where the yield is 60% or more.

31. A process for producing C, Co, linear alpha-olefin comprising contacting a feed material with an alkene selected from the group consisting of ethylene, propylene butene, pentene, hexene, heptene, octene, nonene and mixtures and a metathesis catalyst compound of any one of paragraphs 1 to 10, wherein the feed material is a triacylglyceride, fatty acid, alkyl fatty acid ester, and / or fatty acid ester derived from seed oil.

| - '47/59

32. The process of paragraph 31, in which the alkene is ethylene, the 'alpha olefin is 1-butene, 1-heptene and / or -decene, and the feed material is a methyl ester of fatty acid, and / or ester of fatty acid. Experimental Section For the purposes of this invention and claims to this, Et is ethyl, Me is methyl, Ph is phenyl, Cy is cyclohexyl, THF is tetrahydrofuran, AcCl is acetyl chloride, DMF is dimethylformamide, and TLC is chromatography of thin layer. Typical dry-box procedures for synthesis of sensitive compounds were followed including dry glassware (90ºC, 4 hours) and anhydrous solvents purchased from Sigma Aldrich (St. Louis, MO) which were further dried in a 3A sieve. All reagents were purchased from Sigma-Aldrich, unless otherwise noted. Spectra of * H, ** C, and ** P were | recorded on Bruker 250 and 500 spectrometers. IR data were re- | 15 recorded on a Bruker Tensor 27 FT-IV spectrometer. The yields of 'metathesis product and catalyst transformation numbers from: data recorded on an Agilent 6890 GC spectrometer as shown below. Typically, a sample of metathesis product will be taken and analyzed by GC. An internal standard, usually tetradecane, is used | to derive the amount of metathesis product that is obtained. The amount | of metathesis product is calculated from the area under the desired peak in the GC trace, in relation to the internal standard. ] Yield is reported as a percentage and defined as 100 * [micromoles of metathesis products obtained by GCY / [micromoles of | heavy feed material in the reactor]. Selectivity is reported as a percentage and is defined as 100 * [area under the peak of desired metastasis products / [sum of areas of the cross methane peaks and the products of homometathesis]. Catalyst transformers for the production of metathesis products is defined as [micromoles of metallosel product / ([micromoles of catalyst]. In a particular embodiment, methyl oleate metathesis with s. 48/59 | NE | | ethylene will generate metathesis by-products of 1-decene and methyl-9-decenoate ms In addition to the desired products, methyl oleate can homometatize to produce small amounts of 9-octadecene, a less desirable product, and 1,18-dimethyl- 9-octadecenedioate, a second less desirable product.

The yield is defined as 100 x [micromoles of ethanol products obtained from GCY [micromoles of methyl oleate weighed in the reactor]. The selectivity of 1-decene is shown as a percentage and is defined as 100 x [peak area of 1-decene GC & methyl-9-decenoate] // [sum of peak areas of 1-decene GC, methyl -9-decenoate, and the homometatase products, 9-octadecene, and 1,18-dimethyl-9-octadecenedioate]. The transformation of catalysts to 1-decene production is defined as [micromoles of 1-decene obtained from GCY / ([micromoles of catalyst]. Examples The synthetic protocols for representative alkylidene binders and the corresponding ruthenium alkylidene complexes are as follows Other alkylidene binders and their respective metal complexes can: be derived in an analogous manner.

Example 1: Synthesis of (PPh3) CIRu (3-3,5-dimethoxyphenyl-6,8-dimethoxyinden-1-ylidene) Bis (3,5-dimethoxyphenyl)] methane! (A): 3,5-Dimethoxybenzaldehyde (5.0 9, 30 mmol) was dissolved in 150 ml THF in a 500 ml round bottom flask. 3,5-Dimethoxyphenyl magnesium chloride (1 M in THF, 45 mL) was added slowly.

The reaction was heated to 40ºC for 4 hours, then quenched with saturated ammonium chloride.

The mixture was extracted with 3 portions of ether. The combined organic layers were washed with brine, dried over anhydrous MgSO, then concentrated to a crude pale yellow solid which was taken to the next step .: * H NMR (250 MHz, CsDs): ô 3.29 (d, J = 5.0 Hz, 12H), 6.46 (m, 2H), 6.56 (m, 1H), 6.76 (m, 2H), 7.04 (t, J = 8.2 Hz, 1H). Bis (3,5-dimethoxypheni) methanone (B): Pyridinium chlorochromate (PCC) (12.9 g, 30 mmol) was suspended in 30 ml of dichloromethane in a 200 ml round bottom flask.

Bis (3,5-dimethoxyphenyl) methane! 1 crude acid

-. 49/59 ma (compound A) was suspended in 30 ml of dichloromethane then added to the chromate suspension.

The dark solution was allowed to stir at room temperature for 18 hours then diluted with ether.

After decanting, the organic solution was washed twice with IN NaOH, twice with 10% HCl, NaHCO; saturated, and then with brine.

It was dried over anhydrous MgSO;, filtered and concentrated to generate a yellowish brown solid.

The brownish yellow solid was purified by column chromatography using 50% acetone / hexane as the eluent to generate the product as a yellow solid in 63% yield during 2 steps: IV (cm): 2960, 2938,2834,1660, 1592, 1456, 1425, 1349, 1304, 1205, 1157, 1066, 744; 'H NMR (250 MHz, CEDs): ô 3.21 (s, 12H), 6.67 (t, J = 2.2 Hz, 2H), 7.21 (d J = 2.5 Hz, 4H) ; * “C NMR (63 MHz, CDs): 54.9 (4C), 105.3 (2C), 108.0 (4C), 140.2 (2C), 161.1 (4C), 195.2. 1,1-Bis (3,5-dimethoxyphenyl) prop-2-in-1-01 (C): In a 100 mL bottle, bis (3,5-dimethoxy-phenyl) methanone (compound B, 1,2 g, 3.9 mmol) was dissolved in 20 ml of diethyl ether.

Approximately 5 mL THF was added to adjust to solvate the ketone followed by slow addition of ethylmagnesium bromide (0.5 M in THF, 12 mL). The reaction was monitored by TLC and the consumption of the starting material, 2N HCI was added to the flask.

The mixture was extracted 3 times with ethyl acetate and the combined organic layers were washed with brine, dried over MgSOSO, anhydrous, filtered and concentrated to generate a yellow oil.

Purification was achieved with column chromatography using a 30% to 50% acetone / hexane gradient.

The product was obtained as a pale yellow oil in 73% yield: Rr 0.14 (30:70 acetone / hexane); IR (cm): 3441, 3280, 2940, 2837, 1598, 1460, 1289, 1205, 1156, 1053, 834, 748, 689; * H NMR (250 MHz, CDs): 8 2.38 (s, 1H), 2.94 (br s, 1H), 3.27 (s, 12H), 6.42 (t, J = 2.5 Hz, 2H), 3.99 (d, J = 2.5 Hz, 4H); * C NMR (63 MHz, CsDs): 54.8 (4C), 74.5, 75.3, 86.8, 100.1 (2C), 104.9 (4C), 147.6 (2C), 161.2 (4C).

| S, 50/59 Scheme 1: Synthesis of 1,1-bis (3,5-dimethoxyphenyl) prop-2-in-1-01 (C) 'oH' o NT.

Mer "Oo" PO | IT IS.

Ç due. OMe CH2Cl2, 63% Meo. x OMe - per Meo.

To Q OMe in OO OMe 6 OMe OMe c OMe (PPh3) CLRu (3-3,5-dimethoxyphenyl-6,8-dimethoxyinden-1-ylidene) (D): Acetyl chloride (5 - 10 ul) was added to a solution of (PPh3); RuClz (336 mg, 0.35 mmol) and 1.1 di (3,5-dimethoxy) phenyl 2-propin-1-0l (compound C, 172mg, 0.525 mmol) in 6 ml THF .

Propinol was added as a 0.2 M solution in THF.

The solution was left at reflux for 18 hours, after which the reaction flask was placed in a high vacuum to remove the solvent.

Isopropanol (12 mL) was added to the reaction flask and the purple material: it was removed from the walls by intense stirring overnight.

The resulting suspension was filtered and washed with 5 ml of isopropanol followed by two washes with pentane (5 ml each). Any remaining solvent was removed from the red-brown powder in a vacuum at 60ºC, generating 240 mg (92%). The product was characterized by NMR spectrum (* H, ºC, and? * P). The results are as follows: 1H NMR (250 MHz, CD2Cl2, 30ºC): õ = 7.4 (bt, 11H), 6.0-7.0 (m, 6H), 4.57 (s, 0.5H ), 3.74-4.0 (m, 6H, R-OCH; 3 x 2), 3.64 (s, 68H, R-OCH; 3 x 2). ºC NMR (500 MHz, CD2Cb, 30ºC): õ = 289.7 (d, Jpc = 100 Hz). P NMR (250 MHz, CDC, 30 ° C): õ = 54 ppm.

s . 51/59 1 | Scheme 2: Synthesis of (PPh3) CIRu (3-3,5-dimethoxyphenyl-6,8-dimethoxyinden-1- | ylidene) (D)

HO Meo. OMe ci PPhs ACC, THF and OMe eme - Ove en sf, "eo O (O? E OMe + OMe DRPIPhO: p Example 2: Synthesis of (PPh3) ClRu (3-pentafluorfenil-6,8-di-isopropoxyinden- 1 -ilidene) (J) Isopropyl 3,5-diisopropoxybenzoate (E): In a 1 L round-bottom flask, 3,5-dihydroxybenzoic acid (109, 64 mmol), potassium carbonate (42 g, 260 mmol) and cesium carbonate (30 g, 92 mmol) were dissolved in 300 ml of dimethylformamide.After stirring at room temperature for approximately 20 min, 2-iodopropane (43 g, 256 mmol) was added The reaction was left to stir overnight, then quenched with water and extracted with three portions of ethyl acetate The combined organic layers were washed twice with water and brine, then dried (MgSO;) , filtered and concentrated to a yellow oil: R; 0.48 (30:70 acetone / hexane); IV (cm): 2978, 2935, 1715, 1593, 1449, 1372, 1296, 1234, 1183,1112,1038, 769; * H NMR (250 MHz, CsDs): 8 1.07 (dd, J = 6.7, 12.0 Hz, 18H), 4.20 (qn, J = 6.2 Hz, 2H), 5.22 (qn, J = 6.2 Hz, 1H), 6.75 (t, J = 2.5 Hz, 1H), 7.56 (d, J = 2, 5 Hz, 2H); * C NMR (63 MHz, CsDs): 23.7 (2C), 23.8 (4C), 70.2, 71.8 (20), 110.9, 111.1 (20), 135.5, 161.6 (2C), 167.9. 3,5-diisopropoxybenzoic acid (F): Crude isopropoxybenzoate above (compound E) was dissolved in 200 ml THF / H2O (1: 1) in a 500 ml bottle. Excess lithium hydroxide (10 g) was added and the reaction was refluxed for 48 hours. The mixture was cooled, acidified with HCl! to pH 2, then extracted with several portions of diethyl ether. The organic layers were washed with brine, dried over MgSO4, and concentrated to an

| | S . 52/59 white solid in 55% yield over 2 stages: IV (cm): 3064, Ú 2978, 2933, 2639, 1693, 1594, 1300, 1158, 1114, 1040, 767; * H NMR (250 MHz, CD3OD): 8 1.30 (dd, J = 2.3, 5.9 Hz, 12H), 4.59 (qn, J = 6.2 Hz, 2H), 6.61 (t, J = 2.3 Hz, 1H), 7.10 (d, J = 2.5 Hz, 2H); * C NMR (63 MHz, CD; OD): | 5 22.2 (4C) 71.2 (2C), 109.8, 109.9, 133.8, 160.3 (2C), 169.7. 3,5-diisopropoxy-N-methoxy-N-methylbenzamide (G): Diisopropoxybenzoic acid (compound F, 10g, 41 mmol) was dissolved in benzene (100 mL) in a 500-ml round-bottom flask ml.

Thionyl chloride (12.2 mL, 168 mmol) was added and the reaction heated to reflux for 1 hour.

The mis- | 10 tura was then cooled to room temperature and concentrated under pressure | reduced.

The resulting residue was re-dissolved in dichloromethane and concentrated again to generate 3,5-diisopropoxybenzoyl chloride.

In a separate 200 ml flask, N, O-dimethylhydroxylamine-HCI (4.0 g, 42 mmol) was suspended in 80 ml of dichloromethane at 0ºC.

Triethylamine (12.4 mL, 88 mmol) was added slowly, followed by crude 3,5-diisopropoxybenzoyl chloride.

The reaction flask was allowed to warm to room temperature and stirred overnight.

The reaction was quenched with water and extracted with three portions of dichloromethane.

The combined organic layers were washed with brine, dried over MgSO;, filtered and concentrated under reduced pressure.

Purification of the resulting brown oil by column chromatography (30% acetone / hexane) generated Weinreb's amide (compound G) as a yellow oil in 60% yield from 3,5-dihydroxybenzoic acid: Rr 0.33 (30:70 acetone / hexane); IR (cm): 2977, 1647, 1590, 1441, 1374, 1184, 1155, 1113, 1037, 964; * H NMR (250 MHz, CsDs): 8 1.06 (dd, J = 2.5, 5.9Hz, 12H), 3.00 (s, 3H), 3.05 (s, 3H), 4, 19 (qn, J = 6.2 Hz, 2H), 6.689 (t, J = 2.5 Hz, 1H), 7.10 (d, J = 2.5 Hz, 2H); ºC NMR (63 MHz, CsDs): 21.9 (4C), 33.4, 60.4, 69.8 (2C), 106.6, 108.1 (2C), 137.0, 159.3 ( 2C), 169.8. 3,5-diisopropoxyphenylperfluorfenylmethanone (H): In a 200 ml round-bottomed flask, Weinreb's amide (compound G, 1 g, 3.5 mmol) - dissolved in ether and cooled.

Pentafluorfenylmagnesium bromide (0.5 M in THF, 8.52 mL) was added slowly and the reaction stirred under ambient conditions overnight.

The mixture was quenched with ammonium chloride

S . 53/59 saturated and extracted with three portions of ether.

The combined organic layers were washed with brine, dried over MgSO ;, anhydrous, filtered and concentrated to generate a dark brown oil that on the chromato- | graph (40% acetone / hexane) crystallized to the desired ketone in 46% yield: R; 0.60 (30:70 acetone / hexane); IR (cm): 2980, 1682, 1588, 1501, 1320, 1185, 1160, 1113, 991, 770; * H NMR (250 MHz, CDs): ô 1.02 (d, J = 5.0 Hz, 12 H), 4.10 (qn, J = 7.5 Hz, 2H), 6.66 (t, J = 2.2 Hz, 1H), 7.13 (d, J = 2.2 Hz, 2H); * C NMR (63 MHz, CDs): 21.6 (4C), 70.2 (2C), 109.1 (2C), 109.8, 138.5, 160.1 (2C), 184.9. 1- (3,5-diisopropoxyphenyl) -1-perfluorphenylprop-2-in-1-01 (1): The above methanone (compound H, 3.2 g, 8.2 mmol) was dissolved in 40 mL ether in a 100 mL round bottom flask.

Ethinylmagnesium bromide (0.5 M in THF, 24.6 mL) was added slowly and the reaction stirred overnight.

The reaction was quenched with saturated ammonium chloride and extracted with three portions of ether.

The combined organic layers were washed with brine, dried over MgSO, anhydrous, filtered and concentrated.

The resulting oil was purified by column chromatography (40% acetone / hexane) and generated the desired propargyl alcohol as a dark brown oil in 47% yield: R; 0.15 (40:60 acetone / hexane); IR (cm): 3423, 3309, 2979, 1595, 1524, 1492, 1115, 985; * H NMR (250 MHz, CsDs): 8 1.10 (d, J = 7.5 Hz, 12H), 2.29 (s, 1H), 2.67 (s, 1H), 4.26 (qn , J = 6.7 Hz, 2H), 6.54 (t, J = 2.3 Hz, 1H), 7.11 (d, J = 2.5 Hz, 2H); * C NMR (63 MHz, CDs): 21.9 (4C), 69.8 (2C), 71.9, 75.7, 83.7, 103.6, 105.8 (2C), 145.2 , 159.8 (2C). Scheme 3: Synthesis of 1- (3,5-diisopropoxyphenyl) -1-perfluorphenylprop-2-in-1-01 (1) Ho. O. 2-slodopropane To nor ro "1) SOC, benzene K2CO3, DMF THF, HO 2) MEOMENH-HCI, du% e% r CH3Ch, 60% Yo À nine" boneinde. <"RA Fo ss" Nes F QE EE ooo sm o vv c YF "+ F 1

S . 54/59 (PPh3) CIRu (3-pentafluorfenyl-6,8-diisopropoxyinden-1-ylidene): (J): A 100 ml bottle was loaded with 1- (3,5 diisopropoxyphenyl), 1- (penfluorfenyl) -2-propin-1-0l (compound H, 503 mg, 1.2 mmol). THF (47 mL) was then added followed by Ru (PPh3) 3Cl2 (1.17 g, 1.2 mmol) and —acetyl chloride (ACCI) (86 µL in 0.86 mL THF). The reaction was refluxed for 1.5 hours after which all the solvent was removed under a stream of N, 7. The residue | it was suspended in 45 ml of isopropanol with vigorous stirring at 40ºC for 1 hour. The resulting suspension was filtered and washed three times with isoprop- | nol (20 mL each) and vacuum dried. The crude material was loaded onto a rapid column dissolved in 50% hexane / dichloromethane, and eluted with 100% dichloromethane. The solvent was removed in vacuo yielding 240 mg (23%) of the desired compound. Additional crude material was eluted with 1% and 2% Me-OH in dichloromethane. This material contained PPh3 and an unidentified decomposition product observed at 28.6 ppm in the ** P spectrum. The product was characterized by NMR spectrum (H, "ºC, and ** P). The results are: as follows:: 1H NMR (500 MHz, CD2Clb, 30ºC): õ = 6.0-7, 0 (m, 15H), 6.62 (s, 1H), 6.56 (d, J = 1 Hz, 1H), 6.50 (d, J = 1.5 Hz, 1H), 5.17 ( sept d, J = 2, 6 Hz, 1H), 4.61 (sept, J = 6 Hz, 1H), 1.75 (d, J = 6 Hz, 6H), 1.36 (d, J = 6 Hz, 6H ); ** F NMR (250 MHz, CD2Clh2, 30ºC): ô = -137.39 (d, J = 17.5Hz, 2F), -154.66 (t, J = 22.5Hz, 1F), - 162.6 (dt, J = 6.5, 22.5Hz, 2F);? P NMR (250 MHz, CD2Cl>, 30 ° C): δ = 63 ppm.

Scheme 4: Synthesis of (PPh3) CIRu (3-pentafluorfenyl-6,8-di-isopropoxyinden- 1-ylidene) (J) o e: ei PP E EF

TOO OX F F AcCl, THE Y (CD FX o | F 18 h, reflux S: DA: CRU (PPh3) s 95 '

| S . 55/59 Example 3: Synthesis of (PCy3) Cl2Ru (3-pentafluorfenyl-6,8-diisopropoxyinden- '1-ylidene) (K) (PCy3) ClRu (3-pentafluorfenyl-6,8-di-isopropoxyinden- 1-ylidene) (K): A 10 ml vial was loaded with (PPh3) ClaRu (3-pentafluorfenyl-6,8-diisopropoxyinden-1-ylidene) (compound J, 0.40 grams). Benzene (2 mL) | was then added followed by tricyclohexylphosphine (0.13 gram). The reaction | was left to settle overnight. Excess Cu (l) CI was added, approximately 0.50 grams. The resulting slurry was dried in vacuo and penane was used to extract the product (0.038 g) from the solids. The product was characterized by NMR spectrum (H, Pe, and 'P). The results are as follows: * H NMR (250 MHz, CD2Cl2, 30ºC): d = 7.35 (s, 1H), 6.64 (s, 1H), 6.38 (s, 1H), 4, 62 (sept, 1H), 4.26 (sept, 1H), 1.72 (d, 6H), 1.36 (d, 6H), 1.5-2.4 (m, 33H); * F NMR (250 MHz, CD2Cb, 30ºC): õ = -137.34 (d, J = 17.5Hz, 2F), -154.4 (t, J = 22.5Hz, 1P), -161.6 (dt, J = 6.5, 22.5Hz, 2P); ** P NMR (250 MHz, CD2Cl2, 30 ° C): 5 = 68 ppm. : Scheme 5: Synthesis of (PCy3) Cl; Ru (3-pentafluorfenyl-6,8-di-isopropoxyin-. Den-1-ylidene) (K) ht <A PCys, CsH af RN cr ”O Ç) F Ya , CeHe crf o> F Yº (RX Cu (nel Y (> fx

RO X-Ray Crystallography X-ray quality crystals of these ruthenium complexes can grow by dissolving the crude material in a minimal amount of a solvent such as dichloromethane and then adding a different polarity excess, for example, isopropanol or hexanes. This solution is then allowed to evaporate at room temperature, usually in a nitrogen atmosphere, to generate crystals of the desired ruthenium complex. The crystals are usually removed from the solvent using a glass frit. Any solid isolated from the filtrate usually contains crystals

S . 56/59 impure. 'For example, X-ray quality crystals of compound J, above, were grown by dissolving the crude material in a minimal amount of dichloromethane and adding ten times the excess of isoprop- | —Nol.

This solution was allowed to partially evaporate overnight at 1 room temperature under an atmosphere of N, to generate quality crystals. X-ray quality.

Structure of Compound J solid state [(PPh3) Cl-Ru (3-pentafluorfenyl-6,8-di-isopropoxyinden-1-ylidene)] as determined by single decrystal X-ray diffraction Collection parameters and key data: RuC39H32PCI202F5s , FW 830.62, irregular red-brown, 0.6 x 0.3 x 0.06 mm, orthorhombic, a = 13.268 (1) A, b = 20.385 (2) A, c = 27.051 (3) A, V = 7316 (1) A ?, Pbca (É61), Z 2 = 8, deac = 1.508, mu = 6.77 in ”, Obs Obs = 8342, No.

Variables = 452, R1 (1> 20 ())) = 0.115, wR2 (all reflections) = 0.1826, GOF = 1.137, peak =] 0.61, hole = -0.49, max displacement / error = 0.001. . Atomic coordinates and Biso / Beg and 57/59 |

S . 58/59 [Rem] x [o [| = [| | |

Where Beq = 8/3 n2 (U11 (aa ") 2 + Uza (bb") 2 + Uga (cc ") 2 + 2U12 (aa * bb *) cos y + 2U13 (aa * cc *) cos B + 2U23 (bb * cc *) cos a). Cross metathesis reactions Representative experimental protocols for cross metathesis reactions are represented in the examples below. - Example 4: Ethylenolysis of methyl oleate with ethylene using compound D [triphenylphosphinorutene (3- (3,5-dimethoxyphenyl) -5,7-dimethoxy-indenylidene)]. In a 120 ml vial, triphenylphosphinoruthenium (3- (3,5-dimethoxyphenyl) -5,7-dimethoxy-indenylidene) (compound D, 5.0 mg, 6.57 umol) was combined with 100 ml dichloromethane to produce a stock solution.

Some of this stock solution of ruthenium catalyst compound (3.8 mL, 250 nmol) was added to a 20 mL scintillation flask along with 1 tricyclohexylphosphine equivalent (250 nmol, added as a dichloromethane solution). Tetradecan (0.152 g) was then added as a standard for gas chromatography analysis.

The contents of the flask were transferred to a 100 ml Fisher-Porter container equipped with a stir bar which was then closed and loaded with ethylene (150 psi). The bottle was then placed in an oil bath heated to 40ºC for 2 hours.

The bottle was depressurized, opened and a few drops (- 0.1 mL) of ethyl vinyl ether were added before analysis. 1-Decene and methyl-9-decenoate generates corresponding to 1800 decovers of decene per ruthenium equivalent.

| | i | Ss. 59/59 Example 5: Ethylenolysis of Methyl Oleate using Compound K, (PCy3) CLlRu (3- 'pentafluorfenyl-6,8-diisopropoxyinden-1-ylidene) Ethylenolysis of methyl oleate was used as a test to determine the activity of (PCy3) Cl2Ru (3-pentafluorfenyl-6,8-diisopropoxyinden-1lidene). A stock solution of catalyst compound (0.1379 mM) was prepared by dissolving the catalyst compound in anhydrous dichloromethane. | Methyl oleate (0.87 g, 1.0 mL), catalyst compound stock solution (0.906 g), dichloromethane (4.12 g), and tetradecane (0.152 g) as an internal standard were placed in a Fisher-Porter container equipped with a | 10 stirring bar. The container was then filled with ethylene at (150 psig) and placed in an oil bath at 40ºC for 3 hours. The vessel was then depressurized and 5 g of ethyl vinyl ether added to stop the reaction. One sample was analyzed by gas chromatography. The cross-metathesis reaction generated 18.5% 1-decene and methyl-9-decenoate with 99% selectivity 1-Decene and methyl-9-decenoate, corresponding to 4300 december turkeys per ruthenium equivalent.

'All documents described herein are incorporated by reference here, including any priority documents and / or extension testing procedures that are not inconsistent with this text, provided, however, that any priority documents not named in the initially filed order or archived documents is NOT incorporated as a reference here. As is apparent from the general description and the specific modalities, while forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. Thus, it is not intended that the invention be limited by it. Likewise, the term "comprising" is considered synonymous with the term "including" for the purposes of Australian law.

Claims (17)

EN 1/5 CLAIMS i 1. Metathesis catalyst compound characterized by the fact that it is represented by the formula: x q & NÉ pa Ss O R G: G G - where M is a Group 8 metal, preferably Ru; X and X 'are ligands — ionic; L is a neutral two-electron donor; L 'is N, O, P, or S, preferably N or O; R is a group C, at Ca9 hydrocarbyl or a group C, at C3o substituted hydrocarbyl; G * is selected from the group consisting of hi- | drogen, a group C, to C39 hydrocarbyl, and C, to substituted hydrocarbyl C39; R 'is selected from the group consisting of hydrogen, a C; Cao hydro carbyl, and C; the substituted hydrocarbyl C39; and G is independently selected from the group consisting of hydrogen, halogen, C, C39 hydrocarbyl and C; the substituted hydrocarbon chao, preferably the compound comprises one or more of: triphenylphosphinodichloretorutene (3- (3,5-dimethoxyphenyl) -6,8-dimethoxyinden-1-ylidene); triphenylphosphinodichloretorutene (3-pentafluorfenyl-6,8-diisopropoxyinden-1-ylidene); tricyclohexylphosphinodichloretorutene (3-penta-fluorophenyl-6,8-diisopropoxyinden-1-ylidene); or mixtures thereof. 2. Catalyst compound according to claim 1, characterized by the fact that X and X 'are, independently, a halogen, an alkoxide, aryloxide, or an alkyl sulfonate. Catalyst compound according to claim 1 or 2, characterized in that at least one of X and X 'is chloride, preferably both X and X' are chloride. "The 2/5 4. Catalyst compound, according to any of claims 1 to 3, characterized by the fact that L is selected from the group consisting of a phosphine, an N-heterocyclic carbene and a cyclic alkyl carbene amine. 5. Catalyst compound according to any of claims 1 to 4, characterized by the fact that G * is selected from the group consisting of hydrogen, an alkyl and substituted alkyl. 6. Catalyst compound, according to any one of claims 1 to 5, characterized by the fact that each G is independently a C ;; substituted or unsubstituted C39 alkyl, or a C, substituted or unsubstituted C3o aryl. 7. Catalyst compound, according to any one of claims 1 to 6, characterized by the fact that R 'is a methoxy substituted - by phenyl. . 8. Catalyst compound, according to any one of claims 1 to 7, characterized by the fact that L and X are joined to form a monoanionic multidentate group or a dianionic group and can form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms. Process for producing alpha-olefin, characterized in that it comprises contacting a feed material with the catalyst compound as defined in any one of claims 1 to 8, wherein the alpha olefin is preferably an alpha olefin linear having 4 to 24 carbon atoms, more preferably butene-1, decene-1 and / or heptene-1. 10. Process according to claim 9, characterized by the fact that the feed material is selected from the group consisting of canola oil, corn oil, soybean oil, rapeseed oil, seaweed oil, oil peanut oil, mustard oil, sunflower oil, tung oil, perilla oil, grape seed oil, linseed oil, safflower oil, pumpkin oil, palm oil, jatropha oil, soy oil rich in oleic oil, safflower oil rich in oleic oil, sunflower oil rich in oleic oil, mixtures of animal and vegetable fats and oils, castor bean oil, RB. oo 3/5 dehydrated castor bean, cucumber oil, poppy seed oil, oil: linseed oil, lesquerella oil, walnut oil, cottonseed oil, limante seed oil, tuna oil, sesame oils and mixtures thereof. 1 Process for producing the alpha-olefin of claim 9, characterized in that it comprises contacting a triacylglyceride with an alkene and the catalyst compound as defined in any of claims 1 to 8, preferably in which the alpha olefin is produced it has at least one carbon atom more than the alkene. 12. Process according to claim 11, characterized in that the triacylglyceride is contacted with alcohol and converted to a fatty acid ester or alkyl fatty acid ester before contacting the alkene and the catalyst compound as defined in any one of claims 1 to 8; or wherein the triacylglyceride is contacted with water or an alkaline reagent and converted to a fatty acid before contacting the alkylene and the catalyst compound as defined in any of the kings. vindications 1 to 8. Process according to claim 9, characterized in that it comprises contacting an unsaturated fatty acid or an unsaturated fatty acid ester, preferably an unsaturated fatty acid alkyl ester, such as a fatty acid methyl ester, with an alkene and the catalyst compound as defined in any one of claims 1 to 8, preferably wherein the alpha olefin produced has at least one more carbon atom than the alkene. Process according to any one of claims 9 to 13, characterized in that the alkene is ethylene, propylene, butene, hexene or octene. 15. Process according to any one of claims 11 to 14, characterized in that the triacylglyceride, fatty acid, ester - fatty acid alkyl, fatty acid ester is derived from biodiesel. 16. Process according to any of claims 9 to 15, characterized by the fact that the process has one or more of the following | o | 4/5 following characteristics: Ú the process productivity is at least 200 g of linear alpha-olefin per mmol of catalyst per hour; the selectivity of the process is at least 20% by weight of al- | 5 linear fa-olefin based on the weight of the material leaving the reactor; the transformation number, defined as moles of alpha olefin formed per mole of catalyst, of the process is at least 10,000; the yield, when converting unsaturated fatty acids, unsaturated fatty acid esters, alkyl esters of unsaturated fatty acid or mixtures thereof, is 30% or more, preferably 60% or more, said yield being defined as moles of alpha olefin formed by mol of unsaturated fatty acids, esters of unsaturated fatty acid, alkyl esters of unsaturated fatty acid or mixtures thereof introduced in. reactor; the yield, when converting TAGs as represented in the * formula below, is 30% or more, said yield defined as the z moles of f alpha olefin formed divided by (moles of unsaturated Rº + moles of unsaturated Rº + moles of unsaturated Rº ) introduced into the reactor, HC —O— & - R? [ll Hc —o — d— Rr | o HC— O - & - Rº where Rº, Rº and Rº each, independently, represents a chain of saturated or unsaturated hydrocarbons. 17. Process according to any one of claims 1 to 16, characterized in that it is to produce linear alpha olefin Ca to C24, The process comprising contacting a feed material with an alkene selected from the group consisting of ethylene, propylene butene, penny, hexene, heptene, octene, nonene and mixtures thereof and a compound . ) 1 . 5/5 metathesis catalyst post as defined in any one of claims 1 to 8, wherein the feed material is a triacylglyceride, fatty acid, alkyl fatty acid ester, and / or fatty acid ester derived from seed, and preferably where the alkene is ethylene, the alpha olefin is 1-: —butene, 1-heptene and / or -decene, and the feed material is a methyl ester of fatty acid and / or ester of fatty acid. FZ RD o: Pa, 11 FIGURE 1 and PR A c15s 2 Í | Cc5 cs Re NE ca Cc14? Nest c16 c7 MW C13 Ox t c17 Sa E nF F4 F3 bi c18 F5 c32 Ss c31 c20 c33: c12 ERA Rui o & CO O c30 F2 N cu1 <c21 c28 (NS c29 FL Ç23 - $ c22 c37 O oO c24 c27 c38 S c26 | c39 c25 o2 c34 DD c35; c36