WO2008060383A2 - Methods of making organic acid and organic aldehyde compounds by metathesis - Google Patents

Abstract

The invention is directed to methods of making organic compounds (e.g., organic acid or aldehyde compounds) by metathesis followed by oxidation and either oxidative or reductive cleavage. The methods may be used to make certain industrially important organic acid compounds, for example, azelaic acid. The methods of the invention make use of a cross-metathesis step with a short-chain olefin to chemically modify the starting composition in order to produce a functionalized alkene intermediate that has a pre-determined carbon-carbon double bond position. Upon separation of the functionalized alkene intermediate from the other cross-metathesis products, it is oxidized and then may be oxidatively cleaved to form an organic acid or reductively cleaved to form an aldehyde.

Description

METHODS OF MAKING ORGANIC ACID AND ORGANIC ALDEHYDE COMPOUNDS BY METATHESIS

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application having Serial No. 60/851 ,364, filed October 13, 2006, and entitled METHODS OF MAKING ORGANIC ACID AND ORGANIC ALDEHYDE COMPOUNDS BY METATHESIS, the disclosure of which is incorporated herein by reference. BACKGROUND

Azelaic acid (HOOC(CH₂)₇COOH) has traditionally been manufactured via the ozonolysis of oleic acid. This process oxidatively cleaves the carbon-carbon double bond that is present between the 9^th and 10^th carbons in oleic acid, resulting in the formation of azelaic acid and the co-product pelargonic acid. The simplified reaction scheme is shown below.

Oleic Acid + Ozone/Oxygen — ► Azelaic Acid + Pelargonic Acid

CH₃(CH₂)₇CH=CH(CH₂)₇COOH + O₃/O₂→ HOOC(CH₂)₇COOH + CH₃(CH₂)₇COOH

Typically, the source of oleic acid for the above process is beef tallow. As a starting composition, however, oleic acid that is sourced from beef tallow is typically contaminated with positional isomers of oleic acid that do not have a carbon-carbon double bond between the 9^th and 10^th carbons. When subjected to ozonolysis, these positional isomers produce organic acids other than azelaic acid or pelargonic acid. This results in a loss of purity of the azelaic acid as well as a loss of efficiency of the overall process.

Oleic acid, when derived from either animal fat or vegetable oil, typically contains some residual stearic acid. Azelaic acid, once produced, must be separated from the stearic acid that entered the process with the feedstock. Due to the similarity in volatility of these two acids, they cannot be readily separated by conventional distillation. Rather, azelaic acid and stearic acid are typically separated using a hot water extraction process followed by crystallization. While this process effectively separates azelaic acid from stearic acid, the separation efficiency is low, leading to a loss in the overall yield of azelaic acid from the process. As an alternative to beef tallow, vegetable oil may be used as a source of oleic acid. Many vegetable oils, however, contain significant amounts of polyunsaturated fatty acids (e.g., glycerides of linoleic and linolenic acid). When subjected to ozonolysis, these polyunsaturated species consume a significantly larger amount of ozone than oleic acid and also produce unwanted short-chain organic by- products other than pelargonic acid.

The source material impurities and separation challenges that are present in the above-described process make it difficult to readily provide a commercial azelaic acid product having a high purity. When using oleic acid derived from beef tallow, it is difficult to make a final product with a purity greater than about 89% azelaic acid by weight. For example, the product specification of commercially available azelaic acid typically specifies that it contains up to about 4% wt. impurities with a chain length of less than C9 and up to about 7% wt. impurities with a chain length of C9 or greater. Although this purity level may be acceptable for many applications, certain applications such as polyesters and polyamides (e.g., crystalline polyamides) may benefit from a high purity azelaic acid.

In view of the foregoing, what is desired is an improved process for the production of azelaic acid that overcomes one or more of the deficiencies present in the current process.

SUMMARY The invention is directed to methods of making organic compounds (e.g., organic acid or aldehyde compounds) by metathesis followed by oxidation and either oxidative or reductive cleavage. The methods may be used to make certain industrially important organic acid compounds, for example, azelaic acid. Advantageously, the methods of the invention make use of a cross-metathesis step with a short-chain olefin to chemically modify the starting composition in order to produce a functionalized alkene intermediate that has a pre-determined carbon- carbon double bond position. Upon separation of the functionalized alkene intermediate from the other cross-metathesis products, it is oxidized and then may be oxidatively cleaved to form an organic acid or reductively cleaved to form an aldehyde.

The cross-metathesis step allows the use of starting compositions that contain multiple unsaturated species (e.g., including polyunsaturated species) to produce the desired organic compounds. Accordingly, starting compositions comprising multiple unsaturated species may be used in the method without prior purification. In addition, due to the nature of the cross-metathesis products, the functional ized alkene intermediate can be readily isolated at high purity levels from the olefin co-products using conventional separation methods. Upon cleavage of the carbon-carbon double bond, the functionalized alkene intermediate forms an organic acid product (e.g., azelaic acid) or an organic aldehyde product.

In one aspect, the invention provides a method of making organic acid compounds by metathesis, ozonolysis, and oxidative cleavage. The method comprises the steps of:

(a) providing a starting composition comprising an unsaturated fatty acid, an unsaturated fatty ester, a carboxylate salt of unsaturated fatty acid, or a mixture thereof;

(b) cross-metathesizing the starting composition of step (a) with a short- chain olefin in the presence of a metathesis catalyst to form cross-metathesis products comprising:

(i) an olefin compound; and

(ii) an acid-, ester-, or carboxylate salt- functional ized alkene having at least one double bond; (c) separating at least a portion of the acid-, ester-, or carboxylate salt- functionalized alkene from the cross-metathesis products; and

(d) oxidatively cleaving the double bond of the acid-, ester, or carboxylate salt-functionalized alkene to form:

(i) a first organic acid having the structure X-(CH₂)_n-COOH where X is an ester group, a carboxylic acid group, or a carboxylate salt; and n is 3 to 1 1 ; and - A -

(ii) a second organic acid.

In another aspect, the invention provides a method of making organic aldehyde compounds by metathesis, ozonolysis, and reductive cleavage. The method comprising the steps of: (a) providing a starting composition comprising an unsaturated fatty acid, an unsaturated fatty ester, a carboxylate salt of unsaturated fatty acid, or a mixture thereof;

(b) cross-metathesizing the starting composition of step (a) with a short- chain olefin in the presence of a metathesis catalyst to form cross-metathesis products comprising:

(i) one or more olefin compounds; and (ii) one or more acid-, ester-, or carboxylate salt-functional ized alkenes having at least one double bond;

(c) separating at least a portion of the one or more acid-, ester-, or carboxylate salt-functionalized alkene from the cross-metathesis products; and

(d) reacting the acid-, ester-, or carboxylate salt-functionalized alkene with ozone to form an ozonide; and

(e) reductively cleaving the ozonide to form:

(i) an organic aldehyde having the structure: X-(CH₂)_n-CHO where X is an ester group, a carboxylic acid group, or a carboxylate salt; and n is 3 to 1 1 ; and (ii) one or more co-product aldehyde compounds.

Useful starting compositions (see, step (a)) include unsaturated compounds (e.g., unsaturated fatty acids, unsaturated fatty esters, and carboxylate salts of unsaturated fatty acids). The unsaturated compounds may be derived from natural oils such as vegetable oils or animal fats. Useful vegetable oils include soybean oil, rapeseed oil, corn oil, sesame oil, cottonseed oil, sunflower oil, canola oil, safflower oil, palm oil, palm kernel oil, linseed oil, castor oil, olive oil, peanut oil, and mixtures thereof. Other natural oils include tall oil, fish oil, lard, tallow, and mixtures thereof. In some embodiments, the starting composition comprises an unsaturated fatty acid, ester, or carboxylate salt having the formula:

CH₃-(CH₂)_nl-[-(CH₂)_n3-CH=CH-]_x-(CH₂)_n2-COOR where: R is hydrogen (fatty acid), an aliphatic group (fatty ester), or a metal ion

(carboxylate salt); nl is an integer equal to or greater than 0 (typically 0 to 15; more typically 0, 3, or 6); n2 is an integer equal to or greater than 0 (typically 2 to 1 1 ; more typically 3, 4, 7, 9, or 1 1); n3 is an integer equal to or greater than 0 (typically 0 to 6; more typically 1); and x is an integer equal to or greater than 1 (typically 1 to 6, more typically 1 to

3). In some embodiments, the starting composition comprises an unsaturated polyol ester. The unsaturated polyol ester may have the formula:

R (O-Y)_n, (OH)_n (O-X)b

where R is an organic group having a valency of (n+m+b); m is an integer from 0 to (n+m+b- 1), typically 0 to 2; b is an integer from 1 to (n+m+b), typically 1 to 3; n is an integer from 0 to (n+m+b- 1), typically 0 to 2;

(n+m+b) is an integer that is 2 or greater; X is -(O)C-(CH₂)_n2-[-CH=CH-(CH₂)_n3-]_x-(CH₂)_nl-CH₃;

Y is -(O)C-R^';

R' is a straight or branched chain alkyl or alkenyl group; n 1 is an integer equal to or greater than 0 (typically 0 to 15; more typically 0, 3, or 6); n2 is an integer equal to or greater than 0 (typically 2 to 1 1 ; more typically 3, 4, 7, 9, or 1 1); n3 is an integer equal to or greater than 0 (typically 0 to 6; more typically 1); and x is an integer equal to or greater than 1 (typically 1 to 6, more typically 1 to 3).

In some embodiments, the unsaturated polyol ester comprises an unsaturated glyceride having the formula:

CH₂A-CHB-CH₂C

where -A; -B; and -C are selected from

-OH;

-O(O)C-(CH₂)_n2-[-CH=CH-(CH₂)_n3-]χ-(CH₂)_n,-CH₃; and -0(O)C-R'; with the proviso that at least one of -A, -B, or -C is -O(O)C-(CH₂)_n2-[-CH=CH-(CH₂)_n3-]_x-(CH₂)_{n I}-CH_3.

In the above formula:

R' is a straight or branched chain alkyl or alkenyl group; n 1 is an integer equal to or greater than O (typically O to 15; more typically O, 3, or 6); n2 is an integer equal to or greater than O (typically 2 to 1 1 ; more typically 3, 4, 7, 9, or 1 1); n3 is an integer equal to or greater than O (typically O to 6; more typically 1); and x is an integer equal to or greater than 1 (typically 1 to 6, more typically 1 to 3).

Useful starting compositions include Δ9 unsaturated fatty acids/esters/salts; Δ6 unsaturated fatty acids/esters/salts; Δ5 unsaturated fatty acids/esters/salts; Δl 1 unsaturated fatty acids/esters/salts; and Δ13 unsaturated fatty acids/esters/salts. Mixtures thereof may also be used. Examples of Δ9 unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, and mixtures thereof. Unsaturated glycerides comprising of Δ9 unsaturated fatty acids may be derived from soybean oil. In the methods of the invention, the starting composition is cross- metathesized (see, step (b)) with a short-chain olefin in the presence of a metathesis catalyst. In some embodiments, the short-chain olefin has the structure:

R⁷R⁸C=CR⁹R¹⁰ where R⁷, R⁸, R⁹, and R¹⁰ are each, independently, hydrogen or an organic group, with the proviso that at least one of R or R is an organic group. In many embodiments, the short-chain olefin is a short-chain internal olefin. For example, the short-chain internal olefin may have the structure:

R⁷R⁸C=CR⁹R¹⁰ where R⁷, R⁸, R⁹, and R¹⁰ are each, independently, hydrogen or an organic group, with the proviso that at least one of R⁷ or R⁸ is an organic group, and at least one of R⁹ or R¹⁰ is an organic group. Useful short-chain internal olefins may be symmetric or asymmetric. When symmetric, the short-chain internal olefin may have the structure: R⁷CH=CHR⁹ where R⁷ and R⁹ are the same organic group. Examples of symmetric short- chain internal olefins include 2-butene, 3-hexene, and 4-octene. Examples of asymmetric short-chain internal olefin include 2-pentene, 2-hexene, 2-heptene, 3- heptene, 2-octene, 3-octene, 2-nonene, 3-nonene, and 4-nonene. In some embodiments, the short-chain olefin is an α-olefin having the structure:

CH₂=CH-R¹⁰ where -R¹⁰ is an organic group. Examples of α-olefin include 1 -propene, 1 - butene, 1 -pentene, 1 -hexene, 1 -heptene, 1 -octene, and 1 -nonene.

After cross-metathesis, at least a portion of the acid-, ester-, or salt- functional ized alkene is separated from the other cross-metathesis products. Useful separation processes include distillation, reactive distillation, chromatography, fractional crystallization, membrane separation, liquid/liquid extraction, or a combination thereof.

After separation, in some embodiments, the carbon-carbon double bond of the separated acid-, ester, or salt-functionalized alkene is oxidatively cleaved to form (i) a first organic acid having the structure X-(CH₂)_n-COOH, where X is an ester group, a carboxylic acid group, or a carboxylate salt; and n is 3 to 1 1 ; and (ii) a second organic acid. Oxidative cleavage may be achieved, for example, using ozonolysis. Organic acids that may be manufactured using the method of the invention include, for example, azelaic acid, glutaric acid, adipic acid, or brassylic acid. In some embodiments, the separated acid-, ester-, or carboxylate salt- functionalized alkene is reacted with ozone to form an ozonide, and the ozonide is reductively cleaved to form an (i) an organic aldehyde having the structure: X- (CH₂)_n-CHO where X is an ester group, a carboxylic acid group, or a carboxylate salt; and n is 3 to 11; and (ii) one or more co-product aldehyde compounds. In some embodiments the diacid that is formed by the method of the invention has a high level of purity, for example, about 90% wt. or greater, about 95% wt. or greater, about 99% wt. or greater, or about 99.9% wt. or greater.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process flow diagram of an embodiment of the method of the invention.

FIGS. 2, 2A, and 2B are process flow diagrams of various embodiments of the methods of the invention.

FIG. 3 is a process flow diagram of an embodiment of the method of the invention. DETAILED DESCRIPTION

Starting Composition (Step (a)):

As a starting composition, the method of the present invention uses unsaturated fatty acids, unsaturated fatty esters, salts of unsaturated fatty acids, or a mixture. As used herein the term "unsaturated fatty acid" refers to compounds that have an alkene chain with a terminal carboxylic acid group. The alkene chain may be a linear or branched and may optionally include one or more functional groups in addition to the carboxylic acid group. For example, some carboxylic acids include one or more hydroxyl groups. The alkene chain typically contains about 4 to about 30 carbon atoms, more typically about 4 to about 22 carbon atoms. In many embodiments, the alkene chain contains 18 carbon atoms (i.e., a Cl 8 fatty acid). The unsaturated fatty acids have at least one carbon-carbon double bond in the alkene chain (i.e., a monounsaturated fatty acid), and may have more than one double bond (i.e., a polyunsaturated fatty acid) in the alkene chain. In exemplary embodiments, the unsaturated fatty acid has from 1 to 3 carbon-carbon double bonds in the alkene chain.

Also useful as starting compositions are unsaturated fatty esters. As used herein the term "unsaturated fatty ester" refers to a compounds that have an alkene chain with a terminal ester group. The alkene chain may be linear or branched and may optionally include one or more functional groups in addition to the ester group. For example, some unsaturated fatty esters include one or more hydroxyl groups in addition to the ester group. Unsaturated fatty esters include "unsaturated monoesters" and "unsaturated polyol esters". Unsaturated monoesters have an alkene chain that terminates in an ester group, for example, an alkyl ester group such as a methyl ester. The alkene chain of the unsaturated monoesters typically contains about 4 to about 30 carbon atoms, more typically about 4 to 22 carbon atoms. In exemplary embodiments, the alkene chain contains 18 carbon atoms (i.e., a Cl 8 fatty ester). The unsaturated monoesters have at least one carbon-carbon double bond in the alkene chain and may have more than one double bond in the alkene chain. In exemplary embodiments, the unsaturated fatty ester has 1 to 3 carbon- carbon double bonds in the alkene chain.

Also useful as a starting composition are metal salts of unsaturated fatty acids (i.e., carboxylate salts of unsaturated fatty acids). The metal salts may be salts of alkali metals (e.g., a group IA metal such as Li, Na, K, Rb, Cs, and Fr); alkaline earth metals (e.g., group HA metals such as Be, Mg, Ca, Sr, Ba, and Ra); group IHA metals (e.g., B, Al, Ga, In, and Tl); group IVA metals (e.g., Sn and Pb), group VA metals (e.g., Sb and Bi), transition metals (e.g., Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag and Cd), lanthanides or actinides.

In many embodiments, the unsaturated fatty acid, ester, or carboxylate salt has a straight alkene chain and can be represented by the general formula:

CH₃-(CH₂)_nl-[-(CH₂)_n3-CH=CH-]_x-(CH₂)_n2-COOR where:

R is hydrogen (fatty acid), an aliphatic group (fatty ester), or a metal ion (carboxylate salt); nl is an integer equal to or greater than 0 (typically 0 to 15; more typically 0,

3, or 6); n2 is an integer equal to or greater than 0 (typically 2 to 1 1 ; more typically 3,

4, 7, 9, or 1 1); n3 is an integer equal to or greater than 0 (typically 0 to 6; more typically 1); and x is an integer equal to or greater than 1 (typically 1 to 6, more typically 1 to

3).

A summary of some unsaturated fatty acids and esters is provided in TABLE

A.

TABLE A: Unsaturated Fatty Acids/Esters

Unsaturated monoesters may be alkyl esters (e.g., methyl esters) or aryl esters and may be derived from unsaturated fatty acids or unsaturated glycerides by transesterifying with a monohydric alcohol. The monohydric alcohol may be any monohydric alcohol that is capable of reacting with the unsaturated free fatty acid or unsaturated glyceride to form the corresponding unsaturated monoester. In some embodiments, the monohydric alcohol is a Cl to C20 monohydric alcohol, for example, a Cl to C 12 monohydric alcohol, a Cl to C8 monohydric alcohol, or a Cl to C4 monohydric alcohol. The carbon atoms of the monohydric alcohol may be arranged in a straight chain or in a branched chain structure, and may be substituted with one or more substituents. Representative examples of monohydric alcohols include methanol, ethanol, propanol (e.g., isopropanol), and butanol.

Transesterification of an unsaturated triglyceride can be represented as follows.

1 Unsaturated Triglyceride + 3 Alcohol — ► 1 Glycerol + 3 Monoesters

Depending upon the make-up of the unsaturated triglyceride, the above reaction may yield one, two, or three moles of unsaturated monoester. Transesterification is typically conducted in the presence of a catalyst, for example, alkali catalysts, acid catalysts, or enzymes. Representative alkali transesterification catalysts include NaOH, KOH, sodium and potassium alkoxides (e.g., sodium methoxide), sodium ethoxide, sodium propoxide, sodium butoxide. Representative acid catalysts include sulfuric acid, phosphoric acid, hydrochloric acid, and sulfonic acids. Heterogeneous catalysts may also be used for transesterification. These include alkaline earth metals or their salts such as CaO, MgO, calcium acetate, barium acetate, natural clays, zeolites, Sn, Ge or Pb, supported on various materials such as ZnO, MgO, TiO₂, activated carbon or graphite, and inorganic oxides such as alumina, silica-alumina, boria, oxides of P, Ti, Zr, Cr, Zn, Mg, Ca, and Fe. In exemplary embodiments, the triglyceride is transesterified with methanol (CH₃OH) in order to form free fatty acid methyl esters. In some embodiments, the unsaturated fatty esters are unsaturated polyol esters. As used herein the term "unsaturated polyol ester" refers to compounds that have at least one unsaturated fatty acid that is esterified to the hydroxyl group of a polyol. The other hydroxyl groups of the polyol may be unreacted, may be esterified with a saturated fatty acid, or may be esterified with an unsaturated fatty acid. The fatty acids in the polyol ester may be linear or branched and may optionally have functional groups other than the carboxylic acid such as one or more hydroxyl groups. Examples of polyols include glycerol, ethylene glycol, propylene glycol, 1 ,3-propanediol, trimethylolpropane, erythritol, pentaerythritol, and sorbitol. In many embodiments, unsaturated polyol esters have the general formula:

R (O-Y)_m (OH)_n (O-X)₁,

where R is an organic group having a valency of (n+m+b); m is an integer from 0 to (n+m+b- 1), typically 0 to 2; b is an integer from 1 to (n+m+b), typically 1 to 3; n is an integer from 0 to (n+m+b- 1), typically 0 to 2; (n+m+b) is an integer that is 2 or greater; X is -{O)C-(CH₂)_n2-[-CH-CH-(CH₂)_n3-]_x-(CH₂)_n,-CH₃;

Y iS -(O)C-R^';

R' is a straight or branched chain alkyl or alkenyl group; nl is an integer equal to or greater than 0 (typically 0 to 15; more typically 0, 3, or 6); n2 is an integer equal to or greater than 0 (typically 2 to 1 1 ; more typically 3, 4, 7, 9, or 1 1); n3 is an integer equal to or greater than 0 (typically 0 to 6; more typically 1); and x is an integer equal to or greater than 1 (typically 1 to 6, more typically 1 to 3). In many embodiments, the unsaturated polyol esters are unsaturated glycerides. As used herein the term "unsaturated glyceride" refers to a polyol ester having at least one (e.g., 1 to 3) unsaturated fatty acid that is esterified with a molecule of glycerol. The fatty acid groups may be linear or branched and may include pendant hydroxyl groups. In many embodiments, the unsaturated glycerides are represented by the general formula:

CH₂A-CHB-CH₂C

where -A; -B; and -C are selected from

-OH;

-O(O)C-(CH₂)_n2-[CH=CH-(CH₂)_n3-]_x-(CH₂)_n,-CH₃; and -0(O)C-R'; with the proviso that at least one of -A, -B, or -C is -O(O)C-(CH₂)_n2-[CH=CH-(CH₂)_π3-]_x-(CH₂)_nl-CH_3.

In the above formula:

R^' is a straight or branched chain alkyl or alkenyl group; n 1 is an integer equal to or greater than O (typically O to 15; more typically O, 3, or 6); n2 is an integer equal to or greater than O (typically 2 to 1 1 ; more typically 3, 4, 7, 9, or 1 1); n3 is an integer equal to or greater than 0 (typically 0 to 6; more typically 1); and x is an integer equal to or greater than 1 (typically 1 to 6, more typically 1 to 3).

Unsaturated glycerides having two -OH groups (e.g., -A and -B are -OH) are commonly known as unsaturated monoglycerides. Unsaturated glycerides having one -OH group are commonly known as unsaturated diglycerides. Unsaturated glycerides having no -OH groups are commonly known as unsaturated triglycerides. As shown in the formula above, the unsaturated glyceride may include monounsaturated fatty acids, polyunsaturated fatty acids, and saturated fatty acids that are esterified to the glycerol molecule. The main chain of the individual fatty acids may have the same or different chain lengths. Accordingly, the unsaturated glyceride may contain up to three different fatty acids so long as at least one fatty acid is an unsaturated fatty acid.

In many embodiments, useful starting compositions are derived from natural oils such as plant-based oils or animal fats. Representative examples of plant-based oils include canola oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil, castor oil, and the like. Representative examples of animal fats include lard, tallow, chicken fat (yellow grease), and fish oil. Tall oil and algae oil may also be used.

In many embodiments, the plant-based oil is soybean oil. Soybean oil comprises unsaturated glycerides, for example, in many embodiments about 95% weight or greater (e.g., 99% weight or greater) triglycerides. Major fatty acids making up soybean oil include saturated fatty acids, for example, palmitic acid (hexadecanoic acid) and stearic acid (octadecanoic acid), and unsaturated fatty acids, for example, oleic acid (9-octadecenoic acid), linoleic acid (9, 12-octadecadienoic acid), and linolenic acid (9,12,15-octadecatrienoic acid). Soybean oil is a highly unsaturated vegetable oil with many of the triglyceride molecules having at least two unsaturated fatty acids.

The method of the invention can be used to produce multiple organic acid compounds. As discussed below, the position of the carbon-carbon double bond closest to the carboxylic acid, ester, or carboxylate salt group dictates the chain length of the organic acid compound that is formed by the method of the invention. Δ9 Starting Compositions

In many embodiments, the starting composition comprises a Δ9 unsaturated fatty acid, a Δ9 unsaturated fatty ester (e.g., monoesters or polyol esters), a Δ9 unsaturated fatty acid salt, or a mixture of two or more of the foregoing. Δ9 unsaturated starting materials have a carbon-carbon double bond located between the 9^th and 10^th carbon atoms (i.e., between C9 and ClO) in the alkene chain of the unsaturated fatty acid, ester, or salt. In determining this position, the alkene chain is numbered beginning with the carbon atom in the carbonyl group of the unsaturated fatty acid, ester, or salt. Δ9 unsaturated fatty acids, esters, and salts include polyunsaturated fatty acids, esters, or salts (i.e., having more than one carbon-carbon double bond in the alkene chain) so long as one of the carbon-carbon double bonds is located between C9 and ClO. For example, included within the definition of Δ9 unsaturated fatty acids, esters, or salts are Δ9, 12 unsaturated fatty acids, esters or salts, and Δ9, 12, 15 unsaturated fatty acids, esters or salts.

In many embodiments, the Δ9 unsaturated starting materials have a straight alkene chain and may be represented by the general structure:

CH₃-(CH₂)_{n l}-[(CH₂)_n3-CH=CH]_x-(CH₂)₇-COOR where

R is hydrogen (fatty acid), an aliphatic group (fatty monoester) or a metal ion (carboxylate salt); nl is an integer equal to or greater than 0 (typically 0 to 6; more typically 0, 3, 6); n3 is an integer equal to or greater than 0 (typically 1); and x is an integer equal to or greater than 1 (typically 1 to 6, more typically 1 to 3).

In exemplary embodiments, the Δ9 unsaturated starting materials have a total of 18 carbons in the alkene chain. Examples include

CH₃-(CH₂)₇-CH=CH-(CH₂)₇-COOR;

CH₃-(CH₂^-CH=CH-CH₂-CH=CH-(CH₂)_T-COOR; and CH₃-CH₂-CH=CH-CH₂-CH=CH-CH₂-CH=CH-(CH₂)₇-COOR.

where R is hydrogen (fatty acid), an aliphatic group (fatty monoester) i or a metal ion (fatty acid salt); Δ9 unsaturated fatty esters may be monoesters or polyol esters. In many embodiments, the Δ9 unsaturated polyol esters have the general structure

CH₂A-CHB-CH₂C

where -A; -B; and -C are independently selected from -OH;

-0(O)C-R'; and

-O(O)C-(CH₂)₇-[-CH=CH-(CH₂)_n3-]_x--(CH₂)_nl-CH₃; with the proviso that at least one of -A, -B, or -C is

-O(O)C-(CH₂)₇-[-CH=CH-(CH₂)_n3-]_x.-(CH₂)_{n l}-CH₃. In the above formula:

R^' is a straight or branched chain alkyl or alkenyl group; nl is an integer equal to or greater than O (typically O to 6; more typically O, 3, 6); n3 is an integer equal to or greater than O (typically 1); and x is an integer equal to or greater than 1 (typically 1 to 6, more typically 1 to 3).

In exemplary embodiments, the starting composition comprises one or more

Cl 8 fatty acids, for example, oleic acid (i.e., 9-octadecenoic acid), linoleic acid (i.e., 9, 12-octadecadienoic acid), and linolenic acid (i.e., 9, 12, 15-octadecatrienoic acid). In other exemplary embodiments, the starting composition comprises one or more Cl 8 fatty esters, for example, methyl oleate, methyl linoleate, and methyl linolenate. In yet another exemplary embodiment, the starting composition comprises an unsaturated glyceride comprising Δ9 fatty acids, for example, Cl 8 Δ9 fatty acids. Δ9 starting compositions may be derived, for example, from vegetable oils such as soybean oil, rapeseed oil, corn oil, sesame oil, cottonseed oil, sunflower oil, canola oil, safflower oil, palm oil, palm kernel oil, linseed oil, castor oil, olive oil, peanut oil, and the like. Since these vegetable oils yield predominately in glyceride form, the oils are typically processed (e.g., by transesterification) to yield unsaturated free fatty esters, unsaturated free fatty acids, or carboxylate salts thereof. Δ9 starting materials may also be derived from tung oil which typically contains oleic acid, linoleic acid, and elostearic acid (C 18; Δ9, 1 1, 13) in glyceride form. Δ9 starting materials may also be derived from tall oil, fish oil, lard, and tallow. Δ5 Starting Compositions Also useful as a starting composition in the methods of the present invention are Δ5 unsaturated fatty acids, esters, or carboxylate salts. As used herein "Δ5" refers to unsaturated fatty acids, esters, or carboxylate salts having a carbon-carbon double bond located between the 5th and 6th carbon atom in the alkene chain of the unsaturated fatty acid, ester, or salt. In some embodiments, Δ5 unsaturated fatty acids, esters, and carboxylate salts have the general structure:

CH₃-(CH₂)_{n l}-[(CH₂)_n3-CH=CH]_x-(CH₂)₃-COOR where

R is hydrogen (fatty acid), an aliphatic group (fatty monoester) or a metal ion (carboxylate salt); nl is an integer equal to or greater than 0 (typically 0 to 15; more typically 0, 3, or 6); n3 is an integer equal to or greater than 0 (typically 0 to 6; more typically 1); and x is an integer equal to or greater than 1 (typically 1 to 6, more typically 1 to 3).

The Δ5 unsaturated fatty esters may be monoesters or polyol esters (e.g., unsaturated glycerides). In many embodiments, the Δ5 unsaturated polyol esters have the general structure: CH₂A-CHB-CH₂C

where -A; -B; and -C are independently selected from

-OH;

-0(O)C-R'; and -O(O)C-(CH₂)₃-[-CH=CH-(CH₂)_π3-]_x-(CH₂)_nl-CH₃; with the proviso that at least one of -A, -B, or -C is

-O(O)C-(CH₂)₃-[-CH=CH-(CH₂)_n3-]_x-(CH₂)_n,-CH₃; In the above formula:

R' is a straight or branched chain alkyl or alkenyl group; n 1 is an integer equal to or greater than 0 (typically 0 to 15; more typically 0, 3, or 6); n3 is an integer equal to or greater than 0 (typically 0 to 6; more typically 1); and x is an integer equal to or greater than 1 (typically 1 to 6, more typically 1 to 3).

Δ5 starting compositions may be derived, for example, from meadowfoam oil which contains a twenty carbon (C20) monounsaturated Δ5 unsaturated fatty acid (C20: 1 ; Δ5) in glyceride form. Δ6 Starting Compositions

Also useful as a starting composition in the methods of the present invention are Δ6 unsaturated fatty acids, esters, or salts. As used herein "Δ6" refers to unsaturated fatty acids, esters, or salts having a carbon-carbon double bond located between the 6th and 7th carbon atom in the alkene chain of the unsaturated fatty acid, ester, or salt. In some embodiments, Δ6 unsaturated fatty acids, esters, and salts have the general structure:

CH₃-(CH₂)ni-[-(CH₂)_n3-CH=CH]_x-(CH₂)₄-COOR where

R is hydrogen (fatty acid), an aliphatic group (fatty monoester) or a metal ion (carboxylate salt); nl is an integer equal to or greater than 0 (typically 0 to 10); n3 is an integer equal to or greater than 0; (typically 0); and x is an integer equal to or greater than 1 (typically 1 to 6, more typically 1).

The Δ6 unsaturated fatty esters may be monoesters or polyol esters (e.g., unsaturated glycerides). In many embodiments, the Δ6 unsaturated polyol esters have the general structure:

CH₂A-CHB-CH₂C where -A; -B; and -C are independently selected from -OH;

-0(O)C-R'; and -O(O)C-(CH₂)₄-[-CH=CH-(CH₂)_n3-]_x-(CH₂)_nl-CH₃; with the proviso that at least one of -A, -B, or -C is

-O(O)C-(CH₂)₄-[-CH=CH-(CH₂)_n3-]_x-(CH₂)_nl-CH₃. In the above formula:

R' is a straight or branched chain alkyl or alkenyl group; n 1 is an integer equal to or greater than O (typically O to 10); n3 is an integer equal to or greater than O; (typically 0); and x is an integer equal to or greater than 1 (typically 1 to 6, more typically 1).

Δ6 starting compositions may be derived from coriander oil which contains an 18 carbon unsaturated fatty acid (C 18: 1 ; Δ6) in glyceride form. Al 1 Starting Compositions

Also useful as a starting composition in the methods of the present invention are Δl 1 unsaturated fatty acids, esters, or salts. As used herein "Δl 1" refers to unsaturated fatty acids, esters, or salts having a carbon-carbon double bond located between the 1 1^th and 12^th carbon atom in the alkene chain of the unsaturated fatty acid, ester, or salt. In some embodiments, Δl 1 unsaturated fatty acids, esters, and salts have the general structure:

CH₃-(CH₂)_nl-[(CH₂)_n3-CH=CH]_x-(CH₂)₉-COOR where

R is hydrogen (fatty acid), an aliphatic group (fatty monoester) or a metal ion (carboxylate salt); nl is an integer equal to or greater than 0 (typically 0 to 7; more typically 7); n3 is an integer equal to or greater than 0 (typically 0); and x is an integer equal to or greater than 1 (typically 1 to 6, more typically 1). The Δl 1 unsaturated fatty esters may be monoesters or polyol esters (e.g., unsaturated glycerides). In many embodiments, the Δl 1 unsaturated polyol esters have the general structure: CH₂A-CHB-CH₂C where -A; -B; and -C are independently selected from -OH;

-0(O)C-R'; and

-O(O)C-(CH₂)₉-[-CH=CH-(CH₂)_n3]_x-(CH₂)_{n l}CH₃; with the proviso that at least one of -A, -B, or -C is

-O(O)C-(CH₂)₉-[-CH=CH-(CH₂)_n3]_x-(CH₂)_nlCH₃. In the above formula:

R' is a straight or branched chain alkyl or alkenyl group; nl is an integer equal to or greater than O (typically O to 7; more typically 7); n3 is an integer equal to or greater than O (typically O); and x is an integer equal to or greater than 1 (typically 1 to 6, more typically 1).

Sources of Δl 1 starting compositions include camelina oil which contains gondoic acid (C20: l Δl 1) at approximately 15% of the fatty acid composition. Al 3 Starting Compositions

Also useful as a starting composition in the methods of the present invention are Δ 13 unsaturated fatty acids, esters, or salts. As used herein "Δ13" refers to unsaturated fatty acids, esters, or salts having a carbon-carbon double bond located between the 13^th and 14^th carbon atom in the alkene chain of the unsaturated fatty acid, ester, or salt. In some embodiments, Δ13 unsaturated fatty acids, esters, and salts have the general structure:

CH₃-(CH₂)_nl-[-(CH₂)_n3-CH=CH]_x-(CH₂)π-COOR where

R is hydrogen (fatty acid), an aliphatic group (fatty monoester) or a metal ion (carboxylate salt); nl is an integer equal to or greater than 0 (typically 7); n3 is an integer equal to or greater than 0 (typically 0) x is an integer equal to or greater than 1 (typically 1 to 6, more typically 1). The Δl 3 unsaturated fatty esters may be monoesters or polyol esters (e.g., unsaturated glycerides). In many embodiments, the Δ13 unsaturated polyol esters have the general structure

CH₂A-CHB-CH₂C where -A; -B; and -C are independently selected from

-OH;

-0(O)C-R'; and

-0(O)C-(CH₂), ,-[-CH=CH-(CH₂)_n3-]_x-(CH₂)_nl-CH_{3 ;} with the proviso that at least one of -A, -B, or -C is -0(O)C-(CH₂), ,-[-CH=CH-(CH₂)_n3-]_x-(CH₂)_n,-CH₃.

In the above formula:

R^' is a straight or branched chain alkyl or alkenyl group; nl is an integer equal to or greater than O (typically 7); n3 is an integer equal to or greater than O (typically O) x is an integer equal to or greater than 1 (typically 1 to 6, more typically 1).

Sources of Δ 13 starting compositions include crambe oil, fish oil, and high erucic acid rapeseed oil which are high in erucic acid (C22: l Δ13) in glyceride form.

Other useful starting compositions include, for example, Δ8 and Δ4 starting materials. Δ4 starting materials may be obtained, for example, from fish oil which typically includes an amount of docosahexaenoic acid (C22:6; Δ4, 7, 10, 13, 16, 19). Δ8 starting materials may also be obtained from fish oil which typically includes an amount of eicosatetraenoic acid (C20:4; Δ8, 1 1, 14, 17).

A summary of some useful starting compositions is provided in TABLE B. TABLE B

Cross-Metathesis (Step (bϊ):

According to the method of the invention, the starting composition is cross- metathesized with a short-chain olefin in the presence of a metathesis catalyst to form cross-metathesis products comprising: (i) one or more olefin compounds; and (ii) one or more acid-, ester-, or carboxylate salt-functionalized alkenes having at least one carbon-carbon double bond.

Short-chain olefins are short chain length organic compounds that have at least one carbon-carbon double bond. In many embodiments, the short chain olefins have between about 3 and about 9 carbon atoms. Short chain olefins can be represented by the structure (II): R⁷R⁸C=CR⁹R¹⁰ (H)

where R⁷, R⁸, R⁹, and R¹⁰ are each, independently, hydrogen or an organic group, with the proviso that at least one of of R or R is an organic group.

The organic group may be an aliphatic group, an alicyclic group, or an aromatic group. Organic groups may optionally include heteroatoms (e.g., O, N, or S atoms), as well as functional groups (e.g., carbonyl groups). The term aliphatic group means a saturated or unsaturated, linear or branched, hydrocarbon group. This term is used to encompass alkyl groups. The term alkyl group means a monovalent, saturated, linear, branched, or cyclic hydrocarbon group. Representative examples include of alkyl groups include methyl, ethyl, propyl (n-propyl or i-propyl), butyl (n- butyl or t-butyl), pentyl, hexyl, and heptyl. An alicyclic group is an aliphatic group arranged in one or more closed ring structures. The term is used to encompass saturated (i.e., cycloparaffϊns) or unsaturated (cycloolefins or cycloacetylenes) groups. An aromatic or aryl group is an unsaturated cyclic hydrocarbon having a conjugated ring structure. Included within aromatic or aryl groups are those possessing both an aromatic ring structure and an aliphatic or alicyclic group. In many embodiments, the short-chain olefin is a short-chain internal olefin.

Short-chain internal olefins may be represented by structure (II):

R⁷R⁸C=CR⁹R¹⁰

(II) where R⁷, R⁸, R⁹, and R¹⁰ are each, independently, hydrogen or an organic group, with the proviso that at least one of R⁷ or R⁸ is an organic group, and at least one of R⁹ or R¹⁰ is an organic group.

Short-chain internal olefins may be symmetric or asymmetric. Symmetric short-chain internal olefins having one carbon-carbon double bond may be represented by structure (H-A): R⁷CH=CHR⁹

(H-A) where -R⁷ and -R⁹ are same organic group.

Representative examples of symmetric short-chain internal olefins include 2- butene, 3-hexene, and 4-octene. In some embodiments, the short-chain internal olefin is asymmetric. Representative examples of asymmetric short-chain internal olefins include 2-pentene, 2-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, 2- nonene, 3-nonene, and 4-nonene. In many embodiments, symmetric short-chain internal olefins are preferred for cross-metathesis because the cross-metathesis products that result will include fewer products than if an asymmetric short-chain internal olefin is used for cross- metathesis. For example, as shown below, when a first double-bond containing compound (i.e., A=B) is cross-metathesized with a symmetric short-chain internal olefin (i.e., represented by C=C), two cross-metathesis products are produced. By contrast, when the same double-bond containing compound is cross-metathesized with an asymmetric short-chain internal olefin (i.e., represented by C=D), four cross-metathesis products are produced.

Metathesis of Symmetric Short-chain Internal Olefin (C=C)

A=B + C=C <→ A=C + B=C

Metathesis of Asymmetric Short-chain Internal Olefin (C=D):

A=B + C=D o A=C + B=C + A=D + B=D

In some embodiments, the short-chain olefin is an α-olefin. Alpha olefins are included in general structure (II) when R⁷, R⁸, and R⁹ are all hydrogen. Representative α-olefin are shown in general structure (H-B):

CH₂=CH-R¹⁰

(H-B) where -R¹⁰ is an organic group. Representative -R¹⁰ groups include -{CH₂)_n-CH₃, where n ranges from 0 to 6. Exemplary alpha olefin compounds include 1-propene, 1-butene, 1-pentene, 1 - hexene, 1-heptene, 1 -octene, and 1-nonene. Metathesis Catalysts:

The metathesis reaction is conducted in the presence of a catalytically effective amount of a metathesis catalyst. The term "metathesis catalyst" includes any catalyst or catalyst system which catalyzes the metathesis reaction.

Any known or future-developed metathesis catalyst may be used, alone or in combination with one or more additional catalysts. Exemplary metathesis catalysts include metal carbene catalysts based upon transition metals, for example, ruthenium, molybdenum, osmium, chromium, rhenium, and tungsten. Exemplary ruthenium-based metathesis catalysts include those represented by structures 12 (commonly known as Grubbs's catalyst), 14 and 16, where Ph is phenyl, Mes is mesityl, and Cy is cyclohexyl.

12 14 16

Structures 18, 20, 22, 24, 26, and 28, illustrated below, represent additional ruthenium-based metathesis catalysts, where Ph is phenyl, Mes is mesityl, py is pyridine, Cp is cyclopentyl, and Cy is cyclohexyl. Techniques for using catalysts 12, 14, 16, 18, 20, 22, 24, 26, and 28, as well as additional related metathesis catalysts, are known in the art.

18 20 22

Catalysts C627, C682, C697, C712, and C827 are additional ruthenium- based catalysts, where Cy is cyclohexyl in C827.

C627

C712

C697 C682

Additional exemplary metathesis catalysts include, without limitation, metal carbene complexes selected from the group consisting of molybdenum, osmium, chromium, rhenium, and tungsten. The term "complex" refers to a metal atom, such as a transition metal atom, with at least one ligand or complexing agent coordinated or bound thereto. Such a ligand typically is a Lewis base in metal carbene complexes useful for alkyne or alkene-metathesis. Typical examples of such ligands include phosphines, halides and stabilized carbenes. Some metathesis catalysts may employ plural metals or metal co-catalysts (e.g., a catalyst comprising a tungsten halide, a tetraalkyl tin compound, and an organoaluminum compound).

An immobilized catalyst can be used for the metathesis process. An immobilized catalyst is a system comprising a catalyst and a support, the catalyst associated with the support. Exemplary associations between the catalyst and the support may occur by way of chemical bonds or weak interactions (e.g. hydrogen bonds, donor acceptor interactions) between the catalyst, or any portions thereof, and the support or any portions thereof. Support is intended to include any material suitable to support the catalyst. Typically, immobilized catalysts are solid phase catalysts that act on liquid or gas phase reactants and products. Exemplary supports are polymers, silica or alumina. Such an immobilized catalyst may be used in a flow process. An immobilized catalyst can simplify purification of products and recovery of the catalyst so that recycling the catalyst may be more convenient.

The metathesis process can be conducted under any conditions adequate to produce the desired metathesis products. For example, stoichiometry, atmosphere, solvent, temperature and pressure can be selected to produce a desired product and to minimize undesirable byproducts. The metathesis process may be conducted under an inert atmosphere. Similarly, if the olefin reagent is supplied as a gas, an inert gaseous diluent can be used. The inert atmosphere or inert gaseous diluent typically is an inert gas, meaning that the gas does not interact with the metathesis catalyst to substantially impede catalysis. For example, particular inert gases are selected from the group consisting of helium, neon, argon, nitrogen and combinations thereof.

Similarly, if a solvent is used, the solvent chosen may be selected to be substantially inert with respect to the metathesis catalyst. For example, substantially inert solvents include, without limitation, aromatic hydrocarbons, such as benzene, toluene, xylenes, etc.; halogenated aromatic hydrocarbons, such as chlorobenzene and dichlorobenzene; aliphatic solvents, including pentane, hexane, heptane, cyclohexane, etc.; and chlorinated alkanes, such as dichloromethane, chloroform, dichloroethane, etc.

In certain embodiments, a ligand may be added to the metathesis reaction mixture. In many embodiments using a ligand, the ligand is selected to be a molecule that stabilizes the catalyst, and may thus provide an increased turnover number for the catalyst. In some cases the ligand can alter reaction selectivity and product distribution. Examples of ligands that can be used include Lewis base ligands, such as, without limitation, trialkylphosphines, for example tricyclohexylphosphine and tributyl phosphine; triarylphosphines, such as triphenylphosphine; diarylalkylphosphines, such as, diphenylcyclohexylphosphine; pyridines, such as 2,6-dimethylpyridine, 2,4,6-trimethylpyridine; as well as other Lewis basic ligands, such as phosphine oxides and phosphinites. Additives may also be present during metathesis that increase catalyst lifetime. Any useful amount of the selected metathesis catalyst can be used in the process. For example, the molar ratio of the unsaturated polyol ester to catalyst may range from about 5: 1 to about 10,000,000: 1 or from about 50: 1 to 500,000: 1.

The metathesis reaction temperature may be a rate-controlling variable where the temperature is selected to provide a desired product at an acceptable rate. The metathesis temperature may be greater than -40°C, may be greater than about -2O⁰C, and is typically greater than about O⁰C or greater than about 2O⁰C. Typically, the metathesis reaction temperature is less than about 15O⁰C, typically less than about 120⁰C. An exemplary temperature range for the metathesis reaction ranges from about 20°C to about 120⁰C. The metathesis reaction can be run under any desired pressure. Typically, it will be desirable to maintain a total pressure that is high enough to keep the cross- metathesis reagent in solution. Therefore, as the molecular weight of the cross- metathesis reagent increases, the lower pressure range typically decreases since the boiling point of the cross-metathesis reagent increases. The total pressure may be selected to be greater than about 1OkPa, in some embodiments greater than about 30 kP, or greater than about 10OkPa. Typically, the reaction pressure is no more than about 7000 kPa, in some embodiments no more than about 3000 kPa. An exemplary pressure range for the metathesis reaction is from about 100 kPa to about 3000 kPa.

In some embodiments, the metathesis reaction is catalyzed by a system containing both a transition and a non-transition metal component. The most active and largest number of catalyst systems are derived from Group VI A transition metals, for example, tungsten and molybdenum. Separation Step (step (cϊ):

After cross-metathesis with a short-chain olefin, at least a portion of the acid- , ester-, or carboxylate salt-functionalized alkene is separated from the remaining cross-metathesis products. If cross-metathesis is conducted on an unsaturated glyceride starting composition the resulting cross-metathesis products should be transesterified prior to separation. This allows the separation step to separate the ester-functionalized alkene from any ester functional ized alkane that may be present in the transesterification products. Useful techniques for separating the acid-, ester-, or carboxylate salt- functionalized alkene from the remaining cross-metathesis products include, for example, distillation, reactive distillation, chromatography, fractional crystallization, membrane separation, liquid/liquid extraction, or a combination thereof. Advantageously, when the acid-, ester- or carboxylate salt-functionalized alkene has a chain length less than about 16 carbon atoms, it is readily separated from any stearic acid that may be present in the starting composition. This eliminates separation problems between azelaic acid and stearic acid that have conventionally been present in prior art azelaic acid production processes.

In many embodiments, the acid-, ester-, or carboxylate salt-functionalized alkene can be purified to a high degree using one or more of the above-described techniques. For example, the acid-, ester-, or carboxylate salt-functionalized alkene can be purified to a level of 90% wt. or greater (e.g., 95% wt. or greater, 96% wt. or greater, 97% wt. or greater, 98% wt. or greater, 99% wt. or greater, 99.5% wt. or greater, or 99.9% wt. or greater). Using the method of the invention, a high purity functionalized alkene intermediate can be obtained using one or more conventional separation processes. Achieving a high purity functionalized alkene intermediate allows for the production of a high purity organic acid product such as azelaic acid. For example, in some embodiments, the azelaic acid has a purity of 90% wt. or greater (e.g., 95% wt. or greater, 96% wt. or greater, 97% wt. or greater, 98% wt. or greater, 99% wt. or greater, 99.5% wt. or greater, or 99.9% wt. or greater). Oxidative/Reductive Cleavage (step (dϊ): After separation, the carbon-carbon double bond of the acid-, ester-, or carboxylate salt-functional ized alkene may be directly oxidized to a carboxylic acid, or may be ozonized and the resulting ozonide oxidatively cleaved or reductively cleaved. Oxidative cleavage can be used to produce products having carboxylic acid groups. Reductive cleavage can be used to produce products having aldehyde groups.

When oxidatively cleaved, the reaction results in the formation of: (i) a first organic acid having the structure

X-(CH₂)_n-COOH where X is an ester group, a carboxylic acid group, or a carboxylate salt; and n is 3 to 1 1 ; and (ii) one or more co-product acid compounds.

Oxidative cleavage may be conducted by any useful technique for converting a carbon-carbon double bond directly or indirectly into a carboxylic acid group. Representative examples of useful techniques include ozonolysis, chemical oxidation using hydrogen peroxide and/or air, or chemical oxidation using potassium permanganate, potassium dichromate, chromic acid, sodium hypochlorite, ruthenium tetroxide, or ruthenium dioxide. In an exemplary process, the oxidative cleavage of step (d) is conducted by ozonolysis. As used herein, the term "ozonolysis" refers to the process in which ozone is used to oxidatively cleave a carbon-carbon double bond to form carboxylic acid groups. Mechanistically, ozonolysis is understood to take place in multiple reaction steps. In the first step, ozone reacts with the carbon-carbon double bond on the target molecule to form an ozonide. In the next step, the ozonide is cleaved by reaction with oxygen to form a carboxylic acid and an aldehyde. Further oxidation converts the aldehyde into a carboxylic acid group. Ozonide formation is typically conducted by contacting the target molecule with ozone in an ozone absorber. The ozone absorber provides for intimate mixing between the ozone gas and the target molecule, which is typically in a liquid phase. Examples of solvents for the liquid phase include carboxylic acids, for example, C2 to C9 carboxylic acids, and other saturated organic compounds. After formation of the ozonide, the ozonide is fed into an oxidation reactor where it is contacted with oxygen (e.g., in the form of a stream of air). The oxygen reacts with the ozonide causing it to split into a carboxylic acid-terminated molecule and an aldehyde- terminated molecule. Further reaction with oxygen then converts the aldehyde- terminated molecule into a second carboxylic acid-terminated molecule. Typically, the oxidation reaction is conducted at a temperature of about 50°C or greater, for example, about 5O⁰C to about 100°C. Additional details regarding ozonolysis are reported, for example, in U.S. Patent No. 2,813,1 13.

In another exemplary process, oxidative cleavage is achieved by first reacting the target molecule with hydrogen peroxide (H₂O₂) to form a vicinal diol. In many embodiments, this reaction is conducted in the presence of a catalyst. Examples of catalysts include tungstic acid (see, US 5,569,1 1 1), supported tungstic acid (e.g., alumina or silica supported tungstic acid) (see, e.g., Noureddini and Kanabur, JAOCS, 1999, 76(3), 305-312), phosphorotungstic acid (see, e.g., JP 05004938), or ammonium metavanadate (see, e.g., US 5,869,049). After formation of the vicinal diol, the vicinal diol is cleaved by oxidation with either hydrogen peroxide or air to form two carboxylic acid molecules. Additional details of oxidative cleavage reactions can be found, for example, in J. Am. Oil Chem Soc. 1997, 54, 870A-872A; Fat ScL Technol. 1995, 97(10), 359-367; J. Mat. ScL Lett. 1998, 17, 1305-1307; J Am. Oil Chem. Soc. 1999, 76(3), 305-312; J. MoI. Catal A: Chemical 1999, 150, 105-1 1 1 ; Ind. Eng. Chem. Res. 200, 39, 2766-2771.

Oxidative cleavage can also be accomplished by a two step process that proceeds via ketonization. The unsaturated fatty acid is first ketonized at the double bond using a modified Wacker process (e.g., PdSO₄/heteropolyacid/O₂). Subsequently, the keto fatty acid is cleaved using Mn²⁺/O₂. The product is typically a mixture of 2 dicarboxylic acids. The process is most suitable for use with terminal double bonds. An alternative process for compound containing internal double bonds is the conversion of the alkene to an epoxide followed by isomerization of the epoxide to a ketone. The ketone can then be oxidatively cleaved as described herein.

In some embodiments, the carbon-carbon double bond is cleaved to form an aldehyde functional group. Such cleavage can be accomplished by first reacting the functionalized alkene intermediate with ozone to form an ozonide. The ozonide is then reductively cleaved to form an organic aldehyde compound and one or more co-product aldehyde compounds. Reductive cleavage of an ozonide may be accomplished using a number of different methods. Common techniques include treatment by 1) zinc/acetic acid, 2) sodium borohydride, 3) triphenylphosphine, 4) trimethylphosphite, 5) dimethylsulfide, 6) palladium on carbon catalyst and hydrogen followed by acid, 7) thiourea, or 8) tetracyanoethylene.

Once formed, the organic aldehyde may be reduced to an omega-hydroxy carboxylic acid compound (i.e., HO(CH₂)_nCOOH) or may be reductively aminated to form an omega-amino carboxylic acid (i.e., H₂N(CH₂)_nCOOH). Omega-hydroxy carboxylic acids may be used, for example, to make polyester polymers and omega- amino carboxylic acids may be used, for example, to make polyamide polymers. Product Organic Compounds

The methods of the invention can be employed to produce desired organic acids or aldehyde compounds. The structure of the organic acid or aldehyde that is formed depends upon the starting composition that is chosen for use in the method. For acid compounds, Δ9 starting compositions may be used to manufacture azelaic acid according to the method of the invention. Similarly, Δ5 starting compositions may be used to manufacture glutaric acid according to the method of the invention. A summary of certain starting compositions and the organic acids produced therefrom is provided in TABLE D. TABLE D

X is an ester group, a carboxylic acid group, or a carboxylate salt.

In the methods of the invention, a co-product acid is produced along with the organic acid product. The structure of the co-product acid depends upon the short- chain olefin that is chosen for use in the cross-metathesis step (i.e., step (b)). Advantageously, if the short-chain olefin is symmetric, the method of the invention will produce a single co-product acid. For example, if 3-hexene is used as the short- chain olefin, the co-product acid will be propionic acid. When the co-product acid is asymmetric, the method of the invention will yield two co-product acids. A summary of short-chain olefins and the corresponding co-product acid(s) is provided in TABLE E.

TABLE E

In similar fashion, reductive cleavage (i.e. ozonization followed by reductive cleavage) may be employed to produce certain organic aldehyde compounds. A summary of certain starting compositions and the organic aldehydes produced therefrom is provided in TABLE F. A summary of short-chain olefins and the corresponding co-product aldehyde(s) is provided in TABLE G.

TABLE F

TABLE G

The method of the invention will now be described with reference to FlG. 1 to FIG. 3. Referring now to FIG. 1 , a process flow diagram of an embodiment of the method 10 of the invention is shown. In the method 10, starting composition 12 is provided that comprises a Δ9 starting composition. In reaction 14, starting composition 12 is cross-metathesized with a short-chain olefin 16 in the presence of a metathesis catalyst 17 to produce cross-metathesis products 18 comprising (i) one or more olefin compounds 20; and (ii) one or more acid-, ester-, or carboxylate salt- functionalized alkenes 22. Unreacted starting material (including unreacted unsaturated species and saturated species) may also be present with the cross- metathesis products 18. If the starting composition comprises an unsaturated glyceride, the unsaturated glyceride may be transesterified to form unsaturated monoesters prior to being cross-metathesized with the short-chain internal olefin, or the unsaturated glyceride may be cross-metathesized with the short-chain internal olefin followed by transesterification to form unsaturated monoesters. FoI lowing cross-metathesis, at least a portion of the acid-, ester-, or carboxylate salt-functionalized alkene 22 is separated 23 from the remaining cross- metathesis products 18. As part of this separation, any saturated species that are present may be removed and any unreacted starting material may be removed and recycled back into the starting composition feed.

In one embodiment, after separation, the double bond of the isolated acid-, ester-, or carboxylate salt-functionalized alkene 22 is oxidatively cleaved 24 to form (i) an organic acid 30 having the structure: X-(CH₂)_I1-COOH (where X is an ester group, a carboxylic acid group, or a carboxylate salt; and n is 3 to 1 1); and (ii) one or more co-product acid compounds 32.

In another embodiment, after separation, the double bond of the isolated acid-, ester-, or carboxylate salt-functionalized alkene 22 is reacted with ozone to form an ozonide compound 34. The ozonide compound' 34 is then reductively cleaved 36 to form (i) an aldehyde compound 38 having the structure: X-(CH₂)_n- CHO (where X is an ester group, a carboxylic acid group, or a carboxylate salt; and n is 3 to 1 1); and (ii) one or more co-product aldehyde compounds 40.

Referring now to FlG. 2, a process flow diagram of an embodiment of the method 100 of the invention is shown. In this embodiment, a fatty acid triglyceride starting composition is converted into free fatty esters prior to cross-metathesizing the free fatty esters with a short-chain olefin. In a first step of the method, triglyceride 102 and alcohol 104 are trans-esterified 106 in the presence of trans- esterification catalyst 105. Trans-esterification reaction 106 converts triglyceride 102 into glycerol 108 and free fatty esters 1 10. Together, the glycerol 108 and free fatty acid esters 1 10 are referred to as trans-esterification products 1 15. After trans- esterification reaction 106, a separation 1 14 (e.g., water wash or distillation) is conducted on the trans-esterification products 1 15 in order to separate the glycerol 108 from the free fatty acid esters 1 10.

After separation, a cross-metathesis reaction 1 18 is conducted between the free fatty esters 1 10 and short-chain olefin 1 16. The cross-metathesis 1 18 is conducted in the presence of a metathesis catalyst 120 in order to form cross- metathesis products 122 comprising (i) one or more olefin compounds 124; and (ii) an ester- functional ized alkene having at least one double bond 126. Following this, at least a portion of the ester-functionalized alkene 126 is separated 128 (e.g., using distillation) from the cross-metathesis products 122. The isolated ester- functional ized alkene 126 is then oxidatively cleaved 129 to form (i) an organic acid 134 having the structure: X-(CH₂)_n-COOH (where X is an ester group, a carboxylic acid group, or a carboxylate salt; and n is 3 to 1 1); and (ii) one or more co-product acid compounds 136.

Referring to FlG. 3, a process flow diagram of another embodiment of the method 200 of the invention is shown. In this embodiment, a triglyceride starting composition is cross-metathesized with a short-chain internal olefin followed by trans-esterification to liberate an unsaturated free fatty ester. In the first reaction of method 200, triglyceride 202 and short-chain internal olefin 216 are cross- metathesized 218 in the presence of a metathesis catalyst 220 to form cross- metathesis products 222. Cross-metathesis products 222 comprise (i) one or more olefin compounds 224; and (ii) one or more ester-functionalized alkenes 225. Saturated species and unreacted starting material may also be present with the cross- metathesis products 222. In this embodiment, the ester-functionalized alkenes 225 are triglycerides. After cross-metathesis, at least a portion of the ester- functionalized alkene 225 is separated from the remaining cross-metathesis products 222. Spent metathesis catalyst 220 may also be removed at this point. Following this, the ester-functionalized alkene 225 is trans-esterified 206 with an alcohol 204 in the presence of a trans-esterification catalyst 205. Trans-esterification reaction 206 converts the ester-functionalized alkene 225 into trans-esterification products 215 comprising glycerol 208 and ester-functionalized alkene 240. Ester- functionalized alkanes may also be present at this point. After trans-esterification reaction 206, a separation 214 is conducted in order to isolate the ester- functionalized alkene 240. After separation, the isolated ester-functionalized alkene 240 is then oxidatively cleaved to form (i) an organic acid 234 having the structure: X-(CH₂)_n-COOH (where X is an ester group, a carboxylic acid group, or a carboxylate salt; and n is 3 to 1 1); and (ii) one or more co-product acid compounds 236.

In an exemplary embodiment, as shown in FIG. 2A, triglyceride 102A is reacted with methanol 104A in trans-esterification reaction 106A in the presence of trans-esterification catalyst 105A. Trans-esterification reaction 106A converts triglyceride 102A into glycerol 108A and free fatty acid methyl esters HOA. Collectively, glycerol 108 A and free fatty acid methyl esters 1 1OA are referred to as trans-esterification products 1 15A. In this embodiment, the free fatty acid methyl esters 1 1OA comprise methyl oleate (i.e., the methyl ester of oleic acid), methyl linoleate (i.e., the methyl ester of linoleic acid), and methyl linolenate (i.e., the methyl ester of linolenic acid). Palmitic and/or stearic acid may also be present. After trans-esterification reaction 106A, separation process 1 14A is conducted on the trans-esterification products 1 15A in order to separate the glycerol 108 A from the free fatty acid methyl esters 1 1OA. Following separation, the free fatty acid methyl esters HOA and 2-butene 1 16A (i.e., a short-chain internal olefin) are cross- methathesized 1 18A in the presence of a metathesis catalyst 120A to form cross- metathesis products 122A comprising olefins 124A and ester- functional ized alkenes 126A. The cross-metathesis products 122A are then separated by separation process 128 A to isolate the 9-undecenoic acid methyl ester 125A. Next, the 9-undecenoic acid methyl ester 125 A is oxidatively cleaved 140A to form (i) an organic acid 134A having the structure CH₃OOC-(CH₂)₇-COOH; and (ii) acetic acid 136A. Optionally, the ester group of organic acid 134A may be hydrolyzed to form azelaic acid HOOC-(CH₂)₇-COOH. In another exemplary embodiment, as shown in FIG. 2B, triglyceride 102B is reacted with methanol 104B in trans-esterification reaction 106B in the presence of trans-esterification catalyst 105B. Trans-esterification reaction 106B converts triglyceride 102B into trans-esterification products 1 15B including glycerol 108B and free fatty acid methyl ester HOB. After trans-esterification reaction 106B, separation process 1 14B is conducted on the trans-esterification products 1 15 B in order to separate the glycerol 108B from the free fatty acid methyl ester 1 1 OB. Following separation, fatty acid methyl ester 1 1OB and 3-hexene 1 16B (i.e., a short- chain internal olefin) are cross-metathesized 1 18B in the presence of a metathesis catalyst 120B to form cross-metathesis products 122B comprising olefins 124B and ester- functionalized alkenes 126B. Ester- functionalized alkanes may also be present. Cross-metathesis products 122B are separated via separation process 128B to isolate 9-dodecenoic acid methyl ester 125B. Next, 9-dodecenoic acid methyl ester 125 B is oxidatively cleaved 140B to form (i) an organic acid 134B having the structure: CH₃OOC-(CH₂)₇-COOH; and (ii) propionic acid 136B. Optionally, the ester group of organic acid 134A can be hydrolyzed to form azelaic acid HOOC- (CH₂)₇-COOH. Other embodiments of this invention will be apparent to those skilled in the art upon consideration of this specification or from practice of the invention disclosed herein. Various omissions, modifications, and changes to the principles and embodiments described herein may be made by one skilled in the art without departing from the true scope and spirit of the invention which is indicated by the following claims. All patents, patent documents, and publications cited herein are hereby incorporated by reference as if individually incorporated.

Claims

WHAT IS CLAIMED IS:

1. A method of making an organic acid, the method comprising the steps of:

(a) providing a starting composition comprising an unsaturated fatty acid, an unsaturated fatty ester, a carboxylate salt of unsaturated fatty acid, or a mixture thereof;

(b) cross-metathesizing the starting composition of step (a) with a short- chain olefin in the presence of a metathesis catalyst to form cross-metathesis products comprising:

(i) one or more olefin compounds; and (ii) one or more acid-, ester-, or carboxylate salt-functionalized alkenes having at least one double bond;

(c) separating at least a portion of the one or more acid-, ester-, or carboxylate salt-functionalized alkenes from the cross-metathesis products; and

(d) oxidatively cleaving a double bond of the one or more acid-, ester-, or carboxylate salt-functionalized alkenes to form:

(i) an organic acid having the structure:

X-(CH₂)_n-COOH where X is an ester group, a carboxylic acid group, or a carboxylate salt; and n is 3 to 1 1 ; and (ii) one or more co-product acid compounds.

2. The method of claim 1 , wherein the organic acid has an ester group and wherein the method further comprises the step of: converting the ester group of the organic acid to a carboxylic acid.

3. The method of claim 1, wherein the organic acid has a carboxylate salt, and wherein the method further comprises the step of: converting the carboxylate salt to a carboxylic acid.

4. The method of claim 1, wherein the starting composition comprises an unsaturated fatty acid, ester, or carboxylate salt having the formula:

CH₃-(CH₂)_nl-[-(CH₂)_n3-CH=CH-]_x-(CH₂)_n2-COOR where:

R is hydrogen, an aliphatic group, or a metal ion; nl is an integer equal to or greater than 0; n2 is an integer equal to or greater than 0; n3 is an integer equal to or greater than 0; and x is an integer equal to or greater than 1.

5. The method of claim 1, wherein the starting composition comprises an unsaturated polyol ester.

6. The method of claim 5, wherein the unsaturated polyol ester has the formula

R (0-Y)₁₇₁ (OH)_n (O-X)_b where

R is an organic group having a valency of (n+m+b); m is an integer from 0 to (n+m+b- 1 ); b is an integer from 1 to (n+m+b); n is an integer from 0 to (n+m+b- 1);

(n+m+b) is an integer that is 2 or greater;

X is -(O)C-(CH₂)_n2-[-CH=CH-(CH₂)_n3-]_x-(CH₂)_nl-CH₃; Y iS -(O)C-R';

R' is a straight or branched chain alkyl or alkenyl group; n 1 is an integer equal to or greater than 0; n2 is an integer equal to or greater than 0; n3 is an integer equal to or greater than 0; and x is an integer equal to or greater than 1.

7. The method of claim 1 , wherein the starting composition is an unsaturated glyceride.

8. The method of claim 7, wherein the unsaturated glyceride has the formula:

CH₂A-CHB-CH₂C

9. The method of claim 1, wherein the starting composition comprises a Δ9 unsaturated fatty acid, a Δ9 unsaturated fatty ester, a carboxylate salt of a Δ9 unsaturated fatty acid, or a mixture thereof.

10. The method of claim 9, wherein the Δ9 unsaturated fatty acid comprises oleic acid, linoleic acid, linolenic acid, or a mixture thereof.

1 1. The method of claim 9, wherein the Δ9 unsaturated fatty ester comprises an alkyl ester of oleic acid, an alkyl ester of linoleic acid, an alkyl ester of linolenic acid, or a mixture thereof.

12. The method of claim 1 1, wherein the Δ9 unsaturated fatty ester comprises methyl oleate, methyl linoleate, methyl linolenate, or a mixture thereof.

13. The method of claim 9, wherein the Δ9 unsaturated fatty ester is an unsaturated polyol ester.

14. The method of claim 9, wherein the Δ9 unsaturated fatty ester comprises a vegetable oil.

15. The method of claim 14, wherein the vegetable oil comprises soybean oil, rapeseed oil, corn oil, sesame oil, cottonseed oil, sunflower oil, canola oil, safflower oil, palm oil, palm kernel oil, linseed oil, castor oil, olive oil, peanut oil, and mixtures thereof.

16. The method of claim 9, wherein the Δ9 unsaturated fatty ester comprises fish oil, lard, tallow, or mixtures thereof.

17. The method of claim 9, wherein the Δ9 unsaturated fatty acid comprises tall oil.

18. The method of claim 9, wherein the organic acid is azelaic acid.

19. The method of claim 1 , wherein the starting composition comprises a Δ6 unsaturated fatty acid, a Δ6 unsaturated fatty ester, a carboxylate salt of a Δ6 unsaturated fatty acid, or a mixture thereof.

20. The method of claim 19, wherein the starting composition comprises coriander oil.

21. The method of claim 19, wherein the Δ6 unsaturated fatty acid is petroselinic acid.

22. The method of claim 19, wherein the organic acid is adipic acid.

23. The method of claim 1, wherein the starting composition comprises a Δ5 unsaturated fatty acid, a Δ5 unsaturated fatty ester, a carboxylate salt of a Δ5 unsaturated fatty acid, or a mixture thereof.

24. The method of claim 23, wherein the starting composition comprises meadowfoam oil.

25. The method of claim 23, wherein the Δ5 unsaturated fatty acid is 5- eicosenoic acid.

26. The method of claim 23, wherein the organic acid is glutaric acid.

27. The method of claim 1, wherein the starting composition comprises a Δl 1 unsaturated fatty acid, a Δl 1 unsaturated fatty ester, a carboxylate salt of a Δl 1 unsaturated fatty acid, or a mixture thereof.

28. The method of claim 27, wherein the starting composition comprises camelina oil.

29. The method of claim 27, wherein the Δl l unsaturated fatty acid is gondoic acid.

30. The method of claim 27, wherein the organic acid is 1, 1 1-undecanedioc acid.

31. The method of claim 1, wherein the starting composition comprises a Δ13 unsaturated fatty acid, a Δ13 unsaturated fatty ester, a carboxylate salt of a Δ13 unsaturated fatty acid, or a mixture thereof.

32. The method of claim 31 , wherein the starting composition comprises crambe oil or high erucic rapeseed oil.

33. The method of claim 31 , wherein the Δ13 unsaturated fatty acid is erucic acid.

34. The method of claim 31, wherein the organic acid is brassylic acid.

35. The method of claim 1, wherein the short-chain olefin has the structure:

R⁷R⁸C=CR⁹R¹⁰ where R⁷, R⁸, R⁹, and R¹⁰ are each, independently, hydrogen or an organic group, with the proviso that at least one of R⁷ or R⁸ is an organic group.

36. The method of claim 35, wherein the short-chain olefin is a short-chain internal olefin.

37. The method of claim 36, wherein the short-chain internal olefin has the structure R⁷R⁸C=CR⁹R¹⁰ where R⁷, R⁸, R⁹, and R¹⁰ are each, independently, hydrogen or an organic group, with the proviso that at least one of R⁷ or R⁸ is an organic group, and at least one of R⁹ or R¹⁰ is an organic group.

38. The method of claim 36, wherein the short-chain internal olefin is symmetric.

39. The method of claim 38, wherein the symmetric short-chain internal olefin has the structure:

R⁷CH=CHR⁹ where R⁷ and R⁹ are the same organic group.

40. The method of claim 39, wherein the symmetric short-chain internal olefin is selected from the group consisting of 2-butene, 3-hexene, and 4-octene.

41. The method of claim 36, wherein the short-chain internal olefin is

( asymmetric.

42. The method of claim 41 , wherein the asymmetric short-chain internal olefin is 2-pentene, 2-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, 2-nonene, 3- nonene, and 4-nonene.

43. The method of claim 35, wherein the short-chain olefin is an α-olefin having the structure:

CH₂=CH-R¹⁰ where R¹⁰ is an organic group.

44. The method of claim 43, wherein -R¹⁰ is -(CH₂)_n-CH₃, where n ranges from O to 6.

45. The method of claim 43, wherein the α-olefin is selected from the group consisting of 1-propene, 1 -butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1- nonene.

46. The method of claim 1, wherein the metathesis catalyst is selected from the group consisting of:

12 14 16

18 20 22

C627

C712

C697 C682

where Ph is phenyl, Mes is mesityl, py is pyridine, Cp is cyclopentyl, and Cy is cyclohexyl.

47. The method of claim 1 , wherein the separating step comprises distillation, reactive distillation, chromatography, fractional crystallization, membrane separation, liquid/liquid extraction, or a combination thereof.

48. The method of claim 1, wherein the step of oxidatively cleaving comprises ozonolysis.

49. The method of claim 1 , wherein the organic acid is azelaic acid, glutaric acid, adipic acid, 1, 1 1-undecanedioc acid, or brassylic acid.

50. The method of claim 1 , wherein the short-chain olefin is 3-hexene and the co-product acid is propionic acid.

51. The method of claim 1 , wherein the short-chain olefin is 2-butene and the co- product acid is acetic acid.

52. The method of claim 1, wherein the short-chain olefin is 1 -propene and the co-product acid comprises acetic acid and formic acid.

53. The method of claim 1 , wherein the short-chain olefin is 1-butene and the co- product acid comprises propionic acid and formic acid.

54. The method of claim 1, wherein the short-chain olefin is 1-pentene and the co-product acid comprises butyric acid and formic acid.

55. A diacid produced by the method of claim 1.

56. The diacid of claim 55, wherein the diacid is selected from the group consisting of azelaic acid, glutaric acid, adipic acid, 1, 1 1-undecanedioc acid, and brassylic acid.

57. The diacid of claim 55, wherein the diacid has a purity of 90% wt. or greater.

58. The diacid of claim 55, wherein the diacid has a purity of 95% wt. or greater.

59. The diacid of claim 55, wherein the diacid has a purity of 99% wt. or greater.

60. The diacid of claim 55, wherein the diacid has a purity of 99.9% wt. or greater.

61. The diacid of claim 55, wherein the diacid is azelaic acid having a purity of 90% wt. or greater.

62. A method of making an organic aldehyde, the method comprising the steps of: (a) providing a starting composition comprising an unsaturated fatty acid, an unsaturated fatty ester, a carboxylate salt of unsaturated fatty acid, or a mixture thereof;

(b) cross-metathesizing the starting composition of step (a) with a short- chain olefin in the presence of a metathesis catalyst to form cross-metathesis products comprising:

(i) one or more olefin compounds; and

(ii) one or more acid-, ester-, or carboxylate salt- functional ized alkenes having at least one double bond; (c) separating at least a portion of the one or more acid-, ester-, or carboxylate salt-functionalized alkenes from the cross-metathesis products; and

(d) reacting the acid-, ester-, or carboxylate salt-functionalized alkene with ozone to form an ozonide; and

(e) reductively cleaving the ozonide to form: (i) an organic aldehyde having the structure:

X-(CH₂)_n-CHO where X is an ester group, a carboxylic acid group, or a carboxylate salt; and n is 3 to 1 1 ; and (ii) one or more co-product aldehyde compounds.

63. The method of claim 62, further comprising the step of reducing the aldehyde to an alcohol.

64. The method of claim 62, further comprising the step of reductively aminating the aldehyde to an amine.