Method for synthesizing pheromone derivatives by Z-selective olefin metathesis

Abstract

This invention provides a method for synthesizing aliphatic olefin metathesis products with high Z-isomer purity from olefin starting materials with low Z-isomer purity. [Solution] This method includes contacting an internal olefin with an olefin metathesis reaction partner, such as an acylated alkenol or alkenal acetal, in the presence of a Z-selective metathesis catalyst to form an aliphatic olefin metathesis product. In various embodiments, the aliphatic olefin metathesis product is an insect pheromone. Pheromone compositions and methods of use thereof are also described.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 032,932, filed on June 1, 2020, which is incorporated herein by reference in its entirety. [Background technology]

[0002] Background of the Invention As global demand for food increases, the need for effective pest control is growing. Conventional insecticides are among the most popular chemical control agents due to their easy availability, rapid action, and reliability. However, the overuse, misuse, and abuse of these chemicals are leading to resistant pests, changes in the natural environment, and in some cases, environmental damage.

[0003] The use of insect pheromones to control pest populations is gaining popularity as a viable, safe, and environmentally friendly alternative to conventional insecticides. Since their discovery in the late 1950s, these molecules have demonstrated effectiveness in reducing insect populations through various methods, including mass capture, attraction and death, and mating disruption. The latter method, in particular, has become a non-toxic pest control method, utilizing the ability of synthetic pheromones to cause confusion and mating disruption by masking natural pheromones.

[0004] While pheromones hold significant potential in agricultural insect control, the cost of synthesizing them using currently available technologies is extremely high, preventing the widespread use of this sustainable technology beyond high-value crops. Therefore, there is a need to develop novel technologies for the cost-effective production of insect pheromones and related fragrances, scents, and polymer intermediates. This invention addresses this need with a synthetic method capable of forming a wide range of unsaturated aliphatic olefin metathesis products with high Z-isomer purity, including synthetic insect pheromones, from low-cost raw materials. [Brief explanation of the drawing]

[0005] [Figure 1] Shows the catalytic hydrogenation of methyl oleate to form oleyl alcohol. [Figure 2] Shows the synthesis of Z9-14Ac by stereospecific olefin cross-metathesis using oleyl acetate and (Z)-deca-5-ene. [Figure 3] Shows the synthesis of Z9-12Ac by stereospecific olefin cross-metathesis using oleyl acetate and (Z)-hexa-3-ene. [Figure 4] Shows the synthesis of metathesis jojoba oil acetate by stereospecific olefin cross-metathesis using jojoba oil acetate and (Z)-hexa-3-ene. [Figure 5] Shows the synthesis of cross-metathesis jojoba oil alcohol by stereospecific olefin cross-metathesis using commercially available jojoba oil and (Z)-hexa-3-ene followed by reduction. SUMMARY OF THE INVENTION

[0006] Brief Summary of the Invention A method for synthesizing Z-enriched aliphatic olefin metathesis products is provided herein. The method includes contacting an olefin metathesis reaction partner and an internal olefin in the presence of a Group 8 transition metal metathesis catalyst to form a Z-enriched aliphatic olefin metathesis product, where the aliphatic olefin metathesis product is an acylated alkenol or an alkenal acetal, the olefin metathesis reaction partner includes a mixture of Z-olefin and E-olefin in a starting Z:E ratio, the aliphatic olefin metathesis product includes a mixture of Z-olefin and E-olefin in a product Z:E ratio, the product Z:E ratio is higher than the starting Z:E ratio.

[0007] In some embodiments, the invention is of formula I: A method for synthesizing an aliphatic olefin metathesis product of TIFF2026086750000002.tif16128, wherein to form the aliphatic olefin metathesis product, formula III: The olefin metathesis reaction partners of TIFF2026086750000003.tif16128 and formula IV: The process includes contacting the internal olefin of TIFF2026086750000004.tif10128 with a metathesis catalyst, in which, R 1 H and C 1~6 Selected from the group consisting of alkyl groups; R 2 C 1~18 Alkyl and C 2~18 Selected from the group consisting of alkenils; R 3 C 1~18 It is alkyl; The subscript y is an integer in the range of 0 to 17; The subscript z is an integer in the range of 0 to 17; This invention provides a method in which the metathesis catalyst is a Z-selective group 8 transition metal catalyst.

[0008] In some embodiments, the metathesis catalyst is a Z-selective ruthenium catalyst or a Z-selective osmium catalyst.

[0009] In some embodiments, the metathesis catalyst used in a method for synthesizing an aliphatic olefin metathesis product of formula I is formula V: This is a Z-selective metathesis catalyst having the structure TIFF2026086750000005.tif38128. During the ceremony, M is selected from the group consisting of ruthenium and osmium; X and Y are independently selected from the group consisting of S and O; Z is selected from the group consisting of O, S (=O), N, and halogens; Each subscript m and subscript n is an integer independently selected from 0, 1, 2, 3, and 4; Each Ra is independently selected from the group consisting of halogen, C1-C6 alkyl, alkoxy, aryl, and heteroaryl; or one R a and an adjacent R a together form an unsubstituted or substituted bicyclic or unsubstituted or substituted polycyclic ring; each R b is independently selected from the group consisting of halogen, C1-C6 alkyl, alkoxy, aryl, and heteroaryl; or one R b and an adjacent R b together form an unsubstituted or substituted bicyclic or unsubstituted or substituted polycyclic ring; R c is selected from the group consisting of hydrogen and C1-C6 alkyl; each R d , R e , R f and R g is independently selected from the group consisting of hydrogen and C1-C6 alkyl; R 12 and R 13 are independently selected from the group consisting of 2,4,6-tri-isopropylphenyl, 2,6-di-isopropylphenyl, 2,6-di-adamantylphenyl, 2-isopropyl-6-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, and 2,6-di-tert-butylphenyl; each R 14 is independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, benzyl, and phenyl; R 15 is selected from the group consisting of hydrogen, halogen, and C1-C6 alkyl, or R 15 and one R 14 together form a bond.

[0010] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of Formula I is an acylating agent and Formula II: The process further includes a step of contacting the alkenol of TIFF2026086750000006.tif10128 with the alkenol to form an olefin metathesis reaction partner of formula III.

[0011] In some embodiments, a method for synthesizing aliphatic olefin metathesis products is given by formula IIa: The process further includes the step of reducing an unsaturated aliphatic carboxyl derivative of TIFF2026086750000007.tif16128 to form an alkenol of formula II, In the formula, R 4 H and C 1~8 Selected from the group consisting of alkyl groups.

[0012] In some embodiments, the synthesis of an aliphatic olefin metathesis product includes a step of forming an internal olefin by contacting a terminal olefin with a metathesis catalyst. [Invention 1001] A method for synthesizing a Z-enriched aliphatic olefin metathesis product, comprising the step of contacting an olefin metathesis reaction partner and an internal olefin in the presence of a group 8 transition metal metathesis catalyst in order to form a Z-enriched aliphatic olefin metathesis product, wherein The aliphatic olefin metathesis product is an acylated alkenol or alkenal acetal. The olefin metathesis reaction partner contains a mixture of Z-olefin and E-olefin in a starting Z:E ratio. The aliphatic olefin metathesis product contains a mixture of Z-olefin and E-olefin in a Z:E ratio. Methods in which the product Z:E ratio is higher than the starting Z:E ratio. [Invention 1002] The method of the present invention 1001, wherein the metathesis catalyst is a Z-selective ruthenium catalyst or a Z-selective osmium catalyst. [Invention 1003] The method of the present invention 1001, wherein the aliphatic olefin metathesis product is at least 97% to 99% Z. [Invention 1004] The method of the present invention 1001, wherein the aliphatic olefin metathesis product is more than 99% Z. [Invention 1005] The method of the present invention 1001, wherein the metathesis reaction partner is approximately 1% to approximately 50% E. [Invention 1006] Aliphatic olefin metathesis product is given by formula I: TIFF2026086750000008.tif16128 is an acylated alkenol; Metathesis reaction partner is Equation III: It is a compound of TIFF2026086750000009.tif16128; Internal olefin is formula IV: It is a compound of TIFF2026086750000010.tif10128; R 1 However, H and C 1~6 Selected from the group consisting of alkyl groups; R 2 However, C 1~18 Alkyl and C 2~18 Selected from the group consisting of alkenils; R 3 C 1~18 It is alkyl; The subscript y is an integer in the range of 0 to 17; The subscript z is an integer in the range of 0 to 17; The Group 8 transition metal metathesis catalyst is a Z-selective Group 8 transition metal catalyst. The method of the present invention 1001. [Invention 1007] The Z-selective metathesis catalyst has the structure of formula V: It has TIFF2026086750000011.tif38128, During the ceremony, M is selected from the group consisting of ruthenium and osmium; X and Y are independently selected from the group consisting of S and O; Z is selected from the group consisting of S (=O), O, N, and halogens; The subscript m is an integer selected from 2, 4, 3, 1, and 0; The subscript n is an integer selected from 0, 1, 2, 3, or 4; Each R a R is independently selected from the group consisting of halogens, C1-C6 alkyls, alkoxys, aryls, and heteroaryls; or one R a is adjacent to R a Together with other elements, they form unsubstituted or substituted biringu or unsubstituted or substituted polyringu; Each R b R is independently selected from the group consisting of halogens, C1-C6 alkyls, alkoxys, aryls, and heteroaryls; or one R b is adjacent to R b Together with other elements, they form unsubstituted or substituted biringu or unsubstituted or substituted polyringu; R c It is selected from the group consisting of hydrogen and C1-C6 alkyl groups; Each R d , R e , R f , and R g These are independently selected from the group consisting of hydrogen and C1-C6 alkyl groups; R 12 and R 13 These are independently selected from the group consisting of 2,6-di-isopropylphenyl, 2,4,6-tri-isopropylphenyl, 2,6-di-adamantylphenyl, 2-isopropyl-6-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, and 2,6-di-tert-butylphenyl; Each R 14 These are independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, benzyl, phenyl, and hydrogen; R 15 R is selected from the group consisting of hydrogen, halogens, and C1-C6 alkyl groups, or 15 and one R 14 They come together to form a bond. The method of the present invention 1006. [Invention 1008] M is ruthenium; X and Y are S; Z is selected from the group consisting of S (=O) and O; The subscript m is 2; The index n is 0; Each R a These are independently selected from the group consisting of halogens, C1-C6 alkyls, and aryls; R c is hydrogen; Each R d , R e , R f , and R g is hydrogen; Each R 14 These are independently selected from the group consisting of methyl, isopropyl, benzyl, and tert-butyl. The method of the present invention 1007. [Invention 1009] Metathesis catalysts are a group consisting of the following: A method of the present invention 1007, selected from TIFF2026086750000012.tif48137. [Invention 1010] The synthesis of aliphatic olefin metathesis products involves an acylating agent and formula II: The method of the present invention 1006, comprising the step of forming an olefin metathesis reaction partner of formula III by contacting it with the alkenol of TIFF2026086750000013.tif10128. [Invention 1011] The method of the present invention 1010, wherein the acylating agent is acetic anhydride. [Invention 1012] The synthesis of aliphatic olefin metathesis reaction partners is given by formula IIa: TIFF2026086750000014.tif16128 (in the formula, R 4 H and C 1~8 (Selected from the group consisting of alkyl groups) The method of the present invention 1010, comprising the step of reducing an unsaturated aliphatic carboxyl derivative to form an alkenol of formula II. [Invention 1013] The method of the present invention 1012, wherein the step of forming the alkenol of formula II includes the step of contacting an unsaturated aliphatic carboxyl derivative with a base in the presence of a hydrogenation catalyst and hydrogen gas. [Invention 1014] The method of the present invention 1012, wherein the step of forming the alkenol of formula II includes the step of contacting an unsaturated aliphatic carboxyl derivative with a reducing agent. [Invention 1015] The method of the present invention 1014, wherein the reducing agent is sodium bis(2-methoxyethoxy)aluminum hydride. [Invention 1016] The method of the present invention 1012, wherein the unsaturated aliphatic carboxyl derivative is derived from natural oil. [Invention 1017] The method of the present invention 1016, wherein the natural oil is selected from the group consisting of almond oil, canola oil, avocado oil, argan oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, grape seed oil, olive oil, palm oil, peanut oil, hemp seed oil, macadamia oil, safflower oil, sesame oil, soybean oil, sunflower oil, flaxseed oil, palm kernel oil, tuna oil, jatropha oil, jojoba oil, mustard oil, shepherd's purse oil, custard oil, castor oil, and combinations thereof. [Invention 1018] The method of the present invention 1016, further comprising the step of distilling an unsaturated aliphatic carboxyl derivative, alkenol, or olefin metathesis reaction partner before metathesis in order to remove plant-derived impurities. [Invention 1019] Aliphatic olefin metathesis product is given by formula VI: It is an alkenal acetal of TIFF2026086750000015.tif16128; Metathesis reaction partner is formula VII: It is a compound of TIFF2026086750000016.tif16128; Internal olefin is formula IV: It is a compound of TIFF2026086750000017.tif10128; R 1 C 1~6It is alkyl; R 2 However, C 1~18 Alkyl and C 2~18 Selected from the group consisting of alkenils; R 3 C 1~18 It is alkyl; The subscript y is an integer in the range of 0 to 17; The subscript z is an integer in the range of 0 to 17; The Group 8 transition metal metathesis catalyst is a Z-selective Group 8 transition metal catalyst. The method of the present invention 1001. [Invention 1020] Metathesis product is given by formula VIII: The method of the present invention 1019, further comprising the step of converting TIFF2026086750000018.tif16128 to alkenal. [Invention 1021] The method of the present invention 1001, wherein the synthesis of an aliphatic olefin metathesis product includes a step of forming an internal olefin by contacting a terminal olefin with a metathesis catalyst in order to form an internal olefin. [Invention 1022] The internal olefin is given by formula VIa: It is a compound of TIFF2026086750000019.tif12128; Terminal olefin is formula IVb: The method of the present invention 1021, which is a compound of TIFF2026086750000020.tif10128. [Invention 1023] The method of the present invention 1021 or 1022, wherein the metathesis catalyst for forming the internal olefin is a Z-selective ruthenium catalyst or a Z-selective tungsten catalyst. [Invention 1024] R 1 C 1~3 It is alkyl, R 2 C 1~12 It is alkyl, R 3 C 1~12 The method of the present invention 1006, wherein the element is alkyl, y is an integer in the range of 5 to 15, and z is an integer in the range of 0 to 7. [Invention 1025] The metathesis reaction partner in Equation III is aliphatic C 12 ~C 30 It is an olefin acetate; The internal olefin in formula IV is C4~C 20 It is an internal olefin; The aliphatic olefin metathesis product of formula I is C8~C 28 (Z)-unsaturated aliphatic ester acetate, The method of the present invention 1006. [Invention 1026] The olefin metathesis reaction partner in formula III is (Z)-octadeca-9-en-1-yl acetate; The internal olefin in formula IV is (Z)-deca-5-ene; The aliphatic olefin metathesis product of formula I is (Z)-tetradeca-9-en-1-yl acetate. The method of the present invention 1006. [Invention 1027] The olefin metathesis reaction partner in formula III is (Z)-octadeca-9-en-1-yl acetate; The internal olefin of formula IV is (Z)-hexa-3-ene; The aliphatic olefin metathesis product of formula I is (Z)-dodeca-9-en-1-yl acetate. The method of the present invention 1006. [Invention 1028] The olefin metathesis reaction partner in formula III is (Z)-icosa-11-en-1-yl acetate; The internal olefin of formula IV is (Z)-hexa-3-ene; The aliphatic olefin metathesis product of formula I is (Z)-tetradeca-11-en-1-yl acetate. The method of the present invention 1006. [Invention 1029] The method of the present invention 1001, wherein the synthesis of an aliphatic olefin metathesis product comprises a step of contacting the olefin metathesis reaction partner with a pretreatment reagent before contacting the internal olefin. [Invention 1030] The method of the present invention 1029, wherein the pretreatment reagent is selected from the group consisting of alumina, triethylaluminum, and magnesium aluminum isopropoxide. [Modes for carrying out the invention]

[0013] Detailed description of the invention I. Introduction This invention provides a method for synthesizing high-purity aliphatic olefin derivatives (e.g., linear lepidopteran pheromones; SCLPs) through stereochemical retention olefin cross-metathesis of internal olefins with low isomer purity. By using various low-purity aliphatic olefin derivative and internal olefin raw materials in combination with a Z-selective olefin metathesis catalyst, a wide variety of pheromones with high Z purity can be obtained. This invention enables the use of commercially available olefin raw materials with low isomer purity for the preparation of high-purity SCLPs, thereby greatly increasing the industrial applicability of this technology.

[0014] II. Definition The following definitions and abbreviations are to be used in interpreting the present invention. As used herein, the terms “invention” or “this invention” are non-limiting and are not intended to refer to any single embodiment, but rather encompass all possible embodiments.

[0015] The terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains,” and “containing,” as used in this invention, or any other variations thereof, are intended to encompass non-exclusive inclusion. A composition, mixture, process, method, article, or apparatus containing a list of elements is not necessarily limited to those elements and may include other elements that are not expressly enumerated or specific to the composition, mixture, process, method, article, or apparatus. Furthermore, unless expressly contradictory, “or” means inclusive “or” and not exclusive “or.”

[0016] The terms “about” and “around” as used herein to modify numerical values ​​indicate a closed range around the express value. If “X” is a value, then “about X” or “around X” would refer to values ​​between 0.9X and 1.1X, and in specific cases, values ​​between 0.95X and 1.05X or 0.98X and 1.02X. Any reference to “about X” or “around X” specifically refers to at least the values ​​X, 0.95X, 0.96X, 0.97X, 0.98X, 0.99X, 1.01X, 1.02X, 1.03X, 1.04X, and 1.05X. Thus, “about X” and “around X” are intended to teach and present written support for a limitation in a claim, for example, “0.99X.”

[0017] As used herein, the term “substantially” describes a range of values, such as approximately 85–100%, for example, 85–99.9%, 90–99.9%, 95–99.9%, 98–99.9%, or 99–99.9%.

[0018] As used herein, the term “mostly” means a percentage in the range of more than 50%, for example, in the range of approximately 51–100%, 75–99.9%, 85–98.5%, or approximately 95–99%.

[0019] As used herein and in the appended claims, the singular forms “a,” “an,” and “the” include multiple subjects unless otherwise clearly indicated in the context. For example, a reference to “aliphatic olefin metathesis product” includes one aliphatic olefin metathesis product and a combination or mixture of two or more aliphatic olefin metathesis products (e.g., a mixture of aliphatic Z-olefin and aliphatic E-olefin metathesis products), a reference to “unsaturated aliphatic carboxyl derivative” includes one unsaturated aliphatic carboxyl derivative and a combination or mixture of two or more unsaturated aliphatic carboxyl derivatives, a reference to “alkenol” includes one alkenol and a combination or mixture of two or more alkenols, and a reference to “substituent” includes one substituent and a combination of two or more substituents, and so on.

[0020] As used herein, the term “metathesis product” means an olefin containing at least one double bond formed by a metathesis reaction. As used herein, the term “aliphatic olefin metathesis product” means one olefin-containing compound formed by a metathesis reaction (i.e., one metathesis product formed from an olefin and a metathesis reaction partner) having the structure RC(O)O-R', where R is an alkyl group listed below, and R' is a linear alkenyl group containing at least four carbon atoms, e.g., 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, or 40 carbon atoms. In some embodiments, R' is C4~C 30 It is a linear alkenyl group. As a non-restrictive example, "unsaturated aliphatic ester acetate" is an RC(O)O-R' where R is a methyl group and R' is C2~C26 This refers to an aliphatic olefin metathesis product obtained by cross-metathesis between an olefin and a linear alkenyl group, which is an olefin metathesis reaction partner. In this invention, "C8~C 28 (Z)-Unsaturated aliphatic ester acetates are also non-limiting examples of aliphatic olefin metathesis products. In some embodiments, the aliphatic olefin metathesis product is a pheromone, such as a linear lepidopteran pheromone (SCLP).

[0021] As used herein, the term “metathesis” refers to a catalytic reaction involving the exchange of alkylidene units (i.e., R2C= units) between compounds containing one or more carbon-carbon double bonds (e.g., olefinic compounds) through the formation and cleavage of carbon-carbon double bonds. Metathesis can occur between two molecules having the same structure (often called self-metathesis) and / or between two molecules having different structures (often called cross-metathesis).

[0022] As used herein, the term “pheromone” means a substance or characteristic mixture of substances secreted and released by an organism and detected by a second organism of the same or closely related species. Typically, the detection of a pheromone by a second organism facilitates a specific response, such as a certain behavioral response or developmental process. For example, insect pheromones can influence behaviors such as mating and aggregation. Examples of pheromones include compounds produced by lepidopterans (i.e., moths and butterflies belonging to the Geometridae, Noctuidae, Arctiidae, and Lymantriidae families), such as C 10 ~C 18 Acetate, C 10 ~C 18 Alcohol, C 10 ~C 18 Aldehydes, and C 17 ~C 23 Polyenes are examples, but are not limited to them. "Unsaturated pheromones" means any pheromone that has at least one carbon-carbon double bond.

[0023] As used herein, the term "contacting" means a process of bringing at least two distinct species into contact such that they can react. However, it should be recognized that the resulting reaction product can be generated directly from the reaction between the added reagents or from intermediates derived from one or more of the added reagents that can be generated in the reaction mixture.

[0024] As used herein, the term "metathesis reaction partner" means a compound having a carbon-carbon double bond that can react with an olefin in a metathesis reaction to form a new carbon-carbon double bond. A metathesis reaction partner can be an aliphatic olefin-containing compound, such as an olefin metathesis reaction partner. The term "olefin metathesis reaction partner" means a compound having the structure R-C(O)O-R', where R is an alkyl group as described below and R' is a linear alkenyl group containing at least 4 carbon atoms, such as 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, or 40 carbon atoms. In some embodiments, R' is a C6~C 34 linear alkenyl group. For example, an "unsaturated aliphatic alcohol acetate" is an olefin metathesis reaction partner where R in R-C(O)O-R' is a methyl group and R' is a C4~C 28 linear alkenyl group. Further non-limiting examples of olefin metathesis reaction partners include those where R in R-C(O)O-R' is a methyl group and R' is a C 10 ~C 28 linear alkenyl group, an "aliphatic C 12 ~C 30 olefin acetate" and an "acetate ester of a C 10 ~C 28 aliphatic alkenol".

[0025] As used herein, the term "olefin" means a straight-chain (e.g., linear) or branched hydrocarbon compound containing at least one carbon-carbon double bond, and derivatives thereof. The olefin may be unsubstituted or substituted with one or more functional groups including alcohol groups, protected alcohol groups, carboxylate groups, and carboxylic acid ester groups. The term "olefin" as used herein encompasses hydrocarbons having two or more carbon-carbon double bonds (e.g., diolefins, triolefins, etc.). Hydrocarbons having two or more carbon-carbon double bonds, and derivatives thereof, are also referred to as "polyenes". The term "aliphatic olefin" means an olefin having at least 4 carbon atoms, and the aliphatic olefin may have, for example, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, or 40 carbon atoms. The olefin may contain terminal double bonds ("terminal olefins") and / or internal double bonds ("internal olefins"). In some embodiments, the olefin used in the method of the present invention has 4 to 26 carbon atoms. In certain other embodiments, the olefin used in the method of the present invention comprises a mixture of olefins having 4 to 26 carbon atoms somewhere therein.

[0026] As used herein, the term "internal olefin" means an olefin in which each olefinic carbon (i.e., the carbon of the carbon-carbon double bond; C=C) is substituted with at least one non-hydrogen substituent (e.g., R 1' R 2' C=CR 3' R 4' ; wherein at least one of R 1' and R 2' is not hydrogen, and at least one of R 3' and R 4' is not hydrogen). The internal olefin can be disubstituted, trisubstituted, or tetrasubstituted (e.g., disubstituted internal olefin: R 5' HC=CHR 8' and / or HR 6' C=CR7' H; Trisubstituted internal olefin: R 5' R 6' C=CHR 8' , R 5' R 6' C=CR 7' H, R 5' HC=CR 7' R 8' , and / or HR 6' C=CR 7' R 8' ; and tetrasubstituted internal olefins: R 5' R 6' C=CR 7' R 8' ; In the formula, R 5' , R 6' , R 7' , and R 8' These may be the same or different, and each may be independently substituted (aliphatic group, heteroaliphatic group, or functional group).

[0027] As used herein, the term “terminal olefin” refers to an olefin (e.g., R) in which one olefinic carbon (i.e., the carbon of a carbon-carbon double bond; C=C) is substituted with at least one non-hydrogen substituent and the other olefinic carbon is unsubstituted. 9' R 10' C=CH2; where R 9' and R 10' This means that at least one or both of these are not hydrogen. Terminal olefins can be monosubstituted or disubstituted (e.g., monosubstituted terminal olefins: R 9' HC=CH2 and / or HR 10' C=CH2; and disubstituted terminal olefins: R 9' R 10' C=CH2; where R 9' and R 10' These may be the same or different, and each may be independently substituted (aliphatic group, heteroaliphatic group, or functional group).

[0028] "Aliphatic olefin derivative" means an olefin starting material used in the method of the present invention or a compound obtained from an aliphatic olefin starting material. Examples of aliphatic olefin derivatives include, but are not limited to, unsaturated aliphatic alcohols (i.e., alkenols), unsaturated aliphatic alcohol acetates and unsaturated aliphatic ester acetates (e.g., olefin metathesis reaction partners and aliphatic olefin metathesis products), unsaturated aliphatic aldehydes, unsaturated aliphatic carboxyl derivatives (e.g., unsaturated fatty acids, unsaturated fatty acid alkyl esters), and polyenes. In the present invention, both "metathesis product" and "aliphatic olefin metathesis product" are types of aliphatic olefin derivatives. In some embodiments, the aliphatic olefin derivative used in the method of the present invention has 6 to 34 carbon atoms. In some embodiments, the aliphatic olefin derivative synthesized according to the method of the present invention has 6 to 30 carbon atoms. In certain other embodiments, the aliphatic olefin derivative used in the method of the present invention includes a mixture of aliphatic olefin derivatives having 4 to 34 carbon atoms somewhere. In certain other embodiments, the aliphatic olefin derivatives synthesized according to the method of the present invention include a mixture of aliphatic olefin derivatives having 4 to 30 carbon atoms somewhere.

[0029] Δ 9 -Unsaturated olefins are olefins in which the 9th carbon-carbon bond from the end of the olefin chain is a double bond (for example, Δ 9 - Unsaturated aliphatic alcohols, Δ 9 - Unsaturated aliphatic alcohol acetate, Δ 9 -Unsaturated aliphatic ester acetate, Δ 9 -unsaturated aliphatic aldehyde, Δ 9 -Unsaturated aliphatic carboxyl derivatives, Δ 9 -unsaturated fatty acids, Δ 9 - This refers to unsaturated fatty acid alkyl esters, etc. For example, Δ 9 -Unsaturated fatty acids refer to olefinic carboxylic acids in which the 9th carbon-carbon bond from the carboxylic acid end of the olefin chain is a double bond. 9-Examples of unsaturated fatty acids include, but are not limited to, 9-10-hydroxy-2-decenoic acid, oleic acid (i.e., (Z)-octadeca-9-enoic acid), and elaidic acid (i.e., (E)-octadeca-9-enoic acid). Another non-limiting example is Δ 9 - An unsaturated aliphatic ester acetate refers to an olefinic ester acetate in which the 9th carbon-carbon bond from the acetate end of the olefin chain is a double bond. 9 - Examples of unsaturated aliphatic ester acetates include, but are not limited to, 9-decenyl acetate, (Z)-tetradeca-9-en-1-yl acetate, and (E)-tetradeca-9-en-1-yl acetate.

[0030] Similarly, Δ 11 -Unsaturated olefins are olefins in which the 11th carbon-carbon bond from the end of the olefin chain is a double bond (e.g., Δ 11 - Unsaturated aliphatic alcohols, Δ 11 - Unsaturated aliphatic alcohol acetate, Δ 11 -Unsaturated aliphatic ester acetate, Δ 11 -unsaturated aliphatic aldehyde, Δ 11 -Unsaturated aliphatic carboxyl derivatives, Δ 11 -unsaturated fatty acids, Δ 11 - This refers to unsaturated fatty acid alkyl esters, etc. For example, Δ 11 -Unsaturated fatty acids refer to olefinic carboxylic acids in which the 11th carbon-carbon bond, counting from the carboxylic acid end of the olefin chain, is a double bond. 11 -Examples of unsaturated fatty acids include, but are not limited to, 11-dodecenoic acid, gondonic acid (i.e., (Z)-icosa-11-enoic acid or (Z)-eicosa-11-enoic acid), and trans-gondoic acid (i.e., (E)-icosa-11-enoic acid or (E)-eicosa-11-enoic acid). The prefixes "icosa" and "eicosa" refer to hydrocarbon chains having 20 carbon atoms (e.g., fully saturated C). 20 Hydrocarbon chains, i.e., alkyl groups; or C containing one or more unsaturated units. 20It should be noted that it is used interchangeably to mean hydrocarbon chains (i.e., alkenyls or olefins). Another non-restrictive example is Δ 11 - An unsaturated aliphatic ester acetate refers to an olefinic ester acetate in which the 11th carbon-carbon bond from the acetate end of the olefin chain is a double bond. 11 - Examples of unsaturated aliphatic ester acetates include, but are not limited to, 11-dodecenyl acetate, (Z)-tetradeca-11-en-1-yl acetate, and (E)-tetradeca-11-en-1-yl acetate.

[0031] As used herein, the terms “alkenol” and “aliphatic alkenol” are interchangeable and mean a compound having the structure R'-OR, where R' is a linear alkenyl group containing at least four carbon atoms, e.g., 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, or 30 carbon atoms, and R is a hydrogen or alcohol protecting group. In some embodiments, R' is C6~C 34 It is a linear alkenyl group. As a non-restrictive example, "C 10 ~C 28 "Aliphatic alkenol" is an R'-OR where R is hydrogen and R' is carbon. 10 ~C 28 This refers to alkenols (i.e., aliphatic alkenols), which are linear alkenyl groups.

[0032] As used herein, the term “unsaturated aliphatic carboxyl derivative” means an aliphatic olefin compound that includes a carboxyl moiety and is used in the methods of the present invention. As used herein, the term “carboxyl” represents a group of the formula “-C(O)O-”. In the present invention, unsaturated aliphatic carbonyl derivatives include “unsaturated fatty acids” and “unsaturated fatty acid alkyl esters”. As used herein, the term “unsaturated fatty acid” means a compound having the structure R'-C(O)OH, where R' is a linear alkenyl group containing at least four carbon atoms, for example, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, or 40 carbon atoms. In some embodiments, R' in R'-C(O)OH is C6~C 34 It is a linear alkenyl group. As a non-restrictive example, "C 12 ~C 30 "Unsaturated fatty acids" are those in R'-C(O)OH where R' is C 11 ~C 29 This refers to an unsaturated fatty acid that has a linear alkenyl group. As used herein, the term “unsaturated fatty acid alkyl ester” means a compound having the structure R'-C(O)OR, where R' is a linear alkenyl group containing at least four carbon atoms, e.g., 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, or 40 carbon atoms, and R is an alkyl group as described below. In some embodiments, R' in R'-C(O)OR is C6~C 34 It is a linear alkenyl group. As a non-restrictive example, "C 12 ~C 30 "Unsaturated fatty acid methyl ester" is R'-C(O)OR where R is a methyl group and R' is C 10 ~C 28 These are alkyl esters of unsaturated fatty acids, which are linear alkenyl groups. Unsaturated aliphatic carboxyl derivatives can be mixtures of different unsaturated fatty acids or mixtures of different alkyl esters of unsaturated fatty acids. In some embodiments, unsaturated aliphatic carboxyl derivatives are obtained from natural oils or natural oil derivatives.

[0033] As used herein, the term "isomer" means a molecule that has the same chemical formula as another molecule but has a different chemical structure. That is, isomers contain the same number of atoms of each element but have different arrangements of atoms of each element. Isomers include "structural isomers" and "stereoisomers." In "structural isomers" (also called "constitutional isomers"), the atoms have different bonding orders. Structural isomers have different IUPAC names and may or may not belong to the same functional group. This type of isomer includes skeletal isomers, in which the hydrocarbon chain has an unspecified amount of branching, and positional isomers, which relate to the position of the functional group on the chain; as well as functional group isomers, in which the molecular formula is the same but the functional group is different.

[0034] As used herein, the term “positional isomer” means a first compound having the same carbon skeleton and functional groups as a second compound, but with different positions of the functional groups on or within the carbon skeleton. In certain embodiments, one positional isomer may differ from the position of its positional isomer in the carbon skeleton of the functional groups (e.g., alkenes, hydroxyls, aldehydes, and acetyls). For example, the positional isomer of (Z)-tetradeca-9-en-1-yl acetate is (Z)-tetradeca-11-en-1-yl acetate. This is because (Z)-tetradeca-9-en-1-yl acetate is produced by cross-metathesis between (Z)-octadeca-9-en-1-yl acetate and (Z)-deca-5-ene, and (Z)-tetradeca-11-en-1-yl acetate is produced by cross-metathesis between (Z)-icosa-11-en-1-yl acetate and (Z)-hexa-3-ene.

[0035] In stereoisomers, the bond structure is the same, but the geometric arrangement of atoms and functional groups in space differs. This class of isomers includes enantiomers, which are mirror images of each other and cannot be superimposed, and diastereomers, which are non-mirror images of each other. Geometric isomers, or cis / trans isomers, are diastereomers that differ in the stereochemical orientation of the substituent atoms in the bond. The double bond in the olefins and aliphatic olefin derivatives described herein prevents molecular rotation by fixing the molecule to one of two possible stereoconfigurations, each representing a different molecule, a geometric isomer. These geometric isomers are called E (derived from the German word Entgegen, meaning opposite) when the carbon chain is connected to the opposite side (trans side) of the double bond, and Z (Zzanmen, meaning together) when it is connected to the same side (cis side). Thus, the olefins and aliphatic olefin derivatives described herein may be in (E) configuration, (Z) configuration, or a mixture of (E) and (Z) configurations. Conformational isomers (or conformers), which are another type of isomer, can be rotational isomers, diastereomers, or enantiomers, depending on the particular compound.

[0036] As used herein, the term “stereoselectivity” describes the ability to produce a particular stereoisomer of a compound (i.e., an olefin or aliphatic olefin derivative as described herein) in an isomerically pure form (e.g., about 90% Z isomer or about 90% E isomer), or to produce a particular stereoisomer of an aliphatic olefin derivative in the presence of a metathesis catalyst according to the methods described herein. In the present invention, “stereoselective” or “selective” means a cross-metathesis reaction that preferentially produces one stereoisomer over a second stereoisomer, i.e., a metathesis product or aliphatic olefin metathesis product in which the ratio of a desired stereoisomer to a less desired stereoisomer is greater than 1:1.

[0037] "Z stereoselectivity" or "Z selectivity" describes the ability to produce Z isomers of a compound (i.e., an olefin or aliphatic olefin derivative as described herein) in a Z-isomerically pure form, a mostly pure form, or a substantially pure form; or, in the presence of a metathesis catalyst, i.) a mixture of E and Z isomers of a metathesis reaction partner (e.g., an acylated olefin metathesis reaction partner) and ii.) an olefin that may be at least 95% Z, even if it is a mixture of E and Z isomers, in accordance with the method described herein. Furthermore, in the present invention, "Z stereoselective" or "Z-selective" means a cross-metathesis reaction that preferentially produces Z isomers over E isomers, i.e., produces a Z-aliphatic olefin metathesis product in which the ratio of Z isomers to E isomers is greater than 1:1. "Z-selective catalyst" means a Group 8 transition metal catalyst described herein that preferentially produces Z-aliphatic olefin metathesis products in the cross-metathesis reaction method of the present invention. Z selectivity may be expressed as the proportion of the isomer products formed. For example, aliphatic olefin derivatives (e.g., metathesis products, aliphatic olefin metathesis products, etc.) prepared according to the method of the present invention have at least 80% Z, usually more than 85% Z, or 90% Z, or 95% Z, preferably more than 97% Z, or more than 98% Z, or more than 99% Z, or more than 99.5% Z, or more than 99.9% Z.

[0038] For individual isomers, the terms “isomeric purity” or “isomerically pure” are used interchangeably and refer to the amount or concentration of a particular isomer of the olefin or aliphatic olefin derivative relative to the total amount or total concentration of all isomeric forms of the olefin or aliphatic olefin derivative. Each aliphatic olefin derivative prepared according to the method of the present invention (e.g., metathesis product, aliphatic olefin metathesis product, etc.) is substantially Z-isomerically pure. In other words, aliphatic olefin derivatives prepared according to the method of the present invention (e.g., metathesis product, aliphatic olefin metathesis product, etc.) are more than 80% Z-isomer, usually more than 85% Z-isomer, or 90% Z-isomer, or 95% Z-isomer, more preferably more than 97% Z-isomer, or more than 98% Z-isomer, or more than 99% Z-isomer, or more than 99.5% Z-isomer, or more than 99.9% Z-isomer.

[0039] As used herein, the term "Z:E ratio" means the ratio of the amount of Z isomers (e.g., Z-aliphatic olefin metathesis products) to the amount of E isomers (e.g., E-aliphatic olefin metathesis products). As used herein, the term "Z-enriched" means a material (e.g., metathesis product) having a higher Z:E ratio than the precursor material (e.g., metathesis reaction partner).

[0040] As used herein, the term "low isomer purity" means olefins, metathesis reaction partners, olefin starting materials, olefin-containing reactants, and aliphatic olefin derivatives (e.g., alkenols, unsaturated aliphatic alcohol acetates, unsaturated aliphatic ester acetates, olefin metathesis reaction partners, aliphatic olefin metathesis products, unsaturated aliphatic aldehydes, unsaturated aliphatic carboxyl derivatives, metathesis products, etc.) used in or produced from the methods of the present invention, which are less than 90% Z isomers (i.e., 10% or more E isomers).

[0041] As used herein, the term “highly Z-selective” means that more than 85% of the metathesis products and / or aliphatic olefin metathesis products formed are in the Z configuration.

[0042] As used herein, the term “metathesis catalyst” means any catalyst or catalytic system that catalyzes a metathesis reaction. Those skilled in the art will recognize that a metathesis catalyst may participate in a metathesis reaction to increase the reaction rate, but is not consumed by itself during the reaction. “Ruthenium catalyst” means a metathesis catalyst having one or more ruthenium atoms. “Osmium catalyst” means a metathesis catalyst having one or more osmium atoms.

[0043] As used herein, the terms “form” and “convert” are interchangeable and mean to form an intermediate species or product by reacting a starting material with at least one reagent. Forming or converting may also include forming a further intermediate species or product by reacting the intermediate with at least one reagent.

[0044] The term "functional group" encompasses any functional group known in the art.

[0045] As used herein, the term "acyl" means the functional group -C(O)-R in which R is the alkyl group described below.

[0046] As used herein, the term "acylation" means converting an alcohol group (-OH) to an ester group (-OC(O)-R) where R is one of the alkyl groups listed below.

[0047] As used herein, the term "acylation agent" means a compound that can react with a substrate compound to add a -C(O)-R moiety to a compound. By using an acylation agent, for example, an ester (i.e., -C(O)OR) can be formed on a compound having a hydroxyl moiety (i.e., -OH). One or more acylation agents useful in the present invention are C1-C 20 The acylating agent may be a linear or branched alkyl or aryl carboxylic acid anhydride, a carboxylic acid halide, a diketene, or an acetoacetate ester. Examples of carboxylic acid anhydrides suitable for use as an acylating agent in the present invention include, but are not limited to, acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, hexanoic anhydride, 2-ethylhexanoic anhydride, nonanoic anhydride, lauric anhydride, palmitic anhydride, stearic anhydride, benzoic anhydride, substituted benzoic anhydride, phthalic anhydride, and isophthalic anhydride. Examples of carboxylic acid halides suitable for use as an acylating agent in the present invention include acetyl chloride, propionyl chloride, butyryl chloride, hexanoyl chloride, 2-ethylhexanoyl chloride, lauroyl chloride, palmitoyl chloride, and stearoyl chloride. Examples of acetoacetate esters suitable for use as an acylating agent in the present invention include, but are not limited to, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, and tert-butyl acetoacetate.

[0048] As used herein, the term “alkenyl” means an alkyl group as defined herein having one or more double bonds. The term “heteroalkenyl” means an alkenyl group in which one or more carbon atoms are replaced by heteroatoms (i.e., nitrogen, oxygen, or sulfur; including any oxidized form of nitrogen or sulfur, and any quaternized form of basic nitrogen).

[0049] As used herein, the term "reduction" means electron density transfer from a hydrogenation catalyst or reducing agent to a substrate compound. Typically, electron density transfer occurs through processes that involve the addition of hydrogen to the substrate compound.

[0050] As used herein, the term “reducing agent” means any reagent effective in reducing a carboxylic acid group (i.e., -C(O)OH) to an alcohol group (i.e., -CH2-OH). Examples of reducing agents include, but are not limited to, sodium borohydride, sodium triacetoxyborohydride, sodium cyanoborohydride, lithium aluminum hydride, and sodium bis(2-methoxyethoxy)aluminum hydride.

[0051] As used herein, the term "hydrogenation catalyst" means any catalyst effective in hydrogenating an alkyl ester group (i.e., -C(O)OR) where R is one of the alkyl groups listed below to an alcohol group (i.e., -CH2-OH). The hydrogenation catalyst may be heterogeneous or homogeneous.

[0052] In the present invention, the term "heterogeneous" means reaction conditions in which one or more reagents or involved substances (i.e., heterogeneous catalysts) do not dissolve in the reaction medium; in other words, reaction conditions in which one or more reagents or involved substances are in a different phase (e.g., a solid catalyst) than other solvents, reagents, compounds, or substrates (e.g., liquids or vapors) when mixed together. The term "homogeneous" means reaction conditions in which all reagents or involved substances (i.e., homogeneous catalysts) are soluble in the reaction medium (i.e., in the same phase as other solvents, reagents, compounds, or substrates when mixed together). The terms "heterogeneous" and "homogeneous" may also refer to catalysts. For example, "heterogeneous catalyst" means a catalyst that does not dissolve in the reaction medium; in other words, a catalyst that is in a different phase (e.g., a solid catalyst) than other solvents, reagents, compounds, or substrates (e.g., liquids or vapors) when mixed together. "Homogeneous catalyst" means a catalyst that is soluble in the reaction medium (i.e., in the same phase as other solvents, reagents, compounds, or substrates when mixed together).

[0053] As used herein, the terms “aliphatic” or “aliphatic group” mean a linear (i.e., unbranched) or branched substituted or unsubstituted hydrocarbon chain that is fully saturated or contains one or more unsaturated units, or a monocyclic, bicyclic, or tricyclic hydrocarbon (also referred herein as “carbocyclic” or “alicyclic”) that is fully saturated or contains one or more unsaturated units, but is not aromatic and has one bond to the rest of the molecule. Unless otherwise specified, an aliphatic group contains 1 to 30 aliphatic carbon atoms. In some embodiments, an aliphatic group contains 1 to 20 aliphatic carbon atoms. In other embodiments, an aliphatic group contains 1 to 10 aliphatic carbon atoms. In yet another embodiment, an aliphatic group contains 1 to 5 aliphatic carbon atoms, and in yet another embodiment, an aliphatic group contains 1, 2, 3, or 4 aliphatic carbon atoms. In some embodiments, "alicyclic" (or "carbocyclic") refers to monocyclic C3-C6 hydrocarbons or C8-C6 hydrocarbons that are fully saturated or contain one or more unsaturated units, but are not aromatic and have one bond site to the rest of the molecule. 10 This refers to bicyclic hydrocarbons. Suitable aliphatic groups include, but are not limited to, linear or branched substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, and their hybrids, such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl, or (cycloalkyl)alkenyl. The term "heteroaliphatic" means an aliphatic group in which at least one carbon atom of the aliphatic group is replaced by a heteroatom (i.e., nitrogen, oxygen, or sulfur; including any oxidized form of nitrogen or sulfur, and any quaternized form of basic nitrogen).

[0054] As used herein, the term "alkyl" is given in the common sense of the art and includes straight-chain (i.e., linear) or branched saturated aliphatic groups having an indicated number of carbon atoms. Straight-chain or branched alkyls have approximately 1 to 40 carbon atoms in their backbone, for example, 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, or 40 carbon atoms. In some embodiments, straight-chain or linear alkyls are C1-C 30 Therefore, branched alkyl groups are C3~C 30 In some cases, a linear or branched alkyl group has about 1 to 20 carbon atoms in its skeleton. In some embodiments, a linear or branched alkyl group has about 1 to 10 carbon atoms in its skeleton, for example, C 1~2 , C 1~3 , C 1~4 , C 1~5 , C 1~6 , C 1~7 , C 1~8 , C 1~9 , C 1~10 , C 2~3 , C 2~4 , C 2~5 , C 2~6 , C 3~4 , C 3~5 , C 3~6 , C 4~5 , C 4~6 , and C 5~6 For example, C 1~10 Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, and decyl. In some embodiments, the alkyl group can be a lower alkyl group, where the lower alkyl group contains 1 to 4 carbon atoms (for example, C1 to C4 in a linear lower alkyl group).

[0055] As used herein, the term "heteroalkyl" is given in the common sense of the art and means an alkyl group as described herein in which one or more carbon atoms are replaced by heteroatoms (e.g., oxygen, nitrogen, sulfur, etc.). Examples of heteroalkyl groups include, but are not limited to, alkoxy, poly(ethylene glycol)-, and alkyl-substituted aminos.

[0056] As used herein, the term “alkoxy” means the -OR portion where R is an alkyl group as defined above. The term “silylalkyl” means an alkyl group as defined herein in which at least one carbon atom is replaced by a silicon atom. The term “silyloxy” means the -OSiR3 portion where each R is independently selected from the group consisting of alkyl, substituted alkyl, aryl, and substituted aryl groups as defined herein.

[0057] As used herein, the term "cycloalkyl" means a saturated monocyclic, bicyclic, or tricyclic hydrocarbon group having one bond site to the rest of the molecule. Cycloalkyl groups include alkyl-substituted cycloalkyl groups and cycloalkyl-substituted alkyl groups. In some embodiments, the cycloalkyl ring has about 3 to 10 carbon atoms in the ring structure, or about 5, 6, or 7 carbon atoms in the ring structure, with the ring being monocyclic or bicyclic.

[0058] As used herein, the term "alkynyl" means an alkyl group as defined herein having one or more triple bonds.

[0059] As used herein, the term “aryl,” used alone or as part of a larger phrase such as “aralkyl,” “aralkoxy,” or “aryloxyalkyl,” means a monocyclic or bicyclic system having a total of 5 to 14 ring members, with at least one ring in the system being aromatic, and each ring in the system containing 3 to 7 ring members. The term “aryl” is interchangeable with the term “aryl ring.” In certain aspects of the present invention, “aryl” means an aromatic ring system, including but not limited to phenyl, biphenyl, naphthyl, and anthracyl, which may have one or more substituents. Groups in which an aromatic ring is condensed to one or more non-aromatic rings, such as indanyl, phthalimidyl, naphthimidyl, phenantridinyl, or tetrahydronaphthyl, are also included in the scope of the term “aryl” as used herein. The term “aryloxy” means the –OR part where R is the aryl group as defined above.

[0060] As used herein, the terms “heteroaryl” and “heteroar-” are used alone or as part of a larger phrase, such as “heteroaralkyl” or “heteroaralkoxy,” and mean a group having 5 to 10 ring atoms (i.e., monocyclic or bicyclic), in some embodiments a group having 5, 6, 9, or 10 ring atoms. In some embodiments, the ring has 6, 10, or 14 π electrons shared in the cyclic arrangement and has 1 to 5 heteroatoms in addition to the carbon atoms. The term “heteroatom” means nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quaternized form of basic nitrogen. Examples of heteroaryl groups include, but are not limited to, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl, pyridadinyl, pyrimidinyl, pyrazinyl, indolidinyl, prinyl, naphthilidinyl, and pteridinyl. As used herein, the terms "heteroaryl" and "heteroaryl-" also include groups in which an aromatic heterocycle is fused to one or more aryl rings, alicyclic rings, or heterocyclyl rings, and the bonding group or bond site is located on the aromatic heterocycle. Non-limiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzothiazolyl, quinolyl, isoquinolyl, synnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolidinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and pyrido[2,3-b]-1,4-oxazine-3(4H)-one. Heteroaryl groups can be monocyclic or bicyclic. The term "heteroaryl group" is interchangeable with the terms "heteroaryl ring," "heteroaryl group," or "aromatic heterocycle," and any of these terms may include a ring that is substituted.The term "heteroaralkyl" means an alkyl group substituted with a heteroaryl group, where the alkyl and heteroaryl groups may be substituted independently.

[0061] Examples of aryl and heteroaryl groups include, but are not limited to, phenyl, pyrrolyl, furanyl, thiophenyl, imidazolyl, oxazolyl, thiazolyl, triazolyl, pyrazolyl, pyridinyl, pyrazinyl, pyridadinyl, and pyrimidinyl. When aryl and heteroaryl groups are used as ligands to coordinate to a metal center, it should be understood that the aryl and heteroaryl groups may have sufficient ionicity to coordinate to the metal center. For example, when a heteroaryl group such as pyrrole is used as a nitrogen-containing ligand as described herein, it should be understood that the pyrrole group has sufficient ionicity to coordinate to a metal center (e.g., it is sufficiently deprotonated to determine pyrrolyl). In some cases, the aryl or heteroaryl group may contain at least one functional group, such as a biphenolate group, that has sufficient ionicity to coordinate to a metal center.

[0062] As used herein, the terms “heterocycle,” “heterocyclyl,” “heterocyclic group,” and “heterocyclic ring” are interchangeable and refer to stable 5- to 7-membered monocyclic or 7- to 10-membered bicyclic heterocyclic parts that are saturated or partially unsaturated and have one or more heteroatoms as defined above (e.g., 1 to 4 heteroatoms) in addition to the carbon atom. When used in relation to the ring atoms of a heterocycle, the term “nitrogen” includes substituted nitrogen. For example, in a saturated or partially unsaturated ring having 1 to 3 heteroatoms selected from oxygen, sulfur, or nitrogen, nitrogen is N (e.g., in 3,4-dihydro-2H-pyrrolyl), NH (e.g., in pyrrolidinyl), or + It can be NR (for example, in N-substituted pyrrolidinyl).

[0063] The heterocycle can be bonded to its pendant group at any heteroatom or carbon atom that results in a stable structure, and any ring atom may be substituted. Examples of these saturated or partially unsaturated heterocyclic groups include, but are not limited to, tetrahydrofuranyl, tetrahydrothiophenyl, pyrrolidinyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl, and quinuclidinyl. The terms “heterocyclic,” “heterocyclyl,” “heterocyclyl ring,” “heterocyclic group,” “heterocyclic moiety,” and “heterocyclic radical” are used interchangeably herein and include groups in which a heterocyclyl ring is fused to one or more aryl rings, heteroaryl rings, or alicyclic rings, such as indolinyl, 3H-indolyl, chromanyl, phenantridinyl, or tetrahydroquinolinyl. The heterocyclyl group may be monocyclic or bicyclic. The term “heterocyclylalkyl” means an alkyl group substituted with a heterocyclyl, where the alkyl moiety and the heterocyclyl moiety may be substituted independently.

[0064] The terms "halogen" and "halo" are used interchangeably to mean F, Cl, Br, or I.

[0065] As used herein, the term “protecting group” refers to a chemical moiety that makes a functional group unreactive but can also be removed to restore the functional group. Examples of “alcohol protecting groups” include, but are not limited to, benzyl; tert-butyl; trityl; tert-butyldimethylsilyl (TBDMS; TBS); 4,5-dimethoxy-2-nitrobenzyloxycarbonyl (Dmnb); and propargyloxycarbonyl (Poc). Examples of "amine protecting groups" include, but are not limited to, benzyloxycarbonyl; 9-fluorenylmethyloxycarbonyl (Fmoc); tert-butyloxycarbonyl (Boc); allyloxycarbonyl (Alloc); p-toluenesulfonyl (Tos); 2,2,5,7,8-pentamethylchroman-6-sulfonyl (Pmc); 2,2,4,6,7-pentamethyl-2,3-dihydrobenzofuran-5-sulfonyl (Pbf); mesityl-2-sulfonyl (Mts); 4-methoxy-2,3,6-trimethylphenylsulfonyl (Mtr); acetamide; phthalimide; etc. (Green and Wuts, Protective Groups in Organic Synthesis, 4) th Other alcohol protecting groups and amine protecting groups, including, for example, those described in Ed. 2007 (Wiley-Interscience, New York), are known to those skilled in the art.

[0066] As described herein, the compounds of the present invention may include “substituted” moieties. Generally, the term “substituted” means that one or more hydrogens of a specified moiety are replaced with preferred substituents, whether or not preceded by the term “optionally.” Unless otherwise indicated, an “substituted” group may have preferred substituents at each of its substituted positions, and if two or more positions in any given structure are substituted with two or more substituents selected from a particular group, the substituents may be the same or different at each position. Generally, the substituent combinations envisioned by the present invention result in the formation of stable or chemically viable compounds. As used herein, “stable” means a compound that is substantially unaltered when subjected to conditions that enable its production, detection, and, in certain embodiments, its recovery, purification, and use for one or more purposes disclosed herein.

[0067] A suitable monovalent substituent on the substitutable carbon atom of the "may be substituted" group is independently a halogen; -(CH2) 0~4 R α ; -(CH2) 0~4 Ure α -O(CH2) 0~4 R α -O-(CH2) 0~4 C(O)OR α ; -(CH2) 0~4 CH(OR α )2; -(CH2) 0~4 SR α ; R α It may be replaced by -(CH2) 0~4 Ph; R α It may be replaced by -(CH2) 0~4 O(CH2) 0~1 Ph; R α -CH=CHPh; R α It may be replaced by -(CH2) 0~4 O(CH2) 0~1 -Pyridyl; -NO2; -CN; -N3; ​​-(CH2) 0~4N(R α )2; -(CH2) 0~4 N(R α )C(O)R α ; -N(R O )C(S)R α ; -(CH2) 0~4 N(R α )C(O)NR α 2; -N(R α )C(S)NR α 2; -(CH2) 0~4 N(R α )C(O)OR α ; -N(R α )N(R α )C(O)R α ; -N(R α )N(R α )C(O)NR α 2; -N(R α )N(R α )C(O)OR α ; -(CH2) 0~4 C(O)R α ; -C(S)R α ; -(CH2) 0~4 C(O)OR α ; -(CH2) 0~4 C(O)SR α ; -(CH2) 0~4 C(O)OSiR α 3; -(CH2) 0~4 OC(O)R α ; -OC(O)(CH2) 0~4 SR-SC(S)SR α ; -(CH2) 0~4 SC(O)R α ; -(CH2) 0~4 C(O)NR α 2; -C(S)NR α 2; -C(S)SR α ; -SC(S)SR α ; -(CH2) 0~4 OC(O)NR α 2; -C(O)N(OR α )R α ; -C(O)C(O)R α ; -C(O)CH2C(O)R α ; -C(NORα )R α ; -(CH2) 0~4 SSR α ; -(CH2) 0~4 S(O)2R α ; -(CH2) 0~4 S(O)2OR α ; -(CH2) 0~4 OS(O)2R α -S(O)2NR α 2; -(CH2) 0~4 S(O)R α -N(R α )S(O)2NR α 2; -N(R α )S(O)2R α ; -N(OR α )R α -C(NH)NR α 2; -P(O)2R α ; -P(O)R α 2; -OP(O)R α 2; -OP(O)(OR α )2; SiR α 3; -(C 1~4 Linear or branched alkylene ON(R) α )2; or -(C 1~4 Linear or branched alkylene C(O)ON(R α )2, where each R α The following substitutions may be made as defined below, and independently of hydrogen, C 1~6 Aliphatic, -CH2Ph, -O(CH2) 0~1 Ph, -CH2- (a 5-6 membered heteroaryl ring), or a 5-6 membered saturated, partially unsaturated, or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or, notwithstanding the above definition, two independently occurring R α Together with the intervening atoms, they form monocyclic or bicyclic 3-12 member saturated, partially unsaturated, or aromatic rings, which may be substituted as defined below, and have 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0068] Rα (or two independently occurring R α A suitable monovalent substituent on the ring formed by combining these atoms with the interposed atoms is independently a halogen; -(CH2) 0~2 R β ; -(HaroR β ); -(CH2) 0~2 OH; -(CH2) 0~2 Ure β ; -(CH2) 0~2 CH(OR β )2; -O(HaroR β ); -CN; -N3; ​​-(CH2) 0~2 C(O)R β ; -(CH2) 0~2 C(O)OH; -(CH2) 0~2 C(O)OR β ; -(CH2) 0~2 SR β ; -(CH2) 0~2 SH; -(CH2) 0~2 NH2; -(CH2) 0~2 NHR β ; -(CH2) 0~2 NR β 2; -NO2; SiR β 3; -OSiR β 3; -C(O)SR β ; -(C 1~4 Linear or branched alkylene)C(O)OR β ; or -SSR β And here each R β It is either unsubstituted, or if preceded by "halo", it is substituted by only one or more halogens, and C 1~4 Aliphatic, -CH2Ph, -O(CH2) 0~1 Ph, or independently selected from a 5-6 membered saturated ring, partially unsaturated ring, or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. α Suitable divalent substituents on the saturated carbon atom include =O and =S.

[0069] Suitable divalent substituents on the saturated carbon atom of the "may be substituted" group include =O; =S; =NNR γ 2; =NNHC(O)R γ ; =NNHC(O)OR γ ; =NNHS(O)2R γ ; =NR γ ; =NOR γ -O(C(R γ 2)) 2~3 O-; or -S(C(R γ 2)) 2~3 S- is given, and here each R that appears independently γ C may be substituted with hydrogen as defined below. 1~6 The group is selected from an aliphatic, or an unsubstituted 5-6 membered saturated, partially unsaturated, or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. A suitable divalent substituent to bond to an adjacent substituted carbon of the "may be substituted" group is -O(CR β 2) 2~3 O- is listed, and here each R that appears independently β C may be substituted with hydrogen as defined below. 1~6 The rings are selected from aliphatic, or unsubstituted 5-6 member saturated, partially unsaturated, or aromatic rings having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0070] R γ Suitable substituents on the aliphatic group include halogens and -R δ ,-(HaroR δ ), -OH, -OR δ ,-O(HaroR δ ), -CN, -C(O)OH, -C(O)OR δ -NH2, -NHR δ , -NR δ 2, or -NO2, where each R δ It is either unsubstituted, or if preceded by "halo", it is substituted by only one or more halogens, and independently C 1~4 Aliphatic, -CH2Ph, -O(CH2) 0~1It is a 5-6 member saturated, partially unsaturated, or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0071] A suitable substituent on the substituted nitrogen of the "may be substituted" group is -R ε , -NR ε 2, -C(O)R ε , -C(O)OR ε ,-C(O)C(O)R ε , -C(O)CH2C(O)R ε -S(O)2R ε -S(O)2NR ε 2, -C(S)NR ε 2, -C(NH)NR ε 2, or -N(R ε )S(O)2R ε These are listed, and here each R ε C is independently a hydrogen atom, which may be substituted as defined below. 1~6 An aliphatic, unsubstituted-OPh, or unsubstituted 5-6 member saturated, partially unsaturated, or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur, or, notwithstanding the above definition, two independently occurring R ε These atoms, together with the intervening atoms, form unsubstituted, monocyclic or bicyclic 3-12 member saturated, partially unsaturated, or aromatic rings having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0072] R ε Suitable substituents on the aliphatic group are, independently, halogens and -R δ ,-(HaroR δ ), -OH, -OR δ -CN, -C(O)OH, -C(O)OR δ -NH2, -NHR δ , -NR δ 2, or -NO2, where each R δ It is either unsubstituted, or if preceded by "halo", it is substituted by only one or more halogens, and independently C 1~4Aliphatic, -CH2Ph, -O(CH2) 0~1 It is a 5-6 member saturated, partially unsaturated, or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur.

[0073] In some aspects, the term “substituted” is assumed to include all permissible substituents of an organic compound, and “permissible” is in the context of the laws of valence chemistry known to those skilled in the art. In some cases, “substituted” may generally mean the replacement of a hydrogen atom by a substituent as described herein. However, as used herein, “substituted” does not imply that a molecule replaces and / or modifies the major functional group it identifies, for example, such that the “substituted” functional group becomes a different functional group through substitution. For example, a “substituted phenyl” group must still contain the phenyl moiety and, in this definition, cannot be modified by substitution to become, for example, a cyclohexyl group. In a broad context, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of an organic compound. Exemplary substituents include, for example, those described herein. Permissible substituents may be one or more, the same or different, for a given organic compound. For example, a substituted alkyl group may be CF3. In the present invention, a heteroatom such as nitrogen may have a hydrogen substituent and / or any acceptable substituent of the organic compound described herein that satisfies the valence of the heteroatom. The present invention is by no means intended to be limited by the acceptable substituents of the organic compound.

[0074] Examples of substituents include, but are not limited to, alkyl, aryl, arylalkyl, cyclic alkyl, heterocycloalkyl, hydroxy, alkoxy, aryloxy, perhaloalkoxy, arylalkoxy, heteroaryl, heteroaryloxy, heteroarylalkyl, heteroarylalkoxy, azide, amino, halogen, alkylthio, oxo, acylalkyl, carboxyester, carboxyl, carboxamide, nitro, acyloxy, aminoalkyl, alkylaminoaryl, alkylaryl, alkylaminoalkyl, alkoxyaryl, arylamino, arylalkylamino, alkylsulfonyl, carboxamidealkylaryl, carboxamidearyl, hydroxyalkyl, haloalkyl, alkylaminoalkylcarboxy, aminocarboxamidealkyl, cyano, alkoxyalkyl, perhaloalkyl, and arylalkyloxyalkyl.

[0075] As used herein, the term “natural oil” means an oil derived from a plant source or an animal source. Unless otherwise indicated, the term “natural oil” includes natural oil derivatives. Unless otherwise indicated, the plant source or animal source may be a modified plant source or animal source (e.g., a genetically modified plant source or animal source). Examples of natural oils include, but are not limited to, vegetable oils, algal oils, fish oils, animal fats, tall oils, derivatives of these oils, and any combination of these oils.

[0076] The term "vegetable oil" means natural oils or natural oil derivatives derived from any suitable component or any combination of components of plants (e.g., vegetables, fruits, leaves, stems, shrubs, flowers, seeds, or nuts). Representative and non-limiting examples of vegetable oils include almond oil, canola oil, avocado oil, argan oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, grape seed oil, olive oil, palm oil, peanut oil, hemp seed oil, macadamia oil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tuni oil, jatropha oil, jojoba oil, mustard oil, shepherd's purse oil, cinnamon oil, and castor oil. Representative and non-limiting examples of animal fats include lard, beef tallow, poultry fat, yellow grease, and fish oil. Tall oil is a by-product of wood pulp production. "Natural seed oil" refers to a type of natural vegetable oil that is obtained specifically from the seeds of plants rather than from the fruits (or other components) of those plants. Therefore, not all vegetable oils are seed oils. For example, olive oil and peanut oil are not natural seed oils. Representative and non-exclusive examples of natural seed oils include almond oil, canola oil, avocado oil, argan oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, grape seed oil, hemp seed oil, macadamia oil, safflower oil, sesame oil, soybean oil, sunflower oil, flaxseed oil, palm kernel oil, tuni oil, jatropha oil, jojoba oil, mustard oil, shepherd's purse oil, custard oil, and castor oil.

[0077] "Natural oil derivatives" means compounds (or mixtures of compounds) derived from natural oils using one or a combination of methods known in the art. These methods include, but are not limited to, saponification, oleolysis, transesterification, esterification, hydrogenation (partial or complete), isomerization, oxidation, reduction, and metathesis. Typical and non-limiting examples of natural oil derivatives include gums, phospholipids, soda oil residues, dark oils, distillates or distillate sludges, fatty acids, and fatty acid alkyl esters (non-limiting examples such as 2-ethylhexyl esters), as well as their hydroxy-substituted varieties. For example, natural oil derivatives may be fatty acid methyl esters ("FAMEs") derived from natural oil glycerides.

[0078] The term "contaminant" broadly and non-limitingly refers to any impurities mixed with the substrate used in olefin metathesis, regardless of their abundance. "Catalyst-poisoning contaminant" refers to a contaminant that may adversely affect the performance of the metathesis catalyst. Examples of catalyst-poisoning contaminants include, but are not limited to, water, peroxides, and hydroperoxides.

[0079] III. Methods for synthesizing aliphatic olefin metathesis products In some embodiments, the present invention relates to a method for synthesizing a Z-enriched aliphatic olefin metathesis product, comprising the step of contacting an olefin metathesis reaction partner and an internal olefin in the presence of a group 8 transition metal metathesis catalyst in order to form a Z-enriched aliphatic olefin metathesis product, wherein The aliphatic olefin metathesis product is an acylated alkenol or alkenal acetal. The olefin metathesis reaction partner contains a mixture of Z-olefin and E-olefin in a starting Z:E ratio. The aliphatic olefin metathesis product contains a mixture of Z-olefin and E-olefin in a Z:E ratio. This method provides a way in which the product Z:E ratio is higher than the starting Z:E ratio.

[0080] The method of the present invention is highly Z-selective, with over 80% of the metathesis products formed being in the Z configuration. More specifically, the method of the present invention produces aliphatic olefin metathesis products that are at least 97% Z, such as the compound of formula I. Furthermore, the present invention provides a method for producing aliphatic olefin metathesis products with high Z isomer purity from olefin starting materials with low Z isomer purity.

[0081] In some embodiments, Equation I: A method for synthesizing aliphatic olefin metathesis products of TIFF2026086750000021.tif16128 is provided. This method uses formula III to form aliphatic olefin metathesis products. The olefin metathesis reaction partners of TIFF2026086750000022.tif16128 and formula IV: The process includes contacting the internal olefin of TIFF2026086750000023.tif10128 with a metathesis catalyst, in which, R 1 H and C 1~6 Selected from the group consisting of alkyl groups; R 2 is C 1~18 Alkyl and C 2~18 Selected from the group consisting of alkenils; R 3 is C 1~18 It is alkyl; The subscript y is an integer in the range of 0 to 17; The subscript z is an integer in the range of 0 to 17; Metathesis catalysts are Z-selective group 8 transition metal catalysts.

[0082] In some embodiments, the aliphatic olefin metathesis product is given by formula VI: It is an alkenal acetal of TIFF2026086750000024.tif16128; The metathesis reaction partner is given by formula VII: It is a compound of TIFF2026086750000025.tif16128; The internal olefin is given by formula IV: It is a compound of TIFF2026086750000026.tif10128; R 1 is C 1~6 It is alkyl; R 2 is C 1~18 Alkyl and C 2~18 Selected from the group consisting of alkenils; R 3 is C 1~18 It is alkyl; The subscript y is an integer in the range of 0 to 17; The subscript z is an integer in the range of 0 to 17; Group 8 transition metal metathesis catalysts are Z-selective Group 8 transition metal catalysts.

[0083] Metathesis of aliphatic olefin derivatives In some embodiments, Equation I: The method for synthesizing the aliphatic olefin metathesis product of TIFF2026086750000027.tif16128 is to form the aliphatic olefin metathesis product using formula III: The olefin metathesis reaction partners of TIFF2026086750000028.tif16128 and formula IV: The process includes contacting the internal olefin of TIFF2026086750000029.tif10128 with a Z-selective Group 8 transition metal catalyst metathesis catalyst (e.g., a Z-selective ruthenium catalyst or a Z-selective osmium catalyst), wherein, R 1 H and C 1~6 Selected from the group consisting of alkyl groups; R 2 is C 1~18 Alkyl and C 2~18 Selected from the group consisting of alkenils; R 3 is C 1~18 It is alkyl; The subscript y is an integer in the range of 0 to 17; The subscript z is an integer in the range of 0 to 17.

[0084] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I is provided, using an acylating agent and formula II: The process further includes a step of contacting the alkenol of TIFF2026086750000030.tif10128 with the alkenol to form an olefin metathesis reaction partner of formula III.

[0085] In some embodiments, the acylating agent used to form the olefin metathesis reaction partner of formula III by contacting it with the alkenol of formula II is acetic anhydride.

[0086] Any acyling agent suitable for forming the olefin metathesis reaction partner of formula III can be used in the method of the present invention. Examples of suitable acyling agents include acid anhydrides (e.g., acetic anhydride), acid chlorides (e.g., acetyl chloride), activated esters (e.g., pentafluorophenyl carboxylic acids), and carboxylic acids used with coupling agents such as dicyclohexylcarbodiimide or carbonyldiimidazole. Typically, 1 to 10 molar equivalents of the acyling agent are used relative to the alkenol. For example, 1 to 5 equivalents or 1 to 2 equivalents of the acyling agent can be used. In some embodiments, about 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5 molar equivalents of the acyling agent (e.g., acetic anhydride) are used relative to the alkenol to form the olefin metathesis reaction partner of formula III.

[0087] The use of a base can promote the acylation of alkenols by an acylating agent. Suitable bases include potassium carbonate, sodium carbonate, sodium acetate, Hünig base (i.e., N,N-diisopropylethylamine), lutidine including 2,6-lutidine (i.e., 2,6-dimethylpyridine), triethylamine, tributylamine, pyridine, 2,6-di-tert-butylpyridine, 1,8-diazabicycloundeca-7-ene (DBU), quinuclidine, and colidine. Combinations of two or more bases can be used. Typically, less than 1 molar equivalent of the base is used in the method of the present invention relative to the alkenol. For example, 0.05 to 0.9 molar equivalents or 0.1 to 0.5 molar equivalents of the base can be used. In some embodiments, about 0.05, 0.1, 0.15, or 0.2 molar equivalents of the base (e.g., sodium acetate) relative to the alkenol is used in combination with an acylating agent (e.g., acetic anhydride) to form the olefin metathesis reaction partner of formula III.

[0088] Any suitable solvent can be used to acylate the alkenol. Suitable solvents include, but are not limited to, toluene, methylene chloride, ethyl acetate, acetonitrile, tetrahydrofuran, benzene, chloroform, diethyl ether, dimethylformamide, dimethyl sulfoxide, petroleum ether, and mixtures thereof. Alternatively, an alkenol such as (Z)-octadeca-9-en-1-ol (i.e., oleyl alcohol) may be combined with an acylating agent such as acetic anhydride and a base such as sodium acetate without further solvent. Typically, the acylation reaction is carried out at a temperature in the range of about 25°C to about 100°C for a period of time sufficient to form the olefin metathesis reaction partners of formula III. The reaction can be carried out for a period ranging from a few minutes to several hours or longer, depending on the specific alkenol and acylating agent used in the reaction. For example, the reaction can be carried out at approximately 40°C, 50°C, 60°C, 70°C, or 80°C for approximately 10 minutes, 30 minutes, 1 hour, 2 hours, 4 hours, 8 hours, or 12 hours.

[0089] Therefore, in some embodiments, the present invention relates to formula I: A method for synthesizing an aliphatic olefin metathesis product of TIFF2026086750000031.tif16128, wherein formula III: To form an olefin metathesis reaction partner in TIFF2026086750000032.tif16128, an acylating agent and formula II: The process of contacting the alkenol of TIFF2026086750000033.tif10128; and To form an aliphatic olefin metathesis product, use an olefin metathesis reaction partner and formula IV: The process includes contacting the internal olefin of TIFF2026086750000034.tif10128 with a Z-selective ruthenium catalyst or a Z-selective osmium catalyst, wherein, R1 H and C 1~6 Selected from the group consisting of alkyl groups; R 2 C 1~18 Alkyl and C 2~18 Selected from the group consisting of alkenils; R 3 C 1~18 It is alkyl; The subscript y is an integer in the range of 0 to 17; This provides a method where the subscript z is an integer in the range of 0 to 17.

[0090] In some embodiments, a method for synthesizing aliphatic olefin metathesis products is given by formula IIa: The process further includes the step of reducing an unsaturated aliphatic carboxyl derivative of TIFF2026086750000035.tif16128 to form an alkenol of formula II, In the formula, R 4 H and C 1~8 Selected from the group consisting of alkyl groups.

[0091] In some embodiments, the step of forming the alkenol of formula II includes contacting an unsaturated aliphatic carboxyl derivative of formula IIa with a base in the presence of a hydrogenation catalyst and hydrogen gas. Homogeneous or heterogeneous conditions can be used. Examples of homogeneous conditions include, but are not limited to, hydrogenolysis using a linked transition metal catalyst (Werkmeister, S. et al. Org. Process Res. Dev. 2014, 18, 289-302; Tan, et al. Org. Lett. 2015, 17 (3), 454; Spasyuk, D. et al. J. Am. Chem. Soc. 2015, 137, 3743; WO 2014 / 139030) and metal hydride catalyzed reduction reactions using a silane reagent (Mimoun, HJ Org. Chem. 1999, 64, 2582; U.S. Patent No. 6,533,960). Examples of heterogeneous conditions include, but are not limited to, the hydrogenation of unsaturated aliphatic carboxyl derivatives of formula IIa using ZnO or CuO / ZnO supported on chromite, alumina, or other materials to form alkenols of formula II. Any suitable combination of conditions for reducing unsaturated aliphatic carboxyl derivatives of formula IIa to alkenols of formula II can be used in the method of the present invention.

[0092] In some embodiments, the hydrogenation catalyst used to form alkenols of formula IIa from unsaturated aliphatic carboxyl derivatives of formula IIa is a homogeneous transition metal catalyst containing a pincer-type or tridentate or tetradentate ligand. Non-limiting examples of suitable homogeneous transition metal catalysts include dichlorotriphenylphosphine[bis(2-(ethylthio)ethyl)amine]ruthenium(II) and dichlorotriphenylphosphine[2-(diphenylphosphino)-N-(2-pyridinylmethyl)ethaneamine]ruthenium(II). Those skilled in the art will be able to select a suitable hydrogenation catalyst for reducing unsaturated aliphatic carboxyl derivatives (e.g., alkyl ester-containing compounds) to the corresponding alkenols (e.g., alcohol-containing compounds). Other homogeneous transition metal catalysts suitable for hydrogenating alkyl ester groups to alcohol groups are known to those skilled in the art, including, for example, the catalyst described in Werkmeister, S. et al. Org. Process Res. Dev. 2014, 18, 289-302. Typically, the hydrogenation catalyst is used in a quasi-stoichiometric amount (e.g., catalytic amount) in the presence of hydrogen gas and a suitable base, such as sodium ethoxide, sodium methoxide, or sodium tert-butoxide. In some embodiments, the step of forming the alkenol of formula II includes contacting an unsaturated aliphatic carboxyl derivative of formula IIa, which is an unsaturated fatty acid alkyl ester, with a base in the presence of the hydrogenation catalyst and hydrogen gas. In some embodiments, the step of forming the alkenol of formula II includes contacting the R of formula IIa 4 C 1~8 The process includes contacting an alkyl unsaturated aliphatic carboxyl derivative of formula IIa with a base in the presence of a hydrogenation catalyst and hydrogen gas.

[0093] In some embodiments, the step of forming the alkenol of formula II includes contacting an unsaturated aliphatic carboxyl derivative of formula IIa with a reducing agent. Any suitable reducing agent, such as sodium borohydride, sodium triacetoxyborohydride, sodium cyanoborohydride, lithium aluminum hydride, diisobutylaluminum hydride (CN 103319704; Chandrasekhar, et al. Tetrahedron Lett. 1998, 39, 909), and sodium bis(2-methoxyethoxy)aluminum hydride ("SMEAH"; also known by trade names RED-AL, SYNHYDRIDE, and VITRIDE), can be used to reduce the unsaturated aliphatic carboxyl derivative of formula IIa to the alkenol of formula II. In some embodiments, the reducing agent is sodium bis(2-methoxyethoxy)aluminum hydride.

[0094] Typically, 1 to 2 molar equivalents of a reducing agent are used with respect to an unsaturated aliphatic carboxyl derivative. In some embodiments, about 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5 molar equivalents of a reducing agent are used with respect to an unsaturated aliphatic carboxyl derivative to form the corresponding alkenol. In some embodiments, the step of forming the alkenol of formula II includes contacting an unsaturated aliphatic carboxyl derivative of formula IIa, which is an unsaturated fatty acid, with a reducing agent. In some embodiments, the step of forming the alkenol of formula II includes contacting an R of formula IIa 4 The process includes contacting an unsaturated aliphatic carboxyl derivative of formula IIa, where H is present, with a reducing agent. Typically, the unsaturated fatty acid reduction reaction is carried out at a temperature in the range of about -78°C to about 25°C for a period of time sufficient to form an alkenol. Depending on the specific unsaturated fatty acid and reducing agent used in the reaction, the reaction can be carried out for a period of time ranging from a few minutes to several hours or longer. For example, the reduction of (Z)-icosa-11-enoic acid with an aluminum reagent (e.g., sodium bis(2-methoxyethoxy)aluminum hydride) can be carried out at a temperature in the range of about 0°C to about 20°C for 1 to 2 hours.

[0095] Any suitable solvent can be used to reduce the unsaturated aliphatic carboxyl derivative of formula IIa (e.g., with a base and a hydrogenation catalyst and hydrogen gas, or with a reducing agent). Suitable solvents include, but are not limited to, toluene, methylene chloride, ethyl acetate, acetonitrile, tetrahydrofuran, benzene, chloroform, diethyl ether, dimethylformamide, dimethyl sulfoxide, petroleum ether, and mixtures thereof.

[0096] Therefore, in some embodiments, the present invention relates to formula I: A method for synthesizing an aliphatic olefin metathesis product of TIFF2026086750000036.tif16128, wherein formula II: To form the alkenol of TIFF2026086750000037.tif10128, formula IIa: A process for reducing the unsaturated aliphatic carboxyl derivative of TIFF2026086750000038.tif16128; Formula III: The steps of contacting an acylating agent with an alkenol to form an olefin metathesis reaction partner of TIFF2026086750000039.tif16128; and To form an aliphatic olefin metathesis product, use an olefin metathesis reaction partner and formula IV: The process includes contacting the internal olefin of TIFF2026086750000040.tif10128 with a Z-selective ruthenium catalyst or a Z-selective osmium catalyst, wherein, R 1 H and C 1~6 Selected from the group consisting of alkyl groups; R 2 C 1~18 Alkyl and C 2~18 Selected from the group consisting of alkenils; R 3 C 1~18 It is alkyl; R 4 H and C 1~8 Selected from the group consisting of alkyl groups; The subscript y is an integer in the range of 0 to 17; This provides a method where the subscript z is an integer in the range of 0 to 17.

[0097] In some embodiments, the synthesis of an aliphatic olefin metathesis product of formula I according to any of the methods described herein may further include contacting the olefin metathesis reaction partner of formula III with a pretreatment reagent before contacting the olefin with the olefin. In some embodiments, the pretreatment reagent is selected from the group consisting of alumina and magnesium aluminum isopropoxide. In some embodiments, the pretreatment reagent is alumina. In some embodiments, the pretreatment reagent is magnesium aluminum isopropoxide.

[0098] In some embodiments, R in formulas I and III 1 H and C 1~6 Selected from the group consisting of alkyl groups. In some embodiments, R 1 H is H. In some embodiments, R 1 is C 1~6 It is alkyl. In some embodiments, R 1 The group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, and 1-ethyl-2-methylpropyl. In some embodiments, R 1R is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl. In some embodiments, R 1 H and C 1~3 Selected from the group consisting of alkyl groups. In some embodiments, R 1 R is selected from the group consisting of H, methyl, ethyl, and propyl. In some embodiments, R 1 R is selected from the group consisting of H, methyl, and ethyl. In some embodiments, R 1 R is selected from the group consisting of H and methyl. In some embodiments, R 1 It is methyl.

[0099] In some embodiments, R in equations IIa, II, and III 2 is C 1~18 Alkyl and C 2~18 Selected from the group consisting of alkenyls. In some embodiments, R 2 is C 1~18 It is alkyl. In some embodiments, R 2 is C 2~18 It is an alkenil. In some embodiments, R 2 is C 1~18 Alkyl, C 2~18 Alkyl, C 3~18 Alkyl, C 4~18 Alkyl, C 5~18 Alkyl, C 6~18 Alkyl, C 6~18 Alkyl, C 7~18 Alkyl, C 8~18 Alkyl, C 9~18 Alkyl, C 10~18 Alkyl, C 11~18 Alkyl, C 12~18 Alkyl, C 13~18 Alkyl, C 14~18 Alkyl, C 15~18 Alkyl, C 16~18 Alkyl, and C 17~18 Selected from the group consisting of alkyl groups. In some embodiments, R 2 is C 2~18 Alkenil, C 3~18 Alkenil, C 4~18 Alkenil, C 5~18Alkenil, C 6~18 Alkenil, C 7~18 Alkenil, C 8~18 Alkenil, C 9~18 Alkenil, C 10~18 Alkenil, C 11~18 Alkenil, C 12~18 Alkenil, C 13~18 Alkenil, C 14~18 Alkenil, C 15~18 Alkenil, C 16~18 Alkenyl and C 17~18 Selected from the group consisting of alkenyls. In some embodiments, R 2 The linear C is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl. 1~18 It is alkyl. In some embodiments, R 2 This refers to a straight-chain C hydrocarbon having a carbon-carbon double bond at any position in the hydrocarbon chain, selected from the group consisting of vinyl, propenyl, n-butenyl, n-pentenyl, n-hexenyl, n-heptenyl, n-octenyl, n-nonenyl, n-decenyl, n-undecenyl, n-dodecenyl, n-tridecenyl, n-tetradecenyl, n-pentadecenyl, n-hexadecenyl, n-heptadecenyl, and n-octadecenyl. 2~18 It is Alkenil.

[0100] In some embodiments, R in equations IIa, II, and III 2 is C 1~12 Alkyl and C 2~12 Selected from the group consisting of alkenyls. In some embodiments, R 2 R is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, vinyl, propenyl, n-butenyl, n-pentenyl, n-hexenyl, n-heptenyl, n-octenyl, n-nonenyl, n-decenyl, n-undecenyl, and n-dodecenyl. In some embodiments, R2 is C 1~12 It is alkyl. In some embodiments, R 2 R is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl. In some embodiments, R 2 R is selected from the group consisting of n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl. In some embodiments, R 2 R is selected from the group consisting of n-pentyl, n-hexyl, n-heptyl, n-octyl, and n-nonyl. In some embodiments, R 2 R is selected from the group consisting of n-hexyl, n-heptyl, and n-octyl. In some embodiments, R 2 is n-octyl. In some embodiments, R 2 It is not H.

[0101] In some embodiments, R in Equation III 3 is C 1~18 It is alkyl. In some embodiments, R 3 is C 1~18 Alkyl, C 1~17 Alkyl, C 1~16 Alkyl, C 1~15 Alkyl, C 1~14 Alkyl, C 1~13 Alkyl, C 1~12 Alkyl, C 1~11 Alkyl, C 1~10 Alkyl, C 1~9 Alkyl, C 1~8 Alkyl, C 1~7 Alkyl, C 1~6 Alkyl, C 1~5 Alkyl, C 1~4 Alkyl, C 1~3 Alkyl, and C 1~2 Selected from the group consisting of alkyl groups. In some embodiments, R 3The linear C is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl. 1~18 It is alkyl. In some embodiments, R 3 is C 1~12 It is alkyl. In some embodiments, R 3 R is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl. In some embodiments, R 3 R is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. In some embodiments, R 3 R is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl. In some embodiments, R 3 R is selected from the group consisting of ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl. In some embodiments, R 3 is n-butyl. In some embodiments, R 3 is n-propyl. In some embodiments, R 3 is ethyl. In some embodiments, R 3 It is not H.

[0102] In some aspects, R in equation IIa 4 H and C 1~8 Selected from the group consisting of alkyl groups. In some embodiments, R 4 H is H. In some embodiments, R 4 is C 1~8 It is alkyl. In some embodiments, R 4The group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, and octyl. In some embodiments, R 4 R is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. In some embodiments, R 4 H and C 1~3 Selected from the group consisting of alkyl groups. In some embodiments, R 4 R is selected from the group consisting of H, methyl, ethyl, and propyl. In some embodiments, R 4 R is selected from the group consisting of H, methyl, and ethyl. In some embodiments, R 4 R is selected from the group consisting of H and methyl. In some embodiments, R 4 H is H. In some embodiments, R 4 R is methyl. 4 When is H, the unsaturated aliphatic carboxyl derivative of formula IIa is an unsaturated fatty acid. 4 C 1~8 Alkyl or C 1~3 When it is alkyl, the unsaturated aliphatic carboxyl derivative of formula IIa is an unsaturated fatty acid alkyl ester.

[0103] In some embodiments, the subscript y in equations I, IIa, II, and III is an integer in the range of 0 to 17. In some embodiments, the subscript y is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17. In some embodiments, the subscript y is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16. In some embodiments, the subscript y is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15. In some embodiments, the subscript y is an integer in the range of 5 to 15. In some embodiments, the subscript y is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15. In some embodiments, the subscript y is 6, 7, 8, 9, 10, 11, 12, or 13. In some embodiments, the subscript y is 7, 9, 11, or 13. In some embodiments, the subscript y is 7. In some embodiments, the subscript y is 9. In some embodiments, the subscript z in equations I and IV is an integer in the range of 0 to 17. In some embodiments, the subscript z is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17. In some embodiments, the subscript z is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14. In some embodiments, the subscript z is an integer in the range of 0 to 7. In some embodiments, the subscript z is 0, 1, 2, 3, 4, 5, 6, or 7. In some embodiments, the subscript z is an integer in the range of 0 to 5. In some embodiments, the subscript z is 0, 1, 2, 3, 4, or 5. In some embodiments, the subscript z is 1, 2, 3, or 4. In some embodiments, the subscript z is 1. In some embodiments, the subscript z is 2. In some embodiments, the subscript z is 3.

[0104] In some embodiments, an aliphatic olefin metathesis product of formula I is prepared by using the method described herein, where y is 0 and z is 4; or y is 1 and z is 3; or y is 3 and z is 1; or y is 4 and z is 0; or y is 0 and z is 5; or y is 1 and z is 4; or y is 2 and z is 3; or y is 3 and z is 2; or y is 4 and z is 1; or y is 5 and z is 0; or y is 0 and z is 6; or y is 1 and z is 5; or y is 2 and z is 4; or y is 4 and z is 2; or y is 5 and z is 1; or y is 6 and z is 0; or y is 0 and z is 7; Alternatively, y is 1 and z is 6; or y is 2 and z is 5; or y is 3 and z is 4; or y is 4 and z is 3; or y is 5 and z is 2; or y is 6 and z is 1; or y is 7 and z is 0; or y is 0 and z is 8; or y is 1 and z is 7; or y is 2 and z is 6; or y is 3 and z is 5; or y is 5 and z is 3; or y is 6 and z is 2; or y is 7 and z is 1; or y is 8 and z is 0; or y is 0 and z is 9; or y is 1 and z is 8; or y is 2 and z is 7; Alternatively, y is 3 and z is 6; or y is 4 and z is 5; or y is 5 and z is 4; or y is 6 and z is 3; or y is 7 and z is 2; or y is 8 and z is 1; or y is 9 and z is 0; or y is 0 and z is 10; or y is 1 and z is 9; or y is 2 and z is 8; or y is 3 and z is 7; or y is 4 and z is 6;Alternatively, y is 6 and z is 4; or y is 7 and z is 3; or y is 8 and z is 2; or y is 9 and z is 1; or y is 10 and z is 0; or y is 0 and z is 11; or y is 1 and z is 10; or y is 2 and z is 9; or y is 3 and z is 8; or y is 4 and z is 7; or y is 5 and z is 6; or y is 6 and z is 5; or y is 7 and z is 4; or y is 8 and z is 3; or y is 9 and z is 2; or y is 10 and z is 1; or y is 11 and z is 0; or y is 0 and z is 12; Alternatively, y is 1 and z is 11; or y is 2 and z is 10; or y is 3 and z is 9; or y is 4 and z is 8; or y is 5 and z is 7; or y is 7 and z is 5; or y is 8 and z is 4; or y is 9 and z is 3; or y is 10 and z is 2; or y is 11 and z is 1; or y is 12 and z is 0; or y is 0 and z is 13; or y is 1 and z is 12; or y is 2 and z is 11; or y is 3 and z is 10; or y is 4 and z is 9; or y is 5 and z is 8; or y is 6 and z is 7; Alternatively, y is 7 and z is 6; or y is 8 and z is 5; or y is 9 and z is 4; or y is 10 and z is 3; or y is 11 and z is 2; or y is 12 and z is 1; or y is 13 and z is 0; or y is 0 and z is 14; or y is 1 and z is 13; or y is 2 and z is 12; or y is 3 and z is 11; or y is 4 and z is 10;Alternatively, y is 5 and z is 9; or y is 6 and z is 8; or y is 8 and z is 6; or y is 9 and z is 5; or y is 10 and z is 4; or y is 11 and z is 3; or y is 12 and z is 2; or y is 13 and z is 1; or y is 14 and z is 0; or y is 0 and z is 15; or y is 1 and z is 14; or y is 2 and z is 13; or y is 3 and z is 12; or y is 4 and z is 11; or y is 5 and z is 10; or y is 6 and z is 9; or y is 7 and z is 8; or y is 8 and z is 7; Alternatively, y is 9 and z is 6; or y is 10 and z is 5; or y is 11 and z is 4; or y is 12 and z is 3; or y is 13 and z is 2; or y is 14 and z is 1; or y is 15 and z is 0; or y is 0 and z is 16; or y is 1 and z is 15; or y is 2 and z is 14; or y is 3 and z is 13; or y is 4 and z is 12; or y is 5 and z is 11; or y is 6 and z is 10; or y is 7 and z is 9; or y is 9 and z is 7; or y is 10 and z is 6; Alternatively, y is 11 and z is 5; or y is 12 and z is 4; or y is 13 and z is 3; or y is 14 and z is 2; or y is 15 and z is 1; or y is 16 and z is 0; or y is 1 and z is 16; or y is 2 and z is 15; or y is 3 and z is 14; or y is 4 and z is 13; or y is 5 and z is 12; or y is 6 and z is 11; or y is 7 and z is 10;Alternatively, y is 8 and z is 9; or y is 9 and z is 8; or y is 10 and z is 7; or y is 11 and z is 6; or y is 12 and z is 5; or y is 13 and z is 4; or y is 14 and z is 3; or y is 15 and z is 2; or y is 16 and z is 1; or y is 17 and z is 0; or y is 0 and z is 17; or y is 1 and z is 17; or y is 2 and z is 16; or y is 3 and z is 15; or y is 4 and z is 14; or y is 5 and z is 13; or y is 6 and z is 12; Alternatively, y is 7 and z is 11; or y is 8 and z is 10; or y is 10 and z is 8; or y is 11 and z is 7; or y is 12 and z is 6; or y is 13 and z is 5; or y is 14 and z is 4; or y is 15 and z is 3; or y is 16 and z is 2; or y is 17 and z is 1. In some embodiments, both y and z are 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17.

[0105] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I includes the step of contacting an olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where R 1 is C 1~3 It is alkyl, R 2 is C 1~12 It is alkyl, R 3 is C 1~12 It is an alkyl group, where y is an integer in the range of 5 to 15, and z is an integer in the range of 0 to 7. In some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I includes the step of contacting the olefin metathesis reaction partner of formula III with the internal olefin of formula IV, where R1 R is selected from the group consisting of H and methyl; 2 These are n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; R 3 R is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl; y is an integer in the range of 6 to 14; and z is an integer in the range of 1 to 4. In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I comprises the step of contacting an olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where R 1 is methyl; R 2 R is selected from the group consisting of n-hexyl, n-heptyl, and n-octyl; 3 R is selected from the group consisting of ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; y is an integer selected from the group consisting of 7, 9, 11, and 13; and z is an integer selected from the group consisting of 1, 2, and 3. In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I comprises the step of contacting an olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where R 1 is methyl; R 2 is n-octyl; R 3 is selected from the group consisting of ethyl and n-butyl; y is an integer selected from the group consisting of 7, 9, 11, and 13; and z is an integer selected from the group consisting of 1 and 3.

[0106] In some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I includes the step of contacting the olefin metathesis reaction partner of formula III with the internal olefin of formula IV, where the metathesis reaction partner of formula III is aliphatic C 12 ~C 30 It is an olefin acetate; the internal olefin in formula IV is C4~C 20 It is an internal olefin; the aliphatic olefin metathesis product of formula I is C8~C 28(Z)-unsaturated aliphatic ester acetate. In some embodiments, the metathesis reaction partner of formula III is aliphatic C 16 ~C 28 It is an olefin acetate; the internal olefin in formula IV is C4~C 12 It is an internal olefin; the aliphatic olefin metathesis product of formula I is C 12 ~C 24 (Z)-unsaturated aliphatic ester acetate. In some embodiments, the metathesis reaction partner of formula III is aliphatic C 18 ~C 26 It is an olefin acetate; the internal olefin in formula IV is C6~C 10 It is an internal olefin; the aliphatic olefin metathesis product of formula I is C 14 ~C 22 It is a (Z)-unsaturated aliphatic ester acetate.

[0107] In some embodiments, the present invention provides a method for synthesizing an aliphatic olefin metathesis product of formula I described herein, where the olefin metathesis reaction partner of formula III is selected from the group comprising octadeca-9-en-1-yl acetate, eicosa-11-en-yl acetate, docosa-13-en-1-yl acetate, tetracosa-15-en-1-yl acetate, or mixtures thereof. In some embodiments, the olefin metathesis reaction partner comprises octadeca-9-en-1-yl acetate and at least one member selected from the group comprising eicosa-11-en-yl acetate, docosa-13-en-1-yl acetate, and tetracosa-15-en-1-yl acetate. In some embodiments, the olefin metathesis reaction partner is selected from the group consisting of octadeca-9-en-1-yl acetate, eicosa-11-en-yl acetate, docosa-13-en-1-yl acetate, and tetracosa-15-en-1-yl acetate. In some embodiments, the olefin metathesis reaction partner is octadeca-9-en-1-yl acetate. In some embodiments, the olefin metathesis reaction partner is eicosa-11-en-1-yl acetate. In some embodiments, the olefin metathesis reaction partner is docosa-13-en-1-yl acetate. In some embodiments, the olefin metathesis reaction partner is tetracosa-15-en-1-yl acetate.

[0108] In some embodiments, the present invention provides a method for synthesizing an aliphatic olefin metathesis product of formula I as described herein, where the olefin of formula IV is selected from the group comprising hexadeca-8-ene, tetradeca-7-ene, dodeca-6-ene, deca-5-ene, octa-4-ene, or hexa-3-ene. In some embodiments, the olefin is selected from the group comprising hexadeca-8-ene, tetradeca-7-ene, dodeca-6-ene, deca-5-ene, octa-4-ene, and hexa-3-ene. In some embodiments, the olefin is selected from the group comprising tetradeca-7-ene, dodeca-6-ene, deca-5-ene, octa-4-ene, and hexa-3-ene. In some embodiments, the olefin is selected from the group comprising dodeca-6-ene, deca-5-ene, octa-4-ene, and hexa-3-ene. In some embodiments, the olefin is selected from the group consisting of deca-5-ene, octa-4-ene, and hexa-3-ene. In some embodiments, the olefin is deca-5-ene. In some embodiments, the olefin is octa-4-ene. In some embodiments, the olefin is hexa-3-ene.

[0109] In some embodiments, the present invention provides a method for synthesizing an aliphatic olefin metathesis product of formula I as described herein, wherein the aliphatic olefin metathesis product is (Z)-tetradeca-9-en-1-yl acetate, (Z)-hexadeca-11-en-1-yl acetate, (Z)-octadeca-13-en-1-yl acetate, (Z)-icosa-15-en-1-yl acetate, (Z)-trideca-9-en-1-yl acetate, (Z)-pentadeca-11-en-1-yl acetate, (Z)-heptadeca-13-en-1-yl acetate, (Z)-nonadeca-15-en-1-yl acetate, (Z)-dodeca-9-en-1-yl acetate, (Z)-tetradeca-11-en-1-yl The group comprises acetate, (Z)-hexadeca-13-en-1-yl acetate, (Z)-octadeca-15-en-1-yl acetate, or mixtures thereof. In some embodiments, the aliphatic olefin metathesis product comprises at least one member selected from the group consisting of (Z)-tetradeca-9-en-1-yl acetate, (Z)-hexadeca-11-en-1-yl acetate, (Z)-octadeca-13-en-1-yl acetate, and (Z)-icosa-15-en-1-yl acetate. In some embodiments, the aliphatic olefin metathesis product comprises at least one member selected from the group consisting of (Z)-trideca-9-en-1-yl acetate, (Z)-pentadeca-11-en-1-yl acetate, (Z)-heptadeca-13-en-1-yl acetate, and (Z)-nonadeca-15-en-1-yl acetate. In some embodiments, the aliphatic olefin metathesis product comprises at least one member selected from the group consisting of (Z)-dodeca-9-en-1-yl acetate, (Z)-tetradeca-11-en-1-yl acetate, (Z)-hexadeca-13-en-1-yl acetate, and (Z)-octadeca-15-en-1-yl acetate.In some embodiments, the aliphatic olefin metathesis product is selected from the group consisting of (Z)-tetradeca-9-en-1-yl acetate, (Z)-dodeca-9-en-1-yl acetate, and (Z)-tetradeca-11-en-1-yl acetate.

[0110] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I comprises the step of contacting an olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the olefin metathesis reaction partner of formula III comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-yl acetate, (Z)-icosa-11-en-1-yl acetate, (Z)-docosa-13-en-1-yl acetate, and (Z)-tetracosa-15-en-1-yl acetate; the internal olefin of formula IV is selected from the group consisting of (Z)-deca-5-ene, (Z)-octa-4-ene, and (Z)-hexa-3-ene; and the aliphatic olefin metathesis product of formula I is (Z)-tetradeca-9-en-1-yl acetate, (Z)-hexadeca-11-en-1-yl The material comprises at least one member selected from the group consisting of acetate, (Z)-octadeca-13-en-1-yl acetate, (Z)-icosa-15-en-1-yl acetate, (Z)-trideca-9-en-1-yl acetate, (Z)-pentadeca-11-en-1-yl acetate, (Z)-heptadeca-13-en-1-yl acetate, (Z)-nonadeca-15-en-1-yl acetate, (Z)-dodeca-9-en-1-yl acetate, (Z)-tetradeca-11-en-1-yl acetate, (Z)-hexadeca-13-en-1-yl acetate, and (Z)-octadeca-15-en-1-yl acetate.

[0111] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I comprises the step of contacting an olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the olefin metathesis reaction partner of formula III comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-yl acetate, (Z)-icosa-11-en-1-yl acetate, (Z)-docosa-13-en-1-yl acetate, and (Z)-tetracosa-15-en-1-yl acetate; the internal olefin of formula IV is (Z)-deca-5-ene; and the aliphatic olefin metathesis product of formula I is (Z)-tetradeca-9-en-1-yl acetate, (Z)-hexadeca-11-en-1-yl acetate, and (Z)-octadeca-13-en-1-yl It includes at least one member selected from the group consisting of acetate and (Z)-icosa-15-en-1-yl acetate.

[0112] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I comprises the step of contacting an olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the olefin metathesis reaction partner of formula III comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-yl acetate, (Z)-icosa-11-en-1-yl acetate, (Z)-docosa-13-en-1-yl acetate, and (Z)-tetracosa-15-en-1-yl acetate; the internal olefin of formula IV is (Z)-octa-4-en; and the aliphatic olefin metathesis product of formula I is (Z)-trideca-9-en-1-yl acetate, (Z)-pentadeca-11-en-1-yl acetate, and (Z)-heptadeca-13-en-1-yl It includes at least one member selected from the group consisting of acetate and (Z)-nonadeca-15-en-1-yl acetate.

[0113] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I comprises the step of contacting an olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the olefin metathesis reaction partner of formula III comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-yl acetate, (Z)-icosa-11-en-1-yl acetate, (Z)-docosa-13-en-1-yl acetate, and (Z)-tetracosa-15-en-1-yl acetate; the internal olefin of formula IV is (Z)-hexa-3-ene; and the aliphatic olefin metathesis product of formula I is (Z)-dodeca-9-en-1-yl acetate, (Z)-tetradeca-11-en-1-yl acetate, and (Z)-hexadeca-13-en-1-yl It includes at least one member selected from the group consisting of acetate and (Z)-octadeca-15-en-1-yl acetate.

[0114] In some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I includes contacting an olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the olefin metathesis reaction partner of formula III is (Z)-octadeca-9-en-1-yl acetate; the internal olefin of formula IV is (Z)-deca-5-ene; and the aliphatic olefin metathesis product of formula I is (Z)-tetradeca-9-en-1-yl acetate. In some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I includes contacting an olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the olefin metathesis reaction partner of formula III is (Z)-octadeca-9-en-1-yl acetate; the internal olefin of formula IV is (Z)-hexa-3-ene; and the aliphatic olefin metathesis product of formula I is (Z)-dodeca-9-en-1-yl acetate. In some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I comprises the step of contacting an olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the olefin metathesis reaction partner of formula III is (Z)-icosa-11-en-1-yl acetate; the internal olefin of formula IV is (Z)-hexa-3-ene; and the aliphatic olefin metathesis product of formula I is (Z)-tetradeca-11-en-1-yl acetate.

[0115] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I includes the steps of contacting an acylating agent with an alkenol of formula II to form an olefin metathesis reaction partner of formula III, and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where R 1 is C 1~3 It is alkyl, R 2 is C 1~12 It is alkyl, R 3 is C 1~12It is an alkyl group, where y is an integer in the range of 5 to 15, and z is an integer in the range of 0 to 7. In some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I comprises the steps of contacting an acylating agent with an alkenol of formula II to form an olefin metathesis reaction partner of formula III, and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where R 1 R is selected from the group consisting of H and methyl; 2 These are n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; R 3 R is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl; y is an integer in the range of 6 to 14; and z is an integer in the range of 1 to 4. In some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I comprises the steps of contacting an acylating agent with an alkenol of formula II to form an olefin metathesis reaction partner of formula III, and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, wherein R 1 is methyl; R 2 R is selected from the group consisting of n-hexyl, n-heptyl, and n-octyl; 3 a is selected from the group consisting of ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; y is an integer selected from the group consisting of 7, 9, 11, and 13; and z is an integer selected from the group consisting of 1, 2, and 3. In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I comprises the steps of contacting an acylating agent with an alkenol of formula II to form an olefin metathesis reaction partner of formula III, and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, wherein R 1 is methyl; R 2 is n-octyl; R 3is selected from the group consisting of ethyl and n-butyl; y is an integer selected from the group consisting of 7, 9, 11, and 13; and z is an integer selected from the group consisting of 1 and 3.

[0116] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I includes the steps of contacting an acylating agent with an alkenol of formula II to form an olefin metathesis reaction partner of formula III, and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the alkenol of formula II is C 10 ~C 28 It is an aliphatic alkenol; the metathesis reaction partner in formula III is C 10 ~C 28 It is an acetate ester of an aliphatic alkenol; the internal olefin of formula IV is C4~C 20 It is an internal olefin; the aliphatic olefin metathesis product of formula I is C8~C 28 (Z)-Unsaturated aliphatic ester acetate. In some embodiments, the alkenol of formula II is C 14 ~C 26 It is an aliphatic alkenol; the metathesis reaction partner in formula III is C 14 ~C 26 It is an acetate ester of an aliphatic alkenol; the internal olefin of formula IV is C4~C 12 It is an internal olefin; the aliphatic olefin metathesis product of formula I is C 12 ~C 24 (Z)-Unsaturated aliphatic ester acetate. In some embodiments, the alkenol of formula II is C 16 ~C 24 It is an aliphatic alkenol; the metathesis reaction partner in formula III is C 16 ~C 24 It is an acetate ester of an aliphatic alkenol; the internal olefin of formula IV is C6~C 10 It is an internal olefin; the aliphatic olefin metathesis product of formula I is C 14 ~C 22 It is a (Z)-unsaturated aliphatic ester acetate.

[0117] In some embodiments, the present invention provides a method for synthesizing an aliphatic olefin metathesis product of formula I described herein, where the alkenol of formula II is selected from the group comprising octadeca-9-en-1-ol, eicosa-11-en-1-ol, docosa-13-en-1-ol, tetracosa-15-en-ol, or mixtures thereof. In some embodiments, the alkenol is selected from the group comprising octadeca-9-en-1-ol, eicosa-11-en-1-ol, docosa-13-en-1-ol, and tetracosa-15-en-ol. In some embodiments, the alkenol is octadeca-9-en-1-ol. In some embodiments, the alkenol is eicosa-11-en-1-ol. In some embodiments, the alkenol is docosa-13-en-1-ol. In some embodiments, the alkenol is tetracosa-15-en-ol.

[0118] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I comprises the steps of contacting an acylating agent with an alkenol of formula II to form an olefin metathesis reaction partner of formula III, and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the alkenol of formula II comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-ol, (Z)-icosa-11-en-1-ol, (Z)-docosa-13-en-1-ol, and (Z)-tetracosa-15-en-ol; and the olefin metathesis reaction partner of formula III comprises (Z)-octadeca-9-en-1-yl acetate, (Z)-icosa-11-en-1-yl acetate, (Z)-docosa-13-en-1-yl acetate, and (Z)-tetracosa-15-en-1-yl Formula IV comprises at least one member selected from the group consisting of acetates; the internal olefin of formula IV is selected from the group consisting of (Z)-deca-5-ene, (Z)-octa-4-ene, and (Z)-hexa-3-ene; the aliphatic olefin metathesis product of formula I is (Z)-tetradeca-9-en-1-yl acetate, (Z)-hexadeca-11-en-1-yl acetate, (Z)-octadeca-13-en-1-yl acetate, (Z)-icosa-15-en-1-yl acetate, (Z)-trideca-9-en-1-yl acetate, (Z)-pentadeca-11-en-1-yl acetate, (Z)-heptadeca-13-en-1-yl acetate, and (Z)-nonadeca-15-en-1-yl It comprises at least one member selected from the group consisting of acetate, (Z)-dodeca-9-en-1-yl acetate, (Z)-tetradeca-11-en-1-yl acetate, (Z)-hexadeca-13-en-1-yl acetate, and (Z)-octadeca-15-en-1-yl acetate.

[0119] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I comprises the steps of contacting an acylating agent with an alkenol of formula II to form an olefin metathesis reaction partner of formula III, and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the alkenol of formula II comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-ol, (Z)-icosa-11-en-1-ol, (Z)-docosa-13-en-1-ol, and (Z)-tetracosa-15-en-ol; and the olefin metathesis reaction partner of formula III comprises (Z)-octadeca-9-en-1-yl acetate, (Z)-icosa-11-en-1-yl acetate, (Z)-docosa-13-en-1-yl acetate, and (Z)-tetracosa-15-en-1-yl The product comprises at least one member selected from the group consisting of acetates; the internal olefin of formula IV is (Z)-deca-5-ene; the aliphatic olefin metathesis product of formula I comprises at least one member selected from the group consisting of (Z)-tetradeca-9-en-1-yl acetate, (Z)-hexadeca-11-en-1-yl acetate, (Z)-octadeca-13-en-1-yl acetate, and (Z)-icosa-15-en-1-yl acetate.

[0120] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I comprises the steps of contacting an acylating agent with an alkenol of formula II to form an olefin metathesis reaction partner of formula III, and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the alkenol of formula II comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-ol, (Z)-icosa-11-en-1-ol, (Z)-docosa-13-en-1-ol, and (Z)-tetracosa-15-en-ol; and the olefin metathesis reaction partner of formula III comprises (Z)-octadeca-9-en-1-yl acetate, (Z)-icosa-11-en-1-yl acetate, (Z)-docosa-13-en-1-yl acetate, and (Z)-tetracosa-15-en-1-yl The product comprises at least one member selected from the group consisting of acetates; the internal olefin of formula IV is (Z)-octa-4-ene; the aliphatic olefin metathesis product of formula I comprises at least one member selected from the group consisting of (Z)-trideca-9-en-1-yl acetate, (Z)-pentadeca-11-en-1-yl acetate, (Z)-heptadeca-13-en-1-yl acetate, and (Z)-nonadeca-15-en-1-yl acetate.

[0121] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I comprises the steps of contacting an acylating agent with an alkenol of formula II to form an olefin metathesis reaction partner of formula III, and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the alkenol of formula II comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-ol, (Z)-icosa-11-en-1-ol, (Z)-docosa-13-en-1-ol, and (Z)-tetracosa-15-en-ol; and the olefin metathesis reaction partner of formula III comprises (Z)-octadeca-9-en-1-yl acetate, (Z)-icosa-11-en-1-yl acetate, (Z)-docosa-13-en-1-yl acetate, and (Z)-tetracosa-15-en-1-yl The product comprises at least one member selected from the group consisting of acetates; the internal olefin of formula IV is (Z)-hexa-3-ene; the aliphatic olefin metathesis product of formula I comprises at least one member selected from the group consisting of (Z)-dodeca-9-en-1-yl acetate, (Z)-tetradeca-11-en-1-yl acetate, (Z)-hexadeca-13-en-1-yl acetate, and (Z)-octadeca-15-en-1-yl acetate.

[0122] In some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I comprises the steps of contacting an acylating agent with an alkenol of formula II to form an olefin metathesis reaction partner of formula III, and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the alkenol of formula II is (Z)-octadeca-9-en-1-ol; the olefin metathesis reaction partner of formula III is (Z)-octadeca-9-en-1-yl acetate; the internal olefin of formula IV is (Z)-deca-5-ene; and the aliphatic olefin metathesis product of formula I is (Z)-tetradeca-9-en-1-yl acetate. In some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I comprises the steps of contacting an acylating agent with an alkenol of formula II to form an olefin metathesis reaction partner of formula III, and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the alkenol of formula II is (Z)-octadeca-9-en-1-ol; the olefin metathesis reaction partner of formula III is (Z)-octadeca-9-en-1-yl acetate; the internal olefin of formula IV is (Z)-hexa-3-ene; and the aliphatic olefin metathesis product of formula I is (Z)-dodeca-9-en-1-yl acetate. In some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I comprises the steps of contacting an acylating agent with an alkenol of formula II to form an olefin metathesis reaction partner of formula III, and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the alkenol of formula II is (Z)-icosa-11-en-1-ol; the olefin metathesis reaction partner of formula III is (Z)-icosa-11-en-1-yl acetate; the internal olefin of formula IV is (Z)-hexa-3-ene; and the aliphatic olefin metathesis product of formula I is (Z)-tetradeca-11-en-1-yl acetate.

[0123] In some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I includes the steps of: reducing an unsaturated aliphatic carboxyl derivative of formula IIa to form an alkenol of formula II; contacting an acylating agent with the alkenol of formula II to form an olefin metathesis reaction partner of formula III; and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where R 1 is C 1~3 It is alkyl, R 2 is C 1~12 It is alkyl, R 3 is C 1~12 It is alkyl, R 4 H and C 1~3 Selected from the group consisting of alkyl groups, where y is an integer in the range of 5 to 15 and z is an integer in the range of 0 to 7. In some embodiments, R 1 is C 1~3 It is alkyl, R 2 is C 1~12 It is alkyl, R 3 is C 1~12 It is alkyl, R 4 is C 1~3 It is an alkyl group, where y is 7 and z is an integer in the range of 1 to 5. In some embodiments, R 1 is C 1~3 It is alkyl, R 2 is C 1~12 It is alkyl, R 3 is C 1~12 It is alkyl, R 4 H is an integer between 5 and 15, and z is an integer between 1 and 5.

[0124] In some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I includes the steps of: reducing an unsaturated aliphatic carboxyl derivative of formula IIa to form an alkenol of formula II; contacting an acylating agent with the alkenol of formula II to form an olefin metathesis reaction partner of formula III; and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where R 1R is selected from the group consisting of H and methyl; 2 These are n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; R 3 R is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl; 4 is selected from the group consisting of H and methyl; y is an integer in the range of 6 to 14; z is an integer in the range of 1 to 4. In some embodiments, R 1 is methyl; R 2 R is selected from the group consisting of n-hexyl, n-heptyl, and n-octyl; 3 R is selected from the group consisting of ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; 4 is methyl; y is an integer selected from the group consisting of 7, 9, 11, and 13; z is an integer selected from the group consisting of 1, 2, and 3. In some embodiments, R 1 is methyl; R 2 R is selected from the group consisting of n-hexyl, n-heptyl, and n-octyl; 3 R is selected from the group consisting of ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; 4 H is; y is an integer selected from the group consisting of 7, 9, 11, and 13; and z is an integer selected from the group consisting of 1, 2, and 3.

[0125] In some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I includes the steps of: reducing an unsaturated aliphatic carboxyl derivative of formula IIa to form an alkenol of formula II; contacting an acylating agent with the alkenol of formula II to form an olefin metathesis reaction partner of formula III; and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where R 1 is methyl; R 2 is n-octyl; R 3R is selected from the group consisting of ethyl and n-butyl; 4 is methyl; y is an integer selected from the group consisting of 7, 9, 11, and 13; z is an integer selected from the group consisting of 1 and 3. In some embodiments, R 1 is methyl; R 2 is n-octyl; R 3 R is selected from the group consisting of ethyl and n-butyl; 4 is methyl; y is an integer selected from the group consisting of 7; z is an integer selected from the group consisting of 1 and 3. In some embodiments, R 1 is methyl; R 2 is n-octyl; R 3 R is selected from the group consisting of ethyl and n-butyl; 4 H is; y is an integer selected from the group consisting of 7, 9, 11, and 13; z is an integer selected from the group consisting of 1 and 3. In some embodiments, R 1 is methyl; R 2 is n-octyl; R 3 R is selected from the group consisting of ethyl and n-butyl; 4 H is an integer selected from the group consisting of 7; z is an integer selected from the group consisting of 1 and 3.

[0126] In some aspects, R in equation IIa 4 C 1~8 Alkyl (e.g., C 1-3 When the unsaturated aliphatic carboxyl derivative is an unsaturated fatty acid alkyl ester (such as alkyl or methyl), the unsaturated aliphatic carboxyl derivative is an unsaturated fatty acid alkyl ester. Therefore, in some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I includes the steps of reducing an unsaturated fatty acid alkyl ester of formula IIa to form an alkenol of formula II, contacting the alkenol of formula II with an acylating agent to form an olefin metathesis reaction partner of formula III, and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the unsaturated fatty acid alkyl ester of formula IIa is C11 ~C 29 It is an unsaturated fatty acid methyl ester; the alkenol of formula II is C 10 ~C 28 It is an aliphatic alkenol; the metathesis reaction partner in formula III is C 10 ~C 28 It is an acetate ester of an aliphatic alkenol; the internal olefin of formula IV is C4~C 20 It is an internal olefin; the aliphatic olefin metathesis product of formula I is C8~C 28 (Z)-Unsaturated aliphatic ester acetate. In some embodiments, the unsaturated fatty acid alkyl ester of formula IIa is C 15 ~C 27 It is an unsaturated fatty acid methyl ester; the alkenol of formula II is C 14 ~C 26 It is an aliphatic alkenol; the metathesis reaction partner in formula III is C 14 ~C 26 It is an acetate ester of an aliphatic alkenol; the internal olefin of formula IV is C4~C 12 It is an internal olefin; the aliphatic olefin metathesis product of formula I is C 12 ~C 24 (Z)-Unsaturated aliphatic ester acetate. In some embodiments, the unsaturated fatty acid alkyl ester of formula IIa is C 17 ~C 25 It is an unsaturated fatty acid methyl ester; the alkenol of formula II is C 16 ~C 24 It is an aliphatic alkenol; the metathesis reaction partner in formula III is C 16 ~C 24 It is an acetate ester of an aliphatic alkenol; the internal olefin of formula IV is C6~C 10 It is an internal olefin; the aliphatic olefin metathesis product of formula I is C 14 ~C 22 It is a (Z)-unsaturated aliphatic ester acetate.

[0127] In some embodiments, the present invention provides a method for synthesizing an aliphatic olefin metathesis product of formula I as described herein, where the unsaturated fatty acid alkyl ester of formula IIa is selected from the group comprising methyl octadeca-9-enoate, methyl eicosa-11-enoate, methyl docosa-13-enoate, methyl tetracosa-15-enoate, or mixtures thereof. In some embodiments, the unsaturated fatty acid alkyl ester comprises methyl octadeca-9-enoate and at least one member selected from the group comprising methyl eicosa-11-enoate, methyl docosa-13-enoate, and methyl tetracosa-15-enoate. In some embodiments, the unsaturated fatty acid alkyl ester is selected from the group comprising methyl octadeca-9-enoate, methyl eicosa-11-enoate, methyl docosa-13-enoate, and methyl tetracosa-15-enoate. In some embodiments, the unsaturated fatty acid alkyl ester is methyl octadeca-9-enoate. In some embodiments, the unsaturated fatty acid alkyl ester is methyl eicosa-11-enoate. In some embodiments, the unsaturated fatty acid alkyl ester is methyl docosa-13-enoate. In some embodiments, the unsaturated fatty acid alkyl ester is methyl tetracosa-15-enoate.

[0128] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I comprises the steps of: reducing an unsaturated fatty acid alkyl ester of formula IIa to form an alkenol of formula II; contacting the alkenol of formula II with an acylating agent to form an olefin metathesis reaction partner of formula III; and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, wherein the unsaturated fatty acid alkyl ester of formula IIa comprises at least one member selected from the group consisting of methyl (Z)-octadeca-9-enoate, methyl (Z)-icosa-11-enoate, methyl (Z)-docosa-13-enoate, and methyl (Z)-tetracosa-15-enoate; The alkenol of formula II comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-ol, (Z)-icosa-11-en-1-ol, (Z)-docosa-13-en-1-ol, and (Z)-tetracosa-15-en-ol; the olefin metathesis reaction partner of formula III comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-yl acetate, (Z)-icosa-11-en-1-yl acetate, (Z)-docosa-13-en-1-yl acetate, and (Z)-tetracosa-15-en-1-yl acetate; the internal olefin of formula IV is selected from the group consisting of (Z)-deca-5-ene, (Z)-octa-4-ene, and (Z)-hexa-3-ene;The aliphatic olefin metathesis products of formula I are (Z)-tetradeca-9-en-1-yl acetate, (Z)-hexadeca-11-en-1-yl acetate, (Z)-octadeca-13-en-1-yl acetate, (Z)-icosa-15-en-1-yl acetate, (Z)-trideca-9-en-1-yl acetate, (Z)-pentadeca-11-en-1-yl acetate, (Z)-heptadeca-13-en-1-yl acetate, (Z)-nonadeca-15-en-1-yl acetate, (Z)-dodeca-9-en-1-yl acetate, (Z)-tetradeca-11-en-1-yl acetate, and (Z)-hexadeca-13-en-1-yl acetate. It includes at least one member selected from the group consisting of acetate and (Z)-octadeca-15-en-1-yl acetate.

[0129] In some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I comprises the steps of: reducing an unsaturated fatty acid alkyl ester of formula IIa to form an alkenol of formula II; contacting the alkenol of formula II with an acylating agent to form an olefin metathesis reaction partner of formula III; and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the unsaturated fatty acid alkyl ester of formula IIa is methyl (Z)-octadeca-9-enoate; the alkenol of formula II is (Z)-octadeca-9-en-1-ol; the olefin metathesis reaction partner of formula III is (Z)-octadeca-9-en-1-yl acetate; the internal olefin of formula IV is (Z)-deca-5-ene; and the aliphatic olefin metathesis product of formula I is (Z)-tetradeca-9-en-1-yl acetate.

[0130] In some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I comprises the steps of: reducing an unsaturated fatty acid alkyl ester of formula IIa to form an alkenol of formula II; contacting the alkenol of formula II with an acylating agent to form an olefin metathesis reaction partner of formula III; and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the unsaturated fatty acid alkyl ester of formula IIa is methyl (Z)-octadeca-9-enoate; the alkenol of formula II is (Z)-octadeca-9-en-1-ol; the olefin metathesis reaction partner of formula III is (Z)-octadeca-9-en-1-yl acetate; the internal olefin of formula IV is (Z)-hexa-3-ene; and the aliphatic olefin metathesis product of formula I is (Z)-dodeca-9-en-1-yl acetate.

[0131] In some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I comprises the steps of: reducing an unsaturated fatty acid alkyl ester of formula IIa to form an alkenol of formula II; contacting the alkenol of formula II with an acylating agent to form an olefin metathesis reaction partner of formula III; and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the unsaturated fatty acid alkyl ester of formula IIa is methyl (Z)-eicosa-11-enoate; the alkenol of formula II is (Z)-eicosa-11-en-1-ol; the olefin metathesis reaction partner of formula III is (Z)-eicosa-11-en-1-yl acetate; the internal olefin of formula IV is (Z)-hexa-3-ene; and the aliphatic olefin metathesis product of formula I is (Z)-tetradeca-11-en-1-yl acetate. The prefixes "icosa" and "eicosa" are used interchangeably to refer to hydrocarbon chains having 20 carbon atoms (i.e., methyl (Z)-eicosa-11-enoate, (Z)-eicosa-11-en-1-ol, and (Z)-eicosa-11-en-1-yl acetate correspond to methyl (Z)-icosa-11-enoate, (Z)-icosa-11-en-1-ol, and (Z)-icosa-11-en-1-yl acetate, respectively).

[0132] In some aspects, R in equation IIa 4 When is H, the unsaturated aliphatic carboxyl derivative is an unsaturated fatty acid. Therefore, in some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I includes the steps of reducing an unsaturated fatty acid of formula IIa to form an alkenol of formula II, contacting the alkenol of formula II with an acylating agent to form an olefin metathesis reaction partner of formula III, and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the unsaturated fatty acid of formula IIa is C 10 ~C 28 It is an unsaturated fatty acid; the alkenol in formula II is C 10 ~C28 It is an aliphatic alkenol; the metathesis reaction partner in formula III is C 10 ~C 28 It is an acetate ester of an aliphatic alkenol; the internal olefin of formula IV is C4~C 20 It is an internal olefin; the aliphatic olefin metathesis product of formula I is C8~C 28 (Z)-Unsaturated aliphatic ester acetate. In some embodiments, the unsaturated fatty acid of formula IIa is C 14 ~C 26 It is an unsaturated fatty acid; the alkenol in formula II is C 14 ~C 26 It is an aliphatic alkenol; the metathesis reaction partner in formula III is C 14 ~C 26 It is an acetate ester of an aliphatic alkenol; the internal olefin of formula IV is C4~C 12 It is an internal olefin; the aliphatic olefin metathesis product of formula I is C 12 ~C 24 (Z)-Unsaturated aliphatic ester acetate. In some embodiments, the unsaturated fatty acid of formula IIa is C 16 ~C 24 It is an unsaturated fatty acid; the alkenol in formula II is C 16 ~C 24 It is an aliphatic alkenol; the metathesis reaction partner in formula III is C 16 ~C 24 It is an acetate ester of an aliphatic alkenol; the internal olefin of formula IV is C6~C 10 It is an internal olefin; the aliphatic olefin metathesis product of formula I is C 14 ~C 22 It is a (Z)-unsaturated aliphatic ester acetate.

[0133] In some embodiments, the present invention provides a method for synthesizing an aliphatic olefin metathesis product of formula I as described herein, where the unsaturated fatty acid of formula IIa is selected from the group comprising octadec-9-enoic acid, eicosa-11-enoic acid, docosa-13-enoic acid, tetracosa-15-enoic acid, or a mixture thereof. In some embodiments, the unsaturated fatty acid comprises octadec-9-enoic acid and at least one member selected from the group comprising eicosa-11-enoic acid, docosa-13-enoic acid, and tetracosa-15-enoic acid. In some embodiments, the unsaturated fatty acid is selected from the group comprising octadec-9-enoic acid, eicosa-11-enoic acid, docosa-13-enoic acid, and tetracosa-15-enoic acid. In some embodiments, the unsaturated fatty acid is octadec-9-enoic acid. In some embodiments, the unsaturated fatty acid is eicosa-11-enoic acid. In some embodiments, the unsaturated fatty acid is docosa-13-enoic acid. In some embodiments, the unsaturated fatty acid is tetracosa-15-enoic acid.

[0134] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I comprises the steps of: reducing an unsaturated fatty acid of formula IIa to form an alkenol of formula II; contacting the alkenol of formula II with an acylating agent to form an olefin metathesis reaction partner of formula III; and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, wherein the unsaturated fatty acid of formula IIa comprises at least one member selected from the group consisting of (Z)-octadeca-9-enoic acid, (Z)-icosa-11-enoic acid, (Z)-docosa-13-enoic acid, and (Z)-tetracosa-15-enoic acid; and the alkenol of formula II comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-ol, (Z)-icosa-11-en-1-ol, (Z)-docosa-13-en-1-ol, and (Z)-tetracosa-15-en-ol; The olefin metathesis reaction partner of formula III comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-yl acetate, (Z)-icosa-11-en-1-yl acetate, (Z)-docosa-13-en-1-yl acetate, and (Z)-tetracosa-15-en-1-yl acetate; the internal olefin of formula IV is selected from the group consisting of (Z)-deca-5-ene, (Z)-octa-4-ene, and (Z)-hexa-3-ene;The aliphatic olefin metathesis products of formula I are (Z)-tetradeca-9-en-1-yl acetate, (Z)-hexadeca-11-en-1-yl acetate, (Z)-octadeca-13-en-1-yl acetate, (Z)-icosa-15-en-1-yl acetate, (Z)-trideca-9-en-1-yl acetate, (Z)-pentadeca-11-en-1-yl acetate, (Z)-heptadeca-13-en-1-yl acetate, (Z)-nonadeca-15-en-1-yl acetate, (Z)-dodeca-9-en-1-yl acetate, (Z)-tetradeca-11-en-1-yl acetate, and (Z)-hexadeca-13-en-1-yl acetate. It includes at least one member selected from the group consisting of acetate and (Z)-octadeca-15-en-1-yl acetate.

[0135] In some embodiments, the unsaturated aliphatic carboxyl derivative of formula IIa is derived from a natural oil. In some embodiments, the unsaturated aliphatic carboxyl derivative of formula IIa is an unsaturated fatty acid obtained from a natural oil or natural oil derivative. Suitable natural oils or natural oil derivatives for use in the methods of the present invention include natural oils and / or derivatives thereof containing (Z)-octadeca-9-enoic acid, (Z)-icosa-11-enoic acid, (Z)-docosa-13-enoic acid, (Z)-tetracosa-15-enoic acid, or mixtures thereof. In some embodiments, the unsaturated fatty acid of formula IIa is obtained from natural oils selected from the group consisting of almond oil, canola oil, avocado oil, argan oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, grape seed oil, olive oil, palm oil, peanut oil, hemp seed oil, macadamia oil, safflower oil, sesame oil, soybean oil, sunflower oil, flaxseed oil, palm kernel oil, tuni oil, jatropha oil, jojoba oil, mustard oil, shepherd's purse oil, custard oil, castor oil, and combinations thereof. In some embodiments, the unsaturated fatty acid of formula IIa is obtained from natural oils selected from the group consisting of canola oil, avocado oil, olive oil, safflower oil, jojoba oil, and combinations thereof. In some embodiments, the unsaturated fatty acid of formula IIa is obtained from natural oils selected from the group consisting of canola oil, avocado oil, jojoba oil, and combinations thereof. In some embodiments, the unsaturated fatty acid of formula IIa is obtained from natural oils selected from the group consisting of canola oil and jojoba oil. In some embodiments, the unsaturated fatty acid of formula IIa is obtained from jojoba oil.

[0136] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I comprises the steps of: reducing an unsaturated fatty acid of formula IIa to form an alkenol of formula II; contacting the alkenol of formula II with an acylating agent to form an olefin metathesis reaction partner of formula III; and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, wherein the unsaturated fatty acid of formula IIa is obtained from natural oil or a derivative thereof and comprises at least one member selected from the group consisting of (Z)-octadeca-9-enoic acid, (Z)-icosa-11-enoic acid, (Z)-docosa-13-enoic acid, and (Z)-tetracosa-15-enoic acid; The alkenol of formula II comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-ol, (Z)-icosa-11-en-1-ol, (Z)-docosa-13-en-1-ol, and (Z)-tetracosa-15-en-ol; the olefin metathesis reaction partner of formula III comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-yl acetate, (Z)-icosa-11-en-1-yl acetate, (Z)-docosa-13-en-1-yl acetate, and (Z)-tetracosa-15-en-1-yl acetate; the internal olefin of formula IV is (Z)-deca-5-en; and the aliphatic olefin metathesis product of formula I is (Z)-tetradeca-9-en-1-yl It comprises at least one member selected from the group consisting of acetate, (Z)-hexadeca-11-en-1-yl acetate, (Z)-octadeca-13-en-1-yl acetate, and (Z)-icosa-15-en-1-yl acetate.

[0137] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I comprises the steps of: reducing an unsaturated fatty acid of formula IIa to form an alkenol of formula II; contacting the alkenol of formula II with an acylating agent to form an olefin metathesis reaction partner of formula III; and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, wherein the unsaturated fatty acid of formula IIa is obtained from natural oil or a derivative thereof and comprises at least one member selected from the group consisting of (Z)-octadeca-9-enoic acid, (Z)-icosa-11-enoic acid, (Z)-docosa-13-enoic acid, and (Z)-tetracosa-15-enoic acid; The alkenol of formula II comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-ol, (Z)-icosa-11-en-1-ol, (Z)-docosa-13-en-1-ol, and (Z)-tetracosa-15-en-ol; the olefin metathesis reaction partner of formula III comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-yl acetate, (Z)-icosa-11-en-1-yl acetate, (Z)-docosa-13-en-1-yl acetate, and (Z)-tetracosa-15-en-1-yl acetate; the internal olefin of formula IV is (Z)-octa-4-en; and the aliphatic olefin metathesis product of formula I is (Z)-trideca-9-en-1-yl It comprises at least one member selected from the group consisting of acetate, (Z)-pentadeca-11-en-1-yl acetate, (Z)-heptadeca-13-en-1-yl acetate, and (Z)-nonadeca-15-en-1-yl acetate.

[0138] In some embodiments, a method for synthesizing an aliphatic olefin metathesis product of formula I comprises the steps of: reducing an unsaturated fatty acid of formula IIa to form an alkenol of formula II; contacting the alkenol of formula II with an acylating agent to form an olefin metathesis reaction partner of formula III; and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, wherein the unsaturated fatty acid of formula IIa is obtained from natural oil or a derivative thereof and comprises at least one member selected from the group consisting of (Z)-octadeca-9-enoic acid, (Z)-icosa-11-enoic acid, (Z)-docosa-13-enoic acid, and (Z)-tetracosa-15-enoic acid; The alkenol of formula II comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-ol, (Z)-icosa-11-en-1-ol, (Z)-docosa-13-en-1-ol, and (Z)-tetracosa-15-en-ol; the olefin metathesis reaction partner of formula III comprises at least one member selected from the group consisting of (Z)-octadeca-9-en-1-yl acetate, (Z)-icosa-11-en-1-yl acetate, (Z)-docosa-13-en-1-yl acetate, and (Z)-tetracosa-15-en-1-yl acetate; the internal olefin of formula IV is (Z)-hexa-3-ene; and the aliphatic olefin metathesis product of formula I is (Z)-dodeca-9-en-1-yl It comprises at least one member selected from the group consisting of acetate, (Z)-tetradeca-11-en-1-yl acetate, (Z)-hexadeca-13-en-1-yl acetate, and (Z)-octadeca-15-en-1-yl acetate.

[0139] In some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I comprises the steps of: reducing an unsaturated fatty acid of formula IIa to form an alkenol of formula II; contacting the alkenol of formula II with an acylating agent to form an olefin metathesis reaction partner of formula III; and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the unsaturated fatty acid of formula IIa is (Z)-octadeca-9-enoic acid; the alkenol of formula II is (Z)-octadeca-9-en-1-ol; the olefin metathesis reaction partner of formula III is (Z)-octadeca-9-en-1-yl acetate; the internal olefin of formula IV is (Z)-deca-5-ene; and the aliphatic olefin metathesis product of formula I is (Z)-tetradeca-9-en-1-yl acetate.

[0140] In some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I comprises the steps of: reducing an unsaturated fatty acid of formula IIa to form an alkenol of formula II; contacting the alkenol of formula II with an acylating agent to form an olefin metathesis reaction partner of formula III; and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the unsaturated fatty acid of formula IIa is (Z)-octadeca-9-enoic acid; the alkenol of formula II is (Z)-octadeca-9-en-1-ol; the olefin metathesis reaction partner of formula III is (Z)-octadeca-9-en-1-yl acetate; the internal olefin of formula IV is (Z)-hexa-3-ene; and the aliphatic olefin metathesis product of formula I is (Z)-dodeca-9-en-1-yl acetate.

[0141] In some embodiments, a method for synthesizing the aliphatic olefin metathesis product of formula I comprises the steps of: reducing an unsaturated fatty acid of formula IIa to form an alkenol of formula II; contacting the alkenol of formula II with an acylating agent to form an olefin metathesis reaction partner of formula III; and contacting the olefin metathesis reaction partner of formula III with an internal olefin of formula IV, where the unsaturated fatty acid of formula IIa is (Z)-icosa-11-enoic acid; the alkenol of formula II is (Z)-icosa-11-en-1-ol; the olefin metathesis reaction partner of formula III is (Z)-icosa-11-en-1-yl acetate; the internal olefin of formula IV is (Z)-hexa-3-ene; and the aliphatic olefin metathesis product of formula I is (Z)-tetradeca-11-en-1-yl acetate.

[0142] (E)-Reaction partner and (Z)-Metathesis product from olefins By using the methods described herein, an aliphatic olefin metathesis product of formula I is prepared from a metathesis reaction partner and an olefin, where the aliphatic olefin metathesis product is substantially in the Z configuration and the metathesis reaction partner and / or olefin contains E-configured isomers. In some embodiments, an aliphatic olefin metathesis product containing more than 97% Z isomers is formed according to the methods described herein, where the metathesis reaction partner contains 1% or more E isomers and the olefin contains 0% to 15% or more E isomers.

[0143] Therefore, in some embodiments, the present invention relates to formula I: A method for synthesizing an aliphatic olefin metathesis product of TIFF2026086750000041.tif16128, wherein to form the aliphatic olefin metathesis product, formula III: The olefin metathesis reaction partners of TIFF2026086750000042.tif16128 and formula IV: The process includes contacting the internal olefin of TIFF2026086750000043.tif10128 with a Z-selective ruthenium catalyst or a Z-selective osmium catalyst, wherein, R 1 H and C 1~6 Selected from the group consisting of alkyl groups; R 2 C 1~18 Alkyl and C 2~18 Selected from the group consisting of alkenils; R 3 C 1~18 It is alkyl; The subscript y is an integer in the range of 0 to 17; The subscript z is an integer in the range of 0 to 17; This invention provides a method in which the aliphatic olefin metathesis product is at least 97% Z.

[0144] In some embodiments, Equation I: A method for synthesizing the aliphatic olefin metathesis product of TIFF2026086750000044.tif16128 is given by formula III: To form an olefin metathesis reaction partner in TIFF2026086750000045.tif16128, an acylating agent and formula II: The process of contacting the alkenol of TIFF2026086750000046.tif10128; and To form an aliphatic olefin metathesis product, use an olefin metathesis reaction partner and formula IV: A step of contacting the internal olefin of TIFF2026086750000047.tif10128 in the presence of a Z-selective ruthenium catalyst or a Z-selective osmium catalyst. Including, in the formula, R 1 H and C 1~6 Selected from the group consisting of alkyl groups; R 2 is C 1~18 Alkyl and C 2~18 Selected from the group consisting of alkenils; R 3 is C1~18 It is alkyl; The subscript y is an integer in the range of 0 to 17; The subscript z is an integer in the range of 0 to 17; The aliphatic olefin metathesis product is at least 97% Z.

[0145] In some embodiments, Equation I: A method for synthesizing the aliphatic olefin metathesis product of TIFF2026086750000048.tif16128 is given by formula II: To form the alkenol of TIFF2026086750000049.tif10128, formula IIa: A process for reducing the unsaturated aliphatic carboxyl derivative of TIFF2026086750000050.tif16128; Formula III: The steps of contacting an acylating agent with an alkenol to form an olefin metathesis reaction partner of TIFF2026086750000051.tif16128; and To form an aliphatic olefin metathesis product, use an olefin metathesis reaction partner and formula IV: A step of contacting the internal olefin of TIFF2026086750000052.tif10128 in the presence of a Z-selective ruthenium catalyst or a Z-selective osmium catalyst. Including, in the formula, R 1 H and C 1~6 Selected from the group consisting of alkyl groups; R 2 is C 1~18 Alkyl and C 2~18 Selected from the group consisting of alkenils; R 3 is C 1~18 It is alkyl; R 4 H and C 1~8 Selected from the group consisting of alkyl groups; The subscript y is an integer in the range of 0 to 17; The subscript z is an integer in the range of 0 to 17; The aliphatic olefin metathesis product is at least 97% Z.

[0146] In some embodiments, the aliphatic olefin metathesis product of formula I is prepared by using the method described herein, where the aliphatic olefin metathesis product is over 97% Z. In some embodiments, the aliphatic olefin metathesis product of formula I is about 97.1% Z to about 99.9% Z. In some embodiments, the aliphatic olefin metathesis product of formula I is approximately 97.2% Z, 97.4% Z, 97.5% Z, 97.6% Z, 97.8% Z, 97.9% Z, 98.0% Z, 98.1% Z, 98.2% Z, 98.4% Z, 98.5% Z, 98.6% Z, 98.8% Z, 98.9% Z, 99.0% Z, 99.1% Z, 99.2% Z, 99.3% Z, 99.4% Z, 99.5% Z, 99.6% Z, 99.7% Z, 99.8% Z, or approximately 99.9% Z. In some embodiments, the aliphatic olefin metathesis product of formula I is greater than 98% Z. In some embodiments, the aliphatic olefin metathesis product of formula I is greater than 99% Z. In some embodiments, the aliphatic olefin metathesis product of formula I has a concentration of approximately 99.1% Z, 99.2% Z, 99.3% Z, 99.4% Z, 99.5% Z, 99.6% Z, 99.7% Z, 99.8% Z, approximately 99.9% Z, or approximately 100.0% Z.

[0147] Accordingly, the present invention provides a method for synthesizing the aliphatic olefin metathesis product of formula I described herein, where the aliphatic olefin metathesis product is (Z)-tetradeca-9-en-1-yl acetate, (Z)-hexadeca-11-en-1-yl acetate, (Z)-octadeca-13-en-1-yl acetate, (Z)-icosa-15-en-1-yl acetate, (Z)-trideca-9-en-1-yl acetate, (Z)-pentadeca-11-en-1-yl acetate, (Z)-heptadeca-13-en-1-yl acetate, (Z)-nonadeca-15-en-1-yl acetate, (Z)-dodeca-9-en-1-yl acetate, (Z)-tetradeca-11-en-1-yl Selected from the group comprising acetate, (Z)-hexadeca-13-en-1-yl acetate, (Z)-octadeca-15-en-1-yl acetate, or mixtures thereof, wherein the aliphatic olefin metathesis product is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0148] In some embodiments, the aliphatic olefin metathesis product comprises at least one member selected from the group consisting of (Z)-tetradeca-9-en-1-yl acetate, (Z)-hexadeca-11-en-1-yl acetate, (Z)-octadeca-13-en-1-yl acetate, and (Z)-icosa-15-en-1-yl acetate, where the aliphatic olefin metathesis product is at least 97% Z, greater than 98% Z, or greater than 99% Z. In some embodiments, the aliphatic olefin metathesis product comprises at least one member selected from the group consisting of (Z)-trideca-9-en-1-yl acetate, (Z)-pentadeca-11-en-1-yl acetate, (Z)-heptadeca-13-en-1-yl acetate, and (Z)-nonadeca-15-en-1-yl acetate, where the aliphatic olefin metathesis product is at least 97% Z, greater than 98% Z, or greater than 99% Z. In some embodiments, the aliphatic olefin metathesis product comprises at least one member selected from the group consisting of (Z)-dodeca-9-en-1-yl acetate, (Z)-tetradeca-11-en-1-yl acetate, (Z)-hexadeca-13-en-1-yl acetate, and (Z)-octadeca-15-en-1-yl acetate, where the aliphatic olefin metathesis product is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0149] In some embodiments, the aliphatic olefin metathesis product is selected from the group consisting of (Z)-tetradeca-9-en-1-yl acetate, (Z)-dodeca-9-en-1-yl acetate, and (Z)-tetradeca-11-en-1-yl acetate, where the aliphatic olefin metathesis product is at least 97% Z, greater than 98% Z, or greater than 99% Z. In some embodiments, the aliphatic olefin metathesis product is (Z)-tetradeca-9-en-1-yl acetate, where (Z)-tetradeca-9-en-1-yl acetate is at least 97% Z, greater than 98% Z, or greater than 99% Z. In some embodiments, the aliphatic olefin metathesis product is (Z)-dodeca-9-en-1-yl acetate, where (Z)-dodeca-9-en-1-yl acetate is at least 97% Z, greater than 98% Z, or greater than 99% Z. In some embodiments, the aliphatic olefin metathesis product is (Z)-tetradeca-11-en-1-yl acetate, where (Z)-tetradeca-11-en-1-yl acetate is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0150] In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, where one or more of the unsaturated aliphatic carboxyl derivative of formula IIa, the alkenol of formula II, the olefin metathesis reaction partner of formula III, and / or the olefin of formula IV is at least 1% E. In some embodiments, one or more of the unsaturated aliphatic carboxyl derivative of formula IIa, the alkenol of formula II, the olefin metathesis reaction partner of formula III, and / or the olefin of formula IV are about 1.5% E to about 50% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% E, greater than 98% E, or greater than 99% E, and one or more of the unsaturated aliphatic carboxyl derivative of formula IIa, the alkenol of formula II, the olefin metathesis reaction partner of formula III, and / or the olefin of formula IV are about 1.5% E, about 3.0% E, about 5.0% E, about 8.0% E, about 10% E, about 15% E, about 20% E, about 25% E, about 30% E, about 35% E, about 40% E, about 45% E, or about 50% E. In some embodiments, one or more of the unsaturated aliphatic carboxyl derivatives of formula IIa, alkenols of formula II, olefin metathesis reaction partners of formula III, and / or olefins of formula IV are present in amounts of about 1.5% E to about 45% E, about 3.0% E to about 40% E, about 5.0% E to about 35% E, about 8.0% E to about 30% E, about 10% E to about 25% E, or about 15% E to about 20% E. In some embodiments, the E:Z (trans:cis) ratio for one or more of the unsaturated aliphatic carboxyl derivatives of formula IIa, alkenols of formula II, olefin metathesis reaction partners of formula III, and / or olefins of formula IV is about 1:30, about 1:20, about 1:10, about 1:6, about 1:4, about 1:3, about 1:2.5, about 1:2, about 1:1.5, about 1:1.2, or about 1:1.

[0151] In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, where the olefin metathesis reaction partner of formula III is at least 1% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partner of formula III is about 1.5% E to about 50% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partner of formula III is about 1.5% E, about 3.0% E, about 5.0% E, about 8.0% E, about 10% E, about 15% E, about 20% E, about 25% E, about 30% E, about 35% E, about 40% E, about 45% E, or about 50% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partner of formula III is approximately 1.5% E to about 45% E, about 3.0% E to about 40% E, about 5.0% E to about 35% E, about 8.0% E to about 30% E, about 10% E to about 25% E, or about 15% E to about 20% E. In some embodiments, the E:Z (trans:cis) ratio of the olefin metathesis reaction partner of formula III is approximately 1:30, about 1:20, about 1:10, about 1:6, about 1:4, about 1:3, about 1:2.5, about 1:2, about 1:1.5, about 1:1.2, or about 1:1, and the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0152] Accordingly, in some embodiments, the aliphatic olefin metathesis product of formula I prepared according to any of the methods described herein is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partner of formula III is selected from the group comprising octadeca-9-en-1-yl acetate, eicosa-11-en-yl acetate, docosa-13-en-1-yl acetate, tetracosa-15-en-1-yl acetate, or mixtures thereof, where the olefin metathesis reaction partner is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partner consists of octadeca-9-en-1-yl acetate and at least one member selected from the group consisting of eicosa-11-en-yl acetate, docosa-13-en-1-yl acetate, and tetracosa-15-en-1-yl acetate, where the olefin metathesis reaction partner is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partner is selected from the group consisting of octadeca-9-en-1-yl acetate, eicosa-11-en-yl acetate, docosa-13-en-1-yl acetate, and tetracosa-15-en-1-yl acetate, where the olefin metathesis reaction partner is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E.

[0153] In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partner of formula III is octadeca-9-en-1-yl acetate, where octadeca-9-en-1-yl acetate is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partner is eicosa-11-en-1-yl acetate, where eicosa-11-en-1-yl acetate is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partner is docosa-13-en-1-yl acetate, where docosa-13-en-1-yl acetate is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin metathesis reaction partner is tetracosa-15-en-1-yl acetate, where tetracosa-15-en-1-yl acetate is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E.

[0154] In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, where the olefin of formula IV is at least 1% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin of formula IV is about 1.5% E to about 50% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin of formula IV is about 1.5% E, about 3.0% E, about 5.0% E, about 8.0% E, about 10% E, about 15% E, about 20% E, about 25% E, about 30% E, about 35% E, about 40% E, about 45% E, or about 50% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin of formula IV is approximately 1.5% E to about 45% E, about 3.0% E to about 40% E, about 5.0% E to about 35% E, about 8.0% E to about 30% E, about 10% E to about 25% E, or about 15% E to about 20% E. In some embodiments, the E:Z (trans:cis) ratio of the olefin of formula IV is approximately 1:30, about 1:20, about 1:10, about 1:6, about 1:4, about 1:3, about 1:2.5, about 1:2, about 1:1.5, about 1:1.2, or about 1:1, and the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0155] Accordingly, in some embodiments, the aliphatic olefin metathesis product of formula I prepared according to any of the methods described herein is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin of formula IV is selected from the group comprising hexadeca-8-ene, tetradeca-7-ene, dodeca-6-ene, deca-5-ene, octa-4-ene, or hexa-3-ene, where the olefin is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin is selected from the group consisting of hexadeca-8-ene, tetradeca-7-ene, dodeca-6-ene, deca-5-ene, octa-4-ene, and hexa-3-ene, where the olefin is approximately 8.0% to approximately 30% E, approximately 10% to approximately 25% E, or approximately 15% to approximately 20% E.

[0156] In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin of formula IV is selected from the group consisting of dodeca-6-ene, deca-5-ene, octa-4-ene, and hexa-3-ene, where the olefin is approximately 8.0% to approximately 30% E, approximately 10% to approximately 25% E, or approximately 15% to approximately 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin is selected from the group consisting of deca-5-ene, octa-4-ene, and hexa-3-ene, where the olefin is approximately 8.0% to approximately 30% E, approximately 10% to approximately 25% E, or approximately 15% to approximately 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin is deca-5-ene, where deca-5-ene is approximately 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin is octa-4-ene, where octa-4-ene is approximately 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the olefin is hexa-3-ene, where hexa-3-ene is approximately 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E.

[0157] In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, where the alkenol of formula II is at least 1% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the alkenol of formula II is about 1.5% E to about 50% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the alkenol of formula II is about 1.5% E, about 3.0% E, about 5.0% E, about 8.0% E, about 10% E, about 15% E, about 20% E, about 25% E, about 30% E, about 35% E, about 40% E, about 45% E, or about 50% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the alkenol of formula II is approximately 1.5% E to about 45% E, about 3.0% E to about 40% E, about 5.0% E to about 35% E, about 8.0% E to about 30% E, about 10% E to about 25% E, or about 15% E to about 20% E. In some embodiments, the E:Z (trans:cis) ratio of the alkenol of formula II is approximately 1:30, about 1:20, about 1:10, about 1:6, about 1:4, about 1:3, about 1:2.5, about 1:2, about 1:1.5, about 1:1.2, or about 1:1, and the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0158] Accordingly, in some embodiments, the aliphatic olefin metathesis product of formula I prepared according to any of the methods described herein is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the alkenol of formula II is selected from the group comprising octadeca-9-en-1-ol, eicosa-11-en-1-ol, docosa-13-en-1-ol, tetracosa-15-en-ol, or mixtures thereof, where the alkenol is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the alkenol is selected from the group consisting of octadeca-9-en-1-ol, eicosa-11-en-1-ol, docosa-13-en-1-ol, and tetracosa-15-en-ol, where the alkenol is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E.

[0159] In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the alkenol of formula II is octadeca-9-en-1-ol, where octadeca-9-en-1-ol is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the alkenol is eicosa-11-en-1-ol, where eicosa-11-en-1-ol is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the alkenol is docosa-13-en-1-ol, where docosa-13-en-1-ol is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the alkenol is tetracosa-15-en-ol, where tetracosa-15-en-ol is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E.

[0160] In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, where the unsaturated aliphatic carboxyl derivative of formula IIa is at least 1% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated aliphatic carboxyl derivative of formula IIa is about 1.5% E to about 50% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated aliphatic carboxyl derivative of formula IIa is about 1.5% E, about 3.0% E, about 5.0% E, about 8.0% E, about 10% E, about 15% E, about 20% E, about 25% E, about 30% E, about 35% E, about 40% E, about 45% E, or about 50% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated aliphatic carboxyl derivative of formula IIa is approximately 1.5% E to about 45% E, about 3.0% E to about 40% E, about 5.0% E to about 35% E, about 8.0% E to about 30% E, about 10% E to about 25% E, or about 15% E to about 20% E. In some embodiments, the E:Z (trans:cis) ratio of the unsaturated aliphatic carboxyl derivative of formula IIa is approximately 1:30, about 1:20, about 1:10, about 1:6, about 1:4, about 1:3, about 1:2.5, about 1:2, about 1:1.5, about 1:1.2, or about 1:1, and the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z.

[0161] Accordingly, in some embodiments, the aliphatic olefin metathesis product of formula I prepared according to any of the methods described herein is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid alkyl ester of formula IIa is selected from the group comprising methyl octadeca-9-enoate, methyl eicosa-11-enoate, methyl docosa-13-enoate, methyl tetracosa-15-enoate, or mixtures thereof, where the unsaturated fatty acid alkyl ester is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid alkyl ester of formula IIa consists of methyl octadeca-9-enoate and at least one member selected from the group consisting of methyl eicosa-11-enoate, methyl docosa-13-enoate, and methyl tetracosa-15-enoate, where the unsaturated fatty acid alkyl ester is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid alkyl ester is selected from the group consisting of methyl octadeca-9-enoate, methyl eicosa-11-enoate, methyl docosa-13-enoate, and methyl tetracosa-15-enoate, where the unsaturated fatty acid alkyl ester is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E.

[0162] In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid alkyl ester of formula IIa is methyl octadeca-9-enoate, where methyl octadeca-9-enoate is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid alkyl ester is methyl eicosa-11-enoate, where methyl eicosa-11-enoate is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid alkyl ester is methyl docosa-13-enoate, where methyl docosa-13-enoate is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid alkyl ester is methyl tetracosa-15-enoate, where methyl tetracosa-15-enoate is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E.

[0163] Accordingly, in some embodiments, the aliphatic olefin metathesis product of formula I prepared according to any of the methods described herein is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid of formula IIa is selected from the group comprising octadeca-9-enoic acid, eicosa-11-enoic acid, docosa-13-enoic acid, tetracosa-15-enoic acid, or mixtures thereof, where the unsaturated fatty acid is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid of formula IIa consists of octadec-9-enoic acid and at least one member selected from the group consisting of eicosa-11-enoic acid, docosa-13-enoic acid, and tetracosa-15-enoic acid, where the unsaturated fatty acid is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid of formula IIa is selected from the group consisting of octadeca-9-enoic acid, eicosa-11-enoic acid, docosa-13-enoic acid, and tetracosa-15-enoic acid, where the unsaturated fatty acid is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E.

[0164] In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid of formula IIa is octadeca-9-enoic acid, where octadeca-9-enoic acid is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid is eicosa-11-enoic acid, where eicosa-11-enoic acid is about 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid is docosa-13-enoic acid, where docosa-13-enoic acid is approximately 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E. In some embodiments, the aliphatic olefin metathesis product of formula I is at least 97% Z, greater than 98% Z, or greater than 99% Z, and the unsaturated fatty acid is tetracosa-15-enoic acid, where tetracosa-15-enoic acid is approximately 8.0% to about 30% E, about 10% to about 25% E, or about 15% to about 20% E.

[0165] Metathesis catalyst In some embodiments, the metathesis catalyst used in the above method for synthesizing aliphatic olefin metathesis products has the structure of formula V: This is a Z-selective metathesis catalyst having TIFF2026086750000053.tif38128, During the ceremony, M is selected from the group consisting of ruthenium and osmium; X and Y are independently selected from the group consisting of S and O; Z is selected from the group consisting of O and S (=O); Each subscript m and subscript n is an integer independently selected from 0, 1, 2, 3, and 4; Each R aR is independently selected from the group consisting of halogens, C1-C6 alkyls, alkoxys, aryls, and heteroaryls; or one R a is adjacent to R a Together with other elements, they form unsubstituted or substituted biringu or unsubstituted or substituted polyringu; Each R b R is independently selected from the group consisting of halogens, C1-C6 alkyls, alkoxys, aryls, and heteroaryls; or one R b is adjacent to R b Together with other elements, they form unsubstituted or substituted biringu or unsubstituted or substituted polyringu; R c It is selected from the group consisting of hydrogen and C1-C6 alkyl groups; Each R d , R e , R f , and R g These are independently selected from the group consisting of hydrogen and C1-C6 alkyl groups; R 12 and R 13 These are independently selected from the group consisting of 2,4,6-tri-isopropylphenyl, 2,6-di-isopropylphenyl, 2,6-di-adamantylphenyl, 2-isopropyl-6-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, and 2,6-di-tert-butylphenyl; Each R 14 These are independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, benzyl, and phenyl; R 15 R is selected from the group consisting of hydrogen, halogens, and C1-C6 alkyl groups, or R 15 and one R 14 They come together to form a bond.

[0166] In some embodiments, the Z-selective metathesis catalyst has the structure of formula V, where M is ruthenium; X and Y are S; Z is selected from the group consisting of O and S (=O); the subscript m is 2; the subscript n is 0; and each Ra R is independently selected from the group consisting of halogens, C1-C6 alkyls, and aryls; c is hydrogen; each R d , R e , R f , and R g is hydrogen; R 12 and R 13 Each R is independently selected from the group consisting of 2,4,6-tri-isopropylphenyl, 2,6-di-isopropylphenyl, 2,6-di-adamantylphenyl, 2-isopropyl-6-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, and 2,6-di-tert-butylphenyl; 14 R is independently selected from the group consisting of methyl, isopropyl, benzyl, and tert-butyl; 15 R is selected from the group consisting of hydrogen, halogens, and C1-C6 alkyl groups, or R 15 and one R 14 They come together to form a bond.

[0167] In some embodiments, the metathesis catalyst used in a method for synthesizing the aliphatic olefin metathesis product of formula I is comprised of the following: This is a Z-selective metathesis catalyst selected from TIFF2026086750000054.tif48136.

[0168] In some embodiments, the catalyst The filename is TIFF2026086750000055.tif36128.

[0169] Other catalysts useful in the methods provided herein include, but are not limited to, those described in WO 2018 / 191373, WO 2018 / 038928, WO 2018 / 034931, WO 2017 / 100585, which are incorporated herein in their entirety by reference, and those described in U.S. Patents 10,857,350; 10,774,035; 9,938,253; and 6,921,735. Catalysts described by Zachmann et al. (Chem. Eur. J. 2021, 27, 7663-7666) and Grudzien et al. (Chem. Eur. J. 2014, 20, 2819-2828) may also be used.

[0170] Metathesis reaction conditions Typically, a Z-selective metathesis catalyst is given in a quasi-stoichiometric amount (e.g., catalytic amount) in the reaction mixture. In certain embodiments, the amount is in the range of about 0.001 to about 50 mol% (0.1 to 5000 ppm) relative to the limiting reagent of the chemical reaction, depending on which reagent is in stoichiometric excess. In some embodiments, the catalyst is present at a concentration of about 40 mol% or less relative to the limiting reagent. In some embodiments, the catalyst is present at a concentration of about 30 mol% or less relative to the limiting reagent. In some embodiments, the catalyst is present at a concentration of less than about 20 mol%, less than about 10 mol%, less than about 5 mol%, less than about 2.5 mol%, less than about 1 mol%, less than about 0.5 mol%, less than about 0.1 mol%, less than about 0.015 mol%, less than about 0.01 mol%, less than about 0.0015 mol%, or less relative to the limiting reagent. In some embodiments, the catalyst is present in the range of about 2.5 mol% to about 5 mol% relative to the limiting reagent. In some embodiments, the reaction mixture contains approximately 0.01 to 0.1 mol% of the catalyst (e.g., 0.5 mol% of the catalyst). If the molecular formula of the catalyst complex contains two or more metals, the amount of catalyst complex used in the reaction can be adjusted accordingly.

[0171] The amount of catalyst added can also be expressed in relation to the olefin content of the reaction mixture. For example, the metathesis catalyst may be present in an amount ranging from approximately 0.1 ppm to approximately 500 ppm relative to the total number of double bonds in the reaction mixture. The reaction mixture may contain 0.1 to 100 ppm, or approximately 1 to 100 ppm, or approximately 1 to 75 ppm, or approximately 1 to 50 ppm, or approximately 3 to 50 ppm of catalyst per double bond.

[0172] In some cases, the methods described herein can be carried out in the absence of a solvent (e.g., undiluted). In some cases, the methods may involve the use of one or more solvents. Examples of solvents that may be suitable for use in the present invention include, but are not limited to, benzene, p-cresol, toluene, xylene, diethyl ether, glycol, diethyl ether, petroleum ether, hexane, cyclohexane, pentane, methylene chloride, chloroform, carbon tetrachloride, dioxane, tetrahydrofuran (THF), dimethyl sulfoxide, dimethylformamide, hexamethyl phosphate triamide, ethyl acetate, pyridine, triethylamine, picoline, and mixtures thereof. In some embodiments, the solvent is selected from benzene, toluene, pentane, methylene chloride, and THF. In certain embodiments, the solvent is benzene.

[0173] In some embodiments, the method is carried out under reduced pressure. This may be advantageous when volatile byproducts such as ethylene may be generated during the metathesis reaction. For example, by removing the ethylene byproduct from the reaction vessel, the equilibrium of the metathesis reaction may be advantageously shifted toward the formation of the desired product. In some embodiments, the method is carried out at a pressure of less than about 760 torr. In some embodiments, the method is carried out at a pressure of less than about 700 torr. In some embodiments, the method is carried out at a pressure of less than about 650 torr. In some embodiments, the method is carried out at a pressure of less than about 600 torr. In some embodiments, the method is carried out at a pressure of less than about 550 torr. In some embodiments, the method is carried out at a pressure of less than about 500 torr. In some embodiments, the method is carried out at a pressure of less than about 450 torr. In some embodiments, the method is carried out at a pressure of less than about 400 torr. In some embodiments, the method is carried out at a pressure of less than about 350 torr. In some embodiments, the method is carried out at a pressure of less than about 300 torr. In some embodiments, the method is carried out at a pressure of less than approximately 250 torr. In some embodiments, the method is carried out at a pressure of less than approximately 200 torr. In some embodiments, the method is carried out at a pressure of less than approximately 150 torr. In some embodiments, the method is carried out at a pressure of less than approximately 100 torr. In some embodiments, the method is carried out at a pressure of less than approximately 90 torr. In some embodiments, the method is carried out at a pressure of less than approximately 80 torr. In some embodiments, the method is carried out at a pressure of less than approximately 70 torr. In some embodiments, the method is carried out at a pressure of less than approximately 60 torr. In some embodiments, the method is carried out at a pressure of less than approximately 50 torr. In some embodiments, the method is carried out at a pressure of less than approximately 40 torr. In some embodiments, the method is carried out at a pressure of less than approximately 30 torr. In some embodiments, the method is carried out at a pressure of less than approximately 20 torr. In some embodiments, the method is carried out at a pressure of approximately 20 torr.

[0174] In some embodiments, the method is carried out at a pressure of approximately 19 torr. In some embodiments, the method is carried out at a pressure of approximately 18 torr. In some embodiments, the method is carried out at a pressure of approximately 17 torr. In some embodiments, the method is carried out at a pressure of approximately 16 torr. In some embodiments, the method is carried out at a pressure of approximately 15 torr. In some embodiments, the method is carried out at a pressure of approximately 14 torr. In some embodiments, the method is carried out at a pressure of approximately 13 torr. In some embodiments, the method is carried out at a pressure of approximately 12 torr. In some embodiments, the method is carried out at a pressure of approximately 11 torr. In some embodiments, the method is carried out at a pressure of approximately 10 torr. In some embodiments, the method is carried out at a pressure of approximately 10 torr. In some embodiments, the method is carried out at a pressure of approximately 9 torr. In some embodiments, the method is carried out at a pressure of approximately 8 torr. In some embodiments, the method is carried out at a pressure of approximately 7 torr. In some embodiments, the method is carried out at a pressure of approximately 6 torr. In some embodiments, the method is carried out at a pressure of approximately 5 torr. In some embodiments, the method is carried out at a pressure of approximately 4 torr. In some embodiments, the method is carried out at a pressure of approximately 3 torr. In some embodiments, the method is carried out at a pressure of approximately 2 torr. In some embodiments, the method is carried out at a pressure of approximately 1 torr. In some embodiments, the method is carried out at a pressure of less than approximately 1 torr.

[0175] In some embodiments, the two metathesis reactants (i.e., the metathesis reaction partner and the olefin) are present in equimolar amounts. In some embodiments, the two metathesis reactants are not present in equimolar amounts. In certain embodiments, the two reactants are present in molar ratios of approximately 20:1, 19:1, 18:1, 17:1, 16:1, 15:1, 14:1, 13:1, 12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, or 1:20. In certain embodiments, the two reactants exist in a molar ratio of approximately 10:1. In certain embodiments, the two reactants exist in a molar ratio of approximately 7:1. In certain embodiments, the two reactants exist in a molar ratio of approximately 5:1. In certain embodiments, the two reactants exist in a molar ratio of approximately 2:1. In certain embodiments, the two reactants exist in a molar ratio of approximately 1:10. In certain embodiments, the two reactants exist in a molar ratio of approximately 1:7. In certain embodiments, the two reactants exist in a molar ratio of approximately 1:5. In certain embodiments, the two reactants exist in a molar ratio of 1:2.

[0176] In some embodiments, 1 molar equivalent of olefin is brought into contact with 1 molar equivalent of olefin metathesis reaction partner. In some embodiments, about 1.5, 2, 2.5, or 3 molar equivalents of olefin are brought into contact with 1 molar equivalent of metathesis reaction partner. In some embodiments, about 1.5 molar equivalents of olefin are brought into contact with 1 molar equivalent of metathesis reaction partner.

[0177] Generally, reactions with many of the Z-selective metathesis catalysts disclosed herein yield more than 15%, for example, more than 50%, more than 75%, or more than 90%. Furthermore, the reactants and products are selected to produce a difference of at least 5°C in boiling points, for example, more than 20°C or more than 40°C. In addition, since the product is formed much more rapidly than by-products with the use of Z-selective metathesis catalysts, it is sometimes desirable to carry out these reactions as quickly as possible. In particular, the reaction is carried out in less than about 24 hours, for example, less than 12 hours, or less than 8 hours, or less than 4 hours. Advantageously, the method of the present invention produces metathesis products on a scale ranging from a few milligrams to several hundred kilograms or more. For example, the method can be carried out using about 1 to 10 grams of the internal olefin of formula IV, or about 10 to 100 grams of the internal olefin of formula IV, or about 100 to 500 grams of the internal olefin of formula IV, or about 500 to 1000 grams of the internal olefin of formula IV. This method can be carried out using at least 1, 5, 10, 25, 50, 100, or 1,000 kilograms of starting material. The metathesis reaction can be carried out using a metathesis reactor as described, for example, in WO 2011 / 046872, which can be operated in combination with one or more downstream separation devices for separating and / or reusing a specific product stream or byproduct stream (e.g., an olefin stream, a C2-C3 compound stream, or a C3-C5 compound stream). Operating the metathesis reactor and separation device in combination with one or more adsorbent beds can facilitate the separation of metathesis products from the catalyst, as well as the cleaning and drying of the equipment for the purification of the desired product. The reduction, acylation, and metathesis reactions can be carried out to obtain products on a metric ton scale.

[0178] Those skilled in the art will recognize that time, temperature, and solvent may be interdependent, and that changing one may necessitate changing others when preparing the metathesis product in the method of the present invention. The metathesis step can proceed at a variety of temperatures and times. Generally, the reaction in the method of the present invention is carried out using reaction times ranging from a few minutes to several days. For example, reaction times of about 12 hours to about 7 days can be used. In some embodiments, reaction times of 1 to 5 days can be used. In some embodiments, reaction times of about 10 minutes to about 10 hours can be used. Generally, the reaction in the method of the present invention is carried out at a temperature ranging from about 0°C to about 200°C. For example, the reaction can be carried out at 15 to 100°C. In some embodiments, the reaction can be carried out at 20 to 80°C (e.g., 20 to 60°C). In some embodiments, the reaction can be carried out at 100 to 150°C.

[0179] The olefins, metathesis reaction partners, olefin starting materials, olefin-containing reactants, and aliphatic olefin derivatives (e.g., alkenols, unsaturated aliphatic alcohol acetates, unsaturated aliphatic ester acetates, olefin metathesis reaction partners, aliphatic olefin metathesis products, unsaturated aliphatic aldehydes, unsaturated aliphatic carboxyl derivatives, metathesis products, etc.) used in the methods of the present invention can be obtained from any suitable source. In some embodiments, the metathesis reaction partners used in the methods of the present invention are obtained from natural oils and / or derivatives thereof (e.g., the unsaturated fatty acids mentioned above).

[0180] In some embodiments, the materials to be reacted during the metathesis reaction, including materials derived from natural oils, contain one or more contaminants that may adversely affect the performance of the metathesis catalyst. These contaminants may be referred to as “catalyst poisons” or “catalyst-poisoned contaminants.” The levels of contaminants can be reduced according to the methods described herein. In some embodiments, the materials contain multiple contaminants, and the method includes reducing the levels of two or more contaminants. In some embodiments, the materials contain multiple contaminants, and the method includes reducing the levels of three or more contaminants. In some embodiments, the materials contain multiple contaminants, and the method includes reducing the levels of four or more contaminants. In some embodiments, the materials contain multiple contaminants, and the method includes reducing the levels of five or more contaminants.

[0181] Typical contaminants include, but are not limited to, water, peroxides, peroxide decomposition products, hydroperoxides, protic materials, polar materials, Lewis basic catalyst poisons, and combinations thereof. It should be understood that some contaminants can be appropriately classified into multiple categories (for example, alcohols can be considered both protic and polar materials). Furthermore, it should be understood that different catalysts may exhibit different sensitivities to specific contaminants and contaminants that adversely affect the performance of a particular catalyst.

[0182] Typical protic materials that may be found as contaminants in the substrate to be reacted during a metathesis reaction include, but are not limited to, materials having hydrogen atoms bonded to oxygen (e.g., carboxylic acids, alcohols, etc.) and / or materials having hydrogen atoms bonded to nitrogen (e.g., primary amines, secondary amines, etc.). In some embodiments, particularly in natural oil substrates, but not exclusively in natural oil substrates, the protic material contaminants may include carboxylic acid functional groups, hydroxyl functional groups, or combinations thereof. In some embodiments, the protic materials are selected from the group consisting of free fatty acids, hydroxyl-containing materials, MAG, DAG, etc., and combinations thereof.

[0183] Typical polar materials that may be found as contaminants in the substrate to be reacted during a metathesis reaction include, but are not limited to, heteroatom-containing materials such as oxygenates. In some embodiments, the polar material is selected from the group consisting of alcohols, aldehydes, ethers, and combinations thereof.

[0184] Typical Lewis basic catalyst poisons that may be found as contaminants in the substrate to be reacted during a metathesis reaction include, but are not limited to, heteroatom-containing materials. In some embodiments, the Lewis basic catalyst poison is selected from the group consisting of N-containing materials, P-containing materials, S-containing materials, and combinations thereof.

[0185] Reacting materials containing contaminants can be treated with one or more modifiers that mitigate the potentially harmful effects of one or more contaminants. Modifiers usable in the method of the present invention (individually, in combination, sequentially, or simultaneously) include heat, molecular sieves, alumina (aluminum oxide), silica gel, montmorillonite clay, Fuller's earth, bleached earth, diatomaceous earth, zeolite, kaolin, activated metals (e.g., Cu, Mg, etc.), acid anhydrides (e.g., acetic anhydride, etc.), activated carbon (i.e., activated charcoal), soda ash, metal hydrides (e.g., alkaline earth metal hydrides such as CaH2), metal sulfates (e.g., alkaline earth metal sulfates such as calcium sulfate and magnesium sulfate; alkali metal sulfates such as potassium sulfate and sodium sulfate); Examples include other metal sulfates (such as aluminum sulfate and potassium magnesium sulfate), metal halides (e.g., alkaline earth metal halides such as potassium chloride), metal carbonates (e.g., calcium carbonate, sodium carbonate, etc.), metal silicates (e.g., magnesium silicate, etc.), phosphorus pentoxide, metal aluminum hydrides (e.g., alkali metal aluminum hydrides such as LiAlH4, NaAlH4, etc.), alkylaluminum hydrides (e.g., DIBALH), metal boron hydride (e.g., alkali metal boron hydride such as LiBH4, NaBH4, etc.), organometallic reagents (e.g., Grignard reagents; organolithium reagents such as n-butyllithium, t-butyllithium, sec-butyllithium; trialkylaluminum such as triethylaluminum, tributylaluminum, triisobutylaluminum, triisopropylaluminum, trioctylaluminum, etc.), metal amides (e.g., lithium diisopropylamide and metal bis(trimethylsilyl)amides such as KHMDS), palladium-carbon (Pd / C) catalysts, and combinations thereof.

[0186] In some embodiments, the regulator is a metal alkyl compound. In some embodiments, the metal M may be lithium, sodium, potassium, magnesium, calcium, zinc, cadmium, aluminum, or gallium. Suitable alkyl groups R include, but are not limited to, methyl, ethyl, butyl, hexyl, decyl, tetradecyl, and eicosyl (i.e., eicosyl). Examples of metal alkyl compounds include Mg(CH3)2, Mg(C2H5)2, Mg(C2H5)(C4H9), Mg(C4H9)2, Mg(C6H 13 )2, Mg(C 12 H 25 )2, Zn(CH3)2, Zn(C2H5)2, Zn(C4H9)2, Zn(C4H9)(C8H 17 ), Zn(C6H 13 )2, Zn(C6H3)2, Al(C2H5)3, Al(CH3)3, Al(n-C4H9)3, Al(C8H 17 )3, Al(iso-C4H9)3, Al(C 12 H 25 Examples of metal alkyl compounds include, but are not limited to, 3, and combinations thereof. Examples of metal alkyl compounds include substances having one or more halogen groups or hydride groups, such as ethylaluminum dichloride, diethylaluminum chloride, diethylaluminum hydride, Grignard reagents, and diisobutylaluminum hydride.

[0187] In some embodiments, the treatment of a metathesis reaction material (e.g., natural oil or natural oil derivative) may involve contacting the reaction material with a metal alkyl compound, and simultaneously or separately, contacting the reaction material with a hydride-containing compound. In some embodiments, when the reaction material is contacted simultaneously with the metal alkyl compound and the hydride-containing compound, the hydride-containing compound may be included in the metal alkyl compound. For example, in some cases, a specific concentration of the hydride-containing compound can be formed by a process used to produce a specific metal alkyl compound, such as a trialkylaluminum compound. However, in other embodiments, the metal alkyl compound can be combined with one or more hydride-containing compounds. Alternatively, in some embodiments, the metathesis reaction material may be treated with the hydride-containing compound in a separate reaction step, which may be performed before, after, or both before and after the treatment of the reaction material with the metal alkyl compound.

[0188] Any suitable hydride-containing compound can be used. In some embodiments, the hydride-containing compound is selected from the group consisting of metallic aluminum hydrides (e.g., alkali metal aluminum hydrides such as LiAlH4 and NaAlH4), alkylaluminum hydrides (e.g., DIBALH), and combinations thereof. In some embodiments, the hydride-containing compound is an alkylaluminum hydride such as DIBALH.

[0189] In some embodiments, contact between the metathesis reaction material and the hydride-containing compound is carried out in the same process as contact between the reaction material and the metal alkyl compound. In some embodiments, the weight-to-weight ratio of the metal alkyl compound to the hydride-containing compound in the treatment composition is 2:1 or 5:1 or 10:1 or 15:1 or 20:1 to 1000:1. In some embodiments, the weight-to-weight ratio of the metal alkyl compound to the hydride-containing compound in the treatment composition is at least 2:1 or at least 5:1 or at least 10:1 or at least 15:1 or at least 20:1.

[0190] In certain cases, the effectiveness of a Z-selective metathesis catalyst can be improved by slowly adding it to the substrate (e.g., increasing the turnover number or decreasing the total amount of catalyst added). When added slowly, the total amount of catalyst added can be reduced by at least 10%, at least 20%, or at least 30% while achieving the same turnover number as a single full batch addition. Slowly adding the total amount of catalyst may involve adding divided amounts of catalyst to the reactants at an average rate of about 10 ppm (ppmwt / hour), 5 ppmwt / hour, 1 ppmwt / hour, 0.5 ppmwt / hour, 0.1 ppmwt / hour, 0.05 ppmwt / hour, or 0.01 ppmwt / hour. In some embodiments, the catalyst is added slowly at a rate of about 0.01–10 ppmwt / hour, 0.05–5 ppmwt / hour, or 0.1–1 ppmwt / hour. Slow addition of the catalyst can be performed by batch adding at frequencies of every 5 minutes, every 15 minutes, every 30 minutes, every hour, every 2 hours, every 4 hours, every 12 hours, or every day. In other embodiments, slow addition is performed in a continuous addition process.

[0191] In some embodiments, an internal olefin (Z5-decene) and a metathesis reaction partner (e.g., oleyl acetate) are combined in a ratio ranging from 2:1 to 10:1 (e.g., 5:1), treated with an aluminum reagent (e.g., 1 wt% magnesium aluminum isopropoxide), and then a metathesis catalyst (e.g., ruthenium catalyst 3 described below) is added at an amount of 1 to 100 ppm (e.g., 3 to 50) per double bond.

[0192] Preparation of internal olefins In some embodiments, the synthesis of an aliphatic olefin metathesis product includes a step of forming an internal olefin by contacting a terminal olefin with a metathesis catalyst. In some embodiments, the internal olefin is of formula VIa: It is a compound of TIFF2026086750000056.tif12128; The terminal olefin is formula IVb: This is the compound TIFF2026086750000057.tif10128.

[0193] In some embodiments, the internal olefin is prepared using a Z-selective ruthenium catalyst or a Z-selective tungsten catalyst. In some embodiments, the internal olefin has the structure of formula XI: Prepared using a metathesis catalyst containing TIFF2026086750000058.tif26128, During the ceremony, M is tungsten; R 206a aryl, heteroaryl, alkyl, or cycloalkyl, each of which may be substituted; R 210a These are pyrrolyl, imidazolyl, indolyl, pyrazolyl, azaindolyl, or indazolyl, and may be substituted; R 211a is an aryl that may be substituted; R 208a is a hydrogen atom, alkyl, or alkoxy; R 207b This is a hydrogen atom, -O-(C 1~6 Alkyl), -CH2-O-(C 1~6 Alkyl), heteroalkoxy, or -N(C 1~6 Alkyl)2; R 207c and R 207d The hydrogen atom and C are independent of each other. 1~6 Alkyl, C 1~6 It is an alkoxy, halogen atom, -NO2, amide, or sulfonamide.

[0194] In some embodiments, R 210a R is pyrrolyl, imidazolyl, pyrazolyl, azaindolyl, or indazolyl, and each may be substituted; R 208a R is a hydrogen atom. 206ais phenyl, 2,6-dichlorophenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2-trifluoromethylphenyl, pentafluorophenyl, tert-butyl, or 1-adamantyl. In some embodiments, R 207b is methoxy, and R 207c is hydrogen, R 207d is hydrogen. In some embodiments, R 206a teeth The filename is TIFF2026086750000059.tif28128.

[0195] In some embodiments, the internal olefin has the structure of formula XII: Prepared using a metathesis catalyst containing TIFF2026086750000060.tif47128, During the ceremony, M 300 It is ruthenium; L 301 The structure is as follows: It is a ligand that has TIFF2026086750000061.tif19128, During the ceremony, Q 300 Q is selected from hydrocarbilene, substituted hydrocarbilene, heteroatom-containing hydrocarbilene, or substituted heteroatom-containing hydrocarbilene, where two or more substituents on adjacent atoms in Q may be linked to form a further ring structure. R 303 and R 304 These are independently selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; Q 301 is M 300 and R 303 It is a bond between the carbon atoms; R 305 , R 306 , R 307 , and R 308Each is independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom-containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate, where R 305 , R 306 , R 307 , and R 308 Any combination of these may be linked together to form one or more cyclic groups; X 301 This is selected from the group consisting of halides, nitrates, alkyl, aryl, alkoxy, alkylcarboxylate, aryloxy, alkoxycarbonyl, aryloxycarbonyl, arylcarboxylate, acyl, acyloxy, alkylsulfonate, arylsulfonate, alkylsulfanyl, arylsulfanyl, alkylsulfinyl, and arylsulfinyl; Y 300 is a heteroatom selected from the group consisting of N, O, S, and P; Y 300 If is O or S, then the subscript q is 1, and Y 300 If is N or P, then the subscript q is 2; Z 300The functional group is selected from hydrogen, alkyl, aryl, functionalized alkyl, or functionalized aryl, where the functional group is independently selected from alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; and from the group consisting of methyl, isopropyl, sec-butyl, t-butyl, neopentyl, benzyl, phenyl, and trimethylsilyl.

[0196] "Hydrocarbyl" refers to a monovalent hydrocarbyl group containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated, and unsaturated species, such as alkyl groups, alkenyl groups, and aryl groups. "Hydrocarbylene" refers to a divalent hydrocarbyl moiety containing 1 to about 30 carbon atoms.

[0197] In some cases, Q 300 is a hydrocarbylene group (e.g., ethylene). In some embodiments, ligand L 301 R is the 1,3-disubstituted 4,5-dihydroimidazole-2-ylidene moiety. In some embodiments, R 303 is an adamantyl group or a substituted adamantyl group, or a substituted C 3~12 It is a cycloalkyl group. In some embodiments, R 304 This is a disubstituted aryl group (for example, a phenyl group in which both ortho ring positions are substituted with, for example, isopropyl groups) or a trisubstituted aryl group (for example, a phenyl group in which both ortho ring positions and para ring positions are substituted with, for example, methyl groups).

[0198] In some embodiments, R 305 , R 306 , R 307 , and R 308 is hydrogen. In some embodiments, Y 300 is O. In some forms, Z 300is alkyl (e.g., isopropyl). In some embodiments, X 301 It is nitrate.

[0199] Metathesis reactions for the preparation of internal olefins (e.g., Z5-decene) from terminal olefins (e.g., 1-hexene) can be carried out as previously described for the preparation of acylated alkenol metathesis products and alkenal acetal metathesis products. In some embodiments, the terminal olefin of formula IVb (e.g., 1-hexene) and the ruthenium catalyst shown below are used: Combine it with TIFF2026086750000062.tif34128.

[0200] In some embodiments, the catalyst is present in an amount ranging from about 1 ppm to about 50 ppm (e.g., 3 to 50 ppm or 5 to 10 ppm) relative to the total number of double bonds in the reaction mixture. In some embodiments, the reaction is carried out at a temperature ranging from about 20°C to about 60°C (e.g., 50°C) for 1 to 8 hours or longer. The reaction may be carried out undiluted and in the absence of further solvents.

[0201] Composition and its use In some embodiments, the aliphatic olefin metathesis product prepared according to the method described herein is a pheromone. Therefore, the pheromones prepared herein can be formulated for use as insect control compositions. The pheromone composition may include a carrier and / or be contained in a dispenser. The carrier may, but is not limited to, an inert liquid or solid.

[0202] Examples of solid carriers include, but are not limited to, fillers such as kaolin, bentonite, dolomite, calcium carbonate, talc, powdered magnesia, fuller's earth, wax, gypsum, diatomaceous earth, rubber, plastics, silica, and china clay. Examples of liquid carriers include, but are not limited to, water; alcohols such as ethanol, butanol, or glycol, and their ethers or esters such as methyl glycol acetate; ketones such as acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, or isophorone; alkanes such as hexane, pentane, or heptane; aromatic hydrocarbons such as xylene or alkylnaphthalene; mineral oil or vegetable oil; aliphatic chlorinated hydrocarbons such as trichloroethane or methylene chloride; aromatic chlorinated hydrocarbons such as chlorobenzene; water-soluble or strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, or N-methylpyrrolidone; liquefied gases; and mixtures thereof. Feed or feeding stimulants may be added to the carrier.

[0203] Pheromone compositions can be formulated to be released slowly into the atmosphere and / or protected from degradation after release. For example, pheromone compositions can be contained in carriers such as microcapsules, biodegradable flakes, and paraffin wax-based matrices.

[0204] The pheromone composition may contain other pheromones or attractants, provided that the other compounds do not substantially interfere with the activity of the composition. The pheromone composition may also contain insecticides. Examples of suitable insecticides include, but are not limited to, buprofezin, pyriproxyfen, flonicamide, acetamiprid, dinotefuran, clothianidin, acephate, malathion, quinolphos, chloropyriphos, profenophos, benziocarb, bifenthrin, chlorpyriphos, cyfluthrin, diazinon, pyrethrum, fenpropatrin, quinoprene, insecticidal soaps or insecticidal oils, and mixtures thereof.

[0205] A pheromone composition can be used in combination with a dispenser for releasing the composition in a specific environment. Any suitable dispenser known in the art can be used. Examples of such dispensers include, but are not limited to, bubble caps containing a reservoir with a permeable barrier through which the pheromone is slowly released, pads, beads, tubes, rods, spirals, or balls, which are made of rubber, plastic, leather, cotton, absorbent cotton, wood, or wood products and are impregnated with the pheromone composition. Examples include polyvinyl chloride laminates, pellets, granules, ropes or spirals from which the pheromone composition evaporates, or rubber septums. Those skilled in the art will be able to select a carrier and / or dispenser suitable for any desired manner relating to application, storage, transport, or handling.

[0206] Various pheromones such as (Z)-tetradeca-9-en-1-yl acetate, (Z)-dodeca-9-en-1-yl acetate, and (Z)-tetradeca-11-en-1-yl acetate can be prepared according to the method of the present invention and formulated as described above. For example, by using the method of the present invention, a fall armyworm (Spodoptera frugiperda) pheromone, which is (Z)-tetradeca-9-en-1-yl acetate, can be prepared. The fall armyworm pheromone can be used in combination with a pheromone sustained release device having a polymer container that contains a mixture of the fall armyworm pheromone and a fatty acid ester (such as sebacate, laurate, palmitate, stearate, or arachidate) or an aliphatic alcohol (such as undecanol, dodecanol, tridecanol, tridecenol, tetradecanol, tetradecenol, tetradecadienol, pentadecanol, pentadecenol, hexadecanol, hexadecenol, hexadecadienol, octadecenol, and octadecadienol). The polymer container may be a tube, ampoule, or bag made of polyolefin or an olefin component-containing copolymer. Sex pheromones of other pests such as tobacco budworm (Helicoverpa armigera), pear fruit moth (Grapholita molesta), and tortricidae can be used in this type of pheromone sustained release device. Typically, sex pheromones contain one or more aliphatic acetate compounds having 10 to 16 carbon atoms (e.g., decyl acetate, decenyl acetate, decadienyl acetate, undecyl acetate, undecenyl acetate, dodecyl acetate, dodecenyl acetate, dodecadienyl acetate, tridecyl acetate, tridecenyl acetate, tridecadienyl acetate, tetradecyl acetate, tetradecenyl acetate, tetradecadienyl acetate, etc.) and / or one or more aliphatic aldehyde compounds having 10 to 16 carbon atoms (e.g., 7-hexadecenal, 11-hexadecenal, 13-octadecenal, etc.).

[0207] Pheromones prepared according to the method of the present invention, and compositions containing said pheromones, can be used to control insect behavior and / or reproduction in various environments. These pheromones can be used to attract, for example, male or female insects to or repel specific target areas. They can also be used to attract insects away from vulnerable crop areas. Furthermore, these pheromones can be used to attract insects as part of strategies for, for example, insect monitoring, mass capture, seduction / attraction and death, or mating disruption.

[0208] Mass capture involves placing high-density traps within a crop so that a high proportion of insects are removed before the crop to be protected suffers damage. The lure / attraction and kill technique is similar, except that insects are exposed to a killer when attracted to a lure. If the killer is an insecticide, the dispenser may contain bait or feeding stimulants that induce insects to ingest an effective amount of the insecticide.

[0209] Those skilled in the art will recognize that various different traps are possible. Preferred examples of such traps include water traps, sticky traps, and unidirectional traps. There are many types of sticky traps. One example of a sticky trap has a cardboard structure, a triangular or wedge-shaped cross-section, and an inner surface coated with a non-drying sticky material. Insects are trapped upon contact with the sticky surface. A water trap includes a dish of water and detergent used to capture insects. The detergent drowns insects attracted to the dish by breaking the surface tension of the water. A unidirectional trap attracts insects into the trap but prevents them from escaping. The traps of the present invention may be brightly colored to add to their attractiveness to insects.

[0210] The trap is positioned in an area where insects invade (or are likely to invade). Generally, the trap is located on or near a tree or large plant, and pheromones attract the insects to the trap. There, the insects are captured, immobilized, and / or may die within the trap due to a killer present in the trap, for example.

[0211] Furthermore, mating can be disrupted using pheromones prepared according to the method of the present invention. Mating disruption strategies include confusion, trajectory obscuration, and trajectory mistracking. By constantly exposing insects to high concentrations of pheromones, it is possible to prevent male insects from responding to the normal levels of hormones released by female insects. Trajectory obscuration is achieved by using pheromones to disrupt the trajectory of pheromones released by female insects. Trajectory mistracking is achieved by placing numerous spots of pheromone at high concentrations, thereby presenting male insects with many false trajectories to track. When released in sufficiently large quantities, male insects will be unable to find the natural source of sex pheromones (female insects), and therefore mating cannot occur.

[0212] Insect populations can be surveyed or monitored by counting the number of insects in a target area (e.g., the number of insects caught in traps). Inspections by gardeners can provide information about the life stage of the population. Knowing where insects are, how many there are, and their life stages allows for informed decisions about where and when insecticides or other treatments are permissible. For example, the discovery of a large insect population may inevitably lead to the use of methods for insect control. Early warning of invasion into new habitats can allow action to be taken before the population becomes unmanageable. Conversely, the discovery of a small insect population may lead to the decision that continued monitoring of the population is sufficient. Insect populations can be regularly monitored so that insects are controlled only when they reach a certain threshold. This results in cost-effective insect control and reduces the environmental impact of insecticide use.

[0213] As will be apparent to those skilled in the art, the amount of pheromone or pheromone composition used for a particular application may vary depending on several factors, including the type and level of intrusion; the type of composition used; the concentration of the active ingredient; how the composition is dispensed, for example, the type of dispenser used; the type of location being treated; the length of time the method should be used; and environmental factors such as temperature, wind speed and direction, rainfall, and humidity. Those skilled in the art will be able to determine the amount of pheromone or pheromone composition that is effective for use in a given application. [Examples]

[0214] IV. Examples Example 1 Synthesis of oleyl alcohol Commercially available oleyl alcohol contains isomerized impurities (i.e., elaidyl alcohol) due to the extreme conditions inevitably associated with the heterogeneous catalyst (i.e., copper chromate) used in the process. In some cases, high-purity oleyl alcohol can be prepared using homogeneous catalysts such as [Ru-SNS] or [Ru-PNP] and relatively mild conditions (see Figure 1).

[0215] In a typical preparation, methyl oleate is combined in a reactor with a base (i.e., sodium ethoxide), possibly a solvent (i.e., tetrahydrofuran), and a catalytic amount of ester hydrogenation catalyst (i.e., [Ru-SNS] or [Ru-PNP]). The reactor is then heated to 30–60°C and pressurized to 5–30 bar with hydrogen gas. When the reaction is complete, the reactor is reduced in pressure and the contents are washed with water or an aqueous solution (i.e., an aqueous hydrochloric acid solution) to remove reaction byproducts. If necessary, the product may be further purified by distillation or other methods. Oleyl alcohols produced using Ru-SNS and Ru-PNP exhibit a Z selectivity of over 98% and an excess reduction of double bonds of less than 1.0%.

[0216] Example 2 Synthesis of oleyl acetate Condition A: Oleyl alcohol (1 molar equivalent), dichloromethane, and NEt3 (3 molar equivalents) were added to a round-bottom flask equipped with a magnetic stirrer. The flask was placed under an inert atmosphere and cooled in an external ice bath. Acetic anhydride (2 molar equivalents) was added dropwise to the flask, followed by a catalytic amount of 4-dimethylaminopyridine. The reaction mixture was slowly heated to room temperature overnight. After 16 hours, the reaction was stopped with water, and the organic layer was washed with saturated ammonium chloride aqueous solution. After further washing with saturated aqueous solutions of both sodium bicarbonate and sodium chloride, the resulting organic layer was dried using anhydrous magnesium sulfate. Magnesium sulfate was filtered off, and all volatile components were removed under reduced pressure to obtain a yellow to colorless oily substance in yield of over 95%.

[0217] Condition B: Oleyl alcohol (1 molar equivalent) and a catalytic amount of anhydrous sodium acetate were added to a round-bottom flask equipped with a magnetic stirrer. The flask was placed under an inert atmosphere and heated to 60°C with stirring. Acetic anhydride (1.2 molar equivalents) was added at a rate that did not exceed 60°C. After 16 hours, the reaction mixture was cooled to ambient temperature and the reaction was stopped with water. The organic layer was washed with water and then dried using anhydrous magnesium sulfate. Magnesium sulfate was filtered off to obtain a yellow to colorless oily substance in yield of over 95%.

[0218] Depending on the commercial source of oleyl alcohol, the Z:E ratio of the oleyl acetate obtained by these procedures was as low as 80:20 and generally did not exceed 95:5.

[0219] Example 3 Synthesis of Z-internal olefins for metathesis reactions

[0220] General procedure for the synthesis of Z-internal olefins Z-internal olefins are synthesized by metathesis of terminal olefins using a cis-selective metal metathesis catalyst (e.g., tungsten or ruthenium catalyst). The ethylene produced during the metathesis reaction is sparged with an inert gas, such as nitrogen or argon. Alternatively, the ethylene may be removed by applying an appropriate reduced pressure while leaving the starting materials in the reaction system.

[0221] Add 1.0 mol of terminal olefin (less than 100 ppm water; peroxide value (PV) less than 0.1 meq / kg) to a reactor containing a reflux condenser and an optional inert gas inlet, and degas with an inert gas for 15 minutes. If using a tungsten catalyst, add a saturated ester such as methyl caprate (1000-5000 mol ppm relative to the internal olefin). Add triethylaluminum (TEAl; 1000-3000 mol ppm per 1 mol of terminal olefin) and stir for 1 to 24 hours (e.g., 4 to 8 hours). If using a ruthenium catalyst, filtering the starting material through an activated alumina plug is an efficient pretreatment to obtain less than 100 ppm water and less than 0.1 meq / kg of PV.

[0222] Add the cis-selective catalyst (3-50 mol ppm per 1 mol of terminal olefin) in a single step and start stirring. Initiate inert gas sparging at a flow rate of 15-30 L / h / Kg. Alternatively, ethylene removal may be accelerated by using reduced pressure, typically in the range of 400 Torr-30 Torr. Maintain the starting materials in the reactor using a reflux condenser. Carry out the metathesis reaction for 1-30 hours, usually 4-8 hours.

[0223] The tungsten catalyst is inactivated with 3000-5000 mol ppm of alcohol (e.g., methanol, ethanol, isopropanol, oleyl alcohol, etc.) per 1 mol of terminal olefin. Careful selection of the alcohol allows for the recycling of the starting materials and intermediates. The addition of alcohol inactivates the metathesis catalyst and decomposes excess triethylaluminum. Tetraethylenepentamine (TEPA; 100 mol excess relative to the catalyst) is added to the ruthenium catalyst and heated under reflux for 1 hour. The typical reaction yield with both catalysts is 50%-70%, and the Z selectivity is over 97%.

[0224] Z5-Decene Synthesis The synthesis of Z5-decene involves the self-metathesis of undiluted 1-hexene using a Z-selective catalyst. The resulting ethylene is removed from the reaction mixture under reduced pressure. Efficient removal of ethylene contributes to high yield and high Z selectivity. 40.8 g (0.49 mol) of 1-hexene (water concentration less than 50 ppm and peroxide value (PV) less than 0.1 meq / kg) was added to a 250 mL round-bottom three-neck flask containing a reflux condenser, an inert gas inlet, and a magnetic stirrer. The material was degassed with nitrogen for 15-30 minutes while raising the temperature to 50°C. Ruthenium catalyst 1 (2.6 mg, 3.92 x 10) -6 A single dose of 8 ppm (moles / double bond) was added. The top of the reflux condenser was connected to a diaphragm pump, and reduced pressure was applied. The reduced pressure was controlled between 160 Torr and 90 Torr. TIFF2026086750000063.tif40128

[0225] After 7 hours, GC analysis showed a yield of 75.9% and a Z selectivity of 99% for Z5-decene. TEPA (100 molar equivalents relative to the catalyst) was added to stop the ruthenium catalyst reaction. The reaction mixture was distilled under reduced pressure (170 Torr, boiling point 114°C) to obtain Z5-decene (24.2 g, 0.17 mol) with an isolation yield of 71.4% and a Z selectivity of 99%. See Experiments 3-14 in Table 1.

[0226] (Table 1) Synthesis of Z5-decene using ruthenium catalyst 1 TIFF2026086750000064.tif217131 a GC area (%). b [((Z+E)5-Decene area% x EOR mass) / 5-Decene theoretical mass] x 100

[0227] Further experiments, summarized in Table 1, involved reacting 1-hexene with ruthenium catalyst 1 at 20°C–60°C to obtain Z5-decene in yields of 60%–80% and a Z selectivity of 99%. Ruthenium catalyst 1 is air and moisture resistant, which is particularly advantageous for facilitating handling during the production of fine chemicals such as insect pheromones. Ruthenium catalyst 1 was found to consistently show improved Z:E ratios and increased yields compared to other cis-selective catalysts, for example, a 10% increase in yield. These advantages enable an unparalleled economical production process.

[0228] Z5-Decene Synthesis 1-Hexene was reacted with tungsten catalyst 2 at 20°C to 40°C to obtain Z5-decene in a yield of 60% to 70% and a Z selectivity of over 97%. See Tables 2 and 3. TIFF2026086750000065.tif63128

[0229] Synthesis of Z3-hexene 1-butene is reacted with catalyst 1 or catalyst 2 at -10°C to 10°C to obtain Z3-hexene. The reaction is work-up when the Z selectivity drops to 97%, or after 24 hours. A yield of over 35% is obtained.

[0230] Z4-Octene Synthesis 1-pentene is reacted with catalyst 1 or catalyst 2 at 15°C to 30°C to obtain Z4-octene. The reaction is work-up when the Z selectivity drops to 97%, or after 24 hours. A yield of over 50% is obtained.

[0231] Synthesis of Z3-hexene and Z5-decene As a technique to increase the efficiency of 1-butene, 1-hexene saturated with 1-butene is reacted with catalyst 1 or catalyst 2 at 10°C to 40°C to obtain Z5-decene, Z3-octene, and Z3-hexene. The reaction is work-up when the Z selectivity drops to 97%, or after 24 hours. A yield of over 60% of the total Z5-decene, Z3-octene, and Z3-hexene is obtained relative to the 1-hexene and 1-butene used.

[0232] (Table 2) Synthesis of Z5-decene using tungsten catalyst 2 TIFF2026086750000066.tif23844* The yield of deca-5-ene is calculated by multiplying the GC-FID area %(E+Z) by the reaction completion (EOR) mass and dividing by the theoretical mass of deca-5-ene.

[0233] (Table 3) Synthesis of Z5-decene using tungsten catalyst 2 TIFF2026086750000067.tif23856* The yield of deca-5-ene is calculated by multiplying the GC-FID area %(E+Z) by the reaction completion (EOR) mass and dividing by the theoretical mass of deca-5-ene.

[0234] Synthesis of Z7-tetradecene 1-Octene is reacted with catalyst 1 or catalyst 2 at 15°C to 30°C to obtain Z7-tetradecene. The reaction is work-up when the Z selectivity drops to 97%, or after 24 hours. A yield of over 50% is obtained.

[0235] Synthesis of Z9-octadecene 1-decene is reacted with catalyst 1 or catalyst 2 at 15°C to 30°C to obtain Z9-octadecene. The reaction is work-up when the Z selectivity drops to 97%, or after 24 hours. A yield of over 60% is obtained.

[0236] Self-metathesis of methyl 9-decenoate (9-DAME) to Z9-octadecene-dioate 1,18-dimethyl ester (ODDA) 9-DAME is reacted with catalyst 1 or catalyst 2 at 20°C to 40°C under reduced pressure of less than 1 Torr to obtain ODDA. The reaction is worked up when the Z selectivity drops to 97%, or after 24 hours. ODDA is purified by thin-film evaporation.

[0237] Self-metathesis of 9-decenyl acetate to Z9-octadecene-dinyl 1,18-diacetate (ODDAc2) ODDAc2 is obtained by reacting 9-decenyl acetate with catalyst 1 or catalyst 2 at 20°C to 40°C under reduced pressure of less than 1 Torr. The reaction is work-up when the Z selectivity decreases to 97%, or after 24 hours. ODDAc2 is purified by thin-film evaporation.

[0238] Self-metathesis from 8-nonenyl acetate to Z8-hexadecene-dinyl 1,16-diaacetate (HDDAc2) HDDAc2 is obtained by reacting 8-nonenyl acetate with catalyst 1 or catalyst 2 at 20°C to 40°C under reduced pressure of less than 1 Torr. The reaction is work-up when the Z selectivity decreases to 97%, or after 24 hours. HDDAc2 is purified by thin-film evaporation.

[0239] Self-metathesis of 7-octenyl acetate to Z7-tetradecene-dinyl 1,14-diacetate (TDDAc2) 7-octenyl acetate is reacted with catalyst 1 or catalyst 2 at 20°C to 40°C under reduced pressure of less than 1 Torr to obtain Z7-tetradecene-dinyl 1,14-diacetate TDDAc2. The reaction is work-up when the Z selectivity decreases to 97%, or after 24 hours. TDDAc2 is purified by thin-film evaporation.

[0240] Self-metathesis from 9-decenal acetal to Z9-octadecene-1,18-dial 1,18-diale (ODDA(acetal)2) 9-decenal acetal (the acetal may be, but is not limited to, dimethyl acetal, diethyl acetal, ethylene glycol acetal, or propylene glycol acetal) is reacted with catalyst 1 or catalyst 2 at 20°C to 40°C under reduced pressure of less than 1 Torr to obtain ODDA(acetal)2. The reaction is work-up when the Z selectivity drops to 97%, or after 24 hours. ODDA(acetal)2 is purified by thin-film evaporation.

[0241] Example 4 Cross-metathesis between oleyl acetate and (Z)-deca-5-ene Commercially available oleyl acetate (Z9-18Ac) is a low-cost raw material for the production of Z9 pheromones such as Z9-12Ac and Z9-14Ac. However, due to the nature of the hydrogenation and distillation used in the production of oleyl acetate, a significant amount (approximately 20%) of cis / trans isomerization occurs, resulting in the formation of elaidyl alcohol (E9-18Ac). Therefore, it was expected that metathesis products prepared from available materials would contain a significant amount of E-olefin impurities. However, as detailed below, it has now been found that when the metathesis reaction was carried out with catalysts such as catalyst 3, catalyst 4, and catalyst 5, surprisingly high Z content (over 99%) was obtained in the product.

[0242] As shown in Figure 2, cross-metathesis between oleyl acetate (Z9-18Ac or "OA") and (Z)-deca-5-ene in the presence of catalyst 3, catalyst 4, or catalyst 5 forms (Z)-tetradeca-9-en-1-yl acetate (Z9-14Ac) and metathesis co-products.

[0243] General Procedures for Cross-Metathesis Screening Reactions In an inert atmosphere, olefin starting materials (i.e., OA and (Z)-deca-5-ene) and a magnetic stirrer were added to a vial. A stock solution of the metathesis catalyst (e.g., catalyst 3, catalyst 4, or catalyst 5) in dichloromethane was prepared. The required amount of catalyst solution was added to a vial containing oleyl acetate and (Z)-deca-5-ene, and the resulting mixture was stirred at ambient temperature (approximately 30°C). After stirring the reaction mixture for typically 2 hours, an excess of tris(hydroxymethyl)phosphine relative to the amount of metathesis catalyst added was added. Next, water and dichloromethane were added to the reaction-stopped sample. The organic layer was then separated, dried over magnesium sulfate, and analyzed by gas chromatography (GC). GC analysis was performed using an HP-5 or HP-88 capillary column. GC data were analyzed using the following formula. TIFF2026086750000068.tif63128

[0244] Oleyl acetate pretreatment to maximize catalyst efficiency Using the general procedure described above for cross-metathesis, 0.5 mmol of oleyl acetate (pre-treated or unpre-treated), 1.5 mmol of (Z)-deca-5-ene, and 0.113 μmol or 0.038 μmol of catalyst 3 or catalyst 4 were combined. Pre-treated oleyl acetate was purified by storage on an alumina bed or by reaction with homogeneous magnesium aluminum isopropoxide (MgAl2(Oi-Pr)8). In the case of pre-treatment using MgAl2(Oi-Pr)8, the reagent and oleyl acetate starting material were mixed and stored at ambient temperature for approximately 20 hours, after which the screening reaction was performed without removing the pre-treatment reagent. The reaction was analyzed using GC. The effect of oleyl acetate pre-treatment on catalytic efficiency is shown in Table 4.

[0245] (Table 4) TIFF2026086750000069.tif87137

[0246] Triethylaluminum (TEAl) may be used as a pretreatment, as described below.

[0247] Optimization of magnesium aluminum isopropoxide pretreatment conditions Using the general procedure for cross-metathesis described above, 0.5 mmol of oleyl acetate (pre-treated or unpre-treated with MgAl2(Oi-Pr)8), 1.5 mmol of (Z)-deca-5-ene, and 0.113 μmol or 0.038 μmol of catalyst 3 or catalyst 4 were combined. The pre-treated oleyl acetate was purified by reaction with homogeneous MgAl2(Oi-Pr)8, in which the MgAl2(Oi-Pr)8 and oleyl acetate starting materials were mixed and stored at ambient temperature for approximately 1, 2, 4, 8, or 20 days before the screening reaction was carried out without removing the pre-treatment reagents. The results of GC analysis of these pre-treatment optimized screening reactions are shown in Table 5.

[0248] (Table 5) TIFF2026086750000070.tif166163

[0249] Dynamics of E / Z isomerization of the product in cross-metathesis between oleyl acetate and (Z)-deca-5-ene Using the general procedure described above, 0.5 mmol of oleyl acetate, 1.5 mmol of (Z)-deca-5-ene, and 0.113 μmol of catalyst 3 or catalyst 4 were combined. Aliquots were acquired at 0.5 hours, 1 hour, 2 hours, 3 hours, 4 hours, or 5 hours after the start of the reaction, and the effect of longer reaction times on the Z content of the product was determined by GC analysis. The results of the GC analysis of these E / Z isomerization screening reactions are shown in Table 6.

[0250] (Table 6) TIFF2026086750000071.tif88128

[0251] Preparative cross-metathesis of oleyl acetate and (Z)-deca-5-ene In an argon-filled glove box, (Z)-deca-5-ene (620.4 g, 4.42 mol) and oleyl acetate (458.5 g, 1.48 mol), both pre-treated with activated alumina, were added to a 3-liter round-bottom flask equipped with a stirring bar. Ruthenium catalyst 3 (0.375 g, 0.442 mmol) was added to the flask, and the reaction mixture was stirred at ambient temperature. After 5 hours, the contents of the flask were transferred to a 5-liter jacketed flask. Tris(hydroxymethyl)phosphine (30 mL, 68 equivalents of 1 M isopropanol solution) was added, and the contents were stirred at 60°C for 18 hours. The reaction mixture was then washed twice with 1 liter of water. The organic layer was separated, dried over anhydrous magnesium sulfate, and filtered through a fritted medium-porous funnel to obtain a pale yellow liquid. The mixture was purified by fractional distillation under reduced pressure at less than 0.1 Torr. GC analysis revealed that the main fraction, 183g, was 85% pure Z9-14Ac (0.63 mol, molar yield 43% relative to oleyl acetate). This fraction was collected at a head temperature of 89-100°C.

[0252] Example 5 Cross-metathesis of oleyl acetate and (Z)-hexa-3-ene As shown in Figure 3, cross-metathesis between oleyl acetate (Z9-18Ac or "OA") and (Z)-hexa-3-ene in the presence of catalyst 3 forms (Z)-dodeca-9-en-1-yl acetate (Z9-12Ac) and metathesis co-products (not shown).

[0253] In a flask equipped with a stirring bar, add (Z)-hexa-3-ene (3 mol) and oleyl acetate (1 mol), both of which have already been purified. Add the amount of catalyst 3 required to reach the equilibrium conversion rate to the flask and stir the reaction mixture at ambient temperature. When the reaction is complete, inactivate the catalyst by adding tris(hydroxymethyl)phosphine and heat the contents while stirring. Next, wash the reaction mixture with water and separate the organic layer. After drying the organic layer, purify it by fractional distillation under reduced pressure to obtain pure (Z)-dodeca-9-en-1-yl acetate (Z9-12Ac).

[0254] Example 6 Testing of starting material compositions in cross-metathesis of oleyl acetate and (Z)-deca-5-ene Synthesis of Z9-14Ac (Z9-tetradecenyl acetate) from oleyl acetate and Z5-decene Oleyl alcohol (Jarchem or BASF) was acetylated with acetic anhydride and a catalytic amount of sodium acetate, worked up, and purified by thin-film evaporation. The Z:E ratio of oleyl acetate was low at 80:20 and generally did not exceed 95:5. Oleyl acetate (310 g, 1.0 mol) and Z5-decene (700 g, 5.0 mol) were added to a 2 L round-bottom three-neck flask containing an inert gas inlet and a magnetic stirrer, both with water concentrations less than 100 ppm and PV less than 0.1 meq / Kg. The reaction mixture was degassed with nitrogen for 30 minutes. Magnesium aluminum isopropoxide (CAS number 69207-83-6) (10 g, 1 wt%) was added, and the reaction mixture was stirred at 45°C for 24 hours. Ruthenium stereochemically retained metathesis catalyst 4 (304 mg, 0.4 mmol; 50 mol ppm per 1 mol of internal double bonds) was added in one step, and stirring was started. The reaction mixture was stirred at 45°C for 5 hours. After 5 hours, TEPA (100 molar excess relative to the catalyst) was added, and the mixture was heated at 120°C for 1 hour. The reaction mixture was cooled to 45°C, and the excess and TEPA-catalyst complex were removed with 250 mL of 1 M HCl. Sodium bicarbonate (200 mL, saturated aqueous solution) was added, mixed, and the aqueous phase was removed.

[0255] The crude reaction mixture was purified by vacuum distillation in a fractional distillation column accommodating at least eight theoretical plates. Z5-decene and Z5-tetradecene were removed under reduced pressure of 160 Torr. The product Z9-14Ac (203 g, 0.8 mol, boiling point 105°C–110°C at 0.2 Torr) was obtained in good yield and with excellent selectivity using ruthenium catalyst 4. The product was isolated with a purity of 95% and a Z selectivity of 99.4%. The main impurity was Z9-octadecene (3%). The Z9-octadecene concentration can be minimized by increasing the equivalent amount of Z5-decene added in the metathesis reaction and by using improved distillation conditions. Furthermore, ruthenium catalyst 4 is a crystalline material that does not tend to generate static charge, which is particularly advantageous for handling during production.

[0256] The effect of bond geometry in non-functionalized olefins such as Z5-decene was also tested. Oleyl acetate was reacted with a mixture of 5-decene isomers having different E / Z ratios. This isomer mixture was prepared by mixing Z5-decene (95% Z) with a thermodynamic mixture of 5-decene isomers in different ratios (E / Z = 81.5 / 18.5%). The results are shown in Table 7 below. A remarkable Z selectivity of approximately 95% was observed even when the decene starting material was approximately 60% E5-decene.

[0257] (Table 7) TIFF2026086750000072.tif41164 a Yield calculated from GC area percentage.

[0258] Example 7 Synthesis of jojoba oil acetate In a round-bottom flask, commercially available jojoba oil (3.5 kg) was reduced in toluene at approximately 0°C using 1.2 molar equivalents of bis(2-methoxyethoxy)aluminum sodium hydride. The reaction mixture was stopped with an aqueous sulfuric acid solution and then washed with water. Next, the crude jojoba oil alcohol was acetylated in toluene at 75-95°C using an excess amount of acetic anhydride and a catalytic amount of sodium acetate anhydride. After workup, the final molar yield of jojoba oil acetate was over 85%. GC analysis revealed that the final product consisted of (Z)-octadeca-9-en-1-yl acetate 5.2 area%, (Z)-icosa-11-en-1-yl acetate 55.6 area%, (Z)-docosa-13-en-1-yl acetate 30.4 area%, (Z)-tetracosa-15-en-1-yl acetate 6.17 area%, and unidentified 2.6 area%.

[0259] Example 8 Cross-metathesis of jojoba oil acetate and (Z)-hexa-3-ene As shown in Figure 4, cross-metathesis of a mixture of jojoba oil acetate ("JOA") prepared from commercially available jojoba oil in the presence of catalyst 3, catalyst 4, or catalyst 5 and (Z)-hexa-3-ene forms (Z)-dodeca-9-en-1-yl acetate (Z9-12Ac), (Z)-tetradeca-11-en-1-yl acetate (Z11-14Ac), (Z)-hexadeca-13-en-1-yl acetate (Z13-16Ac), (Z)-octadeca-15-en-1-yl acetate (Z15-18Ac), and metathesis co-products.

[0260] General Procedures for Cross-Metathesis Screening Reactions In an inert atmosphere, olefin raw materials (i.e., jojoba oil acetate and 2-4 molar excess of (Z)-hexa-3-ene) and a magnetic stirrer were added to a flask. A stock solution of catalyst 3 or catalyst 4 in dichloromethane was prepared. The required amount of catalyst solution was added to a flask containing jojoba oil acetate (JOA) and (Z)-hexa-3-ene, and the resulting mixture was stirred at ambient temperature (approximately 30°C). After stirring the reaction mixture for typically 2 hours, an excess of tris(hydroxymethyl)phosphine relative to the amount of metathesis catalyst added was added. Next, water and dichloromethane were added to the reaction-stopped sample. The organic layer was then separated, dried over magnesium sulfate, and analyzed by gas chromatography (GC). GC analysis was performed using an HP-5 or HP-88 capillary column. GC data were analyzed using the following formula. TIFF2026086750000073.tif46142

[0261] Cross-metathesis of jojoba oil acetate with varying amounts of (Z)-hexa-3-ene Using the general procedure for cross-metathesis described above, 100 mmol of prepared JOA and 2 or 4 molar equivalents of (Z)-hexa-3-ene were combined with catalyst 3 at a concentration of 75 ppm (mol) per double bond for 1 hour to investigate the effect of substrate addition on reaction yield and selectivity. The reaction was analyzed using GC. The results are shown in Table 8.

[0262] (Table 8) TIFF2026086750000074.tif28142

[0263] Cross-metathesis of jojoba oil acetate and (Z)-hexa-3-ene using catalyst 3 or catalyst 4 Using the general procedure for cross-metathesis described above, the effects of catalysts on reaction yield and selectivity were investigated by combining 100 mmol of prepared JOA and 300 mmol of (Z)-hexa-3-ene with catalyst 3 or 4 at concentrations of 2000 ppm, 300 ppm, or 150 ppm (mol) per double bond. The reactions were analyzed using GC. The results are shown in Table 9.

[0264] (Table 9) TIFF2026086750000075.tif61149

[0265] Cross-metathesis of jojoba oil acetate and (Z)-hexa-3-ene using various amounts of catalysts. Using the general procedure for cross-metathesis described above, the effects of catalyst addition on reaction yield and selectivity were investigated by combining 100 mmol of prepared JOA and 300 mmol of (Z)-hexa-3-ene with catalyst 3 at 2000 ppm, 300 ppm, or 150 ppm (mol) per double bond. The reactions were analyzed using GC. The results are shown in Table 10.

[0266] (Table 10) TIFF2026086750000076.tif48152

[0267] Example 9 Cross-metathesis of jojoba oil and (Z)-hexa-3-ene As shown in Figure 5 below, cross-metathesis of commercial jojoba oil (i.e., a fatty acid mixture) with (Z)-hexa-3-ene in the presence of catalyst 4 or catalyst 6 forms cross-metathesis jojoba oil fatty acids and metathesis co-products (not shown). The cross-metathesis jojoba oil fatty acids are then reduced to the corresponding cross-metathesis jojoba oil alcohols: (Z)-dodeca-9-en-1-ol (Z9-12OH), (Z)-tetradeca-11-en-1-ol (Z11-14OH), (Z)-hexadeca-13-en-1-ol (Z13-16OH), and (Z)-octadeca-15-en-1-ol (Z15-18OH).

[0268] Cross-metathesis of jojoba oil and (Z)-hexa-3-ene using catalyst 4 or catalyst 6 Using the general procedure for cross-metathesis described above, commercially available jojoba oil ("JO") (50 mmol) and (Z)-hexa-3-ene (300 mmol) were subjected to cross-metathesis using metathesis catalyst 4 or metathesis catalyst 6. The reaction was carried out at ambient temperature for 2 hours. Prior to GC analysis, the cross-metathesis JO sample (i.e., a mixture of cross-metathesis jojoba oil fatty acids) was subjected to reduction using sodium bis(2-methoxyethoxy)aluminum hydride according to the procedure described in Example 7, "Synthesis of Jojoba Oil Acetate". The content of (Z)-tetradeca-11-en-1-ol (Z11-14OH) and the Z selectivity of the Z11-14OH product were determined by analysis without further analysis of the resulting cross-metathesis JO alcohol. The GC data were analyzed using the following formula. The results are shown in Table 11. TIFF2026086750000077.tif47159

[0269] (Table 11) TIFF2026086750000078.tif44164

[0270] Example 10 Synthesis of functionalized olefin products for agricultural use General cross-metathesis reaction conditions using ruthenium stereopreserving metathesis catalyst Add 1.0 mol of functionalized internal olefin (e.g., oleyl acetate) and 3-6 molar equivalents of unfunctionalized Z-internal olefin (e.g., Z5-decene) to a reactor equipped with an inert gas inlet, both with less than 100 ppm of water and less than 0.1 meq / kg of PV. Degas the internal olefin with an inert gas for 15 minutes. Add triethylaluminum (1000-3000 mol ppm per 1 mol of internal olefin) and stir for 1-24 hours. Alternatively, filtering the starting materials through an activated alumina plug is an efficient pretreatment to obtain less than 100 ppm and less than 0.1 meq / kg of PV. Add a ruthenium stereo-retaining metathesis catalyst (3-50 ppm per internal double bond), such as catalyst 3, catalyst 4, or catalyst 5, in one step and start stirring. The reaction is usually carried out at 20°C-60°C. Add TEPA (100 mol excess relative to the catalyst) and heat to reflux temperature for 1 hour to inactivate the catalyst. The typical reaction yields for both catalysts are 50% to 85%, and the Z selectivity is over 97%. Purification and isolation are achieved by packed-bed vacuum fractionation.

[0271] Synthesis of Z9-14Ac from ODDAc2 and Z5-decene ODDAc2 (1 mol) and Z5-decene (4-8 mol of Z5-decene per mol of ODDAc2) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereochemically retained metathesis catalyst (e.g., catalyst 3, catalyst 4, or catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-14Ac is isolated by packed-bed vacuum fractionation to obtain Z9-14Ac with a Z selectivity of over 97%.

[0272] Synthesis of Z9-12Ac (Z7-dodecenyl acetate) from oleyl acetate and Z3-hexene As described above, oleyl alcohol is converted to oleyl acetate and purified. Oleyl acetate (1 mol) and Z3-hexene (3-6 mol of Z3-hexene per 1 mol of oleyl acetate) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereochemically retained metathesis catalyst (e.g., catalyst 3, catalyst 4, or catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-12Ac is isolated by packed-bed vacuum fractionation with a Z selectivity of over 97%. The level of impurities such as Z9-octadecene is maintained at less than 3%.

[0273] Synthesis of Z9-12Ac from ODDAc2 and Z3-decene ODDAc2 (1 mol) and Z3-hexene (4-8 mol of Z3-hexene per mol of ODDAc2) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum for 1-8 hours. A ruthenium stereochemically retained metathesis catalyst (e.g., catalyst 3, catalyst 4, or catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-12Ac is isolated by packed-bed vacuum fractionation to obtain Z9-12Ac with a Z selectivity of over 97%.

[0274] Synthesis of Z9-14Ac and Z9-12Ac from oleyl acetate and Z3-octene As described above, oleyl alcohol is converted to oleyl acetate and purified. Oleyl acetate (1 mol) and Z3-octene (3-6 mol of Z3-octene per 1 mol of oleyl acetate) are stirred, degassed under nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereochemically retained metathesis catalyst (e.g., catalyst 3, catalyst 4, or catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-14Ac and Z9-12Ac are isolated by packed-bed vacuum fractionation. Both Z9-14Ac and Z9-12Ac are isolated with a purity of over 95% and a Z selectivity of over 97%. The level of impurities such as Z9-octadecene is maintained at less than 3%.

[0275] Synthesis of Z9-14Ac and Z9-12Ac from ODDAc2 and Z3-octene ODDAc2 (1 mol) and Z3-octene (4-8 mol of Z3-octene per mol of ODDAc2) are stirred, degassed under nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereochemically retained metathesis catalyst (e.g., catalyst 3, catalyst 4, or catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-14Ac and Z9-12Ac are isolated by packed-bed vacuum fractionation. Both Z9-14Ac and Z9-12Ac are isolated with a purity of over 95% and a Z selectivity of over 97%.

[0276] Synthesis of Z8-12Ac (Z8-dodecenyl acetate) from HDDAc2 and Z4-octene HDDAc2 (1 mol) and Z4-octene (3-6 mol of Z4-octene per 1 mol of HDDAc2) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereochemically retained metathesis catalyst (e.g., catalyst 3, catalyst 4, or catalyst 5) is added, and the reaction is monitored by GC analysis. Z8-12Ac is isolated by packed-bed vacuum fractionation with a purity of over 95% and a Z selectivity of over 97%.

[0277] Synthesis of Z7-12Ac from TDDAc2 and Z5-Decene TDDAc2 (1 mol) and Z5-decene (3-6 mol of Z5-decene per 1 mol of TDDAc2) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereochemically retained metathesis catalyst (e.g., catalyst 3, catalyst 4, or catalyst 5) is added, and the reaction is monitored by GC analysis. Z7-12Ac is isolated by packed-bed vacuum fractionation with a purity of over 95% and a Z selectivity of over 97%.

[0278] Synthesis of Z9-16Ac (Z9-hexadecenyl acetate) from oleyl acetate and Z7-tetradecene As described above, oleyl alcohol is converted to oleyl acetate and purified. Oleyl acetate (1 mol) and Z7-tetradecene (4-8 mol of Z7-tetradecene per 1 mol of oleyl acetate) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereochemically retained metathesis catalyst (e.g., catalyst 3, catalyst 4, or catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-16Ac is isolated by packed-bed vacuum fractionation with a purity of over 95% and a Z selectivity of over 97%. The level of impurities such as Z9-octadecene is maintained at less than 1%.

[0279] Synthesis of Z9-16Ac from ODDAc2 and Z7-tetradecene ODDAc2 (1 mol) and Z7-tetradecene (4-8 mol of Z7-tetradecene per mol of ODDAc2) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereochemically retained metathesis catalyst (e.g., catalyst 3, catalyst 4, or catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-16Ac is isolated by packed-bed vacuum fractionation with a purity of over 95% and a Z selectivity of over 97%.

[0280] Synthesis of Z9-16 acetal (Z9-16 acetal is Z9-hexadecenal acetal) from ODDA (acetal) 2 and Z7-tetradecene. ODDA(acetal)2 (1 mol) and Z7-tetradecene (4-8 mol of Z7-tetradecene per 1 mol of ODDA(acetal)2) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereochemically retained metathesis catalyst (e.g., catalyst 3, catalyst 4, or catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-16 acetal is isolated by packed-bed vacuum fractionation with a purity of over 90% and a Z selectivity of over 95%.

[0281] Synthesis of Z9-18Ac (Z9-18Ac is Z9-octadecenyl acetate) from ODDAc2 and Z9-octadecene. ODDAc2 (1 mol) and Z9-octadecene (4-8 mol of Z9-octadecene per 1 mol of ODDAc2) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereochemically retained metathesis catalyst (e.g., catalyst 3, catalyst 4, or catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-18Ac is isolated by packed-bed vacuum fractionation with a purity of over 95% and a Z selectivity of over 97%.

[0282] Synthesis of Z9-18 acetal (Z9-18 acetal is Z9-octadecenal acetal) from ODDA (acetal) 2 and Z9-octadecene. ODDA(acetal)2 (1 mol) and Z9-octadecene (4-8 mol of Z9-octadecene per 1 mol of ODAc2) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereochemically retained metathesis catalyst (e.g., catalyst 3, catalyst 4, or catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-18 acetal is isolated by packed-bed vacuum fractionation with a purity of over 90% and a Z selectivity of over 95%.

[0283] Synthesis of jojoba acetate by reduction and acetylation of jojoba oil. Jojoba oil (Greenchem) is diluted with an equal volume of anhydrous toluene and reduced to 1 mole of jojoba ester with 1.5 molar equivalents of Vitride. After the reduction is complete, the reaction mixture is carefully diluted with sulfuric acid until the aqueous phase pH is less than 1, and washed with brine. The organic phase is isolated and anhydrous by azeotropic removal of water. Anhydrous jojoba alcohol is acetylated with oleyl acetate as previously described. Jojoba acetate is purified by thin-film evaporation in a yield of approximately 80%. The composition of the jojoba acetate is approximately 5% Z9-18Ac, 55% Z11-20Ac, 35% Z13-22Ac, and 5% Z15-24Ac.

[0284] Synthesis of Z9-12Ac, Z11-14Ac (Z11-tetradecenyl acetate), and Z13-16Ac (Z13-hexadecenyl acetate) from jojoba acetate and Z3-hexene. Jojoba acetate (1 mol) and Z3-hexene (4-8 mol of Z3-hexene per mol of jojoba acetate) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereochemically retained metathesis catalyst (e.g., catalyst 3, catalyst 4, or catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-12Ac, Z11-14Ac, and Z13-16Ac are isolated by packed-bed vacuum fractionation. Z9-12Ac, Z11-14Ac, and Z13-16Ac are isolated with a purity of over 95% and a Z selectivity of over 97%.

[0285] Synthesis of Z9-14Ac, Z11-16Ac (Z11-hexadecenyl acetate), and Z13-18Ac (Z13-hexadecenyl acetate) from jojoba acetate and Z5-decene. Jojoba acetate (1 mol) and Z5-decene (4-8 mol of Z5-decene per mol of jojoba acetate) are stirred, degassed under nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereochemically retained metathesis catalyst (e.g., catalyst 3, catalyst 4, or catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-14Ac, Z11-16Ac, and Z13-18Ac are isolated by packed-bed vacuum fractionation. Z9-14Ac, Z11-16Ac, and Z13-18Ac are isolated with a purity of over 95% and a Z selectivity of over 97%.

[0286] Synthesis of jojoba acetal by reduction, oxidation, and acetal formation from jojoba oil. Jojoba alcohol is prepared as described above. Anhydrous jojoba alcohol is oxidized to an aldehyde (e.g., by Stahl oxidation, Swern oxidation, or tetrapropylammonium perthenate (TPAP) oxidation). The jojoba aldehyde is converted to an acetal (e.g., dimethyl acetal, diethyl acetal, ethylene glycol acetal, or propylene glycol acetal) using an excess amount of alcohol and a catalytic amount of acid. The acetal is purified by thin-film evaporation with an isolation yield of approximately 70%. The composition of the jojoba acetal is approximately 5% Z9-18 acetal, approximately 55% Z11-20 acetal, approximately 35% Z13-22 acetal, and approximately 5% Z15-24 acetal.

[0287] Synthesis of Z9-14 acetal (Z9-tetradecenal acetal), Z11-16 acetal (Z11-hexadecenal acetal), and Z13-18 acetal (Z13-octadecenal acetal) from jojoba acetal and Z5-decene. Jojoba acetal (1 mol) and Z5-decene (4-8 mol of Z5-decene per 1 mol of jojoba acetal) are stirred, degassed with nitrogen for 15 minutes, and treated with triethylaluminum. A ruthenium stereochemically retained metathesis catalyst (e.g., catalyst 3, catalyst 4, or catalyst 5) is added, and the reaction is monitored by GC analysis. Z9-14 acetal, Z11-16 acetal, and Z13-18 acetal are isolated by packed-bed vacuum fractionation. Z9-14 acetal, Z11-16 acetal, and Z13-18 acetal are isolated with a purity of over 80% and a Z selectivity of over 90%.

[0288] Exemplary embodiments Exemplary embodiments provided in accordance with the subject matter disclosed herein include, but are not limited to, the claims and the embodiments described below.

[0289] 1. A method for synthesizing a Z-enriched aliphatic olefin metathesis product, comprising the step of contacting an olefin metathesis reaction partner and an internal olefin in the presence of a group 8 transition metal metathesis catalyst in order to form a Z-enriched aliphatic olefin metathesis product, wherein The aliphatic olefin metathesis product is an acylated alkenol or alkenal acetal. The olefin metathesis reaction partner contains a mixture of Z-olefin and E-olefin in a starting Z:E ratio. The aliphatic olefin metathesis product contains a mixture of Z-olefin and E-olefin in a Z:E ratio. Methods in which the product Z:E ratio is higher than the starting Z:E ratio.

[0290] 2. The aliphatic olefin metathesis product is given by formula I: It is an acylated alkenol of TIFF2026086750000079.tif16128; Metathesis reaction partner is Equation III: It is a compound of TIFF2026086750000080.tif16128; Internal olefin is formula IV: It is a compound of TIFF2026086750000081.tif10128; R 1 However, H and C 1~6 Selected from the group consisting of alkyl groups; R 2 However, C 1~18 Alkyl and C 2~18 Selected from the group consisting of alkenils; R 3 C 1~18 It is alkyl; The subscript y is an integer in the range of 0 to 17; The subscript z is an integer in the range of 0 to 17; The Group 8 transition metal metathesis catalyst is a Z-selective Group 8 transition metal catalyst. The method described in Embodiment 1.

[0291] 3. The method according to embodiment 1 or 2, wherein the metathesis catalyst is a Z-selective ruthenium catalyst or a Z-selective osmium catalyst.

[0292] 4. The method according to any one of embodiments 1 to 3, wherein the aliphatic olefin metathesis product is at least 97% Z.

[0293] 5. The method according to any one of embodiments 1 to 3, wherein the aliphatic olefin metathesis product is more than 98% Z.

[0294] 6. The method according to any one of embodiments 1 to 3, wherein the aliphatic olefin metathesis product is more than 99% Z.

[0295] 7. The method according to any one of embodiments 1 to 6, wherein the metathesis reaction partner is approximately 1% to approximately 50% E.

[0296] 8. Synthesis of aliphatic olefin metathesis products using acylating agents and formula II: A method according to any one of embodiments 2 to 7, comprising the step of contacting an alkenol of TIFF2026086750000082.tif10128 to form an olefin metathesis reaction partner of formula III.

[0297] 9. The method according to embodiment 8, wherein the acylating agent is acetic anhydride.

[0298] 10. Synthesis of aliphatic olefin metathesis reaction partners is given by formula IIa: TIFF2026086750000083.tif16128 (in the formula, R 4 H and C 1~8 (Selected from the group consisting of alkyl groups) The method according to embodiment 8 or 9, comprising the step of reducing an unsaturated aliphatic carboxyl derivative to form an alkenol of formula II.

[0299] 11. The method according to embodiment 10, wherein the step of forming the alkenol of formula II includes a step of contacting an unsaturated aliphatic carboxyl derivative with a base in the presence of a hydrogenation catalyst and hydrogen gas.

[0300] 12. The method according to embodiment 10, wherein the step of forming the alkenol of formula II includes a step of contacting an unsaturated aliphatic carboxyl derivative with a reducing agent.

[0301] 13. The method according to embodiment 12, wherein the reducing agent is sodium bis(2-methoxyethoxy)aluminum hydride.

[0302] 14. The method according to any one of embodiments 8 to 13, wherein the alkenol of formula II is approximately 1% to approximately 50% E.

[0303] 15. Aliphatic olefin metathesis product is given by formula VI: It is an alkenal acetal of TIFF2026086750000084.tif16128; Metathesis reaction partner is formula VII: It is a compound of TIFF2026086750000085.tif16128; Internal olefin is formula IV: It is a compound of TIFF2026086750000086.tif10128; R 1 C 1~6 It is alkyl; R 2 However, C 1~18 Alkyl and C 2~18 Selected from the group consisting of alkenils; R 3 C 1~18 It is alkyl; The subscript y is an integer in the range of 0 to 17; The subscript z is an integer in the range of 0 to 17; The Group 8 transition metal metathesis catalyst is a Z-selective Group 8 transition metal catalyst. The method described in Embodiment 1.

[0304] 16. Metathesis product is given by formula VIII: The method according to embodiment 15, further comprising the step of converting TIFF2026086750000087.tif16128 into alkenal.

[0305] 17. The method according to any one of embodiments 1 to 16, wherein the synthesis of an aliphatic olefin metathesis product includes a step of forming an internal olefin by contacting a terminal olefin with a metathesis catalyst.

[0306] 18. Internal olefin is formula VIa: It is a compound of TIFF2026086750000088.tif12128; Terminal olefin is formula IVb: The method according to embodiment 20, wherein the compound is TIFF2026086750000089.tif10128.

[0307] 19. The method according to embodiment 17 or 18, wherein the metathesis catalyst for forming the internal olefin is a Z-selective ruthenium catalyst or a Z-selective tungsten catalyst.

[0308] 20. Equation I: A method for synthesizing an aliphatic olefin metathesis product of TIFF2026086750000090.tif16128, Formula III: To form olefin metathesis reaction partners in TIFF2026086750000091.tif16128, an acylating agent and formula II: The process of contacting the alkenol of TIFF2026086750000092.tif10128; and To form an aliphatic olefin metathesis product, use an olefin metathesis reaction partner and formula IV: The process includes contacting the internal olefin of TIFF2026086750000093.tif10128 with a Z-selective ruthenium catalyst or a Z-selective osmium catalyst, wherein, R 1 However, H and C1~6 Selected from the group consisting of alkyl groups; R 2 However, C 1~18 Alkyl and C 2~18 Selected from the group consisting of alkenils; R 3 C 1~18 It is alkyl; The subscript y is an integer in the range of 0 to 17; The subscript z is an integer in the range of 0 to 17; A method for which the aliphatic olefin metathesis product is at least 97% Z.

[0309] 21. The method according to embodiment 20, wherein the acylating agent is acetic anhydride.

[0310] 22. The method according to embodiment 20 or 21, wherein the alkenol of formula II is approximately 1% to approximately 50% E.

[0311] 23. Equation I: A method for synthesizing an aliphatic olefin metathesis product of TIFF2026086750000094.tif16128, Formula II: To form the alkenol of TIFF2026086750000095.tif10128, formula IIa: A process for reducing the unsaturated aliphatic carboxyl derivative of TIFF2026086750000096.tif16128; Formula III: The steps of contacting an acylating agent with an alkenol to form an olefin metathesis reaction partner of TIFF2026086750000097.tif16128; and To form an aliphatic olefin metathesis product, use an olefin metathesis reaction partner and formula IV: The process includes contacting the internal olefin of TIFF2026086750000098.tif10128 with a Z-selective ruthenium catalyst or a Z-selective osmium catalyst, wherein, R 1 However, H and C 1~6Selected from the group consisting of alkyl groups; R 2 However, C 1~18 Alkyl and C 2~18 Selected from the group consisting of alkenils; R 3 C 1~18 It is alkyl; R 4 However, H and C 1~8 Selected from the group consisting of alkyl groups; The subscript y is an integer in the range of 0 to 17; The subscript z is an integer in the range of 0 to 17; A method for which the aliphatic olefin metathesis product is at least 97% Z.

[0312] 24. The method according to embodiment 23, wherein the step of reducing an unsaturated aliphatic carboxyl derivative of formula IIa to form an alkenol of formula II includes a step of contacting the unsaturated aliphatic carboxyl derivative with a base in the presence of a hydrogenation catalyst and hydrogen gas.

[0313] 25. The method according to embodiment 23, wherein the step of reducing an unsaturated aliphatic carboxyl derivative of formula IIa to form an alkenol of formula II includes a step of contacting the unsaturated aliphatic carboxyl derivative with a reducing agent.

[0314] 26. The method according to embodiment 25, wherein the reducing agent is sodium bis(2-methoxyethoxy)aluminum hydride.

[0315] 27. The method according to any one of embodiments 23 to 26, wherein the acylating agent is acetic anhydride.

[0316] 28. The method according to any one of embodiments 23 to 27, wherein the alkenol of formula II is approximately 1% to approximately 50% E.

[0317] 29. R 1 C 1~3 It is alkyl, R 2 C 1~12 It is alkyl, R 3 C 1~12The method according to any one of aspects 2 to 28, wherein R is alkyl, y is an integer in the range of 5 to 15, and z is an integer in the range of 0 to 7.

[0318] 30. R 1 is C 1~3 alkyl, and R 2 is C 1~12 alkyl, and R 3 is C 1~12 alkyl, and R 4 is C 1~3 alkyl, y is 7, and z is an integer in the range of 1 to 5. The method according to any one of aspects 10, 11, 23, and 24.

[0319] 31. R 1 is C 1~3 alkyl, and R 2 is C 1~12 alkyl, and R 3 is C 1~12 alkyl, and R 4 is H, y is an integer in the range of 5 to 15, and z is an integer in the range of 1 to 5. The method according to any one of aspects 10, 12, 23, and 25.

[0320] 32. The olefin metathesis reaction partner of formula III is an aliphatic C 12 ~C 30 olefin acetate; The internal olefin of formula IV is a C4~C 20 internal olefin; The aliphatic olefin metathesis product of formula I is a C8~C 28 (Z)-unsaturated aliphatic ester acetate, The method according to any one of aspects 2 to 7.

[0321] 33. The olefin metathesis reaction partner of formula III is (Z)-octadec-9-en-1-yl acetate; The internal olefin of formula IV is (Z)-deca-5-ene; The aliphatic olefin metathesis product of formula I is (Z)-tetradec-9-en-1-yl acetate. The method according to any one of Aspects 2 to 7 and 32.

[0322] 34. The olefin metathesis reaction partner of Formula III is (Z)-octadec-9-en-1-yl acetate; The internal olefin of Formula IV is (Z)-hex-3-ene; The aliphatic olefin metathesis product of Formula I is (Z)-dodec-9-en-1-yl acetate, The method according to any one of Aspects 2 to 7 and 32.

[0323] 35. The olefin metathesis reaction partner of Formula III is (Z)-eicosa-11-en-1-yl acetate; The internal olefin of Formula IV is (Z)-hex-3-ene; The aliphatic olefin metathesis product of Formula I is (Z)-tetradec-11-en-1-yl acetate, The method according to any one of Aspects 2 to 7 and 32.

[0324] 36. The alkenol of Formula II is a C 10 ~C 28 aliphatic alkenol; The olefin metathesis reaction partner of Formula III is a C 10 ~C 28 acetate ester of an aliphatic alkenol; The internal olefin of Formula IV is a C4~C 20 internal olefin; The aliphatic olefin metathesis product of Formula I is a C8~C 28 (Z)-unsaturated aliphatic ester acetate, The method according to any one of Aspects 8 to 31.

[0325] 37. The alkenol of Formula II is (Z)-octadec-9-en-1-ol; The olefin metathesis reaction partner of Formula III is (Z)-octadec-9-en-1-yl acetate; The internal olefin in formula IV is (Z)-deca-5-ene; The aliphatic olefin metathesis product of formula I is (Z)-tetradeca-9-en-1-yl acetate. The method described in any one of the descriptions in Actuals 10 to 36.

[0326] 38. The alkenol in formula II is (Z)-octadeca-9-en-1-ol; The olefin metathesis reaction partner in formula III is (Z)-octadeca-9-en-1-yl acetate; The internal olefin of formula IV is (Z)-hexa-3-ene; The aliphatic olefin metathesis product of formula I is (Z)-dodeca-9-en-1-yl acetate. The method described in any one of the descriptions in Actuals 10 to 36.

[0327] 39. The alkenol in formula II is (Z)-icosa-11-en-1-ol; The olefin metathesis reaction partner in formula III is (Z)-icosa-11-en-1-yl acetate; The internal olefin of formula IV is (Z)-hexa-3-ene; The aliphatic olefin metathesis product of formula I is (Z)-tetradeca-11-en-1-yl acetate. The method described in any one of the descriptions in Actuals 10 to 36.

[0328] 40. The method according to any one of embodiments 1 to 38, wherein the synthesis of an aliphatic olefin metathesis product includes a step of contacting the olefin metathesis reaction partner with a pretreatment reagent before contacting the internal olefin.

[0329] 41. The method according to embodiment 40, wherein the pretreatment reagent is selected from the group consisting of alumina, triethylaluminum, and magnesium aluminum isopropoxide.

[0330] 42. The method according to any one of embodiments 10-12 and 23-25, wherein the unsaturated aliphatic carboxyl derivative is derived from natural oil.

[0331] 43. The method according to embodiment 42, wherein the natural oil is selected from the group consisting of almond oil, canola oil, avocado oil, argan oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, grape seed oil, olive oil, palm oil, peanut oil, hemp seed oil, macadamia oil, safflower oil, sesame oil, soybean oil, sunflower oil, flaxseed oil, palm kernel oil, tuna oil, jatropha oil, jojoba oil, mustard oil, shepherd's purse oil, custard oil, castor oil, and combinations thereof.

[0332] 44. The method according to embodiment 42 or 43, further comprising the step of distilling an unsaturated aliphatic carboxyl derivative of formula IIa, an alkenol of formula II, or an olefin metathesis reaction partner of formula III prior to metathesis in order to remove plant-derived impurities.

[0333] 45. The method according to embodiment 44, wherein the plant-derived impurity comprises one or more proteins.

[0334] 46. ​​The structure of the Z-selective metathesis catalyst is given by formula V: It has TIFF2026086750000099.tif38128, During the ceremony, M is selected from the group consisting of ruthenium and osmium; X and Y are independently selected from the group consisting of S and O; Z is selected from the group consisting of O, S(=O), N, and halogens; Each subscript m and subscript n is an integer independently selected from 0, 1, 2, 3, and 4; Each R a R is independently selected from the group consisting of halogens, C1-C6 alkyls, alkoxys, aryls, and heteroaryls; or one R a is adjacent to R a Together with other elements, they form unsubstituted or substituted biringu or unsubstituted or substituted polyringu; Each R b R is independently selected from the group consisting of halogens, C1-C6 alkyls, alkoxys, aryls, and heteroaryls; or one R b is adjacent to R b Together with other elements, they form unsubstituted or substituted biringu or unsubstituted or substituted polyringu; R c It is selected from the group consisting of hydrogen and C1-C6 alkyl groups; Each R d , R e , R f , and R g These are independently selected from the group consisting of hydrogen and C1-C6 alkyl groups; R 12 and R 13 These are independently selected from the group consisting of 2,4,6-tri-isopropylphenyl, 2,6-di-isopropylphenyl, 2,6-di-adamantylphenyl, 2-isopropyl-6-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, and 2,6-di-tert-butylphenyl; Each R 14 These are independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, benzyl, and phenyl; R 15 R is selected from the group consisting of hydrogen, halogens, and C1-C6 alkyl groups, or R 15 and one R 14 They come together to form a bond. The method described in any one of the descriptions in Appearances 2 to 45.

[0335] 47. M is ruthenium; X and Y are S; Z is selected from the group consisting of O and S (=O); The subscript m is 2; The index n is 0; Each R a These are independently selected from the group consisting of halogens, C1-C6 alkyls, and aryls; Rc is hydrogen; Each R d , R e , R f , and R g is hydrogen; Each R 14 These are independently selected from the group consisting of methyl, isopropyl, benzyl, and tert-butyl. The method described in aspect 46.

[0336] 48. Metathesis catalysts comprise the following group: The method according to embodiment 46 or 47, selected from TIFF2026086750000100.tif48137.

[0337] While the above inventions have been described in some detail with illustrations and examples for clarity and understanding, those skilled in the art will recognize that certain changes and modifications can be carried out within the scope of the appended claims. All publications, patents, patent applications, and sequence accession numbers cited herein are incorporated herein by reference in their entirety for all purposes.

Claims

1. A method for synthesizing a Z-enriched aliphatic olefin metathesis product, comprising the step of contacting an olefin metathesis reaction partner and an internal olefin in the presence of a group 8 transition metal metathesis catalyst in order to form a Z-enriched aliphatic olefin metathesis product, wherein The aliphatic olefin metathesis product is an acylated alkenol or alkenal acetal. The olefin metathesis reaction partner contains a mixture of Z-olefin and E-olefin in a starting Z:E ratio. The aliphatic olefin metathesis product contains a mixture of Z-olefin and E-olefin in a Z:E ratio. Methods in which the product Z:E ratio is higher than the starting Z:E ratio.

2. The method according to claim 1, wherein the metathesis catalyst is a Z-selective ruthenium catalyst or a Z-selective osmium catalyst.

3. The method according to claim 1, wherein the aliphatic olefin metathesis product is at least 97% to 99% Z.

4. The method according to claim 1, wherein the aliphatic olefin metathesis product is more than 99% Z.

5. The method according to claim 1, wherein the metathesis reaction partner is approximately 1% to approximately 50% E.

6. Aliphatic olefin metathesis product is given by formula I: It is an acylated alkenol; Metathesis reaction partner is Equation III: It is a compound of; Internal olefin is formula IV: It is a compound of; R 1 However, H and C 1～6 Selected from the group consisting of alkyl groups; R 2 However, C 1～18 Alkyl and C 2～18 Selected from the group consisting of alkenils; R 3 C 1～18 It is alkyl; The subscript y is an integer in the range of 0 to 17; The subscript z is an integer in the range of 0 to 17; The Group 8 transition metal metathesis catalyst is a Z-selective Group 8 transition metal catalyst. The method according to claim 1.

7. The Z-selective metathesis catalyst has the structure of formula V: It has, During the ceremony, M is selected from the group consisting of ruthenium and osmium; X and Y are independently selected from the group consisting of S and O; Z is selected from the group consisting of S (=O), O, N, and halogens; The subscript m is an integer selected from 2, 4, 3, 1, and 0; The subscript n is an integer selected from 0, 1, 2, 3, or 4; Each R a is independently selected from the group consisting of halogen, C 1 -C 6 alkyl, alkoxy, aryl, and heteroaryl; or one R a together with an adjacent R a forms an unsubstituted or substituted bicyclic or unsubstituted or substituted polycyclic ring; Each R b They are independent of halogen and C 1 ~C 6 Selected from the group consisting of alkyl, alkoxy, aryl, and heteroaryl; or one R b is adjacent to R b Together with other elements, they form unsubstituted or substituted biringu or unsubstituted or substituted polyringu; R c is hydrogen and C 1 ~C 6 Selected from the group consisting of alkyl groups; Each R d , R e , R f , and R g Hydrogen and C are independent of each other. 1 ~C 6 Selected from the group consisting of alkyl groups; R 12 and R 13 These are independently selected from the group consisting of 2,6-di-isopropylphenyl, 2,4,6-tri-isopropylphenyl, 2,6-di-adamantylphenyl, 2-isopropyl-6-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, and 2,6-di-tert-butylphenyl; Each R 14 These are independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, benzyl, phenyl, and hydrogen; R 15 These are hydrogen, halogens, and C 1 ~C 6 Selected from the group consisting of alkyl groups, or R 15 and one R 14 They come together to form a bond. The method according to claim 6.

8. M is ruthenium; X and Y are S; Z is selected from the group consisting of S (=O) and O; The subscript m is 2; The index n is 0; Each R a They are independent of halogen and C 1 ~C 6 Selected from the group consisting of alkyl and aryl; R c is hydrogen; Each R d , R e , R f , and R g is hydrogen; Each R 14 These are independently selected from the group consisting of methyl, isopropyl, benzyl, and tert-butyl. The method according to claim 7.

9. Metathesis catalysts are a group consisting of the following: The method according to claim 7, which is more selected.

10. The synthesis of aliphatic olefin metathesis products involves an acylating agent and formula II: The method according to claim 6, comprising the step of contacting with an alkenol to form an olefin metathesis reaction partner of formula III.

11. The method according to claim 10, wherein the acylating agent is acetic anhydride.

12. The synthesis of aliphatic olefin metathesis reaction partners is given by formula IIa: (In the formula, R 4 H and C 1～8 (Selected from the group consisting of alkyl groups) The method according to claim 10, comprising the step of reducing an unsaturated aliphatic carboxyl derivative to form an alkenol of formula II.

13. The method according to claim 12, wherein the step of forming the alkenol of formula II includes the step of contacting an unsaturated aliphatic carboxyl derivative with a base in the presence of a hydrogenation catalyst and hydrogen gas.

14. The method according to claim 12, wherein the step of forming the alkenol of formula II includes the step of contacting an unsaturated aliphatic carboxyl derivative with a reducing agent.

15. The method according to claim 14, wherein the reducing agent is sodium bis(2-methoxyethoxy)aluminum hydride.

16. The method according to claim 12, wherein the unsaturated aliphatic carboxyl derivative is derived from natural oil.

17. The method according to claim 16, wherein the natural oil is selected from the group consisting of almond oil, canola oil, avocado oil, argan oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, grape seed oil, olive oil, palm oil, peanut oil, hemp seed oil, macadamia oil, safflower oil, sesame oil, soybean oil, sunflower oil, flaxseed oil, palm kernel oil, tuna oil, jatropha oil, jojoba oil, mustard oil, shepherd's purse oil, custard oil, castor oil, and combinations thereof.

18. The method according to claim 16, further comprising the step of distilling an unsaturated aliphatic carboxyl derivative, alkenol, or olefin metathesis reaction partner prior to metathesis in order to remove plant-derived impurities.

19. Aliphatic olefin metathesis product is given by formula VI: It is an alkenal acetal; Metathesis reaction partner is formula VII: It is a compound of; Internal olefin is formula IV: It is a compound of; R 1 C 1～6 It is alkyl; R 2 However, C 1～18 Alkyl and C 2～18 Selected from the group consisting of alkenils; R 3 C 1～18 It is alkyl; The subscript y is an integer in the range of 0 to 17; The subscript z is an integer in the range of 0 to 17; The Group 8 transition metal metathesis catalyst is a Z-selective Group 8 transition metal catalyst. The method according to claim 1.

20. Metathesis product is given by formula VIII: The method according to claim 19, further comprising the step of converting to alkenal.

21. The method according to claim 1, wherein the synthesis of an aliphatic olefin metathesis product includes the step of forming an internal olefin by contacting a terminal olefin with a metathesis catalyst in order to form an internal olefin.

22. The internal olefin is given by formula VIa: It is a compound of; Terminal olefin is formula IVb: The method according to claim 21, wherein the compound is [the compound].

23. The method according to claim 21 or 22, wherein the metathesis catalyst for forming the internal olefin is a Z-selective ruthenium catalyst or a Z-selective tungsten catalyst.

24. R 1 C 1～3 It is alkyl, R 2 C 1～12 It is alkyl, R 3 C 1～12 The method according to claim 6, wherein the element is alkyl, y is an integer in the range of 5 to 15, and z is an integer in the range of 0 to 7.

25. The metathesis reaction partner in Equation III is aliphatic C 12 ~C 30 It is an olefin acetate; The internal olefin in formula IV is C 4 ~C 20 It is an internal olefin; The aliphatic olefin metathesis product of formula I is C 8 ~C 28 (Z)-unsaturated aliphatic ester acetate, The method according to claim 6.

26. The olefin metathesis reaction partner in formula III is (Z)-octadeca-9-en-1-yl acetate; The internal olefin in formula IV is (Z)-deca-5-ene; The aliphatic olefin metathesis product of formula I is (Z)-tetradeca-9-en-1-yl acetate. The method according to claim 6.

27. The olefin metathesis reaction partner in formula III is (Z)-octadeca-9-en-1-yl acetate; The internal olefin of formula IV is (Z)-hexa-3-ene; The aliphatic olefin metathesis product of formula I is (Z)-dodeca-9-en-1-yl acetate. The method according to claim 6.

28. The olefin metathesis reaction partner in formula III is (Z)-icosa-11-en-1-yl acetate; The internal olefin of formula IV is (Z)-hexa-3-ene; The aliphatic olefin metathesis product of formula I is (Z)-tetradeca-11-en-1-yl acetate. The method according to claim 6.

29. The method according to claim 1, wherein the synthesis of an aliphatic olefin metathesis product includes a step of contacting an olefin metathesis reaction partner with a pretreatment reagent before contacting the internal olefin.

30. The method according to claim 29, wherein the pretreatment reagent is selected from the group consisting of alumina, triethylaluminum, and magnesium aluminum isopropoxide.

Images