process

Abstract

The present invention relates to a process for the hydrogenation of glycerol esters, comprising treating a composition comprising glycerol esters with a base and a transition metal catalyst in the presence of molecular hydrogen, wherein the base is present in at least 7 wt. %, based on the total weight of the composition, and the catalyst is present in an amount of 0.05 wt. % or less, based on the total weight of the composition.

Description

[Technical Field]

[0001] The present invention relates to a process for the hydrogenation of glycerol esters. [Background technology]

[0002] The reduction of esters is an essential transformation in the chemical industry as a route to primary alcohols. Ester reduction has traditionally been carried out using reagents such as sodium metal in ethanol (stoichiometric or excess amounts) (Bouveault-Blanc reduction), or more recently, using metal hydride reagents such as LiAlH4 or NaBH4. However, these reduction reactions are difficult to carry out effectively on a large scale, particularly due to safety concerns associated with the extremely exothermic quenching step. Therefore, large-scale catalytic reduction reactions use hydrogen gas. Cu- or Zn-based heterogeneous catalysts are primarily used for ester reduction in the very large-scale natural detergent alcohol (NDA) market. However, these methods require very high pressures and / or temperatures in large-scale dedicated production facilities. The chemoselectivity of ester reduction relative to other sensitive functional groups can also be an issue in some cases using these methods. Furthermore, industrial processes for converting glycerol esters to primary alcohols using Cu- or Zn-based heterogeneous catalysts currently include an intermediate step of hydrolyzing the glycerol esters to produce fatty acids, which are then transesterified with lower alcohols to form fatty acid esters. Alternatively, glycerol esters can be directly transesterified with lower alcohols to form fatty acid esters. Direct reduction of glycerol esters is not commercially viable due to the reduction of glycerol to propylene glycol, which requires more hydrogen, higher catalyst costs, and destroys valuable glycerol by-products.

[0003] Therefore, there is a need to provide an improved process for the hydrogenation of glycerol esters that requires lower catalyst loading while still maintaining high catalyst activity and TON. Summary of the Invention

[0004] The present invention provides an improved process for the hydrogenation of glycerol esters. The process is simple, economical, safe, and can be operated in standard hydrogenation vessels. In certain embodiments, the process may have environmental benefits by requiring the use of much less catalyst than is used in conventional processes.

[0005] In a first aspect, the present invention provides a process for the hydrogenation of glycerol esters, comprising treating a composition comprising glycerol esters with a base and a transition metal catalyst in the presence of molecular hydrogen, wherein the base is present in at least 7 wt. %, based on the total weight of the composition, and the catalyst is present in an amount of 0.05 wt. % or less, based on the total weight of the composition.

[0006] In a further aspect, the present invention provides a hydrogenated composition obtained or obtainable by the above-described process.

[0007] In a further aspect, the present invention provides a method of making a compound, the method comprising a process as described hereinabove.

[0008] definition The point of attachment of a moiety or substituent is represented by "-". For example, -OH is attached through an oxygen atom.

[0009] As used herein, the term "alkyl" refers to a straight-chain or branched-chain saturated hydrocarbon group. In certain embodiments, an alkyl group can have 1 to 20 carbon atoms, in certain embodiments, 1 to 15 carbon atoms, and in certain embodiments, 1 to 8 carbon atoms. An alkyl group can be unsubstituted. Alternatively, an alkyl group can be substituted. Unless otherwise specified, an alkyl group can be attached at any suitable carbon atom, and if substituted, can be substituted at any suitable atom. Typical alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, and the like.

[0010] As used herein, the term "alkenyl" refers to a straight or branched chain unsaturated hydrocarbon group containing at least one carbon-carbon double bond.

[0011] As used herein, the term "alkynyl" refers to a straight or branched chain unsaturated hydrocarbon group containing at least one carbon-carbon triple bond.

[0012] As used herein, the term "cycloalkyl" is used to represent a saturated carbocyclic hydrocarbon group. A cycloalkyl group may have a single ring or multiple condensed rings. In certain embodiments, a cycloalkyl group may have 3 to 15 carbon atoms, in certain embodiments, 3 to 10 carbon atoms, and in certain embodiments, 3 to 8 carbon atoms. A cycloalkyl group may be unsubstituted. Alternatively, a cycloalkyl group may be substituted. Unless otherwise specified, a cycloalkyl group may be attached at any suitable carbon atom, and if substituted, may be substituted at any suitable atom. Typical cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and the like.

[0013] As used herein, the term "cycloalkenyl" refers to an unsaturated non-aromatic carbocyclic ring (non-aromatic carbon ring). Thus, a cycloalkenyl group has at least one carbon-carbon double bond, but can have more. In certain embodiments, a cycloalkenyl group can have 3 to 15 carbon atoms, in certain embodiments, 3 to 10 carbon atoms, and in certain embodiments, 3 to 8 carbon atoms. A cycloalkenyl group can be unsubstituted. Alternatively, a cycloalkenyl group can be substituted. Unless otherwise specified, a cycloalkenyl group can be attached at any suitable carbon atom, and if substituted, can be substituted at any suitable atom. Typical cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like.

[0014] As used herein, the term "alkoxy" refers to an optionally substituted group of formula alkyl-O- or cycloalkyl-O-, where alkyl and cycloalkyl are as defined above.

[0015] As used herein, the term "aryl" refers to an aromatic carbocyclic group. An aryl group may have a single ring or multiple fused rings. In certain embodiments, an aryl group may have 6 to 20 carbon atoms, in certain embodiments, 6 to 15 carbon atoms, and in certain embodiments, 6 to 12 carbon atoms. An aryl group may be unsubstituted. Alternatively, an aryl group may be substituted. Unless otherwise specified, an aryl group may be attached at any suitable carbon atom, and if substituted, may be substituted at any suitable atom. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, anthracenyl, and the like.

[0016] As used herein, the term "arylalkyl" refers to an optionally substituted group of formula aryl-alkyl-, where aryl and alkyl are as defined above.

[0017] As used herein, the terms "halogen," "halo," or "hal" refer to -F, -Cl, -Br, and -I.

[0018] As used herein, the term "heteroalkyl" refers to a straight-chain or branched-chain saturated hydrocarbon group in which one or more carbon atoms are independently replaced with one or more heteroatoms (e.g., nitrogen, oxygen, phosphorus, and / or sulfur atoms). A heteroalkyl group can be unsubstituted. Alternatively, a heteroalkyl group can be substituted. Unless otherwise specified, a heteroalkyl group can be attached at any suitable atom, and if substituted, can be substituted at any suitable atom. Examples of heteroalkyl groups include, but are not limited to, ethers, thioethers, primary amines, secondary amines, tertiary amines, and the like.

[0019] As used herein, the term "heterocycloalkyl" refers to a saturated cyclic hydrocarbon group in which one or more carbon atoms are independently replaced with one or more heteroatoms (e.g., nitrogen, oxygen, phosphorus, and / or sulfur atoms). A heterocycloalkyl group can be unsubstituted. Alternatively, a heterocycloalkyl group can be substituted. Unless otherwise specified, a heterocycloalkyl group can be attached at any suitable atom, and if substituted, can be substituted at any suitable atom. Examples of heterocycloalkyl groups include, but are not limited to, epoxide, morpholinyl, piperadinyl, piperazinyl, thiiranyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, thiazolidinyl, thiomorpholinyl, and the like.

[0020] As used herein, the term "heteroaryl" refers to an aromatic carbocyclic group in which one or more carbon atoms are independently replaced with one or more heteroatoms (e.g., nitrogen, oxygen, phosphorus, and / or sulfur atoms). A heteroaryl group can be unsubstituted. Alternatively, a heteroaryl group can be substituted. Unless otherwise specified, a heteroaryl group can be attached at any suitable atom, and if substituted, can be substituted at any suitable atom. Examples of heteroaryl groups include, but are not limited to, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, thiadiazolyl, thiophenyl, oxadiazolyl, pyridinyl, pyrimidyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, indolyl, quinolinyl, and the like.

[0021] As used herein, the term "heterocycle" encompasses both heterocycloalkyl and heteroaryl groups.

[0022] As used herein, the term "substituted" refers to a group in which one or more hydrogen atoms are each independently replaced with the same or different substituents (e.g., 1, 2, 3, 4, 5 or more). Examples of substituents include -halo, -C(halo), -R c , =O, =S, -OR c , -SR c , -NR c R d , -CN, -NO2, -C(O)-R c , -COOR d , -C(S)-R c , -C(S)OR d , -S(O)2OH, -S(O)2-R c , -S(O)NR c R d , -OS(O)-R c and -CONR c R d , e.g., -halo, -C(halo)3 (e.g., -CF3), -R c , -OR c , -NRc R d Examples include, but are not limited to, -CN, or -NO. c and R d are independently selected from the group consisting of H, alkyl, aryl, arylalkyl, heteroalkyl, heteroaryl, or R c and R d together with the atom to which they are attached form a heterocycloalkyl group. c and R d may be unsubstituted or further substituted as defined herein.

[0023] As used herein, the term "bidentate ligand" refers to a ligand that donates two pairs of electrons to a metal atom.

[0024] As used herein, the term "tridentate ligand" refers to a ligand that donates three pairs of electrons to a metal atom.

[0025] As used herein, the term "tetradentate ligand" refers to a ligand that donates four pairs of electrons to a metal atom.

[0026] As used herein, the term "Ru-SNS, dichlorotriphenylphosphine[bis(2-(ethylthio)ethyl)amine]ruthenium(II)" refers to dichlorotriphenylphosphine[bis(2-(ethylthio)ethyl)amine]ruthenium(II).

[0027] As used herein, the term "Ru-PNN, dichlorotriphenylphosphine[2-(diphenylphosphino)-N-(2-pyridinylmethyl)ethanamine]ruthenium(II)" refers to dichlorotriphenylphosphine[2-(diphenylphosphino)-N-(2-pyridinylmethyl)ethanamine]ruthenium(II).

[0028] As used herein, the term "glycerol ester" refers to an ester formed from glycerol and at least one fatty acid. A glycerol ester formed from glycerol and one fatty acid is also known as a monoglyceride. A glycerol ester formed from glycerol and two fatty acids is also known as a diglyceride. A glycerol ester formed from glycerol and three fatty acids is also known as a triglyceride. The glycerol esters hydrogenated in the process of the present invention can be from natural, non-natural, synthetic, or semi-synthetic sources. For example, when natural olive oil, a composition containing glycerol esters, is subjected to the process of the present invention, the glycerol esters present therein are directly hydrogenated.

[0029] As used herein, the term "fatty acid" refers to a carboxylic acid having a long aliphatic chain (e.g., >6 carbon atoms) that can be either saturated or unsaturated. The aliphatic chain of the fatty acid can be branched or unbranched. In certain embodiments, the aliphatic chain of the fatty acid contains 12-24 carbon atoms. In certain embodiments, the aliphatic chain of the fatty acid contains 0-5 carbon-carbon double bonds.

[0030] As used herein, the term "S / C, substrate / catalyst" is an abbreviation for "substrate / catalyst" and is used to describe the catalyst loading used in a reaction, i.e., the molar ratio of ester to catalyst present in the reaction mixture. If the glycerol ester contains more than one ester moiety, the S / C value is adjusted accordingly. For example, a molar ratio of triglyceride to catalyst of 10,000:1 is equivalent to an S / C of 30,000:1 (because the triglyceride contains three ester moieties).

[0031] As used herein, unless otherwise specified, "wt. %" describes the weight of the specified material (e.g., base, catalyst, etc.) as a percentage of the in-process weight of the composition comprising the glycerol ester. The "wt. %" amount given for a particular material (e.g., base, catalyst, etc.) is the amount of that material used in the reaction chamber (i.e., where the hydrogenation reaction takes place).

[0032] As used herein, the term "turnover number" (TON) refers to the number of moles of substrate that one mole of catalyst can convert before it is deactivated.

[0033] As used herein, the term "neat conditions" is used to describe a reaction that begins with a reaction mixture that comprises at least 95% by volume of a mixture of compositions that include a glycerol ester and a base.

[0034] As used herein, the term "hydrogenation" refers to hydrogenation using molecular hydrogen.

[0035] As used herein, the term "NMR conversion" refers to the percentage ratio of hydrogenation product to total unreacted esters as determined by NMR. For example, an NMR conversion of 89% refers to a reaction mixture containing 89% product alcohol and 11% unreacted esters as determined by NMR. [Brief explanation of the drawings]

[0036] [Figure 1] 1 is a hydrogen uptake curve (ie, hydrogen uptake in mM (y-axis) versus time (x-axis)) for the experiments of Example 2, entries 1-4. [Figure 2] 1 is a hydrogen uptake curve (ie, hydrogen uptake in mM (y-axis) versus time (x-axis)) for the experiments of Example 2, entries 5-8. DETAILED DESCRIPTION OF THE INVENTION

[0037] Preferred and / or optional features of the invention will now be described. Any aspect of the invention may be combined with any other aspect of the invention unless the context requires otherwise. Any preferred or optional feature of any aspect of the invention may be combined with any aspect of the invention, singly or in any combination, unless the context requires otherwise.

[0038] The present invention provides a process for the hydrogenation of glycerol esters, comprising treating a composition comprising glycerol esters with a base and a transition metal catalyst in the presence of molecular hydrogen, wherein the base is present in at least 7 wt. %, based on the total weight of the composition, and the catalyst is present in an amount of 0.05 wt. % or less, based on the total weight of the composition.

[0039] In a preferred process of the present invention, the base is present in an amount of at least 7.5 wt.% based on the total weight of the composition comprising glycerol esters, preferably at least 8 wt.% based on the total weight of the composition comprising glycerol esters, more preferably at least 8.5 wt.% based on the total weight of the composition comprising glycerol esters, even more preferably at least 9 wt.% based on the total weight of the composition comprising glycerol esters, even more preferably at least 9.5 wt.% based on the total weight of the composition comprising glycerol esters, even more preferably at least 10 wt.% based on the total weight of the composition comprising glycerol esters, even more preferably at least 15 wt.% based on the total weight of the composition comprising glycerol esters, even more preferably at least 20 wt.% based on the total weight of the composition comprising glycerol esters, even more preferably at least 25 wt.% based on the total weight of the composition comprising glycerol esters, and even more preferably at least 30 wt.% based on the total weight of the composition comprising glycerol esters. Without wishing to be bound by theory, it is believed that the use of a large amount of base in the process of the present invention allows for the use of a lower catalyst loading compared to known processes. In some cases, extremely low catalyst loadings have been achieved, for example, 0.006 wt. % or less of catalyst based on the total weight of the composition including the glycerol ester.

[0040] In preferred processes of the present invention, the base is present in less than 50 wt. % based on the total weight of the composition comprising glycerol esters, more preferably less than 45 wt. % based on the total weight of the composition comprising glycerol esters, more preferably less than 40 wt. % based on the total weight of the composition comprising glycerol esters, and even more preferably less than 35 wt. % based on the total weight of the composition comprising glycerol esters.

[0041] In a preferred process of the present invention, the base is present in at least 30 mol% based on the total amount of glycerol esters, preferably at least 35 mol% based on the total amount of glycerol esters, preferably at least 40 mol% based on the total amount of glycerol esters, more preferably at least 45 mol% based on the total amount of glycerol esters, even more preferably at least 50 mol% based on the total amount of glycerol esters, even more preferably at least 60 mol% based on the total amount of glycerol esters, even more preferably at least 70 mol% based on the total amount of glycerol esters, even more preferably at least 80 mol% based on the total amount of glycerol esters, even more preferably at least 90 mol% based on the total amount of glycerol esters, even more preferably at least 100 mol% based on the total amount of glycerol esters, and even more preferably at least 125 mol% based on the total amount of glycerol esters. Without wishing to be bound by theory, it is believed that the use of a large amount of base in the process of the present invention allows for the use of lower catalyst loadings compared to known processes. In some cases, extremely low catalyst loadings, eg, S / C=40,000 / 1 or greater, have been achieved.

[0042] In preferred processes of the present invention, the base is present at 200 mol % or less, based on the total amount of glycerol esters, more preferably 175 mol % or less, based on the total amount of glycerol esters, more preferably 150 mol % or less, based on the total amount of glycerol esters, and even more preferably 130 mol % or less, based on the total amount of glycerol esters.

[0043] In a preferred process of the present invention, the base is a metal alkoxide. The metal alkoxide is preferably a metal methoxide, a metal ethoxide, a metal isopropoxide, or a metal tert-butoxide. Preferred metal alkoxides include lithium ethoxide, sodium ethoxide, and potassium ethoxide.

[0044] In a preferred process of the present invention, the base is an alkali metal alkoxide. The alkali metal alkoxide is preferably an alkali metal methoxide, an alkali metal ethoxide, an alkali metal isopropoxide, or an alkali metal tert-butoxide. More preferably, the alkali metal alkoxide is an alkali metal methoxide or an alkali metal ethoxide.

[0045] In a particularly preferred process of the present invention, the base is an alkali metal ethoxide, preferably lithium ethoxide, sodium ethoxide, or potassium ethoxide, more preferably sodium ethoxide.

[0046] In a preferred process of the present invention, the base is in solid form.

[0047] In a preferred process of the present invention, the base is supported, more preferably the base is supported on a resin.

[0048] In a preferred process of the present invention, the process is carried out in the absence of a solvent, which has the advantage of making the process easier and cheaper to carry out.

[0049] In an alternative preferred process of the present invention, the process is carried out under neat conditions.

[0050] In an alternative preferred process of the present invention, the process is carried out in the presence of at least one solvent.

[0051] Preferably, the at least one solvent is selected from alcohol, toluene, THF, and Me-THF. More preferably, the at least one solvent is selected from methanol, ethanol, toluene, THF, and Me-THF. Most preferably, the at least one solvent is selected from methanol, ethanol, and toluene.

[0052] In some cases, the use of an alcohol solvent, such as ethanol, has been found to minimize the time delay before the hydrogenation reaction begins.

[0053] In a preferred process of the present invention, the at least one solvent is present in an amount of 10 to 100% by volume based on the total volume of the composition including the glycerol ester, preferably 15 to 95% by volume based on the total volume of the composition including the glycerol ester, and more preferably 20 to 90% by volume based on the total volume of the composition including the glycerol ester (e.g., 50% by volume based on the total volume of the composition including the glycerol ester).

[0054] In a preferred process of the present invention, the volume ratio of the at least one solvent to the composition comprising glycerol esters is not more than 1:1, preferably not more than 1:2.

[0055] In a preferred process of the present invention, the volume ratio of the at least one solvent to the composition comprising glycerol esters is in the range of 1:2 to 1:1, preferably in the range of 1:2 to 1:1.5.

[0056] In a preferred process of the invention, the process is carried out in the presence of two or more solvents. Preferred solvents are as described above.

[0057] In an alternative preferred process of the present invention, the process is carried out in the presence of a first solvent and a second solvent.

[0058] In a preferred process of the present invention, the first solvent is selected from toluene, THF and Me-THF. In a preferred process of the present invention, the second solvent is an alcohol, preferably ethanol.

[0059] In some cases, the use of an alcohol solvent, such as ethanol, as the second solvent has been found to minimize the time delay before the hydrogenation reaction begins.

[0060] In a particularly preferred process of the present invention, the first solvent is toluene and the second solvent is an alcohol, preferably ethanol.

[0061] In an alternative particularly preferred process of the present invention, the first solvent is THF and the second solvent is an alcohol, preferably ethanol.

[0062] In a preferred process of the present invention, the first solvent is present in an amount of 10 to 100% by volume based on the total volume of the composition including the glycerol ester, preferably 15 to 95% by volume based on the total volume of the composition including the glycerol ester, and more preferably 20 to 90% by volume based on the total volume of the composition including the glycerol ester (e.g., 50% by volume based on the total volume of the composition including the glycerol ester).

[0063] In a preferred process of the present invention, the volume ratio of the first solvent to the composition comprising the glycerol ester is not more than 1:1, preferably not more than 1:2.

[0064] In a preferred process of the present invention, the volume ratio of the first solvent to the composition containing glycerol ester is in the range of 1:2 to 1:1, preferably in the range of 1:2 to 1:1.5.

[0065] In a preferred process of the present invention, the second solvent is present in an amount of 1 to 15% by volume based on the total volume of the composition including the glycerol ester, preferably in an amount of 1 to 10% by volume based on the total volume of the composition including the glycerol ester, preferably in an amount of 1 to 7.5% by volume based on the total volume of the composition including the glycerol ester, and more preferably in an amount of 1 to 5% by volume based on the total volume of the composition including the glycerol ester.

[0066] In a preferred process of the present invention, the first solvent is present in an amount of 10 to 100% by volume based on the total volume of the composition including the glycerol ester, and the second solvent is present in an amount of 1 to 10% by volume based on the total volume of the composition including the glycerol ester; preferably, the first solvent is present in an amount of 15 to 95% by volume based on the total volume of the composition including the glycerol ester, and the second solvent is present in an amount of 1 to 7.5% by volume based on the total volume of the composition including the glycerol ester; more preferably, the first solvent is present in an amount of 20 to 90% by volume based on the total volume of the composition including the glycerol ester, and the second solvent is present in an amount of 1 to 5% by volume based on the total volume of the composition including the glycerol ester.

[0067] In a preferred process of the present invention, the process is carried out at a temperature in the range of 20 to 150°C, more preferably 20 to 140°C, more preferably 25 to 130°C, more preferably 25 to 120°C, more preferably 30 to 100°C, more preferably 30 to 90°C, more preferably 30 to 80°C, more preferably 35 to 75°C, even more preferably 37.5 to 60°C, even more preferably 40 to 55°C, and most preferably 40 to 50°C (e.g., 40°C). The preferred process of the present invention is carried out at a relatively low temperature, which means that the energy input to the reaction is lower, making the process more economical. It is believed that lower temperatures for ester hydrogenation may also help improve catalyst stability.

[0068] Preferred processes of the present invention are carried out at a pressure which is at least 5 bar, more preferably at least 10 bar, even more preferably at least 20 bar, even more preferably at least 30 bar, even more preferably at least 40 bar, and most preferably at least 50 bar.

[0069] Preferred processes of the present invention are carried out at pressures in the range of from 5 to 100 bar, more preferably in the range of from 10 to 95 bar, even more preferably in the range of from 20 to 90 bar, even more preferably in the range of from 25 to 70 bar, and most preferably in the range of from 30 to 50 bar.

[0070] The preferred process of the present invention is carried out over a period of from 1 to 24 hours, more preferably from 2 to 16 hours, even more preferably from 3 to 10 hours, and most preferably from 4 to 8 hours.

[0071] The process of the present invention requires low catalyst loadings while still achieving commercially useful TONs and conversions for ester hydrogenation. Lower catalyst loadings mean the reaction is more environmentally friendly and more efficient. Lower catalyst loadings also mean the cost of the reaction can be reduced.

[0072] In the process of the present invention, the catalyst is present at 0.05 wt% or less, based on the total weight of the composition comprising glycerol esters. In a preferred process of the present invention, the catalyst is present at 0.04 wt% or less, based on the total weight of the composition comprising glycerol esters, more preferably 0.03 wt% or less, based on the total weight of the composition comprising glycerol esters, even more preferably 0.02 wt% or less, based on the total weight of the composition comprising glycerol esters, even more preferably 0.01 wt% or less, based on the total weight of the composition comprising glycerol esters, even more preferably 0.009 wt% or less, based on the total weight of the composition comprising glycerol esters, even more preferably 0.008 wt% or less, based on the total weight of the composition comprising glycerol esters, even more preferably 0.007 wt% or less, based on the total weight of the composition comprising glycerol esters, even more preferably 0.006 wt% or less, based on the total weight of the composition comprising glycerol esters, even more preferably 0.005 wt% or less, based on the total weight of the composition comprising glycerol esters. More preferably, the glycerol ester is present at no more than 0.004 wt. % based on the total weight of the composition comprising the glycerol ester, even more preferably no more than 0.003 wt. % based on the total weight of the composition comprising the glycerol ester, even more preferably no more than 0.002 wt. % based on the total weight of the composition comprising the glycerol ester, even more preferably no more than 0.001 wt. % based on the total weight of the composition comprising the glycerol ester, even more preferably no more than 0.0009 wt. % based on the total weight of the composition comprising the glycerol ester, even more preferably no more than 0.0008 wt. % based on the total weight of the composition comprising the glycerol ester, even more preferably no more than 0.0007 wt. % based on the total weight of the composition comprising the glycerol ester, even more preferably no more than 0.0006 wt. % based on the total weight of the composition comprising the glycerol ester, and even more preferably no more than 0.0005 wt. % based on the total weight of the composition comprising the glycerol ester.

[0073] In some embodiments of the process of the present invention, the catalyst is present at 0.0004 wt. % or greater, based on the total weight of the composition including the glycerol ester.

[0074] In the process of the present invention, the substrate / catalyst (S / C) loading is 5,000 / 1 or greater. In preferred processes of the invention, the substrate / catalyst loading is at least 6,000 / 1, more preferably at least 7,000 / 1, more preferably at least 8,000 / 1, even more preferably at least 9,000 / 1, more preferably at least 10,000 / 1, even more preferably at least 15,000 / 1, even more preferably at least 20,000 / 1, even more preferably at least 30,000 / 1, even more preferably at least 40,000 / 1, even more preferably at least 50,000 / 1, even more preferably at least 60,000 / 1, even more preferably at least 70,000 / 1, even more preferably at least 80,000 / 1, even more preferably at least 90,000 / 1, even more preferably at least 100,000 / 1, even more preferably at least 200,000 / 1, even more preferably at least 300,000 / 1, even more preferably at least 400,000 / 1.

[0075] In some embodiments of the process of the present invention, the substrate / catalyst loading is 500,000 / 1 or less.

[0076] The process of the present invention uses a transition metal catalyst. The transition metal catalyst may be preformed or may be formed in situ during the ester hydrogenation reaction. Preferably, the transition metal catalyst is preformed. Alternatively, the transition metal catalyst is formed in situ during the ester hydrogenation reaction.

[0077] In preferred processes of the present invention, the transition metal in the transition metal catalyst is a Group 6, 7, 8, or 9 transition metal. More preferably, the transition metal in the transition metal catalyst is a Group 7, 8, or 9 transition metal. Even more preferably, the transition metal in the transition metal catalyst is a Group 8 transition metal.

[0078] In a preferred process of the present invention, the transition metal in the transition metal catalyst is selected from Mo, Mn, Fe, Ru, Co and Os. More preferably, the transition metal in the transition metal catalyst is selected from Ru and Os. Most preferably, the transition metal in the transition metal catalyst is Ru.

[0079] In a preferred process of the present invention, the transition metal catalyst used in the process of the present invention comprises a tridentate ligand.

[0080] In a preferred process of the present invention, the transition metal catalyst comprises a tridentate ligand having the formula (I):

[0081] [ka] During the ceremony, X is -SR a , -OR a , -CR a , -NR a R b , -PR a R b , -P(=O)R a R b , -OPR a R b , and -NHPR a R b is selected from R 1 and R x are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 Heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, or R1 , and R 3a and R 3b One of the following, or R x , and R 3a and R 3b together with the atoms to which they are attached form a ring, Or X is a heteroatom, and R 1 When combined with R x When is absent, it forms an optionally substituted heterocycle, Y is -SR a , -OR a , -CR a , -NR a R b , -PR a R b , -P(=O)R a R b , -OPR a R b , and -NHPR a R b is selected from R 2 and R y are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, or R 2 , and R 4a and R 4b One of the following, or R y , and R 4a and R 4b together with the atoms to which they are attached form a ring, Or, Y is a heteroatom and R 2 When combined with R y When is absent, it forms an optionally substituted heterocycle, R 3a , R 3b , R 4a and R 4b are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, or R 3a , and R 4a and R 4b One of the following, or R 3b , and R 4a and R 4b together with the atoms to which they are attached form a heterocyclic ring, R 5 is hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, each m and n is independently 1 or 2; R a and R b each independently, if present, is hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, or X and / or Y are -NR a R b , -PR a R b , -OPR a R b , or -NHPR a R b If R a and R b together with the heteroatom to which they are attached form a heterocyclic ring.

[0082] In the tridentate ligand of formula (I), X is preferably -SR a , -CR a , -NR a R b , -PR a R b , and -NHPR a R b More preferably, X is selected from -SR a , -PR a R b , and -NHPR a R b Even more preferably, X is selected from -SR a , and -PR a R b Most preferably, X is selected from -SRa is.

[0083] In the tridentate ligand of formula (I), R 1 and R x are each independently preferably hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 1~20 -heteroalkyl, and substituted or unsubstituted C 3~20 -cycloalkyl. More preferably, R 1 and R x are each independently hydrogen and substituted or unsubstituted C 1~20 -alkyl. Even more preferably, R 1 and R x are each hydrogen.

[0084] In alternative preferred tridentate ligands of formula (I), X is a heteroatom and R 1 When combined with R x When R is absent, it forms an optionally substituted heterocycle. More preferably, X is a heteroatom and R 1 When combined with R x When is absent, it forms an optionally substituted heteroaromatic ring. More preferably, the optionally substituted heteroaromatic ring is an optionally substituted nitrogen-containing heteroaromatic ring. Even more preferably, the optionally substituted nitrogen-containing heteroaromatic ring is selected from pyridinyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, thiadiazolyl, oxadiazolyl, pyrimidyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, indolyl, and quinolinyl. Even more preferably, the optionally substituted nitrogen-containing heteroaromatic ring is selected from pyridinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, and pyrimidyl. Most preferably, the optionally substituted nitrogen-containing heteroaromatic ring is pyridinyl.

[0085] In the tridentate ligand of formula (I), Y is preferably -SR a , -CR a , -NR a R b , -PR a R b , and -NHPR a R b More preferably, Y is selected from -SR a , -PR a R b , and -NHPR a R b Even more preferably, Y is selected from -SR a and -PR a R b Most preferably, Y is selected from -SR a is.

[0086] In the tridentate ligand of formula (I), R 2 and R y are each independently preferably hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 1~20 -heteroalkyl, and substituted or unsubstituted C 3~20 -cycloalkyl. More preferably, R 2 and R y are each independently hydrogen and substituted or unsubstituted C 1~20 -alkyl. Even more preferably, R 2 and R y are each hydrogen.

[0087] In alternative preferred tridentate ligands of formula (I), Y is a heteroatom and R 2 When combined with R y When R is absent, it forms an optionally substituted heterocycle. More preferably, Y is a heteroatom and R 2 When combined with R yWhen is absent, it forms an optionally substituted heteroaromatic ring. More preferably, the optionally substituted heteroaromatic ring is an optionally substituted nitrogen-containing heteroaromatic ring. Even more preferably, the optionally substituted nitrogen-containing heteroaromatic ring is selected from pyridinyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, thiadiazolyl, oxadiazolyl, pyrimidyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, indolyl, and quinolinyl. Even more preferably, the optionally substituted nitrogen-containing heteroaromatic ring is selected from pyridinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, and pyrimidyl. Most preferably, the optionally substituted nitrogen-containing heteroaromatic ring is pyridinyl.

[0088] In the tridentate ligand of formula (I), R 3a , R 3b , R 4a and R 4b are each independently preferably hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 1~20 -heteroalkyl, and substituted or unsubstituted C 3~20 -cycloalkyl. More preferably, R 3a , R 3b , R 4a , and R 4b are each independently hydrogen and substituted or unsubstituted C 1~20 -alkyl. Even more preferably, R 3a , R 3b , R 4a , and R 4b are each hydrogen.

[0089] In alternative preferred tridentate ligands of formula (I), R 3a , and R 4a and R 4b One of the following, or R 3b , and R 4a and R 4btogether with the atoms to which they are attached form a heterocycle. Preferably, the heterocycle is a 6-membered heterocycle.

[0090] In the tridentate ligand of formula (I), R 5 is preferably hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 1~20 -heteroalkyl, and substituted or unsubstituted C 3~20 -cycloalkyl. More preferably, R 5 is hydrogen and substituted or unsubstituted C 1~20 -alkyl. Even more preferably, R 5 is hydrogen.

[0091] In the tridentate ligand of formula (I), each m and n is preferably 1.

[0092] In the tridentate ligand of formula (I), R a and R b are, when present, each independently preferably hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl. More preferably, R a and R b each independently, if present, is hydrogen, substituted or unsubstituted C 1~20 -Alkyl (e.g., C 1~10 -alkyl), and substituted or unsubstituted C 6~20 -aryl. Particularly preferred C 1~20 -Alkyl groups include ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and hexyl, more preferably methyl, ethyl, isopropyl, tert-butyl, and even more preferably ethyl. 6~20-aryl groups include phenyl, tolyl, xylyl, and methoxyphenyl, more preferably phenyl.

[0093] In alternative preferred tridentate ligands of formula (I), X and / or Y are -NR a R b , -PR a R b , -OPR a R b , or -NHPR a R b If R a and R b together with the heteroatom to which they are attached form a heterocyclic ring.

[0094] In a preferred process of the present invention, the transition metal catalyst comprises a tridentate ligand having the formula (I): During the ceremony, X is -SR a , -CR a , -NR a R b , -PR a R b , and -NHPR a R b is selected from R 1 and R x are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, Or X is a heteroatom, and R 1When combined with R x when absent, forms an optionally substituted heteroaromatic ring, wherein the heteroaromatic ring is a nitrogen-containing heteroaromatic ring; Y is -SR a , -CR a , -NR a R b , -PR a R b , and -NHPR a R b is selected from R 2 and R y are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, or Y is a heteroatom, and R 2 When combined with R y when absent, forms an optionally substituted heteroaromatic ring, wherein the heteroaromatic ring is a nitrogen-containing heteroaromatic ring; R 3a , R 3b , R 4a , R 4b and R 5 are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, each m and n is independently 1 or 2; R a and R b each independently, if present, is hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, or X and / or Y are -NR a R b , -PR a R b or -NHPR a R b If R a and R b together with the heteroatom to which they are attached form a heterocyclic ring.

[0095] In a preferred process of the present invention, the transition metal catalyst comprises a tridentate ligand having the formula (I): During the ceremony, X is -SR a , -PR a R b , and -NHPR a R b is selected from R 1 and R xare each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, Or X is a heteroatom, and R 1 When combined with R x when is absent, forms an optionally substituted heteroaromatic ring, the heteroaromatic ring being a nitrogen-containing heteroaromatic ring selected from pyridinyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, thiadiazolyl, oxadiazolyl, pyrimidyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, indolyl, and quinolinyl; Y is -SR a , -PR a R b , and -NHPR a R b is selected from R 2 and R y are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20-heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, or Y is a heteroatom, and R 2 When combined with R y when is absent, forms an optionally substituted heteroaromatic ring, the heteroaromatic ring being a nitrogen-containing heteroaromatic ring selected from pyridinyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, thiadiazolyl, oxadiazolyl, pyrimidyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, indolyl, and quinolinyl; R 3a , R 3b , R 4a , R 4b and R 5 are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, each m and n is independently 1 or 2; R a and R b each independently, if present, is hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, or X and / or Y are selected from -PR a R b or -NHPR a R b If R a and R b together with the heteroatom to which they are attached form a heterocyclic ring.

[0096] In a preferred process of the present invention, the transition metal catalyst comprises a tridentate ligand having the formula (I): During the ceremony, X is -SR a and -PR a R b is selected from R 1 and R x are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, Or X is a heteroatom, and R 1 When combined with R xwhen is absent, forms an optionally substituted heteroaromatic ring, the heteroaromatic ring being a nitrogen-containing heteroaromatic ring selected from pyridinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, and pyrimidyl; Y is -SR a and -PR a R b is selected from R 2 and R y are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, or Y is a heteroatom, and R 2 When combined with R y when is absent, forms an optionally substituted heteroaromatic ring, the heteroaromatic ring being a nitrogen-containing heteroaromatic ring selected from pyridinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, and pyrimidyl; R 3a , R 3b , R 4a , R 4b and R 5 are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, each m and n is independently 1 or 2; R a and R b each independently, if present, is hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, or X and / or Y are selected from -PR a R b If R a and R b together with the heteroatom to which they are attached form a heterocyclic ring.

[0097] In a preferred process of the present invention, the transition metal catalyst comprises a tridentate ligand having the formula (I), wherein: X is -SR a and R 1 and R x are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20-alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, Y is -SR a and R 2 and R y are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, R 3a , R 3b , R 4a , R 4b and R 5 are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 Heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20-heteroaryl, each m and n is independently 1 or 2; R a are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl.

[0098] Preferably, the transition metal catalyst comprises a tridentate ligand having the formula (I), wherein: X is -SR a and R 1 and R x are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 1~20 -heteroalkyl, and substituted or unsubstituted C 3~20 -cycloalkyl, Y is SR a and R 2 and R y are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 1~20 -heteroalkyl, and substituted or unsubstituted C 3~20 -cycloalkyl, R 3a , R 3b , R 4a , R 4b and R 5 are each independently hydrogen, substituted or unsubstituted C 1~20-alkyl, substituted or unsubstituted C 1~20 -heteroalkyl and substituted or unsubstituted C 3~20 -cycloalkyl, each m and n is independently 1 or 2; R a are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 1~20 -heteroalkyl, and substituted or unsubstituted C 3~20 -cycloalkyl.

[0099] More preferably, the transition metal catalyst comprises a tridentate ligand having the formula (I), wherein: X is -SR a and R 1 and R x are each independently hydrogen and substituted or unsubstituted C 1~20 -alkyl, Y is SR a and R 2 and R y are each independently hydrogen and substituted or unsubstituted C 1~20 -alkyl, R 3a , R 3b , R 4a , R 4b and R 5 are each independently hydrogen and substituted or unsubstituted C 1~20 -alkyl, each m and n is independently 1 or 2; R a are each independently hydrogen and substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 1~20 -heteroalkyl, and substituted or unsubstituted C 3~20 -cycloalkyl.

[0100] Even more preferably, the transition metal catalyst comprises a tridentate ligand having the formula (I), wherein: X and Y are SRa and R 1 , R x , R 2 , R y , R 3a , R 3b , R 4a , R 4b and R 5 are each hydrogen, m and n are each 1; R a are each independently a substituted or unsubstituted C 1~20 Alkyl, preferably C 1~10 It is alkyl.

[0101] Even more preferably, the transition metal catalyst comprises a tridentate ligand having the formula (I), wherein: X and Y are each SEt; R 1 , R x , R 2 , R y , R 3a , R 3b , R 4a , R 4b and R 5 are each hydrogen, m and n are each 1.

[0102] In an alternative preferred process of the present invention, the transition metal catalyst comprises a tridentate ligand having the formula (I), wherein: X is a heteroatom and R 1 When combined with R x When is absent, it forms an optionally substituted heteroaromatic ring, Y-PR a R b and R 2 and R y are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, R 3a , R 3b , R 4a , R 4b and R 5 are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 Heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, each m and n is independently 1 or 2; R a and R b are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20-heteroaryl, or R a and R b together with the heteroatom to which they are attached form a heterocyclic ring.

[0103] Preferably, the transition metal catalyst comprises a tridentate ligand having the formula (I), wherein: X is a nitrogen atom, and R 1 When combined with R x when absent, forms an optionally substituted heteroaromatic ring, which heteroaromatic ring is a nitrogen-containing heteroaromatic ring; Y-PR a R b and R 2 and R y are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 1~20 -heteroalkyl, and substituted or unsubstituted C 3~20 -cycloalkyl, R 3a , R 3b , R 4a , R 4b and R 5 are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 3~20 -cycloalkyl, each m and n is independently 1 or 2; R a and R b are each independently a substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl.

[0104] More preferably, the transition metal catalyst comprises a tridentate ligand having the formula (I), wherein: X is a nitrogen atom, and R 1 When combined with R x when is absent, forms an optionally substituted heteroaromatic ring, the heteroaromatic ring being a nitrogen-containing heteroaromatic ring selected from pyridinyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, thiadiazolyl, oxadiazolyl, pyrimidyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, indolyl, and quinolinyl; Y-PR a R b and R 2 , R y , R 3a , R 3b , R 4a , R 4b and R 5 are each hydrogen, each m and n is 1; R a and R b are each independently a substituted or unsubstituted C 1~20 -alkyl and substituted or unsubstituted C 6~20 -aryl.

[0105] Even more preferably, the transition metal catalyst comprises a tridentate ligand having the formula (I), wherein: X is a nitrogen atom, and R 1 When combined with R x when absent, forms an optionally substituted heteroaromatic ring, the heteroaromatic ring being a nitrogen-containing heteroaromatic ring selected from pyridinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, and pyrimidyl; Y-PR a R b and R 2 , R y , R 3a、 R 3b , R4a , R 4b and R 5 are each hydrogen, each m and n is 1; R a and R b are each independently selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, phenyl, tolyl, xylyl, and methoxyphenyl.

[0106] Even more preferably, the transition metal catalyst comprises a tridentate ligand having the formula (I), wherein: X is a nitrogen atom, and R 1 When combined with R x When is absent, it forms an optionally substituted pyridinyl ring. Y-PR a R b and R 2 , R y , R 3a , R 3b , R 4a , R 4b and R 5 are each hydrogen, each m and n is 1; R a and R b are each independently selected from methyl, ethyl, isopropyl, tert-butyl, phenyl, tolyl, xylyl, and methoxyphenyl.

[0107] Even more preferably, the transition metal catalyst comprises a tridentate ligand having the formula (I), wherein: X is a nitrogen atom, and R 1 When combined with R x When is absent, it forms an optionally substituted pyridinyl ring, Y-PR a R b and R 2 , R y , R 3a , R 3b , R4a , R 4b and R 5 are each hydrogen, each m and n is 1; R a and R b are each phenyl.

[0108] In a preferred process of the present invention, the transition metal catalyst has formula (II) or formula (III): [M(L 1 )(L 2 ) d ](II) [M(L 1 )(L 2 ) d ]W(III) During the ceremony, M is a transition metal; L 1 is a tridentate ligand as defined above, L 2 are ligands which may be the same or different, d is 1, 2 or 3; W is a non-coordinating anionic ligand.

[0109] In preferred processes of the present invention, M is a Group 6, 7, 8 or 9 transition metal. More preferably, M is a Group 7, 8 or 9 transition metal. Even more preferably, M is a Group 8 transition metal.

[0110] In a preferred process of the present invention, M is a transition metal selected from Mo, Mn, Fe, Co, Ru, and Os. More preferably, M is a transition metal selected from Ru and Os. Most preferably, M is Ru.

[0111] In a preferred process of the present invention, d is 3.

[0112] As will be appreciated by those skilled in the art, each L 2 L 2Ligands may be monodentate or polydentate, provided that the combination of ligands is permitted by the valence rules. In a preferred process of the present invention, each L 2 is a monodentate ligand. Preferably, each L 2 is independently a neutral monodentate ligand or an anionic monodentate ligand. In a preferred process of the present invention, each L2 is independently selected from -H, -CO, -CN, -P(R')3, -As(R')3, -CR', -OR', -O(C=O)R', -NR'2, halogen (e.g., -Cl, -Br, -I), and solvent, where each R' is independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl. Preferably, each L 2 are independently selected from -H, -CO, -P(R')3, and halogen. More preferably, each L 2 is independently selected from -CO, -PPh3, and -Cl. 2 When is a solvent, the solvent is preferably selected from THF, Me-THF, MeCN, H2O and alcohols (e.g., methanol, ethanol, isopropanol, etc.).

[0113] In the transition metal catalyst of formula (III), W is a non-coordinating anionic ligand. By "non-coordinating anionic ligand" is meant that the anionic ligand is forced to reside in the outer sphere of the metal center. Thus, the anionic ligand is dissociated from the metal center. This is in contrast to a neutral complex in which the anionic ligand is bound to the metal within the coordination sphere. Anionic ligands can generally be identified as non-coordinating by analyzing the X-ray crystal structure of the cationic complex. Preferably, W is a triflate (i.e., TfO). - or CF3SO3 - ), tetrafluoroborates (i.e. -BF4), hexafluoroantimonate (i.e. - SbF6), hexafluorophosphate (PF6 - ), [B[3,5-(CF3)2C6H3]4] - ([BAr F 4] - ), halides (e.g., Cl - , Br - , I - ) and mesylate (MsO - or MeSO3 - ) is selected from the group consisting of

[0114] Preferably, the transition metal catalyst is of formula (II).

[0115] Alternatively, the transition metal catalyst is a transition metal catalyst of formula (III).

[0116] In a preferred process of the present invention, the transition metal catalyst is:

[0117] [ka]

[0118] In a preferred process of the present invention, the transition metal catalyst is Ru-SNS or Ru-PNN.

[0119] In a preferred process of the present invention, the transition metal catalyst is:

[0120] [ka]

[0121] In a preferred process of the present invention, the transition metal catalyst used in the process of the present invention comprises a bidentate ligand.

[0122] In a preferred process of the present invention, the transition metal catalyst comprises a bidentate ligand having formula (IV):

[0123] [ka] During the ceremony, X' is -NHR ax and Y' is -SR ax ,-OR ax ,-CR ax ,-NR ax R bx ,-PR ax R bx ,-P(=O)R ax R bx ,-OPR ax R bx , and -NHPR ax R bx is selected from R 8a ,R 8b ,R 9a and R 9b are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 Heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, p is 1 or 2; R ax and R bx each independently, if present, is hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20-alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, or X' and / or Y' are selected from -NR ax R bx ,-PR ax R bx ,-OPR ax R bx , or -NHPR ax R bx If R ax and R bx together with the heteroatom to which they are attached form a heterocyclic ring.

[0124] In a preferred process of the present invention, the transition metal catalyst has formula (V) or formula (VI): [M(L 1 e L 2 f ] [M(L 1 e L 2 f ]W During the ceremony, M is a transition metal; L 1 are bidentate ligands as defined above, which may be the same or different, L 2 are ligands, if present, which may be the same or different, e is 1 or 2, and when e is 1, f is 2, 3, or 4, and when e is 2, f is 0, 1, or 2; W is a non-coordinating anionic ligand.

[0125] M, L 2 and W are generally as described above.

[0126] In a preferred process of the present invention, the transition metal catalyst used in the process of the present invention comprises a tetradentate ligand.

[0127] In a preferred process of the present invention, the transition metal catalyst comprises a tetradentate ligand having formula (VII):

[0128] [ka] During the ceremony, Q is -SR ay ,-OR ay ,-CR ay ,-NR ay R by ,-PR ay R by ,-P(=O)R ay R by ,-OPR ay R by , and -NHPR ay R by is selected from R 15 and R q are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, or Q is a heteroatom and R 15 When combined with R q When is absent, it forms an optionally substituted heterocycle, W is S, O, NR a , and PR a is selected from R 16 , R w and R z are each independently hydrogen or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, or R 16 is R z When combined with R w When is absent, it forms an optionally substituted heterocycle, Z is -SR ay , -OR ay , -CR ay , -NR ay R by , -PR ay R by , -P(=O)R ay R by , -OPR ay R by , and -NHPR ay R by is selected from R 10a , R 10b , R 11a and R 11b are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 Heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, or R 10a and R 11a and R 11b One of the following, or R 10b and R 11a and R 11b form a ring with the atoms to which they are attached, R 12a , R 12b , R 13a , R 13b and R 14 are each independently hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20 -cycloalkenyl, substituted or unsubstituted C 2~20 -heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, each q and r is independently 1 or 2; s is 0, 1 or 2; R ay and R by each independently, if present, is hydrogen, substituted or unsubstituted C 1~20 -alkyl, substituted or unsubstituted C 2~20 -alkenyl, substituted or unsubstituted C 2~20 -alkynyl, substituted or unsubstituted C 1~20 -heteroalkyl, substituted or unsubstituted C 1~20 -alkoxy, substituted or unsubstituted C 3~20 -cycloalkyl, substituted or unsubstituted C 3~20-cycloalkenyl, substituted or unsubstituted C 2~20 --heterocycloalkyl, substituted or unsubstituted C 6~20 -aryl, and substituted or unsubstituted C 4~20 -heteroaryl, or Q and / or Z are -NR ay R by ,-PR ay R by ,-OPR ay R by , or -NHPR ay R by If R ay and R by together with the heteroatom to which they are attached form a heterocyclic ring.

[0129] In a preferred process of the present invention, the transition metal catalyst has formula (VIII) or formula (IX): [M(L 1 )(L 2 g ] (VIII) [M(L 1 ,L 2 g ]W (IX) During the ceremony, M is a transition metal; L 1 is a tetradentate ligand as defined above, L 2 are ligands, if present, which may be the same or different, g is 0, 1 or 2; W is a non-coordinating anionic ligand.

[0130] M, L 2 and W are generally as described above.

[0131] In a preferred process of the present invention, the transition metal catalyst is removed from the reaction mixture by a precipitation step using a co-solvent.

[0132] In an alternative preferred process of the present invention, the transition metal catalyst is removed from the reaction mixture by distillation of the product.

[0133] In an alternative preferred process of the present invention, the transition metal catalyst is removed from the reaction mixture by crystallization of the product.

[0134] In an alternative preferred process of the present invention, the transition metal catalyst is removed from the reaction mixture using a metal scavenger.

[0135] In a preferred process of the present invention, the glycerol esters are hydrogenated by treating the composition containing the glycerol esters with a base and a transition metal catalyst in the presence of molecular hydrogen.

[0136] In a preferred process of the present invention, the composition comprises a mixture of glycerol esters.

[0137] In a preferred process of the present invention, the composition comprises glycerol esters.

[0138] In a preferred process of the present invention, the composition consists of a mixture of glycerol esters.

[0139] In a preferred process of the present invention, the composition comprising glycerol esters is from a natural source.

[0140] In an alternative preferred process of the present invention, the composition comprising glycerol esters is derived from a non-natural source.

[0141] In a further alternative preferred process of the present invention, the composition comprising glycerol esters is from a synthetic or semi-synthetic source.

[0142] In a preferred process of the present invention, the composition comprising the glycerol ester is a natural oil.

[0143] Preferably, the natural oil is selected from almond oil, avocado oil, bellflower seed oil, Brazil nut oil, cashew nut oil, castor oil, chia seed oil, cocoa butter oil, palm oil, corn oil, cottonseed oil, linseed oil, grape seed, hemp seed, macadamia nut oil, mustard oil, olive oil, palm oil, palm kernel oil, peanut oil, pecan nut oil, perilla oil, poppy seed oil, prakash oil, rice oil, safflower oil, sea buckthorn oil, sesame oil, soybean oil, sunflower oil, black gram oil, and walnut oil. More preferably, the natural oil is selected from linseed oil, olive oil, palm oil, palm kernel oil, rapeseed oil, and sunflower oil. Even more preferably, the natural oil is selected from olive oil, rapeseed oil, and sunflower oil.

[0144] In a preferred process of the present invention, the glycerol ester present in the composition comprises at least one fatty acid residue, the saturated or unsaturated aliphatic chain of which contains 12 to 24 carbon atoms, preferably 14 to 22 carbon atoms, more preferably 16 to 20 carbon atoms (e.g., 18 carbon atoms), and the saturated or unsaturated aliphatic chain of the fatty acid residue may be unsubstituted or substituted.

[0145] Preferably, the glycerol esters present in the composition comprise at least one fatty acid residue, the saturated or unsaturated aliphatic chain of which comprises 12 carbon atoms.

[0146] Preferably, the glycerol esters present in the composition comprise at least one fatty acid residue, the saturated or unsaturated aliphatic chain of which comprises 14 carbon atoms.

[0147] Preferably, the glycerol esters present in the composition comprise at least one fatty acid residue, the saturated or unsaturated aliphatic chain of which comprises 16 carbon atoms.

[0148] Preferably, the glycerol esters present in the composition comprise at least one fatty acid residue, the saturated or unsaturated aliphatic chain of which comprises 18 carbon atoms.

[0149] Preferably, the glycerol esters present in the composition comprise at least one fatty acid residue, the saturated or unsaturated aliphatic chain of which comprises 20 carbon atoms.

[0150] Preferably, the glycerol esters present in the composition comprise at least one fatty acid residue, the saturated or unsaturated aliphatic chain of which comprises 22 carbon atoms.

[0151] Preferably, the glycerol esters present in the composition comprise at least one fatty acid residue, the saturated or unsaturated aliphatic chain of which comprises 24 carbon atoms.

[0152] In a preferred process of the present invention, the glycerol ester present in the composition comprises at least one fatty acid residue, the aliphatic chain of which is unsaturated and contains 1 to 5 carbon-carbon double bonds, preferably 1 to 4 carbon-carbon double bonds, more preferably 1 to 3 carbon-carbon double bonds, and more preferably 1 to 2 carbon-carbon double bonds. The unsaturated aliphatic chain of the fatty acid residue may be unsubstituted or substituted. The unsaturated aliphatic chain may contain cis and / or trans double bonds.

[0153] Preferably, the glycerol esters present in the composition comprise at least one fatty acid residue, the aliphatic chain of which is unsaturated and contains one carbon-carbon double bond.

[0154] Preferably, the glycerol esters present in the composition comprise at least one fatty acid residue, the aliphatic chain of which is unsaturated and contains two carbon-carbon double bonds.

[0155] In a preferred process of the present invention, the glycerol esters present in the composition comprise at least one fatty acid residue selected from omega-9 fatty acids, omega-7 fatty acids, omega-6 fatty acids, and omega-3 fatty acids.

[0156] Suitable omega-9 fatty acids include hypogeic acid, oleic acid, elaidic acid, gondoiic acid, mead acid, erucic acid, nervonic acid, and ximenic acid.

[0157] Suitable omega-7 fatty acids include 5-dodecenoic acid, 7-tetradecenoic acid, palmitoleic acid, vaccenic acid, rumenic acid, paulic acid, 15-docosenoic acid, and 17-tetracosenoic acid.

[0158] Suitable omega-6 fatty acids include linoleic acid, gamma-linolenic acid, calendic acid, eicosadienoic acid, dihomo-gamma-linolenic acid, arachidonic acid, docosadienoic acid, adrenic acid, osbondic acid, tetracosatetraenoic acid, and tetracosapentaenoic acid.

[0159] Suitable omega-3 fatty acids include hexadecatrienoic acid, alpha-linolenic acid, stearidonic acid, eicosatrienoic acid, eicosatetraenoic acid, eicosapentaenoic acid, heneicosapentaenoic acid, docosapentaenoic acid, clupanodonic acid, docosahexaenoic acid, tetracosapentaenoic acid, and tetracosahexaenoic acid.

[0160] In a preferred process of the present invention, the glycerol esters present in the composition comprise at least one fatty acid residue selected from linoleic acid and oleic acid.

[0161] In a preferred process of the present invention, the glycerol ester present in the composition comprises one fatty acid residue. In an alternative preferred process of the present invention, the glycerol ester present in the composition comprises two fatty acid residues. In a further alternative preferred process of the present invention, the glycerol ester present in the composition comprises three fatty acid residues. Preferred fatty acid residues are discussed above.

[0162] As will be appreciated by those skilled in the art, the products of the process of the present invention are fatty alcohols and glycerol. In preferred processes of the present invention, the process does not produce hemiacetal by-products.

[0163] When the glycerol esters present in the composition contain one or more alkenyl and / or alkynyl moieties, the process of the present invention preferably selectively hydrogenates the ester moiety over at least one of the unsaturated carbon-carbon bonds of the alkene and / or alkyne. In some known processes, hydrogenation of such substrates results in hydrogenation of only the alkenyl and / or alkynyl moieties, which means that a two-step procedure is required to achieve hydrogenation of the ester moiety. Thus, an advantage of the present invention is that the presence of the alkenyl and / or alkynyl moieties is not detrimental to the reduction of the ester moiety; rather, the unsaturated C-C bond can be preserved under the reaction conditions, if desired.

[0164] Alternatively, when the glycerol esters present in the composition contain one or more alkenyl and / or alkynyl moieties, the process of the present invention preferably hydrogenates both the ester moieties and the unsaturated carbon-carbon bonds of the alkenes and / or alkynes.

[0165] When the glycerol esters present in the composition contain ketone and / or aldehyde moieties, the process of the present invention preferably hydrogenates both the ester moieties and the carbon-oxygen double bonds of the ketones and / or aldehydes.

[0166] When the glycerol esters present in the composition contain one or more alkenyl and / or alkynyl moieties and a ketone and / or aldehyde moiety, the process of the present invention preferably selectively hydrogenates both the ester moiety and the carbon-oxygen double bond of the ketone and / or aldehyde over at least one of the unsaturated carbon-carbon bonds of the alkene and / or alkyne. Alternatively, when the glycerol esters present in the composition contain one or more alkenyl and / or alkynyl moieties and a ketone and / or aldehyde moiety, the process of the present invention preferably hydrogenates the ester moiety, the unsaturated carbon-carbon bond of the alkene and / or alkyne, and the carbon-oxygen double bond of the ketone and / or aldehyde.

[0167] In a preferred process of the present invention, the process is a batch process.

[0168] In a preferred process of the present invention, the process is a flow process. Preferably, the process is a flow process in which any excess base is recycled.

[0169] The present invention also provides a hydrogenated composition obtained or obtainable by the above process.

[0170] The present invention also provides a method of making a compound, the method comprising the process described hereinabove.

[0171] The invention will now be further described with the following non-limiting examples. [Example]

[0172] material Ru-SNS and Ru-PNN are commercially available from Johnson Matthey.

[0173] NaOEt is commercially available from, for example, Sigma Aldrich, Fisher Scientific, Alfa Aesar, Acros Organics, etc.

[0174] Rapeseed oil (RS1) is commercially available. GC analysis of the rapeseed oil used in the following examples revealed the following substrate composition: C16: 0-5.6%, C18: 0-1.3%, C18: 1-61.6%, C18: 2-21.4%.

[0175] Olive oil (OO1) is commercially available. GC analysis of the olive oil used in the following examples revealed the following substrate composition: C16: 0-1.3%, C18: 0-2.4%, C18: 1-73.0%, C18: 2-9.3%.

[0176] Sunflower oil (SO1) is commercially available. GC analysis of the sunflower oil used in the following examples revealed the following matrix composition: C16: 0-6.1%, C18: 0-2.5%, C18: 1-23.3%, C18: 2-66.1%.

[0177] Measurement method Gas chromatography (GC) measurements were performed using a Varian 3900 or 3800 gas chromatograph system.

[0178] Nuclear magnetic resonance (NMR) measurements were carried out using a Bruker Avance III 400 (400 MHz) spectrometer.

[0179] General Procedure for the Hydrogenation of Glycerol Esters To an 8 mL vial, the catalyst Ru-SNS or Ru-PNN was added, followed by the solid base, NaOEt, then the solvent (if needed), then the oil (RS1, OO1, or SO1). The vial was then added to a Biotage Endeavor screening system, after which the stir head was sealed and the reaction mixture was purged with nitrogen. The purge sequence involved pressurizing to approximately 45 psi of nitrogen and then releasing the pressure (repeated five times). The reactor was then pressurized with hydrogen, then heated and pressurized to the set pressure of hydrogen. Upon completion of the reaction time (typically 16 hours), the reaction was cooled to room temperature. A nitrogen purge cycle (repeated five times) was then performed to remove the hydrogen.

[0180] The reaction mixture was then analyzed by GC and NMR. Before analysis could be performed, a small amount of EtOH had to be added to the crude reaction mixture and heated at 100° C. for 1 hour. The reaction mixture was then cooled. For GC analysis, the reaction mixture was diluted with EtOH in a GC vial and subjected to GC analysis. For NMR analysis, the resulting residue was subjected to a workup procedure: (i) dilution with toluene and water, followed by the addition of 4 M HCl; (ii) separation of the aqueous layer; and (iii) removal of the organic solvent in vacuo.

[0181] Example 1: Examination of changes in base amount The general procedure described above was carried out on a sample of rapeseed oil (RS1). The temperature, pressure, catalyst, and catalyst loading were kept constant for each set of experiments, but the amount of solid base NaOEt used was varied. When the Ru-SNS catalyst was used, toluene was also used as a solvent. Since Example 1 was a screening experiment, the crude reaction mixture was not worked up, meaning that NMR conversion was not available. Instead, the reaction was monitored by GC analysis and hydrogen uptake. The results are shown in Table 1 below.

[0182] The results in Table 1 show that increasing the amount of base significantly increases the C18:1 conversion of the hydrogenation reaction, even though the catalyst loading remains very low. This was observed for both sets of experiments, i.e., those containing the Ru-PNN catalyst (entry 1 vs. entry 2, and entry 3 vs. entry 4) and those containing the Ru-SNS catalyst (entry 5 vs. entry 6). In each set of experiments, the C18:1 conversion was found to increase as the amount of base increased from 6.2 wt% to 18.7 wt%.

[0183] Example 2: Examination of reaction initiation delay The general procedure described above was carried out on a sample of rapeseed oil (RS1) using the Ru-SNS catalyst. The reaction was carried out using toluene as the solvent, but the amount of EtOH was varied to further determine whether this affected the progress of the reaction. Since Example 2 was a screening experiment, most of the crude reaction mixture was not worked up, meaning that NMR conversion was not available (except for entry 2, which was worked up and found to have 80% NMR conversion). Instead, the reaction was monitored by GC analysis and hydrogen uptake. The results are shown in Table 2 below.

[0184] As can be seen from Table 2, all reactions performed at 50° C. were found to proceed with complete C18:1 conversion via GC, except for Entry 1, which did not contain any EtOH additive. As can be seen from Figure 1, the delay to reaction initiation, as monitored by hydrogen uptake, decreased significantly upon addition of EtOH to the reaction mixture (i.e., a delay of about 16 hours for Entry 1 (no EtOH) versus about 2 hours for Entry 2, about 0.5 hours for Entry 3, and about 2.5 hours for Entry 4).

[0185] All reactions performed at 60° C. were found to proceed with complete C18:1 conversion via GC. As can be seen in Figure 2, the delay to reaction initiation, monitored by hydrogen uptake, again significantly decreased upon addition of EtOH to the reaction mixture (i.e., a delay of about 13 hours for entry 5 (no EtOH) versus about 3 hours for entry 6, about 1 hour for entry 7, and about 1 hour for entry 8).

[0186] The results shown in Table 2 and Figures 1 and 2 may also suggest that lower temperatures are more preferable.

[0187] Example 3: Glycerol ester hydrogenation A sample of rapeseed oil (RS1) was subjected to the general procedure described above. The conditions used for each reaction are listed below in Table 3. The results for each reaction are also shown in Table 3.

[0188] Example 4: Glycerol ester hydrogenation The general procedure described above was carried out on samples of rapeseed oil (RS1), olive oil (OO1), and sunflower oil (SO1). The conditions used for each reaction are listed below in Table 4. The results for each reaction are also shown in Table 4.

[0189] The results in Tables 3 and 4 demonstrate that the process of the present invention can achieve high NMR conversions and mass recoveries for the hydrogenation of a range of oils (i.e., compositions comprising glycerol esters) at extremely low catalyst loadings (e.g., about 0.0114 wt. % based on the amount of oil (equivalent to about 19,000 / 1 to 20,000 / 1 S / C) for the experiments in Table 3, and about 0.0059 wt. % based on the amount of oil (equivalent to about 38,000 / 1 to 40,000 / 1 S / C) for the experiments in Table 4). These results also demonstrate that hydrogenation reactions can be performed using a variety of different transition metal catalysts containing tridentate ligands.

[0190] A comparison of entries 1 and 2 in Table 3 shows comparable results. Thus, when all other variables remain constant, the hydrogenation reaction performed using Ru-SNS achieves high NMR conversion and mass recovery even at a much lower pressure of 10 bar (compared to 30 bar in entry 2 of Table 3). The same is true for the hydrogenation reaction performed using Ru-PNN (entries 3 and 4 of Table 3). The ability to operate the ester hydrogenation reaction of the present invention at lower pressures provides the additional benefits of reduced cost and improved safety. In addition, the need for specialized equipment that must withstand high pressures is avoided.

[0191] In some cases, the process of the present invention is carried out in the absence of a solvent, while in other cases, the presence of a solvent has been found to be beneficial. The addition of a small amount of alcohol (e.g., EtOH) has also been found to be beneficial in some cases (see Example 2 above). In the experiments shown in Tables 3 and 4, for RS1, the process involving the Ru-SNS catalyst was found to work best in the presence of toluene as a solvent, while the Ru-PNN catalyst worked best without a solvent. While OO1 and SO1 were able to better tolerate a range of solvent conditions, the best conditions for both catalysts were found to be the use of toluene as the solvent. However, all of the experiments in Tables 3 and 4 were found to benefit from the addition of a small amount of EtOH, as this was found to help minimize the time delay until the hydrogenation reaction began. Thus, the results shown in Tables 3 and 4 demonstrate that the process of the present invention can be effectively carried out using a range of different solvent conditions. As will be appreciated by those skilled in the art, optimized solvent conditions may vary for different substrates.

[0192] Example 5: Parr Scale Glycerol Ester Hydrogenation Rapeseed oil (RS1) (91 g, 100 mL), toluene (60 mL, 60% by volume based on RS1), and then solid NaOEt (28.1 g, 30.9% by weight based on RS1 substrate) were added to a Parr 600 mL reaction vessel. The vessel and stirrer head were clamped together and assembled to a heating mantle. A nitrogen purge was completed on the vessel while stirring the reaction mixture was set to approximately 750 rpm. The mixture was heated to 40 °C and maintained at this level. Once the system temperature reached equilibrium, the nitrogen was vented from the system, and a slurry of EtOH (12 mL, 12% by volume based on RS1) and Ru-SNS catalyst (10.4 mg, 0.0114% by weight based on RS1 substrate) was added to the vessel via the inlet. Five hydrogen purges were completed, then the reaction pressure was set to 30 bar and stirring was changed to approximately 1500 rpm. Hydrogen pressure was maintained throughout the reaction, and uptake was monitored. After overnight reaction, the reactor was cooled, the hydrogen was carefully vented, and the reaction vessel was inert with a nitrogen purge.

[0193] The crude reaction mixture was treated with 4 M HCl (105 mL) and an additional 100 mL of toluene was added to support the organic phase. The organic phase was separated and concentrated in vacuo to give 79 g of crude product (86.8 wt. % of the original substrate mass). Analysis by NMR showed 95% conversion of the ester content to alcohol.

[0194] Example 6: Parr Scale Glycerol Ester Hydrogenation The reaction of Example 5 was repeated using 20.2 g of NaOEt (22.2 wt. % relative to RS1 substrate). After treatment as described above for Example 5, 85 g of crude product was obtained (93.4 wt. % of the original substrate mass). Analysis by NMR showed 96% conversion of the ester content to alcohol.

[0195] [Table 1] 1 An approximation of the S / C ratio can be made by assuming that the RS1 oil composition is entirely 100% C18:1 (ie, mw=846) triglycerides. 2 The amount of base can be converted to an approximate mol% value for ester content by assuming the oil composition is entirely triglycerides with 100% C18:1 (i.e., mw=846). Taking entry 2 as an example, the amount of base used is equal to about 77 mol% of the ester content.

[0196] [Table 2] 1 An approximation of the S / C ratio can be made by assuming that the RS1 oil composition is entirely 100% C18:1 (ie, mw=846) triglycerides. 2 The amount of base can be converted to an approximate mol% value for ester content by assuming the oil composition is entirely triglycerides with 100% C18:1 (i.e., mw=846). Taking entry 1 as an example, the amount of base used is equal to about 129 mol% of the ester content.

[0197] [Table 3] 1 An approximation of the S / C ratio can be made by assuming that the RS1 oil composition is entirely 100% C18:1 (ie, mw=846) triglycerides. 2 The amount of base can be converted to an approximate mol% value for ester content by assuming that the RS1 oil composition is a perfect triglyceride with 100% C18:1 (i.e., mw=846). Taking entry 1 as an example, the amount of base used is equal to about 129 mol% of the ester content.

[0198] For the results in Table 3, the post-processed chain distribution (%) was as follows (order = C16:0, C18:0, C18:1, C18:2, ethyl oleate): Entry 1: 4.3, 0, 62.8, 20.4, 0 Entry 2: 4.2, 0, 63.0, 20.5, 0 Entry 3: 4.3, 1.0, 63.1, 20.4, 0 Entry 4: 4.3, 1.0, 63.3, 20.6, 0

[0199] [Table 4] 1 An approximation of the S / C ratio can be made by assuming the oil composition is entirely 100% C18:1 (ie, mw=846) triglycerides. 2 The amount of base can be converted to an approximate mol% value for ester content by assuming the oil composition is entirely triglycerides with 100% C18:1 (i.e., mw=846). Taking entry 1 as an example, the amount of base used is equal to about 129 mol% of the ester content.

[0200] For the results in Table 4, the post-processed chain distribution (%) was as follows (order = C16:0, C18:0, C18:1, C18:2, ethyl oleate): Entry 1: 4.3, 0, 60.8, 19.5, 0 Entry 2: 11.2, 2.8, 73.7, 8.3, 0 Entry 3: 11.2, 2.7, 74.2, 8.3, 0 Entry 4: 6.1, 3.6, 26.4, 61.2, 0 Entry 5: 6.3, 3.4, 26.6, 62.0, 0 The present disclosure may include the following aspects. [Aspect 1] 1. A process for the hydrogenation of glycerol esters, comprising treating a composition comprising glycerol esters with a base and a transition metal catalyst in the presence of molecular hydrogen, wherein the base is present in at least 7 wt. % based on the total weight of the composition and the catalyst is present in an amount of 0.05 wt. % or less based on the total weight of the composition. [Aspect 2] 2. The process of embodiment 1, wherein the base is present in at least 7.5 wt. %, based on the total weight of the composition including glycerol esters, preferably at least 8 wt. %, based on the total weight of the composition including glycerol esters. [Aspect 3] 3. The process of any one of the preceding aspects, wherein the base is present in at least 8.5 wt. %, based on the total weight of the composition comprising glycerol esters, preferably at least 9 wt. %, based on the total weight of the composition comprising glycerol esters. [Aspect 4] Aspect 4. The process of any one of aspects 1 to 3, wherein the base is a metal alkoxide, preferably an alkali metal alkoxide. [Aspect 5] Aspect 5. The process of any one of aspects 1 to 4, wherein the base is an alkali metal ethoxide selected from lithium ethoxide, sodium ethoxide, or potassium ethoxide, preferably sodium ethoxide. [Aspect 6] The process of any one of aspects 1 to 5, wherein the process is carried out in the absence of a solvent. [Aspect 7] The process of any one of aspects 1 to 5, wherein the process is carried out in the presence of at least one solvent, preferably selected from an alcohol, toluene, THF, and Me-THF. [Aspect 8] 8. The process of embodiment 7, wherein the at least one solvent is present in an amount of 10 to 100% by volume, based on the total volume of the composition including glycerol esters. [Aspect 9] Aspect 6. The process of any one of aspects 1 to 5, wherein the process is carried out in the presence of a first solvent and a second solvent. [Aspect 10] Aspect 10. The process of aspect 9, wherein the first solvent is toluene or THF and the second solvent is an alcohol, preferably ethanol. [Aspect 11] 11. The process of any one of claims 9 to 10, wherein the first solvent is present in an amount of 10 to 100% by volume, based on the total volume of the composition including the glycerol ester. [Aspect 12] 12. The process of any one of aspects 9-11, wherein the second solvent is present in an amount of 1 to 15% by volume, based on the total volume of the composition including the glycerol ester. [Aspect 13] Aspect 13. The process according to any one of aspects 1 to 12, wherein the temperature is in the range of 20 to 150°C, preferably in the range of 20 to 140°C. [Aspect 14] 14. The process according to any one of aspects 1 to 13, wherein the pressure is in the range of from 5 to 100 bar, preferably in the range of from 10 to 95 bar. [Aspect 15] 15. The process of any one of aspects 1-14, wherein the catalyst is present in no more than 0.04 wt. %, based on the total weight of the composition comprising glycerol esters, preferably no more than 0.03 wt. %, based on the total weight of the composition comprising glycerol esters, more preferably no more than 0.02 wt. %, based on the total weight of the composition comprising glycerol esters, and more preferably no more than 0.01 wt. %, based on the total weight of the composition comprising glycerol esters. [Aspect 16] 16. The process of any one of aspects 1-15, wherein the catalyst is present in an amount of 0.005 wt. % or less, based on the total weight of the composition comprising glycerol esters, more preferably 0.001 wt. % or less, based on the total weight of the composition comprising glycerol esters. [Aspect 17] 17. The process of any one of embodiments 1 to 16, wherein the transition metal catalyst comprises a tridentate ligand. [Aspect 18] the transition metal catalyst comprises a tridentate ligand having the formula (I):

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[0023] The process of embodiment 17, wherein:

[0024] together with the heteroatom to which they are attached form a heterocycle. [Aspect 19] The transition metal catalyst has formula (II) or formula (III), [M(L 1 )(L 2 ) d ](II) [M(L 1 )(L 2 ) d ]W(III) During the ceremony, M is a transition metal; L 1 is a tridentate ligand according to embodiment 18; L 2 are ligands which may be the same or different, d is 1, 2, or 3; 21. The process of any one of embodiments 1 to 20, wherein W is a non-coordinating anionic ligand. [Aspect 20] 20. The process of embodiment 19, wherein M is a transition metal selected from Ru and Os, preferably Ru. [Aspect 21] Each L 2 are independently -H, -CO, -CN, -P(R') 3 , -As(R') 3 , -CR', -OR', -O(C=O)R', -NR' 2 , a halogen (e.g., —Cl, —Br, —I), and a solvent; and wherein each R′ is independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl. [Aspect 22] 22. The process of any one of aspects 1 to 21, wherein the transition metal catalyst is:

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Claims

1. 1. A process for producing fatty alcohols and glycerol by hydrogenation of glycerol esters, comprising treating a composition comprising a glycerol ester with a base and a transition metal catalyst in the presence of molecular hydrogen, wherein the glycerol ester is an ester of glycerol and at least one fatty acid, the base is a metal alkoxide, the base is present in at least 7 wt % based on the total weight of the composition, and the catalyst is present in no more than 0.05 wt % based on the total weight of the composition, and the transition metal catalyst comprises a transition metal selected from Ru and Os and a tridentate ligand having formula (I): 【Chemistry 1】 During the ceremony, X is -SR ａ , -OR ａ , -CR ａ , -NR ａ R ｂ , -PR ａ R ｂ , -P(=O)R ａ R ｂ , -OPR ａ R ｂ , and -NHPR ａ R ｂ is selected from R １ and R ｘ are each independently hydrogen, substituted or unsubstituted C １～２０ - alkyl, substituted or unsubstituted C ２～２０ -alkenyl, substituted or unsubstituted C ２～２０ -alkynyl, substituted or unsubstituted C １～２０ -heteroalkyl, substituted or unsubstituted C １～２０ -alkoxy, substituted or unsubstituted C ３～２０ -cycloalkyl, substituted or unsubstituted C ３～２０ -cycloalkenyl, substituted or unsubstituted C ２～２０ Heterocycloalkyl, substituted or unsubstituted C ６～２０ -aryl, and substituted or unsubstituted C ４～２０ -heteroaryl, or R １ , and R ３ａ and R ３ｂ or R ｘ , and R ３ａ and R ３ｂ together with the atoms to which they are attached form a ring, Or X is a heteroatom, and R １ When combined with R ｘ When is absent, it forms an optionally substituted heterocycle, Y is -SR ａ , -OR ａ , -CR ａ , -NR ａ R ｂ , -PR ａ R ｂ , -P(=O)R ａ R ｂ , -OPR ａ R ｂ , and -NHPR ａ R ｂ is selected from R ２ and R ｙ are each independently hydrogen, substituted or unsubstituted C １～２０ - alkyl, substituted or unsubstituted C ２～２０ -alkenyl, substituted or unsubstituted C ２～２０ -alkynyl, substituted or unsubstituted C １～２０ -heteroalkyl, substituted or unsubstituted C １～２０ -alkoxy, substituted or unsubstituted C ３～２０ -cycloalkyl, substituted or unsubstituted C ３～２０ -cycloalkenyl, substituted or unsubstituted C ２～２０ Heterocycloalkyl, substituted or unsubstituted C ６～２０ -aryl, and substituted or unsubstituted C ４～２０ -heteroaryl, or R ２ , and R ４ａ and R ４ｂ or R ｙ , and R ４ａ and R ４ｂ together with the atoms to which they are attached form a ring, or Y is a heteroatom, and R ２ When combined with R ｙ When is absent, it forms an optionally substituted heterocycle, R ３ａ , R ３ｂ , R ４ａ and R ４ｂ are each independently hydrogen, substituted or unsubstituted C １～２０ - alkyl, substituted or unsubstituted C ２～２０ -alkenyl, substituted or unsubstituted C ２～２０ -alkynyl, substituted or unsubstituted C １～２０ -heteroalkyl, substituted or unsubstituted C １～２０ -alkoxy, substituted or unsubstituted C ３～２０ -cycloalkyl, substituted or unsubstituted C ３～２０ -cycloalkenyl, substituted or unsubstituted C ２～２０ Heterocycloalkyl, substituted or unsubstituted C ６～２０ -aryl, and substituted or unsubstituted C ４～２０ -heteroaryl, or R ３ａ , and R ４ａ and R ４ｂ or R ３ｂ , and R ４ａ and R ４ｂ together with the atoms to which they are attached form a heterocyclic ring, R ５ is hydrogen, substituted or unsubstituted C １～２０ - alkyl, substituted or unsubstituted C ２～２０ -alkenyl, substituted or unsubstituted C ２～２０ -alkynyl, substituted or unsubstituted C １～２０ -heteroalkyl, substituted or unsubstituted C １～２０ -alkoxy, substituted or unsubstituted C ３～２０ -cycloalkyl, substituted or unsubstituted C ３～２０ -cycloalkenyl, substituted or unsubstituted C ２～２０ -heterocycloalkyl, substituted or unsubstituted C ６～２０ -aryl, and substituted or unsubstituted C ４～２０ -heteroaryl, each m and n is independently 1 or 2; R ａ and R ｂ each independently, if present, is hydrogen, substituted or unsubstituted C １～２０ - alkyl, substituted or unsubstituted C ２～２０ -alkenyl, substituted or unsubstituted C ２～２０ -alkynyl, substituted or unsubstituted C １～２０ -heteroalkyl, substituted or unsubstituted C １～２０ -alkoxy, substituted or unsubstituted C ３～２０ -cycloalkyl, substituted or unsubstituted C ３～２０ -cycloalkenyl, substituted or unsubstituted C ２～２０ -heterocycloalkyl, substituted or unsubstituted C ６～２０ -aryl, and substituted or unsubstituted C ４～２０ -heteroaryl, or X and / or Y are selected from -NR ａ R ｂ , -PR ａ R ｂ , -OPR ａ R ｂ , or -NHPR ａ R ｂ If R ａ and R ｂ The process by which alkyl groups, together with the heteroatom to which they are attached, form a heterocyclic ring.

2. 10. The process of claim 1, wherein the base is present at at least 7.5 wt. %, based on the total weight of the composition including glycerol esters.

3. 3. The process of claim 1 or 2, wherein the base is present at at least 8.5 wt. %, based on the total weight of the composition including glycerol esters.

4. 4. The process of any one of claims 1 to 3, wherein the base is an alkali metal ethoxide selected from lithium ethoxide, sodium ethoxide, or potassium ethoxide.

5. The process of any one of claims 1 to 4, wherein the process is carried out in the absence of a solvent.

6. The process according to any one of claims 1 to 4, wherein the process is carried out in the presence of at least one solvent.

7. 7. The process of claim 6, wherein the at least one solvent is present in an amount of 10 to 100% by volume, based on the total volume of the composition including glycerol esters.

8. The process of any one of claims 1 to 4, wherein the process is carried out in the presence of a first solvent and a second solvent.

9. 9. The process of claim 8, wherein the first solvent is toluene or THF and the second solvent is an alcohol.

10. 10. The process of claim 8 or 9, wherein the first solvent is present in an amount of 10 to 100% by volume, based on the total volume of the composition including glycerol esters.

11. 11. The process of any one of claims 8 to 10, wherein the second solvent is present in an amount of 1 to 15% by volume, based on the total volume of the composition including glycerol esters.

12. The process of any one of claims 1 to 11, wherein the temperature is in the range of 20 to 150°C.

13. A process according to any one of claims 1 to 12, wherein the pressure is in the range of from 5 to 100 bar.

14. 14. The process of any one of claims 1 to 13, wherein the catalyst is present at 0.04 wt% or less, based on the total weight of the composition including glycerol esters.

15. 15. The process of any one of claims 1 to 14, wherein the catalyst is present at 0.005 wt% or less, based on the total weight of the composition including glycerol esters.

16. The transition metal catalyst has formula (II) or formula (III): [M(L] １ )(L ２ ) ｄ ](II) [M(L １ )(L ２ ) ｄ ]W(III) During the ceremony, M is a transition metal selected from Ru and Os; L １ is the tridentate ligand according to claim 1, L ２ are ligands which may be the same or different, d is 1, 2, or 3; The process of any one of claims 1 to 15, wherein W is a non-coordinating anionic ligand.

17. Each L ２ are independently —H, —CO, —CN, —P(R′) ３ , -As(R') ３ , -CR', -OR', -O(C=O)R', -NR' ２ , a halogen, and a solvent, wherein each R' is independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl.

18. 18. The process of any one of claims 1 to 17, wherein the transition metal catalyst is: 【Chemistry 2】

19. The process of any one of claims 1 to 18, wherein the composition comprising glycerol esters is a natural oil.

20. 20. The process of claim 19, wherein the natural oil is selected from almond oil, avocado oil, angelica seed oil, Brazil nut oil, cashew nut oil, castor oil, chia seed oil, cocoa butter oil, coconut oil, corn oil, cottonseed oil, linseed oil, grape seed, hemp seed, macadamia nut oil, mustard oil, olive oil, palm oil, palm kernel oil, peanut oil, pecan nut oil, perilla oil, poppy seed oil, prakashi oil, rice oil, safflower oil, sea buckthorn oil, sesame oil, soybean oil, sunflower oil, black gram oil, and walnut oil.

21. A method of making a compound, comprising the process of any one of claims 1 to 20.

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