Method for producing aliphatic aldehydes and their derivatives

Abstract

The present invention relates to a process for converting alcohols to aldehydes, particularly aliphatic alcohols to aliphatic aldehydes, which utilizes a catalyst, which is capable of providing high conversion of the alcohol, e.g., on a large scale, which uses relatively small amounts of solvent in the reaction and purification, and which is capable of removing catalyst from the product aldehyde in the purification.

Description

[Technical field]

[0001] The present invention relates to a process for converting alcohols to aldehydes, particularly aliphatic alcohols to aliphatic aldehydes, which utilizes a catalyst, which can provide high conversion of the alcohol, for example, on a large scale, which uses relatively small amounts of solvent in the reaction and purification, and which can remove the catalyst from the product aldehyde in the purification. [Background technology]

[0002] Economical and sustainable oxidation of primary alcohols to aldehydes on an industrial scale is one of the challenges in the chemical industry. Many methods have been reported in the literature, but most of them are problematic because they utilize toxic reagents, expensive chemicals, have limited functional group tolerance, give low reaction yields, or require harsh conditions.

[0003] There are several oxidation protocols in the academic literature that use aminoxyl radical copper complexes as catalysts. Usually, the copper complexes are generated in situ by mixing a copper precursor; the copper precursor is, for example, [Cu I (CH 3 CN) 4 ] + X -where X is usually an anion, such as tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, or a halogen with a ligand, typically 2,2′-bipyridine (BIPY). In many cases, the catalyst system also includes a base, such as 1-methyl-imidazole (MeIM). The aminoxyl radical is typically (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) or its derivatives, such as (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)oxyl (4-OH-TEMPO). The aminoxyl radical can also be generated in situ from hydroxylamine or oxoammonium salts. The catalyst system has been reported to achieve nearly quantitative aldehyde yields when primary alcohols are oxidized with molecular oxygen. However, these reactions are usually carried out on a small scale with large amounts of solvent (i.e. low substrate concentrations) and purification is expensive. It has not been possible to achieve good yields and reaction selectivities when using these methods on industrial raw materials such as complex mixtures of alcohols and more concentrated solutions. It is equally difficult to cost-effectively remove / recover the catalyst from the reaction medium.

[0004] A typical process for the oxidation of alcohols and subsequent removal of catalyst components has been reported by Stahl and coworkers (J. Am. Chem. Soc. 2011, 133, 16901-16910). The process is carried out on a 1 mmol alcohol scale. Although the process gives acceptable results in the laboratory, it cannot be used for large-scale production of aliphatic aldehydes; the large number of steps and the need for column chromatography make catalyst removal too expensive. In addition, the solvent volume of 60 ml of dichloromethane per ml of reaction mixture further increases the cost.

[0005] Kumpulainen and Ari MP Koskinen have reported a method that does not require column chromatography (Chem. Eur. J. 2009, 15, 10901-10911). The method is carried out on a 10 mmol scale of alcohol (1-decanol, 1.58 g). However, the method requires multiple steps and large volumes of solvent, making industrialization of the method impossible.

[0006] Norman Lui et al., Tetrahedron Letters 48 (2007) 8823-8828, describes a novel ligand and CuBr TEMPO with oxidative and thermoresponsive modes under fluorous biphasic conditions.

[0007] Hoover et al., J. Am. Chem. Soc. 2011, 133, 42, 16901-16910, relates to a Cu / TEMPO catalytic system for the aerobic oxidation of primary alcohols.

[0008] Steves et al., J. Am. Chem. Soc. 2013, 135, 42, 15742-15745, relates to a Cu / TEMPO catalytic system for the aerobic oxidation of unhindered primary alcohols.

[0009] Wei et al., Green Chem. 2019, 21, 4069, relates to the oxidation of alcohols to aldehydes or ketones using inorganic ligand-supported copper catalysts.

[0010] US Patent Application No. 5,155,280A1 relates to the preparation of aldehydes which involves reacting the corresponding alkanol with a stable solubilizing free radical nitrogen oxide.

[0011] The large number of steps involved in the above process is also problematic because each step involves product losses, which are further increased when the conversion is carried out at higher concentrations. Moreover, the acids used during the process, although somewhat effective in removing the basic components of the reaction mixture (ligands and added bases), do not remove the commonly used aminoxyl radicals (such as 4-hydroxy-TEMPO or TEMPO; which are highly soluble in the aliphatic aldehyde product mixture). A further drawback of most of the reported processes is the use of strong acids (e.g., sulfuric acid) to remove the copper. Such acids are known to cause side reactions that reduce the overall purity of the product.

[0012] For a mixture feedstock of pheromone alcohols, we have observed rapid catalyst deactivation, which limits the concentration and amount of desired aldehyde in the product and therefore requires expensive and complex purification such as distillation or chromatography, making it unfeasible on an industrial scale.

[0013] Thus, there is an unmet need for new processes for the conversion of primary alcohols (such as aliphatic alcohols) to the corresponding aldehydes (such as aliphatic aldehydes). To meet this need, the processes need to be scalable and applicable to raw material mixtures. Summary of the Invention

[0014] The present inventors have discovered a suitable method for converting an alcohol composition to an aldehyde composition, which uses a relatively small amount of solvent, is scalable to industrial scale (scalable to batch sizes of 100 kilograms or more), and provides a high purity product, especially with respect to removal of the catalyst composition. The method is particularly suitable for converting an aliphatic alcohol composition to a corresponding aliphatic aldehyde composition; since the method provides a high degree of conversion of the aliphatic alcohol composition. Furthermore, the method described herein has the advantage of providing a significantly higher conversion of alcohol to aldehyde than to acid, since it limits the competing reaction that oxidizes the alcohol to the corresponding acid.

[0015] In one aspect, the present disclosure provides a method for converting an aliphatic alcohol to an aliphatic aldehyde, the method comprising the steps (a) and (b) of: (a) providing a reaction mixture comprising an aliphatic alcohol, a catalyst comprising a copper source, and a solvent; and (b) a sufficient amount of O to convert more than 50 wt. % of the fatty alcohol to aliphatic aldehydes and less than 50 wt. % to fatty acids. 2 to the reaction mixture, thereby oxidizing the fatty alcohol.

[0016] In a further aspect, the present disclosure provides a method for converting aliphatic alcohols to aliphatic aldehydes on a large scale, the method comprising the steps (a) and (b) of: (a) providing a reaction mixture comprising at least one kilogram of an aliphatic alcohol, a catalyst comprising a copper source, at least one kilogram of a solvent, and a water-absorbing or water-adsorbing material that absorbs or adsorbs water; and (b)O 2 By adding a gas or liquid containing 2 or at least 0.001 μmol O per μmol initial aliphatic alcohol per minute. 2into the reaction mixture, thereby oxidizing greater than 50 wt. % of the fatty alcohols to fatty aldehydes and less than 50 wt. % to fatty acids.

[0017] In a further aspect, the present disclosure provides a method for converting an aliphatic alcohol to an aliphatic aldehyde, the method comprising the steps (a) and (b) of: (a) providing a reaction mixture comprising at least one kilogram of an aliphatic alcohol, a catalyst comprising a copper source, at least one kilogram of a solvent, and a water-absorbing or water-adsorbing material that absorbs or adsorbs water; and (b)O 2 By adding a gas or liquid containing 2 or at least 0.001 μmol O per μmol initial aliphatic alcohol per minute. 2 into the reaction mixture, thereby oxidizing greater than 50 wt. % of the fatty alcohols to fatty aldehydes and less than 50 wt. % to fatty acids.

[0018] In another aspect of the present disclosure, there is provided a method for converting an alcohol to an aldehyde, the method comprising the steps (a) and (b) of: (a) providing a reaction mixture comprising an alcohol composition comprising an alcohol, a catalyst composition as disclosed herein, and a solvent as disclosed herein; and (b) exposing the reaction mixture to a stream of oxygen as disclosed herein by bubbling a gas mixture containing oxygen through the reaction mixture, thereby obtaining the aldehyde.

[0019] One embodiment of the present disclosure provides a method for purifying an aliphatic aldehyde, comprising the following steps (a) to (c): (a) providing a crude reaction product comprising: (i) (iii) (i) Aliphatic aldehydes; (ii) copper ions; and (iii) a polar solvent; (b) combining the crude reaction product with a non-polar aprotic solvent and an acid to create a non-polar phase and a polar phase; and (c) separating the non-polar phase from the polar phase.

[0020] In one aspect of the disclosure, there is provided an aldehyde composition obtained by a process comprising the steps (a) and (b) of: (a) providing a reaction mixture comprising an alcohol composition comprising an alcohol, a catalyst composition as disclosed herein, and a solvent as disclosed herein; and (b) exposing the reaction mixture to an oxygen stream as disclosed herein by bubbling a gas mixture containing oxygen through the reaction mixture, thereby obtaining the aldehyde composition.

[0021] In one aspect of the disclosure, there is provided a method for converting an alcohol to an acetal, the method comprising the steps of: (a) providing a reaction mixture comprising an alcohol composition comprising an alcohol, a catalyst composition as disclosed herein, and a solvent as disclosed herein; (b) exposing the reaction mixture to a stream of oxygen as disclosed herein by bubbling a gas mixture containing oxygen through the reaction mixture, thereby obtaining the aldehyde; and (c) converting the aldehyde functionality of said aldehyde to an acetal functionality, thereby obtaining said acetal.

[0022] One aspect of the present disclosure provides a method for converting an alcohol to an α-hydroxysulfonic acid, the method comprising the steps of: (a) providing a reaction mixture comprising an alcohol composition comprising an alcohol, a catalyst composition as disclosed herein, and a solvent as disclosed herein; (b) exposing the reaction mixture to a stream of oxygen as disclosed herein by bubbling a gas mixture containing oxygen through the reaction mixture, thereby obtaining an aldehyde; and (c) converting the aldehyde functional group of the aldehyde into an α-hydroxysulfonic acid functional group, thereby obtaining an α-hydroxysulfonic acid.

[0023] In one aspect of the disclosure, a pheromone component is provided that is produced from renewable feedstocks, the pheromone component having at least 80% bio-based carbon content.

[0024] In a further aspect, the present disclosure provides a composition comprising greater than 93% by weight of an aliphatic aldehyde, less than 7% by weight of an aliphatic alcohol, and less than 2% by weight of water.

[0025] In a further aspect, there is provided a composition comprising greater than 93% by weight of an aliphatic aldehyde, less than 7% by weight of an aliphatic alcohol, and less than 2% by weight of water. [Brief description of the drawings]

[0026] [Figure 1] Conversion of aliphatic alcohols to aliphatic aldehydes at high oxygen feed rates. The reaction was continued for 2 hours, during which time the temperature rose from 22°C to 52°C after 1 hour and dropped to 42°C after 2 hours. The reaction yield steadily increased, exceeding 70% after 73 minutes and further increasing to 87% at 150 minutes. [Diagram 2] Conversion of aliphatic alcohols to aliphatic aldehydes in the presence of a water adsorbent at high oxygen feed rates. The reaction was continued for 2 hours, during which time the temperature increased from 22° C. to 52° C. after 1 hour and decreased to 42° C. after 2 hours. The conversion steadily increased to over 95% at 139 minutes. [Diagram 3]Conversion of aliphatic alcohols to aliphatic aldehydes in the presence of a water adsorbent at very high oxygen feed rates. The reaction was continued for 2 hours, during which time the temperature rose from 23°C to 51°C after 1 hour and 13 minutes, and then dropped to 22°C after 6 hours. The conversion steadily increased to over 99% at 110 minutes. [Figure 4] Oxidation of aliphatic alcohol mixture in a 4 m3 reactor as described in Example 16. Figure 4 shows the reaction data. [Diagram 5] Oxidation of a mixture of aliphatic alcohols in a 4 m3 reactor as described in Example 16. Figure 5 shows the conversion over time. [Figure 6] Oxidation of aliphatic alcohol mixture in a 4 m3 reactor as described in Example 17. Figure 6 shows the reaction data for the oxidation process. [Figure 7] Oxidation of a mixture of aliphatic alcohols in a 4 m3 reactor as described in Example 17. Figure 7 shows the conversion over time. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] definition A phrase such as "X comprises Y in the range of n to m" in this specification means that X comprises at least n and at most m of Y; that is, the phrase indicates that X comprises no less than n and no more than m of Y. As an example, when a composition is expressed as comprising Y in the range of 5% to 60%, the composition comprises no less than 5% of Y and no more than 60% of Y.

[0028] The singular terms "a" and "the" herein are synonymous with and used interchangeably with "one or more" and "at least one," unless otherwise indicated by the phrase and / or context. Thus, for example, when the specification or claims refer to "a solvent" or "the solvent," it can mean a single solvent or two or more solvents.

[0029] As used herein, "solvent" includes a liquid that is capable of substantially dissolving or dispersing another substance.

[0030] Unless expressly stated otherwise, the term "fatty alcohol" or "fatty aldehyde" is intended to include both the singular and plural forms of the term. As an example, a "composition comprising 50 wt.% fatty alcohol" can either contain a single fatty alcohol in an amount equal to 50 wt.% of the composition, or it can contain a mixture of two or more fatty alcohols in an amount equal to 50 wt.% of the composition.

[0031] The terms "unsaturated" and "desaturation" are used synonymously when describing a compound having a carbon-carbon double bond. The following terms are used throughout this specification: Δi desaturated compound; where i is an integer, the compound refers to a compound having a carbon-carbon double bond or a carbon-carbon triple bond between the carbon atom at the i position of the carbon chain and the carbon atom at the i+1 position of the carbon chain. Thus, the carbon chain length is at least equal to i+1. For example, Δ12 desaturated compound refers to a compound having a carbon-carbon double bond or a carbon-carbon triple bond between carbon 12 and carbon 13, and is referred to herein as a carbon chain having a carbon-carbon bond at the 12 position. The Δ12 desaturated compound may have a carbon chain length of 13 or more. The double or triple bond may be in the E or Z configuration. Thus, an Ei or Zi desaturated compound is referred to herein as a compound having a carbon-carbon double bond in the E or Z configuration, respectively, between carbon i and carbon i+1 of a carbon chain, where the desaturated compound has a total length at least equal to i+1. For example, an E12 desaturated aliphatic alcohol has a desaturation in the E configuration at the 12 position (i.e., a double bond between carbon atoms 12 and 13) and a carbon chain length of 13 or greater.

[0032] Furthermore, terms such as "(E)7, (Z)9", "(E7), (Z9)", "E7, Z9", "(E7, Z9)", "(7E, 9Z)", "(7E), (9Z)", "(7)E, (9)Z" and other variations thereof herein are synonymous. That is, when specifying the stereochemistry of a double bond in a carbon chain, the term or part of the term may be bracketed individually or the entire group of stereochemical descriptors, or combinations thereof, or the brackets may be omitted entirely; the position may be either before or after the descriptor. This is true for any combination of any number of stereochemical descriptors used herein.

[0033] The term "chain length" or "carbon chain length" as used herein refers to the number of consecutive carbon atoms in a molecule. As an example, the molecule hexadecan-1-ol has a chain length of 16.

[0034] Unless otherwise specified, reference to positions in an organic molecule by position number is based on numbering from the functional group in the organic molecule, e.g., by numbering the carbon atom bearing the hydroxyl group of a primary alcohol as carbon atom 1, or the carbon atom moiety of the carbonyl group of an aldehyde as carbon atom 1.

[0035] Cloud point: The cloud point of a surfactant in solution (e.g., an aqueous solution), especially a non-ionic surfactant, or of a glycol solution, is the temperature at which a mixture of the surfactant and the solution (e.g., the aqueous solution) begins to phase separate, two phases appear, and therefore the mixture becomes cloudy. This behavior is characteristic of non-ionic surfactants containing polyoxyethylene chains, which exhibit reverse solubility in water with temperature change, and therefore "become cloudy" at a certain temperature point with increasing temperature. Glycols that exhibit this behavior are known as "cloud point glycols". The cloud point is affected by salinity, and generally, the cloud point is lower in liquids with higher salinity.

[0036] Cloud concentration: as used herein, this term refers to the concentration of surfactant, particularly non-ionic surfactant, or glycol solution, at a given temperature in said solution, where the mixture of said surfactant and said solution begins to phase separate and two phases appear, thus becoming cloudy.For example, the cloud concentration of a surfactant at a given temperature in an aqueous solution is the minimum concentration of said surfactant that will produce two phases when mixed with an aqueous solution.The information about cloud concentration can be obtained from the surfactant manufacturer, or it can be determined experimentally by making a dose curve to determine the concentration at which the mixture phases separate.

[0037] The expression "X%Y" (where Y is a gas) in this specification refers to a gas or air mixture where Y constitutes a partial pressure that is X% of the total pressure of the gas or air mixture. By way of example, a gas mixture consisting of a partial pressure of 0.2 bar oxygen and a partial pressure of 0.8 bar nitrogen would be referred to as "20% oxygen" or a "20% oxygen gas mixture."

[0038] References herein to a volume of gas may refer to the volume of the pure gas or to a mixture of gases containing a larger volume of the gas. As an example, "1.5 ml of oxygen" may refer to either 1.5 ml of pure oxygen or 7.5 ml of a gas mixture containing 20% ​​oxygen.

[0039] Unless otherwise specified, references to volumes of gas should be taken as being at a pressure of 1.00 bar.

[0040] As used herein, when referring to the gas "oxygen" it is O 2 means...

[0041] As used herein, the term "alcohol" includes the term "fatty alcohol." As used herein, the term "alcohol composition" includes the term "fatty alcohol composition."

[0042] As used herein, the term "aldehyde" includes the term "aliphatic aldehyde." As used herein, the term "aldehyde composition" includes the term "aliphatic aldehyde composition."

[0043] As used herein, the term "acetal" includes the term "aliphatic acetal." As used herein, the term "acetal composition" includes the term "aliphatic acetal composition."

[0044] As used herein, the term "alpha-hydroxysulfonic acid" includes the term "aliphatic alpha-hydroxysulfonic acid." As used herein, the term "alpha-hydroxysulfonic acid composition" includes the term "aliphatic alpha-hydroxysulfonic acid composition."

[0045] The units ppm in this specification are by weight unless otherwise specified.

[0046] The term "waste" in this specification refers to oxidizing agent that has already acted as an oxidizing agent. 2 is an oxidizing agent, while H 2 O is the corresponding spent oxidant. As an example, the compound TEMPO is an oxidant, while the compound N-hydroxy-2,2,6,6-tetramethylpiperidine is the corresponding spent oxidant. Spent oxidants are sometimes called exhausted oxidants. Spent oxidants are often the reduced form of the corresponding oxidant.

[0047] Fatty alcohols The present disclosure relates to a fatty alcohol composition comprising at least one fatty alcohol. In one embodiment of the present disclosure, the fatty alcohol composition consists of or comprises a single fatty alcohol. In another embodiment, the fatty alcohol composition consists of or comprises a mixture of a small number of fatty alcohols (such as 2-5 fatty alcohols, i.e., 2, 3, 4 or 5 fatty alcohols). In yet another embodiment, the fatty alcohol composition consists of or comprises a plurality of fatty alcohols (such as 6 or more fatty alcohols).

[0048] In a preferred embodiment of the present disclosure, the aliphatic alcohol is primary aliphatic alcohol.Specifically, in an embodiment of the present disclosure, the conversion of aliphatic alcohol to aliphatic aldehyde as disclosed herein is the conversion of primary alcohol functional group to aldehyde functional group.In a preferred embodiment of the present disclosure, the conversion is the oxidation of primary alcohol functional group to aldehyde functional group.

[0049] It is believed that the method disclosed herein can be used to convert many different primary alcohols into their corresponding aldehydes.The method is particularly suitable for converting aliphatic alcohols into their corresponding aliphatic aldehydes, since other known methods either result in incomplete conversion, produce undesirable by-products, and / or require large amounts of solvent.

[0050] The fatty alcohol may be a saturated fatty alcohol or an unsaturated fatty alcohol. In one embodiment of the present disclosure, the fatty alcohol composition comprises only saturated fatty alcohols. In another embodiment, the fatty alcohol composition comprises only unsaturated fatty alcohols. In yet another embodiment of the present disclosure, the alcohol composition comprises both saturated and unsaturated fatty alcohols.

[0051] In one embodiment, the chain length of the fatty alcohol is 8. In another embodiment, the chain length of the fatty alcohol is 9. In another embodiment, the chain length of the fatty alcohol is 10. In another embodiment, the chain length of the fatty alcohol is 11. In another embodiment, the chain length of the fatty alcohol is 12. In another embodiment, the chain length of the fatty alcohol is 13. In another embodiment, the chain length of the fatty alcohol is 14. In another embodiment, the chain length of the fatty alcohol is 15. In another embodiment, the chain length of the fatty alcohol is 16. In another embodiment, the chain length of the fatty alcohol is 17. In another embodiment, the chain length of the fatty alcohol is 18. In another embodiment, the chain length of the fatty alcohol is 19. In another embodiment, the chain length of the fatty alcohol is 20. In another embodiment, the chain length of the fatty alcohol is 21. In another embodiment, the chain length of the fatty alcohol is 22.

[0052] The fatty alcohols may be branched or unbranched (i.e., linear or "straight-chain") In a preferred embodiment of the present disclosure, the fatty alcohol is unbranched.

[0053] In a preferred embodiment of the present disclosure, the chain length of the aliphatic alcohol is 12 to 16. In a further embodiment of the present disclosure, the aliphatic alcohol is unbranched and has a chain length of 12 to 16. In a further preferred embodiment of the present disclosure, the aliphatic alcohol is unbranched and has a chain length of 12. In another further preferred embodiment, the aliphatic alcohol is unbranched and has a chain length of 14. In another further preferred embodiment, the aliphatic alcohol is unbranched and has a chain length of 16.

[0054] In one embodiment of the present disclosure, the fatty alcohol is a saturated fatty alcohol. In one embodiment of the present disclosure, the fatty alcohol is a saturated fatty alcohol whose carbon chain length is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22.

[0055] In one embodiment of the present disclosure, the aliphatic alcohol is an unsaturated aliphatic alcohol. The double bond of the unsaturated aliphatic alcohol may be either E-configuration or Z-configuration, except when the double bond is a terminal double bond. In one embodiment of the present disclosure, the aliphatic alcohol comprises one or more double bonds of E-configuration. In one embodiment of the present disclosure, the aliphatic alcohol comprises one or more double bonds of Z-configuration. In yet another embodiment, the aliphatic alcohol comprises one or more double bonds of E-configuration and one or more double bonds of Z-configuration.

[0056] In some embodiments, the fatty alcohol is an unsaturated fatty alcohol. Such compounds are naturally produced, for example, by insect cells, where they act as pheromones. The unsaturated fatty alcohols may be: (Z)-Δ3 desaturated fatty alcohols having a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ3 desaturated fatty alcohols, the carbon chain length of which is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ5 desaturated fatty alcohols, the carbon chain length of which is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ5 desaturated fatty alcohols, the carbon chain length of which is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ6 desaturated fatty alcohols having a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ6 desaturated fatty alcohols, the carbon chain length of which is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ7 desaturated fatty alcohols, the carbon chain length of which is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ7 desaturated fatty alcohols, the carbon chain length of which is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ8 desaturated fatty alcohols, the carbon chain length of which is 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ8 desaturated fatty alcohols, the carbon chain length of which is 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ9 desaturated fatty alcohols, the carbon chain length of which is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ9 desaturated fatty alcohols, the carbon chain length of which is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ10 unsaturated fatty alcohols, the carbon chain length of which is 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ10 unsaturated fatty alcohols, the carbon chain length of which is 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ11 unsaturated fatty alcohols, the carbon chain length of which is 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ11 desaturated fatty alcohols, the carbon chain length of which is 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ12 desaturated fatty alcohols, the carbon chain length of which is 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ12 desaturated fatty alcohols, the carbon chain length of which is 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ13 unsaturated fatty alcohols, the carbon chain length of which is 14, 15, 16, 17, 18, 19, 20, 21 or 22; and (E)-Δ13 unsaturated fatty alcohols, the carbon chain length of which is 14, 15, 16, 17, 18, 19, 20, 21 or 22.

[0057] In some embodiments, the fatty alcohols are unsaturated fatty alcohols whose carbon chain length is 12, including unsaturated fatty alcohols such as: (Z)-Δ5 desaturated fatty alcohols, the carbon chain length of which is 12; (E)-Δ5 desaturated fatty alcohols, the carbon chain length of which is 12; (Z)-Δ6 desaturated fatty alcohols, the carbon chain length of which is 12; (E)-Δ6 desaturated fatty alcohols, the carbon chain length of which is 12; (Z)-Δ7 desaturated fatty alcohols, the carbon chain length of which is 12; (E)-Δ7 desaturated fatty alcohols, the carbon chain length of which is 12; (Z)-Δ8 desaturated fatty alcohols, the carbon chain length of which is 12; (E)-Δ8 desaturated fatty alcohols, the carbon chain length of which is 12; (Z)-Δ9 desaturated fatty alcohols, the carbon chain length of which is 12; (E)-Δ9 desaturated fatty alcohols, the carbon chain length of which is 12; (Z)-Δ10 desaturated fatty alcohols, the carbon chain length of which is 12; (E)-Δ10 desaturated fatty alcohols, the carbon chain length of which is 12; (Z)-Δ11 desaturated fatty alcohols, the carbon chain length of which is 12; and (E)-Δ11 desaturated fatty alcohols, the carbon chain length of which is 12.

[0058] In some embodiments, the fatty alcohols are unsaturated fatty alcohols whose carbon chain length is 14, including unsaturated fatty alcohols such as: (Z)-Δ5 desaturated fatty alcohols, the carbon chain length of which is 14; (E)-Δ5 desaturated fatty alcohols, the carbon chain length of which is 14; (Z)-Δ6 desaturated fatty alcohols, the carbon chain length of which is 14; (E)-Δ6 desaturated fatty alcohols, the carbon chain length of which is 14; (Z)-Δ7 desaturated fatty alcohols, the carbon chain length of which is 14; (E)-Δ7 desaturated fatty alcohols, the carbon chain length of which is 14; (Z)-Δ8 desaturated fatty alcohols, the carbon chain length of which is 14; (E)-Δ8 desaturated fatty alcohols, the carbon chain length of which is 14; (Z)-Δ9 desaturated fatty alcohols, the carbon chain length of which is 14; (E)-Δ9 desaturated fatty alcohols, the carbon chain length of which is 14; (Z)-Δ10 desaturated fatty alcohols, the carbon chain length of which is 14; (E)-Δ10 desaturated fatty alcohols, the carbon chain length of which is 14; (Z)-Δ11 desaturated fatty alcohols, the carbon chain length of which is 14; (E)-Δ11 desaturated fatty alcohols, the carbon chain length of which is 14; (Z)-Δ12 desaturated fatty alcohols, the carbon chain length of which is 14; (E)-Δ12 desaturated fatty alcohols, the carbon chain length of which is 14; (Z)-Δ13 desaturated fatty alcohols, the carbon chain length of which is 14; and (E)-Δ13 desaturated fatty alcohols, the carbon chain length of which is 14.

[0059] In some embodiments, the fatty alcohols are unsaturated fatty alcohols whose carbon chain length is 16, including unsaturated fatty alcohols such as: (Z)-Δ5 desaturated fatty alcohols, the carbon chain length of which is 16; (E)-Δ5 desaturated fatty alcohols, the carbon chain length of which is 16; (Z)-Δ6 desaturated fatty alcohols, the carbon chain length of which is 16; (E)-Δ6 desaturated fatty alcohols, the carbon chain length of which is 16; (Z)-Δ7 desaturated fatty alcohols, the carbon chain length of which is 16; (E)-Δ7 desaturated fatty alcohols, the carbon chain length of which is 16; (Z)-Δ8 desaturated fatty alcohols, the carbon chain length of which is 16; (E)-Δ8 desaturated fatty alcohols, the carbon chain length of which is 16; (Z)-Δ9 desaturated fatty alcohols, the carbon chain length of which is 16; (E)-Δ9 desaturated fatty alcohols, the carbon chain length of which is 16; (Z)-Δ10 desaturated fatty alcohols, the carbon chain length of which is 16; (E)-Δ10 desaturated fatty alcohols, the carbon chain length of which is 16; (Z)-Δ11 desaturated fatty alcohols, the carbon chain length of which is 16; (E)-Δ11 desaturated fatty alcohols, the carbon chain length of which is 16; (Z)-Δ12 desaturated fatty alcohols, the carbon chain length of which is 16; (E)-Δ12 desaturated fatty alcohols, the carbon chain length of which is 16; (Z)-Δ13 desaturated fatty alcohols, the carbon chain length of which is 16; and (E)-Δ13 desaturated fatty alcohols, the carbon chain length of which is 16.

[0060] For example, the fatty alcohol is an (E)7,(Z)9 desaturated fatty alcohol having a carbon chain length of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22. In some embodiments, the fatty alcohol is an (E)3,(Z)8,(Z)11 desaturated fatty alcohol having a carbon chain length of 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22, e.g., 14. In some embodiments, the fatty alcohol is an (Z)9,(E)11,(E)13 desaturated fatty alcohol having a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21, or 22. In some embodiments, the fatty alcohol is a (Z)11,(Z)13 desaturated fatty alcohol having a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21, or 22. In some embodiments, the fatty alcohol is a (Z)9,(E)12 desaturated fatty alcohol having a carbon chain length of 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22. In some embodiments, the fatty alcohol is an (E)7,(E)9 desaturated fatty alcohol having a carbon chain length of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22. In some embodiments, the fatty alcohol is an (E)8,(E)10 unsaturated fatty alcohol having a carbon chain length of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22.

[0061] In another embodiment, the fatty alcohol is an (E)7,(Z)9 desaturated fatty alcohol having a carbon chain length of 14. In another embodiment, the desaturated fatty alcohol is an (E)3,(Z)8,(Z)11 desaturated fatty alcohol having a carbon chain length of 14. In another embodiment, the desaturated fatty alcohol is an (Z)9,(E)11,(E)13 desaturated fatty alcohol having a carbon chain length of 14. For example, the fatty alcohol is an (E)7,(Z)9 desaturated fatty alcohol having a carbon chain length of 12. In another embodiment, the desaturated fatty alcohol is an (E)3,(Z)8,(Z)11 desaturated fatty alcohol having a carbon chain length of 12. In another embodiment, the unsaturated fatty alcohol is a (Z)9,(E)11,(E)13 desaturated fatty alcohol having a carbon chain length of 12. In another embodiment, the unsaturated fatty alcohol is a (E)8,(E)10 desaturated fatty alcohol having a carbon chain length of 12. In another embodiment, the unsaturated fatty alcohol is a (E)7,(E)9 desaturated fatty alcohol having a carbon chain length of 11. In another embodiment, the unsaturated fatty alcohol is a (Z)11,(Z)13 desaturated fatty alcohol having a carbon chain length of 16. In another embodiment, the unsaturated fatty alcohol is a (Z)9,(E)12 desaturated fatty alcohol having a carbon chain length of 14.

[0062] In some embodiments, the fatty alcohol is (Z9,E12)-tetradecadien-1-ol. Microbial cell factories and methods for obtaining (Z9,E12)-tetradecadien-1-ol from yeast cells are described in detail in EP21183447.8, entitled "Methods and yeast cells for production of desaturated compounds," filed by the applicant on July 2, 2021.

[0063] In some embodiments, the fatty alcohol is (Z11,Z13)-hexadecadien-1-ol. Microbial cell factories and methods for obtaining (Z11,Z13)-hexadecadien-1-ol from yeast cells are described in detail in EP21183459.3, entitled "Methods and yeast cells for production of desaturated compounds," filed by the applicant on July 2, 2021.

[0064] In some embodiments, the aliphatic alcohol is (E8,E10)-dodecadien-1-ol. Microbial cell factories and methods for obtaining (E8,E10)-hexadecadien-1-ol from yeast cells are described in detail in WO2021 / 123128.

[0065] In some embodiments, the fatty alcohol is (Z11)-hexadecen-1-ol. Microbial cell factories and methods for obtaining (Z11)-hexadecen-1-ol from yeast cells are described in detail in WO2016 / 207339.

[0066] In a preferred embodiment of the disclosure, the fatty alcohol has a double bond at the 9, 11, or 13 positions, or a double bond at the 9 and 11 positions, or a double bond at the 11 and 13 positions; alternatively, the fatty alcohol has a double bond at the 9 or 12 positions, or a double bond at the 9 and 12 positions. In a further preferred embodiment of the disclosure, the fatty alcohol has a chain length of 12 and a double bond at the 9 or 11 positions, or a double bond at the 9 and 11 positions; alternatively, the fatty alcohol has a chain length of 14 and a double bond at the 9 or 12 positions, or a double bond at the 9 and 12 positions; alternatively, the fatty alcohol has a chain length of 14 and a double bond at the 9, 11, or 13 positions, or a double bond at the 9 and 11 positions, or a double bond at the 11 and 13 positions. In another more preferred embodiment of the disclosure, the fatty alcohol has a chain length of 14 and a double bond at position 9 or 11, or a double bond at positions 9 and 11. In another more preferred embodiment of the disclosure, the fatty alcohol has a chain length of 16 and a double bond at position 9 or 11, or a double bond at positions 9 and 11. In another embodiment, the fatty alcohol has a chain length of 16 and a double bond at position 11 or 13, or a double bond at positions 11 and 13. In another embodiment, the fatty alcohol has a chain length of 12 and a double bond at position 8 or 10, or a double bond at positions 8 and 10.

[0067] In a particular embodiment, the aliphatic alcohol is selected from the group consisting of tetradecane-1-ol, pentadecane-1-ol, hexadecane-1-ol, pentadecene-1-ol, (Z)-9-hexadecen-1-ol, (Z)-11-hexadecen-1-ol, (7E,9E)-undeca-7,9-dien-1-ol, (11Z,13Z)-hexadecadien-1-ol, (9Z,12E)-tetradecadien-1-ol, and (8E,10E)-dodecadien-1-ol.In a particular embodiment, the aliphatic alcohol is (Z)-11-hexadecen-1-ol or (Z)-9-tetradecen-1-ol.

[0068] The fatty alcohol composition may consist entirely of fatty alcohols or may include fatty alcohols and other compounds. In one embodiment of the present disclosure, the fatty alcohol composition comprises 5 wt% to 10 wt% of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises 10 wt% to 20 wt% of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises 20 wt% to 30 wt% of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises 30 wt% to 40 wt% of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises 40 wt% to 50 wt% of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises 50 wt% to 60 wt% of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises 60 wt% to 70 wt% of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises 70 wt% to 80 wt% of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises 80 wt% to 90 wt% of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises 90 wt% to 100 wt% of one or more fatty alcohols. In a preferred embodiment of the present disclosure, the fatty alcohol composition comprises one or more fatty alcohols in the range of 50% to 100%. In a further preferred embodiment, the fatty alcohol composition comprises one or more fatty alcohols in the range of 60% to 100%.

[0069] In one embodiment of the present disclosure, the fatty alcohol composition comprises at least 30 wt% of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises at least 35 wt% of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises at least 40 wt% of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises at least 45 wt% of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises at least 50 wt% of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises at least 55 wt% of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises at least 60 wt% of one or more fatty alcohols.

[0070] In a preferred embodiment of the present disclosure, the fatty alcohol composition is substantially dry; i.e., contains only a small amount of water at most.In a preferred embodiment of the present disclosure, the fatty alcohol composition does not contain any compounds that adversely interfere with the oxidation.Compounds that may be harmful to the reaction conditions include, for example, carboxylic acids, amino acids, amines, 1,2-diols, 1,3-diols, sulfides, and other chelating compounds.

[0071] The methods disclosed herein are intended to be particularly useful for the oxidation of alcohols or pheromone alcohols derived from industrial feedstocks. In one embodiment of the disclosure, the fatty alcohol composition is derived from an industrial feedstock. In one embodiment of the disclosure, the fatty alcohol composition comprises pheromone alcohols.

[0072] In one embodiment, the fatty alcohol composition comprises one or more fatty alcohols disclosed herein, wherein each of the one or more fatty alcohols is present in an amount of 0.1 wt% to 100 wt%. In one particular embodiment of the present disclosure, the fatty alcohol composition comprises (Z)-11-hexadecen-1-ol. In a further particular embodiment of the present disclosure, the fatty alcohol composition comprises 10 wt% to 100 wt% (Z)-11-hexadecen-1-ol. In a further particular embodiment of the present disclosure, the fatty alcohol composition comprises 50 wt% to 100 wt% (Z)-11-hexadecen-1-ol. In a further particular embodiment of the present disclosure, the fatty alcohol composition comprises (Z)-9-hexadecen-1-ol. In a further specific embodiment of the present disclosure, the aliphatic alcohol composition comprises 1 wt% to 10 wt% of (Z)-9-hexadecen-1-ol. In a specific embodiment of the present disclosure, the aliphatic alcohol composition comprises hexadecan-1-ol. In a further specific embodiment of the present disclosure, the aliphatic alcohol composition comprises 1 wt% to 15 wt% of hexadecan-1-ol. In a specific embodiment of the present disclosure, the alcohol composition comprises 50 wt% to 98 wt% of (Z)-11-hexadecen-1-ol, 1 wt% to 10 wt% of (Z)-9-hexadecen-1-ol, and 1 wt% to 15 wt% of hexadecan-1-ol.

[0073] In one embodiment of the present disclosure, the fatty alcohol composition comprises 10 wt% to 100 wt% of (Z)-11-hexadecen-1-ol. In one embodiment of the present disclosure, the fatty alcohol composition comprises 1 wt% to 10 wt% of (Z)-9-hexadecen-1-ol. In one embodiment of the present disclosure, the fatty alcohol composition comprises 1 wt% to 15 wt% of hexadecan-1-ol. In one embodiment of the present disclosure, the fatty alcohol composition comprises 1 wt% to 20 wt% of monounsaturated pentadecen-1-ol. In one particular embodiment, the fatty alcohol composition comprises 10 wt% to 100 wt% (Z)-11-hexadecen-1-ol, 1 wt% to 10 wt% (Z)-9-hexadecen-1-ol, 1 wt% to 15 wt% hexadecan-1-ol, and 1 wt% to 20 wt% monounsaturated pentadecen-1-ol.

[0074] Aliphatic aldehydes The present disclosure relates to an aliphatic aldehyde composition comprising at least one aliphatic aldehyde. In one embodiment of the present disclosure, the aliphatic aldehyde composition comprises or consists of a single aliphatic aldehyde. In another embodiment, the aliphatic aldehyde composition comprises or consists of a mixture of several aliphatic aldehydes (e.g., 2 to 5 aliphatic aldehydes). In yet another embodiment, the aliphatic aldehyde composition comprises or consists of a plurality of aliphatic aldehydes (e.g., 6 or more aliphatic aldehydes).

[0075] The aliphatic aldehyde may be a saturated aliphatic aldehyde or an unsaturated aliphatic aldehyde. In one embodiment of the present disclosure, the aliphatic aldehyde composition comprises only saturated aliphatic aldehydes. In another embodiment, the aliphatic aldehyde composition comprises only unsaturated aliphatic aldehydes. In yet another embodiment of the present disclosure, the aldehyde composition comprises both saturated aliphatic aldehydes and unsaturated aliphatic aldehydes.

[0076] In one embodiment, the chain length of the aliphatic aldehyde is 8. In another embodiment, the chain length of the aliphatic aldehyde is 9. In another embodiment, the chain length of the aliphatic aldehyde is 10. In another embodiment, the chain length of the aliphatic aldehyde is 11. In another embodiment, the chain length of the aliphatic aldehyde is 12. In another embodiment, the chain length of the aliphatic aldehyde is 13. In another embodiment, the chain length of the aliphatic aldehyde is 14. In another embodiment, the chain length of the aliphatic aldehyde is 15. In another embodiment, the chain length of the aliphatic aldehyde is 16. In another embodiment, the chain length of the aliphatic aldehyde is 17. In another embodiment, the chain length of the aliphatic aldehyde is 18. In another embodiment, the chain length of the aliphatic aldehyde is 19. In another embodiment, the chain length of the aliphatic aldehyde is 20. In another embodiment, the chain length of the aliphatic aldehyde is 21. In another embodiment, the chain length of the aliphatic aldehyde is 22.

[0077] The aliphatic aldehydes may be branched or unbranched (i.e., linear or "straight-chain") In a preferred embodiment of the present disclosure, the aliphatic aldehyde is unbranched.

[0078] In a preferred embodiment of the present disclosure, the aliphatic aldehyde has a chain length of 12 to 16. In a further embodiment of the present disclosure, the aliphatic aldehyde is unbranched and has a chain length of 12 to 16. In a further preferred embodiment of the present disclosure, the aliphatic aldehyde is unbranched and has a chain length of 12. In another further preferred embodiment, the aliphatic aldehyde is unbranched and has a chain length of 14. In another further preferred embodiment, the aliphatic aldehyde is unbranched and has a chain length of 16.

[0079] In one embodiment of the present disclosure, the aliphatic aldehyde is a saturated aliphatic aldehyde. In one embodiment of the present disclosure, the aliphatic aldehyde is a saturated aliphatic aldehyde whose carbon chain length is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22.

[0080] In one embodiment of the present disclosure, the aliphatic aldehyde is an unsaturated aliphatic aldehyde. The double bond of the unsaturated aliphatic aldehyde can be either E or Z configuration, except when the double bond is a terminal double bond. In one embodiment of the present disclosure, the aliphatic aldehyde comprises one or more double bonds of E configuration. In one embodiment of the present disclosure, the aliphatic aldehyde comprises one or more double bonds of Z configuration. In yet another embodiment, the aliphatic aldehyde comprises one or more double bonds of E configuration and one or more double bonds of Z configuration.

[0081] In some embodiments, the aliphatic aldehyde is an unsaturated aliphatic aldehyde. The unsaturated aliphatic aldehydes can be: (Z)-Δ3 unsaturated aliphatic aldehydes, the carbon chain length of which is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ3 unsaturated aliphatic aldehydes, the carbon chain length of which is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ5 unsaturated aliphatic aldehydes, the carbon chain length of which is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ5 unsaturated aliphatic aldehydes, the carbon chain length of which is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ6 unsaturated aliphatic aldehydes, the carbon chain length of which is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ6 unsaturated aliphatic aldehydes, the carbon chain length of which is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ7 unsaturated aliphatic aldehydes, the carbon chain length of which is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ7 unsaturated aliphatic aldehydes, the carbon chain length of which is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ8 unsaturated aliphatic aldehydes, the carbon chain length of which is 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ8 unsaturated aliphatic aldehydes, the carbon chain length of which is 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ9 unsaturated aliphatic aldehydes, the carbon chain length of which is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ9 unsaturated aliphatic aldehydes, the carbon chain length of which is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ10 unsaturated aliphatic aldehydes, the carbon chain length of which is 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ10 unsaturated aliphatic aldehydes, the carbon chain length of which is 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ11 unsaturated aliphatic aldehydes, the carbon chain length of which is 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ11 unsaturated aliphatic aldehydes, the carbon chain length of which is 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ12 unsaturated aliphatic aldehydes, the carbon chain length of which is 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ12 unsaturated aliphatic aldehydes, the carbon chain length of which is 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ13 unsaturated aliphatic aldehydes, the carbon chain length of which is 14, 15, 16, 17, 18, 19, 20, 21 or 22; and (E)-Δ13 unsaturated aliphatic aldehydes, the carbon chain length of which is 14, 15, 16, 17, 18, 19, 20, 21 or 22.

[0082] In some embodiments, the aliphatic aldehydes are unsaturated aliphatic aldehydes whose carbon chain length is 12, including unsaturated aliphatic aldehydes such as: (Z)-Δ5 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 12; (E)-Δ5 desaturated aliphatic aldehydes, the carbon chain length of which is 12; (Z)-Δ6 unsaturated aliphatic aldehydes, the carbon chain length of which is 12; (E)-Δ6 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 12; (Z)-Δ7 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 12; (E)-Δ7 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 12; (Z)-Δ8 unsaturated aliphatic aldehydes, the carbon chain length of which is 12; (E)-Δ8 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 12; (Z)-Δ9 unsaturated aliphatic aldehydes, the carbon chain length of which is 12; (E)-Δ9 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 12; (Z)-Δ10 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 12; (E)-Δ10 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 12; (Z)-Δ11 unsaturated aliphatic aldehydes, the carbon chain length of which is 12; and (E)-Δ11 unsaturated aliphatic aldehydes, the carbon chain length of which is 12.

[0083] In some embodiments, the aliphatic aldehydes are unsaturated aliphatic aldehydes whose carbon chain length is 14, including unsaturated aliphatic aldehydes such as: (Z)-Δ5 unsaturated aliphatic aldehydes, the carbon chain length of which is 14; (E)-Δ5 desaturated aliphatic aldehydes, the carbon chain length of which is 14; (Z)-Δ6 unsaturated aliphatic aldehydes, the carbon chain length of which is 14; (E)-Δ6 unsaturated aliphatic aldehydes, the carbon chain length of which is 14; (Z)-Δ7 unsaturated aliphatic aldehydes, the carbon chain length of which is 14; (E)-Δ7 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 14; (Z)-Δ8 unsaturated aliphatic aldehydes, the carbon chain length of which is 14; (E)-Δ8 desaturated aliphatic aldehydes, the carbon chain length of which is 14; (Z)-Δ9 unsaturated aliphatic aldehydes, the carbon chain length of which is 14; (E)-Δ9 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 14; (Z)-Δ10 unsaturated aliphatic aldehydes, the carbon chain length of which is 14; (E)-Δ10 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 14; (Z)-Δ11 unsaturated aliphatic aldehydes, the carbon chain length of which is 14; (E)-Δ11 unsaturated aliphatic aldehydes, the carbon chain length of which is 14; (Z)-Δ12 unsaturated aliphatic aldehydes, the carbon chain length of which is 14; (E)-Δ12 unsaturated aliphatic aldehydes, the carbon chain length of which is 14; (Z)-Δ13 unsaturated aliphatic aldehydes, the carbon chain length of which is 14; and (E)-Δ13 unsaturated aliphatic aldehydes, the carbon chain length of which is 14.

[0084] In some embodiments, the aliphatic aldehydes are unsaturated aliphatic aldehydes whose carbon chain length is 16, including unsaturated aliphatic aldehydes such as: (Z)-Δ5 desaturated aliphatic aldehydes, the carbon chain length of which is 16; (E)-Δ5 desaturated aliphatic aldehydes, the carbon chain length of which is 16; (Z)-Δ6 unsaturated aliphatic aldehydes, the carbon chain length of which is 16; (E)-Δ6 desaturated aliphatic aldehydes, the carbon chain length of which is 16; (Z)-Δ7 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 16; (E)-Δ7 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 16; (Z)-Δ8 desaturated aliphatic aldehydes, the carbon chain length of which is 16; (E)-Δ8 desaturated aliphatic aldehydes, the carbon chain length of which is 16; (Z)-Δ9 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 16; (E)-Δ9 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 16; (Z)-Δ10 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 16; (E)-Δ10 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 16; (Z)-Δ11 unsaturated aliphatic aldehydes, the carbon chain length of which is 16; (E)-Δ11 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 16; (Z)-Δ12 unsaturated aliphatic aldehydes, the carbon chain length of which is 16; (E)-Δ12 unsaturated aliphatic aldehydes, the carbon chain length of which is 16; (Z)-Δ13 unsaturated aliphatic aldehydes, the carbon chain length of which is 16; and (E)-Δ13 unsaturated aliphatic aldehydes, the carbon chain length of which is 16.

[0085] For example, the aliphatic aldehyde is an (E)7,(Z)9 unsaturated aliphatic aldehyde having a carbon chain length of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22. In some embodiments, the aliphatic aldehyde is an (E)3,(Z)8,(Z)11 unsaturated aliphatic aldehyde having a carbon chain length of 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22, e.g., 14. In some embodiments, the aliphatic aldehyde is a (Z)9,(E)11,(E)13 unsaturated aliphatic aldehyde having a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21, or 22. In some embodiments, the aliphatic aldehyde is a (Z)11,(Z)13 unsaturated aliphatic aldehyde having a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21, or 22. In some embodiments, the aliphatic aldehyde is a (Z)9,(E)12 unsaturated aliphatic aldehyde having a carbon chain length of 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22. In some embodiments, the aliphatic aldehyde is an (E)7,(E)9 desaturated aliphatic aldehyde having a carbon chain length of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22. In some embodiments, the aliphatic aldehyde is an (E)8,(E)10 desaturated aliphatic aldehyde having a carbon chain length of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22.

[0086] In another embodiment, the aliphatic aldehyde is an (E)7,(Z)9 desaturated aliphatic aldehyde having a carbon chain length of 14. In another embodiment, the desaturated aliphatic aldehyde is an (E)3,(Z)8,(Z)11 desaturated aliphatic aldehyde having a carbon chain length of 14. In another embodiment, the desaturated aliphatic aldehyde is a (Z)9,(E)11,(E)13 desaturated aliphatic aldehyde having a carbon chain length of 14. For example, the aliphatic aldehyde is an (E)7,(Z)9 desaturated aliphatic aldehyde having a carbon chain length of 12. In another embodiment, the unsaturated aliphatic aldehyde is an (E)3,(Z)8,(Z)11 unsaturated aliphatic aldehyde having a carbon chain length of 12. In another embodiment, the unsaturated aliphatic aldehyde is a (Z)9,(E)11,(E)13 unsaturated aliphatic aldehyde having a carbon chain length of 12. In another embodiment, the unsaturated aliphatic aldehyde is an (E)8,(E)10 unsaturated aliphatic aldehyde having a carbon chain length of 12. In another embodiment, the unsaturated aliphatic aldehyde is an (E)7,(E)9 unsaturated aliphatic aldehyde having a carbon chain length of 11. In other embodiments, the unsaturated aliphatic aldehyde is a (Z)11,(Z)13 unsaturated aliphatic aldehyde having a carbon chain length of 16. In other embodiments, the unsaturated aliphatic aldehyde is a (Z)9,(E)12 unsaturated aliphatic aldehyde having a carbon chain length of 14.

[0087] In some embodiments, the aliphatic aldehyde is (Z9,E12)-tetradecadien-1-al. Microbial cell factories and methods for obtaining the corresponding alcohol (Z9,E12)-tetradecadien-1-ol from yeast cells are described in detail in EP21183447.8, entitled "Methods and yeast cells for production of desaturated compounds," filed by the applicant on July 2, 2021. This alcohol can be converted to (Z9,E12)-tetradecadien-1-al using the methods disclosed herein.

[0088] In some embodiments, the aliphatic aldehyde is (Z11,Z13)-hexadecadien-1-al. Microbial cell factories and methods for obtaining the corresponding alcohol (Z11,Z13)-hexadecadien-1-ol from yeast cells are described in detail in EP21183459.3, entitled "Methods and yeast cells for production of desaturated compounds," filed by the applicant on July 2, 2021. This alcohol can be converted to Z11,Z13)-hexadecadien-1-al using the methods disclosed herein.

[0089] In some embodiments, the aliphatic aldehyde is (E8,E10)-dodecadien-1-al. A microbial cell factory and method for obtaining the corresponding alcohol (E8,E10)-hexadecadien-1-ol from yeast cells is described in detail in WO2021 / 123128. This alcohol can be converted to (E8,E10)-dodecadien-1-al using the methods disclosed herein.

[0090] In some embodiments, the aliphatic aldehyde is (Z11)-hexadecen-1-al. A microbial cell factory and method for obtaining the corresponding alcohol (Z11)-hexadecen-1-ol from yeast cells is described in detail in WO2016 / 207339. This alcohol can be converted to (Z11)-hexadecen-1-al using the methods disclosed herein.

[0091] In a preferred embodiment of the disclosure, the aliphatic aldehyde has a double bond at the 9, 11, or 13 positions, or a double bond at the 9 and 11 positions, or a double bond at the 11 and 13 positions; or the aliphatic aldehyde has a double bond at the 9 or 12 positions, or a double bond at the 9 and 12 positions. In a further preferred embodiment of the disclosure, the aliphatic aldehyde has a chain length of 12 and a double bond at the 9 or 11 positions, or a double bond at the 9 and 11 positions; or the aliphatic aldehyde has a chain length of 14 and a double bond at the 9 or 12 positions, or a double bond at the 9 and 12 positions; or the aliphatic aldehyde has a chain length of 14 and a double bond at the 9, 11, or 13 positions, or a double bond at the 9 and 11 positions, or a double bond at the 11 and 13 positions. In another more preferred embodiment of the disclosure, the aliphatic aldehyde has a chain length of 14 and a double bond at the 9 or 11 position, or a double bond at the 9 and 11 positions. In another more preferred embodiment of the disclosure, the aliphatic aldehyde has a chain length of 16 and a double bond at the 9 or 11 position, or a double bond at the 9 and 11 positions. In another embodiment, the aliphatic aldehyde has a chain length of 16 and a double bond at the 11 or 13 position, or a double bond at the 11 and 13 positions. In another embodiment, the aliphatic aldehyde has a chain length of 12 and a double bond at the 8 or 10 position, or a double bond at the 8 and 10 positions.

[0092] In a particular embodiment, the aliphatic aldehyde is selected from the group consisting of tetradecane-1-al, pentadecane-1-al, hexadecan-1-al, pentadecen-1-al, (Z)-9-hexadecen-1-al, (Z)-11-hexadecen-1-al, (7E,9E)-undeca-7,9-dien-1-al, (11Z,13Z)-hexadecadien-1-al, (9Z,12E)-tetradecadien-1-al, and (8E,10E)-dodecadien-1-al.

[0093] In one particular embodiment, the aliphatic aldehyde is (Z)-11-hexadecenal or (Z)-9-tetradecenal.

[0094] The aliphatic aldehyde composition may consist entirely of aliphatic aldehydes, or may include aliphatic aldehydes and other compounds. In one embodiment of the present disclosure, the aliphatic aldehyde composition comprises 5 wt% to 10 wt% of one or more aliphatic aldehydes. In another embodiment, the aliphatic aldehyde composition comprises 10 wt% to 20 wt% of one or more aliphatic aldehydes. In another embodiment, the aliphatic aldehyde composition comprises 20 wt% to 30 wt% of one or more aliphatic aldehydes. In another embodiment, the aliphatic aldehyde composition comprises 30 wt% to 40 wt% of one or more aliphatic aldehydes. In another embodiment, the aliphatic aldehyde composition comprises 40 wt% to 50 wt% of one or more aliphatic aldehydes. In another embodiment, the aliphatic aldehyde composition contains one or more aliphatic aldehydes in an amount of 50 wt% to 60 wt%. In another embodiment, the aliphatic aldehyde composition contains one or more aliphatic aldehydes in an amount of 60 wt% to 70 wt%. In another embodiment, the aliphatic aldehyde composition contains one or more aliphatic aldehydes in an amount of 70 wt% to 80 wt%. In another embodiment, the aliphatic aldehyde composition contains one or more aliphatic aldehydes in an amount of 80 wt% to 90 wt%. In another embodiment, the aliphatic aldehyde composition contains one or more aliphatic aldehydes in an amount of 90 wt% to 100 wt%. In a preferred embodiment of the present disclosure, the aliphatic aldehyde composition contains one or more aliphatic aldehydes in a range of 50% to 100%. In a further preferred embodiment, the aliphatic aldehyde composition contains one or more kinds of aliphatic aldehydes in the range of 60% to 100%.

[0095] In one embodiment of the present disclosure, the aliphatic aldehyde composition comprises at least 30 wt% of one or more aliphatic aldehydes. In another embodiment, the aliphatic aldehyde composition comprises at least 35 wt% of one or more aliphatic aldehydes. In another embodiment, the aliphatic aldehyde composition comprises at least 40 wt% of one or more aliphatic aldehydes. In another embodiment, the aliphatic aldehyde composition comprises at least 45 wt% of one or more aliphatic aldehydes. In another embodiment, the aliphatic aldehyde composition comprises at least 50 wt% of one or more aliphatic aldehydes. In another embodiment, the aliphatic aldehyde composition comprises at least 55 wt% of one or more aliphatic aldehydes. In another embodiment, the aliphatic aldehyde composition comprises at least 60 wt% of one or more aliphatic aldehydes. In a preferred embodiment, the aliphatic aldehyde composition comprises at least 70 wt% of one or more aliphatic aldehydes. In another preferred embodiment, the aliphatic aldehyde composition comprises at least 80 wt% of one or more aliphatic aldehydes. In another preferred embodiment, the aliphatic aldehyde composition comprises at least 90 wt% of one or more aliphatic aldehydes.

[0096] The embodiments of the aldehyde compositions as outlined herein preferably refer to isolated and purified aldehyde compositions.

[0097] catalyst composition The present disclosure relates to the oxidation of primary alcohols to the corresponding aldehydes. The oxidation of the primary alcohol to the aldehyde is catalyzed by a catalyst composition.

[0098] The catalyst composition includes a copper(I) source, such as a copper(I) salt, which is a material or mixture of materials that includes a copper(I) compound that is available for the desired catalytic activity. Examples include, inter alia, copper(I) chloride, copper(I) bromide, copper(I) iodide, copper(I) cyanide, copper(I) oxide, copper(I) trifluoromethanesulfonate, tetrakis(acetonitrile)copper(I) tetrafluoroborate, tetrakis(acetonitrile)copper(I) tetraphenylborate, tetrakis(acetonitrile)copper(I) hexafluorophosphate, tetrakis(acetonitrile)copper(I) trifluoromethanesulfonate, copper(I) sulfide, copper(I) thiocyanate, Cu[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]CI, Cu[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]Br, CuBr(1,10-phenanthroline). 2 , CuCl(1,10-phenanthroline)] 2 , Cul(1,10-phenanthroline) 2 , copper(I) trifluoroacetate, [Cu(PPh 3 ) 3 ]Br, [Cu(PPh 3 ) 3 ]F, [Cu(PPh 3 ) 3 ]Cl, Cu(OCOR 2 ), Cu(SR 2 ), Cu(SR 2 2 )Br, Cu(SR 2 2 )Cl, Cu(SR 2 2 )I, Cu(OSO 2 R 2 ), CuOR 2 Here, R 2is selected from: alkyl, preferably C1-C20 alkyl, optionally substituted with one or more aryl, alkoxy and aryloxy; aryl, preferably C5-C7 aryl, optionally substituted with one or more alkyl, aryl, alkoxy and aryloxy; and mixtures thereof. Additionally, the copper(I) source may be a material or mixture of materials containing copper in any other oxidation state, provided that it can be converted to copper in the +1 oxidation state by means of reduction or oxidation, either chemically or electrochemically.

[0099] In a preferred embodiment of the present disclosure, the copper(I) source comprises copper present in the +1 oxidation state.

[0100] In one embodiment of the present disclosure, the copper(I) source is soluble in an organic solvent. In a preferred embodiment, the organic solvent is acetonitrile. The solubility of the reagent generally improves the reaction rate. In a preferred embodiment of the present disclosure, the copper(I) source is a copper(I) salt that includes a counterion that exhibits good solubility in an organic solvent, i.e., a negatively charged ion. Examples of negatively charged ions that are generally considered to exhibit good solubility in organic solvents such as acetonitrile include triflate, tetrafluoroborate, hexafluorophosphate, and halides.

[0101] The copper(I) source may further include a ligand coordinated to copper. Examples of copper(I) sources with ligands include tetrakisacetonitrile copper(I) triflate, tetrakisacetonitrile copper(I) tetrafluoroborate, tetrakisacetonitrile copper(I) hexafluorophosphate, tetrakisacetonitrile copper(I) halide, CuBr(1,10-phenanthroline). 2 , CuCl(1,10-phenanthroline)] 2 , and Cul (1,10-phenanthroline) 2 Examples include:

[0102] In a preferred embodiment of the present disclosure, the copper(I) source is selected from the group consisting of tetrakisacetonitrile copper(I) triflate, tetrakisacetonitrile copper(I) tetrafluoroborate, tetrakisacetonitrile copper(I) hexafluorophosphate, and tetrakisacetonitrile copper(I) halide.

[0103] Copper(I) ions can be generated in situ by a copper(II) compound and a reducing agent. Thus, in one embodiment, the copper(I) source comprises a copper(II) compound and a reducing agent. In one embodiment, the copper(I) source is a copper(II) compound and a reducing agent.

[0104] In one embodiment, the copper(II) compound is a copper(II) salt. In one embodiment, the copper(II) salt comprises a counterion that is soluble in an organic solvent. The counterion that is soluble in an organic solvent typically comprises a large organic moiety and / or a negative charge that can be delocalized (e.g., by resonance or induction). In one embodiment, the copper(II) salt is selected from the group consisting of copper(II) triflate, copper(II) tetrafluoroborate, copper(II) hexafluorophosphate, copper(II) bromide, copper(II) chloride, copper(II) iodide, and copper(II) perchlorate.

[0105] The reducing agent as disclosed herein can reduce copper(II) to copper(I). The reducing agent can be either an organic reducing agent or an inorganic reducing agent. In one embodiment of the present disclosure, the reducing agent is selected from the group consisting of copper metal, zinc metal, aluminum metal, sodium hydrogen sulfate, formic acid, salts of formic acid, oxalic acid, and salts of oxalic acid. The metal-based reducing agent can be in powder, pellet, shavings, or micronized form, which has advantages. The reducing agent can be advantageously selected to produce no by-products or to produce by-products that are easy to remove (e.g., by evaporation). In one embodiment of the present disclosure, the copper(I) source comprises a copper(II) salt and copper metal.

[0106] In one embodiment of the present disclosure, the catalyst composition of the present disclosure includes a ligand whose role is expected to be to coordinate to the copper(I) of the catalyst composition, thereby improving the solubility of copper(I), stabilizing the catalyst composition, and / or improving the catalytic activity of the catalyst composition.

[0107] Suitable ligands include those that coordinate through nitrogen, oxygen, phosphorus, or other atoms with lone pairs of electrons. In one embodiment of the present disclosure, the ligand coordinates through a moiety selected from the group consisting of pyridine, triarylphosphine, diarylphosphine, amine, imidazole, pyrazole, pyrrole, triazole, tetrazole, imine, enamine, phenol, or a moiety that includes any of the moieties listed above. In a preferred embodiment, the ligand coordinates through a pyridine moiety.

[0108] The ligand may be monodentate or polydentate. In one embodiment of the present disclosure, the ligand is monodentate. In another embodiment of the present disclosure, the ligand is bidentate. In another embodiment, the ligand is polydentate, which coordinates to three or more atoms.

[0109] In one embodiment of the present disclosure, the catalyst composition comprises a single type of ligand as described herein. In another embodiment of the present disclosure, the catalyst composition comprises a mixture of two or more types of ligands as described herein.

[0110] In one embodiment of the present disclosure, the ligand is DETA, PMDETA, TETA, HMTETA, Me 6 TREN, Cyclam, Me 6In one embodiment of the present disclosure, the ligand is a secondary amine, such as a secondary amine with a bulky substituent (i.e., reducing the nucleophilicity of the amine). In one embodiment of the present disclosure, the ligand is a nitrogen bidentate ligand. In one embodiment, the ligand comprises a 2,2'-bipyridine moiety or a 2,2'-bipyrimidine moiety. In one embodiment, the ligand is selected from the group consisting of 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 2,2'-bipyrimidine, 2,2'-bipyridine-4,4'-dicarboxylic acid or ester thereof, 2,2'-bipyridine-5,5'-dicarboxylic acid or ester thereof. In a preferred embodiment of the present disclosure, the ligand is 2,2'-bipyridine (bpy).

[0111] The catalyst composition of the present disclosure preferably comprises an aminoxyl radical compound, i.e., a compound having a NO· functional group. In a further embodiment of the present disclosure, the aminoxyl radical compound is a dialkylaminoxyl radical compound. In a further embodiment of the present disclosure, the aminoxyl radical compound is piperidine N-oxide or a derivative thereof. In a further embodiment, the aminoxyl radical compound is a substituted piperidine N-oxide. In a further embodiment, the aminoxyl radical compound is (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) or a derivative thereof. In one embodiment of the present disclosure, the aminoxyl radical compound is selected from the group consisting of TEMPO, (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)oxyl (4-OH-TEMPO), 4-acetamido-TEMPO, 4-hydroxy-TEMPO benzoate, 4-amino-TEMPO, 2-azaadamantane-N-oxyl, 9-azabicyclo[3.3.1]nonane-N-oxyl, 4-carboxy-TEMPO, 4-maleimido-TEMPO, 4-methoxy-TEMPO, 1-methyl-2-azaadamantane-N-oxyl, 4-oxo-TEMPO, and functionalized polymers having any of the aminoxyl radical compounds.In a preferred embodiment of the present disclosure, the aminoxyl radical compound is selected from the group consisting of TEMPO or (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)oxyl (4-OH-TEMPO). The aminoxyl radical compounds are intended to be part of a catalytic cycle that results in the oxidation of the fatty alcohol compositions of the present disclosure. TEMPO and its derivatives described herein convert oxidants into O 2 It should be noted that TEMPO acts as a catalyst for the oxidation of alcohol functional groups to aldehyde functional groups as an oxidizing agent. However, as used herein, TEMPO and its derivatives disclosed herein are also referred to as "oxidizing agents."

[0112] In one embodiment of the present disclosure, the catalyst composition comprises a base. Although some specific bases are described herein below, it is expected that many different bases will be useful in the practice of the present disclosure. In one embodiment of the present disclosure, the base is an organic base. It may be advantageous to use an organic base because the organic base may be soluble in the reaction medium as disclosed herein. In one embodiment of the present disclosure, the base is a nitrogen base. In one embodiment, the base is a Schiff base. In one embodiment, the base is an oxygen base. In one embodiment of the present disclosure, the base is selected from the group consisting of 1-methylimidazole, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,1,3,3-tetramethylguanidine, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and potassium t-butoxide. In one embodiment of the present disclosure, the base is selected from the group consisting of 1-methylimidazole, potassium tert-butoxide, or 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU).

[0113] In one embodiment of the present disclosure, the components of the catalyst composition as provided herein may be mixed to form the catalyst composition prior to adding the catalyst composition to the reaction mixture. In another embodiment, the components of the catalyst composition may be added separately to the reaction mixture. In another embodiment, some of the components of the catalyst composition may be mixed and then added to the reaction mixture, while the remaining components of the catalyst composition are added separately and / or premixed and then added to the reaction mixture.

[0114] Oxidation Method The present disclosure provides a method for converting a fatty alcohol composition to a fatty aldehyde composition. In particular, the conversion of the fatty alcohol composition to the fatty aldehyde composition is the oxidation of the fatty alcohol composition.

[0115] The method disclosed herein is expected to be useful for the conversion of a variety of different primary alcohol compositions, for example compositions containing primary alcohols with a chain length of at least 2 carbon atoms. However, the method disclosed herein is particularly suitable for the oxidation of primary alcohols with a chain length of 8 carbon atoms or more (i.e., fatty alcohols) as further defined in the "Fatty Alcohols" and "Fatty Aldehydes" sections herein. Other known oxidation methods often only produce aliphatic aldehyde compositions with low yield and / or purity. "Peroxidation", i.e., further oxidation of aldehydes to the corresponding carboxylic acids, is often a major contributing factor to the low reaction yield and / or low purity of the aldehyde composition. Other known oxidation methods for short primary alcohols may not be suitable for the oxidation of aliphatic alcohols, because oxidation may be incomplete, "peroxidation" may occur, and / or purification of the reaction product may be infeasible. Furthermore, as outlined in the background section, other known methods of oxidizing aliphatic alcohols to aliphatic aldehydes often use relatively large volumes of solvent and / or purification of the reaction product. In contrast, the methods disclosed herein use relatively small volumes of solvent for the oxidation reaction and relatively small volumes of solvent for purification of the reaction product. The methods disclosed herein also have the advantage of being scalable, i.e., effective both on a small scale (e.g., less than 10 g of aliphatic alcohol composition) or on a large scale (e.g., more than 100 g of aliphatic alcohol composition, such as more than 500 g of aliphatic alcohol composition). Other known methods of oxidizing aliphatic alcohols to the corresponding aliphatic aldehydes may be effective on a small scale (e.g., less than 10 g of aliphatic alcohol composition), but are not scalable, i.e., it is difficult to obtain good reaction yields or product purity on a larger scale (e.g., more than 100 g of aliphatic alcohol composition, such as more than 500 g of aliphatic alcohol composition).Obtaining an aldehyde composition that is relatively free of by-products (such as the corresponding aliphatic carboxylic acid or unreacted aliphatic alcohol) is advantageous because it eliminates the need for time-consuming or costly purification steps such as distillation. Each of the above features (small solvent volume, scalability, and substrate range) make the methods disclosed herein particularly suitable for industrial applications.

[0116] One embodiment of the present disclosure provides a method for converting an aliphatic alcohol to an aliphatic aldehyde, the method comprising the steps (a) and (b): (a) providing a reaction mixture comprising an aliphatic alcohol composition comprising the aliphatic alcohol, a catalyst composition, and a solvent; and (b) exposing the reaction mixture to at least 0.25 ml of oxygen per gram of aliphatic alcohol per minute by bubbling a gas mixture containing oxygen through the reaction mixture, thereby obtaining the aliphatic aldehyde.

[0117] In one embodiment of the present disclosure, a method for converting aliphatic alcohols to aliphatic aldehydes on a large scale is provided, the method comprising the steps (a) and (b) of: (a) providing a reaction mixture comprising at least one kilogram of an aliphatic alcohol, a catalyst comprising a copper source, at least one kilogram of a solvent, and a water-absorbing or water-adsorbing material that absorbs or adsorbs water; and (b)O 2 By adding a gas or liquid containing 2 or at least 0.001 μmol O per μmol initial aliphatic alcohol per minute. 2 into the reaction mixture, thereby oxidizing greater than 50 wt. % of the fatty alcohols to fatty aldehydes and less than 50 wt. % to fatty acids.

[0118] The method disclosed herein can be carried out without external cooling and heating. However, since the oxidation reaction is generally exothermic, the reaction mixture is expected to experience a temperature increase during the course of the reaction. In one embodiment of the present disclosure, the reaction is carried out at 5°C to 80°C (such as 10°C to 70°C, such as 15°C to 65°C). In a further embodiment of the reaction, the reaction mixture is exposed to oxygen at 5°C to 80°C (such as 10°C to 70°C, such as 15°C to 65°C).

[0119] The process disclosed herein can be carried out under ambient pressure or under elevated pressure. In one embodiment, the reaction mixture is exposed to oxygen under a pressure of 0.5-40 bar, such as 0.5-30 bar, such as 0.6-20 bar, such as 0.7-10 bar, such as 0.8-5 bar. In one embodiment, the reaction mixture is exposed to oxygen under a pressure of 0.5-0.8 bar, 0.8-1.2 bar, 1.2-1.5 bar, 1.5-2 bar, 2-5 bar, 5-10 bar, 10-20 bar, or 20-30 bar. In one embodiment of the present disclosure, the reaction mixture is exposed to oxygen under a pressure of 0.8-1.2 bar. However, it is contemplated that the process disclosed herein can be carried out under a pressure of less than 0.5 bar or less than 0.8 bar, provided that the amount of oxygen fed to the reaction mixture is as disclosed herein. In one embodiment, the pressures disclosed herein are the pressures in the reaction vessel where the reaction mixture is exposed to oxygen, hi one embodiment, the pressures disclosed herein are the oxygen partial pressures in the reaction vessel.

[0120] In additional or alternative embodiments, O 2 A gas (such as air) or liquid (optionally containing O 2 (which may be a concentrated form of O 2 ) is mixed into the reaction mixture to add O 2 to the reaction medium. 2 The mixture is added to O 2 This can be achieved by bubbling a gas mixture comprising:

[0121] In some embodiments, the copper source of the present disclosure comprises a copper(I) salt or a combination of copper(II) and a reducing agent.

[0122] Oxygen Delivery Rate It is an essential element of the present disclosure that the oxygen supply to the reaction mixture is above a certain threshold. The inventors have unexpectedly discovered that higher oxygen supply rates result in improved reaction yields.

[0123] In one embodiment of the present disclosure, the reaction mixture is exposed to at least 0.3 ml of oxygen per gram of fatty alcohol composition per minute (such as at least 0.4 ml, 0.5 ml, 0.6 ml, 0.7 ml, 0.8 ml, 0.9 ml, 1.0 ml, 1.1 ml, 1.2 ml, 1.3 ml, 1.4 ml, etc., at least 1.5 ml of oxygen per gram of fatty alcohol composition per minute). In a preferred embodiment of the present disclosure, the reaction mixture is exposed to at least 1.5 ml of oxygen per gram of fatty alcohol composition per minute.

[0124] In one embodiment of the present disclosure, the reaction mixture is exposed to at least 0.3 ml of oxygen per gram of aliphatic alcohol per minute (such as at least 0.4 ml, 0.5 ml, 0.6 ml, 0.7 ml, 0.8 ml, 0.9 ml, 1.0 ml, 1.1 ml, 1.2 ml, 1.3 ml, 1.4 ml, etc., at least 1.5 ml of oxygen per gram of aliphatic alcohol per minute). In a preferred embodiment of the present disclosure, the reaction mixture is exposed to at least 1.5 ml of oxygen per gram of aliphatic alcohol per minute.

[0125] Whenever a gas volume is mentioned in this specification, it is intended that this corresponds essentially to the gas volume under a pressure of 1 bar.

[0126] In one embodiment of the present disclosure, the reaction mixture is exposed to at least 60 ml of oxygen per mole of aliphatic alcohol per minute (such as at least 100 ml, 150 ml, 200 ml, 250 ml, 300 ml, 350 ml, 400 ml, etc., at least 450 ml of oxygen per mole of aliphatic alcohol per minute). In a preferred embodiment of the present disclosure, the reaction mixture is exposed to at least 450 ml of oxygen per mole of aliphatic alcohol per minute.

[0127] In one embodiment of the present disclosure, the reaction mixture is exposed to at least 10 μmoles of oxygen per gram of aliphatic alcohol per minute (at least 12 μmoles, 16 μmoles, 20 μmoles, 24 μmoles, 28 μmoles, 32 μmoles, 36 μmoles, 40 μmoles, 44 μmoles, 48 ​​μmoles, 52 μmoles, 56 μmoles, 60 μmoles of oxygen per gram of aliphatic alcohol per minute, etc.).In a preferred embodiment of the present disclosure, the reaction mixture is exposed to at least 60 μmoles of oxygen per gram of aliphatic alcohol per minute.

[0128] In one embodiment of the present disclosure, the reaction mixture is exposed to at least 2.5 millimoles of oxygen per mole of aliphatic alcohol per minute (at least 4 millimoles, 6 millimoles, 8 millimoles, 10 millimoles, 12 millimoles, 14 millimoles, 16 millimoles, etc., per mole of aliphatic alcohol per minute, such as at least 18 millimoles of oxygen per mole of aliphatic alcohol per minute).In a preferred embodiment of the present disclosure, the reaction mixture is exposed to at least 18 millimoles of oxygen per mole of aliphatic alcohol per minute.

[0129] The oxygen provided to the reaction mixture of the present disclosure may be provided as pure oxygen or as a gas mixture containing oxygen. In one embodiment of the present disclosure, the gas mixture contains 5% to 100% oxygen. In a further embodiment of the present disclosure, the gas mixture contains 15% to 25% oxygen. In one embodiment of the present disclosure, the gas mixture contains at least 90% oxygen. In one embodiment of the present disclosure, the gas mixture is substantially pure oxygen. As outlined in the "Water Removal" section of this specification, it is beneficial to minimize the amount of water present in the reaction mixture. Thus, in a preferred embodiment of the present disclosure, the gas mixture is H 2 Does not contain O.

[0130] Although sufficient oxygen exposure to the reaction mixture is achieved in part by using sufficient oxygen supply as outlined herein, it is also expected that sufficient oxygen exposure to the reaction mixture will be achieved by high interface contact between the feed gas mixture and the liquid phase of the reaction mixture. To ensure sufficient oxygen exposure to the reaction mixture, it is important to have high interface contact, such as by ensuring sufficient oxygen dissolution in the liquid phase of the reaction mixture. This can be achieved by using equipment (such as, for example, diffusion equipment) to bubble gas into the liquid. By increasing the diffusion of the gas mixture into the solution, it is expected that the oxygen supply rate will be improved. By increasing the partial pressure of oxygen supplied to the reaction mixture, it is expected that the oxygen supply rate will be improved. By stirring the reaction mixture, it is expected that the oxygen supply rate will be improved. Therefore, it is desirable to stir the reaction mixture of the present disclosure. In one embodiment of the present disclosure, a gas mixture containing oxygen is bubbled into the reaction mixture. In a further embodiment of the present disclosure, the gas mixture is bubbled into the reaction using a diffusion equipment. In one embodiment of the present disclosure, the reaction mixture is stirred while exposed to oxygen.

[0131] In one embodiment of the present disclosure, the reaction mixture is exposed to oxygen for at least 5 minutes (such as at least 10 minutes, such as at least 20 minutes, such as at least 30 minutes, such as at least 40 minutes, such as at least 50 minutes, such as at least 60 minutes, such as at least 70 minutes, 80 minutes, 90 minutes, etc., at least 100 minutes, etc.). It is anticipated that oxygen exposure need not be maintained for a continuous period of time as specified herein and can be interrupted. Thus, in one embodiment of the present disclosure, the reaction mixture is exposed to oxygen for a continuous period of time of at least 60 minutes (such as at least 70 minutes, 80 minutes, 90 minutes, etc., at least 100 minutes). In another embodiment of the present disclosure, the reaction mixture is exposed to oxygen for two or more periods, where the combined periods total at least 60 minutes (such as at least 70 minutes, 80 minutes, 90 minutes, etc., at least 100 minutes, etc.).

[0132] In one embodiment of the present disclosure, a bubble column reactor or a trickle bed reactor is used to 2 Conduct exposure to.

[0133] It is expected that longer reaction time may reduce the conversion rate and / or yield of the aldehyde composition of the present disclosure.This is expected to be due to, for example, overoxidation of aldehyde and / or introduction of water into the reaction mixture beyond the drying capacity of drying means.In one embodiment of the present disclosure, the reaction mixture is exposed to oxygen for up to 2000 minutes (up to 1900 minutes, 1800 minutes, 1700 minutes, 1600 minutes, 1500 minutes, 1400 minutes, 1300 minutes, 1200 minutes, 1100 minutes, 1000 minutes, 900 minutes, 800 minutes, 700 minutes, 600 minutes, 500 minutes, 400 minutes, 350 minutes, 325 minutes, 300 minutes, 275 minutes, etc., up to 250 minutes, etc.).

[0134] It is important to balance the amount of oxygen added to the reaction medium with the amount of aliphatic alcohol in the reaction medium and / or the amount and effectiveness of the catalyst. The oxygen supply to the reaction medium for optimal aldehyde production may also be affected by the amount of fatty acid in the reaction medium, with high levels of fatty acid production necessitating increased oxygen supply. Thus, in additional or alternative embodiments, the methods described herein provide the reaction mixture with at least 0.010 μmol (such as at least 0.020, such as at least 0.030, such as at least 0.040, such as at least 0.049, such as at least 0.060, such as at least 0.070, such as at least 0.080, such as at least 0.090, such as at least 0.100 μmol) of dissolved O per μmol copper per minute. 2 and / or to the reaction mixture at least 0.0010 μmoles (such as at least 0.0020, such as at least 0.0025, such as at least, such as at least 0.0050, such as at least 0.0075, such as at least 0.0100 μmoles) of dissolved O per μmol of initial aliphatic alcohol per minute. 2 and / or to the reaction mixture at least 0.010 μmol (such as at least 0.015, such as at least 0.020, such as at least 0.025, such as at least 0.030, such as at least 0.050, such as at least 0.075, such as at least 0.100 μmol) of dissolved O per μmol of fatty acid per minute. 2 This includes adding

[0135] In some embodiments, the disclosed method provides the reaction mixture with at least 0.049 μmol of dissolved O per μmol of copper per minute. 2 The method further comprises dissolving the

[0136] In some embodiments, the disclosed method provides the reaction mixture with at least 0.02 μmol of dissolved O per μmol of copper per minute. 2 (The reaction mixture is at least 0.04 μmol of dissolved O per μmol of copper per minute, such as at least 0.03 μmol of dissolved O per μmol of copper per minute.) 2etc.)

[0137] In some embodiments, the disclosed method comprises adding to the reaction mixture 0.01 to 1.00 μmol of dissolved O per μmol of copper per minute. 2 (The reaction mixture is added with 0.01 to 0.80 μmol, such as 0.01 to 0.60 μmol, such as 0.01 to 0.40 μmol, such as 0.01 to 0.20 μmol, such as 0.01 to 0.10 μmol of dissolved O per μmol of copper per minute. 2 etc.)

[0138] In some embodiments, the disclosed method provides the reaction mixture with at least 0.0025 μmol of dissolved O per μmol of initial aliphatic alcohol per minute. 2 The method further comprises dissolving the

[0139] In some embodiments, the disclosed method provides the reaction mixture with at least 0.002 μmol of dissolved O per μmol of initial aliphatic alcohol per minute. 2 (The reaction mixture is provided with at least 0.004 μmol of dissolved O per μmol of initial aliphatic alcohol per minute, such as at least 0.003 μmol. 2 etc.)

[0140] In some embodiments, the disclosed method comprises providing the reaction mixture with 0.001 to 1.00 μmol of dissolved O per μmol of initial aliphatic alcohol per minute. 2 (The reaction mixture is added with 0.001 to 0.80 μmol, such as 0.001 to 0.60 μmol, such as 0.001 to 0.40 μmol, such as 0.001 to 0.20 μmol, such as 0.001 to 0.10 μmol of dissolved O per μmol of initial aliphatic alcohol per minute. 2 etc.)

[0141] In some embodiments, the disclosed methods provide the reaction mixture with at least 0.025 μmol of dissolved O per μmol of fatty acid per minute. 2The method further comprises dissolving the

[0142] In some embodiments, the disclosed methods provide the reaction mixture with at least 0.01 μmol of dissolved O per μmol of fatty acid per minute. 2 (The reaction mixture is provided with at least 0.04 μmol of dissolved O per μmol of fatty acid per minute, such as at least 0.02 μmol, such as at least 0.03 μmol. 2 etc.)

[0143] In some embodiments, the disclosed method provides the reaction mixture with at least 10 μmoles of O per gram of aliphatic alcohol per minute. 2 (At least 20 μmol O 2 , at least 40 μmol O 2 , or at least 60 μmol O 2 thereby obtaining the fatty aldehyde, optionally wherein the fatty alcohol and the fatty aldehyde are desaturated.

[0144] In some embodiments, the methods of the present disclosure provide a reaction medium containing at least 80% O 2 during the course of the oxidation reaction. 2 Saturated (at least 85% O 2 Saturated, at least 90% O 2 Saturated, at least 95% O 2 Saturated, at least 100% O 2 saturation) to the reaction medium. 2 The method further comprises dissolving the

[0145] In some embodiments, the O 2 The gas or liquid containing is air, and optionally O 2 may be concentrated.

[0146] In some embodiments, a method of the present disclosure is provided, wherein O 2 The supply of a gas or liquid containing O2 This is accomplished by pumping or bubbling a gas or liquid mixture containing the compound into the reaction mixture.

[0147] Reaction conditions In the present disclosure, the conversion of aliphatic alcohol compositions to aliphatic aldehyde compositions is achieved using a relatively small volume of solvent. In particular, previously reported methods of converting aliphatic alcohols to aliphatic aldehydes, as outlined herein, use a relatively large volume of solvent in the reaction mixture. In large-scale production, large solvent volumes are often considered unfeasible; this is due to the cost of the solvent, the environmental footprint, and the potential difficulty in handling large reaction volumes. Therefore, the oxidation method disclosed herein can be advantageously used for large-scale production of aliphatic aldehyde compositions, since it requires a relatively small volume of solvent. "Relatively small volume of solvent volume" means a volume as outlined herein.

[0148] In one embodiment of the present disclosure, the reaction mixture comprises a solvent. The solvent that is part of the reaction mixture may be a substantially pure solvent or a solvent mixture. Thus, in one embodiment, the reference to a solvent in the reaction mixture may also refer to a solvent mixture that comprises two or more solvents.

[0149] In one embodiment of the present disclosure, the solvent is selected from the group consisting of acetonitrile, dimethylsulfoxide (DMSO), dimethylformamide (DMF), alkanes (such as pentane, hexane, and heptane), cycloalkanes, petroleum ether (such as heavy petroleum ether or light petroleum ether), dioxane, diethyl ether, dichloromethane, tetrahydrofuran, ethyl acetate, acetone, nitromethane, propylene carbonate, and solvent mixtures comprising any of the foregoing solvents.

[0150] In one embodiment, the solvent is an aprotic solvent. It is advantageous for the solvent to be aprotic; this is because protons, such as protons from OH groups or amines, can adversely interfere with components, such as the catalyst composition, such as by inactivating the base. In one embodiment of the present disclosure, the solvent is selected from the group consisting of acetonitrile, dimethylsulfoxide (DMSO), dimethylformamide (DMF), alkanes (such as pentane, hexane, and heptane), cycloalkanes, petroleum ether (such as heavy oil ether or light oil ether), dioxane, diethyl ether, dichloromethane, tetrahydrofuran, ethyl acetate, acetone, nitromethane, propylene carbonate, and solvent mixtures comprising any of the above solvents. In a preferred embodiment, the solvent is selected from the group consisting of acetonitrile, DMSO, DMF, and solvent mixtures comprising any of the above solvents. In a further preferred embodiment, the solvent is acetonitrile, or the solvent comprises acetonitrile. In another preferred embodiment of the present disclosure, the solvent is acetonitrile.

[0151] In one embodiment, the solvent is a polar solvent. It is advantageous for the solvent to be polar; it improves the solubility of at least some of the components of the reaction mixture and / or the components of the gas mixture. In one embodiment of the present disclosure, the solvent is selected from dichloromethane, tetrahydrofuran, ethyl acetate, acetone, dimethylformamide (DMF), acetonitrile, dimethylsulfoxide (DMSO), nitromethane, propylene carbonate, and a solvent mixture comprising any of the above solvents. In a preferred embodiment, the solvent is selected from the group consisting of acetonitrile, DMSO, DMF, or a solvent mixture comprising any of the above solvents. In yet a further preferred embodiment, the solvent is acetonitrile or a solvent mixture comprising acetonitrile. In yet a further preferred embodiment, the solvent is acetonitrile.

[0152] In assessing the relative amount of a solvent used in a chemical reaction, the amount of solvent can be compared to the amount of a reagent or the amount of one of the reagents converted in the chemical reaction, or the amount of a product or the amount of one of the products obtained in the chemical reaction.

[0153] The amount of solvent in the reaction mixture can be compared to the amount of the fatty alcohol composition. In one embodiment of the present disclosure, the weight of the solvent in the reaction mixture is 0-2000% (such as 100-2000%, such as 100-1500%, such as 100-1000%, such as 100-500%) of the weight of the fatty alcohol composition. The fatty alcohol composition may contain compounds other than fatty alcohols. In assessing the amount of the solvent, it is preferred to exclude these other compounds when calculating the amount of the solvent. Furthermore, the fatty alcohol composition may contain one or more solvents, i.e., "fatty alcohol composition solvents". In a preferred embodiment of the present disclosure, the fatty alcohol composition solvent is ignored when assessing the amount of the fatty alcohol composition. In one embodiment of the present disclosure, the weight of the solvent corresponds to 100-2000% (such as 100-1500%, such as 100-1000%, such as 100-500%) of the weight of the fatty alcohol or fatty alcohols of the fatty alcohol composition.

[0154] The amount of the solvent in the reaction mixture can be compared with the amount of the aliphatic aldehyde composition obtained from the reaction mixture. In one embodiment of the present disclosure, the weight of the solvent in the reaction mixture is 100-2000% (such as 100-1500%, such as 100-1000%, such as 100-500%) of the weight of the aliphatic aldehyde composition. The aliphatic aldehyde composition may contain compounds other than the aliphatic aldehyde. In assessing the amount of the solvent, it is preferable to exclude these other compounds when calculating the amount of the solvent. Furthermore, the aliphatic aldehyde composition may contain one or more solvents, i.e., "aliphatic aldehyde composition solvents". In a preferred embodiment of the present disclosure, the aliphatic aldehyde composition solvent is ignored when assessing the amount of the aliphatic aldehyde composition. In one embodiment of the present disclosure, the weight of the solvent corresponds to 100 to 2000% (such as 100 to 1500%, such as 100 to 1000%, such as 100 to 500%) of the weight of the aliphatic aldehyde or aliphatic aldehydes of the aliphatic aldehyde composition.

[0155] In some embodiments, the solvent is a non-halogenated solvent. In some embodiments, the solvent is selected from acetonitrile, dimethylsulfoxide (DMSO), dimethylformamide (DMF), pentane, hexane, heptane, a cycloalkane, petroleum ether, dioxane, diethyl ether, tetrahydrofuran, ethyl acetate, acetone, nitromethane, propylene carbonate, or a combination thereof.

[0156] Transformation The methods of the present disclosure are effective for converting aliphatic alcohol compositions to aliphatic aldehyde compositions with high yield and / or low production of by-products. Conversion herein may be based on either the amount of material of substrate and / or product, or amount by weight of substrate.

[0157] In one embodiment of the present disclosure, the conversion of the aliphatic alcohol is at least 80% (such as at least 82%, such as at least 84%, such as at least 86%, such as at least 88%, such as at least 90%) when measured by the amount of material. In another embodiment of the present disclosure, the conversion of the aliphatic alcohol is at least 80% (such as at least 82%, such as at least 84%, such as at least 86%, such as at least 88%, such as at least 90%) when measured by the weight of the aliphatic alcohol. In a preferred embodiment, the conversion of the aliphatic alcohol to the aliphatic aldehyde is at least 80% (such as at least 82%, such as at least 84%, such as at least 86%, such as at least 88%, such as at least 90%) when measured by the amount of material. In a preferred embodiment, the conversion of the fatty alcohol to the fatty aldehyde, as assessed by weight of the fatty alcohol and the fatty aldehyde, is at least 80% (such as at least 82%, such as at least 84%, such as at least 86%, such as at least 88%, such as at least 90%, such as at least 92%, such as at least 94%, such as at least 96%, such as at least 98%).

[0158] The conversion can be specifically calculated as the ratio of the amount of substance of aldehyde to the total amount of substance of aldehyde and alcohol [i.e., n(aldehyde) / (n(aldehyde)+n(alcohol)); where n means the amount of substance. In one embodiment of the present disclosure, n(aldehyde) / (n(aldehyde)+n(alcohol)) is at least 80% (such as at least 82%, such as at least 84%, such as at least 86%, such as at least 88%, such as at least 90%) when evaluated by the amount of substance. In a preferred embodiment, the conversion of aliphatic alcohol to aliphatic aldehyde is at least 80% (such as at least 82%, such as at least 84%, such as at least 86%, such as at least 88%, such as at least 90%, such as at least 92%, such as at least 94%, such as at least 96%, such as at least 98%).

[0159] The method of the present disclosure is effective in converting fatty alcohols to fatty aldehydes with little by-product formation such as the corresponding fatty acids (i.e., little "overoxidation"). For the catalytic oxidation of alcohols to aldehydes, it is paramount to avoid the formation of carboxylic acids (such as fatty acids) since it is expected that carboxylic acids may deactivate the catalytic composition. In one embodiment of the present disclosure, less than 10% (such as less than 8%, such as less than 6%, such as less than 5%) of the fatty alcohols are converted to fatty acids. In another embodiment, less than 10% (such as less than 8%, such as less than 6%, such as less than 5%) of the fatty aldehydes formed are converted to fatty acids. In one embodiment of the present disclosure, the ratio of fatty acids to fatty aldehydes in the fatty aldehyde composition is less than 10:90 (such as less than 8:92, such as less than 6:94, such as less than 5:05). In this specification, "ratio" refers to molar ratio. In some aspects, the ratio of fatty acids produced to aliphatic aldehydes produced is less than 10:90.

[0160] The disclosed method is expected to be useful for the conversion of other alcohol compositions to aldehyde compositions. For example, the disclosed method is expected to be useful for the conversion of C2-C7 alcohols (i.e., ethanol, propanol, butanol, pentanol, hexanol, and heptanol) to the corresponding C2-C7 aldehydes (i.e., ethanal, propanal, butanal, pentanal, hexanal, and heptanal). When the substrates include primary alcohols, it is expected that both linear and branched derivatives of these substrates may be converted using the disclosed method. As an example, the disclosed method is expected to be useful for the conversion of n-butanol to n-butanal, and iso-butanol to iso-butanal. The disclosed method is also expected to be useful for the conversion of unsaturated (i.e., unsaturated) derivatives of the above substrates.

[0161] In some embodiments, the present disclosure provides a process wherein the conversion of aliphatic alcohol to aliphatic aldehyde is at least 60 wt% (such as at least 80 wt%, such as at least 85 wt%, such as at least 87 wt%, such as at least 90 wt%, such as at least 95 wt%, such as at least 99 wt%).

[0162] In some embodiments, the present disclosure provides a process in which the conversion of fatty alcohols to fatty acids is less than 40 wt% (such as less than 30 wt%, such as less than 20 wt%, such as less than 15 wt%, such as less than 10 wt%, such as less than 5 wt%, such as less than 1 wt%).

[0163] water removal Many chemicals and solvents have trace amounts of water. Chemicals and solvents are often described as "dry" if they contain no water or only a small amount of water. Water may also be produced during the course of a chemical reaction. It is expected that the reaction yield may be better if efforts are made to remove water from the reaction mixture, since water is expected to degrade the catalyst composition.

[0164] In one embodiment of the present disclosure, substantially dry solvents and reagents (including gas mixtures and gases) are used in the methods of the present invention.

[0165] Some reagents and / or solvents may be difficult to dry completely before use in the methods disclosed herein. Thus, water may be removed from the reaction mixture during the method. In one embodiment of the present disclosure, water is removed from the reaction mixture. In one embodiment of the present disclosure, water is continuously removed from the reaction mixture by exposing the reaction mixture to oxygen. In one embodiment of the present disclosure, water is removed from the reaction mixture by adding a means for drying the reaction mixture. In one embodiment of the present disclosure, the drying means is a water absorbing material. In one embodiment of the present disclosure, the drying means is a water adsorbing material. In one embodiment of the present disclosure, the drying means is selected from the group consisting of molecular sieves, silica gel, alumina, bentonite clay, calcium oxide, alkali metal carbonates, bicarbonates, or alkaline earth metal carbonates.

[0166] In one embodiment, water is removed from the reaction mixture, such as with a goal of achieving a water content of less than about 2 wt. % (based on the weight of the reaction mixture), such as less than 2 wt. %. In one embodiment, water is removed from the reaction mixture, such as with a goal of achieving a water content of less than about 1 wt. % (based on the weight of the reaction mixture), such as less than 1 wt. %.

[0167] In additional or alternative embodiments, the methods described herein include removing water from the reaction medium before, during, or after oxidation of the aliphatic alcohol. The step may include adding a water-absorbing or water-adsorbing material to the reaction medium that absorbs or adsorbs water. Such water-absorbing or water-adsorbing materials include, but are not limited to, molecular sieves, silica gel, aluminas, bentonite clay, calcium oxides, alkali metal carbonates, bicarbonates, or alkaline earth metal carbonates, or combinations thereof. In some embodiments, the water-absorbing or water-adsorbing material is selected from molecular sieves, silica gel, aluminas, bentonite clay, calcium oxides, alkali metal carbonates, bicarbonates, or alkaline earth metal carbonates, or combinations thereof.

[0168] With regard to the amount of water absorbing or adsorbing material, it is preferably added to the reaction medium in an amount such that the water content of the reaction medium after the oxidation process is 2% or less by weight, and optionally the molar conversion of the aliphatic alcohol to aliphatic aldehydes is greater than 93%. In some embodiments, optionally when the water absorbing or adsorbing material is a molecular sieve, the amount of water absorbing or adsorbing material added is at least 10 g per millimole of aliphatic alcohol present in the reaction medium before oxidation (such as at least 15 g per millimole of aliphatic alcohol, such as at least 19 g per millimole of aliphatic alcohol).

[0169] Providing a fatty alcohol composition The methods disclosed herein may first include the initial step of producing a fatty alcohol composition as disclosed herein, or producing a fatty alcohol as disclosed herein.

[0170] In one embodiment of the disclosure, there is provided a method as disclosed herein, wherein the method further comprises an initial step of producing said fatty alcohol, said initial step comprising the steps (i) and (ii) of: (i) providing a yeast cell capable of producing the fatty alcohol; and (ii) incubating the yeast cells in a medium, thereby producing the fatty alcohol.

[0171] In one embodiment of the disclosure, there is provided a method as disclosed herein, wherein the method further comprises an initial step of producing the fatty alcohol composition, the initial step comprising the steps (i) and (ii) of: (i) providing a yeast cell capable of producing the fatty alcohol composition; and (ii) incubating the yeast cells in a medium, thereby producing the fatty alcohol composition.

[0172] In one embodiment of the disclosure, there is provided a method as disclosed herein, wherein the method further comprises an initial step of producing the fatty alcohol, the initial step comprising the steps (i)-(iii) of: (i) providing a yeast cell capable of synthesizing alkanoyl-CoA; wherein the yeast cell is further capable of expressing: Desaturases; and · Alcohol-forming fatty acyl-CoA reductase; (ii) expressing the desaturase and the alcohol-forming fatty acyl-CoA reductase in the yeast cell; and (iii) incubating the yeast cells in a medium; The desaturase is capable of converting at least a portion of the alkanoyl-CoA to alkenoyl-CoA, and the alcohol-forming fatty acyl-CoA reductase is capable of converting at least a portion of the alkanoyl-CoA to a fatty alcohol, thereby producing the fatty alcohol. The implementation of the above production of fatty alcohols is disclosed in detail in EP3313997B1. In a further embodiment of the present disclosure, the fatty alcohol is (Z)-11-hexadecen-1-ol, where the alkanoyl-CoA is hexadecanoyl-CoA, where the desaturase is a Δ11-desaturase, where the alkenoyl-CoA is (Z)-11-hexadecenyl-CoA.

[0173] One embodiment of the present disclosure provides a method as disclosed herein, wherein the method further comprises an initial step of producing the fatty alcohol composition, the initial step comprising the steps (i)-(iii) of: (i) providing a yeast cell capable of synthesizing alkanoyl-CoA; wherein the yeast cell is further capable of expressing: Desaturases; and · Alcohol-forming fatty acyl-CoA reductase; (ii) expressing the desaturase and the alcohol-forming fatty acyl-CoA reductase in the yeast cell; and (iii) incubating the yeast cells in a medium; The desaturase is capable of converting at least a portion of the alkanoyl-CoA to alkenoyl-CoA, and the alcohol-forming fatty acyl-CoA reductase is capable of converting at least a portion of the alkanoyl-CoA to fatty alcohol, thereby producing the fatty alcohol composition. The implementation of the above-mentioned production of fatty alcohol composition is disclosed in detail in EP3313997B1. In a further embodiment of the present disclosure, the fatty alcohol is (Z)-11-hexadecen-1-ol, where the alkanoyl-CoA is hexadecanoyl-CoA, where the desaturase is Δ11-desaturase, where the alkanoyl-CoA is (Z)-11-hexadecenyl-CoA. The implementation of the above-mentioned process of producing fatty alcohol is disclosed in detail in WO2016 / 207339.

[0174] In one embodiment of the disclosure, there is provided a method as disclosed herein, wherein the method further comprises an initial step of producing said fatty alcohol, said initial step comprising the steps (i) and (ii) of: (i) providing a fatty yeast cell capable of producing a desaturated fatty alcohol; wherein the yeast cell further comprises: capable of expressing at least one heterologous fatty acyl-CoA desaturase capable of introducing at least one double bond into a fatty acyl-CoA to produce a desaturated fatty acyl-CoA; capable of expressing at least one heterologous fatty acyl-CoA reductase capable of converting at least a portion of the desaturated fatty acyl-CoA to an desaturated fatty alcohol; having a mutation that reduces the activity of fatty alcohol oxidase and having a mutation that reduces the activity of at least one of fatty aldehyde dehydrogenase, peroxisome biogenesis factor, and glycerol-3-phosphate acyltransferase; and (ii) incubating the yeast cells in a medium, thereby producing the fatty alcohol. Methods for carrying out the above steps of producing the fatty alcohol are disclosed in detail in WO2018 / 109163.

[0175] In one embodiment of the disclosure, there is provided a method as disclosed herein, wherein the method further comprises an initial step of producing the fatty alcohol composition, the initial step comprising the steps (i) and (ii) of: (i) providing a fatty yeast cell capable of producing a desaturated fatty alcohol; wherein the yeast cell further comprises: capable of expressing at least one heterologous fatty acyl-CoA desaturase capable of introducing at least one double bond into a fatty acyl-CoA to produce a desaturated fatty acyl-CoA; capable of expressing at least one heterologous fatty acyl-CoA reductase capable of converting at least a portion of the desaturated fatty acyl-CoA to an desaturated fatty alcohol; having a mutation that reduces the activity of fatty alcohol oxidase and having a mutation that reduces the activity of at least one of fatty aldehyde dehydrogenase, peroxisome biogenesis factor, and glycerol-3-phosphate acyltransferase; and (ii) incubating the yeast cells in a medium, thereby producing the fatty alcohol composition. Methods for carrying out the above steps of producing the fatty alcohol composition are disclosed in detail in WO2018 / 109163.

[0176] In one embodiment of the disclosure, there is provided a method as disclosed herein, wherein the method further comprises an initial step of producing said fatty alcohol, said initial step comprising the steps (i) and (ii) of: (i) providing a yeast cell capable of producing a desaturated fatty alcohol; wherein the yeast cell comprises: at least one heterologous fatty acyl-CoA desaturase capable of introducing at least one double bond into a fatty acyl-CoA with a carbon chain length of 14, said desaturase being selected from the group consisting of Δ9 desaturases and Δ11 desaturases, said desaturase having a higher specificity for tetradecanoyl-CoA and therefore a higher specificity for hexadecanoyl-CoA; Heterologous fatty acyl-CoA desaturase; and at least one heterologous fatty acyl-CoA reductase capable of converting at least a portion of the desaturated fatty acyl-CoA into an desaturated fatty alcohol; expresses; and (ii) incubating the yeast cells in a medium, thereby producing the fatty alcohol. Methods for carrying out the above steps of producing the fatty alcohol are disclosed in detail in WO2018 / 109167.

[0177] In one embodiment of the disclosure, there is provided a method as disclosed herein, wherein the method further comprises an initial step of producing the fatty alcohol composition, the initial step comprising the steps (i) and (ii) of: (i) providing a yeast cell capable of producing a desaturated fatty alcohol; wherein the yeast cell comprises: at least one heterologous fatty acyl-CoA desaturase capable of introducing at least one double bond into a fatty acyl-CoA with a carbon chain length of 14, said desaturase being selected from the group consisting of Δ9 desaturases and Δ11 desaturases, said desaturase having a higher specificity for tetradecanoyl-CoA and therefore a higher specificity for hexadecanoyl-CoA; Heterologous fatty acyl-CoA desaturase; and at least one heterologous fatty acyl-CoA reductase capable of converting at least a portion of the desaturated fatty acyl-CoA into an desaturated fatty alcohol; expresses; and (ii) incubating the yeast cells in a medium, thereby producing the fatty alcohol composition. Methods for carrying out the above steps of producing the fatty alcohol composition are disclosed in detail in WO2018 / 109167.

[0178] In one embodiment of the disclosure, there is provided a method as disclosed herein, wherein the method further comprises an initial step of producing the fatty alcohol composition, the initial step comprising the steps (i) and (ii) of: (i) providing a yeast cell capable of producing a desaturated fatty alcohol; wherein the yeast cell comprises: a heterologous Δ12 fatty acyl-CoA desaturase capable of introducing a double bond at position 12 of a saturated or desaturated fatty acyl-CoA (preferably an unsaturated fatty acyl-CoA) having a carbon chain length of at least 13 and n double bonds; where n and n' are integers; where 0 ≤ n ≤ 3. and 1 ≦ n′ ≦ 4, and at least one heterologous fatty acyl-CoA reductase capable of converting at least a portion of the desaturated fatty acyl-CoA into an desaturated fatty alcohol; expresses; and (ii) incubating the yeast cells in a medium, thereby producing the fatty alcohol composition. Methods for carrying out the above steps of producing the fatty alcohol composition are described in detail in EP 21183447.8, filed by the applicant on July 2, 2021, entitled "Methods and yeast cells for production of desaturated compounds."

[0179] In one embodiment of the disclosure, there is provided a method as disclosed herein, wherein the method further comprises an initial step of producing the fatty alcohol composition, the initial step comprising the steps (i) and (ii) of: (i) providing a yeast cell capable of producing a desaturated fatty alcohol; wherein the yeast cell comprises: a heterologous Δ13 fatty acyl-CoA desaturase capable of introducing a double bond at position 13 of a saturated or desaturated fatty acyl-CoA (preferably an unsaturated fatty acyl-CoA) having a carbon chain length of at least 14 and n double bonds; where n and n' are integers; where 0 ≤ n ≤ 3. and 1≦n′≦4; and at least one heterologous fatty acyl-CoA reductase capable of converting at least a portion of the desaturated fatty acyl-CoA into an desaturated fatty alcohol; expresses; and (ii) incubating the yeast cells in a medium, thereby producing the fatty alcohol composition. Methods for carrying out the above steps of producing the fatty alcohol composition are described in detail in EP 21183459.3, entitled "Methods and yeast cells for production of desaturated compounds," filed by the applicant on July 2, 2021.

[0180] In one embodiment of the disclosure, there is provided a method as disclosed herein, wherein the method further comprises an initial step of producing the fatty alcohol composition, the initial step comprising the steps (i) and (ii) of: (i) providing a yeast cell capable of producing E8,E10-dodecadien-1-ol; wherein the yeast cells express the following heterologous desaturases and heterologous fatty acyl-CoA reductases: at least one heterologous desaturase capable of introducing one or more double bonds into a fatty acyl-CoA having a carbon chain length of 12, thereby converting said fatty acyl-CoA into a desaturated fatty acyl-CoA; wherein at least a portion of the desaturated fatty acyl-CoA is E8,E10-dodecadienyl coenzyme A (E8,E10-C12:CoA); where (a) the at least one desaturase is Cpo CPRQ (Accession No. AHW98354), or a functional variant thereof having at least 80% identity thereto (such as at least 81%, such as at least 82%, such as at least 83%, such as at least 84%, such as at least 85%, such as at least 86%, such as at least 87%, such as at least 88%, such as at least 89%, such as at least 90%, such as at least 91%, such as at least 92%, such as at least 93%, such as at least 94%, such as at least 95%, such as at least 96%, such as at least 97%, such as at least 98%, such as at least 99% identity to Cpo_CPRQ); or (b) the at least one desaturase is at least two desaturases, and wherein at least one of the two desaturases is Cpo_CPRQ (Accession No. AHW98354), or has at least 80% identity thereto (such as at least 81%, such as at least 82%, such as at least 83%, such as at least 84%, such as at least 85%, such as at least 86%, such as at least 87%, such as at least 88%, such as at least 89%, such as at least 90%, such as at least 91%, such as at least 92%, such as at least 93%, such as at least 94%, such as at least 95%, such as at least 96%, such as at least 97%, such as at least 98%, such as at least 99% identity), and the other desaturase is a desaturase capable of introducing at least one double bond into a fatty acyl-CoA with a carbon chain length of 12 (such as a Z9-12 desaturase); and at least one heterologous fatty acyl-CoA reductase capable of converting at least a portion of the E8,E10-dodecadienyl coenzyme A to E8,E10-dodecadien-1-ol; and (ii) incubating the yeast cells in a medium, thereby producing the fatty alcohol composition. Methods for carrying out the above steps of producing the fatty alcohol composition are disclosed in detail in WO2021 / 123128.

[0181] In one embodiment of the disclosure, there is provided a method as disclosed herein, wherein the method further comprises an initial step of producing said fatty alcohol, said initial step comprising providing a yeast cell capable of producing said fatty alcohol and culturing said yeast cell in a medium under conditions capable of producing said fatty alcohol, wherein said culture medium comprises an extractant in an aqueous solution (such as said medium) in an amount equal to or greater than its haze concentration measured at the culture temperature, wherein said extractant is a non-ionic ethoxylated surfactant, thereby producing said fatty alcohol.

[0182] In one embodiment of the disclosure, there is provided a method as disclosed herein, wherein the method further comprises an initial step of producing the fatty alcohol composition, the initial step comprising providing a yeast cell capable of producing the fatty alcohol composition and culturing the yeast cell in a medium under conditions capable of producing the fatty alcohol composition, wherein the culture medium comprises an extractant in an aqueous solution (such as the medium) in an amount equal to or greater than its haze concentration measured at the culture temperature, and wherein the extractant is a non-ionic ethoxylated surfactant, thereby producing the fatty alcohol composition.

[0183] In one embodiment of the disclosure, there is provided a method as disclosed herein, wherein the method further comprises an initial step of producing said fatty alcohol, said initial step comprising the steps (i) and (ii) of: (i) providing a yeast cell capable of producing a fatty alcohol ester and culturing the yeast cell in a medium under conditions capable of producing the fatty alcohol ester; wherein the culture medium comprises an extractant in an aqueous solution (such as the medium) in an amount equal to or greater than its haze concentration measured at the culture temperature, and wherein the extractant is a non-ionic ethoxylated surfactant, thereby producing the fatty alcohol ester; and (ii) converting the fatty alcohol ester to the fatty alcohol, thereby producing the fatty alcohol.

[0184] In one embodiment of the disclosure, there is provided a method as disclosed herein, wherein the method further comprises an initial step of producing the fatty alcohol composition, the initial step comprising the steps (i) and (ii) of: (i) providing a yeast cell capable of producing a fatty alcohol ester and culturing the yeast cell in a medium under conditions capable of producing the fatty alcohol ester; wherein the culture medium comprises an extractant in an aqueous solution (such as the medium) in an amount equal to or greater than its haze concentration measured at the culture temperature, and wherein the extractant is a non-ionic ethoxylated surfactant, thereby producing the fatty alcohol ester; and (ii) converting the fatty alcohol ester to the fatty alcohol, thereby producing the fatty alcohol composition.

[0185] A detailed description of a method for culturing yeast cells in a medium containing an extractant in an amount equal to or greater than the cloud concentration of the yeast cells is provided in WO2021 / 078452.

[0186] Additionally or alternatively, disclosed herein is a composition that comprises more than 93% by weight of aliphatic aldehyde, less than 7% by weight of aliphatic alcohol, and less than 2% by weight of water.In some embodiments, the amount of aldehyde can be 94% or more by weight (such as 95% or more by weight, such as 96% or more by weight, such as 97% or more by weight, such as 98% or more by weight, such as 99% or more by weight), while the amount of non-converted aliphatic alcohol is less than 6% by weight (such as less than 5% by weight, such as less than 4% by weight, such as less than 3% by weight, such as less than 2% by weight, such as less than 1% by weight), and the amount of water is less than 2% by weight (such as less than 1.5% by weight, such as less than 1% by weight).

[0187] purification The present disclosure provides methods for purifying aliphatic aldehydes (such as the aliphatic aldehydes disclosed herein) and aliphatic aldehyde compositions (such as the aliphatic aldehyde compositions disclosed herein).

[0188] One embodiment of the present disclosure provides a method for purifying an aliphatic aldehyde, comprising the steps of: (a) providing a crude reaction product comprising: (i) (iii) (i) Aliphatic aldehydes; (ii) copper ions; and (iii) a polar solvent; (b) combining the crude reaction product with a non-polar aprotic solvent and an acid to create a non-polar phase and a polar phase; and (c) separating the non-polar phase from the polar phase.

[0189] One embodiment of the present disclosure provides a method for purifying an aliphatic aldehyde as disclosed herein, wherein the crude reaction product comprises: (iv) 5 to 80% of the aliphatic aldehyde; (v) 0.05 to 5.0% copper ions; and (vi) 20 to 95% of said polar solvent.

[0190] In some embodiments, the present disclosure provides a method for purifying the aliphatic aldehyde, further comprising the steps (a)-(c) of: (a) providing a purified mixture comprising: (i) (a) a first mixture containing: (i) Aliphatic aldehydes; (ii) copper ions; and (iii) a polar solvent; (b) combining the purified mixture with a non-polar aprotic solvent and an acid to create an extraction mixture comprising a non-polar phase and a polar phase that enables extraction of the aliphatic aldehyde from the polar phase to the non-polar phase; and (c) separating the non-polar phase containing the purified aldehyde from the polar phase.

[0191] In some embodiments, the purified mixture comprises 0.05-5.0 wt% copper ions (such as 0.05-2.0 wt% copper ions, such as 0.05-1.0 wt% copper ions).

[0192] A representative embodiment of the crude reaction product as disclosed herein may comprise about 30% aliphatic aldehyde, about 1.0% ligand, about 0.4% copper, about 0.6% aminoxyl radical, about 0.5% base, and about 62% polar solvent. Another representative embodiment of the crude reaction product as disclosed herein may comprise about 30% aliphatic aldehyde, about 1.0% bipyridine, about 0.4% copper, about 0.6% 4-OH-TEMPO, about 0.5% 1-methylimidazole, and about 62% acetonitrile.

[0193] In one embodiment, there is provided a method for purifying an aliphatic aldehyde as disclosed herein, wherein the crude reaction product contains 0.05-5.0% copper ions, such as 0.05-2.0% copper ions, such as 0.05-1.0% copper ions. In this disclosure, references to weight or weight percent of copper, copper ions, copper salts, etc. refer to the weight content of copper in an isolated state, i.e., without counter ions.

[0194] In one embodiment, there is provided a method for purifying an aliphatic aldehyde as disclosed herein, wherein the crude reaction product further comprises a ligand (such as 0.1-10% ligand, such as 0.1-5% ligand, such as 0.1-2% ligand, such as about 1% ligand). In one embodiment of the disclosure, the ligand is a nitrogen bidentate ligand, such as a nitrogen bidentate ligand selected from the group consisting of 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 2,2'-bipyrimidine, 2,2'-bipyridine-4,4'-dicarboxylic acid or ester thereof, 2,2'-bipyridine-5,5'-dicarboxylic acid or ester thereof.

[0195] In one embodiment, there is provided a method for purifying an aliphatic aldehyde as disclosed herein, wherein the crude reaction product further comprises an aminoxyl radical compound (such as 0.01-10% aminoxyl radical compound, such as 0.01-5% aminoxyl radical compound, such as about 0.01-2% aminoxyl radical compound, such as about 0.5% aminoxyl radical compound). In one embodiment of the present disclosure, the aminoxyl radical compound is selected from the group consisting of TEMPO, (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)oxyl (4-OH-TEMPO), 4-acetamido-TEMPO, 4-hydroxy-TEMPO benzoate, 4-amino-TEMPO, 2-azaadamantane-N-oxyl, 9-azabicyclo[3.3.1]nonane N-oxyl, 4-carboxy-TEMPO, 4-maleimido-TEMPO, 4-methoxy-TEMPO, 1-methyl-2-azaadamantane-N-oxyl, 4-oxo-TEMPO, and functionalized polymers comprising any of the aminoxyl radical compounds.

[0196] In one embodiment, there is provided a method for purifying an aliphatic aldehyde as disclosed herein, wherein the crude reaction product further comprises a base (such as 0.1-10% base, such as 0.1-5% base, such as 0.1-2% base, such as about 0.5% base). In one embodiment of the disclosure, the base is selected from the group consisting of 1-methylimidazole, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,1,3,3-tetramethylguanidine, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and potassium t-butoxide.

[0197] In one embodiment of the present disclosure, the aliphatic aldehyde is a saturated aliphatic aldehyde as disclosed herein. In one embodiment of the present disclosure, the aliphatic aldehyde is an unsaturated aliphatic aldehyde as disclosed herein. In one embodiment of the present disclosure, the aliphatic aldehyde is an aliphatic aldehyde as disclosed in the "Aliphatic Aldehydes" section. In one embodiment, the aliphatic aldehyde is selected from the group consisting of an (E)7,(Z)9 unsaturated aliphatic aldehyde having a carbon chain length of 14, an (E)3,(Z)8,(Z)11 unsaturated aliphatic aldehyde having a carbon chain length of 14, an (Z)9,(E)11,(E)13 unsaturated aliphatic aldehyde having a carbon chain length of 14, an (E)7,(Z)9 unsaturated aliphatic aldehyde having a carbon chain length of 12, an (E)3,(Z)8,(Z)11 unsaturated aliphatic aldehyde having a carbon chain length of 12, an (Z)9,(E)11,(E)13 unsaturated aliphatic aldehyde having a carbon chain length of 12, and an (E)8,(E)10 unsaturated aliphatic aldehyde having a carbon chain length of 12. In one embodiment, the aliphatic aldehyde is selected from the group consisting of tetradecane-1-al, pentadecane-1-al, hexadecan-1-al, pentadecen-1-al, (Z)-9-hexadecen-1-al, (Z)-11-hexadecen-1-al, and (7E,9E)-undeca-7,9-dien-1-al.

[0198] In one embodiment, the copper ions are copper(I) and / or copper(II) ions. In one embodiment, the copper ions are copper(II) ions.

[0199] In one embodiment, the polar solvent is selected from the group consisting of acetonitrile, dimethylformamide, acetonitrile, propionitrile, butyronitrile, dimethylsulfoxide, dimethylacetamide, and propylene carbonate, hi one embodiment, the polar solvent is acetonitrile.

[0200] In one embodiment, the non-polar aprotic solvent is selected from the group consisting of linear alkanes, branched alkanes, and cyclic alkanes. In one embodiment, the non-polar aprotic solvent is selected from the group consisting of pentanes, hexanes, heptanes, and octanes. In one embodiment, the non-polar aprotic solvent is selected from the group consisting of heptane, pentane, hexane, cyclohexane, and octane.

[0201] In one embodiment, the acid has a pKa value of 3-6. In one embodiment, the acid is a carboxylic acid. In one embodiment, the carboxylic acid is a C2-C8 carboxylic acid. In one embodiment, the carboxylic acid is selected from the group consisting of C2-C8 monocarboxylic acids, C2-C8 dicarboxylic acids, and C6-C8 tricarboxylic acids. In one embodiment, the carboxylic acid is selected from the group consisting of acetic acid, citric acid, propanoic acid, lactic acid, glycolic acid, and polyacrylic acid. In one embodiment, at least 1.0 molar equivalent of carboxylic acid relative to copper is used. In one embodiment, at least 2.0 molar equivalents of carboxylic acid relative to copper are used, such as at least 2.4 equivalents. In one embodiment, 2.0 to 2.4, 2.4 to 2.8, 2.8 to 3.2, 3.2 to 3.6, 3.6 to 4.0, 4.0 to 5.0, 5.0 to 6.0, 6.0 to 7.0, 7.0 to 8.0, 8.0 to 9.0, 9.0 to 10.0 equivalents or more of carboxylic acid are used relative to copper. "Equivalent" means molar equivalent.

[0202] In one embodiment of the present disclosure, the crude reaction product further comprises an oxidizing agent and / or a spent oxidizing agent. In one embodiment, the oxidizing agent or the spent oxidizing agent is selected from the group consisting of TEMPO, (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)oxyl (4-OH-TEMPO), 4-acetamido-TEMPO, 4-hydroxy-TEMPO benzoate, 4-amino-TEMPO, 2-azaadamantane-N-oxyl, 9-azabicyclo[3.3.1]nonane-N-oxyl, 4-carboxy-TEMPO, 4-maleimido-TEMPO, 4-methoxy-TEMPO, 1-methyl-2-azaadamantane-N-oxyl, 4-oxo-TEMPO, and a functionalized polymer comprising any of the aminoxyl radical compounds; or a spent oxidizing agent thereof, or water.

[0203] In one embodiment, the method for purifying an aliphatic aldehyde as disclosed herein further comprises evaporating the non-polar aprotic solvent. In one embodiment, the evaporation of the non-polar aprotic solvent is carried out under low pressure (such as less than 100 mbar, such as less than 50 mbar, such as less than 40 mbar, such as less than 30 mbar).

[0204] One embodiment of the present disclosure provides a method for converting a composition comprising a fatty alcohol into a fatty aldehyde enriched composition, the method comprising the steps of: (a) converting a composition comprising a fatty alcohol to a composition comprising a fatty aldehyde using the method for oxidizing fatty alcohols disclosed herein; and (b) purifying the composition comprising an aliphatic aldehyde using the aliphatic aldehyde purification method disclosed herein. In a further embodiment, the fatty alcohol and the fatty aldehyde are unsaturated.

[0205] In an exemplary embodiment of the present disclosure, the crude reaction product, including the catalytic system (copper complex, TEMPO or derivative, N-methyl-imidazole or another base), the product of oxidation to an aliphatic aldehyde, and any unreacted alcohol, is dissolved or suspended in acetonitrile or another highly polar solvent, such as dimethylformamide, dimethylsulfoxide, or a similar solvent. The reaction mixture is then extracted with an organic solvent that is immiscible in the reaction solvent, typically an alkane, such as pentane, heptane, or hexane. The extraction can be performed using a separatory funnel, mixer settler, pulse column, or any other method for liquid-liquid separation. The phases separate rapidly without forming bubbles or suspensions. The heavy phase contains almost all of the catalytic components, while the reaction products are almost entirely present in the light phase. The product aliphatic aldehyde is obtained by evaporation of the extraction solvent. Optionally, an additive can be included to improve the removal of one or more components, such as copper ions. Such an additive can be an organic acid, such as acetic acid or citric acid.

[0206] product In one embodiment of the present disclosure, a composition is provided comprising an aliphatic aldehyde obtained by the method disclosed herein. In one embodiment of the present disclosure, aliphatic aldehyde obtained by the method disclosed herein is provided. In a further embodiment, the aliphatic aldehyde is unsaturated.

[0207] Copper ions in solution (aqueous or non-aqueous) are often blue in color. In one embodiment of the present disclosure, the composition exhibits an absorbance of at most 0.5 at 680 nm when using a 5 mm path length cuvette. In one embodiment, the absorbance at 680 nm is at most 0.4 (such as at most 0.3, such as at most 0.2, such as at most 0.1, such as at most 0.08, such as at most 0.06, such as at most 0.05) when using a 5 mm path length cuvette. In one embodiment, the aliphatic aldehyde composition contains less than 0.4% copper (such as less than 0.3%, such as less than 0.2%, such as less than 0.1%, such as less than 0.08%, such as less than 0.06%, such as less than 0.05%, such as less than 0.04%).

[0208] The aliphatic aldehydes disclosed herein may be produced from renewable raw materials. The aliphatic aldehydes or any sustained release composition thereof act as a pheromone component. Thus, in one embodiment of the present disclosure, a pheromone component produced from renewable raw materials is provided. In one embodiment of the present disclosure, a pheromone component produced from renewable raw materials is provided, the pheromone component having at least 80% biobased carbon content. In one embodiment, "biobased carbon" content refers to an organic compound, where the carbon is derived from a biological source or precursor. In one embodiment, the pheromone component comprises an aliphatic aldehyde composition and / or an aliphatic aldehyde as disclosed herein. In one embodiment, the pheromone component comprises a sustained release composition as disclosed herein. In one embodiment, the pheromone component comprises an aliphatic acetal and / or an alpha-hydroxysulfonic acid as disclosed herein.

[0209] In some embodiments, compositions are provided that contain greater than 93% by weight of an aliphatic aldehyde, less than 7% by weight of an aliphatic alcohol, and less than 2% by weight of water, optionally including free / unbound water.

[0210] In some embodiments, the composition is provided, wherein the absorbance at 680 nm is at most 0.4 (such as at most 0.3, such as at most 0.2, such as at most 0.1, such as at most 0.08, such as at most 0.06, such as at most 0.05) when using a 5 mm pathlength cuvette.

[0211] Method for Producing Aliphatic Acetals and α-Hydroxy Sulfonic Acids Aliphatic aldehydes may be converted to other compounds that can actually be converted back to the aliphatic aldehydes by inversion. Such inversion to aliphatic aldehydes may be by bond hydrolysis, bond cleavage, and / or functional group conversion. Such other compounds may act as better reservoirs for the aliphatic aldehydes, since the aliphatic aldehydes are gradually released as the compound is inverted. For example, the compounds may be less volatile than the corresponding aliphatic aldehydes, and volatile aliphatic aldehydes may be continuously released as the compound is converted to aliphatic aldehydes. Suitable compounds that can be produced from aliphatic aldehydes include acetals and α-hydroxysulfonic acids.

[0212] In one embodiment of the present disclosure, there is provided a method for converting an aliphatic alcohol to an aliphatic acetal, the method comprising the steps (a)-(c) of: (a) providing a reaction mixture comprising an aliphatic alcohol composition comprising an aliphatic alcohol as disclosed herein, a catalyst composition as disclosed herein, and a solvent as disclosed herein; (b) exposing the reaction mixture to at least 0.25 ml of oxygen per gram of aliphatic alcohol per minute by bubbling a gas mixture containing oxygen through the reaction mixture, thereby obtaining an aliphatic aldehyde; and (c) converting the aldehyde functional group of the aliphatic aldehyde to an acetal functional group, thereby obtaining the aliphatic acetal. In a further embodiment, the aliphatic alcohol is an unsaturated aliphatic alcohol. In yet a further embodiment, the aliphatic aldehyde is an unsaturated aliphatic aldehyde. In yet a further embodiment, the aliphatic acetal is an unsaturated aliphatic acetal.

[0213] In one embodiment of the present disclosure, there is provided a method for converting an aliphatic alcohol to an aliphatic acetal, the method comprising the steps (a) and (b): (a) converting the fatty alcohol to an aliphatic aldehyde as disclosed herein; and (b) converting the aldehyde functional group of the aliphatic aldehyde to an acetal functional group, thereby obtaining the aliphatic acetal. In a further embodiment, the aliphatic alcohol is an unsaturated aliphatic alcohol. In yet a further embodiment, the aliphatic aldehyde is an unsaturated aliphatic aldehyde. In yet a further embodiment, the aliphatic acetal is an unsaturated aliphatic acetal.

[0214] In one embodiment, there is provided an aliphatic acetal obtained by the process disclosed herein.

[0215] In one embodiment of the present disclosure, a method for converting an aliphatic alcohol to an aliphatic α-hydroxysulfonic acid is provided, the method comprising the steps of: (a) providing a reaction mixture comprising an aliphatic alcohol composition comprising an aliphatic alcohol as disclosed herein, a catalyst composition as disclosed herein, and a solvent as disclosed herein; (b) exposing the reaction mixture to at least 0.25 ml of oxygen per gram of aliphatic alcohol per minute by bubbling a gas mixture containing oxygen through the reaction mixture, thereby obtaining an aliphatic aldehyde; and (c) converting the aldehyde functional group of the aliphatic aldehyde to an α-hydroxysulfonic acid functional group, thereby obtaining the aliphatic α-hydroxysulfonic acid. In a further embodiment, the aliphatic alcohol is an unsaturated aliphatic alcohol. In yet a further embodiment, the aliphatic aldehyde is an unsaturated aliphatic aldehyde. In a further embodiment, the aliphatic α-hydroxysulfonic acid is an unsaturated aliphatic α-hydroxysulfonic acid.

[0216] In one embodiment of the present disclosure, there is provided a method for converting an aliphatic alcohol to an aliphatic α-hydroxysulfonic acid, the method comprising the steps of: (a) and (b); (a) converting the fatty alcohol to an aliphatic aldehyde as disclosed herein; and (b) converting the aldehyde functional group of the aliphatic aldehyde to an α-hydroxysulfonic acid functional group, thereby obtaining the aliphatic α-hydroxysulfonic acid. In a further embodiment, the aliphatic alcohol is an unsaturated aliphatic alcohol. In yet a further embodiment, the aliphatic aldehyde is an unsaturated aliphatic aldehyde. In a further embodiment, the aliphatic α-hydroxysulfonic acid is an unsaturated aliphatic α-hydroxysulfonic acid.

[0217] In one embodiment of the present disclosure, there is provided an aliphatic α-hydroxysulfonic acid obtained by the methods disclosed herein.

[0218] Pheromones and their controlled release The compounds of the present disclosure may act as pheromones. In one embodiment of the present disclosure, the pheromone composition as disclosed herein may include one or more aldehydes as disclosed herein, one or more acetals as disclosed herein, and / or one or more α-hydroxysulfonic acids as disclosed herein. In a particular embodiment of the present disclosure, the pheromone composition as disclosed herein may include one or more aliphatic aldehydes as disclosed herein, one or more aliphatic acetals as disclosed herein, and / or one or more aliphatic α-hydroxysulfonic acids as disclosed herein.

[0219] It may be advantageous to control the release of the pheromone from the pheromone composition in order to control the concentration of the pheromone in the air (e.g., the air around a crop). The pheromone composition may be formulated to provide a sustained release into the environment and / or to prevent degradation after release. In one embodiment of the present disclosure, the pheromone composition is included in a carrier, such as microcapsules, biodegradable flakes, or a paraffin wax-based matrix. In one embodiment of the present disclosure, the pheromone composition is formulated as a sustained release sprayable formulation.

[0220] In certain embodiments, the pheromone composition may include one or more polymeric agents known to those skilled in the art to control the release of the composition into the environment. In some embodiments, the polymerizable attractant composition is resistant to environmental conditions. The polymeric agent may also be a sustained or controlled release chemical capable of continuously releasing the pheromone composition into the environment. In one embodiment of the present disclosure, the polymeric agent is selected from the group consisting of cellulose, cellulose derivatives, proteins (such as casein), fluorocarbon-based polymers, hydrogenated rosins, lignins, melamine, polyurethanes, vinyl polymers (such as polyvinyl acetate (PVAC)), polycarbonates, polyvinylidene dinitrile, polyamides, polyvinyl alcohol (PVA), polyamide-aldehyde, polyvinyl aldehyde, polyesters, polyvinyl chloride (PVC), polyethylenes, polystyrenes, polyvinylidene, silicones, and combinations thereof. In one embodiment of the present disclosure, the cellulose derivative is selected from the group consisting of methyl cellulose, ethyl cellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose propionate, and combinations thereof.

[0221] In one embodiment of the present disclosure, the sustained release pheromone composition comprises one or more fatty acid esters or one or more fatty alcohols. In one embodiment of the present disclosure, the one or more fatty alcohols are selected from the group consisting of undecanol, dodecanol, tridecanol, tridecenol, tetradecanol, tetradecenol, tetradecadienol, pentadecanol, pentadecenol, hexadecanol, hexadecenol, hexadecadienol, octadecenol, and octadecadienol. In one embodiment of the present disclosure, the fatty acid ester is selected from the group consisting of undecanyl ester, dodecanyl ester, tridecanyl ester, tridecenyl ester, tetradecanyl ester, tetradecenyl ester, tetradecadienyl ester, pentadecanyl ester, pentadecenyl ester, hexadecanyl ester, hexadecenyl ester, hexadecadienyl ester, octadecenyl ester, and octadecadienyl ester. In one embodiment of the present disclosure, the fatty acid ester is selected from the group consisting of alkyl undecanoates, alkenyl undecanoates, alkyl dodecanoates, alkenyl dodecanoates, alkyl tridecanoates, alkenyl tridecanoates, alkyl tridecenoates, alkenyl tridecenoates, alkyl tetradecanoates, alkenyl tetradecanoates, alkyl tetradecenoates, alkenyl tetradecenoates, alkyl tetradecadienoates, alkenyl ... In one embodiment, the alkyl group is selected from the group consisting of alkyl pentadecanoate, alkenyl pentadecanoate, alkyl pentadecenoate, alkenyl pentadecenoate, alkyl hexadecanoate, alkenyl hexadecanoate, alkyl hexadecenoate, alkenyl hexadecenoate, alkyl hexadecadienoate, alkenyl hexadecadienoate, alkyl octadecenoate, alkenyl octadecenoate, alkyl octadecadienoate, and alkenyl octadecadienoate.

[0222] Another method of controlling pheromone release is to use a compound that decomposes into active pheromones when applied to the component. Aldehydes, such as the aliphatic aldehydes disclosed herein, react readily with alcohols to produce dialkyl acetals. The alcohol may be another pheromone alcohol (e.g., Z11-hexanedecen-1-ol, Z9-hexanedecen-1-ol, or similar unsaturated alcohol). Alternatively, the alcohol may be a short chain alcohol (such as methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol, and butan-2-ol). Additionally, when the alcohol is a diol, cyclic acetals may be produced. Examples of diols include ethylene glycol, 1,3-propylene glycol, and 1,2-propylene glycol. Alternatively, a mixture of alcohols may be used. The aliphatic acetals may be produced using the methods disclosed herein. In one embodiment of the present disclosure, the aliphatic acetal is produced from an aliphatic aldehyde as disclosed herein and two similar or different alcohols. In one embodiment, the acetal is produced from an aliphatic aldehyde as disclosed herein and two similar or different alcohols as disclosed herein. In one embodiment of the present disclosure, the aliphatic acetal is produced from an aliphatic aldehyde as disclosed herein and two similar or different aliphatic alcohols as disclosed herein. In one embodiment, the aliphatic acetal is produced from an aliphatic aldehyde as disclosed herein and two similar or different C1-C7 alcohols. In one embodiment of the present disclosure, the aliphatic acetal is produced from an aliphatic aldehyde as disclosed herein and two similar or different alcohols selected from the group consisting of methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol, and butan-2-ol. In one embodiment of the present disclosure, the acetal is produced from an aliphatic aldehyde and a diol as disclosed herein.In one embodiment, the acetal is produced from an aliphatic aldehyde, as disclosed herein, and a diol selected from the group consisting of ethylene glycol, 1,3-propylene glycol, and 1,2-propylene glycol.

[0223] The term "produced from" with respect to acetals is not intended to limit the acetal to a particular method of production. The term is used solely for the purpose of providing structural information about the acetal. For example, acetals can be produced by reacting a hemiacetal with an alcohol. As an example, an acetal produced from 1-methoxyethan-1-ol (hemiacetal) is equivalent to an acetal produced from ethanol and two molecules of methanol.

[0224] The aliphatic aldehydes of the present disclosure may also be present in the pheromone composition as oligomeric cyclic compounds. Thus, in one embodiment of the present disclosure, the aliphatic aldehydes are present in the pheromone composition as trioxanes and / or tetraoxanes. These oligomers act as reservoirs for the aldehydes and allow for controlled release of the aldehydes. Aldehyde oligomers can be produced in the presence of an acid catalyst. Examples of acids that may be used for acetal or oxane formation include hydrochloric acid, sulfuric acid, phosphoric acid, or hydrogen sulfates. Hydrogen sulfates are particularly advantageous for the production of oxanes.

[0225] Other suitable sustained release compounds are alpha-hydroxysulfonic acids. These compounds are easily produced from aqueous solutions of bisulfites, especially sodium bisulfite. In one embodiment of the present disclosure, the sustained release pheromone composition comprises alpha-hydroxysulfonic acids.

[0226] The acetal-type sustained release pheromones slowly revert to aldehydes when exposed to weak acids and moisture. The release rate will depend on the nature of the acetal species allowing custom compositions to be adapted to specific environments. The α-hydroxysulfonic acid slowly releases the pheromone under both acidic and alkaline conditions.

[0227] In one embodiment of the present disclosure, a sustained release aliphatic aldehyde composition is provided, comprising the aliphatic acetal disclosed herein.In one embodiment of the present disclosure, a method for producing the sustained release aliphatic aldehyde composition disclosed herein is provided, comprising carrying out the method disclosed herein to obtain aliphatic acetal, and formulating the aliphatic acetal as a sustained release composition.In a further embodiment, the aliphatic aldehyde is an unsaturated aliphatic aldehyde.In yet a further embodiment, the aliphatic acetal is an unsaturated aliphatic acetal.

[0228] In one embodiment of the present disclosure, a sustained release aliphatic aldehyde composition is provided, comprising the aliphatic α-hydroxysulfonic acid disclosed herein.In one embodiment of the present disclosure, a method for producing the sustained release aliphatic aldehyde composition disclosed herein is provided, comprising carrying out the method disclosed herein to obtain aliphatic α-hydroxysulfonic acid, and formulating the aliphatic α-hydroxysulfonic acid as a sustained release composition.In a further embodiment, the aliphatic aldehyde is an unsaturated aliphatic aldehyde.In yet a further embodiment, the aliphatic α-hydroxysulfonic acid is an unsaturated aliphatic acetal.

[0229] The sustained release pheromones can be optionally formulated with substances that further modify the release of the compound. These compositions may optionally include substances that control moisture and pH. The sustained release compositions can be mixtures of the acetals, aldehydes, alcohols, and alpha-hydroxysulfonic acids described above.

[0230] Minimizing the number of steps in a chemical synthesis is advantageous, for example, to reduce costs and minimize waste. Advantageously, the acetals and α-hydroxysulfonic acids disclosed herein are produced in as few steps as possible. This can be achieved by producing the acetals and α-hydroxysulfonic acids directly from the reaction mixture used to produce the aliphatic aldehydes.

[0231] Biological production of fatty alcohols Methods are available in the art for producing unsaturated fatty alcohols, unsaturated fatty alcohol acetates, and unsaturated fatty aldehydes in microbial cell factories, particularly yeast.

[0232] In particular, the desaturated compounds may be obtained by the methods described in WO2016 / 207339, WO2018 / 109163, WO2018 / 109167, WO2021 / 078452, WO2020 / 169389, WO2021 / 123128, as well as EP21183447.8, filed by the applicant on July 2, 2021, entitled "Methods and yeast cells for production of desaturated compounds", and EP21183459.3, filed by the applicant on July 2, 2021, entitled "Methods and yeast cells for production of desaturated compounds".

[0233] Briefly, by introducing one or more suitable heterologous fatty acyl-CoA desaturases, which introduce at least one double bond into a fatty acyl-CoA, and one or more suitable heterologous fatty acyl reductases (FARs), desaturated fatty alcohols can be produced in yeast cells, particularly Saccharomyces or Yarrowia cells, such as Saccharomyces yeast or Yarrowia lipolytica cells. These desaturated fatty alcohols can then be converted to desaturated fatty aldehydes using the methods disclosed herein.

[0234] Working Example Example 1: Oxidation of a mixture of aliphatic alcohols at low oxygen feed rates 1755 g of acetonitrile was added to 800 g of the aliphatic alcohol mixture (Table 1). Catalysts including 26.2 g of 2.2′-bipyridine, 62.7 g of tetrakisacetonitrile copper(I) triflate, 17.5 g of 4-hydroxy-TEMPO and 13.8 g of 1-methylimidazole were added to the reaction mixture. The airflow was 1 dm 3 / min to initiate the reaction, but after 160 min, the reaction 3 / min. The conversion of alcohol to aldehyde plateaued at 60%.

[0235] Reaction Sampling Remove 1 ml of the reaction mixture from the reactor and add 1 ml of saturated NaHCO 3 After stopping at 100°C, 1 ml of ethyl acetate was added and the sample was vigorously shaken. 1 μl of the organic phase was taken in a GC vial and diluted with 1 ml of ethyl acetate. This sample was analyzed by GC-FID. For reaction monitoring, the relative peak area % was used to confirm the progress of the reaction. Reaction sampling was also performed in the following examples.

[0236] [Table 1]

[0237] Example 2: Oxidation of a mixture of aliphatic alcohols at moderate oxygen feed rates 1755 g of acetonitrile was added to 800 g of the aliphatic alcohol mixture. Catalysts including 26.2 g of 2,2′-bipyridine, 62.7 g of tetrakisacetonitrile copper(I) triflate, 17.5 g of 4-hydroxy-TEMPO, and 13.8 g of N-methylimidazole were added to the reaction mixture. The airflow was 1 dm 3 Start the reaction using 1 dm 3 / min. The conversion of alcohol to aldehyde leveled off at 83%.

[0238] Example 3: Oxidation of a mixture of aliphatic alcohols at high oxygen feed rates 218 g of acetonitrile was added to 100 g of the aliphatic alcohol mixture. A catalyst including 1.56 g of 2.2′-bipyridine, 3.77 g of tetrakisacetonitrile copper(I) triflate, 1.03 g of 4-hydroxy-TEMPO, and 82 g of N-methylimidazole was added to the reaction mixture. The airflow was 1 dm 3 Start the reaction using 1 dm 3 / min. The conversion of alcohol to aldehyde leveled off at 93%.

[0239] Example 4: Oxidation of a mixture of fatty alcohols 800 g of a mixture of fatty alcohols containing fatty alcohols was oxidized; this oxidation was carried out by adding 2.2 dm 3 The reaction was carried out by bubbling air at a rate of 1 / min. A catalyst containing 62 g of tetrakisacetonitrile copper(I) trifluoromethanesulfonate, 26 g of 2.2'-bipyridine, 10 g of 4-hydroxyTEMPO, and 13.6 g of 1-methyl-imidazole was added to the reaction mixture. The reaction was allowed to proceed for 2 hours, during which the temperature increased from 22°C to 52°C after 1 hour and decreased to 42°C after 2 hours. The reaction yield steadily increased to over 70% after 73 minutes and further increased to 87% at 150 minutes. Figure 1 shows the reaction yield as a function of time.

[0240] Example 5: Oxidation of a mixture of aliphatic aldehydes using an adsorbent that adsorbs the water of reaction A solution of 252 g of an aliphatic alcohol mixture containing the aliphatic alcohols shown in Table 2 and 625 g of acetonitrile was added to 2 dm 3 The above aliphatic alcohol mixture was oxidized by bubbling air at a rate of 1000 / min. A catalyst including 18 g of tetrakisacetonitrile copper(I) trifluoromethanesulfonate, 8.2 g of 2.2'-bipyridine, 5.5 g of 4-hydroxyTEMPO, 8.5 g of 1-methyl-imidazole, and 20 g of 4 Å molecular sieves was added to the reaction mixture. The reaction was allowed to proceed for 2 hours, during which the temperature increased from 22° C. to 52° C. after 1 hour and decreased to 42° C. after 2 hours. The conversion steadily increased and exceeded 95% at 139 minutes. Figure 2 shows the reaction yield as a function of time.

[0241] [Table 2]

[0242] Example 6: Oxidation of aliphatic alcohol mixtures using a water adsorbent that adsorbs water from the solvent and reaction water 800 g of a mixture of fatty alcohols containing the fatty alcohols of Table 3 was oxidized; the oxidation was carried out by adding 6 dm 3 The reaction was carried out by bubbling air at a rate of 100 / min. A catalyst containing 62 g of tetrakisacetonitrile copper(I) trifluoromethanesulfonate, 26 g of 2.2'-bipyridine, 10.6 g of 4-hydroxyTEMPO, 16.6 g of N-imidazole, and 65 g of 4 Å molecular sieves was added to the reaction mixture. The reaction was allowed to proceed for 2 hours, during which the temperature increased from 23° C. to 51° C. after 1 hour and 13 minutes, and then decreased to 22° C. after 6 hours. The conversion steadily increased and exceeded 99% at 110 minutes. Figure 3 shows the reaction yield as a function of time.

[0243] [Table 3]

[0244] Example 7: Comparison of slow, medium, and fast oxygen delivery rates The fatty alcohol composition, catalyst composition, and solvent were mixed as outlined in the previous examples. Table 4 summarizes the conversion of fatty alcohol to fatty aldehyde, expressed as ald / (alc+ald), at the indicated diffusion rates and diffusion times. A 20% oxygen gas mixture was used.

[0245] [Table 4]

[0246] At low oxygen feed rates (diffusion = 0.2 L / h), the conversion of aliphatic alcohols to aliphatic aldehydes was only moderate at long reaction times (1427 min). At medium oxygen feed rates (1 L / h), the conversion was better but required long reaction times. At high oxygen feed rates (2.2 L / h), the conversion of aliphatic alcohols was good. At long reaction times (305-320 min), the yields were somewhat lower, 87-93%, while at shorter reaction times (110-174 min), the conversion tended to be good, 97-99%.

[0247] Furthermore, further improvement in yield was observed by removing the water produced during the reaction (Table 5). Since water is involved in the production of carboxylic acid, water removal is known to further improve the yield. Note that it is not necessary to completely adsorb the water, it is sufficient to add enough molecular sieves to reduce the final water content by about 16 mol %.

[0248] [Table 5]

[0249] Example 8: Purification of the reaction mixture method Calibration standards containing dodecan-1-ol, (Z)-11-hexadecenal, (Z)-9-hexadecenal, hexadecanal, tetradecanal, tetradecan-1-ol, pentadecanal, pentadecane-1-ol, hexadecan-1-ol, (Z)-9-hexadecan-1-ol, and (Z)-11-hexadecan-1-ol in the concentration range of 0.01 mg / mL to 1 mg / mL were prepared. To 1 mL of standard, 10 µL of 10 mg / mL methyl nonadecanoate was added to obtain a calibration curve. Monounsaturated pentadecenals were quantified with pentadecanal.

[0250] UV visible light spectrometer A Thermo Genesys 5S was used for UV-visible spectroscopy. The concentrated sample was placed in a 5 mm quartz cuvette and the spectrum was measured from 350 nm to 1100 nm. max was measured at 680 nm.

[0251] GC-FID sample preparation Three aliquots of approximately 50 mg each were transferred to individual 50 mL volumetric flasks, weighed, and ethyl acetate was added to the volume mark. 1000 μL of each dilution was transferred to a GC vial and 10 μL of the internal standard solution was added. The internal standard solution was 10 mg / mL methyl nonadecanoate in ethyl acetate.

[0252] Analysis conditions Qualitative analysis was performed on an Agilent GC 7820A interfaced with an MS 5977B (split / splitless inlet and a DB-Fat wax UI column (30 m length, 0.25 mm internal diameter, and 0.25 μm film thickness)). Operating parameters were: Injection of 1 μL, split ratio = 20:1, injector temperature = 220 °C, steady flow = 1 mL / min helium, heating temperature settings = 80 °C for 1 min, 15 °C / min to 150 °C for 7 min, 10 °C / min to 210 °C for 7 min, and 20 °C / min to 230 °C for 5 min.

[0253] Qualitative analysis was performed on an Agilent GC 7890B interfaced with a FID, using a split / splitless inlet and an HP-5 column (30 m length, 0.32 mm internal diameter, and 0.25 μm film thickness). Operating parameters were: Injection of 1 μL, split ratio = 1:40, injector temperature = 220 °C, steady flow = 2 mL / min hydrogen, heating temperature settings = 80 °C for 1 min, 15 °C / min to 150 °C for 7 min, 10 °C / min to 210 °C, and 20 °C / min to 300 °C.

[0254] analytical standards (Z)-11-Hexadecenal from Pherobank was 99.1% pure. Pentadecane-1-ol from Alfa Aesar was 99% pure. Hexadecane-1-ol purchased from Merck was 99% pure. (Z)-9-Hexadecen-1-ol and (Z)-11-Hexadecen-1-ol purchased from Pherobank were 98% pure. Tetradecane-1-ol and methyl nonadecanoate purchased from Larodan were 99% pure.

[0255] qualitative analysis The following compounds were identified based on match to the spectra and retention times of analytical standards: tetradecanal (14:Ald), pentadecanal (15:Ald), (Z)-9-hexadecenal (Z9-16:Ald), (Z)-11-hexadecenal (Z11-16:Ald), hexadecanal (16:Ald), and (Z)-11-hexadecen-1-ol (Z11-16:OH).

[0256] The monounsaturated pentadecenal (15-1:Ald) was identified based on a spectral match to the NIST library.

[0257] Preparation of reaction mixture 200 g of a mixture of aliphatic alcohols containing 78% Z9-hexadecenol and Z11-hexadecenol was added to 1 dm 3A jacketed reaction vessel was added to the reactor. 16 g of 4 Å molecular sieves, 6.4 g of 2,2′-bipyridine, 3.6 g of 4-hydroxy-TEMPO, and 3.4 g of N-methylimidazole were added to the vessel. A solution of 15.6 g of tetrakisacetonitrile copper(I) trifluoromethanesulfonate in 400 ml of acetonitrile was added. Air was bubbled through the solution at 2 L / min for 2 hours.

[0258] A representative embodiment of the crude reaction product produced using this method comprises about 30% aliphatic aldehyde, about 1.0% bipyridine, about 0.4% copper, about 0.6% 4-OH-TEMPO, about 0.5% 1-methylimidazole, and about 62% acetonitrile.

[0259] purification 100 g of the reaction mixture was taken and extracted with 165 g of n-heptane. After 5 min of vigorous stirring, the mixture was left to stand for 30 min to allow the phases to separate. The lower phase, containing acetonitrile and bulk copper, bipyridine, N-methylimidazole and OH-TEMPO, was discarded and the upper phase, containing mainly n-heptane and the pheromone product, was collected and the heptane was evaporated at 15 mbar and 65° C. 32 g of product was obtained, containing 74% Z9-hexadecenol and Z11-hexadecenol.

[0260] Example 9: Purification of the reaction mixture 100 g of the reaction mixture prepared in Example 8 was taken and extracted with 165 g of n-heptane and 1 g of glacial acetic acid. After 5 minutes of vigorous stirring, the mixture was left to stand for 30 minutes to allow the phases to separate. The lower phase was discarded and the upper phase was collected, and the heptane was evaporated at 15 mbar and 65° C. 30 g of product was obtained, containing 74.9% Z9-hexadecenol and Z11-hexadecenol.

[0261] Example 10: Purification of the reaction mixture 100 g of the reaction mixture prepared in Example 7 was taken and extracted with 165 g of n-heptane and 1.2 g of glacial acetic acid. After 5 minutes of vigorous stirring, the mixture was left to stand for 30 minutes to allow the phases to separate. The lower phase was discarded and the upper phase was collected, and the heptane was evaporated at 15 mbar and 65° C. 30.2 g of product was obtained, containing 73.8% Z9-hexadecenol and Z11-hexadecenol.

[0262] Example 11: Purification of the reaction mixture 100 g of the reaction mixture prepared in Example 7 was taken and extracted with 165 g of n-heptane and 2 g of glacial acetic acid. After 5 minutes of vigorous stirring, the mixture was left to stand for 30 minutes to allow the phases to separate. The lower phase was discarded and the upper phase was collected, and the heptane was evaporated at 15 mbar and 65° C. 35.6 g of product was obtained, containing 74.2% Z9-hexadecenol and Z11-hexadecenol.

[0263] Example 12: Comparative example of a typical oxidation method for oil-based and aqueous work up of Z11-16:OH (Z11-hexadecenol) In a 500 ml bottle equipped with an air bubbler and reflux condenser, add 100 g of starting material (total alcohol purity 86%; 0.36 molar, 60.04% active pheromone Z11-16:OH (Z11-hexadecenol)) and 200 ml of CH 3 CN was added. To this suspension was then added 2.87 g of copper(I) bromide (5 mol%; 0.02 mol), 2.79 g of 2,2'-bipyridine (Bipy) (5 mol%; 0.02 mol), 1.40 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-OH-TEMPO) (2.5 mol%; 0.01 mol), and 1.43 ml of N-methylimidazole (5 mol%; 0.02 mol; 1.47 g). The reaction was stirred until the Z11-16:OH signal disappeared by GCMS (16 / 20 hours).

[0264] The acetonitrile in the mixture was evaporated under low pressure. The residue was diluted with 200 ml of ethyl acetate and transferred to a separatory funnel. This solution was diluted with 200 ml of 0.5NH 2 SO4 The organic fractions were washed twice with 100 ml of saturated sodium thiosulfate solution or until the blue coloration of the organic layer disappeared. This solution was further washed once with 100 ml of saturated sodium thiosulfate solution and once with 50 ml of saturated NaCl solution. The combined organic fractions were dried over sodium sulfate, filtered, and then concentrated under reduced pressure.

[0265] Example 13: Comparison of purification protocols and product stability result Table 7 shows a comparison of the copper, oxidant, and ligand contents in the purified reaction products outlined in Examples 7-12.

[0266] [Table 6]

[0267] The methods of the present disclosure (Examples 8-11) yielded purified products with much lower non-constituent content (12%) than the product obtained using the comparative purification method of Example 12 (18%).

[0268] The copper content, assessed by absorbance at 680 nm using a 5 mm cuvette, was higher in Comparative Example 12, with an absorbance of 0.7. Example 8, which did not add any acid during purification, had a similar copper content, as evidenced by an absorbance value of 0.76. Example 9, which added 1 g of acetic acid during purification, had a much lower absorbance of 0.035, indicating a lower copper content. This trend was similar in both Examples 10 and 11, which added 1.5 g and 2 g of acetic acid, respectively. Specifically, the product of Example 11 showed the lowest absorbance of 0.02. Based on these findings, it is expected that carboxylic acids and / or carboxylates can coordinate to copper ions and thus facilitate the separation of copper ions from the purified product.

[0269] The content of 4-OH-TEMPO and its reduced form in the product of Comparative Example 12 was relatively high at 1.5%. In contrast, the content of 4-OH-TEMPO in the purified products of Examples 8-11 was relatively low at 0.60-0.66%, indicating that the purification protocol was also effective in removing this by-product.

[0270] With regard to the ligand BIPY, the purification protocol of the present disclosure resulted in less than quantifiable amounts, a performance similar to that of the comparative protocol of Example 12.

[0271] Example 14: Stability of purified products Impurities present in the purified product have a significant adverse effect on product stability. Table 8 shows the initial purity and purity after 25 days.

[0272] [Table 7]

[0273] The reduction in the amount of copper significantly improved product stability. The product of Example 8, with an absorbance at 680 nm of 0.76, showed approximately a 25% reduction in (Z)-hexadeca-9-enal + (Z)-hexadeca-11-enal after 25 days. In contrast, the purified products of Examples 9-11, with lower copper content (absorbance at 680 nm of 0.035-0.02), showed only a 15%, 7%, and 8% reduction in (Z)-hexadeca-9-enal + (Z)-hexadeca-11-enal, respectively, after 25 days. Similar trends in stability were observed for the total fatty alcohol content and aldehyde content quantified. Thus, the purification protocol disclosed herein provides a more stable fatty alcohol composition.

[0274] Example 15: 1.5m 3 Preparation of catalyst in reactor 23.6 kg of copper(II) trifluoromethanesulfonate was added to a 1500 L stainless steel vessel equipped with an anchor stir bar and reflux condenser. 17.5 kg of copper shot powder (0.8-2.0 mm) and 12.2 kg of copper granules (3+14 mesh) were added to the tank. 630 kg of acetonitrile was added. The mixture was stirred at 40 rpm and heated to 85°C-90°C. After refluxing for approximately 3 hours, the mixture was cooled to room temperature.

[0275] The mixture was filtered using a Guedu filter. The filtration rate was 60-70 liters / hour, yielding approximately 770 liters of catalyst-containing solution. A total of 640 kg of catalyst solution was obtained. It was divided into two portable containers containing approximately 320 kg each, and used in Examples 16 and 17.

[0276] Example 16:4m 3 Oxidation of aliphatic alcohol mixtures in a reactor. An aliphatic alcohol mixture consisting primarily of Z11-hexadecen-1-ol, Z9-hexadecen-1-ol and hexadecan-1-ol in the proportions listed in Table 9.

[0277] [Table 8]

[0278] To a 4000 L reaction vessel equipped with a dissolved oxygen probe was added the following: 315 kg of Bioferro Z11-Hexadecenol Mixture 315 kg of acetonitrile 10kg of 2,2-bipyridine 5.5kg of 4-hydroxyTEMPO 5.5 kg of 1-methylimidazole 25kg of 4Å molecular sieves

[0279] The DO probe was calibrated by introducing air into the medium while stirring the vessel. 320 kg of the catalyst solution in acetonitrile was then transferred to the fermenter. At that point, the reaction was started. The reaction setup is shown in Table 10.

[0280] [Table 9]

[0281] The oxidation reaction was closely monitored and samples were taken every 30 minutes. Figure 4 shows the reaction data. At t=0, catalyst addition was terminated and airflow was switched on. After 1 hour of reaction time, it can be seen that the dissolved oxygen level increases considerably and the temperature drops again, indicating complete oxidation to the aldehyde form. Based on the DO and GC analysis information, it was decided to stop the airflow at 1.5 hours of reaction time.

[0282] Between 1.5 and 3 hours the reaction contents were in a waiting phase. Between 1.5 and 2.5 hours the temperature was maintained at 30° C. At the 2.5 hour point the temperature was maintained at approximately 15° C.

[0283] At the 3 hour mark, the vessel was emptied. This was accomplished by applying air pressure to the head of the vessel; the air flow was forced out of the vessel. At the 4 hour mark, the vessel contents were completely transferred into two IBCs (Intermediate Bulk Cargo Containers). The mass of the oxidized mixture was estimated to be 980 kg.

[0284] After 1 hour, 94% conversion was reached. Final conversion achieved was 99%. There is a slight increase in conversion from 97% to 99% during the waiting period (1.5 hours to final sample).

[0285] Table 11 and Figure 5 show the conversion of Z11-hexadecenal over time.

[0286] [Table 10]

[0287] Example 17:4m 3 Oxidation of aliphatic alcohol mixtures in a reactor. To a 4000 L reaction vessel equipped with a dissolved oxygen sensor was added the following: 254 kg of BioferroZ11-Hexadecenol (as shown in Example 16) 315 kg of acetonitrile 10kg of 2,2-bipyridine 5.5kg of 4-hydroxyTEMPO 5.5 kg of 1-methylimidazole 25kg of 4Å molecular sieves

[0288] The oxidation reaction was carried out in a 4000L 40R10 fermenter. First, the reaction recipe contents in the IBC (Intermediate Bulk Cargo Container) were pressure-injected into the fermenter. Then, 25 kg of molecular sieves were added into the vessel from the top. The DO probe was then calibrated by introducing air into the medium while stirring the vessel.

[0289] The catalyst solution of Example A was transferred to the fermentor with the agitation speed set at 51 RPM and aeration started. The reaction set-up is shown in Table 12.

[0290] [Table 11]

[0291] The oxidation reaction was sampled every 30 minutes. Figure 6 shows the on-line reaction data of the oxidation process. At t=98.5, the catalyst solution was introduced into the vessel. At about 99 hours, the airflow was switched on and maintained at 85-100 kg / hr for 2.5 hours. Between 101.5 and 104 hours was the waiting phase of the fermenter contents. During the course of this phase, the sparger delivered an airflow of 3.5 kg / hr.

[0292] The maximum temperature was about 34° C. (t=99-99.5 hours). The liquid was cooled to about 15° C. at t=103 hours.

[0293] [Table 12]

[0294] Example 18: Oxidation of Z11,Z13-16:OH to the corresponding aldehyde Z11,Z13-16:Ald A mixture of aliphatic primary alcohols containing 73 wt % Z11,Z13-16:OH ((Z11,Z13)-hexadecadien-1-ol) was used as a representative sample for conversion to aldehydes.

[0295] Z11, Z13-16:OH mixture (8 g), 2,2'-bipyridine (0.25 g), 2,2,6,6-tetramethylpiperidinyloxyl (0.14 g) and 1-methylimidazole (0.13 g) were added to acetonitrile (20 ml). To the solution was added tetrakisacetonitrile copper(I) trifluoromethanesulfonate in 10 ml of acetonitrile.

[0296] The temperature of the reaction mixture was controlled to 30° C. while diffusing air into the solution at a rate of 1 L / min. After 164 min, the air diffusing was stopped, the reaction mixture was diluted with 1-heptane (40 ml), and the mixture was extracted with water (20 ml). The upper phase was evaporated at 10 mbar and 60° C. to obtain a product containing 65.5 wt% Z11,Z13-16:Ald((Z11,Z13)-hexadecadienal, with a residual amount of 3.4 wt% Z11,Z13-16:OH.

[0297] [Table 13]

[0298] These data indicate that the aliphatic alcohol Z11,Z13-16:OH was chemically oxidized to the corresponding aldehyde, Z11,Z13-16:Ald.

[0299] Example 19: Comparative Example of Small Scale vs. Large Scale Oxidation Small scale 1 Oxidation of 24 g of aliphatic alcohol mixture containing the aliphatic alcohols in Table 3 was carried out; the oxidation was carried out using the above aliphatic alcohol mixture and 5 g of acetonitrile in a shake flask exposed to air. A catalyst including 1.88 g of tetrakisacetonitrile copper(I) trifluoromethanesulfonate, 0.78 g of 2.2'-bipyridine, 0.43 g of 4-hydroxyTEMPO, 0.41 g of N-imidazole, and 5.4 g of 4 Å molecular sieves was added to the reaction mixture. The reaction was carried out at 30° C. for 2 hours. The conversion steadily increased, exceeding 97% at 120 min and finally reaching 100% at 180 min.

[0300] Small scale 2 250 g of the aliphatic alcohol mixture containing the aliphatic alcohols in Table 3 was oxidized in a glass reactor equipped with a stir bar and air sparger. To the aliphatic alcohol mixture diluted with 545 g of acetonitrile was added 19 g of tetrakisacetonitrile copper(I) trifluoromethanesulfonate, 8 g of 2.2'-bipyridine, 5.3 g of 4-hydroxyTEMPO, and 6.5 g of N-imidazole. The reaction was stirred at room temperature throughout the reaction time. Conversion steadily increased to over 58% at 120 min and eventually reached 93% after 20 h.

[0301] Large scale Step 1: Copper(II) trifluoromethane and metallic copper to the catalyst Cu(ACN) 4 An OTf solution was prepared. 100 L of acetonitrile was added to a stainless steel vessel equipped with an anchor stir bar. Then, with gentle stirring, 2.81 kg of Cu(Otf) 2 and 2.8 kg of copper pellets were added. The mixture was heated to 85° C. After 5.5 hours of reflux, the mixture was cooled to room temperature. The mixture was then pressure filtered to remove the remaining copper pellets. This process yielded 90 L of a pale yellowish solution, which was used in the following process.

[0302] Step 2: The oxidation reaction was carried out in a 300 L steel vessel equipped with an air sparger. To this tank were added 60.8 kg of Z11-hexadecenol mixture, 50 L of acetonitrile, 2.4 kg of 2,2-bipyridine, 1.1 kg of 4-hydroxyTEMPO, and 1.3 kg of 1-methylimidazole. Finally, the catalyst solution from step 1 was transferred to the oxidation vessel and air was bubbled through the mixture at 10 Kg / h under constant stirring. After 16 hours of reaction time, the conversion reached 67%.

[0303] conclusion This comparative example shows that traditional oxidation methods developed for small scale oxidation are not always feasible for large scale (e.g., kilogram scale) applications. At larger scales, such as commercial chemical production, high conversion and clean reaction profiles are key process parameters, and the disclosed method provides a specific solution to these industrial needs.

[0304] References Stahl et al. J. Am. Chem. Soc. 2011, 133, 16901-16910 Kumpulainen and Koskinen, Chem. Eur. J. 2009, 15, 10901-10911

[0305] item Further, embodiments of the present invention will now be described in detail below: [Item 1] 1. A process for converting an aliphatic alcohol to an aliphatic aldehyde, comprising: (a) providing a reaction mixture comprising an aliphatic alcohol, a catalyst comprising a copper source, and a solvent; and (b) a sufficient amount of O to convert more than 50 wt. % of the fatty alcohol to aliphatic aldehydes and less than 50 wt. % to fatty acids. 2 to the reaction mixture, A method comprising: [Item 2] The method of claim 1, further comprising: 2 to the reaction mixture. [Item 3] The method of any preceding item, further comprising: providing at least 0.0025 μmol of dissolved O per μmol of initial aliphatic alcohol per minute. 2 to the reaction mixture. [Item 4] The method of any preceding item, further comprising: 2 to the reaction mixture. [Item 5] The method of any preceding item, further comprising: 2 (At least 20 μmol O 2 At least 40 µmol O 2 etc., or at least 60 μmol O 2 etc.) to the reaction mixture, thereby obtaining the aliphatic aldehyde, and optionally, wherein the aliphatic alcohol and the aliphatic aldehyde are desaturated. [Item 6] The method of any preceding item, wherein O 2 by mixing a gas or liquid containing O 2 wherein optionally O 2 wherein the compound is concentrated. [Item 7] The method of any preceding item, wherein O 2 wherein mixing is performed by bubbling a gas mixture comprising: [Item 8] 2. The process of claim 1, wherein said converting is the conversion of a primary alcohol functionality to an aldehyde functionality. [Item 9] The process of any preceding item, wherein the conversion is the oxidation of a primary alcohol functionality to an aldehyde functionality. [Item 10] The method of any preceding item, wherein the aliphatic alcohol is a primary alcohol. [Item 11] The method of any preceding item, wherein the fatty alcohol is a saturated fatty alcohol. [Item 12] The method of any preceding item, wherein the fatty alcohol is an unsaturated fatty alcohol. [Item 13] The method of any preceding item, wherein the fatty alcohol is a C10 to C26 fatty alcohol. [Item 14] The method of any preceding item, wherein the fatty alcohol is a C10 to C22 fatty alcohol. [Item 15] The method of any preceding item, wherein the fatty alcohol is a C12 to C20 fatty alcohol. [Item 16] The method of any preceding item, wherein the fatty alcohol is a C12 to C18 fatty alcohol. [Item 17] The method of any preceding item, wherein the fatty alcohol is a C12, C14, C16 or C18 fatty alcohol. [Item 18] The method of any preceding item, wherein the unsaturated fatty alcohol has a double bond at the 9, 11 or 13 positions, or wherein the unsaturated fatty alcohol has a double bond at the 9 and 11 positions, or the 11 and 13 positions. [Item 19] The method of any preceding item, wherein the unsaturated fatty alcohol has a double bond at the 9- or 12-position, or wherein the unsaturated fatty alcohol has double bonds at the 9- and 12-positions. [Item 20] The method of any preceding item, wherein the unsaturated fatty alcohol has a double bond at the 8- or 10-position, or wherein the unsaturated fatty alcohol has double bonds at the 8- and 10-positions. [Item 21] The method of any preceding item, wherein the fatty alcohol has a carbon chain length of 12, 14, or 16. [Item 22] The method of any preceding item, wherein the fatty alcohol is an unbranched fatty alcohol. [Item 23] The method of any preceding item, wherein the fatty alcohol is: (Z)-Δ3 desaturated fatty alcohols, wherein the carbon chain length is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ3 desaturated fatty alcohols, having carbon chain lengths of 8, 9, 10, 11, 12, 13, 14, 15, 18, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ5 desaturated fatty alcohols, having carbon chain lengths of 8, 9, 10, 11, 12, 13, 14, 15, 18, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (E)-Δ5 desaturated fatty alcohols, wherein the carbon chain length is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ6 desaturated fatty alcohols, having carbon chain lengths of 8, 9, 10, 11, 12, 13, 14, 15, 18, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (E)-Δ6 desaturated fatty alcohols, wherein the carbon chain length is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ7 desaturated fatty alcohols, wherein the carbon chain length is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ7 desaturated fatty alcohols, wherein the carbon chain length is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ8 desaturated fatty alcohols, wherein the carbon chain length is 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ8 desaturated fatty alcohols, wherein the carbon chain length is 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ9 desaturated fatty alcohols, wherein the carbon chain length is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ9 desaturated fatty alcohols, wherein the carbon chain length is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ10 unsaturated fatty alcohols, wherein the carbon chain length is 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ10 unsaturated fatty alcohols, wherein the carbon chain length is 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ11 unsaturated fatty alcohols, wherein the carbon chain length is 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ11 unsaturated fatty alcohols, wherein the carbon chain length is 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ12 desaturated fatty alcohols, wherein the carbon chain length is 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ12 desaturated fatty alcohols, wherein the carbon chain length is 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ13 unsaturated fatty alcohols, the unsaturated fatty alcohols having a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21, or 22; and (E)-Δ13 unsaturated fatty alcohols, the carbon chain length of which is 14, 15, 16, 17, 18, 19, 20, 21 or 22; The method of claim 1, wherein the method is selected from the group consisting of: [Item 24] The method of any preceding item, wherein the fatty alcohol is: (E) 7,(Z)9 unsaturated fatty alcohols having a carbon chain length of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E) 3, (Z) 8, (Z) 11 unsaturated fatty alcohols having a carbon chain length of 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)9, (E)11, (E)13 unsaturated fatty alcohols having a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)11, (Z)13 unsaturated fatty alcohols having a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z) 9,(E) 12 unsaturated fatty alcohols having a carbon chain length of 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E) 7,(E) 9 unsaturated fatty alcohols having a carbon chain length of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22, and (E8, E10) Unsaturated aliphatic alcohols having a carbon chain length of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; The method of claim 1, wherein the method is selected from the group consisting of: [Item 25] The method of any preceding item, wherein the fatty alcohol is: (E) 7,(Z)9 unsaturated fatty alcohols having a carbon chain length of 14; (E) 3, (Z) 8, or (Z) 11 unsaturated fatty alcohols having a carbon chain length of 14; (Z) 9, (E) 11, and (E) 13 unsaturated fatty alcohols, the carbon chain length of which is 14; (E) 7,(Z)9 unsaturated fatty alcohols having a carbon chain length of 12; (E) 3, (Z) 8, or (Z) 11 unsaturated fatty alcohols having a carbon chain length of 12; (Z) 9, (E) 11, and (E) 13 unsaturated fatty alcohols, the unsaturated fatty alcohols having a carbon chain length of 12; (E) 8,(E) 10 unsaturated fatty alcohols, the unsaturated fatty alcohols having a carbon chain length of 12; (E) 7,(E) 9 desaturated fatty alcohols having a carbon chain length of 11; (Z)11, (Z)13 unsaturated fatty alcohols having a carbon chain length of 16, and (Z) 9, (E) 12 unsaturated aliphatic alcohols having a carbon chain length of 14; The method of claim 1, wherein the method is selected from the group consisting of: [Item 26] The method of any preceding item, wherein the aliphatic alcohol is selected from the group consisting of tetradecan-1-ol, pentadecan-1-ol, hexadecan-1-ol, pentadecen-1-ol, (Z)-9-hexadecen-1-ol, (Z)-11-hexadecen-1-ol, (7E,9E)-undeca-7,9-dien-1-ol, (11Z,13Z)-hexadecadien-1-ol, (9Z,12E)-tetradecadien-1-ol, and (8E,10E)-dodecadien-1-ol. [Item 27] The method of any preceding item, wherein the fatty alcohol composition comprises at least 30 wt% of one or more fatty alcohols (at least 40 wt%, 50 wt%, 55 wt%, etc., such as 60 wt% of one or more fatty alcohols). [Item 28] The method of any preceding item, wherein the aliphatic aldehyde obtained is an aliphatic aldehyde composition comprising at least 30 wt.% of one or more aliphatic aldehydes (such as at least 40 wt.%, 50 wt.%, 55 wt.%, etc., such as 60 wt.% of one or more aliphatic aldehydes). [Item 29] The method of any preceding item, wherein the aliphatic aldehyde is a saturated aliphatic aldehyde. [Item 30] The method of any preceding item, wherein the aliphatic aldehyde is an unsaturated aliphatic aldehyde. [Item 31] The method of any preceding item, wherein the aliphatic aldehyde is a C10 to C26 aliphatic aldehyde. [Item 32] The method of any preceding item, wherein the aliphatic aldehyde is a C10 to C22 aliphatic aldehyde. [Item 33] The method of any preceding item, wherein the aliphatic aldehyde is a C12 to C20 aliphatic aldehyde. [Item 34] The method of any preceding item, wherein the aliphatic aldehyde is a C12, C14, or C16 aliphatic aldehyde. [Item 35] The method of any preceding item, wherein the aliphatic aldehyde is an unbranched aliphatic aldehyde. [Item 36] The method of any preceding item, wherein the unsaturated aliphatic aldehyde has a double bond at the 9, 11 or 13 positions, or wherein the unsaturated aliphatic aldehyde has a double bond at the 9 and 11 positions, or the 11 and 13 positions. [Item 37] The method of any preceding item, wherein the unsaturated aliphatic aldehyde has a double bond at the 9- or 12-position, or wherein the unsaturated aliphatic aldehyde has double bonds at the 9- and 12-positions. [Item 38] The method of any preceding item, wherein the unsaturated aliphatic aldehyde has a double bond at the 8- or 10-position, or wherein the unsaturated aliphatic aldehyde has double bonds at the 8- and 10-positions. [Item 39] The method according to any one of the preceding claims, wherein the aliphatic aldehyde has a carbon chain length of 12, 14, or 16. [Item 40] The method of any preceding item, wherein the aliphatic aldehyde is: (Z)-Δ3 unsaturated aliphatic aldehydes, which have a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (E)-Δ3 unsaturated aliphatic aldehydes, which have a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ5 unsaturated aliphatic aldehydes, which have a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (E)-Δ5 unsaturated aliphatic aldehydes, which have a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ6 unsaturated aliphatic aldehydes, which have a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (E)-Δ6 unsaturated aliphatic aldehydes, which have a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ7 unsaturated aliphatic aldehydes, which have a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (E)-Δ7 unsaturated aliphatic aldehydes, which have a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ8 unsaturated aliphatic aldehydes, which have a carbon chain length of 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (E)-Δ8 unsaturated aliphatic aldehydes, which have a carbon chain length of 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ9 unsaturated aliphatic aldehydes, which have a carbon chain length of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (E)-Δ9 unsaturated aliphatic aldehydes, which have a carbon chain length of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ10 unsaturated aliphatic aldehydes, which have a carbon chain length of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (E)-Δ10 unsaturated aliphatic aldehydes, which have a carbon chain length of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ11 unsaturated aliphatic aldehydes, which have a carbon chain length of 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ11 unsaturated aliphatic aldehydes, which have a carbon chain length of 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ12 unsaturated aliphatic aldehydes, which have a carbon chain length of 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ12 unsaturated aliphatic aldehydes, which have a carbon chain length of 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ13 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21, or 22; and (E)-Δ13 unsaturated aliphatic aldehydes, which have a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21 or 22; The method of claim 1, wherein the method is selected from the group consisting of: [Item 41] The method of any preceding item, wherein the aliphatic aldehyde is: (E)7,(Z)9 unsaturated aliphatic aldehydes, which have carbon chain lengths of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)3,(Z)8,(Z)11 unsaturated aliphatic aldehydes, which have carbon chain lengths of 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)9,(E)11,(E)13 unsaturated aliphatic aldehydes, which have carbon chain lengths of 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)11,(Z)13 unsaturated aliphatic aldehydes having a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)9,(E)12 unsaturated aliphatic aldehydes, which have carbon chain lengths of 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)7,(E)9 unsaturated aliphatic aldehydes, including unsaturated aliphatic aldehydes having carbon chain lengths of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; and (E)8,(E)10 unsaturated aliphatic aldehydes, which have a carbon chain length of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; The method of claim 1, wherein the method is selected from the group consisting of: [Item 42] The method of any preceding item, wherein the aliphatic aldehyde is: (E) 7,(Z) 9 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 14; (E) 3, (Z) 8, (Z) 11 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 14; (Z)9,(E)11,(E)13 unsaturated aliphatic aldehydes, including unsaturated aliphatic aldehydes having a carbon chain length of 14; (E)7,(Z)9 unsaturated aliphatic aldehydes having a carbon chain length of 12; (E) 3, (Z) 8, (Z) 11 unsaturated aliphatic aldehydes, wherein the carbon chain length is 12; (Z)9,(E)11,(E)13 unsaturated aliphatic aldehydes, including unsaturated aliphatic aldehydes having a carbon chain length of 12; (E)8,(E)10 unsaturated aliphatic aldehydes, including unsaturated aliphatic aldehydes having a carbon chain length of 12; (E)7,(E)9 unsaturated aliphatic aldehydes, including unsaturated aliphatic aldehydes having a carbon chain length of 11; (Z)11,(Z)13 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 16; and (Z) 9,(E) 12 unsaturated aliphatic aldehydes, including unsaturated aliphatic aldehydes having a carbon chain length of 14; The method of claim 1, wherein the method is selected from the group consisting of: [Item 43] The method of any preceding item, wherein the aliphatic aldehyde is selected from the group consisting of tetradecane-1-al, pentadecane-1-al, hexadecan-1-al, pentadecen-1-al, (Z)-9-hexadecen-1-al, (Z)-11-hexadecen-1-al, (7E,9E)-undeca-7,9-dien-1-al, (11Z,13Z)-hexadecadien-1-al, (9Z,12E)-tetradecadien-1-al, and (8E,10E)-dodecadien-1-al. [Item 44] The method of any preceding item, wherein the copper(I) source is a copper(I) salt. [Item 45] The method of any preceding item, wherein the copper(I) source is selected from the group consisting of tetrakisacetonitrile copper(I) triflate, tetrakisacetonitrile copper(I) tetrafluoroborate, tetrakisacetonitrile copper(I) hexafluorophosphate, and tetrakisacetonitrile copper(I) halide, and tetrakisacetonitrile copper(I) perchlorate. [Item 46] The method of any preceding item, wherein the copper(I) source comprises a copper(II) compound and a reducing agent. [Item 47] The method of any preceding item, wherein the copper(II) compound is a copper(II) salt. [Item 48] The method of any preceding item, wherein the copper(II) salt is selected from the group consisting of copper(II) triflate, copper(II) tetrafluoroborate, copper(II) hexafluorophosphate, copper(II) bromide, copper(II) chloride, copper(II) iodide, and copper(II) perchlorate. [Item 49] The method of any preceding item, wherein the reducing agent is selected from the group consisting of copper metal, zinc metal, aluminum metal, sodium hydrogen sulfate, formic acid, salts of formic acid, oxalic acid, and salts of oxalic acid. [Item 50] The method of any preceding item, wherein the copper(I) source is a copper(II) salt and copper metal. [Item 51] The method of any preceding item, wherein the catalyst composition comprises a ligand. [Item 52] The method of any preceding item, wherein the ligand coordinates to copper(I) through nitrogen. [Item 53] The method of any preceding item, wherein the ligand comprises a pyridine moiety. [Item 54] The method of any preceding item, wherein the ligand is a nitrogen bidentate ligand. [Item 55] The method of any preceding item, wherein the ligand comprises a 2,2'-bipyridine or 2,2'-bipyrimidine moiety. [Item 56] The method of any preceding item, wherein the ligand is selected from the group consisting of 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 2,2'-bipyrimidine, 2,2'-bipyridine-4,4'-dicarboxylic acid or ester thereof, and 2,2'-bipyridine-5,5'-dicarboxylic acid or ester thereof. [Item 57] The method of any preceding item, wherein the catalyst composition comprises an aminoxyl radical compound. [Item 58] The method of any preceding item, wherein the aminoxyl radical compound is selected from the group consisting of TEMPO, (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)oxyl (4-OH-TEMPO), 4-acetamido-TEMPO, 4-hydroxy-TEMPO benzoate, 4-amino-TEMPO, 2-azaadamantane-N-oxyl, 9-azabicyclo[3.3.1]nonane N-oxyl, 4-carboxy-TEMPO, 4-maleimido-TEMPO, 4-methoxy-TEMPO, 1-methyl-2-azaadamantane-N-oxyl, 4-oxo-TEMPO, and a functionalized polymer having any of the aminoxyl radical compounds. [Item 59] The method of any preceding item, wherein the aminoxyl radical compound is (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) or a TEMPO derivative. [Item 60] The method of any preceding item, wherein the catalyst composition comprises a base. [Item 61] The method of any preceding item, wherein the base is an organic base. [Item 62] The method of any preceding item, wherein the base is selected from the group consisting of 1-methylimidazole, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,1,3,3-tetramethylguanidine, 7-methyl-1,5,7-triazabicyclo[4.4.0]-dec-5-ene, and potassium t-butoxide. [Item 63] The method of any preceding item, wherein O of the reaction mixture is 2 wherein the exposure to is carried out at 5-80°C (such as 10-70°C, such as 15-65°C). [Item 64] The method of any preceding item, wherein O of the reaction mixture is 2 wherein the exposure to is carried out under a pressure of 0.5 to 40 bar (such as 0.5 to 30 bar, such as 0.6 to 20 bar, such as 0.7 to 10 bar, such as 0.8 to 5 bar). [Item 65] The method of any preceding item, wherein O of the reaction mixture is 2 wherein the exposure to is carried out at a pressure of 0.8 to 1.2 bar. [Item 66] The method of any preceding item, wherein O of the reaction mixture is 2 wherein the exposure to is carried out at ambient pressure. [Item 67] The method of any preceding item, wherein the method comprises measuring at least 0.3 ml of O per gram of fatty alcohol composition per minute when evaluated at a pressure of 1 bar. 2 (At least 0.4 ml, 0.5 ml, 0.6 ml, 0.7 ml, 0.8 ml, 0.9 ml, 1.0 ml, 1.1 ml, 1.2 ml, 1.3 ml, 1.4 ml, etc., per gram of fatty alcohol composition per minute, at least 1.5 ml of O per gram of fatty alcohol composition per minute 2 and the like. [Item 68] The method of any preceding item, wherein when evaluated at a pressure of 1 bar, the method comprises the step of producing at least 0.3 ml of O per gram of aliphatic alcohol per minute. 2 (At least 0.4 ml, 0.5 ml, 0.6 ml, 0.7 ml, 0.8 ml, 0.9 ml, 1.0 ml, 1.1 ml, 1.2 ml, 1.3 ml, 1.4 ml, etc. per gram of fatty alcohol per minute, at least 1.5 ml of O per gram of fatty alcohol per minute 2 and the like. [Item 69] The method of any preceding item, wherein the reaction is carried out at a rate of at least 60 ml O per mole of aliphatic alcohol per minute when evaluated at a pressure of 1 bar. 2 (At least 100ml, 150ml, 200ml, 250ml, 300ml, 350ml, 400ml, etc., at least 450ml of O per mole of aliphatic alcohol per minute) 2 and the like. [Item 70] The method of any preceding item, wherein the method comprises: 2 (at least 12 μmol, 16 μmol, 20 μmol, 24 μmol, 28 μmol, 32 μmol, 36 μmol, 40 μmol, 44 μmol, 48 μmol, 52 μmol, 56 μmol, 60 μmol O per gram of aliphatic alcohol per minute) 2 exposing the reaction mixture to [Item 71] The method of any preceding item, wherein the method comprises: 2 (At least 4 mmol, 6 mmol, 8 mmol, 10 mmol, 12 mmol, 14 mmol, 16 mmol, etc., at least 18 mmol of O per gram of aliphatic alcohol per minute) 2 and the like. [Item 72] The method of any preceding item, wherein the gas mixture is 5 to 100% O 2A method comprising: [Item 73] The method of any preceding item, wherein the gas mixture is 15-25% O 2 A method comprising: [Item 74] The method of any preceding item, wherein the gas mixture is at least 90% O 2 A method comprising: [Item 75] The method of any preceding item, wherein the solvent is an aprotic polar solvent. [Item 76] The method of any preceding item, wherein the solvent is selected from the group consisting of acetonitrile, dimethylformamide, acetonitrile, propionitrile, butyronitrile, dimethylsulfoxide, dimethylacetamide, and propylene carbonate. [Item 77] The method of any preceding item, wherein the amount of solvent corresponds to 0-2000% (such as 100-2000%, such as 100-1500%, such as 100-1000%, such as 100-500%) of the weight of the fatty alcohol composition. [Item 78] The method of any preceding item, wherein the amount of the solvent corresponds to 100-2000% (such as 100-1500%, such as 100-1000%, such as 100-500%) of the weight of the aliphatic alcohol. [Item 79] The method of any preceding item, wherein O 2 wherein exposure to is maintained for at least 5 minutes (such as at least 10 minutes, such as at least 20 minutes, such as at least 30 minutes, such as at least 40 minutes, such as at least 50 minutes, such as at least 60 minutes, such as at least 70 minutes, 80 minutes, such as 90 minutes, such as at least 100 minutes). [Item 80] The method of any preceding item, wherein O 2 wherein the exposure to is carried out in a bubble column reactor or a trickle bed reactor. [Item 81] The method of any preceding item, wherein the conversion of the aliphatic alcohol is at least 60 wt% (such as at least 80 wt%, such as at least 85 wt%, such as 87 wt%, such as at least 90 wt%, such as at least 95 wt%, such as at least 99 wt%). [Item 82] The method of any preceding item, wherein the ratio of fatty acids produced to aliphatic aldehydes produced is less than 10:90. [Item 83] The method of any preceding item, wherein the conversion of fatty alcohols to fatty acids is less than 40 wt% (such as less than 30 wt%, such as less than 20 wt%, such as less than 15 wt%, such as less than 10 wt%, such as less than 5 wt%, such as less than 1 wt%). [Item 84] The method of any preceding item, further comprising removing water from the reaction mixture. [Item 85] The process of any preceding item, wherein removing water from the reaction mixture comprises removing substantially all of the water from the reaction mixture. 2 A method achieved through exposure to. [Item 86] The process of any preceding item, wherein water removal from the reaction mixture is accomplished using an adsorbent material. [Item 87] The method of any preceding item, wherein the adsorbent material is selected from the group consisting of molecular sieves, silica gel, alumina, bentonite clay, calcium oxide, alkali metal carbonates, bicarbonates, or alkaline earth metal carbonates. [Item 88] The method of any preceding item, further comprising the step of removing water from the reaction medium before, during, or after the oxidation of the aliphatic alcohol. [Item 89] The method of item 88, further comprising adding a water absorbing or adsorbing material to the reaction medium that absorbs or adsorbs water, optionally the water absorbing or adsorbing material may be selected from molecular sieves, silica gel, aluminas, bentonite clay, calcium oxides, alkali metal carbonates, bicarbonates, or alkaline earth metal carbonates or combinations thereof. [Item 90] The process of items 88-89, wherein the water-absorbing or water-adsorbing material is added to the reaction medium in an amount such that the water content of the reaction medium after the oxidation process is less than 2% by weight, and optionally the molar conversion of aliphatic alcohols to aliphatic aldehydes is greater than 93%. [Item 91] The process of items 88 to 90, wherein prior to oxidation, the water absorbing or adsorbing material is added to the reaction medium in an amount of at least 10 g per millimole of aliphatic alcohol (such as at least 15 g per millimole of aliphatic alcohol, such as at least 19 g per millimole of aliphatic alcohol), and wherein optionally, the water absorbing or adsorbing material may be a molecular sieve. [Item 92] The method of any preceding item, wherein the method further comprises an initial step of producing the fatty alcohol, preferably wherein the fatty alcohol is desaturated, the initial step comprising: (i) providing a yeast cell capable of producing the fatty alcohol; and (ii) incubating the yeast cells in a medium, thereby producing the fatty alcohol; A method comprising: [Item 93] The method of any preceding item, wherein the method further comprises an initial step of producing the fatty alcohol, the initial step comprising the steps (i) and (ii) of: (i) providing a yeast cell capable of synthesizing alkanoyl-CoA; wherein the yeast cell comprises: Desaturases; and Alcohol-forming fatty acyl-CoA reductase, and (ii) expressing the desaturase and the alcohol-forming fatty acyl-CoA reductase in the yeast cell; and (iii) incubating the yeast cells in a medium whereby the desaturase is capable of converting at least a portion of the alkanoyl-CoA to an alkenoyl-CoA, and whereby the alcohol forming fatty acyl-CoA reductase is capable of converting at least a portion of the alkenoyl-CoA to a fatty alcohol, thereby producing the fatty alcohol; A method comprising: [Item 94] The method of any preceding item, wherein the aliphatic alcohol is (Z)-11-hexadecen-1-ol, wherein the alkanoyl-CoA is hexadecanoyl-CoA, wherein the desaturase is a Δ11-desaturase, and wherein the alkenoyl-CoA is (Z)-11-hexadecenyl-CoA. [Item 95] The method of any preceding item, wherein the method further comprises an initial step of producing the fatty alcohol, the initial step comprising the steps (i) and (ii): (i) providing a fatty yeast cell capable of producing a desaturated fatty alcohol; wherein the yeast cell further comprises: capable of expressing at least one heterologous fatty acyl-CoA desaturase capable of introducing at least one double bond into a fatty acyl-CoA to produce a desaturated fatty acyl-CoA; capable of expressing at least one heterologous fatty acyl-CoA reductase capable of converting at least a portion of the desaturated fatty acyl-CoA to an desaturated fatty alcohol; having a mutation that reduces the activity of fatty alcohol oxidase and having a mutation that reduces the activity of at least one of fatty aldehyde dehydrogenase, a peroxisome biogenesis factor, and glycerol-3-phosphate acyltransferase; and (ii) incubating the yeast cells in a medium, thereby producing the fatty alcohol; A method comprising: [Item 96] The method according to any one of the preceding paragraphs, wherein the method further comprises an initial step of producing the fatty alcohol, the initial step comprising the steps (i) and (ii): (i) providing a yeast cell capable of producing a desaturated fatty alcohol; wherein the yeast cell comprises: at least one heterologous fatty acyl-CoA desaturase capable of introducing at least one double bond into a fatty acyl-CoA of carbon chain length 14, wherein the desaturase is selected from the group consisting of Δ9 desaturases and Δ11 desaturases, wherein the desaturase has a higher specificity for tetradecanoyl-CoA and therefore a higher specificity for hexadecanoyl-CoA; and at least one heterologous fatty acyl-CoA reductase capable of converting at least a portion of the desaturated fatty acyl-CoA into an desaturated fatty alcohol; expresses; and (ii) incubating the yeast cells in a medium, thereby producing the fatty alcohol; A method comprising: [Item 97] The method of any preceding item, wherein the method further comprises an initial step of producing the fatty alcohol, the initial step comprising providing a yeast cell capable of producing the fatty alcohol, and culturing the yeast cell in a medium under conditions capable of producing the fatty alcohol, wherein the culture medium comprises an extractant in an amount equal to or greater than the haze concentration measured in an aqueous solution (such as the medium) at the culture temperature, and wherein the extractant is a non-ionic ethoxylated surfactant, thereby producing the fatty alcohol. [Item 98] The method of any preceding item, wherein the method further comprises an initial step of producing the fatty alcohol, preferably wherein the fatty alcohol is a desaturated fatty alcohol, and wherein the initial step comprises: (i) providing a yeast cell capable of producing a fatty alcohol ester and culturing the yeast cell in a medium under conditions capable of producing the fatty alcohol ester; wherein the culture medium comprises an extractant in an amount equal to or greater than the haze concentration measured in an aqueous solution (such as the medium) at the culture temperature, and wherein the extractant is a non-ionic ethoxylated surfactant, thereby producing the fatty alcohol ester; and (ii) converting the fatty alcohol ester to the fatty alcohol, thereby producing the fatty alcohol; A method comprising: [Item 99] A method for purifying an aliphatic aldehyde, the method comprising the following steps (a) to (c): (a) providing a crude reaction product, comprising: (i) Aliphatic aldehydes; (ii) copper ions; and (iii) a polar solvent; providing a crude reaction product comprising: (b) combining the crude reaction product with a non-polar aprotic solvent and an acid to form a non-polar phase and a polar phase; and (c) separating the non-polar phase from the polar phase; A method for purifying an aliphatic aldehyde, comprising: [Item 100] The process for purifying an aliphatic aldehyde of any preceding item, wherein the crude reaction product is: (i) 5 to 80% of the aliphatic aldehyde; (ii) 0.05 to 5.0% copper ion; and (iii) 20 to 95% polar solvent; A method for purifying an aliphatic aldehyde, comprising: [Item 101] The method for purifying an aliphatic aldehyde of any preceding item, wherein the crude reaction product contains 0.05 to 5.0% copper ions (such as 0.05 to 2.0% copper ions, such as 0.05 to 1.0% copper ions). [Item 102] The method of any preceding item, wherein the crude reaction product further comprises a ligand (such as 0.1-10% ligand, such as 0.1-5% ligand, such as 0.1-2% ligand, such as about 1% ligand). [Item 103] The method of any preceding item, wherein the ligand is a nitrogen bidentate ligand selected from the group consisting of 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine2,2'-bipyrimidine, 2,2'-bipyridine-4,4'-dicarboxylic acid or ester thereof, 2,2'-bipyridine-5,5'-dicarboxylic acid or ester thereof, and the like. [Item 104] The method of any preceding item, wherein the crude reaction product further comprises an aminoxyl radical compound (such as 0.01-10% aminoxyl radical compound, such as 0.01-5% aminoxyl radical compound, such as about 0.01-2% aminoxyl radical compound, such as about 0.5% aminoxyl radical compound). [Item 105] The method of purifying an aliphatic aldehyde of any preceding item, wherein the aminoxyl radical compound is selected from the group consisting of TEMPO, (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)oxyl (4-OH-TEMPO), 4-acetamido-TEMPO, 4-hydroxy-TEMPO benzoate, 4-amino-TEMPO, 2-azaadamantane-N-oxyl, 9-azabicyclo[3.3.1]nonane N-oxyl, 4-carboxy-TEMPO, 4-maleimido-TEMPO, 4-methoxy-TEMPO, 1-methyl-2-azaadamantane-N-oxyl, 4-oxo-TEMPO, and a functionalized polymer having any of the aminoxyl radical compounds. [Item 106] The method of any preceding item, wherein the crude reaction product further comprises a base (such as 0.1-10% base, such as 0.1-5% base, such as 0.1-2% base, such as about 0.5% base). [Item 107] The method of any preceding claim, wherein the base is selected from the group consisting of 1-methylimidazole, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,1,3,3-tetramethylguanidine, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and potassium t-butoxide. [Item 108] The process for purifying an aliphatic aldehyde of any preceding item, wherein the aliphatic aldehyde is a saturated aliphatic aldehyde. [Item 109] The process for purifying an aliphatic aldehyde of any preceding item, wherein the aliphatic aldehyde is an unsaturated aliphatic aldehyde. [Item 110] The method for purifying an aliphatic aldehyde according to any preceding item, wherein the aliphatic aldehyde is a C10 to C26 aliphatic aldehyde. [Item 111] The method for purifying an aliphatic aldehyde according to any preceding item, wherein the aliphatic aldehyde is a C10-C22 aliphatic aldehyde. [Item 112] The process for purifying an aliphatic aldehyde according to any preceding item, wherein the aliphatic aldehyde is a C12 to C20 aliphatic aldehyde. [Item 113] The method for purifying an aliphatic aldehyde of any preceding item, wherein the aliphatic aldehyde is a C12, C14, or C16 aliphatic aldehyde. [Item 114] The process for purifying an aliphatic aldehyde of any preceding item, wherein the aliphatic aldehyde is an unbranched aliphatic aldehyde. [Item 115] The method of any preceding item for purifying an aliphatic aldehyde, wherein the aliphatic aldehyde is produced by: (Z)-Δ3 unsaturated aliphatic aldehydes, which have a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (E)-Δ3 unsaturated aliphatic aldehydes, which have a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ5 unsaturated aliphatic aldehydes, which have a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (E)-Δ5 unsaturated aliphatic aldehydes, which have a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ6 unsaturated aliphatic aldehydes, which have a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (E)-Δ6 unsaturated aliphatic aldehydes, which have a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ7 unsaturated aliphatic aldehydes, which have a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (E)-Δ7 unsaturated aliphatic aldehydes, which have a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ8 unsaturated aliphatic aldehydes, which have a carbon chain length of 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (E)-Δ8 unsaturated aliphatic aldehydes, which have a carbon chain length of 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ9 unsaturated aliphatic aldehydes, which have a carbon chain length of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (E)-Δ9 unsaturated aliphatic aldehydes, which have a carbon chain length of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ10 unsaturated aliphatic aldehydes, which have a carbon chain length of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (E)-Δ10 unsaturated aliphatic aldehydes, which have a carbon chain length of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22; (Z)-Δ11 unsaturated aliphatic aldehydes, which have a carbon chain length of 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ11 unsaturated aliphatic aldehydes, which have a carbon chain length of 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ12 unsaturated aliphatic aldehydes, which have a carbon chain length of 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)-Δ12 unsaturated aliphatic aldehydes, which have a carbon chain length of 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)-Δ13 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21, or 22; and (E)-Δ13 unsaturated aliphatic aldehydes, which have a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21 or 22; 1. A method for purifying an aliphatic aldehyde, comprising the steps of: [Item 116] The method of any preceding item for purifying an aliphatic aldehyde, wherein the aliphatic aldehyde is produced by: (E)7,(Z)9 unsaturated aliphatic aldehydes, which have carbon chain lengths of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)3,(Z)8,(Z)11 unsaturated aliphatic aldehydes, which have carbon chain lengths of 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)9,(E)11,(E)13 unsaturated aliphatic aldehydes, which have carbon chain lengths of 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z11, Z13) unsaturated aliphatic aldehydes having a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z9,E12) unsaturated aliphatic aldehydes having a carbon chain length of 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (7E,9E) unsaturated aliphatic aldehydes having a carbon chain length of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; and (E8, E10) Unsaturated aliphatic aldehydes having a carbon chain length of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; 1. A method for purifying an aliphatic aldehyde, comprising the steps of: [Item 117] The method of any preceding item for purifying an aliphatic aldehyde, wherein the aliphatic aldehyde is produced by: (E)7,(Z)9 unsaturated aliphatic aldehydes having a carbon chain length of 14; (E) 3, (Z) 8, (Z) 11 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 14; (Z)9, (E)11, and (E)13 unsaturated aliphatic aldehydes, each of which has a carbon chain length of 14; (E)7,(Z)9 unsaturated aliphatic aldehydes having a carbon chain length of 12; (E)3,(Z)8,(Z)11 unsaturated aliphatic aldehydes, where the carbon chain length is 12; (Z)9, (E)11, and (E)13 unsaturated aliphatic aldehydes, including unsaturated aliphatic aldehydes having a carbon chain length of 12; and (E)8,(E)10 unsaturated aliphatic aldehydes, which have a carbon chain length of 12; (E)7,(E)9 unsaturated aliphatic aldehydes, including unsaturated aliphatic aldehydes having a carbon chain length of 11; (Z)11,(Z)13 unsaturated aliphatic aldehydes, the unsaturated aliphatic aldehydes having a carbon chain length of 16; and (Z) 9, (E) 12 unsaturated aliphatic aldehydes, the carbon chain length of which is 14; 1. A method for purifying an aliphatic aldehyde, comprising the steps of: [Item 118] The method for purifying an aliphatic aldehyde of any preceding item, wherein the aliphatic aldehyde is selected from the group consisting of tetradecane-1-al, pentadecane-1-al, hexadecan-1-al, pentadecen-1-al, (Z)-9-hexadecen-1-al, (Z)-11-hexadecen-1-al, (7E,9E)-undeca-7,9-dien-1-al, (11Z,13Z)-hexadecadien-1-al, (9Z,12E)-tetradecadien-1-al, and (8E,10E)-dodecadien-1-al. [Item 119] The method for purifying an aliphatic aldehyde of any preceding item, wherein the copper ion is copper(II) ion. [Item 120] The method of any preceding claim, wherein the polar solvent is selected from the group consisting of acetonitrile, dimethylformamide, acetonitrile, propionitrile, butyronitrile, dimethylsulfoxide, dimethylacetamide, and propylene carbonate. [Item 121] The method for purifying an aliphatic aldehyde of any preceding item, wherein the polar solvent is acetonitrile. [Item 122] The method for purifying an aliphatic aldehyde of any preceding item, wherein the non-polar aprotic solvent is selected from the group consisting of linear alkanes, branched alkanes, and cyclic alkanes. [Item 123] The method of any preceding claim, wherein the non-polar aprotic solvent is selected from the group consisting of pentanes, hexanes, heptanes, and octanes. [Item 124] The method of any preceding claim, wherein the non-polar aprotic solvent is selected from the group consisting of heptane, pentane, hexane, cyclohexane, and octane. [Item 125] The method for purifying an aliphatic aldehyde according to any preceding item, wherein the pKa value of the acid is 3-6. [Item 126] The method for purifying an aliphatic aldehyde of any preceding item, wherein the acid is a carboxylic acid. [Item 127] The method for purifying an aliphatic aldehyde according to any preceding item, wherein the carboxylic acid is a C2-C8 carboxylic acid. [Item 128] The method for purifying an aliphatic aldehyde of any preceding item, wherein the carboxylic acid is selected from the group consisting of C2 to C8 monocarboxylic acids, C2 to C8 dicarboxylic acids, and C6 to C8 tricarboxylic acids. [Item 129] The method of any preceding claim, wherein the carboxylic acid is selected from the group consisting of acetic acid, citric acid, propanoic acid, lactic acid, glycolic acid, and polyacrylic acid. [Item 130] The process for purifying an aliphatic aldehyde of any preceding item, wherein at least 1.0 molar equivalent of carboxylic acid relative to copper is used. [Item 131] The method of any preceding claim, wherein at least 2.0 molar equivalents (such as at least 2.4 equivalents) of carboxylic acid relative to copper are used. [Item 132] The process for purifying an aliphatic aldehyde of any preceding item, wherein the crude reaction product further comprises an oxidizing agent and / or a spent oxidizing agent. [Item 133] The method for purifying an aliphatic aldehyde of any preceding item, wherein the oxidant or spent oxidant is selected from the group consisting of TEMPO, (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)oxyl (4-OH-TEMPO), 4-acetamido-TEMPO, 4-hydroxy-TEMPO benzoate, 4-amino-TEMPO, 2-azaadamantane-N-oxyl, 9-azabicyclo[3.3.1]nonane N-oxyl, 4-carboxy-TEMPO, 4-maleimido-TEMPO, 4-methoxy-TEMPO, 1-methyl-2-azaadamantane-N-oxyl, 4-oxo-TEMPO, and functionalized polymers having any of the aminoxyl radical compounds; or spent materials thereof. [Item 134] The method of any preceding claim, further comprising evaporating the non-polar aprotic solvent. [Item 135] The method of any preceding item for purifying an aliphatic aldehyde, wherein evaporation of the non-polar aprotic solvent is carried out under low pressure (such as less than 100 mbar, such as less than 50 mbar, such as less than 40 mbar, such as less than 30 mbar). [Item 136] 1. A method for converting a composition comprising a fatty alcohol to a composition enriched in a fatty aldehyde, the method comprising: (a) converting a fatty alcohol-containing composition to a fatty aldehyde-containing composition using the method of any preceding paragraph; and (b) purifying the aliphatic aldehyde-containing composition using the aliphatic aldehyde purification method of any preceding paragraph; Including, Optionally, the process wherein said fatty alcohol and said fatty aldehyde are desaturated. [Item 137] A composition comprising an aliphatic aldehyde obtained by the method of any preceding item, optionally wherein the aliphatic aldehyde is unsaturated. [Item 138] A composition comprising an aliphatic aldehyde of any preceding item, wherein the composition exhibits an absorbance at 680 nm of a maximum of 0.5 when using a 5 mm path length cuvette. [Item 139] 13. A composition comprising an aliphatic aldehyde of any preceding item, wherein the absorbance at 680 nm is at most 0.4 (such as at most 0.3, such as at most 0.2, such as at most 0.1, such as at most 0.08, such as at most 0.06, such as at most 0.05) when using a 5 mm pathlength cuvette. [Item 140] A composition comprising an aliphatic aldehyde of any preceding item, wherein the aliphatic aldehyde composition comprises less than 0.4% (such as less than 0.3%, such as less than 0.2%, such as less than 0.1%, such as less than 0.08%, such as less than 0.06%, such as less than 0.05%, such as less than 0.04%) copper. [Item 141] A composition comprising greater than 93% by weight of an aliphatic aldehyde, less than 7% by weight of an aliphatic alcohol, and less than 2% by weight of water. [Item 142] 1. A process for converting an aliphatic alcohol to an aliphatic acetal, the process comprising: (a) providing a reaction mixture comprising an aliphatic alcohol composition comprising an aliphatic alcohol of any preceding item, a catalyst composition of any preceding item, and a solvent of any preceding item; (b)O 2 at least 10 μmoles of O per gram of aliphatic alcohol per minute by bubbling a gas mixture containing 2exposing the reaction mixture to, thereby obtaining an aliphatic aldehyde; and (c) converting the aldehyde functional group of the aliphatic aldehyde to an acetal functional group, thereby obtaining the aliphatic acetal; Including, Optionally, the process wherein said aliphatic alcohol and said aliphatic acetal are unsaturated. [Item 143] 2. An aliphatic acetal obtained by the process of any preceding item, optionally wherein the aliphatic acetal is unsaturated. [Item 144] A sustained release aliphatic aldehyde composition comprising the aliphatic acetal of any preceding item. [Item 145] A method for producing an aliphatic aldehyde sustained release composition of any preceding item, comprising carrying out the method of any preceding item to provide an aliphatic acetal, and formulating the aliphatic acetal into a sustained release composition, optionally wherein the aliphatic acetal is unsaturated. [Item 146] 1. A process for converting an aliphatic alcohol to an aliphatic α-hydroxysulfonic acid, the process comprising: (a) providing a reaction mixture comprising an aliphatic alcohol composition comprising an aliphatic alcohol of any preceding item, a catalyst composition of any preceding item, and a solvent of any preceding item; (b)O 2 at least 10 μmoles of O per gram of aliphatic alcohol per minute by bubbling a gas mixture containing 2 exposing the reaction mixture to, thereby obtaining an aliphatic aldehyde; and (c) converting the aldehyde functional group of the aliphatic aldehyde into an α-hydroxysulfonic acid functional group, thereby obtaining the aliphatic α-hydroxysulfonic acid; Including, Optionally, the method wherein said aliphatic alcohol and said aliphatic α-hydroxysulfonic acid are unsaturated. [Item 147] An aliphatic α-hydroxysulfonic acid obtained by the process of any preceding item, optionally wherein the aliphatic α-hydroxysulfonic acid is unsaturated. [Item 148] 2. A sustained release aliphatic aldehyde composition comprising an aliphatic α-hydroxysulfonic acid of any preceding item, optionally wherein the aliphatic α-hydroxysulfonic acid is unsaturated. [Item 149] A method for producing an aliphatic aldehyde sustained release composition of any preceding item, the method comprising carrying out the method of any preceding item to provide an aliphatic α-hydroxysulfonic acid, and formulating the aliphatic α-hydroxysulfonic acid into a sustained release composition, thereby obtaining the aliphatic aldehyde sustained release composition. [Item 150] 1. A pheromone component produced from renewable feedstocks, the pheromone component having at least 80% bio-based carbon content. [Item 151] The fatty aldehyde composition of any preceding item and / or the pheromone component of any preceding item comprising the fatty aldehyde.

Claims

1. A method for converting a large-scale aliphatic alcohol to an aliphatic aldehyde, said method comprising: (a) providing a reaction mixture comprising at least 1 kilogram of an aliphatic alcohol, a catalyst comprising a copper source, at least 1 kilogram of a solvent, and a water absorbent or adsorbent material that absorbs or adsorbs water; and (b) O ２ By adding a gas or a liquid containing it to the reaction medium, at least 0.01 μmol of O per μmol of copper per minute ２ is dissolved in the reaction mixture, or at least 0.001 μmol of O per μmol of the initial aliphatic alcohol per minute ２ is dissolved in the reaction mixture, thereby oxidizing more than 50 wt% of the aliphatic alcohol to an aliphatic aldehyde and less than 50 wt% to a fatty acid. A method comprising.

2. The method according to claim 1, further comprising dissolving in the reaction mixture at least 0.049 μmol of dissolved O per μmol of copper per minute. ２ in the reaction mixture. **Claim 3**: The method according to claim 1, further comprising dissolving in the reaction mixture at least 0.0025 μmol of dissolved O per μmol of the initial aliphatic alcohol per minute. ２ The method according to claim 1, further comprising dissolving in the reaction mixture at least 0.0025 μmol of dissolved O per μmol of the initial aliphatic alcohol per minute. **Claim 4**: The method according to claim 1, further comprising dissolving in the reaction mixture at least 0.025 μmol of dissolved O per μmol of fatty acid per minute. ２ which further comprises dissolving ２ **Claim 5**: The method according to claim 1, comprising dissolving in the reaction mixture at least 10 μmol of O per gram of aliphatic alcohol per minute ２ (at least 20 μmol of O ２ , at least 40 μmol of O ２ , or at least 60 μmol of O ２ etc.), thereby obtaining the aliphatic aldehyde, and optionally, wherein the aliphatic alcohol and the aliphatic aldehyde may be unsaturated.

6. O ２ wherein the gas or liquid containing O is air, and optionally O ２ may be concentrated, the method according to claim 1.

7. Gas supply of the gas or liquid containing O to the reaction medium is achieved by pumping a gas or liquid mixture containing O or aerating it to foam in the reaction mixture. The method according to claim 1. ２ The gas supply of the gas or liquid containing O to the reaction medium is achieved by pumping a gas or liquid mixture containing O or aerating it to foam in the reaction mixture. ２ The method according to claim 1, wherein the gas supply of the gas or liquid containing O to the reaction medium is achieved by pumping a gas or liquid mixture containing O or aerating it to foam in the reaction mixture.

8. The method according to claim 1, wherein the copper source comprises a copper(I) salt or a combination of copper(II) and a reducing agent.

9. The method according to claim 1, wherein the catalyst further comprises a ligand such as a ligand selected from the group consisting of 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine 2,2'-bipyrimidine, 2,2'-bipyridine-4,4'-dicarboxylic acid or its ester, 2,2'-bipyridine-5,5'-dicarboxylic acid or its ester.

10. The method according to claim 1, wherein the catalyst comprises an aminoxyl radical compound such as an aminoxyl radical compound selected from the group consisting of TEMPO, (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)oxyl (4-OH-TEMPO), 4-acetamido-TEMPO, 4-hydroxy-TEMPO benzoate, 4-amino-TEMPO, 2-azabicyclo[3.3.1]nonane N-oxyl, 9-azabicyclo[3.3.1]nonane N-oxyl, 4-carboxy-TEMPO, 4-maleimide-TEMPO, 4-methoxy-TEMPO, 1-methyl-2-azabicyclo[3.3.1]nonane N-oxyl, 4-oxo-TEMPO, and a functionalized polymer having any of the above aminoxyl radical compounds.

11. The method according to claim 1, wherein the catalyst comprises a base such as a base selected from the group consisting of 1-methylimidazole, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,1,3,3-tetramethylguanidine, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and potassium t-butoxide.

12. The method according to claim 1, wherein the solvent is a non-halogenated solvent.

13. The method according to claim 12, wherein the solvent is selected from acetonitrile, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), pentane, hexane, heptane, cycloalkane, petroleum ether, dioxane, diethyl ether, tetrahydrofuran, ethyl acetate, acetone, nitromethane, propylene carbonate, or a combination thereof.

14. The method according to claim 1, wherein the conversion rate of the aliphatic alcohol to the aliphatic aldehyde is at least 60 wt% (such as at least 80 wt%, such as at least 85 wt%, such as at least 87 wt%, such as at least 90 wt%, such as at least 95 wt%, such as at least 99 wt%).

15. The method according to claim 1, wherein the ratio of the produced fatty acid to the produced aliphatic aldehyde is less than 10:

90.

16. The method according to claim 1, wherein the conversion rate of the aliphatic alcohol to the fatty acid is less than 40 wt% (such as less than 30 wt%, such as less than 20 wt%, such as less than 15 wt%, such as less than 10 wt%, such as less than 5 wt%, such as less than 1 wt%).

17. The method according to claim 1, wherein the water-absorbing material or water-adsorbing material is selected from molecular sieves, silica gel, aluminas, bentonite clay, calcium oxides, alkali metal carbonates, bicarbonates, or alkaline earth metal carbonates, or a combination thereof.

18. The method according to claim 1, wherein the water content of the reaction medium after the oxidation process is less than 2% by weight, and the water-absorbing material or water-adsorbing material is added to the reaction medium in an amount such that, optionally, the molar conversion rate of the aliphatic alcohol to the aliphatic aldehydes is more than 93%.

19. The method according to claim , wherein the amount of the water-absorbing material or water-adsorbing material before oxidation is added such that it is at least 10 g per millimole of aliphatic alcohol in the reaction medium (such as at least 15 g per millimole of aliphatic alcohol, such as at least 19 g per millimole of aliphatic alcohol), and optionally, the water-absorbing material or water-adsorbing material may be a molecular sieve.

20. The aliphatic aldehyde is: (Z)-Δ3 unsaturated aliphatic aldehydes, wherein the carbon chain length is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (E)-Δ3 unsaturated aliphatic aldehydes, wherein the carbon chain length is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (Z)-Δ5 unsaturated aliphatic aldehydes, wherein the carbon chain length is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (E)-Δ5 unsaturated aliphatic aldehydes, wherein the carbon chain length is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (Z)-Δ6 unsaturated aliphatic aldehydes, wherein the carbon chain length is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (E)-Δ6 unsaturated aliphatic aldehydes, wherein the carbon chain length is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (Z)-Δ7 unsaturated aliphatic aldehydes, wherein the carbon chain length is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (E)-Δ7 unsaturated aliphatic aldehydes, wherein the carbon chain length is 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (Z)-Δ8 unsaturated aliphatic aldehydes, wherein the carbon chain length is 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (E)-Δ8 unsaturated aliphatic aldehydes, wherein the carbon chain length is 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (Z)-Δ9 unsaturated aliphatic aldehydes, wherein the carbon chain length is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (E)-Δ9 unsaturated aliphatic aldehydes, wherein the carbon chain length is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (Z)-Δ10 unsaturated aliphatic aldehydes, wherein the carbon chain length is 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; Unsaturated aliphatic aldehydes having (E)-Δ10, wherein the carbon chain length is 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (Z)-Δ11 unsaturated aliphatic aldehydes, wherein the carbon chain length is 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (E)-Δ11 unsaturated aliphatic aldehydes, wherein the carbon chain length is 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (Z)-Δ12 unsaturated aliphatic aldehydes, wherein the carbon chain length is 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (E)-Δ12 unsaturated aliphatic aldehydes, wherein the carbon chain length is 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (Z)-Δ13 unsaturated aliphatic aldehydes, wherein the carbon chain length is 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; and (E)-Δ13 unsaturated aliphatic aldehydes, wherein the carbon chain length is 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (For example, (E)7, (Z)9 unsaturated aliphatic aldehydes, wherein the carbon chain length is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (E)3, (Z)8, (Z)11 unsaturated aliphatic aldehydes, wherein the carbon chain length is 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (Z)9, (E)11, (E)13 unsaturated aliphatic aldehydes, wherein the carbon chain length is 14, 15, 16, 17, 18, 19, 20, 21 or 22 unsaturated aliphatic aldehydes; (Z)11, (Z) 13 unsaturated aliphatic aldehydes with a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21 or 22; (Z)9, (E) 12 unsaturated aliphatic aldehydes with a carbon chain length of 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; (E)7, (E) 9 unsaturated aliphatic aldehydes with a carbon chain length of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; and (E)8, (E) 10 unsaturated aliphatic aldehydes with a carbon chain length of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22; etc., for example, (E)7, (Z) 9 unsaturated aliphatic aldehyde with a carbon chain length of 14; (E)3, (Z) 8, (Z) 11 unsaturated aliphatic aldehyde with a carbon chain length of 14; (Z)9, (E) 11, (E) 13 unsaturated aliphatic aldehyde with a carbon chain length of 14; (E)7, (Z) 9 unsaturated aliphatic aldehyde with a carbon chain length of 12; (E)3, (Z) 8, (Z) 11 unsaturated aliphatic aldehyde with a carbon chain length of 12; (Z)9, (E) 11, (E) 13 unsaturated aliphatic aldehyde with a carbon chain length of 12; (E)8, (E) 10 unsaturated aliphatic aldehyde with a carbon chain length of 12; (E)7, (E) 9 unsaturated aliphatic aldehyde with a carbon chain length of 11; (Z)11, (Z) 13 unsaturated aliphatic aldehyde with a carbon chain length of 16; or (Z)9, (E) 12 unsaturated aliphatic aldehyde with a carbon chain length of 14; etc., or Tetradecan-1-ol, pentadecan-1-ol, hexadecan-1-ol, pentadecene-1-ol, (Z)-9-hexadecene-1-ol, (Z)-11-hexadecene-1-ol, (7E,9E)-undeca-7,9-dien-1-ol, (11Z,13Z)-hexadecadien-1-ol, (9Z,12E)-tetradecadien-1-ol, and (8E,10E)-dodecadien-1-ol, etc., The method according to claim 1, selected from the group consisting of:

21. The method is as follows: (a) A step of providing a purified mixture; wherein the purified mixture is: (i) the aliphatic aldehyde; (ii) copper ions; and (iii) a polar solvent, containing, (b) A step of mixing the purified mixture with a nonpolar aprotic solvent and an acid for the purpose of creating an extraction mixture containing a nonpolar phase and a polar phase that enables extraction of the aliphatic aldehyde from the polar phase to the nonpolar phase; and (c) A step of separating the nonpolar phase containing the purified aldehyde from the polar phase, The method according to claim 1, further comprising the step of purifying the aliphatic aldehyde, including:

22. The method according to claim 21, wherein the purified mixture contains 0.05 to 5.0 wt% of copper ions (such as 0.05 to 2.0 wt% of copper ions, such as 0.05 to 1.0 wt% of copper ions).

23. The method according to any one of claims 21 to 22, wherein the acid is selected from the group consisting of C2-C8 monocarboxylic acids, C2-C8 dicarboxylic acids, and C6-C8 tricarboxylic acids (such as acetic acid or citric acid).

24. An aliphatic aldehyde purification method, wherein at least 2.0 molar equivalents (such as at least 2.4 equivalents) of an acid are used with respect to the copper ions. The aliphatic aldehyde purification method according to any one of claims 21 to 22.

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