CN117897373A

CN117897373A - Process for producing fatty aldehyde and derivative thereof

Info

Publication number: CN117897373A
Application number: CN202280052586.9A
Authority: CN
Inventors: A·加布里埃尔松; A·马齐奥塔
Original assignee: Fmc Agricultural Solutions Co ltd
Current assignee: Fmc Agricultural Solutions Co ltd
Priority date: 2021-08-06
Filing date: 2022-08-02
Publication date: 2024-04-16

Abstract

The present invention relates to a process for converting alcohols to aldehydes, in particular fatty alcohols, to fatty aldehydes, which process utilizes a catalyst, wherein the process is capable of providing high conversion of the alcohols, such as large scale conversion, wherein the reaction and purification use relatively small amounts of solvent, and wherein the purification is capable of removing the catalyst from the product aldehyde.

Description

Process for producing fatty aldehyde and derivative thereof

Technical Field

Background

Economical and sustainable oxidation of primary alcohols to aldehydes on an industrial scale is a challenging problem for the chemical industry. Although many methods are described in the literature, most methods are problematic because they use toxic reagents, expensive chemicals, have limited functional group tolerance, have low reaction yields, or require harsh conditions.

There are several oxidation schemes in the academic literature that use copper aminoxy complexes as catalysts. Copper complexes are generally prepared by reacting a copper precursor such as [ Cu ] ^I (CH ₃ CN) ₄ ] ⁺ X ^- Mix to generate in situ, where X is typically an anion, such as tetrafluoroborate, triflate, hexafluorophosphate or halogen, with a ligand, typically 2,2' -Bipyridine (BIPY). Typically, the catalyst system further comprises a base, such as 1-methyl-imidazole (MeIM). The aminooxy group is usually (2, 6-tetramethylpiperidin-1-yl) oxy (TEMPO) or a derivative thereof, for example (4-hydroxy-2, 6-tetramethylpiperidin-1-yl) oxy (4-OH-TEMPO). The aminooxy groups can also be generated in situ from hydroxylamine or an oxyammonium salt. It has been reported that this catalyst system can almost achieve quantitative aldehyde yields when primary alcohols are oxidized by molecular oxygen. However, these reactions are typically carried out on a small scale, using large amounts of solvent (i.e., low concentrations of substrate) and expensive purification. When these methods are applied to industrial raw materials such as complex alcohol mixtures and more concentrated solutions, it is impossible to achieve good reaction yields and selectivities. It is also difficult to remove/recover the catalyst from the reaction medium in a cost effective manner.

Stahl and colleagues describe a typical procedure for oxidizing alcohols and subsequently removing catalyst components (J.Am. Chem. Soc.2011,133, 16901-16910). The procedure was performed on the 1mmol alcohol scale. While this procedure provides acceptable results in the laboratory, it is not suitable for large-scale production of fatty aldehydes, as the large number of steps and the need for column chromatography makes catalyst removal extremely expensive. In addition, the solvent volume of 60 ml of dichloromethane per ml of reaction mixture further increases the cost.

Kumpulain and Ari m.p.koskinen have published methods that do not require column chromatography (chem.eur.j.2009, 15, 10901-10911). The process was carried out on the scale of 10mmol of alcohol (1-decanol, 1.58 g). However, this method requires a large number of steps and a large amount of solvent, making the method unsuitable for industrialization.

Norman Lui et al Tetrahedron Letters (2007) 8823-8828 is directed to novel ligands and CuBrTEMPO for oxidation under fluorous biphasic conditions and thermal form.

Hoover et al, J.am.chem.Soc.2011,133,42,16901-16910 are directed to Cu/TEMPO catalyst systems for the aerobic oxidation of primary alcohols.

Steves et al, j.am.chem.soc.2013,135,42,15742-15745 relate to Cu/TEMPO catalyst systems for the aerobic oxidation of unhindered primary alcohols.

Wei et al, green chem.,2019,21,4069, involve the oxidation of alcohols to aldehydes or ketones using an inorganic ligand supported copper catalyst.

US5155280A1 relates to the preparation of aldehydes which comprise reacting the corresponding alkanol with dissolved stable free radical nitroxides.

The large number of steps involved in the above process is also a problem, as each step is associated with a loss of product. If the conversion is carried out at higher concentrations, the losses increase even further. Furthermore, while the acid used in the work-up has a certain effect in removing the basic components of the reaction mixture (ligand and added base), it does not remove the usual aminooxy radicals, such as 4-Hydroxy-TEMPO or TEMPO, which are very soluble in the fatty aldehyde product mixture. Another disadvantage of most published methods is the use of strong acids (e.g., sulfuric acid) to remove copper. Acids are known to cause side reactions that reduce the overall purity of the product.

For the starting material of the pheromone alcohol mixture, the inventors observed a rapid deactivation of the catalyst. This limits the concentration and amount of aldehyde required in the product, thus requiring expensive and complicated purification, such as distillation or chromatography, which is not feasible on an industrial scale.

Accordingly, there is an unmet need for new processes for converting primary alcohols, such as fatty alcohols, to the corresponding aldehydes, such as fatty aldehydes. To meet this need, the process must be scalable and adaptable to the raw material mixture.

Disclosure of Invention

The present inventors have discovered a convenient method of converting an alcohol composition to an aldehyde composition. The process uses relatively small amounts of solvent, can be extended to industrial scale, even to batch sizes of 100 kg or more, and provides high purity product, particularly in terms of removal of the catalyst composition. The process is particularly suitable for converting a fatty alcohol composition to the corresponding fatty aldehyde composition, as it provides a high degree of conversion of the fatty alcohol composition. Furthermore, the process described herein has the advantage that it limits the competing reactions of oxidation of alcohols to the corresponding acids, and thus the process provides for an alcohol to aldehyde conversion that is significantly higher than the alcohol to acid conversion.

In one aspect, the present disclosure provides a process for converting a fatty alcohol to a fatty aldehyde, the process comprising the steps of:

a) Providing a reaction mixture comprising a fatty alcohol, a catalyst comprising a copper source, and a solvent, and

b) By adding O to the reaction mixture ₂ To oxidize fatty alcohols, O ₂ Is sufficient to convert greater than 50% by weight of the fatty alcohol to fatty aldehyde and less than 50% by weight of the fatty alcohol to fatty acid.

In another aspect, the present invention provides a process for large scale conversion of fatty alcohols to fatty aldehydes, the process comprising the steps of:

a) Providing a reaction mixture comprising at least 1 kg of fatty alcohol, a catalyst comprising a copper source, at least 1 kg of solvent, and a water absorbing or adsorbing material that absorbs or adsorbs water, and

b) By incorporating O into ₂ Is fed into the reaction medium, at least 0.01. Mu. Mol O per minute per. Mol copper in the reaction mixture ₂ Or at least 0.001. Mu. Mol O per minute per. Mu. Mol of starting fatty alcohol in the reaction mixture ₂ Dissolving into the reaction mixture, thereby oxidizing more than 50% by weight of the fatty alcohol to fatty aldehyde and less than 50% by weight of the fatty alcoholAnd forming fatty acid.

In another aspect, the present invention provides a process for converting a fatty alcohol to a fatty aldehyde, the process comprising the steps of:

b) By incorporating O into ₂ Is fed into the reaction mixture, at least 0.01. Mu. Mol O per mu. Mol copper per minute in the reaction mixture ₂ Or at least 0.001. Mu. Mol O per minute per. Mu. Mol of starting fatty alcohol in the reaction mixture ₂ Dissolving into the reaction medium in the reaction mixture, thereby oxidizing more than 50% by weight of the fatty alcohol to fatty aldehyde and less than 50% by weight of the fatty alcohol to fatty acid.

In another aspect of the present disclosure, a process for converting an alcohol to an aldehyde is provided, the process comprising the steps of:

a. providing a reaction mixture comprising an alcohol composition, a catalyst composition disclosed herein, and a solvent disclosed herein, the alcohol composition comprising the alcohol, and

b. the process comprises exposing the reaction mixture to an oxygen stream as disclosed herein by bubbling a gas mixture comprising oxygen through the reaction mixture,

thus, aldehydes were obtained.

One embodiment of the present invention provides a method for purifying fatty aldehydes, comprising the steps of: a. providing a crude reaction product comprising:

i. a fatty aldehyde, and a fatty acid,

copper ions

Polar solvent;

b. mixing the crude reaction product with a non-polar aprotic solvent and an acid to produce a non-polar phase and a polar phase; and

c. the nonpolar phase is separated from the polar phase.

One aspect of the present disclosure provides an aldehyde composition obtained from a process comprising the steps of:

thus obtaining an aldehyde composition.

One aspect of the present disclosure provides a process for converting an alcohol to an acetal, the process comprising the steps of:

a. providing a reaction mixture comprising an alcohol composition, the alcohol composition comprising the alcohol,

b. exposing the reaction mixture to the oxygen stream disclosed herein by bubbling a gas mixture comprising oxygen through the reaction mixture, thereby obtaining an aldehyde, and

c. The aldehyde functionality of the aldehyde is converted to an acetal functionality, thereby yielding an acetal.

One aspect of the present disclosure provides a process for converting an alcohol to an α -hydroxysulfonic acid, the process comprising the steps of:

c. converting the aldehyde functionality of the aldehyde to an alpha-hydroxysulfonic acid functionality,

thereby obtaining the alpha-hydroxysulfonic acid.

One aspect of the present disclosure provides a pheromone component produced from a renewable feedstock, the pheromone component having a biobased carbon content of at least 80%.

In another aspect, the present disclosure provides a composition comprising greater than 93 wt.% fatty aldehyde, less than 7 wt.% fatty alcohol, and less than 2 wt.% water.

In another aspect, a composition is provided that comprises greater than 93% by weight fatty aldehyde, less than 7% by weight fatty alcohol, and less than 2% by weight water.

Drawings

Fig. 1: conversion of fatty alcohols to fatty aldehydes at high oxygen transfer rates. The reaction was left for 2 hours during which the temperature increased from 22 ℃ to 52 ℃ after 1 hour, followed by a decrease in temperature to 42 ℃ after 2 hours. After 73 minutes the reaction yield steadily increased to over 70% and further increased to 87% at 150 minutes.

Fig. 2: conversion of fatty alcohols to fatty aldehydes at high oxygen transfer rates and in the presence of water adsorbents. The reaction was left for 2 hours during which the temperature increased from 22 ℃ to 52 ℃ after 1 hour, followed by a decrease in temperature to 42 ℃ after 2 hours. The conversion rate steadily increased to over 95% at 139 minutes.

Fig. 3: conversion of fatty alcohols to fatty aldehydes at very high oxygen transfer rates and in the presence of water adsorbents. The reaction was left for 2 hours during which the temperature was increased from 23 ℃ to 51 ℃ after 1 minute and 13 minutes, followed by a decrease in temperature to 22 ℃ after 6 hours. The conversion rate steadily increased to more than 99% at 110 minutes.

Fig. 4: at 4m as described in example 16 ³ The fatty alcohol mixture is oxidized in the reactor. FIG. 4 shows the reaction data.

Fig. 5: at 4m as described in example 16 ³ The fatty alcohol mixture is oxidized in the reactor. Fig. 5 shows the conversion over time.

Fig. 6: at 4m as described in example 17 ³ The fatty alcohol mixture is oxidized in the reactor. FIG. 6 shows the reaction data of the oxidation process.

Fig. 7: at 4m as described in example 17 ³ The fatty alcohol mixture is oxidized in the reactor. Fig. 7 shows the conversion over time.

Detailed Description

Definition of the definition

As used herein, terms such as "X comprises Y in the range of n to m" mean that X comprises Y of at least n and up to m. The term means that X does not contain less than n Y and does not contain more than m Y. For example, if a composition is described as comprising Y in the range of 5% to 60%, the composition does not comprise 5% less Y and does not comprise more than 60% Y.

As used herein, the singular terms "a," "an," and "the" are synonymous and used interchangeably with "one or more" and "at least one," unless the language and/or context clearly indicates otherwise. Thus, for example, reference to "a solvent" or "the solvent" in this document or in the appended claims may refer to a single solvent or to more than one solvent.

As used herein, "solvent" includes liquids capable of dissolving or substantially dispersing another substance.

Unless explicitly stated otherwise, reference to "fatty alcohol" or "fatty aldehyde" encompasses both singular and plural forms of the term. For example, a "composition comprising 50 wt% fatty alcohol" may comprise a single fatty alcohol in an amount equal to 50 wt% of the composition, or it may comprise a mixture of two or more fatty alcohols in an amount equal to 50 wt% of the composition.

When describing compounds having carbon-carbon double bonds, the terms "unsaturated" and "desaturated" are used synonymously. The following nomenclature is used throughout this document: Δi desaturated compounds, where i is an integer, refers to compounds having a carbon-carbon double bond or carbon-carbon triple bond between a carbon atom at position i of the carbon chain and a carbon atom at position i+1 of the carbon chain. Thus, the carbon chain length is at least equal to i+1. For example, Δ12 desaturated compounds refer to compounds having a carbon-carbon double bond or carbon-carbon triple bond between carbon 12 and carbon 13, and are referred to herein as carbon chains having a carbon-carbon bond at position 12. The Δ12 desaturated compounds can have a carbon chain length of 13 or greater. The double or triple bond may be in the E or Z configuration. Thus, herein, an Ei or Zi desaturated compound will refer to a compound having a carbon-carbon double bond in the E-configuration or Z-configuration, respectively, between carbon i and carbon i+1 of the carbon chain, wherein the total length of the desaturated compound is at least equal to i+1. For example, an E12 desaturated fatty alcohol has desaturation at position 12 (i.e., a double bond between carbon atom 12 and carbon atom 13) in the E configuration, and has a carbon chain length of 13 or greater.

Furthermore, as used herein, terms such as "(E) 7, (Z) 9", "(E7), (Z9)", "E7, Z9", "(E7, Z9)", "(7E, 9Z)", "(7E), (9Z)", "(7) E, (9) Z", and other variants thereof are synonymous. That is, when stereochemistry of double bonds in a carbon chain is specified, brackets may be written around a term or a part of a term alone, or brackets may be written around the whole stereochemical descriptor set or a combination thereof, or brackets may be omitted entirely, and the position may be given before or after the descriptor. This applies to any combination of any number of stereochemical descriptors used herein.

As used herein, the term "chain length" or "carbon chain length" refers to the number of consecutive carbon atoms in a molecule. For example, the chain length of the molecule hexadecan-1-ol (hexadecan-1-ol) is 16.

Unless otherwise indicated, reference to a position in an organic molecule by position numbering is based on numbering the organic molecule from a functional group, for example by designating the carbon atom to which the hydroxyl group of a primary alcohol is attached as carbon atom 1, or by designating the carbon atom of the portion of the carbonyl group forming the aldehyde as carbon atom 1.

Cloud point: the cloud point of a surfactant (especially a nonionic surfactant) or glycol solution in a solution (e.g., an aqueous 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 occur, and thereby become cloudy. This behavior is characteristic of nonionic surfactants containing polyoxyethylene chains, which exhibit opposite temperature versus solubility behavior in water, and therefore "haze" at some point when the temperature is increased. Diols exhibiting this behavior are referred to as "cloud point diols". The cloud point is affected by salinity, and is generally lower in liquids with higher salt content.

Turbidity concentration: the term is used herein to refer to the concentration of a surfactant, in particular a nonionic surfactant or glycol solution, above which a mixture of the surfactant and the solution begins to phase separate at a given temperature, two phases appear, and become cloudy. For example, the turbidity concentration of a surfactant in an aqueous solution at a given temperature is the minimum concentration of the surfactant that produces two phases when mixed with the aqueous solution. The haze concentration may be obtained from the manufacturer of the surfactant or may be determined experimentally by making a dose curve and determining the concentration at which the mixture phase separates.

As used herein, "X% Y", where Y is a gas, refers to a gas or air mixture, where the Y problem constitutes a partial pressure that is X% of the total pressure of the gas or air mixture. For example, a gas mixture consisting of oxygen at a partial pressure of 0.2 bar and nitrogen at a partial pressure of 0.8 bar is referred to as "20% oxygen" or "20% oxygen mixture".

As used herein, any reference to a volume of gas may refer to the volume of pure gas or a larger volume of gas mixture comprising the gas. For example, "1.5ml oxygen" may refer to 1.5ml pure oxygen or 7.5ml of a gas mixture comprising 20% oxygen.

Unless otherwise specified, any reference to gas volume should be considered at a pressure of 1.00 bar.

As used herein in the context of gases, any reference to "oxygen" refers to O ₂ 。

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

As used herein, the term "aldehyde" includes the term "fatty aldehyde". As used herein, the term "aldehyde composition" includes the term "fatty aldehyde composition".

As used herein, the term "acetal" includes the term "fatty acetal". As used herein, the term "acetal composition" includes the term "fatty acetal composition".

As used herein, the term "alpha-hydroxysulfonic acid" includes the term "fatty alpha-hydroxysulfonic acid". As used herein, the term "a-hydroxysulfonic acid composition" includes the term "aliphatic a-hydroxysulfonic acid composition".

The unit ppm as used herein is on a weight basis unless otherwise indicated.

As used herein, the term "used" refers to an oxidizing agent that has acted as a peroxidative agent. For example, O ₂ Is an oxidizing agent, and H ₂ O is its corresponding spent oxidant. For example, the compound TEMPO is the oxidizing agent, while the compound N-hydroxy-2, 6-tetramethylpiperidine is its corresponding waste oxidizing agent. Spent oxidant may also be referred to as spent oxidant. The spent oxidant is typically a reduced form of the corresponding oxidant.

Fatty alcohols

The present disclosure relates to fatty alcohol compositions 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 several fatty alcohols, e.g. 2 to 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, for example 6 or more fatty alcohols.

In a preferred embodiment of the present disclosure, the fatty alcohol is a primary fatty alcohol. In particular, in one embodiment of the present disclosure, the conversion of a fatty alcohol to a fatty aldehyde as disclosed herein is the conversion of a primary alcohol functional group to an aldehyde functional group. In a preferred embodiment of the present disclosure, the conversion is oxidation of a primary alcohol functional group to an aldehyde functional group.

It is believed that a number of different primary alcohols can be converted to the corresponding aldehydes using the methods disclosed herein. The process is particularly suitable for converting fatty alcohols to the corresponding fatty aldehydes, since other known processes either produce incomplete conversion or produce undesired by-products, and/or require large amounts of solvent.

The fatty alcohol may be saturated fatty alcohol or 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 desaturated fatty alcohols. In yet another embodiment of the present disclosure, the alcohol composition comprises both saturated fatty alcohols and desaturated fatty alcohols.

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

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

In a preferred embodiment of the present disclosure, the fatty alcohol has a chain length of 12 to 16. In another embodiment of the present disclosure, the fatty alcohol is unbranched and has a chain length of 12 to 16. In a preferred embodiment of the present disclosure, the fatty alcohol is unbranched and has a chain length of 12. In another even more preferred embodiment, the fatty alcohol is unbranched and has a chain length of 14. In another even more preferred embodiment, the fatty alcohol is unbranched with a chain length of 16.

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 fatty alcohol having a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22.

In one embodiment of the present disclosure, the fatty alcohol is a desaturated fatty alcohol. The double bond of the desaturated fatty alcohol can have an E or Z configuration unless the double bond is a terminal double bond. In one embodiment of the present disclosure, the fatty alcohol comprises one or more E-configuration double bonds. In one embodiment of the present disclosure, the fatty alcohol comprises one or more Z-configuration double bonds. In yet another embodiment, the fatty alcohol comprises one or more E-configured double bonds and one or more Z-configured double bonds.

In some embodiments, the fatty alcohol is a desaturated fatty alcohol. Such compounds are naturally occurring, e.g., produced by insect cells, which act as pheromones. The desaturated fatty alcohols can be:

-a (Z) - Δ3 desaturated fatty alcohol having a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-an (E) - Δ3 desaturated fatty alcohol having a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-a (Z) - Δ5 desaturated fatty alcohol having a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-an (E) - Δ5 desaturated fatty alcohol having a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-a (Z) - Δ6 desaturated fatty alcohol having a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-an (E) - Δ6 desaturated fatty alcohol having a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-a (Z) - Δ7 desaturated fatty alcohol having a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-an (E) - Δ7 desaturated fatty alcohol having a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-a (Z) - Δ8 desaturated fatty alcohol having a carbon chain length of 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-an (E) - Δ8 desaturated fatty alcohol having a carbon chain length of 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-a (Z) - Δ9 desaturated fatty alcohol having a carbon chain length of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-an (E) - Δ9 desaturated fatty alcohol having a carbon chain length of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-a (Z) - Δ10 desaturated fatty alcohol having a carbon chain length of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-an (E) - Δ10 desaturated fatty alcohol having a carbon chain length of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

(Z) - Δ11 desaturated fatty alcohols having carbon chain lengths of 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-an (E) - Δ11 desaturated fatty alcohol having a carbon chain length of 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-a (Z) - Δ12 desaturated fatty alcohol having a carbon chain length of 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-an (E) - Δ12 desaturated fatty alcohol having a carbon chain length of 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-a (Z) - Δ13 desaturated fatty alcohol having a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21 or 22; and

-an (E) - Δ13 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 desaturated fatty alcohol having a carbon chain length of 12, for example:

-a (Z) - Δ5 unsaturated fatty alcohol having a carbon chain length of 12;

-a (E) - Δ5 desaturated fatty alcohol having a carbon chain length of 12;

-a (Z) - Δ6 desaturated fatty alcohol with a carbon chain length of 12;

-an (E) - Δ6 desaturated fatty alcohol having a carbon chain length of 12;

-a (Z) - Δ7 desaturated fatty alcohol with a carbon chain length of 12;

-a (E) - Δ7 desaturated fatty alcohol with a carbon chain length of 12;

-a (Z) - Δ8 desaturated fatty alcohol with a carbon chain length of 12;

-a (E) - Δ8 desaturated fatty alcohol having a carbon chain length of 12;

-a (Z) - Δ9 desaturated fatty alcohol with a carbon chain length of 12;

-a (E) - Δ9 desaturated fatty alcohol having a carbon chain length of 12;

-a (Z) - Δ10 unsaturated fatty alcohol having a carbon chain length of 12;

-an (E) - Δ10 unsaturated fatty alcohol having a carbon chain length of 12;

-a (Z) - Δ11 unsaturated fatty alcohol having a carbon chain length of 12; and

-a (E) - Δ11 desaturated fatty alcohol with a carbon chain length of 12.

In some embodiments, the fatty alcohol is a desaturated fatty alcohol having a carbon chain length of 14, for example: -a (Z) - Δ5 unsaturated fatty alcohol having a carbon chain length of 14;

-an (E) - Δ5 desaturated fatty alcohol having a carbon chain length of 14;

-a (Z) - Δ6 unsaturated fatty alcohol having a carbon chain length of 14;

-an (E) - Δ6 desaturated fatty alcohol having a carbon chain length of 14;

-a (Z) - Δ7 desaturated fatty alcohol with a carbon chain length of 14;

-a (E) - Δ7 desaturated fatty alcohol with a carbon chain length of 14;

-a (Z) - Δ8 desaturated fatty alcohol with a carbon chain length of 14;

-an (E) - Δ8 desaturated fatty alcohol having a carbon chain length of 14;

-a (Z) - Δ9 desaturated fatty alcohol with a carbon chain length of 14;

-a (E) - Δ9 desaturated fatty alcohol with a carbon chain length of 14;

-a (Z) - Δ10 desaturated fatty alcohol with a carbon chain length of 14;

-a (E) - Δ10 desaturated fatty alcohol with a carbon chain length of 14;

-a (Z) - Δ11 desaturated fatty alcohol with a carbon chain length of 14;

-a (E) - Δ11 desaturated fatty alcohol with a carbon chain length of 14;

-a (Z) - Δ12 desaturated fatty alcohol with a carbon chain length of 14;

-a (E) - Δ12 desaturated fatty alcohol with a carbon chain length of 14;

-a (Z) - Δ13 desaturated fatty alcohol with a carbon chain length of 14; and

-a (E) - Δ13 desaturated fatty alcohol with a carbon chain length of 14.

In some embodiments, the fatty alcohol is a desaturated fatty alcohol having a carbon chain length of 16, for example: -a (Z) - Δ5 unsaturated fatty alcohol having a carbon chain length of 16;

-a (E) - Δ5 desaturated fatty alcohol with a carbon chain length of 16;

-a (Z) - Δ6 desaturated fatty alcohol with a carbon chain length of 16;

-an (E) - Δ6 desaturated fatty alcohol with a carbon chain length of 16;

-a (Z) - Δ7 desaturated fatty alcohol with a carbon chain length of 16;

-a (E) - Δ7 desaturated fatty alcohol with a carbon chain length of 16;

-a (Z) - Δ8 desaturated fatty alcohol with a carbon chain length of 16;

-a (E) - Δ8 desaturated fatty alcohol with a carbon chain length of 16;

-a (Z) - Δ9 desaturated fatty alcohol with a carbon chain length of 16;

-a (E) - Δ9 desaturated fatty alcohol with a carbon chain length of 16;

-a (Z) - Δ10 desaturated fatty alcohol with a carbon chain length of 16;

-a (E) - Δ10 desaturated fatty alcohol with a carbon chain length of 16;

-a (Z) - Δ11 desaturated fatty alcohol with a carbon chain length of 16;

-a (E) - Δ11 desaturated fatty alcohol with a carbon chain length of 16;

-a (Z) - Δ12 desaturated fatty alcohol with a carbon chain length of 16;

-a (E) - Δ12 desaturated fatty alcohol with a carbon chain length of 16;

-a (Z) - Δ13 desaturated fatty alcohol with a carbon chain length of 16; and

-a (E) - Δ13 desaturated fatty alcohol with a carbon chain length of 16.

For example, the fatty alcohol is (E) 7, (Z) 9 desaturated fatty alcohol having carbon chain lengths of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20. In some embodiments, the fatty alcohol is a (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 a (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 (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 (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 (E7, (E9) a 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 (E8, (E10) a desaturated fatty alcohol having a carbon chain length of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22.

In other embodiments, the fatty alcohol is (E) 7, (Z) 9 desaturated fatty alcohol having a carbon chain length of 14. In other embodiments, the desaturated fatty alcohol is (E) 3, (Z) 8, (Z) 11 desaturated fatty alcohol having a carbon chain length of 14. In other embodiments, the desaturated fatty alcohol is a (Z) 9, (E) 11, (E) 13 desaturated fatty alcohol having a carbon chain length of 14. For example, the fatty alcohol is (E) 7, (Z) 9 desaturated fatty alcohol with a carbon chain length of 12. In other embodiments, the desaturated fatty alcohol is (E) 3, (Z) 8, (Z) 11 desaturated fatty alcohol having a carbon chain length of 12. In other embodiments, the desaturated fatty alcohol is a (Z) 9, (E) 11, (E) 13 desaturated fatty alcohol having a carbon chain length of 12. In other embodiments, the desaturated fatty alcohol is (E) 8, (E) 10 desaturated fatty alcohol having a carbon chain length of 12. In other embodiments, the desaturated fatty alcohol is (E) 7, (E) 9 desaturated fatty alcohol having a carbon chain length of 11. In other embodiments, the desaturated fatty alcohol is a (Z) 11, (Z) 13 desaturated fatty alcohol having a carbon chain length of 16. In other embodiments, the desaturated fatty alcohol is a (Z) 9, (E) 12 desaturated fatty alcohol having a carbon chain length of 14.

In some embodiments, the fatty alcohol is (Z9, E12) -tetradecadien-1-ol. The microbial cell factory and the method of obtaining (Z9, E12) -tetradecadien-1-ol from yeast cells are described in detail in application EP21183447.8 entitled "Methods andyeast cells forproduction ofdesaturated compounds (method for producing desaturated compounds and yeast cells)" filed by the same applicant at day 7, month 2 of 2021.

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 application EP21183459.3 entitled "Methods and yeast cells forproduction of desaturated compounds (method for producing desaturated compounds and yeast cells)" filed by the same applicant at month 7 and 2 of 2021.

In some embodiments, the fatty 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 application WO 2021/123128.

In some embodiments, the fatty alcohol is (zl) -hexadecen-1-ol. Microbial cell factories and methods for obtaining (Z11) -hexadecen-1-ol from yeast cells are described in detail in application WO 2016/207339.

In a preferred embodiment of the invention, the fatty alcohol has a double bond in position 9, 11 or 13, or in positions 9 and 11 or in positions 11 and 13; alternatively, the fatty alcohol has a double bond at the 9-or 12-position, or double bonds at the 9-and 12-positions. In an even more preferred embodiment of the present disclosure, the fatty alcohol has a chain length of 12 and a double bond at the 9 or 11 positions, or double bonds 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 position, or a double bond at the 9 and 12 positions; or the fatty alcohol has a chain length of 14 and has a double bond at positions 9, 11 or 13, or has double bonds at positions 9 and 11, or at positions 11 and 13. In another more preferred embodiment of the invention, the fatty alcohol has a chain length of 14 and has a double bond at the 9-or 11-position, or has double bonds at the 9-and 11-positions. In another more preferred embodiment of the invention, the fatty alcohol has a chain length of 16 and has double bonds at positions 9 and 11, or double bonds at positions 9 and 11. In other embodiments, the fatty alcohol has a chain length of 16 and has a double bond at the 11 or 13 positions, or has double bonds at the 11 and 13 positions. In other embodiments, the fatty alcohol has a chain length of 12, a double bond at the 8-or 10-position, or a double bond at the 8-and 10-positions.

In a specific embodiment, the fatty alcohol is selected from the group consisting of: tetradecan-1-ol, pentadecyl-1-ol, hexadecan-1-ol, pentadecyl-1-ol, (Z) -9-hexadecen-1-ol, (Z) -11-hexadecen-1-ol, (7E, 9E) -undec-7, 9-dien-1-ol, (11Z, 13Z) -hexadecen-1-ol, (9Z, 12E) -tetradecan-dien-1-ol, and (8E, 10E) -dodecadien-1-ol. In a specific embodiment, the fatty alcohol is (Z) -11-hexadecen-1-ol or (Z) -9-tetradecen-1-ol.

The fatty alcohol composition may consist entirely of fatty alcohols, or it may comprise fatty alcohols and other compounds. In one embodiment of the present disclosure, the fatty alcohol composition comprises from 5 to 10 weight percent of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises from 10 to 20 weight percent of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises from 20 to 30 weight percent of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises from 30 to 40 weight percent of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises from 40 to 50 weight percent of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises from 50 to 60 weight percent of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises from 60 to 70 weight percent of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises from 70 to 80 weight percent of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises from 80 to 90 weight percent of one or more fatty alcohols. In another embodiment, the fatty alcohol composition comprises from 90 to 100 weight percent 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 an even more preferred embodiment, the fatty alcohol composition comprises one or more fatty alcohols in the range of 60% to 100%.

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

In a preferred embodiment of the present disclosure, the fatty alcohol composition is substantially dry, i.e. it contains at most only a small amount of water. In a preferred embodiment of the present disclosure, the fatty alcohol composition does not comprise any compounds that would detrimentally interfere with oxidation. Compounds which are considered to be detrimental to the reaction conditions are, for example: carboxylic acids, amino acids, amines, 1, 2-diols, 1, 3-diols, sulfides and other chelating compounds.

The presently disclosed process is believed to be particularly useful for the oxidation of alcohols or pheromone alcohols derived from raw materials. In one embodiment of the present disclosure, the fatty alcohol composition is derived from a feedstock. In one embodiment of the present disclosure, the fatty alcohol composition comprises a pheromone alcohol.

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 to 100 weight percent. In a specific embodiment of the present disclosure, the fatty alcohol composition comprises (Z) -11-hexadecen-1-ol. In another specific embodiment of the present invention, the fatty alcohol composition comprises from 10 to 100% by weight of (Z) -11-hexadecen-1-ol. In another specific embodiment of the present disclosure, the fatty alcohol composition comprises 50 to 100 weight percent (Z) -11-hexadecen-1-ol. In a specific embodiment of the present disclosure, the fatty alcohol composition comprises (Z) -9-hexadecen-1-ol. In another specific embodiment of the present invention, the fatty alcohol composition comprises 1 to 10% by weight of (Z) -9-hexadecen-1-ol. In a specific embodiment of the present disclosure, the fatty alcohol composition comprises hexadecan-1-ol. In another specific embodiment of the present disclosure, the fatty alcohol composition comprises 1 to 15 weight percent 1 hexadecan-1-ol. In a specific embodiment of the present disclosure, the alcohol composition comprises 50 to 98 wt% of (Z) -11-hexadecen-1-ol, 1 to 10 wt% of (Z) -9-hexadecen-1-ol, and 1 to 15 wt% of hexadecan-1-ol.

In one embodiment of the present disclosure, the fatty alcohol composition comprises 10 to 100 weight percent (Z) -11-hexadecen-1-ol. In one embodiment of the present disclosure, the fatty alcohol composition comprises 1 to 10 weight percent (Z) -9-hexadecen-1-ol. In one embodiment of the present disclosure, the fatty alcohol composition comprises 1 to 15 weight percent hexadecan-1-ol. In one embodiment of the present disclosure, the fatty alcohol composition comprises 1 to 20 weight percent monounsaturated pentadecen-1-ol. In a specific embodiment, the fatty alcohol composition comprises from 10 to 100 weight percent (Z) -11-hexadecen-1-ol, from 1 to 10 weight percent (Z) -9-hexadecen-1-ol, from 1 to 15 weight percent hexadecan-1-ol, and from 1 to 20 weight percent monounsaturated pentadecen-1-ol.

Fatty aldehyde

The present disclosure relates to fatty aldehyde compositions comprising at least one fatty aldehyde. In one embodiment of the present disclosure, the fatty aldehyde composition consists of or comprises a single fatty aldehyde. In another embodiment, the fatty aldehyde composition consists of or comprises a mixture of several fatty aldehydes, for example 2 to 5 fatty aldehydes. In yet another embodiment, the fatty aldehyde composition consists of or comprises several fatty aldehydes, for example 6 or more fatty aldehydes.

The fatty aldehyde may be a saturated fatty aldehyde, a desaturated fatty aldehyde. In one embodiment of the present disclosure, the fatty aldehyde composition comprises only saturated fatty aldehydes. In another embodiment, the fatty aldehyde composition comprises only desaturated fatty aldehydes. In yet another embodiment of the present disclosure, the aldehyde composition comprises both saturated fatty aldehydes and desaturated fatty aldehydes.

In one embodiment, the fatty aldehyde has a chain length of 8. In another embodiment, the fatty aldehyde has a chain length of 9. In another embodiment, the fatty aldehyde has a chain length of 10. In another embodiment, the fatty aldehyde has a chain length of 11. In another embodiment, the fatty aldehyde has a chain length of 12. In another embodiment, the fatty aldehyde has a chain length of 13. In another embodiment, the fatty aldehyde has a chain length of 14. In another embodiment, the fatty aldehyde has a chain length of 15. In another embodiment, the fatty aldehyde has a chain length of 16. In another embodiment, the fatty aldehyde has a chain length of 17. In another embodiment, the fatty aldehyde has a chain length of 18. In another embodiment, the fatty aldehyde has a chain length of 19. In another embodiment, the fatty aldehyde has a chain length of 20. In another embodiment, the fatty aldehyde has a chain length of 21. In another embodiment, the fatty aldehyde has a chain length of 22.

The fatty aldehyde may be branched or unbranched (i.e., linear chain or "straight chain"). In a preferred embodiment of the invention, the fatty aldehyde is unbranched.

In a preferred embodiment of the present disclosure, the fatty aldehyde has a chain length of 12 to 16. In another embodiment of the present disclosure, the fatty aldehyde is unbranched and has a chain length of 12 to 16. In a preferred embodiment of the present disclosure, the fatty aldehyde is unbranched and has a chain length of 12. In another even more preferred embodiment, the fatty aldehyde is unbranched and has a chain length of 14. In another even more preferred embodiment, the fatty aldehyde is unbranched and has a chain length of 16.

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

In one embodiment of the present disclosure, the fatty aldehyde is a desaturated fatty aldehyde. The double bond of the desaturated fatty aldehyde can have an E or Z configuration unless the double bond is a terminal double bond. In one embodiment of the present disclosure, the fatty aldehyde comprises one or more E-configuration double bonds. In one embodiment of the present disclosure, the fatty aldehyde comprises one or more Z-configuration double bonds. In yet another embodiment, the fatty aldehyde comprises one or more E-configured double bonds and one or more Z-configured double bonds.

In some embodiments, the fatty aldehyde is a desaturated fatty aldehyde. The desaturated fatty aldehydes can be: -a (Z) - Δ3 desaturated fatty aldehyde having a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-an (E) - Δ3 desaturated fatty aldehyde having a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-a (Z) - Δ5 desaturated fatty aldehyde having a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-an (E) - Δ5 desaturated fatty aldehyde having a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-a (Z) - Δ6 desaturated fatty aldehyde having a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-an (E) - Δ6 desaturated fatty aldehyde having a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-a (Z) - Δ7 desaturated fatty aldehyde having a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-an (E) - Δ7 desaturated fatty aldehyde having a carbon chain length of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-a (Z) - Δ8 desaturated fatty aldehyde having a carbon chain length of 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-an (E) - Δ8 desaturated fatty aldehyde having a carbon chain length of 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

(Z) - Δ9 desaturated fatty aldehydes having a carbon chain length of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-an (E) - Δ9 desaturated fatty aldehyde having a carbon chain length of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-a (Z) - Δ10 unsaturated fatty aldehyde having a carbon chain length of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-an (E) - Δ10 desaturated fatty aldehyde having a carbon chain length of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

(Z) - Δ11 desaturated fatty aldehydes having a carbon chain length of 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-an (E) - Δ11 desaturated fatty aldehyde having a carbon chain length of 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

(Z) - Δ12 desaturated fatty aldehydes having a carbon chain length of 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-an (E) - Δ12 desaturated fatty aldehyde having a carbon chain length of 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

-a (Z) - Δ13 desaturated fatty aldehyde having a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21 or 22; and

-an (E) - Δ13 desaturated fatty aldehyde having a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21 or 22.

In some embodiments, the fatty aldehyde is a desaturated fatty aldehyde having a carbon chain length of 12, for example:

-a (Z) - Δ5 desaturated fatty aldehyde with a carbon chain length of 12;

-a (E) - Δ5 desaturated fatty aldehyde with a carbon chain length of 12;

-a (Z) - Δ6 desaturated fatty aldehyde with a carbon chain length of 12;

-a (E) - Δ6 desaturated fatty aldehyde with a carbon chain length of 12;

-a (Z) - Δ7 desaturated fatty aldehyde with a carbon chain length of 12;

-a (E) - Δ7 desaturated fatty aldehyde with a carbon chain length of 12;

-a (Z) - Δ8 desaturated fatty aldehyde with a carbon chain length of 12;

-a (E) - Δ8 desaturated fatty aldehyde with a carbon chain length of 12;

-a (Z) - Δ9 desaturated fatty aldehyde with a carbon chain length of 12;

-a (E) - Δ9 desaturated fatty aldehyde with a carbon chain length of 12;

-a (Z) - Δ10 desaturated fatty aldehyde with a carbon chain length of 12;

-a (E) - Δ10 desaturated fatty aldehyde with a carbon chain length of 12;

-a (Z) - Δ11 desaturated fatty aldehyde with a carbon chain length of 12; and

-a (E) - Δ11 desaturated fatty aldehyde with a carbon chain length of 12.

In some embodiments, the fatty aldehyde is a desaturated fatty aldehyde having a carbon chain length of 14, for example: -a (Z) - Δ5 desaturated fatty aldehyde with a carbon chain length of 14;

-a (E) - Δ5 desaturated fatty aldehyde with a carbon chain length of 14;

-a (Z) - Δ6 desaturated fatty aldehyde with a carbon chain length of 14;

-a (E) - Δ6 desaturated fatty aldehyde with a carbon chain length of 14;

-a (Z) - Δ7 desaturated fatty aldehyde with a carbon chain length of 14;

-a (E) - Δ7 desaturated fatty aldehyde with a carbon chain length of 14;

-a (Z) - Δ8 desaturated fatty aldehyde with a carbon chain length of 14;

-a (E) - Δ8 desaturated fatty aldehyde with a carbon chain length of 14;

-a (Z) - Δ9 desaturated fatty aldehyde with a carbon chain length of 14;

-a (E) - Δ9 desaturated fatty aldehyde with a carbon chain length of 14;

-a (Z) - Δ10 desaturated fatty aldehyde with a carbon chain length of 14;

-a (E) - Δ10 desaturated fatty aldehyde with a carbon chain length of 14;

-a (Z) - Δ11 desaturated fatty aldehyde with a carbon chain length of 14;

-a (E) - Δ11 desaturated fatty aldehyde with a carbon chain length of 14;

-a (Z) - Δ12 desaturated fatty aldehyde with a carbon chain length of 14;

-a (E) - Δ12 desaturated fatty aldehyde with a carbon chain length of 14;

-a (Z) - Δ13 desaturated fatty aldehyde with a carbon chain length of 14; and

-a (E) - Δ13 desaturated fatty aldehyde with a carbon chain length of 14.

In some embodiments, the fatty aldehyde is a desaturated fatty aldehyde having a carbon chain length of 16, for example: -a (Z) - Δ5 desaturated fatty aldehyde with a carbon chain length of 16;

-a (E) - Δ5 desaturated fatty aldehyde with a carbon chain length of 16;

-a (Z) - Δ6 desaturated fatty aldehyde with a carbon chain length of 16;

-a (E) - Δ6 desaturated fatty aldehyde with a carbon chain length of 16;

-a (Z) - Δ7 desaturated fatty aldehyde with a carbon chain length of 16;

-a (E) - Δ7 desaturated fatty aldehyde with a carbon chain length of 16;

-a (Z) - Δ8 desaturated fatty aldehyde with a carbon chain length of 16;

-a (E) - Δ8 desaturated fatty aldehyde with a carbon chain length of 16;

-a (Z) - Δ9 desaturated fatty aldehyde with a carbon chain length of 16;

-a (E) - Δ9 desaturated fatty aldehyde with a carbon chain length of 16;

-a (Z) - Δ10 desaturated fatty aldehyde with a carbon chain length of 16;

-a (E) - Δ10 desaturated fatty aldehyde with a carbon chain length of 16;

-a (Z) - Δ11 desaturated fatty aldehyde with a carbon chain length of 16;

-a (E) - Δ11 desaturated fatty aldehyde with a carbon chain length of 16;

-a (Z) - Δ12 desaturated fatty aldehyde with a carbon chain length of 16;

-a (E) - Δ12 desaturated fatty aldehyde with a carbon chain length of 16;

-a (Z) - Δ13 desaturated fatty aldehyde with a carbon chain length of 16; and

-a (E) - Δ13 desaturated fatty aldehyde with a carbon chain length of 16.

For example, the fatty aldehyde is (E) 7, (Z) 9 desaturated fatty 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 fatty aldehyde is a (E) 3, (Z) 8, (Z) 11 desaturated fatty 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 fatty aldehyde is a (Z) 9, (E) 11, (E) 13 desaturated fatty aldehyde having a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21, or 22. In some embodiments, the fatty aldehyde is a (Z) 11, (Z) 13 desaturated fatty aldehyde having a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21, or 22. In some embodiments, the fatty aldehyde is a (Z) 9, (E) 12 desaturated fatty aldehyde having a carbon chain length of 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22. In some embodiments, the fatty aldehyde is (E7, (E9) desaturated fatty 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 fatty aldehyde is (E8, (E10) a desaturated fatty aldehyde having a carbon chain length of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22.

In other embodiments, the fatty aldehyde is (E) 7, (Z) 9 desaturated fatty aldehyde having a carbon chain length of 14. In other embodiments, the desaturated fatty aldehyde is (E) 3, (Z) 8, (Z) 11 desaturated fatty aldehyde having a carbon chain length of 14. In other embodiments, the desaturated fatty aldehyde is a (Z) 9, (E) 11, (E) 13 desaturated fatty aldehyde having a carbon chain length of 14. For example, the fatty aldehyde is (E) 7, (Z) 9 desaturated fatty aldehyde with a carbon chain length of 12. In other embodiments, the desaturated fatty aldehyde is (E) 3, (Z) 8, (Z) 11 desaturated fatty aldehyde having a carbon chain length of 12. In other embodiments, the desaturated fatty aldehyde is a (Z) 9, (E) 11, (E) 13 desaturated fatty aldehyde having a carbon chain length of 12. In other embodiments, the desaturated fatty aldehyde is (E) 8, (E) 10 desaturated fatty aldehyde having a carbon chain length of 12. In other embodiments, the desaturated fatty aldehyde is (E) 7, (E) 9 desaturated fatty aldehyde having a carbon chain length of 11. In other embodiments, the desaturated fatty aldehyde is a (Z) 11, (Z) 13 desaturated fatty aldehyde having a carbon chain length of 16. In other embodiments, the desaturated fatty aldehyde is a (Z) 9, (E) 12 desaturated fatty aldehyde having a carbon chain length of 14.

In some embodiments, the fatty aldehyde is (Z9, E12) -tetradecadiene-1-aldehyde. Microbial cell factories and methods for obtaining the corresponding alcohols (Z9, E12) -tetradecadien-1-ols from yeast cells are described in detail in application EP21183447.8 entitled "Methods and yeast cells for production ofdesaturated compounds (method for producing desaturated compounds and yeast cells)" filed by the same applicant at month 7 and 2 of 2021. The alcohol can be converted to (Z9, E12) -tetradecadiene-1-aldehyde using the methods disclosed herein.

In some embodiments, the fatty aldehyde is (Z11, Z13) -hexadecadiene-1-aldehyde. Microbial cell factories and methods for obtaining the corresponding alcohols (Z11, Z13) -hexadecadien-1-ols from yeast cells are described in detail in application EP21183459.3 entitled "Methods and yeast cells for production ofdesaturated compounds (method for producing desaturated compounds and yeast cells)" filed by the same applicant at month 7 and 2 of 2021. The alcohol can be converted to Z11, Z13) -hexadecadiene-1-aldehyde using the methods disclosed herein.

In some embodiments, the fatty aldehyde is (E8, E10) -dodecadien-1-al. The microbial cell factory and the method of obtaining the corresponding alcohol (E8, E10) -hexadecadien-1-ol from yeast cells are described in detail in application WO 2021/123128. The alcohol can be converted to (E8, E10) -dodecene-1-aldehyde using the methods disclosed herein.

In some embodiments, the fatty aldehyde is (zl) -hexadecene-1-aldehyde. The microbial cell factory and the method of obtaining the corresponding alcohol (Z11) -hexadecen-1-ol from yeast cells are described in detail in application WO 2016/207339. The alcohol can be converted to (Z11) -hexadecene-1-aldehyde using the methods disclosed herein.

In a preferred embodiment of the invention, the fatty aldehyde has a double bond in position 9, 11 or 13, or in positions 9 and 11 or in positions 11 and 13; alternatively, the fatty aldehyde has a double bond at the 9-or 12-position, or double bonds at the 9-and 12-positions. In an even more preferred embodiment of the present disclosure, the fatty aldehyde has a chain length of 12 and a double bond at the 9 or 11 positions, or double bonds at the 9 and 11 positions; alternatively, the fatty aldehyde has a chain length of 14 and a double bond at the 9 or 12 position, or a double bond at the 9 and 12 positions; or the fatty aldehyde has a chain length of 14 and has a double bond at the 9-, 11-or 13-position, or has a double bond at the 9-and 11-positions, or at the 11-and 13-positions. In another more preferred embodiment of the present invention, the fatty aldehyde has a chain length of 14 and has a double bond at the 9-or 11-position, or has double bonds at the 9-and 11-positions. In another more preferred embodiment of the present invention, the fatty aldehyde has a chain length of 16 and has double bonds at positions 9 and 11, or double bonds at positions 9 and 11. In other embodiments, the fatty aldehyde has a chain length of 16 and has a double bond at the 11 or 13 positions, or double bonds at the 11 and 13 positions. In other embodiments, the fatty aldehyde has a chain length of 12, a double bond at the 8-or 10-position, or a double bond at the 8-and 10-positions.

In a specific embodiment, the fatty aldehyde is selected from the group consisting of: tetradecane-1-aldehyde, pentadecyl-1-aldehyde, hexadecane-1-aldehyde, pentadecyl-1-aldehyde, (Z) -9-hexadecene-1-aldehyde, (Z) -11-hexadecene-1-aldehyde, (7E, 9E) -undecane-7, 9-diene-1-aldehyde, (11Z, 13Z) -hexadecene-1-aldehyde, (9Z, 12E) -tetradecene-1-aldehyde and (8E, 10E) -dodecene-1-aldehyde.

In a specific embodiment, the fatty aldehyde is (Z) -11-hexadecenal or (Z) -9-tetradecenal.

The fatty aldehyde composition may consist entirely of fatty aldehydes, or it may comprise fatty aldehydes and other compounds. In one embodiment of the present disclosure, the fatty aldehyde composition comprises 5 to 10 weight percent of one or more fatty aldehydes. In another embodiment, the fatty aldehyde composition comprises from 10 to 20 weight percent of one or more fatty aldehydes. In another embodiment, the fatty aldehyde composition comprises 20 to 30 weight percent of one or more fatty aldehydes. In another embodiment, the fatty aldehyde composition comprises from 30 to 40 weight percent of one or more fatty aldehydes. In another embodiment, the fatty aldehyde composition comprises 40 to 50 weight percent of one or more fatty aldehydes. In another embodiment, the fatty aldehyde composition comprises from 50 to 60 weight percent of one or more fatty aldehydes. In another embodiment, the fatty aldehyde composition comprises from 60 to 70 weight percent of one or more fatty aldehydes. In another embodiment, the fatty aldehyde composition comprises from 70 to 80 weight percent of one or more fatty aldehydes. In another embodiment, the fatty aldehyde composition comprises 80 to 90 weight percent of one or more fatty aldehydes. In another embodiment, the fatty aldehyde composition comprises from 90 to 100 weight percent of one or more fatty aldehydes. In a preferred embodiment of the present disclosure, the fatty aldehyde composition comprises one or more fatty aldehydes in the range of 50% to 100%. In an even more preferred embodiment, the fatty aldehyde composition comprises one or more fatty aldehydes in the range of 60% to 100%.

In one embodiment of the present disclosure, the fatty aldehyde composition comprises at least 30% by weight of one or more fatty aldehydes. In another embodiment, the fatty aldehyde composition comprises at least 35% by weight of one or more fatty aldehydes. In another embodiment, the fatty aldehyde composition comprises at least 40% by weight of one or more fatty aldehydes. In another embodiment, the fatty aldehyde composition comprises at least 45% by weight of one or more fatty aldehydes. In another embodiment, the fatty aldehyde composition comprises at least 50% by weight of one or more fatty aldehydes. In another embodiment, the fatty aldehyde composition comprises at least 55% by weight of one or more fatty aldehydes. In another embodiment, the fatty aldehyde composition comprises at least 60% by weight of one or more fatty aldehydes. In a preferred embodiment, the fatty aldehyde composition comprises at least 70% by weight of one or more fatty aldehydes. In another preferred embodiment, the fatty aldehyde composition comprises at least 80% by weight of one or more fatty aldehydes. In another preferred embodiment, the fatty aldehyde composition comprises at least 90% by weight of one or more fatty aldehydes.

Embodiments of the aldehyde compositions outlined herein preferably refer to isolated, purified aldehyde compositions.

Catalyst composition

The present disclosure relates to the oxidation of primary alcohols to produce the corresponding aldehydes. The oxidation of primary alcohols to aldehydes is catalyzed by the catalyst composition.

The catalyst composition comprises a copper (I) source such as, for example, a copper (I) salt. The copper (I) source is a source containing copper (II) useful in the processAnd substances or mixtures of substances of the copper (I) compounds for the desired catalysis of copper (I). Examples include copper (I) chloride, copper (I) bromide, copper (I) iodide, copper (I) cyanide, copper (I) oxide, copper (I) triflate, copper (I) tetraacetonitrile tetrafluoroborate, copper (I) tetraphenylborate, copper (I) tetraacetonitrile hexafluorophosphate, copper (I) tetraacetonitrile triflate, copper (I) sulfide, copper (I) thiocyanate, cu [1, 3-bis (2, 6-diisopropylphenyl) imidazol-2-ylidene]Cl, 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 Wherein R is ² Selected from alkyl groups, preferably C ₁ -C ₂₀ Alkyl optionally substituted with one or more aryl, alkoxy and aryloxy groups and selected from aryl, preferably C ₅ -C ₇ Aryl optionally substituted with one or more alkyl, aryl, alkoxy, and aryloxy groups, and mixtures thereof. Furthermore, the copper (I) source may be a substance or mixture of substances containing copper in any other oxidation state, provided that it can be converted to copper in the +1 oxidation state by chemical or electrochemical reduction or oxidation.

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

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 reagents generally increases the reaction rate. In a preferred embodiment of the invention, the copper (I) source is a copper (I) salt comprising a counter ion (i.e. a negatively charged ion) which has good solubility in organic solvents. Examples of negatively charged ions that are generally considered to have good solubility in organic solvents such as acetonitrile include triflate, tetrafluoroborate, hexafluorophosphate, and halides.

The copper (I) source may also comprise a ligand that coordinates to copper. Examples of copper sources with coordinating ligands include copper (I) tetraacetonitrile triflate, copper (I) tetraacetonitrile tetrafluoroborate, copper (I) tetraacetonitrile hexafluorophosphate, copper (I) tetraacetonitrile halide, cuBr (1, 10-phenanthroline) ₂ CuCl (1, 10-phenanthroline)] ₂ And Cul (1, 10-phenanthroline) ₂ 。

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

Copper (I) ions may be generated in situ from copper (II) compounds 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.

In one embodiment, the copper (II) compound is a copper (II) salt. In one embodiment, the copper (II) salt comprises a counter ion that is soluble in an organic solvent. The organic solvent-soluble counterions typically comprise a larger organic moiety and/or a negative charge that is delocalizable (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.

The reducing agents disclosed herein are capable of reducing copper (II) to copper (I). The reducing agent may be an organic or inorganic reducing agent. In one embodiment of the invention, the reducing agent is selected from the group consisting of copper metal, zinc metal, aluminum metal, sodium bisulphite, formic acid, formate, oxalate and oxalate. The metal-based reducing agent may advantageously be in the form of a powder, pellets, shavings or other finely divided form. The reducing agent may advantageously be selected to not produce any by-products, or to produce by-products that are easily removed, for example by evaporation. In one embodiment of the invention, the copper (I) source comprises a copper (II) salt and copper metal.

In one embodiment of the present disclosure, the catalyst composition of the present disclosure comprises a ligand. The ligand is expected to coordinate with 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.

Suitable ligands include ligands coordinated by nitrogen, oxygen, phosphorus, or other atoms having lone pair electrons. In one embodiment of the present disclosure, the ligand is coordinated by a moiety selected from the group consisting of pyridine, triarylphosphine, diaryl phosphine, amine, imidazole, pyrazole, pyrrole, triazole, tetrazole, imine, enamine, phenol, or a moiety comprising any of the listed moieties. In a preferred embodiment, the ligand is coordinated by a pyridine moiety.

The ligand may be a monodentate ligand or a polydentate ligand. In one embodiment of the present disclosure, the ligand is a monodentate ligand. In another embodiment of the present disclosure, the ligand is a bidentate ligand. In another embodiment, the ligand is a multidentate ligand that coordinates to 3 or more atoms.

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.

In one embodiment of the present disclosure, the ligand is selected from the group consisting of DETA, PMDETA, TETA, HMTETA, me ₆ TREN、cyclam、Me ₆ cyclam, DMCBCy, bpy, dNbpy, 1,10-Phen, tpy, tNtpy, BPMPrA, BPMOA, BPMODA, TPMA and TPEA. In one embodiment of the present disclosure, the ligand is a secondary amine, such as a secondary amine having a large substituent (i.e., to reduce the nucleophilicity of the amine). In one embodiment of the present disclosure, the ligand is a bidentate nitrogen 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' -dimethyl-2, 2' -bipyridine, 2' -bipyrimidine, 2' -bipyridine-4, 4' -dicarboxylic acid or an ester thereof, 2' -bipyridine-5, 5' -dicarboxylic acid or an ester thereof. In a preferred embodiment of the invention, the ligand is 2,2' -bipyridine (bpy).

The catalyst composition of the invention preferably comprises an aminooxy radical compound, i.e. having N-O ^· A compound of a functional group. In another embodiment of the invention, the aminooxy radical compound is a dialkylaminooxy radical compound. In another embodiment of the invention, the aminooxy radical compound is piperidine N-oxide or a derivative thereof. In a further embodiment, the aminooxy radical compound is a substituted piperidine N-oxide. In a further embodiment, the aminooxy compound is (2, 6-tetramethylpiperidin-1-yl) oxy (TEMPO) or a derivative thereof. In one embodiment of the present disclosure, the aminooxy radical compound is selected from TEMPO, (4-hydroxy-2, 6-tetramethylpiperidin-1-yl) oxy (4-OH-TEMPO), 4-acetamido-TEMPO, 4-hydroxy-TEMPO benzoate, 4-amino-TEMPO, 2-azaadamantan-N-oxy, 9-azabicyclo [3.3.1 ]Nonane N-oxy, 4-carboxy-TEMPO, 4-maleimido-TEMPO, 4-methoxy-TEMPO, 1-methyl-2-azaadamantan-N-oxy, 4-oxo-TEMPO, and polymers functionalized with any of the aminooxy radical compounds. In a preferred embodiment of the invention, the aminooxy radical compound is selected from TEMPO or (4-hydroxy-2, 6-tetramethylpiperidin-1-yl) oxy (4-OH-TEMPO). The aminooxy radical compound is expected to be part of the catalytic cycle that achieves the oxidation of the fatty alcohol composition of the present disclosure. It is well recognized that TEMPO and its derivatives as described herein act as catalysts for the oxidation of alcohol functions to aldehyde functions, while the oxidizing agent is O ₂ . However, TEMPO and derivatives disclosed herein are also referred to as "oxidizing agents" as used herein.

In one embodiment of the present disclosure, the catalyst composition comprises a base. Although specific bases are mentioned below, it is contemplated that many different bases will be useful in the practice of the present disclosure. In one embodiment of the invention, the base is an organic base. The use of an organic base may be advantageous because it can affect the solubility of the base in the reaction medium disclosed herein. In one embodiment of the present disclosure, the base is a nitrogen base. In one embodiment, the base is a Schiffbase (Schiffbase). 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, 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: 1-methylimidazole, potassium tert-butoxide or 1, 8-diazabicyclo (5.4.0) undec 7-ene (DBU).

In one embodiment of the present disclosure, the elements of the catalyst compositions provided herein may be mixed to form a catalyst composition prior to adding the catalyst composition to the reaction mixture. In another embodiment, the elements of the catalyst composition may be added separately to the reaction mixture. In another embodiment, a subset of the elements of the catalyst composition may be mixed and added to the reaction mixture, while the remaining elements of the catalyst composition are added individually and/or pre-mixed and then added to the reaction mixture.

Oxidation process

The present disclosure provides a process for converting a fatty alcohol composition to a fatty aldehyde composition. Specifically, the conversion of the fatty alcohol composition to the fatty aldehyde composition is the oxidation of the fatty alcohol composition.

The presently disclosed methods are contemplated for use in converting a variety of different primary alcohol compositions, such as compositions comprising primary alcohols having a chain length of at least two carbon atoms. However, the disclosed methods are particularly suitable for the oxidation of primary alcohols (i.e., fatty alcohols) having a chain length of eight or more carbon atoms, as further defined herein in the "fatty alcohols" and "fatty aldehydes" sections. Other known methods of performing oxidation generally produce only low yields and/or low purity fatty aldehyde compositions. "over oxidation", i.e., the further oxidation of the aldehyde to the corresponding carboxylic acid, is generally the primary cause of low reaction yield and/or purity of the aldehyde composition. Other known methods of conducting short primary alcohol oxidation may not be suitable for oxidation of fatty alcohols, as oxidation may not be complete, "over oxidation" may occur, and/or purification of the reaction product may not be feasible. Further related to the oxidation of fatty alcohols to fatty aldehydes, other known methods typically employ relatively large amounts of solvents and/or purification of the reaction products, as outlined in the background section. However, the presently disclosed methods use relatively small amounts of solvent for the oxidation reaction, and relatively small amounts of solvent for the purification of the reaction product. The presently disclosed methods are also advantageous because they are scalable, i.e., they can function on both small scale (e.g., less than 10g fatty alcohol composition) and large scale (e.g., greater than 100g fatty alcohol composition, e.g., greater than 500g fatty alcohol composition). Other known methods of oxidizing fatty alcohols to the corresponding fatty aldehydes may work well on a small scale (e.g., less than 10g of fatty alcohol composition), but they may not be scalable, i.e., they may not provide good reaction yields or product purity on a larger scale (e.g., more than 100g of fatty alcohol composition, e.g., more than 500g of fatty alcohol composition). Obtaining aldehyde compositions that are relatively free of byproducts, such as the corresponding fatty carboxylic acids or unreacted fatty alcohols, is advantageous because it eliminates the need for time consuming or expensive purification steps, such as distillation. Each of the above-described features (small solvent volume, scalability, and substrate range) makes the presently disclosed methods particularly suitable for use in industry.

One embodiment of the present disclosure provides a method of converting a fatty alcohol to a fatty aldehyde, the method comprising the steps of:

a. providing a reaction mixture comprising a fatty alcohol composition comprising the fatty alcohol, a catalyst composition, and a solvent, and

b. the reaction mixture is exposed to at least 0.25ml of oxygen per minute per gram of fatty alcohol by bubbling a gaseous mixture comprising oxygen through the reaction mixture.

Thereby obtaining fatty aldehyde.

In one embodiment of the present disclosure, a process for the large scale conversion of fatty alcohols to fatty aldehydes is provided, the process comprising the steps of:

b) By incorporating O into ₂ Is fed into the reaction medium, at least 0.01. Mu. Mol O per mu. Mol copper per minute in the reaction mixture ₂ Or at least 0.001. Mu. Mol O per minute per. Mu. Mol of starting fatty alcohol in the reaction mixture ₂ Is dissolved into the reaction mixture, whereby more than 50% by weight of the fatty alcohol is oxidized to fatty aldehyde and less than 50% by weight of the fatty alcohol is oxidized to fatty acid.

The disclosed process can be performed without any external cooling and without any external heating. However, current oxidation reactions are typically exothermic, and thus the temperature of the reaction mixture is expected to increase during the reaction. In one embodiment of the present disclosure, the reaction is carried out at 5 ℃ to 80 ℃, such as 10 ℃ to 70 ℃, such as 15 ℃ to 65 ℃. In another embodiment of the reaction, the reaction mixture is exposed to oxygen at 5 to 80 ℃, e.g., 10 to 70 ℃, e.g., 15 to 65 ℃.

The presently disclosed process may be carried out at ambient or elevated pressure. In one embodiment, the exposure of the reaction mixture to oxygen is performed at 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. In one embodiment, exposing the reaction mixture to oxygen is performed at a pressure of 0.5 to 0.8 bar, 0.8 to 1.2 bar, 1.2 to 1.5 bar, 1.5 to 2 bar, 2 to 5 bar, 5 to 10 bar, 10 to 20 bar, or 20 to 30 bar. In one embodiment of the present disclosure, the exposure of the reaction mixture to oxygen is performed at a pressure of 0.8 to 1.2 bar. However, it is contemplated that the presently disclosed process may be carried out at a pressure of less than 0.5 bar or 0.8 bar, provided that the amount of oxygen provided to the reaction mixture is as disclosed herein. In one embodiment, the pressure disclosed herein is the pressure in the reaction vessel in which the exposure of the reaction mixture to oxygen is performed. In one embodiment, the pressure disclosed herein is the partial pressure of oxygen in the reaction vessel.

In an additional or alternative embodiment, the reaction mixture is prepared by reacting a reaction mixture with a catalyst comprising O ₂ Or a liquid (optionally enriched in O) ₂ ) Mixing to mix O ₂ Added to the reaction mediumIn the middle of the mass. The mixing may be accomplished by including O ₂ Bubbling a gas mixture through the reaction mixture.

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

Oxygen transfer rate

An essential element of the present disclosure is that the amount of oxygen supplied to the reaction mixture is above a certain threshold. The inventors have found that the reaction yield is surprisingly improved at high oxygen transfer rates.

In one embodiment of the present disclosure, the reaction mixture is exposed to at least 0.3ml of oxygen per gram of fatty alcohol composition per minute, for example at least 0.4ml, 0.5ml, 0.6ml, 0.7ml, 0.8ml, 0.9ml, 1.0ml, 1.1ml, 1.2ml, 1.3ml, 1.4ml, such as at least 1.5ml 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 1.5ml of oxygen per gram of fatty alcohol composition per minute.

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

As used herein, whenever a gas volume is described, it is intended to correspond to a gas volume at a pressure of substantially 1 bar.

In one embodiment of the present disclosure, the reaction mixture is exposed to at least 60ml of oxygen per mole of fatty alcohol per minute, e.g., at least 100ml, 150ml, 200ml, 250ml, 300ml, 350ml. ml, 400ml, for example at least 450ml oxygen per minute per mole of fatty alcohol. In a preferred embodiment of the invention, the reaction mixture is exposed to at least 450ml of oxygen per minute per mole of fatty alcohol.

In one embodiment of the present disclosure, the reaction mixture is exposed to at least 10 μmol of oxygen per gram of fatty alcohol per minute, e.g., 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 of oxygen per gram of fatty alcohol per minute. In a preferred embodiment of the present disclosure, the reaction mixture is exposed to at least 60 μmol oxygen per gram of fatty alcohol per minute.

In one embodiment of the present disclosure, the reaction mixture is exposed to at least 2.5mmol of oxygen per mole of fatty alcohol per minute, e.g., at least 4mmol, 6mmol, 8mmol, 10mmol, 12mmol, 14mmol, 16mmol, e.g., at least 18mmol of oxygen per mole of fatty alcohol per minute. In a preferred embodiment of the invention, the reaction mixture is exposed to at least 18mmol oxygen per mole of fatty alcohol per minute.

The oxygen provided to the reaction mixture of the present disclosure may be provided as pure oxygen or as a gas mixture comprising oxygen. In one embodiment of the invention, the gas mixture comprises 5% to 100% oxygen. In another embodiment of the present disclosure, the gas mixture comprises 15-25% oxygen. In one embodiment of the present disclosure, the gas mixture comprises 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 herein, it is advantageous if the amount of water present in the reaction mixture is minimized. Thus, in a preferred embodiment of the invention, the gas mixture does not contain H ₂ O。

It is contemplated that sufficient exposure of oxygen to the reaction mixture is accomplished in part using the sufficient oxygen supply outlined herein, but also by ensuring a high contact surface between the supplied gas mixture and the liquid phase of the reaction mixture. A high contact surface is important to ensure a sufficiently high exposure of oxygen to the reaction mixture, for example by ensuring a sufficiently high dissolution of oxygen in the liquid phase of the reaction mixture. This may be achieved by using a device for bubbling a gas through the liquid, such as a spraying device. Increasing the injection of the gas mixture through the solution is expected to increase the oxygen transfer rate. It is expected that increasing the partial pressure of oxygen supplied to the reaction mixture may improve the oxygen transfer rate. Stirring the reaction mixture is expected to increase the oxygen transfer rate. Thus, it is desirable to agitate the reaction mixture of the present disclosure. In one embodiment of the present disclosure, a gas mixture comprising oxygen is bubbled through the reaction mixture. In another embodiment of the present disclosure, bubbling the gas mixture through the reaction is performed with a sparging device. In one embodiment of the present disclosure, the reaction mixture is stirred while the reaction mixture is exposed to oxygen.

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, such as at least 100 minutes. It is contemplated that exposure to oxygen need not be maintained for a continuous time as specified herein, but may be discontinued. Thus, in one embodiment of the present disclosure, the reaction mixture is exposed to oxygen for an uninterrupted time of at least 60 minutes, such as at least 70 minutes, 80 minutes, 90 minutes, such as at least 100 minutes. In another embodiment of the present disclosure, the reaction mixture is exposed to oxygen for two or more time periods, wherein the combined time periods add up to at least 60 minutes, such as at least 70 minutes, 80 minutes, 90 minutes, such as at least 100 minutes.

In one embodiment of the present disclosure, exposure to O ₂ In a bubble column reactor or a trickle bed reactor.

It is expected that longer reaction times may result in lower conversions and/or lower yields of the disclosed aldehyde compositions. This is expected to be caused by, for example, excessive oxidation of the aldehyde and/or the introduction of water into the reaction mixture exceeding the drying capacity of the drying apparatus. In one embodiment of the present disclosure, the reaction mixture is exposed to oxygen for up to 2000 minutes, e.g., 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, e.g., up to 250 minutes.

Important isIt is the amount of oxygen added to the reaction medium that balances the amount of fatty alcohol and/or the amount and effectiveness of the catalyst in the reaction medium. The supply of oxygen to the reaction medium for optimal aldehyde formation may also be affected by the amount of fatty acids in the reaction medium, wherein the formation of higher amounts of acids requires an increased oxygen supply. Thus, in additional or alternative embodiments, the methods described herein include adding at least 0.010, 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, at least 0.070, such as at least 0.080, such as at least 0.090, such as at least 0.100. Mu. Mol dissolved O per minute, such as per. Mu. Mol copper in the reaction mixture ₂ And/or at least 0.0010, such as at least 0.0020, such as at least 0.0025, such as at least 0.0030, such as at least 0.0050, such as at least 0.0075, such as at least 0.0100. Mu. Mol of dissolved O per mu. Mol of starting fatty alcohol in the reaction mixture per minute ₂ And/or at least 0.010, 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. Mu. Mol dissolved O per mu. Mol fatty acid in the reaction mixture per minute ₂ 。

In some embodiments, the methods of the present disclosure further comprise: at least 0.049. Mu. Mol of dissolved O per mu. Mol of copper per minute is dissolved in the reaction mixture ₂ 。

In some embodiments, the methods of the present disclosure further comprise: at least 0.02. Mu. Mol of dissolved O per mu. Mol of copper per minute is dissolved in the reaction mixture ₂ For example at least 0.03. Mu. Mol, for example at least 0.04. Mu. Mol of dissolved O per mu. Mol of copper per minute in the reaction mixture ₂ 。

In some embodiments, the methods of the present disclosure further comprise: dissolving 0.01 to 1.00. Mu. Mol of dissolved O per mu. Mol of copper per minute in the reaction mixture ₂ For example 0.01 to 0.80. Mu. Mol, for example 0.01 to 0.60. Mu. Mol, for example 0.01 to 0.40. Mu. Mol, for example 0.01 to 0.20. Mu. Mol, for example 0.01 to 0.10. Mu. Mol of dissolved O per mu. Mol of copper per minute in the reaction mixture ₂ 。

In some embodiments, the methods of the present disclosure further comprise: in the reaction mixingAt least 0.0025. Mu. Mol of dissolved O per mu. Mol of starting fatty alcohol per minute in the composition ₂ 。

In some embodiments, the methods of the present disclosure further comprise: at least 0.002. Mu. Mol of dissolved O per mu. Mol of starting fatty alcohol per minute is dissolved in the reaction mixture ₂ For example at least 0.003. Mu. Mol, for example at least 0.004. Mu. Mol of dissolved O per mu. Mol of starting fatty alcohol per minute in the reaction mixture ₂ 。

In some embodiments, the methods of the present disclosure further comprise: 0.001 to 1.00. Mu. Mol of dissolved O per mu. Mol of starting fatty alcohol per minute in the reaction mixture ₂ For example, 0.001 to 0.80. Mu. Mol, for example, 0.001 to 0.60. Mu. Mol, for example, 0.001 to 0.40. Mu. Mol, for example, 0.001 to 0.20. Mu. Mol, for example, 0.001 to 0.10. Mu. Mol of dissolved O per. Mu. Mol of starting fatty alcohol in the reaction mixture per minute ₂ 。

In some embodiments, the methods of the present disclosure further comprise: at least 0.025. Mu. Mol of dissolved O per. Mu. Mol of fatty acid per minute is dissolved in the reaction mixture ₂ 。

In some embodiments, the methods of the present disclosure further comprise: at least 0.01. Mu. Mol of dissolved O per. Mu. Mol of fatty acid per minute is dissolved in the reaction mixture ₂ For example at least 0.02. Mu. Mol, for example at least 0.03. Mu. Mol, for example at least 0.04. Mu. Mol of dissolved O per. Mu. Mol of fatty acid per minute in the reaction mixture ₂ 。

In some embodiments, the methods of the present disclosure further comprise: at least 10. Mu. Mol O per gram of fatty alcohol per minute is dissolved in the reaction mixture ₂ For example at least 20. Mu. Mol O ₂ At least 40 mu mol O ₂ Or at least 60. Mu. Mol O ₂ Thereby obtaining fatty aldehydes, optionally wherein the fatty alcohols and fatty aldehydes are desaturated.

In some embodiments, the methods of the present disclosure further comprise: to a level sufficient to maintain at least 80% O in the reaction medium during the oxidation reaction ₂ Saturation, e.g. at least 85% O ₂ Saturation, e.g. at least 90% O ₂ Saturation, e.g. at least 95% O ₂ Saturation, e.g. at least 100% O ₂ The rate of saturation will be O ₂ Dissolved in the reaction medium.

In some embodiments, comprises O ₂ Is air, optionally enriched in O ₂ 。

In some embodiments, methods of the present disclosure are provided wherein O will be comprised ₂ Is fed into the reaction medium by feeding a gas or liquid comprising O ₂ Is pumped or bubbled through the reaction mixture.

Reaction conditions

The present disclosure uses a relatively small volume of solvent to effect conversion of a fatty alcohol composition to a fatty aldehyde composition. In particular, the previously reported methods of converting fatty alcohols to fatty aldehydes as outlined herein use relatively large amounts of solvent for the reaction mixture. Large solvent volumes are generally considered not viable in large scale production because of solvent costs, environmental footprint, and processing large reaction volumes can be challenging. Thus, the presently disclosed oxidation process can be advantageously used for large-scale production of fatty aldehyde compositions due to the relatively small solvent volumes required. "relatively small solvent volume" refers to the volume outlined herein.

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

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

In one embodiment, the solvent is an aprotic solvent. Advantageously, the solvent is aprotic, as protons such as those derived from OH groups or amines can deleteriously interfere with components such as the catalyst composition, for example by inactivating the base. In one embodiment of the present disclosure, the solvent is selected from the list consisting of: acetonitrile, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), alkanes such as pentane, hexane and heptane, cycloalkanes, petroleum ethers such as heavy or light petroleum ether, dioxane, diethyl ether, dichloromethane, tetrahydrofuran, ethyl acetate, acetone, nitromethane, propylene carbonate, and solvent mixtures comprising any of the solvents. In a preferred embodiment, the solvent is selected from the list consisting of: acetonitrile, DMSO, DMF, and solvent mixtures comprising any of the solvents. In a further preferred embodiment, the solvent is or comprises acetonitrile. In another preferred embodiment of the present invention, the solvent is acetonitrile.

In one embodiment, the solvent is a polar solvent. The solvent is polar, as this improves the solubility of at least some of the components of the reaction mixture and/or of the components of the gas mixture. In one embodiment of the present invention, the solvent is selected from the group consisting of dichloromethane, tetrahydrofuran, ethyl acetate, acetone, dimethylformamide (DMF), acetonitrile, dimethyl sulfoxide (DMSO), nitromethane, propylene carbonate, and solvent mixtures comprising any one of the solvents. In a preferred embodiment, the solvent is selected from the group consisting of acetonitrile, DMSO, DMF, or a solvent mixture comprising any one of the solvents. In an even further preferred embodiment, the solvent is acetonitrile or a solvent mixture comprising acetonitrile. In yet another preferred embodiment, the solvent is acetonitrile.

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

The amount of solvent in the reaction mixture can be compared to the amount of fatty alcohol composition. In one embodiment of the present disclosure, the weight of solvent in the reaction mixture is from 0 to 2000%, such as from 100 to 1500%, such as from 100 to 1000%, such as from 100% to 500% by weight of the fatty alcohol composition. The fatty alcohol composition may comprise other chemical compounds in addition to the fatty alcohol. In order to evaluate the amount of solvent, it is preferable to exclude these other compounds when calculating the amount of solvent. In addition, the fatty alcohol composition may comprise one or more solvents, i.e. "fatty alcohol composition solvent". In a preferred embodiment of the present disclosure, the fatty alcohol composition solvent is ignored when assessing the amount of fatty alcohol 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 one or more fatty alcohols in the fatty alcohol composition.

The amount of solvent in the reaction mixture can be compared to the amount of fatty aldehyde composition obtained from the reaction mixture. In one embodiment of the invention, the weight of solvent in the reaction mixture is 100 to 2000%, such as 100 to 1500%, such as 100 to 1000%, such as 100 to 500% by weight of the fatty aldehyde composition. The fatty aldehyde composition may comprise other chemical compounds in addition to the fatty aldehyde. In order to evaluate the amount of solvent, it is preferable to exclude these other compounds when calculating the amount of solvent. In addition, the fatty aldehyde composition may comprise one or more solvents, i.e. "fatty aldehyde composition solvent". In a preferred embodiment of the present disclosure, the fatty aldehyde composition solvent is ignored when assessing the amount of fatty 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 one or more fatty aldehydes in the fatty aldehyde composition.

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, cycloalkane, petroleum ether, dioxane, diethyl ether, tetrahydrofuran, ethyl acetate, acetone, nitromethane, propylene carbonate, or combinations thereof.

Transformation

The presently disclosed process is capable of efficiently converting fatty alcohol compositions to fatty aldehyde compositions in high yields and/or with little formation of by-products. As used herein, conversion may be based on the amount of substrate and/or product material, or based on the weight of the substrate.

In one embodiment of the present disclosure, the conversion of fatty 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%, as assessed by amount of material. In another embodiment of the present disclosure, the conversion of the fatty 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%, as assessed by weight of the fatty alcohol. In a preferred embodiment, the conversion of fatty alcohol to 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%, as assessed by amount of material. In a preferred embodiment, the conversion of fatty alcohol to 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%, as assessed by weight of fatty alcohol and fatty aldehyde.

The conversion can in particular be calculated as the ratio of the amount of substance of the aldehyde to the total amount of substance of aldehyde and alcohol, i.e. n (aldehyde)/(n (aldehyde) +n (alcohol)), where n designates 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%, as assessed by amount of substance. In a preferred embodiment, the conversion of fatty alcohol to 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%.

The disclosed process effectively converts fatty alcohols to fatty aldehydes with little formation of by-products, such as the corresponding fatty acids, i.e., little "over-oxidation". For the catalytic oxidation of alcohols to aldehydes, avoiding the formation of carboxylic acids, such as fatty acids, is of paramount importance, as it is expected that carboxylic acids may deactivate the catalyst 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 alcohol is converted to fatty acid. 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 acid to fatty aldehyde 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. As used herein, "ratio" refers to molar ratio. In some aspects, the ratio of fatty acid produced to fatty aldehyde produced is less than 10:90.

It is contemplated that the disclosed methods can also be used to convert other alcohol compositions to aldehyde compositions. For example, it is contemplated that the disclosed methods may be used to apply C ₂ -C ₇ Alcohols, i.e. ethanol, propanol, butanol, pentanol, hexanol and heptanol, are converted to the corresponding C ₂ -C ₇ Aldehydes, i.e., acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde and heptanal. It is contemplated that both linear and branched derivatives of these substrates can be converted using the disclosed methods, so long as the substrate comprises a primary alcohol. For example, it is contemplated that the disclosed methods can be used to convert n-butanol to n-butyraldehyde and isobutanol to isobutyraldehyde. It is contemplated that the disclosed methods may also be used for desaturation, i.e., unsaturated derivatives of the above substrates.

In some embodiments, the present disclosure provides a process wherein the conversion of fatty alcohol to fatty 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%.

In some embodiments, the present disclosure provides a method wherein the conversion of fatty alcohol to 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%.

Dewatering

Water is present in trace amounts in many chemicals and solvents. If the chemicals and solvents contain no water or only a small amount of water, they are often referred to as "drying". Water may also be produced during the chemical reaction. It is expected that better reaction yields may be obtained if efforts are made to remove water from the reaction mixture. This is because water is expected to deteriorate the catalyst composition.

In one embodiment of the present disclosure, substantially dry solvents and reagents, including gas mixtures and gases, are employed in the methods of the present invention.

Some reagents and/or solvents may be difficult to dry completely before use in the presently disclosed methods. Thus, while the process is being carried out, water can be removed from the reaction mixture. In one embodiment of the present disclosure, water is removed from the reaction mixture. In one embodiment of the invention, water is continuously removed from the reaction mixture throughout the exposure of oxygen to the reaction mixture. In one embodiment of the present disclosure, water is removed from the reaction mixture by adding a drying means to 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 absorbing material. In one embodiment of the present disclosure, the drying means is selected from molecular sieves, silica gel, alumina, bentonite, calcium oxide, alkali metal carbonates, bicarbonates or alkaline earth metal carbonates.

In one embodiment, water is removed from the reaction mixture, for example to a water content of about less than 2 wt% (relative to the weight of the reaction mixture), for example less than 2 wt%. In one embodiment, water is removed from the reaction mixture, for example to a water content of about less than 1 wt% (relative to the weight of the reaction mixture), for example less than 1 wt%.

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

The water absorbing or adsorbing material is added to the reaction medium in an amount such that the water content in the reaction medium after the oxidation process is 2 wt% or less and optionally the molar conversion of fatty alcohol to fatty aldehyde exceeds 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 10g per mmol of fatty alcohol present in the reaction medium prior to oxidation, such as at least 15g per mmol of fatty alcohol, such as at least 19g per mmol of fatty alcohol.

Providing fatty alcohol compositions

The methods disclosed herein may include: first, a fatty alcohol composition disclosed herein is produced or an initial step of producing a fatty alcohol disclosed herein.

An embodiment of the present disclosure provides a method as disclosed herein, wherein the method further comprises an initial step of producing fatty alcohols, the initial step comprising the steps of: i. providing yeast cells capable of producing fatty alcohols

incubating the yeast cells in a culture medium,

thereby producing fatty alcohols.

An embodiment of the present disclosure provides a method as disclosed herein, wherein the method further comprises an initial step of producing a fatty alcohol composition, the initial step comprising the steps of:

i. providing yeast cells capable of producing fatty alcohol compositions, and

incubating the yeast cells in a culture medium,

thereby producing a fatty alcohol composition.

An embodiment of the present disclosure provides a method as disclosed herein, wherein the method further comprises an initial step of producing fatty alcohols, the initial step comprising the steps of: i. providing a yeast cell capable of synthesizing alkanoyl-coa, said yeast cell further capable of expressing:

-desaturase, and

alcohol-forming fatty acyl-CoA reductase,

expressing said desaturase and said alcohol-forming fatty acyl-CoA reductase from said yeast cell,

and is also provided with

incubating the yeast cells in a culture medium

Whereby a desaturase is capable of converting at least a portion of said alkanoyl-CoA to enoyl-CoA, and whereby said alcohol-forming fatty acyl-CoA reductase is capable of converting at least a portion of said enoyl-CoA to a fatty alcohol, thereby producing said fatty alcohol. Details of carrying out the above fatty alcohol production are disclosed in EP 3313997B 1. In another embodiment of the present disclosure, the fatty alcohol is (Z) -11-hexadecen-1-ol, wherein the alkanoyl-CoA is hexadecanoyl-CoA, wherein the desaturase is Δ11-desaturase, wherein the enoyl-CoA is (Z) -11-hexadecenoyl-CoA.

An embodiment of the present disclosure provides a method as disclosed herein, wherein the method further comprises an initial step of producing a fatty alcohol composition, the initial step comprising the steps of: i. providing a yeast cell capable of synthesizing alkanoyl-coa, said yeast cell further capable of expressing:

-desaturase, and

alcohol-forming fatty acyl-CoA reductase,

Expressing said desaturase and said alcohol-forming fatty acyl-coa reductase from said yeast cell, and

incubating the yeast cells in a culture medium

Whereby a desaturase is capable of converting at least a portion of said alkanoyl-CoA to enoyl-CoA, and whereby said alcohol-forming fatty acyl-CoA reductase is capable of converting at least a portion of said enoyl-CoA to a fatty alcohol, thereby producing said fatty alcohol composition. Details of the production of the above fatty alcohol composition are disclosed in EP 3313997B 1. In another embodiment of the present disclosure, the fatty alcohol is (Z) -11-hexadecen-1-ol, wherein the alkanoyl-CoA is hexadecanoyl-CoA, wherein the desaturase is Δ11-desaturase, wherein the enoyl-CoA is (Z) -11-hexadecenoyl-CoA. Details on how to carry out the above-described steps for producing fatty alcohols are disclosed in WO 2016/207339.

An embodiment of the present disclosure provides a method as disclosed herein, wherein the method further comprises an initial step of producing fatty alcohols, the initial step comprising the steps of: i. providing oleaginous yeast cells capable of producing a desaturated fatty alcohol, the yeast cells further comprising:

capable of expressing at least one heterologous fatty acyl-CoA desaturase capable of introducing at least one double bond in fatty acyl-CoA, thereby forming a desaturated fatty acyl-CoA,

Capable of expressing at least one heterologous fatty acyl-CoA reductase capable of converting at least part of said desaturated fatty acyl-CoA to a desaturated fatty alcohol,

-having a mutation resulting in a decrease in fatty alcohol oxidase activity and having a mutation resulting in a decrease in activity of at least one of fatty aldehyde dehydrogenase, peroxisome biogenesis factor and 3-phosphoglycerate acyltransferase, and

incubating the yeast cells in a culture medium,

thereby producing fatty alcohols. Details on how to perform the above-described steps for producing fatty alcohols are disclosed in WO 2018/109163.

An embodiment of the present disclosure provides a method as disclosed herein, wherein the method further comprises an initial step of producing a fatty alcohol composition, the initial step comprising the steps of: i. providing oleaginous yeast cells capable of producing a desaturated fatty alcohol, the yeast cells further comprising:

incubating the yeast cells in a culture medium,

thereby producing a fatty alcohol composition. Details on how to perform the above-described steps for producing fatty alcohol compositions are disclosed in WO 2018/109163.

An embodiment of the present disclosure provides a method as disclosed herein, wherein the method further comprises an initial step of producing fatty alcohols, the initial step comprising the steps of: i. providing a yeast cell capable of producing a desaturated fatty alcohol, said yeast cell expressing:

-at least one heterologous fatty acyl-CoA desaturase capable of introducing at least one double bond in a fatty acyl-CoA having a carbon chain length of 14, wherein the desaturase is selected from the group consisting of Δ9 desaturase and Δ11 desaturase, wherein the desaturase has a higher specificity for tetradecyl-CoA than for hexadecyl-CoA, and

-at least one heterologous fatty acyl-CoA reductase capable of converting at least part of said desaturated fatty acyl-CoA to a desaturated fatty alcohol, and

incubating the yeast cells in a culture medium,

thereby producing fatty alcohols. Details on how to perform the above-described steps for producing fatty alcohols are disclosed in WO 2018/109167.

An embodiment of the present disclosure provides a method as disclosed herein, wherein the method further comprises an initial step of producing a fatty alcohol composition, the initial step comprising the steps of: i. providing a yeast cell capable of producing a desaturated fatty alcohol, said yeast cell expressing:

incubating the yeast cells in a culture medium,

thereby producing a fatty alcohol composition. Details on how to perform the above-described steps for producing fatty alcohol compositions are disclosed in WO 2018/109167.

heterologous delta 12 fatty acyl-CoA desaturase capable of introducing a double bond at position 12 in a saturated or desaturated fatty acyl-CoA, preferably a desaturated fatty acyl-CoA, having a carbon chain length of at least 13 and having n double bonds,

where n and n' are integers,

wherein 0.ltoreq.n.ltoreq.3 and wherein 1.ltoreq.n'.ltoreq.4, and

incubating the yeast cells in a culture medium,

thereby producing a fatty alcohol composition. Details on how to perform the above-described steps for producing fatty alcohol compositions are disclosed in application EP21183447.8 entitled "Methods and yeast cells for production of desaturated compounds (method for producing desaturated compounds and yeast cells)" filed by the same applicant on month 7 and 2 of 2021.

heterologous delta 13 fatty acyl-CoA desaturase capable of introducing a double bond at position 13 in a saturated or desaturated fatty acyl-CoA, preferably a desaturated fatty acyl-CoA, having a carbon chain length of at least 14 and having n double bonds,

where n and n' are integers,

wherein 0.ltoreq.n.ltoreq.3 and wherein 1.ltoreq.n'.ltoreq.4, and

incubating the yeast cells in a culture medium,

thereby producing a fatty alcohol composition. Details on how to perform the above-mentioned steps for producing fatty alcohol compositions are disclosed in application EP21183459.3 entitled "Methods and yeast cells for production of desaturated compounds (method for producing desaturated compounds and yeast cells)" filed by the same applicant on day 7 and 2 of 2021.

An embodiment of the present disclosure provides a method as disclosed herein, wherein the method further comprises an initial step of producing a fatty alcohol composition, the initial step comprising the steps of: i. providing a yeast cell capable of producing E8, E10-dodecadienol-1-ol, said yeast cell expressing: -at least one heterologous desaturase capable of introducing one or more double bonds in a fatty acyl-CoA having a carbon chain length of 12, thereby converting said fatty acyl-CoA to a desaturated fatty acyl-CoA, wherein at least a portion of said desaturated fatty acyl-CoA is E8, E10-dodecadienyl CoA (E8, E10-C12: coA), wherein:

a) At least one desaturase is Cpo CPRQ (accession No. AHW 98354), or a functional variant thereof having at least 80% identity thereto, e.g., having at least 81%, e.g., at least 82%, e.g., at least 83%, e.g., at least 84%, e.g., at least 85%, e.g., at least 86%, e.g., at least 87%, e.g., at least 88%, e.g., at least 89%, e.g., at least 90%, e.g., at least 91%, e.g., at least 92%, e.g., at least 93%, e.g., at least 94%, e.g., at least 95%, e.g., at least 96%, e.g., at least 97%, e.g., at least 98%, e.g., at least 99% identity to cpo_cprq; or alternatively

b) The at least one desaturase is at least two desaturases, wherein at least one of the two desaturases is cpo_cprq (accession No. AHW 98354), or a functional variant thereof having at least 80% identity thereto, e.g., a desaturase having at least 81%, e.g., at least 82%, e.g., at least 83%, e.g., at least 84%, e.g., at least 85%, e.g., at least 86%, e.g., at least 87%, e.g., at least 88%, e.g., at least 89%, e.g., at least 90%, e.g., at least 91%, e.g., at least 92%, e.g., at least 93%, e.g., at least 94%, e.g., at least 95%, e.g., at least 96%, e.g., at least 97%, e.g., at least 98%, e.g., at least 99% identity thereto, and the other desaturase is one desaturase having the ability to introduce at least one double bond in fatty acyl-CoA, e.g., having a carbon chain length of 12; and

-at least one heterologous fatty acyl-CoA reductase capable of converting at least part of said E8, E10-dodecenyl CoA to E8, E10-dodecenyl-1-ol, and

incubating the yeast cells in a culture medium,

thereby producing a fatty alcohol composition. Details on how to perform the above-described steps for producing fatty alcohol compositions are disclosed in application WO 2021/123128.

An embodiment of the present disclosure provides a method as disclosed herein, wherein the method further comprises an initial step of producing fatty alcohols, the initial step comprising: providing a yeast cell capable of producing a fatty alcohol and culturing the yeast cell in a medium under conditions that allow production of the fatty alcohol, wherein the medium comprises an extractant in an amount equal to or greater than its turbidity concentration measured in an aqueous solution, such as a medium, at a culture temperature, wherein the extractant is a nonionic ethoxylated surfactant, thereby producing a fatty alcohol.

An embodiment of the present disclosure provides a method as disclosed herein, wherein the method further comprises an initial step of producing a fatty alcohol composition, the initial step comprising: providing a yeast cell capable of producing a fatty alcohol composition and culturing the yeast in a medium under conditions that allow production of the fatty alcohol composition, wherein the medium comprises an extractant in an amount equal to or greater than its turbidity concentration measured in an aqueous solution, such as a culture medium, at a culture temperature, wherein the extractant is a nonionic ethoxylated surfactant, thereby producing a fatty alcohol composition.

One embodiment of the present disclosure provides a method as disclosed herein, wherein the method further comprises an initial step of producing fatty alcohols, said initial step comprising

i. Providing a yeast cell capable of producing a fatty alcohol ester, and culturing the yeast cell in a medium under conditions permitting production of the fatty alcohol ester, wherein the medium comprises an extractant in an amount equal to or greater than its turbidity concentration measured in an aqueous solution, such as a medium, at a culture temperature, wherein the extractant is a nonionic ethoxylated surfactant, thereby producing a fatty alcohol ester, and

converting the fatty alcohol ester to a fatty alcohol,

thereby producing fatty alcohols.

One embodiment of the present disclosure provides a method as disclosed herein, wherein the method further comprises an initial step of producing a fatty alcohol composition, the initial step comprising

Converting the fatty alcohol ester to a fatty alcohol,

thereby producing a fatty alcohol composition.

Details of how to perform a yeast cell culture in a medium comprising an amount of extractant equal to or greater than its turbidity concentration are described in detail in application WO 2021/078452.

Additionally or alternatively, disclosed herein is a composition comprising greater than 93 wt.% fatty aldehyde, less than 7 wt.% fatty alcohol, and less than 2 wt.% water. In some embodiments, the amount of aldehyde may be 94 wt% or more, such as 95 wt% or more, such as 96 wt% or more, such as 97 wt% or more, such as 98 wt% or more, such as at least 99 wt%, while the amount of unconverted fatty alcohol is less than 6 wt%, such as less than 5 wt%, such as less than 4 wt%, such as less than 3 wt%, such as less than 2 wt%, such as 1 wt% or less, while the amount of water is less than 2 wt%, such as less than 1.5 wt%, such as 1 wt% or less.

Purification

The present disclosure provides methods of purifying fatty aldehydes (e.g., fatty aldehydes disclosed herein) and fatty aldehyde compositions (e.g., fatty aldehyde compositions disclosed herein).

One embodiment of the present disclosure provides a method for purifying fatty aldehydes, comprising the steps of: a. providing a crude reaction product comprising:

i. A fatty aldehyde, and a fatty acid,

copper ions, and

polar solvent;

c. the nonpolar phase is separated from the polar phase.

An embodiment of the present disclosure provides a fatty aldehyde purification process as disclosed herein, wherein the crude reaction product comprises:

from 5% to 80% of fatty aldehydes,

0.05 to 5.0% copper ions,

20% to 95% of a polar solvent.

In some embodiments, the present disclosure provides a method further comprising a step of purifying a fatty aldehyde, the step comprising:

a) Providing a purification mixture comprising:

i. a fatty aldehyde, and a fatty acid,

copper ions, and

polar solvent;

b) Mixing the purification mixture with a non-polar aprotic solvent and an acid to produce an extraction mixture comprising a non-polar phase and a polar phase such that fatty aldehydes are extracted from the polar phase to the non-polar phase, and

c) The nonpolar phase containing the purified aldehyde is separated from the polar phase.

In some embodiments, the purification mixture comprises 0.05 to 5.0 wt% copper ions, such as 0.05 to 2.0 wt% copper ions, such as 0.05 to 1.0 wt% copper ions.

Representative embodiments of the crude reaction products disclosed herein may comprise about 30% fatty aldehyde, about 1.0% ligand, about 0.4% copper, about 0.6% aminoxy, about 0.5% base, and about 62% polar solvent. Another representative embodiment of the crude reaction product disclosed herein may comprise about 30% fatty aldehyde, about 1.0% bipyridine, about 0.4% copper, about 0.6%4-OH-TEMPO, about 0.5% 1-methylimidazole, and about 62% acetonitrile.

One embodiment provides a fatty aldehyde purification process as disclosed herein, wherein the crude reaction product comprises 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. As disclosed herein, references to the weight or weight percent of copper, copper ions, copper salts, and the like, refer to the weight content of copper that is isolated, i.e., without a counter ion.

An embodiment provides a fatty aldehyde purification process as disclosed herein, wherein the crude reaction product further comprises a ligand, e.g., 0.1% to 10% ligand, e.g., 0.1% to 5% ligand, e.g., 0.1% to 2% ligand, e.g., about 1% ligand. In one embodiment of the invention, the ligand is a bidentate nitrogen ligand, for example a bidentate nitrogen ligand selected from 2,2 '-bipyridine, 4' -dimethyl-2, 2 '-bipyridine, 5' -dimethyl-2, 2 '-bipyridine 2,2' -bipyrimidine, 2 '-bipyridine-4, 4' -dicarboxylic acid or an ester thereof, 2 '-bipyridine-5, 5' -dicarboxylic acid or an ester thereof.

An embodiment provides a fatty aldehyde purification process as disclosed herein, wherein the crude reaction product further comprises an aminooxy radical compound, such as from 0.01 to 10% aminooxy radical compound, such as from 0.01 to 5% aminooxy radical compound, such as from about 0.01% to 2% aminooxy radical compound, such as about 0.5% aminooxy radical compound. In one embodiment of the present disclosure, the aminooxy radical compound is selected from TEMPO, (4-hydroxy-2, 6-tetramethylpiperidin-1-yl) oxy (4-OH-TEMPO), 4-acetamido-TEMPO, 4-hydroxy-TEMPO benzoate, 4-amino-TEMPO, 2-azaadamantan-N-oxy, 9-azabicyclo [3.3.1] nonane-oxy, 4-carboxy-TEMPO, 4-maleimido-TEMPO, 4-methoxy-TEMPO, 1-methyl-2-azaadamantan-N-oxy, 4-oxo-TEMPO, and polymers functionalized with any of the aminooxy radical compounds.

One embodiment provides a fatty aldehyde purification process as disclosed herein, wherein the crude reaction product further comprises a base, such as 0.1% to 10% base, such as 0.1% to 5% base, such as 0.1% to 2% base, such as about 0.5% base. In one embodiment of the invention, 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, 3-tetramethylguanidine, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene and potassium tert-butoxide.

In one embodiment of the present disclosure, the fatty aldehyde is a saturated fatty aldehyde as disclosed herein. In one embodiment of the present disclosure, the fatty aldehyde is an unsaturated fatty aldehyde disclosed herein. In one embodiment of the invention, the fatty aldehyde is as disclosed in the "fatty aldehyde" moiety. In one embodiment, the fatty aldehyde is selected from: (E) 7, (Z) 9 desaturated fatty aldehyde of carbon chain length 14, (E) 3, (Z) 8, (Z) 11 desaturated fatty aldehyde of carbon chain length 14, (Z) 9, (E) 11, (E) 13 desaturated fatty aldehyde of carbon chain length 14, (E) 7, (Z) 9 with desaturated fatty aldehyde of carbon chain length 12, (E) 3, (Z) 8, (Z) 11 desaturated fatty aldehyde of carbon chain length 12, (Z) 9, (E) 11, (E) 13 desaturated fatty aldehyde of carbon chain length 12, and (E) 8, (E) 10 desaturated fatty aldehyde of carbon chain length 12. In one embodiment, the fatty aldehyde is selected from the group consisting of tetradecane-1-aldehyde, pentadecane-1-aldehyde, hexadecane-1-aldehyde, pentadecene-1-aldehyde, (Z) -9-hexadecene-1-aldehyde, (Z) -11-hexadecene-1-aldehyde, and (7E, 9E) -undecane-7, 9-diene-1-aldehyde.

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

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

In one embodiment, the non-polar aprotic solvent is selected from the group consisting of straight paraffins, branched paraffins, and naphthenes. In one embodiment, the non-polar aprotic solvent is selected from the group consisting of pentane, hexane, heptane and octane. In one embodiment, the non-polar aprotic solvent is selected from the group consisting of heptane, pentane, hexane, cyclohexane and octane.

In one embodiment, the acid has a pKa value between 3 and 6. In one embodiment, the acid is a carboxylic acid. In one embodiment, the carboxylic acid is C ₂ -C ₈ Carboxylic acids. In one embodiment, the carboxylic acid is selected from the group consisting of C ₂ -C ₈ Monocarboxylic acid, C ₂ -C ₈ Dicarboxylic acid and C ₆ -C ₈ Tricarboxylic acids. In one embodiment, the carboxylic acid is selected from the group consisting of acetic acid, citric acid, propionic acid, lactic acid, glycolic acid, 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, for example at least 2.4 equivalents, are used. In one embodiment, 2.0 to 2.4, 2 relative to copper is used. 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, or more than 10.0 equivalents of carboxylic acid. "equivalent" refers to molar equivalent.

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 waste oxidizing agent is selected from TEMPO, (4-hydroxy-2, 6-tetramethylpiperidin-1-yl) oxy (4-OH-TEMPO), 4-acetamido-TEMPO, 4-hydroxy-TEMPO benzoate, 4-amino-TEMPO, 2-azaadamantane-N-oxy, 9-azabicyclo [3.3.1] nonane N-oxy, 4-carboxy-TEMPO, 4-maleimido-TEMPO, 4-methoxy-TEMPO, 1-methyl-2-azaadamantane-N-oxy, 4-oxo-TEMPO, and polymers functionalized with any of the aminoxy radical compounds; or a waste agent thereof, or water.

In one embodiment, the fatty aldehyde purification methods disclosed herein further comprise the step of evaporating the non-polar aprotic solvent. In one embodiment, the evaporation of the non-polar aprotic solvent is performed under reduced pressure, e.g. below 100 mbar, e.g. below 50 mbar, e.g. below 40 mbar, e.g. below 30 mbar.

One embodiment of the present disclosure provides a method of converting a composition comprising a fatty alcohol to a composition rich in fatty aldehydes, the method comprising:

a. converting a composition comprising fatty alcohol to a composition comprising fatty aldehyde using the methods of oxidizing fatty alcohol disclosed herein, and

b. the composition comprising fatty aldehydes is purified using the fatty aldehyde purification methods disclosed herein.

In a further embodiment, the fatty alcohols and fatty aldehydes are desaturated.

In one exemplary embodiment of the present disclosure, the crude reaction product containing the catalyst system (copper complex, TEMPO or derivative, N-methyl-imidazole or another base), the product from oxidation to fatty aldehydes, 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, typically an alkane, is then extracted with an organic solvent that is immiscible with the reaction solvent, such as pentane, heptane or hexane. Extraction may use a separating funnel, a mixer-settler, a pulsed column or any other liquid-liquid separation method. Sedimentation of the phases occurs rapidly without any foam or suspension being formed. The heavy phase contains almost all of the catalyst components and the reaction product is almost entirely in the light phase. Evaporation of the extraction solvent yields the product fatty aldehyde. Optionally, additives may be included to improve removal of one or more components, such as copper ions. Such additives may be organic acids, such as acetic acid or citric acid.

Product(s)

One embodiment of the present disclosure provides a composition comprising a fatty aldehyde obtained by the methods disclosed herein. One embodiment of the present disclosure provides fatty aldehydes obtained from the methods disclosed herein. In a further embodiment, the fatty aldehyde is desaturated.

Copper ions in solution (aqueous or non-aqueous) typically have a blue color. In one embodiment of the present disclosure, the composition exhibits an absorbance at 680nm of at most 0.5 in a cuvette having an optical path length of 5 mm. In one embodiment, the absorbance at 680nm in a cuvette of 5mm optical path length 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. In one embodiment, the fatty aldehyde composition comprises less than 0.4% copper, such as less than 0.3%, such as 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%.

The fatty aldehydes disclosed herein can be produced from renewable raw materials. The fatty aldehyde or any sustained release composition thereof acts as a pheromone component. Accordingly, one embodiment of the present disclosure provides a pheromone component produced from renewable raw materials. One embodiment of the present disclosure provides a pheromone component produced from renewable raw materials, the pheromone component having a biobased carbon content of at least 80% or more. In one embodiment, "biobased carbon" content refers to an organic compound in which the carbon is derived from a biological source or precursor. In one embodiment, the pheromone component comprises the fatty aldehyde composition and/or the fatty aldehyde disclosed herein. In one embodiment, the pheromone component comprises a sustained release composition as disclosed herein. In one embodiment, the pheromone component comprises the fatty acetals and/or alpha-hydroxysulfonic acid disclosed herein.

In some embodiments, provided compositions comprise greater than 93% by weight fatty aldehyde, less than 7% by weight fatty alcohol, and less than 2% by weight water, optionally free/unbound water.

In some embodiments, compositions are provided wherein the absorbance of light at 680nm in a cuvette having an optical path length of 5mm 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.

A process for producing a fatty acetal and an alpha-hydroxysulfonic acid.

Fatty aldehydes may be usefully converted into other compounds that can be converted back into the fatty aldehyde. This conversion back to fatty aldehydes can be carried out by hydrolysis of the bond, cleavage of the bond and/or conversion of the functional group. Such other compounds may be used to better store fatty aldehydes, which are gradually released when the compound is converted back. For example, the compound may be less volatile than the corresponding fatty aldehyde, whereby the more volatile fatty aldehyde is continuously released as the compound is converted to the fatty aldehyde. Suitable compounds that can be produced from the fatty aldehydes include acetals and alpha-hydroxysulfonic acid.

One embodiment of the present disclosure provides a process for converting a fatty alcohol to a fatty acetal, the process comprising the steps of:

a. Providing a reaction mixture comprising a fatty alcohol composition comprising a fatty alcohol as disclosed herein, a catalyst composition as disclosed herein, and a solvent as disclosed herein,

b. exposing the reaction mixture to at least 0.25ml of oxygen per gram of fatty alcohol per minute by bubbling a gaseous mixture comprising oxygen through the reaction mixture, thereby obtaining fatty aldehydes, and

c. the aldehyde function of the fatty aldehyde is converted to an acetal function,

thus obtaining the fatty acetal. In a further embodiment, the fatty alcohol is a desaturated fatty alcohol. In yet another embodiment, the fatty aldehyde is a desaturated fatty aldehyde. In yet another embodiment, the fatty acetal is a desaturated fatty acetal.

a. conversion of fatty alcohols to fatty aldehydes as disclosed herein

b. The aldehyde function of the fatty aldehyde is converted to an acetal function,

One embodiment provides a fatty acetal obtained by the methods disclosed herein.

One embodiment of the present disclosure provides a process for converting a fatty alcohol to a fatty α -hydroxysulfonic acid, the process comprising the steps of:

c. converting the aldehyde functionality of the fatty aldehyde to an alpha-hydroxysulfonic acid functionality,

thus obtaining the fatty alpha-hydroxysulfonic acid. In a further embodiment, the fatty alcohol is a desaturated fatty alcohol. In yet another embodiment, the fatty aldehyde is a desaturated fatty aldehyde. In a further embodiment, the fatty α -hydroxysulfonic acid is a desaturated fatty α -hydroxysulfonic acid.

a. converting a fatty alcohol to a fatty aldehyde as disclosed herein, and

b. Converting the aldehyde functionality of the fatty aldehyde to an alpha-hydroxysulfonic acid functionality,

One embodiment of the present disclosure provides fatty alpha-hydroxysulfonic acid obtained from the methods disclosed herein.

Pheromone and controlled release thereof

The presently disclosed compounds may act as pheromones. In one embodiment of the present disclosure, a pheromone composition disclosed herein may comprise one or more aldehydes disclosed herein, one or more acetals disclosed herein, and/or one or more alpha-hydroxysulfonic acids disclosed herein. In particular embodiments of the present disclosure, a pheromone composition disclosed herein may comprise one or more fatty aldehydes disclosed herein, one or more fatty acetals disclosed herein, and/or one or more fatty alpha-hydroxysulfonic acids disclosed herein.

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, for example the air above the crop. The pheromone composition may be formulated to be released slowly into the atmosphere and/or to prevent degradation after release. In one embodiment of the present disclosure, the pheromone composition is contained in a carrier, such as a microcapsule, a biodegradable sheet or a paraffin-based matrix. In one embodiment of the present disclosure, the pheromone composition is formulated as a slow release spray.

In certain embodiments, the pheromone composition may include one or more polymeric agents known to those of skill in the art to control the release of the composition to the environment. In some embodiments, the polymeric attractant composition is not affected by environmental conditions. The polymeric agent may also be a sustained release (or slow release or controlled release) agent that enables continuous release of 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 rosin, lignin, melamine, polyurethane, vinyl polymers such as polyvinyl acetate (PVAC), polycarbonate, polyvinylidene nitrile, polyamide, polyvinyl alcohol (PVA), polyamide aldehyde, polyvinyl aldehyde, polyester, polyvinyl chloride (PVC), polyethylene, polystyrene, polyvinylidene, silicone, and combinations thereof. In one embodiment of the present invention, the cellulose derivative is selected from the group consisting of methylcellulose, ethylcellulose, cellulose acetate butyrate, cellulose acetate propionate, cellulose propionate, and combinations thereof.

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 invention, the one or more fatty alcohols are selected from undecanol, dodecanol, tridecanol, tridecenol, tetradecenol, pentadecanol, hexadecanol, hexadecenol, octadecenol, and octadecenol. In one embodiment of the present disclosure, the fatty acid ester is selected from the group consisting of undecyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, pentadecyl ester, hexadecyl ester, octadecyl ester, and octadecyl ester. In one embodiment of the present disclosure, the fatty acid ester is selected from the group consisting of alkyl undecanoate, alkenyl undecanoate, alkyl dodecanoate, alkenyl dodecanoate, alkyl tridecanoate, alkenyl tridecanoate, alkyl tetradecanoate, alkenyl tetradecanedienoate, alkyl pentadecanoate, alkyl tridecanoate alkenyl pentadecanoate, alkyl pentadecanoate, alkenyl pentadecanoate, alkyl hexadecanoate, alkenyl hexadecanoate, alkyl hexadecenoate, alkenyl hexadecenoate, alkyl hexadecadienoate, alkenyl hexadecadienoate, alkyl octadecenoate, alkenyl octadecenoate, alkyl octadecadienoate, and alkenyl octadecadienoate.

An alternative method for controlling the release of pheromones is to use compounds that degrade to active pheromones when subjected to an element. Aldehydes, such as the fatty aldehydes disclosed herein, readily react with alcohols to form dialkyl acetals. The alcohol may be another pheromone alcohol (e.g., Z11-1-hexen-1-ol, Z9-1-hexen-1-ol, or a similar unsaturated alcohol). Alternatively, the alcohol may be a short chain alcohol such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol. Furthermore, when the alcohol is a diol, a cyclic acetal may be formed. Examples of diols are ethylene glycol, 1, 3-propanediol and 1, 2-propanediol. Alternatively, a mixture of alcohols may be used. Fatty acetals can be produced using the methods disclosed herein. In one embodiment of the present disclosure, a fatty acetal is produced from a fatty aldehyde disclosed herein and two similar or different alcohols. In one embodiment, the acetal is produced from a fatty aldehyde disclosed herein and two similar or different alcohols disclosed herein. In one embodiment of the present disclosure, the fatty acetals are produced from a fatty aldehyde disclosed herein and two similar or different fatty alcohols disclosed herein. In one embodiment, the fatty acetal is composed of a fatty aldehyde as disclosed herein and two similar or different C' s ₁ -C ₇ Alcohol production. In one embodiment of the present disclosure, the fatty acetals are produced from fatty aldehydes disclosed herein and two similar or different alcohols selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol. In one embodiment of the present disclosure, acetals are produced from fatty aldehydes and diols disclosed herein. In one embodiment, the acetals are produced from fatty aldehydes disclosed herein and diols selected from the group consisting of ethylene glycol, 1, 3-propanediol, and 1, 2-propanediol.

The term "produced from … …" in connection with acetals is not intended to limit acetals to a specific method of production thereof. The term is used only to provide structural information about the acetal. For example, acetals may be produced from the reaction of hemiacetals with an alcohol. For example, the acetal produced from 1-methoxyethanol-1-ol (hemiacetal) corresponds to the acetal produced from ethanol and two molecules of methanol.

The fatty 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 fatty aldehyde is present in the pheromone composition as trioxane and/or tetraxane. These oligomers act as reservoirs of aldehydes, allowing for controlled release of aldehydes. The aldehyde oligomer can be produced in the presence of an acid catalyst. Examples of acids that may be used for acetal formation or for oxetane formation include hydrochloric acid, sulfuric acid, phosphoric acid or bisulphate. Bisulphates are particularly advantageous for the formation of oxacyclohexanes.

Another suitable slow-release compound is alpha-hydroxysulfonic acid. These compounds are readily formed from aqueous solutions of bisulfites, particularly sodium bisulfites. In one embodiment of the present disclosure, the slow release pheromone composition comprises alpha-hydroxysulfonic acid.

The acetal-type slow-release pheromone described above gradually reverts to an aldehyde when exposed to weak acids and moisture. The release rate will depend on the nature of the type of acetal, allowing the tailored composition to be tailored to certain circumstances. Alpha-hydroxysulfonic acid can slowly release pheromone under both acidic and basic conditions.

One embodiment of the present disclosure provides a fatty aldehyde sustained-release composition comprising a fatty acetal as disclosed herein. An embodiment of the present disclosure provides a method of producing a fatty aldehyde sustained release composition disclosed herein, the method comprising: the methods disclosed herein are practiced to provide fatty acetals and formulate the fatty acetals in a sustained release composition. In a further embodiment, the fatty aldehyde is a desaturated fatty aldehyde. In yet another embodiment, the fatty acetal is a desaturated fatty acetal.

One embodiment of the present disclosure provides a fatty aldehyde sustained release composition comprising a fatty alpha-hydroxysulfonic acid disclosed herein. An embodiment of the present disclosure provides a method of producing a fatty aldehyde sustained release composition disclosed herein, the method comprising: the methods disclosed herein are practiced to provide fatty alpha-hydroxysulfonic acid and formulate the fatty alpha-hydroxysulfonic acid in a sustained release composition. In a further embodiment, the fatty aldehyde is a desaturated fatty aldehyde. In yet another embodiment, the fatty α -hydroxysulfonic acid is a desaturated fatty acetal.

The slow release pheromone may optionally be formulated with an agent to further modulate the release of the compound. These compositions optionally contain agents to adjust humidity and pH. The slow release composition may be a mixture of the above acetals, aldehydes, alcohols and alpha-hydroxysulfonic acid.

It is advantageous to minimize the number of steps in chemical synthesis, for example, to reduce costs and minimize waste. Advantageously, the acetals and alpha-hydroxysulfonic acids disclosed herein are produced in as few steps as possible. This can be achieved by producing the acetal and the α -hydroxysulfonic acid directly from the reaction mixture for producing the fatty aldehyde.

Biological production of fatty alcohols

Methods for producing desaturated fatty alcohols, desaturated fatty alcohol acetates and desaturated fatty aldehydes in microbial cell factories, particularly in yeast, are available in the art.

In particular, the desaturated compounds can be obtained as described in WO2016/207339, WO2018/109163, WO2018/109167, WO2021/078452, WO2020/169389, WO2021/123128 and in EP21183459.3 entitled "Methods and yeast cells for production ofdesaturated compounds (method for producing desaturated compounds and yeast cells)" filed by the same applicant on month 7 of 2021 and entitled "Methods and yeast cells forproduction ofdesaturated compounds (method for producing desaturated compounds and yeast cells)" filed by the same applicant on month 7 of 2021.

Briefly, desaturated fatty alcohols can be produced in yeast cells, particularly in Saccharomyces or yarrowia cells, e.g., saccharomyces cerevisiae or yarrowia lipolytica cells, by introducing one or more suitable heterologous fatty acyl-CoA desaturases that introduce at least one double bond in fatty acyl-CoA and one or more suitable heterologous fatty acyl-reductase (FARs). These desaturated fatty alcohols can then be converted to desaturated fatty aldehydes using the methods disclosed herein.

Examples

Example 1: oxidation of fatty alcohol mixtures with low oxygen transfer rates

1755g acetonitrile was added to 800g fatty alcohol mixture (Table 1). To the reaction mixture was added a catalyst comprising 26.2 g of 2.2' -bipyridine, 62.7 g of copper (I) tetraacetonitrile trifluoromethane sulfonate, 17.5 g of 4-hydroxy-TEMPO and 13.8 g of 1-methylimidazole. The reaction was started with a gas flow of 1dm3/min and after 160 minutes was reduced to 0.2dm3/min. The conversion of alcohol to aldehyde was stabilized at 60%.

Reaction sampling

1ml of the reaction mixture was taken out of the reactor and quenched with 1ml of saturated NaHCO3, 1ml of ethyl acetate was added, and the sample was vigorously shaken. Mu.l of the organic phase was taken out and diluted in a GC vial with 1ml of ethyl acetate. Samples were analyzed by GC-FID. For reaction monitoring, the relative peak area% was used to determine the progress of the reaction. Reaction sampling was similarly performed in the following examples.

Table 1: the feed composition of example 1.

Example 2: oxidation of fatty alcohol mixtures with moderate oxygen transfer rates

1755g acetonitrile was added to 800g fatty alcohol mixture. To the reaction mixture was added a catalyst comprising 26.2 g of 2.2' -bipyridine, 62.7 g of copper (I) tetraacetonitrile trifluoromethane sulfonate, 17.5 g of 4-hydroxy-TEMPO and 13.8 g of N-methylimidazole. The reaction was started with a gas flow of 1dm3/min and maintained at 1dm3/min. The conversion of alcohol to aldehyde was stabilized at 83%.

Example 3: oxidation of fatty alcohol mixtures with high oxygen transfer rates

To 100g of the fatty alcohol mixture was added 218g of acetonitrile. To the reaction mixture was added a catalyst comprising 1.56 g of 2.2' -bipyridine, 3.77 g of copper (I) tetraacetonitrile trifluoromethane sulfonate, 1.03 g of 4-hydroxy-TEMPO and 0.82 g of N-methylimidazole. The reaction was started with a gas flow of 1dm3/min and maintained at 1dm3/min. The conversion of alcohol to aldehyde was stabilized at 93%.

Example 4: oxidation of fatty alcohol mixtures

800g of a fatty alcohol mixture comprising fatty alcohol was oxidized using air bubbling through the above fatty alcohol mixture and a 1600ml solution of acetonitrile at a rate of 2.2dm 3/min. To the reaction mixture was added a catalyst comprising 62g of copper (I) tetraacetonitrile triflate, 26g of 2.2' -bipyridine, 10g of 4-hydroxy TEMPO and 13.6g of 1-methyl-imidazole. The reaction was left for 2 hours during which the temperature increased from 22 ℃ to 52 ℃ after 1 hour, followed by a decrease in temperature to 42 ℃ after 2 hours. After 73 minutes the reaction yield steadily increased to over 70% and further increased to 87% at 150 minutes. FIG. 1 shows the reaction yield as a function of time.

Example 5: oxidation of fatty aldehyde mixtures using adsorbent adsorption of reaction water

Air was used at 2dm ³ The rate per min was bubbled through a solution of the above fatty alcohol mixture and 625g of acetonitrile to oxidize 252g of the fatty alcohol mixture containing the fatty alcohols in Table 2. To the reaction mixture was added a catalyst comprising 18 grams of copper (I) tetraacetonitrile triflate, 8.2 grams of 2.2' -bipyridine, 5.5 grams of 4-hydroxy TEMPO, 8.5 grams of 1-methylimidazole, and 20 grams of 4 angstrom molecular sieve. The reaction was left for 2 hours during which the temperature increased from 22 ℃ to 52 ℃ after 1 hour, followed by a decrease in temperature to 42 ℃ after 2 hours. The conversion rate steadily increased to over 95% at 139 minutes. FIG. 2 shows the reaction yield as a function of time.

Table 2: composition of the alcohol mixture used in the examples.

Example 6: oxidation of fatty alcohol mixtures using water adsorbents to adsorb water from solvents and reaction water

800g of a fatty alcohol mixture comprising the fatty alcohols in Table 3 was oxidized using air bubbling through a solution of the above fatty alcohol mixture and acetonitrile 1766g at a rate of 6dm 3/min. To the reaction mixture was added a catalyst comprising 62 grams of copper (I) tetraacetonitrile triflate, 26 grams of 2, 2' -bipyridine, 10.6 grams of 4-hydroxy TEMPO, 16.6 grams of N-imidazole, and 65 grams of 4 angstrom molecular sieve. The reaction was left for 2 hours during which the temperature was increased from 23 ℃ to 51 ℃ after 1 minute and 13 minutes, followed by a decrease in temperature to 22 ℃ after 6 hours. The conversion rate steadily increased to more than 99% at 110 minutes. FIG. 3 shows the reaction yield as a function of time.

Table 3: composition of the alcohol mixture used in example 6.

Compounds of formula (I)	Average,% (w/w)
		Monounsaturated tetradecen-1-ol	<LOQ
Tetradecan-1-ol	<LOQ
		Monounsaturated pentadecen-1-ols	5.9
Pentadec-1-ol	0.8
		(Z) -11-hexadecenal	<LOQ
(Z) -9-hexadecen-1-ol	3.2
		(Z) -11-sixteenCarbene-1-ols	78.2
Hexadecan-1-ol	7.6
		Other fatty alcohols	<6％
Total GC-FID quantification	>99％

Example 7: low, medium and high oxygen transfer rate comparison

As outlined in the previous examples, the fatty alcohol composition, the catalyst composition and the solvent are mixed. Table 4 summarizes the conversion of fatty alcohol to fatty aldehyde, given as ald/(alc+ald), providing the specified injection rate and injection time. A 20% oxygen mixture was used.

Table 4: conversion of fatty alcohols to fatty aldehydes

The low oxygen transfer rate (sparge 0.2L/h) only provides moderate conversion of fatty alcohol to fatty aldehyde at long reaction times (1427 minutes). Moderate oxygen transfer rates (1L/h) provide better conversion but also require longer reaction times. The high oxygen transfer rate (2.2L/h) provides excellent conversion of fatty alcohols. There is a trend that longer reaction times (305-320 minutes) result in slightly lower yields, 87-93%, while shorter reaction times (110-174 minutes) result in excellent conversions of 97-99%.

Furthermore, it was observed that the removal of water formed during the reaction further improved the yield (table 5). Water is known to participate in the formation of carboxylic acids, and thus removal of water further improves yield. It should be noted that not all of the water needs to be adsorbed, and that the addition of sufficient molecular sieve is sufficient to reduce the final water content by about 16 mole%.

Table 5: the reaction yield is improved by partial removal of water during the oxidation.

Example 8: purification of the reaction mixture

Method

Calibration standards containing dodecane-1-ol, (Z) -11-hexadecenal, (Z) -9-hexadecenal, hexadecal, tetradecal, tetradecan-1-ol, pentadecan-1-ol, hexadecan-1-ol, (Z) -9-hexadecan-1-ol and (Z) -11-hexadecan-1-ol were prepared at concentrations ranging from 0.01mg/mL to 1 mg/mL. mu.L of 10mg/mL methyl nonate was added to 1mL of the standard, and a calibration curve was obtained. Monounsaturated pentadecenal was quantified with pentadecenal.

UV-vis spectrometer: thermo Genesys 5S was used for UV-vis spectrometry. The samples were placed in concentrated form in 5mm quartz cuvettes and spectra were measured from 350nm to 1100 nm. Lambda of Cu adsorption _max Measured at 680 nm.

Sample preparation of GC-FID:

three aliquots of approximately 50mg each of the sample were transferred to 50mL volumetric flasks, weighed, and ethyl acetate was added to the graduation marks. 1000 μl of each diluted aliquot was transferred to GC vials and 10 μl of internal standard solution was added. The internal standard solution was 10mg/mL ethyl acetate solution of methyl nonadecanate.

Analysis conditions:

qualitative analysis was performed on an Agilent GC 7820A coupled to MS 5977B, split/no-jet injector, and DB-Fatwax UI column (30 m, 0.25mm inside diameter, and 0.25 μm membrane). The operating parameters are: injection amount is 1 muL, split ratio is 20:1, injector temperature is 220 ℃, constant flow rate is 1mL/min helium, oven temperature is raised to 80 ℃ for 1 minute, 15 ℃/min to 150 ℃ for 7 minutes, 10 ℃/min to 210 ℃ for 7 minutes, 20 ℃/min to 230 ℃ for 5 minutes.

Quantitative analysis was performed on an Agilent GC 7890B coupled with FID, split/no-jet injector and HP-5 column (30 m, 0.32mm inside diameter and 0.25 μm membrane). The operating parameters are: the injection quantity is 1 mu L, the split ratio is 1:40, the injector temperature is 220 ℃, the constant flow rate is 2mL/min of hydrogen, the temperature of the oven is increased to 80 ℃ for 1 minute, 15 ℃/min to 150 ℃ for 7 minutes, 10 ℃/min to 210 ℃ and 20 ℃/min to 300 ℃.

Analysis criteria:

the purity of (Z) -11-hexadecenal from Pherobank was 99.1%. Pentadecan-1-ol from AlfaAesar was 99% pure. Hexadecan-1-ol was purchased from Merck at 99% purity. (Z) -9-hexadecen-1-ol and (Z) -11-hexadecen-1-ol were purchased from Pherobank in 98% purity. Tetradecan-1-ol and methyl nonate were purchased from Larodan at 99% purity.

Qualitative analysis:

the following compounds were identified based on their spectra and retention times matching the analytical criteria: tetradecaldehyde (14:Ald), pentadecanol (15:Ald), (Z) -9-hexadecenal (Z9-16:Ald), (Z) -11-hexadecenal (Z11-16:Ald), hexadecal (16:Ald) and (Z) -11-hexadecen-1-ol (Z11-16:OH).

Monounsaturated pentadecenal (15-1: ald) was identified based on its match to spectra in the NIST library.

Preparation of the reaction mixture

200g of a fatty alcohol mixture comprising 78% of Z9-hexadecenol and Z11-hexadecenol was added to 1dm ³ In a jacketed reaction vessel. 16 grams of 4 angstrom molecular sieve, 6.4 grams of 2,2' -bipyridine, 3.6 grams of 4-hydroxy-TEMPO, and 3.4 grams of N-methylimidazole were added to the vessel. A solution of 15.6g of copper (I) tetrafluoroacetonitrile in 400ml of acetonitrile was added. Air was blown into the solution at a rate of 2l/min for 2 hours.

Representative embodiments of the crude reaction products produced using this process comprise about 30% fatty aldehyde, about 1.0% bipyridine, about 0.4% copper, about 0.6%4-OH-TEMPO, about 0.5% 1-methylimidazole, and about 62% acetonitrile.

Purification

100g of the reaction mixture are taken out and extracted with 165g of n-heptane. After vigorous stirring for 5 minutes, the mixture was left for 30 minutes to allow the phases to settle. The lower phase containing acetonitrile and a large amount of copper, bipyridine, N-methylimidazole and OH-TEMPO was discarded, the upper phase containing mainly N-heptane and pheromone products was collected and heptane was evaporated at 65℃and 15 mbar. 32g of a product containing 74% of Z9-hexadecenol and Z11-hexadecenol are obtained.

Example 9: purification of the reaction mixture

100g of the reaction mixture produced in example 8 are taken off and extracted with 165g of n-heptane and 1g of glacial acetic acid. After vigorous stirring for 5 minutes, the mixture was left for 30 minutes to effect phase separation. The lower phase was discarded and the upper phase was collected and heptane was evaporated at 65 ℃ to 15 mbar. 30g of product are produced, which contain 74.9% of Z9-hexadecenol and Z11-hexadecenol.

Example 10: purification of the reaction mixture

100g of the reaction mixture produced in example 7 are taken off and extracted with 165g of n-heptane and 1.2g of glacial acetic acid. After vigorous stirring for 5 minutes, the mixture was left for 30 minutes to effect phase separation. The lower phase was discarded and the upper phase was collected and heptane was evaporated at 65 ℃ to 15 mbar. 30.2g of product are produced, which contains 73.8% of Z9-hexadecenol and Z11-hexadecenol.

Example 11: purification of the reaction mixture

100g of the reaction mixture produced in example 7 are taken off and extracted with 165g of n-heptane and 2g of glacial acetic acid. After vigorous stirring for 5 minutes, the mixture was left for 30 minutes to effect phase separation. The lower phase was discarded and the upper phase was collected and heptane was evaporated at 65 ℃ to 15 mbar. 35.6 g of product are obtained, which contain 74.2% of Z9-hexadecenol and Z11-hexadecenol.

Example 12: comparative examples of typical oxidation procedures for Z11-16 OH (Z11-hexadecenol) oil and aqueous work-up

100g (86% total alcohol purity; 0.36mol and 60.04% of the activin Z11-16: OH (Z11-hexadecenol)) and 200ml of CH of starting material were added to a 500ml bottle equipped with a bubbler and reflux condenser ₃ CN. Then 2.8 is added to the suspension7g of copper (I) bromide (5 mol%;0.02 mol), 2.79g of 2,2' -bipyridine (Bipy) (5 mol%;0.02 mol), 1.40g of (4-hydroxy-2, 6-tetramethylpiperidin-1-oxyl (4-OH-TEMPO)) (2.5 mol%; 0.01 mol), 1.43ml of N-methylimidazole (5 mol%;0.02mol;1.47 g). The reaction was stirred until the Z11-16:OH signal had disappeared (16/20 hours) on GCMS.

Acetonitrile in the mixture was evaporated under reduced pressure. The residue was diluted with 200ml of ethyl acetate and transferred to a separatory funnel. The solution was treated with 2X 200ml of 0.5N H ₂ SO ₄ The solution was washed, or until the organic layer lost blue.

The solution was further washed with 1X 100ml of saturated sodium thiosulfate solution and 1X 50ml of saturated NaCl solution. The combined organic fractions were dried over sodium sulfate, filtered, and concentrated under reduced pressure.

Example 13: comparison of purification protocol and product stability

Results

Table 7 shows a comparison of copper, oxidant and ligand content in the purified reaction products as outlined in examples 7 to 12.

Table 7: impurity content in the purified products of examples 8 to 12.

The process of the present disclosure (examples 8 to 11) provides a purified product having a much lower content of unaccounted for components (12%) than the product (18%) obtained using the comparative purification process of example 12.

Comparative example 12 is higher in copper content, with an absorbance of 0.7, as assessed by absorbance at 680nm in a 5mm cuvette. Example 8 (where no acid was added during purification) had a similar amount of copper as demonstrated by an absorbance of 0.76. Example 9, in which 1g of acetic acid was added during purification, showed a much lower absorption of 0.035, indicating a low copper content. This trend continued for examples 10 and 11, which added 1.5g and 2g of acetic acid, respectively. Specifically, the product of example 11 showed a minimum absorption of 0.02. Based on these findings, carboxylic acids and/or carboxylates are expected to coordinate copper ions, thereby facilitating their separation from the purified product.

The content of 4-OH-TEMPO in the product of comparative example 12 and its reduced form was relatively high, 1.5%. In contrast, the purified products of examples 8 to 11 were relatively low in 4-OH-TEMPO, ranging from 0.60 to 0.66%, indicating that the purification scheme is also effective in removing this by-product.

For ligand BIPY, the purification schemes of the present disclosure provide lower levels than quantifiable levels, which perform similarly to the comparative scheme of example 12.

Example 14: stability of the purified product

Impurities present in the purified product have a significant and negative impact on product stability. Table 8 shows the initial purity and the purity after 25 days.

Table 8: product stability. * Tetradecal, tetradecyl, pentadecenal, pentadecen-1-ol, (Z) -9-hexadecenal, (Z) -11-hexadecenal, hexadecal, (Z) -hexadecal-9-en-1-ol, (Z) -hexadecal-11-en-1-ol, and hexadecan-1-ol.

As the copper amount decreases, the product stability increases significantly. The product of example 8 showed an absorbance at 680nm of 0.76 and experienced a reduction of about 25% in (Z) -9-hexadecenal + (Z) -11-hexadecenal after 25 days. In contrast, the purified products of examples 9 to 11 exhibited lower copper content (absorbance at 680nm of 0.035 to 0.02), and after 25 days the reduction of (Z) -hexadecenal of (Z) -9-hexadecenal + (Z) -11-hexadecenal was only 15%, 7% and 8%, respectively. Similar stability trends also occur for total quantitative fatty alcohol and aldehyde content. Thus, the presently disclosed purification schemes provide for more fatty alcohol table compositions.

Example 15: preparation of the catalyst in a 1.5m3 reactor

23.6kg of copper (II) triflate was added to a 1500L stainless steel vessel equipped with an anchor stirrer and reflux condenser. 17.5 kg of copper pellets (0.8-2.0 mm) and 12.2 kg of copper particles (3+14 mesh) were added to the tank. 630kg of acetonitrile was added. The mixture was stirred at 40rpm and heated to 85-90 ℃. After refluxing for about 3 hours, the mixture was cooled to room temperature.

The mixture was filtered using a Guedu filter. The filtration rate was 60-70 liters per hour, yielding about 770 liters of catalyst-containing liquid. A total of 640kg of catalyst solution was produced. It was divided into 2 transportable containers, each weighing approximately 320kg and used in examples 16 and 17.

Example 16: oxidation of fatty alcohol mixtures in a 4m3 reactor

A fatty alcohol mixture consisting essentially of zl-1-hexadecen-1-ol, Z9-1-hexadecen-1-ol and hexadecan-1-ol in the proportions listed in table 9.

TABLE 9

A 4000l reaction vessel equipped with a dissolved oxygen probe was equipped with:

315kg Biophero Z11-hexadecenol mixtures

315kg acetonitrile

10kg of 2, 2-bipyridine

5.5kg of 4-hydroxy TEMPO

5.5kg of 1-methylimidazole

25kgMolecular sieve

The DO probe is calibrated by introducing air into the medium while agitating the vessel.

320kg of catalyst in acetonitrile was then transferred to the fermenter. At this point, the reaction started.

The reaction set up is shown in table 10.

Table 10: MOT2106 oxidation reaction setup

Parameters (parameters)	Setting value
		Rotational speed of stirrer	200rpm
Temperature (temperature)	Controlled at 30 DEG C
		Aeration quantity	93kg/h
Pressure of	0.5 gauge pressure (1.5 absolute)

The oxidation reaction was closely monitored and sampled every 30 minutes. FIG. 4 shows the reaction data. At t=0, catalyst addition is complete and the gas flow is turned on. It can be seen that after a reaction time of 1 hour, the dissolved oxygen level greatly increased and the temperature also decreased again. These indicate that oxidation of the aldehyde form has been completed. Based on the information from the DO and GC analyses, it was decided to stop the gas flow after 1.5 hours of reaction time.

The reaction contents were in a waiting phase over a period of 1.5 to 3 hours. After 1.5-2.5 hours, the temperature was maintained at 30 ℃. After 2.5 hours, the temperature was kept at about 15 ℃.

After 3 hours, the container was emptied. This is accomplished by the air pressure at the head of the container, which does show up in a trend as an air flow. After 4 hours, the vessel was completely emptied and filled with 2 IBCs. The mass of the oxidation mixture was estimated to be 980kg.

After 1 hour, 94% conversion was achieved. The final conversion reaches 99%. The conversion increased slightly from 97% to 99% during the waiting time (1.5 hours-final sample).

Table 11 and FIG. 5 show the Z11-hexadecenal conversion over time.

TABLE 11

Time (h)	Z11_16:Ald	Z11_16:OH	Total peak area	Conversion rate
					0	34617	94691	129308	27
0.5	152447	106319	258766	59
					1	248650	14862	263512	94
1.5	247098	6364	253462	97
					Final sample (2 h)	253196	3136	256332	99

Example 17: fatty alcohol mixture at 4m ³ Oxidation in a reactor

A 4000L reaction vessel equipped with a dissolved oxygen sensor was equipped with:

254kg Biophero Z11-hexadecenol, as shown in example 16

315kg acetonitrile

10kg of 2, 2-bipyridine

5.5kg of 4-hydroxy TEMPO

5.5kg of 1-methylimidazole

25kgMolecular sieve

The oxidation reaction was carried out in 4000L 40R10 fermentors. First, the IBC content containing the reaction formulation was pressed into a fermenter. Next, 25kg of molecular sieve was added to the vessel from the top. The DO probe is then calibrated by introducing air into the medium while stirring the vessel.

The catalyst solution from example a was transferred to a fermenter set at a stirring speed of 51RPM and aeration was started. The reaction set up is shown in table 12.

Table 12

Parameters (parameters)	Setting value
		Rotational speed of stirrer	51rpm
Temperature (temperature)	Controlled at 30 DEG C
		Aeration quantity	93kg/h
Pressure of	0.5 gauge pressure (1.5 absolute)

The oxidation reaction was sampled every 30 minutes. FIG. 6 shows on-line reaction data for an oxidation process. At t=98.5, the catalyst solution was introduced into the vessel. The air flow was turned on and maintained between 85 and 100kg/h for about 2.5 hours. Between 101.5 and 104 hours, the contents of the fermenter are in a waiting phase. During this phase, 3.5kg/h of gas flow was passed through the ejector.

A maximum temperature of about 34 ℃ was observed (between t=99 and 99.5 hours. The liquid was cooled to about 15 ℃ at t=103 hours.

Table 13: conversion of Z11-hexadecenal over time during MOU2101

Time (h)	Z11_16:Ald	Z11_16:OH	Total peak area	Conversion%
					0	46645	150376	197021	24
0.5	53873	97395	151268	36
					1	140358	102612	242970	58
1.5	200203	48008	248211	81
					2	213234	7071	220305	97
2.5	218600	1917	220517	99

Example 18: z11, Z13-16: oxidation of OH to the corresponding aldehyde Z11, Z13-16:Ald

A primary fatty alcohol mixture containing 73 wt% Z11, Z13-16:oh ((Z11, Z13) -hexadecadien-1-ol) in the mixture was used as a representative sample for conversion to aldehyde.

Z11, Z13-16 OH mixture (8 g), 2' -bipyridine (0.25 g), 2, 6-tetramethylpiperidinyloxy (0.14 g) and 1-methylimidazole (0.13 g) were added to acetonitrile (20 ml). To the above solution was added 10ml of acetonitrile solution of copper (I) tetraacetonitrile trifluoromethane sulfonate.

The temperature of the reaction mixture was controlled to 30 ℃ while air was sprayed through the solution at a rate of 1 liter/min. After 164 minutes the air sparging was stopped, the reaction mixture was diluted in 1-heptane (40 ml) and the mixture was extracted with water (20 ml). The upper phase was evaporated to 10mbar at 60℃to give a product containing 65.5% by weight of Z11, Z13-16:Ald ((Z11, Z13) -hexadecadienal) with a residual amount of 3.4% by weight of Z11, Z13-16:OH.

These data show that fatty alcohols Z11, Z13-16:OH are chemically oxidized to the corresponding aldehydes Z11, Z13-16:Ald.

EXAMPLE 19 comparative examples of Small Scale Oxidation and Large Scale Oxidation

Small scale 1

24g of a fatty alcohol mixture comprising the fatty alcohols in Table 3 was oxidized in an open shake flask with the above fatty alcohol mixture and 5g acetonitrile. To the reaction mixture was added a catalyst comprising 1.88g of copper (I) tetrafluoroacetonitrile triflate, 0.78g of 2,2' -bipyridine, 0.43g of 4-hydroxy TEMPO, 0.41N-imidazole, and 5.4g A catalyst of molecular sieve. The reaction was left at 30℃for 2 hours. The conversion rate steadily increases, reaching more than 97% at 120 minutes and finally reaching 100% at 180 minutes.

Small scale 2

250g of a fatty alcohol mixture comprising the fatty alcohols in Table 3 was oxidized in a glass reactor equipped with a stirrer and an air-jet. To a fatty alcohol mixture diluted with 545g of acetonitrile was added 19g of copper (I) tetraacetonitrile triflate, 8g of 2.2' -bipyridine, 5.3g of 4-hydroxy TEMPO and 6.5g N-imidazole. The reaction was mixed at room temperature for the whole reaction time. The conversion rate steadily increased to above 58% at 120 minutes, eventually reaching 93% after 20 hours.

Large scale of

Step 1: preparation of catalyst Cu (ACN) from copper (II) trifluoromethane and metallic copper ₄ OTf solution. 100L of acetonitrile was added to a stainless steel vessel with an anchor stirrer. Then, 2.81kg Cu (Otf) was added with gentle stirring ₂ And 2.8kg copper particles. The mixture was heated to 85 ℃. After refluxing for 5.5 hours, the mixture was cooled to room temperature. Subsequently, the mixture is pressed through a filter to removeRemoving the residual copper particles. This procedure provided 90L of pale yellow solution for the subsequent step.

Step 2: the oxidation reaction was carried out in a 300L steel vessel with an air sparger. To the tank was added 60.8kg of the Z11-hexadecenol mixture, 50L of acetonitrile, 2.4kg of 2, 2-bipyridine, 1.1kg of 4-hydroxy TEMPO and 1.3kg of 1-methylimidazole. Finally, the catalyst solution of step 1 was transferred to an oxidation vessel and 10Kg/h of air was introduced into the mixture with constant mixing. After 16 hours of reaction time, the conversion reached 67%.

Conclusion(s)

This comparative example shows that conventional oxidation processes developed for small scale oxidation are not always suitable for large scale, e.g. kilogram scale. On a larger scale, for example for commercial chemical production, high conversion and clean reaction profiles are critical process parameters, and the methods of the present disclosure provide a practical solution to these needs in the industry.

Reference to the literature

Stahl et al.J.Am.Chem.Soc.2011,133,16901-16910

Kumpulain and Koskinen, chem. Eur. J.2009,15,10901-10911

Project

The following progressive embodiments are further described herein:

1. A process for converting fatty alcohols to fatty aldehydes, said process comprising the steps of:

2. The method of item 1, comprising: at least 0.049. Mu. Mol of dissolved O per mu. Mol of copper per minute is added to the reaction mixture ₂ 。

3. The method of any of the preceding items, comprising: every mu mol of primary in the reaction mixtureAt least 0.0025. Mu. Mol of dissolved O is added per minute to the starting fatty alcohol ₂ 。

4. The method of any of the preceding items, comprising: at least 0.025. Mu. Mol of dissolved O per. Mu. Mol of fatty acid per minute is added to the reaction mixture ₂ 。

5. The method of any of the preceding items, comprising: at least 10 mu mol O ₂ For example at least 20. Mu. Mol O ₂ At least 40 mu mol O ₂ Or at least 60. Mu. Mol O ₂ Each gram of fatty alcohol per minute is added to the reaction mixture to obtain the fatty aldehyde, optionally wherein the fatty alcohol and the fatty aldehyde are desaturated.

6. The method of any one of the preceding items, wherein the reaction mixture is purified by reacting the reaction mixture with a catalyst comprising O ₂ Optionally enriched in O ₂ ) Mixing to add O ₂ 。

7. The method of any one of the preceding items, wherein the method is performed by causing a catalyst comprising O ₂ The mixing is performed by bubbling a gaseous mixture through the reaction mixture.

8. The method of clause 1, wherein the conversion is the conversion of a primary alcohol functional group to an aldehyde functional group.

9. The method of any of the preceding items, wherein the converting is oxidizing a primary alcohol functional group to an aldehyde functional group.

10. The method of any of the preceding items, wherein the fatty alcohol is a primary alcohol.

11. The method of any one of the preceding items, wherein the fatty alcohol is a saturated fatty alcohol.

12. The method of any one of the preceding items, wherein the fatty alcohol is a desaturated fatty alcohol.

13. The method of any one of the preceding items, wherein the fatty alcohol is a C10 to C26 fatty alcohol.

14. The method of any one of the preceding items, wherein the fatty alcohol is a C10 to C22 fatty alcohol.

15. The method of any one of the preceding items, wherein the fatty alcohol is a C12 to C20 fatty alcohol.

16. The method of any one of the preceding items, wherein the fatty alcohol is a C12 to C18 fatty alcohol.

17. The method of any one of the preceding items, wherein the fatty alcohol is a C12, C14, C16, or C18 fatty alcohol.

18. The method of any one of the preceding items, wherein the desaturated fatty alcohol has a double bond at position 9, 11, or 13, or wherein the desaturated fatty alcohol has a double bond at positions 9 and 11, or at positions 11 and 13.

19. The method of any one of the preceding items, wherein the desaturated fatty alcohol has a double bond at the 9-position or the 12-position, or wherein the desaturated fatty alcohol has double bonds at the 9-position and the 12-position.

20. The method of any one of the preceding items, wherein the desaturated fatty alcohol has a double bond at the 8-position or 10-position, or wherein the desaturated fatty alcohol has a double bond at the 8-position and 10-position.

21. The method of any one of the preceding items, wherein the fatty alcohol has a carbon chain length of 12, 14, or 16.

22. The method of any one of the preceding items, wherein the fatty alcohol is a unbranched fatty alcohol.

23. The method of any one of the preceding items, wherein the fatty alcohol is selected from the group consisting of:

24. The method of any one of the preceding items, wherein the fatty alcohol is selected from the group consisting of:

(E) 7, (Z) 9 desaturated fatty alcohols having carbon chain lengths of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22,

(E) 3, (Z) 8, (Z) 11 desaturated fatty alcohols having carbon chain lengths of 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22,

(Z) 9, (E) 11, (E) 13 desaturated fatty alcohols having carbon chain lengths of 14, 15, 16, 17, 18, 19, 20, 21 or 22,

(Z) 11, (Z) 13 desaturated fatty alcohols having carbon chain lengths of 14, 15, 16, 17, 18, 19, 20, 21 or 22,

(Z) 9, (E) 12 desaturated fatty alcohols having a carbon chain length of 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22,

(E) 7, (E) 9 desaturated 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) desaturated fatty alcohols having carbon chain lengths of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22.

25. The method of any one of the preceding items, wherein the fatty alcohol is selected from the group consisting of:

(E) 7, (Z) 9 desaturated fatty alcohols having a carbon chain length of 14,

(E) 3, (Z) 8, (Z) 11 desaturated fatty alcohols with a carbon chain length of 14,

(Z) 9, (E) 11, (E) 13 desaturated fatty alcohols with a carbon chain length of 14,

(E) 7, (Z) 9 desaturated fatty alcohols with a carbon chain length of 12,

(E) 3, (Z) 8, (Z) 11 desaturated fatty alcohols with carbon chain length of 12,

(Z) 9, (E) 11, (E) 13 desaturated fatty alcohols with a carbon chain length of 12,

(E) 8, (E) 10 desaturated 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 desaturated fatty alcohols with a carbon chain length of 16, and

(Z) 9, (E) 12 desaturated fatty alcohols with a carbon chain length of 14.

26. The method of any one of the preceding items, wherein the fatty alcohol is selected from the group consisting of: tetradecan-1-ol, pentadecyl-1-ol, hexadecan-1-ol, pentadecyl-1-ol, (Z) -9-hexadecen-1-ol, (Z) -11-hexadecen-1-ol, (7E, 9E) -undec-7, 9-dien-1-ol, (11Z, 13Z) -hexadecen-1-ol, (9Z, 12E) -tetradecadien-1-ol, and (8E, 10E) -dodecadien-1-ol.

27. The method of any of the preceding items, wherein the fatty alcohol composition comprises at least 30 wt% of one or more fatty alcohols, such as at least 40 wt%, 50 wt%, 55 wt%, e.g., 60 wt% of one or more fatty alcohols.

28. The method according to any of the preceding items, wherein the obtained fatty aldehydes are obtained as a fatty aldehyde composition comprising at least 30 wt.% of one or more fatty aldehydes, such as at least 40 wt.%, 50 wt.%, 55 wt.%, such as 60 wt.% of one or more fatty aldehydes.

29. The method of any one of the preceding items, wherein the fatty aldehyde is a saturated fatty aldehyde.

30. The method of any one of the preceding items, wherein the fatty aldehyde is a desaturated fatty aldehyde.

31. The method of any one of the preceding items, wherein the fatty aldehyde is a C10 to C26 fatty aldehyde.

32. The method of any one of the preceding items, wherein the fatty aldehyde is a C10 to C22 fatty aldehyde.

33. The method of any one of the preceding items, wherein the fatty aldehyde is a C12 to C20 fatty aldehyde.

34. The method of any one of the preceding items, wherein the fatty aldehyde is a C12, C14, or C16 fatty aldehyde.

35. The method of any one of the preceding items, wherein the fatty aldehyde is an unbranched fatty aldehyde.

36. The method of any one of the preceding items, wherein the desaturated fatty aldehyde has a double bond at position 9, 11, or 13, or wherein the desaturated fatty aldehyde has a double bond at positions 9 and 11, or at positions 11 and 13.

37. The method of any one of the preceding items, wherein the desaturated fatty aldehyde has a double bond at the 9-position or the 12-position, or wherein the desaturated fatty aldehyde has a double bond at the 9-position and the 12-position.

38. The method of any one of the preceding items, wherein the desaturated fatty aldehyde has a double bond at the 8-position or 10-position, or wherein the desaturated fatty aldehyde has a double bond at the 8-position and 10-position.

39. The method of any one of the preceding items, wherein the fatty aldehyde has a carbon chain length of 12, 14, or 16.

40. The method of any one of the preceding items, wherein the fatty aldehyde is selected from the group consisting of:

(Z) - Δ3 desaturated fatty aldehydes having carbon chain lengths of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22;

(E) - Δ3 desaturated fatty aldehydes having carbon chain lengths of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22;

(Z) - Δ5 desaturated fatty aldehydes having carbon chain lengths of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22;

(E) - Δ5 desaturated fatty aldehydes having carbon chain lengths of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22;

(Z) - Δ6 desaturated fatty aldehydes having carbon chain lengths of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22;

(E) - Δ6 desaturated fatty aldehydes having carbon chain lengths of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22;

(Z) - Δ7 desaturated fatty aldehydes having carbon chain lengths of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22;

(E) - Δ7 desaturated fatty aldehydes having carbon chain lengths of 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22;

(Z) - Δ8 desaturated fatty aldehydes having carbon chain lengths of 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22;

(E) - Δ8 desaturated fatty aldehydes having carbon chain lengths of 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22;

(Z) - Δ9 desaturated fatty aldehydes having a carbon chain length of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22;

(E) - Δ9 desaturated fatty aldehydes having a carbon chain length of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22;

(Z) - Δ10 unsaturated fatty aldehydes having a carbon chain length of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22;

(E) - Δ10 desaturated fatty aldehydes having carbon chain lengths of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22;

(Z) - Δ11 desaturated fatty aldehydes having carbon chain lengths of 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22;

(E) - Δ11 desaturated fatty aldehydes having carbon chain lengths of 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22;

(Z) - Δ12 desaturated fatty aldehydes having a carbon chain length of 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22;

(E) - Δ12 desaturated fatty aldehydes having a carbon chain length of 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22;

(Z) - Δ13 desaturated fatty aldehydes having carbon chain lengths of 14, 15, 16, 17, 18, 19, 20, 21, or 22; and

(E) -delta 13 desaturated fatty aldehydes having carbon chain lengths of 14, 15, 16, 17, 18, 19, 20, 21 or 22.

41. The method according to any one of the preceding items, wherein the fatty aldehyde is selected from the group consisting of:

(E) 7, (Z) 9 desaturated fatty aldehydes 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 desaturated fatty aldehydes of carbon chain length 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22,

(Z) 9, (E) 11, (E) 13 desaturated fatty aldehydes having a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21 or 22,

(Z) 11, (Z) 13 desaturated fatty aldehydes having a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21 or 22,

(Z) 9, (E) 12 desaturated fatty aldehydes having a carbon chain length of 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22,

(E) 7, (E) 9 desaturated fatty aldehydes of carbon chain length 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22

(E) 8, (E) 10 desaturated fatty aldehydes having carbon chain lengths of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22.

42. The method of any one of the preceding items, wherein the fatty aldehyde is selected from the group consisting of:

(E) 7, (Z) 9 unsaturated fatty aldehyde having a carbon chain length of 14,

(E) 3, (Z) 8, (Z) 11 desaturated fatty aldehydes with a carbon chain length of 14,

(Z) 9, (E) 11, (E) 13 desaturated fatty aldehydes with a carbon chain length of 14,

(E) 7, (Z) 9 desaturated fatty aldehydes with a carbon chain length of 12,

(E) 3, (Z) 8, (Z) 11 desaturated fatty aldehydes with a carbon chain length of 12,

(Z) 9, (E) 11, (E) 13 desaturated fatty aldehydes with a carbon chain length of 12,

(E) 8, (E) 10 desaturated fatty aldehydes with carbon chain length of 12

(E) 7, (E) 9 desaturated fatty aldehydes with a carbon chain length of 11,

(Z) 11, (Z) 13 desaturated fatty aldehydes with a carbon chain length of 16, and

(Z) 9, (E) 12 desaturated fatty aldehydes with a carbon chain length of 14.

43. The method of any one of the preceding items, wherein the fatty aldehyde is selected from the group consisting of tetradecane-1-aldehyde, pentadecane-1-aldehyde, hexadecane-1-aldehyde, pentadecene-1-aldehyde, (Z) -9-hexadecene-1-aldehyde, (Z) -11-hexadecene-1-aldehyde, (7 e,9 e) -undecane-7, 9-diene-1-aldehyde, (11Z, 13Z) -hexadecene-1-aldehyde, (9Z, 12 e) -tetradecene-1-aldehyde, and (8 e,10 e) -dodecadienol-1-aldehyde.

44. The method of any one of the preceding items, wherein the copper (I) source is a copper (I) salt.

45. The method of any one of the preceding items, wherein the copper (I) source is selected from the group consisting of copper (I) tetraacetonitrile triflate, copper (I) tetraacetonitrile tetrafluoroborate, copper (I) tetraacetonitrile hexafluorophosphate, and copper (I) tetraacetonitrile halide (I and copper (I) tetraacetonitrile perchlorate).

46. The method of any one of the preceding items, wherein the copper (I) source comprises a copper (II) compound and a reducing agent.

47. The method of any one of the preceding items, wherein the copper (II) compound is a copper (II) salt.

48. The method of any one of the preceding items, 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.

49. The method of any one of the preceding items, wherein the reducing agent is selected from the group consisting of copper metal, zinc metal, aluminum metal, sodium bisulfite, formic acid, formate, oxalate, and oxalate.

50. The method of any one of the preceding items, wherein the copper (I) source is a copper (II) salt and copper metal.

51. The method of any one of the preceding items, wherein the catalyst composition comprises a ligand.

52. The method of any one of the preceding items, wherein the ligand coordinates to copper (I) via nitrogen.

53. The method of any one of the preceding items, wherein the ligand comprises a pyridine moiety.

54. The method of any one of the preceding items, wherein the ligand is a bidentate nitrogen ligand.

55. The method of any one of the preceding items, wherein the ligand comprises a 2,2 '-bipyridine moiety or a 2,2' -bipyrimidine moiety.

56. The method of any one of the preceding items, wherein the ligand is selected from the group consisting of 2,2 '-bipyridine, 4' -dimethyl-2, 2 '-bipyridine, 5' -dimethyl-2, 2 '-bipyridine 2,2' -bipyrimidine, 2 '-bipyridine-4, 4' -dicarboxylic acid or an ester thereof, 2 '-bipyridine-5, 5' -dicarboxylic acid or an ester thereof.

57. The method of any one of the preceding items, wherein the catalyst composition comprises an aminooxy radical compound.

58. The method of any of the preceding items, wherein the aminooxy radical compound is selected from TEMPO, (4-hydroxy-2, 6-tetramethylpiperidin-1-yl) oxy (4-OH-TEMPO), 4-acetamido-TEMPO, 4-hydroxy-TEMPO benzoate, 4-amino-TEMPO, 2-azaadamantan-N-oxy, 9-azabicyclo [3.3.1] nonane-N-oxy, 4-carboxy-TEMPO, 4-maleimido-TEMPO, 4-methoxy-TEMPO, 1-methyl-2-azaadamantan-N-oxy, 4-oxo-TEMPO, and polymers functionalized with any of the aminooxy radical compounds.

59. The method of any one of the preceding items, wherein the aminooxy radical compound is (2, 6-tetramethylpiperidin-1-yl) oxy (TEMPO) or TEMPO derivative.

60. The method of any one of the preceding items, wherein the catalyst composition comprises a base.

61. The method of any one of the preceding items, wherein the base is an organic base.

62. The method of any one of the preceding items, 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, 3-tetramethylguanidine, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, and potassium t-butoxide.

63. The method according to any one of the preceding items, wherein exposing the reaction mixture to O2 is performed at 5 to 80 ℃, such as 10 to 70 ℃, such as 15 to 65 ℃.

64. The process according to any one of the preceding items, wherein exposing the reaction mixture to O2 is performed at 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.

65. The process of any one of the preceding items, wherein exposing the reaction mixture to O2 is performed at a pressure of 0.8 bar to 1.2 bar.

66. The method of any one of the preceding items, wherein exposing the reaction mixture to O2 is performed at ambient pressure.

67. The method of any one of the preceding items, wherein the reaction mixture is exposed to at least 0.3ml O2 per gram of fatty alcohol composition per minute, e.g., at least 0.4ml, 0.5ml, 0.6ml, 0.7ml, 0.8ml, 0.9ml, 1.0ml, 1.1ml, 1.2ml, 1.3ml, 1.4ml, e.g., at least 1.5ml O2 per gram of fatty alcohol composition per minute, as assessed at a pressure of 1 bar.

68. The method according to any of the preceding items, wherein the reaction mixture is exposed to at least 0.3ml O2 per gram of fatty alcohol per minute, e.g. at least 0.4ml, 0.5ml, 0.6ml, 0.7ml, 0.8ml, 0.9ml, 1.0ml, 1.1ml, 1.2ml, 1.3ml, 1.4ml, e.g. at least 1.5ml O2 per gram of fatty alcohol per minute, as assessed at a pressure of 1 bar.

69. The method according to any of the preceding items, wherein the reaction mixture is exposed to at least 60ml O2 per minute per mole of fatty alcohol, e.g. at least 100ml, 150ml, 200ml, 250ml, 300ml, 350ml, 400ml, e.g. at least 450ml O2 per minute per mole of fatty alcohol, as assessed at a pressure of 1 bar.

70. The method of any of the preceding items, wherein the reaction mixture is exposed to at least 10 μmol O2 per gram of fatty alcohol per minute, e.g., 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 O2 per gram of fatty alcohol per minute.

71. The process according to any of the preceding items, wherein the reaction mixture is exposed to at least 2.5mmol O2 per minute per mole of fatty alcohol, e.g. at least 4mmol, 6mmol, 8mmol, 10mmol, 12mmol, 14mmol, 16mmol, e.g. at least 18mmol O2 per minute per mole of fatty alcohol.

72. The method of any one of the preceding items, wherein the gas mixture comprises 5% to 100% O ₂ 。

73. The method of any one of the preceding items, wherein the gas mixture comprises 15% to 25% O ₂ 。

74. The method of any of the preceding items, wherein the gas mixture comprises at least 90% O ₂ 。

75. The method of any one of the preceding items, wherein the solvent is an aprotic polar solvent.

76. The method of any one of the preceding items, wherein the solvent is selected from the group consisting of acetonitrile, dimethylformamide, acetonitrile, propionitrile, butyronitrile, dimethylsulfoxide, dimethylacetamide, and propylene carbonate.

77. The method according to any of the preceding items, wherein the amount of solvent corresponds to 0 to 2000%, such as 100 to 1500%, such as 100 to 1000%, such as e.g. such as 100 to 500% by weight of the fatty alcohol composition.

78. The method according to any of the preceding items, wherein the amount of solvent corresponds to 100 to 2000%, such as 100 to 1500%, such as 100 to 1000%, such as 100 to 500% by weight of fatty alcohol.

79. The method of any of the preceding items, wherein the exposure to O2 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, 90 minutes, such as at least 100 minutes.

80. The method of any of the preceding items, wherein the exposure to O ₂ Is carried out in a bubble column reactor or a trickle bed reactor.

81. The method according to any of the preceding items, wherein the conversion of fatty alcohol is at least 60 wt%, such as at least 80 wt%, such as at least 85 wt%, 87 wt%, such as at least 90 wt%, such as at least 95 wt%, such as at least 99 wt%.

82. The method of any one of the preceding items, wherein the ratio of fatty acid produced to fatty aldehyde produced is less than 10:90.

83. The method according to any of the preceding items, wherein the conversion of fatty alcohol to 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%.

84. The method of any of the preceding items, further comprising: water is removed from the reaction mixture.

85. The method of any of the preceding items, wherein substantially upon exposure to O ₂ Water is removed from the reaction mixture throughout.

86. The method of any one of the preceding items, wherein removing water from the reaction mixture is achieved using an adsorbent material.

87. The method of any one of the preceding items, wherein the adsorbent material is selected from the group consisting of molecular sieves, silica gel, alumina, bentonite, calcium oxide, alkali metal carbonates, bicarbonates, or alkaline earth metal carbonates.

88. The method of any of the preceding items, further comprising: a step of removing water from the reaction medium before, during or after oxidation of the fatty alcohol.

89. The method of any of the preceding items, further comprising: to the reaction medium that absorbs or adsorbs water is added a water absorbing or adsorbing material, optionally selected from molecular sieves, silica gel, alumina, bentonite, calcium oxide, alkali metal carbonates, bicarbonates, or alkaline earth metal carbonates or combinations thereof.

90. The method of clauses 88 to 89, wherein the water absorbing or adsorbing material is added to the reaction medium in an amount such that the water content in the reaction medium after the oxidation process is 2 weight percent or less, and optionally the molar conversion of fatty alcohol to fatty aldehyde is over 93 percent.

91. The method of clauses 88 to 90, wherein the amount of water absorbing or adsorbing material added is at least 10g per mmol of fatty alcohol present in the reaction medium prior to oxidation, such as at least 15g per mmol of fatty alcohol, such as at least 19g per mmol of fatty alcohol, and wherein optionally the water absorbing or adsorbing material is a molecular sieve.

92. The method according to any of the preceding items, wherein the method further comprises an initial step of producing a fatty alcohol, preferably wherein the fatty alcohol is desaturated, the initial step comprising the steps of:

i. Providing yeast cells capable of producing fatty alcohols

incubating the yeast cells in a culture medium,

thereby producing fatty alcohols.

93. The method according to any one of the preceding items, wherein the method further comprises an initial step of producing fatty alcohols, the initial step comprising the steps of:

i. providing a yeast cell capable of synthesizing alkanoyl-coa, said yeast cell further capable of expressing:

-desaturase, and

alcohol-forming fatty acyl-CoA reductase,

incubating the yeast cells in a culture medium

Whereby a desaturase is capable of converting at least a portion of said alkanoyl-CoA to enoyl-CoA, and whereby said alcohol-forming fatty acyl-CoA reductase is capable of converting at least a portion of said enoyl-CoA to a fatty alcohol, thereby producing said fatty alcohol.

94. The method of any one of the preceding items, wherein the fatty alcohol is (Z) -11-hexadecen-1-ol, wherein the alkanoyl-CoA is hexadecanoyl-CoA, wherein the desaturase is Δ11-desaturase, and wherein the enoyl-CoA is (Z) -11-hexadecenoyl-CoA.

95. The method according to any one of the preceding items, wherein the method further comprises an initial step of producing fatty alcohols, the initial step comprising the steps of:

i. providing oleaginous yeast cells capable of producing a desaturated fatty alcohol, the yeast cells further comprising:

-being capable of expressing at least one heterologous fatty acyl-coa reductase capable of converting at least part of said desaturated fatty acyl-coa to a desaturated fatty alcohol, -having a mutation resulting in a reduction of fatty alcohol oxidase activity and having a mutation resulting in a reduction of activity of at least one of a fatty aldehyde dehydrogenase, a peroxisome biogenesis factor and a 3-phosphoglyceroyl transferase, and

incubating the yeast cells in a culture medium,

thereby producing fatty alcohols.

96. The method according to any one of the preceding items, wherein the method further comprises an initial step of producing fatty alcohols, the initial step comprising the steps of:

i. Providing a yeast cell capable of producing a desaturated fatty alcohol, said yeast cell expressing:

incubating the yeast cells in a culture medium,

thereby producing fatty alcohols.

97. The method according to any one of the preceding items, wherein the method further comprises an initial step of producing fatty alcohols, said initial step comprising: providing a yeast cell capable of producing a fatty alcohol and culturing the yeast cell in a medium under conditions that allow production of the fatty alcohol, wherein the medium comprises an extractant in an amount equal to or greater than its turbidity concentration measured in an aqueous solution, such as a medium, at a culture temperature, wherein the extractant is a nonionic ethoxylated surfactant, thereby producing a fatty alcohol.

98. The process according to any one of the preceding items, wherein the process further comprises an initial step of producing a fatty alcohol, preferably wherein the fatty alcohol is a desaturated fatty alcohol, said initial step comprising

i. Providing a yeast cell capable of producing a fatty alcohol ester, and culturing the yeast cell in a medium under conditions allowing production of the fatty alcohol ester, wherein the medium comprises an extractant in an amount equal to or greater than its turbidity concentration measured in an aqueous solution, e.g., medium, at a culture temperature, wherein the extractant is a nonionic ethoxylated surfactant, thereby producing a fatty alcohol ester, and ii. Converting the fatty alcohol ester to a fatty alcohol,

thereby producing fatty alcohols.

99. A method for purifying fatty aldehydes, comprising the steps of:

a. providing a crude reaction product comprising:

i. a fatty aldehyde, and a fatty acid,

copper ions, and

polar solvent;

c. the nonpolar phase is separated from the polar phase.

100. The fatty aldehyde purification process of any one of the preceding items, wherein the crude reaction product comprises:

i.5% to 80% of fatty aldehyde,

0.05 to 5.0% copper ions,

20% to 95% of a polar solvent.

101. The fatty aldehyde purification process of any one of the preceding items, wherein the crude reaction product comprises 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.

102. The fatty aldehyde purification process according to any one of the preceding items, wherein the crude reaction product further comprises a ligand, e.g. 0.1 to 10% of a ligand, e.g. 0.1 to 5% of a ligand, e.g. 0.1 to 2% of a ligand, e.g. about 1% of a ligand.

103. The fatty aldehyde purification process according to any one of the preceding items, wherein the ligand is a bidentate nitrogen ligand, for example a bidentate nitrogen ligand selected from the group consisting of 2,2 '-bipyridine, 4' -dimethyl-2, 2 '-bipyridine, 5' -dimethyl-2, 2 '-bipyridine 2,2' -bipyrimidine, 2 '-bipyridine-4, 4' -dicarboxylic acid or an ester thereof, 2 '-bipyridine-5, 5' -dicarboxylic acid or an ester thereof.

104. The fatty aldehyde purification process of any one of the preceding items, wherein the crude reaction product further comprises an aminooxy radical compound, such as 0.01 to 10% aminooxy radical compound, such as 0.01 to 5% aminooxy radical compound, such as about 0.01 to 2% aminooxy radical compound, such as about 0.5% aminooxy radical compound.

105. The fatty aldehyde purification process of any one of the preceding items, wherein the aminooxy radical compound is selected from TEMPO, (4-hydroxy-2, 6-tetramethylpiperidin-1-yl) oxy (4-OH-TEMPO), 4-acetamido-TEMPO, 4-hydroxy-TEMPO benzoate, 4-amino-TEMPO, 2-azaadamantane-N-oxy, 9-azabicyclo [3.3.1] nonane N-oxy, 4-carboxy-TEMPO, 4-maleimido-TEMPO, 4-methoxy-TEMPO, 1-methyl-2-azaadamantane-N-oxy, 4-oxo-TEMPO, and polymers functionalized with any of the aminooxy radical compounds.

106. The fatty aldehyde purification process of any one of the preceding items, wherein the crude reaction product further comprises a base, such as 0.1% to 10% base, such as 0.1% to 5% base, such as 0.1% to 2% base, such as about 0.5% base.

107. The fatty aldehyde purification process according to any one of the preceding items, 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, 3-tetramethylguanidine, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, and potassium t-butoxide.

108. The fatty aldehyde purification process according to any one of the preceding items, wherein the fatty aldehyde is a saturated fatty aldehyde.

109. The fatty aldehyde purification process of any one of the preceding items, wherein the fatty aldehyde is a desaturated fatty aldehyde.

110. The fatty aldehyde purification process of any one of the preceding items, wherein the fatty aldehyde is a C10 to C26 fatty aldehyde.

111. The fatty aldehyde purification process of any one of the preceding items, wherein the fatty aldehyde is a C10 to C22 fatty aldehyde.

112. The fatty aldehyde purification process of any one of the preceding items, wherein the fatty aldehyde is a C12 to C20 fatty aldehyde.

113. The fatty aldehyde purification process of any one of the preceding items, wherein the fatty aldehyde is a C12, C14 or C16 fatty aldehyde.

114. The fatty aldehyde purification process according to any one of the preceding items, wherein the fatty aldehyde is an unbranched fatty aldehyde.

115. The fatty aldehyde purification process according to any one of the preceding items, wherein the fatty aldehyde is selected from the group consisting of:

116. The fatty aldehyde purification process according to any one of the preceding items, wherein the fatty aldehyde is selected from the group consisting of:

(Z) 9, (E) 11, (E) 13 desaturated fatty aldehydes of carbon chain length 14, 15, 16, 17, 18, 19, 20, 21 or 22, and

(Z11, Z13) desaturated fatty aldehydes having a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21 or 22,

(Z9, E12) desaturated fatty aldehydes having a carbon chain length of 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22,

(7E, 9E) desaturated fatty aldehydes of carbon chain length 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22

(E8, E10) desaturated fatty aldehydes having carbon chain lengths of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22.

117. The fatty aldehyde purification process according to any one of the preceding items, wherein the fatty aldehyde is selected from the group consisting of:

(E) 7, (Z) 9 unsaturated fatty aldehyde having a carbon chain length of 14,

(E) 7, (Z) 9 desaturated fatty aldehydes with a carbon chain length of 12,

(Z) 9, (E) 11, (E) 13 desaturated fatty aldehydes of carbon chain length 12, and

(E) 8, (E) 10 desaturated fatty aldehydes with carbon chain length of 12

(E) 7, (E) 9 desaturated fatty aldehydes with a carbon chain length of 11,

(Z) 9, (E) 12 desaturated fatty aldehydes with a carbon chain length of 14.

118. The fatty aldehyde purification method according to any one of the preceding items, wherein the fatty aldehyde is selected from the group consisting of tetradecane-1-aldehyde, pentadecane-1-aldehyde, hexadecane-1-aldehyde, pentadecene-1-aldehyde, (Z) -9-hexadecene-1-aldehyde, (Z) -11-hexadecene-1-aldehyde, (7 e,9 e) -undecane-7, 9-diene-1-aldehyde, (11Z, 13Z) -hexadecene-1-aldehyde, (9Z, 12 e) -tetradecene-1-aldehyde, and (8 e,10 e) -dodecadienol-1-aldehyde.

119. The fatty aldehyde purification process according to any one of the preceding items, wherein the copper ions are copper (II) ions.

120. The fatty aldehyde purification process of any one of the preceding items, wherein the polar solvent is selected from the group consisting of acetonitrile, dimethylformamide, acetonitrile, propionitrile, butyronitrile, dimethylsulfoxide, dimethylacetamide, and propylene carbonate.

121. The fatty aldehyde purification process of any one of the preceding items, wherein the polar solvent is acetonitrile.

122. The fatty aldehyde purification process according to any one of the preceding items, wherein the non-polar aprotic solvent is selected from the group consisting of straight paraffins, branched paraffins, and naphthenes.

123. The fatty aldehyde purification process according to any one of the preceding items, wherein the non-polar aprotic solvent is selected from the group consisting of pentane, hexane, heptane and octane.

124. The fatty aldehyde purification process of any one of the preceding items, wherein the non-polar aprotic solvent is selected from the group consisting of heptane, pentane, hexane, cyclohexane, and octane.

125. The fatty aldehyde purification process according to any one of the preceding items, wherein the acid has a pKa value between 3 and 6.

126. The fatty aldehyde purification process of any one of the preceding items, wherein the acid is a carboxylic acid. 127. The fatty aldehyde purification process of any one of the preceding items, wherein the carboxylic acid is a C2-C8 carboxylic acid.

128. The fatty aldehyde purification process of any one of the preceding items, wherein the carboxylic acid is selected from the group consisting of a C2-C8 monocarboxylic acid, a C2-C8 dicarboxylic acid, and a C6-C8 tricarboxylic acid.

129. The fatty aldehyde purification process of any one of the preceding items, wherein the carboxylic acid is selected from the group consisting of acetic acid, citric acid, propionic acid, lactic acid, glycolic acid, polyacrylic acid.

130. The fatty aldehyde purification process according to any one of the preceding items, wherein at least 1.0 molar equivalent of carboxylic acid to copper is used.

131. The fatty aldehyde purification process according to any of the preceding items, wherein at least 2.0 molar equivalents of carboxylic acid, e.g. at least 2.4 equivalents, are used relative to copper.

132. The fatty aldehyde purification process of any one of the preceding items, wherein the crude reaction product further comprises an oxidizing agent and/or a spent oxidizing agent.

133. The fatty aldehyde purification process of any preceding item, wherein the oxidizing agent or spent oxidizing agent is selected from TEMPO, (4-hydroxy-2, 6-tetramethylpiperidin-1-yl) oxy (4-OH-TEMPO), 4-acetamido-TEMPO, 4-hydroxy-TEMPO benzoate, 4-amino-TEMPO, 2-azaadamantan-N-oxy, 9-azabicyclo [3.3.1] nonane-N-oxy, 4-carboxy-TEMPO, 4-maleimido-TEMPO, 4-methoxy-TEMPO, 1-methyl-2-azaadamantan-N-oxy, 4-oxo-TEMPO, and polymers functionalized with any of the aminoxy radical compounds; or a waste agent thereof.

134. The fatty aldehyde purification process according to any one of the preceding items, further comprising the steps of: evaporating the non-polar aprotic solvent.

135. The fatty aldehyde purification process according to any of the preceding items, wherein evaporation of the non-polar aprotic solvent is performed under reduced pressure, e.g. below 100 mbar, e.g. below 50 mbar, e.g. below 40 mbar, e.g. below 30 mbar.

136. A method of converting a composition comprising a fatty alcohol to a composition rich in fatty aldehydes, the method comprising:

a. converting a composition comprising a fatty alcohol to a composition comprising a fatty aldehyde using the method of any of the preceding items, and

b. purifying the composition comprising fatty aldehyde using the fatty aldehyde purification method of any of the preceding items,

optionally, wherein the fatty alcohol and fatty aldehyde are desaturated.

137. A composition comprising a fatty aldehyde obtained from the method of any one of the preceding items, optionally wherein the fatty aldehyde is desaturated.

138. The composition comprising fatty aldehyde of any of the preceding items, wherein the composition exhibits an absorbance at 680nm of at most 0.5 in a cuvette having an optical path length of 5 mm. 139. A composition comprising a fatty aldehyde of any of the preceding items, wherein the absorbance at 680nm in a cuvette of 5mm optical path length 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.

140. The fatty aldehyde-containing composition of any preceding item, wherein the fatty aldehyde composition comprises less than 0.4% copper, such as less than 0.3%, such as 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%.

141. A composition comprising greater than 93 wt.% fatty aldehyde, less than 7 wt.% fatty alcohol, and less than 2 wt.% water.

142. A process for converting fatty alcohols to fatty acetals, said process comprising the steps of: a. providing a reaction mixture comprising a fatty alcohol composition comprising a fatty alcohol of any of the preceding items, a catalyst composition of any of the preceding items, and a solvent of any of the preceding items, b. Exposing the reaction mixture to at least 10. Mu. Mol O2 per minute per gram of fatty alcohol by bubbling a gas mixture comprising O2 through the reaction mixture, thereby obtaining a fatty aldehyde, and c. Converting the aldehyde functionality of the fatty aldehyde to an acetal functionality,

thereby obtaining a fatty acetal, optionally wherein the fatty alcohol and the fatty acetal are desaturated.

143. A fatty acetal obtained by the process of any of the preceding items, optionally wherein the fatty acetal is desaturated.

144. A fatty aldehyde extended release composition comprising a fatty acetal of any of the preceding items.

145. A method of producing a fatty aldehyde extended release composition of any of the preceding items, the method comprising: the method of any of the preceding clauses is practiced to provide a fatty acetal and formulating the fatty acetal in a sustained release composition, optionally wherein the fatty acetal is desaturated.

146. A process for converting fatty alcohols to fatty α -hydroxysulfonic acids, the process comprising the steps of: a. providing a reaction mixture comprising a fatty alcohol composition comprising a fatty alcohol of any of the preceding items, a catalyst composition of any of the preceding items, and a solvent of any of the preceding items, b. Exposing the reaction mixture to at least 10. Mu. Mol O2 per minute per gram of fatty alcohol by bubbling a gas mixture comprising O2 through the reaction mixture, thereby obtaining a fatty aldehyde, and c. Converting the aldehyde functionality of the fatty aldehyde to an alpha-hydroxysulfonic acid functionality,

thereby obtaining fatty alpha-hydroxysulfonic acid, optionally wherein the fatty alcohol and fatty alpha-hydroxysulfonic acid are desaturated.

147. A fatty alpha-hydroxysulfonic acid obtained by the process of any one of the preceding items, optionally wherein the fatty alpha-hydroxysulfonic acid is desaturated.

148. A fatty aldehyde sustained release composition comprising fatty alpha-hydroxysulfonic acid of any preceding item, optionally wherein the fatty alpha-hydroxysulfonic acid is desaturated.

149. A method of producing a fatty aldehyde extended release composition of any of the preceding items, the method comprising performing the method of any of the preceding items to provide a fatty α -hydroxysulfonic acid and formulating the fatty α -hydroxysulfonic acid into an extended release composition, thereby obtaining a fatty aldehyde extended release composition.

150. A pheromone component produced from a renewable feedstock, the pheromone component having a biobased carbon content of at least 80%.

151. A pheromone component according to any preceding item comprising a fatty aldehyde composition and/or a fatty aldehyde of any preceding item.

Claims

1. A process for large scale conversion of fatty alcohols to fatty aldehydes, said process comprising the steps of:

b) By incorporating O into ₂ Is fed into the reaction medium, at least 0.01. Mu. Mol O per minute per. Mol copper in the reaction mixture ₂ Or at least 0.001. Mu. Mol O per minute per. Mu. Mol of starting fatty alcohol in the reaction mixture ₂ To dissolve into the reaction mixture, therebyMore than 50 wt.% of the fatty alcohol is oxidized to fatty aldehyde and less than 50 wt.% of the fatty alcohol is oxidized to fatty acid.

2. The method of claim 1, further comprising: at least 0.049. Mu. Mol of dissolved O per mu. Mol of copper per minute is dissolved in the reaction mixture ₂ 。

3. The method of any of the preceding claims, further comprising: at least 0.0025. Mu. Mol of dissolved O per mu. Mol of starting fatty alcohol per minute is dissolved in the reaction mixture ₂ 。

4. The method of any of the preceding claims, further comprising: at least 0.025. Mu. Mol of dissolved O per. Mu. Mol of fatty acid per minute is dissolved in the reaction mixture ₂ 。

5. The method according to any of the preceding claims, comprising: at least 10 mu mol O ₂ For example at least 20. Mu. Mol O ₂ At least 40 mu mol O ₂ Or at least 60. Mu. Mol O ₂ Each gram of fatty alcohol per minute is dissolved into the reaction mixture to obtain the fatty aldehyde, optionally wherein the fatty alcohol and the fatty aldehyde are desaturated.

6. The method of any one of the preceding claims, wherein the comprising O ₂ Is air, optionally enriched in O ₂ 。

7. The method of any of the preceding claims, wherein O is to be included ₂ Is fed into the reaction medium by feeding a gas or liquid comprising O ₂ Is pumped or bubbled through the reaction mixture.

8. The method of any of the preceding claims, wherein the copper source comprises a copper (I) salt or a combination of copper (II) and a reducing agent.

9. The process according to any one of the preceding claims, wherein the catalyst further comprises a ligand, for example a ligand selected from 2,2 '-bipyridine, 4' -dimethyl-2, 2 '-bipyridine, 5' -dimethyl-2, 2 '-bipyridine 2,2' -bipyrimidine, 2 '-bipyridine-4, 4' -dicarboxylic acid or an ester thereof, 2 '-bipyridine-5, 5' -dicarboxylic acid or an ester thereof.

10. The process of any of the preceding claims, wherein the catalyst comprises an aminoxy radical compound, such as an aminoxy radical compound selected from TEMPO, (4-hydroxy-2, 6-tetramethylpiperidin-1-yl) oxy (4-OH-TEMPO), 4-acetamido-TEMPO, 4-hydroxy-TEMPO benzoate, 4-amino-TEMPO, 2-azaadamantane-N-oxy, 9-azabicyclo [3.3.1] nonane N-oxy, 4-carboxy-TEMPO, 4-maleimido-TEMPO, 4-methoxy-TEMPO, 1-methyl-2-azaadamantane-N-oxy, 4-oxo-TEMPO, and polymers functionalized with any of the aminoxy radical compounds.

11. The process according to any of the preceding claims, wherein the catalyst comprises a base, such as a base selected from 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, 3-tetramethylguanidine, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene and potassium tert-butoxide.

12. The method of any one of the preceding claims, wherein the solvent is a non-halogenated solvent.

13. The method of 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 any of the preceding claims, wherein the conversion of fatty alcohol to fatty 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 of any one of the preceding claims, wherein the ratio of fatty acid produced to fatty aldehyde produced is less than 10:90.

16. The method according to any of the preceding claims, wherein the conversion of fatty alcohol to 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 of any one of the preceding claims, wherein the water absorbing or adsorbing material is selected from molecular sieves, silica gel, alumina, bentonite, calcium oxide, alkali metal carbonates, bicarbonates, or alkaline earth metal carbonates, or combinations thereof.

18. The method of any one of the preceding claims, wherein the water absorbing or adsorbing material is added to the reaction medium in an amount such that the water content in the reaction medium after the oxidation process is 2 wt% or less and optionally the molar conversion of fatty alcohol to fatty aldehyde is above 93%.

19. The method according to any of the preceding claims, wherein the amount of water absorbing or adsorbing material added is at least 10g per mmol of fatty alcohol present in the reaction medium prior to oxidation, such as at least 15g per mmol of fatty alcohol, such as at least 19g per mmol of fatty alcohol, and wherein optionally the water absorbing or adsorbing material is a molecular sieve.

20. The method of any one of the preceding claims, wherein the fatty aldehyde is selected from the group consisting of:

(E) - Δ13 desaturated fatty aldehydes having carbon chain lengths of 14, 15, 16, 17, 18, 19, 20, 21, or 22;

such as

(E) 8, (E) 10 desaturated fatty aldehydes having carbon chain lengths of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22,

such as

(E) 7, (Z) 9 unsaturated fatty aldehyde having a carbon chain length of 14,

(E) 7, (Z) 9 desaturated fatty aldehydes with a carbon chain length of 12,

(E) 8, (E) 10 desaturated fatty aldehydes with carbon chain length of 12

(E) 7, (E) 9 desaturated fatty aldehydes with a carbon chain length of 11,

(Z) 11, (Z) 13 desaturated fatty aldehydes of carbon chain length 16, or

(Z) 9, (E) 12 desaturated fatty aldehydes with a carbon chain length of 14,

or such as

Tetradecane-1-aldehyde, pentadecyl-1-aldehyde, hexadecane-1-aldehyde, pentadecyl-1-aldehyde, (Z) -9-hexadecene-1-aldehyde, (Z) -11-hexadecene-1-aldehyde, (7E, 9E) -undecane-7, 9-diene-1-aldehyde, (11Z, 13Z) -hexadecene-1-aldehyde, (9Z, 12E) -tetradecene-1-aldehyde and (8E, 10E) -dodecene-1-aldehyde.

21. The method of any of the preceding claims, further comprising: a step of purifying a fatty aldehyde, the step comprising:

a) Providing a purification mixture comprising:

i. a fatty aldehyde, and a fatty acid,

copper ions

Polar solvent;

b) Mixing the purification mixture with a non-polar aprotic solvent and an acid to produce an extraction mixture comprising a non-polar phase and a polar phase such that the fatty aldehyde is extracted from the polar phase to the non-polar phase, and

c) Separating a nonpolar phase comprising purified aldehyde from the polar phase.

22. The method of claim 19, wherein the purification mixture comprises 0.05 to 5.0 wt% copper ions, such as 0.05 to 2.0 wt% copper ions, such as 0.05 to 1.0 wt% copper ions.

23. The method according to claims 19 to 20, wherein the carboxylic 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. The fatty aldehyde purification process according to any one of claims 19 to 21, wherein at least 2.0 molar equivalents of carboxylic acid, such as at least 2.4 equivalents, are used relative to the copper.

25. A composition comprising greater than 93 wt.% fatty aldehyde, less than 7 wt.% fatty alcohol, and less than 2 wt.% water.

26. The composition of claim 23, wherein the light absorbance at 680nm 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 in a cuvette having a path length of 5 mm.