Process for purifying a crude product mixture

Abstract

The present invention relates to the field of organic synthesis and more specifically it concerns a process for purifying an organic reaction product from a crude product mixture.

Description

[0001] PROCESS FOR PURIFYING A CRUDE PRODUCT MIXTURE

[0002] Technical field

[0003] The present invention relates to the field of organic synthesis and more specifically it concerns a process for purifying an organic reaction product from a crude product mixture.

[0004] Background

[0005] Within the production of organic compounds useful as fragrances and flavors or as intermediates for producing them, the purification of raw materials poses significant challenges. The process demands precision and expertise to eliminate impurities and retain essential aromatic components. Distillation, extraction, and filtration techniques must navigate the complexities of natural sources, presenting hurdles such as the preservation of delicate fragrance compounds. Highly relevant is the removal of metal and in particular transition metal salts, whose potential to have irritating or even toxic properties makes their removal in the purification process important.

[0006] There is still a need to develop a more efficient process for purifying organic compounds, in particular to be used as perfumery ingredient, which are in particular not affected in their desired properties, for example in case of perfumery ingredients in their olfactive properties by avoiding the introduction of for example undesired off-notes.

[0007] The present invention allows obtaining a desired organic reaction product in high purity by adding a polyamine to a crude product mixture and subsequently conducting a purification step.

[0008] Summary of the Invention

[0009] The invention relates to a novel process allowing the efficient purification of an organic reaction product from a crude product mixture, in particular without affecting their desired properties.

[0010] In a first aspect, the object of the invention is to provide a method of purifying an organic reaction product from a crude product mixture, the method comprises the step of: adding a polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably a polyethylene amine, to a crude product mixture and conducting a purification step for removing at least one impurity from the crude product mixture selected from the group consisting of a metal compound, a Lewis acid, a Bronsted acid, an organic halide and a combination thereof, wherein diethylene triamine and triethylene tetramine are excluded.

[0011] In a second aspect, the invention relates to the use of polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, as additive for purifying an organic reaction product from a crude product, wherein diethylene triamine and triethylene tetramine are excluded.

[0012] Description of the invention

[0013] As used herein, the term “organic reaction product” relates to the organic compound or compounds that was intended to be produced in a chemical reaction and was actually produced. The organic compound has a low reactivity towards amines. Said compound may have at least one functional group with low reactivity towards amines. A compound having a low reactivity towards amines encompasses aliphatic hydrocarbons and aromatic hydrocarbons. A compound having at least one functional group with low reactivity towards amines encompasses an alkene group an alkyne group, a fluorine, a nitro group, a compound with an alcohol group, an amide, an ether, an acetal, a sterically hindered ketone and a sterically hindered ester. It is to be understood that a sterically hindered ketone and a sterically hindered ester have a low reactivity towards amines. Such low reactivity can be estimated by routine experiments known in the art. For example, reactivity of a ketone towards an amine may be estimated by adding 2,4-dinitrophenylhydrazin to a sample. If the ketone is not sterically hindered, it will react with 2,4-dinitrophenylhydrazin and the related product could be determined by standardized melting point estimation. The organic reaction product may also encompass aldehydes, not sterically hindered ketones and not sterically hindered esters, optionally protected by a protecting group. Suitable protecting groups that do not react with an amine and their use are generally known in the art (e.g. Theodora W. Greene; Peter G. M. Wuts (1999). Protecting Groups in Organic Synthesis (3 ed.). J. Wiley). For example, aldehydes and ketones may be protected by acetals formed by reacting them with ethylene glycol or 1,3-propanediol. In a certain embodiment, the organic reaction product is an aliphatic hydrocarbon or an aromatic hydrocarbon compound optionally comprising one or more functional groups selected from the group consisting of an alkene group an alkyne group, fluorine, a nitro group, an alcohol group, an amide, an ether, an acetal and combinations thereof.

[0014] As used herein, the term “crude product mixture” is a, preferably liquid , mixture of substances generated during a chemical reaction. The crude product mixture thus typically contains the organic reaction product along with impurities such as unreacted starting materials, catalysts, reagents, intermediate compounds, and further by-products. The crude product mixture thereby typically comprises the organic reaction product. The term "crude" indicates that the mixture has not undergone extensive purification processes and may include impurities. The crude product mixture serves as an initial stage in the production of organic end products or intermediates such as compounds of use in the production of fragrances and flavors, requiring at least one subsequent processing step of purification. Hence, the crude product mixture may have been subjected to a first purification step before the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is added.

[0015] As used herein, the term “metal compound” relates to compounds comprising at least one metal. The term “metal” includes the metalloids. In particular, B, Si, Ge, As, Sb, Te and Se. It is to be understood, that metal compounds include salts of metals, coordination complexes formed by metals with ligands, clusters comprising metals and ligands and / or counter ions, elementoid metal clusters and organometallic compounds such as Grignard compounds or organolithium compounds. The term “metal compounds” further refers to organometal compounds. Non-limiting examples of organometal compounds are organoboron compounds, silicones and organotin compounds. It is to be understood that organoboron compounds, also referred to as organoboranes, combine boron and carbon; typically, they are organic derivatives of borane (BH3), as for example in the trialkyl boranes. It is to be understood that organotin compounds are organometallic compounds containing tin-carbon bonds and include any organic derivative of tin(IV), tin (III), tin (II) and tin(I) such as stannoxanes and hypercoordinated stannanes. It is to be understood that silicone, also called polysiloxane, is an oligomer or polymer composed of repeating units of siloxane (-O-R2Si-O-SiR2-, where R represents any hydrocarbon-based moiety).

[0016] As used herein, the term “transition metal compound” relates to compounds comprising at least one of the metals in groups 3 to 12 of the periodic table. It is to be understood, that transition metal compounds include salts of transitions metals, coordination complexes formed by transitions metals with ligands, clusters comprising transitions metals and ligands and / or counter ions, elementoid transitions metal clusters and organometallic compounds comprising transitions metals such as organozinc compounds.

[0017] As used herein, the term “Lewis acid” relates to a molecular entity that is an electron-pair acceptor and therefore able to react with a Lewis base to form a Lewis adduct, by sharing the electron pair furnished by the Lewis base as defined by IUPAC ('Lewis acid' in IUPAC Compendium of Chemical Terminology, 3rd ed. International Union of Pure and Applied Chemistry; 2006. Online version 3.0.1, 2019).

[0018] As used herein, the term “Bronsted acid” relates to a molecular entity capable of donating a proton to a base or the corresponding chemical species as defined by IUPAC ('Bronsted acid' in IUPAC Compendium of Chemical Terminology, 3rd ed. International Union of Pure and Applied Chemistry; 2006. Online version 3.0.1, 2019).

[0019] As used herein, the term “organic halides” relates to organic compounds in which one or more carbon atoms are linked by covalent bonds with one or more halogen atoms chlorine, bromine or iodine. Such compounds may also be referred to as organochlorine compounds, organobromine compounds, and organoiodine compounds.

[0020] As used herein, the term “compound with an alcohol group” relates to alcohols as defined by the IUPAC ('alcohols' in IUPAC Compendium of Chemical Terminology, 3rd ed. International Union of Pure and Applied Chemistry; 2006. Online version 3.0.1, 2019), enols as defined by the IUPAC ('enols' in IUPAC Compendium of Chemical Terminology, 3rd ed. International Union of Pure and Applied Chemistry; 2006. Online version 3.0.1, 2019) and phenols as defined by the IUPAC ('phenols' in IUPAC Compendium of Chemical Terminology, 3rd ed. International Union of Pure and Applied Chemistry; 2006. Online version 3.0.1, 2019). Particularly, the term “compound with an alcohol group” relates to alcohols as defined by the IUPAC ('alcohols' in IUPAC Compendium of Chemical Terminology, 3rd ed. International Union of Pure and Applied Chemistry; 2006. Online version 3.0.1, 2019) and phenols as defined by the IUPAC ('phenols' in IUPAC Compendium of Chemical Terminology, 3rd ed. International Union of Pure and Applied Chemistry; 2006. Online version 3.0.1, 2019). More particularly, the term “compound with an alcohol group” relates to alcohols as defined by the IUPAC ('alcohols' in IUPAC Compendium of Chemical Terminology, 3rd ed. International Union of Pure and Applied Chemistry; 2006. Online version 3.0.1, 2019).

[0021] Surprisingly, it has now been discovered that polyethylene amine could be used in a simple process as scavenger of various impurities out of residual metallic salts or complexes, Lewis acids, traces of acidity and / or Bronsted acids and their salts respectively or organic halides. Even traces of toxic metal can be removed. The organic reaction product can be separated more easy and more efficient from the reaction product formed by polyethylene amine and the impurity. The inventions purification process is thus suitable for the removal of metal compounds, particularly metal salts and more particularly traces of toxic metals and / or their salts, Lewis acids, Bronsted acids and organic halides.

[0022] Furthermore, it has also now been discovered that by avoiding lower polyethylene amine compounds that are diethylene triamine and triethylene tetramine the olfactive perception of the purified perfumery ingredients is not affected by off-notes associated with even minimum amounts thereof. It has been for example discovered that in particular diethylene amine and triethylene tetramine for example negatively affect the olfactive perception of purified perfumery ingredients such as contributing with a fishy off-note.

[0023] Therefore, a first aspect of the present invention is a process of purifying an organic reaction product from a crude product mixture, the method comprises the step of: adding a polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, to a crude product mixture and conducting a purification step for removing at least one impurity from the crude product mixture selected from the group consisting of a metal compound, a Lewis acid, a Bronsted acid, an organic halide and a combination thereof, wherein diethylene triamine and triethylene tetramine are excluded.

[0024] In other words, provided is a process of purifying an organic reaction product from a crude product mixture, the method comprises the step of: adding a polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, to a crude product mixture and enriching an organic reaction product by removing at least one impurity from the crude product mixture selected from the group consisting of a metal compound, a Lewis acid, a Bronsted acid, an organic halide and a combination thereof, wherein diethylene triamine and triethylene tetramine are.

[0025] According to any embodiment, the process of purifying an organic reaction product from a crude product mixture, the method comprises the step of: adding a polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, to a crude product mixture comprising an organic reaction product and enriching the organic reaction product by removing at least one impurity selected from the group consisting of a metal compound, a Lewis acid, a Bronsted acid, an organic halide and any combinations thereof.

[0026] In one embodiment the process of purifying an organic reaction product from a crude product mixture, the method comprises the step of: adding a polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, to a crude product mixture comprising an organic reaction product and enriching the desired organic reaction product by removing all metal compounds, Lewis acids, Bronsted acids and organic halides.

[0027] The term “copolymer” is herein understood as a copolymer of polyethylene amines and polypropylene amines. The term is furthermore herein understood as a polymeric compound comprising recurring units derived from both polyethylene amine monomers, such as derived from ethylenediamine, and polypropylene amine monomers, such as derived from 1,2-propylenediamine or 1,3-propylenediamine. The copolymer may be a random, block, or alternating copolymer, in particular depending on synthesis method (e.g. step-growth polymerization, condensation, etc.).

[0028] According to any embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is water soluble.

[0029] According to any embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is a linear or branched polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, preferably a linear polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine. Thus, in a preferred embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine is a linear polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine. In another embodiment the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is a branched polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine.

[0030] According to any embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof has the following formula (I’): wherein each R is independently from each other H or Ci-Cs alkyl, optionally substituted with a terminal amino group; and wherein p is an integer of 2 or 3, q is an integer from 2 or 3 and n is an integer from 1-100, preferably n is an integer from 2-100, more preferably n is an integer from 3-100.

[0031] According to any embodiment, diethylene triamine and triethylene tetramine are excluded as a polyethylene amine.

[0032] According to any embodiment, each R is independently from each other H or Ci-Ce alkyl. In one embodiment, each R is independently from each other H or C1-C4 alkyl. In a preferred embodiment, each R is H. In another embodiment, each R is independently from each other C1-C4 alkyl.

[0033] According to any embodiment, n is an integer from 1-50, preferably 2-50, more preferably 3-50. In one embodiment, n is an integer from 1-25, preferably 2-25, more preferably 3-25. In another embodiment, n is an integer from 2-20, preferably 3-20. In a further preferred embodiment, n is an integer from 3-10.

[0034] According to any embodiment, p is an integer from 2 or 3, preferably 2, and q is an integer from 2 or 3, preferably 2. According to a preferred embodiment, p is 2 and q is 2. According to another embodiment, p is 3 and q is 3.

[0035] According to any embodiment, the polyethylene amine has the following formula

[0036] (I), wherein each R is independently from each other H or Ci-Cs alkyl, optionally substituted with a terminal amino group; and wherein n is an integer from 1-100, preferably n is an integer from 2-100, more preferably n is an integer from 3-100.

[0037] According to any embodiment diethylene triamine and triethylene tetramine are excluded as a polyethylene amine.

[0038] According to any embodiment, each R is independently from each other H or Ci-Ce alkyl. In one embodiment, each R is independently from each other H or C1-C4 alkyl. In a preferred embodiment, each R is H. In another embodiment, each R is independently from each other C1-C4 alkyl.

[0039] According to any embodiment, n is an integer from 1-50, preferably 2-50, more preferably 3-50. In one embodiment, n is an integer from 1-25, preferably 2-25, more preferably 3-25. In another embodiment, n is an integer from 2-20, preferably 3-20. In a further preferred embodiment, n is an integer from 3-10.

[0040] It is to be understood that any embodiment relating to R in formula (I’) and (I) can be combined with any embodiment relating to n in formula (I’) and (I), such as each R is independently from each other H or Ci-Ce and n is an integer from 2-20, preferably 3-20; or each R is independently from each other H or C1-C4 alkyl and n is an integer from 2-20, preferably 3-20; or each R is independently from each other H or C1-C4 alkyl and n is an integer from 3-10 etc.

[0041] According to any embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof is selected from the group consisting of tetraethylene pentamine, tetrapropylene pentamine, pentaethylene hexamine, pentapropylene hexamine, hexaethylene heptamine, hexapropylene heptamine, heptaethylene octamine, higher polyethylene polyamines such as octaethylene nonamine, nonaethylene decamine, decaethylene undecamine, undecaethylene dodecamine, dodecaethylene tridecamine, tri decaethylene tetradecamine and / or tetradecaethylene pentadecamine, isomers thereof and mixtures thereof.

[0042] In another embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof comprises at least two polyethylene amines, polypropylene amines or copolymers thereof, preferably polyethylene amines, selected from the group consisting of tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, heptaethylene octamine and higher polyethylene polyamines, polypropylene amines or copolymers thereof. It is to be understood, that the term “higher polyethylene amines or polyamines or polypropylene amines or polyamines” relate to polyethylene polyamines or polypropylene polyamines having a higher monomer content as the aforementioned one, for example octaethylene nonamine is one example of a higher polyethylene polyamine. Further examples of “higher polyethylene amines or higher polypropylene amines” are for example nonaethylene decamine, decaethylene undecamine, undecaethylene dodecamine, dodecaethylene tridecamine, tri decaethylene tetradecamine and / or tetradecaethylene pentadecamine, Therefore, the content of monomers in higher polyethylene polyamines may be from 9 to 100, 9 to 50, 9 to 25 or 9 to 15 as defined for n in formula (I).

[0043] According to any embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is selected from the group consisting of tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, heptaethylene octamine, higher polyethylene polyamines, polypropylene polyamines or copolymers, preferably polyethylene poly amines, having a maximum content of 100 monomers, isomers thereof and mixtures thereof.

[0044] According to any embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is selected from the group consisting of tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, heptaethylene octamine, higher polyethylene polyamines, polypropylene polyamines or copolymers, preferably polyethylene polyamines, having a maximum content of 50 monomers, isomers thereof and mixtures thereof.

[0045] According to any embodiment, the polyethylene amine, polypropylene polyamine, copolymer or mixtures thereof, preferably polyethylene amine, is selected from the group consisting of tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, heptaethylene octamine, higher polyethylene polyamines, polypropylene polyamines or copolymers, preferably polyethylene polyamines, having a maximum content of 25 monomers, isomers thereof and mixtures thereof.

[0046] According to any embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is selected from the group consisting of tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, heptaethylene octamine, higher polyethylene polyamines, polypropylene polyamines or copolymers, preferably polyethylene poly amines, having a maximum content of 15 monomers, isomers thereof and mixtures thereof.

[0047] According to any embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is pentaethylene hexamine or higher polyethylene polyamine, polypropylene polyamine or copolymer, preferably polyethylene polyamines, preferably pentaethylene hexamine.

[0048] According to any embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is pentaethylene hexamine or higher polyethylene polyamine, polypropylene polyamine or copolymer, preferably polyethylene polyamine, having a maximum content of 15 monomers, preferably pentaethylene hexamine.

[0049] According to any embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is hexaethylene heptamine or higher polyethylene polyamine, polypropylene polyamine or copolymer, preferably polyethylene polyamine, preferably hexaethylene heptamine.

[0050] According to any embodiment, the polyethylene amine , polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is hexaethylene heptamine or higher polyethylene polyamine, polypropylene polyamine or copolymer, preferably polyethylene polyamine, having a maximum content of 15 monomers, preferably hexaethylene heptamine.

[0051] According to any embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is heptaethylene octamine or higher polyethylene polyamine, polypropylene polyamine or copolymer, preferably polyethylene polyamine, preferably heptaethylene octamine.

[0052] According to any embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is heptaethylene octamine or higher polyethylene polyamine, polypropylene polyamine or copolymer, preferably polyethylene polyamine, having a maximum content of 15 monomers, preferably heptaethylene octamine.

[0053] In one embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is selected from the group consisting of tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, heptaethylene octamine, isomers thereof and mixtures thereof.

[0054] In a further embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, comprises at least two polyethylene amines , polypropylene amines or copolymers thereof, preferably polyethylene amines, selected from the group consisting of tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine and heptaethylene octamine.

[0055] In one embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, comprises a mixture of hexaethylene heptamine and heptaethylene octamine. Preferably, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is a mixture of hexaethylene heptamine and heptaethylene octamine.

[0056] It has also now been discovered that by avoiding lower polyethylene amine compounds such as diethylene triamine and triethylene tetramine the olfactive perception of the purified organic compounds when applied as perfumery ingredients is not affected by off-notes associated with even minimum amounts thereof. It has been for example discovered that in particular diethylene amine and triethylene tetramine for example negatively affect the olfactive perception of purified perfumery ingredients, such as contributing with a fishy off-note. In a particular embodiment, polyethylene amines, polypropylene amines, copolymers or mixtures thereof, preferably polyethylene amines, according to formula (I’) and (I) with n being an integer of 1 or 2, preferably n being an integer of 1 and 2, are excluded.

[0057] According to any embodiment, the crude product mixture is obtained from a catalytic oxidation, a catalytic reduction, a metathesis reaction, a coupling reaction, a rearrangement, a condensation, an elimination or a substitution reaction. In an embodiment, the crude product mixture is obtained from a catalytic hydrogenation; a catalytic hydration, a catalytic dehydrogenation; a metathesis reaction; a rearrangement, preferably an isomerization reaction; a coupling reaction; or a cyclization reaction, preferably a hetero cyclization reaction. Preferably, the crude product mixture is obtained from a catalytic hydrogenation, a catalytic hydration, a catalytic dehydrogenation, a metathesis reaction, a coupling reaction or a cyclization reaction, preferably a hetero cyclization reaction.

[0058] According to an embodiment, the organic reaction product comprises a Ce-20, preferably C9-16, hydrocarbyl group, optionally substituted with one or more of hydroxy, carboxyl ester, keto, aldehyde and / or C1-3 alkoxy groups.

[0059] According to a particular embodiment, the organic reaction product comprises a Ce- 20, preferably C9-16, cycloalkyl, cycloalkenyl, alkyl or alkenyl group, optionally substituted with one or more of hydroxy, carboxyl ester, keto, aldehyde and / or C1-3 alkoxy groups.

[0060] According to a particular embodiment, the organic reaction product comprises a Ce- 20, preferably C9-16, linear or branched cycloalkyl, cycloalkenyl, alkyl or alkenyl group, optionally substituted with one or more of hydroxy, carboxyl ester, keto, aldehyde and / or C1-3 alkoxy groups.

[0061] According to a particular embodiment, the organic reaction product comprises a C9- 16 linear or branched cycloalkyl, cycloalkenyl, alkyl or alkenyl group, optionally substituted with one or more of hydroxy, carboxyl ester, keto, aldehyde and / or C1-3 alkoxy groups.

[0062] According to any embodiment, the organic reaction product comprises one or more hydroxy group(s).

[0063] According to a particular embodiment, the organic reaction product comprises one or more hydroxy group(s) attached to a Ce-20, preferably C9-16, hydrocarbyl group, optionally substituted with one or more of carboxyl ester, keto, aldehyde and / or C1-3 alkoxy groups.

[0064] According to a particular embodiment, the organic reaction product comprises one or more hydroxy group(s) attached to a C6-20, preferably C9-16, cycloalkyl, cycloalkenyl, alkyl or alkenyl group, optionally substituted with one or more of carboxyl ester, keto, aldehyde and / or C1-3 alkoxy groups.

[0065] According to a particular embodiment, the organic reaction product comprises one or more hydroxy group(s) attached to a C6-20, preferably C9-16, linear or branched cycloalkyl, cycloalkenyl, alkyl or alkenyl group, optionally substituted with one or more of carboxyl ester, keto, aldehyde and / or C1-3 alkoxy groups.

[0066] According to a particular embodiment, the organic reaction product comprises one or more hydroxy group(s) attached to a C9-16 linear or branched cycloalkyl, cycloalkenyl, alkyl or alkenyl group, optionally substituted with one or more of carboxyl ester, keto, aldehyde and / or C1-3 alkoxy groups.

[0067] According to any embodiment, the organic reaction product is a perfumery ingredient or a starting material for a perfumery ingredient.

[0068] According to a particular embodiment, the organic reaction product is a C6-20, preferably a C9-16, perfumery ingredient or a starting material for a C6-20, preferably a C9-16, perfumery ingredient.

[0069] The term “hydrocarbyl group” is herein understood as an organic group consisting exclusively of carbon and hydrogen atoms. The hydrocarbyl group may be aliphatic (e.g., alkyl, alkenyl, alkynyl), alicyclic (e.g., cycloalkyl, cycloalkenyl), or aromatic (e.g., aryl), and may be linear, branched, or cyclic. The hydrocarbyl group may be optionally substituted by functional groups comprising oxygen, amine or sulfur. The hydrocarbyl group may optionally substituted by one or more hydroxy groups, one or more carboxyl ester groups, one or more keto groups, one or more aldehyde groups and / or one or more Ci- 3 alkoxy groups

[0070] The term “perfumery ingredient” is herein understood as a synthetic derivable compound or composition capable of imparting a detectable pleasant scent, aroma, or olfactory effect to a composition to which it is added. According to any embodiment, the organic reaction product is a compound with an alcohol group and the impurity is an organic acid, i.e. a Bronsted acid. In one embodiment, the organic acid is selected from the group comprising a carboxylic acid, a sulfonic acid, a phosphoric acid, a phosphonic acids, a phosphinic acid and any mixture thereof. In one embodiment, the impurity has no alcohol group.

[0071] According to any embodiment, the crude product mixture comprises at least an organic reaction product and at least a metal compound, preferably a transition metal compound or a Lewis acid or a Bronsted acid as impurity.

[0072] In one embodiment, the crude product mixture comprises at least a compound with an alcohol group as organic reaction product and at least a metal compound, preferably a transition metal compound or a Lewis acid or a Bronsted acid as impurity.

[0073] In one embodiment, the impurity comprises at least a metal compound, preferably a transition metal compound and / or a Lewis acid and / or a Bronsted acid as impurity.

[0074] In another embodiment, the impurity in the crude product mixture is a metal compound, preferably a transition metal compound.

[0075] According to any embodiment, the metal of the metal compound is selected from the group consisting of Al, Ga, In, Ti, Ge, Sn, Sb, Pb, Bi, Fe, Ru, Os, Co, Rh, Ir, Mn, Re, Ni, Pd, Pt, Cu, Zn and combinations thereof.

[0076] In one embodiment, the transition metal of the transition metal compound is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Zn and combinations thereof.

[0077] The metal compound may be a metal catalyst or a transition metal catalyst respectively. The metal catalyst or transition metal catalyst respectively is part of the crude product mixture. Catalysts generally react with one or more reactants to form intermediates that subsequently give the final reaction product, in the process of regenerating the catalyst. In theory, catalysts are not consumed by the reaction and remain unchanged after it. However, in practice, catalysts may become ineffective after some time of use due to side reactions, as they are blocked by by-products. It is thus to be understood that the terms “metal catalyst” and “ transition metal catalyst” in the crude reaction mixture include metal compounds that are by-products of the metal catalyst. The formation of by-products depends on the very nature of the reaction and the particular conditions applied. It is to be understood that for the purpose of the present invention, the identity of the metal compounds that are by-products of the metal catalyst is not of certain relevance, since the polyamine reacts with the metal itself, as it is specified by the metal catalyst used. If required, such by-products can be easily identified by known methods such as mass spectrometry, NMR and X-ray crystallography.

[0078] Thus, according to any embodiment, the metal compound in the crude product mixture is consisting of the metal catalyst and any metal compounds that are by-products of the metal catalyst. In one embodiment, the transition metal compound is consisting of the transition metal catalyst and any transition metal compounds that are by-products of the transition metal catalyst.

[0079] According to any embodiment, the crude product mixture comprises at least a metal catalyst, preferably a transition metal catalyst and / or a Lewis acid and / or a Bronsted acid as impurity. In another embodiment, the impurity in the crude product mixture is a metal catalyst, preferably a transition metal catalyst.

[0080] According to any embodiment, the metal of the metal catalyst is selected from the group consisting of Al, Ga, Ag, In, Ti, Ge, Sn, Sb, Pb, Bi, Fe, Ru, Os, Co, Rh, Ir, Mn, Re, Ni, Pd, Pt, Cu, Zn and combinations thereof.

[0081] In one embodiment, the transition metal of the transition metal catalyst is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Zn and combinations thereof.

[0082] According to any embodiment, the metal compound is a catalyst for catalytic, hydrogenation, catalytic hydration, catalytic dehydrogenation, a metathesis catalyst, an isomerization catalyst, or a coupling catalyst.

[0083] In one embodiment, the transition metal compound is a catalyst for catalytic, hydrogenation, catalytic hydration, catalytic dehydrogenation, a metathesis catalyst, a coupling catalyst, a cyclization catalyst, preferably a hetero cyclization catalyst.

[0084] In another embodiment, the metal compound is a hydrogenation catalyst or a metathesis catalyst, preferably selected from the group consisting of platinum-based catalysts, palladium-based catalysts, ruthenium-based catalysts, iridium-based catalysts, rhodium-based catalysts, nickel-based catalysts, cobalt-based catalysts iron-based catalysts, copper-based catalysts, molybdenum-based catalysts, tungsten-based catalysts and zinc-based catalysts. In yet another embodiment, the metal compound is a catalyst for hydrogenation.

[0085] In yet another embodiment, the catalyst for hydrogenation is selected from the group consisting of platinum-based catalysts, palladium-based catalysts, ruthenium-based catalysts, iridium-based catalysts, rhodium-based catalysts, nickel-based catalysts, cobaltbased catalysts and iron-based catalysts.

[0086] In a certain embodiment, the catalyst for catalytic hydrogenation is a platinum catalyst, preferably selected from the group consisting of platinum sponge, platinum on activated carbon (Pt / C), platinum black, platinum(II) chloride, and platinum(IV)-oxide (Adams catalyst). In an embodiment the platinum catalyst is selected from the group consisting of platinum sponge and platinum(II) chloride.

[0087] In a further embodiment, the catalyst for catalytic hydrogenation is a palladium catalyst, preferably selected from the group consisting of the palladium on activated carbon (Pd / C), colloidal palladium, palladium (Il)-oxide, palladium on BaSCL, Pd(OH)2 on BaSCL, Lindlar catalyst, palladium on CaCCL and palladium black. In an embodiment the palladium catalyst is colloidal palladium.

[0088] In a further embodiment, the catalyst for catalytic hydrogenation is a ruthenium catalyst, preferably selected from the group consisting of ruthenium on activated carbon (Ru / C), ruthenium(III) chloride, ruthenium tris(bipyridine) complexes, ruthenium phosphine complexes, ruthenium-TsDPEN (N-(p-tosyl)-l,2-diphenylethylene-l,2- diamine) complexes, ruthenium(II) acetate (Ru(0Ac)2), ruthenium-PNNP (3,5- bis(diphenylphosphinomethyl)pyrazolato) complexes and ruthenium(II) olefin complexes.

[0089] In yet a further embodiment, the catalyst for catalytic hydrogenation is an iridium catalyst, preferably selected from the group consisting of iridium bisphosphine complexes, iridium(III) complexes with chiral ligands, iridium-N-heterocyclic carbene complexes, iridium(I) olefin complexes, iridium triphenylphosphine complexes, iridium(III) acetylacetonate.

[0090] In yet a further embodiment, the catalyst for hydrogenation is a rhodium catalyst, preferably selected from the group consisting of rhodium phosphine complexes, rhodium(I) olefin complexes, rhodium(II) acetylacetonate, rhodium(II) acetate, rhodium trichloride and rhodium on activated carbon (Rh / C).

[0091] In another embodiment, the catalyst for catalytic hydrogenation is a nickel catalyst, preferably selected from the group consisting of Raney -Nickel, nickel boride, nickel(II) acetate and nickel(II) hydroxide. In another embodiment, the catalyst for catalytic hydrogenation is a cobalt catalyst, preferably selected from the group consisting of Raney-Cobalt, Cobalt-Molybdenum catalyst, cobalt nitride and cobalt(II) acetate.

[0092] In a certain embodiment, the catalyst for catalytic hydrogenation is selected from the group consisting of platinum on activated carbon (Pt / C), platinum black platinum(IV)- oxide (Adams catalyst), palladium on activated carbon (Pd / C), palladium (Il)-oxide, palladium black, Noyori Catalyst (prepared in situ from BINAP, (C0D)Ru(2- methylallyl)2), rhodium(II) acetylacetonate, Crabtree's catalyst ([CsH lrP^eHi sCsHsNJPFg), Wilkinson catalyst ([RhCl(PPh3)3]), Raney-Nickel and nickel boride.

[0093] In one embodiment, the metal compound is a dehydrogenation catalyst. Thus, in another embodiment, the transition metal compound is a dehydrogenation catalyst.

[0094] In a certain embodiment, the dehydrogenation catalyst is selected from the group consisting of silver metal, iron(III) oxide, iron(III) molybdates, vanadium oxides or transition metal pincer complex, a transition metal pincer complex is a type of coordination complex with a pincer ligand. Pincer ligands are chelating agents that binds tightly to three adjacent coplanar sites in a meridional configuration. Pincer complexes may be Ir-based, Ru-based, Rh-based, Pd-based or Pt-based.

[0095] In one embodiment, the metal compound is a metathesis catalyst. Thus, in another embodiment, the transition metal compound is a metathesis catalyst.

[0096] In a certain embodiment, the metathesis catalyst is selected from the group consisting of a platinum-based catalyst, a ruthenium-based catalyst, a molybdenum-based catalyst and a tungsten-based catalyst.

[0097] In a certain embodiment, the metathesis catalyst is selected from the group consisting of a Grubbs I catalyst, a Grubbs II catalyst, aHoveyda-Grubbs catalyst, a Grubbs III catalyst or a Schrock catalyst.

[0098] In one embodiment, the metal compound is a coupling catalyst. Thus, in another embodiment, the transition metal compound is a coupling catalyst.

[0099] In yet another embodiment, the coupling catalyst is selected from the group consisting of platinum-based catalysts, palladium-based catalysts, ruthenium-based catalysts, iridium-based catalysts, rhodium-based catalysts, nickel-based catalysts, copperbased catalysts and iron-based catalysts. In a certain embodiment, the coupling catalyst is selected from the group consisting of a Tsuji-Trost catalyst (prepared for example from Pd(0) complexes such as Pd(COD)Ch and triphenylphosphine or the Trost ligand), a Buchwald-Hartwig catalyst (tris(dibenzylidenaceton)dipalladium(O) or prepared for example from Pd(0) complexes such as Pd(COD)Ch and phosphines).

[0100] According to any embodiment, the crude reaction mixture comprises as an impurity at least one Lewis acid.

[0101] In one embodiment, the Lewis acid impurity is selected from the group consisting of aluminum trichloride (AlCh), boron trifluoride (BF3 or BF3 Et2O), iron(III) chloride (FeCL), zinc chloride (ZnCh), tin(IV) chloride (SnCL), boron trichloride (BCI3), beryllium chloride (BeCh), Titanium tetrachloride (TiCL), antimony pentafluoride (SbFs), bismuth pentafluoride (BiFs), Iron(II) chloride (FeCh), bismuth triflate (Bi(OTI 3), Copper triflate (CU(OTI 2), zinc triflate (Zn(0TI)2), indium chloride (InCL) or combinations thereof.

[0102] According to any embodiment, the crude reaction mixture comprises as an impurity at least one Bronsted acid.

[0103] In one embodiment, the Bronsted acid impurity is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, formic acid, acetic acid, oxalic acid, triflic acid, methanesulfonic acid, and combinations therefrom.

[0104] According to any embodiment, the purification step is conducted by distillation or liquid-liquid extraction, preferably by distillation.

[0105] According to any embodiment, the purification step comprises distilling the crude product mixture. The crude product mixture is distilled to obtain the desired organic product. During distillation, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, may act as both, a ballast and as a scavenger of undesired products, in particular impurities. In one embodiment the crude product is distilled by fractionated distillation. In another embodiment the crude product is distilled by azeotropic distillation. In a further embodiment the crude product is distilled by steam distillation.

[0106] According to any embodiment, the temperature for distillation is between 50°C and 300°C, or between 100°C and 250°C, or between 150°C and 200°C, or between 160°C and 190°C. In one embodiment, the pressure for distillation is between 0.1 to 100 mbar or between 1 to 100 mbar, or between 1 to 80 mbar, or between 2 to 70 mbar or between 5 to 60 mbar, or between 10 to 50 mbar, or between 15 to 30 mbar. It is to be understood that the individual condition for distilling the crude product mixture is dependent from the desired product. Therefore, the ranges for temperature and pressure as defined above can be combined in any way, such as for example the temperature for distillation is between 150°C and 200°C and the pressure for distillation is between 15 to 30 mbar or the temperature for distillation is between 160°C and 190°C and the pressure for distillation is between 1 to 5 mbar etc.

[0107] According to any embodiment, the purification step comprises an aqueous work-up. Polyethylene amines, polypropylene amines, copolymers or mixtures thereof, preferably polyethylene amine, are water soluble, particularly when protonated. Due to the water solubility of the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, even compounds which are barely or even not at all water soluble could be removed without employing additional purification steps.

[0108] According to any embodiment, the crude product mixture is subjected to one or more purification steps. According to one embodiment, the one or more further purification steps may be selected from the group consisting of liquid chromatography, filtration, solvent extraction, acid-base extraction, crystallization, recrystallization, sublimation, enantiomeric resolution and combinations thereof.

[0109] According to any embodiment, one or more purification steps are performed before the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is added to the crude product mixture. These purification steps do not lead to the product extensively purified.

[0110] According to any embodiment, one or more purification steps are performed after the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is added to the crude product mixture. These purification steps may lead to the product extensively purified.

[0111] According to any embodiment the process is performed without adding a solvent. In one embodiment, the process is performed neat, i.e. in the absence of a solvent.

[0112] According to any embodiment, the crude product mixture is diluted in a solvent. In one embodiment, the solvent is the one used in the preceding reaction step. In another embodiment, the crude product mixture is diluted into a new solvent. The choice of the solvent is a function of the nature of the complex and the substrate, and the person skilled in the art is well able to select the solvent most convenient in each case to optimize the purification.

[0113] Non-limiting examples include Ce-io aromatic solvents such as toluene or xylene; C5-12 hydrocarbon solvents such as hexane or cyclohexane; C4-8 ethers such as tetrahydrofuran or MTBE; C4-10 esters such as ethyl acetate; C1-2 chlorinated hydrocarbon, such as dichloromethane; C2-6 primary or secondary alcohols, such as isopropanol or ethanol; C2-6 polar solvents such as acetonitrile or mixtures thereof. In particular, said solvent can be an apolar aprotic solvent such as an aromatic solvent or a hydrocarbon solvent. Thus, in one embodiment, the solvent is selected from the group consisting of Ce- 10 aromatic solvents, C5-12 hydrocarbon solvents, C1-2 chlorinated hydrocarbon, C4-8 ethers, C2-6 primary or secondary alcohols or mixtures thereof.

[0114] In another embodiment the solvent is selected from the group consisting of, toluene, xylene ethylbenzene, pentane, hexane, cyclohexane, heptane, petroleum ether, isoparaffins, chloromethane, dichloromethane, chloroethane, ethylene dichloride, diethylether, tetrahydrofuran, MTBE, ETBE, 1,4-di oxane, methyl ethyl ether, butyl glycol ether, ethylene glycol dimethyl ether, methanol, ethanol, n-propanol, isopropanol, bn-butanol, isoamylalcohol acetonitrile or mixtures thereof.

[0115] In one embodiment, the solvent does not comprise DMF and / or DMSO and / or acetonitrile.

[0116] In a second aspect, the invention provides use of polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, as additive for purifying an organic reaction product from a crude product mixture, wherein diethylene triamine and triethylene tetramine are excluded.

[0117] According to any embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is used as a metal scavenger, an acid scavenger or a complexation aid.

[0118] In one embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is used as a complexation aid.

[0119] In another embodiment, the crude product mixture comprises: at least an organic reaction product and at least a metal compound, preferably a transition metal compound and / or a Lewis acid and / or a Bronsted acid as impurity. In another embodiment, the crude product mixture comprises: at least a compound with an alcohol group as organic reaction product and at least a metal compound, preferably a transition metal compound and / or a Lewis acid and / or a Bronsted acid as impurity.

[0120] In a further embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is used during a purification step of the crude product mixture.

[0121] In yet another embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is used during a purification step of the crude product mixture by distillation or liquid-liquid extraction. In a certain embodiment, the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is used during a purification step of the crude product mixture by distillation.

[0122] It is to be understood that all definitions, embodiments and advantages disclosed for the first aspect equally apply to the second aspect and vice versa.

[0123] Examples

[0124] The invention will now be described in further details by way of the following example, wherein the abbreviations have the usual meaning in the art, the temperatures are indicated in degrees centigrade (°C) and the pressure is indicated in bar.

[0125] Example 1

[0126] Use of polyamine as a metal / acid scavenger in a distillation process

[0127] A crude product mixture of 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-en-l-ol was prepared by the catalyzed homogeneous ruthenium complex hydrogenation of 2-ethyl- 4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-enal. The reaction has been performed as described in Example 6 of WO 2014 / 139854 Al on page 39.

[0128] 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-en-l-ol crude containing both traces of homogeneous ruthenium and heavy carboxylic acid such as biphenylcarboxy lie acid was distilled in the presence of 2% PEHA (pentaethylene hexamine). 200g 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-en-l-ol crude (2-ethyl-4-(2,2,3- trimethylcyclopent-3-en-l-yl)but-2-en-l-ol, E / Z 91,4% / 3,6% sum 95%; 2-ethyl-4-(2,2,3- trimethylcyclopent-3-en-l-yl)but-2-enal 0,46%) was distilled in the presence of 4g of PEHA at Tmass up to = 180°C / 20mbar. 197,5g of a heart fraction of 2-ethyl-4-(2,2,3- trimethylcyclopent-3-en-l-yl)but-2-en-l-ol was obtained with a purity 2-ethyl-4-(2,2,3- trimethylcyclopent-3-en-l-yl)but-2-en-l-ol E / Z 91,9% / 3,6% sum 95,5%; 2-ethyl-4-(2,2,3- trimethylcyclopent-3-en-l -yl)but-2-enal 0,46%

[0129] Comparative experiment without PEHA

[0130] 200g 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-en-l-ol crude (2-ethyl-4-(2,2,3- trimethylcyclopent-3-en-l-yl)but-2-en-l-ol E / Z 91,4% / 3,6% sum 95%; 2-ethyl-4-(2,2,3- trimethylcyclopent-3-en-l-yl)but-2-enal 0,46%) was distilled at Tmass up to = 180°C / 20mbar. 178g of a heart fraction of 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l- yl)but-2-en-l-ol was obtained with a purity 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l- yl)but-2-en-l-ol E / Z 83% / 5,4% sum 88,4%; 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l- yl)but-2-enal 5,5%

[0131] Conclusion

[0132] The presence of PEHA in the distillation process of 2-ethyl-4-(2,2,3-trimethylcyclopent-3- en-l-yl)but-2-en-l-ol crude prevents 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2- en-l-ol from undesired side reaction promoted by residual ruthenium and acid such as dehydrogenation, E / Z isomerization and polymerization.

[0133] Example 2

[0134] Use of polyamine as a metal / acid scavenger in liquid-liquid extraction process

[0135] A crude product mixture of 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-en-l-ol was prepared by the catalyzed homogeneous ruthenium complex hydrogenation of 2-ethyl- 4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-enal. The reaction has been performed as described in Example 6 of WO 2014 / 139854 Al on page 39. 680g of the crude product mixture 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-en-

[0136] 1-ol E / Z 91,4% / 3,6% sum 95%; 2-ethy l-4-(2, 2 -trimethy Icy clopent-3 -en-l-yl)but-2-enal 0,46%) and 20g of PEHA were stirred and heated at 165°C under nitrogen over 2h. Then the mixture was cooled to 90°C and washed twice with 300ml of water. The resulting oil was directly subjected to a fractional distillation at a temperature up to 180°C / 2mbar. 656g of heart fractions were obtained with a purity 97,5% 2-ethyl-4-(2,2,3-trimethylcyclopent- 3-en-l-yl)but-2-en-l-ol in a yield of 98,5%. The amount of 2-ethyl-4-(2,2,3- trimethylcyclopent-3-en-l-yl)but-2-enal was 0,01%.

[0137] Conclusion

[0138] The liquid-liquid extraction of 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-en-l-ol crude in the presence of PEHA efficiently removes the residual metal and acid from the organic material. The resulting crude material can be directly fractionated affording pure

[0139] 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-en-l-ol exempt from undesired side reaction promoted by residual ruthenium and acid such as dehydrogenation, E / Z isomerization and polymerization.

[0140] Example 3

[0141] Use of poly amine as a metal / acid scavenger in a distillation of a metathesis reaction product

[0142] A crude product mixture of 5-(2-oxocyclopentyl)pent-3-en-2-yl acetate was prepared by a cross metathesis reaction of 2-allylcyclopentan-l-one and 2 eq but-3-en-2-yl acetate using a homogeneous ruthenium complex. The reaction has been performed as described in Example 12 of WO 2021 / 176009 Al, pages 32-33, but without the addition 1,4-Bis(2- isocyanopropyljpiperazine and by using PEHA (pentaethylene hexamine) instead.

[0143] GC analysis of the crude by using l,4-Bis(2-isocyanopropyl)piperazine, CAS 51641-96-4) as metal scavenger (excluding but-3-en-2-yl acetate): 7.3% allylcyclopentan- 1 -one, 56.4% 5-(2-oxocyclopentyl)pent-3-en-2-yl acetate, 23.9% 2,2'-(but-2-ene-l,4- diyl)bis(cyclopentan-l-one, 11.6% hex-3-ene-2,5-diyl diacetate, GC analysis of the cruede by using PEHA as metal scavenger (excluding but-3-en-2-yl acetate): 6.9% allylcyclopentan-1 -one, 54.9% 5-(2-oxocyclopentyl)pent-3-en-2-yl acetate, 21.4% 2,2'- (but-2-ene-l,4-diyl)bis(cyclopentan-l-one, 11.4% hex-3-ene-2,5-diyl diacetate).

[0144] 24.71 g of the crude product mixture (18.8% but-3-en-2-yl acetate, 5.0% allylcyclopentan-

[0145] 1-one, 42.3% 5-(2-oxocyclopentyl)pent-3-en-2-yl acetate, 17.6 % 2,2'-(but-2-ene-l,4- diyl)bis(cyclopentan-l-one, 9.1% hex-3-ene-2,5-diyl diacetate) was distilled over 0.49 g PEHA (0.4 mbar, up to 150°C). 9.1 g 5-(2-oxocyclopentyl)pent-3-en-2-yl acetate, 2.3 g hex-3-ene-2,5-diyl diacetate and 1.3 g allylcyclopentan-1 -one were obtained.

[0146] Conclusion:

[0147] The presence of PEHA in the distillation process of the metathesis crude efficiently removes the residual metal and prevents undesired side reaction promoted by residual ruthenium such as isomerization and polymerization.

[0148] Example 4

[0149] Use of polyamine as a metal / acid scavenger in a distillation process

[0150] 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-en-l-ol was synthesized according to some homogeneous ruthenium catalyzed hydrogenation reaction of 2-ethyl-4-(2,2,3- trimethylcyclopent-3-en-l-yl)but-2-enal in the presence of benzoic acid (0.5 mol.%) and [(2-(diphenylphosphino)ethanamine)][9.9-dimethyl-4,5-bis(diphenylphosphino)xanthene] ruthenium(bispivalate) complex (0.005 mol.%) as described in Example 6 of WO 2014 / 139854 on page 39. Crude 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-en-l- ol was obtained in 95% GC purity as a 96 / 4 E / Z isomers ratio mixture and still containing 0.46 GC % of 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-enal. Still also containing benzoic acid (0.5 mol.%) and some ruthenium species (0.005 mol.%), it was kept under inert atmosphere before being divided into 3 parts which were then transferred into dedicated equipment where each part was subjected to purification by distillation up to 180°C under 20mbar. The first part was distilled in the absence of any polyethylene amine additive. The second part was distilled in the presence at of 1.89 wt.% (2.7 mol.%, 10.8 mol% nitrogen atoms) TETA (tri ethylenetetramine) whereas the third part was distilled in the presence of 2 wt.% (1.8 mol.%, 10.8 mol.% nitrogen atoms) PEHA (pentaethylene hexamine). a. Results from distillation without polyethylene amine additive

[0151] Distillation of 200g of crude 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-en-l-ol displaying 95% GC purity as a 96 / 4 E / Z isomers ratio mixture and still containing 0.46 GC % of 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-enal without additive afforded 178 g of distilled product containing 88.4% GC of 2-ethyl-4-(2,2,3-trimethylcyclopent-3- en-l-yl)but-2-en-l-ol as a94 / 6 E / Z isomers ratio mixture and 5.5% GC of2-ethyl-4-(2,2,3- trimethylcyclopent-3-en-l-yl)but-2-enal. b. Results from distillation in the presence of TETA

[0152] Distillation of 200g of crude 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-en-l-ol displaying 95% GC purity as a 96 / 4 E / Z isomers ratio mixture and still containing 0.46 GC % of 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-enal in the presence of 3.78 g TETA (25.8 mmol) afforded 197.5 g of distilled product containing 95.5% GC of 2-ethyl- 4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-en-l-ol as a 96 / 4 E / Z isomers ratio and 0.46% GC of 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-enal.

[0153] Olfactive assessment of product obtained according to this distillation procedure revealed fishy off-note in addition to the expected Sandalwood profile. Presence of TETA in distilled product was detected by GC analysis upon derivatization using MSTFA (N-Methyl-N- (trimethylsilyl)trifluoroacetamide). c. Results from distillation in the presence of PEHA

[0154] Distillation of 200g of crude 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-en-l-ol displaying 95% GC purity as a 96 / 4 E / Z isomers ratio mixture and still containing 0.46 GC % of 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-enal in the presence of 4 g PEHA (17.2 mmol) afforded 197.5 g of distilled product containing 95.5% GC of 2-ethyl-4-(2,2,3- trimethylcyclopent-3-en-l-yl)but-2-en-l-ol as a 96 / 4 E / Z isomers ratio and 0.46% GC of 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-enal. Product obtained according to this distillation procedure was displaying the expected Sandalwood profile without any additional off notes. Furthermore, no residual PEHA was detected in the distilled product by GC analysis upon derivatization using MSTFA (N- Methyl-N-(trimethylsilyl)trifluoroacetamide).

[0155] Conclusion:

[0156] From the above it can be seen that distillation of 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en- l-yl)but-2-en-l-ol crude in the presence of TETA and PEHA prevents 2-ethyl-4-(2,2,3- trimethylcyclopent-3-en-l-yl)but-2-en-l-ol from undesired side reaction promoted by residual ruthenium. However, distillation with TETA resulted in product having undesired olfactive properties, namely a fishy off-note, and GC analysis upon derivatization using MSTFA of distilled product clearly demonstrates that TETA is not adapted to avoid olfactive contamination during such a process, contrary to PEHA.

Claims

Claims1. A method of purifying an organic reaction product from a crude product mixture, the method comprises the step of: adding a polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, to a crude product mixture and conducting a purification step for removing at least one impurity from the crude product mixture selected from the group consisting of a metal compound, aLewis acid, a Bronsted acid, an organic halide and a combination thereof wherein di ethylene triamine and triethylene tetramine are excluded.

2. The method according to claim 1, wherein the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is a linear or branched polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, preferably linear polyethylene amine.

3. The method according to any of the preceding claims, wherein the polyethylene amine, polypropylene amine, copolymer or mixtures thereof has the following formula (T):wherein each R is independently from each other H or Ci-Cs alkyl, optionally substituted with a terminal amino group; and wherein p is an integer of 2 or 3, q is an integer from 2 or 3 and n is an integer from 1-100.

4. The method according to any of the preceding claims, wherein the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, has the following formula (I)(I), wherein each R is independently from each other H or Ci-Cs alkyl, optionally substituted with a terminal amino group; and wherein n is an integer from 1-100.

5. The method according to claim 3 or 4 wherein the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is a mixture of hexaethylene heptamine and heptaethylene octamine.

6. The method according to claim 3 or 4, wherein the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is pentaethylene hexamine or higher polyethylene polyamine, preferably pentaethylene hexamine.

7. The method according to any one of the preceding claims, wherein the metal of the metal compound is selected from the group consisting of Al, Ga, In, Ti, Ge, Sn, Sb, Pb, Bi, Fe, Ru, Os, Co, Rh, Ir, Mn, Re, Ni, Pd, Pt, Cu, Zn and combinations thereof.

8. The method according to any of the preceding claims, wherein the metal compound is a metal catalyst, preferably a transition metal catalyst.

9. The method according to any one of the preceding claims, wherein the metal compound is a hydrogenation catalyst or a metathesis catalyst, preferably selectedfrom the group consisting of platinum-based catalysts, palladium-based catalysts, ruthenium-based catalysts, iridium-based catalysts, rhodium-based catalysts, nickel-based catalysts, cobalt-based catalysts, iron-based catalysts, copper-based catalysts, molybdenum-based catalysts, tungsten-based catalysts and zinc-based catalysts.

10. The method according to any of the preceding claims, wherein the purification step is conducted by distillation or liquid-liquid extraction, preferably distillation.

11. Use of polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, as additive for purifying an organic reaction product from a crude product mixture, wherein di ethylene triamine and tri ethylene tetramine are excluded as a polyethylene amine.

12. Use according to claim 11, wherein the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is used as a metal scavenger, an acid scavenger or a complexation aid, preferably as a complexation aid.

13. Use according to any of claims 11 and 12, wherein the crude product mixture comprises at least an organic reaction product and at least a metal compound, preferably a transition metal compound and / or a Lewis acid and / or a Bronsted acid as impurity.

14. Use according to any of claims 11 to 13, wherein the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is used during a purification step of the crude product mixture.

15. Use according to any of claims 11 to 14, wherein the polyethylene amine, polypropylene amine, copolymer or mixtures thereof, preferably polyethylene amine, is used during a purification step of the crude product mixture by distillation or liquid-liquid extraction, preferably distillation.