DE102016010503A1 - Chain multiplication of unsaturated fatty acids - Google Patents

Abstract

The present invention relates to a process for producing a compound of general formula (1), more particularly to a process for producing a compound of general formula (8) by further reacting the compound of general formula (1).

Description

insbesondere ein Verfahren zur Herstellung einer Verbindung der allgemeinen Formel (8)

durch weiteres Umsetzen der Verbindung der allgemeinen Formel (1).The present invention relates to a process for producing a compound of the general formula (1)

in particular a process for the preparation of a compound of general formula (8)

by further reacting the compound of the general formula (1).

Terminally functionalized long-chain aliphatic compounds are important binders in biological and technical systems. Ultra-long-chain compounds with methylene sequences that significantly exceed the length of a typical fatty acid chain are of particular importance. For example, these occur as ceramides - one of the major components of the stratum corneum of the epidermis layer of the human skin - and are part of the cell walls of several algal species (algaenans) and plants (cutin and suberin). The highly hydrophobic character of the α, ω-difunctional building blocks is exploited here to produce an insoluble polymer that protects organisms from undesirable environmental influences and from loss of water. Furthermore, such chain lengths correspond to the typical lamellar thickness of polymer crystals, which is why they are of particular interest for convenient access to nanocrystals and refractory polymers. In addition, their length corresponds to the typical thickness of phospholipid bilayers, offering the potential for synthetic structures that mimic these ubiquitous structures of biological systems.

However, there are currently very few known syntheses of these compounds, which still achieve very low yields. In addition, the reagents used here and occurring undesirable by-products do not allow application of these syntheses in large-scale industrial processes.

Thus, it is an object of the present invention to provide a process which makes it possible to prepare terminally functionalized long-chain aliphatic compounds, in particular from readily available starting materials, and preferably does not consume further reagents via individual catalytic steps and does not generate excessive amounts of undesirable by-products.

This object is achieved by the embodiments characterized in the claims.

umfassend die Schritte

• (a) Umsetzen einer Verbindung der allgemeinen Formel (2) in Gegenwart eines Isomerisationskatalysators
  
  zur Herstellung einer Verbindung der allgemeinen Formel (3)
  
• (b) Abtrennen der Verbindung der allgemeinen Formel (3) und
• (c) Umsetzen der (abgetrennten) Verbindung der allgemeinen Formel (3) in Gegenwart eines Metathesekatalysators zur Herstellung der Verbindung der allgemeinen Formel (1),

wobei n und m jeweils unabhängig voneinander eine ganze Zahl von 1 bis 200 sind,
p = (m + n – 1) ist und
Y ausgewählt ist aus der Gruppe, bestehend aus einem Wasserstoffatom, einer Alkylgruppe, einer Cycloalkylgruppe, einer Arylgruppe, einer Heteroarylgruppe, -NR¹R² und -OR³, wobei jedes von R¹ bis R³ unabhängig voneinander ein Wasserstoffatom, eine Alkylgruppe, eine Cycloalkylgruppe, eine Arylgruppe oder eine Heteroarylgruppe ist.More particularly, the present invention relates to a process for producing a compound of the general formula (1)

comprising the steps

• (a) reacting a compound of the general formula (2) in the presence of an isomerization catalyst
  
  for the preparation of a compound of general formula (3)
  
• (b) separating the compound of the general formula (3) and
• (c) reacting the (separated) compound of the general formula (3) in the presence of a metathesis catalyst to prepare the compound of the general formula (1),

where n and m are each independently an integer from 1 to 200,
p = (m + n-1) and
Y is selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, -NR ¹ R ² and -OR ³ , wherein each of R ¹ to R ^{3 is} independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group.

The process according to the invention makes it possible inter alia to selectively shift an internal double bond of the compound of the general formula (2) to a chain end, the compound of the general formula (3) being obtained (steps (a) and (b) of the process according to the invention, eg. by a dynamic isomerization / crystallization process, see, for example 1 ). This isomerization is carried out with the aid of an isomerization catalyst in a solution, initially forming an equilibrium of isomers of the compound of the general formula (2), based on the position of the double bond in the chain (see, for example 2 ).

Surprisingly, an almost quantitative conversion to the compound of the general formula (3) can be achieved by means of a separation (eg by physical methods such as targeted crystallization by temperature change, selective absorption and selective crystallization by means of an auxiliary compound or chemical methods such as a subsequent reaction, for example, by selective metathesis) from the continuous dynamic equilibrium. For example, the compound of the general formula (3) may preferentially crystallize due to its lower solubility and slightly different polarity as compared with the other isomers even at a low equilibrium concentration. The choice of a suitable solvent and temperature gradient as well as the continuous replenishment of the compound of general formula (3) by the persistent isomerization equilibrium thereby form the net driving force for reacting the compound of general formula (2) to the compound of general formula (3) in this type of Separation. A decreasing concentration of the entirety of the double bond isomers in the solution with increasing amount of already crystallized material is compensated by the reduction of the temperature (for example, win 3 ). Any co-precipitated foreign isomers can be removed by recrystallization and returned to the dynamic isomerization / Are fed to crystallization. After removal of the isomerization catalyst, for example by filtration over silica, further isomerizations can thus be carried out without significant loss of activity and selectivity.

With the aid of the subsequent olefin metathesis step (c), an approximate doubling of the chain length of the compound of general formula (3) used to form the compound of general formula (1), with simultaneous cleavage of only a small C ₄ fragment (without Consideration of any carbon atom-containing radicals Y) achieved. In this case, this self-metathesis can be supported by the presence of short-chain olefin co-reagents. In such a two-step one-pot approach, self-metathesis occurs after prior cross-metathesis of the compound of general formula (3) with the co-reagent (see, for example, U.S. Pat 4 ). The olefin co-reagents used can later be separated and reused. As described above, the step (c) can also be used for separation in the step (b) by selectively reacting the compound of the general formula (3) as compared with the other double bond isomers. The steps (a) to (c) are then preferably carried out as a one-pot reaction.

As stated above, it is possible with the aid of the method according to the invention to produce terminally functionalized long-chain aliphatic compounds via individual catalytic steps without consumption of further reagents, without producing excessive amounts of undesirable by-products. The quasi-chain-doubled product can thereafter serve as the starting material for a further sequence of isomerization / separation processes (steps (a) and (b)) and self-metathesis (step (c)), thereby starting a chain amplification from the starting material originally used can be achieved.

The compounds of the present invention (ie, the compounds of the general formulas (1) to (8)) may be substituted or unsubstituted. The possible substituents of these compounds are not subject to any particular restriction, it being specified that the substitution of a product corresponds to the substitution of the starting compound (wherein any reaction-induced substitution changes may occur). For example, the compound of the general formula (1) has a substitution corresponding to the compound of the general formula (3). Thus, apart from this specification, instead of hydrogen atoms, all substituents known in the art may be attached to the other positions of the compounds of the present invention. The carbon atoms within a repeating unit (characterized by the integers m, n and p) can be substituted differently. For example, the possible substituents are selected from the group consisting of halogen, -NZ ¹ Z ² , -NO ₂ , -CN, -OZ ³ , -C (O) Z ⁴ , -C (O) NZ ⁵ Z ⁶ , - COOZ ⁷ , an alkyl group, a cycloalkyl group, an aryl group and a heteroaryl group, each of Z ¹ to Z ^{7 is} independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group, especially a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group. Preferably, the possible substituents are selected from the group consisting of halogen, -OZ ³ , an alkyl group, and an aryl group, more preferably selected from the group consisting of an alkyl group and an aryl group. Most preferably, the compounds of the present invention are unsubstituted.

Here, the term "halogen" refers in particular to fluorine atoms, chlorine atoms and bromine atoms, preferably chlorine atoms.

Further, the term "alkyl" or "alkyl group" denotes a branched or unbranched alkyl group having 1 to 10 carbon atoms, preferably 1 to 6, and more preferably 1 to 4 carbon atoms, which alkyl group may be optionally substituted as defined above.

Further, the term "cycloalkyl" or "cycloalkyl group" means a cycloalkyl group having 3 to 14 carbon atoms, preferably 4 to 10 carbon atoms, and more preferably 5 or 6 carbon atoms, which cycloalkyl group may be optionally substituted as defined above.

The term "aryl" or "aryl group" denotes an aryl group consisting of, for example, 1 to 3 rings, such as a phenyl group or a naphthyl group, which aryl group may be substituted as defined above.

The term "heteroaryl" or "heteroaryl group" denotes a heteroaryl group consisting of, for example, 1 to 3 rings, such as a pyridyl group, a pyrimidinyl group, a Thienyl group, a furyl group or a pyrrolyl group, wherein the heteroaryl group may be substituted as defined above.

When one of the compounds of the present invention is present as an E / Z double bond isomer mixture, the corresponding E / Z ratio is not particularly limited unless otherwise specified. This E / Z double bond isomer mixture can thus assume any ratio. In addition, the E / Z ratio may change from connection to connection. For example, the compound of the general formula (1) may have a different E / Z ratio than the compound of the general formula (3). The E / Z ratio of the compound of the general formula (1) may be, for example, greater than 1:50, in particular greater than 1:10, preferably greater than 1: 1, in particular greater than 2: 1, greater than 10: 1, greater than 20: 1, greater than 30: 1, greater than 40: 1, and most preferably greater than 50: 1.

According to the invention, n and m are each independently an integer from 1 to 200 and p = (m + n-1). In particular, m and n are each independently an integer from 2 to 100, preferably from 3 to 60, more preferably from 4 to 40, even more preferably from 6 to 20. Preferably, m = (n + 1), d. H. the chains on the opposite sides of the double bond of the compound of the general formula (2) have the same chain length. More preferably, m is an integer from 7 to 11 and n is an integer from 6 to 10, preferably at first / once through the steps (a) to (c) of the method according to the invention.

In the present invention, Y is selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, -NR ¹ R ² and -OR ³ , wherein each of R ¹ to R ³ independently represents a hydrogen atom, an alkyl group , a cycloalkyl group, an aryl group or a heteroaryl group. Preferably, Y is selected from the group consisting of a hydrogen atom, an alkyl group, -NR ¹ R ² and -OR ³ , more preferably Y is OR ³ . Preferably, R ¹ to R ^{3 are} independently a hydrogen atom, an alkyl group or an aryl group. R ³ is more preferably a hydrogen atom or an alkyl group, more preferably an alkyl group, especially an alkyl group having 1 to 4 carbon atoms. Most preferably, R ^{3 is} a methyl group since, for example, any crystallizations will give very good results. The steps (a) to (c) of the process according to the invention can also be carried out if, instead of the C (O) Y groups, CN groups are present.

In the steps (a) and (b) of the process of the present invention, the compound of the general formula (3) is obtained by a dynamic isomerization / separation method from the compound of the general formula (2). In step (a), the compound of general formula (2) is first reacted in the presence of an isomerization catalyst in a solution. As used herein, the term "isomerization catalyst" refers particularly to catalysts capable of isomerizing double bonds along alkyl chains attached thereto.

As isomerization catalysts, it is possible to use both solid, heterogeneous and homogeneous, soluble catalysts. These can be purely organic as well as containing metals. As a carrier, the heterogeneous catalysts may contain organic or inorganic solids, preferably inorganic oxides such as silica or aluminum oxides or carbon. The isomerization catalysts preferably contain transition metals. Examples of particularly suitable transition metals are nickel or palladium. These may be present in elemental form or in the form of complexes.

Complexes are preferably one or more mono- or polydentate phosphines as ligands which can coordinate via one or more phosphorus atoms at the metal center. In the phosphorus-containing ligands are as substituents R " ¹ -R" ³ on the phosphorus atom PR " ¹ R" ² R " ³ , independently of one another the same or different H, open-chain or cyclic aliphatic C ₁ to C ₃₀ radicals, aromatic C ₁ to C ₃₀ radicals, and via heteroatoms such as N, O or S bonded open-chain or cyclic aliphatic C ₁ to C ₃₀ radicals and aromatic C ₁ to C ₃₀ radicals suitable. The radicals R ^'1 to R'^'3 may also contain in the side chain heteroatoms such as O, N, S or P. Particularly suitable radicals are tert-butyl groups and isopropyl groups. The ligand may contain a plurality of phosphorus atoms which are bridged via one or more of the R '' radicals. Particularly suitable bridging radicals are those which bridge the phosphorus atoms over three or four atoms. Particularly suitable bridging radicals are -CH ₂ -C ₆ H ₄ -CH ₂ - and - (CH ₂ ) ₃ -. Examples of suitable phosphorus ligands are: 1,3-bis (di-tert-butylphosphino) propane; 1,3-bis butane (di-tert-butylphosphino); 1,3-bis (di-tert-butylphosphino) -2,2'-dimethyl-propane; 1,2-bis [(di-tert-butylphosphino) methyl] benzene (dtbpx), triphenylphosphine or tri-tert-butylphosphane. One type of phosphorus-containing ligand or a mixture of several phosphorus-containing ligands can be used.

Examples of suitable palladium compounds are palladium acetate, palladium hexanoate, palladium octanoate, bis (dibenzylideneacetone) palladium, tetrakis (triphenylphosphine) palladium, (1,5-cyclooctadiene) dimethylpalladium, (1,5-cyclooctadiene) dichloropalladium, (1,5-cyclooctadiene) methylchloropalladium, Tetrakis (acetonitrile) palladium (II) tetrafluoroborate, and diacetonitrile dichloropalladium.

The catalyst may optionally contain other components, for example organic or inorganic acids or their salts. Examples of suitable further components include trifluoromethanesulfonic acid, methanesulfonic acid, perchloric acid, p-toluenesulfonic acid, [H (OEt ₂ )] [BAr ^F ₄ ], NaBAr ^F ₄ with Ar ^F = 3,5-bis (trifluoromethyl) phenyl.

The catalyst components can be mixed together in any order. The mixture can take place in or outside the reaction vessel. In particular, preformed palladium complexes of the phosphine can be used. An example of a suitable preformed complex as an isomerization catalyst is [Pd (dtbpx) (OTf) ₂ ]. Most preferred is the isomerization catalyst [Pd (dtbpx) (OTf) ₂ ].

The steps (a) and (b) of the process according to the invention can be carried out in a solvent or solvent-free. Preferably, steps (a) and (b) are carried out in a solvent. The potential solvent in steps (a) and (b) of the process according to the invention is not particularly limited. For example, the solvent may be water, a solvent (mixture) based on one or more organic solvents, or a mixed solvent of water and one or more organic solvents. Preferably, the solvent for steps (a) and (b) of the process of the invention is selected from the group consisting of one or more alcohols, dichloromethane, chloroform, dioxane, ethyl acetate, tetrahydrofuran, DMF, DMSO, acetonitrile, aromatic and / or aliphatic Hydrocarbons such as pentane, heptane, cyclohexane, benzene and toluene, and water or combinations of two or more thereof. The term "alcohol" as used herein refers to an alkanol having 1 to 6, preferably 1 to 4, more preferably 1 or 2, carbon atoms, and 1 or 2 hydroxyl groups, preferably a hydroxyl group. Even more preferably, the solvent for steps (a) and (b) of the process of the invention is one or more alcohols, preferably methanol or ethanol, since these give the best yields.

The (initial) concentration of the compound of general formula (2) at the beginning of step (a) is not particularly limited. For example, the compound of the general formula (2) may be in a concentration of 0.001 to 3.0 M, especially 0.01 to 2.0 M, of 0.05 to 1.0 M, of 0.1 to 0.5 M, and most preferably from 0.2 to 0.3M. Outside the stated limits, solubility problems may occur that adversely affect selectivity.

For example, the isomerization catalyst in a concentration of 0.0001 to 10 mol%, particularly 0.02 to 5.0 mol%, from 0.05 to 2.0 mol%, from 0.1 to 1.0 mol%, and most preferably from 0.3 to 0.7 mol%, based on the starting concentration of the compound of the general formula (2). Depending on the substrate, the isomerization catalyst may be present not only in catalytic amounts but also in (approximately) stoichiometric amounts or in amounts less than the amounts indicated.

In step (b) of the process according to the invention, the compound of general formula (3) is separated off. For example, the separation by physical methods such as a targeted crystallization by temperature change, a selective absorption and a selective crystallization by means of an auxiliary compound or chemical methods such as a subsequent reaction, for. Example, by selective conversion by metathesis (for example by a one-pot reaction in combination with step (c)) take place. The separation in step (b) is preferably carried out by controlled crystallization by temperature change, the combination of steps (a) and (b) representing a dynamic isomerization / crystallization process. In this preferred embodiment, a mixture or a solution comprising the compound of the general formula (2) and the isomerization catalyst is tempered to a temperature at which the compound of the general formula (3) starts to precipitate selectively. The term "tempering" as used herein means that from a higher temperature at which the compounds of general formulas (2) and (3) and also present double bond isomers are not present as solids, to a lower temperature at which the compound of general formula (3) begins to precipitate selectively, is cooled and this lower temperature is initially kept constant.

The temperature to which temperature is controlled in the step (b) (tempering temperature) is not particularly limited and is determined mainly by the properties and concentration of the compound of the general formula (3) and the solvent. In this case, all commonly used in the prior art tempering can be used. For example, the temperature at which the solution is heated in step (b) from -150 to 500 ° C, especially from -100 to 250 ° C, from -80 to 200 ° C, from -60 to 100 ° C, and most preferably from -40 to 70 ° C. The period of time for which the temperature is maintained is not particularly limited. For example, the period may be from 1 minute to 21 days, especially from 1 hour to 7 days, from 2 hours to 3 days, from 3 hours to 2 days, and most preferably from 4 hours to 24 hours. Depending on the solvent used and the concentration used, the crystallization point may shift, as the solubilities may differ greatly. With better solvents, a lower crystallization temperature can be achieved.

After tempering, it is possible to (further) cool down. In this case, all known in the art cooling methods can be used. Thereby, it is advantageously possible to further precipitate the compound of general formula (3). The double bond isomer equilibrium ensures that further (initially dissolved) material is replicated on the compound of general formula (3). The temperature gradient (between the tempering temperature and the final temperature after (further) cooling) is not particularly limited and is determined mainly by the properties and concentration of the compound of general formula (3), the dissolution behavior of the other isomers and the solvent. For example, it may be cooled by from 0.01 to 500 ° C, more preferably by from 0.1 to 200 ° C, by from 1 to 150 ° C, by from 10 to 100 ° C, and most preferably by from 20 to 60 ° C , The time interval between the start of the (further) cooling and the reaching of the final temperature in step (b) is not subject to any particular restrictions and is determined mainly by the resulting selectivity of the precipitated products. For example, the time interval may be from 1 minute to 21 days, especially from 1 hour to 7 days, from 2 hours to 3 days, from 3 hours to 2 days, and most preferably from 4 hours to 24 hours.

In a preferred embodiment, the process according to the invention after step (b) and before step (c) further comprises a step (b1) of adding an isomerization interrupting agent. By adding the Isomerisationsunterbrechungsmittels further isomerization and thus the isomerization equilibrium is interrupted. Otherwise, the isomerization equilibrium could be adjusted again in the further process if the catalyst is still active. In addition, different chain lengths could result in the metathesis step, which is undesirable. Suitable isomerization interruption agents are known to those skilled in the art. Examples of isomerization interruption agents are organic amines of the type NA ¹ A ² A ³ having three organic radicals A ¹ , A ² , A ³ which, independently of one another, are identical or different H, open-chain or cyclic aliphatic C ₁ to C ₃₀ radicals, aromatic C ₁ to C ₃₀ radicals, and via heteroatoms such as N, O or S bonded open-chain or cyclic aliphatic C ₁ to C ₃₀ radicals and aromatic C ₁ to C ₃₀ radicals may be. The radicals A ¹ to A ³ may also contain heteroatoms in the side chain, for example O, N, S or P. Examples of isomerization interruption agents are trimethylamine, triethylamine, tripropylamine, ammonia, 1,5-diazabicyclo (4.3.0) non-5 or 1,8-bis (N, N-dimethylamino) -naphthalene. Preferably, the isomerization interruption agent is triethylamine. The concentration of the isomerization-interrupting agent in the solution in step (b1) is not particularly limited. For example, the isomerization disrupting agent may be present in a concentration of from 0.0001 to 20 M, more preferably from 0.0005 to 10 M, from 0.001 to 1.0 M, from 0.005 to 0.5 M, and most preferably from 0.01 to 0 , 1 M are present.

In a preferred embodiment, the process according to the invention after step (b) (and optional step (b1)) and before step (c) further comprises a step (b2) of purifying the compound of general formula (3) (from the remaining constituents, such as liquid ingredients / the solution, the isomerization catalyst and the optional isomerization-interrupting agent) if steps (b) and (c) are not carried out in a one-pot reaction. In this case, all commonly used in the prior art purification process can be used. In particular, step (b2) may include liquid component removal / solution (eg, by filtration), dissolving the compound of general formula (3) in (little) solvent, removing the isomerization catalyst from the solution of the compound of general formula (3) (e.g., by filtration), removing the solvent from the solution of the compound of the general formula (3) (e.g., by evaporation), and recrystallizing the compound of the general formula (3) in this order , The solvents for dissolving or recrystallizing the compound of the general formula (3) are not particularly limited and are known to those skilled in the art. Examples of the solvent for dissolving the compound of the general formula (3) are dichloromethane, chloroform, tetrachloroethane, tetrahydrofuran, dioxane, toluene and Chlorobenzene. Examples of the solvent for recrystallizing the compound of the general formula (3) are methanol, ethanol, propanol, iso-propanol, heptane, hexane, octane, cyclohexane, pentane, butane and butenes.

In step (c) of the process according to the invention, the (separated) compound of general formula (3) is reacted in the presence of a metathesis catalyst to produce the compound of general formula (1). Here, the term "metathesis catalyst" refers in particular to olefin metathesis catalysts. Examples of metathesis catalysts are ruthenium metathesis catalysts, such as Grubbs first generation catalysts (G1, benzylidene bis (tricyclohexylphosphine) dichlororuthenium), Grubbs second generation catalysts (G2, benzylidene [1,3-bis (2,4,6-trimethylphenyl) - 2-imidazolidinylidene] dichloro (tricyclohexylphosphine) ruthenium), Hoveyda-Grubbs first generation catalysts (HG1, dichloro (o-isopropoxyphenylmethylene) (tricyclohexylphosphine) ruthenium), Hoveyda-Grubbs second generation catalysts (HG2, 1,3-bis ( 2,4,6-trimethylphenyl) -2-imidazolidinylidene) dichloro (o-isopropoxyphenylmethylene) ruthenium), rapidly initiating Grubbs catalysts (G3, dichloro [1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene] (benzylidene) bis (3-bromopyridine) ruthenium), Piers first generation catalysts (P1, dichloro (tricyclohexylphosphine) - [(tricyclohexylphosphoranyl) methylidene] ruthenium tetrafluoroborate), Piers second generation catalysts (P2, dichloro [1,3-b is (2,4,6-trimethylphenyl) -2-imidazolidinylidene] - [(tricyclohexylphosphoranyl) methylidene] ruthenium tetrafluoroborate), Grela catalysts ((1,3-dimesitylimidazolidin-2-ylidene) (2-isopropoxy-5-nitrobenzylidene) ruthenium chloride), and structurally related metathesis catalysts of the type mentioned with carbene ligands of the type benzylidene, dimethylvinyl, indenylidene, Allenalkyliden and benzylidene derivatives having one to several substituents on the aromatic. In addition to the ruthenium-based catalysts, metathesis catalysts with early transition metals are also possible, for example Schrock catalysts (S1, 2,6-diisopropylphenylimidoneophylidene molybdenum bis (hexafluoro-t-butoxide).) The use of multicomponent metathesis catalysts is likewise possible, for example tungsten hexachloride with tetrabutylstannane If these catalysts can be supported or used in molecular form, it is preferable to use silica, alumina or carbon as the support material Preferably, the metathesis catalyst is selected from the group consisting of G2, G3, HG2 and P2 Most preferably, the metathesis catalyst is HG2.

The step (c) of the process according to the invention can be carried out in a solvent or solvent-free. Preferably, step (c) is carried out in a solvent. The optional solvent in step (c) of the process of the invention is not particularly limited. For example, the solvent may be water, a solvent (mixture) based on one or more organic solvents, or a mixed solvent of water and one or more organic solvents. Preferably, the solvent for step (c) of the process of the invention is selected from the group consisting of dichloromethane, heptane, benzene, toluene, chloroform, hexane, cyclohexane, pentane, methanol, ethanol, t-butyl methyl ether, 1,2-dichloroethane, chlorobenzene , Ethyl acetate, acetone, tetrahydrofuran, acetic acid and water, or combinations of two or more thereof. More preferably, the solvent for step (c) of the process of the invention is selected from dichloromethane, toluene and / or heptane.

The (initial) concentration of the compound of general formula (3) in the solution at the beginning of step (c) is not particularly limited. For example, the compound of the general formula (3) in a concentration of 0.0001 to 5.0 M, especially from 0.001 to 3.0 M, from 0.01 to 2.0 M, from 0.05 to 1.5 M, and most preferably from 0.1 to 1.0M. Outside these ranges, the rate of decomposition of metathesis catalysts could be adversely affected. Low concentrations can also lead to low space-time yields.

For example, the metathesis catalyst in step (c) may be present in a concentration of from 0.00001 to 20 mole%, more preferably from 0.001 to 10 mole%, and most preferably from 0.01 to 2.0 mole%, based on the Initial concentration of the compound of general formula (3), are present. Depending on the substrate, the metathesis catalyst may be present not only in catalytic amounts but also in approximately stoichiometric amounts or in amounts less than that indicated.

In a preferred embodiment of the process according to the invention, step (c) is carried out in the presence of an isomerization suppressant. By the presence of an isomerization-suppressing agent, it is advantageously possible to inhibit potential isomerization of the double bond (based on the position of the double bond) by the metathesis catalyst, whereby excellent chain length selectivity can be achieved. The concentration of the isomerization-suppressing agent in step (c) is not particularly limited. For example, the isomerization suppressant may be used in a concentration of 0.00002 to 50 mol%, especially 0.002 to 20 mol%, and most preferably from 0.02 to 5.0 mol%, based on the initial concentration of the compound of the general formula (3). Preferably, the isomerization suppressant is 1,4-benzoquinone since this gives the best results.

Preferably, the process of the invention in step (c) is further carried out in the presence of an alkene of 2 to 18 carbon atoms, more preferably 4 to 8 carbon atoms, even more preferably 6 carbon atoms, most preferably in the presence of 2/3 hexene. By the presence of such an alkene, it is advantageously possible to promote the self-metathesis of the compound of general formula (3) via an initial cross-metathesis between the compound of general formula (3) and the alkene. The concentration of the alkene in step (c) is not particularly limited. For example, the alkene may be in a molar ratio, based on the starting concentration of the compound of the general formula (3), from 0.01 to 5000 equivalents, especially from 0.1 to 1000 equivalents, from 1.0 to 100 equivalents, and most preferably from 5.0 to 30 equivalents.

The (reaction) temperature in step (c) is not particularly limited. For example, the temperature in step (c) may be from -50 to 500 ° C, especially from -20 to 200 ° C, from -10 to 100 ° C, and most preferably from 0 to 60 ° C.

The (reaction) time in step (c) is not particularly limited. For example, the reaction time in step (c) may be from 1 minute to 7 days, more preferably from 3 minutes to 24 hours, and most preferably from 15 minutes to 1 hour.

In a preferred embodiment, after step (c), the process according to the invention further comprises a step (c1) of removing volatile components from the reaction mixture of step (c). Methods for removing volatile components from a reaction mixture are known to those skilled in the art. For example, volatile components can be removed from a reaction mixture by applying a negative pressure. By removing volatile components from the reaction mixture of step (c), it is advantageously possible to achieve complete conversion to the compound of general formula (1).

In a preferred embodiment, the process according to the invention further comprises after step (c) a step (c2) of adding a metathesis interrupting agent. The addition of the metathesis disrupting agent prevents further metathesis reactions. Suitable metathesis interruption agents are known to those skilled in the art. Examples of metathesis interruption agents are ethyl vinyl ether, potassium isocyanoacetate, tri (hydroxymethyl) phosphine, triphenylphosphine oxide, lead (IV) acetate and DMSO. Preferably, the metathesis disrupting agent is ethyl vinyl ether because it gives the best results. The concentration of the metathesis interrupting agent in the solution in step (c2) is not particularly limited. For example, the metathesis disrupting agent may be present at a level of from 0.001 to 10 M, more preferably from 0.01 to 5.0 M, and most preferably from 0.1 to 1.5 M.

In a preferred embodiment, the process according to the invention after step (c) (and optional steps (c1) and / or (c2)) further comprises a step (c3) of separating the compound of general formula (1) (from the remaining constituents such as the solution, the metathesis catalyst and the optional metathesis interruption agent). In this case, all commonly used in the prior art separation processes can be used. In particular, step (c3) may comprise removing the metathesis catalyst from the solution of the compound of general formula (1) (eg by filtration), removing the solvent (and the metathesis disrupting agent) from the solution of the compound of general formula (1). (eg, by evaporation) and recrystallizing the compound of general formula (1) in this order. Suitable solvents for recrystallizing the compound of general formula (1) are known to those skilled in the art. Examples of solvents for recrystallizing the compound of the general formula (1) are methanol, ethanol, isopropanol, toluene, benzene, chlorobenzene, heptane, hexane, cyclohexane and / or dichloromethane.

• (a0) Umsetzen einer Verbindung der allgemeinen Formel (4) in Gegenwart eines Metathesekatalysators
  
  zur Herstellung einer Verbindung der allgemeinen Formel (5)
  
• (a1) optionales Verestern oder Amidieren der Verbindung der allgemeinen Formel (5) zur Herstellung einer Verbindung der allgemeinen Formel (2) mit Y = -NR¹R² bzw. Y = -OR³ mit R³ ≠ H,

wobei X ausgewählt ist aus der Gruppe, bestehend aus einem Wasserstoffatom, einer Alkylgruppe, einer Cycloalkylgruppe, einer Arylgruppe und einer Heteroarylgruppe. Wenn Y H ist, dann entspricht die Verbindung der allgemeinen Formel (5) der Verbindung der allgemeinen Formel (2).Preferably, the method according to the invention further comprises the steps before step (a)

• (a0) reacting a compound of the general formula (4) in the presence of a metathesis catalyst
  
  for the preparation of a compound of general formula (5)
  
• (a1) optionally esterifying or amidating the compound of general formula (5) to produce a compound of general formula (2) with Y = -NR ¹ R ² or Y = -OR ³ with R ³ ≠ H,

wherein X is selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group and a heteroaryl group. When Y is H, then the compound of the general formula (5) corresponds to the compound of the general formula (2).

Preferably, X is selected from the group consisting of a hydrogen atom, an alkyl group, and an aryl group. More preferably, X is a hydrogen atom or an alkyl group. More preferably, X is an alkyl group, especially of 1 to 15 carbon atoms, of 4 to 12 carbon atoms, of 6 to 10 carbon atoms, and most preferably of 8 carbon atoms. The compound of the general formula (4) is preferably a monounsaturated fatty acid, especially a naturally occurring monounsaturated fatty acid such as palmitoleic acid (ie m = 7 and X = n-hexyl, double bond cis), oleic acid (ie m = 7 and X = n-octyl; double bond cis) and erucic acid (ie m = 11 and X = n-octyl; double bond cis), since these are easily accessible. More preferably, the compound of the general formula (4) is selected from the group consisting of oleic acid and erucic acid. Most preferably, the compound of general formula (4) is oleic acid.

In optional step (a0) of the process according to the invention, the same metathesis catalyst as in step (c) can be used. The definitions and explanations given in step (c) regarding the metathesis catalyst, the solvent (if present), the (reaction) temperature, the (reaction) time, the isomerization suppressant and a metathesis interruption agent apply analogously, the concentrations of the metathesis catalyst and of the isomerization-suppressing agent to the concentration of the compound of the general formula (4).

The (initial) concentration of the compound of the general formula (4) at the beginning of step (a0) is not particularly limited. For example, the compound of the general formula (4) may be present in a concentration of 0.001 to 5.0 M, more preferably 0.01 to 4.0 M, and most preferably 1.0 to 3.0 M. Outside the preferred ranges, the yield may be negatively impacted since only equilibrium conditions (i.e., 50% of theoretical yield) could be achieved. Preferably, step (a0) is carried out without solvent, ie with the compound of the general formula (4) as the medium.

Preferably, the compound of the general formula (5) precipitates from the reaction mixture in the optional step (a0). Thereby, a potential reaction equilibrium can be shifted to the compound of the general formula (5). The precipitation is preferably induced by the formation of the compound of the general formula (5). Preferably, the reaction temperature is chosen to be above the melting point of the fatty acid used. Due to a higher melting point and a lower solubility of the reaction product, precipitation occurs automatically after reaching a certain conversion.

In optional step (a1) of the process according to the invention, the compound of general formula (5) is esterified (Y = -OR ³ , R ³ ≠ H) or amidated (Y = -NR ¹ R ² ), wherein a compound of the general Formula (2) with Y = -OR ³ (with R ³ ≠ H) or -NR ¹ R ^{2 is} prepared. Suitable processes for esterification or amidation are known to the person skilled in the art. For example, in the case of esterification, the alcohol R ³ OH may be added as solvent or in excess, based on the compound of the general formula (5). Furthermore, the esterification acidic, for example, by H ₂ SO ₄ or p-toluenesulfonic acid, take place.

• (d) Hydrieren der Verbindung der allgemeinen Formel (1) zur Herstellung einer Verbindung der allgemeinen Formel (6)
  
• (e) Reduzieren der Verbindung der allgemeinen Formel (6) zur Herstellung einer Verbindung der allgemeinen Formel (7)
  
• (f) Umsetzen der Verbindungen der allgemeinen Formeln (6) und (7) zur Herstellung einer Verbindung der allgemeinen Formel (8)
  

wobei x eine ganze Zahl von 1 bis 1000 ist.In a preferred embodiment, the method according to the invention after step (c) (and the optional steps (c1), (c2) and (c3)), when Y is OR ³ , further comprises the steps

• (d) hydrogenating the compound of general formula (1) to produce a compound of general formula (6)
  
• (e) reducing the compound of the general formula (6) to produce a compound of the general formula (7)
  
• (f) reacting the compounds of the general formulas (6) and (7) to produce a compound of the general formula (8)
  

where x is an integer from 1 to 1000.

By the optional steps (d) to (f) it is advantageously possible to produce polymers with preferably high melting points and strongly hydrophobic character. These polymers are thus preferably water-repellent and particularly light-stable (for example in comparison to polymers having high melting points but aromatic building blocks). These polymers can be used, for example, in polymer blends or in fuel cells.

Preferably, x is an integer from 1 to 1000, more preferably from 10 to 500, and most preferably from 15 to 100.

In the step (d), the compound of the general formula (1) is hydrogenated to produce the compound of the general formula (6). Suitable hydrogenation processes are known to those skilled in the art. Examples of suitable hydrogenating agents are Pd / C, PdO, Pd (OH) ₂ / BaSO ₄ , platinum black, palladium black or Cu / SiO ₂ and H ₂ , or homogeneous soluble complexes such as ruthenium, iridium or rhodium complexes containing phosphine ligands can be used in step (f). The hydrogen pressure may be, for example, in the range of 0.1 to 1000 atm (1.0133 x 10 ⁴ to 1.0133 x 10 ⁸ Pa), preferably 1 to 100 atm (1.0133 x 10 ⁵ to 1.0133 x 10 ⁷ Pa), and more preferably from 5 to 50 atm (5.0665 x 10 ⁵ to 5.0665 x 10 ⁶ Pa). The hydrogenation temperature may be, for example, from -50 to 500 ° C, preferably from 0 to 200 ° C, particularly preferably from 20 to 100 ° C. The reaction time in step (d) may be, for example, in the range from 1 minute to 7 days, preferably from 1 hour to 2 days, particularly preferably from 4 hours to 20 hours. Examples of suitable solvents in step (d) are tetrahydrofuran, dioxane, cyclohexane, toluene, methanol, ethanol, isopropanol, ethyl acetate, water, acetic acid, dichloromethane, heptane and / or butanol, preferably tetrahydrofuran, dioxane, methanol and / or ethanol. particularly preferably tetrahydrofuran and / or methanol are used. A solvent-free process is equally feasible. For the (initial) Concentrations of the starting compounds of general formula (1) are not particularly limited. For example, concentrations of from 0.0001 to 2.0 M, preferably from 0.001 to 1.5 M, particularly preferably from 0.1 to 1.0 M can be used. The amount of catalyst can be, for example, in the range from 0.01 to 50% by weight, preferably from 0.5 to 20% by weight, particularly preferably from 2.0 to 10% by weight, based on the compound of the general formula (1), be.

In the step (e), the compound of the general formula (6) is reduced to produce the compound of the general formula (7). Suitable methods of reduction are known to those skilled in the art. As the reducing agent, for example, LiAlH ₄ can be used in step (e). Furthermore, homogeneous catalysts may also be used, for example dichlorobis [2- (diphenylphosphino) ethylamine] ruthenium or carbonylhydrido [6- (di-t-butylphosphinomethylene) -2- (N, N-diethylaminomethyl) -1,6-dihydropyridine] ruthenium. The same conditions and preferences apply as already done for step (d).

Further, steps (d) and (e) can be reacted together in a reaction with a homogeneous catalyst. Suitable methods of reduction are known to those skilled in the art. As the catalyst, for example, carbonyl chlorohydrido [2- (di-iso-propylphosphino) -N- (2-pyridinylmethyl) ethanamine] ruthenium can be used. Here, the same conditions and preferences apply as already done for step (d).

In the step (f), the compounds of the general formulas (6) and (7) are reacted to give the compound of the general formula (8). Suitable methods for preparing the compound of the general formula (8), such as a polycondensation, are known to those skilled in the art.

For example, a polycondensation in the form of a melt polycondensation, solution polymerization or solid polymerization can take place. The polymerizations can be carried out in a temperature program and under different pressures. Preferably, a melt polycondensation is carried out.

The temperature to which the monomers are heated may be, for example, from 0 to 500 ° C, especially from 50 to 250 ° C, from 80 to 200 ° C, and most preferably from 80 to 150 ° C. The period of time for which the temperature is maintained is not particularly limited. For example, the period may be from 1 second to 21 hours, especially from 1 minute to 7 days, from 10 minutes to 24 hours, and most preferably from 30 minutes to 6 hours.

Preferably, the reaction is started under pressure. The pressure is not subject to any special restrictions. For example, the pressure may be from 1.0 to 1000 atm (1.0133 x 10 ⁵ to 1.0133 x 10 ⁸ Pa), preferably from 1.1 to 100 atm (1.11463 x 10 ⁵ to 1.0133 x 10 ⁷ Pa), and more preferably from 1.2 to 5 atm (1.21596 x 10 ⁵ to 5.0665 x 10 ⁵ Pa).

The temperature gradient for the reaction is not particularly limited. For example, the reaction mixture in step (f) may be heated by 0.0 to 200 ° C, especially by 1.0 to 100 ° C, and most preferably by 20 to 80 ° C (further). The time interval between the start of the reaction in step (f) and the reaching of the final temperature in step (f) is not particularly limited. For example, the time interval in step (f) may be from 1 minute to 7 days, more preferably from 30 minutes to 2 days, and most preferably from 2 hours to 12 hours.

As the reaction temperature proceeds, a pressure reduction is preferably carried out. The pressure reduction is subject to no particular restrictions. The pressure may be, for example, from 0.0 to 1000 atm (0.0 to 1.0133 x 10 ⁸ Pa), preferably from 0.1 to 100 atm (1.0133 x 10 ⁴ to 1.0133 x 10 ⁷ Pa), and most preferably reduced by 0.5 to 5 atm (5.0665 x 10 ⁴ to 5.0665 x 10 ⁵ Pa).

The final temperature reached in step (f) is preferably maintained for a certain period of time. The duration is not subject to any special restrictions. For example, the final temperature of 1 s to 7 d, preferably from 1 min to 2 d, and more preferably maintained from 1 h to 12 h.

Suitable catalysts are known to those skilled in the art. For example, step (f) may be carried out in the presence of a catalyst selected from the group consisting of [Ti (OiPr) ₄ ], [Ti (OnBu) ₄ ], [Zr (OiPr) ₄ ], [Zr (OnBu) ₄ ], Tin (2-ethylhexanoate), zinc acetate, antimony (III) oxide and dibutyltin oxide. Preferably, [Ti (OiPr) ₄ ] or [Ti (OnBu) ₄ ] is used as the catalyst in step (f).

The figures show:

1 Steps (a) to (c) (and the optional steps (a0) and (a1)) of the inventive method using the example of oleic acid as starting material.

2 ¹ H-NMR spectrum of a double bond isomer mixture in step (a) of the process according to the invention using the example of the compound 2a in FIG 1 when reacted with 1 mol% of [Pd (dtbpx) (OTf) ₂ ] at 30 ° C in a mixture of CDCl ₃ and CD ₃ OD (4/1).

3 : Temperature gradient for isomerization / crystallization steps using the example of compound 3a 1 ,

4 "Chain doubling" in step (c) of the process according to the invention via cross-metathesis with short-chain olefins using the example of compounds 3a and 4a 1 (Cat1 = HG2).

5 GC study of a crude product after "chain doubling" in step (c) with 2- / 3-hexene using compound 3a as an example.

6 : Optional steps (d) to (f) of the method according to the invention using the example of compound 4a 1 ,

The present invention will be further illustrated by the following non-limiting examples.

General:

All reactions and processing of moisture and air sensitive substances were conducted under an inert gas atmosphere using standard Schlenk or glove box techniques. Solvents were dried under an inert atmosphere as follows: toluene was distilled over sodium prior to use, MeOH was distilled over magnesium turnings. All dry, degassed solvents were stored under an inert atmosphere. Oleic acid (1, Dakolub MB6098 high oleic sunflower oil with 92.5% oleic acid), supplied by Dako AG, was degassed prior to use. 2- / 3-hexene was prepared from 1-hexene (Sigma Aldrich) which was isomerized with Cat2 and then distilled off. Benzoquinone (available from Sigma Aldrich) was sublimed before use. A pure sample of dimethyl-1,32-dotricont-16-endioate (4a) for comparative GC analysis was obtained by a Wittig reaction of methyl 16-oxohexadecanoate and methyl 16-bromohexadecanoate. [Pd (dtbpx) (OTf) ₂ ] (= Cat2) was prepared by a known method ( Stempfle, F .; Quinzler, D .; Heckler, I .; Mecking, S. Macromolecules 2011, 44, 4159-4166 ). The Hoveyda-Grubbs second generation catalyst (HG2; Cat1) (available from Carbosynth) was stored in a glove box under a protective gas atmosphere. Titanium tetrabutoxide ([Ti (OnBu) ₄ ]) (available from Sigma Aldrich) was stored under a protective gas atmosphere. All deuterated solvents for NMR spectroscopy are available from Euriotop. Organic syntheses were monitored by thin layer chromatography on Merck TLC Kieselgel 60 F254 plates on plastic sheets with F254 fluorescence indicator. The TLC plates were stained with an ethanolic phosphomolybdic acid solution for spot analysis. NMR spectra were recorded on a Bruker Avance 400 spectrometer. ¹ H and ¹³ C chemical shifts were referenced to the solvent signals. NMR spectroscopy of polymers was performed in 1,1,2,2-tetrachloroethane-d ₃ at 130 ° C. GPC analyzes of polymers were performed on a Polymer Laboratories GPC220 instrument equipped with PLgel Olexis columns using a refractive index detector. Molecular weights were determined by calibration with PE standards at 160 ° C in 1,2,4-trichlorobenzene (flow rate: 1.0 mL min ^-1 ). GC analyzes were performed using a Perkin Elmer 500 Clarus gas chromatograph with an autosampler equipped with an Elite-5 crossbond 5% diphenyl-95% dimethylpolysiloxane column 30 m in length, 0.25 mm I.D. and 0.25 μm layer thickness , Helium was used as carrier at a constant flow rate of 1.5 mL per minute. The oven temperature was maintained at 90 ° C for 1 minute and thereafter heated from 90 ° C to 280 ° C at a heating rate of 30 ° C per minute. The final temperature was maintained for 8 minutes. The injector was kept at 300 ° C and the detector at 280 ° C. The injection volume was 1.0 μL. For ultra-long chain compounds (up to C ₃₂ ), the following conditions were used. An Elite-5 crossbond 5% diphenyl-95% dimethylpolysiloxane column of 15 m length, 0.32 mm inner diameter and 0.10 μm layer thickness was used. The carrier flow rate was maintained at 1.5 mL per minute. The oven temperature was heated from 75 ° C to 230 ° C at a heating rate of 25 ° C per minute. Thereafter, the temperature was raised to 330 ° C at a heating rate of 10 ° C per minute, and the final temperature was maintained for 10 minutes. The injector and detector were kept at 350 ° C. For Compounds with longer chains have been modified in this program (final temperature 350 ° C, carrier flow rate 6.0 mL per minute). Retention times and peak area analysis was performed using Perkin Elmer's TotalChrom software. The DSC analysis was performed at a heating rate of 10 ° C per minute in a temperature range of -50 ° C to 160 ° C on a Netzsch DSC 204 F1. All data given are from second heating cycles. All elemental analyzes were performed on an Elementar vario MICRO cube elemental analyzer. ESI-MS measurements were performed on a Bruker o-TOF II instrument in acetonitrile solution.

The present invention is further illustrated by the starting compounds oleic acid (1a) and erucic acid (1b), but it is not limited thereto.

Example 1: General procedure for the optional steps (a0) and (a1) of the process according to the invention with reference to the compounds 1a and 1b

• 2a (x = 1): 'H NMR (CDCl₃, 400 MHz, 25°C): δ = 5,42–5,23 (m, 2H, H-7), 3,66 (s, 6H, H-1), 2,29 (t, ³J_HH = 7.5 Hz, 4H, H-3), 1,99–1,91 (m, 4H, H-6), 1,66–1,56 (m, 4H, H-4), 1,37–1,24 (m, 16H, H-5) ppm; ¹³C{¹H} NMR (CDCl₃, 100 MHz, 25°C): δ = 174,4 (C-2), 130,5 (C-7), 51,6 (C-1), 34,3 (C-3), 32,7 (C-6), 29,7–29,1 (C-5), 25,1 (C-4) ppm; Elementaranalyse (%): ber.: 70.55 (C); 10,66 (H); gefunden: 70,64 (C); 10,36 (H).
• 2b (x = 5): 'H NMR (CDCl₃, 400 MHz, 25°C): δ = 5,42–5,23 (m, 2H, H-7), 3,66 (s, 6H, H-1), 2,29 (t, ³J_HH = 7,4 Hz, 4H, H-3), 1,98–1,93 (m, 4H, H-6), 1,65–1,56 (m, 4H, H-4), 1,37–1,21 (m, 32H, H-5) ppm; ¹³C{¹H} NMR (CDCl₃, 100 MHz, 25°C): δ = 174,4 (C-2), 130,5 (C-7), 51,5 (C-1), 34,3 (C-3), 32,8 (C-6), 29,9–29,3 (C-5), 25,1 (C-4) ppm; Elementaranalyse (%): ber.: 74,29 (C); 11,58 (H); gefunden: 74,23 (C); 11,44 (H).

In a 100 mL round bottom flask with nitrogen inlet, 20.00 mL of the respective unsaturated fatty acid 1a or 1b were added and then degassed at 45 ° C. After adding 20 mL of dry heptane, 0.5 mol% of Cat1 (= HG2) and 1.0 mol% of benzoquinone were added and stirred at 45 ° C. Upon precipitation of the diacid and solidification of the reaction mixture (typically 5-15 min), the reaction was quenched by the addition of 2 mL of ethyl vinyl ether. After 15 minutes at room temperature, the precipitate was dissolved in hot petroleum ether or ethyl acetate and crystallized at 6 ° C. After filtration of the crude product, the diacid was esterified with a large excess of methanol at 65 ° C with the addition of 2 mL sulfuric acid. The solution was heated at reflux for 2 h and the solvent removed under vacuum. The residue was dissolved in dichloromethane, washed successively with water and brine and then dried over MgSO _4. After removal of the solvent, the pure diesters 2a and 2b (see 1 ) by crystallization from methanol or heptane or isolated by column chromatography (petroleum ether / ethyl acetate 19/1) to give compounds 2a and 2b in 62% (6.65 g) and 40% (4.60 g) yield receive.

• 2a (x = 1): 'H NMR _(CDCl3, 400 MHz, 25 ° C): δ = 5.42 to 5.23 (m, 2H, H-7), 3.66 (s, 6H, H -1), 2.29 (t, ³ J _HH = 7.5 Hz, 4H, H-3), 1.99 to 1.91 (m, 4H, H-6), 1.66 to 1.56 (m , 4H, H-4), 1.37-1.24 (m, 16H, H-5) ppm; ¹³ C ^{1 H} NMR (CDCl _3, 100 MHz, 25 ° C): δ = 174.4 (C-2), 130.5 (C-7), 51.6 (C-1), 34, 3 (C-3), 32.7 (C-6), 29.7-29.1 (C-5), 25.1 (C-4) ppm; Elemental Analysis (%): calc .: 70.55 (C); 10.66 (H); found: 70.64 (C); 10.36 (H).
• 2b (x = 5): 'H NMR _(CDCl3, 400 MHz, 25 ° C): δ = 5.42 to 5.23 (m, 2H, H-7), 3.66 (s, 6H, H -1), 2.29 (t, ³ J _HH = 7.4 Hz, 4H, H-3), 1.98 to 1.93 (m, 4H, H-6), 1.65 to 1.56 (m, 4H, H-4), 1.37-1.21 (m, 32H, H-5) ppm; ¹³ C ^{1 H} NMR (CDCl _3, 100 MHz, 25 ° C): δ = 174.4 (C-2), 130.5 (C-7), 51.5 (C-1), 34, 3 (C-3), 32.8 (C-6), 29.9-29.3 (C-5), 25.1 (C-4) ppm; Elemental Analysis (%): calc .: 74.29 (C); 11.58 (H); found: 74.23 (C); 11:44 (H).

Example 2: General procedure for steps (a) and (b) of the method according to the invention with reference to compounds 2a and 2b

• 3a (x = 1): Tm = 65°C; ¹H NMR (CDCl₃, 400 MHz, 25°C): δ = 6,96 (dt, ³J_HH = 15,6, 7,0 Hz, 1H, H-7), 5,81 (dt, ³J_HH = 15,6 Hz, ⁴J_HH = 1,6 Hz, 1H, H-8), 3,72 (s, 3H, H-1'), 3,66 (s, 3H, H-1), 2,29 (t, ³J_HH = 7,5 Hz, 2H, H-3), 2,19 (qd, ³J_HH = 7,3 Hz, ⁴J_HH = 1,6 Hz, 2H, H-6), 1,65–1,56 (m, 2H, H-4), 1,48–1,39 (m, 2H, H-4'), 1.34–1,22 (m, 20H, H-5) ppm; ¹³C{¹H} NMR (CDCl₃, 100 MHz, 25°C): δ = 174,4 (C-2), 167,3 (C-2'), 149,9 (C-7), 120,9 (C-8), 51,5 (C-1), 51,5 (C-1'), 34,3 (C-3) 32,4 (C-6), 29,7–29,3 (C-5), 28,2 (C-4'), 25,1 (C-4) ppm; Elementaranalyse (%): ber.: 70,55 (C); 10,66 (H); gefunden: 70,57 (C); 10,77 (H); ESI-MS (m/z): 363,24 [M+Na]⁺.
• 3b (x = 9): Tm = 82°C; 'H NMR (CDCl₃, 400 MHz, 25°C): δ = 6,96 (dt, ³J_HH = 15,7, 6,9 Hz, 1H, H-7), 5,82 (dt, ³J_HH = 15,7 Hz, ⁴J_HH = 1,5 Hz, 1H, H-8), 3,72 (s, 3H, H-1'), 3,66 (s, 3H, H-1), 2,30 (t, ³J_HH = 7,5 Hz, 2H, H-3), 2,19 (qd, ³J_HH = 7,5 Hz, ⁴J_HH = 1,5 Hz, 2H, H-6), 1,66–1,57 (m, 2H, H-4), 1,49–1,40 (m, 2H, H-4'), 1,34–1,22 (m, 36H, H-5) ppm; ¹³C{¹H] NMR (CDCl₃, 100 MHz, 25°C): δ = 174,4 (C-2), 167,3 (C-2'), 149,9 (C-7), 121,0 (C-8), 51,5 (C-1), 51,5 (C-1'), 34,3 (C-3), 32,4 (C-6), 29,8–29,3 (C-5), 28,2 (C-4'), 25,1 (C-4) ppm; Elementaranalyse (%): ber.: 74,29 (C); 11,58 (H); gefunden: 74,50 (C); 11,73 (H); ESI-MS (m/z): 475,37 [M+Na]⁺.

In a 1 L round bottom flask with a nitrogen inlet was added 25.00 g of diester 2a or 2b, which was degassed and then dissolved in 900 mL of dry alcohol. The solution was transferred by cannula to a 1 L double-walled glass reactor equipped with a magnetic stir bar and fitted with a cryostat. A solution of 0.5 mol% of the isomerization catalyst Cat2 (= [Pd (dtbpx) (OTf) ₂ ]) in 5 mL of the corresponding alcohol was added to the solution, whereupon the reactor was sealed and stirred at 250 rpm. By means of the cryostat, the reactor was cooled to a temperature in the range of 6 to 10 ° C for diester 2a and in the range of 30 to 35 ° C for diester 2b, in which the solution becomes cloudy due to the formation of the initial crystals. Subsequently, the reaction was cooled to the final temperature of -30 ° C for diester 2a and -10 ° C for diester 2b in the designated time of 12 h for diester 2a and 16 h for diester 2b. The temperature gradients included 4 equal time segments. Diester 2a was tempered by 2 ° C. in segment 1, by 5 ° C. in segment 2, by 10 ° C. in segment 3 and by the desired final temperature in segment 4. Diester 2b was tempered in segment 1 by 2 ° C, in segment 2 by 8 ° C, in segment 3 by 15 ° C and in segment 4 to the desired final temperature. After reaching this temperature, the isomerization was quenched by the addition of 5 mL of triethylamine and the slightly yellow Precipitate filtered off. The precipitate was dissolved in a small amount of dichloromethane and filtered through a small amount of silica to remove the residual catalyst. After subsequent recrystallization from methanol (in the case of 2a) or heptane (in 2b) gives the pure diesters 3a (63% yield) and 3b (57% yield) in a purity of more than 99% (determined by ¹ H-NMR spectroscopy).

• 3a (x = 1): Tm = 65 ° C; ¹ H NMR _(CDCl3, 400 MHz, 25 ° C): δ = 6.96 (dt, ³ J _HH = 15.6, 7.0 Hz, 1H, H-7), 5.81 (dt, ³ J _HH = 15.6 Hz, ⁴ J _HH = 1.6 Hz, 1H, H-8), 3.72 (s, 3H, H-1 '), 3.66 (s, 3H, H-1) , 2.29 (t, ³ J _HH = 7.5 Hz, 2H, H-3), 2.19 (qd, ³ J _HH = 7.3 Hz, ⁴ J _HH = 1.6 Hz, 2H, H -6), 1.65-1.56 (m, 2H, H-4), 1.48-1.39 (m, 2H, H-4 '), 1.34-1.22 (m, 20H, H -5) ppm; ¹³ C { ¹ H} NMR (CDCl ₃ , 100 MHz, 25 ° C): δ = 174.4 (C-2), 167.3 (C-2 '), 149.9 (C-7), 120 , 9 (C-8), 51.5 (C-1), 51.5 (C-1 '), 34.3 (C-3) 32.4 (C-6), 29.7-29, 3 (C-5), 28.2 (C-4 '), 25.1 (C-4) ppm; Elemental Analysis (%): calc .: 70.55 (C); 10.66 (H); Found: 70.57 (C); 10.77 (H); ESI-MS (m / z): 363.24 [M + Na] ⁺ .
• 3b (x = 9): Tm = 82 ° C; 'H NMR _(CDCl3, 400 MHz, 25 ° C): δ = 6.96 (dt, ³ J _HH = 15.7, 6.9 Hz, 1H, H-7), 5.82 (dt, ³ J _HH = 15.7 Hz, ⁴ J _HH = 1.5 Hz, 1H, H-8), 3.72 (s, 3H, H-1 '), 3.66 (s, 3H, H-1) , 2.30 (t, ³ J _HH = 7.5 Hz, 2H, H-3), 2.19 (qd, ³ J _HH = 7.5 Hz, ⁴ J _HH = 1.5 Hz, 2H, H -6), 1.66-1.57 (m, 2H, H-4), 1.49-1.40 (m, 2H, H-4 '), 1.34-1.22 (m, 36H , H-5) ppm; ¹³ C ^{1 H] NMR _(CDCl3, 100 MHz, 25 ° C): δ = 174.4 (C-2), 167.3 (C-2 '), 149.9 (C-7), 121 , 0 (C-8), 51.5 (C-1), 51.5 (C-1 '), 34.3 (C-3), 32.4 (C-6), 29.8-29 , 3 (C-5), 28.2 (C-4 '), 25.1 (C-4) ppm; Elemental Analysis (%): calc .: 74.29 (C); 11.58 (H); found: 74.50 (C); 11.73 (H); ESI-MS (m / z): 475.37 [M + Na] ⁺ .

Example 3 Step (c) of the Process of the Invention Based on the Synthesis of Dimethyl-1,32-dotricont-16-endioate (4a)

• 4a (x = 1): Tm = 77°C; ¹H NMR (CDCl₃, 400 MHz, 25°C): δ = 5,44–5,32 (m, 2H, H-7), 3,66 (s, 6H, H-1), 2,30 (t, ³J_HH = 7,5 Hz, 2H, H-3), 2,03–1,90 (m, 2H, H-6), 1,66–1,57 (m, 4H, H-4), 1,37–1,22 (m, 44H, H-5) ppm; ¹³C{¹H} NMR (CDCl₃, 100 MHz, 25°C): δ = 174,5 (C-2), 130,5 (C-7), 51,6 (C-1), 34,3 (C-3), 32,8 (C-6), 29,8–29,3 (C-5), 25,1 (C-4) ppm; Elementaranalyse (%): ber.: 76,06 (C); 12,02 (H); gefunden: 76,04 (C); 11,94 (H); ESI-MS (m/z): 559,46 [M+Na]⁺.

250.0 mg (0.73 mmol) of the α, β-unsaturated diester 3a were degassed in a Schlenk tube. The diester was suspended in 1.0 mL dry heptane and 0.92 mL 2- / 3-hexene. 2.3 mg (3.7 μmol) of Cat1 (= HG2) and 0.8 mg (7.3 μmol) of benzoquinone were dissolved in 0.1 mL of dry dichloromethane and added to the reaction mixture. The reaction mixture immediately turned dark green and was stirred at 40 ° C for 20 minutes. At 30 ° C, the solvent was removed in vacuo and the reaction was held at this temperature for 15 minutes. The reaction was quenched by the addition of 1 mL of ethyl vinyl ether and stirred at room temperature for 5 min. After adding 2 mL of dichloromethane, the mixture was stirred for a further 10 minutes. The dark green solution was filtered through a small amount of silica and washed with dichloromethane. The solvent was removed by rotary evaporation and the colorless solid dried under vacuum. After recrystallization from methanol or heptane, the ultra-long-chain diester 4a was obtained in the form of colorless crystals in 86% yield in a purity of more than 99% (determined by GC analysis).

• 4a (x = 1): Tm = 77 ° C; ¹ H NMR _(CDCl3, 400 MHz, 25 ° C): δ = 5.44 to 5.32 (m, 2H, H-7), 3.66 (s, 6H, H-1), 2.30 (t, ³ J _HH = 7.5 Hz, 2H, H-3), 2.03 to 1.90 (m, 2H, H-6), 1.66 to 1.57 (m, 4H, H 4), 1.37-1.22 (m, 44H, H-5) ppm; ¹³ C ^{1 H} NMR (CDCl _3, 100 MHz, 25 ° C): δ = 174.5 (C-2), 130.5 (C-7), 51.6 (C-1), 34, 3 (C-3), 32.8 (C-6), 29.8-29.3 (C-5), 25.1 (C-4) ppm; Elemental Analysis (%): calc .: 76.06 (C); 12.02 (H); found: 76.04 (C); 11.94 (H); ESI-MS (m / z): 559.46 [M + Na] ⁺ .

Example 4 Step (c) of the Process According to the Invention Using the Synthesis of Dimethyl 1,48-octatetracont-24-endioate (4b)

• 4a (x = 9; siehe Beispiel 3): Tm = 95°C; ¹H NMR (CDCl₃, 400 MHz, 25°C): δ = 5,44–5,32 (m, 2H, H-7), 3,67 (s, 6H, H-1), 2,30 (t, ³J_HH = 7,5 Hz, 2H, H-3), 2,05–1,90 (m, 2H, H-6), 1,68–1,57 (m, 4H, H-4), 1,38–1,19 (m, 76H, H-5) ppm; ¹³C{¹H} NMR (CDCl₃, 100 MHz, 25°C): δ = 174,5 (C-2), 130,5 (C-7), 51,6 (C-1), 34,3 (C-3), 32,8 (C-6), 29,8–29,3 (C-5), 25,1 (C-4) ppm; Elementaranalyse (%): ber.: 78,88 (C); 12,71 (H); gefunden: 78,78 (C); 13,15 (H); ESI-MS (m/z): 783,74 [M+Na]⁺.

5.00 g (11.04 mmol) of diester 4b were placed in a Schlenk flask and degassed. 5 mL of dry dichloromethane and 13.87 mL of 2- / 3-hexene (9.29 g, 110.44 mmol) were added and the reaction heated to 40 ° C. After the diester was dissolved, 34.6 mg (55.2 μmol) of Cat1 (= HG2) and 11.9 mg (100.4 μmol) of 1,4-benzoquinone in 0.5 mL of dry dichloromethane were added. The solution was stirred at 40 ° C for 15 min stirred before cooling to room temperature and adding 10 mL of dry heptane. Subsequently, the volatiles were removed slowly under vacuum. The resulting solid was dissolved in dichloromethane and ethyl vinyl ether added to quench the reaction. After stirring at room temperature for 15 min, the solution was diluted with dichloromethane and filtered through a small amount of silica to remove the residual catalyst. After recrystallization from heptane, the ultra-long-chain diester 4b was obtained as colorless crystals in 92% yield in greater than 99% purity (determined by GC analysis).

• 4a (x = 9, see Example 3): Tm = 95 ° C; ¹ H NMR _(CDCl3, 400 MHz, 25 ° C): δ = 5.44 to 5.32 (m, 2H, H-7), 3.67 (s, 6H, H-1), 2.30 (t, ³ J _HH = 7.5 Hz, 2H, H-3), 2.05-1.90 (m, 2H, H-6), 1.68 to 1.57 (m, 4H, H 4), 1.38-1.19 (m, 76H, H-5) ppm; ¹³ C ^{1 H} NMR (CDCl _3, 100 MHz, 25 ° C): δ = 174.5 (C-2), 130.5 (C-7), 51.6 (C-1), 34, 3 (C-3), 32.8 (C-6), 29.8-29.3 (C-5), 25.1 (C-4) ppm; Elemental Analysis (%): calc .: 78.88 (C); 12.71 (H); found: 78.78 (C); 13:15 (H); ESI-MS (m / z): 783.74 [M + Na] ⁺ .

Example 4 Optional Step (d) of the Process of the Invention by Synthesis of Dimethyl-1,32-Dioctocontanedioate (7)

• T_m = 92°C; ¹H NMR (CDCl₃, 400 MHz, 25°C): δ = 3,66 (s, 6H, H-1), 2,30 (t, ³J_HH = 7.6 Hz, 4H, H-3), 1,66–1,57 (m, 4H, H-4), 1,33–1,24 (m, 52H, H-5) ppm; ¹³C{¹H} NMR (CDCl₃, 100 MHz, 25°C): δ = 174,5 (C-2), 51,6 (C-1), 34,3 (C-3), 29,9–29,3 (C-5), 25,1 (C-4) ppm; Elementaranalyse (%): ber.: 75,78 (C); 12,35 (H); gefunden: 75,74 (C); 12,15 (H); ESI-MS (m/z): 329,1 [M+H]⁺.

In a Schlenk tube, 3.80 g (7.07 mmol) of diester 4a and 0.2 g of Pd / C (10% by weight of Pd) were degassed and suspended in 12 mL of dry THF and 4 mL of dry methanol. The mixture was transferred by means of a cannula into a stainless steel pressure reactor and placed under 20 bar (2.0000 × 10 ⁶ Pa) of hydrogen pressure. After stirring for 18 hours at 60 ° C, the reactor was cooled to room temperature and vented. The solvent was removed, the crude product dissolved in chloroform and filtered through a small amount of silica to remove the catalyst. After removing the solvent, the obtained compound was recrystallized from ethanol to obtain the diester 7 in the form of a white powder in 95% yield.

• T _m = 92 ° C; ¹ H NMR _(CDCl3, 400 MHz, 25 ° C): δ = 3.66 (s, 6H, H-1), 2.30 (t, ³ J _HH = 7.6 Hz, 4H, H-3), 1.66-1.57 (m, 4H, H-4), 1.33-1.24 (m, 52H, H-5) ppm; ¹³ C ^{1 H} NMR (CDCl _3, 100 MHz, 25 ° C): δ = 174.5 (C-2), 51.6 (C-1), 34.3 (C-3), 29, 9-29.3 (C-5), 25.1 (C-4) ppm; Elemental Analysis (%): calc .: 75.78 (C); 12.35 (H); found: 75.74 (C); 12.15 (H); ESI-MS (m / z): 329.1 [M + H] ⁺ .

Example 5 Optional Step (e) of the Process of the Invention with Synthesis of 1,32-Dotriacontanediol (8)

• T_m,1 = 112°C; T_m,2 = 118°C; ¹H NMR (400 MHz, CDCl₃, 55°C): δ = 3,64 (t, ³J_HH = 6,6 Hz, 4H, H-1), 1,62–1,54 (m, 4H, H-2), 1,41–1,25 (m, 56H, H-3, H-4), 1,14 (s (br), 2H, OH) ppm; ¹³C{¹H} NMR (100 MHz, CDCl₃, 55°C): δ = 63,3 (C-1), 33,1 (C-2), 29,9–29,6 (C-4), 26,0 (C-3) ppm; Elementaranalyse (%): ber.: 79,60 (C); 13,78 (H); gefunden: 79,68 (C); 13,86 (H); ESI-MS (m/z): 329,1 [M+H]⁺.

0.54 g (1.01 mmol) of diester 7 were dissolved in 50 mL of THF and cooled to 0 ° C. 95.6 mg (2.52 mmol) of LiAlH ₄ were added portionwise, forming a suspension. The mixture was stirred for 15 minutes at 0 ° C before being heated to 90 ° C. After stirring for 3 hours under reflux, the reaction mixture was cooled to room temperature and the excess LiAlH _{4 was} quenched by sequential addition of 3 mL MeOH, 1 mL water and 2 mL 2M NaOH solution. The suspension was heated and filtered through a small amount of silica with hot THF. After removing the solvent, the crude product was recrystallized from chloroform, whereby the diol 8 was obtained in the form of colorless crystals in 92% yield.

• Tm _{, 1} = 112 ° C; Tm _{, 2} = 118 ° C; ¹ H NMR (400 MHz, _CDCl3, 55 ° C): δ = 3.64 (t, ³ J _HH = 6.6 Hz, 4H, H-1), 1.62 to 1.54 (m, 4H , H-2), 1.41-1.25 (m, 56H, H-3, H-4), 1.14 (s (br), 2H, OH) ppm; ¹³ C ^{1 H} NMR (100 MHz, _CDCl3, 55 ° C): δ = 63.3 (C-1), 33.1 (C-2), 29.9 to 29.6 (C-4 ), 26.0 (C-3) ppm; Elemental Analysis (%): calc .: 79.60 (C); 13.78 (H); Found: 79.68 (C); 13.86 (H); ESI-MS (m / z): 329.1 [M + H] ⁺ .

Example 6: Optional step (f) of the process according to the invention on the basis of the polymerization of diester 7 and diol 8 for the synthesis of the polyester-32,32

1.12 g (2.07 mmol) of diester 7 and 1.00 g (2.07 mmol) of diol 8 were degassed at 120 ° C. in a 100 mL two-necked Schlenk flask with stirrer. After adding 500 ppm [Ti (OnBu) ₄ ] (a solution of 0.35 mg (1.0 μmol) in 0.20 mL dry toluene), the temperature was gradually increased (10 ° C per hour) to a final temperature of Increased 200 ° C with gradual reduction of pressure. After reaching the final temperature, the highly viscous colorless polymer melt was stirred for a further 16 h under vacuum. The resulting polymer was dissolved in toluene at 100 ° C and precipitated in methanol to give the polyester-32,32 as a colorless solid in quantitative yield.

QUOTES INCLUDE IN THE DESCRIPTION

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Cited non-patent literature

• Stempfle, F .; Quinzler, D .; Heckler, I .; Mecking, S. Macromolecules 2011, 44, 4159-4166 [0073]

Claims (12)

Process for the preparation of a compound of general formula (1)

comprising the steps of (a) reacting a compound of general formula (2) in the presence of an isomerization catalyst

for the preparation of a compound of general formula (3)

(b) separating the compound of the general formula (3) and (c) reacting the compound of the general formula (3) in the presence of a metathesis catalyst to produce the compound of the general formula (1), wherein n and m are each independently an integer from 1 to 200, p = (m + n-1), and Y is selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, -NR ¹ R ² and -OR ³ wherein each of R ¹ to R ^{3 is} independently hydrogen, alkyl, cycloalkyl, aryl or heteroaryl. The process of claim 1, wherein the isomerization catalyst comprises transition metals selected from nickel or palladium in elemental form or in the form of complexes, the complexes comprising one or more mono- or polydentate phosphines PR " ¹ R" ² R " ³ and optionally comprise organic or inorganic acids or salts thereof, wherein R '' ¹ to R '' ^{3 are} independently identical or different H, open-chain or cyclic aliphatic C ₁ to C ₃₀ radicals, aromatic C ₁ to C ₃₀ radicals, as well as heteroatoms such as N, O or S bonded open-chain or cyclic aliphatic C ₁ to C ₃₀ radicals and aromatic C ₁ to C ₃₀ radicals and the R '' ¹ to R '' ³ may contain heteroatoms in the side chain. A process according to claim 1 or 2, wherein the isomerization catalyst is [Pd (dtbpx) (OTf) ₂ ]. The process of any one of claims 1 to 3, wherein the solvent in steps (a) and (b) is selected from the group consisting of one or more alcohols, dichloromethane, chloroform, dioxane, ethyl acetate, tetrahydrofuran, DMF, DMSO, acetonitrile , aromatic and / or aliphatic hydrocarbons and water or combinations of two or more thereof. The process of any one of claims 1 to 4, wherein the metathesis catalyst is selected from the group consisting of Grubbs first generation catalysts (G1, benzylidenebis (tricyclohexylphosphine) dichlororuthenium), Grubbs second generation catalysts (G2, benzylidene [1,3-bis (2,4,6 trimethylphenyl) -2-imidazolidinylidene] dichloro (tricyclohexylphosphine) ruthenium), Hoveyda-Grubbs first generation catalysts (HG1, dichloro (o-isopropoxyphenylmethylene) (tricyclohexylphosphine) ruthenium), Hoveyda-Grubbs second generation catalysts (HG2, 1,3- Bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene) dichloro (o-isopropoxyphenylmethylene) ruthenium), fast-initiating Grubbs catalysts (G3, dichloro [1,3-bis (2,4,6-trimethylphenyl) -2 -imidazolidinylidene] (benzylidene) bis (3-bromopyridine) ruthenium), Piers First generation catalysts (P1, dichloro (tricyclohexylphosphine) - [(tricyclohexylphosphoranyl) methylidene] ruthenium tetrafluoroborate), Piers second generation catalysts (P2, dichloro [1, 3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene] - [(tricyclohexylphosphoranyl) methylidene] ruthenium tetrafluoroborate), Grela catalysts ((1,3-dimesitylimidazolidin-2-ylidene) (2-isopropoxy-5-nitrobenzylidene ruthenium chloride) and structurally related metathesis catalyst of the abovementioned type with carbene ligands of the type benzylidene, dimethylvinylalkylidene, indenylidene, allenylidene and benzylidene derivatives having one to several substituents on the aromatic, and 2,6-diisopropylphenylimidoneophylidene-molybdenum bis (hexafluoro-t-butoxide). A process according to any one of claims 1 to 5, wherein step (c) is further carried out in the presence of an alkene of 2 to 18 carbon atoms. A process according to any one of claims 1 to 6, further comprising before step (a) the steps of (a0) reacting a compound of general formula (4) in the presence of a metathesis catalyst

for the preparation of a compound of general formula (5)

(a1) optionally esterifying or amidating the compound of the general formula (5) to produce a compound of the general formula (2) wherein Y = -NR ¹ R ² or Y = -OR ³ with R ³ ≠ H, wherein X is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl and heteroaryl. A process according to any one of claims 1 to 7, wherein step (c) and / or step (a0) is carried out in the presence of 1,4-benzoquinone. Method according to one of claims 1 to 8, further comprising after step (c), when Y is OR ³ , the steps (d) hydrogenating the compound of general formula (1) to produce a compound of general formula (6)

(e) reducing the compound of the general formula (6) to produce a compound of the general formula (7)

(f) reacting the compounds of the general formulas (6) and (7) to produce a compound of the general formula (8)

where x is an integer from 1 to 1000. The process of claim 9 wherein step (d) is in the presence of a hydrogenating agent selected from the group consisting of Pd / C, PdO, Pd (OH) ₂ / BaSO ₄ , platinum black, palladium black, Cu / SiO _2, and homogeneous soluble complexes. selected from ruthenium, iridium or rhodium complexes which may contain phosphine ligands and H ₂ . A process according to claim 9 or 10 wherein step (e) is in the presence of a reducing agent selected from the group consisting of LiAlH ₄ , dichlorobis [2- (diphenylphosphino) ethylamine] ruthenium, carbonylhydrido [6- (di-t-butylphosphinomethylene) - 2- (N, N-diethylaminomethyl) -1,6-dihydropyridine] ruthenium and carbonylchlorohydrido [2- (di-iso-propylphosphino) -N- (2-pyridinylmethyl) ethanamine] ruthenium. A process according to any one of claims 9 to 11, wherein step (f) is carried out in the presence of a catalyst selected from the group consisting of [Ti (OiPr) ₄ ], [Ti (OnBu) ₄ ], [Zr (OiPr) ₄ ], [Zr (OnBu) ₄ ], tin (2-ethylhexanoate), zinc acetate, antimony (III) oxide and dibutyltin oxide.

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