JP2015527305A - Process for producing unsaturated compounds - Google Patents

Abstract

The present invention relates to a method for producing a composition comprising an unsaturated compound, wherein (A) one or more unsaturated monocarboxylic acids having 10 to 24 carbon atoms or esters of the monocarboxylic acids, and ( B) One or more unsaturated dicarboxylic acids or esters thereof having 4 to 20 carbon atoms are subjected to a tandem isomerization / metathesis reaction in the presence of a palladium catalyst and a ruthenium catalyst, provided that the palladium catalyst used Is at least one structural element Pd-P (R1R2R3) wherein R1 to R3 groups each independently have 2 to 10 carbon atoms and are each aliphatic, alicyclic, aromatic or The palladium catalyst may be a heterocycle, provided that at least one R1-R3 group contains β-hydrogen. Used in situ, provided that the process is carried out in the absence of a substance having a pKa of 3 or less.

Description

  The present invention relates to a method for producing an unsaturated compound. The process of the present invention is a tandem isomerization / metathesis where a catalyst system comprising first a specific palladium catalyst and second a ruthenium catalyst is used.

  Processes for the production of unsaturated α, ω-dicarboxylic acid diesters starting from unsaturated carboxylic acids are described in the prior art. Ngo et al. Describe the metathesis of unsaturated carboxylic acids using first and second generation Grubbs catalysts (JAOCS, 83, 7, 629-634, 2006).

  WO 2010/020368 describes a process for the production of unsaturated α, ω-dicarboxylic acids and α, ω-dicarboxylic acid diesters, in which unsaturated carboxylic acids and / or unsaturated carboxylic acids are produced. The ester is converted in the presence of two specific ruthenium catalysts.

International Publication No. 2010/020368

Ngo et al., JAOCS, 83, 7, 629-634, 2006.

  The object of the present invention is a novel process which makes it possible to produce unsaturated compounds (understood to mean compounds with C═C double bonds) from unsaturated monocarboxylic acids and esters of monocarboxylic acids. Is to provide a method.

The present invention provides a method for producing a composition comprising an unsaturated compound, wherein (A) one or more unsaturated monocarboxylic acids having 10 to 24 carbon atoms or esters of these monocarboxylic acids, And (B) subjecting one or more unsaturated dicarboxylic acids having 4 to 20 carbon atoms or their esters to a tandem isomerization / metathesis reaction in the presence of a palladium catalyst and a ruthenium catalyst, The palladium catalyst used is at least one structural element Pd—P (R ¹ R ² R ³ ), wherein each of the R ^{1 to} R ³ groups independently has 2 to 10 carbon atoms. and aliphatic respectively, cycloaliphatic, may be aromatic or heterocyclic, provided that at least one of R ¹ to R ³ radicals is a compound containing a] containing β- hydrogen, the palladium catalyst By itself, or is used to cause in situ, however, the method of the present invention is carried out in the absence of a substance having three following pKa.

The method of the present invention is tandem isomerization / metathesis and has a number of advantages:
• The catalyst does not require any kind of chemical activation. More specifically, palladium catalysts that provide C = C isomerization before and after the metathesis step are, for example, protic solvents and / or strong acids (this is referred to herein as acids having a pKa of 3 or less). Works by itself, without the need to be activated).
Only an appropriate amount of bimetallic Pd / Ru catalyst system is required.
The catalyst system is such that the Pd catalyst (which leads to C = C isomerization) and the Ru catalyst (which leads to metathesis) do not reduce or interfere with each other, which is not known.
The catalyst system works not only when the compound (A) used is a compound having only one C═C double bond, but also when a plurality of C═C double bonds are present. To do. This is also unknown. In carrying out the action, this is very advantageous if, for example, the compound (A) used is oleic acid. In this case, such oleic acid need not have a very high purity. Alternatively, it is also possible to use industrial grade purity oleic acid, for example, containing about 80% oleic acid and 20% linoleic acid.
The catalyst system inhibits the formation of lactones (originally expected when unsaturated fatty acids such as oleic acid are mixed with the isomerization catalyst).
The method of the present invention can be carried out without using a solvent if desired.
• The method of the present invention requires only a very mild temperature.

The product distribution is shown.

Reactant [Reactant (A)]
The compound (A) is an unsaturated monocarboxylic acid having 10 to 24 carbon atoms or an ester of the monocarboxylic acid. The monocarboxylic acid may optionally be branched. The C = C double bond of the monocarboxylic acid can exist in either cis or trans coordination. It is possible for one or more C═C double bonds to be present.

The unsaturated monocarboxylic acid (A) used is preferably a compound of the formula R ¹ —COOH, wherein the R ¹ group contains 9 to 23 carbon atoms. The R ¹ group may be a cyclic or acyclic group, and the R ¹ group is preferably acyclic and may be branched or unbranched. Monocarboxylic acids having an unbranched R ¹ group are preferred.

  The following shorthand notation is used to describe the unsaturated monocarboxylic acid: the first number is the total number of carbon atoms in the monocarboxylic acid, the second number is the number of double bonds, and the number in parentheses Describes the position of the double bond in relation to the carboxyl group. Thus, the shorthand notation for oleic acid is 18: 1 (9). If the double bond is in trans coordination, this is represented by the abbreviation “tr”. Thus, the abbreviated notation for elaidic acid is 18: 1 (tr9).

  Suitable monounsaturated monocarboxylic acids are, for example, myristoleic acid [14: 1 (9), (9Z) -tetradec-9-enoic acid], palmitoleic acid [16: 1 (9); (9Z) -hexadeca- 9-enoic acid], petroceric acid [(6Z) -octadeca-6-enoic acid], oleic acid [18: 1 (9); (9Z) -octadeca-9-enoic acid], elaidic acid [18: 1 (tr9 ); (9E) -octadeca-9-enoic acid)], vaccenic acid [18: 1 (tr11); (11E) -octadeca-11-enoic acid], gadoleic acid [20: 1 (9); (9Z) -Eicosa-9-enoic acid], eicosenoic acid (= gondoic acid) [20: 1 (11); (11Z) -eicosa-11-enoic acid], cetoleic acid [22: 1 (11); (11Z)- Docosa-11-enoic acid], erucic acid [22: 1 (13); (13Z) -docosa-13-enoic acid], nervonic acid [24: 1 (15); (15Z) -tetracosa-15-e It is an acid]. Additionally suitable are functionalized monounsaturated monocarboxylic acids such as ricinoleic acid, furan fatty acids, methoxy fatty acids, keto fatty acids and epoxy fatty acids such as vernolic acid (cis-12,13-epoxyoctadeca-cis-9 -Enoic acid), and finally branched monocarboxylic acids such as phytanic acid.

  Suitable polyunsaturated monocarboxylic acids are, for example, linoleic acid [18: 2 (9,12); (9Z, 12Z) -octadeca-9,12-dienoic acid], α-linolenic acid [18: 3 (9, 12,9); (9Z, 12Z, 15Z) -octadeca-9,12,15-trienoic acid], γ-linolenic acid [18: 3 (6,9,12); (6Z, 9Z, 12Z) -octadeca -6,9,12-trienoic acid], calendic acid [18: 3 (8,10,12); (8E, 10E, 12Z) -octadeca-8,10,12-trienoic acid], punicic acid [18: 3 (9,11,13); (9Z, 11E, 13Z) -octadeca-9,11,13-trienoic acid], α-eleostearic acid [18: 3 (9,11,13); (9Z, 11E, 13E) -octadeca-9,11,13-trienoic acid], arachidonic acid [20: 4 (5,8,11,14), (5Z, 8Z, 11Z, 14Z) -eicosa-5,8,11 , 14-Tetraenoic acid Thymnodonic acid [20: 5 (5,8,11,14,17), (5Z, 8Z, 11Z, 14Z, 17Z) -eicosa-5,8,11,14,17-pentaenoic acid], crupanodonic acid [ 22: 5 (7,10,13,16,19), (7Z, 10Z, 13Z, 16Z, 19Z) -docosa-7,10,13,16,19-pentaenoic acid], cervonic acid [22: 6 ( 4,7,10,13,16,19), (4Z, 7Z, 10Z, 13Z, 16Z, 19Z) -docosa-4,7,10,13,16,19-hexaenoic acid).

Suitable reactants (A) are furthermore esters of the above mono- or polyunsaturated monocarboxylic acids. Suitable esters are in particular esters of the monocarboxylic acid with an alcohol R ² —OH, wherein R ² is an alkyl group having 1 to 8 carbon atoms. Examples of suitable R ² groups include: methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-methylpropyl group, pentyl group, 2,2-dimethylpropyl group, 2- Methylbutyl group, 3-methylbutyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, heptyl group and octyl group .

  Suitable reactants (A) are furthermore the esters (= glyceryl esters) of the abovementioned mono- or polyunsaturated monocarboxylic acids with glycerol. In this case, glyceryl monoesters (= monoglycerides, monoacylglycerols), glyceryl diesters (= diglycerides, diacylglycerols) and glyceryl triesters (= triglycerides, triacylglycerols) and mixtures of these different glyceryl esters are also suitable.

  The unsaturated monocarboxylic acids or esters of unsaturated monocarboxylic acids may be present individually or mixed with one another. As long as exclusively one unsaturated monocarboxylic acid or only one ester of an unsaturated monocarboxylic acid is used, the reaction carried out in connection with the process of the invention is a reaction that can be classified as an isomerization self-metathesis. When using a variety of different unsaturated monocarboxylic acids or esters of various unsaturated monocarboxylic acids, the reaction performed with respect to the process of the present invention is a reaction that can be classified as an isomerized cross-metathesis.

  In a preferred embodiment of the invention, monounsaturated monocarboxylic acids and / or esters of monounsaturated monocarboxylic acids and / or mixtures of monounsaturated monocarboxylic acids or mixtures of esters of monounsaturated monocarboxylic acids are used.

[Reactant (B)]
The reactant (B) used in the process of the present invention is an unsaturated dicarboxylic acid having 4 to 20 carbon atoms and contains at least one C═C double bond per molecule. The reactant (B) preferably contains 4 to 10 carbon atoms per molecule. The dicarboxylic acid may be linear or branched. C = C double bonds may exist in cis and trans coordination.

  Compound (B) may contain additional functional groups that are inert under the reaction conditions. Examples of such functional groups are, for example, COOR, OH, OR, C = C, halogen and CN [wherein R represents an alkyl group].

  Examples of suitable reactants (B) are unsaturated dicarboxylic acids and dicarboxylic acids having 4 to 10 carbon atoms, preferably having 4 to 8 carbon atoms, in particular having 4 to 6 carbon atoms. Is a derivative. Examples of these are maleic acid and its esters, and (E) -3-hexenedicarboxylic acid and its esters.

  With respect to the method of the present invention, the metathesis step of the tandem isomerization / metathesis reaction is cross-metathesis because one or more reactants (B) are also used in addition to reactant (A).

  It has been found that the cross-metathesis of oleic acid and short chain dicarboxylic acids results in the production of mono- and dicarboxylic acids with predominantly moderate chain lengths. In the case of maleic acid, the cross-metathesis rate was much lower than the self-metathesis rate of oleic acid. However, in the case of (E) -3-hexene dicarboxylic acid, it has been found that cross-metathesis proceeds at the same rate as self-metathesis. The product distribution suggested the following: Both oleic acid and (E) -3-hexenedicarboxylic acid were quantitatively converted. The average chain length of all product fractions was substantially lower than the self-metathesis rate of oleic acid, with the dicarboxylic acid fraction being dominant. In this regard, reference is made to FIG.

  In the process of the invention, in addition to reactant (A), one or more reactants (B) are also used, the molar ratio of (A) :( B) being preferably 1: 0.05 to 1: Set to a value in the range of 5.

〔catalyst〕
The process according to the invention is carried out in the presence of specific palladium and ruthenium catalysts.

[Palladium catalyst]
The palladium catalyst used is at least one structural element Pd—P (R ¹ R ² R ³ ), wherein each of the R ^{1 to} R ³ groups independently has 2 to 10 carbon atoms, Each of which may be aliphatic, cycloaliphatic, aromatic or heterocyclic, with the proviso that at least one of the R ^{1 to} R ³ groups contains β-hydrogen. Used by itself or used as it occurs in situ.

  The aliphatic group may be linear or branched, may be in a cyclic form, and the above structural elements may be present in combination. The aromatic group may have an alkyl substituent. Β-hydrogen is present when the Pd—P—C—C—H configuration is present in the palladium catalyst.

  As explained above, the palladium catalyst is used by itself or is generated in situ.

  It is clearly emphasized that the palladium catalyst used in accordance with the present invention works by itself, which is understood to mean that it does not require chemical activation with an additional activator.

  The palladium catalyst may be mononuclear or polynuclear.

  In one embodiment, a palladium catalyst containing two palladium atoms per molecule is used.

  In one embodiment, a palladium catalyst containing two palladium atoms per molecule is used, wherein the two palladium atoms are joined to one another via a spacer X.

  Thus, these palladium catalysts contain the structural element Pd—X—Pd.

  The type of spacer is not limited in itself. Suitable spacers X are, for example, halogen, oxygen, O-alkyl, sulfur, sulfur-alkyl, disubstituted nitrogen, carbon monoxide, nitrile, diolefin.

［式中、
Ｘはハロゲン、酸素およびＯ-アルキルから選択されるスペーサーであり、Ｙ^１はＰ(Ｒ^１Ｒ^２Ｒ^３）基〔式中、Ｒ^１、Ｒ^２およびＲ^３は、それぞれ、上記で定義したものである〕であり、Ｙ^２はＰ(Ｒ^４Ｒ^５Ｒ^６）基〔式中、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立して、２〜１０個の炭素原子を有し、それぞれ脂肪族、脂環式、芳香族または複素環であってよい〕である］
である。 In a preferred embodiment, the palladium catalyst used is compound (I):

[Where:
X is a spacer selected from halogen, oxygen and O-alkyl, Y ¹ is a P (R ¹ R ² R ³ ) group, wherein R ¹ , R ² and R ³ are each as defined above Y ² is a P (R ⁴ R ⁵ R ⁶ ) group, wherein R ⁴ , R ⁵ and R ⁶ each independently have 2 to 10 carbon atoms, Each may be aliphatic, cycloaliphatic, aromatic or heterocyclic]]
It is.

For this definition, compound (I) contains at least one β-hydrogen in structural element Pd—Y ¹ (due to the R ^{1 to} R ³ groups present therein). In the structural element Pd—Y ² , β-hydrogen is not necessarily present.

  The compound (I) in which the spacer is halogen (particularly bromine) is particularly preferred.

Compounds (I) in which the spacer is bromine and the R ¹ , R ² and R ³ groups are each defined as tert-butyl are very particularly preferred.

［式中、
Ｘはハロゲン、酸素およびＯ-アルキルから選択されるスペーサーであり、Ｙ^１はＰ(Ｒ^１Ｒ^２Ｒ^３）基〔式中、Ｒ^１、Ｒ^２およびＲ^３は、それぞれ、上記で定義したものである〕であり、Ｙ^２はＰ(Ｒ^４Ｒ^５Ｒ^６）基〔式中、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ独立して、２〜１０個の炭素原子を有し、それぞれ脂肪族、脂環式、芳香族または複素環であってよい〕である］
である。 In a preferred embodiment, the palladium catalyst used is compound (Ia):

[Where:
X is a spacer selected from halogen, oxygen and O-alkyl, Y ¹ is a P (R ¹ R ² R ³ ) group, wherein R ¹ , R ² and R ³ are each as defined above Y ² is a P (R ⁴ R ⁵ R ⁶ ) group, wherein R ⁴ , R ⁵ and R ⁶ each independently have 2 to 10 carbon atoms, Each may be aliphatic, cycloaliphatic, aromatic or heterocyclic]]
It is.

  The compound (Ia) in which the spacer is halogen (particularly bromine) is particularly preferred.

The compound (Ia) in which the spacer is bromine and the R ¹ , R ² and R ³ groups are each defined as tert-butyl is very particularly preferred.

As already mentioned, the palladium catalyst is used by itself or is generated in situ. For example, for a palladium catalyst of type (I) or (Ia), it occurs in situ that a compound having no β-hydrogen is L ₃ -Pd-X-Pd-L ₃ [wherein L is a phosphine coordination group. Can be used to mean conversion to compound (I) or (Ia) by ligand exchange in situ.

  In one embodiment, the palladium catalyst is a homogeneous catalyst.

In one embodiment, the palladium catalyst is a heterogeneous catalyst. In a particular embodiment, the palladium catalyst of formula (I) is immobilized on a solid substrate or in an ionic liquid via Y ¹ and / or Y ² groups.

  The palladium catalyst is preferably used in an amount ranging from 0.01 to 2.0 mol%, particularly preferably in the range from 0.1 to 1.0 mol%, based on the amount of reactant (A) used.

[Ruthenium catalyst]
The chemical nature of the ruthenium catalyst is not critical per se.

  Examples of suitable ruthenium catalysts are:

を有する触媒（ＩＩ-ａ）。
この触媒の化学名は、ジクロロ[１,３-ビス(メシチル)-２-イミダゾリジニリデン]-(３-フェニル-１Ｈ-インデン-１-イリデン)(トリシクロヘキシルホスフィン)ルテニウム(ＩＩ）、ＣＡＳ Ｎｏ.５３６７２４-６７-１である。これは、Neolyst^{(登録商標)}M2の名称でUmicore社より市販されている。 The following structural formula:

Catalyst (II-a) having
The chemical name of this catalyst is dichloro [1,3-bis (mesityl) -2-imidazolidinylidene]-(3-phenyl-1H-indene-1-ylidene) (tricyclohexylphosphine) ruthenium (II), CAS No. .536724-67-1. It is commercially available from Umicore under the name Neolyst ^(TM) M2.

を有する触媒（ＩＩ-ｂ）。
この触媒の化学名は、[１,３-ビス(２,４,６-トリメチルフェニル)-２-イミダゾリジニリデン]-[２-[[(４-メチルフェニル)イミノ]メチル]-４-ニトロフェノリル]-[３-フェニル-１Ｈ-インデン-１-イリデン]ルテニウム(ＩＩ)クロリド、ＣＡＳ Ｎｏ.９３４５３８-０４-２である。これは、例えばNeolyst^{(登録商標)}M41の名称で、Umicore社より市販されている。 The following structural formula:

Catalyst (II-b) having
The chemical name of this catalyst is [1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene]-[2-[[(4-methylphenyl) imino] methyl] -4-nitro. Phenolyl]-[3-phenyl-1H-indene-1-ylidene] ruthenium (II) chloride, CAS No. 934538-04-2. This, for example, under the name Neolyst ^{(registered trademark)} M41, commercially available from Umicore Company.

を有する触媒（ＩＩ-ｃ）。
この触媒の化学名は、３-ビス(メシチル)-２-イミダゾリジニリデン]-[２-[[(２-メチルフェニル)イミノ]メチル]フェノリル]-[３-フェニル-１Ｈ-インデン-１-イリデン]ルテニウム(ＩＩ)クロリド、ＣＡＳ Ｎｏ.１０３１２６２-７６-６である。これは、例えばNeolyst^{(登録商標)}M31の名称で市販されている。 The following structural formula:

Catalyst (II-c) having
The chemical name of this catalyst is 3-bis (mesityl) -2-imidazolidinylidene]-[2-[[(2-methylphenyl) imino] methyl] phenolyl]-[3-phenyl-1H-indene-1- Iridene] ruthenium (II) chloride, CAS No. 1031262-76-6. This is for example Neolyst sold under the name ^(R) M31.

を有する触媒（ＩＩ-ｄ）。
この触媒の化学名は、３-ビス(メシチル)-２-イミダゾリジニリデン]-[２-[[(２-メチルフェニル)イミノ]メチル]フェノリル]-[３-フェニル-１Ｈ-インデン-１-イリデン]−ルテニウム(ＩＩ)クロリド、ＣＡＳ Ｎｏ.９３４５３８-１２-２である。これは、例えばNeolyst^{(登録商標)}M42の名称で、Umicore社より市販されている。 The following structural formula:

Catalyst (II-d) having
The chemical name of this catalyst is 3-bis (mesityl) -2-imidazolidinylidene]-[2-[[(2-methylphenyl) imino] methyl] phenolyl]-[3-phenyl-1H-indene-1- Iridene] -ruthenium (II) chloride, CAS No. 934538-12-2. This, for example, under the name Neolyst ^{(registered trademark)} M42, commercially available from Umicore Company.

を有する触媒（ＩＩ-ｅ）。
この触媒の化学名は、ジクロロ(ｏ-イソプロポキシフェニルメチレン)(トリシクロヘキシルホスフィン)-ルテニウム(ＩＩ)、ＣＡＳ Ｎｏ.２０３７１４-７１-０である。これは、例えば第１世代Hoveyda-Grubbs触媒の名称で市販されている。 The following structural formula:

Catalyst (II-e) having
The chemical name of this catalyst is dichloro (o-isopropoxyphenylmethylene) (tricyclohexylphosphine) -ruthenium (II), CAS No. 203714-71-0. This is marketed, for example, under the name of the first generation Hoveyda-Grubbs catalyst.

  The ruthenium catalyst is preferably used in an amount in the range of 0.01-5 mol%, particularly preferably in an amount in the range of 0.3-1.5 mol%, based on the amount of reactant (A) used.

Reaction conditions (temperature)
The process according to the invention is preferably carried out at a temperature in the range from 25 to 90 ° C, in particular 40 to 80 ° C. A range of 50 to 70 ° C. is particularly preferable.

〔solvent〕
The process of the present invention may be carried out in a conventional organic solvent in which reactant (A) or reactants (A) and (B) and the catalyst used (when using the catalyst in homogeneous catalyst form) are dissolved.
In the context of the present invention, the compounds included in the definition of reactants (A) and (B) are not solvents, which means that the solvent must be structurally different from compounds (A) and (B). I will state that clearly.
It is preferred to use an aprotic solvent such as a hydrocarbon (eg hexane or tetrahydrofuran).

  In a further preferred embodiment of the invention, the method of the invention is carried out without using a solvent.

[Other parameters]
The reaction is preferably carried out in the absence of an acid having a pKa of 3 or less. Examples of acids having a pKa of 3 or less are, for example, mineral acids, p-toluenesulfonic acid, methanesulfonic acid.

  The process of the invention is preferably carried out in the absence of oxygen, for example under an inert gas stream (for example under nitrogen or argon, or using the passage of nitrogen or argon) or under reduced pressure. If desired, component (B) itself can also act as an inert gas when component (B) is used and is present in the gaseous state under reaction conditions.

[Purification]
The process of the invention which is an isomerization metathesis (= tandem isomerization / metathesis reaction) results in a mixture of substances whose complexity is the molar ratio of reactants A and B, the type of reactant B, the gaseous reactant B Can be controlled by process parameters including partial pressure, reaction state under reduced pressure, molar ratio of catalyst, reaction time and temperature. If desired, the substance mixture can be subjected to separation by conventional methods, for example by distillation, by fractional crystallization or by extraction.

  Optionally, the product obtained by the process of the invention can be subjected to hydrogenation or another cross-metathesis. The latter (another cross-metathesis) may be a desirable choice if it is desired to convert the monocarboxylate present in the product mixture to a dicarboxylate.

〔use〕
The mixture of olefins, monocarboxylates and dicarboxylates obtained from unsaturated fatty acids according to the present invention is itself similar to the fuel used under the name “metathesized biodiesel”, but desired If so, it can also be fractionated into a monoester fraction and a diester fraction, each with its own possible use. Monocarboxylate mixtures are suitable for plastic applications, surfactants, hydraulic oils and lubricating oils, for example. Unsaturated dicarboxylates cannot be obtained from mineral oils but play an important role in the production of odorants, adhesives and special antibiotics. At the same time, it can be further modified due to the existing double bonds, for example for new bio-based polyesters, polyamides, polyurethanes, resins, fibers, coatings and adhesives.

Catalyst (A) used: Pd dimer (Pd (dba) ₂ = 1,2-bis (di-t-butylphosphinomethyl) -benzene (B): Umicore M4 ₂
The chemical name of this catalyst is 3-bis (mesityl) -2-imidazolidinylidene]-[2-[[(2-methylphenyl) imino] methyl] phenolyl]-[3-phenyl-1H-indene-1- Iridene] ruthenium (II) chloride.
(C): 2nd generation Hoveyda-Grubbs The chemical name of this catalyst is dichloro (o-isopropoxyphenylmethylene) (tricyclohexyl-phosphine) ruthenium (II).

Example 1:
Oleic acid and maleic acid isomerization cross-metathesis catalyst (A) (5.8 mg, 7.5 μmol, 0.0075 equivalent), catalyst (B) in a 20 ml reaction vessel equipped with a beaded rim and a stir bar. (12.7 mg, 15 μmol, 0.015 eq) and maleic acid (234 mg, 2.0 eq) were initially charged, the vessel closed with a septum and purged with argon three times. THF (3.0 ml) and oleic acid (90%, 314 mg, 1.0 mmol) were added via syringe and the mixture was stirred at 70 ° C. for 16 hours.

  After cooling to room temperature, methanol (2 ml) and concentrated sulfuric acid (50 μl) were added by syringe and the mixture was stirred at 70 ° C. for 2 hours. The GC of the mixture shows complete conversion (> 97%) to a mixture of olefin, unsaturated monoester and diester, as shown in Table 1.

Example 2:
Isomerized cross-metathesis of methyl oleate and maleic acid In a 20 ml reaction vessel equipped with bead rim and stir bar, catalyst (A) (6.1 mg, 7.5 μmol, 0.0075 equivalent), catalyst (B) (12. 7 mg, 15 μmol, 0.015 eq) and maleic acid (348 mg, 3.0 eq) were initially charged, the vessel closed with a septum and purged with argon three times. Methyl oleate (90% purity, 329 mg, 1.0 mmol) was added with stirring and the mixture was stirred at 70 ° C. for 16 hours. After cooling to room temperature, methanol (2 ml) and concentrated sulfuric acid (50 μl) were added by syringe and the mixture was stirred at 70 ° C. for 2 hours.

  The GC of the mixture indicates complete conversion (> 97%) to a mixture of olefin, unsaturated monomethyl ester and dimethyl ester.

Example 3: Isomerization cross-metathesis of methyl oleate and dimethyl maleate In a 20 ml reaction vessel equipped with bead rim and stir bar, catalyst (A) (5.3 mg, 6.5 μmol, 0.0065 eq) and catalyst ( C) (9.0 mg, 15 μmol, 0.015 equiv) was initially charged, the vessel closed with a septum, and purged with argon three times. Methyl oleate (90% purity, 329 mg, 1.0 mmol) and dimethyl maleate (144 mg, 1.0 mmol, 1.0 equiv) were added via syringe and the mixture was stirred at 70 ° C. for 16 h. The GC of the mixture showed 88% conversion to a mixture of olefin, unsaturated monomethyl ester and dimethyl ester as shown in Table 2.

Example 4: Isomerization cross-metathesis of methyl oleate and maleic acid Into a 20 ml reaction vessel equipped with bead rim and stir bar, catalyst (A) (1.5 mg, 1.9 μmol, 0.0075 eq), catalyst (B ) (3.2 mg, 3.8 μmol, 0.015 eq) and maleic acid (58 mg, 0.5 mmol, 2.0 eq) were initially charged, the vessel closed with a septum and purged with argon three times. THF (1.5 ml) and methyl oleate (90% purity, 82 mg, 0.25 mmol) were added via syringe and the mixture was stirred at 70 ° C. for 16 hours.

  After cooling to room temperature, methanol (2 ml) and concentrated sulfuric acid (50 μl) were added by syringe and the mixture was stirred at 70 ° C. for 2 hours. GC of the mixture indicated complete conversion (> 97%) to a mixture of olefin, unsaturated monomethyl ester and dimethyl ester.

Example 5: Isomerization cross-metathesis of methyl oleate and fumaric acid Into a 20 ml reaction vessel equipped with bead rim and stir bar, catalyst (A) (5.1 mg, 6.3 μmol, 0.025 eq), catalyst (B ) (3.2 mg, 3.8 μmol, 0.015 eq) and fumaric acid (88 mg, 0.75 mmol, 3.0 eq) were initially charged, the vessel closed with a septum and purged with argon three times. Toluene (1.5 ml) and methyl oleate (90% purity, 82 mg, 0.25 mmol) were added via syringe and the mixture was stirred at 70 ° C. for 16 hours. After cooling to room temperature, methanol (2 ml) and concentrated sulfuric acid (50 μl) were added by syringe and the mixture was stirred at 70 ° C. for 2 hours. GC of the mixture indicated complete conversion (> 97%) to a mixture of olefin, unsaturated monomethyl ester and dimethyl ester.

Example 6: Isomerization cross-metathesis of methyl oleate and fumaric acid Into a 20 ml reaction vessel equipped with bead rim and stir bar, catalyst (A) (5.1 mg, 6.3 μmol, 0.025 eq), catalyst (B ) (3.2 mg, 3.8 μmol, 0.015 eq) and fumaric acid (88 mg, 0.75 mmol, 3.0 eq) were initially charged, the vessel closed with a septum and purged with argon three times. THF (1.5 ml) and methyl oleate (90% purity, 82 mg, 0.25 mmol) were added via syringe and the mixture was stirred at 70 ° C. for 16 hours. After cooling to room temperature, methanol (2 ml) and concentrated sulfuric acid (50 μl) were added by syringe and the mixture was stirred at 70 ° C. for 2 hours. GC of the mixture indicated complete conversion (> 97%) to a mixture of olefin, unsaturated monomethyl ester and dimethyl ester.

Example 7: Isomerization cross-metathesis of oleic acid and maleic acid In a 20 ml reaction vessel equipped with bead rim and stir bar, catalyst (A) (5.8 mg, 7.5 μmol, 0.075 equivalent), catalyst (B) (12.7 mg, 15 μmol, 0.015 eq) and maleic acid (234 mg, 2.0 mmol, 2.0 eq) were initially charged, the vessel closed with a septum and purged with argon three times. Hexane (3.0 ml) and oleic acid (90% purity, 314 mg, 1.0 mmol) were added via syringe and the mixture was stirred at 70 ° C. for 16 hours.
After cooling to room temperature, methanol (2 ml) and concentrated sulfuric acid (50 μl) were added by syringe and the mixture was stirred at 70 ° C. for 2 hours. GC of the mixture showed 85% conversion to a mixture of olefin, unsaturated monomethyl ester and dimethyl ester.

Claims (14)

A method for producing a composition comprising an unsaturated compound, comprising (A) one or more unsaturated monocarboxylic acids having 10 to 24 carbon atoms or esters of the monocarboxylic acids, and (B) 4 to 4 Subjecting one or more unsaturated dicarboxylic acids having 20 carbon atoms or an ester of the unsaturated dicarboxylic acid to a tandem isomerization / metathesis reaction in the presence of a palladium catalyst and a ruthenium catalyst, wherein the palladium catalyst used Is at least one structural element Pd—P (R ¹ R ² R ³ ) [wherein the R ^{1 to} R ³ groups each independently have 2 to 10 carbon atoms, , alicyclic, may be aromatic or heterocyclic, provided that at least one of said R ¹ to R ³ radicals is a compound containing a] containing β- hydrogen, the palladium catalyst by itself Or, is used to cause in situ, however, the method is carried out in the absence of a substance having more than 3 pKa, manufacturing method.   The process according to claim 1, wherein the palladium catalyst contains two palladium atoms per molecule.   The two palladium atoms are joined to one another via a spacer X, the spacer being selected from halogen, oxygen, O-alkyl, sulfur, sulfur-alkyl, disubstituted nitrogen, carbon monoxide, nitrile, diolefin; The method of claim 2. The palladium catalyst used is of the formula (I):

[Wherein X is a spacer selected from halogen, oxygen and O-alkyl, Y ¹ is P (R ¹ R ² R ³ ) [wherein R ¹ , R ² and R ³ are each And Y ² is P (R ⁴ R ⁵ R ⁶ ), wherein R ⁴ , R ⁵ and R ⁶ are each independently 2 to 10 carbons. A group having atoms, each of which may be aliphatic, alicyclic, aromatic or heterocyclic]
The method of Claim 1 which is a compound shown by these. The palladium catalyst used is of the formula (Ia):

[Wherein X is a spacer selected from halogen, oxygen and O-alkyl, Y ¹ is a P (R ¹ R ² R ³ ) group [wherein R ¹ , R ² and R ³ are Each is as defined above], and Y ² is a P (R ⁴ R ⁵ R ⁶ ) group, wherein R ⁴ , R ⁵ and R ⁶ are each independently 2-10 Having carbon atoms, each may be aliphatic, alicyclic, aromatic or heterocyclic]]
The method of Claim 1 which is a compound shown by these. The palladium catalyst used is of the formula (Ia):

[Wherein spacer X is bromine and R ¹ , R ² and R ³ groups are each defined as tert-butyl]
The method of Claim 1 which is a compound shown by these.   The method according to claim 1, wherein the palladium catalyst is a homogeneous catalyst or a heterogeneous catalyst.   The method according to any one of claims 1 to 7, wherein the compound (B) used is an unsaturated dicarboxylic acid or dicarboxylic acid derivative having 4 to 10 carbon atoms.   The method according to any one of claims 1 to 9, wherein the reaction is carried out in an aprotic solvent.   The method according to any one of claims 1 to 9, wherein the reaction is carried out in the absence of a solvent.   The method according to any one of claims 1 to 11, which is carried out in the absence of an acid having a pKa of 3 or less.   The method according to claim 1, wherein the reaction is carried out in the absence of oxygen.   Compound (A) is selected from the group of unsaturated carboxylic acids having 14 to 24 carbon atoms and esters of unsaturated carboxylic acids having 14 to 24 carbon atoms. The method described in 1.   The method according to claim 1, wherein the reaction is carried out at 40 to 80 ° C.

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