JP2013142060A - Method for producing olefin - Google Patents

Abstract

An object of the present invention is to provide a method for producing an olefin, which can selectively obtain a target olefin in a high yield.
A method for producing an olefin comprising a decarbonylation reaction step of a carboxylic acid having β hydrogen atom or a derivative thereof, wherein the decarbonylation reaction step is carried out in the presence of the following components (a) and (b): A process for producing olefins.
(A) One or more metal components selected from Group 9 metals and Group 10 metals (b) The number of bridging atoms between the coordination atoms having two or more coordination atoms selected from phosphorus atoms and nitrogen atoms Is a ligand component.
[Selection figure] None

Description

  The present invention relates to a method for producing an olefin using a carboxylic acid having a β hydrogen atom or a derivative thereof as a raw material. More specifically, the present invention relates to a method for producing an olefin that is suitably used as an intermediate material for surfactants, various chemicals, and pharmaceuticals.

  As a method for producing an olefin from a carboxylic acid by a catalytic reaction, a method comprising producing a catalyst containing an element selected from Group 8 metal, Group 9 metal, Group 10 metal and copper and an acid anhydride (Patent Document) 1), a method of producing Pd or Rh complex catalyst at a reaction temperature of 280 ° C. (Non-patent Document 1), pivalic anhydride in a polar solvent (such as dimethylpropylene urea (DMPU)) in addition to the Pd complex catalyst In addition, a method for producing an α-olefin at a reaction temperature of 110 ° C. using an amine-based organic base (such as diazabicycloundecene (DBU)) has been reported.

  In addition, the present inventors also have a compound containing one or more metal elements selected from Group 6 metals to Group 11 metals and iodine element, or Group 8 metal, Group 9 metal, Group 10 metal and copper. A method for producing olefins (patent document 2) using a combination of a catalyst containing an element selected from the above and an iodide has been found and applied.

US Pat. No. 5,077,447 JP 2010-168340 A

J. Am. Oil. Chem. Soc., 1976, 53, 737 Tetrahedron, Lett., 2010, 51, 3712

Regarding the technologies described in Patent Documents 1 and 2 and Non-Patent Documents 1 and 2, the target olefin can be produced from a carboxylic acid by a catalytic reaction, but the yield of the target olefin is low (Patent Document 1). 2) Due to the adoption of a high reaction temperature to improve the catalyst activity, the catalyst life is short and the olefin selectivity is low (Non-Patent Document 1), or specially for improving the olefin selectivity. There is a problem of requiring a simple solvent (Non-patent Document 2).
An object of the present invention is to provide a method for selectively producing a target olefin in a high yield without requiring a special solvent and additive.

  As a result of studying the ligand of the metal complex catalyst, the present inventors have used a catalyst containing a specific metal component and a ligand component having 3 bridging atoms between coordination atoms. The present inventors have found that the above problems can be solved.

That is, the present invention provides the following invention as means for solving the problems.
A process for producing an olefin comprising a step of decarbonylating a carboxylic acid having β hydrogen atom or a derivative thereof,
The method for producing olefin, wherein the decarbonylation reaction step is performed in the presence of the following components (a) and (b).
(A) One or more metal components selected from Group 9 metals and Group 10 metals (b) The number of bridging atoms between the coordination atoms having two or more coordination atoms selected from phosphorus atoms and nitrogen atoms Is a ligand component (excluding diazabicycloundecene and dimethylpropyleneurea as component (b))

  By the production method of the present invention, it is possible to synthesize an olefin suitably used as an intermediate raw material of a base such as a surfactant in a high yield without requiring a special solvent or additive.

The figure which shows the presumed reaction mechanism for demonstrating the process of performing the decarbonylation reaction in the manufacturing method of this invention.

The method for producing an olefin of the present invention includes a step of decarbonylating a carboxylic acid having a β hydrogen atom or a derivative thereof.
The carboxylic acid having a β hydrogen atom or a derivative thereof used in the present invention is not particularly limited as long as it has at least one hydrogen atom at the β-position of the carbonyl group. However, a saturated monovalent carboxylic acid or a derivative thereof is preferable.

  Examples of the carboxylic acid derivative having a β hydrogen atom include a carboxylic acid anhydride having a β hydrogen atom, a carboxylic acid halide having a β hydrogen atom, a carboxylic acid ester having a β hydrogen atom, and a carboxylic acid amide having a β hydrogen atom. A carboxylic acid anhydride having a β hydrogen atom and a carboxylic acid halide having a β hydrogen atom are preferred, and a carboxylic acid anhydride having a β hydrogen atom is more preferred.

  As the carboxylic acid having a β hydrogen atom or a derivative thereof, one having 2 to 30 carbon atoms in the alkyl moiety of the carboxylic acid including an acyl group, that is, a carbonyl carbon is preferable, and one having 10 to 22 is preferable, Are more preferred. When the carboxylic acid or derivative thereof is an acid anhydride, one having 2 to 30 carbon atoms, more preferably 8 to 22 carbon atoms, of at least one of two acyl groups constituting the acid anhydride is preferable. More preferred are those of ˜18.

  Specific examples of the carboxylic acid having a β hydrogen atom include 3-methylbutanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, eicosanoic acid, behenic acid, 9-decenoic acid, Examples thereof include 10-undecenoic acid, oleic acid, 2,4-hexadienoic acid, 6-octadesinic acid, ricinoleic acid, adipic acid, azelaic acid, 3-phenylpropionic acid, hydonocarpic acid, and gorulinic acid.

Specific examples of carboxylic acid anhydrides having β hydrogen atoms include 3-methylbutanoic anhydride, caproic anhydride, caprylic anhydride, capric anhydride, lauric anhydride, myristic anhydride, palmitic anhydride , Stearic anhydride, eicosanoic anhydride, behenic anhydride, 9-decenoic anhydride, 10-undecenoic anhydride, oleic anhydride, 2,4-hexadienoic anhydride, 6-octadesinic anhydride Products, ricinoleic acid anhydride, succinic acid anhydride, adipic acid anhydride, azelaic acid anhydride, 3-phenylpropionic acid anhydride, hydnocarpinic acid anhydride, gorulinic acid anhydride, and the like.
Further, formic acid, acetic acid, propionic acid, butyric acid, the carboxylic acid mentioned in the specific examples of the carboxylic acid having β hydrogen atom, and the carboxylic acid mentioned in the specific examples of the carboxylic acid having β hydrogen atom It may be a carboxylic acid anhydride in which different carboxylic acids are condensed.
Furthermore, a low-boiling acid anhydride such as acetic anhydride or pivalic anhydride is mixed with the above preferred carboxylic acid having β hydrogen to form the above preferred carboxylic anhydride having β hydrogen on the spot. May be.

  Specific examples of the carboxylic acid halide having a β hydrogen atom include 3-methylbutanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, eicosanoic acid, behenic acid, 9-decene. Acid, 10-undecenoic acid, oleic acid, 2,4-hexadienoic acid, 6-octadesinic acid, ricinoleic acid, adipic acid, azelaic acid, 3-phenylpropionic acid, hydronocarpic acid, gorlic acid, chlorinated products, brominated products, Iodide is mentioned.

  Specific examples of the carboxylic acid ester having a β hydrogen atom include 3-methylbutanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, eicosanoic acid, behenic acid, and 9-decenoic acid. Methyl esters such as 10-undecenoic acid, oleic acid, 2,4-hexadienoic acid, 6-octadesinic acid, ricinoleic acid, adipic acid, azelaic acid, 3-phenylpropionic acid, hydonocarpic acid, golphosphoric acid, ethyl ester, etc. Can be mentioned.

  Specific examples of the carboxylic acid amide having a β hydrogen atom include 3-methylbutanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, eicosanoic acid, behenic acid, and 9-decenoic acid. Amides such as 10-undecenoic acid, oleic acid, 2,4-hexadienoic acid, 6-octadesinic acid, ricinoleic acid, adipic acid, azelaic acid, 3-phenylpropionic acid, hydonocarpic acid, golphosphoric acid, monomethylamide, dimethylamide , Diethylamide and the like.

The decarbonylation reaction step of the present invention comprises
(A) one or more metal components selected from Group 9 metals and Group 10 metals (b) having two or more coordination atoms selected from phosphorus atoms and nitrogen atoms, and the number of bridging atoms between the coordination atoms Is a ligand component (excluding diazabicycloundecene and dimethylpropyleneurea as component (b))
Done in the presence of.

The decarbonylation reaction step of the present invention includes
(A ′) a compound containing one or more metal components selected from Group 9 metals and Group 10 metals;
(B ′) A compound having two or more coordination atoms selected from a phosphorus atom and a nitrogen atom and having 3 bridging atoms between the coordination atoms can be added.

The decarbonylation reaction step of the present invention includes
(Ab) one or more metal components selected from Group 9 metals and Group 10 metals, and two or more coordination atoms selected from a phosphorus atom and a nitrogen atom, and the number of bridging atoms between the coordination atoms is 3 can be carried out by adding a compound containing both ligand components.
When carrying out the decarbonylation reaction step using this (ab), since both the component (a) and the component (b) are included, the reaction can be carried out as it is or separately from the other component (a). Or you may carry out by adding (b) component.

  (A) One or more metal components selected from Group 9 metals and Group 10 metals include Co, Rh, Ir, Ni, Pd, Pt, etc. Among these, Co, Rh, Ni Ni is more preferable.

Specific examples of the compound containing at least one metal component selected from Group 9 metals and Group 10 metals of (a ′) include [RhCl (CO) ₂ ] ₂ , RhCl ₃ , NiCl ₂ , PdCl. ₂ , CoCl ₂ , PtCl ₂ , Ir (CO) ₃ Cl, IrCl _{3 and the} like.
Among these, [RhCl (CO) ₂ ] ₂ , CoCl ₂ , and NiCl ₂ are preferable, and NiCl ₂ is particularly preferable.
(Ab) one or more metal components selected from Group 9 metals and Group 10 metals, and two or more coordination atoms selected from phosphorus atoms and nitrogen atoms, and the number of bridging atoms between the coordination atoms Examples of the compound containing both of the ligand components of which 3 is (DPPP) Rh (CO) Cl, (Py (CH ₂ ) ₂ PPh ₂ ) Rh (CO) Cl, (DPPP) NiCl ₂ , (Py (CH ₂ ) ₂ PPh ₂ ) NiCl ₂ , (DPPP) PdCl ₂ , (Py (CH ₂ ) ₂ PPh ₂ ) PdCl ₂ , (DPPP) CoCl ₂ , (Py (CH ₂ ) ₂ PPh ₂ ) CoCl ₂ , ( _{DPPP) PtCl 2, (Py (} CH 2) 2 PPh 2) PtCl 2, (DPPP) Ir (CO) Cl, (Py (CH 2) 2 PPh 2) Ir (CO) Cl
(In the formula, Ph represents a phenyl group, Py represents a pyridyl group, DPPP represents a 1,3-bis (diphenylphosphino) propyl group, and Py (CH ₂ ) ₂ PPh ₂ represents 2- [2- ( Diphenylphosphino) ethyl] pyridyl group, and the same applies to the following.

  The amount of the compound containing one or more metal components selected from Group 9 metals and Group 10 metals is 0.00001 to 0 per metal atom with respect to 1 mol of a carboxylic acid or derivative thereof having a β hydrogen atom. 0.8 mol is preferable, 0.0001 to 0.5 mol is more preferable, 0.001 to 0.4 mol is more preferable, and 0.005 to 0.3 mol is particularly preferable.

The component (b) used in the method for producing an olefin of the present invention has two or more coordination atoms selected from a phosphorus atom and a nitrogen atom, and the ligand component has 3 bridging atoms between the coordination atoms. (However, diazabicycloundecene and dimethylpropyleneurea are excluded as component (b)).
The number of coordinating atoms contained in the component (b) is 2 or more, preferably 2 to 4, and more preferably 2 from the viewpoint of reactivity. The ligand component includes a part of the compound other than the ligand component in which the number of bridging atoms between the coordination atoms in (b) is 3, for example, a compound in which the number of atoms between the coordination atoms is 2 However, it is preferably not included in solving the problems of the present invention.
When two coordination atoms are bridged by a plurality of chains, the number of bridged atoms constituting the shorter chain is 3 as the component (b) of the present application. For example, diazabicycloundecene, dimethylpropyleneurea and the like have two chains bridging between two nitrogen atoms, but the shorter one is not preferable.
In these compounds, two nitrogen atoms form one functional group such as an amidino group and a urea group, and do not function as two ligands. Similarly, in the imidazole group and imidazoline group, two nitrogen atoms jointly form one functional group. Therefore, in the present invention, these functional groups are regarded as a single ligand for the entire group, and when counting the number of bridging atoms between coordinating atoms, they are counted according to the number of atoms between closer coordinating atoms. To do.

As the ligand component of the component (b), a ligand having 3 bridging atoms between coordinating atoms represented by the following general formula (1) is preferably used.
In addition, the ligand component of the component (b) includes both those in a state where they are coordinated to a metal and become a molecular component, and those in which the compound is a simple substance ((b ′) compound) It is.

Y ₁ and Y ₂ are preferably a bidentate ligand selected from one or more of an imidazole group, an imidazoline group, a pyridyl group and a tertiary phosphine, and a bidentate ligand of a pyridyl group and a tertiary phosphine. Alternatively, a bidentate ligand of tertiary phosphine and tertiary phosphine is more preferable.

A ₁ , A ₂ and A ₃ are preferably an alkylene chain or an alkylidene chain. Further, it may constitute one side or two sides of the (hetero) aromatic ring. There is no problem even if the alkylene chain or the alkylidene chain has a substituent, but from the viewpoint of reducing the steric hindrance of the ligand, a linear alkyl group or a linear alkylene group is preferred when it has a substituent.

Specific ligand components include 1,3-bis (diphenylphosphino) propane, 1,3-bis (dicyclohexylphosphino) propane, 1,3-bis (dimethylphosphino) propane, 1,3- Bis (diethylphosphino) propane, 1,3-bis (dipropylphosphino) propane, 1,3-bis [bis (2,4-dimethylphenyl) phosphino] propane ^{* 1)} , 1,3-bis [bis (2,5-dimethylphenyl) phosphino] propane ^{* 1)} , 1,3-bis [bis (4-trifluoromethylphenyl) phosphino] propane, (2S, 4S) -2,4-bis [bis (4- Trifluoromethylphenyl) phosphino] pentane, 2- [2- (diphenylphosphino) ethyl] pyridine, 2- [2- {bis (2,4-dimethylphenyl) phos I Roh} ethyl] pyridine ^* 2), 2- [2- {bis (4-trifluoromethylphenyl) phosphino} ethyl] pyridine ^* 2), 2- [2- {bis (2,5-dimethylphenyl) phosphino } Ethyl] pyridine ^{* 2)} , 2- [2- {bis (2,4,6-trimethylphenyl) phosphino} ethyl] pyridine, 2- [2- {bis (2-methylphenyl) phosphino} ethyl] pyridine, 2- [2- (dicyclohexylphosphino) ethyl] pyridine, 2- [2- {bis (tert-butyl) phosphino} ethyl] pyridine, 2- [2- {bis (i-propyl) phosphino} ethyl] pyridine, Examples include di (2-pyridyl) methanone, di (2-pyridyl) methane, di (2-imidazolyl) methane, 1,3-di (1-imidazolyl) propane, and the like. These ligand components may be used alone or in combination of two or more.
Among these, 1,3-bis (diphenylphosphino) propane, 2- [2- (diphenylphosphino) ethyl] pyridine, and di (2-pyridyl) methanone are particularly preferable.

  The above * 1) ligand can be synthesized by the method described in Tetrahedron Lett., 2003, 44, 8373, and * 2) the ligand is Org. Lett, 2002., 4, 761. It can synthesize | combine by description of.

  The amount of the component (b) used is from the viewpoint of obtaining good catalyst stability and reaction rate, with respect to 1 mole of the metal atom of the group 9 metal and the group 10 metal which are the metal components of the component (a). 0.1-1000 mol is preferable, 0.2-500 mol is more preferable, 0.3-100 mol is further more preferable.

In the olefin production method of the present invention, the decarbonylation reaction step can be carried out at a reaction pressure and a reaction temperature within the following ranges.
The reaction pressure is preferably 1 to 300 kPa, more preferably 5 to 150 kPa, and even more preferably 25 to 110 kPa from the viewpoint of the reaction rate.
The reaction temperature is preferably 20 to 300 ° C, more preferably 80 to 270 ° C, and still more preferably 120 to 260 ° C, from the viewpoint of obtaining good selectivity for olefins.
The reaction is preferably performed in an inert gas atmosphere. Examples of the inert gas include nitrogen and argon.
It is preferable to appropriately remove elimination components such as water, alcohol, hydrogen halide and ammonia produced by the reaction. Although it is preferable to remove carbon monoxide generated by the decarbonylation reaction, the reaction rate can be increased by allowing the carbon monoxide to remain appropriately.
As other components, it can be carried out in the presence of a solvent, a ligand, a dehydrating agent and the like.

The olefin production method of the present invention can be carried out by adding an acid anhydride having no β hydrogen atom. As the acid anhydride having no β hydrogen atom, acetic anhydride is preferable.
The amount of the acid anhydride having no β hydrogen atom is preferably 10 mol or less, more preferably 2 mol or less, based on 1 mol of the carboxylic acid having β hydrogen atom or its derivative. Moreover, the usage-amount of the acid anhydride which does not have (beta) hydrogen atom has more preferable 0.01 mol or more.

The olefin production method of the present invention can be further carried out in the presence of iodine as component (c).
(C) Specifically, there are two methods of carrying out the reaction in the presence of the component, namely the following production method 1 and production method 2.
Production Method 1: Performed by adding an iodide of an element selected from Group 1 to Group 8 and Group 11 to Group 14 elements, or a quaternary ammonium compound represented by the following general formula (2) Method,
_{[R- (X) n] 4} N + I - (2)
(Wherein, R represents a hydrocarbon group having 1 to 22 carbon atoms, X is -Z- (CH _{2) m} - represents a group represented by, Z is an ether group, an amino group, an amido group or ester group, More specifically, —O—, —NH—, —CONH—, —NHCO—, —COO— or —OCO—, m represents a number of 1 to 6, n represents 0 or 1, R, X and n may be the same or different from each other, and a cyclic structure may be formed between [R— (X) _n ].

  Production method 2: One or more metal components selected from Group 9 metals and Group 10 metals, and a method comprising adding a compound containing iodine,

The iodide used in Production Method 1 is an iodide of an element selected from Group 1 elements to Group 8 elements and Group 11 elements to Group 14 elements, or a quaternary compound represented by the following general formula (2): An ammonium compound is mentioned.
_{[R- (X) n] 4} N + I - (2)
(Wherein, R represents a hydrocarbon group having 1 to 22 carbon atoms, X is -Z- (CH _{2) m} - represents a group represented by, Z is an ether group, an amino group, an amido group or ester group, More specifically, —O—, —NH—, —CONH—, —NHCO—, —COO— or —OCO—, m represents a number of 1 to 6, n represents 0 or 1, R, X and n may be the same or different from each other, and a cyclic structure may be formed between [R- (X) _n ].

  The iodide is preferably an iodide of an element selected from Group 1 elements and Group 12 elements. Specifically, KI, LiI, and NaI are preferable, and KI and NaI are more preferable.

As the quaternary ammonium compound represented by the general formula (2), R is an alkyl group having 1 to 7 carbon atoms or a benzyl group (preferably an alkyl group having 1 to 7 carbon atoms), and n is 0. Quaternary ammonium compounds are preferred, Et ₄ N ⁺ I ⁻ , (n-Bt) ₄ N ⁺ I ⁻ (where Et represents an ethyl group, n-Bt represents an n-butyl group), and the like is more preferable. ₄ N ⁺ I ⁻ is preferred.

  The amount of iodide used is preferably 0.001 to 10 moles, more preferably 0.01 to 3 moles per mole of carboxylic acid having a β hydrogen atom or a derivative thereof.

In the production method 2, a compound containing one or more metal components selected from Group 9 metals and Group 10 metals and iodine is used.
From the viewpoint of reactivity and selectivity, one or more metal components selected from Group 9 metals and Group 10 metals include Co, Rh, Ir, Ni, Pd, and Pt. Co, Rh Ni is preferred, and Ni is more preferred.

As a specific example of a compound containing one or more metal components selected from Group 9 metals and Group 10 metals and iodine,
CoI ₂ , CoI ₂ (CO) (C ₅ H ₅ ), CoI ₂ (DPPP), CoI ₂ [Py (CH ₂ ) ₂ PPh ₂ ], RhI ₃ , [RhI (CO) ₂ ] ₂ , RhI (CO) (DPPP), RhI [Py (CH ₂ ) ₂ PPh ₂ ], IrI ₄ , IrI (CO) (DPPP), IrI (CO) [Py (CH ₂ ) ₂ PPh ₂ ], NiI ₂ , NiI ₂ (NH ₃ ) ₆ , NiI (1,5-cyclooctadiene), NiI ₂ (DPPP), NiI ₂ [Py (CH ₂ ) ₂ PPh ₂ ], PdI ₂ , PdI ₂ (DPPP), PdI ₂ [Py (CH ₂ ) ₂ PPh ₂ ], PtI ₂ (1,5-cyclooctadiene), PtI ₂ (DPPP), (PtI ₂ [Py (CH ₂ ) ₂ PPh ₂ ].
(In the formula, Ph represents a phenyl group, Py represents a pyridyl group, DPPP represents a 1,3-bis (diphenylphosphino) propyl group, Py (CH ₂ ) ₂ PPh ₂ represents 2- [2- ( Diphenylphosphino) ethyl] pyridyl group, and so on)) and the like.
Among these, CoI ₂ , RhI ₃ , [RhI (CO) ₂ ] ₂ and NiI ₂ are preferable, and NiI ₂ is more preferable.

The amount of the compound containing one or more metal components selected from Group 9 metals and Group 10 metals and iodine is from 0.00001 to 1 mol per 1 atom of the carboxylic acid or derivative thereof having a β hydrogen atom. 0.8 mol is preferable, 0.0001 to 0.5 mol is more preferable, 0.001 to 0.4 mol is more preferable, and 0.005 to 0.3 mol is particularly preferable.
Since this compound contains the component (a) and the component (c), in addition to this, the component (a) or the component (c) may not be added, and may be added separately.

Although the detailed reason why the problems of the invention can be solved by the method for producing olefin of the present invention is unknown, it is estimated as follows at the time of filing this application. Hereinafter, description will be given with reference to FIG.
The presence of the component (a) and the component (b) in the reaction system forms a catalyst in which the component (b) is coordinated to the metal of the component (a).
In the course of the subsequent catalytic reaction,
1) a step (oxidative addition) that proceeds in a state where a ligand is coordinated to a metal;
2) When at least one of the ligands coordinated to the metal is eliminated and frees the coordination field, and then there is a step (alkyl transfer of the acyl complex) in which the alkyl moves to the free coordination field and proceeds. Thought,
3) The target olefin can be obtained by further extracting β hydrogen and proceeding with olefin elimination.
In other words, in order for these reactions to proceed efficiently, not only does the ligand coordinate to the metal, but it also needs to form an empty coordination field efficiently, so the ligand is somewhat flexible. It is considered necessary to have That is, from the viewpoint of flexibility, it is considered that the number of atoms between coordination atoms needs to be 3 as in the component (b) used in the present invention.
In Non-Patent Document 2, dimethylpropylene urea (DMPU) and diazabicycloundecene (DBU) are used, and these have a bridging chain having 3 carbon atoms between nitrogen atoms. However, these are cyclic compounds, and there is another chain bridging between coordinating atoms, and the far bond distance between nitrogen atoms is 3, but the near bond distance is 1, so many It does not function as a bidentate ligand.
In fact, [—C (═NR) —NR ₂ ] of DBU is known as a substance that acts as a strongly basic functional group called an amidino group as a group, and [—NR—C (= O) -NR-] is known as a substance that functions as a highly polar functional group called urea (urea) as a group, and the reactions 1) to 3) as described above cannot proceed.

The olefin obtained by the production method of the present invention may be not only a structure having a double bond at the terminal, but also an internal olefin having a double bond in the interior isomerized therefrom.
The olefin obtained by the method of the present invention can be suitably used as an intermediate raw material for a base such as a surfactant.

Hereinafter, unless otherwise specified, “%” represents “mol%”.
In addition, the Example corresponding to the manufacturing method 1 is shown in Table 1 and Table 2, and the Example corresponding to the manufacturing method 2 is Example 2 shown in Table 3. Example 3 shown in Table 3 is an embodiment containing no component (c).

Example 1-1a
In a 50 mL eggplant-shaped flask, stearic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.13 g (7.5 mmol), NiCl ₂ (manufactured by SIGMA ALDRICH) 19.4 mg (0.15 mmol), 1, 3-bis (diphenylphosphino) propane (DPPP) 123.7 mg (0.3 mmol), KI (manufactured by SIGMA ALDRICH) 249.0 mg (1.5 mmol) were added, and after purging with nitrogen, 0.03 MPa was maintained. The mixture was stirred at 180 ° C.
After 1.5 hours, the heating was stopped, 33.3 mg of anisole was added as an internal standard, and ¹ H-NMR (Mercury 400, manufactured by Varian) was measured (vinyl proton of terminal olefin, vinyl proton of internal olefin, and internal The raw material conversion rate, olefin selectivity, and olefin yield were calculated based on the quantitative values of raw materials and products obtained by comparing the standard integration ratio of methyl groups of anisole, which is a standard).
The conversion rate of stearic anhydride was 100%, and the terminal olefin was obtained in a yield of 3% and the internal olefin was obtained in a yield of 95% with respect to the prepared stearic anhydride.

Example 1-2a
A stirrer, stearic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.13 g (7.5 mmol), NiCl ₂ (manufactured by SIGMA ALDRICH) 19.4 mg (0.15 mmol), 2-mL [2- (Diphenylphosphino) ethyl] pyridine (PyCH ₂ CH ₂ PPh ₂ ) (manufactured by SIGMA ALDRICH) 87.4 mg (0.3 mmol), KI (manufactured by SIGMA ALDRICH) 249.0 mg (1.5 mmol) In addition, after purging with nitrogen, stirring was performed at 180 ° C. while maintaining 0.03 MPa.
After 1.5 hours, the heating was stopped, 33.3 mg of anisole was added as an internal standard, and ¹ H-NMR measurement was performed (the olefin yield was calculated in the same manner as in Example 1-1).
The conversion rate of stearic anhydride was 100%, and the terminal olefin was 31% and the internal olefin was 69% with respect to the charged stearic anhydride.

Comparative Example 1-1a
The procedure was the same as Example 1-1a except that 1,2-bis (diphenylphosphino) ethane (DPPE) (manufactured by SIGMA ALDRICH) was used instead of DPPP. The conversion of stearic anhydride was 0%.

Comparative Example 1-2a
The procedure was the same as Example 1-1a except that 1,4-bis (diphenylphosphino) butane (DPPB) (manufactured by SIGMA ALDRICH) was used instead of DPPP. The conversion of stearic anhydride was 0%.

Comparative Example 1-3a
In a 50 mL eggplant-shaped flask, stearic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.13 g (7.5 mmol), NiCl ₂ (manufactured by SIGMA ALDRICH) 19.4 mg (0.15 mmol), triphenyl Phosphine (PPh ₃ ) (manufactured by SIGMA ALDRICH) 157.4 mg (0.6 mmol) and KI (manufactured by SIGMA ALDRICH) 249.0 mg (1.5 mmol) were added, and after purging with nitrogen, 0.03 MPa was maintained. And stirring at 180 ° C.
After 1.5 hours, the heating was stopped, 33.3 mg of anisole was added as an internal standard, and ¹ H-NMR measurement was performed (the olefin yield was calculated in the same manner as in Example 1-1).
The conversion rate of stearic anhydride was 54%, and the terminal olefin was obtained in a yield of 23% and the internal olefin was obtained in a yield of 26% with respect to the prepared stearic anhydride.
Table 1 summarizes the results of Examples 1-1a and 1-2a and Comparative Examples 1-1a, 1-2a, and 1-3a.

Example 1-1b
In a 50 mL eggplant-shaped flask, stearic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.13 g (7.5 mmol), NiCl ₂ (manufactured by SIGMA ALDRICH) 19.4 mg (0.15 mmol), di ( 2-pyridyl) methanone (manufactured by SIGMA ALDRICH) 55.3 mg (0.3 mmol) and KI (manufactured by SIGMA ALDRICH) 249.0 mg (1.5 mmol) were added, and after nitrogen substitution, 0.10 MPa was maintained. And stirring at 250 ° C.
After 1.5 hours, the heating was stopped, 33.3 mg of anisole was added as an internal standard, and ¹ H-NMR measurement was performed (the olefin yield was calculated in the same manner as in Example 1-1).
The conversion rate of stearic anhydride was 44%, and the terminal olefin was obtained in a yield of 14% and the internal olefin was obtained in a yield of 7% with respect to the prepared stearic anhydride.

Comparative Example 1-1b
Example 1 except that 2,2′-pyridyl (1,2-di (2-pyridinyl) ethane-1,2-dione, manufactured by SIGMA ALDRICH) was used in place of di (2-pyridyl) methanone. Same as 1b. The conversion of stearic anhydride was 0%.

Comparative Example 1-2b
The procedure was the same as Example 1-1b except that 2,2′-pyridyl (manufactured by SIGMA ALDRICH) was used instead of di (2-pyridyl) methanone. The conversion rate of stearic anhydride was 24%, and the terminal olefin was obtained in a yield of 1% and the internal olefin was obtained in a yield of 0% with respect to the prepared stearic anhydride.
Table 2 summarizes the results of Example 1-1b and Comparative Examples 1-1b and 1-2b.

Example 2
In a 50 mL eggplant-shaped flask, stearic acid (manufactured by Kao Corporation, LUNAC S98) 4.27 g (15.0 mmol), CoI ₂ (manufactured by SIGMA ALDRICH) 93.8 mg (0.30 mmol), DPPP (SIGMA (ALDRICH) 123.7 mg (0.30 mmol) and acetic anhydride (SIGMA ALDRICH) 1.53 g (15.0 mmol) were added. After purging with nitrogen, stirring was continued at 250 ° C. while maintaining 0.10 MPa. went.
After 3 hours, the heating was stopped, 33.3 mg of anisole was added as an internal standard, and ¹ H-NMR measurement was performed (the olefin yield was calculated in the same manner as in Example 1-1).
The conversion rate of stearic acid was 71%, and the terminal olefin was obtained in a yield of 13% and the internal olefin was obtained in a yield of 10% with respect to the prepared stearic acid.

Example 3
In a 50 mL eggplant-shaped flask, a stirrer and 4.27 g (15.0 mmol) of stearic acid (manufactured by Kao Corporation, LUNAC S98), [Rh (CO) ₂ Cl] ₂ (RhCl ₃ .nH ₂ O (Tanaka Kikinzoku Sales) 29.2 mg (0.075 mmol), DPPP (manufactured by SIGMA ALDRICH) 61.9 mg (0.15 mmol), acetic anhydride (manufactured by SIGMA ALDRICH) 1.53 g (15.0 mmol) were added. After substituting with nitrogen, stirring was performed at 250 ° C. while maintaining 0.10 MPa.
After 3 hours, the heating was stopped, 33.3 mg of anisole was added as an internal standard, and ¹ H-NMR measurement was performed (the olefin yield was calculated in the same manner as in Example 1-1).
The conversion rate of stearic acid was 74%, and the terminal olefin was obtained in a yield of 4% and the internal olefin was obtained in a yield of 51% with respect to the prepared stearic acid.
The results of Examples 2 and 3 are summarized in Table 3.

Claims (9)

A process for producing an olefin comprising a step of decarbonylating a carboxylic acid having β hydrogen atom or a derivative thereof,
The method for producing olefin, wherein the decarbonylation reaction step is performed in the presence of the following components (a) and (b).
(A) One or more metal components selected from Group 9 metals and Group 10 metals (b) The number of bridging atoms between the coordination atoms having two or more coordination atoms selected from phosphorus atoms and nitrogen atoms Is a ligand component (excluding diazabicycloundecene and dimethylpropyleneurea as component (b))   The decarbonylation reaction step is coordinated with a compound containing one or more metal components selected from Group 9 metals and Group 10 metals, and two or more coordination atoms selected from phosphorus atoms and nitrogen atoms The method for producing an olefin according to claim 1, which is carried out by adding a compound having 3 bridge atoms between atoms.   The decarbonylation reaction step includes one or more metal components selected from Group 9 metals and Group 10 metals, and two or more coordination atoms selected from phosphorus atoms and nitrogen atoms, and bridging between coordination atoms The method for producing an olefin according to claim 2, which is carried out by adding a compound containing both a ligand component having 3 atoms. The method for producing an olefin according to any one of claims 1 to 3, wherein the decarbonylation reaction step is further performed in the presence of iodine as the component (c). In the decarbonylation reaction step, an iodide of an element selected from Group 1 to Group 8 elements and Group 11 to Group 14 elements, or a quaternary ammonium compound represented by the following general formula (2) The method for producing an olefin according to claim 4, which is carried out by adding
_{[R- (X) n] 4} N + I - (2)
(Wherein, R represents a hydrocarbon group having 1 to 22 carbon atoms, X is -Z- (CH _{2) m} - represents a group represented by, Z is an ether group, an amino group, an amido group or ester group, m represents a number from 1 to 6, n represents 0 or 1, and a plurality of R, X and n may be the same or different from each other, and [R- (X) _n ] An annular structure may be formed.)   The olefin production according to claim 4 or 5, wherein the decarbonylation reaction step is carried out by adding one or more metal components selected from Group 9 metals and Group 10 metals and a compound containing iodine. Method. The olefin according to any one of claims 1 to 6, wherein the ligand component having 3 bridging atoms between coordinating atoms of the component (b) is a ligand represented by the following general formula (1). Manufacturing method.

(Where
A1, A2 and A3 are carbon atoms which may have a substituent, and A1 and A2 and A2 and A3 are connected by a single bond, a double bond or a triple bond,
Y1 and Y2 are groups independently selected from any one of an imidazole group, an imidazoline group, a pyridyl group, a tertiary amino group, and a tertiary phosphine group, and each of A1 or A3 via an N atom or a P atom Is bound to. )   The method for producing an olefin according to any one of claims 1 to 7, wherein the metal component selected from a Group 9 metal and a Group 10 metal is Co, Rh, or Ni.   The method for producing an olefin according to any one of claims 1 to 8, wherein an acid anhydride having no β hydrogen atom is allowed to coexist in the decarbonylation reaction step.

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