JP4957105B2 - Method for producing dihalogenononadien - Google Patents

Description

  The present invention relates to a novel process for producing dihalogenononadienes. More specifically, it is a method for producing a dihalogenononadien comprising a ring-opening cross metathesis reaction of 1,4-dihalogeno-2-butene and cyclopentene.

  In recent years, polyamide resins with high heat resistance and low water absorption have attracted attention as materials for lead-free solder. On the other hand, non-yellowing, weather-resistant and flexible polyurethane resins are attracting attention as materials for paints and adhesives. Each resin uses a monomer raw material (having a functional group such as an amino group or a hydroxyl group at the terminal) having 6 or more carbon atoms and having an aliphatic hydrocarbon having a chain structure in the skeleton.

  Dihalogenononadiene has a halogen group that can be easily converted into an amino group or a hydroxyl group at the end of the carbon chain, and therefore is expected as an intermediate for the monomer raw materials of the above polyamide and polyurethane resins. As a method for producing dihalogenononadienes, a production route by formylation with 1,6-heptadiine as a raw material, reduction with paraformaldehyde, reduction, and then chlorination is known (for example, see Non-Patent Document 1).

  However, it is necessary to use 1,6-heptadiyne, which is difficult to obtain in this manufacturing method, this 1,6-heptadiine is difficult to handle because it has two triple bonds, and liquid ammonia that is difficult to handle must be used for reduction. In addition, there are problems such as having to go through a multistage process.

P. Lennon et al. Am. Chem. Soc. 105, 1233-1124 (1983)

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a novel method for producing dihalogenononadienes which can be produced in a one-stage process using readily available raw materials.

  As a result of intensive studies to solve the above-described problems, the present inventors have found a novel method for producing dihalogenononadienes and have completed the present invention. That is, the present invention is characterized in that 1,4-dihalogeno-2-butene and cyclopentene represented by the following general formula (1) are subjected to a ring-opening cross-metathesis reaction in the presence of a metathesis reaction catalyst. This is a method for producing nonadiene.

（式中、Ｘはそれぞれ独立して塩素原子、臭素原子又はヨウ素原子を表す。）
以下、本発明について詳細に説明する。

(In the formula, each X independently represents a chlorine atom, a bromine atom or an iodine atom.)
Hereinafter, the present invention will be described in detail.

  The present invention is represented by the following general formula (2) in which 1,4-dihalogeno-2-butene and cyclopentene represented by the following general formula (1) are subjected to a ring-opening cross-metathesis reaction in the presence of a metathesis reaction catalyst. This is a method for producing dihalogenononadienes.

（式中、Ｘはそれぞれ独立して塩素原子、臭素原子又はヨウ素原子を表す。）

(In the formula, each X independently represents a chlorine atom, a bromine atom or an iodine atom.)

（式中、Ｘはそれぞれ独立して塩素原子、臭素原子又はヨウ素原子を示す。）
本発明の製造方法で製造される上記一般式（２）で表されるジハロゲノノナジエンとしては、例えば、１，９−ジクロロ−２，７−ノナジエン、１，９−ジブロモ−２，７−ノナジエン、１，９−ジヨード−２，７−ノナジエン、１−クロロ−９−ブロモ−２，７−ノナジエン、１−クロロ−９−ヨード−２，７−ノナジエン、１−ブロモ−９−ヨード−２，７−ノナジエン等があげられる。これらのうち、安定性が高いこと等から、一般式（２）におけるＸが両方とも塩素原子である１，９−ジクロロ−２，７−ノナジエン、一般式（２）におけるＸが両方とも臭素原子である１，９−ジブロモ−２，７−ノナジエン、一般式（２）におけるＸが両方ともヨウ素原子である１，９−ジヨード−２，７−ノナジエンが好ましい。特に安定性が高いこと及び原料の入手が容易であること等から、一般式（２）におけるＸが両方とも塩素原子である１，９−ジクロロ−２，７−ノナジエンがさらに好ましい。

(In the formula, each X independently represents a chlorine atom, a bromine atom or an iodine atom.)
Examples of the dihalogenononadiene represented by the general formula (2) produced by the production method of the present invention include 1,9-dichloro-2,7-nonadiene and 1,9-dibromo-2,7-. Nonadiene, 1,9-diiodo-2,7-nonadiene, 1-chloro-9-bromo-2,7-nonadiene, 1-chloro-9-iodo-2,7-nonadiene, 1-bromo-9-iodo- 2,7-nonadiene and the like. Among these, because of high stability, X in the general formula (2) is 1,9-dichloro-2,7-nonadiene, both of which are chlorine atoms, and both X in the general formula (2) are bromine atoms. 1,9-dibromo-2,7-nonadiene and 1,9-diiodo-2,7-nonadiene in which X in the general formula (2) are both iodine atoms are preferable. In particular, 1,9-dichloro-2,7-nonadiene, in which both X in the general formula (2) are chlorine atoms, is more preferable because of its high stability and easy availability of raw materials.

  The 1,4-dihalogeno-2-butene represented by the above general formula (1) used in the production method of the present invention is produced by the reaction of butadiene and chlorine, and the cyclopentene is produced by partial hydrogenation of cyclopentadiene. For example, 1,4-dichloro-2-butene, 1,4-dibromo-2-butene, 1,4-diiodo-2-butene, 1 -Chloro-4-bromo-2-butene, 1-chloro-4-iodo-2-butene, 1-bromo-4-iodo-2-butene and the like.

  Here, the ring-opening cross-metathesis reaction is a reaction that uses a cyclic olefin and an acyclic olefin as raw materials, the cyclic olefin opens by the metathesis reaction, and further causes a metathesis reaction with the acyclic olefin to give a coupling product. For example, “Fifth Edition Experimental Chemistry Course 18 Synthesis of Organic Compounds VI Organic Synthesis Using Metals” (edited by Chemical Society of Japan, Maruzen Co., Ltd.), pages 311 and 322.

  In the ring-opening cross metathesis reaction in the production method of the present invention, a metathesis reaction catalyst is usually used. The metathesis reaction catalyst is a transition metal compound of Groups 4 to 9 of the periodic table, and any catalyst that undergoes the ring-opening cross-metathesis reaction of 1,4-dihalogeno-2-butene and cyclopentene can be used. As the metathesis reaction catalyst, for example, (i) a catalyst by a combination of a transition metal compound and an alkylating agent or a Lewis acid that functions as a co-catalyst, (ii) a transition metal-carbene complex catalyst, (iii) a support Examples include solid catalysts carrying transition metal compounds. For example, “Fifth Edition Experimental Chemistry Lecture 18 Synthesis of Organic Compounds VI Organic Synthesis Using Metals” (edited by Chemical Society of Japan, Maruzen Co., Ltd.) pp. 313 to 314 Page, "Catalyst Course Vol. 8 (Industrial Catalysis Reaction 2) Industrial Catalysis Reaction I" (Catalyst Society, Kodansha Scientific), pages 70-71 The catalyst can be used that is.

The transition metal compound in the catalyst (i) is not particularly limited as long as it retains high catalytic activity and stability. For example, titanium compounds such as TiCl ₄ and TiBr ₄ ; VOCl ₃ , vanadium compounds such as VOBr ₃ ; niobium compounds such as NbBr ₅ , NbCl ₅ and Nb (OEt) ₅ ; tantalum compounds such as TaBr ₅ , TaCl ₅ , Ta (OMe) ₅ and Ta (OBu) ₅ ; MoBr ₂ , MoBr ₃ , MoBr ₄ , MoCl ₄ , MoCl ₅ , MoF ₄ , MoOCl ₄ , MoOF _{4 and} other molybdenum compounds; WBr ₂ , WCl ₂ , WBr ₄ , WCl ₄ , WCl ₅ , WCl ₆ , WF ₄ , WF ₄ , WF _{4 WI 2, WOBr 4, WOCl 4} , WOF 4, WCl 4 (OC 6 H 4 Cl 2) 2, W ( _O) tungsten compounds such as _{6; CH 3 ReO 3, ReCl} 5, ReCl (CO) rhenium compounds such as _{5, RuBr 3, RuCl 3,} Ru 3 (CO) ruthenium compounds such as _12; RhCl _3, etc. Rhodium compounds; iridium compounds such as IrCl _{3 and the} like.

  The alkylating agent or Lewis acid that functions as a co-catalyst in the catalyst (i) is not particularly limited as long as it can exhibit high catalytic activity. For example, trimethylaluminum, triethylaluminum, Isobutylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum, tribenzylaluminum, diethylaluminum monochloride, di-n-butylaluminum monochloride, diethylaluminum monohydride, ethylaluminum sesquichloride, ethylaluminum dichloride, methylaluminoxane , Organoaluminum compounds such as isobutylaluminoxane; tetramethyltin, diethyldimethyltin, tetraethyltin, dibutyldiethyltin, teto Butyltin, tetraoctyltin, trioctyltin fluoride, trioctyltin chloride, trioctyltin bromide, trioctyltin iodide, dibutyltin difluoride, dibutyltin dichloride, dibutyltin dibromide, dibutyltin diiodide, butyltin trifluoride, Organotin compounds such as butyltin trichloride and butyltin tribromide; Organolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium and phenyllithium; methylmagnesium iodide, ethylmagnesium bromide, methylmagnesium Organomagnesium compounds such as bromide, n-propylmagnesium bromide, t-butylmagnesium chloride, arylmagnesium chloride; Organic zinc compounds such as tilzinc; Organic sodium compounds such as cyclopentyl sodium; trimethylboron, triethylboron, tri-n-butylboron, triphenylboron, tris (perfluorophenyl) boron, N, N-dimethylanilinium And organic boron compounds such as tetrakis (perfluorophenyl) borate and trityltetrakis (perfluorophenyl) borate; and organic antimony compounds such as triphenylantimony.

  Furthermore, alcohols such as methanol and ethanol, phenols and the like may be added as a third component to the extent that the ring-opening cross-metathesis reaction is not affected.

The transition metal (ii) - The carbene complex catalyst is not particularly limited as long as it can exhibit a high catalytic activity, for _{^{example, W (N-2,6-Pr}} i 2 C 6 H 3 ^{_{) (CHBu t) (OBu t}} ) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe 2 CF 3) 2, W (N-2,6-Pr i 2 ^{_{C 6 H 3) (CHBu t}} ) (OCMe (CF 3) 2) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OBu t) 2, W (N- ^{_{2,6-Pr i 2 C 6 H}} 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe (CF ₃ ) ₂ ) Tungsten-carbene complexes such as ₂ ; Mo (N-2) ^{_{, 6-Pr i 2 C 6}} H 3) (CHBu t) (OBu t) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe 2 CF 3) 2, Mo ^{_{(N-2,6-Pr i 2}} C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) ^{_{(OBu t) 2, Mo (}} N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2, Mo (N-2,6-Pr i 2 C 6 H 3 _{) (CHCMe 2 Ph) (OCMe} (CF 3) 2) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (BIPHEN), Mo (N-2,6-Pr ^{_{i 2 C 6 H 3) (}} CHCMe 2 Ph) (BINO) (THF) , etc. Molybdenum - carbene ^{complexes, Re (CBu t) (CHBu} t) (O-2,6-Pr i 2 C 6 H 3) 2, Re (CBu t) (CHBu t) (O-2-Bu t C 6 H ₄ ) ₂ , Re (CBu ^t ) (CHBu ^t ) (OCMe ₂ CF ₃ ) ₂ , Re (CBu ^t ) (CHBu ^t ) (OCMe (CF ₃ ) ₂ ) ₂ , Re (CBu ^t ) (CHBu ^t ) Rhenium-carbene complexes such as (O-2,6-Me ₂ C ₆ H ₃ ) ₂ ; benzylidene (1,3-dimesityl-2-imidazolidineylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3 -Dimesityl-2-imidazolidineylidene) (3-methyl-2-buteneylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1 3-Dimesityl-2-octahydrobenzimidazolylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-bis (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride , Benzylidene (1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4) , 5-Tetrahydro-1H-1,2,4-triazole-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphos ) Ruthenium dichloride, benzylidene (1,3-dimesityl-2-imidazolidine ylidene) pyridine ruthenium dichloride, benzylidene bis (1,3-dicyclohexyl-2-imidazolidine ylidene) ruthenium dichloride, benzylidene bis (1,3 -Diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride, (1,3-dimesitylmimidazolidine-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butylvinylidene) (1, 3-diisopropyl-4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylidenerutheniumdi Chloride, benzylidene-bis (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-2-imidazolidineylidene) (o-isopropoxyphenylmethylene) ruthenium dichloride, tricyclohexylphosphine (o-isopropoxyphenylmethylene) ruthenium Examples thereof include ruthenium-carbene complexes such as dichloride, (3-methyl-2-buteneylidene) bis (tricyclopentylphosphine) ruthenium dichloride, and (3-methyl-2-buteneylidene) bis (tricyclohexylphosphine) ruthenium dichloride.

Here, in the above formula, the Pr ⁱ isopropyl group, a Bu ^t is tert- butyl group, Me is a a methyl group, Ph refers to a phenyl group, BIPHEN is 5,5 ', 6,6'-tetramethyl −3,3′-di-tert-butyl-1,1′-biphenyl-2,2′-dioxy group, BINO represents 1,1′-dinaphthyl-2,2′-dioxy group, and THF represents tetrahydrofuran. Respectively.

The transition metal compound in the solid catalyst (iii) is not particularly limited as long as it has high stability. For example, V ₂ O ₅ , Nb ₂ O ₅ , Ta ₂ O ₅ , MoO ₂ , oxides such as MoO ₃ , WO ₃ , Re ₂ O ₇ , ReO ₃ , CH ₃ ReO ₇ , RuO ₂ , Rh ₂ O ₃ , Ir ₂ O ₃ ; MoS ₃ , MoS ₂ , WS ₂ , Re ₂ sulfides such as S _7, and the like. Further, the carrier is not particularly limited. For example, Al ₂ O ₃ , SiO ₂ , TiO ₂ , MgO, ZrO ₂ , Ta ₂ O ₅ , Nb ₂ O ₅ , WO ₃ , SnO ₂ , SiO _2- Al ₂ O _{3 and the} like.

  These metathesis reaction catalysts can be used alone or in combination of two or more. Of these, a transition metal-carbene complex catalyst is preferably used because of its high catalytic activity and excellent handling safety, and ruthenium-carbene complexes are more preferably used.

  The amount of the metathesis reaction catalyst used is not particularly limited, and the ring-opening cross-metathesis reaction can be efficiently performed. Therefore, 0.000001 to 10.0 mol with respect to 1 mol of 1,4-dihalogeno-2-butene as a raw material. %, Preferably 0.00001 to 5.0 mol%, more preferably 0.0001 to 1.0 mol%.

  The charging ratio of 1,4-dihalogeno-2-butene and cyclopentene in the ring-opening cross-metathesis reaction of the present invention is not particularly limited, but since the catalytic activity is increased, 1 mol of 1,4-dihalogeno-2-butene is added. On the other hand, the amount of cyclopentene is 0.001 to 200 mol, preferably 0.01 to 100 mol, more preferably 0.05 to 50 mol. Here, 1,4-dihalogeno-2-butene has a trans isomer and a cis isomer, but there is no significant difference as a raw material in the production of the dihalogenononadiene of the present invention. It can be used as.

  Here, the ring-opening cross metathesis reaction of 1,4-dihalogeno-2-butene and cyclopentene represented by the general formula (1) can be performed in a solvent or without a solvent. Examples of such a solvent include, but are not limited to, aliphatic hydrocarbons such as butane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; Cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cyclooctane, decahydronaphthalene and other alicyclic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; ethyl ether, tetrahydrofuran, dioxane, diglyme, triglyme, etc. Ethers such as acetone, methyl ethyl ketone, cyclohexanone, etc .; esters such as methyl acetate, ethyl acetate; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, etc. It is. Further, cyclopentene or 1,4-dihalogeno-2-butene, which is one of the raw materials, can be used as a solvent. These solvents can be used alone or in combination of two or more.

The temperature in the ring-opening cross metathesis reaction is not particularly limited, and is, for example, −50 to 250 ° C., preferably −20 to 150 ° C. The reaction pressure is not particularly limited, but is usually 0.01 to 30 kg / cm ² in absolute pressure, preferably 0.1 to 3 kg / cm ² . The reaction time depends on the temperature and the substrate concentration of the raw material and cannot be determined in general, but is usually 5 minutes to 500 hours. The atmosphere during the reaction is not particularly limited, but it is desirable to perform the reaction while avoiding air and moisture. For example, the reaction is preferably performed in an inert gas atmosphere such as nitrogen, argon, or helium. Moreover, it is preferable that the raw material and the solvent are sufficiently dried.

  In the ring-opening cross-metathesis reaction of the present invention, the reaction method is not particularly limited, and a batch type in which raw materials 1,4-dihalogeno-2-butene, cyclopentene, a catalyst and, if necessary, a solvent are charged into a reactor at once. 1,4-dihalogeno-2-butene as raw materials, cyclopentene, and if necessary, a solvent or the like is continuously supplied, and unreacted raw materials and a fixed bed or a suspension bed in which a reaction solution is continuously extracted Any of the equations can be implemented. The reaction state is not particularly limited, and the reaction can be performed in a liquid phase or a gas phase, and further in a gas-liquid mixed state.

  Since the dihalogenononadiene of the present invention has functional groups that can be easily converted into amino groups, hydroxyl groups, etc. at both ends of the chain hydrocarbons, it is an intermediate between monomer raw materials and raw materials for pharmaceutical and agrochemicals of polyamide resins and polyurethane resins. It can be suitably used as a body.

  The present invention provides an efficient production method of dihalogenononadiene useful as an intermediate for a monomer raw material of polyamide or polyurethane resin and a raw material for medical and agricultural chemicals, and is very useful industrially.

  Examples of the present invention are shown below, but the present invention is not limited to these examples.

  The measurement methods used in the examples are shown below.

<Gas chromatographic analysis>
Tetradecane was added as an internal standard to the reaction solution, and 0.4 μl of the reaction solution was injected into a gas chromatograph (GC-1700 manufactured by Shimadzu Corporation) equipped with a TC-1 column (trade name) manufactured by GL Sciences, and analysis was performed.

^<1 H- nuclear magnetic resonance (hereinafter, referred to as NMR) measurement>
¹ H-NMR measurement was performed using a nuclear magnetic resonance apparatus (trade name JNMGX400, manufactured by JEOL Ltd.).

<GC-MS measurement>
Measurement was performed using a gas chromatograph mass spectrometer (GC part; manufactured by Hewlett-Packard, trade name HP6890, MS part; manufactured by JEOL, trade name JMS-700).

Example 1
(1,3 dimesityl-2-imidazolidine ylidene) (o-isopropoxyphenylmethylene) ruthenium dichloride (Aldrich, trade name ^{Hoveyda-Grubbs} Catalyst 2 nd Generation) and 6.8 mg (10.9Myumol) and dichloromethane 20ml Place in a 50 ml Schlenk tube. Next, 2.11 g (31.0 mmol) of cyclopentene was added, and further 1.50 g (12.0 mmol) of 1,4-dichloro-2-butene (cis isomer: trans isomer = 36: 64) was added. The Schlenk tube was heated to 40 ° C. in an oil bath and stirred for 3 hours to perform a ring-opening cross metathesis reaction. After completion of the reaction, the Schlenk tube was cooled to obtain a reaction solution.

  The reaction solution was placed in a column chromatograph packed with silica gel (trade name Wakogel, manufactured by Wako Pure Chemical Industries, Ltd.) and developed with 300 ml of a mixture of hexane and dichloromethane (volume ratio 2: 1) to remove the catalyst from the reaction solution. The obtained liquid was subjected to vacuum distillation (40 ° C., 4 mmHg to separate a colorless transparent liquid).

¹ H-NMR and GC-MS measurement of the obtained liquid was performed.

^{As a result of 1} H-NMR (CDCl ₃ solvent) measurement, a peak based on one methylene group in the middle of the three methylene groups in the center of the carbon chain at δ 1.46 to 1.55 ppm (m), δ 2.00 to 2.10 ppm (m) is the peak based on two methylene groups adjacent to the double bond among the three methylene groups in the center of the carbon chain, and δ 4.06 ppm (d) is the carbon-terminated terminal adjacent to the chlorine atom. A peak based on four hydrogen atoms at the double bond site was observed at δ 5.60-5.75 ppm (m), a peak based on two methylene groups.

  As a result of GC-MS measurement, molecular ion peaks were confirmed at m / e 192 and 194 as main components.

  From these results, this liquid was identified as 1,9-dichloro-2,7-nonadiene.

  On the other hand, as a result of analyzing the reaction solution by gas chromatography, the conversion rate of 1,4-dichloro-2-butene was 55.0%, and the selectivity of 1,9-dichloro-2,7-nonadiene was 60.0%. there were. These are shown in Table 1.

実施例２〜４
表１に示すメタセシス反応触媒、１，４−ジクロロ−２−ブテン及び反応条件を用いた以外は、実施例１と同様にして開環クロスメタセシス反応を行い、反応液を得た。

Examples 2-4
A ring-opening cross-metathesis reaction was performed in the same manner as in Example 1 except that the metathesis reaction catalyst, 1,4-dichloro-2-butene and reaction conditions shown in Table 1 were used to obtain a reaction solution.

  As a result of analyzing the reaction liquid by gas chromatography, it can be identified as 1,9-dichloro-2,7-nonadiene, the conversion rate of 1,4-dichloro-2-butene, 1,9-dichloro-2,7- The selectivity for nonadiene was as shown in Table 1, respectively.

Example 5
Ring-opening cross metathesis in the same manner as in Example 1 except that 2.57 g (12.0 mmol) of 1,4-dibromo-2-butene (trans form) was used instead of 1,4-dichloro-2-butene. Reaction was performed and the reaction liquid was obtained.

  The reaction solution was placed in a column chromatograph packed with silica gel (trade name Wakogel, manufactured by Wako Pure Chemical Industries, Ltd.) and developed with 300 ml of a mixture of hexane and dichloromethane (volume ratio 2: 1) to remove the catalyst from the reaction solution. The obtained liquid was subjected to vacuum distillation (40 ° C., 4 mmHg to separate a colorless transparent liquid).

¹ H-NMR and GC-MS measurement of the obtained liquid was performed.

^{As a result of 1} H-NMR (CDCl ₃ solvent) measurement, a peak based on one methylene group in the middle of the three methylene groups in the middle of the carbon chain at δ 1.5.0 to 1.60 ppm (m), δ 2. A peak based on two methylene groups adjacent to a double bond among three methylene groups at the center of the carbon chain at 02 to 2.13 ppm (m), a carbon chain adjacent to a bromine atom at δ 3.95 ppm (d) A peak based on the two methylene groups at the end and a peak based on four hydrogen atoms at the double bond site were observed at δ 5.64 to 5.88 ppm (m).

  As a result of GC-MS measurement, molecular ion peaks were confirmed at m / e 280 and 282 as main components.

  From these results, the main component of this liquid was identified as 1,9-dibromo-2,7-nonadiene.

  On the other hand, as a result of analyzing the reaction solution by gas chromatography, the conversion rate of 1,4-dibromo-2-butene was 42.5%, and the selectivity of 1,9-dibromo-2,7-nonadiene was 59.3%. there were.

Comparative Example A ring-opening cross-metathesis reaction was performed in the same manner as in Example 1 except that cyclopentene was not used, to obtain a reaction solution.

As a result of analyzing the reaction solution by gas chromatography, 1,9-dichloro-2,7-nonadiene was not obtained. The results are shown in Table 1.

Claims (4)

1,4-dihalogeno-2-butene represented by the following general formula (1) and cyclopentene are subjected to a ring-opening cross-metathesis reaction in the presence of a metathesis reaction catalyst, and represented by the following general formula (2) Process for producing dihalogenononadienes.

(In the formula, each X independently represents a chlorine atom, a bromine atom or an iodine atom.)

(In the formula, each X independently represents a chlorine atom, a bromine atom or an iodine atom.) 2. The method for producing dihalogenononadiene according to claim 1, wherein both X in the general formula (2) are a chlorine atom, a bromine atom or an iodine atom. The method for producing a dihalogenononadiene according to claim 1 or 2, wherein the metathesis reaction catalyst is a transition metal-carbene complex catalyst. The method for producing a dihalogenononadiene according to any one of claims 1 to 3, wherein the transition metal-carbene complex catalyst is a ruthenium-carbene complex.