阅读说明：本技术 三环[5.2.1.02,6]癸烷-2-羧酸酯的制造方法 (Method for producing tricyclo [5.2.1.02,6] decane-2-carboxylate ) 是由 品川诗织 北村光晴 长尾伸一 杉户健 于 2019-02-12 设计创作，主要内容包括：本发明的三环[5.2.1.0<Sup>2,6</Sup>]癸烷-2-羧酸酯的制造方法为在酸催化剂的存在下,使含有三环[5.2.1.0<Sup>2,6</Sup>]癸-3-烯的稀释液中的前述三环[5.2.1.0<Sup>2,6</Sup>]癸-3-烯与一氧化碳反应,接着与醇反应,制造三环[5.2.1.0<Sup>2,6</Sup>]癸烷-2-羧酸酯的方法,相对于前述三环[5.2.1.0<Sup>2,6</Sup>]癸-3-烯100质量份,前述稀释液含有三环[5.2.1.0<Sup>2,6</Sup>]癸烷异构体混合物100质量份以上,前述三环[5.2.1.0<Sup>2,6</Sup>]癸烷异构体混合物含有桥式-三环[5.2.1.0<Sup>2,6</Sup>]癸烷(TCD的Endo体)和挂式-三环[5.2.1.0<Sup>2,6</Sup>]癸烷(TCD的Exo体),其构成比(TCD的Endo体/TCD的Exo体)大于1.0。(Tricyclic [5.2.1.0 ] s of the invention 2,6 ]The decane-2-carboxylic ester is produced by reacting a compound containing tricyclo [5.2.1.0 ] in the presence of an acid catalyst 2,6 ]The aforementioned tricyclo [5.2.1.0 ] in dilutions of dec-3-ene 2,6 ]Dec-3-ene is reacted with carbon monoxide followed by reaction with an alcohol to produce a tricyclo [5.2.1.0 2,6 ]Method for preparing decane-2-carboxylic ester, relative to the aforementioned tricyclo [5.2.1.0 2,6 ]100 parts by mass of dec-3-ene, the diluent containing tricyclo [ 5.2.1.0% 2,6 ]Decane isomer mixture 100 parts by mass or more of the above tricyclo [5.2.1.0 2,6 ]Decane isomer mixture containing bridged tricyclo [5.2.1.0 2,6 ]Decane (Endo form of TCD) and exo-tricyclo [5.2.1.0 2,6 ]Decane (Exo form of TCD), whose composition ratio (Endo form of TCD/Exo form of TCD) is greater than 1.0.)

1. Tricyclic [5.2.1.0 ]^2,6]A process for producing decane-2-carboxylic acid ester, which comprises reacting a compound containing tricyclo [5.2.1.0 ] in the presence of an acid catalyst^2,6]Said tricyclo [5.2.1.0 ] in dilutions of dec-3-ene^2,6]Reaction of dec-3-ene with carbon monoxide followed by reaction with alcoholProducing tricyclo [5.2.1.0 ]^2,6]A process for the preparation of decane-2-carboxylic acid ester,

relative to the tricyclic [5.2.1.0 ]^2,6]100 parts by mass of deca-3-ene, wherein the diluent contains tricyclo [ 5.2.1.0%^2,6]The decane isomer mixture is 100 parts by mass or more,

said tricyclo [5.2.1.0^2,6]Decane isomer mixture containing bridged tricyclo [5.2.1.0^2,6]decane-Endo body and exo-tricyclo [5.2.1.0 ] of TCD^2,6]Decane, the Exo body of TCD, has a composition ratio of greater than 1.0, i.e., Endo body of TCD/Exo body of TCD.

2. Tricyclic [5.2.1.0 ] according to claim 1^2,6]A method for producing decane-2-carboxylic acid ester, wherein the amount of the acid catalyst used is based on the amount of the tricyclo [5.2.1.0 ]^2,6]The mole of the deca-3-ene is 4-25 times.

3. Tricyclic [5.2.1.0 ] according to claim 1 or 2^2,6]A method for producing decane-2-carboxylic acid ester, wherein said tricyclo [5.2.1.0 ] is contained^2,6]Said tricyclo [5.2.1.0 ] in dilutions of dec-3-ene^2,6]And when the deca-3-ene reacts with the carbon monoxide, the partial pressure of the carbon monoxide is 0.5-5 MPaG.

4. Tricyclic [5.2.1.0 ] according to any one of claims 1 to 3^2,6]A method for producing decane-2-carboxylic acid ester, wherein the alcohol contains ethanol.

5. Tricyclic [5.2.1.0 ] according to any one of claims 1 to 4^2,6]A process for producing decane-2-carboxylic acid ester, wherein the acid catalyst is a hydrogen fluoride-containing catalyst.

Technical Field

The invention relates to tricyclo [5.2.1.0 ]^2,6]A process for producing decane-2-carboxylic acid ester.

Background

Conventionally, as a method for producing a carboxylic ester from a monoolefin, a method is known in which an olefin is reacted with carbon monoxide and water in a strong acid by a Koch reaction, and the obtained carboxylic acid is esterified in an acid catalyst.

Tricyclic [5.2.1.0^2,6]Decane-2-carboxylic acid ester (hereinafter also referred to as TCDCE) is excellent in fragrance and is useful as a perfume or a perfume component. In the case of TCDCE production, tricyclo [5.2.1.0 ] obtained by hydrogenating dicyclopentadiene (hereinafter also referred to as DCPD) is used^2,6]Deca-3-ene (dihydrodicyclopentadiene, hereinafter also referred to as DHDCPD) forms a tricyclo [5.2.1.0 ] by reaction with carbon monoxide and water in a strong acid such as sulfuric acid^2,6]Decane-2-carboxylic acid (hereinafter also referred to as TCDC), and a method of esterifying the same. However, cycloolefins are easily polymerized in the carbonylation reaction and TCDC cannot be obtained in high yield.

Thus, patent document 1 describes a tricyclic [5.2.1.0 ] obtained by reacting DCPD with formic acid and then hydrogenating the reaction product^2,6]Deca-8-yl formate is contacted with an inorganic strong acid catalyst and simultaneously reacted to obtain tricyclo [5.2.1.0^2,6]A decane-2-carboxylic acid.

In order to utilize TCDC as a fragrance, esterification is required. Esterification of tertiary carboxylic acids is generally difficult, especially in the case of TCDC, the effect of steric hindrance is large. Thus, patent document 2 discloses a method of esterifying an alcohol after deriving an acid halide from TCDC. In patent documents 2 and 3, a dialkyl sulfate as an esterifying agent is allowed to act on TCDC to esterify the dialkyl sulfate.

Further, patent document 4 discloses a method for obtaining TCDCE in high yield by reacting DHDCPD, carbon monoxide and an alcohol in Hydrogen Fluoride (HF) by the reaction shown in scheme 1 below, and simultaneously performing a carbonylation reaction and an esterification reaction. This method is a promising method in industrial practice because it can obtain an ester in situ without separating a carboxylic acid and also recovery of HF (catalyst) is easy.

Scheme 1

Patent document 5 describes a process for producing TCDCE by reacting DHDCPD with carbon monoxide in the presence of HF to obtain an acyl fluoride, and then reacting the acyl fluoride with an alcohol.

Disclosure of Invention

Problems to be solved by the invention

However, the method described in patent document 1 is uneconomical because a large amount of strong acid such as sulfuric acid and HF is consumed.

When the method described in patent document 2 is used, an expensive halogenating agent is used in a large amount, which is uneconomical. In addition, the dialkyl sulfate used is expensive, and there is a problem that decomposition occurs due to water produced by the reaction.

When the method described in patent document 3 is used, the dialkyl sulfate used is expensive, and there is a problem that decomposition occurs due to water produced by the reaction.

When the method described in patent document 4 is used, it is necessary to obtain TCDCE under conditions of a low reaction temperature of-10 ℃ or lower and a molar ratio of HF to DHDCPD (HF/DHDCPD) of 15 times or more. Under these conditions, the reaction yield is low, and since a large amount of HF is used as a catalyst, the productivity is significantly lowered, and the method is industrially difficult to implement.

When the method described in patent document 5 is used, TCDCE cannot be obtained in a high yield, and there is room for improvement.

The present invention has been made in view of the above problems, and an object thereof is to provide a method for industrially easily and efficiently producing TCDCE, which is an excellent perfume, in a high yield.

Means for solving the problems

The present inventors have found that the reason why the reaction yield is reduced in the method described in patent document 4 is that the acid strength of HF is reduced by the ester and unreacted alcohol formed in the system.

Accordingly, the present inventors have conducted extensive studies on a method for improving the reaction yield by separating the steps of carbonylation and esterification and maintaining the acid strength of an acid catalyst such as a catalyst containing Hydrogen Fluoride (HF) (hereinafter also referred to as an HF catalyst), and as a result, have found that the use of a catalyst corresponding to tricyclo [5.2.1.0 ] in the carbonylation reaction^2,6]100 parts by mass of dec-3-ene containing tricyclo [5.2.1.0^2,6]Decane (hereinafter also referred to as TCD) isomer mixture containing bridge-tricyclo [5.2.1.0 ] in an amount of 100 parts by mass or more^2,6]Decane (Endo form of TCD) and exo-tricyclo [5.2.1.0^2,6]Decane (TCD Exo form) containing the above tricyclo [5.2.1.0 ] and having a composition ratio (TCD Endo form/TCD Exo form) of more than 1.0^2,6]The present inventors have completed the present invention by obtaining TCDCE which is useful as a perfume or a perfume component with excellent fragrance characteristics in an industrially simple and efficient manner in a high yield from a diluted solution of dec-3-ene.

That is, the present invention includes the following embodiments.

[1]Tricyclic [5.2.1.0 ]^2,6]A process for producing decane-2-carboxylic acid ester, which comprises reacting a compound containing tricyclo [5.2.1.0 ] in the presence of an acid catalyst^2,6]The aforementioned tricyclo [5.2.1.0 ] in dilutions of dec-3-ene^2,6]Dec-3-ene is reacted with carbon monoxide followed by reaction with an alcohol to produce a tricyclo [5.2.1.0^2,6]Method for preparing decane-2-carboxylic ester, relative to the aforementioned tricyclo [5.2.1.0^2,6]100 parts by mass of dec-3-ene, the diluent containing tricyclo [ 5.2.1.0%^2,6]100 parts by mass or more of decane isomer mixture, the tricyclo [5.2.1.0^2,6]Decane isomer mixture containing bridged tricyclo [5.2.1.0^2,6]decane-Endo body and exo-tricyclo [5.2.1.0 ] of TCD^2,6]Decane, the Exo body of TCD, has a composition ratio of greater than 1.0, i.e., Endo body of TCD/Exo body of TCD.

[2]According to [1]The tricyclic [5.2.1.0 ]^2,6]A method for producing decane-2-carboxylic acid ester, wherein the amount of the acid catalyst used is based on the amount of the tricyclo [5.2.1.0 ]^2,6]The mole of the deca-3-ene is 4-25 times.

[3]According to [1]Or [ 2]]The tricyclic [5.2.1.0 ]^2,6]A method for producing decane-2-carboxylic acid ester, wherein the tricyclo [5.2.1.0 ] is contained^2,6]The aforementioned tricyclo [5.2.1.0 ] in dilutions of dec-3-ene^2,6]When deca-3-ene reacts with the carbon monoxide, the partial pressure of the carbon monoxide is 0.5 to 5 MPaG.

[4]According to [1]～[3]The tricyclo [5.2.1.0 ] of any one of^2,6]A method for producing decane-2-carboxylic acid ester, wherein the alcohol contains ethanol.

[5]According to [1]～[4]The tricyclo [5.2.1.0 ] of any one of^2,6]A process for producing decane-2-carboxylic acid ester, wherein the acid catalyst is a hydrogen fluoride-containing catalyst.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the production method of the present invention, TCDCE useful as a perfume raw material can be industrially obtained easily and efficiently in high yield, and therefore, the method is extremely useful industrially.

Detailed Description

The following describes a mode for carrying out the present invention (hereinafter, simply referred to as "the present embodiment"). The following embodiments are merely examples for illustrating the present invention, and the present invention is not limited to the embodiments.

The method for producing TCDCE according to the present embodiment includes a step of carbonylating DHDCPD in a diluted solution containing DHDCPD with carbon monoxide to obtain a carbonyl compound, and a step of subsequently esterifying the carbonyl compound with an alcohol.

[ carbonylation of DHDCPD ]

The carbonyl reaction of DHDCPD is carried out in the presence of an acid catalyst under pressure of carbon monoxide, and DHDCPD in a diluted solution containing DHDCPD is carbonylated with carbon monoxide to obtain a carbonyl compound.

In this embodiment, a diluent containing DHDCPD supplied to the raw material to be carbonylated is obtained by diluting DHDCPD with a TCD isomer mixture. The diluent may contain an organic solvent as required. The diluent contains 100 parts by mass or more of the TCD isomer mixture, preferably 100 to 300 parts by mass, and more preferably 150 to 300 parts by mass, per 100 parts by mass of DHDCPD. When the amount of the TCD isomer mixture is less than this range, the effect of improving the yield is small, and when it is more than this range, the effect of improving the yield is small, the cost for separating TCD increases, and the volumetric efficiency of the apparatus may decrease.

DHDCPD as a raw material is usually produced by hydrogenating DCPD by a conventional method, and is not particularly limited.

TCD isomer mixture containing at least bridged tricyclo [ 5.2.1.0%^2,6]Decane (hereinafter also referred to as "Endo form of TCD") may contain a hanging-tricyclo [5.2.1.0^2,6]Decane (hereinafter also referred to as the Exo isomer of TCD). Embodiments of only the Endo isomer of TCD are also included in the TCD isomer mixtures of this embodiment. The composition ratio of Endo form of TCD to Exo form of TCD (Endo form of TCD/Exo form of TCD) is generally greater than 1.0, preferably greater than 1.5, more preferably only the Endo form of TCD (Endo form of TCD/Exo form of TCD 100/0).

Inhibition of DHDCPD polymerization in acid catalysts can be effectively obtained by using TCD isomer mixtures as dilution solvents. TCD is obtained by hydrogenating all 2 double bonds of DCPD, but since many compounds are produced in the carbonylation reaction of DHDCPD in an acid catalyst, TCD is also considered to be an equilibrium product in the present reaction system. Although it is assumed that the addition of TCD in advance in the present reaction system can suppress the by-production of TCD and the like during the carbonylation reaction, and it is considered that the yield of the desired TCDCE is improved.

The mixture of TCD isomers may be obtained by completely hydrogenating DCPD and used as long as the composition ratio of Endo form of TCD to Exo form of TCD satisfies the above range, or may be used by recovering by-products in the reaction.

The organic solvent is not particularly limited, and examples thereof include aliphatic hydrocarbon solvents such as n-hexane, n-heptane, cyclohexane, and isooctane. These can be used alone 1 or a combination of 2 or more. The organic solvent is not particularly limited, and is usually 10 to 150 parts by mass per 100 parts by mass of DHDCPD.

The acid contained in the acid catalyst is not particularly limited, and a known acid can be used. Specific examples thereof include halogen-containing acids such as hydrochloric acid (HCl), Hydrogen Fluoride (HF) and hydrogen bromide (HBr), inorganic acids such as sulfuric acid, p-toluenesulfonic acid, phosphoric acid, boron trifluoride-phosphoric acid and boron trifluoride hydrate, organic acids such as methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid, boron trifluoride-methanol, and mixtures thereof. These acid catalysts may be used alone in 1 or appropriately mixed with 2 or more.

Among them, the HF catalyst is more preferable from the viewpoint that the acyl fluoride can be obtained in a high yield and TCDCE can be efficiently obtained in a high yield. The reason why the yield of the acid fluoride is increased by using the HF catalyst is considered to be that the by-production of TCD during the carbonylation reaction can be effectively suppressed in addition to the polymerization inhibitory effect of DHDCPD as a raw material in HF.

In the present embodiment, a cuprous compound may be added as a catalyst component. When the reaction temperature is set to a relatively low temperature, the addition of the cuprous compound can improve the carbonylation reaction even under the above conditionsActive, TCDCE can be obtained with high selectivity and high yield. Examples of the cuprous compound include Cu₂O、CuOH、Cu₂S、Cu₂SO₃·H₂O and Cu₂Cl₂And the like. These cuprous compounds can be used alone in 1 kind or properly mixed with 2 or more kinds. The amount of the cuprous compound is not particularly limited, but is usually in the range of 0 to 10% by weight based on the total weight of the catalyst.

When the acid catalyst contains 2 or more catalyst components, it is preferable to produce the acid catalyst by mixing or dissolving the respective catalyst components.

The amount of the acid catalyst to be used is not particularly limited, but is preferably 4 to 25 times by mol, more preferably 5 to 15 times by mol, based on DHDCPD. When the molar ratio of the acid catalyst is too low, the carbonylation reaction does not proceed sufficiently, and side reactions such as non-homogenization and polymerization may occur, resulting in a decrease in yield. Further, even if the acid catalyst is used in an amount exceeding this range, the effect of improving the yield and the like is small, the cost for separating the acid catalyst increases, and the volumetric efficiency of the apparatus may decrease.

In the case of using an HF catalyst, the HF catalyst is preferably an essentially anhydrous HF catalyst.

The carbon monoxide may contain inert gases such as nitrogen and methane.

The partial pressure of carbon monoxide is not particularly limited, but is preferably 0.5 to 5MPaG, more preferably 1 to 3 MPaG. When the partial pressure of carbon monoxide is too low, the carbonylation reaction does not proceed sufficiently, and side reactions such as non-homogenization and polymerization may occur, resulting in a decrease in yield. Even if the partial pressure of carbon monoxide is higher than this range, the advantages in reaction cannot be obtained, which may cause problems such as the need for a high-pressure apparatus.

The temperature of the carbonylation reaction is not particularly limited, but is preferably 0 to 90 ℃ and more preferably 20 to 70 ℃. When the reaction temperature is lower than this range, the amount of by-produced polymerization product may increase. In addition, when the reaction temperature is high, the amount of by-produced polymerization products increases, and in this case, a large amount of TCDCE isomer is also by-produced, which may result in a decrease in yield.

The reaction system for the carbonylation is not particularly limited, and known methods such as a semi-continuous method and a continuous method can be used.

In the present embodiment, in order to remove the by-product generated in the carbonylation reaction, a step of removing the by-product may be provided separately after the carbonylation step.

In the case where an HF catalyst is used, if the isomer ratio of the acyl fluoride or the like is lower than a desired isomer ratio, an isomerization step may be separately provided after the carbonylation step. In this case, isomerization of the acyl fluoride may be carried out in an HF catalyst to adjust the isomer ratio.

[ esterification with alcohol ]

The TCDCE of the present embodiment is obtained by reaction with an alcohol after the aforementioned carbonylation. In this case, although the by-product produced in the carbonylation reaction may be once separated and then esterified with the alcohol again under the acid catalyst, a method of producing TCDCE by directly reacting the alcohol with the synthesis solution as it is to which the acid catalyst is added is generally employed. In this case, a predetermined amount of alcohol is preferably added to the synthesis solution. In the method of adding the synthetic liquid to an alcohol, an acid coexists in an excess amount of the alcohol, and thus water may be generated. If water is produced in the present system, the corrosiveness is significantly increased, which causes a process trouble, and therefore, this is not preferable.

In the present embodiment, the alcohol is not particularly limited, but lower alcohols having 1 to 3 carbon atoms such as methanol, ethanol, n-propanol, and isopropanol are preferable, and ethanol is preferable from the viewpoint of excellent aroma of TCDCE. These alcohols can be used alone in 1 or appropriate mixed 2 or more.

The alcohol is not particularly limited, but is preferably 1.0 to 1.5 times by mol with respect to DHDCPD. If the molar ratio of the alcohol is too low, the esterification reaction does not proceed sufficiently, and the yield may be lowered. Further, even if the alcohol is used in an amount higher than this range, the effect of improving the yield is small, the cost for separating the alcohol increases, and the volumetric efficiency of the apparatus may decrease.

The reaction temperature for esterification is not particularly limited, but is preferably 20 ℃ or lower. If the temperature is higher than 20 ℃, the decomposition of the ester and the dehydration reaction of the added alcohol occur, so that there is a possibility that the risk of water by-production in the system increases.

In the present embodiment, the acid catalyst is distilled off from the obtained esterification product, and then the esterification product is purified by a conventional method such as distillation to obtain TCDCE.