JP2005089401A - Method for producing refined tricyclo[5.2.1.02,6]decane-2-carboxylic acid ethyl ester - Google Patents
Method for producing refined tricyclo[5.2.1.02,6]decane-2-carboxylic acid ethyl ester Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003377 acid catalyst Substances 0.000 claims abstract description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 12
- GVRWIAHBVAYKIZ-UHFFFAOYSA-N dec-3-ene Chemical compound CCCCCCC=CCC GVRWIAHBVAYKIZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012043 crude product Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- KGKUZGKMSKOEOK-UHFFFAOYSA-N ethyl 2-methyldecanoate Chemical compound CCCCCCCCC(C)C(=O)OCC KGKUZGKMSKOEOK-UHFFFAOYSA-N 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 32
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract description 30
- 239000003205 fragrance Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000004821 distillation Methods 0.000 description 11
- -1 aldehyde compound Chemical class 0.000 description 10
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 9
- 239000004927 clay Substances 0.000 description 9
- HANKSFAYJLDDKP-UHFFFAOYSA-N dihydrodicyclopentadiene Chemical compound C12CC=CC2C2CCC1C2 HANKSFAYJLDDKP-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000001577 simple distillation Methods 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000005810 carbonylation reaction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- SAOSCTYRONNFTC-UHFFFAOYSA-N 2-methyl-decanoic acid Chemical compound CCCCCCCCC(C)C(O)=O SAOSCTYRONNFTC-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 101100465000 Mus musculus Prag1 gene Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ZKDKHHRIOHJUSY-UHFFFAOYSA-N decan-3-yl formate Chemical compound CCCCCCCC(CC)OC=O ZKDKHHRIOHJUSY-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical group CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、トリシクロ［５．２．１．０2,6］デカン−２−カルボン酸エチルエステルの粗精製物から、微量の不純物アルデヒドなどを効果的に除去し、香料又は香料成分として好適な精製トリシクロ［５．２．１．０2,6］デカン−２−カルボン酸エチルエステルを工業的に有利に製造する方法に関する。 The present invention effectively removes trace amounts of impurity aldehydes from a crude product of tricyclo [5.2.1.0 2,6 ] decane-2-carboxylic acid ethyl ester, and is suitable as a fragrance or a fragrance component. The present invention relates to a method for industrially advantageously producing purified tricyclo [5.2.1.0 2,6 ] decane-2-carboxylic acid ethyl ester.
トリシクロ［５．２．１．０2,6］デカン−２−カルボン酸のエステル類は、優れた香気性を有し、かつ熱安定性が良く長期にわたって着色、変質等の変化を受けず、更に酸、アルカリに対する安定性も非常に高いことが知られている（例えば、特許文献１参照）。また、この特許文献１には、特にトリシクロ［５．２．１．０2,6］デカン−２−カルボン酸のエチルエステルが香りが強く、好ましいことが記載されている。
このトリシクロ［５．２．１．０2,6］デカン−２−カルボン酸エチルエステル（以下、ＴＣＤＥと称すことがある。）の製法に関しては、コッホ反応のように、ジシクロペンタジエン（以下、ＤＣＰＤと称すことがある。）を水素化して得られるトリシクロ［５．２．１．０2,6］デカ−３−エン（ジヒドロジシクロペンタジエン、以下、ＤＨＤＣＰＤと称すことがある。）を硫酸等の強酸中で一酸化炭素と水との反応によりトリシクロ［５．２．１．０2,6］デカン−２−カルボン酸（以下、ＴＣＤＣと称すことがある。）とし、これをエチルエステル化する方法、ＤＣＰＤとギ酸を反応させた後水添して得られるトリシクロ［５．２．１．０2,6］デク−８−イルホルメートと無機強酸性触媒を接触させながら反応させ（例えば、特許文献２参照）、これをエチルエステル化する方法（例えば、特許文献１、特許文献３参照）、またＨＦ中でＤＨＤＣＰＤと一酸化炭素及びエタノールを反応させる方法（例えば、特許文献４参照）等が知られている。
Esters of tricyclo [5.2.1.0 2,6 ] decane-2-carboxylic acid have excellent aroma and heat stability and are not subject to changes such as coloring and alteration over a long period of time. Furthermore, it is known that the stability to acid and alkali is very high (for example, see Patent Document 1). In addition, Patent Document 1 describes that tricyclo [5.2.1.0 2,6 ] decane-2-carboxylic acid ethyl ester is particularly strong and preferable.
Regarding the production method of this tricyclo [5.2.1.0 2,6 ] decane-2-carboxylic acid ethyl ester (hereinafter sometimes referred to as TCDE), as in the Koch reaction, dicyclopentadiene (hereinafter, Tricyclo [5.2.1.0 2,6 ] dec-3-ene (dihydrodicyclopentadiene, hereinafter sometimes referred to as DHDCPD) obtained by hydrogenating DCPD). To a tricyclo [5.2.1.0 2,6 ] decane-2-carboxylic acid (hereinafter sometimes referred to as TCDC) by reacting carbon monoxide with water in a strong acid such as ethyl ester. The reaction of DCPD and formic acid followed by hydrogenation followed by reaction while bringing tricyclo [5.2.1.0 2,6 ] dec-8-ylformate into contact with a strongly acidic acidic catalyst (for example, Patent text 2), a method of esterifying this (for example, see Patent Documents 1 and 3), a method of reacting DHDCPD with carbon monoxide and ethanol in HF (for example, see Patent Document 4), etc. It has been.
このうち、ＨＦ中でＤＨＤＣＰＤと一酸化炭素及びエタノールを反応させる方法は、高収率にＴＣＤＥを得ることができ、しかも触媒であるＨＦの回収も容易なことから工業的に実施する上で有望な方法である。
しかしながら、ＨＦ中でＤＨＤＣＰＤ、一酸化炭素、及びエタノールを反応させて得られたＴＣＤＥ粗精製物中には、目的生成物以外に微量の不純物が混入することが判明した。この微量の不純物は、分子量がＴＣＤＣより１６だけ小さいこと、および質量分析のフラグメントパターンから、トリシクロ［５．２．１．０2,6］デカン骨格を有するアルデヒド化合物（以下、不純物アルデヒドと称す。）と同定された。
ＴＣＤＥを香料として使用するにあたっては、この不純物アルデヒドの香気が悪影響を及ぼすことから、この含有量を０．５質量％以下とすることが望まれている。しかし、この不純物アルデヒドは、沸点が目的生成物であるＴＣＤＥと非常に近いため、蒸留によりこれらを分離しようとした場合、分離効率の高い蒸留塔を用い、高い還流比をかけて蒸留を行う必要があり、したがって、精製工程における歩留まりと生産性の低下を免れないという問題があった。
Of these, the method of reacting DHDCPD with carbon monoxide and ethanol in HF is promising for industrial implementation because TCDE can be obtained in high yield and HF as a catalyst can be easily recovered. It is a simple method.
However, it was found that a trace amount of impurities other than the target product is mixed in the TCDE crude product obtained by reacting DHDCPD, carbon monoxide, and ethanol in HF. This trace amount of impurities is an aldehyde compound having a tricyclo [5.2.1.0 2,6 ] decane skeleton (hereinafter referred to as an impurity aldehyde) because of its molecular weight 16 smaller than that of TCDC and the fragment pattern of mass spectrometry. ).
When TCDE is used as a fragrance, the odor of the impurity aldehyde has an adverse effect, so that the content is desired to be 0.5% by mass or less. However, since the impurity aldehyde has a boiling point very close to that of the target product, TCDE, when it is attempted to separate them by distillation, it is necessary to perform distillation using a distillation column with high separation efficiency and a high reflux ratio. Therefore, there is a problem that the yield and productivity in the purification process are unavoidable.
本発明は、このような状況下で、ＴＣＤＥ粗精製物から、微量の不純物アルデヒドなどを効果的に除去し、香料又は香料成分として好適な精製ＴＣＤＥを工業的に有利に製造する方法を提供することを目的とするものである。 Under such circumstances, the present invention provides a method for industrially advantageously producing purified TCDE suitable as a fragrance or a fragrance component by effectively removing trace amounts of impurity aldehydes from the TCDE crude product under such circumstances. It is for the purpose.
本発明者らは、上記課題を解決するために鋭意検討を行った結果、ＴＣＤＥ粗精製物に酸触媒と特定のグリコールを添加し、加熱下で処理を行うことにより、不純物アルデヒドがＴＣＤＥより高沸点のアセタール化合物に変化し、また生成したアセタール化合物は簡単な蒸留操作で分離できることを見出した。本発明は、かかる知見に基づいて完成したものである。
すなわち、本発明は、
（１）ＨＦの存在下、トリシクロ［５．２．１．０2,6］デカ−３−エンを一酸化炭素及びエタノールと反応させてトリシクロ［５．２．１．０2,6］デカン−２−カルボン酸エチルエステルを製造する方法において、トリシクロ［５．２．１．０2,6］デカン−２−カルボン酸エチルエステルの粗精製物を、酸触媒の存在下に一般式（Ｉ）
As a result of intensive studies to solve the above-mentioned problems, the present inventors have added an acid catalyst and a specific glycol to the TCDE crude product, and processed under heating, so that the impurity aldehyde is higher than that of TCDE. It turned out that it changed to the acetal compound of boiling point, and the produced acetal compound was separable by simple distillation operation. The present invention has been completed based on such findings.
That is, the present invention
(1) Tricyclo [5.2.1.0 2,6 ] dec-3-ene is reacted with carbon monoxide and ethanol in the presence of HF to obtain tricyclo [5.2.1.0 2,6 ] decane. In the process for producing -2-carboxylic acid ethyl ester, a crude product of tricyclo [5.2.1.0 2,6 ] decane-2-carboxylic acid ethyl ester is represented by the general formula (I) in the presence of an acid catalyst. )
（式中、Ｒ1〜Ｒ6は、それぞれ水素原子、メチル基又はエチル基を示し、それらはたがいに同一でも異なっていてもよく、ｎは０又は１を示す。）
で表されるグリコールと接触処理させたのち、蒸留することを特徴とする精製トリシクロ［５．２．１．０2,6］デカン−２−カルボン酸エチルエステルの製造方法、
（２）トリシクロ［５．２．１．０2,6］デカン−２−カルボン酸エチルエステルの粗精製物を、酸触媒の存在下に前記グリコールと接触処理させるに際し、該接触処理を１００〜１８０℃の範囲の温度で実施する上記（１）の方法、
を提供するものである。
(Wherein, R 1 to R 6 are each a hydrogen atom, a methyl group or an ethyl group and may be the same with or different from each other, n represents 0 or 1.)
A process for producing purified tricyclo [5.2.1.0 2,6 ] decane-2-carboxylic acid ethyl ester, which is subjected to contact treatment with glycol represented by
(2) When the crude product of tricyclo [5.2.1.0 2,6 ] decane-2-carboxylic acid ethyl ester is contact-treated with the glycol in the presence of an acid catalyst, The method of (1) above carried out at a temperature in the range of 180 ° C .;
Is to provide.
本発明の方法によれば、ＴＣＤＥ粗精製物に特定の処理を施すことにより、分離効率の高い蒸留塔を用いることなく、通常の蒸留処理で不純物アルデヒドなどを効果的に除去することができ、香料又は香料成分として好適な精製ＴＣＤＥを工業的に有利に製造することができる。 According to the method of the present invention, by subjecting the TCDE crude product to a specific treatment, impurity aldehydes and the like can be effectively removed by ordinary distillation treatment without using a distillation column with high separation efficiency, Purified TCDE suitable as a fragrance or a fragrance component can be produced industrially advantageously.
本発明において用いられるＴＣＤＥ粗精製物は、ＨＦの存在下、ＤＨＤＣＰＤを一酸化炭素及びエタノールと反応させた後、ＨＦを留去させて得ることができる。この際、一酸化炭素及びエタノールを同時に供給してカルボニル化反応とエステル化反応を同時に行ってもよいし、一酸化炭素を供給してカルボニル化反応をさせた後にエタノールを供給してエステル化反応を行ってもよい。得られた粗エステルは、そのまま酸触媒下でグリコールと接触処理を行うこともできるが、簡単な蒸留操作にて低沸分および高沸分を除いた後に処理してもよい。
本発明においては、このようにして得られたＴＣＤＥ粗精製物を、酸触媒の存在下にグリコールと接触処理させたのち、蒸留することにより、精製ＴＣＤＥを製造する。
The TCDE crude product used in the present invention can be obtained by reacting DHDCPD with carbon monoxide and ethanol in the presence of HF and then distilling off HF. At this time, carbon monoxide and ethanol may be supplied simultaneously to perform the carbonylation reaction and the esterification reaction at the same time. Alternatively, carbon monoxide may be supplied to cause the carbonylation reaction, and then ethanol may be supplied to perform the esterification reaction. May be performed. The obtained crude ester can be subjected to contact treatment with glycol in the presence of an acid catalyst, but may be treated after removing low and high boiling points by a simple distillation operation.
In the present invention, the TCDE crude product thus obtained is subjected to contact treatment with glycol in the presence of an acid catalyst and then distilled to produce purified TCDE.
前記酸触媒としては、硫酸等の液体の酸、活性白土、酸性白土、ホージヤサイト、Ｘ型ゼオライト、Ｙ型ゼオライト、モルデナイト、シリカアルミナ、強酸性イオン交換樹脂等の固体酸が挙げられる。これらは一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。この酸触媒の添加量については、特に限定されないが、通常ＴＣＤＥ粗精製物に対し、０．１〜１０．０質量％の範囲である。該酸触媒を０．１質量％以上添加することにより、不純物アルデヒドを十分に低減することができ、簡単な蒸留操作のみで、製品中の不純物アルデヒドの含有量を０．５質量％以下にすることが可能となる。また、ＴＣＤＥと酸触媒の分離コストなどの面から、酸触媒の添加量は１０．０質量％以下が有利である。該酸触媒の好ましい添加量は０．５〜５．０質量％の範囲である。
一方、グリコールとしては、一般式（Ｉ）
Examples of the acid catalyst include liquid acids such as sulfuric acid, and solid acids such as activated clay, acid clay, faujasite, X-type zeolite, Y-type zeolite, mordenite, silica alumina, and strongly acidic ion exchange resin. These may be used individually by 1 type, and may be used in combination of 2 or more types. The addition amount of the acid catalyst is not particularly limited, but is usually in the range of 0.1 to 10.0% by mass with respect to the TCDE crude product. By adding the acid catalyst in an amount of 0.1% by mass or more, the impurity aldehyde can be sufficiently reduced, and the content of the impurity aldehyde in the product is reduced to 0.5% by mass or less by only a simple distillation operation. It becomes possible. Further, from the viewpoint of separation cost of TCDE and acid catalyst, the addition amount of the acid catalyst is advantageously 10.0% by mass or less. A preferable addition amount of the acid catalyst is in the range of 0.5 to 5.0% by mass.
On the other hand, as the glycol, the general formula (I)
で表されるグリコールを用いることができる。
前記一般式（Ｉ）において、Ｒ1〜Ｒ6は、それぞれ水素原子、メチル基又はエチル基を示し、それらはたがいに同一でも異なっていてもよく、ｎは０又は１を示す。
前記一般式（Ｉ）で表されるグリコールを用いることにより、不純物アルデヒドのアセタール化が十分に進行し、簡単な蒸留操作により、該不純物アルデヒドを除去することができる。一般式（Ｉ）で表されるグリコールとしては、例えばエチレングリコール、トリメチレングリコール、プロピレングリコール、ネオペンチルグリコールなどを挙げることができ、これらは一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
The glycol represented by these can be used.
In the general formula (I), R 1 ~R 6 are each a hydrogen atom, a methyl group or an ethyl group and may be the same with or different from each other, n represents 0 or 1.
By using the glycol represented by the general formula (I), the acetalization of the impurity aldehyde proceeds sufficiently, and the impurity aldehyde can be removed by a simple distillation operation. Examples of the glycol represented by the general formula (I) include ethylene glycol, trimethylene glycol, propylene glycol, neopentyl glycol and the like. These may be used alone or in combination of two or more. May be used.
本発明においては、前記グリコールの添加量としては、ＴＣＤＥ粗精製物に対し、通常０．１〜１０．０質量％、好ましくは０．５〜５．０質量％の範囲で選定される。また、接触処理温度としては、反応速度や、添加するグリコールの留出ロス及び製品の留出ロスなどを考慮すると、８０〜２００℃の範囲が好ましく、特に１００〜１８０℃の範囲が好ましい。処理時間は１〜５時間程度で十分である。
本発明において、不純物アルデヒドをアセタール化合物に変換する反応は平衡反応であるため、生成する水を系外に除去することにより、反応を促進させることができる。水除去の手段に関しては、ＴＣＤＥ粗精製物に対して不活性な気体、例えば、窒素を流して水を同伴させる方法、ＴＣＤＥ粗精製物と反応しない脱水剤、例えば、無水硫酸ナトリウムなどを添加する方法、また、水と混和しない適当な沸点をもつ溶媒を加え、この溶媒の還流下で水を除去する方法などがある。
処理後は、酸触媒を中和、水洗あるいは濾過にて除去した後、蒸留により精製することによって製品のＴＣＤＥが得られる。
In the present invention, the addition amount of the glycol is usually selected in the range of 0.1 to 10.0% by mass, preferably 0.5 to 5.0% by mass with respect to the TCDE crude product. The contact treatment temperature is preferably in the range of 80 to 200 ° C., particularly preferably in the range of 100 to 180 ° C. in consideration of the reaction rate, the distillation loss of the glycol to be added, the product distillation loss, and the like. A treatment time of about 1 to 5 hours is sufficient.
In the present invention, since the reaction for converting the impurity aldehyde into an acetal compound is an equilibrium reaction, the reaction can be promoted by removing generated water from the system. Regarding means for removing water, a gas inert to the TCDE crude product, for example, a method of entraining water by flowing nitrogen, a dehydrating agent that does not react with the TCDE crude product, such as anhydrous sodium sulfate, is added. And a method of adding a solvent having an appropriate boiling point that is immiscible with water and removing water under reflux of the solvent.
After the treatment, the acid catalyst is removed by neutralization, washing with water or filtration, and then purified by distillation to obtain a product TCDE.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
合成例１
ナックドライブ式攪拌機と上部に３個の入口ノズル、底部に１個の抜き出しノズルを備え、ジャケットにより内部温度を制御できる内容積１０リットルのステンレス製オートクレーブを一酸化炭素で置換した後、フッ化水素３ｋｇ（１５０モル）を導入し、一酸化炭素で２ＭＰａまで加圧した。
反応温度を４０℃に保持し、かつ反応圧力を２ＭＰａに保ちながら、ＤＨＤＣＰＤ／ｎ−ヘプタン＝１／０．７５（質量比）の組成の原料液２９５０ｇをオートクレーブ上部より供給しカルボニル化を行った。原料供給終了後、反応液の温度を０℃に下げ、常圧まで落圧した後、エタノール５７５ｇを供給し、エステル化反応を行った。さらに１時間攪拌を継続した後、触媒のフッ化水素を蒸留により除去し、得られた反応液を２質量％ＮａＯＨ水溶液で中和水洗後、理論段数５段の蒸留塔を用いて精留を行い、ＴＣＤＥ粗精製物を得た。この粗精製物のＴＣＤＥ純度は９７．０１質量％であり、不純物アルデヒドが１．１４質量％含まれていた。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Synthesis example 1
A stainless steel autoclave with an internal volume of 10 liters equipped with a Nack drive type stirrer, three inlet nozzles at the top and one extraction nozzle at the bottom and whose internal temperature can be controlled by a jacket is replaced with carbon monoxide, and then hydrogen fluoride. 3 kg (150 mol) was introduced and pressurized to 2 MPa with carbon monoxide.
While maintaining the reaction temperature at 40 ° C. and maintaining the reaction pressure at 2 MPa, 2950 g of a raw material solution having a composition of DHDCPD / n-heptane = 1 / 0.75 (mass ratio) was supplied from the top of the autoclave to perform carbonylation. . After the end of the raw material supply, the temperature of the reaction solution was lowered to 0 ° C. and dropped to normal pressure, and then 575 g of ethanol was supplied to carry out an esterification reaction. After further stirring for 1 hour, the hydrogen fluoride of the catalyst was removed by distillation, and the resulting reaction solution was neutralized with 2% by weight NaOH aqueous solution and then subjected to rectification using a distillation column having 5 theoretical plates. The TCDE crude product was obtained. The crude product had a TCDE purity of 97.01% by mass and contained 1.14% by mass of an impurity aldehyde.
実施例１
メカニカル攪拌機、窒素導入ノズル、温度計、排ガスラインを装備した２リットル４つ口フラスコに、ＴＣＤＥ粗精製物５００ｇと、活性白土１０ｇ、エチレングリコール１０ｇを仕込み、窒素気流下で１５０℃に加熱・攪拌を行った。３時間同条件を維持した後、室温まで冷却した。冷却後、活性白土を濾別し、得られた液をガスクロマトグラフィー（ＧＣ）分析したところ、ＴＣＤＥ純度９６．４０質量％、不純物アルデヒド含有量は０．４４質量％であり、その他不純物アルデヒドとエチレングリコールのアセタール化合物が０．８９質量％生成していることが確認された。
活性白土を濾別して得られた液のうち４００ｇを理論段数２０段の精留塔を用いて精留を行ったところ、主留部分としてＴＣＤＥ純度９９．５８質量％、不純物アルデヒド含有量０．４２質量％のものが得られた。このものは甘い果実様の香気を有しており、香料組成物として優れた香気特性であった。
Example 1
A 2-liter 4-neck flask equipped with a mechanical stirrer, nitrogen introduction nozzle, thermometer, and exhaust gas line was charged with 500 g of TCDE crude product, 10 g of activated clay, and 10 g of ethylene glycol, and heated and stirred at 150 ° C. under a nitrogen stream. Went. After maintaining the same conditions for 3 hours, it was cooled to room temperature. After cooling, the activated clay was filtered off, and the obtained liquid was analyzed by gas chromatography (GC). As a result, the TCDE purity was 96.40% by mass, the impurity aldehyde content was 0.44% by mass, It was confirmed that 0.89% by mass of an acetal compound of ethylene glycol was produced.
When 400 g of the liquid obtained by filtering off activated clay was rectified using a rectification tower having a theoretical plate number of 20 plates, a TCDE purity of 99.58% by mass and an impurity aldehyde content of 0.42 were obtained as the main fraction. The thing of the mass% was obtained. This product had a sweet fruit-like fragrance and had excellent fragrance characteristics as a fragrance composition.
比較例１
ＴＣＤＥ粗製品４００ｇをそのまま、実施例１と同じ蒸留塔を用いて同様の方法で精留を行ったところ、主留部分としてＴＣＤＥ純度９８．３４質量％、不純物アルデヒド含有量１．１０質量％のものが得られた。このサンプルは、上記実施例のサンプルと比較して甘さが劣り、匂いに固さが感じられ、そのままでは香料組成物として適さなかった。
実施例１及び比較例１に示すように、不純物アルデヒドは理論段数２０段の精留塔を用いて精留を行っても、０．０２〜０．０４質量％の除去しかできず、精留前に不純物アルデヒド濃度を下げておく必要があることが分かる。
Comparative Example 1
When 400 g of the crude TCDE product was rectified by the same method using the same distillation column as in Example 1, the main fraction portion had a TCDE purity of 98.34% by mass and an impurity aldehyde content of 1.10% by mass. Things were obtained. This sample was inferior in sweetness as compared with the sample of the above-mentioned example, and the smell was firm, and as such was not suitable as a fragrance composition.
As shown in Example 1 and Comparative Example 1, the impurity aldehyde can be removed only by 0.02 to 0.04% by mass even when rectification is performed using a rectification column having 20 theoretical plates, and rectification is performed. It can be seen that the impurity aldehyde concentration needs to be lowered before.
実施例２
処理温度を１１０℃とした以外は実施例１と同様の操作を行った。活性白土を濾別して得られた液のＧＣ分析を行ったところ、ＴＣＤＥ純度９６．３０質量％、不純物アルデヒド含有量は０．４８質量％であり、その他に不純物アルデヒドとエチレングリコールのアセタール化合物が０．７８質量％認められた。
Example 2
The same operation as in Example 1 was performed except that the treatment temperature was 110 ° C. GC analysis of the liquid obtained by filtering off activated clay revealed that the TCDE purity was 96.30% by mass, the impurity aldehyde content was 0.48% by mass, and that the acetal compound of impurity aldehyde and ethylene glycol was 0. .78% by mass was observed.
実施例３
エチレングリコールをトリメチレングリコールに変えた以外は実施例１と同様の処理を行った。活性白土を濾別して得られた液のＧＣ分析を行ったところ、ＴＣＤＥ純度９６．３５質量％、不純物アルデヒド含有量は０．４９質量％であり、その他に不純物アルデヒドとトリメチレングリコールのアセタール化合物が０．７３質量％認められた。
Example 3
The same treatment as in Example 1 was performed except that ethylene glycol was changed to trimethylene glycol. When the GC analysis of the liquid obtained by filtering off activated clay was conducted, the TCDE purity was 96.35% by mass, the impurity aldehyde content was 0.49% by mass, and in addition, an acetal compound of impurity aldehyde and trimethylene glycol was obtained. 0.73% by mass was observed.
比較例２
エチレングリコールの代わりにｎ−ブタノールを用い、処理温度を１１０℃とした以外は実施例１と同様の操作を行った。活性白土を濾別して得られた液のＧＣ分析を行ったところ、ＴＣＤＥ純度９６．３８質量％、不純物アルデヒド含有量は１．０５質量％であり、不純物アルデヒドとｎ−ブタノールのアセタール化合物はほとんど検出されなかった。
Comparative Example 2
The same operation as in Example 1 was performed except that n-butanol was used in place of ethylene glycol and the treatment temperature was 110 ° C. When GC analysis was performed on the liquid obtained by filtering off activated clay, the TCDE purity was 96.38% by mass, the impurity aldehyde content was 1.05% by mass, and almost no acetal compound of impurity aldehyde and n-butanol was detected. Was not.
比較例３
エチレングリコールの代わりに１，４−ブタンジオールを用いた以外は実施例１と同様の操作を行った。活性白土を濾別して得られた液のＧＣ分析を行ったところ、ＴＣＤＥ純度９６．４２質量％、不純物アルデヒド含有量は１．００質量％であり、不純物アルデヒドと１，４−ブタンジオールのアセタール化合物はほとんど検出されなかった。
比較例２，３に示すように、本発明範囲外のグリコールを用いた場合には、不純物アルデヒドとアセタールを形成しにくく、不純物アルデヒドの低減は不十分である。
Comparative Example 3
The same operation as in Example 1 was performed except that 1,4-butanediol was used instead of ethylene glycol. When GC analysis of the liquid obtained by filtering off activated clay was conducted, the TCDE purity was 96.42% by mass, the impurity aldehyde content was 1.00% by mass, and the acetal compound of impurity aldehyde and 1,4-butanediol Was hardly detected.
As shown in Comparative Examples 2 and 3, when a glycol outside the scope of the present invention is used, it is difficult to form an impurity aldehyde and an acetal, and the reduction of the impurity aldehyde is insufficient.
本発明によれば、不純物アルデヒドなどが低減されてなる香気性に優れる精製ＴＣＤＥを工業的に有利に得ることができる。この精製ＴＣＤＥは、香料又は香料成分として好適に用いられる。
ADVANTAGE OF THE INVENTION According to this invention, the refinement | purification TCDE which is excellent in the aroma property by which impurity aldehyde etc. are reduced can be obtained industrially advantageously. This purified TCDE is suitably used as a fragrance or a fragrance component.
Claims (2)
で表されるグリコールと接触処理させたのち、蒸留することを特徴とする精製トリシクロ［５．２．１．０2,6］デカン−２−カルボン酸エチルエステルの製造方法。 Tricyclo [5.2.1.0 2,6 ] dec-3-ene is reacted with carbon monoxide and ethanol in the presence of HF to give tricyclo [5.2.1.0 2,6 ] decan-2- In the method for producing carboxylic acid ethyl ester, a crude product of tricyclo [5.2.1.0 2,6 ] decane-2-carboxylic acid ethyl ester is prepared in the presence of an acid catalyst in the general formula (I).
A process for producing purified tricyclo [5.2.1.0 2,6 ] decane-2-carboxylic acid ethyl ester, which is subjected to contact treatment with the glycol represented by
When the crude product of tricyclo [5.2.1.0 2,6 ] decane-2-carboxylic acid ethyl ester is contacted with the glycol in the presence of an acid catalyst, the contact treatment is performed at 100 to 180 ° C. The process of claim 1, wherein the process is carried out at a range of temperatures.
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| DE602004008002T DE602004008002T2 (en) | 2003-09-19 | 2004-09-14 | Preparation process for high purity tricyclo- (5.2.1.0 2,6) decane-2-carboxylic acid ester |
| EP04104426A EP1522537B1 (en) | 2003-09-19 | 2004-09-14 | Production process for high purity tricyclo-¬5. 2.1.0 2,6|decane-2-carboxylic acid ester |
| US10/942,880 US7253300B2 (en) | 2003-09-19 | 2004-09-17 | Production process for high purity tricyclo-[5.2.1.02,6]decane-2-carboxylic acid ester |
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