JP4873777B2 - Process for producing β-picoline - Google Patents
Process for producing β-picoline Download PDFInfo
- Publication number
- JP4873777B2 JP4873777B2 JP2000368079A JP2000368079A JP4873777B2 JP 4873777 B2 JP4873777 B2 JP 4873777B2 JP 2000368079 A JP2000368079 A JP 2000368079A JP 2000368079 A JP2000368079 A JP 2000368079A JP 4873777 B2 JP4873777 B2 JP 4873777B2
- Authority
- JP
- Japan
- Prior art keywords
- picoline
- metal
- triallylamine
- group
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 title claims description 27
- 238000000034 method Methods 0.000 title description 14
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000011949 solid catalyst Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000011787 zinc oxide Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical class [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Pyridine Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、β−ピコリンの製造方法に関する。
【０００２】
【従来の技術】
トリアリルアミンからβ−ピコリンを製造する方法としては、例えばHelvetica Chimica Acta, Vol.57, 17-23(1974) に記載されている方法が知られている。この方法は、トリアリルアミンをトリメチルベンゼン、シクロヘキサン等の希釈剤と混合し、気相中で熱分解する方法である。
【０００３】
しかしながら、この方法では、目的とするβ−ピコリンの収率が３〜５５％程度と低い。また、この方法では、希釈剤として使用されるトリメチルベンゼン、シクロヘキサン等の有機溶剤を、熱分解終了後にβ−ピコリンと分離する必要がある。そのため、上記方法は、β−ピコリンの工業的製造法として不適当である。
【０００４】
【発明が解決しようとする課題】
本発明は、目的とするβ−ピコリンを高収率で製造し得る方法を提供することを課題とする。
【０００５】
本発明は、トリメチルベンゼン、シクロヘキサン等の有機溶剤を希釈剤として使用する必要がなく、そのため反応終了後に希釈剤とβ−ピコリンとを分離する工程を必要としないβ−ピコリンの製造方法を提供することを課題とする。
【０００６】
本発明は、β−ピコリンの工業的に有利な製造法を提供することを課題とする。
【０００７】
【課題を解決するための手段】
本発明者は、上記課題を解決するために種々の研究を重ねてきた。その結果、気体状のトリアリルアミンを脱水素能を有する固体触媒と接触させることにより、上記課題を解決できることを見い出した。本発明は、このような知見に基づき完成されたものである。
【０００８】
即ち、本発明は、気体状のトリアリルアミンを脱水素能を有する固体触媒と接触させてβ−ピコリンを得ることを特徴とするβ−ピコリンの製造方法に係る。
【０００９】
【発明の実施の形態】
本発明においては、気体状のトリアリルアミンを脱水素能を有する固体触媒と接触させる。
【００１０】
本発明で使用される触媒は、脱水素能を有する固体触媒であり、金属、金属の化合物及び金属イオンの少なくとも一種を活性成分として含有する。
【００１１】
脱水素能を有する固体触媒としては、公知のものを広く使用でき、例えば単元系金属酸化物、複合系金属酸化物及び層状化合物並びに上記化合物を構成する金属及び／又は金属イオンを含有するもの等を挙げることができる。
【００１２】
脱水素能を有する固体触媒は、金属、金属の化合物及び金属イオンからなる群より選ばれた少なくとも一種を含有する触媒であって、且つ前記金属が周期律表第４族に属する金属、同第１１族に属する金属及び同第１２族に属する金属からなる群より選ばれた少なくとも一種の金属である触媒が好ましい。
【００１３】
周期律表第４族に属する金属としては、例えばチタン、ジルコニウム等が挙げられる。周期律表第１１族に属する金属としては、例えば銅、銀等が挙げられる。周期律表第１２族に属する金属としては、例えば亜鉛、カドミウム等が挙げられる。これらの中でも、ジルコニウム、銅及び亜鉛が特に好ましい。
【００１４】
このような脱水素能を有する固体触媒としては、具体的には酸化亜鉛、酸化ジルコニウム、酸化銅、酸化銀、酸化亜鉛、酸化カドミウム等の単元系金属酸化物、酸化チタン／酸化ジルコニウム、酸化銅／酸化亜鉛、酸化亜鉛／酸化ジルコニウム等の複合系金属酸化物、ケイ酸アルミニウムの亜鉛塩等の層状化合物等を例示でき、これらはシリカ、アルミナ等の担体に担持されていてもよい。
【００１５】
本発明においては、不活性ガス雰囲気下に、トリアリルアミンと固体触媒とを接触させるのが好ましい。
【００１６】
不活性ガスとしては、公知のものを広く使用でき、例えば窒素ガス、ヘリウムガス、ネオンガス、アルゴンガス、水蒸気等を挙げることができる。これらの中でも、窒素ガスが好ましい。
【００１７】
トリアリルアミンと脱水素能を有する固体触媒とを接触させてβ−ピコリンを得る反応は、固定床反応器又は流動床反応器を用いて行われる。
【００１８】
固定床反応器を用いる場合には、例えば、反応管に上記固体触媒を充填し、反応管の触媒充填部を、通常２５０〜５５０℃、好ましくは３００〜５００℃に昇温する。次に該反応管の触媒充填部にトリアリルアミンを供給して気相接触反応を行う。トリアリルアミンの液空間速度（以下、「ＬＨＳＶ」という）は、通常０．００１〜５ｇ／（ｍｌ触媒・ｈｒ）程度、好ましくは０．０１〜２ｇ／（ｍｌ触媒・ｈｒ）程度である。また、不活性ガスを使用する場合には、トリアリルアミン及び不活性ガスからなる混合ガスの空間速度（以下、「ＳＶ」という）は、通常３０〜１００００ｈｒ-1、好ましくは１００〜３０００ｈｒ-1である。トリアリルアミンと不活性ガスの混合割合は、通常前者１モルに対して後者を０．１〜２０モル程度、好ましくは０．５〜５モル程度とするのがよい。
【００１９】
本発明の反応は、常圧下、減圧下又は加圧下のいずれでも実施することができる。
【００２０】
【発明の効果】
本発明によれば、目的とするβ−ピコリンを高収率で製造し得る。
【００２１】
本発明によれば、トリメチルベンゼン、シクロヘキサン等の有機溶剤を希釈剤として使用する必要がなく、そのため反応終了後に希釈剤とβ−ピコリンとを分離する工程を必要としない。
【００２２】
そのため、本発明の方法は、β−ピコリンの工業的製造法として極めて有利である。
【００２３】
【実施例】
以下に実施例及び比較例を掲げて、本発明をより一層明らかにする。
【００２４】
実施例１
酸化亜鉛８ｍｌを内径１８ｍｍのパイレックス製反応管に充填し、該反応管の触媒充填部を４２５℃に昇温した。この触媒充填部にトリアリルアミンをＬＨＳＶ０．５ｇ／（ｍｌ触媒・ｈｒ）で及び窒素を１１ｍｌ／分（トリエチルアミン１モルに対して１モル）で供給した。このときの混合ガスのＳＶは１７０ｈｒ-1であった。反応管から流出する反応生成ガスを１５分間、メタノール７０ｍｌ中に通じ、反応生成ガス中の可溶性成分をメタノールに溶解した。得られた溶液をガスクロマトグラフィーで分析した。その結果、トリアリルアミンの転化率は１００％、β−ピコリンの収率は７４％、選択率は７４％であった。
【００２５】
実施例２
実施例１において酸化亜鉛に代えて酸化ジルコニウムを使用した以外は、実施例１と同様に行った。その結果、トリアリルアミンの転化率は１００％、β−ピコリンの収率は６５％、選択率は６５％であった。
【００２６】
実施例３
実施例１において酸化亜鉛に代えて酸化銅／酸化亜鉛／アルミナ（重量比３０／６０／１０）を使用した以外は、実施例１と同様に行った。その結果、トリアリルアミンの転化率は１００％、β−ピコリンの収率は７６％、選択率は７６％であった。
【００２７】
実施例４
実施例１において酸化亜鉛に代えてミズカナイト（商品名、水澤化学株式会社製、天然のケイ酸アルミニウムの亜鉛塩：二層構造の層状化合物）を使用した以外は、実施例１と同様に行った。その結果、トリアリルアミンの転化率は１００％、β−ピコリンの収率は７５％、選択率は７５％であった。
【００２８】
実施例５
実施例３においてトリアリルアミンのＬＨＳＶを１．０ｇ／（ｍｌ触媒・ｈｒ）とし、且つ窒素を供給しない以外は、実施例３と同様に行った。その結果、トリアリルアミンの転化率は１００％、β−ピコリンの収率は６９％、選択率は６９％であった。
【００２９】
比較例
実施例１において酸化亜鉛を使用しない以外は、実施例１と同様に行った。その結果、トリアリルアミンの転化率は１００％、β−ピコリンの収率は４３％、選択率は４３％であった。
【００３０】
上記の結果を表１にまとめて示す。
【００３１】
【表１】
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing β-picoline.
[0002]
[Prior art]
As a method for producing β-picoline from triallylamine, for example, a method described in Helvetica Chimica Acta, Vol. 57, 17-23 (1974) is known. In this method, triallylamine is mixed with a diluent such as trimethylbenzene or cyclohexane and thermally decomposed in a gas phase.
[0003]
However, in this method, the yield of target β-picoline is as low as about 3 to 55%. Further, in this method, it is necessary to separate an organic solvent such as trimethylbenzene or cyclohexane used as a diluent from β-picoline after completion of thermal decomposition. Therefore, the above method is unsuitable as an industrial production method of β-picoline.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a method capable of producing a target β-picoline in a high yield.
[0005]
The present invention provides a method for producing β-picoline that does not require the use of an organic solvent such as trimethylbenzene or cyclohexane as a diluent, and therefore does not require a step of separating the diluent and β-picoline after the reaction is completed. This is the issue.
[0006]
An object of the present invention is to provide an industrially advantageous process for producing β-picoline.
[0007]
[Means for Solving the Problems]
The inventor has conducted various studies in order to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by bringing gaseous triallylamine into contact with a solid catalyst having dehydrogenation ability. The present invention has been completed based on such findings.
[0008]
That is, the present invention relates to a method for producing β-picoline, characterized in that β-picoline is obtained by contacting gaseous triallylamine with a solid catalyst having a dehydrogenating ability.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, gaseous triallylamine is brought into contact with a solid catalyst having dehydrogenation ability.
[0010]
The catalyst used in the present invention is a solid catalyst having a dehydrogenating ability, and contains at least one of a metal, a metal compound and a metal ion as an active component.
[0011]
As the solid catalyst having dehydrogenating ability, known ones can be widely used, for example, single metal oxides, composite metal oxides and layered compounds, and those containing the metal and / or metal ions constituting the above compounds, etc. Can be mentioned.
[0012]
The solid catalyst having dehydrogenation ability is a catalyst containing at least one selected from the group consisting of metals, metal compounds, and metal ions, and the metal belongs to Group 4 of the periodic table. A catalyst that is at least one metal selected from the group consisting of metals belonging to Group 11 and metals belonging to Group 12 is preferred.
[0013]
Examples of the metal belonging to Group 4 of the periodic table include titanium and zirconium. Examples of metals belonging to Group 11 of the periodic table include copper and silver. Examples of metals belonging to Group 12 of the periodic table include zinc and cadmium. Among these, zirconium, copper, and zinc are particularly preferable.
[0014]
Specific examples of the solid catalyst having such dehydrogenating ability include single-component metal oxides such as zinc oxide, zirconium oxide, copper oxide, silver oxide, zinc oxide, and cadmium oxide, titanium oxide / zirconium oxide, and copper oxide. Examples include layered compounds such as composite metal oxides such as / zinc oxide and zinc oxide / zirconium oxide, and zinc salts of aluminum silicate, which may be supported on a carrier such as silica and alumina.
[0015]
In the present invention, triallylamine and the solid catalyst are preferably contacted in an inert gas atmosphere.
[0016]
As the inert gas, known ones can be widely used, and examples thereof include nitrogen gas, helium gas, neon gas, argon gas, and water vapor. Among these, nitrogen gas is preferable.
[0017]
The reaction for obtaining β-picoline by contacting triallylamine with a solid catalyst having dehydrogenating ability is carried out using a fixed bed reactor or a fluidized bed reactor.
[0018]
When using a fixed bed reactor, for example, the solid catalyst is filled in the reaction tube, and the temperature of the catalyst filling portion of the reaction tube is usually raised to 250 to 550 ° C, preferably 300 to 500 ° C. Next, triallylamine is supplied to the catalyst filling portion of the reaction tube to perform a gas phase catalytic reaction. The liquid space velocity of triallylamine (hereinafter referred to as “LHSV”) is usually about 0.001 to 5 g / (ml catalyst · hr), preferably about 0.01 to 2 g / (ml catalyst · hr). In the case of using an inert gas, the space velocity of the mixed gas consisting of triallylamine and inert gas (hereinafter, referred to as "SV") is usually 30～10000Hr -1, preferably 100～3000Hr -1 is there. The mixing ratio of triallylamine and inert gas is usually about 0.1 to 20 mol, preferably about 0.5 to 5 mol, with respect to 1 mol of the former.
[0019]
The reaction of the present invention can be carried out under normal pressure, reduced pressure or increased pressure.
[0020]
【Effect of the invention】
According to the present invention, the target β-picoline can be produced in a high yield.
[0021]
According to the present invention, it is not necessary to use an organic solvent such as trimethylbenzene or cyclohexane as a diluent, and therefore a step of separating the diluent and β-picoline after the reaction is not required.
[0022]
Therefore, the method of the present invention is extremely advantageous as an industrial production method of β-picoline.
[0023]
【Example】
The present invention will be further clarified by the following examples and comparative examples.
[0024]
Example 1
8 ml of zinc oxide was filled into a Pyrex reaction tube having an inner diameter of 18 mm, and the temperature of the catalyst filling portion of the reaction tube was raised to 425 ° C. Triallylamine was supplied at 0.5 g / LHSV / (ml catalyst · hr) and nitrogen was supplied at 11 ml / min (1 mol per 1 mol of triethylamine) to the catalyst packed portion. The SV of the mixed gas at this time was 170 hr −1 . The reaction product gas flowing out of the reaction tube was passed into 70 ml of methanol for 15 minutes, and the soluble components in the reaction product gas were dissolved in methanol. The resulting solution was analyzed by gas chromatography. As a result, the conversion of triallylamine was 100%, the yield of β-picoline was 74%, and the selectivity was 74%.
[0025]
Example 2
The same operation as in Example 1 was performed except that zirconium oxide was used instead of zinc oxide in Example 1. As a result, the conversion of triallylamine was 100%, the yield of β-picoline was 65%, and the selectivity was 65%.
[0026]
Example 3
The same procedure as in Example 1 was performed except that copper oxide / zinc oxide / alumina (weight ratio 30/60/10) was used instead of zinc oxide in Example 1. As a result, the conversion of triallylamine was 100%, the yield of β-picoline was 76%, and the selectivity was 76%.
[0027]
Example 4
Example 1 was carried out in the same manner as in Example 1 except that Mizkanite (trade name, manufactured by Mizusawa Chemical Co., Ltd., natural zinc silicate: layered compound having a two-layer structure) was used instead of zinc oxide. . As a result, the conversion rate of triallylamine was 100%, the yield of β-picoline was 75%, and the selectivity was 75%.
[0028]
Example 5
The same procedure as in Example 3 was performed except that LHSV of triallylamine was 1.0 g / (ml catalyst · hr) and nitrogen was not supplied. As a result, the conversion of triallylamine was 100%, the yield of β-picoline was 69%, and the selectivity was 69%.
[0029]
Comparative Example The same procedure as in Example 1 was performed except that zinc oxide was not used. As a result, the conversion of triallylamine was 100%, the yield of β-picoline was 43%, and the selectivity was 43%.
[0030]
The results are summarized in Table 1.
[0031]
[Table 1]
Claims (4)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2000368079A JP4873777B2 (en) | 2000-12-04 | 2000-12-04 | Process for producing β-picoline |
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| JP2000368079A JP4873777B2 (en) | 2000-12-04 | 2000-12-04 | Process for producing β-picoline |
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| JP2002173480A JP2002173480A (en) | 2002-06-21 |
| JP4873777B2 true JP4873777B2 (en) | 2012-02-08 |
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| JPH0674256B2 (en) * | 1986-12-24 | 1994-09-21 | 広栄化学工業株式会社 | Method for producing pyrazines |
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