JPS60130568A - Production of 7-alkyl-8-hydroxyquinoline - Google Patents
Production of 7-alkyl-8-hydroxyquinolineInfo
- Publication number
- JPS60130568A JPS60130568A JP58238922A JP23892283A JPS60130568A JP S60130568 A JPS60130568 A JP S60130568A JP 58238922 A JP58238922 A JP 58238922A JP 23892283 A JP23892283 A JP 23892283A JP S60130568 A JPS60130568 A JP S60130568A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxyquinoline
- alkyl
- alkenyl
- solvent
- reaction
- 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.)
- Granted
Links
- 229960003540 oxyquinoline Drugs 0.000 title claims abstract description 22
- 239000005725 8-Hydroxyquinoline Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 229910052705 radium Inorganic materials 0.000 claims description 2
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 10
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 abstract 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 150000001455 metallic ions Chemical class 0.000 abstract 1
- 238000000638 solvent extraction Methods 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 16
- 229910052763 palladium Inorganic materials 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- -1 aliphatic amines Chemical class 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- GWEBMPLMIBHPCC-UHFFFAOYSA-N 7-undecylquinolin-8-ol Chemical compound C1=CC=NC2=C(O)C(CCCCCCCCCCC)=CC=C21 GWEBMPLMIBHPCC-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- ODFJUYPWADMCSY-UHFFFAOYSA-N 3-(5,5,7,7-tetramethyloct-1-enyl)quinolin-8-ol Chemical compound CC(CCC=CC=1C=NC2=C(C=CC=C2C1)O)(CC(C)(C)C)C ODFJUYPWADMCSY-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 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
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 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
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Quinoline Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は７−アルキル−８−７１イドロキシキノリンの
製造方法に関する。更に詳しくは７−アルケニル−８−
ノ九イドロキシキノリンを水素加圧下にアミン類及びパ
ラジウム触媒の存在下接触還元する事を特徴とする７−
アルキル−８−ハイドロキシキノリンの製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 7-alkyl-8-71 idroxyquinoline. More specifically, 7-alkenyl-8-
7-, which is characterized by catalytic reduction of noihydroxyquinoline in the presence of amines and a palladium catalyst under hydrogen pressure.
The present invention relates to a method for producing alkyl-8-hydroxyquinoline.
７−アルケニル又は７−アルキル−８−ノ嶌イドロキシ
キノリンは銅、ニッケル、コノクルト等はエレクトロニ
クス産業の重要な素材の一つであるガリウムの抽出剤と
しても注目されている。7-alkenyl or 7-alkyl-8-hydroxyquinoline is attracting attention as an extractant for copper, nickel, and gallium, which is one of the important materials in the electronics industry.
例えば特開昭５１−３２４１１．％開昭５３−５２２８
９ 、ドイツ特許公開２７１０４９１等にはこれらの化
合物を金属イオンの抽出剤として用いる方法についての
記載があり又製品としてはアシュランド社のテレックス
−１００，同−１２０等の名で市販されている。′特開
昭５３−５２２８９に記載されているように７−アルケ
ニル−８−ハイドロキシキノリンは抽出剤としてくり返
えし使用すると劣化が激しいが７−アルキル−８−ハイ
ドロキシキノリンは劣化がほとんど起らない為、実用面
からは７−アルキル−８−ハイドロキシキノリンの方が
抽出剤としてすぐれている。For example, JP-A-51-32411. % Kaisho 53-5228
9, German Patent Publication No. 2710491, etc., there are descriptions of methods of using these compounds as extractants for metal ions, and the products are commercially available under the names of Ashland's Terex-100, Terex-120, etc. 'As described in JP-A-53-52289, 7-alkenyl-8-hydroxyquinoline deteriorates severely when used repeatedly as an extractant, but 7-alkyl-8-hydroxyquinoline hardly deteriorates. Therefore, from a practical point of view, 7-alkyl-8-hydroxyquinoline is superior as an extractant.
７−アルクニル−８−ハイドロキシキノリンを接触還元
すれば７−アルキル−８−ノ・イドロキシキノリンが得
られることは公知であり、−方炭素・炭素二重結合の水
素化触媒としてパラジウム触媒が適していることも広く
知られている。しかしながら７−アルケニル−８−ハイ
ドロキシキノリンをパラジウム触媒を用いて水素化する
と主成分の７−アルキルτ８−ハイドロキシキノリンの
他に、複素環が水素化された７−アルキル−８−ハイド
ロキシ−Ｐｙ−テトラヒドロキノリンが副生ずる。副生
成物の生成を抑えるために例えば室温常圧の条件で接触
還元すると複素環の水素化は幾分抑制されるが、炭素・
炭素二重結合の水素化も遅くなり実用的な反応速度が得
られず、純度の高１／−１７−アルキルー８−ハイドロ
キシキノリンを得るための精製に多大の労力と費用を要
し収量が悪くなることはさけられない。It is known that 7-alkyl-8-hydroxyquinoline can be obtained by catalytic reduction of 7-alknyl-8-hydroxyquinoline, and a palladium catalyst is suitable as a hydrogenation catalyst for the carbon-carbon double bond. It is also widely known that However, when 7-alkenyl-8-hydroxyquinoline is hydrogenated using a palladium catalyst, in addition to the main component 7-alkyl Quinoline is produced as a by-product. In order to suppress the formation of by-products, for example, catalytic reduction at room temperature and normal pressure suppresses the hydrogenation of heterocycles to some extent;
Hydrogenation of carbon double bonds is also slow, making it impossible to obtain a practical reaction rate, and refining to obtain highly pure 1/-17-alkyl-8-hydroxyquinoline requires a great deal of effort and expense, resulting in poor yields. It cannot be avoided.
本発明者らはこれらの欠点を改良すべく７−アルケニル
−８−ハイドロキシキノリンの接触還元法について鋭意
検討した結果、アミン類及びパラジウム触媒の存在下で
７−アルケニル−８−ハイドロキシキノリンを水素化す
る事により高純度、高収率で７−アルキル−８−ノ・イ
ドロキシキノリンが得られる事を見出し本発明に到達し
た。The present inventors conducted intensive studies on the catalytic reduction method of 7-alkenyl-8-hydroxyquinoline to improve these drawbacks, and as a result, hydrogenation of 7-alkenyl-8-hydroxyquinoline in the presence of amines and a palladium catalyst was conducted. The present invention was achieved by discovering that 7-alkyl-8-no-idroxyquinoline can be obtained with high purity and high yield by doing this.
本発明の方法によれば複素環の水素化がほとんど起らず
、また充分な反応速度が得られるため、工業的にきわめ
て有利に７−アルキル−８−ハイドロキシキノリンを製
造する事ができる。According to the method of the present invention, hydrogenation of heterocycles hardly occurs and a sufficient reaction rate can be obtained, so that 7-alkyl-8-hydroxyquinoline can be produced industrially very advantageously.
以下本発明の方法を詳細に説明する。The method of the present invention will be explained in detail below.
本発明で用いるアミン類としては、メチルアミン、エチ
ルアミン、ブチルアミン、エタノールアミンの如き脂肪
族−級アミン類、ジメチルアミン、ジエチルアミン、ジ
ブチルアミン、ヘキサメチレンペンクミンの如き脂肪族
二級アミン類、トリメチルアミン、トリエチルアミン、
トリエタノールアミンの如き脂肪族第三級アミン類、ア
ニリン、トルイジン、Ｎ−メチルアニリン、Ｎ、Ｎ−ジ
メチルアニリンの如き芳香族アミン類、ピリジン、アル
キルピリジン、ヒペリジン、モルフォリンの如き複素環
式アミン類を挙げる事ができる。これらのアミン類は単
独で又二種以上混合して用いられ、その添加量は７−ア
ルクニル−８−ノ・イドロキシキノリンに対して重量比
で１〜５０％、好ましくは２〜２０％である。又パラジ
ウム触媒としては、コロイドパラジウム、パラジウム黒
、活性炭、アルミナ、シリカ、硫酸バリウム等の担体上
に担持されたパラジウムが用いられる。これらノくラジ
ウム触媒の使用量は被還元物に対して０１〜３０％であ
る。The amines used in the present invention include aliphatic amines such as methylamine, ethylamine, butylamine, and ethanolamine; aliphatic secondary amines such as dimethylamine, diethylamine, dibutylamine, and hexamethylenepencumine; trimethylamine; triethylamine,
Aliphatic tertiary amines such as triethanolamine, aromatic amines such as aniline, toluidine, N-methylaniline, N,N-dimethylaniline, heterocyclic amines such as pyridine, alkylpyridine, hyperidine, morpholine. I can list several types. These amines may be used alone or in combination of two or more, and the amount added is 1 to 50%, preferably 2 to 20% by weight based on 7-alknyl-8-no-idroxyquinoline. be. As the palladium catalyst, palladium supported on a carrier such as colloidal palladium, palladium black, activated carbon, alumina, silica, barium sulfate, etc. is used. The amount of these radium catalysts used is 01 to 30% based on the product to be reduced.
本発明の方法では反応溶媒として例えばメタノール、エ
タノール、グロバノールの如キアルコール類、ベンゼン
、トルエン、キシレンのような芳香族炭化水素類、テト
ラヒドロフラン、ジオキサン、エチルセロソルブの如き
エーテル類、酢酸エチル、酢酸ブチルの如きエステル類
等が用いられる。この溶媒の種類、使用量は任意に選ぶ
事ができるが、実用的には被還元物に対して１／２から
１０倍（重量比）量用いるのがよい。またこれらの溶媒
と水とを任意の割合で混合した溶媒も用いる事ができる
。In the method of the present invention, reaction solvents include alcohols such as methanol, ethanol, and globanol, aromatic hydrocarbons such as benzene, toluene, and xylene, ethers such as tetrahydrofuran, dioxane, and ethyl cellosolve, ethyl acetate, and butyl acetate. Esters such as are used. The type and amount of this solvent can be selected arbitrarily, but it is practically preferable to use an amount that is 1/2 to 10 times (weight ratio) the amount of the product to be reduced. Moreover, a solvent obtained by mixing these solvents and water in any proportion can also be used.
反応温度は２０〜１５０℃、好ましくは４０〜８０℃で
実施する。水素圧は常圧以上の任意の圧力範囲を採用で
きるが、好ましくは３ ｋｙ ／ｃｍ２から２０にν撫
２で実施する。The reaction temperature is 20-150°C, preferably 40-80°C. Although the hydrogen pressure can be in any pressure range above normal pressure, it is preferably carried out at 3 ky/cm2 to 20 ky/cm2.
本発明において原料として用いる７−アルケニル−８−
ハイドロキシキノリンは８−キノリルキル基、Ｘはハロ
ゲンを表わす）と共に加熱する事により合成する事がで
きる。これらの方法は例えば米国特許３，６３７，７１
１、ドイツ特許公開２，７１０，４９１等に記載されて
いる。７位のアルケニルとしてはＣ５〜Ｃ＋ｓの直鎖ま
たは枝分れしたものが用いられる。本発明の一般的操作
は次のように行うがこれらに限定さ・れるものではない
。7-Alkenyl-8- used as a raw material in the present invention
Hydroxyquinoline can be synthesized by heating with an 8-quinolyl group (X represents a halogen). These methods are described, for example, in U.S. Pat.
1, as described in German Patent Publication No. 2,710,491, etc. As the alkenyl at the 7-position, a C5 to C+s linear or branched alkenyl is used. The general operation of the present invention is as follows, but is not limited thereto.
オートクレーブに所定量の溶媒、７−アルケニル−８−
ハイドロキシキノリン、ア呵ン類を加えて混合する。次
に所定量のパラジウム触媒を加え、オートクレーブ内を
窒素次いで水素で置換した後水素加圧（例えば８ ｋｇ
／ ｃｍ２ゲージ）５０℃の温度に保って攪拌し、水
素吸収が無くなるまで水素を供給する。反応終了後（水
素吸収停止後）オートクレーブを冷却し内容物の温度が
室温まで下った時攪神を停止して残存する水素を放出す
る。触媒はｐ過により反応液から回収して次回の反応に
使用する。得られた反応液から溶媒、アミンを蒸留除去
し７−アルキル−８−ハイドロキシキノリンを単離する
。エラれた７−アルキル−８−ハイドロキシキノリンは
必要なら蒸留等公知の方法により精製するこトモ出来る
。別の方法は溶媒に懸濁したパラジウム触媒、７−アル
ケニル−８−ハイドロキシキノリン、溶媒に溶解したア
ミンを連続的に、反応条件を保ったオートクレーブに仕
込み、所定の帯留時間を経て７−アルキル−８−ハイド
ロキシキノリン、アミン及びパラジウム触媒を含む反応
液を連続的に抜き出すいわゆる連続反応である。以下実
施例を挙げて本発明を説明する。A predetermined amount of solvent, 7-alkenyl-8-
Add hydroxyquinoline and ingredients and mix. Next, a predetermined amount of palladium catalyst is added, and the inside of the autoclave is replaced with nitrogen and then hydrogen, and then pressurized with hydrogen (e.g. 8 kg
/ cm2 gauge) Maintain the temperature at 50°C, stir, and supply hydrogen until hydrogen absorption disappears. After the reaction is completed (after hydrogen absorption has stopped), the autoclave is cooled, and when the temperature of the contents drops to room temperature, the agitation is stopped and the remaining hydrogen is released. The catalyst is recovered from the reaction solution by p-filtration and used for the next reaction. The solvent and amine are distilled off from the resulting reaction solution to isolate 7-alkyl-8-hydroxyquinoline. If necessary, the purified 7-alkyl-8-hydroxyquinoline can be purified by a known method such as distillation. Another method is to continuously charge a palladium catalyst suspended in a solvent, 7-alkenyl-8-hydroxyquinoline, and an amine dissolved in a solvent into an autoclave maintained under reaction conditions, and after a predetermined residence time, 7-alkenyl- This is a so-called continuous reaction in which a reaction solution containing 8-hydroxyquinoline, an amine, and a palladium catalyst is continuously extracted. The present invention will be explained below with reference to Examples.
実施例１゜
オートクレーブにエタノール］、５０ｃｃ、７−［ｌ２
−（２−ウンデセニル）〕−〕８−ハイドロキシキノリ
ン５ｏ、ｏＰ ジエチルアミンＩｇ−、２％−パラジウ
ムー炭素３Ｐ、を入れる。オートクレーブを水素置換後
、昇温昇圧し反応温度４０’Ｃ１反応圧力８ｋｇ ／
ｏｎ２ゲージに保って攪拌しながら水素吸収がなくなる
まで水素を供給する。反応終了に３０分を要した。２５
℃まで冷却後常圧に戻して内容物を取り出した。パラジ
ウム触媒を戸別した後ジエチルアミン及びエタノールを
蒸留除去して７−ウンデシル−８−ハイドロキシキノリ
ン９．９１を得た。ＧＣ分析純度９９．０％であった。Example 1゜Ethanol in autoclave], 50cc, 7-[l2
-(2-undecenyl)]-]8-hydroxyquinoline 5o,oP Diethylamine Ig-, 2%-palladium-carbon 3P, is added. After purging the autoclave with hydrogen, raise the temperature and pressure to a reaction temperature of 40'C1 reaction pressure of 8kg/
While maintaining the on2 gauge and stirring, hydrogen is supplied until hydrogen absorption disappears. It took 30 minutes to complete the reaction. 25
After cooling to ℃, the pressure was returned to normal and the contents were taken out. After removing the palladium catalyst, diethylamine and ethanol were removed by distillation to obtain 9.91 g of 7-undecyl-8-hydroxyquinoline. The purity by GC analysis was 99.0%.
実施例２゜
オートクレーブにエタノール１００ｃｃ、７−、 ［：
３−（５，５，７，７−テトラメチル−１−オクテニ
ル）−８−ハイドロキシキノリンｉｏ、ｏψ、ピリジン
１ｒ、５％パラジウム−炭素２ｇ−を入れる。Example 2 100 cc of ethanol was added to an autoclave, 7-[:
Add 3-(5,5,7,7-tetramethyl-1-octenyl)-8-hydroxyquinoline io, oψ, pyridine 1r, and 5% palladium-carbon 2g.
実施例１と同じ条件で反応を行った。反応時間は４０分
であった。触媒を濾過し、エタノール及びピリジンを蒸
留除去して７−Ｃ３−（５，５，７，７−テトラメチル
オクチル））−８−ノーイドロキシキノリン９．７ｇ−
を得た。ＧＣ純度９８．５％であった。The reaction was carried out under the same conditions as in Example 1. The reaction time was 40 minutes. The catalyst was filtered and ethanol and pyridine were distilled off to give 9.7 g of 7-C3-(5,5,7,7-tetramethyloctyl)-8-noydroxyquinoline.
I got it. The GC purity was 98.5%.
（比較例）
アミンを加えない以外は実施例１と同条件で反応を行っ
た。反応時間が１時間を過ぎても水素吸収が若干あった
だけで反応は停止した。触媒を濾過し、溶媒を蒸留除去
して７−ウンデシル−８−ハイドロキシキノリン１０．
１Ｐを得た。ＧＣ分析で７−ウンデシル−８−ハイドロ
キシキノリン６３．５％、７−ウンデシル−８−ノーイ
ドロキシ−Ｐｙ−テトラヒドロキノリン３６５％であっ
た。(Comparative Example) A reaction was carried out under the same conditions as in Example 1 except that no amine was added. Even after the reaction time exceeded 1 hour, the reaction stopped with only a slight amount of hydrogen absorption. The catalyst was filtered and the solvent was distilled off to give 7-undecyl-8-hydroxyquinoline10.
I got 1P. GC analysis showed that 7-undecyl-8-hydroxyquinoline was 63.5% and 7-undecyl-8-nohydroxy-Py-tetrahydroquinoline was 365%.
特許出願人 日本化薬株式会社Patent applicant: Nippon Kayaku Co., Ltd.
Claims (1)
水素加圧下にアミン類及びノくラジウム触媒の存在下接
触還元する事を特徴とする７−アルキル−８−ノ１イド
ロキシキノリンの製造方法。A method for producing 7-alkyl-8-hydroxyquinoline, which comprises catalytically reducing (117-alkenyl-8-)-hydroxyquinoline in the presence of an amine and a radium catalyst under hydrogen pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58238922A JPS60130568A (en) | 1983-12-20 | 1983-12-20 | Production of 7-alkyl-8-hydroxyquinoline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58238922A JPS60130568A (en) | 1983-12-20 | 1983-12-20 | Production of 7-alkyl-8-hydroxyquinoline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60130568A true JPS60130568A (en) | 1985-07-12 |
| JPH0319229B2 JPH0319229B2 (en) | 1991-03-14 |
Family
ID=17037262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58238922A Granted JPS60130568A (en) | 1983-12-20 | 1983-12-20 | Production of 7-alkyl-8-hydroxyquinoline |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60130568A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087970C (en) * | 1997-08-06 | 2002-07-24 | 湖南化工研究院 | Preparation and use method of catalyst for synthesis of 2,6-dimethylaniline |
| WO2003091218A1 (en) * | 2002-04-26 | 2003-11-06 | Nissan Chemical Industries, Ltd. | Method for producing a 7-alkyl-8-hydroxyquinoline by hydrogenation of 7-alkenyl-8 hydroxyquinoline |
-
1983
- 1983-12-20 JP JP58238922A patent/JPS60130568A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087970C (en) * | 1997-08-06 | 2002-07-24 | 湖南化工研究院 | Preparation and use method of catalyst for synthesis of 2,6-dimethylaniline |
| WO2003091218A1 (en) * | 2002-04-26 | 2003-11-06 | Nissan Chemical Industries, Ltd. | Method for producing a 7-alkyl-8-hydroxyquinoline by hydrogenation of 7-alkenyl-8 hydroxyquinoline |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0319229B2 (en) | 1991-03-14 |
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