JPH03153649A - Production of n-alkylaminophenols - Google Patents
Production of n-alkylaminophenolsInfo
- Publication number
- JPH03153649A JPH03153649A JP1293392A JP29339289A JPH03153649A JP H03153649 A JPH03153649 A JP H03153649A JP 1293392 A JP1293392 A JP 1293392A JP 29339289 A JP29339289 A JP 29339289A JP H03153649 A JPH03153649 A JP H03153649A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- catalyst
- platinum
- weight
- aldehydes
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 14
- 150000002576 ketones Chemical class 0.000 claims abstract description 14
- 230000000737 periodic effect Effects 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 238000006722 reduction reaction Methods 0.000 claims description 20
- 238000005932 reductive alkylation reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000000975 dye Substances 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000005804 alkylation reaction Methods 0.000 abstract description 2
- 239000007850 fluorescent dye Substances 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 229910052745 lead Inorganic materials 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 33
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 8
- -1 amine phenols Chemical class 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229940018563 3-aminophenol Drugs 0.000 description 4
- 239000013065 commercial product Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical compound O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- NYYLZXREFNYPKB-UHFFFAOYSA-N 1-[ethoxy(methyl)phosphoryl]oxyethane Chemical compound CCOP(C)(=O)OCC NYYLZXREFNYPKB-UHFFFAOYSA-N 0.000 description 1
- AEEZXQFUVDKVFT-UHFFFAOYSA-N 2-(benzylamino)phenol Chemical compound OC1=CC=CC=C1NCC1=CC=CC=C1 AEEZXQFUVDKVFT-UHFFFAOYSA-N 0.000 description 1
- WTFYGNVWNFVUIK-UHFFFAOYSA-N 2-(butylamino)phenol Chemical compound CCCCNC1=CC=CC=C1O WTFYGNVWNFVUIK-UHFFFAOYSA-N 0.000 description 1
- NQTSBOHCYASAMX-UHFFFAOYSA-N 2-(cyclohexylamino)phenol Chemical compound OC1=CC=CC=C1NC1CCCCC1 NQTSBOHCYASAMX-UHFFFAOYSA-N 0.000 description 1
- NOXLTVYOJPQDLQ-UHFFFAOYSA-N 2-(dibutylamino)phenol Chemical compound CCCCN(CCCC)C1=CC=CC=C1O NOXLTVYOJPQDLQ-UHFFFAOYSA-N 0.000 description 1
- BCESCHGDVIYYPC-UHFFFAOYSA-N 2-(ethylamino)phenol Chemical compound CCNC1=CC=CC=C1O BCESCHGDVIYYPC-UHFFFAOYSA-N 0.000 description 1
- BLCSQUZTWKPKSR-UHFFFAOYSA-N 2-(propan-2-ylamino)phenol Chemical compound CC(C)NC1=CC=CC=C1O BLCSQUZTWKPKSR-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- WSYQICTYJNDJGM-UHFFFAOYSA-N 2-[ethyl(pentyl)amino]phenol Chemical compound CCCCCN(CC)C1=CC=CC=C1O WSYQICTYJNDJGM-UHFFFAOYSA-N 0.000 description 1
- UYCQPUOZMLYRFO-UHFFFAOYSA-N 3-(cyclohexylamino)phenol Chemical compound OC1=CC=CC(NC2CCCCC2)=C1 UYCQPUOZMLYRFO-UHFFFAOYSA-N 0.000 description 1
- HDTPORVRVIZAKJ-UHFFFAOYSA-N 3-(diethylamino)hex-2-enal Chemical compound CCCC(=CC=O)N(CC)CC HDTPORVRVIZAKJ-UHFFFAOYSA-N 0.000 description 1
- WAVOOWVINKGEHS-UHFFFAOYSA-N 3-(diethylamino)phenol Chemical compound CCN(CC)C1=CC=CC(O)=C1 WAVOOWVINKGEHS-UHFFFAOYSA-N 0.000 description 1
- ITIUWGUDYZNQFM-UHFFFAOYSA-N 3-[ethyl(2-methylpropyl)amino]phenol Chemical compound CC(C)CN(CC)C1=CC=CC(O)=C1 ITIUWGUDYZNQFM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- JOKPITBUODAHEN-UHFFFAOYSA-N sulfanylideneplatinum Chemical compound [Pt]=S JOKPITBUODAHEN-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 229940075420 xanthine Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明ハ、アミノフェノール類とアルデヒド類、又はア
ミノフェノール類とケトン類を、有機溶媒、還元用触媒
及び水素の存在下に、還元アルキル化反応に付してＮ−
アルキルアミノフェノール類を製造する方法に関する。Detailed Description of the Invention <Industrial Application Field> The present invention iii) Reductive alkylation of aminophenols and aldehydes, or aminophenols and ketones in the presence of an organic solvent, a reduction catalyst, and hydrogen. When subjected to reaction, N-
The present invention relates to a method for producing alkylaminophenols.
Ｎ−アルキルアミノフェノール類は、感熱・感圧紙用染
料、キサンチン系染料、蛍光染料等の中間体として工業
的に極めて重要な化合物である。N-alkylaminophenols are industrially extremely important compounds as intermediates for heat-sensitive and pressure-sensitive paper dyes, xanthine dyes, fluorescent dyes, and the like.
〈従来の技術〉 従来、アミノフェノール類とアルデヒド類。<Conventional technology> Traditionally, aminophenols and aldehydes.
又はアミンフェノール類とケトン類を、有機溶媒、還元
用触媒、及び水素の存在下に、還元アルキル化反応に付
してＮ−アルキルアミノフェノール類を製造する方法は
公知である。Alternatively, a method for producing N-alkylaminophenols by subjecting amine phenols and ketones to a reductive alkylation reaction in the presence of an organic solvent, a reducing catalyst, and hydrogen is known.
しかし、還元アルキル化反応に従来より用いられている
白金系、パラジウム系などの貴金属類の触媒は、芳香環
に対する還元能力を有しているため、そのまま使用する
場合には１反応条件によっては、副反応として芳香環の
核水添が起こり、その結果、目的物であるＮ−アルキル
アミノフェノール類の収率が低下してしまうという問題
があった。また、工業的には、これらの貴金属触媒は高
価であるので９通常、触媒を繰返して使用することが必
須となるが、触媒を繰返して使用した場合には、芳香環
の核水添の他、アミンフェノール類とアルデヒド類、又
はアミノフェノール類とケトン類との重質化反応の発生
、更に、アルデヒド類又はケトン類が還元されることに
よるアルコールの副生が増加するなど、工業的に問題が
あった。However, since platinum-based, palladium-based, and other noble metal catalysts conventionally used in reductive alkylation reactions have the ability to reduce aromatic rings, depending on the reaction conditions when used as is, There is a problem in that nuclear hydrogenation of aromatic rings occurs as a side reaction, and as a result, the yield of the target product, N-alkylaminophenols, decreases. In addition, industrially, since these precious metal catalysts are expensive9, it is usually necessary to use the catalyst repeatedly; , the occurrence of heavy reactions between amine phenols and aldehydes, or aminophenols and ketones, and an increase in alcohol by-products due to the reduction of aldehydes or ketones. was there.
上記の問題のうち、アルコールの副生に対しては２例え
ば、特開昭５７−１６５３４９号公報、特開昭５８−２
６８４４号公報、特開昭５８−１９４８４３号公報に。Among the above-mentioned problems, regarding the by-product of alcohol, there are two problems, for example, JP-A-57-165349 and JP-A-58-2.
No. 6844 and Japanese Unexamined Patent Publication No. 194843/1984.
還元アルキル化反応の際に、固体の硫黄化合物を添加し
たり、硫化白金触媒を用いることによリアルコールの副
生を抑制する技術が記載されている。Techniques have been described for suppressing the by-product of real alcohol by adding a solid sulfur compound or using a platinum sulfide catalyst during the reductive alkylation reaction.
しかしながら、この技術により、アルコールの副生はあ
る程度抑制できるが、一方、主反応である還元アルキル
化反応の反応速度も同時に抑制されるため、アミンフェ
ノール類の不安定なシッフベースの重質化反応が生起し
てしまうという問題があり、更に、触媒を繰返して使用
した場合に、触媒から硫黄が脱離することにより１反応
の制御が困難になるといった問題がある。However, although this technology can suppress alcohol by-products to some extent, it also suppresses the reaction rate of the main reaction, the reductive alkylation reaction, so that the unstable Schiff base-heavy reaction of amine phenols is Furthermore, when the catalyst is used repeatedly, sulfur is eliminated from the catalyst, making it difficult to control one reaction.
更に、これら従来技術には、芳香環の核水添を抑制する
技術に関してほとんど記載されておらｆ、’ＩＩにＮ−
アルキルアミノフェノール類の製法に於ける核水添抑制
の技術については、従来、知られていなかった。Furthermore, these conventional techniques hardly describe techniques for suppressing nuclear hydrogenation of aromatic rings.
Techniques for suppressing nuclear hydrogenation in the production of alkylaminophenols have not been previously known.
〈発明が解決しようとする課題〉
本発明は、上記芳香環の核水添反応及び重質化反応など
の好ましくない副反応を抑制し、高収率のもと、触媒を
繰返して使用し得るという。<Problems to be Solved by the Invention> The present invention suppresses undesirable side reactions such as the above-mentioned nuclear hydrogenation reaction and heavyization reaction of the aromatic ring, and enables repeated use of the catalyst with high yield. That's what it means.
工業的に非常に有利なＮ−アルキルアミノフェノール類
の製法を提供することを主たる目的とするものである。The main purpose of this invention is to provide a method for producing N-alkylaminophenols that is industrially very advantageous.
く課題を解決するための手段〉 本発明者らは、上記の目的を達成するために。Means to solve problems〉 In order to achieve the above objectives, the inventors.
鋭意検討した結果９周期律表より選ばれた特定の金属元
素を含有する白金又はパラジウム触媒を使用することに
より、その目的が達成されるという知見を得９本発明に
到達したものである。As a result of extensive studies, the present invention was achieved based on the knowledge that the objective can be achieved by using a platinum or palladium catalyst containing a specific metal element selected from the periodic table.
すなわち９本発明は、有機溶媒及び水素の存在下、アミ
ノフェノール類とアルデヒド類、又はアミンフェノール
類とケトン類から、還元アルキル化反応によりＮ−アル
キルアミノフェノール類を製造するにあたり９周期律表
第ＩＢ族。That is, 9. The present invention is directed to the production of N-alkylaminophenols from aminophenols and aldehydes, or aminephenols and ketones by reductive alkylation reaction in the presence of an organic solvent and hydrogen. IB tribe.
第１［Ｂ族、第ＩＶＢ族、第ＶＢ族及び第ＶＩＢ族から
選ばれる一種以上の金属元素及び白金を活性炭に担持さ
せてなる還元用触媒、又は上記周期律表より選ばれた一
種以上の金属元素及びパラジウムを活性炭に担持させて
なる還元用触媒を用いることを特徴とするＮ−アルキル
アミノフェノール類の製造方法に係るものである。1 [a reduction catalyst comprising one or more metal elements selected from Group B, Group IVB, Group VB, and Group VIB and platinum supported on activated carbon; or one or more catalysts selected from the periodic table above; The present invention relates to a method for producing N-alkylaminophenols, which is characterized by using a reduction catalyst in which a metal element and palladium are supported on activated carbon.
以下、具体的に説明する。This will be explained in detail below.
本発明のアミンフェノール類とは、具体的には、０−ア
ミンフェノール、ｍ−アミンフェノール、ｐ−アミンフ
ェノール等である。Specifically, the amine phenols of the present invention include 0-amine phenol, m-amine phenol, p-amine phenol, and the like.
アルデヒド類とは、ホルムアルデヒド、アセトアルデヒ
ド、プロピオンアルデヒド、ブチルアルデヒド、イソア
ミルアルデヒド等の脂肪族アルデヒド、シクロヘキシル
アルデヒド、フルフラール等の環式アルデヒド、ベンズ
アルデヒド、ｐ−トルアルデヒド等の芳香族アルデヒド
等が例示される。Examples of aldehydes include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and isoamylaldehyde, cyclic aldehydes such as cyclohexylaldehyde and furfural, and aromatic aldehydes such as benzaldehyde and p-tolualdehyde.
ケトン類とは、アセトン、２−ブタノン、４−メチル−
２−ペンタノン、等の脂肪族ケトン。Ketones include acetone, 2-butanone, 4-methyl-
Aliphatic ketones such as 2-pentanone.
シクロペンタノン、シクロヘキサノン等の環式％式％ エノン等の芳香族ケトンが例示される。Cyclic % formula% such as cyclopentanone, cyclohexanone, etc. Examples include aromatic ketones such as enone.
Ｎ−アルキルアミノフェノール類とは、Ｎ−エチルアミ
ノフェノール、Ｎ−プロピルアミンフェノール、Ｎ−ブ
チルアミノフェノール＋Ｎ−シクロへキシルアミノフェ
ノール、Ｎ−ベンジルアミノフェノール、Ｎ−イソプロ
ピルアミノフェノール等のＮ−モノアルキルアミノフェ
ノール類＋ ＮＩ Ｎ−ジエチルアミノフェノール。N-alkylaminophenols are N-monophenols such as N-ethylaminophenol, N-propylaminephenol, N-butylaminophenol + N-cyclohexylaminophenol, N-benzylaminophenol, and N-isopropylaminophenol. Alkylaminophenols + NI N-diethylaminophenol.
Ｎ、Ｎ−ジブチルアミノフェノール、Ｎ−エチル−Ｎ−
インブチルアミノフェノール、Ｎ−エチル−Ｎ−インア
ミルアミノフェノール等のＮ。N,N-dibutylaminophenol, N-ethyl-N-
N such as imbutylaminophenol, N-ethyl-N-amylaminophenol, etc.
Ｎ−ジアルキルアミノフェノール類が例示される。Examples include N-dialkylaminophenols.
本発明で使用される有機溶媒としては、脂肪族アルコー
ル、例えば、メタノール、エタノール等が用いられる。The organic solvent used in the present invention includes aliphatic alcohols such as methanol and ethanol.
本発明の最大の特徴は、以下に述べる特定の還元用触媒
を用いる点にある。すなわち１本発明で使用される還元
用触媒は２周期律表第ＩＢ族、第１［Ｂ族、第ＩＶＢ族
、第ＶＢ族及び第ＶＩＢ族から選ばれる一種以上の金属
元素及び白金を活性炭に担持させてなる還元用触媒、又
は上記周期律表より選ばれた一種以上の金属元素及びパ
ラジウムを活性炭に担持させてなる還元用触媒である。The greatest feature of the present invention is that it uses a specific reduction catalyst described below. That is, 1. The reduction catalyst used in the present invention consists of 2. Platinum and one or more metal elements selected from Group IB, Group 1[B, Group IVB, Group VB, and Group VIB of the Periodic Table] and platinum on activated carbon. The present invention is a reduction catalyst formed by supporting a reduction catalyst, or a reduction catalyst formed by supporting one or more metal elements selected from the periodic table and palladium on activated carbon.
周期律表から選ばれる金属元素の具体例としては、 Ｃ
ｕ、 Ｚｎ、 Ｃｄ、 Ｓｎ、 Ｐｂ、 Ａｓ、 Ｓｂ
、 Ｓｅ、 Ｔｅ等が例示される。Specific examples of metal elements selected from the periodic table include C.
u, Zn, Cd, Sn, Pb, As, Sb
, Se, Te, etc. are exemplified.
これら金属の還元用触媒中の含有量としては。The content of these metals in the reduction catalyst.
白金又はパラジウム１重量部あたり０．００１〜０．５
重量部であることが好ましく、より好ましくは０．００
５〜０．５の範囲である。０．００１重量部未満では。0.001 to 0.5 per part by weight of platinum or palladium
It is preferably in parts by weight, more preferably 0.00
It is in the range of 5 to 0.5. Less than 0.001 part by weight.
芳香環の核水添を抑制する効果が不十分な場合がある。The effect of suppressing nuclear hydrogenation of aromatic rings may be insufficient.
一方、０．５重量部を超えると、主反応である環元アル
キル化反応に対する還元用触媒の活性が低下し、その結
果、アミノフェノール類とアルデヒド類、又はアミノフ
ェノール類とケトン類とが縮合して１重質化が増大する
ことがある。On the other hand, if the amount exceeds 0.5 parts by weight, the activity of the reduction catalyst for the ring alkylation reaction, which is the main reaction, decreases, resulting in condensation of aminophenols and aldehydes, or aminophenols and ketones. This may lead to an increase in monoheavy weight.
本発明の反応は、前記有機溶媒、水素及び還元用触媒の
存在下、アミンフェノール類とアルデヒド類、又はアミ
ノフェノール類とケトン類から、還元アルキル化反応に
よりＮ−アルキルアミノフェノール類を得る反応である
。本反応は、アミノフェノール類、有機溶媒及び還元用
触媒を仕込んで、水素加圧下に、アルデヒド類又はケト
ン類を連続供給、又は−括供給して反応することができ
るが、より反応を円滑に行なわせるためには、アルデヒ
ド類又はケトン類を連続的に供給するのが好ましく、又
アルデヒド類又はケトン類の供給に合せて、酢酸等の有
機カルボン酸類を少量、連続添加することがより好まし
い。通常１反応温度は常温〜１５０’Ｃ，反応圧力は２
〜３０ｋｇ／ｃｍ２Ｇで十分である。The reaction of the present invention is a reaction in which N-alkylaminophenols are obtained by a reductive alkylation reaction from aminephenols and aldehydes, or from aminophenols and ketones in the presence of the organic solvent, hydrogen, and a reduction catalyst. be. This reaction can be carried out by charging aminophenols, an organic solvent, and a reducing catalyst, and continuously or batch-supplying aldehydes or ketones under hydrogen pressure, but it is possible to carry out the reaction more smoothly. In order to achieve this, it is preferable to continuously supply aldehydes or ketones, and it is more preferable to continuously add a small amount of organic carboxylic acids such as acetic acid in conjunction with the supply of aldehydes or ketones. Usually 1 reaction temperature is room temperature to 150'C, reaction pressure is 2
~30 kg/cm2G is sufficient.
還元用触媒の使用量は、原料のアミノフェノール類１重
量部に対して、触媒中の白金、又はパラジウム量で、
０．０００１〜０．０２重量部が好ましく。The amount of reduction catalyst used is the amount of platinum or palladium in the catalyst per 1 part by weight of aminophenols as raw materials.
0.0001 to 0.02 parts by weight is preferred.
より好ましい範囲は０．００１〜０．０１重量部である
。A more preferable range is 0.001 to 0.01 parts by weight.
ｏ、ｏｏｏｉ重量部未満では、主反応の速度が遅くなり
。If the amount is less than o or oooi parts by weight, the speed of the main reaction becomes slow.
副反応の重質化が促進されることがあり、又。Side reactions may become heavier.
０．０２重量部を超えると、芳香環の還元が促進される
場合がある。還元用触媒は、１回限りの使用でも良いが
、工業的には通常繰返し使用される。If it exceeds 0.02 parts by weight, reduction of aromatic rings may be promoted. Although the reduction catalyst may be used only once, it is usually used repeatedly in industry.
特に１本発明で用いられる還元用触媒は、−度反応に供
した後でも、前記周期律表より選ばれた金属元素は、触
媒上にほぼ全量残ってＬｚるので、この還元用触媒を繰
返して使用する場合にも特別の処理は必要とせず１本発
明の効果は持続される。なお、繰返し使用する場合には
、触媒の微細化による損失及び濾過回収時の損失等があ
るので１反応を安定に実施するために、必要に応じて少
量の新触媒を追加して２次回の還元アルキル化反応に供
することもできる。In particular, in the reduction catalyst used in the present invention, even after being subjected to the -degree reaction, almost all of the metal elements selected from the periodic table remain on the catalyst, so this reduction catalyst is repeatedly used. Even when used in a vacuum cleaner, no special treatment is required and the effects of the present invention are maintained. In addition, when using the catalyst repeatedly, there is loss due to fineness of the catalyst and loss during filtration recovery, so in order to carry out one reaction stably, a small amount of new catalyst may be added as necessary for the second reaction. It can also be subjected to a reductive alkylation reaction.
〈実施例〉
次に、実施例をあげて本発明をさらに詳細に説明するが
１本発明はこれらに限定されるものではない。<Examples> Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
実施例−１ 撹拌機付きＳＵＳ製５００ ｃｃオートクレーブに。Example-1 In a SUS 500cc autoclave with a stirrer.
ｍ−アミンフェノール３２．７ｇ（０，３０モル）、メ
タノール１８５．５ｇ 、及び白金１重量部に対し０．
１電型部の鉛を含有する５重量％白金担持活性炭触媒（
市販品）１．６ｇを仕込み、４０°Ｃ９水素圧力１０ｋ
ｇ／Ｃｍ２一定の条件下で、４５重１％のアセトアルデ
ヒドを含むメタノール溶液６７．６ｇ（アセトアルデヒ
ド０．６９モル）、及び酢酸０．２０ｇ （０，００３
３モル）を１時間かけて連続導入を行なった。アセトア
ルデヒド導入終了後、同温度でさらに１５０分保持した
後、冷却し、触媒を濾過分離して得られる反応液を、ガ
スクロマトグラフィー、液体クロマトグラフィー、及び
ＧＰＧ （ゲルパーミュエーションクロマトグラフィー
）分析ヲ行なった結果２ｍ−アミンフェノール転化率（
消費されたｍ−アミンフェノール／仕込みｍ−アミンフ
ェノール刈００） １００％、Ｎ、Ｎ−ジエチル−ｍ−
アミノフェノール選択率９５．９％、ベンゼン環の核水
添物（核水添物：３−（ジエチルアミノ）−２−ヘキセ
ン−１−オン） 選択率０．５９６．重質物選択率８２
．１％（選択率はいずれもｍ−アミノフェノールに対す
る値である。）であった。32.7 g (0.30 mol) of m-amine phenol, 185.5 g of methanol, and 0.3 g (0.30 mol) per part by weight of platinum.
5 wt% platinum-supported activated carbon catalyst containing 1 part lead (
Commercially available product) 1.6g was prepared at 40°C9 hydrogen pressure 10k.
g/Cm2 Under constant conditions, 67.6 g of a methanol solution containing 45% by weight of acetaldehyde (0.69 mol of acetaldehyde) and 0.20 g of acetic acid (0,003
3 mol) was continuously introduced over 1 hour. After the introduction of acetaldehyde, the temperature was maintained for an additional 150 minutes, cooled, and the catalyst was separated by filtration. The resulting reaction solution was analyzed by gas chromatography, liquid chromatography, and GPG (gel permeation chromatography). As a result, the conversion rate of 2m-aminephenol (
Consumed m-amine phenol/Prepared m-amine phenol 00) 100%, N,N-diethyl-m-
Aminophenol selectivity 95.9%, benzene ring nuclear hydrogenation product (nuclear hydrogenation product: 3-(diethylamino)-2-hexen-1-one) selectivity 0.596. Heavy matter selectivity 82
．． The selectivity was 1% (all selectivity values are based on m-aminophenol).
実施例−２，、３，４ 実施例−１で使用後回収した触媒を用いて。Example-2, 3, 4 Using the catalyst recovered after use in Example-1.
実施例−１と同様の操作で反応を行なった。以後、同様
に、順次回収した触媒を用いて反応を行なった結果を表
−１に示す。The reaction was carried out in the same manner as in Example-1. Thereafter, reactions were carried out in the same manner using successively recovered catalysts, and the results are shown in Table 1.
表−１
実施例−５〜８
触媒として、白金１重量部に対し０．０６重量部のテル
ルを含有する５重量％白金担持活性炭触媒（市販品）１
．６ｇを触媒として用いた他は、実施例−１〜４と同様
の操作で反応を行なった。Table-1 Examples-5 to 8 5 wt% platinum-supported activated carbon catalyst (commercial product) containing 0.06 parts by weight of tellurium per 1 part by weight of platinum as a catalyst 1
．． The reaction was carried out in the same manner as in Examples 1 to 4, except that 6 g was used as a catalyst.
結果を表−２に示す。The results are shown in Table-2.
表−２
実施例−９〜１２
触媒として、白金１重量部に対し０．１５重量部の銅を
含有する５重量％白金担持活性炭触媒（市販品）１．６
ｇを触媒として用いた他は、実施例−１〜４と同様の操
作で反応を行なった。Table 2 Examples 9 to 12 5 wt% platinum-supported activated carbon catalyst (commercial product) containing 0.15 parts by weight of copper per 1 part by weight of platinum as a catalyst 1.6
The reaction was carried out in the same manner as in Examples 1 to 4, except that g was used as a catalyst.
結果を表−３に示す。The results are shown in Table-3.
（圧）ｍ−アミノフェノール転化率はスヘて１００％比
較例−１〜４
触媒として、５重量％白金担持活性炭触媒（本発明の周
期律表より選ばれた金属元素を含有しない市販品）１．
６ｇを触媒として用いた他は、実施例−１〜４と同様の
操作で反応を行なった。結果を表−４に示す。(Pressure) The conversion rate of m-aminophenol was 100% Comparative Examples-1 to 4 As a catalyst, 5% by weight platinum-supported activated carbon catalyst (commercial product containing no metal elements selected from the periodic table of the present invention) 1 ．．
The reaction was carried out in the same manner as in Examples 1 to 4, except that 6 g was used as a catalyst. The results are shown in Table 4.
表−４
（注）ｍ−アミノフェノール転化率はすべて１００％本
比較例において、特に触媒を繰返して使用した場合に核
水添物が大量に副生じ、ＤＥＭＰの収率は大幅に低下し
てしまった。Table 4 (Note) All m-aminophenol conversion rates were 100%. In this comparative example, a large amount of nuclear hydrogenated products were produced as a by-product, especially when the catalyst was used repeatedly, and the yield of DEMP was significantly reduced. Oops.
実施例−１３〜１６
４５重量％のアセトアルデヒドを含むメタノール溶液の
代わりに、 ５０重量％のｎ−ブチルアルデヒドを含む
メタノール溶液１０３．８ｇ（ｎ−ブチルアルデヒド０
．７２モル）を使用して１時間かけて連続導入した他は
、実施例−１〜４と同様の操作で反応を行ない、 Ｎ、
Ｎ−ジブチル−ｍ −アミノフェノールの合成を行な
った。結果を表−５に示す。Examples 13 to 16 Instead of a methanol solution containing 45% by weight of acetaldehyde, 103.8 g of a methanol solution containing 50% by weight of n-butyraldehyde (n-butyraldehyde 0
．． The reaction was carried out in the same manner as in Examples 1 to 4, except that 72 mol) was used and continuously introduced over 1 hour.
N-dibutyl-m-aminophenol was synthesized. The results are shown in Table-5.
表−５
２０，３６モル）を使用して３０分かけて連続導入した
他は、実施例−１〜４と同様の操作で反応を行ｆＬい、
Ｎ−シクロへキシル−ｍ−アミノフェノールの合成を行
なった。結果を表−６に示す。Table 5 The reaction was carried out in the same manner as in Examples 1 to 4, except that 20.36 mol) was used and continuously introduced over 30 minutes.
N-cyclohexyl-m-aminophenol was synthesized. The results are shown in Table-6.
表−６
実施例−１７〜２０
４５ｉｆｉ％のアセトアルデヒドを含むメタノール溶液
の代わりに５０重量％のシクロヘキサノンを含むメタノ
ール溶液７０．６ｇ（シクロヘキサノ実施例−２１〜２
４
実施例−１〜４と同様の操作を行ない、Ｎ−エチル−Ｎ
−イソブチル−ｍ−アミノフェノールの合成を行なった
。撹拌機付きＳＵＳ製５００ＣＣオートクレーブに９ｍ
−アミノフェノール３２．７ ｇ （０，３０モル）、
メタノール１８５．５ ｇ 、及び白金１重量部に対し
０．１重量部の鉛を含有する５重１％白金担持活性炭触
媒（市販品）１゜６ｇを仕込み、 ４０’Ｃ，水素圧力
１０ｋｇ／’ｃｍ２一定の条件下で。Table-6 Examples-17 to 20 70.6 g of methanol solution containing 50% by weight of cyclohexanone instead of methanol solution containing 45ifi% of acetaldehyde (cyclohexano Examples-21 to 2)
4 Perform the same operations as in Examples 1 to 4 to prepare N-ethyl-N
-Isobutyl-m-aminophenol was synthesized. 9m in SUS 500CC autoclave with stirrer
- aminophenol 32.7 g (0.30 mol),
185.5 g of methanol and 1.6 g of 5 weight 1% platinum-supported activated carbon catalyst (commercial product) containing 0.1 part by weight of lead per 1 part by weight of platinum were charged, and the temperature was 40'C and hydrogen pressure was 10 kg/'. cm2 under constant conditions.
５０重量％のイソブチルアルデヒドを含むメタノール溶
液４７．６ ｇ （イソブチルアルデヒド０．３３モル
）を３０分かけて連続導入を行なった。イソブチルアル
デヒド導入終了後、同温度でさらに６０分保持した後、
４５重量％のアセトアルデヒドを含むメタノール溶液４
１．１ ｇ （アセトアルデヒド０．４２モル）、及び
酢酸０．２０ ｇ （０，００３３モル）を３０分かけ
て連続導入を行ない、アセトアルデヒド導入終了後、同
温度でさらに７０分保持した後、冷却し触媒を濾過分離
して得られる反応液をガスクロマトグラフィー、液体ク
ロマトグラフィー、及びＧＰＣ（ゲルパーミュエーショ
ンクロマトグラフィー）分析を行なった。回収された触
媒は。47.6 g (0.33 mol of isobutyraldehyde) of a methanol solution containing 50% by weight of isobutyraldehyde was continuously introduced over 30 minutes. After the introduction of isobutyraldehyde, the temperature was maintained for an additional 60 minutes,
Methanol solution containing 45% by weight of acetaldehyde 4
1.1 g (acetaldehyde 0.42 mol) and acetic acid 0.20 g (0,0033 mol) were continuously introduced over 30 minutes, and after the completion of acetaldehyde introduction, the temperature was maintained for an additional 70 minutes, and then cooled. The reaction solution obtained by filtering and separating the catalyst was analyzed by gas chromatography, liquid chromatography, and GPC (gel permeation chromatography). The recovered catalyst.
再び次の反応で使用した。結果を表−７に示す。It was used again in the next reaction. The results are shown in Table-7.
表−７
実施例−２５〜２８
５０重量％のイソブチルアルデヒドを含むメタノール溶
液の代わりに、５０重量％のイソアミルアルデヒドを含
むメタノール溶液５６．８ ｇ （イソアミルアルデヒ
ド０．３３モル）を使用して３０分かけて連続導入した
他は、実施例−２】〜２４と同様の操作で反応を行ない
、Ｎ−エチル−Ｎ−インアミル−ｍ−アミンフェノール
の合成を行なった。Table 7 Examples 25 to 28 Using 56.8 g (0.33 mol of isoamylaldehyde) of a methanol solution containing 50% by weight of isoamylaldehyde in place of the methanol solution containing 50% by weight of isobutyraldehyde. N-ethyl-N-ynamyl-m-aminephenol was synthesized by carrying out the reaction in the same manner as in Examples 2 to 24, except that the mixture was introduced continuously over several minutes.
結果を表−８に示す。The results are shown in Table-8.
表−８
的に罹めて有利にＮ−アルキルアミノフェノール類を製
造する方法を提供することカイできｔこ。Table 8 It is possible to provide a method for producing N-alkylaminophenols in a cost effective and advantageous manner.
キャン−ｌ−オン 〈発明の効果〉can-l-on <Effect of the invention>
Claims (3)
とアルデヒド類、又はアミノフェノー類とケトン類から
、還元アルキル化反応によりＮ−アルキルアミノフェノ
ール類を製造するにあたり、周期律表第 I Ｂ族、第II
Ｂ族、第IVＢ族、第ＶＢ族及び第VIＢ族から選ばれる一
種以上の金属元素及び白金を活性炭に担持させてなる還
元用触媒、又は上記周期律表より選ばれた一種以上の金
属元素及びパラジウムを活性炭に担持させてなる還元用
触媒を用いることを特徴とするＮ−アルキルアミノフェ
ノール類の製造方法。(1) In the production of N-alkylaminophenols from aminophenols and aldehydes, or aminophenols and ketones by reductive alkylation reaction in the presence of an organic solvent and hydrogen, N-alkylaminophenols from group IB of the periodic table are used. , No. II
A reduction catalyst comprising one or more metal elements selected from Group B, Group IVB, Group VB and Group VIB and platinum supported on activated carbon, or one or more metal elements selected from the periodic table above and platinum. A method for producing N-alkylaminophenols, which comprises using a reduction catalyst in which palladium is supported on activated carbon.
パラジウム１重量部あたり０．００１〜０．５重量部で
ある還元用触媒を用いる請求項（１）記載の方法。(2) The method according to claim (1), wherein the reduction catalyst contains a metal element selected from the periodic table in an amount of 0.001 to 0.5 parts by weight per part by weight of platinum or palladium.
は銅である請求項（１）又は（２）記載の方法。(3) The method according to claim (1) or (2), wherein the metal element selected from the periodic table is lead, tellurium or copper.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1293392A JPH0761989B2 (en) | 1989-11-10 | 1989-11-10 | Method for producing N-alkylaminophenols |
| CA 2029499 CA2029499C (en) | 1989-11-10 | 1990-11-07 | Process for preparing n-alkylaminophenols |
| DE1990608488 DE69008488T2 (en) | 1989-11-10 | 1990-11-09 | Process for the preparation of N-alkylaminophenols and of N, N-dialkylaminophenols. |
| EP19900312304 EP0427572B1 (en) | 1989-11-10 | 1990-11-09 | Process for preparing N-alkylaminophenols and N,N-dialkylaminophenols |
| US07/692,437 US5202485A (en) | 1989-11-10 | 1991-04-29 | Process for preparing N-alkylaminophenols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1293392A JPH0761989B2 (en) | 1989-11-10 | 1989-11-10 | Method for producing N-alkylaminophenols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03153649A true JPH03153649A (en) | 1991-07-01 |
| JPH0761989B2 JPH0761989B2 (en) | 1995-07-05 |
Family
ID=17794172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1293392A Expired - Fee Related JPH0761989B2 (en) | 1989-11-10 | 1989-11-10 | Method for producing N-alkylaminophenols |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0761989B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009173553A (en) * | 2008-01-22 | 2009-08-06 | Koei Chem Co Ltd | Method for producing 2-(isopropylamino)ethanol |
| CN113649024A (en) * | 2021-08-10 | 2021-11-16 | 北京旋光普利生物医药科技开发有限公司 | Preparation of catalyst for producing ethyl p-butylaminobenzoate |
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| JPS61100551A (en) * | 1984-10-23 | 1986-05-19 | Kanzaki Paper Mfg Co Ltd | Preparation of cycloalkylaminophenol derivative |
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1989
- 1989-11-10 JP JP1293392A patent/JPH0761989B2/en not_active Expired - Fee Related
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|---|---|---|---|---|
| JPS5798241A (en) * | 1980-10-16 | 1982-06-18 | Basf Ag | Manufacture of primary aromatic amine |
| JPS61100551A (en) * | 1984-10-23 | 1986-05-19 | Kanzaki Paper Mfg Co Ltd | Preparation of cycloalkylaminophenol derivative |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009173553A (en) * | 2008-01-22 | 2009-08-06 | Koei Chem Co Ltd | Method for producing 2-(isopropylamino)ethanol |
| CN113649024A (en) * | 2021-08-10 | 2021-11-16 | 北京旋光普利生物医药科技开发有限公司 | Preparation of catalyst for producing ethyl p-butylaminobenzoate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0761989B2 (en) | 1995-07-05 |
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