JPH0665662B2 - Method for producing triphenylamine or nuclear substitution product thereof - Google Patents
Method for producing triphenylamine or nuclear substitution product thereofInfo
- Publication number
- JPH0665662B2 JPH0665662B2 JP60023521A JP2352185A JPH0665662B2 JP H0665662 B2 JPH0665662 B2 JP H0665662B2 JP 60023521 A JP60023521 A JP 60023521A JP 2352185 A JP2352185 A JP 2352185A JP H0665662 B2 JPH0665662 B2 JP H0665662B2
- Authority
- JP
- Japan
- Prior art keywords
- substitution product
- nuclear substitution
- phenol
- diphenylamine
- product
- 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 - Lifetime
Links
- 238000006467 substitution reaction Methods 0.000 title claims description 23
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 49
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 32
- 239000000047 product Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 description 17
- 125000002243 cyclohexanonyl group Chemical class *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 description 11
- 125000006617 triphenylamine group Chemical class 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 1
- JTMODJXOTWYBOZ-UHFFFAOYSA-N 2-methyl-n-phenylaniline Chemical compound CC1=CC=CC=C1NC1=CC=CC=C1 JTMODJXOTWYBOZ-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- TWPMMLHBHPYSMT-UHFFFAOYSA-N 3-methyl-n-phenylaniline Chemical compound CC1=CC=CC(NC=2C=CC=CC=2)=C1 TWPMMLHBHPYSMT-UHFFFAOYSA-N 0.000 description 1
- MNVMYTVDDOXZLS-UHFFFAOYSA-N 4-methoxyguaiacol Natural products COC1=CC=C(O)C(OC)=C1 MNVMYTVDDOXZLS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- XCVKVYNICFBSJQ-UHFFFAOYSA-N [Re].[C] Chemical compound [Re].[C] XCVKVYNICFBSJQ-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical group 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明はトリフエニルアミンまたはその核置換体（以下
トリフエニルアミン類と略記）の製造方法に関する。さ
らに詳しくは、水素移動触媒の存在下に、ジフエニルア
ミンまたはその核置換体（以下ジフエニルアミン類と略
記）、フエノールまたはその核置換体（以下フエノール
類と略記）、及びこのフエノール類に対応するシクロヘ
キサノンまたはその環置換体（以下シクロヘキサノン類
と略記）、を反応させ、縮合及び脱水素反応によりトリ
フエニルアミン類を製造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing triphenylamine or a nuclear substitution product thereof (hereinafter abbreviated as triphenylamines). More specifically, in the presence of a hydrogen transfer catalyst, diphenylamine or its nuclear substitution product (hereinafter abbreviated as diphenylamines), phenol or its nuclear substitution product (hereinafter abbreviated as phenols), and cyclohexanone corresponding to this phenol or its The present invention relates to a method for producing triphenylamines by reacting a ring-substituted product (hereinafter abbreviated as cyclohexanone), and performing condensation and dehydrogenation reaction.
トリフエニルアミン類は、一般化学工業中間体特に染
料、農薬、ゴム薬等の中間体として有用な化合物であ
る。Triphenylamines are compounds useful as intermediates for general chemical industry, especially as intermediates for dyes, agricultural chemicals, rubber drugs and the like.
従来の技術 従来、トリフエニルアミン類の製造方法としては、アニ
リン類もしくはジフエニルアミン類のカリウム塩とブロ
ムベンゼンとを加熱反応させる方法、ジフエニルアミン
とアニリンとを塩酸存在下に反応させる方法（USP 205
1123）、銅クロム酸化物触媒の存在下にアニリンとフエ
ノールを反応させる方法（特公昭52−48969公報）ジフ
エニルアミンと当モル量のシクロヘキサノンとをパラジ
ウム触媒の存在下反応させる方法（USP 3219704）等が
知られている。2. Description of the Related Art Conventionally, as a method for producing triphenylamines, a method of heating a potassium salt of aniline or diphenylamines and bromobenzene by heating, a method of reacting diphenylamine and aniline in the presence of hydrochloric acid (USP 205
1123), a method of reacting aniline and phenol in the presence of a copper chromium oxide catalyst (Japanese Patent Publication No. 52-48969), a method of reacting diphenylamine and an equimolar amount of cyclohexanone in the presence of a palladium catalyst (USP 3219704) and the like. Are known.
発明が解決しようとする問題点 従来技術においては、反応工程が煩雑であったり、多量
の酸、塩基を必要とする等の欠点があり、また、本発明
方法と類似のUSP 3219704記載の方法では収率14％と極
めて収率が低く工業的なトリフエニルアミン類の製造方
法としては満足できるものではなかった。Problems to be Solved by the Invention In the prior art, there are drawbacks such as a complicated reaction step, a large amount of acid, and a need for a base, and in the method of USP 3219704 described similar to the method of the present invention. The yield was 14%, which was extremely low and was not satisfactory as an industrial method for producing triphenylamines.
問題を解決するための手段 本発明者等は上記欠点を改良すべく鋭意検討の結果、水
素移動触媒の存在下に、ジフエニルアミン類、過剰量の
フエノール類及び上記反応に用いるフエノール類に対応
する触媒量のシクロヘキサノン類を加熱反応させるか、
または最初から反応系中にシクロヘキサノン類を共存さ
せておくことなく、過剰に仕込んだフエノール類を、ジ
フエニルアミン類中で水素加圧下にその一部を対応する
シクロヘキサノン類に変換させつつ、フエノール類及び
ジフエニルアミン類を加熱反応させることにより高収率
で高品質のトリフエニルアミン類が製造できることを見
い出し本発明に到達した。Means for Solving the Problem As a result of intensive studies to improve the above-mentioned drawbacks, the present inventors have found that in the presence of a hydrogen transfer catalyst, diphenylamines, an excess amount of phenols and a catalyst corresponding to the phenols used in the above reaction are used. Heat reaction of cyclohexanones in an amount,
Or, from the beginning, without allowing coexistence of cyclohexanones in the reaction system, excess charged phenols are partially converted to corresponding cyclohexanones under hydrogen pressure in diphenylamines, while the phenols and diphenylamines are converted. It was found that high-quality and high-quality triphenylamines can be produced by heating and reacting the compounds with each other to reach the present invention.
本発明方法におけるフエノール類は水素受容体であり、
且つその結果生成されるシクロヘキサノン類の供給源で
もある為、反応中に副生される水素は系内において完全
に利用されるとともに、目的生成物のトリフエニルアミ
ン類を取出す際、分離されるシクロヘキサノン類を含ん
だフエノール類は、混合物のまま反応系に循環再使用で
きる。さらに核置換体トリフエニルアミン類のある種の
製造において、相当する適当なシクロヘキサノン類の入
手が困難である場合も、フエノール類さえあればシクロ
ヘキサノン類の替りに過剰量のフエノール類を使用して
あらかじめ水素を仕込み、フエノール類の一部をシクロ
ヘキサノンに変換しつつ反応させればよい等適用範囲が
広い等数々の利点がある。The phenols in the method of the present invention are hydrogen acceptors,
Since it is also the source of the resulting cyclohexanones, the hydrogen produced as a by-product during the reaction is completely utilized in the system, and the cyclohexanone separated when the triphenylamines of the desired product are taken out. The phenols containing the compounds can be reused as a mixture in the reaction system by recycling. Furthermore, in the production of certain types of nuclear-substituted triphenylamines, even when it is difficult to obtain the corresponding appropriate cyclohexanones, it is necessary to use an excess amount of phenols instead of cyclohexanones as long as there are phenols. There are various advantages such as wide application range such as charging hydrogen and reacting while converting a part of the phenols into cyclohexanone.
本発明の方法において、原料として使用されるジフエニ
ルアミン類としては公知のいかなるものでも良いが、例
えばジフエニルアミン、２−メチル−ジフエニルアミ
ン、３−メチル−ジフエニルアミン、2,2′−ジメチル
−ジフエニルアミン等核がアルキル基によって置換され
たジフエニルアミン、同じくアルコキシ基置換ジフエニ
ルアミン、ハロゲン置換ジフエニルアミン、カルボン酸
基置換ジフエニルアミン、ニトリル基置換ジフエニルア
ミン、Ｐ−フエニルジフエニルアミン等が挙げられる。
また２−メチル−４−クロル−ジフエニルアミン等核に
置換されている官能基が異なったジフエニルアミンでも
よい。In the method of the present invention, the diphenylamines used as a raw material may be any known ones, for example, diphenylamine, 2-methyl-diphenylamine, 3-methyl-diphenylamine, 2,2'-dimethyl-diphenylamine, etc. Examples thereof include diphenylamine substituted by a group, similarly alkoxy group-substituted diphenylamine, halogen-substituted diphenylamine, carboxylic acid group-substituted diphenylamine, nitrile group-substituted diphenylamine, P-phenyldiphenylamine and the like.
Further, diphenylamine having different functional groups substituted in the nucleus, such as 2-methyl-4-chloro-diphenylamine, may be used.
フエノール類としては公知のいかなるものでも良いが、
例えばフエノール、メチルフエノール、エチルフエノー
ル、イソプロピルフエノール、ブチルフエノール、2,4
−ジメチルフエノール、2,4,6−トリメチルフエノール
等アルキルフエノール、４−メトキシフエノール等アル
コキシフエノール等が挙げられる。特に本反応はアニリ
ン類とフエノールとの反応にくらべて比較的に反応が遅
いので立体障害の小さいフエノール類即ちフエノールま
たはＰ−置換フエノールが好ましい。その使用量はシク
ロヘキサノン類を始めから共存させる場合はジフエニル
アミンと当量以上であれば特に問題ないが、通常は溶媒
としても使用されるので、ジフエニルアミン類に対し２
〜20モル倍の過剰量、好ましくは４〜10モル倍使用する
のが良い。Any known phenols may be used,
For example, phenol, methylphenol, ethylphenol, isopropylphenol, butylphenol, 2,4
-Dimethylphenol, alkylphenols such as 2,4,6-trimethylphenol, and alkoxyphenols such as 4-methoxyphenol. In particular, this reaction is relatively slow as compared with the reaction between anilines and phenol, and therefore phenols having small steric hindrance, that is, phenol or P-substituted phenol is preferable. When cyclohexanone is used together from the beginning, there is no particular problem as long as it is equivalent to or more than diphenylamine, but since it is usually also used as a solvent, it is 2
It is preferable to use an excess amount of up to 20 mol times, preferably 4 to 10 mol times.
またシクロヘキサノン類としては前述のフエノール類に
対応するシクロヘキサノン類が用いられ、その使用量は
ジフエニルアミン類に対し触媒量の約0.03モル倍以上で
あれば特に問題ないが、好ましくは0.05〜0.40モル倍が
良い。As cyclohexanones, cyclohexanones corresponding to the above-mentioned phenols are used, and the amount thereof is not particularly problematic if it is about 0.03 mol times or more of the catalyst amount with respect to diphenylamines, but preferably 0.05 to 0.40 mol times. good.
また反応の最初からシクロヘキサノン類を使用しない場
合はフエノール類に対し、前記の適量のシクロヘキサノ
ン類を生成するに相当する量、即ち。約0.06モル倍以
上、好ましくは0.10〜0.80モル倍の水素を反応器に封入
後加熱反応すれば良い。When cyclohexanones are not used from the beginning of the reaction, an amount equivalent to the above-mentioned suitable amount of cyclohexanones is produced with respect to phenols. About 0.06 mol times or more, preferably 0.10 to 0.80 mol times of hydrogen may be charged in the reactor and heated for reaction.
本発明の方法において使用される触媒としては脱水素反
応及び還元反応の両方の機能を有する触媒である必要が
あるが、通常好適な水素化還元触媒は脱水素反応にも適
する。具体的には、ラネーニツケル、還元ニツケル、も
しくはニツケル担体触媒、ラネーコバルト、還元コバル
ト、もしくはコバルト担体触媒、ラネー銅、還元銅もし
くは銅担体触媒、周期律表第８族金属触媒もしくはその
貴金属が担体として、炭素、アルミナ、炭酸バリウム等
に担持された触媒、レニウム−炭素等のレニウム触媒、
銅−クロム酸化物触媒等が挙げられる。これらの触媒の
内、好ましくはパラジウムであり、特にパラジウム−炭
素、パラジウム−アルミナ及びパラジウム−酸化マグネ
シウム等の担体に担持されたパラジウム触媒が好まし
い。その使用量は前記ジフエニルアミン類に対し金属原
子として通常0.001〜0.2グラム原子、好ましくは0.004
〜0.2グラム原子が良い。The catalyst used in the method of the present invention needs to be a catalyst having both functions of dehydrogenation reaction and reduction reaction, but usually a suitable hydrogenation reduction catalyst is also suitable for dehydrogenation reaction. Specifically, Raney-Nickel, reduced Nickel, or Nickel-supported catalysts, Raney cobalt, reduced cobalt, or cobalt-supported catalysts, Raney copper, reduced copper or copper-supported catalysts, Group 8 metal catalysts of the Periodic Table or noble metals thereof as carriers. , A catalyst supported on carbon, alumina, barium carbonate, etc., a rhenium catalyst such as rhenium-carbon,
Examples include copper-chromium oxide catalysts. Of these catalysts, palladium is preferable, and a palladium catalyst supported on a carrier such as palladium-carbon, palladium-alumina and palladium-magnesium oxide is particularly preferable. The amount thereof is usually 0.001 to 0.2 gram atom, preferably 0.004 as a metal atom with respect to the diphenylamines.
~ 0.2 grams atom is good.
尚、本発明の方法においては反応終了後の反応マスから
目的生成物を分離後、シクロヘキサノンは分離すること
なく反応液は繰り返し連続的に循環使用するのが好まし
く、その際フエノール類を自溶媒として過剰使用するの
が有利であり、その他の反応溶媒を使用する必要は無い
が、勿論使用しても何ら支障はない。In the method of the present invention, after the target product is separated from the reaction mass after completion of the reaction, it is preferable that the reaction solution is repeatedly and continuously circulated without separating cyclohexanone, in which case the phenols are used as self-solvents. It is advantageous to use in excess, and it is not necessary to use another reaction solvent, but of course there is no problem even if it is used.
反応の際の温度は通常150〜400℃、好ましくは180〜350
℃の範囲で選ばれる。The temperature during the reaction is usually 150 to 400 ° C, preferably 180 to 350
It is selected in the range of ° C.
生成したトリフエニルアミン類は反応終了後の混合物を
蒸溜、晶析等の常法に従って処理することにより得られ
る。The produced triphenylamines can be obtained by treating the mixture after the reaction according to a conventional method such as distillation and crystallization.
次に、本発明方法を実施例によって具体的に説明する。Next, the method of the present invention will be specifically described with reference to examples.
実施例１ 内容積500mlのステンレス製オートクレーブにジフエニ
ルアミン67.7g（0.4モル）、フエノール188.2g（2.0モ
ル）、シクロヘキサノン3.0g（0.03モル）及び５％のパ
ラジウム−炭素（日本エンゲルハルド社製）11.0gを仕
込んだ。オートクレーブ内を窒素置換した後、280℃に
昇温した。攪拌下にその温度で16時間反応させた後、室
温に冷却後反応混合液を過して触媒を分離した。液
の一部を採取し、ガスクロマトグラフイーにより分析し
て末反応原料及び生成物を定量した。その結果、末反応
のジフエニルアミンが13.2g（転化率80.5％）残存し、
トリフエニルアミンが67.2g（選択率85.1％）生成して
いた。液を源圧濃縮して末反応フエノール（シクロヘ
キサノンが濃度0.6％含まれていた）及びジフエニルア
ミンを分離回収した後、濃縮物をｎ−ヘキサンで再結晶
し、融点125.6〜126.9℃、ガスクロマトグラフイーによ
る純度99.2％のトリフエニルアミン53.8gを得た。Example 1 67.7 g (0.4 mol) of diphenylamine, 188.2 g (2.0 mol) of phenol, 3.0 g (0.03 mol) of cyclohexanone, and 11.0 g of 5% palladium-carbon (manufactured by Nippon Engelhard) in an autoclave of stainless steel having an internal volume of 500 ml. Was charged. After replacing the inside of the autoclave with nitrogen, the temperature was raised to 280 ° C. After reacting at that temperature for 16 hours with stirring, the reaction mixture was cooled to room temperature and the reaction mixture was passed through to separate the catalyst. A part of the liquid was collected and analyzed by gas chromatography to quantify the unreacted starting materials and products. As a result, 13.2 g (80.5% conversion) of unreacted diphenylamine remained,
67.2 g (selectivity 85.1%) of triphenylamine was formed. The liquid was concentrated under source pressure to separate and collect unreacted phenol (containing cyclohexanone at a concentration of 0.6%) and diphenylamine, and then the concentrate was recrystallized with n-hexane and had a melting point of 125.6 to 126.9 ° C by gas chromatography. 53.8 g of triphenylamine having a purity of 99.2% was obtained.
実施例２〜５ 実施例１と同様にして、種々のジフエニルアミン類及び
シクロヘキサノン類を用いて反応を行った。結果は以下
の通りであった。Examples 2 to 5 In the same manner as in Example 1, various diphenylamines and cyclohexanones were used for the reaction. The results were as follows.
実施例６ 実施例１に用いた内容積500mlのオートクレーブに最初
の仕込みにシクロヘキサノンが無い以外、実施例１の通
り仕込んだ。オートクレーブ内を窒素置換した後、水素
で7kg／cm2Gに加圧した。この水素量はジフエニルアミ
ンに対しシクロヘキサノンとして約0.14モル倍に相当す
る。引き続き実施例１と同様に加熱反応、処理した。そ
の結果、トリフエニルアミンが選択率79.8％で生成し
た。 Example 6 The autoclave having the internal volume of 500 ml used in Example 1 was charged as in Example 1 except that cyclohexanone was not added to the initial charge. After replacing the inside of the autoclave with nitrogen, the inside of the autoclave was pressurized to 7 kg / cm 2 G with hydrogen. This amount of hydrogen corresponds to about 0.14 mol times as cyclohexanone with respect to diphenylamine. Subsequently, the same heat reaction and treatment as in Example 1 were carried out. As a result, triphenylamine was produced with a selectivity of 79.8%.
また回収したフエノール留分中にはシクロヘキサノンが
存在し、その濃度は0.8％含まれていた。Cyclohexanone was present in the recovered phenol fraction and its concentration was 0.8%.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 255/58 // Ｂ０１Ｊ 31/28 Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display area C07C 255/58 // B01J 31/28 C07B 61/00 300
Claims (10)
ンまたはその核置換体、過剰量のフェノールまたはその
核置換体、及び上記反応に用いるフェノールまたはその
核置換体に対応する触媒量のシクロヘキサノンまたはそ
の環置換体を加熱反応させることを特徴とするトリフェ
ニルアミンまたはその核置換体の製造方法。1. A diphenylamine or its nuclear substitution product, an excess amount of phenol or its nuclear substitution product, and a catalytic amount of cyclohexanone or its corresponding to the phenol or its nuclear substitution product used in the above reaction in the presence of a hydrogen transfer catalyst. A method for producing triphenylamine or a nuclear substitution product thereof, which comprises reacting a ring substitution product with heating.
ミンまたはその核置換体を分離後、副生成物のシクロヘ
キサノン類を含むフェノールまたはその核置換体を反応
系へ循環して再使用する特許請求の範囲第（１）項記載
の方法。2. After separating triphenylamine or its nuclear substitution product obtained from a heated reaction mass, the phenol containing the by-product cyclohexanone or its nuclear substitution product is recycled to the reaction system for reuse. The method according to item (1).
の範囲第（１）項記載の方法。3. The method according to claim 1, wherein the heating reaction temperature is 150 to 300 ° C.
の範囲第（１）項記載の方法。4. The method according to claim 1, wherein the hydrogen transfer catalyst is palladium.
ルアミンまたはその核置換体に対し、４〜10モル倍の過
剰量用いる特許請求の範囲第（１）項記載の方法。5. The method according to claim 1, wherein the phenol or the nuclear substitution product thereof is used in an excess amount of 4 to 10 mol times with respect to the diphenylamine or the nuclear substitution product thereof.
ールまたはその核置換体を、ジフェニルアミンまたはそ
の核置換体中で水素加圧下に、その一部を対応するシク
ロヘキサノンまたはその環置換体に変換させつつ、フェ
ノールまたはその核置換体、及びジフェニルアミンまた
はその核置換体と加熱反応させることを特徴とするトリ
フェニルアミンまたはその核置換体の製造方法。6. An excess amount of phenol or a nuclear substitution product thereof in the presence of a hydrogen transfer catalyst is pressurized under hydrogen in diphenylamine or a nuclear substitution product thereof, and a part thereof is converted to a corresponding cyclohexanone or a ring substitution product thereof. A method for producing triphenylamine or a nuclear substitution product thereof, which comprises reacting phenol or a nuclear substitution product thereof and diphenylamine or a nuclear substitution product thereof with heating while converting.
ミンまたはその核置換体を分離後、副生成物のシクロヘ
キサノン類を含むフェノールまたはその核置換体を反応
系へ循環して再使用する特許請求の範囲第（６）項記載
の方法。7. A method for separating triphenylamine or a nuclear substitution product thereof obtained from a heated reaction mass, and then recycling the phenol containing a by-product cyclohexanone or a nuclear substitution product thereof to the reaction system for reuse. The method according to item (6).
の範囲第（６）項記載の方法。8. The method according to claim 6, wherein the heating reaction temperature is 150 to 300 ° C.
の範囲第（６）項記載の方法。9. The method according to claim 6, wherein the hydrogen transfer catalyst is palladium.
ニルアミンまたはその核置換体に対し、４〜10モル倍の
過剰量用いる特許請求の範囲第（６）項記載の方法。10. The method according to claim 6, wherein the phenol or its nuclear substitution product is used in an excess amount of 4 to 10 mol times with respect to diphenylamine or its nuclear substitution product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60023521A JPH0665662B2 (en) | 1985-02-12 | 1985-02-12 | Method for producing triphenylamine or nuclear substitution product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60023521A JPH0665662B2 (en) | 1985-02-12 | 1985-02-12 | Method for producing triphenylamine or nuclear substitution product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61183250A JPS61183250A (en) | 1986-08-15 |
| JPH0665662B2 true JPH0665662B2 (en) | 1994-08-24 |
Family
ID=12112750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60023521A Expired - Lifetime JPH0665662B2 (en) | 1985-02-12 | 1985-02-12 | Method for producing triphenylamine or nuclear substitution product thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0665662B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100193156B1 (en) * | 1992-10-28 | 1999-06-15 | 사또 아끼오 | Method for producing diphenylamine or its nuclear-substituted derivatives |
| US5654483A (en) * | 1994-12-26 | 1997-08-05 | Mitsui Toatsu Chemicals, Inc. | Process for producing alkoxy-substituted triphenylamines |
-
1985
- 1985-02-12 JP JP60023521A patent/JPH0665662B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61183250A (en) | 1986-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR870001998B1 (en) | Method for preparing diphenylamine or N, N'-diphenyl-phenylenediamine | |
| JPH0665662B2 (en) | Method for producing triphenylamine or nuclear substitution product thereof | |
| EP0630881A1 (en) | Process for the preparation of diphenylamine | |
| JPH0533215B2 (en) | ||
| JP3213502B2 (en) | Method for producing triphenylamines | |
| JP3135436B2 (en) | Method for producing diphenylamine or its nuclear-substituted product | |
| JP3234655B2 (en) | Process for producing diphenylamine or its nuclear substituted product | |
| EP0595332B1 (en) | Process for the preparation of diphenylamine or nucleus-substituted derivative thereof | |
| JP3177351B2 (en) | Method for producing tris (diarylamino) benzenes | |
| JP2516229B2 (en) | Process for producing 4- (4-hydroxyphenyl) -cyclohexanol and 4,4'-biphenol | |
| JP3177350B2 (en) | Method for producing dinonyldiphenylamine | |
| JP3137828B2 (en) | Method for producing aminodiphenylamine | |
| JPH0528216B2 (en) | ||
| JP3972441B2 (en) | Process for producing diarylamines | |
| JPH051256B2 (en) | ||
| JP2503038B2 (en) | Method for producing 4,4'-biphenol, precursor thereof and method for producing precursor | |
| JPH0770003A (en) | Method for producing diphenylamines | |
| JPH01100152A (en) | Production of diphenylamine nucleus-substituted compound | |
| JPH053459B2 (en) | ||
| JP3154598B2 (en) | N- (4'-nonylcyclohexyl) -4-nonylaniline and method for producing the same | |
| JP2863646B2 (en) | Method for producing isopropylaniline | |
| JP2523140B2 (en) | Method for producing (4-hydroxyphenyl) -cyclohexanecarboxylic acid | |
| JPH01100151A (en) | Production of triphenylamine and its nucleus-substituted compound | |
| JPH0725836A (en) | Method for producing dinonyldiphenylamine | |
| JPH0725833A (en) | Method for producing nonylaniline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |