JPH01100151A - Production of triphenylamine and its nucleus-substituted compound - Google Patents
Production of triphenylamine and its nucleus-substituted compoundInfo
- Publication number
- JPH01100151A JPH01100151A JP62258545A JP25854587A JPH01100151A JP H01100151 A JPH01100151 A JP H01100151A JP 62258545 A JP62258545 A JP 62258545A JP 25854587 A JP25854587 A JP 25854587A JP H01100151 A JPH01100151 A JP H01100151A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- phenol
- triphenylamine
- amount
- catalyst
- 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.)
- Pending
Links
- 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 14
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 150000001875 compounds Chemical class 0.000 title abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract 2
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 10
- 239000000975 dye Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 238000010626 work up procedure Methods 0.000 abstract 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 14
- 239000002994 raw material Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 125000006617 triphenylamine group Chemical class 0.000 description 9
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- TXTHKGMZDDTZFD-UHFFFAOYSA-N n-cyclohexylaniline Chemical compound C1CCCCC1NC1=CC=CC=C1 TXTHKGMZDDTZFD-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZUYKJZQOPXDNOK-UHFFFAOYSA-N 2-(ethylamino)-2-thiophen-2-ylcyclohexan-1-one;hydrochloride Chemical class Cl.C=1C=CSC=1C1(NCC)CCCCC1=O ZUYKJZQOPXDNOK-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- FHMZRXAOGIFMFL-UHFFFAOYSA-N 3-methyl-n,n-diphenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 FHMZRXAOGIFMFL-UHFFFAOYSA-N 0.000 description 2
- KSMVBYPXNKCPAJ-UHFFFAOYSA-N 4-Methylcyclohexylamine Chemical compound CC1CCC(N)CC1 KSMVBYPXNKCPAJ-UHFFFAOYSA-N 0.000 description 2
- IULUNTXBHHKFFR-UHFFFAOYSA-N 4-methyl-n,n-diphenylaniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 IULUNTXBHHKFFR-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910000510 noble metal 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
- 238000006722 reduction reaction Methods 0.000 description 2
- 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
- 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
- MNVMYTVDDOXZLS-UHFFFAOYSA-N 4-methoxyguaiacol Natural products COC1=CC=C(O)C(OC)=C1 MNVMYTVDDOXZLS-UHFFFAOYSA-N 0.000 description 1
- AGHYMXKKEXDUTA-UHFFFAOYSA-N 4-methyl-n-phenylaniline Chemical compound C1=CC(C)=CC=C1NC1=CC=CC=C1 AGHYMXKKEXDUTA-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000003946 cyclohexylamines Chemical group 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 description 1
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- FJJAMFVUPPQQKI-UHFFFAOYSA-N oxorhodium rhodium Chemical compound [Rh]=O.[Rh] FJJAMFVUPPQQKI-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔本発明の目的〕
本発明はトリフェニルアミンまたはその核置換体（以下
トリフェニルアミン類と略記する）の新規な製造方法に
関する。トリフェニルアミン類は、染料、ゴム薬等を製
造するための中間体として有用な化合物である。DETAILED DESCRIPTION OF THE INVENTION [Object of the present invention] The present invention relates to a novel method for producing triphenylamine or its nuclear substituted products (hereinafter abbreviated as triphenylamines). Triphenylamines are compounds useful as intermediates for producing dyes, rubber drugs, and the like.
従来、水素移動触媒を用いるトリフェニルアミン類の製
造方法としては、特開昭６０−２１５６５３号に、ジフ
ェニルアミン類及び過剰量のシクロヘキサノン類とを加
熱反応する方法が、又、特開昭６１−１８３２５０号に
は、ジフェニルアミン類、過剰量のフェノール類及びフ
ェノール類に対応する触媒量のシクロヘキサノン類とを
加熱反応する方法が開示されている。しかしながら、特
開昭６０−２１５６５３号の方法では過剰量のシクロヘ
キサノン類を、又、特開昭６１−１８３２５０号の方法
では過剰量のフェノール類を用いているため反応１回あ
たりのトリフェニルアミン類の生成濃度は大きくなく、
工業的製法としては満足できるものとは云い難い。Conventionally, as a method for producing triphenylamines using a hydrogen transfer catalyst, there is a method in which diphenylamines and an excess amount of cyclohexanone are heated and reacted in JP-A-60-215653, and JP-A-61-183250. No. 2, No. 2003-116106 discloses a method of thermally reacting diphenylamines, an excess amount of phenols, and a catalytic amount of cyclohexanones corresponding to the phenols. However, since the method of JP-A No. 60-215653 uses an excess amount of cyclohexanones, and the method of JP-A No. 61-183250 uses an excess amount of phenols, triphenylamines are produced per reaction. The concentration of produced is not large,
As an industrial manufacturing method, it is difficult to say that it is satisfactory.
本発明者等は、トリフェニルアミン類の製造方法を更に
検討した結果、水素移動触媒の存在下にフェノール類及
び一般式（Ｉ）で表わされるアミン類とを加熱反応する
と、容易に脱水素反応及び縮合反応が起きトリフェニル
アミン類が生成することを見いだし、本発明に到達した
。As a result of further studies on the method for producing triphenylamines, the present inventors found that when phenols and amines represented by general formula (I) are heated and reacted in the presence of a hydrogen transfer catalyst, dehydrogenation can easily occur. It was discovered that a condensation reaction occurs and triphenylamines are produced, and the present invention was achieved based on this discovery.
本発明の方法において原料として使用されるフェノール
類としては、フェノール、メチルフェノール、エチルフ
ェノール、イソプロピルフェノール、ブチルフェノール
、２，４−ジメチルフェノール、２，４．６− ）−ジ
メチルフェノール等のアルキルフェノール、３−メトキ
シフェノール、４−メトキシフェノール等のアルコキシ
フェノール等を例示することができる。その使用量は一
般式（Ｉ）で表わされるアミン類に対し等モル倍以上で
あれば実施可能であるが、反応終了液中のトリフェニル
アミン類の濃度を高くするには。The phenols used as raw materials in the method of the present invention include alkylphenols such as phenol, methylphenol, ethylphenol, isopropylphenol, butylphenol, 2,4-dimethylphenol, 2,4.6-)-dimethylphenol, etc. Examples include alkoxyphenols such as -methoxyphenol and 4-methoxyphenol. It can be used in an amount equal to or more than the equimolar amount of the amine represented by the general formula (I), but in order to increase the concentration of triphenylamine in the reaction-completed solution.
一般式（Ｉ）で表わされるアミン類に対し１〜５モル倍
とすることが好ましい。It is preferable to use 1 to 5 moles of the amine represented by the general formula (I).
本発明の方法において使用できる一般式（Ｉ）で表わさ
れるアミン類とは、具体的にはシクロヘキシルアミン、
ジシクロヘキシルアミン、Ｎ−シクロへキシルアニリン
及び炭素原子数１〜４のアルキル基すなわちメチル基、
エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチ
ル基、５ｅｅ−ブチル基、ｔａｒｔ−ブチル基、イソブ
チル基で置換されたシクロヘキシルアミン類、ジシクロ
ヘキシルアミン類、Ｎ−シクロヘキシルアニリン類であ
る。Specifically, the amines represented by the general formula (I) that can be used in the method of the present invention include cyclohexylamine,
dicyclohexylamine, N-cyclohexylaniline and an alkyl group having 1 to 4 carbon atoms, that is, a methyl group,
These are cyclohexylamines, dicyclohexylamines, and N-cyclohexylanilines substituted with ethyl group, n-propyl group, isopropyl group, n-butyl group, 5ee-butyl group, tart-butyl group, and isobutyl group.
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に機能する触媒であることが必
要であるが、通常の水素化還元触媒は脱水素触媒として
使用可能である。The catalyst used in the method of the present invention needs to be a catalyst that functions in both dehydrogenation and reduction reactions, but ordinary hydrogenation-reduction catalysts can be used as dehydrogenation catalysts.
具体的には、ラネーニッケル、還元ニッケル。Specifically, Raney nickel, reduced nickel.
ニッケルをケイソウ土、アルミナ、シリカ等の種々の担
体に担持したニッケル担体触媒；ラネーコバルト、還元
コバルト、コバルト担体触媒等のコバルト触媒；ラネー
銅、還元銅、銅担体触媒等の銅触媒；ラネーパラジウム
、パラジウム−炭素、パラジウム−アルミナ、パラジウ
ム−炭酸カルシウム、パラジウム−硫酸バリウム、パラ
ジウム黒等のパラジウム触媒；白金−炭素、白金黒、酸
化白金、ロジウム−白金等の白金触媒；ロジウム−炭素
、酸化ロジウム等のロジウム触媒；ルテニウム−炭素、
酸化ルテニウム等のルテニウム触媒；周期律表第８族の
貴金属触媒あるいはその貴金属担体触媒、銅クロム酸化
物触媒、酸化モリブデン触媒等を例示することができる
。これらの触媒のうちでは、パラジウム触媒を用いるこ
とが好ましく、特にパラジウム−炭素触媒の使用が好ま
しい。Nickel supported catalysts in which nickel is supported on various supports such as diatomaceous earth, alumina, and silica; Cobalt catalysts such as Raney cobalt, reduced cobalt, and cobalt supported catalysts; Copper catalysts such as Raney copper, reduced copper, and copper supported catalysts; Raney palladium Palladium catalysts such as , palladium-carbon, palladium-alumina, palladium-calcium carbonate, palladium-barium sulfate, palladium black; Platinum catalysts such as platinum-carbon, platinum black, platinum oxide, rhodium-platinum; rhodium-carbon, rhodium oxide rhodium catalysts such as; ruthenium-carbon,
Ruthenium catalysts such as ruthenium oxide; noble metal catalysts of group 8 of the periodic table or noble metal carrier catalysts thereof, copper chromium oxide catalysts, molybdenum oxide catalysts, etc. can be exemplified. Among these catalysts, it is preferable to use a palladium catalyst, and it is particularly preferable to use a palladium-carbon catalyst.
触媒の使用量は、仕込原料混合液量に対し、触媒の金属
重量として、通常０．０１〜２．０重量％、好ましくは
０．０５〜１．０重量％の範囲である。これ以下の触媒
の使用量であると反応速度が小さくなる。The amount of the catalyst used is usually in the range of 0.01 to 2.0% by weight, preferably 0.05 to 1.0% by weight, based on the metal weight of the catalyst, based on the amount of the raw material mixture. If the amount of catalyst used is less than this, the reaction rate will be low.
ｃ本発明の反応条件〕
反応温度は、通常１５０〜３５０℃の範囲で、好ましく
は２００〜３００℃の範囲から選ばれる。c Reaction conditions of the present invention] The reaction temperature is usually selected from the range of 150 to 350°C, preferably from the range of 200 to 300°C.
反応は生成水を逐次系外へ留出させながら行えば速く進
行させることができる。The reaction can proceed quickly if the produced water is successively distilled out of the system.
本発明の方法では、反応−回あたりのトリフェニルアミ
ン類の生成濃度が大きく、目的とするトリフェニルアミ
ン類は、触媒を分離した反応液を蒸留、晶析等の常法に
よる処理で簡単に単離することができる。In the method of the present invention, the concentration of triphenylamines produced per reaction is large, and the target triphenylamines can be easily obtained by treating the reaction solution from which the catalyst has been separated by conventional methods such as distillation and crystallization. Can be isolated.
これら反応後の後処理が容易で、且つ反応−回あたりの
トリフェニルアミン類の生成濃度が高いので、経済的に
有利で、工業的実施に適した製造方法といえる。Since post-treatment after these reactions is easy and the concentration of triphenylamines produced per reaction is high, it can be said to be an economically advantageous production method suitable for industrial implementation.
以下実施例をもって本発明を更に具体的に説明する。 The present invention will be explained in more detail with reference to Examples below.
実施例１
撹拌機、温度計、圧力計、生成水留出ライン及び冷却器
を備えた内容積０．５ａのオートクレーブに、シクロヘ
キシルアミン４９．６ｇ（０，５モル）。Example 1 49.6 g (0.5 mol) of cyclohexylamine was placed in an autoclave having an internal volume of 0.5 a and equipped with a stirrer, a thermometer, a pressure gauge, a produced water distillation line, and a cooler.
フェノール１４１．２ ｇ （Ｉ，５モル）、及び５％
パラジウム−炭素（日本エンゲルハルト社ｉｌり ７．
６ｇを仕込み、密閉後、撹拌昇温し、２７０℃とした。141.2 g (I, 5 mol) of phenol, and 5%
Palladium-carbon (Japan Engelhard Co., Ltd.) 7.
After charging 6 g and sealing the container, the temperature was raised to 270° C. with stirring.
この時の圧力は約１１Ｋｇ／ａＪＧであった。以後２７
０℃を保って２時間毎に圧を抜いて（約１５→５ｋｇ／
ｄＧ）生成水を留出させながら１５時間反応を行った。The pressure at this time was approximately 11 kg/aJG. 27 thereafter
Maintain the temperature at 0℃ and release the pressure every 2 hours (approximately 15 → 5 kg/
dG) The reaction was carried out for 15 hours while distilling the produced water.
反応終了液を約６０℃に冷却後、グラスフィルターで濾
過して触媒を分離した。炉液の一部をガスクロマトグラ
フィーにより分析して未反応原料及び生成物を定量した
結果、フェノール４２．８ｇ、ジフェニルアミン１９．
５ｇ及びトリフェニルアミン８４ 、９ｇ （収率６９
．２％対ジシクロヘキシルアミンであった０反応仕込原
料混合液量に対するトリフェニルアミンの生成量は４４
．５重量％であった。反応液を精留して、フェノール及
びジフェニルアミンを前留分として留出させ、トリフェ
ニルアミン（沸点２０３℃／１０ｍｍ１ｇ） ８３．８
ｇヲ主留分として得た。得られたトリフェニルアミンは
、純度９９．２％であった。After the reaction completed liquid was cooled to about 60°C, it was filtered through a glass filter to separate the catalyst. A portion of the furnace liquid was analyzed by gas chromatography to determine the amount of unreacted raw materials and products. As a result, 42.8 g of phenol and 19.8 g of diphenylamine were found.
5 g and triphenylamine 84,9 g (yield 69
．． The amount of triphenylamine produced was 44% relative to the amount of reaction raw material mixture, which was 2% to dicyclohexylamine.
．． It was 5% by weight. The reaction solution was rectified to distill out phenol and diphenylamine as a pre-distillate, triphenylamine (boiling point 203°C/10mm 1g) 83.8
g was obtained as the main fraction. The resulting triphenylamine had a purity of 99.2%.
実施例２
ジシクロヘキシルアミン９０．７ ｇ （０，５モル）
、フェノール９４．１ ｇ （Ｉ，０モル）及び５％パ
ラジウム−炭素７．４ｇを実施例１と同様に反応して、
反応終了液の一部を濾過後、反応終了液の組成を分析し
た結果、フェノール８．９ｇ、ジフェニルアミン１７．
４ｇ及びトリフェニルアミン７２．１ｇ（収率５８．８
％対レジシクロヘキシルアミンであった。Example 2 Dicyclohexylamine 90.7 g (0.5 mol)
, 94.1 g (I, 0 mol) of phenol and 7.4 g of 5% palladium-carbon were reacted in the same manner as in Example 1,
After filtering a portion of the reaction-completed liquid, the composition of the reaction-completed liquid was analyzed and found to be 8.9 g of phenol and 17.9 g of diphenylamine.
4g and triphenylamine 72.1g (yield 58.8
% vs. recyclohexylamine.
反応仕込原料混合液量に対するトリフェニルアミンの生
成量は３９．０重量％であった。The amount of triphenylamine produced was 39.0% by weight based on the amount of the reaction raw material mixture.
実施例３
Ｎ−２２口へキシルアニリン８７．６ｇ（０，５モル）
、フェノール９４．１ｇ（Ｉ，０モル）及び５％パラジ
ウム−炭素７．３ｇを実施例１と同様に反応して、反応
終了液の一部を濾過後１反応液の組成を分析した結果、
フェノール８．２ｇ、ジフェニルアミン１６．４ ｇ及
びトリフェニルアミン６８．７ｇ（収率５６゜θ％対Ｎ
−シクロヘキシルアニリン）であった０反応仕込原料混
合液量に対するトリフェニルアミンの生成量は３７．８
重量％であった。Example 3 N-22hexylaniline 87.6g (0.5 mol)
, 94.1 g (I, 0 mol) of phenol and 7.3 g of 5% palladium-carbon were reacted in the same manner as in Example 1, and after filtering a portion of the reaction solution, the composition of the first reaction solution was analyzed.
8.2 g of phenol, 16.4 g of diphenylamine and 68.7 g of triphenylamine (yield 56°θ% vs. N
-cyclohexylaniline) The amount of triphenylamine produced was 37.8 with respect to the amount of the mixed solution of raw materials for the reaction.
% by weight.
実施例４
４−メチルシクロヘキシルアミン５６．６ ｇ （０，
５モル）、フェノール１４１．２ ｇ （Ｉ，５モル）
及び５％パラジウム−炭素７．９ｇを実施例１と同様に
反応して、反応終了液の一部を濾過後、反応液の組成を
分析した結果、フェノール５３．６ ｇ、４−メチルジ
フェニルアミン２０．２ｇ及び４−メチルトリフェニル
アミン５９．３ｇ（収率４５．８％対４−メチルシクロ
ヘキシルアミン）であった８反応仕込原料混合液量に対
する４−メチルトリフェニルアミンの生成量は３０．０
重量％であった。Example 4 4-methylcyclohexylamine 56.6 g (0,
5 mol), phenol 141.2 g (I, 5 mol)
and 7.9 g of 5% palladium-carbon were reacted in the same manner as in Example 1, and after filtering a portion of the reaction solution, the composition of the reaction solution was analyzed. As a result, 53.6 g of phenol, 20 g of 4-methyldiphenylamine. The amount of 4-methyltriphenylamine produced was 30.0 g with respect to the amount of the mixed liquid of raw materials for 8 reactions, which was 59.3 g (yield 45.8% vs. 4-methylcyclohexylamine) of 4-methyltriphenylamine.
% by weight.
実施例５
ジシクロヘキシルアミン９０．７ ｇ （０，５モル）
、３−メチルフェノール１０８．１ ｇ （Ｉ，０モル
）及び５％パラジウム−炭素８．０ｇを実施例１と同様
に反応して１反応終了液の一部を濾過後、反応終了液の
組成を分析した結果、３−メチルフェノール５８゜４ｇ
、ジフェニルアミン２０．３ｇ及び３−メチルトリフェ
ニルアミン５５．７ｇ（収率４３．０％対フジシクロヘ
キシルアミンであった。反応仕込原料混合液量に対する
３−メチルトリフェニルアミンの生成量は２８．０重量
％であった。Example 5 Dicyclohexylamine 90.7 g (0.5 mol)
, 108.1 g (I, 0 mol) of 3-methylphenol and 8.0 g of 5% palladium-carbon were reacted in the same manner as in Example 1. After filtering a portion of the reaction completed liquid, the composition of the reaction completed liquid was obtained. As a result of analysis, 3-methylphenol 58゜4g
, 20.3 g of diphenylamine and 55.7 g of 3-methyltriphenylamine (yield 43.0% vs. Fujicyclohexylamine. The amount of 3-methyltriphenylamine produced relative to the amount of the reaction raw material mixture was 28.0 g. % by weight.
実施例６
５％パラジウム−炭素７．６ｇの代りに、５％パラジウ
ム−アルミナ（日本エンゲルハルト社製）７゜６ｇを使
用した以外は実施例１と同様に反応を行った。反応終了
液の一部を演過後、反応終了液の組成を分析した結果、
フェノール４４．２ｇ、ジフェニルアミン２２．０ｇ及
びトリフェニルアミン７８．５ｇ（収率６４．０％対ジ
シクロヘキシルアミンであった１反応仕込原料混合液量
に対するトリフェニルアミンの生成量は４１．１重量％
であった。Example 6 The reaction was carried out in the same manner as in Example 1, except that 7.6 g of 5% palladium-alumina (manufactured by Nippon Engelhard) was used instead of 7.6 g of 5% palladium-carbon. As a result of analyzing the composition of the reaction-completed liquid after passing through a portion of the reaction-completed liquid,
44.2 g of phenol, 22.0 g of diphenylamine, and 78.5 g of triphenylamine (yield 64.0% vs. dicyclohexylamine. The amount of triphenylamine produced was 41.1% by weight based on the amount of mixed liquid of raw materials for one reaction.
Met.
実施例７〜１４ 実施例１と同じ条件により下記第１表の原料。Examples 7-14 The raw materials in Table 1 below were prepared under the same conditions as in Example 1.
触媒を使用して、それぞれの目的生成物を得た。Catalysts were used to obtain the respective desired products.
第１表Table 1
Claims (1)
置換体及び一般式（ I ）で表わされるアミン類を加熱
反応す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。 一般式（ I ） ▲数式、化学式、表等があります▼〔式中Ｒ＿１は、水
素原子、シクロ ヘキシル基又はフェニル基を 示し、Ｒ＿２は、水素原子又は 低級アルキル基を示す。〕 ２、水素移動触媒が、パラジウム触媒である特許請求の
範囲第１項記載の方法。 ３、加熱反応温度が、２００〜３００℃である特許請求
の範囲第１項記載の方法。[Claims] 1. Triphenylamine or a nuclear substituted product thereof, characterized in that phenol or a nuclear substituted product thereof and amines represented by the general formula (I) are heated and reacted in the presence of a hydrogen transfer catalyst. manufacturing method. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, R_1 represents a hydrogen atom, a cyclohexyl group, or a phenyl group, and R_2 represents a hydrogen atom or a lower alkyl group. 2. The method according to claim 1, wherein the hydrogen transfer catalyst is a palladium catalyst. 3. The method according to claim 1, wherein the heating reaction temperature is 200 to 300°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62258545A JPH01100151A (en) | 1987-10-13 | 1987-10-13 | Production of triphenylamine and its nucleus-substituted compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62258545A JPH01100151A (en) | 1987-10-13 | 1987-10-13 | Production of triphenylamine and its nucleus-substituted compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01100151A true JPH01100151A (en) | 1989-04-18 |
Family
ID=17321717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62258545A Pending JPH01100151A (en) | 1987-10-13 | 1987-10-13 | Production of triphenylamine and its nucleus-substituted compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01100151A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0632014A1 (en) * | 1993-06-30 | 1995-01-04 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member and electrophotographic apparatus using same |
| JP2002019229A (en) * | 2000-07-11 | 2002-01-23 | Sato Corp | Portable printer |
-
1987
- 1987-10-13 JP JP62258545A patent/JPH01100151A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0632014A1 (en) * | 1993-06-30 | 1995-01-04 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member and electrophotographic apparatus using same |
| US5616442A (en) * | 1993-06-30 | 1997-04-01 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member and electrophotographic apparatus using same |
| JP2002019229A (en) * | 2000-07-11 | 2002-01-23 | Sato Corp | Portable printer |
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