JPS6335548A - Production of triarylamine - Google Patents
Production of triarylamineInfo
- Publication number
- JPS6335548A JPS6335548A JP61177752A JP17775286A JPS6335548A JP S6335548 A JPS6335548 A JP S6335548A JP 61177752 A JP61177752 A JP 61177752A JP 17775286 A JP17775286 A JP 17775286A JP S6335548 A JPS6335548 A JP S6335548A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- biphenyl
- catalyst
- diphenylamine
- transition metal
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 125000005259 triarylamine group Chemical group 0.000 title claims description 7
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims abstract description 26
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- NXYICUMSYKIABQ-UHFFFAOYSA-N 1-iodo-4-phenylbenzene Chemical group C1=CC(I)=CC=C1C1=CC=CC=C1 NXYICUMSYKIABQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims abstract description 4
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 4
- 150000007514 bases Chemical class 0.000 claims abstract description 3
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract 6
- PKJBWOWQJHHAHG-UHFFFAOYSA-N 1-bromo-4-phenylbenzene Chemical group C1=CC(Br)=CC=C1C1=CC=CC=C1 PKJBWOWQJHHAHG-UHFFFAOYSA-N 0.000 claims abstract 2
- GPYDMVZCPRONLW-UHFFFAOYSA-N 1-iodo-4-(4-iodophenyl)benzene Chemical group C1=CC(I)=CC=C1C1=CC=C(I)C=C1 GPYDMVZCPRONLW-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 abstract description 7
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract description 6
- 235000010290 biphenyl Nutrition 0.000 abstract description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 abstract description 2
- 239000004305 biphenyl Substances 0.000 abstract description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 150000004820 halides Chemical class 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- HQJQYILBCQPYBI-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)benzene Chemical group C1=CC(Br)=CC=C1C1=CC=C(Br)C=C1 HQJQYILBCQPYBI-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- -1 diphenylamino group Chemical group 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium 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)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はトリアリールアミンの新規な製造法に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a novel method for producing triarylamines.
詳しくは、ヨウ素化ビフェニル又は臭素化ビフェニルに
ジフェニルアミンを反応させるピフェニル系のトリアリ
ールアミンの製造法に関するものでらる。これらの芳香
族アミンは、有機精密化学品の合成原料などとして重要
な化合物であるが、近年有機光導電体のＯＴ材などの原
料として注目されている。Specifically, the present invention relates to a method for producing a piphenyl-based triarylamine, which involves reacting iodinated biphenyl or brominated biphenyl with diphenylamine. These aromatic amines are important compounds as raw materials for the synthesis of organic fine chemicals, and have recently attracted attention as raw materials for OT materials for organic photoconductors.
（従来技術）
これらの芳香族アミンは重要な化合物にもかかわらず、
その製法が固層なこともあり、従来あまシ工業的力関心
が大きい化合物とは言えず、その工業的製造法が探索さ
れているが、工業的に意味のある製造方法は従来からも
ほとんど提案されていない。例えば、４．４’−ビスジ
フェニルアミノピフェニルの製造方法としては、トリフ
ェニルアミンの電屏酸化２量化法が提案されている（
Ｚ、 ＰｈｙｓＯｈａｍ １２５（１）、 ３５（１９
８１） ］が収率も悪く、工業的製造法と言えるもので
はない。(Prior Art) Although these aromatic amines are important compounds,
Because its manufacturing method is a solid phase, it cannot be said that it has traditionally been a compound of great industrial interest, and industrial manufacturing methods are being searched for, but there have been few industrially meaningful manufacturing methods. Not proposed. For example, as a method for producing 4,4'-bisdiphenylaminopiphenyl, a method for dimerizing triphenylamine by dielectric oxidation has been proposed (
Z, PhysOham 125(1), 35(19
81)] has a poor yield and cannot be called an industrial production method.
（間ａｔ解決するための手段及び作用）本発明者らは上
記観点から鋭意研究を重ね念結果、工業的に安価な製品
であるピフェニルヵ為ら容易に合成できるヨウ素化ピフ
ェニル又は臭素化ピフェニルを原料として用い、これら
にジフェニルアミンを反応させることによシ、極めて容
易に高収率で目的化合物を得ることができることを見出
した。本発明は以上の知見に基づくものであシ、ヨウ素
化ピフェニル又は臭素化ピフェニルを塩基性化合物、遷
移金属又は遷移金属化合物触媒、溶媒の存在下に、−）
フェニルアミンと反応させることを特徴とするトリアリ
ールアミンの製造方法である。(Means and effects for solving the problem) The present inventors have conducted intensive research from the above point of view and have found that iodinated piphenyl or brominated piphenyl, which can be easily synthesized from piphenyl, which is an industrially inexpensive product, is used as a raw material. It has been found that by reacting these with diphenylamine, the target compound can be obtained very easily and in high yield. The present invention is based on the above findings.
This is a method for producing triarylamine, which is characterized by reacting it with phenylamine.
本発明で得られるトリアリールアミンは、例えば次の様
なものである。４−Ｊ）フェニルアミノピフェニル、４
．４’−ビスジフェニルアミノピフェニル、２−ジフェ
ニルアミノピフェニル、２．４’−ビスジフェニルアミ
ノピフェニル、２．２’−ヒスジフェニルアミノピフェ
ニル、２．６−ヒスジフェニルアミノピフェニル、２．
４−ビスジフェニルアミノピフェニルなどでちる。The triarylamine obtained in the present invention is, for example, as follows. 4-J) Phenylaminopiphenyl, 4
．． 4'-bisdiphenylaminopiphenyl, 2-diphenylaminopiphenyl, 2.4'-bisdiphenylaminopiphenyl, 2.2'-hisdiphenylaminopiphenyl, 2.6-hisdiphenylaminopiphenyl, 2.
Dilute with 4-bisdiphenylaminopiphenyl, etc.
本発明で用いられるヨウ素化ピフェニル及び臭素化ピフ
ェニルはピフェニルから容易に得ることができる。例え
ばヨウ素化ピフェニルは、ピフェニルとヨウ素を硝酸の
存在下に、酸と過酸化水素又は酸素の存在下に反応させ
ることにょシ容易に得ることができる。臭素化ピフェニ
ルは、ピフェニルと臭素を低温下に反応させることによ
シ容易に得ることができる。これらのハロゲン化ピフェ
ニルのうちで好ましく用いられるものは、４−ヨートヒ
フェニル、４−ブロモピフェニル、４．４’−ジョーＰ
ビフェニル、４．４’−ジブロモピフェニル等である。Iodinated piphenyl and brominated piphenyl used in the present invention can be easily obtained from piphenyl. For example, iodinated piphenyl can be easily obtained by reacting piphenyl and iodine in the presence of nitric acid and an acid in the presence of hydrogen peroxide or oxygen. Brominated piphenyl can be easily obtained by reacting piphenyl and bromine at low temperature. Among these halogenated piphenyls, those preferably used are 4-iothohyphenyl, 4-bromopyphenyl, 4.4'-joP
biphenyl, 4,4'-dibromopyphenyl, and the like.
これらのパラ置換ハロゲン化ピフェニルは、ピフェニル
とハロゲン力λら製造する場合に他のハロゲン化ビフェ
ニルよシも有利に製造できる。更には、生成物であるノ
ぞう位にジフェニルアミノ基を有するピフェニル化合物
は、よシ幅広い工業的用途を有している。またヨウ素化
ピフェニルト臭素化ヒフェニルとでは、ジフェニルアミ
ンとの反応性という観点からは、ヨウ素化ピフェニルの
方がかなシ反応性が良く、反応条件を相当温和にできる
ため好ましい。When these para-substituted halogenated piphenyls are produced from piphenyl and halogen λ, other halogenated biphenyls can also be advantageously produced. Furthermore, the product, a piphenyl compound having a diphenylamino group at the no-position, has a wide range of industrial uses. In addition, between iodinated piphenyl and brominated hypohenyl, iodinated piphenyl is preferable from the viewpoint of reactivity with diphenylamine because it has better reactivity and the reaction conditions can be made considerably milder.
本発明で用いられる塩基性化合物としては、アルカリ金
属の水酸化物、炭酸塩、炭酸水素塩、アルコラードなど
が一般的に用いられるが、第４級アンモニウム化合物や
脂肪族アミンや芳香族アミンの様な有機塩基を用いるこ
とも可能である。このなかで、アルカリ金属や第４級ア
ンモニウムの炭酸塩や炭酸水素塩、又はジフェニルアミ
ンが好ましいものとして用いられる。水酸化物、アルコ
ラード、ジフェニルアミン以外の有機塩基を用いると、
ヒＰロキシ基、アルコキシ基や有機塩基がジフェニルア
ミンの代シに導入された化合物が副生じてくる場合があ
る。更に、反応速度及び熱安定性という観点からアルカ
リ金属の炭酸塩や炭酸水素塩が最も好ましい。As the basic compound used in the present invention, alkali metal hydroxides, carbonates, hydrogen carbonates, alcolades, etc. are generally used, but quaternary ammonium compounds, aliphatic amines, aromatic amines, etc. It is also possible to use organic bases. Among these, carbonates and hydrogen carbonates of alkali metals and quaternary ammonium, and diphenylamine are preferably used. When organic bases other than hydroxide, alcoholade, and diphenylamine are used,
A compound in which a hydroxyl group, an alkoxy group, or an organic base is introduced instead of diphenylamine may be produced as a by-product. Furthermore, carbonates and hydrogen carbonates of alkali metals are most preferred from the viewpoint of reaction rate and thermal stability.
本発明で用いられる遷移金属又は遷移金属化合物として
は、例えばＯｕ、 Ｆｅ、 Ｏｏ、 Ｎｌ 、 Ｏｒ、
Ｖ、 Ｐｄ。Examples of the transition metal or transition metal compound used in the present invention include Ou, Fe, Oo, Nl, Or,
V, Pd.
ｐｔ、λｇ等の金属及びそれらの化合物が用いられるが
、収率の点から銅及びノセラジウムとそれらの化合物が
好ましい。銅化合物としては特に限定はなく、はとんど
の銅化合物が用いられるが、沃化第一銅、塩化第一銅、
酸化第一銅、臭化第一銅、シアン化第−銅、硫酸第一銅
、硫酸第二銅、塩化第二銅、水酸化第二銅、酸化第二銅
、臭化第二銅、燐酸第二銅、硝酸第一銅、硝酸第二銅、
炭酸銅、酢酸第一銅、酢酸第二銅などが好ましい。Metals such as pt and λg and their compounds are used, but copper, noceradium and their compounds are preferred from the viewpoint of yield. There are no particular limitations on the copper compound, and most copper compounds can be used, including cuprous iodide, cuprous chloride,
Cuprous oxide, cuprous bromide, cuprous cyanide, cuprous sulfate, cupric sulfate, cupric chloride, cupric hydroxide, cupric oxide, cupric bromide, phosphoric acid cupric, cuprous nitrate, cupric nitrate,
Copper carbonate, cuprous acetate, cupric acetate, and the like are preferred.
その中でも特に０ｕＯ１，０ｕＯｊ１２ 、０ｕＢｒ
、 Ｑｕ１３ｒｌ 、 ＯｕＩ 。Among them, especially 0uO1, 0uOj12, 0uBr
, Qu13rl, OuI.
ＯｕＯ、０ｕ２０ 、０ｕＳＯ４、Ｏｕ （００００Ｈ
３）２１ｄ容易に入手可能である点で好適である。パラ
ジウム化合物としても、ハロゲン化物、硫酸塩、硝酸塩
、有機酸塩などを用いることができる。遷移金属及びそ
の化合物の使用量は、反応させるハロゲン化ビフェニル
の０．１〜１５０モル％である。OuO, 0u20, 0uSO4, Ou (0000H
3) 21d is suitable because it is easily available. As the palladium compound, halides, sulfates, nitrates, organic acid salts, etc. can be used. The amount of the transition metal and its compound used is 0.1 to 150 mol% of the halogenated biphenyl to be reacted.
本発明で用いられる溶媒は、一般的に用いられる溶媒で
あれば良いが、ニトロベンゼン、ジメチルホルムアミド
、ジメチルスルホキシＹ、 Ｎ−メチルピロリドン等の
非プロトン性極性溶媒が好ましく用いられる。The solvent used in the present invention may be any commonly used solvent, but aprotic polar solvents such as nitrobenzene, dimethylformamide, dimethylsulfoxy Y, and N-methylpyrrolidone are preferably used.
本発明の反応は、一般的には常圧下１００〜２５０℃の
温度で行なわれるが、加圧下に行なってももちろんかま
わない。反応終了後、反応液中に析出し九固形物を除去
した後、溶媒を除去し生成物を得ることができる。The reaction of the present invention is generally carried out at a temperature of 100 to 250°C under normal pressure, but it may of course be carried out under pressure. After the reaction is completed, the solids precipitated in the reaction solution are removed, and then the solvent is removed to obtain a product.
（発明の効果）
上述の様に、本発明は、入手容易な安価な原料分用い、
簡単な工程により新規々トリアリールアミンの製造法を
提供するものであシ、工秦的価値は高い。(Effect of the invention) As mentioned above, the present invention uses easily available and inexpensive raw materials,
It provides a new method for producing triarylamine using a simple process, and is of high value in terms of engineering.
（実施例） 次に実施例により本発明を更に詳細に説明する。(Example) Next, the present invention will be explained in more detail with reference to Examples.
尚、生成物の選択率及び収率はハロゲン化ピフェニルを
基準とした。Note that the selectivity and yield of the product were based on halogenated piphenyl.
実施例１
４−ヨードビフェニル１５ｔ（０，０５３モル）、ジフ
ェニルアミン９５Ｆ （０，０５３モル）、炭酸カリウ
ム９．５９ （０，０６９モル）、銅粉２．Ｏｒ （ｏ
、ｏａモル）及びニトロベンゼン１５０２を１２の還流
冷却器付４つロフラスコに入れ、窒素気流下に１９０℃
で１０時間攪拌反応させた。反応終了後、反応液にテト
ラヒＰロアラン１００１を加え、次いで固形物を吸引口
過した。７液をガスクロマトグラフィーで分析した結果
、４−ヨードビフェニルの転化率は９５％であり、４−
ジフェニルアミノピフェニルへの選択率は９０％であっ
た。Example 1 4-iodobiphenyl 15t (0,053 mol), diphenylamine 95F (0,053 mol), potassium carbonate 9.59 (0,069 mol), copper powder 2. Or (o
, oa mole) and nitrobenzene 1502 were placed in a 4-hole flask equipped with a reflux condenser and heated to 190°C under a nitrogen stream.
The mixture was stirred and reacted for 10 hours. After the reaction was completed, TetrahyPloalane 1001 was added to the reaction solution, and then the solid matter was filtered through the suction port. As a result of analyzing the 7 liquids by gas chromatography, the conversion rate of 4-iodobiphenyl was 95%, and the conversion rate of 4-iodobiphenyl was 95%.
The selectivity to diphenylamino piphenyl was 90%.
実施例２
４．４′−ショートピフェニル２５ ｔ （０，０６２
モル）、ジフェニルアミン２５．７ ｆ （０，１５モ
ル）、炭酸力ＩＪウム２６．１ ｙ （０，１９モル）
、銅粉２．５ ｆ （０，０３９モル）、及びニトロペ
ンぜン１５０ｔを１ｉ、の還流冷却器付４つロフラスコ
に入れ、窒素気流下に１９０℃で３０時間攪拌反応させ
た。反応液にテトラヒｒロフラン１００？を加え、次い
で固形物を吸引口過した。Example 2 4.4'-Short piphenyl 25 t (0,062
mol), diphenylamine 25.7 f (0.15 mol), carbonic acid IJum 26.1 y (0.19 mol)
, 2.5 f (0,039 mol) of copper powder, and 150 t of nitropenzene were placed in a 4-hole flask equipped with a 1i reflux condenser, and stirred and reacted at 190° C. for 30 hours under a nitrogen stream. Tetrahydrofuran 100 in the reaction solution? was added, and the solid was then passed through the suction port.
７液をガスクロマトグラフィーで分析した結果、４．４
′−ショートピフェニルの転化率は１００％であり、４
．４’−ビスジフェニルアミノビフェニルへの選択率は
９２％であった。７液からＴＨＦを蒸留除去後、アセト
ンを添加すると目的生成物が結晶と°して２６９析出し
た。As a result of analyzing the 7 liquids by gas chromatography, the result was 4.4.
The conversion rate of '-short piphenyl was 100%, and 4
．． The selectivity to 4'-bisdiphenylaminobiphenyl was 92%. After THF was distilled off from the solution 7, acetone was added, and the desired product crystallized and precipitated.
実施例３
実施例１において、銅粉２ｏｙ６用いる代シにヨウ化鋼
２．Ｏｔ （ｏ、ｏｔモル）を用い、且つ反応時間を２
５時間にする他は実施例１と同様にして反応を行なった
。４−ジフェニルアミノピフェニルの収率は９２％であ
った。Example 3 In Example 1, 2.0 y. of iodized steel was used instead of 2.6 y. of copper powder. Ot (o, ot mol) and reaction time 2
The reaction was carried out in the same manner as in Example 1, except that the reaction time was 5 hours. The yield of 4-diphenylaminopiphenyl was 92%.
実施例４
４−ヨードビフェニル１５？ （０，０５３モル）、
ジフェニルアミン３０ ｙ （０，１７７モル）、塩化
パラジウム２．Ｏｙ （０，０１１モル）及びジメチル
スルホキシド１５（ｌｉｔｕの還流冷却器付４つロフラ
スコに入れ窒素気流下に１７０℃で１５時間攪拌反応さ
せた。Example 4 4-iodobiphenyl 15? (0,053 mol),
Diphenylamine 30 y (0,177 mol), palladium chloride 2. Oy (0,011 mol) and dimethyl sulfoxide 15 (Litu) were placed in a 4-hole flask equipped with a reflux condenser and reacted with stirring at 170° C. for 15 hours under a nitrogen stream.
反応終了後、固形物を除去し７液をガスクロマトグラフ
ィーで分析した結果、４−ジフェニルアミノピフェニル
の収率は６２％であった。After the reaction was completed, the solid matter was removed and the 7 liquids were analyzed by gas chromatography. As a result, the yield of 4-diphenylaminopiphenyl was 62%.
実施例５
４．４′−ジブロモビフェニル２ｓｒ（ｏ、ｏｓモル）
。Example 5 4.4'-dibromobiphenyl 2sr (o, osmol)
.
ジフェニルアミン６８ ｙ （０，４１モル）、 炭
酸水素ナトリウム２ｒｔ（ｏ、３ｓモル）、 酸化第２
銅３ ｆ（０，０３８モル）及びジメチルスルホキシド
１５０ｆを１１．０還流冷却器付４つロフラスコに入れ
、窒素気流下に３０時間攪拌反応させた。反応終了後、
７液をガスクロマトグラフィーで分析した結果、４．４
’−ビスジフェニルアミノピフェニルの収率は４５％で
あった。Diphenylamine 68 y (0,41 mol), sodium bicarbonate 2rt (o, 3 s mol), 2nd oxide
3 f (0,038 mol) of copper and 150 f of dimethyl sulfoxide were placed in a four-bottle flask equipped with an 11.0 reflux condenser, and reacted with stirring under a nitrogen stream for 30 hours. After the reaction is complete,
As a result of analyzing the 7 liquids by gas chromatography, the result was 4.4.
The yield of '-bisdiphenylaminopiphenyl was 45%.
Claims (4)
性化合物、遷移金属又は遷移金属化合物触媒、溶媒の存
在下にジフェニルアミンと反応させることを特徴とする
トリアリールアミンの製造法(1) A method for producing triarylamine, which comprises reacting iodinated biphenyl or brominated biphenyl with diphenylamine in the presence of a basic compound, a transition metal or transition metal compound catalyst, and a solvent.
４，４′−ジヨードビフェニルである特許請求の範囲第
１項記載の方法(2) The method according to claim 1, wherein the iodinated biphenyl is 4-iodobiphenyl or 4,4'-diiodobiphenyl.
，４′−ジブロムビフエニルである特許請求の範囲第１
項記載の方法(3) Brominated biphenyl is 4-brombiphenyl or 4
, 4'-dibromubiphenyl
Method described in section
びそれらの化合物である特許請求の範囲第１項記載の方
法(4) The method according to claim 1, wherein the transition metal or transition metal compound is copper, palladium, or a compound thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61177752A JPS6335548A (en) | 1986-07-30 | 1986-07-30 | Production of triarylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61177752A JPS6335548A (en) | 1986-07-30 | 1986-07-30 | Production of triarylamine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6335548A true JPS6335548A (en) | 1988-02-16 |
Family
ID=16036505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61177752A Pending JPS6335548A (en) | 1986-07-30 | 1986-07-30 | Production of triarylamine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6335548A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1018505A3 (en) * | 1999-01-08 | 2000-09-13 | Orient Chemical Industries, Ltd. | Process for preparing a triarylamine dimer |
| WO2002076922A1 (en) * | 2001-03-16 | 2002-10-03 | Idemitsu Kosan Co., Ltd. | Method for producing aromatic amino compound |
| JP2004536798A (en) * | 2001-04-24 | 2004-12-09 | マサチューセッツ インスチテュート オブ テクノロジー | Copper-catalyzed formation of carbon-heteroatom and carbon-carbon bonds |
| JP2006143712A (en) * | 2004-10-20 | 2006-06-08 | Mitsubishi Chemicals Corp | Method for producing amine compound and amine compound and electrophotographic photoreceptor, cartridge and apparatus for forming image |
| WO2023136334A1 (en) * | 2022-01-14 | 2023-07-20 | 富士フイルム株式会社 | Method for producing compound represented by formula (i) |
-
1986
- 1986-07-30 JP JP61177752A patent/JPS6335548A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1018505A3 (en) * | 1999-01-08 | 2000-09-13 | Orient Chemical Industries, Ltd. | Process for preparing a triarylamine dimer |
| WO2002076922A1 (en) * | 2001-03-16 | 2002-10-03 | Idemitsu Kosan Co., Ltd. | Method for producing aromatic amino compound |
| JPWO2002076922A1 (en) * | 2001-03-16 | 2004-07-15 | 出光興産株式会社 | Method for producing aromatic amino compound |
| US7250532B2 (en) | 2001-03-16 | 2007-07-31 | Idemitsu Kosan Co., Ltd. | Method for producing aromatic amino compound |
| JP2004536798A (en) * | 2001-04-24 | 2004-12-09 | マサチューセッツ インスチテュート オブ テクノロジー | Copper-catalyzed formation of carbon-heteroatom and carbon-carbon bonds |
| JP2006143712A (en) * | 2004-10-20 | 2006-06-08 | Mitsubishi Chemicals Corp | Method for producing amine compound and amine compound and electrophotographic photoreceptor, cartridge and apparatus for forming image |
| WO2023136334A1 (en) * | 2022-01-14 | 2023-07-20 | 富士フイルム株式会社 | Method for producing compound represented by formula (i) |
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