JPS6377843A - Production of n,n,n',n'-tetraarylbenzidine compound - Google Patents
Production of n,n,n',n'-tetraarylbenzidine compoundInfo
- Publication number
- JPS6377843A JPS6377843A JP61217952A JP21795286A JPS6377843A JP S6377843 A JPS6377843 A JP S6377843A JP 61217952 A JP61217952 A JP 61217952A JP 21795286 A JP21795286 A JP 21795286A JP S6377843 A JPS6377843 A JP S6377843A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- copper
- reaction
- alkali
- solvent
- 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
- 150000001875 compounds Chemical class 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- 125000004429 atom Chemical group 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 9
- 239000010949 copper Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical class C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001555 benzenes Chemical class 0.000 abstract description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 4
- UDHAWRUAECEBHC-UHFFFAOYSA-N 1-iodo-4-methylbenzene Chemical compound CC1=CC=C(I)C=C1 UDHAWRUAECEBHC-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 229910052740 iodine Inorganic materials 0.000 abstract description 3
- 229940094933 n-dodecane Drugs 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 abstract 2
- DRGMQKFBFLKDOX-UHFFFAOYSA-N 2-methyl-4-[3-methyl-4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]-n,n-bis(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C(=CC(=CC=1)C=1C=C(C)C(N(C=2C=CC(C)=CC=2)C=2C=CC(C)=CC=2)=CC=1)C)C1=CC=C(C)C=C1 DRGMQKFBFLKDOX-UHFFFAOYSA-N 0.000 abstract 1
- 238000004440 column chromatography Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 108091008695 photoreceptors Proteins 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- NUMXHEUHHRTBQT-AATRIKPKSA-N 2,4-dimethoxy-1-[(e)-2-nitroethenyl]benzene Chemical class COC1=CC=C(\C=C\[N+]([O-])=O)C(OC)=C1 NUMXHEUHHRTBQT-AATRIKPKSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- RHPVVNRNAHRJOQ-UHFFFAOYSA-N 4-methyl-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1NC1=CC=C(C)C=C1 RHPVVNRNAHRJOQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N N-phenyl aniline Natural products C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 239000007997 Tricine buffer Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- -1 diphenylamine compound Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- SNHMUERNLJLMHN-IDEBNGHGSA-N iodobenzene Chemical group I[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 SNHMUERNLJLMHN-IDEBNGHGSA-N 0.000 description 1
- 150000008424 iodobenzenes Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- RUDCBGCNXOSCTI-UHFFFAOYSA-N n-methoxy-4-[4-(methoxyamino)phenyl]aniline Chemical compound C1=CC(NOC)=CC=C1C1=CC=C(NOC)C=C1 RUDCBGCNXOSCTI-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000003799 water insoluble solvent 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)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、Ｎ、Ｎ、Ｎ−、ｌ＼−−テ］・うｊ７り−ル
ベンジジン化合物の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing N,N,N-,l\--te]-rubenzidine compounds.
従来の技術
Ｎ、Ｎ、Ｎ′、Ｎ−−テトラアリールベンジジン化合物
は、電子写真感光体にあける重荷輸送剤として有用な化
合物でおるか、従来このものの合成法としては、（１）
Ｎ、Ｎ＝−ジフェニルベンジジンをヨードベンピン化合
物と、炭酸カリ及び銅系触媒の存在下で縮合する方法（
特開昭５４−５４０３８号公報、米国特許第３，２６５
，４９６号明細書）及び（２＞４．４′−ショートビフ
ェニルを４，４−−ジメチルジフェニルアミンと炭酸カ
リ及び銅触媒の存在下で縮合する方法（特開昭５５−７
９４５０号公報）等が知られている。BACKGROUND OF THE INVENTION N,N,N',N--tetraarylbenzidine compounds are useful compounds as heavy transport agents for electrophotographic photoreceptors.
A method of condensing N,N=-diphenylbenzidine with an iodobenpine compound in the presence of potassium carbonate and a copper-based catalyst (
JP-A-54-54038, U.S. Patent No. 3,265
, 496) and a method of condensing (2>4.4'-short biphenyl with 4,4-dimethyldiphenylamine in the presence of potassium carbonate and a copper catalyst)
9450) etc. are known.
弁明が解決しようとする問題点
ところが、上記（１）の方法は、原料物質である＼、Ｎ
′−ジフェニルベンジジン化合物を製造するために粗原
料からの幾つかの工程が必要になり、したがって、目的
とするＮ、Ｎ、Ｎ′、Ｎ”−テ［〜ラアリールベンジジ
ン化合物を製造するのに手間が掛かるという欠点があっ
た。The problem that the defense attempts to solve However, the method (1) above does not work when the raw material is
Several steps are required from the crude raw material to produce the '-diphenylbenzidine compound, and therefore, to produce the desired N,N,N',N''-te[~raarylbenzidine compound. The drawback was that it was time-consuming.
また（２）の方法は、原料物質として置換基を有する４
、４′−ショートジフェニルを合成するのが困り］１で
入手し難く、したがって、ビフェニル骨格に買換基含有
する凶、Ｎ、Ｎ−２Ｎ−−テトラアリールベンジジン化
合物を製造するのが困難であった。In addition, method (2) uses 4 having a substituent as a raw material.
, 4'-Short diphenyl is difficult to obtain], and therefore it is difficult to produce N,N-2N-tetraarylbenzidine compounds containing an exchange group in the biphenyl skeleton. Ta.
本発明者省は、従来の技術における上記の問題点に鑑み
、先に、ビフェニル骨格に置換基を有する４、４′−シ
ョートビフェニル／８−製造する方法と共に、得られた
置換基を有する４、４′−ショートごフェニルをジフェ
ニルアミン化合物と縮合させることによって、Ｎ、Ｎ、
Ｎ”、Ｎ−−テトラアリールベンジジン化合物を製造す
る方法を提案したが、ざらに研究を進めた結果、入手が
容易な原料物質を用いて簡単な工程で目的とするＮ。In view of the above-mentioned problems in the prior art, the Ministry of the Inventor first proposed a method for producing 4,4'-short biphenyl/8- having a substituent on the biphenyl skeleton, and , 4'-short phenyl is condensed with a diphenylamine compound to form N, N,
We proposed a method for producing N'', N--tetraarylbenzidine compounds, but after extensive research, we found that the desired N could be produced in a simple process using easily available raw materials.
Ｎ、Ｎ′、Ｎ′−テトラアリールベンジジン化合物を製
造する方法を見出だし、本発明を完成するに至った。We have discovered a method for producing N,N',N'-tetraarylbenzidine compounds, and have completed the present invention.
したがって、本発明の目的は、入手か容易な原料物質か
ら簡単４．１′工程で高純度のＮ、Ｎ、Ｎ′。Therefore, the object of the present invention is to produce highly pure N, N, and N' in a simple 4.1' process from readily available raw materials.
Ｎ−−テトラアリールベンジジン化合物を高目×率で得
る方法を提供することにある。The object of the present invention is to provide a method for obtaining N--tetraarylbenzidine compounds at a high yield.
問題点を解決するための手段
本発明の上記目的は、一般式（Ｉ）で示されるハロゲン
化ベンゼン誘導体を
（式中、Ｒ１は水素原子、アルキル基またはアルコキシ
塁を示し、Ｘはよう素原子または臭素原子を示ず〉
一般式（ＩＩ）で示されるベンジジン誘導体とを（式中
、Ｒ２は水素原子、アルキル基又はアルコキシ桔を示す
）
銅系触媒及びアルカリの存在下で反応させることにより
、−、般式（Ｉ［Ｉ）で示されるＮ、Ｎ、Ｎ−。Means for Solving the Problems The above object of the present invention is to provide a halogenated benzene derivative represented by the general formula (I) (wherein R1 represents a hydrogen atom, an alkyl group or an alkoxy group, and X represents an iodine atom). or no bromine atom> by reacting with a benzidine derivative represented by general formula (II) (wherein R2 represents a hydrogen atom, an alkyl group, or an alkoxy group) in the presence of a copper-based catalyst and an alkali, -, N, N, N- represented by the general formula (I[I).
＼′−テトラアリールベンジジン化合物を製造すること
によって達成される。This is accomplished by producing a \'-tetraarylbenzidine compound.
ＩＲ１
（式中Ｒ１及びＲ２は前記と同じ意味を有する）本発明
の詳細な説明すると、原ね物質でおる一般式Ｎ）で示さ
れるハロゲン化ベンゼン誘導体は、容易に入手できるも
ので、本発明においては、特にヨードヘンセン誘導体が
好ましく、１シ１１えは、ヨードベンゼン、２−２３−
または４−ヨード１〜ルエン等を必げることかできる。IR1 (wherein R1 and R2 have the same meanings as above) To explain the present invention in detail, the halogenated benzene derivative represented by the general formula N), which is a raw material, is easily available and can be used in the present invention. In particular, iodobenzene derivatives are preferred, and one example is iodobenzene, 2-23-
Alternatively, 4-iodine to luene, etc. can be included.
また、一般式ＮＩ）で示されるベンジジン誘導体も容易
に入手てきるちので、例えば、２．２′−または３，３
′−ジメチルベンジジン、２゜２−一または３，３′−
ジメトキシベンジジン等をあげることかてきる。In addition, benzidine derivatives represented by the general formula NI) are also readily available; for example, 2,2'- or 3,3
'-Dimethylbenzidine, 2°2-1 or 3,3'-
You can also give dimethoxybenzidine, etc.
上記一般式（Ｉ）で示されるハロゲン化ｌ＼ンゼン誘導
体と上記一般式（ｎ）で示されるベンジジン誘導体との
縮合反応は、銅系触媒とアルカリの存在下、反応溶媒を
用い、または用いずに、加熱することによって行なうこ
とかできる。The condensation reaction between the halogenated l\zene derivative represented by the above general formula (I) and the benzidine derivative represented by the above general formula (n) is carried out in the presence of a copper-based catalyst and an alkali, with or without using a reaction solvent. This can be done by heating.
反応溶媒を用いる場合における反応溶媒としては、例え
ば、ドデカン、トリデカン等の高９１１点炭化水素系溶
媒が好ましく用いられる。この反応は、脱水反応でおる
ので、水の影響を受は易く、水の溶解性の悪い炭化水素
系溶媒が好ましい。炭化水素系溶媒を用いた場合、高収
率で不純物の精製も少なく、カラム等の手間のかかる精
製方法を使わずに精製ができる。When using a reaction solvent, for example, a high 911 point hydrocarbon solvent such as dodecane or tridecane is preferably used. Since this reaction is a dehydration reaction, it is easily affected by water, and a hydrocarbon solvent with poor water solubility is preferred. When a hydrocarbon solvent is used, the yield is high and impurities are less purified, and purification can be performed without using labor-intensive purification methods such as columns.
銅系触媒としては、銅粉末、Ｃｕ２Ｏ，Ｃｕｌ。Examples of copper-based catalysts include copper powder, Cu2O, and Cul.
Ｃ：、 ｕ Ｏ等を用いることができ、またアルカリと
しては、Ｋ ＯＨ１Ｋ２ＣＯ３、ＮａＨ等を用いること
かできる。C:, uO, etc. can be used, and as the alkali, KOH1K2CO3, NaH, etc. can be used.
また、縮合反応は、一般に１５０°Ｃ〜２３０’Ｃの範
囲の温度で行われる。Additionally, the condensation reaction is generally carried out at a temperature in the range of 150°C to 230'C.
本発明において、一般式（Ｉ）で示されるハロゲン化ベ
ンゼン誘導体は、一般式（ＩＩ＞で示されるベンジジン
誘導体１モルに対して反応当量以上、即ち４モルより過
剰に加えるのが好ましい。In the present invention, the halogenated benzene derivative represented by the general formula (I) is preferably added in an amount equal to or more than a reaction equivalent, that is, in excess of 4 moles, per mole of the benzidine derivative represented by the general formula (II>).
本発明において、目的生成物は、−反応終了後、取り出
すことができる。即ち、反応終了後、水を０口え、目的
生成物を溶解し、かつ水に不溶の溶媒を用いて抽出し、
抽出液を活性白土で処理し、適当な溶媒で再結晶して取
り出す。しかしながら目的生成物は、反応工程の途中で
取り出し・でもよい。In the present invention, the desired product can be removed after the reaction has ended. That is, after the reaction is complete, add 0 sips of water, dissolve the desired product, and extract using a water-insoluble solvent.
The extract is treated with activated clay, recrystallized with a suitable solvent and recovered. However, the desired product may be removed during the reaction process.
例えば、反応を一時中断し、目的生成物を溶媒等で抽出
して取り出し、その後、新ら！：に触媒、アルカリ及び
Ｉ京料物質を７Ｊ［］えて、反応を続ｉテさせてもよく
、この場合には、劣化した触媒やアルカリ等を除去する
ことができ、反応時間も）、９くなる。For example, the reaction is temporarily stopped, the desired product is extracted with a solvent, etc., and then a new product is extracted. The reaction may be continued by adding 7J[] of catalyst, alkali, and a raw material to the : In this case, the deteriorated catalyst, alkali, etc. can be removed, and the reaction time can also be reduced. It becomes.
本発明によって合成されるＮ、＼、＼′、Ｎ′−テトラ
アリールベンジジン化合物としては、例えば次ぎのちの
を例示することができる。Examples of the N,\,\',N'-tetraarylbenzidine compounds synthesized according to the present invention include the following.
なお、式中、１＼＝Ｉ ｅはメチル基を示す。In addition, in the formula, 1\=Ie represents a methyl group.
発明の効果
本発明によれば、容易に入手し得る化合物を出発原料物
質として用い、一工程で目的とするＮ。Effects of the Invention According to the present invention, easily available compounds are used as starting materials to obtain the desired N in one step.
Ｎ、Ｎ”’、Ｎ−−テトラアリールベンジジン化合物を
高純度かつ高収率で得ることができる。N,N"',N-tetraarylbenzidine compounds can be obtained with high purity and high yield.
本発明によって得られるＮ、Ｎ、Ｎ−、Ｎ−−テトラア
リールベンジジン化合物は、電子写真感光体における電
荷輸送剤として優れた持［生を示す。The N,N,N-,N-tetraarylbenzidine compound obtained by the present invention exhibits excellent durability as a charge transport agent in electrophotographic photoreceptors.
実施例 以下、本発明を実施例によって説明する。Example Hereinafter, the present invention will be explained by examples.
実施例１
へ、Ｎ、Ｎ−、Ｎ−−テトラキス−（４−メチルフェニ
ル）−３，３−−ジメヂルベンシシンの合成
０−トリシン３．１４Ｑ （１３，８ｍｍｏ Ｉ ）、
ＫＯＨ４０ｇ、ＣｕＩ４００ｍｙ及びｎ−ドデカン３０
ｍ１を、丸底フラスコ中で、窒素気流下、１８０’Ｃに
加熱し、４−ヨードトルエン２４．０９ （１１０ｍｍ
ｏ ｌ ＞を滴下した。１８０’Ｃで５時間反応させた
後、水を１１０え、トルエンで抽出した。更に反応を完
全にするために、溶剤を留去した後、ＫＯＨ４０９、Ｃ
ｕＩ４００ｍｆｆ及び４−ヨードトルエン２４．０９
（１１０ｍｍｏ ｌ ＞を加え、窒素気流下、１８０’
Ｃで、５時間反応させた。Example 1 Synthesis of N,N-,N-tetrakis-(4-methylphenyl)-3,3-dimethylbenshicine O-tricine 3.14Q (13,8mmol I),
KOH 40g, CuI 400my and n-dodecane 30g
m1 was heated to 180'C in a round-bottomed flask under a stream of nitrogen, and 4-iodotoluene 24.09 (110 mm
o l> was added dropwise. After reacting at 180'C for 5 hours, water was added at 110C and extracted with toluene. In order to further complete the reaction, after distilling off the solvent, KOH409,C
uI 400mff and 4-iodotoluene 24.09
(Add 110 mmol >, add 180 mmol under nitrogen stream,
The reaction was carried out at C for 5 hours.
水を加え、トルエンで抽出し、Ｎ ａ ２ Ｓ Ｏ４で
乾燥した後、活性白土て処理し、溶媒を留去して、Ｎ
、 ｌ＼、＼−、Ｎ−−テトラキスー（４−メチルフェ
ニル）−３，３−−ジメチルベンジジン５．９１ （収
率７５．７％）を得た。ざらにトルエン、アセトン及び
ヘキサンの混合溶媒で再結晶を行ない、４．３２ｙ （
最終収率５４．７％）の白色結晶を１９だ（融点１７４
〜１７５°Ｃ）。高速液体クロマトグラフィーによる純
度の測定の結果、純度し高いことか分った。（純度９９
．９％）実施例２
Ｎ、Ｎ、Ｎ＝、Ｎ−−テトラフェニル−３，３′−シメ
チルベンジジンの合成
〇−トリジン４．２５ｙ （２０，０ｍｍｏ ｌ ＞、
Ｋ ＯＨ５０ｇ、Ｃｕ１５００ｍｇ及びｎ−ドデカン３
０ｍ１を、丸底フラスコ中で、窒素気流下、１８０’Ｃ
に加熱し、ヨードベンゼン２４．４８ｇ（１２０ｍｍｏ
ｌ ）を滴下した。１８０’Ｃで６時間反応させた後
、水勺加え、ｉ−ルエンて抽出し、Ｎａ２ＳＯ４で）＋
２燥した後、活性白土て鷺理し、溶媒を留去して、Ｎ、
Ｎ、Ｎ”、Ｎ−−テトラフェニル−３，３−一シメヂル
ベンジジン６．３０９（収率６０．９％）を得た。さら
に、ベンセン／ノルマルｌベキサンの混合溶媒で再結晶
して、４．７９ｙ（収率４６．３％）の白色結晶を（Ｆ
７だ（融点１７５〜′１７８°Ｃ）。Add water, extract with toluene, dry with Na2SO4, treat with activated clay, evaporate the solvent, and extract with N.
, l\,\-,N--Tetrakis-(4-methylphenyl)-3,3-dimethylbenzidine 5.91 (yield 75.7%) was obtained. Roughly recrystallize with a mixed solvent of toluene, acetone and hexane to obtain 4.32y (
19 (final yield 54.7%) white crystals (melting point 174)
~175°C). As a result of measuring the purity by high performance liquid chromatography, it was found to be highly pure. (Purity 99
．． 9%) Example 2 Synthesis of N,N,N=,N--tetraphenyl-3,3'-simethylbenzidine〇-Tolidine 4.25y (20.0mmol>,
K OH 50g, Cu 1500mg and n-dodecane 3
0 ml in a round bottom flask at 180'C under nitrogen flow.
24.48g (120mmol) of iodobenzene
l) was added dropwise. After reacting at 180'C for 6 hours, water was added, extracted with i-luene, and extracted with Na2SO4)+
2. After drying, it is washed with activated clay, the solvent is distilled off, and N,
6.309 (yield: 60.9%) of N,N'',N--tetraphenyl-3,3-monocymedylbenzidine was obtained.Furthermore, it was recrystallized from a mixed solvent of benzene/n-bexane. White crystals of 4.79y (yield 46.3%) were collected from (F
7 (melting point 175-'178°C).
Claims (1)
導体と ▲数式、化学式、表等があります▼（ I ） （式中、Ｒ＿１は水素原子、アルキル基またはアルコキ
シ基を示し、Ｘはよう素原子または臭素原子を示す） 一般式（II）で示されるベンジジン誘導体とを ▲数式、化学式、表等があります▼（II） （式中、Ｒ＿２は水素原子、アルキル基又はアルコキシ
基を示す） 銅系触媒及びアルカリの存在下で反応させることを特徴
とする一般式（III）で示されるＮ，Ｎ，Ｎ′，Ｎ′−
テトラアリールベンジジン化合物の製造方法。 ▲数式、化学式、表等があります▼（III） （式中Ｒ＿１及びＲ＿２は前記と同じ意味を有する）(1) There are halogenated benzene derivatives represented by the general formula (I) and ▲mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 represents a hydrogen atom, an alkyl group, or an alkoxy group, and atom or bromine atom) ▲ Numerical formula, chemical formula, table, etc. are available▼(II) (In the formula, R_2 represents a hydrogen atom, an alkyl group, or an alkoxy group) Copper N, N, N', N'- represented by the general formula (III), characterized in that the reaction is carried out in the presence of a system catalyst and an alkali.
A method for producing a tetraarylbenzidine compound. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (R_1 and R_2 in the formula have the same meaning as above)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61217952A JPS6377843A (en) | 1986-09-18 | 1986-09-18 | Production of n,n,n',n'-tetraarylbenzidine compound |
| US07/098,333 US4933245A (en) | 1986-09-18 | 1987-09-18 | Electrophotographic photoreceptor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61217952A JPS6377843A (en) | 1986-09-18 | 1986-09-18 | Production of n,n,n',n'-tetraarylbenzidine compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6377843A true JPS6377843A (en) | 1988-04-08 |
Family
ID=16712285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61217952A Pending JPS6377843A (en) | 1986-09-18 | 1986-09-18 | Production of n,n,n',n'-tetraarylbenzidine compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6377843A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4480827B2 (en) * | 1998-12-25 | 2010-06-16 | 保土谷化学工業株式会社 | Method for producing triarylamine derivative |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61134354A (en) * | 1984-12-01 | 1986-06-21 | Ricoh Co Ltd | 3,3'-dimethylbenzidine derivative |
-
1986
- 1986-09-18 JP JP61217952A patent/JPS6377843A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61134354A (en) * | 1984-12-01 | 1986-06-21 | Ricoh Co Ltd | 3,3'-dimethylbenzidine derivative |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4480827B2 (en) * | 1998-12-25 | 2010-06-16 | 保土谷化学工業株式会社 | Method for producing triarylamine derivative |
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