JPS6045178B2 - Paramethylation method for anilines - Google Patents
Paramethylation method for anilinesInfo
- Publication number
- JPS6045178B2 JPS6045178B2 JP51101615A JP10161576A JPS6045178B2 JP S6045178 B2 JPS6045178 B2 JP S6045178B2 JP 51101615 A JP51101615 A JP 51101615A JP 10161576 A JP10161576 A JP 10161576A JP S6045178 B2 JPS6045178 B2 JP S6045178B2
- Authority
- JP
- Japan
- Prior art keywords
- anilines
- methanol
- toluidine
- xylidine
- methylation
- 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
Links
- 238000000034 method Methods 0.000 title claims description 11
- 150000001448 anilines Chemical class 0.000 title claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000007069 methylation reaction Methods 0.000 claims description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 230000011987 methylation Effects 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000012808 vapor phase Substances 0.000 claims description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 16
- CZZZABOKJQXEBO-UHFFFAOYSA-N 2,4-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1 CZZZABOKJQXEBO-UHFFFAOYSA-N 0.000 description 10
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 10
- 239000002808 molecular sieve Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 8
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical class CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HDFQKJQEWGVKCQ-UHFFFAOYSA-N 1,3-dimethyl-2-nitrobenzene Chemical group CC1=CC=CC(C)=C1[N+]([O-])=O HDFQKJQEWGVKCQ-UHFFFAOYSA-N 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- BBUPBICWUURTNP-UHFFFAOYSA-N 2,4-dimethyl-1-nitrobenzene Chemical group CC1=CC=C([N+]([O-])=O)C(C)=C1 BBUPBICWUURTNP-UHFFFAOYSA-N 0.000 description 1
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical group CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- QCIFLGSATTWUQJ-UHFFFAOYSA-N n,4-dimethylaniline Chemical compound CNC1=CC=C(C)C=C1 QCIFLGSATTWUQJ-UHFFFAOYSA-N 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 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
- 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】
本発明はパラ位に水素原子を有するアニリン類をメタ
ノールを用いて気相接触核メチル化するときにアルカリ
金属型合成ゼオライトを接触として用いることを特徴と
するアニリン類のパラメチル化方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention is a process for producing anilines having a hydrogen atom at the para position, which is characterized in that an alkali metal type synthetic zeolite is used as a catalyst when anilines having a hydrogen atom at the para position are subjected to vapor phase catalytic nuclear methylation using methanol. Relating to a paramethylation method.
本発明の方法の主要な目的生成物の一つである２・４
−キシリジンは、染料、農薬の中間体として有用である
。2.4, which is one of the main target products of the method of the present invention.
-Xylidine is useful as an intermediate for dyes and agricultural chemicals.
従来、このものは、ｍ−キシレンをニトロ化して、生
成する４−ニトローｍ−キシレンと２−ニトローｍ−キ
シレンを分離した後、前者を還元して製造されていたが
、廃液処理の問題、副生成物の問題等があり、好適な製
造法とは言えない。Conventionally, this product was produced by nitrating m-xylene, separating the produced 4-nitro m-xylene and 2-nitro m-xylene, and then reducing the former, but there were problems with waste liquid treatment; It cannot be said to be a suitable manufacturing method due to problems such as by-products.
しかし、本発明方法によれば、例えば安価な０−トル
イジンとメタノールを原料にして、簡単な装置及び操作
により連続的に、しかも廃液を排出することなく、２・
４−キシリジンを得ることができるので、従来の方法に
比較して有利である。同様に、本発明方法により染顔料
、農薬、医薬等の中間体として有用なパラメチルアニリ
ン誘導体を経済的に、また多量の異性体の副生の問題を
避けて製造することができる。 アニリン類の核メチル
化についてはドイツ特許出願公開第２２４０３６訝公報
にＭｏＯ。However, according to the method of the present invention, for example, inexpensive 0-toluidine and methanol are used as raw materials, and 2.
This method is advantageous compared to conventional methods because 4-xylidine can be obtained. Similarly, by the method of the present invention, para-methylaniline derivatives useful as intermediates for dyes and pigments, agricultural chemicals, medicines, etc. can be produced economically and without the problem of large amounts of isomer by-products being produced. Regarding the nuclear methylation of anilines, see MoO in German Patent Application No. 224036.
一月。００の存在下、アニリン類をメタノールで気相メ
チル化してメシジンを得ることが記載されている。January. It is described that gas phase methylation of anilines with methanol in the presence of 00 to give mesidine.
しかし、この特許の目的はメシジンの製造にあり、中
間生成物のキシリジンの組成については全く触れていな
い。However, the purpose of this patent is the production of mesidine and does not mention at all the composition of the intermediate product xylidine.
また本発明者がこの特許の追試を行つてみたところ、メ
シジンの製造には適しているものの、２・４−キシリジ
ンを選択的に製造する目的は、まつたく適さないことが
わかつた。また高官は早稲田大学理工学研究所報告第６
９輯（１９７５）、２１〜２５頁に、「遷移金属ゼオラ
イト触媒を用いたアニリンのメタノールによるＮ−メチ
ル化反応」と題する報文の中で、Ｕ、Ｃ、Ｃ、製Ｙ型モ
レキユラーシーブＳＫ−４０（ＮａＹ）を種々の金属イ
オンで、イオン交換して調整した触媒を、アニリンのＮ
−メチル化に使用するとき、トルイジン類（ｐ−トルイ
ジン、Ｎ−メチルｐ−トルイジン）力唱１生することを
述べている。しカルこの報文はＮ−メチル化反応が主目
的であり核メチル化については、詳細な記述はない。
また、Ｕ、Ｃ、Ｃ、製Ｙ型・モレキユラーシーブＳＫ−
４０（ＮａＹ）そのものについての触媒作用にはまつた
く触れていない。Further, when the present inventor conducted a follow-up test on this patent, it was found that although it is suitable for the production of methidine, it is not suitable for the purpose of selectively producing 2,4-xylidine. In addition, high-ranking officials said that Waseda University Institute of Science and Engineering Report 6
9 (1975), pp. 21-25, in a report entitled "N-methylation reaction of aniline with methanol using a transition metal zeolite catalyst", Y-type molecular molecules manufactured by U, C, C, A catalyst prepared by ion-exchanging Sieve SK-40 (NaY) with various metal ions was mixed with N of aniline.
- It is stated that toluidines (p-toluidine, N-methyl p-toluidine) are used for methylation. The main purpose of this report is the N-methylation reaction, and there is no detailed description of nuclear methylation.
In addition, U, C, C, Y type molecular sieve SK-
The catalytic action of 40 (NaY) itself is not mentioned at all.
本発明者はパラ位に少くとも１個の水素原子を有する
アニリン類とメタノールの気相接触反応について検討し
たところ、アルカリ金属型合成ゼオライトが、選択的パ
ラメチル化の高活性触媒であることを見い出した。The present inventor investigated the gas phase catalytic reaction of methanol and anilines having at least one hydrogen atom at the para position, and discovered that alkali metal type synthetic zeolite is a highly active catalyst for selective para-methylation. Ta.
本発明て使用する合成ゼオライトの中でも組成がＳｊＯ
２５Ｏ〜８０％、，Ａｌ２Ｏ３７〜３０％、Ｎａ２Ｏｌ
．５〜２０％てあり細孔径が８−１０Ａのものが好まし
く、具体的にはＵ．Ｃ．Ｃ．製Ｙ型モレキユラーシーブ
ＳＫ４Ｏ（ＮａＹ）、およびノートン製モレキユラーシ
ーブ・ゼオロン９００Ｎａが特に好ましい触媒作用を示
す。Among the synthetic zeolites used in the present invention, the composition is SjO.
25O~80%, Al2O37~30%, Na2Ol
．． 5 to 20% and a pore size of 8 to 10A, specifically, one with a pore size of 8 to 10A. C. C. Y-type molecular sieve SK4O (NaY) manufactured by Norton Corporation and Zeolon 900Na manufactured by Norton Corporation exhibit particularly preferable catalytic activity.
これらのモレキユラーシーブ中のＮａをＨ＋や多価金属
イオンで交換したものは、活性が弱く、ノートン製モレ
キユラーシーブ●ゼオロン９００Ｈにいたつては核メチ
ル化能は無視しうる。本発明に用いる触媒は、市販のモ
レキユラーシーブを４００〜７００℃にて、含酸素ガス
中で焼成して調成することが好ましい。Molecular sieves in which Na is exchanged with H+ or polyvalent metal ions have weak activity, and the nuclear methylation ability of Norton's molecular sieve Zeolon 900H can be ignored. The catalyst used in the present invention is preferably prepared by calcining a commercially available molecular sieve at 400 to 700°C in an oxygen-containing gas.
又必要な粒度に破砕すれは固定床にも流動床にも使用で
きる。本発明方法によれば、所定の温度に保つた触媒床
に、所定の比率の原料アニリン類とメタノールを気相で
接触させることによつて反応を行なう。Furthermore, it can be used in both fixed beds and fluidized beds after being crushed to the required particle size. According to the method of the present invention, a reaction is carried out by bringing a predetermined ratio of raw material anilines and methanol into contact in a gas phase with a catalyst bed maintained at a predetermined temperature.
この場合、必要によつては、窒素や水素、水蒸気等の不
活性ガスの流通存在下に実施してもよい。本発明方法は
、ｏ−トルイジンを原料にして、２・４ーキシリジンを
製造する目的に特に有用であり、又アニリンを原料にし
てｐ−トルイジンを製造するときにも使用できる。一般
にバラ位に水素原子を有するアルキル、ハロゲン、アル
コキシ、アミノ、アルキルアミノ等，の置換基を有する
アニリンを原料になし得る。In this case, if necessary, the reaction may be carried out in the presence of a flowing inert gas such as nitrogen, hydrogen, or water vapor. The method of the present invention is particularly useful for producing 2,4-xylidine using o-toluidine as a raw material, and can also be used for producing p-toluidine using aniline as a raw material. In general, aniline having a substituent such as alkyl, halogen, alkoxy, amino, alkylamino, etc. having a hydrogen atom at the rose position can be used as a raw material.
反応温度は３８０乃至５００℃が好ましく、特に４２０
乃至４７０℃が好ましい。低温ではＮ−メチル体の副生
が多く、高温では脱メチル化、ハルツ化等の分解反応が
進行する。原料アニリンに対するメタノールのモル比は
、１〜４が好ましく、特に２〜３がよい。The reaction temperature is preferably 380 to 500°C, particularly 420°C.
The temperature range is preferably from 470°C to 470°C. At low temperatures, many N-methyl forms are produced as by-products, and at high temperatures, decomposition reactions such as demethylation and harzation proceed. The molar ratio of methanol to raw material aniline is preferably 1 to 4, particularly preferably 2 to 3.
原料アニリンのメタノール溶液の液空間速度は０．０５
〜１．０が好ましく、特に０．３〜０．６がよい。The liquid space velocity of the methanol solution of raw material aniline is 0.05
-1.0 is preferable, and 0.3-0.6 is especially good.
又反応は加圧下でも常圧下でも減圧下でも行なこい得る
。反応生成ガスは冷却して、凝縮捕集し、メタノールと
水を留去した後、メチルアニリン誘導体を得、更に精留
等の方法で各成分に分離する。次に実施例によつて、本
発明を具体的に説明する。Moreover, the reaction can be carried out under increased pressure, normal pressure, or reduced pressure. The reaction product gas is cooled, condensed and collected, and methanol and water are distilled off to obtain a methylaniline derivative, which is further separated into each component by a method such as rectification. Next, the present invention will be specifically explained with reference to Examples.
実施例１
市販の、Ｕ．Ｃ．Ｃ．製Ｙ型モレキユラーシーブＳＫ−
４０（ＮａＹ）（高さ２Ｔ！ｒ！！Ｌ１外径２７７！７
７！の円柱状に成型されたもの）、２０ｍ１をＳＵＳ−
３２のステンレス製反応管（内径１５．５ＴｆｒＩｎ１
外径２０７ｍ１長さ印ａ）に充填し、空気を流しながら
、外部を電気炉で加熱ノし、５００〜６００℃で３時間
、焼成した。Example 1 Commercially available U. C. C. Y type molecular sieve manufactured by SK-
40 (NaY) (Height 2T!r!!L1 outer diameter 277!7
7! molded into a cylindrical shape), 20m1 of SUS-
32 stainless steel reaction tubes (inner diameter 15.5TfrIn1
It was filled into a container with an outer diameter of 207 m and a length marked a), and while air was flowing, the outside was heated in an electric furnace and fired at 500 to 600°C for 3 hours.
そして、空気を窒素に切りかえ、１５ｍ１ノＭｊｎの流
量に保ち、反応温度を４４０℃に保つた後、ｏ−トルイ
ジンのメタノール溶液（メタノール対０−トルイジン、
モル比２）を注入器により、６．４ｍ１１ｈｒの流量で
注入する。反応生成物を凝縮管に捕集後、ガスクロマト
グラフィーで分析したところ、次の結果を得た。但し、
重量％で示す。Then, the air was replaced with nitrogen, the flow rate was kept at 15 ml, and the reaction temperature was kept at 440°C. Then, a methanol solution of o-toluidine (methanol vs. o-toluidine,
A molar ratio of 2) is injected using a syringe at a flow rate of 6.4 ml/hr. After collecting the reaction product in a condensation tube, it was analyzed by gas chromatography, and the following results were obtained. however,
Expressed in % by weight.
０−トルイジン２１．３％、２・６ーキシリジン２．３
％、２・４ーキシリジン６５．４％、メシジン１１．０
％、粗収率＝ーヱ？五拭ＹＹ一刈叩＝１０４％
注入した原料６り実施例２
実施例１において、ｏ−トルイジンのかわりに、アニリ
ンを使用したほかはすべて同じ方法で活性試験を行なつ
たところ、次に結果を得た。0-Toluidine 21.3%, 2,6-xylidine 2.3
%, 2,4-xylidine 65.4%, methidine 11.0
%, gross yield=ーヱ? Five wipes YY one blow = 104%
Injected Raw Materials Example 2 An activity test was conducted in the same manner as in Example 1 except that aniline was used instead of o-toluidine, and the following results were obtained.
アニリン１７．８％、ｏ−トルイジン３．８％、ｐ−ト
ルイジン７５．８％、２・４ーキシリジン２．６％、粗
収率＝１０２％実施例３
実施例１において、Ｕ．Ｃ．Ｃ．製Ｙ型モレキユラーシ
ーブＳＫ−４０（ＮａＹ）のかわりに、ノートン製モレ
キユラーシーブ・ゼオロン９００Ｎａを使用したほかは
すべて、同じ方法で活性試験を行なつたところ次の結果
を得た。Aniline 17.8%, o-toluidine 3.8%, p-toluidine 75.8%, 2,4-xylidine 2.6%, crude yield = 102% Example 3 In Example 1, U. C. C. An activity test was conducted in the same manner except that Molecular Sieve Zeolon 900Na manufactured by Norton Co., Ltd. was used instead of Y-type molecular sieve SK-40 (NaY) manufactured by Y. Co., Ltd. The following results were obtained.
０−トルイジン２９．７％、２●６ーキシリジン２．７
％、２・４ーキシリジン５２・３％、メシジン１５．３
％、粗収率＝９２．３％。0-Toluidine 29.7%, 2●6-xylidine 2.7
%, 2,4-xylidine 52.3%, methidine 15.3
%, crude yield = 92.3%.
Claims (1)
を用いて、気相接触核メチル化するときに、アルカリ金
属型合成ゼオライトを接触として用いることを特徴とす
るアニリン類のパラメチル化方法。1. A method for paramethylating anilines, which comprises using an alkali metal type synthetic zeolite as a contact when anilines having a hydrogen atom at the para position are subjected to vapor phase catalytic nuclear methylation using methanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51101615A JPS6045178B2 (en) | 1976-08-27 | 1976-08-27 | Paramethylation method for anilines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51101615A JPS6045178B2 (en) | 1976-08-27 | 1976-08-27 | Paramethylation method for anilines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5328128A JPS5328128A (en) | 1978-03-16 |
| JPS6045178B2 true JPS6045178B2 (en) | 1985-10-08 |
Family
ID=14305298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP51101615A Expired JPS6045178B2 (en) | 1976-08-27 | 1976-08-27 | Paramethylation method for anilines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6045178B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE33549E (en) * | 1983-12-07 | 1991-03-05 | E. I. Du Pont De Nemours And Company | Process for preparing a mixture of methyl- or ethyl-substituted primary anilines |
| US5126484A (en) * | 1983-12-07 | 1992-06-30 | E. I. Du Pont De Nemours And Company | Process for preparing methyl- and ethyl-substituted primary anilines |
| US4593124A (en) * | 1983-12-07 | 1986-06-03 | E. I. Du Pont De Nemours And Company | Process for preparing a mixture of methyl- or ethyl-substituted primary anilines |
| US5171890A (en) * | 1983-12-07 | 1992-12-15 | E. I. Du Pont De Nemours And Company | Process for preparing methyl- and ethyl-substituted primary anilines |
| US5093527A (en) * | 1983-12-07 | 1992-03-03 | E. I. Du Pont De Nemours And Company | Process for preparing methyl- and ethyl-substituted primary anilines |
| US4804784A (en) * | 1983-12-07 | 1989-02-14 | E. I. Du Pont De Nemours And Company | Process for preparing methyl- and ethyl-substituted primary anilines |
| US4795833A (en) * | 1987-02-04 | 1989-01-03 | E. I. Du Pont De Nemours And Company | Process for preparing a mixture of methyl-substituted primary anilines |
| US5081302A (en) * | 1989-04-27 | 1992-01-14 | First Chemical Corporation | Selective c-alkylation of aniline in the presence of zeolite catalysts to para-aniline |
| US4973754A (en) * | 1989-05-15 | 1990-11-27 | Shell Oil Company | Preparation of bis(p-aminocumyl)benzenes |
-
1976
- 1976-08-27 JP JP51101615A patent/JPS6045178B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5328128A (en) | 1978-03-16 |
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