JPS62226950A - Production of p-alkoxydiphenylamine compound - Google Patents
Production of p-alkoxydiphenylamine compoundInfo
- Publication number
- JPS62226950A JPS62226950A JP61071630A JP7163086A JPS62226950A JP S62226950 A JPS62226950 A JP S62226950A JP 61071630 A JP61071630 A JP 61071630A JP 7163086 A JP7163086 A JP 7163086A JP S62226950 A JPS62226950 A JP S62226950A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- reaction
- copper
- formula
- alkoxydiphenylamines
- 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 8
- 150000001875 compounds Chemical class 0.000 title abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 239000005749 Copper compound Substances 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 239000007859 condensation product Substances 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 238000006114 decarboxylation reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002516 radical scavenger Substances 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract description 10
- 239000007795 chemical reaction product Substances 0.000 abstract description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract description 5
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000011541 reaction mixture Substances 0.000 abstract description 4
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052740 iodine Inorganic materials 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 238000006482 condensation reaction Methods 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 7
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CDGNLUSBENXDGG-UHFFFAOYSA-N meta-Cresidine Chemical compound COC1=CC=C(N)C(C)=C1 CDGNLUSBENXDGG-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ATCRIUVQKHMXSH-UHFFFAOYSA-N 2,4-dichlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1Cl ATCRIUVQKHMXSH-UHFFFAOYSA-N 0.000 description 2
- LNEVUNYUJNORRV-UHFFFAOYSA-N 2-chloro-4-methoxyaniline Chemical compound COC1=CC=C(N)C(Cl)=C1 LNEVUNYUJNORRV-UHFFFAOYSA-N 0.000 description 2
- RQRMTSCQUFXYNI-UHFFFAOYSA-N 2-ethyl-4-methoxyaniline Chemical compound CCC1=CC(OC)=CC=C1N RQRMTSCQUFXYNI-UHFFFAOYSA-N 0.000 description 2
- GQMOFUZZCSQSNP-UHFFFAOYSA-N 4-ethoxy-2-methylaniline Chemical compound CCOC1=CC=C(N)C(C)=C1 GQMOFUZZCSQSNP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- ULHFFAFDSSHFDA-UHFFFAOYSA-N 1-amino-2-ethoxybenzene Chemical compound CCOC1=CC=CC=C1N ULHFFAFDSSHFDA-UHFFFAOYSA-N 0.000 description 1
- -1 2,3-dimethyl-4-ethoxyaniline Chemical compound 0.000 description 1
- MRUDNSFOFOQZDA-UHFFFAOYSA-N 2,6-dichlorobenzoic acid Chemical compound OC(=O)C1=C(Cl)C=CC=C1Cl MRUDNSFOFOQZDA-UHFFFAOYSA-N 0.000 description 1
- XRXMNWGCKISMOH-UHFFFAOYSA-N 2-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Br XRXMNWGCKISMOH-UHFFFAOYSA-N 0.000 description 1
- YGLYYWZISFBCPU-UHFFFAOYSA-N 4-ethoxy-2-methyl-n-phenylaniline Chemical compound CC1=CC(OCC)=CC=C1NC1=CC=CC=C1 YGLYYWZISFBCPU-UHFFFAOYSA-N 0.000 description 1
- CYMPUOGZUXAIMY-UHFFFAOYSA-N 4-methoxy-2-methyl-n-phenylaniline Chemical compound CC1=CC(OC)=CC=C1NC1=CC=CC=C1 CYMPUOGZUXAIMY-UHFFFAOYSA-N 0.000 description 1
- ZTKDMNHEQMILPE-UHFFFAOYSA-N 4-methoxy-n,n-dimethylaniline Chemical compound COC1=CC=C(N(C)C)C=C1 ZTKDMNHEQMILPE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 150000008061 acetanilides Chemical class 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- XRYSCSFJNUNNAU-UHFFFAOYSA-N n-chloro-n-phenylaniline Chemical compound C=1C=CC=CC=1N(Cl)C1=CC=CC=C1 XRYSCSFJNUNNAU-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 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)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ｐ−アルコキシジフェニルアミン類の製造方
法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing p-alkoxydiphenylamines.
（従来の技術）
ｐ−アルコキシジフェニルアミン類は、感熱及び感圧色
素として用いられるフルオラン系色素の重要な中間体で
ある。かかるｐ−アルコキシジフェニルアミン類を製造
する方法は、従来、種々知られている。例えば、特公昭
５２−５４８９号公報には、ｐ−アルコキシフェニルア
ミン類をＮ−アセチル化した後、銅粉、ヨウ素及び炭酸
カリウムの存在下にブロムベンゼンと高温にて反応させ
て縮合させ、次いで、得られた縮合生成物を加水分解さ
せる方法が記載されている。また、特開昭５２−８２２
４．３号公報には、ｐ−アルコキシブロムベンゼン類と
アセトアニリド誘導体とを高温で縮合させた後、得られ
た縮合生成物を加水分解させる方法が記載されている。(Prior Art) p-Alkoxydiphenylamines are important intermediates for fluoran dyes used as heat- and pressure-sensitive dyes. Various methods for producing such p-alkoxydiphenylamines are conventionally known. For example, Japanese Patent Publication No. 52-5489 discloses that p-alkoxyphenylamines are N-acetylated and then reacted with bromobenzene at high temperature in the presence of copper powder, iodine and potassium carbonate to condense the compound. , describes a method for hydrolyzing the condensation product obtained. Also, JP-A-52-822
Publication No. 4.3 describes a method in which p-alkoxybromobenzenes and acetanilide derivatives are condensed at high temperature and then the resulting condensation product is hydrolyzed.
しかし、これらの方法によれば、いずれも、原料である
アリールアミンの有するアミノ基を例えばアセチル基に
て保護しつつ、所要の縮合反応を行なった後、保護基を
脱離させ、更に、得られた縮合生成物を強塩基の存在下
に加水分解させるので、多数の工程を要して、反応操作
が煩瑣であると共に、縮合反応に高温長時間を要し、ま
た、加水分解反応にも、１８０〜２００℃程度の高温で
長時間加熱する必要があって、エネルギー費用が高く、
且つ、生産性に劣る。However, according to these methods, after carrying out the necessary condensation reaction while protecting the amino group of the raw material arylamine with, for example, an acetyl group, the protecting group is removed, and then the Since the resulting condensation product is hydrolyzed in the presence of a strong base, it requires many steps and the reaction operation is cumbersome, and the condensation reaction requires a high temperature and a long time. , it is necessary to heat at a high temperature of about 180 to 200 degrees Celsius for a long time, and the energy cost is high.
Moreover, productivity is poor.
（発明の目的）
本発明は、ｐ−アルコキシジフェニルアミン類の製造に
おける上記した問題を解決するためになされたものであ
って、高収率高生産性にて且つ低度にｐ−アルコキシジ
フェニルアミン類を製造する方法を提供することを目的
とする。(Object of the Invention) The present invention has been made to solve the above-mentioned problems in the production of p-alkoxydiphenylamines, and it is possible to produce p-alkoxydiphenylamines with high yield, high productivity, and to a low degree. The purpose is to provide a method for manufacturing.
（発明の構成）
本発明によるｐ−アルコキシジフェニルアミン類の製造
方法は、一般式（１）
（式中、Ｒ１及びＲ２はそれぞれ独立にアルキル基を示
し、ＸＩは塩素、臭素及びフッ素より選ばれるハロゲン
を示し、ｍ及びｎはそれぞれ０〜４の数を示す。但し、
ｍ ＋ ｎは４以下である。）で表わされる化合物と、
一般式（ＩＩ）（式中、Ｒ２及びＸＩ は前記と同じで
あり、Ｘ２は塩素、臭素及びヨウ素より選ばれるハロゲ
ンを示し、ｐ及びｑはそれぞれθ〜４の数を示す。但し
、ｐ＋ｑは４以下である。）
で表わされる化合物とを、銅又は銅化合物と、酸捕捉剤
との存在下に溶剤中にて縮合させ、次いで、生成した縮
合生成物を加熱して、脱炭酸させることを特徴とする。(Structure of the Invention) The method for producing p-alkoxydiphenylamines according to the present invention is based on the general formula (1) (wherein R1 and R2 each independently represent an alkyl group, and XI is a halogen selected from chlorine, bromine, and fluorine. , and m and n each represent a number from 0 to 4.However,
m + n is 4 or less. ) and a compound represented by
General formula (II) (wherein R2 and XI are the same as above, X2 represents a halogen selected from chlorine, bromine and iodine, and p and q each represent a number from θ to 4. However, p+q is 4 or less) with copper or a copper compound in a solvent in the presence of an acid scavenger, and then heating the resulting condensation product to decarboxylate it. It is characterized by
即ち、本発明の方法は、次の反応工程に示すように、先
ず、縮合生成物（ＩＩＩ）を得、これを分離することな
しに、そのまま脱炭酸させて、目的とするｐ−アルコキ
シジフェニルアミン＠（■）を得るものである。That is, in the method of the present invention, as shown in the following reaction step, the condensation product (III) is first obtained, and this is directly decarboxylated without separation to produce the target p-alkoxydiphenylamine@ (■) is obtained.
（ＩＩＩ）
（ＩＶ）
前記一般式Ｎ）で表わされるｐ−アルコキシフェニルア
ミン類において、アルキル基は好ましくは炭素数１〜５
の低級アルキル基であり、特に好ましくは炭素数１〜３
である。例えば、メチル基又はエチル基が好ましい。従
って、かかる化合物の好ましい具体例として、例えば、
２−メチル−４−メトキシアニリン、２−メチル−４−
エトキシアニリン、２．３−ジメチル−４−エトキシア
ニリン等を挙げることができる。かかる化合物は、いず
れも既に知られている方法にて容易に製造することがで
き、又は容易に入手することができる。(III) (IV) In the p-alkoxyphenylamines represented by the general formula N), the alkyl group preferably has 1 to 5 carbon atoms.
is a lower alkyl group having 1 to 3 carbon atoms, particularly preferably
It is. For example, a methyl group or an ethyl group is preferred. Therefore, as preferred specific examples of such compounds, for example,
2-Methyl-4-methoxyaniline, 2-methyl-4-
Examples include ethoxyaniline, 2,3-dimethyl-4-ethoxyaniline, and the like. All such compounds can be easily produced by already known methods or can be easily obtained.
また、一般式（ＩＩ）で表わされる０−ハロ安息香酸類
において、アルキル基は好ましくは炭素数１〜５の低級
アルキル基であり、特に好ましくは炭素数１〜３である
。例えば、メチル基又はエチル基が好ましい。従って、
かかる化合物の好ましい具体例として、０−クロロ安息
香酸、０−ブロム安息香酸、２，４−ジクロロ安息香酸
等を挙げることができる。かかる化合物も容易に入手す
ることができる。Further, in the 0-halobenzoic acids represented by the general formula (II), the alkyl group is preferably a lower alkyl group having 1 to 5 carbon atoms, particularly preferably 1 to 3 carbon atoms. For example, a methyl group or an ethyl group is preferred. Therefore,
Preferred specific examples of such compounds include 0-chlorobenzoic acid, 0-brobenzoic acid, 2,4-dichlorobenzoic acid, and the like. Such compounds are also readily available.
尚、後述する本発明による反応条件下においては、上記
ｐ−アルコキシフェニルアミン類（１）がハロゲンを有
しても、この化合物相互の間の自己縮合は起こらず、ま
た、０−ハロ安息香酸類（ｎ）がカルボキシル基の〇−
位置以外にハロゲンを有する場合も、ｐ−アルコキシフ
ェニルアミン類（Ｉ）との縮合反応は、カルボキシル基
の０−位置のハロゲンにおいて選択的に起こる。Note that under the reaction conditions according to the present invention described later, even if the p-alkoxyphenylamines (1) have halogen, self-condensation between these compounds does not occur, and 0-halobenzoic acids (n) is carboxyl group〇-
Even when a halogen is present at a position other than the position, the condensation reaction with p-alkoxyphenylamine (I) occurs selectively at the halogen at the 0-position of the carboxyl group.
本発明の方法においては、上記ｐ−アルコキシフェニル
アミン類（１）と０−クロル安息香酸類（ＩＩ）との縮
合反応は、銅又は銅化合物を触媒とし、酸捕捉剤の存在
下に、通常、有機溶剤中において加熱することによって
行なわれ、前記縮合生成物（ＩＩＩ）が生成する。ここ
に、上記溶剤としては、この縮合反応に不活性であると
共に、上記縮合生成物を溶解するものであれば、特に限
定されるものではないが、例えば、アルコール類やグリ
コール類が好ましく用いられる。特に、縮合生成物の収
率や、後述するように、この縮合生成物の加熱脱炭酸時
における溶剤の回収の容易性等から、ブタノール、アミ
ルアルコール、エチレングリコール、エチルグリコール
等が好ましく用いられる。In the method of the present invention, the condensation reaction between the p-alkoxyphenylamines (1) and the 0-chlorobenzoic acids (II) is carried out using copper or a copper compound as a catalyst, usually in the presence of an acid scavenger. This is carried out by heating in an organic solvent to produce the condensation product (III). Here, the above-mentioned solvent is not particularly limited as long as it is inert to this condensation reaction and dissolves the above-mentioned condensation product, but for example, alcohols and glycols are preferably used. . In particular, butanol, amyl alcohol, ethylene glycol, ethyl glycol, etc. are preferably used in view of the yield of the condensation product and the ease of recovering the solvent during thermal decarboxylation of the condensation product as described later.
上記触媒としての銅は、例えば、粉末やスポンジ状で用
いられる。また、銅化合物としては、例えば、塩化銅、
酸化銅、酢酸銅等が用いられる。Copper as the catalyst is used, for example, in the form of powder or sponge. In addition, examples of copper compounds include copper chloride,
Copper oxide, copper acetate, etc. are used.
触媒の使用量は、通常、ウルマン反応において知られて
いる量でよく、例えば、０−クロル安息香酸類に対して
、０．３〜１０重量％、好ましくは０゜５〜２重景重量
範囲で用いられる。また、上記酸捕捉剤は、前記縮合反
応において副生ずるハロゲン化水素を捕捉し得るものあ
れば、特に限定されるものではなく、無機又は有機塩基
が適宜に用いられが、例えば、アルカリ金属の水酸化物
、炭酸塩、炭酸水素塩や、第３繰合機アミン等が好適で
ある。特に、炭酸塩が好ましく、なかでも炭酸カリウム
が好ましい。酸捕捉剤の使用量は、０−ハロ安息香酸類
の中和量乃至その２倍量までの範囲が適当である。The amount of the catalyst to be used may be the amount known in the Ullmann reaction, for example, 0.3 to 10% by weight, preferably in the range of 0.5 to 2 weight percent based on 0-chlorobenzoic acid. used. The acid scavenger is not particularly limited as long as it can capture the hydrogen halide produced as a by-product in the condensation reaction, and an inorganic or organic base may be used as appropriate. Oxides, carbonates, hydrogen carbonates, third recombinant amines, and the like are suitable. Carbonates are particularly preferred, and potassium carbonate is especially preferred. The amount of acid scavenger used is suitably within the range of the neutralizing amount of 0-halobenzoic acids to twice that amount.
縮合反応温度は、通常、８０〜１５０℃の範囲であり、
好ましくは９０〜１１０℃の範囲である。The condensation reaction temperature is usually in the range of 80 to 150°C,
Preferably it is in the range of 90 to 110°C.
また、反応時間は、原料としても化合物や反応温度等に
もよるが、通常、３〜２０時間で反応は終了する。Although the reaction time depends on the raw materials, compounds, reaction temperature, etc., the reaction is usually completed in 3 to 20 hours.
本発明の方法においては、上述した縮合反応の終了の後
、縮合生成物であるｐ−アルコキシジフェニルアミンカ
ルボン酸！ （ＩＩＩ）を分離することなしにそのまま
、１７０〜２５０°Ｃ１好ましくは１９０〜２００°Ｃ
の温度に昇温しで、その温度に数時間保持し、かくして
、縮合生成物を脱炭酸させて、目的とするｐ−アルコキ
シジフェニルアミンこれを適宜の溶剤中で加熱して、脱
炭酸させてもよいのは勿論である。尚、本発明において
は、縮合生成物の加熱による脱炭酸時に同時に溶剤を留
去させ、回収するのが望ましい。In the method of the present invention, after the above-mentioned condensation reaction is completed, the condensation product p-alkoxydiphenylaminecarboxylic acid! (III) without separation, at 170-250°C, preferably at 190-200°C
The condensation product is decarboxylated by heating to a temperature of Of course it's good. In the present invention, it is desirable to simultaneously distill off and recover the solvent when the condensation product is decarboxylated by heating.
反応終了後、反応混合物を冷却し、温水を加え、洗浄し
、脱塩した後、分液し、油分を蒸留することによって、
白色乃至淡黄色のｐ−アルコキシジフェニルアミン類を
得ることができる。本発明の方法によれば、通常、原料
であるｐ−アルコキシフェニルアミン類に基づいて、ｐ
−アルコキシジフェニルアミン類を約７０％以上の高収
率にて得ることができる。After the reaction is completed, the reaction mixture is cooled, added with warm water, washed, desalted, separated into layers, and distilled to remove the oil.
White to pale yellow p-alkoxydiphenylamines can be obtained. According to the method of the present invention, based on p-alkoxyphenylamines as raw materials, p-
-Alkoxydiphenylamines can be obtained in a high yield of about 70% or more.
（発明の効果）
以上のように、本発明によれば、容易に入手し得る原料
を用いて、穏やかな反応条件下での縮合及び脱炭酸から
なる工程にて容易且つ高生産性、高収率にて目的とする
ｐ−アルコキシフェニルジアミン類を得ることができる
。特に、本発明の方法によって、縮合反応後の反応混合
物をそのまま加熱して脱炭酸指せると共に、この脱炭酸
工程において溶剤を回収することによって、経済性高く
、目的物を得ることができる。(Effects of the Invention) As described above, according to the present invention, a process consisting of condensation and decarboxylation under mild reaction conditions can be carried out easily, with high productivity, and with high yield, using easily available raw materials. The target p-alkoxyphenyldiamines can be obtained at a high yield. In particular, according to the method of the present invention, the reaction mixture after the condensation reaction is directly heated to perform decarboxylation, and the solvent is recovered in this decarboxylation step, thereby making it possible to obtain the desired product with high economic efficiency.
（実施例）
以下に実施例を挙げて本発明を説明するが、本発明はこ
れら実施例により何ら限定されるものではない。(Examples) The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples in any way.
実施例１
０−クロロ安息香酸２２．６ ｇ、炭酸カリウム１０．
４．ｇ、２−メチル−４−メトキシアニリン１９゜２ｇ
＆ヒ６Ｉｉ４粉０．２３８をｎ−アミルアルコール中に
投入し、攪拌しつつ昇温し、１００〜１２０°Ｃの温度
にて約１０時間攪拌下に反応させた。Example 1 0-chlorobenzoic acid 22.6 g, potassium carbonate 10.
4. g, 2-methyl-4-methoxyaniline 19°2g
0.238 of &hi6Ii4 powder was put into n-amyl alcohol, heated while stirring, and reacted with stirring at a temperature of 100 to 120°C for about 10 hours.
次いで、反応生成物を分離することなしに、反応混合物
をそのまま、１９５℃まで昇温しながら、ｎ−７ミルア
ルコールを留去して回収し、１９５〜２００℃の温度で
攪拌しつつ、脱炭酸させた。Next, without separating the reaction product, the reaction mixture was heated as it was to 195°C, and the n-7 methyl alcohol was distilled off and recovered. Carbonated.
反応終了後、反応生成物を冷却し、温水を加えて洗浄、
分液を繰り返して脱塩した。この後、減圧蒸留して、２
−メチル−４−メトキシジフェニルアミン２２．７ｇ（
２−メチル−４−メトキシアニリンに対する収率７６％
）を得た。After the reaction is completed, the reaction product is cooled and washed with hot water.
Desalting was performed by repeating liquid separation. After this, distillation under reduced pressure is carried out to obtain 2
-Methyl-4-methoxydiphenylamine 22.7g (
Yield 76% based on 2-methyl-4-methoxyaniline
) was obtained.
実施例２
０−クロロ安息香酸２２．６ ｇとエチルグリコールと
の混合物に銅粉０．２３ ｇを投入し、８０〜８５℃の
温度に昇温し、この温度で約１時間攪拌した後、炭酸カ
リウム１０．４ ｇを加え、更に、４−メトキシアニリ
ン１７．２ ｇを加えて、１００〜１０５°Ｃの温度に
昇温し、約１０時間攪拌下に反応させた。Example 2 0.23 g of copper powder was added to a mixture of 22.6 g of 0-chlorobenzoic acid and ethyl glycol, and the temperature was raised to 80 to 85°C. After stirring at this temperature for about 1 hour, 10.4 g of potassium carbonate was added, and further 17.2 g of 4-methoxyaniline was added, the temperature was raised to 100-105°C, and the mixture was reacted with stirring for about 10 hours.
この後、反応生成物を分離することなしに、１９５℃ま
で昇温し、１９５〜２００°Ｃの温度でエチルグリコー
ルを回収しつつ、６時間攪拌して、脱炭酸させた。Thereafter, the temperature was raised to 195° C. without separating the reaction product, and while ethyl glycol was recovered at a temperature of 195 to 200° C., it was stirred for 6 hours to perform decarboxylation.
反応終了後、反応生成物を冷却し、温水を加えて洗浄、
分液を繰り返して脱塩した。この後、減圧蒸留して、４
−メトキシジフェニルアミン２０゜６ｇ （４−メトキ
シアニリンに対する収率７４％）を得た。After the reaction is completed, the reaction product is cooled and washed with hot water.
Desalting was performed by repeating liquid separation. After this, distillation under reduced pressure is carried out to obtain 4
20.6 g of -methoxydiphenylamine (yield 74% based on 4-methoxyaniline) was obtained.
実施例３
実施例２において、４−メトキシアニリンに代えて、２
，３−ジメチル−４−メトキシアニリン２１．１ｇを用
いた以外は、実施例２と同様にして、２．３−ジメチル
−４−メトキシジフェニルアミン２３．８ｇ（２，３−
ジメチル−４−メトキシアニリンに対する収率７５％）
を得た。Example 3 In Example 2, instead of 4-methoxyaniline, 2
, 23.8 g of 2,3-dimethyl-4-methoxydiphenylamine (2,3-
75% yield based on dimethyl-4-methoxyaniline)
I got it.
実施例４
実施例１において、０−クロル安息香酸に代えて、２．
４−ジクロル安息香酸２７．５ ｇを用いた以外は、実
施例１と同様にして、２−メチル−４−メトキシ−３′
−クロルジフェニルアミン２３．０ ｇ（２−メチル−
４−メトキシアニリンに対する収率７０％）を得た。Example 4 In Example 1, 2.
2-Methyl-4-methoxy-3' was prepared in the same manner as in Example 1 except that 27.5 g of 4-dichlorobenzoic acid was used.
-23.0 g of chlordiphenylamine (2-methyl-
A yield of 70% based on 4-methoxyaniline was obtained.
実施例５
実施例１において、溶剤としてエチルグリコールを用い
、反応種として４−エトキシ−２−メチルアニリンと０
−ブロム安息香酸を用いた以外は、実施例１と同じ条件
にて反応を行なって、２−メチル−４−エトキシジフェ
ニルアミンを収率８２％（４−エトキシ−２−メチルア
ニリンに対して）を得た。純度は９８．５％であった。Example 5 In Example 1, ethyl glycol was used as the solvent, and 4-ethoxy-2-methylaniline and 0
-The reaction was carried out under the same conditions as in Example 1 except that bromobenzoic acid was used, and 2-methyl-4-ethoxydiphenylamine was obtained in a yield of 82% (based on 4-ethoxy-2-methylaniline). Obtained. Purity was 98.5%.
実施例６
実施例１において、反応種として４−メトキシ−２−エ
チルアニリンと０−ヨウ化安息香酸を用いた以外は、実
施例１と同じ条件にて反応を行なって、２−エチル−４
−メトキシジフェニルアミンを収率８３％（４−メトキ
シ−２−エチルアニリンに対して）を得た。純度は９８
．６％であった。Example 6 In Example 1, the reaction was carried out under the same conditions as in Example 1, except that 4-methoxy-2-ethylaniline and 0-iodobenzoic acid were used as the reactants, and 2-ethyl-4
-Methoxydiphenylamine was obtained in a yield of 83% (based on 4-methoxy-2-ethylaniline). Purity is 98
．． It was 6%.
実施例７
実施例１において、反応種として４−メトキシ−２−ク
ロルアニリンと０−クロル安息香酸を用いた以外は、実
施例１と同じ条件にて反応を行なって、２−クロル−４
−メトキシジフェニルアミンを収率７５％（４−メトキ
シ−２−クロルアニリンに対して）を得た。純度は９８
．２％であった。Example 7 In Example 1, the reaction was carried out under the same conditions as in Example 1, except that 4-methoxy-2-chloroaniline and 0-chlorobenzoic acid were used as the reactive species, and 2-chloro-4
-Methoxydiphenylamine was obtained in a yield of 75% (based on 4-methoxy-2-chloroaniline). Purity is 98
．． It was 2%.
実施例８
実施例１において、反応種として４−メトキシアニリン
と２，６−ジクロル安息香酸を用いた以外は、実施例１
と同じ条件にて反応を行なって、３−クロル−４゛−メ
トキシジフェニルアミンを収率７４％（４−メトキシア
ニリンに対して）を得た。Example 8 Example 1 except that 4-methoxyaniline and 2,6-dichlorobenzoic acid were used as the reactive species in Example 1.
The reaction was carried out under the same conditions as above to obtain 3-chloro-4'-methoxydiphenylamine in a yield of 74% (based on 4-methoxyaniline).
純度は９７．８％であった。Purity was 97.8%.
Claims (3)
を示し、Ｘ＾１は塩素、臭素及びフッ素より選ばれるハ
ロゲンを示し、ｍ及びｎはそれぞれ０〜４の数を示す。 但し、ｍ＋ｎは４以下である。） で表わされる化合物と、一般式（II） ▲数式、化学式、表等があります▼ （式中、Ｒ＾２及びＸ＾１は前記と同じであり、Ｘ＾２
は塩素、臭素及びヨウ素より選ばれるハロゲンを示し、
ｐ及びｑはそれぞれ０〜４の数を示す。 但し、ｐ＋ｑは４以下である。） で表わされる化合物とを、銅又は銅化合物と、酸捕捉剤
との存在下に溶剤中にて縮合させ、次いで、生成した縮
合生成物を加熱して、脱炭酸させることを特徴とするｐ
−アルコキシジフェニルアミン類の製造方法。(1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 and R^2 each independently represent an alkyl group, and X^1 is selected from chlorine, bromine, and fluorine. Indicates a halogen, and m and n each represent a number from 0 to 4. However, m+n is 4 or less. In, R^2 and X^1 are the same as above, and X^2
represents a halogen selected from chlorine, bromine and iodine,
p and q each represent a number from 0 to 4. However, p+q is 4 or less. ) is condensed with copper or a copper compound in a solvent in the presence of an acid scavenger, and then the resulting condensation product is heated to decarboxylate it.
- A method for producing alkoxydiphenylamines.
を特徴とする特許請求の範囲第１項記載のｐ−アルコキ
シジフェニルアミン類の製造方法。(2) The method for producing p-alkoxydiphenylamines according to claim 1, characterized in that during decarboxylation, the solvent is distilled off and recovered.
して、脱炭酸させることを特徴とする特許請求の範囲第
１項又は第２項記載のｐ−アルコキシジフェニルアミン
類の製造方法。(3) A method for producing p-alkoxydiphenylamines according to claim 1 or 2, characterized in that the condensation product is decarboxylated by heating without separating it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61071630A JPS62226950A (en) | 1986-03-28 | 1986-03-28 | Production of p-alkoxydiphenylamine compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61071630A JPS62226950A (en) | 1986-03-28 | 1986-03-28 | Production of p-alkoxydiphenylamine compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62226950A true JPS62226950A (en) | 1987-10-05 |
Family
ID=13466166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61071630A Pending JPS62226950A (en) | 1986-03-28 | 1986-03-28 | Production of p-alkoxydiphenylamine compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62226950A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106946720A (en) * | 2017-03-23 | 2017-07-14 | 康爱特维迅（蓬莱）化学有限公司 | A kind of preparation method of diphenylamines |
| CN110467538A (en) * | 2019-09-20 | 2019-11-19 | 山东道可化学有限公司 | A kind of synthetic method of 2- methyl -4- methoxy diphenylamine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54163541A (en) * | 1978-06-15 | 1979-12-26 | Hitachi Chemical Co Ltd | Production of mephenamic acid |
-
1986
- 1986-03-28 JP JP61071630A patent/JPS62226950A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54163541A (en) * | 1978-06-15 | 1979-12-26 | Hitachi Chemical Co Ltd | Production of mephenamic acid |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106946720A (en) * | 2017-03-23 | 2017-07-14 | 康爱特维迅（蓬莱）化学有限公司 | A kind of preparation method of diphenylamines |
| CN110467538A (en) * | 2019-09-20 | 2019-11-19 | 山东道可化学有限公司 | A kind of synthetic method of 2- methyl -4- methoxy diphenylamine |
| CN110467538B (en) * | 2019-09-20 | 2022-08-26 | 山东道可化学有限公司 | Synthesis method of 2-methyl-4-methoxydiphenylamine |
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