JPH0456022B2 - - Google Patents
Info
- Publication number
- JPH0456022B2 JPH0456022B2 JP58129895A JP12989583A JPH0456022B2 JP H0456022 B2 JPH0456022 B2 JP H0456022B2 JP 58129895 A JP58129895 A JP 58129895A JP 12989583 A JP12989583 A JP 12989583A JP H0456022 B2 JPH0456022 B2 JP H0456022B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- water
- compound
- aminodiphenylamine
- layer
- 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 - Lifetime
Links
- 239000002253 acid Substances 0.000 claims description 12
- -1 aminodiphenylamine compound Chemical class 0.000 claims description 10
- 239000012442 inert solvent Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000005749 Copper compound Substances 0.000 claims description 5
- 150000001880 copper compounds Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229940100198 alkylating agent Drugs 0.000 claims description 4
- 239000002168 alkylating agent Substances 0.000 claims description 4
- 238000005804 alkylation reaction Methods 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000029936 alkylation Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000002152 alkylating effect Effects 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- 238000006243 chemical reaction Methods 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000008096 xylene Substances 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical group [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 239000012954 diazonium Substances 0.000 description 4
- 150000001989 diazonium salts Chemical class 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- FMMQDMHSGNXJSQ-UHFFFAOYSA-N n,n-diphenylhydroxylamine Chemical compound C=1C=CC=CC=1N(O)C1=CC=CC=C1 FMMQDMHSGNXJSQ-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- 150000003613 toluenes Chemical class 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical class NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 2
- 229940008406 diethyl sulfate Drugs 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YHYKLKNNBYLTQY-UHFFFAOYSA-N 1,1-diphenylhydrazine Chemical class C=1C=CC=CC=1N(N)C1=CC=CC=C1 YHYKLKNNBYLTQY-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- NFCPRRWCTNLGSN-UHFFFAOYSA-N 2-n-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC=C1NC1=CC=CC=C1 NFCPRRWCTNLGSN-UHFFFAOYSA-N 0.000 description 1
- JTTMYKSFKOOQLP-UHFFFAOYSA-N 4-hydroxydiphenylamine Chemical class C1=CC(O)=CC=C1NC1=CC=CC=C1 JTTMYKSFKOOQLP-UHFFFAOYSA-N 0.000 description 1
- OBHGSIGHEBGGFS-UHFFFAOYSA-N 4-methoxy-n-phenylaniline Chemical compound C1=CC(OC)=CC=C1NC1=CC=CC=C1 OBHGSIGHEBGGFS-UHFFFAOYSA-N 0.000 description 1
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 1
- 150000008061 acetanilides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 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
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- VRZVPALEJCLXPR-UHFFFAOYSA-N ethyl 4-methylbenzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=C(C)C=C1 VRZVPALEJCLXPR-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical class C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- OQNVOZIVWQHKGC-UHFFFAOYSA-N n-ethoxy-n-phenylaniline Chemical compound C=1C=CC=CC=1N(OCC)C1=CC=CC=C1 OQNVOZIVWQHKGC-UHFFFAOYSA-N 0.000 description 1
- ZJHJWUVWYXNFLY-UHFFFAOYSA-N n-methoxy-n-phenylaniline Chemical compound C=1C=CC=CC=1N(OC)C1=CC=CC=C1 ZJHJWUVWYXNFLY-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- JTTWNTXHFYNETH-UHFFFAOYSA-N propyl 4-methylbenzenesulfonate Chemical compound CCCOS(=O)(=O)C1=CC=C(C)C=C1 JTTWNTXHFYNETH-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 150000003738 xylenes Chemical class 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)
Description
【発明の詳細な説明】
本発明は、アルコキシジフエニルアミン類の新
規な製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing alkoxydiphenylamines.
アルコキシジフエニルアミン類、特に４−アル
コキシジフエニルアミン誘導体は、記録材料の色
素原体として用いられるフルオラン化合物の中間
体として有用な化合物である。これらの化合物の
合成に関しては、古くから研究が行なわれ、種々
の方法が知られている。 Alkoxydiphenylamines, particularly 4-alkoxydiphenylamine derivatives, are compounds useful as intermediates for fluoran compounds used as chromogens in recording materials. Research has been conducted for a long time regarding the synthesis of these compounds, and various methods are known.
例えば、
(1) Ｎ−アシル−４−アルコキシフエニルアミン
誘導体をブロモベンゼンまたはその誘導体とを
還流下40〜48時間反応させて得られるＮ−アシ
ル−４−アルコキシジフエニルアミン誘導体を
加水分解する方法（特公昭52−5489号公報）、
(2) ４−アルコキシブロモベンゼンとアセトアニ
リド誘導体とを190〜200℃で48時間反応させて
得られるＮ−アシル−４−アルコキシジフエニ
ルアミン誘導体を加水分解する方法（特開昭52
−82243号公報）、
(3) ４−アミノフエノール誘導体とアニリン誘導
体の塩酸塩、あるいは、４−アミノフエノール
誘導体の塩酸塩とアニリン誘導体とを190〜200
℃で反応して、４−ヒドロキシジフエニルアミ
ン誘導体を合成し、それをアルキル化する方法
（特開昭55−136252号公報）等が知られている。 For example, (1) Hydrolyzing the N-acyl-4-alkoxydiphenylamine derivative obtained by reacting the N-acyl-4-alkoxyphenylamine derivative with bromobenzene or its derivative under reflux for 40 to 48 hours. Method (Japanese Patent Publication No. 52-5489), (2) Hydrolyzing an N-acyl-4-alkoxydiphenylamine derivative obtained by reacting 4-alkoxybromobenzene and an acetanilide derivative at 190 to 200°C for 48 hours. How to
-82243 Publication), (3) The hydrochloride of a 4-aminophenol derivative and an aniline derivative, or the hydrochloride of a 4-aminophenol derivative and an aniline derivative at 190 to 200
A method is known in which a 4-hydroxydiphenylamine derivative is synthesized by reacting at .degree. C. and then alkylated (Japanese Patent Application Laid-open No. 136252/1983).
しかしながら、これらの方法は、かなりの高温
で縮合反応を行なうため、副反応が多く、タール
状物質が生成したり、収率が低い等、種々の問題
を有しており、工業的に有利な方法とはいえなか
つた。特にハロゲン基を有するアルコキシジフエ
ニルアミン類を得ようとする場合には、従来の方
法では、脱ハロゲン化などの副反応が著しく、収
率、純度共に極端に低いという問題があつた。 However, these methods involve various problems such as the condensation reaction being carried out at a considerably high temperature, resulting in many side reactions, generation of tar-like substances, and low yields, making them difficult to use industrially. It could not be called a method. In particular, when attempting to obtain alkoxydiphenylamines having a halogen group, conventional methods have had the problem of significant side reactions such as dehalogenation, resulting in extremely low yields and purity.
本発明者等は、このアルコキシジフエニルアミ
ン類の有利な製造法について鋭意検討した結果、
従来とは全く異なつた画期的な製造法を見出し、
本発明を完成するに至つた。 As a result of intensive study on an advantageous method for producing these alkoxydiphenylamines, the present inventors found that
Discovering a revolutionary manufacturing method that is completely different from conventional methods,
The present invention has now been completed.
すなわち、本発明は、アミノジフエニルアミン
化合物をジアゾ化し、次いで希酸中で加熱処理を
行なつてヒドロキシジフエニルアミン化合物と
し、次いで、アルキル化剤でアルキル化すること
を特徴とするアルコキシフエニルアミン類の製造
法である。 That is, the present invention provides an alkoxyphenyl amine compound characterized in that an aminodiphenylamine compound is diazotized, then heated in a dilute acid to form a hydroxydiphenylamine compound, and then alkylated with an alkylating agent. This is a method for producing amines.
本発明において特徴とするところは、アミノジ
フエニルアミン化合物をジアゾ化し、次いでヒド
ロキシ基に置換し、次いで連続的にアルキル化し
てアルコキシ基に変換することにある。 The present invention is characterized in that the aminodiphenylamine compound is diazotized, then substituted with a hydroxy group, and then continuously alkylated to convert it into an alkoxy group.
本発明において出発原料となるアミノジフエニ
ルアミン類としては、例えば、次のものが挙げら
れる。 Examples of aminodiphenylamines used as starting materials in the present invention include the following.
２−クロロ−４−アミノジフエニルアミン、２
−ブロモ−４−アミノジフエニルアミン、２−メ
チル−４−アミノジフエニルアミン、４−アミノ
ジフエニルアミン、２−メトキシ−４−アミノジ
フエニルアミン、３−メチル−４−アミノジフエ
ニルアミン、３−アミノジフエニルアミン、２−
アミノジフエニルアミン、４−アミノ−4′−メチ
ルジフエニルアミン、４−アミノ−3′−メチルジ
フエニルアミン、４−アミノ−2′−クロロジフエ
ニルアミン、４−アミノ−3′−ブロモジフエニル
アミン。 2-chloro-4-aminodiphenylamine, 2
-bromo-4-aminodiphenylamine, 2-methyl-4-aminodiphenylamine, 4-aminodiphenylamine, 2-methoxy-4-aminodiphenylamine, 3-methyl-4-aminodiphenylamine, 3-aminodiphenylamine, 2-
Aminodiphenylamine, 4-amino-4'-methyldiphenylamine, 4-amino-3'-methyldiphenylamine, 4-amino-2'-chlorodiphenylamine, 4-amino-3'-bromodiphenylamine Enilamine.
本発明において、アミノジフエニルアミン化合
物のジアゾ化は、冷時、好ましくは、15℃以下
で、希酸中、好ましくは、１〜40％希酸中で、ニ
トロシル硫酸、または亜硝酸ソーダを用いて実施
することができる。 In the present invention, the diazotization of the aminodiphenylamine compound is carried out using nitrosyl sulfuric acid or sodium nitrite in a dilute acid, preferably 1 to 40% dilute acid, at a temperature of 15° C. or below. It can be implemented by
希酸の酸としては、ハロゲン化水素を除く無機
酸、例えば硫酸、リン酸等が使用できる。 As the dilute acid, inorganic acids other than hydrogen halides, such as sulfuric acid and phosphoric acid, can be used.
ジアゾニウム基をヒドロキシ基に置換するに
は、ジアゾニウム化合物を、希酸中、好ましく
は、１〜30％の希酸中で、高温、好ましくは70〜
110℃で加熱処理することによつて達成できる。
この際、硫酸銅、酢酸銅、硝酸銅などの銅化合
物、リン酸ソーダ等の塩類、トルエン、キシレ
ン、モノクロルベンゼン、ベンゼン、ニトロベン
ゼン、ジクロルベンゼン、デカリン、エチルベン
ゼン、パークレン、トリクレン等の非水溶性不活
性溶媒を添加しておくと、選択性、反応率、収率
向上の面で効果的である。特に銅化合物と非水溶
性不活性溶媒を同時に併用したときその効果が著
しい。このとき使用する銅化合物、塩類は、反応
溶媒の１〜50重量％、非水溶性不活性溶媒は、３
〜40重量％であるのが好ましい。 To replace a diazonium group with a hydroxy group, the diazonium compound is heated in a dilute acid, preferably 1 to 30% dilute acid, at high temperature, preferably 70 to 70%.
This can be achieved by heat treatment at 110°C.
At this time, copper compounds such as copper sulfate, copper acetate, copper nitrate, salts such as sodium phosphate, water-insoluble substances such as toluene, xylene, monochlorobenzene, benzene, nitrobenzene, dichlorobenzene, decalin, ethylbenzene, perchlorobenzene, trichlorobenzene, etc. Adding an inert solvent is effective in improving selectivity, reaction rate, and yield. In particular, the effect is remarkable when a copper compound and a water-insoluble inert solvent are used together. The copper compounds and salts used at this time are 1 to 50% by weight of the reaction solvent, and the water-insoluble inert solvent is 3% by weight.
~40% by weight is preferred.
ジアゾニウム化合物を加熱処理する方法として
は、ジアゾニウム化合物の希酸溶液あるいはスラ
リーを、そのまま加熱してもよいし、あるいは、
場合によつては銅化合物、塩類、非水溶性不活性
溶媒を添加し、高温に加熱した水の中に、ジアゾ
ニウム化合物の希酸溶液あるいはスラリーを滴下
してもよい。 As a method for heat treating the diazonium compound, a dilute acid solution or slurry of the diazonium compound may be heated as it is, or
A dilute acid solution or slurry of a diazonium compound may be added dropwise to water heated to a high temperature, with the addition of a copper compound, salts, or a water-insoluble inert solvent as the case may be.
こうして生成したヒドロキジフエニルアミン類
は、オイル状で分離しているので、好ましくは非
水溶性溶媒で抽出する等の方法によつて希酸水と
分離する。ヒドロキシ置換の際、非水溶性不活性
溶媒を添加した場合はヒドロキシジフエニルアミ
ン類は溶媒層に溶解しているのでそのまま分液す
ることにより希酸と分離できる。 Since the hydroxydiphenylamine thus produced is separated in the form of an oil, it is preferably separated from the dilute acid water by a method such as extraction with a non-aqueous solvent. When a water-insoluble inert solvent is added during hydroxy substitution, the hydroxydiphenylamines are dissolved in the solvent layer and can be separated from the dilute acid by liquid separation.
次いで、アルキル化するのには、アルキル化剤
を適当な脱酸剤と共に使用して反応を行なう。 The alkylation is then carried out using an alkylating agent together with a suitable deoxidizing agent.
ジアゾニウム基をヒドロキシ基に置換する際、
非水溶性不活性溶媒を添加しておくと、生成した
ヒドロキシジフエニルアミン類は溶媒層に存在す
るので、そのまま分液して、引き続き、アルキル
化反応が行なえるので有利である。 When replacing a diazonium group with a hydroxy group,
Addition of a water-insoluble inert solvent is advantageous because the produced hydroxydiphenylamines are present in the solvent layer, so that they can be separated as they are and then the alkylation reaction can be carried out.
アルキル化剤としては、ジメチル硫酸、ジエチ
ル硫酸等のアルキル硫酸類、ｐ−トルエンスルホ
ン酸メチルエステル、ｐ−トルエンスルホン酸エ
チルエステル、ｐ−トルエンスルホン酸プロピル
エステル等のトルエンスルホン酸のアルキルエス
テル類、ヨウ化メチル、ヨウ化エチル、臭化プロ
ピル、臭化ブチル、塩化ブチル、塩化ペンチル等
のハロゲン化アルキル類があげられる。 Examples of the alkylating agent include alkyl sulfates such as dimethyl sulfate and diethyl sulfate, alkyl esters of toluenesulfonic acid such as p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid ethyl ester, and p-toluenesulfonic acid propyl ester; Examples include alkyl halides such as methyl iodide, ethyl iodide, propyl bromide, butyl bromide, butyl chloride, and pentyl chloride.
脱酸剤としては、炭酸ナトリウム、炭酸カルシ
ウム、炭酸カリウム、水酸化ナトリウム、水酸化
カリウム、有機アミン類等があげられる。 Examples of the deoxidizer include sodium carbonate, calcium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, organic amines, and the like.
本発明によれば、非常に選択性よく高純度のア
ルコキシジフエニルアミン類を高収率で得ること
ができる。特にハロゲン原子を有するアルコキシ
ジフエニルアミン類の製造には有用である。 According to the present invention, highly selective and highly pure alkoxydiphenylamines can be obtained in high yield. It is particularly useful for producing alkoxydiphenylamines containing halogen atoms.
以下実施例により本発明を更に詳しく説明す
る。実施例中、部、％はそれぞれ重量部、重量％
を表わす。 The present invention will be explained in more detail with reference to Examples below. In the examples, parts and % are parts by weight and % by weight, respectively.
represents.
実施例 １
20％硫酸200部に４−アミノ−２−クロロジフ
エニルアミン21.9部を分散し、15℃以下で亜硝酸
ナトリウム6.9部を加えてジアゾ化する。Example 1 21.9 parts of 4-amino-2-chlorodiphenylamine is dispersed in 200 parts of 20% sulfuric acid and diazotized by adding 6.9 parts of sodium nitrite at 15°C or below.
一方、水800部に硫酸銅80部を溶解し、トルエ
ン120部を加え、これを90℃に加熱する。同温度
に保温しながら、これに前記ジアゾニウム溶液を
滴下する。滴下終了後、同温度で30分間保温し、
その後室温まで冷却する。反応液を静置分液し
て、トルエン層と水層に分ける。このトルエン層
にジメチル硫酸12.6部を加えた後、10〜20℃で20
％水酸化ナトリウム溶液24部を滴下する。 Meanwhile, 80 parts of copper sulfate is dissolved in 800 parts of water, 120 parts of toluene is added, and this is heated to 90°C. The diazonium solution was added dropwise to the solution while keeping it at the same temperature. After dropping, keep at the same temperature for 30 minutes,
Then cool to room temperature. Separate the reaction solution by standing to separate it into a toluene layer and an aqueous layer. After adding 12.6 parts of dimethyl sulfate to this toluene layer,
% sodium hydroxide solution are added dropwise.
滴下終了後、同温度で３時間保温して反応を終
了させる。反応液を静置分液して、トルエン層と
水層に分ける。トルエン層のトルエンを留去した
後、残つた反応生成物を減圧蒸留して、２−クロ
ロ−４−メトキシジフエニルアミン14.0部が得ら
れた。 After the dropwise addition is completed, the reaction is completed by keeping the mixture at the same temperature for 3 hours. Separate the reaction solution by standing to separate it into a toluene layer and an aqueous layer. After distilling off the toluene in the toluene layer, the remaining reaction product was distilled under reduced pressure to obtain 14.0 parts of 2-chloro-4-methoxydiphenylamine.
留出温度；135−140℃／３mmＨｇ
元素分析値 Ｃ Ｈ Ｎ
Cl
実測値（％） 66.92 5.20 5.98 15.16
理論値（％） 66.81 5.14 6.00 15.20
実施例 ２
10％硫酸300部に４−アミノ−２−クロロジフ
エニルアミン21.9部を分散し、15℃以下で亜硝酸
ナトリウム6.9部を加えてジアゾ化する。 Distillation temperature: 135-140℃/3mmHg Elemental analysis value C H N
Cl Actual value (%) 66.92 5.20 5.98 15.16 Theoretical value (%) 66.81 5.14 6.00 15.20 Example 2 21.9 parts of 4-amino-2-chlorodiphenylamine was dispersed in 300 parts of 10% sulfuric acid, and nitrous acid was dissolved at 15°C or below. Add 6.9 parts of sodium to diazotize.
一方、水1000部に硫酸銅150部を溶解し、キシ
レン150部を加え、これを90℃に加熱する。同温
度に保温しながら、これに前記ジアゾニウム溶液
を滴下する。滴下終了後、同温度で30分間保温
し、その後室温まで冷却する。反応液を静置分液
してキシレン層と水層に分ける。このキシレン層
にジエチル硫酸15.4部を加えた後、10〜20℃で20
％水酸化カリウム溶液33.6部を滴下する。滴下終
了後、同温度で３時間保温して反応を終了させ
る。反応液を静置分液して、キシレン層と水層に
分ける。キシレン層のキシレンを留去した後、残
つた反応生成物を減圧蒸留して、２−クロロ−４
−エトキシジフエニルアミン16.6部が得られた。 On the other hand, dissolve 150 parts of copper sulfate in 1000 parts of water, add 150 parts of xylene, and heat this to 90°C. The diazonium solution was added dropwise to the solution while keeping it at the same temperature. After dropping, keep at the same temperature for 30 minutes, then cool to room temperature. The reaction solution is separated into a xylene layer and an aqueous layer by standing. After adding 15.4 parts of diethyl sulfate to this xylene layer,
% potassium hydroxide solution is added dropwise. After the dropwise addition is completed, the reaction is completed by keeping the mixture at the same temperature for 3 hours. Separate the reaction solution by standing to separate it into a xylene layer and an aqueous layer. After distilling off the xylene in the xylene layer, the remaining reaction product was distilled under reduced pressure to obtain 2-chloro-4
-16.6 parts of ethoxydiphenylamine were obtained.
留出温度：143−150℃／３mmＨｇ
元素分析値 Ｃ Ｈ Ｎ
Cl
実測値（％） 67.75 5.59 5.71 14.6
理論値（％） 67.88 5.66 5.68 14.3
実施例 ３
20％硫酸100部に４−アミノ−２−クロロジフ
エニルアミン21.9部を分散し、15℃以下で亜硝酸
ナトリウム6.9部を加えてジアゾ化する。 Distillation temperature: 143-150℃/3mmHg Elemental analysis value C H N
Cl Actual value (%) 67.75 5.59 5.71 14.6 Theoretical value (%) 67.88 5.66 5.68 14.3 Example 3 21.9 parts of 4-amino-2-chlorodiphenylamine was dispersed in 100 parts of 20% sulfuric acid, and nitrous acid was dissolved at 15°C or below. Add 6.9 parts of sodium to diazotize.
一方、水1000部に硝酸銅100部を溶解し、トル
エン100部を加え、これを90℃に加熱する。同温
度に保温しながら、これに前記ジアゾニウム溶液
を滴下する。滴下終了後、同温度で30分保温し、
その後室温まで冷却する。反応液を静置分液し
て、トルエン層と水層に分ける。このトルエン層
にヨウ化メチル14.2部を加え、還流下で20％水酸
化ナトリウム溶液24部を滴下する。滴下終了後、
還流下で５時間反応して反応を終了させる。室温
まで冷却後、静置分液して、トルエン層と水層に
分ける。トルエン層のトルエンを留去した後、残
つた反応生成物を減圧蒸留して、２−クロロ−４
−メトキシジフエニルアミン15.2部が得られた。 On the other hand, dissolve 100 parts of copper nitrate in 1000 parts of water, add 100 parts of toluene, and heat this to 90°C. The diazonium solution was added dropwise to the solution while keeping it at the same temperature. After dropping, keep at the same temperature for 30 minutes,
Then cool to room temperature. Separate the reaction solution by standing to separate it into a toluene layer and an aqueous layer. Add 14.2 parts of methyl iodide to this toluene layer, and dropwise add 24 parts of 20% sodium hydroxide solution under reflux. After finishing dropping,
The reaction was completed under reflux for 5 hours. After cooling to room temperature, the mixture is allowed to stand still and separated into a toluene layer and an aqueous layer. After distilling off the toluene in the toluene layer, the remaining reaction product was distilled under reduced pressure to obtain 2-chloro-4
-15.2 parts of methoxydiphenylamine were obtained.
留出温度：145−150℃／３mmＨｇ
元素分析値 Ｃ Ｈ Ｎ
Cl
実測値（％） 66.76 5.20 5.96 15.31
理論値（％） 66.81 5.14 6.00 15.20
実施例 ４
10％硫酸200部に４−アミノジフエニルアミン
18.4部を分散し、15℃以下で亜硝酸ナトリウム
6.9部を加えてジアゾ化する。 Distillation temperature: 145-150℃/3mmHg Elemental analysis value C H N
Cl Actual value (%) 66.76 5.20 5.96 15.31 Theoretical value (%) 66.81 5.14 6.00 15.20 Example 4 4-aminodiphenylamine in 200 parts of 10% sulfuric acid
Disperse 18.4 parts of sodium nitrite at below 15℃
Add 6.9 parts to diazotize.
一方、水1000部に硫酸銅100部を溶解し、トル
エン100部を加え、これを90℃に加熱する。同温
度に保温しながら、これに前記ジアゾニウム溶液
を滴下する。滴下終了後、同温度で30分間保温
し、その後室温まで冷却する。反応液を静置分液
して、トルエン層と水層に分ける。このトルエン
層にｐ−トルエンスルホン酸メチルエステル18.6
部、ソーダ灰6.4部を加え、100〜110℃で７時間
保温して、反応を終了させる。反応終了後、トル
エンを留去し、残つた反応生成物を減圧蒸留し
て、４−メトキシジフエニルアミン13.8部が得ら
れた。 On the other hand, dissolve 100 parts of copper sulfate in 1000 parts of water, add 100 parts of toluene, and heat this to 90°C. The diazonium solution was added dropwise to the solution while keeping it at the same temperature. After dropping, keep at the same temperature for 30 minutes, then cool to room temperature. Separate the reaction solution by standing to separate it into a toluene layer and an aqueous layer. In this toluene layer, p-toluenesulfonic acid methyl ester 18.6
1 part and 6.4 parts of soda ash were added and kept at 100-110°C for 7 hours to complete the reaction. After the reaction was completed, toluene was distilled off and the remaining reaction product was distilled under reduced pressure to obtain 13.8 parts of 4-methoxydiphenylamine.
留出温度：123−128℃／３mmＨｇ 元素分析値 Ｃ Ｈ Ｎ 実測値（％） 78.44 6.60 7.12 理論値（％） 78.39 6.53 7.04 Distillation temperature: 123-128℃/3mmHg Elemental analysis value C H N Actual value (%) 78.44 6.60 7.12 Theoretical value (%) 78.39 6.53 7.04
Claims (1)
し、次いで希酸中で加熱処理を行なつてヒドロキ
シジフエニルアミン化合物とし、次いでアルキル
化剤でアルキル化することを特徴とするアルコキ
シジフエニルアミン類の製造法。 ２ 希酸中で加熱処理を行なう際、銅化合物およ
び非水溶性不活性溶媒を添加し、生成するヒドロ
キシジフエニルアミン化合物を非水溶性不活性溶
媒層に抽出し、次いで、その非水溶性不活性溶媒
中でアルキル化する特許請求の範囲第１項記載の
方法。[Scope of Claims] 1. An alkoxydiphenyl characterized by diazotizing an aminodiphenylamine compound, then heat-treating it in a dilute acid to obtain a hydroxydiphenylamine compound, and then alkylating it with an alkylating agent. Method for producing amines. 2. When performing heat treatment in a dilute acid, a copper compound and a water-insoluble inert solvent are added, the hydroxydiphenylamine compound produced is extracted into the water-insoluble inert solvent layer, and then the water-insoluble inert solvent is extracted. A method according to claim 1, wherein the alkylation is carried out in an active solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58129895A JPS6023353A (en) | 1983-07-15 | 1983-07-15 | Preparation of alkoxydiphenylamines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58129895A JPS6023353A (en) | 1983-07-15 | 1983-07-15 | Preparation of alkoxydiphenylamines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6023353A JPS6023353A (en) | 1985-02-05 |
| JPH0456022B2 true JPH0456022B2 (en) | 1992-09-07 |
Family
ID=15021015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58129895A Granted JPS6023353A (en) | 1983-07-15 | 1983-07-15 | Preparation of alkoxydiphenylamines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6023353A (en) |
-
1983
- 1983-07-15 JP JP58129895A patent/JPS6023353A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6023353A (en) | 1985-02-05 |
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