CN1989096A - 制备单烷基化二胺类的方法 - Google Patents

制备单烷基化二胺类的方法 Download PDF

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CN1989096A
CN1989096A CNA2005800253447A CN200580025344A CN1989096A CN 1989096 A CN1989096 A CN 1989096A CN A2005800253447 A CNA2005800253447 A CN A2005800253447A CN 200580025344 A CN200580025344 A CN 200580025344A CN 1989096 A CN1989096 A CN 1989096A
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alkyl
compound
formula
nhcor
ocor
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沃纳·赫伯特·鲁斯
麦克尔·哈钦斯
瓦伦·詹姆斯·埃伯纳泽
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Dystar Textilfarben GmbH and Co Deutschland KG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
    • C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/51—Phenylenediamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
    • C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

本发明关于制备式(I)化合物的方法，通过使式(II)化合物在NaY八面沸石型沸石存在下与式(III)化合物反应或与式(IV)化合物反应。其中Ar，X，R，n分别如权利要求1中所定义。

Description

制备单烷基化二胺类的方法
发明领域
本发明涉及制备单-N-烷化的芳族二胺类的方法，其为有用的中间物，例如，用于制备染料。
背景技术
J.Org.Chem.2003，68，7374-7378公开了芳族胺类在NaY八面沸石(faujasite)型沸石存在下用碳酸二甲酯进行甲基化。
现在令人惊奇地发现该方法当用于芳族二胺类时，仅对一个氨基进行选择性单-N-烷化，而第二个氨基保持不变。
发明内容
本发明涉及制备式(I)化合物的方法，
其中
Ar为芳族或杂芳族环系；
X为取代基；
n为0至6；和
R为烷基，羟烷基或苯甲基；
通过使式(II)化合物在NaY八面沸石型沸石存在下
Figure A20058002534400042
其中Ar，X，n分别如上定义，
与式(III)化合物反应
(RO)2CO    (III)
其中R如上定义，
或与式(IV)化合物反应
本发明的优选方法中，
Ar为苯环，稠合苯环，吡啶环或嘧啶环；
X为C1～C4-烷基，-COOR1，-COR1，-OR1，-NHCOR1，-SO2R2，卤素，氰基，硝基，-SO3M，或被OR1、OCOR1或NHCOR1取代的C1～C4-烷基；
其中R1为氢，C1～C4-烷基，或被OR1、OCOR1或NHCOR1取代的C1-C4-烷基；
其中R2为C1～C4-烷基，卤素，或被OH或OCOR1取代的C1～C4-烷基；
其中M为氢或碱金属，例如钠、钾或锂；
n为0，1或2；
R为C1～C4-烷基，或羟基-C1～C4-烷基；
其中-NH2与-NHR可彼此为邻位或间位。
C1～C4-烷基可为直链或支链，例子有甲基，乙基，正丙基，异丙基，正丁基，异丁基，仲丁基或叔丁基。这些定义也适用于羟基-C1～C4-烷基。卤素为例如氟、氯或溴。
本发明的优选方法中，
Ar为苯环；
X为甲基，乙基，甲氧基，乙氧基，-COOH，-COOMe，-COOEt，-NHCOMe，氯，氰基或硝基；
n为0，1或2；和
R为甲基，乙基或羟乙基。
本发明更优选的方法中，式(I)化合物具有式(Ia)
本发明另一更优选的方法中，所用催化剂为NaY八面沸石型的改性沸石，最好是加入锂盐共催化剂来改性，例如，加入碳酸氢锂或碳酸锂。
本发明方法的另一变化中，是在压力下的密闭反应器中进行，使反应温度可高于反应混合物的沸点。反应混合物可置于压力下，例如，至高达约20巴(bar)。
本发明方法的另一变化中，反应混合物的加热(在一些例子中是必须的)在微波炉中进行。
本发明方法的另一变化中，是在惰性气体下进行，例如，氮或氩，以避免反应物或产物发生不希望的反应，例如，氧化反应。
NaY八面沸石型的沸石为公知的，并可由市面上购得。
式(I)化合物为有用的中间物，例如，用于制备染料，例如，反应性染料，如EP 0 256 650 A1和EP 0315 045 A1中所述。
实施方式
实施例1
将1.0g NaY八面沸石型的预干燥沸石与1.0g(9.2mmol)邻苯二胺及30mL(0.31 mol)碳酸二甲酯混合。混合物沸腾回流5小时直到层析检查显示转化完全。将此反应混合物冷却至室温，滤掉催化剂后用甲醇清洗。合并滤液，减压蒸发而浓缩得出0.84g粘稠黄色油状N-甲基-邻苯二胺。
所得化合物的1H NMR与质谱完全符合预期。与对照试样(得自Aldrich)的共同层析也显示一致，且未发现有更高程度烷化的化合物。
实施例2至8
类似上述实施例1，也可将下式(II)化合物转化成对应式(I)的最终产物。下表中DMC指碳酸二甲酯，DEC指碳酸二乙酯，EC指碳酸乙二酯(下述式(IV)化合物)。

Claims (6)

1.一种制备式(I)化合物的方法，
其中
Ar为芳族或杂芳族环系；
X为取代基；
n为0至6；和
R为烷基、羟烷基或苯甲基；
通过使式(II)化合物在NaY八面沸石型沸石存在下
Figure A2005800253440002C2
其中Ar，X，n分别如上定义，
与式(III)化合物反应
(RO)2CO(III)
其中R如上定义，
或与式(IV)化合物反应
2.权利要求1的方法，其中
Ar为苯环，稠合苯环，吡啶环或嘧啶环；
X为C1～C4-烷基，-COOR1，-COR1，-OR1，-NHCOR1，-SO2R2，
卤素，氰基，硝基，-SO3M，或被OR1、OCOR1、或NHCOR1取代的C1～C4-烷基；
其中R1为氢，C1～C4-烷基，或被OR1、OCOR1或NHCOR1取代的C1～C4-烷基；
其中R2为C1～C4-烷基，卤素，或被OH或OCOR1取代的C1～C4-烷基；
其中M为氢或碱金属，如钠、钾或锂；
n为0，1或2；
R为C1～C4-烷基，或羟基-C1～C4-烷基；
其中-NH2与-NHR可彼此为邻位或间位。
3.权利要求1和/或2的方法，其中
Ar为苯环；
X为甲基，乙基，甲氧基，乙氧基，-COOH，-COOMe，-COOEt，-NHCOMe，氯，氰基，或硝基；
n为0，1或2；和
R为甲基，乙基或羟乙基。
4.权利要求1至3中任一项的方法，其中式(I)化合物具有式(Ia)
Figure A2005800253440003C1
5.权利要求1至4中任一项的方法，其中所用催化剂为NaY八面沸石型的改性沸石。
6.权利要求5的方法，其中通过加入锂盐共催化剂进行改性，例如，加入碳酸氢锂或碳酸锂。
CNA2005800253447A 2004-07-29 2005-07-22 制备单烷基化二胺类的方法 Pending CN1989096A (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101260049B (zh) * 2008-04-15 2011-06-08 中国科学院山西煤炭化学研究所 一种非均相合成4，4'-四甲基二氨基二苯甲烷的方法
CN102557964A (zh) * 2010-12-09 2012-07-11 宜昌长江药业有限公司 一种n-甲基邻苯二胺（盐）及其同分异构体的合成方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3737537A1 (de) * 1987-11-05 1989-05-18 Basf Ag Verdoppelte kupfer-formazanreaktivfarbstoffe und ihre verwendung
ITPD20020325A1 (it) * 2002-12-18 2004-06-19 Consorzio Interuniversitario Nazionale La Chimic Sintesi di aniline funzionalizzate mono-n-sostituite.

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101260049B (zh) * 2008-04-15 2011-06-08 中国科学院山西煤炭化学研究所 一种非均相合成4，4'-四甲基二氨基二苯甲烷的方法
CN102557964A (zh) * 2010-12-09 2012-07-11 宜昌长江药业有限公司 一种n-甲基邻苯二胺（盐）及其同分异构体的合成方法

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JP2008508233A (ja) 2008-03-21
US20080125603A1 (en) 2008-05-29
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