N-(o-Tolyl)-2-aminomethyl-pyridin | 7137-98-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-(o-Tolyl)-2-aminomethyl-pyridin
• 英文别名: 2-methyl-N-(1-pyridin-2-ylethyl)aniline
• CAS: 7137-98-6
• 化学式: C₁₄H₁₆N₂
• 分子量: 212.294
• InChiKey: RYJBQIXBHDAACX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  24.9
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-(o-Tolyl)-2-aminomethyl-pyridin 以 水 、 甲苯 为溶剂， 反应 3.0h， 生成
  参考文献：
  名称：

  基于单烷基-N-芳基取代的亚氨基吡啶铁配合物的催化剂制备高度立体有规的 1,3-丁二烯和异戊二烯聚合物：合成和表征

  摘要：

  合成并表征了一些新的单烷基-N-芳基取代的亚氨基吡啶氯化铁络合物，其在亚胺碳和芳环的邻位取代基的性质不同。对于其中之一，获得了单晶，这可以确定其晶体结构，其中铁中心与氯化物和配体的两个氮原子配位。铁周围的配位是扭曲的四面体，FeCl 2很少发现配位模式与二齿氮配体的加合物。所有配合物都与甲基铝氧烷结合使用，用于 1,3-丁二烯和异戊二烯的聚合，提供间同立构 1,2 聚（1,3-丁二烯）和聚（异戊二烯），主要为顺式-1， 4/3,4 交替结构，其中存在三个或五个单元的短顺式-1,4 序列，其长度取决于铁原子上配体的性质。报告了所得聚（异戊二烯）的详细 NMR 表征（1 H-、13 C- 和 2D 实验），并提出了形成新型异戊二烯聚合物的暂定方案。

  DOI：

  10.1021/acs.macromol.1c01291
• 作为产物：
  描述：

  N--2-acetimidoyl-pyridin 在 sodium tetrahydroborate 作用下， 生成 N-(o-Tolyl)-2-aminomethyl-pyridin
  参考文献：
  名称：

  基于单烷基-N-芳基取代的亚氨基吡啶铁配合物的催化剂制备高度立体有规的 1,3-丁二烯和异戊二烯聚合物：合成和表征

  摘要：

  合成并表征了一些新的单烷基-N-芳基取代的亚氨基吡啶氯化铁络合物，其在亚胺碳和芳环的邻位取代基的性质不同。对于其中之一，获得了单晶，这可以确定其晶体结构，其中铁中心与氯化物和配体的两个氮原子配位。铁周围的配位是扭曲的四面体，FeCl 2很少发现配位模式与二齿氮配体的加合物。所有配合物都与甲基铝氧烷结合使用，用于 1,3-丁二烯和异戊二烯的聚合，提供间同立构 1,2 聚（1,3-丁二烯）和聚（异戊二烯），主要为顺式-1， 4/3,4 交替结构，其中存在三个或五个单元的短顺式-1,4 序列，其长度取决于铁原子上配体的性质。报告了所得聚（异戊二烯）的详细 NMR 表征（1 H-、13 C- 和 2D 实验），并提出了形成新型异戊二烯聚合物的暂定方案。

  DOI：

  10.1021/acs.macromol.1c01291

文献信息

• PROCESS FOR PREPARING CONJUGATED DIENE (CO)POLYMERS IN THE PRESENCE OF A CATALYTIC SYSTEM COMPRISING A PYRIDYL IRON (III) COMPLEX
  申请人：Versalis S.p.A.

  公开号：US20190270832A1

  公开（公告）日：2019-09-05

  A process for preparing conjugated diene (co)polymers comprising polymerizing at least one conjugated diene in the presence of a catalytic system comprising: (a) at least one pyridyl iron (III) complex having general formula (I) or (II): wherein: —R 1 , R 2 , R 3 and R 4 , identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; —R 5 represents a hydrogen atom, or is selected from linear or branched, optionally halogenated C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; —X, identical or different, represent a halogen atom such as, for example, chlorine, bromine, iodine; or are selected from linear or branched C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, —OCOR 6 groups or —OR 6 groups wherein R 6 is selected from linear or branched C 1 -C 20 , preferably C 1 -C 15 , alkyl groups. —n is 3; (b) at least one co-catalyst selected from organo-aluminum derivatives, preferably from: (b 1 ) aluminum compounds having general formula (III): Al(R 7 )(R 8 )(R 9 ) (IIl) wherein R 7 represents a hydrogen atom, or is selected from linear or branched C 1 -C 20 alkyl groups, cycloalkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, alkoxy groups; R 8 and R 9 , identical or different, are selected from linear or branched C 1 -C 20 alkyl groups, cycloalkyl groups, aryl groups, alkylaryl groups, arylalkyl groups; (b 2 ) aluminoxanes having general formula (IV): (R 10 ) 2 —Al—O—[-AI(R 11 )—O-] m -AI-(R 12 ) 2 (IV), wherein R 10 , R 11 and R 12 , identical or different, represent a hydrogen atom, or a halogen atom such as chlorine, bromine, iodine, fluorine; or are selected from linear or branched C 1 -C 20 alkyl groups, cycloalkyl groups, aryl groups, said groups being optionally substituted with one or more silicon or germanium atoms; and m is an integer ranging from 0 to 1000; (b 3 ) partially hydrolyzed organo-aluminum derivatives; (b 4 ) haloaluminum alkyls having general formula (V) or (VI): AI(R 13 ) p (X′) 3-p (V) AI 2 (R 13 ) q (X′) 3-q (VI) wherein p is 1 or 2; q is an integer ranging from 1 to 5; R 13 , identical or different, are selected from linear or branched C 1 -C 20 alkyl groups; X′ represents a chlorine or bromine atom, preferably chlorine; provided that said co-catalyst (b) is not selected from organo-boron derivatives.

  一种制备共轭二烯（共）聚合物的方法，包括在催化体系的存在下聚合至少一种共轭二烯，所述催化体系包括：（a）至少一种具有一般式（I）或（II）的吡啶基铁（III）配合物：其中：-R1，R2，R3和R4，相同或不同，表示氢原子；或选自线性或支链的，可选卤代的C1-C20，优选C1-C15，烷基，可选取代的环烷基，可选取代的芳基；-R5表示氢原子，或选自线性或支链的，可选卤代的C1-C20，优选C1-C15，烷基，可选取代的环烷基，可选取代的芳基；-X，相同或不同，表示卤原子，例如氯、溴、碘；或选自线性或支链的C1-C20，优选C1-C15，烷基，-OCOR6基团或-OR6基团，其中R6选自线性或支链的C1-C20，优选C1-C15，烷基。-n为3；（b）至少一种有机铝衍生物的协同催化剂，优选自：（b1）具有一般式（III）的铝化合物：Al（R7）（R8）（R9）（III），其中R7表示氢原子，或选自线性或支链的C1-C20烷基，环烷基，芳基，烷基芳基基，芳基烷基基，烷氧基；R8和R9，相同或不同，选自线性或支链的C1-C20烷基，环烷基，芳基，烷基芳基基，芳基烷基基；（b2）具有一般式（IV）的铝氧烷：（R10）2-Al-O-[-AI（R11）-O-]m-AI-（R12）2（IV），其中R10，R11和R12，相同或不同，表示氢原子，或卤原子，例如氯、溴、碘、氟；或选自线性或支链的C1-C20烷基，环烷基，芳基，所述基团可以选择性地取代一个或多个硅或锗原子；m为0至1000的整数；（b3）部分水解的有机铝衍生物；（b4）具有一般式（V）或（VI）的卤代铝烷：Al（R13）p（X′）3-p（V）或AI2（R13）q（X′）3-q（VI），其中p为1或2；q为1至5的整数；R13，相同或不同，选自线性或支链的C1-C20烷基；X′表示氯或溴原子，优选氯；前提是所述协同催化剂（b）不选自有机硼衍生物。
• Process for preparing conjugated diene (co)polymers in the presence of a catalytic system comprising a pyridyl iron (III) complex
  申请人：Versalis S.p.A.

  公开号：US10793653B2

  公开（公告）日：2020-10-06

  A process for preparing conjugated diene (co)polymers comprising polymerizing at least one conjugated diene in the presence of a catalytic system comprising: (a) at least one pyridyl iron (III) complex having general formula (I) or (II): wherein: —R1, R2, R3 and R4, identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated C1-C20, preferably C1-C15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; —R5 represents a hydrogen atom, or is selected from linear or branched, optionally halogenated C1-C20, preferably C1-C15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; —X, identical or different, represent a halogen atom such as, for example, chlorine, bromine, iodine; or are selected from linear or branched C1-C20, preferably C1-C15, alkyl groups, —OCOR6 groups or —OR6 groups wherein R6 is selected from linear or branched C1-C20, preferably C1-C15, alkyl groups. —n is 3; (b) at least one co-catalyst selected from organo-aluminum derivatives, preferably from: (b1) aluminum compounds having general formula (III): Al(R7)(R8)(R9) (IIl) wherein R7 represents a hydrogen atom, or is selected from linear or branched C1-C20 alkyl groups, cycloalkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, alkoxy groups; R8 and R9, identical or different, are selected from linear or branched C1-C20 alkyl groups, cycloalkyl groups, aryl groups, alkylaryl groups, arylalkyl groups; (b2) aluminoxanes having general formula (IV): (R10)2—Al—O—[-AI(R11)—O-]m-AI-(R12)2 (IV), wherein R10, R11 and R12, identical or different, represent a hydrogen atom, or a halogen atom such as chlorine, bromine, iodine, fluorine; or are selected from linear or branched C1-C20 alkyl groups, cycloalkyl groups, aryl groups, said groups being optionally substituted with one or more silicon or germanium atoms; and m is an integer ranging from 0 to 1000; (b3) partially hydrolyzed organo-aluminum derivatives; (b4) haloaluminum alkyls having general formula (V) or (VI): AI(R13)p(X′)3-p (V) AI2(R13)q(X′)3-q (VI) wherein p is 1 or 2; q is an integer ranging from 1 to 5; R13, identical or different, are selected from linear or branched C1-C20 alkyl groups; X′ represents a chlorine or bromine atom, preferably chlorine; provided that said co-catalyst (b) is not selected from organo-boron derivatives.

  一种制备共轭二烯（共）聚合物的工艺，包括在催化体系存在下聚合至少一种共轭二烯，该催化体系包括： (a) 至少一种具有通式(I)或(II)的吡啶基铁(III)络合物： 其中：-R1、R2、R3 和 R4，相同或不同，代表氢原子；或选自直链或支链、任选卤化的 C1-C20，优选 C1-C15，烷基、任选取代的环烷基、任选取代的芳基；-R5 代表氢原子，或选自直链或支链、任选卤化的 C1-C20，优选 C1-C15，烷基、任选取代的环烷基、任选取代的芳基；-X，相同或不同，代表卤原子，例如氯、溴、碘；或选自直链或支链 C1-C20，优选 C1-C15，烷基、-OCOR6 基团或-OR6 基团，其中 R6 选自直链或支链 C1-C20，优选 C1-C15，烷基。-(b) 至少一种助催化剂，选自有机铝衍生物，最好选自： (b1) 具有通式 (III) 的铝化合物：Al(R7)(R8)(R9) (IIl) 其中 R7 代表氢原子，或选自直链或支链 C1-C20 烷基、环烷基、芳基、烷芳基、芳烷基、烷氧基；R8 和 R9 相同或不同，选自直链或支链 C1-C20 烷基、环烷基、芳基、烷芳基、芳烷基； (b2) 具有通式(IV)的铝氧烷：(R10)2-Al-O-[-AI(R11)-O-]m-AI-(R12)2 (IV)，其中 R10、R11 和 R12 相同或不同，代表氢原子或卤素原子，如氯、溴、碘、氟；(b2) 部分水解的有机铝衍生物； (b3) 部分水解的有机铝衍生物； (b4) 具有通式 (V) 或 (VI) 的卤代烷基铝：AI(R13)p(X′)3-p(V) AI2(R13)q(X′)3-q(VI) 其中p是1或2；q是1至5的整数；R13，相同或不同，选自直链或支链C1-C20烷基；X′代表氯或溴原子，最好是氯；条件是所述助催化剂(b)不选自有机硼衍生物。
• [EN] PROCESS FOR PREPARING CONJUGATED DIENE (CO)POLYMERS IN THE PRESENCE OF A CATALYTIC SYSTEM COMPRISING A PYRIDYL IRON (III) COMPLEX<br/>[FR] PROCÉDÉ DE PRÉPARATION DE (CO) POLYMÈRES DE DIÈNE CONJUGUÉS EN PRÉSENCE D'UN SYSTÈME CATALYTIQUE COMPRENANT UN COMPLEXE PYRIDYLE FER (III)
  申请人：VERSALIS SPA

  公开号：WO2018073795A1

  公开（公告）日：2018-04-26

  A process for preparing conjugated diene (co)polymers comprising polymerizing at least one conjugated diene in the presence of a catalytic system comprising: (a) at least one pyridyl iron (III) complex having general formula (I) or (II): wherein: - R1, R2, R3 and R4, identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated C1-C20, preferably C1-C15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; - R5 represents a hydrogen atom, or is selected from linear or branched, optionally halogenated C1-C20, preferably C1-C15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; - X, identical or different, represent a halogen atom such as, for example, chlorine, bromine, iodine; or are selected from linear or branched C1- C20, preferably C1-C15, alkyl groups, -OCOR6 groups or -OR6 groups wherein R6 is selected from linear or branched C1-C20, preferably C1-C15, alkyl groups. - n is 3; (b) at least one co-catalyst selected from organo-aluminum derivatives, preferably from: (b1) aluminum compounds having general formula (III): Al(R7)(R8)(R9) (IIl) wherein R7 represents a hydrogen atom, or is selected from linear or branched C1-C20 alkyl groups, cycloalkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, alkoxy groups; R8 and R9, identical or different, are selected from linear or branched C1-C20 alkyl groups, cycloalkyl groups, aryl groups, alkyaryl groups, arylalkyl groups; (b2) aluminoxanes having general formula (IV): (R10)2-Al-O-[-AI(R11)-O-]m-AI-(R12)2 (IV), wherein R10, R11 and R12, identical or different, represent a hydrogen atom, or a halogen atom such as chlorine, bromine, iodine, fluorine; or are selected from linear or branched C1-C20 alkyl groups, cycloalkyl groups, aryl groups, said groups being optionally substituted with one or more silicon or germanium atoms; and m is an integer ranging from 0 to 1000; (b3) partially hydrolyzed organo-aluminum derivatives; (b4) haloaluminum alkyls having general formula (V) or (VI): AI(R13)p(X')3-p (V) AI2(R13)q(X')3-q (VI) wherein p is 1 or 2; q is an integer ranging from 1 to 5; R13, identical or different, are selected from linear or branched C1-C20 alkyl groups; X' represents a chlorine or bromine atom, preferably chlorine; provided that said co-catalyst (b) is not selected from organo-boron derivatives.
• Highly Stereoregular 1,3-Butadiene and Isoprene Polymers through Monoalkyl-<i>N-</i>Aryl-Substituted Iminopyridine Iron Complex-Based Catalysts: Synthesis and Characterization
  作者：Giovanni Ricci、Giuseppe Leone、Giorgia Zanchin、Benedetta Palucci、Antonella Caterina Boccia、Anna Sommazzi、Francesco Masi、Stefano Zacchini、Massimo Guelfi、Guido Pampaloni

  DOI：10.1021/acs.macromol.1c01291

  日期：2021.11.9

  and poly(isoprene)s with a predominantly cis-1,4/3,4 alternating structure, in which short cis-1,4 sequences of three or five units, whose length depends on the nature of the ligand on the iron atom, are present. A detailed NMR characterization (1H-, 13C-, and 2D experiments) of the resultant poly(isoprene)s is reported, and a tentative scheme for the formation of the novel isoprene polymers is proposed

  合成并表征了一些新的单烷基-N-芳基取代的亚氨基吡啶氯化铁络合物，其在亚胺碳和芳环的邻位取代基的性质不同。对于其中之一，获得了单晶，这可以确定其晶体结构，其中铁中心与氯化物和配体的两个氮原子配位。铁周围的配位是扭曲的四面体，FeCl 2很少发现配位模式与二齿氮配体的加合物。所有配合物都与甲基铝氧烷结合使用，用于 1,3-丁二烯和异戊二烯的聚合，提供间同立构 1,2 聚（1,3-丁二烯）和聚（异戊二烯），主要为顺式-1， 4/3,4 交替结构，其中存在三个或五个单元的短顺式-1,4 序列，其长度取决于铁原子上配体的性质。报告了所得聚（异戊二烯）的详细 NMR 表征（1 H-、13 C- 和 2D 实验），并提出了形成新型异戊二烯聚合物的暂定方案。