N--2-acetimidoyl-pyridin | 7137-96-4

• 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--2-acetimidoyl-pyridin
• 英文别名: N-(2-methylphenyl)-1-pyridin-2-ylethanimine
• CAS: 7137-96-4
• 化学式: C₁₄H₁₄N₂
• 分子量: 210.279
• InChiKey: HLGUAVMAMZECCK-UHFFFAOYSA-N

物化性质

• 沸点：
  93 °C
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  25.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N--2-acetimidoyl-pyridin 在 lithium hexamethyldisilazane 作用下， 以 正己烷 为溶剂， 反应 12.0h， 以56.2%的产率得到
  参考文献：
  名称：

  第一行过渡金属和锂吡啶-烯-酰胺络合物，具有N-和C-异构体以及基于苄基CH键的配体活化

  摘要：

  Ene-amines Z-3-(2-pyridyl)-1-aza(2,6-Pr-i(2)-Ph)propene, (pynac)H, and 2-(2-pyridy1)-1-aza(2,6-R,R'-Ph)propene, (pyEA-ArRR')H, were synthesized by condensation procedures; corresponding lithium or potassium ene-amides were prepared via standard deprotonation protocols. Addition of 2 equiv of (pynac)H to {(Me3Si)(2)N}(2)Fe(THF) or 2 Li(pynac) to FeBr2(THF)(2) afforded (pynac)(2)Fe (1), while treatment of CrCl2(THE)(2), MnCl2, FeBr2(THF)(2), and CoCl(2)py(4) with 2 equiv of (pyEA-(ArPr2)-Pr-i)K afforded pseudotetrahedral (pyEA-(ArPr2)-Pr-i)(2)M (2-M, M = Cr, Mn, Fe) and (pyEA-(ArPr2)-Pr-i)(2)Co-py (2-Co-py). Diamagnetic (kappa-C,N-pyEA-(ArPr2)-Pr-i)(3)Co (3) was prepared in low yield (similar to 7%) from CoCl2, and its Co-C(sp(3)) linkages are unusually low in field strength. Reactivity studies yielded little clean reactivity, but thermolysis of 2-Co-py afforded the bis-indolamide derivative -{kappa-N,N-N(C6H3(2-Pr-i)CMe2C(Me)(2-py)}(2)Co (5-Co), and related thermolyses of 2-M (M = Cr, Mn, Fe), conducted on NMA. tube scales, generated related 5-M (M = Cr, Mn, Fe) at roughly the same rates. This observation prompted thermolyses of (pyEA-ArRR')Li, which rearrange to their corresponding indolamides in >90% yields. Rate studies, accompanied by KLE and EIE observations, revealed that an initial hydrogen transfer is reversible and is likely to correspond to an anionic rearrangement, whereas C-C bond formation is rate-determining, as suggested by accompanying calculations. X-ray structure determinations of 1, 2-Fe, 2-Co-py, 3, and 5-Co were conducted.

  DOI：

  10.1021/acs.organomet.5b00385
• 作为产物：
  描述：

  2-乙酰基吡啶 、 邻甲苯胺 以 甲醇 为溶剂， 反应 4.0h， 以91%的产率得到N--2-acetimidoyl-pyridin
  参考文献：
  名称：

  螯合配体支持的锌配合物的合成和X射线晶体结构：α-亚氨基吡啶与ZnEt2的各种反应

  摘要：

  α‐氨基吡啶（α‐IP）是重要的氧化还原非清纯配体。α-IP的亚氨基官能团上的取代基对与二乙基锌的反应选择性有重要影响。对于亚氨基碳上具有氢取代基的α-IPs，非大体积N-取代基苯基和2-甲基苯基的还原反应发生，而空间较大的N-取代基2可以选择性地实现烷基加成和偶联反应2。 6-二甲基苯基或2,4,6-三甲基苯基。但是，对于亚氨基碳上具有CH 3取代基的α-IP，无论N为何，都会发生去质子化反应2-甲基苯基或2,6-二甲基苯基的取代基。所有产品均经过分离，并通过单晶X射线衍射进行表征。还讨论了这些反应的可能机理。

  DOI：

  10.1002/zaac.201800120

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 the preparation of syndiotactic 1,2-polybutadiene in the presence of a catalytic system comprising a pyridyl iron complex
  申请人：Versalis S.P.A.

  公开号：US10954326B2

  公开（公告）日：2021-03-23

  Process for the preparation of syndiotactic 1,2-polybutadiene comprising polymerising 1,3-butadiene in the presence of a catalytic system comprising: —at least one pyridyl iron complex having the general formula (I), in which: —R1 represents a hydrogen atom; or a methyl group; —R2 represents a hydrogen atom; or is selected from linear or branched C1-C10 alkyl groups; —X, identical or different to one another, represent a halogen atom; or are selected from linear or branched, C1-C20 alkyl groups, —OCOR3 groups or —OR3 groups in which R3 is selected from linear or branched C1-C20 alkyl groups; —n is 2 or 3; —at least one aluminoxane having the general formula (II), (R4)2-AI-O-[-AI(R5)—O-]m-AI-(R6)2 (ll) in which R4, R5 and R6, identical or different to one another, represent a hydrogen atom, or a halogen atom; or are selected from linear or branched C1-C20 alkyl groups, cycloalkyi groups, aryl groups, said groups being optionally substituted with one or more silicon atoms or germanium; and m is an integer ranging from 0 to 1000; in which the molar ratio between the aluminium present in the aluminoxane having the general formula (II) and the iron present in the pyridyl iron complex having the general formula (I) is ranging from 5 to 20.

  制备顺式1,2-聚丁二烯的过程包括在催化体系的存在下聚合1,3-丁二烯，所述催化体系包括：至少一种具有通式(I)的吡啶基铁配合物，其中：R1代表氢原子或甲基基团；R2代表氢原子或选自线性或支链C1-C10烷基基团；X，相同或不同，代表卤素原子或选自线性或支链C1-C20烷基基团、OCOR3基团或OR3基团，其中R3选自线性或支链C1-C20烷基基团；n为2或3；至少一种具有通式(II)的氧化铝烷，(R4)2-AI-O-[-AI(R5)—O-]m-AI-(R6)2(II)，其中R4、R5和R6，相同或不同，代表氢原子或卤素原子，或选自线性或支链C1-C20烷基基团、环烷基基团、芳基基团，所述基团可选地被一个或多个硅原子或锗原子取代；m为0到1000的整数；其中通式(II)中的氧化铝烷中铝与通式(I)中吡啶基铁配合物中铁的摩尔比为5到20。
• PROCESS FOR THE PREPARATION OF POLYISOPRENE WITH A MAINLY ALTERNATING CIS-1,4- ALT-3,4 STRUCTURE IN THE PRESENCE OF A CATALYTIC SYSTEM COMPRISING A PYRIDYL IRON COMPLEX
  申请人：VERSALIS S.P.A.

  公开号：US20200369805A1

  公开（公告）日：2020-11-26

  Process for the preparation of polyisoprene with a mainly alternating cis-1,4-alt-3,4 structure comprising polymerizing isoprene in the presence of a catalytic system comprising: (a) at least one pyridyl iron complex having general formula (I): wherein: R 1 is selected from linear or branched C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; R 2 is selected from linear or branched C 1 -C 10 , preferably C 1 -C 3 , alkyl groups; X, mutually identical or different, represent a halogen atom such as, for example, chlorine, bromine, iodine; or they are selected from linear or branched C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, —OCOR 3 groups or —OR 3 groups wherein R 3 is selected from linear or branched C 1 -C 20 , preferably C 1 -C 15 , alkyl groups. n is 2 or 3; (b) at least one co-catalyst selected from organo-derivative compounds of aluminum, preferably from (b 1 ) aluminoxanes having general formula (II): (R 4 ) 2 —Al—O—[—Al(R 5 )—O—] m —Al—(R 6 ) 2 (II) wherein R 4 , R 5 and R 6 , mutually identical or different, represent a hydrogen atom, or a halogen atom such as, for example, chlorine, bromine, iodine, fluorine; or they 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 2 ) aluminum compounds having general formula (III): Al(R 7 )(R 8 )(R 9 )  (III) wherein R 7 is 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 , mutually identical or different, are selected from linear or branched C 1 -C 20 alkyl groups, cycloalkyl groups, aryl groups, alkylaryl groups, arylalkyl groups; wherein the molar ratio between the aluminum present in the co-catalyst and the iron present in the iron pyridyl complex having general formula (I) is ranging from 5 to 60, preferably from 8 to 55.

  制备具有主要交替顺反式-1,4-交替-3,4结构的聚异戊二烯的方法，包括在催化体系的存在下聚合异戊二烯，该催化体系包括：（a）至少一种具有通式（I）的吡啶基铁配合物，其中：R1选自线性或支链C1-C20，优选C1-C15烷基，可选取代环烷基，可选取代芳基；R2选自线性或支链C1-C10，优选C1-C3烷基；X，相互相同或不同，表示卤素原子，例如氯、溴、碘；或选自线性或支链C1-C20，优选C1-C15烷基，-OCOR3基或-OR3基，其中R3选自线性或支链C1-C20，优选C1-C15烷基；n为2或3；（b）至少一种选自铝的有机衍生物的协同催化剂，优选从（b1）具有通式（II）的铝氧烷氧化物中选取：（R4）2-Al-O-[—Al（R5）-O-]m-Al-（R6）2（II），其中R4、R5和R6相互相同或不同，表示氢原子或卤素原子，例如氯、溴、碘、氟；或选自线性或支链C1-C20烷基、环烷基、芳基，该基团可选取代有一个或多个硅或锗原子；m为0到1000的整数；（b2）具有通式（III）的铝化合物，其中R7为氢原子，或选自线性或支链C1-C20烷基、环烷基、芳基、烷基芳基、芳基烷基，烷氧基；R8和R9相互相同或不同，选自线性或支链C1-C20烷基、环烷基、芳基、烷基芳基、芳基烷基。其中，协同催化剂中铝的摩尔比与具有通式（I）的吡啶基铁配合物中的铁的摩尔比之比在5到60之间，优选在8到55之间。
• 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。
• Synthesis and X-ray Crystal Structures of Zinc Complexes Supported by Chelating Ligands: Various Reactions of α-Iminopyridines with ZnEt₂
  作者：Haimang Wang、Zhiqiang Guo、Jihong Yang、Wei Cao、Yupeng Hua、Xuehong Wei、Jianfeng Li

  DOI：10.1002/zaac.201800120

  日期：2018.7.17

  redox‐noninnocent ligand. The substituents on the imino function of α‐IPs have important impact on the reaction selectivity with diethylzinc. For the α‐IPs with a hydrogen substituent on the imino carbon, reduction occurred for the non‐bulky N‐substituents phenyl and 2‐methylphenyl groups, whereas alkyl addition and coupling reactions can be selectively achieved for the sterically bulky N‐substituents 2,6‐dimethylphenyl

  α‐氨基吡啶（α‐IP）是重要的氧化还原非清纯配体。α-IP的亚氨基官能团上的取代基对与二乙基锌的反应选择性有重要影响。对于亚氨基碳上具有氢取代基的α-IPs，非大体积N-取代基苯基和2-甲基苯基的还原反应发生，而空间较大的N-取代基2可以选择性地实现烷基加成和偶联反应2。 6-二甲基苯基或2,4,6-三甲基苯基。但是，对于亚氨基碳上具有CH 3取代基的α-IP，无论N为何，都会发生去质子化反应2-甲基苯基或2,6-二甲基苯基的取代基。所有产品均经过分离，并通过单晶X射线衍射进行表征。还讨论了这些反应的可能机理。