2,6-dimethylphenyl-1'-methyl-2'-methoxyethyl-imine | 85385-06-4

• 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: 2,6-dimethylphenyl-1'-methyl-2'-methoxyethyl-imine
• 英文别名: N-(2', 6'-dimethylphenyl)-1-methoxymethyl-ethylideneamine；N-(2,6-dimethylphenyl)-1-methoxy-2-iminopropane；N-(2',6'-dimethylphenyl)-1-methoxymethyl-ethylideneamine；N-(2,6-dimethylphenyl)-1-methoxypropan-2-imine
• CAS: 85385-06-4
• 化学式: C₁₂H₁₇NO
• 分子量: 191.273
• InChiKey: WULZMAWITCAHDR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,6-dimethylphenyl-1'-methyl-2'-methoxyethyl-imine 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 生成 N-(2',6'-dimethylphenyl)-1-methoxymethylethylamine
  参考文献：
  名称：

  氧取代的丙二烯的分子间加氢胺化。合成N，O螯合的锆和钛酰胺基络合物的新途径†

  摘要：

  使用双（氨基甲酸酯）双（酰胺基）钛（IV）配合物（1）作为前催化剂，进行了由大体积的芳基胺进行的杂原子取代的烯丙基的分子间加氢胺化。的反应2,6-二甲基苯胺在配合物1的存在下，用氧取代的丙二烯2c或2d与酮亚胺的区域异构体一起作为排他性产物。此类酮亚胺产物的还原导致形成氨基醚，该氨基醚进一步用作形成N，O-螯合的五元钛环和锆环的配体。这样的空间要求N，O螯合配体导致单连接产物的高产率制备。所有配合物的固态分子结构均显示出金属中心周围扭曲的三角双锥几何形状，在金属和氧供体原子之间具有导数键。使用加氢胺作为配体制备关键步骤获得的这些新配合物本身也被证明是有用的环加氢胺预催化剂。

  DOI：

  10.1039/c1dt10448a
• 作为产物：
  描述：

  1-甲氧基-2-丙酮 、 2,6-二甲基苯胺 生成 2,6-dimethylphenyl-1'-methyl-2'-methoxyethyl-imine
  参考文献：
  名称：

  手性磷化-亚磷酰胺配体对受阻位N-芳烃的高效Ir催化不对称加氢反应

  摘要：

  已经开发出一种温和的，铱催化的，具有新的H 8 -BINOL衍生的膦-亚磷酰胺配体的空间受阻的N-芳胺类化合物的高对映体选择性氢化。本催化体系的特征在于用于多种空间受阻的N-芳基丙氨酸的氢化的高周转数（高达100000）和良好至完美的对映选择性（高达99％ee）。

  DOI：

  10.1021/ol301618r

文献信息

• Chiral phosphine-phosphoramidite ligands for highly enantioselective hydrogenation of N-arylimines
  作者：Qing Li、Chuan-Jin Hou、Xiao-Ning Liu、De-Zhi Huang、Yan-Jun Liu、Rui-Feng Yang、Xiang-Ping Hu

  DOI：10.1039/c4ra16062b

  日期：——

  The asymmetric hydrogenation of N-arylimines with the chiral phosphine-phosphoramidite ligand, (Sc,Sa)-PEAPhos 2b, has been developed. The results revealed that the presence of the substituents on the 3,3′-positions of the binaphthyl backbone significantly improved the enantioselectivity. The utility of this methodology was demonstrated in the synthesis of the chiral fungicide (R)-metalaxyl.

  已经开发了具有手性膦-亚磷酰胺配体（S c，S a）-PEAPhos 2b的N-芳基丙氨酸的不对称氢化。结果表明，在联萘骨架的3，3'-位置上的取代基的存在显着提高了对映选择性。该方法的实用性在手性杀菌剂（R）-甲霜灵的合成中得到了证明。
• Chiral Xyliphos Complexes for the Catalytic Imine Hydrogenation Leading to the Metolachlor Herbicide: Isolation of Catalyst–Substrate Adducts
  作者：Romano Dorta、Diego Broggini、Robert Stoop、Heinz Rüegger、Felix Spindler、Antonio Togni

  DOI：10.1002/chem.200305218

  日期：2004.1.5

  afforded [Ir(Cl)(cod)[(S)-(R)-4]] (7), which reacted with AgBF(4) to form [Ir(cod)[(S)-(R)-4]]BF(4) (8). Complexes 7 and 8 reacted with iodide to yield [Ir(I)(cod)[(S)-(R)-4]] (9). When 9 was treated with one and two equivalents of HBF(4), two isomers of the cationic Ir(III) iodo hydrido complex [Ir(I)(H)(cod)[(S)-(R)-4]]BF(4) were solated (10 and 11, respectively). Complex 9 was oxidized with one equivalent

  制备并表征了与先正Me甲草胺（3）工艺中的2-甲基-6-乙基苯基-1'-甲基-2'-甲氧基乙基亚胺（MEA-亚胺，1）的催化对映选择性氢化有关的铱配合物。二膦（S）-1-[（R）-2-（二苯基膦基）二茂铁基]乙基二（3,5-二甲苯基）膦（（S）-（R）-木脂基，（S）-（R）- 4）与[Ir（2）（micro-Cl）（2）（cod）（2）]（cod = 1,5-环辛二烯）一起提供[Ir（Cl）（cod）[（S）-（R）- [4]]（7），其与AgBF（4）反应形成[Ir（cod）[（S）-（R）-4]] BF（4）（8）。配合物7和8与碘化物反应生成[Ir（I）（cod）[（S）-（R）-4]]（9）。当用一当量和两当量的HBF（4）处理9时，阳离子Ir（III）碘氢杂合物[Ir（I）（H）（cod）[（S）-（R）-4]的两个异构体] BF（4）被隔离（分别为10和11）。用一当量的I（
• Chiral organic catalysts for the stereoselective reduction of carbon-nitrogen double bonds for the preparation of enantiomerically enriched amines
  申请人：UNIVERSITA' DEGLI STUDI DI MILANO

  公开号：EP2065371A1

  公开（公告）日：2009-06-03

  The invention relates to compounds of general formula (I): wherein R1-R7 are as defined in the description for use as catalysts in the stereoselective reduction of imines in the presence of trichlorosilane as reducing agent.

  本发明涉及一般式(I)的化合物：其中R1-R7如描述中定义，用作催化剂，存在三氯硅烷还原剂的情况下进行亚胺的立体选择性还原。
• Ferrocenyl diphosphines as ligands for homogeneous catalysts
  申请人：Ciba-Geigy Corporation

  公开号：US05463097A1

  公开（公告）日：1995-10-31

  A complex of the formula V or VI, [X.sub.1 M.sub.1 YZ] X.sub.1 M.sub.1 Y].sup..sym. A.sub.1.sup..crclbar. wherein X.sub.1 is two C.sub.2 -C.sub.12 olefins or one C.sub.5 -C.sub.12 diene, Z is Cl, Br or I, A.sub.1.sup..crclbar. is the anion of an oxyacid or complex acid, M.sub.1 is Rh or Ir, and Y is a compound of the formula I ##STR1## wherein R.sub.1 is C.sub.1 -C.sub.8 alkyl, phenyl or phenyl which is substituted by 1 to 3 C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy groups; R.sub.2 and R.sub.3 are identical and are C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl or C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, --SiR.sub.4 R.sub.5 R.sub.6, halogen, --SO.sub.3 M, --CO.sub.2 M, --PO.sub.3 M, --NR.sub.7 R.sub.8 and --[.sup..sym. NR.sub.7 R.sub.8 R.sub.9 ]X.sup..crclbar. ; or R.sub.2 and R.sub.3 are different and are C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, phenyl or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, --SiR.sub.4 R.sub.5 R.sub.6, halogen, --SO.sub.3 M, --CO.sub.2 M, --PO.sub.3 M.sub.2, --NR.sub.7 R.sub.8 and --[.sup..sym. NR.sub.7 R.sub.8 R.sub.9 ]X.sup..crclbar. ; or the group --PR.sub.2 R.sub.3 is a radical of formula II ##STR2## and R.sub.4, R.sub.5 and R.sub.6 are each independently of one another C.sub.1 -C.sub.12 alkyl or phenyl, R.sub.7 and R.sub.8 are H, C.sub.1 -C.sub.12 alkyl, phenyl or R.sub.7 and R.sub.8, taken together, are tetramethylene, pentamethylene or 3-oxa-1,5-pentylene, R.sub.9 is H or C.sub.1 -C.sub.4 alkyl, M is H or an alkali metal, X.sup..crclbar. is the anion of a monobasic acid, and * is a stereogenic carbon atom, in the form of their racemates and diastereoisomers or mixtures of diastereoisomers.

  该公式复合物为 V 或 VI，[X.sub.1 M.sub.1 YZ] X.sub.1 M.sub.1 Y].sup..sym. A.sub.1.sup..crclbar.，其中 X.sub.1 为两个 C.sub.2-C.sub.12 烯烃或一个 C.sub.5-C.sub.12 二烯，Z 为 Cl、Br 或 I，A.sub.1.sup..crclbar. 为氧酸或配酸的阴离子，M.sub.1 为 Rh 或 Ir，Y 为式I的化合物 ##STR1## 其中 R.sub.1 为 C.sub.1-C.sub.8 烷基、苯基或被 1 至 3 个 C.sub.1-C.sub.4 烷基或 C.sub.1-C.sub.4 烷氧基取代的苯基；R.sub.2 和 R.sub.3 相同且为 C.sub.1-C.sub.12 烷基、C.sub.5-C.sub.12 环烷基或 C.sub.1-C.sub.4 烷基或 C.sub.1-C.sub.4 烷氧基取代的 C.sub.5-C.sub.12 环烷基，或被选自 C.sub.1-C.sub.4 烷基、C.sub.1-C.sub.4 烷氧基、--SiR.sub.4 R.sub.5 R.sub.6、卤素、--SO.sub.3 M、--CO.sub.2 M、--PO.sub.3 M、--NR.sub.7 R.sub.8 和 --[.sup..sym. NR.sub.7 R.sub.8 R.sub.9 ]X.sup..crclbar. 组成的一到三个相同或不同成员取代的苯基；或 R.sub.2 和 R.sub.3 不同且为 C.sub.1-C.sub.12 烷基、C.sub.5-C.sub.12 环烷基、C.sub.1-C.sub.4 烷基或 C.sub.1-C.sub.4 烷氧基取代的 C.sub.5-C.sub.12 环烷基、苯基或被选自 C.sub.1-C.sub.4 烷基、C.sub.1-C.sub.4 烷氧基、--SiR.sub.4 R.sub.5 R.sub.6、卤素、--SO.sub.3 M、--CO.sub.2 M、--PO.sub.3 M.sub.2、--NR.sub.7 R.sub.8 和 --[.sup..sym. NR.sub.7 R.sub.8 R.sub.9 ]X.sup..crclbar. 组成的一到三个相同或不同成员取代的苯基；或 --PR.sub.2 R.sub.3 组为式II的基团 ##STR2## 其中 R.sub.4、R.sub.5 和 R.sub.6 各自独立地为 C.sub.1-C.sub.12 烷基或苯基，R.sub.7 和 R.sub.8 为 H、C.sub.1-C.sub.12 烷基、苯基或 R.sub.7 和 R.sub.8 一起为四亚甲基、五亚甲基或 3-氧杂-1,5-戊亚甲基，R.sub.9 为 H 或 C.sub.1-C.sub.4 烷基，M 为 H 或碱金属，X.sup..crclbar. 为一元酸的阴离子，* 为手性碳原子，以其外消旋体和对映异构体或对映异构体混合物的形式存在。
• Chiral Lewis base promoted trichlorosilane reduction of ketimines. An enantioselective organocatalytic synthesis of chiral amines
  作者：Stefania Guizzetti、Maurizio Benaglia、Franco Cozzi、Rita Annunziata

  DOI：10.1016/j.tet.2009.06.015

  日期：2009.8

  The reduction of the carbon-nitrogen double bond is an important transformation. Here we report our studies on a family of chiral organic catalysts able to promote the stereoselective reduction of ketimines with trichlorosilane. The very cheap, metal-free catalysts were easily prepared in one step from commercially available products, namely a chiral aminoalcohol and picolinic acid derivatives. The catalyst structure was extensively modified in a study that allowed to identify an extremely active species, able to promote the reduction on a large variety of substrates with high efficiency (up to 95% ee). A three component methodology has been also developed, where the enantiomerically enriched amine was isolated after performing the reaction by mixing a ketone and an amine in the presence of trichlorosilane and the catalyst. Its synthetic potentiality was demonstrated by employing the present metal-free catalytic procedure in the preparation of (S)-metolachlor, a potent and widely used herbicide. (C) 2009 Elsevier Ltd. All rights reserved.