racemic 1,3-diphenyl-1,3-propanediamine | 19293-52-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: racemic 1,3-diphenyl-1,3-propanediamine
• 英文别名: (+/-)-1,3-diphenyl-1,3-propanediamine；(dl)-1,3-diphenyl-1,3-propanediamine；(1R,3R)-1,3-diphenylpropane-1,3-diamine
• CAS: 19293-52-8；59132-37-5；59158-71-3；59169-20-9；64364-63-2
• 化学式: C₁₅H₁₈N₂
• 分子量: 226.321
• InChiKey: ILDQIFPNBGCLRH-HUUCEWRRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  52
• 氢给体数：
  2
• 氢受体数：
  2

安全信息

• 海关编码：
  2921590090

反应信息

• 作为反应物：
  描述：

  racemic 1,3-diphenyl-1,3-propanediamine 在 sodium tetrahydroborate 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 4.0h， 生成 (1R^*,3R^*)-N,N'-dibenzyl-1,3-diphenyl-1,3-propanediamine
  参考文献：
  名称：

  A Diastereoselective Synthesis of (dl)-1,3-Diphenyl-1,3-propanediamines

  摘要：

  通过高度对映选择性的苯基铈二氯化物对1-叔丁氧羰基-4,5-二氢-5-苯基吡唑（3）的加成反应，成功实现了外消旋1,3-二苯基-1,3-丙二胺（1）的大规模实用合成。将烷基铈加成反应应用于相应的5-烷基取代的1-Boc-4,5-二氢吡唑时，效果不佳，主要得到环裂解产物。此外，还描述了将二胺1进一步衍生化为N-取代衍生物8a-f的过程，这些衍生物带有N-甲基、N-乙基、N-异丙基、N-新戊基、N-苄基和N-三甲基甲基基团。

  DOI：

  10.1055/s-1992-34183
• 作为产物：
  描述：

  (R,R)-1,3-diphenylpropane-1,3-diol bis-mesylate 在 lithium aluminium tetrahydride 、 sodium azide 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 17.0h， 生成 racemic 1,3-diphenyl-1,3-propanediamine
  参考文献：
  名称：

  Synthesis of novel C2-symmetric ligands based on (R,R)- and (S,S)-diphenyl-1,3-propanediol

  摘要：

  A range of novel Ct-symmetric dioxygen and dinitrogen ligands can readily be obtained through the interconversion of the parent 1,3-diphenyl-1,3-propanediol enantiomers which are, in turn, accessed in good yields via a Sharpless asymmetric epoxidative resolution. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00074-9

文献信息

• A Diastereoselective Synthesis of (<i>dl</i>)-1,3-Diphenyl-1,3-propanediamines
  作者：Scott E. Denmark、Jung-Ho Kim

  DOI：10.1055/s-1992-34183

  日期：——

  A large-scale and practical synthesis of (dl)-1,3-diphenyl-1,3-propanediamine (1) has been achieved by a highly diastereoselective phenylcerium dichloride addition to 1-tert-butoxycarbonyl-4,5-dihydro-5-phenylpyrazole (3). Alkylcerium addition reaction to the corresponding 5-alkyl substituted 1-Boc-4,5-dihydropyrazoles was less satisfactory mainly giving ring-cleaved products. Further elaboration of the diamine 1 to the N-substituted derivatives 8a-f bearing N-methyl, N-ethyl, N-isopropyl, N-neopentyl, N-benzyl, and N-mesitylmethyl groups is described.

  通过高度对映选择性的苯基铈二氯化物对1-叔丁氧羰基-4,5-二氢-5-苯基吡唑（3）的加成反应，成功实现了外消旋1,3-二苯基-1,3-丙二胺（1）的大规模实用合成。将烷基铈加成反应应用于相应的5-烷基取代的1-Boc-4,5-二氢吡唑时，效果不佳，主要得到环裂解产物。此外，还描述了将二胺1进一步衍生化为N-取代衍生物8a-f的过程，这些衍生物带有N-甲基、N-乙基、N-异丙基、N-新戊基、N-苄基和N-三甲基甲基基团。
• OsXCl(phosphine)₂(diamine) and OsXCl(diphosphine)(diamine) (X = Cl, H) Complexes for Ketone Hydrogenation
  作者：Cinzia Barbato、Salvatore Baldino、Maurizio Ballico、Rosario Figliolia、Santo Magnolia、Katia Siega、Eberhardt Herdtweck、Paolo Strazzolini、Giorgio Chelucci、Walter Baratta

  DOI：10.1021/acs.organomet.7b00737

  日期：2018.1.8

  ethylenediamine (en), whereas the diphosphine derivatives trans-[OsCl2(dppf)(NN)] (NN = en (3), bn (4; bn = 1,4-butanediamine)) and trans-[OsCl2(dpbp)(en)] (5) were obtained from 1a, dppf or dpbp, and the corresponding NN ligand in CH2Cl2 or toluene. An X-ray diffraction study has been provided for 3. The isolation of the chiral derivatives trans-[OsCl2(diphosphine)((R,R)-dpen)] (diphosphine = dppf (6), dpbp (7)

  通过[OsCl 2（PPh 3）3 ]（1a）与乙二胺（en）反应制得O络合物反式-[OsCl 2（PPh 3）2（en）]（2），而二膦衍生物反式-[[ OSCL 2（DPPF）（NN）]（NN = EN（3），BN（4 ; BN = 1,4-丁二胺））和反式- [OSCL 2（DPBP）（烯）]（5从获得）1A，dppf或dpbp，以及CH 2 Cl 2中相应的NN配体或甲苯。X射线衍射研究已经提供了3。分离了手性衍生物反式-[OsCl 2（diphosphine）（（R，R）-dpen）]（diphosphine = dppf（6），dpbp（7），（R，R）-skewphos（8））使1a与二膦和（R，R）-dpen在甲苯中反应。所述前体[Os中治疗2氯4（P（米间-甲苯基）3）5 ]（图1b）带连接，得到[OSCL2（P（米间-甲苯基）3）2（烯）]（9），而反应1B与DPPB和Ñ，Ñ
• Addition of diethylzinc to aryl aldehydes catalyzed by (1S,3S)-N,N1-bis[benzyl]-1,3-diphenyl-1,3-propanediamine and its dilithium salt: a mechanistic rationale investigation.
  作者：Dario Pini、Alberto Mastantuono、Gloria Uccello-Barretta、Anna Iuliano、Piero Salvadori

  DOI：10.1016/s0040-4020(01)80230-1

  日期：——

  substituted 1,3-diamine , synthesized in high optical purity, and the corresponding dilithium salt are used, for the first time, as chiral catalysts in the addition of ZnEt2 to aromatic aldehydes. Both 1a and 1b are able to promote the reaction but the products obtained exhibited low enantiomeric excesses. By 1H NMR and UV-CD investigation, experimental evidences about the structure of some reaction intermediates

  以高光学纯度合成的N，N I-双苄基取代的1,3-二胺和相应的二锂盐首次用作将ZnEt 2加至芳族醛中的手性催化剂。既1A和1B是能够促进反应而得到的产物表现出低对映体过量。通过1 H NMR和UV-CD研究，获得了一些反应中间体的结构的实验证据：反应途径与光谱数据一致，可以推测其化学和立体化学结果。
• Novel ruthenium complexes and process for preparing alcoholic compounds using these
  申请人：Kanto Kagaku Kabushiki Kaisha

  公开号：US20030166978A1

  公开（公告）日：2003-09-04

  The invention provides novel ruthenium complexes having an optically active diphosphine compound, which has asymmetry on carbon and is easy to synthesize, as the ligand and a process for preparing optically active alcoholic compounds using said complexes as the catalysts, wherein said process is the process for preparing optically active alcoholic compounds, which are excellent in terms of reactivity, enatioselectivity and the like in an asymmetric hydrogenation of carbonyl compounds compared with conventional ruthenium complex catalysts having an optically active diphosphine compound having the axial chirality or the asymmetry on carbon as the ligand. In a preferred embodiment, the invention provides an optically active ruthenium complex represented by the general formula (1) 1 wherein X and Y, which can be identical to or different from each other, represent a hydrogen atom or an anion group, R 1 and R 2 , which can be identical to or different from each other, represent a chain or cyclic hydrocarbon group of carbon number 1 to 20, which can be substituted, R 3 and R 4 , which can be identical to or different from each other, represent a hydrogen atom or a hydrocarbon group of carbon number 1 to 3, and R 5 , R 6 , R 7 and R 8 , which can be identical to or different from one another, represent a hydrocarbon group of carbon number 1 to 30, which can be substituted, with the proviso that when X and Y are bromine, R 1 and R 2 are a methyl group, and when R 3 and R 4 are a hydrogen atom, at least one of R 5 , R 6 , R 7 and R 8 is not a phenyl group.

  这项发明提供了具有光学活性二膦化合物的新型钌配合物，该二膦化合物在碳上具有不对称性且易于合成，作为配体，并提供了一种利用该配合物作为催化剂制备光学活性醇化合物的方法，其中所述方法是制备光学活性醇化合物的方法，与具有轴向手性或在碳上具有不对称性的光学活性二膦化合物作为配体的传统钌配合物催化剂相比，在羰基化合物的不对称氢化中具有较高的反应活性、对映选择性等方面表现出色。在优选实施方式中，该发明提供了一种由通式（1）1表示的光学活性钌配合物，其中X和Y可以相同或不同，表示氢原子或阴离子基团，R1和R2可以相同或不同，表示碳数为1至20的链状或环烃基团，可以被取代，R3和R4可以相同或不同，表示碳数为1至3的氢原子或烃基团，R5、R6、R7和R8可以相同或不同，表示碳数为1至30的烃基团，可以被取代，但当X和Y为溴时，R1和R2为甲基基团，且当R3和R4为氢原子时，R5、R6、R7和R8中至少有一个不是苯基团。
• Catalysts
  申请人：Hems Patrick William

  公开号：US20070066850A1

  公开（公告）日：2007-03-22

  Catalysts suitable for asymmetric hydrogenation reactions is described comprising the reaction product of a group (8) transition metal compound a chiral phosphine and a chiral diamine of formula (1) in which R 1 , R 2 R 3 or R 4 are independently hydrogen, a saturated or unsaturated alkyl, or cycloalkyl group, an aryl group, a urethane or sulphonyl group and R 5 , R 6 , R 7 or R 8 are independently hydrogen, a saturated or unsaturated alkyl or cycloalkyl group, or an aryl group, at least one of R 1 , R 2 , R 3 or R 4 is hydrogen and A is a linking group comprising one or two substituted or unsubstituted carbon atoms.

  本文描述了用于不对称氢化反应的催化剂，包括式（1）中的手性膦和手性二胺与8族过渡金属化合物的反应产物，其中R1、R2、R3或R4独立地为氢、饱和或不饱和烷基、环烷基、芳基、脲基或磺酰基，R5、R6、R7或R8独立地为氢、饱和或不饱和烷基或环烷基、或芳基，其中至少有一个为氢，A为含有一个或两个取代或未取代碳原子的连接基。