(E)-1-diphenylphosphanyl-3,3-dimethyl-N-[(E)-(4-nitrophenyl)methylideneamino]butan-2-imine | 157064-01-2

• 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: (E)-1-diphenylphosphanyl-3,3-dimethyl-N-[(E)-(4-nitrophenyl)methylideneamino]butan-2-imine
• CAS: 157064-01-2
• 化学式: C₂₅H₂₆N₃O₂P
• 分子量: 431.474
• InChiKey: AWSRZVNCPYQBGV-HTBZSNLMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  70.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1,5-cyclooctadiene)dimethylplatinum(II) 、 (E)-1-diphenylphosphanyl-3,3-dimethyl-N-[(E)-(4-nitrophenyl)methylideneamino]butan-2-imine 以 not given 为溶剂， 以69%的产率得到[PtMe2(PPh2CH2C(t-Bu)=NN=CH(C6H4NO2-4))]
  参考文献：
  名称：

  型的吖嗪膦的环金属化Ž，ë -PPh 2 CH 2 C（卜吨Y = H，I或;）N-NCHR（R =芳基或杂环基），涉及X-Y（X = C，N或O Br）铂（II）引起的键裂变

  摘要：

  膦Z -PPh 2 CH 2 C（Bu t）NNH 2 1被证明是一种方便的“试剂”，用于将芳基或杂环醛转化为嗪，然后可以容易地用C–H，C–I，C进行环铂化-Br，NH或OH键裂变。1与苯甲醛衍生物（RCHO）缩合得到Z型，E -PPh 2 CH 2 C（Bu t）N–N CHR [R = Ph 2a，C 6 H 2（OMe）3 -3,4， 5 2b，C6 ħ 4 NO 2 -4 2C，C 6 H ^ 4 I-2 2d中，C 6 H ^ 4 BR-2 2E，C 6 H ^ 4 CL-2 2F或C 6 H ^ 2（OH-2）（OME） 2 - 4,6 2克]。嗪2a - 2f在20°C下与[PtMe 2（cod）]（cod =环辛-1,5-二烯）反应，得到二甲基铂（ II）配合物[[图略]CHR}] 3a - 3f分别含有六元螯合环。用[PtMe 2（cod）]处理2g，会发生O-H键裂变

  DOI：

  10.1039/dt9950000641
• 作为产物：
  描述：

  对硝基苯甲醛 、 2-Butanone, 1-(diphenylphosphino)-3,3-dimethyl-, hydrazone, (2Z)- 以 乙醇 为溶剂， 以79%的产率得到(E)-1-diphenylphosphanyl-3,3-dimethyl-N-[(E)-(4-nitrophenyl)methylideneamino]butan-2-imine
  参考文献：
  名称：

  型的吖嗪膦的环金属化Ž，ë -PPh 2 CH 2 C（卜吨Y = H，I或;）N-NCHR（R =芳基或杂环基），涉及X-Y（X = C，N或O Br）铂（II）引起的键裂变

  摘要：

  膦Z -PPh 2 CH 2 C（Bu t）NNH 2 1被证明是一种方便的“试剂”，用于将芳基或杂环醛转化为嗪，然后可以容易地用C–H，C–I，C进行环铂化-Br，NH或OH键裂变。1与苯甲醛衍生物（RCHO）缩合得到Z型，E -PPh 2 CH 2 C（Bu t）N–N CHR [R = Ph 2a，C 6 H 2（OMe）3 -3,4， 5 2b，C6 ħ 4 NO 2 -4 2C，C 6 H ^ 4 I-2 2d中，C 6 H ^ 4 BR-2 2E，C 6 H ^ 4 CL-2 2F或C 6 H ^ 2（OH-2）（OME） 2 - 4,6 2克]。嗪2a - 2f在20°C下与[PtMe 2（cod）]（cod =环辛-1,5-二烯）反应，得到二甲基铂（ II）配合物[[图略]CHR}] 3a - 3f分别含有六元螯合环。用[PtMe 2（cod）]处理2g，会发生O-H键裂变

  DOI：

  10.1039/dt9950000641

文献信息

• General strategy for inducing C–H bond fission (cycloiridation) in some aryl, heterocyclic, alkenyl or alkyl groups in azines derived from aldehydes or methyl ketones
  作者：Sarath D. Perera、Bernard L. Shaw、Mark Thornton-Pett

  DOI：10.1039/dt9950001689

  日期：——

  [IrCl(CO)2(H2NC6H4Me-p)] in benzene at 75 °C for 5 min it underwent an aryl C–H bond fission to give the cyclometallated chlorocarbonyliridium(III) hydride [[graphic omitted]H(OMe)3-3,4,5]}]1a. The crystal structure of 1a showed that (i) oxidative addition of the aryl C–H bond to iridium was cis with the hydride ligand trans to chloride, and (II) the cyclometallated azine ligand was in the terdentate mer

  膦Z -PPh 2 CH 2 C（Bu t）NNH 2 I已被证明是一种方便的“试剂”，用于将醛或酮转化为嗪，然后可以通过CH键裂变快速环化以生成铱（III）氢化物。的缩合我与一系列取代的苯甲醛的（RCHO），得到类型的混合吖嗪Ž，ë -PPh 2 CH 2 C（卜吨）N-N CHR [R = C 6 H ^ 2（OME）3 -3,4， 5 IIA，博士IIb，C 6 H 4 OMe-4 IIc，C 6 H 4 NO 2 -4 IId，C 6 H 4 Br-2 IIe，C 6 H 4 Cl-2 IIf，C 6 H 4 F-2 IIg，C 6 H 4 OH-2 IIh或C 6 H 2（OH-2）（OMe）2 -4,6，IIi ]。该ž，ē构型对于随后的环金属化是必要的，并且当将嗪IIa在苯中于75°C下用[IrCl（CO）2（H 2 NC 6 H 4 Me- p）]处理5分钟时，它会发生芳基
• A general method of promoting oxidative addition of C–H bonds to iridium(<scp>I</scp>) using azine phosphines
  作者：Sarath D. Perera、Bernard L. Shaw

  DOI：10.1039/c39940001203

  日期：——

  Treatment of [IrCl(CO)2(p-toludine)] with azine phosphines of type Z,E-PPh2CH2C(But)N–NC(Q)R, Q = H or Me, R = an organic group, activates aryl, heterocyclic, alkenyl or aliphatic C–H bonds to give cyclometallated iridium(III) hydrides.

  用 Z,E-PPh2CH2C(But)N−NC(Q)R 型吖嗪膦处理 [IrCl(CO)2(p-toludine)]，Q = H 或 Me，R = 有机基团，活化芳基、杂环、烯基或脂肪族C-H键，得到环金属化铱(III)氢化物。
• A general method of generating agostic interaction between Ru^IIand C–H bonds of tert-butyl, methyl, aryl, heterocyclic or alkenyl groups using azine phosphines
  作者：Sarath D. Perera、Bernard L. Shaw

  DOI：10.1039/dt9950003861

  日期：——

  Treatment of [RuCl2(PPh(3))(3)] 2 with the azine phosphine Z,E-PPh(2)CH(2)C(Bu(t))=N-N=C(Me) Bu(t) 3a, derived from MeC(=O)Bu(t), gave the delta-agostic tert-butyl complex mer,trans-[RuCl2(PPh(3))PPh(2)CH(2)-C(Bu(t))=N-N=C(Me)Bu(t)}] 4a, in which all nine hydrogens of the tert-butyl group are agostically interacting with ruthenium on the NMR time-scale at 20 degrees C. The analogous delta-agostic tert-butyl complex mer,trans-[RuCl2(PPh(3))PPh(2)CH(2)C(Bu(t))=N-N=C(H)Bu(t)}] 4b was also prepared. Treatment of 2 with the symmetrical azine diphosphine Z,Z-PPh(2)CH(2)C(Bu(t))=N-N=C(Bu(t))CH(2)PPh(2) 5 gave the delta-agostic tert-butyl complex mer,trans-[RuCl2(PPh(3))PPh(2)CH(2)C(Bu(t))=N-N=C(Bu(t))CH(2)PPh(2)}] 6, in which one of the PPh, groups is unco-ordinated. Treatment of 2 with the azine phosphine Z,E-PPh(2)CH(2)C(Bu(t))=N-N=C10H16 7, derived from pinacolone-fenchone mixed azine, gave the F-agostic methyl complex mer,trans-[RuCl2(PPh(3))PPh(2)CH(2)C(Bu(t))=N-N=C10H16}] 8, in which the methyl group ((CH3)-H-10) in the 1-position of the fenchone residue interacts with ruthenium (fenchone = 1,3,3-trimethylbicyclo[2.2.1]heptan-2-one). The unsymmetrical camphor azine monophosphine Z,Z-PPh(2)-C10H15N-N=C10H16 9 also gave a similar delta-agostic methyl complex mer,trans-[RuCl2(PPh(3))PPh(2)C(10)H(15)N-N=C10H16}] 10 (camphor = 1,7,7-trimethylbicyclo[2.2.1]heptan-2-one). Treatment of 2 with the azine Z,E-PPh(2)CH(2)C(Bu(t))=N-N=CH(C(6)H(4)NMe(2)-4) 11a, derived from 4-dimethylaminobenzaldehyde, gave the delta-agostic complex mer,trans-[RuCl2(PPh(3))PPh(2)CH(2)C(Bu(t))=N-N=CH(C(6)H(4)NMe(2)- 4)}] 12a, in which the hydrogens in the 2 and 6 positions of the aryl group are agostically interacting with ruthenium. Similarly, the azines 11b and 11c, derived from 4-methoxybenzaldehyde or 4-nitrobenzaldehyde, gave the delta-agostic complexes 12b and 12c, respectively. Treatment of 2 with the azine 13, derived from 1-methylpyrrole-2-carbaldehyde. gave the delta-agostic complex 14, in which the hydrogen in the 3-position of the heterocyclic group is agostically interacting with ruthenium. Treatment of 2 with the azine 15, derived from benzylideneacetone, gave the delta-agostic alkenyl complex 16. Proton, P-31-H-1} and some C-13-H-1} NMR data are given.
• Cyclometallation of azine phosphines of type Z,E-PPh₂CH₂C(Bu^t)N–NCHR (R = an aromatic or heterocyclic group) involving X–Y (X = C, N or O; Y = H, I or Br) bond fission by platinum(<scp>II</scp>)
  作者：Sarath D. Perera、Bernard L. Shaw

  DOI：10.1039/dt9950000641

  日期：——

  converting aryl or heterocyclic aldehydes into azines which can then be cycloplatinated readily with C–H, C–I, C–Br, N–H or O–H bond fission. Condensation of 1 with benzaldehyde derivatives (RCHO) gave mixed azines of type Z,E-PPh2CH2C(But)N–NCHR [R = Ph 2a, C6H2(OMe)3-3,4,5 2b, C6H4NO2-4 2c, C6H4I-2 2d, C6H4Br-2 2e, C6H4Cl-2 2f or C6H2(OH-2)(OMe)2-4,6 2g]. The azines 2a–2f reacted with [PtMe2(cod)](cod = cycloocta-1

  膦Z -PPh 2 CH 2 C（Bu t）NNH 2 1被证明是一种方便的“试剂”，用于将芳基或杂环醛转化为嗪，然后可以容易地用C–H，C–I，C进行环铂化-Br，NH或OH键裂变。1与苯甲醛衍生物（RCHO）缩合得到Z型，E -PPh 2 CH 2 C（Bu t）N–N CHR [R = Ph 2a，C 6 H 2（OMe）3 -3,4， 5 2b，C6 ħ 4 NO 2 -4 2C，C 6 H ^ 4 I-2 2d中，C 6 H ^ 4 BR-2 2E，C 6 H ^ 4 CL-2 2F或C 6 H ^ 2（OH-2）（OME） 2 - 4,6 2克]。嗪2a - 2f在20°C下与[PtMe 2（cod）]（cod =环辛-1,5-二烯）反应，得到二甲基铂（ II）配合物[[图略]CHR}] 3a - 3f分别含有六元螯合环。用[PtMe 2（cod）]处理2g，会发生O-H键裂变