tert-butyl diphenylphosphinomethyl ketone dimethylhydrazone | 144091-89-4

• 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: tert-butyl diphenylphosphinomethyl ketone dimethylhydrazone
• CAS: 144091-89-4
• 化学式: C₂₀H₂₇N₂P
• 分子量: 326.422
• InChiKey: KSVFCMWWWHGCML-XUTLUUPISA-N

物化性质

• 沸点：
  417.7±47.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.08
• 重原子数：
  23.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  15.6
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  tert-butyl diphenylphosphinomethyl ketone dimethylhydrazone 在 一水合肼 、 溶剂黄146 作用下， 以 乙醇 为溶剂， 反应 2.0h， 以94%的产率得到2-Butanone, 1-(diphenylphosphino)-3,3-dimethyl-, hydrazone, (2Z)-
  参考文献：
  名称：

  新的双齿配体PPh 2 CH 2 C（Bu t）NNR 2（R = H或Me）和PPh 2 CH 2 C（Bu t）NNCHPh及其与6族金属羰基化合物的配合物

  摘要：

  的治疗叔丁基甲基酮二甲基腙与礼部，接着PPH 2氯，得到结晶膦二甲基腙PPH 2 CH 2 C（卜吨）NNMe 2 2a中具有与c NNMe 2中的组Ž配置。该具有[Mo（CO）4（nbd）]（nbd =降冰片二烯）的膦得到的[Me 2 }] 3a具有六元螯合环。相应地制备了相应的钨3b和铬3c配合物。当将膦2a与[Mo（CO）[图6 ]与同分异构体[NMe 2 }] 4一起形成了一些3a，其中五元螯合环和围绕CNNMe 2的E排列。当在二甘醇二甲醚[MeO（CH 2） 2 O（CH 2） 2 OMe]中加热3a时，温度约为。在150℃下形成膦亚胺络合物[H]] 5。带有肼的化合物2a以超过90％的产率得到了含有CNNH 2部分的相应的膦2c。膦2a或2c与硫反应，得到相应的膦硫化物。具有[M（CO）4（nbd）]的膦2c给出[[未图示] H 2 }]（M ＝ Mo 3d，W 3e或Cr

  DOI：

  10.1039/dt9920002361
• 作为产物：
  描述：

  3,3-Dimethyl-2-butanone N,N-dimethylhydrazone 、 二苯基氯化膦 在 正丁基锂 作用下， 生成 tert-butyl diphenylphosphinomethyl ketone dimethylhydrazone
  参考文献：
  名称：

  新的双齿配体PPh 2 CH 2 C（Bu t）NNR 2（R = H或Me）和PPh 2 CH 2 C（Bu t）NNCHPh及其与6族金属羰基化合物的配合物

  摘要：

  的治疗叔丁基甲基酮二甲基腙与礼部，接着PPH 2氯，得到结晶膦二甲基腙PPH 2 CH 2 C（卜吨）NNMe 2 2a中具有与c NNMe 2中的组Ž配置。该具有[Mo（CO）4（nbd）]（nbd =降冰片二烯）的膦得到的[Me 2 }] 3a具有六元螯合环。相应地制备了相应的钨3b和铬3c配合物。当将膦2a与[Mo（CO）[图6 ]与同分异构体[NMe 2 }] 4一起形成了一些3a，其中五元螯合环和围绕CNNMe 2的E排列。当在二甘醇二甲醚[MeO（CH 2） 2 O（CH 2） 2 OMe]中加热3a时，温度约为。在150℃下形成膦亚胺络合物[H]] 5。带有肼的化合物2a以超过90％的产率得到了含有CNNH 2部分的相应的膦2c。膦2a或2c与硫反应，得到相应的膦硫化物。具有[M（CO）4（nbd）]的膦2c给出[[未图示] H 2 }]（M ＝ Mo 3d，W 3e或Cr

  DOI：

  10.1039/dt9920002361

文献信息

• Complexes of the bidentate ligands Z-PPh₂CH₂C(Bu^t)NNR₂(R = Me or H) with rhodium and iridium
  作者：Sarath D. Perera、Bernard L. Shaw

  DOI：10.1039/dt9950000633

  日期：——

  hydrazone Z-PPh2CH2C(But)NNH2(L2) gave the chelate complexes [[graphic omitted]R2}](R = Me 1a or H 1b). Complex 1a reacts with another mole of L1 to give the bis(phosphine)rhodium(I) complex trans-[RhCl(CO)-PPh2CH2C(But)NNMe2}2]2a. The analogous iridium(I) complex 2b was prepared by treating [IrCl(CO)2(H2NC6H4Me-p)] with 2 mol equivalents of L1. Complex 2a reacts with [PtCl2(cod)](cod = cycloocta-1,5-diene)

  0.5治疗当量的[的RhCl（CO）2 } 2 ]与膦二甲基腙Ž -PPh 2 CH 2 C（卜吨）NNMe 2（L 1）或膦腙Ž -PPh 2 CH 2 C（卜吨）NNH 2（L 2）得到螯合物[[R 2＝ Me 1a或H 1b ]] 。配合物1a与另一摩尔L 1反应，生成双（膦）铑（I）复杂反式-[RhCl（CO）-PPh 2 CH 2 C（Bu t）NNMe 2 } 2 ] 2a。通过用2摩尔当量的L 1处理[IrCl（CO）2（H 2 NC 6 H 4 Me- p）]制备类似的铱（I）配合物2b。络合物2a与[PtCl 2（cod）]（cod =环辛-1,5-二烯）反应，得到螯合物1a和[[省略图示] -Me 2 }的1：1混合物。[IrCl（CO）2的处理（H 2 NC 6 H 4 Me- p）]与2当量的L 2给出氢化铱（III）配合物顺式-[[图略] H 2 } 2 ] Cl
• Novel chemistry of rhodium induced by a new type of ligand, a phosphino-N-benzoylhydrazone: crystal structure of [Rh (CO){C(CO2Me)CHCO2 Me}{P PPh2CH[C(CO 2Me)C  (CO2 Me)]C -(But)N –N C(Ph)O }]
  作者：Mustaffa Ahmad、Sarath D. Perera、Bernard L. Shaw、Mark Thornton-Pett

  DOI：10.1039/a702196h

  日期：——

  Treatment of the phosphino-N,N-dimethylhydrazone Z-PPh 2 CH 2 C(Bu t )NNMe 2 with benzohydrazide in the presence of acetic acid gave the phosphino-N-benzoylhydrazone PPh 2 CH 2 C(Bu t )NNHC(O)Ph I. Treatment of the phosphine I with 0.5 equivalent of [RhCl(CO) 2 } 2 ] gave the rhodium(I) complex [Rh(CO)PPh 2 CH 2 C(Bu t )N–NC(Ph)O}] 1 containing two fused five-membered chelate rings. Complex 1 readily reacted with Br 2 to give the dibromorhodium(III) complex [RhBr 2 (CO)PPh 2 CH 2 C(Bu t )N–NC(Ph) O }] 2. Similarly, it underwent oxidative-addition reactions with MeI or HCCCH 2 Cl to give rhodium(III) complexes of type [RhX(R)(CO) PPh 2 CH 2 C(Bu t ) N–NC(Ph) O }] (R = Me, X = I 3; R = CHCCH 2 , X = Cl 4). In contrast, treatment of 1 with allyl bromide caused loss of the carbon monoxide ligand to give the η 3 -allylrhodium(III) complex [RhBr(η-3-C 3 H 5 ) PPh 2 CH 2 C(Bu t )  N–NC(Ph)O }] 5. Treatment of 1 with MeO 2 CCCCO 2 Me gave the cyclometallated alkenylrhodium(III) complex [Rh(CO)C(CO 2 Me)CHCO 2 Me } PPh 2 CH[C(CO 2 Me) C(CO 2 Me)]C(Bu t )  N–NC(Ph)O }] 6, in which the phosphine ligand is tetradentate through P, N, O and C; in the formation of 6 one alkyne has attacked the methylene carbon of the phosphine ligand and the second has added to Rh–H to give RhC(CO 2 Me)CH(CO 2 Me). On the prolonged heating 6 isomerised to give the rhodium(III) complex 7; in this isomer the C(CO 2 Me)CH(CO 2 Me) ligand is trans to phosphorus whereas in 6 it is cis. The crystal structure of 6 has been determined.

  在乙酸存在下，用苯甲酰基吡嗪处理膦-N,N-二甲基腙 Z-PPh 2 CH 2 C(Bu t )NNMe 2，得到膦-N-苯甲酰基腙 PPh 2 CH 2 C(Bu t )NNHC(O)Ph I。用 0.5 等量的 [RhCl(CO) 2 } 2 ]处理膦 I，可得到含有两个融合的五元螯合环的铑(I)络合物 [Rh(CO)PPh 2 CH 2 C(Bu t )NâNC(Ph)O}] 1。络合物 1 很容易与 Br 2 反应，生成二溴铑(III)络合物 [RhBr 2 (CO)PPh 2 CH 2 C(Bu t )NâNC(Ph) O }] 2。同样，它与 MeI 或 HCCCH 2 Cl 发生氧化-加成反应，得到[RhX(R)(CO)PPh 2 CH 2 C(Bu t )âNâNC(Ph) O }] 类型的铑(III)配合物（R = Me，X = I 3；R = CHCCH 2，X = Cl 4）。相反，用烯丙基溴处理 1 会导致一氧化碳配体的损失，从而得到δ- 3 -烯丙基铑(III)配合物[RhBr(δ--3-C 3 H 5 ) PPh 2 CH 2 C(Bu t )â NâNC(Ph)O }] 5。用 MeO 2 CCCCO 2 Me 处理 1 得到环金属化烯基铑(III)络合物 [Rh(CO)C(CO 2 Me)CHCO 2 Me } PPh 2 CH[C(CO 2 Me)âC(CO 2 Me)]C(Bu t ) âNâNC(Ph)O }] 6。6 中，膦配体通过 P、N、O 和 C 具有四价性；在形成 6 的过程中，一个炔烃侵蚀了膦配体的亚甲基碳，第二个炔烃加入到 RhâH 中，得到 RhC(CO 2 Me)CH(CO 2 Me)。在长时间加热后，6 发生异构化，得到铑（III）络合物 7；在该异构体中，C（CO 2 Me）CH（CO 2 Me）配体反式为磷，而在 6 中则是顺式。6 的晶体结构已经确定。
• Complexes of tert-butyl diphenylphosphinomethyl ketone N-phenylhydrazone, Z-PPh2CH2C (But) = NNHPh, with molybdenum, palladium or platinum: crystal structure of cis-[PdCl2{Z-PPh2CH2C(But) = NNHPh}2]
  作者：Mustaffa Ahmad、Sarath D. Perera、Bernard L. Shaw、Mark Thornton-Pett

  DOI：10.1016/0020-1693(95)04806-5

  日期：1996.4

  the tetracarbonylmolybdenum(0) complex [Mo(CO)4PPh2CH2C(But) = NNHPh}] (3) in which 1 is bidentate; [Mo(CO)4(nbd)] with 2 equiv. of 1 gave the bis(phosphine)molybdenum (0) complex cis-[Mo(CO)4PPh2CH2C(But) = NNHPh}2] (4) in which 1 is monodentate through P. Treatment of [PdCl2(NCPh)2] or [PtCl2(cod)] (cod = cycloocta-1,5-diene) with 2 equiv. of 1 gave the complexes cis-[MCl2PPh2CH2C(But) = NNHPh}2]

  叔丁基二苯基膦甲基酮Ñ -phenylhydrazone，Z-PPH 2 CH 2 C（卜吨）= NNHPh（1）中，通过加热所述膦制备N，N- -dimethylhydrazone，Z-PPH 2 CH 2 C（卜吨）= NNMe 2与PhNHNH 2在乙醇中，在乙酸作为催化剂的情况下。将该膦转化为相应的氧化膦2a和硫化膦2b。用1当量处理[Mo（CO）4（nbd）]（nbd =去甲二烯）。共1得到四羰基钼（0）络合物[Mo（CO）4 PPh 2 CH 2 C（Bu t）= NNHPh}]（3），其中1是二齿的；[Mo（CO）4（nbd）]与2当量 的1得到双（膦）钼（0）配合物顺式-[Mo（CO）4 PPh 2 CH 2 C（Bu t）= NNHPh} 2 ]（4），其中1是通过P单齿的。 PdCl 2（NCPh）2 ]或[PtCl 2（cod）]（cod =环辛-1,5-二烯），当量为2。的1，得到配合物的顺式-
• Complexes of the bidentate ligands PPh₂CH₂C(Bu^t)NNR₂(R = H or Me) and PPh₂CH₂C(Bu^t)N–NCHPh with palladium and platinum. X-Ray crystal structure of cis-[Pt{PPh₂CH₂C(Bu^t)NNH}₂]
  作者：King Kuok Hii、Sarath D. Perera、Bernard L. Shaw、Mark Thornton-Pett

  DOI：10.1039/dt9940000103

  日期：——

  tert-Butyl diphenylphosphinomethyl ketone dimethylhydrazone L1 reacts with [PtCl2(cod)] (cod = cycloocta-1,5-diene) to give the chelate [PtCl2PPh2CH2C(Bu(t))=NNMe2}] with a six-membered chelate ring; the corresponding palladium complex was also prepared. The phosphino dimethylhydrazone L1 or the phosphino hydrazone L2 also react with [PtMe2(cod)] to give (PtMe2PPh2CH2C(But)=NNR2}], (R = Me or H); these platinum(II) complexes react with methyl iodide to give the corresponding trimethylplatinum(IV) complexes [PtMe3IPPh2CH2C(But)=NNR2}]. Treatment of [PtCl2(cod)] with 2 equivalents of L2 gave the dication cis-[PtPPh2CH2C(But)=NNH2}2]2+ isolated as the chloride or chloride hexafluorophosphate salts. The dicationic dichloride reacted with 2 moles of sodium ethoxide to give the neutral cis-[PtPPhCH2C(But)=NNH}2]. Treatment of [PdCl2(NCPh)2] with L2 gave [PdPPh2CH2C(But)=NNH2}2]Cl2, which with sodium ethoxide gave the neutral trans[PdPPh2CH2C(But)=NNH}2]. The mixed azine monophosphine PPh2CH2C(But)=N-N=CHPh L3 with [PdCl2(NCPh)2] gave the chelate complex [PdCl2PPh2CH2C(But)=N-N=CHPh}] and with [PtMe2(cod)] it gave [PtMe2PPh2CH2C(But)=N-N=CHPh)]. Treatment of [PtCl2(NCMe)2] with 2 equivalents of L3 gave trans-[PtCl2PPh2CH2C(But)=N-N=CHPh}2] which on heating gave the dicationic dichloride salt cis-[PtPPh2CH2C(But)=N-N=CHPh}2]Cl2. Successive treatments of this salt with 1 mole of sodium methoxide gave cis-[PPh2CH2C(But)=N-N=CHPh}PtPPh2CH=C(But)N-N=CHPh}]+ and cis-[PtPPh2CH=C(But)N-N=CHPh}2]. Proton, C-13-H-1}, P-31-H-1) NMR and infrared data have been obtained. Crystals of cis-[PtPPh2CH2C(But)=NNH2}2 are monoclinic, space group P2(1)/c, with a = 1261.5(2), b = 1794.6(3), c = 1792.0(4) pm and Z = 4; final R = 0.0451 for 4088 observed reflections.
• Some chlorocarbonylruthenium(II) complexes of P,N-donor ligands: crystal structures of [RuCl(CO) {PPh2CH2C(But)NNH2}2]Cl and fac,cis-[RuCj2(CO) {PPh2CH2C(But)NNC(But)CH2PPh2}]
  作者：Bernard L. Shaw、Uchenna U. Ike、Sarath D. Perera、Mark Thornton-Pett

  DOI：10.1016/s0020-1693(98)00045-0

  日期：1998.9

  Treatment of the phosphino N,N-dimethylhydrazone Z-PPh2CH2C(Bu')=NNMe2 (1) with [RuCl2(CO)(2)](x) gave the dichlorodicarbonyl-ruthenium (II) complex cis,cis-[RuCl2(CO)2PPh2CH(2)C(Bu-t)=NNMe2}] (4). Treatment of the phosphino hydrazone Z-PPh2CH2C-(Bu-t)=NNH2 (2) with [RuCl2(CO)(2)](x) gave the chloromonocarbonylruthenium(II) complex salt [RuCl(CO)PPh2CH2C-(Bu-t)=NNH2}(2),]Cl (5). Treatment of the azine diphosphine Z,Z-PPh2CH2C(Bu-t)-N-N=C( Bu-t)CH2PPh2 (3) with [RuCl2(CO)(2)](x) gave the dichlorocarbonylruthenium(II) complexes fac,cis-[RuCl2(CO)PPh2CH2C(Bu-t)=N-N=C(Bu-t)CH2PPh2}] (6) and mer,cis-[RuCl2(CO) PPh2CH2C(Bu-t)=N-N=C(Bu-t)CH2PPh2}] (7), which were easily separated. Irradiation of 7 in chloroform solution with a mercury are lamp yielded 6 quantitatively. When a solution of 6 in 2-methoxyethanol was put aside at 20 degrees C in daylight, it rearranged to 7 with mer,trans-[RuCl2(CO) PPh2CH2C(Bu-t)=N-N=C(Bu-t) CH2PPh2}] (8) as a probable intermediate. (C) 1998 Elsevier Science S.A. All rights reserved.