[(i-PrNH)PN-t-Bu]2 | 1226854-30-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: [(i-PrNH)PN-t-Bu]2
• 英文别名: [i-PrNHPN-t-Bu]2；1,3-ditert-butyl-2-N,4-N-di(propan-2-yl)-1,3,2,4-diazadiphosphetidine-2,4-diamine
• CAS: 1226854-30-3；1313588-54-3
• 化学式: C₁₄H₃₄N₄P₂
• 分子量: 320.398
• InChiKey: NMOCQGPRKAMZIN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  30.5
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [(i-PrNH)PN-t-Bu]2 、 马来酸二甲酯 以 甲苯 为溶剂， 反应 24.0h， 以89%的产率得到(i-Pr-NH)P(μ-N-t-Bu)2P(NH-i-Pr)=C(CO2Me)CH2(CO2Me)
  参考文献：
  名称：

  Cyclodiphosph(III)azane chemistry – Ylides from the reaction of [(RNH)P-N(t-Bu)]2 [R=t-Bu, i-Pr] with dimethyl maleate and chiral ansa-type derivatives from reaction of [ClP-N(t-Bu)]2 with a substituted BINOL

  摘要：

  Use of a simple inorganic ring system with the cyclodiphosph(III) azane skeleton [e.g. [(RNH)P-N(t-Bu)](2) [R = t-Bu (7), i-Pr (8)] to probe some of the intermediates proposed in phosphine mediated organic reactions is highlighted. Thus the reaction of 7-8 with the allenylphosphine oxide Ph2P(O)C(Ph)=C=CH2 (9) affords the phosphinimines [(RNH)P(mu-N-t-Bu)(2)P(=N-R)-C(=CH2) CH(Ph)-P(O)Ph-2] [R= t-Bu (10), i-Pr (11)], while a similar reaction of 7-8 with dimethyl maleate (or dimethyl fumarate) affords the ylides [(RNH) P(mu-N-t-Bu)(2)P(NH-R)=C(CO2Me)-CH2(CO2Me) [R = t-Bu (18), i-Pr (19)]. The implication of such reactions on phosphine mediated organic transformations including Morita-Baylis-Hillman reaction is mentioned. In a rather rare type of situation, an unusually long phosphoryl (P=O) bond [1.538 (5) angstrom] as revealed the X-ray structure of {(R)-6,6'-(t-Bu)(2)-1,1'-(C10H5)(2)-2,2'-O-2-}{P(O)(N-t-Bu)(2)-P(Se)} (27) is rationalized by means of crystallographic disorder in packing after comparing the data with that in the literature and {1,1'-(C10H6)(2)-2,2'-O-2}{P(Se)(N-t-Bu)(2)-P(Se)} (29). X-ray structures of the new compounds 10-11, 18-19, 27 and 29 are discussed. Compound 10 crystallizes in the chiral space group Pca2(1) with (S)-chirality at the carbon center [-C(=CH2) CH(Ph)-P] suggesting a case of spontaneous resolution through crystallization. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2010.12.072

文献信息

• Cyclodiphosphazanes as synthetic probes: P-C/P-N bond formation from the reaction with functionalized propargyl alcohols and N-hydroxy substrates
  作者：G GANGADHARARAO、K C KUMARA SWAMY

  DOI：10.1007/s12039-015-0772-7

  日期：2015.2

  Phosphano-indoles were synthesized in a fairly straightforward route from the reaction of simple cyclodiphosphazanes [XP(μ-N-t-Bu)2PY] [X = Y = NH-t-Bu (1a); X = Y = NH-i-Pr (1b)] with o-aminophenyl functionalized propargyl alcohols. The reaction occurs via an allene intermediate formed by P III-O-C → P V(O)-C rearrangement, followed by cyclization utilizing the central allenic carbon and the –NH2

  从简单的环二磷氮烷[XP（μ- N- t -Bu）2 PY] [X = Y = NH- t -Bu（1a）; X = Y = NH - Pr（1b）]和邻氨基苯基官能化的炔丙醇。反应通过P III -OC→P V（O）-C重排形成的烯丙基中间体发生，然后利用中心烯丙基碳和–NH 2官能团进行环化。环二磷氮烷[XP（μ- N- t -Bu）2PY] [X = Y = Cl（1c）; X = Cl，Y = NH- t -Bu（1d）]已用N-羟基底物处理以获得新颖的P III -ON→P V（O）-N重排产物。2-（1-苯基-乙基）-3-[（t -Bu）NH）P（μ- N- t -Bu）2 P（O）]-吲哚这四种产物的X射线结构[ 14 ] ，顺式- [ - C（= O）-C 6 H ^ 4 -C（= O） - ] - NP（= O）-N-吨-Bu} 2 [顺式- 18 ]，反式- [ -
• Unusual nitrogen based heterocycles via allenic intermediates from the reaction of propargyl alcohols with P(III) substrates
  作者：G. Gangadhararao、K.C. Kumara Swamy

  DOI：10.1016/j.tet.2014.02.064

  日期：2014.4

  The apparently simple reaction of the P(III) precursors [(RNH)P(μ-N-t-Bu)2PY] (Y=NH-t-Bu, Cl), (OCH2CMe2CH2O)PCl, and Ph2PCl with functionalized propargyl alcohols is examined. In most cases, the final products are not the expected allenes but several previously unpredicted structural motifs, such as substituted oxazabenzocycloheptenones, indolinones, and fused heterocycles as revealed by X-ray crystallography

  P（III）前体[（RNH）P（μ-N- t - Bu）2 PY ]（Y = NH- t- Bu，Cl），（OCH 2 CMe 2 CH 2 O）PCl的表面反应很简单和Ph 2检查具有官能化炔丙醇的PC1。在大多数情况下，最终产品不是预期的异戊烯，而是一些以前无法预测的结构基序，例如X射线晶体学显示的取代的氧杂苯并环庚烯酮，吲哚满酮和稠合杂环。还讨论了这些新颖反应的机理方面，以及可能的用途和产物的结构化学。许多这些化合物的P–C或P–N键断裂导致产生无磷的2-取代的吲哚，喹啉酮和四氢idine啶。
• Exploring organic reactions using simple cyclodiphosphazanes
  作者：K.C. Kumara Swamy、G. Gangadhararao、R. Rama Suresh、N.N. Bhuvan Kumar、Manab Chakravarty

  DOI：10.1016/j.jorganchem.2009.11.001

  日期：2010.4

  cyclodiphosphazane is also described. X-ray structures of the new compounds [(t-BuNH)(PhCH2CH(CN)CH2–)P(μ-N-t-Bu)2P(NH-t-Bu)]+[HCO3]− (13), [(t-BuNH)P(μ-N-t-Bu)2P(N-t-Bu)-C(CH2)CH(C6H4-4-Me)-P(O)(OCH2CMe2CH2O)] (18), [(i-PrNH)P(μ-N-t-Bu)2P(N-i-Pr)-N(CO2-i-Pr)-NH(CO2-i-Pr)] (24), [(S)-(2-OH-1-C10H6-1′-C10H6-2′-O-P(O)(NH-t-Bu)2] (36) and [(t-BuNH)(O)P(μ-N-t-Bu)2P(O)(CHCCMe2)] (40) are also reported.

  炔烃/烯烃/丙二烯的膦活化反应以及Mitsunobu反应涉及大量的磷化学反应。借助于简单的环二磷氮烷，已经完成了许多与拟议的中间体相似的化合物的表征。强调了在Pd催化的N-芳基化反应中使用环二磷氮烷。讨论了磷化合物中分子非化学计量的结果以及使用手性磷系统的结果。还描述了涉及环二磷氮烷的烯丙基磷酰胺的合成。新的化合物的X射线结构[（吨-BuNH）（的PhCH 2 CH（CN）CH 2 - ）P（μ-N-吨-Bu）2 P（NH-吨-Bu）]+ [HCO 3 ] - （13），[（吨-BuNH）P（μ-N-吨-Bu）2 P（N-吨-Bu）-C（CH 2）CH（C 6 H ^ 4 -4- Me）-P（O）（OCH 2 CMe 2 CH 2 O）]（18），[（i -PrNH）P（μ-N- t -Bu）2 P（N- i -Pr）-N（CO 2 -我-Pr）-NH（CO 2 -我-Pr）]（24）[（小号）
• Cyclodiphosph(III)azane chemistry – Ylides from the reaction of [(RNH)P-N(t-Bu)]2 [R=t-Bu, i-Pr] with dimethyl maleate and chiral ansa-type derivatives from reaction of [ClP-N(t-Bu)]2 with a substituted BINOL
  作者：K.C. Kumara Swamy、G. Gangadhararao、Venu Srinivas、N.N. Bhuvan Kumar、E. Balaraman、Manab Chakravarty

  DOI：10.1016/j.ica.2010.12.072

  日期：2011.6

  Use of a simple inorganic ring system with the cyclodiphosph(III) azane skeleton [e.g. [(RNH)P-N(t-Bu)](2) [R = t-Bu (7), i-Pr (8)] to probe some of the intermediates proposed in phosphine mediated organic reactions is highlighted. Thus the reaction of 7-8 with the allenylphosphine oxide Ph2P(O)C(Ph)=C=CH2 (9) affords the phosphinimines [(RNH)P(mu-N-t-Bu)(2)P(=N-R)-C(=CH2) CH(Ph)-P(O)Ph-2] [R= t-Bu (10), i-Pr (11)], while a similar reaction of 7-8 with dimethyl maleate (or dimethyl fumarate) affords the ylides [(RNH) P(mu-N-t-Bu)(2)P(NH-R)=C(CO2Me)-CH2(CO2Me) [R = t-Bu (18), i-Pr (19)]. The implication of such reactions on phosphine mediated organic transformations including Morita-Baylis-Hillman reaction is mentioned. In a rather rare type of situation, an unusually long phosphoryl (P=O) bond [1.538 (5) angstrom] as revealed the X-ray structure of (R)-6,6'-(t-Bu)(2)-1,1'-(C10H5)(2)-2,2'-O-2-}P(O)(N-t-Bu)(2)-P(Se)} (27) is rationalized by means of crystallographic disorder in packing after comparing the data with that in the literature and 1,1'-(C10H6)(2)-2,2'-O-2}P(Se)(N-t-Bu)(2)-P(Se)} (29). X-ray structures of the new compounds 10-11, 18-19, 27 and 29 are discussed. Compound 10 crystallizes in the chiral space group Pca2(1) with (S)-chirality at the carbon center [-C(=CH2) CH(Ph)-P] suggesting a case of spontaneous resolution through crystallization. (C) 2011 Elsevier B.V. All rights reserved.