2,4-di-tert-butylphenyl phosphorodichloridite

• 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: 2,4-di-tert-butylphenyl phosphorodichloridite
• 英文别名: dichloro(2,4-di-tert-butylphenoxy)phosphite；dichloro-2,4-di-tert-butylphenyl phosphite；2,4-t-Bu2-C6H3-phosphorodichloridite；2,4-di-tert-butylphenoxydichlorophosphine；2,4-di-tert-butylphenyl dichlorophosphite；Dichloro-(2,4-ditert-butylphenoxy)phosphane
• 化学式: C₁₄H₂₁Cl₂OP
• 分子量: 307.2
• InChiKey: MAPNNXUXBGIKKV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,4-di-tert-butylphenyl phosphorodichloridite 以0%的产率得到
  参考文献：
  名称：

  Gloede Joerg, Phosph., sulfur and Silicon and Relat. Elem., 75 (1993) N 1-4, S 217-220

  摘要：

  DOI：
• 作为产物：
  描述：

  2,4-二叔丁基苯酚 在 三乙胺 、 三氯化磷 作用下， 以 甲苯 为溶剂， 反应 18.0h， 以96%的产率得到2,4-di-tert-butylphenyl phosphorodichloridite
  参考文献：
  名称：

  Chiral triaryl phosphite-based palladacycles and platinacycles: synthesis and application to asymmetric Lewis acid catalysis

  摘要：

  通过将PCl2(OAr)与R-或S-BINOL反应，制备了光学纯的单膦酸酯P(OAr)(BINOLate) (7, 其中Ar = 2,4-二叔丁基苯基)。将[PdCl2(NCMe)2]与7反应，根据反应条件得到[PdCl2(7)2] (9)或二核邻金属配合物[Pd2Cl2(7-H)2] (8)。8的桥断裂反应得到当L = PPh3或7时与碳反式排列的[PdCl(7-H)(L)]，当L = N-杂环卡宾时与碳顺式排列。将[PtCl2(NCtBu)2]与7反应得到[PtCl2(7)2] (18)，进一步与PtCl2反应得到二核[Pt2Cl2(7-H)2] (17)和顺式-[PtCl(7-H)(7)] (19)的混合物。含环金属化7的钯配合物被筛选用于催化苯硼酸对环己烯-2-酮的1,4-共轭加成和苯甲醛与三丁基锡烯烃的烯丙基化反应。每种情况下的转化率一般都很高，但对映选择性较低（最好的情况下为15% 对映体过量）。8、17和[PdCl(7-H)(NHC)] (10a, 其中NHC = 1,3-(二甲基)咪唑啉-2-亚基)的X射线晶体结构已经确定。

  DOI：

  10.1039/b907333g

文献信息

• NMR and X-ray crystallographic studies of unsymmetrical 25,26;27,28-dibridged para-tert-butyl calix[4]arene bisphosphites with a large “through-space” P–P coupling
  作者：Pathik Maji、Setharampattu S. Krishnamurthy、Munirathinam Nethaji

  DOI：10.1039/b903771c

  日期：——

  Three 25,26-bridged para-tert-butyl-calix[4]arene phosphites, 1–3, have been synthesized by linking two proximal phenolic oxygen atoms of para-tert-butyl-calix[4]arene to a P(OR) [R = 2,6-But2–4-Me-C6H2 (1), 2,6-Pri2-C6H3 (2) or 2,4-But2-C6H3 (3)] moiety. NMR spectroscopic data and X-ray crystallographic studies (1 and 2 only) show that the calixarene framework in 1 adopts a cone conformation, whereas in 2 and 3 it assumes a partial cone conformation. Unsymmetrical 25,26;27,28-dibridged para-tert-butyl-calix[4]arene bisphosphites 5–7 have been synthesized by the reaction of 25,26-bridged para-tert-butyl-calix[4]arene phosphite 1 with (R′O)PCl2 [R′ = 2,4-But2-C6H3 (5), 2,6-Pri2-C6H3 (6) or (1R,2S,5R)-(−)menthyl (7)]. NMR investigations (homonuclear 31P COSY) revealed an unprecedented “through-space” phosphorus–phosphorus coupling of 223–244 Hz for these unsymmetrical 25,26;27,28-dibridged para-tert-butyl-calix[4]arene bisphosphites. The molecular structure of unsymmetrical 25,26;27,28-bridged bisphosphite 5 was determined by X-ray crystallography; the two phosphorus atoms are in close proximity and the P⋯P distance (3.543(2) Å) is less than the sum of their van der Walls radii.

  通过将对叔丁基杯[4]芳烃的两个近端酚羟基氧原子连接到P(OR) [R = 2,6-二丁基-4-甲基苯(1), 2,6-二异丙基苯(2)或2,4-二丁基苯(3)]基团上，合成了三种25,26-桥联的对叔丁基杯[4]芳烃膦酸酯1-3。核磁共振(NMR)光谱数据和X射线晶体学研究(仅1和2)显示，1中的杯芳烃骨架采用圆锥构型，而在2和3中则为部分圆锥构型。通过25,26-桥联的对叔丁基杯[4]芳烃膦酸酯1与(R'O)PCl2 [R' = 2,4-二丁基苯(5), 2,6-二异丙基苯(6)或(1R,2S,5R)-(+)-薄荷基(7)]反应，合成了三种不对称25,26;27,28-双桥联的对叔丁基杯[4]芳烃双膦酸酯5-7。NMR研究(同核31P COSY)揭示了这些不对称25,26;27,28-双桥联的对叔丁基杯[4]芳烃双膦酸酯中前所未有的“跨空间”磷-磷耦合，耦合常数为223-244 Hz。通过X射线晶体学确定了不对称25,26;27,28-双桥联双膦酸酯5的分子结构;两个磷原子距离很近，P···P距离(3.543(2) Å)小于它们范德华半径之和。
• HETEROCYCLIC SELENAPHOSPHITES AND PROCESS FOR PREPARATION THEREOF
  申请人：EVONIK DEGUSSA GMBH

  公开号：US20170158721A1

  公开（公告）日：2017-06-08

  Novel heterocyclic selenaphosphites, process for preparation thereof and use thereof as ligand for employment in complexes.

  新型杂环硒磷酸酯，其制备方法及用作配合物中配体的用途。
• Substituted 3,7,9-trioxa-1-aza-2,8-diphosphaspiro(4,5)decanes and
  申请人：Ciba-Geigy Corporation

  公开号：US05132426A1

  公开（公告）日：1992-07-21

  3,7,9-Trioxa-1-aza-2,8-diphosphaspiro[4.5]decanes of formula I ##STR1## wherein R.sub.1 and R.sub.2 are independently hydrogen, alkyl, cycloalkyl, bicycloalkyl, tricycloalkyl or aryl; or can be halogen when n or m is zero, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are independently hydrogen, alkyl, aralkyl or aryl; X and Y are independently --O--, --S-- or --NR.sub.16 -- where R.sub.16 is alkyl, cycloalkyl, alkenyl, aryl or aralkyl; W and Z are independently O or S; and n, m, o and p are independently zero or 1, are effective in stabilizing organic materials against the deleterious effects of oxygen, heat and/or actinic radiation.

  三氧杂-1-氮-2,8-二磷螺[4.5]癸烷的结构式为I，其中R.sub.1和R.sub.2分别为氢、烷基、环烷基、双环烷基、三环烷基或芳基；或当n或m为零时可以是卤素，R.sub.3、R.sub.4、R.sub.5和R.sub.6分别为氢、烷基、芳基烷基或芳基；X和Y分别为--O--、--S--或--NR.sub.16--，其中R.sub.16为烷基、环烷基、烯基、芳基或芳基烷基；W和Z分别为O或S；n、m、o和p分别为零或1，对稳定有机材料抵抗氧气、热和/或光辐射的有害影响具有有效作用。
• Substituted 3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decanes and
  申请人：Ciba-Geigy Corporation

  公开号：US05075482A1

  公开（公告）日：1991-12-24

  3,7,9-Trioxa-1-aza-2,8-diphosphaspiro[4.5]decanes of formula I ##STR1## wherein R.sub.1 and R.sub.2 are independently hydrogen, alkyl, cycloalkyl, bicycloalkyl, tricycloalkyl or aryl; or can be halogen when n or m is zero, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are independently hydrogen, alkyl, aralkyl or aryl; X and Y are independently --O-- --S--, or --NR.sub.16 -- where R.sub.16 is alkyl, cycloalkyl, alkenyl, aryl or aralkyl; W and Z are independently O or S; and n, m, o and p are independently zero or 1, are effective in stabilizing organic materials against the deleterious effects of oxygen, heat and/or actinic radiation.

  公式I中的3,7,9-Trioxa-1-aza-2,8-diphosphaspiro[4.5]decanes，其中R.sub.1和R.sub.2独立地为氢、烷基、环烷基、双环烷基、三环烷基或芳基；或当n或m为零时，可以是卤素，R.sub.3、R.sub.4、R.sub.5和R.sub.6独立地为氢、烷基、芳基烷基或芳基；X和Y独立地为--O--、--S--或--NR.sub.16--，其中R.sub.16为烷基、环烷基、烯基、芳基或芳基烷基；W和Z独立地为O或S；n、m、o和p独立地为零或1。这些化合物可以有效地稳定有机材料，抵抗氧气、热和/或光辐射的有害影响。
• Substituted 3,7,9-trioxa-1-aza-2,8-diphosphaspiro[4.5]decanes and stabilized compositions
  申请人：CIBA-GEIGY AG

  公开号：EP0474592A1

  公开（公告）日：1992-03-11

  3,7,9-Trioxa-1-aza-2,8-diphosphaspiro[4.5]decanes of formula I wherein R₁ and R₂ are independently hydrogen, alkyl, cycloalkyl, bicycloalkcyl, tricycloalkyl or aryl; or can be halogen when n or m is zero, R₃, R₄, R₅ and R₆ are independently hydrogen, alkyl, aralkyl or aryl; X and Y are independently -O-, -S- or -NR₁₆- where R₁₆ is alkyl, cycloalkcyl, alkenyl, aryl or aralkyl; W and Z are independently O or S; and n, m, o and p are independently zero or 1, are effective in stabilizing organic materials against the deleterious effects of oxygen, heat and/or actinic radiation.

  式 I 的 3,7,9-三氧杂-1-氮杂-2,8-二磷杂螺[4.5]癸烷 其中 R₁ 和 R₂ 独立地为氢、烷基、环烷基、双环烷基、三环烷基或芳基；或者当 n 或 m 为零时为卤素、 R₃、R₄、R₅ 和 R₆ 独立为氢、烷基、芳烷基或芳基； X 和 Y 独立地为-O-、-S-或-NR₁₆-，其中 R₁₆ 是烷基、环烷基、烯基、芳基或芳烷基； W 和 Z 独立地为 O 或 S；以及 n、m、o 和 p 独立地为 0 或 1，可有效稳定有机材料，使其免受氧气、热量和/或光辐射的有害影响。