α,α'-bis<3,5-bis(chloromethyl)phenoxy>-p-xylene | 135989-92-3

• 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: α,α'-bis<3,5-bis(chloromethyl)phenoxy>-p-xylene
• 英文别名: 1,4-bis((3,5-bis(chloromethyl)phenoxy)methyl)benzene；α,α'-bis[3,5-bis(chloromethyl)phenoxy]-p-xylene；1-[[4-[[3,5-Bis(chloromethyl)phenoxy]methyl]phenyl]methoxy]-3,5-bis(chloromethyl)benzene
• CAS: 135989-92-3
• 化学式: C₂₄H₂₂Cl₄O₂
• 分子量: 484.249
• InChiKey: IOEQYSKUCYEVTJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  30
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  α,α'-bis<3,5-bis(chloromethyl)phenoxy>-p-xylene 在 氢氧化钾 、 乙二胺 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醇 、 水 、 苯 为溶剂， 反应 26.0h， 生成 28-bromo-4,11-dioxa-18,38,43,47-tetrathianonacyclo[22.17.3.314,32.26,9.13,40.112,16.126,30.020,25.031,36]dopentaconta-1,3(45),6(52),7,9(51),12,14,16(50),20,22,24,26,28,30(49),31(36),32,34,40-octadecaene
  参考文献：
  名称：

  Synthesis of self-filled, vaulted, and intracavity functionalized cappedophanes

  摘要：

  Two approaches to the synthesis of vaulted cappedophanes 3v are described. In the first, the walls and ceiling were prefabricated as in tetrathiol 5 (10a and 10b, Scheme II, are specific examples), which was then coupled with a m-terphenyl tetrabromide such as 4. This route was most successful when the m-terphenyl base carried a large substituent (Ph, Br) in the 5' position. Thus tetrathiol 10a and tetrabromide 25 gave vaulted cappedophane 27v in good yield (Scheme VIII). In the absence of a 5' substituent, the major product was the self-filled conformer. For example, 10a and 4 gave mainly 11sf (62%) and only 2% of its vaulted conformer 11v (Scheme III), and tetrathiol 10b reacted with 4 to give (79%) only the self-filled conformer 15sf (Scheme IV). In the second approach, a cuppedophane with suitably functionalized walls was first constructed, and the cap was attached in a second step. For example, bisphenol 29, when coupled with p-xylylene dibromide, gave mainly vaulted conformer 11v (51%) and only a trace of 11sf (Scheme IX). Extension of this method to several other dihalides, however, gave mainly self-filled conformers (Schemes XI and XII) and even p-xylylene dibromide gave only self-filled product 33sf when the bisphenol contained a substituent at C2' of the m-terphenyl base (Scheme XIII). The reasons for the predominant formation of self-filled vis-a-vis vaulted cappedophane conformers are discussed. These studies open the way for the synthesis of vaulted cappedophanes containing functionality within the molecular cavity.

  DOI：

  10.1021/jo00019a032
• 作为产物：
  描述：

  α,α'-bis<3,5-bis(hydroxymethyl)phenoxy>-p-xylene 在 吡啶 、 氯化亚砜 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以92%的产率得到α,α'-bis<3,5-bis(chloromethyl)phenoxy>-p-xylene
  参考文献：
  名称：

  Synthesis of self-filled, vaulted, and intracavity functionalized cappedophanes

  摘要：

  Two approaches to the synthesis of vaulted cappedophanes 3v are described. In the first, the walls and ceiling were prefabricated as in tetrathiol 5 (10a and 10b, Scheme II, are specific examples), which was then coupled with a m-terphenyl tetrabromide such as 4. This route was most successful when the m-terphenyl base carried a large substituent (Ph, Br) in the 5' position. Thus tetrathiol 10a and tetrabromide 25 gave vaulted cappedophane 27v in good yield (Scheme VIII). In the absence of a 5' substituent, the major product was the self-filled conformer. For example, 10a and 4 gave mainly 11sf (62%) and only 2% of its vaulted conformer 11v (Scheme III), and tetrathiol 10b reacted with 4 to give (79%) only the self-filled conformer 15sf (Scheme IV). In the second approach, a cuppedophane with suitably functionalized walls was first constructed, and the cap was attached in a second step. For example, bisphenol 29, when coupled with p-xylylene dibromide, gave mainly vaulted conformer 11v (51%) and only a trace of 11sf (Scheme IX). Extension of this method to several other dihalides, however, gave mainly self-filled conformers (Schemes XI and XII) and even p-xylylene dibromide gave only self-filled product 33sf when the bisphenol contained a substituent at C2' of the m-terphenyl base (Scheme XIII). The reasons for the predominant formation of self-filled vis-a-vis vaulted cappedophane conformers are discussed. These studies open the way for the synthesis of vaulted cappedophanes containing functionality within the molecular cavity.

  DOI：

  10.1021/jo00019a032

文献信息

• Decorating Poly(alkyl aryl-ether) Dendrimers with Metallacarboranes
  作者：Rosario Núñez、Emilio José Juárez-Pérez、Francesc Teixidor、Rosa Santillan、Norberto Farfán、Arturo Abreu、Rebeca Yépez、Clara Viñas

  DOI：10.1021/ic101306w

  日期：2010.11.1

  A new family of polyanionic poly(alkyl aryl-ether) metallodendrimers decorated with four and eight cobaltabisdicarbollide units have been obtained in high yield by the ring-opening reaction of cyclic oxonium [3,3'-Co(8-(C2H4O)(2)-1,2-C2B9H10)-(1',2'-C2B9H11 )] with alkoxides formed by deprotonation of terminal alcohols in the alpha,alpha'-bis[3,5-bis(hydroxymehyl)phenoxy]-p-xylene, alpha,alpha'-bis[3,5-bis(hydroxymehyl)phenoxy]-m-xylene, alpha,alpha'-bis[3,5-bis-[3,5-bis(hydroxymethyl)phenoxy]methylen]phenoxy]-m-xylene and alpha,alpha'-bis[3,5-bis-[3,5-bis(hydroxymethyl)phenoxy]methylen]-phenoxy]-m-xylene dendrimers. The crystal structure of the precursor alpha,alpha'-bis[3,5-bis(chloromethyl)phenoxy]-p-xylene is also described. Final products are fully characterized by FTIR, NMR, UV vis spectroscopies and elemental analysis. For metallodendrimers, the UV vis absorptions have been a good tool for estimating the experimental number of cobaltabisdicarbollide units peripherally attached to the dendrimeric structure and consequently to corroborate the complete functionalization of the dendrimers.
• New soluble multi-site phase transfer catalysts and their catalysis for dichlorocarbene addition to citronellal assisted by ultrasound—A kinetic study
  作者：Eagambaram Murugan、Gurusamy Tamizharasu

  DOI：10.1016/j.molcata.2012.05.020

  日期：2012.11

  Two new soluble multi-site phase transfer catalysts (MPTCs), viz., 1,4-bis-(triethylmethylene ammonium chloride)-2,5-dimethyl benzene (BTMACD) containing di-site and 1.4-bis((3,5-bis(triethylmethyleneammonium chloride)phenoxy)methyl)benzene (TEMACPB) containing tetra-site were prepared and proved by FT-IR, H-1 NMR, C-13 NMR, mass and elemental analysis. The enhancement of C-N peak intensity at 1179 cm(-1) noticed in FT-IR, the agreement of m/z values, viz., 405 and 888 for di-site and tetra-site respectively with their theoretical values and the percentage of C. H, N elements noticed in elemental analysis has strongly supported the presence of di-site and tetra-site in the BTMACD and TEMACPB catalysts. Further, the presence of number of active-sites in each catalyst was again confirmed by determining their pseudo-first order rate constant for dichlorocarbene addition to citronellal in the presence of ultrasonic irradiation/mechanical stirring. The comparative study reveals that the k(obs), determined with the combination of ultrasound and mechanical stirring has shown more activity (3 fold) than with their individual effect. Further, the detailed kinetic study performed with superior tetra-site MPTC (TEMACPB) reveals that the k(obs) are dependent with the stirring speed, [substrate]center dot[catalyst]center dot[NaOH] and temperature. Based on the kinetic results, thermodynamic parameters are evaluated and an interfacial mechanism is proposed. (C) 2012 Elsevier B.V. All rights reserved.
• Synthesis of self-filled, vaulted, and intracavity functionalized cappedophanes
  作者：Thottumkara K. Vinod、Harold Hart

  DOI：10.1021/jo00019a032

  日期：1991.9

  Two approaches to the synthesis of vaulted cappedophanes 3v are described. In the first, the walls and ceiling were prefabricated as in tetrathiol 5 (10a and 10b, Scheme II, are specific examples), which was then coupled with a m-terphenyl tetrabromide such as 4. This route was most successful when the m-terphenyl base carried a large substituent (Ph, Br) in the 5' position. Thus tetrathiol 10a and tetrabromide 25 gave vaulted cappedophane 27v in good yield (Scheme VIII). In the absence of a 5' substituent, the major product was the self-filled conformer. For example, 10a and 4 gave mainly 11sf (62%) and only 2% of its vaulted conformer 11v (Scheme III), and tetrathiol 10b reacted with 4 to give (79%) only the self-filled conformer 15sf (Scheme IV). In the second approach, a cuppedophane with suitably functionalized walls was first constructed, and the cap was attached in a second step. For example, bisphenol 29, when coupled with p-xylylene dibromide, gave mainly vaulted conformer 11v (51%) and only a trace of 11sf (Scheme IX). Extension of this method to several other dihalides, however, gave mainly self-filled conformers (Schemes XI and XII) and even p-xylylene dibromide gave only self-filled product 33sf when the bisphenol contained a substituent at C2' of the m-terphenyl base (Scheme XIII). The reasons for the predominant formation of self-filled vis-a-vis vaulted cappedophane conformers are discussed. These studies open the way for the synthesis of vaulted cappedophanes containing functionality within the molecular cavity.