4-tritylphenyl 10-bromodeca-5,7,9-triynoate | 1426234-06-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚酯
• 英文名称: 4-tritylphenyl 10-bromodeca-5,7,9-triynoate
• 英文别名: (4-tritylphenyl) 10-bromodeca-5,7,9-triynoate
• CAS: 1426234-06-1
• 化学式: C₃₅H₂₅BrO₂
• 分子量: 557.486
• InChiKey: DFNPQUMRSWASBS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.4
• 重原子数：
  38
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-tritylphenyl 10-bromodeca-5,7,9-triynoate 反应 0.02h， 以43%的产率得到(E)-9,10-dibromoicosa-9-ene-5,7,11,13,15-pentaynedioic acid bis(4-tritylphenyl)ester
  参考文献：
  名称：

  A multistep single-crystal-to-single-crystal bromodiacetylene dimerization

  摘要：

  有机分子在结晶状态下往往会显示出在溶液中无法观察到的不寻常物理或化学性质，原因就在于填料的限制和官能团的精确定位。在此，我们报告了溴二乙烯的单晶-单晶二聚反应，其中涉及异常大的原子位移以及多个键的裂解和形成。密度泛函理论计算支持这样一种机理，即二聚化是由晶体结构中碳碳短接触的性质促成的[2Â +Â 1]光环加成反应引发的。反应进行到理论转化程度时，结晶度没有降低，而且在制备规模上进行的反应产率也很高。此外，它还代表了(E)-1,2-二溴-1,2-二乙炔基乙烯的第一条合成途径，可作为制备分子碳支架的合成中间体。我们的发现既扩大了单晶到单晶反应的范围，又突出了其作为复杂转化合成工具的潜力。光化学诱导的固态溴端低聚（乙炔）二聚化反应可制备出 1,2-二溴乙炔。这种单晶到单晶的转化是通过多步反应进行的，除了大原子位移外，还涉及多个键的生成和断裂。该反应代表了一种原子高效、无催化剂的富碳功能分子支架途径。

  DOI：

  10.1038/nchem.1575
• 作为产物：
  描述：

  4-tritylphenyl 10-(trimethylsilyl)deca-5,7,9-triynoate 在 N-溴代丁二酰亚胺(NBS) 、 silver fluoride 作用下， 以 二氯甲烷 为溶剂， 生成 4-tritylphenyl 10-bromodeca-5,7,9-triynoate
  参考文献：
  名称：

  寡炔两亲物及其轮烷的简便合成

  摘要：

  含有一系列共轭三键（寡炔）的富含碳的有机化合物是相关的合成目标，但需要改进获得带有官能团的寡炔的途径。在这里，我们报告了两种具有糖苷或羧酸极性头基的寡炔两亲物的直接合成，研究了它们在水性介质中的自组装行为，以及它们作为前体用于形成具有环糊精主体的寡炔轮烷的前体。为此，我们使用了单、二或三乙炔结构单元，可以在原位获得相应的乙炔锌，并通过几个合成步骤有效地延长低聚炔链段。Negishi 耦合协议。此外，我们表明获得的寡炔衍生物可以脱保护以产生相应的两亲物。根据它们的头部基团，这些两亲物的超分子自组装在水性介质中产生了不同类型的富碳胶体聚集体。此外，它们的两亲性被用于在水中使用简单的主客体化学制备新型低聚环糊精轮烷。

  DOI：

  10.1039/c4sc03154g

文献信息

• Method for the preparation of a coating comprising oligomeric alkynes
  申请人：ÉCOLE POLYTECHNIQUE FÉDÉRALE DE LAUSANNE (EPFL) EPFL-TTO

  公开号：US10787576B2

  公开（公告）日：2020-09-29

  The invention relates to a method for the preparation of a coating comprising at least one coating layer on a substrate, the method comprising the steps of a. providing monomers of the type R—(N)x-(L)m-(C═C)n-(L′)o-(N′)y—R′, wherein R is a head moiety, R′ is a tail moiety, (C≡C)n is an oligoyne moiety, L and L′ are linker moieties, N and N′ independently are branched or unbranched optionally substituted C1-C25 alkyl moieties optionally containing 1 to 5 heteroatoms, x, m, o, and y are independently 0 or 1, n is 4 to 12, and wherein the head moiety allows for an interaction with the surface of the substrate; b. bringing the monomers into contact with the substrate wherein the interaction of the head moieties of the monomers with the surface of the substrate induces at least a part of the monomers to align in a defined manner thereby forming a film on the surface and bringing the oligoyne moieties of the monomers into close contact with each other; c. inducing a reaction between oligoyne moieties by providing an external stimulus so as to at least partially cross-link the aligned monomers, thereby forming a coating layer on the substrate. The invention further relates to a coating obtainable according to the method of the invention, the use of a coating obtainable according to the method of the invention, a substrate comprising a coating obtainable according to the invention and the use of solid substrate. The invention further relates to a method for the synthesis of the monomers according to the invention.

  本发明涉及一种在基底上制备包含至少一个涂层的涂层的方法，该方法包括以下步骤 a.提供R-(N)x-(L)m-(C═C)n-(L′)o-(N′)y-R′类型的单体，其中R是头部分子，R′是尾部分子，(C≡C)n是低碳原子分子，L和L′是连接分子、N和N′独立地是支链或未支链的任选取代的C1-C25烷基，任选含有1至5个杂原子，x、m、o和y独立地是0或1，n是4至12，其中头部分子允许与基质表面相互作用；b.使单体与基底接触，其中单体的头部分子与基底表面的相互作用诱导至少一部分单体以确定的方式排列，从而在表面上形成薄膜，并使单体的低聚酰亚胺分子彼此紧密接触； c. 通过提供外部刺激，诱导低聚酰亚胺分子之间发生反应，使排列的单体至少部分交联，从而在基底上形成涂层。本发明进一步涉及根据本发明方法可获得的涂层、根据本发明方法可获得的涂层的使用、包含根据本发明可获得的涂层的基底以及固体基底的使用。本发明进一步涉及根据本发明合成单体的方法。
• METHOD FOR THE PREPARATION OF A COATING COMPRISING OLIGOMERIC ALKYNES
  申请人：ECOLE POLYTECHNIQUE FEDERALE DE LAUSANNE (EPFL) EPFL-TTO

  公开号：US20190048202A1

  公开（公告）日：2019-02-14

  The invention relates to a method for the preparation of a coating comprising at least one coating layer on a substrate, the method comprising the steps of a. providing monomers of the type R—(N) x -(L) m -(C═C) n -(L′) o -(N′) y —R′, wherein R is a head moiety, R′ is a tail moiety, (C≡C) n is an oligoyne moiety, L and L′ are linker moieties, N and N′ independently are branched or unbranched optionally substituted C 1 -C 25 alkyl moieties optionally containing 1 to 5 heteroatoms, x, m, o, and y are independently 0 or 1, n is 4 to 12, and wherein the head moiety allows for an interaction with the surface of the substrate; b. bringing the monomers into contact with the substrate wherein the interaction of the head moieties of the monomers with the surface of the substrate induces at least a part of the monomers to align in a defined manner thereby forming a film on the surface and bringing the oligoyne moieties of the monomers into close contact with each other; c. inducing a reaction between oligoyne moieties by providing an external stimulus so as to at least partially cross-link the aligned monomers, thereby forming a coating layer on the substrate. The invention further relates to a coating obtainable according to the method of the invention, the use of a coating obtainable according to the method of the invention, a substrate comprising a coating obtainable according to the invention and the use of solid substrate. The invention further relates to a method for the synthesis of the monomers according to the invention.
• [EN] METHOD FOR THE PREPARATION OF A COATING<br/>[FR] PROCÉDÉ DE PRÉPARATION D'UN REVÊTEMENT
  申请人：ECOLE POLYTECHNIQUE FED DE LAUSANNE (EPFL) EPFL-TTO

  公开号：WO2016174266A2

  公开（公告）日：2016-11-03

  The invention relates to a method for the preparation of a coating comprising at least one coating layer on a substrate, the method comprising the steps of a. providing monomers of the type R- (N)x-(L)m- (C=C)n-(L')o- (N')y-R', wherein R is a head moiety, R' is a tail moiety, (C≡C)n is an oligoyne moiety, L and L' are linker moieties, N and N' independently are branched or unbranched optionally substituted C1-C25 alkyl moieties optionally containing 1 to 5 heteroatoms, x, m, o, and y are independently 0 or 1, n is 4 to 12, and wherein the head moiety allows for an interaction with the surface of the substrate; b. bringing the monomers into contact with the substrate wherein the interaction of the head moieties of the monomers with the surface of the substrate induces at least a part of the monomers to align in a defined manner thereby forming a film on the surface and bringing the oligoyne moieties of the monomers into close contact with each other; c. inducing a reaction between oligoyne moieties by providing an external stimulus so as to at least partially cross-link the aligned monomers, thereby forming a coating layer on the substrate. The invention further relates to a coating obtainable according to the method of the invention, the use of a coating obtainable according to the method of the invention, a substrate comprising a coating obtainable according to the invention and the use of solid substrate. The invention further relates to a method for the synthesis of the monomers according to the invention.
• Facile synthesis of oligoyne amphiphiles and their rotaxanes
  作者：Stephen Schrettl、Emmanuel Contal、Tobias N. Hoheisel、Martin Fritzsche、Sandor Balog、Ruth Szilluweit、Holger Frauenrath

  DOI：10.1039/c4sc03154g

  日期：——

  organic compounds containing a series of conjugated triple bonds (oligoynes) are relevant synthetic targets, but an improved access to oligoynes bearing functional groups would be desirable. Here, we report the straightforward synthesis of two series of oligoyne amphiphiles with glycoside or carboxylate polar head groups, investigate their self-assembly behavior in aqueous media, and their use as precursors

  含有一系列共轭三键（寡炔）的富含碳的有机化合物是相关的合成目标，但需要改进获得带有官能团的寡炔的途径。在这里，我们报告了两种具有糖苷或羧酸极性头基的寡炔两亲物的直接合成，研究了它们在水性介质中的自组装行为，以及它们作为前体用于形成具有环糊精主体的寡炔轮烷的前体。为此，我们使用了单、二或三乙炔结构单元，可以在原位获得相应的乙炔锌，并通过几个合成步骤有效地延长低聚炔链段。Negishi 耦合协议。此外，我们表明获得的寡炔衍生物可以脱保护以产生相应的两亲物。根据它们的头部基团，这些两亲物的超分子自组装在水性介质中产生了不同类型的富碳胶体聚集体。此外，它们的两亲性被用于在水中使用简单的主客体化学制备新型低聚环糊精轮烷。
• A multistep single-crystal-to-single-crystal bromodiacetylene dimerization
  作者：Tobias N. Hoheisel、Stephen Schrettl、Roman Marty、Tanya K. Todorova、Clémence Corminboeuf、Andrzej Sienkiewicz、Rosario Scopelliti、W. Bernd Schweizer、Holger Frauenrath

  DOI：10.1038/nchem.1575

  日期：2013.4

  Packing constraints and precise placement of functional groups are the reason that organic molecules in the crystalline state often display unusual physical or chemical properties not observed in solution. Here we report a single-crystal-to-single-crystal dimerization of a bromodiacetylene that involves unusually large atom displacements as well as the cleavage and formation of several bonds. Density functional theory computations support a mechanism in which the dimerization is initiated by a [2 + 1] photocycloaddition favoured by the nature of carbon–carbon short contacts in the crystal structure. The reaction proceeded up to the theoretical degree of conversion without loss of crystallinity, and it was also performed on a preparative scale with good yield. Moreover, it represents the first synthetic pathway to (E)-1,2-dibromo-1,2-diethynylethenes, which could serve as synthetic intermediates for the preparation of molecular carbon scaffolds. Our findings both extend the scope of single-crystal-to-single-crystal reactions and highlight their potential as a synthetic tool for complex transformations. The photochemical-induced dimerization of bromine-terminated oligo(ethynylene)s in the solid state is shown to give 1,2-dibromoeneynes on a preparative scale. This single-crystal-to-single-crystal transformation proceeds through a multistep reaction that involves the making and breaking of several bonds in addition to large atom displacements. The reaction represents an atom-efficient and catalyst-free pathway towards functional carbon-rich molecular scaffolds.

  有机分子在结晶状态下往往会显示出在溶液中无法观察到的不寻常物理或化学性质，原因就在于填料的限制和官能团的精确定位。在此，我们报告了溴二乙烯的单晶-单晶二聚反应，其中涉及异常大的原子位移以及多个键的裂解和形成。密度泛函理论计算支持这样一种机理，即二聚化是由晶体结构中碳碳短接触的性质促成的[2Â +Â 1]光环加成反应引发的。反应进行到理论转化程度时，结晶度没有降低，而且在制备规模上进行的反应产率也很高。此外，它还代表了(E)-1,2-二溴-1,2-二乙炔基乙烯的第一条合成途径，可作为制备分子碳支架的合成中间体。我们的发现既扩大了单晶到单晶反应的范围，又突出了其作为复杂转化合成工具的潜力。光化学诱导的固态溴端低聚（乙炔）二聚化反应可制备出 1,2-二溴乙炔。这种单晶到单晶的转化是通过多步反应进行的，除了大原子位移外，还涉及多个键的生成和断裂。该反应代表了一种原子高效、无催化剂的富碳功能分子支架途径。