2-cyanoprop-2-yl 4-methoxydithiobenzoate | 851729-43-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-cyanoprop-2-yl 4-methoxydithiobenzoate
• 英文别名: 2-Cyanopropan-2-yl 4-methoxybenzenecarbodithioate
• CAS: 851729-43-6
• 化学式: C₁₂H₁₃NOS₂
• 分子量: 251.373
• InChiKey: QBGCZLWFMRCBHX-UHFFFAOYSA-N

物化性质

• 沸点：
  377.8±52.0 °C(Predicted)
• 密度：
  1.198±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  90.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  偶氮二异丁腈 、 bis(4-methoxyphenyl thiocarbonyl)disulfide 以 乙酸乙酯 为溶剂， 以86%的产率得到2-cyanoprop-2-yl 4-methoxydithiobenzoate
  参考文献：
  名称：

  Searching for More Effective Agents and Conditions for the RAFT Polymerization of MMA:  Influence of Dithioester Substituents, Solvent, and Temperature

  摘要：

  A series of tertiary dithiobenzoates differently substituted on the phenyl group (Z) were synthesized in order to investigate the RAFT-mediated polymerization of MMA. The chain-transfer agent 2-eyanoprop-2-yl dithiobenzoate, although an excellent RAFT agent for polymerization of MMA, does not yield a very narrow polydispersed polymer at low conversion. The introduction of electron-withdrawing substituents on the dithiobenzoate aromatic ring improves the activity of the chain-transfer agent narrowing the molecular weight distribution, especially in the first 2 h of the process; conversely, electron-donating substituents deteriorate the performance of the process in the early stages. Substituents on the dithiobenzoate that, for reasons of steric hindrance reduce the conjugation of the phenyl with the C=S double bond of the dithiogroup, diminish the effectiveness of the chain-transfer agent. The nature of the leaving group (R) also has a strong influence on the process: the substitution of 2-cyanoprop-2-yl with the bulkier 2-cyano-4-methylpent-2-yl as leaving group improves remarkably the MMA polymerization, especially in the early stages. The solvent effect on MMA RAFT polymerization using benzene, acetonitrile, and DMF was also investigated. The lower propagation rate constant of MMA in benzene gives rise to reduced rates of polymerization but narrower polydispersities of the polymer, especially at low conversions. The RAFT polymerizations of MMA were carried out at 60 and 90 degrees C to assess the temperature dependence of the process. The higher temperature increases both the rate of polymerization and the transfer constant of the RAFT agent, resulting in lower polydispersities at a given conversion. Ab initio calculations confirmed the observed experimental results.

  DOI：

  10.1021/ma0480650

文献信息

• POLYMER COMPOSITION AND PHOTORESIST COMPRISING SAME
  申请人：Kramer John W.

  公开号：US20120328983A1

  公开（公告）日：2012-12-27

  A polymer comprises the polymerized product of monomers comprising an acid-deprotectable monomer, a base-soluble monomer, a lactone-containing monomer, and a photoacid-generating monomer; a chain transfer agent of the formula; wherein Z is a y valent C 1-20 organic group, x is 0 or 1, R d is a substituted or unsubstituted C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, or C 7-20 aralkyl; and optionally, an initiator.

  这段话的意思是：该聚合物包括由单体聚合而成的产物，其中单体包括具有去保护酸单体、可溶于碱的单体、含有内酯的单体和光酸生成单体；以及具有以下式子的链转移剂：其中Z是一个y价的C1-20有机基团，x为0或1，Rd是取代或未取代的C1-20烷基、C3-20环烷基、C6-20芳基或C7-20芳基烷基；可选地，还包括引发剂。
• Polymer composition and photoresist comprising same
  申请人：Kramer John W.

  公开号：US10025181B2

  公开（公告）日：2018-07-17

  A polymer comprises the polymerized product of monomers comprising an acid-deprotectable monomer, a base-soluble monomer, a lactone-containing monomer, and a photoacid-generating monomer; a chain transfer agent of the formula; wherein Z is a y valent C1-20 organic group, x is 0 or 1, Rd is a substituted or unsubstituted C1-20 alkyl, C3-20 cycloalkyl, C6-20 aryl, or C7-20 aralkyl; and optionally, an initiator.

  一种聚合物由以下单体的聚合产物组成：一种可酸保护的单体、一种碱溶性单体、一种含内酯的单体和一种产生光酸的单体；一种链转移剂，其化学式为 其中 Z 是 y 价 C1-20 有机基团，x 是 0 或 1，Rd 是取代或未取代的 C1-20 烷基、C3-20 环烷基、C6-20 芳基或 C7-20 芳烷基；以及可选的引发剂。
• CHLOROPRENE-BASED BLOCK COPOLYMER, SOAPLESS POLYCHLOROPRENE-BASED LATEX, AND PROCESSES FOR PRODUCING THE SAME
  申请人：Ozoe Shinji

  公开号：US20090036608A1

  公开（公告）日：2009-02-05

  An object of the present invention is to provide a novel polychloroprene-based copolymer, a soapless polychloroprene-based latex, and a process for producing the same in a simple and convenient manner, which are intended to be used for the improvement in adhesiveness and water resistance of a conventional polychloroprene adhesive or the improvement in oil resistance and adhesiveness of a styrene-butadiene block copolymer. The invention relates to a chloroprene-based block copolymer comprising a polymer (A) having a composition represented by the following formula (1) and a chloroprene-based polymer (B), the polymer (A) being linked to one terminal or both terminals of the chloroprene-based polymer (B), and the total amount of the 1,2-bond and the isomerized 1,2-bond in the chloroprene-based polymer (B) as determined by carbon-13 nuclear magnetic resonance spectrometry being 2.0 mol % or less; a soapless polychloroprene-based latex comprising an amphipathic chloroprene copolymer having a hydrophobic chloroprene-based polymer and a hydrophilic oligomer or polymer having an acidic functional group linked to the hydrophobic chloroprene-based polymer and 2 wt % or less of an emulsifying agent; and a process for producing the same: wherein U represents hydrogen, a methyl group, a cyano group, or a substituted alkyl group; V represents a phenyl group, a substituted phenyl group, a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, an allyloxycarbonyl group, a substituted allyloxycarbonyl group, an acyloxy group, a substituted acyloxy group, an amido group, or a substituted amido group; X represents hydrogen, a methyl group, chlorine, or a cyano group; Y represents hydrogen, chlorine, or a methyl group; Q represents a polymerization residue of maleic anhydride, citraconic acid, maleic acid, fumalic acid, a maleate ester, or a fumalate ester; and k, n, and m each represents an integer of 0 or more.
• Searching for More Effective Agents and Conditions for the RAFT Polymerization of MMA:  Influence of Dithioester Substituents, Solvent, and Temperature
  作者：Massimo Benaglia、Ezio Rizzardo、Angelo Alberti、Maurizio Guerra

  DOI：10.1021/ma0480650

  日期：2005.4.1

  A series of tertiary dithiobenzoates differently substituted on the phenyl group (Z) were synthesized in order to investigate the RAFT-mediated polymerization of MMA. The chain-transfer agent 2-eyanoprop-2-yl dithiobenzoate, although an excellent RAFT agent for polymerization of MMA, does not yield a very narrow polydispersed polymer at low conversion. The introduction of electron-withdrawing substituents on the dithiobenzoate aromatic ring improves the activity of the chain-transfer agent narrowing the molecular weight distribution, especially in the first 2 h of the process; conversely, electron-donating substituents deteriorate the performance of the process in the early stages. Substituents on the dithiobenzoate that, for reasons of steric hindrance reduce the conjugation of the phenyl with the C=S double bond of the dithiogroup, diminish the effectiveness of the chain-transfer agent. The nature of the leaving group (R) also has a strong influence on the process: the substitution of 2-cyanoprop-2-yl with the bulkier 2-cyano-4-methylpent-2-yl as leaving group improves remarkably the MMA polymerization, especially in the early stages. The solvent effect on MMA RAFT polymerization using benzene, acetonitrile, and DMF was also investigated. The lower propagation rate constant of MMA in benzene gives rise to reduced rates of polymerization but narrower polydispersities of the polymer, especially at low conversions. The RAFT polymerizations of MMA were carried out at 60 and 90 degrees C to assess the temperature dependence of the process. The higher temperature increases both the rate of polymerization and the transfer constant of the RAFT agent, resulting in lower polydispersities at a given conversion. Ab initio calculations confirmed the observed experimental results.