2,3,5,6-tetracyanohydroquinone | 3533-07-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 2,3,5,6-tetracyanohydroquinone
• 英文别名: tetracyanohydroquinone；Tetracyanohydrochinon；TCHQ；2.3.5.6-Tetracyan-hydrochinon；Tetracyano-hydrochinon；Tetracyanhydrochinon；3,6-Dihydroxybenzene-1,2,4,5-tetracarbonitrile
• CAS: 3533-07-1
• 化学式: C₁₀H₂N₄O₂
• 分子量: 210.151
• InChiKey: WNFOACCKIUYYII-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  136
• 氢给体数：
  2
• 氢受体数：
  6

安全信息

• 海关编码：
  2926909090

反应信息

• 作为反应物：
  描述：

  2,3,5,6-tetracyanohydroquinone 在 sodium nitrate 、 溴 、 silver nitrate 作用下， 以 水 为溶剂， 反应 1.17h， 生成 monosodium(1+) salt of 3,6-dihydroxy-1,2,4,5-benzenetetracarbonitrile
  参考文献：
  名称：

  Cyanil. Synthesis and characterization of the strongest isolated electron acceptor and its reduced forms

  摘要：

  The strong acceptor tetracyano-1,4-benzoquinone, cyanil, Q[nu(C=N) at 2210 w and 2241 w cm-1; nu(C=O) at 1697 s cm-1 (CH2Cl2); nu(C=C) 1616 s cm-1 (Raman)], as well as tetracyanohydrobenzoquinone, QH2(2241 m and 2263 m cm-1), the radical anion, [Q].-[nu(C=N) approximately 2216 m cm-1 (MeCN)], anion [QH]-, dianions [Q]2- (2185 s cm-1), [H]+[Q]2-, and the dimer dianion [Q]2(2-)(2217 m and 2226 sh cm-1) have been prepared. QH2 was prepared from NaCN and p-bromanil, and Q was prepared from the bromine oxidation of the disilver salt of QH2, QAg2. QAg2 is a versatile synthon for the preparation of Q, [QH]-, [H]+[Q]2-, and [Q]2-. The single-crystal X-ray structures of QH2, Na+[H]+[Q]2-, [Me4N]+[H]+[Q]2-, [Et4N]+[QH]-, [n-Bu4N]+[QH]-, {[Et4N]+}2[Q]2(2-), {[(Ph3P)2N]+}2[Q]2-, Q, [Fe(C5Me5)2].+[H]+[Q]2-, and {[Fe(C5Me5)2].+}2[Q]2(2-) have been determined. The average CO (OC-CCN, and NC-CN) distances are 1.204 (1.488, and 1.338), 1.233 (1.463, and 1.378),1.268 (1.426, and 1.414), and 1.322 (1.413, and 1.372) angstrom for Q, [Q]-, [Q]2-, and QH2, respectively. Several salts exhibit very strong intermolecular hydrogen bonding with O...O separations less than 2.5 angstrom observed for the [Et4N]+[QH]- (2.38 angstrom), [Me4N]+[H]+[Q]2- (2.43 angstrom), and Na+[H]+[Q]2- (2.48 angstrom) salts. (The former is the shortest reported for an an organic system with intermolecular hydrogen bonding.) The degree of protonation varies with counterion with examples of [QH]- and [H]+[Q]2- being observed and strongly influences the electronic and nu(C=N) absorptions. The radical anion was structurally characterized as its diamagnetic dimer dianion, [Q]2(2-), with an intradimer separation of 2.88 angstrom. The EPR of [Q].- in dilute CH2Cl2/MeCN displays hyperfine interaction with four equivalent nitrogens (a(CN) = 0.32 G) and two types of C-13 (2.58 and 5.25 G). Cyanil is the strongest acceptor that has been isolated in the neutral form and has three quasi-reversible one-electron reductions at 0.90,0.09, and -1.81 V vs SCE in MeCN. It is unstable in aqueous media. The reduction potential of cyanil is 0.30 V or more greater than those of DDQ, n-C4(CN)6, and perfluoro-7,7,8,8-tetracyano-p-quinodimethane (TCNQF4). Q dehydrogenates 2,3-dichloro-5,6-dicyanohydroquinone (H2DDQ); thus it is a stronger hydrogen abstraction reagent than conventionally used DDQ. Molecular orbital (ab initio) calculations are in general agreement with the above results, and optimized geometries were used to understand the complex crystal structures.

  DOI：

  10.1021/jo00053a017
• 作为产物：
  描述：

  2.3.4.5-Tetracyan-p-phenylendiamin 生成 2,3,5,6-tetracyanohydroquinone
  参考文献：
  名称：

  Tetracyano-p-phenylenediamine

  摘要：

  DOI：

  10.1021/jo01020a535

文献信息

• Composition consisting of a dendrimer and an active substance
  申请人：DSM N.V.

  公开号：EP0684044A2

  公开（公告）日：1995-11-29

  The invention relates to a composition consisting of a dendrimer provided with blocking agents and an active substance occluded in the dendrimer. According to the invention a blocking agent is a compound which is sterically of sufficient size, which readily enters into a chemical bond with the terminal groups of a dendrimer and which can also be split off from the dendrimer or be modified without thereby affecting the chemical structure of the dendrimer and the active substance. The blocking agent can be provided with protective groups. Such conjugates have the advantage that the time at which the releasing of the active substance starts, can be controlled. The invention also relates to a process for the preparation of such a composition and to a process for the controlled release of the active substance.

  本发明涉及一种组合物，该组合物由含有阻断剂的树枝状聚合物和湮没在树枝状聚合物中的活性物质组成。 根据本发明，阻断剂是一种化合物，其立体尺寸足够大，容易与树枝状聚合物的末端基团发生化学键合，也可以从树枝状聚合物中分离出来或进行改性而不影响树枝状聚合物和活性物质的化学结构。阻断剂可以带有保护基团。 这种共轭物的优点是可以控制活性物质开始释放的时间。 本发明还涉及制备这种组合物的工艺和控制释放活性物质的工艺。
• BUCSIS L.; FRIEDRICH K., CHEM. BER. <CHBE-AM>, 1976, 109, NO 7, 2462-2468
  作者：BUCSIS L.、 FRIEDRICH K.

  DOI：——

  日期：——
• US4379939A
  申请人：——

  公开号：US4379939A

  公开（公告）日：1983-04-12
• US4571435A
  申请人：——

  公开号：US4571435A

  公开（公告）日：1986-02-18
• Cyanil. Synthesis and characterization of the strongest isolated electron acceptor and its reduced forms
  作者：Carlos Vazquez、Joseph C. Calabrese、David A. Dixon、Joel S. Miller

  DOI：10.1021/jo00053a017

  日期：1993.1

  The strong acceptor tetracyano-1,4-benzoquinone, cyanil, Q[nu(C=N) at 2210 w and 2241 w cm-1; nu(C=O) at 1697 s cm-1 (CH2Cl2); nu(C=C) 1616 s cm-1 (Raman)], as well as tetracyanohydrobenzoquinone, QH2(2241 m and 2263 m cm-1), the radical anion, [Q].-[nu(C=N) approximately 2216 m cm-1 (MeCN)], anion [QH]-, dianions [Q]2- (2185 s cm-1), [H]+[Q]2-, and the dimer dianion [Q]2(2-)(2217 m and 2226 sh cm-1) have been prepared. QH2 was prepared from NaCN and p-bromanil, and Q was prepared from the bromine oxidation of the disilver salt of QH2, QAg2. QAg2 is a versatile synthon for the preparation of Q, [QH]-, [H]+[Q]2-, and [Q]2-. The single-crystal X-ray structures of QH2, Na+[H]+[Q]2-, [Me4N]+[H]+[Q]2-, [Et4N]+[QH]-, [n-Bu4N]+[QH]-, [Et4N]+}2[Q]2(2-), [(Ph3P)2N]+}2[Q]2-, Q, [Fe(C5Me5)2].+[H]+[Q]2-, and [Fe(C5Me5)2].+}2[Q]2(2-) have been determined. The average CO (OC-CCN, and NC-CN) distances are 1.204 (1.488, and 1.338), 1.233 (1.463, and 1.378),1.268 (1.426, and 1.414), and 1.322 (1.413, and 1.372) angstrom for Q, [Q]-, [Q]2-, and QH2, respectively. Several salts exhibit very strong intermolecular hydrogen bonding with O...O separations less than 2.5 angstrom observed for the [Et4N]+[QH]- (2.38 angstrom), [Me4N]+[H]+[Q]2- (2.43 angstrom), and Na+[H]+[Q]2- (2.48 angstrom) salts. (The former is the shortest reported for an an organic system with intermolecular hydrogen bonding.) The degree of protonation varies with counterion with examples of [QH]- and [H]+[Q]2- being observed and strongly influences the electronic and nu(C=N) absorptions. The radical anion was structurally characterized as its diamagnetic dimer dianion, [Q]2(2-), with an intradimer separation of 2.88 angstrom. The EPR of [Q].- in dilute CH2Cl2/MeCN displays hyperfine interaction with four equivalent nitrogens (a(CN) = 0.32 G) and two types of C-13 (2.58 and 5.25 G). Cyanil is the strongest acceptor that has been isolated in the neutral form and has three quasi-reversible one-electron reductions at 0.90,0.09, and -1.81 V vs SCE in MeCN. It is unstable in aqueous media. The reduction potential of cyanil is 0.30 V or more greater than those of DDQ, n-C4(CN)6, and perfluoro-7,7,8,8-tetracyano-p-quinodimethane (TCNQF4). Q dehydrogenates 2,3-dichloro-5,6-dicyanohydroquinone (H2DDQ); thus it is a stronger hydrogen abstraction reagent than conventionally used DDQ. Molecular orbital (ab initio) calculations are in general agreement with the above results, and optimized geometries were used to understand the complex crystal structures.