3,6-bis(1-methylethoxy)-1,2-benzenedicarbonitrile | 201140-18-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 3,6-bis(1-methylethoxy)-1,2-benzenedicarbonitrile
• 英文别名: 3,6-di(isopropoxy)phthalonitrile；1,2-Benzenedicarbonitrile, 3,6-bis(1-methylethoxy)-；3,6-di(propan-2-yloxy)benzene-1,2-dicarbonitrile
• CAS: 201140-18-3
• 化学式: C₁₄H₁₆N₂O₂
• 分子量: 244.293
• InChiKey: OTNJVPFKUAGOTC-UHFFFAOYSA-N

物化性质

• 熔点：
  191-193 °C
• 沸点：
  412.5±45.0 °C(Predicted)
• 密度：
  1.10±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  66
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,6-bis(1-methylethoxy)-1,2-benzenedicarbonitrile 在 氨 、 sodium 作用下， 以 乙二醇 为溶剂， 生成 1-imino-4,7-bis(1-methylethoxy)-1H-isoindolin-3-amine
  参考文献：
  名称：

  Synthesis and structural characterization of 2,3,7,8,12,13,17,18-octakis(propyl), N, N, N′, N′-tetramethylaminoporphyrazines and 2,3,9,10,16,17,23,24-octa substituted phthalocyanine and the kinetic studies of their Co(II) and Cu(II) metalated complexes

  摘要：

  Three tetrapyrrole macrocyclic compounds 2,3,7,8,12,13,17,18-octakis(propyl)porphyrazine, N, N, N', N'-tetramethylamino porphyrazine hybrid and 2,3,9,10,16,17,23,24-octa substituted phthalocyanine were synthesized and characterized using elemental analysis, FTIR, H-1, C-13 NMR and UV-vis spectroscopic techniques. Kinetics of their metalation with Cu(II) and Co(II) and redox reaction of the complexes was studied and are reported here for the first time. It is suggested that deformation of the ring, which is a function of their peripheral functionalities, is essential for effective coordination of the ligands. The kinetic studies indicated metal based oxidation and ring based reduction for the reductants and oxidant respectively. The redox activity of the metal ions is dependent on the availability of their low energy level d-orbitals for charge transfer. It was therefore inferred that the nature of the metal ion and the peripheral substituents of these ligands and their complexes had significant effect on their reactivity. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.dyepig.2014.05.013
• 作为产物：
  描述：

  3,6-二羟基邻苯二甲腈 、 2-溴丙烷 在 potassium carbonate 作用下， 生成 3,6-bis(1-methylethoxy)-1,2-benzenedicarbonitrile
  参考文献：
  名称：

  酞菁锌衍生物的脂质囊泡对粪肠球菌的体外光动力活性

  摘要：

  带有八个非外围2-丙氧基取代基的酞菁锌（II）进行了物理化学研究，并掺入脂质囊泡后，被评估为抗菌光动力疗法的潜在光敏剂。通过MS和NMR技术对在大环化反应中获得的酞菁衍生物进行了表征。此外，通过HPLC分析确认了其化学纯度。X射线结构分析表明，酞菁衍生物的过度拥挤会导致大环核心π系统的强烈平面外扭曲。在酞菁锌（II）的UV-Vis吸收光谱中，发现了两个特征带：Soret（300-450 nm）和Q带（600-800 nm）。用时间分辨荧光光谱研究了单和双质子化酞菁衍生物的光物理性质。由于化合物在较高的酸浓度下分解，因此无法获得其三和四质子化形式。提出的锌（II）酞菁具有单重态氧产生值ΦΔ  = 0.18和0.16，光分解Φ的量子产率P  = 3.06∙10 -4和1.23∙10 -5和荧光Φ的量子产率FL  = 0.005和0.004，分别指定为在DMF和DMSO。为了生物学研究，已将酞菁

  DOI：

  10.1016/j.jphotobiol.2018.04.025

文献信息

• Phthalocyanines with bulky substituents at non-peripheral positions – Synthesis and physico-chemical properties
  作者：Adam Tillo、Magdalena Stolarska、Michal Kryjewski、Lukasz Popenda、Lukasz Sobotta、Stefan Jurga、Jadwiga Mielcarek、Tomasz Goslinski

  DOI：10.1016/j.dyepig.2015.12.017

  日期：2016.4

  equipped with bulky substituents at non-peripheral positions were synthesized and their physico-chemical properties were analyzed. Singlet oxygen generation as well as the aggregation properties of the phthalocyanines with different sizes of peripheral substituents were thoroughly studied. An insertion of benzyloxy or 3,5-bis(benzyloxy)benzyloxy groups to the non-peripheral positions of phthalocyanines

  合成了三种在非周边位置均具有大取代基的新型酞菁衍生物，并对其理化性质进行了分析。深入研究了具有不同外围取代基尺寸的酞菁的单线态氧生成以及聚集性质。与被2-丙氧基取代的酞菁相比，将苄氧基或3,5-双（苄氧基）苄氧基插入到酞菁的非外围位置提高了单线态氧的产生效率。
• Synthesis of Near-IR Absorbing/Emitting Porphyrazine Derivatives with Tunable Solubility
  作者：Sangwan Lee、Andrew J. P. White、David J. Williams、Anthony G. M. Barrett、Brian M. Hoffman

  DOI：10.1021/jo001220y

  日期：2001.1.1

  We report the synthesis of porphyrazines (pzs), or tetraazaporphyrins, of the form H(2)[pz(A(n;)B(4-n))], where A is [S(CH(2))(3)COOR](2) (R = n-Pr, H) and B is a fused beta,beta'-diisopropyloxybenzo group, including the compounds with n = 4 (6), n = 3 (7) and the trans compound with n = 2 (8) (Scheme 1). The synthesis employs Linstead crossover macrocyclization of dimethyl 6,7-dicyano-5,8-dithia-6(Z)dodecenedioate, MNT(C(4)O(2)Me)2 (2), with 1-imino-4,7-bis(1-methylethoxy)-1H-isoindole-3-amine (4). These pigments were characterized by (1)H NMR, 13C NMR, absorbance/fluorescence spectroscopy, mass spectrometry, and microanalysis. An X-ray crystal structure of 8 is presented. Of particular note, 6-8 display intense near-IR absorbance and dual UV-visible/near-IR emission which are very important in potential biomedical applications, both for cancer therapy (photodyanamic therapy, PDT) and cancer diagnosis (optical tumor imaging). For example, the trans-porphyrazine 8 has an intense long-wavelength absorption at ca. 800 nm (log epsilon = 4.18) and S1 fluorescence at similar to 820 nm, where mammalian tissue is effectively penetrated by light. Transformation of the ester group permits a wide range of functionality and solubility to be generated without change in optical properties. As an example, hydrolysis of these compounds by LiOH in THF/H(2)O gives the corresponding carboxylato-functionalized pigments 9-11, which are described. The last of these dissolves without aggregation in fetal calf serum.
• The chemical stabilities of phthalocyanine monomers vs. aggregations
  作者：Xin Fang、Jun-Dong Wang、Mei-Jin Lin

  DOI：10.1016/j.molcata.2013.02.004

  日期：2013.6

  Two unsymmetrical phthalocyanines (Pcs) having a strong tendency toward forming aggregations were synthesized and the electronic absorption spectral studies revealed that their monomers are much easier to be protonated or decomposed than the aggregations in acidic or oxidative conditions. Before being protonated or decomposed, the aggregations are always disassembled into the monomers in the solutions. This conclusion is undoubtedly of considerable realistic significance for the practical application as molecular catalysis. (C) 2013 Elsevier B.V. All rights reserved.
• A Facile and Regioselective Synthesis of Trans-Heterofunctionalized Porphyrazine Derivatives
  作者：Timothy P. Forsyth、D. Bradley G. Williams、Antonio Garrido Montalban、Charlotte L. Stern、Anthony G. M. Barrett、Brian M. Hoffman

  DOI：10.1021/jo971683c

  日期：1998.1.1

  New methodology was developed for the selective synthesis of regiochemically defined porphyrazines of the form M[pz(A(2);B-2)] (shown in Chart 1) where A and B represent peripheral functionalization attached to the P-positions of the pyrroles. Specifically, phthalonitriles or derivatives thereof with sterically bulky groups in positions 3 and 6, in particular 4,7-bis(isopropyloxy)-1,3-diiminoisoindoline (3) act as a "trans director" when macrocyclized with heteroatom-appended maleonitriles under Linstead conditions, the result being preferential formation of the trans-h[pz(A(2);B-2)] pigment where A = SR, NMe2, OR, as well as R (shown in Chart 2). Linstead crossover macrocyclization of 3 with 4, 11, 15, and 18 gave pigments 10, 14, 17, and 19, respectively. These pigments were characterized by H-1 NMR, C-13 NMR, UV-visible spectroscopy, mass spectrometry, microanalysis, and 17 was characterized by single-crystal X-ray analysis.
• In vitro photodynamic activity of lipid vesicles with zinc phthalocyanine derivative against Enterococcus faecalis
  作者：Lukasz Sobotta、Jolanta Dlugaszewska、Piotr Kasprzycki、Sebastian Lijewski、Anna Teubert、Jadwiga Mielcarek、Maria Gdaniec、Tomasz Goslinski、Piotr Fita、Ewa Tykarska

  DOI：10.1016/j.jphotobiol.2018.04.025

  日期：2018.6

  concentrations. The presented zinc(II) phthalocyanine showed values of singlet oxygen generation ΦΔ = 0.18 and 0.16, the quantum yield of the photodecomposition ΦP = 3.06∙10−4 and 1.23∙10−5 and the quantum yield of fluorescence ΦFL = 0.005 and 0.004, designated in DMF and DMSO, respectively. For biological studies, phthalocyanine has been incorporated into modified liposome vesicles containing ethanol

  带有八个非外围2-丙氧基取代基的酞菁锌（II）进行了物理化学研究，并掺入脂质囊泡后，被评估为抗菌光动力疗法的潜在光敏剂。通过MS和NMR技术对在大环化反应中获得的酞菁衍生物进行了表征。此外，通过HPLC分析确认了其化学纯度。X射线结构分析表明，酞菁衍生物的过度拥挤会导致大环核心π系统的强烈平面外扭曲。在酞菁锌（II）的UV-Vis吸收光谱中，发现了两个特征带：Soret（300-450 nm）和Q带（600-800 nm）。用时间分辨荧光光谱研究了单和双质子化酞菁衍生物的光物理性质。由于化合物在较高的酸浓度下分解，因此无法获得其三和四质子化形式。提出的锌（II）酞菁具有单重态氧产生值ΦΔ  = 0.18和0.16，光分解Φ的量子产率P  = 3.06∙10 -4和1.23∙10 -5和荧光Φ的量子产率FL  = 0.005和0.004，分别指定为在DMF和DMSO。为了生物学研究，已将酞菁