2,3-dichloro-1,4-dihydroxynaphthalene | 7474-86-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2,3-dichloro-1,4-dihydroxynaphthalene
• 英文别名: 2,3-dichloronaphthalene-1,4-diol；2,3-dichloro-naphthalene-1,4-diol；2,3-Dichlor-naphthalin-1,4-diol；2,3-Dichlor-1,4-naphthohydrochinon
• CAS: 7474-86-4
• 化学式: C₁₀H₆Cl₂O₂
• 分子量: 229.062
• InChiKey: NSMQVSICUVTJPT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,3-dichloro-1,4-dihydroxynaphthalene 在 吡啶 、 potassium sulfide 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 生成 1,4-dihydroxynaphthyl-1,2-thiole-2-thione hexanoate
  参考文献：
  名称：

  Tetrathiafulvalene quinones, hydroquinones and esters

  摘要：

  Benzocyclohexa-2,5-diene-1,4-dione-1,3-thiole-2-thione (2) was synthesized starting with 2,3-dichloronapthoquinone (1). Compounds 3 and 4 were also obtained; however, the yield of 2 can be increased through control of the temperature and reaction time. Reaction of 2 with triethylphosphite gave 5 and the tetrathiafulvalene ester 6. The tetrathiafulvalenequinone (9) was obtained by hydrolysis of 6 followed by oxidation of & Compound 9 was obtained more directly by hydrogenation of 2 followed by coupling with triethylphosphite and oxidation. Chloranil was used to prepare the dithiafulvene quinone 12 which was reduced, coupled with triethylphosphite to form, presumably, polymer 13. The reactions were repeated using the hexanoic acid esters of the corresponding hydroquinone thiafulvalenes. The crystal structures of 2, 3, 4, 5, 6a and 10 were determined by X-ray diffraction. Cyclic voltammetry studies show the tetrathiafulvalene quinones reduce like quinones, but do not exhibit the oxidation properties of tetrathiafulvalenes.

  DOI：

  10.1016/s0040-4020(01)89885-9
• 作为产物：
  描述：

  2,3-二氯-1,4-萘醌 在 氢气 作用下， 以 四氢呋喃 为溶剂， 30.0 ℃ 、101.33 kPa 条件下， 生成 2,3-dichloro-1,4-dihydroxynaphthalene
  参考文献：
  名称：

  通过使用非均相Au-Pt纳米粒子作为催化剂的连续和连续流加氢衍生化作用，由醌直接合成对苯二酚

  摘要：

  固定在二甲基聚硅烷上的Pt-Au双金属纳米颗粒催化剂（Pt-Au /（DMPSi-Al 2 O 3））已开发用于将醌选择性加氢为对苯二酚。在连续流动条件下证实了催化剂的高反应活性，选择性和坚固性。在连续和连续流动条件下成功进行了醌的各种直接衍生化反应，例如甲基化，乙酰化，三氟甲磺酰化，甲基丙烯酸化和苯甲酰化，以良好的产率提供了所需的产品，甚至具有优异的收率。尤其是，对空气敏感的氢醌，如蒽氢醌和萘氢醌，可以在封闭的连续和连续流动条件下成功生成并衍生化而不会分解。

  DOI：

  10.1002/anie.201904159

文献信息

• Chemistry of L-ascorbic acid. Part 3. Photoreduction of quinones with 5,6-O-isopropylidene-L-ascorbic acid†
  作者：Mukund G. Kulkarni、Sandesh D. Kate

  DOI：10.1039/b005120i

  日期：——

  Upon irradiation with UV light, instead of undergoing the Paternò–Büchi reaction, 5,6-O-isopropylidene-L-ascorbic acid reduced quinones quite efficiently and rapidly to the corresponding hydroquinones.

  在紫外线照射下，5,6- O-异亚丙基-L-抗坏血酸未发生Paternò–Büchi反应醌 相当有效和迅速地对应 对苯二酚。
• Diels–Alder trapping of in situ generated dienes from 3,4-dihydro-2H-pyran with p-quinone catalysed by p-toluenesulfonic acid
  作者：Radhakrishnan Mohan Raj、Kalpattu K. Balasubramanian、Deivanayagam Easwaramoorthy

  DOI：10.1039/c6ob02006b

  日期：——

  for the reaction between p-quinones and 3,4-dihydro-2H-pyran, than the Lewis acids. The products were accomplished by the Diels–Alder cycloaddition reaction and their mechanistic pathways have been formulated. The impact of C2 and C2,5 substituents of the p-quinones on the cycloaddition reaction has been explored. Remarkably, it is the first report to explore this kind of in situ generated diene for

  此综合性研究的portrays该p -甲苯磺酸是对之间的反应更有效的催化剂p -quinones和3,4-二氢-2- ħ吡喃，比路易斯酸。这些产物是通过Diels-Alder环加成反应完成的，其机械途径已经确定。已经研究了对苯醌的C 2和C 2,5取代基对环加成反应的影响。值得注意的是，这是第一个针对Diels-Alder环加成反应探索这种原位生成的二烯的报告。
• Palladium-catalyzed chemo- and regioselective cross-coupling reactions of 2,3-dichloronaphthalene-1,4-bistriflate
  作者：Zahid Hassan、Sulaiman Al-Shidhani、Ahmed Al-Ghafri、Ahmed Al-Harrasi、Javid Hussain、Rene Csuk

  DOI：10.1016/j.tetlet.2015.11.013

  日期：2015.12

  Palladium-catalyzed chemoselective and regioselective cross-coupling reactions of 2,3-dichloro-1,4-(trifluoromethanesulfonyloxy)naphthalene with aryl boronic acids selectively afforded a variety of mono-, di-, and tetraphenylnaphthalenes. These reactions proceeded with excellent chemoselectivity in favor of the triflate functional group at the C-1 and C-4 positions of naphthalene.

  2,3-二氯-1,4-（三氟甲磺酰氧基）萘与芳基硼酸的钯催化的化学选择性和区域选择性交叉偶联反应选择性地提供了各种单，二和四苯基萘。这些反应以优异的化学选择性进行，有利于萘的C-1和C-4位置的三氟甲磺酸酯官能团。
• Synthesis, biological evaluation, molecular docking and structure-activity relationship studies of halogenated quinone and naphthoquinone derivatives
  作者：Ghulam Abbas、Zahid Hassan、Ahmed Al-Harrasi、Ajmal khan、Ahmed Al-Adawi、Majid Ali

  DOI：10.1016/j.molstruc.2019.06.002

  日期：2019.11

  Alzheimer's disease. In this study, we synthesized a series of previously unexplored molecular analogues of halogenated quinone and naphthoquinone to investigate their therapeutic potency against protein glycation, free radical production and acetyl cholinesterase enzyme. The study on protein glycation resulted in the identification of two novel antiglycation agents such as 2,3-dichloronaphthalene-1

  摘要 蛋白质糖化、氧化应激和乙酰胆碱酯酶 (AChE) 与糖尿病并发症和阿尔茨海默病的发病机制密切相关。在这项研究中，我们合成了一系列以前未开发的卤代醌和萘醌的分子类似物，以研究它们对蛋白质糖化、自由基产生和乙酰胆碱酯酶的治疗效力。对蛋白质糖化的研究导致鉴定了两种新型抗糖化剂，例如 2,3-二氯萘-1,4-二氟甲磺酸酯 (3) 和 2,3-二溴萘-1,4-二 (三氟甲磺酸酯) (6)，IC50值小于 16 微摩尔范围。此外，2,3-二氯-1,4-萘醌(DCNQ)(1)、2,3-二溴单萘醌(4)、2,3-二溴萘-1,4-二醇(5)和2,3,5， 6-四氯苯-1，4-bis(trifluoromethane-sulfonate) (8) 表现出有效的抗糖化活性，与 IC50 值为 98 的标准抑制剂芦丁相比，IC50 值分别为 54 ± 1.02、43 ± 0.5、65 ± 1.00 和 60
• Hydration effects on the triplet exciplex between 2,3-dihalo-1,4-naphthoquinone and furan studied by steady-state and laser flash photolyses
  作者：Minoru Yamaji、Masanori Kurumi、Hiroko Kimura、Haruo Shizuka

  DOI：10.1039/a809483g

  日期：——

  Photochemical interactions of triplet 2,3-dibromo- and 2,3-dichloro-1,4-naphthoquinones (DBNQ and DCNQ) with furan in acetonitrile (ACN) and a mixture of ACN and water (4:1 v/v) were investigated by means of product analysis, steady-state and nanosecond laser flash photolysis. The photoproducts of DBNQ and DCNQ in the presence of furan in ACN were 2-bromo- and 2-chloro-3-(2-furyl)-1,4-naphthoquinones with the quantum yields for production (Φpro) of 0.12 and 0.05, respectively, whereas in aqueous ACN, 2,3-dibromo- and 2,3-dichloro-1,4-dihydroxynaphthalenes Φpro=0.12 and 0.17, respectively. By nanosecond laser photolysis at 355 nm, it was found that triplet DBNQ and DCNQ were quenched by furan with rate constants (kq) of 2.0×109 and 3.0×109 d mol-1 s-1 in ACN and 6.1×109 and 6.4×109 d mol s-1 in aqueous ACN, respectively. After depletion of triplet DBNQ and DCNQ, no transient absorption in the region 360–600 nm was observed in ACN while the corresponding anion radicals having molar absorption coefficients (εani) of 7700 and 7900 d mol-1 cm-1 at 400 nm, respectively, were formed in aqueous ACN. The initial interaction of triplet DBNQ and DCNQ with furan in aqueous ACN was found to be electron transfer with efficiencies (αet) of 0.22 and 0.23, respectively, while that in ACN was presumed to be dominated by induced quenching. The deactivation mechanism of triplet DBNQ and DCNQ by furan was discussed from the viewpoint of the free energy changes (ΔG) for electron transfer. It was suggested that the triplet exciplex with weak charge-transfer character played an important role being controlled by the solvation energy in the ΔG term.

  三重态 2,3-二溴-和 2,3-二氯-1,4-萘醌（DBNQ 和 DCNQ）与呋喃在乙腈 (ACN) 以及 ACN 和水的混合物 (4:1 v/v) 中的光化学相互作用通过产物分析、稳态和纳秒激光闪光光解进行研究。在乙腈中存在呋喃的情况下，DBNQ 和 DCNQ 的光产物分别是 2-溴-和 2-氯-3-(2-呋喃基)-1,4-萘醌，生产量子产率 (Φpro) 分别为 0.12 和 0.05，分别，而在乙腈水溶液中，2,3-二溴-和2,3-二氯-1,4-二羟基萘分别Φpro=0.12和0.17。通过355 nm纳秒激光光解，发现三线态DBNQ和DCNQ被呋喃猝灭，速率常数(kq)分别为2.0×109和3.0×109 d mol-1 s-1，在ACN和6.1×109和6.4×分别在乙腈水溶液中为 109 d mol s-1。三线态 DBNQ 和 DCNQ 耗尽后，ACN 中在 360–600 nm 区域没有观察到瞬态吸收，而相应的阴离子自由基在 400 nm 处的摩尔吸收系数 (μani) 分别为 7700 和 7900 d mol-1 cm-1 ，在乙腈水溶液中形成。发现三线态 DBNQ 和 DCNQ 与呋喃在乙腈水溶液中的初始相互作用是电子转移，效率 (αet) 分别为 0.22 和 0.23，而在乙腈中则推测主要是诱导猝灭。从电子转移自由能变化（ΔG）的角度讨论了呋喃对三线态 DBNQ 和 DCNQ 的失活机制。这表明具有弱电荷转移特性的三线态激基复合物在ΔG项中受溶剂化能控制发挥了重要作用。