2-(1-hydroxy-1-(p-cyanophenyl)methyl)-1,3-dithiane | 220176-07-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-(1-hydroxy-1-(p-cyanophenyl)methyl)-1,3-dithiane
• 英文别名: 1,3-dithian-2-yl-(4-methoxyphenyl)methanol；1,3.dithian-2-yl-4-methoxyphenylmethanol
• CAS: 220176-07-8
• 化学式: C₁₂H₁₆O₂S₂
• 分子量: 256.39
• InChiKey: NMUZKWQJSJDKIL-UHFFFAOYSA-N

物化性质

• 熔点：
  84-87 °C
• 沸点：
  430.4±40.0 °C(Predicted)
• 密度：
  1.244±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  80.1
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-(1-hydroxy-1-(p-cyanophenyl)methyl)-1,3-dithiane 在 N-溴代丁二酰亚胺(NBS) 、 sodium hydride 、 barium carbonate 作用下， 以 四氢呋喃 、 丙酮 、 甲苯 为溶剂， 反应 3.0h， 生成 4-methoxy-benzoic acid benzyl ester
  参考文献：
  名称：

  苯胺介导的空气中α-烷氧基醛的氧化性CC键裂解和合成α-（d）-氨基酸衍生物的模型反应†

  摘要：

  无金属和 4-甲基苯胺已经开发了介导的氧化碳-碳键裂解的方法。该反应使用分子氧作为氧化剂在空气中进行，在短时间内以中等至良好的收率提供了一个碳短的酯。而且，它通过与L-脯氨酸催化的曼尼希反应结合，为（D）-丝氨酸酯的高度对映选择性合成提供了模型反应。

  DOI：

  10.1039/c3ob40685g
• 作为产物：
  描述：

  2-lithio-1,3-dithiane 、 4-甲氧基苯甲醛 以 四氢呋喃 为溶剂， 生成 2-(1-hydroxy-1-(p-cyanophenyl)methyl)-1,3-dithiane
  参考文献：
  名称：

  Mercury(II) Chloride-Mediated Cyclization−Rearrangement of O-Propargylglycolaldehyde Dithioacetals to 3-Pyranone Dithioketals:  An Expeditious Access to 3-Pyranones

  摘要：

  O-Propargyl glycolaldehyde dithioacetals undergo a unique cyclization-rearrangement in the presence of mercuric chloride and calcium carbonate to afford 3-pyranones exclusively or along with 2,5-dihydrofuran-3-carboxaldehydes via their dithioketals and dithioacetals.

  DOI：

  10.1021/ol047893a

文献信息

• Mercuric Chloride and Iodide Mediated Cyclization of Tethered Alkynedithioacetals as a General Route to Five- and Six-Membered Rings:  Tuning of Regioselectivity by Alkyne Substitution
  作者：Goutam Biswas、Subir Ghorai、Anup Bhattacharjya

  DOI：10.1021/ol0527274

  日期：2006.1.1

  Mercuric chloride mediated cyclization of tethered alkynedithioacetals has been established as a general route to five- and six-membered carbocycles and heterocycles. Substitution at the alkyne terminus leads to preferential formation of five-membered rings, whereas unsubstituted alkynedithioacetals give six-membered rings as the major products. Mercuric iodide interrupts the reaction at the intermediate dithioacetal

  [反应：见正文]氯化汞介导的链状炔二硫缩醛的环化已被确立为通向五元和六元碳环和杂环的一般途径。在炔基末端的取代导致优先形成五元环，而未取代的炔二硫缩醛以六元环为主要产物。碘化汞在中间二硫缩醛阶段中断反应。
• Lewis Base Catalyzed 1,3-Dithiane Addition to Carbonyl Compounds Using 2-Trimethylsilyl-1,3-dithiane
  作者：Makoto Michida、Teruaki Mukaiyama

  DOI：10.1246/cl.2008.26

  日期：2008.1.5

  1,3-Dithiane addition to various aldehydes and ketones using 2-trimethylsilyl-1,3-dithiane in the presence of a catalytic amount of a Lewis base such as tetrabutylammonium phenoxide (PhONn-Bu4) proceeds smoothly to afford the corresponding α-hydroxy dithiane compounds in good to high yields under mild conditions.

  1,3-二硫烷在存在催化量路易斯碱（如四丁基铵苯氧化物（PhONn-Bu4））的条件下与各种醛和酮的加成反应，使用2-三甲基硅基-1,3-二硫烷，可以顺利进行，得到相应的α-羟基二硫烷化合物，产率良好到高，并且反应条件温和。
• P(i-PrNCH2CH2)3N: an efficient catalyst for TMS-1,3-dithiane addition to aldehydes
  作者：Kuldeep Wadhwa、John G. Verkade

  DOI：10.1016/j.tetlet.2009.05.010

  日期：2009.7

  Herein we report the use of commercially available P(i-PrNCH2CH2)3N (1a) as an efficient catalyst for 2-trimethylsilyl-1,3-dithiane (TMS–dithiane) addition to aldehydes at room temperature. The catalyst loading required for these reactions (5 mol %) is the lowest recorded in the literature, and the majority of the reaction times for this transformation are the shortest thus far reported. A variety

  在本文中，我们报告了在室温下使用市售P（i -PrNCH 2 CH 2）3 N（1a）作为将2-三甲基甲硅烷基-1,3-二硫杂环丁烷（TMS-dithiane）加成醛的有效催化剂。这些反应所需的催化剂负载量（5mol％）是文献中记录的最低值，迄今为止，该转化的大多数反应时间是最短的。芳基醛底物上具有多种官能团。
• Electronic control of product formation in the rearrangement of 1,3-dithian-2-yl-arylmethanols
  作者：Chi Wi Ong、Chien Yen Yu

  DOI：10.1016/j.tet.2003.09.100

  日期：2003.11

  1,3-Dithian-2-yl-phenylmethanols undergo efficient rearrangement to afford 2-phenyl-6,7-dihydro-5H-1,4-dithiepines. The reactions were found to show remarkable variation in products formation that is dictated by the substituents on the aryl ring.

  1,3-二噻吩-2-基-苯基甲醇经过有效的重排，得到2-苯基-6,7-二氢-5 H -1,4-二硫平。发现反应显示出产物形成的显着变化，这由芳基环上的取代基决定。
• An Efficient Photo-SET-Induced Cleavage of Dithiane−Carbonyl Adducts and Its Relevance to the Development of Photoremovable Protecting Groups for Ketones and Aldehydes
  作者：William A. McHale、Andrei G. Kutateladze

  DOI：10.1021/jo981697y

  日期：1998.12.1

  Irradiation of dithiane-aldehyde/ketone adducts in the presence of benzophenone leads to C-C bond cleavage regenerating the carbonyl compounds. It is established that the mechanism of this reaction involves photochemically induced single electron transfer from the dithiane moiety to the excited molecule of ET-photosensitizer, accompanied by mesolytic C-C cleavage in the generated cation-radical, which is assisted by the anion-radical of benzophenone. This mechanism is confirmed by a Hammett plot study of the cleavage in the dithiane adducts of substituted aromatic aldehydes and a deuterium kinetic isotope effect study. Ab initio computations at UHF/6-31G* and MP2/6-31G* levels of theory in conjunction with self-consistent reaction field (self-consistent isodensity-polarized continuum model), to account for the solvent effect, also support the experimental findings. The reaction is most efficient for protection of aromatic aldehydes and ketones and aliphatic ketones, and is a novel method for protecting carbonyl functionalities with a photoremovable group.