2,5-dimethylphenyl methanesulfonate | 496837-65-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,5-dimethylphenyl methanesulfonate
• 英文别名: 2,5-dimethylphenyl mesylate；(2,5-dimethylphenyl) methanesulfonate
• CAS: 496837-65-1
• 化学式: C₉H₁₂O₃S
• 分子量: 200.258
• InChiKey: SRHWWXIRDISSAE-UHFFFAOYSA-N

物化性质

• 沸点：
  322.7±42.0 °C(Predicted)
• 密度：
  1.198±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,5-dimethylphenyl methanesulfonate 、 二甲胺 在 potassium phosphate 、 bis[chloro(1,2,3-trihapto-allylbenzene)palladium(II)] 、 N-[2-二(1-金刚烷)磷苯基]吗啉 作用下， 以 1,4-二氧六环 、 叔丁醇 为溶剂， 以80%的产率得到N,N,2,5-tetramethylaniline
  参考文献：
  名称：

  应对甲磺酸烷基酯的钯催化交叉偶联中的挑战：酮和伯烷基胺的单芳基化

  摘要：

  甲基（甲酸酯）的Mor（DalPhos）：描述了使用甲磺酸甲磺酸酯偶合伙伴进行酮单α-芳基化和脂肪族伯胺单芳基化的第一个实例。与二烷基酮，伯胺和仲胺以及否则具有挑战性的偶联伙伴丙酮和甲胺一起使用了一系列官能化的甲磺酸烷基酯。Ad =金刚烷基。

  DOI：

  10.1002/anie.201303305
• 作为产物：
  描述：

  对二甲苯 在 bis(methanesulfonyl)peroxide 作用下， 反应 24.0h， 以74%的产率得到2,5-dimethylphenyl methanesulfonate
  参考文献：
  名称：

  后期芳烃碳氢氧合

  摘要：

  尽管在药物发现和开发中需要代谢物合成，但用于形成氧化芳族 CO 键的合成方法很少。我们报告了一种用于芳烃后期 CO 键形成的新方法。即使对于高度官能化的底物，该反应也以优异的官能团耐受性进行。所得的甲磺酸芳基酯提供了获取潜在的人类药物代谢物的途径，并可直接用于安装 CF 键以阻断代谢热点。试剂双（甲磺酰基）过氧化物和底物芳烃之间的电荷转移相互作用可能与芳烃相对于其他官能团的化学选择性官能化有关。

  DOI：

  10.1021/jacs.8b09208

文献信息

• PROCESS FOR PRODUCING AROMATIC AMINES
  申请人：TAKASAGO INTERNATIONAL CORPORATION

  公开号：US20020035295A1

  公开（公告）日：2002-03-21

  The present invention provides an activator in arylamination using a palladium compound as a catalyst, which is superior to conventional phosphines in stability and performance. With the phosphine sulfide as an activator, an arylamination reaction achieves improved selectivity to produce a desired aromatic amine in an obviously increased yield as compared with a reaction using the corresponding phosphine compound. Moreover, the phosphine sulfide of the invention is impervious to oxidation and exists stably in air and therefore sufficiently withstands use on an industrial scale.

  本发明提供了一种在芳基化反应中使用钯化合物作为催化剂的活化剂，其在稳定性和性能方面优于传统的膦化合物。通过使用膦硫化物作为活化剂，芳基化反应实现了改善的选择性，以明显增加的产量生产所需的芳香胺，与使用相应的膦化合物的反应相比。此外，本发明的膦硫化物不受氧化影响，在空气中存在稳定，因此足以在工业规模上使用。
• Enantioselective Intermolecular Heck and Reductive Heck Reactions of Aryl Triflates, Mesylates, and Tosylates Catalyzed by Nickel
  作者：Xiaolei Huang、Shenghan Teng、Yonggui Robin Chi、Wenqiang Xu、Maoping Pu、Yun‐Dong Wu、Jianrong Steve Zhou

  DOI：10.1002/anie.202011036

  日期：2021.2.8

  Nickel‐catalyzed intermolecular Heck reaction of cycloalkenes proceeds well with aryl triflates, mesylates and tosylates in excellent enantiomeric ratios. The asymmetric reductive Heck reaction also works with a 2‐cyclopentenone ketal, which is equivalent to conjugate arylation of the enone itself.

  镍催化的环烯烃的分子间Heck反应与芳基三氟甲磺酸酯，甲磺酸酯和甲苯磺酸酯的对映体比率极好。不对称的还原性Heck反应也适用于2-环戊烯酮缩酮，这相当于烯酮本身的共轭芳基化。
• 2,2 (Diarlyl) Vinylphosphine compound, palladium catalyst thereof, and process for producing arylamine, diaryl, or arylalkyne with the catalyst
  申请人：——

  公开号：US20020058837A1

  公开（公告）日：2002-05-16

  A novel 2,2-(diaryl)vinylphosphine compound represented by the following general formula (1): 1 (wherein R 1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic group having 5 to 7 carbon atoms, etc.; R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 may be the same or different and each is an alkyl group having 1 to 6 carbon atoms, an alicyclic group having 5 to 7 carbon atoms, etc., provided that R 4 and R 5 taken together and/or R 6 and R 7 taken together may represent a fused benzene ring, a substituted fused benzene ring, a trimethylene group, etc.; and p, q, r, and s each is 0 to 5, provided that p+q and r+s each is in the range of from 0 to 5); a palladium-phosphine catalyst obtained by causing a palladium compound to act on the novel 2,2-(diaryl)vinylphosphine compound; and a process for obtaining an arylamine, a diaryl and an arylalkyne in the presence of the palladium-phosphine catalyst.

  一种由以下通用公式（1）表示的新型2,2-(二芳基)乙烯膦化合物：其中R1是氢原子、具有1至6个碳原子的烷基基团、具有5至7个碳原子的脂环基团等；R2、R3、R4、R5、R6和R7可能相同或不同，每个是具有1至6个碳原子的烷基基团、具有5至7个碳原子的脂环基团等，但要求R4和R5一起和/或R6和R7一起可能代表融合苯环、取代融合苯环、三亚甲基基团等；p、q、r和s每个为0至5，但要求p+q和r+s分别在0至5的范围内；通过使钯化合物作用于新型2,2-(二芳基)乙烯膦化合物而获得的钯-膦催化剂；以及在钯-膦催化剂存在下获得芳胺、二芳基和芳基炔的方法。
• REACTION CATALYST FOR CROSS-COUPLING AND METHOD FOR MANUFACTURING AROMATIC COMPOUND
  申请人：HOKKO CHEMICAL INDUSTRY CO., LTD.

  公开号：US20150360214A1

  公开（公告）日：2015-12-17

  The object of the present invention is to provide a new organic phosphorus ligand that can efficiently promote cross-coupling reaction to obtain the target substance at high yield, as well as a method of manufacturing such ligand whose steric characteristics and electronic characteristics can be fine-tuned and which can be used to cause cross-coupling reaction at high yield. As a means for achieving the aforementioned object, a phosphine compound expressed by General Formula (1) below is provided. (In the formula, R 1 and R 2 are each independently a secondary alkyl group, tertiary alkyl group, or cycloalkyl group, while R 3 and R 4 are each independently a hydrogen, aliphatic group, heteroaliphatic group, aromatic group, alicyclic group, or heterocyclic group. Note that R 3 and R 4 have no phosphorus atom and that R 3 and R 4 are not both hydrogen at the same time).

  本发明的目的是提供一种新的有机磷配体，可以高效地促进交叉偶联反应，以高产率获得目标物质，以及一种制造此类配体的方法，其立体特性和电子特性可以微调，并且可以用于高产率地引起交叉偶联反应。为了实现上述目的，提供了以下通式（1）所表示的膦化合物。（在公式中，R1和R2分别独立地为二级烷基、三级烷基或环烷基，而R3和R4分别独立地为氢、脂肪基、杂原子脂肪基、芳香族、脂环族或杂环族。请注意，R3和R4不具有磷原子，并且R3和R4不同时为氢）。
• Ligand for catalyst or pre-catalyst and method of forming C(SP2)-N bond
  申请人：DALHOUSIE UNIVERSITY

  公开号：US10322410B2

  公开（公告）日：2019-06-18

  A compound having a chemical formula according to Formula (I) is disclosed where one of Z1, Z2 and Z3 is and one of the Z1, Z2, and Z3 that is bonded to a carbon atom that is adjacent to the carbon atom bonded to is P(AR1)(A′R2). Metal-based catalyst and pre-catalysts, such as nickel-based catalysts and precatalysts, where the metal is complexed to the compound are also disclosed. Methods of forming C(sp2)-N bonds are also disclosed.

  本发明公开了一种具有根据式(I)的化学式的化合物，其中Z1、Z2和Z3之一是与碳原子键合的碳原子，与碳原子键合的碳原子相邻的Z1、Z2和Z3之一是P(AR1)(A′R2)。还公开了金属基催化剂和前催化剂，如镍基催化剂和前催化剂，其中金属与化合物络合。还公开了形成 C（sp2）-N 键的方法。