2-methoxyphenyl N,N-dimethylsulfamate | 1137-57-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-methoxyphenyl N,N-dimethylsulfamate
• 英文别名: Dimethylsulfamic acid 2-methoxyphenyl ester；(2-methoxyphenyl) N,N-dimethylsulfamate
• CAS: 1137-57-1
• 化学式: C₉H₁₃NO₄S
• mdl: MFCD16172083
• 分子量: 231.273
• InChiKey: DJVWDJPAALBNLJ-UHFFFAOYSA-N

物化性质

• 熔点：
  38-42 °C
• 沸点：
  120 °C(Press: 0.5 Torr)
• 密度：
  1.269±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.333
• 拓扑面积：
  64.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-methoxyphenyl N,N-dimethylsulfamate 、 二对甲苯基硼酸 在 bis(triphenylphosphine)nickel(II) chloride 、 potassium phosphate monohydrate 、 1-丁基-3-甲基咪唑溴盐 作用下， 以 甲苯 为溶剂， 反应 10.0h， 以80%的产率得到1-甲氧基-2-(4-甲基苯基)苯
  参考文献：
  名称：

  N-杂环卡宾辅助的双（膦）镍催化的二芳基硼酸与芳基氯化物，甲苯磺酸盐和氨基磺酸盐的交叉偶联

  摘要：

  二芳基硼酸与芳基氯化物，甲苯磺酸盐和氨基磺酸盐的高效双（膦）镍催化交叉偶联已经在由N，N'-二烷基咪唑鎓盐（例如N）原位生成的N-杂环卡宾（NHC）的帮助下进行了丁基- ñ '甲基咪唑溴化物（[BMIM] BR），在用k甲苯3 PO 4 ·3H 2 O为基础。与双（NHC）镍催化的传统Suzuki芳基硼酸偶联反应不同，Ni（PPh 3）2 Cl 2原位生成单（NHC）双（膦）镍物种/ [Bmim] Br在二芳基硼酸的交叉偶联中显示出高催化活性。发现二芳基硼酸的结构影响很小，而芳基氯化物，甲苯磺酸盐和氨基磺酸盐的电子因素则显着影响偶联。以1.5 mol％NiCl 2（PPh 3）2 / [Bmim] Br作为催化剂前体可以有效地实现电子活化的芳基氯化物，甲苯磺酸盐和氨基磺酸盐的偶联，从而以3-5 mol％的高收率得到联芳基产品。加载必须用于非激活和停用的耦合。小邻里芳基氯，甲苯磺酸酯和氨基磺

  DOI：

  10.1021/jo501291y
• 作为产物：
  描述：

  phenyl N,N-dimethylsulfamate 在 potassium phosphate 、 双氧水 、 仲丁基锂 、 sodium hydroxide 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 水 为溶剂， 生成 2-methoxyphenyl N,N-dimethylsulfamate
  参考文献：
  名称：

  Suzuki−Miyaura Cross-Coupling of Aryl Carbamates and Sulfamates: Experimental and Computational Studies

  摘要：

  The first Suzuki-Miyaura cross-coupling reactions of the synthetically versatile aryl O-carbamate and O-sulfamate groups are described. The transformations utilize the inexpensive, bench-stable catalyst NiCl2(PCy3)(2) to furnish biaryls in good to excellent yields. A broad scope for this methodology has been demonstrated. Substrates with electron-donating and electron-withdrawing groups are tolerated, in addition to those that possess ortho substituents. Furthermore, heteroaryl substrates may be employed as coupling partners. A computational study providing the full catalytic cycles for these cross-coupling reactions is described. The oxidative addition with carbamates or sulfamates occurs via a five-centered transition state, resulting in the exclusive cleavage of the aryl C-O bond. Water is found to stabilize the Ni-carbamate catalyst resting state, which thus provides rationalization of the relative decreased rate of coupling of carbamates. Several synthetic applications are presented to showcase the utility of the methodology in the synthesis of polysubstituted aromatic compounds of natural product and bioactive molecule interest.

  DOI：

  10.1021/ja200398c

文献信息

• Aryl and aryloxyalkyl sulfamate esters useful as anticonvulsants
  申请人：A. H. Robins Co., Inc.

  公开号：US05025031A1

  公开（公告）日：1991-06-18

  Herein disclosed is a method of treating convulsions with a pharmaceutical composition containing a compound of the formula: (HO).sub.p --A--[OSO.sub.2 NR.sup.1 R.sup.2 ].sub.z where A is an aryl, arylalkyl, or aryloxyalkyl group and is substituted on 1 or more carbon atoms with a sulfamate group (--OSO.sub.2 NR.sup.1 R.sup.2) wherein R.sup.1 and R.sup.2, same or different, are hydrogen or loweralkyl wherein p is 0 or 1 and is the number of untreated hydroxyl groups and z is 1 or 2 and is the number of --OS(O.sub.2)NR.sup.1 R.sup.2 groups. Aryl is selected from phenyl, substituted phenyl, pyridinyl, naphthyl, quinolinyl, and the like. Phenyl substituents are selected from hydrogen, halo, hydroxy, phenyl, phenoxy, benzoyl, loweralkyl, loweralkoxy, carboxy, amino, loweralkylamino, diloweralkylamino, acetamido, cyano, nitro, loweralkoxycarboyl, aminosulfonyl, imidazolyl, triazolyl, and the like. Novel compounds not previously disclosed are also described.

  以下披露了一种使用含有化合物的药物组合物来治疗惊厥的方法：(HO).sub.p --A--[OSO.sub.2 NR.sup.1 R.sup.2 ].sub.z，其中A是芳基、芳基烷基或芳氧烷基基团，并在1个或多个碳原子上用磺酰胺基团(--OSO.sub.2 NR.sup.1 R.sup.2)取代，其中R.sup.1和R.sup.2，相同或不同，是氢或较低烷基，其中p为0或1，是未处理的羟基团的数量，z为1或2，是--OS(O.sub.2)NR.sup.1 R.sup.2基团的数量。芳基选自苯基、取代苯基、吡啶基、萘基、喹啉基等。苯基取代基选自氢、卤素、羟基、苯基、苯氧基、苯甲酰基、较低烷基、较低烷氧基、羧基、氨基、较低烷基氨基、二较低烷基氨基、乙酰胺基、氰基、硝基、较低烷氧羰基、氨基磺酰基、咪唑基、三唑基等。还描述了以前未披露的新化合物。
• Air‐Stable Fe₃O₄@SiO₂‐EDTA‐Ni(0) as an Efficient Recyclable Magnetic Nanocatalyst for Effective Suzuki‐Miyaura and Heck Cross‐Coupling via Aryl Sulfamates and Carbamates
  作者：Iman Dindarloo Inaloo、Sahar Majnooni、Hassan Eslahi、Mohsen Esmaeilpour

  DOI：10.1002/aoc.5662

  日期：2020.8

  The synthesis of inexpensive and novel air‐stable Ni(0) nanoparticles immobilized on the EDTA‐modified Fe3O4@SiO2 nanocatalyst was investigated in Suzuki‐Miyaura and Heck cross‐coupling reactions. This catalytic system displayed a greatly improved substrate scope for the carbon–carbon bond formations starting from a wide range of green and economical electrophiles aryl and heteroaryl carbamates and

  廉价且新颖的，稳定的，稳定在EDTA修饰的Fe 3 O 4 @SiO 2上的Ni（0）纳米颗粒的合成在Suzuki-Miyaura和Heck交叉偶联反应中研究了纳米催化剂。该催化体系通过在温和，操作简单的反应条件下通过高效方法，从广泛的绿色和经济亲电氨基甲酸酯和杂芳基氨基甲酸酯和氨基磺酸盐开始，显着改善了碳-碳键形成的底物范围。合成的多相催化剂还通过FT-IR，TEM，XRD，DLS，FE-SEM，UV-Vis，EDX，XPS，TGA，NMR，VSM，ICP和元素分析技术进行了全面表征。可以通过外部磁场容易地回收异质磁性纳米催化剂，并且在催化剂的沥滤可忽略不计并且活性没有实质性降低的情况下，至少七次重复用于接下来的反应至少七次。所有这些亮点使本协议变得有趣，
• Compounds having one or more aminosulfaonyloxy radicals useful as
  申请人：A. H. Robins Company, Incorporated

  公开号：US05194446A1

  公开（公告）日：1993-03-16

  Methods of treating chronic arthritis and osteoporosis which utilize both known and novel compounds which would fall under the general formula: (HO)p--A--[--OS(O).sub.2 NR.sup.1 R.sup.2 ].sub.z wherein A encompasses a wide range of values including but not limited to aryl, loweralkyl, cycloalkyl, and carbohydrates including sucrose and fructose; p is equal to the number of unreacted hydroxy groups contained on the molecule and may be zero; z is the number of --OS(O).sub.2 NR.sup.1 R.sup.2 groups and is always at least one; R.sup.1 and R.sup.2 are selected from hydrogen, loweralkyl, carboxy and the like; a novel process for preparing the compounds is provided wherein an appropriate sulfamic acid aryl ester is reacted with a hydroxy substituted A radical which may or may not contain thereon protected carboxyl, amino or hydroxy substituents, in an aprotic solvent containing a tertiary amine base. Pharmaceutical compositions for the treatment of chronic arthritis and osteoporosis are also provided.

  治疗慢性关节炎和骨质疏松症的方法利用已知和新颖的化合物，这些化合物可归入一般公式：(HO)p--A--[--OS(O).sub.2 NR.sup.1 R.sup.2 ].sub.z，其中A包括一系列值，包括但不限于芳基、较低烷基、环烷基和碳水化合物，包括蔗糖和果糖；p等于分子中未反应的羟基数，可以为零；z是--OS(O).sub.2 NR.sup.1 R.sup.2基团的数量，始终至少为一；R.sup.1和R.sup.2从氢、较低烷基、羧基等中选择；提供了一种制备这些化合物的新方法，其中适当的磺酸酯与含有保护羧基、氨基或羟基取代基的羟基取代的A基团在含有三级胺碱的无水溶剂中反应。还提供了用于治疗慢性关节炎和骨质疏松症的药物组合物。
• 1,2-Bis(arylthio)arene synthesis <i>via</i> aryne intermediates
  作者：Milad Mesgar、Justin Nguyen-Le、Olafs Daugulis

  DOI：10.1039/c9cc03863a

  日期：——

  Lithium 1,1-diadamantylamide (LDAM) base-promoted insertion of arynes into disulfide S–S bonds is described. After generation of arynes from readily available aryl halides and triflates, reactions with diaryl and diisopropyl disulfides afford the insertion products in moderate to excellent yields. Use of 1-cyclohexenyl triflate gave an excellent yield of 1,2-bis(phenylthio)cyclohexene.

  描述了1,1-二金刚酰胺锂（LDAM）碱促进的芳烃插入二硫键的S–S键。从易于得到的芳基卤化物和三氟甲磺酸酯生成芳烃后，与二芳基和二异丙基二硫化物的反应可中等至极好地获得插入产物。使用1-环己烯基三氟甲磺酸酯具有极好的1,2-双（苯硫基）环己烯收率。
• <i>N</i>-Arylation of (hetero)arylamines using aryl sulfamates and carbamates <i>via</i> C–O bond activation enabled by a reusable and durable nickel(0) catalyst
  作者：Iman Dindarloo Inaloo、Sahar Majnooni、Hassan Eslahi、Mohsen Esmaeilpour

  DOI：10.1039/d0nj01610a

  日期：——

  elemental analysis techniques. The reaction proceeded via carbon–oxygen bond cleavage of (hetero)aryl carbamates and sulfamates under simple and mild conditions without the use of any external ligands. This method demonstrated functional group tolerance in the N-arylation of various nitrogen-containing compounds as well as aliphatic amines, anilines, pyrroles, pyrazoles, imidazoles, indoles, and indazoles

  已经开发出了一种有效且通用的芳基胺化方案，使用了可磁回收的Ni（0）基纳米催化剂。该新型稳定催化剂是在EDTA改性的Fe 3 O 4 @SiO 2上制备的，并通过FT-IR，EDX，TEM，XRD，DLS，FE-SEM，XPS，NMR，TGA，VSM，ICP和元素分析技术进行了研究。该反应通过在简单温和的条件下不使用任何外部配体的情况下，通过（杂）芳基氨基甲酸酯和氨基磺酸酯的碳-氧键裂解来进行。该方法证明了N中的官能团耐受性各种含氮化合物以及脂肪族胺，苯胺，吡咯，吡唑，咪唑，吲哚和吲唑的芳基化，收率良好。此外，该催化剂可以通过使用外部磁场容易地回收，并且可以直接重复使用至少六次而不会显着降低其活性。