Sulfonylation of aromatic compounds with sulfonic acids using silica gel-supported AlCl3 as a heterogeneous Lewis acid catalyst

Silica gel-supported aluminum chloride (SiO₂–AlCl₃) has been shown to be a mild, efficient, and chemoselective heterogeneous Lewis acid catalyst for direct conversion of arenes to sulfones using sulfonic acids as sulfonylating agents. The catalyst can be prepared easily with cheap starting materials and is stable (as a bench-top catalyst) and reusable.     

Facile Synthesis of 5-Arylidene Thiohydantoin by Sequential Sulfonylation/Desulfination Reaction

The sequential sulfonylation/desulfination reactions of 5-benzylthiohydantoin with excess arylsulfonyl chlorides in the presence of triethylamine have been developed to afford a wide range of 5-arylidene thiohydantoin derivatives in moderate to excellent yields. A plausible sulfonylation/desulfination mechanism was proposed. The bioassay showed that these compounds exhibit certain fungicidal activities with the 71.9% inhibition rate of 2K against B. cinerea, and 57.6% inhibition rate of 2m against A. solani, respectively.     

1-氯甲基磺酰胺类化合物的合成

以吡啶为催化剂,实现了氯甲基磺酰氯和芳香伯胺的磺酰化反应。考察了催化剂、溶剂、物料比、反应温度等条件对反应产率的影响。结果表明,最优反应条件为:n(胺)∶n(磺酰氯)=1∶1.3,吡啶为催化剂,二氯甲烷为溶剂,先0℃再室温下反应,反应时间为4～8h。在最优条件下,以42%～95%的产率合成了9种具有不同取代基的磺酰胺类化合物。利用IR、~1HNMR、~(13)CNMR对目标产物的结构进行了确证。     

Iodide/tert‐Butyl Hydroperoxide‐Mediated Benzylic C–H Sulfonylation and Peroxidation of Phenol Derivatives

We disclose here the first iodine/tert‐butyl hydroperoxide (I₂/TBHP)‐mediated benzylic C–H sulfonylation of phenol derivatives. This new methodology provides an economic, operationally simple and metal‐free approach toward C(sp³)–S bond formation with medium to excellent yields at room temperature. Moreover, a novel sulfonylative and peroxidative bifunctionalization of phenol derivatives was also achieved by changing the amount of the oxidant. The reaction mechanism is exemplified via a radical pathway.

     

β-环糊精磺酰化及改性聚酰胺纤维研究

以对甲苯磺酰氯（β-TsCl）直接在β-环糊精的2号碳仲羟基处进行取代反应，合成了β-环糊精-2-磺酰酯，借助IR、UV以及溶解度的测定对产物进行了表征．探讨了β-环糊精-2-磺酰酯的合成条件及其对聚酰胺纤维的改性应用．结果表明：用β-环糊精-2-磺酰酯对聚酰胺纤维进行改性，将环糊精接到聚酰胺纤维上，可以改善聚酰胺纤维的吸水性、染色性等性能．     

Synthesis and Characterization of Bifunctional Periodic Silica with Surface and Framework Benzene Functionality

Novel organic-inorganic hybrid mesoporous molecular sieve of MCM-41 type containing both bridge-bonded phenyl groups in the walls and terminally bonded phenyl groups protruding into the channel space was synthesized using TEOS, 1,4-bis(triethoxysilyl)benzene (BTESB) and (triethoxysilyl)benzene (TESB) as precursors, cetyl pyridine bromide (CPBr) as template under acidic conditions. This new material was characterized by means of FT-IR, PXRD and nitrogen adsorption-desorption isotherms. The mesoporous organosilica was in-situ sulfonylated and reacted with diamines.     

A simple and efficient approach for the sulfonylation of indoles catalyzed by CuI

In this paper, a simple and efficient protocol for the chemoselective sulfonation of indoles using aryl sulfonyl chlorides in the presence of CuI is reported. The reaction proceeds under mild conditions and is applicable to indoles bearing a selection of functional groups without NH protection.     

Copper‐Mediated Oxidative Radical Addition/Cyclization Cascade: Synthesis of Trifluoromethylated and Sulfonated Quinoline‐2,4(1H,3H)‐diones

A copper‐mediated oxidative radical addition/cyclization cascade of o‐cyanoarylacrylamides with sodium trifluoromethanesulfonate (Langlois’ reagent) has been achieved. The reaction proceeds through radical addition, cyclization, and imine hydrolysis, in which the cyclization was accomplished by an intramolecular addition of the carbon radical to the nitrile. This transformation exhibits a wide substrate scope and good functional group tolerance, thus providing a highly efficient and practical access to a variety of trifluoromethylated quinoline‐2,4(1H,3H)‐diones. Furthermore, using other sulfinic acid sodium salts as sulfonylating agents, sulfonated quinolinediones were also obtained through a similar radical cascade.

     

Copper‐Catalyzed Remote C−H Functionalization of 8‐Aminoquinolines with Sodium and Lithium Sulfinates

A simple and mild copper‐catalyzed sulfonylation of 8‐aminoquinolines with sodium and lithium sulfinates is reported. In the presence of manganese(III) acetate [Mn(OAc)₃] as cooxidant a highly site‐selective C−H functionalization at the C‐5 position takes place. The reaction proceeds readily at room temperature in air and various sulfones were synthesized in moderate to high yields. Moreover, a straightforward procedure for the conversion of organolithium reagents and sulfur dioxide into C‐5 sulfonylated quinolines was developed.

     

Amines vs. N‐Oxides as Organocatalysts for Acylation,Sulfonylation and Silylation of Alcohols: 1‐Methylimidazole N‐Oxide as an Efficient Catalyst for Silylation of Tertiary Alcohols

A comparison of the relative catalytic efficiencies of Lewis‐basic amines vs. N‐oxides for the acylation, sulfonylation and silylation of primary, secondary and tertiary alcohols is reported. Whilst the amines are generally superior to the N‐oxides for acylation, the N‐oxides are superior for sulfonylation and silylation. In particular, 1‐methylimidazole N‐oxide (NMI‐O) is found to be a highly efficient catalyst for sulfonylation and silylation reactions. To the best of our knowledge, NMI‐O is the first amine or N‐oxide Lewis basic organocatalyst capable of promoting the efficient silylation of tert‐alcohols in high yield with low catalyst loading under mild reaction conditions.