Formation of 2-arylindane-1,3-diones and 3-alkylphthalides from methyl o-[α-phenylsulfonyl]toluate

2-Aryl-1,3-indanedione and phthalide derivatives have attracted considerable interest due to their anticoagulant, parasiticidal and a range of biological activities. The synthesis of 2-aryl-1,3-indanedione by the condensation of the title sulfone with aryl aldehydes through an interesting pathway and a previously unreported approach to 3-alkylphthalide from C-alkylated derivatives of 1 under microwave and conventional heating conditions are described.     

Synthesis and antibacterial activity of 2-phenyl-4H-benzo[b]thiopyran-4-ones (Thioflavones) and related compounds

A number of 2-phenyl-4H-benzo[b]thiopyran-4-ones (thioflavones) and related compounds have been prepared to test their antibacterial activity. The flavone derivatives were also prepared to compare with their antibacterial activity. It was found that hydroxythioflavones were easily prepared by demethylation of methoxythioflavones with aluminium chloride. In the test of antimicrobial activity, methoxy- or hydroxythioflavones were found to be inactive. It is suggested that the sulfone or sulfoxide of thioflavone is required for antimicrobial activities against yeast funguses and molds. These thioflavone derivatives exhibit low acute toxicity.     

A Simple,Efficient One‐Pot Synthesis of 2‐Isoxazoline Derivatives and their Antimicrobial Activity

Synthesis of substituted 2‐isoxazolines derivatives with sulfone functional groups was accomplished by 1,3‐dipolar cycloaddition reaction. The 1,3‐dipolar nitrile oxides generated in situ by reacting α‐formaldoximes with N‐bromosuccinimide in the presence of triethylamine on reaction with activated alkenes in toluene at room temperature afford the corresponding 2‐isoxazolines in high yields. All the 2‐isoxazoline derivatives were assayed for their antibacterial activities against Staphylococcus aureus, Bacillus cereus, Escherichia coli, and Pseudomonas aeruginosa and antifungal activities against Aspergillus niger and Candida albicans. Most of the compounds showed good antibacterial and antifungal activities.     

Reactions of some alken-1-yl and cycloalken-1-yl bromomethyl sulfones with dimethyl malonate and malononitrile

Bromomethyl cyclopent-1-enyl sulfone and bromomethyl cyclohex-1-enyl sulfone reacted with dimethyl malonate and malononitrile sodium salts in THF at 20?C50°C to give products of Michael-induced Ramberg-B?cklund reaction, functionalized derivatives of methylidenecyclopentane and methylidenecyclohexane. Reactions of bromomethyl hex-1-en-1-yl sulfone and bromomethyl hept-1-en-1-yl sulfones with the same sodium enolates followed the Michael-induced ring closure pattern with formation of tetrahydrothiophene 1,1-dioxide derivatives containing allylmalonic acid derivatives as impurities. Factors responsible for the different reaction pathways of cyclic and acyclic bromomethyl sulfones are discussed.     

Enzymatic Deprotection of Methylthiomethyl Esters: Synthesis of O-(Carbamoyl) and O-(Sulfamoyl)salicylic Acids

An enzymatic selective deprotection of methylthiomethyl esters via their sulfone derivatives in presence of labile carbamoyloxy as well as sulfamoyloxy functionalities lead to the formation of O-(carbamoyl) and O-(sulfamoyl)salicylic acids respectively.     

CuCl/I2催化末端烯烃与磺酰氯反应合成烯基砜类化合物研究

研究了用CuCl/I2催化一系列端基烯烃和磺酰氯反应合成烯基砜类化合物,反应体系中添加催化剂量的分子碘,可以大幅度提高该反应的产率,最高可获得97%的产率.同时,考察了各种铜盐的催化活性以及反应介质对反应的影响.     

Synthesis and antifungal activity of novel sulfone derivatives containing 1,3,4-oxadiazole moieties

A series of new sulfone compounds containing 1,3,4-oxadiazole moieties were synthesized. The structures of these compounds were confirmed by spectroscopic data (IR, 1H- and 13C-NMR) and elemental analyses. Antifungal tests indicated that all the title compounds exhibited good antifungal activities against eight kinds of plant pathogenic fungi, and some showed superiority over the commercial fungicide hymexazol. Among them, compounds 5d, 5e, 5f, and 5i showed prominent activity against B. cinerea, with determined EC?? values of 5.21 μg/mL, 8.25 μg/mL, 8.03 μg/mL, and 21.00 μg/mL, respectively. The present work demonstrates that sulfone derivatives such as 5d containing a 1,3,4-oxadiazole moiety can be used as possible lead compounds for the development of potential agrochemicals.     

Metalation of alkyl aryl sulfones: qualitative and quantitative product determination

The metalation of methyl phenyl sulfone (I) and methyl naphthyl sulfone (II) was investigated under a variety of conditions. The product species were determined qualitatively and quantitatively after characterization with some electrophilic agents. After the primary metalation at the methyl position, species of various metalation degrees were prsent simultaneously, including the 1,1,1-trimetalated derivatives. With high LiR/sulfone ratios, in addition to the products of the primary metalation, compounds arising from metalation of the aromatic ring were formed as well as those from reduction, cleavage, etc.     

The 1.4 and 248 nm radiation response of chemically amplified resists containing arylmethyl sulfone photoacid generators

The X-ray (1.4 nm) and deep UV (248 nm) radiation responses of chemically amplified photoresists incorporating arylmethyl sulfone photoacid generators were evaluated. The arylmethyl sulfones were primarily derivatives of benzyl phenyl sulfone, selected to reveal the importance of desulfonylation and internal abstraction with regard to the photochemical efficiency of acid generation. At 1.4 nm, benzyl phenyl sulfone gave a much more sensitive resist than dibenzyl sulfone, while the methyl derivatives of benzyl phenyl sulfone did not give much improvement over the parent compound. This suggests that desulfonylation is more important than internal abstraction for increased photochemical efficiency. At 248 nm, similar trends were observed, but with some modifications arising from the variation in extinction coefficient among the sulfones. Sensitivities at or below 20 mJ/cm² were obtained for both wavelength ranges.     

聚苯撑醚砜缩聚过程的研究

本文报导了聚苯撑醚砜碱法缩聚动力学的研究。首先合成了有关的单体及二聚体的模拟化合物,然后进行了反应速率常数的测定。其结果是:(1)两组带有取代基的苯衍生物相互作用时,其反应速率常数等于不带取代基的苯衍生物和带取代基的反应速率常数以及取代基组成相反的另一组速率常数的乘积。(2)对于聚苯撑醚砜缩聚反应必须采用多个反应速率常数来计算动力学过程。     

Vicarious Nucleophilic Substitution of Hydrogen and Formation of Aziridine Rings in Reactions of Benzonaphthyridines and their N-Oxides with Chloromethyl Phenyl Sulfone

 Treatment of benzonaphthyridines with chloromethyl phenyl sulfone in the presence of base led to the formation of aziridine rings annelated to the benzonaphthyridine skeleton, whereas their N-oxides underwent vicarious nucleophilic substitution of hydrogen (VNS), thus leading to the corresponding phenylsulfonylmethyl derivatives.     

Traceless solid-phase synthesis of nitrogen-containing heterocycles and their biological evaluations as inhibitors of neuronal sodium channels

The preparation of pyrimidine-2-thione, pyrimidine-2-one, pyrimidine, and benzo[b][1,4]diazepine derivatives using traceless solid-phase sulfone linker strategy is described. Key steps involved are (i) sulfinate S-alkylation, (ii) sulfone anion alkylation with an epoxide, (iii) gamma-hydroxyl sulfone --> gamma-ketosulfone oxidation, and (iv) traceless product release by a one-pot elimination-cyclization process. Elimination-cyclization was carried out under basic conditions with thiourea, methyl thiourea, methyl urea, guanidine hydrochloride, benzamidine hydrochloride and ortho-phenylene diamine. Twenty-three compounds were prepared, and 14 of them were evaluated by the Batrachotoxin (BTX) radioligand binding assay for their binding affinity to neuronal sodium channels. Compound 7c was found to be a potential neuronal sodium channels blocker.     

吸电子基团取代的苯和三氧化硫的反应研究

研究了室温下多种吸电子基团取代的苯和三氧化硫的反应, 用^1H NMR测定反应产物. 苯甲醛, 苯甲酸, 苯磺酸, 二苯砜, 二苯甲酮等均首先得到3-磺酸衍生物, 进一步反应得到少量的3,5-二磺酸衍生物. 苯磺酸还得到少量的3,3'-二磺酸二苯砜和3,5,3'-三磺酸二苯砜. 硝基苯只能进行单磺化反应. 苯甲酸甲酯则得到磺酸取代的苯甲酸和硫酸甲酯     

Synthesis of Allyl Aryl Sulfone Derivatives from Baylis?Hillman Acetates in Water

Various phenyl and p‐tolyl allyl sulfone derivatives were prepared stereoselectively by reacting Baylis? Hillman acetates with sodium 4‐R‐benzenesulfinate (R=H, Me) in H₂O. The reaction was very efficient in providing the corresponding sulfone derivatives in good to excellent yields (Table).     

Solid-phase synthesis of pyrazolines and isoxazolines with sodium benzenesulfinate as a traceless linker

[reaction: see text] The preparation of pyrazoline and isoxazoline derivatives with traceless solid-phase sulfone linker strategy is described. Key steps involved in the solid-phase synthetic procedure include (i) sulfinate S-alkylation, (ii) sulfone anion alkylation, (iii) gamma-hydroxy sulfone --> gamma-ketosulfone oxidation, and (iv) traceless product release via elimination-cyclization. A library of 12 pyrazolines and isoxazolines was synthesized.     

Vicarious Nucleophilic Substitution of Hydrogen and Formation of Aziridine Rings in Reactions of Benzonaphthyridines and their N-Oxides with Chloromethyl Phenyl Sulfone

Summary.  Treatment of benzonaphthyridines with chloromethyl phenyl sulfone in the presence of base led to the formation of aziridine rings annelated to the benzonaphthyridine skeleton, whereas their N-oxides underwent vicarious nucleophilic substitution of hydrogen (VNS), thus leading to the corresponding phenylsulfonylmethyl derivatives. Received December 11, 2000. Accepted (revised) January 22, 2001     

A new efficient route to 2-substituted azulenes based on sulfonyl group directed lithiation

Directed lithiation of p-tolyl 1-azulenyl sulfone (1) at the 2-position of the azulenyl group was achieved by using lithium 2,2,6,6-tetramethylpiperidide (LTMP). The azulenyllithium thus generated could be efficiently trapped with various electrophiles to form 2-substituted derivatives 2 in moderate to good yields. p-Tolyl 2-trimethylsilyl-1-azulenyl sulfone (2a) was transformed into cyclic sulfone derivative 3a through the directed lithiation in the p-tolyl group and subsequent intramolecular ring closure at the 8-position. 2-(Phenylsulfanyl)-1-azulenyl p-tolyl sulfone (2b) suffered from desulfonylation to form 2-phenylsulfanylazulene (4). The Suzuki coupling reaction of 2-iodo-1-azulenyl p-tolyl sulfone (2d) with arylboronic acids followed by desulfonylation efficiently gave 2-arylazulenes 10.     

Preparation of affinity carriers for the study of binding properties of aspartic proteinases

We have chosen aromatic amino acids and their derivatives as ligands for the affinity chromatography of aspartic proteinases (pepsins and pepsinogens). The following ligands were used: L‐tyrosine, L‐phenylalanine, tyramine, and N‐acetyl‐L‐phenylalanine, and their iodinated derivatives (mono‐ and di‐substituted) with free or blocked amino group. Two types of reactions were used for coupling ligands to Sepharose activated with divinyl sulfone (DVS): via amino group or via carboxyl group. Ligands with free amino group were directly coupled to the activated matrix (L‐tyrosine, 3‐iodo‐L‐tyrosine, 3,5‐diiodo‐L‐tyrosine, L‐phenylalanine, 4‐iodo‐L‐phenylalanine, tyramine); ligands with blocked amino group (N‐acetyl‐L‐phenylalanine, BOC‐L‐tyrosine, BOC‐3,5‐diiodo‐L‐tyrosine; BOC: tert‐butoxy carbonyl) were coupled to Sepharose containing linked ethylenediamine using the carbodiimide reaction. Alternatively, ethylenediamine was bound to free carboxyl croup using the same reaction and these ligand derivatives reacted with divinyl sulfone activated Sepharose. The prepared affinity carriers were used to study the binding properties of porcine pepsin and pepsinogen.     

Solid-phase synthesis of novel isoxazolocyclobutanones and isoxazolinocyclobutenones

[reaction: see text] The preparation of novel isoxazolocyclobutanone and isoxazolinocyclobutenone derivatives via a traceless solid-phase sulfone linker strategy is described. Key steps in the solid-phase protocol reported here include (i) sulfinate right arrow sulfone alkylation, (ii) four-member ring formation by sulfone dianion alkylation, (iii) heterocycle formation by nitrile oxide 1,3-dipolar cycloaddition, and (iv) traceless product release by cyclobutanol right arrow cyclobutanone oxidation with concomitant linker cleavage by sulfinate elimination.     

1,3-Dipolar cycloadditions with azomethine ylide species generated from aminocyclopropanes

Two types of bicyclic N-cyclopropyl glycine ester derivatives have been prepared and put under scrutiny as possible precursors of azomethine ylides. The results demonstrate that they can indeed participate in 1,3-dipolar cycloaddition reactions with dipolarophiles, as illustrated in the cases of phenyl vinyl sulfone, N-phenylmaleimide, diethyl fumarate and diethyl maleate. The relative configurations of the major diastereoisomers produced are consistent with the predicted generation of azomethine ylide species, reacting in concerted cycloaddition processes. This unprecedented way of generating such 1,3-dipoles provides access to functionalised pyrrolizidine and pyrrolidine derivatives, that would be difficult to make directly by more classic methods. It was also found that using phenyl vinyl sulfone or N-phenylmaleimide as the dipolarophile reactant, a domino nucleophilic conjugate addition/1,3-dipolar cycloaddition process may operate competitively.