Arylsulfonyl Group Research Articles

Tetrahydroisoquinoline Based Sulfonamide Hydroxamates as Potent Matrix Metalloproteinase Inhibitors.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Reaction of Arendiazonium Salts and SO2with α-Nitroolefins

In reaction of β-nitrostyrene and 2-(2-nitrovinyl)furan with arenediazonium chlorides and SO2 in the presence of copper(II) chloride products were obtained resulting from addition of arylsulfonyl group and a hydrogen atom across the C=C bond: 2-nitro-1-phenylethylsulfonylarenes and 2-(1-arylsulfonyl-2-nitroethyl)furans respectively. An anion-radical mechanism of the reaction was suggested.

Novel Trifunctional Building Blocks for Fluorescent Polymers.

Herein, we describe the synthesis of fluorescent 2-(arylsulfonyl)methacrylates and its polymers. These novel trifunctional monomers, possessing a fluorescent arylsulfonyl (ArSO2) group, an alkyl group (R), and a polymerizable olefin, serve as useful building blocks for functionalized fluorescent polymers.

Tetrahydroisoquinoline based sulfonamide hydroxamates as potent matrix metalloproteinase inhibitors

The synthesis and MMP inhibitory activity of a series of tetrahydroisoquinoline based sulfonamide hydroxamates are described. In nine MMPs tested, most of the compounds display potent inhibition activity except for MMP-7. Some subtle isozyme selectivity is observed by varying the substituents at the 6- and 7-positions and aromatic ring of arylsulfonyl groups.

Oligomeric guanidine synthesis assisted by TFA-sensitive arylsulfonylthiourea

Through arylsulfonyl activation of thiourea, efficient synthesis of oligomeric guanidines can be achieved in either solution or solid-phase. Incorporation of TFA-sensitive arylsulfonyl groups, such as Pbf, during the synthesis greatly simplifies deprotection procedures for obtaining the final oligomeric guanidine products.

π-Deficient α-arylsulfonyl esters as soft nucleophiles in organic synthesis

Different π-deficient arylsulfonyl groups have been studied as candidates for the stabilization of α-sulfonyl esters. The 3,5-bis(trifluoromethyl)phenylsulfonyl group has been shown to be the best substituent for the stereoselective synthesis of E-aconitates by a dialkylation–dehydrosulfinylation integrated process under PTC conditions using K2CO3 as base.

Conversion of N-(1-Arylsulfonyl-2,2-dichloroethenyl)carboxamides into Derivatives of 4,5-Dimercaptooxazole

In reaction of excess thiols with α-arylsulfonyl-substituted enamides containing two chlorine atoms in β-position to the amide moiety the chlorine atoms and the arylsulfonyl group attached to the C = C bond are replaced by alkylthio or arylthio groups. The sulfur-containing enamides obtained undergo cyclization when treated with phosphorus pentachloride or thionyl chloride to furnish 4,5-dimercaptooxazoles used for preparation of the corresponding disulfonyl derivatives. The latter were also obtained by treating in succession the N-(1-arylsulfonyl-2,2-dichloroethenyl)carboxamides with sodium hydrosulfide, then with alkyl halides, and hydrogen peroxide in acetic acid.

Synthesis and Nonlinear Optical, Photophysical, and Electrochemical Properties of Subphthalocyanines

Novel boron(III) subphthalocyanines (SubPcs) soluble in organic solvents containing a variety of donor and acceptor substituent groups have been synthesized by boron trihalide-induced cyclotrimerization of adequately substituted derivatives of phthalonitrile in 1-chloronaphthalene. The choice of the substituents on the 1,2-dicyanobenzene derivatives has been made taking into account the high reactivity of the Lewis acid BCl3 toward many functional groups. Considering this limitation, we set out to synthesize phthalodinitriles equipped with iodo, nitro, alkyl- or arylthio, alkyl- or arylsulfonyl groups that are sufficiently stable under the required reaction conditions and also provide an easily accessible set of acceptor/donor substituents. The quadratic and cubic hyperpolarizabilities of these compounds as well as their linear optical and electrochemical properties have been measured by several techniques, including EFISH (at two wavelengths), HRS, and THG, steady-state and time-resolved absorption and fluorescence, laser-induced optoacoustic calorimetry, time-resolved near-infrared emission spectroscopy, and cyclic voltammetry. βHRS has been measured at 1.46 μm, where the contamination from the multiphoton-induced fluorescence can be ruled out. βHRS reachs high values that markedly depend on substitution. It shows a clear enhancement with the acceptor character of the substituents, the highest values being obtained for the compounds bearing the strongest acceptor groups. They are comparable or even superior to many efficient second-order compounds. A main outcome of these results is that an adequate choice of the substituents offers a promising route for optimization of the quadratic response of the SubPcs. This kind of compounds is less prone to aggregation than their expanded analogues, the phthalocyanines, fluoresces with quantum yields ca. 0.25, lower than those typical for phthalocyanines, and has larger triplet quantum yields. The triplet-state lifetime is in the 100-μs time range, long enough for efficient oxygen quenching. Indeed, subphthalocyanines sensitize singlet molecular oxygen, O2(1Δg), with quantum yields ranging from 0.23 to 0.75. The ground-state oxidation potentials are similar to those of phthalocyanines, while the reduction potentials are clearly more negative; i.e., they are more difficult to reduce. In contrast, electronically excited subphthalocyanines are more easily oxidized than the corresponding phthalocyanines by ca. 500 mV which results in lower photostability, especially in polar solvents.

The Reaction of N-Magnesium Derivatives of Pyrroles with N-Mesylchloromethylpyrroles: A Synthesis of Dipyrrylmethanes

Attachment of an alkyl- or arylsulfonyl group at the nitrogen atom of a pyrrole reduces the aromaticity and electron availability of the system. This is confirmed by the structure of an N-tosylated chloromethylpyrrole determined by X-ray crystallography. In agreement, N-mesylated chloromethylpyrroles are handleable materials which react smoothly with N-magnesium derivatives of pyrroles to provide a novel route for synthesis of dipyrrylmethanes. Several examples of this synthesis are described, including the construction of molecules carrying deuterium at the interpyrrolic methylene group.

Silane-mediated direct condensation of nitroarenes with cinnamyl-type sulfones. The way to 2-aryl-4-X-quinolines and their hetero analogs

DBU/silane mediated double condensation of nitroarenes with cinnamyl-type sulfones proceeds smoothly to yield 2-aryl-4-arylsulfonyl quinolines and their hetero analogs. Arylsulfonyl group can be easily replaced by different nucleophiles.

Synthesis of 2-Bis(trifluoromethyl)hydroxymethyl Substituted Cyclic Amines through Novel Intramolecular Substitution of an Arylsulfonyl Group

Abstract ω-Amino-1,1-bis(trifluoromethyl)-2-sulfonyl-1-pentanol or -hexanol provided the corresponding pyrrolidine or piperidine having BTHM group at the 2-position via intermediary epoxide by treating with NaOH in the presense of phase-transfer catalyst.

ChemInform Abstract: Highly Substituted Cyclopentadienes with Arylthio‐ and Arylsulfonyl Groups.

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Synthesis of Aristotelia‐type alkaloids. Part VII. Syntheses of (±)‐sorelline, (±)‐serratenone, and (±)‐aristotelin‐19‐one

AbstractThe imine obtained by condensing indole‐protected 2‐(indol‐3‐yl)acetaldehyde (5) with the terpinylamine derivative (±)‐4 was cyclized in 51% yield to the 19‐substituted hobartine derivative (±)‐20 upon exposure to anhydrous HCOOH. This pivotal intermediate was further elaborated into the indole alkaloids (±)‐serratenone ((±)‐22) and (±)‐sorelline ((±)‐29). In the course of these investigations, a novel rearrangement was uncovered; a Lewis acid‐catalyzed 1,3‐migration of an arylsulfonyl group from the indole N‐atom into the benzene ring. The discovery that synthetic (±)‐aristotelin‐19‐one ((±)‐34) has decidedly different spectroscopic properties than aristolasicone, a metabolite for which the structure has been recently proposed, led to a revision of the structure of the latter.

Hochsubstituierte Cyclopentadiene mit Arylthio‐ und Arylsulfonyl‐Gruppen

Highly Substituted Cyclopentadienes with Arylthio and Arylsulfonyl GroupsCyclopentadienes 1 react with diaryl disulfides 2 to form the tetrakis(arylthio)cyclopentadienides 3, which have been oxidized with m‐chloroperbenzoic acid to give the tetrakis(arylsulfonyl)cyclopentadienides 5. Protonation of 5 yields the tetrakis(arylsulfonyl)cyclopentadienes 7 by migration of arylsulfonyl groups. Oxidation of 3 by iodine leads to the dihydropentafulvalenes 11. By reaction of 3 with arylthiosulfonates 14 the pentakis(arylthio)cyclopentadienes 15 have been obtained. Their salts 16 may be oxidized to form the pentakis(arylsulfonyl)cyclopentadienides 17, or condensed with sulfenyl chlorides to give the hexakis(arylthio)cyclopentadienes 19. The structure of the phenylthio compound 19a was confirmed by an X‐ray structure analysis.

Diels-Alder reactions of 1,2-(1,1'-binaphthalene-2,2'-diyldisulfonyl)ethylene with symmetrical and unsymmetrical dienes

The C 2 -symmetrical chiral reagent 1,2-(1,1'-binaphthalene-2,2'-diyldisulfonyl) ethylene (1) is a reactive dienophile and forms Diels-Alder adducts with symmetrical and unsymmetrical dienes. In the case of unsymmetrical dienes the reaction affords, in most cases, a single diastereomeric adduct whose stereochemistry has been determined by NMR spectroscopy and confirmed by X-ray structure determination of selected adducts. The arylsulfonyl groups can be removed with formation of a double bond, making 1 a chiral synthetic equivalent of acetylene in [4+2]-cycloaddition reactions. The binaphthyl auxiliary can be recovered and recycled

Oxygen‐17 NMR spectral studies of selected aromatic sulfones

AbstractOxygen‐17 NMR spectra of several organosulfur compounds containing the arylsulfonyl group (ArSO2–) are reported. Shielding effects are interpreted in terms of γ‐ortho CH interactions with the sulfonyl oxygens rather than conjugative interactions involving the aryl substituent and the attached SO2 group. The lanthanide shift reagent Eu(fod)3 is useful for discriminating ‘internal and external’ accidental chemical shift coincidence.

Oxamates derived from 5‐aminopyrazoles

AbstractSeveral oxamates were prepared from ethyl oxalyl chloride and 5‐amino‐4‐cyanopyrazoles substituted in the 1‐position with aryl, aroyl and arylsulfonyl groups. Both aroyl and arylsulfonyl groups suffered chloride‐induced cleavage during this process. The synthesis of 7‐(6‐chloro‐3‐pyridazinyl)‐7H‐pyrazolo[3,4‐d]‐1,2,3‐tri‐azin‐4(3H)‐one (11) and its reaction with methanol to give 1‐(6‐chloro‐3‐pyridazinyl)‐5‐methoxy‐1H‐pyrazole‐4‐carboxamide (12) are also reported. A mechanism for this interesting transformation is presented.

ChemInform Abstract: DIAZO REACTIONS WITH UNSATURATED COMPOUNDS. III. ANIONOARYLSULFONYLATION OF SOME DIENE HYDROCARBONS

AbstractDiene (I) reagieren mit Diazoniumsalzen (All) und Schwefeldioxid in Gegenwart von Kupfersalzen unter 1,4‐Addition zu den Sulfonen b8 (III).

Polysulfonylethenes. Communication 3. Reactions of tetrakis(alkylsulfonyl) ethenes with amines

1. The reaction of tetrakis(alkylsulfonyl)ethenes and tetrakis(arylsulfonyl)ethanes with secondary or bulky primary amines gave good yields of previously unreported di(alkylsulfonyl)acetamides and di(arylsulfonyl)acetamides which are the products of the hydrolysis of unstable tris(alkylsulfonyl)vinylamines and tris(arylsulfonyl)vinylamines. 2. The analogous reaction with primary amines gave, in addition to acetamides, previously unreported 1,1-di(alkylsulfonyl)-2,2-di(alkylamino)ethenes and 1,1-di(arylsulfonyl)-2,2-di(arylamino)ethenes, which are the products of the replacement of two alkylsulfonyl or arylsulfonyl groups. 3. Concurrent fragmentation is characteristic only for highly basic amines with pKb < 5–6.

Antibiotic X-5108. IX. Chemical conversion of mocimycin to aurodox and derivatives of aurodox, goldinamine and mocimycin.

Mocimycin was converted to the acylesters by selective acylation of the hydroxyl group of the 4-hydroxy-1-methyl-2(1H)pyridinone moiety. Subsequent N-methylation at the nuclear nitrogen and removal of the protective group from the resulting reaction products afforded aurodox. Mono-O-acetylmocimycin and several analogous aurodox esters thus prepared possess antibacterial activity in vitro and growth-promotion properties in poultry. Esters of aurodox involving the hydroxyl group of the 4-hydroxy-1-methyl-2(1H)pyridinone moiety are activated. Accordingly, acetic acid treatment of the aurodox esters generates O-acylgoldinamines which undergo transacylation furnishing N-acylgoldinamines. Alternatively, N-acylgoldinamines can be prepared by selective mono--o-arylsulfonylation of aurodox, liberating o-arylsulfonylgoldinamine by treatment with acetic acid followed by N-acylation and removal of the protective arylsulfonyl group. A third approach to N-acylgoldinamines consists in direct N-acylation of goldinamine itself which is prepared by acetic acid treatment of aurodox. None of these derivatives prepared, however, exhibited significant antimicrobial or growth-promoting properties, suggesting that goldinonic acid moiety, or a closely related derivative thereof, is required for biological activity.