- Remote Site-Specific Radical Alkynylation of Unactivated C-H Bonds
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A method for remote radical C-H alkynylation at unactivated sites is reported. C-H functionalization proceeds via 1,5-hydrogen atom transfer (HAT) to amidyl radicals that are generated via an addition/fragmentation reaction. The readily installed N-allylsulfonyl moiety is used as a precursor of the N-centered radical. Unactivated secondary and tertiary as well as selected primary C-H bonds can be functionalized by this method.
- Wang, Lin,Xia, Yong,Bergander, Klaus,Studer, Armido
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- Site-Selective Remote Radical C?H Functionalization of Unactivated C?H Bonds in Amides Using Sulfone Reagents
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A general and practical strategy for remote site-selective functionalization of unactivated aliphatic C?H bonds in various amides by radical chemistry is introduced. C?H bond functionalization is achieved by using the readily installed N-allylsulfonyl moiety as an N-radical precursor. The in situ generated N-radical engages in intramolecular 1,5-hydrogen atom transfer to generate a translocated C radical which is subsequently trapped with various sulfone reagents to afford the corresponding C?H functionalized amides. The generality of the approach is documented by the successful remote C?N3, C?Cl, C?Br, C?SCF3, C?SPh, and C?C bond formation. Unactivated tertiary and secondary C?H bonds, as well as activated primary C?H bonds, can be readily functionalized by this method.
- Xia, Yong,Wang, Lin,Studer, Armido
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- Solvent-free, metal-free, aza-prins cyclization: Unprecedented access to δ-sultams
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Aza-Prins and the pauper: Aza-Prins cyclization between γ,δ-unsaturated tosylamines and aldehydes was successfully performed under solvent-free and metal-free conditions. When applied to β,γ-unsaturated sulfonamides, the corresponding δ-sultams were isolated in good yields (see scheme). This approach constitutes a new route to cyclic sulfonamides. Copyright
- Clarisse, Damien,Pelotier, Béatrice,Fache, Fabienne
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- Ring closing metathesis and metal-catalyzed cyclopropanation for the preparation of sultone derivatives
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Ring closing metathesis (RCM) using Grubbs catalyst 2nd generation as a catalyst was applied to prepare series of novel unsaturated sultones with high yields. Many attempts, were applied for the cyclopropanation of the allylic sultones by Simmon-smith cyclopropanation using diethyl zinc/diiodomethane or Zn-Cu/diiodomethane but in each case the corresponding cyclic adduct was not formed. A novel palladium or preferably rhodium-catalyzed cyclopropanation of unsaturated sultones with ethyl diazoacetate was achieved by the transition metal-catalyzed transfer of a CH-CO2Et unit. The reaction was applied by a portion-wise addition of ethyl diazoacetate over 6h to a mixture of the sultones and palladium(II) acetate or rhodium(II) acetate dimer under low temperature (0-20 o C). The desired products of the cyclopropanation were achieved in each case, as a single diastereomer with 33- 37% yield in the allylic sultones and 10% for vinylic sultone.
- Ali, Korany A.,Metz, Peter
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- 3H-1,2-benzoxathiepine 2,2-dioxides: a new class of isoform-selective carbonic anhydrase inhibitors
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A new chemotype with carbonic anhydrase (CA, EC 4.2.1.1) inhibitory action has been discovered, the homo-sulfocoumarins (3H-1,2-benzoxathiepine 2,2-dioxides) which have been designed considering the (sulfo)coumarins as lead molecules. An original synthetic strategy of a panel of such derivatives led to compounds with a unique inhibitory profile and very high selectivity for the inhibition of the tumour associated (CA IX/XII) over the cytosolic (CA I/II) isoforms. Although the CA inhibition mechanism with these new compounds is unknown for the moment, we hypothesize that it may be similar to that of the sulfocoumarins, i.e. hydrolysis to the corresponding sulfonic acids which thereafter anchor to the zinc-coordinated water molecule within the enzyme active site.
- Pustenko, Aleksandrs,Stepanovs, Dmitrijs,?alubovskis, Raivis,Vullo, Daniela,Kazaks, Andris,Leitans, Janis,Tars, Kaspars,Supuran, Claudiu T.
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- Preparation method of allylsulfonyl chloride
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The invention discloses a preparation method of allylsulfonyl chloride. The method comprises the following steps: simultaneously adding sodium allysulfonate, a catalyst, a polymerization inhibitor and an inert solvent into a reaction container, heating while stirring, dropwise adding thionyl chloride at the reaction temperature, and carrying out heat preservation reaction to obtain reaction liquid of allylsulfonyl chloride; and after the reaction is finished, filtering to obtain filtrate, and carrying out post-treatment on the filtrate to obtain the product allylsulfonyl chloride. According to the preparation method of the allylsulfonyl chloride, the prepared allylsulfonyl chloride has two reaction functional groups, namely a sulfonyl chloride group and an allyl double bond, so that the allylsulfonyl chloride serving as a raw material or an intermediate is better in selectivity and wider in application range. In the reaction process, a proper combined catalyst and a proper combined polymerization inhibitor are selected, so that the reaction activity is greatly improved, the stability of the product is ensured, the product polymerization is effectively prevented, and the reaction yield is improved.
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Paragraph 0017-0020
(2021/06/23)
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- Process for preparing 2 - (methylsulfonyl) - ethylene oxide and derivatives thereof
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The invention relates to 2 - (methylsulfonyl) - ethylene oxide and a preparation method thereof, belonging to the technical field of synthesis of ethylene oxide derivatives, and the method comprises the following steps: raw materials are vinyl methyl sulfone or allyl methyl sulfone 1:2:4 or methylallyl sulfonic acid ester. @timetimepieces are added dropwise to m-chloroperoxybenzoic acid by dropwise adding time of 30 min, 25 min, 10 min, heating reflux 15 - 30h and cooling to room temperature filtration. When the starting material is a vinyl methyl sulfone, the product is 2 - (methylsulfonyl) - ethylene oxide. When the starting material is allyl methyl sulfone, the product is methyl -2 and 3 - propylene oxide sulfonate. When the starting material is methylallyl sulfonate, the product is methyl -2 and 3 - epoxypropane sulfonate. The molar ratio of the raw material and the m-chloroperbenzoic acid is 1: (1.8 - 2.4). The preparation method is simple and high in yield.
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Paragraph 0038-0040; 0051-0053
(2021/09/29)
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- Aryl derivatives of 3H-1,2-benzoxathiepine 2,2-dioxide as carbonic anhydrase inhibitors
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A new series of homosulfocoumarins (3H-1,2-benzoxathiepine 2,2-dioxides) possessing various substitution patterns and moieties in the 7, 8 or 9 position of the heterocylic ring were prepared by original procedures and investigated for the inhibition of four physiologically relevant carbonic anhydrase (CA, EC 4.2.1.1) isoforms, the human (h) hCA I, II, IX and XII. The 8-substituted homosulfocoumarins were the most effective hCA IX/XII inhibitors followed by the 7-substituted derivatives, whereas the substitution pattern in position 9 led to less effective binders for the transmembrane, tumour-associated isoforms IX/XII. The cytosolic isoforms hCA I and II were not inhibited by these compounds, similar to the sulfocoumarins/coumarins investigated earlier. As hCA IX and XII are validated anti-tumour targets, with one sulphonamide (SLC-0111) in Phase Ib/II clinical trials, finding derivatives with better selectivity for inhibiting the tumour-associated isoforms over the cytosolic ones, as the homosulfocoumarins reported here, is of crucial importance.
- Pustenko, Aleksandrs,Nocentini, Alessio,Bala?ova, Anastasija,Alafeefy, Ahmed,Krasavin, Mikhail,?alubovskis, Raivis,Supuran, Claudiu T.
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p. 245 - 254
(2019/12/11)
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- Olefination with Sulfonyl Halides and Esters: E-Selective Synthesis of Alkenes from Semistabilized Carbanion Precursors
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Carbanions of sulfonyl halides and activated sulfonates add to carbonyl compounds, and so-formed aldol-type adducts spontaneously fragment into olefins. This transformation mimics the one-pot Julia olefination with (hetero)aryl sulfones, but the mechanism of fragmentation involves a four-membered intermediate, typical for reactivity of phosphorus reagents. Moreover, in contrast to the reactions of sulfones, sulfonates of fluorinated alcohols (TFE and HFI) produce byproducts that are easily removed during workup. In our report, we focus on reactions of unstabilized and semistabilized carbanion precursors: alkylsulfonates, and allyl- and benzylsulfonates, respectively. In particular for semistabilized systems, olefins were synthesized as predominant E isomers in good yields. The presented studies reveal that optimal reaction conditions, including the type of base and alcohol groups of the sulfonates, are different depending on stabilization of the carbanion precursors and structure of the carbonyl substrates. The practical synthetic guide is supplemented with a discussion of the mechanism, based on reactivity studies of intermediates and identification of side-products.
- Górski, Bartosz,Basiak, Dariusz,Talko, Alicja,Basak, Tymoteusz,Mazurek, Tomasz,Barbasiewicz, Micha?
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supporting information
p. 1774 - 1784
(2018/04/27)
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- 6-MEMBERED URACIL ISOSTERES
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Provided herein are dUTPase inhibitors, compositions comprising such compounds and methods of using such compounds and compositions.
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Paragraph 0780
(2018/06/12)
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- HYDANTOIN CONTAINING DEOXYURIDINE TRIPHOSPHATASE INHIBITORS
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Provided herein are dUTPase inhibitors, compositions comprising such compounds and methods of using such compounds and compositions.
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Paragraph 0993
(2018/06/12)
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- NOVEL INHIBITORS OF PROTEIN KINASES
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Protein kinases are regulators of cellular signaling and their functional dysregulation is common in carcinogenesis and many other disease states or disorders. The present invention relates to novel chemical entities that have biological activity to modulate mammalian protein kinase enzymes. In particular, compounds of the invention display potent inhibition of breast tumor related kinase (BRK).
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Paragraph 0088; 0108
(2017/09/08)
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- COLORED CHARGED SILSESQUIOXANES
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The present invention provides compounds of Formula (1A), wherein Formula (II) is Formula (III) and Formula (1B) wherein Formula (IV) is Formula (V) and electrophoretic devices comprising the compounds of formula (1A) or (1B).
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Paragraph 0758; 0788-0790; 0793-0794
(2018/02/10)
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- DABCO-bis (sulfur dioxide), DABSO, as a convenient source of sulfur dioxide for organic synthesis: Utility in sulfonamide and sulfamide preparation
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The charge-transfer complex generated from the combination of DABCO and sulfur dioxide, DABSO, is a bench-stable colorless solid suitable for use in organic synthesis as a replacement for gaseous sulfur dioxide. The complex can be combined with Grignard reagents to form sulfinates, which can then be converted in situ to a series of sulfonamides. Alternatively, reaction with anilines and iodine leads to the formation of a series of sulfamides. Cheletropic addition between DABSO and 2,3-dimethylbutadiene provides the corresponding sulfolene.
- Woolven, Holly,Gonzalez-Rodriguez, Carlos,Marco, Isabel,Thompson, Amber L.,Willis, Michael C.
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supporting information; experimental part
p. 4876 - 4878
(2011/12/05)
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- BCl3-mediated ene reaction of sulfur dioxide and-unfunctionalized alkenes
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The first ene reactions of SO2 and unfunctionalized alkenes are reported. Calculations suggest that the endergonic ene reactions of SO 2 with alkenes can be used to generate β,γ-unsaturated sulfinyl and sulfonyl compounds. Indeed, in the presence of one equivalent of BCl3, the unstable sulfinic acid form stable sulfinic acid-BCl 3 complexes that can be reacted in situ with NCS to generate corresponding sulfonyl chlorides, or with a base to generate corresponding sulfinates. The latter can be reacted with electrophiles to generate sulfones, or with silyl chloride to form β,γ-unsaturated silyl sulfinates. The sulfinic acid-BCl3 complexes can be reacted with ethers that act as oxygen nucleophiles to produce corresponding sulfinic esters. Thus one-pot, three-component synthesis of β,γ-unsaturated sulfonamides, sulfinyl esters and sulfones have been developed starting from alkenes and sulfur dioxide (reagent and solvent).
- Markovic, Dean,Volla, Chandra M. R.,Vogel, Pierre,Varela-Alvarez, Adrian,Sordo, Jose A.
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supporting information; experimental part
p. 5969 - 5975
(2010/09/04)
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- The catalyzed desulfinylative allylation of carbonyl compounds with alk-2-enesulfonyl chlorides and silyl alk-2-enesulfinates
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Coupling up with sulfonyl chlorides: An ene reaction of alkenes with SO2·BCl3 permits the one-pot conversion of simple alkenes into b,g-unsaturated sulfonyl chlorides or sulfinic silyl esters. These compounds can then be used as nucleophilic allylating agents with aldehydes and ketones to generate the corresponding homoallylic alcohols (see scheme) with good chemo-and diastereoselectivity in the presence of a suitable catalyst and reducing agent.
- Volla, Chandra M. R.,Markovic, Dean,Laclef, Sylvain,Vogel, Pierre
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supporting information; scheme or table
p. 8984 - 8988
(2010/10/02)
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- Ligandless iron-catalyzed desulfinylative C-C allylation reactions using Grignard reagents and alk-2-enesulfonyl chlorides
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Alk-2-enesulfonyl chlorides 1-4 were synthesized by the BCl3-promoted ene reaction of alkenes with SO2. These sulfonyl chlorides were then used as electrophilic partners in iron-catalyzed desulfinylative cross-coupling reactions with different Grignard reagents (aromatic, aliphatic, and heteroaromatic). The reaction can be catalyzed with even 2 mol-% of the simple iron salt Fe(acac)3. The regioselectivity of these allylations was studied by using sulfonyl chlorides 3 and 4 with aryl Grignard reagents. The scope of these allylations was further extended by the coupling of ester-substituted alk-2-enesulfonyl chloride 10 with aromatic Grignard reagents. Symmetrical products were synthesized by double C-C allylation with the use of 2-methylidenepropane-1,3-disulfonyl chloride (12). Wiley-VCH Verlag GmbH & Co. KGaA.
- Volla, Chandra M. R.,Markovic, Dean,Dubbaka, Srinivas Reddy,Vogel, Pierre
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experimental part
p. 6281 - 6288
(2011/02/28)
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- Palladium-catalyzed desulfinylative C-C allylation of Grignard reagents and enolates using allylsulfonyl chlorides and esters
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2-Methylprop-2-ene-, prop-2-ene-, 1-methylprop-2-ene-, and (E)-but-2-enesulfonyl chlorides have been used as electrophilic partners in desulfinylative palladium-catalyzed C-C coupling with Grignard reagents and sodium salts of dimethyl malonate and methyl
- Rao Volla, Chandra M.,Dubbaka, Srinivas Reddy,Vogel, Pierre
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scheme or table
p. 504 - 511
(2009/04/07)
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- Delayed fibril formation of amylin(20-29) by incorporation of alkene dipeptidosulfonamide isosteres obtained by solid phase olefin cross metathesis
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The synthesis of a new peptidomimetic structure, the alkene dipeptidosulfonamide isostere, is described. The synthesis is based on a cross metathesis reaction between two allylic building blocks, both in solution and on the solid phase. This method was also applicable to the solid phase synthesis of alkene dipeptide isosteres. Derivatives of amylin(20-29) containing the alkene dipeptidosulfonamide isostere as well as the alkene dipeptide isostere were successfully synthesized using the solid phase cross metathesis method. Investigation of relations between structure and fibril formation of these amylin(20-29) derivatives showed retardation of fibril formation and altered secondary structures, compared to native amylin(20-29).
- Brouwer, Arwin J.,Elgersma, Ronald C.,Jagodzinska, Monika,Rijkers, Dirk T.S.,Liskamp, Rob M.J.
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- Sulfonyl chloride formation from thiol derivatives by N-chlorosuccinimide mediated oxidation
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Oxidation of several thiol derivatives by a combination of N-chlorosuccinimide and dilute hydrochloric acid proceeded smoothly, affording the corresponding sulfonyl chlorides in good yield. Georg Thieme Verlag Stuttgart.
- Nishiguchi, Atsuko,Maeda, Kazuhiro,Miki, Shokyo
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p. 4131 - 4134
(2008/03/13)
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- PYRAZOLE DERIVATIVE, MEDICINAL COMPOSITION CONTAINING THE SAME, MEDICINAL USE THEREOF, AND INTERMEDIATE FOR PRODUCTION THEREOF
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The present invention provides pyrazole derivatives represented by the general formula: wherein R1 represents H, an optionally substituted C1-6 alkyl group etc.; one of Q and T represents a group represented by the general formula: or a group represented by the general formula: while the other represents an optionally substituted C1-6 alkyl group etc.; R2 represents H, a halogen atom, OH, an optionally substituted C1-6 alkyl group etc.; X represents a single bond, O or S; Y represents a single bond, a C1-6 alkylene group etc. ; Z represents CO or SO2; R4 and R5 represent H, an optionally substituted C1-6 alkyl group etc.; and R3, R6 and R7 represent H, a halogen atom etc., pharmaceutically acceptable salts thereof or prodrugs thereof, which exhibit an excellent inhibitory activity in human SGLT1 and are useful as agents for the prevention or treatment of a disease associated with hyperglycemia such as diabetes, diabetic complications or obesity, and pharmaceutical compositions comprising the same, pharmaceutical uses thereof, and intermediates for production thereof.
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Page/Page column 41-42
(2008/06/13)
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- Synthesis of cyclic sulfonamides via intramolecular copper-catalyzed reaction of unsaturated iminoiodinanes
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(equation presented) Olefinic primary sulfonamides were treated with iodebenzene diacetate and potassium hydroxide in methanol to give intermediate iminoiodinanes. Catalytic copper(I) or (II) triflate then provided intramolecular nitrene delivery leading to aziridene formation except in one case where a rare copper-catalyzed C-H insertion was observed. The aziridines could be opened by various nucleophiles (methanol, thiophenol, allylmagnesium bromide, benzylamine) to give the corresponding substituted cyclic sulfonamides.
- Dauban, Philippe,Dodd, Robert H.
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p. 2327 - 2329
(2007/10/03)
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- Synthesis of 1-alkene-1,3-sultones from 2,3-epoxy-alkanesulfonyl chlorides
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Dehydrochlorination of αβ-epoxy sulfonyl chlorides 3 leads to 1-alkene-1,3-sultones 1 most probably via epoxy sulfenes 2.
- Bonini, Bianca F.,Kemperman, Gerjan,Willems, Sander T.H.,Fochi, Mariafrancesca,Mazzanti, Germana,Zwanenburg, Binne
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p. 1411 - 1413
(2007/10/03)
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- The thermal desulfination of allylic sulfonyl halides
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Allylic sulfonyl halides can be generated by halogenolysis of the corresponding triorganotin sulfinates. Allylic sulfonyl bromides and iodides undergo a first order, thermal desulfination with allylic rearrangement to yield the corresponding allylic halides. The desulfination of a cyclic allylic sulfonyl bromide is stereospecific, proceeding with γ-syn bromine migration.
- King, Malcolm D.,Sue, Rodney E.,White, Rodney H.,Young, David J.
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p. 4493 - 4496
(2007/10/03)
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- Mechanisms of hydrolysis and related nucleophilic displacement reactions of alkanesulfonyl chlorides: pH dependence and the mechanism of hydration of sulfenes
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pH-rate profiles, primary kinetic isotope effects, deuterium substitution patterns, and pH-product ratios in the presence of added nucleophiles provide evidence for the following overlapping set of mechanisms for the hydrolysis of methanesulfonyl chloride (1) (in 0.1 M KCl at 25 °C): (a) pH ≤ 1-6.7, reaction with water by direct nucleophilic attack on the sulfonyl chloride; (b) pH ≥ 6.7-11.8, rate-determining attack by hydroxide anion to form sulfene (2), which is then trapped by water in a fast step; and (c) pH ≥ 11.8, sulfene formation and sulfene trapping by hydroxide anion; careful inspection showed no sign of sulfene formation in the reaction with water or of direct displacement by hydroxide anion. This pattern, with appropriate variations in the values of pHi (the pH at which two competing mechanisms have the same rate), is apparently general for simple alkanesulfonyl chlorides having at least one hydrogen on the carbon bearing the sulfonyl group. Azide and acetate anions react with 1 below pHi for 1 (6.7) by direct nucleophilic substitution at the sulfur, but above pHi by trapping of the sulfene. 2-Chlorophenoxide anion reacts with 1 below pH 6.7 by both (a) direct displacement to form the ester and (b) elimination to form the sulfene. Above pH 6.7, sulfene is formed from the sulfonyl chloride by reaction with either 2-chlorophenoxide or hydroxide ion; this is followed by trapping of the sulfene with 2-chlorophenoxide, water, or hydroxide. The possibility of the 2-chlorophenoxide anion acting as a general base promoting the reaction of water with either 1 and 2 was examined, but no sign of either process was detected.
- King,Lam,Skonieczny
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p. 1743 - 1749
(2007/10/02)
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- N-sulfonyl-N-dihalophenylimidazolidinediones
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3-(3' -Dihalophenyl)-1-sulfonylimidazolidine-2,4-5'-diones of the formula: STR1 wherein X is a halogen atom, R1 is a C1 -C12 alkyl group, a C2 -C4 alkenyl group or a halogenated C1 -C4 alkyl group having 1 to 3 halogen atoms, and R2 and R3 are individually a hydrogen atom or a methyl group, which show high microbicidal activities against various fungi and bacteria without any material toxicity to mammals and which plants and can be produced by reacting the corresponding 1-unsubstituted compound with a sulfonyl halide.
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- Anthraquinone disperse dyestuffs
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1-Amino-4-hydroxy 2-p-alkoxy-benzenesulfonyloxy anthraquinone disperse dyestuffs have been prepared.
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