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Ring closure of 2-thia- and 2-sulfonyl-5-hexenyl radicals
Reductive cyclisation of the 2-sulfonyl-5-hexenyl radical with tributyltin hydride in benzene at 80°C affords a 73:23 mixture of the sulfones derived from 5-exo- and 6-endo- ring closure with a small quantity (4%) of reduced material; under identical conditions, the 2-thia-5-hexenyl radical gives a 70:13:17 mixture of the corresponding sulfides. (C) 2000 Elsevier Science Ltd.
Della,Graney
p. 7987 - 7990
(2000)
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Regioselective chlorination of phenols in the presence of tetrahydrothiopyran derivatives
Four six-membered cyclic sulfides, namely tetrahydrothiopyran, 3-methyltetrahydrothiopyran, 4-methyltetrahydrothiopyran and 4,4-dimethyltetrahyrdrothiopyran have been used as moderators in chlorination reactions of various phenols with sulfuryl chloride in the presence of aluminum or ferric chloride. On chlorination of phenol, ortho-cresol and meta-cresol the para/ortho chlorination ratios and yields of the para-chloro isomers are higher than when no cyclic sulfide is used for all of the cyclic sulfides, but chlorination of meta-xylenol is less consistent, with some cyclic sulfides producing higher p/o ratios and others producing lower ratios than reactions having no sulfide present.
Smith, Keith,Williams, Des,El-Hiti, Gamal A.
p. 529 - 538
(2019/06/13)

Synthesis, structure, and reactions of a copper-sulfido cluster comprised of the parent Cu2S unit: {(NHC)Cu}2(μ-S)
The synthesis of the first CuI2(μ-S) complex, {(IPr?)Cu}2(μ-S) (IPr? = 1,3-bis(2,6-(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene; 1), has been accomplished via three synthetic routes: (1) salt metathesis between (IPr?)CuCl and Na2S; (2) silyl-deprotection reaction between (IPr?)Cu(SSiMe3) and (IPr?)CuF; and (3) acid-base reaction between (IPr?)Cu(SH) and (IPr?)Cu(OtBu). The X-ray crystal structure of 1 exhibits two two-coordinate copper centers connected by a bent Cu-S-Cu linkage. Application of these synthetic routes to analogous precursors containing the sterically smaller ligand IPr (1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene), in place of IPr?, resulted in the formation of a transient product proposed as {(IPr)Cu}2(μ-S) (2), which decomposes quickly in solution. The instability of 2 probably results from the insufficient steric protection provided by IPr ligands to the unsaturated Cu2(μ-S) core; in contrast, 1 is stable both in solution and solid state for weeks. The nucleophilic sulfido ligand in 1 reacts with haloalkyl electrophiles (benzyl halides and dibromoalkanes) with formation of C-S bonds, affording (IPr?)Cu(SCH2Ph) and cyclic thioethers, respectively.
Zhai, Junjie,Filatov, Alexander S.,Hillhouse, Gregory L.,Hopkins, Michael D.
p. 589 - 595
(2015/12/26)

Synthesis of common-sized heterocyclic compounds by intramolecular cyclization over halide cluster catalysts
Five- to seven-membered common-sized heterocyclic compounds containing an oxygen, sulfur, or nitrogen were synthesized by the intramolecular condensation of α,ω-hydroxy, mercapto, or amino alkanes, respectively, over halide cluster complexes as a thermally stable molecular solid weak acid catalyst in the gas phase at temperatures ≥150 °C. From ω- mercapto and ω-amino alcohols, cyclic sulfides and amines were obtained, respectively. These unimolecular reactions are thermodynamically and kinetically favored.
Nagashima, Sayoko,Sasaki, Tomoaki,Kamiguchi, Satoshi,Chihara, Teiji
supporting information
p. 764 - 766
(2015/06/22)

Synthesis of 3,6-diaryl-1,4,5-thiadiazepines from substituted 2-thiocyano acetophenone and investigation of reaction mechanism
In this work, we have studied the reaction of substituted 2-thiocyanoacetophenone and hydrazine hydrate as a novel and simple pathway for the preparation of the substituted 1,4,5-thiodiazepine ring system. The mechanism of this reaction revealed that in the initial step condensation of hydrazine with carbonyl groups of substituted 2-thiocyanoacetophenons 2a-2f gives the corresponding substituted aromatic dithiocyano azide intermediates which in turn undergo cyclization to1,4,5-thiadiazepines in the presence of hydrazine. This cyclization is a novel method for the preparation of sulfide bond from the reaction of hydrazine and a dithiocyano intermediate. An account of the reaction mechanism is given.
Rahimizadeh,Feizyzadeh,Bakavoli,Eshghi
p. 276 - 283
(2013/08/26)

Aerobic oxidation of thiols to disulfides using iron metal-organic frameworks as solid redox catalysts
Aerobic oxidation of thiols to disulfides has been carried out using iron metal-organic frameworks (MOFs) as solid redox catalysts with very high yield and selectivity in acetonitrile under mild reaction conditions.
Dhakshinamoorthy, Amarajothi,Alvaro, Mercedes,Garcia, Hermenegildo
scheme or table
p. 6476 - 6478
(2010/10/21)

Bicyclic 6-alkylidene-penems as class-D beta-lactamases inhibitors
This invention relates to certain bicyclic 6-alkylidene penems which act as a inhibitor of class-D enzymes. β-Lactamases hydrolyze β-lactam antibiotics, and as such serve as the primary cause of bacterial resistance. The compounds of the present invention when combined with β-lactam antibiotics will provide an effective treatment against life threatening bacterial infections. In accordance with the present invention there are provided compounds of general formula I or a pharmaceutically acceptable salt or in vivo hydrolyzable ester R5 thereof: wherein: One of A and B denotes hydrogen and the other an optionally substituted fused bicyclic heteroaryl group; and X═O or S.
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(2010/11/25)

The regiochemistry of cyclization of α-sulfenyl-, α-sulfinyl-, and α-sulfonyl-5-hexenyl radicals: Procedures leading to regioselective syntheses of cyclic sulfones and sulfoxides
A study of the cyclization of α-sulfenyl-, α-sulfinyl-, and α-sulfonyl-5-hexenyl and 5-methyl-5-hexenyl radicals reveals a unique contrast in the mode of ring closure of the radicals. In the case of the 5-hexenyl radicals, the sulfinyl-substituted species displays unexpected regioselectivity relative to its analogues. Thus, while the α-S- and α-SO2-5-hexenyl radicals give measurable and increasing quantities of 6-endo product, the α-sulfinyl species cyclizes with high selectivity (95.5:4.5) via a 5-exo mode. By contrast, ring closure of the 5-methyl-5-hexenyl radicals is found to give substantially the 6-endo product in all cases. It is the α-sulfonyl-5-methyl-5-hexenyl radical that now exhibits high regioselectivity (97.5:2.5) for 6-endo closure: an illustration of the synthetic value of this observation is the independent synthesis of the model cyclohexyl sulfone 61 in high yield. It is found that ring closure under the conditions employed occurs irreversibly in all cases.
Della, Ernest W.,Graney, Sean D.
p. 3824 - 3835
(2007/10/03)

Kinetics of Intramolecular Alkyl Radical Attack on Sulfur in Disulfides and Thioesters
The 4-(alkyldithio)butyl radicals 8a and c, and the 4-(phenyldithio)butyl radical 8b, generated from the corresponding esters of N-hydroxypyridine-2(1H)-thione, undergo fast exo-cyclisation by SHi attack at sulfur.Similarly, the 5-(alkyldithio)pentyl radical 8d undergoes 1,6-ring formation.The rate constants for cyclisation were determined by photolysis of the radical precursors in the presence of appropriate thiols.Butyl and pentyl radicals bearing ω-acetylthio or ω-benzoylthio substituents also undergo ring closure but much more slowly.The kinetics of these intramolecular SH2 reactions are discussed and compared with those for the intermolecular attack of hexyl radicals on diphenyl disulfide and on dibutyl disulfide.
Beckwith, Athelstan L. J.,Duggan, Sandhya A. M.
p. 1509 - 1518
(2007/10/02)

The macrocyclization reaction of terminal dibromoalkanes with sulfide on alumina. The use of a solid support as an alternative to the high dilution technique
The reaction of a series of terminal dibromoalkanes with S-2 on Al2O3 has been examined. The use of a solid support for the macrocyclization represents a viable alternate procedure to the more traditional high dilution technique in solution. The cyclization also occur with thioacetamide on unactivated alumina.
Tan,Pagni,Kabalka,Hillmeyer,Woosley
p. 7709 - 7712
(2007/10/02)

4H-BENZOCYLOHEPTATHIOPHENES AND 9,10-DIHYDRO DERIVATIVES-SULFONIUM ANALOGUES OF PIZOTIFEN AND KETOTIFEN; CHIRALITY OF KETOTIFEN: SYNTHESIS OF THE 2-BROMO DERIVATIVE OF KETOTIFEN
Reaction of ketone IX with 4-tetrahydrothiopyranylmagnesium bromide and the following dehydration with thionyl chloride afforded the sulfide III which was transformed to the methiodide II (sulfonium analogue of pizotifen).Similar sequence starting from ketone XXIV and concluded by dehydration of the alcohol XX, cleavage of the enol ether, and by treatment with methyl iodide resulted in the formation of the sulfonium analogue of ketotifen (V).Three modified routes leading to ketotifen (IV) are being described.The chirality of ketotifen was proven by (1)H NMR spectrscopy with the help of,optically active NMR shift reagent.The resolution of racemic ketotifen (IV) was achieved by crystallization of salts with optically active O,O'-diacyltartaric acids and homogenous anantiomers were obtained.The X-ray crystallographic analysis of (+)-IV-O,O'-di(p-toluoyl)-(R)-tartrate led to the three- dimensional structure of the molecule of (+)-ketotifen which enabled to determine its absolute configuration to be (R).One of the products of bromination of the ketone IX, the following methanolysis and dehydrobromonation, identified as XXVII, was transformed by reaction with 1-methyl-4-piperidylmagnesium chloride, by the following acid-catalyzed dehydration, and cleavage of the enol ether to the 2-bromo derivative of ketotifen XXXIV. (R)(+)-Ketotifen (IV) was found to be the more active ketotifen enantiomer but the stereoselectivity of its action is only a partial one.The 2-bromo derivative of ketotifen (XXXIV) is much less active than ketotifen in the line antihistamine activity.
Polivka, Zdenek,Budesinsky, Milos,Holubek, Jiri,Schneider, Bohdan,Sediva, Zdenek,et al.
p. 2443 - 2469
(2007/10/02)

Nucleophilic and Electrophilic Mercaptanylations via 2-(Trimethylsilyl)ethanethiol-Derived Reagents
2-(Trimethylsilyl)ethanethiol reacts with carboxylic acids, alkyl halides, epoxides, and enones to provide acyl- and alkyl-substituted 2-(trimethylsilyl)ethyl sulfides.Electrophilic mercaptanylation is effected by a thiol-sulfonate reagent derived from 2-(trimethylsilyl)ethanethiol.
Anderson, M.B.,Ranasinghe, M.G.,Palmer, J.T.,Fuchs, P.L.
p. 3125 - 3127
(2007/10/02)

THE CHEMISTRY OF α,ω-MERCAPTOALCOHOLS IN THE PRESENCE OF DIETHOXYTRIPHENYLPHOSPHORANE. TEMEPERATURE DEPENDENCE OF CYCLODEHYDRATIONS AND S-ETHYLATIONS
Diethoxytriphenylphosphorane (DTPP) is easily prepared by oxidative addition of triphenylphosphine with diethyl peroxide.DTPP converts a variety of mercaptoalcohols to cyclic sulfides as well as hydroxythioethers.The temperature dependence (+25 --> -25 deg C) of the product distribution has synthetic petential.
Robinson, Philip L.,Kelly, Jeffery W.,Slayton, A. Evans
p. 59 - 70
(2007/10/02)

DIOXYPHOSPHORANES, AN EMERGING CLASS OF VERSATILE REAGENTS FOR ORGANIC SYNTHESIS
Several ?-dioxyphosphoranes have been prepared and their structural characterizations using NMR techniques support the trigonal bipyramidal conformer as the most stable for the acyclic phosphoranes.Their utility in smooth conversions of hydroxylated substrates to the corresponding X-heterocycles is documented.
Kelly, Jeffery W.,Robinson, Philip L.,Evans, Slayton A.
p. 147 - 150
(2007/10/02)

POTENTIAL ANTIHISTAMINE AGENTS: 4-(6,11-DIHYDRODIBENZOTHIEPIN-11-YLIDENE)-1-METHYLTETRAHYDROTHIOPYRANIUM IODIDE AND SIMILAR SULFONIUM SALTS DERIVED FROM RELATED TRICYCLIC SYSTEMS
Thioxanthone, 10,11-dihydrodibenzocyclohepten-5-one, dibenzothiepin-11(6H)-one, its 2-methyl derivative, and thieno-2-benzothiepin-4(9H)-one were reacted with 4-tetrahydrothiopyranylmagnesium bromide and the obtained tertiary alcohols IVabc, VIc, and XIX were dehydrated to the olefinic sulfides IXabc, Xc, and XXI.Addition of methyl iodide afforded the title compounds XIabc, XIIc, and XXII.The Grignard reactions were accompanied by the 1,6-addition giving the ketones XVI-XVIII as by-products.The reductive properties of tetrahydrothiopyranylmagnesium bromide were most striking in the case of reaction with 2-chlorothioxanthone; the isolation of thioxanthene and thioxanthone showed that nuclear dehalogenation took also place.Reactions of 11-chloro-6,11-dihydrodibenzothiepin and benzhydryl chloride with tetrahydrothiopyran-4-ol gave the sulfides XXV and XXVIII; whereas the latter reacted with methyl iodide under the formation of sulfonium salt XXIX, the former was cleaved and gave 4-hydroxyl-1-methyltetrahydrothiopyranium iodide (XXVI).The sulfonium salts are free of the central effects but their antihistamine activity is rather low.
Polivka, Zdenek,Holubek, Jiri,Budesinsky, Milos,Matousova, Oluse,Svatek, Emil,et al.
p. 2758 - 2774
(2007/10/02)

CYANO AND FLUORODESTANNYLATION: A NEW METHODOLOGY USING SOME POWERFUL SULFUR TRANSFER REAGENTS, THE ORGANOTIN SULFIDES
Fluoride and cyanide ions destannylate bis(aralkyl)tin sulfides and trialkyltin sulfides giving, in the presence of a variety of alkyl and activated halides, the corresponding thioether derivatives in excellent yield.The conditions are mild, neutral and anhydrous; a strong solvent effect is noted.Special comments are made concerning work-up procedures.
Harpp, David N.,Gingras, Marc
p. 4373 - 4376
(2007/10/02)

A SIMPLE, BIOGENETICALLY MODELED SYNTHESIS OF 4-(METHYLTHIO)BUTYL THIOCYANATE: THE REACTION OF THIOCYANATE ANION WITH S-METHYL-(1,n)-EPITHIONIUM IONS
The reaction of S-methylthiolanium fluorosulphate with thiocyanate ion gives predominantly 4-(methylthio)butyl thiocyanate, a result which is in accord with a hypothesis for the biogenesis of this compound, and which has implications for the natural occurrence of analogous thiocyanates.
Benn, M. H.,Singh, Vinod K.
p. 940 - 942
(2007/10/02)

PHOTOCHEMICAL REDUCTION OF N-TOSYLSULFILIMINES WITH THIOLATE ANION
The reaction between N-tosyldiarylsulfilimines and p-toluenethiolate anion did not take place in the dark even upon heating up to 62o but proceeded smoothly upon irradiation with visible light in DMF at room temperature, affording S-N bond cleavage products.
Fujimori, K.,Togo, H.,Pelchers, Y.,Nagata, T.,Furukawa, N.,Oae, S.
p. 775 - 778
(2007/10/02)

Organosulfur Chemistry. II. Use of Dimethyl Sulfoxide; a Facile Synthesis of Cyclic Sulfides
A versatile and short-reaction-time synthesis of twelve four-, five- and six-membered thiacycloalkanes (IIa-l)from the appropriate α,ω-dibromoalkanes (Ia-l)has been developed.Technical-grade dimethyl sulfoxide was proved to be by far the best for this cyclization.The pronounced effect for ring formation was recognized to be in order of five-membered ring (thiolanes) > six-membered ring (thianes) > four-membered ring (thietanes).Startling were 2-methylthiolane (IIf) and 2,5-dimethylthiolane (IIg; cis/trans mixture), both obtained in high yields although α-methyl - and α,α'-dimethyl substitution in general showing a remarkable retardation for cyclization.On the other hand, in both 3,3-dimethylthietane (IId) and 4,4-dimethylthiane (IIl) cyclization was much more efficient than other counterparts in each series, which is referred to as the gem-dimethyl effect.Keywords: thiacycloalkane; thietane; thiolane; thiane; dimethyl sulfoxide; cyclization: α,ω-dibromoalkane; sodium sulfide nonahydrate; refractive index
Nagasawa, Kazuo,Yoneta, Akemi
p. 5048 - 5052
(2007/10/02)

THIOETHER PROTECTION VIA SELECTIVELY CLEAVABLE SULFONIUM SALTS
There are few protecting groups available for the thioether functionality.The selective cleavage of 4-phthalimidobutyl- and p-methoxybenzylsulfonium salts make these derivatives ideal for thioether protection.
Doi, Joyce Takahashi,Luehr, Gary W.
p. 6143 - 6146
(2007/10/02)

FACILE REDUCTION OF SULFOXIDES AND SULFILIMINES TO SULFIDES BY USING METAL/CHLOROMETHYLSILANES
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Nagasawa, Kazuo,Umezawa, Toshiyuki,Itoh, Kei-ichi
p. 463
(2007/10/02)

PUMMERER REARRANGEMENTS USING CHLOROTRIMETHYLSILANE
Pummerer rearrangements of 3-carbomethoxythian-4-one S-oxide (1) have been investigated and chlorotrimethylsilane found to be the reagent of choice for preparing the corresponding α,β-unsaturated sulphides (2 and 3).Related chlorotrimethylsilane-induced Pummerer rearrangements are also reported.
Lane, Simon,Quick, Stephen J.,Taylor, Richard J. K.
p. 1039 - 1042
(2007/10/02)

Pummerer Rearrangements Using Chlorotrimethylsilane
Attempted Pummerer rearrangement of 3-methoxycarbonylthian-4-one S-oxide in refluxing acetic anhydride gives unexpected products in which β-carbon oxidation and ring contraction has taken place.Treatment of 3-methoxycarbonylthian-4-one with N-chlorosuccinimide gives similar rearrngement products.These rearrangements are rationalised by the intermediacy of a common thiiranium ion.Chlorotrimethylsilane in refluxing tetrachloromethane efficiently effects the expected Pummerer rearrangement of 3-methoxycarbonylthian-4-one S-oxide into the corresponding α,β-unsaturated sulphides.Reactions of this reagent with related sulphoxides are also described.
Lane, Simon,Quick, Stephen J.,Taylor, Richard J. K.
p. 2549 - 2552
(2007/10/02)

FORMATION OF SULPHUR COMPOUNDS IN HYDRODENITROGENATION OF QUINOLINE, 1,2,3,4-TETRAHYDROQUINOLINE, PYRIDINE, PIPERIDINE AND 1-PENT-4-ENYLAMINE ON A NICKEL-TUNGSTEN CATALYST IN THE PRESENCE OF HYDROGEN SULPHIDE
Hydrodenitrogenation (HDN) of quinoline and 1,2,3,4-tetrahydroquinoline on a sulphided nickel-tungsten catalyst in the presence of hydrogen and of its mixture with hydrogen sulphide has been studied in an autoclave at 350 deg C.The results show that hydrogen sulphide exhibits rate-accelerating effect on HDN of the above compounds by formation of sulphur compounds.It was found that neutral portion of the reaction mixture contains octahydro-2H-1-benzothiopyran, octahydro-1H-2-benzothiopyran, octahydro-2-methylbenzo(b)thiophene and other sulphur compounds.The reaction scheme for HDN of quinoline that accounts for favourable effect of hydrogen sulphide is proposed.In the neutral portion of the reaction mixture from HDN of piperidine and 1-pent-4-enylamine in the presence of hydrogen sulphide further sulphur-containing compounds were identified.
Cerny, Mirko,Trka, Antonin
p. 1749 - 1758
(2007/10/02)

FORMATION OF SULFUR COMPOUNDS IN THE HYDRODENITROGENATION OF PIPERIDINE, PYRIDINE, 1-PENTYLAMINE AND 1-PENT-4-ENYLAMINE ON A NICKEL-TUNGSTEN CATALYST IN THE PRESENCE OF HYDROGEN SULFIDE
Hydrogenations of piperidine, pyridine, 1-pentylamine, and 1-pent-4-enylamine were carried out in an autoclave at 300 deg C on a sulfidized nickel-tungsten catalyst using either pure hydrogen or a mixture of hydrogen with hydrogen sulfide.Hydrogen sulfide was found to raise the degree of conversion of the starting substances and accelerate the hydrodenitrogenation by formation of sulfur compounds; 1-pentanethiol, di(1-pentyl)sulfide, 2-methylthiacyclopentane, thiacyclohexane and other sulfur compounds were detected in the reaction mixtures in the presence of hydrogensulfide.A reaction pathway is suggested of the hydrodenitrogenation of piperidine in the presence of hydrogen sulfide, accounting for the favourable effect of the latter on the hydrodenitrogenation of nitrogen compounds.
Cerny, Mirko
p. 928 - 935
(2007/10/02)

Heterocyclisation alkylante radicalaire par photolyse de sulfures ethyleniques. III. Photolyse de sulfures de butene-3 yle-1 et hexene-5 yle-1
Photolysis of allyl but-3-en-1-yl sulfide (I) gives the thiolan 3 and the 3-allylthiolan 4 resulting from "forbidden" 5-endotrig cyclization.Photolysis of allyl hex-5-en-1-yl sulfide (III) gives, besides the mixture of six- and seven-membered non-alkylated heterocycles 10 and 11, exclusively the alkylated 2-(but-3-enyl) thian 12.These and other results confirm and generalize the mechanism proposed earlier for the photolytic cyclization of pent-4-enyl sulfides.Photolitic cleavage of unsaturated allyl or benzyl sulfides gives the unsaturated thiyl radical.The unsaturated radical undergoes an intramolecular reversible addition out of the cage.Then the more stable cyclized radical is trapped selectively by the allyl or benzyl radical.
Bastien, Gerard,Surzur, Jean-Marie
p. 84 - 88
(2007/10/02)