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Copper-Catalyzed Direct Synthesis of Aryl Thiols from Aryl Iodides Using Sodium Sulfide Aided by Catalytic 1,2-Ethanedithiol
A copper-catalyzed direct and effective synthesis of aryl thiols from aryl iodides using readily available Na 2 S·9H 2 O and 1,2-ethanedithiol was described. A variety of aryl thiols were readily obtained in yields of 76-99%. In this protocol, Na 2 S·9H 2 O was used as ultimate sulfur source, and 1,2-ethanedithiol functioned as an indispensable catalytic reagent.
Xue, Hongyu,Jing, Bing,Liu, Shasha,Chae, Junghyun,Liu, Yajun
p. 2272 - 2276
(2017/10/06)

Method for preparing sulfhydryl compounds by hydroxyl substitution and sulfhydryl compounds
The invention provides a method for preparing sulfhydryl compounds by hydroxyl substitution and the sulfhydryl compounds. According to the method, low-cost and easily-obtained benzene or fused ring compounds with phenolic hydroxyl groups or benzyl hydroxyl substituents serving as raw materials to react with the raw materials such as inorganic sulfide under the catalysis conditions to prepare the corresponding sulfhydryl compounds. The method has the advantages that the preparation method is simple, convenient and rapid, low in cost, mild in reaction condition, high in reaction site selectivity and high in yield, a post-processing process is simple, and no pollution is caused.
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Paragraph 0058; 0059; 0060; 0067; 0068; 0069

(2017/06/02)

SINGLE-STEP SYNTHESIS METHOD OF ARYL THIOL AND APPLICATION THEREOF
The present invention relates to a single-step synthesis method of aryl thiol, and more specifically, to a method of synthesizing aryl thiol in a single-step by making aryl halide react with alkane dithiol in the presence of a transition metal catalyst. According to the present invention, a single-step synthesis method using the transition metal catalyst, the synthesis method which is capable of synthesizing aryl thiol from aryl halide at a high yield, can be provided. Various aryl halides may be applied to the synthesis method. Further, the synthesis method has advantages that an easily usable reagent may be used, operations are simple, and reactions can be performed under mild conditions. In addition, the synthesized aryl thiol may be used in the synthesis of advanced molecules such as diaryl sulfides and benzothiophenes.COPYRIGHT KIPO 2017
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Paragraph 0032; 0033; 0063; 0067; 0068; 0070

(2017/09/02)

Copper(II)-Catalyzed Single-Step Synthesis of Aryl Thiols from Aryl Halides and 1,2-Ethanedithiol
A highly efficient transition metal-catalyzed single-step synthesis of aryl thiols from aryl halides has been developed employing copper(II) catalyst and 1,2-ethanedithiol. The key features are use of readily available reagents, a simple operation, and relatively mild reaction conditions. This new protocol shows a broad substrate scope with excellent functional group compatibility. A variety of aryl thiols are directly prepared from aryl halides in high yields. Furthermore, the aryl thiols are used in situ for the synthesis of more advanced molecules such as diaryl sulfides and benzothiophenes.
Liu, Yajun,Kim, Jihye,Seo, Heesun,Park, Sunghyouk,Chae, Junghyun
supporting information
p. 2205 - 2212
(2015/07/27)

Vinyl sulfone-based peptidomimetics as anti-trypanosomal agents: Design, synthesis, biological and computational evaluation
A series of vinyl sulfone-containing peptidomimetics were rationally designed, synthesized, and evaluated against Trypanosoma brucei brucei. These electrophilic compounds are likely to exert their antitrypanosomal activity via inhibition of trypanosomal cysteine proteases, TbCatB and rhodesain, through alkylation of a key cysteine residue within the protease active site. The series was designed to present complementary groups to naturally recognized peptide substrates while probing tolerance to a range of substitutions at the P1, P1′, and P2 positions. The most potent compound, 29 (EC50 = 70 nM, T. b. brucei whole cell assay), displayed minimal toxicity (>785 times selectivity) when assayed for cytotoxicity against the human promyelocytic leukemia (HL-60) cell line. Cells treated with compound 29, as with K777 (2), exhibited an increase in both the number of multinucleated cells and cells with swollen flagellar pockets. Computational analysis revealed a strong correlation between the hypothetical binding mode in TbCatB/rhodesain and trypanocidal activity in vitro.
Dunny, Elizabeth,Doherty, William,Evans, Paul,Malthouse, J. Paul G.,Nolan, Derek,Knox, Andrew J.S.
supporting information
p. 6638 - 6650
(2013/10/01)

Palladium catalyzed synthesis of aryl thiols: Sodium thiosulfate as a cheap and nontoxic mercapto surrogate
A Pd-catalyzed coupling reaction of ArBr/ArCl/ArOTf with sodium thiosulfate takes place in presence of Cs2CO3 at 80 °C. The reaction mixture is directly treated with Zn/HCl to afford aryl thiols in good to excellent yields.
Yi, Jun,Fu, Yao,Xiao, Bin,Cui, Wei-Chen,Guo, Qing-Xiang
experimental part
p. 205 - 208
(2011/02/26)

Copper-catalyzed coupling of thiourea with aryl iodides: The direct synthesis of aryl thiols
A general, economical and efficient protocol for the direct copper-catalyzed coupling of thiourea with aryl iodides is developed and it will be potentially applied in large-scale industry as a preferred process.
Qiao, Shu,Xie, Kun,Qi, Junsheng
scheme or table
p. 1441 - 1443
(2011/01/04)

One-pot synthesis of unsymmetrical diaryl thioethers by palladium-catalyzed coupling of two aryl bromides and a thiol surrogate
Extraordinarily simple, convenient, and efficient: A general and operationally simple one-pot synthesis of unsymmetrical diaryl sulfides by coupling two different bromoarenes and triisopropylsilanethiol (TIPS-SH) is reported. This protocol overcomes the narrow availability of arene thiols and their instability to oxidation. These reactions catalyzed by palladium complexes generated from the alkylbisphosphine CyPF-tBu occur in good to excellent yields with wide scope and high tolerance of functional groups.
Fernandez-Rodriguez, Manuel A.,Hartwig, John F.
supporting information; experimental part
p. 2355 - 2359
(2010/07/02)

A novel, practical and highly chemoselective methodology for reduction of disulphides to thiols
A novel, simple and efficient method for the reduction of disulfides to thiols using In/NH4Cl is described.
Vidya Sagar Reddy,Venkat Rao,Iyengar
p. 859 - 862
(2007/10/03)

Interaction of naphthyl heterocycles with DNA: Effects of thiono and thio groups
The intercalation and photocleavage of DNA by N-[β-(N′,N′-dimethylamino)ethyl]dithiono-1,8-naphthalimide (2) were extremely effective compared to the use of the oxygen-containing counterpart (1). Their photocleavage action under 366 nm UV light is proposed to proceed by electron transfer from bases to the triplet state of the naphthalimides. The enhancement of the intercalation of DNA and the photocleavage of DNA were also observed for other compounds possessing a thiono or thio group compared with their oxygen-containing counterparts.
Qian, Xuhong,Huang, Tian-Bao,Wei, Dong-Zhi,Zhu, Dong-Hui,Fan, Ming-Cai,Yao, Wei
p. 715 - 718
(2007/10/03)

Non-aqueous reduction of aromatic sulfonyl chlorides to thiols using a dichlorodimethylsilane-zinc-dimethylacetamide system
A new and efficient method for the non-aqueous reduction of sulfonyl chlorides to affored the corresponding thiols by use of a dichlorodimethylsilane-zinc-dimethylacetamide system was successfully developed. Various aromatic thiols were prepared in high yield by easy operation. Continuous reactions with the above reduction using the prepared thiol were also demonstrated.
Uchiro, Hiromi,Kobayashi, Susumu
p. 3179 - 3182
(2007/10/03)

A versatile synthetic route to 1,5-dithiocins from o-mercapto aromatic aldehydes
An earlier procedure for the facile preparation of benzo-fused 1,5-dithiocins 2a-2c from o-mercaptobenzaldehydes has been improved and shown to be capable of extension to the preparation of several naphthalene-derived analogues. The general method also afforded several N-alkylated 1,5-dithiocins 4, 5 by replacing NH3 with the appropriate primary amine. It was found that N-acylation of the 1,5-dithiocins was successful only with methyl chloroformate. Attempted N-phenylation met with limited success but was shown to be unnecessary since even the less reactive aniline readily undergoes the general reaction of primary amines. When simple α-amino acids, or their methyl esters, were employed as the primary amine in the reaction with o-mercaptobenzaldehyde, the formation of the N-alkylated 1,5-dithiocins 4a, 17a, 17b with accompanying loss of -COOH or -COOMe was observed, in preparatively useful yields. A mechanism is proposed for this interesting transformation.
Still, Ian W.J.,Natividad-Preyra, Rosanne,Toste, F. Dean
p. 113 - 121
(2007/10/03)

Reduction of symmetric disulfides to thiols using Mg in methanol
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Sridhar, Madabhushi,Vadivel, Subramanian K.,Bhalerao, Uday T.
p. 1347 - 1350
(2007/10/03)

POTASSIUM TRIISOPROPYLSILANETHIOLATE: VINYL AND ARYL SULFIDES THROUGH Pd-CATALYZED CROSS COUPLING
Vinyl and aryl halides are efficiently converted, under Pd catalysis, with KSTIPS (1) to the corresponding silyl sulfides (2, 3).The naphthyl derivative was easily hydrolyzed to the mercaptan 4, or alkylated or alkenylated to provide unsymmetrical sulfides (5, 6).
Rane, Anil M.,Miranda, Edgar I.,Soderquist, John A.
p. 3225 - 3226
(2007/10/02)

Cycloadditions. 23. The Thermal Reactivity of S-(1-Naphthyl) and S-(9-Anthryl)-2-methyl-2,3-butadienethioates
Heating of the S-(1-naphthyl)esters of 2-methyl-2,3-butadiene thioacid and of 2-methyl-4,4-diphenyl-2,3-butadiene thioacid (3a resp. 3b) furnishes mixtures of the Diels-Alder products 5a,b and the cyclobutenone 7 and the naphthol derivative 8, resp.The corresponding S-(9-anthryl)esters 4a,b are not isolable; under the conditions of their synthesis (allenecarboxylic acids 1a u. b, 9-thioanthrol 2b, DCC and DMAP) they isomerise spontaneously to the Diels-Alder products 9.
Himbert, Gerhard,Fink, Dieter
p. 654 - 657
(2007/10/02)

HIGH-TEMPERATURE ORGANIC SYNTHESIS. XLI. REACTIONS OF AROMATIC HALOGEN COMPOUNDS WITH HYDROGEN SULFIDE IN THE PRESENCE OF SULFUR
The reactions of halogenoarenes containing a sufficiently mobile halogen atom with hydrogen sulfide in the presence of elemental sulfur at 90-230 deg C lead to the corresponding sulfides (with yields of up to 87percent).The disulfides, thiols, and arenes are formed at the same time.In the reactions of bromophenols with hydrogen sulfide in the presence of sulfur migration of the halogen atom is observed, and this leads to the formation of isomeric bis(hydroxyphenyl) sulfides and disulfides and 2,4-dibromophenol.It was established that the yield of the reaction products depends on the time, temperature, halogenophenol-sulfur ratio, and delivery rate of hydrogen sulfide.The radical mechanism of the formation of these substances is discussed.
Papernaya, L. K.,Panova, G. M.,Deryagina, E. N.,Voronkov, M. G.
p. 1856 - 1862
(2007/10/02)

RADIKALIONEN 89. EINELEKTRONEN-OXIDATIONEN VON DIARYLDISULFIDEN MIT AlCl3/H2CCl2
The single electron oxidation of 14 alkyl and alkoxy substituted diaryldisulfides by AlCl3/H2CCl2 has been investigated by ESR/ENDOR spectroscopy.The radical cations observed prove the following skeletal rearrangements: Those with ring hydrogens in ortho positions to the disulfide bridge preferentially form thianthrene derivatives.The isomeric dinaphthyl disulfides react differently, the 2,2'-isomer yielding the dibenzothianthrene radical cation and the 1,1'-isomer the well-known naphthalene-1,8-disulfide radical cation.For all diaryl disulfides with completely alkyl- or methoxy-blocked ortho positions, oxidative desulfuration is observed.As substantiated by additional (2)D and (33)S isotope marking, the bis(2,5-dimethoxyphenyl)disulfide reacts both to the corresponding thianthrene derivative as well as via desulfuration to the radical cation of the monosulfide.Accompanying cyclovoltammetric and photoelectron spectroscopic measurements prove that all ESR spectroscopically detected radical cations result from compounds Ar-S-Ar, Ar-SS-Ar and Ar(S)2Ar with rather low oxidation or ionisation potentials and thus suggest that each the most easily oxidized paramagnetic species is observed in the rather complex product mixtures, which form on AlCl3/H2CCl2 oxidation of diaryldisulfides. Key words: Diaryl disulfides; one-electron oxidation; radical cations; ESR/ENDOR spectra.
Bock, Hans,Rittmeyer, Peter
p. 261 - 292
(2007/10/02)

Photochemical Anion-Promoted Carbon-Sulfur Cleavage Reactions of Diaryl Sulfides, Alkyl Aryl Sulfides, and Related Sulfoxides and Sulfones
Diaryl sulfides and the related sulfoxides and sulfones react with substances such as diethyl phosphite anion, pinacolone enolate, and diphenylphosphide anion under irradiation to cleave one carbon-sulfur bond and form diethyl arylphosphonates, arylmethyl tert-butyl ketones, and aryldiphenylphosphines.Alkyl aryl sulfides and the related sulfones also experience carbon-sulfur bond cleavage under these conditions to produce arenethiols.Generally, these reactions occur in synthetically useful yields.The reactions of the anions with these sulfides, sulfoxides, and sulfones all require irradiation, but is notable that the reactions of diphenylphosphide anion occur in the visible region of the spectrum.Several lines of evidence suggest that the reaction proceeds via the familiar SRN1 pathway and that the photochemically-induced electron transfer occurs in an arene-anion complex.Thermochemical considerations dictate the cleavage direction in the anion radicals of unsymmetrical sulfides.
Cheng, Carlos,Stock, Leon M.
p. 2436 - 2443
(2007/10/02)

THE REACTION BETWEEN ARENEDIAZONIUM TETRAFLUOROBORATES AND ALKALINE THICARBOXYLATES IN DMSO: A CONVENIENT ACCESS TO ARYL THIOLESTERS AND OTHER AROMATIC SULFUR DERIVATIVES.
The reaction between potassium thioacetate or sodium thiobenzoate and arenediazonium tetrafluoroborates in DMSO leads to the corresponding aryl thiolesters 1 which can either be isolated or further reacted providing a convenient one-pot access to a number of other aromatic sulfur derivatives.
Petrillo, Giovanni,Novi, Marino,Garbarino, Giacomo,Filiberti, Marcos
p. 7411 - 7420
(2007/10/02)

Conformational Effects in the Alkali-Metal Reduction of Diaryl Sulfides. 2. Evidence for Episulfide Intermediates
Alkali-metal reduction of a series of diaryl sulfides shows that, if both aryl moieties possess aromatic stabilization energies less than that of the phenyl group ( i.e., able to generate relatively more stable radical anions), the diaryl sulfide forms an episulfide intermediate via regiospecific coupling of the aryl moieties at the stage of a reactive intermediate.The formation of the episulfide intermediate explains why double carbon-sulfur bond cleavage and extrusion of sulfur is observed only in such diaryl sulfides and why there is preference for the formation ofsingle regioisomeric biaryl.
Francisco, Manuel A.,Kurs, Argo,Katritzky, Alan R.,Rasala Danuta
p. 4821 - 4826
(2007/10/02)

HIGH-TEMPERATURE ORGANIC SYNTHESIS. XXVII. REACTIONS OF ALKANETHIONES WITH THE CHLORINE DERIVATIVES OF BENZENE, THIOPHENE, AND NAPHTHALENE
Alkanethiols react effectively with chlorobenzene, its derivatives, 1-chloronaphthalene, and 2-chlorothiophene at 600-660 deg C with the preferential formation of the corresponding aromatic or heteroatomic thiols.Ethanethiol is most reactive.When it is used instead of hydrogen sulfide in reactions with chlorobenzene or its 4-substituted derivatives, the yield of the aromatic thiols, from which the phenylthiyl radicals are generated with greater difficulty, increases more sharply than the yield of the thiophenols, which generate the more stable 4-XC6H4S radicals.The side products of the reactions are the corresponding diaryl sulfides, thiophene, benzothiophene, and toluene.
Voronkov, M. G.,Deryagina, E. N.,Sukhomazova, E. N.
p. 755 - 760
(2007/10/02)

HIGH-TEMPERATURE ORGANIC SYNTHESIS. XXVIII. LIQUID-PHASE REACTIONS OF THIOLS WITH AROMATIC BROMINE COMPOUNDS
In the liquid phase at 125-215 deg C thiophenol only reacts effectively with 2- and 4-bromophenol, 1-bromo-2-napthol, 1-bromonapthalene, and 9-bromoanthracene, forming the corresponding phenyl aryl sulfides. 2-Thiophenethiol and 1-thionapthol reduce the same bromine derivatives to the corresponding arenes.The disulfides formed here undergo secondary transformations.The reactions of thiophenol with 2- and 4-bromophenol and 1-bromo-2-napthol are convenient preparative methods for the synthesis of the previously difficulty obtainable phenyl hydroxyaryl sulfides.
Papernaya, L. K.,Panova, G. M.,Deryagina, E. N.,Voronkov, M. G.
p. 1774 - 1777
(2007/10/02)

1-THIONAPHTHOL - A NEW COLLECTOR FOR THE FLOTATION OF POLYMETALLIC ORES.
This work studied the possible use of 1-thionaphthol as a collector in the flotation of lead-zinc ores. This reagent may be obtained by the reaction of the corresponding chloroderivative with hydrogen sulfide upon heating to 500-600 degree C in the presence of methylene chloride initiator. The tests were carried out in an industrial process by a direct selective flotation scheme. The results of the flotation experiments using 1-thionaphthol and potassium butyl xanthogenate, which was used as the major collector in the enrichment plant, are given.
Leonov,Nikol'skaya,Kletsko,Deryagina,Sukhomazova,Voronkov
p. 2059 - 2061
(2007/10/02)

The Synthesis of Dinaphthothiophenes
The synthesis of dinaphthothiophene (6), dinaphthothiophene (15), dinaphthothiophene (20), dinaphthothiophene (26), dinaphthothiophene (37) and dinaphthothiophene (45) has been accomplished.
Tedjamulia, Marvin L.,Tominaga, Yoshinori,Castle, Raymond N.,Lee, Milton L.
p. 1143 - 1148
(2007/10/02)

Reduction of Sulfonic Acids and Related Organosulfur Compounds with Triphenylphosphine-Iodine System
Arenesulfonic acids, their sodium salts, and alkyl arenesulfonates can be reduced readily to the corresponding arenethiols quantitatively by treatment with a mixture of triphenylphosphine and a catalytic amount of iodine, while alkanesulfonic acids, sulfinic acids, disulfides, thiosulfonic S-esters, and sulfonates are also readily reduced to the corresponding thiols similarly.Upon treatment with a mixture of triphenylphosphine and excess iodine, however, these aliphatic sulfur compounds are converted eventually to the corresponding alkyl iodides.The relative reactivities of these sulfonyl derivatives in the reaction with the triphenylphosphine-iodine system are the following.Aromatic series: ArSO2Cl, ArSO2SAr' > ArSO2H > ArSO3R > ArSO3-HNBu3+ (or PyH+) > ArSO3H > ArSO2SO2Ar >> ArSO2CH2C(CH3)3, ArSO3Ar'.Aliphatic series: RSO2Cl, RSO2SR', RSO2-HNBu3+ > RSO3-HNBu3+ > RSSR, RSO2H > RSO3H > RSH > RSO3R'.In these reactions, the arenesulfonic acids bearing electron-donating substituents can be reduced more readily than those having electron-withdrawing substituents.
Oae, Shigeru,Togo, Hideo
p. 3802 - 3812
(2007/10/02)

Simple Syntheses of Aryl Alkyl Thioethers and of Aromatic Thiols from Unactivated Aryl Halides and Efficient Methods for Selective Dealkylation of Aryl Alkyl Ethers and Thioethers
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Testaferri, L.,Tiecco, M.,Tingoli, M.,Chianelli, D.,Montanucci, M.
p. 751 - 755
(2007/10/02)

HIGH-TEMPERATURE ORGANIC SYNTHESIS. XVII. REACTION OF CHLOROBENZENE AND ITS DERIVATIVES WITH DIALKYL DISULFIDES
The products from the reaction of chlorobenzene with dialkyl disulfides in the gas phase at 550-650 deg C are benzene, thiophenol, diphenyl sulfide, and also toluene, thiophene, and benzothiophene.Diethyl disulfide is most reactive.Its copyrolysis with chlorobenzene is distinguished by high selectivity for the formation of thiophenol, the yield of which amounts to 60percent.In the reaction of substituted chlorobenzenes and also 2-chlorothiophene and 1-chloronaphthalene with diethyl disulfide the corresponding thiols were obtained with high yields.Two paths for the formation of thiophene during the pyrolysis of dialkyl disulfide were established, i.e., from vinyl hydrosulfide and S-butyl radical.The last reaction is realized at a high rate.
Voronkov, M. G.,Deryagina, E. N.,Sukhomazova, E. N.
p. 1516 - 1522
(2007/10/02)

CONFORMATIONAL ANALYSIS AND PHOTOCHeMICAL BEHAVIOUR OF SULFOXIDES IN THE NAPHTHOTHIOPYRAN AND NAPHTHOTHIOPYRAN SERIES
The sulfoxides derived from 2,3-dihydro-4H-naphthothiopyran and its 4-phenyl and 4-oxo derivatives, as well as the analogous sulfoxides in the 2,3-dihydro-1H-naphthothiopyran series, have been synthesized and their structures established by spectroscopic methods, especially 1H and 13C nmr.On the photolysis these sulfoxides have been found to react by a rather inefficient photochemical deoxygenation pathway.
Still, Ian W. J.,Arora, Parkash C.,Hasan, S. Khaquan,Kutney, Gerald W.,Lo, LAwrence Y. T.,Turnbull, Kenneth
p. 199 - 209
(2007/10/02)

[3,3]-Sigmatropic rearrangement of allyl and 2-butenyl 1-naphthyl sulfides
The [3,3]-sigmatropic rearrangement of alkenyl 1-naphthyl sulfides in solutions with various polarities was investigated at 138-190 °C. The reaction proceeds through the formation of 2-alkenyl-1-naphthalene thiols, which subsequently undergo cyclization to compounds of the 2,3-dihydronaphtho[1,2-b]thiophene and naphtho[1,2-b]dihydrothiopyran series. 2-Butenyl 1-naphthyl sulfide, in addition to its passing directly through a [3,3]-sigmatropic rearrangement, to a considerable extent undergoes a prior [1,3]-sigmatropic rearrangement, which ultimately leads to the formation of four cyclic products. The kinetic parameters of the rearrangement of the sulfides were determined. The more negative entropies of activation constitute evidence for the high symmetry of the transition state.
Aukharieva,Danilova,Anisimov,Viktorova
p. 443 - 446
(2007/10/02)

Reaction of 1,8-Dehydronaphthalene with Carbon Disulphide
The reaction of carbon disulphide with 1,8-dehydronaphthalene, generated by oxidation of 1-amino-1H-naphthotriazine (7), gave naphthothiet (10) (6-8percent), naphtho-1,3-dithiin-2-thione (11) (3-5percent), naphthothiophen-2-thione (12) (4-5percent), and naphthothiophen-2-one (13) (4-5percent).The results can be explained by radical addition of 1,8-dehydronaphthalene to the sulphur atom of carbon disulphide forming a new 1,5-diradical intermediate (8), from which the final products are derived.
Nakayama, Juzo,Dan, Shigeyuki,Hoshino, Masamatsu
p. 413 - 414
(2007/10/02)

IODINE CATALYZED REDUCTION OF ARENESULFONIC ACID TO THE ARENETHIOL WITH TRIPHENYLPHOSPHINE
Arenesulfonic acids, its sodium salts, and alkyl arenesulfonates were reduced readily to the corresponding arenethiols quantitatively with triphenylphosphine in the presence of iodine.
Fujimori, Ken,Togo, Hideo,Oae, Shigeru
p. 4921 - 4924
(2007/10/02)

A CONVENIENT SYNTHESIS OF AROMATIC THIOLS FROM UNACTIVATED ARYL HALIDES
Aromatic thiols are obtained in good yields from unactivated aryl halides and excess MeSNa in HMPA.
Testaferri, L.,Tingoli, M.,Tiecco, M.
p. 3099 - 3100
(2007/10/02)

Electrophilic additions to allenes. VI. The role of steric versus electronic effects in the reactions of arenesulphenyl halides with allenes
The role of steric and electronic effects during the rate and product determining steps for the addition of arenesulphenyl chlorides to 1,3-disubstituted allenes has been briefly examined.Both effects appear to be generally of minimal importance during the rate determinig step.The available rate data indicate the presence of little, if any, build up of positive charge on sulphur.These results are interpreted in terms of an SN2 attack on bivalent sulphur leading to an alkylidenethiiranium ion intermediate.Steric effects are of greater importance in the product determinig step, particularly when the sulphenyl chlorides possess two bulky ortho substituents, as in the case of 2,4,6-triisopropylbenzenesulphenyl chloride.
Garratt, Dennis G.,Beaulieu, Pierre L.
p. 2738 - 2744
(2007/10/02)