cas 3795-79-7, methyl 4-methylsulfanylbenzoate

Articles about 3795-79-7Total 37 be found

Article title
Article abstract
Author
Journal number and time
Download

Paired Electrolysis Enabled Ni-Catalyzed Unconventional Cascade Reductive Thiolation Using Sulfinates
Herein, we have reported a nickel-catalyzed cascade reductive thiolation of aryl halides with sulfinates driven by paired electrolysis. This protocol uses sulfinates as the sulfur source, and various thioethers could be synthesized under mild conditions. By mechanism exploration, we find that a cascade chemical step is allowed on the electrode interface and could alter the reaction pathway in paired electrolysis, whose findings could help the discovery of novel cascade reactions with unique reactivity.
Kang, Jun-Chen,Li, Zi-Hao,Chen, Chao,Dong, Li-Kun,Zhang, Shu-Yu
supporting information
p. 15326 - 15334
(2021/10/25)

Modulation of photochemical oxidation of thioethers to sulfoxides or sulfones using an aromatic ketone as the photocatalyst
We have developed an eco-friendly and chemo-selective photocatalytic synthesis of sulfoxides or sulfones via oxidation of sulfides (thioethers) at ambient temperature using air or O2 as the oxidant. An inexpensive thioxanthone was used as the photocatalyst. Our method offers excellent chemical yields and good functional group tolerance. The hydrogen bonding between hexafluoro-2-propanol (HFIP) and sulfoxides may play an important role in minimizing the over-oxidization of sulfoxides.
Zhao, Bin,Hammond, Gerald B.,Xu, Bo
supporting information

(2021/09/13)

Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers
We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide- and thiol-free reaction shows high functional group tolerance and great efficiency for the late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility and utility in multistep synthesis.
Delcaillau, Tristan,Boehm, Philip,Morandi, Bill
supporting information
p. 3723 - 3728
(2021/04/07)

Palladium-Catalyzed Chlorocarbonylation of Aryl (Pseudo)Halides Through In Situ Generation of Carbon Monoxide
An efficient palladium-catalyzed chlorocarbonylation of aryl (pseudo)halides that gives access to a wide range of carboxylic acid derivatives has been developed. The use of butyryl chloride as a combined CO and Cl source eludes the need for toxic, gaseous carbon monoxide, thus facilitating the synthesis of high-value products from readily available aryl (pseudo)halides. The combination of palladium(0), Xantphos, and an amine base is essential to promote this broadly applicable catalytic reaction. Overall, this reaction provides access to a great variety of carbonyl-containing products through in situ transformation of the generated aroyl chloride. Combined experimental and computational studies support a reaction mechanism involving in situ generation of CO.
Bismuto, Alessandro,Boehm, Philip,Morandi, Bill,Roediger, Sven
supporting information
p. 17887 - 17896
(2020/08/19)

Palladium-catalyzed carbonylative transformation of phenols via in-situ triflyl exchangement
Phenols are attractive starting materials due to their ready availability. Herein, we developed a novel method on palladium-catalyzed alkoxycarbonylation of phenols. By using commercially available Pd(OAc)2 and PtBu3·HBF4 as the catalyst system and aryl triflates as triflyl source to activate the other phenol, various carboxylic acid esters were prepared in moderate to good yields via Tf exchange and then O-Tf bond cleavage. Notably, phenols generated from aryl triflates after Tf transfer or other additional aliphatic alcohols can all be employed as nucleophiles to synthesize the corresponding esters.
Li, Chong-Liang,Wang, Hai,Wu, Xiao-Feng,Zhang, Youcan
p. 502 - 505
(2020/07/21)

B2cat2-Mediated Reduction of Sulfoxides to Sulfides
An efficient and operationally simple method for the reduction of sulfoxides to sulfides has been developed using bis(catecholato)diboron (B2cat2) as a reducing agent. The present method accommodates various functional groups which are generally prone to reduction: halides, alkynes, carbonyls, nitriles, and heterocycles are totally intact, and only sulfoxide moieties undergo reduction chemoselectively. Moreover, the remaining diboron and the resulting boron-containing wastes are readily removable, the practicality of this protocol being thus demonstrated.
Takahashi, Fumiya,Nogi, Keisuke,Yorimitsu, Hideki
supporting information
p. 3009 - 3012
(2020/03/25)

Transition-Metal-Free Aryl-Heteroatom Bond Formation via C-S Bond Cleavage
Aryl-heteroatom bonds (C-Het) are almost ubiquitously present in chemical molecules. However, methods for diverse C-Het bond formations from a simple substrate are limited. Herein, we report a convenient and efficient C-S bond transformation of aryl sulfoniums to various C-Het bonds (C-O, C-S, C-Sn, C-Si, C-Se) in the absence of any transition-metal catalyst. These reactions proceeded in mild conditions with a wide substrate scope.
Zhao, Jian-Nan,Kayumov, Muzaffar,Wang, Dong-Yu,Zhang, Ao
supporting information
p. 7303 - 7306
(2019/10/02)

A visible-light photocatalytic thiolation of aryl, heteroaryl and vinyl iodides
The general catalytic synthesis of aryl and vinyl thioethers from readily available halides remains a challenge. Herein we report a unified method for the thiolation of aryl and vinyl iodides with dialkyl disulfides using visible light photoredox catalysis. A range of thioether products bearing diverse functional groups can be accessed in high yield and with excellent chemoselectivity. We demonstrate the versatility of this method through the expedient synthesis of a family of thioether-rich natural products. A detailed investigation of the photocatalytic mechanism is presented from both steady-state and time-resolved luminescent quenching as well as transient absorption spectroscopy experiments.
Czyz,Weragoda,Monaghan,Connell,Brzozowski,Scully,Burton,Lupton,Polyzos
supporting information
p. 1543 - 1551
(2018/03/08)

Cesium carbonate-promoted synthesis of aryl methyl sulfides using: S -methylisothiourea sulfate under transition-metal-free conditions
In the presence of cesium carbonate, an efficient synthesis of aryl methyl sulfides by the reactions of aryl halides with commercially available S-methylisothiourea sulfate is developed. This odourless and highly crystalline solid can be used as the subst
Zhang, Caiyang,Zhou, You,Huang, Jintao,Tu, Canhui,Zhou, Xiaoai,Yin, Guodong
p. 6316 - 6321
(2018/09/10)

Phosphite-catalyzed alkoxycarbonylation of aryl diazonium salts
In this communication, an interesting phosphite-catalyzed alkoxycarbonylation of aryl diazonium salts has been reported. At room temperature and under CO pressure, moderate to good yields of the desired esters can be produced in the absence of bases or an
Xu, Jian-Xing,Franke, Robert,Wu, Xiao-Feng
supporting information
p. 6180 - 6182
(2018/09/10)

Palladium-Catalyzed Thiomethylation via a Three-Component Cross-Coupling Strategy
In this report, the combination of masked inorganic sulfur and dimethyl carbonate was designed to achieve thiomethylated cross coupling of aryl chlorides. Remarkably, this powerful strategy realized thiomethylation of nucleosides bearing unprotected ribose, chloride-containing pharmaceuticals with late-stage coupling, and herbicides possessing multiple heteroatoms and steric hindrance. Moreover, this protocol is practically amenable to multigram-scale synthesis with a lower catalysis loading and a higher yield.
Wang, Ming,Qiao, Zongjun,Zhao, Jiaoyan,Jiang, Xuefeng
supporting information
p. 6193 - 6197
(2018/09/25)

Pummerer rearrangement using bis(p-nitrophenyl) phosphorazidate as an azidation reagent: A novel synthesis of azidomethyl sulfides
A novel method for the synthesis of azidomethyl sulfides by Pummerer rearrangement using bis(p-nitrophenyl) phosphorazidate (p-NO2DPPA) as an azidation reagent was developed. Various methyl sulfoxides were converted into the corresponding azidomethyl sulfides. Importantly, this reaction enables the preparation of azidomethyl sulfides without the use of toxic or explosive azide sources.
Ishihara, Kotaro,Shioiri, Takayuki,Matsugi, Masato
supporting information
p. 3932 - 3935
(2017/09/20)

Methyl aryl thioether compound, and synthetic method and applications thereof
The invention discloses a methyl aryl thioether compound represented by formula 2, and a synthetic method and applications thereof. According to the synthetic method, in a reaction solvent, an aryl halide or an aromatic halide, dimethyl carbonate, and potassium thioacetate are taken as reaction raw materials, reaction is carried out in the presence of metal palladium catalyst under the action of a ligand and an alkali so as to obtain the methyl aryl thioether compound. The reaction conditions of the synthetic method are mild; the raw materials are cheap and easily available; reaction operation is simple; yield is relatively high. The methyl aryl thioether compound can be used for providing skeleton structures for the synthesis of a plurality of natural products and medicines, and can be widely applied in industrialized large-scale production.
-
Paragraph 0080; 0081; 0082

(2017/07/21)

Conversion of alcohols to alkyl esters and carboxylic acids using heterogeneous palladium-based catalysts
Disclosed are methods for synthesizing an ester or a carboxylic acid from an organic alcohol. To form the ester one reacts, in the presence of oxygen gas, the alcohol with methanol or ethanol. This reaction occurs in the presence of a catalyst comprising palladium and a co-catalyst comprising bismuth, tellurium, lead, cerium, titanium, zinc and/or niobium (most preferably at least bismuth and tellurium). Alternatively that catalyst can be used to generate an acid from that alcohol, when water is also added to the reaction mix.
-
Sheet 3

(2017/04/28)

Efficient and selective palladium-catalyzed direct oxidative esterification of benzylic alcohols under aerobic conditions
A highly efficient palladium-catalyzed approach for the direct oxidative esterification of benzylic alcohols with methanol and long-chain aliphatic alcohols under mild conditions has been achieved. This practical catalyst system exhibits a broad substrate scope and good functional group tolerance. Catalytic amount of Bi(OTf)3 is used as co-catalyst to improve the activity and selectivity of the reactions. A variety of esters are obtained in yields of 43–96%.
Hu, Yongke,Li, Bindong
p. 7301 - 7307
(2017/11/29)

Metal-Free, DTBP-Mediated Methylthiolation of Arylboronic Acids with Dimethyldisulfide
An efficient method for the C-S bond formation via the coupling reaction of arylboronic acids with dimethyldisulfide has been developed under the metal-free conditions. This novel protocol provides an attractive route for the synthesis of aryl methyl sulf
Wu, Xiang-Mei,Lou, Jia-Ming,Yan, Guo-Bing
supporting information
p. 2269 - 2273
(2016/10/30)

NOVEL SINGLE STEP ESTERIFICATION PROCESS OF ALDEHYDES USING A HETEROGENEOUS CATALYST
The present invention relates to a novel simple, efficient and single-step process for esterification of aldehydes using a heterogeneous catalyst with high yields. More particularly, the present invention relates to a novel simple, efficient and single-step process for esterification of aldehydes using Titanium superoxide with greater than 80% yields.
-
Page/Page column 7; 16

(2016/06/20)

Rhodium-Catalyzed ipso-Borylation of Alkylthioarenes via C-S Bond Cleavage
Rhodium-catalyzed transformation of alkyl aryl sulfides into arylboronic acid pinacol esters via C-S bond cleavage is reported. In combination with transition-metal-catalyzed sulfanyl group-guided regioselective C-H borylation reactions of alkylthioarenes, this method allows the synthesis of a diverse range of multisubstituted arenes.
Uetake, Yuta,Niwa, Takashi,Hosoya, Takamitsu
supporting information
p. 2758 - 2761
(2016/06/15)

A mild and facile synthesis of aryl and alkenyl sulfides via copper-catalyzed deborylthiolation of organoborons with thiosulfonates
An efficient deborylthiolation of aryl- and alkenylborons with thiosulfonates has been achieved under mild conditions using a copper catalyst. All steps of the experimental process were free from unpleasant odors. The mild reaction conditions as well as ready availability of boron compounds and thiosulfonates enabled easy access to an array of sulfides, including those bearing sensitive functional groups.
Yoshida, Suguru,Sugimura, Yasuyuki,Hazama, Yuki,Nishiyama, Yoshitake,Yano, Takahisa,Shimizu, Shigeomi,Hosoya, Takamitsu
supporting information
p. 16613 - 16616
(2015/11/25)

Titanium superoxide-a stable recyclable heterogeneous catalyst for oxidative esterification of aldehydes with alkylarenes or alcohols using TBHP as an oxidant
Titanium superoxide efficiently catalysed the oxidative esterification of aldehydes with alkylarenes or alcohols, under truly heterogeneous conditions, to afford the corresponding benzyl and alkyl esters in excellent yields. Mechanistic studies have established that this "one pot" direct oxidative esterification process proceeds through a radical pathway, proven by a FTIR spectral study of a titanium superoxide-aldehyde complex as well as spin trapping experiments with TEMPO. The intramolecular version of this protocol has been successfully demonstrated in the concise synthesis of 3-butylphthalide, an anti-convulsant drug.
Dey, Soumen,Gadakh, Sunita K.,Sudalai
p. 10631 - 10640
(2015/11/17)

Hydrogenation of sulfoxides to sulfides under mild conditions using ruthenium nanoparticle catalysts
The first demonstration of the hydrogenation of sulfoxides under atmospheric H2 pressure is reported. The highly efficient reaction is facilitated by a heterogeneous Ru nanoparticle catalyst. The mild reaction conditions enable the selective hydrogenation of a wide range of functionalized sulfoxides to the corresponding sulfides. The high redox ability of RuO x nanoparticles plays a key role in the hydrogenation.
Mitsudome, Takato,Takahashi, Yusuke,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
supporting information
p. 8348 - 8351
(2014/08/18)

Pd/C-catalyzed aerobic oxidative esterification of alcohols and aldehydes: A highly efficient microwave-assisted green protocol
We herein describe an environmentally friendly microwave-assisted oxidative esterification of alcohols and aldehydes in the presence of molecular oxygen and a heterogeneous catalysis (Pd/C, 5 mol %). This efficient and ligandless conversion procedure does not require the addition of an organic hydrogen acceptor. The reaction rate is strongly enhanced by mild dielectric heating. Furthermore, it is a versatile green procedure which generally enables the isolation of esters to be carried out by simple filtration in almost quantitative yields.
Caporaso, Marina,Cravotto, Giancarlo,Georgakopoulos, Spyros,Heropoulos, George,Martina, Katia,Tagliapietra, Silvia
supporting information
p. 1454 - 1461
(2014/07/22)

Catalytic methyl transfer from dimethylcarbonate to carboxylic acids
Although methylation reactions are commonplace, currently used reagents are hazardous, toxic, and/or unstable. Dimethylcarbonate has been put forth as an inexpensive, nontoxic, and green potential methylating reagent. Herein we report a general, base-catalyzed methyl transfer from dimethylcarbonate to carboxylic acids. High selectivity for esterification is observed even in the presence of unprotected phenols, and the mild reaction conditions enable conservation of stereochemistry at epimerizable stereocenters. Isotope-labeling studies suggest a mechanism proceeding by direct methyl transfer from dimethylcarbonate to the substrate.
Ji, Yuan,Sweeney, Jessica,Zoglio, Jillian,Gorin, David J.
p. 11606 - 11611
(2013/12/04)

Aerobic oxidation of diverse primary alcohols to methyl esters with a readily accessible heterogeneous Pd/Bi/Te catalyst
Efficient aerobic oxidative methyl esterification of primary alcohols has been achieved with a heterogeneous catalyst consisting of 1 mol % Pd/charcoal (5 wt %) in combination with bismuth(III) nitrate and tellurium metal. The Bi and Te additives significantly increase the reaction rate, selectivity, and overall product yields. This readily accessible catalyst system exhibits a broad substrate scope and is effective with both activated (benzylic) and unactivated (aliphatic) alcohols bearing diverse functional groups.
Powell, Adam B.,Stahl, Shannon S.
supporting information
p. 5072 - 5075
(2013/10/22)

N-Heterocyclic carbene catalyzed esterification of aromatic aldehydes with alcohols under aerobic conditions
A simple, organocatalytic procedure for the direct oxidative esterification of a variety of aromatic aldehydes with alcohols has been described that affords the corresponding aromatic esters in high yields. The method employs N-heterocyclic carbenes as catalysts and molecular O2 as an oxidant under ambient conditions.
Kiran, I. N. Chaithanya,Lalwani, Komal,Sudalai, Arumugam
p. 1695 - 1698
(2013/03/13)

Selective oxidation of alcohols to esters using heterogeneous Co 3O4-N@C catalysts under mild conditions
Novel cobalt-based heterogeneous catalysts have been developed for the direct oxidative esterification of alcohols using molecular oxygen as benign oxidant. Pyrolysis of nitrogen-ligated cobalt(II) acetate supported on commercial carbon transforms typical homogeneous complexes to highly active and selective heterogeneous Co3O4-N@C materials. By applying these catalysts in the presence of oxygen, the cross and self-esterification of alcohols to esters proceeds in good to excellent yields.
Jagadeesh, Rajenahally V.,Junge, Henrik,Pohl, Marga-Martina,Radnik, Joerg,Brueckner, Angelika,Beller, Matthias
supporting information
p. 10776 - 10782
(2013/08/23)

Anticancer prodrug studies: DielsAlder chemistry of 1-methylthio-1-(p- tolylsulfonyl)ethene
The reactivity of 1-methylthio-1-(p-tolylsulfonyl)ethene (1) as a dienophile in DielsAlder chemistry is investigated. Cycloaddition reactions were carried out with a range of pyran-2-ones and isobenzofurans. The initial DielsAlder adducts have the potenti
Pratt, Andrew J.,Rendle, Phillip M.,Steel, Peter J.
experimental part
p. 945 - 950
(2012/08/27)

Efficient synthesis of aryl methyl sulfide derivatives using (methylthio)trimethylsilane as methylthiolation reagent
The synthesis of various aryl methyl sulfides has been achieved by treatment of nitroarenes with a combination of (methylthio)trimethylsilane and cesium carbonate in dimethylsulfoxide. This reaction gives access to aryl methyl sulfide derivatives in high yields. Copyright
Qiao, Qi,Dominique, Romyr,Sidduri, Achyutharao,Lou, Jianping,Goodnow, Robert A.
scheme or table
p. 3691 - 3698
(2010/12/25)

The first general and selective palladium(II)-catalyzed alkoxycarbonylation of arylboronates: Interplay among benzoquinone-ligated palladium(0) complex, organoboron, and alcohol solvent
Methoxycarbonylation of aryl- and alken-ylboron compounds was performed using the palladium (II) acetate/triphenylphosphine [PdACHTUNGTRENNUNG(OAc) 2/PPh3] catalyst with p-benzoquinone as a stoichiometric oxidant in methanol at ambient temperature to obtain the corresponding methyl esters in good yields. A wide variety of functional groups including various carbonyl functionalities, nitrile, nitro, sulfone, and unprotected pyrrole rings were tolerated in the methoxycarbonlation, while the use of higher alcohols except for tert-butanol afforded various pchlorobenzoates in moderate to high yields. The catalytic alkoxycarbonylation proceeded without any acid or base additive, and an oxidative transmetalation step is proposed to explain the exceptional efficacy of this protocol. DFT and MP2 calculations support the proposed mechanism.
Yamamoto, Yoshihiko
supporting information; experimental part
p. 478 - 492
(2010/07/03)

Catalyzed dehydrogenative coupling of primary alcohols with water, methanol, or amines
A working partnership: Metal-ligand cooperativity is responsible for the high activity of the rhodium amido complex 1 in the dehydrogenative coupling of primary alcohols with water, methanol, or amines, including ammonia (see scheme), to give carboxylic acids, methyl carboxylates, or amides, respectively. The catalysis proceeds under mild reaction conditions in the presence of a recyclable hydrogen acceptor A. The multistep mechanism was elucidated by computational methods. (Chemical Equation Presented)
Zweifel, Theo,Naubron, Jean-Valere,Gruetzmacher, Hansjoerg
supporting information; experimental part
p. 559 - 563
(2009/04/14)

Facile conversion of dithioesters into carboxylic acids or esters using alkaline hydrogen peroxide
Simple, mild, and environmentally friendly procedures for the direct conversion of dithioesters into either carboxylic acids or esters using hydrogen peroxide under alkaline conditions are described. Georg Thieme Verlag.
Grellepois, Fabienne,Portella, Charles
experimental part
p. 3443 - 3446
(2009/05/09)

Highly chemoselective methylation and esterification reactions with dimethyl carbonate in the presence of NaY faujasite. The case of mercaptophenols, mercaptobenzoic acids, and carboxylic acids bearing OH substituents
In the presence of NaY faujasite, the reactions of dimethyl carbonate (DMC) with several ambident nucleophiles such as o- and p-mercaptophenols (1a,b), o- and p-mercaptobenzoic acids (2a,b), o- and p-hydroxybenzoic acids (3a,b), mandelic and phenyllactic acids (4, 5), have been explored under batch conditions. Highly chemoselective reactions can be performed: at 150 °C, compounds 1 and 2 undergo only a S-methylation reaction, without affecting OH and CO2H groups; at 165 °C, acids 3-5 form the corresponding methyl esters, while both their aromatic and aliphatic OH substituents are fully preserved from methylation and/or transesterification processes. Typical selectivities are of 90-98% and isolated yields of products (S-methyl derivatives and methyl esters, respectively) are in the range of 85-96%. A comparative study with K2CO3 as a catalyst is also reported. Although the base (K2CO3) turns out to be more active than the zeolite, the chemoselectivity is elusive: compounds 2a,b undergo simultaneous S-methylation and esterification reactions, and acids 3-5 yield complex mixtures of products of O-methylation, O-methoxycarbonylation, and esterification of their OH and CO2H groups, respectively. Overall, the combined use of a nontoxic reagent/solvent (DMC) and a safe promoter (NaY) imparts a genuine ecofriendly nature to the investigated synthesis.
Selva, Maurizio,Tundo, Pietro
p. 1464 - 1470
(2007/10/03)

Nanoscale aryleneethynylene molecular wires with reversible fluorenone electrochemistry for self-assembly onto metal surfaces
Two rigid-rod conjugated molecules (11 and 12) of ca. 4 and 7 nm length, respectively, bearing protected terminal thiol groups have been synthesized via multistep Sonogashira coupling reactions and shown to possess reversible cathodic solution electrochem
Wang, Changsheng,Batsanov, Andrei S.,Bryce, Martin R.,Sage, Ian
p. 2181 - 2184
(2007/10/03)

An efficient and selective conversion of hydrazides into esters and acids
Hydrazides are selectively oxidised to esters/acids in high yields using Oxone in the presence of an appropriate alcohol/water as a nucleophile at ambient temperature. A variety of functional groups including alkenes, alcohols, ethers, cyclopropyl groups and nitriles are unaffected.
Srinivas,Subba Reddy,Yadav,Ramalingam
p. 376 - 377
(2007/10/03)

Alkyl- and Arylthiodediazoniations of Dry Arenediazonium o-Benzenedisulfonimides. Efficient and Safe Modifications of the Stadler and Ziegler Reactions to Prepare Alkyl Aryl and Diaryl Sulfides
The reaction between dry arenediazonium o-benzenedisulfonimides 1 and sodium thiolates in anhydrous methanol represents an efficient and safe procedure, of general validity, for the preparation of unfunctionalized or variously functionalized alkyl aryl and diaryl sulfides. As a rule, the reaction temperature was maintained at 0-5°C for the alkylthiodediazoniations and at room temperature (20-25°C) for the arylthiodediazoniations. The sulfide yields are generally high; of the 63 considered examples, 43 gave yields greater than 80% and 13 were between 70% and 80%. Lower yields were obtained only when sterically hindered diazonium salts or thiols were used. A good amount of the o-benzenedisulfonimide (8) was always recovered from the reactions and could be reused to prepare salts 1. The copious experimental data collected in homogeneous conditions have offered several starting points for the study of the mechanism of these reactions.
Barbero, Margherita,Degani, Iacopo,Diulgheroff, Nicola,Dughera, Stefano,Fochi, Rita,Migliaccio, Mara
p. 5600 - 5608
(2007/10/03)

A New Indirect Application of Aggregative Activation: Synthesis of Esters by Cobalt-Catalyzed Carbonylation of Aryl, Heterocyclic, and Vinyl Halides under Atmospheric Pressure
Sun lamp illuminated alkoxycarbonylation of aryl, heteroaryl, and vinyl halides was performed under atmospheric pressure of CO in the presence of a cobalt catalyst in situ generated from Co(OAc)2.Illunination through a Pyrex flask was sufficient to catalyze the reaction.This process avoids the use of Co2(CO)8 and excess CH3I, which were required in the earlier procedure.A SRN1 mechanism is proposed.
Marchal, Joel,Bodiguel, Jacques,Fort, Yves,Caubere, Paul
p. 8336 - 8340
(2007/10/02)

Correlation of Carbon-13 Substituent-Induced Chemical Shifts: meta- and para-Substituted Methyl Benzoates
Carbon-13 NMR spectra are reported for 69 substituted methyl benzoates in deuteriochloroform or in its mixture with dimethyl sulphoxide-d6.The substituent-induced chemical shifts (SCS) of the CO carbon correlate poorly with dual substituent parameters (DSP) in all possible modifications, and for meta derivatives in particular this correlation is both overparameterized and imprecise.A much better correlation was obtained with parameters (designated Bm, Bp and Cp) derived previously by principal component analysis (PCA) from a larger set.The SCS of the CH3 carbon correlate very well with the original simple Hammett equation, and no DSP treatment is needed.The clustering of substituents is not consequential in such a large set.KEY WORDS Methyl benzoates 13C NMR Substituent effects
Budesinsky, Milos,Exner, Otto
p. 585 - 591
(2007/10/02)