- Thiocyanation and 2-Amino-1,3-thiazole Formation in Water Using Recoverable and Reusable Glycosylated Resorcin[4]arene Cavitands
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A family of three spatially directional resorcin[4]arene cavitand glycoconjugates (RCGs) have been applied as efficient recoverable and reusable inverse phase transfer catalysts for eco- A nd environmentally friendly thiocyanation and 2-amino-1,3-thiazole formation reactions in water. The results show that RCGs (1 mol %) were capable of hosting and catalyzing various water-insoluble bromo/thiocyanato substrates in water without the use of any co-organic solvents. The recoverability and reusability of RCG catalytic systems, that is, RCG1 and RCG3, were also examined upon a simple extraction of the desired products using DCM or ethyl acetate, followed by subjecting the recovered aqueous solution containing the RCG catalysts to the next reaction cycles.
- Husain, Ali A.,Bisht, Kirpal S.
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p. 9928 - 9935
(2020/09/03)
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- PEG-DIL-based MnCl42?: A novel phase transfer catalyst for nucleophilic substitution reactions of benzyl halides
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Poly(ethylene glycol) dicationic ionic liquid-based MnCl42? was prepared by nucleophilic substitution of poly(ethylene glycol) dichloride with methylimidazole followed by reaction with MnCl2. The structural properties of the catalyst were systematically investigated using Fourier transform infrared, UV–visible and Raman spectra and thermogravimetric analysis. The application of this catalyst allows the synthesis of a variety of benzyl thiocyanates and azides in high yield under reflux conditions in water. The main advantages of this method are its easy nature, rapidity, environmental benignity and high yields.
- Goodajdar, Bijan Mombeni,Akbari, Farideh,Davarpanah, Jamal
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- Iron-Catalyzed Decarboxylation of Trifluoroacetate and Its Application to the Synthesis of Trifluoromethyl Thioethers
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Nucleophilic CF3 has been generated by decarboxylation of potassium trifluoroacetate, arguably the most easy-to-handle, inexpensive, and sustainable source of trifluoromethyl groups. Simple iron(II) chloride catalyzes the decarboxylation as well as a subsequent trifluoromethylation of organothiocyanates, resulting in a straightforward synthesis of trifluoromethyl thioethers. The KCN byproduct is absorbed by iron(II) with formation of nontoxic potassium hexacyanoferrate. An analogous trifluoromethylation of aldehydes with trifluoroacetate underlines the synthetic potential of such iron-catalyzed decarboxylative trifluoromethylations.
- Exner, Benjamin,Bayarmagnai, Bilguun,Jia, Fan,Goossen, Lukas J.
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supporting information
p. 17220 - 17223
(2016/01/25)
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- A convenient, rapid, and general synthesis of α-oxo thiocyanates using clay supported ammonium thiocyanate
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A very rapid, convenient, and general method for the synthesis of α-oxo thiocyanates has been described by using clay supported ammonium thiocyanate. The procedure avoids the use of additional catalyst, solvent, aqueous work-up and the yields are high. Moreover, the method is applicable for a variety of aryl, heteroaryl, alkyl α-halo carbonyls, β-keto tosylates, α-halo β-dicarbonyl, α-tosyl, β-dicarbonyl, alkyl halide, and alkyl tosylates.
- Meshram,Thakur, Pramod B.,Madhu Babu,Bangade, Vikas M.
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experimental part
p. 1780 - 1785
(2012/05/04)
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- β-cyclodextrin immobilized onto dowex resin: A unique microvessel and heterogeneous catalyst in nucleophilic substitution reactions
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The catalytic activity of β-cyclodextrin immobilized on Dowex resin as an efficient solid-liquid phase transfer catalyst was developed for the synthesis of alkyl thiocyanates and phenacyl derivatives in water. The nucleophilic substitution reactions were performed under mild reaction condition and gave the products in excellent yields. Furthermore, the catalyst could be recycled by facile separation without any loss of activity.
- Kiasat, Ali Reza,Zarinderakht, Nasrollah,Sayyahi, Soheil
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experimental part
p. 699 - 702
(2012/05/05)
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- Ionic liquid brush as a highly efficient and reusable catalyst for on-water nucleophilic substitutions
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A very efficient and reusable catalyst has been developed for the on-water nucleophilic substitution of alkyl halides and tosylates with azide or thiocyanate in excellent to quantitative yields. The reaction proceeds smoothly and cleanly without any organic cosolvent or other adductive, and the brush can be reused at least 10 times without noticeable loss of the catalytic activity. The high efficiency, simplicity of product and catalyst isolation, outstanding recyclability, and organic-solvent-free conditions show promise for the use of this catalyst in the laboratory and in industry. A highly efficient and reusable ionic liquid brush catalyst has been developed for the on-water nucleophilic substitution of alkyl halides and tosylates with azide or thiocyanate in excellent to quantitative yields without any organic cosolvent or other adductive. The catalyst can be reused at least 10 times without noticeable loss of the catalytic activity. Copyright
- Li, Jing,Cao, Jing-Jing,Wei, Jun-Fa,Shi, Xian-Ying,Zhang, Li-Hui,Feng, Jin-Juan,Chen, Zhan-Guo
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supporting information; experimental part
p. 229 - 233
(2011/03/20)
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- A new synthesis of alkane and polyfluoroalkanesulfonyl chlorides
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This study describes a new and advantageous procedure for the synthesis of alkanesulfonyl chlorides (2) by the reaction of alkyl thiocyanates (1) with sulfuryl chloride in a mixture of acetic acid and water. The alkanesulfonyl chlorides were obtained in good yields.
- Benfodda, Zohra,Guillen, Franck,Arnion, Helene,Dahmani, Abdelkader,Blancou, Hubert
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experimental part
p. 355 - 361
(2010/07/16)
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- Polymer-supported thiocyanate as new, versatile and efficient polymeric reagent for conversion of alkyl halides to corresponding alkyl thiocyanates under mild conditions
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Crosslinked poly(N-methyl-4-vinylpyridinium)thiocyanate [P 4-Me]SCN (II) is prepared easily and is used as a new polymeric reagent for synthesis of alkyl thiocyanates from alkyl halides under mild and nonaqueous conditions. The used polymeric reagent usually can be removing quantitatively and be regenerated.
- Zarchi, Mohammad Ali Karimi
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p. 1299 - 1302
(2008/02/13)
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- Efficient conversion of thiols to thiocyanates by in situ generated Ph3P(SCN)2
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A new, novel, rapid and simple method is described for the one-pot conversion of thiols to thiocyanates by use of in situ generated PPh3(SCN)2 at room temperature.
- Iranpoor, Nasser,Firouzabadi, Habib,Shaterian, Hamid Reza
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p. 3439 - 3441
(2007/10/03)
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- Thiocyanation of alkyl halides with alkyl thiocyanates in the presence of quaternary phosphonium halides
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Alkyl thiocyanates undergo simple SN2 reactions with the counter ions of quaternary phosphonium salts in nonpolar solvents and thiocyanate ions are liberated as the leaving ion. Depending on the nucleophile, the reaction proceeded irreversibly or reversibly. The reaction of benzyl thiocyanate with azide ions afforded a quantitative yield of benzyl azide. The reactions of alkyl thiocyanates with halide ions gave an equilibrium mixture where the reverse reaction of the alkyl halides produced with the liberated thiocyanate ions took place simultaneously. Thus, thiocyanate-halide exchange reactions between an alkyl thiocyanate and an alkyl halide were possible in the presence of a catalytic amount of a quaternary salt.
- Ohtani, Noritaka,Murakawa, Shigeki,Watanabe, Kohji,Tsuchimoto, Daisuke,Sato, Daiki
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p. 1851 - 1856
(2007/10/03)
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- Syntheses of Organic N,N-Dialkyldithiocarbamates or Organic Thiocyanates from Organozincs and Corresponding Thio-Anions via the Inversion of Electronic Reactivity of the Anions with NCS-Oxidation
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Novel displacement of metal ions from organometallic compounds with nucleophilic reagents was achieved in the reaction between organozinc compounds and N,N-dialkyldithiocarbamate ions (N,N-DAD-) or thiocyanate ion by the assistance of NCS, whereby alkyl or aryl N,N-DAD or alkyl, alkenyl, alkynyl, aryl, or heteroaryl thiocyanates were obtained in moderate to excellent yields as the result of novel bond construction between carbon fragments from organozinc compounds and thio-anions.
- Takagi, Kentaro,Takachi, Hideaki,Sasaki, Ken
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p. 6552 - 6556
(2007/10/03)
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- Preparation of zirconium (benzyldiethylammoniomethylphosphonate chloride) and PTC reactions
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Zirconium (benzyldiethylammoniomethylphosphonate chloride)phosphate Zr(HPO4)2-x (O2PCH2N+Et2CH2ph·Cl-)x·H2O, (0.25 x 0.75, ZBEPC-ZP) were prepared for the first time and characterized by IR and elemental analyses. ZBEPC-ZP catalyzed some typical PTC reactions in L/S/L phases were carried out to give good results. ZBEPC-ZP can be easily separated from the reaction mixture and recovered about 70-100%, and can be reused and did not show any change in activity after 10 cycles.
- Fu,Wen
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p. 2435 - 2442
(2007/10/02)
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- Facile Synthesis of Organic Thiocyanates from Organozinc(II) Thiocyanates and N-chlorosuccinimide
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The reaction of organozinc(II) compounds, generated in situ from organolithiums and zinc(II) thiocyaniate, with N-chlorosuccinimide (NCS) afforded the corresponding organic thiocyanates in good yields.
- Takagi, Kentaro,Takachi, Hideaki,Hayama, Naomi
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p. 509 - 510
(2007/10/02)
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- Nucleophilic Substitution Reactions of Alkyl Halides By Using New Polymer-Supported Reagents Containing Hemin
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A new polymer reagent consisting of hemin, divinylbenzene, and 2-methyl-5-vinylpyridine was synthesized by suspension copolymerization.Substitution reactions of primary, secondary, and tertiary alkyl halides with the hemin copolymer combined with cyanide, azide, and thiocyanate ions were given satisfactory yields.This reaction mechanism was revealed to be a SNi type on the basis of stereochemical study.The hemin copolymer was not only a polymer-supported reagent with functional capabilities, but also served to separate the product from the reaction mixture.
- Saito, Kiyoshi,Harada, Kaoru
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p. 2562 - 2566
(2007/10/02)
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- Quaternary ammonium salts used as phase transfer catalyst
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Novel quaternary ammonium salts of general formula (I) STR1 wherein: R is a saturated or unsaturated, linear or branched alkyl radical of C1 to C8. R' is a saturated or unsaturated, linear or branched alkyl radical of C1 to C12, or a benzyl radical. n is a number equal to 2 or 3. Xθ is a halogenide anion, such as Clθ, Brθ, Iθ, are used as phase transfer catalysts, in heterogeneous ionic reactions wherein the reagents are in different phase and have different polarity.
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- Cationic Complexes of Transition Metals as a New Type of Phase-transfer Catalyst
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Cationic complexes of the type (+)Cl(-) (M = Rh, Ir, Fe; L = 2,2'-bipyridyl or 1,10-phenanthroline) were found to act as phase-transfer catalysts that can be used as bifunctional catalysts in consecutive reactions of metal-complex and phase-transfer catalysis.
- Goldberg, Yuri Sh.,Iovel, Irina G.,Shymanska, Mariya V.
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p. 286 - 287
(2007/10/02)
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- The efficiency of diphenylalkylsulfonium salts as alkylating agents
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A series of the title reagents have been used for the alkylation of a number of nucleophiles including iodide, cyanide, thiocyanate and fluoride ions as well as ethyl acetoacetate, phenylacetonitrile and a variety of nitrogen heterocyclic compounds.The results compared favorably with literature methods.
- Badet, Bernard,Julia, Marc,Lefebvre, Christian
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p. 431 - 434
(2007/10/02)
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- Ion-pair extraction of thiocyanate from plasma and its gas chromatographic determination using on-column alkylation
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Tributylsulfonium thiocyanate may be extracted from aqueous solutions with organic solvents. Injection into the heated injection port of a gas chromatograph results in conversion to the volatile derivative butyl thiocyanate. Tributylsulfonium selenocyanate undergoes analogous extraction and thermal conversion to the butyl derivative. A procedure has been developed for the extraction of thiocyanate from human plasma and gas chromatographic determination using selenocyanate as an internal standard. The method has good sensitivity and precision and has been applied to behavioral and pharmacologic studies of smokers.
- Jacob III,Savanapridi,Yu,et al.
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p. 1692 - 1695
(2007/10/02)
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- COMPARISON OF UNSTIRRED, SONICATED AND STIRRED MIXTURES ON THE TWO-PHASE DISPLACEMENT OF HALIDE BY THIOCYANATE ION
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The two-phase catalytic reaction of alkyl halides with aqueous thiocyanate ion has been found to proceed readily in stirred, unstirred, and sonicated solutions.
- Reeves, W. Preston,McClusky, John V.
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p. 1585 - 1588
(2007/10/02)
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- Betylates. 4. The synthesis and preparative nucleophilic substitution reactions of alkyl S-betylates
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Alkyl S-betylates (S,S-dialkyl-S-3propylsulfonium salts), the first examples of S-betylates (sulfonioalkanesulfonic esters), have been synthesized by two routes, and their suitability as intermediates in the transformation of alcohols by nucleophilic substitution reactions examined.They have been found to react readily in stoichiometric phase transfer processes, including substrate-reagent ion-pair reactions, like their previously studied nitrogen analogues, with the following particular features: (a) they may be used with basic nucleophiles (unlike betylates), (b) they are more simply made from commercially available starting materials than betylates, and (c) they can be made by a route that avoids a final alkylation step.
- King, James Frederick,Skonieczny, Stanislaw,Poole, Gary Allan
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p. 235 - 243
(2007/10/02)
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- Reaction of Guanidinium Salts with Alkyl Bromides and Acid Chlorides
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The guanidinium salt 1a reacts with alkyl bromides 2a-g and acid chlorides 2h-k to give the nitriles 3a-g and the acyl cyanides 3h-k, respectively.Acyl isocyanates 4a,b have been obtained from the guanidinium cyanate 1d and the acid chlorides 2h,l.Reaction of the alkyl bromides 2b,c,m,n and acid chlorides 2h,l with the guanidinium thiocyanate 1e affords alkyl thiocyanates 5a-d and acyl isothiocyanates 6a,b, respectively.
- Kantlehner, Willi,Kapassakalidis, Johannis J.,Speh, Peter,Braeuner, Hans-Juergen
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p. 389 - 393
(2007/10/02)
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