- An ionic liquid supported on magnetite nanoparticles as an efficient heterogeneous catalyst for the synthesis of alkyl thiocyanates in water
-
The present study describes a convenient method to synthesize alkyl thiocyanates from alkyl halides with the use of a novel nanomagnetic-supported organocatalyst (MNP@PEG-ImCl). The new supported ionic liquid is fully characterized by field-emission scanning electron microscopy (FESEM), Fourier-transform infrared (FT-IR), energy dispersive X-ray analysis (EDAX), X-ray powder diffraction (XRD), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM) as well as thermogravimetric analysis (TGA) techniques. It is noteworthy that we observed easy separation of the catalyst from the reaction mixture by a simple magnetic decantation and its reutilization many times without any appreciable loss of activities.
- Fallah-Mehrjardi, Mehdi,Sayyahi, Soheil
-
p. 335 - 345
(2021/02/26)
-
- AIBN-initiated direct thiocyanation of benzylic sp3C-H with: N -thiocyanatosaccharin
-
Direct thiocyanations of benzylic compounds have been implemented. Here, a new strategy, involving a free radical reaction pathway initiated by AIBN, was used to construct the benzylic sp3 C-SCN bond. In this way, the disadvantage of other strategies involving introducing leaving groups in advance to synthesize benzyl thiocyanate compounds was overcome. The currently developed protocol also involved the use of readily available raw materials and resulted in high product yields (up to 100%), both being great advantages for synthesizing benzyl thiocyanates.
- Wu, Di,Duan, Yongjie,Liang, Kun,Yin, Hongquan,Chen, Fu-Xue
-
supporting information
p. 9938 - 9941
(2021/10/12)
-
- Thiocyanation and 2-Amino-1,3-thiazole Formation in Water Using Recoverable and Reusable Glycosylated Resorcin[4]arene Cavitands
-
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.
-
p. 9928 - 9935
(2020/09/03)
-
- A rings-in-pores net: Crown ether-based covalent organic frameworks for phase-transfer catalysis
-
We herein present a new family of crown ether-based covalent organic frameworks (CE-COFs) for the first time. The CE-COFs show excellent phase-transfer catalytic performance in various nucleophilic substitution reactions.
- Guo, Wen-Di,Hu, Bingwen,Jiang, Wei-Ling,Lou, Xiaobing,Ma, De-Li,Qi, Qiao-Yan,Shen, Ji-Chuang,Shen, Ming,Yang, Hai-Bo,Zhao, Xin
-
supporting information
p. 595 - 598
(2020/01/29)
-
- Selectfluor-initiated cyanation of disulfides to thiocyanates
-
A Selectfluor-initiated cyanation of disulfides to thiocyanates has been developed. In this process, Selectfluor was employed as the oxidant and trimethylsilyl cyanide was used as the cyanation reagent. It provides an eco-friendly and simple way to synthesize the thiocyanates.
- Zhou, Pengpeng,Chen, Chuan,Li, Shubai
-
p. 376 - 380
(2020/02/13)
-
- Sulfuryl Fluoride Promoted Thiocyanation of Alcohols: A Practical Method for Preparing Thiocyanates
-
A novel SO 2F 2-promoted thiocyanation method for the one-step synthesis of thiocyanates through C-O bond cleavage of readily available alcohols with ammonium thiocyanate as the thiocyanating agent was developed. The method avoids the use of additional catalyst, and a variety of (hetero)arene, alkene and aliphatic alcohols reacted with high efficiency in ethyl acetate under mild conditions to afford the corresponding thiocyanates in excellent to quantitative yields with broad functional-group compatibility.
- Zhang, Guofu,Xuan, Lidi,Zhao, Yiyong,Ding, Chengrong
-
supporting information
p. 1413 - 1417
(2020/10/02)
-
- Fluorium-Initiated Dealkylative Cyanation of Thioethers to Thiocyanates
-
Thioethers are converted to thiocyanates via fluorium-initiated dealkylative cyanation. Selectfluor is used as the oxidant, and trimethylsilyl cyanide is used as the cyanation reagent. The well-streamlined procedure is user-friendly, operationally simple, and step-economical. The current mechanistic studies show that the sulfur radical cation and cyano radical are both involved. They combine to deliver cyanosulfonium, an intermediate toward thiocyanate after dealkylation. Alternatively, a nucleophilic mechanism is also possible. Our dealkyaltive cyanation is also efficient in synthesizing thiocyanates with strongly electrophilic functionalities.
- Chen, Yang,Qi, Hongyi,Chen, Ning,Ren, Demin,Xu, Jiaxi,Yang, Zhanhui
-
p. 9044 - 9050
(2019/08/12)
-
- Electrochemical ipso-Thiocyanation of Arylboron Compounds
-
An operationally simple electrochemical method for the transition-metal-free ipso-thiocyanation of arylboronic acids and aryl trifluoroborates has been developed. The SCN electrophile is generated in situ by anodic oxidation of thiocyanate anions, which avoids formation of salt waste and prevents unwanted side reactions arising from chemical oxidants. The reaction proceeds regiospecifically, and the scope extends to non-activated aromatic systems. (Figure presented.).
- Dyga, Marco,Hayrapetyan, Davit,Rit, Raja K.,Goo?en, Lukas J.
-
supporting information
p. 3548 - 3553
(2019/04/26)
-
- PEG-DIL-based MnCl42?: A novel phase transfer catalyst for nucleophilic substitution reactions of benzyl halides
-
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
-
-
- Crown ether functionalized magnetic hydroxyapatite as eco-friendly microvessel inorganic-organic hybrid nanocatalyst in nucleophilic substitution reactions: an approach to benzyl thiocyanate, cyanide, azide and acetate derivatives
-
In this paper, high catalytic activity of 4′,4″-diformyl dibenzo-18-crown-6 anchored onto the functionalized magnetite hydroxyapatite (γ-Fe2O3@HAp–Crown) as a new, versatile and magnetically recoverable catalyst, was prepared. It evaluated as phase-transfer catalyst and molecular host system for nucleophilic substitution reactions of benzyl halides with thiocyanate, cyanide, azide and acetate anions in water. No evidence for the formation of by-products was observed and the products obtained in pure form without further purification. The nanocomposite was easily removed from solution via application of a magnetic field, allowing straightforward recovery and reuse. The synthesized nanocomposite was characterized by several techniques such as FT-IR, TGA-DTG, EDX, XRD, BET, FE-SEM, TEM and VSM.
- Azaroon, Maedeh,Kiasat, Ali Reza
-
-
- Potent anti-proliferative activities of organochalcogenocyanates towards breast cancer
-
The pharmacological importance, particularly the anti-cancer and chemopreventive potentials, of organochalcogen compounds has attracted wide research attention recently. Herein we describe the synthesis of a series of organochalcogenocyanates that have one or more selenocyanate or thiocyanate units in a single molecule. The anti-proliferative activity of these organochalcogenocyanates in different breast cancer cells shows that selenocyanates exhibit much higher anti-proliferative activities than thiocyanates in general. Our study reveals that the activity of benzyl selenocyanate (1, BSC) could be significantly enhanced by 4-nitro substitution (12), which was more selective towards triple-negative breast cancer cells (MDA-MB-231) over other ER+ breast cancer cells (MCF-7 and T-47D). Furthermore, to the best of our knowledge, this is the first report on the synthesis of compounds having more than two selenocyanate units with promising anti-proliferative activities. Our studies further indicate that the apoptotic activities of selenocyanates are associated with modulation of cellular morphology and cell cycle arrest at S-phase. Selenocyanates also inhibited cellular migration and exhibited weak antioxidant activities. An effective binding interaction of compound 12 with serum albumin indicates its feasible transport in the bloodstream for its enhanced anti-cancer properties. Mechanistic studies by western blot analysis demonstrate that benzylic selenocyanates exhibit anti-proliferative activities by modulating key cellular proteins such as Survivin, Bcl-2 and COX-2; this was further supported by molecular docking studies. The results of this study would be helpful in designing suitable chemotherapeutic and chemopreventive drugs in the future.
- Banerjee, Kaustav,Padmavathi, Ganesan,Bhattacherjee, Debojit,Saha, Suchismita,Kunnumakkara, Ajaikumar B.,Bhabak, Krishna P.
-
p. 8769 - 8782
(2018/11/30)
-
- Preparation method for thiocyanide compound
-
The invention discloses a preparation method for a thiocyanide compound. The preparation method comprises the following steps: taking a sulfhydryl compound, thiocyanate as raw materials, taking rose-bengal, eosine Y or eosin B as a catalyst, performing illumination, generating a thiocyanide compound after the illumination reaction. According to the preparation method provided by the invention, thiocyanide is decomposed into thiocyanate ions; the sulfhydryl compound generates sulfhydryl radical under the action of light and the catalyst, and the sulfhydryl radical is used for attacking carbon atoms in thiocyanate ions to obtain a intermediate; sulfide is removed from the intermediate to obtain the thiocyanide compound. The rose-bengal, the eosine Y or the eosin B used by the method containno heavy metal ion, and the adverse effect on the performance of the thiocyanide compound by the heavy metal ion residue is avoided; in addition, the catalyst is easily removed, so that a favorable condition is provided for the preparation of the thiocyanide compound with higher purity.
- -
-
Paragraph 0170; 0171; 0176; 0177
(2018/06/16)
-
- Direct Photocatalytic S-H Bond Cyanation with Green cN Source
-
Herein we report a novel C-S bond cleavage and reconstruction strategy for the synthesis of thiocyanates through direct photocatalytic S-H bond cyanation from thiols and inorganic thiocyanate salts. In our strategy, the unprecedented example of cutting off C-S bond of SCN- to deliver the green CN sources is demonstrated. This transformation features nontoxic and inexpensive CN sources, available starting materials, metal-/base-/ligand-/peroxide-free, high step economy and mild conditions. It leads to the construction of various thiocyanates and some medicinally and biologically active thiocyanate-containing molecules.
- Guo, Wei,Tan, Wen,Zhao, Mingming,Zheng, Lvyin,Tao, Kailiang,Chen, Deliang,Fan, Xiaolin
-
supporting information
p. 6580 - 6588
(2018/05/29)
-
- One-pot synthesis of (ethoxycarbonyl)difluoromethylthioethers from thiocyanate sodium and ethyl 2-(trimethylsilyl)-2,2-difluoroacetate (TMS-CF2CO2Et)
-
An efficient one-pot cascade methodology for the synthesis of (ethoxycarbonyl)difluoromethyl thioethers is described. Benzyl, allyl, alkyl halides or diazonium salts as the starting materials together with thiocyanate sodium and TMS-CF2CO2Et in the presence of CsF or NaOAc afford a variety of the fluoroalkylthiolated products in moderate to good yields.
- Xu, Lijun,Wang, Hongyu,Zheng, Changwu,Zhao, Gang
-
p. 6057 - 6066
(2017/09/23)
-
- 2,4,4,6-Tetrabromo-2,5-cyclohexadienone as an efficient reagent for phosphine-free electrophilic transformation of alcohols and epoxides
-
In this study, 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TABCO) was prepared and used successfully as a stable phosphine-free reagent for the conversion of alcohols into alkyl thiocyanates and epoxides into 2-hydroxythiocyanates. The reactions seem to proceed via in situ generation of electrophilic sulfur species by reaction of NH4SCN and TABCO. This combined reagent worked well with both alcohols and epoxides in acetonitrile solvent and under solvent-free conditions.
- Khajeh-Kolaki, Aslan,Mokhtari, Babak
-
p. 251 - 258
(2016/06/01)
-
- Synthesis of difluoromethyl thioethers from difluoromethyl trimethylsilane and organothiocyanates generated in situ
-
A copper-CF2H complex generated in situ from copper thiocyanate and TMS-CF2H smoothly converts organothiocyanates into valuable difluoromethyl thioethers. This reaction step can be combined with several thiocyanation methods to one-pot protocols, allowing late-stage difluoromethylthiolations of widely available alkyl halides and arenediazonium salts. This strategy enables the introduction of difluoromethylthio groups - a largely unexplored substituent with highly promising properties - into drug-like molecules. A copper-CF2H complex generated in situ from copper thiocyanate and TMS-CF2H smoothly converts organothiocyanates into valuable difluoromethyl thioethers. This reaction step can be combined with several thiocyanation methods to one-pot protocols, allowing late-stage difluoromethylthiolations of widely available alkyl halides and arenediazonium salts.
- Bayarmagnai, Bilguun,Matheis, Christian,Jouvin, Kvin,Goossen, Lukas J.
-
supporting information
p. 5753 - 5756
(2015/06/10)
-
- Tetrazole regioisomers in the development of nitro group-containing antitubercular agents
-
Tetrazole derivatives containing nitro substituents have been identified as promising antitubercular agents. In this study, the antitubercular potency, selectivity and toxicity of tetrazole 1,5- and 2,5-regioisomers were examined. We prepared a series of 1- and 2-alkyl-5-benzylsulfanyl-2H-tetrazoles and their selenium analogs with various nitro group substitutions. These 1,5- and 2,5-regioisomers were isolated and unambiguously identified using 1H and/or 13C NMR. Among the prepared compounds, 1- and 2-alkyl-5-[(3,5-dinitrobenzyl)sulfanyl]-2H-tetrazole derivatives and their selenium bioisosteres showed the highest antimycobacterial activity, with minimal inhibitory concentration (MIC) values of approximately 1 μM (0.37-0.46 μg mL-1) against Mycobacterium tuberculosis CNCTC My 331/88. The 2-alkyl regioisomers exhibited consistently higher antimycobacterial activity and lower in vitro toxicity against a mammalian cell line compared to the 1-alkyl isomers. The antimycobacterial activity of the 2-alkyl regioisomers was less influenced by the type of alkyl substituent in contrast to 1-alkyl isomers. Furthermore, the 3,5-dinitrobenzyl moiety per se is not the carrier of mutagenicity. These findings encourage further optimization of the 2-alkyl chain to improve the pharmacokinetic properties and toxicity of 2-alkyl-5-[(3,5-dinitrobenzyl)sulfanyl]-2H-tetrazole lead compounds. This journal is
- Karabanovich, Galina,Roh, Jaroslav,Soukup, Ondej,Pvkov, Ivona,Pasdiorov, Markta,Tambor, Vojtch,Stolakov, Jiina,Vejsov, Marcela,Vvrov, Kateina,Klimeov, Vra,Hrablek, Alexandr
-
supporting information
p. 174 - 181
(2015/02/02)
-
- Synthesis, characterization and theoretical studies of 5-(benzylthio)-1- cylopentyl-1H-tetrazole
-
In this study, 5-(benzylthio)-1-cylopentyl-1H-tetrazole (5B1C1HT) have been synthesized. Boiling points of the obtained compound have been determined and it has been characterized by FT-IR, 1H NMR, 13C-APT and LC-MS spectroscopy techniques. The FT-IR, 1H NMR and 13C-APT spectral measurements of the 5B1C1HT compound and complete assignment of the vibrational bands observed in spectra has been discussed. The spectra were interpreted with the aid of normal coordinate analysis following full structure optimization and force field calculations based on Density Functional Theory (DFT) at 6-311++G**, cc-pVDZ and cc-pVTZ basis sets. The optimized geometry with 6-311++G ** basis sets were used to determine the total energy distribution, harmonic vibrational frequencies, IR intensities.
- Saglam,Disli,Erdogdu,Marchewka,Kanagathara,Bay,Güllüo?lu
-
p. 1011 - 1018
(2014/11/08)
-
- Nitromethane as a cyanating reagent for the synthesis of thiocyanates
-
Nitromethane has been developed to be an effective cyanating reagent for the synthesis of thiocyanates. In the presence of iodine and base, a wide range of disulfides were reacted with nitromethane smoothly to give diverse thiocyanates in moderate to good yields.
- Wang, Zuo-Hui,Ji, Xiao-Ming,Hu, Mao-Lin,Tang, Ri-Yuan
-
supporting information
p. 5067 - 5070
(2015/08/06)
-
- Synthesis of alkyl thiocyanates from alcohols using a polymer-supported thiocyanate ion promoted by cyanuric chloride/dimethylformamide
-
A convenient procedure for one-pot conversion of alcohols into the corresponding alkyl thiocyanates in the presence of cross-linked poly (N-propyl-4-vinylpyridinium) thiocyanate ion [P4-VP]Pr-SCN, promoted by cyanuric chloride/dimethylformamide, is described. Various alcohols were converted to their corresponding alkyl thiocyanates and it was observed that substituted benzyl alcohol with electron-withdrawing or electron-donating groups were transformed into the corresponding benzyl thiocyanate derivatives in high to excellent yields in a short reaction time but, sterically hindered alcohols produced the corresponding thiocyanates in very low yields.
- Karimi Zarchi, Mohammad Ali,Tabatabaei Bafghi, Asmaosadat
-
p. 403 - 412
(2015/06/22)
-
- Preparation of 2'-13c-l-histidine starting from 13c-thiocyanate: Synthetic access to any site-directed stable isotope enriched l-histidine
-
1-Benzyl-2-(methylthio)-imidazole-5-ketone is obtained in a few simple steps starting from thiocyanate and glycine amide (glycin). Subsequent treatment with diethyl phosphorocyanidate and functional group manipulations gives 1-benzyl-5-chloromethylimidazolium chloride. This compound is converted under mild O'Donnell conditions into the corresponding L-histidine derivative. After deprotection L-histidine is obtained in good yield and 99% enantiomeric excess. 2'-13C-L-Histidine has been obtained via this new scheme with high (99%) 13C incorporation starting with commercially available 13C- thiocyanate. This synthetic scheme allows access to any isotopomer of L-histidine and many other biologically important imidazole derivatives.
- Talab, Sarra,Taha, Kamal Khalifa,Lugtenburg, Johan
-
p. 1023 - 1033
(2014/02/14)
-
- Chlorodiphenylphosphine as highly selective and efficient reagent for the conversion of alcohols, tetrahydropyranyl and silyl ethers to thiocyanates and isothiocyanates
-
(Equation present) A simple, highly selective and efficient method is described for the conversion of primary alcohols, tetrahydropyranyl and silyl ethers to thiocyanates by use of chlorodiphenylphosphine and ammonium thiocyanate. Secondary substrates produce both the two isomeric products, thiocyanate and isothiocyanate, while tertiary ones give isothiocyanates as the only products by this new method. In contrast to previously reported methods based on trivalent phosphorus for this transformation, the present method does not require an electrophile in the presence of trivalent phosphorus (ClPPh 2). The order of activity of these substrates is silyl ether> alcohol > tetrahydropyranyl ether. The present method not only interestingly distinguishes between primary, secondary and tertiary substrates but also converts them to the corresponding thiocyanates with excellent chemoselectivity in the presence of several other functional groups. 2014 Copyright Taylor & Francis Group, LLC.
- Aghapour, Ghasem,Asgharzadeh, Ameneh
-
p. 796 - 802
(2014/07/08)
-
- Copper-catalyzed cyanation of disulfides by azobisisobutyronitrile leading to thiocyanates
-
The copper-catalyzed cyanation of disulfides by azobisisobutyronitrile (AIBN) was developed, leading to thiocyanates in moderate to good yields. This procedure tolerates a series of functional groups, such as chloro, nitro, methyl and methoxycarbonyl in the phenyl ring of disulfides. Notably, it enables the use of two ArS units in (ArS)2. CuI was found to be essential for the in situ formation of cyanide anions. This journal is
- Teng, Fan,Yu, Jin-Tao,Yang, Haitao,Jiang, Yan,Cheng, Jiang
-
supporting information
p. 12139 - 12141
(2014/12/11)
-
- Nanomagnetic double-charged diazoniabicyclo[2.2.2]octane dichloride silica as a novel nanomagnetic phase-transfer catalyst for the aqueous synthesis of benzyl acetates and thiocyanates
-
Abstract Nanomagnetic double-charged diazoniabicyclo[2.2.2]octane dichloride silica hybrid (Fe3O4@SiO2/DABCO) was used as an efficient and magnetically recoverable phase-transfer catalyst (PTC) for nucleophilic substitution reactions of benzyl halides for the synthesis of benzyl acetates and thiocyanates in good to excellent yields at 100 C in water. No evidence for the formation of by-products, for example, isothiocyanate or benzyl alcohol was observed and the products were obtained in pure form without further purification. The catalyst was easily separated with the assistance of an external magnetic field from the reaction mixture and reused for several consecutive runs without significant loss of its catalytic efficiency.
- Davarpanah, Jamal,Kiasat, Ali Reza
-
-
- Synthesis and applications of quaternized highly branched polyacrylamide as a novel multi-site polymeric phase transfer catalyst
-
In current study, quaternized highly branched polyacrylamide (HBAA) was synthesized and used as an efficient multi-site polymeric phase transfer catalyst in nucleophilic substitution reactions and also in synthesis of α, β-unsaturated nitriles from reaction of acetonitrile and carbonyl compounds. The quaternized HBAA was synthesized via two steps. First, HBAA was synthesized via self-condensing vinyl polymerization of acrylamide at appropriate molar ratio of monomer to diperiodatocuprate(III). In the second step, 3-acrylamidopropyl trimethylammonium iodide was polymerized on peripheral area of the HBAA in the presence of diperiodatocuprate(III) solution again. The thermal behavior of HBAA and that of the quaternized HBAA were studied by DSC and TGA analysis. This phase transfer catalyst was easily recovered after reaction and reused several times without any loss of activity.
- Mahdavi, Hossein,Amirsadeghi, Mehdi
-
p. 791 - 797
(2013/07/27)
-
- Microwave-assisted synthesis of alkyl thiocyanates
-
Microwave irradiation accelerated the reaction of t-alkyl, allyl, and benzyl halides with Zn(SCN)2 to afford thiocyanates in excellent yields and high selectivity with the formation of isothiocyanates only in minor proportions. Because thiocyanates are stable intermediates to thiols, the method also affords facile access to corresponding thiols.
- Bound, D. James,Bettadaiah,Srinivas
-
p. 1138 - 1144
(2013/03/28)
-
- β-Cyclodextrin conjugated magnetic nanoparticles as a novel magnetic microvessel and phase transfer catalyst: Synthesis and applications in nucleophilic substitution reaction of benzyl halides
-
This paper presents a feasible protocol for the preparation of β-cyclodextrin conjugated Fe3O4 magnetic nanoparticles as an efficient microvessel and host system for nucleophilic substitution reaction of benzyl halides in water. No evidence for the formation of by-product for example isothiocyanate or benzyl alcohol was observed and the products were obtained in pure form without further purification. The characteristics results of FT-IR, XRD, TGA and SEM shows that β-CD is grafted onto Fe3O4 nanoparticles. The nanomagnetic catalyst could be readily separated from solution via application of an external magnet, allowing straightforward recovery and reuse.
- Kiasat, Ali Reza,Nazari, Simin
-
p. 363 - 368
(2013/07/26)
-
- β-cyclodextrin immobilized onto dowex resin: A unique microvessel and heterogeneous catalyst in nucleophilic substitution reactions
-
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
-
experimental part
p. 699 - 702
(2012/05/05)
-
- Antimicrobial volatile glucosinolate autolysis products from Hornungia petraea (L.) Rchb. (Brassicaceae)
-
Plant samples of Hornungia petraea were analyzed for glucosinolate (GLS) autolysis metabolites for the first time. GC-MS analysis of the autolysate and the synthesis of a series (12 compounds) of possible glucosinolate breakdown products revealed/corroborated the presence of glucoaubrietin, glucolimnanthin, glucolepigramin and glucotropaeolin in this species as the most likely "mustard oil" precursors. GLS degradation products identified in the autolysate of H. petraea, benzyl isothiocyanate, 3- and 4-methoxybenzyl isothiocyanate, along with several other structurally related compounds were evaluated for antimicrobial activity in order to possibly pinpoint the role of the latter secondary metabolites in the plant tissues. The assays showed a very high antibacterial activity of the tested isothiocyanates against Sarcina lutea and an antifungal effect against Aspergillus fumigatus and Candida albicans with MIC values in the order of 1 μg/ml value.
- Radulovi?, Niko S.,Deki?, Milan S.,Stojanovi?-Radi?, Zorica Z.
-
experimental part
p. 351 - 357
(2012/07/16)
-
- Magnetic nanoparticles grafted with β-cyclodextrin-polyurethane polymer as a novel nanomagnetic polymer brush catalyst for nucleophilic substitution reactions of benzyl halides in water
-
The polymer coated magnetic nanoparticles has gained significant attention for potential applications in biomedicine, separations, and magnetic storage. In this study, β-cyclodextrin-polyurethane polymer coated Fe 3O4 magnetic nanoparticle as a novel class of hybrid organic/inorganic molecular catalyst was successfully prepared and evaluated as solid-liquid phase-transfer catalyst and molecular host system for nucleophilic substitution reactions. The nanocomposite has demonstrated the ability to catalytic the nucleophilic substitution reaction of benzyl halides with thiocyanate, azide, cyanide and acetate anions in water. No evidence for the formation of by-products for example isothiocyanate or alcohol was observed and the products obtained in pure form without further purification. The nanomagnetic polymer brush catalyst was easily removed from solution via application of a magnetic field, allowing straightforward recovery and reuse. Results obtained from scanning electron microscopy (SEM) and vibrating sample magnetometery (VSM) show that the synthesized magnetic nanocomposite are superparamagnetic with a mean diameter of 59 nm. The grafting of β-cyclodextrin-polyurethane polymer to Fe3O4 magnetic nanoparticle is confirmed by Fourier transform infrared spectroscopy (FT-IR).
- Kiasat, Ali Reza,Nazari, Simin
-
-
- Selectfluor F-TEDA-BF4 mediated thiocyanation or isothiocyanation of alcohols by in situ generation of [+SCN] under heterogeneous and neutral conditions
-
A convenient approach for thiocyanation of alcohols has been developed using ammonium thiocyanate as thiocyanating agent in the presence of a catalytic amount of Selectfluor F-TEDA-BF4 in aqueous acetonitrile. In this method various alcohols generally afforded the corresponding thiocyanates or isothiocyanates directly in good to high yield under heterogeneous and neutral conditions.
- Khazaei, Ardeshir,Rahmati, Sadegh,Khalafi-Nezhad, Ali,Saednia, Shahnaz
-
experimental part
p. 123 - 125
(2012/05/05)
-
- A convenient, rapid, and general synthesis of α-oxo thiocyanates using clay supported ammonium thiocyanate
-
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.
-
experimental part
p. 1780 - 1785
(2012/05/04)
-
- 2-Chloro-1-methylpyridinium iodide, an efficient reagent for the conversion of alcohols into alkyl thiocyanates both under solvent and solvent-free conditions
-
A new application of the Mukaiyama reagent for the simple phosphine-free conversion of alcohols into the corresponding alkyl thiocyanates is described. This transformation can be achieved either in acetonitrile or under solvent-free conditions and the products obtained in good to excellent yields. The solvent-free procedure described here is the first report on the solvent-free thiocyanation of alcohols.
- Mokhtari, Babak,Azadi, Roya,Mardani, Edris
-
experimental part
p. 491 - 493
(2012/02/01)
-
- Phosphine-free conversion of alcohols into alkyl thiocyanates using trichloroisocyanuric acid/NH4SCN
-
A convenient and efficient phosphine-free procedure for the one-pot conversion of primary, secondary and tertiary alcohols into the corresponding alkyl thiocyanates or alkyl isothiocyanates is described using trichloroisocyanuric acid/NH4SCN.
- Azadi, Roya,Mokhtari, Babak,Makaremi, Mohamad-Ali
-
experimental part
p. 77 - 80
(2012/03/26)
-
- Ionic liquid brush as a highly efficient and reusable catalyst for on-water nucleophilic substitutions
-
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
-
supporting information; experimental part
p. 229 - 233
(2011/03/20)
-
- A novel and efficient synthesis of alkyl thiocyanates from alkyl halides in water using phase transfer catalysts
-
1,4-Bis(triphenylphosphonium)-2-butene dichloride (BTPBDC) and 1,4-bis(triphenyl phosphonium)-2-butene dithiocyanate (BTPBDT) were prepared and used as phase-transfer catalysts. Alkyl halides were converted efficiently to the corresponding alkyl thiocyanates under mild reaction conditions in water. No evidence for the formation of isothiocyanates as by-product of the reaction was observed.
- Gorjizadeh, Maryam,Sayyahi, Soheil
-
experimental part
p. 659 - 662
(2012/01/05)
-
- Rhodium(I)-catalyzed addition of arylboronic acids to (benzyl-/ arylsulfonyl)acetonitriles: Efficient synthesis of (Z)-β- sulfonylvinylamines and β-Keto sulfones
-
An efficient rhodium(I)-catalyzed addition of arylboronic acids to (benzyl-/arylsulfonyl)acetonitrile is described. Novel β-sulfonylvinylamine products are formed in a stereoselective fashion (Z-alkene). Upon hydrolysis, useful β-keto sulfones are obtained with a broad scope of aryl and sulfonyl substituents.
- Tsui, Gavin Chit,Glenadel, Quentin,Lau, Chan,Lautens, Mark
-
supporting information; experimental part
p. 208 - 211
(2011/03/19)
-
- One-pot reductive sulfenylation and thiocyanation of carbonyl compounds in ionic liquid media
-
The first example of an efficient one-pot reductive sulfenylation and thiocyanation of carbonyl compounds in environmentally benign ionic liquid (IL) media is reported. The process involves reduction of carbonyl compounds with NaBH4 in the IL [bmim]BF4 followed by I2-catalyzed reaction of the resulting alcohols with aromatic/aliphatic thiols or ammonium thiocyanate in the same vessel to afford sulfides or thiocyanates, respectively, in excellent yields (78-93%). Notably, the protocol precludes the necessity to prepare and isolate the intermediate alcohols in a separate step as they are formed in situ, and the IL used can be recycled easily for further use without any loss of efficiency. Copyright
- Yadav, Lal Dhar S.,Garima,Kapoor, Ritu
-
p. 100 - 112
(2011/03/17)
-
- Heterogeneous thiocyanation of benzylic alcohols and silyl and THP ethers, and deprotection of silyl and THP-ethers by [PCl3-n(SiO 2)n] (silphos)
-
Silicaphosphite (silphos), [PCl3-n(SiO2) n], as a heterogeneous phosphorous compound, catalyzes the thiocyanation of benzylic alcohols and silyl and THP ethers in the presence of I2 and NH4SCN in refluxing CH3CN. The produced silphos oxide byproduct can be easily separated by a simple filtration. Silphos is also used for the efficient and selective deprotection of silyl and THP-ethers to their corresponding alcohols. Copyright
- Iranpoor,Firouzabadi,Bahador,Jamalian
-
experimental part
p. 1972 - 1978
(2010/11/16)
-
- Tetrazine phototriggers: Probes for peptide dynamics
-
(Presented Chemical Equation) Surrender your secrets, peptides! Of several 3, 6-disubstituted tetrazines examined as phototriggers for the investigation of peptide dynamics, the most useful candidates were disulfenyl tetrazines. The thiocyanate fragments resulting from photol-ysis (see scheme) were detected by ultrafast infrared spectroscopy. Chromophore insertion into oxytocin and photofragmentation to trigger peptide relaxation were both demonstrated.
- Tucker, Matthew J.,Courter, Joel R.,Chen, Jianxin,Atasoylu, Onur,Smith III, Amos B.,Hochstrasser, Robin M.
-
scheme or table
p. 3612 - 3616
(2010/08/08)
-
- 4-Aminophenyl diphenylphosphinite (APDPP) as a heterogeneous and acid scavenger reagent for thiocyantion or isothiocyanation of alcohols and protected alcohols
-
4-Aminophenyl diphenylphosphinite (APDPP) as a heterogeneous phosphinite reagent is used for the efficient conversion of alcohols, trimethylsilyl- and tetrahydropyranyl ethers, α-hydroxy phosphonates, and - trimethylsilyloxyphosphonates to their corresponding thiocyanates or isothiocyanates in the presence of Br2 and NH4SCN.
- Iranpoor, Nasser,Firouzabadi, Habib,Gholinejad, Mohammad
-
experimental part
p. 2010 - 2019
(2010/03/24)
-
- In situ-generated N-thiocyanatosuccinimide (NTS) as a highly efficient reagent for the one-pot thiocyanation or isothiocyanation of alcohols
-
The first application of in situ-generated N-thiocyanatosuccinimide (NTS) for the thiocyanation of alcohols is described. This method can be easily applied for the facile conversion of primary, secondary and tertiary alcohols into the corresponding alkyl thiocyanates or alkyl isothiocyanates in good to excellent yields.
- Mokhtari, Babak,Azadi, Roya,Rahmani-Nezhad, Samira
-
experimental part
p. 6588 - 6589
(2011/02/21)
-
- Acyl-isothiocyanates as efficient thiocyanate transfer reagents
-
An unprecedented transfer of a thiocyanate (-SCN) group from aroyl/acyl isothiocyanate to alkyl or benzylic bromide is observed in the presence of a tertiary amine. This process is most effective when the bromomethyl proton is less acidic, while the prese
- Palsuledesai, Charuta C.,Murru, Siva,Sahoo, Santosh K.,Patel, Bhisma K.
-
supporting information; experimental part
p. 3382 - 3385
(2009/12/01)
-
- Decoupling deprotonation from metalation: Thia-fries rearrangement
-
(Chemical Equation Presented) Label-enabled: Studies with 2H-, 18O-, and 34S-labeled aryl triflates show that lithium diisopropylamide-mediated thia-Fries rearrangement proceeds through an irreversible ortho deprotonation (see scheme; DIPA = diisopropylamine, LDA = lithium diisopropylamide). In contrast, ortho metalation results exclusively in the generation of a benzyne.
- Dyke, Alan M.,Gill, Duncan M.,Harvey, Jeremy N.,Hester, Alison J.,Lloyd-Jones, Guy C.,Munoz, M. Paz,Shepperson, Ian R.
-
supporting information; experimental part
p. 5067 - 5070
(2009/03/11)
-
- Piperylene sulfone: A labile and recyclable DMSO substitute
-
The properties and uses of piperylene sulfone as a new, recyclable dipolar, aprotic solvent for conducting organic reactions are presented. The Royal Society of Chemistry.
- Vinci,Donaldson,Hallett,John,Pollet,Thomas,Grilly,Jessop,Liotta,Eckert
-
p. 1427 - 1429
(2008/02/03)
-
- Polymer-supported thiocyanate as new, versatile and efficient polymeric reagent for conversion of alkyl halides to corresponding alkyl thiocyanates under mild conditions
-
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
-
p. 1299 - 1302
(2008/02/13)
-
- 2-Hydroxy-N,N,N-tributylethanaminium thiocyanate as solvent and reagent for the preparation of alkyl thiocyanates
-
2-Hydroxy-N,N,N-tributylethanaminium thiocyanate was utilized as both solvent and reagent for the conversion of alkyl halides to the corresponding alkyl thiocyanates in good yields under mild conditions.
- Mohanazadeh, Farajollah,Aghvami, Magid
-
p. 7240 - 7242
(2008/03/11)
-
- Revisiting nucleophilic substitution reactions: Microwave-assisted synthesis of azides, thiocyanates, and sulfones in an aqueous medium
-
A practical, rapid, and efficient microwave (MW) promoted synthesis of various azides, thiocyanates, and sulfones is described in an aqueous medium. This general and expeditious MW-enhanced nucleophilic substitution approach uses easily accessible starting materials such as halides or tosylates in reaction with alkali azides, thiocyanates, or sulfinates in the absence of any phase-transfer catalyst, and a variety of reactive functional groups are tolerated.
- Ju, Yuhong,Kumar, Dalip,Varma, Rajender S.
-
p. 6697 - 6700
(2007/10/03)
-
- Preparation of thiocyanates and isothiocyanates from alcohols, thiols, trimethylsilyl-, and tetrahydropyranyl ethers using triphenylphosphine/2,3-dichloro-5,6-dicyanobenzoquinone (DDQ)/n-Bu4NSCN system
-
A combination of triphenylphosphine (PPh3) and 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) provides a safe and easily available mixed reagent system for the conversion of 1° and 2° alcohols, thiols, trimethylsilyl-, and tetrahydropyranyl ethers to their corresponding thiocyanates and the 3° ones to isothiocyanates in good to high yields.
- Iranpoor, Nasser,Firouzabadi, Habib,Nowrouzi, Najmeh
-
p. 5498 - 5501
(2007/10/03)
-
- A new diphenylphosphinite ionic liquid (IL-OPPh2) as reagent and solvent for highly selective bromination, thiocyanation or isothiocyanation of alcohols and trimethylsilyl and tetrahydropyranyl ethers
-
A new diphenylphosphinite ionic liquid (IL-OPPh2) is introduced. This ionic liquid is used as both a reagent and a solvent to convert alcohols and trimethylsilyl and tetrahydropyranyl (THP) ethers into their corresponding alkyl bromides, thiocyanates or isothiocyanates in the presence of Br2 and SCN- at 80 °C. In this ionic liquid, bromination and thiocyanation of alcohols occurs highly selectively in the presence of trimethylsilyl and THP-ethers and also between different classes of alcohols. The use of this ionic liquid allows easy separation of the desired products from the phosphinate by-product.
- Iranpoor, Nasser,Firouzabadi, Habib,Azadi, Roya
-
p. 5531 - 5534
(2007/10/03)
-
