- AIBN-initiated direct thiocyanation of benzylic sp3C-H with: N -thiocyanatosaccharin
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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
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supporting information
p. 9938 - 9941
(2021/10/12)
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- Sulfuryl Fluoride Promoted Thiocyanation of Alcohols: A Practical Method for Preparing Thiocyanates
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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
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supporting information
p. 1413 - 1417
(2020/10/02)
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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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- One-pot synthesis of (ethoxycarbonyl)difluoromethylthioethers from thiocyanate sodium and ethyl 2-(trimethylsilyl)-2,2-difluoroacetate (TMS-CF2CO2Et)
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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
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p. 6057 - 6066
(2017/09/23)
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- Microwave-assisted synthesis of alkyl thiocyanates
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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
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p. 1138 - 1144
(2013/03/28)
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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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- 2-Hydroxy-N,N,N-tributylethanaminium thiocyanate as solvent and reagent for the preparation of alkyl thiocyanates
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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
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p. 7240 - 7242
(2008/03/11)
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- Efficient conversion of silyl ethers to thiocyanates with Ph3P(SCN)2
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A new and efficient method for the conversion of primary and secondary alkyl, aryl, allyl and benzyl silyl ethers to their corresponding thiocyanates by in-situ generation of Ph3P(SCN)2 is described. The reactions occur immediately at room temperature and provide high to excellent yields of thiocyantes.
- Iranpoor,Firouzabadi,Shaterian
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- Versatile route to functionalized 1H-2-benzothiopyrans and 1H-2- naphthothiopyrans by electrophilic cyclization of Bis(arylmethylthio)acetylenes: 2-Benzo- and 2-naphthothiopyrylium salts
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Substituted 1H-2-benzothiopyrans find applications as pharmaceutically active compounds or synthons for more complex sulfur heterocycles. However, restricted variability in their synthesis limits the application for research or industrial purposes. To develop a direct and fast route to substituted and functionalized 1H-2-benzothiopyrans, we investigated the ring closure of symmetrical bis(arylmethylthio)acetylenes with iodine monochloride or bromine. This facile reaction yielded 1H-3-halo-4-arylmethylthio-2-benzo- and 2-naphthothiopyrans via postulated vinyl cations in yields of 47-86%. Substituted 2-benzo- and 2-naphthothiopyrylium salts were prepared by hydride abstraction with triphenylcarbenium tetrafluoroborate from the products, further enhancing the synthetic potential of the found cyclization reaction.
- Klein,Bergemann,Yehia,Fanghanel
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p. 4626 - 4631
(2007/10/03)
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- Photolysis of Vinyl Halides. Reaction of Photogenerated Vinyl Cations with Cyanate and Thiocyanate Ions
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The title reaction was conducted in a two-phase system of dichloromethane and water using a tetrabutylammonium halide as a phase-transfer catalyst.The reaction of the photogenerated arylvinyl cation with cyanate ion gave only isoquinolone derivatives, whereas the reaction with thiocyanate ion afforded products derived from S attack, vinyl thiocyanates, and products derived from N attack, vinyl isothiocyanates or thioisoquinolones.The ambident nature of thiocyanate ion is compared with the reaction of benzyl bromides.
- Kitamura, Tsugio,Kobayashi, Shinjiro,Taniguchi, Hiroshi
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p. 1801 - 1805
(2007/10/02)
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- Substitution Reaction of Organic Halide by Trimethylsilyl Isothiocyanate: Formation of Thiocyanate and Its Rearrangement to Isothiocyanate
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The reaction of organic halide with trimethylsilyl isothiocyanate (TMSTC) gave thiocyanate 1 and its isomerized isothiocyanate 2.Details of the substitution and the isomerization reactions were examined.
- Nishiyama, Kozaburo,Oba, Makoto
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p. 2692 - 2694
(2007/10/02)
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- Nucleophilic Substitution on 4-Methylbenzyl Thiocyanate with Nucleophiles
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The reactions of 4-methylbenzyl thiocyanate (1) with several nucleophiles have been investigated.Compound 1 possesses three electrophilic sites, i.e., benzylic carbon, sulfur and cyano carbon, to receive nucleophilic attack.PhS- and CN- which have HOMO's of high energy levels appear to attack preferentially the sulfur atom.MeO- was found to attack preferably the cyanide carbon, while amines which have HOMO's of low energy levels prefer benzylic carbon to attack.The nucleophilic substitution on the sulfur or the cyanide carbon generates CN- or p-xylene-α-thiolate anion, strong nucleophiles, as the primary products, which then initiate the complex secondary reactions.The selective reactivities of three attacking sites for nucleophiles in 1 have been rationalized in terms of MO theory.
- Oae, Shigeru,Yamada, Norihiro,Fujimori, Ken,Kikuchi, Osamu
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p. 248 - 256
(2007/10/02)
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- Heterocycles in Organic Synthesis. Part 36. An Alternative to the Gattermann Reaction for the Conversion of Anilines into Thiocyanates
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5,6-Dihydro-2,4-diphenylnaphthopyrylium thiocyanate is prepared in high yield.It reacts with primary arylamines to yield the corresponding fused pyridinium thiocyanates which when pyrolysed with a KNCS-NaCNS eutectic at ca. 220 deg C give the aryl thiocyanates in yields averaging 80percent.
- Katritzky, Alan R.,Thind, Sukhpal S.
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p. 865 - 868
(2007/10/02)
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