- Na2S2O8-mediated efficient synthesis of isothiocyanates from primary amines in water
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We have developed two green, practical, and efficient procedures, including a one-pot one, to synthesize isothiocyanates from amines and carbon disulfide via desulfurization with sodium persulfate. Water is used as the solvent. Basic conditions are necessary for good chemoselectivity for isothiocyanates. Structurally diverse linear and branched alkyl amines and aryl amines are readily converted to isothiocyanates by the two procedures in satisfactory yields. Halogens, benzylic C-H bonds, methylthio, nitro, ester, alkenyl, electron-rich or -deficient (hetero)aryls, acetylenyl, and even phenolic and alcoholic hydroxyls are well tolerated. The one-pot procedure in water can also be used to realize the preparation of chiral isothiocyanates from chiral amines, and the modification of bioactive structures with free amino groups. In large-scale preparation, simple and practical purification procedures independent of column chromatography are developed.
- Fu, Zhicheng,Yuan, Wenhao,Chen, Ning,Yang, Zhanhui,Xu, Jiaxi
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supporting information
p. 4484 - 4491
(2018/10/17)
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- Reaction of Thiocarbonyl Fluoride Generated from Difluorocarbene with Amines
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The reaction of thiocarbonyl fluoride, generated from difluorocarbene, with various amines under mild conditions is described. Secondary amines, primary amines, and o-phenylenediamines are converted to thiocarbamoyl fluorides, isothiocyanates, and difluoromethylthiolated heterocycles, respectively. Thiocarbamoyl fluorides were further transformed into trifluoromethylated amines by using a one-pot process. Thiocarbonyl fluoride is generated in situ and is rapidly fully converted in one pot under mild conditions; therefore, no special safety precautions are needed.
- Yu, Jiao,Lin, Jin-Hong,Xiao, Ji-Chang
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supporting information
p. 16669 - 16673
(2017/12/07)
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- ISOTHIOCYANATE COMPOUNDS, PHARMACEUTICAL COMPOSITIONS, AND USES THEREOF
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Provided herein are compositions of matter and pharmaceutical compositions thereof, for use in inhibiting the growth of various microbial pathogens, including bacteria, fungi, protozoa, and viral pathogens. Also provided herein are methods of treating microbial diseases/infections and cancer with the compositions. The compositions are additionally useful in wood preservation and food preservation by inhibition of microbial growth.
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Paragraph 0315; 0330
(2015/10/05)
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- Multiple binding modes of isothiocyanates that inhibit macrophage migration inhibitory factor
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Macrophage migration inhibitory factor (MIF) is a pleiotropic cytokine that has roles in the innate immune response, and also contributes to inflammatory disease. While the biological properties of MIF are closely linked to protein-protein interactions, M
- Spencer, Emma S.,Dale, Edward J.,Gommans, Aimée L.,Rutledge, Malcolm T.,Vo, Christine T.,Nakatani, Yoshio,Gamble, Allan B.,Smith, Robin A.J.,Wilbanks, Sigurd M.,Hampton, Mark B.,Tyndall, Joel D.A.
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p. 501 - 510
(2015/04/27)
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- Contrasting Reactivity of CS2 with Cyclic vs. Acyclic Amidines
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The interaction between carbon dioxide (CO2) and amidines such as 1,8-diazabicyclo[5.4.0]undecane (DBU) has been extensively studied, but the reaction of isovalent CS2 with such bases has been largely ignored, apart from a single crystallography report. Acyclic acetamidines are cleaved by CS2 at room temperature to give an isothiocyanate and a thioacetamide. Because the pathway to that cleavage involves a rotation that is difficult for cyclic amidines, the reaction of CS2 with cyclic amidines produces an entirely different product: a cyclic carbamic carboxylic trithioanhydride structure. The path to that product involves sp3 C-H activation leading to the formation of a new C-C bond at a carbon α to the central carbon of the amidine group. Alkylation and ring-opening of the cyclic carbamic carboxylic trithioanhydride has also been demonstrated under ambient conditions.
- Ang, M. Trisha C.,Phan, Lam,Alshamrani, Aliyah K.,Harjani, Jitendra R.,Wang, Ruiyao,Schatte, Gabriele,Mosey, Nicholas J.,Jessop, Philip G.
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p. 7334 - 7343
(2015/11/25)
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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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- Synthesis and spectroscopic analysis of substituted 2-aminothiazolines
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2-Aminothiazolines can exist in two tautomeric species, amino and imino forms, which can theoretically exist as two stereoisomers. Several methods and techniques have been used to evaluate tautomeric process, but in this case 15N NMR spectrosco
- Ferreira, Renan B.,Tormena, Claudio F.,Almeida, Wanda P.
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p. 186 - 190
(2013/05/22)
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- Selectfluor F-TEDA-BF4 mediated thiocyanation or isothiocyanation of alcohols by in situ generation of [+SCN] under heterogeneous and neutral conditions
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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
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experimental part
p. 123 - 125
(2012/05/05)
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- 2-Chloro-1-methylpyridinium iodide, an efficient reagent for the conversion of alcohols into alkyl thiocyanates both under solvent and solvent-free conditions
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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
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experimental part
p. 491 - 493
(2012/02/01)
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- A general and facile one-pot process of isothiocyanates from amines under aqueous conditions
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A general and facile one-pot protocol for the preparation of a broad range of alkyl and aryl isothiocyanates has been developed from their corresponding primary amines under aqueous conditions. This synthetic process involves an in situ generation of a dithiocarbamate salt from the amine substrate by reacting with CS2 followed by elimination to form the isothiocyanate product with cyanuric acid as the desulfurylation reagent. The choice of solvent is of decisive importance for the successful formation of the dithiocarbamate salt particularly for highly electron-deficient substrates. This novel and economical method is suitable for scale-up activities.
- Sun, Nan,Li, Bin,Shao, Jianping,Mo, Weimin,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
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experimental part
p. 61 - 70
(2012/04/04)
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- Heterogeneous thiocyanation of benzylic alcohols and silyl and THP ethers, and deprotection of silyl and THP-ethers by [PCl3-n(SiO 2)n] (silphos)
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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
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experimental part
p. 1972 - 1978
(2010/11/16)
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- Highly efficient and catalyst-free synthesis of unsymmetrical thioureas under solvent-free conditions
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A highly efficient and simple synthesis of unsymmetrical thioureas is reported based on the reaction of readily synthesized dithiocarbamates with amines, without using any catalyst under solvent-free conditions. The short reaction time, high yields, and s
- Halimehjani, Azim Ziyaei,Pourshojaei, Yaghoub,Saidi, Mohammad R.
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scheme or table
p. 32 - 34
(2009/04/10)
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- ISOTHIOCYANATE COMPOUNDS, PHARMACEUTICAL COMPOSITIONS, AND USES THEREOF
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Provided herein are compositions of matter and pharmaceutical compositions thereof, for use in inhibiting the growth of various microbial pathogens, including bacteria, fungi, protozoa, and viral pathogens. Also provided herein are methods of treating microbial diseases/infections and cancer with the compositions. The compositions are additionally useful in wood preservation and food preservation by inhibition of microbial growth.
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Page/Page column 67; 71-72
(2008/12/07)
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- Isothiocyanates from tosyl chloride mediated decomposition of in situ generated dithiocarbamic acid salts
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(Chemical Equation Presented) A facile and general protocol for the preparation of isothiocyanates from alkyl and aryl amines is reported. This method relies on a tosyl chloride mediated decomposition of a dithiocarbamate salt that is generated in situ by treatment of an amine with carbon disulfide and triethylamine. Utilizing this protocol, we have prepared 19-alkyl- and arylisothiocyanates in moderate to excellent yield.
- Wong, Rince,Dolman, Sarah J.
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p. 3969 - 3971
(2008/02/01)
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- A new method for the synthesis of isothiocyanates from dithiocarbamates or alkyl amines using chlorosilanes as decomposition reagents
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A series of isothiocyanates were prepared in good yields by the decomposition of dithiocarbamates using chlorosilanes such as Me 3SiCl, Me2SiCl2, MeSiCl3, and SiCl4 as decomposition reagents. Alkyl isothiocyanates were obtained by a facile one-pot method in high yield from alkyl amines using these inexpensive decomposition reagents in the presence of a base. Copyright Taylor & Francis Group, LLC.
- Bian, Gaofeng,Qiu, Huayu,Jiang, Jianxiong,Wu, Jirong,Lai, Guoqiao
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p. 503 - 508
(2007/10/03)
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- Oxalic acid-catalyzed reaction of alcohols with NaSCN: The effects of additives NaI and i2
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Oxalic acid-mediated conversion of alcohols to thiocyante and/or isothiocyanate is described. Aliphatic tertiary alcohols give isothiocyanate by the reaction with NaSCN in the presence of I2, whereas they give thiocyanate without it. Copyright
- Miyake, Hideyoshi,Nakao, Yuichi,Sasaki, Mitsuru
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p. 1262 - 1263
(2008/02/05)
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- A one-pot preparation of isothiocyanates from amines using two phosgene substitutes: bis-(trichloromethyl) carbonate and trichloromethyl chloroformates
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A series of isothiocyanates have been prepared in high yields in a one-pot reaction from commercial amines and carbon disulfide under mild conditions using bis(trichloromethyl)carbonate (BTC) and trichloromethyl chloroformate (TCF) as reagents in the presence of base.
- Bian, Gaofeng,Shan, Weiguang,Su, Weike
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p. 585 - 586
(2007/10/03)
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- A general synthesis of isothiocyanates from dithiocarbamates using claycop
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A Convenient and simple synthesis of alkyl, aryl and amino acid isothiocyanates is described by the decomposition of ammonium dithiocarbamates using Claycop in mild conditions.
- Mesheram, Harashadas M.,Dale, Srinivas,Yadav
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p. 8743 - 8744
(2007/10/03)
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- A facile one-pot preparation of isothiocyanates from aldoximes
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Isothiocyanates 2a-l were prepared in excellent yields in a one-pot reaction from aldoxime derivatives 1a-l by successive treatment of aldoxime with N-chlorosuccinimide (NCS), thiourea, and triethylamine. The use of HCl/DMF/Oxone system in the reaction instead of NCS was equally effective.
- Kim, Jae Nyoung,Jung, Keum Shin,Lee, Hong Jung,Son, Ji Suk
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p. 1597 - 1598
(2007/10/03)
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- The invention of radical reactions. Part XXVI. New thio- and seleno-hydroxamic acids; radical chemistry of their O-acyl derivatives
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New thio- and seleno-hydroxamic acids have been synthesized from various 4,4-disubstituted thiazolidine 2,5-dithiones. Their corresponding O-acyl derivatives rearrange photochemically, with visible light, in an identical manner to the acyl derivatives of
- Barton,Tachdjian
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p. 7091 - 7108
(2007/10/02)
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