- Synthesis of thiocarbamoyl fluorides and isothiocyanates using CF3SiMe3 and elemental sulfur or AgSCF3 and KBr with amines
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Reactions of thiocarbonyl fluoride derived from cheap, readily available, and widely used CF3SiMe3, elemental sulfur, and KF with secondary amines and primary amines at room temperature in THF provided a wide variety of thiocarbamoyl fluorides and isothiocyanates in moderate to excellent yields, respectively. The two reactions show broad substrate scope and good functional group tolerance. Moreover, AgSCF3 reacts with secondary/primary amines under KBr at room temperature, affording quantitative thiocarbamoyl fluorides/isothiocyanates, which feature late-stage application.
- Zhen, Long,Fan, Hui,Wang, Xiaoji,Jiang, Liqin
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supporting information
p. 2106 - 2110
(2019/03/26)
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- Synthesis methods for isothiocyanate derivative
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The invention discloses synthesis methods for an isothiocyanate derivative. The first synthesis method includes reacting raw materials, including primary amine, trifluoromethyltrimethylsilane, potassium fluoride and sulfur, with an organic solvent at the room temperature to obtain the isothiocyanate derivative. The synthetic isothiocyanate derivative has the advantages of simple operation, safety,high efficiency, non-toxicity, low raw material price, mild condition, high yield, wide application range of substrates, high compatibility of functional groups and the like. The second synthesis method includes reacting raw materials, including the primary amine, silver trifluoromethane and potassium bromide, with the organic solvent at the room temperature to obtain the isothiocyanate derivative. The isothiocyanate derivative has the advantages of simple operation, safety, high efficiency, easy availability of the raw materials, nearly quantitative yield, wide application range of the substrates, applicability to selective post-modification of drugs or complex compounds, and the like.
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Paragraph 0033; 0034; 0035; 0036; 0113; 0114; 0115; 0116
(2019/05/22)
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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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- 2,4,4,6-Tetrabromo-2,5-cyclohexadienone as an efficient reagent for phosphine-free electrophilic transformation of alcohols and epoxides
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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
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p. 251 - 258
(2016/06/01)
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- Facile and versatile synthesis of alkyl and aryl isothiocyanates by using triphosgene and cosolvent
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A mild and efficient method for the conversion of alkyl and aryl amines to isothiocyanates via dithiocarbamates has been developed using (CH 3)2CO-CS2 as co-solvent and triphosgene as dehydrosulfurization reagent. High yields, mild reaction conditions and excellent functional group compatibility make it become a versatile synthetic method for the preparation of isothiocyanates compared with reported methods. [Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications for the following free supplemental resource(s): Full experimental and spectral details.]
- Liu, Pengfei,Li, Chunyan,Zhang, Jingwei,Xu, Xiaoyong
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supporting information
p. 3342 - 3351
(2013/10/01)
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- Phosphine-free conversion of alcohols into alkyl thiocyanates using trichloroisocyanuric acid/NH4SCN
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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
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experimental part
p. 77 - 80
(2012/03/26)
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- In situ-generated N-thiocyanatosuccinimide (NTS) as a highly efficient reagent for the one-pot thiocyanation or isothiocyanation of alcohols
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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
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experimental part
p. 6588 - 6589
(2011/02/21)
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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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- Kinetic studies on the reactivity of triphenylmethyl cations adsorbed on silica, alumina, and aluminosilicate
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The apparent rate constants ka?2 of different surface-mediated reactions of three nucleophiles 1,4-cyclohexadiene, triethylsilane, and isobutylvinyl ether with triphenylmethylium ions have been determined for three different solid acid catalysts and various triphenylmethylium precursors (R1R2R3C-X, X = SCN, OH, Cl, or Br). Generation of triphenylmethylium ions [R1R2R3C+] was used for kinetic measurements when R1R2R3C-X derivates are chemisorbed to the solid acid catalysts. The catalysis of those surface-mediated reactions by a silica, an alumina, and an aluminosilicate has been studied in a slurry of dichloromethane at ambient temperature. The value of ka?2 increases in the order OH- - - - and silica s of the corresponding HX from R1R2R3C-X or the acidity of the solid acid (Adolph, S.; Spange, S.; Zimmermann, Y. J. Phys. Chem. B 2000, 104, 6429-6438) indicating the importance of the effective surface concentration of [R1R2R3C+] on the apparent rate constant. It is also shown that the specific rate constant of the surface-mediated reaction can be interpreted in terms of Mayr's nucleophilicity parameters of the ??-nucleophile (N) and the pKR+ values of the carbenium ion derived from polar reactions in homogeneous solution.
- Spange, Stefan,Adolph, Simone,Walther, Ralph,Zimmermann, Yvonne
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p. 298 - 305
(2007/10/03)
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- A Convenient Synthesis of Tertiary Isothiocyanates and Acyl Isothiocyanates Using Phosphoryl Isothiocyanate.
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Phosphoryl iosthiocyanate, PO(NCS)3, reacts readily with tertiary alcohols and carboxylic acids, giving the respective tertiary isothiocyanates and acyl isothiocyanates in good yields and purity.
- Kniezo, Ladislav,Bernat, Juraj
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p. 509 - 513
(2007/10/02)
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- NOVEL HIGHLY STEREOSPECIFIC METHOD OF 1,2-CIS-GLYCOSYLATION. SYNTHESIS OF α-D-GLUCOSYL-D-GLUCOSES
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Triphenylmethylium perchlorate-catalysed glycosylation of 2-, 3-, 4-, and 6-O-trityl-D-glucose derivatives with β-D-glucopyranosyl thiocyanates bearing a nonparticipating substituent at O-2 affords stereospecific derivatives of α-D-glucosyl-D-glucose
- Kochetkov, Nikolay K.,Klimov, Evgeny M.,Malysheva, Nelly N.
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p. 5459 - 5462
(2007/10/02)
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