- 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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- Preparation method for alpha-benzene methane sulfonic acid derivative with optical activity
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The invention discloses a preparation method for alpha-benzene methane sulfonic acid derivative with optical activity. The preparation method comprises the following steps: Step A: mixing a sodium thiocyanate aqueous solution with compound (I) to react, carrying out postprocessing after reaction is finished to obtain a compound (II); Step B: mixing the compound (II), acetic acid and concentrated sulfuric acid, carrying out oxidation reaction after hydrogen peroxide is added, and carrying out postprocessing after reaction is finished to obtain the alpha-benzene methane sulfonic acid derivative. According to the preparation method, the sodium thiocyanate is adopted as an reaction reagent, reaction yield is effectively improved, and meanwhile, preparation method is simple in operation, is friendly to environment and is easy in carrying out industrial production.
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Paragraph 0049-0056
(2018/04/01)
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- A simple, one-pot and phosphine-free procedure for thiocyanation of alcohols Using N-(p-toluenesulfonyl) imidazole (TsIm)
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An efficient, one-pot, phosphine-free thiocyanation of alcohols has been achieved utilising potassium thiocyanate and N-(p-toluenesulfonyl) imidazole (TsIm) as a coupling agent in the presence of triethylamine in anhydrous DMF at 70 °C. This method converts primary alcohols into the corresponding thiocyanates, without isomerisation to isothiocyanates, in good to excellent yields. A total of 17 thiocyananates were prepared, five of which are novel. Using one equivalent of KSCN, the method shows good selectivity in the thiocyanation of a primary alcohol in the presence of a secondary alcohol.
- Rad, Mohammad Navid Soltani
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p. 583 - 587
(2016/10/18)
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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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- Synthesis of alkyl thiocyanates from alcohols using a polymer-supported thiocyanate ion promoted by cyanuric chloride/dimethylformamide
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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
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p. 403 - 412
(2015/06/22)
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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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- 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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- 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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- 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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- One-pot reductive sulfenylation and thiocyanation of carbonyl compounds in ionic liquid media
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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
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p. 100 - 112
(2011/03/17)
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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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- 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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- Simple and quick preparation of α-thiocyanate ketones in hydroalcoholic media. Access to 5-aryl-2-imino-1,3-oxathiolanes
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A simple preparation on gram-scale of thiocyanate derivatives via nucleophilic substitution of halogenated compounds with SCN salts at high substrate concentrations in a few minutes and excellent yields was successfully accomplished in hydroalcoholic media. The obtained compounds were employed for the efficient synthesis of valuable 5-aryl-2-imino-1,3-oxathiolane derivatives (a one-pot approach is also presented).
- Bisogno, Fabricio R.,Cuetos, Anibal,Lavandera, Ivan,Gotor, Vicente
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supporting information; experimental part
p. 452 - 454
(2010/04/22)
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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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- 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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- Conversion of Alcohols, Thiols, Carboxylic Acids, Trimethylsilyl Ethers, and Carboxylates to Thiocyanates with Triphenylphosphine/ Diethylazodicarboxylate/NH4SCN
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A novel and highly selective method is described using triphenylphosphine/ diethylazodicarboxylate (DEAD)/NH4SCN for the conversion of alcohols, thiols, carboxylic acids, silyl ethers, and silyl carboxylates to their corresponding thiocyanates.
- Iranpoor, Nasser,Firouzabadi, Habib,Akhlaghinia, Batool,Azadi, Roya
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- Optimized access to alkyl thiocyanates
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Functionalized alkyl thiocyanates are synthesized in high yields from corresponding halides via in situ formation of tetra n-butylammonium thiocyanate. Use of this mild but efficient thiocyanation reagent limits the amounts of by-products.
- Renard, Pierre-Yves,Schwebel, Hervé,Vayron, Philippe,Leclerc, Eric,Dias, Sonia,Mioskowski, Charles
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p. 8479 - 8481
(2007/10/03)
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- The Functionalization of Saturated Hydrocarbons. Part 26. Ionic Substitution Reactions in GoAggIV Chemistry: The Construction of C-N, C-S and C-C Bonds
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Utilization of the GoAggIV system in the presence of sodium azide, sodium nitrite, sodium thiocyanate, sodium disulfide and tetraethylammonium cyanide converts saturated hydrocarbons into the corresponding alkyl azides, nitroalkanes, alkyl thiocyanates, dialkyl disulfides and alkyl cyanides, respectively.Mechanistic studies suggest an Fe-centered ligand coupling reaction pathway.Key Words: Gif systems; Selective functionalization, Iron catalysts, C-N bond formation, C-S bond formation, C-C bond formation
- Barton, Derek H. R.,Warinthorn, Chavasiri
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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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