- Facile Synthesis of Organic Thiocyanates from Organozinc(II) Thiocyanates and N-chlorosuccinimide
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The reaction of organozinc(II) compounds, generated in situ from organolithiums and zinc(II) thiocyaniate, with N-chlorosuccinimide (NCS) afforded the corresponding organic thiocyanates in good yields.
- Takagi, Kentaro,Takachi, Hideaki,Hayama, Naomi
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- Selectfluor-initiated cyanation of disulfides to thiocyanates
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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
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p. 376 - 380
(2020/02/13)
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- An electrochemical method for deborylative seleno/thiocyanation of arylboronic acids under catalyst- And oxidant-free conditions
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An electrochemical deborylative seleno/thiocyanation of arylboronic acids has been well established to synthesize the corresponding aryl seleno/thiocyanates with good functional group tolerance under ambient conditions. A gram-scale reaction has been performed to highlight the advantages of the protocol. Preliminary mechanistic studies indicate that the oxidation of the seleno/thiocyanate anion occurs prior to that of the arylboronic acid substrate in galvanostatic mode, and that free radicals are involved in the process.
- He, Dongdong,Yao, Jiaojiao,Ma, Boling,Wei, Jinghao,Hao, Guangguo,Tuo, Xun,Guo, Shengmei,Fu, Zhengjiang,Cai, Hu
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supporting information
p. 1559 - 1564
(2020/03/26)
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- Fluorium-Initiated Dealkylative Cyanation of Thioethers to Thiocyanates
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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
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p. 9044 - 9050
(2019/08/12)
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- Direct Photocatalytic S-H Bond Cyanation with Green cN Source
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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
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supporting information
p. 6580 - 6588
(2018/05/29)
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- Preparation method for thiocyanide compound
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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.
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Paragraph 0122; 0123; 0128; 0129
(2018/06/16)
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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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- Synthesis of perfluoroalkyl thioethers from aromatic thiocyanates by iron-catalysed decarboxylative perfluoroalkylation
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Easily available aryl and heteroaryl thiocyanates were converted into the corresponding perfluoroalkyl thioethers via decarboxylation of potassium perfluoroalkylcarboxylates, catalysed by the inexpensive and environmentally benign iron(III) chloride.
- Exner, Benjamin,Bayarmagnai, Bilguun,Matheis, Christian,Goossen, Lukas J.
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supporting information
p. 89 - 93
(2017/06/23)
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- Transition-metal-free synthesis of thiocyanato- or nitro-arenes through diaryliodonium salts
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A transition-metal-free approach to facile synthesis of thiocyanato- and nitro-arenes was developed from KSCN (potassiumthiocyanate) or NaNO2with diaryliodonium salts in good yields under mild conditions. The reaction was compatible with a variety of sensitive functional substituents such as halides and nitro and ester groups. The usefulness of arylation products has been realized. (Formula Present).
- Li, Xiao-Hua,Li, Liang-Gui,Mo, Xue-Ling,Mo, Dong-Liang
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p. 963 - 970
(2016/07/07)
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- Molybdenum-doped α-MnO2 as an efficient reusable heterogeneous catalyst for aerobic sulfide oxygenation
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Oxygenation of sulfides to sulfoxides and/or sulfones is an important transformation, and the development of efficient heterogeneous catalysts for oxygenation, which can utilize O2 as the terminal oxidant, is highly desired. In this study, we have successfully developed manganese oxide-based efficient heterogeneous catalysts for aerobic oxygenation of sulfides. Firstly, we prepared four kinds of manganese oxides possessing different crystal structures, such as α-MnO2, β-MnO2, γ-MnO2, and δ-MnO2, and their structure-activity relationships were examined for the aerobic oxygenation of thioanisole. Amongst them, α-MnO2 showed the best catalytic performance for the oxygenation. Moreover, α-MnO2 was highly stable during the catalytic oxygenation possibly due to the tunnel K+ ions. In order to further improve the catalytic performance of α-MnO2, substitutional doping of transition metal cations, such as Mo6+, V5+, Cr3+, and Cu2+, into the framework was carried out. Undoped α-MnO2 possessed a fibrous morphology. When high-valent transition metal cations were doped, especially Mo6+, the lengths of the fibers drastically shortened to form grain-like aggregates of ultrafine nanocrystals, resulting in an increase in specific surface areas and the numbers of catalytically active surface sites. In the presence of Mo6+-doped α-MnO2 (Mo-MnO2), various kinds of sulfides could efficiently be oxidized to the corresponding sulfoxides as the major products. The observed catalysis was truly heterogeneous, and Mo-MnO2 could repeatedly be reused while keeping its high catalytic performance. Besides sulfide oxygenation, Mo-MnO2 could efficiently catalyze several aerobic oxidative functional group transformations through single-electron transfer oxidation processes, namely, oxygenation of alkylarenes, oxidative α-cyanation of trialkylamines, and oxidative S-cyanation of benzenethiols.
- Uematsu, Tsubasa,Miyamoto, Yumi,Ogasawara, Yoshiyuki,Suzuki, Kosuke,Yamaguchi, Kazuya,Mizuno, Noritaka
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p. 222 - 233
(2015/12/31)
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- Iron-Catalyzed Decarboxylation of Trifluoroacetate and Its Application to the Synthesis of Trifluoromethyl Thioethers
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Nucleophilic CF3 has been generated by decarboxylation of potassium trifluoroacetate, arguably the most easy-to-handle, inexpensive, and sustainable source of trifluoromethyl groups. Simple iron(II) chloride catalyzes the decarboxylation as well as a subsequent trifluoromethylation of organothiocyanates, resulting in a straightforward synthesis of trifluoromethyl thioethers. The KCN byproduct is absorbed by iron(II) with formation of nontoxic potassium hexacyanoferrate. An analogous trifluoromethylation of aldehydes with trifluoroacetate underlines the synthetic potential of such iron-catalyzed decarboxylative trifluoromethylations.
- Exner, Benjamin,Bayarmagnai, Bilguun,Jia, Fan,Goossen, Lukas J.
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supporting information
p. 17220 - 17223
(2016/01/25)
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- Nitromethane as a cyanating reagent for the synthesis of thiocyanates
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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
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supporting information
p. 5067 - 5070
(2015/08/06)
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- Transition-metal-free cross-coupling of thioethers with aryl(cyano)iodonium triflates: A facile and efficient method for the one-pot synthesis of thiocyanates
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A novel transition-metal-free cross-coupling method for the one-step synthesis of thiocyanates via the C-S bond cleavage of readily available thioethers with aryl(cyano)-iodonium triflates as the cyanating agent is developed. This process features relatively broad substrate scopes, less-toxic hypervalent iodine reagents, mild operating conditions, excellent functional group compatibilities, and affords various thiocyanates in moderate to good yields. This journal is
- Zhu, Dan,Chang, Denghu,Shi, Lei
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supporting information
p. 7180 - 7183
(2015/04/27)
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- A mild copper-catalyzed aerobic oxidative thiocyanation of arylboronic acids with TMSNCS
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A facile and efficient transformation of arylboronic acids to their corresponding aryl thiocyanates has been successfully developed. Based on the CuCl-catalyzed oxidative cross-coupling reaction between arylboronic acids and trimethylsilylisothiocyanate (TMSNCS) under oxygen atmosphere, the transformation can be readily conducted at ambient temperature. The newly-developed protocol provided a competitive synthetic approach to aryl thiocyanates that can tolerate a broad range of reactive functional groups and/or strong electron-withdrawing groups.
- Sun, Nan,Che, Liusheng,Mo, Weimin,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
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supporting information
p. 691 - 696
(2015/02/19)
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- Practical access to aromatic thiocyanates by CuCN-mediated direct aerobic oxidative cyanation of thiophenols and diaryl disulfides
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The practical and mild aerobic oxidative CuCN-mediated cyanation of thiophenols and diaryl disulfides was investigated. The reaction was performed in air at room temperature and reached aromatic thiocyanates in moderate to good yields starting from a broad range of diversely functionalized substrates.
- Castanheiro, Thomas,Gulea, Mihaela,Donnard, Morgan,Suffert, Jean
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supporting information
p. 7814 - 7817
(2015/02/19)
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- Copper-catalyzed cyanation of disulfides by azobisisobutyronitrile leading to thiocyanates
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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
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supporting information
p. 12139 - 12141
(2014/12/11)
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- Synthesis of aryl thiocyanates via copper-catalyzed aerobic oxidative cross-coupling between arylboronic acids and KSCN
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A new protocol for the preparation of aryl thiocyanates by the cross-coupling reaction of arylboronic acids with KSCN salt is described. The coupling reaction was catalyzed by 20 mol% of copper acetate in the presence of 2.0 equivalents 4-methylpyridine serving both as ligand and base under 0.2 MPa of molecular oxygen. A variety of arylboronic acids, including those with substituents at ortho position, were suitable under the reaction conditions. Georg Thieme Verlag Stuttgart · New York.
- Sun, Nan,Zhang, Han,Mo, Weimin,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
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supporting information
p. 1443 - 1447
(2013/07/26)
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- Synthesis of aryl thiocyanates using Al2O3/MeSO 3H (AMA) as a novel heterogeneous system
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Indoles and various aromatic and heteroaromatic compounds undergo smooth thiocyanation with ammonium thiocyanate in the presence of a mixture of Al 2O3, MeSO3H (AMA) under mild conditions without use of any organic solvent
- Hosseini-Sarvari, Mona,Tavakolian, Mina
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experimental part
p. 318 - 321
(2009/04/16)
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- Catalytic thiocyanation of aryldiazonium salts in the presence of copper salts
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Aryldiazonium fluoroborates readily react with potassium thiocyanate in the presence of the CuI/CuII/Phen catalytic system to give arylthiocyanates in high yields.
- Beletskaya, Irina P.,Sigeev, Alexander S.,Peregudov, Alexander S.,Petrovskii, Pavel V.
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p. 250 - 251
(2007/10/03)
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- Improved procedure to aryl thiocyanates: A new synthetic application of dry arenediazonium o-benzenedisulfonimides
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Aryl thiocyanates 3 (22 examples) were easily prepared by reaction of dry arenediazonium o-benzenedisulfonimides 1 and sodium thiocyanate (2) in anhydrous acetonitrile at room temperature (20-25 °C) in the presence of copper powder (Procedure A) and at 50 °C or room temperature without the metal catalyst (Procedure B). The yields were from very good to excellent in Procedure A (average yield = 83%), and from modest to excellent in Procedure B (average yield = 63%). In comparison with the thiocyanod-ediazoniation carried out under traditional Sandmeyer-type conditions, the yields of 3 were higher and the isothiocyanate isomers were formed only in traces. Moreover, the results obtained in the absence of copper confirm the role of the anion of salts 1 as an electron transfer agent.
- Barbero,Degani,Diulgheroff,Dughera,Fochi
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p. 585 - 590
(2007/10/03)
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- An efficient synthetic route to aryl thiocyanates from arenesulfinates
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An efficient procedure for the conversion ot the inexpensive and readily available arenesulfinate (sodium) salts in three steps into the corresponding aryl thiocyanates is described. Overall yields are high, and the presence of both electron-with drawing and electron-donating substituents is well tolerated.
- Still,Watson
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p. 1355 - 1359
(2007/10/03)
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- A new preparative method of thiocanates by the solid state thiosulfonate/cyanide reaction
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The mixing and heating of thiosulfonates with potassium cyanide in the solid state gave a variety of thiocyanates in good yield. This method provides easy access to aryl thiocyanates.
- Fujiki, Kiyoko,Yoshida, Eiji
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p. 3289 - 3294
(2007/10/03)
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- Thiocyanatoarylation of α,β,β-Trifluorostyrene
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Reactions of α,β,β-trifluorostyrene with arenediazonium tetrafluoroborates and potassium thiocyanate result in addition of the aryl and thiocyanato group across the double bond. Unlike other related reactions, the process requires no catalyst. The reaction is accompanied by formation of aryl thiocyanates and aryl isothiocyanates as by-products.
- Bilaya,Obushak,Ganushchak
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p. 995 - 998
(2007/10/03)
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- Copper(I)-mediated novel thiocyanation of nonactivated aryl iodides
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Various aryl thiocyanates 2 were easily prepared in acceptable yields by heating aryl iodides 1 with cuprate complex K[Cu(SCN)2] in N,N-dimethylformamide (DMF).
- Suzuki, Hitomi,Abe, Hajime
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p. 3413 - 3419
(2007/10/03)
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- Syntheses of Organic N,N-Dialkyldithiocarbamates or Organic Thiocyanates from Organozincs and Corresponding Thio-Anions via the Inversion of Electronic Reactivity of the Anions with NCS-Oxidation
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Novel displacement of metal ions from organometallic compounds with nucleophilic reagents was achieved in the reaction between organozinc compounds and N,N-dialkyldithiocarbamate ions (N,N-DAD-) or thiocyanate ion by the assistance of NCS, whereby alkyl or aryl N,N-DAD or alkyl, alkenyl, alkynyl, aryl, or heteroaryl thiocyanates were obtained in moderate to excellent yields as the result of novel bond construction between carbon fragments from organozinc compounds and thio-anions.
- Takagi, Kentaro,Takachi, Hideaki,Sasaki, Ken
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p. 6552 - 6556
(2007/10/03)
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- Facile Synthesis of Thiocyanate Using Trimethylsilyl Cyanide
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Arenethiocyanate can be prepared by reaction of trimethylsilyl cyanide with sodium arenesulphinate or arenesulphonyl chloride.
- Kagabu, Shinzo,Maehara, Masaki,Sawahara, Keisuke,Saito, Katsuhiro
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p. 1485 - 1486
(2007/10/02)
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- NEW METHODS AND REAGENTS IN ORGANIC SYNTHESIS. 23. DIETHYL PHOSPHOROCYANIDATE(DEPC): A USEFUL REAGENT FOR AN UNPRECEDENTED TRANSFORMATION OF SULFINIC ACIDS TO THIOCYANATES
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Diethyl phosphorocyanidate(DEPC) can be efficiently used for a simple, one-step transformation of sulfinic acids to thiocyanates.
- Harusawa, Shinya,Shioiri, Takayuki
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p. 447 - 448
(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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- Effect of Solvation on the Nucleophilic Reaction of Stable Carbanions with Diaryl Disulfides
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Stable carbanions react with diaryl disulfides in aqueous solution by direct displacement (SN2) reaction to yield an arylthiol anion and the corresponding sulfide as products.The reaction of 1,3-dicarbonyl carbanions with 5,5'-dithiobis(2-nitrobenzoic acid) is characterized by Broensted βC value of 0.5.Nitroalkane carbanions react 102-104 slower than 1,3-dicarbonyl carbanions of the same pK and are correlated by a Broensted βC of 0.95.The second-order rate constants for the reaction of nitroalkane carbanions increase by factors of 104-106 as the solvent is changed from water to dimethyl sulfoxide.Smaller increases are observed in the rate constants for reaction of 2,4-pentadienone carbanion (102) and malonitrile carbanion (100.6) with the same sulfide.A linear correlation is found between log (kMe2SO4/kHOH) and the increase in pK for the carbon acid ionization on changing the solvent from water to dimethyl sulfoxide.The effect is attributed to large differences in ground-state carbanion solvation which are reduced or absent in the transition state.Parallels are drawn between the nucleophilic reaction of stable carbanions with diaryl disulfides and proton-transfer reactions of the same carbanions.
- Gilbert, H. F.
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p. 7059 - 7065
(2007/10/02)
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