85071-27-8Relevant academic research and scientific papers
Sulfuryl Fluoride Promoted Thiocyanation of Alcohols: A Practical Method for Preparing Thiocyanates
Zhang, Guofu,Xuan, Lidi,Zhao, Yiyong,Ding, Chengrong
supporting information, p. 1413 - 1417 (2020/10/02)
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.
One-pot synthesis of (ethoxycarbonyl)difluoromethylthioethers from thiocyanate sodium and ethyl 2-(trimethylsilyl)-2,2-difluoroacetate (TMS-CF2CO2Et)
Xu, Lijun,Wang, Hongyu,Zheng, Changwu,Zhao, Gang
, p. 6057 - 6066 (2017/09/23)
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.
Phosphine-free conversion of alcohols into alkyl thiocyanates using trichloroisocyanuric acid/NH4SCN
Azadi, Roya,Mokhtari, Babak,Makaremi, Mohamad-Ali
experimental part, p. 77 - 80 (2012/03/26)
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.
Synthetic scope, computational chemistry and mechanism of a base induced 5-endo cyclization of benzyl alkynyl sulfides
Motto, John M.,Castillo, álvaro,Greer, Alexander,Montemayer, Laura K.,Sheepwash, Erin E.,Schwan, Adrian L.
supporting information; experimental part, p. 1002 - 1010 (2011/03/19)
We present an experimental and computational study of the reaction of aryl substituted benzyl 1-alkynyl sulfides with potassium alkoxide in acetonitrile, which produces 2-aryl 2,3-dihydrothiophenes in poor to good yields. The cyclization is most efficient with electron withdrawing groups on the aromatic ring. Evidence indicates there is rapid exchange of protons and tautomerism of the alkynyl unit prior to cyclization. Theoretical calculations were also conducted to help rationalize the base induced 5-endo cyclization of benzyl 1-propynyl sulfide (1a). The potential energy surface was calculated for the formation of 2,3-dihydrothiophene in a reaction of benzyl 1-propynyl sulfide (1a) with potassium methoxide. Geometries were optimized with CAM-B3LYP/6-311+G(d,p) in acetonitrile with the CPCM solvent model. It is significant that the benzyl propa-1,2-dien-1-yl sulfane (6) possessed a lower benzylic proton affinity than the benzyl prop-2-yn-1-yl sulfane (8) thus favoring the base induced reaction of the former. From benzyl(propa-1,2-dien-1- yl sulfane (6), 2,3-dihydrothiophene can be formed via a conjugate base that undergoes 5-endo-trig cyclization followed by a protonation step.
4-Aminophenyl diphenylphosphinite (APDPP) as a heterogeneous and acid scavenger reagent for thiocyantion or isothiocyanation of alcohols and protected alcohols
Iranpoor, Nasser,Firouzabadi, Habib,Gholinejad, Mohammad
experimental part, p. 2010 - 2019 (2010/03/24)
4-Aminophenyl diphenylphosphinite (APDPP) as a heterogeneous phosphinite reagent is used for the efficient conversion of alcohols, trimethylsilyl- and tetrahydropyranyl ethers, α-hydroxy phosphonates, and - trimethylsilyloxyphosphonates to their corresponding thiocyanates or isothiocyanates in the presence of Br2 and NH4SCN.
In situ-generated N-thiocyanatosuccinimide (NTS) as a highly efficient reagent for the one-pot thiocyanation or isothiocyanation of alcohols
Mokhtari, Babak,Azadi, Roya,Rahmani-Nezhad, Samira
experimental part, p. 6588 - 6589 (2011/02/21)
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.
Substitution Reactions toward 2-Nitrobenzyl Pseudohalides. The Crystal Structure of 2-Nitrobenzyl Tellurocyanate
Grung, Knut Eric,Roemming, Christian,Songstad, Jon
, p. 518 - 526 (2007/10/02)
The reactions between 2-nitrobenzyl pseudohalides, 2-NO2-PhCH2XCN, and pseudohalide ions, NCX- (X = S, Se or Te) have been studied kinetically in acetonitrile at 25.0 deg C.The reactions proceed through nucleophilic attack at the methylene carbon atom, forming exclusively the exchange products.The average nucleophilicity order, NCTe- >> NCSe- > NCS-, and the average leaving group order, NCTe- >/= NCSe- >/= NCS-, lead to a carbon basicity order NCTe- > NCSe- >/= NCS-, which is confirmed with equilibrium studies.A crystal structure determination of 2-nitrobenzyl tellurocyanate at ca. 135 deg C has revealed that the TeCN group is syn-clinal (gauche) to the C(CH2)-C(Ar) bond with a torsion angle of -48.5(5) deg.The TeCC plane forms an angle of 103.4(5) deg with the phenyl ring plane.In this conformation the steric influence of the 2-NO2 group in substitution reactions at the methylene carbon atom will be negligible except for bulky nucleophiles.The tellurium atom forms two fairly strong intermolecular bonds to nitrogen atoms from neighbouring tellurocyanate groups, viz. 2.889(6) Angstroem trans to the cyano group and 3.382(6) Angstroem trans to the methylene group.In the crystalline state the compound may be considered both as a tellurium(II) complex and as an organic pseudohalide.No intermolecular tellurium-oxygen contacts could be observed.
