- Attempts to Synthesize a Thiirane, Selenirane, and Thiirene by Dealkylation of Chalcogeniranium and Thiirenium Salts
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Thiiranium salts [Ad2SR]+X? (5, 8, 9, 11, 12; X?=Tf2N? (Tf=CF3SO2), SbCl6?) and seleniranium salts [Ad2SeR]+X? (14, 16, 17, 23–25; X?=Tf2N?, BF4?, CHB11Cl11?, SbCl6?) are synthesized from strained alkene bis(adamantylidene) (1). The disulfides and the diselenides (Me3SiCH2CH2E)2 (4, 13), (tBuMe2SiCH2CH2E)2 (7, 22), and (NCCH2CH2E)2 (10, 15; E=S, Se) have been used. The thiirenium salts [tBu2C2SR]+X? (34) and [Ad2C2SR]+X? (35, 36) are prepared from the bis-tert-butylacetylene (2) and bis-adamantyl-acetylene (3) with R=Me3SiCH2CH2 and tBuMe2SiCH2CH2. Attempts to cleave off the groups Me3SiCH2CH2, tBuMe2SiCH2CH2, and NCCH2CH2 resulted in thiiranes 27, 30. No selenirane Ad2Se (33) is formed from seleniranium salts, instead cleavage to the alkene (1) and diselenide (13, 15) occurs. The thiirenium salt [Ad2C2SCH2CH2SiMe3]+Tf2N? (35) does not yield the thiirene Ad2C2S (37), the three-membered ring is cleaved, forming the alkyne (3) and disulfide (4). All compounds are characterized by ESI mass spectra, NMR spectra, and by quantum chemical calculations. Crystal structures of the salts 8, 12, 25, 17, 26, 36 and the thiiranes 27, 30 are presented.
- Poleschner, Helmut,Seppelt, Konrad
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p. 649 - 659
(2020/10/23)
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- Green synthesis of thiiranes from epoxides catalyzed by magnetically separable CuFe2O4/Mg(OH)2 nanocomposite in water under benign conditions
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The magnetically separable CuFe2O4/Mg(OH)2 nanocomposite was prepared and characterized by FT-IR, XRD, SEM, EDS, and VSM techniques. The synthesized nanoparticles were used as a new and efficient heterogeneous catalyst for the conversion of various epoxides to the corresponding thiiranes with thiourea in water solvent at room temperature. The reactions were completed within 1–3.7 h to give thiiranes in 70–99% yields. The applied CuFe2O4/Mg(OH)2 nanocomposite was separated easily using an external magnet and reused for several times without any considerable loss of activity.
- Hassanzadeh, Shadi,Eisavi, Ronak,Abbasian, Mojtaba
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p. 240 - 255
(2019/01/30)
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- A green method for solvent-free conversion of epoxides to thiiranes using NH4SCN in the presence of NiFe2O4 and MgFe2O4 magnetic nanocatalysts
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Nickel and magnesium ferrite magnetic nanoparticles were fabricated and applied as efficient and reusable catalysts in the solvent-free conversion of various epoxides to the corresponding thiiranes with ammonium thiocyanate under oil bath (60°C) conditions. NiFe2O4 and MgFe2O4 nanoparticles can catalyze the reactions at short times in high to excellent yields. The catalysts can also be recovered easily using an external magnetic field and be reused four times without any significant loss of activity.
- Eisavi, Ronak,Ahmadi, Fatemeh,Ebadzade, Behrooz,Ghadernejad, Seiran
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p. 614 - 624
(2017/10/03)
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- A green protocol for rapid and efficient conversion of epoxides to thiiranes using alumina immobilized thiourea at solvent-free conditions
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Solvent-free conversion of various epoxides to the corresponding thiiranes was carried out successfully with alumina-immobilized thiourea at room temperature. The reactions were completed within 2-9 min to give thiiranes with 83-98% yields. The utilized alumina can be reused for several times without losing its activity.
- Eisavi, Ronak,Zeynizadeh, Behzad
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- Magnetically separable nano CuFe2O4: an ef?cient and reusable heterogeneous catalyst for the green synthesis of thiiranes from epoxides with thiourea
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The magnetically separable nano CuFe2O4 was prepared and used as an efficient heterogeneous catalyst for conversion of various epoxides to the corresponding thiiranes with thiourea in refluxing ethanol. The reactions were completed within 34?45 min to give thiiranes in 80?95% yields. The utilized nano CuFe2O4 can be reused for several times without losing its activity.
- Eisavi, Ronak,Ghadernejad, Seiran,Zeynizadeh, Behzad,Mohammad Aminzadeh, Farkhondeh
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p. 537 - 545
(2016/10/03)
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- An efficient and improved method for the conversion of oxiranes into thiiranes using graphite oxide
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An efficient and improved procedure has been developed for the conversion of oxiranes into thiiranes using sodium thiocyanate in the presence of graphite oxide under solvent-free conditions at an ambient temperature in excellent yields and in short reaction times.
- Mirza-Aghayan, Maryam,Molaee Tavana, Mahdieh
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- Odourless strategy for deep eutectic solvent-mediated ring opening of epoxides with in situ generated S -alkylisothiouronium salts
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A general, straightforward and odourless ring-opening reaction allows the preparation of β-hydroxy sulfides from in situ generated S-alkylisothiouronium salts in urea-choline chloride-based deep eutectic solvent (DES). In addition, reaction of epoxides with thiourea in DES yields the corresponding thiiranes. Georg Thieme Verlag Stuttgart New York.
- Azizi, Najmedin,Yadollahy, Zahra,Rahimzadeh-Oskooee, Amin
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p. 1085 - 1088
(2014/05/20)
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- Zeolite molecular sieve 4: A reusable catalyst for fast and efficient conversion of epoxides to thiiranes with thiourea
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Various epoxides are readily converted to their corresponding thiiranes by thiourea/zeolite molecular sieve 4 system in refluxing MeOH. All reactions were carried out within 12-25 min to give thiiranes in 80%-99% yields. The catalyst saves its catalytic activity for several times at this transformation. Stereospecific conversion of (R)-(+)-styrene oxide to (S)-(+)-styrene episulfide was achieved by this combination system. Taylor & Francis Group, LLC.
- Eisavi, Ronak,Zeynizadeh, Behzad,Baradarani, Mohammad Mehdi
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experimental part
p. 1902 - 1909
(2011/10/09)
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- A practical and eco-friendly method for conversion of epoxides to thiiranes with immobilized thiourea on CaCO3
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Solvent-free conversion of various epoxides to the corresponding thiiranes was carried out efficiently with immobilized thiourea on CaCO3. The reactions were completed within 1-12 min under oil bath (60 °C-70 °C) conditions to afford thiiranes in 88%-98% yields. Copyright Taylor & Francis Group, LLC.
- Zeynizadeh, Behzad,Baradarani, Mohammad Mehdi,Eisavi, Ronak
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experimental part
p. 2208 - 2215
(2012/04/04)
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- Solvent-free conversion of epoxides to thiiranes by thiourea/NH4Cl system
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Epoxides were readily converted to the corresponding thiiranes by thiourea/NH4Cl system under solvent-free conditions. The reactions were completed within 15-75 min at 60-70°C. The thiiranes were obtained in 65-96% yields. Copyright Taylor & Francis Group, LLC.
- Zeynizadeh, Behzad,Yeghaneh, Samal
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experimental part
p. 2280 - 2286
(2009/08/07)
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- Synthesis of thiiranes from oxiranes in water using polymeric cosolvents
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Poly(vinylamine) (PVA) and poly(allylamine) (PAA) were prepared and used as polymeric cosolvents. Oxiranes were converted efficiently to the corresponding thiiranes under mild reaction conditions in water with ammonium thiocyanate (NH4SCN) using these polymeric cosolvents. The polymeric cosolvents are reusable.
- Tamami, Bahman,Kolahdoozan, Majid
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p. 1535 - 1537
(2007/10/03)
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- Synthesis of thiiranes from oxiranes in the presence of β-cyclodextrin in water
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A mild and highly efficient, user-friendly procedure has been developed for the conversion of oxiranes to thiiranes under supramolecular catalysis in the presence of β-cyclodextrin in water at ambient temperature in excellent yields. The use of β-cyclodextrin in this transformation overcomes the use of heavy metal halides as promoters and chlorinated hydrocarbons and other hazardous organic solvents.
- Srilakshmi Krishnaveni,Surendra,Somi Reddy,Nageswar,Rama Rao
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p. 395 - 397
(2007/10/03)
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- A convenient synthesis of phosphorodithioates and novel conversion of epoxides to thiiranes
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Alumina-supported ammonium acetate under microwave irradiation was found to be an efficient reagent for the preparation of phosphorodithioates from phosphorus pentasulfide under solvent-free condition. A simple, efficient, and new method has been developed for the synthesis of thiiranes from epoxides through a one-pot reaction of epoxides with the mixture of phosphorus pentasulfide in the presence of ammonium acetate and acidic alumina under reflux in EtOH or solvent-free conditions under microwave irradiation. These methods are easy, rapid, and good-yielding reactions for the synthesis of phosphorodithioates and thiiranes.
- Kaboudin, Babak,Norouzi, Hamid
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p. 2035 - 2039
(2007/10/03)
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- [Bmim]PF6: A novel and recyclable ionic liquid for conversion of oxiranes to thiiranes in aqueous media
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A variety of epoxides respond rapidly with potassium thiocyanate in [bmim]PF6-H2O (2:1) solvent system at room temperature under mild and convenient conditions to produce the corresponding thiiranes in high to quantitative yields. Enhanced rates, improved yields, and recyclability of ionic liquids are the remarkable features observed in ionic liquids (ILs). The use of ionic liquids for this transformation avoids the use of heavy metal halides as promoters and chlorinated hydrocarbons as solvents. The ionic liquid was recycled in five to six subsequent runs with gradual decrease in activity.
- Yadav,Reddy,Srinivas, Ch.,Rajasekhar, Reddy K.
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p. 2525 - 2527
(2007/10/03)
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- LiBF4: A mild and efficient catalyst for conversion of oxiranes to thiiranes with thiourea
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Oxiranes are efficiently converted to the corresponding thiiranes by thiourea in the presence of catalytic amounts of LiBF4 with excellent yields under mild and non-aqueous conditions.
- Kazemi,Kiasat,Ebrahimi
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p. 595 - 600
(2007/10/03)
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- Efficient conversion of oxiranes to thiiranes with ammonium thiocyanate catalysed with LiBF4
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Oxiranes are efficiently converted into the corresponding thiiranes by ammonium thiocyanate in the presence of catalytic amounts of LiBF4 in excellent yields under mild and non-aqueous conditions.
- Kazemi,Kiasat,Ebrahim
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p. 176 - 177
(2007/10/03)
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- Synthesis of thiiranes through direct sulfur transfer to cycloalkenes in the thermolysis of a thiophene endoperoxide
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Thiophene endoperoxide 2, which was prepared by photo-oxygenation of thiophene 1, transfers a sulfur atom to form thiiranes when thermolysed in the presence of cycloalkenes, an unexpectedly efficient process which can be catalysed by the cobalt-tetraphenylporphine complex.
- Adam, Waldemar,Weinkoetz, Stephan
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p. 177 - 178
(2007/10/03)
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- Cerium(IV) catalysis: Efficient conversion of epoxides to thiiranes
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Cerium(IV) as ceric ammonium nitrate (CAN), catalyzes the conversion of different epoxides to their corresponding thiiranes in excellent yields. The reaction occurs efficiently in the presence of ammonium thiocyanate in tert-butanol at room temperature.
- Iranpoor,Kazemi
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p. 821 - 822
(2007/10/03)
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- A Convenient Synthesis of Thiirans by the Use of Dimethylthioformamide
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Dimethylthioformamide (DMTF) reacts with oxirans in the presence of a catalytic amount of trifluoroacetic acid under mild condition to form the corresponding thiirans in good yield.
- Takido, Toshio,Kobayashi, Yoshio,Itabashi, Kunio
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p. 779 - 780
(2007/10/02)
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