- Non-phase-transition luminescence mechanochromism of a copper(I) coordination polymer
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A copper(I) coordination polymer, [Cu2I2L2]n (CP 1), shows luminescence mechanochromism with a color change from greenish-blue to yellow upon the application of pressure. Powder X-ray diffraction and Raman studies reveal that the changes in the bond lengths in crystalline CP 1 are the main cause of luminescence mechanochromism. The luminescence mechanochromic process of CP 1 preserves its crystallinity with a small lattice distortion, despite very high pressure, and it is a non-phase-transition process. After the addition of several drops of acetonitrile to the ground and compressed samples, the original greenish-blue emissive and crystalline states are restored. Therefore, the luminescence color conversion processes are fully reversible.
- Kwon, Eunjin,Kim, Jineun,Lee, Kang Yeol,Kim, Tae Ho
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Read Online
- Method for preparing thionocarbamates and co-producing 2-mercaptoethanol or O-alkylthioethyl xanthogenate
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The invention belongs to field of mineral flotation collecting agent materials and in particular discloses a method for preparing thionocarbamates. The method comprises the following steps: carrying out esterification reaction on xanthogenate and 2-halogenated ethanol to obtain O-alkyl-S-hydroxyethyl xanthogenate; carrying out ammonolysis reaction on the O-alkyl-S-hydroxyethyl xanthogenate and fatty amine to obtain a mixture of the thionocarbamates and 2-mercaptoethanol; after carrying out alkali washing on the mixture of the thionocarbamates and the 2-mercaptoethanol, carrying out oil-water separation, wherein an oil phase is the thionocarbamates and a water phase is 2-hydroxyethanethiol salt; carrying out acid washing on the 2-hydroxyethanethiol salt to obtain 2-mercaptoethanol. The invention further provides O-alkylthioethyl xanthogenate which is prepared by enabling the 2-hydroxyethanethiol salt and alkyl halide to react to obtain 2-alkylthioethyl ethanol and enabling the 2-alkylthioethyl ethanol to react with carbon disulfide and alkali. According to the method provided by the invention, the yield of the prepared thionocarbamates, 2-mercaptoethanol and O-alkylthioethyl xanthogenate is high and the purity is high; a product is easy to separate and purity and co-production is realized; the cost is saved and the reaction efficiency is also improved; the method is green and environmentally friendly.
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Paragraph 0101; 0102
(2018/10/11)
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- Silica-promoted facile synthesis of thioesters and thioethers: A highly efficient, reusable and environmentally safe solid support
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An efficient, mild and rapid procedure for the acylation and alkylation of aromatic and aliphatic thiols mediated on a silica gel surface at room temperature is described. The protocol allows the protection of thiols under neutral heterogeneous conditions without requiring any bases or Lewis acids, and the silica gel used as the promoter can be recycled for several runs without any loss of activity.
- Basu, Basudeb,Paul, Susmita,Nanda, Ashis K.
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experimental part
p. 767 - 771
(2010/09/05)
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- Synthesis of sulfides under solvent- and catalyst-free conditions
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A simple, highly efficient, and green protocol has been developed for preparation of sulfides from alkyl or aryl thiols and benzyl-, allyl-, t-butyl, and adamantyl halides under solvent- and catalyst-free conditions.
- Movassagh, Barahman,Soleiman-Beigi, Mohammad
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experimental part
p. 409 - 411
(2010/05/01)
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- The epoxy-Ramberg-Baecklund reaction (ERBR): A sulfone-based method for the synthesis of allylic alcohols
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The epoxy-Ramberg-Baecklund reaction (ERBR) is outlined, in which α,β-epoxy sulfones are converted into a range of mono-, di- and tri-substituted allylic alcohols, on treatment with base. Modification of this method enabled the preparation of enantio-enriched allylic alcohols following the diastereoselective epoxidation of enantio-enriched vinyl sulfones that were accessed efficiently from the chiral pool. The scope, optimisation and limitations of the ERBR as a method for the preparation of allylic alcohols are discussed. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Evans, Paul,Johnson, Paul,Taylor, Richard J. K.
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p. 1740 - 1754
(2007/10/03)
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- A mild and highly convenient chemoselective alkylation of thiols using Cs2CO3-TBAI
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A mild and improved method for the synthesis of thioethers has been developed. In the presence of cesium carbonate, tetrabutylammonium iodide, and DMF, various alkyl and aryl thiols underwent S-alkylation to afford structurally diverse sulfides in high yield. Unprotected mercaptoalcohols and thioamines reacted chemoselectively at the sulfur moiety exclusively. An example of a one-pot, solid-phase synthesis of a thioether is also described.
- Salvatore, Ralph Nicholas,Smith, Robert A.,Nischwitz, Adam K.,Gavin, Terrence
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p. 8931 - 8935
(2007/10/03)
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- A facile and efficient method for the reduction of sulfoxides into sulfides with an Al-NiCl2·6H2O system
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It has been observed that alkyl aryl and dialkyl sulfoxides can be conveniently and rapidly converted to the corresponding sulfides with an Al-NiCl2-6H2O system in high yields. Ketones are not affected under these reaction conditions.
- Raju, B. Rama,Devi, Gitali,Nongpluh, Yoofisaca S.,Saikia, Anil K.
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p. 358 - 360
(2007/10/03)
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- N-H insertion reactions of rhodium carbenoids. Part 3. The development of a modified Bischler indole synthesis and a new protecting-group strategy for indoles
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A modified version of the Bischler indole synthesis has been developed in which the key step is the N-H insertion reaction of rhodium carbene intermediates derived from α-diazo-β-ketoesters with anilines. Thus N-methylanilines 1 react with diazoketoesters 2 in the presence of dirhodium(II) acetate to give (N-arylamino)ketones 3, cyclisation of which using boron trifluoride-ethyl acetate or acidic ion exchange resin gives the indoles 4. In order to extend this method to the synthesis of N-unsubstituted indoles, a new protecting group strategy for indoles was developed. In this, anilines are reacted with α,β-unsaturated-esters or -sulfones to give the conjugate addition products 6 and 9, cyclisation of which gives indoles 8 and 11. The N-(2-ethoxycarbonylethyl)- and -(2-sulfonylethyl)- protecting groups are readily removed from indoles 8 and 11 by treatment with base.
- Bashford, Katherine E.,Cooper, Anthony L.,Kane, Peter D.,Moody, Christopher J.,Muthusamy, Sendogagounder,Swanna, Elizabeth
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p. 1672 - 1687
(2007/10/03)
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- Organosulfur compounds as potential fungicides: The preparation and properties of some substituted benzyl 2-hydroxyethyl oligosulfides
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Compounds of the general type ArCH2SnCH2CH2OH (n = 1 - 4, Ar = Ph, 2-MeC6H4. 4-MeC6H4, 4-ClC6H4, 4-MeOC6H4; n = 1 - 3, Ar = 2-ClC6H4; n = 2, Ar = 4-FC6H4; n = 3 or 4, Ar = 2-furyl) have been prepared as analogues of the trisulfide PhCH2SSSCH2CH2OH (an antimicrobial compound which occurs in the plant Petiveria alliacea) and their potential for application as agricultural fungicides has been examined. In vitro tests against Fusarium culmorum, Fusarium oxysporum and Gauennmyceles graminis showed that all compounds gave > 80% control of these organisms at 1000 ppm. Tests at 100 and 10 ppm showed varying levels of control but the activity did not depend significantly on the number of sulfur atoms present. Selected compounds were also shown to be active in vivo against Erysiphe graminis on barley seedlings, Botrytis fabae and Uromyces viciae-fabae on bean seedlings, Podosphaera leucotricha on apple seedlings, and Phytophthora infestans on potato leaf. The compounds were phytotoxic at concentrations greater than 0.33%.
- Ayodele, Ezekiel T.,Hudson, Harry R.,Ojo, Isaac A. O.,Pianka, Max
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p. 123 - 142
(2007/10/03)
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- Construction of 1,3-oxathiane ring through Pummerer reaction of γδ- unsaturated sulfinyl compounds
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Several γ,δ-unsaturated sulfinyl compounds were prepared and their reactions with p-toluenesulfonic acid were examined. Conformationally rigid γ,δ-unsaturated sulfinyl compounds such as endo-(alkylsulfinyl)norbornene or 1-(alkylsulfinyl)-2-isopropenylbenzene derivatives afforded 1,3-oxathianes through intramolecular Pummerer rearrangement.
- Abe, Hitoshi,Fujii, Hiroyuki,Masunari, Chieko,Itani, Junko,Kashino, Setsuo,Shibaike, Kentaro,Harayama, Takashi
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p. 778 - 785
(2007/10/03)
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- The Epoxy-Ramberg-Backlund reaction: A new route to allylic alcohols
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A new variant of the Ramberg-Backlund reaction is described, the epoxy-Ramberg-Backlund reaction (ERBR), in which α,β-epoxysulfones, on treatment with base, are converted into a range of mono-, di- and tri-substituted allylic alcohols. The scope and limitations of the ERBR are discussed.
- Evans, Paul,Taylor, Richard J. K.
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p. 3055 - 3058
(2007/10/03)
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- Oxidation potential as a measure of the reactivity of anionic nucleophiles. Behaviour of different classes of nucleophiles
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Anodic peak potentials for 42 anionic nucleophiles are reported along with the rate constants for the reactions of the anions with benzyl chloride.By comparing these rate constants with those of the reactions of outer-sphere electron-transfer reagents (radical anions), it has been demonstrated that the reactions of the anions with benzyl chloride are typical single-step SN2 reactions as opposed to a two-step process comprising dissociative single electron transfer (SET) to benzyl chloride followed by radical combination.The data suggest that very electron-rich nucleophilic anions with potentials of -1.5 to -2.2 V (and more negative) with respect to the ferrocenium/ferrocene couple might participate in a SET reaction.The 42 anions studied included representatives of four classes of nucleophiles, viz. sulfur-, carbon-, oxygen- and nitrogen-centred anions.The previously observed correlation of rate constants and anodic peak potential was again found for these anions with the most reactive species having the most negative peak potentials.Correlations by class indicate that the sensitivity of rate constants to changes in peak potential is greatest (and equivalent) for the sulfur-, carbon- and oxygen-anions and for representatives with the same peak potential, the rate constants by class follow the order sulfur > carbon > oxygen.The nitrogen nucleophiles show a significantly lower sensitivity of rate constant to changes in peak potential than do the other three classes.
- Niyazymbetov, Murat E.,Rongfeng, Zhou,Evans, Dennis H.
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p. 1957 - 1962
(2007/10/03)
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- B12 Mimicry in a Weak Ligand Environment: Oxidation and Alkylation of Thiols
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The first examples of alkylation and oxidation of thiols by cobalt in weakly coordinating ligand (MeCN) environments is presented as a mimic to B12-dependent nonenzymatic reaction.
- Chowdhury, Shantanu,Samuel, Purnima M.,Das, Indira,Roy, Sujit
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p. 1993 - 1994
(2007/10/02)
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- NEW ROUTE TO THE PREPARATION OF 1,3,2 OXATHIAPHOSPHOLANES 2-SULFIDE DERIVATIVES
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5-Substituted 2-alkyl (or aryl, heteroaryl,...)thio 1,3,2 oxathiaphospholanes 2-sulfide 5 are readily accessible by reaction of the triethylammonium salt 1 of a diester of the phosphorotetrathioic acid with appropriate epoxide in the presence of BF3*Et2O as catalyst.
- Comel, Alain,Kirsch, Gilbert,Paquer, Daniel
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- Chemoselective alkylation of thiols: A detailed investigation of reactions of thiols with halides
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Arylthiols, aralkylthiols and alkane thiols can be readily alkylated by alkyl/aralkyl halides in presence of K2CO3/DMF to yield unsymmetrical sulphides in nearly quantitative yields. 2-Mercaptoethanol gave the thioether chemoselectively.
- Khurana,Sahoo
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p. 1691 - 1702
(2007/10/02)
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- SYNTHESIS OF 1,3,2-OXATHIAPHOSPHOLANE-2-SULFIDE DERIVATIVES
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5-Substituted 2-alkyl (or aryl, heteroaryl, ...)thio-1,3,2-oxathiaphospholane-2-sulfides 5 are readily accessible by reaction of the triethylammonium salt 1 of a diester of the phosphorotetrathioic acid with appropriate epoxides in the presence of BF3/Et2O as catalyst.Key words: BF3/Et2O; cyclisation reaction; NMR; oxathiaphospholane derivatives; oxiranes; phosphorotetrathioic acid; triethylammonium salts.
- Comel, Alain,Kirsch, Gilbert,Paquer, Daniel
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p. 229 - 234
(2007/10/02)
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- Ar(alk)ylsulfonyl ethyl groups as phosphorus-protecting functions
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Various 2-ethanols were prepared and subsequently converted into the corresponding phosphorodichloridites in almost quantitative yield via a convenient synthetic route.The versatility of the method, which obviates the necessity of a distillation step, is demonstrated by the preparation of other (Ar(alk)yl phosphorodichloridites, including the unstable benzyl phosphorodichloridite.
- Claesen, C. A. A.,Segers, R. P. A. M.,Tesser, G. I.
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p. 119 - 122
(2007/10/02)
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