598-98-1Relevant articles and documents
A methodical selection process for the development of ketones and esters as bio-based replacements for traditional hydrocarbon solvents
Byrne, Fergal P.,Forier, Bart,Bossaert, Greet,Hoebers, Charly,Farmer, Thomas J.,Hunt, Andrew J.
, p. 4003 - 4011 (2018)
A "top down" approach to the development of sustainable, greener, low-polarity solvents is presented. Methyl butyrate, ethyl isobutyrate, methyl pivalate and pinacolone were identified as potential target solvents from trends in Hansen solubility parameters and known physical properties. Solubility, flammability and physical properties were determined which showed their potential to replace traditional, hazardous, volatile, non-polar solvents such as toluene. Each new candidate then demonstrated their suitability to replace these traditional solvents in solubility tests, despite being esters and ketones, each candidate demonstrated their similarity to traditional volatile non-polar solvents in terms of their solubility properties by their ability to dissolve natural rubber, a particularly low-polarity solute. This was reinforced by their performance in a model Menschutkin reaction and a radical-initiated polymerisation for the production of pressure-sensitive adhesives, where their performance was found to be similar to that of toluene. Importantly, a preliminary toxicity test (Ames test) suggested non-mutagenicity in all candidates. Each of the four candidates can be synthesised via a catalytic route from potentially renewable resources, thus enhancing their green credentials.
Unified Approach to Imidodiphosphate-Type Br?nsted Acids with Tunable Confinement and Acidity
Schwengers, Sebastian A.,De, Chandra Kanta,Grossmann, Oleg,Grimm, Joyce A. A.,Sadlowski, Natascha R.,Gerosa, Gabriela G.,List, Benjamin
supporting information, p. 14835 - 14844 (2021/09/18)
We have designed and realized an efficient and operationally simple single-flask synthesis of imidodiphosphate-based Br?nsted acids. The methodology proceedsviaconsecutive chloride substitutions of hexachlorobisphosphazonium salts, providing rapid access to imidodiphosphates (IDP), iminoimidodiphosphates (iIDP), and imidodiphosphorimidates (IDPi). These privileged acid catalysts feature a broad acidity range (pKafrom ~11 to 95:5 er) sulfoxidation of methyln-propyl sulfide. Furthermore, the methodology delivers a novel, rationally designed super acidic catalyst motif, imidodiphosphorbis(iminosulfonylimino)imidate (IDPii), the extreme reactivity of which exceeds commonly employed super-Br?nsted acids, such as trifluoromethanesulfonic acid. The unique reactivity of one such IDPii catalyst has been demonstrated in the first α-methylation of a silyl ketene acetal with methanol as the electrophilic alkylating reagent.
Catalytic conversion of ketones to esters: Via C(O)-C bond cleavage under transition-metal free conditions
Subaramanian, Murugan,Ramar, Palmurukan M.,Rana, Jagannath,Gupta, Virendra Kumar,Balaraman, Ekambaram
supporting information, p. 8143 - 8146 (2020/09/09)
The catalytic conversion of ketones to esters via C(O)-C bond cleavage under transition-metal free conditions is reported. This catalytic process proceeds under solvent-free conditions and offers an easy operational procedure, broad substrate scope with excellent selectivity, and reaction scalability. This journal is
Nickel-catalysed direct alkylation of thiophenes via double C(sp3)-H/C(sp2)-H bond cleavage: The importance of KH2PO4
Wang, Xie,Xie, Peipei,Qiu, Renhua,Zhu, Longzhi,Liu, Ting,Li, You,Iwasaki, Takanori,Au, Chak-Tong,Xu, Xinhua,Xia, Yuanzhi,Yin, Shuang-Feng,Kambe, Nobuaki
supporting information, p. 8316 - 8319 (2017/07/26)
A Ni-catalyzed oxidative C-H/C-H cross-dehydrogenative coupling (CDC) reaction was developed for constructing various highly functionalized alkyl (aryl)-substituted thiophenes. This method employs thiophenes and aliphatic (aromatic) amides that contain an 8-aminoquinoline as a removable directing group in the presence of a silver oxidant. The approach enables the facile one-step synthesis of substituted thiophenes with high functional group compatibility via double C-H bond cleavage without affecting C-Br and C-I bonds. DFT calculations verify the importance of KH2PO4 as an additive for promoting C-H bond cleavage and support the involvement of a Ni(iii) species in the reaction.
Acid-catalyzed oxidation of levulinate derivatives to succinates under mild conditions
Wang, Yuran,Vogelgsang, Ferdinand,Román-Leshkov, Yuriy
, p. 916 - 920 (2015/03/18)
Levulinate derivatives are an attractive platform for the production of renewable chemicals. Here we report on the oxidation of methyl levulinate into dimethyl succinate with peroxides under mild conditions using Br?nsted and Lewis acid catalysts. Selectivities to succinate and acetate derivatives of approximately 60 and 40 %, respectively, were obtained with strong Br?nsted acids in methanol. Although the molecular structure (i.e., carbon-chain length and branching around the C=O group) and the oxidant type affect the product distribution, solvent choice has the strongest impact on changing the location of oxygen insertion into the carbon backbone. Specifically, switching the solvent from methanol to heptane resulted in a decrease in the succinate/acetate ratio from 1.6 to 0.3. In contrast to Br?nsted acids, we demonstrate that the nature of the metal cation is responsible for changing the reaction selectivity of water-tolerant Lewis acidic triflate salts.
Methyl salicylate as a selective methylation agent for the esterification of carboxylic acids
Chen, Si,Jia, Lei,Li, Xiaonan,Luo, Meiming
, p. 263 - 268 (2014/03/21)
Methyl salicylate is a selective and inexpensive methylating agent for the esterification of carboxylic acids with a wide range of functional group tolerance. The intramolecular hydrogen bonds between the carboxylate and hydroxyl groups in methyl salicylate are essential for the transformation. Allyl, benzyl, methallyl, and propargyl salicylates can also be used as alkylating agents for the preparation of the corresponding alkyl carboxylates.
Design and synthesis of sulfonated carbons with amphiphilic properties
Jia, Rong,Ren, Jiawen,Liu, Xiaohui,Lu, Guanzhong,Wang, Yanqin
, p. 11195 - 11201 (2014/07/21)
A new type of sulfonated carbon material with amphiphilic properties was synthesized by the hydrothermal carbonization of a mixture of furfural-sodium dodecylbenzene sulfonate at 180 °C in an autoclave. The addition of SDBS is necessary for the production of materials with long carbon chains and is possibly used to improve the solubilization of long carbon-chain and steric compounds such as pivalic acid. The resulting material was characterized by N2 adsorption, XPS, 13C NMR, XRD and FTIR. The synthesized material was proven to be a highly efficient solid-acid catalyst in reactions such as the esterification of pivalic acid with alcohols, and catalytic performance much better than that of conventional solid acid catalysts, e.g. Amberlyst-15 and Nafion resin, was observed.
Conversion of levulinate into succinate through catalytic oxidative carbon-carbon bond cleavage with dioxygen
Liu, Junxia,Du, Zhongtian,Lu, Tianliang,Xu, Jie
, p. 2255 - 2258 (2014/01/06)
Grand Cleft Oxo: Levulinate, available from biomass, is oxidized into succinate through manganese(III)-catalyzed selective cleavage of C-C bonds with molecular oxygen. In addition to levulinate, a wide range of aliphatic methyl ketones also undergo oxidative C-C bond cleavage at the carbonyl group. This procedure offers a route to valuable dicarboxylic acids from biomass resources by nonfermentive approaches. Copyright
SUBSTITUTED HETEROAROMATIC PYRAZOLE-CONTAINING CARBOXAMIDE AND UREA DERIVATIVES AS VANILLOID RECEPTOR LIGANDS
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Page/Page column 104, (2013/03/26)
The invention relates to substituted heteroaromatic pyrazole-containing carboxamide and urea derivatives as vanilloid receptor ligands, to pharmaceutical compositions containing these compounds and also to these compounds for use in the treatment and/or prophylaxis of pain and further diseases and/or disorders.
Substituted Heteroaromatic Pyrazole-Containing Carboxamide and Urea Compounds as Vanilloid Receptor Ligands
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Paragraph 0666, (2013/03/26)
Substituted heteroaromatic pyrazole-containing carboxamide and urea compounds as vanilloid receptor ligands, pharmaceutical compositions containing these compounds and also to a method of using these compounds for treating and/or inhibiting pain and further diseases and/or disorders.