- Synthesis of novel oil-soluble fluorinated surfactants via Wittig-Horner reaction
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In this paper, the synthesis and characterization of novel oil-soluble fluorinated surfactants were reported. Both Wittig and Wittig-Horner reaction were used for constructing the perfluorinated branch-chain structure, and the latter provided a better method through a three-step synthesis route which was easy worked up and low cost. The surface tension of novel products in toluene, n-hexane and nitromethane with concentrations of 0.1 mol/L, 0.05 mol/L, 0.025 mol/L, 0.0125 mol/L, 0.00625 mol/L and 0 mol/L were examined. The surface tension research of these surfactants showed that they can reduce the surface tension of organic reagents dramatically. For example, compound 1e can reduce the surface tension of nitromethane from 36.6 mN/m to 24.2 mN/m in the concentration of 0.1 mol/L, and the surface tension of toluene was reduced from 28.0 mN/m to 22.7 mN/m when the concentration of compound 1a was 0.1 mol/L.
- Zhang, Ding,Sha, Min,Xing, Ping,Pan, Renming,Lin, Xiangyang,Jiang, Biao
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Read Online
- Enhanced cellular uptake of amphiphilic gold nanoparticles with ester functionality
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Gold nanoparticles (AuNPs) coated with ester-headed or ether-headed PEG ligands were synthesized. Ester-headed AuNPs, but not ether-headed, were transferred from the organic phase (CH2Cl2) to the alkali aqueous phase, indicating that the hydrolysis of the ester moiety triggered the phase transfer of the AuNPs. We found that AuNPs with ester-headed ligands (ester-AuNPs) were internalized into HeLa cells at a greater level than were ether-headed AuNPs.
- Kobayashi, Kenya,Niikura, Kenichi,Takeuchi, Chie,Sekiguchi, Shota,Ninomiya, Takafumi,Hagiwara, Kyoji,Mitomo, Hideyuki,Ito, Yoshihiro,Osada, Yoshihito,Ijiro, Kuniharu
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Read Online
- Dehydrative Allylation of Alkenyl sp2C-H Bonds
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We designed a cooperative catalytic system by combining commercially available Ca(NTf2)PF6 and Pd(PPh3)4 to address the dehydrative allylation of alkenyl sp2 C-H bonds in an environmentally benign manner. A novel C-OH bond cleavage method was found to be crucial for this practical protocol. A variety of alkenes and allylic alcohols equipped with wide-spectrum functional groups can be successfully incorporated into the desired cross-coupling, affording 1,4-dienes with moderate to excellent yields and high stereo- and regioselectivity.
- Cai, Xinying,Xing, Huicong,Qiu, Ju,Li, Bowen,Xie, Peizhong
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supporting information
p. 4368 - 4373
(2021/05/26)
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- Cross coupling of sulfonyl radicals with silver-based carbenes: A simple approach to β-carbonyl arylsulfones
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A coupling reaction between sulfonyl radicals and silver-based carbenes has been well established. This simple radical-carbene coupling (RCC) process provided an efficient approach to a variety of β-carbonyl arylsulfones from sodium arylsulfinates and diazo compounds, and was characterized by wide substrate scope, easy scale-up, simple manipulation, accessible starting materials, and mild reaction conditions.
- Li, Jingjing,Lian, Pengcheng,Wan, Xiaobing,Wang, Hanghang,Zheng, Yonggao
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supporting information
p. 2163 - 2169
(2020/03/27)
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- A Tunable Route to Prepare α,β-Unsaturated Esters and α,β-Unsaturated-γ-Keto Esters through Copper-Catalyzed Coupling of Alkenyl Boronic Acids with Phosphorus Ylides
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A tunable strategy to prepare α,β-unsaturated esters and α,β-unsaturated-γ-keto esters in good to excellent yields was developed through copper-catalyzed oxidative coupling of phosphorus ylides with alkenyl boronic acids under mild conditions. The reaction without water afforded α,β-unsaturated esters, ketones, and amides while α,β-unsaturated-γ-keto esters, 1,4-α,β-unsaturated diketones and α,β-unsaturated-γ-keto amides were obtained when using 5.0 equiv. of water. H2O18 labeling experiments showed that water played an important role in the formation of α,β-unsaturated-γ-keto esters. A plausible formation mechanism for α,β-unsaturated esters and α,β-unsaturated-γ-keto esters was proposed based on mechanistic studies. Phosphonium salts could also be used directly as coupling partners instead of phosphorus ylides. The reaction exhibited a broad substrate scope, good functional group tolerance, good regioselectivity, and diverse coupling products. (Figure presented.).
- Bi, Hong-Yan,Liu, Feng-Ping,Liang, Cui,Su, Gui-Fa,Mo, Dong-Liang
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supporting information
p. 1510 - 1516
(2018/03/05)
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- Phosphine-Catalyzed Domino β/γ-Additions of Benzofuranones with Allenoates: A Method for Unsymmetrical 3,3-Disubstituted Benzofuranones
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A phosphine-catalyzed domino process of benzofuranones with allenoates has been developed which furnishes highly functionalized unsymmetrical 3,3-disubstituted benzofuranones in synthetically useful yields. The mechanism for the transformation is a tandem β-umpolung/γ-umpolung process.
- Huang, Zhusheng,Yang, Xiuqin,Yang, Fulai,Lu, Tao,Zhou, Qingfa
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supporting information
p. 3524 - 3527
(2017/07/17)
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- Photoinduced Intermolecular [4+2] Cycloaddition Reaction for Construction of Benzobicyclo[2.2.2]octane Skeletons
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A novel and efficient method for the synthesis of highly substituted benzobicyclo[2.2.2]octane skeletons has been explored. Under UV-light irradiation, o-divinylbenzenes underwent a pericyclic reaction to form the cyclic o-quinodimethane intermediates which were subsequently reacted with olefins through [4+2] addition to construct the benzobicyclo[2.2.2]octane skeletons in mild conditions. Gram scale reactions demonstrated the synthetic potential application of this protocol.
- Liu, Qiang,Wang, Junlei,Li, Dazhi,Yang, Chao,Xia, Wujiong
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p. 1389 - 1402
(2017/02/10)
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- Cycloaddition of Fluorenone N-Aryl Nitrones with Methylenecyclopropanes and Sequential 1,3-Rearrangement: An Entry to Synthesis of Spirofluorenylpiperidin-4-ones
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A facile synthesis of various spirofluorenylpiperidin-4-ones has been achieved in good yields from fluorenone N-aryl nitrones and methylenecyclopropanes. This method involved an initial cycloaddition to form a 5-spirocyclopropane-isoxazoline, which underwent a highly selective 1,3-rearrangement to give the desired product. The stereochemistry of the spirofluorenylpiperidin-4-one could be controlled by the cycloaddition and sequential rearrangement strategy. Furthermore, the spirofluorenylpiperidin-4-ones could be not only prepared in one-pot procedure but also converted to useful scaffolds by reduction or oxidation conditions.
- Ma, Xiao-Pan,Zhu, Jie-Feng,Wu, Si-Yi,Chen, Chun-Hua,Zou, Ning,Liang, Cui,Su, Gui-Fa,Mo, Dong-Liang
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p. 502 - 511
(2017/04/26)
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- Novel ibuprofen prodrugs with improved pharmacokinetics and non-ulcerogenic potential
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In the present study, we evaluated the anti-inflammatory activity with pharmacokinetic, ulcerogenic properties of various synthesized prodrugs of ibuprofen in experimental animals. Prodrugs 2, 6, 9, 10, 12, and 14 were found to possess significant anti-inflammatory activity with almost non-ulcerogenic potential than standard drug ibuprofen 1a in both normal and inflammation-induced rats. Metabolic stability of prodrugs 2, 6, 9, 10, 12, and 14 were also studied in rat liver microsomes and oral bioavailability was determined by estimating area under curve (AUC) and plasma concentration of these prodrugs at various time intervals. The experimental findings elicited higher AUC and plasma concentration at 1 and 2 h indicating improved oral bioavailability as compared to parent ibuprofen. These prodrugs are found to have least gastric ulceration with retain anti-inflammatory activity observed in experimental animals. Therefore, present experimental findings demonstrated significant improvement of various pharmacokinetic properties with least ulcerogenic potential of ester prodrugs of ibuprofen an anti-inflammatory agent
- Dhakane, Valmik D.,Chavan, Hemant V.,Thakare, Vishnu N.,Adsul, Laxman K.,Shringare, Sadanand N.,Bandgar, Babasaheb P.
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p. 503 - 517
(2014/03/21)
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- In situ generation technology of β-butoxycarbonyliodonium ylide: A hypervalent analogue of the Darzens reagent
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An ester exchange reaction of β-butoxy-β-acyloxyvinyl- λ3-iodane with lithium bases (ROLi and nBuLi) efficiently generates highly labile monoester iodonium ylide at low temperature. The iodonium ylide generated in situ cleanly undergoes Darzens condensation with aromatic aldehydes to afford trans-epoxy ester selectively. The reactivity of monoester iodonium ylide is investigated. Highly labile mono ester iodonium ylide generated in situ from β-butoxy-β-acyloxyvinyl- λ3-iodane through an ester exchange reaction cleanly undergoes Darzens-type condensation with aromatic aldehydes to afford trans-epoxy ester selectively. Copyright
- Miyamoto, Kazunori,Suzuki, Mai,Suefuji, Takashi,Ochiai, Masahito
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supporting information
p. 3662 - 3666
(2013/07/19)
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- Tandem ionic liquid antimicrobial toxicity and asymmetric catalysis study: Carbonyl-ene reactions with trifluoropyruvate
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The asymmetric carbonyl-ene reaction of trifluoropyruvate with five alkenes catalysed by [Pd{(R)-BINAP}](SbF6)2 were carried out in good yields and enantioselectivities (up to 96% yield and 96% ee) in low antimicrobial toxicity C2-substituted imidazolium ionic liquids (ILs). Toxicity data was included in the selection criteria for reaction optimisation after a preliminary IL screen. The Pd(ii) catalyst immobilised in an IL was recycled and reused up to 7 times without decrease of either yield or ee. One IL prepared, which was determined to be of high antimicrobial toxicity was assigned a low priority for future applications.
- Gore, Rohitkumar G.,Truong, Thi-Kim-Thu,Pour, Milan,Myles, Lauren,Connon, Stephen J.,Gathergood, Nicholas
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p. 2727 - 2739
(2013/10/08)
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- NOVEL MACROCYLES AND METHODS FOR THEIR PRODUCTION
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There are provided compounds of formula (I) or a pharmaceutically acceptable salt thereof: wherein the variables R1-R3 are as described in the description, said compounds being useful as anti-inflammatory agents with reduced systemic effects.
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Page/Page column 47
(2011/05/05)
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- BIODEGRADABLE SOLVENTS FOR THE CHEMICAL INDUSTRY
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This invention relates to ionic liquid (ILs) solvents for chemical synthesis based on an alkyl - imidazolium cation core containing ionic liquids which have enhanced biodegradability and reduced toxicity relative to existing imidazolium bases ILs such as 1-butyl-3-methylimidazolium (bmmim) salts. Many of the described ILs produce a score of over 60% biodegradability over 28 days in a biodegradability test such as the Sturm Test, the Closed Bottle Test (OECD 301D) or the CO2 Headspace Test (ISO 14593). The ILs of the invention comprise an alkyl substituted imidazolium cationic core having a -C=OX- side chain in the 3-position of the imidazole ring, wherein X = O, NH, N or S and an associated counteranion characterized in that the -C=OX side chain comprises at least one ether linkage. The biodegradable and non-toxic IL may be used as green solvents for the chemical, pharmaceutical, biofuel and biomass industries. The ILs of the invention are particularly useful in hydrogenation, pericyclic and metathesis reactions.
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(2009/04/25)
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- Biodegradable, non-bactericidal oxygen-functionalised imidazolium esters: A step towards 'greener' ionic liquids
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A series of imidazolium ionic liquids was prepared and screened against 7 bacterial strains. The incorporation of ether groups into the ester side-chain significantly reduced the toxicity compared with alkyl ester derivatives. Biodegradation data are also presented for 15 of the ionic liquids - including 6 examples which can be classed as readily biodegradable.
- Morrissey, Saibh,Pegot, Bruce,Coleman, Deborah,Garcia, M. Teresa,Ferguson, Damien,Quilty, Brid,Gathergood, Nicholas
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supporting information; experimental part
p. 475 - 483
(2010/04/22)
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- Use of enantio-, chemo- and regioselectivity of acylase I. Resolution of polycarboxylic acid esters
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Acylase I was used to catalyze the enantioselective butanolysis of trimethyl 2-[(carboxymethyl)oxy]succinate (E=30) and N-carboxymethylaspartate (E=9) exclusively at the most sterically hindered of the three ester groups (the position α to the asymmetric centre). Gram-scale resolution allowed the preparation of the less reactive trimethyl (S)-2-[(carboxymethyl)oxy]succinate (96% e.e.), that of the (R)-butyldimethyl regioisomer (78% e.e.) at 55% conversion and finally the preparation of the corresponding trisodium carboxylate by saponification. Acylase I was shown to transform (±)-methyl N-acetylmethionine and (±)-valine to the corresponding (S)-amino acids through ester hydrolysis-N-acetyl transfer sequence with absolute chemo- and enantioselectivity. Butanolysis of methyl N-acetylmethionine stopped in the formation of the butyl ester (E=12), the valine derivative being totally unreactive.
- Liljeblad, Arto,Aksela, Reijo,Kanerva, Liisa T.
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p. 2059 - 2066
(2007/10/03)
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- Phenoxyphenyl phosphinates
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Novel phenoxy-, phenylthio, anilino-, benzyl-, pyridyloxy-, pyridylthio-, pyridylamino-, or pyridylmethyl-phenyl substituted phosphinates and phosphinothioates, synthesis thereof, intermediates therefore, and the use of said novel compounds for the control of weeds.
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