Search results for "ALK"

Lithium enediolates and dienediolates of carboxylic acids in synthesis: Alkylation with secondary halides

1998

Abstract High yields in the alkylation of dianions of α,β-unsaturated carboxylic acids with secondary halides can be obtained despite elimination reactions occurring. α-Regioselectivity for the alkylation of but-2-enoic acids ( 1–4 ) is seldom obtained. Although double bond stereoselectivity is higher than 99% for γ-alkylated products, stereoselectivity is rather poor for most of the α-alkylated products.

ChemInform Abstract: Synthetic Approaches to Antiinflammatory Macrolactones of the Oxacyclododecindione Type.

2015

A variety of attempts to synthesize oxacyclododecindione macrolactones through carbonylative ring-closure, intramolecular alkyne hydroacyalation, and Ru-catalyzed double bond isomerization fails.

Merging shuttle reactions and paired electrolysis for reversible vicinal dihalogenations

2021

Vicinal dibromides and dichlorides are important commodity chemicals and indispensable synthetic intermediates in modern chemistry that are traditionally synthesized using hazardous elemental chlorine and bromine. Meanwhile, the environmental persistence of halogenated pollutants necessitates improved approaches to accelerate their remediation. Here, we introduce an electrochemically assisted shuttle (e-shuttle) paradigm for the facile and scalable interconversion of alkenes and vicinal dihalides, a class of reactions that can be used both to synthesize useful dihalogenated molecules from simple alkenes and to recycle waste material through retro-dihalogenation. The reaction is demonstrated…

Positive and negative electrospray ionization-collision-induced dissociation of sulfur- containing zwitterionic liquids.

2011

The mass spectrometric properties of several (1,2-dimethyl-1 H-imidazol-3-ium-3-yl)-alkane-1-sulfonates (alkane=ethyl, propyl and butyl) are investigated in this study. These substances, named zwitterionic liquids (ZILs), were synthesized using classical transformations and analyzed in positive and negative electrospray ionization mode using collision-induced dissociation (0–50 eV). We have also performed regioselective deuterium labeling of the alkyl chain of 3-(1,2-dimethyl-1 H-imidazol-3-ium-3-yl)-propane-1-sulfonates. Thus, the mass spectra of isotopically-labeled compounds were used for the confirmation of fragmentation pathways of ZILs. Briefly, the data obtained in this study show t…

Encapsulation of secondary and tertiary ammonium salts by resorcinarenes and pyrogallarenes: the effect of size and charge concentration

2015

The binding of different categories of alkyl ammonium (secondary and tertiary mono- and di-ammonium) salts with resorcinarenes and a pyrogallarene through weak interactions was analysed in all phases. 1H NMR spectroscopy and electrospray ionisation mass spectrometry were utilized in analysing the complexes in solution and in the gas phase, respectively. The 1H NMR titration studies in methanol-d4 reveal that the association constants for the 1:1 complexes vary according to the electronic properties of the hosts as well as the size, geometric orientation and charge concentration of the guest cations with binding constants of up to 950 M−1 in some cases. Mass spectrometry reveals 1:1 monomeri…

ChemInform Abstract: Lithium Enediolates and Dienediolates of Carboxylic Acids in Synthesis: Alkylation with Secondary Halides.

2010

Abstract High yields in the alkylation of dianions of α,β-unsaturated carboxylic acids with secondary halides can be obtained despite elimination reactions occurring. α-Regioselectivity for the alkylation of but-2-enoic acids ( 1–4 ) is seldom obtained. Although double bond stereoselectivity is higher than 99% for γ-alkylated products, stereoselectivity is rather poor for most of the α-alkylated products.

ChemInform Abstract: Enzymatic Formation of Raucaffricine, the Major Indole Alkaloid of Rauwolfia serpentina Cell-Suspension Cultures.

2010

Complexation of C-methyl pyrogallarene with small quaternary and tertiary alkyl ammonium cations

2007

Complexation properties of pyrogallarene 1 towards small quaternary and tertiary alkyl ammonium cations were studied in gas phase, solution and in solid state. In gas phase both dimeric capsules and monomeric 1 : 1 complexes of all cations 2a+–d+ are detected but only in the case of 2a+ is the abundance of the capsule form higher than the monomeric 1 : 1 complex. A similar trend is observed in NMR experiments, which reveal a favourable dimeric complex for 2a+ and a weaker dimeric complex for 2b+ but only monomeric complexes for 2c+ and 2d+. Also in solid state, 2a+ and 2b+ form capsules when crystallized from MeOH while 2c+ and 2d+ form dimeric 1 : 1 complexes. As a reference, hetero-confor…

Organocatalytic synthesis of new telechelic polycarbonates and study of their chemical reactivity

2015

Abstract A two-step versatile process for telechelic polycarbonates synthesis is described. 1-n-butyl-3-methylimidazolium-2-carboxylate (BMIM-2-CO2) was used as thermolabile precursor of N-heterocyclic carbene (NHC) organocatalyst. In a first step, synthesized branched fatty diols or commercially available linear diols were reacted with an excess of dimethylcarbonate (DMC) to afford oligocarbonates with methylcarbonate end-groups. Then, the methylcarbonate groups were reacted with hydroxyl groups of 9-decen-1-ol, 4-hexyn-1-ol and 4-hydroxybenzene ethanol leading to telechelic oligomers with alkene, alkyne and phenol functionalities. Reactivity of these end-groups towards polymerization was …

Efficiency Boosting of Surfactants with Poly(ethylene oxide)-Poly(alkyl glycidyl ether)s: A New Class of Amphiphilic Polymers

2020

Twenty years ago, it was found that adding small amounts of amphiphilic block copolymers like poly(ethylene propylene)-co-poly(ethylene oxide) (PEP-b-PEO) to microemulsion systems strongly increases the efficiency of medium-chain surfactants to solubilize water and oil. Although being predestined to serve as a milestone in microemulsion research, the effect has only scarcely found its way into applications. In this work, we propose new types of efficiency boosters, namely, poly(ethylene oxide)-poly(alkyl glycidyl ether carbonate)s (PEO-b-PAlkGE) and their "carbonated" poly(ethylene oxide)-poly(carbonate alkyl glycidyl ether) analogs. Their synthesis via anionic ring-opening polymerization (…