Formation of polyketone particle structure by hexafluoroisopropanol solvent evaporation and effects of plasticizer addition

Few solvents are capable of dissolving polyketones (PKs). 1,1,1,3,3,3‐Hexafluoro‐2‐propanol (hexafluoroisopropanol, HFIP) is a better solvent than trifluoroethanol and m‐cresol. When HFIP was evaporated from a PK/HFIP solution, a porous cast‐film with a microparticle structure was formed because the isotactic PKs adopted a helical conformation, and convection during evaporation of the high polarity and low‐boiling‐point HFIP caused aggregation and rolling of the polymer molecules. The addition of plasticizer suppressed particle formation, improving the surface structure and mechanical properties of the film. In particular, the dielectric properties of the film improved significantly. This will enable PKs, which are rigid insulating materials, to be used as dielectric materials, broadening their range of applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 887–892     

New Straightforward Synthesis of β‐Damascenone and β‐Damascone Derivatives from β‐Ionone via Retro‐α‐ionol

β‐Damascenone and β‐damascone derivatives, important fragrant compounds, were directly obtained from β‐ionone by a new way via retro‐α‐ionol.     

Unified,Efficient, and Scalable Synthesis of Halichondrins: Zirconium/Nickel‐Mediated One‐Pot Ketone Synthesis as the Final Coupling Reaction

Unified, efficient, and scalable syntheses of the halichondrin natural products are reported. A newly developed Zr/Ni‐mediated one‐pot ketone synthesis was used to couple the two halves of the final product at a late stage in the synthesis. With the use of a slight excess of the left halves, the desired ketones were isolated in yields of 80–90 %. The halichondrins were obtained from these ketones in two steps, namely desilylation and [5,5]‐spiroketal formation. The new synthetic route was effective for the total synthesis of all members in the homohalichondrin subgroup. The scalability of this process was demonstrated with halichondrin B; 150 mg of halichondrin B (68 % overall yield) were obtained from 200 mg of the right‐half precursor.     

Enzymatic synthesis of chiral heteroaryl alcohols using plant fragments as the only biocatalyst and reducing agent

Abstract

The enzymatic reduction of prochiral heterocyclic ketones by carrot (Daucus carota) root in water afforded the corresponding S-alcohols in accordance with the Prelog's rule. The reaction was performed under various conditions in order to optimize the procedure of bioreduction regarding reaction time, yield, and optimal mass of carrot. The optimized procedure was used to test the ability of other plants to carry out the reaction. In the latter experiment, it was observed that, with regard to stereospecificity, most vegetables tested were poorer reducing agents compared to D. carota.     

Synthesis of 2,3-dihydroquinazolin-4(1H)-ones from anthranilamide and ketones over Hβ zeolite in aqueous media*

The synthesis of 2,3-dihydroquinazolin-4(1H)-ones by cyclocondensation of anthranilamide with ketones in aqueous media using Hβ zeolite is reported. The scope of the reaction was explored by various ketones such as aromatic, aliphatic and cyclic ketones. Based on the preliminary mechanistic results, a tentative mechanism for the formation of 2,3-dihydroquinazolin-4(1H)-ones using zeolite catalyst (Hβ) is predicted. The reusability study, large-scale experiment and water as solvent showed significant benefits of this catalytic protocol in comparing to earlier methods.     

Reactivity of Various α-Halo Ketones in One-Pot Synthesis of γ-Iminolactones

The highly reactive 1:1 intermediate generated in the reaction of tert-butyl isocyanide and dialkyl acetylenedicarboxylate is trapped by α-halo ketones to produce halogenated iminolactones as the sole product in good yields.     

The Synthesis of 1,3-Bis(Phenylseleno)-2-Propanol

A general and efficient synthetic method of 1,3-bis(phenylseleno)-2-propanol by reducing diphenyl diselenides with sodium borohydride in basic environment and then reacting with epichlorohydrin are described.     

Synthesis of 1-p-Methoxyphenyl and 1-p-Methoxyphenyl-4-methylbicyclo-[2.2.1]heptan-7-one. The Oxidation of 7-Hydroxy-1-p-methoxyphenyl-4-methylbicyclo[2.2.1]heptan-7-carboxylic Acid with Lead Tetraacetate

A simple synthetic route to 1-p-methoxyphenyl and 1-p-methoxyphenyl-4-methylbicyclo [2.2.1]heptan-7-one 6b,a has been developed through benzilic acid rearrangement of the bicyclo[2.2.1]octandiones 2b,a. The oxidation of 7-hydroxy-1-p-methoxyphenyl-4-methylbicyclo[2.2.1]heptan-7-carboxylic acid 3a with lead tetraacetate gives the carbolactone 7a which is also formed by the reaction of the ketone 6a with m-chloroperbenzoic acid.     

New Steroidal Saponins from the Leaves of Yucca elephantipes

Two new spirostanol saponins, namely elephanosides G and H ( 1 and 2 , resp.) were isolated from the leaves of Yucca elephantipes (Agavaceae), together with the two known furostanol saponins 3 and 4 and the six known flavonoid O‐ and C‐glycosides 5 – 10 . The new structures were elucidated as (3β,25S)‐spirost‐5‐en‐3‐yl O‐β‐D ‐glucopyranosyl‐(1→3)‐O‐β‐D ‐glucopyranosyl‐(1→4)‐β‐D ‐galactopyranoside ( 1 ) and (3β,5β,25R)‐3‐[(2‐O‐β‐D ‐glucopyranosyl‐β‐D ‐galactopyranosyl)oxy]spirostan‐12‐one ( 2 ) on the basis of detailed spectroscopic analysis and acidic hydrolysis.     

Rapid Aqueous Borohydride Reduction of Carbonyls Under Sealed-Tube Microwave Conditions

Ketones and aldehydes are conveniently and rapidly reduced to the corresponding alcohols in good yields using sodium borohydride under sealed-tube microwave conditions in either 95% ethanol or water. In purely aqueous systems, highly aliphatic substrates are sluggish, but this can be overcome by introducing sodium dodecyl sulfate (SDS) at the critical micelle concentration. With a 2:1 substrate/borohydride ratio and a reaction temperature of 100 °C, reduction is typically complete within 1 min in 95% ethanol and 5 min in water/SDS. The methodology is well suited for parallel and combinatorial synthetic approaches.