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Emergent Anti-Ferroelectric Ordering and the Coupling of Liquid Crystalline and Polar Order
Jordan Hobbs ; Calum J. Gibb ; Richard. J. Mandle arXiv,2404,12271. DOI: 10.48550/arXiv.2404.12271
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Abstract: Polar liquid crystals possess three dimensional orientational order coupled with unidirectional electric polarity, yielding fluid ferroelectrics. Such polar phases are generated by rod-like molecules with large electric dipole moments. 2,5-Disubstituted 1,3-dioxane is commonly employed as a polar motif in said systems, and here we show this to suffer from thermal instability as a consequence of equatorial-trans to axial-trans isomerism at elevated temperatures. We utilise isosteric building blocks as potential replacements for the 1,3- dioxane unit, and in doing so we obtain new examples of fluid ferroelectric systems. For binary mixtures of certain composition, we observe the emergence of a new fluid antiferroelectric phase - a finding not observed for either of the parent molecules. Our study also reveals a critical tipping point for the emergence of polar order in otherwise apolar systems. These results hint at the possibility for uncovering new highly ordered polar LC phases and delineate distinct transition mechanisms in orientational and polar ordering.
Purchased from AmBeed: 121219-03-2 ; 2105-94-4 ; 148893-72-5 ; 773134-12-6
CAS No. : | 2105-94-4 | MDL No. : | MFCD00011722 |
Formula : | C6H4BrFO | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | RYVOZMPTISNBDB-UHFFFAOYSA-N |
M.W : | 191.00 | Pubchem ID : | 2724981 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
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67% | With sodium carbonate;palladium on activated charcoal; In solmix; for 6h;Reflux; Inert atmosphere; | Preparation of 4'-ethoxy-2',3,3'-trifluorobiphenyl-4-ol (T-5) The compound (T-3) (88.8 g) obtained in the above procedure, 4-bromo-2-fluorophenol (T-4) (76.4 g), sodium carbonate (50.8 g) and Pd-C (NX type) (0. 21 g) were dissolved in Solmix (400 ml) and the mixture was heated to reflux for 6 hours under an atmosphere of nitrogen. After the completion of the reaction, the reaction mixture was filtered through Celite, and the filtrate was extracted with toluene. The organic layer was washed with an aqueous 2N-sodium hydroxide solution, a saturated aqueous solution of sodium hydrogencarbonate, water and brine, and then dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to leave pale brown solids. Recrystallization (heptane:toluene= 4:1 by volume) gave 4'-ethoxy-2',3,3'-trifluorobiphenyl-4-ol (T-5) as colorless powders (72.0 g) in 67% yield. |
Yield | Reaction Conditions | Operation in experiment |
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95% | With potassium carbonate; In 1,4-dioxane; at 80℃; for 18h;Inert atmosphere; | To a stirred solution of 4-bromo-2-fluorophenol (110 muL, 1.0 mmol) and potassium carbonate (553 mg, 4.0 mmol) in 1,4-dioxane (5.0 mL) at r.t. under N2 was added <strong>[2895-21-8]2-chloro-N-isopropylacetamide</strong> (176 mg, 1.30 mmol) and the reaction heated at 80 ^C for 18 h. The solvents were removed under reduced pressure and the residue partitioned between EtOAc (20 mL) and H2O (20 mL). The layers were separated and the aqueous portion extracted with EtOAc (2 x 15 mL). The combined organics were dried (phase separator) and concentrated. The crude product was purified by flash column chromatography (SiO2, eluting with 30-60% EtOAc in Pet. Ether) giving 2-(4-bromo-2- fluoro-phenoxy)-N-isopropylacetamide (307 mg, 0.95 mmol, 95% yield) as a brown oil. LC-MS (ES+, Method C): 2.80 min, m/z 292.0 [M+H]+. |