104-43-8Relevant articles and documents
Controlling the formation of heliconical smectic phases by molecular design of achiral bent-core molecules
Alaasar, Mohamed,Cai, Xiaoqian,Eremin, Alexey,Kurachkina, Marharyta,Lehmann, Anne,Liu, Feng,Nagaraj, Mamatha,Poppe, Marco,Poppe, Silvio,Tamba, Maria-Gabriela,Tschierske, Carsten,Vij, Jagdish K.
supporting information, p. 3316 - 3336 (2020/03/23)
Fluids with spontaneous helical structures formed by achiral low molecular mass molecules is a newly emerging field with great application potential. Here, we explore the chemical mechanisms of the helix formation by systematically modifying the structure of a bent 4-cyanoresorcinol unit functionalized with two different phenyl benzoate based aromatic rods and terminated with two alkyl chains of variable length. The majority of these achiral compounds self-assemble, forming a short-pitch heliconical liquid crystalline phase in broad temperature ranges. In some cases, it occurs without any competing low-temperature phase. We demonstrate that the mirror symmetry broken mesophase occurs at the paraelectric-(anti)ferroelectric transition if the tilt angle of the molecules in the smectic layers is around 18-20° and if this transition coincides with a change of the tilt correlation between the layers. In the close vicinity of this transition, a field-induced heliconical phase develops as well as a new heliconical phase with polarization-randomized structure. These investigations provide a blueprint for the future design of achiral molecules capable of spontaneous mirror symmetry breaking by the formation of heliconical liquid crystalline phases.
Synthesis of 4 - n-alkyl substituted phenol method
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Paragraph 0021-0024, (2018/04/01)
The invention discloses a synthesis method of 4-n-alkyl substituted phenol. Under the catalysis of zinc chloride, aniline and n-alkyl alcohol with the carbon number being 4-30 react in methylbenzene or xylene to obtain the 4-n-alkyl substituted aniline, and then the 4-n-alkyl substituted aniline reacts with sodium nitrite and acid to obtain the 4-n-alkyl substituted phenol. The synthesis method is easy to implement, an intermediate directly enters the next reaction without being separated or purified, and therefore the reaction efficiency is improved. The final product is high in purity and is good in depth of parallelism when reappearing, and technological conditions are suitable for mass production.
Head group specificity of novel functionalized surfactants: Synthesis, self-assembly and calcium tolerance
Sarkar, Deboleena,Shukla, Ravi Kant,Gadgil, Vijay,Pramanik, Amitava
supporting information, p. 5925 - 5931 (2015/01/16)
The present work describes the synthesis, characterization and application of functionalized surfactants derived through simple organic reaction steps. These surfactants have been particularly tailor made to resist hardness due to calcium ions in water. It is unique of its kind because here the surfactants have an analogous hydrophobic chain but differ structurally in the composition of the head groups in terms of the position of attachment of the chain. The effect of this small variability in the head group on the surfactant property, adsorption, self assembly and calcium tolerance behaviour has been studied in detail. This kind of phenol-keto surfactants has not been reported before. It was also found that one of the surfactants was more tolerant towards Ca2+ion than the other. The individual packing behaviour of the surfactants at the air-water interface has been projected to cause this difference which is very interesting.
Syntheses and properties of graphyne fragments: Trigonally expanded dehydrobenzo[12]annulenes
Tahara, Kazukuni,Yamamoto, Yuki,Gross, Dustin E.,Kozuma, Hiroyoshi,Arikuma, Yoko,Ohta, Koji,Koizumi, Yoshiko,Gao, Yuan,Shimizu, Yo,Seki, Shu,Kamada, Kenji,Moore, Jeffrey S.,Tobe, Yoshito
supporting information, p. 11251 - 11260 (2013/09/02)
We present herein the synthesis and properties of the largest hitherto unknown graphyne fragment, namely trigonally expanded tetrakis(dehydrobenzo[12] annulene)s (tetrakis-DBAs). Intramolecular three-fold alkyne metathesis reactions of hexakis(arylethynyl)DBAs 9 a and 9 b using Fuerstner's Mo catalyst furnished tetrakis-DBAs 8 a and 8 b substituted with tert-butyl or branched alkyl ester groups in moderate and fair yields, respectively, demonstrating that the metathesis reaction of this protocol is a powerful tool for the construction of graphyne fragment backbones. For comparison, hexakis(arylethynyl)DBAs 9 c-g have also been prepared. The one-photon absorption spectrum of tetrakis-DBA 8 a bearing tert-butyl groups revealed a remarkable bathochromic shift of the absorption cut-off (λ cutoff) compared with those of previously reported graphyne fragments due to extended π-conjugation. Moreover, in the two-photon absorption spectrum, 8 a showed a large cross-section for a pure hydrocarbon because of the planar para-phenylene-ethynylene conjugation pathways. Hexakis(arylethynyl)- DBAs 9 c-e and 9 g and tetrakis-DBA 8 b bearing electron-withdrawing groups aggregated in chloroform solutions. Comparison between the free energies of 9 e and 8 b bearing the same substituents revealed the more favorable association of the latter due to stronger π-π interactions between the extended π-cores. Polarized optical microscopy observations, DSC, and XRD measurements showed that 8 b and 9 e with branched alkyl ester groups displayed columnar rectangular mesophases. By the time-resolved microwave conductivity method, the columnar rectangular phase of 8 b was shown to exhibit a moderate charge-carrier mobility of 0.12 cm2 V-1 s-1. These results indicate that large graphyne fragments can serve as good organic semiconductors. Copyright
Synthesis and critical micelle concentration of a series of gemini alkylphenol polyoxyethylene nonionic surfactants
Yang, Fang,Li, Gang,Xu, Nian,Liu, Rong,Zhang, Song-Mei,Wu, Zeng-Jiang
, p. 339 - 345 (2012/06/30)
A series of gemini n-alkylphenol polyoxyethylene surfactants (GAP) were successfully synthesized and their molecular structure were confirmed by NMR and FTIR spectrum. Using the same synthesis route, a Gemini nonylphenol polyoxyethylene surfactant (GNP) was synthesized using an industrial nonylphenol product and paraformaldehyde, and its molecular structure was also characterized by 1H-NMR and FTIR spectra. The optimal reaction conditions were established. The critical micelle concentration (CMC) values of GAP were determined by means of Wilhelmy plate method and steady-state fluorescence probe method. The experimental results show how the lengths of the hydrophilic polyoxyethylene chain and the hydrophobic tail alter the CMC values. The CMC values of the GAP are found to be much lower than those of corresponding conventional single tail nonionic surfactants of the polyethoxylated alkylphenol type, which indicates that the gemini species exhibit a better surface activity. AOCS 2011.
Comparisons of photo-Fries rearrangements of 4-dodecylphenyl phenylacetate and two structurally related esters in hexane and polyethylene cages. How important are anchoring chains?
Luo, Chuping,Passin, Philippe,Weiss, Richard G.
, p. 163 - 170 (2008/02/10)
Photo-Fries rearrangements of 4-dodecylphenyl phenylacetate have been investigated in polyethylene films with 0-71% crystallinity and in hexane over a range of temperatures. The results are compared to those reported previously from phenyl phenylacetate and 1-naphthyl tetradecanoate to assess the influence of a long alkyl chain on the in-cage motions of the intermediate singlet radical pairs. It is demonstrated that the reactivity and selectivity of intimate singlet radical pairs can be tuned by judicious placement of long-chain substituents and selection of a specific polyethylene type as the reaction matrix.
Selectivity in the photodimerization of 6-alkylcoumarins
Yu, Xiuling,Scheller, Dieter,Rademacher, Otto,Wolff, Thomas
, p. 7386 - 7399 (2007/10/03)
Coumarin and 6-alkylcoumarins (alkyl = C1 to C16) were photodimerized in homogeneous solvents differing in polarity and in aqueous micellar solutions. The four possible photodimers, syn head-to-head (hh), anti head-to-head, syn head-to-tail (ht), and anti head-to-tail, were identified through a combination of X-ray analysis and NMR spectroscopy. In 6-methylcoumarin the concentration-corrected dimerization (quantum) yield increases with decreasing concentration of the educt; anti- hh was formed exclusively in nonpolar solvents and upon triplet sensitization and was the main product under all conditions except for ionic micellar systems, which direct to preferred syn-hh dimerization. Long alkyl substituents, however, lead to anti-hh in polar solvents and in micelles, too. Predominating ht dimer formation was observed for nonsubstituted coumarin in polar solvents only. Thus, syn/anti and hh/ht selectivity can be steered by varying the 6-alkyl substituent. Syn- hh photodimers of 6-methylcoumarin can be photochemically split into the monomers; they partly proved thermally unstable against acids, bases, methanol, and on SiO2 surfaces.
Novel fluorescent quater- and quinquifurans: Syntheses and photophysical properties
Kauffman, Joel M.,Moyna, Guillermo
, p. 981 - 988 (2007/10/03)
In the quest for fast fluors for use in waveshifting polystyrene fibers, symmetrical oligofurans were investigated. Furan moieties were coupled by means of the Ullmann Reaction or by palladium-catalyzed unsymmetrical coupling; the latter gave higher yields. While the benzoxazole-terminated quater- and quinquifurans we prepared were both stable and fast, exhibiting a green fluorescence and decay times of about 2.4 nsec, they were inferior to other types of fluors in solubility and emission intensity when incorporated into polystyrene.
Convenient cleavage of water-insoluble allylic substrates in the presence of per(2,6-di-O-methyl)-β-cyclodextrin
Widehem, Rodrigue,Lacroix, Thibaut,Bricout, Herve,Monflier, Eric
, p. 722 - 724 (2007/10/03)
The removal of allylic protecting groups promoted by a water soluble palladium complex of the trisulfonated triphenylphosphine is achieved in very high yields (95-100%) on a wide range of water-insoluble substrates in a genuine two-phase system by using the per(2,6-di-O-methyl)-β-cyclodextrin as inverse phase transfer catalyst. The catalytic activities were up to 1000 times higher than those observed without cyclodextrin.
Tilt Angle Variation as a Function of Chain Length and Temperature in the Smectic C Phases of p,Alkoxyphenyl-p,Alkoxybenzoates
Heinrich, B.,Guillon, D.
, p. 21 - 44 (2007/10/02)
The variation of the tilt angle with temperature in the smectic C phase has generally been shown to be non-existent or very slow for compounds or mixtures with the nematic-smectic C transition, while in the case of systems with the smectic A-smectic C transition, a relation between the steepness of this variation, near the transition, and the width of the smectic A domain has been observed.In this work, the variation of tilt angle in the smectic C phase is described for p-alkoxyphenyl-p-alkoxybenzoate homologous series, for which the evolution of polymorphism can be controlled systematically, by varying stepwise the length of the aliphatic chains, and for which large domains can be obtained for each type of phase sequence, nematic-, smectic A- and isotropic-smectic C.After completing the discussion made previously on the incidence of chain length on polymorphism, we confirm that the variation of tilt angle with temperature is slowest for compounds with intermediate chain lengths corresponding to the largest smectic A temperature range; this variation becomes continuously steeper when the smectic A domain becomes narrow.In addition, we show that the same description can be extended to the other types of phase sequences, by using the hypothesis of a virtual smectic A-smectic C transition above the observed nematic- or isotropic-smectic C transition.In fact, short chain lengths for homologues with a nematic/smectic C transition, or long chain lengths for homologues with an isotropic/smectic C transition, lead to an increase of the tilt angle at the phase transition and to a decrease of the amplitude of its variation with temperature; in our description, this behaviour corresponds to an increase of the temperature range between the real and virtual transitions.As a consequence, the homologues with very short and very long chain lengths show a quasi temperature-independent tilt angle, while the other homologues present a tilt angle variation similar to that observed for compounds exhibiting a smectic C/smectic A transition.This feature indicates that there is no need to distinguish between different types of smectic C phase.
