Difluoromethylation of arylidene Meldrum's acid derivatives
Fluorine-containing compounds gained significant attention during the past decade1. About 20% of novel pharmaceuticals and 40% of novel agrochemicals every year contain at least one fluorine atom in the molecule. For a long time the most frequently used was trifluoromethyl group, but nowadays the most promising is the chemistry of partially-fluorinated groups. For example, the difluoromethyl substituent (CHF2) exhibits unique pharmacoforic properties capable of serving as lipophilic hydrogen bond donor thus being bioisosteric to hydroxyl group2. There are several general approaches for the formation of a required fluorinated fragment, one of them is direct nucleophilic fluoroalkylation. This approach is well-developed for trifluoromethylation reactions, such as addition of CF3-anion equivalents to C=O, C=N and electron-deficient C=C bonds or metal-catalyzed substitution in haloarenes3. However the similar difluoromethylation processes are still quite challenging. Herein we present a novel and convenient protocol for the synthesis of β-CF2H functionalized carbonyl compounds and carbinols by nucleophilic difluoromethylation of electron-deficient olefines. The process is based on a 1,4-addition of in situ generated4 phosphorus ylide Ph3P=CF2 2 to the arylidene Meldrum's acid conjugates 1. The resulting phosphobetaines 3 are hydrolized/protodephosphorilated without isolation, giving β-CF2H substituted carboxylic acids 4. The latter may be easily transformed to the corresponding ethers 5 and alcohols 6 without preliminary purification.
First photochromic diarylethenes with cyclohexenone ethene "bridge"
Photochromism is determined as reversible transformation between two chemical species, induced by action of light [1]. Herewith, initial form and photoinduced isomer have different properties, first of all, spectral. The phenomenon is attractive for the design of hi-tech materials for different applications, including optical memory elements and molecular switches. Diarylethenes are the most promising class of organic photochromic compounds due to outstanding thermal stability of both isomers and high photostability [2, 3]. Photochromism of diarylethenes explained by reversible electrocyclic reaction of hexatriene system, provoked by UV light, back reaction is induced by visible light. In this work we have proposed a new class of photochromic diarylethenes with cyclohexenone ethene “bridge” 4. The key stage of the synthesis is “one-pot” reaction of ketoesters 1 and chalkones 2 in ethanol in the presence of sodium ethoxide that includes Michael reaction and subsequent intramolecular condensation of the resulting product. The final decarboxylation of semi-product 3 results in target diarylethenes 4. We have prepared a wide range of photochromic diarylethenes with thiophene, oxazole, imidazole and benzene derivatives as aryl moieties. The spectral characteristics of compounds obtained have also been discussed.
Findings of new oscillations in BR reaction
The Briggs Rauscher reaction, i. e., BR reaction, which is one of the oscillation reactions, produces iodide ion and iodine repeatedly. Continual color changes of the solution from colorless to deep blue, and vice versa, are observed during the reaction due to the so-called “iodine test” reaction. In this work, we studied the effects of the presence of the redox active indicators on the oscillation behavior of the BR reaction. To the reaction mixture of KIO3, H2SO4, H2O2, C3H4O4, MnSO4, and starch, which are used for the general BR reaction as added a redox active reagent (indicator). Then, the changes in color and voltage of the reaction solution were recorded by a photosensor of the LEGO MINDSTORMS and a voltmeter using Pt electrodes. Under general reaction conditions, the oscillation reaction continued for ca. 5 minutes, including 18 times of oscillations. When an indicator, such as BTB, was added instead of starch to the reaction solution, splits of the voltage wave were observed, which should be a kind of new oscillation. Moreover, we found that the addition of K3[Fe(CN)6], which exhibits high redox activity, in the reaction solution instead of starch made the life-time and the numbers of the oscillation in the reaction greater by 3 times (14 min.) in time and more than 4 times (81 times) in the frequency. It’s also a kind of new oscillation. These results suggested that the oxidation-reduction reactions by the addition of ferricyanate ion effectively promotes the redox process of iodine and iodide ion. The experiments we wrote above were conducted without starch. Thus, as a reference, we conducted the same experiments under the presence of starch and got interesting results. We also studied the effects of K4[Fe(CN)6], suggeting that not only redox reaction between ferricyanide and ferrocyanide ion, but also the redox reaction with BR solution should occur in these reactions.