Photo-on-Demand In Situ One-Pot Synthesis of Carbonate Esters from Tetrachloroethylene.

The present study reports a novel one-pot synthesis of carbonate esters with photo-oxidized tetrachloroethylene (TCE). Acyclic and cyclic alkyl carbonate esters could be synthesized through base-promoted condensation reactions of alcohols with the photo-oxidized TCE that was prepared by irradiation with UV-C or visible light under O2 or O2/Cl2 (∼4%) bubbling, respectively. Cyclic carbonate esters could also be synthesized from a solution of TCE and the ethylene glycol derivative by irradiation of UV-C light under O2 bubbling. With respect to the reaction mechanism, the photochemical oxidation of TCE mainly provides the highly toxic and corrosive trichloroacetyl chloride (TCAC), which then reacts in situ with the alcohol to give the corresponding trichloroacetic acid ester (TCAE). The subsequent intermolecular or intramolecular base-catalyzed condensation reaction of TCAE with or without the addition of alcohol leads to elimination of CHCl3 in the corresponding carbonate ester. The present reactions enable the in situ one-pot synthesis of a variety of alkyl carbonate esters under mild conditions without the direct handling of TCAC. This is beneficial in terms of safety, cost, and reduced environmental impact.

Photo-on-Demand In Situ Phosgenation Reactions That Cross Three Phases of a Heterogeneous Solution of Chloroform and Aqueous NaOH.

Here, we report a novel photo-on-demand in situ phosgenation reaction that crosses three phases of a heterogeneous solution of chloroform (CHCl3) and aqueous NaOH containing an aryl alcohol or amine. This reaction system enables the safe, convenient, and inexpensive synthesis of carbonate esters, polycarbonates, and N-substituted ureas from aryl alcohols, aryl diols, and primary/secondary amines, respectively, on a practical scale and with good yield. The photochemical oxidation of CHCl3 to phosgene (COCl2) occurs upon irradiation with UV light from a low-pressure mercury lamp of both the gas and liquid phases of the reaction system under O2 bubbling of the vigorously stirred sample solution. The following reaction mechanisms are suggested: The aryl alcohol reacts in situ with the generated COCl2 at the interfaces of the organic/aqueous phases and aqueous/gas phases, in competition with the decomposition of COCl2 due to hydrolysis. Nucleophilicity and hydrophilicity are enhanced by the formation of aryl alkoxide ion through the reaction with NaOH, whereas the reaction of amine proceeds through neutralization of the generated HCl by the aqueous NaOH.

Photo-on-Demand In Situ Synthesis of N-Substituted Trichloroacetamides with Tetrachloroethylene and Their Conversions to Ureas, Carbamates, and Polyurethanes.

N-substituted trichloroacetamides (NTCAs), which serve as blocked isocyanates, were synthesized in ∼97% yields by in situ photo-on-demand trichloroacetylation of amines with tetrachloroethylene (TCE). The reactions were performed by photo-irradiation of TCE solutions containing an amine under O2 bubbling over 70 °C with a low-pressure mercury lamp. TCE underwent photochemical oxidation to afford trichloroacetyl chloride having high toxicity and corrosivity, which then reacts in situ with the amine to afford NTCA. Compared with conventional NTCA synthesis with hexachloroacetone, the present reaction has the advantage of being widely applicable to a variety of amines, even those with low nucleophilicity such as amides, fluorinated amines, and amine HCl salts. NTCAs could be converted to the corresponding N-substituted ureas and carbamates through base-catalyzed condensation with amines and alcohols, respectively, with the elimination of CHCl3. The reaction may proceed by the initial formation of isocyanate and its subsequent addition reaction with the amine or alcohol. This photochemical reaction also enables the synthesis of fluorinated NTCAs, which accelerate the reactions, and realizes the synthesis of novel fluorinated chemicals including polyurethanes.

Photo-On-Demand Synthesis of α-Amino Acid N-Carboxyanhydrides with Chloroform.

Amino acid N-carboxyanhydrides (NCAs) are conventionally synthesized from α-amino acids and phosgene. The present study reports in situ photo-on-demand phosgenation reactions of amino acids with CHCl3 for synthesizing NCAs. A series of NCAs were obtained on a gram scale upon photo-irradiation of a mixture solution of CHCl3 and CH3CN containing an amino acid at 60-70 °C under O2 bubbling. This method presents a safe and convenient reaction controlled by light without special apparatuses and reagents.

Reactivity and Product Selectivity of Fluoroalkyl Carbonates in Substitution Reactions with Primary Alcohols and Amines.

The present study reports a systematic investigation of the substitution reactions of a series of symmetric and unsymmetric fluoroalkyl carbonates with primary alcohols or amines. The reactivity of the haloalkyl carbonate depends mainly on the electrophilicity and steric crowdedness of the carbonyl group and the leaving ability of the haloalkyl alcohols. Diethyl carbonate as a reference substrate showed no reaction with the alcohol or amine. However, bis(2,2,2-trifluoroethyl) carbonate [(F3-EtO)2CO] having electron-withdrawing trifluoroethyl groups enabled substitution reactions, with relatively higher reactivities to those for diphenyl carbonate [(PhO)2CO]. Furthermore, (F6-iPrO)2CO, bearing two sets of hexafluoroisopropyl groups, showed dramatic acceleration of the reactions, in which the observed reactivities were similar to those for bis(perfluorophenyl) carbonate [(F5-PhO)2CO]. The electrophilicity of the carbonyl group and the leaving ability of the alcohols in the series of haloalkyl carbonates were found to be correlated with the wavenumbers of their carbonyl groups in IR spectra and pKa for the eliminated alcohols, respectively. Since the eliminated fluoroalkyl alcohols exhibit weak affinity with the organic products and have lower boiling points owing to a characteristic property of the fluoroalkyl group, they could be readily removed from the product by simple evaporation below 100 °C with or without reduced pressure.

Direct Syntheses of Diphenylmethanol Derivatives from Substituted Benzenes and CHCl3 through Friedel-Crafts Alkylation and Post-Synthetic Hydrolysis or Alcoholysis Catalyzed by Alumina.

The present study reports an innovative finding that alumina containing water or primary alcohol catalyzes the hydrolysis or alcoholysis, respectively, of the product formed through AlCl3 -mediated Friedel-Crafts alkylation of methyl-substituted benzenes and CHCl3 . The former and later reactions mainly provided hydroxy- and alkoxy-substituted diarylmethanes, respectively, while the reference reactions without alumina provided bisarylchloromethane. This method enables the selective syntheses of diphenylmethanol derivatives with very simple procedures, without expensive reagents and apparatuses. Furthermore, the alumina used in the reaction could be recycled by washing with water and subsequent drying. From the viewpoint of material recycling, this function is very important for the development of sustainable chemical reactions.

Photo-on-Demand Phosgenation Reactions with Chloroform for Selective Syntheses of N-Substituted Ureas and Isocyanates.

Two new reaction processes involving the in situ oxidative photochemical conversion of CHCl3 to COCl2 allowed selective syntheses of N-substituted ureas and isocyanates from amines. (I) A CHCl3 solution containing an amine and an organic base under O2 bubbling provided the urea derivative under exposure to UV light generated from a low-pressure mercury lamp at 20-40 °C. (II) A two-step reaction involving the oxidative photodecomposition of CHCl3 at lower temperatures and subsequent sequential injections of an amine and organic base into the sample solution provided the isocyanate in high yield. The reaction processes of (I) and (II) capitalize on the solution conditions of [COCl2] < [amine] and [COCl2] > [amine], respectively, to result in 1:2 and 1:1 reactions. In general, isocyanates, especially aromatic and haloalkyl ones, readily undergo hydrolysis in the presence of an organic base. However, with the advantage of synthesizing the isocyanates in CHCl3 solvent, direct addition of monoalcohols and diols to the as-prepared sample solution containing the diisocyanate allowed the one-pot syntheses of biscarbamates and polyurethanes, respectively. The reactions developed in this study are simple, safe, and inexpensive methods of synthesizing N-substituted ureas and isocyanates, and derivatives of isocyanates such as carbamates and polyurethanes. The present new methods can replace current synthetic methods using COCl2 in both academia and industry.

Photo-on-Demand Base-Catalyzed Phosgenation Reactions with Chloroform: Synthesis of Arylcarbonate and Halocarbonate Esters.

Carbonate esters are utilized as solvents and reagents for C1 building blocks in organic synthesis. This study reports a novel photo-on-demand in situ synthesis of carbonate esters with CHCl3 solutions containing a mixture of an aromatic or haloalkyl alcohol having relatively high acidity, and an organic base. We found that the acid-base interaction of the alcohol and base in the CHCl3 solution plays a key role in enabling the photochemical reaction. This reaction allows practical syntheses of diphenyl carbonate derivatives, haloalkyl carbonates, and polycarbonates, which are important chemicals and materials in industry.

Photo-on-Demand Synthesis of Vilsmeier Reagents with Chloroform and Their Applications to One-Pot Organic Syntheses.

The Vilsmeier reagent (VR), first reported a century ago, is a versatile reagent in a variety of organic reactions. It is used extensively in formylation reactions. However, the synthesis of VR generally requires highly toxic and corrosive reagents such as POCl3, SOCl2, or COCl2. In this study, we found that VR is readily obtained from a CHCl3 solution containing N,N-dimethylformamide or N,N-dimethylacetamide upon photo-irradiation under O2 bubbling. The corresponding Vilsmeier reagents were obtained in high yields with the generation of gaseous HCl and CO2 as byproducts to allow their isolations as crystalline solid products amenable to analysis by X-ray crystallography. With the advantage of using CHCl3, which bifunctionally serves as a reactant and a solvent, this photo-on-demand VR synthesis is available for one-pot syntheses of aldehydes, acid chlorides, formates, ketones, esters, and amides.

A Chiral Metal-Organic 1D-Coordination Polymer Upon Complexation of Phenylene-Bridged Bipyrrole and Palladium (II) Ion.

Metal-organic 1D-coordination polymers, having unique electronic and optical properties, are expected to be a novel advanced functional material capable of fabricating smart plastics, films, and fibers. In this study, we have synthesized a novel metal-organic 1D-coordination polymer composed of a phenylene-bridged bipyrrole bearing N-alkylimino groups (BPI) and palladium(II) ion. The BPI and Pd(II) form square planar bis(bidentate) complex to form a metal coordinated π-conjugation polymer (Poly-BPI/Pd). It is stable in solutions at room temperature, and allowed measurement of its average molecular weight in SEC (M w = 106,000 and M n = 18,000, M w/M n = 5.88). It also provided a reversible multi redox profile in cyclic voltammetry, most likely originating from strong π-electronic interactions between the BPI components via Pd ion. A variety of substituent groups can be attached to the imino-nitrogens of BPI. A coordination polymer composed of a BPI derivative bearing chiral alkyl chains and Pd(II) showed strong circular dichroism (CD) in the solution due to the unidirectional chiral conformation of the BPI components in the polymer backbone.

Photo-on-Demand Synthesis of Chloroformates with a Chloroform Solution Containing an Alcohol and Its One-Pot Conversion to Carbonates and Carbamates.

Chloroformates are key reagents for synthesizing carbonates and carbamates. The present study reports a novel photo-on-demand in situ synthesis of chloroformates with a CHCl3 solution containing a primary alkyl alcohol. It further allowed the one-pot synthesis of carbonates and carbamates through subsequent addition of alcohols or amines, respectively.

Hydroxychalcone dyes that serve as color indicators for pH and fluoride ions.

A chalcone, which is composed of two aromatic rings bridged by an α,ß-unsaturated carbonyl group, exhibits a variety of biological activities. With an objective to develop a novel chalcone-based functional dye, we have synthesized a chalcone diol CLN1, bearing two OH groups at the 2-positions on both phenyl rings, as well as reference compounds CLN2-6, and found that it serves as color indicators for pH and fluoride ions. CLN1 showed a vivid color change from colorless to yellow (halochromism) in water at pH ≥ 10. Furthermore, it presented a selective color change from colorless to red upon the addition of TBAF in an organic solvent such as CH3CN. CLN1 provided a strong red-shifted absorption band in the visible region under alkaline conditions in water and upon the addition of TBAF in CH3CN. The absorption spectral study together with TD-DFT calculations and X-ray crystallographic analysis revealed that the characteristic π-resonant structures of CLN1 caused by the ionization or OH-F- interactions and the planar conformation due to its intramolecular hydrogen bonding may provide a strong charge transfer (CT) absorption in the visible region.

An Acid-Responsive Single Trichromatic Luminescent Dye That Provides Pure White-Light Emission.

A novel acid-responsive single trichromatic luminescent dye capable of emitting pure white light (WL) is reported. A newly designed p-phenylene-bridged bipyrrole bearing N-alkylimino groups (1 a) specifically provides WL emission upon mixing with trifluoroacetic acid (TFA) in a CH2Cl2 solution. The emission originates from the trichromatic luminescent behavior of 1 a upon protonation of the imino groups. The blue-light-emitting 1 a exhibits dramatic color changes in fluorescence to orange and green upon mono- and diprotonation, respectively, providing a wide emission band in the range of λ=400-800 nm that provide WL when the compound is in a dynamic equilibrium between the three states. The sample also exhibits low self-absorption of the emitted light and a high fluorescence quantum yield upon excitation with UV light.

Formation of Discrete Ladders and a Macroporous Xerogel Film by the Zipperlike Dimerization of Meso-Meso-Linked Zinc(II) Porphyrin Arrays with Di(pyrid-3-yl)acetylene.

Metal porphyrins assemble to form a supramolecular architecture with a characteristic structure and characteristic properties and functions upon complexation with appropriate ligands. However, there are few applications of these assembly processes to the construction of polymeric porphyrin arrays with useful functionalities. In this study, we found that meso-meso-linked Zn(II) porphyrin arrays underwent zipperlike dimerization upon complexation with di(pyrid-3-yl)acetylene (DPA) in chloroform to form discrete double-stranded porphyrin ladders. Similarly, the assembly of poly(zinc(II) porphyrinylene) with DPA gave a thermoresponsive gel, whose three-dimensional network structure was so strong that a macroporous xerogel film was obtained.

Photochromism in sound-induced alignment of a diarylethene supramolecular nanofibre.

A photochromic supramolecular nanofibre, composed of a diarylethene derivative, exhibits hydrodynamic alignment upon exposure to the audible sound. The aligned nanofibre outputs linear dichroism (LD), whose wavelength region can be switched reversibly with UV and visible light.

Control of reaction pathways in the photochemical reaction of a quinone with tetramethylethylene by metal binding.

The present study reports a novel supramolecular photochemical reaction that focuses on the direct electronic interactions between a host reaction substrate and guest metal salts. The reaction pathways in the photochemical reactions of quinone derivatives bearing a methoxy group and a long oligoether sidearm QEn (n = 0 and 3) with tetramethylethylene (TME) are changed upon noncovalent complexations of the host reactant with alkali and alkaline earth metal ions and a transition metal salt. The photochemical reaction of QEn with TME provides a mixture of [2 + 2] cycloadducts 1aEn and 1bEn, hydroquinone H2QEn, and monoallyl ether adducts of hydroquinones 2aEn and 2bEn. The photochemical reaction proceeds by the photoinduced electron transfer mechanism, where photoirradiation brings about formation of a radical ion pair [QEn˙(-), TME˙(+)] as the primary intermediate. We found that the yields and selectivity of these photoproducts are changed upon electronic interactions of QEn˙(-) with the metal salts. The photochemical reaction in the absence of metal salts provides H2QEn as its major product, whereas QE3, having the long sidearm, dominantly produces 2aE3 at the expense of 1aE3, 1bE3, and H2QE3 when it forms a size-favorable host-guest complex with divalent Ca(2+). In contrast, QEn selectively provides oxetanes 1aEn and 1bEn in the presence of Pd(OAc)2, which can form complexes with the quinone through metal-olefin and coordination interactions in the ground and photoexcited states of the quinone.

A physical operation of hydrodynamic orientation of an azobenzene supramolecular assembly with light and sound.

Photoisomerizations of a newly designed azobenzene derivative reversibly change its self-assembly in a solution to form twisted supramolecular nanofibers and amorphous aggregates, respectively. When irradiating the sample solution with audible sound, the former assembly exhibits a LD response due to its hydrodynamic orientation, but the latter one is LD silent, in the sound-induced fluid flows.

Acoustic Alignment of a Supramolecular Nanofiber in Harmony with the Sound of Music.

Audible sound with a low-frequency vibration brings about hydrodynamic alignment of a supramolecular nanofiber in solution. Design of the nanoscale molecules and molecular assemblies, which can sense a wide range of frequencies of the audible sound wave with high sensitivity, develops sound-driven molecular machines and sound-responsive nanomaterials, and is also interesting for investigation of unknown physical interactions between the molecules and audible sound vibrations. In this study, it was found that a supramolecular nanofiber, composed of an anthracene derivative AN, in an n-hexane solution aligned upon exposure to an audible sound wave at frequencies up to 1000 Hz, with quick responses to the sound and silence, and to amplitude and frequency changes of the sound wave. These properties are of great advantage to sense dynamic changes of fluid flows, such as those induced by the sound of music. Music is composed of multiple complex sounds and silence, which characteristically change in the course of its playing time. When classical music was playing, the AN nanofiber aligned itself in harmony with the sound of the music. Time course linear dichroism spectroscopy revealed the dynamic acoustic alignments of the AN nanofiber in the solution upon playing the music. The sound vibrations of music, which generate acoustic streaming flows in liquid media, allowed shear-induced alignments of the nanofiber.

Acoustic Alignment of a Supramolecular Nanofiber in Harmony with the Sound of Music.

Invited for this month's cover is the group of Prof. Akihiko Tsuda from Kobe University and Kobe City Collage of Technology. The cover picture shows the alignment of a supramolecular nanofiber, composed of an anthracene derivative, while the Kobe University Symphony Orchestra was playing classical music. Read the full text of the article at 10.1002/cplu.201300400.