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The thermal polymerization of styrene in the presence of polymer initiators, copoly(arylene phthalides) of the diphenyl oxide series with different ratios of two adjacent (“head-to-head”) and single (“head-to-tail”) phthalide groups, was studied. Depending on the composition of copoly(arylene phthalides), either copolymers enriched in styrene units, or copolymers with prevailing arylphthalide groups are formed. Diphilic macromolecules of the copolymers form micelles in solutions, the size of which is determined by the ratio of styrene and phthalide units.

Electrospun polyimide (PI) ultrafine non-woven fibrous mats (UFMs) with good heat-fusibility via hot press procedure were successfully fabricated. For this purpose, two organo-soluble PI resins were prepared via a two-step chemical imidization procedure from two isomeric oxydiphthalic dianhydrides, including the asymmetrical ODPA (2,3,3′,4′-oxydiphthalic dianhydride, or aODPA) and symmetrical ODPA (4,4′-oxydiphthalic dianhydride, or ODPA) with an aromatic diamine containing phenolphthalein unit in the main chain, 3,3-bis[4-(4-aminophenoxy)phenyl]phthalide (BAPPT), respectively. The derived PI-1 (aODPA-BAPPT) and PI-2 (ODPA-BAPPT) resins showed high numerical average molecular weights (Mn) over 105 g/mol and were easily soluble in polar aprotic solvents, such as N-methyl-2-pyrrolidinone (NMP) and N, N-dimethylacetamide (DMAc). PI-1 and PI-2 UFMs were successfully prepared from the PI solutions in DMAc via the one-step electrospinning procedure. Different rotating speeds of 500–2500 round per minute (rpm) for the cylindrical collector were set to investigate the effects of the fiber morphologies on the properties of the PI UFMs. The derived PI UFMs showed good thermal stability with the glass transition temperatures (Tg) over 280 °C and 5 % weight loss temperatures (T5%) higher than 510 °C in nitrogen. The PI UFMs could be successfully heat-sealed via the hot-press temperature at 320 °C (about 40 °C higher than Tg) for 60s with the pressure of 0.5 MPa.

The roots of Ligusticum porteri J.M. Coult. & Rose, Apiaceae, are used in Mexican traditional medicine for the treatment of gastrointestinal disorders. The dimeric phthalide (Z´)-diligustilide found in their organic extracts is associated with the gastroprotective properties. In this study, the gastroprotective effect of nanoemulsion of the volatile oil from the roots of L. porteri (at doses of 1, 3, 10, and 30 mg/kg) in the indomethacin-induced gastric damage model was tested, and nitric oxide (NO) and hydrogen sulfide (H2S) gastric levels were determinate. The volatile oil obtained by steam distillation (0.63% yield) contained 37 constituents, as assessed by GC-MS analysis, where the significant compounds were 4-phenyl-3-buten-2-ol (20.54%) and (Z)-3-butylidenephthalide (20.54%) that correspond to phthalide monomers. These results demonstrate that nanoemulsion of the volatile oil from L. porteri (at 10 and 30 mg/kg) shows a significant gastroprotective effect (72 and 92% respectively) against indomethacin-induced gastric damage, which is not different from the gastroprotective effect of omeprazole (69%) (p

Mechanistic studies relating to the photochemistry of 3-hydroxy-2-phenyl-4H-chromen-4-one (3HF) and 6-chloro-3-hydroxy-2-phenyl-4H-chromen-4-one (Cl-3HF) have been reinvestigated in selected solvents. The UV-visible spectra of the photoproduct(s) of 3HF and Cl-3HF have been computed in situ via subtracting the spectra of unreacted substrates, with acetonitrile (ACN) and methanol (MeOH) as solvents. These spectra turn out to be different from the spectra of the corresponding isolated photoproducts: 3-hydroxy-3-phenyl-indan-1,2-dione and 6-chloro-3-hydroxy-3-phenyl-indan-1,2-dione (referred to as dione ). Analyses of the photoproduct(s) via GC-MS show the formation of a single detectable product, i.e., the corresponding dione. On the basis of some experimental observations, it is proposed that the primary photoproduct in situ is 2,3-epoxy-2-hydroxy-1-indanone (referred to as epoxide) instead of dione as reported in previous years. Earlier, epoxide has been proposed to be the intermediate in the mechanism for the formation of dione. This is the first report where the formation of epoxide has been directly detected in the selected solvents. On the other hand, both dione and epoxide (2 : 1) are shown to be formed with MeOH as solvent. The second important finding is that epoxide and dione interconvert in the dark, depending upon the environment. With ACN as solvent, pure dione in the dark is kinetically and partially converted to epoxide. With MeOH as solvent, epoxide is instantly and partially converted to dione until both are in equilibrium. However, a solution of dione in MeOH remains stable in the dark. The photoformation of epoxide is quantitative with ACN as solvent and it is sufficiently stable. It has been further observed that epoxide solutions of 3HF and Cl-3HF in ACN are quantitatively converted into 3-phenylisobenzofuran-1(3H)-one and 6-chloro-3-phenylisobenzofuran-1(3H)-one, i.e., the corresponding phthalides, through the loss of CO when kept in the dark for some days. A mechanism has been proposed where epoxide has been shown to give dione and/or phthalide via selective C-O or C-C bond cleavage in the oxiranyl ring, respectively. The selection of this cleavage depends mainly on the solvent system and the substituents in the parent flavones.

We report an efficient, catalyst-free, one-pot synthesis of (E)-N′-benzylidene-2-(hydroxymethyl)benzohydrazide derivatives by the one-pot reaction of phthalide, hydrazine hydrate and aldehyde. Advantages of this synthetic approach include mild reaction conditions and environmentally friendly nature, and the ability to provide a wide range of desired compounds in moderate to excellent yields. Here we introduce a green and efficient one-pot three-component protocol for the synthesis of (E)-N′-benzylidene-2-(hydroxymethyl)benzohydrazide derivatives in ethanol without any catalyst.

A 70% ethanol extract from the root portion of Reynoutria japonica afforded one new and three known juglone derivatives, namely, 2-methoxy-6-acetyl-7-methyljuglone (1), 2-ethoxy-6-acetyl-7-methyljuglone (2), 2-methoxy-7-acetonyljuglone (3), and 3-acetyl-7-methoxy-2-methyljuglone (4) together with two phenolics (5 and 6), an anthraquinone (7), a stilbene (8) and a phthalide (9). Their structures were elucidated on the basis of comprehensive spectroscopic studies including IR, MS, and 1H, 13C, 2D NMR spectra. Compound 3 is a new compound in nature, and compounds 4–6 have been isolated for the first time from R. japonica. The isolates were evaluated for their antibacterial activity against three strains (43504, 51, and 26695) of Helicobacter pylori. The four isolated juglone derivatives (1–4) showed potent growth inhibitory activity. Among them, compounds 1–3 exhibited stronger inhibitory activity than those of the positive controls, juglone and metronidazole, for the three strains and that of another reference, clarithromycin, for the 43504 and 51 strains. Specifically, the new juglone compound 3 displayed the most potent antibacterial activity against all three strains, 43504, 51, and 26695, with MIC values of 0.06, 0.06 and 0.13 μM, respectively, and MIC50 values of 0.14, 0.11 and 0.15 μM, respectively.

Two semi-alicyclic polyimide (PI) films with light colors, good thermal stability, and enhanced flame retardancy were successfully developed from an aromatic diamine containing phenolphthalein unit, 3,3-bis[4-(4-aminophenoxy)phenyl]phthalide (BAPPT) and alicyclic dianhydrides, including 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride (HPMDA) and 3,3',4,4'-bicyclohexanetetracarboxylic acid dianhydride (HBPDA). For this target, two organo-soluble PI resins, including PI-1 (HPMDA-BAPPT) and PI-2 (HBPDA-BAPPT) were first synthesized by a high-temperature polymerization route. The derived preimidized PI resins were soluble in N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAc), and other polar aprotic solvents. Corresponding PI films with pale-yellow appearances at the thickness of 25 μm were prepared by casting the PI solutions on glass substrates, followed by thermally baking at elevated temperatures up to 280 °C in nitrogen. The obtained PI films exhibited the cutoff wavelengths (λcut) lower than 300 nm, the optical transmittances as high as 84.5% at the wavelength of 450 nm, the yellow indices (b*) as low as 3.10, and the haze values as low as 3.71%. Both of the PI films exhibited good thermal stability with the 5% weight loss temperatures (T5%) higher than 480 °C in nitrogen, char yields higher than 40% at 700 °C, and glass transition temperatures (Tg) as high as 318.1 °C. In addition, the semi-alicyclic PI films showed acceptable high-temperature dimensional stability with the linear coefficients of thermal expansion (CTE) values of 52.3 × 10–6/K for PI-1 and 60.4 × 10–6/K for PI-2 in the temperature range of 50–200 °C, respectively. At last, the PI-1 film showed good flame retardancy with the limited oxygen index (LOI) of 32.8%, the flame retardancy class of UL94 VTM-0, and good smoke suppression properties.

Backgrounds The dried rhizome of Ligusticum sinense Oliv.cv. Chaxiong has been used to treat cardiovascular and cerebrovascular diseases, atherosclerosis, anemia and stroke. A high purity extract from chaxiong (VOC, brownish yellow oil) was extracted and separated. Its main components were senkyunolide A (SA, 33.81%), N-butylphthalide (NBP, 1.38%), Neocnidilide (NOL, 16.53%), Z-ligustilide (ZL, 38.36%), and butenyl phthalide (BP, 2.48%), respectively. Little is known about the pharmacokinetics of these phthalides in Chaxiong, and different preparations to improve the physicochemistry and pharmacokinetics of VOC have not been investigated. Methods At different predetermined time points after oral administration or intravenous administration, the concentrations of SA, NBP, NOL, ZL and BP in the rat plasma were determined using LC-MS/MS, and the main PK parameters were investigated. VOC-P188 solid dispersion and VOC-β-CD inclusion compound were prepared by melting solvent method and grinding method, respectively. Moreover, the physicochemical properties, dissolution and pharmacokinetics of VOC-P188 solid dispersion and VOC-β-CD inclusion compound in rats were assessed in comparison to VOC. Results The absorptions of SA, NBP, NOL, ZL and BP in VOC were rapid after oral administration, and the absolute bioavailability was less than 25%. After the two preparations were prepared, dissolution rate was improved at pH 5.8 phosphate buffer solution. Comparing VOC and physical mixture with the solid dispersion and inclusion compound, it was observed differences occurred in the chemical composition, thermal stability, and morphology. Both VOC-P188 solid dispersion and VOC-β-CD inclusion compound had a significantly higher AUC and longer MRT in comparison with VOC. Conclusion SA, NBP, NOL, ZL and BP in VOC from chaxiong possessed poor absolute oral bioavailability. Both VOC-P188 solid dispersion and VOC-β-CD inclusion compound could be prospective means for improving oral bioavailability of SA, NBP, NOL, ZL and BP in VOC.

The present study describes the first successful report on in vitro propagation through direct organogenesis for multiple shoot induction of Angelica glauca. Rhizomes were used as explant, and maximum shoot multiplication was observed on MS medium supplemented with 6-Benzylaminopurine 8.0 µM and Indole-3-acetic acid 0.1 µM. Roots were observed within 14 days in the MS medium enriched with 0.5 µM IAA and 0.1 µM Naphthalene acetic acid (NAA) with an average production of 4.2 roots per shoot. Rooted plantlets were successfully hardened under greenhouse conditions and subsequently established in field, with a recorded survival rate of 72% after 45 days. The total phenolic content showed significant difference (p

The new phthalide arenophthalide D (1) was isolated from Helichrysum arenarium and characterized using 1D and 2D NMR spectral methods and HR-ESI-MS.

A new phthalide that was identified using NMR and mass spectral data as (±)-3-methoxysedanenolide (1) and the nine known compounds sedanenolide (2), Z-ligustilide (3), Z-butylidenephthalide (4), methyl ferulate (5), trans-ferulic (6) and trans-isoferulic acids (7), falcarindiol (8), β-sitosterol (9), and daucosterol (10) were isolated from the MeOH extract of roots of Ligusticum wallichii. Compounds 7 and 8 exhibited high inhibitory activity against NO formation in RAW264.7 cells.

From the seeds of the traditional medicinal plant Ziziphus jujuba growing in Uzbekistan, the fungal endophyte Alternaria sp. was isolated. Extracts of this fungus grown on solid rice and liquid Wickerham culture media yielded 21 natural products. These natural products include the new phthalide natural product (±)7-methoxyphthalide-3-acetic acid (1) in addition to 20 known compounds including 19 polyketides and one alkaloid. Moreover, the OSMAC (One Strain MAny Compounds) approach is applied in this study. The unambiguous structure of the new compound was elucidated on the basis of one- and two-dimensional NMR spectroscopy in addition to HR-ESI-MS. Compounds 2, 3, 4, and 7 exhibited a cytotoxic activity against mouse lymphoma cell lines (L5178Y) with IC50 values of 1.7, 7.8, 6.8, and 6.2 μM, respectively when compared with the positive control kahalalide F (IC50 4.3 μM).

Vanadia species formed on the surface depend on the K/V atomic ratio. At small K/V ratios, Raman spectra show the formation of the K-doped and K-perturbed monomeric species. At K/V = 1, kristalline KVO3 is mainly present on the surface. In situ high temperature XRD-results exhibit a promoting effect on the anatase to rutile phase transformation in the presence of 0.03 and 0.21 wt% potassium. Large amount of K (3 wt%) provides thermal stability of V/Ti/O catalyst and no transformation is found up to 600 °C. Reduction of vanadia K-doped vanadia catalysts is moved to higher temperatures than for the catalyst without potassium. The catalyst having 0.21 wt% K possesses the highest activity in o-xylene oxidation. Furthermore, the K-doped monomeric vanadia species in this catalyst leads to a promoted adsorption or a prevented desorption of phthalide, resulting in a decreased selectivity towards phthalide and COx and a increased PA selecticity.

A number of copoly(arylene ether ketones) containing the phenolfluorene and bisphenol A fragments were synthesized. By the example of these compounds, it was shown for the first time that the effect of reversible electronic switching can exhibit in the copolymer films even if this effect is absent in the corresponding homopolymer films.

Three new phthalide derivatives, emefuranones A1, A2 and B (1-3); six new phthalane derivatives, emefuran A, B1, B2, C1, C2 and D (4-9); three new farnesylated phthalide derivatives, farnesylemefuranones A-C (10-12); xylarinol C (13); and emericelloxide (14), along with four known compounds (dustanin, sorbicillin, aspergillodiol and xylarinol A), were isolated from the culture extracts of Emericella sp. IFM57991. Structures of 1-14 were elucidated on the basis of spectroscopic analysis and chemical evidence. Compounds 4-7 and 13 showed moderate antibacterial activities against Bacillus subtilis.

Literature data on the electron-acceptor properties of poly(diphenylene phthalide) (PDP) and poly(diphenylene sulfophthalide) (PDSP) are briefly generalized. Different types of electron affinity (EA) are calculated (in eV) in the B3LYP/6-311+G(d,p) approximation for model compounds of diphenyl phthalide (DPP) and diphenyl sulfophthalide (DPSP): vertical EAver = 0.21 and 0.06, adiabatic EAad = 0.66 and 0.58, and effective (taking into account the С—О bond cleavage in the phthalide and sulfophthalide cycles) EAeff = 1.21 and 2.21, respectively. The activation energies of the С—О bond cleavage in the phthalide and sulfophthalide cycles in radical anions (RAs) of DPP and DPSP are 0.34 and 0.07 eV, respectively. In reactions with alkaline metal atoms (Li and Na), the ring opening in DPSP occurs without a barrier, while in DPP the barrier is 0.34 and 0.31 eV for ring opening by the Li and Na atoms, respectively. The easiness of opening of the sulfophthalide ring compared to the phthalide one is the main reason for a longer lifetime of DPSP RA relatively to electron autodetachment compared to the the DPP RA (which was found earlier by negative ion mass spectrometry) and for dissociative PDSP reduction chemistry with formation of distonic RA. The high dipole moments of the phthalide (∼5 D) and sulfophthalide (∼6 D) fragments of the studied polymers provide a basis for the formation of physical dipole traps in them. The EA were calculated for the compounds modeling defect and end groups in PDP and PDSP. Macromolecules of PDP and PDSP are considered as a system of physical dipole and chemical electron traps related to the main, defect, and end electron-acceptor groups of the polymers. In the case of PDP, the EA of the anthraquinone end groups (AEGs) significantly exceeds the affinity of the main phthalide fragments, and the presence of AEGs should be taken into account when considering the reductive, electroactive, and luminescence properties of PDP. According to the calculations, the biphenyl fragments have the lowest ionization potentials (IP) among all structural units of the PDP and PDSP chains. A significant increase in the EA and a decrease in the IP of the triplet states of the model compounds indicate the possibility of participation of the triplet states of the PDP fragments in the charge separation and prolonged recombination photoluminescence observed in this polymer. In the framework of the polarizable continuum model (PCM), the influence of the solvents (DMSO and DMF) and polymer environment on the values of EA and IP of singlet and triplet states was estimated for the most analyzed model compounds. The electron-acceptor properties of the compounds modeling the chemically modified polymer units, radicals and carbocations of the triarylmethyl type, were considered. The experimental manifestations of electron traps were considered: the electronic and ESR spectra of the corresponding RAs, including AEG RAs. The possibility of participation of electron traps in the formation of the volume charge and in the electroactive phenomena in PDP (as transport units) was discussed. Phthalide ring opening in PDP in reactions involving electron seems to be poorly probable, and AEGs play an important role in these reactions.

The new phthalide derivative 3-[2′(R)-hydroxybutyl]-7-hydroxyphthalide (2) and the five known compounds (−)-3-butyl-7-hydroxyphthalide (1), isopatulin (3), m-hydroxybenzyl alcohol (4), cyclopenin (5), and cyclopeptine (6) were isolated from the marine isolate of the fungus Penicillium claviforme associated with the seagrass Zostera marina. The structures of the compounds were established using NMR spectroscopy and mass spectrometry. The absolute configuration of the C-2′ asymmetric center was determined using a modified Mosher method.

Polymerization of 3-methylidene phthalide in media of various organic solvents was studied. The stereochemical composition of macromolecules of polymethylidene phthalide (PMP) formed under different conditions of methylidene phthalide (MP) polymerization was determined by 1H and 13C NMR spectroscopy using 2D NOESY, HSQC, and COSY procedures. According to the X-ray diffraction data, no substantial differences are observed in packing of PMP macromolecules with different ratios of syndio-or isotriads: the predominant feature of the X-ray diffraction patterns is the presence of two intense amorphous halos. The diffraction patterns of a series of PMP films cast from solutions contain rather narrow low-intensity peaks probably caused by the formation of a small amount of crystalline microdomains.

A new phthalide was isolated from the roots of Pittosporum illicioides Makino. Its structure was established as (S)-3-ethyl-4,7-dimethoxyphthalide based on physicochemical properties and extensive spectroscopic analysis including 1D, 2D NMR, and HR-MS spectra.

Several studies have revealed that phthalides are suitable scaffolds for the design of high potency monoamine oxidase (MAO) inhibitors, in which C6-substituted phthalides have been shown high binding affinities to the MAO-A and MAO-B isoenzyme without delineating the underlying mechanism. By means of molecular modeling, we proposed a structural basis of such activity, in which these compounds could successfully dock into the active pocket of human MAO isoforms with predicted affinities in comparison to phthalide. Our study indicated that the interaction of hydrogen bond was more important factor for C6-substituted phthalides binding to MAO-A, and the orientations of inhibitors and the bound residues had the major impact on the binding to MAO-B. These results, therefore, suggested that C6-substituted phthalides served as promising leads for the development of drug treatments to neurodegenerative disorders such as Parkinson’s disease.

Reduction of poly(diphenylene phthalide) (PDP) with metallic lithium in DMF at room temperature was studied by electronic and ESR spectroscopies. The main feature of the process is the presence of a long induction period (about 50 to 80 min) which is probably caused by the formation of small lithium particles and by adsorption of the polymer on the metal. At least four types of nonparamagnetic color centers characterized by overlapping absorption bands at 570, 660, 750, and 810 nm were detected in the reduced solution. The amounts of all types of the color centers in the solution show a complex dynamic behavior. Reduction of the polymer in the bulk of the solution is due to lithium colloid particles which give rise to a narrow asymmetric ESR singlet (g = 2.0023, ΔH = 0.03 mT, A/B ≈ 1.1–1.8) and absorb light in the region λ ∼300–400 nm. Paramagnetic species with quartet ESR signal with a splitting of 0.1 mT and g = 2.0045 observed in the solutions being reduced at a polymer concentration of 0.2 mol L−1 were attributed to radical anions of terminal anthraquinone groups (TAGs). The electron affinities of some molecules simulating the phthalide-containing unit of the polymer backbone, TAG, and a defect anthrone group were calculated in the B3LYP/6-311+G(d,p) approximation. For diphenylphthalide, the vertical electron affinity EAvert = 0.21 eV, the adiabatic electron affinity EAad = 0.66 eV, the effective electron affinity EAeff (with allowance for cleavage of C-O bond in the phthalide ring) = 1.23 eV. For anthrone group, one has EAad ∼1.2 eV and for anthraquinone group, EAad ∼2 eV. The electron affinities of the model compounds were also calculated with inclusion of the energy of solvation in two solvents (DMF and DMSO) and the energy of polarization in the PDP film. The electronic spectra of some compounds chosen as models for the expected products of reduction (anions and dianions) of the main phthalide-containing fragments in the polymer, TAGs, and defect anthrone groups were also calculated by the TD DFT B3LYP/6-311G(d,p) method. The presence of three types of chemical electron traps and the possibility of manifestation of strong absorption bands of these anions and dianions in the spectral region 500–900 nm precludes unambiguous selection and assignment of complex experimental electronic spectra observed in the course of PDP reduction. The possible role of TAGs in the electronic and photophysical processes in PDP is discussed.

The roots of Angelica glauca Edgew., a high value critically endangered plant, were collected from two alpine Himalayan locations of Uttarakhand (India). The essential oils were obtained by hydro-distillation, analyzed by gas chromatography (GC) and gas chromatography–mass spectrometry (GC–MS) in order to determine the variation of concentration in their constituents. A total of 26 compounds were identified in both the oils, representing 97.7–98.2 % of total oil compositions. The major components of A. glauca oils were characterised as (Z)-ligustilide (40.6–53.0 %), (Z)-butylidene phthalide (20.7–32.8 %), (E)-butylidene phthalide (2.5–5.9 %) and (E)-ligustilide (2.1–2.3 %). Due to the higher relative area quantum of monomeric lactones (phthalides and ligustilides) in A. glauca populations (69.3–90.6 %) growing in Uttarakhand, there is a need to develop propagation protocol for mass multiplication and in situ and ex situ conservation.

A pure benzoxazine synthesized from phenolphthalein through Mannich reaction, 3,3′-bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazinyl)-1(3H)-isobenzofuranone (Boz-BP), was characterized by FTIR and 1H NMR. Its curing behavior was different with that of 2,2′-bis(4-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl)isopropane (Boz-BA) because Boz-BP possesses highly steric and inactivated phenol rings. During curing period, the reactivity of ortho position of phenolic hydroxyl group was retarded and the addition of -CH2- group generated in ring-opening reaction preferred to taking place on para position of aniline ring, which is beneficial for better thermal properties. Furthermore, additional hydrogen bonding would be formed between carbonyl groups on phthalide structure and hydroxyl groups in Boz-BP based polymer (P(Boz-BP)). Compared with the analogous polymer from Boz-BA (P(Boz-BA)), P(Boz-BP) displayed higher glass transition temperature, better thermal stability, better dimensional stability and flame-retardant properties.

A method was developed for the synthesis of 1-oxo-1H-isothiochromenes from 2-benzofuran-1(3H)-one (phthalide). 3-Bromo-6-chloro- and 3,6-dibromo-2-benzofuran-1(3H)-ones were prepared by the bromination of 6-chloro- and 6-bromo-2-benzofuran-1(3H)-ones and were converted by hydrolysis into 5-chloro- or 5-bromo-2-formylbenzoic acids. The condensation of these acids with rhodanine followed by recyclization gave 7-chloro- and 7-bromo-1-oxo-1H-isothiochromene-3-carboxylic acids.

In this study, an LC method for the simultaneous determination of six bioactive compounds from Angelica tenuissima, namely chlorogenic acid, ferulic acid, Z-ligustilide, nodakenin, decursin and decursinol angelate was developed and validated. Chromatographic analysis was carried out on a C18 column with a mobile phase consisting of 0.1% formic acid, methanol and acetonitrile at a flow rate of 0.8 mL min−1 and the effluent from the column was monitored by UV detector at 325 nm. The excellent linear behavior was observed over the investigated concentration range for reported compounds. The intra- and inter-day precision over the concentration range of compounds were lower than 1.7% (as relative standard deviation), and accuracy was between 97.2 and 106.0%. These results showed that the developed method is accurate, reproducible, and consequently applicable for the quantitation of bioactive components from the ethanolic extract of Angelica tenuissima Nakai.

We discuss the results of measurements of the optical characteristics of thin organic films of unconjugated poly(arylene ether ketone) polymer. We have observed persistent electroluminescence for this polymer. We have established an interrelationship between the polarity of the voltage applied to the experimental structure and the electroluminescence spectrum.

Gas chromatography — mass spectrometry (GC-MS) coupled with chemometric resolution upon two-dimensional data was employed to analyze the constituents of essential oils of essential oils of Angelica sinensis. Constituents in essential oils of Angelica sinensis root were identified by GC-MS with the help of subwindow factor analysis (SFA) method resolving two-dimensional original data into mass spectra and chromatograms. 76 of 97 separated constituents in essential oil of Angelica sinensis root were identified and quantified, and they account for about 91. 36% of the total content. The results show that ligustilide, butylene phthalide, 2-methoxy-4-vinylphenol, carvacrol, alloocimene,2,6,6-trimethylbicyclo-[3,1,1]hept-2-ene are the main constituents in essential oil of Angelica sinensis root.

Electrodes modified with poly(arylene phthalide ketones) were developed for the voltammetric determination of isomers of aromatic nitro compounds. A polynomial algorithm for processing analytical signals from a sensor array was tested in the analysis of ternary mixtures. It is shown that the sensor array offers promise for analyzing multicomponent mixtures in the case when analytical signals overlap.

Condensation of hetarene carboxaldehydes with phthalide gave 2-(3-hydroxy-1-oxoinden-2-yl)benzo[b]furan and 2-(3-hydroxy-1-oxoinden-2-yl)-5-ethylthieno[2,3-b]thiophene. Starting from hetaryl acetic acids gave 3-(3-hydroxy-1-oxoinden-2-yl)benzo[b]furan and 3-(3-hydroxy-1-oxoinden-2-yl)benzo[b]thiophene. Acylation of 3-hydroxy-1-oxoinden-2-yl-substituted heterocycles using acetic anhydride in the presence of 70% HClO4 leads to the formation of pentacyclic pyrilium salts. Pentacyclic indenopyridines are prepared by treating the pyrilium salts with ammonia. The reaction of the carbonyl group in the indenopyridines with hydroxylamine, hydrazine hydrate, and in reduction using NaBH4 has been studied.

A novel fluorinated diamine monomer, 3,3-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]phthalide (II), was prepared through the nucleophilic substitution reaction of 2-chloro-5-nitrobenzotrifluoride with phenolphthalein in the presence of potassium carbonate to yield the intermediate dinitro compound I, followed by catalytic reduction with hydrazine and Pd/C. Polyimides V were synthesized from diamine II and various aromatic dianhydrides IIIa–f via thermal or chemical imidization of poly(amic acid)s. These polymers had inherent viscosities ranging from 0.63 to 0.95 dL/g and were soluble in a variety of organic solvents. Va–f films had tensile strengths of 105–125 MPa, elongations to break of 9–12%, and initial modulus of 2.35–2.65 GPa. The glass transition temperatures of these polymers were recorded 259–320 °C, and no significant weight loss was observed below a temperature of 500 °C in nitrogen or in air. Compared with nonfluorinated homologues VI, V showed better solubility and lower color intensity, dielectric constant (2.70–3.11 at 1 MHz), and moisture absorption (0.12–0.27 wt %). In particular, Vc–f afforded lightly colored films, which had cutoff wavelengths lower than 380 nm and yellowness index (b* values) ranging from 9 to 25. On comparing thermal imidized polymers with chemical imidized ones, films Va–f(C) showed a lower color intensity than Va–f(H) did.

Procedures were developed for preparing unsaturated phthalides: phthalideneacetic acid and methylene phthalide, which are promising monomers for radical polymerization. The structures of the monomers were studied, and their copolymerization with methyl methacrylate was performed.

The applicability to vinyl polymers of the procedure for quantitative determination of phthalide groups in polymeric molecules from the color of their sulfuric acid solutions was examined. The correlation between the intensity of the color of sulfuric acid solutions of polymers (polymethyl methacrylate, polystyrene) and the content of phthalide fragments incorporated into the polymer molecule was studied systematically on a quantitative level.

New activated phthalide-containing dihalogeno derivatives were synthesized, and cardo polyarylene ether ketones based on them were prepared. The effect of the type of the halogen atom (fluorine, chlorine, or bromine) on the efficiency of polycondensation was estimated. It was demonstrated that high-molecular-weight cardo polyarylene ether ketones can be obtained only from the difluoro derivative. The synthesized polymers are amorphous compounds characterized by high glass transition temperatures (210–250°C). These polymers are soluble in many organic solvents and form strong transparent films.

6,11-Dihydrodibenz[b,e]oxepin-11-ones were obtained by cyclodehydration of 2-(phenoxymethyl)-benzoic acids prepared by reaction of the corresponding phenols with phthalids. Cyclodehydration was found to be most effective using polyphosphoric acid ester. The structure of one of the title compounds was determined by X-ray crystal structure analysis.

3(Bis(alkylthio)methylene)-3H-isobenzofuran-1-ones2a–e and 2-(bis(alkylthio)methylene)-3(2H)-benzofuranone derivatives4a–c are obtained by reaction of phthalides1a–d or 3(2H)-benzofuranone (coumaranone3), respectively, with carbon disulfide under basic conditions followed by alkylation. The reaction behaviour of the new compounds2 and4 is investigated. 2-((2-Dimethylthio-1-oxo)ethyl)benzoic acid N,N-dimethylamide (7a) and 2-((2-dimethylthio-1-oxo)ethyl)-benzoic acid 2-methylpiperidide (7b) are surprisingly formed instead of the methylthio substitution products by treatment of2a with the corresponding amine in the presence of aluminum chloride.

The elimination kinetics of α-bromo-o-toluic acid have been studied over the temperature range of 623.3–673.6 K and pressure range of 22–43 Torr. The reaction products are phthalide and HBr gas. The rate coefficient for the homogeneous unimolecular elimination is expressed by the following equation: log k1 (s−1)=(11.69±0.13)−(182.1±1.6)kJ mol−1(2.303RT)−1. The formation of phthalide product suggests participation of the carbonyl oxygen of the COOH group. The present result provides additional evidence of an intimate ion pair mechanism in the gas phase pyrolysis of some type of haloacids in the gas phase.

Indandione, its enol acetate, and the products of a parallel reaction — a mixture of isomeric acidsE, Z-5, and phthalide — are formed in the reaction of substituted phenylacetic acid with phthalic anhydride in acetic anhydride and triethylamine. 2-Substituted indandione derivatives were obtained.

Hydrogenation of vermistatin, a metabolite ofPenicillium vermiculatum, affordedcis- andtrans-3-(2′-carboxy-4′,6′-dimethoxybenzyl)-6-propyltetrahydro-4H-pyran-4-one and 4,6-dimethoxy-3-(4′-propylcyclopentanon-2′-yl)phthalide. The latter compound was found to be the strongest inhibitor of RNA synthesis in P 388 leukemia cells of all compounds tested.

The stereospecific position of the H4 proton in the PMR spectra of 3-benzyl-idenephthalides identifies unambiguously the E and Z isomers in a mixture. The IR spectra of off-planar deformation vibrations of the C=C bond in the 990–970 cm−1 region have strong absorption bands, assigned to the E and Z isomers. The strong short-wave band (260 nm) for 3-benzylidenephthalides, having only one benzene ring in the indan moiety, suggests the presence of the E form (e=28,000). The long-wave absorption band at 390–430 nm belongs to the Z isomers (e=21,000–31,000). 3-Benzylidenephthalides which have no carbonyl groups in their molecules, show fluorescence (λf1=540–560 nm in EtOH).

Relative reactivity of o-xylene, o-tolualdehyde, phthalide, and phthalane and the rate of phthalic anhydride formation from them have been determined. The main route of o-xylene oxidation to phthalic anhydride is due to the o-arrangement of methyl groups, proceeding through bicyclic products, such as dihydrobenzofuran (phthalane) and 3,4-benzofuran.

The photo-induced degradation of naphthalene, 1,4-naphthoquinone, 1-naphthol and 1-NO(2) naphthalene, adsorbed on silica gel, and with the addition of nitrogenous air pollutants e.g. NO(2) (as KNO(2)) was investigated. Results indicate that compounds adsorbed onto a solid carrier are degraded when irradiated with UV light (lambda290 nm) in the presence of nitrites. The key species initiating the naphthalene degradation is the OH-radical which is generated through the photolysis of NO(2). Reaction products identified were 2-formyl-cinnamaldehyde, 1,4-naphthoquinone, nitronaphthol, o-phthaldialdehyde, phthalide and nitronaphthalene. A mass balance between 40-50% was achieved. Under the same irradiation conditions, 1-NO(2) naphthalene is mainly degraded by direct photolysis while degradation of 1-naphthol and 1,4-naphthoquinone proceeds via the reaction with OH-radicals. Identified products were hydroxy-nitro-nitroso- and quinones compounds.

The product of the condensation of the Fischer base with unsubstituted 8-hydroxy-1-naphthaldehyde is a bisindolinespirooxepine. 5,7-Dinitro-8-hydroxy-1-naphthaldehyde reacts with the Fischer base to give a merocyanine that does not display a tendency to undergo conversion to the cyclic form. 2H-Naphtho[1,8-bc]furan derivatives are formed in the reaction of the Fischer base with 5-nitro-, 5-bromo-, and 5,7-dibromo-8-hydroxy-1-naphthaldehydes. The structures of the compounds obtained were established on the basis of data from the PMR and 13C NMR spectra. It was shown by means of the 13C NMR spectra that the product of the condensation of phthalic monoaldehyde with the Fischer base is not a seven-membered spirolactone, as previously assumed, but rather a phthalide derivative.

In the Dieckmann-Shapiro condensation of phthalides with p-dimethylaminobenzaldehyde the reaction rate decreases with an increase in the electron-donor effect of the substituent in the phthalide and becomes comparable to the rate of a competing reaction — Claisen condensation of ethyl acetate with the aldehyde.

We have prepared a series of highly pure phthalimidines in high yield by reaction of phthalides with aqueous ammonia. The synthetic conditions depend markedly on the structure of the starting phthalide.

As the result of a study of the influence of solvents on the parameters of the NMR spectra of a number of phthalide-isoquinoline alkaloids it has been established that benzene causes changes of different magnitudes in the CSs of the 4′-OCH3, 5′-OCH3, and N-CH3 protons in the erythro and threo series. Furthermore, it has been found that TFA causes specific changes in the CSs and SSCCs of the H1 and H9 protons in the bases of these series. The possibility has been shown of using the results of the influence of different solvents to solve structural and stereochemical problems in the study of the alkaloids phthalide-isoquinoline series.

The separation of industrial trace products such as bischloromethyl ether and phthalide on particular gas-liquid-solid chromatography columns are shown. Separations of environmental interest are also reported. The column characteristics are discussed to obtain the best separation power.

1. In a study of the infrared and ultraviolet spectra of o-carboxybenzoylferrocene and some of its derivatives it was shown that both in the crystals and in solutions these substances exist in the open carboxy form and, within the limits of the sensitivity of the spectrographic method, show no signs of the presence of the cyclic phthalide form. 2. o-Hydroxybenzoylferrocene was prepared by the condensation of salicyloyl chloride with ferrocene in presence of aluminum chloride. o-Hydroxybenzoylferrocene was converted into various derivatives. 3. According to the infrared and ultraviolet spectra, o-hydroxybenzoylferrocene molecules contain an intermolecular chelating hydrogen bond O-H...O. 4. The reduction of o-hydroxybenzoylferrocene with lithium aluminum hydride gaveα-o-hydroxyphenylferrocenemethanol, which is extremely readily alkylated.