Ethyl Aniline Research Articles

Hydrophobic deep eutectic solvent-based vortex assisted liquid–liquid microextraction for the determination of famciclovir in water samples coupled with high performance liquid chromatography

Deep eutectic solvents (DESs), as a new generation of green solvents, have the advantages of simple preparation procedure, low toxicity, non-volatility and good extraction performance in replacing traditional volatile organic solvents. In this work, a series of hydrophobic DESs were prepared and used as extraction solvent for the vortex-assisted liquid–liquid micro-extraction and determination of famciclovir in environmental water samples coupled with high performance liquid chromatography. The key factors affecting the extraction efficiency were investigated by using single-factor test and response surface methodology. The optimized conditions were as follows: the DES type (thymol: ethyl aniline formate, molar ratio 3:1), DES dosage 50 mg, extraction time 1.5 min, solution pH 6.0, diluent volume 100 µL. Under the optimal conditions, calibration curve of the proposed method was in the range of 0.7–2000 μg/L with correlation coefficient (r2) higher than 0.9997. The limit of detection (LOD, S/N = 3) and the limit of quantitation (LOQ, S/N = 10) were 0.2 and 0.7 μg/L, and the intra-day and inter-day precision were less than 2.3 % and 1.6 %, respectively. Finally, this method was successfully used for the determination of trace famciclovir in environmental water samples with recoveries in the range of 86 %-118 %.

Preparation, Molecular Structure and Morphological Studies of DBSA Doped (M-Toluidine-Co-2-Ethylaniline) Copolymer Composites for flexible Sensor Applications in Agricultural Field

A new series of dodecyl benzene sulphonic acid(DBSA) doped copolymer was synthesized using two different monomers m-toluidine and 2-ethylaniline with silver nanoparticles. The synthesized copolymer nanocomposite is soluble in Dimethylformamide (DMF), Tetrahydrofuran (THF), Dimethyl sulfoxide (DMSO), and N-Methylpyrrolidone (NMP). The synthesized polymer is analysed by various characterisation techniques. The absorption peaks around 316 and 598 nm confirm the presence of ? – ?* transition and n – ?* transition. The increase in the ethyl aniline ratio in the feed induced blue shift in the absorption peak. FTIR spectra confirms the presence of benzenoid and quinoid ring. The XRD pattern indicates the amorphous pattern of the polymer. SEM image revealed a large number of smooth surfaced particles agglomerate together. Ordered spherical sized growth of the particles with layered architectures, Nano sized tubular or nanotube growth along with porous structures was observed in the SEM image. The electroactive study of the composite confirms the semiconducting nature 1.04 × 10-6 to 2.86 × 10-8 S/cm, which can be used as basic materials for the manufacturing electric and electronic components in sensor field. The application of this electroactive materials are under taken for moisture sensor studies in the future for precision agriculture.

Effects of different mixing methods on the conductivities of poly(2-ethyl aniline)/graphene and poly(2-ethyl aniline)/expanded graphite composites

In this study, the preparation of poly(2-ethyl aniline) (PEAn)/Graphene and PEAn/Expanded Graphite (EG) composites using different mixing methods and the effect of the preparation conditions of composites on their electrical conductivities were investigated. Herein, it was examined both the effect of the sonication time of EG and Graphene in HCl medium before the polymerization on their homogeneous dispersion in the PEAn matrix and the effect of the three different mixing methods, including magnetic stirring, ultrasonication, and ball milling, on the formation of network in the composites. From the morphological characterization obtained by SEM, due to π-π* electron interaction, 2-EAn molecules were polymerized on the surface of graphene and EG. It was determined that the composite with the highest conductivity was obtained by in situ polymerization of 2-EAn in the presence of graphene via a ball milling method for 10 h, after the sonication of graphene in aqueous HCl medium for 6 h. The conductivity of this PEAn/Graphene (1:1 by weight) composite increased from 3.5x10−7 Scm−1 to 1.57 Scm−1 compared to pure PEAn.

Anticorrosion Coatings from Poly (Aniline-co-2-Ethylaniline) Micro/Nanostructures

PANI copolymer micro/nanostructures with different surface wettability were obtained from the chemical oxidation copolymerization of aniline (Ani) with 2-ethyl aniline (EA) at diverse [EA]/[Ani+EA] molar ratios, by employing ammonium persulfate as an oxidant. The results revealed that the poly (aniline-co-2-ethyl aniline) (PANI-EA) copolymer micro/nanostructures exhibited satisfactory anticorrosion performance for carbon steel, and the corrosion protection efficiency increased with the increase of water repellent property. Poly (2-ethyl aniline) (PEA) showed the largest contact angle (CA=145°) and show the best corrosion protection for the carbon steel (η = 87.29%). It is found that the superior anticorrosion property of PEA is attributed to its high hydrophobicity, low conductivity and low porosity.

A non-gassing electroosmotic pump with sandwich of poly(2-ethyl aniline)-Prussian blue nanocomposite and PVDF membrane.

Low voltage, non-gassing electroosmotic pump (EOP) was assembled with poly(2-ethyl aniline) (EPANI)-Prussian blue nanocomposite electrode and commercially available hydrophilic PVDF membranes. The nanocomposite material combines excellent oxidation/reduction capacity of EPANI with exceptional stability by shuttling of proton between Prussian blue nanoparticles and EPANI redox matrix. The flow rate was highly dependent on the electrode composition but it was linear with applied voltage. The flow rate at 5V for different nanocomposite, EPANI, EPANI-A, EPANI-B, and EPANI-C were 127.29, 187.41, 148.51, and 95.47µL/min cm2 , respectively, which increases substantially with increase in the Prussian blue content. The obtained best electro osmotic flux was 43µL/min/V/cm2 for EPANI-A. It was higher than most of the EOP assembled using polyquinone and polyanthraquinone redox polymers. The assembled EOP remained exceptionally stable until the electrode charge capacity was fully utilized. The best EOP produces a maximum stall pressure of 1.2kPa at 2V. These characteristics make it suitable for a variety of microfluidic/device applications.

Study of Pb (II) adsorption from aqueous solutions by TiO2 functionalized with hydroxide ethyl aniline (PHEA/n-TiO2)

In this study, the crystalline Nano particles of TiO2 were modified with hydroxide ethyl aniline and were used for the elimination of Pb (II) ions from the liquid solutions. The adsorbent was synthesized via chemical oxidization method and characterized by FTIR, SEM and XRD analysis. Variations in pH, adsorbent dosage, initial metal ion concentration, contact time, temperature and ionic strength were considered as the effective parameters on the adsorbent performance in batch mode adsorption. Optimum condition was cleared through the batch experiments as follow: pH = 5.5, adsorbent dosage = 2 g L−1, initial concentration of Pb (II) ions = 100 mg L−1, temperature = 328 k, contact time = 3 h and agitation speed = 150 rpm. The maximum adsorption capacity under the optimum conditions was obtained 26.05 mg g−1. Webber-Morris model and Langmuir isotherm were the best mathematical models for prediction of kinetic and equilibrium behavior, respectively. Thermodynamic studies demonstrate that the adsorption of Pb (II) ions is spontaneous and endothermic.

Synthesis and evaluation of novel antibacterial monoazo disperse dyes based on sulfonamide derivatives on polyester

PurposeThis paper aims to present the design and synthesis of a series of novel antibacterial monoazo disperse dyes based on sulfonamide derivatives to combine the dyeing and functional finishing steps on polyester into one process.Design/methodology/approachThe diazoniom salts of sulfonamides, namely, 4-amino-N-(2-pyrimidinyl) benzenesulfonamide, 4-amino-N-(4-methyl-2-pyrimidinyl) benzenesulfonamide and 4-amino-N-(4,6-dimethyl-2-pyrimidinyl) benzenesulfonamide were prepared and then coupled to N,N-diethyl aniline, N,N-dicyanoethyl aniline and N,N-dihydroxy ethyl aniline, respectively, to produce the dyes.FindingsThe structures of the dyes were characterized using their spectral data (FTIR, 1H-NMR, UV-Vis) and elemental analysis. The results indicated that all the dyes exhibit positive solvatochromism in more polar solvents. Dispersion of the dyes was prepared in water and applied to polyester fabrics. The synthesized dye 3a which had good exhaustion on the fabric (89.98 per cent) and were tinctorially stronger (28899 l/mol.cm) showed higher visual colour yield (16.51). The antibacterial efficacy of the dyes was assessed, and they showed activity against both gram-positive and gram-negative bacteria but in different levels depending on their structures.Research limitations/implicationsA simple way to combing functional finishing and dyeing in one process was successfully performed via design and synthesis of disperse dyes with an antibacterial moiety incorporated into dye molecules. The dyes were fully charaterized and evaluated on polyester.Originality/valueA series of novel antibacterial monoazo disperse dyes based on sulfonamide derivatives were synthesized. The authors studied their application for dyeing of polyester fabric. The dyes offered good results in terms of preparation, yield, purity, visual colour yield, fastness properties and activity against bacteria.

Electrochemical corrosion behavior of carbon steel coated by polyaniline copolymers micro/nanostructures

A series of polyaniline (PANI) copolymers micro/nanostructures were prepared in order to investigate the effect of different groups with different hydrophilicities on the corrosion protection behavior of polyanilines. Hydrophilic groups (–SO3H and –COOH) and hydrophobic groups (–CH3 and –C2H5) were introduced into the polyaniline molecular structure by the copolymerization of aniline (ANI) and 3-aminobenzenesulfonic acid, 3-aminobenzoic acid, 3-toluidine and 2-ethyl aniline using ammonium persulfate as an oxidant. The carbon steel coated by the resultant PANI copolymers micro/nanostructures were investigated and compared regarding their electrochemical corrosion in 0.1 M H2SO4. Potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) were used. It was found that neither PANI nor PANI copolymers micro/nanostructures provide anodic corrosion protection for carbon steel, but they can effectively restrict the cathodic reaction. Moreover, the ability to restrict the cathodic reaction depends on the surface wettability of the PANI and PANI copolymers micro/nanostructures. The corrosion protection of PANI and PANI copolymers increased along with their water repellency. A well-fitting correlation between the contact angle (θ) of the PANI or PANI copolymers micro/nanostructures coatings and their corrosion protection efficiency (η) was found to be η = 102.22 − 102.78exp(−θ/84). The PANI copolymer with the hydrophobic –C2H5 group (PANI-C2H5) showed the largest static water contact angle (CA = 125°) and the most effective protection with an inhibition efficiency of 78.98%.

Nanomaterials Based on Polyanilines and MoSe2

Polyaniline, poly(N-methyl aniline), poly(2-ethyl aniline) and poly(2-propyl aniline) were intercalated into layered molybdenum diselenide by using the exfoliation/restacking property of LixMoSe2. MoSe2 was reacted with n-butyllithium to form LixMoSe2. The LixMoSe2 was exfoliated in N-methylformamide (NMF) with the help of ultrasonication which lead to the formation of single layers of MoSe2. Addition of NMF solutions of the polymers to the exfoliated layers resulted in their intercalation into MoSe2. The products were characterized by powder X-ray diffraction. Fourier transform infra-red spectroscopy, and four-probe van der Pauw technique electrical conductivity measurements are reported here for the first time.

Photoelectrochemical Studies on CdS/Poly Ethyl-Aniline Interfaces

An inorganic/organic/interface (IOI) consisting of CdS/poly ethyl aniline (PEA) assemblies was subjected to photoelectrochemical studies in nanoparticle suspensions and in thin solid film forms . The effects that PEA modifiers have on the photoelectrochemical behavior of the IOI were investigated using [Fe(CN)6]4-as a photoactive hydrated electron donor agent. Results show that the adsorption process of [Fe(CN)6]3- (the photolysis product) controls the photoactivity outcome of IOI assemblies. CdS/PEA shows lower heterogeneous photochemical response than native CdS. Native CdS amorphous nanoparticles adsorb more [Fe(CN)6]3- with a very steady adsorption/desorption process than the CdS/PEA. The interface activities were explained by analyzing the IOI junction’s properties such as electron affinity, work function and hole/electrons barrier heights. The lower hole barrier height versus electron barrier height suggests that charge injection is mediated at the IOI interface through hole transfer. The aqueous nano systems retained moderate stability as indicated by the reproducibility of their photocatalytic activities. Both [Fe(CN)6]4- and PEA contributed to the stability of native CdS surfaces.

Excess Volumes, Speeds of Sound, Isentropic Compressibilities and Viscosities of Binary Mixtures of N-Ethyl Aniline with Some Aromatic Ketones at 303.15 K

Densities (<TEX>${\rho}$</TEX>), Viscosities (<TEX>${\eta}$</TEX>) and ultrasonic speeds (u) of pure acetophenone (AP), propiophenone (PP), <TEX>$p$</TEX>-methyl acetophenone (<TEX>$p$</TEX>-MeAP), <TEX>$p$</TEX>-chloroacetophenone (<TEX>$p$</TEX>-ClAP) and those of their binary mixtures with <TEX>$N$</TEX>-ethyl aniline (<TEX>$N$</TEX>-EA) as a common component, were measured at 303.15 K over the entire composition range. These experimental data were used to calculate the excess volume <TEX>$V^E$</TEX>, deviation in ultrasonic speeds <TEX>${\Delta}u$</TEX>, isentropic compressibility <TEX>$K_s$</TEX>, intermolecular free length <TEX>$L_f$</TEX>, acoustic impedance Z, deviations in isentropic compressibility <TEX>${\Delta}K_s$</TEX>, deviation in viscosity <TEX>${\Delta}{\eta}$</TEX> and excess Gibbs free energy of activation of viscous flow (<TEX>$G^{*E}$</TEX>) at all mole fractions of <TEX>$N$</TEX>-ethyl aniline. These parameters, especially excess functions, are found to be quite sensitive towards the intermolecular interactions between component molecules. Theoretical values of viscosity of the binary mixtures were calculated using different empirical relations and theories. The relative merits of these relations and theories were discussed. The experimental results were correlated by using the polynomial proposed by Redlich-Kister equation.

Binary Mixtures of Nonyl Phenol with Alkyl Substituted Anilines as Corrosion Inhibitors for Mild Steel in Acidic Medium

The present study deals with the evaluation of the corrosion inhibition effectiveness of the two binary mixtures of nonyl phenol (NPH) with 2, 4 dimethyl aniline (DMA) and 2 ethyl aniline (EA) at different concentration ratios (from 1:7 to 7:1) for mild steel in H2SO4 (pH=1) solution by weight loss and potentiodynamic polarization method. Corrosion inhibition ability of the compounds has been tested at different exposure periods (6 h to 24 h) and at different temperatures (303 K to 333 K). The binary mixture of NPH and EA (at 7:1 concentration ratio) has afforded maximum inhibition (IE% 93.5%) at 6 h exposure period and at room temperature. The adsorption of both the inhibitors is found to accord with Temkin adsorption isotherm. Potentiodynamic polarization study reveals that the tested inhibitors are mixed type inhibitor and preferentially act on cathodic areas. Electrochemical impedance study suggests formation of an inhibition layer by the adsorption of the inhibitors on the metal surface. An adsorption model of the inhibitor molecules on the metal surface has been proposed after immersion test in the inhibited acid showed characteristic shift of N‐H and O‐H bond frequencies towards lower side compared to that of the respective pure samples which indicated the donation of electron pair through N and O atom of the inhibitor molecule in the surface adsorption phenomena. SEM study has revealed formation of semi globular inhibitor products on the metal surface. The comparisons of the protection efficiencies of these compounds according to their relative electron density on the adsorption centre and projected molecular area of the inhibitor molecules have been made.

Synthesis, Characterization and In Vitro Antibacterial Activity of Coordination Polymers Based on Bis Bidentate Ligand

A novel bis (bidentate) ligand, namely 5, 5′- (2, 2′- (phenyl azanediyl) bis (ethane-2, 1 - diyl) bis (oxy) bis (methylene) diquinolin −8 - ol) (PBEQ), was synthesized by condensation of 5 –chloromethyl −8 - hydroxyquinoline hydrochloride with N, N – Di (2 - hydroxy ethyl) aniline in the presence of a base catalyst. This ligand was characterized by IR, 1H-NMR, and elemental analysis. Coordination polymers of this bis-ligand (PBEQ) were prepared with Cu(II), Ni(II), Co(II), Mn(II), and Zn(II) metal ions. All of these coordination polymers were characterized by elemental analyses, IR spectral and diffuse reflectance spectral studies. The thermal stability was evaluated by thermogravimetric analyses. In addition, all of the coordination polymers have been characterized by their magnetic susceptibilities. The microbicidal activity of all the samples has been monitored against plant pathogens.

In situ STM study of the adsorption and electropolymerization of o-, m-, and p-ethylaniline molecules on Au(111) electrode

Cyclic voltammetry (CV) and in situ scanning tunneling microscopy (STM) were employed to study the adsorption and polymerization of the geometric isomers of ethylaniline (EA) on a Au(111) single-crystal electrode in 0.5 M H(2)SO(4). All three isomers, namely o-, m-, and p-EA, were adsorbed in highly ordered structures, identified as Au(111)-(4 x 2 square root(3))rect for m- and p-EA and (4 square root(3) x 4 square root(3))R30 degrees for o-EA, at the onset potentials (approximately 0.9 V [vs. reversible hydrogen electrode]) for electropolymerization. Raising the potential in excess of 0.9 V resulted in oxidation and polymerization of m- and o-EA, but decomposition of p-EA. Molecular-resolution STM imaging revealed that poly(m-EA) and poly(o-EA), denoted respectively as m- and o-PEA, exhibited distinctively different molecular shapes. More specifically, m-PEA molecules were predominantly linear and aligned preferentially in the 121 directions of the Au(111) surface; whereas o-PEA molecules were ill-defined in shape and in dimension. These differences in molecular conformation stemmed from unlike arrangements of adsorbed monomers at 0.9 V. Notably, m-EA were adsorbed in zigzags with two nearest neighbors separated by approximately 0.5 nm, which were spatially so similar to the backbones of m-PEA that m-EA molecules coupled readily when the potential was raised high enough to induce the oxidation of m-EA. In contrast, the arrangement of o-EA molecules was so different from the ideal configuration of its polymer that molecules coupled randomly to yield crooked polymer chains less than 20 nm in length. The effect of potential on the structure of m-PEA was examined also, revealing notable branching of linear m-PEA if the electrochemical potential was set at 1.1 V.

Preparation of poly(2-ethyl aniline)/kaolinite composite materials and investigation of their properties

Conductive poly(2-ethyl aniline) (PEAn)/kaolinite composite was prepared by chemical polymerization in aqueous HCl medium in the presence of kaolinite particles by using potassium chromate (K 2CrO 4) as oxidant. Effects of polymerization conditions, such as concentrations of oxidant and 2-ethyl aniline, polymerization time and temperature on PEAn content and conductivity of composite, were investigated. The prepared composite material, having the highest PEAn content and conductivity, was obtained in the polymerization carried out at 20 °C for 2 h with 0.2 M K 2CrO 4 and 0.2 M EAn. It was observed that the micro-hardness of prepared composites increased with the increase in the PEAn contents of composites. The highest micro-hardness value of 7.92 kg mm −2 was reached at 24.6% PEAn content. Characterization of composites was carried out by FTIR spectroscopy, XRD, TGA and SEM techniques.

Sulphonic acids doped poly(N‐ethyl aniline): A material for humidity sensing application

AbstractSubstituted polyaniline, poly(N‐ethyl aniline) (PNEA), doped with camphor sulphonic acid (CSA) and p‐toluene sulphonic acid (p‐TSA), was synthesized by single‐step chemical polymerization method using ammonium persulphate as an oxidizing agent. This is a single‐step polymerization process to synthesize directly the conducting emeraldine salt phase of the polymer using CSA and p‐toluene sulphonic acid as dopants. The synthesized polymers were characterized by UV–vis and FTIR spectroscopy, scanning electron microscopy, TGA/SDTA, DSC, and conductivity measurements. This single‐step chemical synthesis method offers a polymer having very good physicochemical properties with good electrical conductivity. High temperature conductivity measurements show “thermal activated behavior.” The change in resistance with respect to % relative humidity (% RH) is observed, when pressed pellets of the polymer were exposed to the broad range of humidity (ranging between 20 and 100% RH). POLYM. ENG. SCI., 47:1621–1629, 2007. © 2007 Society of Plastics Engineers

Comparison of electrorheological properties of some polyaniline derivatives

In this study, electrorheological (ER) properties of various polyaniline derivatives, namely: poly( o-toluidine) (POT), poly( N-methyl aniline) (PNMAn), poly( N-ethyl aniline) (PNEAn), and poly(2-ethyl aniline) (P2EAn) were investigated. Effects of various parameters such as; particle size, particle conductivity, suspension's sedimentation stability, flow times, concentration, electric field strength, shear rate, frequency and temperature onto ER activity of these polyaniline derivatives/silicone oil (SO) suspensions were investigated. Average particle diameters ( d 50) of four samples were determined by dynamic light scattering as 8.51, 9.08, 11.22 and 13.46 μm for P2EAn, PNEAn, PNMAn and POT, respectively. It was found that POT has the highest conductivity with a value of 6.87 × 10 −7 S m −1, and P2EAn has the lowest with 1.01 × 10 −7 S m −1, among the polyaniline derivatives examined. Fifty four percent of sedimentation ratio was measured after 30 days for all the polyaniline derivatives/SO suspensions studied. The highest electric field viscosity was observed for POT/SO suspensions as η = 1.04 kPa s. The maximum excess shear stress was obtained for the POT suspensions (25 wt.%) as Δ τ = 917 Pa at E = 2 kV/mm.

Core-shell poly(styrene/sulfonatedn-hydroxy ethyl aniline) latex particles prepared by chemical oxidative polymerization in emulsion polymerization

The kinetic behavior of emulsion polymerizations of styrene in the presence of sulfonated N-hydroxy ethyl aniline (SHEA) was investigated with two initiators: 2,2′-azobisisobutyronitrile (AIBN) and potassium persulfate (KPS). SHEA was synthesized using a stepwise polyurethane reaction method from 3-hydroxy-1-propane sulfonic acid sodium salt, isophorone diisocyanate (IPDI), andN-(2-hydroxyethyl) aniline. Stable core-shell poly(styrene/sulfonated N-hydroxy ethyl aniline, St/SHEA) latex particles were successfully prepared by using an appropriate amount of AIBN, in which SHEA plays the role of ‘surfmer’, i.e., acting as both a surfactant in the emulsion polymerization and a monomer in the chemical oxidative polymerization. The kinetic behavior was dissimilar to that of typical emulsion polymerization systems. A long inhibition period and low rate of polymerization were observed due to radical loss by the oxidative polymerization of SHEA. It was concluded, due to the low water-solubility of AIBN and retardation reaction by SHEA, that the initial loci of polymerization were monomer droplets. However, growing polymer particles as polymerization loci became predominant as polymerization proceeded. It was suggested that AIBN was more effective than KPS in the preparation of the core-shell type poly(St/SHEA) latex particles. With KPS, no substantial polymerization was observed in any of the samples.

Novel alkyl substituted polyanilines/molybdenum disulfide nanocomposites

Polyaniline (PANI), poly( N-methyl aniline) (PMA), poly(ethyl aniline) (PEA) and poly(propyl aniline) (PPA) were synthesized in their salt form, and then characterized by FT-IR spectroscopy and charge transport measurements. The solubility of the polymers was tested in a variety of solvents and N-methylformamide (NMF) was found to be the best solvent. While polyaniline gave a colloidal suspension in NMF, the solubility of the polymer increased with increasing length of the alkyl group, resulting in a concomitant decrease in electrical conductivity. The solubility of the polymers was exploited and their intercalation was performed in molybdenum disulfide by using the exfoliating/restacking property of LiMoS 2. Powder X-ray diffraction showed that genuine intercalation compounds were formed. The resulting nanocomposites were also characterized by thermogravimetric analysis (TGA).

Synthesis of Some New Fused and Spiro 1,4-Benzoxazine Derivatives

4-Methyl-3,4-dihydro-2H-1,4-benzoxazin-3-one 1 reacted with CS 2 and halo compounds to give thieno-1,4-benzoxazines 2a , b and 2-(1,3-dithiol-2-yliden)-1,4-benzoxazines 3a , b , respectively. Reaction of compound 1 with cyanoketene S,S diacetal afforded pyrano-1,4-benzoxazine derivatives 4 , 5 . Treatment of compound 1 with bromine in 1:2 molar ratio afforded 2,2-dibromo derivative 6 . Compound 6 reacted with bidentates, or with CS 2 and reactive methylenes to give the corresponding spiro compounds 7a–f and 8a–d , respectively. 2-(2-Bromo-4-methyl-3,4-dihydro-2H-1,4-benzoxazin-3-yliden)malononitrile 10 was allowed to react with ethyl thioglycolate, aniline or benzylamine to yield thiopyrano-1,4-benzoxazine 11 or pyrrolo-1,4-benzoxazines 12a , b , respectively. 2-(1-Ethoxy-methyliden)-4-methyl-3,4-dihydro-2H-1,4-benzoxazin-3-one 13 reacted with CS 2 and reactive methylenes or malononitrile to give spiro dithiolane 14a–c and 2-(4-methyl-3-oxo–3,4-dihydro-2H-1,4-benzoxazin-2-ylidenmethyl)malononitrile 15 , respectively. Reaction of compound 15 with some reactive methylene compounds gave the corresponding spiro cyclopentenes 16a–c .