IRANIAN SEMINAR OF ORGANIC CHEMISTRY | Year:2012 | دوره:19 |Papers Count:50

2-AZETIDINONES, COMMONLY KNOWN AS B-LACTAMS, ARE WELLKNOWN HETEROCYCLIC COMPOUNDS. A LARGE NUMBER OF 3-CHLORO MONOCYCLIC B -LACTAMS HAVING SUBSTITUTION AT POSITIONS 1 AND 4 POSSESS POWERFUL ANTI-BACTERIAL, ANTI-MICROBIAL, SEDATIVE, ANTI-FUNGAL AND ANTI-TUBERCULAR ACTIVITY. HEREIN WE DESCRIBED THE SYNTHESIS OF A SERIES OF NOVEL B -LACTAMS. THE EFFICIENT AND RAPID SYNTHESIS OF NOVEL B-LACTAMS HAS BEEN ESTABLISHED IN GOOD YIELDS STARTING FROM 3-PHENYL-2, 3, 6, 7-TETRAHYDROIMIDAZO [2, 1-B] THIAZOLO [5, 4-D] ISOXAZOLE1 THAT HAS BEEN SYNTHESIZED IN RECENT LITERATURE. IN THE FIRST, 3-PHENYL-2, 3, 6, 7-TETRAHYDROIMIDAZO [2, 1-B] THIAZOLO [5, 4-D] ISOXAZOLE1 ON CONDENSATION WITH ETHYLCHLORO ACETATE YIELDED ETHYL 2- (3-PHENYL-3, 6, 7-TRIHYDROIMIDAZO [2, 1-B] THIAZOLO [5, 4-D] ISOXAZOLE-2 (3H) -YL) ACETATE2, WHICH ON AMINATION WITH HYDRAZINE HYDRATE YIELDED 2- (3-PHENYL-3, 6, 7-TRIHYDROIMIDAZO [2, 1-B] THIAZOLO [5, 4-D] ISOXAZOL -2 (3H) -YL) ACETOHYDRAZIDE3. THEN COMPOUND 3, ON CONDENSATION WITH VARIOUS AROMATIC ALDEHYDES WAS CONVERTED TO SCHIFF BASE DERIVATIVES 4A-J, WHICH UPON DEHYDRATIVE ANNULATION IN THE PRESENCE OF CHLOROACETYL CHLORIDE AND TRIETHYLAMINE YIELDED 3-CHLORO-4- (ARYL) -1- (2-OXO-2- (3-PHENYL-5, 6-DIHYDROIMIDAZO [2, 1-B] THIAZOLO [5, 4-D] ISOXAZOL -2 (3H) -YL) ETHYLAMINO) AZETIDIN-2-ONE5A-J, ACCORDING TO THE LITERATURE [4-5]. ALL SYNTHESIZED COMPOUNDS WERE CHARACTERIZED BY ELEMENTAL ANALYSES, IR, 1H-NMR AND 13C-NMR DATA.

HETEROCYCLIC COMPOUNDS ARE FINDING AN INCREASING USE AS INTERMEDIATES IN ORGANIC SYNTHESIS.PYRANOPYRIDINES ARE CHEMICALLY INTERESTING MOLECULES DUE TO THEIR STRUCTURAL SIMILARITY TO QUINOLINES, SUBSTITUTED PYRIDINES AND BENZOPYRANES AND ARE IMPORTANT INTERMEDIATES IN THE SYNTHESIS OF BIOLOGICALLY ACTIVE COMPOUNDS. IN THIS WORK, MULTICOMPONENT REACTIONS (MCRS) ARE CONVERGENT REACTIONS, IN WHICH THREE STARTING MATERIALS REACT THROUGH A ONE-POT PROCESS TO FORM A NEW PRODUCT THAT INCORPORATES ALL OR MOST OF THE CONTRIBUTED ATOMS. AN EFFICIENT AND STRAIGHTFORWARD PROCEDURE FOR THE SYNTHESIS OF PYRANO [3, 2-C] PYRIDINES DERIVATIVES HAS BEEN REPORTED THROUGH THE ONEPOT CONDENSATION OF MALONONITRILE, ETHYLACETOACETATE AND ARYL ALDEHYDES IN THE PRESENCE OF PIPERAZINE AS CATALYST UNDER SOLVENT-FREE MEDIA CONDITIONS BY A MICROWAVE-ASSISTED PROCESS. THE FTIR, 1H-NMR, 13C-NMR SPECTRA AND ELEMENTAL ANALYSIS CONFIRM THE STRUCTURE OF COMPOUNDS.

MULTICOMPONENT REACTIONS (MCRS) ARE AN IMPORTANT CLASS OF CONVERGENT ORGANIC REACTIONS, IN WHICH THREE OR MORE STARTING MATERIALS REACT TO FORM A PRODUCT THAT CONTAINS ATOMS DERIVED FROM ALL STARTING MATERIALS AND OFTEN HAS A HIGH ATOM ECONOMY. BECAUSE OF EXISTENCE OF THIS IMPORTANT ABILITY, IN THESE DECADE RESEARCH ON THIS AREA HAS RAPIDLY GROWN.HERE IN WE WISH TO REPORT THE FOUR-COMPONENT REACTION OF 2-FORMYLBENZOIC ACIDS, BARBITURIC ACID/THIOBARBITURIC ACID, ISOCYANIDES AND MEOH/ETOH IN WHICH PROCEEDED TO GIVE NEW BARBITURIC ACID AND THIOBARBITURIC ACID DERIVATIVES IN HIGH YIELDS IN THE ABSENCE OF ANY CATALYST UNDER REFLUX CONDITION. THE STRUCTURE OF PRODUCTS WERE DEDUCED FROM THE IR, 1H NMR, AND 13C NMR SPECTROSCOPY ANALYSIS.

1, 4-DIHYDROPYRIDINES (DHPS) ARE VERY INTERESTING COMPOUNDS DUE TO THEIR PHARMACOLOGICAL AND BIOLOGICAL PROPERTIES [1] STRUCTURE-ACTIVITY STUDIES FOR SOME DHPS INDICATE THAT THE NATURE AND POSITION OF THE SUBSTITUENTS ON THE DHP RING HAVE VERY IMPORTANT EFFECT ON THEIR BIOLOGICAL ACTIVITIES. IN VIEW OF THE IMPORTANCE OF THE UNSYMMETRICAL NATURE AT C3 AND C5 POSITIONS, SOME NEW UNSYMMETRICALLY SUBSTITUTED 1, 4-DIHYDROPYRIDINES HAVE BEEN SYNTHESIZED, IN WHICH A CARBOETHOXY GROUP (ESTER) AND ACETYL GROUP (KETO) ARE LOCATED ON THE 3- AND 5- POSITIONS, RESPECTIVELY AND INVESTIGATED CONFORMATIONAL ANALYSIS OF THEM.1, 4-DIHYDROPYRIDINES ARE FLEXIBLE MOLECULES, IN WHICH THE ARYL RING AND THE CARBONYL GROUPS CAN ROTATE, AND THE CONFORMATION OF DIHYDROPYRIDINE RING CAN CHANGE. IN THE PRESENT STUDY WE WISH TO REPORT THE THEORETICAL STUDIES ON THE ROTAMERS AND DYNAMIC BEHAVIORS OF ONE OF NEW UNSYMMETRICAL 1, 4-DIHYDROPYRIDINES: ETHYL-5-ACETYL-4-PHENYL-2, 6-DIMETHYL-1, 4-DIHYDROPYRIDINE-3-CARBOXYLATE. THE POTENTIAL ENERGY SURFACES (PES) OF ETHYL-5-ACETYL-4-PHENYL-2, 6-DIMETHYL-1, 4-DIHYDROPYRIDINE-3-CARBOXYLATE HAVE BEEN EXPLORED USING DENSITY FUNCTIONAL THEORY (DFT) B3LYP METHODS WITH 6-31G BASIS SET. IN ADDITION, THE BARRIER TO ARYL RING ROTATION OF THIS COMPOUND HAS BEEN COMPARED WITH THAT OF THE CARBONYL GROUPS ROTATION.

MICROWAVE-ASSISTED SYNTHESIS HAS BEEN UTILIZED AS A POWERFUL AND EFFECTIVE TECHNIQUE TO PROMOTE A GROUP OF CHEMICAL REACTIONS. SINCE THE FIRST PUBLICATIONS ON THE USE OF MICROWAVE IRRADIATION IN ORGANIC CHEMISTRY, THE ACCELERATED PROCESS DESCRIBED HAVE BEEN A LURE FOR CHEMISTS TO FURTHER APPLY NEW REACTIONS TO THIS TECHNOLOGY. HUISGEN’S 1, 3-DIPOLAR CYCLOADDITION OF ALKYNES AND AZIDES YIELDING TRIAZOLES IS, UNDOUBTEDLY, THE PREMIER EXAMPLE OF CLICK CHEMISTRY REACTIONS. A FAST ONE-POT MICROWAVE-ASSISTED SOLVENT FREE SYNTHESIS OF 4-NITRO-5-PHENYL-4, 5-DIHYDRO-1H- TRIAZOLE BY 1, 3-DIPOLAR CYCLOADDITION REACTIONS WITH TRIMETHYLSILYL AZIDE (ME3SI-N3) ON B-NITROSTYRENE IN GOOD YIELD IS DESCRIBED.

THERE ARE SIGNIFICANT AND INTERESTING DIFFERENCES BETWEEN COMPOUNDS WITH THIOCARBONYL AND SELENOCARBONYL GROUPS. THE C=S BOND LENGTH (~1.8 Å) IS CONSIDERABLY LONGER THAN C=S (~1.6 Å). AS A RESULT, ONE WOULD EXPECT TO BE STRENGTHS TO DIFFER SIGNIFICANTLY. THE  P-BOND ALSO MIGHT BE EXPECT TO BE STRONGLY AFFECTED IN VIEW OF THE ORBITAL SIZE MISMATCH BETWEEN SECOND AND THIRD ROW ATOMS. ON THE OTHER HAND, SELENOAMIDES ARE KNOWN TO HAVE LARGER ROTATIONAL BARRIERS THAN THIOAMIDES, WHERE THE BARRIER ARISES FROM THE INTERACTION NITROGEN WITH THE ADJACENT C=S OR C=SE GROUP. THE GEOMETRY OPTIMIZATIONS FOR THE GROUND STATE AND, TRANSITION STATES, WERE CARRIED OUT USING GAUSSIAN 03 PROGRAM WITH B3LYP LEVEL OF THEORY IN COMBINATION OF 6-311G (D, P) BASIS SET. ONE OF THE MOST IMPORTANT QUANTITIES THAT CHARACTERIZE A BOND IS THE STRENGTH. THIS CAN BE EXPRESSED EITHER AS THE BOND DISSOCIATION ENERGY OR THE FORCE CONSTANT FOR STRETCHING THE BOND. THE FIRST REFERS TO COMPLETE CLEAVAGE, AND THE LATTER TO THE EFFECTS OF SMALL DEVIATIONS FROM THE EQUILIBRIUM GEOMETRY. VIBRATIONAL FORCE CONSTANTS ARE USUALLY OBTAINED VIA A NORMAL COORDINATE ANALYSIS OR A CALCULATION OF THE VIBRATIONAL FREQUENCIES. THIS PRESENTS PROBLEMS BECAUSE THERE IS ALWAYS COUPLING BETWEEN THE C=S (OR C=SE) VIBRATION WITH OTHER VIBRATIONAL MODES. THERE IS CONSIDERABLE NO DIFFERENCE IN ELECTRONEGATIVITY BETWEEN SELENIUM AND SULFUR, AND THEREFORE THE CHARGE DISTRIBUTION SHOULD BE NO DIFFERENT BETWEEN SELENOCARBONYL AND THIOCARBONYL COMPOUND.

IN THE PAST DECADE, IR SPECTROSCOPY HAS BECOME IMPORTANT TECHNIQUES FOR OBTAINING INFORMATION ON CHEMICAL STRUCTURES AND IS APPLIED IN VIRTUALLY ALL BRANCHES OF CHEMISTRY. VIBRATIONAL SPECTROSCOPY IS USED EXTENSIVELY IN ORGANIC CHEMISTRY FOR THE IDENTIFICATION OF FUNCTIONAL GROUPS OF ORGANIC COMPOUNDS AS WELL AS FOR STUDIES ON MOLECULAR CONFORMATION, REACTION KINETICS, ETC.DENSITY FUNCTIONAL THEORY (DFT) HAS BECOME A MAJOR TOOL IN THE METHODOLOGICAL ARSENAL OF COMPUTATIONAL ORGANIC CHEMISTS. FOR A PROPER UNDERSTANDING OF IR AND RAMAN SPECTRA, A RELIABLE ASSIGNMENT OF ALL VIBRATIONAL BANDS IS ESSENTIAL.FOR THIS PURPOSE, THE QUANTUM CHEMICAL METHODS, RANGING FROM SEMI-EMPIRICAL TO DFT APPROACHES, ARE INVALUABLE TOOLS [2], EACH METHOD HA- VING ITS OWN ADVANTAGES.1, 2- DIHYDRO ACENAPHTYLIDENE-1, 2-DION WITH 4-AMINO-3- HYDRAZINE - 5 - MERCAPTO-1, 2, 4-TRIAZOLE AND THIOSEMICARBAZIDE GAVE ACENAPHTHYIENE-1, 2-BIS- (4-AMINO-5-SULFANYL-4H-1, 2, 4-TRIAZOL-3-YL) DIHYDRAZON AND 1 (2H) -ACENAPHTHYLEN-THIOSAMICARBAZONE. THESE COMPOUNDS WERE REACTED WITH DIMTHYLACETYLENDICARBOXYLATE TO OBTAIN ACENAPHTHYIENE-1, 2-BIS- [(E) -METHYL-2- (7-OXO-5H- [1, 2, 4] TRIAZOLO [3, 4-B] [1, 3, 4] THIADIAZIN-6 (7H) -YLIDEN) ACETAT-3-YL] DIHYDRAZON AND ACENAPHTHYIENE-1, 2-BIS- [(Z) -METHYL-2- (5-OXOTHIAZOLIDINE-4YL) ACETAT-3-YL] DIHYDRAZON, RESPECTIVELY IN GOOD YIELDS.THE STRUCTURES DETERMINED BY IR, NMR. EXPERIMENTAL STRUCTURES COMPARED WITH THEORETICAL CALCULATED BY DFT METHOD AT B3LYP/6-311G (D, P).

BENZODIAZEPINES ARE KNOWN AS DRUGS AFFECTING THE CENTRAL NERVOUS SYSTEM [1, 2]. ALPRAZOLAM IS ONE OF THE NEWEST AND MOST EFFECTIVE DRUGS IN THIS FAMILY. [3].CONVENTIONAL METHODS FOR PREPARING THIS COMPOUND INCLUDE THE USE OF TOXIC SUBSTANCES SUCH AS PYRIDINE AND P2S5 [4].IN THIS STUDY, A NEW METHOD FOR THE PREPARATION OF ALPRAZOLAM FROM CHLORDIAZEPOXIDE HAS BEEN DEVELOPED. CHLORDIAZEPOXIDE IS CHEAP AND AVAILABLE IN THE INDUSTRIAL SCALE. ALPRAZOLAM WAS PREPARED IN THREE STEPS. REACTION CONDITIONS WERE OPTIMIZED FOR EACH STAGE. CHLORDIAZEPOXIDE WAS CONVERTED TO ITS NITROSO DERIVATIVE BY SODIUM NITRITE. ALPRAZOLAM OXIDE WAS OBTAINED BY REACTION OF NITROSO COMPOUND WITH ACETYL HYDRAZINE. IN A DEOXYGENATION REACTION BY PHOSPHORUS TRICHLORIDE ALPRAZOLAM OXIDE WAS CONVERTED TO ALPRAZOLAM. THIS COMPOUND WAS TESTED ON USP 31. IT PASSED ALL OF THE TESTS.

SOLID-PHASE EXTRACTION (SPE) IS ONE OF THE MOST USED TECHNIQUES FOR SEPARATION OF SELECTED ANALYTES DUE TO ITS FLEXIBILITY, ENVIRONMENTAL FRIENDLY, AND SIMPLICITY. HOWEVER, THE BASIC DISADVANTAGE OF TRADITIONAL SPE ADSORBENTS IS LACK OF SELECTIVITY FOR METAL IONS WHICH LEADS TO THE INTERFERENCE OF OTHER SPECIES FOR THE DETERMINATION OF THE TARGET METAL IONS. RECENTLY, IT WAS EXTENSIVELY REPORTED THAT THE SELECTIVITY OF SPE CAN BE ENHANCED BY USING MOLECULARLY IMPRINTED POLYMER (MIP), WHICH HAVE SYNTHETIC RECOGNITION SITES WITH HIGH SELECTIVITY AND AFFINITY FOR THE TEMPLATE. ION IMPRINTING POLYMER (IIP) IS SIMILAR TO MIP, BUT THEY RECOGNIZE METALIONS [1]. THE SYNTHESIS PROCESS CAN BE EXPLAINED GENERALLY AS FOLLOWS: (1) TEMPLATE MOLECULES (ION) GRAFT ON FUNCTIONAL MONOMER UNTIL REACHING SATURATION; (2) POST-IMPRINTING OF TEMPLATE MOLECULES IS CONDUCED TOWARDS THE GRAFTED POLYMERS USING CROSS-LINKING AGENT; (3) THE POLYMER GRAFTS ON THE SURFACE OF MATRIX MATERIAL AND FORMS A THIN POLYMER LAYER [2]. IN THIS STUDY CROSSLINKED PB (II) -IMPRINTED CHITOSAN WERE PREPARED FROM CHITOSAN.WHICH CAN BE USED FOR SELECTIVE ADSORPTION OF PB (II) AT SOLID-PHASE EXTRACTION.USINGPB (II) AS TAMPLATE, KH-560 (3- (2, 3-EPOXY PROPOXY) PROPYLTRIMETHOXYSILANE) AS COUPLING AND CROSS LINKER AGENT AND MCM-41 AS SUBSTRATE.THEPB (II) IMPRINTED CHITOSAN WERE CARACTERIZED BY FOURIER INFRARED SPECTROSCOPY, X-RAY DIFFRACTION AND TG/DTG TECHNIQUE.THE RESULT SHOWED THAT THE ADSORPTION OF PB (II) -IMPRINTED CHITOSAN AFFECTED BY THE INITIAL PH, THE INITIAL CONCENTRATION, CONTACT TIME AND AMOUNT OF SORBENT, AS WELL AS TEMPERATURE.THE OPTIMAL CONDITION WERE RECOGNIZED AS; PH=5, CONTACT TIME OF 60MIN, INITIAL CONCENTRATION OF PB (II) AS 250MG/L AND ADSORBENT DOSE AS 0.1G. DATA SHOWED THE MAXIMUM ADSORPTION CAPACITY OF THE PB (II) -IMPRINTED POLYMER AND NON-IMPRINTED ONE, WAS RESPECTIVELY 44.8AND 27 MGG-1.

THE GENUSARTEMISIA FROM THE FAMILY ASTERACEAE IS A GENUS OF SMALL HERBS OR SHRUBS AND IS REPRESENTED BY 34 SPECIES GROWING IN DIFFERENT PARTS OF IRAN.ARTEMISIA LEHMANNIANA BUNGE IS A SHRUB GENERALLY 30-40 CM IN HEIGHT, WITH A WOODY ROOTSTOCK. SEVERALARTEMISIA SPECIES HAVE MEDICINAL IMPORTANCE AND ARE USED IN TRADITIONAL MEDICINE FOR THE TREATMENT OF A VARIETY OF DISEASES AND COMPLAINTS. THE ESSENTIAL OIL OF SOMEARTEMISIA SPECIES ARE ALSO USED IN SOAPS, DETERGENTS, COSMETICS, AND PERFUMES, AS AROMATHERAPY CLAIMS. THE OIL OFA. LEHMANNIANA IS USED AS A PERFUME IN THE KHODZHENT SOAP-BOILING FACTORY. THERE ARE MANY METHODS TO OBTAIN ESSENTIAL OILS FROM THE PLANT MATERIALS. MICROWAVE-ASSISTED HYDRODISTILLATION (MAHD) IS AN ADVANCED HYDRODISTILLATION (HD) TECHNIQUE, IN WHICH A MICROWAVE OVEN IS USED IN THE EXTRACTION PROCESS.IN THIS STUDY, A. LEHMANNIANA WAS COLLECTED FROM HEZAR MOUNTAIN IN THE RAYEN AREA, KERMAN PROVINCE, IRAN IN SEPTEMBER 2011 AT THE FULL FLOWERING STAGE. HD AND MAHD METHODS HAVE BEEN COMPARED FOR THEIR EFFECTIVENESS IN THE ISOLATION OF ESSENTIAL OILS FROM AERIAL PARTS OF THE PLANT. THE COMPOSITION OF THE EXTRACTED OILS WAS INVESTIGATED BY GC AND GC/MS. THE MAHD METHOD WAS SUPERIOR IN TERMS OF SAVING ENERGY AND EXTRACTION TIME (20 MIN, COMPARED TO 3 H IN HD). THE COMPONENTS OF THE ESSENTIAL OILS EXTRACTED BY BOTH HD AND MAHD METHODS WERE SIMILAR AND THE TWO OILS CONTAINED THE SAME DOMINANT CONSTITUENTS: CAMPHOR (44.7% AND 47.8%), 1, 8-CINEOLE (22.8% AND 23.6%), B-THUJONE (12.6% AND 11.2%), AND CAMPHENE (5.4% AND 5.2%), RESPECTIVELY.AS A RESULT, THE USE OF MICROWAVE IRRADIATION DID NOT ADVERSELY INFLUENCE THE COMPOSITION OF THE ESSENTIAL OIL. IN ADDITION, COMPARED TO MANY SOLVENT EXTRACTION TECHNIQUES, MAHD CAN BE SUGGESTED AS AN “ENVIRONMENTALLY FRIENDLY” AND GREEN EXTRACTION METHOD.

AZINES ARE A CLASS OF COMPOUNDS THAT UNDERGOES A WIDE VARIETY OF CHEMICAL PROCESSES AND HAVE INTERESTING CHEMICAL PROPERTIES [1]. NEW AZINES STUDIED IN THE PRESENT PAPER HAVE BEEN SYNTHESIS IN THREE STEPS. AT FIRST, A SERIES OF 2-KETOMETHYLQUINOLINES HAVE BEEN PREPARED USING THE LITERATURE METHODS [2]. TAUTOMERISM FOR THIS GROUP OF COMPOUNDS WAS ALSO REPORTED BY SEVERAL INVESTIGATORS [3]. IN THE NEXT STEP 2-KETOMETHYLQUINOLINES IN REACTION WITH HYDRAZINE IN ETHANOL SOLUTION AND A DROP OF ACETIC ACID AS A CATALYST WAS CONVERTED TO 2-KETOMETHYLQUINOLINEHYDRAZONES IN GOOD TO HIGH YIELDS. STRUCTURE OF ALL COMPOUNDS HAS BEEN ELUCIDATED USING SPECTROSCOPIC METHODS AND ELEMENTAL ANALYSIS. OUR STUDY SHOW THAT IN CHLOROFORM SOLUTION GENERALLY TWO TAUTOMERIC FORMS ARE IN EQUILIBRIUM. HOWEVER, IN SOME CASES ONLY ONE TAUTOMER WAS DETECTED.

1, 3-OXAZOLINES REPRESENT A SIMPLE HETEROCYCLIC FRAME WHICH HAS BEEN SCARCELY EXPLORED COMPARED TO THE NON-AROMATIC COUNTERPART 1, 3-OXAZOLIDINE STRUCTURE. SURPRISINGLY FOR THIS SIMPLE HETEROCYCLE, ONLY BASIC STRUCTURES RELATED TO ACETOL HAVE BEEN CONVERTED INTO 1, 3-OXAZOLINE-2-THIONES. SYNTHESIS OF 1, 3-OXAZOLINES WERE REPORTED USING EITHER CONDENSATION OF THIOCYANIC ACID OR ISOTHIOCYANATES WITH AN A-HYDROXYCARBONYL, OR CONDENSATION OF THIOPHOSGEN WITH AN AMINOKETONE. THE POSSIBLE BALANCE OF REACTIVITY OF A-HYDROXYCARBONYL SYSTEMS WITH THIOCYANIC ACID TOWARD THE FORMATION OF 1, 3-OXAZOLINE HAVE BEEN RECENTLY REPORTED.THUS, THE REACTION OF AMMONIUM THIOCYANATE1, ACID CHLORIDES 2, ALKYLBROMIDE 3 IN THE PRESENCE OF N-METHYLIMIDAZOLE UNDER SOLVENT-FREE CONDITIONS, PRODUCED 1, 3-OXAZOLES 4 IN GOOD YIELDS.

OXAZOLINES HAVE A WIDE VARIETY OF APPLICATIONS SUCH AS PHARMACEUTICAL AND BIOLOGICAL ACTIVITIES. N-ACYL ACTIVATED AZIRIDINES EASILY AFFORD RING OPENING AND CAN BE TRANSFORMED INTO THE CORRESPONDING OXAZOLINES THROUGH A RING EXPANSION REACTION IN THE PRESENCE OF SOME DIFFERENT LEWIS ACIDS. THE MAJORITY OF THESE RING ENLARGEMENTS PROCEED WITH FULL STEREOCHEMICAL CONTROL.DESPITE A FEW WORK REPORTED ON THE REACTIVITY OF AZIRIDINES, FURTHER DEVELOPMENTS IN UTILIZATION OF AZIRIDINES DERIVATIVES AS USEFUL SYNTHETIC PRECURSORS IS STILL REQUIRED. IN ADDITION, SO FAR, NO EXAMPLE HAS BEEN REPORTED IN THE LITERATURE DESCRIBING THE SYNTHESIS OF TWO REGIOISOMERS OF OXAZOLINES FROM THE SAME N-ACYL AZIRIDINES. HEREIN SEVERALN -ACYL-2-BENZOYLAZIRIDINES WERE PREVIOUSLY PREPARED CONVENIENTLY AND USED IN THE PREPARATION OF 5-BENZOYL-2, 4-DIARYL OXAZOLINES IN THE PRESENCE OF NAI, IN THIS WORK, SYNTHESIS OF SOMETRANS- 4-BENZOYL-2, 5-DIARYL OXAZOLINES BY A REGIO- AND STEREO-CONTROLLED REACTION IN THE PRESENCE OF IRON (III) NITRATE AT ROOM TEMPERATURE IS REPORTED. A PLAUSIBLE MECHANISM HAS BEEN PROPOSED FOR RING EXPANSION OF N -ACYL AZIRIDINES TO OXAZOLINES.

THE PRONOUNCED REACTIVITY OF NITROGEN-CONTAINING HETEROCYCLES TOWARDS DIALKYL ACETYLENEDICARBOXYLATES IS WELL DOCUMENTED. MULTI-COMPONENT REACTIONS (MCRS) HAVE BEEN FREQUENTLY USED BY SYNTHETIC CHEMISTS AS A FACILE MEANS TO GENERATE MOLECULAR DIVERSITY FROM BIFUNCTIONAL SUBSTRATES THAT REACT SEQUENTIALLY IN AN INTRAMOLECULAR FASHION. THE 2-PYRIDONE MOIETY IS FOUND IN A LARGE NUMBER OF PHARMACEUTICALS, AGROCHEMICALS, AND FUNCTIONAL MATERIALS. IT IS ALSO A VERSATILE SYNTHON THAT CAN ACT AS A COMMON INTERMEDIATE FOR THE PREPARATION OF A WIDE VARIETY OF ALKALOIDS. WE WISH TO REPORT HEREIN THE RESULTS OF OUR STUDIES ON THE REACTION OF ACTIVATED ACETYLENIC COMPOUNDS WITH PRIMARY AMINES IN THE PRESENCE OF CATALYTIC AMOUNT OFN METHYLIMIDAZOL UNDER SOLVENT-FREE CONDITIONS AT ROOM TEMPERATURE.

PYRROLE DERIVATIVES ARE AN IMPORTANT CLASS OF HETEROCYCLES. NITROGEN HETEROCYCLES ARE OF SYNTHETIC INTEREST BECAUSE THEY CONSTITUTE AN IMPORTANT CLASS OF NATURAL AND NON-NATURAL PRODUCT, MANY OF WHICH EXHIBIT USEFUL BIOLOGICAL ACTIVITY. ISOCYANIDE-BASED MULTICOMPONENT REACTIONS (IMCR) NOW OCCUPY A POSITION OF IMPORTANCE IN SYNTHETIC ORGANIC CHEMISTRY, MAINLY DUE TO THE CONTRIBUTIONS OF UGI AND CO-WORKERS. ORGANIC ISOCYANATES ARE POWERFUL TOOLS IN ORGANIC SYNTHESIS. GENERALLY, ISOCYANATES EASILY UNDERGO POLAR CYCLOADDITIONS WITH A LARGE VARIETY OF UNSATURATED SUBSTRATES. THE REACTIVITY OF NUCLEOPHILIC CARBENES SUCH AS ISOCYANIDES TOWARDS DIMETHYL ACETYLENEDICARBOXYLATE (DMAD) IS WELL DOCUMENTED. IN SUMMARY, WE HAVE FOUND THAT THE REACTION OF ALKYL/ARYL ISOCYANIDES WITH DIALKYL ACETYLENEDICARBOXYLATES IN THE PRESENCE OF PHENYL ISOCYANATE LEADS TO THE ONE-POT AND SIMPLE SYNTHESIS OF HIGHLY FUNCTIONALIZED 2, 5-DIHYDRO-5-OXO-1-PHENYL-1H -PYRROLE DERIVATIVES. THE STRUCTURE OF COMPOUNDS 3A-H WAS DEDUCED FROM THEIR IR, 1H NMR, 13C NMR, MASS SPECTRAL DATA AND ELEMENTAL ANALYSIS.

MULTICOMPONENT REACTIONS (MCRS), AN IMPORTANT SUBCLASS OF TANDEM REACTIONS, ARE ONE-POT PROCESSES IN WHICH THREE OR MORE EASILY ACCESSIBLE COMPONENTS REACT TO FORM A SINGLE PRODUCT, WHICH INCORPORATES ESSENTIALLY ALL OF THE ATOMS OF THE STARTING MATERIALS. MCRS ARE HIGHLY FLEXIBLE, (CHEMO) SELECTIVE, CONVERGENT, AND ATOM-EFFICIENT PROCESSES OF HIGHEXPLORATORY POWER. WE DESCRIBE AN EFFICIENT, THREE-COMPONENT, AS PART OF CURRENT STUDIES, WE DESCRIBERESULTS OF OUR STUDIES INVOLVING AN EFFICIENT, THREECOMPONENT AND ONE-POT REACTION OF ISATOIC ANHYDRIDE AND NUCLEOPHILES SUCH AS ALCOHOLS AND THIOLS IN THE PRECENCE OF PHENACYL BROMIDES TO PRODUCE THE NEW CARBOXYLIC ACID DERIVATIVES. THE PRODUCTS WERE CHARACTERIZED ON THE BASIS OF THEIR ELEMENTAL ANALYSES AND THEIR IR, 1H NMR, 13C NMR AND MASS SPECTRA.

THE GENUSZOSIMIA, BELONGING TO THE UMBELLIFERAE FAMILY, IS REPRESENTED IN THE FLORA OF IRAN BY ONLY TWO SPECIES AS ZOSIMIA ABSINTHIFOLIA (VENT.) LINK. AND Z. RADIANS BOISS. & HOHEN. Z. ABSINTHIFOLIAIS WIDELY DISTRIBUTED IN IRAN AND NEIGHBORING COUNTRIES. THE COMPOSITION OF THE OIL OF DRIED FRUITS OF Z. ABSINTHIFOLIA FROM TURKEY HAS BEEN REPORTED. N -OCTYL ACETATE (38.1%) AND N OCTYL HEXANOATE (31.9%) WERE THE MAIN CONSTITUENTS. IN ADDITION, THE COMPOSITION OF THE ESSENTIAL OIL FROM AERIAL PARTS OF THE PLANT, GROWING WILD IN IRAN, HAS BEEN REPORTED. THE MAJOR COMPONENTS WEREN -OCTYL ACETATE (24.7%) AND B-CARYOPHYLLENE (22.2%). TWO NEW FLAVONOIDS WERE ALSO ISOLATED AND IDENTIFIED FROM METHANOL EXTRACT OF THE AERIAL PARTS OF THE PLANT. IN THIS STUDY, Z. ABSINTHIFOLIA WAS COLLECTED FROM BARDSIR, THE KHANSAR REGION, KERMAN PROVINCE, IRAN IN JUNE 2011. THE AIR-DRIED FRUITS OF THE PLANT (100 G) WERE POWDERED AND SUBJECTED TO HYDRODISTILLATION FOR 3 H USING A CLEVENGER-TYPE APPARATUS. THE CLEAR YELLOWISH OIL WAS ISOLATED IN THE YIELD OF 0.8% (W/W). THE COMPOSITION OF THE EXTRACTED OIL WAS ANALYZED BY GC AND GC/MS. GC ANALYSIS WAS CARRIED OUT USING A SHIMADZU 15A INSTRUMENT COUPLED TO A FLAME IONIZATION DETECTOR (FID). AN AGILENT 5975C MASS SPECTROMETER COUPLED TO AN AGILENT 7890A GAS CHROMATOGRAPH EQUIPPED WITH A HP-5MS CAPILLARY COLUMN WAS USED FOR GC/MS ANALYSIS. FOURTEEN COMPOUNDS WERE IDENTIFIED IN THE FRUIT OIL OF Z. ABSINTHIFOLIA, REPRESENTING 99.2% OF THE TOTAL OIL. THE OIL WAS CHARACTERIZED BY A HIGH CONTENT OF N -OCTYL ACETATE (69.8%) AS THE MAIN COMPOUND, FOLLOWED BY NOCTANOL (8.3%), Α-PINENE (4.6%), BORNYL ACETATE (4.3%), B -CARYOPHYLLENE (3.1%), AND CAMPHENE (2.0%). CONSEQUENTLY, THE FRUIT OIL OFZ. ABSINTHIFOLIA WAS RICH IN NONTERPENOID COMPOUNDS (79.7%).

1, 3-DIPOLAR CYCLOADDITION OF AZOMETHINE YLIDES IS A POWEFULL METHOD FOR THE SYNTHESIS OF HIGHLY FUNCTIONALISED FIVE-MEMBERED RING HETEROCYCLES. SOME SPIROPYRROLIDINES ARE POTENTIAL AS ANTILEUKEMIC AND ANTICONVULSANT AGENTS AND POSSESS ANTIVIRAL AND LOCAL ANAESTHETIC ACTIVITIES. IN THIS REPORT, AT FIRST WE PREPARED CHIRAL NON-RACEMIC DIPOLAROPHILES FROM THE REACTION OF ACRYLATES WITH PURE OXAZOLIDINONE AS ACHIRAL AUXILIARY. THEN THE REACTIONS WERE CARRIED OUT IN A ONEPOT AND PROCEEDED THROUGH A 1, 3-DIPOLAR CYCLOADDITION REACTION OF THE CHIRAL DIPOLAROPHILES WITH NON-STABILIZED AZOMETHINE YLIDES GENERATEDIN SITU BY THE CONDENSATION REACTION OF ISATINS WITH LPROLINE.AFTER REMOVAL OF OXAZOLIDINONE THE NEW CHIRAL SPIRO OXINDOLO- PYRROLIZIDINES WERE OBTAINED IN HIGH YIELD AND ENANTIOMERIC EXCESS. THE CONFIGURATION OF ONE OF THE CYCLOADDITION PRODUCTS CONFIRMED BY X-RAY SINGLE CRYSTAL, AND THEORETICAL CALCULATIONS.

BECAUSE OF THE STRAIN INDUCED BY THE PRESENCE OF A THREE MEMBERED RING [1], EPOXIDES ARE SIGNIFICANTLY MORE REACTIVE THAN TO OTHER ETHERS. THUS, THEY BECOME AS USEFUL BUILDING BLOG COMPOUNDS IN ORGANIC SYNTHESIS. SYNTHETIC PROCEDURES FOR EPOXIDE RING OPENING CAN BE BASED ON NUCLEOPHILIC OR PROTIC/LEWIS ACID-MEDIATED ELECTROPHILIC RING OPENING. A NUMBER OF PROCEDURES WHICH FEATURE THE OXYPHILIC LEWIS CHARACTER OF METAL IONS AND NON-METALLIC LEWIS ACIDS HAVE BEEN DEVELOPED. SUITABLE EPOXIDE OPENING CATALYSTS INCLUDE LEWIS ACIDS, LEWIS BASES, BRONSTED ACIDS, THIOXANTHENONE-FUSED AZACROWN ETHERS, SCHIFF BASE AND PORPHYRIN COMPLEXES.ALSO, COMPOUNDS CONTAINING AN IMINE GROUP ARE INCREASINGLY IMPORTANT IN ORGANIC SYNTHESIS AND THE MECHANISM OF THE CIS/TRANS ISOMERIZATION OF IMINES IS BEING STUDIED IN DETAIL. THE 1, 3-OXATHIOLANE-2-IMINE STRUCTURES INCLUDES AN EXOCYCLIC IMINE GROUP AND CAN BE USED IN ORGANIC SYNTHESIS FOR THE PREPARATION OF BIOLOGICALLY ACTIVE COMPOUNDS. AS PART OF OUR CURRENT STUDIES ON THE DEVELOPMENT OF NEW ROUTES IN HETEROCYCLIC SYNTHESIS, WE REPORT AN EFFICIENT PROCEDURE FOR DIRECT SYNTHESIS OF 1, 3-OXATHIOLAN DERIVATIVES4 FROM THE REACTION OF EOPXIDE 1, CARBON DISULFIDE 2 AND CHACIDS 3MICROWAVE CONDITIONS AT 70OC IN EXCELLENT YIELD (SCHEME 1).

RECOVERY OF ALDEHYDES AND KETONES FROM OXIMES IS ONE OF THE MOST IMPORTANT REACTIONS IN ORGANIC SYNTHESIS, BECAUSE OXIMES ARE SERVED AS AN EFFICIENT PROTECTIVE GROUP FOR CARBONYL COMPOUNDS WHICH ARE EXTENSIVELY USED FOR THE PURIFICATION OF CARBONYL COMPOUNDS. AT THE SAME TIME, OXIMES COULD BE PREPARED FROM NON-CARBONYL COMPOUNDS, AND THE REGENERATION OF CARBONYL COMPOUNDS FROM OXIMES REPRESENTS A POTENTIAL ROUTE FOR SYNTHESIS OF ALDEHYDES AND KETONES.VARIOUS METHODS INCLUDING HYDROLYSIS BY ACIDS, REDUCTIVE DEOXIMATION AND OXIDATIVE DEOXIMATION HAVE BEEN DEVELOPED FOR THIS PROCESS. UNFORTUNATELY IN MOST OF THE REPORTED PROTOCOLS, USING STOICHIOMETRIC AMOUNTS OF ACID, OXIDIZING OR REDUCING AGENTS INCORPORATED WITH LOW TO MODERATE YIELDS ARE MAJOR SHORTCOMINGS AND PUTS SOME RESTRICTIONS FOR THE APPLICATION FOR LARGE SCALE SYNTHESIS. THEREFORE, THE DEVELOPMENT OF CLEAN, SELECTIVE AND EFFICIENT PROTOCOL FOR CLEAVAGE OF NITROGEN-CONTAINING DERIVATIVES SPECIALLY OXIMES TO AFFORD CARBONYL COMPOUNDS IS HIGHLY DESIRABLE.WE REPORT HERE AN EFFICIENT AND RAPID DEOXIMATION METHOD USING NANO CRO3-ALCL3 SYSTEM, FOR CONVERSION OF VARIOUS OXIMES TO THE CORRESPONDING CARBONYLS UNDER SOLVENT-FREE CONDITIONS. THIS METHOD OFFERS SOME ADVANTAGES IN TERM OF CLEAN REACTION CONDITIONS, SHORT REACTION TIMES, EASY WORK-UP PROCEDURE AND HIGH YIELDS (SCHEME).

THE ADDITION REACTION BETWEEN ELECTRON-DEFICIENT ACETYLENIC COMPOUNDS AND NITROGEN-CONTAINING HETEROCYCLES HAS BEEN EXTENSIVELY INVESTIGATED.1 THE REACTION OF PYRIDINE WITH DIMETHYL ACETYLENEDICARBOXYLATE (DMAD) YIELDS A ZWITTERIONIC COMPOUND WHICH CAN BE TRAPPED BY VARIOUS ELECTROPHILES.1, 2 WHEN THE REACTION OF PYRIDINE AND DMAD WAS CARRIED OUT IN THE PRESENCE OF CHACIDS SUCH AS DIMEDONE, OR 1, 3-INDANDIONE 1, 4-DIIONIC DERIVATIVES WERE OBTAINED.2 HERE WE REPORT THE REACTION BETWEEN 2, 6-DICHLOROPYRIDINE (DCP) WITH DIMETHYL ACETYLENEDICARBOXYLATE IN DIFFERENT ALCOHOLS AS SOLVENT. THUS REACTION BETWEEN DMAD AND DCP IN METHANOL AFTER 2 H STIRRING AT ROOM TEMPERATURE AFFORDED VINYL ETHER DERIVATIVE 3A. SIMILAR REACTIONS WERE CARRIED OUT WITH ETHANOL AND ISOPROPYL ALCOHOL AND SIMILAR PRODUCTS WERE OBTAINED IN GOOD YIELDS. THE NMR SPECTRA OF PRODUCTS SHOWED THE PRESENCE OF TWO REGIOISOMERS. THIS REACTINS MAY ALSO HAVE BEEN DONE WITH CATALYTIC AMOUNTS OF DCP (20 MOL%).

SCHIFF BASES AND THE RELEVANT METAL COMPLEXES HAVE GREAT INTEREST IN COORDINATION CHEMISTRY ALTHOUGH THIS SUBJECT HAS BEEN EXTENSIVELY STUDIED. THESE COMPOUNDS EXHIBIT BIOLOGICAL ACTIVITY AS ANTIVIRAL AND ANTITUMOR, THEY HAVE ATTRACTED MUCH INTEREST IN RECENT YEARS DUE TO THEIR SIGNIFICANCE IN THE DEVELOPMENT OF NEW THERAPEUTIC AGENT.THERE ARE NO REPORTED MACROACYCLIC SCHIFF BASE LIGAND DERIVED FROM 2-HYDROXY NAPHTHALDEHYDE INCORPORATING PENDANT ALCOHOL FUNCTION. IN THIS RESEARCH WORK WE REPORT THE SYNTHESIS AND CHARACTERIZATIONOF2- [3- (2-FORMYLNAPHTHOXY) -2-HYROXYPROPOXY] NAPHTHALDEHYDE AND ITS TWO MACROACYCLE SCHIFF BASE LIGANDS. THE HYDROXYL GROUP AT THE C-BACKBONE IN THESE COMPOUNDS HAS BEEN CHOSEN BECAUSE IT IS EASILY TRANSFORMED TO AMINES OR OTHER SUBSTITUENTS WITH LINKING POTENTIAL FOR ATTACHMENT TO OTHER SUBSTRATES TO PRODUCE, FOR EXAMPLE, IMMOBILIZED SYSTEMS FOR METAL-ION SCAVENGING.2- [3- (2-FORMYLNAPHTHOXY) -2-HYROXYPROPOXY] NAPHTHALDEHYDE WAS PREPARED BY THE METHOD OF LINDOY AND ARMSTRONG [4] WITH MINOR MODIFICATION. ALL OF THESE THREE COMPOUNDS SYNTHESIZED FOR FIRST TIME AND CHARACTERIZED BY FT-IR, 1H AND13C NMR AND ELEMENTAL ANALYSIS TECHNIQUES.

IMIDAZOLES AND BENZIMIDAZOLES ARE FREQUENTLY FOUND IN A DIVERSE ARRAY OF COMPOUNDS, INCLUDING BIOLOGICALLY AND THERAPEUTICALLY ACTIVE AGENTS, NATURAL PRODUCTS AND FUNCTIONAL MATERIALS [1, 2].VARIOUS HETEROCYCLIC DERIVATIVES OF 4-PYRONES HAVE ALSO BEEN THE SUBJECT OF SEVERAL SYNTHETIC STUDIES, OWING TO THEIR VARIOUS BIOLOGICAL PROPERTIES SUCH ASANTICOAGULATION [3]. THROUGHOUT OUR RECENT WORKS ON SYNTHESIS OF NEW POLYCYCLIC AND FUNCTIONAL 4-PYRONES BASED ON BAYLIS-HILLMAN CHEMISTRY OR CROSS COUPLING REACTIONS [4, 5], WE REPORT HERE THE SYNTHESIS OF NEW IMIDAZOLYL AND BENZIMIDAZOLYL DERIVATIVES OF 4-PYRONES BY PD (OAC) 2 CATALYZED COUPLING OF THESE AZAARYLS WITH 3, 5-DIBROMO-2, 6-DIARYL-4-PYRONES IN THE PRESENCE OF N, N’-DIBUTYLBENZIMIDAZOL-2-YLIDENE AS LIGAND IN DMF AT 120OC. A MIXTURE OF N - AND C - MONOARYLATED PRODUCTS WERE OBTAINED WHICH WERE PURIFIED USING PLC AND CHARACTERIZED WITH SPECTROSCOPIC METHODS.

1, 4-DIHYDROPYRIDINES (DHPS) ARE VERY INTERESTING COMPOUNDS DUE TO THEIR PHARMACOLOGICAL AND BIOLOGICAL PROPERTIES. THE OXIDATION OF DIHYDROPYRIDINES PROVIDES AN EFFICIENT ACCESS TO THE CORRESPONDING PYRIDINES. IT IS IMPORTANT TO STUDY THE OXIDATION OF 1, 4-DIHYDROPYRINE DERIVATIVES, BECAUSE THE TREATMENT OF HYPERTENSION PROCEEDS THROUGH THE OXIDATION OF 1, 4-DIHYDROPYRIDINES.IN CONNECTION WITH OUR PREVIOUS WORK ON THE CHEMISTRY OF 1, 4-DIHYDROPYRIDINES [4, 5], WE WISH TO REPORT THE RESULTS OBTAINED FROM A STUDY OF THE OXIDATION OF SOME 1, 4-DIHYDROPYRIDINES WITH POTASSIUM PERMANGANATE ABSORBED ON THE VERY INEXPENSIVE AND READILY AVAILABLE SUPPORT, AL2O3 UNDER SOLVENT FREE CONDITIONS. THIS PROCEDURE GIVES PRODUCTS IN GOOD YIELDS.WE HAVE ALSO INVESTIGATED THE OXIDATION OF THESE COMPOUNDS USING CITED REAGENTS UNDER MICROWAVE IRRADIATION. WE HAVE OBSERVED THAT THE TYPE OF FORMED PRODUCTS UNDER BOTH CONDITIONS (WITH AND WITHOUT MICROWAVE) IS THE SAME; HOWEVER THE REACTION IS ACCELERATED UNDER MICROWAVE IRRADIATION.WE HAVE ALSO INVESTIGATED THE EFFECT OF THE TYPE AND NATURE OF THE 4-SUBSTITUENTS.

THE DEVELOPMENT OF NEW AND SIMPLE SYNTHETIC APPROACHES FOR FULLY USED ORGANIC COMPOUNDS FROM READILY AVAILABLE REAGENTS IS ONE OF THE MAJOR AIMS IN ORGANIC SYNTHESIS. THE MULTICOMPONENT REACTIONS (MCRS), BY VIRTUE OF THEIR CONVERGENCE, PRODUCTIVITY, FACILE EXECUTION AND GENERALLY HIGH YIELDS OF PRODUCTS, HAVE ATTRACTED MUCH ATTENTION FROM THE VANTAGE POINT OF SYNTHETIC CHEMISTRY. IN PARTICULAR, ISOCYANIDE-BASED MULTICOMPONENT REACTIONS APPLY TO THE SYNTHESIS OF VARIOUS FURAN AND FURAN DERIVATIVES. WE NOW REPORT THE RESULT OF OUR INVESTIGATIONS FOR THE REACTION BETWEEN ALKYL (ARYL) ISOCYANIDES1 AND DIALKYL ACETYLENEDICARBOXYLATES 2 IN THE PRESENCE OF ETHYL TRIFLUOROACETATE3 IN REFLUXING CH2CL2. THE ONE-POT THREE-COMPONENT CONDENSATION REACTION WAS PROCEEDED AT 38OC AND COMPLETED AFTER 24H TO AFFORD DIALKYL 5- [ALKYL (ARYL) IMINO] -2-ETHOXY-2- (TRIFLUOROMETHYL) -2, 5-DIHYDROFURAN-3, 4-DICARBOXYLATE4 IN GOOD ISOLATED YIELDS IN THE ABSENCE OF A CATALYST. THE STRUCTURE OF COMPOUNDS4A-J WAS DEDUCED FROM THEIR IR, 1H NMR, 13C NMR, 19F NMR, MASS SPECTRAL DATA AND ELEMENTAL ANALYSIS. THE PRESENT PROCEDURE HAS THE ADVANTAGE THAT NOT ONLY THE REACTION IS PERFORMED UNDER NEUTRAL CONDITIONS BUT ALSO THE REACTANTS CAN BE MIXED WITHOUT ANY ACTIVATION OR MODIFICATION.

THE ASYMMETRIC MANNICH REACTION HAS BEEN KNOWN AS ONE OF PIVOTAL SYNTHETIC ROUTES FOR C-C BOND FORMING REACTIONS TO PRODUCE CHIRAL B-AMINO CARBONYL COMPOUNDS FROM ENOLIZABLE KETONE AND A SCHIFF BASE. THESE PRODUCTS AS KEY INTERMEDIATES HAS BEEN DRAWING ATTENTION DUE TO THEIR ATOMECONOMY AND APPLICATIONS IN NATURALLY, PHARMACEUTICALLY AND BIOLOGICALLY ACTIVE COMPOUNDS. IN THIS INVESTIGATION WE DESIGNING THE DIRECT, THREE- COMPONENT MANNICH REACTIONS IN ETHANOLIC MIXTURE OF CYCLOHEXANON SYSTEMS WITH A VARIETY OF AROMATIC ALDEHYDES AND ANILINE DERIVATIVES PROCEEDED TO AFFORD THE CORRESPONDING B -AMINO KETONES WITH ANTI SELECTIVITY IN GOOD TO HIGH YIELDS WITHIN SHORT TIME. THE PROCESS IS MILD, HIGHLY EFFICIENT AND RECYCLABLE WITH THE USE OF VERY CATALYTIC AMOUNT OF HETROPOLYACID.

POLYIMIDES HAVE BEEN USED EXTENSIVELY IN THE AEROSPACE AND ELECTRONICS FIELDS BECAUSE OF THEIR THERMAL STABILITY AND EXCELLENT MECHANICAL AND ELECTRICAL PROPERTIES. DESPITE THEIR WIDESPREAD USE, POLYIMIDES ARE GENERALLY INTRACTABLE AND LACK THE PROPERTIES ESSENTIAL FOR SUCCESSFUL FABRICATION INTO USEFUL FORMS BECAUSE OF THEIR HIGH MELTING AND THEIR LIMITED SOLUBILITY IN ORGANIC SOLVENTS.ONE OF THE IMPORTANT MODIFICATIONS FOR MAKING PROCESSABLE POLYIMIDES IS COPOLYMERIZATION. IT HAS BEEN GENERALLY RECOGNIZED THAT FLEXIBLE LINKAGES AND THE BULKY LATERAL GROUPS IMPART BETTER SOLUBILITY AND MELT-PROCESSING CHARACTERISTICS COMPARED WITH POLYMERS WITHOUT THESE LINKAGES.THREE SERIES OF MODIFIED POLY (IMIDE-AMIDE) S, PIAS, WERE PREPARED FROM DICARBOXYLIC ACIDS, 1, 2, A N D 3, WITH VARIOUS DIAMINES BY THE DIRECT POLYCONDENSATION IN N -METHYL-2-PYRROLIDINONE (NMP) USING TRIPHENYL PHOSPHITE AND PYRIDINE AS CONDENSING AGENTS. THE CHARACTERIZATION OF THE POLYMERS WAS PERFORMED WITH INHERENT VISCOSITY MEASUREMENTS, SOLUBILITY TESTS, FT-IR, AND 1H-NMR SPECTROSCOPY AND THERMOGRAVIMETRY. ALL THE POLYMERS WERE OBTAINED IN QUANTITATIVE YIELDS WITH INHERENT VISCOSITIES OF 0.39-0.65 DL G-1. FOR COMPARATIVE PURPOSES, THE CORRESPONDING UNSUBSTITUTED PIAS WERE ALSO PREPARED BY REACTING A DICARBOXYLIC ACID MONOMER4 (LACKING PENDENT GROUP) WITH THE SAME DIAMINES UNDER SIMILAR CONDITIONS. THE SOLUBILITIES OF MODIFIED POLYMERS IN COMMON ORGANIC SOLVENTS AS WELL AS THEIR THERMAL STABILITY WERE ENHANCED COMPARED TO THOSE OF THE CORRESPONDING UNMODIFIED PIAS.

IN RECENT YEARS, AN INCREASING INTEREST HAS BEEN FOCUSED ON THE SYNTHESIS OF 1, 4-DIHYDROPYRIDYL COMPOUNDS OWING TO THEIR SIGNIFICANT BIOLOGICAL ACTIVITY. GENERALLY, THE BASIC SKELETON OF DHP WAS FIRST DISCOVERED BY HANTZSCH IN 1882 AND THIS CLASSICAL METHOD INVOLVES THE THREE-COMPONENT COUPLING OF AN ALDEHYDE WITH ETHYL ACETOACETATE AND AMMONIA IN ACETIC ACID OR IN REFLUXING ALCOHOL. NUMEROUS METHODS HAVE BEEN REPORTED FOR THE SYNTHESIS OF POLYHYDROQUINOLINE DERIVATIVES, BECAUSE OF THE BIOLOGICAL IMPORTANCE ASSOCIATED WITH 1, 4-DHP RING AND POLYHYDROQUINOLINE DERIVATIVES. HOWEVER, THESE METHODS SUFFER FROM DRAWBACKS SUCH AS A LONG REACTION TIME, AN EXCESS OF ORGANIC SOLVENT, LOWER PRODUCT YIELDS, AND HARSH REFLUXING CONDITIONS. IN RECENT YEARS, THE DIRECTION OF SCIENCE AND TECHNOLOGY HAS BEEN SHIFTING MORE TOWARDS ECOFRIENDLY, NATURAL PRODUCT RESOURCES AND REUSABLE CATALYSTS. THUS, NATURAL BIOPOLYMERS ARE ATTRACTIVE CANDIDATES IN THE SEARCH FOR SUCH SOLID SUPPORT CATALYSTS. THE PRESENT STUDY DESCRIBES A CONVENIENT AND EFFICIENT PROCESS FOR THE SYNTHESIS OF POLYHYDROQUINOLINE DERIVATIVES THROUGH A FOUR-COMPONENT COUPLING OF VARIOUS AROMATIC ALDEHYDES, 5, 5-DIMETHYL-1, 3-CYCLOHEXANEDIONE, ETHYL ACETOACETATE, AND AMMONIUM ACETATE IN A SOLVENT-FREE MEDIA AT 100OC USING STARCH SUPPORTED HCLO4 (STARCH/HCLO4) AS A HETEROGENEOUS CATALYST. THE CATALYST IS HIGHLY ACTIVE, STABLE, AND COULD BE REUSED SEVERAL TIMES WITHOUT MUCH LOSS OF ITS ACTIVITY.

ONE OF THE POWERFUL TOOLS USED TO JOIN ECONOMIC ASPECTS WITH THE ENVIRONMENTAL CONCERNS IS PERFORMING ORGANIC REACTIONS IN WATER; THIS STRATEGY CONSISTS OF TWO OR MORE SYNTHETIC STEPS, WHICH ARE CARRIED OUT IN WATER AS A CHEAP, NONTOXIC, ENVIRONMENTALLY FRIENDLY SOLVENT, IN A ONE-STEP REACTION, WITHOUT ISOLATION OF ANY INTERMEDIATE THUS REDUCING TIME, SAVING MONEY, ENERGY AND RAW MATERIALS. MULTICOMPONENT REACTIONS (MCRS), WITH THREE OR MORE REACTANTS COMBINE IN A ONE-POT PROCEDURE TO GIVE A SINGLE PRODUCT, HAVE BECOME INCREASINGLY POPULAR DURING THE LAST DECADE.MCRS ARE PERFECTLY SUITED FOR COMBINATORIAL LIBRARY SYNTHESIS, AND THUS ARE FINDING INCREASED USE IN THE DISCOVERY PROCESS FOR NEW DRUGS AND AGROCHEMICALS.HEREIN WE DESCRIBE AN EFFICIENT SYNTHESIS OF CYCLOPENTADIENE DERIVATIVES5 VIA THE REACTION OF TRIPHENYLPHOSPHINE1, DIALKYL ACETYLENEDICARBOXYLAT 2, 3, AND PRIMARY AMINES 4 IN WATER AS THE SOLVENT AT 80OC IN GOOD YIELDS WITHOUT USING ANY CATALYST AND LOW TIME.

1, 4-DIHYDROPYRIDINES ARE VERY INTERESTING COMPOUNDS AND PLAY AN IMPORTANT ROLE IN SYNTHETIC THERAPEUTIC AND BIOORGANIC CHEMISTRY. THE OXIDATIVE AROMATIZATION OF DIHYDROPYRIDINES TO THE CORRESPONDING PYRIDINE DERIVATIVES CONSTITUTES THE PRINCIPAL METABOLIC ROUTE IN PARTICULAR IN BIOLOGICALLY SIGNIFICANT NADH REDOX PROCESS.POTASSIUM PERMANGANATE IS A GOOD REAGENT FOR OXIDATION OF MANY COMPOUNDS. IT WAS SHOWN THAT THE ADSORPTION ON TO SOLID SUPPORTS CAN CHANGE THE REACTIVITY AND SELECTIVITY OF KMNO4 IN OXIDATION REACTIONS.IN CONNECTION WITH OUR PREVIOUS WORK ON THE CHEMISTRY OF 1, 4-DIHYDROPYRIDINES, WE WISH TO REPORT THE RESULTS OBTAINED FROM A STUDY OF THE OXIDATION OF SOME 1, 4-DIHYDROPYRIDINES WITH POTASSIUM PERMANGANATE ABSORBED ON THE MONTMORILLONITE K10 UNDER SOLVENT FREE CONDITIONS. THIS METHOD PROVIDES PYRIDINES IN GOOD YIELDS. WEHAVE ALSO INVESTIGATED THE EFFECT OF THE TYPE AND NATURE OF THE 4-SUBSTITUENTS.

OUR NANOCATALYST, THE MCM-41 SUPPORTED SCHIFF BASE COMPLEX OF TUNGSTEN WAS PREPARED AND CHARACTERIZED WITH FT-IR, ATOMIC ABSORPTION SPECTROSCOPY, XRD AND BET NITROGEN SORPTION METHOD ACCORDING TO THE PREVIOUS WORK. SOME OF THE REAGENTS REPORTED FOR OXIDATION ARE OFTEN HAZARDOUS OR VERY TOXIC OR EXPENSIVE, THEY NEED TO BE FRESHLY PREPARED OR THE REACTION REQUIRE DRASTIC CONDITIONS, LONG REACTION TIMES AND TEDIOUS WORKUP. THUS A MILDER, GREEN, SELECTIVE, NONHAZARDOUS AND INEXPENSIVE REAGENT IS STILL IN DEMAND.H2O2 IS KNOWN TO BRING ABOUT CERTAIN DESIRABLE CHEMICAL TRANSFORMATIONS WITHOUT CREATING UNWANTED BYPRODUCTS, THEREBY ELIMINATING MANY PROBLEMS AND COSTS ASSOCIATED WITH ENVIRONMENTAL CLEANUP.THIS ARTICLE DESCRIBES THE DEVELOPMENT OF GREEN, EFFICIENT H2O2 -BASED OXIDATION SYSTEM.NEW TYPE OF HETEROGENEOUS NANOCATALYST FOR DEOXIMATION BASED ON TUNGSTEN OXIDE SUPPORTED ON MESOPOROUS MOLECULAR SIEVE MCM-41WAS DEVELOPED. THIS NEW SYSTEM REPRESENTES INEXPENSIVE AND HIGHLY ACTIVE HETEROGENEOUS NANOCATALYST FOR OXIDATION UNDER GREEN AND MILD REACTION CONDITIONS.PRIMARY AND SECONDARY BENZYLIC ALCOHOLS WERE OXIDIZED TO THE CORRESPONDING CARBONYL COMPOUNDS IN GOOD TO HIGH YIELDS BY ENVIRONMENTALLY FRIENDLY AND GREEN OXIDANT, H2O2 CATALYZED BY TUNGSTEN OXIDE SUPPORTED ON MESOPOROUS MOLECULAR SIEVE MCM-41. NEW TYPE OF HETEROGENEOUS NANOCATALYST FOR OXIDATION BASED ON TUNGSTEN OXIDE SUPPORTED ON MESOPOROUS MOLECULAR SIEVE MCM-41 WAS DEVELOPED. THIS NEW SYSTEM REPRESENTES INEXPENSIVE AND HIGHLY ACTIVE HETEROGENEOUS NANOCATALYST FOR OXIDATION UNDER GREEN AND MILD REACTION CONDITIONS.

IRON IS ONE OF THE MOST ABUNDANT AND ENVIRONMENTALLY FRIENDLY METALS ON THE EARTH AND SEVERAL GROUPS HAVE REPORTED VARIOUS IRON METAL-CATALYZED ORGANIC TRANSFORMATIONS DURING THE PAST DECADES.1 IRON CATALYSTS IN ORGANIC REACTIONS HAVE RECENTLY RECEIVED MUCH ATTENTION IN VIEW OF THEIR CHEAPNESS AND ENVIRONMENTAL FRIENDLINESS. AMOUNG THEM FERRIC PERCHLORATE AND FERRIC PERCHLORATE ADSORBED ON SILICA GEL ARE RANKED AS POWERFUL LEWIS ACIDS FOR AFFECTING VARIOUS ORGANIC TRANSFORMATIONS.2LATELY, FERRIC PERCHLORATE ADSORBED ON SILICA GEL HAS ALSO BEEN FOUND TO BE EFFECTIVE FOR THE RAPID ORGANIC FUNCTIONAL GROUP TRANSFORMATIONS SUCH AS DIMERIZATION OF ALKYNES, AROMATIC HYDROCARBONS, SELECTIVE OXIDATION OF THIOLS TO DISULFIDES, AND TRANSANNULAR REACTION IN 1, 5-CYCLOOCTADIENES ON GRINDING USING PESTLE AND MORTAR IN THE SOLID STATE AND ALUMINA-SUPPORTED IRON (III) PERCHLORATE [FE (CLO4) 3.AL2O3] HAVE BEEN EFFECTIVELY USED AS A LEWIS ACID CATALYST FOR NAZAROV CYCLIZATION/MICHAEL ADDITION OF PYRROLE DERIVATIVES.1ON GOING PREVIOUSLY OUR RESEARCH TO INTRODUCE THE CATALYTIC PROTOCOL FOR THE SYNTHESIS OF HETEROCYCLIC COMPOUNDS USING ECO-FRIENDLY CATALYSTS, 3, 4 CATALYTIC SYNTHESIS OF PYRANOAND FURANOQUINOLINES USING ARYL AMINES, 3, 4-DIHYDRO-2H-PYRAN (DHP) AND 2, 3-DIHYDROFURAN (DHF) IS REPORTED IN THE PRESENCE OF LEWIS ACIDS SUCH AS FE (CLO4) 3.6H2O AND FE (CLO4) 3/SIO2) AS CATALYST UNDER MILD CONDITION WITHOUT SOLVENT (SCHEME 1).

TOBACCO IS AN AGRICULTURAL PRODUCT PROCESSED FROM THE LEAVES OF PLANTS IN THE GENUS NICOTIANA. IT CAN BE CONSUMED, USED AS A PESTICIDE AND, IN THE FORM OF NICOTINE TARTRATE, USED IN SOME MEDICINES. IT IS MOST COMMONLY USED AS A DRUG, AND IS A VALUABLE CASH CROP FOR COUNTRIES SUCH AS CUBA, CHINA AND THE UNITED STATES. TOBACCO IS A NAME FOR ANY PLANT OF THE GENUS NICOTIANA OF THE SOLANACEAE FAMILY (NIGHTSHADE FAMILY) AND FOR THE PRODUCT MANUFACTURED FROM THE LEAF AND USED IN CIGARS AND CIGARETTES, SNUFF, AND PIPE AND CHEWING TOBACCO. TOBACCO PLANTS ARE ALSO USED IN PLANT BIOENGINEERING, AND SOME OF THE 60 SPECIES ARE GROWN AS ORNAMENTALS. THE ALKALOID NICOTINE IS THE MOST CHARACTERISTIC CONSTITUENT OF TOBACCO AND IS RESPONSIBLE FOR ITS ADDICTIVE NATURE. THE HARMFUL EFFECTS OF TOBACCO DERIVE FROM THE THOUSANDS OF DIFFERENT COMPOUNDS GENERATED IN THE SMOKE, INCLUDING POLYCYCLIC AROMATIC HYDROCARBONS (SUCH AS BENZPYRENE), FORMALDEHYDE, CADMIUM, NICKEL, ARSENIC, RADIOACTIVE POLONIUM-210, TOBACCO-SPECIFIC NITROSAMINES (TSNAS), PHENOLS, AND MANY OTHERS. IN THIS INVESTIGATION WE ARE DESCRIBED SEPARATION AND IDENTIFICATION OF COMPOUNDS IN THE VIRGINIA TOBACCO AT NORTH OF IRAN. BY SPECTROSCOPIC METHOD, WAS IDENTIFIED SOME COMPONENT OF THIS SPECIE OF TOBACCO.

POLYURETHANES (PU) S ARE A CLASS OF VERSATILE ENGINEERING MATERIALS BECAUSE OF THEIR EXCELLENT PROPERTIES SUCH AS HIGH ABRASION RESISTANCE, EXCELLENT FLEXIBILITY, CHEMICAL RESISTANCE, AND DAMPING ABILITY. DESPITE THE MERITS OF THIS VERSATILE POLYMER, ITS THERMAL STABILITY IS A POINT OF CONCERN, WHICH RESTRICTS ITS APPLICATION ABOVE 150°C, WHERE ITS ACCEPTABLE MECHANICAL PROPERTIES VANISH.THEREFORE, SIGNIFICANT SYNTHETIC EFFORTS HAVE BEEN FOCUSED ON IMPROVING THE HEAT-RESISTANCE OF PUS BY ALLOYING OR COPOLYMERIZATION WITH POLYIMIDES WHILE MAINTAINING THEIR EXCELLENT PHYSICAL, MECHANICAL AND ELECTRICAL PROPERTIES OVER A WIDE TEMPERATURE RANGE. POLYMERS WITH OPTICALLY ACTIVE PROPERTIES HAVE FOUND SUCCESSFUL USES AS CHIRAL STATIONARY PHASES FOR ENANTIOMERIC SEPARATIONS AND SHOWN POTENTIAL APPLICATIONS IN ASYMMETRIC CATALYTIC REACTIONS, AND BIOMEDICAL DEVICES [6], ETC. THE OBJECTIVE OF THIS STUDY IS TO SYNTHESIZE AND CHARACTERIZE THE OPTICALLY ACTIVE POLY (IMIDE–URETHANE) S (PIU) S DERIVED FROM DIACYLAZIDE1 AND VARIOUS AROMATIC DIOLS IN DRY TOLUENE UNDER REFLUXING IN THE PRESENCE OF 1, 4-DIAZABICYCLO [2.2.2] OCTANE (DABCO, TRIETHYLENEDIAMINE) AS A CATALYST VIA ‘‘ONE-POT’’ PROCEDURE. THE THERMAL AND CHIROPTICAL PROPERTIES OF THE PRODUCTS AS WELL AS THEIR SOLUBILITIES ARE PRESENTED.

DERIVATIVES CONTAINING THE IMIDAZO [1, 2-A] PYRIDINE RING SYSTEM HAVE BEEN SHOWN TO POSSESS A BROAD RANGE OF USEFUL PHARMACOLOGICAL ACTIVITIES, INCLUDING ANTIBACTERIAL, ANTIFUNGAL, ANTHELMINTIC, ANTIVIRAL, ANTIPROTOZOAL, ANTI-INFLAMMATORY, ANTICONVULSANT, AND IMMUNOMODULATORY (KIFUNENSINE) ACTIVITIES [1-2].SEVERAL METHODS HAVE BEEN REPORTED FOR THE SYNTHESIS OF IMIDAZO [1, 2-A] PYRIDINE DERIVATIVES VIA A THREE-COMPONENT CONDENSATION OF 2-AMINOPYRIDIN WITH ALDEHYDES AND AN ISOCYANIDE [3-5].HOWEVER, IN MOST CASES THE YIELDS ARE GOOD AT HIGH TEMPERATURES AND SOME OF THE REAGENTS REQUIRE LONGER REACTION TIMES AND TEDIOUS PURIFICATION PROCEDURES. THUS, THERE IS A CERTAIN NEED FOR THE DEVELOPMENT OF AN ALTERNATIVE ROUTE FOR THE PRODUCTION OF IMIDAZO [1, 2-A] PYRIDINE, WHICH SURPASSESTHOSE LIMITATIONS.IN CONTINUATION OF OUR EFFORTS TO DEVELOP EFFICIENT AND ENVIRONMENTALLY BENIGN PROTOCOLS FOR THE SYNTHESIS OF HETEROCYCLES [6], WE REPORT HEREIN AN EFFICIENT SYNTHESIS OF THE IMIDAZO [1, 2-A] PYRIDINE DERIVATIVES BY THREE-COMPONENT CONDENSATION OF AN 2-AMINOPYRIDIN, AN ALDEHYDE, AND AN ISOCYANIDE IN THE PRESENCE OF CATALYTIC AMOUNTS OF CE (SO4) 2 AS AN INEXPENSIVEN CATALYST IN EXCELLENT YIELDS UNDER SOLVENT-FREE CONDITIONS.

IN THIS STUDY, THE NITRATION OF PHENYLACETYLENE (H-C≡C-PH) WAS INVESTIGATED. THE INVESTIGATION OF THE PRODUCT HAS SHOWN THAT THE TRIPLE BOND OF THE ACETYLENIC PART OF PHENYLACETYLENE HAS PARTICIPATED IN THE NITRATION PROCESS. IT MEANS THAT IN THE REACTION CONDITION THE ADDITIONAL REACTION ON THE-C≡C- OF PHENYLACETYLENE IS MUCH BETTER THAN THE SUBSTITUTION REACTION ON PH- GROUP. THE STRUCTURES OF THE PRODUCTS WERE ANALYZED BY THE DATA OF IR, 1H-NMR, 13C-NMR AND MS SPECTROSCOPY. THE B3LYP/6-31G* SHOWS THAT THE TRANS-B-NITROSTYRENE IS MORE STABLE THAN ITS CISFORM.THE HOMO LEVEL OF THE TRANS- AND CIS- ISOMERS OF B -NITROSTYRENE ARE -6.95 AND -6.90EV, RESPECTIVELY. THE EXPERIMENTAL AND THEORETICAL ASPECTS OF THIS STUDY WILL BE PRESENTED.

SALVIA, THE LARGEST GENUS OF THE FAMILY LAMIACEAE, INCLUDES ABOUT 900 SPECIES WIDESPREAD ALL OVER THE WORLD. FIFTY-EIGHT SPECIES ARE FOUND IN IRAN, 17 OF WHICH ARE ENDEMIC.SALVIA MIRZAYANII RECH. F. & ESFAND., ENDEMIC TO IRAN, GROWS IN THE SOUTHERN PARTS OF THE COUNTRY. MANY SALVIA SPECIES ARE USED AS HERBAL TEA AND FOR FOOD FLAVORING, AS WELL AS IN COSMETICS, PERFUMERY, AND THE PHARMACEUTICAL INDUSTRIES THROUGHOUT THE WORLD. IN FOLK MEDICINE, S. MIRZAYANII IS USED FOR THE TREATMENT OF DIARRHEA, STOMACH ACHE, HEADACHE, HYPER CHOLESTEROLEMIA, AND DIABETES. SEVERAL STUDIES HAVE ALSO SHOWN THE VARIOUS BIOLOGICAL ACTIVITIES OF THIS PLANT INCLUDING ITS ANTIBACTERIAL PROPERTIES.MICROWAVE-ASSISTED HYDRODISTILLATION (MAHD) IS AN ADVANCED HYDRODISTILLATION (HD) TECHNIQUE UTILIZING A MICROWAVE OVEN IN THE EXTRACTION PROCESS. IN THIS STUDY, HD AND MAHD METHODS HAVE BEEN COMPARED FOR THEIR EFFECTIVENESS IN THE ISOLATION OF ESSENTIAL OILS FROM THE AERIAL PARTS OF S. MIRZAYANII. THE COMPOSITION OF THE ESSENTIAL OILS WAS ANALYZED BY GC AND GC/MS. THE MAHD METHOD WAS SUPERIOR IN TERMS OF SAVING ENERGY AND EXTRACTION TIME (40 MIN, COMPARED TO 3 H IN HD). THE CONSTITUENTS OF THE ESSENTIAL OILS WERE SIMILAR AND THE TWO OILS CONTAINED THE SAME DOMINANT COMPONENTS: 1, 8-CINEOLE (15.2% HD AND 14.2% MAHD), A-MUUROLOL (11.6% AND 16.4%), B-PINENE (13.6% AND 7.6%), A-PINENE (9.8% AND 4.8%), BORNEOL (8.2% AND 8.3%),  D-CADINENE (8.1% AND 10.8%), AND Γ-CADINENE (3.7% AND 5.6%). CONSEQUENTLY, AS AN EXCELLENT ALTERNATIVE TO HD, MAHD MAY HAVE NO ADVERSE EFFECTS ON THE COMPOSITION OF EXTRACTED ESSENTIAL OILS. MAHD CAN BE SUGGESTED AS A MODERN, FAST AND GREEN EXTRACTION METHOD.

PYRAZOLE DERIVATIVES HAVE A WIDE RANGE OF BIOLOGICAL ACTIVITIES. THEY CAN BE USED AS ANTIPYRETIC, GASTRIC SECRETION STIMULATORY, ANTI-RHEUMATOID ARTHRITIS, ANTIBACTERIAL, ANTICONVULSANT, ANTITUMOR, INSECTICIDES, ANTIMICROBIAL, ANTIVIRAL, ANTIFUNGAL ANT FILARIAL AGENTS, AND ANTI-INFLAMMATORY. THEY ALSO SERVE AS HERBICIDES, FUNGICIDES, PESTICIDES, DYESTUFFS, ANTIDEPRESSANT, AND ANTIPSYCHOTIC.CATALYTIC PROPERTIES OF SNO2/TIO2 COMPOSITIONS IN TOTAL METHANE OXIDATION, DEGRADATION OF 4-CHLOROPHENOL, AND PHOTO CATALYTIC DEGRADATION OF METHYL ORANGE.IN THIS INVESTIGATION WE REPORT THE FORMATION OF THE NANO SNO2/TIO2 COMPOSITE BY SOL-GEL METHOD BY HYDROLYSIS OF TIN (IV) CHLORIDE AND TITANIUM (IV) CHLORIDE AT ROOM TEMPERATURE IN THE PRESENT OF POLYETHYLENE GLYCOL 200, NH (C2H4OH) 2 AND DISTILLED WATER.THE REPORTED PROTOCOL FOR THE SYNTHESIS OF PYRAZOLE DERIVATIVES IS THE MIXING OF 1, 3-DIKETONE, HYDRAZINE DERIVATIVES AND NANO SNO2/TIO2 COMPOSITE WAS HEATED.THE FT-IR, 1H-NMR, 13C-NMR SPECTRA AND ELEMENTAL ANALYSIS CONFIRM THE STRUCTURE OF COMPOUNDS. THE SEM IMAGE SHOWS THAT THE OXIDE POWDER IS OF AN EQUABLE DISTRIBUTION EXCEPT FOR A FEW AGGREGATED PARTICULATES. THE AVERAGE GRAIN SIZE CALCULATED BY PROPORTION OF THE PHOTOGRAPH IS ABOUT 40-50 NM, WHICH IS UNIFORM WITH THE RESULT OF THE XRD PATTERNS.

PCP (PHENCYCLIDINE, OR 1-PHENYL-CYCLOHEXYLPIPERIDINE IS THE ONE CLASS OF DRUGS PROMISING NATURE OF PCP AS AN ANESTHETIC IN WHICH SHOWS SEDATIVE EFFECTS, AND INTERACTIONS WITH OTHER CENTRAL NERVOUS SYSTEM DEPRESSANTS SUCH AS ALCOHOL AND BENZODIAZEPINES CAN LEAD TO COMA OR ACCIDENTAL OVERDOSE. SUBSTITUTION OF A HYDROGEN ATOM WITH FLUORINE IN BIOACTIVE MOLECULES CAN AFFECT THE BIOLOGICAL ACTIVITIES OF THESE MOLECULES.IN THIS RESEARCH WORK WE HAVE PREPARED THE ANALOG OF PHENCYCLIDINE PCP WITH FLUORINE ATOM AT THEP- POSITION OF PHENYL RING. WE ALSO HAVE PREPARED AN ANALOG OF PCP WITH SEVEN MEMBERED RING FLUORINATED WHERE THE PIPERIDINE RING OF PHENCYCLIDINE IS REPLACED WITH HEXAMETHYLENIMINE. THE STRUCTURE OF PRODUCT WAS DEDUCED FROM THIS IR, 1H NMR, AND 13C NMR SPECTRA.

THE METHODS OF GREEN CHEMISTRY CONTINUE TO GROW IN IMPORTANCE. ALTERNATIVE PROCESSES HELP TO CONSERVE RESOURCES AND CAN EVEN REDUCE COSTS. THE REPLACEMENT OF CONVENTION SOLVENTS WITH WATER OR SOLVENT-FREE CONDITIONS, WHICH IS HARMLESS TO HEALTH AND IS AVAILABLE IN LARGE QUANTITIES, IS ONE OF THE MOST INTERESTING BASIC APPROACHES ALONG THESE LINES. MULTICOMPONENT REACTIONS (MCRS) HAVE BEEN GENERALLY USED BY SYNTHETIC CHEMISTS AS A BASIC MEANS TO GENERATE MOLECULAR DIVERSITY FROM BIFUNCTIONAL SUBSTRATES THAT REACT REPEATEDLY IN AN INTRAMOLECULAR METHOD. HIGHLY SUBSTITUTED PYRROLE PLAY AN IMPORTANT ROLE IN ORGANIC CHEMISTRY, NOT ONLY AS KEY STRUCTURAL UNITS IN MANY NATURAL PRODUCTS, COMMON SUBUNITS IN PHARMACEUTICALS, FRAGRANCES, AND FLAVORS, BUT ALSO AS USEFUL BUILDING BLOCKS IN SYNTHETIC CHEMISTRY.HEREIN, WE REPORT AN EFFICIENT SYNTHESIS OF FUNCTIONALIZED PYRROLES4 FROM THE REACTION OF PRIMARY AMINES1, ACTIVATED ACETYLENES 2 AND ACTIVATED CARBONYL COMPOUNDS SUCH AS NINHYDRINE 3 UNDER SOLVENT-FREE CONDITIONS AT 50OC IN GOOD YIELD.

BAYLIS-HILLMAN (BH) REACTION HAVE RECEIVED SIGNIFICANT ATTENTION DUE TO THEIR MULTIPLE APPLICATIONS IN THE SYNTHESIS OF NATURAL PRODUCTS, BIOACTIVE MOLECULES, AND VARIOUS HETEROCYCLIC AND CARBOCYCLIC COMPOUNDS TO PRODUCE SIMPLE C-C BOND. IT IS ALSO USEFUL METHOD AS AN ATOM-ECONOMIC ONE-POT PROCEDURE. IN CONTINUATION OF OUR PREVIOUS EXPERIENCEON VARIOUS REACTIONS OF THIOPYRAN-4-ONE (1) RING , WE WOULD LIKE HERE TO REPORT BAYLIS-HILLMAN REACTION OF 2H -THIOPYRAN-4 (3 H) -ONE SYSTEM BY USING CATALYTIC AMOUNTS OF DBU (1, 8-DIAZABICYCLO [5.4.0] UNDEC-7-ENE) AS ANORGANOCATALYST, UNDER AQUEOUS CONDITION. REACTIONS PROCEEDED IN GOOD TO HIGH YIELDS AT ROOM TEMPERATURE VIA A VERY INEXPENSIVE AND ENVIRONMENTALLY BENIGN PROCEDURE WITH A VERY STRAIGHTFORWARD AND EASY WORKUP. THE STRUCTURE OF THE PRODUCTS IS ASSIGNED BASED ON THEIR SPECTROSCOPIC DATA.

IN RECENT YEARS THE THREE-COMPONENT REACTIONS OF TRIPHENYLPHOSPHINE, ELECTRON-DEFICIENT SYSTEMS AND XHACIDS (X=C, O, N, S) THAT LEADS TO PHOSPHORUS YLIDES HAVE BEEN REPORTED. THESE YLIDES ARE FINAL PRODUCTS OF REACTIONS OR INTERMEDIATES IN OTHER SYNTHESES.WE HERE REPORT THE REACTION OF 3- (2, 4-DINITROPHENY) -2, 4-PENTANEDIONE2 (ACTING AS A CH-ACID) AND DIALKYLACETYLENEDICARBOXYLATES1 IN THE PRESENCE OF TRIPHENYLPHOSPHINE. THESE COMPOUNDS UNDERGO INTRAMOLECULAR WITTIG REACTION IN ROOM TEMPERATURE TO PRODUCE CYCLOBUTENES, WHICH SPONTANEOUSLY UNDERGO RING-OPENING REACTION TO PRODUCE DIASTEREOMERIC 1, 3- DIENE ISOMERS3 IN MIDDLING YIELDS. THE STRUCTURE OF COMPOUNDS IS SUPPORTED WITH SPECTRAL DATA (1HNMR, 13CNMR, IR) AND ELEMENTAL ANALYSIS.

THE O-DEALKYLATION OF ETHERS, OR ETHER CLEAVAGE, REMAINS AN INTEGRAL FUNCTIONAL GROUP DEPROTECTION STEP TO UNMASK A HYDROXYL GROUP. THE REAGENT SELECTIVITY RELATIVE TO OTHER TYPES OF HYDROXYL PROTECTING GROUPS WILL BE HIGHLIGHTED, AS THIS REMAINS A KEY FACTOR IN THE CHOICE OF REAGENT, ESPECIALLY IN POLY FUNCTIONAL MOLECULES [1]. METHYL ETHERS OF BOTH ALIPHATIC AND AROMATIC MOIETIES ARE ONE OF THEM, BUT A MAJOR DRAWBACK INVOLVED IN THIS IS THEIR ROBUSTNESS AND THE DIFFICULTIES ENCOUNTERED DURING THEIR CLEAVAGE [2]. AROMATIC METHYL ETHERS ARE MORE EASILY CLEAVED THAN THEIR ALIPHATIC COUNTERPARTS [3]. THE CHOICE OF REAGENT CAPABLE OF CLEAVING THE ALKYL ARYL ETHER BOUND IS VERY IMPORTANT.WE HAVE FOUND THAT THE DEMETHYLATION OF ARYL METHYL ETHERS CAN BE SELECTIVITY ACHIEVED BY THE TREATMENT OF ANTIMONY PENTACHLORIDE IN ACETONITRILE IN EXCELLENT YIELDS.THE ABOVE STUDIES PROMPTED US TO SELECT THE USE OF SBCL5 IN CH3CN ANHYDROUS UNDER ROOM TEMPERATURE TO PROBE THE SCOPE OF THE DEMETHYLATION REACTION. SBCL5 AS LEWIS ACID CAN PLAY CERTAINLY DIFFERENT ROLE ON POLY-SUBSTITUTED ETHERS COMPOUNDS. IN THIS CASE, SBCL5 SELECTIVELY DEPROTECT ONE OF THE SEVERAL METHOXY GROUPS ON SUBSTRATE. UNDER THE RELATIVELY MILD REACTION CONDITIONS, THE METHYL GROUP CAN BE READILY CLEAVED TO AFFORD CLEAN PHENOL-DERIVED PRODUCT EXCELLENT YIELDS. THE VERSATILE BY-PRODUCTS CAN BE CONVENIENTLY REMOVED BYCOLUMN CHROMATOGRAPHY.

THE ISOQUINOLINE AND QUINOLINE SKELETON IS FOUND IN A LARGE NUMBER OF NATURALLY OCCURRING AND SYNTHETIC BIOLOGICALLY ACTIVE HETEROCYCLIC COMPOUNDS. IN PARTICULAR, 1, 2-DIHYDROISOQUINOLINE DERIVATIVES ACT AS DELIVERY SYSTEMS THAT TRANSPORT DRUGS THROUGH THE OTHERWISE HIGHLYIMPERMEABLE BLOOD–BRAIN BARRIER. THESE COMPOUNDS ALSO EXHIBIT SEDATIVE, ANTIDEPRESSANT, ANTITUMOR, AND ANTIMICROBIAL ACTIVITIES. IN RECENT TIMES, MULTICOMPONENT REACTIONS (MCRS) HAVE BEEN GENERALLY USED FOR THE SYNTHESIS OF VARIOUS AND COMPLEX COMPOUNDS AS WELL AS SMALL AND DRUG-LIKE HETEROCYCLES.HERE WE DESCRIBE A ONE-POT AND EFFICIENT METHOD FOR SYNTHESIS OF 1, 2-DISUBSTITUTED 1, 2-DIHYDROQUINOLINES DERIVATIVES VIA THE REACTION OF QUINOLINE, DIALKYL ACETYLENEDICARBOXYLATE AND NPHENYL CARBAMATES, AT ROOM TEMPERATURE (SCHEME 1). THE PRODUCTS WERE CHARACTERIZED ON THE BASIS OF THEIR ELEMENTAL ANALYSES AND THEIR IR, 1H NMR, 13C NMR AND MASS SPECTRA.

A NEW SERIES OF 5- (ISOMERIC PYRIDYL) - 1, 3, 4- OXADIAZOLE 3 (A-C) AND THIADIAZOLE 4 (A-C), DERIVATIVES WERE SYNTHESIZED IN EXCELLENT YIELD AND TO OBTAIN NEW COMPOUNDS WITH POTENTIAL SIGNIFICANT BIOLOGICAL ACTIVITY. THE STARTING COMPOUND, THIOSEMICARBAZIDES 2 (A-C), WERE USED AS THE KEY INTERMEDIATES FOR THE SYNTHESIS OF HETEROCYCLIC COMPOUNDS. THE STRUCTURE OF THE TARGET COMPOUNDS WERE CONFIRMED BY IR, 1H-NMR, AND MS SPECTROSCOPY.THE NEW OXADIAZOLE AND THIADIAZOLE DERIVATIVES WERE PREPARED FOLLOWING THE REACTION SEQUENCES DEPICTED IN SCHEME 1. THE STARTING MATERIAL FOR THE SYNTHESIS OF THE TARGETED COMPOUNDS IS THIOSEMICARBAZIDE, WHICH WAS PREPARED BY THE REACTION 4-HALO PHENYL ISOTHIOCYANATE AND ISOMERIC PYRIDINE CARBOXYLIC ACID HYDRAZIDES 1 (A-C) IN ETHANOL MEDIA.THEREFORE 2- (4- HALOANILINE) - 5 - (ISOMERIC PYRIDYL) - 1, 3, 4- THIADIAZOLE AND 2- (4- HALOANILINE)-5- (ISOMERIC PYRIDYL) - 1, 3, 4-OXADIAZOLE WERE REACTED WITH CORRESPONDING REAGENTS PRODUCTS. FROM THE PRESENT STUDY, IT CAN PROMOT FUTURE RESEARCHER TO SYNTHESIZE A SERIES OF THESE COMPOUNDS CONTAINING WIDE VARIETIES OF SUBSTITUENT WITH THE AIM OF OBTAINING SOME NOVEL HETEROCYCLIC SYSTEMS WITH ENHANCED MEDICAL PROPERTIES.

THE ENERGY CONTENT IN ALKYNES MAY BE INCREASED FURTHER BY BENDING THE NORMALLY LINEAR TRIPLE BOND, AS IN THE SMALL CYCLOALKYNES. THE STRAIN ENERGY IN THE CYCLOALKYNES INCREASES AS THE SIZE OF THE RING DECREASES. CYCLOADDITIONS OF 1, 3-DIPOLES WITH ALKYNES MAY OCCUR BY CONCERTED MECHANISMS. IN THIS STUDY, THE REACTIVITY AND STRAIN ENERGY EFFECT OF THE CYCLOALKYNES WITH SUBSTITUTED TRIAZOLES R-N3 (R=H, CH3 AND PH) BY THE USE OF B3LYP/6-31G* LEVEL METHOD WILL BE DISCUSSED. THE INVESTIGATION OF THE STRUCTURED PROPERTIES, THEORETICAL THERMODYNAMIC AND KINETIC DATA I.E. DRG, DG* AND RATE CONSTANTS OF THE REACTIONS IN 298K WILL BE PRESENTED.

BENZO- AND NAPHTHOPYRAN DERIVATIVES ARE IMPORTANT CLASS OF HETEROCYCLIC COMPOUNDS POSSESSING BIOLOGICAL AND PHARMACOLOGICAL ACTIVITIES, SUCH AS ANTICOAGULANT, SPASMOLYTIC, DIURETIC, ANTICANCER AND ANTIANAPHYLACTIN. THREE-COMPONENT SYNTHESIS OF 4H-BENZO [B] PYRANS AND THEIR DERIVATIVES ARE OF CONSIDERABLE INTEREST BECAUSE OF THEIR WIDE RANGE OF BIOLOGICAL ACTIVITIES AS MENTIONED ABOVE.4H PYRANS ALSO CONSTITUTE THE STRUCTURAL UNIT OF A SERIES OF NATURAL PRODUCTS. VARIOUS METHODS FOR PREPARING THESE COMPOUNDS HAVE BEEN REPORTED. SEVERAL CONVENTIONAL SYNTHESES OF THESE POLY FUNCTIONALIZED BENZOPYRANS INVOLVING THE CONDENSATION OF MALONONITRILE WITH AN ALDEHYDE AND PHENOL OR NAPHTHOL USING BASES OR AMIDES AS CATALYSTS HAVE BEEN WELL-DEVELOPED. HEREIN, WE WISH TO DISCLOSE AN EFFICIENT MULTI-COMPONENT CONDENSATION REACTION UTILIZING BASE FUNCTIONALIZED SILICA AS A GREEN, NONE TOXIC, REUSABLE AND CHEAP CATALYST FOR THE SYNTHESIS OF 3-AMINO-2-CYANO-1- (R) -1H-BENZOCHROMENES BY REACTING AROMATIC ALDEHYDE DERIVATIVES, 1 OR 2-NAPHTHOL, AND MOLONONITRILE UNDER SOLVENT FREE CONDITIONS, SHORT REACTION TIME AND HIGH YIELD OF THE PRODUCTS ARE MAIN ADVANTAGES OF THIS PROTOCOL.

1, 2, 4- TRIAZOLES ARE NITROGEN HETROCYCLES, WHICH HAVE IMPORTANT INDUSTRIAL, AGROCHEMICAL, CORROSION INHIBITION USES [1-3]. NEW 1, 2, 4- TRIAZOLES CONTAINING ISOMERIC PYRIDYL WERE OBTAINED FROM CYCLIZATION OF CORRESPONDING THIOSEMICARBAZIDES UNDER ACIDIC AND NEUTRAL CONDITIONS.HERE WE REPORT SYNTHESES OF SOME 1, 2, 4- TRIAZOLES 3 (A-C) BY THE REACTION OF 1, 4- DISUBSTITUTED THIOSEMICARBAZIDES 2 (A-C) WITH SODIUM HYDROXIDE THEN ALKYLATION WITH METHYL IODIDE AND ETHYL IODIDE IN OH- MEDIUM LED TO THE FORMATION 4 (A-C) IN REFLUX.THEREFORE 4- (4- HALIDOPHENYL) - 5- (ISOMERIC PYRIDYL) - 1, 2, 4- TRIAZOLE 3- THIOLS WERE REACTED WITH CORRESPONDING REAGENTS IN BASIC AQUEOUS ALCOHOL TO GIVE THIO SUBSTITUTED PRODUCTS. ONE THE OTHER HAND THE REACTION WITH ALKYL IODIDE IN AQUEOUS ALCOHOL RESULTED NEW TYPE PRODUCTS. ALL THE NEWLY SYNTHESIZED COMPOUNDS GAVE SATISFACTORY ANALYSES FOR THE PROPOSED STRUCTURES, WHICH WERE CONFIREMED ON THE BASIS OF THEIR MS, 1H-NMR, FT-IR AND ALL OF THE COMPONENTS WERE FORMED IN GOOD YIELD (80-97%).

STABLE CRYSTALLINE PHOSPHORUS YLIDES WERE OBTAINED IN EXCELLENT YIELDS FROM THE 1:1:1 ADDITION REACTION BETWEEN TRIPHENYLPHOSPHINE AND DIALKYL ACETYLENEDICARBOXYLATES, IN THE PRESENCE OF 2- CHLOROANILINE, 2-FLUOROANILINE AND 2-AMINOACETOPHENONE.THESE STABLE YLIDES EXIST IN SOLUTION AS A MIXTURE OF TWO GEOMETRICAL ISOMERS AS A RESULT OF RESTRICTED ROTATION AROUND THE CARBON-CARBON PARTIAL DOUBLE BOND RESULTING FROM THE CONJUGATION OF THE YLIDE MOIETY WITH THE ADJACENT CARBONYL GROUP. THE SYNTHESIS OF PHOSPHORUS YLIDES IS IMPORTANT IN ORGANIC CHEMISTRY BECAUSE OF THEIR APPLICATION IN THE SYNTHESIS OF ORGANIC PRODUCTS. PHOSPHORUS YLIDES ARE REACTIVE INTERMEDIATES, WHICH TAKE PART IN MANY VALUABLE REACTIONS IN ORGANIC SYNTHESIS. THESE YLIDES MOST OFTEN ARE PREPARED BY TREATMENT OF A PHOSPHONIUM SALT WITH A BASE AND PHOSPHONIUM SALTS USUALLY ARE MADE FROM THE PHOSPHINE AND AN ALKYL HALIDE. THE STRUCTURES OF COMPOUNDS 3A-C WERE DEDUCED FROM THEIR IR, 1H, 13C AND 31P NMR SPECTRUM. THE MASS SPECTRUM OF THEM DISPLAYED MOLECULAR ION PEAKS AT APPROPRIATE M/Z VALUES.

AMIDES ARE ONE OF THE MOST IMPORTANT AND PROLIFIC FUNCTIONAL GROUPS, WITH A GREAT IMPORTANCE IN BOTH RESEARCH AND INDUSTRIAL CHEMISTRY DUE TO THEIR PREVALENCE IN DETERGENTS, LUBRICANTS, BIOLOGICALLY ACTIVE COMPOUNDS AND PHARMACEUTICALS. ALTHOUGH, THERE ARE MANY STRATEGIES TO PREPARE THEM, HOWEVER, THE ENORMOUS AMOUNT OF WASTES’ PRODUCTION BY STANDARD PROTOCOLS FORCES THE INDUSTRY TO LOOK FORWARD FOR BETTER STRATEGIES.REARRANGEMENT OF A KETOXIMES TO THE CORRESPONDING AMIDES WHICH IS KNOWN AS BECKMANN REARRANGEMENT, IS ONE OF THE MOST IMPORTANT METHODS IN ORGANIC SYNTHESIS. AS A PART OF OUR RESEARCH PROGRAM, WE ENCOURAGED TO DEVELOP SOME IMPROVED PROCEDURES FOR BECKMANN REARRANGEMENT OF KETOXIMES DUE TO CONTINUING INTEREST AND IMPORTANCE IN ORGANIC CHEMISTRY. HEREIN, WE WISH TO REPORT SULFURIC ACID SUPPORTED ON CHARCOAL AS AN EFFICIENT PROMOTER FOR FAST AND EFFICIENT REARRANGEMENT OF KETOXIMES TO THE CORRESPONDING AMIDES IN TERMS OF SIMPLICITY, MILDNESS AND ECOFRIENDLY ASPECTS (SCHEME).