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Microwave (MW) irradiation facilitated synthesis provides fast, safe, simple, and green reaction conditions. MW irradiation of 2-aminobenzophenones with heteroaromatic ketones afforded quinolines via Friedlander condensation in high yields with intact halogen substituents for further modifications. Dibenzo[b,f][1,5]diazocines were found as minor products and in some instances as the only products as the result of self-condensation of 2-aminobenzophenones. Different acid catalysts were found to affect these cyclization processes. Mini library of quinolines and dibenzo[b,f][1,5]diazocines were created in order to understand the substituents effect on the reaction. Resultant quinolines and dibenzo[b,f][1,5]diazocines are anticipated to serve as an interesting library for high throughput screening of various biological applications.

To develop a luminescent material with high color purity, luminous efficiency, and stability, we synthesized diketone by carbonylative Suzuki coupling in the presence of Pd(NHC) complex as the catalyst. Carbonylative coupling of 4,4’-diiodobiphenyl and phenylboronic acid was investigated to study in detail the catalytic ability of the Pd(NHC) complex. Reactions were carried out using both CO and metal carbonyls. Bis-(1,3-dihydro-1,3-dimethyl-2H-imidazol- 2-ylidene) diiodo palladium was used as the catalytic complex. Reaction products biphenyl-4,4’-diylbis (phenyl- methanone) 3 and (4’-iodobiphenyl-4-yl)(phenyl) methanone 4 were obtained as a result of CO insertion into the palladium(II)-aryl bond. However, when pyridine-4-yl boronic acid was used in place of phenylboronic acid as the starting reagent, synthetic reaction yielding 3 and 4 were found not to occur.

luminescence (CL) flow injection system. The CL intensities of polyphenols are considerably weaker than those of luminal and acridinium ester, which are representative CL compounds. Hence, trans-4-(3-propionic acid) phenylboronic acid and 4-biphenylboronic acid in the presence of peroxidase or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide have been used as an enhancer for highly sensitive polyphenol CL determination. However, methods to derive polyphenols with strong CL intensity have not been reported yet. 18 In recent times, after a new polymer, poly(amidoamine) dendrimer, was synthesized, dendrimers have been applied to material engineering based on optics in nanoscale science. The poly(propylene amine) family that was functionalized in the periphery with fluorescent dansyl units interacts with Co 2+ . More recently, acridinium dendrimers have been conjugated with bovine serum albumin, and its CL was estimated to be six times that of the acridinium salt. In this paper, we report the design of new types of polyphenol dendrimers having an increased number of chemiluminophores for high CL intensity; they also have hydroxyl groups in their periphery to form hydrogen bonds with an analyte. Polyphenol dendrimers having GA in the periphery were synthesized, and their CL was measured. We synthesized first-generation polyphenol dendrimers with GA units in the periphery by employing a divergent method using phenol, pyrocatechol, resorcinol, hydroquinone, 1,2,4-tri

phenol yielded 2a in 80%. After the debenzylation of 2a, we were able to separate 3a and the byproduct by chromatographic purification. Therefore, the desired zero-generation ester 3a was not isolated. Compounds 4a and 5a were synthesized by repeating this esterification and debenzylation, respectively, but the yield of the first-generation ester 5a was 91%. The esteri- fication of 3,4,5-trihydroxybenzoyl chloride with pyrocatechol, 3,4,5-trihydroxybenzoyl chloride with resorcinol, and 3,4,5- trihydroxybenzoyl chloride with hydroquinone yielded 2b (95%), 2c (96%), and 2d (91%), respectively. The zero-gene- ration esters 3b, 3c, and 3d and first-generation esters 5b, 5c, and 5d were synthesized as described above. The yields of the polyphenol dendrimers decreased with increasing dendrimer

Microwave (MW) irradiation facilitated synthesis provides fast, safe, simple, and green reaction conditions. MW irradiation of 2-aminobenzophenones with heteroaromatic ketones afforded quinolines via Friedlander condensation in high yields with intact halogen substituents for further modifications. Dibenzo[b,f][1,5]diazocines were found as minor products and in some instances as the only products as the result of self-condensation of 2-aminobenzophenones. Different acid catalysts were found to affect these cyclization processes. Mini library of quinolines and dibenzo[b,f][1,5]diazocines were created in order to understand the substituents effect on the reaction. Resultant quinolines and dibenzo[b,f][1,5]diazocines are anticipated to serve as an interesting library for high throughput screening of various biological applications.

Benzodiazepines are interesting compounds because of their pharmacological properties. Many members of this family are, in fact, nowadays widely used as tranquilizing and anticonvulsant agents. Although the first benzodiazepine was introduced as a drug nearly 30 years ago, the research in this area is still very active and is directed towards the synthesis of compounds of enhanced pharmacological activity. Some benzodiazepine derivatives are also used in industry, such as in photography (as dyes for acrylic fibers), and also as anti-inflammatory agents. 1H-1,5Benzodiazepines are used as starting materials for the preparation of some fused ring benzodiazepine derivatives, such as triaxol and oxadiazol. Despite their wide range of pharmacological activity, industrial and synthetic application, the synthesis of 1H-1,5-benzodiazepines has received little attention. As a part of research program related to the synthetic study of pharmacologically interesting benzodiazepine compounds, herein we now report the synthesis of 1H-1,5-benzodiazepine derivatives with heteroaromatic ketones (2-acetylfuran 2a, 2-acetylthiophene 2b, 2-acetylpyridine 2c, 3-acetylpyridine 2d, and 4-acetylpyridine 2e) by using conc-HCl, SiO2, or polyphosphoric acid (PPA) (Scheme 1). Specially we report synthesis of quinoxaline derivatives with phenylenediamine 1a and acetylpyridines 2c, 2e in aqueous 10% conc-HCl solution (Scheme 2). Moreover we describe the structural analysis of 7-chloro2,2,4-trimethyl-2,3-dihydro-1H-1,5-benzodiazepine 3f and 8-chloro-2,2,4-trimethyl-2,3-dihydro-1H-1,5-benzodiazepine 3g synthesized by 4-chloro-1,2-phenylenediamine 1b with acetone. Earlier we reported the synthesis of 2,4,4,-trimethyl-3H-5hydro-1,5-benzodiazepine and 2,4-diphenyl-4-methyl-3H-5hydro-1,5-benzodiazepine by using various reagents instead of PPA. When 1a was treated with 2a in the presence of PPA at 4045 °C for 5 h, a yellow crystalline solid, 3a was isolated

In order to synthesize new bioactive compounds and contrasting agents, reactions of glycine and glutamic acid as an animo acid with paraformaldehyde and hypophosphorous acid were executed. Products are 3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-diazadiphosphocine-1,5-diacetic acid 1 and 3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-diazadiphosphocine-1,5-di-(2-glutaric acid) 3. 2-[5-(1,2-Dicarboxyethyl)-3,7-dihydroxy-3,7-dioxo-315.715-[1,5,3,7] diazadiphosphocan-1-yl]-succinic acid 2 by using aspartic acid was not obtained. Esterification of 3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-diaza-diphosphocine-1,5-diacetic acid 1 by treatment of methanol, ethanol, and propanol were executed. 3,7-Dihydroxy-3,7-dioxoperhydro-1,5,3,7-diazadiphosphocine-1,5-diacetic acid methyl ester 4, 3.7-dihydroxy-3,7-dioxoperhydro-1,5,3, 7-diazadiphosphocine-1.5-diacetic acid ethyl ester 5, and 3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-diazadiphosphocine-1,5-diacetic acid propyl ester 6 were respectively synthesized in good yields. Continuously, we will try synthesis of novel compounds and evaluation of biological activity.

The synthesis of a new class of spiro-β-lactams (VIII) having an 8-azabicyclo[3.2.1]octan-3-one ring is described using the Staudinger reaction as key step.

Quinolines 3a–f, 5a–f, and dibenzo[b,f][1,5]diazocines 4, 6 were synthesized in the presence of 0.5 equiv. of diphenyl phosphate (DPP) under microwave irradiation. The obtained yield of 6,12-diphenyl-dibenzo[b,f][1,5]diazocine 4 was higher when using anhydrous DPP than when using HCl, H3PO4, and CH3COOH.

Tropane alkaloids have received a great deal of attention because of their remarkable pharmaceutical significance. Therefore a variety of synthetic approaches to tropane alkaloids have been investigated. Especially, a series of tropanes showed anticonvulsant activity against pentylenetetrazol-induced convulsions in mice and antiarrhythmic activity in rabbit previously treated with ouabain. *Corresponding Author. E-mail : As a part of a research program related to the synthetic study of pharmacologically interesting tropane compounds, we now report the synthesis of di-(N-tropinonyl)benzenes and di-(N-tropinonyl)alkanes in the reaction of phenylenediamines (or diaminoalkanes) with 2,5-dimethoxytetrahydrofuran, and acetonedicarboxylic acid at 0 C. Earlier we reported the synthesis of N-substituted nortropinones in the reaction of amines with 2,5-dimethoxytetrahydrofuran, and acetonedicarboxylic acid. A representative experimental procedure for the synthesis of 1,4-di-(8-azabicyclo[3,2,1]octan-3-onyl)benzene (7) is as follows: A mixture of 2,5-dimethoxytetrahydrofuran (6.6 g, 0.05 mol), acetonedicarboxylic acid (5.84 g, 0.04 mol), water (20 mL), and c-HCl (0.5 mL) was stirred for 30 min. p-Phenylenediamine (2.16 g, 0.02 mol) in water (10 mL) was added by using a dropping funnel at 0 C. After the reaction mixture was stirred under N2 at room temperature for 22 h, a crude brown solid was precipitated. The reaction mixture was diluted with water (20 mL) and neutralized with saturated NaHCO3 solution. The neutralized solution was extracted with dichloromethane (100 mL × 3). The organic layer was dried (Na2SO4), filtered and concentrated. The residue was chromatographed on a silica gel (n-hexane : ethyl acetate = 1 : 3, v/v) to yield 7 (4.47 g, 69%) as a brown crystalline solid. H-NMR showed a singlet at δ 4.49 for four protons of C1 and C5, a doublet at δ 1.78 for four protons of C6n and C7n, a doublet at δ 2.17 for four protons of C6x and C7x, a doublet at δ 2.22 (H-2(4)α, J = 3 Hz). for four protons of C2α and C4α, and a doublet at δ 2.70 (H-2(4)α, J = 10 Hz) for four protons of C2β and C4β. Aromatic protons were at δ 6.89 as a singlet.

A new synthesis of chromones and flavones based on the ortho-directed metalation of methoxymethyl aryl ethers with alkyllithium reagents is described. It entails reaction of the ortho-lithiated intermediates with a conjugated unsaturated aldehyde followed by oxidation of the allylic alcohol product with «periodinane» to yield an ortho-allylic ketone. The latter on heating in acetic acid undergoes loss of the methoxymethyl protecting group and cyclization to a chromanone (or flavanone, if a β-phenyl substituent is present). Dehydrogenation by treatment with pyrrolidone hydrotribromide (PHT) in dimethyl sulfoxide yields the corresponding chromones (or flavones). This synthetic approach appears general in its applicability

Aromatic nitro compounds containing o-, m- or p-electron withdrawing groups, such as carbonyl, halogen and nitro, were selectively and rapidly reduced to their corresponding amino derivatives in good yields using Bakers' Yeast in basic solution.

As a part of a research program related to the synthetic study of pharmacologically and agrochemically important imidazolidines, we chose to identify imidazolidine-2,4,5-trione and imidazolidine-2,4,5-trione or 2-thioxo-imidazolidine-4,5-dione rings as active components for the desired property. We currently report the synthesis of(imidazolidine-2,4,5-dionyl)methyl-imidazolidine-2,4,5-triones 1, 4,5-dioxo-2-thioxo-imidazolidin-1-yl-methyl-imidazolidine-2,4,5-triones 2, and 4,5-dioxo-2-thioxo-imidazolidin-1-yl- methyl-imidazolidine-2-thioxo-4,5-dione 3.

Quinolines 3a–f, 5a–f, and dibenzo[b,f][1,5]diazocines 4, 6 were synthesized in the presence of 0.5 equiv. of diphenyl phosphate (DPP) under microwave irradiation. The obtained yield of 6,12-diphenyl-dibenzo[b,f][1,5]diazocine 4 was higher when using anhydrous DPP than when using HCl, H3PO4, and CH3COOH.

Reissert compounds derived from α,β-unsaturated acid chlorides were prepared. The conjugate base obtained from these Reissert compounds exhibited the following carbanion reactions: 1) Alkylation, 2) Condensation with benzaldehyde, 3) Rearrangement to give dimeric compounds rather than simple rearranged compounds. In the case of alkylated isoquinoline Reissert compounds, the attempted rearrangement led to ring annellated amines.

A novel one-pot synthesis of angular polycyclic hydrocarbon ring systems is described. The method involves Ti(IV)-promoted aldol-type condensation of silyl enol ethers with 2-arylacetaldehydes with concurrent cyclization and double dehydration of the adducts. Dehydrogenation of the partially saturated polyarene products either catalytically over palladium or with quinone oxidants, such as DDQ, affords fully aromatic polycyclic hydrocarbons. Examples of the synthesis of various phenanthrene, chrysene, benz[a]anthracene, and benz[j]acephenanthrylene derivatives via this route are presented.

Benzodiazepines are interesting compounds because of their pharmacological properties. Many members of this family are, in fact, nowadays widely used as tranquilizing and anticonvulsant agents. Although the first benzodiazepine was introduced as a drug nearly 30 years ago, the research in this area is still very active and is directed towards the synthesis of compounds of enhanced pharmacological activity. Some benzodiazepine derivatives are also used in industry, such as in photography (as dyes for acrylic fibers), and also as anti-inflammatory agents. 1H-1,5Benzodiazepines are used as starting materials for the preparation of some fused ring benzodiazepine derivatives, such as triaxol and oxadiazol. Despite their wide range of pharmacological activity, industrial and synthetic application, the synthesis of 1H-1,5-benzodiazepines has received little attention. As a part of research program related to the synthetic study of pharmacologically interesting benzodiazepine compounds, herein we now report the synthesis of 1H-1,5-benzodiazepine derivatives with heteroaromatic ketones (2-acetylfuran 2a, 2-acetylthiophene 2b, 2-acetylpyridine 2c, 3-acetylpyridine 2d, and 4-acetylpyridine 2e) by using conc-HCl, SiO2, or polyphosphoric acid (PPA) (Scheme 1). Specially we report synthesis of quinoxaline derivatives with phenylenediamine 1a and acetylpyridines 2c, 2e in aqueous 10% conc-HCl solution (Scheme 2). Moreover we describe the structural analysis of 7-chloro2,2,4-trimethyl-2,3-dihydro-1H-1,5-benzodiazepine 3f and 8-chloro-2,2,4-trimethyl-2,3-dihydro-1H-1,5-benzodiazepine 3g synthesized by 4-chloro-1,2-phenylenediamine 1b with acetone. Earlier we reported the synthesis of 2,4,4,-trimethyl-3H-5hydro-1,5-benzodiazepine and 2,4-diphenyl-4-methyl-3H-5hydro-1,5-benzodiazepine by using various reagents instead of PPA. When 1a was treated with 2a in the presence of PPA at 4045 °C for 5 h, a yellow crystalline solid, 3a was isolated

A new synthesis of chromones and flavones based on the ortho-directed metalation of methoxymethyl aryl ethers with alkyllithium reagents is described. It entails reaction of the ortho-lithiated intermediates with a conjugated unsaturated aldehyde followed by oxidation of the allylic alcohol product with «periodinane» to yield an ortho-allylic ketone. The latter on heating in acetic acid undergoes loss of the methoxymethyl protecting group and cyclization to a chromanone (or flavanone, if a β-phenyl substituent is present). Dehydrogenation by treatment with pyrrolidone hydrotribromide (PHT) in dimethyl sulfoxide yields the corresponding chromones (or flavones). This synthetic approach appears general in its applicability

The tropane class of alkaloids has continued to elicit the unabated interests among organic chemists because of their pharmacological significance, and a great deal of efforts has been focused on the stereochemical synthetic methodologies. Cocaine, a notorious member of this alkaloidal family, is found in erythroxylon coca, indigenous to the higher elevations of peru. The natives of this region, descendants of the Incas, still chew the coca leaf for its stimulatory properties. In particular, a series of tropans showed anticonvulsant activity against pentylenetetrazolinduced convulsions in mice and antiarrhythmic activity in rabbit previously treated with ouabain. As a part of ongoing research for the pharmacologically interesting tropane compounds, herein we report a new synthetic conditions of corresponding 2-substituted 8-azabicyclo[3.2.1]octan-3-one, 3, by aldol condensation from 8substituted 8-azabicyclo[3.2.1]octan-3-one, 1. We already reported a synthesis of 2,4-disubstituted 8-azabicyclo[3.2.1]octan-3-one, 2, derived from the reaction of N-substituted 8azabicyclo[3.2.1]octan-3-one, 1, with aldehydes (R1CHO) in the presence of ethanol and aqueous 5 N NaOH. We also reported the synthesis of di-(N-tropinonyl)alkanes from the reaction of phenylenediamines (or diaminoalkanes) with 2,5-dimethoxytetrahydrofuran and acetonedicarboxylic acid. Then our attempt to prepare 2-substituted 8-azabicyclo[3.2.1]octan-3-one, 3, from 8-substituted 8-azabicyclo[3.2.1]octan-3-one, 1, was unsuccessful, under various reaction conditions: sodium hydride, sodium methoxide, or butyl lithium. But M. Majewski and R. Lazny reported that their synthesized compound, 2-benzylidene-8-methyl-8-azabicyclo[3.2.1]octan-3-one was done through three-step treatment of chiral lithium amide, Ac2O, and SiO2 (Scheme 1). In brief, as their synthetic method had three-step reactions and three times work-ups, it was so complicated. Recently, Peter A. Crooks et al. reported two-step synthesis by treatment of lithium diisopropylamide or lithium bis(trimethylsilyl)amide. In order to synthesize 2-substituted 8-azabicyclo[3.2.1]octan-3-one, 3, simply and efficiently, we conducted research on the effect of aqueous NaOH concentration variations (1 N, 0.5 N, 0.1 N, 0.02 N, or 0.01 N). Yield comparison of compound 3e according to concentration variation of aqueous NaOH solution is expressed in Table 1. In case of higher concentrations over aqueous 0.01 N NaOH solution, the ratio of 2,4-disubstituted 8-azabicyclo[3.2.1]octan-3-one, 2, was produced somewhat higher than that of 2-substituted 8-azabicyclo[3.2.1]octan-3-one, 3. Yield of 8-benzylidene-8-phenyl-8-azabicyclo[3.2.1]octan

Aromatic nitro compounds containing o-, m- or p-electron withdrawing groups, such as carbonyl, halogen and nitro, were selectively and rapidly reduced to their corresponding amino derivatives in good yields using Bakers' Yeast in basic solution.

Various di-Reissert compounds and analogs were prepared from quinazoline by use of trimethylsilyl cyanide together with a catalytic amount of anhydrous aluminum chloride. Reactions of these quinazoline di-Reissert compounds are reported.