A series of thiadiazole and selenadiazole derivatives was synthesized via oxidative cyclization of some semicarbazone derivatives of the types 3 and fa. The later compounds were formed via reaction of coumarin-6-sulphonyl chloride I with m-, p-aminoacetophenone and / or o- and p-hydroxyacetophenone to give coumarin-6-sulphonamides 2 or the esters. Condensation of 2 and 5 with semicarbazide hydrochloride afforded the semicar-bazones 3 and. Oxidative cyclization of 3 and with thionyl chloride led to the formation of the thiadiazole derivatives I and Z. On the other hand, oxidative cyclization of 3 and 6 with selenium dioxide led to the formation of selenadiazole derivatives la and 9.

Coumarin-6-sulphonamides 2a-c were synthesized through reactions of coumarin-6-sulphonyl chloride 1 with semicarbazide, thiosemicarbazide and guanidine. The reaction of diethylmalonate, acetylacetone, and ethyl acetoacetate with 2 gave the pyremidine derivatives 4, 6, 8, 9, 13 and 17, via the intermediates 3, 6, 8, 9, 12 and 16.

A series of thiadiazole and selenadiazole derivatives was synthesized via oxidative cyclization of some semicarbazone derivatives of the types 3 and 6. The later compounds were formed via reaction of coumarin-6-sulphonyl chloride 1 with m-, p-aminoacetophnone and/or o- and p-hydroxyacetophenone to give coumarin-6-sulphonamides 2 or the esters 5. Condensation of 2 and 5 with semicarbazide hydrochloride afforded the semicarbazones 3 and 6. Oxidative cyclization of 3 and 6 with thionyl chloride led to the formation of the thiadiazole derivatives 4 and 7. On the other hand, oxidative cyclization of 3 and 6 with selenium dioxide led to the formation of selenadiazole derivatives 8 and 9.

The sugar hydrazones (4a-c) double under bar were produced via reactions of the acid hydrazide (3) double under bar with arabinose, mannose and glucose, respectively. The triazolyiderivative (6) double under bar was formed via the reactions of (3) double under bar with methylisothiocyanate yielding the thiosemicarbazide derivatives (5b) double under bar followed by cyclization with NaOH solution. Reaction of (3) double under bar with phenylisothiocyanate afforded (5a) double under bar. Reaction of (3) double under bar with CS2 and KOH gave either the oxadiazolyl derivative (7) double under bar or the potassium thiocarbazate (8) double under bar depending on the reaction conditions. Fusion of (8) double under bar with hydrazine hydrate gave the 1,2,4-triazolyl derivative (9) double under bar. The 1,2,4-triazoloquinoxalines (13) double under bar, (15) double under bar, (16) double under bar and (18) double under bar were synthesized through the reactions of 2-hydrazinoquinoxaline (11) double under bar with CS2 ethyl chloroformate, formic acid and p-chlorobenzaidehyde. Ethyl chloroacetate reacted with (11) double under bar to give the triazinoquinoxaline (20) double under bar via the intermediate (19) double under bar.

The present investigation is designed to study the effect of some active methylene compounds on coumarin-6-sulphonyl hydrazones 3a-b. The following active methylene compounds were used: malononitrile, ethyl cyanoacetate, diethylmalonate and 2,4-pentanedione. It was found that, the active methylene compound is added to the double bond of the hydrazone to give an adduct, which cyclized directly to pyrazole or pyrazoline-5-one derivatives 6, 8, 9 and 10.

Sulphanilamide reacts with xanthotoxin-5-sulphonyl chloride, visnagin-9-sulphonyl chloride and aesculetin-3-sulphonyl chloride through the sulphonamide group, while the aromatic amino group remained unaffected through the reaction.

It is reported here synthesis of new sultam derivatives containing benzimidazole, imidazole, oxadiazole, triazole or selenadiazole moieties. N-[2-benzimidazolo]-2,4-dimethyl-1,3-butadiene-1,4-sultam (2) double under bar was synthesized through reaction of the sultone (1) double under bar with 2-aminobenzimidazole. The esters (3a,b) double under bar were formed by reactions of (2) double under bar with ethyl chloroformate and ethyl chloroacetate. (3a) double under bar Reacted with ethylenediamine to give the pyrazoline (4) double under bar. The oxadiazole derivatives (8) double under bar and (10) double under bar were prepared via reactions of the acid hydrazide (5) double under bar with carbon disulphide and 2-thiophenaldehyde followed by cyclization. Reaction of 5 with methylisothiocyanate yielded the corresponding triazole (12) double under bar, while (5) double under bar reacted with phenylisothiocyanate to give the thiosemicarbazide derivative (13) double under bar. The sultone (1) double under bar condensed with aminoacetophenones to afford the sultams (18a,b) double under bar, which reacted with semicarbazide to give the semicarbazones (19a,b) double under bar. Oxidative cyclization of (19) double under bar with SeO2 gave the selenadiazole (20) double under bar. On the other hand, the thiadiazoles (21) double under bar were formed on boiling (19) double under bar with thionyl chloride.

A series of sugar hydrazones and Schiff bases 2 and 4 were prepared by condensation of 2-hydrazino-2,3-dihydro-3-methylbenzothiazole 1 and 2-aminobenzimidazole 3 with monosaccharides such as arabinose, xylose, ribose, mannose and glucose. Acetylation of 2 and 4 with acetic anhydride in pyridine for 8 h furnished the O-acetyl derivatives 5 and 6. On the other hand, acetylation of B and 4 for 24 h gave peracetylated sugar derivatives 7 and 8. Treatment of 2 and 4 with thioglycolic acid led to the formation of the C-nucleosides 9 and 10. Reaction of 3 with ethyl acetoacetate, diethyl malonate and 2,4-pentanedione gave the intermediates 12, 15 and 17 which cyclized to the corresponding pyrimidino-benzimidazoles 14, 16 and 18 on treatment with Na2SO4 and NaHCO3 in boiling ethanol. On the other hand, 1 reacted with 2,4-pentanedione, malononitrile or ethyl acetoacetate to give the pyrazole derivatives 20, 22 or 24 via the intermediates 19, 21 and 23. The compounds 25, 26 and 27 were prepared through Mannich reaction of 1 or 3 with amino or hydroxy compounds.

A new series of pyrimido[1,2-a]benzimidazole derivatives were prepared via reaction of 2-aminobenzimidazole Schiff base 1 with active methylene compounds. 2-Aminobenzimidazole reacted with p-anisaldehyde to give Schiff base 1. Reaction of 1 with malononitrile yielded the aminocyano compound 4. Trimethylorthoformate reacted with 4 to afford the methoxymethylene derivative 6. Reaction of 6 with hydrazine hydrate at room temperature gave the hydrazinomethylene 7, which cyclized to 8 on boiling with dioxane. Coupling of the diazonium salt 9 with aromatic amines gave the open chain triazines 10a,b. Refluxing solutions of 10a,b in ethanol gave the corresponding closed chain triazines 12a,b. The pyrimidobenzimidazole derivatives 14, 18, 21, 24 and 25 were formed via reaction of 1 with diethylmalonate, ethyl acetoacetate, acetylacetone, ethyl chloroacetate and ethyl cyanoacetate. The fused ring system 15 was formed through reaction of 14 with 2-aminobenzimidazole.

2,4-Dimethyl-1,3-butadiene-1,4-sultone 1 reacted with 3-aminomethylbenzoate to give 2. Reaction of 2 with hydrazine hydrate or ammonia solution gave the acid hydrazide 3a or the amide 3b respectively. On hydrolysis of 2 with sodium methoxide the corresponding acid 4 was obtained. The reaction of 3a with benzaldehyde, salicylaldehyde or 4-anisaldehyde afforded the corresponding arylide ne carboxyhydrazide 5a-c, respectively. Treatment of 5a-c with acetic anhydride gave the corresponding 1,3,4-oxadiazole derivatives 6a-c, respectively. Reaction of 3a with isocyanates or isothiocyanates gave the corresponding semicarbazide derivatives 7a-d.

Several coumarin-6-sulphonamides 2a-c and 3a-c were prepared through reaction of coumarin-6-sulphonyl chloride 1 with different aromatic amino compounds. The imidazole derivatives 4a-b were formed by reaction of 3a-c with ethylene diamine. Reaction of 3a-c with hydrazine hydrate afforded the acid hydrazides 5a-c. The oxadiazole 7 was synthesized through reaction of 5c with benzoyl chloride to give the compound 6 which cyclized to the oxadiazole derivative 7 by heating with POCI3. The thiadiazole derivative 9 was synthesized through reaction of 5c with phenylisothiocyanate, followed by treatment with POCI3. Reaction of 3a-c with excess hydrazine hydrate (1:5 mol) proceeded with alpha-pyrone ring fission to give the corresponding cinnamoyl hydrazide derivatives 10a-c. Condensation of 10b with furfural gave the hydrazone 11 which cyclized to the oxadiazole on treatment with acetic anhydride.

Various benzothiazole derivatives were prepared through reactions of 5-hydrazino-2,3-dihydro-3-methylbenzothiazole 1. The compounds 2a-e and 3a-d were synthesized by Mannich reaction of 1 with amino compounds and formaldehyde solution. Sulphanilamide undergoes Mannich reaction with 1 and formaldehyde through sulphonamido group while aromatic amino group remains unaffected. Reaction of 1 with aldehydes afforded the hydrazones 7 which cyclized to give the corresponding thiazolidinone 8 through reaction with thioglycolic acid. The pyrazole derivatives 10 and 12 were synthesized by reaction of 1 with diethyl malonate and ethyl cyanoacetate.

Triazoles 3a-d, oxadiazoles 4a,b and thiadiazoles 4c,d were obtained by different routes of cyclization of 2a-d depending on the reaction condition. Reaction of 1 with CS2, in boiling ethanol, gave the mercapto-oxadiazole 5; while the potassium thiocarbazide salt 6 was obtained when the reac tion takes place at r.t. 6 with hydrazine hydrate was cyclized to the amino-triazole 7. Triazolo-thiazoles 8a,b were formed when 7 reacted with either formic acid or acetic anhydride, respectively. Aroyl hydrazides 9a-d were obtained through reaction of 1 with the appropriate acid chloride. Cyclization of 9a-d using phosphorous oxychloride afforded the corresponding oxadiazoles 10a-d (Chart-1).

A number of xanthotoxin-4-sulfono-derivatives 2a-c, 3a-c and 4a-e were prepared by the reaction of xanthotoxin-4-sulfonyl chloride 1 with amino-compounds or phenolic-compounds. The action of hydrazine hydrate on 1 was studied. Also, the action of hydrazine derivatives on xanthotoxin-4-sulfono derivatives 1, 2a was discussed.

Coumarin-B-sulphonyl chloride 1 reacts with 4-aminobenzenesulphonamide or 2-amino-1,3,4-thiadiazole-5-sulphonamide at the sulphonamido amino group, while the amino group that attached to the ring is not affected through the reaction. Reaction of 1 with 4-aminoacetophenone, o-, m-, and p-phenylenediamine gives the sulphonamides 7 and 9a-c. 7 reacts with hydrazine hydrate or phenylhydrazine to yield the hydrazones 8ab. Cyclization of 9a with aldehydes gives the benzimidazol derivatives 10a-d.

Various coumarin-6-sulphonic acid esters 2a-c are prepared through reaction of coumarin-6-sulphonyl chloride 1 with some phenolic compounds. The reaction of 2a with primary amines led to the Schiff's bases 3a-c. Aceturic or hippuric acid reacts with 2b to give the oxazolone 4a,b. 1 Reacts with some sulphonamides yielding coumarin-6-sulphonamide derivatives 5a-d. Also, coumarin-6-sulphonyl urea derivatives 6a-c and 7a-c were pepared.

Butane-($) under bar 1,($) under bar 2-sultone ($) double under bar 2 and propane-($) under bar 1,($) under bar 3-sultone ($) double under bar 10 react with sulphanilamide through the sulphonamido amino group, while the aromatic amino group remains unaffected through the reaction, The structure of the produced ($) under bar N-substituted aminosulphonic acids is confirmed synthetically.

Coumarin-6-sulphonyl chloride 1 reacted with o-,m-.p-phenylenediamine to give the sulphonamides 2a-c. Phenylisocyanate or phenylisothiocyanate reacted with 2a-c yielding the urea derivatives 3a-f. Condensation of 2a-c with acetaldehyde or acetophenone gave the imins 4a-f. The sulphonic acid esters 5a-c were formed through condensation of 1 with phenolic derivatives.

The optimum conditions for stearamide preparation from stearic acid and urea are determined. The molar ratio, time of reaction, reaction temperature and the catalyst were found to be determining factors for the reaction. From the kinetic study, the reaction was found to be a second order reaction. The reaction rates at different reaction conditions were calculated and the energy of activation was evaluated.

Pyrrolysis of N-substituted-2,4-dimethyl-1,3-butadienesultams-(1,4) 2a,b gave the pyrrol derivatives 3a,b. The carbamates 4a,b were prepared by reaction of the sultams 2c,d with methylisocyanate. Bromination of 2d with Br2 yielded the monobromosultam 5. The hydrazones 6a,b were obtained by condensation of 4-aminoacetophenone with hydrazides. 2,4-dimethyl-1,3-butadienesultone-(1,4) 1 reacted with 6a,b to give the sultams 7a,b. Propanesultone-(1,3) 8 reacted with amino-compounds yielding the corresponding 3N substituted-aminopropane-1-sulphonic acids 9a-c, 11, 12, and 13a-c. Dehydration of 9 with POCl3 gave the N-substituted-propane-sultams-(1,3) 10a-c. Butanesultone-(1,4) 14 reacted with amino-compount to give the amino-sulphonic acids 15a,b which cyclized to the sultams 16a,b.