Ahmed Khodairy

Substituted Quinolinones, Part 14: Synthesis of Novel Dispiro(heterocycle-N,2′-[1,3]dithietane-4′,3″-quinolinedione) Derivatives Under PTC Conditions

Abstract The four-membered spiro-heterocycles ethyl cyano(1-methyl-2,4-dioxospiro{1,3-quinoline-3,4′-[1,3]dithietane}-4′-ylidene)-acetate 2a, -malononitrile 2b, -acetylacetone 2c, and thiazetidine isomer 3 were prepared under phase transfer catalysis (PTC) conditions. The thermal treatment of dithietanes 2a–c led to the bis-quinolinyl sulfide 4. Some interesting nucleophilic additions followed by cyclization reactions were carried out with the dithietane 2a to give the corresponding novel dispiro derivatives 5–8, 10–13, and 15. Supplemental materials are available for this article. Go to the publishers online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. GRAPHICAL ABSTRACT

Synthesis of 3,4-biheterylthieno[2,3-b]-thiophenes. Part I: Synthesis of 3,4-Bi(1', 3', 4'-thiadiazolyl-, s-triazolyl-, 1', 3', 4'-thiadiazinyl-, 1',3', 4'-triazinyl-, thiazolyl-, 1', 3'-thiazinyl- and primidinyl)-thieno[2,3-b]thiophenes

3,4-Diamino-2,5-dicarbethoxythieno[2,3-b]thiophene ( 1 ) was allowed to react with NaNO 2 and active methylenes to afford the corresponding azo compounds 2a-c . Hydrazonyl chloride 2a was treated with carbon disulfide, phenyl isothiocyanate, benzonitrile, benzyl cyanide, malononitrile, benzalaniline, ethyl mercaptoacetate, and ethyl glycinate to give 1,3,4-thiadiazolyl-, s-triazolyl-, 1,3,4-thiadiazinyl-, 1,3,4-triazinylthieno[2,3-b]thiophenes 3-6 respectively. The reaction of 2b,c with urea, thiourea, and guanidine afforded pyrimidinyl- and thiazinylazothieno [2,3-b]thiophenes 7-10 respectively. Bithiazolylthieno[2,3-b]thiophenes 11 and 13 were synthesized by treating compound 1 with CS 2 along with halo compounds. The addition of S,S-, N,S-, and N,O-acetals to the Schiff base 14 afforded compounds 15-17 respectively.

Synthesis, in vitro Antibacterial and in vivo Anti-Inflammatory Activity of Some New Pyridines

Reaction of 4,6-diamino-3-cyano-2-methylthiopyridine (I) with chloroacetyl chloride or acetic acid afforded the corresponding 6-acetamide derivatives IIa and IIb, respectively. Chloroacetamide derivative IIa reacted with various thiols, secondary amines, potassium thiocyanate, compounds containing active methylene group, 1-anilino-2,2-dicyanoethenethiolate, and o-mercatocyanopyridines to give S-alkyl, N-alkyl, thiazole, pyrrole, thiophene, and thienopyridine derivatives, respectively. Antibacterial and anti-inflammatory activities of some new pyridine derivatives were studied.

Utility of Hydrazinopiperidinomethanethione in Synthesis of Thiadiazole, Thiadiazine, and Pyrazole Derivatives

Hydrazinopiperidinomethanethione 2 was prepared and reacted with active halo compounds, carbon disulfide, phenyliso-thiocyanate, ylidenenitriles, and N,S-acetyls to give thiadiazine 4–7 , thiadiazole 8–10 , and pyrazole 11,13 , 14–17 derivatives, respectively.

Crystal structure of ethyl 4-(2-meth-oxy-phen-yl)-6-methyl-2-sulfanyl-idene-1,2,3,4-tetra-hydro-pyrimidine-5-carboxyl-ate.

In the title compound, C15H18N2O3S, the hydropyrimidine ring adopts a sofa conformation with the methine C atom as the flap. The benzene ring is almost perpendicular to the mean plane of the hydropyrimidine ring, making a dihedral angle of 85.51 (8)°, and the methoxy O atom lies over the centre of the pyrimidine ring. In the crystal, weak N—H⋯S interactions form a zigzag chain running along the b-axis direction.

Crystal structure of (4Z)-4-[(di-methyl-amino)-methyl-idene]-3,5-dioxo-2-phenyl-pyrazolidine-1-carbaldehyde.

In the title compound, C13H13N3O3, the pyrazolidine ring adopts a shallow envelope conformation, with the carbonyl C atom closest to the benzene ring as the flap [deviation of 0.126 (1) Å from the plane through the remaining atoms (r.m.s. deviation = 0.011 Å)]. The dihedral angle between the pyrazolidine ring (all atoms) and the benzene ring is 51.09 (4)°. An extremely short (2.08 Å) intramolecular C—H⋯O contact is seen. In the crystal, molecules are linked by C—H⋯O bonds, generating [010] chains. Extremely weak C—H⋯π interactions are also observed.