Erdal Ertas

A Berzelius Reagent, Phosphorus Decasulfide (P4S10), in Organic Syntheses

2.3. Amides and Lactams 3435 2.4. Imides 3448 2.5. Thiophenes 3451 2.6. Thiazolines, Thiazoles, and Thiazines 3454 2.7. Dithiazoles 3456 2.8. Thiadiazoles 3456 2.9. Imidazolines and Pyrimidines 3456 2.10. Alcohols 3458 2.11. PdO to PdS 3461 2.12. Reduction 3462 2.13. Nucleotides, Purines, and Pyrimidines 3463 2.14. Miscellaneous 3467 2.15. P4S10 vs Lawesson’s Reagent (LR) 3473 3. Conclusion 3473 4. Acknowledgments 3473 5. References 3473

A Highly Functionalized BEDT-TTF Derivative

The synthesis of a highly functionalized BEDT-TTF derivative containing phenyl-1,4-dithiin and 2,3-dihydroxybutane-1,4-dithio peripherals is described.

Bis(vinylenedithio)tetrathiafulvalene analogues of BEDT-TTF

Summary This review aims to give an overview of the current status of our research on the synthesis of π-electron donor bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF, ET) analogues prepared from 1,8-diketones via a ring forming reaction. The new synthesized π-electron donors have vinyl moieties producing extended π-electron delocalization over the substituent phenyl rings at the peripheries.

Intramolecular interactions in ethyl bis-(2,4-dinitrophenyl)acetate

The crystal structure of ethyl bis(2,4-dinitrophenyl)acetate, determined by room temperature X-ray diffraction, shows that this crowded molecule contains two short intramolecular interactions between nitro oxygen atoms and electron deficient carbon atoms. One mimics an early stage of the nucleophilic addition to a carbonyl group (O...C, 2.730 Å), and the other mimics an early stage of a Michael reaction (O...C, 2.854 Å). Crystal data: C16H12N4O10, Mr = 420.29, a = 10.079(1), b = 11.139(1), c = 16.162(1) Å, β = 91.319(7)°, monoclinic, P21/c, Z = 4.

Synthesis and Properties of Thiophene and Dithiin Functionalized Tetrathiafulvalenes

Abstract Syntheses of two analogues of tetrathiafulvalene (TTF), fused to 1,4-dithiin and thiophene rings, substituted with thiophene moieties, have been illustrated. The syntheses were accomplished through the reaction of a 1,8-diketone with phosphorus pentasulfide or Lawessons reagent in boiling dry toluene. Conversion of the thioketones to their the oxo forms with mercury (II) acetate, was followed by self-coupling in freshly distilled boiling triethyl phosphite. Attempts for their electro-polymerizations through the thiophene groups at the peripherals were unsuccessful. Computational chemistry studies revealed that the thiophene groups did not exhibit enough spin densities to perform polymerization. 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

3,4-Bis[(4-methoxy­benzo­yl)methyl­sulfanyl]thio­phene

A new type of thiophene derivative having alpha-thioketone groups at the 3- and 4-positions, viz. the title compound, C22H20O4S3, has been prepared and studied by NMR spectroscopy and single-crystal X-ray diffraction techniques. The molecule is nearly planar, the dihedral angles between the essentially planar thiophene and benzene rings being 9.4 (1) and 10.6 (1) degrees. One of the thioketone O atoms is involved in an intermolecular C-H...O hydrogen-bonding interaction.

5,6-Diphenyl[1,3]dithiolo[4,5-b]-dithiine-2-thione.

In the title compound, C(17)H(10)S(5), the dithiine ring adopts a boat conformation while the dithiole ring has an envelope conformation. The phenyl groups are planar and make dihedral angles of 40.7 (2) and 59.8 (2) degrees with the best plane of the thiine ring. The shortest intermolecular S...S contact is 3.305 (2) A.

5,6-Diphenylthieno[2,3-d][1,3]-dithiole-2-thione

The title compound, C(17)H(10)S(4), has two independent molecules in the asymmetric unit. In both molecules, the fused heterocycle is almost planar and the phenyl groups make dihedral angles of 42.88 (9) and 52.79 (8) degrees with the fused heterocycle in one molecule, and angles of 40.62 (9) and 52.28 (8) degrees in the other. The crystal packing is governed by short intermolecular S.S interactions, the shortest contact being 3.333 (1) A.

5-Benzyl-5-phenyl[1,3]dithiolo[4,5-d]-[1,3]dithiole-2-thione.

In the title compound, C(17)H(12)S(5), the dithiole ring bearing the aryl substituents assumes an envelope conformation with the maximum deviation from planarity being -0.053 A. The phenyl and benzyl rings are twisted by 33.0 (1) and 31.1 (1) degrees, respectively, out of the dithiole plane. The crystal packing is governed by short S...S interactions, with the shortest being 3.550 (2) A.

An important application of the 1,8-diketone ring formation reaction: a concise synthesis of 5,6-diphenyl[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione and its coupling product

Syntheses of fully unsaturated 5,6-diphenyl[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione and its coupling product, a fully unsaturated analogue of BEDT-TTF, have been achieved by a 1,8-diketone ring formation reaction.