Organic Sulfur Compounds. XII

Abstract

In the solid state, a characteristic reaction is observed on heating of ground mixtures of 1-methyl-4-oxo-cis-2,6-diphenylthianium tetrafluoroborate (1) and alkali halides. These reactions occurred via ion exchange.These reaction products were 4-oxo-cis-2,6-diphenylthiane (6) and 5-(methylthio)-1,5-diphenyl-(E)-1-penten-s-trans-3-one (3) in KC1, mainly dibenzalacetone (4) in KBr, 1,5-bis(methylthio)-1,5-diphenylpentan-3-one (5), 3, 4, and 6 in KI, 3, 4, and 6 in NaCI, respectively, and different from those at room temperature. Moreover, the existence of three crystal forms (form I, II and III) and an amorphous form of 1 was confirmed by powder X-ray diffraction.Polymorphic transformations caused by heating, standing and by mechanical treatment such as grinding.In the solid-state reaction, grinding of mixture occurs the interaction such as adsorption.Moreover, thermal solid-state reaction by differential thermal analysis was affected by the grinding times and amount of alkali halide.

Structures of 2,6-bis(benzylidene)cyclohexanone (III) and 3,5-bis(4-dimethylaminobenzylidene)-1-methyl-4-piperidone (IV)

“…C1N2-N2-C12-CI 1 C2N2--N2-C 12-C 11 C 1N3-N3-C18--CI7 C2N3-N3-C18-C 19 N 1-C2-C3-C4 C 1-C2-C3-C4 -41.0 (2) C2-C3-C8-C9 5.9 (2) C4-C 5-C 6-N 1 C4-C5-C6-C 1 28.5 (2) C6-C5-C7-C 15 -0.5 (3) C5-C7-C 15-C20 -28.7 (2) C3-C8-C9-C 14 40.1 (2) C8-C9-C14-C 13 179.7 (2) C7-C 15-C20-C 19 177.6 (1) (5) C8-C9, C7-C15 bonds at the expense of the conjugation energy of the system. Similar effects have been observed previously (Tokuno, Matsui, Miyoshi, Asao, Ohashi & Kihara, 1986). For example, the opening of the angle C5-C7-C15 leads to a value of 130.5(1) ° (III), 132.2(3) ° (IV).…”

Solvent-free and time-efficient Suzuki–Miyaura reaction in a ball mill: the solid reagent system KF–Al2O3under inspection

“…Over the last two decades, a major trend in the field of organic chemistry has been evident: environmentally friendly processes using safer reagents, generating fewer side products and requiring less use of solvents are in vogue [ 1 – 2 ]. This trend has led to an explosive growth in the fields of solvent-free synthesis [ 3 – 13 ] and solid-supported reagents [ 14 – 18 ] such as potassium fluoride on alumina (KF–Al 2 O 3 ) [ 19 – 20 ]. This versatile reagent was originally introduced in 1979 by Ando et al as a useful agent for inducing alkylation reactions [ 21 ].…”