Acetonitrile benzene, substituted

Cesium fluoroxysulfate in acetonitrile medium at 35 C converts primary alcohols and alkyl and aryl aldehydes into acid fluorides in high yields.i" Hammett correlation analysis of the fluorination of various benzene-substituted aldehydes gives the reactivity constant31 q = —0.38. It has been shown that solvent polarity plays an extremely important role in the conversion of aldehydes into fluorides the conversion is almost quantitative in acetonitrile, but completely stopped in dichloromethane, hexane or tetrahydrofuran. The presence of ni-... 

The reaction was extended to PhCH2X (X = Cl or Br) which gives the hexa(phenyl-ethyl)benzene complex. The new free aromatic ligand is easily disengaged by photolysis in acetonitrile [76a] Eq. (20). This line of research is now offering us the perspective of making new discotic liquid crystals using suitably substituted... 

Novel ruthenium-amidinate complexes of the type (j -CgHsRlRufamidina-te)X (R = Me, OMe, F X = Cl, Br, OTf) and [Ru(amidinate)(MeCN)4][PF6] have been synthesized by photochemical displacement of the benzene ligand in (j -CgHglRufamidinatelX by substituted arenes or MeCN. The acetonitrile ligands of [Ru(amidinate)(MeCN)4][PF6] are easily replaceable by other cr-donor ligands (L) such as pyridines, phosphines, and isocyanides to afford the corresponding derivatives [Ru(amidinate)(MeCN) (L)4 ][PF6] n — 1, 2). These reactions are summarized in Scheme 142. ... 

Reactions between aromatic hydrocarbon radicabcations and cyanide ions, with few exceptions, give low yields of nuclear substitution products [76], In some cases, better results have been obtained by anodic oxidation of the aromatic compound in an emulsion of aqueous sodium cyanide and dichloromethane with tetra-butylammonium hydrogen sulphate as a phase transfer agent [77, 78]. Methoxy-benzenes give exceptionally good yields from reactions in acetonitrile containing tetraethylammonium cyanide, sometimes with displacement of methoxide [79, 80]... 

Cesium fluoroxysulfate reacts with various substituted benzene derivatives in acetonitrile at room temperature, and a Hammett correlation parameter r>+ = —3.5 has been established.1- ... 

The course of the reaction of methyl-substituted benzene derivatives with cesium fluoroxysulfate in acetonitrile at 35-40 C strongly depends on the structure of the molecule. Toluene (16, R1 = R2 = H) and other alkyl-substituted benzenes 16 and 17 are mainly functionalized on the side chain, while 1,3.5-trimethylbenzene (18) gives mainly ring-substituted products 24 however. 1.2.4,5-tetramethylbenzene (19) and hexamethylbenzene again give mainly or exclusively side-chain products.25... 

Since these substitution reactions follow a two-term rate law, it is clear that solvent effects are very significant. Poorly coordinating solvents are benzene, carbon tetrachloride and sterically hindered alcohols and strongly coordinating solvents are water, lower alcohols, DMF, DMSO, acetonitrile and nitromethane. The first-order rate constants are greater in DMSO than in water. Since the majority of precursor platinum complexes used in synthetic and mechanistic studies are halo complexes, the replacement of halide ligands by solvent and the reversibility of this reaction are important features of platinum halide chemistry. 

A number of indoles of type 315 have been made (80TL281 83JOC3639) by stirring f-butyl and some other isocyanides in benzene or acetonitrile with various arylnitropropenes (314), and the reaction is thought to proceed as indicated. 5-,6-, and 7-Substituted and benzole]- and -[g]-l-hydroxyindoles have also been obtained yields varied from 15-87%. 

The synthetically useful a,/J-unsaturated [nC]-labelled precursors, [nC]acrylonitrile (192) and [11C]cinnamonitrile (193), have been prepared189-191 with potassium [nC]cyanide (equation 101). The substitution reactions have been performed in MeCN, benzene, 1,2-dichlorobenzene, DMSO and THF solvents, but the highest radiochemical yields were obtained in acetonitrile. 192 was used in a model reaction (equation 102) to synthesize 2-cyano[nC]ethyldimethyl malonate 194 from sodium hydride/dimethyl malonate. 

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