Aryl effect

Benzylidene anilines formed from benzaldehydes and anilines have been found to undergo ortho arylation effectively when a ruthenium catalyst such as [RuC12(/ 6-C6H6)]2 is used in the presence of K2C03 as base (Eqs. 11 and 12) [17]. A polar solvent such as NMP is used. In this reaction the substrates have no acidic hydrogen and thus ortho metalation seems to occur via coordination of the neutral nitrogen to the metal center, as in the reaction of phosphinite (Scheme 3). Similarly, 2-phenylpyridine [18] (Eq. 13) and 2-phenyl-lH-imidazole (Eq. 14) [19] are arylated. 

The reactions of P-donor nucleophiles with the metal carbonyl cluster Rh4COi2 have been studied over a considerable time period.It is widely accepted that the reaction is associative. This latest investigation is aimed at quantifying the effects of the electronic and steric properties of the nucleophiles upon the kinetic parameters. A rapid substitution reaction step using an excess of the nucleophile was monitored by SF spectrophotometry. Second-order rate constants were obtained from the variation of the pseudo-first-order rate constants with nucleophile concentration. Contributions to these constants from the properties steric effect, TT-activity, and, in addition, an aryl effect of the nucleophiles were assessed in a multi-parameter equation. The outcome is a successful understanding of the relative reactivities of many P-donors toward the rhodium cluster. The data were also represented by a three-dimensional potential energy surface. 

Application of standard quantitative analysis of ligand effects (QALE) methodology enabled the rate constants for the reactions of Ru3(GO)i2 with 32 phosphine ligands to be analyzed according to the electronic and steric properties of the nucleophiles. It was unexpectedly found necessary to include what has become known as the aryl effect in this analysis, together with a positive contribution to the rates due to the 7r-acidity of phosphite nucleo-philes. ... 

The reaction of a halide with 2-butene-1,4-diol (104) affords the aldehyde 105, which is converted into the 4-substituted 2-hydroxytetrahydrofuran 106, and oxidized to the 3-aryl-7-butyrolactone 107[94], Asymmetric arylation of the cyclic acetal 108 with phenyl triflate[95] using Pd-BINAP afforded 109, which was converted into the 3-phenyllactone 110 in 72% ee[96]. Addition of a molecular sieve (MS3A) shows a favorable effect on this arylation. The reaction of the 3-siloxycyclopentene 111 with an alkenyl iodide affords the. silyl... 

The benzoic acid derivative 457 is formed by the carbonylation of iodoben-zene in aqueous DMF (1 1) without using a phosphine ligand at room temperature and 1 atm[311]. As optimum conditions for the technical synthesis of the anthranilic acid derivative 458, it has been found that A-acetyl protection, which has a chelating effect, is important[312]. Phase-transfer catalysis is combined with the Pd-catalyzed carbonylation of halides[3l3]. Carbonylation of 1,1-dibromoalkenes in the presence of a phase-transfer catalyst gives the gem-inal dicarboxylic acid 459. Use of a polar solvent is important[314]. Interestingly, addition of trimethylsilyl chloride (2 equiv.) increased yield of the lactone 460 remarkabiy[3l5]. Formate esters as a CO source and NaOR are used for the carbonylation of aryl iodides under a nitrogen atmosphere without using CO[316]. Chlorobenzene coordinated by Cr(CO)j is carbonylated with ethyl formate[3l7]. 

The infrared spectra of a set of 2-thiazolylthioureas are reported in Ref. 486. The ultraviolet spectra of l-aryl-3-(2-thiazolyl)thioureas are characterized by two bands of approximate equal intensity around 282 and 332 nm (492). For l-alkyl-3-(2-thiazolyl)thioureas these bands are shifted to 255 and 291 nm, respectively (492). The shape of the spectrum is modified further when l.l -dialkyl-3-(2-thiazolyl)thioureas are considered (491). Fragmentation patterns of various 2-thiazolylthioureas have been investigated (100, 493), some of which are shown in Scheme 158. Paper and thin-layer chromatography provide an effective tool for the analysis of these heterocyclic thioureas (494. 495). 

The carbon-halogen bonds of aryl halides are both shorter and stronger than the carbon-halogen bonds of alkyl halides In this respect as well as m their chemical behavior they resemble vinyl halides more than alkyl halides A hybridization effect seems to be responsible because as the data m Table 23 1 indicate similar patterns are seen for both carbon-hydrogen bonds and carbon-halogen bonds An increase m s... 

The preference for O acylation of phenols arises because these reactions are kmetically controlled O acylation is faster than C acylation The C acyl isomers are more stable how ever and it is known that aluminum chloride is a very effective catalyst for the conversion of aryl esters to aryl ketones This isomerization is called the Fries rearrangement... 

Sulfur tetrafluoride [7783-60-0] SF, replaces halogen in haloalkanes, haloalkenes, and aryl chlorides, but is only effective (even at elevated temperatures) in the presence of a Lewis acid catalyst. The reagent is most often used in the replacement of carbonyl oxygen with fluorine (15,16). Aldehydes and ketones react readily, particularly if no alpha-hydrogen atoms are present (eg, benzal fluoride [455-31-2] from benzaldehyde), but acids, esters, acid chlorides, and anhydrides are very sluggish. However, these reactions can be catalyzed by Lewis acids (HP, BF, etc). 

Aromatic perfluoroaLkylation can be effected by fluorinated aUphatics via different techniques. One category features copper-assisted coupling of aryl hahdes with perfluoroalkyl iodides (eg, CF I) (111,112) or difluoromethane derivatives such as CF2Br2 (Burton s reagent) (113,114), as well as electrochemical trifluoromethylation using CF Br with a sacrificial copper anode (115). Extmsion of spacer groups attached to the fluoroalkyl moiety, eg,... 

A combination of Cp nCX —A CXC) (where = cyclopentadienyl) effectively promotes the Friedel-Crafts coupling of glycosyl fluorides with aromatic compounds, such as trimethoxyben2ene or methoxynaphthalenes. The derived C-aryl glycosides are potent antitumor agents (39). 

Superacids such as HF-SbF effect cyclo alkylation of aryl alkyl ketones to give tetralone derivatives (58). Tandem iatramolecular cyclo alkylatioas can be achieved when functional groups are located ia close proximity (59). 

Toxicity. Inorganic mercury compounds, aryl mercury compounds, and alkoxy mercurials are generahy considered to be quite similar in their toxicity. Alkyl mercury compounds are considered to be substantiahy more toxic and hazardous. Mercury and its compounds can be absorbed by ingestion, absorption through the skin, or by inhalation of the vapor. The metal itself, however, rarely produces any harmful effects when ingested (16). 

Phosphoms compounds are effective flame retardants for oxygenated synthetic polymers such as polyurethanes and polyesters. Aryl phosphates and chloroalkyl phosphates are commonly used, although other compounds such as phosphonates are also effective. The phosphoms compounds can promote char formation, thereby inhibiting further ignition and providing an efficient thermal insulation to the underlying polymer. 

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