Results in Acetonitrile

On the basis of the results in acetonitrile, it might be reasonable to assume that the values for A//het(R-R ) and AG°het(R-R ) are apparently close to each other also in sulfolane, since the dielectric constant (43.3) and the donor number (14.8) of this solvent are close to those of acetonitrile (37.5 and 14.1, respectively). On the basis of this assumption, Arnett s equation (28) was examined for reactions of type (23). For these reactions, except for [3-2], only the AGhet(R-R ) values are avtiilable. As shown in Fig. 3, the values for this system are about 10 kcal moP less than predicted from (28). The negative deviation can also be ascribed to steric congestion in these hydrocarbon molecules. The large negative deviations, similar to those observed in sulfolane, are also seen in Fig. 3 for the values of AGSet(R-R ) in DMSO. 

Lowe and Tuck (1986) used PIX in the case of a nonenzymic substitution reaction at phosphorus that possibly involved a metaphosphate intermediate. These workers prepared ADP with label in the bridge position and incubated samples under a variety of reaction conditions. Should the P—O bond break and re-form, as expected if an ion pair involving metaphosphate formed, then PIX could be expected to occur. No PIX is observed in aqueous solution, but it does occur when acetonitrile is used as a solvent. However, the result in acetonitrile establishes the existence of an intermediate, but does not define its structure. The possibilities for the intermediate include an ion pair of metaphosphate and AMP, but do not preclude phosphorylated solvent and AMP as an alternative set of intermediates. 

The low stabilities of the complex compounds of class (a) metal ions with weak ligands are also reflected in the shapes of the potentiometric titration curves, which show no inflexions in contrast to the results in acetonitrile or trimethyl phosphate, where the stabilities are much higher. 

In contrast to the situation in the absence of catalytically active Lewis acids, micelles of Cu(DS)2 induce rate enhancements up to a factor 1.8710 compared to the uncatalysed reaction in acetonitrile. These enzyme-like accelerations result from a very efficient complexation of the dienophile to the catalytically active copper ions, both species being concentrated at the micellar surface. Moreover, the higher affinity of 5.2 for Cu(DS)2 compared to SDS and CTAB (Psj = 96 versus 61 and 68, respectively) will diminish the inhibitory effect due to spatial separation of 5.1 and 5.2 as observed for SDS and CTAB. 

In contrast to SDS, CTAB and C12E7, CufDSjz micelles catalyse the Diels-Alder reaction between 1 and 2 with enzyme-like efficiency, leading to rate enhancements up to 1.8-10 compared to the reaction in acetonitrile. This results primarily from the essentially complete complexation off to the copper ions at the micellar surface. Comparison of the partition coefficients of 2 over the water phase and the micellar pseudophase, as derived from kinetic analysis using the pseudophase model, reveals a higher affinity of 2 for Cu(DS)2 than for SDS and CTAB. The inhibitory effect resulting from spatial separation of la-g and 2 is likely to be at least less pronoimced for Cu(DS)2 than for the other surfactants. 

Health and Safety Factors. The following toxicides for acetonitrile have been reported oral LD q (lats), 3030—6500 mg/kg skin LD q (rabbits), 3884—7850 mg/kg and inhalation LC q (i ts), 7500—17,000 ppm (29). Humans can detect the odor of acetonitrile at 40 ppm. Exposure for 4 h at up to 80 ppm has not produced adverse effects. However, exposure for 4 h at 160 ppm results in reddening of the face and some temporary bronchial tightness. 

With solvents having a nitrile group like acetonitrile, the selectivity of y-butyrolactone is increased, resulting in a yield of 60%. 

Cyalohexylideneaaetonit ri-le. A 1-L three-necked, round-bottomed flask equipped with a reflux condenser, mechanical stirrer and addition funnel, is charged with potassium hydroxide (855 pellets, 33.0 g, 0.5 mol. Note 1) and acetonitrile (250 ml. Notes 2 and 3). The mixture is brought to reflux and a solution of cyclohexanone (49 g, 0.5 mol. Note 4) in acetonitrile (100 mL) is added over a period of 0.5-1.0 hr. Heating at reflux is continued for 2 hr (Note 5) after the addition is complete and the hot solution is then poured onto cracked ice (600 gl. The resulting binary mixture is separated... 

The radical stabilization provided by various functional groups results in reduced bond dissociation energies for bonds to the stabilized radical center. Some bond dissociation energy values are given in Table 12.6. As an example of the effect of substituents on bond dissociation energies, it can be seen that the primary C—H bonds in acetonitrile (86 kcal/mol) and acetone (92kcal/mol) are significantly weaker than a primaiy C—H... 

Aqueous hydrofluoric acid dissolved in acetonitrile is a good catalyst for intramolecular Diels-Alder reactions [9] This reagent promotes highly stereoselective cyclizations of different triene esters (equation 8) The use of other acids, such as hydrochloric, acetic, and trifluoroacetic acid, results in complete polymerization of the starting trienes [9] (equation 8)... 

The volume calculation results in a cavity radius of 3.65. The acetonitrile solution produces only subtle changes in the molecule s structure. The only significant change is a decrease of 0.3-0.4° in the O-C-H bond angle. 

It has been shown that TMSI is capable of mediating the reaction at room temperature. The classical three component coupling was carried out using aldehyde 82 and ketoester 83 with ammonium acetate in acetonitrile at room temperature with in situ generated TMSI. This gave a 73-80% yield of 1,4-dihydropyridines 84 in 6-8 h. The best results were obtained with 1 equivalent of TMSCl and 1 equivalent of Nal. 

With [RUjfCOlij], dinuclear species 161 emerges (88JCS(D)1437). In contrast, with [Os3(CO) q(AN)J, two isomers, 162 and 163, result (88JOM (353)251). Isomer 162 enters the CO/AN monosubstitution reaction in acetonitrile in the presence of Mc3N0-2H20, the product on subsequent thermolysis forms the hexanuclear complex 164. 

The addition of co-solvents to ionic liquids can result in dramatic reductions in the viscosity without alteration of the cations or anions in the system. The haloaluminate ionic liquids present a challenge, due to the reactivity of the ionic liquid. Nonetheless, several compatible co-solvents including benzene, dichloromethane, and acetonitrile have been investigated [33-37]. The addition of as little as 5 wt. % acetonitrile or 15 wt. % benzene or methylene chloride was able to reduce the... 

The results in the ionic liquid were compared with those obtained in four conventional organic solvents. Interestingly, the reaction in the ionic liquid proceeded with very high selectivity to give the a-arylated compound, whereas variable mixtures of the a- and (3-isomers were obtained in the organic solvents DMF, DMSO, toluene, and acetonitrile. Furthermore, no formation of palladium black was observed in the ionic liquid, while this was always the case with the organic solvents. 

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