Acetonitrile surface reactions

A silica-supported Sn—V—P—O catalyst (Sn/V/P = 1/9/3) was investigated by Onsan and Trimm [244]. Working with a flow reactor at about 520°C, a maximum selectivity of 75% to acrylonitrile was reached at a contact time of ca. 230 g sec l-1 and an oxygen/propene/ammonia ratio of 2/1/1.75. The authors assume that the six principal products (acrylonitrile, acetonitrile, HCN, CO, C02, N2) are formed by six parallel reactions and in the first instance apply power rate equations. A more detailed analysis reveals that a Langmuir—Hinshelwood type rate equation, surface reaction being rate-determining, properly describes the production of acrolein plus acrylonitrile from propene, viz. 

In this way, it is possible to attach both aromatic and aliphatic carboxyUc acids to nanodiamond. The reaction is conducted wet-chemically in a suitable dispersing agent like hexane, cyclohexane, THF, or DMF. In acetonitrile, a reaction occurs with the solvent itself The radical initiator abstracts a hydrogen atom of the methyl group and the resulting alkyl is attached to a radical center on the diamond surface (Figure 5.44). This allows for estabhshing nitriles on the diamond that constitute valuable for further syntheses. 

Previous sections have detailed numerous examples where ultrasound has been used to activate a metal surface. Reaction with species in solution then provides a rapid route to a variety of organometalhc products. However, these effects are not confined to organometalhc systems and there are already a number of examples where inorganic bases can be used under heterogeneous conditions in wholly organic reactions. Shibata and-co-workers [200] have described the cyanomethylation of a variety of chalcones by Michael addition of the anion derived from acetonitrile. Sonolysis for 15 min in the presence of KO2 gave the adducts (44) as the major product in each case (Scheme 93). 

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. 

The reaction time depends on the quality of the potassium hydroxide employed. An induction period is often observed when older potassium hydroxide samples are used, possibly because surface formation of carbonates reduces the solubility of the salt in acetonitrile. An attempt was made to monitor the cinnamonitrile reaction by GLC, following loss of starting... 

In order to prepare thin fdms of (SN) on plastic or metal surfaces, several processing techniques have been investigated, e.g., the electroreduction of [SsNs]" salts. Powdered (SN) is prepared by the reaction of (NSC1)3 with trimethylsilyl azide in acetonitrile/ The sublimation of (SN) at 135°C and at pressure of 3 x 10 Torr. produces a gas-phase species, probably the cyclic [SsNs] radical, that reforms the polymer as epitaxial fibres upon condensation/... 

However, even if electrolytes have sufficiently large voltage windows, their components may not be stable (at least ki-netically) with lithium metal for example, acetonitrile shows very large voltage windows with various salts, but is polymerized at deposited lithium if this reaction is not suppressed by additives, such as S02 which forms a protective ionically conductive layer on the lithium surface. Nonetheless, electrochemical stability ranges from CV experiments may be used to choose useful electrolytes. 

The performance of various solvents can be explained with the help of the role of these solvents in the reaction. These solvents help in keeping teth benzene and hydrogen peroxide in one phase. This helps in the easy transport of both the reactants to the active sites of the catalyst. The acetonitrile, and acetone adsorption data on these catalysts (Fig. 6), suggests that acetonitrile has a greater affinity to the catalytic surface than acetone. There by acetonitrile is more effective in transporting the reactants to the catalyst active sites. At the same time, they also help the products in desorbing and vacating the active sites. 

Surface Modification. A polydiene film (supported on a microscope slide) was immersed in a stirred, room temperature, RTD-acetonitrile solution of known concentration contained in a large glass-stoppered test tube. After a specific reaction time, the film was removed from the solution, washed with acetonitrile, water, and acetonitrile again, and dried under vacuum (Step 1). Films subsequently treated with base were immersed in aqueous solutions for 5-15 min. They were then washed with water and CH3CN, and vacuum dried (Step 2). Some films were aged in air at room temperature. 

When the reaction times for Step 1 are 5 min or longer, the samples severely crack, curl, or dissolve. These results suggest that substantial reaction is occurring in the bulk of the polymer. Significant hydrophilization can occur with reaction times as short as 5 s with RTD concentrations of 0.2-0.5 M. However, 0.002-0.02 M solutions of MeTD or PhTD do not allow sufficient reaction rates for surface hydrophilization at the shorter reaction times. Thus, diffusion of MeTD and PhTD into the polymer must occur readily from the acetonitrile solutions. Acetonitrile was used because it does not swell or dissolve the polymer or RTD-polymer adduct, and the RTDs are soluble and stable in it. This solvent is quite polar (dielectric constant, 38) (25), and this is probably a major factor in the partitioning of the relatively nonpolar RTDs between the polydiene film and the solvent. As noted below, more polar RTDs show less tendency to diffuse into the polymer. 

Water is involved in most of the photodecomposition reactions. Hence, nonaqueous electrolytes such as methanol, ethanol, N,N-d i methyl forma mide, acetonitrile, propylene carbonate, ethylene glycol, tetrahydrofuran, nitromethane, benzonitrile, and molten salts such as A1C13-butyl pyridium chloride are chosen. The efficiency of early cells prepared with nonaqueous solvents such as methanol and acetonitrile were low because of the high resistivity of the electrolyte, limited solubility of the redox species, and poor bulk and surface properties of the semiconductor. Recently, reasonably efficient and fairly stable cells have been prepared with nonaqueous electrolytes with a proper design of the electrolyte redox couple and by careful control of the material and surface properties [7], Results with single-crystal semiconductor electrodes can be obtained from table 2 in Ref. 15. Unfortunately, the efficiencies and stabilities achieved cannot justify the use of singlecrystal materials. Table 2 in Ref. 15 summarizes the results of liquid junction solar cells prepared with polycrystalline and thin-film semiconductors [15]. As can be seen the efficiencies are fair. Thin films provide several advantages over bulk materials. Despite these possibilities, the actual efficiencies of solid-state polycrystalline thin-film PV solar cells exceed those obtained with electrochemical PV cells [22,23]. 

In 2002 Mehnert and co-workers were the first to apply SILP-catalysis to Rh-catalysed hydroformylation [74], They described in detail the preparation of a surface modified silica gel with a covalently anchored ionic liquid fragment (Scheme 7.7). The complex N-3-(3-triethoxysilylpropyl)-4,5-dihydroimidazole was reacted with 1-chlorobutane to give the complex l-butyl-3-(3-triethoxysilylpropyl)- 4,5-dihydroimidazolium chloride. The latter was further treated with either sodium tetrafluoroborate or sodium hexafluorophosphate in acetonitrile to introduce the desired anion. In the immobilisation step, pre-treated silica gel was refluxed with a chloroform solution of the functionalised ionic liquid to undergo a condensation reaction giving the modified support material. Treatment of the obtained monolayer of ionic liquid with additional ionic liquid resulted in a multiple layer of free ionic liquid on the support. 

The next step is the analysis of the behaviour of the wave function coefficients c,, the natural solvent coordinates s = T.s, and the corresponding diagonal elements of the transformed solvent force constant matrix Kmm along the ESP. For perspective, the ESP is reported in Fig.2, superimposed on the full nonequilibrium free energy surface for the reaction system in acetonitrile (the justification for the coordinates choice R and s3 will be given below). 

Conducted in 10% CH2Cl2-90% acetonitrile for compounds [54] and [56] and in acetonitrile [55] upon addition of 2 equiv of the respective cation supporting electrolyte, 0.10 mol dm-3 TBABF4. The potential of the reduction current peak r, reversible q, quasi-reversible s, single reduction peak without corresponding reoxidation peak ec, electron transfer followed by a chemical reaction ec, ad, electron transfer followed by a chemical reaction with insoluble product which adsorbs on to the electrode surface. Prewaves are in parentheses. 

In the presence of an oxidant, e.g., chlorate or bromate ions, the electrode reaction is transposed into an adsorption coupled regenerative catalytic mechanism. Figure 2.85 depicts the dependence of the azobenzene net peak current with the concentration of the chlorate ions used as an oxidant. Different curves in Fig. 2.85 correspond to different adsorption strength of the redox couple that is controlled by the content of acetonitrile in the aqueous electrolyte. In most of the cases, parabolic curves have been obtained, in agreement with the theoretically predicted effect for the surface catalytic reaction shown in Fig. 2.81. In a medium containing 50% (v/v) acetonitrile (curve 5 in Fig. 2.85) the current dramatically increases, confirming that moderate adsorption provides the best conditions for analytical application. 

Irradiation of BeP in hexane solution did not lead to the formation of the major derivates produced on adsorbed phases. This result suggests that BeP in nonpolar solvents photodegrades through a different reaction pathway than when adsorbed on surfaces. The type of solvent may affect, on the other hand, BeP photodegradation. In acetonitrile, for example, the photodegradation rate is faster than in hexane, and dione has been detected as one of the products. 

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