Aqueous conditions

The nitration of sensitive compounds with dinitrogen pentoxide has the advantage of avoiding the use of strong acids or aqueous conditions this has been exploited in the nitration of benzylidyne trichloride and benzoyl chloride, which reacted in carbon tetrachloride smoothly and without hydrolysis. 

The theory that the catalysed nitration proceeds through nitrosation was supported by the isolation of some />-nitrosophenol from the interrupted nitration of phenol, and from the observation that the ortho.-para ratio (9 91) of strongly catalysed nitration under aqueous conditions was very similar to the corresponding ratio of formation of nitrosophenols in the absence of nitric acid. ... 

Phenohc resins (qv), once a popular matrix material for composite materials, have in recent years been superseded by polyesters and epoxies. Nevertheless, phenohc resins stiU find considerable use in appHcations where high temperature stabiHty and fire resistance are of paramount importance. Typical examples of the use of phenoHc resins in the marine industry include internal bulkheads, decks, and certain finishings. The curing process involves significant production of water, often resulting in the formation of voids within the volume of the material. Further, the fact that phenoHcs are prone to absorb water in humid or aqueous conditions somewhat limits their widespread appHcation. PhenoHc resins are also used as the adhesive in plywood, and phenohc molding compounds have wide use in household appliances and in the automotive, aerospace, and electrical industries (12). 

Aminopyrazines and 2-aminoquinoxalines, like their pyridine analogs, react with nitrous acid under aqueous conditions to give the 2(l//)-pyrazinones and 2(l//)-quinoxalinones. 2-Aminoquinoxalines are more readily hydrolyzed than typical heterocyclic amines and 2-amino-3-methylquinoxaline, for example, undergoes hydrolysis on heating at 100 °C with dilute sodium hydroxide (59JCS1132). 

This reagent forms aiyl benzoates under aqueous conditions. (It also acylates amines and carboxylic acids.)... 

Only particles of linear or very slightly cross-linked <0.6%) polymers may be produced by dispersion polymerization. Obviously, dispersion polymerization may be used for the production of monosized seed particles, which, after transfer to aqueous conditions, are used for the production of different cross-linked and macroporous particles by the activated swelling and polymerization method. 

The characteristics of these alloys make them ideal for boat and shipbuilding, for which a long history of satisfactory performance is on record for the higher magnesium alloys. Where strength is less critical the lower magnesium alloys may be used with similar success and are recommended for aqueous conditions. 

K has the value of about 1 x 10 at 298 K, and in solutions of copper ions in equilibrium with metallic copper, cupric ions therefore greatly predominate (except in very dilute solutions) over cuprous ions. Cupric ions are therefore normally stable and become unstable only when the cuprous ion concentration is very low. A very low concentration of cuprous ions may be produced, in the presence of a suitable anion, by the formation of either an insoluble cuprous salt or a very stable complex cuprous ion. Cuprous salts can therefore exist in contact with water only if they are very sparingly soluble (e.g. cuprous chloride) or are combined in a complex, e.g. [Cu(CN)2) , Cu(NH3)2l. Cuprous sulphate can be prepared in non-aqueous conditions, but because it is not sparingly soluble in water it is immediately decomposed by water to copper and cupric sulphate. 

More generally, Valez et al. have reviewed the corrosion behaviour of silicate and borate glasses in contact with alkali metals and molten salts, as well as in aqueous conditions. 

The 14e compound MTO readily forms coordination complexes of the type MTO-L and MTO-L2 with anionic and uncharged Lewis bases [96], These yellow adducts are typically five- or six-coordinate complexes, and the Re-L system is highly labile. Apart from their fast hydrolysis in wet solvents, MTO-L adducts are much less thermally stable then MTO itself. The pyridine adduct of MTO, for instance, decomposes even at room temperature. In solution, methyltrioxorhenium displays high stability in acidic aqueous media, although its decomposition is strongly accelerated at increased hydroxide concentrations [97, 98], Thus, under basic aqueous conditions MTO decomposes as shown in Equation (4). 

Unactivated aziridines, such as 24, are not as reactive as their N-sulfonyl analogues. Nevertheless, in aqueous conditions they react with different nucleophiles, as Scheme 12.23 illustrates. Treatment with buffered azide at 50 °C gave 25 in 90% yield. Hydrazine proved potent even at room temperature and 26 was fonned in 95 % yield, while phenyltetrazole required heating at reflux in water. The resulting amines participated in dipolar cycloadditions with alkynes and condensations with P-diketones. 

Goerdeler and Deselaers (1958) showed that even under aqueous conditions the nitrosoamine 3.12 can be obtained if a relatively low concentration of H2S04 (1 m) or at least one equivalent of H2S04 is used. 

Alternatively, 3-phenyl pyrazinone was prepared via Suzuki reaction, when a polymer-bound pyrazinone was irradiated with 4 equiv of phenylboronic acid, 5 equiv of Na2C03 and 20 mol % of Pd[P(Ph)3]4 as the catalyst in DMF as the solvent (Scheme 36). Contrary to the results obtained in solution phase [29], all attempts to drive the reaction toward the formation of disub-stituted compound, using higher equivalents of reagents or longer reaction times, were unsuccessful. Apphcation of aqueous conditions afforded mixtures of 3-mono and 3,5-disubstituted pyrazinones. 

For many cases one needs to have values of thermodynamic variables for conditions very different from 298 K and 1.0 bar. These cases include reactions occurring above the tropo-pause, where pressures are several orders of magnitude less than 1.0 bar and temperatures are less than 200 K. The important reactions occurring in the high-temperature and high-pressure aqueous conditions of the mid-ocean rift zone, and the high-temperature and high-pressure conditions where important mineral transformations occur far below the Earth s surface are examples. 

The regeneration of carbonyl compounds from 1,3-dithianes can be achieved using potassium hydrogen persulfate, Oxone , supported on wet alumina <96SL767> and by periodic acid under non-aqueous conditions <96TL4331>. The deprotection of benzyl substituted 1,3-dithianes can be achieved using the one electron oxidant [Fe(phen)3](PF6)3 <96SL315>. 

Green tea consists of a wealth of simple phenolics (monomers), whereas black tea provides more complex polyphenols (dimers and polymers). It was found that with lipids the simple compounds were more effective antioxidants, while under aqueous conditions, polymers tended to have more activity. Weisburger (2001) suggested that polymers formed from a 2-5 unit polymerisation state seemed to be optimal, probably because the monomer is metabolised and excreted too rapidly, whereas the higher 6-10 unit polymers may suffer from difficulty in penetrating cellular membranes and be poorly absorbed. 

Under aqueous conditions, flavonoids and their glycosides will also reduce oxidants other than peroxyl radicals and may have a role in protecting membranal systems against pro-oxidants such as metal ions and activated oxygen species in the aqueous phase. Rate constants for reduction of superoxide anion show flavonoids to be more efficient than the water-soluble vitamin E analogue trolox (Jovanovic et al, 1994), see Table 16.1. 

The viabiUty of using site-isolated Ta(V) centers for cyclohexene epoxi-dation was explored by grafting ( PrO)2Ta[OSi(O Bu)3]3 onto a mesoporous silica material [83]. After calcinations, the material formed is less active and selective in the oxidation of cyclohexene than the surface-supported Ti(IV) catalysts using organic peroxides however, the site-isolated Ta(V) catalysts are more active under aqueous conditions. 

Good bonding was obtained to several substrates under aqueous conditions. Values obtained were 41 to 10-3 MPa to composite resins, and 9-8 to 15-6 MPa to stainless steel (Table 9.6). They were also reported as adhering to porcelain. No adhesion was obtained to untreated dentine or enamel. The cements could be bonded to enamel etched with add (3-5 MPa) and to dentine conditioned with poly(acrylic acid) (10 MPa). 

Further studies by Bode and co-workers have shown that enolate formation from a-chloroaldehydes and subsequent reaction with 4-oxo-enoates or unsaturated a-ketoesters 232 generates dihydropyranones 233 in excellent diastereo- and enantio-selectivities, and with impressively low catalyst loadings [90], This work has been extended to the generation of enolate equivalents from bisulfite adducts of a-haloaldehydes 234 under aqueous conditions (Scheme 12.50) [91]. 

Fig. 8.34 Lefty, outcrop rocks found at the crater wall of Eagle Crater, where the rover Opportunity landed on 24 January 2004. Clearly, the sedimentary structure is seen. Right) in the spectrum, taken on sol 33 (sol = Martian day) of the mission, the mineral Jarosite, an Fe -sulfate, could be identified at the Meridiani Planum landing site. It forms only under aqueous conditions at low pH (< 3 ) and is therefore clear mineralogical evidence for aqueous processes on Mars...

Thorium generally exists as a neutral hydroxide species in the oceans and is highly insoluble. Its behavior is dominated by a tendency to become incorporated in colloids and/or adhere to the surfaces of existing particles (Cochran 1992). Because ocean particles settle from the water column on the timescale of years, Th isotopes are removed rapidly and have an average residence time of = 20 years (Fig. 1). This insoluble behavior has led to the common assertion that Th is always immobile in aqueous conditions. While this is generally true in seawater, there are examples of Th being complexed as a carbonate (e.g.. Mono Lake waters, Anderson et al. 1982 Simpson et al. 1982) in which form it is soluble. 

We also wanted to evaluate the disassembly of our dendritic system under physiological conditions. Thus, we synthesized a self-immolative AB6 dendron 32 with water-soluble tryptophan tail units and a phenylacetamide head as a trigger (Fig. 5.26) to evaluate disassembly in aqueous conditions. The phenylacetamide is selectively cleaved by the bacterial enzyme penicillin G amidase (PGA). The trigger was designed to disassemble through azaquinone methide rearrangement and cyclic dimethylurea elimination to release a phenol intermediate that will undergo six quinone methide elimination reactions to release the tryptophan tail units. 

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