Aqueous media, reactions compounds

By the action of indium, various allylic or propargylic dihalo compounds can be converted to the respective dianion equivalents. In some cases, the reaction with electrophiles proceeds stepwise, whereas in other cases novel diindium reagents are involved. Via an indium-mediated Barbier-type reaction in an aqueous medium, carbonyl compounds react with a trimethylenemethane dianion equivalent to give the corresponding diols (Equation (39)).218... 

With Unsaturated Compounds. The reaction of unsaturated organic compounds with carbon monoxide and molecules containing an active hydrogen atom leads to a variety of interesting organic products. The hydroformylation reaction is the most important member of this class of reactions. When the hydroformylation reaction of ethylene takes place in an aqueous medium, diethyl ketone [96-22-0] is obtained as the principal product instead of propionaldehyde [123-38-6] (59). Ethylene, carbon monoxide, and water also yield propionic acid [79-09-4] under mild conditions (448—468 K and 3—7 MPa or 30—70 atm) using cobalt or rhodium catalysts containing bromide or iodide (60,61). 

The intramolecular /zetero-Diels-Alder reactions of 4-O-protected acyl-nitroso compounds 81, generated in situ from hydroxamic acids 80 by periodate oxidation, were investigated under various conditions in order to obtain the best endo/exo ratio of adducts 82 and 83 [65h] (Table 4.15). The endo adducts are key intermediates for the synthesis of optically active swainsonine [66a] and pumiliotoxin [66b]. The use of CDs in aqueous medium improves the reaction yield and selectivity with respect to organic solvents. 

The nitroso moiety of the N-acylnitroso function is a powerful dienophile and therefore N-acylnitroso compounds are trapped rapidly, especially in an intramolecular reaction, with a diene allowing the Diels Alder reaction to occur also in water, although N-acylnitroso compounds are short-lived in aqueous medium. 

These conclusions were supported by the results obtained in a study of the reactions of various types of acetylenes with TTN (94). Hydration of the C=C bond was found to occur to a very minor extent, if at all, with almost all of the compounds studied, and the nature of the products formed was dependent on the structure of the acetylene and the solvent employed. Oxidation of diarylacetylenes with two equivalents of TTN in either aqueous acidic glyme or methanol as solvent resulted in smooth high yield conversion into the corresponding benzils (Scheme 23). The mechanism of this oxidation in aqueous medium most probably involves oxythallation of the acetylene, ketonization of the initially formed adduct (XXXV) to give the monoalkylthallium(III) derivative (XXXVI), and conversion of this intermediate into a benzoin (XXXVII) by a Type 1 process. Oxidation of (XXXVII) to the benzil (XXXVIII) by the second equivalent of reagent would then proceed in exactly the same manner as described for the oxidation of chalcones, deoxybenzoins, and benzoins to benzils by TTN. The mechanism of oxidation in methanol solution is somewhat more complex and has not yet been fully elucidated. 

The indium-mediated allylation carried out with allylstannanes in combination with indium chloride in aqueous medium was reported by Marshall et al.113 Allylindium was proposed as the reaction intermediate. Various aldehydes can be alkylated very efficiently with 3-bromo-2-chloro-l-propene mediated by indium in water at room temperature. Subsequent treatment of the compound with ozone in methanol followed by workup with sodium sulfite provided the desired hydroxyl ester in high yield.114... 

The hetero-Diels-Alder reaction has also utilized dienophiles in which both reactive centers are heteroatoms. Kibayashi reported that the intramolecular hetero-Diels-Alder cycloaddition of chiral acylnitroso compounds, generated in situ from periodate oxidation of the precursor hydroxamic acid, showed a marked enhancement of the trans-selectivity in an aqueous medium compared with the selectivity in nonaqueous conditions (Eq. 12.55).125 The reaction was readily applied to the total synthesis of (—)-pumiliotoxin C (Figure 12.5).126... 

Kanasawud and Crouzet have studied the mechanism for formation of volatile compounds by thermal degradation of p-carotene and lycopene in aqueous medium (Kanasawud and Crouzet 1990a,b). Such a model system is considered by the authors to be representative of the conditions found during the treatment of vegetable products. In the case of lycopene, two of the compounds identified, 2-methyl-2-hepten-6-one and citral, have already been found in the volatile fraction of tomato and tomato products. New compounds have been identified 5-hexen-2-one, hexane-2,5-dione, and 6-methyl-3,5-heptadien-2-one, possibly formed from transient pseudoionone and geranyl acetate. According to the kinetics of their formation, the authors concluded that most of these products are formed mainly from all-(E) -lycopene and not (Z)-isomers of lycopene, which are also found as minor products in the reaction mixture. 

Numerous examples of the synthesis of tricyclic systems based on indolizine derivative 232 have been reported <2000M959>. The product obtained from the reaction of 232 with carbon disulfide depends on the reaction medium. Thus, in aqueous potassium hydroxide the pyrimidine-dithione 233 is formed, whereas in pyridine the iminothiazine-thione 234 is obtained. In aqueous potassium hydroxide, compound 234 rearranges to 233 (Scheme 12) <2000M959>. 

Dissolve mono(lactosylamido) mono(succinimidyl)suberate in dry DMF to prepare a concentrated solution from which an aliquot may be taken and added to a final aqueous reaction medium. The compound is extremely soluble in DMF, and solutions of 100 mg/ ml may be prepared. The use of dry solvent is essential to prevent hydrolysis of the NHS ester. However, make only enough of this stock solution so that a small amount added to the protein reaction will provide the appropriate molar excess desired for the modification reaction. 

The biotinylation of amine-dendrimers may be accomplished using either an organic reaction environment or an aqueous medium. For modification of PAMAM dendrimers with a biotinidase resistant biotin compound, Wilbur et al. (1998) performed the reaction in DMF with triethylamine as catalyst (proton acceptor). The following protocol illustrates this type of procedure using the biotinylation reagent NHS-PEG/pbiotin, which closely compares to the biotinidase insensitive compound used in the published procedure. 

Fluorescein-5-thiosemicarbazide is soluble in DMF or in buffered aqueous solutions at pH values above 7.0. The reagent may be dissolved in DMF as a concentrated stock solution before adding a small aliquot to an aqueous reaction medium. The compound itself and all solutions made with it should be protected from light to avoid decomposition of its fluorescent properties. 

Biotin-BMCC is insoluble in water and must be dissolved in an organic solvent prior to addition to an aqueous reaction mixture. Preparing a concentrated stock solution in DMF or DMSO allows transfer of a small aliquot to a buffer reaction. The upper limit of biotin-BMCC solubility in DMSO is approximately 33 mM or 17 mg/ml. In DMF, it is only soluble to a level of about 7 mM (4 mg/ml). Upon addition of an organic solution of the reagent to an aqueous environment (do not exceed 10 percent organic solvent in the aqueous medium to prevent protein precipitation), biotin-BMCC may form a micro-emulsion. This is normal and during the course of the reaction, the remainder of the compound will be driven into solution as it couples or hydrolyzes. 

A photolytic study with a 5-azidotetrazole derivative also led to the formation of a tetrazolo[l,5-/z]quinazoline compound, although the yield was fairly low. Araki et al. published findings that irradiation of 110 in aqueous medium resulted in formation of the mesoionic enolate 112 in 8% yield <2000JHC1129> (Scheme 20). The authors concluded that the formation of the tricyclic structure can be rationalized by an intramolecular insertion of the triplet nitrene formed from 110 to a C-H bond of an ortho-methyl group to give at first intermediate 111, which was converted under the applied reaction conditions to produce 112. 

The only copper complexes of tridentate azo compounds are 1 1 structures, since copper(II) has a CN of 4. They can be prepared by the reaction of the azo compound with a copper(II) salt in an aqueous medium at 60 °C. The major application for copper-complex azo dyes is as direct or reactive dyes for the dyeing of cellulosic fibres. They are seldom developed for use on wool or nylon, although various orange and red 1 1 copper-complex azopyrazolones (5.42) were synthesised recently and evaluated on these fibres by application from a weakly acidic dyebath [24]. 

This is an alternative method of introducing copper into an o-hydroxyazo dye structure. The azo compound is treated with a copper(II) salt and an oxidant in an aqueous medium at 40-70 °C and pH 4.5-7.0. Sodium peroxide, sodium perborate, hydrogen peroxide or other salts of peroxy acids may be used as oxidants, the function of which is to introduce a second hydroxy group in the o -position [25]. This process is reminiscent of earlier work on Cl Acid Red 14 (5.51 X = H), an o-hydroxyazo dye that will not react with a chromium (III) salt to form a 1 1 complex but will do so by oxidation with an acidified dichromate solution. This oxidation product was later found to be identical with that obtained by conventional reaction of Cl Mordant Black 3 (5.51 X = OH) with a chromium(III) salt [7]. 

Another variety of the continuous-coupling technique operates by transporting the coupling component suspension as a laminar flow upwards inside a vertical reaction tube. Portions of the diazonium compound, dissolved in an acidic aqueous medium, are added through appropriately located inlets in the walls of the reaction tube. The concentration of the added solution decreases as the reaction mixture flows upward and is designed to synchronize the uppermost inlet for the diazonium salt solution with the stoichiometric end point of the coupling reaction. 

The diazonium ions 13 with electron-withdrawing substituents are not h texoaromatic compounds and therefore do not strictly come within the scope of this chapter. They are formally related to the alkenediazonium ions. Nevertheless, they are discussed here because in their properties they bear a close resemblance to heteroaromatic and arenedi-azonium ions rather than to alkenediazonium ions. In particular they can be obtained by direct diazotization of the amines, they are stable in an aqueous medium and they are capable of undergoing an azo coupling reaction. 

The mechanism of the global 4-electron electrochemical reduction of aromatic nitro compounds to hydroxylamines in aqueous medium shown in reaction 37 was investigated by polarography and cyclic voltametry. The nitro group is converted first to a dihy-droxylamine, that on dehydration yields a nitroso group the latter is further reduced to a... 

Parlar, H. Photoinduced reactions of two toxaphene compounds in aqueous medium and adsorbed on silica gel, Chemosphere, 17(11) 2141-2150, 1988. 

The digestion and absorption of fat is considerably more complex than that of carbohydrate or protein because it is insoluble in water, whereas almost aU enzymes catalyse reactions in an aqueous medium. In such media, fat can form small droplets, an emulsion, which is stable in this medium. Formation of an emulsion is aided by the presence of detergents these possess hydrophobic and hydrophilic groups, so that they associate with both the fat and the aqueous phases. Such compounds are known as emulsifying agents and those involved in digestion are mainly the bile salts and phospholipids. 

Sharpless et al. recently introduced the term click chemistry for the use of simple (but selective), high-yielding reactions forming mostly carbon-heteroatom bonds, preferably in aqueous medium, using only easily available compounds [72]. The authors urge the synthetic community to concentrate on the development of new properties rather than new compounds. 

Although the acidity of Meldrum s acid is quite similar to that of barbituric acids, the same reaction conducted with this dicarbonylic compound in aqueous medium gave a complex mixture instead of the expected adduct [107]. The reaction... 

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