Organic solvents reactions

Recent experiments have shown that the concentration of aromatic compound needed to maintain zeroth-order kinetics (see below) was much greater than for nitrations with solutions of nitric acid in some inert organic solvents reactions which were first order in the concentration of the aromatic were obtained when [ArH] < c. 2 x io mol 1 . ... 

The same rearrangement for the protected analog under organic solvent reaction conditions had considerable difficulties and often resulted in the elimination of acetaldehyde.158... 

The Hildebrand parameter as the unit of solubility of non-electrolytes in organic solvents/ reaction products is high... 

The most important route to 1-acylaminoanthraquinones involves reaction of 1-aminoanthraquinone with acid chlorides in an organic solvent. Reaction of 1-aminoanthraquinone with benzoylchloride in nitrobenzene at 100 to 150°C affords 1-benzoylaminoanthraquinone, a yellow pigment which is registered as Colour Index Constitution No. 60515. The reaction may also be performed in the presence of a tertiary amine, which acts as a proton acceptor ... 

Very recently, Belokon and North have extended the use of square planar metal-salen complexes as asymmetric phase-transfer catalysts to the Darzens condensation. These authors first studied the uncatalyzed addition of amides 43a-c to aldehydes under heterogeneous (solid base in organic solvent) reaction conditions, as shown in Scheme 8.19 [47]. It was found that the relative configuration of the epoxyamides 44a,b could be controlled by choice of the appropriate leaving group within substrate 43a-c, base and solvent. Thus, the use of chloro-amide 43a with sodium hydroxide in DCM gave predominantly or exclusively the trans-epoxide 44a this was consistent with the reaction proceeding via a thermodynamically controlled aldol condensation... 

The more electrophilic reagent Pd(OAc)2 is another usefril reagent in organopalladium chemistry. It is monomeric in benzene at 80 °C, but is trimeric at room temperature in benzene. For even greater reactivity, Pd(02CCF3)2 can be used. Both the acetate and trifluoroacetate are soluble in organic solvents. Reaction of palladium acetate with acetylacetone produces Pd(acac)2. This acetylacetonate and especially the hexafluoroacetylacetonate, Pd(hfac)2, are useful as volatile sources of palladium in metalorganic chemical vapor deposition. 

In addition to the application of ABRE in wood chemistry, it has been widely applied to other biomass conversion fields, particularly enzyme catalysed hydrolysis reactions such as the conversion of biopolymers (including cellulose and starch) to monosaccharides and oligosaccharides. In this area, PEG ABS systems offer a benign non-denaturing environment in contrast to organic solvent reaction media. 

Fig. 4. Rates with Pd-MMA and Pd-PAME catalysts in organic solvents. Reaction mixture 1 cc. nitrobenzene, 10 mg. Pd. Curve (1) 400 mg, MMA, 50 cc. glacial acetic acid (2) 250 mg. MMA, 50 cc. acetone (3) 400 mg. MMA, 50 cc. glacial acetic acid, 10 cc. cyclohexane (4) 400 mg. MMA, 50 cc. glacial acetic acid, 10 cc. benzene (5) 400 mg. MMA, 50 cc. glacial acetic acid, 10 cc. acetone (6) 400 mg. PAME, 50 cc. glacial acetic acid (7) 400 mg. PAME, 50 cc. glacial acetic acid, 5 cc. acetone (8) 250 mg. MMA(monomeric), 50 cc. acetone. [From Rampino and Nord, J. Am. Chem. Soc. 63, 2745 (1947), Figure 4, p. 2748.]...

Polymerization conducted in aqueous interfaeial systems suffers from hydrolytic decomposition. The decomposition reaction can be minimized when contact with water is avoided. In the case of polymerization in nonaqueous interfacial environments, products with number average molecular weights up to 5000 can be obtained. Various aromatic polymers were prepared from the reaction of equimolar amounts of the acid dissolved in an aqueous base and the corresponding diacid chloride dissolved in an organic solvent. Reaction occurred between dibasic acid in one phase and an acid chloride in the other. Polar solvents for this reaction include dimethylformamide and 1,4-dicya-nobutane. 

While phase-transfer catalysis (PTC) is a well established method with diverse applications in organic synthesis, conventional catalysts suffer several drawbacks including hygroscopicity, low thermal stability and difficulty in separation and recovery. Ironically, the high solubilities of conventional catalysts are a drawback to recovery and a problem to product purification. The concept of triphase catalysis, whereby the catalyst is immobilised onto a support material and the resulting supported PTC is then used in a biphasic aqueous-organic solvent reaction mixture is recognised as a viable solution to many of these problems.144-146... 

Ion-pair formation can also result in an uncharged species having solubility characteristics suitable for their extraction into organic solvents. Reactions involving ion-pair formation are widely used for the extraction of metal ions as well as nonmetallic inorganic and organic ions. Typical... 

Glue can be modified by a variety of chemical reactions, including acetylation of the hydroxyl groups, alcoholysis to yield amino acid esters, and aryl sulfonation to give complexes insoluble in water but soluble in organic solvent. Reaction with fatty amines improves water resistance. Quatemization yields cationic molecules. The literature abounds with ideas for modification. 

Beyond reactions, which were studied for synthetic purposes (see above), only a few electrochemical studies on the reactions of fullerenes and their anions were performed. These include protonation of Ceo anions [51,91] in organic solvents, reactions of 50 anions with water and oxygen [93,94], reactions of C o and C70 with dimethylamine [17,95] and strong electron donors [42]. 

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