Organic Reactions of

Reactions of the Dlfluoroamlno Radical with Other Radicals 

Photolysis of CH3I, C2H5I, or CF3I in presence of N2F4 gives the corresponding difluoroaminoalkanes (119,120). 

In the reaction with N2F4, however, the only products isolated were CF3ONF2, (CF3)202, NF3, and Oz. 

The difluoroamino radical is able in some instances to abstract hydrogen from an organic substrate, producing a radical which can then itself react with NF2. The best known examples of this type are the reactions of N2F4 with some aldehydes (234), the following reaction being typical  

With thiophenol at 50°C there is a 74% yield of HNF2, the other product in this case being the disulfide (C6H5)2S2 rather than C6H5SNF2 (123). Yields are not as high with aliphatic thiols, which have a greater tendency to reduce the tetrafluorohydrazine to molecular nitrogen. 

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A rational classification of reactions based on mechanistic considerations is essential for the better understanding of such a broad research field as that of the organic chemistry of Pd. Therefore, as was done in my previous book, the organic reactions of Pd are classified into stoichiometric and catalytic reactions. It is essential to form a Pd—C cr-bond for a synthetic reaction. The Pd— C (T-bond is formed in two ways depending on the substrates. ir-Bond formation from "unoxidized forms [1] of alkenes and arenes (simple alkenes and arenes) leads to stoichiometric reactions, and that from oxidized forms of alkenes and arenes (typically halides) leads to catalytic reactions. We first consider how these two reactions differ. 

Other organic reactions of sulfamic acid are described ia the Hterature (30,31). 

Numerous organic reactions of sulfur monochloride are of practical and commercial importance. Of particular importance is the reaction of sulfur monochloride with olefins to yield various types of addition products (142). With ethylene, the severe vesicant bis(2-chloroethyl) sulfide [505-60-2] (mustard gas) forms with elemental sulfur and polysulfides (see Chemicals IN war). Propylene reacts similarly ... 

The major organic reactions of BrCl consist of electrophilic brominations of aromatic compounds. Many aromatic compounds do not react in aqueous solution unless the reaction involves activated aromatic compounds (an example being phenol). Bromine chloride undergoes free-radical reactions more readily than bromine. 

The principal organic reaction of ozone is its addition to the carbon-carbon double bond of an ethylenic compd. The resulting ozone-olefin addition compd is known as an ozonide. Decompn of the ozonide gives a mixt of oxygenated products containing carbonyl compds and acids. 

As an example, bulk modification by the organic reaction of unsaturated PHA with sodium permanganate resulted in the incorporation of dihydroxyl or carboxyl functional groups [106]. Due to the steric hindrance of the isotactic pendant chains, complete conversion could not be obtained. However, the solubility of the modified polymers was altered in such a way that they were now completely soluble in acetone/water and water/bicarbonate mixtures, respectively [106]. Solubility can play an important role in certain applications, for instance in hydrogels. Considering the biosynthetic pathways, the dihydroxyl or carboxyl functional groups are very difficult to incorporate by microbial synthesis and therefore organic chemistry actually has an added value to biochemistry. 

The usual etherifying agents are the alkyl chlorides or sulfates. The advantage, usually found in organic reactions, of using the alkyl iodides and bromides because of their greater reactivity as compared to the chlorides is overshadowed by their much slower diffusion rate, lower solubility in the alkali and greater rate of saponification. The sulfates are relatively costly. Alkyl sulfites have also been proposed ... 

In this context, an avalanche of studies were devoted to acid-base reactions in their broadest sense (i.e., the Lewis picture), also involving complexation reactions, to the typical organic reactions of addition, substitution, and elimination types, involving nucleophilic and electrophilic reagents including the case of radicalar reactions and excited states (for a review see Ref. [11]) in which our group has... 

A comparative study [10] into the Rh-catalysed carbonylation of ROH (R = Me, Et, Pr) shows that in all cases, the reaction rate is 1st order in both [Rh] and added [HI] and independent of CO pressure. The only Rh species observed by IR under catalytic conditions was 1. The rates of carbonylation decreased in the stated order of R, with relative rates of 21 1 0.47, respectively at 170 °C. This order of the R-groups and the large differences between them is a common feature for organic reactions of this type. All the data are consistent with ratedetermining nucleophilic attack by the Rh complex anion on the corresponding alkyl iodide. 

Ion-radical organic reactions of the Sj j l type are less sterically restricted than classical Sj reactions. Generally, the nucleophilic (not Sj j ) reactivity varies with the steric demand at the reaction center. The electron-transfer reactivity does not depend on steric effects. To illustrate this, one can compare electron transfer and nucleophilic reactivity between ketene silyl acetals and cationic electrophiles (Fukuzumi et al. 2001). Nevertheless, space strains may determine the overall results of these reactions if either intermediate radicals or forming products are sterically hindered. 

Methyl bromide is used as a pesticide, which is very effective against parasitic nematodes (e.g., hookworms). Silver bromide is used in photography. Compounds of bromide are used as flame-retardants, water purifiers, dyes, and pharmaceuticals. Bromine has many applications when it is combined with organic compounds. For example, it is used as a reagent to study the organic reactions of many other compounds. It is also used as a disinfectant, a fumigant, and a sedative. In the nineteenth century, many people took a bromide to ease tension. 

Alkaline earth metal oxides have been used as solid base catalysts for a variety of organic transformations. Excellent reviews by Tanabe 4) and Hattori 2,3,7) provide detailed information about the catalytic behavior of alkaline earth metal oxides for several organic reactions of importance for industrial organic synthesis. In this section, we describe in detail reactions that have been reported recently to be catalyzed by alkaline earth metal oxides. 

An organic reaction of interest is the Diels-Alder reaction that sulfur dioxide undergoes with butadiene and other acyclic dienes. With butadiene, the product is suhblene, C4H6S, a five-membered S-heterocyclic ring compound which is hydrogenated to form sulfolane, C4H8S. 

The field of gas-phase organic reactions of ionic species has blossomed in the last 15 years to the point where a single review article becomes a formidable task. The scope of the present report covers gas-phase reactions initiated by nucleophilic attack with special emphasis on displacement reactions. This choice was dictated by the analogy with well-known reactions in solution, which may be considered as a classical chapter of physical organic chemistry. 

One of the interesting features of these reactions is the noten-tial for comparing the stereochemistry of oligomerization with that of alkylation protonation or other organic reactions of general interest. For instance, Table 1 shows that the methyla-tion of the Li and Na salts of anion [2a] is highly stereoselective. 

Hydrogenation catalysts, particularly metals, are also relatively well characterized because of extensive study. This has occurred partly for commercial reasons catalyzed organic reactions of great industrial importance—e.g.y hydrogenation and reforming—involve reducing conditions. In part, however, this has occurred because of the esthetic attrac-... 

The third section will contain direct reactions of stable chelates. This is a large and diffuse topic and many examples of reactions of this type are included in Chapter 7.4. In the current chapter, a more detailed discussion of the most important areas, namely complexes of fl-diketones and q-amino acids and their derivatives, will be offered. Also some important organic reactions of carbonyl compounds will be considered with regard to the nature of their chelated transition states and the effects these have on product formation. 

The metal-promoted reactions of 1,2-dihydrazones with formaldehyde (see Scheme 35) can be compared with the purely organic reactions of 1,2-dihydrazones with orthoesters, which lead directly to macrocyclic compounds from which complexes of structural type (85) can be prepared.189190... 

In this section, consideration switches to several very important organic reactions of carbonyl compounds which are not normally thought of as reactions of coordinated ligands. However, recent developments have resulted from a closer investigation of the chelating nature of intermediates and transition states. 

The organic reactions of interest are those involving formal motion of hydride ion between electron deficient centres. Before proceeding to detail of these transfers, examination of some relevant characteristics of the ion itself is in order. 

Marcus analysis of organic reactions of certain non-metallic inorganic redox reagents... 

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