Reactions and Derivatives

Cyclopentadiene contains conjugated double bonds and an active methylene group and can thus undergo a Diels-Alder diene addition reaction with almost any unsaturated compound, eg, olefins, acetylene, maleic anhydride, etc. The number of its derivatives is extensive only the reactions and derivatives considered most important are discussed. 

In the following account of some reactions and derivatives of the two alkaloids the Leuchs variation (IIIB note the different system of numbering adopted) is sometimes used for the convenience of readers, who may... 

The chemical reactions and derivatives of kojic acid will be grouped according to these centers of its reactivity. 

White Compound. See under TNT article in Vol 9 in the following sections Preparation , T241-L Purification , T244, Table 1 Chemical Reactions and Derivatives , T248-R and in Vol 8, N84-R... 

Some reactions and derivs of cellulose are given under Cellulose(above). The derivs of interest in the expl industry and allied applications are included here ... 

The expln mentioned above occurred during faulty manual removal of white compound , an insoluble TNT oxidation by-product, which has periodically coated the nitrator cooling coils (the chemical structure and mode of formation of this material are given under the section on Chemical Reactions and Derivatives ). It was found (Ref 21) that its formation resulted from high carry-back of TNT oxidation products from one of the nitrators in stage 3 to stage 2. This again pointed to the desirability of cleaner separation of acid and nitrobody, since white compd deposition was not a problem in plants where better separation occurred... 

This purification process is quite sensitive to pH (Ref 23). As shown in Fig 6, yield loss rises sharply above pH 7.5, because of the formation of the water-soluble complex of 2,4,6-TNT with Na sulfite. In addition, at pH values above about 8 (see Fig 7 and Table 1), the formation of two by-products [hexanitrobibenzyl (HNBB), and methylpentanitrodiphenylme thane (MFDM)] increases strongly. (The chemical structures and modes of formation of these compds are given in the section on Chemical Reactions and Derivatives ). These compds have an adverse effect on the mode of crystn of TNT, resulting in the formation of cracks and voids in the finished cast expl (Ref 13). It is also apparent from Table 1 that meta TNT isomers are not completely removed, and that the amounts of all of the DNT Isomers and of five of the oxidation products remain unchanged... 

The melting points (more accurately termed the decomposition points) of sugars and some of their derivatives, e.g. osazones, are not so definite as those of other classes of organic compounds they vary with the rate of heating and the differences between individual members are not always large. There are, however, a number of reactions and derivatives which will assist in the characterisation of the simple sugars. 

Almost simultaneously with our first investigations About Reactions and Derivatives of Iron Carbonyl (Section II,A) we concerned ourselves at Heidelberg with the effect of halogens on iron pentacarbonyl, initially in the expectation of obtaining a pure surface-active iron(II) halide. However, to our surprise at the time, reaction occurred according to the equation... 

DECOMPOSITION REACTIONS AND DERIVED SYNTHETIC APPLICATIONS OF ALKYLIDYNETRICOBALT NONACARBONYL COMPLEXES... 

In general, the alkylalkoxysilanes behave like the alkylchloro-silanes in that they hydrolyze to form the various silicols or their dehydration products. It is not necessary to go through the separate classes of compounds, for their reactions and derivatives may be inferred from the known properties of the halides and the previously discussed properties of the silicon esters. Some of the representative compounds are listed in the index which follows this chapter,66 and a list of alkyltrialkoxysilanes is given in Krause and von Grosse.67... 

Example 8.11 Time variation of entropy production in simultaneous chemical reactions Consider two simultaneous reactions and derive relations for the time variation of the entropy production. Assuming that linear laws hold for a two-reaction system, we have... 

Preparation, reactions, and derivatives of Meldrum s acid are described (1). 

Ruthenium has been investigated by many laboratories as a possible catalyst for ammonia synthesis. Recently, Becue et al. [T. Becue, R. J. Davis, and J. M. Garces, J. Catal., 179 (1998) 129] reported that the forward rate (far from equilibrium) of ammonia synthesis at 20 bar total pressure and 623 K over base-promoted ruthenium metal is first order in dinitrogen and inverse first order in dihydrogen. The rate is very weakly inhibited by ammonia. Propose a plausible sequence of steps for the catalytic reaction and derive a rate equation consistent with experimental observation. 

The indirect reduction of many organic substrates, in particular alkyl and aryl halides, by means of radical anions of aromatic and heteroaromatic compounds has been the subject of numerous papers over the last 25 years [98-121]. Many issues have been addressed, ranging from the exploration of synthetic aspects to quantitative descriptions of the kinetics involved. Saveant et al. coined the expression redox catalysis for an indirect reduction, in which the homogeneous reaction is a pure electron-transfer reaction with no chemical modification of the mediator (i.e., no ligand transfer, hydrogen abstraction, or hydride shift reactions). In the following we will consider such reactions and derive the relevant kinetic equations to show the kind of kinetic information that can be extracted. 

Syntheses.—The important synthetic methods for its preparation have all been discussed and from them and the reactions and derivatives of the acid its constitution has been fully estalbished as mono-carboxy benzene. 

After consulting these three single-volume references, one would turn to more comprehensive multivolume sources such as the Dictionary of Organic Compounds, Fifth Edition. This dictionary, still known as Heilbron, the name of its former editor, now comprises seven volumes of specific information, with primary literature references, on the synthesis, reactions, and derivatives of more than 50,000 compounds. Rodd s Chemistry of Carbon Compounds, another valuable multivolume work with primary literature references, is organized by functional group rather than in dictionary form. Elsevier s Encyclopedia of Organic Compounds in about twenty volumes is an incomplete reference work on the chemical and physical properties of compounds. It is useful for those areas it covers. References to Elsevier are found in the Handbook of Chemistry and Physics. 

Compounds from Petroleum Hydrocarbons. (Reactions and derivatives of tertiary mercaptans.)... 

---