Successive reactions

2 Voltammetry for Assisted-Ion-Transfer Reaction 1.4.2.1 Successive Reactions 

A pioneering series of papers to analyze the voltammetric response of assisted ion transfer of higher stoichiometry (l n) was published by Kudo et al. mainly to treat polarographic data obtained with an ascending or dropping electrolyte system [169-171], The theory for successive ion-transfer reactions was then thoroughly extended by Reymond et al. [172], 

Assuming that all the diffusion coefficients are equal in a given phase, the mass transport equations can be reduced for each phase to two Pick equations for these total quantities  

the computation of the cyclic voltammograms can be classically carried out, for example, by the method of Nicholson and Shain [173]. 

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Glycosidic thiol groups can be introduced into glycosyl bromides by successive reactions with thiourea and aqueous sodium disulfite (D. Horton, 1963 M. Cemy, 1961, 1963). Such thiols are excellent nucleophiles in weakly basic media and add to electrophilic double bonds, e.g., of maleic esters, to give Michael adducts in high yields. Several chiral amphiphiles have thus been prepared without any need for chromatography (J.-H. Fuhrhop, 1986 A). 

Many complexation reactions occur in a stepwise fashion. For example, the reaction between Cd + and NH3 involves four successive reactions... 

Polyesters. Successive reactions between diols and dicarboxylic acids ... 

General. Successive reactions between difunctional monomer A-A and difunctional monomer B-B ... 

BenZotrichloride Method. The central carbon atom of the dye is supphed by the trichloromethyl group from iJ-chlorobenzotrichloride. Both symmetrical and unsymmetrical triphenyhnethane dyes suitable for acryhc fibers are prepared by this method. 4-Chlorobenzotrichloride is condensed with excess chlorobenzene in the presence of a Lewis acid such as aluminium chloride to produce the intermediate aluminium chloride complex of 4,4, 4"-trichlorotriphenylmethyl chloride (18). Stepwise nucleophihc substitution of the chlorine atoms of this intermediate is achieved by successive reactions with different arylamines to give both symmetrical (51) and unsymmetrical dyes (52), eg, N-(2-chlorophenyl)-4-[(4-chlorophenyl) [4-[(3-methylphenyl)imino]-2,5-cyclohexadien-l-yhdene]methyl]benzenaminemonohydrochloride [85356-86-1J (19) from. w-toluidine and o-chloroaniline. 

Recent Developments. A considerable amount of cellulose acetate is manufactured by the batch process, as described previously. In order to reduce production costs, efforts have been made to develop a continuous process that includes continuous activation, acetylation, hydrolysis, and precipitation. In this process, the reaction mixture, ie, cellulose, anhydride, catalyst, and solvent, pass continuously through a number of successive reaction zones, each of which is agitated (92,93). In a similar process, the reaction mass is passed through tubular zones in which the mixture is forced through screens of successively small openings to homogenize the mixture effectively (94). Other similar methods for continuous acetylation of cellulose have been described (95,96). 

An interesting method for the substitution of a hydrogen atom in rr-electron deficient heterocycles was reported some years ago, in the possibility of homolytic aromatic displacement (74AHC(16)123). The nucleophilic character of radicals and the important role of polar factors in this type of substitution are the essentials for a successful reaction with six-membered nitrogen heterocycles in general. No paper has yet been published describing homolytic substitution reactions of pteridines with nucleophilic radicals such as alkyl, carbamoyl, a-oxyalkyl and a-A-alkyl radicals or with amino radical cations. 

Successful reactions have been run with this induction period lasting from 1 hr to overnight. 

It is advantageous to use a mechanical stirrer, but successful reactions have been carried out using manual stirring. A run in which no stirring was employed gave acceptable results. 

The irradiation of 2-methoxytropone (A) leads to methyl 4-oxo-2-cyclopentenyl-acetate (D). The reaction can be followed by analytical gas chromatography and two intermediates are observed. These have the structures B and C. Indicate a mechanism by which each of the three successive reactions might occur. The first two steps are photochemical, while the third is probably an acid-catalyzed reaction which occurs under the photolysis conditions. 

A polymethacrylate copolymer is modified by successive reaction with epichlorohydrin, w-aminophenylboric acid, and nitric acid to introduce a 1-amino-(2 -nitrophenyl-5 -boric acid)-2-hydroxyl-3-o-propyl group. The modified polymethacrylates are used as chromatographic support materials and can be used to analyze biological materials without prior deproteinization (35). 

This chapter has a mechanistic emphasis designed to achieve a practical result. By understanding the mechanisms by which alkyl halides undergo nucleophilic substitution, we can choose experimental conditions best suited to cariying out a particular- functional group transfonnation. The difference between a successful reaction that leads cleanly to a desired product and one that fails is often a subtle one. Mechanistic analysis helps us to appreciate these subtleties and use them to our advantage. 

The aniline derivative 332, prepared from 2-fluoro-6-nitrotoluene, was transformed through successive reactions as shown in Scheme 60 to give the functionalized indole 333. It was then reduced with LiAlH4 to the dimethylaminopropyl derivative which was quaternized with Mel to the trimethyl ammonium salt 334. Subsequent cyclization and functionalization afforded the pyrroloquinoline 335. The latter could be transformed to the tetracyclic acid 336 (90JHC2151). (Scheme 60)... 

Since various substituents are tolerated, the Friedlander reaction is of preparative value for the synthesis of a large variety of quinoline derivatives. The benzene ring may bear for example alkyl, alkoxy, nitro or halogen substituents. Substituents R, R and R" also are variable. The reaction can be carried out with various carbonyl compounds, that contain an enolizable a-methylene group. The reactivity of that group is an important factor for a successful reaction. 

The Japp-Klingemann reaction is a special case of the aliphatic diazo coupling. For a successful reaction, the dicarbonyl substrate 2 should bear a sufficiently CH-acidic hydrogen. 

The 2-cyano-6-methoxy-naphthalene is in turn converted by successive reactions into ... 

The methylene intermediate abstracts a hydrogen and is converted to an adsorbed methyl. Reaction of the methyl with the methylene produces an ethyl-metal species. Successive reactions of the methylene with the formed ethyl produces a long chain adsorbed alkyl. 

Unlike benzene, pyridine undergoes electrophilic aromatic substitution reactions with great difficulty. Halogenation can be carried out under drastic conditions, but nitration occurs in very low yield, and Friedel-Crafts reactions are not successful. Reactions usually give the 3-substituted product. 

Cellulose is an important part of woody plants, occurring in cell walls and making up part of the structural material of stems and trunks. Cotton and flax are almost pure cellulose. Chemically, cellulose is a polysaccharide—a polymer made by successive reaction of many glucose molecules giving a high molecular weight (molecular weight ->- 600,000). This polymer is not basically different from the polymers that were discussed in Section 18-6 ... 

We have found in our studies that the use of the lithium counter ion in the base is essential for successful reaction with regiochemical control and allows cyclization to proceed under mild thermal conditions. In contrast, use of sodium (NaH, NaN(SiMe3)2) or potassium (KH, KN(SiMe3)2) bases require elevated temperatures, and results in poor yields of the desired product, and a mixture of several by-products, including the regioisomeric 4-hydroxymethy-2-oxazolidinone,6 resulting from alternate processes. Thus, the lithium ion plays a very important role in the mechanism of this reaction. 

The kinetic data fit a mechanism of successive reactions sequent to only one primary ion equally well, provided that the first step can yield 1.37 methyl radical/100 e.v. and is pressure dependent and that the succeeding pressure independent step yields methyl radicals with a lesser efficiency and leads to a pressure independent yield of 0.58 methyl radicals/100 e.v. If the first step is either Reaction 9a or Reaction 17b, one can once more use the rate constant ratios given earlier to estimate the yields of the possible primary precursor ions. Hence, either G-(C2H2+) = 1.9 ions/100 e.v., or G(C2H4+) = 1.52 ions/100 e.v. The... 

During the transfer from the gas phase to the solvent CH2C12, the formation, of NO is so strongly preferred that the following two events can take place the chain termination due to formation of carbinol end groups and nitrations as successive reactions, both of which could be experimentally detected to be disturbances of the cationic propagation 122). 

Attempts to prepare related hpp complexes of tantalum were only partially successful. Reaction of 2 equivalents of either (hpplSiMes or in situ generated Li[hpp] with Tads afforded a solid that analyzed correctly for the compound (hpp)2TaCl3. X-ray structural analysis of the crystallized product identified the coordination isomer [Ta(hpp)4][TaCl6], with a distorted dodecahedral cation and a regular octahedral anion (Figure 28). °... 

The best way of preparation seems to be the successive reaction of the respective elements (94), as described in detail for the sulfide bro-... 

The mechanism is probably also similar. In this case, a base is not needed since the carbon already has an available pair of electrons. The reaction with diazo aldehydes is especially notable, since successful reactions cannot be obtained with a-halo aldehydes. ... 

It is by means of successive reactions of this sort that simple alkanes like methane and ethane give rert-butyl cations in super acid solutions (p. 219). °... 

When the reactant is of the form ZCH2Z, aldehydes react much better than ketones and few successful reactions with ketones have been reported. However, it is possible to get good yields of alkene from the condensation of diethyl malonate, CH2(COOEt)2, with ketones, as well as with aldehydes, if the reaction is run with TiCU and pyridine in THF. In reactions with ZCH2Z, the catalyst is most often a secondary amine (piperidine is the most common), though many other catalysts have been used. When the catalyst is pyridine (to which piperidine may or may not be added) the reaction is known as the Doebner modification of the Knoevenagel reaction. Alkoxides are also common catalysts. 

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