Reaction cleavage

This cleavage reaction is more often seen in structural analysis than in synthesis The substitution pattern around a dou ble bond is revealed by identifying the carbonyl containing compounds that make up the product Hydrolysis of the ozonide intermediate in the presence of zinc (reductive workup) permits aide hyde products to be isolated without further oxidation... 

Further steps m glycolysis use the d glyceraldehyde 3 phosphate formed m the aldolase catalyzed cleavage reaction as a substrate Its coproduct dihydroxyacetone phosphate is not wasted however The enzyme triose phosphate isomerase converts dihydroxyacetone phosphate to d glyceraldehyde 3 phosphate which enters the glycol ysis pathway for further transformations... 

Cleavage reactions of carbohydrates also occur on treatment with aqueous base for prolonged periods as a consequence of base catalyzed retro aldol reactions As pointed out m Section 18 9 aldol addition is a reversible process and (3 hydroxy carbonyl com pounds can be cleaved to an enolate and either an aldehyde or a ketone... 

More recent work reports the onset of thermal degradation at lower temperatures and provides a clearer picture of the role of oxygen (73—75). In the presence of oxygen, backbone oxidation and subsequent cleavage reactions initiate decomposition. In the absence of oxygen, dehydrofluorination eventually occurs, but at significantly higher temperatures. 

Substitution Reactions on Side Chains. Because the benzyl carbon is the most reactive site on the propanoid side chain, many substitution reactions occur at this position. Typically, substitution reactions occur by attack of a nucleophilic reagent on a benzyl carbon present in the form of a carbonium ion or a methine group in a quinonemethide stmeture. In a reversal of the ether cleavage reactions described, benzyl alcohols and ethers may be transformed to alkyl or aryl ethers by acid-catalyzed etherifications or transetherifications with alcohol or phenol. The conversion of a benzyl alcohol or ether to a sulfonic acid group is among the most important side chain modification reactions because it is essential to the solubilization of lignin in the sulfite pulping process (17). 

Ethylene also is a by-product of the cleavage reaction with tetrahydrofuran (99). The rate of loss for / -butyUithium in a variety of ether solvents is given in Table 6. 

A typical phenol plant based on the cumene hydroperoxide process can be divided into two principal areas. In the reaction area, cumene, formed by alkylation of benzene and propylene, is oxidized to form cumene hydroperoxide (CHP). The cumene hydroperoxide is concentrated and cleaved to produce phenol and acetone. By-products of the oxidation reaction are acetophenone and dimethyl benzyl alcohol (DMBA). DMBA is dehydrated in the cleavage reaction to produce alpha-methylstyrene (AMS). 

The concentrated cumene hydroperoxide solution from the cumene stripping section is fed to the cleavage reaction. The cleavage reaction is carried... 

Production of a-methylstyrene (AMS) from cumene by dehydrogenation was practiced commercially by Dow until 1977. It is now produced as a by-product in the production of phenol and acetone from cumene. Cumene is manufactured by alkylation of benzene with propylene. In the phenol—acetone process, cumene is oxidized in the Hquid phase thermally to cumene hydroperoxide. The hydroperoxide is spHt into phenol and acetone by a cleavage reaction catalyzed by sulfur dioxide. Up to 2% of the cumene is converted to a-methylstyrene. Phenol and acetone are large-volume chemicals and the supply of the by-product a-methylstyrene is weU in excess of its demand. Producers are forced to hydrogenate it back to cumene for recycle to the phenol—acetone plant. Estimated plant capacities of the U.S. producers of a-methylstyrene are Hsted in Table 13 (80). 

Fig. 3. Cleavage reactions of sulfonates where Ar is an aryl group.

Unlike the 2-aLkyl-2-imida2olines, this stmcture is stable and resistant to hydrolysis. After ring cleavage, reaction with sodium chloroacetate yields linear products ... 

In practice, these cleavage reactions are difficult to control, and usually mixtures of products form, even with stoichiometric quantities of reagents. Selectivity improves at lower temperatures, higher dilutions, and in the presence of polar solvents, eg, pyridine. This method is not used to prepare the lower alkylated—arylated organotins outside the laboratory. 

Release by Silver-Assisted Cleavag e. A soluble silver complex formed imagewise in the undeveloped areas of the silver haUde layer may be used to effect a cleavage reaction that releases a dye or a dye precursor. The process yields positive dye transfer images directiy with negative-working emulsions (46). An example is the silver-assisted cleavage of a dye-substituted thiazolidine compound, as shown in equation 7. 

Unsubstituted 3-alkyl- or 3-aryl-isoxazoles undergo ring cleavage reactions under more vigorous conditions. In these substrates the deprotonation of the H-5 proton is concurrent with fission of the N—O and C(3)—-C(4) bonds, giving a nitrile and an ethynolate anion. The latter is usually hydrolyzed on work-up to a carboxylic acid, but can be trapped at low temperature. As shown by Scheme 33, such reactions could provide useful syntheses of ketenes and /3-lactones (79LA219). 

Dibenzo[6,e][l,4]dioxin, 2-nitro-bromination, 3, 974 cleavage reactions, 3, 973 Dibenzo[b,e][l,4]dioxin, 2,3,7,8-tetrachloro-synthesis, 3, 985 toxicity, 3, 992 Dibenzodioxins... 

Triazole, 5-azido-1,4-diphenyl-cleavage reactions, 5, 697 reactions, 5, 98... 

Photolytic cleavage reactions (e.g., of o-nitrobenzyl, phenacyl, nitrophenylsul-fenyl derivatives) take place in high yield on irradiation of the protected compound for a few hours at 254-350 nm. For example, the o-nitrobenzyl group, used to protect alcohols, amines, and carboxylic acids,has been removed by irradiation. Protective groups that have been removed by photolysis are described at the appropriate places in this book in addition, the reader may wish to consult five review articles. 

CF3COOH, anisole, CH2Cl2. Anisole is present to scavenge the diphenylmethyl cation liberated during the cleavage reaction. 

Si02, benzene, 25°, 16 h, 81% yield.This cleavage reaction is carried out on a column. 

In this type of cleavage reaction it appears that the axial benzoate is the preferred product. If water is excluded from the reaction, a bromo benzoate is obtained. ... 

DMSO, NaCN, 125-180°, 5-48 h, 65-90% yield.This cleavage reaction is successful for aromatic systems containing ketones, amides, and carboxylic acids mixtures are obtained from nitro-substituted aromatic compounds there is no reaction with 5-methoxyindole (180°, 48 h). 

The great reactivity of the sulfurane prepared by this procedure toward active hydrogen compounds, coupled with an indefinite shelf life in the absence of moisture, makes this compound a useful reagent for dehydrations,amide cleavage reactions, epoxide formation, sulfilimine syntheses, and certain oxidations and coupling reactions. 

This reaction is referred to as the type-I or a-cleavage reaction of carbonyl omnpnunds. This type of reaction is not so common in solution, although some cyclic ketooes do undergo decarbonylation ... 

Table 11 Prechromatographic denvatization involving hydrolytic and enzymatic cleavage reactions...

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