Degradation with Acids

Trialkylphosphites as strong Lewis bases are extremely sensitive to acids [151]. Their hydrolysis is accelerated even in the presence of small amounts of acids [152]. The proposed mechanism for acid catalyzed hydrolysis is shown in 

The protonation of one oxygen atom in the first step is a less likely event, but it has to be considered in the hydrolysis of phosphoramidites, where preferred protonation of the stronger base nitrogen is possible (see also Section 2.3.3). Therefore, phosphoramidites could be even more sensitive to acids than phosphites 

---

Further studies on RG-II provided structures for most of the oligosaccharides formed when it is extensively degraded with acid. A strategy... 

There are a number of well-known colour tests for monosaccharides, such as condensation of the acid degradation products with phenolic substances. Perhaps the most frequently cited example of this is the Molisch test in which carbohydrates give a purple colour with a-naphthol in the presence of concentrated sulphuric acid. The presence of ketoses and of 3,6-anhydro-hexoses is often detected by the characteristic red colour rapidly developed with acid resorcinol (Seliwanoff test), and the presence of 2-deoxypentoses may be shown by the deep blue colour they yield with diphenylamine after degradation with acid to 5-hydroxy-levulinaldehyde. Before an individual sugar can be identified, however, it must be isolated as a pure substance in crystalline form or converted to a characteristic crystalline derivative. The derivative the author considers the best for the characterisation of the better known monosaccharides is given in Table I (p. 57). 

Edman degradation (Section 27 13) Method for determining the N terminal amino acid of a peptide or protein It in volves treating the material with phenyl isothiocyanate (CgH5N=C=S) cleaving with acid and then identifying the phenylthiohydantoin (PTH derivative) produced Elastomer (Section 10 11) A synthetic polymer that possesses elasticity... 

Polyacrylamides are used in many other oilfield appUcations. These include cement additives for fluid loss control in well cementing operations (127), viscosity control additives for drilling muds (128), and fracturing fluids (129). Copolymers [40623-73-2] of acrylamide and acrylamidomethylpropanesulfonic acid do not degrade with the high concentrations of acids used in acid fracturing. 

Guar gum [9000-30-0] derived from the seed of a legume (11,16), is used as a flocculant in the filtration of mineral pulps leached with acid or cyanide for the recovery of uranium and gold (16). It is also used as a retention aid, usually in a chemically modified form (14,17). Starch and guar gum are subject to biological degradation in solution, so they are usually sold as dry powders that are dissolved immediately before use. Starch requires heating in most cases to be fully dissolved. 

PTMEG is a polymeric ether susceptible to both thermal and oxidative degradation. It usually contains 300—1000 ppm of an antioxidant such as 2,6-di-/ f2 -butyl-4-hydroxytoluene (BHT) to prevent oxidation under normal storage and handling conditions. Thermal decomposition in an inert atmosphere starts at 210—220°C (410—430°E) with the formation of highly flammable THE. In the presence of acidic impurities, the decomposition temperature can be significantly reduced contact with acids should therefore be avoided, and storage temperatures have to be controlled to prevent decomposition to THF (261). 

Quantum, by contrast, converted an ethylene—carbon monoxide polymer into a polyester-containing terpolymer by treatment with acidic hydrogen peroxide, the Baeyer-Villiger reaction (eq. 11). Depending on the degree of conversion to polyester, the polymer is totally or partially degraded by a biological mechanism. 

Tendering Effects. CeUulosic materials dyed with sulfur black have been known to suffer degradation by acid tendering when stored under moist warm conditions. This effect may result from the Hberation of small quantities of sulfuric acid which occurs when some of the polysulfide links of the sulfur dye are mptured. A buffer, such as sodium acetate, or a dilute alkaH in the final rinse, especially after oxidation in acidic conditions, may prevent this occurrence. Copper salts should never be used with sulfur black dyes because they cataly2e sulfuric acid generation. Few instances of tendering with sulfur dyes other than black occur and the problem is largely confined to cotton. 

Deoxyribonuclease (DNAase), an enzyme that degrades deoxyribonucleic acid, has been used in patients with chronic bronchitis, and found to produce favorable responses presumably by degrading the DNA, contributed by cell nuclei, to inflammatory mucus (213). Lysozyme [9001 -63-2] hydrolyzes the mucopeptides of bacterial cell walls. Accordingly, it has been used as an antibacterial agent, usually in combination with standard antibiotics. Topical apphcations are also useful in the debridement of serious bums, cellulitis, and dermal ulceration. 

In general,. alkoxy- or silyloxy-isoxazolidines when treated with acid produce 2-isoxazo-lines <77AHC(2i)207, 74MIP41601). Other isoxazolidines are cleaved at the N—O bond with further degradation then following <77AHC(2i)207). The treatment of (182) with HCl generated cinnamic acid and a small amount of benzoic acid, whereas treatment of (182) with... 

In the one application reported for the conversion of the 17jff-acetyl side-chain to the 17-ketone, the intermediate oxime was not isolated, but hydrolyzed in situ with acid in an overall yield of about 20 %. In the case of 17jff-acetyl-D-norandrostanes, which are particularly difficult to degrade to D-norandrostanes, the nitrite procedure proved the most convenient method. The yield is 25 %, nowhere near the much higher yield obtained by a Baeyer-Villiger reaction which, however, must be allowed to proceed for one month at 0°. ... 

Diglycolamine Systems. The Fluor Econamine process uses digl> co lamine (DGA) to sweeten natural gas. The active DGA reagent is 2-(2-tunino-ethoxy) ethanol, w hich is a primary amine. The reactions of DG, with acid gases are the same as for MEA. Degradation products from reactions with COS and CS2 can be regenerated in a reclaimer. 

A major advance was devised by Pehr Edrnan (University of Lund, Sweden) that has become the standard method for N-terminal residue analysis. The Edman degradation is based on the chemistry shown in Figure 27.12. A peptide reacts with phenyl isothiocyanate to give a phenylthiocarbamoyl (PTC) derivative, as shown in the first step. This PTC derivative is then treated with an acid in an anhydrous medium (Edrnan used nitrornethane saturated with hydrogen chloride) to cleave the amide bond between the N-terminal anino acid and the remainder of the peptide. No other peptide bonds are cleaved in this step as amide bond hydrolysis requires water. When the PTC derivative is treated with acid in an anhydrous medium, the sulfur atom of the C=S unit acts as... 

Cleavage at A or G If the DNA is first treated with acid, dimethyl sulfate methylates adenine at the 3-position as well as guanine at the 7-position (not shown). Subsequent reaction with OH and piperidine triggers degradation and displacement of the methylated A or G purine base and strand scission, essentially as indicated here for reaction of dimethyl sulfate with guanine. 

Figure 19 (a) DSC melting curve at atmospheric pressure for PE crystallized at 234°C and 513 MPa for 235 h (b) matching GPC curve after degraded with fuming nitric acid for 10 h. (From Ref. 136.)... 

In another series of experiments, a novel approach to the determination of nucleotide sequence was adopted by A. S. Jones, Stacey, and their co-workers. For example, when calf thymus DNA was treated with mercaptoacetic acid in the presence of zinc chloride and anhydrous sodium sulfate, it yielded aldehydo-apurinic acid bis(carboxymethyl) dithioacetal. When degraded with dilute alkali, this afforded dialyzable fragments, which were separated into at least 20 components. Some were identified, including mono-, di-, and tri-nucleotides, thereby revealing that DNA contain regions of at least three linked pyrimidine nucleotides. The same procedure was applied to the DNA isolated from M. phlei ... 

A number of polymers are capable of fulfilling these demanding requirements. Typically negative photoresists are based on cyclised poly(l,4-isoprene). These polymers are prepared by dissolving poly(l,4-isoprene) in an appropriate solvent and subjecting it to thermal degradation. This is followed by treatment with acid to produce the cyclised material (see Reaction 8.8). 

Improved methods for the disposal of methyl parathion are being considered. In 1981, methyl parathion was considered as a potential candidate for rotary kiln incineration and fluidized bed incineration (EPA 198 lb). An accelerated degradation process for methyl parathion, which involved reducing the compound in soil with acid and zinc to its less toxic degradates, was found to be effective (Butler et al. 1981b). No recent information on disposal is available. 

---