Aliphatic degradation

Aliphatic-aromatic copoly imides, 268 Aliphatic-aromatic polyesters, 18, 19 Aliphatic degradable polyesters, 41 Aliphatic diacids, polyamide synthesis from, 183-184... 

Fig. 22. Aliphatic degradation products derived from tolypomycinone...

Barbier-Wieland degradation A method for the stepwise degradation of aliphatic acids... 

Aliphatic-Garboxylics. There are only two herbicides present in this class, trichloroacetate [76-03-9] (TCA) and dalapon [75-99-0]. These are used primarily for the selective control of annual and perennial grass weeds in cropland and noncropland (2,299). Dalapon is also used as a selective aquatic herbicide (427). Dalapon and TCA are acidic in nature and are not strongly sorbed by sods. They are reported to be rapidly degraded in both sod and water by microbial processes (2,427). However, the breakdown of TCA occurs very slowly when incubated at 14—15°C in acidic sods (428). Timing not only accelerates this degradation but also increases the numbers of TCA-degrading bacteria. An HA has been issued for dalapon, but not TCA (269). 

Chemical degradation studies carried out on streptovaricias A and C, which are the primary components of the cmde complex, yielded substances shown ia Figure 1. Streptovaricia A (4), consumes two moles of sodium periodate to yield variciaal A [21913-68-8] (1), 0 2 200, which accounts for the ahphatic portion of the molecule, and prestreptovarone [58074-37-6] (2), C2C)H2C)N02, which accounts for the aromatic chromophore of the streptovaricias (Fig. 2). Streptovaricia G (9) is the only other streptovaricia that yields prestreptovaroae upoa treatmeat with sodium periodate. Treatmeat of streptovaricias A (4), B (5), C (6), E (8), and G (9) with sodium periodate and osmium tetroxide yields streptovarone [36108-44-8] (3), C24H23NO2, which is also produced by the reaction of prestreptovarone with sodium periodate and osmium tetroxide (4,65). A number of aliphatic products were isolated from the oxidation of streptovaricia C and its derivatives (66). 

A number of physical and chemical properties of 1-propanol are Hsted ia Table 1 (2,3). The chemistry of 1-propanol is typical of low molecular weight primary alcohols (see Alcohols, higher aliphatic). Biologically, 1-propanol is easily degraded by activated sludge and is the easiest alcohol to degrade (4). 

Polyamide or polyimide polymers are resistant to aliphatic, aromatic, and chlorinated or fluorinated hydrocarbons as well as to many acidic and basic systems but are degraded by high-temperature caustic exposures. 

This has a very high resistance to impact damage, even at subzero temperatures. It has good creep strength in dry conditions up to 115°C but degrades by continuous exposures to water hotter than 65°C. It is resistant to aqueous solutions of acids, aliphatic hydrocarbons, paraffins, alcohols (except methanol), animal and vegetable fats and oils, but is attacked by alkalis, ammonia, aromatic and chlorinated hydrocarbons. 

Phenoxaphosphine ring-containing poly (1,3,4-oxa-diazoles) were synthesized by cyclodehydration of poly-hydrazides obtained from (BCPO) and aliphatic and aromatic dihydrazines [152]. All these polymers are soluble in formic acid, w-cresol and concentrated H2SO4. The polyhydrazides yield transparent and flexible films when cast from DMSO solution under reduced pressure at 80-100°C. The polyhydrazides exhibit reduced viscosities of 0.24-0.40 dl/g in DMAC. Phenoxaphosphine ring-containing oxadiazole polymers showed little degradation below 400°C. 

Thermal stability of polyazines of the third group, i.e., polymers with conjugated sections separated by aliphatic blocks, is determined by the thermal stability of the latter. The degradation process takes place gradually, and it is not accompanied by any considerable heat effects41,117-. ... 

An interesting example of regioselective CM with ethylene as a tool in natural product degradation was recently disclosed by Hawaiian authors [149]. Thus, CM using catalyst C and ethylene gas was used to degrade the plant polyacetylene oxylipin (+)-falcarindiol (342) with uncertain stereochemistry at C3. As the reaction provided a meso product (343) in 81% yield by regioselective attack at the aliphatic side chain, the natural compound 342, isolated from a Hawaiian endemic plant, had the 3R,8S configuration shown in Scheme 66. 

Hie ester linkage of aliphatic and aliphatic-aromatic copolyesters can easily be cleaved by hydrolysis under alkaline, acid, or enzymatic catalysis. This feature makes polyesters very attractive for two related, but quite different, applications (i) bioresorbable, bioabsorbable, or bioerodible polymers and (ii) environmentally degradable and recyclable polymers. 

C and is easily processable, whereas the homopolymers do not melt before the onset of thermal degradation, at temperatures as high as 500°C.73,74 Varying copolymer composition permits the adjustment of melting temperature and of other properties (e.g., solubility) to desired values. This method is frequently used for aliphatic and aromatic-aliphatic polyesters as well. 

Depending on dieir structure, properties, and syndietic methods, degradable polyesters can be divided into four groups poly(a-esters), poly(fi-esters), poly(lactones), and polyesters of aliphatic diols and diacids. 

The semicrystalline polyesters of the terephthalate and naphthalate family are resistant to a wide range of chemicals at room temperature, including water, alcohols, ketones, ethers, glycols, chlorinated solvents, aliphatic hydrocarbons, and oils. They are slowly hydrolyzed in boiling water and rapidly degraded in strongly basic or acidic medium. 

Aliphatic hyperbranched polyesters, 56 Aliphatic isocyanate adducts, 202 Aliphatic isocyanates, 210, 225 Aliphatic polyamides, 138 Aliphatic polyesteramides, 56 Aliphatic polyesters, 18, 20, 29, 32, 87 degradable, 85 hyperbranched, 114-116 melting points of, 33, 36 structure and properties of, 40-44 syntheses of, 95-101 thermal degradation of, 38 unsubstituted and methyl-substituted, 36-38... 

The N-bromination of amides with bromine and alkali has been extensively researched as the first step of the Hofmann degradation. However, it is difficult to isolate the N-bromoamides because of their subsequent reaction to produce amines, which proceeds very readily under excessive alkaline conditions. Now, the reaction of amides with a stoichiometric amount of BTMA Br3 and sodium hydroxide in ice-water gave N-bromoamides in fairly good yields. Our method can be applied to various types of aliphatic, aromatic, and heterocyclic amides (Fig. 31) (ref. 39). 

Polymers with hetero-atoms in the chain are suitable for chemical recycling of waste materials. In addition to depolymerisation (nylon 6) and solvolysis (nylon 6,6, PETP, PU) the degradation of aliphatic polyamides with dicarboxylic acids, diamines and cyclic anhydrides, especially trimellitic anhydride, becomes more and more important. The utilisation of the obtained fragments is described. 

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