Ester, defined

Hydrolysis half-lives of carboxylic acid esters, defined as ... 

P-methylvaleric) during the smoking process, led many years later to a series of studies aimed at determining the structure of the sucrose esters in tobacco. Despite the numerous studies, seldom was the precise structure of a sucrose ester defined. The various studies included those of Rivers (3185) in the early 1980s and of Severson et al. (3606), Schlotzhauer et al. (3473), Wahlberg et al. (4102), and Danehower (896) in the mid- to late 1980s. 

Synenyms Hexaderyl 12-hydroxy-9-octadecenoale Hexadecyl (R)-12-hydroxy-oleate 12-Hydroxy-9-octadecenoicacid ester Defin itien Ester of cetyl alcohol and ricinoleic acid Empirical C34HggOj... 

The achiral triene chain of (a//-rrans-)-3-demethyl-famesic ester as well as its (6-cis-)-isoiner cyclize in the presence of acids to give the decalol derivative with four chirai centres whose relative configuration is well defined (P.A. Stadler, 1957 A. Escherunoser, 1959 W.S. Johnson, 1968, 1976). A monocyclic diene is formed as an intermediate (G. Stork, 1955). With more complicated 1,5-polyenes, such as squalene, oily mixtures of various cycliz-ation products are obtained. The 18,19-glycol of squalene 2,3-oxide, however, cyclized in modest yield with picric acid catalysis to give a complex tetracyclic natural product with nine chiral centres. Picric acid acts as a protic acid of medium strength whose conjugated base is non-nucleophilic. Such acids activate oxygen functions selectively (K.B. Sharpless, 1970). 

The stereo-defined enol ester 432 is prepared by the reaction of the vinyl-mercurial 431, obtained by acetoxymercuration of 2-butyne. with mercury(II) carboxylates using a catalytic amount of Pd(OAc)2[392]. 

There are ill-defined limits on EI/CI usage, based mostly on these issues of volatility and thermal stability. Sometimes these limits can be extended by preparation of a suitable chemical derivative. For example, polar carboxylic acids generally give either no or only a poor yield of molecular ions, but their conversion into methyl esters affords less polar, more volatile materials that can be examined easily by EL In the absence of an alternative method of ionization, EI/CI can still be used with clever manipulation of chemical derivatization techniques. 

Nitration is defined in this article as the reaction between a nitration agent and an organic compound that results in one or more nitro (—NO2) groups becoming chemically bonded to an atom in this compound. Nitric acid is used as the nitrating agent to represent C-, 0-, and N-nitrations. O-nitrations result in esters. N-nitrations result in nitramines. 

Sulfation is defined as any process of introducing an SO group into an organic compound to produce the characteristic C—OSO configuration. Typically, sulfation of alcohols utilizes chlorosulfuric acid or sulfur trioxide reagents. Unlike the sulfonates, which show remarkable stability even after prolonged heat, sulfated products are unstable toward acid hydrolysis. Hence, alcohol sulfuric esters are immediately neutralized after sulfation in order to preserve a high sulfation yield. 

Physical Properties. Oligosaccharide antibiotics are colodess soHds, which are often crystalline and have defined melting poiats and optical rotations, [cc] (see Tables 1 and 2). They have a characteristic uv spectmm resulting from the phenoHc ester residue, 285 nm (s ca 22), which shifts... 

Unprotected racemic amines can be resolved by enantioselective acylations with activated esters (110,111). This approach is based on the discovery that enantioselectivity of some enzymes strongly depends on the nature of the reaction medium. For example, the enantioselectivity factor (defined as the ratio of the initial rates for (3)- and (R)-isomers) of subtiHsin in the acylation of CX-methyl-ben zyl amine with tritiuoroethyl butyrate varies from 0.95 in toluene to 7.7 in 3-methyl-3-pentanol (110). The latter solvent has been used for enantioselective resolutions of a number of racemic amines (110). 

Viscosity is defined as the shear stress per unit area at any point in a confined fluid divided by the velocity gradient in the direc tiou perpendicular to the direction of flow. If this ratio is constant with time at a given temperature and pressure for any species, the fluid is caUed a Newtonian fluid. This section is limited to Newtonian fluids, which include all gases and most uoupolymeric liquids and their mixtures. Most polymers, pastes, slurries, waxy oils, and some silicate esters are examples of uou-Newtouiau fluids. 

Saponification number (DIN 51 559). The saponification number is indicative of the presence of ester groups in a resin. The saponification number is defined as the consumption of potassium hydroxide in milligrams by one gram of resin under standardized conditions. 

Adhesion depends on a number of factors. Good adhesion is defined by most customers as substrate failure. The major adhesive manufacturers possess equipment that allows them to make bonds with customer substrates under conditions that closely simulate actual packaging lines. These bonds are peeled either automatically or by hand to gauge adhesion. The most important factors influencing adhesion are the wet-out of the substrate, partieularly by the polymer component of the adhesive system, and the specific adhesion with the substrate. Choice of resin is critical for both. Rosin, rosin esters and terpene phenolics are eommonly added for these purposes in EVA and EnBA-based systems. Adhesion at low temperatures is also influenced by the overall toughness of the system at the test temperature. 

A catalyst is defined as a substance that influences the rate or the direction of a chemical reaction without being consumed. Homogeneous catalytic processes are where the catalyst is dissolved in a liquid reaction medium. The varieties of chemical species that may act as homogeneous catalysts include anions, cations, neutral species, enzymes, and association complexes. In acid-base catalysis, one step in the reaction mechanism consists of a proton transfer between the catalyst and the substrate. The protonated reactant species or intermediate further reacts with either another species in the solution or by a decomposition process. Table 1-1 shows typical reactions of an acid-base catalysis. An example of an acid-base catalysis in solution is hydrolysis of esters by acids. 

Taft began the LFER attack on steric effects as part of his separation of electronic and steric effects in aliphatic compounds, which is discussed in Section 7.3. For our present purposes we abstract from that treatment the portion relevant to aromatic substrates. Hammett p values for alkaline ester hydrolysis are in the range +2.2 to +2.8, whereas for acid ester hydrolysis p is close to zero (see Table 7-2). Taft, therefore, concluded that electronic effects of substituents are much greater in the alkaline than in the acid series and. in fact, that they are negligible in the acid series. This left the steric effect alone controlling relative reactivity in the acid series. A steric substituent constant was defined [by analogy with the definition of cr in Eq. (7-22)] by Eq. (7-43), where k is the rate constant for acid-catalyzed hydrolysis of an orr/to-substituted benzoate ester and k is the corresponding rate constant for the on/to-methyl ester note that CH3, not H, is the reference substituent. ... 

Correlations with o in carboxylic acid derivative reactions have been most successful for variations in the acyl portion, R in RCOX. Variation in the alkyl portion of esters, R in RCOOR, has not led to many good correlations, although use of relative rates of alkaline and acidic reactions, as in the defining relation, can generate linear correlations. The failure to achieve satisfactory correlations with cr for such substrates may be a consequence of the different steric effects of substituents in the acyl and alkyl locations. It has been shown that solvolysis rates of some acetates are related to the pA", of the leaving group, that is, of the parent alcohol. The pK of alcohols has been correlated with but this relationship... 

If the assumptions underlying the Taft treatment of the separation of electronic and steric effects are valid, then the relative rates of acid-catalyzed reactions of esters should be a measure of the steric effect. Taft " accordingly defined a steric constant Es by Eq. (7-52). 

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