Expectation functions

Thus, chloro enamines 113, either under Barbier-type reaction conditions (—40 °C) or in a two-step process (hthiation at —90 °C and Sg reaction at —90 to —40 °C), were lithiated with DTBB (5%) and finally hydrolyzed, after condensation with different electrophiles, giving the expected functionalized enamines 114 (Scheme 44) °. ... 

Hydroxyalkyl thioethers 134 reacted successively with n-butyllithium and lithium containing a catalytic amount of DTBB (5%), both in THF at —78°C, to form intermediates 135, which in a second step were aUowed to react with different electrophiles to yield, after hnal hydrolysis, the expected functionalized alcohols 136 (Scheme 50) " ... 

However, either for aliphatic or aromatic amines, the corresponding S-phenylthio derivatives are adequate precursors in order to generate /i-amido organoUthium intermediates. Starting materials 157 were successively treated with n-butyllithium and lithinm in the presence of a catalytic amount of DTBB (15%) in THF at —78 °C giving the expected functionalized organolithium intermediates 158, which reacted with different electrophiles to afford, after hydrolysis, the corresponding products 159 (Scheme 56) " ". 

The hthiation of the to-chloro acetal 230 using a catalytic amount of naphthalene (4%) in THF at —78°C gave the corresponding masked tu-lithio enolate 231, which reacted with different electrophiles at —78 °C to room temperature yielding, after hydrolysis with water, the expected functionalized acetals 232 (Scheme 78) . 

The reaction of the three chloro pyridines 244 with lithium in the presence of a catalytic amount of naphthalene (4%) and different electrophiles in THF at —78°C gave, after hydrolysis, the expected functionalized pyridines 245 (Scheme 82) . 

Treatment of Af-phenylazetidine 315 with lithium and a catalytic amount of DTBB (5%) in THF at — 15°C led to a solution of the corresponding y-functionalized organohthium intermediate 316, which by reaction with different electrophiles at temperatures ranging between —78 and 20 °C, and final hydrolysis, afforded the expected functionalized amines 317. The same reaction using azetidine 318 yielded products 320, functionalized at the benzylic position, intermediates 319 being involved in the process (Scheme 93) . ... 

Phenyl-Af-isopropylpyrrolidine (351) was opened with lithium and a catalytic amount (4.5%) of DTBB in THF at room temperature to give the most stable benzylic intermediate 352, which after tandem electrophilic substitution reaction at —78°C and final hydrolysis afforded the expected functionalized amines 353 (Scheme 103). ... 

An interesting entry to functionalized dihydropyrans has been intensively studied by Tietze in the 1990s using a three-component domino-Knoevenagel Hetero-Diels-Alder sequence. The overall transformation involves the transient formation of an activated heterodienophile by condensation of simple aldehydes with 1,3-dicarbonyls such as barbituric acids [127], Meldrum s acid [128], or activated carbonyls. In situ cycloaddition with electron-rich alkenes furnished the expected functionalized dihydropyrans. Two recent examples concern the reactivity of 1,4-benzoquinones and pyrazolones as 1,3-dicarbonyl equivalents under microwave irradiation. In the first case, a new three-component catalyst-free efficient one-pot transformation was proposed for the synthesis of pyrano-1,4-benzoquinone scaffolds [129]. In this synthetic method, 2,5-dihydroxy-3-undecyl-1,4-benzoquinone, paraformaldehyde, and alkenes were suspended in ethanol and placed under microwave irradiations to lead regioselectively the corresponding pyrano-l,4-benzoquinone derivatives (Scheme 38). The total regioselectivity was... 

Furazan- and furoxan-carboxylic acids are thermally and hydrolytically unstable decomposing to a-(hydroxyimino)nitriles, but their amide, ester, halide, and nitrile derivatives are readily accessible and all undergo the expected functional group interconversions. Dicyanofuroxan reacts with hydroxylamine to give the fused oxazino compound (63) and the pyridazino analogue (64) is similarly formed with hydrazine <82H(19)1063>. 

This section of the validation plan should describe the expected function and security of the spreadsheet. The requirements should be formulated in a manner... 

Testing A Protein Product For Functional Properties. Chemical analyses for general composition are essentialto adequately do future functional testing. The percentage of protein and other components will invariably supply clues as to the expected functional properties. Physical analyses for size of... 

This testing involves running the program under known conditions with defined inputs, and documented outcomes that can be compared to predefined expectations. Functional testing is sometimes called black box testing. 

Recently, PEO has been grafted onto PAMAM dendrimers by means of AT-suc-cinimidyl propionic acid spacers [138] (see Scheme 17c). When n=16 and 32, experimental and expected functionalization agree satisfactorily. However, for n= 64,128, and 256, progressively lower functionalization is observed. It is not clear whether this result is due to imperfections of the PAMAM dendrimer used or to steric limitations on the extent of the substitution reaction. At present this reaction scheme has been tested only on PEO chains with MW=5000. 

Due to a large number of food additives used in the food manufacturing industry, depending on the type of a food product, expected functions, and characteristics of food additives, the latter are divided into several groups (types), for example ... 

Exploring different methods for the intramolecular radical cyclization of 78 (Scheme 15)95, Usui and Paquette observed that (TMS SiH under normal conditions affords the expected functionalized diquinane 79 in 80% yield and in a a fi ratio of 82 18. MM2 calculations suggest it is the result of a kinetic controlled process. It is worth mentioning that the endothermic reaction 42 is expected to be one of the propagation steps in this chain process (vide infra). By replacing the silane with tin hydride under similar experimental conditions, the unexpected product 80 was obtained in a 77% yield. 

Fig. 4. Third harmonic demodulated signal of the 23Si — 23P2 transition, fit to the expected function...

TABLE 32.1 Some Expected Functions and Applications of Ionic Liquids... 

As expected, functional groups which are sensitive to the vigorous basic conditions of most Wolff-Kishner reduction conditions do not survive intact. Thus, esters and lactones are normally hydrolyzed to the corresponding acids and alcohols (see, for examples, entries 4, 5 and 8, Table 2) and require... 

This example uses a subroutine MODEL that computes only the values fu e) of the expectation function in Eq. (C.6-1). Input values DEL(i)=-lD-2 are used, with IDIF=1 so that GREGPLUS uses forward-difference approximations of the derivatives dfu 0)/d0j. To make these approximations accurate, the elements DEL(I) are refined by GREGPLUS in each iteration, using Eq, (6.B-7). Abbreviated output is requested by using LISTS = 1. Finally, an additional event condition is selected from five candidates, to minimize the volume of the three-parameter HPD region. Details of the implementation of this example in Athena Visual Studio can be found by running the software and selecting Book Examples under the Help menu item. 

Estimation is then performed for two auxiliary functions of the parameters, namely, the parameter 62 and the expectation function f x,6) at a = 10. Finally, conditions for an additional event are chosen for optimal estimation of the parameters (and thus, their auxiliary functions) in the sense of minimum volume of the three-parameter HPD region. 

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