Strong nucleophile

For continuing polymerization to occur, the ion pair must display reasonable stabiUty. Strongly nucleophilic anions, such as C/ , are not suitable, because the ion pair is unstable with respect to THE and the alkyl haUde. A counterion of relatively low nucleophilicity is required to achieve a controlled and continuing polymerization. Examples of anions of suitably low nucleophilicity are complex ions such as SbE , AsF , PF , SbCf, BE 4, or other anions that can reversibly coUapse to a covalent ester species CF SO, FSO, and CIO . In order to achieve reproducible and predictable results in the cationic polymerization of THE, it is necessary to use pure, dry reagents and dry conditions. High vacuum techniques are required for theoretical studies. Careful work in an inert atmosphere, such as dry nitrogen, is satisfactory for many purposes, including commercial synthesis. 

Substitutions. The cyanamide anion is strongly nucleophilic and reacts with most alkylating or acylating reagents (4) addition to a variety of unsaturated systems occurs readily (4). In some cases, a cyanamide salt is used in others, base catalysis suffices. Ethyl iodide reacts with sodium hydrogen cyanamide [17292-62-5] to form a trisubstituted isomelamine. 

DNA binding of (30) and its analogs depends on nucleophilic attack on the oxirane ring at C(10), the preferred position because it is benzylic. With strong nucleophiles such as... 

Strong nucleophiles such as Grignard reagents. In general, ortho esters are difficult to prepare directly from acids and are therefore more often prepared from the nitrile. Simple ortho esters derived from normal alcohols are the least stable in terms of acid stability and stability toward Grignard reagents, but as the ortho ester becomes more constrained its stability increases. 

The simplest method for obtaining selective fluonnation is to conduct reactions under conditions that invigorate the electrophilicity of fluorine In practice this method entails the creation of anionic or strongly nucleophilic reactive centers on substrate molecules while suppressing or reducing the tendency toward radical attack Numerous examples of seleetive fluorine attack on carbanionic, amido and carboxylato species are documented Especially abundant is alpha fluonnation of nitroalkanes in polar solvents [42 43, 44, 45 46] (equations 10-14)... 

Recently developed trifluoromethylatmg agents capable of transferring the trifluoromethyl group as a cation to strongly nucleophilic compounds such as carbanions and sulfur and phosphorus nucleophiles are prepared from o-biphenyl trifluoromethyl sulfoxide [164] and are shown in equation 141... 

However, alcoholic KOH effects a similar quantitative reaction at 25°C. Reaction with liquid NH3 is also smooth particularly in the presence of a strong nucleophile such as NaNH2 ... 

With strong nucleophiles such as methoxide, ring opening follows an Sn2 mechanism. Examine the next to lowest-unoccupied molecular orbital (LUMO+1) for propylene oxide. On which carbon is it most heavily concentrated Is this also the least crowded carbon (Examine a spacefilling model for propylene oxide.) What should be the product of Sn2 addition ... 

Cyanide is a sufficiendy strong nucleophile that it can add directly to aldehydes and ketones, ultimately giving a cyanohydrin. 

The latter, which is not normally isolated, may, under favorable conditions, be trapped in the presence of a strong nucleophile, as in the conversion of 340 into 338. It was surmised that the biogenetically modelled synthesis of strychnine-type systems was a demonstration of such a reaction. 

The conversion of a 4-arylazo-5-oxazolone into a 1,2,4-triazole by reaction with a Grignard reagent is mentioned in Section II, B, 3. In HiTnilar fashion, the rearrangement of compound 30 to derivatives of 3-carboxy-l,5-diphenyl-lfl -l,2,4-triazoles (40) proceeds readily in the presence of strong nucleophiles [Eq. (26)]. This transformation undoubtedly occurs by ring opening and dehydrative cychzation, and, indeed, the acyclic amide and hydrazide 41 have been isolated. ... 

Conjugate addition of strong nucleophiles to the >C=N—C=C< moiety, followed by ring opening of the resulting saturated 5 4H)-oxazolone. Thus, 57 reacts with simple or peptidic amino acid esters [Eq. (31)]. Similarly, 62 gives 63 in methanolic 7i-propylamine, and... 

Stable heterocyclic compounds having the intermediate-complex structure are well known. Where these compounds result from addition of a strongly nucleophilic anion to an A-alkylazinium cation or to a very activated substrate or must pass through a high-energy second... 

Because sodium sulfide is a strong nucleophile, other non nucleophilic reagents such as... 

The presence of a negative charge and an unshared electron pair on carbon makes acetylide anions strongly nucleophilic. As a result, they react with many different kinds of electrophiles. 

When lithiated, the ring strain of the three-membered heterocycle remains important, and this strain, combined with a weakening of the a-C-O bond, due to its greater polarization, make metalated epoxides highly electrophilic species [2], They react with strong nucleophiles (often the base that was used to perform the a-deprotonation) to give olefins following the elimination of M2O (Scheme 5.2, Path B), a process often referred to as reductive alkylation . 

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