Reaction-controlling additives

The glass polyalkenoate cement system was not viable until Wilson and Crisp discovered the action of (+)-tartaric acid as a reaction-controlling additive (Wilson Crisp, 1975,1976,1980 Wilson, Crisp Ferner, 1976 Crisp Wilson, 1976 Crisp, Lewis Wilson, 1979). It may be regarded as an essential constituent and is invariably included in glass polyalkenoate cements as a reaction-controlling additive. 

No other additive has the same effect although many alternatives were examined by Wilson, Crisp Femer (1976) and Prosser, Jerome Wilson (1982). Other multifunctional carboxylic acids, including citric acid, had little effect, apart from a slight tendency to shorten working time and increase the setting rate. That the effect is a subtle one is shown by the fact 

Liquid 50% acrylic-itaconic acid copolymer, 5% tartaric acid 

Ethanolamines and polyphosphates slow the reaction down as a whole. Both tetrahydrofurantetracarboxylic acid and polyphosphates are sometimes to be found in commercial examples. 

Merson Wilson (1980) found that the addition of metal fluorides to formulations had the effect of accelerating cement formation and increasing the strength of set cements the effect was enhanced by the presence of (-I-)-tartaric acid (Table 5.13). Strength of cements formed from an SiOj-AljOg-Cag (P04)2 glass, G-247, can be almost doubled by this technique. 

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A phosphine-based nickel(II) bromide complex (Ni-2) also induces living radical polymerization of MMA specifically when coupled with a bromide initiator in the presence of Al(0-i-Pr)3 as an additive in toluene at 60 and 80 °C.133 The reaction rates and the effects of radical inhibitors are similar to those with Ni-1, whereas chloride initiators are not effective in reaction control. Additives are not necessary when the polymerization is carried out in the bulk or at high concentrations of monomer, either methacrylate or /v-butyl acrylate (nBA).134 An alkylphosphine complex (Ni-3) is thermally more stable and can be employed for MMA, MA, and nBA in a wide range of temperatures (60—120 °C) without additives.135 A fast polymerization proceeds at 120 °C to reach 90% conversion in 2.5 h. A zerovalent nickel complex (Ni-4) is another class of catalyst for living radical polymerization of MMA in conjunction with a bromide initiator and Al(0-i-Pr)3 to afford polymers with narrow MWDs MJMn = 1.2—1.4) and controlled molecular weights.136 The Ni(0) activity is similar to that of Ni(II) complexes whereas the controllability... 

There are significant differences between tliese two types of reactions as far as how they are treated experimentally and theoretically. Photodissociation typically involves excitation to an excited electronic state, whereas bimolecular reactions often occur on the ground-state potential energy surface for a reaction. In addition, the initial conditions are very different. In bimolecular collisions one has no control over the reactant orbital angular momentum (impact parameter), whereas m photodissociation one can start with cold molecules with total angular momentum 0. Nonetheless, many theoretical constructs and experimental methods can be applied to both types of reactions, and from the point of view of this chapter their similarities are more important than their differences. 

Both propylene and isobutylene ate comonomers that are incorporated along the chain, resulting in additional short-chain branching. One important factor in controlling polymer crystallinity is the choice of chain-transfer agent. Ethane and methane, for example, are inefficient agents whose presence in the monomer feed stream must be considered in reaction control. 

Acylthiophenes. Manufacturing methods introducing the carboxaldehyde group into the 2- or 5-positions of thiophene and alkylthiophenes utilise the Vilsmeier-Haack reaction. To synthesize 2-thiophenecarboxaldehyde (Table 5), a controlled addition of phosphoms oxychloride to thiophene in /V, /V- dim ethyl form am i de is carried out, causing the temperature to rise. Completion of the reaction is followed by an aqueous quench, neutralization, and solvent extraction to isolate the product. 

With pteridine (1) the covalent hydration is a complex matter since the general acid-base catalyzed reaction provides a good example of a kinetically controlled addition to the... 

Next, consider the reactivity of phenyl diazonium ion. Are either of the reactions shown above consistent with nucleophilic attack at the ion s most electron-poor site Examine the lowest-unoccupied molecular orbital (LUMO) of phenyl diazonium ion. What electrophilic sites are identified by the LUMO Are either of the reactions shown above consistent with an orbital-controlled addition ... 

Other possibilities for practical application of resin catalysis include some organic reactions involving addition, cyclization, and structural rearrangement. Increased stability and specific control of structure has led to the increased use of cation exchange resins as catalysts. As in the case of cation exchange resins many... 

Addition of alkynes to a-alkoxy aldehydes is most favorably performed with the corresponding zinc reagents (Table 12)46. As with Grignard reagents, the chelation-controlled addition of zinc alkynes proceeds with higher diastereoselectivity when diethyl ether rather than tetrahydrofuran is used as reaction solvent. 

Allyltrialkoxy- or -tris(dialkylamino)titanium reagents are not capable of chelation-controlled addition reactions with oxy- or amino-substituted carbonyl compounds due to their low Lewis acidity87. To attain chelation control, the application of allylsilanes (Section 1.3.3.3.5.2.2.) and allylstannanes (Section I.3.3.3.6.I.3.2.) in the presence of bidentate Lewis acids like titanium(IV) chloride, tin(lV) chloride or magnesium bromide are the better options. 

The chelation-controlled addition of silylketene acetal, 1-phenoxy-l-trimethylsilyloxyethene, to enantiomerically pure (S)-2-dibenzylaminopropanaI is not easily accomplished. Although the predominant formation of one diastcrcomcr is possible (d.r. 95 5), the reaction is plagued by a low chemical yield9. 

In fact, it has been shown that the stereoselectivity of HCl addition can be controlled by changing the reaction conditions. Addition of HCl to 4 in CH2CI2 at -98°C gave predominantly syn addition, while in ethyl ether at 0°C, the addition was mostly... 

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