Alkylation ester

Additives acting on the pour point also modify the crystal size and, in addition, decrease the cohesive forces between crystals, allowing flow at lower temperatures. These additives are also copolymers containing vinyl esters, alkyl acrylates, or alkyl fumarates. In addition, formulations containing surfactants, such as the amides or fatty acid salts and long-chain dialkyl-amines, have an effect both on the cold filter plugging point and the pour point. 

Some details of the chain-initiation step have been elucidated. With an oxygen radical-initiator such as the /-butoxyl radical, both double bond addition and hydrogen abstraction are observed. Hydrogen abstraction is observed at the ester alkyl group of methyl acrylate. Double bond addition occurs in both a head-to-head and a head-to-tail manner (80). 

Determining the degree of substitution using standard proton nmr refles on the integral ratio between the ceUulosic ring protons ( i 5.0-2.96) and the ester alkyl protons ( i 1.26 for butyryl and propionyl and i 2.06 for acetyl methyl groups). This simple procedure is used extensively to determine the extent of esterification and is currently the fastest, easiest way for determining the DS of mixed cellulose esters. 

Nylons 46, 6, 66, 610, 11 and 12 are polar crystalline materials with exceptionally good resistance to hydrocarbons. Esters, alkyl halides, and glycols have little effect. Alcohols generally have some swelling action and may in fact dissolve some copolymers (e.g. nylon 66/610/6). There are few solvents for the nylons, of which the most common are formic acid, glacial acetic acid, phenols and cresols. 

Medium reactivity contaminants alcohols, ketones, organic acids, esters, alkyl-substituted aromatics, nitro-substituted aromatics, carbohydrates. 

Tabushi and Fujiyoshi have prepared alkylated cyclam derivatives for the purpose of suspending these systems from a polymer backbone. They have utilized a malonic ester alkylation reaction followed by cyclization and reduction to accomplish this end. ... 

Deep fluorinalion of alkanes, ethers, acid fmlides, esters, alkyl chlorides, most ketones, ketals, orthoesters, and combinations of these functional groups produces principally the perfluonnated analogues (Table 2) Chlorine substituents (or chloro groups) usually survive fluorination... 

The product of malonic ester alkylation has one acidic o hydrogen atom left, so the alkylation process can be repeated a second time to yield a dialkyl-ated malonic ester. 

The cyclic /3-keto ester produced in a Dieckmann cyclization can be further alkylated and decarboxylated by a series of reactions analogous to those used in the acetoacetic ester synthesis (Section 22.7). For example, alkylation and subsequent decarboxylation of ethyl 2-oxocyclohexanecarboxylate yields a 2-alkylcvclohexanone. The overall sequence of (1) Dieckmann cyclization, (2) /3-keto ester alkylation, and (3) decarboxylation is a powerful method for preparing 2-substituted cyclohexanones and cyclopentanones. 

X = alkynyl - alkenyl < aryl - nitnle < keto < ester alkyl exothermicity delocalization... 

Disproportionation increases in the series where the ester is methyl suggesting that this process is favored by increasing the bulk of the ester alkyl group. This trend is also seen for polymeric radicals (Section... 

Values of kjkli for polymerizations of EM A and BMA and higher methacrylate esters have been determined.11 lIl>1V7 l5i The extent of disproportionation increases with the size of the ester alkyl group. 

This reaction is rapid and can, under anhydrous conditions, be carried out at mild temperatures (60-120°C). The type of leaving group has a strong effect on attainable molecular weights. The polyamide melt syndtesis with dimediyl tereph-thalate has however not been so successful, because N-methylation takes place at high temperatures. This N-methylation is due to die mediyl ester alkylation of die amines and not due to the presence of medianol.28 40 This N-mediylation reaction is significant at temperatures over 200°C. Widi odier esters, N-alkylation takes place to a much lower extent. 

Note. The parentheses are inserted to distinguish between the ester alkyl group (cited first) and the glycosidic O-alkyl group. 

If the reducing terminal is a uronic ester glycoside, the ester alkyl group is cited at the beginning of the name, and the aglyconic alkyl group is cited with the name of the glycosidic residue. 

However, upon dissolution, an epimerization of the anions can occur in the presence of acidic counter-ions. This is particularly true for 16a-16d [39]. The nature of the solvent (MeOH, CHCI3) plays a crucial role on the kinetics of epimerization and the position of the resulting equilibrium. For anions made with a 2R, 3R) tartaric backbone, a A configuration is always preferred in MeOH the selectivity, obtained after a slow equilibration, being independent of the nature of the ester alkyl chain (diastereomeric ratio (d.r.) 3 1). However, in chloroform, the A diastereomer is rapidly obtained and the selectivity is best if the ester side chain is sterically demanding (d.r. 2 1 to 9 1 from 16a to 16d) (Scheme 16). 

Fig. 13 Molecular structure of 2 OEt-2 OPr-cyclo viewed along the phenylene planes. Both of the ester alkyl moieties are depicted by a propyl group.

Fig. 14 Crystal structure of 2 OEt-2 OPr. Two molecules making a pair (B and C) and two neighbouring molecules in the other pairs (A and D) viewed along the phenylene groups in molecules B and C. All the ester alkyl moieties are depicted by an ethyl group.

C-Alkylation of malonic acid esters Malonic acid esters, alkyl halides... 

Scheme 1.6 gives some examples of alkylation of esters, amides, and nitriles. Entries 1 and 2 are representative ester alkylations involving low-temperature... 

It has been reported that the geometry of olefins obtained from the reaction of dialkyl l-(ethoxycarbonyl)ethylphosphonates and a-phenylpropionaldehyde can be controlled by choice of the phosphonate ester alkyl groups diisopropyl ester gives (E), while dimethyl ester gives (Z). This has now been confirmed for the... 

Model (1) further suggests that, if the substrate is a secondary allylic alcohol (R4 / 11, R5 = H or r4=h, rVh), enantiomeric alcohols are epoxidized at different rates when (R,R)-DAT is used as the chiral auxiliary, (5)-allylic alcohol (R4 f H, R5 = H) suffers less steric hindrance from the tartrate ligand and is oxidized faster than (R)-allylic alcohol (R4 = H, R5 f H).37 As the ester alkyl group of DAT becomes bulkier, the hindrance becomes more intense and the relative... 

Reactions with Carboxylic Acid Esters Alkyl nitrones can be metallized upon treatment with phenyl lithium in ether solution. The Li-derivatives react with carboxylic acid esters to give 3-oxo nitrones (305)- the analogs of 3-diketones and j3-keto esters (545). With the help of the 13C NMR method it has been found that 3-oxo nitrones (305) exist as an equilibrium mixture... 

---