Synthesis of Methyl Methacrylate

This new synthesis employs a palladium catalyst and enjoys 100% atom economy compared to the conventional synthesis, which besides using an extremely poisonous HCN enjoys only 47% atom recovery. 

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Industrial uses of HCN are for synthesis of methyl methacrylate and to form adiponitrile (for adipic acid and nylon) by addition to 1,3-butadiene in the presence of nickel(O) phosphite complexes. Waste HCN is also oxidatively hydrolyzed to give oxamide for use as fertilizer. 

Acetone is an important intermediate in the synthesis of methyl methacrylate eind bisphenol-A, both of... 

Synthesis of methyl methacrylate is fundamental to the production of the transparent plastic polymethyl methacrylate (PMMA), and is estimated at over two million metric tons per year. The monomer is most commonly synthesized via the well-established Acetone Cyanohydrin (ACN) process, as shown below, based on easily available raw materials such as, acetone, hydrogen cyanide, methanol and sulfuric acid. Reaction of acetone and hydrogen cyanide yields acetone cyanohydrin as an intermediate, which is then reacted with excess amount of concentrated sulfuric acid, followed by thermal cracking to form methacrylamide sulfate. The methacrylamide sulfate intermediate is then further hydrolyzed and esterified with aqueous methanol to form methyl methacrylate. 

HCN-free, C -Oxidation Process for Synthesis of Methyl Methacrylate (Isobutylene Catalytic Oxidation) ... 

Synthesis of Methyl Methacrylate Via Propionate—Formaldehyde Route ... 

A very convenient synthesis of methyl methacrylate, developed by the shell corporation is given (Scheme 8). 

Roussel, J., and Boutevin, B. (2001). Synthesis of methyl methacrylate oligomers with substituted tetraphenylethane initiator. Polym. Int., 50(9) 1029 1034. 

Carbon monoxide is an important industrial C-1 Chemicar. The major derived products are methanol and phosgene. The synthesis of methyl methacrylate from acetylene, carbon monoxide and methanol is another industrially useful reaction. Carbon monoxide is a stable carbene, CO, and therefore I have included many of its cycloaddition reactions. The [2-I-2-I-1] cycloaddition reaction which leads to five-membered ring carbonyl compounds is of considerable synthetic value. Copolymers of alkenes and carbon monoxide are a new class of biodegradable polyketones, which can be readily converted into functional polymers. Also copolymers of alkylene oxides and carbon monoxide are known. 

Fig. 5-21 Synthesis of methyl-methacrylate group containing poly(pyrroles). After Stanke et al. References [136, 137], reproduced with permission.

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