Grignard catalysts

Lithium and magnesium alkyl catalysts yield metal-polymer bonds with appreciable covalent character and their cations coordinate strongly with nucleophiles. Therefore, these catalysts will initiate simple anionic polymerization only under the most favorable conditions, e. g., in basic solvents and with monomers which produce resonance stabilized polymer anions. As examples of stereoregular anionic polymerization, a-methyl-methacrylate yields syndiotactic polymer with an alkyl lithium catalyst in 1,2-dimethoxyethane at — 60° C. (211, 212) or with a Grignard catalyst at -40° C. (213). 

Stereoselective polymerizations and copolymerizations of methacrylates have also been realized recently and are potentially of considerable importance. In the case of (RS)-a-methylbenzyl methacrylate with anionic catalysts and 2,3-epoxypropyl methacrylate with an optically active Grignard catalyst selective propagations appear to occur. Copolymerization of (RS)-a-methyl-benzyl methacrylate and methyl methacrylate also proceed stereoselectively. ... 

TT-Allylpalladium chloride (36) reacts with the nucleophiles, generating Pd(0). whereas tr-allylnickel chloride (37) and allylmagnesium bromide (38) reacts with electrophiles (carbonyl), generating Ni(II) and Mg(II). Therefore, it is understandable that the Grignard reaction cannot be carried out with a catalytic amount of Mg, whereas the catalytic reaction is possible with the regeneration of an active Pd(0) catalyst, Pd is a noble metal and Pd(0) is more stable than Pd(II). The carbon-metal bonds of some transition metals such as Ni and Co react with nucleophiles and their reactions can be carried out catalytic ally, but not always. In this respect, Pd is very unique. 

Miscellaneous Reactions. Sodium bisulfite adds to acetaldehyde to form a white crystalline addition compound, insoluble in ethyl alcohol and ether. This bisulfite addition compound is frequendy used to isolate and purify acetaldehyde, which may be regenerated with dilute acid. Hydrocyanic acid adds to acetaldehyde in the presence of an alkaU catalyst to form cyanohydrin the cyanohydrin may also be prepared from sodium cyanide and the bisulfite addition compound. Acrylonittile [107-13-1] (qv) can be made from acetaldehyde and hydrocyanic acid by heating the cyanohydrin that is formed to 600—700°C (77). Alanine [302-72-7] can be prepared by the reaction of an ammonium salt and an alkaU metal cyanide with acetaldehyde this is a general method for the preparation of a-amino acids called the Strecker amino acids synthesis. Grignard reagents add readily to acetaldehyde, the final product being a secondary alcohol. Thioacetaldehyde [2765-04-0] is formed by reaction of acetaldehyde with hydrogen sulfide thioacetaldehyde polymerizes readily to the trimer. 

Using only the phenyhnagnesium chloride without the MnCI catalyst results ia a mixture of products. This mixture iacludes the alcohol(s) resulting from the diaddition of the Grignard reagent to the carbonyl groups. Other catalysts, such as Fe(III) and Ni(II), have also been used to achieve similar results... 

In the reaction of aHyl alcohol and Grignard reagent with [P(CgH )2]2-NiCl2 the catalyst, formation of the carbon—carbon bond proceeds at a high yield (22). 

All lation. Thiophenes can be alkylated in the 2-position using alkyl halides, alcohols, and olefins. Choice of catalyst is important the weaker Friedel-Crafts catalysts, eg, ZnCl2 and SnCl, are preferred. It is often preferable to use the more readily accompHshed acylation reactions of thiophene to give the required alkyl derivatives on reduction. Alternatively, metalation or Grignard reactions, on halothiophenes or halomethylthiophenes, can be utilized. 

Allyl Complexes. Allyl complexes of thorium have been known since the 1960s and are usually stabilized by cyclopentadienyl ligands. AEyl complexes can be accessed via the interaction of a thorium haUde and an aHyl grignard. This synthetic method was utilized to obtain a rare example of a naked aHyl complex, Th(Tj -C2H )4 [144564-74-9] which decomposes at 0°C. This complex, when supported on dehydroxylated y-alumina, is an outstanding heterogeneous catalyst for arene hydrogenation and rivals the most active platinum metal catalysts in activity (17,18). 

Other Rea.ctlons, The anhydride of neopentanoic acid, neopentanoyl anhydride [1538-75-6] can be made by the reaction of neopentanoic acid with acetic anhydride (25). The reaction of neopentanoic acid with acetone using various catalysts, such as titanium dioxide (26) or 2irconium oxide (27), gives 3,3-dimethyl-2-butanone [75-97-8] commonly referred to as pinacolone. Other routes to pinacolone include the reaction of pivaloyl chloride [3282-30-2] with Grignard reagents (28) and the condensation of neopentanoic acid with acetic acid using a rare-earth oxide catalyst (29). Amides of neopentanoic acid can be prepared direcdy from the acid, from the acid chloride, or from esters, using primary or secondary amines. 

Other apphcations for monochlorobenzene include production of diphenyl-ether, ortho- and i ra-phenylphenol, 4,4 -dichlorodiphenylsulfone, which is a primary raw material for the manufacture of polysulfones, diphenyldichlorosilane, which is an intermediate for specialty siUcones, Grignard reagents, and in dinitrochlorobenzene and catalyst manufacture. 

The refined grade s fastest growing use is as a commercial extraction solvent and reaction medium. Other uses are as a solvent for radical-free copolymerization of maleic anhydride and an alkyl vinyl ether, and as a solvent for the polymerization of butadiene and isoprene usiag lithium alkyls as catalyst. Other laboratory appHcations include use as a solvent for Grignard reagents, and also for phase-transfer catalysts. 

Alkyl- and aryl-pyridazines can be prepared by cross-coupling reactions between chloropyridazines and Grignard reagents in the presence of nickel-phosphine complexes as catalysts. Dichloro[l,2-bis(diphenylphosphino)propane]nickel is used for alkylation and dichloro[l,2-bis(diphenylphosphino)ethane]nickel for arylation (78CPB2550). 3-Alkynyl-pyridazines and their A-oxides are prepared from 3-chloropyridazines and their A-oxides and alkynes using a Pd(PPh3)Cl2-Cu complex and triethylamine (78H(9)1397). 

The direct process is less flexible than the Grignard process and is restricted primarily to the production of the, nevertheless all-important, methyl- and phenyl-chlorosilanes. The main reason for this is that higher alkyl halides than methyl chloride decompose at the reaction temperature and give poor yields of the desired products and also the fact that the copper catalyst is only really effective with methyl chloride. 

Catalyst Manufacture, Alvin B. Stiles and Theodore A. Koch Handbook of Grignard Reagents, edited by Gary S. Silverman and Philip E. Rakita... 

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