Reaction with magnesium chloride

A propoxyphene-like analgesic which obeys the empirical morphine rule is pyrroliphene (101). A Mannich reaction involving pyrrolidine, formaldehyde and propiophenone gave amino ketone 99, which was converted to tertiary carbinol 100 by reaction with benzyl magnesium chloride reaction with acetyl... 

Butyroin has been prepared by reductive condensation of ethyl butyrate with sodium in xylene, or with sodium in the presence of chloro-trimethylsilane. and by reduction of 4,5-octanedlone with sodium l-benzyl-3-carbamoyl-l,4-dihydropyridine-4-sulfinate in the presence of magnesium chloride or with thiophenol in the presence of iron polyphthalocyanine as electron transfer agent.This acyloin has also been obtained by oxidation of (E)-4-octene with potassium permanganate and by reaction of... 

One surprising example is how ferric (not ferrous) chloride catalyzes the formation of ketyl radicals in a Gringnard-type reaction between ( 113)3001, Mg, and (0Hj)20=O (Ashby and Wiese-mann 1978). The initially formed tert-butyl magnesium chloride reacts with ferric chloride and gives tert-butyl iron(Ill) dichloride ... 

Coupling of acetylenes and halides, copper-promoted, 50,100 Cuprous chloride, reaction with an organo-magnesium compound, 50,98... 

Acetylenic ketones can be prepared in moderate yield by the reaction of acetylenic Grignard reagents with acid chlorides or anhydrides [Eq. (41) 75-78]. Alkynyl magnesium chloride reacts with acetic anhydride to give acetylenic ketones in good yield (see Table 4, entry 17). 

Many studies of the addition of nucleophiles to palladium-allyl complexes have been conducted. Hayashi has shown that the additions of stabilized anions, such as malonate anions or amine nucleophiles, to chiral, non-racemic allyl complexes occur with inversion of configuration.Addition of excess phosphine and either diethyl malonate or dimethylamine to a chiral, non-racemic allyl complex results in nucleophilic attack with nearly complete inversion. The reaction with sodium dimethylmalonate is shown at the right of Equation 11.40. In contrast, nonstabilized carbanions such as allyl or phenyl magnesium chloride react with the same Ti -allylpalladium complex with retention of configuration as shown at the left of Equation 11.40. The stereochemistry from reaction of the Grignard reagents likely results from nucleophilic attack at the metal, followed by reductive elimination. 

B3LYP/6-31 lG-l-l-(d,p) calculations on the reactions of (1-chlorovinyl)- and (1-chlorocyclopropyl)magnesium chlorides solvated with two molecules of dimethyl ether, with a chloride ion, methyl anion, vinyl anion, or an acetylide anion showed that the reactions with magnesium compounds have lower AG values than either chloroethene or chlorocyclopropane. This is attributed to the longer, more reactive, C-Cl bond in the magnesium compounds. The potential energy surfaces, AG values, and the transition state structures for the reactions are given. 

Now let s draw the forward scheme. Hydrolysis of the nitrile to the carboxylic acid, followed by reaction with thionyl chloride, produces the acid chloride. Reaction with excess methyl magnesium bromide, followed by water work-up, results in the formation of a tertiary alcohol, with the incorporation of two new methyl groups. The tertiary alcohol can then serve as a nucleophile in an acetylation reaction (upon treatment with acetyl chloride) to give the desired ester. 

Alkyl and aryl iodides usually react with magnesium more rapidly than the corresponding bromides, and the bromides very much more rapidly than the chlorides. Aryl (as distinct from alkyl) chlorides have usually only a slow reaction with magnesium and are therefore very rarely used. With alkyl and aryl iodides in particular, however, a side reaction often occurs with the formation of a hydrocarbon and magnesium iodide ... 

Prepare a solution of benzyl magnesium chloride in a 2-litre three-necked flask from 24-3 g. of magnesium turnings, 600 ml. of sodium-dried ether and 126-5 g. (115 ml.) of redistilled benzyl chloride follow the experimental details given under n-Propylbenzene (Section IV,7). Cool the flask in running water or in ice water. Place a solution of 456 g. of n-butyl-p-toluenesulphonate (Section IV,198) in about twice its volume of anhydrous ether in the dropping funnel, and add it slowly with stirring, at such a rate that the ether just boils a white solid soon forms. The addition is complete after about 2 hours. Pour the reaction product... 

The other commercially important routes to alkyltin chloride intermediates utilize an indirect method having a tetraalkjitin intermediate. Tetraalkyltins are made by transmetaHation of stannic chloride with a metal alkyl where the metal is typicaHy magnesium or aluminum. Subsequent redistribution reactions with additional stannic chloride yield the desired mixture of monoalkyl tin trichloride and dialkyltin dichloride. Both / -butjitin and / -octjitin intermediates are manufactured by one of these schemes. 

These reactions have been studied extensively, and many variations exist ia the use of HCl atmospheres to maximize the desired reactions. The dehydration of camaUite occurs with minimum hydrolysis, but results ia a mixed MgCl2—KCl cell feed. The use of magnesium chloride hexammoniate [24349-22-2], MgCl2 hNH, has been proposed, but is not practiced commercially. This salt readily deammoniates to anhydrous MgCl2. 

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