Grignard reagents ketone reactions with

The larger amounts of Grignard reagents, compared with ketones, lead to the formation of greater amounts of addition reaction products. 

Organoiithium compounds react with esters, acid chiorides, and anhydrides in the same way as Grignard reagents. Reaction with carboxyiic acids gives ketones, but 2 moi of organoiithium are required. 

The mam synthetic application of Grignard reagents is their reaction with certain carbonyl containing compounds to produce alcohols Carbon-carbon bond formation is rapid and exothermic when a Grignard reagent reacts with an aldehyde or ketone... 

Alcohol synthesis via the reaction of Grignard reagents with carbonyl com pounds (Section 14 6) This is one of the most useful reactions in synthetic organ ic chemistry Grignard reagents react with formaldehyde to yield primary alco hols with aldehydes to give secondary alcohols and with ketones to form terti ary alcohols... 

The various Grignard reagents react with a variety of aldehydes and ketones to yield primary alcohols (yield, 27 6%), secondary alcohols (yield, 13 1-71 1%), and tertiary alcohols (yield, 24 9-81 7%) Products of the reactions with acetone are given in Table 4... 

Grignard reagents undergo a general and very useful reaction with ketones. Melhylmagnesium bromide, for example, reacts with cyclohexanone to yield a product with the formula C7HuO. What is the structure of this product if it has an IR absorption at 3400 cm-1 ... 

The addition of Grignard reagents to aldehydes, ketones, and esters is the basis for the synthesis of a wide variety of alcohols, and several examples are given in Scheme 7.3. Primary alcohols can be made from formaldehyde (Entry 1) or, with addition of two carbons, from ethylene oxide (Entry 2). Secondary alcohols are obtained from aldehydes (Entries 3 to 6) or formate esters (Entry 7). Tertiary alcohols can be made from esters (Entries 8 and 9) or ketones (Entry 10). Lactones give diols (Entry 11). Aldehydes can be prepared from trialkyl orthoformate esters (Entries 12 and 13). Ketones can be made from nitriles (Entries 14 and 15), pyridine-2-thiol esters (Entry 16), N-methoxy-A-methyl carboxamides (Entries 17 and 18), or anhydrides (Entry 19). Carboxylic acids are available by reaction with C02 (Entries 20 to 22). Amines can be prepared from imines (Entry 23). Two-step procedures that involve formation and dehydration of alcohols provide routes to certain alkenes (Entries 24 and 25). 

The furoxan ring is more susceptible to nucleophilic attack and reduction than it is to reaction with electrophiles or oxidation. Grignard reagents react with disubstituted furoxans primarily at C-3 and, in most cases, the resulting adduct fragments to a nitrile and a nitronate salt which affords a ketone on workup. 

Chiral 2,2-disubstituted cyclobutanones have been obtained by asymmetric rearrangement of chiral sulfinyl- 177,178 and sulfanylcyclopropanes.179 Using readily available cyclopropyl 4-tolyl (/ )-sulfoxide (l),180 the requisite sulfinylcyclopropanes 3 and 3 were obtained by a sequence of lithiation, reaction with carboxylic acid esters and stereoselective addition of Grignard reagents to the ketones 2 thus formed.178 The corresponding sulfanylcyclopropanes 4 and 4 resulted from a sequence of protection, reduction and deprotection.179... 

In the second method, ethyl oxalyl chloride is converted first into ethyl a-oxo-1 //-imidazole-1 -acetate, which is then treated with a Grignard reagent.192 The precedent for this reaction is that acylimidazolides are highly reactive towards Grignard reagents to yield ketones without further significant reaction with the carbonyl function to give tertiary alcohols.193... 

The Grignard Reaction is the addition of an organomagnesium. halide (Grignard reagent) to a ketone or aldehyde, to form a tertiary or secondary alcohol, respectively. The reaction with formaldehyde leads to a primary alcohol. 

To start this chapter, here are four reactions of the same ketone. For each product, the principal absorptions in the IR spectrum are listed. The pair of reactions on the left should come as no surprise to you nucleophilic addition of cyanide or a Grignard reagent to the ketone produces a product with no C—O peak near 1700 cm-1, but instead an O-H peak at 3600 cnrT1. The 2250 cm-1 peak is C=N C=C is at 1650 cm-1. 

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