In situ Sonochemical Activation of Metals

In many syntheses activation is not effected by sonochemical preparation of the metal alone but rather by sonication of a mixture of the metal and an organic reagent(s). The first example was published many years ago by Renaud, who reported the beneficial role of sonication in the preparation of organo-lithium, magnesium, and mercury compounds [86]. For many years, these important findings were not followed up but nowadays this approach is very common in sonochemistry. In another early example an ultrasonic probe (25 kHz) was used to accelerate the preparation of radical anions [87]. Unusually for this synthesis of benzoquinoline sodium species (5) the metal was used in the form of a cube attached to the horn and preparation times in diethyl ether were reduced from 48 h (reflux using sodium wire) to 45 min using ultrasound. 

Today one of the most common chemical applications of ultrasound is the initiation of a reluctant Grignard reaction. The quantitative effects of ultrasound on the induction times for the formation of a Grignard reagent in various grades of ether is given in Tab. 3.2 [88]. 

Type of diethyl ether used Method Induction time 

The Bouveault reaction is the preparation of an aldehyde by a one pot reaction between an organic halide and lithium metal in dimethylformamide. Ultrasound has been found to markedly enhance this reaction when it is performed in tetrahydrofuran [93]. Use of an ultrasonic bath at 10-20 °C affords short reaction times of between 5 and 15 min and generates yields in the range 70-88%. Using this methodology the conversion of 1-bromobutane to pentanal (88%) can be achieved in only 5 minutes. This must be contrasted with the yield of less than 10 % which is obtained under the normal stirred conditions in the same time period. This result confirms that the effect of irradiation goes beyond mere agitation (Eq. 3.11). 

The zinc promoted cycloaddition of a,a -dibromoketones to 1,3-dienes is enhanced by ultrasound to such an extent that compounds such as the highly hindered bicy-clo[3.2.1]oct-6-en-3-ones (13) become easily accessible (Eq. 3.12) [96]. Reactions of this type, in the absence of ultrasound, give only low to moderate yields and require much longer reaction times of the order of 24 h. 

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