Ally bromide

To a refluxing solution 0. phenylmagnesium bromide in 650 ml of diethyl ether, prepared from 1.15 mol of broraobenzene (see Chapter 11, Exp. 5) was added 1.00 mol of ally] bromide at a rate such that refluxing was maintained (about 30 min). 

The perfluoroallylcadmium reagent can be prepared similarly by direct reaction of perfluoroallyl iodide with cadmium metal [146] (equation 113). Reaction of this cadmium reagent with ally bromide gives F2C=CFCp2CH2CH=CH2 in 78% yield [146]. 

Synthesis Diacetylmorphine (Heroin) is demethylated with cyanogene bromide and hydrolyzed to normorphine, which is alkylated to ally bromide (, Weijlard and Erickson (Merck Co.), 1944 Weijlard (Merck Co), 1959 Klee-mann et al. 1999). 

More reactive anions such as the 2-lithio-l,3-dithiane derivatives, phenyllithium and r-butyllithium do not require a special solvent and proceed in high yield in THF. While HMPA is known to suppress the migratory insertion to CO in anionic complexes,127 it does not deter the CO insertion in these cases no example of direct alkylation is reported. The only electrophile which adds without CO insertion is the proton, as discussed above. Good alkylating agents (primary iodides and triflates, ally bromide, benzyl... 

Thus, if we add ally bromide F to the Grignard reagent made from the aryl halide G, we can synthesize E. 

Diallyl tellurium, obtained from ally bromide and sodium telluride, decomposed at 180 with formation of biallyl (1,5-hexadiene)2. 

Ally bromide, purchased from Aldrich Chemical Company, Inc., is distilled and stored in a brown bottle away from light. 

The perfluorobenzyl organometallic analog, (perfluorobenzyl)cadmium halide (C6F5CF2CdX), can be prepared in a similar fashion by direct reaction of perfluoro[(bromomethyl)benzene] and acid-washed cadmium powder in dimethylformamide at room temperature.61 The cadmium reagent is stable at room temperature for several days, but starts to decompose at 50(C. Like (perfluoroallyl)cadmium, (perfluorobenzyl)cadmium undergoes functionalization reactions with electrophiles such as iodine and ally] bromide. 

Reaction of K-allylmckel bromide complexes with guinones. Allylic bromides react with nickel carbonyl to afford ir-allylnickel bromide complexes formulated as (1) in the case of ally bromide itself (2, 291 3, 210). Hegedus el al. have studied the reaction of... 

Jar structures of tlie 17 -cyclopropenyl complex [IVloBrjCOJilbipyXi -C3Pli3)]NCMe and tlie ij -oxocyclobutenyl complex [MoBr(CO)2 (bipy)(T7 -C4Ph30)] thf have been determined crystallographically (Table jH) 320 j pig reaction of [Mo(CO)4(phen)] with ally bromide to give [MoBr(CO)2(phen)(T -C3H5)] has been shown to obey the rate law -d[Mo (CO)4(phen)]/dr = K,[Mo(CO)4(phen)]. The mechanism of the reaction probably proceeds via slow solvent-assisted fission of a Mo—CO bond, followed by reaction with allyl bromide. - ... 

The reaction of V. Meyer can also be used for example, ally) bromide veacl with silver nitrite to yield 3 iiitropropencl CMj == ( II ( lljNO . 

Protection of primary amines (cf. 8, 437). Laguzza and Ganem2 recommend the diallyl derivatives for protection of primary amines. These compounds are prepared by reaction of the amine with ally bromide and ethyldiisopropylamine. Deprotection is accomplished by isomerization of the allyl groups to propenyl groups by Wilkinson s catalyst (5, 736) in refluxing aqueous acetonitrile Under these conditions the resulting enamine is hydrolyzed with evolution of propionaldehyde, and the amine is obtained in (>5 90", yield. 

Ally bromide Trimethylene bromide Trimetliylene glycol... 

Etherification of hindered tribromophenol with ally bromide... 

Indium trichloride in water catalyzed the conversion of dihydrofuran to the corresponding lactol, which was an intermediate in an indium-promoted allylation with various allylic bromides to provide 1,4-diols. The reaction with ally bromide is shown in the following scheme <04SL829>. 

Tribromopropane. sym-Tribromopropane glycerol tribromohydrin tribromohydrin altyl tribromide. CjHsBrj mol wt 280.82. C 12.83%, H 1.79%. Br 85.37%. BrCI 1 jClfBrt I l Br. Prepd by the addn of bromine to ally) bromide in carbon tetrachloride Perkin, Simonsen, J. 

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