Diethyl ethylmalonate, reaction with

Benzoyl fluoride, 46,3 Benzoy lhydrazine, 46, 85 Benzoyl peroxide, as catalyst for reaction of chloroform with as,as 1,5 cyclooctadiene, 47, 11 reaction with diethyl ethylmalonate, 46, 37... 

Ethyl a-nitrobutyrate may be prepared in 75% yield by the reaction of silver nitrite with ethyl a-iodobutyrate.4 It has been prepared in 18% yield by nitration and subsequent decarboxylation of diethyl ethylmalonate.6 The present method offers the advantage of a direct preparation using sodium nitrite. 

Benzophenone, 46, 36 N-(2-Benzothiazolyl)urea, 46, 72 Benzoyl chloride, reaction with hydrogen fluoride, 46, 4 Benzoyl fluoride, 46, 3 Benzoylhydrazine, 46, 8S Benzoyl peroxide, reaction with diethyl ethylmalonate, 45, 37 2-Benzyl-2-carbomethoxycyclopenta-none, 45, 7... 

To a 1-1., three-necked, round-bottomed flask is added 7.2 g. (0.15 mole) of a 50% dispersion of sodium hydride in mineral oil (Note 1). The sodium hydride is washed several times by decantation with dry ether and is then covered with 300 ml. of dry benzene (Note 2). The flask is equipped with dropping funnel, stirrer, and reflux condenser. Diethyl ethylmalonate (28.2 g., 0.15 mole) (Note 1) is added dropwise over a 5-minute period, and the reaction mixture is stirred for 2 hours until a clear solution forms. The solution is cooled in an ice bath, and 24.2 g. (0.1 mole) of benzoyl peroxide (Note 3) in 300 ml. of dry benzene is added dropwise over a 1-hour period with continuous stirring After another 30 minutes, a peroxide test (Note 4) is made to ensure that all the peroxide has reacted. 

Diethyl malonatc13 gives four products upon reaction with perchloryl fluoride diethyl difluoro-malonate, diethyl ethylmalonate, diethyl ethylfluoromalonate and diethyl fluoromalonate the product distribution depends on the reaction conditions. A number of esters are fluo-rinated,14 15 while (pentafluorophenyl)acetonitrile is converted into mono- and disubstituted products in the presence of cesium fluoride.16... 

Catalysis of benzylic bromination, see 1,3-Dibromo-5,5-dimethylhydantoin. Benzoyloxylation of malomc esters. Dibenzoyl peroxide reacts with the sodium derivative of diethyl ethylmalonate to give diethyl (O-benzoyl)ethyltartronate. This is a general reaction for /8-dicarbonyl compounds. 

The lithium enolate of diethyl ethylmalonate adds stereospecifically to the vinyl bromide (89) to give the diester (90) similarly the ethynyl bromide (91) is converted into (92).These potentially useful intermediates afford the corresponding vinyl and ethynyl bromides on treatment with N-bromosuccinimide. The reactions are also successful with the lithium enolate of 2-ethoxycarbonyl-cyclopentanone. 

Reetz studied the polymerization of nBuA initiated by tetrabutylammonium thiolates, which are easily prepared by reaction of thiols with tetrabutylammonium hydroxide ". Nevertheless, only polymers of molecular weight under 2000 were formed " ". This problem was overcome by using the tetra-n-butylammonium salt of diethyl 2-ethylmalonate (37) as initiator (equation 42). PnBuA was obtained with a predictable molecular weight and a low polydispersity index (1.1 < M /M < 1.2). 

Bandermann and coworkers studied the MMA polymerization initiated by 37 . Whenever the initiator is contaminated by traces of diethyl 2-ethylmalonate, an inhibition period is observed, which was accounted for by a transfer reaction of the propagating enolate to diethyl 2-ethylmalonate. The polymerization cannot start until this contaminant is completely consumed. Consistently, no inhibition is observed when the initiator is highly pure. Finally, a Hoffman elimination in the propagating ammonium enolate (38) could occur with formation of dead chains (39) tri-n-butylamine and 1-butene (equation 43) . 

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