Peroxides diacyl, preparation

Petoxycatboxyhc acids also have been prepared by the reaction of acid chlorides, anhydrides, or boric-catboxyhc anhydrides with hydrogen or sodium peroxide. These reactions ate carried out at low temperature and with excess peroxide to avoid the formation of diacyl peroxides (44,168,181,184). 

Synthesis. Symmetrical diacyl peroxides (20, R = R = alkyl or aryl) are prepared by the reaction of an acyl chloride or anhydride with sodium peroxide or hydrogen peroxide and a base ... 

Other unsymmetrical peroxides can be prepared by this reaction by employing other acylating agents, eg, alkyl chloroformates, organosulfonyl chlorides, and carbamoyl chlorides (210). Unsymmetrical and symmetrical di(diacyl peroxides) also are obtained by the reaction of dibasic acid chlorides directiy with peroxycarboxyhc acids or monoacid chlorides directiy with diperoxycarboxyhc acids in the presence of a base (44,187,203). 

Polymeric diacyl peroxides (26) can be prepared from the reaction of dibasic acid chlorides, eg, succinoyl, fumaryl, sebacoyl, and terephthaloyl chlorides, with sodium or hydrogen peroxide (187). 

The decomposition of diacyl peroxides provides a fairly clean method for the production of alkyl radicals and, therefore, it has been used in most quantitative and preparative studies of the alkylation of heterocyclic compounds,... 

In general, aliphatic diacyl peroxide initiators should be considered as sources of alkyl, rather than of aeyloxy radicals. With few exceptions, aliphatic acyloxy radicals have a transient existence at best. For certain diacyl peroxides (36) where R is a secondary or tertiary alkyl group there is controversy as to whether loss of carbon dioxide occurs in concert with 0-0 bond cleavage. Thus, ester end groups observed in polymers prepared with aliphatic diaeyl peroxides are unlikely to arise directly from initiation, but rather from transfer to initiator (see 3.3,2.1.4),... 

Transfer to initiator can be a major complication in polymerizations initiated by diacyl peroxides. The importance of the process typically increases with monomer conversion and the consequent increase in the [initiator] [monomer] ratio.9 105160 162 In BPO initiated S polymerization, transfer to initiator may be lire major chain termination mechanism. For bulk S polymerization with 0.1 M BPO at 60 °C up to 75% of chains are terminated by transfer to initiator or primary radical termination (<75% conversion).7 A further consequence of the high incidence of chain transfer is that high conversion PS formed with BPO initiator tends to have a much narrower molecular weight distribution than that prepared with other initiators (e.g. AIBN) under similar conditions. 

Chidsey and coworkers made pioneering works in preparing covalently bonded monolayer films on silicon surfaces by the radical-initiated reaction of 1-alkenes with the H-Si(lll) surfaces. Reactions were carried out in neat deoxygenated alkenes using thermal decomposition of diacyl peroxides as the... 

Diacyl peroxides and acyl hydroperoxides can similarly be prepared from acyl halides or anhydrides... 

In 1993, Linford firstly reported a quite useful method to prepare monolayers of alkyl chains by thermal hydros-ilylation of hydrogen-terminated silicon surfaces [25]. Alkyl chains are covalently bound to Si surface by Si-C bonds. This thermal hydrosilylation could be attributed to a free-radical process with 1-alkene. First, a diacyl peroxide initiator was used to produce free radicals. However, at higher temperature, only hydrogen-terminated silicon and a neat solution of 1-alkene or 1-alkyne can form Si-C linkages [26]. Furthermore, lately it is found that such Si-C covalent links can be observed even in dilute solutions of 1-alkenes [27]. In that case, the density of monolayer packing strongly depends on the reaction temperature. 

A sample of the peroxide in ether, prepared according to a published procedure [1], was being evaporated to dryness with a stream of air when it exploded violently. Handling the peroxide as a dilute solution at low temperature is recommended [2], See other diacyl peroxides... 

Diacetoxyscirpenol (DAS) immunoassay, 14 144-147 Diacetyl, 23 483 Diacetyl control, 10 293 Diacetyl peroxide, 1 148 Diacetyl rest, in beer making, 3 584 Diacrylamide, 1 293 Diacylglycerols, 10 802 Diacyl hydrazines, 13 599 Diacyl peroxides, 14 281 18 467 decomposition of, 18 473 as free-radical initiators, 14 282-284 hydrolysis and perhydrolysis of, 18 466, 473 preparation of, 18 476 properties of, 18 468-469t reaction with amines, 18 474 reduction of, 18 474 symmetrical or unsymmetrical, 18 477... 

Most of the isolated diacyl (including sulfonyl) peroxides are solids with relatively low decomposition temperatures, and are explosive, sensitive to shock, heat or friction. Several, particularly the lower members, will detonate on the slightest disturbance. Autocatalytic (self-accelerating) decomposition, which is promoted by tertiary amines, is involved [1]. Solvents suitable for preparation of safe solutions of diacetyl, dipropionyl, diisobutyryl and di-2-phenylpropionyl peroxides are disclosed [2], The class is reviewed, including hazards and safety measures [3], Cyclic diacyl peroxides are more stable, but scarcely to be trusted. Individually indexed compounds are ... 

It is also possible to produce covalently bonded alkyl MLs on Si(l 11) surfaces using a variety of chemical reactions with passivated H-terminated Si(l 11), but the preparation methods are more complex than the immersion strategy in part due to the higher reactivity of silicon. This is a major achievement because it allows direct coupling between organic and bio-organic materials and silicon-based semiconductors. Both pyrolysis of diacyl peroxides (Linford Chidsey, 1993) and Lewis acid-catalyzed hydrosilylation of alkenes and direct reaction of alkylmagnesium bromide (Boukherroub et al, 1999) on freshly prepared Si(lll)-H produce surfaces with similar characterishcs. These surfaces are chemically stable and can be stored for several weeks without measurable deterioration. Thienyl MLs covalently bonded to Si(l 11) surfaces have also been obtained, in which a Si(l 11)-H surface becomes brominated, Si(lll)-Br, and is further reacted with lithiated thiophenes (He etal, 1998). 

The RP-HPLC method based on the CL reaction of luminol (124) catalyzed by Co(II) (Section in.B.2.c) can be applied for determination of peroxycarboxylic acids, esters and diacyl peroxides (see examples of LOD in equation 67, Section V.B.2.c) . The biosensor prepared according to equation 70, that is effective in the determination of hydroperoxides (Section V.B.6.b), becomes deactivated after three days of operation when trying to determine t-butyl peracetate. ... 

Carbon-carbon bond formation between sp -hybridized carbons is not easy even with organometallic reagents. John Vederas of the University of Alberta reports (Organic Lett. 5 2963, 2003) that UV irradiation at low temperature of diacyl peroxides such as 4 gives the coupled product 5. The diacyl peroxides can be prepared by the DCC-mediated condensation of acids with peracids,... 

The transformation of carboxylic acids and their functional derivatives to the corresponding peroxycarboxylic acids or diacyl peroxides are generally known reactions.200-201 Among the hydroperoxy derivatives, trifluoroperacetic acid is a frequently used epoxidizing reagent in organic chemistry and is usually prepared in situ.200-201... 

Included in Scheme 2.32 are a series of bis(amino acids) prepared by Spantulescu et al. [63] by the decarboxylation of diacyl peroxides derived from combinations of protected aspartic and glutamic acids. In all cases, the reactions gave yields ranging from 52% to 66%. To prevent the formation of side products, the irradiation was performed on neat samples at low temperatures (—78 °C or — 96 °C). 

Figure 2.40 illustrates some of the methods which can be employed for the preparation of diacyl peroxides [(RC02)2], both symmetrical and asymmetrical.120 122... 

Though many open-chain diacyl peroxides have been described, very few cyclic compounds of this type are known. Monomeric cyclic phthaloyl peroxide (84) is prepared by treatment of phthaloyl chloride in chloroform with aqueous sodium peroxide solution in the presence of phosphate buffer, or by reaction of phthaloyl chloride with ethereal hydrogen peroxide in the presence of sodium carbonate.70-72 Russell71 has also obtained cyclic diacyl peroxides from the dichlorides of the C10, C12, and C14 dicarboxylic acids. Only polymeric diacyl peroxides were obtained from lower dicarboxylic acids. 

With the exception of an isolated reports on the decomposition of diacyl peroxides in acetonitrile in the presence of copper(II) isothiocyanate and potassium dtiocyanate (equation 32), the only preparative methods available for decarboxylative chalcogenation and phosphorylation make use of the 0-acyl duo-hydroxamates. 

The ability of diacyl peroxides to undergo photochemical decomposition with concomitant C-C bond formation was elegantly exploited by Vederas and coworkers for the preparation of functionalized amino acids (Scheme 20) [27,28]. Symmetrical and unsymmetrical diacyl peroxides of amino acids were conveniently prepared from suitably protected aspartic and glutamic acids in a few steps. Photolysis of the peroxides with a 254-nm UV lamp at low temperature and in the absence of solvent led to decarboxylation... 

The alkyl groups of two identical carboxylic acids can be coupled to symmetrical dimers in the presence of a fair number of functional groups (equation 1). Since free radicals are the reactive intermediates, polar substituents need not be protected. This saves the steps for protection and deprotection that are necessary in such cases when electrophilic or nucleophilic C—C bond-forming reactions are involved. Furthermore, carboxylic acids are available in a wide variety from natural or petrochemical sources, or can be readily prepared from a large variety of precursors. Compared to chemicd methods for the construction of symmetrical compounds, such as nucleophilic substitution or addition, decomposition of azo compounds or of diacyl peroxides, these advantages make the Kolbe electrolysis the method of choice for the synthesis of symmetrical target molecules. No other chemical method is available that allows the decarboxylative dimerization of carboxylic acids. 

For the selective preparation of unsymmetrical coupling products on a small scale, the photolysis of peroxides is a favorable alternative to the mixed Kolbe electrolysis. By photolysis of unsymmetrical diacyl peroxides at -60 to -70 C in the solid state two different alkyl groups can be joined selectively. "... 

The two Schotten-Baumann methods of preparing diacyl peroxides suffer from the formation of difficult emulsions in the alkaline medium and loss in yield due to hydrolysis of the acid chloride. Silbert and Swern developed an improved method involving acylation of 50-65% hydrogen peroxide with the acid chloride in ethei pyridine solution and obtained highly pure diacyl peroxides in nearly quantitative yield. For example, a solution of myristoyl chloride in ether is cooled to 0°. hydrogen... 

Dehydrative coupling of hydroxy compounds. Uses of the reagent for coupling two hydroxylic components by elimination of water under mild, neutral conditions have been reviewed. A recent example is the preparation of a symmetrical diacyl peroxide by coupling two moles of an acid with one of hydrogen peroxide. An amount of DCC equivalent to the acid (plus 10% excess) is weighed as a liquid into... 

When the decomposition is carried out in an inert solvent, methyl acetate and ethane are formed, whereas in the gas-phase decomposition methyl acetate is completely absent and ethane is produced in much smaller quantity.85 It was suggested that the dimers in solution represent the recombination of methyl, and the combination of methyl and acetoxy radicals, within the solvent cage. 85 87 The decomposition of diacyl peroxides provides a fairly clean method for the production of alkyl radicals and, therefore, it has been used in most quantitative and preparative studies of the alkylation of heterocyclic compounds. 

---