Cross-condensation reactions

The cross-condensation reaction of benzyl benzoate (46) and 44 was carried out under solvent-free conditions. Treatment of a 1 1 mixture of 46 and 44a with Bu OK at 120 °C for 1 h gave the cross-condensed product 47a in 42% yield (Scheme 7). Similar reaction of 46 with 44b gave 47b in 45% yield. Because heating of46,44, and Bu OK in toluene under reflux for 16 h did not give any product, it is clear that the solvent-free reaction is again effective for the cross-condensation. In these cases, self-condensation of 44 itself did not occur probably because of the high reactivity of 46 [9]. 

Scheme 8-33 [Cp2Zr(H)CI] 1-catalyzed cross-condensation reactions...

A related report has demonstrated that aldehydes can be converted into esters in the presence of allylic alcohols [83]. Dihydrocinnamaldehyde 91 and aUyl alcohol 95 undergo a cross-condensation reaction to give ester 96. The allyl alcohol 95 also serves as a hydrogen acceptor, perhaps via an isomerization/reduction sequence (Scheme 23). 

Claisen-Schmidt reaction The cross condensation reaction of an aromatic aldehyde with a simple aliphatic aldehyde or ketone with 10% KOH to yield the dehydrated product, i.e. an a,P-unsaturated arenone. 

Tetrazines can be produced by condensation of hydrazine with carbonyl compounds at acid oxidation level, followed by oxidation of the dihydro products this generally produces 3,6-identically substimted derivatives, crossed condensation reactions being inefficient. 

Imines are more versatile than preformed iminium salts in reactions with active methylene compounds because the product, a secondary Mannich base, has an additional site on the nitrogen for further elaboration (equation 11). Imine condensation reactions are also superior to the classical method for the synthesis of secondary Mannich bases because cross-condensation reactions do not occur, due to the absence of free aldehyde in solution. The major side reactions occurring in imine condensation reactions are abstraction of enolizable ot-protons and self-condensation reactions of enolizable imines at elevated temperature. 

We showed, over two different series of Al(Ga)PON oxynitrides catalysts, that the nitridation of phosphate precursors has a positive effect on the selectivity to jasminaldehyde for the mixed aldol condensation reaction of heptanal with benzaldehyde. The influence of nitridation on the product distribution was interpreted in terms of changes in the relative density of acid and basic sites on the catalyst surface. Decreasing the acidity and increasing the basicity through nitridation enhances the simultaneous activation of benzaldeyde and heptanal and favors the cross condensation reaction between those two aldehydes, rather than the self-condensation of heptanal. 

FIGURE 19.95 The mechanism of a crossed condensation reaction between a ketone and an ester. 

Provide a mechanistic explanation for the stereochemistry of the crossed condensation reactions that converted 60 —> 61 62. 

P. Ayhan, 1. Simsek, B. Cifci, A.S. Demir, Benzaldehyde lyase catalyzed enantioselective self and cross condensation reactions of acetaldehyde derivatives, Org. Biomol. Chem. 9 (2011) 2602-2605. 

A Reformatskii reagent may be regarded as a zinc enolate and is useful for selectivity in cross condensation reactions. 

The alkylphenylacetyi chloride 843 and benzoyl chloride undergo decarbo-nylative cross-condensation to give the enone 845 in the presence of EtiNf723]. The reaction is e.xplained by the insertion of the ketene 844 into the Pd-aryl bond and, 3-elimination. To support this mechanism, o, d-unsaturuted ketones are obtained by the reaction of ketenes with aroyl chlorides[724]. 

Haward et al.t have reported some research in which a copolymer of styrene and hydroxyethylmethacrylate was cross-linked by hexamethylene diisocyanate. Draw the structural formula for a portion of this cross-linked polymer and indicate what part of the molecule is the result of a condensation reaction and what part results from addition polymerization. These authors indicate that the crosslinking reaction is carried out in sufficiently dilute solutions of copolymer that the crosslinking is primarily intramolecular rather than intermolecular. Explain the distinction between these two terms and why concentration affects the relative amounts of each. 

The base-catalyzed reaction of acetaldehyde with excess formaldehyde [50-00-0] is the commercial route to pentaerythritol [115-77-5]. The aldol condensation of three moles of formaldehyde with one mole of acetaldehyde is foUowed by a crossed Cannizzaro reaction between pentaerythrose, the intermediate product, and formaldehyde to give pentaerythritol (57). The process proceeds to completion without isolation of the intermediate. Pentaerythrose [3818-32-4] has also been made by condensing acetaldehyde and formaldehyde at 45°C using magnesium oxide as a catalyst (58). The vapor-phase reaction of acetaldehyde and formaldehyde at 475°C over a catalyst composed of lanthanum oxide on siHca gel gives acrolein [107-02-8] (59). 

Manufacture. Commercial preparation of neopentyl glycol can be via an alkah-cataly2ed condensation of isobutyraldehyde with 2 moles of formaldehyde (crossed Canni22aro reaction) (2,8). Yields are - 70%. 

Polymerization. Thermal polymerization or curing of an ink film at elevated temperatures can foUow many different chemical paths. Condensation and cross-linking reactions may be accompHshed with or without the use of catalysts. However, this method of drying generally has not been widely used for printing inks, except those used for metal and glass decoration, and some clear coatings. 

The Guerbet reaction can be used to obtain higher alcohols 2-propyl-1-heptanol [10042-59-8] from 1-pentanol condensation and 6-methyl-4-nonanol from 2-pentanol (80—83). Condensations with alkah phenolates as the base, instead of copper catalyst, produce lower amounts of carboxyhc acids and requke lower reaction temperatures (82,83). The crossed Guerbet reaction of 1-pentanol with methanol in the presence of sodium methoxide catalyst afforded 2-heptanol in selectivities of about 75% (84). 

The segments derived from the condensation reaction of the butanediol and the diisocyanate agglomerate into separate phases, which are hard and crystalline. The elastomeric chains are thus cross-linked to form a network similar in many ways to that given by the simple... 

This procedure is representative of a new general method for the preparation of noncyclic acyloins by thiazol ium-catalyzed dimerization of aldehydes in the presence of weak bases (Table I). The advantages of this method over the classical reductive coupling of esters or the modern variation in which the intermediate enediolate is trapped by silylation, are the simplicity of the procedure, the inexpensive materials used, and the purity of the products obtained. For volatile aldehydes such as acetaldehyde and propionaldehyde the reaction Is conducted without solvent in a small, heated autoclave. With the exception of furoin the preparation of benzoins from aromatic aldehydes is best carried out with a different thiazolium catalyst bearing an N-methyl or N-ethyl substituent, instead of the N-benzyl group. Benzoins have usually been prepared by cyanide-catalyzed condensation of aromatic and heterocyclic aldehydes.Unsymnetrical acyloins may be obtained by thiazol1um-catalyzed cross-condensation of two different aldehydes. -1 The thiazolium ion-catalyzed cyclization of 1,5-dialdehydes to cyclic acyloins has been reported. 

As these condensation reactions can occur at the two ortho and the para positions in phenol, w-cresol and 3,5-xylenol, cross-linked structures will be formed. It has been pointed out by Megson that because of steric hindrance the amount of cross-linking that can take place is much less than would involve the three reactive groups of all the phenolic molecules. It is now generally considered that the amount of cross-linking that actually takes place is less than was at one time believed to be the case. 

Above 160°C it is believed that additional cross-linking reactions take place involving the formation and reaction of quinone methides by condensation of the ether linkages with the phenolic hydroxyl groups (Figure 23.14). 

Stannous triflate is an efficient catalyst for aldol-type condensations [ 23, 124, 125 Under conditions of kinetic control, it provides excellent diastereo-selectivity in various cross-aldol reactions (equation 61)... 

A two-step sequence of nitrile oxide-olehn cycloaddition and reduction of the resulting A -isoxazolines offers a unique and attractive alternative to the classical aldol reaction and its many variants (2J). The procedure bypasses traditional problems, including enolate equilibrium and cross condensation (20). 

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