Ester-amides, table

Equilibrium diagrams, 22-26 construction of, 26-29 Equivalent weight of an acid, 1071 Ester-amides, table of, 425 Esterification, 379 -382, 1000, 1001 Esters, hydroxamic acid test for, 1062, 1063 ... 

The alkylidene complex 61 readily converts a wide variety of carbonyl compounds into the corresponding olefins in good yields, with the following order of reactivity aldehydes > ketones > formates > esters > amides (Table 4.20) [134]. Replacement of two neopentoxo groups by chloro, bromo, or iodo ligands reduces... 

There are tremendous variations in the rates of acyl substitution reactions with a common nucleophile such as water. The order of reactivity in a hydrolysis reaction is acyl chloride > acid anhydride > ester > amide (Table 21.3). 

One of the virtues of the Fischer indole synthesis is that it can frequently be used to prepare indoles having functionalized substituents. This versatility extends beyond the range of very stable substituents such as alkoxy and halogens and includes esters, amides and hydroxy substituents. Table 7.3 gives some examples. These include cases of introduction of 3-acetic acid, 3-acetamide, 3-(2-aminoethyl)- and 3-(2-hydroxyethyl)- side-chains, all of which are of special importance in the preparation of biologically active indole derivatives. Entry 11 is an efficient synthesis of the non-steroidal anti-inflammatory drug indomethacin. A noteworthy feature of the reaction is the... 

Many compounds contain more than one functional group Prostaglandin Ei a hormone that regulates the relaxation of smooth muscles con tains two different kinds of carbonyl groups Classify each one (aldehyde ketone carboxylic acid ester amide acyl chloride or acid anhydride) Identify the most acidic proton in prostaglandin Ei and use Table 1 7 to estimate its pK ... 

Selected physical properties of various methacrylate esters, amides, and derivatives are given in Tables 1—4. Tables 3 and 4 describe more commercially available methacrylic acid derivatives. A2eotrope data for MMA are shown in Table 5 (8). The solubiUty of MMA in water at 25°C is 1.5%. Water solubiUty of longer alkyl methacrylates ranges from slight to insoluble. Some functionalized esters such as 2-dimethylaniinoethyl methacrylate are miscible and/or hydrolyze. The solubiUty of 2-hydroxypropyl methacrylate in water at 25°C is 13%. Vapor—Hquid equiUbrium (VLE) data have been pubHshed on methanol, methyl methacrylate, and methacrylic acid pairs (9), as have solubiUty data for this ternary system (10). VLE data are also available for methyl methacrylate, methacrylic acid, methyl a-hydroxyisobutyrate, methanol, and water, which are the critical components obtained in the commercially important acetone cyanohydrin route to methyl methacrylate (11). 

Enzymes are classified into six categories depending on the kind of reaction they catalyze, as shown in Table 26.2. Oxidoreductases catalyze oxidations and reductions hansferases catalyze the transfer of a group from one substrate to another hydrolases catalyze hydrolysis reactions of esters, amides, and related substrates lyases catalyze the elimination or addition of a small molecule such as H2O from or to a substrate isomerases catalyze isomerizalions and ligases catalyze the bonding together of two molecules, often coupled with the hydrolysis... 

While there is clear evidence for complex formation between certain electron donor and electron acceptor monomers, the evidence for participation of such complexes in copolymerization is often less compelling. One of the most studied systems is S-.V1 Al I copolymerization/8 75 However, the models have been applied to many copolymerizations of donor-acceptor pairs. Acceptor monomers have substituents such as carboxy, anhydride, ester, amide, imide or nitrile on the double bond. Donor monomers have substituents such as alkyl, vinyl, aryl, ether, sulfide and silane. A partial list of donor and acceptor monomers is provided in Table 7.6.65.-... 

This procedure, which is based on the work of Ishii and co-workers, affords a mild and general method for converting a wide variety of esters to primary, secondary, and tertiary amides (Table 1). While the preparation of the tertiary amide, N,N-dimethylcyclohexanecarboxamide, described here is carried out in benzene, aluminum amides derived from ammonia and a variety of primary amines have been prepared by reaction with trimethylaluminum in dichloromethane and utilized for aminolysis in this solvent. Although 1 equivalent of the dimethylaluminum amides from amines was generally sufficient for high conversion within 5-48 hours, best results were obtained when 2 equivalents of the aluminum reagent from ammonia was used. Diethyl-aluminum amides can also effect aminolysis, but with considerably slower rates. 

A wide range of groups are tolerated in this position including esters, amides, thioesters, ureas, acyl hydrazines and carbamates exhibiting a wide range of potencies and microsomal stabilities (Table 6.2) [24, 33-36]. 

The direct comparison of 1 and 2 in a variety of RCM reactions also indicates a presumably close relationship between these catalysts (Table 1) [6]. Both of them give ready access to cycloalkenes of almost any ring size > 5, including medium sized and macrocyclic products. Only in the case of the 10-membered jasmine ketolactone 16 was the yield obtained with 2a lower than that with lc this result may be due to a somewhat shorter lifetime of the cationic species in solution. However, the examples summarized in Table 1 demonstrate that the allenylidene species 2 exhibit a remarkable compatibility with polar functional groups in the substrates, including ethers, esters, amides, sulfonamides, ketones, acetals, glycosides and even free hydroxyl groups. 

Although the ruthenium allenylidene complexes 2 have not yet been as comprehensively studied as their carbene counterparts, they also seem to exhibit a closely related application profile [6]. So far, they have proven to tolerate ethers, esters, amides, sulfonamides, ketones, acetals, glycosides and free secondary hydroxyl groups in the substrates (Table 1). 

The amide group shows a prominent directivity in the hydrogenation of cyclic unsaturated amides by a cationic iridium catalyst, and much higher diastereo-selectivity is realized than in the corresponding ester substrates (Table 21.7). In the case of / ,y-unsaturated bicyclic amide (entry 3), the stereoselectivity surpasses 1000 1 [41]. An increase of the distance between the amide carbonyl and olefmic bond causes little decrease in the selectivity (d, -unsaturated amide, entry 6) compared with the case of the less-basic ester functionality (Table 21.6, entry 5). 

Davis et al.111 developed another method for reagent-controlled asymmetric oxidation of enolates to a-hydroxy carbonyl compounds using (+)-camphor-sulfonyl oxaziridine (147) as the oxidant. This method afforded synthetically useful ee (60-95%) for most carbonyl compounds such as acyclic keto esters, amides, and a-oxo ester enolates (Table 4-20). 

DKR for the Synthesis of Esters, Amides and Acids Using Lipases Table 4.4 DKR of various aliphatic amines... 

A bigger effect for H2O than OH is very unusual and is a behavior certainly not shown by the uncoordinated amide. The effect is ascribed to a benefit from cyclization and concerted loss of protonated amide, without formation of the tetrahedral intermediate. Although the coordinated OH is some 10 times less effective than coordinated HjO (Table 6.4), it is still about 10 times faster with 15 than via external attack by OH at pH 7 on the chelated amide 13. Early studies showed that complexes of the type CoN4(H20)OH can promote the hydrolysis of esters, amides and dipeptides and that this probably arises via formation of ester, amide or peptide chelates. These then hydrolyze in the manner above. 

A wide range of a,P-unsaturated acceptors work well under standard reaction conditions with pre-catalyst 75c (Table 7). Acceptors include a,P-unsaturated esters, amides, alkyl ketones, and phosphine oxides, many of which provide the products in greater than 90% ee [68, 69], a,P-Unsaturated phenyl ketones, nitriles, and thioesters also work, albeit with lower enantioselectivity. The scope has been extended to include a variety of vinyl phosphonate precursors providing good chemical yields and moderate to high enantioselectivity (entries 9 and 10). 

Besides the use of this reactiou to syuthesize the plethora of species recorded iu our table for hydroxamic acids, it provided a simple qualitative test, a resultiug purple color, for the carboxylic acid species upou reactiou with Fe . Although this test was uot employed to distiuguish which compouud, the class-depeudeut wide variety of reactivity allowed for distiuguishiug esters, amides, auhydrides aud occasiouaUy the carboxylic acids themselves (after couversiou to their acyl chloride). 

Branched iV-chlorohydroxamic esters exhibit much lower carbonyl frequencies in their IR spectra. Series of Ai-(phenylethyloxy)amides (Table 2, entries 1-7) and Af-butoxy-amides (Table 2, entries 12-16) show a clear movement to lower carbonyl stretch frequencies with branching alpha to the carbonyl, in accord with greater inductive stabilization of the polar resonance form III of the carbonyl (Figure la). Neopentyl (entry 17) is a special case. While the group should contribute much more inductive stabilization than ethyl, its carbonyl stretch frequency is higher. Similar changes have been noted in the IR spectra of branched ketones and have been ascribed to a degree of steric hindrance to solvation and therefore destabilization of the polar resonance form Dl". ... 

A wide range of carbon-carbon double bonds undergo chain polymerization. Table 3-1 shows monomers with alkyl, alkenyl, aryl, halogen, alkoxy, ester, amide, nitrile, and heterocyclic substituents on the alkene double bond. 

The zinc-mediated reaction tolerates a variety of functionality in the p-keto ester. In fact, the method described above has been applied successfully to p-keto amides and p-keto phosphonates, Unsubstituted p-keto esters, amides and phosphonates have been chain-extended in yields that ranged from 58% to 98% (Table I). The primary limitation to this method is the inefficiency with which a-substituted esters and amides undergo methylene insertion. The zinc carbenoid must be employed in at least a threefold excess h... 

Examples of polymeric carriers are presented in Table 1 and typical methods of covalent conjugation are shown below. Drugs may be bound to macromolecular carriers via, e.g., ester, amide, urethane, hydrazone, thioether, and disulfide... 

Trifluoroacrylonitrile can be epoxidized by oxygen with 1,1,2-trichlorotrifluoroethane (CFC-113) as a solvent under pressure at elevated temperatures in moderate yield (Table 2).77 Substituted peroxybenzoic acids are used for the epoxidation of trifluorovinyl alkenes with attached functionalities such as ester, amide or dimethoxyphosphoryl groups (Table 2).7S Functional derivatives of perfluoro-2-methylprop-2-enoic acid are oxidized to the corresponding epoxy compounds in this reaction.78 In the case of ethyl ester 40, the epoxide 41 is contaminated with the adduct of 3-chloroperoxybenzoic acid to the C = C bond, compound 42, that is formed even at low temperatures.78... 

Borane also will reduce esters, amides, and nitriles to the same products as does LiAlH4, but with reduced reactivity (Table 16-6). 

Table 16 Rate Constants for the Base Hydrolysis of Ester, Amide and Peptide Bonds in Various Cobalt(III) Complexes (25 °C, / = 1.0 M)a...

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