Acid anhydrides, reactions tables

As shown in the sixth entry of Table 24 4 C acylation of phenols is observed under the customary conditions of the Friedel-Crafts reaction (treatment with an acyl chloride or acid anhydride m the presence of aluminum chloride) In the absence of aluminum chloride however O acylation occurs instead... 

On reaction with acyl chlorides and acid anhydrides phenols may undergo either acylation of the hydroxyl group (O acylation) or acylation of the ring (C acylation) The product of C acylation is more stable and predominates under conditions of thermodynamic control when alu mmum chloride is present (see entry 6 m Table 24 4 Section 24 8) O acylation is faster than C acylation and aryl esters are formed under conditions of kinetic control... 

The customary method for the laboratory synthesis of acid anhydrides is the reaction of acyl chlorides with carboxylic acids (Table 20.1). 

Sulfonic acids themselves are unfit for electrophilic transfer of sulfonyl groups because of the poor nucleofugality of the hydroxide anion. However, the high acidity obviously leads to an equilibrium between the acids and their anhydrides and water, from which water can be removed either by special reaction conditions (i.e., azeotropic distillation with appropriate solvents) or chemically with anhydride forming agents316 (equation 63). sulfonic acid anhydride sulfonylations are compiled in Table 10. 

TABLE 3 An Overview of Sulfosuccinate Monoester Types Defined by the Reaction Partner(s) of Maleic Acid Anhydride... 

Tin and HCl reduce out the ben/.ylic OH from (43) in high yield.The Mannich base (45) decomposes to (41) simply on heating. Cyanide addition gives (46) which can be hydrolysed to (40), but a short cut is to hydrolyse to amide (47) and reduce out the carbonyl group by the Clemmensen method (Table T 24.1). Under these conditions the amide is hydrolysed to the acid. Cyclisation to (38) occurs with strong acid, acid anhydrides, or by AlClg-catalysed reaction of the acid chloride. 

Catalysis in Transacylation Reactions. The principal objective of the study was to evaluate 4 as an effective organic soluble lipophilic catalyst for transacylation reactions of carboxylic and phosphoric acid derivatives in aqueous and two-phase aqueous-organic solvent media. Indeed 4 catalyzes the conversion of benzoyl chloride to benzoic anhydride in well-stirred suspensions of CH2CI2 and 1.0 M aqueous NaHCC>3 (Equations 1-3). The results are summarized in Table 1 where yields of isolated acid, anhydride and recovered acid chloride are reported. The reaction is believed to involve formation of the poly(benzoyloxypyridinium) ion intermediate (5) in the organic phase (Equation 1) and 5 then quickly reacts with bicarbonate ion and/or hydroxide ion at the interphase to form benzoate ion (Equation 2 and 3). Apparently most of the benzoate ion is trapped by additional 5 in the organic layer or at the interphase to produce benzoic anhydride (Equation 4), an example of normal phase-... 

Reactions of titanocene-methylidene generated from titanacyclobutanes with acyl chlorides 55 [46] or acid anhydrides 56 [47] lead initially to the titanium enolates 57 (Scheme 14.24), which then afford aldols upon treatment with the carbonyl compounds. On the other hand, five-membered cyclic anhydrides are methylenated with dimethyltitanocene (Table 14.5, entry 7) [45]. 

Carboxylic acids were introduced by the reaction of the polysilane(II) with carboxylic acid anhydrides in the presence of an amine. Table 2 shows the results. In order to examine the effect of unsaturated bonds and halides in the side chain on photolysis, double bonds or chloride groups were introduced with the carboxylic acid. Polysilanes(III) were also soluble in polar solvents and basic aqueous solution. The solubility in tetramethyl ammonium hydroxide aqueous solution(TMAH) depended strongly... 

Chemically, nonmetals are usually the opposite of metals. The nonmetallic nature will increase towards the top of any column and toward the right in any row on the periodic table. Most nonmetal oxides are acid anhydrides. When added to water, they will form acids. A few nonmetals oxides, most notably CO and NO, do not react. Nonmetal oxides that do not react are neutral oxides. The reaction of a nonmetal oxide with water is not an oxidation-reduction reaction. The acid that forms will have the nonmetal in the same oxidation state as in the reacting oxide. The main exception to this is N02, which undergoes an oxidation-reduction (disproportionation) reaction to produce HN03 and NO. When a nonmetal can form more than one oxide, the higher the oxidation number of the nonmetal, the stronger the acid it forms. 

Reaction of 98 with a variety of acid anhydrides in the presence of pyridine produced a series of 4-acyl derivatives (A) in which only the group at C-4 varies (Scheme 4, Table X). By reacting the chloroacetyl derivative (A, R = CHjCI) with various amines, a series of 4- (a-aminoacyl) derivatives (B) were prepared. 

Additionally, Wu and co-workers have shown regioselective ring-opening of aziridines with acid anhydrides mediated by imidiazolinylidene 3 [157]. This pathway requires the use of an electron withdrawing tosylated aziridine 310 in order for the reaction to proceed. The mild reaction conditions allow for a variety of products to be formed in high yields (Table 25). 

The activity and selectivity of silicotungstic acid as catalyst has been evaluated in the acylation of thioanisole with iso-butyric anhydride. Reactions were performed using a 3 fold molar excess of thioanisole. The performance of silicotungstic acid was evaluated In both supported (42%STA/slllca) and bulk form. The results are shown in Table 1. 

As the loading of STA on the catalyst support is decreased, incomplete anhydride conversion is observed and significant hydrolysis of the anhydride to form iso-butyric acid is observed (Table 2). Use of silica supported phosphoric acid results in lower ketone yields and significant hydrolysis of the iso-butyric anhydride. Blank reactions (catalyst and anhydride, 90°C, 30 min) indicates that hydrolysis of anhydride is observed in the presence of these catalysts and may result from either dehydroxylation of the silica support or residual water in the catalyst, ffowever this reaction is slow (42%STA/silica, 44% conversion and 70%P[3PO4/silica, 86% conversion respectively). 

If benzyl carbamate is used as the amide component in the reaction with a-oxo acids 23 then the Na-benzyloxycarbonyl-DHA 24 is obtained directly (Scheme 8). Shin and et al.[77 84l widely exploited the above method in the synthesis of various a, 3-didehydropeptides (Table 3). In presence of 3 M thionyl chloride and acetyl chloride, 24 gave the A-carboxy-DHA anhydride ANCA 25, which could be conveniently converted into dehydropeptides.[77 84 Compared with the common saturated A-carboxy-a-amino acid anhydrides (NCAs), ANCAs were found to be stable at room temperature for several months. 

SAMPLE SOLUTION (a) As noted in Table 20.1, the reaction of an acyl chloride with a carboxylic acid yields an acid anhydride. 

After the amines, acid anhydrides constitute the next most commonly used reagents for curing epoxy monomers. The epoxy-acid reaction proceeds through a stepwise mechanism (Sec. 2.2.4) while the reaction of epoxides with cyclic anhydrides, initiated by Lewis bases, proceeds through a chain-wise polymerization, comprising initiation, propagation, and termination or chain transfer steps. Some of the postulated reactions are shown in Table 2.25 (Matejka et al., 1985b Mauri et al., 1997). 

The related elements nitrogen and phosphorus combine with oxygen to form those oxides which are to be expected on the basis of the position of these elements in the periodic table. In addition, nitrogen forms several other oxides (Table 11.10). Although each of these compounds has its own specific uses or participates in certain reactions that render these oxides of scientific interest, the emphasis here is on the relationship between these oxides (acid anhydrides) and the corresponding acids. 

Cyclization of Anhydrides. Instead of the acid chloride, an intramolecular anhydride of the type LXXIX may be used for cyclization by the Friedel-Crafts reaction (Table VII, examples marked by h ). This resembles the intermolecular acylation with succinic anhydride, and a similar procedure is generally followed. The product of ring closure is a keto acid LXXX. Nitrobenzene 9i 6,1120 is a generally effective solvent for the reaction sym-tetrachloroethane also may be used.121... 

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