Epoxides reactions with carboxylic

Epoxides. Epoxy compounds react with the carboxyl groups of CTPB to form polyesters. The reaction rates and extent of reaction of a number of epoxides have been determined with the model compound hexanoic acid (6). It was found that most epoxides undergo side reactions (as evidenced by the more rapid consumption of epoxide species) but that at least one difunctional epoxide, DER-332 (Dow Chemical Co.) (Table IV), exhibits a clean reaction with carboxylic acids, even in the presence of ammonium perchlorate. 

Over the last decade, a considerable number of reactions has been studied (11,35) (i) olefins oxidation (38,39), hydroboration, and halogenation (40) (ii) amines silylation (41,42), amidation (43), and imine formation (44) (iii) hydroxyl groups reaction with anhydrides (45), isocyanates (46), epichloro-hydrin and chlorosilanes (47) (iv) carboxylic acids formation of acid chlorides (48), mixed anhydrides (49) and activated esters (50) (v) carboxylic esters reduction and hydrolysis (51) (vi) aldehydes imine formation (52) (vii) epoxides reactions with amines (55), glycols (54) and carboxyl-terminated polymers (55). A list of all the major classes of reactions on SAMs plus relevant examples are discussed comprehensively elsewhere (//). The following sections will provide a more detailed look at reactions with some of the common functional SAMs, i.e hydroxyl and carboxyl terminated SAMs. 

Reactions of Epoxidized Esters with Carboxylic Acids and High-Oleic Sunflower Fatty Acids (HOSFA). Reactions of epoxidized RME were carried out with acetic acid and heptanoic acid at atmospheric pressure. Operating conditions (temperature, acid quantity, and reaction time) were optimized. The best results were obtained without catalyst, with a molar ratio of esters/acid of 1 2, at 80°C for 12 h. The characteristics of the reaction products are reported in Table 6. 

Cleavage of Epoxidized RME with Carboxylic Acids Chemical Characteristics of Reaction Products ... 

Resins were prepared from crude sucrose esters, soap-free sucrose esters and the insoluble fractions obtained after methanol extraction of soap-free sucrose esters. Details of resins from "tetra"/"penta" esters are given in Tables II and III. Starting from crude esters, the potassium soaps present catalysed the reactions with carboxyl and epoxide groups. However, with soap-free esters or methanol insoluble fractions, a tertiary amine catalyst, e.g. about 0.25% triethyla-mine or benzyldimethylamine, was required to obtain a satisfactory rate of reaction. Reaction times were usually about 6 to 8 hours. 

Crosslinking is an additional task for comonomers. N-methylol acrylamide fulfills this function in acrylic, vinyl acetate and styrene-butadiene latexes for textile binding. Glycidyl methacrylate can crosslink through reaction of its epoxide moiety with carboxyl or amino groups. Isocyanatoethyl methacrylate contains a reactive isocyanate group there are many others. 

Reaction of epoxidized PBD with carboxylic acids gives access to hydroxy esters. The reaction can occur during the epoxidation of PBD with carboxylic peracids (vide infra). The reaction is acid-catalyzed and it should be no surprise that the reaction with acetic acid gives the hydroxyl ester if catalytic amounts of sulfuric acid are present (Scheme 16) [80]. 

Other major industrial applications for hydrogen peroxide include the manufacture of sodium percarbonate and sodium perborate, used as mild bleaches in laundry detergents. It is used in the production of certain organic peroxides such as dibenzoyl peroxide, used in polymerisations and other chemical processes. Hydrogen peroxide is also used in the production of epoxides such as propylene oxide. Reaction with carboxylic acids produces a corresponding peroxy acid. Peracetic acid and meta-chloroperoxybenzoic acid (commonly abbreviated mCPBA) are prepared from acetic acid and /weto-chlorobenzoic acid, respectively. The latter is commonly reacted with alkenes to give the corresponding epoxide. 

The zwitterion (6) can react with protic solvents to produce a variety of products. Reaction with water yields a transient hydroperoxy alcohol (10) that can dehydrate to a carboxyUc acid or spHt out H2O2 to form a carbonyl compound (aldehyde or ketone, R2CO). In alcohoHc media, the product is an isolable hydroperoxy ether (11) that can be hydrolyzed or reduced (with (CH O) or (CH2)2S) to a carbonyl compound. Reductive amination of (11) over Raney nickel produces amides and amines (64). Reaction of the zwitterion with a carboxyUc acid to form a hydroperoxy ester (12) is commercially important because it can be oxidized to other acids, RCOOH and R COOH. Reaction of zwitterion with HCN produces a-hydroxy nitriles that can be hydrolyzed to a-hydroxy carboxyUc acids. Carboxylates are obtained with H2O2/OH (65). The zwitterion can be reduced during the course of the reaction by tetracyanoethylene to produce its epoxide (66). 

The observation that addition of imidazoles and carboxylic acids significantly improved the epoxidation reaction resulted in the development of Mn-porphyrin complexes containing these groups covalently linked to the porphyrin platform as attached pendant arms (11) [63]. When these catalysts were employed in the epoxidation of simple olefins with hydrogen peroxide, enhanced oxidation rates were obtained in combination with perfect product selectivity (Table 6.6, Entry 3). In contrast with epoxidations catalyzed by other metals, the Mn-porphyrin system yields products with scrambled stereochemistry the epoxidation of cis-stilbene with Mn(TPP)Cl (TPP = tetraphenylporphyrin) and iodosylbenzene, for example, generated cis- and trans-stilbene oxide in a ratio of 35 65. The low stereospecificity was improved by use of heterocyclic additives such as pyridines or imidazoles. The epoxidation system, with hydrogen peroxide as terminal oxidant, was reported to be stereospecific for ris-olefins, whereas trans-olefins are poor substrates with these catalysts. 

Isomerization has been observed with many a,j3-unsaturated carboxylic acids such as w-cinnamic 10), angelic, maleic, and itaconic acids (94). The possibility of catalyzing the interconversion of, for example, 2-ethyl-butadiene and 3-methylpenta-l,3-diene has not apparently been explored. The cobalt cyanide hydride will also catalyze the isomerization of epoxides to ketones (even terminal epoxides give ketones, not aldehydes) as well as their reduction to alcohols. Since the yield of ketone increases with pH, it was suggested that reduction involved reaction with the hydride [Co" (CN)jH] and isomerization reaction with [Co (CN)j] 103). A related reaction is the decomposition of 2-bromoethanol to acetaldehyde... 

Acyl substituents at the 3- and/or 4-positions result in decreased hydrolytic stability compared with the alkyl and aryl derivatives described above. Despite this constraint most of the usual reactions of the carbonyl group are possible. Aldehydes <9ILA1211> and ketones are oxidized to the carboxylic acid, borohydride reduction affords the expected alcohols, and epoxides are formed on reaction with diazomethane. Oximes and arylhydrazones are formed with hydroxylamine and arylhydrazines, and the products may subsequently undergo monocyclic rearrangement involving the oxadiazole to give the corresponding isomeric furazans and 1,2,3-triazoles (Section 4.05.5.1.4). 

The effect of structural variation and the use of different caboxylate salts as cocatalysts was investigated by Pietikainen . The epoxidation reactions were performed with the chiral Mn(III)-salen complexes 173 depicted in Scheme 93 using H2O2 or urea hydrogen peroxide as oxidants and unfunctionalized alkenes as substrates. With several soluble carboxylate salts as additives, like ammonium acetate, ammonium formate, sodium acetate and sodium benzoate, good yields (62-73%) and moderate enantioselectivities (ee 61-69%) were obtained in the asymmetric epoxidation of 1,2-dihydronaphthalene. The results were better than with Ai-heterocycles like Ai-methylimidazole, ferf-butylpyridine. 

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