Esters epoxide compounds

Compound types Aromatics Olefins Alcohols Nitriles Acids CHC12 CC13 CH2C1 NO, Diols Ketones Ethers Aldehydes N(Me), Esters Epoxides Nitromethane Nitrogroups Pyridine Dioxane Aromatic bases... 

The diazeniumdiolate anions react with electrophiles to produce stable covalent compounds (Fig. 3.9) [213, 216]. These compounds have the ability to act as prodrugs, releasing nitric oxide only when metabolically or enzymatically converted to the diazeniumdiolate anion [217-219]. Several compounds ofthis class have been synthesized by reaction of alkyl or aryl halides, sulfate esters, epoxides, etc. with the ionic diazeniumdiolates [220, 221]. 

Essential oils may comprise volatile compounds of terpenoid or non-terpe-noid origin. All of them are hydrocarbons and their oxygenated derivatives. Some may also contain nitrogen or sulphur derivatives. They may exist in the form of alcohols, acids, esters, epoxides, aldehydes, ketones, amines, sulphides, etc. Monoterpenes, sesquiterpenes and even diterpenes constitute the composition of many essential oils. In addition, phenylpropanoids, fatty acids and their esters, or their decomposition products are also encountered as volatiles [1-16, 21-33, 36-38]. 

Oxidation-reduction (redox) reactions, along with hydrolysis and acid-base reactions, account for the vast majority of chemical reactions that occur in aquatic environmental systems. Factors that affect redox kinetics include environmental redox conditions, ionic strength, pH-value, temperature, speciation, and sorption (Tratnyek and Macalady, 2000). Sediment and particulate matter in water bodies may influence greatly the efficacy of abiotic transformations by altering the truly dissolved (i.e., non-sorbed) fraction of the compounds — the only fraction available for reactions (Weber and Wolfe, 1987). Among the possible abiotic transformation pathways, hydrolysis has received the most attention, though only some compound classes are potentially hydrolyzable (e.g., alkyl halides, amides, amines, carbamates, esters, epoxides, and nitriles [Harris, 1990 Peijnenburg, 1991]). Current efforts to incorporate reaction kinetics and pathways for reductive transformations into environmental exposure models are due to the fact that many of them result in reaction products that may be of more concern than the parent compounds (Tratnyek et al., 2003). 

Several optically active, /i-unsaturated esters 1, bearing a chiral auxiliary as the ester group, were epoxidized with tor-butyl hydroperoxide in the presence of butyllithium with yields highly dependent on the structure of epoxidized compound and moderate to good diastereose-lectivity 28. (—)-(S )-S -Phenyl-.V-2-phenylvinyl-A, -tosylsulfoximide (3) was epoxidized under the same conditions to give almost quantitatively the crude epoxide 4 (which decomposes on attempted chromatography, isolated yield 20%) with complete diastereoselectivity28. 

The adducts 308 and 308 were also transformed into epoxide 314. Ring opening of the epoxide, followed by ozonolysis and reduction, furnishes keto-ester 315. Compounds 312 and 315 were converted into a variety of racemic C-nucleosides [164]. 

Epoxidized linseed oil, butyl ester Epoxidized linseed oil, 2-ethylhexyl ester Epoxidized soybean oil, butyl ester epoxies, flexibilizing adhesives Castor oil glycidyl ether epoxies, flexibilizing bridge decking compounds... 

Epoxy compounds. Epoxy compounds function both as plasticizers and stabilizers in flexible and semirigid PVC. As stabilizers, epoxies react with liberated HCl. In addition, they react with the polymer chain at labile-chlorine sites—either directly or catalytically by increasing the reactivity of the labile-chlorine site with metal salt stabilizers. Most epoxy stabilizers are derived from unsaturated fatty oils and fatty acid esters. Epoxidized soybean and linseed oils and epoxy tallate are commonly used products. Epoxy tallate also increases light stability. Epoxy compovmds can be formulated with metallic liquid stearates and, thus, can be sold to compounders as a one-package system if a constant ratio of stabilizer-to-epoxy is acceptable. However, since these epoxy compounds are also plasticizers, the balance of the formulation must be adjusted for this effect. 

Plant essential oils are the low molecular weight volatile mixtures, biosynthesized in various plant organs. The chemical nature of essential oils belongs to the composition of terpene compounds (mono-, sesqui-, and diterpenes), which are mainly obtained as hydrocarbon compounds or the derivatives of oxygen molecule. A few components of the essential oil are nitrogenous or sulfury in nature which are found as alcohols, acids, esters, epoxides, aldehydes, ketones, amines, and... 

From the work of Takegami et aL, and Heck, it must foUow that cobalt hydrocarbonyl reacts with epoxides in the acid form. The reaction of epoxide compounds should be accelerated by addition of small amounts of alcohols, ketones, ethers and esters [303], as well as copper oxide or halide, silver oxide and aluminium chloride [304]. 

Primary and secondary amines also react with epoxides (or in situ produced episulfides )r aziridines)to /J-hydroxyamines (or /J-mercaptoamines or 1,2-diamines). The Michael type iddition of amines to activated C—C double bonds is also a useful synthetic reaction. Rnally unines react readily with. carbonyl compounds to form imines and enamines and with carbo-tylic acid chlorides or esters to give amides which can be reduced to amines with LiAlH (p. Ilf.). All these reactions are often applied in synthesis to produce polycyclic alkaloids with itrogen bridgeheads (J.W. Huffman, 1967) G. Stork, 1963 S.S. Klioze, 1975). 

Epo>y Compounds. Epoxidized soya oil (ESO) is the most widely used epoxy-type additive and is found ia most mixed metal stabilized PVC formulations at 1.0—3.0 phr due to its versatiHty and cost effectiveness. Other usefiil epoxy compounds are epoxidized glycerol monooleate, epoxidized linseed oil, and alkyl esters of epoxidized tall oil fatty acid. 

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). 

Telomerization Reactions. Butadiene can react readily with a number of chain-transfer agents to undergo telomerization reactions. The more often studied reagents are carbon dioxide (167—178), water (179—181), ammonia (182), alcohols (183—185), amines (186), acetic acid (187), water and CO2 (188), ammonia and CO2 (189), epoxide and CO2 (190), mercaptans (191), and other systems (171). These reactions have been widely studied and used in making unsaturated lactones, alcohols, amines, ethers, esters, and many other compounds. 

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