Esters unsaturated hydrocarbons

Acids and bases > alcohols and thiols > aldehydes and ketones > halides and esters > unsaturated hydrocarbons > saturated hydrocarbons... 

Esters are most commonly prepared by the reaction of a carboxyHc acid and an alcohol with the elimination of water. Esters are also formed by a number of other reactions utilizing acid anhydrides, acid chlorides, amides, nitriles, unsaturated hydrocarbons, ethers, aldehydes, ketones, alcohols, and esters (via ester interchange). Detailed reviews of esterification are given in References 1—9. 

Unsaturated Hydrocarbons. Olefins from ethylene through octene have been converted into esters via acid-catalyzed nucleophilic addition. With ethylene and propjiene, only a single ester is produced using acetic acid, ethyl acetate and isopropyl acetate, respectively. With the butylenes, two products are possible j -butyl esters result from 1- and 2-butylenes, whereas tert-huty esters are obtained from isobutjiene. The C5 olefins give rise to three j iC-amyl esters and one /-amyl ester. As the carbon chain is lengthened, the reactivity of the olefin with organic acids increases. 

Phthalate esters C(H (COOR)2 are well-characterised, aoderately polar liquid phases [8]. As might be expected, the polarity of the phases declines as the alkyl (R) group increases in size, while their volatility decreases. Hi volatility compared to other available liquid phases has reduced their importance in recent years. Tetraunsaturated hydrocarbons and aromatic hydrocarbons (electron-donor solutes) Iqf... 

The reaction described is of considerable general utility for the preparation of benzoyloxy derivatives of unsaturated hydrocarbons.2"8 Reactions of 2-butyl perbenzoate with various other classes of compounds in the presence of catalytic amounts of copper ions produce benzoyloxy derivatives. Thus this reaction can also be used to effect one-step oxidation of saturated hydrocarbons,9, 10 esters,6,11 dialkyl and aryl alkyl ethers,12 14 benzylic ethers,11,15 cyclic ethers,13,16 straight-chain and benzylic sulfides,12, 17-19 cyclic sulfides,11,19 amides,11 and certain organo-silicon compounds.20... 

Saturated hydrocarbons Unsaturated hydrocarbons Wax esters Steryl esters Long chain aldehydes Triacylglycerols Long chain alcohols Free fatty acids Quinones Sterols... 

A mammal may emit many volatile compounds. Humans, for instance, give off hundreds of volatiles, many of them chemically identified (Ellin etal., 1974). The volatiles include many classes of compound such as acids (gerbil), ketones, lactones, sulfides (golden hamster), phenolics (beaver, elephant), acetates (mouse), terpenes (elephant), butyrate esters (tamarins), among others. The human samples mentioned before contained hydrocarbons, unsaturated hydrocarbons, alcohols, acids, ketones, aldehydes, esters, nitriles, aromatics, heterocyclics, sulfur compounds, ethers, and halogenated hydrocarbons. Sulfur compounds are found in carnivores, such as foxes, coyotes, or mustelids. The major volatile compound in urine of female coyotes, Canis latrans, is methyl 3-methylhut-3-enyl sulfide, which accounts for at least 50% of all urinary volatiles (Schultz etal, 1988). 

The lower members of the homologous series of 1. Alcohols 2. Aldehydes 3. Ketones 4. Acids 5. Esters 6. Phenols 7. Anhydrides 8. Amines 9. Nitriles 10. Polyhydroxy phenols 1. Polybasic acids and hydro-oxy acids. 2. Glycols, poly-hydric alcohols, polyhydroxy aldehydes and ketones (sugars) 3. Some amides, ammo acids, di-and polyamino compounds, amino alcohols 4. Sulphonic acids 5. Sulphinic acids 6. Salts 1. Acids 2. Phenols 3. Imides 4. Some primary and secondary nitro compounds oximes 5. Mercaptans and thiophenols 6. Sulphonic acids, sulphinic acids, sulphuric acids, and sul-phonamides 7. Some diketones and (3-keto esters 1. Primary amines 2. Secondary aliphatic and aryl-alkyl amines 3. Aliphatic and some aryl-alkyl tertiary amines 4. Hydrazines 1. Unsaturated hydrocarbons 2. Some poly-alkylated aromatic hydrocarbons 3. Alcohols 4. Aldehydes 5. Ketones 6. Esters 7. Anhydrides 8. Ethers and acetals 9. Lactones 10. Acyl halides 1. Saturated aliphatic hydrocarbons Cyclic paraffin hydrocarbons 3. Aromatic hydrocarbons 4. Halogen derivatives of 1, 2 and 3 5. Diaryl ethers 1. Nitro compounds (tertiary) 2. Amides and derivatives of aldehydes and ketones 3. Nitriles 4. Negatively substituted amines 5. Nitroso, azo, hy-drazo, and other intermediate reduction products of nitro com-pounds 6. Sulphones, sul-phonamides of secondary amines, sulphides, sulphates and other Sulphur compounds... 

However, the alcohol and acid formed during the hydrolysis of nitric esters are accompanied by a range of other compounds such as aldehydes, ketones, hydroxy-carboxylic acids, unsaturated hydrocarbons, nitrous add, etc. (e.g. reference [107]). 

Unsaturated Hydrocarbons. Olefins from ethylene through octene have been converted into esters via acid-catalyzed nucleophilic addition. 

In 1925, Fischer and Tropsch developed a process for producing a mixture of saturated and unsaturated hydrocarbons, and oxygenated products such as alcohols and esters by the reaction of synthesis gas (a mixture of CO and H2) using heterogeneous catalysts of Fe and Co (eq. 1.1) [1],... 

The components of biodiesel are vegetable oils composed of glycerol esters of fatty acids. In the process of transesterification, the glycerol components of the triglyceride molecules are exchanged for methanol. The products are fatty-acid methyl esters consisting of straight saturated and unsaturated hydrocarbon chains, as described under chemical processes. 

Kishner studied the reaction or the Orignard reagent on the ester of cyclopropane nionocarboxylic acid. He obtained a compound which ue considered to be cyclopropyldimethylcaibinoi,and from this he obtained an unsaturated hydrocarbon,cyclop/-opyImethyl-ethylene, Chg - OH - C = OHa, The cyclic struc-... 

One remarkable group of homogeneous CO reactions 1 that of the conversions with unsaturated hydrocarbons using alkynes. alkcnes or dienes as the adducts, lactones, acids or esters are produced. The two most efficient catalyst metals are rhodium and palladium. This part of CO chemistry is a very fascinating one, because carbon dioxide is fixed in the organic compounds, through the formation of a new carbon-carbon bond. 

Applications The Karl Fischer reagent can be applied directly to the determination of water in a variety of organic compoimds, including saturated or unsaturated hydrocarbons, alcohols, halides, acids, acid anhydrides, esters, ethers, amines, amides, nitroso and nitro compounds, sulfides, hydroperoxides, and dialkyl peroxides. The use of sodium tartrate dihydrate for standardization of the response of the Karl Fischer reagent has been shown to lead to a small error because of occlusion of about 2% (relative) water in the crystal structure. 

Whereas alkylphosphonic diesters react readily with lithium or organomagnesium reagents with the formation of the metallated phosphonate carbanions, the reactions between such esters and the metals themselves result, by contrast, in dealkylation of the ester groups involving both C-0 and P-0 cleavage traces of unsaturated hydrocarbons, even including alkynes and aromatics, are thought to be formed by radical-induced reactions. 

According to Menschutkin, the esters of tertiary alcohols are split up by water into acid and unsaturated hydrocarbons instead of being saponified into the corresponding alcohol and acid. Thus the amyl ester of acetic acid forms acetic acid and amylene according to the equation... 

Electrochemical Nitrations. A method developed in 1936 in Sweden by Ohman for prepn of nitric acid esters has been described in several patents. The method consists in anodic oxidation (using a bright platinum anode) in presence of nitric acid, or its salts (such.as Ca nitrate). The compds to be nitrated are unsaturated hydrocarbons (such as ethylene, propylene, butylene, etc), which can be dissolved in nonaqueous solvents (such as acetone). The OH concn is maintained low during the reaction by adding either coned nitric acid or glacial acetic acid. Water should be absent to prevent the formation of various by-products... 

Outline all steps in a possible laboratory synthesis of each of the unsaturated carbonyl compounds in Table 27.1, p. 866, using any readily available monofunctional compounds simple alcohols, aldehydes, ketones, acids, esters, and hydrocarbons. 

Acrylates Acrylonitriles Allyl Esters Cellulose esters Epoxies Ethylenic (unsaturated) hydrocarbons Poly-hydroxy esters(eg Pentaerythritol tetramethacrylate,Ethylene Glycol diacrylate) Polyolefins Vinyl compound esters, acids)... 

Fig. (5). Lepidopteran pheromone biosynthetic pathways utilize fatty acid synthesis, desatiindiun, specific chain-shortening enzymes, and/or functional modification of tlie carbony l carbon to produce species-apecific acetate ester, aldehyde, alcohol, or hydrocarbon pheromone blends. Unsaturated hydrocarbons can be further modified to epoxides (adapted from ref. [21]).

In addition to the examples already given for the reaction of (diphenylmethylene)cyclo-propane (3) with unsaturated hydrocarbons (see Section 2.2.2.3.2.1.1.2.1.), some highly efficient reactions of unsaturated esters with 3 are known. ... 

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