Saturated Aliphatic Esters

Composition. Shellac is primarily a mixture of aUphatic polyhydroxy acids in the form of lactones and esters. It has an acid number of ca 70, a saponification number of ca 230, a hydroxyl number of ca 260, and an iodine number of ca 15. Its average molecular weight is ca 1000. Shellac is a complex mixture, but some of its constituents have been identified. Aleuritic acid, an optically inactive 9,10,16-trihydroxypalmitic acid, has been isolated by saponification. Related carboxyflc acids such as 16-hydroxy- and 9,10-dihydroxypalmitic acids, also have been identified after saponification. These acids may not be primary products of hydrolysis, but may have been produced by the treatment. Studies show that shellac contains carboxyflc acids with long methylene chains, unsaturated esters, probably an aliphatic aldehyde, a saturated aliphatic ester, a primary alcohol, and isolated or unconjugated double bonds. 

C=O Stretching Vibrations The C=O absorption band of saturated aliphatic esters (except formates) is in the 1750-1735 cm-1 region. The C=0 absorption bands of formates, a,/3-unsaturated, and benzoate esters are in the region of 1730-1715 cm-1. Further conjugation has little or no additional effect upon the frequency of the carbonyl absorption. 

C=0 absorption band of saturated aliphatic esters (except formates) is in the 1750-1735 cm-1 region. 

Hercolube [Aqualon], TM for synthetic lubricant base stocks. J15 Saturated aliphatic ester of pentaerythritol for plasticizing vinylidene chloride. 

Total alkanes Saturated aliphatic esters The acids palmitic, stearic, oleic, lin-oleic, linolenic Catechol... 

With the exception of formates, which absorb in the region 1730-1715 cm (5.78-5.83 pm), saturated aliphatic esters absorb at... 

If the alkyl dciivativcs of the ester aie employed, it is possible to effect the synthesis of a series of ketones and saturated aliphatic acids, according to whcthci the one or other 1 ( ac tion is used. 

In the Diels-Alder reaction with inverse electron demand, the overlap of the LUMO of the 1-oxa-l,3-butadiene with the HOMO of the dienophile is dominant. Since the electron-withdrawing group at the oxabutadiene at the 3-position lowers its LUMO dramatically, the cycloaddition as well as the condensation usually take place at room or slightly elevated temperature. There is actually no restriction for the aldehydes. Thus, aromatic, heteroaromatic, saturated aliphatic and unsaturated aliphatic aldehydes may be used. For example, a-oxocarbocylic esters or 1,2-dike-tones for instance have been employed as ketones. Furthermore, 1,3-dicarbonyl compounds cyclic and acyclic substances such as Meldmm s acid, barbituric acid and derivates, coumarins, any type of cycloalkane-1,3-dione, (1-ketoesters, and 1,3-diones as well as their phosphorus, nitrogen and sulfur analogues, can also be ap-... 

As in the case of the oxidation of saturated esters, the rate of chain copolymerization monomer and dioxygen obeys the equation similar to that for aliphatic ester oxidation. 

A number of other acylsuccinic esters can be prepared in a similar fashion from the appropriate saturated aliphatic aldehydes and maleic esters.2 3 The procedure is equally adaptable to the preparation of a-acyltricarballylic esters from aldehydes and aconitates.2 Good temperature control (80-90°) is most important for success in these reactions. 

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... 

Saponification see Hydrolysis Saponification equivalent of an ester, determination of. 392, 1065 Saturated aliphatic hydrocarbons, 233 reactions and characterisation of 234, 1058 table of, 235 ... 

The carboalkoxylation of saturated aliphatic halides may give mixtures of isomeric products if carried out above about 75°, at least with tetra-carbonylcobalt anion as catalyst. Isomerization occurs because the intermediate alkylcobalt complex isomerizes competitively with the carbonylation at the higher temperatures. The isomerization probably involves stepwise loss of carbon monoxides to the tricarbonylalkylcobalt(I) stage. This complex then may reversibly rearrange by a hydride elimination to a hydride-olefin-71 complex. The hydride may also add back in the reverse direction and produce an isomeric alkyl. Subsequent readdition of carbon monoxides and alcoholysis would produce isomerized ester ... 

Carbonyl compounds will be taken in this chapter to mean any organic compound that contains at least one carbon-oxygen double bond where we limit the substitution to only saturated aliphatic, saturated alicyclic and aryl hydrocarbyl groups. Carbonyl compounds with a variety of unsaturated substituents have earlier been discussed within the context of enones4. Non-hydrocarbyl substituents, X , may be directly attached to the carbonyl and elsewhere in the molecule. The first type of species, RCOX, is alternatively identified as acyl derivatives such as carboxylic acids and their esters, halides and amides and have already been discussed in a recent Patai thermochemistry... 

High boiling ester of pentaerythritol and a saturated aliphatic acid... 

Styrene can be copolymerized with many monomers. The following monomers can be used along with styrene in the manufacture of food contact materials a-methylsty-rcne, vinyltoluene, divinylbenzene, acrylonitrile, ethyleneoxide, butadiene, fumaric and maleic acid esters of the mono functional saturated aliphatic alcohols C1-C8, acrylic acid ester and methacrylic acid, maleic acid anhydride, methylacrylamide-methylol ether, vinylmethyl ether, vinylisobutyl ether. Styrene and/or a-methylstyrene and/or vinyltoluene should be the main mixture component in every case. 

According to literature data vinyl esters of saturated aliphatic carboxylic acid copolymerize randomly with each other (I), the monomers being incorporated into the copolymer in about the same ratio at which they are present in the monomer mixture. This means that for practical purposes the relative reactivity ratios ri and r > can be taken to be equal and unity. 

In El the molecular ion is only weakly observed in the case of linear saturated hydrocarbons. The presence of branching usually entails the disappearance of this peak. However, an unsaturation, and especially an aromatic ring, makes the molecular ion peak more intense. The presence of electronegative saturated heteroatoms (oxygen, fluorine) normally prevents the observation of the molecular ion. In fact, its intensity depends on the groups that are present. Thus an aliphatic ester yields a weak or absent molecular ion, whereas an aromatic one usually yields an intense molecular ion peak. 

In the carbonyl region, at a weak extent of conversion, photooxidation of ABS and BR led to the formation of a thin absorption band with maxima at 1697 cm-1 (a, (3-unsaturated acids) and 1683 cm-1 (a, (3-unsaturated ketone), and to the formation of a broader absorption band with a maximum at 1721 cm-1. As photooxidation proceeded, the intensity of this latter band increased and shifted to 1717 cm-1 whilst the band at 1697 cm-1 became hard to observe. The intensity of the band at 1697 cm-1 ceased to increase after 16 h of irradiation. When the exposure time was longer than 22 h, only one absorption band was observed. Its maximum shifted from 1717 to 1725 cm-1. In parallel, a shoulder was detected in the range 1775-1785 cm-1. It was shown that the absorption around 1725 cm-1 resulted from the convolution of various species saturated carboxylic acid (1717 cm - ), aliphatic ester (1735 cm-1), a, (3-unsatur-ated anhydride (1724-1782 cm-1), saturated aldehyde (1727-2720 cm-1) and saturated ketone (1725 cm-1). The maximum at 1780 cm-1 has been assigned to three types of structure a, (3-unsaturated anhydride (1724 and 1782 cm-1), perester (1789 cm-1) and 7-lactone (1775 and 1175 cm-1). 

Oxidation 1) H+ 2) Pb (OAc), Aromatic P-Arylcyclopropyl Saturated, Aliphatic Methyl ester... 

By using values for the densities of saturated vapour found by Schoop, Schumann found satisfactory agreement with Winkehnann s formula for the vapour pressures of aliphatic esters, whilst Duhring s formula gave very different specific factors. 

Van Wijk and Seeder s viscosity equation, 91 vapour, density of saturated, 324 specific heat of saturated, 336, 346-7, 359 vapour pressure 226 alignment chart, 271 of aliphatic esters, 286 of alkali halides, 237,243 of benzene, 267 boiling-point method for, 235 in capillary tubes, 367 of carbon, 246 centri fugal force, effect of, on 292 constant, 335, 341 over curved surface, 366 determination of, 227-47 dew-point method, 241 of dibasic acids, 243 dynamical method, 235 effusion method, 241. electrification, effect of on, 238, 375 of elements 257 of esters, 250 f., 286 of fusible metal, 230 in... 

Alkyl iodides 244-261 Simple saturated aliphatic 263,265,275. Ester thioamides of aliphatic 253... 

Simplesse 100 and 300 exhibited some fat-like interactions with saturated aliphatic aldehydes C6-C10 (hexanal, heptanal, octanal, nonanal, decanal), while carbohydrate-based and mixed-blend replacers showed no interaction (Fig. 5.26 and 5.27). Little or no interaction was noted between any of the fat replacers and the saturated aliphatic methyl ketones (Fig. 5.26 and 5.27). Unsaturated carbonyls showed more interactions with protein-based than with carbohydrate-based and mixed-blend replacers (Fig. 5.26 and 5.27). Of the sulfur components studied, propanethiol substantially interacted with Simplesse 100 and 300 (Fig. 5.26). Of these two protein-based replacers, Simplesse 100 showed some fat-like interaction with limonene (Fig. 5.27) and with the two esters ethyl caproate and ethyl heptanoate (Fig. 5.28). 

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