Esters melting point

Lanogene [Dow], TM for liquid lanolin consisting of low melting point esters. A crystal-clear, amber, viscous liquid anhydrous. Soluble in mineral and vegetable oils. 

The addition of water-miscible solvent, such as alcohol, acetic acid, or dioxane, will facilitate the reduction of keto acids. In addition, transformation of the acid into low melting point ester and the addition of a certain amount of toluene to retain the ester in a clear surface layer can simplify the reduction and optimize the yield. 

The melting points of these esters are usually much lower than those of the corresponding 3 5 dinitrobenzoates their preparation, therefore, offers no advantages over the latter except for alcohols of high molecular weight and for polyhydroxy compounds. The reagent is, however, cheaper than 3 5 dinitrobenzoyl chloride it hydrolyses in the air so that it should either be stored under light petroleum or be prepared from the acid, when required, by the thionyl chloride or phosphorus pentachloride method. 

Add 1 ml. of the alcohol-free ether to 0-1-0-15 g. of finely-powdered anhydrous zinc chloride and 0 5 g. of pure 3 5-dinitrobenzoyl chloride (Section 111,27,1) contained in a test-tube attach a small water condenser and reflux gently for 1 hour. Treat the reaction product with 10 ml. of 1-5N sodium carbonate solution, heat and stir the mixture for 1 minute upon a boiling water bath, allow to cool, and filter at the pump. Wash the precipitate with 5 ml. of 1 5N sodium carbonate solution and twice with 6 ml. of ether. Dry on a porous tile or upon a pad of filter paper. Transfer the crude ester to a test-tube and boil it with 10 ml. of chloroform or carbon tetrachloride filter the hot solution, if necessary. If the ester does not separate on cooling, evaporate to dryness on a water bath, and recrystallise the residue from 2-3 ml. of either of the above solvents. Determine the melting point of the resulting 3 5 dinitro benzoate (Section 111,27). 

Drop 1 g. of sodium into 10 ml. of ethyl alcohol in a small flask provided with a small water condenser heat the mixture until all the sodium has dissolved. Cool, and add 1 g. of the ester and 0-5 ml. of water. Frequently the sodium salt of the acid will be deposited either at once or after boiling for a few minutes. If this occurs, filter oflF the solid at once, wash it with a little absolute ethyl alcohol (or absolute methylated spirit), and convert it into the p-bromophenacyl ester, p-nitro-benzyl ester or S-benzyl-tso-thiuronium salt (for experimental details, see Section 111,85). If no solid separates, continue the boiling for 30-60 minutes, boil oflF the alcohol, allow to cool, render the product just neutral to phenolphthalein with dilute sulphuric or hydrochloric acid, convert the sodium salt present in solution into a crystalline derivative (Section 111,85), and determine its melting point. 

Crystallise the two lots of crude active aec. -octyl hydrogen phthalates separately twice from 90 per cent, acetic acid use 2 g. of acetic acid to each gram of soUd. The recrystaUised esters, if optically pure (8), will melt sharply at 75° if the melting points are below 75°, further recrystallisation is necessary. The yields of optically pure products, m.p. 75°, are 48 g. and 49 g. respectively. 

Dissolve 5 g. of phenol in 75 ml. of 10 per cent, sodium hydroxide solution contained in a wide-mouthed reagent bottle or conical flask of about 200 ml. capacity. Add 11 g. (9 ml.) of redistilled benzoyl chloride, cork the vessel securely, and shake the mixture vigorously for 15-20 minutes. At the end of this period the reaction is usually practically complete and a sohd product is obtained. Filter oflf the soUd ester with suction, break up any lumps on the filter, wash thoroughly with water and drain well. RecrystaUise the crude ester from rectified (or methylated) spirit use a quantity of hot solvent approximately twice the minimum volume required for complete solution in order to ensure that the ester does not separate until the temperature of the solution has fallen below the melting point of phenyl benzoate. Filter the hot solution, if necessary, through a hot water funnel or through a Buchner funnel preheated by the filtration of some boiling solvent. Colourless crystals of phenyl benzoate, m.p. 69°, are thus obtained. The yield is 8 g. 

C, which decomposes when heated above the melting point. Its solubility at 25°C in g/100 g solvent is water. 111 methanol, 5 ethanol, 1.4 acetone, 0.04 and carbon tetrachloride, 0.004. Because its carbon—fluorine bond is unreactive under most conditions, this salt can be converted by standard procedures to typical carboxylic acid derivatives such as fluoroacetyl esters (11,12), fluoroacetyl chloride [359-06-8] (13), fluoroacetamide (14), or fluoroacetonitrile [503-20-8] (14). 

Rea.ctlons, When free (R-R, R -tartaric acid (4) is heated above its melting point, amorphous anhydrides are formed which, on boiling with water, regenerate the acid. Further heating causes simultaneous formation of pymvic acid, CH COCOOH pyrotartaric acid, HOOCCH2CH(CH2)COOH and, finally, a black, charred residue. In the presence of a ferrous salt and hydrogen peroxide, dihydroxymaleic acid [526-84-1] (7) is formed. Nitrating the acid yields a dinitro ester which, on hydrolysis, is converted to dihydroxytartaric acid [617 8-1] (8), which upon further oxidation yields tartronic acid [80-69-3] (9). 

Evaporation Retardants. Small molecule solvents that make up the most effective paint removers also have high vapor pressure and evaporate easily, sometimes before the remover has time to penetrate the finish. Low vapor pressure cosolvents are added to help reduce evaporation. The best approach has been to add a low melting point paraffin wax (mp = 46-57° C) to the paint remover formulation. When evaporation occurs the solvent is chilled and the wax is shocked-out forming a film on the surface of the remover that acts as a barrier to evaporation (5,6). The addition of certain esters enhances the effectiveness of the wax film. It is important not to break the wax film with excessive bmshing or scraping until the remover has penetrated and lifted the finish from the substrate. Likewise, it is important that the remover be used at warm temperatures, since at cool temperatures the wax film may not form, or if it does it will be brittle and fracture. Rapid evaporation occurs when the wax film is absent or broken. 

Table 4. Melting Points of the Full Methyl Esters of Benzenepolycarboxylic Acids...

The major components of camauba wax are aHphatic and aromatic esters of long-chain alcohols and acids, with smaller amounts of free fatty acids and alcohols, and resins. Camauba wax is very hard, with a penetration of 2 dmm at 25°C and only 3 dmm at 43.3°C. Camauba also has one of the higher melting points for the natural waxes at 84°C, with a viscosity of 3960 rare]/s at 98.9°C, an acid number of 8, and a saponification number of 80. 

The major components of candelilla wax are hydrocarbons, esters of long-chain alcohols and acids, long-chain alcohols, sterols, and neutral resins, and long-chain acids. Typically, candelilla wax has a melting point of 70°C, a penetration of 3 drum at 25°C, an acid number of 14, and a saponification number of 55. Principal markets for candelilla include cosmetics, foods, and pharmaceuticals. The FDA affirmed Candelilla as GRAS for certain food apphcations in 21 CFR 184.1976. 

Bayberry Wax. Bayberry wax [8038-77-5] is removed from the surface of the berry of the bayberry (myrtle) shmb by boiling the berries in water and skimming the wax from the surface of the water. The wax is green and made up primarily of lauric, myristic, and palmitic acid esters. The wax has a melting point of 45°C, an acid number of 15, a saponification number of 220, and an iodine number of 6. The wax has an aromatic odor and is used primarily in the manufacture of candles and other products where the distinctive odor is desirable. 

The composition of montan wax depends on the material from which it is extracted, but all contain varying amounts of wax, resin, and asphalt. Black montan wax may be further processed to remove the resins and asphalt, and is known as refined montan wax. White montan wax has been reacted with alcohols to form esters. The wax component of montan is a mixture of long-chain (C24—C q) esters (62—68 wt %), long-chain acids (22—26 wt %), and long-chain alcohols, ketones, and hydrocarbons (7—15 wt %). Cmde montan wax from Germany typically has a melting point of 80°C, an acid number of 32, and a saponification number of 92. 

Most reported boric acid esters are trialkoxy or triaryloxy boranes. The esters range from colorless low boiling Hquids to soHds that possess high melting points. Boric acid esters usually have an odor similar to the hydroxy compound from which they are derived. A more complete description of the physical... 

Pentaerythritol with its four primary hydroxyl groups is used for the preparation of tetraesters and presents Httie difficulty except for its high melting point of 263°C, when pure. Pentaerythritol tetraesters are used in aircraft lubes, synthetic drying oils, and alkyds. Esters derived from trimethylo1 alkanes and dipentaerythritol are also used in alkyd resins (qv). Esterification may take place in situ during preparation of the alkyd. 

The thermoplastic or thermoset nature of the resin in the colorant—resin matrix is also important. For thermoplastics, the polymerisation reaction is completed, the materials are processed at or close to their melting points, and scrap may be reground and remolded, eg, polyethylene, propjiene, poly(vinyl chloride), acetal resins (qv), acryhcs, ABS, nylons, ceUulosics, and polystyrene (see Olefin polymers Vinyl polymers Acrylic ester polymers Polyamides Cellulose ESTERS Styrene polymers). In the case of thermoset resins, the chemical reaction is only partially complete when the colorants are added and is concluded when the resin is molded. The result is a nonmeltable cross-linked resin that caimot be reworked, eg, epoxy resins (qv), urea—formaldehyde, melamine—formaldehyde, phenoHcs, and thermoset polyesters (qv) (see Amino resins and plastics Phenolic resins). 

This reaction can be used for identification of individual alcohols because of the wide variations noted in the melting points of monoalkyl esters up to the dodecyl derivatives. The reaction can be used to separate alcohols of various classes. Monoesters are converted into the normal diesters by heating with an excess of alcohol and a catalyst however, diesters are generally formed directiy from the corresponding diacids. 

Other derivatives can be prepared by reaction of the alcohol with an acid anhydride. For example, phthalic or 3-nitrophthalic anhydride (I mol) and the alcohol (Imol) are refluxed for half to one hour in a non-hydroxylic solvent, e.g. toluene or alcohol-free chloroform, and then cooled. The phthalate ester crystallises out, is precipitated by the addition of low boiling petroleum ether or is isolated by ev toration of the solvent. It is recrystallised from water, 50% aqueous ethanol, toluene or low boiling petroleum ether. Such an ester has a characteristic melting point and the alcohol can be recovered by acid or alkaline hydrolysis. 

Amides are stable compounds. The lower-melting members (such as acetamide) can be readily purified by fractional distillation. Most amides are solids which have low solubilities in water. They can be recrystallised from large quantities of water, ethanol, ethanol/ether, aqueous ethanol, chloroform/toluene, chloroform or acetic acid. The likely impurities are the parent acids or the alkyl esters from which they have been made. The former can be removed by thorough washing with aqueous ammonia followed by recrystallisation, whereas elimination of the latter is by trituration or recrystallisation from an organic solvent. Amides can be freed from solvent or water by drying below their melting points. These purifications can also be used for sulfonamides and acid hydrazides. 

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