Ethers melting point

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). 

Most polysaccharides are insoluble or sparingly soluble in cold water, insoluble in cold alcohol and ether, and rarely possess melting points. Only inuUn melts at about 178° (dec.) after drying at 130°. 

Sulphonic acids. The aromatic sulphonic acids and their alkali metal salts are soluble in water, but insoluble in ether (Solubility Group II). They are best characterised by conversion into crystalline S-benzyl-iso-thiuronium salts (see Section IV,33,2 and 111,85,5), which possess characteristic melting points. A more time-consuming procedure is to treat the well-dried acid or... 

Acetaldehyde can be isolated and identified by the characteristic melting points of the crystalline compounds formed with hydrazines, semicarbazides, etc these derivatives of aldehydes can be separated by paper and column chromatography (104,113). Acetaldehyde has been separated quantitatively from other carbonyl compounds on an ion-exchange resin in the bisulfite form the aldehyde is then eluted from the column with a solution of sodium chloride (114). In larger quantities, acetaldehyde may be isolated by passing the vapor into ether, then saturating with dry ammonia acetaldehyde—ammonia crystallizes from the solution. Reactions with bisulfite, hydrazines, oximes, semicarb azides, and 5,5-dimethyl-1,3-cyclohexanedione [126-81 -8] (dimedone) have also been used to isolate acetaldehyde from various solutions. 

Meclizine Hydrochloride. Pipera2ine Antivert, and Bonine are trade names for mech2ine dihydrochloride monohydrate [31884-77-2] (20). It is a white or slightly yellowish crystalline powder with a slight odor, no taste, and a melting point of 217—224°C. The hydrochloride is practically insoluble in water and ether. It is freely soluble in chloroform, pyridine, methylacetamide, and mild acid alcohol—water mixtures, and is slightly soluble in dilute acids or alcohol. See Reference 16 for synthesis. 

Phenformin. Phenformin hydrochloride [834-28-6] (1-phenethylbiguanide, A/-(2-phenylethyl)imidodicarbonimidic diamide), is a white to off-white odorless crystalline power having a bitter taste. The melting point is 175—178°C. It is freely soluble in water and alcohol, and practically insoluble in chloroform, ether, and hexane. Its pH in solution is 6.0—7.0. 

Benzophenone. Benzophenone [119-61-9] (diphenyl ketone) exists in a stable form as colorless orthorhombic bisphenoidal prisms when crystallized from alcohol or ether. Other labile forms of lower melting point exist. Benzophenone has been identified as a flavor component of wine grapes and has a geranium-like odor. It is soluble in most organic solvents, and is insoluble in water. 

Properties. o-Nitiotoluene [88-72-2] is a clear yeUow liquid. The solid is dimorphous and the melting points of the a- and P-forms ate —9.55 and —3.85 C, respectively. o-Nitrotoluene is infinitely soluble in benzene, diethyl ether, and ethanol. It is soluble in most organic solvents and only slightly soluble in water (0.065 g in 100 g of water at 30°C). The physical properties of o-nitrotoluene are hsted in Table 9. 

The acid occurs both as colorless triclinic prisms (a-form) and as monoclinic prisms ( 3-form) (8). The P-form is triboluminescent and is stable up to 137°C the a-form is stable above this temperature. Both forms dissolve in water, alcohol, diethyl ether, glacial acetic acid, anhydrous glycerol, acetone, and various aqueous mixtures of the last two solvents. Succinic acid sublimes with partial dehydration to the anhydride when heated near its melting point. 

As shown in Table 3, the glass-transition temperatures of the amorphous straight-chain alkyl vinyl ether homopolymers decrease with increasing length of the side chain. Also, the melting points of the semicrystalline poly(alkyl vinyl ether)s increase with increasing side-chain branching. 

Table 3. Glass-Transition Temperature of Amorphous Poly(Vinyl Ether)s and Melting Points of Crystalline Poly(Vinyl Ether)s ...

The heavy metal salts, ia contrast to the alkah metal salts, have lower melting points and are more soluble ia organic solvents, eg, methylene chloride, chloroform, tetrahydrofiiran, and benzene. They are slightly soluble ia water, alcohol, ahphatic hydrocarbons, and ethyl ether (18). Their thermal decompositions have been extensively studied by dta and tga (thermal gravimetric analysis) methods. They decompose to the metal sulfides and gaseous products, which are primarily carbonyl sulfide and carbon disulfide ia varying ratios. In some cases, the dialkyl xanthate forms. Solvent extraction studies of a large number of elements as their xanthate salts have been reported (19). 

Reaction with hydrogen at 220°C in the presence of reduced nickel catalyst results in total decomposition to hydrogen chloride and carbon. An explosive reaction occurs with butylUthium in petroleum ether solution (4). Tetrachloroethylene also reacts explosively with metallic potassium at its melting point, however it does not react with sodium (5). 

The principal coloring matter in turmeric and its oleoresin is curcumin [458-37-7] (l,6-heptadiene-3,5-dione, l,7-bis[4-hydroxy-3-methoxy-phenyl] (45), an orange-yeUow, crystalline powder, insoluble in water and ether but soluble in ethanol and glacial acetic acid. It has a reported melting point of 180-183°C. 

An unusual method for the preparation of syndiotactic polybutadiene was reported by The Goodyear Tire Rubber Co. (43) a preformed cobalt-type catalyst prepared under anhydrous conditions was found to polymerize 1,3-butadiene in an emulsion-type recipe to give syndiotactic polybutadienes of various melting points (120—190°C). These polymers were characterized by infrared spectroscopy and nuclear magnetic resonance (44—46). Both the Ube Industries catalyst mentioned previously and the Goodyear catalyst were further modified to control the molecular weight and melting point of syndio-polybutadiene by the addition of various modifiers such as alcohols, nitriles, aldehydes, ketones, ethers, and cyano compounds. 

The melting point is not appreciably raised by recrystallization from petroleum ether. The highest melting point recorded in the literature is 53.8°. 

For materials with very low melting points it is sometimes convenient to use dilute solutions in acetone, methanol, pentane, diethyl ether or CHCI3-CCI4. The solutions are cooled to -78° in a dry-ice/acetone bath, to give a slurry which is filtered off through a precooled Buchner funnel. Experimental details, as applied to the purification of nitromethane, are given by Parrett and Sun [J Chem Educ 54 448 7977]. 

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. 

Biquinolyl (a,a -diquinolyl) [119-91-5] M 256.3, m 196 , pKe, 4.2. Decolorised in CHCI3 soln (charcoal), then crystd to constant melting point from EtOH or pet ether [Cumper, Ginman and Vogel J Chem Soc 1188 1962]. 

Bis-(trifluoroacetoxy)iodobenzene [2712-78-9] M 430.0, m 112-114 (dec), 120-121 , 124-126". Cryst from warm trifluoroacetic acid and dry over NaOH pellets. Recrystd from Me2CO/pet ether. Melting point depends on heating rate. [Synthesis 445 1975.]... 

Chlorobenzonitrile [873-32-5] M 137.6, m 45-46°. Crystd to constant melting point from benzene/pet ether (b 40-60°). 

Diethylamine [109-89-7] M 73.1, b 55.5, d 0.707, n 1.38637, pK 11.38. Dried with LiAlH4 or KOH pellets. Refluxed with, and distd from, BaO or KOH. Converted to the p-toluenesulfonamide and crystd to constant melting point from dry pet ether (b 90-120 ), then hydrolysed with HCl, excess NaOH was added, and the amine passed through a tower of activated alumina, redistd and dried with activated alumina before use [Swift 7 Am Chem Soc 64 115 1942]. 

Other purification procedures include the formation of the picrate, prepared in benzene soln and crystd to constant melting point, then decomposed with warm 10% NaOH and extracted into ether the extract was washed with water, and distd under reduced pressure. The oxalate has also been used. The base has been fractionally crystd by partial freezing and also from aq 80% EtOH then from absolute EtOH. It has been distd from zinc dust, under nitrogen. 

L-Malic acid [97-67-6] M 134.1, m 104.5-106 , [ajp -2.3 (c 8.5, HjO), pK, 3.46, pK 5.10. Crystd (charcoal) from ethyl acetate/pet ether (b 55-56°), keeping the temperature below 65°. Or, dissolved by refluxing in fifteen parts of anhydrous diethyl ether, decanted, concentrated to one-third volume and crystd at 0°, repeatedly to constant melting point. 

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