Crystalline products

The following oxidation of camphor to camphor-quinone illustrates the oxidising action of selenium dioxide, and readily gives a crystalline product. 

If the solvent constituting the crystallisation medium has a compara tively high boiling point, it is advisable to wash the solid with a solvent of low boiling point in order that the ultimate crystalline product may be easily dried it need hardly be added that the crystals should be insoluble or only very sparingly soluble in the volatile solvent. The new solvent must be completely miscible with the first, and should not be applied until the crystals have been washed at least once with the original solvent. 

Azlactone of a-benzoylaminocinnamic acid. Place a mi.xture of 27 g. (26 ml.) of redistilled benzaldehyde, 45 g. of Mppuric acid (Section IV,54), 77 g. (71-5) ml. of acetic anhydride and 20-5 g. of anhydrous sodium acetate in a 500 ml. conical flask and heat on an electric hot plate with constant shaking. As soon as the mixture has liquefied completely, transfer the flask to a water bath and heat for 2 hours. Then add 100 ml. of alcohol slowly to the contents of the flask, allow the mixture to stand overnight, filter the crystalline product with suction, wash with two 25 ml. portions of ice-cold alcohol and then wash with two 25 ml. portions of boiling water dry at 100°. The yield of almost pure azlactone, m.p. 165-166°, is 40 g. Recrystallisation from benzene raises the m.p. to 167-168°. 

The reaction between phthalonitrUe and copper also takes place readily in feoihng quinoline or a-methyhiaphthalene the pigment is precipitated as fast as it is formed as a crystalline product. It is separated from the excess of copper by shaking with alcohol, when the metal sinks and the pigment, which remains in suspension, can be poured off the process may be repeated to give the pure compound. 

Place 1 55 g. of clean sodium in a 250 ml. round-bottomed flask equipped with a reflux condenser. Add 40 ml. of absolute alcohol (or rectified spirit). If all the sodium has not disappeared after the vigorous reaction has subsided, warm the flask on a water bath until solution is complete. Cool the mixture and add 10 g. of p-acetylaminophenol. Introduce 15 g. (8 ml.) of ethyl iodide slowly through the condenser and reflux the mixture for 45-60 minutes. Pour 100 ml. of water through the condenser at such a rate that the crystalline product does not separate if crystals do separate, reflux the mixture until they dissolve. Then cool the flask in an ice bath collect the crude phenacetin with suction and wash with a little cold water. Dissolve the crude product in 80 ml. of rectified spirit if the solution is coloured, add 2 g. of decolourising carbon and filter. Treat the clear solution with 125 ml. of hot water and allow to cool. Collect the pure phenacetin at the pump and dry in the air. The yield is 9-5 g., m.p. 137°. 

High vacuum distillation gave a crystalline product, containing small amounts of impurities, inter alia some 2-butynoic acid. Crystallization from a 3 1 mixture of pentane and diethyl ether at low temperature gave the pure acid, m.p. 77°C, in 38-45 yields. 

Phosphonium perchlorate, P(0H)4C104, can be formed as a crystalline product that melts at 46—47°C. This compound is obtained by mixing phosphoric and perchloric acids (65). 

Potassium siUcates are manufactured in a manner similar to sodium siUcates by the reaction of K CO and sand. However, crystalline products are not manufactured and the glass is suppHed as a flake. A 3.90 mole ratio potassium siUcate flake glass dissolves readily in water at ca 88°C without pressure by incremental addition of glass to water. The exothermic heat of dissolution causes the temperature of the solution to rise to the boiling point. Lithium sihcate solutions are usually prepared by dissolving siUca gel in a LiOH solution or mixing colloidal siUca with LiOH. 

Moisture. In relatively pure sugar solutions, moisture is deterrnined as the difference between 100 and Brix. In crystalline products, it is usually deterrnined by loss-on-drying under specified conditions in an oven or by commercial moisture analyzers that have built-in balances. Moisture in molasses and heavy symps is deterrnined by a special loss-on-drying technique, which involves coating the sample onto sand to provide a greater surface area for oven drying. The result of this test is usually considered dry substance rather than moisture. 

The 1995 Canadian and United States sugar alcohol (polyol) production is shown in Table 2. The market share of each is also given. Liquids comprise 48% crystalline product comprises 39% and mannitol comprises 13% of the polyol market. An estimate of total U.S. sorbitol capacity for 1995 on a 70% solution basis was 498,000 t. ADM, Decatur, lU., produced 68,200 t Ethichem, Easton, Pa., 13,600 t Lon2a, Mapleton, lU., 45,400 t Roquette America, Gurnee, lU., 68,200 t and SPI Polyols, New Castle, Del., 75,000 t (204). Hoffman-LaRoche, which produces sorbitol for captive usage in the manufacture of Vitamin C (see Vitamins), produced about 27,300 t in 1995. 

Stannous Oxide. Stannous oxide, SnO ((tin(II) oxide), mol wt 134.70, sp gr 6.5) is a stable, blue-black, crystalline product that decomposes at above 385°C. It is insoluble in water or methanol, but is readily soluble in acids and concentrated alkaHes. It is generally prepared from the precipitation of a stannous oxide hydrate from a solution of stannous chloride with alkaH. Treatment at controUed pH in water near the boiling point converts the hydrate to the oxide. Stannous oxide reacts readily with organic acids and mineral acids, which accounts and for its primary use as an intermediate in the manufacture of other tin compounds. Minor uses of stannous oxide are in the preparation of gold—tin and copper—tin mby glass. 

Stannous Oxide Hydrate. Stannous oxide hydrate [12026-24-3] SnO H2O (sometimes erroneously called stannous hydroxide or stannous acid), mol wt 152.7, is obtained as a white amorphous crystalline product on treatment of stannous chloride solutions with alkaH. It dissolves in alkaH solutions, forming stannites. The stannite solutions, which decompose readily to alkaH-metal stannates and tin, have been used industrially for immersion tinning. 

In general, hydrated borates of heavy metals ate prepared by mixing aqueous solutions or suspensions of the metal oxides, sulfates, or halides and boric acid or alkali metal borates such as borax. The precipitates formed from basic solutions are often sparingly-soluble amorphous soHds having variable compositions. Crystalline products are generally obtained from slightly acidic solutions. 

In 1943 the reaction of anhydrous RhCl and CO at 80°C under pressure with a haUde acceptor, such as copper, was reported to produce a black crystalline product formulated as Rh4(CO) (42). The correct stmcture of the complex was... 

Sodium dichromate, sodium chromate, and mixtures thereof are shipped as concentrated solutions ia tank cars and tmcks. The chloride and sulfate contents are usually somewhat higher than ia the crystalline product. Sodium dichromate is customarily shipped at a concentration of 69%... 

A specific polymorph may be absolutely essential for a crystalline product, for example, one polymorph may have a more desirable color or greater hardness or disperse in water more easily than another polymorph. Often, one polymorphic form is more stable than another (for example, at 80°C the orthorhombic I form of ammonium nitrate is more stable than the trigonal form) at conditions to which a product is exposed. An interesting approach to... 

The complete characterization of a particulate material requires development of a functional relationship between crystal size and population or mass. The functional relationship may assume an analytical form (7), but more frequentiy it is necessary to work with data that do not fit such expressions. As such detail may be cumbersome or unavailable for a crystalline product, the material may be more simply (and less completely) described in terms of a single crystal size and a spread of the distribution about that specified dimension. 

Amorphous nylons are transparent. Heat-deflection temperatures are lower than those of filled crystalline nylon resins, and melt flow is stiffer hence, they are more difficult to process. Mold shrinkage is lower and they absorb less water. Warpage is reduced and dimensional stabiUty less of a problem than with crystalline products. Chemical and hydrolytic stabiUty are excellent. Amorphous nylons can be made by using monomer combinations that result in highly asymmetric stmctures which crystalline with difficulty or by adding crystallization inhibitors to crystalline resins such as nylon-6 (61). 

Isoxazolines with alkyl substituents are also all liquids (or low melting solids) and incorporation of aryl substituents results in crystallinity. Introduction of carboxy substituents and endocyclic carbonyl or imino groups also has the anticipated effect, with crystalline products being isolated. These trends are illustrated by the data compiled in Table 2. 

Coefficient of Variation One of the problems confronting any user or designer of crystallization equipment is the expected particle-size distribution of the solids leaving the system and how this distribution may be adequately described. Most crystalline-product distributions plotted on arithmetic-probability paper will exhibit a straight line for a considerable portion of the plotted distribution. In this type of plot the particle diameter should be plotted as the ordinate and the cumulative percent on the log-probability scale as the abscissa. 

A solution of 7-chloro-2.3-dlhydro-1-acetyl-S-phenyl-1H-1,4-benzodlazepine-4-oxlde 1 (7 0 g, 22 mmol) in AC20 (60 mL) was relKjxed lor 7 h. The solvent was removed m vacuum arxl the residue was triturated with EtaO. The crystalline product after recrystaillzation from hexane CH2CI2 gave 4.6 g ol 2 (59%), irp ITT-ITg-C. 

A. Ethyl Sodium Phthalimidoinalonate.—To a solution of 9.2 g. (0.4 gram atom) of sodium in 300 cc. of absolute alcohol at 60° is added, with efficient stirring, 126 g. (0.41 mole) of ethyl phthalimidomalonate (Org. Syn. Coll. Vol. i, 266). The mixture is rapidly chilled to 0° and the crystalline product filtered at once by suction and washed successively with two 200-cc. portions of absolute alcohol and two 200-cc. portions of ether. After first drying in a vacuum desiccator and then heating for eight hours imder 15 mm. pressure in a flask suspended in an oil bath at 145-155° (Note i), it weighs 108-III g. (82-85 per cent of the theoretical amount). 

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