Carbonate solvents

The two fluids most often studied in supercritical fluid technology, carbon dioxide and water, are the two least expensive of all solvents. Carbon dioxide is nontoxic, nonflammable, and has a near-ambient critical temperature of 31.1°C. CO9 is an environmentally friendly substitute for organic solvents including chlorocarbons and chloroflu-orocarbons. Supercritical water (T = 374°C) is of interest as a substitute for organic solvents to minimize waste in extraction and reaction processes. Additionally, it is used for hydrothermal oxidation of hazardous organic wastes (also called supercritical water oxidation) and hydrothermal synthesis. 

The submitters report that both l,4-diazabicyclo[2.2.2]octane and triethylamine have been used to catalyze this decomposition. Tri-ethylamine was less satisfactory as a catalyst because of its relatively rapid reaction with the solvent, carbon tetrachloride, to form triethylamine hydrochloride and because of difficulty encountered in separating triethylamine from the dicarbonate pi oduct. The 1,4-diazabicyclo-[2.2.2]octane was efficiently separated from the dicarbonate product by the procedure described in which the crude product was washed with very dilute aqueous acid. 

It is shown that solute atoms differing in size from those of the solvent (carbon, in fact) can relieve hydrostatic stresses in a crystal and will thus migrate to the regions where they can relieve the most stress. As a result they will cluster round dislocations forming atmospheres similar to the ionic atmospheres of the Debye- Huckel theory ofeleeti oly tes. The conditions of formation and properties of these atmospheres are examined and the theory is applied to problems of precipitation, creep and the yield point."... 

The free-radical chain reaction may also be terminated by coupling of two carbon-radical species. As solvent carbon tetrachloride is commonly used, where the A-bromosuccinimide is badly soluble. Progress of reaction is then indicated by the decrease of the amount of precipitated NBS and the formation of the succinimide that floats on the surface of the organic liquid layer. 

As a matter of fact, the main advantage in comparison with HPLC is the reduction of solvent consumption, which is limited to the organic modifiers, and that will be nonexistent when no modifier is used. Usually, one of the drawbacks of HPLC applied at large scale is that the product must be recovered from dilute solution and the solvent recycled in order to make the process less expensive. In that sense, SFC can be advantageous because it requires fewer manipulations of the sample after the chromatographic process. This facilitates recovery of the products after the separation. Although SFC is usually superior to HPLC with respect to enantioselectivity, efficiency and time of analysis [136], its use is limited to compounds which are soluble in nonpolar solvents (carbon dioxide, CO,). This represents a major drawback, as many of the chemical and pharmaceutical products of interest are relatively polar. 

It has been proposed that aromatic solvents, carbon disulfide, and sulfur dioxide form a complex with atomic chlorine and that this substantially modifies both its overall reactivity and the specificity of its reactions.126 For example, in reactions of Cl with aliphatic hydrocarbons, there is a dramatic increase in Ihe specificity for abstraction of tertiary or secondary over primary hydrogens in benzene as opposed to aliphatic solvents. At the same time, the overall rate constant for abstraction is reduced by up to two orders of magnitude in the aromatic solvent.1"6 The exact nature of the complex responsible for this effect, whether a ji-coinplex (24) or a chlorocyclohexadienyl radical (25), is not yet resolved.126- 22... 

The addition of 0.24 g of sulfur to 100. g of the solvent carbon tetrachloride lowers the solvent s freezing point by 0.28°C. What is the molar mass and molecular formula of sulfur ... 

The data of Smith [35] is reported graphically in Fig. 11 and shows the effect of pressure on the solubility of adamantane in various supercritical solvents (carbon dioxide, methane, and ethane) at 333 K. 

A graphical representation of diamantane solubility data [36] in various supercritical solvents (carbon dioxide and ethane at 333 K and methane at 353 K) is shown in Fig. 12. 

The reaction was carried out in the nonpolar, aprohc solvent carbon tetrachloride. 

A recent development in liquid-liquid extraction has been the use of supercritical fluids as the extraction-solvent. Carbon dioxide at high pressure is the most commonly used fluid. It is used in processes for the decaffeination of coffee and tea. The solvent can be recovered from the extract solution as a gas, by reducing the pressure. Super critical extraction processes are discussed by Humphrey and Keller (1997). 

When n = 0 or 1, the system appeared to be too rigid to allow the radical pair created upon hydrogen abstraction to form a carbon-carbon bond. Hence a considerable amount of chlorine appears in the product from radical abstraction from the solvent, carbon tetrachloride. When n = 2 the radicals are able to form a carbon-carbon bond. After a five-step workup of the crude irradiation product including reduction with LiAlH4, acetylation, dehydration, oxidation with ruthenium tetroxide, and hydrolysis a 16% yield of previously unreported 12-keto-3a-chlorestanol was obtained. However,... 

Preussmann, R., Angew. Chem., 1963, 75, 642 Removal of the solvent carbon tetrachloride (in which nitrosation had been effected) at ambient, rather than reduced, pressure caused a violent explosion at the end of distillation. Lowest possible temperatures should be maintained in the preparation. Other precursors seem more suitable as sources of diazomethane. 

The product from chlorination of 4,4-dithiodimorpholine exploded violently after vacuum stripping of the solvent carbon tetrachloride. As it was a published process that previously had been operated uneventfully, no cause was apparent. It seems remotely possible that an unstable A-eh loro derivative could have been produced by N—S bond cleavage if chlorination conditions had differed from those previously employed. 

Later on, product distribution studies15 of the ionic addition of chlorine to conjugated dienes, and in particular to cyclopentadiene, 1,3-cyclohexadiene, cis,cis-, trans,trans-and c ,fraws-2,4-hexadienes, and cis- and trans-1,3-pentadienes have supplied the first stereochemical data, showing that the stereochemistry of 1,4-addition is predominantly syn, although to an extent smaller than that of bromine addition. Moreover, the 1,2-addition is generally non stereoselective, except for the addition to the 3,4-bond of cis-and trans-1,3-pentadienes where the attack is 89-95% anti. Finally, appreciable amounts of cis- 1,2-dichlorides were obtained from the two cyclic dienes, whereas 2,4-hexadienes showed a preference for anti 1,2-addition, at least in the less polar solvents (carbon tetrachloride and pentane). On the basis of all these results the mechanism shown in equation 29 was proposed. 

Analogous investigations of deuteriated methanol were carried out on the OD-valency vibration roD = 2689 cm in CCI4 as the standard solvent (Tamres, 1952, Searless and Tamres, 1951). Altogether 12 aromatic compounds, including halogen-substituted ones, were used as solvents. In the series of solvents, carbon tetrachloride, benzene, toluene, 0-, m-, j-xylene and mesitylene, i/qd shifted from 2689 to 2670 in benzene and to 2655 cm in mesitylene. 

Asphaltene (asphaltenes) the brown to black powdery material produced by treatment of petroleum, petroleum residua, or bituminous materials with a low-boiling liquid hydrocarbon (e.g., pentane or heptane) soluble in benzene (and other aromatic solvents), carbon disulfide, and chloroform (or other chlorinated hydrocarbon solvents). 

The separation properties in SFE are dependent on the choice of solvents, as well as on the solutes. The most popular solvent, carbon dioxide, is a rather nonpolar solvent, which dissolves mainly nonpolar solutes. Solubilities of selected compounds in liquid carbon dioxide are given in Table 10.6. The solubility and selectivity can be altered by adding small amounts of polar solvents, called entrainers (e.g., water or ethanol). 

The mixture to be separated is fed, together with the entrainer, to the middle of the first column. Flere, the solvent, carbon dioxide and acetone, is supercritical to provide high solubility of the monoglycerides. The supercritical phase leaves the top of column I and goes to the lower part of column II. In column II, the binary solvent entrainer is subcritical and in the bottom of this column, the monoglyceride leaves, together with the entrainer. Part of it is returned as reflux to column I, whereas the rest goes to distillation for the separation of acetone. With a bottom temperature of... 

In one study of workers at a solvent production plant who breathed hexachlorobutadiene for long periods, the compound was shown to affect the function of the liver. Because the workers were also exposed to other solvents (carbon tetrachloride and perchloroethylene), it is not certain if this effect was caused by hexachlorobutadiene alone. Studies in mice showed that brief exposure to high concentrations of hexachlorobutadiene irritate the nose. The effects of breathing low levels of hexachlorobutadiene are not known. 

Hepatic Effects. Data in humans are limited to one study which reported significant dose-related increases in the concentration of serum bile acids in workers after inhalation exposure to hexachlorobutadiene (0.005-0.02 ppm) (Driscoll et al. 1992). The practical importance of this finding is reduced because workers were also potentially exposed to other solvents (carbon tetrachloride and perchloroethylene) and background information on other confounding variables was minimal. No studies were located regarding other hepatic effects in humans. 

As a solvent, carbon dioxide does have a number of advantages over more conventional techniques. Because the critical point is only at 304 K (i.e., 31°C), temperature sensitive substances can be extracted without any degradation. This is particularly... 

DESORPTION EFFICIENCY OF AROMATIC COMPOUNDS Sorbent Coconut Base Carbon 0.5 grams Solvent Carbon Disulfide 5 mL... 

Current methodologies for the manufacture of energetic materials such as NHTPB, Poly(NiMMO) and Poly(GlyN) etc. use environmentally undesirable solvents such as dichloromethane. However, the adoption of the Montreal Protocol by most of the countries has limited the use of these halogenated hydrocarbons. To address current and futuristic legislations, DERA Scientists have developed various strategies to enable the manufacture of energetic materials in an environmentally friendly manner. Such an approach is to use Uquid or supercritical carbon dioxide as a solvent Carbon dioxide exhibits supercritical fluid behavior at a temperature >31.1 °C and a pressure >73.8 bar. 

Carbonyl compound as solvent carbon cathode divided cell By g.l.c. 

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