Chlorofluorocarbons synthesis

The chlorofluorocarbons react with molten alkah metals and CCI2F2 reacts vigorously with molten aluminum, but with most metals they do not react below 200°C. An exception is the dechlorination of chlorofluorocarbons with two or more carbon atoms in the presence of Zn, Mg, or A1 in polar solvents. A commercial synthesis of chlorotriduoroethylene [79-38-9] employs this reaction ... 

Cmde HCl recovered from production of chlorofluorocarbons by hydrofluorination of chlorocarbons contains unique impurities which can be removed by processes described in References 53—62. CICN—CI2 mixtures generated by reaction of hydrogen cyanide and CI2 during the synthesis of (CICN) can be removed from the by-product HCl, by fractional distillation and recycling (see Cyanides) (59). 

A novel use of a chlorofluorocarbon is in the synthesis of a pyrone (30) from 1,1,1-trichlorotrifluoroethane. The key step involves Cu(I) catalysis. Pyrone (30) is a useful CF3 aromatic synthon, as it readily underwent (4 + 2) cycloaddition followed by spontaneous elimination of C02 (85-TL3947). 

The two SCFs most often studied—CO2 and water—are the two least expensive of all solvents. CO2 is nontoxic and nonflammable and has a near-ambient critical temperature of 31. UC. CO2 is an environmentally friendly substitute for organic solvents including chlorocarbons and chlorofluorocarbons. Supercritical water (Tc = 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. (See also Sec. 15 for additional discussion of supercritical fluid separation processes.)... 

The first reactions of fluorinated olefins in C02 reported by DeSimone et al. involved the free-radical telomerization of 1,1 -difluoroethylene29 and tetrafluor-oethylene.30 This work demonstrated the feasibility of carrying out free-radical reactions of highly electrophilic species in solvents other than expensive fluorocarbons and environmentally detrimental chlorofluorocarbons. The work has since been more broadly applied to the synthesis of tetrafluoroethylene-based, nonaqueous grades of fluoropolymers,31,32 such as poly(tetrafluoroethylene-co-peduoropropylvinyl ether) (Scheme 2). These reactions were typically carried out at between 20 and 40% solids in C02 at initial pressures of between 100 and 150 bars, and 30-35°C (Table 10.1). 

Production, import/Export, Use, Reiease, and Disposai. Although the production of carbon tetrachloride has been declining, humans are at risk of exposure to the compound at specific industrial locations where the compound is used or near chemical waste sites where emission to the environment may occur. Available data indicate that most carbon tetrachloride manufactured in this country is consumed in the synthesis of chlorofluorocarbons, but current quantitative data on the amounts of carbon tetrachloride imported and exported into and from the United States are sparse (CEH 1985 HSDB 1992). According the the Emergency Planning and Community Right-to Know Act of 1986, 43 U.S.C. Section 11023, Industries are required to submit substance release and off-site transfer information to the ERA. The Toxic Release Inventory (TRI), which contains this information for 1990, became available in May of 1992. This database is updated yearly and should provide a list of industrial production facilities and emissions. 

Methane is an important starting material for numerous other chemicals. The most important of these are ammonia, methanol, acetylene, synthesis gas, formaldehyde, chlorinated methanes, and chlorofluorocarbons. Methane is used in the petrochemical industry to produce synthesis gas or syn gas, which is then used as a feedstock in other reactions. Synthesis gas is a mixture of hydrogen and carbon monoxide. It is produced through steam-methane reforming by reacting methane with steam at approximately 900°C in the presence of a metal catalyst CH4 + H20 —> CO + 3H2. Alternately, methane is partially oxidized and the energy from its partial combustion is used to produce syn gas ... 

Carbon tetrachloride is used in the synthesis of chlorinated organic compounds, including chlorofluorocarbon refrigerants. It is also used as an agricultural fumigant and as a solvent in the production of semiconductors, in the processing of fats, oils and rubber and in laboratory applications (Lewis, 1993 Kauppinen et al., 1998). 

The synthesis of fluoropolymers in C02 is of particular interest since these polymers have historically been prepared in chlorofluorocarbons (CFCs) and other fluorinated solvents, as well as in water. Due to the association of CFCs with ozone-layer depletion, these solvents have been banned and replacement solvents must be found. Alternative fluorinated solvents are expensive and also have environmental concerns. 

Chloroform (trichloromethane, CHClj). Chloroform was first used as an anaesthetic in 1847 and its narcotic effects on the central nervous are well documented (ref. 4la). It has important applications as an intermediate in the chemical synthesis of a large number of industrial chemicals chlorofluorocarbons, dyes, drugs and pesticides. Its powerful solvent properties and low boiling point (6l°C) have made it a favorite for extractive and purification operations in preparing antibiotics, alkaloids, flavors and vitamins. 

Most other simple compounds whose history has been examined have been those of obvious industrial interest. Thus, fluorinated compounds have been discussed, especially the now controversial chlorofluorocarbons (CFCs).80 Another aliphatic chemical that has received exhaustive historical treatment, chiefly in the context of its industrial use, is lactic acid.81 The development of urea as a fertilizer has been studied,82 and a history provided of the synthesis of methanol.83... 

Process Economics Program Report SRI International. Menlo Park, CA, Isocyanates IE, Propylene Oxide 2E, Vinyl Chloride 5D, Terephthalic Acid and Dimethyl Terephthalate 9E, Phenol 22C, Xylene Separation 25C, BTX, Aromatics 30A, o-Xylene 34 A, m-Xylene 25 A, p-Xylene 93-3-4, Ethylbenzene/Styrene 33C, Phthalic Anhydride 34B, Glycerine and Intermediates 58, Aniline and Derivatives 76C, Bisphenol A and Phosgene 81, C1 Chlorinated Hydrocarbons 126, Chlorinated Solvent 48, Chlorofluorocarbon Alternatives 201, Reforming for BTX 129, Aromatics Processes 182 A, Propylene Oxide Derivatives 198, Acetaldehyde 24 A2, 91-1-3, Acetic Acid 37 B, Acetylene 16A, Adipic Acid 3 B, Ammonia 44 A, Caprolactam 7 C, Carbon Disulfide 171 A, Cumene 92-3-4, 22 B, 219, MDA 1 D, Ethanol 53 A, 85-2-4, Ethylene Dichloride/Vinyl Chloride 5 C, Formaldehyde 23 A, Hexamethylenediamine (HMDA) 31 B, Hydrogen Cyanide 76-3-4, Maleic Anhydride 46 C, Methane (Natural Gas) 191, Synthesis Gas 146, 148, 191 A, Methanol 148, 43 B, 93-2-2, Methyl Methacrylate 11 D, Nylon 6-41 B, Nylon 6,6-54 B, Ethylene/Propylene 29 A, Urea 56 A, Vinyl Acetate 15 A. 

As described above, the non-oxidative substitution of chlorine by activated fluorine is one of the most important synthetic routes from the industrial point of view. In these reactions, a C—Cl is replaced by a C—F bond using an appropriate fluorinating agent such as HF. Among all technically-relevant catalysed halogen exchange reactions, synthesis of chlorofluorocarbons, hydrochlorofluorocarbons, and hydrofluorocarbons performed according Eqn. (1) are doubtless the most important processes. 

A major impetus to research in this area during the past two decades (especially since the 1987 Montreal Protocol) has been the need to discover catalysts for the synthesis of alternatives to chlorofluorocarbons, specifically hydrofluorocarbons [83], which destroy the protective ozone layer by generating Cl atoms under the influence of UV radiation. 

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