With Organic Compounds

Similar reactions occur with organic compounds which contain hydroxyl groups, thus... 

All new information on chemical matters or original presentations and discussions of known material are published in scientific journals. The most important of these dealing with organic compounds are (the abbreviated names are given in parentheses) ... 

Conversely, these factors dictate that molecular orbital calculations on metals yield less reliable results than with organic compounds. 

The halogen fluorides are binary compounds of bromine, chlorine, and iodine with fluorine. Of the eight known compounds, only bromine trifluoride, chlorine trifluoride, and iodine pentafluoride have been of commercial importance. Properties and appHcations have been reviewed (1 7) as have the reactions with organic compounds (8). Reviews covering the methods of preparation, properties, and analytical chemistry of the halogen fluorides are also available (9). 

Reactions With Organic Compounds. Most organic compounds react vigorously exhibiting incandescence or even explosively with CIF3... 

Reactions with Organic Compounds. Tetrafluoroethylene and OF2 react spontaneously to form C2F and COF2. Ethylene and OF2 may react explosively, but under controlled conditions monofluoroethane and 1,2-difluoroethane can be recovered (33). Benzene is oxidized to quinone and hydroquinone by OF2. Methanol and ethanol are oxidized at room temperature (4). Organic amines are extensively degraded by OF2 at room temperature, but primary aHphatic amines in a fluorocarbon solvent at —42°C are smoothly oxidized to the corresponding nitroso compounds (34). 

Properties. Silver difluoride melts at 690°C, bods at 700°C, and has a specific gravity of 4.57. It decomposes in contact with water. Silver difluoride may react violently with organic compounds, quite often after an initial induction period. Provisions must be made to dissipate the heat of the reaction. Small-scale experiments must be mn prior to attempting large-scale reactions. 

Electrolysis of fluorosulfuric acid produces either S20 E2 [13709-32-5] (24) or SO2E2 [13036-75 ] plus OE2 (25), depending on specific conditions. Various reactions of fluorosulfuric acid with inorganic compounds are shown in Table 2, and with organic compounds in Table 3. 

Organic fluorine compounds were first prepared in the latter part of the nineteenth century. Pioneer work by the Belgian chemist, F. Swarts, led to observations that antimony(Ill) fluoride reacts with organic compounds having activated carbon—chlorine bonds to form the corresponding carbon—fluorine bonds. Preparation of fluorinated compounds was faciUtated by fluorinations with antimony(Ill) fluoride containing antimony(V) haUdes as a reaction catalyst. 

Thus, for a successful fluorination process involving elemental fluorine, the number of coUisions must be drasticaUy reduced in the initial stages the rate of fluorination must be slow enough to aUow relaxation processes to occur and a heat sink must be provided to remove the reaction heat. Most direct fluorination reactions with organic compounds are performed at or near room temperature unless reaction rates are so fast that excessive fragmentation, charring, or decomposition occurs and a much lower temperature is desirable. 

M. G. Voronkov and co-workers, in J. S. Pizey, ed.. Reactions of Sulfur with Organic Compounds, Consultants Bureau, New York, 1987, Chapt. 3. 

Reaction with Organic Compounds. Many organic reactions are catalyzed by acids such as HCl. Typical examples of the use of HCl in these processes include conversion of HgnoceUulose to hexose and pentose, sucrose to inverted sugar, esterification of aromatic acids, transformation of acetaminochlorobenzene to chloroaruHdes, and inversion of methone [1074-95-9]. 

Reaction with Organic Compounds. Aluminum is not attacked by saturated or unsaturated, aUphatic or aromatic hydrocarbons. Halogenated derivatives of hydrocarbons do not generally react with aluminum except in the presence of water, which leads to the forma tion of halogen acids. The chemical stabiUty of aluminum in the presence of alcohols is very good and stabiUty is excellent in the presence of aldehydes, ketones, and quinones. 

H. Adkins, Reactions of Hydrogen with Organic Compounds over Chromium Oxide andNickel Catalysts, University of Wisconsin Press, Madison, 1946. 

Sulfur dichloride undergoes many of the same reactions with organic compounds as described for sulfur monochloride. Addition to olefins affords a route to bis(2-chloroalkyl) sulfides and, ia certain cases, heterocycHc sulfides (159,160). 

The reactions of thionyl chloride with organic compounds having hydroxyl groups are important. Alkyl chlorides, alkyl sulfites, or alkyl chlorosulfites form from its reaction with aUphatic alcohols, depending on reaction conditions, stoichiometry, and the alcohol stmcture ... 

Titanium carbide may also be made by the reaction at high temperature of titanium with carbon titanium tetrachloride with organic compounds such as methane, chloroform, or poly(vinyl chloride) titanium disulfide [12039-13-3] with carbon organotitanates with carbon precursor polymers (31) and titanium tetrachloride with hydrogen and carbon monoxide. Much of this work is directed toward the production of ultrafine (<1 jim) powders. The reaction of titanium tetrachloride with a hydrocarbon-hydrogen mixture at ca 1000°C is used for the chemical vapor deposition (CVD) of thin carbide films used in wear-resistant coatings. 

In both processes, care must be taken in dealing with organic compounds that either steam distill or form azeotropes. 

Reactions with Organic Compounds. The addition of biomine to unsatuiated carbon compounds occurs readily. 

Table 3. Reaction of CI2O With Organic Compounds...

In the recent years intensive studies related to modification of silica with organic compounds of various chemical nature have being conducted in order to concentrate selectively metal ions from solutions and then to perform their analytical determination directly in the sorbent phase, or after that, to elute with appropriate reagents in solution. 

Metal impurities can be determined qualitatively and quantitatively by atomic absorption spectroscopy and the required purification procedures can be formulated. Metal impurities in organic compounds are usually in the form of ionic salts or complexes with organic compounds and very rarely in the form of free metal. If they are present in the latter form then they can be removed by crystallising the organic compound (whereby the insoluble metal can be removed by filtration), or by distillation in which case the metal remains behind with the residue in the distilling flask. If the impurities are in the ionic or complex forms, then extraction of the organic compound in a suitable organic solvent with aqueous acidic or alkaline solutions will reduce their concentration to acceptable levels. 

Chromium trioxide (chromic anhydride) [1333-82-0] M 100.0, m 197°, dec at 250° to Cr203, d 2.70 (pK 0.74, pK 6.49, for H2Cr04, chromic acid). Red crystals from water (0.5mL/g) between 100° and -5°, or from water/conc HNO3 (1 5). It separates when potassium or sodium dichromate are dissolved in cone H2SO4. Dried in a vacuum desiccator over NaOH pellets hygroscopic, powerful oxidant, can ignite with organic compounds. It is a skin and pulmonary IRRITANT. 

In catalytic incineration, there are limitations concerning the effluent streams to be treated. Waste gases with organic compound contents higher than 20% of LET (lower explosion limit) are not suitable, as the heat content released in the oxidation process increases the catalyst bed temperature above 650 °C. This is normally the maximum permissible temperature to which a catalyst bed can be continuously exposed. The problem is solved by dilution-, this method increases the furnace volume and hence the investment and operation costs. Concentrations between 2% and 20% of LET are optimal, The catalytic incinerator is not recommended without prefiltration for waste gases containing particulate matter or liquids which cannot be vaporized. The waste gas must not contain catalyst poisons, such as phosphorus, arsenic, antimony, lead, zinc, mercury, tin, sulfur, or iron oxide.(see Table 1.3.111... 

An alternative oxidizing agent, similar to chromic acid in its reactions with organic compounds, is potassium permanganate (KMn04). 

Solutions of alkali metals in liquid ammonia have been developed as versatile reducing agents which effect reactions with organic compounds that are otherwise difficult or impossible/ Aromatic systems are reduced smoothly to cyclic mono- or di-olefins and alkynes are reduced stereospecifically to frani-alkenes (in contrast to Pd/H2 which gives cA-alkenes). 

P. S. Bailey, Ozonation in Organic Chemistry, Vol. 1, Olefinic Compounds, Academic Press, New York, 1978, 272 pp. Vol. 2, Nonolefinic Compounds, 1982, 496 pp. S. D. Razumovski and G. E. Zaikov, Ozone and Its Reactions with Organic Compounds, Elsevier, Amsterdam, 1984, 404 pp. 

B. Ranby and J. F. Rabek (eds.) Singlet Oxygen Reactions with Organic Compounds and Polymers, Wiley, Chichester, 1978, 331 pp. 

In reactions with organic compounds FCIO3 acts either as an oxidant or as a 1- or 2-centre electrophile which can therefore be used to introduce either F, a -CIO3 group, or both F and O into the molecule. As FCIO3 is highly susceptible to nucleophilic attack at Cl it reacts readily with organic anions ... 

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