Ammonia, fluorination

Initial C-perfluoroalkylation of p diketones occurs during their UV irradiation in the presence of perfluoroalkyl iodides in liquid ammonia Fluorinated enami-noketones are obtained by subsequent ammonolysis of a difluoromethylene group and removal of the acetyl group [131] C-alkylation of dimethyl malonate takes... 

Chlorodifluorophosphine (57) is converted into the phosphorane (58) when it reacts with ammonia. Fluorination of the phosphine (59) leads to the phosphorane... 

CARBONATO de PLOMO (Spanish) (598-63-0) Contact with hot water, acids, acid fumes, or lead oxide causes decomposition with formation of carbon dioxide. Incompatible with acids, ammonia, fluorine, germanium, hydrozoic acid, lead diacetate, magnesium, mercurous chloride, methyl isocyanoacetate, silver nitrate, sodium peroxyborate, titanium, trinitrobenzoic acid, urea nitrate. 

Ammonia reacts violently with halogens. At ordinary temperatures, a mixture of ammonia-fluorine bursts into flame. On heating, the products, nitrogen trihalides resulting from reactions with halogens, explode violently. Violent reactions occur with many interhalogen compounds of fluorine, as well as with many inorganic chlorine compounds. The latter include chlorites, hypochlorites, chlorine monoxide, and certain metal chlorides, such as silver chloride or mercuric chloride, which form shock-sensitive nitrides. 

Evidence for the solvated electron e (aq) can be obtained reaction of sodium vapour with ice in the complete absence of air at 273 K gives a blue colour (cf. the reaction of sodium with liquid ammonia, p. 126). Magnesium, zinc and iron react with steam at elevated temperatures to yield hydrogen, and a few metals, in the presence of air, form a surface layer of oxide or hydroxide, for example iron, lead and aluminium. These reactions are more fully considered under the respective metals. Water is not easily oxidised but fluorine and chlorine are both capable of liberating oxygen ... 

Bromine Ammonia, carbides, dimethylformamide, fluorine, ozone, oleflns, reducing materials including many metals, phosphine, silver azide... 

Chlorine Ammonia, acetylene, alcohols, alkanes, benzene, butadiene, carbon disulflde, dibutyl phthalate, ethers, fluorine, glycerol, hydrocarbons, hydrogen, sodium carbide, flnely divided metals, metal acetylides and carbides, nitrogen compounds, nonmetals, nonmetal hydrides, phosphorus compounds, polychlorobi-phenyl, silicones, steel, sulfldes, synthetic rubber, turpentine... 

Hydrazine Alkali metals, ammonia, chlorine, chromates and dichromates, copper salts, fluorine, hydrogen peroxide, metallic oxides, nickel, nitric acid, liquid oxygen, zinc diethyl... 

Hydrogen chloride Acetic anhydride, aluminum, 2-aminoethanol, ammonia, chlorosulfonic acid, ethylenediamine, fluorine, metal acetylides and carbides, oleum, perchloric acid, potassium permanganate, sodium, sulfuric acid... 

Iodine Acetaldehyde, acetylene, aluminum, ammonia (aqueous or anhydrous), antimony, bromine pentafluoride, carbides, cesium oxide, chlorine, ethanol, fluorine, formamide, lithium, magnesium, phosphorus, pyridine, silver azide, sulfur trioxide... 

Nitric oxide Aluminum, BaO, boron, carbon disulflde, chromium, many chlorinated hydrocarbons, fluorine, hydrocarbons, ozone, phosphine, phosphorus, hydrazine, acetic anhydride, ammonia, chloroform, Fe, K, Mg, Mn, Na, sulfur... 

Chloroacetate esters are usually made by removing water from a mixture of chloroacetic acid and the corresponding alcohol. Reaction of alcohol with chloroacetyl chloride is an anhydrous process which Hberates HCl. Chloroacetic acid will react with olefins in the presence of a catalyst to yield chloroacetate esters. Dichloroacetic and trichloroacetic acid esters are also known. These esters are usehil in synthesis. They are more reactive than the parent acids. Ethyl chloroacetate can be converted to sodium fluoroacetate by reaction with potassium fluoride (see Fluorine compounds, organic). Both methyl and ethyl chloroacetate are used as agricultural and pharmaceutical intermediates, specialty solvents, flavors, and fragrances. Methyl chloroacetate and P ionone undergo a Dar2ens reaction to form an intermediate in the synthesis of Vitamin A. Reaction of methyl chloroacetate with ammonia produces chloroacetamide [79-07-2] C2H ClNO (53). 

Ammonia. Ammonia (qv) reacts with excess fluorine ia the vapor phase to produce N2, NF, N2F2, HF, and NH F. This reaction is difficult to control ia the vapor phase because of the iatense heat of reaction, and ia some cases only N2 and HF are produced. Nitrogen trifluoride was obtained ia 6% yields ia a gas-phase reaction over copper (42). Yields of ca 60% are achieved by the reaction of fluorine and ammonia ia a molten ammonium acid fluoride solution (43,44). 

Fluorine reacts with ammonia in the presence of ammonium acid fluoride to give nitrogen trifluoride, NF. This compound can be used as a fluorine source in the high power hydrogen fluoride—deuterium fluoride (HF/DF) chemical lasers and in the production of microelectronic siUcon-based components. 

In addition, there are other methods of manufacture of cryoHte from low fluorine value sources, eg, the effluent gases from phosphate plants or from low grade fluorspar. In the former case, making use of the fluorosiHcic acid, the siHca is separated by precipitation with ammonia, and the ammonium fluoride solution is added to a solution of sodium sulfate and aluminum sulfate at 60—90°C to precipitate cryoHte (26,27) ... 

CoF is used for the replacement of hydrogen with fluorine in halocarbons (5) for fluorination of xylylalkanes, used in vapor-phase soldering fluxes (6) formation of dibutyl decalins (7) fluorination of alkynes (8) synthesis of unsaturated or partially fluorinated compounds (9—11) and conversion of aromatic compounds to perfluorocycHc compounds (see Fluorine compounds, organic). CoF rarely causes polymerization of hydrocarbons. CoF is also used for the conversion of metal oxides to higher valency metal fluorides, eg, in the assay of uranium ore (12). It is also used in the manufacture of nitrogen fluoride, NF, from ammonia (13). 

Manufacture and Economics. Nitrogen tritiuoride can be formed from a wide variety of chemical reactions. Only two processes have been technically and economically feasible for large-scale production the electrolysis of molten ammonium acid fluoride and the direct fluorination of the ammonia in the presence of molten ammonium fluoride. In the electrolytic process, NF is produced at the anode and H2 is produced at the cathode. In a divided cell of 4 kA having nickel anodes, extensive dilution of the gas streams with N2 was used to prevent explosive reactions between NF and H2 (17). 

Chemica.1 Properties. With few exceptions, SF is chemically inert at ambient temperature and atmospheric pressure. Thermodynamically SF is unstable and should react with many materials, including water, but these reactions are kineticaHy impeded by the fluorine shielding the sulfur. Sulfur hexafluoride does not react with alkah hydroxides, ammonia, or strong acids. 

TiF is a colorless, very hygroscopic soHd and is classified as a soft fluorinating reagent (4), fluorinating chlorosilanes to fluorosilanes at 100°C. It also forms adducts, some of them quite stable, with ammonia, pyridine, and ethanol. TiF sublimes at 285.5°C, and melts at temperatures >400° C. It is soluble in water, alcohol, and pyridine, hydroly2ing in the former, and has a density of 2.79 g/mL. 

Other applications of zirconium tetrafluoride are in molten salt reactor experiments as a catalyst for the fluorination of chloroacetone to chlorofluoroacetone (17,18) as a catalyst for olefin polymerization (19) as a catalyst for the conversion of a mixture of formaldehyde, acetaldehyde, and ammonia (in the ratio of 1 1 3 3) to pyridine (20) as an inhibitor for the combustion of NH CIO (21) in rechargeable electrochemical cells (22) and in dental applications (23) (see Dentalmaterials). 

Magnesium is not attacked seriously by dry chlorine [7782-50-5] iodine [7553-56-2] bromine, or fluorine [7782-41 ] gas. However, the presence of water promotes attack. Similarly, sulfur dioxide, ammonia, and fluorine-containing refrigerants do not attack in the absence of water. 

Tin does not react directly with nitrogen, hydrogen, carbon dioxide, or gaseous ammonia. Sulfur dioxide, when moist, attacks tin. Chlorine, bromine, and iodine readily react with tin with fluorine, the action is slow at room temperature. The halogen acids attack tin, particularly when hot and concentrated. Hot sulfuric acid dissolves tin, especially in the presence of oxidizers. Although cold nitric acid attacks tin only slowly, hot concentrated nitric acid converts it to an insoluble hydrated stannic oxide. Sulfurous, chlorosulfuric, and pyrosulfiiric acids react rapidly with tin. Phosphoric acid dissolves tin less readily than the other mineral acids. Organic acids such as lactic, citric, tartaric, and oxaUc attack tin slowly in the presence of air or oxidizing substances. 

The breadth of reactions catalyzed by cobalt compounds is large. Some types of reactions are hydrotreating petroleum (qv), hydrogenation, dehydrogenation, hydrodenitrification, hydrodesulfurization, selective oxidations, ammonoxidations, complete oxidations, hydroformylations, polymerizations, selective decompositions, ammonia (qv) synthesis, and fluorocarbon synthesis (see Fluorine compounds, organic). 

---