Phosphorus chlorides, chlorination with

Biodegradation. Under aerobic conditions, biodegradation results in the mineralization of an organic compound to carbon dioxide and water and—if the compound contains nitrogen, sulfur, phosphorus, or chlorine—with the release of ammonium (or nitrite), sulfate, phosphate, or chloride. These inorganic products may then enter well-established geochemical cycles. Under anaerobic conditions, methane may be formed in addition to carbon dioxide, and sulfate may be reduced to sulhde. 

Chlorination. When 75 was treated with chlorine in the presence of aluminium chloride, initial chlorination took place at the 5-position, but the reaction was rather unselective 5,8-di-, 5,7,8-tri-, and 5,6,7,8-tetra-chloroisoquinolines were also formed (64JOC329). Perchlorination has been achieved by initial reaction of the isoquinoline-aluminium chloride complex with chlorine, as above, followed by treatment with phosphorus pentachloride at 270°C in an autoclave [66JCS(C)2328]. Treatment of 1,8-dimethylisoquinoline with NCS gave the 5-chloro derivative (91NKK-1193). Meisenheimer reaction of isoquinoline 2-oxides with phosphoryl chloride gave 1-chloroisoquinoline (84MI2). 

Dangerous materials may require special equipment. Chlorination with gaseous chlorine requires quite expensive storage facilities. Chlorination with chlorine, thionyl chloride, sulphuryl chloride, phosphorus oxychloride, phosphorus trichloride, or phosphorus pentachloride, all of which are fairly hazardous, requires off-gas treatment. Some of these reactants can be recycled. Pyrophoric solids such as hydrogenation catalysts, anhydrous aluminium trichloride for Friedel-Crafts reactions, or hydrides used as reducing agents should usually be handled using special facilities. Therefore, all of the above proce.sses are usually carried out in dedicated plants. 

Aryloxymethyl chlorides may be prepared by the reaction of sodium aryloxymethanesulfonates with phosphorus pentachloride. The chlorination of anisole does not, as previously reported, give phenoxymethyl chloride, but rather a mixture of p- and o-chloroanisoles. Similarly, anisole and other unsubstituted methyl aryl ethers undergo ring chlorination with phosphorus pentachloride and chlorine, whereas ring-chlorinated anisoles, such as />-chloroanisole, undergo chlorination at the methyl group with chlorine at 190-195° in the presence of a catalytic amount of phosphorus pentachloride. ... 

Complete chlorination of 4,4 -bipyridine to octachloro-4,4 -bipyridine is accomplished by vapor-phase chlorination at 555°C. Mono-, di-, tri-, and tetrachloro-4,4 -bipyridines substituted at the positions ortho to the nitrogen atoms are obtained at lower temperatures. 2,6-Dihydroxy-3-cyano-4,4 -bipyridine gives 2,5,6-trichloro-3-cyano-4,4 -bipyridine on reaction with phosphorus chlorides, ring substitution accompanying replacement... 

The most convenient synthesis of halogenopyrazines and -quinoxalines is by halogenation of pyrazinones and quinoxalinones with phosphoryl or other acid halides for example, 5-hydroxy-2-pyrazinecarboxylic acid, rather than 5(477)-pyrazinone-2-carboxylic acid, is chlorinated with phosphorus pentachloride/phosphoryl chloride to afford a 63% yield of 5-chloro-2-pyrazinecarbonyl chloride <1994SL814>. Sato and Narita provided an improved synthesis of various halogenopyrazines in which 2(l//)-pyrazinones were activated with chlorotrimethylsilane to give silyl ethers (Section 8.03.7.3). This procedure is most effective for synthesis of bromopyrazines whose overall yields are 62-81% <1999JHC783>. Bromopyrazine is directly prepared by treatment of 2-(l//)-pyrazinone with phosphoryl... 

The compound is produced by evaporating hydrochloric acid solutions of polonium (IV) 6, 26, 74), by heating the dioxide in carbon tetrachloride vapor 74), in hydrogen chloride, thionyl chloride or with phosphorus pentachloride 6) and by heating the metal in dry chlorine at 200°C (6, 25, 74). It is hygroscopic and hydrolyzes in moist air to a white solid, possibly a basic chloride (7)). The tetrachloride is soluble in thionyl chloride and in water with hydrolysis, and is moderately soluble in ethanol, acetone, and... 

Pyridine and quinoline /V-oxides react with phosphorus oxychloride or sulfuryl chloride to form mixtures of the corresponding a- and y-chloropyridines. The reaction sequence involves first formation of a nucleophilic complex (e.g. 270), then attack of chloride ions on this, followed by rearomatization (see also Section 3.2.3.12.5) involving the loss of the /V-oxide oxygen. Treatment of pyridazine 1-oxides with phosphorus oxychloride also results in an a-chlorination with respect to the /V-oxide groups with simultaneous deoxygenation. If the a-position is blocked substitution occurs at the y-position. Thionyl chloride chlorinates the nucleus of certain pyridine carboxylic acids, e.g. picolinic acid — (271), probably by a similar mechanism. 

Heating hydrazinopyrimidine (488) in diethyl oxalate gave 489, which upon chlorination with phosphorus oxychloride yielded (2-ethoxycarbonyl) triazolo[l,5-c]pyrimidine (491). The intermediate hydrazidoyl chloride 490 can be isolated under mild conditions (90T3897) (Scheme 96). 

The most widespread technique, however, is the chlorination of titanium dioxide with chlorine or chlorine-containing substances (carbon tetrachloride, chloroform, sulftuyl chloride, phosphorus oxychloride, silicon tetrachloride). These reactions give high yield at high temperatures (800 °C and more) the chlorination with free chlorine occurs at noticeable speed only in the presence of reducing agents (e.g., coal). If there is a lack of coal, the reaction forms carbon dioxide if there is an excess of coal, it releases carbon oxide ... 

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