Phosphorus Chloride chlorinations

Chlor-oxyd, n. chlorine oxide, -phosphor, m. phosphorus chloride, -pikrin, n. chloropicrin. -platin, n. platinic chloride, -platinsiiure,. chloroplatinic acid, -quecksilber, n. mercury chloride (either one), -raucherung, /. chlorine fumigation. 

When 2.36 g of phosphorus was burned in chlorine, the product was 10.5 g of a phosphorus chloride. Its vapor rook 1.77 times as long to effuse as the same amount of CO, under... 

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. 

Uses. As chlorinating agent manufacture of other phosphorus chloride compounds producing iridescent metallic deposits... 

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... 

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. 

Hydroxy groups in activated positions are displaced by chlorine using phosphorus chlorides as for the pyridazine (680) (71MI42900). Halogen interchange reactions are to be expected. Bromination of the chloropyrazine (681) can be effected using bromine in chloroform (75JHC451). 

The chlorides of the Group VA elements are prepared in the following ways. Phosphorus trichloride is obtained by the reaction of white phosphorus with chlorine using an excess of phosphorus ... 

The application of the amidrazone method is limited. Most of the other published preparations are equally divided between electrophilic halogenation, nucleophilic displacement of halogen or nitro groups, and displacement of diazo or nitrosamino groups. The conversion of triazolinones into chlorotriazoles with phosphorus chlorides may be regarded as a nucleophilic displacement reaction of the hydroxytriazole tautomer, while the preparation of chlorotriazoles by the action of chlorine on thiones is regarded as oxidative chlorination. 

Phosphorus(Ill) chloride is manufactured from white phosphorus and chlorine in an exothermic reaction ... 

In an entirely different way the chlorination is facilitated by the addition of red phosphorus. In this case, phosphorus pentachloride is first formed from the phosphorus and chlorine this, acting on the acetic add, generates acetyl chloride, and this latter, with an excess of the acid, forms the anhydride. Direct experiments have shown that add-chlorides, as well as anhydrides, are substituted by chlorine with much greater ease than the corresponding adds in this fact the action of red phosphorus finds its explanation. Since a small amount of phosphorus is suflident for the chlorination of a large amount of acetic add, the question as to how this is continuously effected remains to be answered. In accordance with the above statements, the following reactions take place ... 

As a substitute for red phosphorus, sulphur is also recommended for the chlorination of aliphatic adds. This acts in a wholly similar manner, since it first forms sulphur chloride, which, reacting on the add, like phosphorus chloride, converts it into an add-chloride. The other phases of the reaction are similar to those given above. 

Replacement of Hydroxyl When (/(-Codeine is treated with phosphorus pentachloride or thionyl chloride allylic rearrangement occurs and a-chlorocodide is formed [238, 428], /3-Chlorocodide results when -codeine is heated under pressure with concentrated hydrochloric acid, but this doubtless arises by rearrangement of the a-isomer first formed [243], Bromocodide is produced by the interaction of (/(-codeine and phosphorus tribromide [428]. With phosphorus pentachloride dihydro- -codeine-A gives 8-chlorodihydrocodide, with thionyl chloride chlorination only occurs in the aromatic nucleus, and with phosphorus tribromide a poor yield of 8-bromodihydrocodide is obtained [240]. Tetrahydro- r-codeine gives tetrahydro-i/j-cblorocodide with phosphorus pentachloride [295]. 

A mixture of trans-3,5- and exo-cw-3,5-dichloro-tricyclo[2.2.1.0 ]heptanes 26 and 27 was obtained in excellent total yields on chlorination of norbornadiene with copper(II) chloride, thal-lium(III) chloride tetrahydrate and antimony(IV) chloride. The use of other halogenating agents such as thionyl chloride, chlorine and phosphorus(V) chloride leads to appreciable amounts of exo-5-.iyn-l- and ex o-cw-S.b-dichloronorbornenes in addition to 26 and 27. ... 

El 5.6 The only isolable nitrogen chloride is NCI3, and it is thermodynamically unstable with respect to its constituent elements (i.e., it is endoergic). The compound NCI3 is unknown. In contrast, both PCI3 and PClj are stable and can be prepared directly from phosphorus and chlorine. 

Phosphorus and Chlorine Contents. Phosphorus and chlorine contents of the samples in char residue at kOO C are shown in Table IV. Phosphorus content did not change by thermal decomposition in all samples. But chlorine content decreased by pyrolysis. Chlorine introduced by stannic chloride treatment hardly decreased, but that by grafting decreased easily by pyrolysis. Stannic chloride is not introduced in cotton in the form of stannic chloride, because the chlorine content of stannic chloride treated cellulose is very lower than that calculated from weight increase. X-ray diffraction trace of burned sample... 

New Jersey adopted a Toxic Catastrophe Prevention Act in 1986, which requires risk assessment by companies.167 The Kanawha Valley Hazardous Assessment Project in West Virginia developed worst-case scenarios for 12 chemical plants in the area.168 The chemicals studied included acrylonitrile, vinylidene chloride, butyl isocyanate, methylene chloride, chlorine, phosphorus trichloride, hydrogen sulfide, methyl isocyanate, phosgene, ethylene oxide, sulfur trioxide, and others... 

Until recently, most of these semi-synthetic penicillin antibiotics were manufactured from penicillin G by chemical methods (Scheme 8.8) [57], which involve many green chemsitry issues, including the use of stoichiometric amounts of the silylating agents, phosphorus chloride, and N,N-dimethylaniline, and a large volume of dichloromethane. Moreover, the chlorination has to be carried out at —40 °C. 

---