ORGANIC PHOSPHORUS COMPOUNDS: II: PREPARATION OF CHLOROMETHANEPHOSPHONYL DICHLORIDE

1953 ◽  
Vol 31 (10) ◽  
pp. 976-983 ◽  
Author(s):  
R. A. B. Bannard ◽  
J. R. Gilpin ◽  
G. R. Vavasour ◽  
A. F. McKay

Hydroxymethanephosphonic acid was prepared by treating paraformaldehyde with phosphorus trichloride at atmospheric pressure and subsequent hydrolysis of the resultant complex. Chloromethanephosphonyl dichloride was obtained by chlorination of hydroxymethanephosphonic acid with thionyl.chloride in the presence of pyridine. On the other hand hydroxymethanephosphonic acid combined slowly with phosphorus pentachloride to give the hitherto unknown dichlorophosphorylmethanephosphonyl dichloride, Cl2P(O)OCH2P(O)Cl2, together with chloromethanephosphonyl dichloride. The structure of dichlorophosphorylmethanephosphonyl dichloride was confirmed by its conversion with phosphorus pentachloride at 78 °C into chloromethanephosphonyl dichloride and phosphorus oxychloride. The preparation of chloromethanephosphonyl dichloride by interaction of paraformaldehyde and phosphorus trichloride in an autoclave at 250 °C was studied in reference to the influence of heating time on the yield.

1977 ◽  
Vol 22 (3) ◽  
pp. 415-422 ◽  
Author(s):  
M. G. Rodel ◽  
D. E. Armstrong ◽  
R. F. Harris

1968 ◽  
Vol 46 (22) ◽  
pp. 3573-3577 ◽  
Author(s):  
Arlen W. Frank

A novel carbon–phosphorus bond cleavage is described. Chloromethylphosphonic dichloride (2) and bis(chloromethyl)phosphinic chloride (1) both react smoothly and quantitatively with phosphorus pentachloride at 95–100°, giving carbon tetrachloride and a P(III) fragment containing one less carbon–phosphorus bond: phosphorus trichloride from 2 and trichloromethylphosphonous dichloride from 1. Under the same conditions, tris(chloromethyl)phosphine oxide (3) forms a complex (4) which subsequently breaks down to trichlorobis(trichloromethyl)phosphorane (5), diphenyl chloromethylphosphonate (7) suffers chlorination without cleavage, and tetrakis(chloromethyl)phosphonium chloride (6) is neither chlorinated nor cleaved. A concerted mechanism is proposed which accounts for ail of these results.


2015 ◽  
Vol 03 (02) ◽  
pp. 39-51 ◽  
Author(s):  
Irenus A. Tazisong ◽  
Zachary N. Senwo ◽  
Zhongqi He

1994 ◽  
Vol 47 (12) ◽  
pp. 2235 ◽  
Author(s):  
MG Banwell ◽  
CJ Cowden

Convergent routes to the title nuclei, (1) and (6), have been developed. Thus, Suzuki coupling of boronic acid (8) with aryl bromide (9) gave the biarylylcarbamate (7) which, on treatment with phosphorus oxychloride (POCl3), underwent Bischler-Napieralski cyclization to give, after acid hydrolysis, the Amaryllidaceae alkaloid crinasiadine (1). The cyclization reaction proceeds via an intermediate chlorophenanthridine (11) which can be isolated and N- methylated. Hydrolysis of the resulting iminium species (17) then afforded N- methylcrinasiadine (2). On the other hand, hydrogenolytic dechlorination of compound (II) affords trisphaeridine (14). Related chemistry has been employed in the preparation of 2,3,4,4a-tetrahydro[1,3] dioxolo [4,5-j]phenanthridin-6(5H)-one (6), the tetracyclic skeleton associated with the narcissus alkaloids lycoricidine (3) and narciclasine (4). Thus, treatment of the gem- dibromocyclopropane (20) with silver cyanate resulted in ring opening thereby affording the allylic isocyanate (25) which could be intercepted with added methanol to give carbamate (24). Suzuki coupling of this last compound with boronic acid (8) gave product (18) which was subjected to treatment with and resulted in the formation of (�)-(6). This latter sequence could be adapted to the preparation of both (R)-(6) and (S)-(6).


2021 ◽  
Vol 271 ◽  
pp. 03054
Author(s):  
Qiamin Gu ◽  
Chuanxin Zhao ◽  
Hailing Xi ◽  
Min Liu ◽  
Gaoyun Chen

Organophosphorus hydrolase can effectively degrade organic phosphorus compounds such as sarin. In this study, we constructed a recombinant Bacillus subtilis mutant expressing organophosphorus hydrolase, measured the effect of the mutant on the degradation rate of nerve agent sarin, and selected the optimal mutation scheme. Three different hydrolase mutant genes, 257L, 257Y and 303T, were ligated to PMA0911 vector and transferred into Bacillus subtilis WB800 to construct the target recombinant strain successfully. The recombinant bacteria secreted the target protein by fermentation. The effect of enzyme protein on the degradation of sarin was determined by the benzidine method. The optimal mutant was screened, and its enzymatic performance was explored. The effects of three organophosphorus hydrolase mutants on the hydrolysis rate of sarin were detected. The results showed that the 257Y mutant accelerated the hydrolysis of sarin significantly. Point mutation can improve the enzyme activity of wild-type organophosphorus hydrolase to a certain extent, laying the foundation for subsequent in-depth research.


Author(s):  
H. W. Harvey

A simple photoelectric meter is described which allows the molybdenum blue formed in sea water, due to the presence of phosphate, to be estimated within that due to ± 0·25 mg. phosphate-P per m.3.The effects of concentration of acid, molybdate, reductant, temperature and suspended particles on the rate of formation, fading and amount of molybdenum blue, formed in sea waters containing phosphate are detailed.Intramolecular changes taking place during storage of molybdate solutions, and while being mixed with acidified sea water, have been investigated.The hydrolysis of organic phosphorus compounds in acidified sea water at 140° C , and the prevention of arsenate formation, are described.Procedures, resulting from these investigations, for the estimation of phosphate, and of total phosphorus, are described.The growth of bacteria and the physical adsorption of organic phosphorus compounds in solution on the walls of glass vessels used for storage of sea water have been investigated, and a method of prevention evolved.


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