Tetraphosphorus decasulfide, reaction

Tetraphosphorus decasulfide, reaction with chloromethylphosphomc di-chlonde, 46, 21... 

The synthesis and some reactions of meso-ionic 1,2-dithioM-ones (388) have been recently reported. The brown compound 388, R = R = Ph, has been prepared by several methods (i) the reaction betw i l,l,3,3-tetrabromo-l,3-diphenylacetone (PhCBrjCOCBrjPh) and potassium ethyl xanthate, (ii) the reaction between 1,3-diphenyl-propanetrione hydrate and tetraphosphorus decasulfide, (iii) 1,3-diphenylpropanetrione with hydrogen sulfide-hydrogen chloride in ethanol-chloroform yields the salt 389, R = R = Ph, X = Cl, which gives the meso-ionic I,2-dithiol-4-one with triethylamine, pyridine, or aqueous sodium bicarbonate. ... 

Pyridine compounds in which phosphorus is directly attached to a ring carbon are relatively rare. Phosphorus nucleophiles are not able to replace ring hydrogen atoms in pyridines and pyridine 1-oxides. Some time ago it was found that pyridine yields a zwitterion (170) when it is heated under reflux in the presence of tetraphosphorus decasulfide (Scheme 105) (68MI20500). Recently, a product that contains a C—P bond was isolated after extended heating under the same conditions followed by treatment with hydrochloric acid (81 JCR(S)285). However, it is uncertain whether free pyridine undergoes reaction in this case. Attack by phosphorus nucleophiles on salts is well established. Af-Methylacridinium methosulfate affords a stable isolable 9,10-dihydro adduct (171) that readily forms a... 

The catalysed reaction of hydrogen sulfide on ketones or their acetals, or the thionation of carbonyl derivatives by tetraphosphorus decasulfide, or some modified version of this phosphorous compound as Lawesson, Davy and Heimgartner reagents are classically used [119, 120] to prepare the thioketones (2). 

More stable than many other thiocarbonyl compounds, thioamides have been known and used for a long time. Reliable methods of synthesis [119] were introduced as early as 1815 by Gay-Lussac for the reaction of nitriles with hydrogen sulfide and 1878 by Hoffman for the thionation of amides by means of tetraphosphorus decasulfide. 

Synthesis of oil soluble micellar calcium thiophosphate was performed in a one-step process involving the reaction of calcium oxide, tetraphosphorus decasulfide and water in the presence of an alkylaryl sulfonic acid. This product could be defined as a calcium thiophosphate hard-core surrounded by a calcium alkylarylsulphonate shell in accordance with a reverse micelle type association in oil. Three micellar products with the same chemical nature core were prepared, each with different core/shell ratio of 0.44, 0.92 and 1.54. Better performances are expected with products of higher core/shell ratios. The antiwear performance of micellar calcium carbonates is directly linked to the size of the mineral CaC03 colloidal particles. At a concentration of 2 % micellar cores, no antiwear effect is observed whatever the micellar size. At an intermediate concentration of 4 % of micellar cores, the wear scar diameter is clearly dependent on the micellar size, slipping from 1.70 mm to 1.10 mm, then to 0.79 mm when the core diameter moves from 4.37 nm to 6.07 nm, then to 6.78 nm. Size dependence is increased at a concentration of 5 % in colloidal cores. This clearly confirms the size dependence of the micellar cores on their antiwear performance (Delfort et al.,... 

The reaction of 2,2,4,4-tetramethyl-l,3-cyclobutanedione with tetraphosphorus decasulfide (P4S10) led to ring cleavage and the formation of the intermediate dimethylthioketene, which underwent [2+2] cycloaddition after 12 h in refluxing pyridine to give 4-isopropylidene-3,3-dimethylthietane-2-thione 88 in nearly quantitative yield (Equation 28) <2004BCJ187>. 

One of the oldest methods is still being used sulfurisation of amides with tetraphosphorus decasulfide (P4S10). Although it involves heterogeneous reactions, it is often an efficient reagent, as in the synthesis of an intermediate towards Vinca alkaloid related compounds [21]. Ultrasonic activation was successful for the preparation of sugar derivatives [22] and thio-lactams [23]. 

Another route to thieno[2,3-6]quinolines is a three-step sequence starting with anilines. The reaction proceeds via conversion of the aniline derivative to an amide, which is then followed by treatment with tetraphosphorus decasulfide to generate dihydrothienoquinolines which are dehydrogenated to the thienoquinolines in fair to good yields (Scheme 49) <77S612>. 

The reaction of tetraphosphorus decasulfide with primary amines (1 12 M ratio) gives fhiophosphoryltriamides, SP(NHR2)3 with a 1 8 ratio, the product is a dithiophos-phoric acid diamide (RNH)2P(S)(SH) (Scheme 23). The dithioacid diamides form metal complexes, for example, Ni[S2P(NHPh)2]2. ... 

A widely used sulfurization agent is tetraphosphorus decasulfide, commonly named phosphorus pentasulfide. This reagent has been used with j -diketones, leading to 1,2-dithiolium salts.Yields seem to be improved when a mild oxidizing agent such as iodine is added. A side reaction, common when phosphorus pentasulfide is used, is the dealkyla-... 

For example, the reaction of alkylchlorides with tetraphosphorus decasulfide under pressure at elevated temperatures (200-270 C) leads to the formation of alkyl dichlorodithio-phosfiiates and dialkyl chlorotrithicphosphates. The transforma-tion of the latter into alkyl dichlorodithiophosphates by reaction with thiophosphoryl trichloride can easily be achieved. This two-step process can also be carried out as a "one-pot reaction" with satisfactory yields (9). 

The retro reaction was accomplished with boron sulfide <77JA5521 > or tetraphosphorus decasulfide <64CB1298>. Several 2-selenones have also been prepared <92ZN(B)898, 94S809>. 

Other Studies. - The P NMR chemical shifts of alcohols, carboxylic acids and phenols phosphitylated with 2-chloro-4,4,5,5-tetramethyl-dioxaphospholane have been correlated with substituent effects of phenols. P NMR spectroscopy has also been used to study activation pathways of aryl H-phosphonate ester condensation reactions, the conversion of allenyl and divinyl phosphines to 1- and 2-phosphadienes, the reaction of tetraphosphorus decasulfide with dialkyl disulfides, the reaction of phosphine with cyclic olefins, the chemical shift tensors of powder samples of phosphole derivatives, the reactions of alcohols and mercaptans with tetraphosphorus trichalcogen diiodides, the structure of aminomethanebisphosphonic acids, and reactions of 00-di-(2-ethylhexyl)dithiophosphoric acids. ... 

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