Synthesis and Properties of Alkylene (Dialkyl) Dithiophosphate Derivatives of Thionyl Chloride

Alkylene (dialkyl) dithiophosphate derivatives of thionyl chloride of the general formula (S)SS(O)Cl and (RO)₂(S)SS(O)Cl where G = ─ CH₂(CH₃)₂CCH₂─, ─ CH₂CH₂CH(CH₃)─, ─ C(CH₃)₂CH₂CH(CH₃)─ and R = i-C₃H₇, have been synthesized by reacting thionyl chloride with alkylene/dialkyl dithiophosphates in a 1:1 molar ratio in refluxing benzene. A similar reaction in a 1:2 molar ratio yields the corresponding products of the type (S₂)₂S═O and [(RO))₂PS₂]₂S═O. It is interesting to note here that the sulfur atom of the thionyl chloride has been retained in the product, which is evidenced by sulfur analysis. The products thus obtained are light yellow colored semi solid (1:1 products) and orange colored liquids (1:2 products); and are soluble in common organic solvents. These new compounds have been characterized by elemental analysis, molecular weight measurements, and spectroscopic [IR and NMR (¹H and ³¹P)] studies. These compounds are found to be biologically active against bacteria S.aureus and E.coli.     

Regioselective Intramolecular Carbon-Hydrogen Insertion in Copper-Catalyzed Carbenoid Decompositions of cis-1-Methyl-3-Arylcyclohexane-1-Diazomethyl Ketones : Some Synthetic Applications

Recently, we have developed¹ a new route for the stereo-specific introduction of an angular carboxyl or functionalized methyl groups² in a rigid hydrophenanthrene moiety. The key step in this approach is a regioselective intramolecular α-keto carbenoid insertion across the benzylic C-H bond (at C-4a) in CuSO₄-catalyzed thermal decomposition of the diazoketones and to the corresponding tetracyclic ketones and in moderate to good yields. A modified procedure³ of carbenoid decomposition of these diazoketones, in the presence of Cu₂O under irradiation with tungsten filament lamp, improves the yields of the desired C-H insertion products. Thus, the ketones and have been prepared now in consistently higher yields (53-55%) from the pure diazoketones , m.p. 125-127°, and , m.p.     

The Structure of o-Hydroxyaryloxy-bis-(o-arylenedioxy)-phosphoranes and their Acid-Base Properties

Abstract

The crystalline phosphoranes have been obtained. IR-, UV- and NMR spectra of phosphoranes (Ia,b) and their interaction products with nitrogen bases have been investigated. It was determined that phosphoranes have structure (I) with pentacoordinate phosphorus and phenolic hydroxy group, while their products of interactions with nitrogen bases have the ionic structure (II) with hexacoordinate phosphorus (II). The X-ray difraction approves the structure (I) for phosphorane Ib.     

PEG-600-mediated,green and efficient,tandem syntheses of N-subtituted-2-styrylquinazolin-4- ones

Polyethylene glycol (PEG)-mediated, green and efficient, tandem syntheses of N-subtituted-2-styrylquinazolinones are being reported. Condensation of anthranilamide (1) with acetic anhydride in PEG-600, at 100°C for 1 hr gave 2-methyl-3H-quinazoline-4-one (2). Treatment of 2 with benzaldehydes in PEG-600, at 100°C for 2–3 hr, gave 2-styrylquinazolinone-4-ones (3) in excellent yields. Treatment of 3 (a–d) either with dimethyl sulfate (DMS), diethyl sulfate (DES), or with Ph-CH₂-Cl, individually in PEG-600, at 100°C for 1–2 hr without using any base, followed by simple processing resulted in N-substituted-2-styrylquinazolin-4-ones 5 (a–l). In an alternative approach, reaction of 4 (a–c) with benzaldehydes in PEG-600, at 100°C for 1–2 hr, without using any base, followed by simple processing resulted in 5 (a–l). 4 (a–c) were prepared by treatment of 2 with either DMS, DES, or with Ph-CH₂-Cl, individually, in the presence of PEG-600 as reaction medium, at 100°C for 1–2 hr without using any base. Both the sequence of reactions, 1 2 3 5 or 1 2 4 5 could be carried out in tandem in an efficient manner in PEG-600 without the isolation of any intermediates. The structures of all the new compounds synthesized in this work have been established on the basis of their spectroscopic data and analytical data.     

Chain-extending of Hydroxytelechelic Polybutadiene: Synthesis and Characterization

Extension of hydroxytelechelic polybutadiene oligomers ( 3200 g/mol) is performed in mild conditions, in order to avoid backbone modifications, using succinic anhydride or methylenedicyclohexyl diisocyanate. The two routes present significative extension of the initial oligomers. Extension through the anhydride route, in the presence of DCC and DMAP, leads to new hydroxytelechelic oligomers ( 8000 g/mol). Extension through the diisocyanate route, catalyzed by DBTL at 65°C leads to hydroxytelechelic oligomers of higher average molecular weight ( 20000 g/mol). New materials are characterized by FTIR/¹H-NMR and changes in their Tg according to , are discussed. The influence of reaction time on the length of the macromolecular chains is also studied.     

Reactions of Ammonium Alkylene Dithiophosphates with Phosphorus Trichloride and Thiophosphoryl Chloride *

Phosphorus trichloride and thiophosphoryl chloride derivatives of alkylene dithiophosphates of the type PCl_{3 ? n} () _n and P(S)Cl_{3? n} () _n (where G = -CH₂CH₂CHMe-, -CMe₂CMe₂-, -CH₂CH₂CH₂CH₂- and -CMe₂CH₂ CHMe-, n = 1, 2, 3] have been synthesized for the first time by reacting the ammonium salt of alkylene dithiophosphoric acid with phosphorus trichloride and thiophosphoryl chloride in different stoichiometric ratios under anhydrous reaction conditions. The newly synthesized derivatives are either colorless liquids or viscous semisolids, hygroscopic in nature and are soluble in common organic solvents. These are characterized by elemental analysis, molecular weight determinations and physicochemical studies IR, NMR (¹H and ³¹P). On the basis of above studies the formation of P-S-P and S = P–S–P(S) chemical linkages have been established. ²³¹P NMR studies provide convincing evidence regarding the chemical bonding mode in these derivatives.