Substituent effects on the 31P NMR chemical shifts of arylphosphorothionates

Hernández, Jesús; Goycoolea, Francisco M.; Zepeda-Rivera, Denisse; Juárez-Onofre, Josué; Martínez, Karla; Lizardi, Jaime; Salas-Reyes, Magali; Gordillo, Barbara; Velázquez-Contreras, Carlos Arturo; García-Barradas, Óscar; Cruz-Sánchez, Samuel; Domínguez, Zaira

doi:10.1016/j.tet.2005.12.053

Cited by 20 publications

(8 citation statements)

References 35 publications

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“…Using 31 P NMR, we have found that the reaction of all 1,2,4‐dithiazolidines 1a , 1b , 1c , 1d , 1e , 1f , 1g with triphenylphosphines in CDCl 3 and CD 3 CN proceeds smoothly and the only products are the corresponding triphenylphosphinsulphides together with phenylisocyanates and carbonylsulfide which is consistent with previous results. Similar experiment with the least reactive triphenyl phosphite used in our previous study surprisingly showed that the parallel oxidation of trivalent phosphorus occurs and the product therefore contains a mixture of the desired triphenyl phosphorothioate (δ(CDCl 3 ) = 53.7 ppm) and triphenyl phosphate (δ(CDCl 3 ) = −17.3 ppm) in the ratios 1:3 – 1:5 depending on the water content (based on integration of peaks at 53.7 ppm and −17.3 ppm in 31 P NMR spectrum). This result could not be caused only by dissolved oxygen in deuterated solvent or by the presence of oxygen in the air above the sample in the NMR tube during measurement because the triphenyl phosphite itself does not undergo oxidation under these conditions.…”

Section: Resultssupporting

confidence: 71%

Mechanism of sulfur transfer from 1,2,4-dithiazolidine-3,5-diones to triphenylphosphines

Пономарьов

Padělková

Hanusek

2013

J. Phys. Org. Chem.

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The mechanism of sulfurization of substituted triphenylphosphines with 4-(3-and 4-substituted)-1,2,4dithiazolidine-3,5-diones in acetonitrile, dichloromethane, tetrahydrofuran and toluene at 25 C was studied. The reaction pathway involves rate-limiting initial nucleophilic attack of the phosphorus at sulfur followed by fast decomposition of the phosphonium intermediate to the corresponding phosphine sulfide, phenylisocyanate and carbonylsulfide. From the Hammett correlations and from the solvent dependency, it was concluded that the transition-state structure is very polar and resembles the zwitter-ionic intermediate. The extent of P-S bond formation and S-S bond cleavage is very similar in the solvents series, but the latter gradually decreases with the decreasing polarity of the solvent.

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Section: Resultssupporting

confidence: 71%

Mechanism of sulfur transfer from 1,2,4-dithiazolidine-3,5-diones to triphenylphosphines

Пономарьов

Padělková

Hanusek

2013

J. Phys. Org. Chem.

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“…The transanular P···P distance is 2.916 Å. The P(1)–S(1) [1.9020(13) Å] and P(3)–S(3) [1.9097(13) Å] and P(1)–S(6) [2.0762(14) Å] and P(3)–S(4) [2.0730(14) Å] distances are comparable to those in other known C 3 P 2 S ring derivatives [31,36,37,39]. The supramolecular structure of 18 consists of a combination of weak intermolecular C–H···S interactions (yellow dashed line), intermolecular C–H···O interactions (pink dashed line), and π–π stacking interactions to build up the multi-stepped supramolecular assembly shown in Figure 4b.…”

Section: Resultssupporting

confidence: 56%

“…2.10 Å] [35] and the P=S double bond [ ca . 1.91 Å] [36], indicating the delocalization of the negative charge over the FPS 2 − fragment. The P–F bond length [1.615(4) Å] is statistically indistinguishable from that in PSe 2 F − [1.604(3)–1.610(5) Å] [25].…”

Section: Resultsmentioning

confidence: 99%

Novel Fluorinated Phosphorus–Sulfur Heteroatom Compounds: Synthesis and Characterization of Ferrocenyl- and Aryl-Phosphonofluorodithioic Salts, Adducts, and Esters

Hua

Surgenor

et al. 2015

Molecules

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A series of novel ferrocenyl-and aryl-phosphonofluorodithioic salts, adducts, and esters has been prepared. The reaction of 2,4-diferrocenyl-1,3,2,4-diathiadiphosphetane 2,4-disulfide {[FcP(μ-S)S]2, FcLR} with dry KF or tetrabutylammonium fluoride (TBAF) led to the corresponding potassium and tetrabutylammonium salts of ferrocenyldithiofluorophosphinic acids. Treating potassium ferrocenyldithiofluorophosphinic acid with an equimolar amount of tetraphenylphosphonium chloride readily yielded the corresponding organic adducts, and with mono-and di-halogenated alkanes generated a series of the corresponding esters of ferrocenylphosphonofluoridodithioates. Similarly, using 1,3-epithionaphtho [1,8-cd]

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“…As for the former, the presence of electron-releasing (ER) groups bound to the phenyl rings of arylphosphorothionates has been reported to increase the P=S bond length and the charge on the phosphorus atom [58]. This would make the phosphorus atom itself more open to nucleophilic attack, increasing, as a consequence, the reactivity of the molecule.…”

Section: Influence Of the Alkyl Chain Length And Ironmentioning

confidence: 99%

Substituent Effect on the Reactivity of Alkylated Triphenyl Phosphorothionates in Oil Solution in the Presence of Iron Particles

2010

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The effect of the substituent attached to the phenyl rings on the reactivity of alkylated triphenyl phosphorothionates (t-butyl TPPT (b-TPPT) and p-nonyl TPPT (n-TPPT)) in oil solution at high temperature (423 and 473 K) was investigated by means of Fourier-transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The FT-IR and NMR results show that the alkylated TPPTs were highly thermally stable and did not completely decompose in oil, even upon heating at 423 K for 168 h and at 473 K for 72 h, with and without steel filings and iron particles (both metallic iron and iron oxide particles). The reaction of alkylated TPPTs was found to start with the scission of the P=S bond to yield alkylated triphenyl phosphate. The kinetics of the thermooxidative reaction was slower when steel filings and iron particles were added to the oil solutions during the heating experiments. The reactivity of the unsubstituted molecule (TPPT) was higher than that of alkylated TPPTs at 423 K, while at 473 K TPPT and n-TPPT were more reactive than b-TPPT. In the case of the experiments performed at 473 K in the presence of steel filings or metallic iron or iron oxide particles, the reactivity of the alkylated TPPT molecules decreased with the length of the alkyl chain bound to the phenyl rings. The XPS results show that a reaction layer consisting of carbon, oxygen, phosphorus and iron was formed on the 100Cr6 steel filings immersed for 72 h in oil solutions containing alkylated TPPTs and heated at 473 K. Sulphur was neither detected on the surface nor in the composition vs depth profile. During the heating experiments, the base oil (PAO) was oxidized. At 423 K, the alkylated TPPTs had a strong antioxidant effect, which was found to be more pronounced upon increasing the length of the alkyl chain bound to the phenyl rings. At 473 K, the TPPTs did not inhibit the oxidation of the base oil as effectively as at 423 K.Keywords Thermo-oxidative degradation Á t-butyl triphenyl phosphorothionate (b-TPPT) Á Irgalube Ò 232 Á p-nonyl triphenyl phosphorothionate (n-TPPT) Á Irgalube Ò 211 Á Ashless anti-wear additives Á Low-SAPS additives Á FT-IR Á NMR Á XPS Á Iron particles 1 Introduction

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Substituent effects on the 31P NMR chemical shifts of arylphosphorothionates

Cited by 20 publications

References 35 publications

Mechanism of sulfur transfer from 1,2,4-dithiazolidine-3,5-diones to triphenylphosphines

Mechanism of sulfur transfer from 1,2,4-dithiazolidine-3,5-diones to triphenylphosphines

Novel Fluorinated Phosphorus–Sulfur Heteroatom Compounds: Synthesis and Characterization of Ferrocenyl- and Aryl-Phosphonofluorodithioic Salts, Adducts, and Esters

Substituent Effect on the Reactivity of Alkylated Triphenyl Phosphorothionates in Oil Solution in the Presence of Iron Particles

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