Catalysis by ionic liquid: a simple, green and efficient procedure for the Michael addition of thiols and thiophosphate to conjugated alkenes in ionic liquid, [pmIm]Br

A room temperature ionic liquid, 1-pentyl-3-methylimidazolium bromide, [pmIm]Br efficiently catalyzes Michael addition of thiols and diethyl dithiophosphate to a variety of conjugated alkenes such as α,β-unsaturated carbonyl compounds, carboxylic esters, nitriles and chalcones without requiring any other organic solvent and catalyst. The ionic liquid can be recycled for subsequent reactions without any appreciable loss of efficiency.     

Cs3UP2S8, a Coordination Polymer Containing the Unprecedented [U=S]2+ Sulfidouranium(2+) Moiety

Although terminal chalcogeno ligands are well known for the group 5 and 6 transition metals, they are highly unusual for the oxophilic group 4 metals and unknown so far for the lanthanides or actinides. Cs₃UP₂S₈, is the first actinide compound containing a terminal M=S group. It was synthesized by reacting uranium metal, Cs₂S, S, and P₂S₅ in a 4:1:8:3 ratio at 700 °C in an eutectic LiCl/CsCl mixture. The crystal structure was determined by single‐crystal X‐ray diffraction techniques. Cs₃UP₂S₈ crystallizes in the rhombohedral space group R$\bar{3}$ [a = 15.5217(8) Å; c = 35.132(2) Å, V = 8305.0(8) ų, Z = 18]. The crystal structure is based on a tetrahedral network type, wherein the uranium atoms are coordinated by a unusual sulfido moiety and thiophosphate groups in a pseudo‐tetrahedral fashion. The U=S distance of 2.635(3) Å observed in the sulfide moiety is approx. 0.2 Å shorter than the average U–S single bond length, indicating a double‐bond type character.     

Synthesis and Characterization of the Rubidium Thiophosphate Rb6(PS5)(P2S10) and the Rubidium Silver Thiophosphates Rb2AgPS4, RbAg5(PS4)2 and Rb3Ag9(PS4)4

The metal thiophosphates Rb₂AgPS₄ ( 2 ), RbAg₅(PS₄)₂ ( 3 ), and Rb₃Ag₉(PS₄)₄ ( 4 ) were synthesized by stoichiometric reactions, whereas Rb₆(PS₅)(P₂S₁₀) ( 1 ) was prepared with excess amount of sulfur. The compounds crystallize as follows: 1 monoclinic, P2₁/c (no. 14), a = 17.0123(7) Å, b = 6.9102(2) Å, c = 23.179(1) Å, β = 94.399(4)°; 2 triclinic, P$\bar{1}$ (no. 2), a = 6.600(1) Å, b = 6.856(1) Å, c = 10.943(3) Å, α = 95.150(2)°, β = 107.338(2)°, γ = 111.383(2)°; 3 orthorhombic, Pbca (no. 61), a = 12.607(1) Å, b = 12.612(1) Å, c = 17.759(2) Å; 4 orthorhombic, Pbcm (no. 57), a = 6.3481(2) Å, b = 12.5782(4) Å, c = 35.975(1) Å. The crystal structures contain discrete units, chains, and 3D polyanionic frameworks composed of PS₄ tetrahedral units arranged and connected in different manner. Compounds 1 – 3 melt congruently, whereas incongruent melting behavior was observed for compound 4 . 1 – 4 are semiconductors with bandgaps between 2.3 and 2.6 eV and thermally stable up to 450 °C in an inert atmosphere.     

O,O-二烷基硫代磷(膦)酸酯与三氯氧磷的异构化/氯化反应机理初探

O,O－二烷基硫代磷(膦)酸酯(1)与三氯氧磷作用得到S-烷基硫代磷酰氯(2)和O-烷基磷酰二氯(3),此反应包含异构化和氧化两个过程.实验结果表明,1的预期氯化产物O-烷基硫代磷(膦)酰氯酯(5)与三氯氧磷不发生反应,而1的预期异构化产物O,S-二烷基硫代磷(膦)酸酯(6)与三氯氧磷能顺利反应得到2.由此推测,在1的异构化/氯化反应中,异构化很可能发生在氯化之前.根据此结果和三角双锥中间体(TBP)概念,提出了该反应初步的可能机理.     

Synthesis of biotinylated diazinon: Lessons learned for biotinylation of thiophosphate esters

Biotinylation permits recovery of a molecule from a complex mixture, with commercially available streptavidin containing products (such as streptavidin-coated beads). As part of a larger effort to evaluate reagents capable of degrading diazinon, a thiophosphate insecticide, we pursued biotinylation of this molecule. Our strategy focused on replacing a single thiophosphate ethyl ester with an ester linkage that contains biotin. Multiple approaches—using published methods—were unsuccessful and resulted in no reactivity, or degradation of starting material. Here, we report a successful strategy for the synthesis of biotinylated diazinon, which is likely applicable to alternative thiophosphate esters and other biotinylated molecules.     

Cs2CO3‐Catalyzed Aerobic Oxidative Cross‐Dehydrogenative Coupling of Thiols with Phosphonates and Arenes

An efficient Cs₂CO₃‐catalyzed oxidative coupling of thiols with phosphonates and arenes that uses molecular oxygen as the oxidant is described. These reactions provide not only a novel alkali metal salt catalyzed aerobic oxidation, but also an efficient approach to thiophosphates and sulfenylarenes, which are ubiquitously found in pharmaceuticals and pesticides. The reaction proceeds under simple and mild reaction conditions, tolerates a wide range of functional groups, and is applicable to the late‐stage synthesis and modification of bioactive molecules.     

O-(α-氰基-间-苯氧基苄基)硫代磷酸酯和磷酰胺的NMR研究

本文合成了20个题示的化合物,研究了它们的¹H和³¹P谱,找出了δ_P与取代基关系的一些规律,观察到了手性中心对δ_H的影响、及一个手性中心对另一个手性中心R、S体不等价的诱导位移,并观察了产物中R、S体的不同含量比例。     

Benign synthesis of thiophosphates,thiophosphinates and selenophosphates in neat condition using N-chalcogenoimides as the source of electrophilic sulfur/selenium

A neat reaction protocol has been developed for synthesis of thiophosphate, thiophosphinate and selenophosphate compounds. N-chalcogenoimides have been used for chalcogenylation of P(O)H moieties of various H-phosphonates under solvent, catalyst and base free condition at room temperature in aerial atmosphere. Both S-aryl and S-alkyl phosphorothioate compounds were prepared by this method in good yields. Selenophosphates were also synthesized using N-(phenylseleno)phthalimide under solvent free condition.     

New Light on an Old Story: The Crystal Structure of Boron Tetrathiophosphate Revisited

The crystal structure of boron tetrathiophosphate BPS₄ was reinvestigated using single‐crystal X‐ray diffraction. The structure shows unidimensional chains similar to SiS₂ as structural motifs. BPS₄ crystallizes in the orthorhombic space group Ibam (no. 72), with a = 5.6173(3), b = 8.9929(4), c = 5.2433(3) Å and V = 264.87(2) ų and is closely related to the orthorhombic high‐temperature modification of AlPS₄ (ht‐AlPS₄). The SiS₂‐like chains are all oriented parallel to the c axis, which explains the needle‐like morphology and that the crystals easily cleave to thinner needles under mechanical stress. While ht‐AlPS₄ shows an ordered Al‐P sublattice, the B‐P sublattice in BPS₄ is substantially disordered. The thermal properties of BPS₄ were investigated by DTA measurements and a detailed analysis of the Raman spectrum assisted by quantum mechanical calculations is presented. The crystallographic disorder in BPS₄ is the result of inter‐chain disorder, whereas local intra‐chain ordering of B and P can be concluded from Raman spectroscopy.     

Reduction of alkyl and aryl azides with sodium thiophosphate in aqueous solutions

A simple aqueous method for the conversion of alkyl and aryl azides into the corresponding amines using trisodium thiophosphate is presented. Thiophosphate is converted into phosphate during these formal reduction processes.