SYNTHETIC,N.M.R. SPECTROSCOPIC AND X-RAY CRYSTALLOGRAPHIC INVESTIGATIONS ON THE PRODUCTS OF THE REACTIONS OF PHENYL (METHYL) PHOSPHONOTHIOIC DICHLORIDE AND THIOPHOSPHORYL CHLORIDE AND PSCL3 WITH PRIMARY AMINES

Abstract

The syntheses in solution of (i) 2,4-dialkylamino-, (ii) 2,4-dimethyl-, and (iii) 2,4-diphenyl-2,4-dithio-cyclodiphosph(V)azanes, [R′P(S)NR]₂ (R′ = NHR, Ph, or Me; R = alkyl), derived from thiophosphoryl trichloride, methylphosphonothioic and phenylphosphonothioic dichlorides and primary alkylamines are described. N.m.r. spectroscopic properties for these cyclodiphosph(V)azanes and their monomeric precursors, R′P(S)(NHR)₂ (R′ = NHR, Ph, or Me; R = alkyl), are presented and structural inferences are drawn from this data. The X-ray crystal structure of [PhP(S)NBuⁱ]₂ is reported.     

2-(N2-O,O-dialkylthiodhosphoryl)-hydfazinobenzothi-azole

Abstract

2-(N₂-O,O-Dialkylthiophosphoryl)hydrazinobenzothiazole (I) could be synthesized with satisfactory yields from the reaction of 2-hydrazinobenzothiazole with thiophosphoryl chlorides. At higher temperature bis(dialkoxy)thiophosphoryl derivatives (11) were given.     

Sulfur Isotopic Exchange Between Two Thiophosphoryl Compounds

Abstract

Thiophosphoryl compounds are useful sulfur donors in thionation reactions (1,2) leading to P=S –> P=O exchange in thiation reagents. Although the reverse conversions P=O –> P=S are also known, mechanisms of both these types of reactions are not thoroughly studied. The analogy of chemical and isotopic exchange reactions in thiophosphoryl moiety push us to investigate the kinetics of isotopic exchange between two thiophosphoryl compounds.     

Synthesis and Characterization of Hg(II) Complexes with 2-Subsituted Benzothiazole Thiophosphates

Some complexes of 3-methyl-2-benzothiazolylidenamido thiophosphoryl dichloride (L₁), (3-methyl-2-benzothiazolylidenamido)–bis-(diethylamido) thiophosphate (L₂), 3-benzyl-2-benzothiazolylidenamido thiophosphoryl dichloride (L₃), and (3-benzyl-2-benzothiazolylidenamido)–bis-(diethylamido) thiophosphate (L₄) have been synthesized by a reaction with mercuric chloride in a 1:1 ratio. The complexes have been characterized by elemental analysis, electrical conductivity, and mass and IR spectral studies. The stability constants of these complexes have also been determined by a spectrophotometric technique and compared with zinc complexes of the previously discussed ligands.     

Phosphoryl and Thiophosphoryl Transfer Reactions: Stereochemical Imperatives for Metaphosphate and Thiometaphosphate

Abstract

The stereochemical courses of phosphoryl transfer reactions in aprotic solvents and thiophosphoryl transfer reactions in protic solvent have been determined. The extensive racemisation observed in both instances is discussed in terms of metaphosphate and thiometaphosphate intermediates of significant life-times.     

PHOSPHORUS-NITROGEN COMPOUNDS. PART 52.1 THE SYNTHESIS OF SOME 1,3,2-BENZODIAZAPHOSPHORINE 2-OXIDES AND 2-SULPHIDES

Abstract

The reactions of 4-methyl-2-[N-(p-toluidinyl)methyl]aniline with phosphorus oxychloride, thiophosphoryl chloride, and their derivatives yield 1,3,2-benzodiazaphosphorine 2-oxides and 2-sulphides. Their ¹H NMR and infrared spectra are discussed. Related 1,3,2-benzodiazophosphorine and 1,3,2-dibenzodiazaphosphocine 2-oxides and 2-sulphides are compared.     

Reactivity Inside a Selenophosphate Dendrimer

Abstract

The divergent synthesis of new series of dendrimers having phosphoryl, thiophosphoryl, and selenophosphoryl branching units has been accomplished by a concise procedure involving phosphitylation of alkanediol derivatives, followed by the corresponding chalcogen addition as the key steps. The backbone of a selenophosphate dendrimer was flexible enough to allow its chemical modification by means of the oxygenation with bulky peroxide.     

REACTION OF BIS-[DIALKOXYPHOSPHORYL]- AND BIS-[DIALKOXYTHIOPHOSPHORYL]- DISULFIDES WITH TRIALKYLSILYLCYANIDES NEW ROUTE TO DIALKYLPHOSPHORO- AND DIALKYLTHIOPHOSPHORO THIOCYANIDATES AND O,O,O,O-TETRAALKYLPYROPHOS- PHOROTRITHIOATES

Abstract

The reaction of organophosphorus disulfides with trialkylsilylcyanide has been investigated. It provided direct evidence for the intermediacy of thiocyanidate >P(X)SCN, X=O, S in this type of reaction. The disulfides studied involved phosphoryl, phosphonyl and/or phosphinyl disulfides. They have been shown to follow the common mechanism. The studied reaction of thiophosphoryl disulfides with trimethylsilylcyanide represents a new and highly efficient route to tetraalkylpyrophosphoro-trithioates.     

Synthesis and Biological Activities of O-Alkyl,O-Aryl,O-{Z-[1-Phenyl-2-(1H-1,2,4-triazol-1-yl)ethylidene]amino} Phosphorothioates

A series of title compounds 2 were efficiently synthesized via the condensation of 1-phenyl-2-(1H-1,2,4-triazol-1-yl)ethanone oxime with various asymmetric thiophosphoryl chlorides in sodium hydroxide powder and acetonitrile system. The structures of title compounds 2 were confirmed by IR, ¹H NMR, ³¹P NMR, EI-MS, and elemental analysis. The results of preliminary bioassays indicated that the title compounds 2 possessed good to moderate insecticidal activity against aphides at the dosage of 250 mg/L, and some of them exhibited moderate fungicidal activities at the concentration of 100 mg/L.     

Acylation of Phosphorus Substituted Ch-Acids Under Phase Transfer Catalysis Conditions

Abstract.

Acylation of phosphoryl- and thiophosphoryl acetonitriles under phase transfer catalysis (PTC) conditions leads in high yields to C-acylated products existing as Z-isomers of the corresponding enol forms. They are stabilized by strong intramolecular H-bonds. On the contrary, acylation of phosphorylacetone proceeds mainly at the oxygene atom and gives Z and E enolacetate. Phosphorus trichloride was used as an acylating agent under PTC conditions. S-Alkyldichlorophosphites were obtained by the reaction with mercaptanes. Alcohols react with PCl₃ in the presence of sodium carbonate to result in dialkylphosphites.     

Novel Synthesis of Macrocylic Systems Containing Phosphorus and Sulfur

Abstract

Macrocyclic systems containing phosphine. phosphoryl or thiophosphoryl functions in the ring demonstrate high ability to complex metal ions Complexed structures of this type show interesting Fatalytic properties and can be used in homogenous and heterogenous catalysis^[1,2] Macrocyclic compounds containg phosphorus are also useful as complexing agents for ammonlum salts. anions. etc [3,4] Generally three types of reactions are used to synthesize phosphorus containing macrocyclic compounds the cyclocondensation, the ring opening reaction and the reaction with metal as a matrix^[5]. We have devoloped a new procedure for the synthesis of the title systems of different sizes and of different P and S contents It is based on a double conjugate addition of dithiolates to divlnyl phosphine oxides and sulfides and makes use of the so-called “cesium effect”.     

REACTIVITIES OF PHOSPHORUS DITHIOACIDS AND S-TRIMETHYLSILYL DITHIOPHOSPHATES IN REACTIONS WITH p-QUINONES

Abstract

Reactions between phosphorus dithioacids and S-trimethylsilyl dithiophosphates and p-quinones yield S-2-hydroxy(trimethylsiloxy)aryl dithiophosphates which are further capable of isomerizing to the respective O-2-mercaptoaryl thiophosphates. On the basis of investigations of the kinetics of dithiophosphate addition to p-benzoquinone in various solvents and kinetic isotopic effect, some conclusions have been reached concerning the mechanism of the reaction. Investigation of the S ? O isomerization of S-aryldithiophosphates suggest that the reaction involves formation of intermediates with hydrothiophosphorane structure. In the case of S-2,4-bis(trimethylsiloxy)phenyl dithiophosphates, the migration of the thiophosphoryl group has been found to be reversible. Isomerization of this kind has also been found to occur in products of addition of dithiophosphates to p-naphthoquinone and N-benzenesulfonyl-p-benzoquinoneimine.     

ALKOXYPHOSPHONIUM SALT INTERMEDIATES IN THE THIONO-THIOLO REARRANGEMENT OF PHOSPHYLTHIONATES IN PROTIC ACID MEDIA

Abstract

The thiono-thiolo rearrangement reaction of phosphylthionates 1 catalyzed by protic acids proceeds with the formation of two types of intermediate alkoxyphosphonium salts 2 and 3. The first of these is formed by the protonation of the substrate 1 at the sulfur atom. Formation of 2 is evident from the changes in chemical shifts in ³¹P NMR spectroscopy of phosphylthionates upon their interaction with trifluoroacetic acid and also from the appearance of electrical conductivity in the solutions of substrates in TFA. The extent of protonation is consistent with the expected substituent effect on the basicity of thiophosphoryl sulfur. The second type of alkoxyphosphonium salt is formed by the alkylation of neutral esters with 2. The formation of 3 is observed in both ¹H and ³¹PNMR spectra. 3 were identified by their spectroscopic comparison with alkoyxphosphonium salts produced by alkylation of 1 with strong alkylation agents. The relative reactivity of a model alkoxyphosphonium salt towards a neutral ester and a phosphylthioate anion was investigated. In the absence of acid the rate of alkylation of the anion exceeds that of the alkylation of a neutral ester by three orders of magnitude. The protonation of phosphylthioate anion under acidic conditions results in a dramatic decrease in the rate of alkylation thereby leading to accumulation of 3 in the acidic reaction media.     

REACTIONS OF SULFUR DIOXIDE WITH AMINOPHOSPHINES

Abstract

The reactions of SO₂ with tris-dimethylaminophosphine, bis-dimethylaminofluorophosphine, bis-dimethylaminochlorophosphine, dimethylaminodifluorophosphine, dimethylaminodichlorophosphine, 1,3-dimethyl-2-fluoro-1,3,2-diazaphospholidine and 1,3-dimethyl-2-chloro-1,3,2-diazaphospholidine have been investigated. The complex reactions are dominated by facile oxidation of the respective phosphine to phosphoryl and thiophosphoryl derivatives. The new heterocyclic phosphines CH₃ NCH₂CH₂N(CH₃)P(O)F and CH₃ NCH₂CH₂N(CH₃)P(S)F have been isolated and characterized by NMR, infrared, and mass spectrometry.     

含噻唑和1,2,3-三唑环的硫代磷酸肟酯的合成与生物活性

为了寻找高效、低毒的新型农用化学品,以2-氯-5-(氯甲基)噻唑为起始原料,设计合成了一系列新型含1,2,3-三唑和噻唑杂环的肟醚硫代磷酸酯衍生物,采用IR, 1H NMR, 31P NMR, MS和元素分析对其进行了结构表征。初步生物活性测试结果表明：该系列化合物具有中等程度的杀虫和杀菌活性。     

Pseudo-halogen behavior of thiophosphoryl azides as a tool for the functionalization of phosphorus macrocycles

Phosphoryl azides are known as azide-transfer agents in organic chemistry; such behavior denotes the pseudo-halogen character of the azide group when linked to a tetracoordinated phosphorus atom, but it was considered up to now only for the functionalization of organic substrates by N₃. We show in this paper that the azide can also be considered as a good leaving group, which facilitates the functionalization of the phosphorus atom which bore it. This reaction is first demonstrated on a small thiophosphoryl azide, then applied to the functionalization of more complex macromolecules, i.e. macrocycles incorporating in their structure thiophosphoryl azido groups.     

A very crowded molecule: formation of bis(2,4,6-tri-t-butylphenyl)phosphinic chloride

Reaction of 2,4,6-ri-t-butylphenyllithium with phosphoryl trichloride gave a very crowded compound, bis(2,4,6-tri-t-butylphenyl)phosphinic chloride ($\text{1}$), and 2,4,6-tri-t-butylchlorobenzene ($\text{3}$), while the reaction with thiophosphoryl trichloride afforded $\text{3}$.     

Studies on Synthesis and Intramolecular Catalyzed Hydrolysis of Thiophosphoramidate Derivatives of Nucleoside

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A New Route to Phosphoryl Thiocarbonyl Mixed Imides - Structure Limitations

Abstract

The rearrangement of N-methyl thiophosphoryl carbonyl mixed imides (I, XYP(S)N(Me)C(O)Z) to N-methyl phosphoryl thiocarbonyl mixed imides (II, XYP(O)N(Me)C(S)Z) was studied as a function of substitution on phosphorus (Ia: X = Y = MeO; Ib: X = Ph, Y = MeO; and Ic: X = Y = Ph) with Z = Ph and as a function of substitution on carbon (Ia: Z = Ph; Id: Z = Me; and Ie: Z = OiBu) with X = Y = MeO. For Ia, Ib, and Id, rearrangement is complete and quantitative. In contrast, Ic rearranges to a 10/90 equilibrium mixture of IIc/Ic and Ie gives no evidence for rearrangement to the phosphoryl thiocarbonyl mixed imide IIe. A relative reactivity order for Ia, Ib, Ic, and Id of 1.00, 0.15, 0.036, and 0.11 respectively, was observed in the rearrangements.