152-18-1

Usage

Uses

Used in Pesticide and Fungicide Manufacturing:
Trimethyl thiophosphate is used as a key ingredient in the production of pesticides and fungicides, contributing to their effectiveness in controlling various pests and diseases in agriculture. Its potent insecticidal and acaricidal properties make it a valuable component in these products.
Used in Agricultural Applications:
In the agricultural industry, trimethyl thiophosphate is used as an active ingredient in pest control formulations for its ability to target a broad spectrum of pests, helping to protect crops from damage and ensure a healthy yield.
Used in Industrial Applications:
Trimethyl thiophosphate may also be utilized in industrial settings for pest management, particularly in areas where a wide range of pests can cause significant damage to infrastructure or stored goods. Its effectiveness in controlling these pests makes it a valuable tool in maintaining cleanliness and preventing infestations.

InChI:InChI=1/C3H9O3PS/c1-5-7(4,6-2)8-3/h1-3H3

Upstream product

• 186581-53-3 diazomethane 
• 1112-38-5 O,O-dimethyl S-hydrogen phosphorothioate 
• 79855-51-9 2-oxabicyclo<3.3.1>nonane-3-thione 
• 79562-75-7 (1R,4S)-2-Thia-bicyclo[2.2.2]oct-5-ene-3,3-dicarbonitrile 
• 79562-74-6 (3R,6S)-3,6-Diphenyl-3,6-dihydro-thiopyran-2,2-dicarbonitrile 
• 55649-26-8 Trimethyl-phosphorthionat 
• 123-11-5 4-methoxy-benzaldehyde 
• 538-75-0 dicyclohexyl-carbodiimide 
• 17071-97-5 5,6,7,8,9-pentathiabenzocycloheptene 
• 121-45-9 phosphorous acid trimethyl ester 
• 15088-78-5 3-phenylethanoic dithioperoxyanhydride 
• 597-82-0 O,O,O-triphenyl phosphorothioate 
• 67-56-1 methanol 
• 122-14-5 MEP 

Downstream Products

• 152-20-5 O,O,S-trimethyl phosphorothioate 
• 2088-72-4 O,O-Dimethyl-S-carbethoxymethyl-phosphorothioat 
• 57212-78-9 O,O-Dimethyl-S-(methoxycarbonylmethyl)-thiophosphorsaeure 
• 32586-90-6 sodium O,S-dimethyl phosphorothioate 
• 1632-76-4 3-methylpyridazine 
• 512-56-1 trimethyl phosphite 
• 115-10-6 Dimethyl ether 
• 44796-56-7 C₄H₁₂O₃PS⁽¹⁺⁾ 
• 186841-54-3 phosphinic acid monomethyl ester 
• 55649-26-8 Trimethyl-phosphorthionat 
• 123-11-5 4-methoxy-benzaldehyde 
• 755-22-6 2,2,3,3,4,4,5,5-Octafluoro-pentanethial 
• 676-88-0 dimethyl(methylthio)sulfonium tetrafluoroborate 

Relevant academic research and scientific papers

Mononuclear versus dinuclear palladacycles derived from 1,3-bis(N,N-dimethylaminomethyl)benzene: Structures and catalytic activity

Mononuclear and dinuclear palladacycles derived from 1,3-bis(N,N- dimethylaminomethyl)benzenes, [{Pd (Cl)}2,6-(Me2NCH2) 2C6H3] (1) and [1-{Pd(H2O)(Py)}-5- {Pd(OTf)(Py)-2,4-(Me2NCH2)2C6H 2]-(OTf) (2), were synthesized and their structures were fully characterized. Complex 1 is a pincer complex with η3-mer NCN phenyl backbone, complex 2 is a bispalladium(II) complex with 1,2- and 4,5- two C,N-ortho phenyl backbone. Whereas the pincer complex 1 acted as a poor catalyst on methanolysis of fenitrothion, complex 2 demonstrated high catalytic activity in the same reactions, but there is no synergetic effect between two palladium ions. The results clearly indicate that a dissociable co-ligand in the palladacycle compounds significantly promotes the catalytic methanolysis.

Reactions of Benzopentathiepin with Trialkyl Phosphites. A New Preparative Method for S-Aryl O,O'-Dialkyl Thiophosphates

Benzopentathiepin readily reacted with trialkyl phosphites to give S--O,O'-dialkyl thiophosphates and/or O,O'-dialkyl S-(2-mercaptophenyl) thiophosphates.The selectivity for formation of these thiophosphates was dramatically affected by the reaction temperature and the solvent used.

SYNTHESIS OF THIOLATED OLIGONUCLEOTIDES WITHOUT A CAPPING STEP

The invention herein describes a synthetic method for preparing thiolated oligonucleotides without needing a capping step, as the sulfurization agent caps the unreacted 5'-OH groups.

1,2,4-Dithiazole-5-ones and 5-thiones as efficient sulfurizing agents of phosphorus(iii) compounds - A kinetic comparative study

The sulfurization efficiency of 25 3-substituted-1,2,4-dithiazole-5-ones and 5-thiones towards triphenyl phosphite in acetonitrile, DCM, THF and toluene at 25 °C was evaluated. All the 1,2,4-dithiazoles are much better sulfurizing reagents than commercially available agents (PADS, TETD, Beaucage's reagent). The most efficient sulfurizing agents in all solvents are 3-phenoxy (4), 3-phenylthio (5) and 3-ethoxy-1,2,4-dithiazole-5-one (1) whose reactivity is at least two orders of magnitude higher than that of other 1,2,4-dithiazoles. Contrary to a previous report, the sulfurization with 1 does not yield carbonylsulfide and ethyl cyanate as the additional reaction products but unstable ethoxythiocarbonyl isocyanate which has been trapped with 4-methoxyaniline. Similar trapping experiments have proven that the site of attack is at the sulfur adjacent to the CO group for compounds 4 and 5. The reaction pathway involves rate-limiting initial nucleophilic attack of the phosphorus at sulfur followed by decomposition of the phosphonium intermediate to the corresponding phosphorothioate and isocyanate/isothiocyanate species. The existence of the phosphonium intermediate during sulfurization of triphenyl phosphine with 3-phenyl-1,2,4-dithiazole-5-thione (7a) was proven using kinetic studies. From the Hammett and Bronsted correlations and from other kinetic measurements it was concluded that the transition-state structure is almost apolar for the most reactive 1,2,4-dithiazoles whereas a polar structure resembling a zwitter-ionic intermediate may be more appropriate for the least reactive 1,2,4-dithiazoles. The extent of P-S bond formation and S-S bond cleavage is very similar in all reaction series but it gradually decreases with the reactivity of the 1,2,4-dithiazole derivatives.

Mechanistic and computational study of a palladacycle-catalyzed decomposition of a series of neutral phosphorothioate triesters in methanol

The methanolytic cleavage of a series of O,O-dimethyl O-aryl phosphorothioates (1a-g) catalyzed by a C,N-palladacycle, (2-[N,N- dimethylamino(methyl)phenyl]-C1,N)(pyridine) palladium(II) triflate (3), at 25 °C and sspH 11.7 in methanol is reported, along with data for the methanolytic cleavage of 1a-g. The methoxide reaction gives a linear log k2-OMe vs sspKa (phenol leaving group) Bronsted plot having a gradient of βlg = -0.47 ± 0.03, suggesting about 34% cleavage of the P-OAr bond in the transition state. On the other hand, the 3-catalyzed cleavage of 1 gives a Bronsted plot with a downward break at sspKa (phenol) ～ 13, signifying a change in the rate-limiting step in the catalyzed reaction, with the two wings having βlg values of 0.0 ± 0.03 and -1.93 ± 0.06. The rate-limiting step for good substrates with low leaving group sspKa values is proposed to be substrate/pyridine exchange on the palladacycle, while for substrates with poor leaving groups, the rate-limiting step is a chemical one with extensive cleavage of the P-OAr bond. DFT calculations support this process and also identify two intermediates, namely, one where substrate/pyridine interchange has occurred to give the palladacycle coordinated to substrate through the S - P linkage and to methoxide (6) and another where intramolecular methoxide attack has occurred on the P - S unit to give a five-coordinate phosphorane (7) doubly coordinated to Pd via the S- and through a bridging methoxide linked to P and Pd. Attempts to identify the existence of the phosphorane by 31P NMR in a d4-methanol solution containing 10 mM each of 3, trimethyl phosphorothioate (a very slow cleaving substrate), and methoxide proved unsuccessful, instead showing that the phosphorothioate was slowly converted to trimethyl phosphate, with the palladacycle decomposing to Pd0 and free pyridine. These results provide the first reported example where a palladacycle-promoted solvolysis reaction exhibits a break in the Bronsted plot signifying at least one intermediate, while the DFT calculations provide further insight into a more complex mechanism involving two intermediates.

An ortho-palladated dimethylbenzylamine complex as a highly efficient turnover catalyst for the decomposition of P=S insecticides. Mechanistic studies of the methanolysis of some P=S-containing phosphorothioate triesters

An ortho-palladated complex Pd(dmba)(py)(OTf) (9), or Pd(N,N- dimethylbenzylamine)(pyridine)-(trifluoromethanesulfonate), was synthesized and its solution properties in methanol studied as a function of s spH. In neutral solution the triflate dissociates from the complex to give a dominant form Pd(dmba)(py)(HOCH3), and in acid the pyridine dissociates to give Pyr-H+ and Pd(dmba)(HOCH3)(HOCH 3). Under basic conditions, Pd(dmba)(py)(HOCH3) ionizes to give Pd(dmba)(py)(-OCH3) from which the pyridine can dissociate to yield a mixture of a bis-methoxy-bridged dimer (Pd(dmba)( -OCH3))2 (15-dimer), and its monomer Pd(dmba)(HOCH3)-(-OCH3). Kinetic studies under buffered conditions reveal that 9 is an effective catalyst for the methanolysis of fenitrothion and other P=S pesticides. The active form of the catalyst is a basic one having one associated methoxide generated with an apparent sspKa of 10.8. Analysis of the change in the UV/vis spectrum as a function of sspH generates a spectrophotometric ssKa of 10.8 ±0.1. This catalytic system is shown to promote the methanolysis of fenitrothion (3), diazinon (4), quinalphos (5), coumaphos (10) and dichlofenthion (11) at 0.05 mol dm-3 triethyl amine buffer, sspH 10.8, 25°C, under turnover conditions where the [phosphorothioate]/[9] ratio is 48.6, 13.4, 13.4, 18.6, and 48.6 respectively. In all cases, the products were derived from displacement of the leaving group by methoxide, the second-order turnover rate constants being 36.9, 0.45, 0.12, > 146.7 and 44.3 dm 3 mol-1 s-1 respectively. An associative mechanism for the catalyzed methanolysis of the P=S pesticides is proposed where a transiently coordinated S=P substrate is intramolecularly attacked by the PdII-coordinated methoxide. The Royal Society of Chemistry 2005.

Method of decomposing organophosphorus compounds

Methods and kits for decomposing organophosphorus compounds in non-aqueous media at ambient conditions are described. Insecticides, pesticides, and chemical warfare agents can be quickly decomposed to non-toxic products. The method comprises combining the organophosphorus compound with a non-aqueous solution, preferably an alcohol, comprising metal ions and at least a trace amount of alkoxide ions. In a first preferred embodiment, the metal ion is a lanthanum ion. In a second preferred embodiment, the metal ion is a transition metal.

Cu(II)-Mediated decomposition of phosphorothionate P=S pesticides. Billion-fold acceleration of the methanolysis of fenitrothion promoted by a simple Cu(II)-ligand system

The kinetics of methanolysis of the title compound (3) were studied in the presence of Cu2+, introduced as Cu(OTf)2, in the presence of 0.5-1.0 eq. of methoxide and in the presence of 1.0 eq. of a ligand such as bipyridyl (5), phenanthroline (6) or 1,5,9-triazacyclododecane (4). In all cases the active species involve Cu2+(-OCH3). In the case of added strongbinding ligands 5 or 6, a plot of the observed rate constant for methanolysis of 3 vs. [Cu2+]total gives a curved line modelled by a process having a [Cu2+]1/2 dependence consistent with an active monomeric species in equilibrium with an inactive dirtier i.e. {LCu2+(-OCH3)} 2→2LCu2+(-OCH3). In the case of the added strong binding ligand 4, the plot of the observed rate constant for methanolysis of 3 vs. [Cu2+]total gives a straight line consistent with the catalytically active species being 4Cu 2+(OCH3) which shows no propensity to form inactive dimers. Turnover experiments where the [3] > [Cu2+] total indicate that the systems are truly catalytic. In the optimum case a catalytic system comprising 1 mM of the complex 4Cu2+( -OCH3) catalyzes the methanolysis of 3 with a t 1/2 of ～58 s accounting for a 1.7 × 109-fold acceleration relative to the background reaction at near neutral sspH (8.75).

Nucleoside H-Phosphonates. 13. Studies on 3H-1,2-Benzodithiol-3-one Derivatives as Sulfurizing Reagents for H-Phosphonate and H-Phosphonothioate Diesters

Formation of O-oxidized products during sulfurization of H-phosphonothioate and H-phosphonate diesters with 3H-1,2-benzodithiol-3-one 1,1-dioxide (1) was found to be due to generation of the O-oxidizing agents, most likely 3H-2,1-benzoxathiol-3-one 1-oxide (4) and 3H-2,1-benzoxathiol-3-one (5), during the course of the reactions.Another source of the side products formation may be the disproportionation of 1 that occurs in the presence of triethylamine.To overcome these problems, a new sulfur-transferring reagent, 3H-1,2-benzodithiol-3-one (3), has been developed.Under aqueous reaction conditions, which are compartible with both solution and solid-phase synthesis of oligonucleotides, the reagent 3 furnished clean and fast conversion of H-phosphonothioate and H-phosphonate diesters into the corresponding phosphorodi- and phosphoromonothioates.

THIONO COMPOUNDS. 10. STRUCTURES AND REACTIONS OF INTERMEDIAATES FROM THE OXIDATION OF PHOSPHOROTHIOATES

Intermediates from the oxidation of phosphorothioates, (RO)3PS, were studied previously at low temperature using 31P NMR, UV and Raman spectra.Now reported is further information about the structure of intermediates and about their reactions, both of which afford significant clues as to how phosphorothioates may produce adverse biological reactions after they have ben oxidized biologically.Mass spectra identified intermediates corresponding to (RO)3PSn with n up to 7 (although presence of some equivalent masses with two oxygens in place of a sulfur atom is possible).HPLC separated unstable intermediates for which UV and MS evidence again was consistent with the structure (RO)3PSn.That intermediates can react as nucleophiles is illustrated by reactions with Ellman's Reagent, which produced a maximum of thiolate ion at about the time 31P NMR and UV indicated a maximum of intermediates.A second illustration of nucleophilicity was reaction with N-ethylmaleimide (and other Michael acceptors), which led to thiiranes and thiirane 1-oxides.That the intermediates can react also as electrophiles is illustrated by reactions (followed by UV and 31P NMR) with trimethyl phosphite, hydroxyl ion, and water (perhaps to some extent); use of H2(18)O did not introduce (18)O into phosphate products, but exchange reactions with H2(18)O did indicate presence of oxygenated species among the intermadiates.Keywords: Ellman's Reagent; N-ethylmaleimide; 31P NMR spectra; Phosphorothioates; Thiiranes; UV spectra.