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Metabolic pathway

Iprobenfos undergoes extensive degradation and metabolism. Primary metabolic pathways include isomerisation to the thionate (P=S) ester, cleavage of the P-S-benzyl and P-O-isopropyl moieties, and transesterification. Benzyl mercaptan, upon cleavage, undergoes additional oxidation reactions to yield the alcohol, carboxylic acid, disulfide and sulfonic acid. The formation of the oxon from the isomerisation product (P=S ester) was minor and was observed only under UV light irradiation. The primary metabolic pathways of iprobenfos are presented in Scheme 1.

Degradation

Iprobenfos (1) is stable to hydrolytic degradation (<50 °C). The DTN value of iprobenfos in aqueous solution was approximately 301-324 days(PM). Iprobenfos degraded rapidly when deposited as a thin film and exposed to UV light (DT50 ca. 10 min). Two major degradation reactions were observed during the initial phase of the irradiation. The first reaction involved the isomerisation of iprobenfos to O,O-diisopropyl O- benzyl phosphorothioate (2) followed by the oxidative desulfuration of compound 2 to yield the corresponding oxon analogue 3 (O,O-diisopropyl O-benzyl phosphate). The second reaction involved the hydrolytic cleavage of the S-C linkage of iprobenfos to yield O,O-diisopropyl hydrogen phosphorothioate (4) and the cleavage of the P-O-benzyl linkage of compound 3 to yield O,O-diisopropyl hydrogen phosphate (5). Other major photolytic degradation reactions include the cleavage of the parent P-S linkage to O,O-diisopropyl phosphonate (6). Benzyl alcohol (7) and benzyl mercaptan (8) were also detected. Further oxidation of compound 7 yielded benzoic acid (9) and the oxidation of compound 8 yielded benzylsulfonic acid (10), dibenzyl disulfide (11) and sulfuric acid as terminal products. Other minor products detected included transesterification products [O,O,S-triisopropyl phosphorothioate (12), O,O,O-triisopropyl phosphate (13)] and benzyl isopropyl sulfide (14).

InChI:InChI=1/C13H21O3PS/c1-11(2)15-17(14,16-12(3)4)18-10-13-8-6-5-7-9-13/h5-9,11-12H,10H2,1-4H3

Upstream product

• 4486-44-6 O,O-diisopropylphosphorothioic acid 
• 100-44-7 benzyl chloride 
• 691-96-3 diisopropyl phosphite 
• 51756-06-0 O,O-diisopropyl thiophosphoric acid triethylammonium salt 
• 100-39-0 benzyl bromide 
• 1809-20-7 diisopropyl hydrogenphosphonate 
• 100-51-6 benzyl alcohol 
• 150-60-7 dibenzyl disulphide 
• 116-17-6 triisopropyl phosphite 
• 16601-02-8 S-benzyl 4-methylbenzenethiosulfonate 
• 103-82-2 phenylacetic acid 
• 63591-85-5 phenylacetic acid N-hydroxysuccinimide ester 
• 4486-44-6 O,O-diisopropyl S-hydrogen phosphorothioate 
• 100-53-8 phenylmethanethiol 

Relevant academic research and scientific papers

Sulfonyl-Promoted Michaelis-Arbuzov-Type Reaction: An Approach to S/Se-P Bonds

By facilitating the chemical conversion of thiols to thiosulfonates, phosphoramidite/phosphite bearing sp3-hybridized carbon serves as an ideal coupling material to forge new connections at room temperature. In this work, a functional group-induced, additive-free, novel, S-P bond-forming approach is presented. This protocol exhibits good functional group tolerance with wide applications that include phosphorylation of cysteine derivatives, development of a one-pot approach to mixed unsymmetrical thiophosphonates, and extension of the concept to different Se-P bonds. Meticulously, our reaction also generated a S-P bond against cyclic 1,2-dithiane-1-dioxide in a byproduct-free manner. These Michaelis-Arbuzov-type reactions are easy to conduct, work efficiently in a reduced reaction time, and are applicable to gram-scale preparation as well.

Photoinduced Decarboxylative Phosphorothiolation of N-Hydroxyphthalimide Esters

A visible-light-induced protocol for the synthesis of phosphorothioates is developed by employing the Ir-catalyzed decarboxylative phosphorothiolation of N-hydroxyphthalimide esters. This novel synthesis method utilizes carboxylic acids as raw material, which is stable, cheap, and commercially available. Scope studies show that this reaction has good compatibility of functional groups. Notably, both the synthesis of steric hindrance phosphorothioates and the later modification of some bioactive compounds are successfully achieved.

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.

Synthetic method for benzyl thiophosphate

The invention provides a synthetic method for benzyl thiophosphate. The method comprises the step of carrying out a stirring reaction for 6-24 hours on benzyl alcohol which is cheap and easily available, wide in source and stable and low in toxicity as an alkylation reagent and sulfur powder and phosphite ester to prepare a benzyl thiophosphate compound in one step at 70-100 DEG C without a catalyst. The method is simple in reaction condition, the raw materials are easily available, excessive alkali is not used, a solvent is not needed, and the method is easy to operate with only one reaction.The method can be also used for amplifying and gram-grade preparation of products conveniently, and has certain research and industrial application prospects.

Lewis Acid Promoted Aerobic Oxidative Coupling of Thiols with Phosphonates by Simple Nickel(II) Catalyst: Substrate Scope and Mechanistic Studies

Exploring new catalysts for efficient organic synthesis is among the most attractive topics in chemistry. Here, using Ni(OAc)2/LA as catalyst (LA: Lewis acid), a novel catalyst strategy was developed for oxidative coupling of thiols and phosphonates to phosphorothioates with oxygen oxidant. The present study discloses that when Ni(OAc)2 alone was employed as the catalyst, the reaction proceeded very sluggishly with low yield, whereas adding non-redox-active metal ions such as Y3+ to Ni(OAc)2 dramatically promoted its catalytic efficiency. The promotional effect is highly Lewis acidity dependent on the added Lewis acid, and generally, a stronger Lewis acid provided a better promotional effect. The stopped-flow kinetics confirmed that adding Y(OTf)3 can obviously accelerate the activation of thiols by Ni(II) and next accelerate its reaction with phosphonate to generate the phosphorothioate product. ESI-MS characterizations of the catalyst disclosed the formation of the heterobimetallic Ni(II)/Y(III) species in the catalyst solution. Additionally, this Ni(II)/LA catalyst can be applied in the synthesis of a series of phosphorothioate compounds including several commercial bioactive compounds. This catalyst strategy has clearly supported that Lewis acid can significantly improve the catalytic efficiency of these traditional metal ions in organic synthesis, thus opening up new opportunities in their catalyst design.

Synthesis of Thiophosphates by Coupling of Phosphates with Bunte Salts under Mild Conditions

A simple, green, and efficient method has been developed for the preparation of thiophosphates with sodium S-benzyl thiosulfates. The method uses an NaBr-catalyzed coupling reaction of Bunte salts with phosphonates in the presence of an acid and hydrogen peroxide (30%), and the desired products were obtained in good yields.

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.

A thiophosphate synthetic method of compound and the method in a plurality of pharmaceutical application in the synthesis of (by machine translation)

The invention discloses a having the general formula (III) of the thiophosphate synthetic method of compound, the purpose is to provide a novel, condition is simple, easy to industrial production of the thiophosphate synthetic method of compound. The method is to have the general formula (I) of the organophosphorus oxygen apperception compound having the general formula (II) with a mercaptan or phenyl-sulfhydryl apperception compound mixed, under the effects of catalyst, obtained by the reaction of the formula (III) of the thiophosphate compound. The method of the invention, can be cheap efficient synthesis of thiophosphate compounds, in actual production will have extensive application prospect. (by machine translation)

Method of preparing kitazin

The invention discloses a method for preparing iprobenfos. The method comprises the following steps: (1) by taking phosphorus trichloride and isopropanol as esterification raw materials, performing deacidification reaction, thereby preparing O,O-diisopropyl phosphite; (2) removing residual 2-chloropropane; (3) reacting O,O-diisopropyl phosphite with sulfur and sodium hydroxide at low temperature in the presence of a solvent, thereby generating O,O-diisopropyl sulfo-sodium phosphate; (4) removing the solvent and filtering; (5) reacting O,O-diisopropyl sulfo-sodium phosphate with benzyl chloride, filtering, and separating the liquid, thereby preparing iprobenfos crude raw oil; (6) washing with water, crystallizing, filtering, and removing the solvent, thereby preparing a iprobenfos active compound. According to the method, as the sodium hydroxide is adopted to prepare salt at low temperature, the decomposition of O,O-diisopropyl phosphite is reduced, the impurities are reduced, no ammonia nitrogen wastewater is generated, and as 2-chloropropane of O,O-diisopropyl phosphite is removed, the generation of a byproduct thiophosphoric acid triisopropyl ester is reduced, and the quality of iprobenfos is improved.

Rearrangement of lithiated S-alkyl O,O-dialkyl thiophosphates: Scope and stereochemistry of the thiophosphate-mercaptophosphonate rearrangement

S-Alkyl O,O-dialkyl thiophosphates are prepared by alkylation of the triethylammonium salt of O,O-diisopropyl thiophosphoric acid. S-Benzyl thiophosphate was metallated at temperatures of ≥-45 °C by trityllithium and LiTMP (lithium 2,2,6,6-tetramethylpiperidide) and S-alkyl thiophosphates only by LiTMP to give dipole-stabilised carbanions which rearrange to α-mercaptophosphonates in yields of up to 45%. Metallation occurs with a high primary kinetic isotope effect (kH/kD up to ≈50). When the lithium (R)-N-isopropyl-1-phenylethylamide was used to induce the isomerisation of S-pentyl thiophosphate an α-mercaptophosphonate with an ee of 22% was isolated. (R)-S-[1-D1]hexyl O,O-diisopropyl thiophosphate was rearranged to a dextrorotary α-mercapto-[1-D 1]hexylphosphonate, whose (R)-configuration was determined by chemical correlation. The thiophosphate-mercaptophosphonate rearrangement proceeds with retention of configuration. The Royal Society of Chemistry 2011.