3689-24-5

Usage

Uses

Used in Pesticide Industry:
SULFOTEP is used as an insecticide and miticide for controlling various pests. It is particularly effective against aphids, thrips, mites, and whiteflies in glasshouses, where it is applied through fumigation. Additionally, it is used to control sciarid and phorid flies in the cultivation of mushrooms.
Used in Chemical Industry:
Due to its chemical properties as a yellow mobile liquid, SULFOTEP can also be utilized in the chemical industry for various purposes, such as a component in the synthesis of other compounds or as an intermediate in chemical reactions. However, it is essential to consider its toxicity and take necessary precautions when handling and using it in this context.

Reactivity Profile

Organothiophosphates, such as TETRAETHYL DITHIOPYROPHOSPHATE, are susceptible to formation of highly toxic and flammable phosphine gas in the presence of strong reducing agents such as hydrides. Partial oxidation by oxidizing agents may result in the release of toxic phosphorus oxides. SULFOTEP is incompatible with the following: Strong oxidizers, iron [Note: Corrosive to iron.] .

Hazard

Toxic by ingestion, inhalation, and skin absorption; cholinesterase inhibitor; use may be restricted. Questionable carcinogen.

Safety Profile

Poison by ingestion, skin contact, inhalation, intramuscular, intraperitoneal, subcutaneous, and intravenous routes. A cholinesterase inhbitor type of insecticide. When heated to decomposition it emits toxic fumes of POx and SOx. See also PARATHION.

Potential Exposure

Sulfotep is used in greenhouse fumigant formulations for control of aphids, spider mites; thrips, whiteflies, etc.

Environmental Fate

Soil. Cleavage of the molecule yields diethyl phosphate, monoethyl phosphate and phosphoric acid (Hartley and Kidd, 1987).Chemical/Physical. Emits toxic oxides of sulfur and phosphorus oxides when heated to decomposition (Lewis, 1990).

Metabolic pathway

Sulfotep and related compounds may be formed photochemically from a number of phosphorodithioate and phosphorothioate insecticides including azinphos-methyl, chlorpyrifos, malathion, methidathion and phosalone (Abdelbagi and Gaston, 1998). Since sulfotep has a rather high mammalian toxicity, this may be of some toxicological sigruficance. Sulfotep is transformed in the environment via oxidative desulfuration to the highly active anti-cholinesterase compounds monosulfotep and tetraethyl pyrophosphate. It is deactivated by hydrolysis to O,O-diethyl phosphorothioate and diethyl phosphate.

Shipping

UN1704 (Sulfotep) Tetraethyl dithiopyrophosphate, Hazard Class: 6.1; Labels: 6.1-Poisonous materials.

Degradation

Sulfotep is relatively slowly hydrolysed with DT50 values of 10.7,8.2 and 9.1 days at pH values 4,7 and 9 respectively (PM).

Toxicity evaluation

Sulfotep is formulated as fumigant. The acute oral LD50 for rats is about 10 mg/kg. Inhalation LC50 (4 h) for rats is about 0.05 mg/L air. NOEL (2 yr) for rats is 10mg/kg diet (0.5mg/kg/d). ADI is 1 μg/kg b.w. Sulfotep is activated by oxidative desulfuration to tetraethyl monothiopyrophosphate and pyrophosphate in the environment. Sulfotep administered to rats is quickly eliminated. The major elimination product is diethyl hydrogen phosphorothioate.

Incompatibilities

Incompatible with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine,bromine, fluorine, etc.); contact may cause fires or explosions. Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides. Hydrolyzes very slowly in aqueous solution. Attacks some forms of plastic, rubber and coating. Corrosive to iron.

Waste Disposal

Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant (≥100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency, or by contacting your regional EPA office. Incineration with added flammable solvent in furnace equipped with afterburner and alkaline scrubber.

InChI:InChI=1/C8H20O6P2S/c1-5-11-15(9,12-6-2)14-16(10,13-7-3)17-8-4/h5-8H2,1-4H3

Synthetic route

3-chloro-2-methyl-quinolin-4-ol (31403-66-4, 83842-53-9) + diethyl phosphorochloridothioate (2524-04-1) → sulfotep (3689-24-5) + Thiophosphoric acid O-(3-chloro-2-methyl-quinolin-4-yl) ester O',O''-diethyl ester (93516-24-6)

Conditions	Yield
With sodium hydroxide; tetra(n-butyl)ammonium hydroxide In tetrachloromethane at 60℃; for 72h;	A n/a B 74%

3-Chlor-4-hydroxy-7-trifluormethylchinolin (65673-93-0) + diethyl phosphorochloridothioate (2524-04-1) → sulfotep (3689-24-5) + Thiophosphoric acid O-(3-chloro-7-trifluoromethyl-quinolin-4-yl) ester O',O''-diethyl ester (93516-26-8)

Conditions	Yield
With sodium hydroxide; tetra(n-butyl)ammonium hydroxide In tetrachloromethane at 60℃; for 72h;	A n/a B 72%

4-hydroxy-2-methylquinoline (607-67-0) + diethyl phosphorochloridothioate (2524-04-1) → sulfotep (3689-24-5) + Quinothion (22439-40-3)

Conditions	Yield
With sodium hydroxide; tetra(n-butyl)ammonium hydroxide In tetrachloromethane at 60℃; for 55h;	A n/a B 70%

7-chloro-4-hydroxylquinoline (86-99-7) + diethyl phosphorochloridothioate (2524-04-1) → sulfotep (3689-24-5) + Thiophosphoric acid O-(7-chloro-quinolin-4-yl) ester O',O''-diethyl ester (93516-22-4)

Conditions	Yield
With sodium hydroxide; tetra(n-butyl)ammonium hydroxide In tetrachloromethane at 60℃; for 55h;	A n/a B 69%

4(1H)-quinolinone (529-37-3) + diethyl phosphorochloridothioate (2524-04-1) → sulfotep (3689-24-5) + Thiophosphoric acid O,O'-diethyl ester O''-quinolin-4-yl ester (93516-19-9)

Conditions	Yield
With sodium hydroxide; tetra(n-butyl)ammonium hydroxide In tetrachloromethane at 60℃; for 55h;	A n/a B 66%

7-trifluoromethyl-quinolin-4-ol (322-97-4) + diethyl phosphorochloridothioate (2524-04-1) → sulfotep (3689-24-5) + Thiophosphoric acid O,O'-diethyl ester O''-(7-trifluoromethyl-quinolin-4-yl) ester (93516-25-7)

Conditions	Yield
With sodium hydroxide; tetra(n-butyl)ammonium hydroxide In tetrachloromethane at 60℃; for 55h;	A n/a B 65%

2,3-dimethylquinolin-4-ol (10352-60-0) + diethyl phosphorochloridothioate (2524-04-1) → sulfotep (3689-24-5) + Thiophosphoric acid O-(2,3-dimethyl-quinolin-4-yl) ester O',O''-diethyl ester (93644-61-2)

Conditions	Yield
With sodium hydroxide; tetra(n-butyl)ammonium hydroxide In tetrachloromethane at 60℃; for 72h;	A n/a B 63%

diethyl phosphorochloridothioate (2524-04-1) + 4,5-dihydro-5-methyl-1,2,4-triazine-6(1H)-one (58861-80-6) → sulfotep (3689-24-5) + (5-Methyl-6-oxo-5,6-dihydro-1H-[1,2,4]triazin-4-yl)-phosphonothioic acid O,O-diethyl ester (135492-37-4)

Conditions	Yield
With potassium carbonate In acetonitrile a) 1 h, 35 deg C, b) 4 h, 50 deg C;	A n/a B 63%

diethyl phosphorochloridothioate (2524-04-1) + 3,7-dichloroquinolin-4-ol (152210-26-9, 93516-30-4) → sulfotep (3689-24-5) + 3,7-Dichloro-1-ethyl-1H-quinolin-4-one (93516-27-9) + Thiophosphoric acid O-(3,7-dichloro-quinolin-4-yl) ester O',O''-diethyl ester (93516-23-5)

Conditions	Yield
With sodium hydroxide; tetra(n-butyl)ammonium hydroxide In tetrachloromethane at 60℃; for 72h;	A n/a B 16% C 62%

5-benzyl-4,5-dihydro-1,2,4-triazin-6(1H)-one (128070-22-4) + diethyl phosphorochloridothioate (2524-04-1) → sulfotep (3689-24-5) + (5-Benzyl-6-oxo-5,6-dihydro-1H-[1,2,4]triazin-4-yl)-phosphonothioic acid O,O-diethyl ester (135492-46-5)

Conditions	Yield
With triethylamine In acetonitrile at 20℃;	A n/a B 53%

3-chloro-quinolin-4-ol (58550-89-3) + diethyl phosphorochloridothioate (2524-04-1) → 3-chloro-1-ethyl-1H-quinolin-4-one (64965-21-5) + sulfotep (3689-24-5) + Thiophosphoric acid O-(3-chloro-quinolin-4-yl) ester O',O''-diethyl ester (93516-21-3)

Conditions	Yield
With sodium hydroxide; tetra(n-butyl)ammonium hydroxide In tetrachloromethane at 60℃; for 72h;	A 17% B n/a C 52%

5-isopropyl-4,5-dihydro-1,2,4-triazin-6-(1H)-one (99822-19-2) + diethyl phosphorochloridothioate (2524-04-1) → sulfotep (3689-24-5) + (5-Isopropyl-6-oxo-5,6-dihydro-1H-[1,2,4]triazin-4-yl)-phosphonothioic acid O,O-diethyl ester (135492-43-2)

Conditions	Yield
With triethylamine In acetonitrile at 20℃;	A n/a B 52%

diethyl phosphorochloridothioate (2524-04-1) + 1,5-dimethyl-4,5-dihydro-1,2,4-triazine-6-one (135492-32-9) → sulfotep (3689-24-5) + (1,5-Dimethyl-6-oxo-5,6-dihydro-1H-[1,2,4]triazin-4-yl)-phosphonothioic acid O,O-diethyl ester (135492-38-5)

Conditions	Yield
With triethylamine In acetonitrile at 20℃;	A n/a B 50%

1,3,4,5-tetrahydro<1,2,4>triazin 6(2H)-one (76990-32-4) + diethyl phosphorochloridothioate (2524-04-1) → sulfotep (3689-24-5) + (6-Oxo-5,6-dihydro-1H-[1,2,4]triazin-4-yl)-phosphonothioic acid O,O-diethyl ester (135492-34-1)

Conditions	Yield
With potassium carbonate In acetonitrile 1.) 35 deg C, 1 h, 2.) 50 deg C, 4 h;	A n/a B 45%

3-methylquinolin-4-ol (64965-46-4) + diethyl phosphorochloridothioate (2524-04-1) → sulfotep (3689-24-5) + 1-(O,O-Diethylphosphorothio)-3-methyl-4-oxo-1,4-dihydroquinoline (93516-28-0) + Thiophosphoric acid O,O'-diethyl ester O''-(3-methyl-quinolin-4-yl) ester (93516-20-2)

Conditions	Yield
With sodium hydroxide; tetra(n-butyl)ammonium hydroxide In tetrachloromethane at 60℃; for 72h;	A n/a B 21% C 31%

5-isopropyl-4,5-dihydro-1,2,4-triazin-6-(1H)-one (99822-19-2) + O,O-dipropyl chlorothiophosphate (2524-05-2) → sulfotep (3689-24-5) + [6-(Dipropoxy-thiophosphoryloxy)-5-isopropyl-5H-[1,2,4]triazin-4-yl]-phosphonothioic acid O,O-dipropyl ester (134202-30-5)

Conditions	Yield
With triethylamine In acetonitrile at 20℃;	A n/a B 28%

5-isopropyl-4,5-dihydro-1,2,4-triazin-6-(1H)-one (99822-19-2) + diethyl phosphorochloridothioate (2524-04-1) → sulfotep (3689-24-5) + [6-(Diethoxy-thiophosphoryloxy)-5-isopropyl-5H-[1,2,4]triazin-4-yl]-phosphonothioic acid O,O-diethyl ester (134202-29-2)

Conditions	Yield
With triethylamine In acetonitrile at 20℃;	A n/a B 25%

diethyl phosphorochloridothioate (2524-04-1) + 4,5-dihydro-5-methyl-1,2,4-triazine-6(1H)-one (58861-80-6) → sulfotep (3689-24-5) + [6-(Diethoxy-thiophosphoryloxy)-5-methyl-5H-[1,2,4]triazin-4-yl]-phosphonothioic acid O,O-diethyl ester (134202-27-0)

Conditions	Yield
With potassium carbonate In acetonitrile 1.) 1 h, 35 deg C, 2.) 4 h, 50 deg C;	A n/a B 20%

pyridine (110-86-1) + Diethyl phosphate (598-02-7) + diethyl phosphorochloridothioate (2524-04-1) → Tetraethyl pyrophosphate (107-49-3) + tetraethyl thiopyrophosphate (645-78-3) + sulfotep (3689-24-5)

Conditions	Yield
das Natrium-Salz reagiert;

diethyl phosphorylchloridite (589-57-1) + sodium diethyl phosphite (2303-76-6, 118080-94-7) → sulfotep (3689-24-5)

Conditions	Yield
und Erhitzen des Reaktionsgemisches mit Schwefel;

O,O,O-triethyl phosphorothioate (126-68-1) → sulfotep (3689-24-5)

Conditions	Yield
With sulfuric acid

diphosphorous acid tetraethyl ester (21646-99-1) → sulfotep (3689-24-5)

Conditions	Yield
With sulfur at 160℃;

sodium diethyl phosphite (2303-76-6, 118080-94-7) + diethyl phosphorochloridothioate (2524-04-1) → sulfotep (3689-24-5)

Conditions	Yield
With Petroleum ether und anschliessenden Erwaermen mit Schwefel;

diethyl phosphorochloridothioate (2524-04-1) + O,O'-diethyl thiophosphoric acid (2465-65-8) → sulfotep (3689-24-5)

Conditions	Yield
With triethylamine

diethyl phosphorochloridothioate (2524-04-1) → sulfotep (3689-24-5)

Conditions	Yield
With pyridine; water

diethyl phosphorylchloridite (589-57-1) + phosphonic acid diethyl ester (762-04-9) → sulfotep (3689-24-5)

Conditions	Yield
With pyridine; sulfur; toluene

diphenylphosphinous acid methyl ester (4020-99-9) + bis(diethylphosphoryl)disulfide (4403-51-4) → O,O-diethyl S-methyl phosphorothioate (2404-05-9) + sulfotep (3689-24-5) + C16H20O4P2S + methyl diphenylphosphinate (1706-90-7)

Conditions	Yield
In dichloromethane 1.) -70 deg C -> room temperature, 2.) room temperature, 30 min; Title compound not separated from byproducts;

tri-n-butyl phosphite (102-85-2) + bis(diethylphosphoryl)disulfide (4403-51-4) → tetraethyl thiopyrophosphate (645-78-3) + sulfotep (3689-24-5) + diethyl S-tert-butyl thiophosphate (7795-74-6) + C12H28O6P2S

Conditions	Yield
With trineopentyl phosphite In dichloromethane 1.) -70 deg C -> room temperature, 2.) room temperature, 30 min; Further byproducts given. Title compound not separated from byproducts;
In dichloromethane 1.) -70 deg C -> room temperature, 2.) room temperature, 30 min; Further byproducts given. Title compound not separated from byproducts;

trineopentyl phosphite (14540-52-4) + bis(diethylphosphoryl)disulfide (4403-51-4) → sulfotep (3689-24-5) + C19H43O6P2S(1+)*C4H10O3PS(1-) + C19H43O6P2S(1+)*C4H10O3PS(1-)

Conditions	Yield
at -100 - -30℃; Mechanism;

bis(diethylphosphoryl)disulfide (4403-51-4) + 2-ethoxy-1,3,2-benzodioxaphosphole (10072-02-3) → O,O,S-triethyl phosphorothioate (1186-09-0) + tetraethyl thiopyrophosphate (645-78-3) + sulfotep (3689-24-5) + Thiophosphoric acid O,O'-diethyl ester O''-(2-oxo-2λ5-benzo[1,3,2]dioxaphosphol-2-yl) ester

Conditions	Yield
In dichloromethane 1.) -70 deg C -> room temperature, 2.) room temperature, 30 min; Further byproducts given. Title compound not separated from byproducts;

sulfotep (3689-24-5) → diethyl phosphorofluoridothioate (358-75-8)

Conditions	Yield
With hydrogen fluoride

Upstream product

• 110-86-1 pyridine 
• 598-02-7 Diethyl phosphate 
• 2524-04-1 diethyl phosphorochloridothioate 
• 589-57-1 diethyl phosphorylchloridite 
• 2303-76-6 sodium diethyl phosphite 
• 21646-99-1 diphosphorous acid tetraethyl ester 
• 2465-65-8 O,O'-diethyl thiophosphoric acid 
• 762-04-9 phosphonic acid diethyl ester 
• 64965-46-4 3-methylquinolin-4-ol 
• 607-67-0 4-hydroxy-2-methylquinoline 
• 10352-60-0 2,3-dimethylquinolin-4-ol 
• 31403-66-4 3-chloro-2-methyl-quinolin-4-ol 
• 4020-99-9 diphenylphosphinous acid methyl ester 
• 4403-51-4 bis(diethylphosphoryl)disulfide 

Relevant academic research and scientific papers

A quantitative synthesis of β-carboxylated thiolophosphates via a Michael reaction

Reactions of O,O′-dialkylthiophosphoric acids with acrylates provide a direct synthetic route to β-carboxylated thiolophosphates. This Michael addition, without solvent, is quantitative at 90°C in 1 h for the 2/1 thiophosphoric acid/acrylate ratio. Moreover, this excess of thiophosphoric acid can be reused for further reactions.

Reaction of (chloromethyl)phosphonic(-phosphinic) chlorides with silylated protic nucleophiles

Reactions of (chloromethyl)phosphonic(-hosphinic) chlorides with trimethylalkoxy(-phenoxy, -dialkylamino)silanes are accompanied by elimination of trimethylchlorosilane and lead to formation of related substitution products. Reactions of bis(chloromethyl)phosphinic chloride and (chloromethyl)phosphinic dichloride with neutral and hydrogen silyl phosphites were studied. The reactions of bis(chloromethyl)phosphinic chloride with tris(trimethylsilyl)phosphite, diethyl trimethylsilyl phosphite, and bis(trimethylsilyl) hydrogen phosphite yield trimethylsilyl bis(chloromethyl)phosphinate. Similar reactions with (chloromethyl)phosphonic dichloride resulted in isolation of bis(trimethylsilyl) (chloromethyl)phosphonate.

Reaction of Three-coordinate Phosphorus Compounds with Organophosphorus Pseudohalogens. 3. Phosphonium and Phosphorane Intermediates in the Desulfurization and Dehalogenation of Bis(phosphinoyl) Disulfides. Influence of Lewis Acids on the Reaction Chemoselectivity

The reactions of bis(phosphinoyl) disulfides RR1P(O)S-S-P(O)RR1 1 with PIII compounds have been investigated and various mechanistic features have been elucidated by variable-temperature 31P NMR spectroscopy.These studies show that in most cases phosphonium intermediates 5 and 6 are involved.In cases were ligands on PIII increase the stability of the five coordinate structures phosphorane intermediates are observed.In the isomerization 5 -> 6, the mode of decomposition (desulfurization, deoxygenation or dealkylation) to give stable end products is influenced by electronic and steric factors.The presence of the Lewis acid BF3 influences considerably the stability of the transient species 5 and 6 and the chemoselectivity of the reaction.

Pesticide compositions and method

Toxicant, especially pesticide compositions, having lowered dermal toxicity are provided. The compositions include a lipophilic-pesticide, a nonionic surfactant and a dry inert diluent carrier. Methods for reducing the dermal toxicity of lipophilic toxicants, especially pesticides are provided, as well as methods for controlling insect pests using the disclosed compositions.

NEW CHEMISTRY AND STEREOCHEMISTRY OF ORGANOPHOSPHORUS PSEUDOHALOGENS

Synthesis, chemistry and stereochemistry of organophosphorus-sulfur(selenium)pseudohalogens are discussed and rationalized.

PHOSPHORYLATION OF 5-ALKYL-4,5-DIHYDRO-1,2,4-TRIAZIN-6(1H)-ONES

5-Alkyl-4,5-dihydro-1,2,4-triazin-6(1H)-ones are phosphorylated by phosphorochloridic and phosphorochloridothioic esters on the N4 atom of the triazine ring and in some cases also on the carbonyl oxygen.The formation of diphosphorylated triazines is explained by the presence of the tautomeric hydroxy form of the triazine, which is realized under the conditions of the reaction.

Pesticide compositions

Toxicant, especially pesticide compositions, having lowered dermal toxicity are provided. The compositions include a microencapsulated lipophilicpesticide, a hydrophilic surfactant and water. Methods for reducing the dermal toxicity of microencapsulated lipophilic toxicants, especially pesticides are provided. Methods for controlling insect pests using the disclosed compositions are provided.

Reactions of Alcohols with O,O-Diethylphosphorothioic and O,O-Diethylphosphorodithioic Acid in the Presence of Triphenylphosphine and Diethyl Azodicarboxylate, II. 31P-N.M.R. Studies

Low temperature 31P-n.m.r. studies of the reaction of O,O-diethylphosphorothioic acid with triphenylphosphine and diethyl azodicarboxylate revealed that, at low temperatures, the only intermediate is the protonated betaine, even in the presence of neopentyl alcohol.Above 0 deg C this species reacts with neopentyl alcohol to produce the neopentoxytriphenylphosphonium salt which decomposes to isomeric diethyl neopentyl phosphorothioates and triphenylphosphine oxide, at elevated temperatures.The reaction of ethanol with O,O-diethylphosphorodithioic acid leads mainly to O,O,S-triethyl phosphorodithioate and triphenylphosphine oxide.In addition, a small amount of O,O,O-triethylphosphorothionate and triphenylphosphine sulfide were detected.The mechanism of these reactions is suggested.

REACTION OF TRICOORDINATE PHOSPHORUS COMPOUNDS WITH PSEUDOHALOGENS. SCOPE AND MECHANISM

The selectivity of sulphur, selenium and oxygen removal from pseudohalogens: phosphorus disulphides 1 and 2, diselenides 3 and oxophosphoranesulphenyl chlorides 4 has been investigated.A mechanistic rationalization is proposed to account for sulphur(selenium)/oxygen extrusion variation as a function of substrates structure and reaction conditions.