2524-03-0

Basic information

• Product Name: Dimethyl chlorothiophosphate
• Synonyms: DIMETHYLPHOSPHOROCHLOROTHIOATE;DMPCT;METHYL PCT;METHYL PHOSPHOROCHLORIDOTHIOATE;METHYL INTERMEDIARY MP-2;MCT;(CH3O)2P(S)Cl;Chlorodimethoxyphosphine sulfide
• CAS NO: 2524-03-0
• Molecular Formula: C₂H₆ClO₂PS
• Molecular Weight: 160.56
• EINECS: 219-754-9
• Product Categories: Pharmaceutical Intermediates;Biochemistry;Nucleosides, Nucleotides & Related Reagents;Phosphorylating and Phosphorothioating Agents;Protecting Agents, Phosphorylating Agents & Condensing Agents
• Mol File: 2524-03-0.mol

Chemical Properties

• Boiling Point: 66-67 °C16 mm Hg(lit.)
• Flash Point: 221 °F
• Appearance: clear colorless to light yellow liquid
• Density: 1.322 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.67 psi ( 20 °C)
• Refractive Index: n20/D 1.482(lit.)
• Water Solubility: slowly hydrolyzes
• CAS DataBase Reference: Dimethyl chlorothiophosphate(CAS DataBase Reference)
• NIST Chemistry Reference: Dimethyl chlorothiophosphate(2524-03-0)
• EPA Substance Registry System: Dimethyl chlorothiophosphate(2524-03-0)

Safety Data

• Hazard Codes: T
• Statements: 23/24/25-34-23-21/22
• Safety Statements: 23-26-36/37/39-45-24/25
• RIDADR: UN 2267 6.1/PG 2
• WGK Germany: 3
• RTECS: TD1830000
• HazardClass: 6.1(a)
• PackingGroup: II
• Hazardous Substances Data: 2524-03-0(Hazardous Substances Data)

Usage

Uses

Used in Chemical Industry:
Dimethyl chlorothiophosphate is used as a chemical intermediate for the production of insecticides, pesticides, and fungicides, due to its ability to enhance the effectiveness of these products in controlling pests and diseases.
Used in Oil and Gas Industry:
It is used as an additive in oil and gasoline to improve the performance and efficiency of these fuels, contributing to better engine operation and reduced emissions.
Used in Plastics Industry:
Dimethyl chlorothiophosphate is used as a plasticizer, which increases the flexibility and workability of plastic materials, making them more suitable for various applications.
Used in Corrosion Inhibition:
It serves as a corrosion inhibitor, protecting metal surfaces from degradation and extending the lifespan of equipment and structures in various industries.
Used in Flame Retardants:
Dimethyl chlorothiophosphate is used in the formulation of flame-retardant materials, which help to slow down the spread of fire and improve safety in various settings.
Used in Mining Industry:
It is used as a flotation agent in the mining industry, aiding in the separation of valuable minerals from waste materials, thus improving the efficiency of the mining process.

Preparation

Dimethyl chlorothiophosphate is prepared by reaction of phosphorus pentasulfide & methyl alcohol followed by reaction of the resulting dimethyl phosphorodithioate with chlorine.

Reactivity Profile

Organothiophosphates, such as Dimethyl chlorothiophosphate, 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.

Health Hazard

Dimethyl chlorothiophosphate is a strong irritant to the eyes, skin, and mucous membranes.

Fire Hazard

Dimethyl chlorothiophosphate may burn but does not ignite readily. Dimethyl chlorothiophosphate may ignite combustibles (wood, paper, oil, etc.). When heated Dimethyl chlorothiophosphate emits very toxic fumes of chlorine containing compounds, phosphorus oxides, and sulfur oxides.

Flammability and Explosibility

Nonflammable

Safety Profile

Poison by inhalation. Moderately toxic by ingestion and skin contact. Corrosive. When heated to decomposition it emits very toxic fumes of Cl-, POx, and SOx

InChI:InChI=1/C2H6ClO2PS/c1-5-6(3,4)7-2/h1-2H3

Synthetic route

Dimethyl phosphite (868-85-9) → dimethyl chlorothiophosphate (2524-03-0)

Conditions	Yield
With chlorine at 20 - 740℃; Reagent/catalyst; Temperature;	98.6%

O,O-dimethyl phosphorodithioic acid (756-80-9) → dimethyl chlorothiophosphate (2524-03-0)

Conditions	Yield
With chlorine; iron In water at 50℃; for 6h;	94.3%
With chlorine at 30 - 40℃; for 3h; Temperature; Green chemistry;	92.1%
With chlorine; benzene
With chlorine In tetrachloromethane at 0℃; Inert atmosphere;
With chlorine; benzene

dimethylthiophosphoric acid (1112-38-5) → dimethyl chlorothiophosphate (2524-03-0)

Conditions	Yield
With trichlorophosphate at 0 - 5℃; for 1h;	93%

methanol (67-56-1) + methyl phosphorodichloridothionate (2523-94-6) → dimethyl chlorothiophosphate (2524-03-0)

Conditions	Yield
With sodium hydroxide In dichloromethane; water at -5 - 5℃; for 1h; Inert atmosphere;	88%

dimethyl thiophosphite (5930-72-3) → dimethyl chlorothiophosphate (2524-03-0)

Conditions	Yield
With sulfuryl dichloride In benzene for 0.5h;	45%

methanol (67-56-1) → dimethyl chlorothiophosphate (2524-03-0)

Conditions	Yield
With phosphorous (V) sulfide; benzene und anschliessendes Behandeln mit Chlor;
With trichlorothiophosphine; sodium hydroxide at -10℃;

O,O,O-trimethylthiophosphate (152-18-1) → dimethyl chlorothiophosphate (2524-03-0)

Conditions	Yield
With phosphorus pentachloride

dimethyl S-methyl phosphorodithioate (2953-29-9) → dimethyl chlorothiophosphate (2524-03-0)

Conditions	Yield
With dichloromethane Irradiation;

methanol (67-56-1) → methyl phosphorodichloridothionate (2523-94-6) + O,O,O-trimethylthiophosphate (152-18-1) + dimethyl chlorothiophosphate (2524-03-0)

Conditions	Yield
With trichlorophosphate at 20℃; Product distribution; multistep reaction; varying of molar ratio of components; time taken in the addition of alcohol; consumption time of reactants; alcoholysis of PSCl3 (estimation of rel. rates);

sodium methylate (124-41-4) → dimethyl chlorothiophosphate (2524-03-0)

Conditions	Yield
With trichlorothiophosphine In methanol; benzene for 3h; Ambient temperature;

O,O-dimethyl-O-(2,5-dichloro-4-cyano-phenyl)-thionophosphate (64582-42-9) → potassium 2,5-dichloro-4-cyano-phenolate + dimethyl chlorothiophosphate (2524-03-0)

dimethyl chlorothiophosphate (2524-03-0) → O,O-dimethyl phosphoramidothioate (17321-47-0)

Conditions	Yield
With ammonium hydroxide In dichloromethane at 0 - 44℃;	99%
With ammonium hydroxide In dichloromethane at 0 - 44℃; pH=8.4 - 9.1;	99%
With ammonia In dichloromethane at 5 - 10℃; for 10h; Solvent; Temperature;	99.8%

dimethyl chlorothiophosphate (2524-03-0) + 2-diethylamino-4-hydroxy-6-methyl-pyrimidine (42487-72-9) → Pirimiphos-methyl (29232-93-7)

Conditions	Yield
Stage #1: 2-diethylamino-4-hydroxy-6-methyl-pyrimidine With potassium carbonate In water; toluene at 78 - 93℃; for 0.5h; Green chemistry; Stage #2: dimethyl chlorothiophosphate at 20℃; Solvent; Temperature; Green chemistry;	98.6%
Stage #1: 2-diethylamino-4-hydroxy-6-methyl-pyrimidine With potassium carbonate In benzene for 3h; Reflux; Stage #2: dimethyl chlorothiophosphate In butanone; benzene at 60 - 95℃; for 2h; Reflux;

methylamine hydrochloride (593-51-1) + dimethyl chlorothiophosphate (2524-03-0) → N-methyl O,O-dimethyl phosphoramidothioate (31464-99-0)

Conditions	Yield
In dichloromethane at 0 - 35℃; for 1h; pH=8.4 - 9.1;	96%

methyl 3-hydroxybenzoate, sodium salt (51114-02-4) + dimethyl chlorothiophosphate (2524-03-0) → carbomethoxydenitrofenitrothion (142827-30-3)

Conditions	Yield
	95%

dimethyl chlorothiophosphate (2524-03-0) + sodium salt of meta-hydroxybenzaldehyde (38697-17-5) → formyldenitrofenitrothion (153174-74-4)

Conditions	Yield
	95%

cefotaxime (65872-41-5) + dimethyl chlorothiophosphate (2524-03-0) → C8H12N3O5PS2

Conditions	Yield
With tributyl-amine; triethylamine In dichloromethane at 0 - 5℃; for 3h; Inert atmosphere;	95%

C8H11N2O2(1-)*Na(1+) (1445137-34-7) + dimethyl chlorothiophosphate (2524-03-0) → etrimfos (38260-54-7)

Conditions	Yield
With dmap; N-benzyl-N,N,N-triethylammonium chloride; sodium dodecyl sulfate; potassium carbonate In water at 50℃; for 2.5h; pH=9.5 - 10;	94.1%

dimethyl chlorothiophosphate (2524-03-0) + sodium salt of 3,5,6-trichloropyridine-2-ol → O,O-dimethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate (5598-13-0)

Conditions	Yield
With dmap; N-benzyl-N,N,N-triethylammonium chloride; sodium dodecyl sulfate; potassium carbonate In water at 50℃; for 2.5h; pH=9.5 - 10;	93.4%

dimethyl chlorothiophosphate (2524-03-0) + 5-hydroxy-2-nitrobenzaldehyde, sodium salt → O,O-dimethyl O-(3-formyl-4-nitro)phenyl phosphorothioate (59417-72-0)

Conditions	Yield
	92%

sodium 3-methylphenoxide (3019-89-4) + dimethyl chlorothiophosphate (2524-03-0) → denitrofenitrothion (4829-03-2)

Conditions	Yield
	91%
With pyridine In toluene

N,N-dimethylammonium chloride (506-59-2) + dimethyl chlorothiophosphate (2524-03-0) → N,N-dimethyl O,O-dimethyl phosphoramidothioate (28167-51-3)

Conditions	Yield
In dichloromethane at 0 - 35℃; for 1h; pH=8.4 - 9.1;	91%
With triethylamine In tetrahydrofuran 0 deg C to RT;

benzamide (55-21-0) + dimethyl chlorothiophosphate (2524-03-0) → N-[dimethoxy(thio)phosphoryl]benzamide (123269-08-9)

Conditions	Yield
With sodium hydride In tetrahydrofuran	90%

dimethyl chlorothiophosphate (2524-03-0) + methylamine (74-89-5) → N-methyl O,O-dimethyl phosphoramidothioate (31464-99-0)

Conditions	Yield
In diethyl ether for 0.5h;	87%
With triethylamine In diethyl ether
With triethylamine In benzene

dimethyl chlorothiophosphate (2524-03-0) + 1-amino-2-propene (107-11-9) → O,O-dimethyl-N-allylaminothiophosphate (36592-38-8)

Conditions	Yield
With triethylamine In dichloromethane Ambient temperature;	87%

cyclooctylamine (5452-37-9) + dimethyl chlorothiophosphate (2524-03-0) → cyclooctyl-thiophosphoramidic acid O,O'-dimethyl ester

Conditions	Yield
With aluminum oxide at 20℃;	87%

dimethyl chlorothiophosphate (2524-03-0) + 3-(hydroxymethyl)phenol, sodium salt (40599-33-5) → O,O-dimethyl O-(3-hydroxymethyl)phenyl phosphorothioate

Conditions	Yield
	85%

dimethyl chlorothiophosphate (2524-03-0) + methylhydrazine (60-34-4) → N1-dimethoxythiophosphoro-N1-methylhydrazide (80254-53-1)

Conditions	Yield
In chloroform for 6h; Ambient temperature;	85%

cyclohexylamine (108-91-8) + dimethyl chlorothiophosphate (2524-03-0) → O,o'-dimethyl-N-cyclohexyl phosphoramido thionate (941-39-9)

Conditions	Yield
With aluminum oxide at 20℃;	85%

dimethyl chlorothiophosphate (2524-03-0) + benzylamine (100-46-9) → dimethyl N-benzylphosphoramidothionate (130012-35-0)

Conditions	Yield
With triethylamine In dichloromethane for 20h; Ambient temperature;	84%
With triethylamine In tetrahydrofuran 0 deg C to RT;

dimethyl chlorothiophosphate (2524-03-0) + Cyclopentamine (1003-03-8) → C7H16NO2PS

Conditions	Yield
With aluminum oxide at 20℃;	83%
In acetonitrile for 4h;

dimethyl chlorothiophosphate (2524-03-0) + methylhydrazine (60-34-4) → C5H16N2O4P2S2

Conditions	Yield
With triethylamine In chloroform for 2h; Ambient temperature;	82%

cycloheptanamine (5452-35-7) + dimethyl chlorothiophosphate (2524-03-0) → C9H20NO2PS

Conditions	Yield
With aluminum oxide at 20℃;	82%

1-bromo-3,5-di-tert-butylbenzene (22385-77-9) + dimethyl chlorothiophosphate (2524-03-0) → 3, 5-di-tert-butyltoluene (15181-11-0)

Conditions	Yield
Stage #1: 1-bromo-3,5-di-tert-butylbenzene With tert.-butyl lithium In tetrahydrofuran; pentane at -78℃; for 1h; Stage #2: dimethyl chlorothiophosphate In tetrahydrofuran; pentane at -78 - 20℃; for 4h; Further stages.;	80%

diethyl amine hydrochloride (660-68-4) + dimethyl chlorothiophosphate (2524-03-0) → N,N-diethyl O,O-dimethyl phosphoramidothioate (31599-85-6)

Conditions	Yield
In dichloromethane at 0 - 35℃; for 1h; pH=8.4 - 9.1;	80%

4-amino-5-fluoro-pyrimidin-2-ol (2022-85-7) + dimethyl chlorothiophosphate (2524-03-0) → O-(4-amino-5-fluoropyrimidin-2-yl) O,O-dimethyl phosphorothioate

Conditions	Yield
Stage #1: 4-amino-5-fluoro-pyrimidin-2-ol With sodium In N,N-dimethyl-formamide at 20℃; for 2h; Stage #2: dimethyl chlorothiophosphate In N,N-dimethyl-formamide at 20℃; for 48h;	80%

6-(4-(trifluoromethoxy)phenylthio)-2,3,7-trimethylquinolin-4-ol + dimethyl chlorothiophosphate (2524-03-0) → O,O-dimethyl O-2,3,7-trimethyl-6-(4-(trifluoromethoxy)phenylthio)quinolin-4-yl phosphorothioate

Conditions	Yield
With sodium hydroxide In dichloromethane at 10℃; for 4h; Reflux;	80%

Upstream product

• 67-56-1 methanol 
• 2523-94-6 methyl phosphorodichloridothionate 
• 152-18-1 O,O,O-trimethylthiophosphate 
• 756-80-9 O,O-dimethyl phosphorodithioic acid 
• 5930-72-3 dimethyl thiophosphite 
• 2953-29-9 dimethyl S-methyl phosphorodithioate 
• 124-41-4 sodium methylate 
• 64582-42-9 O,O-dimethyl-O-(2,5-dichloro-4-cyano-phenyl)-thionophosphate 
• 868-85-9 Dimethyl phosphite 
• 1112-38-5 dimethylthiophosphoric acid 

Downstream Products

• 5836-40-8 Thiophosphorsaeure-O,O-dimethylester-O-<6-oxo-1,6-dihydro-pyridazinyl-(3)-ester> 
• 114223-86-8 N-dimethoxythiophosphoryloxy-phthalimide 
• 5826-85-7 7-dimethoxythiophosphoryloxy-4-methyl-coumarin 
• 61230-81-7 thiophosphoric acid O,O'-dimethyl ester O''-(6-oxo-1-phenyl-1,6-dihydro-pyridazin-3-yl) ester 
• 5826-75-5 3-chloro-7-dimethoxythiophosphoryloxy-4-methyl-coumarin 
• 16604-77-6 thiophosphoric acid S-methyl ester-O,O'-bis-(4-nitro-phenyl ester) 
• 298-00-0 parathion-methyl 
• 867-27-6 demeton-O-methyl 
• 500-28-7 chlorothion 
• 2463-84-5 dicapthon 
• 5826-76-6 Isochlorthion 
• 118979-25-2 thiophosphoric acid O-(4-chloromethanesulfonyl-phenyl ester)-O',O''-dimethyl ester 
• 98546-05-5 thiophosphoric acid O-(2,4-dichloro-5-nitro-phenyl ester)-O',O''-dimethyl ester 
• 4466-82-4 1,4-bis-dimethoxythiophosphoryloxy-benzene 

Relevant articles and documents

PROCESS FOR PREPARATION OF THIOPHOSPHORYL CHLORIDE AND ACEPHATE

The present invention discloses an improved process for preparation of acephate and intermediates thereof. More particularly, the present invention relates to a process for preparation of thiophosphoryl chloride useful for commercial production of pesticides and pharmaceutically active compounds.

PROCESS FOR PREPARATION OF O, O-DIMEHYL PHOSPHORAMIDOTHIOATE AND N-(METHOXY-METHYLSULFANYLPHOSPHORYL) ACETAMIDE

Preparation of O,O-dimethyl phosphoramidothioate and O,O-dimethyl phosphoroamidothioate. A process of making O,O-dimethyl phosphoroamidothioate is described including reacting sulfur with PCl3 to form PSCl3, reacting the PSCl3 formed with methanol to form O-methyl phosphorodichloridothioate, and reacting the O-methyl phosphorodichloridothioate formed with methyl lye to form O,O-dimethyl phosphorochloridothioate in solution in CH2Cl2, and reacting the O,O-dimethyl phosphorochloridothioate formed with sodium hydroxide and ammonium hydroxide to form O,O-dimethyl phosphoroamidothioate in solution in CH2Cl2. Reacting the O,O-dimethyl phosphoroamidothioate formed with catalytic dimethyl sulfate to form methamidophos, and reacting the methamidophos formed with acetic anhydride to form N-(methoxy-methylsulfanylphosphoryl) acetamide is also described. Throughout the process, the O,O-dimethyl phosphorochloridothioate and the O,O-dimethyl phosphoroamidothioate formed are maintained in solution in CH2Cl2 at all times.

Green synthesis method of methyl-chloride

The invention discloses a green synthesis method of methyl-chloride. The method comprises the following steps of S1, in a reaction system for preparing the methyl-chloride by taking the methyl sulfideand the chlorine as the raw materials, utilizing the characteristic that the disulfur dichloride can chlorinate the methyl sulfide, continuously reacting the disulfur dichloride generated during thereaction process with the methyl sulfide to convert into the methyl-chloride and the sulfur by controlling the introduction amount of the chlorine; and S2, after the reaction is completed, adding a catalyst A and a catalyst B into the reaction system, precipitating the sulfur in the system in the form of loose crystals, separating to obtain the sulfur and a methyl-chloride crude product, and carrying out rectification under vacuum to obtain the high-purity methyl-chloride. According to the method, not only the high-purity methyl-chloride can be prepared, the yield is increased, but also the crystalline sulfur with excellent properties can be obtained and can be reused, a large amount of salt-containing wastewater and the elastic sulfur waste residues are effectively avoided, the pollutioncaused by the waste gas is also avoided, the environmental protection is achieved, and the social benefits and the environmental benefits are remarkable.

Synthesis method of O, O-dialkyl thiphosphoryl chloride

The invention discloses a synthesis method of O, O-diakyl thiphosphoryl chloride. In a reaction system where O, O-dialkyl S-hydro-phophorodithioate and chlorine are subjected to a chlorination reaction to prepare O, O-dialkyl thiphosphoryl chloride, an excess chlorine is introduced to make sulphur generated in the reaction be converted into disulfur dichloride, and disulfur dichloride is convertedinto sulfur dichloride afterwards; and by controlling the reaction temperature and arranging the reaction system to be in the negative pressure state, sulfur dichloride is moved out of the reaction system in the reaction process through distillation and condensing. The synthesis method substantially achieves the atomic economy based on a green chemistry concept; the overall cost of raw materialsis far lower than that in a traditional method, the amount of the three wastes is less, and the three wastes are easy to dispose; a traditional solid-liquid separation step is cancelled, automated production is facilitated, and meanwhile, improvement of the safety and environment production level of the device is facilitated; and O, O-dialkyl thiphosphoryl chloride is not in contact with water, disintegration of the product is avoided, the yield rate is as high as 93%, and the product content can reach 99%.

Organophosphorus hapten, wide-spectrum polyspecific antigen, antibody and preparation method and application of hapten, antigen and antibody

The invention discloses an organophosphorus hapten, a wide-spectrum polyspecific antigen, an antibody and a preparation method and application of the hapten, the antigen and the antibody. The technical defect of an existing organophosphorus pesticide residue immunity analysis method is overcome, the organophosphorus wide-spectrum polyspecific immunity analysis concept is provided, and for organophosphorus pesticides, the method is good in accuracy and sensitivity, can be used for detecting organophosphorus in agricultural products and food samples, realizes universal wide-spectrum polyspecific detection and is quite convenient and rapid to implement in actual use. The wide-spectrum polyspecific antigen has the structure shown in the formula (III) (the formula is shown in the description).

Production method for O,O-dialkyl thiophosphoryl chloride

The invention relates to a production method for O,O-dialkyl thiophosphoryl chloride, and belongs to the field of manufacturing of O,O-dialkyl thiophosphoryl chloride through a chemical method. Raw materials comprise dialkyl phosphite, sulfur or sulfide, chlorine or a chlorinating agent and the like. The production method comprises the steps: carrying out a reaction of dialkyl phosphite and sulfur or sulfide in a synthesis kettle for 2 hours, then chloridizing by chlorine or the chlorinating agent to obtain an O,O-dialkyl thiophosphoryl chloride crude product, and then washing with water to obtain the product O,O-dialkyl thiophosphoryl chloride. The total yield can reach 98%-99%, the content of O,O-dialkyl thiophosphoryl chloride can reach more than or equal to 99.5%, the product quality is good, and the purity of the product can reach 99-99.9%; and the production method has the advantages of simple production process, safe production, low energy consumption, and no pollution. The problems in the prior art that a large amount of alcohol is needed to be recycled, consumption of steam is high and energy consumption is high are solved; and the problems that all the process routes need freezing, a large amount of freezing energy and circulating water is needed and the electric energy consumption is high are solved.

Design and synthesis of novel active phosphonate esters and their application in preparation of ceftriaxone

For a series of active phosphonate esters, the anhydride abbreviated as ANPTA (6a) exhibits the highest reactivity in the preparation of ceftriaxone. The synthesis of ceftriaxone was optimized with the pilot-scale yield reaching 95.7%. The results were explained from the structural viewpoint and supported by analysis of the calculated Mulliken atomic charge distribution.

An efficient synthesis of O,O- di propyl (E)-2-[1-methyl 2-oxopropylidene]phosphorohydrazidothiolate (E) oxime and its analogues: A potential marine toxin

An efficient method for the synthesis of Ptychodiscus brevis toxin O,O- di n-propyl (E)-2-[1-methyl 2-oxopropylidene]phosphorohydrazidothiolate (E) oxime (TG-1) and its analogues has been developed using thermally stable and recyclable silica gel and Na2SO4 as a condensing agent and water scavenger, respectively. The compounds were evaluated against fish Rasbora daniconius by determining the LC50 and LC90 values. The results of biological evaluation showed that these compounds have high degree of toxicity. Copyright Taylor & Francis Group, LLC.

Selective Sulfur Oxygenation in Phosphoroamidate, Thionophosphate, and Thiophosphate Agrochemicals by Perfluoro-cis-2,3-dialkyloxaziridine

Several organophsophorus agrochemicals 2a-g with thioether, phosphoramidic, phosphorothioic, and phosphorothionic functions were reacted with perfluoro-cis-2-n-butyl-3-n-propyloxaziridine 1.The selective oxygenation of sulfide function to give sulfoxide derivatives 3a-g occured in high yields without overoxidation to sulfone products.Sulfoxides 3a-e were further oxidized under mild conditions to the corresponding sulfones 4a-e.All the products are themselves of interest as analytical environmental standards and their preparation is described in detail.