61213-25-0

Basic information

• Product Name: Fluorochloridone
• Synonyms: r40244;(3RS,4RS,3RS,4RS)-3-chloro-4-chloromethyl-1-α,α,α-trifluoro-m-tolyl-2-pyrrolidone(3:1);3-chloro-4-(chloromethyl)-1-(3-(trifluoromethyl)phenyl)-2-pyrrolidione;FLUROCHLORIDON (MIXTURE OF ISOMERS),PEST;flurochloridone (bsi,draft e-iso,draft f-iso);raiser;（3RS， 4RS;（3RS，4RS
• CAS NO: 61213-25-0
• Molecular Formula: C₁₂H₁₀Cl₂F₃NO
• Molecular Weight: 312.12
• EINECS: 262-661-3
• Product Categories: HERBICIDE;Alpha sort;E-GAlphabetic;F;FA - FLPesticides&Metabolites;Herbicides;Others;Pesticides&Metabolites
• Mol File: 61213-25-0.mol
• Article Data: 7

Chemical Properties

• Melting Point: 67.65°C
• Boiling Point: 453.7 °C at 760 mmHg
• Flash Point: >100 °C
• Appearance: /
• Density: 1.3924 (estimate)
• Vapor Pressure: 2.02E-08mmHg at 25°C
• Refractive Index: 1.536
• Storage Temp.: under inert gas (nitrogen or Argon) at 2-8°C
• Solubility: DMSO (Slightly), Methanol (Slightly)
• PKA: -3.59±0.60(Predicted)
• CAS DataBase Reference: Fluorochloridone(CAS DataBase Reference)
• NIST Chemistry Reference: Fluorochloridone(61213-25-0)
• EPA Substance Registry System: Fluorochloridone(61213-25-0)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-27-36/37/39
• RTECS: UY5746500
• Hazardous Substances Data: 61213-25-0(Hazardous Substances Data)

Usage

Chemical Properties

Brown solid. Easily soluble in acetone, chlorobenzene, ethanol, xylene and other organic solvents, with a solubility of 100-150g/L. Solubility in kerosene <5g/L. The solubility in water is 28mg/L. Partition coefficient (n-octanol/water) 2300 (20°C). The half-life is 7d at 60°C and pH 4, 18d at 60°C and pH 7, and the half-life in soil is 11-100d.

Uses

Flurochloridone (FLC) is a monophenyl pyrrolidinone selective herbicide that can be used in herbicidal composition to control weed in crop fields. It is commonly used to inhibit weeds that occur during the growth of crop plants, such as grains, sunflowers, and potatoes.

Definition

ChEBI: Flurochloridone is a member of pyrrolidines, a member of (trifluoromethyl)benzenes and an organochlorine compound. It has a role as a carotenoid biosynthesis inhibitor, an agrochemical and a herbicide.

Synthesis

The synthesis of Fluorochloridone is as follows:To a 1L three-neck flask, N-allyl-N-dichloroacetyl-m-trifluoromethylaniline (31.1 g, 0.1 mol) and 715 ml of 1,2-dichloroethane were added as a solvent, dissolved under stirring, and then added. Cuprous chloride (2.97g, 0.03mol) and 2,2-bipyridyl (4.68g, 0.03mol) were reacted at 80°C for 3 hours, cooled to room temperature, and the reaction solution was filtered through a short silica gel column to give dichloromethane. Elution and desolvation yielded 31.3 g of pyrotropone, a content of 97%, an anti-contrast ratio of ≥3:1, and a yield of 97.6%.

Metabolic pathway

From hydrolytic and photolytic studies of flurochloridone in buffer solution, no hydrolysis of flurochloridone occurs at pH 5, 7, or 9 at 25°C or at pH 5 at 40°C. Appreciable hydrolysis occurs at 40°C at pH 7 and 9 with half-lives of 190 and 140 days, respectively. Five hydrolytic degradation products and six photolytic degradation products are identified. The major photolytic degradation product which contains 39% of the radioactivity is 4-(chloromethyl)-3-hydroxy-1-[3- (trifluoromethyl)phenyl]-2-pyrrolidinone with a mixture of cis and trans isomers. The formation of this major degradation product suggests that the major photolytic pathway involves homolytic cleavage of the carbon ? chlorine bond at the 3-position of the pyrrolidinone ring and the free radical intermediate can react with water to give the major product or eliminate the hydrogen radical to form 4- (chloromethyl)-1,5-dihydro-1-[3- (trifluoromethyl)phenyl]pyrrol-2H-one.

Mode of action

Flurochloridone is the active substance of some pre-emergence herbicides. It has an inhibitory effect on the synthesis of carotenoids, which protect chlorophylls against oxidative stress.

Toxicity evaluation

The acute oral LD50 of male rats is 4000 mg/kg, the acute transdermal LD50 of rabbits is >5000 mg/kg, and the acute inhalation of rats is LC50 10.3 mg/L (4h). Slightly irritating to rabbit skin and eyes.

InChI:InChI=1/C12H10Cl2F3NO/c13-5-7-6-18(11(19)10(7)14)9-3-1-2-8(4-9)12(15,16)17/h1-4,7,10H,5-6H2

Synthetic route

N-allyl-N-dichloroacetyl-m-trifluoromethylaniline (61219-95-2) → fluorochloridone (61213-25-0)

Conditions	Yield
With [2,2]bipyridinyl; copper(l) chloride In 1,2-dichloro-ethane at 80℃; for 3h; Temperature;	97.6%

fluorochloridone (61213-25-0) → 4-chloromethyl-1-(3-trifluoromethyl-phenyl)-2-pyrrolidone (61213-51-2)

Conditions	Yield
With hydrogenchloride; copper(II) sulfate In ethanol	41.44 g (93%)

Upstream product

• 61219-95-2 N-allyl-N-dichloroacetyl-m-trifluoromethylaniline 

Downstream Products

• 61213-51-2 4-chloromethyl-1-(3-trifluoromethyl-phenyl)-2-pyrrolidone 

Relevant articles and documents

Synthesis method for improving purity of fluorochloridone

The invention discloses a synthesis method for improving the purity of fluorochloridone, and belongs to the technical field of pesticide intermediates. The synthesis method comprises the following steps: S1, taking a compound shown as a formula (III) and allyl chloride as raw materials, taking an alkaline solution or a salt solution as a solvent, carrying out catalytic reaction at 20-25 DEG C under the action of a phase transfer catalyst, and treating after the reaction is finished to obtain a compound shown as a formula (II); S2, taking the compound as shown in the formula (II) as a raw material, taking anhydrous 1, 2-dichloroethane as a solvent, and carrying out reflux reaction at 80-100 DEG C for 4-6 hours under the combined catalytic action of cuprous chloride and 2, 2-dipyridyl, so as to prepare a mixture containing fluorochloridone; and S3, purifying the fluorochloridone. During purification, an extraction solvent is adopted, large-polarity by-products can be removed to a great extent, and residues are simply stirred and washed by n-hexane, so that a fluorochloridone raw material medicine with the purity of more than 95% can be obtained.

Synergistic herbicidal compositions

Synergistic herbicidal activity is displayed by compositions comprising the following two components: (a) a pyrrolidone of the formula STR1 in which X is selected from the group consisting of hydrogen, chlorine and methyl; Y is selected from the group consisting of hydrogen, chlorine and bromine; Z is selected from the group consisting of chlorine and bromine; R1 is selected from the group consisting of hydrogen and C1 -C4 alkyl; R2 is selected from the group consisting of hydrogen, halogen, C1 -C4 alkyl, acetyl, trifluoromethyl, nitro, cyano, C1 -C4 alkoxy, C1 -C4 alkylthio, C1 -C4 alkylsulfinyl, C1 -C4 alkylsulfonyl, trifluoromethylsulfinyl, trifluoromethylsulfonyl, pentafluoropropionamido, and 3-methylureido; and R3 is selected from the group consisting of hydrogen, C1 -C4 alkyl, chlorine and trifluoromethyl; and (b) a phosphonic acid of the formula STR2 in which R4 is selected from the group consisting of C1 -C4 alkyl, C1 -C4 haloalkyl, and --CH2 NHCH2 COOH, at a weight ratio of (a) to (b) of from about 0.1:1 to about 20:1.

Synergistic herbicidal compositions

Synergistic herbicidal activity is displayed by compositions comprising the following two components: (a) a pyrrolidone of the formula STR1 in which X is selected from the group consisting of hydrogen, chlorine and methyl; Y is selected from the group consisting of hydrogen, chlorine and bromine; Z is selected from the group consisting of chlorine and bromine; R1 is selected from the group consisting of hydrogen and C1 -C4 alkyl; R2 is selected from the group consisting of hydrogen, halogen, C1 -C4 alkyl, acetyl, trifluoromethyl, nitro, cyano, C1 -C4 alkoxy, C1 -C4 alkylthio, C1 -C4 alkylsulfinyl, C1 -C4 alkylsulfonyl, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, pentafluoropropionamido, and 3-methylureido; and R3 is selected from the group consisting of hydrogen, C1 -C4 alkyl, chlorine and trifluoromethyl; and (b) a m-ureidophenyl carbamate of the formula STR2 in which R4 is C1 -C4 alkyl; R5 is C1 -C4 alkyl; and R6 is selected from the group consisting of hydrogen and C1 -C4 alkyl, 1t a weight ratio of (a) to (b) of from about 0.1: to about 50:1.