35367-38-5

Usage

Uses

Used in Agriculture and Forest Management:
Diflubenzuron is used as a selective insecticide for controlling a wide range of leaf-eating insects, particularly moths and weevils, in forestry, woody ornamentals, and fruit trees. It is effective against major pests on cotton, soybean, citrus, and tea crops.
Used in Public Health:
Diflubenzuron is used as a larvicide by public health authorities in India for the control of mosquito larvae, helping to manage vector-borne diseases.
Used in Livestock Production:
Diflubenzuron is used as an ectoparasiticide to control insects in livestock production, ensuring the health and well-being of animals.
Used in Research:
Diflubenzuron serves as an inhibitor of TCDD-induced CYP1a1 expression in HepG2 cells, contributing to scientific research and understanding of insecticide mechanisms.

Air & Water Reactions

Hydrolyzed in alkaline solution above pH 9.0.

Trade name

ADEPT?; ASTONEX?; DIMILIN?; DIMILIN? FLO; DIMILIN? WG-80; DU-112307?; DUPHAR? PH 60-40; ODC-45?; DIFLURON?; DU 112307?; LARGON?; LARVAKIL?; MICROMITE?; OMS 1804?; PDD 60401?; PH 60- 40?; PHILIPS-DUPHAR? PH 60-40; TH 60-40?; THOMPSON-HAYWARD? 6040; VIGILANTE?

Safety Profile

Moderately toxic by skin contact. Mildly toxic by ingestion. Mutation data reported. When heated to decomposition it emits very toxic fumes of Cl-, F-, and NOx.

Environmental Fate

Soil. The half-life in soil is <1 week (Hartley and Kidd, 1987). Di?ubenzuron degrades more rapidly in neutral or basic conditions but more slowly under acidic conditions (pH <6) (Ivie et al., 1980).Chemical/Physical. Hydrolyzes in water to 4-chlorophenylurea (Verschueren, 1983).

Metabolic pathway

Diflubenzuron was the first active substance commercialised as a benzoylurea insect growth regulator and there is extensive published information on its degradation and metabolism. Detailed studies of the degradation in soils have shown that cleavage of the urea linkage is the major process. This also occurs in plants, insects and mammals but the formation of products in which diflubenzuron is hydroxylated in both rings is also an important metabolic process.

Degradation

Diflubenzuron was shown to be stable to hydrolysis in aqueous solution at acidic pH (DT50> 56 days at pH 4) but was readily hydrolysed at pH 10 (DT50 <3 days). In distilled water the DTa was 7 days (Ivie et al., 1980). The major degradation products isolated were 4-chlorophenylurea (2) and 2,6-difluorobenzoic acid (3). An additional minor product was 2,6- difluorobenzamide (4). The hydrolysis products are shown in Scheme 1. Additional products were formed under extreme conditions (121 °C under pressure).Aqueous solutions of diflubenzuron are reported to be unstable to light but the solid is stable in sunlight (PM).

Toxicity evaluation

Diflubenzuron is an odorless, white, crystalline solid with a melting point of 230–232
C. It is almost insoluble in water (0.2 mg l1) and poorly soluble in apolar organic solvents.It is almost nonvolatile. It is relatively stable in acidic and neutral media but hydrolyses under alkaline conditions. Diflubenzuron is difficult to be degraded in sterilized water under neutral or acidic conditions. However, it is degraded rapidly under field conditions. Application of diflubenzuron to water resulted rapid partition to sediment; the parent compound and 4-chlorophenylurea (CPU) may persist on sediment for more than 30 days. The rate of degradation of diflubenzuron in soil is strongly dependent on the particle size. For larger particles (10 microns), the half-life is 8–16 weeks and for smaller particles (2 microns), it is 0.5–1 week. Almost all of the parent compound breaks down to form 2,6-difluorobenzoic acid (DFBA) and CPU. A very minor amount forms 4-chloroaniline (PCA) which rapidly binds to the soil. Under field conditions, diflubenzuron has very low mobility. Very little diflubenzuron is absorbed, metabolized, or translocated in plants. It also is not readily taken up from treated soil. Diflubenzuron has very low vapor pressure (<2×10-7 Pa at 25°C) and its atmospheric half-life is only several hours. Therefore, it is not expected that diflubenzuron will be present in air for extended periods and the long-range transport and redeposition of diflubenzuron is expected to be negligible.

InChI:InChI=1/C14H9ClF2N2O2.C12H6Cl4O2S/c15-8-4-6-9(7-5-8)18-14(21)19-13(20)12-10(16)2-1-3-11(12)17;13-7-1-3-8(4-2-7)19(17,18)12-6-10(15)9(14)5-11(12)16/h1-7H,(H2,18,19,20,21);1-6H

Synthetic route

4-chloro-aniline (106-47-8) + S-allyl N-(2,6-difluorobenzoyl)monothiocarbamate (148931-18-4) → 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5)

Conditions	Yield
With triethylamine In benzene for 2h; Heating;	70%

4-chloro-aniline (106-47-8) + N-(Bis-methylsulfanyl-methylene)-2,6-difluoro-benzamide (119448-98-5) → 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5)

Conditions	Yield
With acetic acid for 6h; Heating;	69%

2,6-difluorobenzoylchloride (18063-02-0) + N-(4-chlorophenyl)urea (140-38-5) → 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5) + N-(4-chlorophenyl)-2,6-difluorobenzamide (122987-01-3)

Conditions	Yield
In toluene for 7h; Heating;	A 67% B 5 g
In toluene for 7h; Heating;	A 5 g B 5 g

1-(4-chlorophenyl)-3-(3,5-difluorobenzyl)urea → 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5)

Conditions	Yield
With 9-(2-mesityl)-10-methylacridinium perchlorate In chloroform at 35℃; for 4h; Irradiation;	64%

2,6-difluorobenzoyl isocyanate (60731-73-9) + C10H13ClN2O2S → 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5) + C18H16ClF2N3O4S

Conditions	Yield
In 1,2-dichloro-ethane at 20℃; for 3h;	A n/a B 60.1%

2,6-difluorobenzoyl isocyanate (60731-73-9) + N-(t-butoxycarbonyl)-4-chloroaniline (18437-66-6) → 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5) + C19H17ClF2N2O4

Conditions	Yield
In 1,2-dichloro-ethane Heating;	A n/a B 59%

1-bromo-2,6-difluorobenzene (64248-56-2) + carbon monoxide (201230-82-2) + N-(4-chlorophenyl)urea (140-38-5) → 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5)

Conditions	Yield
With palladium diacetate; triethylamine; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In 1,4-dioxane at 100℃; under 3361.55 Torr; for 4h; Microwave irradiation;	45%

benzyl N-methylcarbamate (30379-59-0) + 2,6-difluorobenzoyl isocyanate (60731-73-9) + 4-chloro-aniline (106-47-8) → 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5) + C23H18ClF2N3O4S

Conditions	Yield
Stage #1: benzyl N-methylcarbamate With sulfur dichloride Stage #2: 4-chloro-aniline With pyridine In tetrahydrofuran at 20℃; Stage #3: 2,6-difluorobenzoyl isocyanate In 1,2-dichloro-ethane at 20℃;	A n/a B 11.9%

2,6-difluorobenzamide (18063-03-1) + p-chlorphenylisocyanate (104-12-1) → 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5)

Conditions	Yield
In toluene for 5h; Heating;
With sodium hydride In N,N-dimethyl-formamide 1.) 30 min., -10 to 0 deg C, 2.) 4h, room temperature;
In 5,5-dimethyl-1,3-cyclohexadiene at 140℃; for 5h; Temperature; Large scale;

2,6-difluorobenzoyl isocyanate (60731-73-9) + phenyl N-(4-chlorophenyl)carbamate (50882-28-5) → 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5) + N-2,6-difluorobenzoyl-O-phenylcarbamate

4-chloro-aniline (106-47-8) → 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: 51.6 percent / aq. NaOH / dioxane / 15 h / 20 °C 2: 1,2-dichloro-ethane / Heating View Scheme
Multi-step reaction with 2 steps 1: 69 percent / pyridine / tetrahydrofuran / 0.5 h / 20 °C 2: 1,2-dichloro-ethane / 3 h / 20 °C View Scheme

2,6-difluorobenzoyl isothiocyanate → 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5)

Conditions	Yield
Multi-step reaction with 3 steps 1: benzene / 96 h / Ambient temperature 2: 70 percent / benzene / 11 h / Heating 3: 70 percent / Et3N / benzene / 2 h / Heating View Scheme

O-allyl N-(2,6-difluorobenzoyl)monothiocarbamate (148931-10-6) → 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: 70 percent / benzene / 11 h / Heating 2: 70 percent / Et3N / benzene / 2 h / Heating View Scheme

2,6-difluorobenzoylchloride (18063-02-0) → 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.) CH3CN, RT, 5 min, 2.) CH3CN, reflux, 5 h 2: 70 percent / Et3N / benzene / 2 h / Heating View Scheme

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + 2,6-difluorobenzamide (18063-03-1) + p-chlorphenylisocyanate (104-12-1) → 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5)

Conditions	Yield
With N-Bromosuccinimide In methanol; 1,2-dichloro-ethane

p-chlorphenylisocyanate (104-12-1) + 1,1,2,2-tetrachloroethane (79-34-5) → 2,6-difluorobenzamide (18063-03-1) + 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5)

Conditions	Yield
In n-heptane

2,6-difluorobenzylamine (69385-30-4) + p-chlorphenylisocyanate (104-12-1) → 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: dichloromethane / 0.17 h / 0 - 20 °C 2: 9-(2-mesityl)-10-methylacridinium perchlorate / chloroform / 4 h / 35 °C / Irradiation View Scheme

1,3,5-triallylhexahydro-1,3,5-triazine (26028-43-3) + 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5) → 5-allyl-1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)tetrahydro-1,3,5-triazin-2(1H)-one

Conditions	Yield
Stage #1: 1,3,5-triallylhexahydro-1,3,5-triazine With phosphorus pentachloride In dichloromethane at 40℃; for 2.5h; Stage #2: 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea In dichloromethane at 1℃; for 0.25h; Stage #3: With triethylamine In dichloromethane at 1 - 20℃; for 5h;	75%

PhCH2O2CN(CH2Cl)2 + 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5) → 5-benzyloxycarbonyl-1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)tetrahydro-1,3,5-triazin-2(1H)-one

Conditions	Yield
Stage #1: 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea With sodium hydride In DMF (N,N-dimethyl-formamide) at 3℃; for 0.5h; Stage #2: PhCH2O2CN(CH2Cl)2 In tetrahydrofuran; DMF (N,N-dimethyl-formamide) at 1 - 20℃; for 6h;	46.6%

bis-iodomethyl sulfide (98025-72-0) + 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5) → 3-(4-chlorophenyl)-5-(2,6-difluorobenzoyl)tetrahydro-4H-1,3,5-thiadiazin-4-one (596848-90-7)

Conditions	Yield
Stage #1: 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea With sodium hydride In DMF (N,N-dimethyl-formamide) at 3℃; for 0.666667h; Stage #2: bis-iodomethyl sulfide In DMF (N,N-dimethyl-formamide) at 3 - 20℃; for 18h;	20%

1,3,5-trimethyl-1,3,5-triazacyclohexane (108-74-7) + 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5) → 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)-5-methyltetrahydro-1,3,5-triazin-2(1H)-one

Conditions	Yield
Stage #1: 1,3,5-trimethyl-1,3,5-triazacyclohexane With phosphorus pentachloride In dichloromethane at 40℃; for 2.5h; Stage #2: 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea In dichloromethane at 1℃; for 0.25h; Stage #3: With sodium hydroxide; triethylamine more than 3 stages;	19%

bis(2-chloromethyl)ether (542-88-1) + 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5) → 3-(4-chlorophenyl)-5-(2,6-difluorobenzoyl)tetrahydro-4H-1,3,5-oxadiazin-4-one

Conditions	Yield
Stage #1: 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea With sodium hydride In DMF (N,N-dimethyl-formamide) at 3℃; for 0.666667h; Stage #2: bis(2-chloromethyl)ether In DMF (N,N-dimethyl-formamide) at 3 - 20℃; for 2h;	19%

1,3,5-Triisopropyl-1,3,5-triazacyclohexane (10556-98-6) + 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5) → 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)-5-phenyltetrahydro-1,3,5-triazin-2(1H)-one

Conditions	Yield
Stage #1: 1,3,5-Triisopropyl-1,3,5-triazacyclohexane With phosphorus pentachloride In dichloromethane at 40℃; for 4h; Stage #2: 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea In dichloromethane at 1℃; for 0.25h; Stage #3: With sodium hydroxide; triethylamine more than 3 stages;	16%

1,3,5-Triisopropyl-1,3,5-triazacyclohexane (10556-98-6) + 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5) → 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)-5-isopropyltetrahydro-1,3,5-triazin-2-(1H)-one

Conditions	Yield
Stage #1: 1,3,5-Triisopropyl-1,3,5-triazacyclohexane With phosphorus pentachloride In dichloromethane at 40℃; for 3h; Stage #2: 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea In dichloromethane at 1℃; for 0.25h; Stage #3: With sodium hydroxide; triethylamine more than 3 stages;	15%

1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (35367-38-5) + sodium methylate (124-41-4) → methyl 2,6-difluorobenzoate (13671-00-6) + N-(4-chlorophenyl)urea (140-38-5)

Conditions	Yield
In methanol at 25℃; Kinetics; Mechanism; Rate constant;

Upstream product

• 18063-03-1 2,6-difluorobenzamide 
• 104-12-1 p-chlorphenylisocyanate 
• 106-47-8 4-chloro-aniline 
• 119448-98-5 N-(Bis-methylsulfanyl-methylene)-2,6-difluoro-benzamide 
• 148931-18-4 S-allyl N-(2,6-difluorobenzoyl)monothiocarbamate 
• 18063-02-0 2,6-difluorobenzoylchloride 
• 140-38-5 N-(4-chlorophenyl)urea 
• 60731-73-9 2,6-difluorobenzoyl isocyanate 
• 50882-28-5 phenyl N-(4-chlorophenyl)carbamate 
• 18437-66-6 N-(t-butoxycarbonyl)-4-chloroaniline 
• 30379-59-0 benzyl N-methylcarbamate 
• 280-57-9 1,4-diaza-bicyclo[2.2.2]octane 
• 64248-56-2 1-bromo-2,6-difluorobenzene 
• 201230-82-2 carbon monoxide 

Downstream Products

• 13671-00-6 methyl 2,6-difluorobenzoate 
• 140-38-5 N-(4-chlorophenyl)urea 
• 596848-90-7 3-(4-chlorophenyl)-5-(2,6-difluorobenzoyl)tetrahydro-4H-1,3,5-thiadiazin-4-one 

Relevant academic research and scientific papers

Synthesis process and application of diflubenzuron

The invention relates to the field of diflubenzuron preparation, in particular to a synthesis process and application of diflubenzuron. The diflubenzuron synthesis process comprises the steps: mixing an aromatic hydrocarbon solvent and 2,6-difluorobenzamide, increasing the temperature to 130-145 DEG C, carrying out reflux dehydration, cooling, adding p-chlorphenyl isocyanate in a dropwise manner, after dropwise adding is finished, increasing the temperature to 130-145 DEG C, carrying out a reaction, and performing post-treatment to obtain the product. The synthesis process of the diflubenzuron is simple, the yield of the prepared diflubenzuron is greater than 92 wt%, and the purity of the prepared diflubenzuron is greater than 97 wt%.

Hydrogen bond directed aerobic oxidation of amines via photoredox catalysis

An application of H-bonding interactions for directing the α-C-H oxidation of amines to amides and amino-ketones catalyzed by an organic photocatalyst is reported. The high efficiency of this method is demonstrated by the aerobic oxidation of pyrrolidines, diarylamines and benzylamines bearing urea groups with high yields and a wide substrate scope.

New synthesis of aryl and heteroaryl N-acylureas via microwave-assisted palladium-catalysed carbonylation

A new, practical synthesis of aryl and heteroaryl N-acylureas has been developed via palladium-catalysed carbonylation of aryl or heteroaryl halides in the presence of urea nucleophiles. A range of reactions illustrating the wide scope of this reaction was carried out under microwave irradiation, using either carbon monoxide gas in a vessel equipped with a gas inlet adapter, or molybdenum hexacarbonyl as the carbon monoxide source in standard microwave vials. The reactions proceeded in good to excellent yields. To illustrate the usefulness of this method a one-step synthesis of the important insecticide diflubenzuron is reported.

Cis-Alkoxyspiro-Substituted Tetramic Acid Derivatives

The invention relates to novel cis-alkoxyspiro-substituted tetramic acid derivatives of the formula (I), in which A, G, X, Y and Z are as defined above, to a plurality of processes and intermediates for their preparation and to their use as pesticides and/or herbicides, and also to selective herbicidal compositions comprising firstly cis-alkoxyspiro-substituted tetramic acid derivatives and secondly a crop plant compatibility-improving compound.

SUBSTITUTED SPIROCYCLIC KETOENOLS

The present invention relates to novel substituted spirocyclic ketoenols of the formula (I) in which W, X, Y, Z, A, B, D and G are as defined in the disclosure, to a plurality of processes for their preparation and to their use as pesticides, microbicides and herbicides.

Aryl-substituted heterocyclic enaminones

The invention relates to novel heterocyclic enaminones of the general formula (I) in which Ar, Z, K, X, y1, Y2, Y3, Y4, Y5, Y6 and V are as defined in the description, to their use as herbicides, acaricides and insecticides, and to processes for their preparation.

Synthesis and insecticidal evaluation of propesticides of benzoylphenylureas

Two series of benzoylphenylurea derivatives were synthesized as candidate propesticides by a nucleophilic addition reaction between 2,6-difluronbenzoyl isocyanate and N-substitutedaniline. The new compounds were identified by 1H NMR spectroscopy, electron ionization-mass spectrometry, and elemental analyses. The bioactivities of the new compounds were evaluated. All of the propesticides reported here were soluble in most organic solvents, and their hydrophobicities were improved obviously. The result of the bioactivities of the new compounds against Oriental armyworm showed that some of the new compounds are good as compared to diflubenzuron and penfluron.

Glyoxyl acid amides, method for producing them and their use for controlling harmful organisms

The invention relates to novel gloyoxylic acid amides, to a process for their preparation and to their use for controlling harmful organisms.

Optically active 2,5-bisaryl-delta1-pyrrolines and their use as pest control agents

Novel optically active Δ1-pyrrolines of the formula (I) in which R1, R2, R1, R4, and m are each as defined in the description, a plurality of the processes for preparing these substances and their use for controlling pests.

Phenyl-substituted 5,6-dihydrophyne derivatives for use as pesticides and herbicides

The present invention relates to novel phenyl-substituted 5,6-dihydro-pyrone derivatives of the formula (I) in which W, X, Y, Z, G, A, B, Q1 and Q2 are each as defined in the description, to a plurality of processes for their preparation and to their use as pesticides and herbicides.