709-98-8

Usage

References

[1] S. M. Richards, G. Y. H. McClure, T. L. Lavy, J. D. Mattice, R. J. Keller, J. Gandy (2001) Propanil (3,4-Dichloropropionanilide) Particulate Concentrations Within and Near the Residences of Families Living Adjacent to Aerially Sprayed Rice Fields, Arch. Environ. Contam. Toxicol. 41, 112–116 [2] Michael A. Kamrin (1997) Pesticide Profiles: Toxicity, Environmental Impact, and Fate

Air & Water Reactions

Hydrolyzed by acid and alkaline media.

Reactivity Profile

Propanil is incompatible with carbamates and organophosphates.

Hazard

Toxic by ingestion and inhalation.

Trade name

Cekupropanil; DCPA; N-(3,4-Dichlorophenyl) propanamide; 3',4'-Dichlorophenyl propionanilide; 3,4-Dichloropropionanilide; 3',4'-Dichloropropionanilide; Dichloropropionanilide; Dipram; DPA; NSC 31312; Propanamide, N-(3,4-Dichlorophenyl)-; Propanide; Propionanilide, 3',4'-Dichloro-; Propionic acid, 3,4-dichloroanilide

Safety Profile

Poison by ingestion. Moderately toxic by an unspecified route. Mildly toxic by skin contact. Mutation data reported. When heated to decomposition it emits very toxic fumes of Cl and NOx.

Potential Exposure

Propanil is used as a postemergent herbicide for rice and spring wheat. A potential danger to those involved in the manufacture, formulation, and application of this contact herbicide.

Environmental Fate

Biological. In the presence of suspended natural populations from unpolluted aquatic systems, the second-order microbial transformation rate constant determined in the laboratory was reported to be 5 × 10–10 L/organisms-hour (Steen, 1991). Soil. Propanil degrades in soil forming 3,4-dichloroaniline (Bartha, 1968; Bartha and Pramer, 1970; Chisaka and Kearney, 1970; Bartha, 1971; Duke et al., 1991; Pothuluri et al., 1991) which is further degraded by microbial peroxidases to 3,3′,4,4′-tetrachloroazobenzene (Bartha and Pramer, 1967; Bartha et al., 1968; Chisaka and Kearney, 1970), 3,3′,4,4′-tetrachloroazooxybenzene (Bartha and Pramer, 1970), 4-(3,4-dichloroanilo)- 3,3′,4,4′-tetrachloroazobenzene (Linke and Bartha, 1970) and 1,3-bis(3,4-dichlorophenyl)triazine (Plimmer et al., 1970a), propanoic acid, carbon dioxide and unidentified products (Chisaka and Kearney, 1970). Evidence suggests that 3,3′,4,4′-tetrachloroazobenzene reacted with 3,4-dichloroaniline forming a new reaction product, namely 4-(3,4- dichloroanilo)-3,3′,4′-trichloroazobenzene (Chisaka and Kearney, 1970). Under aerobic conditions, propanil in a biologically active, organic-rich pond sediment underwent dechlorination at the para- position forming N-(3-chlorophenyl)propanamide (Stepp et al., 1985). Residual activity in soil is limited to approximately 3–4 months (Hartley and Kidd, 1987). Plant. In rice plants, propanil is rapidly hydrolyzed via an aryl acylamidase enzyme isolated by Frear and Still (1968) forming the nonphototoxic compounds (Ashton and Monaco, 1991) 3,4-dichloroaniline, propionic acid (Matsunaka, 1969; Menn and Still, 1977; Hatzios, 1991) and a 3′,4′-dichloroaniline-lignin complex. This complex was identified as a metabolite of N-(3,4-dichlorophenyl)glucosylamine, a 3,4-dichloroaniline saccharide conjugate and a 3,4-dichloroaniline sugar derivative (Yi et al., 1968). In a rice field soil under anaerobic conditions, however, propanil underwent amide hydrolysis and dechlorination at the para position forming 3,4-dichloroaniline and m-chloroaniline (Pettigrew et al., 1985). In addition, propanil may degrade indirectly via an initial oxidation step resulting in the formation of 3,4-dichlorolacetanilide which is further hydrolyzed to 3,4-dichloroaniline and lactic acid (Hatzios, 1991). In an earlier study, four metabolites were identified in rice plants, two of which were positively identified as 3,4-dichloroaniline and N-(3,4-dichlorophenyl)glucosylamine (Still, 1968). Photolytic. Photoproducts reported from the sunlight irradiation of propanil (200 mg/L) in distilled water were 3′-hydroxy-4′-chloropropionanilide, 3′-chloro-4′-hydroxypropionanilide, 3′,4′-dihydroxypropionanilide, 3′-chloropropionanilide, 4′-chloropropionanilide, propionanilide, 3,4-dichloroaniline, 3-chloroaniline, propionic acid, propionamide, 3,3′,4,4′-tetrachloroazobenzene and a dark polymeric humic substance. The photolysis products resulted from the reductive dechlorination, replacement of chlorine substituents by hydroxyl groups, formation of propionamide, hydrolysis of the amide group and azobenzene formation (Moilanen and Crosby, 1972). Tanaka et al. (1985) studied the photolysis of propanil (100 mg/L) in aqueous solution using UV light (λ = 300 nm) or sunlight. After 26 days of exposure to sunlight, propanil degraded forming a trichlorinated biphenyl product (<1% yield) and hydrogen chloride (Tanaka et al., 1985). Chemical/Physical. Hydrolyzes in acidic and alkaline media to propionic acid (Worthing and Hance, 1991) and 3,4-dichloroaniline (Sittig, 1985; Worthing and Hance, 1991). The half-life of propanil in a 0.50 N sodium hydroxide solution at 20°C was determined to be 6.6 days (El-Dib and Aly, 1976).

Waste Disposal

Hydrolysis in acidic or basic media yields the more toxic substance, 3,4-dichloraniline, and is not recommended.

InChI:InChI=1/C9H9Cl2NO/c1-2-9(13)12-6-3-4-7(10)8(11)5-6/h3-5H,2H2,1H3,(H,12,13)

Synthetic route

3,4-dichloronitrobenzene (99-54-7) + propionic acid (802294-64-0) → Propanil (709-98-8)

Conditions	Yield
With sodium sulfite for 16h; Reflux;	89%
With iodine at 140℃; for 6h;

N-(4-chlorophenyl)propionamide (2759-54-8) → Propanil (709-98-8)

Conditions	Yield
With iron(III) chloride; chlorine In N,N-dimethyl-formamide at 70℃; for 3h; Temperature;	88%

ethene (74-85-1) + 3,4-dichloronitrobenzene (99-54-7) + carbon monoxide (201230-82-2) → Propanil (709-98-8)

Conditions	Yield
With tetrakis(acetonitrile)palladium bistriflate; boric acid; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene In tetrahydrofuran at 80℃; under 750.075 Torr; for 20h; Autoclave; regioselective reaction;	86%

propionic acid (802294-64-0) + m,p-dichloroaniline (95-76-1) → Propanil (709-98-8)

Conditions	Yield
Stage #1: propionic acid With 4-methyl-morpholine; 1,3,5-trichloro-2,4,6-triazine In acetic acid butyl ester for 1h; Stage #2: m,p-dichloroaniline In acetic acid butyl ester at 23℃; for 1h;	73%

ethene (74-85-1) + carbon monoxide (201230-82-2) + m,p-dichloroaniline (95-76-1) → Propanil (709-98-8)

Conditions	Yield
With bis(η3-allyl-μ-chloropalladium(II)); hydroxylamine hydrochloride; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene at 120℃; for 24h; Autoclave; High pressure;	72%

1-[2-(dimethylamino)ethyl]-1,2-dihydro-5H-tetrazole-5-thione (61607-68-9) + 7-amino-3-(3-oxobutyryloxy)methyl-3-cephem-4-carboxylic acid + Propanil (709-98-8) → 7-amino-3-[1-(2-N,N-dimethylaminoethyl)-1H-tetrazol-5-yl]thiomethyl-3-cephem-4-carboxylic acid dihydrochloride

Conditions	Yield
In ethanol; dichloromethane; acetonitrile	93.3%

7-amino-3-(3-carboxypropionyloxy)methyl-3-cephem-4-carboxylic acid + Propanil (709-98-8) + 1-methyl-5-mercaptotetrazole (13183-79-4) → 7-amino-3-(1-methyl-1H-tetrazole-5-ylthiomethyl)-3-cephem-4-carboxylic acid

Conditions	Yield
In acetonitrile	88%

7-amino-3-(2-carboxybenzoyloxy)methyl-3-cephem-4-carboxylic acid + Propanil (709-98-8) + 1-methyl-5-mercaptotetrazole (13183-79-4) → 7-amino-3-(1-methyl-1H-tetrazole-5-ylthiomethyl)-3-cephem-4-carboxylic acid

Conditions	Yield
In water; acetonitrile	86.5%

Propanil (709-98-8) → propionic acid (802294-64-0) + m,p-dichloroaniline (95-76-1)

Conditions	Yield
With zinc(II) oxide for 1.5h; Kinetics; Mechanism; Concentration; Irradiation;

Upstream product

• 123-62-6 propionic acid anhydride 
• 95-76-1 m,p-dichloroaniline 
• 99-54-7 3,4-dichloronitrobenzene 
• 802294-64-0 propionic acid 
• 74-85-1 ethene 
• 201230-82-2 carbon monoxide 
• 2759-54-8 N-(4-chlorophenyl)propionamide 

Downstream Products

• 802294-64-0 propionic acid 
• 95-76-1 m,p-dichloroaniline 
• 2151-01-1 3,4-dichloro-N-hydroxypropionanilide 
• 18598-29-3 3,4-dichloro-2-hydroxypropionanilide 

Relevant academic research and scientific papers

Method for efficiently preparing 3, 4-dichlorophenyl propanamide

The invention discloses a method for efficiently preparing 3, 4-dichlorophenyl propionamide, which is characterized in that 3, 4-dichloroaniline, propionic acid and propionic anhydride are used as raw materials and are subjected to condensation reaction in the presence of a catalyst to synthesize the 3, 4-dichlorophenyl propionamide. The propionic anhydride is added into the raw materials and can react with water formed by reaction to form propionic acid, the effect of a dehydrating agent is achieved, the reaction speed is increased, the condensation time is shortened to 3-3.5 h, the production efficiency is greatly improved, the dehydration step after the condensation reaction is omitted, the technological process is simplified, and the cost and energy consumption are reduced. The water content of the propionic acid recovered after the condensation reaction is below 0.3%, the propionic acid can be directly applied without treatment, the reaction is still normally carried out after the propionic acid is applied, and the product is qualified. The method does not use a phosphorus-containing catalyst, does not generate three wastes, and is more in line with the construction of green chemical industry.

Intermediate formation enabled regioselective access to amide in the Pd-catalyzed reductive aminocarbonylation of olefin with nitroarene

An efficient route for the palladium-catalyzed reductive aminocarbonylation of olefins with nitroarenes was developed using carbon monoxide (CO) as both reductant and carbonyl source, which enables facile access to amides with excellent regioselectivity a

Synthesis method of propanil

The invention discloses a synthesis method of propanil. The synthesis method comprises the following steps: firstly performing an acylation reaction on chlorobenzene as a raw material and propionyl chloride to produce p-chloropropiophenone, then performing a condensation reaction on the p-chloropropiophenone and hydroxylamine hydrochloride to produce 1-(4-chlorophenyl)-1-acetoxime, then rearranging the 1-(4-chlorophenyl)-1-acetoxime under an acidic condition, and finally chlorinating to obtain the propanil. By the synthesis method, the reaction selectivity in each step is relatively high, no obvious side reaction occurs and the reaction conversion rate is high, so that the reaction yield is high and the product purity is high; a reaction condition is mild; the raw material cost is low; a requirement on reaction equipment is low; phosphorus-containing wastewater discharge is avoided; extension and tolerance are strong; the conversion success rate from trial production to large-scale production is high, and even if the reaction is interrupted, the trial production can be continued in the later stage; and therefore, the synthesis method is suitable for industrial mass production.

NOXIOUS ARTHROPOD CONTROL AGENT CONTAINING AMIDE COMPOUND

An object of the present invention is to provide a compound having the controlling activity on a noxious arthropod, and a noxious arthropod controlling agent containing an amide compound of formula (I): wherein X represents a nitrogen atom or a CH group, p represents 0 or 1, A represents a tetrahydrofuranyl group or the like, R1, R2, R3, R4, R5, R6 and R7 represent a hydrogen atom or the like, n represents 1 or 2, Y represents an oxygen atom or the like, m represents any integer of 0 to 7, and Q represents a C1-8 chain hydrocarbon group optionally having a phenyl group or the like, has the excellent noxious arthropod controlling effect.

Palladium-catalyzed hydroaminocarbonylation of alkenes with amines promoted by weak acid

The weak acid has been identified as an efficient basicity-mask to overcome the basicity barrier imparted by aliphatic amines in the Pd-catalyzed hydroaminocarbonylation, which enables both aromatic and aliphatic amines to be applicable in the palladium-catalyzed hydroaminocarbonylation reaction. Notably, by using this protocol, the marketed herbicide of Propanil and drug of Fentanyl could be easily obtained in a one-pot manner.

Reductive acylation of nitroarenes to anilides by sodium sulfite in carboxylic acids

A facile and efficient reductive acylation of aromatic nitro compounds to corresponding anilides using a sodium sulfite-carboxylic acid system for the first time has been reported. The sodium sulfite reagent provides the colorless reductant in combination with stoichiometric amounts of carboxylic acid and enables the formation of anilides from nitroarenes without any additives in good to excellent yields with high purities and simple work-up. Furthermore, this protocol provides a novel and complementary access to some industrially important chemicals in kilogram scale under mild conditions.

BONE CEMENT FORMULA AND BIORESORBABLE HARDENED BONE CEMENT COMPOSITES PREPARED WITH THE SAME

The present invention provides a bone cement formula having a powder component and a setting liquid component, wherein the powder component includes a calcium sulfate source and a calcium phosphate source with a weight ratio of the calcium sulfate source less than 65%, based on the total weight of the calcium sulfate source and the calcium phosphate source, and the setting liquid component comprises ammonium ion (NH4+) in a concentration of about 0.5 M to 4 M, wherein the calcium phosphate source includes tetracalcium phosphate (TTCP) and dicalcium phosphate in a molar ratio of TTCP to dicalcium phosphate of about 0.5 to about 2.5, and the calcium sulfate source is calcium sulfate hemihydrate (CSH), calcium sulfate dehydrate (CSD), or anhydrous calcium sulfate.

REACTIVE FLAME RETARDANT AND FLAME-RETARDANT RESIN PROCESSED ARTICLE

Disclosed is a reactive flame retardant which provides a resin with excellent flame retardance even when it is added in a small amount while being prevented from bleedout. Also disclosed is a flame-retardant resin processed article obtained by using such a reactive flame retardant. An organophosphorus compound represented by the general formula (I) below, wherein at least one or more of X1-X3 represent a group containing phosphorus and having a terminal unsaturated group, is used as a reactive flame retardant which is reactive with resins. A flame-retardant resin processed article can be obtained by solidifying the resin composition containing the organophosphorus compound and then reacting it through heating or application of radiation.

A novel synthesis of N-arylamides from nitroarenes via reductive N-acylation with red phosphorus and iodine

A series of N-arylamides and imides were synthesized via reductive N-acylation of nitroarenes with red phosphorus and carboxylic acids, catalyzed by iodine or iodides; an I /I° redox cycle was proposed to promote the reaction. Georg Thieme Verlag Stuttgart.

Solid mixtures based on sulfonylureas and adjuvants

Solid mixtures comprising a) an active compound from the group consisting of the sulfonylureas, and b) an alkylpolyglucoside.