Tetrachlorantraniliprole: China’s first diamide insecticide with independent intellectual property rights

Tetrachlorantraniliprole is China’s first diamide insecticide product with independent intellectual property rights, which is made by Shenyang Research Institute of Chemical Industry, using chlorantraniliprole as the lead compound, in which the structural substituent group of benzene ring and pyrazole are structurally modified. Through subsequent in-depth research, the temporary registration of the product was granted in 2013 and planned to be launched to market in 2014. The insecticidal range and the mechanism of action of tetrachlorantraniliprole are relatively quite similar to chlorantraniliprole. Because of its experimental code YP-9080, the product is therefore sometimes called ″9080.″

About the product

Name: Tetrachlorantraniliprole

CAS number: 1104384-14-6

Molecular formula: C17H10BrCl4N502

Structural formula: 

Mechanism of action

Tetrachlorantraniliprole is a ryanicide receptor modulator, which, via binding to ryanicide receptor, opens calcium channel, such that calcium ions in the cell are constantly released into the sarcoplasm, where calcium ions bind to the matrix protein in the sarcoplasm, thus causing continuous pest muscle contraction. The target pest will show convulsion, paralysis, refusal to eat and eventually die out. 

Tetrachlorantraniliprole can affect the growth of larvae and pupae, resulting in reduction of body weight and longer development duration. Tetrachlorantraniliprole has no activity against eggs, its activity against young larvae is higher than that against advanced age larvae, with a lasting period of about 17 days.

Tetrachlorantraniliprole is of contact toxicity, stomach toxicity and systemic conduction against a variety of pests, with an obvious activity of contact toxicity against oriental armyworm larvae, but not systemic on mulberry leaves and roots.

Application and insecticidal spectrum

Applicable to: Rice, corn, vegetables and fruit trees

Insecticidal spectrum: Tetrachlorantraniliprole and chlorantraniliprole target at same pests, with satisfactory effect of control of lepidopterous noctuidae, pyralidae, psychidae, tortricid, pieridae, plutella, gelechiidae and gracillariidae such as chilo suppressalis,  tryporyza incertulas, plutella xylostella and asparagus caterpillar. Specific applications have proved an obvious effect of contact toxicity on armyworm as well as an effective control of spodoptera frugiperda. However, its insecticidal activity against corn borer and asparagus caterpillar is just so-so.

Product features

1. Broad insecticidal spectrum: Tetrachlorantraniliprole has an excellent effect of control oof a variety of pests including noctuidae, pyralidae, plutella, geometridae, tortricidae, tortricid and olethreutidae.

   
   

2. Long lasting effect: Activity against young lepidoptera larvae is higher than that against advanced age larvae, with a lasting period of about 17 days.

   
   

3. Good cost performance ratio: Synthesis process of tetrachlorantraniliprole is similar to that of chlorantraniliprole, but the cost of raw material is lower, and the overall market price is at a low side.

   
   

4. Contact toxicity, stomach toxicity and systemicity: Contact toxicity stops pest feeding within a few minutes after application; the super strong stomach toxicity not only controls lepidopteran pests, but is also effective against some sucking pests and coleoptera pests; strong systemicity against leaves and roots, with good rainfastness, being resistant to rain wash 1 hour later after application, without reduction of the efficacy of applications.

   
   

5. Good mixability: Tetrachlorantraniliprole is mixable with a variety of insecticides and fungicides.

Registration status

At present, Shenyang Research Institute of Chemical Industry has been granted registration of tetrachlorantraniliprole 10% SC in China for control of cabbage beet armyworm, rice leaf folder and corn borer.

Synthesis process

Tetrachlorantraniliprole can be made using 2,3,5-trichloropyridine as the starting material, which is superseded by hydrazine hydrate, cyclized with diethyl maleate (DEM), then phosphorus oxybromide brominated, potassium peroxodisulfate oxidated, alkaline hydrolyzed, leading to Ethyl 3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylate, which is further cyclized with 3-amino-2,5-dichlorobenzoic acid, and is then methylamine open-ring amidated, resulting in generation of the target product. 

Among the above, 2,3,5-trichloropyridine is an intermediate of the herbicides clodinafop-propargyl and isoxapyrifop, which can be obtained based upon pentachloropyridine being used as a raw material; 2,3,5-trichloropyridine can be used to make 2,3-dichloropyridine, which is an intermediate of chlorantraniliprole, bearing in mind that the cost of 2-amino-3,5-dichlorobenzoic acid is lower than that of 2-Amino-5-chloro-3-methylbenzoic acid, therefore tetrachlorantraniliprole shows certain cost advantage over chlorantraniliprole.

Future prospects

Tetrachlorantraniliprole is a chlorantraniliprole-based novel compound, with a chemical structure similar to chlorantraniliprole as well as mechanism of action and efficacy similar to chlorantraniliprole. Tetrachlorantraniliprole shows high activity against lepidopteran pests and can be applied to various crops for pest control. The process route of tetrachlorantraniliprole is similar to that of chlorantraniliprole, but with a lower raw material cost.

Due to the concern of safety of organophosphorus insecticides, the occurrence of resistance from pyrethroids and the ban of neonicotinoid insecticides in the EU countries, a promising future market for diamide insecticides is foreseeable. For now, though, China has been the primary market for tetrachlorantraniliprole, which still remains blank in the international market.