123312-89-0

Basic information

• Product Name: Pymetrozine
• Synonyms: Hsdb 7054;6-Methyl-4-((pyridin-3-ylMethylene)aMino)-4,5-dihydro-1,2,4-triazin-3(2H)-one;(E)-4,5-dihydro-6-Methyl-4-[(3-pyridinylMethylene)aMino]-1,2,4-triazin-3(2H)-one;4,5-Dihydro-6-Methyl-4-[(E)-(3-pyridinylMethylene)aMino]-1,2,4-triazin-3(2H)-one;A 9364A;(E)-6-Methyl-4-((pyridin-3-ylMethylene)aMino)-4,5-dihydro-1,2,4-triazin-3(2H)-one;Pymetrozine 0;Pymetrozin Solution, 100ppm
• CAS NO: 123312-89-0
• Molecular Formula: C₁₀H₁₁N₅O
• Molecular Weight: 217.23
• EINECS: 200-258-5
• Product Categories: Agro-Products;Aromatics;Heterocycles;Alpha sort;N-PPesticides&Metabolites;OthersAlphabetic;P;Pesticides;Pesticides&Metabolites;PU - PZ
• Mol File: 123312-89-0.mol
• Article Data: 6

Chemical Properties

• Melting Point: 234.4°
• Flash Point: >230 °C
• Appearance: colorless crystals
• Density: 1.33 g/cm³
• Vapor Pressure: 0Pa at 25.03℃
• Refractive Index: 1.665
• Storage Temp.: 0-6°C
• Solubility: DMSO (Slightly), Methanol (Slightly)
• PKA: 12.90±0.40(Predicted)
• Stability: Hygroscopic
• BRN: 7814151
• CAS DataBase Reference: Pymetrozine(CAS DataBase Reference)
• NIST Chemistry Reference: Pymetrozine(123312-89-0)
• EPA Substance Registry System: Pymetrozine(123312-89-0)

Safety Data

• Hazard Codes: Xn
• Statements: 40-52/53-R52/53-R40
• Safety Statements: 36/37-61-S61-S36/37
• WGK Germany: 2
• RTECS: XZ3018620
• Hazardous Substances Data: 123312-89-0(Hazardous Substances Data)

Usage

Uses

Used in Agriculture:
Pymetrozine is used as an insecticide for controlling various pests, particularly aphids, whiteflies, and leafhoppers. It works by inhibiting the feeding behavior of these pests, leading to their eventual starvation and death. This selective action makes Pymetrozine an environmentally friendly alternative to traditional insecticides.
Used in Horticulture:
In horticulture, Pymetrozine is used as an insecticide to protect ornamental plants and crops from damage caused by sucking pests such as aphids and whiteflies. Its selective nature ensures that beneficial insects, pollinators, and natural predators are not harmed, promoting a balanced ecosystem and sustainable pest management.
Used in Integrated Pest Management (IPM):
Pymetrozine is an essential component of Integrated Pest Management strategies, which aim to reduce the reliance on chemical pesticides and promote a more sustainable approach to pest control. By targeting specific pests and minimizing harm to beneficial organisms, Pymetrozine contributes to the overall success of IPM programs.
Used in Public Health:
Pymetrozine can also be used in public health applications to control pests that transmit diseases or cause nuisances. Its selective action and low toxicity make it suitable for use in areas where human exposure is a concern, such as residential and recreational settings.

Descriptioin

Pymetrozine is a new neuroactive insecticide. It has a remarkable selectivity for sucking insect pests, such as aphids, whiteflies, and plant hoppers, due to its systemic action. Pymetrozine is the only representative of the pyridine azomethines, a new class of insecticides. Pymetrozine has been determined to be of low acute toxicity to humans, birds, aquatic organisms, mammals, and bees. It is also not mutagenic.

Reference

J. Ausborn, H. Wolf, W. Mader, H. Kayser, The insecticide pymetrozine selectively against affects chordotonal mechanoreceptors, Journal of Experimental Biology, 2005, vol. 208, pp. 4451-4466 D. Fuog, S. J. Fergusson, C. Flückiger, Pymetrozine: A Novel Insecticide Affecting Aphids and Whiteflies, Insecticides with Novel Modes of Action, 1998, ISBN 978-3-642-08314-3

InChI:InChI=1/C10H11N5O/c1-8-7-15(10(16)14-13-8)12-6-9-3-2-4-11-5-9/h2-6H,7H2,1H3,(H,14,16)/b12-6+

Synthetic route

3-pyridinecarboxaldehyde (500-22-1) + 2,3,4,5-tetrahydro-3-oxo-4-amino-6-methyl-1,2,4-triazine (123313-07-5) → pymetrozine (123312-89-0)

Conditions	Yield
In ethanol at 50℃; Reflux;	92%

C10H12ClN5O → pymetrozine (123312-89-0)

Conditions	Yield
With potassium carbonate In methanol at 25 - 30℃; for 5h; Reagent/catalyst;	85%

methyl (E)-1- (2-oxopropyl)-2-(pyridin-3-ylmethylene)hydrazine-1-carboxylate → pymetrozine (123312-89-0)

Conditions	Yield
With hydrazine hydrate In tetrahydrofuran at 0 - 25℃; Cooling; Green chemistry;	70%

methyl (E)-1- (2-oxopropyl)-2-(pyridin-3-ylmethylene)hydrazine-1-carboxylate → C11H15N5O2 + pymetrozine (123312-89-0) + hydrazone of pyridine-3-carboxaldehyde (26364-02-3) + 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene (13362-77-1)

Conditions	Yield
With hydrazine hydrate In ethanol at 25℃;	A 28% B 37% C 14% D 15%
With hydrazine hydrate In ethanol at 80℃; Solvent;	A 36% B 16% C 21% D 18%
With hydrazine hydrate In ethanol at 80℃;	A 35% B 15% C 17% D 19%
With hydrazine hydrate In ethanol at 50℃;	A 24% B 21% C 8% D 10%

methyl (E)-1- (2-oxopropyl)-2-(pyridin-3-ylmethylene)hydrazine-1-carboxylate → C11H15N5O2 + pymetrozine (123312-89-0)

Conditions	Yield
With hydrazine hydrate In ethanol at 0 - 25℃;	A 20% B 23%

3-pyridinecarboxaldehyde (500-22-1) + 4-amino-6-methyl-3-oxo-2,3,4,5-tetrahydro-1,2,4-triazine hydrochloride → pymetrozine (123312-89-0)

Conditions	Yield
With sodium hydroxide In methanol; water

3-pyridinecarboxaldehyde (500-22-1) + 2,3,4,5-tetrahydro-3-oxo-4-amino-6-methyl-1,2,4-triazine (123313-07-5) → pymetrozine (123312-89-0)

Conditions	Yield
In methanol at 65℃; for 12h; Temperature; Green chemistry; Large scale;	2080 g

methyl (E)-2-(pyridin-3-ylmethylene)hydrazine-1-carboxylate → pymetrozine (123312-89-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: potassium carbonate / N,N-dimethyl-formamide / 5 h / 25 - 30 °C / Cooling with ice; Green chemistry 2: hydrazine hydrate / tetrahydrofuran / 0 - 25 °C / Cooling; Green chemistry View Scheme

methyl (E)-2-(pyridin-3-ylmethylene)hydrazine-1-carboxylate → C11H15N5O2 + pymetrozine (123312-89-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: potassium carbonate / N,N-dimethyl-formamide / 5 h / 25 - 30 °C / Cooling with ice; Green chemistry 2: hydrazine hydrate / ethanol / 0 - 25 °C View Scheme

methanol (67-56-1) + pymetrozine (123312-89-0) → 5-Methoxy-6-methyl-4-{[1-pyridin-3-yl-meth-(E)-ylidene]-amino}-4,5-dihydro-2H-[1,2,4]triazin-3-one

Conditions	Yield
With tetraethylammonium tosylate for 24h; current (6 V, 200 mA), graphite electrodes;	30%

(2,4-dinitro-phenyl)-hydrazine (119-26-6) + pymetrozine (123312-89-0) → pyridine-3-carbaldehyde-(2,4-dinitro-phenylhydrazone) (1834-93-1) + 2,3,4,5-tetrahydro-3-oxo-4-amino-6-methyl-1,2,4-triazine (123313-07-5)

Conditions	Yield
In ethanol

pymetrozine (123312-89-0) → 5-Hydroxy-6-methyl-4-{[1-pyridin-3-yl-meth-(E)-ylidene]-amino}-4,5-dihydro-2H-[1,2,4]triazin-3-one

Conditions	Yield
With N,N,N,N,-tetramethylethylenediamine; sec.-butyllithium; oxygen; iron(II) sulfate 1.) -78 deg C, 150 min, -78 deg C to 25 deg C, 8 h, rt, overnight, THF, cyclohexane; Yield given. Multistep reaction;
Multi-step reaction with 2 steps 1: 30 percent / tetraethylammonium p-toluenesulfonate / 24 h / current (6 V, 200 mA), graphite electrodes 2: 53 percent / aq. citric acid / tetrahydrofuran / Ambient temperature; overnight View Scheme

Upstream product

• 500-22-1 3-pyridinecarboxaldehyde 
• 123313-07-5 2,3,4,5-tetrahydro-3-oxo-4-amino-6-methyl-1,2,4-triazine 

Downstream Products

• 1834-93-1 pyridine-3-carbaldehyde-(2,4-dinitro-phenylhydrazone) 
• 123313-07-5 2,3,4,5-tetrahydro-3-oxo-4-amino-6-methyl-1,2,4-triazine 

Relevant articles and documents

An efficient protocol for the production of pymetrozine via a new synthetic strategy

A practical four-step synthesis of pymetrozine is reported, starting from a green chemical dimethyl carbonate and using the key intermediate methyl (E)-1-(2-oxopropyl)-2-(pyridin-3-ylmethylene)hydrazine-1-carboxylate. The main advantages of the route include inexpensive starting materials, environmental friendliness, short synthetic route, easy-to-use synthetic method and acceptable overall yield. A scale-up experiment was carried out to provide pymetrozine with 99.84% purity in 53.2% total yield.

Method for preparing pymetrozine

The invention discloses a method for preparing pymetrozine with an aim to provide a synthesis method short in reaction route of the pymetrozine, small in environmental pollution and simple in technology operation, and belongs to the technical field of organic synthesis. The method includes the steps of 1), allowing dimethyl carbonate serving as a raw material to be subjected to hydrazinolysis withhydrazine hydrate to obtain carbazide; 2), subjecting carbazide and smoke aldehyde to condensation reaction to obtain (E)-N'-(pyridine-3-kiya methyl) hydrazine carbon hydrazide; 3), subjecting (E)-N'-( pyridine-3-kiya methyl) hydrazine carbon hydrazide and chloroacetone to condensation reaction to obtain (E)-N'-(Z)-1-chloropropyl-2-subunit)-2-(pyridine-3-kiya methyl) diazanyl-1-carbohydrazide; 4), subjecting (E)-N'-(Z)-1-chloropropyl-2-subunit)-2-(pyridine-3-kiya methyl) diazanyl-1-carbohydrazide to ring formation under the alkaline condition to obtain the pymetrozine.

A high-efficiency green pymetrozine preparation method

The invention discloses a high-efficiency and green method for preparing pymetrozine. According to the method, a byproduct methyl acetate produced in a pymetrozine condensation step serves as a raw material and replaces ethyl acetate in a traditional process for synthesizing acethydrazide, and the produced byproduct methanol can serve as a solvent in a subsequent step, so that the byproduct is recycled, and the raw material utilization rate is improved. Hydrogen chloride or concentrated hydrochloric acid in a traditional process is replaced by adopting a saturated hydrogen chloride methanol solution in the condensation step, and moisture in the system is avoided, so that amino triazone is subjected to a hydrolysis reaction, and byproducts are basically eliminated. According to the method, the yield of the product and the utilization rate of the hydrogen chloride are improved, the reaction time is shortened, emission of wastewater and waste gas is reduced, the comprehensive production cost is reduced, and better conditions are created for industrial large-scale production of the product.

Supramolecular water morphology and methanol solvate in a functionalized pymetrozine host

The crystals of functionalized pymetrozine hydrochloride salts in water (crystal 1) and neutral pymetrozine in methanol (crystal 2) have been obtained. The carbonyl group and the nitrogen atom of Schiff base group of pymetrozine interact with hydrophilic groups (-OH) of methanol or water molecule to form one five-member ring via functional hydrogen bonds. Present results provide new insight and an understanding of the three-dimensional structural aspects of hydrogen bonded liquids with important implications in the structure and behaviour of functional molecules in biological systems.

Active agent combinations

The novel active compound combinations of extracts from seeds of the neem tree and the active compounds of groups (B) to (F) listed in the description have very good insecticidal and acaricidal properties.

Process for the preparation of aminotriazine derivatives

The present invention relates to a process for the preparation of aminotriazine derivatives of the formula I STR1 by the solvolysis of compounds of the formula II STR2 in the presence of gaseous hydrogen chloride in an alcoholic medium. The compounds of formula I are useful as intermediates in the manufacture of insecticides.