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

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

Uses

Different sources of media describe the Uses of 123312-89-0 differently. You can refer to the following data:
1. Pymetrozine ia a pyridine azomethine antifeedant. Pymetrozine is used as insecticide.
2. Insecticide.
3. Pymetrozine is a pyridine azomethine antifeedant. Pymetrozine is used as insecticide.

Definition

ChEBI: A member of the class of 1,2,4-triazines that is 4,5-dihydro-1,2,4-triazin-3(2H)-one substituted by a methyl group at position 6 and a (pyridin-3-ylmethylidene)amino group at position 4.

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

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.

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.