120739-62-0

Basic information

• Product Name: N-[(6-CHLOROPYRIDIN-3-YL)METHYL]-N-METHYLAMINE
• Synonyms: 1-(6-chloro-3-pyridinyl)-N-methylmethanamine 1.4 HCl;1-(6-Chloropyridin-3-yl)-N-MethylMethanaMine dihydrochloride;N-[(6-Chloropyridin-3-yl)methyl]methylamine;1-(6-Chloro-3-pyridinyl)-N-methylmethanamine dihydrochloride;6-chloro-N-methyl-3-pyridinemethanamine;N-[(6-CHLOROPYRIDIN-3-YL)METHYL]-N-METHYLAMINE;2-CHLORO-5-(METHYLAMINOMETHYL)PYRIDINE;[(6-chloropyridin-3-yl)methyl]methylamine dihydrochloride
• CAS NO: 120739-62-0
• Molecular Formula: C₇H₉ClN₂
• Molecular Weight: 156.615
• Mol File: 120739-62-0.mol
• Article Data: 14

Chemical Properties

• Boiling Point: 236.9±25.0 °C(Predicted)
• Appearance: /
• Density: 1.149±0.06 g/cm3(Predicted)
• Storage Temp.: Keep in dark place,Inert atmosphere,Store in freezer, under -20°C
• Solubility: DMSO (Slightly), Methanol (Sparingly)
• PKA: 8.08±0.10(Predicted)
• CAS DataBase Reference: N-[(6-CHLOROPYRIDIN-3-YL)METHYL]-N-METHYLAMINE(CAS DataBase Reference)
• NIST Chemistry Reference: N-[(6-CHLOROPYRIDIN-3-YL)METHYL]-N-METHYLAMINE(120739-62-0)
• EPA Substance Registry System: N-[(6-CHLOROPYRIDIN-3-YL)METHYL]-N-METHYLAMINE(120739-62-0)

Safety Data

• Hazard Codes: Xn
• Statements: 22
• HazardClass: IRRITANT
• Hazardous Substances Data: 120739-62-0(Hazardous Substances Data)

Usage

Uses

N-[(6-Chloropyridin-3-yl)methyl]methylamine is a metabolite of Acetamiprid (A158000), a novel neonicotinid insecticide against Holotrichia consanguinea in sugarcane.

Synthetic route

2-chloro-5-(chloromethyl)pyridine (70258-18-3) + methylamine (74-89-5) → 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0)

Conditions	Yield
Stage #1: methylamine In toluene at -5 - 5℃; Large scale; Stage #2: 2-chloro-5-(chloromethyl)pyridine In toluene at -5 - 2℃; Large scale;	98.5%
In water at 62℃; under 1650.17 Torr; for 1h; Temperature; Pressure;	97.7%
In water at 60℃; for 6h;	95.6%

2-chloro-5-(chloromethyl)pyridine (70258-18-3) → 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0)

Conditions	Yield
With methylamine In ethanol; water

N-benzyl-N,N,N-triethylammonium chloride (56-37-1) + sodium sulfate (7757-82-6) + dimethyl sulfate (77-78-1) + 5-(aminomethyl)-2-chloropyridine (97004-04-1) → 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0)

Conditions	Yield
With sodium hydroxide; formic acid In water; toluene

2-chloro-5-(Trichloromethyl)-pyridine (69045-78-9) → 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0)

Conditions	Yield
With sodium hydroxide; methylamine; aluminum nickel In ethanol; water
With methylamine; aluminum nickel In ethanol; toluene

(E) N'-carbamoyl-N[(6-chloropyridin-3-yl)methyl]-N-methylacetimidamide (215366-29-3) → 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0)

Conditions	Yield
In aq. phosphate buffer at 30℃; for 96h; Time;

N,1-dimethyl-6-(methylthio)-3,5-dinitro-4-phenyl-1,4-dihydropyridin-2-amine (1620024-38-5) + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → N2-((6-chloropyridin-3-yl)methyl)-N2,N6,1-trimethyl-3,5-dinitro-4-phenyl-1,4-dihydropyridine-2,6-diamine (1620024-67-0)

Conditions	Yield
In ethanol at 80℃;	98%

3-(3-chloro-5-fluorophenyl)-2-methylpropanal + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → 6-chloro-N-[3-(3-chloro-5-fluorophenyl)-2-methylpropyl]-N-methyl-pyridin-3-ylmethylamine (360563-40-2)

Conditions	Yield
With sodium tris(acetoxy)borohydride In 1,2-dichloro-ethane at 20℃; for 2h;	97.8%

ethyl N-cyanoacetoimidate (1558-82-3) + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → acetamiprid (135410-20-7)

Conditions	Yield
In ethanol at 65℃;	96.6%

ethyl N‐cyanoethanimidate (1558-82-3) + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → acetamiprid

Conditions	Yield
at 75℃; for 9h; Industrial scale;	96%

2-methyl-4-(3-trifluoromethoxyphenyl)butanal + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → 6-chloro-N-[2-methyl-4-(3-trifluoromethoxyphenyl)-butyl]-N-methyl-pyridin-3-ylmethylamine (374075-93-1)

Conditions	Yield
With sodium tris(acetoxy)borohydride In 1,2-dichloro-ethane at 20℃; for 2.5h;	92.3%

3-(3-fluoro-4-trifluoromethylphenyl)-2-methylpropanal + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → 6-chloro-N-[3-(3-fluoro-4-trifluoromethylphenyl)-2-methylpropyl]-N-methyl-3-pyridylmethylamine (360563-28-6)

Conditions	Yield
With sodium tris(acetoxy)borohydride In 1,2-dichloro-ethane at 20℃; for 1h;	91.2%

2-methyl-3-(4-trifluoromethoxyphenyl)propanal + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → 6-chloro-N-methyl-N-[3-(4-trifluoromethoxyphenyl)-2-methylpropyl]-3-pyridylmethylamine (360563-31-1)

Conditions	Yield
With sodium tris(acetoxy)borohydride In 1,2-dichloro-ethane at 20℃; for 2h;	86.9%

4,5-dichloroisothiazole-3-carboxylic acid chloride (220769-88-0) + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → 4,5-dichloro-N-[(6-chloropyridin-3-yl)methyl]-N-methyl-1,2-thiazole-3-carboxamide

Conditions	Yield
In tetrahydrofuran at 0 - 20℃; for 5h;	86%

3-(3-fluoro-4-trifluoromethoxyphenyl)-2-methylpropanal + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → 6-chloro-N-[3-(3-fluoro-4-trifluoromethoxyphenyl)-2-methylpropyl]-N-methyl-3-pyridylmethylamine (360563-36-6)

Conditions	Yield
With sodium tris(acetoxy)borohydride In 1,2-dichloro-ethane at 20℃; for 2h;	85.3%

diethyl (1-methyl-3-nitro-2-oxo-1,2-dihydroquinolin-4-yl)malonate (193673-40-4) + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → ethyl 3-[N-(6-chloropyridin-3-ylmethyl)-N-methylamino]-2-(1-methyl-3-nitro-2-oxo-1,2-dihydroquinolin-4-yl)-3-oxopropanoate

Conditions	Yield
In toluene for 0.5h; Heating;	83%

3,4-dibromo-5-methoxy-2,5-dihydrofuran-2-one (767-97-5) + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → 3-bromo-4-(((6-chloropyridin-3-yl)methyl)(methyl)amino)-5-methoxy-2,5-dihydrofuran-2-one

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 20℃;	83%

3-(4-t-butylcyclohexyl)-2-methylpropanal + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → N-[3-(4-t-butylcyclohexyl)-2-methylpropyl]-6-chloro-N-methyl-pyridin-3-ylmethylamine (374075-97-5)

Conditions	Yield
With sodium tris(acetoxy)borohydride In 1,2-dichloro-ethane at 20℃; for 1.5h;	82.9%

3-(3,5-difluoro-4-trifluoromethoxyphenyl)-2-methylpropanal + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → 6-chloro-N-[3-(3,5-difluoro-4-trifluoromethoxyphenyl)-2-methylpropyl]-N-methyl-pyridin-3-ylmethylamine (360563-39-9)

Conditions	Yield
With sodium tris(acetoxy)borohydride In 1,2-dichloro-ethane at 20℃; for 2h;	81.6%

N-(1,2,3,3-tetrachloroallylidene)-N'-(4-nitrophenyl)hydrazine (915797-44-3) + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → N-[N-(6-chloropyridin-3-ylmethyl)-N-methylamino-2,3,3-trichloroallylidene]-N'-(4-nitrophenyl)hydrazine

Conditions	Yield
In methanol at 20℃;	80%

2-chloro-5-{[(2E)-2-(2,3,3-trichloro-1-nitroprop-2-en-1-ylidene)-1,3-oxazolidin-3-yl]methyl}pyridine (1175523-43-9) + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → (3Z)-1,1-dichloro-N-[(6-chloropyridin-3-yl)methyl]-3-{3-[(6-chloropyridin-3-yl)methyl]-1,3-oxazolidin-2-ylidene}-N-methyl-3-nitroprop-1-en-2-amine (1175523-55-3)

Conditions	Yield
	80%

formaldehyd (50-00-0) + 4,5-diphenyl-4H-1,2,4-triazole-3-thiol (6596-82-3) + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → 2-{[(6-chloropyridin-3-ylmethyl)methylamino]methyl}-4,5-diphenyl-3H-1,2,4-triazole

Conditions	Yield
With sodium hydroxide In ethanol at 20℃;	72.4%

4,5-dichloro-N’-phenyl-1,2-thiazole-3-carbohydrazide + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → 4,5-dichloro-N-[(6-chloropyridin-3-yl)methyl]-N-methyl-1,2-thiazole-3-carboxamide

Conditions	Yield
In dimethyl sulfoxide for 8h;	69%

formaldehyd (50-00-0) + 3-benzyl-4-phenyl-5-mercapto-1,2,4-triazole (22478-90-6) + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → 2-{[(6-chloropyridin-3-ylmethyl)methylamino]methyl}-5-benzyl-4-phenyl-3H-1,2,4-triazole

Conditions	Yield
With sodium hydroxide In ethanol at 20℃;	64.3%

3,4-dichloro-5-methoxy-2-(5H)furanone (23066-93-5) + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → 3-chloro-4-(((6-chloropyridin-3-yl)methyl)(methyl)amino)-5-methoxy-2,5-dihydrofuran-2-one

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 20℃;	63%

2-chloro-3-nitro-6-ethoxy-pyridine + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → 6-ethoxy-N-((2-chloropyridine-5-yl)methyl)-N-methyl-3-nitropyridine-2-amine

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 50 - 80℃;	51.1%

iso-propyl 4-acetoxybut-2-ynecarboxylate (1258291-70-1) + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → C15H19ClN2O5

Conditions	Yield
In tetrahydrofuran at 20℃; for 16h;	50%

2,2-dimethyl-3-(4-trifluoromethoxyphenyl)propanal + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → 6-chloro-N-[2,2-dimethyl-3-(4-trifluoromethoxyphenyl)propyl]-3-pyridylmethylamine (374075-80-6)

Conditions	Yield
With sodium tris(acetoxy)borohydride; acetic acid In 1,2-dichloro-ethane at 20℃; for 2h;	31.8%

3-chloro-1,2-benzisothiazole 1,1-dioxide (567-19-1) + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → 3-(((6-chloropyridin-3-yl)methyl)(methyl)amino)benzoisothiazole 1,1-dioxide

Conditions	Yield
In acetonitrile for 6h; Reflux;	26%

3-methyl-1H-pyrazolo[3,4-b]quinoxaline (374553-37-4) + formaldehyd (50-00-0) + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → 1-[N-(2-chloropyridin-5-ylmethyl)-N-methylamino]methyl-3-methyl-1H-pyrazolo[3,4-b]quinoxaline

Conditions	Yield
In ethanol; water Mannich reaction; Heating;

1,1,1-trifluoro-4,4-bis(methylthio)-3-butene-2-one (115970-23-5) + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → 1-[N-(6-chloro-3-pyridylmethyl)-N-methyl]amino-1-methylthio-4, 4,4-trifluoro-1-buten-3-one (135325-25-6)

Conditions	Yield
In ethanol	0.88 g (27%)

ethyl acetimidate hydrochloride (2208-07-3) + 1-(6-chloropyridin-3-yl)-N-methylmethanamine (120739-62-0) → N-[(6-chloropyridyl-3-yl)methyl]-N-methylacetamidine (135410-04-7)

Conditions	Yield
In ethanol
In ethanol at 20 - 25℃; for 15h;

Upstream product

• 70258-18-3 2-chloro-5-(chloromethyl)pyridine 
• 69045-78-9 2-chloro-5-(Trichloromethyl)-pyridine 
• 215366-29-3 (E) N'-carbamoyl-N[(6-chloropyridin-3-yl)methyl]-N-methylacetimidamide 
• 74-89-5 methylamine 
• 56-37-1 N-benzyl-N,N,N-triethylammonium chloride 
• 7757-82-6 sodium sulfate 
• 77-78-1 dimethyl sulfate 
• 97004-04-1 5-(aminomethyl)-2-chloropyridine 

Downstream Products

• 374075-80-6 6-chloro-N-[2,2-dimethyl-3-(4-trifluoromethoxyphenyl)propyl]-3-pyridylmethylamine 
• 374075-97-5 N-[3-(4-t-butylcyclohexyl)-2-methylpropyl]-6-chloro-N-methyl-pyridin-3-ylmethylamine 
• 360563-36-6 6-chloro-N-[3-(3-fluoro-4-trifluoromethoxyphenyl)-2-methylpropyl]-N-methyl-3-pyridylmethylamine 
• 360563-39-9 6-chloro-N-[3-(3,5-difluoro-4-trifluoromethoxyphenyl)-2-methylpropyl]-N-methyl-pyridin-3-ylmethylamine 
• 1620024-67-0 N₂-((6-chloropyridin-3-yl)methyl)-N₂,N₆,1-trimethyl-3,5-dinitro-4-phenyl-1,4-dihydropyridine-2,6-diamine 
• 135410-20-7 acetamiprid 

Relevant articles and documents

Degradation of the neonicotinoid insecticide acetamiprid via the N-carbamoylimine derivate (IM-1-2) mediated by the nitrile hydratase of the nitrogen-fixing bacterium Ensifer meliloti CGMCC 7333

The metabolism of the widely used neonicotinoid insecticide acetamiprid (ACE) has been extensively studied in plants, animals, soils, and microbes. However, hydration of the N-cyanoimine group in ACE to the N-carbamoylimine derivate (IM-1-2) by purified microbes, the enzyme responsible for this biotransformation, and further degradation of IM-1-2 have not been studied. The present study used liquid chromatography-mass spectrometry and nuclear magnetic resonance spectroscopy to determine that the nitrogen-fixing bacterium Ensifer meliloti CGMCC 7333 transforms ACE to IM-1-2. CGMCC 7333 cells degraded 65.1% of ACE in 96 h, with a half-life of 2.6 days. Escherichia coli Rosetta (DE3) overexpressing the nitrile hydratase (NHase) from CGMCC 7333 and purified NHase converted ACE to IM-1-2 with degradation ratios of 97.1% in 100 min and 93.9% in 120 min, respectively. Interestingly, IM-1-2 was not further degraded by CGMCC 7333, whereas it was spontaneously hydrolyzed at the N-carbamoylimine group to the derivate ACE-NH, which was further converted to the derivative ACE-NH2. Then, ACE-NH2 was cleaved to the major metabolite IM-1-4. IM-1-2 showed significantly lower insecticidal activity than ACE against the aphid Aphis craccivora Koch. The present findings will improve the understanding of the environmental fate of ACE and the corresponding enzymatic mechanisms of degradation.

METHOD FOR PURIFYING 1-(6-CHLOLOPYRIDINE-3-YL)-N-METHYLMETHANAMINE

The present application provides a method for purifying 1-(6-chloropyridin-3-yl)-N-methylmethanamine. It is possible to obtain 1-(6-chloropyridin-3-yl)-N-methylmethanamine with high purity.

Pyridine methylamino pyridine compound and method for preparing the same

The invention discloses a picolinate amino pyridine compound which is shown in the formula (I) and has sterilizing, insect/mite killing and weeding bioactivity as well as a preparation method thereof, a sterilizing, insect/mite killing and weeding herbicide composition containing the compound, and an application and method for controlling fungi, insects/mites and weeds by using the compound.