5465-96-3

Basic information

• Product Name: 2-Nitroaminoimidazoline
• Synonyms: 4,5-dihydro-n-nitro-1h-imidazol-2-amine;2-Nitroaminoimidazoline;2-(NITROIMINO)IMIDAZOLIDINE;4,5-dihydro-n-nitro-1h-imidazol-2-amin;1H-Imidazol-2-amine, 4,5-dihydro-N-nitro-;N-NITROIMINO IMIDAZOLIDINE;4,5-DIHYDRO-N-NITRO-1H-IMIDAZOL-2-AMINES;2-NITROAMINOIMIDAZOLINE[FOR IMIDACLOPRID]
• CAS NO: 5465-96-3
• Molecular Formula: C₃H₆N₄O₂
• Molecular Weight: 130.11
• Mol File: 5465-96-3.mol
• Article Data: 18

Chemical Properties

• Melting Point: 220 °C
• Boiling Point: 255.06 °C at 760 mmHg
• Flash Point: 108.057 °C
• Appearance: /
• Density: 1.818 g/cm³
• Vapor Pressure: 0.0167mmHg at 25°C
• Storage Temp.: Amber Vial, Refrigerator
• Solubility: DMSO (Slightly), Methanol (Slightly)
• PKA: 8.55±0.20(Predicted)
• CAS DataBase Reference: 2-Nitroaminoimidazoline(CAS DataBase Reference)
• NIST Chemistry Reference: 2-Nitroaminoimidazoline(5465-96-3)
• EPA Substance Registry System: 2-Nitroaminoimidazoline(5465-96-3)

Safety Data

• Hazardous Substances Data: 5465-96-3(Hazardous Substances Data)

Usage

Uses

2-Nitroamino-2-imidazoline is a neonicotinoid substituents that forms water bridge at nicotinic acetylcholine receptor.

InChI:InChI=1/C3H6N4O2/c8-7(9)6-3-4-1-2-5-3/h1-2H2,(H2,4,5,6)/p+1

Synthetic route

S,S-dimethyl N-(nitro)imidodithiocarbonate (141972-53-4) → 2-(nitroimino)imidazolidine (5465-96-3)

Conditions	Yield
With ethylenediamine In chloroform	96.1%

ethylenediamine (107-15-3) + S,S-dimethyl N-(nitro)imidodithiocarbonate (141972-53-4) → 2-(nitroimino)imidazolidine (5465-96-3)

Conditions	Yield
In chloroform at 20℃;	95%
In chloroform at 20 - 27℃;	93.2%
In chloroform at 25 - 27℃; for 3h;	93.2%

S-isopropyl S'-methyl N-nitroimidodithiocarbonate → 2-(nitroimino)imidazolidine (5465-96-3)

Conditions	Yield
With ethylenediamine In chloroform	92.3%

2-nitroguanidine (556-88-7) + ethylenediamine (107-15-3) → 2-(nitroimino)imidazolidine (5465-96-3)

Conditions	Yield
With hydrogenchloride at 56℃; for 8h;	76%
With hydrogenchloride In water at 60℃; for 8h; Inert atmosphere;	62%
With hydrogenchloride In water at 60℃; for 8h;	61%

ethylenediamine (107-15-3) + S-methyl-N3-nitroisothiourea → 2-(nitroimino)imidazolidine (5465-96-3)

Conditions	Yield
In water at 75℃; for 1.5h;	72%

guanidine nitrate (506-93-4) + ethylenediamine (107-15-3) → 2-(nitroimino)imidazolidine (5465-96-3)

Conditions	Yield
Stage #1: guanidine nitrate With sulfuric acid at 5 - 20℃; Stage #2: ethylenediamine With ammonium hydroxide at 45℃; for 12h; Temperature;	70%

nitroguanidine (556-88-7) + ethylenediamine (107-15-3) → 2-(nitroimino)imidazolidine (5465-96-3)

Conditions	Yield
Cyclization;	58%
With hydrogenchloride In water

nitroguanidine (556-88-7) + 1,2-diaminoethane dihydrochloride (333-18-6) → 2-(nitroimino)imidazolidine (5465-96-3)

Conditions	Yield
With potassium hydroxide	37%

methyl nitrocarbamimidothioate (2986-25-6) + water (7732-18-5) + ethylenediamine (107-15-3) → 2-(nitroimino)imidazolidine (5465-96-3)

(Z)-methyl 2-(bromomethyl)-3-(4-(trifluoromethyl)phenyl)acrylate + 2-(nitroimino)imidazolidine (5465-96-3) → C15H15F3N4O4

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 6h; Inert atmosphere;	94%

2-(nitroimino)imidazolidine (5465-96-3) + phenethylamine (64-04-0) → N'-phenethyl-2-imidazolin-2-amine (74387-77-2)

Conditions	Yield
at 60 - 70℃;	92%

2-(nitroimino)imidazolidine (5465-96-3) + (Z)-methyl 2-(bromomethyl)-3-phenylacrylate (103669-71-2) → C14H16N4O4

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 5h; Reagent/catalyst; Inert atmosphere;	92%

2-(nitroimino)imidazolidine (5465-96-3) + 2-bromomethyl-3-p-tolyl-acrylic acid ethyl ester (329329-57-9) → C16H20N4O4

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 5h; Inert atmosphere;	92%

2-(nitroimino)imidazolidine (5465-96-3) + α-Cl-β-thiazolyl chloride (105827-91-6) → (EZ)-1-(2-chloro-1,3-thiazol-5-ylmethyl)-N-nitroimidazolidin-2-ylideneamine

Conditions	Yield
With potassium carbonate In acetonitrile Reflux;	91.5%
With tetrabutylammomium bromide; potassium carbonate In toluene at 47℃; for 7h; Temperature;	91.4%
With potassium carbonate In acetonitrile for 4h; Heating;	66%

2-(nitroimino)imidazolidine (5465-96-3) + methyl (2Z)-2-(bromomethyl)-3-(4-bromophenyl)prop-2-enoate → C14H15BrN4O4

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 5.5h; Inert atmosphere;	91%

(Z)-methyl 2-(bromomethyl)-3-(3-chlorophenyl)acrylate + 2-(nitroimino)imidazolidine (5465-96-3) → C14H15ClN4O4

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 5.5h; Inert atmosphere;	91%

2-(nitroimino)imidazolidine (5465-96-3) + 2-chloro-3-(chloromethyl)-5-methylpyridine + cesium chloride → 1-(2-chloro-5-methyl-3-pyridylmethyl) 2-nitroiminoimidazolidine

Conditions	Yield
With potassium carbonate In acetonitrile	90%
With potassium carbonate In acetonitrile	90%
With potassium carbonate In acetonitrile	90%
With potassium carbonate In acetonitrile	90%

2-(nitroimino)imidazolidine (5465-96-3) + methyl (2Z)-2-(bromomethyl)-3-(4-chlorophenyl)prop-2-enoate (139413-75-5) → C14H15ClN4O4

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 6h; Inert atmosphere;	90%

2-(nitroimino)imidazolidine (5465-96-3) + (Z)-ethyl 2-(bromomethyl)-3-phenylacrylate (88039-49-0) → C15H18N4O4

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 5.5h; Inert atmosphere;	90%

2-(nitroimino)imidazolidine (5465-96-3) + N-[(4-cyano-3-methylsulfanyl-1-phenyl)pyrazol-5-yl]iminomethylenyl ethyl ether (97441-93-5) → 1-[(4-cyano-3-methylthio-1-phenyl)pyrazol-5-yl]iminomethyl-2-nitroiminoimidazolidine (399559-98-9)

Conditions	Yield
With sodium hydride In acetonitrile at 20℃; for 3h;	89%
sodium hydride In acetonitrile	89.3%

2-(nitroimino)imidazolidine (5465-96-3) + 2-chloro-3-(chloromethyl)-5-methyl-6-phenylpyridine (1205671-87-9) → 2-{1-[(2-chloro-5-methyl-6-phenyl-3-pyridyl)methyl]-tetrahydro-1H-2-imidazolyliden}-1-oxo-1-hydraziniumolate (1172115-84-2)

Conditions	Yield
With cesium chloride; potassium carbonate In acetonitrile for 2.5h; Reflux;	89%

2-(nitroimino)imidazolidine (5465-96-3) + ethyl-6-chloro-5-(chloromethyl)-2-phenylnicotinate (1205671-89-1) → 2-(1-{[2-chloro-5-(ethoxycarbonyl)-6-phenyl-3-pyridyl]-methyl}tetrahydro-1H-2-imidazolyliden)-1-oxo-1-hydraziniumolate (1172115-87-5)

Conditions	Yield
With cesium chloride; potassium carbonate In acetonitrile for 2.5h; Reflux;	88%

2-(nitroimino)imidazolidine (5465-96-3) + (2E) 2-bromomethyl-3-(4-methylphenyl)prop-2-enenitrile → N-[1-[(Z)-2-cyano-3-(p-tolyl)allyl]imidazolidin-2-ylidene]nitramide

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 6h; Inert atmosphere;	88%

2-chloro-3-methyl-5-pyridylmethyl chloride (150807-88-8) + 2-(nitroimino)imidazolidine (5465-96-3) → 1-(6-chloro-5-methylpyridin-3-ylmethyl)-2-nitroiminoimidazolidine

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide at 20℃; for 2h;	87%

2-(nitroimino)imidazolidine (5465-96-3) + (E)-2-(bromomethyl)-3-phenylacrylonitrile (139413-81-3) → C13H13N5O2

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 5.5h; Inert atmosphere;	87%

2-(nitroimino)imidazolidine (5465-96-3) + (E)-2-(bromomethyl)-3-(4-chlorophenyl)acrylonitrile (139413-83-5) → N-[1-[(Z)-3-(4-chlorophenyl)-2-cyano-allyl]imidazolidin-2-ylidene]nitramide

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 6.5h; Inert atmosphere;	87%

2-(nitroimino)imidazolidine (5465-96-3) + 2-chloro-5-(chloromethyl)pyridine (70258-18-3) → 1-(6-chloronicotinyl)-2-nitroiminoimidazoline (105827-78-9)

Conditions	Yield
With potassium carbonate In acetonitrile Alkylation; Heating;	86%
With potassium carbonate In acetonitrile Heating / reflux;	83.5%
With N-benzyl-N,N,N-triethylammonium chloride; potassium carbonate In N,N-dimethyl-formamide at 35 - 40℃;	80.5%

2-(nitroimino)imidazolidine (5465-96-3) + 2-chloro-3-(chloromethyl)-5-pentylpyridine (1205671-81-3) → 2-{1-[(2-chloro-5-pentyl-3-pyridyl)methyl]-tetrahydro-1H-2-imidazolyliden}-1-oxo-1-hydraziniumolate (1205672-01-0)

Conditions	Yield
With cesium chloride; potassium carbonate In acetonitrile for 2.5h; Reflux;	86%

2-(nitroimino)imidazolidine (5465-96-3) + methyl-6-chloro-5-(chloromethyl)-2-pyridinecarboxylate (1205671-90-4) → 2-(1-{[2-chloro-6-(methoxycarbonyl)-3-pyridyl]-methyl}-tetrahydro-1H-2-imidazolyliden)-1-oxo-1-hydraziniumolate (1172115-83-1)

Conditions	Yield
With cesium chloride; potassium carbonate In acetonitrile for 2.5h; Reflux;	86%

2-(nitroimino)imidazolidine (5465-96-3) + propyl halogenide → C6H12N4O2 (218764-59-1)

Conditions	Yield
With potassium carbonate In acetonitrile Alkylation; Heating;	85%

2-(nitroimino)imidazolidine (5465-96-3) + [(4-ethoxycarbonyl-3-methio-1-phenyl)pyrazol-5-yl]iminomethyl ethyl ether → 1-[(4-ethoxycarbonyl-3-methylthio-1-phenyl)pyrazol-5-yl]iminomethyl-2-nitroiminoimidazolidine (399559-99-0)

Conditions	Yield
With sodium hydride In acetonitrile at 20℃; for 3h;	84%

2-(nitroimino)imidazolidine (5465-96-3) + 2-chloro-3-(chloromethyl)-5-isopropylpyridine (1205671-80-2) → 2-{1-[(2-chloro-5-isopropyl-3-pyridyl)methyl]-tetrahydro-1H-2-imidazolyliden}-1-oxo-1-hydraziniumolate (1205671-99-3)

Conditions	Yield
With cesium chloride; potassium carbonate In acetonitrile for 2.5h; Reflux;	84%

2-(nitroimino)imidazolidine (5465-96-3) + epichlorohydrin (106-89-8) → 1-(1,2-epoxypropyl)-N-nitroimidazolidin-2-ylamine

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide at 60℃; for 2h; Temperature; Solvent;	83.9%

2-(nitroimino)imidazolidine (5465-96-3) + 2-chloro-3-(chloromethyl)-5-methylpyridine → 2-{1-[(2-chloro-5-methyl-3-pyridyl)methyl]-tetrahydro-1H-2-imidazolyliden}-1-oxo-1-hydraziniumolate (518314-62-0)

Conditions	Yield
With cesium chloride; potassium carbonate In acetonitrile for 2.5h; Reflux;	82%

2-(nitroimino)imidazolidine (5465-96-3) + 2-chloro-3-(chloromethyl)-5-propylpyridine (1205671-78-8) → 2-{1-[(2-chloro-5-propyl-3-pyridyl)methyl]-tetrahydro-1H-2-imidazolyliden}-1-oxo-1-hydraziniumolate (1205671-97-1)

Conditions	Yield
With cesium chloride; potassium carbonate In acetonitrile for 2.5h; Reflux;	82%

Upstream product

• 35878-49-0 nitro-(1-nitroso-4,5-dihydro-1H-imidazol-2-yl)-amine 
• 62-53-3 aniline 
• 556-88-7 nitroguanidine 
• 107-15-3 ethylenediamine 
• 2986-25-6 methyl nitrocarbamimidothioate 
• 6937-92-4 N-(2-chloro-ethyl)-N'-nitro-guanidine 
• 506-93-4 guanidine nitrate 
• 333-18-6 1,2-diaminoethane dihydrochloride 
• 141972-53-4 S,S-dimethyl N-(nitro)imidodithiocarbonate 
• 7732-18-5 water 
• 556-88-7 2-nitroguanidine 

Downstream Products

• 7697-37-2 nitric acid 
• 105827-78-9 1-(6-chloronicotinyl)-2-nitroiminoimidazoline 
• 35878-49-0 nitro-(1-nitroso-4,5-dihydro-1H-imidazol-2-yl)-amine 
• 120-93-4 imidazolidone 
• 19437-45-7 2-amino-2-imidazoline 
• 38941-36-5 benzyl-(4,5-dihydro-1H-imidazol-2-yl)-amine 
• 74387-77-2 N'-phenethyl-2-imidazolin-2-amine 
• 80509-82-6 N-(4,5-dihydro-1H-imidazol-2-yl)-cyclohexylamine 

Relevant articles and documents

Quinoline and 2-nitroimino-1, 3-diazacycloalkane hybrids: Design, synthesis and insecticidal activity

A library of new hybrid molecules comprising quinoline, 2-nitroimino-1, 3-diazacycloalkane motifs were designed and synthesized as plausible neonicotinoid analogues. These compounds were synthesized from 2-chloro/aryloxy-3-formyl quinolines and guanidine nitrate with the coupling of 2-chloro/aryloxy-3-(chloromethyl)quinolines, 2-nitroimino-1, 3-diazacycloalkanes under phase transfer catalysis (PTC) as crucial step. All the compounds were obtained in excellent yields (80–90%) and were characterized by 1H, 13C NMR and mass spectrometry. The newly generated compounds were screened for insecticidal activity against aphids in safflower field and some of them displayed moderate activity.

A MANUFACTURING PROCESS FOR 2-NITROIMINO HETEROCYCLIC COMPOUNDS

The present invention relates to a process for manufacture of 2-nitroimino heterocyclic compounds and intermediates thereof. More particularly, the present invention relates to a convenient manufacturing process for preparation of 2-nitroimino imidazolidine compounds.

Efficient synthesis of N-allylated 2-nitroiminoimidazolidine analogues from Baylis–Hillman bromides

Various Baylis–Hillman–derived new N-allylated 2-nitroiminoimidazolidine analogs were efficiently prepared using potassium carbonate as base. Simple workup procedure, excellent yields, and mild reaction conditions are the salient features of this method. All the synthesized compounds are screened for their larvicidal activity on fourth instar mosquito larvae, Culex quinquefasciatus.