645-09-0

Basic information

• Product Name: 3-NITROBENZAMIDE
• Synonyms: M-NITROBENZAMIDE;3-nitro-benzamid;Benzamide, m-nitro-;m-nitro-benzamid;3-NITROBENZAMIDE;3-Nitrobenzamide,98%;N-nitrobenzamide
• CAS NO: 645-09-0
• Molecular Formula: C₇H₆N₂O₃
• Molecular Weight: 166.13
• EINECS: 211-431-0
• Product Categories: Aromatic Carboxylic Acids, Amides, Anilides, Anhydrides & Salts;Amides;Carbonyl Compounds;Organic Building Blocks;Building Blocks;C2 to C7;Carbonyl Compounds;Chemical Synthesis;Organic Building Blocks;Pharmaceutical Intermediates
• Mol File: 645-09-0.mol
• Article Data: 94

Chemical Properties

• Melting Point: 140-143 °C(lit.)
• Boiling Point: 312.55°C
• Flash Point: 145.852°C
• Appearance: Yellow/Crystalline Powder or Crystals
• Density: 1.4994 (rough estimate)
• Vapor Pressure: 0mmHg at 25°C
• Refractive Index: 1.5880 (estimate)
• Storage Temp.: Sealed in dry,Room Temperature
• PKA: 14.86±0.50(Predicted)
• Stability: Stable. Combustible. Incompatible with strong oxidizing agents.
• BRN: 777185
• CAS DataBase Reference: 3-NITROBENZAMIDE(CAS DataBase Reference)
• NIST Chemistry Reference: 3-NITROBENZAMIDE(645-09-0)
• EPA Substance Registry System: 3-NITROBENZAMIDE(645-09-0)

Safety Data

• Statements: 22-36/37/38
• Safety Statements: 24/25-36/37-26
• WGK Germany: 3
• RTECS: CV5601250
• TSCA: Yes
• Hazardous Substances Data: 645-09-0(Hazardous Substances Data)

Usage

Chemical Properties

yellow powder

General Description

Yellow powder.

Air & Water Reactions

Insoluble in water.

Reactivity Profile

A nitrated amide. Organic amides/imides react with azo and diazo compounds to generate toxic gases. Flammable gases are formed by the reaction of organic amides/imides with strong reducing agents. Amides are very weak bases (weaker than water). Imides are less basic yet and in fact react with strong bases to form salts. That is, they can react as acids. Mixing amides with dehydrating agents such as P2O5 or SOCl2 generates the corresponding nitrile. The combustion of these compounds generates mixed oxides of nitrogen (NOx).

Fire Hazard

Flash point data for 3-NITROBENZAMIDE are not available, however, 3-NITROBENZAMIDE is probably combustible.

InChI:InChI=1/C7H6N2O3/c8-7(10)5-2-1-3-6(4-5)9(11)12/h1-4H,(H2,8,10)

Synthetic route

3-nitrobenzonitrile (619-24-9) → 3-nitrobenzamide (645-09-0)

Conditions	Yield
With cobalt(II,III) oxide; water at 140℃; for 24h;	99%
With potassium tert-butylate In tert-butyl alcohol at 20℃; for 12h; Solvent; Temperature; Inert atmosphere;	99%
With manganese(IV) oxide; water In isopropyl alcohol at 100℃; under 5171.62 Torr; for 0.25h;	98%

3-nitro-benzaldehyde (99-61-6) → 3-nitrobenzamide (645-09-0)

Conditions	Yield
Stage #1: 3-nitro-benzaldehyde With hydroxylamine hydrochloride; caesium carbonate In water; dimethyl sulfoxide at 100℃; Stage #2: With palladium diacetate In water; dimethyl sulfoxide at 100℃; for 12h; chemoselective reaction;	98%
With iron(III) chloride; hydroxylamine hydrochloride; caesium carbonate In water at 100℃; for 26h; chemoselective reaction;	95%
With aluminum oxide; hydroxylamine hydrochloride; methanesulfonyl chloride; water at 100℃; for 1h;	94%

3-nitrobenzaldoxime (3431-62-7) → 3-nitrobenzamide (645-09-0)

Conditions	Yield
With C55H45ClN5P2Ru(1+)*Cl(1-) In water at 110℃; for 12h; Sealed tube;	97%
With silver tetrafluoroborate; chloro(1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene)gold(I) at 100℃; for 20h; Beckmann rearrangement; Sealed tube; Neat (no solvent);	94%
With nickel diacetate In xylene

E-3-nitrobenzaldoxime (3717-29-1) → 3-nitrobenzamide (645-09-0)

Conditions	Yield
With indium(III) chloride; 3-nitrobenzonitrile In 1,2-dichloro-benzene for 16h; Reflux;	93%

methyl 3-nitrobenzoate (618-95-1) → 3-nitrobenzamide (645-09-0)

Conditions	Yield
Stage #1: methyl 3-nitrobenzoate With ammonia In ethylene glycol at 40 - 45℃; for 20h; Stage #2: sodium methylate In ethylene glycol at 40 - 45℃; for 5h; Conversion of starting material;	92%
With ammonia; sodium methylate In methanol at 60 - 65℃; for 26h; Conversion of starting material;	68%
Stage #1: methyl 3-nitrobenzoate With ammonia In butan-1-ol at 40 - 45℃; for 20h; Stage #2: sodium methylate In butan-1-ol at 40 - 45℃; for 8h; Conversion of starting material;

3-nitro-benzaldehyde (99-61-6) → 3-nitrobenzonitrile (619-24-9) + 3-nitrobenzamide (645-09-0)

Conditions	Yield
With [Ru(η6-C6Me6)Cl2(tris(dimethylamino)phosphine)]; hydroxylamine hydrochloride; sodium hydrogencarbonate In water at 100℃; for 7h; Reagent/catalyst; Inert atmosphere; Sealed tube; Green chemistry;	A n/a B 92%

(R)-2-amino-3-(((3-nitrobenzoyl)carbamothioyl)thio)propanoic acid (1628342-22-2) → 3-nitrobenzamide (645-09-0) + (4R)-2-sulfanylidene-1,3-thiazolidine-4-carboxylic acid (98169-56-3)

Conditions	Yield
In water for 1h; Reflux;	A 91% B n/a

3-nitrobenzoic acid (121-92-6) → 3-nitrobenzamide (645-09-0)

Conditions	Yield
With 1H-imidazole; urea for 0.05h; microwave irradiation;	88%
With ammonium chloride; triethylamine at 20℃; for 0.0166667h;	87%
With pyridine; potassium cyanate; 2-chloro-1-methyl-pyridinium iodide; water In acetonitrile for 3h; Reflux; Green chemistry;	85%

3-nitrobenzoyl azide (3532-31-8) → 3-nitrobenzamide (645-09-0)

Conditions	Yield
With copper(ll) sulfate pentahydrate; L-ascorbic acid; water; sodium dodecyl sulfate at 60℃; for 1.5h; Inert atmosphere; Green chemistry;	88%

benzonitrile (100-47-0) → 3-nitrobenzamide (645-09-0)

Conditions	Yield
With nitrourea In sulfuric acid at 0 - 20℃;	85%
With sulfuric acid; potassium nitrate for 16h; Ambient temperature;	73%

3-Nitrobenzyl alcohol (619-25-0) → 3-nitrobenzamide (645-09-0)

Conditions	Yield
Stage #1: 3-Nitrobenzyl alcohol With ammonia; iodine In water at 60℃; for 3h; Stage #2: With ammonia; dihydrogen peroxide In water at 0 - 20℃;	85%
With tert.-butylhydroperoxide; ammonium chloride; calcium carbonate In water; acetonitrile at 80℃; for 6h; Inert atmosphere; Green chemistry;	51%

3-nitro-N-(tert-butyl)benzamide (10222-93-2) → 3-nitrobenzamide (645-09-0)

Conditions	Yield
With t-butyldimethylsiyl triflate In toluene at 100℃; for 8h;	83%

benzamide (55-21-0) → 3-nitrobenzamide (645-09-0)

Conditions	Yield
With tetrammine copper(II) sulphate; nitric acid In dichloromethane; water at 20℃; for 3h; regioselective reaction;	82%
With trichloroisocyanuric acid; N,N-dimethyl-formamide; sodium nitrite for 9h; Reflux;	58%
With sulfuric acid; potassium nitrate

3-nitro-N-(p-tolyl)benzamide (6911-92-8) → 3-nitrobenzamide (645-09-0)

Conditions	Yield
With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In water at 25℃; for 22h; regioselective reaction;	79%

3-nitrobenzylamine (7409-18-9) → 3-nitrobenzamide (645-09-0)

Conditions	Yield
With dihydrogen peroxide at 80℃; for 10h; Inert atmosphere;	75%

2-bromo-1-(5-phenyloxazol-2-yl)ethanone (1171113-63-5) + 3-nitrobenzamidine (3459-99-2) → 2-[2-(3-nitrophenyl)-1H-imidazol-4-yl]-5-phenyloxazole (1171113-77-1) + 3-nitrobenzamide (645-09-0)

Conditions	Yield
With water; potassium hydrogencarbonate In tetrahydrofuran at 80℃;	A 71.5% B n/a

3-nitrobenzonitrile (619-24-9) → 3-Aminobenzamide (3544-24-9) + 3-nitrobenzamide (645-09-0)

Conditions	Yield
With graphitic carbon nitride; hydrazine hydrate In water at 80℃; for 20h; Darkness; Sealed tube; Green chemistry; chemoselective reaction;	A 6% B 68%

m-nitrobenzoic acid chloride (121-90-4) → 3-nitrobenzamide (645-09-0)

Conditions	Yield
With ammonium hydroxide In toluene	60%
With ammonia
With ammonium hydroxide In ethyl acetate for 0.166667h;

(E)-2-iodo-3-nitro-N-(prop-1-enyl)benzamide → (E)-3-nitro-N-(prop-1-enyl)benzamide + 3-nitrobenzamide (645-09-0)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); tetrabutyl-ammonium chloride; triethylamine In N,N-dimethyl-formamide for 168h; Reflux;	A 52% B n/a

urea (57-13-6) + 3-nitrobenzoic acid (121-92-6) → 3-nitrobenzamide (645-09-0)

Conditions	Yield
With formic acid at 130 - 180℃; for 2h;	50%

C7H8N2O3 → 3-nitrobenzamide (645-09-0)

Conditions	Yield
With tert.-butylhydroperoxide; ammonia; tetra-(n-butyl)ammonium iodide In water at 100℃; for 16h; Green chemistry;	49%

ethanol (64-17-5) + 1,2-bis-(3-nitrophenyl)ethane-1,2-dione (5913-06-4) + ammonium cyanide (71680-52-9, 130166-69-7) → 3-nitrobenzamide (645-09-0)

3-nitro-benzoic acid bromoamide (33322-43-9) → 3-nitrobenzamide (645-09-0)

Conditions	Yield
With ethanol; sodium ethanolate

ethyl 3-nitrobenzoate (618-98-4) → 3-nitrobenzamide (645-09-0)

Conditions	Yield
With ammonia

1,2-bis-(3-nitrophenyl)ethane-1,2-dione (5913-06-4) + ammonium cyanide (71680-52-9, 130166-69-7) → 3-nitrobenzamide (645-09-0)

Conditions	Yield
With ethanol

E-3-nitrobenzaldoxime (3717-29-1) → 3-nitrobenzaldoxime (3717-30-4) + 3-nitrobenzamide (645-09-0)

Conditions	Yield
With sulfuric acid

acetic acid-(3-nitro-benzoic acid )-anhydride (4015-57-0) → 3-nitrobenzamide (645-09-0)

Conditions	Yield
With ammonia

bis-(3-nitro-benzoyl)-amine (58010-74-5) + furan-2,3,5(4H)-trione pyridine (1:1) → 3-nitrobenzamide (645-09-0) + 3-nitrobenzoic acid (121-92-6)

3-nitrobenzamidine (3459-99-2) + furan-2,3,5(4H)-trione pyridine (1:1) → 3-nitrobenzonitrile (619-24-9) + 3-nitrobenzamide (645-09-0) + 3-nitrobenzoic acid (121-92-6)

3-nitrobenzamide (645-09-0) + tert-butyl 2-chloropyridine-3-carboxylate (232951-83-6) → tert-butyl 2-(3-nitrobenzamido)nicotinate

Conditions	Yield
With C47H65FeNO3P2PdS*C4H8O; caesium carbonate In 2-methyltetrahydrofuran; N,N-dimethyl-formamide at 40℃; for 24h;	100%
With C47H66FeNO3P2PdS*C4H8O; caesium carbonate In 2-methyltetrahydrofuran at 40℃; for 24h; chemoselective reaction;	99%

8-iodo-6-(phenylthio)-9-(tetrahydro-2H-pyran-2-yl)-9H-purine (1380333-86-7) + 3-nitrobenzamide (645-09-0) → 3-nitro-N-(6-(phenylthio)-9-(tetrahydro-2H-pyran-2-yl)-9H-purin-8-yl)benzamide (1380333-91-4)

Conditions	Yield
With tris-(dibenzylideneacetone)dipalladium(0); caesium carbonate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene In 1,4-dioxane at 120℃; for 4h; Inert atmosphere;	97%

3-nitrobenzamide (645-09-0) → 3-Aminobenzamide (3544-24-9)

Conditions	Yield
With borane-ammonia complex; copper(II) oxide In methanol at 50℃; for 0.333333h; chemoselective reaction;	94%
With potassium fluoride; polymethylhydrosiloxane; palladium diacetate In tetrahydrofuran; water at 20℃; for 0.5h;	92%
With potassium fluoride; polymethylhydrosiloxane; palladium diacetate In tetrahydrofuran at 20℃; for 0.5h;	92%

3-nitrobenzamide (645-09-0) → 3-nitrobenzoic acid (121-92-6)

Conditions	Yield
With phthalic anhydride; silica gel microwave irradiation;	93%
With hydrogenchloride In 1,4-dioxane at 90℃; for 3h; Rate constant;

chloral hydrate (302-17-0) + 3-nitrobenzamide (645-09-0) → N-(2,2,2-trichloro-1-hydroxyethyl)-3-nitrobenzamide (357639-01-1)

Conditions	Yield
at 90 - 100℃;	93%
Heating;

1-methyl-6-nitroquinolinium triflate + 3-nitrobenzamide (645-09-0) → N-(1-methyl-6-nitro-1,2-dihydroquinolin-2-yl)-3-nitrobenzamide

Conditions	Yield
Stage #1: 3-nitrobenzamide With sodium hydride In acetonitrile; mineral oil Stage #2: 1-methyl-6-nitroquinolinium triflate In acetonitrile; mineral oil at 20℃; for 0.5h;	93%

3-nitrobenzamide (645-09-0) → 3-(hydroxyamino)benzamide

Conditions	Yield
With hydrazine hydrate at 60℃; for 0.833333h; Green chemistry; chemoselective reaction;	92%
With ethanol; sulfuric acid (electrochemical reduction);
With sulfuric acid In ethanol at 25℃; (electrochemical reduction);

formaldehyd (50-00-0) + glycine ethyl ester hydrochloride (5680-79-5) + 3-nitrobenzamide (645-09-0) → {[(3-Nitro-benzoylamino)-methyl]-amino}-acetic acid methyl ester; hydrochloride

Conditions	Yield
In 1,4-dioxane at 101℃; for 0.0666667h;	90%

acrylic acid n-butyl ester (141-32-2) + 3-nitrobenzamide (645-09-0) → butyl 3-(3-nitrobenzamido)propanoate (1122008-46-1)

Conditions	Yield
With tetrabutylammomium bromide; potassium carbonate for 0.25h; aza-Michael addition; microwave irradiation;	90%

benzylamine (100-46-9) + 3-nitrobenzamide (645-09-0) → N-benzyl-3-nitrobenzamide (7595-68-8)

Conditions	Yield
With Ce(III) immobilised on an aminated epichlorohydrin-activated agarose matrix at 140℃; for 4h; Green chemistry;	90%
With nanosized zeolite beta In neat (no solvent) at 135℃; for 24h;	68%

3-nitrobenzamide (645-09-0) → 3-nitrobenzonitrile (619-24-9)

Conditions	Yield
With diethyl chlorophosphate at 120℃; for 0.25h; Neat (no solvent);	89%
With di-morpholin-4-yl-phosphinic acid chloride; triethylamine In dichloromethane at 20℃; for 4h;	72%
With lead acetate In dichloromethane for 12h; Reflux;	71%

formaldehyd (50-00-0) + glycine ethyl ester hydrochloride (623-33-6) + 3-nitrobenzamide (645-09-0) → {[(3-Nitro-benzoylamino)-methyl]-amino}-acetic acid ethyl ester; hydrochloride

Conditions	Yield
In 1,4-dioxane at 101℃; for 0.0666667h;	85%

tert-butyl 2'-(2-chloropyridin-4-yl)-4'-oxo-5'-(2,4,6-trimethoxybenzyl)-1',4',5',6'-tetrahydro spiro[piperidine-3,7'-pyrrolo[3,2-c]pyridine]-1-carboxylate + 3-nitrobenzamide (645-09-0) → tert-butyl 2'-(2-(3-nitrobenzamido)pyridin-4-yl)-4'-oxo-5'-(2,4,6-trimethoxybenzyl)-1',4',5',6'-tetrahydro spiro[piperidine-3,7'-pyrrolo[3,2-c]pyridine]-1-carboxylate

Conditions	Yield
With tris-(dibenzylideneacetone)dipalladium(0); caesium carbonate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene In 1,4-dioxane at 150℃; for 0.333333h; Microwave irradiation;	85%

formaldehyd (50-00-0) + 3-nitrobenzamide (645-09-0) → 3-nitro-N-(hydroxymethyl)benzamide (40478-11-3)

Conditions	Yield
With NaY zeolite In water at 100℃; for 24h;	84%
With potassium carbonate
With potassium carbonate In 1,4-dioxane
With potassium carbonate In methanol at 20℃; for 24h;

ethyl Bromopyruvate (70-23-5) + 3-nitrobenzamide (645-09-0) → ethyl 2-(3-nitrophenyl)oxazole-4-carboxylate (1279818-81-3)

Conditions	Yield
With silver hexafluoroantimonate In 1,2-dichloro-ethane at 90℃; for 2h; Inert atmosphere; Microwave irradiation;	81%

phenylacetylene (536-74-3) + 3-nitrobenzamide (645-09-0) → 3-nitro-N-[(Z)-2-phenylvinyl]benzamide (389572-33-2)

Conditions	Yield
With [bis(2-methylallyl)cycloocta-1,5-diene]ruthenium(II); 1,4-bis(dicyclohexylphosphino)butane; ytterbium(III) triflate In water; N,N-dimethyl-formamide at 60℃; for 6h; Inert atmosphere; optical yield given as %de; stereoselective reaction;	80%
With [bis(2-methylallyl)cycloocta-1,5-diene]ruthenium(II); 1,4-bis(dicyclohexylphosphino)butane; water; ytterbium(III) triflate In N,N-dimethyl-formamide at 60℃; for 6h; anti-Markovnikov hydroamidation; Inert atmosphere; optical yield given as %de; stereoselective reaction;	80%

Upstream product

• 64-17-5 ethanol 
• 5913-06-4 1,2-bis-(3-nitrophenyl)ethane-1,2-dione 
• 71680-52-9 ammonium cyanide 
• 33322-43-9 3-nitro-benzoic acid bromoamide 
• 618-98-4 ethyl 3-nitrobenzoate 
• 3717-29-1 E-3-nitrobenzaldoxime 
• 4015-57-0 acetic acid-(3-nitro-benzoic acid )-anhydride 
• 58010-74-5 bis-(3-nitro-benzoyl)-amine 
• 55-21-0 benzamide 
• 3459-99-2 3-nitrobenzamidine 
• 619-24-9 3-nitrobenzonitrile 
• 121-90-4 m-nitrobenzoic acid chloride 
• 5994-87-6 diphenylphosphinamide 
• 121-92-6 3-nitrobenzoic acid 

Downstream Products

• 708258-85-9 4-methyl-2-(3-nitro-phenyl)-oxazole 
• 40478-11-3 N-(hydroxymethyl)-3-nitrobenzamide 
• 108718-21-4 N,N'-methylenebis(3-nitrobenzamide) 
• 6275-72-5 ethyl N-(m-nitrophenyl)carbamate 
• 58010-74-5 bis-(3-nitro-benzoyl)-amine 
• 33341-70-7 N-chloro-3-nitro-benzamide 
• 33322-43-9 3-nitro-benzoic acid bromoamide 
• 59393-77-0 5-amino-2-hydroxy-benzoic acid amide 
• 17437-70-6 3-nitro-benzoic acid-(trichlorophosphoranyliden-amide) 
• 3544-24-9 3-Aminobenzamide 
• 619-24-9 3-nitrobenzonitrile 
• 36841-43-7 4-(chloromethyl)-2-(3-nitrophenyl)oxazole 
• 5843-49-2 isocyanate de nitro-3 benzoyle 
• 51074-01-2 2,6-bis-(3-nitro-phenyl)-benzo[1,2-d;4,5-d']bisoxazole 

Relevant articles and documents

Visible light-mediated synthesis of amides from carboxylic acids and amine-boranes

Here, a photocatalytic deoxygenative amidation protocol using readily available amine-boranes and carboxylic acids is described. This approach features mild conditions, moderate-to-good yields, easy scale-up, and up to 62 examples of functionalized amides with diverse substituents. The synthetic robustness of this method was also demonstrated by its application in the late-stage functionalization of several pharmaceutical molecules.

Ru-based complexes as heterogeneous potential catalysts for the amidation of aldehydes and nitriles in neat water

Five novel heterogeneous mononuclear complex-anchored Ru(III) have been efficiently sono-synthesized and characterized by utilizing several analytical techniques. The assembled complexes could be utilized as effective, robust and recyclable (up to eight consecutive runs) catalysts for one-pot transformation of a vast array of nitriles and aldehydes to primary amides in H2O under aerobic conditions. Moreover, some unreported di- and tetra-amide derivatives were obtained also under the optimal conditions. The results of ICP/OES analysis demonstrated that there is no detected leaching of the recycled catalyst, which suggests the real heterogeneity of the present protocol. The present Ru-complexes exhibited superiority compared to other reported catalysts for amide preparation in terms of low catalyst load, short reaction time, low operating temperature, no hazardous additives required, and high values of TON (990) and TOF (1980 h11).

Fe3O4@GlcA@Cu-MOF: A Magnetic Metal-Organic Framework as a Recoverable Catalyst for the Hydration of Nitriles and Reduction of Isothiocyanates, Isocyanates, and Isocyanides

A novel magnetic metal-organic framework (Fe3O4@GlcA@Cu-MOF) has been prepared and characterized by spectroscopic, microscopic, and magnetic techniques. This magnetically separable catalyst exhibited high catalytic activity for nitrile hydration and the ability to reduce isothiocyanates, isocyanates, and isocyanides with excellent activity and selectivity without any additional reducing agent.