939-80-0

Basic information

• Product Name: 4-CHLORO-3-NITROBENZONITRILE
• Synonyms: 4-CHLORO-3-NITROBENZONITRILE;LABOTEST-BB LT00160147;4-chlor-3-nitrobenzonitril;4-chloro-3-nitro-benzonitril;2-chloro-5-cyanonitrobenzene;2-Nitro-4-cyanophenyl chloride;3-Nitro-4-chlorobenzonitrile;4-Chloro-3-nitrobenzonitrile,97%
• CAS NO: 939-80-0
• Molecular Formula: C₇H₃ClN₂O₂
• Molecular Weight: 182.56
• EINECS: 213-364-2
• Product Categories: Aromatic Nitriles;C6 to C7;Cyanides/Nitriles;Nitrogen Compounds
• Mol File: 939-80-0.mol
• Article Data: 14

Chemical Properties

• Melting Point: 98-100 °C(lit.)
• Boiling Point: 284.758 °C at 760 mmHg
• Flash Point: 126.017 °C
• Appearance: light yellow crystalline powder
• Density: 1.6133 (rough estimate)
• Vapor Pressure: 0.00292mmHg at 25°C
• Refractive Index: 1.5557 (estimate)
• Storage Temp.: Sealed in dry,Room Temperature
• Water Solubility: Slightly soluble in water
• BRN: 1639111
• CAS DataBase Reference: 4-CHLORO-3-NITROBENZONITRILE(CAS DataBase Reference)
• NIST Chemistry Reference: 4-CHLORO-3-NITROBENZONITRILE(939-80-0)
• EPA Substance Registry System: 4-CHLORO-3-NITROBENZONITRILE(939-80-0)

Safety Data

• Hazard Codes: Xi,Xn
• Statements: 36/37/38-20/21/22
• Safety Statements: 26-36-36/37
• WGK Germany: 2
• RTECS: DI3050000
• Hazardous Substances Data: 939-80-0(Hazardous Substances Data)

Usage

Chemical Properties

light yellow crystalline powder

Uses

4-Chloro-3-nitrobenzonitrile may be used in the synthesis of 3-nitro-4-thiocyanobenzonitryl.

General Description

FT-IR and μ-Raman spectra of 4-chloro-3-nitrobenzonitrile have been recorded in the range of 400-4000cm-1 and 100-4000cm-1, respectively. It has been prepred from the reaction of 4-chloro-3-nitrobenzamide and phosphorus oxychloride. Crystal structure of 4-chloro-3-nitrobenzonitrile has been reported. Molecules of 4-chloro-3-nitrobenzonitrile are linked by weak intermolecular C-H…O and C-H…N hydrogen bonds.

InChI:InChI=1/C7H3ClN2O2/c8-6-2-1-5(4-9)3-7(6)10(11)12/h1-3H

Synthetic route

4-Cyanochlorobenzene (623-03-0) → 4-chloro-3-nitrobenzonitrile (939-80-0)

Conditions	Yield
With sulfuric acid; nitric acid In methanol Solvent; Large scale;	95%
With sulfuric acid; potassium nitrate at 3 - 5℃; for 3h;	88%
With nitronium tetrafluoborate In acetonitrile at 0 - 20℃; for 20h;	75.47%

4-chloro-3-nitrobenzamide (16588-06-0) → 4-chloro-3-nitrobenzonitrile (939-80-0)

Conditions	Yield
With trimethylsilyl methanesulfonate; phosphorus pentoxide at 70 - 75℃; for 3h; further reagents;	87%
With trichlorophosphate at 170℃;
With Hexamethyldisiloxane; phosphorus pentoxide In chloroform for 2h; Inert atmosphere; Reflux;

4-chloro-3-nitro-benzaldehyde phenylhydrazone (59670-78-9) → 4-chloro-3-nitrobenzonitrile (939-80-0) + N,N-dimethyl-N'-phenylcarbamimidic chloride (7684-30-2)

Conditions	Yield
With dichloromethylenedimethyliminium chloride In 1,2-dichloro-ethane 1.) room temp., 1 h, 2.) reflux, 4 h;	A 87% B n/a

4-chloro-3-nitro-benzaldehyde (16588-34-4) → 4-chloro-3-nitrobenzonitrile (939-80-0)

Conditions	Yield
With hydroxylamine hydrochloride; ammonium acetate for 0.05h; Microwave irradiation; Neat (no solvent);	81%

potassiumhexacyanoferrate(II) trihydrate + 2,5-dichloronitrobenzene (89-61-2) → 4-chloro-3-nitrobenzonitrile (939-80-0)

Conditions	Yield
With sodium carbonate In water; N,N-dimethyl-formamide at 120℃; for 18h;	74%

4-bromo-1-chloro-2-nitrobenzene (16588-24-2) + formamide (77287-34-4, 77287-35-5, 60100-09-6) → 4-chloro-3-nitrobenzonitrile (939-80-0)

Conditions	Yield
With 1,3,5-trichloro-2,4,6-triazine; palladium on activated charcoal; potassium carbonate; triphenylphosphine at 25 - 130℃; for 12.1667h;	74%

Nitroethane (79-24-3) + 4-chloro-3-nitro-benzaldehyde (16588-34-4) → 4-chloro-3-nitrobenzonitrile (939-80-0) + 2-chloro-5-hydroxyiminomethylnitrobenzene (66399-01-7) + 1-chloro-2-nitro-4-((E)-2-nitro-propenyl)-benzene (134538-49-1)

Conditions	Yield
With ammonium acetate In acetic acid under 760 Torr; for 2h; Heating;	A n/a B n/a C 56%

4-Chloro-3-nitroaniline (635-22-3) → 4-chloro-3-nitrobenzonitrile (939-80-0)

Conditions	Yield
durch Austausch von NH2 gegen CN nach Sandmeyer;

4-hydroxy-3-nitrobenzonitrile (3272-08-0) + p-toluenesulfonyl chloride (98-59-9) + N,N-diethylaniline (91-66-7) → 4-chloro-3-nitrobenzonitrile (939-80-0) + 3-nitro-4-(toluene-4-sulfonyloxy)-benzonitrile

4-Cyanochlorobenzene (623-03-0) + nitric acid (7697-37-2) → 4-chloro-3-nitrobenzonitrile (939-80-0)

Conditions	Yield
at 5℃;

4-chloro-3-nitro-benzoyl chloride (38818-50-7) → 4-chloro-3-nitrobenzonitrile (939-80-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: tetrachloromethane; aqueous ammonia 2: phosphorus oxychloride / 170 °C View Scheme
Multi-step reaction with 2 steps 1: ammonia / dichloromethane; chloroform; methanol / cooling with ice 2: Hexamethyldisiloxane; phosphorus pentoxide / chloroform / 2 h / Inert atmosphere; Reflux View Scheme

4-chloro-3-nitrobenzoate (96-99-1) → 4-chloro-3-nitrobenzonitrile (939-80-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: oxalyl dichloride / N,N-dimethyl-formamide / Dichlorofluoromethane / 2 h / 20 °C 2: ammonia / dichloromethane; chloroform; methanol / cooling with ice 3: Hexamethyldisiloxane; phosphorus pentoxide / chloroform / 2 h / Inert atmosphere; Reflux View Scheme

4-chlorobenzaldehyde (104-88-1) → 4-chloro-3-nitrobenzonitrile (939-80-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: hydroxylamine hydrochloride; sodium acetate / formic acid / 1 h / Reflux 2: sulfuric acid; potassium nitrate / water / 3 h / 0 - 5 °C View Scheme

potassiumhexacyanoferrate(II) trihydrate + 4-chloro-3-nitrophenyl-1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate → 4-chloro-3-nitrobenzonitrile (939-80-0)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In N,N-dimethyl-formamide at 40℃; for 3h; Sealed tube; Green chemistry;

4-chloro-3-nitrobenzonitrile (939-80-0) + cyclohexylamine (108-91-8) → 4-Cyclohexylamino-3-nitrobenzonitrile (28096-55-1)

Conditions	Yield
In DMF (N,N-dimethyl-formamide) Heating / reflux;	100%
With N,N-dimethyl-formamide Heating;	93.2%
Heating;
In N,N-dimethyl-formamide
In N,N-dimethyl-formamide at 100℃;

4-chloro-3-nitrobenzonitrile (939-80-0) → 4-chloro-N'-hydroxy-3-nitrobenzenecarboximideamide (96898-75-8)

Conditions	Yield
With hydroxylamine hydrochloride; triethylamine In ethanol at 20℃; Heating / reflux;	100%

4-chloro-3-nitrobenzonitrile (939-80-0) + glycine ethyl ester hydrochloride (5680-79-5) → 3-oxo-1 ,2,3,4-tetrahydroquinoxaline-6-carbonitrile (186666-78-4)

Conditions	Yield
With sodium hydrogencarbonate In methanol; Pd on carbon; ethanol; ethyl acetate	100%

pyridine (110-86-1) + 4-chloro-3-nitrobenzonitrile (939-80-0) → 1-(4-cyano-2-nitrophenyl)pyridinium chloride

Conditions	Yield
at 90℃; for 1h;	99%
at 90℃;

4-chloro-3-nitrobenzonitrile (939-80-0) + 3,5-dichlorophenol (591-35-5) → 5-cyano-2-(3,5-dichlorophenoxy)nitrobenzene (261761-44-8)

Conditions	Yield
With sodium hydride In tetrahydrofuran for 1h; Heating / reflux;	98.4%

4-chloro-3-nitrobenzonitrile (939-80-0) + ethylenediamine (107-15-3) → 4-(2-Amino-ethylamino)-3-nitro-benzonitrile (125901-97-5)

Conditions	Yield
With triethylamine In dimethyl sulfoxide for 30h; Ambient temperature;	98%

4-chloro-3-nitrobenzonitrile (939-80-0) + phenylboronic acid (98-80-6) → 2-nitro-(1,1'-biphenyl)-4-carbonitrile (166263-24-7)

Conditions	Yield
With caesium carbonate; [PdCl(NNCNHC-nBu)]BF4 In water; N,N-dimethyl-formamide at 120℃; for 1h; Suzuki-Miyaura reaction;	98%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; toluene for 19h; Suzuki-Miyaura cross coupling; Heating;	92%
With 1-methyl-pyrrolidin-2-one; cesium fluoride; bis(triphenylphosphine)palladium(II) dichloride	79%
With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate monohydrate; tris-(dibenzylideneacetone)dipalladium(0) In water; toluene Reflux;	72.2%

4-chloro-3-nitrobenzonitrile (939-80-0) + 4,4,4-trifluorobutan-1-amine (819-46-5) → 3-nitro-4-(4,4,4-trifluorobutylamino)benzonitrile (1243325-58-7)

Conditions	Yield
With triethylamine In acetonitrile at 20℃; for 16h; Product distribution / selectivity;	98%
With triethylamine In acetonitrile at 20℃; for 21h; Inert atmosphere;	92%

4-chloro-3-nitrobenzonitrile (939-80-0) + 4-iodo-3-(trifluoromethyl)-1H-pyrazolo[3,4-b]pyridine (1160502-30-6) → 4-{4-iodo-3-(trifluoromethyl)-1H-pyrazolo[3,4-b]pyridin-1-yl}-3-nitrobenzonitrile (1260539-62-5)

Conditions	Yield
With caesium carbonate In acetonitrile at 70℃; for 4h;	98%

4-chloro-3-nitrobenzonitrile (939-80-0) + 4-(aminomethyl)benzonitrile hydrochloride → 4-(N-4-cyanobenzylamino)-3-nitro-benzonitrile

Conditions	Yield
With potassium carbonate In 1,4-dioxane for 24h; Reflux; Inert atmosphere;	98%

4-chloro-3-nitrobenzonitrile (939-80-0) → 3-amino-4-chloro-benzonitrile (53312-79-1)

Conditions	Yield
With sodium hydrogen sulfide In tetrahydrofuran; water at 45℃;	97%
With ethanol; iron; calcium chloride In water at 60℃; for 0.5h; chemoselective reaction;	90%
	84%

4-chloro-3-nitrobenzonitrile (939-80-0) + diethyl malonate (105-53-3) → diethyl (4-cyano-2-nitrophenyl)malonate

Conditions	Yield
With hydrogenchloride In N,N-dimethyl-formamide; mineral oil	97%

4-chloro-3-nitrobenzonitrile (939-80-0) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → 4-(dimethylamino)-3-nitrobenzonitrile (19005-63-1)

Conditions	Yield
Stage #1: N,N-dimethyl-formamide With ammonia In water at 240℃; for 0.666667h; Stage #2: 4-chloro-3-nitrobenzonitrile In water for 0.333333h;	97%
for 14h; Reflux;	83%

propylamine (107-10-8) + 4-chloro-3-nitrobenzonitrile (939-80-0) → 3-nitro-4-propylaminobenzonitrile (438554-06-4)

Conditions	Yield
With N,N-dimethyl-formamide Heating;	96.4%
With ethanol
Heating;

ethyl 2-pyridylcarbonylacetate (26510-52-1) + 4-chloro-3-nitrobenzonitrile (939-80-0) → (4-cyano-2-nitro-phenyl)-acetic acid ethyl ester

Conditions	Yield
Stage #1: ethyl 2-pyridylcarbonylacetate With potassium tert-butylate In 1,4-dioxane; 1-methyl-pyrrolidin-2-one at 20 - 70℃; Stage #2: 4-chloro-3-nitrobenzonitrile In 1,4-dioxane; 1-methyl-pyrrolidin-2-one at 70℃; Stage #3: With hydrogenchloride	96%

4-chloro-3-nitrobenzonitrile (939-80-0) + 4-bromo-benzenesulfonic acid amide (701-34-8) → 4-bromo-N-(4-cyano-2-nitrophenyl)benzenesulfonamide

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 140℃; for 0.2h; Microwave irradiation;	96%

4-chloro-3-nitrobenzonitrile (939-80-0) + trans-4-hydroxycyclohexylamine (27489-62-9) → 4-(((1R,4R)-4-hydroxycyclohexyl)amino)-3-nitrobenzonitrile (926569-03-1)

Conditions	Yield
With potassium carbonate In acetonitrile at 70℃; Inert atmosphere;	96%

ethyl 2-pyridylcarbonylacetate (26510-52-1) + 4-chloro-3-nitrobenzonitrile (939-80-0) → 2-(4-cyano-2-nitro-phenyl)-3-oxo-3-pyridin-2-yl-propionic acid ethyl ester (698392-52-8)

Conditions	Yield
Stage #1: ethyl 2-pyridylcarbonylacetate With potassium tert-butylate In 1,4-dioxane; 1-methyl-pyrrolidin-2-one at 20 - 70℃; Stage #2: 4-chloro-3-nitrobenzonitrile In 1,4-dioxane; 1-methyl-pyrrolidin-2-one at 70℃; Stage #3: With hydrogenchloride In 1,4-dioxane	95%

4-chloro-3-nitrobenzonitrile (939-80-0) + 2,5-dimethylthiophenol (4001-61-0) → 4-(2,5-dimethylphenylthio)-3-nitrobenzonitrile (1252681-55-2)

Conditions	Yield
With potassium carbonate In tetrahydrofuran for 16h; Reflux;	95%

1-amino-3-methylbutane (107-85-7) + 4-chloro-3-nitrobenzonitrile (939-80-0) → 4-(isopentylamino)-3-nitrobenzonitrile (406945-12-8)

Conditions	Yield
With N,N-dimethyl-formamide Heating;	94.3%
In N,N-dimethyl-formamide	21.0 g (90%)
In N-ethyl-N,N-diisopropylamine at 90℃; for 15h;

4-chloro-3-nitrobenzonitrile (939-80-0) + isopropylamine (75-31-0) → 4-(isopropylamino)-3-nitrobenzonitrile (355022-17-2)

Conditions	Yield
In N,N-dimethyl-formamide at 35℃; for 1h;	94%
With N,N-dimethyl-formamide Heating;	93.8%

4-chloro-3-nitrobenzonitrile (939-80-0) + (R)-S-methyl-S-phenylsulfoximine (60933-65-5) → C14H11N3O3S

Conditions	Yield
With caesium carbonate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; palladium diacetate In toluene at 135℃; for 3h; microwave irradiation;	94%

4-chloro-3-nitrobenzonitrile (939-80-0) + 1-dodecylthiol (112-55-0) → 4-(n-dodecylthio)-3-nitrobenzonitrile (202190-87-2)

Conditions	Yield
With copper(ll) sulfate pentahydrate; sodium carbonate; sodium L-ascorbate; L-proline In water; dimethyl sulfoxide at 70℃; for 12h;	94%

4-chloro-3-nitrobenzonitrile (939-80-0) + 2-CHLOROBENZYLAMINE (89-97-4) → 3-nitro-4-{[(2-chlorophenyl)methyl]amino}benzonitrile

Conditions	Yield
In methanol for 7h; Reflux;	94%

4-chloro-3-nitrobenzonitrile (939-80-0) + N-butylamine (109-73-9) → 4-butylamino-3-nitrobenzonitrile (143193-44-6)

Conditions	Yield
In N,N-dimethyl-formamide for 2h; Heating;	93%
With N,N-dimethyl-formamide Heating;	92.7%
With ethanol
In ethanol Reflux;

4-chloro-3-nitrobenzonitrile (939-80-0) + carbamic acid 2-trimethylsilylethyl ester (3124-37-6) → (4-cyano-2-nitrophenyl)carbamic acid 2-trimethylsilanylethyl ester (1257310-73-8)

Conditions	Yield
With palladium diacetate; caesium carbonate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene In 1,4-dioxane at 120℃; for 15h; Inert atmosphere;	93%

4-aminotetrahydropyran (38041-19-9) + 4-chloro-3-nitrobenzonitrile (939-80-0) → 3-nitro-4-(tetrahydropyran-4-ylamino)benzonitrile (320406-00-6)

Conditions	Yield
With potassium carbonate In acetonitrile at 70℃;	93%

4-chloro-3-nitrobenzonitrile (939-80-0) + 2-amino-1-benzylamine (4403-69-4) → C14H10ClN3O2

Conditions	Yield
With copper(II) cinnamic acid complex In toluene at 110℃; Green chemistry;	92%

4-chloro-3-nitrobenzonitrile (939-80-0) + ethanolamine (141-43-5) → 4-(2'-hydroxyethyl)amino-3-nitrobenzonitrile (90349-40-9)

Conditions	Yield
With N,N-dimethyl-formamide Heating;	91%
With ethanol
In tetrahydrofuran; ethanol

Upstream product

• 623-03-0 4-Cyanochlorobenzene 
• 635-22-3 4-Chloro-3-nitroaniline 
• 3272-08-0 4-hydroxy-3-nitrobenzonitrile 
• 98-59-9 p-toluenesulfonyl chloride 
• 91-66-7 N,N-diethylaniline 
• 16588-06-0 4-chloro-3-nitrobenzamide 
• 59670-78-9 4-chloro-3-nitro-benzaldehyde phenylhydrazone 
• 79-24-3 Nitroethane 
• 16588-34-4 4-chloro-3-nitro-benzaldehyde 
• 7697-37-2 nitric acid 
• 38818-50-7 4-chloro-3-nitro-benzoyl chloride 
• 16588-24-2 4-bromo-1-chloro-2-nitrobenzene 
• 77287-34-4 formamide 
• 89-61-2 2,5-dichloronitrobenzene 

Downstream Products

• 857542-11-1 4-(4-chloro-3-nitro-anilino)-3-nitro-benzonitrile 
• 860563-65-1 3,3'-dinitro-4,4'-biphenyl-2,2'-diyldiamino-di-benzonitrile 
• 860680-95-1 3-amino-4-propoxy-benzoic acid amide 
• 72635-80-4 3-amino-4-propoxy-benzonitrile 
• 33224-23-6 4-Cyano-2-nitroanisol 
• 60979-25-1 3-amino-4-methoxybenzonitrile 
• 136366-43-3 4-ethoxy-3-nitro-benzonitrile 
• 53312-79-1 3-amino-4-chloro-benzonitrile 
• 72635-79-1 4-ethoxy-3-amino-benzonitrile 
• 124839-61-8 4-hydrazino-3-nitro-benzonitrile 
• 16588-06-0 4-chloro-3-nitrobenzamide 
• 6393-40-4 4-Amino 3-nitro-benzonitrile 
• 96-99-1 4-chloro-3-nitrobenzoate 
• 16588-23-1 3-nitro-4-(phenylamino)benzonitrile 

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