99-99-0

Basic information

• Product Name: 4-Nitrotoluene
• Synonyms: Of nitrotoluene;4-Nitrotol;1-Methyl-4-mitrobenaene;1-methyl-4-nitro-benzen;4-methyl-1-nitrobenzene;4-nitrobenzene;Benzene,1-methyl-4-nitro-;nci9579
• CAS NO: 99-99-0
• Molecular Formula: C₇H₇NO₂
• Molecular Weight: 137.14
• EINECS: 202-808-0
• Product Categories: 4-Methylnitrobenzene;Organics;Analytical Chemistry;Environmental Endocrine Disruptors;Estradiol, etc. (Environmental Endocrine Disruptors);Solid WasteMethod Specific;2000/60/ECMore...Close...;8000 Series Solidwaste Methods;Analytical Standards;AromaticsEnvironmental Standards;Chemical Class;Environmental Standards;European Community: ISO and DIN;ExplosivesEPA;Method 8330Alphabetic;N;NA - NIAnalytical Standards;Nitro CompoundsChromatography;Volatiles/ Semivolatiles
• Mol File: 99-99-0.mol
• Article Data: 348

Chemical Properties

• Melting Point: 52-54 °C(lit.)
• Boiling Point: 238 °C(lit.)
• Flash Point: 223 °F
• Appearance: Yellow/Crystalline Solid
• Density: 1.392 g/mL at 25 °C(lit.)
• Vapor Density: 4.7 (vs air)
• Vapor Pressure: 5 mm Hg ( 85 °C)
• Refractive Index: 1.5382
• Storage Temp.: 0-6°C
• Solubility: 0.26g/l
• PKA: 11.27 (Perrin, 1972)
• Explosive Limit: 1.6%(V)
• Water Solubility: 0.35 g/L (20 ºC)
• Stability: Stability May be shock sensitive. Incompatible with sulfuric acid, strong bases, reducing agents, strong oxidizing agents.
• Merck: 14,6650
• BRN: 1906911
• CAS DataBase Reference: 4-Nitrotoluene(CAS DataBase Reference)
• NIST Chemistry Reference: 4-Nitrotoluene(99-99-0)
• EPA Substance Registry System: 4-Nitrotoluene(99-99-0)

Safety Data

• Hazard Codes: T,N,F,Xn
• Statements: 23/24/25-33-51/53-36/37/38-11-36-20/21/22
• Safety Statements: 28-37-45-61-28A-27-16-36/37-26
• RIDADR: UN 3446 6.1/PG 2
• WGK Germany: 2
• RTECS: XT3325000
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 99-99-0(Hazardous Substances Data)

Usage

Chemical Properties

light yellow crystals

Uses

Different sources of media describe the Uses of 99-99-0 differently. You can refer to the following data:
1. used in the synthesis of dyestuffs, explosives, and agricultural chemicals
2. 4-Nitrotoluene is an explosive material.
3. manufacture of dyes, toluidines, nitrobenzoic acids, agricultural and rubber chemicals.

Synthesis Reference(s)

Journal of the American Chemical Society, 79, p. 5528, 1957 DOI: 10.1021/ja01577a053Tetrahedron Letters, 29, p. 97, 1988 DOI: 10.1016/0040-4039(88)80026-1

General Description

A yellow liquid with a weak aromatic odor. Toxic. Insoluble in water. Combustible but may take some effort to ignite. Produces toxic oxides of nitrogen when burned. In a spill, immediate steps should be taken to limit its spread to the environment. Can easily penetrate the soil and contaminate groundwater or nearby streams. Used to make other chemicals.

Air & Water Reactions

Insoluble in water.

Reactivity Profile

4-Nitrotoluene may react violently with sodium, tetranitromethane, strong oxidizing agents , sulfuric acid and other acids.

Hazard

Toxic by inhalation, ingestion, skin absorption. Methemoglobinemia. Questionable carcinogen.

Health Hazard

INHALATION, INGESTION, OR SKIN: Headache, flushed face, dizziness, dyspnea (difficult breathing), cyanosis, nausea, vomiting, muscular weakness, rapid pulse and respiration, irritability, and convulsions.

Fire Hazard

Special Hazards of Combustion Products: Yields toxic oxides of nitrogen when burning.

Safety Profile

A poison. Moderately toxic by ingestion, inhalation, and intraperitoneal routes. Mildly toxic by skin contact. Mutation data reported. Combustible when exposed to heat or flame. To fight fire, use CO2, dry chemical, foam. The residue from vacuum distillation may explode spontaneously. Reacts with sodmm to form an ignitable product. Violent reaction with concentrated sulfuric acid (above 16O°C), sulfuric acid + sulfur trioxide (above 52°C). Mixtures with tetranitromethane are sensitive high explosives. May explode on standing. It has been involved in plant scale explosions. When heated to decomposition it emits toxic fumes of NOx. See also other methylnitrobenzene entries and NITRO COMPOUNDS OF AROMATIC HYDROCARBONS.

Environmental fate

Biological. Under anaerobic conditions using a sewage inoculum, 3- and 4-nitrotoluene both degraded to toluidine (Hallas and Alexander, 1983). Robertson et al. (1992) reported that toluene dioxygenases from Pseudomonas putida F1 and Pseudomonas sp. Strain JS 150 oxidized the methyl group forming 2-methyl-5-nitrophenol and 3-methyl-6-nitrocatechol. Chemical. Though no products were identified, 4-nitrotoluene (1.5 x 10-5 M) was reduced by iron metal (33.3 g/L acid washed 18 to 20 mesh) in a carbonate buffer (1.5 x 10-2 M) at pH 5.9 and 15 °C. Based on the pseudo-first-order disappearance rate of 0.0335/min, the half-life was 20.7 min (Agrawal and Tratnyek, 1996).

Purification Methods

Dry it in air, then dry it in a vacuum desiccator over H2SO4. [Wright & Grilliom J Am Chem Soc 108 2340 1986, Beilstein 5 IV 848.]

Synthetic route

4-nitrobenzeneacetic acid (104-03-0) → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
copper(I) oxide In acetonitrile at 50℃;	100%
With [Rh(OH)(cod)]2; 1,3-bis-(diphenylphosphino)propane; water; sodium hydroxide In toluene at 100℃; for 16h; Inert atmosphere;	87%
With potassium carbonate In chloroform at 20℃; for 24h; Irradiation; Inert atmosphere;	81%

p-nitrobenzene iodide (636-98-6) + (CH3)4Sn → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
polymer supported palladium catalyst In N,N,N,N,N,N-hexamethylphosphoric triamide at 70℃; for 1h; Stille coupling reaction;	100%

4-nitrobenzenediazonium o-benzenedisulfonimide + tetramethylstannane (594-27-4) → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
palladium diacetate In tetrahydrofuran at 40℃; for 0.5h;	100%

4-nitrobenzyl chloride (100-14-1) → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
With sodium tetrahydroborate; cetyltributylphosphonium bromide In water; toluene at 40℃; for 0h; Product distribution;	99%
With phosphonic Acid; iodine In benzene at 100℃; for 36h; Inert atmosphere;	42%
With tri-n-butyl-tin hydride; 2,2'-azobis(isobutyronitrile) In toluene for 3h; Mechanism; Irradiation;	24%

1-bromomethyl-4-nitro-benzene (100-11-8) → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
With sodium tetrahydroborate; cetyltributylphosphonium bromide In water; toluene at 18℃; for 0h; Product distribution;	99%
With sodium tetrahydroborate In aq. phosphate buffer at 70℃; for 2.5h; pH=12; Reagent/catalyst; Green chemistry;	95%
With sodium tetrahydroborate In various solvent(s) at 70℃; for 10h;	88%

potassium (4-methylphenyl)trifluoroborate → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
With bismuth (III) nitrate pentahydrate In toluene at 120℃; for 0.333333h; Reagent/catalyst; Microwave irradiation;	99%
With sodium dihydrogen phosphate monohydrate; dichloro[1,1'-bis(di-t-butylphosphino)ferrocene]palladium(II); sodium nitrite In toluene at 120℃; for 0.5h; Microwave irradiation; Inert atmosphere;	33%

p-toluidine (106-49-0) → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
With calcium tungstate; dihydrogen peroxide In water at 50℃; for 0.5h; Reagent/catalyst; Green chemistry; Large scale;	98%
With oxaziridinium tetrafluoroborate derived from N-methyl-1,2,3,4-tetrahydroisoquinoline In dichloromethane at 0℃; for 10h;	92%
With 1,9-diperoxynonanedioic acid In acetonitrile at 50℃; for 0.5h;	92%

p-nitrobenzene iodide (636-98-6) + tetramethylstannane (594-27-4) → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
With C31H33INPPd In N,N-dimethyl-formamide at 80℃; for 24h; Stille coupling;	98%
With iodophenylbis(triphenylphosphine)palladium In N,N,N,N,N,N-hexamethylphosphoric triamide at 70℃; for 0.5h;	87%

toluene (108-88-3) → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
With sodium nitrate In neat (no solvent) at 20℃; for 0.05h; Catalytic behavior; Reagent/catalyst; Green chemistry;	96%
With nitric acid; sodium dodecyl-sulfate In water at 25℃; for 0.333333h; Micellar solution; Green chemistry; regioselective reaction;	86%
With tetrammine copper(II) sulphate; nitric acid In dichloromethane; water at 20℃; for 3h; regioselective reaction;	85%

2-methyl-5-nitrobenzenediazonium o-benzenedisulfonimide → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
With dihydrogen peroxide In tetrahydrofuran for 0.166667h; Heating;	94%

Trimethylboroxine (823-96-1) + 4-chlorobenzonitrile (100-00-5) → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
With potassium fluoride; 18-crown-6 ether; bis-phenanthrylimidazolium chloride; palladium diacetate In tetrahydrofuran at 20℃; for 8h; Suzuki-Miyaura coupling;	93%

5-methyl-2-nitrobenzoic acid (3113-72-2) → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
With sulfolane; sodium hydrogencarbonate at 230℃; for 2.5h; Temperature; Reagent/catalyst;	92%
With copper(l) iodide; triethylamine In dimethyl sulfoxide at 120℃; under 760.051 Torr; for 20h; Inert atmosphere; Schlenk technique;	88%
With copper(I) oxide; 1,10-Phenanthroline In 1-methyl-pyrrolidin-2-one; quinoline at 190℃; for 0.0833333h; Microwave irradiation;	80%
With copper(I) oxide at 120℃; for 24h; Ionic liquid;

4-methylphenylboronic acid (5720-05-8) → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
With Iron(III) nitrate nonahydrate In toluene at 80℃; for 18h; Catalytic behavior; Reagent/catalyst; Solvent; Temperature; Inert atmosphere;	92%
With N-Bromosuccinimide; [bis(trifluoroacetoxy)iodo]benzene; sodium nitrite In acetonitrile at 20℃; for 3h; regioselective reaction;	92%
With bismuth (III) nitrate pentahydrate In toluene at 70 - 80℃; for 1.5h; Inert atmosphere;	87%

toluene (108-88-3) → 1-methyl-4-nitrobenzene (99-99-0) + 1-methyl-2-nitrobenzene (88-72-2)

Conditions	Yield
With nickel ammonium sulfate; nitric acid In chloroform; water at 20℃; for 4h;	A 88% B 12%
With sodium nitrite for 0.0166667h; Reagent/catalyst; Microwave irradiation;	A 82% B 15%
With bismuth(III) nitrate In tetrachloromethane	A 80% B n/a

4-nitrobenzaldehdye (555-16-8) → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
With n-butylsilane; tris(pentafluorophenyl)borate In dichloromethane	87%
With hydrogen; palladium on activated charcoal In methanol under 760 Torr; for 18h;	33%

p-nitrobenzene iodide (636-98-6) + tris(diethylamino)sulfonium difluorotrimethylsiliconate (59201-86-4) → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
π-allyl-palladium chloride In tetrahydrofuran 1.) room temperature; 2.) 50 deg C, 20 h;	86%

p-tolyllithium (2417-95-0) → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
With dinitrogen tetraoxide In tetrahydrofuran -190 deg C -> room temperature;	86%

4-methyl-N'-[(4-nitrophenyl)methylidene]benzene-1-sulfonohydrazide (1747-50-8) → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
With dichloro bis(1,4-diazabicyclo[2.2.2]octane)(BH4)Zr(IV); toluene-4-sulfonic acid In sulfolane; N,N-dimethyl-formamide at 110℃; for 6h;	86%

para-nitrophenyl triflate (17763-80-3) + potassium trifluoro(methyl)boranuide → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; water; caesium carbonate In tetrahydrofuran Suzuki coupling reaction; Heating;	85%

toluene (108-88-3) → 1-methyl-4-nitrobenzene (99-99-0) + 1-methyl-2-nitrobenzene (88-72-2) + benzoic acid (65-85-0)

Conditions	Yield
With methanesulfonic acid; 1-butyl-3-methylimidazolium nitrate In water for 48h; Heating / reflux;	A n/a B n/a C 85%
With nitric acid; 1-butyl-3-methylimidazolium nitrate In water for 48h; Heating / reflux;	A n/a B n/a C 85%
With nitric acid; 1-n-butyl-3-methylimidazolium methanesulfonate In water for 48h; Heating / reflux;	A n/a B n/a C 70%
With nitric acid; 1-n-butyl-3-methylimidazolium methanesulfonate In water for 48h; Heating / reflux;	A n/a B n/a C 70%

toluene (108-88-3) → 1-methyl-4-nitrobenzene (99-99-0) + 2,4-dinitrotoluene (121-14-2) + 2,6-dinitrotoluene (606-20-2)

Conditions	Yield
With succinic acid anhydride; nitric acid at 4℃; for 50h; Product distribution / selectivity;	A 7.9% B 85% C 6.3%
With nitric acid; dichloroacetic anhydride In dichloromethane at 50℃; for 0.166667h; Time;

p-Toluic acid (99-94-5) → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
With nitronium tetrafluoborate; silver carbonate In N,N-dimethyl acetamide at 90℃; for 12h; Inert atmosphere; Schlenk technique; regioselective reaction;	85%
With 1,3-disulfonic acid imidazolium nitrate In neat (no solvent) at 50℃; for 0.5h; Inert atmosphere;	76%

Dimethyl-p-toluidine (99-97-8) → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
With tert.-butylhydroperoxide; ammonium iodide; water In dimethyl sulfoxide at 90℃; for 4h; Mechanism; Temperature; Reagent/catalyst; Solvent; Time; Sealed tube;	85%

C12H13NO4 → 1-methyl-4-nitrobenzene (99-99-0) + C11H13NO2

Conditions	Yield
With C53H50IrNO2P(1-)*ClO4(1-); 1,8-diazabicyclo[5.4.0]undec-7-ene In tetrahydrofuran at 20℃; for 14h; Reagent/catalyst; Inert atmosphere; Sealed tube; enantioselective reaction;	A n/a B 83%

p-nitrobenzene iodide (636-98-6) + methylmercury(II) iodide (143-36-2) → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
With bis(benzonitrile)palladium(II) dichloride; sodium iodide In N,N-dimethyl-formamide at 20℃; for 0.333333h; Inert atmosphere;	82%
With PhPd(PPh3)2 In N,N,N,N,N,N-hexamethylphosphoric triamide at 70℃; for 1.5h; Product distribution; other solvent, reaction time, temperature;	91 % Chromat.
With iodide; iodophenylbis(triphenylphosphine)palladium In acetone at 20℃; for 0.5h;	98 % Chromat.

tetramethylstannane (594-27-4) + p-nitrobenzenediazonium hydrogen sulfate → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
palladium diacetate In water; acetonitrile at 20℃; for 2h;	81%
With palladium diacetate In water; acetonitrile at 20℃; for 2h;	81%
palladium diacetate In water; acetonitrile at 20℃; for 2h; other aryldiazonium salts;	81%

dihydroxy-methyl-borane (13061-96-6) + para-nitrophenyl triflate (17763-80-3) → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
With potassium carbonate; dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2 In tetrahydrofuran; water for 18h; Suzuki coupling reaction; Heating;	80%

para-nitrophenyl bromide (586-78-7) + (CH3)4Sn → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
polymer supported palladium catalyst In N,N-dimethyl-formamide at 70℃; for 4h; Stille coupling reaction;	80%

bis(4-methylphenyl)iodonium trifluoromethanesulfonate (123726-16-9) → 1-methyl-4-nitrobenzene (99-99-0)

Conditions	Yield
With sodium nitrite In ethyl acetate at 70℃; for 16h; Sealed tube;	80%

toluene (108-88-3) → 1-methyl-3-nitrobenzene (99-08-1) + 1-methyl-4-nitrobenzene (99-99-0) + 1-methyl-2-nitrobenzene (88-72-2)

Conditions	Yield
With copper(II) nitrate on K10 montmorillonite; acetic anhydride In tetrachloromethane for 120h; Ambient temperature;	A 1% B 79% C 20%
With nitric acid In trifluoroacetic acid at 25℃; Rate constant;	A 0.7% B 66.7% C 32.6%
With ortho-methylphenyl iodide; potassium nitrate In trifluoroacetic acid for 0.5h; Product distribution; nitration of aromatic compounds in the presence of aryl iodides; other temperatures, other reagents;	A n/a B 64% C 33%

1-methyl-4-nitrobenzene (99-99-0) → 2,4-dinitrotoluene (121-14-2)

Conditions	Yield
With nitric acid at 50℃; for 3h;	100%
With nitrourea; sulfuric acid at 25℃; for 24h;	99%
With ethylene glycol dinitrate In sulfuric acid at 0 - 20℃;	99%

1-methyl-4-nitrobenzene (99-99-0) → N-(4-methylphenyl)hydroxylamine (623-10-9)

Conditions	Yield
With 5% rhodium-on-charcoal; hydrazine hydrate In tetrahydrofuran at 0℃; for 2.5h; Inert atmosphere;	100%
With 5% rhodium-on-charcoal; hydrazine hydrate In tetrahydrofuran at 0℃; Inert atmosphere;	100%
With rhodium contaminated with carbon; hydrazine hydrate In tetrahydrofuran at 0℃; for 2.5h; Inert atmosphere;	100%

1-methyl-4-nitrobenzene (99-99-0) → 2-methyl-5-nitrobenzene-1-sulfonyl chloride (121-02-8)

Conditions	Yield
With chlorosulfonic acid	100%
With chlorosulfonic acid at 60℃; for 20h;	96%
With chlorosulfonic acid at 5 - 140℃; for 22.5h;	80.6%

1-methyl-4-nitrobenzene (99-99-0) → p-toluidine (106-49-0)

Conditions	Yield
With triethylsilane; palladium dichloride In ethanol at 20℃; for 0.5h; Inert atmosphere;	100%
With hydrazine hydrate In ethanol; water at 80℃; for 1h; chemoselective reaction;	100%
With sodium tetrahydroborate In ethanol; water at 39.84℃; for 2h; Reagent/catalyst;	100%

1-methyl-4-nitrobenzene (99-99-0) → 1-bromomethyl-4-nitro-benzene (100-11-8)

Conditions	Yield
With dihydrogen peroxide; bromine In dichloromethane; water for 4h; Reagent/catalyst; Reflux;	100%
With 2,2'-azobis(isobutyronitrile); hydrogen bromide; dihydrogen peroxide at 70 - 120℃; Reagent/catalyst; Temperature;	99.3%
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In tetrachloromethane for 3h; Reflux;	95%

1-methyl-4-nitrobenzene (99-99-0) + acetic anhydride (108-24-7) → 4-Methylacetanilide (103-89-9)

Conditions	Yield
With ammonium formate; titanium(IV) oxide; β‐cyclodextrin In water for 3.5h; Irradiation; Inert atmosphere;	100%
Stage #1: 1-methyl-4-nitrobenzene With sodium tetrahydroborate In water at 60 - 70℃; Green chemistry; Stage #2: acetic anhydride In water at 60 - 70℃; Green chemistry;	95%
Stage #1: 1-methyl-4-nitrobenzene With sodium tetrahydroborate In water at 20℃; for 0.5h; Green chemistry; Stage #2: acetic anhydride In water at 20℃; for 2.16667h; Green chemistry;	95%

propyl cyanide (109-74-0) + 1-methyl-4-nitrobenzene (99-99-0) → N,N-dibutyl-4-methylaniline (31144-33-9) + N-butyl-4-methylaniline (10387-24-3)

Conditions	Yield
Stage #1: 1-methyl-4-nitrobenzene With ammonium formate; palladium on activated charcoal In methanol; water at 20℃; Stage #2: propyl cyanide In methanol; water	A n/a B 100%

1-methyl-4-nitrobenzene (99-99-0) + propiononitrile (107-12-0) → N-propyl-p-tolylamine (54837-90-0) + 4-methyl-N,N-dipropylaniline (3480-93-1)

Conditions	Yield
Stage #1: 1-methyl-4-nitrobenzene With ammonium formate; palladium on activated charcoal In methanol; water at 20℃; Stage #2: propiononitrile In methanol; water	A 100% B n/a

1-methyl-4-nitrobenzene (99-99-0) + 2,5-hexanedione (110-13-4) → 2,5-dimethyl-1-p-tolyl-1H-pyrrole (5044-26-8)

Conditions	Yield
With formic acid for 12h; Autoclave; Inert atmosphere; Green chemistry;	100%
With indium; acetic acid In toluene at 80℃; for 2.5h; Inert atmosphere;	98%

1-methyl-4-nitrobenzene (99-99-0) → 1-nitro-4-(trichloromethyl)benzene (3284-64-8)

Conditions	Yield
With hypochlorous anhydride In tetrachloromethane at 25℃; for 96h;	99%

1-methyl-4-nitrobenzene (99-99-0) + benzaldehyde (100-52-7) → trans-4-nitrostilbene (1694-20-8)

Conditions	Yield
With 18-crown-6 ether; graphitic carbon nitride In toluene at 25℃; for 0.5h; Catalytic behavior; Reagent/catalyst; Temperature; Solvent; Knoevenagel Condensation;	99%
With potassium carbonate at 90℃; for 2h; neat (no solvent); stereoselective reaction;	71%

heptanal (111-71-7) + 1-methyl-4-nitrobenzene (99-99-0) → N-heptyl-4-methylbenzene amine (371959-15-8)

Conditions	Yield
With Au/Al2O3; hydrogen In toluene at 80℃; under 37503.8 Torr; Temperature; Flow reactor; chemoselective reaction;	99%
With hydrogen In toluene at 110℃; under 22502.3 Torr; Catalytic behavior; Temperature; Flow reactor;	92 %Chromat.

1-methyl-4-nitrobenzene (99-99-0) + p-toluidine (106-49-0) + 1-methylcyclohexan-4-one (589-92-4) → di-p-tolylamine (620-93-9)

Conditions	Yield
palladium-carbon In water; N,N-dimethyl-formamide; benzene	98.6%
palladium-carbon In water; N,N-dimethyl-formamide; benzene	98.6%

1-methyl-4-nitrobenzene (99-99-0) → 4-nitrotoluene-2-sulfonic acid sodium salt (5258-64-0)

Conditions	Yield
Stage #1: 1-methyl-4-nitrobenzene With chlorosulfonic acid at 115℃; for 3h; Stage #2: With sodium carbonate In water at 20℃;	98.2%

1-methyl-4-nitrobenzene (99-99-0) → 2-bromo-4-nitrotoluene (7745-93-9)

Conditions	Yield
With bromine fluoride In ethanol; chloroform at -40℃; for 1h;	98%
With thallium (III) oxide; trifluoroacetic acid; potassium bromide at 20℃; for 165h;	98%
With N-Bromosuccinimide; sulfuric acid In water at 20℃; for 24h;	93%

1-methyl-4-nitrobenzene (99-99-0) → 4-nitrobenzaldehdye (555-16-8)

Conditions	Yield
With oxygen; 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt In tetrahydrofuran Ambient temperature; laccase from Coriolus versicolor;	98%
With dihydrogen peroxide In acetonitrile at 50 - 80℃; for 24h; Reagent/catalyst;	95%
With nickel-doped graphene carbon nitride nanoparticles; air In ethanol at 25℃; for 8h; Irradiation; Green chemistry;	95%

1-methyl-4-nitrobenzene (99-99-0) + ammonium formate (16712-16-6, 64165-14-6, 65387-22-6, 70179-79-2, 540-69-2) → N-(4-methylphenyl)formamide (3085-54-9)

Conditions	Yield
With cobalt nanoparticles coated by N,P-codoped carbon shell pyrolyzed at 800°C In tetrahydrofuran at 120℃; for 12h; Schlenk technique; Inert atmosphere;	98%
With hydrogen; palladium on activated charcoal In acetonitrile at 95℃; for 7h;	89%
With gold nanoparticles supported on titanium dioxide (TiO2) In acetonitrile for 3h; Inert atmosphere; Reflux;	88%
With glycolic Acid at 30℃; for 48h; Catalytic behavior; Reagent/catalyst; Temperature; Irradiation; Inert atmosphere;	85 %Spectr.

1-methyl-4-nitrobenzene (99-99-0) + di-tert-butyl dicarbonate (24424-99-5) → N-(tert-butoxycarbonyl)-4-methylaniline (14618-59-8)

Conditions	Yield
Stage #1: 1-methyl-4-nitrobenzene With sodium tetrahydroborate In water at 20℃; for 0.5h; Green chemistry; Stage #2: di-tert-butyl dicarbonate In water at 20℃; for 1.16667h; Green chemistry;	98%
With tin; ammonium chloride In methanol at 25℃; for 4.5h; Sonication;	87%

formaldehyd (50-00-0) + 1-methyl-4-nitrobenzene (99-99-0) + ethyl acetoacetate (141-97-9) → ethyl 3-(N-methyl-N-4-tolylamino)butanoate

Conditions	Yield
Stage #1: 1-methyl-4-nitrobenzene; ethyl acetoacetate With Decaborane; palladium on activated charcoal In methanol for 1.5h; Heating; Stage #2: With Decaborane In methanol at 20℃; for 2h; Stage #3: formaldehyd With Decaborane In methanol; water at 20℃; for 3h;	98%

Upstream product

• 623-11-0 1-methyl-4-nitrosobenzene 
• 99-87-6 4-methylisopropylbenzene 
• 6746-22-1 tetra(p-tolyl)tin 
• 106-49-0 p-toluidine 
• 546-67-8 lead(IV) tetraacetate 
• 64-19-7 acetic acid 
• 98-95-3 nitrobenzene 
• 2229-07-4 methyl radical 
• 625-58-1 ethyl nitrate 
• 108-88-3 toluene 
• 928-45-0 butyl nitrate 
• 21823-34-7 1-chloro-2-nitrooxy-ethane 
• 591-09-3 nitro acetate 
• 636-98-6 p-nitrobenzene iodide 

Downstream Products

• 1694-20-8 trans-4-nitrostilbene 
• 2844-15-7 4-dimethylamino-4'-nitrostilbene 
• 21259-34-7 N-(4-methyl-phenyl)-α-thiopicolinamide 
• 75358-99-5 N-( p-tolyl)pyridine-4-carbothioamide 
• 147162-28-5 dichloro-(2-[(E)-2-(4-methylphenyl)-1-diazenyl]pyridine) 
• 114306-03-5 (4-nitro-phenyl)-pyruvic acid methyl ester 
• 104509-65-1 N-(2-methyl-5-nitro-benzyl)-succinimide 
• 100-11-8 1-bromomethyl-4-nitro-benzene 
• 623-08-5 N-methyl-p-toluidine 
• 501-60-0 1,2-di(p-tolyl)diazene 
• 408353-86-6 N-(2-methyl-5-nitro-benzyl)-phthalimide 
• 82137-73-3 (2-methyl-5-nitro-phenyl)-(4-nitro-phenyl)-methane 
• 371959-15-8 N-heptyl-4-methylbenzene amine 
• 58966-24-8 2-(chloromethyl)-4-nitrotoluene 

Relevant articles and documents

Intermediate Formation of a ?-Alkyl Iron(III) Complex in the Reduction of 4-Nitrobenzyl Chloride catalysed by Iron(II)-porphyrins

Formation of the ?-alkyl FeIII (TPP)(CH2C6H4NO2-4) complex (TPP = tetraphenylporphyrin) during reduction of 4-nitrobenzyl chloride (1) by sodium ascorbate catalysed by Fe(TPP)(Cl) was detected by visible spectroscopy, and its involvement as an intermediate in the reduction of (1) to 4-nitrotoluene was deduced from a study of the characteristics of this reaction.

Mechanochemical nitration of toluene with metal oxide catalysts

Results of an experimental study of the mechanochemical nitration of toluene are presented. The focus is on the effect of acidity of metal oxide catalysts on the yield of mononitrotoluene. No solvents were used during the reaction. Sodium nitrate served as a source of nitronium. Gas chromatography-mass spectrometry of the products showed that the nitration rate scaled with the catalyst's acidity and specific surface area. Homogenizing NaNO3 with the catalyst by additional milling prior to reaction with toluene led to a rapid, nearly complete nitration. Distribution of nitrate over the surface of catalyst is likely rate limiting when toluene is mechanochemically nitrated without the preliminary milling step. The observed for varied reactant ratios trends in yield and isomer ratios suggest that nitronium participates in the nitration while localized on the active sites of the catalyst. Excess of toluene blocks acid sites, inhibiting the formation of nitronium and impeding the nitration.

Selective Mild Oxidation of Anilines into Nitroarenes by Catalytic Activation of Mesoporous Frameworks Linked with Gold-Loaded Mn3O4 Nanoparticles

This work reports the synthesis and catalytic application of mesoporous Au-loaded Mn3O4 nanoparticle assemblies (MNAs) with different Au contents, i. e., 0.2, 0.5 and 1 wt %, towards the selective oxidation of anilines into the corresponding nitroarenes. Among common oxidants, as well as several supported gold nanoparticle platforms, Au/Mn3O4 MNAs containing 0.5 wt % Au with an average particle size of 3–4 nm show the best catalytic performance in the presence of tert-butyl hydroperoxide (TBHP) as a mild oxidant. In all cases, the corresponding nitroarenes were isolated in high to excellent yields (85–97 %) and selectivity (>98 %) from acetonitrile or greener solvents, such as ethyl acetate, after simple flash chromatography purification. The 0.5 % Au/Mn3O4 catalyst can be isolated and reused four times without a significant loss of its activity and can be applied successfully to a lab-scale reaction of p-toluidine (1 mmol) leading to the p-nitrotulene in 83 % yield. The presence of AuNPs on the Mn3O4 surface enhances the catalytic activity for the formation of the desired nitroarene. A reasonable mechanism was proposed including the plausible formation of two intermediates, the corresponding N-aryl hydroxylamine and the nitrosoarene.

The graphite-catalyzed: ipso -functionalization of arylboronic acids in an aqueous medium: metal-free access to phenols, anilines, nitroarenes, and haloarenes

An efficient, metal-free, and sustainable strategy has been described for the ipso-functionalization of phenylboronic acids using air as an oxidant in an aqueous medium. A range of carbon materials has been tested as carbocatalysts. To our surprise, graphite was found to be the best catalyst in terms of the turnover frequency. A broad range of valuable substituted aromatic compounds, i.e., phenols, anilines, nitroarenes, and haloarenes, has been prepared via the functionalization of the C-B bond into C-N, C-O, and many other C-X bonds. The vital role of the aromatic π-conjugation system of graphite in this protocol has been established and was observed via numerous analytic techniques. The heterogeneous nature of graphite facilitates the high recyclability of the carbocatalyst. This effective and easy system provides a multipurpose approach for the production of valuable substituted aromatic compounds without using any metals, ligands, bases, or harsh oxidants.