1671-49-4

Basic information

• Product Name: 2-Nitro-4-methylsulfonyltoluene
• Synonyms: O-NITRO-P-METHYL SULFONYL TOLUENE;2-NITRO-4-METHYLSULFONYLTOLUENE;4-METHYLSULFONYL-2-NITROTOLUENE;METHYL 3-NITRO-P-TOLYL SULFONE;4-Methy-2-Nitrosulfonyl Toluene 2-Nitro-4-Methylsulfonyl Toluene;4-Methy-2-Nitrosulfonyl Toluene;4- Methylsulfonyl-2-nitritolunen;2-Nitro-4-methylsulf
• CAS NO: 1671-49-4
• Molecular Formula: C₈H₉NO₄S
• Molecular Weight: 215.23
• EINECS: 430-550-0
• Mol File: 1671-49-4.mol
• Article Data: 13

Chemical Properties

• Melting Point: 120-121°C
• Boiling Point: 387.8 °C at 760 mmHg
• Flash Point: 188.3 °C
• Appearance: /
• Density: 1.35 g/cm³
• Vapor Pressure: 7.16E-06mmHg at 25°C
• Refractive Index: 1.551
• Storage Temp.: Sealed in dry,Room Temperature
• Water Solubility: 370mg/L at 25℃
• CAS DataBase Reference: 2-Nitro-4-methylsulfonyltoluene(CAS DataBase Reference)
• NIST Chemistry Reference: 2-Nitro-4-methylsulfonyltoluene(1671-49-4)
• EPA Substance Registry System: 2-Nitro-4-methylsulfonyltoluene(1671-49-4)

Safety Data

• Statements: 23/24/25-36/37/38
• Safety Statements: 26-36/37/39
• RIDADR: 2811
• Hazardous Substances Data: 1671-49-4(Hazardous Substances Data)

Usage

Chemical Properties

white powdery crystal

InChI:InChI=1/C8H9NO4S/c1-6-3-4-7(14(2,12)13)5-8(6)9(10)11/h3-5H,1-2H3

Synthetic route

Methyl p-tolyl sulfone (3185-99-7) → 1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4)

Conditions	Yield
With sulfuric acid; nitric acid In water at 100℃; Flow reactor; chemoselective reaction;	98%
With sulfuric acid; nitric acid
In sulfuric acid

Methyl p-tolyl sulfone (3185-99-7) → 1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4) + Methyl-<3,5-dinitro-4-methyl-phenyl>-sulfon (89977-30-0)

Conditions	Yield
With sulfuric acid; nitric acid In water at 75℃; for 0.00416667h; Temperature; Time; Flow reactor; chemoselective reaction;	A 90% B 9%

1-methyl-2-nitrobenzene (88-72-2) + Methanesulfonic anhydride (7143-01-3) → 1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4)

Conditions	Yield
With trifluorormethanesulfonic acid; tris(trifluoromethanesulfonyloxy)boron at 50℃; for 3h; Substitution;	47 % Chromat.

1-methyl-2-nitrobenzene (88-72-2) + methanesulfonyl chloride (124-63-0) → 1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4) + 2-nitro-6-methylsulphonyltoluene (90764-86-6)

Conditions	Yield
With aluminum (III) chloride; tetrabutyl-ammonium chloride at 160℃; for 16h; Temperature; Inert atmosphere; Large scale;

1-methyl-2-nitrobenzene (88-72-2) → 1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: chlorosulfonic acid / 3.5 h / 110 - 115 °C 1.2: 3 h / 60 - 65 °C 2.1: sodium sulfite; sodium carbonate / water / 3 h / 0 - 25 °C / pH 7.5 - 8 2.2: 14 h / 40 - 100 °C View Scheme

4-methyl-3-nitrobenzenesulfonyl chloride (616-83-1) + chloroacetic acid (79-11-8) → 1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4)

Conditions	Yield
Stage #1: 4-methyl-3-nitrobenzenesulfonyl chloride With sodium carbonate; sodium sulfite In water at 0 - 25℃; for 3h; pH=7.5 - 8; Stage #2: chloroacetic acid With pyrographite In water at 40 - 100℃; for 14h; Temperature;

p-toluenesulfonyl chloride (98-59-9) → 1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: sodium hydrogencarbonate; sodium sulfite / water / 9 h / 75 °C 1.2: 4.5 h / 45 - 130 °C 2.1: sulfuric acid / 0.5 h / 20 °C 2.2: 10 h / 10 °C View Scheme

1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4) → 2-methyl-5-(methylsulphonyl)aniline (1671-48-3)

Conditions	Yield
With hydrogen; platinum(IV) oxide In ethyl acetate under 3800.26 Torr; for 1.25h;	99%
With platinum(IV) oxide; hydrogen In ethyl acetate under 3800.26 Torr; for 1.25h; Autoclave;	99%
With hydrogenchloride; iron
With hydrogenchloride; tin

1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4) → 4-methanesulfonyl-2-nitro-benzoic acid (110964-79-9)

Conditions	Yield
With sulfuric acid; oxygen; nitric acid; vanadia at 140℃; for 11h; Temperature;	98%
With sulfuric acid; oxygen; nitric acid; vanadia at 138 - 140℃; under 37.5038 Torr; Catalytic behavior; Temperature; Autoclave;	96.7%
With oxygen; nitric acid; acetic acid; 2,6-dihydroxypyrrolo[3,4-f]isoindolo-1,3,5,7(2H,6H)tetrone at 150℃; under 37503.8 Torr; for 5h; Catalytic behavior; Reagent/catalyst; Temperature; Pressure; Autoclave;	94.9%

1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4) → 2-nitro-4-methanesulfonyl-α,α,α-trichlorotoluene

Conditions	Yield
With chlorine; sodium carbonate at 20 - 80℃; under 1500.15 - 6000.6 Torr; for 12h; Temperature; Pressure; Autoclave;	93.3%

1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4) + acetic acid (64-19-7) → 4-methanesulfonyl-2-nitro-benzoic acid (110964-79-9)

Conditions	Yield
With 1,1,2,2-tetrabromoethane; cobalt(II) acetate; manganese(III) triacetate dihydrate In water at 210℃; under 22801.5 Torr; for 3h; Reagent/catalyst; Solvent; Temperature; Pressure; Reflux;	92%

1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4) → 2-amino-4-(methylsulfonyl)benzoic acid (393085-45-5)

Conditions	Yield
With selenium; cobalt(II) chloride hexahydrate; nitrobenzene In methanol; water; dimethyl sulfoxide at 90℃; for 5h; Inert atmosphere;	59%
Multi-step reaction with 2 steps 1: KMnO4; aqueous pyridine 2: iron-powder; aqueous HCl View Scheme

1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4) → 2-iodo-1-methyl-4-(methylsulfonyl)benzene (100959-90-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: iron; aqueous HCl View Scheme
Multi-step reaction with 2 steps 1.1: platinum(IV) oxide; hydrogen / ethyl acetate / 1.25 h / 3800.26 Torr / Autoclave 2.1: hydrogenchloride; sodium nitrite / water / 0.5 h / 0 °C 2.2: 1 h / 20 °C View Scheme

1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4) → 3-methanesulfonyl-benzo[4,5]thiazolo[2,3-b]quinazolin-12-one

Conditions	Yield
Multi-step reaction with 3 steps 1: KMnO4; aqueous pyridine 2: iron-powder; aqueous HCl View Scheme

vanadium(V) oxide (788133-24-4) + 1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4) → 4-methanesulfonyl-2-nitro-benzoic acid (110964-79-9)

Conditions	Yield
With nitric acid In sulfuric acid

1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4) → 4-methylsulphonyl-2-nitrobenzoyl chloride (110964-80-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: vanadia; nitric acid / 135 - 160 °C 2: thionyl chloride; N,N-dimethyl-formamide / 1,2-dichloro-ethane / 6 h / 60 - 65 °C View Scheme
Multi-step reaction with 2 steps 1.1: vanadia; sulfuric acid; nitric acid / 13 h / 145 - 165 °C 2.1: N,N-dimethyl-formamide / dichloromethane / 0.5 h 2.2: 5 h / 30 - 80 °C View Scheme
Multi-step reaction with 2 steps 1: oxygen; cobalt(II) chloride; iron(III) sulfate / acetic acid / 300 °C / 18751.9 Torr 2: bis(trichloromethyl) carbonate / N,N-dimethyl-formamide / 3 h / 70 °C View Scheme

1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4) → 3-(4'-methylsulfonyl-2'-nitro-benzoyloxy)-2-cyclohexene-1-one (226944-49-6)

Conditions	Yield
Multi-step reaction with 3 steps 1: vanadia; nitric acid / 135 - 160 °C 2: thionyl chloride; N,N-dimethyl-formamide / 1,2-dichloro-ethane / 6 h / 60 - 65 °C 3: triethylamine / 1,2-dichloro-ethane / 1 h / 5 - 35 °C View Scheme
Multi-step reaction with 3 steps 1.1: vanadia; sulfuric acid; nitric acid / 13 h / 145 - 165 °C 2.1: N,N-dimethyl-formamide / dichloromethane / 0.5 h 2.2: 5 h / 30 - 80 °C 3.1: tetrabutylammomium bromide / water; dichloromethane / 6 h / 2 °C View Scheme

1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4) → mesotrione (104206-82-8)

Conditions	Yield
Multi-step reaction with 4 steps 1: vanadia; nitric acid / 135 - 160 °C 2: thionyl chloride; N,N-dimethyl-formamide / 1,2-dichloro-ethane / 6 h / 60 - 65 °C 3: triethylamine / 1,2-dichloro-ethane / 1 h / 5 - 35 °C 4: triethylamine; 2-hydroxy-2-methylpropanenitrile / 5 h / 20 - 25 °C View Scheme
Multi-step reaction with 4 steps 1.1: vanadia; sulfuric acid; nitric acid / 13 h / 145 - 165 °C 2.1: N,N-dimethyl-formamide / dichloromethane / 0.5 h 2.2: 5 h / 30 - 80 °C 3.1: tetrabutylammomium bromide / water; dichloromethane / 6 h / 2 °C 4.1: triethylamine / dichloromethane / 0.25 h / 30 °C 4.2: 3 h / 30 °C View Scheme
Multi-step reaction with 3 steps 1.1: oxygen; cobalt(II) chloride; iron(III) sulfate / acetic acid / 300 °C / 18751.9 Torr 2.1: bis(trichloromethyl) carbonate / N,N-dimethyl-formamide / 3 h / 70 °C 3.1: 15-crown-5; sodium hydroxide / chloroform / 1.5 h / 35 °C 3.2: 3.5 h / 350 °C View Scheme

1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4) → (R)-6-(methylsulfonyl)-3-(2-phenylbut-3-en-2-yl)-1H-indazole + 6-(methylsulfonyl)-3-(2-phenylbut-3-en-2-yl)-1H-indazole

Conditions

Yield

Multi-step reaction with 5 steps 1: N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) / tetrachloromethane / Inert atmosphere; Reflux 2: ammonia / methanol / 20 °C 3: sodium hydroxide / methanol / Reflux 4: dmap / diethyl ether / 20 °C / Inert atmosphere 5: copper diacetate; (+)-1,2-bis((2S,5S)-2,5-diphenylphospholanyl)ethane; (dimethoxy)methylsilane / tetrahydrofuran / 12 h / 60 °C / Inert atmosphere; Glovebox; Sealed tube View Scheme

1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4) → 6-(methylsulfonyl)-1H-indazol-1-yl 2,4,6-trimethylbenzoate

Conditions	Yield
Multi-step reaction with 4 steps 1: N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) / tetrachloromethane / Inert atmosphere; Reflux 2: ammonia / methanol / 20 °C 3: sodium hydroxide / methanol / Reflux 4: dmap / diethyl ether / 20 °C / Inert atmosphere View Scheme

1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4) → 6-(methylsulfonyl)-1H-indazol-1-ol

Conditions	Yield
Multi-step reaction with 3 steps 1: N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) / tetrachloromethane / Inert atmosphere; Reflux 2: ammonia / methanol / 20 °C 3: sodium hydroxide / methanol / Reflux View Scheme

1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4) → 4-(methylsulfonyl)-2-nitrobenzylamine

Conditions	Yield
Multi-step reaction with 2 steps 1: N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) / tetrachloromethane / Inert atmosphere; Reflux 2: ammonia / methanol / 20 °C View Scheme

1-methyl-4-(methylsulfonyl)-2-nitrobenzene (1671-49-4) → 2-nitro-4-(methylsulphonyl)benzyl bromide

Conditions	Yield
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In tetrachloromethane Inert atmosphere; Reflux;

Upstream product

• 88-72-2 1-methyl-2-nitrobenzene 
• 124-63-0 methanesulfonyl chloride 
• 98-59-9 p-toluenesulfonyl chloride 
• 616-83-1 4-methyl-3-nitrobenzenesulfonyl chloride 
• 79-11-8 chloroacetic acid 
• 3185-99-7 Methyl p-tolyl sulfone 
• 7143-01-3 Methanesulfonic anhydride 
• 1671-48-3 2‐methyl‐5‐(methylsulfonyl)aniline 

Downstream Products

• 110964-80-2 4-methylsulphonyl-2-nitrobenzoyl chloride 
• 226944-49-6 3-(4'-methylsulfonyl-2'-nitro-benzoyloxy)-2-cyclohexene-1-one 
• 104206-82-8 mesotrione 
• 849035-67-2 2-nitro-4-(methylsulphonyl)benzyl bromide 
• 110964-79-9 4-methanesulfonyl-2-nitro-benzoic acid 
• 393085-45-5 2-amino-4-(methylsulfonyl)benzoic acid 
• 1671-48-3 2‐methyl‐5‐(methylsulfonyl)aniline 

Relevant articles and documents

Selective synthesis of sulfoxides and sulfonesviacontrollable oxidation of sulfides withN-fluorobenzenesulfonimide

A practical and mild method for the switchable synthesis of sulfoxides or sulfonesviaselective oxidation of sulfides using cheapN-fluorobenzenesulfonimide (NFSI) as the oxidant has been developed. These highly chemoselective transformations were simply achieved by varying the NFSI loading with H2O as the green solvent and oxygen source without any additives. The good functional group tolerance makes the strategy valuable.

Method for synthesizing aromatic nitro compound by microchannel reactor

The invention discloses a method for synthesizing an aromatic nitro compound by a microchannel reactor. The method comprises the following steps: continuously conveying p-methylsulfonyl toluene, sulfuric acid and nitric acid as raw materials into the microchannel reactor for reaction. The micro-channel reactor is used for preparing 2-nitro-4-sulfonyl methyl toluene, the high specific area of the micro-channel reactor can realize rapid heat transfer and keep constant temperature, reaction materials react rapidly during instant mixing, heat can be conducted out in time, local overheating is eliminated, the production risk is reduced, and the production efficiency is greatly improved.

Method for preparing 2-nitro-4-methylsulfonyltoluene by continuous flow

The invention discloses a method for preparing 2-nitro-4-methylsulfonyltoluene by continuous flow. The method comprises conveying 1-methyl-4-(methylsulfonyl)-benzene, sulfuric acid and nitric acid continuously into a channel reactor, and allowing to react so as to continuously prepare 2-nitro-4-methylsulfonyltoluene, wherein the channel reactor comprises a cooling module, a fluid module and an outlet module which are communicated in sequence. The method of the invention has the advantages of high safety, low byproduct output, high product purity and the like, and also has the advantages of good process simplicity, good operational convenience, high automation level, high preparation efficiency and the like; the method of the invention is suitable for large-scale continuous preparation of 2-nitro-4-methylsulfonyltoluene and has good application value and application prospect.