121-72-2

Basic information

• Product Name: N,N-DIMETHYL-M-TOLUIDINE
• Synonyms: N,N-DIMETHYL-3-TOLUIDINE;N,N-DIMETHYL-3-METHYLANILINE;N,N,3-TRIMETHYLBENZENAMINE;N,N-DIMETHYL-M-TOLUIDINE;TIMTEC-BB SBB008276;3,N,N-TRIMETHYLANILINE;N,N-Dimethyl-3-methylaniline~N,N,3-Trimethylaniline;N,N-Dimethyl-m-toliudine
• CAS NO: 121-72-2
• Molecular Formula: C₉H₁₃N
• Molecular Weight: 135.21
• EINECS: 204-495-6
• Product Categories: Amines;C9 to C10;Nitrogen Compounds
• Mol File: 121-72-2.mol

Chemical Properties

• Melting Point: -15 °C
• Boiling Point: 215 °C(lit.)
• Flash Point: 185 °F
• Appearance: Clear yellow/Liquid
• Density: 0.93 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.00383mmHg at 25°C
• Refractive Index: n20/D 1.55(lit.)
• Storage Temp.: Sealed in dry,Room Temperature
• PKA: 5.22±0.10(Predicted)
• BRN: 1422766
• CAS DataBase Reference: N,N-DIMETHYL-M-TOLUIDINE(CAS DataBase Reference)
• NIST Chemistry Reference: N,N-DIMETHYL-M-TOLUIDINE(121-72-2)
• EPA Substance Registry System: N,N-DIMETHYL-M-TOLUIDINE(121-72-2)

Safety Data

• Hazard Codes: T
• Statements: 23/24/25-33-52/53
• Safety Statements: 28-36/37-45-61
• RIDADR: UN 2810 6.1/PG 3
• WGK Germany: 2
• RTECS: XU5798000
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 121-72-2(Hazardous Substances Data)

Usage

Uses

Used in Chemical Synthesis:
N,N-DIMETHYL-M-TOLUIDINE is used as a building block for the synthesis of more complex compounds, such as BTK (Bruton's tyrosine kinase) inhibitors. It plays a crucial role in the development of pharmaceuticals and other chemical products.
Used in Chemical Research:
N,N-DIMETHYL-M-TOLUIDINE may be utilized in chemical synthesis studies, contributing to the advancement of knowledge in the field of chemistry and the discovery of new applications for this compound.

Air & Water Reactions

Tends to darken upon exposure to air. Insoluble in water.

Reactivity Profile

N,N-DIMETHYL-M-TOLUIDINE neutralizes acids in exothermic reactions to form salts plus water. May be incompatible with isocyanates, halogenated organics, peroxides, phenols (acidic), epoxides, anhydrides, and acid halides. May generate hydrogen, a flammable gas, in combination with strong reducing agents such as hydrides.

Health Hazard

TOXIC; inhalation, ingestion or skin contact with material may cause severe injury or death. Contact with molten substance may cause severe burns to skin and eyes. Avoid any skin contact. Effects of contact or inhalation may be delayed. Fire may produce irritating, corrosive and/or toxic gases. Runoff from fire control or dilution water may be corrosive and/or toxic and cause pollution.

Fire Hazard

Combustible material: may burn but does not ignite readily. When heated, vapors may form explosive mixtures with air: indoors, outdoors and sewers explosion hazards. Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated. Runoff may pollute waterways. Substance may be transported in a molten form.

Purification Methods

Reflux it for 3hours with 2 molar equivalents of Ac2O, then fractionally distil it under reduced pressure. Alternatively, dry over BaO, distil and store it over KOH. The hydrochloride has m 176o (from EtOH) and the picrate has m 131o. Methods described for N,N-dimethylaniline are applicable. [Beilstein 12 H 857, 12 III 1953, 12 IV 1815.]

InChI:InChI=1/C13H21N/c1-4-9-14(10-5-2)13-8-6-7-12(3)11-13/h6-8,11H,4-5,9-10H2,1-3H3

Upstream product

• 141-52-6 sodium ethanolate 
• 22237-91-8 3,N,N,N-tetramethylanilinium 
• 512-56-1 trimethyl phosphite 
• 108-44-1 1-amino-3-methylbenzene 
• 67-56-1 methanol 
• 77-78-1 dimethyl sulfate 
• 74-88-4 methyl iodide 
• 50-00-0 formaldehyd 
• 12109-10-3 (N,N-dimethylaniline)tricarbonylchromium 
• 91-66-7 N,N-diethylaniline 
• 7647-01-0 hydrogenchloride 
• 591-17-3 meta-bromotoluene 
• 67530-30-7 N,N-dimethyl O-(2,4,6-trimethylphenyl-sulfonyl) hydroxylamine 
• 28987-79-3 m-tolylmagnesium bromide 

Downstream Products

• 17485-25-5 3-methyl-N-nitroso-N-methylaniline 
• 56860-14-1 4,4'-bis-dimethylamino-2,2'-dimethyl-benzophenone 
• 32987-59-0 4,4'-bis-dimethylamino-2-methyl-benzophenone 
• 64969-07-9 2-(4-dimethylamino-2-methyl-benzoyl)-benzoic acid 
• 71050-29-8 bis(2-methyl-4-dimethylaminophenyl)-methane 
• 64672-71-5 (4-dimethylamino-2-methyl-phenyl)-ethenetricarbonitrile 
• 94764-43-9 tri-N-methyl-m-toluidinium; bromide 
• 33046-97-8 trimethyl(3-methylphenyl)ammonium iodide 
• 29785-93-1 4-dimethylamino-2-methyl(nitroso)benzene 
• 5066-17-1 2,2'-dimethyl-4-dimethylaminoazobenzene 
• 107153-98-0 3'-Chlor-4-dimethylamino-2-methyl-azobenzol 
• 65786-54-1 4'-chloro-4-dimethylamino-2-methyl-benzophenone 
• 21295-87-4 (4-dimethylamino-2-methyl-phenyl)-bis-(4-dimethylamino-phenyl)-methane 

Relevant articles and documents

Visible-light-promoted radical cross-coupling of: Para-quinone methides with N-substituted anilines: An efficient approach to 2,2-diarylethylamines

An efficient protocol to access 2,2-diarylethylamines via visible-light-promoted radical reactions of para-quinone methides (p-QMs) with N-alkyl anilines has been disclosed. These reactions feature metal-free, redox-neutral, and mild reaction conditions with wide functional group compatibility.

Alcohol promoted N -methylation of anilines with CO2/H2over a cobalt catalyst under mild conditions

N-Methylation of amines with CO2/H2 to N-methylamines over non-noble metal catalysts is very interesting but remains challenging. Herein, we present an alcohol (e.g., ethanol) promoted strategy for the N-methylation of anilines with CO2/H2 with high efficiency under mild conditions (e.g., 125 °C), which is achieved over a cobalt catalytic system composed of Co(OAc)2·4H2O, triphos and Sn(OTf)2. This catalytic system has a broad substrate scope and is tolerant toward a wide range of anilines and N-methyl anilines, and a series of N,N-dimethyl anilines were obtained in high yields. Mechanism investigation indicates that the alcohol solvent shifts the equilibrium of CO2 hydrogenation by forming an alkyl formate, which further reacts with the amine to produce N-formamide, and Sn(OTf)2 promotes the deoxygenative hydrogenation of N-formamides to afford N-methylamines. This is the first example of the N-methylation of amines with CO2/H2 over a cobalt catalytic system, which shows comparable performance to the reported Ru catalysts and may have promising applications.

Method for realizing N-alkylation by using alcohols as carbon source under photocatalysis

The invention discloses a method for realizing N-alkylation by using alcohols as a carbon source under photocatalysis, and belongs to the technical field of catalytic synthesis. Alcohol, a substrate raw material and a catalyst are placed in a reaction device, ultraviolet and/or visible light irradiation is carried out in an inert atmosphere, after the irradiation is finished, solid-liquid separation is carried out to remove the catalyst, and an N-alkylation product can be obtained through extraction, distillation and purification, wherein the substrate raw material comprises any one of an amine compound, an aromatic nitro compound or an aromatic nitrile compound, the alcohol comprises any one or more of soluble primary alcohols, and the catalyst is metal oxide/titanium dioxide or metal sulfide/titanium dioxide. The method is simple and easy to operate, can be used for efficient photocatalysis one-pot multi-step hydrogenation N-alkylation reaction, and is mild in reaction condition, high in chemical selectivity of N-alkylamine, good in catalyst stability and easy to recycle.

Additive-freeN-methylation of amines with methanol over supported iridium catalyst

An efficient and versatile zinc oxide-supported iridium (Ir/ZnO) catalyst was developed to catalyze the additive-freeN-methylation of amines with methanol. Mechanistic studies suggested that the high catalytic reactivity is rooted in the small sizes (1.4 nm) of Ir nanoparticles and the high ratio (93%) of oxidized iridium species (IrOx, Ir3+and Ir4+) on the catalyst. Moreover, the delicate cooperation between the IrOxand ZnO support also promoted its high reactivity. The selectivity of this catalyticN-methylation was controllable between dimethylation and monomethylation by carefully tuning the catalyst loading and reaction solvent. Specifically, neat methanol with high catalyst loading (2 mol% Ir) favored the formation ofN,N-dimethylated amine, while the mesitylene/methanol mixture with low catalyst loading (0.5 mol% Ir) was prone to producing mono-N-methylated amines. An environmentally benign continuous flow system with a recycled mode was also developed for the efficient production ofN-methylated amines. With optimal flow rates and amine concentrations, a variety ofN-methylamines were produced with good to excellent yields in this Ir/ZnO-based flow system, providing a starting point for the clean and efficient production ofN-methylamines with this cost-effective chemical process.

Trialkylammonium salt degradation: Implications for methylation and cross-coupling

Trialkylammonium (most notably N,N,N-trimethylanilinium) salts are known to display dual reactivity through both the aryl group and the N-methyl groups. These salts have thus been widely applied in cross-coupling, aryl etherification, fluorine radiolabelling, phase-transfer catalysis, supramolecular recognition, polymer design, and (more recently) methylation. However, their application as electrophilic methylating reagents remains somewhat underexplored, and an understanding of their arylation versus methylation reactivities is lacking. This study presents a mechanistic degradation analysis of N,N,N-trimethylanilinium salts and highlights the implications for synthetic applications of this important class of salts. Kinetic degradation studies, in both solid and solution phases, have delivered insights into the physical and chemical parameters affecting anilinium salt stability. 1H NMR kinetic analysis of salt degradation has evidenced thermal degradation to methyl iodide and the parent aniline, consistent with a closed-shell SN2-centred degradative pathway, and methyl iodide being the key reactive species in applied methylation procedures. Furthermore, the effect of halide and non-nucleophilic counterions on salt degradation has been investigated, along with deuterium isotope and solvent effects. New mechanistic insights have enabled the investigation of the use of trimethylanilinium salts in O-methylation and in improved cross-coupling strategies. Finally, detailed computational studies have helped highlight limitations in the current state-of-the-art of solvation modelling of reaction in which the bulk medium undergoes experimentally observable changes over the reaction timecourse. This journal is

Nickel-Catalyzed Amination of Aryl Chlorides with Amides

A nickel-catalyzed amination of aryl chlorides with diverse amides via C-N bond cleavage has been realized under mild conditions. A broad substrate scope with excellent functional group tolerance at a low catalyst loading makes the protocol powerful for synthesizing various aromatic amines. The aryl chlorides could selectively couple to the amino fragments rather than the carbonyl moieties of amides. Our protocol complements the conventional amination of aryl chlorides and expands the usage of inactive amides.

CO2-tuned highly selective reduction of formamides to the corresponding methylamines

We herein describe an efficient, CO2-tuned and highly selective C-O bond cleavage of N-methylated formanilides. With easy-to-handle and commercially available NaBH4 as the reductant, a variety of formanilides could be turned into the desired tertiary amines in moderate to excellent yields. The role of CO2 has been investigated in detail, and the mechanism is proposed on the basis of experiments.

Visible-Light-Induced C(sp2)-C(sp3) Cross-Dehydrogenative-Coupling Reaction of N-Heterocycles with N-Alkyl- N-methylanilines under Mild Conditions

Disclosed herein is a cross-dehydrogenative-coupling reaction of N-heterocycles including 1,2,4-triazine-3,5(2H, 4H)-diones and quinoxaline-2(1H)-ones with N-methylanilines to form C(sp2)-C(sp3) under visible-light illumination and ambient air at room temperature. In this process, easily available Ru(bpy)3Cl2·6H2O serves as the catalyst, and air acts as the green oxidant. This method features high atom economy, environmental friendliness, and convenient operation and provides an efficient and practical access to aminomethyl-substituted N-heterocycles with extensive functional group compatibility in 40-86% yields.

Utilization of renewable formic acid from lignocellulosic biomass for the selective hydrogenation and/or N-methylation

Lignocellulosic biomass is one of the most abundant renewable sources in nature. Herein, we have developed the utilization of renewable formic acid from lignocellulosic biomass as a hydrogen source and a carbon source for the selective hydrogenation and further N-methylation of various quinolines and the derivatives, various indoles under mild conditions in high efficiencies. N-methylation of various anilines is also developed. Mechanistic studies indicate that the hydrogenation occurs via a transfer hydrogenation pathway.

Catalyst-free selective: N -formylation and N -methylation of amines using CO2 as a sustainable C1 source

We herein describe catalyst-free selective N-formylation and N-methylation of amines using CO2 as a sustainable C1 source. By tuning the reaction solvent and temperature, the selective synthesis of formamides and methylamines is achieved in good to excellent yields using sodium borohydride (NaBH4) as a sustainable reductant.