100-22-1

Basic information

• Product Name: N,N,N',N'-Tetramethyl-1,4-phenylenediamine
• Synonyms: N,N,N',N'-TETRAMETHYL-1,4-PHENYLENEDIAMINE;N,N,N',N'-TETRAMETHYL-P-PHENYLENEDIAMINE;1,4-BIS(DIMETHYLAMINO)BENZENE;1,4-bis(dimethylamino)-benzen;4-Benzenediamine,N,N,N’,N’-tetramethyl-1;Benzene, 1,4-bis(dimethylamino)-;N,N,N',N'-Tetramethyl-1,4-Benzenediamine;N,N,N',N'-Tetramethyl-p-fenylendiamin
• CAS NO: 100-22-1
• Molecular Formula: C₁₀H₁₆N₂
• Molecular Weight: 164.25
• EINECS: 202-831-6
• Mol File: 100-22-1.mol

Chemical Properties

• Melting Point: 49-51 °C(lit.)
• Boiling Point: 260 °C(lit.)
• Flash Point: >230 °F
• Appearance: off-white to gray/powder
• Density: 0.9743 (rough estimate)
• Refractive Index: 1.5700 (estimate)
• Storage Temp.: Refrigerator (+4°C)
• PKA: 5.92±0.12(Predicted)
• Water Solubility: slightly in cold, more in hot water
• Sensitive: Air & Light Sensitive
• Stability: Stable, but may be air or light sensitive. Combustible. Incompatible with acids, acid chlorides, acid anhydrides, oxidizing agen
• Merck: 14,9228
• BRN: 1564025
• CAS DataBase Reference: N,N,N',N'-Tetramethyl-1,4-phenylenediamine(CAS DataBase Reference)
• NIST Chemistry Reference: N,N,N',N'-Tetramethyl-1,4-phenylenediamine(100-22-1)
• EPA Substance Registry System: N,N,N',N'-Tetramethyl-1,4-phenylenediamine(100-22-1)

Safety Data

• Hazard Codes: Xn
• Statements: 20/21/22-40-36/37/38
• Safety Statements: 28-28A-36-26-22
• RIDADR: UN 2811 6.1/PG 3
• WGK Germany: 1
• RTECS: ST4200000
• F: 10
• TSCA: Yes
• HazardClass: 6.1(a)
• PackingGroup: II
• Hazardous Substances Data: 100-22-1(Hazardous Substances Data)

Usage

Uses

Used in Analytical Chemistry:
N,N,N',N'-Tetramethyl-1,4-phenylenediamine is used as a reagent in the form of its hydrochloride salt. It is particularly useful for the detection of peroxidases on polyacrylamide gels, making it a valuable tool in various research and diagnostic applications.
Used in Enzyme Detection:
In the field of biochemistry and molecular biology, N,N,N',N'-Tetramethyl-1,4-phenylenediamine serves as a reducing co-substrate for heme peroxidases. This application is crucial for the identification and study of these enzymes, which are involved in various biological processes, including the immune response and detoxification.
Used in Pharmaceutical Industry:
Although not explicitly mentioned in the provided materials, N,N,N',N'-Tetramethyl-1,4-phenylenediamine may also find applications in the pharmaceutical industry, potentially as an intermediate in the synthesis of various drugs or as a component in drug formulations due to its chemical properties and reactivity.

Synthesis Reference(s)

The Journal of Organic Chemistry, 29, p. 488, 1964 DOI: 10.1021/jo01025a506

Air & Water Reactions

N,N,N',N'-Tetramethyl-1,4-phenylenediamine may be sensitive to air and heat. . Insoluble in water.

Reactivity Profile

N,N,N',N'-Tetramethyl-1,4-phenylenediamine can burn in air to give toxic NOx gases . 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. Flammable gaseous hydrogen may be generated in combination with strong reducing agents, such as hydrides.

Health Hazard

ACUTE/CHRONIC HAZARDS: When heated to decomposition N,N,N',N'-Tetramethyl-1,4-phenylenediamine emits toxic fumes. It is an irritant.

Fire Hazard

N,N,N',N'-Tetramethyl-1,4-phenylenediamine is probably combustible.

Safety Profile

Poison by ingestion. Moderatelytoxic by inhalation. Mutation data reported. When heatedto decomposition it emits toxic fumes of NOx.

Purification Methods

Crystallise the amine from pet ether or water. It can be sublimed or dried carefully in a vacuum line, and stored in the dark under nitrogen. It has been recrystallised from its melt. [Beilstein 13 H 74, 13 I 22, 13 II 40, 13 III 111, IV 107.]

Upstream product

• 67-56-1 methanol 
• 540-24-9 p-phenylenediamine hydrochloride 
• 624-18-0 benzene-1,4-diamine hydrochloride 
• 536-46-9 4-dimethylaminophenylamine dihydrochloride 
• 99-98-9 4-amino-N,N-dimethylaniline 
• 50-00-0 formaldehyd 
• 106-50-3 1,4-phenylenediamine 
• 74-88-4 methyl iodide 
• 13327-28-1 N,N,N',N'-tetramethyl-para-phenylenediamine hydrochloride 
• 1953-54-4 indol-5-ol 
• 150-75-4 N-methyl-p-aminophenol 
• 619-60-3 4-(N,N-dimethylamino)phenol 
• 20636-41-3 2,4,5-trihydroxypyrimidine 
• 95-54-5 1,2-diamino-benzene 

Downstream Products

• 5369-30-2 N-(4-(dimethylamino)phenyl)-N-methylnitrous amide 
• 5369-34-6 N,N,N'-trimethyl-p-phenylenediamine 
• 24624-25-7 tetra-N-methyl-p-phenylenediamine,radical ion[1+]; bromide 
• 112335-46-3 N,N,N',N'-Tetramethyl-p-phenylenediamine Iodide Cation Radical 
• 34527-55-4 Wuster's blue perchlorate 
• 101586-68-9 2-benzenesulfonyl-tetra-N-methyl-p-phenylenediamine 
• 5369-38-0 N¹,N¹,N¹,N⁴,N⁴,N⁴-hexamethylbenzene-1,4-diaminium iodide 
• 29164-52-1 2,3,4,5-Tetrachlor-p-phenylen-1,4-bis-iso-cyaniddichlorid 
• 67-66-3 chloroform 
• 94752-30-4 1,3-Dinitro-benzene; compound with N,N,N',N'-tetramethyl-benzene-1,4-diamine 
• 85-44-9 phthalic acid anhydride; radical anion 
• 144654-11-5 2-methyl(4-N,N-dimethylaminophenyl)amino-4,6-difluoro-s-triazine 
• 335-65-9 hydroperfluorooctane 
• 355-37-3 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane 

Relevant articles and documents

Mobilities of Radical Cations and Anions, Dimer Radical Anions, and Relative Electron Affinities by Times of Flight in n-Hexane

The mobilities of several radical cations and anions are measured in n-hexane using a thin-sheet time-of-flight (TOF) technique.We observe the radical cations of N,N,N',N'-tetramethyl-p-phenylenediamine, zinc tetraphenylporphine, and pyrene and the radical anions of perfluorobenzene, p-benzoquinone, anthraquinone, chloranil, buckminsterfullerene (C60), and octafluoronaphthalene.For all electron acceptors but C60, the dependence of the anionic TOF on acceptor concentration reveals the appearance of the homodimer radical anion at sufficiently high concentrations.The equilibrium constant for the monomer anion/monomer acceptor association reaction is obtained from the concentration studies.A Born-Haber cycle is then applied to estimate the difference between the electron affinities of the monomer and dimer molecules in the gas phase.

A Fast Kinetic Study of the Formation and Decay of N,N,N',N'-Tetramethyl-p-phenylenediamine Radical Cation in Aqueous Solution

The oxidation of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) by S2O82-, HSO5-, H2O2, MnO4-, Cr2O72-, CeIV and molecular bromine and iodine has been studied.The fast kinetics of formation of the diamine radical cation and its further oxidation at a longer time scale, or with a higher concentration of the oxidants at a shorter time scale, were studied by following the absorption and decay of the radical cation, TMPD+ at 565 or 615 nm.The reaction was found to be second-order overall, but first-order with respect to and .The values of the second-order rate constants for the formation and decay of the radical cation were found to be in line with the oxidation potentials of the oxidants.Reduction of the radical cation by dithionite was found to regenerate the diamine, and the rate constant for this reaction was also determined.

A new route to polykis(dialkylamino)benzenes and -naphthalenes based on protodefluorination of electron-rich fluoroaromatics: Anion radicals of arenes as a simple and effective alternative to 'classical' LAH-based systems

A simple and effective procedure for protodefluorination of electron-rich fluoroaromatic compounds has been developed. It operates with aromatic anion radicals as reducing agents and shows superior results over 'classical' lithium aluminum hydride based s

A FACILE GENERATION OF RADICAL CATIONS VIA THE ACTION OF NITROXIDES

Radical cations of aromatic amines and heteroaromatics were generated via the action of nitroxides in methylene chloride in the presence of trifluoroacetic acid.

Charging a Li-O2 battery using a redox mediator

The non-aqueous Li-air (O2) battery is receiving intense interest because its theoretical specific energy exceeds that of Li-ion batteries. Recharging the Li-O2 battery depends on oxidizing solid lithium peroxide (Li2O2), which is formed on discharge within the porous cathode. However, transporting charge between Li 2O2 particles and the solid electrode surface is at best very difficult and leads to voltage polarization on charging, even at modest rates. This is a significant problem facing the non-aqueous Li-O2 battery. Here we show that incorporation of a redox mediator, tetrathiafulvalene (TTF), enables recharging at rates that are impossible for the cell in the absence of the mediator. On charging, TTF is oxidized to TTF+ at the cathode surface; TTF+ in turn oxidizes the solid Li2O 2, which results in the regeneration of TTF. The mediator acts as an electron-hole transfer agent that permits efficient oxidation of solid Li 2O2. The cell with the mediator demonstrated 100 charge/discharge cycles.

Continuum of outer- and inner-sphere mechanisms for organic electron transfer. Steric modulation of the precursor complex in paramagnetic (ion-radical) self-exchanges

Transient 1:1 precursor complexes for intermolecular self-exchange between various organic electron donors (D) and their paramagnetic cation radicals (D+.), as well as between different electron acceptors (A) paired with their anion radicals (A .), are spectrally (UV-NIR) observed and structurally (X-ray) identified as the cofacial (π-stacked) associates [D, D+.] and [A-.· A], respectively. Mulliken-Hush (two-state) analysis of their diagnostic intervalence bands affords the electronic coupling elements (HOA), which together with the Marcus reorganization energies (λ) from the NIR spectral data are confirmed by molecular-orbital computations. The HDA values are found to be a sensitive function of the bulky substituents surrounding the redox centers. As a result, the steric modulation of the donor/acceptor separation (rDA) leads to distinctive electron-transfer rates between sterically hindered donors/acceptors and their more open (unsubstituted) parents. The latter is discussed in the context of a continuous series of outer- and inner-sphere mechanisms for organic electron-transfer processes in a manner originally formulated by Taube and co-workers for inorganic (coordination) donor/acceptor dyads-with conciliatory attention paid to traditional organic versus inorganic concepts.

Intermolecular electron-transfer reactions involving hydrazines

The self-exchange electron-transfer (ET) rate constant k22 for 1,2,3,4,5-pentamethylferrocene was determined by NMR line broadening to be 8.5(±0.8) × 106 M-1 s-1 (25 °C, CD3CN/0.09 M Et4NBF

Chronoamperometry at Channel Electrodes. Experimental Applications of Double Electrodes

Applications of transient experiments using double-channel electrodes are reported.The current response of a downstream detector electrode to a potential step at an upstream generator electrode is found to be in good agreement with theory.Such experiments are used to (i) demonstrate that the diffusion coefficient of the electrogenerated radical anion of p-chloranil in acetonitrile solution is 0.94 x 10-5 cm2 s-1, which contrasts markedly with that of the parent material (1.75 x 10-5 cm2 s-1), and (ii) characterize the nature of electrolytic processes occuring at the surface of porous silicon electrodes.The latter are shown to be electroactive throughout the depth of the porous surface layer.

A general method for N-methylation of amines and nitro compounds with dimethylsulfoxide

DMSO methylates a broad range of amines in the presence of formic acid, providing a novel, green and practical method for amine methylation. The protocol also allows the one-pot transformation of aromatic nitro compounds into dimethylated amines in the presence of a simple iron catalyst. Not just a solvent: DMSO methylates a broad range of amines in the presence of formic acid, providing a novel, green and practical method for amine methylation. The protocol also allows the one-pot transformation of aromatic nitro compounds into dimethylated amines in the presence of a simple iron catalyst. Copyright

Monophotonic Ionization through a Long-Lived Ion Pair: N,N,N',N'-Tetramethyl-p-phenylenediamine in Acetonitrile Solution

The monophotonic ionization of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) has been studied by means of transient absorption and transient photoconductivity measurements in acetonitrile solution.It has been concluded that the photoionization of TMPD is similar to that of 2,7-bis(dimethylamino)-4,5,9,10-tetrahydropyrene in acetonitrile solution.The formation and decay of the bound ion-pair state which is formed from the fluorescent state of TMPD and gives a quite similar absorption spectrum to the dissociated TMPD cation radical has been observed directly.The decay of the bound ion-pair state has been found to obey the reciprocal square root time dependence in the submicro to tens of microsecond time region.