99-98-9

Basic information

• Product Name: N,N-Dimethyl-1,4-phenylenediamine
• Synonyms: 4-ANIMODIMETHYLANILINE;4-AMINODIMETHYLANILINE;4-AMINO-N,N-DIMETHYLANILINE;4-DIMETHYLAMINOANILINE;Dimethyl-p-phenylenediamine;DIMETHYL(N,N-)-P-PHENYLENEDIAMINE;WURSTER'S RED;4-(dimethylamino)benzenamine
• CAS NO: 99-98-9
• Molecular Formula: C₈H₁₂N₂
• Molecular Weight: 136.19
• EINECS: 202-807-5
• Product Categories: Amines
• Mol File: 99-98-9.mol

Chemical Properties

• Melting Point: 34-36 °C(lit.)
• Boiling Point: 262 °C(lit.)
• Flash Point: 130 °C
• Appearance: black/crystalline
• Density: 1.09
• Vapor Pressure: 0.0107mmHg at 25°C
• Refractive Index: 1.5914 (estimate)
• Storage Temp.: 2-8°C
• PKA: 6?+-.0.12(Predicted)
• Water Solubility: 11 g/L (20 ºC)
• Sensitive: Light Sensitive
• Stability: Stable. Incompatible with acid chlorides, acid anhydrides, strong acids, strong oxidizing agents. Combustible.
• Merck: 14,3254
• BRN: 508105
• CAS DataBase Reference: N,N-Dimethyl-1,4-phenylenediamine(CAS DataBase Reference)
• NIST Chemistry Reference: N,N-Dimethyl-1,4-phenylenediamine(99-98-9)
• EPA Substance Registry System: N,N-Dimethyl-1,4-phenylenediamine(99-98-9)

Safety Data

• Hazard Codes: T
• Statements: 23/24/25-36/37/38
• Safety Statements: 28-45-36/37/39-26
• RIDADR: UN 2811 6.1/PG 2
• WGK Germany: 3
• RTECS: ST0874000
• F: 8-10-23
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 99-98-9(Hazardous Substances Data)

Usage

Uses

Used in Chemical Synthesis:
N,N-Dimethyl-1,4-phenylenediamine is used as a base for the production of methylene blue, a dye with various applications in the chemical industry.
Used in Photodevelopment:
N,N-Dimethyl-1,4-phenylenediamine is used as a photodeveloper, playing a crucial role in the development of photographic films and papers.
Used in Analytical Chemistry:
N,N-Dimethyl-1,4-phenylenediamine is used as a reagent for the detection of hydrogen sulfide, a toxic gas with a characteristic rotten egg smell. It helps in identifying the presence of this gas in various environments.
Used in Cellulose Analysis:
N,N-Dimethyl-1,4-phenylenediamine is used as a reagent for cellulose, a complex carbohydrate found in plant cell walls. It aids in the analysis and characterization of cellulose in various applications.
Used in Organic Synthesis:
N,N-Dimethyl-1,4-phenylenediamine is used in organic synthesis for the preparation of various compounds, including pharmaceuticals, dyes, and other organic chemicals.
Used in Microbiology:
N,N-Dimethyl-1,4-phenylenediamine is used as a reagent for certain bacteria, helping in the identification and classification of bacterial species.
Used in Molecular Compounds Preparation:
N,N-Dimethyl-1,4-phenylenediamine may be used for the preparation of molecular compounds with tetracyano-p-quinodimethane (TCNQ). The polarized absorption spectra of these molecular compounds have been investigated, providing insights into their properties and potential applications.

Synthesis Reference(s)

Chemistry Letters, 9, p. 439, 1980Tetrahedron Letters, 34, p. 2441, 1993 DOI: 10.1016/S0040-4039(00)60436-7

Reactivity Profile

N,N-Dimethyl-1,4-phenylenediamine 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. Incompatible with strong oxidizers, strong acids and acid anhydrides. Also incompatible with alkalis .

Hazard

Toxic by ingestion or inhalation of vapor.

Health Hazard

Lowest toxic dose with skin effect is 14 mg/kg. Irritant to skin and eyes.

Fire Hazard

When heated to decomposition, N,N-Dimethyl-1,4-phenylenediamine emits toxic fumes of nitrogen oxides.

InChI:InChI=1/C8H12N2/c1-9-7-3-5-8(10-2)6-4-7/h3-6,9-10H,1-2H3

Upstream product

• 857814-64-3 N,N'-dibenzoyl-N-(4-dimethylamino-phenyl)-hydrazine 
• 871876-73-2 2,3-dimethyl-4-nitroso-aniline 
• 42344-05-8 4-nitroso-N,N-dimethylaniline hydrochloride 
• 57842-97-4 N,N-dimethyl-p-phenylenediamine,radical ion[1+]; bromide 
• 108-24-7 acetic anhydride 
• 50-00-0 formaldehyd 
• 10050-89-2 4-dimethylamino-4'-(N,N-dimethylamino)benzylideneaniline 
• 64-19-7 acetic acid 
• 62-53-3 aniline 
• 138-89-6 p-dimethylaminonitrosobenzene 
• 121-69-7 N,N-dimethyl-aniline 
• 120-22-9 N,N-diethyl-4-nitrosoaniline 
• 123-31-9 hydroquinone 
• 74-89-5 methylamine 

Downstream Products

• 100715-22-8 thioisonicotinic acid-(4-dimethylamino-anilide) 
• 29202-13-9 N-(p-dimethylaminophenyl)pyridine-2-aldimine 
• 1145-75-1 N,N-dimethyl-N'-[4]pyridylmethylene-p-phenylenediamine 
• 13546-87-7 (E)-4-((furan-2-ylmethylene)amino)-N,N-dimethylaniline 
• 75075-24-0 nicotinic acid-(4-dimethylamino-anilide) 
• 68280-10-4 isonicotinic acid-(4-dimethylamino-anilide) 
• 107003-02-1 N'-[2]quinolylmethylene-N,N-dimethyl-p-phenylenediamine 
• 52688-64-9 N'-[4]quinolylmethylene-N,N-dimethyl-p-phenylenediamine 
• 27746-16-3 2-(4-(dimethylamino)phenyl)isoindoline-1,3-dione 
• 19336-90-4 N-(4-dimethylamino-phenyl)-phthalamic acid 
• 52688-57-0 N'-benzothiazol-2-ylmethylene-N,N-dimethyl-benzene-1,4-diamine 
• 109045-17-2 6-oxo-6H-pyran-2-carboxylic acid-(4-dimethylamino-anilide) 
• 109899-82-3 N,N-dimethyl-N'-(5-nitro-[2]pyridyl)-p-phenylenediamine 
• 1749-06-0 N'-benzo[1,3]dioxol-5-ylmethylene-N,N-dimethyl-benzene-1,4-diamine 

Relevant articles and documents

Developments in Dynamic Covalent Chemistries from the Reaction of Thiols with Hexahydrotriazines

Dynamic covalent chemistries have garnered significant attention for their potential to revolutionize technologies in the material fields (engineering, biomedical, and sensors) and synthetic design strategies as they provide access to stimuli responsiveness and adaptive behaviors. However, only a limited number of molecular motifs have been known to display this dynamic behavior under mild conditions. Here, we identified a dynamic covalent motif - thioaminals - that is produced from the reaction of hexahydrotriazines (HTs) with thiols. Furthermore, we report on the synthesis of a new family of step-growth polymers based on this motif. The condensation efficiently proceeds to quantitative yields within a short time frame and offers versatility in functional group tolerance; thus, it can be exploited to synthesize both small molecule thioaminals as well as high molecular weight polymers from the step-growth polymerization of HTs with dithiols. Careful evaluation of substituted HTs and organic thiols supported by DFT calculations led to a chemically diverse library of polymers based on this motif. Finally, dynamic substitution reactions were employed toward the facile preparation of functional oligomers and macromolecules. This dynamic covalent motif is particularly attractive for a range of applications that include material design and drug delivery due to the economic feasibility of synthesis.

Naphthalimide-Based Azo-Functionalized Supramolecular Vesicle in Hypoxia-Responsive Drug Delivery

Supramolecular materials that respond to external triggers are being extensively utilized in developing spatiotemporal control in biomedical applications ranging from drug delivery to diagnostics. The present article describes the development of self-assembled vesicles in 1:9 (v/v), tetrahydrofuran (THF)-water by naphthalimide-based azo moiety containing amphiphile (NI-Azo) where azo moiety would act as the stimuli-responsive junction. The self-assembly of NI-Azo took place through H-type of aggregation. Microscopic and spectroscopic analyses confirmed the formation of supramolecular vesicles with a dimension of 200-250 nm. Azo (-N=N-) moiety is known to get reduced to amine derivatives in the presence of the azoreductase enzyme, which is overexpressed in the hypoxic microenvironment. The absorbance intensity of this characteristic azo (-N=N-) moiety of NI-Azo (1:9 (v/v), THF-water) at 458 nm got diminished in the presence of both extracellular and intracellular bacterial azoreductase extracted from Escherichia coli bacteria. The same observation was noted in the presence of sodium dithionite (mimic of azoreductase), indicating that azoreductase/sodium dithionite induced azo bond cleavage of NI-Azo, which was confirmed by matrix-assisted laser desorption ionization time-of-flight spectrometric data of the corresponding aromatic amine fragments. The anticancer drug, curcumin, was encapsulated inside NI-Azo vesicles that successfully killed B16F10 cells (cancer cells) in CoCl2-induced hypoxic environment owing to the azoreductase-responsive release of drug. The cancer cell killing efficiency by curcumin-loaded NI-Azo vesicles in the hypoxic condition was 2.15-fold higher than that of the normoxic environment and 2.4-fold higher compared to that of native curcumin in the hypoxic condition. Notably, cancer cell killing efficiency of curcumin-loaded NI-Azo vesicles was 4.5- and 1.9-fold higher than that of noncancerous NIH3T3 cells in normoxic and hypoxic environments, respectively. Cell killing was found to be primarily through the early apoptotic pathway.

Nickel Boride Catalyzed Reductions of Nitro Compounds and Azides: Nanocellulose-Supported Catalysts in Tandem Reactions

Nickel boride catalyst prepared in situ from NiCl2 and sodium borohydride allowed, in the presence of an aqueous solution of TEMPO-oxidized nanocellulose (0.01 wt%), the reduction of a wide range of nitroarenes and aliphatic nitro compounds. Here we describe how the modified nanocellulose has a stabilizing effect on the catalyst that enables low loading of the nickel salt pre-catalyst. Ni-B prepared in situ from a methanolic solution was also used to develop a greener and facile reduction of organic azides, offering a substantially lowered catalyst loading with respect to reported methods in the literature. Both aromatic and aliphatic azides were reduced, and the protocol is compatible with a one-pot Boc-protection of the obtained amine yielding the corresponding carbamates. Finally, bacterial crystalline nanocellulose was chosen as a support for the Ni-B catalyst to allow an easy recovery step of the catalyst and its recyclability for new reduction cycles.

Green synthesized AgNPs decorated on Ketjen black for enhanced catalytic dye degradation

The green synthesis of nanoparticles using plant-based materials as an alternative to chemical and physical routes provides economic and environmental benefits. In the present study, silver nanoparticles (AgNPs) were fabricated using Pseudocydonia sinensis fruit extract. The fabricated NPs were then decorated on commercial Ketjen black-300 (AgNPs@KB-300) and Ketjen black-600 (AgNPs@ KB-600). The synthesized materials were characterized via XRD, FTIR, XPS, SEM-EDX, and HR-TEM studies. The SEM and HR-TEM results revealed that the synthesized AgNPs were spherical and successfully decorated on KB-300 and KB-600. Additionally, the catalytic ability of the synthesized samples during the degradation of methyl orange in the presence of NaBH4 was studied. Notably, the catalytic activity of AgNPs@ KB-600 was higher than that of AgNPs@ KB-300.

Cu/CuxS-Embedded N,S-Doped Porous Carbon Derived in Situ from a MOF Designed for Efficient Catalysis

The reasonable design of the precursor of a carbon-based nanocatalyst is an important pathway to improve catalytic performance. In this study, a simple solvothermal method was used to synthesize [Cu(TPT)(2,5-tdc)] ? 2H2O (Cu-MOF), which contains N and S atoms, in one step. Further in-situ carbonization of the Cu-MOF as the precursor was used to synthesize Cu/CuxS-embedded N,S-doped porous carbon (Cu/CuxS/NSC) composites. The catalytic activities of the prepared Cu/CuxS/NSC were investigated through catalytic reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). The results show that the designed Cu/CuxS/NSC has exceptional catalytic activity and recycling stability, with a reaction rate constant of 0.0256 s?1, and the conversion rate still exceeds 90 % after 15 cycles. Meanwhile, the efficient catalytic reduction of dyes (CR, MO, MB and RhB) confirmed its versatility. Finally, the active sites of the Cu/CuxS/NSC catalysts were analyzed, and a possible multicomponent synergistic catalytic mechanism was proposed.

Manganese Catalyzed Hydrogenation of Azo (N=N) Bonds to Amines

We report the first example of homogeneously catalyzed hydrogenation of the N=N bond of azo compounds using a complex of an earth-abundant-metal. The hydrogenation reaction is catalyzed by a manganese pincer complex, proceeds under mild conditions, and yields amines, which makes this methodology a sustainable alternative route for the conversion of azo compounds. A plausible mechanism involving metal-ligand cooperation and hydrazine intermediacy is proposed based on mechanistic studies. (Figure presented.).

Development of sustainable and efficient nanocatalyst based on polyoxometalate/nickel oxide nanocomposite: A simple and recyclable catalyst for reduction of nitroaromatic compounds

In this paper, we report the synthesis and characterization of NiO@PolyMo nanocomposite. The newly synthesized nanocomposite was characterized by transmission electronmicroscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), and powder X-ray diffraction (XRD). The particle sizes of the NiO@PolyMo nanocatalyst are in the range of 10–20 nm. Powder XRD patterns show that the phase of NiO@PolyMo remains unaltered even after the functionalization of NiO. The lattice fringes of d = 0.20 nm were observed, which correspond to the (111) plane of NiO phase. The newly synthesized material shows excellent catalytic performance and good selectivity for reduction of nitroarenes. The advantages of the present protocols are mild, and can be carried out using water as a solvent, which is an eco-friendly benign.

Photocatalytic reduction of nitroaromatics into anilines using CeO2-TiO2 nanocomposite

The reduction of nitro compounds into amines is an important approach for synthetic and pharmaceutical chemistry. The reduced compounds are used as synthetic intermediates in the synthesis of therapeutic molecules. In the present work, we have fabricated cerium dioxide decorated TiO2 nanoparticles using a sol-gel-hydrothermal method. The synthesized nanocomposite was effectively reduced various nitro-compounds, specifically aromatic nitro compounds, into amines in visible light. All the nitro compounds screened in the photoreduction reaction showed >90% conversion with >96% selectivity. Chromatographic techniques confirmed the products obtained. The nanocomposite photocatalyst has excellent stability under the experimental condition and exhibited up to five cycles with no loss of metal content. The nanomaterials were characterized using various spectroscopic techniques.

Rhodium-terpyridine Catalyzed Transfer Hydrogenation of Aromatic Nitro Compounds in Water

A rhodium terpyridine complex catalyzed transfer hydrogenation of nitroarenes to anilines with i-PrOH as hydrogen source and water as solvent has been developed. The catalytic system can work at a substrate/catalyst (S/C) ratio of 2000, with a turnover frequency (TOF) up to 3360 h?1, which represents one of the most active catalytic transfer hydrogenation systems for nitroarene reduction. The catalytic system is operationally simple and the protocol could be scaled up to 20 gram scale. The water-soluble catalyst bearing a carboxyl group could be recycled 15 times without significant loss of activity.

Optimization of WZ4003 as NUAK inhibitors against human colorectal cancer

NUAK, the member of AMPK (AMP-activated protein kinase) family of protein kinases, is phosphorylated and activated by the LKB1 (liver kinase B1) tumor suppressor protein kinase. Recent work has indicated that NUAK1 is a key component of the antioxidant stress response pathway, and the inhibition of NUAK1 will suppress the growth and survival of colorectal tumors. As a promising target for anticancer drugs, few inhibitors of NUAK were developed. With this goal in mind, based on NUAK inhibitor WZ4003, a series of derivatives has been synthesized and evaluated for anticancer activity. Compound 9q, a derivative of WZ4003 by removing a methoxy group, was found to be the most potential one with stronger inhibitory against NUAK1/2 enzyme activity, tumor cell proliferation and inducing apoptosis of tumor cells. By in vivo efficacy evaluations of colorectal SW480 xenografts, 9q suppresses tumor growth more effectively with an excellent safety profile in vivo and is therefore seen as a suitable candidate for further investigation.