1915-42-0

Basic information

• Product Name: 4,4'-DIPYRIDYLAMINE
• Synonyms: 4,4'-DIPYRIDYLAMINE;DI-4-PYRIDINAMINE;DI-4-PYRIDYLAMINE;N-4-Pyridinyl-4-pyridinamine;4,4'-Dipyridylamine Di-4-pyridylamine;bis(4-pyridyl)amine;N-pyridin-4-ylpyridin-4-amine;4,4'-Iminodi-pyridine
• CAS NO: 1915-42-0
• Molecular Formula: C₁₀H₉N₃
• Molecular Weight: 171.2
• Mol File: 1915-42-0.mol
• Article Data: 4

Chemical Properties

• Melting Point: 281-282℃
• Boiling Point: 354℃
• Flash Point: 168℃
• Appearance: /
• Density: 1.206
• Vapor Pressure: 3.53E-05mmHg at 25°C
• Refractive Index: 1.65
• Storage Temp.: Keep in dark place,Inert atmosphere,Room temperature
• CAS DataBase Reference: 4,4'-DIPYRIDYLAMINE(CAS DataBase Reference)
• NIST Chemistry Reference: 4,4'-DIPYRIDYLAMINE(1915-42-0)
• EPA Substance Registry System: 4,4'-DIPYRIDYLAMINE(1915-42-0)

Safety Data

• Hazardous Substances Data: 1915-42-0(Hazardous Substances Data)

Usage

General Description

4,4'-Dipyridylamine is a chemical compound with the formula (C5H4N)2NH. It's classified as a heterocyclic compound as it contains atoms of at least two different elements, in this case, carbon, hydrogen, and nitrogen. 4,4'-Dipyridylamine is composed of two pyridine rings connected by a single nitrogen atom. It is an off-white crystalline powder at room temperature and mildly soluble in water. This chemical is used in various applications, including selective metal detection and as a starting material in the synthesis of other organic compounds, such as pharmaceuticals and agrochemicals. Exposure to this substance may lead to skin, eye, and respiratory irritation, and long-term or repeated exposure may cause damage to organs.

InChI:InChI=1/C10H9N3/c1-5-11-6-2-9(1)13-10-3-7-12-8-4-10/h1-8H,(H,11,12,13)

Synthetic route

4-aminopyridine (504-24-5) → 4,4'-dipyridylamine (1915-42-0)

Conditions	Yield
With 3-Methylpyridine; phosphorus trichloride at 140℃; for 5h;	87%

4-chlorpyridine hydrochloride (7379-35-3) + 4-amino-pyridine hydrochloride (1003-40-3) → 4,4'-dipyridylamine (1915-42-0)

Conditions	Yield
at 220 - 230℃; for 3h;	44%

pyridine (110-86-1) + 4-aminopyridine (504-24-5) → 4,4'-dipyridylamine (1915-42-0)

Conditions	Yield
Stage #1: pyridine; 4-aminopyridine With phosphorus trichloride at 140℃; for 5h; Stage #2: With hydrogenchloride; water at 105℃; for 1h;	44%

4-aminopyridine (504-24-5) → 4,4'-dipyridylamine (1915-42-0) + tris-[4]pyridylamino-phosphine

Conditions	Yield
With pyridine; phosphorus trichloride at 180℃;

→ 4,4'-dipyridylamine (1915-42-0)

Conditions	Yield
durch trockene Destillation;

→ 4,4'-dipyridylamine (1915-42-0)

Conditions	Yield
durch trockene Destillation;

pyridine (110-86-1) + 4-aminopyridine (504-24-5) → 4,4'-dipyridylamine (1915-42-0) + phosphorous acid tris-<4>pyridylamide

Conditions	Yield
With phosphorus trichloride at 180℃;

4-aminopyridine (504-24-5) + 4-bromopyridin (1120-87-2) → 4,4'-dipyridylamine (1915-42-0)

Conditions	Yield
With hydrogenchloride; potassium phosphate; tris-(dibenzylideneacetone)dipalladium(0); potassium tert-butylate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene In 1,4-dioxane at 100℃; for 12h;

4,4'-dipyridylamine (1915-42-0) + methyl iodide (74-88-4) → C12H15N3(2+)*2I(1-)

Conditions	Yield
for 8h;	99%

4,4'-dipyridylamine (1915-42-0) + nickel(II) chloride hexahydrate + benzene-1,2-dicarboxylic acid (88-99-3) → ([Ni(di(4-pyridyl)amine)(homophtalate)]*1.33water)n

Conditions	Yield
In water High Pressure; heating mixt. of nickel compd., dipyridylamine and phthalic acid in water at 120°C for 48 h; cooling to room temp., isolation of crystals, washing with distd. water,elem. anal.;	91%

4,4'-dipyridylamine (1915-42-0) → 3-nitro-N-(pyridin-4-yl)pyridin-4-amine

Conditions	Yield
With sulfuric acid; nitric acid at 110 - 120℃; for 1h;	90%
With sulfuric acid; nitric acid at 110 - 120℃; for 1h;	86%

4,4'-dipyridylamine (1915-42-0) + cobalt(II) chloride hexahydrate + water (7732-18-5) + benzene-1,2-dicarboxylic acid (88-99-3) → [Co2(phthalate)2(H2O)4(4,4'-dipyridylamine)2]*H2O

Conditions	Yield
In water High Pressure; mixt. of Co compd., dpa, and acid (1:2:1) sealed, heated at 120°Cfor 43 h; crystd., filtered off, washed (water, acetone), dried in air, elem. anal.;	89%

4,4'-dipyridylamine (1915-42-0) + cadmium(II) perchlorate hydrate + 1,3-benzenediacetic acid (19806-17-8) + water (7732-18-5) → ([Cd(1,3-phenylenediacetate)(4,4'-dipyridilamine)(H2O)]*0.5H2O)n

Conditions	Yield
In water High Pressure; Cd(ClO4)2*H2O, dipyridylamine and 1,3-phenylenediacetic acid were placedin H2O in teflon bomb, sealed, heated at 120°C for 48 h, slowly cooled to 25°C; crystals were isolated, washed with H2O, EtOH, acetone, dried in air, elem. anal.;	89%

4,4'-dipyridylamine (1915-42-0) + water (7732-18-5) + copper(II) malonate dihydrate (7195-88-2, 39661-83-1, 40569-43-5) → [Cu2(malonate)2(4,4'-dipyridylamine)(water)2]*(water)

Conditions	Yield
In ethanol; water copper malonate dihydrate dissolved in hot water; 4,4'-dipyridylamine inhot ethanol added; heated to boiling and then allowed to cool to 25.deg ree.C; standing for 2 weeks; elem. anal.;	86.3%

4,4'-dipyridylamine (1915-42-0) + copper(II) choride dihydrate → [CuCl2(bis(4-pyridyl)amine)2]*1.5H2O

Conditions	Yield
In methanol; water; acetonitrile CuCl2*2H2O dissolved in MeOH added to bis(4-pyridyl)amine dissolved in MeCN/H2O, stirred overnight; ppt. filtered, dried in vacuo; elem. anal.;	83%

1,5-pentanedioic acid (110-94-1) + 4,4'-dipyridylamine (1915-42-0) + cobalt(II) chloride hexahydrate → [Cu(1,5-pentanedicarboxylato)(dipyridylamine)](n) (1121586-86-4)

Conditions	Yield
In water High Pressure; placing of CoCl2*6H2O, HN(C5H4N)2 and glutaric acid into H2O in Teflon-lined Parr acid digestion bomb; sealing; heating at 120°C for 48 h; slow cooling to 25°C; crystn., washing with H2O, EtOH, and acetone and drying in air; elem. anal.;	82%

4,4'-dipyridylamine (1915-42-0) + cadmium(II) perchlorate hydrate + water (7732-18-5) + benzene-1,2-dicarboxylic acid (88-99-3) → ([Cd(homophthalate)(4,4'-dipyridilamine)]*H2O)n (1141016-27-4, 1163261-10-6)

Conditions	Yield
In water High Pressure; Cd(ClO4)2*H2O, dipyridylamine and homophthalic acid were placed in H2O in teflon bomb, sealed, heated at 120°C for 48 h, slowly cooled to25°C; crystals were isolated, washed with H2O, EtOH, acetone, dried in air, elem. anal.;	82%

4,4'-dipyridylamine (1915-42-0) + 4-bromo-benzaldehyde (1122-91-4) → 4-(4,4′-dipyridylamino)benzaldehyde (1456692-20-8)

Conditions	Yield
With diphenylether; 18-crown-6 ether; potassium carbonate; copper(II) sulfate at 180℃; for 48h; Ullmann Condensation; Inert atmosphere;	81%

4,4'-dipyridylamine (1915-42-0) + 2,5-bis(4-bromophenyl)thaizolo[5,4-d]thiazole (132624-31-8) → N,N'-(thiazolo[5,4-d]thiazole-2,5-diylbis(4,1-phenylene))bis(N-(pyridine-4-yl)pyridin-4-amine)

Conditions	Yield
With 18-crown-6 ether; potassium carbonate; copper(II) sulfate In diphenylether at 200℃; for 144h; Goldberg Reaction;	81%

4,4'-dipyridylamine (1915-42-0) + 1,3,5-trisbromobenzene (626-39-1) → C16H11Br2N3

Conditions	Yield
With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate In toluene for 2h; Reflux;	80%

4,4'-dipyridylamine (1915-42-0) + silver nitrate → [Ag(bis(4-pyridyl)amine)]NO3

Conditions	Yield
In water; acetonitrile soln. of Ag salt (1 equiv.) in NeCN was added to soln. of ligand (1 equiv.) in MeCN/H2O (3/1); stirred overnight; filtered; dried (vac.); elem. anal.;	78%
In water High Pressure; soln. of Ag salt and ligand in H2O was taken through cycles of freeze-pump-thaw and sealed; heated to 120°C for 2 d in steel blust tube; slowly cooled to room temp.;	31%
In water; acetonitrile; benzene soln. of ligand in MeCN/H2O layered with soln. of Ag salt in C6H6/MeCN was slowly diffused;

4,4'-dipyridylamine (1915-42-0) + cadmium(II) nitrate tetrhydrate + benzene-1,3,5-tricarboxylic acid (554-95-0) → Cd(H2O)(1,3,5-benzenetricarboxylate)(4,4'-dipyridylamine(1+)) (945831-55-0)

Conditions	Yield
With NaOH In water High Pressure; Cd(NO3)2*4H2O, 4,4'-dipyridylamine, 1,3,5-benzenetricarboxylic acid added to H2O, pH adjusted to 11.5 by aq. NaOH, placed in bomb, sealed, heated to 120°C for 26 h, gradually cooled to 23°C; ppt. filtered, washed with H2O and acetone, dried in air; elem. anal.;	76%

4,4'-dipyridylamine (1915-42-0) + cadmium(II) perchlorate hydrate + isophthalic acid (121-91-5) + water (7732-18-5) → ([Cd(isophthalate)(4,4'-dipyridilamine)]*4H2O)n

Conditions	Yield
In water High Pressure; Cd(ClO4)2*H2O, dipyridylamine and isophthalic acid were placed in H2O inteflon bomb, sealed, heated at 120°C for 48 h, slowly cooled to 25°C; crystals were isolated, washed with H2O, EtOH, acetone, dried in air, elem. anal.;	76%

4,4'-dipyridylamine (1915-42-0) + 2-bromo-9,9-dimethyl-9H-fluorene (28320-31-2) → C25H21N3

Conditions	Yield
With copper(l) iodide; 1,10-Phenanthroline; caesium carbonate In toluene at 110℃; for 7h;	76%

4,4'-dipyridylamine (1915-42-0) + zinc(II) nitrate hexahydrate + water (7732-18-5) + maleic acid (110-16-7) → [Zn2(maleate)2(4,4'-dipyridylamine)2]*5H2O

Conditions	Yield
In water Zn(NO3)2*6H2O and maleic acid dissolved in water; soln. of 4,4'-dipyridylamine in ethanol carefully layered on top of aq. soln.; crystal formed after one wk; crystals isolated, washed with water, ethanol and acetone, dried in air;elem. anal.;	75%

4,4'-dipyridylamine (1915-42-0) + para-diiodobenzene (624-38-4) → N,N-bis(4-pyridyl)-4-iodoaniline

Conditions	Yield
With 18-crown-6 ether; potassium carbonate; copper(II) sulfate In diphenylether at 50 - 170℃; for 96h; Inert atmosphere;	75%
With 18-crown-6 ether; potassium carbonate; copper(II) sulfate In diphenylether at 170℃; for 96h; Inert atmosphere; Schlenk technique;

4,4'-dipyridylamine (1915-42-0) + dimethyl sulfate (77-78-1) → C12H14N3(1+)*F6P(1-)

Conditions	Yield
Stage #1: 4,4'-dipyridylamine; dimethyl sulfate In acetonitrile for 8h; Reflux; Stage #2: With potassium hexafluorophosphate In water at 20℃;	74%

heptanedioic acid (111-16-0) + 4,4'-dipyridylamine (1915-42-0) + nickel(II) chloride hexahydrate + water (7732-18-5) → [Ni(pimelate)(4,4'-dipyridylamine)(H2O)]n (1016892-31-1)

Conditions	Yield
With NaOH In water High Pressure; equimolar Ni-compound and organic ligands added to water in autoclave; pH adjusted to 5.7 with aq. NaOH; sealed; heated to 120°C for 53 h; cooled to ambient temp.; filtrated; washed with distilled water and acetone; dried in air; elem. anal.;	73%

octane-1,8-dioic acid (505-48-6) + 4,4'-dipyridylamine (1915-42-0) + copper(II) choride dihydrate → [CuCl(suberate)0.5(4,4'-dipyridylamine)]n

Conditions	Yield
With HCl In water High Pressure; mixt. was placed in digestion bomb, HCl was added to pH=4.7, heated at 150°C for 24 h, cooled slowly in air to 25°C; ppt. was isolated, washed with water and acetone; elem. anal.;	73%

4,4'-dipyridylamine (1915-42-0) + 1-(4-bromophenyl)-2-(4-(tert-butyl)phenyl)ethane-1,2-dione (1174550-84-5) → C28H25N3O2

Conditions	Yield
With 18-crown-6 ether; potassium carbonate; copper(II) sulfate In Diphenylmethane at 180℃; for 48h; Ullmann Condensation; Inert atmosphere;	73%

4,4'-dipyridylamine (1915-42-0) + nickel(II) chloride hexahydrate + malonic acid (141-82-2) → ([Ni2(malonate)2(4,4'-dipyridylamine)(H2O)2]*2H2O)n

Conditions	Yield
With sodium hydroxide In water High Pressure; NiCl2*6H2O, 4,4'-dipyridylamine, malonic acid, NaOH and water were heated at 120°C for 44 h in Teflon-lined Parr digestion bomb; react. mixt. was cooled slowly to 25°C, ppt. was washed with water, i-PrOH and acetone and dried in air; elem. anal.;	72%

4,4'-dipyridylamine (1915-42-0) + silver(I) hexafluorophosphate (26042-63-7) → [Ag(bis(4-pyridyl)amine)]PF6 (911639-41-3)

Conditions	Yield
In water; acetonitrile soln. of Ag salt (1 equiv.) in MeCN/H2O (3/1) was added to soln. of ligand (1 equiv.) in MeCN/H2O (3/1); stirred for 3 d; concd.; Et2O added; filtered; dried (vac.); elem. anal.;	71%

4,4'-dipyridylamine (1915-42-0) + nickel(II) nitrate hexahydrate + diphenic acid (863305-32-2) + water (7732-18-5) → {[Ni(biphenyl-2,2'-dicarboxylate)(4,4'-dipyridylamine)(H2O)2]*H2O}n

Conditions	Yield
With sodium hydroxide at 120℃; for 72h; Sealed tube; High pressure;	71%
With sodium hydroxide at 120℃; for 72h; High pressure;

4,4'-dipyridylamine (1915-42-0) + water (7732-18-5) + potassium bis(oxalato)cuprate(II) → [Cu(oxalate)(4,4′-dipyridylamine)(H2O)]n

Conditions	Yield
at 100℃; for 24h; High pressure;	71%

4,4'-dipyridylamine (1915-42-0) + sodium metavanadate + nickel(II) chloride hexahydrate + water (7732-18-5) → Ni(4,4'-dipyridylamine)V4O12

Conditions	Yield
In water High Pressure; mixt. heated for 34 h at 120°C; cooled to room temp.; elem.anal.;	70%

4,4'-dipyridylamine (1915-42-0) + nickel(II) chloride hexahydrate + molybdenum(VI) oxide → Ni(2+)*2C10H9N3*MoO4(2-) = [Ni(C10H9N3)2(MoO4)]

Conditions	Yield
With Et4NOH In water Parr acid digestion bomb (pH 5.5, 120°C, 72 h); elem. anal.;	70%

4,4'-dipyridylamine (1915-42-0) + 2,6-Naphthalenedicarboxylic acid (1141-38-4) + silver nitrate → [silver(4,4'-dipyridylamine)(H2O)](2,6-naphthalenedicarboxylic acid)

Conditions	Yield
In water at 140℃; for 72h; Autoclave; High pressure;	69%

Upstream product

• 504-24-5 4-aminopyridine 
• 110-86-1 pyridine 
• 1120-87-2 4-bromopyridin 
• 7379-35-3 4-chlorpyridine hydrochloride 
• 1003-40-3 4-amino-pyridine hydrochloride 

Downstream Products

• 1345544-64-0 [Co(5-methoxyisophthalate)2(4,4'-dipyridylamine(+H))2] 
• 1345544-63-9 [Co(5-tert-butylisophthalate)(4,4'-dipyridylamine)(H₂O)] 
• 1258145-81-1 [Co(4,4'-dipyridylamine)(1,3-phenylenediacetate)(H₂O)] 
• 1141016-27-4 ([Cd(homophthalate)(4,4'-dipyridilamine)]*H₂O)n 
• 1055380-42-1 [Ni(di(4-pyridyl)amine)(1,2-phenylenediacetate)(H₂O)]n 

Relevant articles and documents

How N-(pyridin-4-yl)pyridin-4-amine and its methyl and nitro derivatives are arranged in the interlayer space of zirconium sulfophenylphosphonate: a problem solved by experimental and calculation methods

Classical molecular simulation methods were used for a description of an arrangement of intercalated molecules N-(pyridin-4-yl)pyridin-4-amine (AH) and its derivatives, 3-methyl-N-(pyridin-4-yl)pyridin-4-amine (AMe), and 3-nitro-N-(pyridin-4-yl)pyridin-4-amine (ANO2) within a layered structure of zirconium 4-sulfophenylphosphonate. The intercalated molecules were placed between SO3H groups of the host layers. Their mutual positions and orientations were solved by molecular simulation methods and compared with the presented experimental results. Final calculated data showed differences of partially disordered arrangement of the intercalated molecules between zirconium 4-sulfophenylphosphonate layers. The calculation results revealed a dense net of hydrogen bonds connecting water molecules and the guests in the interlayer space and the sulfo groups of the host layers. We calculated the dipole moments of the AH, AMe and ANO2 guests in the final models in order to illustrate potential use of these materials in non-linear optics.

Effect of intercalation and chromophore arrangement on the linear and nonlinear optical properties of model aminopyridine push-pull molecules

Three push-pull aminopyridine derivatives having D-π-A, D-(π-A)2, and D-(π-A)3 arrangements were examined as model organic chromophores capable of intercalation into inorganic layered materials (alpha modification of zirconium hydrogen phosphate, zirconium 4-sulfophenylphosphonate, and gamma modification of titanium hydrogen phosphate). The fundamental properties of these dyes, their methylated analogues as well as their intercalates were studied by X-ray analysis, electrochemistry, UV/Vis absorption spectra, TGA, IR spectra, SHG, and were completed by DFT calculations. The synthesis of tripodal tris(pyridin-4-yl)amine is given for the first time. The HOMO-LUMO gap, the position of the longest-wavelength absorption maxima, and the dipole moment of aminopyridines can easily be tuned by attaching/removing pyridin-4-yl electron withdrawing units and their quaternization (pyridine vs. pyridinium acceptors). Their intercalation proved to be feasible affording novel inorganic-organic hybrid materials. The intercalation is accompanied by protonation of the guest, which enhances its ICT and strongly anchors the aminopyridines into the confined space of the layered host. Moreover, this process results in ordering of the organic chromophores and also brings improved thermal and chemical robustness. As a result, the measured SHG efficiencies of the intercalates are larger than those observed for the pure organic push-pull chromophores. Hence, the methodology of intercalation turned out to be very useful strategy for property tuning of NLO-active organic molecules.