280-57-9

Basic information

• Product Name: 1,4-Diazabicyclo[2.2.2]octane
• Synonyms: 1,4-Diaza[2.2.2]bicyclooctane;1,4-diazabicyclooctane;1,4-Diazobicyclo(2.2.2)octane;1,4-diazobicyclo[2.2.2]octane;1,4-Ethylenepiperazine;Bicyclo(2,2,2)-1,4-diazaoctane;bicyclo(2.2.2)-1,4-diazaoctane;Bicyclo[2.2.2]-1,4-diazaoctane
• CAS NO: 280-57-9
• Molecular Formula: C₆H₁₂N₂
• Molecular Weight: 112.17
• EINECS: 205-999-9
• Product Categories: pharmacetical;Polyamines;API intermediates;Biochemistry;Reagents for Oligosaccharide Synthesis
• Mol File: 280-57-9.mol

Chemical Properties

• Melting Point: 156-159 °C(lit.)
• Boiling Point: 174 °C
• Flash Point: 198 °F
• Appearance: White to pale yellow/Hygroscopic Crystals
• Density: 1.02 g/mL
• Vapor Pressure: 2.9 mm Hg ( 50 °C)
• Refractive Index: n20/D 1.4634(lit.)
• Storage Temp.: 2-8°C
• Solubility: 400g/l
• PKA: 3.0, 8.7(at 25℃)
• Water Solubility: 46 g/100 mL (26 ºC)
• Sensitive: Hygroscopic
• Stability: Stable, but very hygroscopic. Incompatible with strong oxidizing agents, strong acids. Highly flammable.
• Merck: 14,9669
• BRN: 103618
• CAS DataBase Reference: 1,4-Diazabicyclo[2.2.2]octane(CAS DataBase Reference)
• NIST Chemistry Reference: 1,4-Diazabicyclo[2.2.2]octane(280-57-9)
• EPA Substance Registry System: 1,4-Diazabicyclo[2.2.2]octane(280-57-9)

Safety Data

• Hazard Codes: Xn,F
• Statements: 22-36/37/38-52/53-41-36/38-11
• Safety Statements: 26-60-37/39-3-16-36/37-61
• RIDADR: UN 1325 4.1/PG 2
• WGK Germany: 1
• RTECS: HM0354200
• F: 3
• TSCA: Yes
• HazardClass: 8
• PackingGroup: III
• Hazardous Substances Data: 280-57-9(Hazardous Substances Data)

Usage

Uses

Used in Polymerization and Organic Synthesis:
Triethylenediamine is used as a catalyst and reagent in polymerization and organic synthesis due to its highly nucleophilic tertiary amine base properties. It facilitates various chemical reactions and contributes to the formation of polymers with desired properties.
Used in Catalysts and Complexing Ligands:
Triethylenediamine is employed as a catalyst in the Balis-Hillman reaction and serves as a complexing ligand and Lewis base. Its ability to form self-assembled monolayers (SAMs) on various substrates allows it to functionalize surfaces and immobilize surface atoms, making it a valuable component in the development of novel materials and technologies.
Used in Dye Lasers and Fluorescence Microscopy:
Triethylenediamine is utilized in dye lasers and for mounting samples in fluorescence microscopy. Its application in these areas is attributed to its ability to act as an anti-fade reagent, scavenging free radicals that result from fluorochrome excitation.
Used as an Antioxidant:
Triethylenediamine's role as an antioxidant makes it a useful additive in various industrial applications, where it helps to prevent oxidation and degradation of materials, thereby extending their shelf life and maintaining their quality.

Preparation

Triethylenediamine can be produced from ethylenediamine or ethanolamine, diethanolamine, or diethylenetriamine with a variety of different catalysts.

Reactions

Triethylenediamine reacts virtually quantitatively with bromine to give a 1/1 adduct. With alkyl halides it forms quaternary salts, even in nonpolar solvents. Apart from its highly nucleophilic nature, triethylenediamine exhibits catalytic activity in base-catalyzed reactions.

Hazard

Skin irritant.

Flammability and Explosibility

Flammable

Purification Methods

DABCO crystallises from 95% EtOH, pet ether or MeOH/diethyl ether (1:1). Dry it under vacuum over CaCl2 and BaO. It can be sublimed in vacuo, and readily at room temperature. It has also been purified by removal of water during azeotropic distillation of a *benzene solution. It is then recrystallised twice from anhydrous diethyl ether under argon, and stored under argon [Blackstock et al. J Org Chem 52 1451 1987]. [Beilstein 23/3 V 487.]

InChI:InChI=1/C6H12N2/c1-2-8-5-3-7(1)4-6-8/h1-6H2

Synthetic route

C6H8N2O2 → 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
With Rh/Al2O3; hydrogen In tetrahydrofuran at 175℃; under 37503.8 Torr; Reagent/catalyst; Temperature; Solvent; Sealed tube;	87.6%

1-(2-hydroxyethyl)piperazine (103-76-4) → 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
With aluminum phosphate molded body In water at 380℃;	76%
With silica gel In water at 380℃; for 10h; Reagent/catalyst; Gas phase;	75%
With aluminum oxide; silica gel
at 300℃; Leiten des Dampfes ueber einen SiO2/Al2O3-Katalysator;

aminoethylpiperazine (140-31-8) → 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
With H type zeolite(ZSM-5) In water at 380℃;	75%
With water; Na-type ZSM-5(3) at 355 - 370℃;	46.3%

1,4-diamino-1,4-diazonia-bicyclo[2.2.2]octane; dibromide (115050-43-6) → 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
With hydrogen; palladium on activated charcoal In water at 18 - 20℃; under 1.5 - 1.8 Torr;	74%

1-(2-hydroxyethyl)piperazine (103-76-4) → piperazine (110-85-0) + 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
With water; Na-type ZSM-5(2) at 340℃;	A 4.1% B 68.1%

sodium methylate (124-41-4) + 1-[2-(2,4,6-Tri-tert-butyl-phenylphosphanylidene)-ethyl]-4-aza-1-azonia-bicyclo[2.2.2]octane; bromide (126995-92-4) → 1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + C21H35OP (126995-93-5)

Conditions	Yield
In methanol at 60℃; for 1h;	A n/a B 65%
In methanol at 60℃; for 1h; Yield given;

ethylenediamine (107-15-3) + 1,5-diamino-3-azapentane (111-40-0) → piperazine (110-85-0) + 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
With ZSM-5 type zeolite In water at 370℃; pH=10; Temperature; pH-value;	A 63% B 17%
With ZSM-5 type zeolite In water at 330℃; pH=10; Temperature; pH-value;	A 44% B 56%
With ZSM-5 type zeolite with Na exchange rate of 62percent In water at 290℃; Reagent/catalyst; Temperature;
With Na-ion exchanged ZSM-5 type zeolite In water at 290 - 600℃; Gas phase;
With β-type iron silicate at 320℃; Reagent/catalyst;

aminoethylpiperazine (140-31-8) + ethylenediamine (107-15-3) → piperazine (110-85-0) + 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
With ZSM-5 type zeolite In water at 320℃; pH=9; Temperature; pH-value;	A 54% B 46%

aminoethylpiperazine (140-31-8) → piperazine (110-85-0) + 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
With ZSM-5 type zeolite In water at 350℃;	A 26% B 53%
With water; Na-type ZSM-5(2) at 350 - 370℃;	A 20.2% B 47.7%
Na-type ZSM-5(6) at 355 - 380℃;	A 18.9% B 39.9%

triethylentetramine (112-24-3) → piperazine (110-85-0) + 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
With water; Na-type ZSM-5(2) at 360 - 370℃;	A 14.8% B 43.7%

N,N'-bisethylenediamine (113682-68-1) → 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
at 350℃;	30%

methanol (67-56-1) + ethanolamine (141-43-5) → ethyleneimine (151-56-4) + piperazine (110-85-0) + 1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + (2-hydroxyethyl)(methyl)amine (109-83-1)

Conditions	Yield
With Cs-P-Si mixed-oxide at 300℃; under 750.06 Torr; Title compound not separated from byproducts;	A 37 % Chromat. B n/a C n/a D 6%

methanol (67-56-1) + ethanolamine (141-43-5) → piperazine (110-85-0) + 1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + (2-hydroxyethyl)(methyl)amine (109-83-1)

Conditions	Yield
With H-β-zeolite at 250℃; under 750.06 Torr; Title compound not separated from byproducts;	A n/a B n/a C 2%

Chloroethylpiperazine (61308-25-6) → 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
With diethyl ether

1,4-bis(2-hydroxyethyl)piperazine (122-96-3) → 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
With aluminum oxide; silica gel
at 325℃; under 19 Torr; Leiten des Dampfes ueber einen Siliciumdioxid-Aluminiumoxid-Katalysator;

diethanolamine hydrochloride (14426-21-2) → morpholine (110-91-8) + 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
at 220℃;

1-(2-bromo-ethyl)-piperazine; dihydrobromide (89727-93-5) → 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
at 240℃;

1-(2-chloroethyl)-piperazine dihydrochloride (53502-60-6, 54267-47-9, 75256-75-6) → 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
at 240℃;

N,N'-bis(2-bromoethyl)piperazine dihydrobromide (90942-23-7) → piperazine (110-85-0) + 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
at 275℃;

1,4-dimethyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium dibromide (5450-74-8) → 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
at 230 - 240℃; under 0.003 Torr;
at 230 - 240℃; under 0.003 Torr; Pyrolysis;
at 260℃; under 0.001 Torr; Pyrolysis;

1,4-dimethyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium dibromide (5450-74-8) → 1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + 1H,4H-piperazine-N,N’-diium dibromide (59813-05-7)

Conditions	Yield
at 350℃; under 0.002 Torr; Pyrolysis;

triethanolamine hydrochloride (637-39-8) → 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
With ammonium chloride at 230℃;

tris-(2-chloroethyl)amine hydrochloride (817-09-4) → 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
With ammonium chloride at 270℃;

1,5-diamino-3-azapentane (111-40-0) → 1,4-diaza-bicyclo[2.2.2]octane (280-57-9)

Conditions	Yield
With kaolin at 390℃;

aminoethylpiperazine (140-31-8) + formaldehyd (50-00-0) + formic acid (64-18-6) + 1,2-dichloro-ethane (107-06-2) → N,N'-dimethylpiperazine (106-58-1) + 1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + N,N,N,N,-tetramethylethylenediamine (110-18-9) + 1-<2-(diethylamino)ethyl>-4-methylpiperazine + N,N'-dimethyl-N,N'-bis<2-(4-methyl-1-piperazinyl)ethyl>ethylenediamine

Conditions	Yield
Mechanism;

...Expand

aminoethylpiperazine (140-31-8) + formaldehyd (50-00-0) + formic acid (64-18-6) + 1,2-dichloro-ethane (107-06-2) → N,N'-dimethylpiperazine (106-58-1) + 1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + 1-<2-(diethylamino)ethyl>-4-methylpiperazine + N,N'-dimethyl-N,N'-bis<2-(4-methyl-1-piperazinyl)ethyl>ethylenediamine

Conditions	Yield
With 2.) alkali 1.) alcohol; Multistep reaction. Further byproducts given;

aminoethylpiperazine (140-31-8) + formaldehyd (50-00-0) + formic acid (64-18-6) + 1,2-dichloro-ethane (107-06-2) → 1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + N,N,N,N,-tetramethylethylenediamine (110-18-9) + 1-<2-(diethylamino)ethyl>-4-methylpiperazine + N,N'-dimethyl-N,N'-bis<2-(4-methyl-1-piperazinyl)ethyl>ethylenediamine

Conditions	Yield
Multistep reaction. Further byproducts given;

1-Phenethyl-4-aza-1-azonia-bicyclo[2.2.2]octane (73997-41-8) → 1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + styrene (292638-84-7)

Conditions	Yield
With potassium hydroxide; potassium chloride In water at 40℃; Mechanism; Rate constant; further base-solvent system;

1-[2-(4-Nitro-phenyl)-ethyl]-4-aza-1-azonia-bicyclo[2.2.2]octane (73997-39-4) → 1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + 4-nitrostyrene (100-13-0)

Conditions	Yield
With potassium hydroxide; potassium chloride In water at 25℃; Mechanism; Rate constant; Equilibrium constant; further bases;

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + p-nitrobenzene iodide (636-98-6) → 1-(4-Nitro-phenyl)-4-aza-1-azonia-bicyclo[2.2.2]octane; iodide (112473-28-6)

Conditions	Yield
In tetrahydrofuran at 50℃; under 4500360 Torr; for 75h;	100%
In tetrahydrofuran at 50℃; under 4500360 Torr; for 20h; Yield given;

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + ethyldiiodophosphine (13868-72-9) → C14H29N4P(2+)*2I(1-)

Conditions	Yield
In dichloromethane for 6h;	100%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + 4-chlorobenzonitrile (100-00-5) → 1-(4-Nitro-phenyl)-4-aza-1-azonia-bicyclo[2.2.2]octane; chloride (112473-26-4)

Conditions	Yield
In tetrahydrofuran at 50℃; under 4500360 Torr; for 75h;	100%
In tetrahydrofuran at 50℃; under 4500360 Torr; for 20h; Yield given;

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + para-nitrophenyl bromide (586-78-7) → 1-(4-Nitro-phenyl)-4-aza-1-azonia-bicyclo[2.2.2]octane; bromide (112473-27-5)

Conditions	Yield
In tetrahydrofuran at 50℃; under 4500360 Torr; for 75h;	100%
In tetrahydrofuran at 50℃; under 4500360 Torr; for 20h; Yield given;

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + 1-bromomethyl-4-nitro-benzene (100-11-8) → 4-aza-1-p-nitrobenzylazoniabicyclo<2.2.2>octane bromide (136497-64-8)

Conditions	Yield
In diethyl ether for 20h;	100%
In diethyl ether	97%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + trifluorormethanesulfonic acid (1493-13-6) → N,N'-difluoro-1,4-diazoniabicyclo<2.2.2>octane bis(triflate)

Conditions	Yield
With fluorine In various solvent(s)	100%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + ethyl 2-(acetoxy(phenyl)methyl)acrylate (105479-98-9) → Acetate1-((E)-2-ethoxycarbonyl-3-phenyl-allyl)-4-aza-1-azonia-bicyclo[2.2.2]octane;

Conditions	Yield
In tetrahydrofuran; water at 20℃; for 0.25h;	100%
In tetrahydrofuran; water at 20℃; for 0.166667h;

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + 3-acetoxy-2-methylene-3-phenylpropionitrile (138597-12-3, 144299-84-3, 144370-28-5, 143165-00-8) → Acetate1-((E)-2-cyano-3-phenyl-allyl)-4-aza-1-azonia-bicyclo[2.2.2]octane;

Conditions	Yield
In tetrahydrofuran; water at 20℃; for 0.25h;	100%
In tetrahydrofuran; water at 20℃; for 0.166667h;

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + ethyl 2-(acetoxy(2,4-dichlorophenyl)methyl)acrylate → Acetate1-[(E)-3-(2,4-dichloro-phenyl)-2-ethoxycarbonyl-allyl]-4-aza-1-azonia-bicyclo[2.2.2]octane;

Conditions	Yield
In tetrahydrofuran; water at 20℃; for 0.25h;	100%
In tetrahydrofuran; water at 20℃; for 0.166667h;

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + ethyl 2-(acetoxy (p-tolyl)methyl)acrylate → 1-(2-ethoxycarbonyl-3-p-tolyl-allyl)-4-aza-1-azonia-bicyclo[2.2.2]octane; acetate

Conditions	Yield
In tetrahydrofuran; water at 20℃; for 0.25h;	100%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + acetic acid 2-cyano-1-(3-methoxy-phenyl)-allyl ester → Acetate1-[(E)-2-cyano-3-(3-methoxy-phenyl)-allyl]-4-aza-1-azonia-bicyclo[2.2.2]octane;

Conditions	Yield
In tetrahydrofuran; water at 20℃; for 0.25h;	100%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + ethyl 2-(acetoxy(3-methoxyphenyl)methyl)acrylate → Acetate1-[(E)-2-ethoxycarbonyl-3-(3-methoxy-phenyl)-allyl]-4-aza-1-azonia-bicyclo[2.2.2]octane;

Conditions	Yield
In tetrahydrofuran; water at 20℃; for 0.25h;	100%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + 1-bromo-octane (111-83-1) → 1‐octyl‐1,4‐diazabicyclo[2.2.2]octan‐1‐ium bromide

Conditions	Yield
In dichloromethane for 12h; Reflux;	100%
In tetrahydrofuran at 60℃; for 24h;	95%
In ethyl acetate at 20℃; for 24h;	91%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + 4-trifluoromethylbenzyl chloride (939-99-1) → 1-(4-(trifluoromethyl)benzyl)-4-aza-1-azonia-bicyclo[2.2.2]octane chloride

Conditions	Yield
In tetrahydrofuran for 2h; Heating;	100%
In tetrahydrofuran at 20℃; for 12h;	92%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + methyl 2,6-dichloronicotinate (65515-28-8) → 1-(6-chloro-5-methoxycarbonyl-pyridin-2-yl)-4-aza-1-azonia-bicyclo[2.2.2]octane

Conditions	Yield
In tetrahydrofuran at 5 - 20℃; for 16.5h;	100%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + 2-amino 2-methyl 3-((tetrahydro 2H-pyran 2-yl) oxy) propanenitrile + benzenesulfonyl chloride (98-09-9) → N-[1-cyano-1-methyl-2-(tetrahydro-pyran-2-yloxy)-ethyl]-C-benzylsulfonamide

Conditions	Yield
In tetrahydrofuran at 20℃; for 15h;	100%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + 2-(5-hydroxyindane-2-yl)isoindole-1,3-dione (685832-34-2) + N,N-Dimethylthiocarbamoyl chloride (16420-13-6) → dimethylthiocarbamic acid O-[2-(1,3-dioxo-1,3-dihydroisoindol-2-yl)indan-5-yl] ester (685832-35-3)

Conditions	Yield
In DMF (N,N-dimethyl-formamide) at 0 - 20℃; for 18h;	100%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + Methyl 2-Hydroxy-4-[({[3-hydroxy-4-(methoxycarbonyl)-phenyl]methyl}amino)methyl]benzoate Hydrochloride (311343-83-6) + di-tert-butyl dicarbonate (24424-99-5) → Methyl 4-[((tert-butoxy)-N-{[3-hydroxy-4-(methoxycarbonyl)-phenyl]methyl}carbonylamino)methyl]-2-hydroxybenzoate

Conditions	Yield
In methanol; hexane; ethyl acetate	100%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + naphthalene-1,4-dicarboxylic acid (605-70-9) + copper (12775-96-1, 15158-11-9, 15721-63-8, 16941-75-6, 17493-86-6, 19498-52-3, 20499-83-6, 20499-84-7, 20499-85-8, 20499-86-9, 20573-10-8, 20573-11-9, 21595-51-7, 21595-52-8, 22206-52-6, 26445-28-3, 28959-95-7, 37362-93-9, 39417-05-5, 54603-16-6, 54603-23-5, 54603-32-6, 54603-40-6, 54603-48-4, 54603-81-5, 54603-89-3, 56316-56-4, 95985-91-4, 122297-32-9, 7440-50-8) → Cu(II)(1,4-naphthalenedicarboxylate)(DABCO)0.5

Conditions	Yield
With N-methyl-N,N,N-tributylammonium methyl sulfate In methanol at 39℃; for 2h; Electrochemical reaction;	100%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + 1,3-dibromo-propane (109-64-8) → 1,1''-(propane-1,3-diyl)bis(1,4-diazabicyclo[2.2.2]-octan-1-ium)dibromide (97497-67-1)

Conditions	Yield
In methanol at 20℃; for 24h;	100%
In methanol at 20℃; for 20h;	97%
In acetonitrile at 20℃; for 24h;	74%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + 2,3,4,5,6-pentafluorobenzyl iodide → 1-pentafluoro benzylammonium-4-aza-1-azonia bicyclo[2.2.2]octane iodide (1229616-94-7)

Conditions	Yield
In chloroform at 20℃; for 24h;	100%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + 2,3,4,5,6-pentafluorobenzyl chloride (653-35-0) → C13H14F5N2(1+)*Cl(1-) (1229616-83-4)

Conditions	Yield
In chloroform at 20℃; for 24h;	100%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) → 1,4-diazabicyclo [2.2.2] octane-1,4-diium-1,4-disulfinate (119752-83-9)

Conditions	Yield
With sulfur dioxide	100%
With sulfuric acid; sodium carbonate In tetrahydrofuran at 20℃;	99%
With sulfur dioxide at -78℃; Inert atmosphere; Reflux;	98%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + 1,3-propanesultone (1120-71-4) → N,N'-bis(3-sulfopropyl)triethylenediaminium bis(hydrogensulfate)

Conditions	Yield
Stage #1: 1,4-diaza-bicyclo[2.2.2]octane; 1,3-propanesultone In tetrahydrofuran for 24h; Reflux; Stage #2: With sulfuric acid at 170℃; for 20h;	100%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + [(5,15-diphenylporphinato(-H))zinc(II)(CC)iron(II)(η5-C5Me5)(1,2-bis(diphenylphosphino)ethane)]*0.3CH2Cl2 → [(5,15-diphenylporphinato(-H))zinc(II)(pyridine)(CC)iron(II)(η5-C5Me5)(1,2-bis(diphenylphosphino)ethane)] dichloromethane disolvate

Conditions	Yield
In dichloromethane at 20℃; for 3h; Inert atmosphere; Schlenk technique;	100%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + 1-acetyl-N-phenylcyclopropane-1-carboxamide (937733-22-7) → C18H25N3O2

Conditions	Yield
In acetonitrile at 60℃;	100%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + C48H28N4O4Zn + ethylenediamine (107-15-3) → C110H84N18Zn2

Conditions	Yield
In chloroform at 20℃; for 24h;	100%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + C48H28N4O4Zn + Trimethylenediamine (109-76-2) → C114H92N18Zn2

Conditions	Yield
In chloroform at 20℃; for 24h;	100%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + C9H9N3O2S2*C4H10N2 → C9H9N3O2S2*C6H12N2

Conditions	Yield
In ethanol	100%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + C47H21B3F18O6 → C112H78B6F36N6O12

Conditions	Yield
In chloroform at 20℃;	100%

Upstream product

• 61308-25-6 Chloroethylpiperazine 
• 103-76-4 1-(2-hydroxyethyl)piperazine 
• 122-96-3 1,4-bis(2-hydroxyethyl)piperazine 
• 14426-21-2 diethanolamine hydrochloride 
• 89727-93-5 1-(2-bromo-ethyl)-piperazine; dihydrobromide 
• 53502-60-6 1-(2-chloroethyl)-piperazine dihydrochloride 
• 90942-23-7 N,N'-bis(2-bromoethyl)piperazine dihydrobromide 
• 5450-74-8 1,4-dimethyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium dibromide 
• 637-39-8 triethanolamine hydrochloride 
• 817-09-4 tris-(2-chloroethyl)amine hydrochloride 
• 111-40-0 3-azapentane-1,5-diamine 
• 140-31-8 aminoethylpiperazine 
• 50-00-0 formaldehyd 
• 64-18-6 formic acid 

Downstream Products

• 5450-74-8 1,4-dimethyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium dibromide 
• 42790-43-2 N,N'-dibenzyl-1,4-diazonia bicyclo[2.2.2]octane dichloride 
• 14870-72-5 1,4-dimethyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium diiodide 
• 93-97-0 benzoic acid anhydride 
• 18503-52-1 1,4-Diazabicyclo<2.2.2>octane N-oxide 
• 60420-20-4 1-methyl-4-aza-1-azonia-bicyclo[2.2.2]octane; chloride-hydrochloride 
• 81539-93-7 1-Methyl-4-(2-hydroxyethyl)piperazine Benzoate 
• 81539-95-9 Benzoic acid 2-(4-methyl-piperazin-1-yl)-ethyl ester; hydrobromide 
• 81539-88-0 Benzoate₁-methyl-4-aza-1-azonia-bicyclo[2.2.2]octane; 
• 112473-28-6 1-(4-Nitro-phenyl)-4-aza-1-azonia-bicyclo[2.2.2]octane; iodide 
• 122323-92-6 2-(1,4-diazabicyclo<2.2.2>octyl)diphenylcarbinol 
• 108-94-1 cyclohexanone 
• 280-57-9 1,4-diazabicyclo<2.2.2>octane radical cation 
• 4255-62-3 4,4-dimethylcyclohexane-1-one 

Relevant articles and documents

Generation of a Mn(IV)-Peroxo or Mn(III)-Oxo-Mn(III) Species upon Oxygenation of Mono- and Binuclear Thiolate-Ligated Mn(II) Complexes

A thiolate-bridged binuclear complex [PPN]2[(MnII(TMSPS3))2] (1, PPN = bis(triphenylphosphine)iminium and TMSPS3H3 = (2,2′,2″-trimercapto-3,3′,3″-tris(trimethylsilyl)triphenylphosphine)), prepared from the reaction of MnCl2/[PPN]Cl and Li3[TMSPS3], converts into a mononuclear complex [PPN][MnII(TMSPS3)(DABCO)] (2) in the presence of excess amounts of DABCO (DABCO = 1,4-diazabicyclo[2.2.2]octane). Variable temperature studies of solution containing 1 and DABCO by UV-vis spectroscopy indicate that 1 and 2 exist in significant amounts in equilibrium and mononuclear 2 is favored at low temperature. Treatment of 1 or 2 with the monomeric O2-side-on-bound [PPN][MnIV(O2)(TMSPS3)] (3) produces the mono-oxo-bridged dimer [PPN]2[(MnIII(TMSPS3))2(μ-O)] (4). The electrochemistry of 1 and 2 reveals anodic peak(s) for a MnIII/MnII redox couple at shifted potentials against Fc/Fc+, indicating that both complexes can be oxidized by dioxygen. The O2 activation mediated by 1 and 2 is investigated in both solution and the solid state. Microcrystals of 2 rapidly react with air or dry O2 to generate the Mn(IV)-peroxo 3 in high yield, revealing a solid-to-solid transformation and two-electron reduction of O2. Oxygenation of 1 or 2 in solution, however, is affected by diffusion and transient concentration of dioxygen in the two different substrates, leading to generation of 3 and 4 in variable ratios.

Degradation of Organic Cations under Alkaline Conditions

Understanding the degradation mechanisms of organic cations under basic conditions is extremely important for the development of durable alkaline energy conversion devices. Cations are key functional groups in alkaline anion exchange membranes (AAEMs), and AAEMs are critical components to conduct hydroxide anions in alkaline fuel cells. Previously, we have established a standard protocol to evaluate cation alkaline stability within KOH/CD3OH solution at 80 °C. Herein, we are using the protocol to compare 26 model compounds, including benzylammonium, tetraalkylammonium, spirocyclicammonium, imidazolium, benzimidazolium, triazolium, pyridinium, guanidinium, and phosphonium cations. The goal is not only to evaluate their degradation rate, but also to identify their degradation pathways and lead to the advancement of cations with improved alkaline stabilities.

Synthesis method of triethylene diamine

The invention relates to a synthesis method of triethylene diamine, and solves the technical problems of high cost or certain risk of raw materials, no environmental protection, complex synthesis process, low product yield and the like in the existing production process. The synthesis method comprises the following steps: (1) adding oxalic acid diester into a reaction bottle, dissolving piperazinewith a solvent in advance, adding a catalyst, dropwise adding piperazine dissolved with the solvent at the reaction temperature of 30-80 DEG C, stirring for 1-2 hours, filtering, washing an obtainedfilter cake with the solvent, and drying to obtain an intermediate product, namely dioxytriethylene diamine; (2) adding the dioxytriethylene diamine prepared in the step (1) into a high-pressure reaction kettle, adding a solvent until the dioxytriethylene diamine is completely dissolved, adding a catalyst, tightly covering a kettle cover, sealing, heating to 150-200 DEG C, introducing hydrogen into a high-pressure valve until the pressure reaches 2-10MPa, and continuously introducing hydrogen to maintain the pressure in the reaction process to obtain a triethylene diamine crude product; and (3) carrying out post-treatment to obtain the final product triethylene diamine. The method is applied to synthesis of triethylene diamine.

Hetero Face-to-Face Porphyrin Array with Cooperative Effects of Coordination and Host–Guest Complexation

We successfully synthesized a hetero face-to-face porphyrin array composed of ZnTPP and RuTPP(DABCO)2 (TPP: 5, 10, 15, 20-tetraphenylporphyrin, DABCO: 1,4-diazabi-cyclo[2.2.2]octane) in 2:1 molar ratio. A cyclic Zn porphyrin dimer (ZnCP) was also used as the host molecule for the Ru porphyrin. In the latter, the Ru-DABCO bonding in RuTPP(DABCO)2 was stabilized by the host-guest complexation. Reaction progress kinetic analysis of the ligand substitution reaction of RuTPP(DABCO)2 and that in ZnCP revealed the stabilization mechanism of the Ru-DABCO bonding. Photoinduced electron transfer (PET) from the Zn porphyrin to the Ru porphyrin was observed in the porphyrin array. The host-guest stabilization of unstable complex for construction of a donor—acceptor–donor structure is expected to be a new method for an artificial photosynthesis.

METHOD FOR PRODUCING PIPERAZINE AND TRIETHYLENEDIAMINE

PROBLEM TO BE SOLVED: To provide a method for producing piperazine and triethylenediamine in combination, making it possible to provide piperazine with high selectivity and high yields. SOLUTION: Under a basic condition with pH of 8 or more, pentasil type zeolite subjected to ion exchange with alkali metal salt, and one or more amine react with each other, under a condition of 50 wt.% or more substrate concentration. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT

MANUFACTURING METHOD OF PIPERAZINE AND TRIETHYLENE DIAMINE

PROBLEM TO BE SOLVED: To provide a manufacturing method of piperazine and triethylene diamine, in which piperazine is obtained more selectively and at a higher yield. SOLUTION: Ethylene diamines and steam-treated ZSM-5 type zeolite are brought into contact to make react. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT

METHOD FOR PRODUCING BICYCLIC AMINE COMPOUND

PROBLEM TO BE SOLVED: To provide a stable production method for a bicyclic amine compound that inhibits the generation of by-products in the production of a bicyclic amine. SOLUTION: The present invention provides a method for producing a bicyclic amine compound which employs a catalyst comprising an inorganic support and an alkali metal phosphate, and further comprising alkaline earth metal hydroxide and/or hydroxyapatite in an amount of 1.5 wt.% or more and less than 15 wt.% relative to the inorganic support. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPO&INPIT

METHOD FOR PRODUCING PIPERAZINE AND TRIETHYLENEDIAMINE

PROBLEM TO BE SOLVED: To provide a joint production method of piperazine and triethylenediamine capable of obtaining piperazine more selectively and also at a high yield. SOLUTION: Diethylenetriamine and at least one kind of amine selected from the group consisting of ethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and their alkylated bodies are mixed, the mixture is contacted with ZSM-5 type zeolite in which the ion exchange rate in the alkali metal salt is 50% or higher, and reaction is caused. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT

METHOD FOR PRODUCING PIPERAZINE AND TRIETHYLENE DIAMINE

PROBLEM TO BE SOLVED: To provide a method for producing piperazine and triethylene diamine that allows piperazine to be obtained selectively with high yields. SOLUTION: At least one amine selected from the group consisting of ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and their alkylate is brought into contact with zeolite having BEA structure for a reaction. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT

Synthesis of piperazine and method of triethylene diamine

The invention discloses a method for synthesizing piperazidine and triethylenediamine. The method aims to solve the problems of low efficiency and need for expensive high-vacuum rectifiers in the process of converting ethanolamine into piperazidine and triethylenediamine in the prior art. The method comprises the following steps: mixing and gasifying ethanolamine and ammonia, and carrying out amination reaction in a fixed-bed reactor R by using a catalyst A (using a mesoporous-microporous composite molecular sieve MOR/MCM-41 as a support) and a catalyst B (using a mesoporous-microporous composite molecular sieve ZSM-5 MCM-41 as a support); carrying out rectification separation on the reactor outlet product in a rectification tower T1 to distil off unconverted ammonia, piperazidine and triethylenediamine from the tower top, and circulating unreacted ethanolamine and amination byproduct obtained from the tower bottom to the inlet of the fixed-bed reactor R to continue reaction; and sending the top fraction of the rectification tower T1 into a rectification tower T2, and separating to obtain the piperazidine and triethylenediamine. The method is used for synthesizing piperazidine and triethylenediamine.