4067-16-7

Basic information

• Product Name: PENTAETHYLENEHEXAMINE
• Synonyms: N1,N1'-(ethane-1,2-diyl)bis(N2-(2-aMinoethyl)ethane-1,2-diaMine);PentaethylenehexaMine technical grade;bis(N2-(2-aminoethyl);PENTAETHYLENEHEXAMINE;3,6,9,12-TETRAAZATETRADECANE-1,14-DIAMINE;3,6,9,12-tetraazatetradecamethylenediamine;Pentaethylenehexamide;PENTAETHYLENEHEXAMINE, TECH.
• CAS NO: 4067-16-7
• Molecular Formula: C₁₀H₂₈N₆
• Molecular Weight: 232.37
• EINECS: 223-775-9
• Product Categories: Building Blocks;Chemical Synthesis;Nitrogen Compounds;Organic Building Blocks;Polyamines
• Mol File: 4067-16-7.mol
• Article Data: 7

Chemical Properties

• Melting Point: -35 °C
• Boiling Point: 380 °C
• Flash Point: >230 °F
• Appearance: Clear yellow/Liquid
• Density: 0.95 g/mL at 25 °C(lit.)
• Vapor Pressure: 2.91E-06mmHg at 25°C
• Refractive Index: n20/D 1.5096(lit.)
• Storage Temp.: Store below +30°C.
• Solubility: water: soluble500g/L at 20°C
• PKA: 10.07±0.19(Predicted)
• Water Solubility: miscible
• Stability: Stable. Incompatible with strong oxidizing agents, strong acids.
• BRN: 1768042
• CAS DataBase Reference: PENTAETHYLENEHEXAMINE(CAS DataBase Reference)
• NIST Chemistry Reference: PENTAETHYLENEHEXAMINE(4067-16-7)
• EPA Substance Registry System: PENTAETHYLENEHEXAMINE(4067-16-7)

Safety Data

• Hazard Codes: C,N
• Statements: 34-43-50/53-21/22
• Safety Statements: 26-36/37/39-45-60-61
• RIDADR: UN 2735 8/PG 3
• WGK Germany: 2
• RTECS: RZ2680000
• HazardClass: 8
• PackingGroup: III
• Hazardous Substances Data: 4067-16-7(Hazardous Substances Data)

Usage

Chemical Properties

dark yellow-green liquid

Uses

5.Pentaethylenehexamine has been used in the preparation of:polyisobutylene succinimide (PIBSI) dispersants, used as engine oil-additivespoly(glycidyl methacrylate) (P(GMA)) homopolymerspoly(amidoamine)s

General Description

Yellowish liquid with an odor of ammonia.

Air & Water Reactions

Water soluble.

Reactivity Profile

PENTAETHYLENEHEXAMINE 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

Contact with eyes can cause slight to moderate irritation and possible burns. May cause transient fogging of the eyes as a result of corneal edema, which is reversible. May cause moderate skin irritation or allergic skin reaction with symptoms of redness, itching, swelling, or rash. Vapors may irritate the eyes, nose, throat, and respiratory tract. May cause coughing, headache, nausea and vomiting. If swallowed, may cause nausea, vomiting and abdominal pain. May cause burns of the mouth, throat, esophagus, and stomach.

Safety Profile

Moderately toxic by ingestion. Mutation data reported. Whenheated to decomposition it emits toxic fumes of NOx.

Purification Methods

Fractionally distil it twice at 10-20mm, the fraction boiling at 220-250o being collected. It can be further purified via the hydrochloride. Its solution in MeOH (40mL of base in 250mL) is cooled in an ice-bath and conc HCl (~50mL) is added dropwise with stirring. The precipitated hydrochloride is filtered off, washed with Me2CO, and Et2O, then dried in a vacuum desiccator. The free base is then obtained by basification, extraction into Et2O, drying (NaOH), filtering, evaporating and distilling the residue as before. It forms a Cu complex [Cu(C10H28N6)]2+. [Jonassen et al. J Am Chem Soc 79 4279 1957, Beilstein 4 IV 1245.]

InChI:InChI=1/C10H28N6/c11-1-3-13-5-7-15-9-10-16-8-6-14-4-2-12/h13-16H,1-12H2/p+6

Synthetic route

1-<2-<(2-aminoethyl)amino>ethyl>aziridine (23435-23-6) + 1,5-diamino-3-azapentane (111-40-0) → 3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7)

Conditions	Yield
With hydrogen cation In water at 50℃; Rate constant; Thermodynamic data; also at 60 and 70 deg C; Ea, ΔH;
With hydrogen cation In water

C12H24N6O2 → 3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7)

Conditions	Yield
With sodium hydroxide In water at 220℃; for 3.16667h; Autoclave; Inert atmosphere;

3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) + heptadecanoic acid (506-12-7) + guanidine hydrochloride (50-01-1) → C48H100N14O2*ClH

Conditions	Yield
Stage #1: 3,6,9,12-tetraazatetradecane-1,14-diamine; heptadecanoic acid With toluene-4-sulfonic acid at 160℃; for 3.33h; Stage #2: guanidine hydrochloride at 160 - 180℃; for 6h;	97%

3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) + sodium tetraphenyl borate (143-66-8) + cadmium(II) acetate dihydrate (5743-04-4) → {Cd(H2N(CH2CH2NH)4CH2CH2NH2)}(2+)*2B(C6H5)4(1-)={Cd(H2N(CH2CH2NH)4CH2CH2NH2)}(B(C6H5)4)2

Conditions	Yield
In methanol byproducts: NaOOCCH3, H2O; dissolving Cd(OAc)2*2H2O in methanol, dropwise addn. of pentaethylenehexamine in methanol and then NaBPh4 dissolved in methanol with stirring; crystn. after 1 h; filtration, washing with methanol, drying in vac., dynamic vac. for ca. 10 h to remove MeOH, elem. anal.;	86%

3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) + salicylaldehyde (90-02-8) → 2,2'-{ethane-1,2-diylbis[3-(2-{[(1E)-(2-hydroxyphenyl)methylene]amino}ethyl)imidazolidine-1,2-diyl]}diphenol

Conditions	Yield
In methanol at 70℃; for 10h;	80.1%

3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) + 3-methoxy-2-hydroxybenzaldehyde (148-53-8) → 2,2'-{ethane-1,2-diylbis[3-(2-{[(1E)-(2-hydroxy-3-methoxyphenyl)methylene]amino}ethyl)imidazolidine-1,2-diyl]}di(6-methoxyphenol)

Conditions	Yield
In methanol at 70℃; for 10h;	75%

3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) + mono-6-deoxy-6-(p-tolylsulphonyl)-β-cyclodextrin (67217-55-4) → C47H86N6O34

Conditions	Yield
at 75℃; for 8h; Inert atmosphere;	68.5%

cadmium fluoroborate * 6H2O + 3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) → {Cd(H2N(CH2CH2NH)4CH2CH2NH2)}(2+)*2BF4(1-)={Cd(H2N(CH2CH2NH)4CH2CH2NH2)}(BF4)2

Conditions	Yield
In methanol byproducts: H2O; dropwise addn. of a soln. of pentaethylenehexamine to a stirred soln. of Cd(BF4)2*6H2O in methanol; ppt. after 1 h, filtration, washing two times with small amts. of ice-cold methanol, drying in vac., elem. anal.;	66%

ferrocenecarboxaldehyde (12093-10-6) + 3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) → 1,18-diferrocenyl-2,5,8,11,14,17-hexaazaoctadecane (194150-03-3)

Conditions	Yield
With LiAlH4 In tetrahydrofuran; ethanol refluxing the aldehyde and the amine in EtOH for 3 h, evapn. to dryness,dissoln. (THF), addn. of LiAlH4, reflux under argon for 1 h, quenching with H2O; filtration, evapn. to dryness, addn. of basic H2O and CH2Cl2, drying (Na2SO4), chromy. (alumina; CH2Cl2, then CH2Cl2/MeOH); elem. anal.;	65%

(Lithocholoyloxy) succinimide + 3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) → Lithocholic acid, hexaaminopentaethyleneamide, acetate

Conditions	Yield
With triethylamine In MeOH-water; 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran; acetic acid	60%

3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) + (E/Z)-3,7-dimethyl-2,6-octadienal (5392-40-5) → C20H44N6

Conditions	Yield
Stage #1: 3,6,9,12-tetraazatetradecane-1,14-diamine; (E/Z)-3,7-dimethyl-2,6-octadienal With titanium(IV) isopropylate In methanol at 20℃; for 12h; Stage #2: With sodium tetrahydroborate In methanol at 0℃; for 2h;	58%

3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) + mercury dichloride → [Hg(4-(2-aminoethyl)-triethylenetetramine)][HgCl4] (1361409-61-1)

Conditions	Yield
In methanol soln. of ligand added dropwise to MeOH soln. of HgCl2 (1:2 molar ratio) at room temp.; filtered, crystd. on storage, septd., washed (hexane), dried (vac.), elem. anal.;	55%

3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) + (E)-isopropyl cinnamate (60512-85-8) → 3-[2-(2-{2-[2-(2-amino-ethylamino)-ethylamino]-ethylamino}-ethylamino)-ethylamino]-3-phenyl-propionic acid isopropyl ester

Conditions	Yield
at 65℃; for 48h; aza-Michael addition;	53%

cadmium(II) chloride monohydrate + 3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) → [Cd5(N-(2-aminoethyl)piperazine-1,4-diethylamine)2Cl10]

Conditions	Yield
In methanol soln. of ligand added dropwise to MeOH soln. of CdCl2 (2:5 molar ratio) at room temp.; filtered, crystd. on storage, septd., washed (hexane), dried (vac.), elem. anal.;	51%

cobalt(II) chloride hexahydrate + 3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) + arsenic(III) trioxide + sulfur (7704-34-9) → [Co(pentaethylenehexamine)][Co(As3S3)2]

Conditions	Yield
In water at 140℃; for 120h; Autoclave; High pressure;	51%

germanium (7440-56-4) + selenium (7782-49-2) + samarium(III) chloride + 3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) + water (7732-18-5) → [Sm2(μ-OH)2(tetraethylenepentamine)2(μ-Ge2Se6)]

Conditions	Yield
at 170℃; for 168h; Sealed tube; High pressure;	51%

sodium azide + cadmium(II) perchlorate hexahydrate + 3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) → [Cd3(N3)4(N-(2-aminoethyl)piperazine-1,4-diethylamine)2][ClO4]

Conditions	Yield
In methanol soln. of ligand reacted with of MeOH soln. of Cd compd., NaN3 added (2:3:4 molar ratio); filtered, crystd. on storage, septd., washed (hexane), dried (vac.), elem. anal.;	50%

germanium (7440-56-4) + selenium (7782-49-2) + yttrium(III) chloride + 3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) + water (7732-18-5) → C32H96Cl2Ge2N20O4Se6Y4(2+)*C16H48Cl2N10O2Y2(2+)*Ge2Se6(4-)*2ClH*C10H28N6

Conditions	Yield
at 170℃; for 168h; Sealed tube; High pressure;	47%

3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) + (6Z)-3,7,11-trimethyldodeca-2,6,10-trienal → C25H52N6

Conditions	Yield
Stage #1: 3,6,9,12-tetraazatetradecane-1,14-diamine; (6Z)-3,7,11-trimethyldodeca-2,6,10-trienal With titanium(IV) isopropylate In methanol at 20℃; for 12h; Stage #2: With sodium tetrahydroborate In methanol at 0℃; for 2h;	47%

germanium (7440-56-4) + selenium (7782-49-2) + holmium(III) chloride + 3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) + water (7732-18-5) → [Ho2(μ-OH)2(tetraethylenepentamine)2(μ-Ge2Se6)]

Conditions	Yield
at 170℃; for 168h; Sealed tube; High pressure;	46%

germanium (7440-56-4) + selenium (7782-49-2) + erbium(III) chloride + 3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) + water (7732-18-5) → C32H96Cl2Er4Ge2N20O4Se6(2+)*C16H48Cl2Er2N10O2(2+)*Ge2Se6(4-)*ClH*C10H28N6*ClH

Conditions	Yield
at 170℃; for 168h; Sealed tube; High pressure;	43%

cobalt(II) chloride hexahydrate + NH2C2H4(NHC2H4)4NH2*3HCl + 3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) → Co(NH2C2H4(NHC2H4)4NH2)(3+)*3ClO4(1-)*H2O = [Co(NH2C2H4(NHC2H4)4NH2)](ClO4)3*H2O

Conditions	Yield
With O2; HClO4 In water bubbling air through a soln. for 36 h at 25°C; filtered; concentrated; ethanol added; pptd.; filtered; washed with ethanol and ether; chromy. (HClO4); elem. anal.;	40%

selenium (7782-49-2) + tin (7440-31-5) + iron(II) chloride tetrahydrate + 3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) → [Fe(3,6,9,12-tetraazatetradecane-1,14-diamine)](Sn3Se7)n

Conditions	Yield
In methanol at 170℃; for 6h; Autoclave; High pressure;	38%

3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) + carbon dioxide (124-38-9) → C10H28N6*(x)CH2O2

Conditions	Yield
With hydrogen; C29H33BNOP2Ru In tetrahydrofuran; water at 145℃; under 60006 Torr; for 12h;	38%

3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) + 3,5-dichloropyridine (2457-47-8) → N1,N14-bis(5-chloropyridin-3-yl)-3,6,9,12-tetraazatetradecane-1,14-diamine

Conditions	Yield
With 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate; bis(dibenzylideneacetone)-palladium(0) In 1,4-dioxane for 5.5h; Heating;	35%

germanium (7440-56-4) + selenium (7782-49-2) + cerium(IV) chloride (14986-52-8) + 3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) → [Ce4(tetraethylenepentamine)4(μ-GeSe4)(μ-GeSe5)(μ-Ge2Se6)]

Conditions	Yield
at 170℃; for 168h; Sealed tube; High pressure;	33%

2,6-Dibromopyridine (626-05-1) + 3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) + sodium t-butanolate (865-48-5) → 2,5,8,11,14,17,22-heptaazabicyclo[16.3.1]docosa-1(22),18,20-triene + N-(2-aminoethyl)-N'-[2-({2-[(2-{[6-(1,1-dimethylethoxy)pyridin-2-yl]amino}ethyl)amino]ethyl}amino)ethyl]ethane-1,2-diamine

Conditions	Yield
With 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; bis(dibenzylideneacetone)-palladium(0) In 1,4-dioxane Heating;	A 27% B 12%
With 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; bis(dibenzylideneacetone)-palladium(0) In 1,4-dioxane Heating;	A 10% B 21%
With 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; [Pd(dibenzylideneacetone)2] In 1,4-dioxane Heating;	A 10 % Spectr. B 1.5%

3,5-dibromopyridine (625-92-3) + 3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) → 2,5,8,11,14,17,20-heptaazabicyclo[16.3.1]docosa-1(22),18,20-triene + N-(5-bromopyridin-3-yl)-3,6,9,12-tetraazatetradecane-1,14-diamine + N-(5-bromo-pyridin-3-yl)-N'-[2-(2-{2-[2-(5-bromo-pyridin-3-ylamino)-ethylamino]-ethylamino}-ethylamino)-ethyl]-ethane-1,2-diamine

Conditions	Yield
With 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate; bis(dibenzylideneacetone)-palladium(0) In 1,4-dioxane for 8h; Heating;	A n/a B 25% C n/a

3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) + 1,8-dichloroanthracene (14381-66-9) → anthraceno-1,4,7,10,13,16-hexaazacycloheneicosane

Conditions	Yield
With 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In 1,4-dioxane for 72h; Heating;	22%

1-bromo-2,6-dichlorobenzene (19393-92-1) + 3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) → 17-chloro-1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16-hexadecahydro-1,4,7,10,13,16-benzohexaazacyclooctadecine + N1-(2,6-dichlorophenyl)-N2-{2-[2-(2-[2-(2,6-dichlorophenylamino)ethylamino]ethylamino)ethylamino]ethyl}ethane-1,2-diamine

Conditions	Yield
With 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate; bis(dibenzylideneacetone)-palladium(0) In 1,4-dioxane Heating;	A 10% B 21%
With 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In 1,4-dioxane Inert atmosphere; Reflux;	A 10% B 21%

3,5-dibromopyridine (625-92-3) + 3,6,9,12-tetraazatetradecane-1,14-diamine (4067-16-7) → 2,5,8,11,14,17,20-heptaazabicyclo[16.3.1]docosa-1(22),18,20-triene

Conditions	Yield
With sodium t-butanolate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; bis(dibenzylideneacetone)-palladium(0) In 1,4-dioxane for 8h; Heating;	4%

Upstream product

• 23435-23-6 1-<2-<(2-aminoethyl)amino>ethyl>aziridine 
• 111-40-0 3-azapentane-1,5-diamine 

Downstream Products

• 67-56-1 methanol 
• 1326318-83-5 C₁₃₆H₁₉₆N₆O₄₈ 

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