Hexamethyleneimine Property

Melting point:

-37°C

Boiling point:

138 °C749 mm Hg(lit.)

Density 

0.88 g/mL at 25 °C(lit.)

vapor pressure 

7.4 mm Hg ( 21.1 °C)

refractive index 

n20/D 1.466(lit.)

Flash point:

65 °F

storage temp. 

Poison room

form 

Liquid

pka

pK1:11.07 (25°C)

color 

Clear colorless to light yellow

Odor

Ammonia-like.

explosive limit

1.6-9.9%(V)

Water Solubility 

soluble

BRN 

1084

LogP

1.7

CAS DataBase Reference

111-49-9(CAS DataBase Reference)

NIST Chemistry Reference

1H-Azepine, hexahydro-(111-49-9)

EPA Substance Registry System

1H-Azepine, hexahydro- (111-49-9)

Safety

Hazard Codes 

T,T+,F

Risk Statements 

10-20-25-34-28-11

Safety Statements 

26-36/37/39-45-28A-16-1

RIDADR 

UN 2493 3/PG 2

WGK Germany 

3

RTECS 

CM3150000

Autoignition Temperature

255 °C

TSCA 

Yes

HS Code 

2933 99 80

HazardClass 

3

PackingGroup 

II

Hazardous Substances Data

111-49-9(Hazardous Substances Data)

Toxicity

LD50 orally in Rabbit: 410 mg/kg

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Danger

Hazard statements

H225Highly Flammable liquid and vapour

H300Fatal if swallowed

H314Causes severe skin burns and eye damage

H331Toxic if inhaled

Precautionary statements

P210Keep away from heat/sparks/open flames/hot surfaces. — No smoking.

P261Avoid breathing dust/fume/gas/mist/vapours/spray.

P264Wash hands thoroughly after handling.

P264Wash skin thouroughly after handling.

P280Wear protective gloves/protective clothing/eye protection/face protection.

P301+P310IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.

P305+P351+P338IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continuerinsing.

Hexamethyleneimine Chemical Properties,Usage,Production

Chemical Properties

clear colorless to light yellow liquid

Uses

Hexamethyleneimine is used as a pharmaceutical product and raw material for rubber products. It is also used as a intermediate for agrochemicals, zeolites, dyes , inks, rubber chemicals, textile chemicals, corrosion inhibitors, ore flotation.

Uses

A degradation product of herbicide Molinate in pot soil and rice plants.

Production Methods

Hexamethyleneimine is produced in 84% yield by heating hexamethylenediamine at 350 ℃ in a stream of hydrogen. The catalyst, ammonium vanadate on activated alumina, is prereduced with hydrogen at 500 ℃. Residues from the industrial distillation of hexamethylenediamine can be converted into hexamethyleneimine over aluminum silicate or aluminum oxide in a stream of nitrogen. For the preparation from caprolactam]. Hexamethyleneimine can be prepared by dimerizing acrolein, reducing the product to 2- hydroxymethyltetrahydropyran, expanding the ring to give oxepane, followed by treatment with ammonia over aluminum oxide at 350 ℃.

Application

The most important use is the conversion of hexamethyleneimine into S-ethylhexahy- dro-1H-azepine-1-carbothioate, the selective rice herbicide Molinate (C2H5 S–CO–NC6H12 , Zeneca).

Definition

ChEBI: An azacycloalkane that is cycloheptane in which one of the carbon atoms is replaced by a nitrogen atom.

General Description

A colorless liquid with an ammonia-like odor. Flash point 65°F. Toxic by ingestion. Corrosive to metals and tissue. Combustion produces toxic oxides of nitrogen.

Air & Water Reactions

Highly flammable. Soluble in water.

Reactivity Profile

Hexamethyleneimine 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 is generated in combination with strong reducing agents, such as hydrides.

Hazard

Toxic by ingestion, strong irritant to tissue.

Health Hazard

Inhalation of vapor irritates respiratory tract; high concentrations may cause disturbance of the central nervous system. Ingestion causes burns of mouth and stomach. Contact with concentrated vapor may cause severe eye injury. Contact with liquid causes burns of eyes and skin.

Flammability and Explosibility

Highly flammable

Chemical Reactivity

Reactivity with Water No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.

Purification Methods

Purify azepane by dissolving in Et2O and adding ethanolic HCl until all the base separates as the white hydrochloride, filter, wash with Et2O and dry it (m 236o). The salt is dissolved in the minimum volume of H2O and basified to pH ~ 14 with 10N KOH. The solution is extracted with Et2O, the extract is dried over KOH, evaporated and distilled. The free base is a FLAMMABLE and TOXIC liquid, and best kept as the salt. The nitrate has m 120-123o, the picrate has m 145-147o, and the tosylate has m 76.5o (ligroin). [Müller & Sauerwald Monatsh Chem 48 727 1027, Hjelt & Agback Acta Chem Scand 18 194 1964, Beilstein 20 II 1406, 20 III/IV 1406, 20/4 V 3.]