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Diethylene oximide is an organic heteromonocyclic compound whose six-membered ring contains four carbon atoms and one nitrogen atom and one oxygen atom that lies opposite to each other; the parent compound of the morpholine family.
Diethylene oximide is a saturated organic heteromonocyclic parent and a member of morpholines.
Diethylene oximide is a conjugate base of a morpholinium.
CAS: 110-91-8
MF: C4H9NO
MW: 87.12
EINECS: 203-815-1
An aqueous solution with a fishlike odor.
Corrosive to tissue and moderately toxic by ingestion and inhalation.
Diethylene oximide is colorless and hygroscopic liquid at room temperature with a perceptible amine-like odor.
Diethylene oximide can be miscible in water at any ratio and miscible in aromatic hydrocarbon, alcohol, ketone, ether and other organic solvents, slightly miscible in mineral oil and aliphatic hydrocarbon.
Diethylene oximide has slight toxicity.
Diethylene oximide reacts with inorganic acid to generate salt, with organic acid to generate salt or acylamide.
Diethylene oximide can take alkylation reaction, react with epoxyethane and ketone and take Willgerodt reaction.
Diethylene oximide is an organic chemical compound having the chemical formula O(CH2CH2)2NH.
This heterocycle features both amine and ether functional groups.
Because of the amine, Diethylene oximide is a base; its conjugate acid is called morpholinium.
For example, treating Diethylene oximide with hydrochloric acid makes the salt morpholinium chloride.
Diethylene oximide is a colorless liquid with a weak, ammonia- or fish-like odor.
The naming of Diethylene oximide is attributed to Ludwig Knorr, who incorrectly believed it to be part of the structure of morphine.
Diethylene oximide Chemical Properties
Melting point: -7--5 °C (lit.)
Boiling point: 126.0-130.0 °C 129 °C (lit.)
Density: 0.996 g/mL at 25 °C (lit.)
Vapor density: 3 (vs air)
Vapor pressure: 31 mm Hg ( 38 °C)
Refractive index: n20/D 1.454(lit.)
Fp: 96 °F
Storage temp.: Store below +30°C.
Solubility water: miscible
Form: Liquid
pka: 8.33(at 25℃)
Color: APHA: ≤15
Specific Gravity: 0.996
PH: 11.2 (H2O)(undiluted)
Explosive limit: 1.4-15.2%(V)
Water Solubility: MISCIBLE
Freezing Point: -4.9℃
Sensitive: Hygroscopic
Merck: 14,6277
BRN: 102549
Exposure limits: TLV-TWA 20 ppm (～70 mg/m3) (ACGIH, MSHA, and OSHA); STEL skin 30 ppm (ACGIH); IDLH 8000 ppm.
Stability: Stable. Flammable. Incompatible with strong oxidizing agents, strong acids, acid chlorides, acid anhydrides. Hygroscopic.
InChIKey: YNAVUWVOSKDBBP-UHFFFAOYSA-N
CAS DataBase Reference:110-91-8(CAS DataBase Reference)
NIST Chemistry Reference: Morpholine(110-91-8)
IARC: 3 (Vol. 47, 71) 1999
EPA Substance Registry System: Morpholine (110-91-8)
Diethylene oximide is colorless water-absorbing oily liquid and it smells ammonia.
Diethylene oximide is soluble in water and methanol, ethanol, benzene, acetone, ether, ethylene glycol and other commonly used solvents.
Diethylene oximide is a colorless liquid with a weak ammonia or fish-like odor.
The odor threshold is 0.01 ppm.
The chemical reactivity of Diethylene oximide is attributed to the secondary amine function of the molecule; organic condensations, alkylations, and arylations readily occur, with the formation of N-substituted Diethylene oximide products of wide diversity.
Ethers are relatively chemically inert, hence the oxygen is of relatively little consequence except as a member of the heterocyclic ring.
Physical properties
Colorless, mobile, oily, hygroscopic, flammable liquid with a weak ammonia-like odor. Experimentally determined detection and recognition odor threshold concentrations were 40 μg/m3 (11 ppbv) and 25 μg/m3 (70 ppbv), respectively.
Forms explosive vapors at temperatures >35 °C.
Product Features
Diethylene oximide, also known as 1, 4-oxazepine and diethylenimine oxide, is a kind of colorless alkaline oily liquid.
Diethylene oximide smells of ammonia and has hygroscopicity.
Diethylene oximide could evaporate with water vapor and miscible with water.
Diethylene oximide is Soluble in acetone, benzene, ether, pentane, methanol, ethanol, carbon tetrachloride, propylene glycol and other organic solvents.
Diethylene oximide vapor could form an explosive mixture with air and the explosion limit is 1.8% to 15.2% (volume fraction).
Diethylene oximide is a secondary amine, and at the same time it has the property of inorganic acid and organic acid, so that it can generate salt and amide.
Diethylene oximide contains secondary amine groups and it has all the typical reaction characteristics of the secondary amine groups.
Diethylene oximide can react with inorganic acid to form a salt, and also can react with organic acid to form salt or amide.
Diethylene oximide can carry out alkylation reactions and it also carry out ketone reaction or Willgerodt reaction with ethylene oxide.
Because of the unique chemical properties of Diethylene oximide, it has become one of the important petrochemical products with important commercial application.
Diethylene oximide can be applied to produce rubber vulcanization accelerators such as NOBS, DTOS and MDS.
And Diethylene oximide is also applied to produce anti-corrosives, anti-corrosion agents, detergents, detergents, analgesics, local anesthetics, sedatives, respiratory and vascular stimulants, surfactants, optical bleach, fruit preservatives, and textile dyeing auxiliaries.
Morpholine also has a wide range of applications in the field of rubber, pharmaceuticals, pesticides, dyes, coatings and other industries.
In medication it could be applied in the production of Diethylene oximide guanidine, virus Ling, ibuprofen, cough must, naproxen, dichloroaniline, sodium phenylacetate and other important drugs.
The two main production method of Diethylene oximide are DEA method (diethanolamine method) and DEA method (diethylene glycol method)
Diethylene oximide is noteworthy that new polymer monomer acrylic morpholine has obtained a rapid development in recent years.
Diethylene oximide could be produced from the reaction between acrylic acid and morpholine.
Diethylene oximide is a kind of water-soluble monomer, and it is still water-soluble after the polymerization.
So Diethylene oximide could be applied for the modification of aqueous polymers.
Besides, Diethylene oximide is widely used as a reactive diluent for UV curable resins.
With the deepening of applied research, many new specific uses have been developed and Diethylene oximide becomes polymer monomer with rapid development.
Uses
(1) For medicine, Diethylene oximide used as the raw materials for rubber accelerator and fluorescent whitening agent.
(2) Diethylene oximide is the intermediates of fungicide dimethomorph and flumorpholine and organophosphate insecticide phosalphos.
(3) Diethylene oximide is Mainly used for the production of rubber vulcanization accelerator, but also for surfactant, textile auxiliaries, pharmaceuticals, pesticide synthesis.
(4) Diethylene oximide also used as a catalyst for polymerization of butadiene, corrosion inhibitors, optical bleach, the goods are dyes, resins, wax, early glue, casein and other solvents.
At present, the total production of Diethylene oximide in the world is 3-4 million t/a.
(5) Diethylene oximide are also widely used.
Diethylene oximide like morpholine hydrochloride are the organic synthesis of intermediates.
Diethylene oximide can be used as the coating agent of fruits or vegetables epidermal coating agent, and Diethylene oximide could inhibit the base respiration and prevent the epidermis from evaporation of water and epidermal atrophy.
(6) Diethylene oximide is the main raw materials of accelerator NOBS.
For analysis reagents and resins, wax, shellac and other solvents, used in the production of sodium sulfate.
Water glass and ultramarine.
(7) Diethylene oximide is used for the analysis of reagents and resins, wax, casein, shellac and a variety of solvents solvent.
(8) Diethylene oximide could produce salt after reacting with inorganic acid, and it also could produce salt or amide after reacting with organic acid.
Diethylene oximide also can be alkylated, and it also could come up a ketone reaction or Willgerodt reaction with ethylene oxide.
Diethylene oximide is made by dehydrating ethanolamines.
Diethylene oximide's main use is as a rubber accelerator in manufacturing tires.
This process requires high temperature (300°F) and pressure, which increase the hazards.
Diethylene oximide is also used as a boiler water additive, brightener for detergents, and corrosion inhibitor, in the preservation of book paper, in waxes and polishes, and in organic synthesis.
Rubber accelerator, solvent, additive to boilerwater, waxes and polishes, optical brightener fordetergents, corrosion inhibitor, preservation of bookpaper, organic intermediate (catalyst, antioxidants,pharmaceuticals, bactericides, etc.).
Diethylene oximide are mainly used to manufacture rubber accelerant (such as NOBS, OTOS and MDS), sulfuration agent (like DT-DM), cleanser, descaling agent, antirust, anti-scorching agent, antiseptic, surfactant, textile printing & dyeing agent, optical bleaching agent, chemical plating bath, antioxidant, hydrolyzing agent, initiator, developer, fruit preserving agent, deodorizer, brightener and organic solvents.
Diethylene oximide's application in such fields as medicine, pesticide, animal medicine, petroleum and extraction of coke aromatic hydrocarbon have been ceaselessly developed and carried out.
In foreign countries, a great deal of Diethylene oximide is used for antirust, descaling and metal cleaning, especially for antirust and anticorrosive in high temperature conditions.
In boiler maintenance fields, amount of Diethylene oximide is also used as descaling agent.
Owing to its unique chemical characters, Diethylene oximide has become one of the most important fine petroleum chemical products and its applications are very wide.
Industrial uses
The total industrial consumption of Diethylene oximide is 11,000 metric tons/year.
The largest usage for Diethylene oximide is in the rubber industry as an intermediate in the production of delayed-action accelerators for the polymerization of rubber, as stabilizers against heat-aging effects, and as bloom inhibitors in butyl rubber vulcanization.
A second large proportion (25%) of Diethylene oximide production is used as an inhibitor to combat carbonic acid corrosion in condensate return lines of steam boiler systems.
Diethylene oximide is an intermediate in the manufacture of optical brighteners utilized by the soap and detergent industry.
Diethylene oximide reacts readily with fatty acids, forming soaps used in the formulation of self-polishing waxes and polishes and in coatings for the food industry.
Diethylene oximide and TV-ethyl morpholine are used as catalysts in the manufacture of polyurethane foams.
Diethylene oximide derivatives are utilized in pharmaceutical applications, as bactericides, fungicides, and herbicides, and as separating agents for oils.
Other derivatives are utilized in the textile and printing industry as adjuvants, whitening agents, stabilizers, ink eradicators, and paper conditioners.
Metal Corrosion Inhibitors
As a kind of metal corrosion inhibitor, Diethylene oximide is mainly applied for the anti-corrosion of iron, copper, zinc, lead and other metals.
Diethylene oximide remains at its starting stage in China, but outside the country, a considerable proportion of Diethylene oximide are used as a kind of anti-rust agent for metal gas to prevent the metal corrosion caused by atmosphere and it has been widely used in the field of mechanical instruments, automobiles, medical equipment and others.
The metal atmospheric rust inhibitor used earlier such as dicyclohexylamine nitrite and cyclohexylamine do harm to the human body and they are more environmentally toxic.
Instead, Diethylene oximide as a metal gas-liquid corrosion inhibitor, it has the advantages of low toxicity, so the foreground is prosperous.
Rubber Vulcanization Accelerator
Before 1990's, in Europe, the United States, Japan and other developed areas, the consumption of rubber vulcanization accelerator accounted for more than 50% of the total demand for morpholine.
At present, more than 30% consumption of rubber vulcanization accelerator is used for NOBS.
In recent years, the toxicity issue of the harmful nitrosamines in the accelerator which produced during rubber processing is driving more attention internationally.
A number of restrictive laws and regulations are introduced all around the world.
For example, in Germany as early as 1982, the law about the regulations issued nitrosamine content control was established.
The United States, Japan, France, the United Kingdom actively developed new vulcanization accelerator which don’t produce nitrosamine, and they have stopped using nitrosamine which will produce vulcanization accelerator.
Therefore, the consumption of Diethylene oximide in foreign countries has decreased with banning of the accelerator NOBS year by year.
But China has joined the WTO, due to a large number of foreign enter and high requirement about additives localization, Diethylene oximide requires more environmental protection in China's rubber vulcanization accelerator.
Using non-toxic promoter and replacing NOBS becomes the general trend.
China's demand for NOBS is significantly reduced in recent years.
China will no longer use basic decomposition of nitrosamine secondary amine accelerator.
As the main substitute of NOBS, NS (N-tert-butyl-2-benzothiazole sulfonmide), which does not produce nitrosamines, has a large production capacity.
In 2005, the output was 14,000 tons and it is 10.1%, of the total amount.
So there was good development momentum.
Quantitative Analysis
Get 4 parts of methanol solution with 0.1% of bromocresol green and 1 part of 0.1% aqueous solution with 0.1% of methyl red sodium salt.
Mix them and put aside to use as a mixed indicator later.
Get 50ml water in 250ml flask, add 0.4ml mixed indicator, drop 0.1moI/L hydrochloric acid, and wait for the color to turn green.
Accurately weighs the sample 1.4~1.6g, add the flask and mix it.
Use 0.5mol/L hydrochloric acid titration and wait for the color to turn green.
Per ml, 0.5mol/L hydrochloric acid is equivalent to 43.56mg C4H9NO.
Production method
(1) Diethylene oximide could be produced by diethanolamine dehydration cyclization derived from sulfuric acid.
Add diethanolamine to the water reaction pot and drop sulfuric acid in the temperature of 60 ℃, then when the temperature heat at 185-195 ℃, incubate it for 30min.
Cool Diethylene oximide to under 60℃ and drop sodium hydroxide solution to pH = 11.
The next steeps are cooling, filtering, filtrating distillation, collecting the following fractions below 130℃.
The content of spermine is suppose to reach more than 99.5%.
The method is easy to obtain raw materials, so Diethylene oximide has become the main method of producing morpholine in the world.
Diethylene oximide also could be produced in the catalytic reaction between dioxane and ammonia gas.
(2) The preparation method is that we could get Diethylene oximide from the presence of sulfuric acid dehydration cyclization diethanolamine.
In the presence of sulfuric acid ; then add diethanolamine into the reaction kettle and add H2SO4 at a temperature of below 6 °C, then heat it to 185-195 °C for 30 minutes, cool to 60 °C.
Drop NaOH solution to pH = 11, and the last two steeps is cooling and filtrating.
Morpholine could be collected from the fraction below 130 °C.
We can also get morpholine from the reaction between diethylene glycol and ammonia in the presence of catalyst and pressure.
The method is easy to obtain raw materials, thus Diethylene oximide is the main method of producing morpholine around the world.
Hazards & Safety Information
Category: Flammable liquids
Toxicity grading: Poisoning
Acute toxicity: Oral-rat LD 50: 1050 mg/kg; oral-mouse LD 50: 525 mg/kg
Stimulating data: Skin-rabbit 995 mg/24 h severe; eye –rabbit 2 mg severe.
Hazardous characteristic of explosive: Will cause explosion when it mixes with steam and air
Hazardous characteristic of flammability: Flammable; combustion produces toxic chloride gas
Transportation and storing properties: Store Diethylene oximide in low temperature, dry and ventilated environment.
Prevent from fire, friction，spark and Separated from oxidant
Extinguishant: Water spray, dry chemical powder, foam or carbon dioxide
Occupational standards: TLV-TWA 70 mg/m3 STEL 105 mg/m3
Reactivity Profile
Diethylene oximide dissolved in water 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
May cause toxic effects if inhaled or ingested/swallowed.
Contact with substance may cause severe burns to skin and eyes.
Fire will produce irritating, corrosive and/or toxic gases.
Vapors may cause dizziness or suffocation.
Runoff from fire control or dilution water may cause pollution.
Diethylene oximide is extremely irritating, causing severe damage to the eyes, mucous membranes, and skin upon contact.
Eye irritation, with transient corneal edema and temporary foggy vision are common symptoms of overexposure to vapors in the workplace.
Diethylene oximide is readily absorbed through the skin; it causes nasal irritation when inhaled, with coughing, bronchial irritation, and pulmonary edema at increasingly higher concentrations.
Upon ingestion, Diethylene oximide causes hemorrhage in the gastrointestinal tract, with possible diarrhea; liver and kidney damage may occur if sufficient amounts are ingested or inhaled.
Diethylene oximide itself is not a carcinogen on the basis of available data.
Flammable, moderate fire risk. Toxic byingestion and inhalation, irritant to skin, absorbedby skin.
Eye damage and upper respiratory tractirritant.
Questionable carcinogen.
Diethylene oximide is an irritant to the eyes, skin,and mucous membranes.
The irritant actionsin rabbit eyes and skin were severe.
In humans the inhalation of its vapors cancause visual disturbance, nasal irritation, andcoughing.
High concentrations can producerespiratory distress.
Fire Hazard
Flammable/combustible material.
May be ignited by heat, sparks or flames.
Vapors may form explosive mixtures with air.
Vapors may travel to source of ignition and flash back.
Most vapors are heavier than air.
They will spread along ground and collect in low or confined areas (sewers, basements, tanks).
Vapor explosion hazard indoors, outdoors or in sewers.
Runoff to sewer may create fire or explosion hazard.
Containers may explode when heated.
Many liquids are lighter than water.
Carcinogenicity
Diethylene oximide did not produce an increase in tumors in rats that inhaled from 10 to 150 ppm for 2 years.
No tumors were seen in rats fed 5000 ppm Diethylene oximide for 8 weeks and observed for their lifetime.
Diethylene oximide fed concurrently with sodium nitrate increased the numbers of hepatocellular carcinomas and sarcomas of the liver and lungs of rats and mice, probably mediated through the formation of N-nitrosomorpholine.
The authors concluded that Diethylene oximide itself was either weakly carcinogenic or that a nitrate from an unknown source was present.
No cancers were produced when 6330 ppm Diethylene oximide was added to the drinking water of mice for their lifetimes.
Concurrent exposure of Diethylene oximide plus nitrite or nitrogen dioxide increased the tumor incidence in a variety of species.
In a feeding study where Diethylene oximide (0.5% in diet) and sodium nitrate were given concurrently for 23 weeks, rats showed no evidence of cancer.
Metabolism
Early reports indicated that Diethylene oximide was excreted unchanged after administration to rats, dogs, and rabbits.
Sohn et al reported that approximately 80% of a radioactive dose was excreted in the urine within 24 h when administered intraperitoneally to rats, hamsters, and guinea pigs.
Although 99% of the excreted dose was unmetabolized in the rat and hamster, 20% of the dose appeared in the urine of guinea pigs as N-methylmorpholine-N-oxide.
Diethylene oximide and N-methylmorpholine were also detected in extracts of guinea pig tissues.
Studies of the metabolism of Diethylene oximide-containing pharmaceutical agents in humans and animals indicate that the Diethylene oximide moiety may be hydroxylated or oxidized at C2 and C3, with subsequent ring cleavage.
Synonyms
MORPHOLINE
110-91-8
1-Oxa-4-azacyclohexane
Tetrahydro-1,4-oxazine
Diethylene oximide
Diethylenimide oxide
Diethyleneimide oxide
Diethylene imidoxide
Drewamine
Tetrahydro-2H-1,4-oxazine
Tetrahydro-p-oxazine
p-Isoxazine, tetrahydro-
Tetrahydro-1,4-isoxazine
morpholin
BASF 238
Caswell No. 584
2H-1,4-Oxazine, tetrahydro-
4H-1,4-Oxazine, tetrahydro-
NSC 9376
138048-80-3
MFCD00005972
C4H9NO
Tetrahydro-4H-1-4-oxazine
8B2ZCK305O
DTXSID2025688
CHEBI:34856
NSC-9376
DTXCID305688
CAS-110-91-8
CCRIS 2482
HSDB 102
MORPHOLINE,REAG
Tetrahydro-p-isoxazine
MORPHOLINE, PRACT
EINECS 203-815-1
UN2054
EPA Pesticide Chemical Code 054701
BRN 0102549
morphline
UNII-8B2ZCK305O
morpho line
morpholine-
AI3-01231
6LR
4H-1, tetrahydro-
MORPHOLINE [MI]
Morpholine [UN2054] [Flammable liquid]
Morpholine Reagent Grade
MORPHOLINE [FCC]
MORPHOLINE [HSDB]
MORPHOLINE [IARC]
MORPHOLINE [INCI]
Morpholine on Rasta Resin
WLN: T6M DOTJ
EC 203-815-1
NCIMech_000154
Tetrahydro-1, 4-isoxazine
NCIOpen2_007748
Oprea1_317540
Tetryhydro-2H-1,4-oxazine
Tetrahydro-4H-1,4-Oxazine
4-27-00-00015 (Beilstein Handbook Reference)
BIDD:ER0297
Morpholine, analytical standard
CHEMBL276518
NSC9376
AMY22834
BCP24054
STR00194
ZINC1699948
Tox21_202450
Tox21_303240
STL182843
AKOS000118829
Morpholine, ACS reagent, >=99.0%
Morpholine, ReagentPlus(R), >=99%
DB13669
NA 2054
UN 2054
NCGC00249227-01
NCGC00256942-01
NCGC00259999-01
61791-40-0
Morpholine, p.a., ACS reagent, 99.0%
DB-030063
Morpholine [UN2054] [Flammable liquid]
FT-0628993
M0465
EN300-18064
Morpholine purified by distillation from glass
Morpholine, purified by redistillation, >=99.5%
Q410243
J-522715
1-Oxa-4-azacyclohexane ; Tetrahydro-2H-1,4-oxazine
F2190-0339
ScavengePore(TM) phenethyl morpholine, macroporous, 40-70 mesh, extent of labeling: 0.7-1.5 mmol/g loading
StratoSpheres(TM) PL-MPH resin, 50-100 mesh, extent of labeling: 3.0-4.0 mmol/g loading, 1 % cross-linked
