Diethylamin, in w?ssriger L?sung Chemische Eigenschaften,Einsatz,Produktion Methoden
ERSCHEINUNGSBILD
FARBLOSE FLüSSIGKEIT MIT STECHENDEM GERUCH.
PHYSIKALISCHE GEFAHREN
Die D?mpfe sind schwerer als Luft und k?nnen sich am Boden ausbreiten. Fernzündung m?glich.
CHEMISCHE GEFAHREN
Die Substanz zersetzt sich beim Erhitzen oder beim Verbrennen unter Bildung von giftigen Rauchen mit Stickoxiden. Mittelstarke Base. Reagiert mit starken Oxidationsmitteln, S?uren und organischen Stoffen. Feuer- und Explosionsgefahr. Greift Metall, einige Arten von Kunststoff, Gummi und Beschichtungen an.
ARBEITSPLATZGRENZWERTE
TLV: 5 ppm (als TWA), 15 ppm (als STEL) Hautresorption Krebskategorie A4 (nicht klassifizierbar als krebserzeugend für den Menschen); (ACGIH 2008).
EG Arbeitsplatz-Richtgrenzwerte: 5 ppm (als TWA), 10 ppm (als STEL) (EU 2002).
MAK:, 5 ppm 15 mg/m?Spitzenbegrenzung: überschreitungsfaktor I(2); Ein Momentanwert von 10 ml/m?entsprechend 30 mg/m?sollte nicht überschritten werden. Schwangerschaft: Gruppe D (DFG 2008).
AUFNAHMEWEGE
Aufnahme in den K?rper durch Inhalation der D?mpfe, über die Haut und durch Verschlucken.
INHALATIONSGEFAHREN
Beim Verdampfen bei 20°C kann sehr schnell eine gesundheitssch?dliche Kontamination der Luft eintreten.
WIRKUNGEN BEI KURZZEITEXPOSITION
WIRKUNGEN BEI KURZZEITEXPOSITION: Die Substanz ver?tzt die Augen, die Haut und die Atemwege. ?tzend beim Verschlucken. Inhalation kann Lungen?dem verursachen, jedoch nur nachdem anf?ngliche korrossive Effekte auf die Augen und/oder Atemwege aufgetreten sind. Inhalation kann zu Pneumonitis führen. Exposition in hohen Konzentrationen kann zu starker Schwellung im Hals führen. ?rztliche Beobachtung notwendig.
WIRKUNGEN NACH WIEDERHOLTER ODER LANGZEITEXPOSITION
Risiko der Lungensch?digung bei wiederholter oder l?ngerer Dampf-Exposition. M?glich sind Auswirkungen auf die Z?hne mit nachfolgender Zahnerosion.
LECKAGE
Gefahrenbereich verlassen! Pers?nliche Schutzausrüstung: Chemikalienschutzanzug mit umgebungsluftunabh?ngigem Atemschutzger?t. Zündquellen entfernen. NICHT in die Umwelt gelangen lassen. NICHT in die Kanalisation spülen. Belüftung. Ausgelaufene Flüssigkeit in abdichtbaren Kunststoff-Beh?ltern sammeln. Reste sorgf?ltig sammeln. An sicheren Ort bringen.
R-S?tze Betriebsanweisung:
R11:Leichtentzündlich.
R20/21/22:Gesundheitssch?dlich beim Einatmen,Verschlucken und Berührung mit der Haut.
R35:Verursacht schwere Ver?tzungen.
S-S?tze Betriebsanweisung:
S16:Von Zündquellen fernhalten - Nicht rauchen.
S26:Bei Berührung mit den Augen sofort gründlich mit Wasser abspülen und Arzt konsultieren.
S29:Nicht in die Kanalisation gelangen lassen.
S36/37/39:Bei der Arbeit geeignete Schutzkleidung,Schutzhandschuhe und Schutzbrille/Gesichtsschutz tragen.
S45:Bei Unfall oder Unwohlsein sofort Arzt zuziehen (wenn m?glich, dieses Etikett vorzeigen).
S3:Kühl aufbewahren.
Aussehen Eigenschaften
C4H11N; farblose, aminartig riechende Flüssigkeit.
Gefahren für Mensch und Umwelt
Leicht entzündlich. Die Dämpfe sind schwerer als Luft und bilden mit Luft ein explosionsfähiges Gemisch. Bei Kontakt mit
Oxidationsmitteln heftige Reaktion oder Entzündung. Bei Kontakt mit Quecksilber kann explosionsartige Reaktion erfolgen (keine Quecksilberthermometer verwenden).
Diethylamin wirkt als Dampf stark reizend auf die Schleimhäute der Augen und der Atmungsorgane sowie als Flüssigkeit ebenfalls stark reizend auf die Haut. Flüssigkeitskontakt mit dem Auge kann schwere Hornhautschäden bewirken. Sensibilisierung ist möglich und führt zu Lid- und Gesichtsödemen sowie zu Hautentzündungen.
Schwach wassergefährdender Stoff (WGK 1).
Schutzma?nahmen und Verhaltensregeln
Im Abzug arbeiten.
Schutzhandschuhe nur als kurzzeitiger Spritzschutz.
Verhalten im Gefahrfall
Mit flüssigkeitsbindendem Material (Sand, Kieselgur) aufnehmen. Als Sondermüll entsorgen.
Wassernebel, Kohlendioxid, Löschpulver, Schaum.
Erste Hilfe
Nach Hautkontakt: Mit Seife und reichlich Wasser abwaschen. Mit Polyethlenglycol 400 abtupfen.
Nach Augenkontakt: Gründlich mit viel Wasser bei geöffnetem Augenlid mind. 10 Min. mit Wasser spülen. Augenarzt konsultieren.
Nach Einatmen: Frischluft.
Nach Verschlucken: Viel Wasser trinken lassen - möglichst mit Aktivkohlezusatz. Auf
keinen Fall fette Öle oder Milch verabreichen.
Nach Kleidungskontakt: Benetzte Kleidung sofort ausziehen.
Ersthelfer: siehe gesonderten Anschlag
Sachgerechte Entsorgung
Als Sondermüll entsorgen.
Beschreibung
Diethylamine is a colourless, strongly alkaline, fish odour liquid, and highly inflammable. It has an ammonia-like odour and is completely soluble in water. On burning, diethylamine releases ammonia, carbon monoxide, carbon dioxide, and nitrogen oxides. Diethylamine is used in the production of pesticides. It is used in a mixture for the production of DEET which goes into the repellents that are found readily in supermarkets for general use.
Physikalische Eigenschaften
Colorless liquid with a fishy, ammonia-like odor. Experimentally determined detection and recognition odor threshold concentrations were 60 μg/m3 (20 ppbv) and 180 μg/m3 (60 ppbv), respectively (Hellman and Small, 1974). Diethylamine is a very strong base in aqueous solution (pKb = 3.0). Its chemistry is governed by the unshared electron pair on the nitrogen, thus it tends to react with acids to form salts.
Occurrence
Diethylamine occurs in low concentrations in food and other biological materials.
Concentrations (in p.p.m.) in fresh products include: spinach (15), apples (3), butterbeans
(2.4), shelled peas (0.1), bean salad (1.5) and red cabbage (2.4) (HSDB
1989). Pickled vegetables contain 0-3.2 p.p.m. diethylamine while concentrations
(in p.p.m.) in other materials include herring (0-5.2), barley (5.7), hops (3.1), boiled
beef (2), tobacco leaf (0.1-35) and cigarette smoke concentrate (0-0.4). Interest in
the occurrence of diethylamine in foods arises in part because of its possible formation
of a carcinogenic N-nitroso derivative (Neurath et al 1977). Diethylamine has
been reported in the exhaust from a gasoline engine (Hampton et al 1982).
Verwenden
Diethylamine is manufactured by heating ethyl chloride and
alcoholic ammonia under pressure or by hydrogenation of
aziridines in the presence of catalysts. DEA is used as a
solvent, as a rubber accelerator, in the organic synthesis of
resins, dyes, pesticides, and pharmaceuticals, in electroplating,
and as a polymerization inhibitor. Other
applications include uses as a corrosion inhibitor. It was
reported noneffective as a skin depigmentator.
Definition
ChEBI: Diethylamine is a secondary aliphatic amine where both N-substituents are ethyl. It is a conjugate base of a diethylammonium.
Vorbereitung Methode
Diethylamine is produced using the three methods also used for the manufacture of ethylamine with very slight modification.
Diethylamine Synthesis
1. N,N-Diethyl-3-methylbenzamide + Ethylene Glycol + NaOH + Heat
2. Ethylchloride + Ammonia (forms diethylamine HCL)
3. Ethanol + Ammonia + Sulfuric Acid
The most widely used method is the passing of ammonia and ethanol over a catalyst such as alumina or silica (Schweizer et al 1978). Diethylamine can be separated from the mixture by selective distillations and extractions.
Allgemeine Beschreibung
Diethylamine appears as a clear colorless liquid with an ammonia-like odor. Density 5.9 lb / gal. Flash point -15 °F. A respiratory irritant. Corrosive to the eyes and skin. Vapors heavier than air. Toxic oxides of nitrogen produced during combustion.
Air & Water Reaktionen
Highly flammable. Soluble in water. Sensitive to heat. May be sensitive to prolonged exposure to air.
Reaktivit?t anzeigen
It is incompatible with several chemical substances such as strong oxidisers, acids, cellulose nitrate, some metals, and dicyanofuroxan. N-nitrosamines, many of which are known to be potent carcinogens, may be formed when diethylamine comes in contact with nitrous acid, nitrates, or atmospheres with high nitrous oxide concentrations.
Health Hazard
Diethylamine can be harmful if it is inhaled, swallowed, or in contact with skin.
Vapors can irritate the eyes and cause irritation of the respiratory tract, leading to
coughing and chest pain. Liquid diethylamine can cause severe burns to the eyes
and skin. Vision became misty and halos appeared several hours after workmen
were exposed to the vapors of amines such as diethylamine (Grant 1986). The
edema of the corneal epithelium, which is principally responsible for the disturbances
in vision, clears after one or more days, depending on the severity of
exposure. Photophobia and discomfort from roughness of the corneal surface also
can occur after greater exposure to the amine.
Chemische Reaktivit?t
Reactivity with Water No reaction; Reactivity with Common Materials: No hazardous reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Flush with water; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.
Industrielle Verwendung
Diethylamine, like many of the other short chain aliphatic amines, has achieved
widespread industrial use as an intermediate in the manufacture of a number of
commercial products. Among these are included insecticides, pharmaceuticals,
textile finishing agents, and corrosion inhibitors (Hawley 1981; Schweizer et al
1978). It is used as a polymerization inhibitor and/or catalyst in the polymer
industry and in the manufacture of surfactants and rubber processing accelerators.
This amine also is useful as a depilatory agent for animal skins, as a selective
solvent for the removal of impurities from oils, fats, and waxes, and as a flotation
agent in the petroleum industry (NIOSH/OSHA 1981; HSDB 1989).
Toxikologie
Exposure to low vapor concentrations are reported to transiently impair vision in humans (reduction of sensitivity to light): no-effect threshold 0.022 – 0.028 mL/m3 ( 0.08mg/m3 ). The odor threshold in air is ca. 0.02 – 0.3 mL/m3 ( 0.9 mg/m3 ). Transient physiological effects in rats after 90-d exposure to vapors were reported to already be visible at 0.37 – 4.19 mg/m3 with no effects at 0.05 mg/m3 , but with morphological, apparently reversible changes in the lung and cerebral neurons at the highest concentration. On the other hand, 50 mL/m3 (150 mg/m3 ) was the lowest concentration to show mild, but signifi- cant effects in the lung and liver of rabbits on prolonged inhalation. There were no visible signs of toxicity following exposure of rats to 25 mL/m3 (75 mg/m3 ) for 120 d, but a moderate, bronchiolar hyperplasia of lymphoid cells. It was assumed that diethylamine may exert a certain neurotoxic effect, which, however, was not confirmed by others.
Sicherheitsprofil
Moderately toxic by
ingestion, inhalation, and skin contact. A
skin and severe eye irritant. Exposure to
strong vapor can cause severe cough and
chest pains. Contact with liquid can damage
eyes, possibly permanently; contact with
skin causes necrosis and vesciculation. A
very dangerous fire hazard when exposed to
heat, flame, or oxidizers. To fight fire, use
alcohol foam, CO2, dry chemical. Explodes
on contact with dicyanofurazan. Violent
reaction with sulfuric acid. Ignites on
contact with cellulose nitrate of sufficiently
high surface area. When heated to
decomposition it emits toxic fumes of NOx.
See also MINES.
Carcinogenicity
No evidence of mutagenicity was seen
in Ames bacterial assays.8 Diethylamine has
an ammonia-like odor that is detectable at
0.13ppm.
The 2003 ACGIH threshold limit valuetime-
weighted average (TLV-TWA) for
diethylamine is 5ppm (15mg/m3) with
a short-term excursion limit of 15ppm
(45mg/m3) and an A4-not classifiable as a
human carcinogen designation; there is a notation
for skin absorption.
Environmental Fate
Photolytic. Low et al. (1991) reported that the photooxidation of aqueous secondary amine
solutions by UV light in the presence of titanium dioxide resulted in the formation of ammonium
and nitrate ions.
Chemical/Physical. Diethylamine reacted with NOx in the dark forming diethylnitrosamine. In
an outdoor chamber, photooxidation by natural sunlight yielded the following products:
diethylnitramine, diethylformamide, diethylacetamide, ethylacetamide, ozone, acetaldehyde, and
peroxyacetyl nitrate (Pitts et al., 1978).
Reacts with mineral acids forming water-soluble salts (Morrison and Boyd, 1971).
Stoffwechsel
Little information is available regarding the metabolism of diethylamine. The
amine can be readily absorbed from the respiratory and gastrointestinal tract. It has
been reported that following oral administration of diethylamine hydrochloride to
humans, much of the amine was recovered in the urine (Beard and Noe 1978). This
suggests that it is not readily metabolized and, therefore, may not be a substrate for
monoamine oxidase. When administered intraperitoneally to rats, it was moderately
inhibitory with respect to liver monoamine oxidase (Valiev 1974). Diethylamine
may serve as a precursor for the formation of the reportedly carcinogenic
N-nitrosoamines and, indeed, when a diethylamine containing liquid was examined
for nitrosation reactions under simulated conditions of the human stomach,
N-nitrosodiethylamine was formed (Ziebarth 1985).
Lager
Diethylamine should be protected from physical damage. It should be kept stored in a
cool, dry, well-ventilated location, away from incompatible chemical substances and away
from fi re hazard and smoking areas. The containers should be bonded and grounded for
transfer to avoid static sparks. Storage and use areas should be no smoking areas.
l?uterung methode
Dry diethylamine with LiAlH4 or KOH pellets. Reflux with, and distil it from, BaO or KOH. Convert it to the p-toluenesulfonamide and crystallise to constant melting point from dry pet ether (b 90-120o), then hydrolyse with HCl, excess NaOH is added, and the amine is passed through a column of activated alumina. Redistil the amine and dry it with activated alumina before use [Swift J Am Chem Soc 64 115 1942]. [Beilstein 4 III 313.] § A polystyrene diethylaminomethyl supported version is commercially available.
Vorsichtsma?nahmen
Occupational workers and users should be very careful during the use and chemical management
of diethylamine. Workers should wear impervious protective clothing, including
boots, gloves, a laboratory coat, apron or coveralls, as appropriate, to prevent skin contact. The chemical is very hazardous, corrosive, and harmful, and is a very flammable liquid
and vapor. Exposures to vapor may cause fl ash fi re. It causes burns and adverse effects
to the cardiovascular system. Workers should use chemical safety goggles and a full-face
shield to avoid splashing of the chemical substance. An eye-wash fountain and quickdrench
facilities in the work area should be maintained by the chemical management unit.
Diethylamin, in w?ssriger L?sung Upstream-Materialien And Downstream Produkte
Upstream-Materialien
Downstream Produkte
Diethylcyanamid
Tetraethylthiuramdisulfid
Trapidil
2-(N,N-DIETHYLAMINOCARBONYL)PHENYLBORONIC ACID
N,N-Diethylaminoacetonitril
ESFENVALERATE FREE ACID METABOLITE
Zinkbis(diethyldithiocarbamat)
5-AMINO-3-METHYL-THIOPHENE-2,4-DICARBOXYLIC ACID DIMETHYL ESTER
5-(N,N-Diethylaminosulfonyl)-2-methoxybenzoldiazoniumchlorid
2-AMINO-6-METHYL-4,5,6,7-TETRAHYDRO-1-BENZOTHIOPHENE-3-CARBONITRILE
1,4,6-Trimethyl-1H-pyrazolo[3,4-b]pyridin-3-ylamine ,97%
2-AMINO-5,6-DIHYDRO-4H-CYCLOPENTA[B]THIOPHENE-3-CARBONITRILE
2-Amino-4,5,6,7-tetrahydrobenzo[b]thiophen-3-carbonitril
2-AMINO-4,5-DIMETHYL-THIOPHENE-3-CARBONITRILE
Benzylsalicylat
1-(4-Iodphenyl)ethan-1-on
Nikethamid
Lidocainhydrochlorid
Diethylammoniumdiethyldithiocarbamat
3-(DIETHYLAMINO)PROPANOIC ACID
2-Chlor-N,N-diethylpropionamid
Etamsylat
2-Hydroxy-4,6-dimethylnicotinonitril
(5-BROMO-PYRIMIDIN-2-YL)-DIETHYL-AMINE
Procainhydrochlorid
Diethylammoniumchlorid
4-phenyl-1-(p-tolylsulphonyl)piperidine-4-carboxylic acid
Montelukast
BIS(DIETHYLAMINO)CHLOROPHOSPHINE
Benzylcinnamat
2-Chloro-3-cyano-4,6-dimethylpyridine
1,1-Diethylguanidinhydrochlorid
Diethylcarbamoylchlorid
3-Amino-N,N-diethyl-4-methoxyben-zolsulfonamid
N,N-Diethyl-m-toluamid
N,N-Diethyl-1,3-diaminopropan
coating adhesive tiemao 102
N,N-Diethyl-4-methyl-1-piperazincarboxamid
Tris(diethylamino)phosphin
4,6-DIMETHYL-1H-PYRAZOLO[3,4-B]PYRIDIN-3-AMINE
