Piperidin Chemische Eigenschaften,Einsatz,Produktion Methoden
ERSCHEINUNGSBILD
FARBLOSE FLüSSIGKEIT MIT CHARAKTERISTISCHEM GERUCH.
PHYSIKALISCHE GEFAHREN
Die Dämpfe sind schwerer als Luft und können sich am Boden ausbreiten. Fernzündung möglich.
CHEMISCHE GEFAHREN
Zersetzung beim Verbrennen unter Bildung giftiger Rauche mit Stickstoffoxiden. Mittelstarke Base. Reagiert sehr heftig mit Oxidationsmitteln. Reagiert sehr heftig mit Dicyanofurazan, N-Nitrosoacetanilid und 1-Perchlorylpiperidin unter Explosionsgefahr.
ARBEITSPLATZGRENZWERTE
TLV nicht festgelegt (ACGIH 2005).
MAK nicht festgelegt (DFG 2005).
AUFNAHMEWEGE
Aufnahme in den Körper durch Inhalation der Dämpfe, über die Haut und durch Verschlucken.
INHALATIONSGEFAHREN
Nur ungenügende Angaben vorhanden über die Geschwindigkeit, mit der eine gesundheitsschädliche Konzentration in der Luft beim Verdampfen bei 20°C erreicht wird.
WIRKUNGEN BEI KURZZEITEXPOSITION
WIRKUNGEN BEI KURZZEITEXPOSITION: Die Substanz verätzt die Augen, die Haut und die Atemwege. ätzend beim Verschlucken. Inhalation des Dampfes in hoher Konzentration kann zu Lungenödem führen (s.Anm.). Die Auswirkungen treten u.U. verzögert ein. ärztliche Beobachtung notwendig.
LECKAGE
Ausgelaufene Flüssigkeit in abdichtbaren Behältern sammeln. Reste mit Sand oder inertem Absorptionsmittel aufnehmen und an einen sicheren Ort bringen. Persönliche Schutzausrüstung: Umgebungsluftunabhängiges Atemschutzgerät.
R-Sätze Betriebsanweisung:
R61:Kann das Kind im Mutterleib schädigen.
R10:Entzündlich.
R20/21:Gesundheitsschädlich beim Einatmen und bei Berührung mit der Haut.
R34:Verursacht Verätzungen.
R23/24:Giftig beim Einatmen und bei Berührung mit der Haut.
R11:Leichtentzündlich.
S-Sätze Betriebsanweisung:
S53:Exposition vermeiden - vor Gebrauch besondere Anweisungen einholen.
S16:Von Zündquellen fernhalten - Nicht rauchen.
S26:Bei Berührung mit den Augen sofort gründlich mit Wasser abspülen und Arzt konsultieren.
S36/37/39:Bei der Arbeit geeignete Schutzkleidung,Schutzhandschuhe und Schutzbrille/Gesichtsschutz tragen.
S45:Bei Unfall oder Unwohlsein sofort Arzt zuziehen (wenn möglich, dieses Etikett vorzeigen).
S27:Beschmutzte, getränkte Kleidung sofort ausziehen.
Aussehen Eigenschaften
C5H11N; (Hexahydropyridin; Pentamethylenimin). Farblose, nach Ammoniak riechende Flüssigkeit.
Gefahren für Mensch und Umwelt
Piperidin zersetzt sich schlagartig oberhalb 110鳦. Mit starken Oxidationsmitteln kann es zu explosionsartigen Reaktionen kommen. Die Dämpfe sind viel schwerer als Luft und bilden mit Luft explosionsfähige Gemische.
Verursacht starke Reizungen nach Augen- und Hautkontakt. Inhalation führt zu Schleimhautreizungen, Husten und Atemnot. Nach Verschlucken kommt es zu Übelkeit und Erbrechen, Schleimhautirritationen im Mund, Rachen, Speiseröhre und Magen-Darmtrakt. Nach Resorption kommt es zu Speichelfluß, Atemnot, Muskelbeschwerden und Blutdruckanstieg. Nach Aufnahme größerer Mengen an den Beinen beginnende allmählich aufsteigende Lähmung bis zur Atemlähmung bei vollem Bewu&szzlig;tsein.
Wassergefährdender Stoff (WGK 2).
Schutzmaßnahmen und Verhaltensregeln
Alle Arbeiten im Abzug durchführen.
Latex-Schutzhandschuhe nur als kurzfristiger Spritzschutz.
Verhalten im Gefahrfall
Mit flüssigkeitsbindendem Material (z.B. Rench Rapid, Chemizorb) aufnehmen und der Entsorgung zuführen. Mit Wasser nachreinigen.
Wasser, Kohlendioxid, Pulver, Schaum.
Erste Hilfe
Nach Hautkontakt: Mit reichlich Wasser und Seife abwaschen.
Nach Augenkontakt: Bei geöffnetem Lidspalt mind. 10 Min. mit Wasser spülen. Augenarzt konsultieren.
Nach Einatmen: Für viel Frischluft sorgen. Bei Atemstillstand Atemspende oder Gerätebeatmung.
Nach Verschlucken: Erbrechen auslösen. Sofort Arzt hinzuziehen.
Nach Kleidungskontakt: Kontaminierte Kleidung entfernen.
Laxans: Natriumsulfat (1Eßl. auf 1/4 l Wasser).
Ersthelfer: siehe gesonderten Anschlag
Sachgerechte Entsorgung
Als Sondermüll entsorgen.
Chemische Eigenschaften
Piperidine is a clear, colorless liquid. Pepper, ammonia or amine odor.
Occurrence
Piperidine occurs at low levels in a variety of food products (Neurath et al 1977),
including baked ham (0.2 p.p.m.), milk (0.11 p.p.m.) coffee (1 p.p.m. dry) (Singer
and Lijinsky 1976) and canned fish (Tanikawa and Motohiro 1960). It is also
found in black pepper (Windholz 1983), hemp (Obata and Ishikawa 1960),
hemlock (Cromwell 1956) and tobacco (Furia and Bellanca 1975). Piperidine is a
natural constituent of skin (Sax and Lewis 1987), human urine (Von Euler 1944),
brain (Honegger and Honegger 1960) and cerebrospinal fluid (Perry et al 1964).
Humans excrete about 3-20 mg/d in the urine (Reinhardt and Britelli 1981).
Verwenden
Piperidine is an organic heterocyclic amine widely used as building block and reagent in the synthesis of organic compounds including pharmaceuticals.
synthetische
Usually prepared by electrolytic reduction of pyridine.
Definition
piperidine: A saturated heterocycliccompound having a nitrogen atom ina six-membered ring, C
5H
11N; r.d.0.86; m.p. –7°C; b.p. 106°C. The structureis present in many alkaloids
Vorbereitung Methode
Piperidine is usually prepared by the electrolytic reduction of pyridine. It may also
be obtained by heating piperidine with alcoholic KOH or by the cyclization of
1,5-diaminopentane hydrochloride (Windholz 1983). U.S. production in 1983 was
approximately 606,000 pounds (HSDB 1988). Commercial piperidine is supplied
in two grades, 95 and 98 percent pure (Sax and Lewis 1987).
Application
The secondary amine piperidine is highly reactive and is therefore frequently employed as an intermediate for pharmaceuticals and for plant protection agents. It is also used as a vulcanization accelerator in rubber manufacture and as an oil or fuel additive. Piperidine and, in many cases, piperidine acetate are useful catalysts for condensation reactions, e.g., the Knoevenagel reaction, aldol condensation, and the condensation of a nitroparaffin with an aldehyde. However, for the last of these reactions, diethylamine is the preferred catalyst. The use of piperidine is particularly advisable where the reactants or products are unstable in the presence of stronger bases.
Allgemeine Beschreibung
A clear colorless liquid with a pepper-like odor. Less dense than water, but miscible in water. Will float on water. Flash point 37°F. Melting point -15.8°F (-9°C). Boiling point 222.8°F (106°C). May severely irritate skin and eyes. May be toxic by ingestion and inhalation. Vapors heavier than air. Used to make rubber and as a solvent.
Air & Water Reaktionen
Highly flammable. Miscible in water.
Reaktivität anzeigen
1-Oxa-4-azacyclohexane 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
An irritation threshold of 26 p.p.m. has been reported from studies on human
volunteers (Bazarova and Migukina 1975). Levels of 2 to 5 p.p.m. in air have been
recorded during the transfer of piperidine from drums in a semi-closed system. At
this level, the vapors were intolerable but no irritation was observed (ANON
1982). In an accidental case of skin exposure, third-degree burns developed after
only 3 min of skin contact (Linch 1965). Piperidine has a pronounced emetic effect
in humans. When administered to schizophrenic patients at doses of 1 to 6 g/d, it
was shown to cause nausea and a subjective sense of well being (Giacobini 1976;
Tasher et al 1960). The primary, but low-level, means of human exposure,
however, is from the natural piperidine content of foods (HSDB 1988).
Brandgefahr
1-Oxa-4-azacyclohexane evolves explosive concentrations of vapor at normal room temperatures. When heated to decomposition, 1-Oxa-4-azacyclohexane emits highly toxic fumes of nitrogen oxides. Dangerous, when exposed to heat, flame, or oxidizers. Avoid 1-Perchloryl1-Oxa-4-azacyclohexane and oxidizing materials. 1-Oxa-4-azacyclohexane is a reactive compound and forms complexes with the salts of heavy metals. 1-Oxa-4-azacyclohexane evolves explosive concentrations of vapor at normal room temperatures. Keep away from igniting sources and heat.
Industrielle Verwendung
Piperidine is used as a solvent, a curing agent for rubber and epoxy resins, a
catalyst in silicone esters, an intermediate in organic synthesis and as a complexing
agent (HSDB 1988; Reinhardt and Britelli 1981). It is a trace constituent in oils
and fuels (Sax and Lewis 1987). It is used in the manufacture of local anesthetics,
analgesics and other pharmaceuticals, and also for wetting agents and germicides
(Gehring 1983). It is also used as a flavor additive in soups, meats, condiments,
baked goods, candy and non-alcoholic beverages at 0.05-5.0 p.p.m. (Furia and
Bellanca 1975).
Sicherheitsprofil
Poison by ingestion,
skin contact, and intraperitoneal routes.
Moderately toxic by subcutaneous route.
Mildly toxic by inhalation. An experimental
teratogen. Experimental reproductive effects
by inhalation. A skin irritant. Mutation data
reported. A very dangerous fire hazard when
exposed to heat, flame, or oxidizers. Can
react vigorously with oxidzing materials. To
fight fire, use alcohol foam, CO2, dry
chemical. Explodes on contact with 1-
perchloryl-piperidme, dqanofurazan, N-
nitrosoacetadde. When heated to
decomposition it emits highly toxic fumes of
NOx. Used in agriculture and
pharmaceuticals, and as an intermediate for
rubber accelerators. Used in production of
drugs of abuse.
mögliche Exposition
Piperidine is used in agriculture and pharmaceuticals; intermediate for rubber accelerators; as a solvent; as a curing agent for rubber and epoxy resins; catalyst for condensation reactions; as an ingredient in oils and fuels; complexing agent; manufacture of local anesthetics; in analgesics; pharmaceuticals, wetting agents; and germicides; synthetic flavoring. Not registered as a pesticide in the Unied States.
Carcinogenicity
No tumors were produced in
rats given piperidine (0.09%) in drinking water for
1 year. Mice receiving 19 doses of 50 mg/kg by intraperitoneal
injection within 61 weeks followed by an 18-week
observation period showed no increase in cancer incidences
(251). Piperidine and sodium nitrite given together
also failed to produce tumors. The failure of this treatment was surprising because nitrosopiperidine induced a high
incidence of lung and esophageal tumors. The authors
suggest that the relative strong basicity of piperidine
reduced the rate of reaction with nitrite to such an extent
that an ineffective amount of nitrosopiperidine was
formed. In mice that had cholesterol pellets containing
piperidine implanted in their bladders and were given
sodium nitrite in their drinking water, an increase in bladder
cancers was produced. Piperidine given as a series of
24 injections in groups of mice failed to produce lung
tumors in the strain A mouse cancer screen. When
piperidine and sodium nitrite were incubated in the isolated
rat urinary bladder, nitrosopiperidine was detected in the
bladder contents. No studies designed to evaluate the carcinogenic
potential of piperidine alone following lifetime
exposures have been reported.
Stoffwechsel
Piperidine is readily absorbed through the gastrointestinal tract, skin and lungs
(HSDB 1988). In hens, 35 to 70% of an injected dose is rapidly excreted
unchanged in the urine (Williams 1959; Sperber 1949). Rabbits also excrete
piperidine unchanged (Hildebrandt 1900). When injected intraventricularly into
rats, piperidine disappeared exponentially with a half-life of 20 min (Meek 1973).
In a more recent study, Okano et al (1978) found that in rats most of an i.p. dose of
[3H]-piperidine was excreted unchanged. Two major metabolites were identified
as 3- and 4-hydroxypiperidine. Both compounds were also found in untreated
animals and thus are probably metabolites of piperidine of exogenous or endogenous
origin. These metabolites represent a detoxification mechanism, since they
lack the potent pharmacological activities of the parent compound. Two unidentified
metabolites were assumed to be conjugates. In a much earlier study, Novello
et al (1926) claimed that piperidine was excreted as the ethereal sulfate. Metabolic
studies of analgesics and anesthetics containing the piperidine ring have demonstrated
the occurrence of N-hydroxylation, formation of a 6-oxo-derivative, and
C-oxidative ring cleavage (Oelschlager and Al Shaik 1985). N-nitrosopiperidine
has been synthesized from piperidine and sodium nitrite in the gastric contents,R.L. Reed
isolated stomach and isolated small intestine of rats (Alam et al 1971; Epstein
1972).
Versand/Shipping
UN2401 Piperidine, Hazard Class: 8; Labels: 8-Corrosive material, 3-Flammable liquid.
läuterung methode
Dry piperidine with BaO, KOH, CaH2, or sodium, and fractionally distil (optionally from sodium, CaH2, or P2O5). Purify from pyridine by zone melting. [Beilstein 22 H 6, 22
Inkompatibilitäten
Piperidine is a highly flammable liquid. Vapor may form explosive mixture with air (at room temperature). A medium-strong base. Reacts violently with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.); contact may cause fires or explosions. Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides. Piperidine 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.
Piperidin Upstream-Materialien And Downstream Produkte
Upstream-Materialien
Downstream Produkte
ethyl-2-Amino-4,5,6,7-tetrahydrobenzo[b]thiophen-3-carboxylat
5-Nitropyrimidin-2-amin
2',4',5'-Trimethoxycinnamsure
Bis(piperidinothiocarbonyl)tetrasulfid
6-BROMO-3-BUTYRYL-2H-CHROMEN-2-ONE
RARECHEM AL BI 0736
2-Chloro-6-methyl-3-pyridinecarbonitrile
2-AMINO-4-ETHYL-5-METHYL-THIOPHENE-3-CARBOXYLIC ACID METHYL ESTER
7-HYDROXY-2-OXO-2H-CHROMENE-3-CARBOXYLIC ACID METHYL ESTER
1,2,3,5-TETRAHYDRO-8-THIA-5,7-DIAZA-CYCLOPENTA[A]INDENE-4-ONE
3,4-(Methylenedioxy)cinnamic acid
Cloperastin
3-PYRIDIN-2-YL-PROPIONIC ACID H2SO4
5-METHYL-4-ISOXAZOLESULFONYL CHLORIDE
3-ACETAMIDOCOUMARIN
3-(TRIFLUOROMETHOXY)CINNAMIC ACID
2-AMINO-6-METHYL-4,5,6,7-TETRAHYDRO-1-BENZOTHIOPHENE-3-CARBOXAMIDE
NAPHTHALENE-2,3-DICARBOXALDEHYDE
5,6,7,8-TETRAHYDRO-3H-BENZO[4,5]THIENO[2,3-D]-PYRIMIDIN-4-ONE
3-CYANO-7-METHOXYCOUMARIN
3-(3-AMINOPHENYL)-2H-CHROMEN-2-ONE
Benproperinphosphat
4-ETHOXYCINNAMIC ACID
3',5'-Dimethoxycinnamsure
α,α-Diphenylpiperidin-1-butanolhydrochlorid
7-HYDROXY-2-OXO-2H-CHROMENE-3-CARBOXYLIC ACID METHYL ESTER
4-Fluorzimtsaeure
2,4'-Dimethyl-3-piperidinopropiophenonhydrochlorid
N-(2-Aminoethyl)piperidin
1-PIPERIDINEPENTANOL
5-BROMO-2-FLUOROCINNAMIC ACID
Minoxidil
4-Hydroxy-3,5-dimethoxybenzaldehyd
6-CHLORO-2-OXO-2H-CHROMENE-3-CARBOXYLIC ACID
2-AMINO-5,6-DIHYDRO-4H-CYCLOPENTA[B]THIOPHENE-3-CARBOXYLIC ACID ETHYL ESTER
3-(4-AMINO-PHENYL)-CHROMEN-2-ONE
4-Hydroxy-3,5-dimethoxyzimtsure
3-ACETYL-7-HYDROXY-2H-CHROMEN-2-ONE
2-AMINO-5,6-DIHYDRO-4H-CYCLOPENTA[B]THIOPHENE-3-CARBOXYLIC ACID METHYL ESTER
3-(3-METHYL-2-THIENYL)ACRYLIC ACID
