| Use | PREPN OF CRYSTALLINE DERIVATIVES OF AROMATIC NITRO COMPD CONTAINING NUCLEAR HALOGEN ATOMS
SYNTHETIC FLAVOR
Used in the manufacture of local anesthetics, analgesics and other pharmaceuticals, and for wetting agents and germicides.
INT FOR RUBBER VULCANIZATION ACCELERATORS; HARDENING AGENT FOR EPOXY RESINS
SOLVENT & INTERMEDIATE; CATALYST FOR CONDENSATION REACTIONS; INGREDIENT IN OILS & FUELS; COMPLEXING AGENT
Seafood flavor
PROD: (1972) 2.17X10+8 GRAMS
(1975) 1.6X10+8 GRAMS
(1983) 2.75X10+8 g [R1]
IMPT: (1975) 3.57X10+6 GRAMS (PRINCPL CUSTMS DISTS)
(1984) 5.00X10+5 g [R2]
| Apparent Color | Clear, Colorless Liquid
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| Odor | Amine-Like odor ;Heavy, sweet, floral,animal odor
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| Boiling Point | 106 DEG C
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| Melting Point | -7 DEG C
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| Molecular Weight | 85.15
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| Misc | 0.8622 AT 20 DEG C/4 DEG C
PH: STRONG BASE
SOL: SOL IN ALL PROP IN WATER, ALC; SOL IN ETHER, ACETONE, BENZENE, CHLOROFORM
MAX ABSORPTION (GAS): 198 NM (LOG E= 3.5); SADTLER REF NUMBER: 135 (NMR) ; INDEX OF REFRACTION: 1.4534 @ 20 DEG C/D ; IR: 5991 (Sadtler Research Laboratories Spectral Collection) ; UV: 6-55 (Organic Electronic Spectral Data, Phillips et al, John Wiley & Sons, New York) ; MASS: 132 (Atlas of Mass Spectral Data, John Wiley & Sons, New York)
VAPD: 3.0 (AIR= 1)
VAP: 40 mm Hg at 29.2 deg C
SOAPY FEEL; SOLIDIFIES @ -13 DEG C TO -17 DEG C
FORMS COMPLEXES WITH SALTS OF HEAVY METALS
PIPERIDINE BEHAVES CHEMICALLY LIKE A TYPICAL ALIPHATIC SECONDARY AMINE
CONVERSION FACTORS: 1 MG/L IS EQUIV TO 287 PPM & 1 PPM IS EQUIV TO 3.5 MG/CU M
Blush resistence 80 % rh (@ 27 deg C); coefficient of expansion: 0.0011 cu cm/deg C
Heat capacity: 179.9 J/mol K (liquid) at 25 deg C
Orthorhombic prisms from alcohol; mp: 247 deg C; freely sol in water, alcohol /Piperidine hydrochloride/
Henry's Law constant= 4.35x10-6 atm-cu m/mole
DOT: Fire or Explosion: Flammable/combustible material; may be ignited by heat, sparks or flames. Vapors may travel to a source of ignition and flash back. Container may explode in heat of fire. Vapor explosion hazard indoors, outdoors or in sewers. Runoff to sewer may create fire or explosion hazard.
Health Hazards: May be poisonous if inhaled. Contact may cause burns to skin and eyes. Fire may produce irritating or poisonous gases. Runoff from fire control or dilution water may cause pollution.
Emergency Action: Keep unnecessary people away; isolate hazard area and deny entry. Stay upwind; keep out of low areas. Positive pressure self-contained breathing apparatus (SCBA) and structural firefighters' protective clothing will provide limited protection. Isolate for 1/2 mile in all directions if tank, rail car or tank truck is involved in fire. CALL CHEMTREC AT 1-800-424-9300 FOR EMERGENCY ASSISTANCE. If water pollution occurs, notify the appropriate authorities.
Fire: Some of these materials may react violently with water. Small Fires: Dry chemical, CO2, water spray or regular foam. Large Fires: Water spray, fog or regular foam. Move container from fire area if you can do it without risk. Do not get water inside container. Apply cooling water to sides of containers that are exposed to flames until well after fire is out. Stay away from ends of tanks. Withdraw immediately in case of rising sound from venting safety device or any discoloration of tank due to fire.
Spill or Leak: Shut off ignition sources; no flares, smoking or flames in hazard area. Do not touch or walk through spilled material; stop leak if you can do it without risk. Use water spray to reduce vapor; do not get water inside container. Small Spills: Take up with sand or other noncombustible absorbent material and place into containers for later disposal. Large Spills: Dike far ahead of liquid spill for later disposal.
First Aid: Move victim to fresh air and call emergency medical care; if not breathing, give artificial respiration; if breathing is difficult, give oxygen. In case of contact with material, immediately flush skin or eyes with running water for at least 15 minutes. Remove and isolate contaminated clothing and shoes at the site. Keep victim quiet and maintain normal body temperature.
FPOT: Dangerous /fire hazard/, when exposed to heat, flame or oxidizers.
NFPA: Reactivity: 3. 3= Includes materials that, in themselves, are capable of detonation, explosive decomposition, or explosive reaction, but which require a strong initiating source or heating under confinement. This includes materials that are sensitive to thermal and mechanical shock at elevated temperatures and pressures and materials that react explosively with water. Fires involving these materials should be fought from a protected location.
Flammability: 3. 3= Includes Class IB and IC flammable liquids and materials that can be easily ignited under almost all normal temperature conditions. Water may be ineffective in controlling or extinguishing fires in such materials.
Health: 2. 2= Materials that, on intense or continued (but not chronic) exposure, could cause temporary incapacitation or possible residual injury, including those requiring the use of respiratory protective equipment that has an independent air supply. These materials are hazardous to health, but areas may be entered freely if personnel are provided with full-face mask self-contained breathing apparatus that provides complete eye protection.
FIRE: ALCOHOL FOAM, CARBON DIOXIDE, DRY CHEMICAL.
If material on fire or involved in fire: Do not extinguish fire unless flow can be stopped. Use water in flooding quantities as fog. Solid streams of water may be ineffective. Cool all affected containers with flooding quantities of water. Use foam, dry chemical, or carbon dioxide. Keep run-off water out of sewers and water sources.
EXPL: THIS SUBSTANCE ... EVOLVES EXPLOSIVE CONCENTRATIONS OF VAPOR AT NORMAL ROOM TEMPERATURES.
REACTIVITY: DANGEROUS ... CAN REACT VIGOROUSLY WITH OXIDIZING MATERIALS.
Incompatibilities: 1-perchlorylpiperidine
Contact of dicyanofurazan, or its N-oxide (dicyanofuroxan), with ... piperidine ... is instantaneously explosive.
The dry anilide /of N-nitrosoacetanilide/ explodes on contact with a drop of piperidine.
/N-perchlorylpiperidine/ ... has exploded on ... contact with piperidine.
WHEN HEATED TO DECOMPOSITION, IT EMITS HIGHLY TOXIC FUMES OF OXIDES OF NITROGEN ... .
MORE VOLATILE THAN PYRIDINE
SHIP: No person may /transport,/ offer or accept a hazardous material for transportation in commerce unless that material is properly classed, described, packaged, marked, labeled, and in condition for shipment as required or authorized by ... /the hazardous materials regulations (49 CFR 171-177)./ [R3]
Int'l Air Shipments: Chemical: Piperidine. IMO Class: 3. UN 2401. Primary hazard label: Flammable liquid (packaging group II). Additional packaging instructions listed in the table must also be followed.
International Water Shipments: Chemical: Piperidine. IMO Class: 3.2; flammable liquid. UN 2401. Packaging Group: II. Label(s) required: Flammable liquid. [R4]
CLEANUP: If material not on fire and not involved in fire: Keep sparks, flames, and other sources of ignition away. Keep material out of water sources and sewers. Build dikes to contain flow as necessary. Attempt to stop leak if without undue personal hazard. Use water spray to knock-down vapors.
DISPOSAL: (a) Dissolve in such combustible solvent as alcohols, benzene, etc. Spray the solution into the furnace with afterburner and scrubber. (b) Pour into sodium bicarbonate or a mixture of sand/soda ash (9:1). After mixing, transfer into a paper carton filled with packing paper. Burn in an open furnace, or more efficiently in the furnace with afterburner and scrubber.
TOXICITY: ACUTE LOCAL: IRRITANT 3. 3= HIGH: MAY CAUSE DEATH OR PERMANENT INJURY AFTER VERY SHORT EXPOSURE TO SMALL AMT. ACUTE SYSTEMIC: INGESTION 2. 2= MODERATE: MAY INVOLVE BOTH IRREVERSIBLE & REVERSIBLE CHANGES NOT SEVERE ENOUGH TO CAUSE DEATH OR PERMANENT INJURY.
An irritation threshold of 26 ppm has been reported from studies on human volunteers.
Levels of 2 to 5 ppm 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.
In an accidental case of skin exposure, third degree burns developed after only 3 min of skin contact.
Piperidine has a pronounced emetic effect in humans. When administered to schizophrenic patients at doses of 1 to 6 g/day, it was shown to cause nausea and a subjective sense of well being.
NTOX: Exposure of rats and rabbits to 2.87 ppm piperidine 4 hr/day for 4 months decreased body weight gains, altered the cardiovascular system, brain electrical activity and spermatogenesis, and caused dystrophic changes in the liver and kidneys. At 0.57 ppm, arterial pressure was decreased and skin capillary permeability and neuromuscualr irritability were increased.
PIPERIDINE CAUSES MODERATELY SEVERE SKIN IRRITATION WHEN APPLIED TO GUINEA PIG SKIN ... SEVERE EYE DAMAGE WITH PERMANENT CORNEAL INJURY RESULTS FROM INSTILLATION IN RABBIT EYE. ... SUSTAINED ELEVATION OF BLOOD PRESSURE IS OBSERVED FOLLOWING IV INJECTION IN DOGS OR CATS ... /OF/ 5-10 MG/KG.
... DOSES /OF 5-10 MG/KG IV IN DOGS OR CATS/ STIMULATE RESPIRATIONS & INCREASE HEART RATE.
PIPERIDINE ... EXHIBITS RELATIVELY HIGH ... TOXICITY WHEN ADMIN UNDILUTED TO LABORATORY ANIMALS ... . 10% SOLN IN WATER IS ... LESS TOXIC WHEN GIVEN ORALLY TO RATS SINCE SOME ANIMALS SURVIVE 100 MG/KG BUT NOT 200 MG/KG. ANIMALS SHOW WEAKNESS, RESPIRATORY DISTRESS & CONVULSIONS.
PIPERIDINE ... EXHIBITS STRONG PRIMARY IRRITANT PROPERTIES FOR SKIN, MUCOUS MEMBRANES, & EYES, & RELATIVELY HIGH DEGREE OF ACUTE TOXICITY. EFFECTIVE DOSES PRODUCE ... ATAXIA ... .
LARGE DOSES BLOCK GANGLIONIC CONDUCTION. SMALL DOSES CAUSE BOTH PARASYMPATHETIC & SYMPATHETIC STIMULATION DUE TO ACTION ON GANGLIA.
Inhalation of 2.9 ppm piperidine 4 hr/day for 4 mo caused altered spermatogenesis in rats. Decreased embryo weight was caused by inhalation of 4.3 ppm, but not 0.9 ppm, piperidine in rats throughout pregnancy and 29 ppm also caused an increase in the resorption rate.
Piperidine tested negative in the Salmonella/microsome Ames test. It also tested negative in the EPA Genetox Program host-mediated assay.
/Piperidine tested negative in the following assays:/ direct bacterial, host-mediated, and microsomal mutagenesis.
Piperidine was not carcinogenic in the A mouse pulmonary tumor system and no DNA damage was found in an alkaline elution/rat hepatocyte assay.
In testing on rabbit eyes without control of pH, it caused severe injury of the cornea, graded 9 on a scale of 1 to 10 at twenty four hr. Tested in aqueous solution at 0.023 molar concentration by continuous application for ten min after mechanical removal of the corneal epithelium to permit penetration, at pH 11 the solution caused slight reversible graying of the cornea, and at pH 10 caused no significant injury.
NTXV: LD50 Rabbit sc 500 mg/kg
LD50 Rat oral 400 mg/kg
LD50 Mouse oral 30 mg/kg
LD50 Rabbit oral 145 mg/kg
LD50 Mouse ip 50 mg/kg
LC50 Mouse inhalation 1723 ppm, 1 hr
LC50 Guinea pig inhalation 3444 ppm, 1 hr
ADE: ... Piperidine is absorbed through the GI tract, through the skin and by inhalation.
IT IS WELL ABSORBED FROM GASTROINTESTINAL TRACT & ABSORPTION THROUGH SKIN IS SUFFICIENT TO PRODUCE DEATH IN SMALL ANIMALS. ABSORPTION FROM RESPIRATORY TRACT HAS NOT BEEN STUDIED.
PIPERIDINE HAS BEEN ISOLATED & IDENTIFIED IN ANIMAL & HUMAN URINE. MAN EXCRETES ABOUT 3-20 MG/DAY. ... WHEN PIPERIDINE IS INJECTED INTO HENS & RABBITS, MAJOR PORTION IS EXCRETED UNCHANGED.
METB: PIPERIDINE, A STRONG BASE, IS EXCRETED UNCHANGED, & IS NORMAL CONSTITUENT OF URINE PROBABLY ARISING FROM TRACES OF CADAVERINE FORMED BY INTESTINAL MICRO-ORGANISMS.
In hens, 35 to 70% of an injected dose is rapidly excreted unchanged in the urine. ... When injected iv into rats, piperidine disappeared exponentially with a half-life of 20 min. ... In rats most of an ip dose of (3)H 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.
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. N-nitrosopiperidine has been synthesized from piperidine and sodium nitrite in the gastric contents, isolated stomach and isolated small intestine of rats.
ACTN: It has potent nicotine like actions on the peripheral and central nervous systems. In the CNS, it produces a synaptic stimulation followed by depression. It counteracts experimentally induced aggression in mice and rats. ... It has transmittter like properties in the CNS of mollusk.
ENVIRONMENTAL: Piperidine is used commercially as a solvent, chemical intermediate, curing agent, catalyst, and complexing agent and is also found naturally in foods and fish. In soil and water, it is likely to biodegrade and in soil, it is likely to leach. In water at neutral conditions, piperidine will be dissociated and therefore evaporation will be pH dependent. On dry soil, its high vapor pressure would suggest significant evaporation. Because of its low octanol/water partition coefficient, bioconcentration of piperidine in fish is unlikely. Estimations of its fate in the atmosphere suggest a half-life of 3.4 days. Primary human exposure is due to food consumption. (SRC)
Found in small amounts in black pepper(1). Commonly detected in food products(3,4). Found in brain, skin, and urine of animals and in the brain, cerebrospinal fluid, and urine of humans(2). [R5]
Piperidine occurs at low levels in a variety of food products including baked ham (0.2 ppm), milk (0.11 ppm), coffee (1 ppm dry) and canned fish.
ARTS: Piperidine is used as a solvent and chemical intermediate, as a curing agent for rubber and epoxy chemical resins, a catalyst for condensation reactions, an ingredient in oils and fuels, and a complexing agent(1). [R6]
FATE: TERRESTRIAL FATE: Piperidine released to soil is likely to biodegrade, evaporate, or leach. Relative rates of these processes are unknown. Hydrolysis and absorption to soil are not important processes. (SRC)
AQUATIC FATE: Piperidine released to aqueous systems will biodegrade but the relative rates are unknown. Adsorption to sediments or suspended solids and evaporation should not be important because piperidine is highly dissociated at neutral pH and has a low Henry's Law constant. It is unknown whether photodegradation will be important. (SRC)
ATMOSPHERIC FATE: No experimental data relative to the environmental fate of piperidine in the atmosphere is available. Its estimated half-life in the atmosphere based upon reaction with hydroxy radicals is 3.4 days. (SRC)
Piperidine is readily biodegradable in screening tests using mixed soil and sewage(1) or sewage(2) inocula. Greater than 30% BOD theoretical in 2 weeks was observed with the mixed inoculum BOD test(1). There is some evidence from pure culture studies that suggests that under certain situations microorganisms may form N-nitrosopiperidine(3); however, other pure culture studies suggest that piperidine is not nitrosated(4). [R7]
Photolysis of piperidine with 254 nm light in anaerobic aqueous solutions of NaNO2 produced N-nitrosamines and N-nitramines(1). Whether similar reactions will occur in natural waters with sunlight is unknown. Estimates of the half-life in the atmosphere based upon reaction with hydroxyl radical is 3.4 days (assume 25 C and 8x10(+5) hydroxyl radicals per cc)(2). [R8]
The low octanol/water partition coefficient (0.84)(1) and the high amount of dissociation at neutral pH suggests that piperidine will not bioconcentrate in aquatic organisms(SRC). [R9]
The low octanol/water partition coefficient (0.84)(1) and high amount of dissociation at neutral pH suggests that piperidine will not adsorb strongly to soils or sediments(SRC). [R9]
The Henry's Law constant (4.35x10-6 atm-cu m/mole)(1) would suggest that piperidine will not evaporate rapidly from water. Its high vapor pressure (30mm Hg)(2) and low adsorption to soil would suggest that piperidine would evaporate rapidly from dry soil(SRC). [R10]
DRINKING WATER: Detected, not quantitated in District of Columbia drinking water(1). SURFACE WATER: Detected in rivers of Germany-9 samples, 6 pos. 0.5-9 ppb(2). [R11]
Detected, not quantitated, in soils not under cultivation(1). [R12]
Detected in preserved vegetables (eg, coffee, cocoa, tea, wine, barley, hops, malt) (10 samples, 1 pos, 0.1 ppm), pickles (12 samples, 6 pos, 0.1-5.6 ppm), stimulants (eg, coffee, cocoa, tea, wine, barley, hops, malt) (10 samples, 7 pos, 0.1-9 ppm)(1). Baked ham-0.2 ppm(2). Coffee-1 ppm(2). Fish sausage-9 ppb(3). Baked ham-0.81 ppm(3). [R13]
Detected in fish (6 samples, 4 pos., 0.2-0.7 ppm)(2). Cod roe-0.210 ppm(1). [R14]
Canned milk-0.3 ppm; whole milk-0.11 ppm(1). [R15]
Detected (0.8-16 ppm) in cigarette smoke condensate; not detected in unburned tobacco(1). [R15]
Primary human exposure appears to be from consumption of food containing natural amounts of piperidine. (SRC)
AIR INTAKE: Insufficient data; WATER INTAKE: (assume 1-10 ppb,see also WATC) 2-20 ug; FOOD INTAKE: (assume 0.01-0.1 ppm,see also FOOD and MILK)16-160 ug.
Piperidine is a food additive permitted for direct addition to food for human consumption as a synthetic flavoring substance and adjuvant in accordance with the following conditions: 1) the quantity added to food does not exceed the amount reasonably required to accomplish its intended physical, nutritive, or other technical effect in food, and 2) when intended for use in or on food it is of appropriate food grade and is prepared and handled as a food ingredient. [R16]
DETECTION OF PIPERIDINE WITH CHLORANIL ON TLC. [R17]
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