79-09-4 Usage
Description
Propionic acid, also known as propanoic acid and methylacetic acid, is a short-chain saturated fatty acid with the chemical formula CH3CH2COOH. It is a clear, oily, aqueous liquid with a pungent rancid odor and is corrosive to most metals and tissue. Propionic acid is the shortest fatty acid that exhibits the classic behaviors of similar compounds and has a role as an antifungal drug.
Uses
1. Used in Food Industry:
Propionic acid is used as a mold inhibitor and preservative for grains and wood chips, as well as in the manufacture of fruit flavors and perfume bases. It is also used as the sodium, calcium, and potassium salts as a preservative, which yield the free acid in the pH range of the food in which they are used. It functions principally against mold.
2. Used in Pharmaceutical Industry:
Propionic acid has a role as an antifungal drug, making it useful in the pharmaceutical industry for treating various fungal infections.
3. Used in Chemical Industry:
Propionic acid is used in nickel electroplating solutions, which makes it an essential component in the chemical industry.
4. Used in Perfumery:
Due to its strong odor, propionic acid is used in the production of perfumes, contributing to the creation of various fragrances.
5. Used in Flavor Industry:
Propionic acid is used in the manufacture of artificial flavors, enhancing the taste of various food products.
6. Used in Manufacturing Propionates:
Propionic acid is used in the production of propionates, which are essential for various industrial applications.
Taste Threshold Values:
Propionic acid has taste characteristics at 60 ppm, described as acidic, dairy with a pronounced fruity lift.
Occurrence:
Propionic acid is found in various fruits, vegetables, and other food items such as apple, apple juice, banana, currants, pineapple, raspberry, papaya, onion, sauerkraut, tomato, vinegar, beef, beef broth, beer, blackberry juice, bread, cheese, cherry juice, butter, yogurt, milk, cream, lean and fatty fish, cured pork, cooked beef and mutton, chicken fat, cognac, rum, whiskies, cider, sherry, roasted cocoa bean, cocoa powder, coffee, black currant juice, white currant juice, grape juice, grape musts and port wine, grapefruit juice, grape syrup, orange juice, Valencia orange oil, orange essence, roasted peanuts, pecans, potato chips, honey, soybean, Arctic bramble, coconut meat, cloudberry, mushroom, sesame seed, cardamom, rice, jackfruit, sake, buckwheat, laurel, peated malt, cassava, Bourbon vanilla, oyster, mussels, and scallop.
Production Methods
Propionic acid can be obtained from wood pulp waste liquor by
fermentation. It can also be prepared from ethylene, carbon
monoxide and steam; from ethanol and carbon monoxide using
boron trifluoride catalyst; from natural gas; or as a by-product in
the pyrolysis of wood. Very pure propionic acid can be obtained
from propionitrile. Propionic acid can be found in dairy products in
small amounts.
Biotechnological Production
Generally, propionic acid is produced via petrochemical routes. However, fermentative
processes are interesting for food-grade production, although the price
of biotechnologically produced propionic acid may be twice that of petrochemistry-
based propionic acid. The microbial production of propionic acid is done
with propionibacteria (e.g. Propionibacterim freudenreichii) . Several
fermentation methods have been studied. For example, an extractive fermentation
is suggested to avoid low productivity and yields caused by product inhibition
. With this technique, a product concentration of 75 g.L-1 propionic acid, a
yield of 0.66 g propionic acid per gram lactose, and a productivity of approximately
1 g.L-1.h-1 are reached .
Different substrates, such as glycerol , wheat flour , or mixtures of
glycerol and glucose , have been analyzed to reduce costs. Also, techniques of
cell immobilization show promising results . Fibrous-bed reactor systems show
the highest product concentrations: up to 106 g.L-1 propionic acid and a yield of
0.56 g propionic acid per gram glycerol. In recent years, metabolic engineering
has been used to improve the acid tolerance and to reduce byproduct formation .
104 H. Quitmann et al.
For example, the acetate kinase gene has been inactivated by mutation of Propionibacterium
acidipropionici . Additionally, an adaptive evolution has been
carried out. As result, the productivity was enhanced by approximately 50 %, up to
0.25 g.L-1.h-1 and a yield of 0.59 g propionic acid per gram glycerol, using
immobilized cells adapted to high acid concentration.
Air & Water Reactions
Dilution with water causes release of heat.
Reactivity Profile
Propionic acid reacts as an acid to neutralize bases in exothermic reactions. Burns when exposed to heat, flame or oxidizers. When heated to decomposition emits acrid smoke and irritating fumes [Lewis, 3rd ed., 1993, p. 1090].
Hazard
Moderate fire risk. Strong eye, skin and
upper respiratory tract irritant.
Health Hazard
Propionic acid is a toxic and corrosive liquid. Contact with the eyes can result ineye injury. Skin contact may cause burns.Acute exposures to its vapors can causeeye redness, mild to moderate skin burns,and mild coughing (ACGIH 1986). Ingestionof high amounts of this acid may producecorrosion of the mouth and gastrointestinaltract in humans. Other symptoms includevomiting, diarrhea, ulceration, and convulsions. Oral LD50 value in rats is about3500–4300 mg/kg. The LD50 value by skinabsorption in rabbits is 500 mg/kg..
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.
Flammability and Explosibility
Flammable
Pharmaceutical Applications
Propionic acid is primarily used as an antioxidant and antimicrobial
preservative in foods, and in oral and topical pharmaceutical
applications. It is also used as an esterifying agent.
Clinical Use
Propionic acid is an antifungal agent that is nonirritatingand nontoxic. After application, it is present in perspiration in low concentration ( 0.01%). Salt forms with sodium,potassium, calcium, and ammonium are also fungicidal.Propionic acid is a clear, corrosive liquid with a characteristicodor. It is soluble in water and alcohol. Thesalts are usually used because they are nonvolatile andodorless.
Safety Profile
Poison by
intraperitoneal route. Moderately toxic by
ingestion, skin contact, and intravenous
routes. A corrosive irritant to eyes, skin, and
mucous membranes. Flammable liquid.
Highly flammable when exposed to heat,
flame, or oxidizers. To fight fire, use alcohol
foam. When heated to decomposition it
emits acrid smoke and irritating fumes.
Safety
Propionic acid is generally regarded as a nontoxic and nonirritant
material when used in low levels as an excipient. Up to 1% may be used in food applications (up to 0.3% in flour and cheese products).
Propionic acid is readily metabolized.
The pure form of propionic acid is corrosive and will cause burns
to any area of contact. Both liquid and vapor forms are flammable.
Concentrated propionic acid is harmful if swallowed, inhaled or
absorbed through the skin. See also Sodium Propionate.
(mouse, IV): 0.63 g/kg
(rabbit, skin): 0.5 g/kg
(rat, oral): 2.6 g/kg
Synthesis
Commercial processes produce propionic acid by chemical synthesis and in small quantities by bacterial fermentation. Industrially Propionic acid is produced by hydrocarboxylation of ethylene in presence nickel carbonyl as a catalyst.
Potential Exposure
Propionic acid is used in the manufac-
ture of inorganic propionates and propionate esters which
are used as mold inhibitors, electroplating additives; emul-
sifying agents; flavors and perfumes. It is an intermediate
in pesticide manufacture, pharmaceutic manufacture; and in
the production of cellulose propionate plastics. Also used
as grain preservative.
Carcinogenicity
Rats fed high levels of propionic
acid (4%) in a powdered diet developed forestomach neoplasia,
which was believed to have arisen from sustained high
levels of cellular proliferation. When administered at
4% in the diet as a pellet rather than as a powder, cellular
hyperplasia and the associated severe inflammatory response
were absent. In another study whereWistar ratswere fed
75%bread containing5%of the salt, sodiumpropionate rather
than the acid for 1 year, no histopathology of the forestomach
was reported. This suggests that the form of chemical (salt
versus free acid), as well as the type of diet, is also an
important factor in eliciting this effect. Harrison
notes that a variety of chemicals, chemical and mechanical
irritants, parasites, and dietary deficiencies cause forestomach
tumors in rats. The predictive value of this finding in humans
is, therefore, problematic because humans have no forestomach
and food transit times are much faster. Interestingly,
propionic acid inhibited the growth of the human adenocarcinoma
cell line HT29 derived from similar epithelial tissue of
human colon cancer patients, whereas other short-chain fatty
acids, such as acetate, enhance transformation.
Environmental Fate
The widespread use of propionic acid has led to its detection in
waste streams and groundwater. It is a degradation product of
longer chain fatty acids, and has been detected in waste streams
following olive oil production and other processes. Additionally,
propionic acid has been qualitatively detected as a volatile
component of cooked potatoes and meats as well as in other
foods and beverages, including dairy products. Propionic acid
is a major component of the gas phase of the smoke of unfiltered
cigarettes, with quantities estimated at 100–300 mg per
cigarette.
In a direct fashion, propionic acid is released to the environment
through effluents from the manufacture, use, and
disposal of coal-derived and shale oil liquid fuels as well as
through wood-preserving chemical waste byproducts. Textile
mills and sewage treatment facilities may also be sources of
propionic acid-containing waste. Landfills and hazardous
waste sites can leach propionic acid to groundwater supplies.
Propionic acid can exist as a vapor in the ambient atmosphere
with a vapor pressure of 3.53 mmHg at 25 °C, and can
be degraded in the atmosphere by reaction with photochemically
produced hydroxyl radicals; the half-life for this reaction
in air is estimated to be 11 days. Photolysis of propionic acid is
not expected to be important, and wet deposition of propionic
acid is expected to occur readily as an atmospheric removal
process.
Biodegradation is likely to be the most important removal
mechanism of propionic acid from both soil and water. In
terrestrial environments, propionic acid will exist as a ratio of the
free acid and its conjugate base due to its pKa of 4.87. With an
estimated HenryK’s law constant of 4.15 ×10-7 atmm3 mol-1,
it is not expected to volatilize from soil. Its mobility in soil is
expected to be high, with an estimated Koc of 36. The high water
solubility of propionic acid and its existence as a charged species
result in low absorption by particulate and organic matter in
aquatic environments.
storage
Although stable, propionic acid is flammable. It should be stored in
an airtight container away from heat and flames.
Shipping
UN1848 Propionic acid, Hazard class: 8; Labels:
8-Corrosive material. UN3463 Propionic acid, with not
＜90% acid by mass, Hazard Class 8; Labels: 8-Corrosive
material, 3-Flammable liquid.
Purification Methods
Dry the acid with Na2SO4 or by fractional distillation, then redistil after refluxing with a few crystals of KMnO4. An alternative purification uses conversion to the ethyl ester, fractional distillation and hydrolysis. [Bradbury J Am Chem Soc 74 2709 1952.] Propionic acid can also be heated for 0.5hour with an amount of benzoic anhydride equivalent to the amount of water present (in the presence of CrO3 as catalyst), followed by fractional distillation. [Cham & Israel J Chem Soc 196 1960, Beilstein 2 IV 695.]
Toxicity evaluation
The behavior of propionic acid is largely pH dependent, and it
can alter the local pH in areas where it is applied or ingested.
It can behave as a moderately strong acid when concentrated,
and can be corrosive under such conditions. There has been
some evidence that propionic acid inhibits CO2 production
from palmitate in fibroblast cells and ureagenesis in rat liver
slices. This is perhaps related to fatty degeneration of the liver
and hyperammonemia in propionic and methylmalonic
acidemia – an autosomal disorder that results from a defect of
propionyl coenzyme A carboxylase. In the latter case, symptoms
can include vomiting, lethargy, hypotonia, and metabolic
ketoacidosis.
Incompatibilities
Propionic acid is a medium strong acid. Incompatible with sulfuric acid, strong bases; ammonia, isocyanates, alkylene oxides; epichlorohydrin. Reacts with bases; strong oxidizers; and amines, causing fire and explo- sion hazard. Attacks many metals forming flammable/ explosive hydrogen gas. It can be salted out of aqueous solutions by the addition of calcium chloride or other salts.
Waste Disposal
Incineration in admixture
with flammable solvent.
Regulatory Status
GRAS listed. Accepted for use in Europe as a food additive. In
Japan, propionic acid is restricted to use as a flavoring agent.
Check Digit Verification of cas no
The CAS Registry Mumber 79-09-4 includes 5 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 2 digits, 7 and 9 respectively; the second part has 2 digits, 0 and 9 respectively.
Calculate Digit Verification of CAS Registry Number 79-09:
(4*7)+(3*9)+(2*0)+(1*9)=64
64 % 10 = 4
So 79-09-4 is a valid CAS Registry Number.
InChI:InChI=1/C3H6O2/c1-2-3(4)5/h2H2,1H3,(H,4,5)
79-09-4Relevant articles and documents
Long term continuous chemoenzymatic dynamic kinetic resolution of rac-1-phenylethanol using ionic liquids and supercritical carbon dioxide
Lozano, Pedro,De Diego, Teresa,Mira, Corina,Montague, Kimberley,Vaultier, Michel,Iborra, Jose L.
, p. 538 - 542 (2009)
The long term continuous dynamic kinetic resolution (DKR) of rac-phenylethanol in IL/scCO2 biphasic systems was carried out by simultaneously using immobilized lipase (Novozym 435) and acidic zeolite catalysts at 50 °C and 100 bar, providing go
Interaction of Rhizopus delemar lipase with 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane and structurally related pesticides: Importance of 1:1 pesticide-lipase complexes
Kaneki,Nakauchi,Tanaka
, p. 263 - 273 (1988)
-
Catalytic carbonylation of ethylene in the presence of the Pd(acac)2-m-Ph2PC6H4So3Na(H)-AcOH system
Chepaikin, E. G.,Bezruchenko, A.P.,Leshcheva, A. A.,Boiko, G. N.
, p. 360 - 363 (1994)
Catalytic systems based on phosphine complexes of palladium have been developed for synthesizing propionic acid (monocarbonylation) and alternating (1:1) ethylene-carbon monoxide copolymers, i.e., polyketones (polycarbonylation). m-(Diphenylphosphino)benzenesulfonic acid or its sodium salt were used as ligands.Monocarbonylation proceeds at atmospheric pressure in dioxane or acetic acid solvents.Under high pressure, the reaction pathway can change from monocarbonylation, which occurs in the presence of the sodium salt of the ligand, to polycarbonylation when the sodium ion at the sulfo group is completely replaced by a proton.This change in reaction selectivity is observed when the process is performed in acetic acid.When the ligand is present both in the acid and the neutral form, products of di- and oligocarbonylation are formed along with propionic acid and the polyketone.These products were characterized by 1H and 13C NMR spectra as alternating keto acids C2H5(COCH2CH2)nCOOH, where n = 1-3.Kinetic equations were derived for the selective synthesis of propionic acid and polyketones. - Key words: carbonylation of ethylene; propionic acid; polyketone; Pd-based catalysts.
Selective gas phase hydrogenation of maleic anhydride over Ni-supported catalysts: Effect of support on the catalytic performance
Regenhardt, Silvina A.,Meyer, Camilo I.,Garetto, Teresita F.,Marchi, Alberto J.
, p. 81 - 87 (2012)
The gas phase hydrogenation of maleic anhydride to obtain γ-butyrolactone was studied using Ni supported on SiO2, SiO2-Al2O3 and zeolite H-BEA as catalysts. The samples were prepared by incipient wetness impregnation and characterized by N2 adsorption at -196 °C (Sg), X-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed desorption of NH3 (TPD-NH3) and chemisorption of H2. The reaction was carried out at 170 °C and 220 °C in a fixed bed reactor operating at atmospheric pressure. From the characterization results, it was determined that the degree of Ni2+-support interaction varies according to the following pattern: Ni/HBEA > Ni/SiO2-Al 2O3 > Ni/SiO2. All catalysts were very active in the hydrogenation of maleic anhydride to succinic anhydride. However, hydrogenolytic activity and stability of nickel-based catalyst varies with the degree of interaction Ni2+-support. Ni/H-BEA, in which Ni 2+-support interaction is the highest, was active in the hydrogenolysis of succinic anhydride to γ-butyrolactone but it was not stable. By contrast, Ni/SiO2-Al2O3 and Ni/SiO2, with medium or low degree of Ni2+-support interaction, were more stable than Ni/H-BEA. In addition, Ni/SiO 2-Al2O3, with a medium degree of Ni 2+-support interaction, was the most stable and selective to γ-butyrolactone, especially when the reaction was carried out at 220 °C.
Palladium(II) and/or copper(II)-catalyzed carboxylation of small alkanes such as methane and ethane with carbon monoxide
Nakata, Kazuyuki,Yamaoka, Yoshinori,Miyata, Tsutomu,Taniguchi, Yuki,Takaki, Ken,Fujiwara, Yuzo
, p. 329 - 334 (1994)
Small alkanes such as methane and ethane react with carbon monoxide in the presence of transition metal catalysts to give the corresponding carboxylic acids in high yields.For the reaction of ethane, the Pd(OAc)2/Cu(OAc)2 mixed catalyst is the best, whereas that of methane proceeds most efficiently by the Cu(OAc)2 catalyst system. Key words: Palladium; Carbon monoxide; Alkane activation; Copper; Methane; Ethane
Novel scorpionate and pyrazole dioxovanadium complexes, catalysts for carboxylation and peroxidative oxidation of alkanes
Silva, Telma F. S.,Luzyanin, Konstantin V.,Kirillova, Marina V.,Fatima Guedes Da Silva,Martins, Luisa M. D. R. S.,Pombeiro, Armando J. L.
, p. 171 - 187 (2010)
The dioxovanadium(V) complexes [VO2(3,5-Me2Hpz)3] [BF4] (1) (pz = pyrazolyl), [VO2{SO3C(PZ)3}] (2), [VO2{HB(3,5-Me2pz)3}] (3) and [VO2(HC(pz)3}j[BF4] (4), bearing pyrazole or scorpionate ligands, were obtained by reaction of triethyl vanadate [VO(OEt)3] with hydrotris(3,5-dimethyl-1-pyrazolyl)methane [HC(3,5-Me2pz)3] or 3,5-dimethylpyrazole (3,5-Me2HpZ; 1), lithium tris(1-pyrazolyl)methanesulfonate {Li[SO3C(pz)3], 2}, potassium hydrotris(3,5-dimethyl-l-pyrazolyl)borate {K[HB (3,5-Me2pz)3], 3} and hydrotris(1-pyrazolyl)methane [HC(pz)3, 4], respectively. Treatment of [VO(OEt)3] with potassium hydrotris(1-pyrazolyl)borate (K[HB(pz)3]) led to the mixed η3-tris(pyrazolyl)-borate and η2-bis(pyrazolyl)borate oxovanadium(IV) complex [VO{HB(pz)3}{H2B(pz)2}, 5]. The compounds were characterized by elemental analyses, IR, NMR and EPR spectroscopy, FAB and ESI mass spectrometry, cyclic voltammetry and, for 5, also by single crystal X-ray diffraction analysis. All complexes exhibit catalytic activity in the single-pot carboxylation [in trifluoroacetic acid/potassium peroxodisulfate (CF3COOH/K2S2O8)] of gaseous alkanes (methane and ethane) to carboxylic acids (yields up to 40%, TONs up to 157) and in the peroxidative oxidation [in water/acetonitrile (H2O/NCMe)] of liquid alkanes (cyclohexane and cyclopentane) to the corresponding alcohols and ketones (yields up to 24%, TONs up to 117), under mild conditions.
Selective Carbonylation of Propane in HF-SbF5: Control of the Activation Step via the Hydrocarbon/Carbon Monoxide Ratio
Delavarenne, Serge,Simon, Michel,Fauconet, Michel,Sommer, Jean
, p. 1049 - 1050 (1989)
The selectivity of propane carbonylation in HF-SbF5 is found to depend on the propane/CO ratio, and is rationalized in terms of two competing activation processes for the alkane.
CO2 as oxidant: an unusual light-assisted catalyst free oxidation of aldehydes to acids under mild conditions
Aniya, Vineet,Jain, Suman L.,Khan, Shafiur Rehman,Khatri, Praveen K.,Kumari, Alka,Naresh, K.,Ray, Anjan,Saini, Sandhya
, p. 2208 - 2211 (2022/02/17)
A novel visible light-driven catalyst-free oxidation of aldehydes using CO2 both in batch and flow photoreactors to get corresponding acids along with the formation of CO in the effluent gas is described.
Green, homogeneous oxidation of alcohols by dimeric copper(II) complexes
Maurya, Abhishek,Haldar, Chanchal
, p. 885 - 904 (2020/12/18)
Three pyrazole derivatives, 3,5-dimethyl-1H-pyrazole (DMPz) (I), 3-methyl-5-phenyl-1H-pyrazole (MPPz) (II), and 3,5-diphenyl-1H-pyrazole (DPPz) (III), were prepared via reacting semicarbazide hydrochloride with the acetylacetone, 1-phenylbutane-1,3-dione, and 1,3-diphenylpropane-1,3-dione, respectively. Complexes 1–3 were isolated by reacting CuCl2·2H2O with I–III, respectively, and characterized by CHNS elemental analyses, FT-IR, UV-Vis, 1H and 13C NMR, EPR spectra, and TGA/DTA. Molecular structures of the pyrazole derivatives I–III and copper(II) complexes 2 and 3 were studied through single-crystal XRD analysis to confirm their molecular structures. Overlapping of hyperfine splitting in the EPR spectra of the dimeric copper(II) complexes 1–3 indicates that both copper centers do not possess the same electronic environment in solution. The copper(II) complexes are dimeric in solid state as well as in solution and catalyze the oxidation of various primary and secondary alcohols selectively. Catalysts 1–3 show more than 92% product selectivity toward ketones during the oxidation of secondary alcohols. Surprisingly primary alcohols, which are relatively difficult to oxidize, produce carboxylic acid as a major product (48%–90% selectivity) irrespective of catalytic systems. The selectivity for carboxylic acid rises with decreasing the carbon chain length of the alcohols. An eco-friendly and affordable catalytic system for oxidation of alcohols is developed by the utilization of H2O2, a green oxidant, and water, a clean and greener solvent, which is a notable aspect of the study.
