109-06-8 Usage
Description
2-Picoline, also known as 2-Methylpyridine, is a colorless liquid with a strong, unpleasant odor. It is a chemical compound that is highly stable in aqueous solutions but decomposes when heated to emit NOx. The chemical may also react with oxidizing agents. It is poisonous and produces poisonous vapor.
Uses
Used in Dye and Resin Industries:
2-Picoline is used as a solvent and as a chemical intermediate in the dye and resin industries. It serves to prepare dyes and resins.
Used in Pharmaceutical and Agrochemical Industries:
2-Picoline is used as an intermediate in agrochemicals and pharmaceuticals. It is also used in the synthetic pathway for the preparation of dearomatized, allylated, and carbon-hydrogen bond activated pyridine derivatives.
Used in Cigarette Smoke, Bone Oil, Coal Tar, and Coke Oven Emissions:
2-Picoline finds application as a constituent in cigarette smoke, bone oil, coal tar, and coke oven emissions.
Used as a Precursor:
2-Picoline acts as a precursor of 2-vinylpyridine, picolinic acid, and nitrapyrin.
Used in Studying Electron and Proton Transfer Reactions:
2-Picoline is employed to study the electron and proton transfer reactions of lumiflavin.
Used as a Reagent in Synthesis:
2-Picoline is used as a reagent in the synthesis of 2-Picolineborane, a non-toxic alternative to sodium borohydride for the labeling of oligosaccharides.
Industrial Uses:
2-Methylpyridine is used to make 2-vinylpyridine, which is then made into a terpolymer with styrene and butadiene. The latexes of these terpolymers are extensively employed in adhesives for bonding textiles to elastomers. It is also a chemical intermediate for 2-chloro-6-(trichloromethyl)pyridine and 2-vinylpyridine.
Occurrence:
2-Methylpyridine is released in atmospheric emissions from coal during processing into tar, pitch, and coke. It is also a byproduct of coal gasification and liquefaction processes and oil shale retorting. It is present in coal and is released in stack emissions. 2-Methylpyridine has been identified in effluents from timber products, organic chemicals, pharmaceuticals, and public waste treatment facilities. It is also a constituent of tobacco smoke and is biodegradable.
Production Methods
2-Methylpyridine is synthesized by distillation of coal tar or bone oil or by vapor phase reaction of acetaldehyde and ammonia in a 3:1 ratio followed by isolation of 2-methylpyridine from the reaction mixture (Considine 1974). It also can be synthesized from cyclohexylamine with excess ammonia and ZnCl2 at 350°C, resulting in a 40-50% yield; or prepared from ethylene-mercuric acetate adduct with ammonia water with a 70% yield (Windholz et al 1983). Production in 1977 probably exceeded one million pounds (Opresko 1982).
Synthesis Reference(s)
Journal of the American Chemical Society, 86, p. 5355, 1964 DOI: 10.1021/ja01077a077Synthesis, p. 26, 1976Tetrahedron Letters, 17, p. 383, 1976 DOI: 10.1016/S0040-4039(00)93738-9
Air & Water Reactions
Highly flammable. Water soluble.
Reactivity Profile
2-Picoline is hygroscopic. 2-Picoline reacts with hydrogen peroxide, iron(II) sulfate, sulfuric acid, oxidizing agents, acids, and metals.
Health Hazard
INHALATION, INGESTION OR SKIN ABSORPTION: Narcosis, headache, nausea, giddiness, vomiting. EYES: Severe irritation. SKIN: Causes burns. INGESTION: Irritation and gastric upset.
Health Hazard
2-Methylpyridine causes local irritation on contact with the skin, mucous membranes and cornea (Reinhardt and Brittelli 1981). Clinical signs of intoxication caused by the methyl pyridines include weight loss, diarrhea, weakness, ataxia and unconsciousness (Reinhardt and Brittelli 1981) as well as narcosis headache, nausea, giddiness and vomiting (Ketchen and Porter 1979). Chronic exposure to methylpyridine results in anemia and ocular and facial paralysis in addition to the previously mentioned symptoms (Ketchen and Porter 1979).
Flammability and Explosibility
Flammable
Safety Profile
Poison by
intraperitoneal route. Moderately toxic by
ingestion and skin contact. Mildly toxic by
inhalation. A skin and severe eye irritant.
Mutation data reported. Flammable liquid
when exposed to heat or flame. To fight
fire, use CO2, dry chemical. Mixtures with
hydrogen peroxide + iron(II) sulfate +
sulfuric acid may igmte and then explode.
When heated to decomposition it emits
toxic fumes of NOx.
Metabolism
Methylpyridines are absorbed by inhalation, ingestion or percutaneous absorption (Parmeggiana 1983). 2-Methylpyridine was rapidly absorbed and penetrated to the liver, heart, spleen, lungs and muscle during the first 10-20 min following oral administration of 0.5 g/kg to rats (Kupor 1972). The percentage uptake of 2-methylpyridine by rats increased with dosage and its elimination occurred in two phases which also were dose dependent (Zharikov and Titov 1982).Data on the biotransformation of 2-methylpyridine have been summarized by Williams (1959) and DeBruin (1976). In rabbits and dogs, the compound is oxidized to α-picolinic acid and then conjugated with glycine to form α-picolinuric acid which is excreted in the urine. In hens, it is excreted partially as α-pyridinornithuric acid. About 96% of a 100 mg/kg oral dose of 2-methylpyridine in rats was excreted in the urine as picolinuric acid (Hawksworth and Scheline 1975). There also is evidence that 2-methylpyridine forms an 2-methylated derivative in dogs (Williams 1959). Since 3-methylpyridine is converted to its N-oxide in various species (Gorrod and Damani 1980), it is likely that 2-methyl-pyridine also is similarly oxidized.
Purification Methods
Biddiscombe and Handley [J Chem Soc 1957 1954] steam distilled a boiling solution of the base in 1.2 equivalents of 20% H2SO4 until about 10% of the base had been carried over, along with non-basic impurities. Excess aqueous NaOH is then added to the residue, the free base is separated, dried with solid NaOH and fractionally distilled. 2-Methylpyridine can also be dried with BaO, CaO, CaH2, LiAlH4, sodium or Linde type 5A molecular sieves. An alternative purification is via the ZnCl2 adduct, which is formed by adding 2-methylpyridine (90mL) to a solution of anhydrous ZnCl2 (168g) and 42mL conc HCl in absolute EtOH (200mL). Crystals of the complex are filtered off, recrystallised twice from absolute EtOH (to give m 118.5-119.5o), and the free base is liberated by addition of excess aqueous NaOH. It is steam distilled, and solid NaOH is added to the distillate to form two layers, the upper one of which is then dried with KOH pellets, stored for several days with BaO and fractionally distilled. Instead of ZnCl2, HgCl2 (430g in 2.4L of hot water) can be used. The complex, which separates on cooling, can be dried at 110o and recrystallised from 1% HCl (to m 156-157o). The hydrochloride has m 78-79o, and the picrate has m 165.5o(from EtOH) and 180o(from H2O). [Beilstein 20 III/IV 2679, 20/5 V 464.]
Check Digit Verification of cas no
The CAS Registry Mumber 109-06-8 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 1,0 and 9 respectively; the second part has 2 digits, 0 and 6 respectively.
Calculate Digit Verification of CAS Registry Number 109-06:
(5*1)+(4*0)+(3*9)+(2*0)+(1*6)=38
38 % 10 = 8
So 109-06-8 is a valid CAS Registry Number.
InChI:InChI=1/C6H7N/c1-6-4-2-3-5-7-6/h2-5H,1H3
109-06-8Relevant articles and documents
(Oligo)mannose functionalized hydroxyethyl starch nanocapsules: En route to drug delivery systems with targeting properties
Freichels, Helene,Wagner, Manfred,Okwieka, Patricia,Meyer, Ralf Georg,Mailaender, Volker,Landfester, Katharina,Musyanovych, Anna
, p. 4338 - 4348 (2013)
Hydroxyethyl starch nanocapsules (NCs) are potentially interesting hydrophilic drug delivery carriers, since they do not show non-specific interactions with the living cells. Only the presence of a targeting agent on their surface allows them to target specifically the desired site of action. In this paper, we report the synthesis and cell uptake of crosslinked hydroxyethyl starch (HES) NCs decorated with (oligo)mannose, which is an effective targeting agent for macrophage and dendritic cells. The crosslinked HES NCs were prepared via the interfacial polyaddition of HES with 2,4-toluene diisocyanate (TDI) in inverse (water-in-oil) miniemulsion and then functionalized with (oligo)mannose following two different strategies. To compare the activity and availability of a targeting agent, different types of mannose molecules such as α-d-mannopyranosylphenyl isothiocyanate, 3-O-(α-d-mannopyranosyl)-d- mannose and α3,α6-mannotriose were used for the functionalization of NCs. The availability of the mannose was unambiguously assessed by interaction with a fluorescent lectin. Moreover, the accessibility of the pilot molecule was improved by the presence of a PEG linker at the surface of the NCs. To simulate in vivo conditions, where proteins interact with nanoparticles with a possible hindrance of the accessibility to the targeting agent, the mannosylated NCs were first incubated with human serum before interaction with the fluorescent lectin. Enhancement of uptake into dendritic cells demonstrates the targeting ability in in vitro studies. The Royal Society of Chemistry 2013.
Direct Phosphonation of Quinolinones and Coumarins Driven by the Photochemical Activity of Substrates and Products
Kim, Inwon,Min, Minsik,Kang, Dahye,Kim, Kiho,Hong, Sungwoo
, p. 1394 - 1397 (2017)
Light-promoted phosphonation of quinolinones and coumarins was developed without the need for an external photocatalyst. Investigations support a mechanism whereby both starting materials and products act as photosensitizers upon excitation using compact fluorescent light sources to photochemically promote the dissociation of the N-O bond in the pyridinium salt by a single electron transfer pathway. A wide range of quinolinone and coumarin substrates can be utilized in the phosphonation process under mild reaction conditions.
Preparation of 2-picolylarsonic acid and its reductive cleavage by ascorbic acid/iodine and by thiophenol
Ioannou, Panayiotis V.,Afroudakis, Pantelis A.,Siskos, Michael G.
, p. 2773 - 2783 (2002)
Contrary to dialkylaminoethyl halides, 2-picolyl chloride reacts with alkaline arsenite to give nearly quantitative yields 2-picolylarsonic acid. This acid is decomposed by ascorbic acid in the presence of catalytic amounts of iodine to 2-picoline and arsenious acid, most likely by hydride transfer from the ascorbic acid. Thiophenol decomposes this arsonic acid very quickly to 2-picoline, diphenyl disulfide and triphenyl trithioarsenite. In this case a proton from the thiophenol is transferred to the incipient 2-picolyl carbanion.
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Charman,Rowe
, p. 476 (1971)
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Additional volatile compounds produced by pyrolysis of sulfur containing amino acids
Kato,Kurata,Ishiguro,Fujimaki
, p. 1759 - 1761 (1973)
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Coordination Chemistry of Borane in Solution: Application to a STING Agonist
Lemaire, Sébastien,Zhdanko, Alexander,van der Worp, Boris A.
, (2022/04/09)
Equilibrium constants were determined for ligand exchange reactions of borane complexes with various oxygen, sulfur, nitrogen, and phosphorus nucleophiles in solution, and a binding affinity scale was built spanning a range of 12 orders of magnitude. While the Keq are minimally dependent on the solvent, the rate of ligand exchange varies significantly. The fastest and slowest rates were observed in THF and CDCl3, respectively. Moreover, the ligand exchange rate differs in a very broad range depending on stability of the starting complex. Binding of BH3 was found to be much more sensitive to steric factors than protonation. Comparing nitrogen bases having equal steric properties, a linear correlation of BH3 binding affinity vs. Br?nsted acidity was found. This correlation can be used to quickly estimate the BH3 binding affinity of a substrate if pKa is known. Kinetic studies suggest the ligand exchange to occur as a bimolecular SN2 reaction unless other nucleophilic species were present in the reaction mixture.
Synthesis and characterization of a well-defined carbon nanohorn- supported molybdenum dioxo catalyst by SMART-EM imaging. surface structure at the atomic level
Kratish, Yosi,Nakamuro, Takayuki,Liu, Yiqi,Li, Jiaqi,Tomotsuka, Issei,Harano, Koji,Nakamura, Eiichi,Marks, Tobin J.
supporting information, p. 427 - 432 (2021/03/15)
The molybdenum dioxo catalyst CNH/MoO2 is prepared via direct grafting of (dme)MoO2Cl2 (dme = 1,2-dimethoxyethane) onto the graphitic surfaces of carbon nanohorn (CNH) substrates. The structure of this heterogeneous catalyst was characterized by SMART-EM, XPS, and ICP, and is found to have single isolated MoO2 species on the surface as well as a few multi-Mo species. The CNH/MoO2 complex exhibits excellent catalytic activity for polyethylene terephthalate (PET) hydrogenolysis, N-oxide reductions, and reductive carbonyl coupling, representing an informative model catalyst for structural and mechanistic investigations.
Microporous and Micro-meso-macroporous Y Zeolites in the Synthesis of 2-Methyl-5-ethylpyridine
Grigor’eva,Filippova,Bubennov,Khazipova,Kutepov,Dyakonov
, p. 364 - 369 (2021/03/19)
Abstract: The study investigates the catalytic properties of microporous (H–Y) andmicro-meso-macroporous (H–Y-mmm) FAU-type zeolites in the synthesis of2-methyl-5-ethylpyridine (MEP) by the reaction of acetaldehyde with ammonia. At150°C, an acetaldehyde to ammonia molar ratio of 1 : 3, and a catalyst contentof 10 wt %, a MEP yield of 58% (0.95H–Y) and 63% (0.95H–Y-mmm) was achieved witha MEP selectivity of 91 and 93%, respectively. The examination of the catalyststability revealed that hierarchical H–Y-mmm zeolites ensure a 100% MEPselectivity during 4–5 cycles with a slight decline in the catalytic activity,while H–Y zeolites are active during the first cycle only.