3-Methylpyridine
Names
Preferred IUPAC name
3-Methylpyridine
Other names
3-Picoline
Identifiers
3D model (JSmol)
1366
ChEBI
ChEMBL
ChemSpider
DrugBank
ECHA InfoCard 100.003.307
EC Number
  • 203-636-9
2450
RTECS number
  • TJ5000000
UNII
UN number 2313
  • InChI=1S/C6H7N/c1-6-3-2-4-7-5-6/h2-5H,1H3
    Key: ITQTTZVARXURQS-UHFFFAOYSA-N
  • Cc1cccnc1
Properties
C6H7N
Molar mass 93.13 g/mol
Appearance Colorless liquid
Density 0.957 g/mL
Melting point −19 °C (−2 °F; 254 K)
Boiling point 144 °C (291 °F; 417 K)
Miscible
-59.8·10−6 cm3/mol
Hazards
GHS labelling:
GHS02: FlammableGHS05: CorrosiveGHS06: ToxicGHS07: Exclamation mark
Danger
H226, H302, H311, H314, H315, H319, H331, H332, H335
P210, P233, P240, P241, P242, P243, P260, P261, P264, P270, P271, P280, P301+P312, P301+P330+P331, P302+P352, P303+P361+P353, P304+P312, P304+P340, P305+P351+P338, P310, P311, P312, P321, P322, P330, P332+P313, P337+P313, P361, P362, P363, P370+P378, P403+P233, P403+P235, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

3-Methylpyridine or 3-picoline, is an organic compound with formula 3-CH3C5H4N. It is one of three positional isomers of methylpyridine, whose structures vary according to where the methyl group is attached around the pyridine ring. This colorless liquid is a precursor to pyridine derivatives that have applications in the pharmaceutical and agricultural industries. Like pyridine, 3-methylpyridine is a colorless liquid with a strong odor and is classified as a weak base.[1]

Synthesis

3-Methylpyridine is produced industrially by the reaction of acrolein, with ammonia. These ingredients are combined as gases which flows over an oxide-based heterogeneous catalyst. The reaction is multistep, culminating in cyclisation.

2  CH2CHCHO + NH3 → CH3C5H4N + 2 H2O

This process also affords substantial amounts of pyridine, which arises by demethylation of the 3-methylpyridine. A route that gives better control of the product starts with acrolein, propionaldehyde, and ammonia:[1]

CH2CHCHO + CH3CH2CHO + NH3 → 3-CH3C5H4N + 2 H2O + H2

It may also be obtained as a co-product of pyridine synthesis from acetaldehyde, formaldehyde, and ammonia via Chichibabin pyridine synthesis. Approximately 9,000,000 kilograms were produced worldwide in 1989. It has also been prepared by dehydrogenation of 3-methylpiperidine, derived from hydrogenation of 2-Methylglutaronitrile.[2]

Uses

3-Picoline is a useful precursor to agrochemicals, such as chlorpyrifos.[1] Chlorpyrifos is produced from 3,5,6-trichloro-2-pyridinol, which is generated from 3-picoline by way of cyanopyridine. This conversion involves the ammoxidation of 3-methylpyridine:

CH3C5H4N + 1.5 O2 + NH3 → NCC5H4N + 3 H2O

3-Cyanopyridine is also a precursor to 3-pyridinecarboxamide,[3][4][5] which is a precursor to pyridinecarbaldehydes:

3-NCC5H3N + [H] + catalyst → 3-HC(O)C5H4N

Pyridinecarbaldehydes are used to make antidotes for poisoning by organophosphate acetylcholinesterase inhibitors.

Environmental behavior

Pyridine derivatives (including 3-methylpyridine) are environmental contaminants, generally associated with processing fossil fuels, such as oil shale or coal.[6] They are also found in the soluble fractions of crude oil spills. They have also been detected at legacy wood treatment sites. The high water solubility of 3-methyl pyridine increases the potential for the compound to contaminate water sources. 3-methyl pyridine is biodegradable, although it degrades more slowly and volatilize more readily from water samples than either 2-methyl- or 4-methyl-pyridine.,[7][8]

3-Methylpyridine is the main precursor to niacin, one of the B vitamins. Approximately 10,000 tons of niacin are produced annually worldwide.[9]

See also

Toxicity

Like most alkylpyridines, the LD50 of 2-methylpyridine is modest, being 400 mg/kg (oral, rat).[9]

References

  1. 1 2 3 Shinkichi Shimizu; Nanao Watanabe; Toshiaki Kataoka; Takayuki Shoji; Nobuyuki Abe; Sinji Morishita; Hisao Ichimura (2002). "Pyridine and Pyridine Derivatives". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a22_399. ISBN 978-3527306732.
  2. ↑ Eric F. V. Scriven; Ramiah Murugan (2005). "Pyridine and Pyridine Derivatives". Kirk-Othmer Encyclopedia of Chemical Technology. XLI. doi:10.1002/0471238961.1625180919031809.a01.pub2. ISBN 0471238961.
  3. ↑ Nagasawa, Toru; Mathew, Caluwadewa Deepal; Mauger, Jacques; Yamada, Hideaki (1988). "Nitrile Hydratase-Catalyzed Production of Nicotinamide from 3-Cyanopyridine in Rhodococcus rhodochrous J1". Appl. Environ. Microbiol. 54 (7): 1766–1769. Bibcode:1988ApEnM..54.1766N. doi:10.1128/AEM.54.7.1766-1769.1988. PMC 202743. PMID 16347686.
  4. ↑ Hilterhaus, L.; Liese, A. (2007). "Building Blocks". In Ulber, Roland; Sell, Dieter (eds.). White Biotechnology. Advances in Biochemical Engineering / Biotechnology. Vol. 105. Springer Science & Business Media. pp. 133–173. doi:10.1007/10_033. ISBN 9783540456957. PMID 17408083.
  5. ↑ Schmidberger, J. W.; Hepworth, L. J.; Green, A. P.; Flitsch, S. L. (2015). "Enzymatic Synthesis of Amides". In Faber, Kurt; Fessner, Wolf-Dieter; Turner, Nicholas J. (eds.). Biocatalysis in Organic Synthesis 1. Science of Synthesis. Georg Thieme Verlag. pp. 329–372. ISBN 9783131766113.
  6. ↑ Sims, Gerald K.; O'Loughlin, Edward J.; Crawford, Ronald L. (January 1989). "Degradation of pyridines in the environment". Critical Reviews in Environmental Control. 19 (4): 309–340. Bibcode:1989CRvEC..19..309S. doi:10.1080/10643388909388372. ISSN 1040-838X.
  7. ↑ Sims, Gerald K.; Sommers, Lee E. (June 1986). "Biodegradation of pyridine derivatives in soil suspensions". Environmental Toxicology and Chemistry. 5 (6): 503–509. doi:10.1002/etc.5620050601. ISSN 0730-7268.
  8. ↑ Sims, Gerald K.; Sommers, Lee E. (October 1985). "Degradation of Pyridine Derivatives in Soil". Journal of Environmental Quality. 14 (4): 580–584. Bibcode:1985JEnvQ..14..580S. doi:10.2134/jeq1985.00472425001400040022x. ISSN 0047-2425.
  9. 1 2 Manfred Eggersdorfer; et al. (2000). "Vitamins". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a27_443. ISBN 3527306730.
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