Anisole - Misplaced Pages

P210, P233, P240, P241, P242, P243, P264, P280, P302+P352, P303+P361+P353, P305+P351+P338, P321, P332+P313, P337+P313, P362, P370+P378, P403+P235, P501

NFPA 704 (fire diamond)

1 2 0

Lethal dose or concentration (LD, LC):

LD₅₀ (median dose)

3700 mg/kg (rat, oral)

Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa).

Y verify (what is ?) Infobox references

Chemical compound

Anisole, or methoxybenzene, is an organic compound with the formula CH₃OC₆H₅. It is a colorless liquid with a smell reminiscent of anise seed, and in fact many of its derivatives are found in natural and artificial fragrances. The compound is mainly made synthetically and is a precursor to other synthetic compounds. Structurally, it is an ether (−O−) with a methyl (−CH₃) and phenyl (−C₆H₅) group attached. Anisole is a standard reagent of both practical and pedagogical value.

Reactivity

Anisole undergoes electrophilic aromatic substitution reaction at a faster speed than benzene, which in turn reacts more quickly than nitrobenzene. The methoxy group is an ortho/para directing group, which means that electrophilic substitution preferentially occurs at these three sites. The enhanced nucleophilicity of anisole vs. benzene reflects the influence of the methoxy group, which renders the ring more electron-rich. The methoxy group strongly affects the pi cloud of the ring as a mesomeric electron donor, more so than as an inductive electron withdrawing group despite the electronegativity of the oxygen. Stated more quantitatively, the Hammett constant for para-substitution of anisole is –0.27.

Illustrative of its nucleophilicity, anisole reacts with acetic anhydride to give 4-methoxyacetophenone:

CH₃OC₆H₅ + (CH₃CO)₂O → CH₃OC₆H₄C(O)CH₃ + CH₃CO₂H

Unlike most acetophenones, but reflecting the influence of the methoxy group, methoxyacetophenone undergoes a second acetylation. Many related reactions have been demonstrated. For example, phosphorus pentasulfide (P₄S₁₀) converts anisole to Lawesson's reagent, [(CH₃OC₆H₄)PS₂]₂.

Also indicating an electron-rich ring, anisole readily forms π-complexes with metal carbonyls, e.g. Cr(η-anisole)(CO)₃.

The ether linkage is highly stable, but the methyl group can be removed with strong acids, such as hydroiodic acid or boron trichloride:

CH₃OC₆H₅ + HI → HOC₆H₅ + CH₃I

Birch reduction of anisole gives 1-methoxycyclohexa-1,4-diene.

Synthesis

Anisole was first synthesized in 1841 by Auguste Cahours by barium anisate decarboxylation while heating p-anisic acid he made earlier from the anise essence with barium oxide:

2 CH₃OC₆H₄COOH + BaO → (CH₃OC₆H₄COO)₂Ba + H₂O

(CH₃OC₆H₄COO)₂Ba → 2 CH₃OC₆H₅ + BaCO₃

It can be prepared by the Williamson ether synthesis from sodium phenoxide and dimethyl sulfate or methyl chloride:

2 C₆H₅O Na + (CH₃O)₂SO₂ → 2 C₆H₅OCH₃ + Na₂SO₄

Applications

Anisole is a precursor to perfumes, insect pheromones, and pharmaceuticals. For example, synthetic anethole is prepared from anisole.

Safety

Anisole is relatively nontoxic with an LD₅₀ of 3700 mg/kg in rats. Its main hazard is its flammability.

Popular culture

In the board game Scrabble, the word "anisole" is the 39th-most-likely word (out of over 25,000 possibilities) for a "bingo"/"bonus", i.e. the deployment of all seven letters in one's own hand simultaneously.

References

^ Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. pp. 702–703. doi:10.1039/9781849733069-00648. ISBN 978-0-85404-182-4. Anisole, C₆H₅−O−CH₃, is the only name in the class of ethers which is retained both as a preferred IUPAC name and for use in general nomenclature. For preferred IUPAC names, no substitution is allowed; for general nomenclature substitution is allowed on the ring and on the side chain under certain conditions (see P-34.1.1.4).
Smith, Michael B.; March, Jerry (2007), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (6th ed.), New York: Wiley-Interscience, ISBN 978-0-471-72091-1
I. Thomsen; K. Clausen; S. Scheibye; S.-O. Lawesson (1984). "Thiation with 2,4-Bis(4-Methoxyphenyl)-1,3,2,4-Dithiadiphosphetane 2,4-Disulfide: N-Methylthiopyrrolidone". Organic Syntheses. 62: 158. doi:10.15227/orgsyn.062.0158.
E. Peter Kündig (2004). "Synthesis of Transition Metal η-Arene Complexes". Topics Organomet Chem. Topics in Organometallic Chemistry. 7: 3–20. doi:10.1007/b94489. ISBN 978-3-540-01604-5.
^ Helmut Fiege; Heinz-Werner Voges; Toshikazu Hamamoto; Sumio Umemura; Tadao Iwata; Hisaya Miki; Yasuhiro Fujita; Hans-Josef Buysch; Dorothea Garbe; Wilfried Paulus. "Phenol Derivatives". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_313. ISBN 978-3527306732.
A. J. Birch and K. B. Chamberlain (1977). "TricarbonylIron and TricarbonylIron(1+) Hexafluorophosphate(1−) from Anisole". Organic Syntheses. 57: 107. doi:10.15227/orgsyn.057.0107.
Wisniak, Jaime (2013-10-01). "Auguste André Thomas Cahours". Educación Química. 24 (4): 451–460. doi:10.1016/S0187-893X(13)72500-X. ISSN 0187-893X.
Crochard (París); Arago, François; Gay-Lussac, Joseph Louis (1841). Annales de chimie et de physique (in French). Chez Crochard.
G. S. Hiers and F. D. Hager (1929). "Anisole". Organic Syntheses. 9: 12. doi:10.15227/orgsyn.009.0012.
^ MSDS Archived July 1, 2010, at the Wayback Machine
"Fun with analytics: Probabilities and Scrabble". www.illumine8.com. Retrieved 2023-12-08.

External links

International Chemical Safety Card 1014
Pherobase pheromone database entry

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