A convenient preparation of pure menthol and menthone isomers

Haut, Stephen A.

doi:10.1021/jf00062a031

Cited by 11 publications

(12 citation statements)

References 4 publications

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“…It is oxidized to menthone by oxidizing agents such as chromic acid or dichromate, though under some conditions the oxidation can go further and break open the ring. Kinetics of oxidation of menthol (I) has been taken up several groups workers in recent past [1][2][3][4][5][6][7].…”

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Kinetics of Oxidation of L - Menthol by Hypervalent Manganese in Aqueous Bisulfate and Micellar Media

Prasad¹

2020

IJRASET

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Present study authors have taken up the kinetics of oxidation of L-Menthol by hypervalent manganese (Mn(VII) or MnO 4 − ) in aqueous acid and cationic micelle (cetyltrimethylammonium bromide (CTAB)) media. Reaction obeyed second order kinetics with first order dependence on [Menthol] and [Mn(VII)], and afforded menthone as product of oxidation. Addition of cationic (CTAB) micelle decreased the rate of oxidation. The mechanism in CTAB medium was explained by the stabilization of (CTAMnO 4 ) due to the electrostatic interactions operating between anionic or (MnO 4 − ) species and cetyltrimethyl ammonium cation [(CH 3 (CH 2 ) 15 N(CH 3 ) 3 ) + or (CTA) + ] moiety. This species is more selective than strongly oxidizing HMnO 4 reagent, and could be useful to control over oxidation caused by HMnO 4. Mechanism of CTAB catalysed reaction could be explained by Menger -Portnoy's enzymatic model.

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Kinetics of Oxidation of L - Menthol by Hypervalent Manganese in Aqueous Bisulfate and Micellar Media

Prasad¹

2020

IJRASET

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“…Several industrial synthetic routes to (−)-menthol ( 10 ) have been developed, which has increased worldwide capacity, notably the Symrise process from m -cresol (involving a resolution crystallization), the Takasago process (using an asymmetric hydrogenation of a myrcene derivative and a diastereoselective cyclization), and the BASF process [exploiting a catalytic ene-cyclization of (+)-citronellal to isopulegol, then hydrogenation to (−)-menthol] . Synthesis of (+)-neoisomenthol has been reported by reduction of (+)-isomenthone using LiAlH 4 …”

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“…4 Synthesis of (+)-neoisomenthol has been reported by reduction of (+)-isomenthone using LiAlH 4 . 5 The use of biosynthetically engineered microorganisms potentially offers an attractive alternative "green" approach to (−)-menthol (10, Scheme 1) and to a diverse range of other monoterpenoids, including those less available from harvested biomass. The peppermint biosynthetic pathway of Mentha piperita (Scheme 1) converts limonene (1) ultimately into the menthol systems (9−12).…”

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“…6 This provided a proof-of-principle for a new bioengineered synthesis approach to high-value menthols. The native biosynthetic pathway (Scheme 1) produces several potentially useful intermediates en route from limonene (1) through to (+)-pulegone (5), which are found in significantly lower abundance in peppermint essential oil than the menthols. The oil contains a high level of (−)-menthol (10), a moderate level of menthone (7), and low levels of (+)-pulegone (5) and (+)-menthofuran (6), making these the commercially available substrates from the extraction process.…”

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confidence: 99%

“…The native biosynthetic pathway (Scheme 1) produces several potentially useful intermediates en route from limonene (1) through to (+)-pulegone (5), which are found in significantly lower abundance in peppermint essential oil than the menthols. The oil contains a high level of (−)-menthol (10), a moderate level of menthone (7), and low levels of (+)-pulegone (5) and (+)-menthofuran (6), making these the commercially available substrates from the extraction process. This leaves half of the compounds [(−)-trans-isopiperitenol (2), (−)-isopiperitenone (3), (+)-cis-isopulegone (4), (+)-isomenthone (8), and (+)-neoisomenthol (12)] in the biosynthetic pathway unobtainable in reasonable yields from natural sources.…”

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Chemoenzymatic Synthesis of the Intermediates in the Peppermint Monoterpenoid Biosynthetic Pathway

et al. 2018

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A chemoenzymatic approach providing access to all four intermediates in the peppermint biosynthetic pathway between limonene and menthone/isomenthone, including noncommercially available intermediates (-)- trans-isopiperitenol (2), (-)-isopiperitenone (3), and (+)- cis-isopulegone (4), is described. Oxidation of (+)-isopulegol (13) followed by enolate selenation and oxidative elimination steps provides (-)-isopiperitenone (3). A chemical reduction and separation route from (3) provides both native (-)- trans-isopiperitenol (2) and isomer (-)- cis-isopiperitenol (18), while enzymatic conjugate reduction of (-)-isopiperitenone (3) with IPR [(-)-isopiperitenone reductase)] provides (+)- cis-isopulegone (4). This undergoes facile base-mediated chemical epimerization to (+)-pulegone (5), which is subsequently shown to be a substrate for NtDBR ( Nicotiana tabacum double-bond reductase) to afford (-)-menthone (7) and (+)-isomenthone (8).

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The Synthesis of Monoterpenes 1980—1986

Thomas

Bessière²

1988

Total Synthesis of Natural Products

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A convenient preparation of pure menthol and menthone isomers

Cited by 11 publications

References 4 publications

Kinetics of Oxidation of L - Menthol by Hypervalent Manganese in Aqueous Bisulfate and Micellar Media

Kinetics of Oxidation of L - Menthol by Hypervalent Manganese in Aqueous Bisulfate and Micellar Media

Chemoenzymatic Synthesis of the Intermediates in the Peppermint Monoterpenoid Biosynthetic Pathway

The Synthesis of Monoterpenes 1980—1986

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