42822-86-6

Basic information

• Product Name: p-Menthane-3,8-diol
• Synonyms: 2-hydroxy-alpha,alpha,4-trimethylcyclohexanemethanol;2-(2-hydroxypropan-2-yl)-5-methyl-cyclohexan-1-ol;PARA-MENTHANE-3,8-DIOL;1-(2-Hydroxy-4-methylcyclohexyl)-1-methylethanol;2-Hydroxy-4,α,α-trimethylcyclohexanemethanol;p-Menthane-3,8-diol;p-Methane-3,8-diol;2-(2-Hydroxypropan-2-yl)-5-Methylcyclohexanol
• CAS NO: 42822-86-6
• Molecular Formula: C₁₀H₂₀O₂
• Molecular Weight: 172.26
• EINECS: 255-953-7
• Product Categories: Cosmetics;Food additive;Insecticide;Spice
• Mol File: 42822-86-6.mol

Chemical Properties

• Melting Point: 82-83 °C
• Boiling Point: 267.6 °C at 760 mmHg
• Flash Point: 120.7 °C
• Appearance: /
• Density: 1.009 g/cm³
• Vapor Pressure: 0.00109mmHg at 25°C
• Refractive Index: 1.486
• Storage Temp.: Sealed in dry,Room Temperature
• Solubility: Chloroform (Slightly), Methanol (Slightly)
• PKA: 15.18±0.29(Predicted)
• CAS DataBase Reference: p-Menthane-3,8-diol(CAS DataBase Reference)
• NIST Chemistry Reference: p-Menthane-3,8-diol(42822-86-6)
• EPA Substance Registry System: p-Menthane-3,8-diol(42822-86-6)

Safety Data

• Hazardous Substances Data: 42822-86-6(Hazardous Substances Data)

Usage

Uses

Used in Insect Repellent Industry:
p-Menthane-3,8-diol is used as an active ingredient in insect repellents for the purpose of repelling insects such as mosquitoes, biting flies, and gnats. It is particularly effective due to its cooling effect, which is approximately 9.5 times that of (-)-menthol. p-Menthane-3,8-diol can be used in two types of consumer pesticide products: a spray and a lotion.
Used in Protection Measures for Tick-Borne Diseases:
p-Menthane-3,8-diol, under the name 2-Hydroxy-α,α,4-trimethylcyclohexanemethanol, is used as an acaricide in protection measures to prevent tick-borne diseases.
Occurrence:
p-Menthane-3,8-diol is reportedly present in the lemon eucalyptus plant (Eucalyptus citriodora tree), which is native to Australia but is now cultivated in many warm places around the world.
Regulatory Status:
Refined OLE, which contains approximately 64% p-Menthane-3,8-diol (a mixture of the cis and trans isomers of p-menthane-3,8-diol), has been notified under the European Biocidal Products Directive (BPD) 98/8/EC (now BPR Regulation (EU) No. 528/212) under its generic name "p-Menthane-3,8-diol rich botanic oil" and is currently proceeding through the registration process with the Health and Safety Executive in the UK. It is also registered with Canada's Pest Management Regulatory Agency under the generic name "p-Menthane-3,8-diol and related oil of lemon eucalyptus compounds".

Preparation

In a patented method, citronellal is treated with aqueous sulfuric acid to produce p-menthane-3,8-diol. Also produced by an extraction process utilizing lemon eucalyptus oil.

InChI:InChI=1/C10H20O2/c1-7-4-5-8(9(11)6-7)10(2,3)12/h7-9,11-12H,4-6H2,1-3H3

Upstream product

• 15356-60-2 (1S,2R,5S)-(+)-menthol 
• 5949-05-3 (S)-Citronellal 
• 106-23-0 3,7-dimethyl-oct-6-enal 
• 2385-77-5 (R)-Citronellal 
• 76735-22-3 (1RS,4SR,5RS)-1,3,3-trimethyl-2-oxabicyclo<2.2.2>octan-5-ol 
• 470-82-6 1,8-Cineole 
• 87791-00-2 6-(1-hydroxy-1-methylethyl)-3-methyl-2-cyclohexen-1-one 
• 89-79-2 isopulegol 
• 89-79-2 Isopulegol 
• 7732-18-5 water 
• 7782-77-6 cis-nitrous acid 
• 7664-93-9 sulfuric acid 
• 7647-01-0 hydrogenchloride 
• 13834-13-4 isopulegol epoxide 

Downstream Products

• 859181-11-6 isopulegol ether 
• 89-49-6 Isopulegol acetate 
• 3304-24-3 8-hydroxy-p-menthan-3-one 
• 89-79-2 Isopulegol 

Relevant articles and documents

Effect of the Stereoselectivity of para-Menthane-3,8-diol Isomers on Repulsion toward Aedes albopictus

Vector-borne diseases cause around 700,000 deaths every year. Insect repellents are one of the strategies to limit them. Para-menthane-3,8-diol (PMD), a natural compound, is one of the most promising alternatives to conventional synthetic repellents. This work describes a diastereodivergent method to synthesize each diastereoisomer of PMD from enantiopure citronellal and studies their repellence activity against Aedes albopictus. We found that cis-PMD is the kinetic control product of the cyclization of citronellal, while trans-PMD is the thermodynamic control product. X-ray diffraction analysis of crystals highlighted some differences in hydrogen-bond patterns between cis or trans isomers. The present paper demonstrates that (1R)-(+)-cis-PMD has the highest repellency index using a new evaluation system for 24 h. (1S)-(-)-cis-PMD has somewhat lower and (1S)-(+)-trans-PMD and (1R)-(-)-trans-PMD have a slight effect. Volunteer tests show that (1R)-(+)-cis-PMD is the most efficient. This effect could be ascribed to the interaction of PMD/insect odorant receptors and their physical properties, that is, the evaporation rate.

Synthesis of: P-menthane-3,8-diol from citronellal over lignin-derived carbon acid catalysts

p-Menthane-3,8-diol (PMD) is receiving growing attention as a natural mosquito repellent with lower toxicity compared to the widely-used N,N-diethyl m-toluamide (DEET). In this study, sustainable carbon acid catalysts derived from alkaline lignin (AL) were prepared for synthesizing PMD from a popular chemical (±)-citronellal in an environmentally friendly solvent of water. The catalytic performances of the AL-derived carbon acid catalysts prepared at different pyrolysis temperatures were better than those of other catalysts such as carbon black and H-USY. In particular, when the AL pyrolyzed at 500 °C was used as the carbon acid catalyst, the conversion of (±)-citronellal was as high as 97% with a high PMD yield of 86%, indicating that waste alkaline lignin from pulp and paper industries can be used as a source of acid catalysts. It is found that the formation of PMD is preferred over catalysts with weaker acid sites, whereas isopulegol was more easily formed over stronger acid sites. Moreover, the reaction route of the citronellal cyclization-hydration reaction was more dominant via the carbocation-hydration pathway rather than the isopulegol hydration route on the weaker carbon acid catalyst. This journal is

Metal Nanoparticles Supported on Perfluorinated Superacid Polymers: A Family of Bifunctional Catalysts for the Selective, One-Pot Conversion of Vegetable Substrates in Water

We describe the rational design of a new versatile family of bifunctional catalytic materials based on the combination of supported metal nanoparticles (Pd, Rh, Ru) and the superacid, perfluorinated Aquivion PFSA polymer. The heterogeneous catalysts were tested in the multi-step valorisation of representative plant derivatives to high-added-value chemicals. Particularly, the conversion of (+)-citronellal to (-)-menthol and levulinic acid to γ-valerolactone was achieved in one pot and in one stage in the water phase and shows full selectivity at a high conversion level under mild reaction conditions. The results are discussed in terms of the catalyst micro-structure.

Selective C-H bond hydroxylation of cyclohexanes in water by supramolecular control

A new approach for selective hydroxylation of non-activated cyclohexanes using dioxirane generated in situ in water through supramolecular control has been developed. Using β-CD and γ-CD as the supramolecular hosts, selective hydroxylation of cyclohexane substrates, including trans/cis-1,4-, 1,3-and 1,2-dimethylcyclohexanes and trans/cis-decahydronaphthalene, was achieved in up to 54% yield in water. Furthermore, site-selective C-H bond hydroxylation of (+)-menthol was achieved by obstructing the approach of dioxirane to the C-H bond with higher steric hindrance through inclusion complexation with β-CD and γ-CD in water.

Solvent-free synthesis of novel para-menthane-3,8-diol ester derivatives from citronellal using a polymer-supported scandium triflate catalyst

The use of natural resources as a chemical feedstock for the synthesis of added-value products is gaining interest; as such we report an environmentally friendly method for the synthesis of para-menthane-3,8-diol from natural citronellal oil in 96% yield, under solvent free aqueous conditions. The acylation of para-menthane-3,8-diol with various acid anhydrides over polymer-supported scandium triflate (PS-Sc(OTf)3) catalyst was subsequently developed, where both hydroxy groups of para-menthane-3,8-diol could be simultaneous acylated under mild reaction conditions to form the corresponding diesters in good yields. The advantages of this method include a simple procedure from natural resources, using solvent-free reaction conditions.

P-MENTHANE-3,8-DIOL ISOMER MIXTURE, COOLING SENSATION COMPOSITION COMPRISING THE SAME, AND PRODUCT COMPRISING THE COOLING SENSATION COMPOSITION

The present invention relates to a p-menthane-3,8-diol isomer mixture 50% by mass or more of which is constituted of (1S)-isomers and a cooling sensation composition containing this mixture. The present invention also relates to a flavor and/or fragrance composition, food, beverage, cosmetic, daily use product, oral cavity composition, or pharmaceutical containing the p-menthane-3,8-diol isomer mixture in an amount of 0.0001 to 90% by mass.

Biotransformations of terpenes by fungi from amazonian Citrus plants

The biotransformations of (RS)-linalool (1), (S)-citronellal (2), and sabinene (3) with fungi isolated from the epicarp of fruits of Citrus genus of the Amazonian forest (i.e., C. limon, C. aurantifolia, C. aurantium, and C. paradisiaca) are reported. The

Selective monoterpene-like cyclization reactions achieved by water exclusion from reactive intermediates in a supramolecular catalyst

A polyanionic supramolecular assembly (1) is shown to catalytically cyclize the monoterpene citronellal and two homologues. In contrast to cyclization in acidic aqueous solution, the hydrophobic interior of 1 prevents the capture of reactive intermediates by water. This effect was also observed in the gold-catalyzed cycloisomerization of an enyne. Due to the steric confinement of the catalyst's interior, Prins cyclizations in 1 proceed cleanly both for substrates containing and lacking gem-dimethyl substitution. Encapsulation in 1 consequently imposes a degree of mechanistic control that, similar to enzyme catalysis, is not observed in bulk aqueous solution.

Hydroxylation of (+)-menthol by Macrophomina phaseolina

Biotransformation of (+)-menthol with Macrophomina phaseolina led to hydroxylations at C-1, C-2, C-6, C-7, C-8 and C-9, with the C-8 position being preferentially oxidized. The resulting metabolites were identified as 8-hydroxymenthol (2), 6R-hydroxymenthol (3), 1R-hydroxymenthol (4), 9-hydroxymenthol (5), 2R,8-dihydroxymenthol (6), 8S,9-dihydroxymenthol (7), 6R,8-dihydroxymenthol (8), 1R,8-dihydroxymenthol (9) and 7,8-dihydroxymenthol (10). Metabolites 6-10 are described here for the first time. Their structures were characterized by spectroscopic analysis.

A METHOD OF PRODUCING CYCLIC DIOLS

The invention described a method of producing a 5-alkyl-2-α-hydroxyalkyl-cyclohexanol of the formula (I), the method including the step of exposing a 6,7-unsaturated aldehyde or ketone starting material of the formula (II) in a two phase reaction system, one phase being an aqueous phase, to an acid catalyst at a temperature of above 100 degree Celcius [deg C] and 250 deg C, the amount of acid being between about 0.05 and 4.0 % (m/m) to produce the 5-alkyl-2-α-hydroxyalkyl-cyclohexanol (I).