99-86-5

Usage

Chemical Properties

Different sources of media describe the Chemical Properties of 99-86-5 differently. You can refer to the following data:
1. clear colorless to light yellow liquid
2. p-Mentha-1,3-diene has a woody, terpene, lemon odor with a lemony flavor, becoming bitter at high levels.

Occurrence

Reported found in roots, stems, leaves and flowers of Echinacea species. Also reported found in in tea tree oil, papaya fruit, grapefruit, lemon, lime, mandarin, oranage, spearmint, citrus peel oils, cranberry, currants, guava, grapes, raspberry, peach, carrot, celery, cinnamon, clove, cumin seed, ginger, peppermint and corn mint oils, other mentha oils, nutmeg, pepper, mace, parsley, thymus, rum, tea, filberts, pecans, soybeans, passion fruit, beans, sweet marjoram, starfruit, mango, cardamom, coriander seed, origanum, prickly pear, litchi, calamus, dill herb, lovage seed and leaf, juniper berries, laurel, fennel, rosemary, buchu oil, tur meric, sage, nectarines and many other sources.

Uses

Different sources of media describe the Uses of 99-86-5 differently. You can refer to the following data:
1. It can be used as a chemical fragrance essential oil and spices. It is used as a flavoring and fragrance chemical used in the personal care and cosmetic and food industries. Also used in the pharmaceutical, electronics, food processing, semi-conductor manufacturing industries.
2. α-Terpinene is suitable for use in a study to evaluate the antimycotic properties of Melaleuca alternifolia essential oil (tea tree oil, TTO). 1 It is suitable for use to investigate the in vitro antibacterial activity of the essential oils extracted from the fruits of Coriandrum sativum L. and Foeniculum vulgare Miller var. vulgare (Miller).

Preparation

May be obtained by isolation from the terpene fraction of sweet orange oil or orange terpenes (8 to 10% of the total monoterpenes); by isolation from fractions of American turpentine oil; from 1-methyl-4-isopropylcyclohexadien-1,3-one-2; also from terpinene dihydrochloride with aniline.

Aroma threshold values

Aroma characteristics at 10%: citrusy, woody, terpy with camphoraceous and thymol notes; it has spicy and juicy citrus nuances.

Taste threshold values

Taste characteristics at 5 to 100 ppm: terpy, woody, piney, citrus lemon and lime with spice and mint nuances.

General Description

α-Terpinene, a volatile essential oil derived from Melaleuca alternifolia, shows antimicrobial properties against various human pathogens.

Flammability and Explosibility

Flammable

Biochem/physiol Actions

Odor at 10%

Pharmacology

Combinations of terpenes, such as terpinene, with nonionic surfactants and stabilizers have been patented for use as gallstone solvents. Artificial or human cholesterol calculi placed in terpinene with or without human bile at 37°C were dissolved within 1-2 hr (Hisamitsu Pharmaceutical Co., Inc., 1973).

Safety Profile

Moderately toxic by ingestion. When heated to decomposition it emits acrid smoke and irritating fumes.

InChI:InChI=1S/C10H16/c1-8(2)10-6-4-9(3)5-7-10/h4,6,8H,5,7H2,1-3H3

Upstream product

• 110-86-1 pyridine 
• 63343-17-9 1,2-dibromo-p-menthane 
• 91-22-5 quinoline 
• 31383-92-3 6-bromo-p-menth-1-ene 
• 854823-91-9 2,4-dichloro-p-menthane 
• 67-56-1 methanol 
• 7785-70-8 (+)-α-pinene 
• 109-63-7 trifluoroborane diethyl ether 
• 917-64-6 methyl magnesium iodide 
• 513-20-2 sabinaketone 
• 64-18-6 formic acid 
• 98-55-5 terpineol 
• 99-83-2 p-mentha-1,5-diene 
• 65370-78-7 1,8-Cineol 

Downstream Products

• 512-85-6 ascaridole 
• 13901-85-4 6-methyl-2,5-heptanedione 
• 25570-96-1 1,4-dibromo-p-menthane 
• 99-82-1 Menthane 
• 99-87-6 4-methylisopropylbenzene 
• 122-00-9 para-methylacetophenone 
• 33596-66-6 2-(4-methylphenyl)propanal 
• 60-29-7 diethyl ether 
• 103049-87-2 4-[1,3-dimethyl-1,3-bis-(4-methyl-cyclohex-3-enyl)-butyl]-phenol 
• 59922-36-0 cis-1,4-Dimethoxy-p-menthan 
• 90786-13-3 1-Isopropyl-1,4-dimethoxy-4-methyl-cyclohexane 
• 90786-10-0 (3R,4R)-1-Isopropyl-3,4-dimethoxy-4-methyl-cyclohexene 
• 74545-77-0 4-Isopropyl-1-methyl-3-(2-p-tolyl-propenyl)-1-cyclohexene 
• 74545-76-9 4-Isopropyl-1-methyl-6-(2-p-tolyl-propenyl)-1-cyclohexene 

Relevant academic research and scientific papers

Preparation of α-terpineol and perillyl alcohol using zeolites beta

The preparation of α-terpineol by direct hydration of limonene catalyzed by zeolites beta was studied. The same catalyst was used to prepare perillyl alcohol by isomerization of β-pinene oxide in the presence of water. The aim was to optimize the reaction conditions to achieve high conversions of starting material and high selectivity to the desired products. In the case of limonene, it was found that the highest selectivity to α-terpineol was 88% with conversion of 36% under the conditions: 50?wt% of catalyst beta 25, 10% aqueous acetic acid (10?mL) (volume ratio limonene:H2O = 1:4.5), temperature 50?°C, after 24?h. In the case of β-pinene oxide, it was found that the highest selectivity to perillyl alcohol, which was 36% at total conversion, was obtained in the reaction under the following conditions: dimethyl?sulfoxide as solvent (volume ratio β-pinene oxide:DMSO = 1:5), catalyst beta 25 without calcination (15?wt%), demineralized water (molar ratio β-pinene oxide:H2O = 1:8), temperature 70?°C, 3?h. The present study shows that the studied reactions are suitable for the selective preparation of chosen compounds.

Thioderivatives of Resorcin[4]arene and Pyrogallol[4]arene: Are Thiols Tolerated in the Self-Assembly Process?

Three novel thiol bearing resorcin[4]arene and pyrogallol[4]arene derivatives were synthesized. Their properties were studied with regards to self-assembly, disulfide chemistry, and Br?nsted acid catalysis. This work demonstrates that (1) one aromatic thiol on the resorcin[4]arene framework is tolerated in the self-assembly process to a hexameric hydrogen bond-based capsule, (2) thio-derivatized resorcin[4]arene analogs can be covalently linked through disulfides, and (3) the increased acidity of aromatic thio-substituent is not sufficient to replace HCl as cocatalyst for capsule catalyzed terpene cyclizations.

A Straightforward Synthesis of Trideuterated α-Terpinene for Mechanistic Studies

Regiospecifically trideuterated (2,6,6-2H3)-α-terpinene was prepared in six steps and with a deuterium incorporation of >99 % in 24 % yield from 1,4-cyclohexanedione monoethylene ketal. The synthetic procedure involved twofold cross-coupling reactions of alkylcuprates (lithium dimethylcuprate and chloromagnesium cyano(isopropyl)cuprate, respectively) with enol triflates to introduce the alkyl substituents on the 1,3-cyclohexadiene backbone. By changing the alkylcuprates, the synthetic approach could serve as a prototype for the synthesis of various 1,4-dialkyl-substituted 1,3-cyclohexadiene derivatives, which could be deuterium-labeled as well, for example for mechanistic studies.

Requirements for Terpene Cyclizations inside the Supramolecular Resorcinarene Capsule: Bound Water and Its Protonation Determine the Catalytic Activity

The elucidation of the requirements for efficient catalysis within supramolecular host systems is an important prerequisite for developing novel supramolecular catalysts. The resorcinarene hexamer has recently been shown to be the first supramolecular catalyst to promote the tail-to-head terpene cyclization in a biomimetic fashion. We herein present the synthesis of a number of resorcinarene-based macrocycles composed of different ratios of resorcinol and pyrogallol units capable of self-assembly and compare the corresponding assemblies regarding their catalytic activity in the cyclization of monoterpenes. The assemblies were investigated in detail with respect to a number of properties including the encapsulation of substrate and ion pairs, the structural incorporation of water, and the response to externally added acid (HCl). The results obtained strongly indicate that water incorporated into the hydrogen-bond network of the self-assembled structure plays an integral role for catalysis, effectively acting as a proton shuttle to activate the encapsulated substrate. These findings are also supported by molecular dynamics simulations, providing further insight into the protonation pathway and the relative energies of the intermediates involved.

Sesquiterpene Cyclizations inside the Hexameric Resorcinarene Capsule: Total Synthesis of δ-Selinene and Mechanistic Studies

The synthesis of terpene natural products remains a challenging task due to the enormous structural diversity in this class of compounds. Synthetic catalysts are unable to reproduce the tail-to-head terpene cyclization of cyclase enzymes, which create this diversity from just a few simple linear terpene substrates. Recently, supramolecular structures have emerged as promising enzyme mimetics. In the present study, the hexameric resorcinarene capsule was utilized as an artificial cyclase to catalyze the cyclization of sesquiterpenes. With the cyclization reaction as the key step, the first total synthesis of the sesquiterpene natural product δ-selinene was achieved. This represents the first total synthesis of a sesquiterpene natural product that is based on the cyclization of a linear terpene precursor inside a supramolecular catalyst. To elucidate the reaction mechanism, detailed kinetic studies and kinetic isotope measurements were performed. Surprisingly, the obtained kinetic data indicated that a rate-limiting encapsulation step is operational in the cyclization of sesquiterpenes.

Transition metal triflate catalyzed conversion of alcohols, ethers and esters to olefins

Herein, we report an efficient transition metal triflate catalyzed approach to convert biomass-based compounds, such as monoterpene alcohols, sugar alcohols, octyl acetate and tea tree oil, to their corresponding olefins in high yields. The reaction proceeds through C-O bond cleavage under solvent-free conditions, where the catalytic activity is determined by the oxophilicity and the Lewis acidity of the metal catalyst. In addition, we demonstrate how the oxygen containing functionality affects the formation of the olefins. Furthermore, the robustness of the used metal triflate catalysts, Fe(OTf)3 and Hf(OTf)4, is highlighted by their ability to convert an over 2400-fold excess of 2-octanol to octenes in high isolated yields.

Elucidating the Importance of Hydrochloric Acid as a Cocatalyst for Resorcinarene-Capsule-Catalyzed Reactions

This survey of resorcinarene-capsule-catalyzed reactions demonstrates that HCl functions as a crucial cocatalyst by increasing the capsule's inherent Br?nsted acidity to enable or accelerate cationic reactions. The presence of HCl appears to be without consequences for other reactions.

Terpene Cyclizations inside a Supramolecular Catalyst: Leaving-Group-Controlled Product Selectivity and Mechanistic Studies

The tail-to-head terpene cyclization is arguably one of the most complex reactions found in nature. The hydrogen-bond-based resorcinarene capsule represents the first man-made enzyme-like catalyst that is capable of catalyzing this reaction. Based on noncovalent interactions between the capsule and the substrate, the product selectivity can be tuned by using different leaving groups. A detailed mechanistic investigation was performed to elucidate the reaction mechanism. For the cyclization of geranyl acetate, it was found that the cleavage of the leaving group is the rate-determining step. Furthermore, the studies revealed that trace amounts of acid are required as cocatalyst. A series of control experiments demonstrate that a synergistic interplay between the supramolecular capsule and the acid traces is required for catalytic activity.

High density fuels from oxygenated terpenoids

A method for the efficient synthesis of useful deoxygenated terpenoids from an abundant renewable source, using catalytic conversion of oxygenated terpenoids. Oxygenated terpenoids such as 1,4-cineole and 1,8-cineole are, for example, major components of turpentine and essential oils. These oxygenated terpenoids can also be produced from sugars via a biosynthetic approach. Catalytic deoxygenation of these substrates can be used to efficiently generate commercially important chemicals and high density fuels for turbine or diesel propulsion.

Hybrid catalysts based on platinum and palladium nanoparticles for the hydrogenation of terpenes under slurry conditions

Catalysts based on platinum and palladium nanoparticles immobilized in mesoporous phenolformaldehyde polymers modified with sulfo groups have been used for the hydrogenation of a number of terpenes, such as (S)-(–)-limonene, α-terpinene, γ-terpinene, and terpinolene. It has been found that Pd-containing catalysts exhibit higher activity in the exhaustive hydrogenation of terpenes, whereas Pt-containing catalysts have high selectivity for p-menthene.