185329-56-0

Basic information

• Product Name: 1-methyl-4-(1-methylethenyl)-1,2-cyclohexanediol
• Synonyms: 1-methyl-4-(1-methylethenyl)-1,2-cyclohexanediol
• CAS NO: 185329-56-0
• Molecular Weight: 170.252
• Mol File: 185329-56-0.mol

Chemical Properties

• CAS DataBase Reference: 1-methyl-4-(1-methylethenyl)-1,2-cyclohexanediol(CAS DataBase Reference)
• NIST Chemistry Reference: 1-methyl-4-(1-methylethenyl)-1,2-cyclohexanediol(185329-56-0)
• EPA Substance Registry System: 1-methyl-4-(1-methylethenyl)-1,2-cyclohexanediol(185329-56-0)

Safety Data

• Hazardous Substances Data: 185329-56-0(Hazardous Substances Data)

Upstream product

• 5989-27-5 D-limonene 
• 124-38-9 carbon dioxide 
• 6909-30-4 (1S,2R,4R)-limonene-1,2-epoxide 
• 4680-24-4 cis-(R)-limonene oxide 
• 1195-92-2 (4R)-limonene 1,2-epoxide 

Downstream Products

• 7086-79-5 (R)-4-methyl-3-(3'-oxobutyl)pent-4-enal 
• 324769-85-9 2-Hydroxy-5-isopropenyl-2-methyl-cyclohexanon 

Relevant articles and documents

Synthesis, spectral investigation and catalytic aspects of entrapped VO(IV) and Cu(II) complexes into the supercages of zeolite-Y

VO(IV) and Cu(II) complexes with Schiff base ligand derived from 1-phenyl-3-methyl-4-formyl-2-pyrazolin-5-one (PMFP) and 2-amino phenol have been synthesized as their neat and entrapped complexes into the supercages of zeolite-Y. The compounds were characterized by chemical analysis (ICP-OES and elemental), electronic and/or UV reflectance spectra, FTIR spectroscopy, X-ray powder diffraction patterns, SEMs, BET and thermogravimetric (TG) analysis. All the prepared catalysts were tested on the liquid phase limonene oxidation reaction, using 30% H2O2 as an oxidant. Limonene glycol, carveol, carvone and limonene 1,2-epoxide were the main products obtained. It was observed that zeolite-Y entrapped complexes exhibited higher catalytic activity than neat complexes. The catalysts undergo no metal leaching and can be easily recovered and reused. The use of inexpensive catalyst and oxidant are significant practical advantages of this environmentally friendly process.

Selective Formation of Epoxylimonene Catalyzed by Phosphonyl/Arsonyl Derivatives of Trivacant Polyoxotungstates at Low Temperature

The catalytic performances of three organophosphonyl/arsonyl derivatives of POMs were evaluated for the epoxidation of limonene in acetonitrile, using aqueous H2O2 as the oxidant. All three W-based POMs catalysts operated without any additional transition-metal ions and displayed excellent conversion for limonene at temperatures varying from 4 to 50 °C. Furthermore, the use of B,α-[NaHAsW9O33{P(O)R}2]3– (R = tBu, -CH2CH2CO2H) complexes led to the complete conversion of limonene to epoxylimonene at 4 °C. The selectivity of the reaction was modulated by varying the reaction solvent, and it was found that allylic reactions were favored in ethanol. The effect of the catalyst protonation was also investigated by DFT calculations, highlighting the role of protons in the epoxidation process.

Catalytic oxidation of limonene over zeolite-Y entrapped oxovanadium (IV) complexes as heterogeneous catalysts

A series of VO(IV) complexes with Schiff base ligands derived from vanillin thiophene-2-carboxylic hydrazone (VTCH), vanillin furoic-2-carboxylic hydrazone (VFCH), salicylaldehyde thiophene-2-carboxylic hydrazone (H2STCH) and/or salicylaldehyde furoic-2-carboxylic hydrazone (H2SFCH) have been synthesized as neat and their entrapped complexes into the nanopores of zeolite-Y. These materials were characterized by several techniques: chemical analysis (ICP-OES and elemental) and spectroscopic methods (FT-IR, electronic, XRD, SEMs and BET). All the prepared catalysts were tested over the liquid phase limonene oxidation reaction, using t-butyl hydroperoxide (TBHP) and/or 30% H2O2 as oxidants. Limonene glycol, carveol and carvone were the main products obtained. It was observed that zeolite-Y based entrapped complexes exhibited higher catalytic activity than neat VO(IV) complexes. These zeolite-Y based entrapped complexes are stable and recyclable under current reaction conditions. Amongst them, [VO(VTCH)2]-Y showed higher catalytic activity (97.7%) with limonene glycol (45.1%), selectivity.

Synthesis and characterization of novel chiral sulfonato-salen- manganese(III) complex in a zinc-aluminium LDH host

A novel heterogeneous catalyst, [Zn2.15Al0.86(OH) 6.02] [Mn]0.19[C6H5COO] 0.48·2H2O, where {[Mn] = chiral sulfonato- -salen-manganese(III) complex, Na2MnC20H 22N2S2O12Cl, intercalated into Zn11-Al111 layered double hydroxide host), has been synthesized and found to be an effective heterogeneous catalyst for the stereoselective epoxidation of R-(+)-limonene using molecular oxygen. The catalyst could be recycled without loss of performance.

Lipase catalysed oxidations in a sugar-derived natural deep eutectic solvent

Chemoenzymatic oxidations involving the CAL-B/H2O2 system was developed in a sugar derived Natural Deep Eutectic Solvent (NaDES) composed by a mixture of glucose, fructose and sucrose. Good to excellent conversions of substrates like cyclooctene, limonene, oleic acid and stilbene to their corresponding epoxides, cyclohexanone to its corresponding lactone and 2-phenylacetophenone to its corresponding ester, demonstrate the viability of the sugar NaDES as a reaction medium for epoxidation and Baeyer-Villiger oxidation.

Selective Catalytic Synthesis of 1,2- and 8,9-Cyclic Limonene Carbonates as Versatile Building Blocks for Novel Hydroxyurethanes

The selective catalytic synthesis of limonene-derived monofunctional cyclic carbonates and their subsequent functionalisation via thiol–ene addition and amine ring-opening is reported. A phosphotungstate polyoxometalate catalyst used for limonene epoxidation in the 1,2-position is shown to also be active in cyclic carbonate synthesis, allowing a two-step, one-pot synthesis without intermittent epoxide isolation. When used in conjunction with a classical halide catalyst, the polyoxometalate increased the rate of carbonation in a synergistic double-activation of both substrates. The cis isomer is shown to be responsible for incomplete conversion and by-product formation in commercial mixtures of 1,2-limomene oxide. Carbonation of 8,9-limonene epoxide furnished the 8,9-limonene carbonate for the first time. Both cyclic carbonates underwent thiol–ene addition reactions to yield linked di-monocarbonates, which can be used in linear non-isocyanate polyurethanes synthesis, as shown by their facile ring-opening with N-hexylamine. Thus, the selective catalytic route to monofunctional limonene carbonates gives straightforward access to monomers for novel bio-based polymers.

Heteropoly acid catalysis for the isomerization of biomass-derived limonene oxide and kinetic separation of the trans-isomer in green solvents

Terpenes are an abundant class of natural products, which is important for flavor and fragrance industry. Many acid catalyzed reactions used for upgrading terpenes still involve mineral acids as homogeneous catalysts and/or toxic solvents. Heteropoly acids represent a well-established eco-friendly alternative to conventional acid catalysts. As these reactions are usually performed in the liquid phase, solvents play a critical role for the process sustainability. In the present work, we developed a catalytic route to valuable fragrance ingredients, dihydrocarvone and carvenone, from limonene oxide by its isomerization using silica-supported tungstophosphoric acid as a heterogeneous catalyst and dialkylcarbonates as green solvents. The reaction pathway can be switched between dihydrocarvone and carvenone (obtained in 90% yield each) simply by changing the reaction temperature. In addition, we developed an efficient method for kinetic separation of trans-limonene oxide from commercial cis/trans-limonene oxide mixture and stereoselective synthesis of trans-dihydrocarvone.

Enhanced solvent-free selective oxidation of cyclohexene to 1,2-cyclohexanediol by polyaniline@halloysite nanotubes

One-dimensional polyaniline@halloysite (PANI@HA) nanotubes with enhanced selective oxidation activity of cyclohexene are fabricated by employing aniline (ANI) chemical polymerization on halloysite nanotubes in situ. By facilely controlling the doping acid, acidity, and ANI/HA weight ratio during the fabrication, PANI with a controllable doping degree, redox state, and content is grown on halloysite nanotubes. The cyclohexene selective oxidation result shows that PANI@HA nanotubes are effective catalysts in a solvent-free reaction system with H2O2 as the oxidant, and their catalytic activity relies on the doping acid, acidity, and ANI/HA weight ratio in the fabrication. PANI@HA synthesized with HCl as a doping acid to condition the acidity at 1 M and 2.04 ANI/HA weight ratio (PANI@HA/1 M/2.04-HCl) demonstrates highest catalytic activity (98.17% conversion and 99.50% selectivity to 1,2-cyclohexanediol). The cyclohexene selective catalytic activity matches well with the PANI doping degree in PANI@HA. In addition, the optimal reaction condition is 20 mg catalyst, 2.5 mL H2O2, 70 °C, and 24 h. Furthermore, PANI@HA/1 M/2.04-HCl exhibits superior dihydroxylation activity toward 2,3-dimethyl-2-butene and cycling performance with 99.11% conversion and 96.92% selectivity to 1,2-cyclohexanediol after five cycles. The CV of PANI@HA indicates that the cyclohexene selective oxidation is attributed to a reversible redox reaction of PANI in PANI@HA for catalytic decomposition of H2O2.

Zeolite Y encaged Ru(III) and Fe(III) complexes for oxidation of styrene, cyclohexene, limonene, and α-pinene: An eye-catching impact of H2SO4 on product selectivity

A novel Ru(III) and Fe(III) complexes of ligands 1 and/or 2 {where 1 = 2,2'-((1E,1'E)-((azanediylbis(ethane-2,1-diyl))bis(azanylylidene))bis(methanylylidene))diphenol and 2 = 2,2'-((1E,1'E)-((azanediylbis(ethane-2,1-diyl))bis(azanylylidene))bis(methanylylidene)) bis(4-nitrophenol)} have been synthesized as ‘neat’ and zeolite Y encapsulated complexes. These catalysts are characterized by various analytical tools such as FTIR, UV–vis, elemental analysis, ICP-AES, molar conductivity, 1H- and 13C NMR, TGA, SEM, AAS, BET, magnetic susceptibility and powder XRD to endorse the complex formation, absence of peripheral redundant ligands and complexes, conservation of zeolite Y morphology and crystallinity, and the encapsulation of complexes without devastation in the zeolite Y framework. Out of these synthesized catalysts, 5Y is found to be a potent candidate for styrene (Conv. 76.1%, TOF: 2130 h?1), cyclohexene (Conv. 84.4%, TOF: 2351 h?1), limonene (Conv. 81.6%, TOF: 2273 h?1), and α-pinene (Conv. 72.6%, TOF: 2023 h?1) oxidation with high selectivity of respective allylic products excluding the styrene oxidation, which undergoes epoxidation only. The addition of H2SO4 in an identical reaction catalyzed by 5Y not only surge the conversion up to 100% in a short time span with high TOF but also increase the selectivity of respective epoxidation products. This switchover in the selectivities could be credited to the presence of H2SO4 that facilitates the heterolytic [sbnd]O[sbnd]O[sbnd] bond cleavage of metal hydroperoxide and stimulates the epoxidation over allylic oxidation. Furthermore, the results establish that the heterogeneous systems are effortlessly recovered and reused without ample drop in the activity and selectivity.

The studies on the limonene oxidation over the microporous TS-1 catalyst

The studies on the oxidation of limonene with 60 wt% hydrogen peroxide over the titanium silicalite TS-1 catalyst were carried out. The influence of the following parameters was examined: the temperature 0-120 °C, the molar ratio of limonene/H2O2 = 1:2-5:1, methanol concentration 60-95 wt%, TS-1 content 0.25-8 wt% and the reaction time 15 min to 11 days. The studies showed that the most beneficial conditions for the obtaining of high selectivity of 1,2-epoxylimonene, at simultaneously high values of the conversion of reactants and the efficiency of hydrogen peroxide, are as follows: the temperature 80 °C, the molar ratio of limonene/H2O2 = 1:1, the methanol concentration 80 wt%, the TS-1 content 3 wt% and the reaction time 10 days. Moreover, the research showed that the process of limonene oxidation is very complicated, because during this process also other very useful oxygenated derivatives of limonene can be obtained, for example: perillyl alcohol, carveol, carvone and 1,2-epoxylimonene diol. The studies on the reuse of the TS-1 catalyst showed that it is very stable catalyst at the studied conditions and it can be recycled to the oxidation process at least three times.