772-36-1

Upstream product

• 60661-95-2 1,6-dichloro-p-menthane-2,8-diol 
• 80-56-8 Pinene 
• 99-49-0 Carvone 
• 110202-13-6 1,2-dibromo-p-menthan-8-ol 
• 1686-14-2 (1R,2R,4S,6R)-2,7,7-trimethyl-3-oxatricyclo[4.1.1.0.^2,4]octane 
• 80-26-2 terpinyl acetate 
• 71697-84-2 (-)-trans-sobrerol 
• 56423-45-1 (4R,8RS)-8,9-epoxy-p-menth-6-en-2-one 
• 1197-06-4 cis-2-methyl-5-(1-methylethenyl)-2-cyclohexen-1-ol 
• 326598-95-2 (1R,3S,4S,5R)-5-acetoxy-3-hydroxy-4-methyl-1-(methoxycarbonyl)cyclohexane 
• 75-16-1 methylmagnesium bromide 
• 326622-28-0 (4R,6R)-6-acetoxy-1-methyl-4-(methoxycarbonyl)cyclohexene 
• 10482-56-1 (-)-(S)-α-terpineol 
• 98-55-5 terpineol 

Downstream Products

• 38223-90-4 p-menthane-1,2,6,8-tetraol 
• 498-71-5 (1SR,5RS)-5-(2-hydroxypropan-2-yl)-2-methylcyclohex-2-enol 
• 454-77-3 5-(2-hydroxypropan-2-yl)-2-methylcyclohex-2-enol 
• 34182-03-1 (R)-5-(1-hydroxy-1-methylethyl)2-methylcyclohex-2-enone 
• 7712-46-1 5-(1-Hydroxy-1-methyl-ethyl)-2-methyl-cyclohex-2-enone 
• 38235-58-4 trans-sobrerol 
• 71697-84-2 (-)-trans-sobrerol 
• 106262-55-9 Octanoic acid 5-(1-hydroxy-1-methyl-ethyl)-2-methyl-cyclohex-2-enyl ester 
• 137821-91-1 (-)-(1S,5R)-sobrerol 
• 68754-15-4 6,8-diacetoxy-p-menth-1-ene 

Relevant academic research and scientific papers

Biomimetic conversion of α-pinene with H2O2 to sobrerol over V2O5: Dihydroxylation by a peroxo vanadium peracid vectoring gentle synergistic oxidation

In this communication, we report the gentle preparation of sobrerol from dihydroxylation of α-pinene synergistically catalyzed by V2O5-H2O2 under benign conditions. It was proposed that a “peroxo vanadium acid”, VVO(OH)(OOH), was formed by HOO? insertion and proton transfer between V2O5 and H2O2. Theoretical DFT calculations that using the dimer?vanadium peracid as a model of the catalytically active species revealed that peroxo vanadium acid exhibited bifunctional catalytic capabilities resembling epoxidation of α-pinene by peracetic acid and then open-ring hydration with an acetic media.

Hot water-promoted SN1 solvolysis reactions of allylic and benzylic alcohols

During the studies of hydrolysis of epoxides in water, we found that the hydrolysis of (-)-α-pinene oxide at 20 °C gave enantiomerically pure trans-(-)-sobrerol, whereas the same reaction in water heated at reflux unexpectedly gave a racemic mixture of trans- and cis-sobrerol (trans/cis=6:4). We have examined this remarkable difference in detail and found that hot water, whose behavior is quite different compared with room- or high-temperature water, could promote SN1 solvolysis reactions of allylic alcohols and thus caused the racemization of trans-(-)-sobrerol. The effect of reaction temperature, the addition of organic co-solvent, and the concentration of the solute on the rate of the racemization of trans-(-)-sobrerol were further examined to understand the role that hot water played in the reaction. It was proposed that the catalytic effects of hot water are owing to its mild acidic characteristic, thermal activation, high ionizing power, and better solubility of organic reactant. Further investigation showed that the racemization of other chiral allylic/benzylic alcohols could efficiently proceed in hot water.

Unique salt effect on highly selective synthesis of acid-labile terpene and styrene oxides with a tungsten/Hcatalytic system under acidic aqueous conditions

Acid-labile epoxides such as terpene and styrene oxides are effectively synthesized in high yields with good selectivities using tungsten-catalyzed hydrogen peroxide epoxidation in the presence of NaO The salt effect is thought to originate with the addition of a saturated amount of NaOto aqueous H this addition strongly inhibited the undesired hydrolysis of the acid-labile epoxy products, despite the biphasic conditions of substrate as oil phase and Has acidic aqueous phase.

Unique salt effect on the high yield synthesis of acid-labile terpene oxides using hydrogen peroxide under acidic aqueous conditions

Acid-labile epoxides such as -pinene oxide are (effectively) synthesized in high yield from the epoxidation of terpenes with aqueous H2O 2 catalyzed by Na2WO4, [Me(n-C 8H17)3N]HSO4, and PhP(O)(OH) 2 in the presence of Na2SO4 as an auxiliary additive under organic solvent-free conditions at ambient temperature. Origin of the salt effect is considered that the addition of a saturated amount of Na2SO4 to aqueous H2O2 strongly inhibited the undesired hydrolysis of the acid-labile epoxide products, despite the highly acidic reaction conditions. Georg Thieme Verlag Stuttgart · New York.

Phosphotungstic acid as a versatile catalyst for the synthesis of fragrance compounds by α-pinene oxide isomerization: Solvent-induced chemoselectivity

The remarkable effect of the solvent on the catalytic performance of H 3PW12O40, the strongest heteropoly acid in the Keggin series, allows direction of the transformations of α-pinene oxide (1) to either campholenic aldehyde (2), trans-carveol (3), trans-sobrerol (4a), or pinol (5). Each of these expensive fragrance compounds was obtained in good to excellent yields by using an appropriate solvent. Solvent polarity and basicity strongly affect the reaction pathways: nonpolar nonbasic solvents favor the formation of aldehyde 2; polar basic solvents favor the formation of alcohol 3; whereas in polar weakly basic solvents, the major products are compounds 4a and 5. On the other hand, in 1,4-dioxane, which is a nonpolar basic solvent, both aldehyde 2 and alcohol 3 are formed in comparable amounts. The use of very low catalyst loading (0.005-1 mol%) and the possibility of catalyst recovery and recycling without neutralization are significant advantages of this simple, environmentally benign, and low-cost method. This method represents the first example of the synthesis of isomers from α-pinene oxide, other than campholenic aldehyde, with a selectivity that is sufficient for practical usage.

A convenient, large scale synthesis of trans-(+)-sobrerol

A convenient and highly efficient synthesis of optically pure trans(+)-sobrerol (1), starting from methyl 3,5-dihydroxy-4-methyl benzoate 2 in 8 steps with overall yield 26%, is reported. The key intermediate 4 is prepared in remarkably high yield by selectively esterification of 3 using lipase as catalyst. A critical step to stereoselectively inverse the configuration of 7 is realized under Mistunobu conditions.

Asymmetrization of all-cis-3,5-dihydroxy-1-(methoxycarbonyl)cyclohexane and of the 4-methyl and 4-ethyl substituted homologues

Enantiomerically pure mono acylated derivatives of cis,cis-3,5-dihydroxy-1-(methoxycarbonyl)cyclohexane 1, all-cis-3,5-dihydroxy-4-methyl-1-(methoxycarbonyl)cyclohexane 2 and all-cis-3,5-dihydroxy-4-ethyl-1-(methoxycarbonyl)cyclohexane 3 were obtained upon lipase catalyzed asymmetrization. PPL-catalyzed transesterification of 1 with vinyl acetate led in high yield to the (S)-monoacetate (+)-13. With substrates 2 and 3 this process was slower and gave the (R)-monoacetates (-)-14 and (-)-15; the best results were obtained with SAM II lipase. On the other hand, enantiotoposelective hydrolysis of their diacetates and especially dibutyrates gave useful results only for the 4-substituted substrates and produced the (S)-monoesters. Copyright (C) 2000 Elsevier Science Ltd.

Comparative autoxidation of 3-Carene and α-Pinene: Factors governing regioselective hydrogen abstraction reactions

Autoxidation reactions of 3-Carene 1 and α-Pinene 2 were performed using various homogeneous catalysts. Different product and regio- selectivities were observed. The factors that promote hydrogen abstraction (HA) reactions in both molecules are discussed, and it is proposed that the difference in the product selectivities is due to the lack of 'cyclic activation' in 2. Oxidation of 1 produced mainly 3-carene-5-one 3, while 2 yielded 2,3-epoxypinane 6 as the major product.

EVIDENCE FOR THE INVOLVEMENT OF CYTOCHROME P-450-DEPENDENT MONOOXYGENASES IN THE ALLYLIC HYDROXYLATION OF TERPINEOLS BY NICOTIANA TABACUM CELL CULTURES

A microsomal preparation isolated from suspension cells of Nicotiana tabacum was able to catalyse the hydroxylation of terpineols and their acetates at the allylic positions.The hydroxylase activities depend strictly on the presence of NADPH as the reducing cofactor and on molecular oxygen as the donor.The hydroxylases were inhibited by cytochrome P-450 enzyme inhibitors, such as carbon monoxide, metyrapone and miconazole.Thus it was established that the hydroxylases are cytochrome P-450-dependent monooxygenases. - Key words: Nicotiana tabacum; Solanaceae; cell cultures; monooxygenase; hydroxylase; allylic hydroxylation; cytochrome P-450; terpineols.

Pheromone Synthesis, CIV.- Synthesis of the Enantiomers of α-Phellandren-8-ol (p-Mentha-1,5-dien-8-ol), a Monoterpene from Bark Beetles

Enantiomerically pure (R)-α-phellandren-8-ol (p-mentha-1,5-dien-8-ol, 1a) was synthesized from (R)-carvone (2).Similarly (S)-1a was synthesized from (S)-2.