20307-86-2

Upstream product

• 2244-16-8 (S)-p-mentha-6,8-dien-2-one 
• 555-31-7 aluminum isopropoxide 
• 5989-27-5 D-limonene 
• 31198-76-2 carvoxime 
• 138-86-3 limonene. 
• 1195-92-2 Limonene oxide 
• 5989-54-8 (-)-(S)-limonene 
• 6485-40-1 (R)-Carvone 
• 99-49-0 Carvone 
• 1134-95-8 2-methyl-5-(prop-1-en-2-yl)cyclohex-2-en-1-yl acetate 
• 136476-14-7 [(S)-2,2-Dimethyl-1-((E)-2-methyl-buta-1,3-dienyloxy)-propyl]-benzene 
• 78-79-5 isoprene 
• 175522-76-6 [(R)-2,2-Dimethyl-1-((E)-2-methyl-buta-1,3-dienyloxy)-propyl]-benzene 
• 136476-12-5 [(S)-2-Methyl-1-((E)-2-methyl-buta-1,3-dienyloxy)-propyl]-benzene 

Downstream Products

• 56169-11-0 (-)-α-phellandrene 
• 913815-72-2 C₁₆H₃₀OSi 
• 1423157-23-6 (5R)-2-methyl-5-(prop-1-en-2-yl)cyclohex-2-enyl 4-((E)-2-nitrovinyl)benzoate 
• 22567-15-3 p-menth-6-en-2,9-diol 
• 73354-61-7 cis-5-isopropenyl-2-methyl-2-cyclohexenyl diethyl phosphate 
• 57429-67-1 (+/-)-O-(3.5-dinitro-benzoyl)-cis-carveol 

Relevant academic research and scientific papers

Cytochrome P-450 dependent (+)-limonene-6-hydroxylation in fruits of caraway (Carum carvi)

Microsomal preparations from fruits of annual and biennial forms of caraway (Carum carvi L.) catalyze the C-6 hydroxylation of (+)-limonene to (+)-trans-carveol, the key intermediate in the biosynthesis of carvone. The enzyme activities from both caraway forms had similar properties (pH optimum, K(m), cofactor requirements, etc). Both activities were dependent on NADPH and O2, and were inhibited by N-substituted imidazoles, metyrapone, cytochrome c and CO, and thus meet many of the established criteria for cytochrome P-450-dependent mixed function oxygenases.

Tin-containing hydrotalcite-like compounds as catalysts for the Meerwein-Ponndorf-Verley reaction

Hydrotalcite-like compounds (HTs) containing Mg/Al or Mg/Al/Sn were prepared and used as precursors to obtain basic catalysts by calcination at 450 C. The catalysts were used in the Meerwein-Ponndorf-Verley (MPV) reaction of benzaldehyde and cyclohexanone in the presence of 2-propanol as hydrogen donor. The mixed oxide obtained by calcining the tin-containing HT was found to be more catalytically active than that obtained from the Mg/Al HT and the pure magnesium oxide. This result can be ascribed to the mechanism of the reaction, which involves acid-base sites on the catalyst surface. The most active catalyst was used in the MPV reactions of other carbonyl compounds including aldehydes and ketones with excellent conversion and selectivity.

Towards the bio-production of trans-carveol and carvone from limonene: Induction after cell growth on limonene and toluene

Rhodococcus opacus PW4 cells were found to produce trans- and cis-carveol and/or carvone as result of limonene metabolism, depending on the type and concentration of the carbon source used for cell growth. In aqueous systems, cells grown on ethanol and toluene only produced trans-carveol, whilst cells grown on limonene and on toluene with a larger head-space available produced both trans-carveol and carvone. In biphasic systems, limonene was converted to trans- and cis-carveol as well as to carvone, regardless of the carbon source used, although carveol and carvone production rates were higher in toluene and limonene grown cells, respectively. A good and stable emulsion was obtained in a magnetically stirred two-phase reactor but both trans-carveol and carvone were produced at low rates: 0.08 and 0.02 nmol/min mg prot, respectively. No cis-carveol was formed. When (-)-carveol was added, carvone production increased 4.7 fold to 0.12 nmol/min mg prot. Using an aerated two-phase reactor, carvone production was enhanced even with cells grown on toluene. The highest trans- and cis-carveol and carvone production rates were attained with cells grown on limonene by continuously supplying limonene to the reactor through the air stream, carvone production reaching 0.58 nmol/min mg prot. The best trans-/cis-carveol ratio (2.26) was observed with cells grown on toluene when limonene was supplied in the gas phase. When 50 mM limonene was added initially, carvone was produced 27.9 and 141.4 times faster than trans-carveol with cells grown on toluene and limonene, respectively.

Regio- and stereoselective allylic hydroxylation of D-limonene to (+)-trans-carveol with cellulosimicrobium cellulans EB-8-4

Cellulosimicrobium cellulans EB-8-4 was discovered by screening of microorganisms as a pow-erful catalyst for the regio- and stereoselective allylic hydroxylation of D-limonene to (+)-trans-carveol that is a useful and valuable fragrance and flavour compound. Cells of strain EB-8-4 were easily obtained, demonstrated more than 99% regio- and stereoselectivity, showed a specific hydroxylation activity of 4.0 U/g cdw (cell dry weight), and accepted 62 mM D-limonene without inhibition. The hydroxylation was possibly catalyzed by an nicotinamide adenine dinucleotide (NADH)-dependent oxygenase involved in the degradation of aromatic ring during cell growth. 13.4 mM of (+)-trans-carveol were obtained by biohydroxylation of D-limonene with resting cells of C. cellulans EB-8-4, thus being 11 times higher than that obtained with the best biocatalyst known thus far. High conversion and high yield were obtained in the biohydroxylation of 11.6 mM of D-limonene with the resting cells as catalyst in a closed shaking flask, giving 10 mM of (+)-irans-carveol, and 0.30 mM of carvone as the only by-product. Thus, a unique biocatalyst for the regio- and stereoselective allylic hydroxylation of D-limonene and an efficient synthesis of natural identical (.+)-trans-carveol by biohydroxylation have been developed.

Pt/Ferric Hydroxyphosphate: An Effective Catalyst for the Selective Hydrogenation of Α,Β-Unsaturated Aldehydes (Ketones) into Α,Β-Unsaturated Alcohols

Abstract: Four micro (nano)-sized mesoporous ferric hydroxyphosphates (FHP) are synthesized by a reverse microemulsion-solvothermal method, and then are used as supports to prepare supported Pt catalysts. The mean particle diameter of Pt nanoparticles (NPs) was 4.5–4.6?nm. When the four different Pt/FHP catalysts were used into the hydrogenation of α,β-unsaturated aldehydes (ketones) to their corresponding unsaturated alcohols, Pt/FHP (c) catalyst showed better catalytic performance than the other three partners. Under the optimal experimental conditions, several tested α,β-unsaturated aldehydes could be effectively transformed into corresponding unsaturated alcohols over Pt/FHP (c) catalyst. The catalyst could be recycled and reused several times without activity loss. We propose the stronger interaction between the Pt NPs and ferric ions of the FHP (c) are responsible for its good catalytic performance, and this stronger interaction should be rooted in its enhanced Lewis acid strength.

Photooxidation and phototoxicity of π-extended squaraines

This paper describes the synthesis of π-extended squaraines and their photooxidation properties and gives an in-depth characterization of these molecules as photosensitizing agents. Squaraines show a strong absorption in the tissue transparency window (600-800 nm), and upon irradiation, they undergo a photooxidation process, leading to the formation of peroxide and hydroperoxide radicals according to a type I radical chain process. Confocal laser microscopy demonstrates that the designed squaraines efficiently internalize in the cytoplasm and not in the nucleus of the cell. In the dark, they are scarcely cytotoxic, but after irradition, they promote a strong dose-dependent phototoxic effect in four different cancer cells. In HeLa and MCF-7 cells, squaraines 4 and 5, thanks to their hydrocarbon tails, associate to the membranes and induce lipid peroxidation, as indicated by a marked increase of malonyldialdehyde after photodynamic treatment, in agreement with in vitro photooxidation studies. FACS, caspase-3/7 assays and time-lapse microscopy demonstrate that the designed squaraines cause cell death primarily by necrosis.

Specific adducts formed through a radical reaction between peptides and contact allergenic hydroperoxides

The first step in the development of contact allergy (allergic contact dermatitis) includes the penetration of an allergy-causing chemical (hapten) into the skin, where it binds to macromolecules such as proteins. The protein - hapten adduct is then recognized by the immune system as foreign to the body. For hydroperoxides, no relevant hapten target proteins or protein - hapten adducts have so far been identified. In this work, bovine insulin and human angiotensin I were used as model peptides to investigate the haptenation mechanism of three hydroperoxide haptens: (5R)-5-isopropenyl-2-methyl-2- cyclohexene-1-hydroperoxide (Lim-2-OOH), cumene hydroperoxide (CumOOH), and 1-(1-hydroperoxy-1-methylethyl) cyclohexene (CycHexOOH). These hydroperoxides are expected to react via a radical mechanism, for which 5,10,15,20-tetraphenyl- 21H,23H-porphine iron(III) chloride (Fe(III)TPPCl) was used as a radical initiator. The reactions were carried out in 1:1 ethanol/10 mM ammonium acetate buffer pH 7.4, for 3 h at 37 °C, and the reaction products were either enzymatically digested or analyzed directly by MALDI/ TOF-MS, HPLC/MS/MS, and 2D gel electrophoresis. Both hydroperoxide-specific and unspecific reaction products were detected, but only in the presence of the iron catalyst. In the absence of catalyst, the hydroperoxides remained unreacted. This suggests that the hydroperoxides can enter into the skin and remain inert until activated. Through the detection of a Lim-2-OOH adduct bound at the first histidine (of two) of angiotensin I, it was confirmed that hydroperoxides have the potential to form specific antigens in contact allergy.

Isomerization of α-pinene oxide in the presence of methyltrioxorhenium(VII)

The catalytic performance of methyltrioxorhenium(VII) (MTO) has been investigated for the first time in the isomerization of α-pinene oxide (PinOx) into campholenic aldehyde (CPA). The high isomerization activity of MTO is coupled with high selectivity to CPA: CPA yield of up to 87% (100% conversion) was obtained by using α,α,α-trifluorotoluene as solvent at 15 C. Catalyst recycling is possible in a relatively simple fashion by using MTO coupled to an appropriate ionic liquid. The catalytic application of MTO in the isomerization of PinOx versus the integrated epoxidation- isomerization process of the conversion of α-pinene into CPA is discussed.

REACTION OF CIS-CARVEOL WITH TRIPHENYLPHOSPHINE AND TETRACHLOROMETHANE: A NOTE ON THE MECHANISM OF THE LEE REACTION

The title reaction yielded trans-carvyl chloride 2 and pinol 3.The formation of pinol and the specific rotation of the carvyl chloride are affected by the presence of acid.The implications of these findings on the understanding of the course of he reaction are discussed.Use of an acid scavenger is recommended in application of the PPh3-CCl4 reagent for acid sensitive compounds.A bimolecular, concerted group transfer mechanism (Scheme 2) is suggested for the decomposition of the intermediate alkoxytriphenylphosphonium halide 7.

Nickel-Catalyzed Arylation of C(sp3)-O Bonds in Allylic Alkyl Ethers with Organoboron Compounds

A nickel-catalyzed cross-coupling of allylic alkyl ethers with organoboron compounds through the cleavage of the inert C(sp3)-O(alkyl) bonds is described. Several types of allylic alkyl ethers can be coupled with various boronic acids or their derivatives to give the corresponding products in good to excellent yields with wide functional group tolerance and excellent regioselectivity. The gram-scale reaction and late-stage modification of biologically active compounds further prove the practicality of this synthetic method.