936-91-4

Upstream product

• 498-15-7 (+)-Δ³-carene 
• 5405-84-5 pinane hydroperoxide 
• 105663-03-4 4β-chloro-3α,10α-epoxycarene 
• 99530-90-2 4β-chloro-3(10)-carene 
• 19079-29-9 (1R,6R)-3,7,7-trimethylbicyclo[4.1.0]hepta-3-ene 
• 498-15-7 Δ³-carene 
• 13466-78-9 3-carene 
• 4497-92-1 2-carene 

Downstream Products

• 4017-88-3 4-isocaranol 
• 4017-82-7 (+)-trans-car-2-en-4-ol 
• 4017-83-8 (-)-(1R,3R,6S)-4-methylene-7,7-dimethylbicyclo[4.1.0]heptan-3-ol 
• 4017-81-6 (1S,3S,6R)-(-)-4-Caren-3α-ol 
• 38344-42-2 (R)-(-)-α-phellandren-8-ol 
• 13956-29-1 CBD 
• 22972-55-0 abnormal cannabidiol 
• 5957-75-5 delta-8-tetrahydrocannabinol 
• 1972-08-3 dronabinol 
• 4176-04-9 (1R,4S,6S)-4,7,7-Trimethyl-bicyclo[4.1.0]heptan-3-one 
• 242127-32-8 (-)-p-Menth-4-en-2-one 
• 119439-21-3 (+)-p-Menth-4-en-2-one 
• 23733-65-5 (S)-3-isopropyl-6-methylcyclohex-2-enone 
• 4017-89-4 (1S,3S,4R)-caran-4-ol 

Relevant academic research and scientific papers

Synthesis of new enantiopure trans-3,4-diaminocaranes from (+)-3-carene

A synthetic strategy to obtain new enantiopure trans-3,4-diaminocaranes derived from (+)-3-carene via a stereoselective methodology is described. The stereoselective preparation of 3,4-α-carene- or 3,4-β-carene-epoxide is followed by a ring opening by sodium azide to obtain the azido-alcohols. Subsequent cyclization affords the corresponding aziridine diastereoisomers, which are converted to azido amines by opening of the aziridine rings by sodium azide and then reduced to the final diamine diastereoisomers. The absolute configurations of the final diamines and of novel intermediates are established by 1H NMR spectra correlated with conformational analysis supported by molecular modeling.

Computational modeling of a stereoselective epoxidation: Reaction of carene with peroxyformic acid

(Chemical Equation Presented) Electronic structure theory was used to model the epoxidation of 3-carene by peroxyformic acid. Reactants, products, and transition states were optimized at the B3LYP/6-31G* level of theory, followed by B3LYP/6-311+G** and MP2/6-311+G** single point calculations. The reaction pathway yielding the trans-epoxide product was found to have a significantly lower reaction barrier (7.8 kcal/mol) than that leading to the cis-epoxide product (9.4 kcal/mol), in agreement with expectations. Magnetic shieldings of the two isomeric carene epoxides were also calculated, using the GIAO method, and compared to experimental 1H and 13C NMR spectra. Although the calculated carbon spectra proved inconclusive, the proton shieldings calculated for the trans-epoxide correlated much more closely to the experimental values for the major epoxidation product than did the shieldings calculated for the cis-epoxide, serving to verify the identity of the major product.

Synthesis of Aminoalkylated Aziridines from (+)-3-Carene

Aminoalkylated carane-type aziridines were synthesized via epoxidation of (+)-3-carene by H2O2 solution (7%) in EtOAc catalyzed by α-Al2O3 nanoparticles, opening of the epoxide by NaN3, and cyclization of the azidoalcohol by Ph3P followed by condensation of the resulting aziridines with formalin and secondary amines. The cytotoxicity of the aminoalkylated aziridines with heteroorganic substituents increased on going from a five-membered pyrrolidine ring substituent to a six-membered piperidine ring and decreased sharply upon replacing a piperidine by a morpholine ring or increased on going to a piperazine ring. The structures of products were established using IR and NMR spectroscopy and an X-ray crystal structure analysis.

RUTHENIUM COMPLEX AND PRODUCTION METHOD THEREOF, CATALYST, AND PRODUCTION METHOD OF OXYGEN-CONTAINING COMPOUND

PROBLEM TO BE SOLVED: To provide a ruthenium complex that is particularly useful as a catalyst for oxidizing a substrate having a carbon-hydrogen bond. SOLUTION: The ruthenium complex represented by the general formula (i) or a cis conformer thereof is provided. In the general formula (i), R1 represents H, a phenyl group or a substituted phenyl group; R2 represents H, a phenyl group or an alkyl group; L1 represents halogen or water molecule; L2 represents triphenylphosphine, pyridine, imidazole or dimethylsulfoxide; X represents halogen; and n represents 1 or 2. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPO&INPIT

Sustainable catalytic epoxidation of biorenewable terpene feedstocks using H2O2as an oxidant in flow microreactors

Solvent-free continuous flow epoxidation of the alkene bonds of a range of biorenewable terpene substrates have been carried out using a recyclable tungsten-based polyoxometalate phase transfer catalyst and aqueous H2O2 as a benign oxidant. These sustainable flow epoxidation reactions are carried out in commercial microreactors containing static mixing channels that enable common monoterpenes (e.g. untreated crude sulfate turpentine, limonene, etc.) to be safely epoxidized in short reaction times and in good yields. These flow procedures are applicable for the flow epoxidation of trisubstituted and disubstituted alkenes for the safe production of multigram quantities of a wide range of epoxides. This journal is

Sustainable catalytic protocols for the solvent free epoxidation and: Anti -dihydroxylation of the alkene bonds of biorenewable terpene feedstocks using H2O2 as oxidant

A tungsten-based polyoxometalate catalyst employing aqueous H2O2 as a benign oxidant has been used for the solvent free catalytic epoxidation of the trisubstituted alkene bonds of a wide range of biorenewable terpene substrates. This epoxidation protocol has been scaled up to produce limonene oxide, 3-carene oxide and α-pinene oxide on a multigram scale, with the catalyst being recycled three times to produce 3-carene oxide. Epoxidation of the less reactive disubstituted alkene bonds of terpene substrates could be achieved by carrying out catalytic epoxidation reactions at 50 °C. Methods have been developed that enable direct epoxidation of untreated crude sulfate turpentine to afford 3-carene oxide, α-pinene oxide and β-pinene oxide. Treatment of crude epoxide products (no work-up) with a heterogeneous acid catalyst (Amberlyst-15) results in clean epoxide hydrolysis to afford their corresponding terpene-anti-diols in good yields.

Carane amino alcohols as organocatalysts in asymmetric aldol reaction of isatin with acetone

Carane-derived β-amino alcohols with amino and hydroxy groups at positions 3 and 4 differing in their mutual arrangement and configuration were synthesized. Their application as organocatalysts in the asymmetric aldol reaction of isatin with acetone allowed one to obtain adducts with up to 84% enantiomeric excess.

Stereoselective Synthesis of Carane-Type Hydroxythiols and Disulfides Based on Them

Isomeric 10-sulfanylcaran-4-ols and 4-sulfanylcaran-3-ols were synthesized and used to prepare disulfides in high yields.

Regioselective and Stereospecific Copper-Catalyzed Deoxygenation of Epoxides to Alkenes

Two copper salts (Cu(CF3CO2)2 and IMesCuCl) were identified as earth-abundant, inexpensive, but effective metal catalysts together with diazo malonate for chemo-/regioselective and stereospecific deoxygenation of various epoxides with tolerance of common functional groups (alkene, ketone, ester, p-methoxybenzyl, benzyl, tert-butyldimethylsilyl, and triisopropylsilyl). In particular, the unprecedented regioselectivity allowed for the first time monodeoxygenation of diepoxides to alkenyl epoxides. Density functional theory mechanistic studies showed that the deoxygenation occurred by collapsing the free ylide, unfavoring the possible intuitive pathway via cycloreversion of possible oxetane.

Switching the reaction pathways of electrochemically generated β-haloalkoxysulfonium ions - Synthesis of halohydrins and epoxides

β-Haloalkoxysulfonium ions generated by the reaction of electrogenerated Br+ and I+ ions stabilized by dimethyl sulfoxide (DMSO) reacted with sodium hydroxide and sodium methoxide to give the corresponding halohydrins and epoxides, respectively, whereas the treatment with triethylamine gave α-halocarbonyl compounds.