14575-93-0

Usage

Uses

Used in Pharmaceutical Industry:
[1S-(1alpha,2beta,5alpha)]-2,6,6-trimethylbicyclo[3.1.1]heptan-3-one is used as an active ingredient for its analgesic and anti-inflammatory properties, making it a valuable component in medicinal products.
Used in Pesticidal Products:
Camphor is used as a key component in the production of mothballs, leveraging its natural insect-repelling properties to protect fabrics and clothing from damage.
Used in Culinary Industry:
[1S-(1alpha,2beta,5alpha)]-2,6,6-trimethylbicyclo[3.1.1]heptan-3-one is utilized as an ingredient in cooking spices, adding a unique flavor and aroma to various dishes.
Used in Flavoring and Fragrance Industry:
[1S-(1alpha,2beta,5alpha)]-2,6,6-trimethylbicyclo[3.1.1]heptan-3-one is used as a flavoring agent in the food and beverage industry, as well as in the creation of fragrances due to its distinct and pleasant odor.
Used in Chemical Synthesis:
[1S-(1alpha,2beta,5alpha)]-2,6,6-trimethylbicyclo[3.1.1]heptan-3-one is employed in the synthesis of various pharmaceuticals, highlighting its versatility and importance in the chemical industry.
Used in Flavoring and Fragrance Industry (specifically for its stereochemistry):
The stereochemistry of [1S-(1alpha,2beta,5alpha)]-2,6,6-trimethylbicyclo[3.1.1]heptan-3-one is particularly important for its biological activity, making it a crucial component in the production of various chemical products within the flavoring and fragrance industry.

Upstream product

• 1196-00-5 (+)-isopinocampheol 
• 35998-01-7 (1S,2S,3R,5R)-(-)-neoisopinocampheol 
• 99956-72-6 (1R,2R,5R)-2α-(Carboxy)-pinan-3-on 
• 19894-98-5 6,6-dimethyl-2-methylene-bicyclo[3.1.1]heptan-3-ol 
• 7785-70-8 (+)-α-pinene 
• 80-56-8 rac-α-pinene 
• 80-56-8 Pinene 
• 1686-14-2 2α,3α-epoxypinane 
• 473-61-0 (1RS:2SR:3RS)-Pinanol-⁽³⁾ 
• 64-19-7 acetic acid 
• 99956-70-4 (1R,2S,5R)-2α-(Hydroxymethyl)-pinan-3-on 
• 7785-26-4 (-)-α-pinene 
• 303801-38-9 (1S,5S)-2,6,6-trimethylbicyclo[3.1.1]heptane 
• 34413-88-2 pinocarvone 

Downstream Products

• 1845-25-6 (-)-(2R,3R,5R)-2-hydroxy-3-pinanone 
• 141243-74-5 (+)-(1R,2R)-2,7,7-Trimethyl-3-oxabicyclo<4.1.1>octan-4-one 
• 34182-03-1 (R)-5-(1-hydroxy-1-methylethyl)2-methylcyclohex-2-enone 

Relevant academic research and scientific papers

Stereochemistry in the oxidation of primary amines to nitro compounds by dimethyldioxirane

Oxidation of the chiral amines, (+) and (-)-isopinocampheylamine, with dimethyldioxirane (1) gives the corresponding nitro compounds with retention of configuration at the amine-hearing carbon atom. When lower amounts of I are used in the oxidation the amines give the nitroso dimers as the major products. Treatment of the nitroso dimer from the (-)-amine with additional 1 gave the same nitro compound as obtained from the amine oxidation. To further indicate that no racemization occurs during the amine oxidation we have synthesized the oxime of the nitroso intermediate and shown that it does not tautomerize under the reaction conditions.

Asymmetric Synthesis of Oxygenated Monoterpenoids of Importance for Bark Beetle Ecology

Herein we report the asymmetric syntheses of a number of oxygenated terpenoids that are of importance in the chemical ecology of bark beetles. These are pinocamphones, isopinocamphones, pinocarvones, and 4-thujanols (= sabinene hydrates). The camphones were synthesized from isopinocampheol, the pinocarvones from β-pinene, and the thujanols from sabinene. The NMR spectroscopic data, specific rotations, and elution orders of their stereoisomers on a chiral GC-phase (β-cyclodextrin) are also reported. This enables facile synthesis of pure compounds for biological activity studies and identification of stereoisomers in mixed natural samples.

Catalytic olefin epoxidation with a carboxylic acid-functionalized cyclopentadienyl molybdenum tricarbonyl complex Dedicated to Prof. Maria José Calhorda on the occasion of her 65th birthday and in recognition of her outstanding contributions to the field of computational organometallic chemistry.

The complex CpMo(CO)3CH2COOH (1) (Cp = η5-C5H5) has been examined as a precatalyst for the epoxidation of cis-cyclooctene and α-pinene using tert-butylhydroperoxide (TBHP) as oxidant. A high turnover frequency of ca. 600 mol molMo-1 h-1 was achieved in the epoxidation of cyclooctene, giving the epoxide as the only reaction product. With α-pinene as substrate, the added-value products α-pinene oxide and campholenic aldehyde were obtained. Two different approaches to facilitate catalyst recovery and reuse were explored: (1) use of an ionic liquid (IL) as solvent, and (2) intercalation of 1 in a Zn,Al layered double hydroxide (LDH) by a direct synthesis (coprecipitation) route. Characterization of the LDH by powder X-ray diffraction, thermogravimetric analysis, FT-IR and 13C CP MAS NMR spectroscopies showed that the CpMo(CO)3CH 2COO- anions intercalate in a bilayer arrangement, resulting in an interlayer spacing of 20.7 A?. In the epoxidation of cyclooctene, catalytic activity in the first batch run was very high for the catalyst/IL mixture and moderate for the LDH. Characterization of the LDH after catalysis indicated that nearly complete oxidative decarbonylation of supported complexes had occurred (by reaction with TBHP), resulting in the presence of immobilized oxomolybdenum species. However, catalytic activities for both the recovered LDH and catalyst/IL decreased in consecutive runs, due in part to progressive removal of active species during either the catalytic reaction (for the LDH) or the solvent extraction/work-up (for the catalyst/IL mixture).

Enantioselectivity in the Biotransformation of Bicycloheptanes with the Cultured Cells of Nicotiana tabacum

The biotransformation of the enantiomeric pairs of bicycloheptane derivatives with the cultured cells of Nicotiana tabacum was investigated.The hydrogenation of the C-C double bond of verbenone took place enantioselectively in preference of the (1S,5S)-enantiomer and the hydrogen attack occurred stereospecifically from the re-face at its C-2.The oxidation of the hydroxyl group of neoisopinocampheol occurred enantioselectively in preference of the (1S,2S,3R,5R)-enantiomer, whereas such an enantioselective oxidation was not the case for neoisoverbanol.

Aminium Salts Catalyzed Rearrangement of α-Pinene and β-Ionone Oxides

β-ionone and α-pinene oxides 1,3 isomerize rapidly and selectively to 1-(1,2,2-trimethylcyclopent-1-yl)-pent-2-en-1,4-dione 2 and the industrially important 2,2,3-trimethyl-3-cyclopentene acetaldehyde 4, under the influence of catalytic amounts of aminium salts A, B.In order to find insights into the mechanism of our procedure, protic and Lewis acids-catalyzed rearrangements have also been reconsidered.

Enantioselective deprotometalation of alkyl ferrocenecarboxylates using bimetallic bases

The enantioselective deprotometalation of alkyl ferrocenecarboxylates (FcCO2R) using mixed lithium-zinc or lithium-cadmium bases is described. By using FcCO2Me as the substrate, chiral lithium alkyl-amidozincates prepared from exo-(αR)- or endo-(αS)-N-(α-phenylethyl)bornylamine (H-exo-born-R or H-endo-born-S) were tested; the best results (27% yield and 62% ee in favor of the RP enantiomer) were obtained by using Bu2(endo-born-S)ZnLi in tetrahydrofuran (THF) at -30 °C before iodolysis. Due to the low compatibility of FcCO2Me with alkyl-containing lithium zincates, 1?:?1 mixtures of lithium and zinc amides were tested. Chiral (H-exo-born-R or H-endo-born-S) or/and achiral (lithium 2,2,6,6-tetramethylpiperidide or lithium diisopropylamide) secondary amines gave good results, the best (81% yield and 44% ee in favor of the RP enantiomer) being obtained by using (endo-born-S)3ZnLi in THF at room temperature. Among other secondary amines also prepared and/or tested, commercial (S,S)-bis(α-phenylethyl)amine (H-PEA-S) proved promising. After optimization of the reaction conditions, the best enantioselectivity (26% yield and 80% ee in favor of the RP enantiomer) was observed by treating a THF solution of FcCO2Me and Zn(PEA-S)2 with Li-PEA-S at -80 °C before iodolysis. That no reaction took place with cadmium instead of zinc suggests the formation of 'ate complexes upon treatment of Cd(PEA-S)2 by Li-PEA-S while Zn(PEA-S)2 and Li-PEA-S would rather work in tandem (Li-PEA-S as the base and Zn(PEA-S)2 as the in situ trap for the formed ferrocenyllithium). While FcCO2Me, FcCO2tBu and FcCO2iPr could be converted into their racemic 2-iodinated derivatives with a yield of 84 to 87% by employing LiTMP (2 equiv.) in the presence of ZnCl2·TMEDA (1 equiv.) as an in situ trap, their enantioselective deprotometalation rather required Li-PEA-S together with Zn(PEA-S)2 to produce the enantio-enriched derivatives with yields of 45-82% and 71% ee. This journal is

Synthesis of bimetallic Zr(Ti)-naphthalendicarboxylate MOFs and their properties as Lewis acid catalysis

Bimetallic Zr(Ti)-NDC based metal-organic frameworks (MOFs) have been prepared by incorporation of titanium(iv) into zirconium(iv)-NDC-MOFs (UiO family). The resulting materials maintain thermal (up to 500 °C), chemical and structural stability with respect to parent Zr-MOFs as can be deduced from XRD, N2 adsorption, FTIR and thermal analysis. The materials have been studied in Lewis acid catalyzed reactions, such as, domino Meerwein-Ponndorf-Verley (MPV) reduction-etherification of p-methoxybenzaldehyde with butanol, isomerization of α-pinene oxide and cyclization of citronellal.

Ring-opening of epoxides promoted by organomolybdenum complexes of the type [(η5-C5H4R)Mo(CO)2(η3-C3H5)] and [(η5-C5H5)Mo(CO)3(CH2R)]

The cyclopentadienyl molybdenum carbonyl complexes [(η5-C5H4R)Mo(CO)2(η3-C3H5)] and [(η5-C5H5)Mo(CO)3(CH2R)] (R = H, COOH) have been shown to promote acid-catalysed reactions in liquid phase, under moderate conditions. The catalytic alcoholysis of styrene oxide with ethanol at 35 °C gave 2-ethoxy-2-phenylethanol in 100% yield within 30 min for the dicarbonyl complexes and 3-6 h for the tricarbonyl complexes. Steady catalytic performances were observed in consecutive runs with the same catalytic solution, suggesting fairly good catalytic stability. In the second acid-catalysed reaction studied, the isomerization of α-pinene oxide at 55 °C gave campholenic aldehyde and trans-carveol in a total yield of up to 86% at 100% conversion. Chemoselectivity is shown to be solvent dependent.

Mechanistic dichotomy in the asymmetric allylation of aldehydes with allyltrichlorosilanes catalyzed by chiral pyridine N-oxides

Detailed kinetic and computational investigation of the enantio- and diastereoselective allylation of aldehydes 1 with allyltrichlorosilanes 5, employing the pyridine N-oxides METHOX (9) and QUINOX (10) as chiral organocatalysts, indicate that the reaction can proceed through a dissociative (cationic) or associative (neutral) mechanism: METHOX apparently favors a pentacoordinate cationic transition state, while the less sterically demanding QUINOX is likely to operate via a hexacoordinate neutral complex. In both pathways, only one molecule of the catalyst is involved in the rate- and selectivity-determining step, which is supported by both experimental and computational data. Copyright

ANALGESIC COMPOUNDS, METHODS, AND FORMULATIONS

Provided are analgesic compounds, and salts thereof, of formula: (I) wherein A is: (A) Additionally, pharmaceutical formulations and methods of use employing the above compounds are provided.