464-49-3

Usage

Uses

1. Chiral Intermediate and Auxiliary:
D-CAMPHOR is used as a chiral intermediate and auxiliary in the synthesis of various compounds, contributing to its importance in the chemical industry.
2. Skin Antipruritic:
D-CAMPHOR serves as a skin antipruritic, helping to relieve itching and irritation on the skin.
3. Anti-infective Agent:
Due to its anti-infective properties, D-CAMPHOR is used as an anti-infective agent, providing protection against various infections.
4. Culinary Flavoring Agent:
In some parts of Asia, D-CAMPHOR is used as a culinary flavoring agent, adding a unique taste to certain dishes.
5. Insecticidal Activity:
D-CAMPHOR exhibits insecticidal activity, making it useful in controlling and reducing insect populations, particularly in agricultural settings.
6. Building Block in Synthesis:
D-CAMPHOR has been used as a building block in the synthesis of cannabinergic ligands, highlighting its versatility in chemical applications.
7. Quantification of Analytes:
D-CAMPHOR may be used as a reference material for the quantification of analytes in Saraca asoca and coriander using chromatography techniques, aiding in the analysis and quality control of these plants.
8. Aroma and Taste:
D-CAMPHOR's warm, minty, and almost ethereal aroma, along with its medicinal, camphoraceous, mentholic, and woody taste characteristics, make it a valuable component in the fragrance and flavor industries.
Occurrence:
D-CAMPHOR is frequently found in nature as the dor l-form, with the optically inactive form being seldom encountered. The d-form has been reported in various plants, including Cinnamomum camphora, Sassafras officinale, Lavandula spica, and other Labiatae. The l-form is found in the essential oils of Salvia grandiflora, Matricaria parthenium, and Artemisia herba alba. Additionally, D-CAMPHOR is reported in orange peel oil, lemon peel oil, apricot, raspberry, anise, cinnamon root bark, ginger, pepper, coriander, calamus, sweet fennel, and rosemary.

Air & Water Reactions

Flammable. Insoluble in water.

Reactivity Profile

D-CAMPHOR is incompatible with strong oxidizing agents, strong reducing agents and chlorinated solvents.

Fire Hazard

D-CAMPHOR is combustible.

Flammability and Explosibility

Flammable

Synthesis

Natural camphor is obtained by distillation from the plants of Cinnamomum or Laurus camphora from China and Japan, together with the corresponding essential oils; the raw camphor contains several impurities. It is separated from the water and the essential oil by pressure or by centrifugation and subsequently purified by sublimation or crystallization. Synthetic camphor is prepared from pinene isolated by fractional distillation of turpentine oil; pinene is reacted to bornyl chloride with gaseous HCl under pressure and then to camphene. The distilled and purified camphene is then oxidized to camphor with Na+ or K+ bichromate in the presence of H2SO4.

Purification Methods

Crystallise it from EtOH, 50% EtOH/water, MeOH, or pet ether or from glacial acetic acid by addition of water. It can be sublimed (50o/14mm) and also fractionally crystallised from its own melt. It is steam volatile. It should be stored in tight containers as it is appreciably volatile at room temperature. The solubility is 0.1% (H2O), 100% (EtOH), 173% (Et2O) and 300%

InChI:InChI=1/C10H16O/c1-9(2)7-4-5-10(9,3)8(11)6-7/h7H,4-6H2,1-3H3/t7?,10-/m0/s1

Upstream product

• 124-76-5 (+)-borneol 
• 14487-70-8 3-diazocamphor 
• 507-70-0 1,7,7-trimethyl bicyclo[2.2.1]heptan-2-ol 
• 464-43-7 d-borneol 
• 62280-85-7 1-methyl,7,7-dimethyl,bicyclo<2.2.1>heptane,2-carboxylic acid 
• 6627-72-1 rac-endo-borneol 
• 6535-09-7 (-)-2exo-bromo-2endo-nitro-bornane 
• 15099-93-1 (1R)-bornen-⁽²⁾-one-⁽⁶⁾ 
• 64-19-7 acetic acid 
• 67-56-1 methanol 
• 119593-84-9 C₁₈H₂₂O₂S 
• 124-76-5 isoborneol 
• 464-17-5 (-)-bornylene 
• 2792-42-9 (R,R)-camphor oxime 

Downstream Products

• 67396-44-5 p-Anisylisoborneol 
• 91278-70-5 2-methyl-isoborneol 
• 68330-43-8 (+)-R-methylisoborneol 
• 4501-58-0 campholenyc aldehyde 
• 75-07-0 acetaldehyde 
• 124-76-5 isoborneol 
• 464-43-7 d-borneol 
• 124-83-4 D-(+)-camphoric acid 
• 10334-26-6 (R)-camphorquinone 
• 2792-42-9 (R,R)-camphor oxime 
• 3144-16-9 (1S)-10-camphorsulfonic acid 
• 1130-49-0 (S)-(2,2,3-trimethyl-5-oxo-cyclopent-3-enyl)-acetic acid 
• 6627-72-1 rac-endo-borneol 
• 53402-10-1 thiocamphor 

Relevant academic research and scientific papers

Molybdenum(0)-Catalyzed Reductive Dehalogenation of α-Halo Ketones with Phenylsilane

Reductive dehalogenation of α-halo ketones and esters is effectively achieved by using a novel reducing system comprised of phenylsilane and catalytic amounts of molybdenum hexacarbonyl and triphenylphosphine.Reactions are carried out at 60-80 deg C in variety of solvents, including THF, benzene, toluene, and diglyme.With respect to α-halo carbonyl reduction, this combination of Mo(0) and phenylsilane is superior to our previously described palladium (0)/diphenylsilane system and produces higher yields and cleaner products.

Straightforward synthesis of (1S)-10-dimethylaminomethylcamphor: An enantiospecific model procedure to C10-C-substituted camphor-derived chiral sources

Enantiopure 3,3-dimethyl-2-methylenenorbornan-1-ol, readily obtained from commercially available camphor, is able to react with Eschenmoser's salt under very soft reaction conditions. This reaction constitutes the first example in which a non-mesomerically activated olefin easily adds the Eschenmoser's salt. The addition takes place regiospecifically and it is followed by an enantiospecific Wagner-Meerwein rearrangement of the norbornane skeleton to afford enantiopure 10-dimethylaminomethylcamphor, an interesting chiral δ-amino ketone, with excellent yield. The obtained amino ketone is a key intermediate to new valuable C10-C-substituted camphor-derived chiral sources.

A Structural View on the Stereospecificity of Plant Borneol-Type Dehydrogenases

The development of sustainable processes for the valorization of byproducts and other waste streams remains an ongoing challenge in the field of catalysis. Racemic borneol, isoborneol and camphor are currently produced from α-pinene, a side product from the production of cellulose. The pure enantiomers of these monoterpenoids have numerous applications in cosmetics and act as reagents for asymmetric synthesis, making an enzymatic route for their separation into optically pure enantiomers a desirable goal. Known short-chain borneol-type dehydrogenases (BDHs) from plants and bacteria lack the required specificity, stability or activity for industrial utilization. Prompted by reports on the presence of pure (?)-borneol and (?)-camphor in essential oils from rosemary, we set out to investigate dehydrogenases from the genus Salvia and discovered a dehydrogenase with high specificity (E>120) and high specific activity (>0.02 U mg?1) for borneol and isoborneol. Compared to other specific dehydrogenases, the one reported here shows remarkably higher stability, which was exploited to obtain the first three-dimensional structure of an enantiospecific borneol-type short-chain dehydrogenase. This, together with docking studies, led to the identification of a hydrophobic pocket in the enzyme that plays a crucial role in the stereo discrimination of bornane-type monoterpenoids. The kinetic resolution of borneol and isoborneol can be easily integrated into the existing synthetic route from α-pinene to camphor thereby allowing the facile synthesis of optically pure monoterpenols from an abundant renewable source.

Borneol dehydrogenase from Pseudomonas sp. TCU-HL1 possesses novel quinuclidinone reductase activities

Borneol dehydrogenase (BDH) catalyses the last step of the camphor biosynthetic pathway in plants and the first reaction in the borneol degradation pathway in soil microorganisms. Native or engineered BDH can be used to produce optically pure borneol and camphor. The recently reported apo-form crystal structure of BDH (PDB ID: 6M5N) from Pseudomonas sp. TCU-HL1 superimposes well with that of 3-quinuclidinone reductase (QR) (PDB ID: 3AK4) from Agrobacterium tumefaciens. QR catalyses the conversion of 3-quinuclidinone into (R)-3-(?)-quinuclidinol, an important chiral synthone for several drugs. However, the kinetic parameter, kcat, of QR was not determined in the previous reports even though both BDH and QR have various potential industrial applications. Here, we aimed to further characterise their structural and functional relationship. Recombinant QR with the native sequence was cloned, expressed in E. coli, and purified. We found that 3-quinuclidinone can be used as an alternative substrate for BDH. Only (R)-3-(?)-quinuclidinol was detected in this BDH-catalysed reaction. The results of 3 D molecular docking simulation show that 3-quinuclidinone and (+)-/(-)- borneol were docked to two different parts of the QR active site. In contrast, all three compounds are docked uniformly to the alpha-1 helix of BDH. There results explain why BDH can turnover 3-quinuclidinone, while QR can not act on (+)-/(-)-borneol.

Dysprosium-doped zinc tungstate nanospheres as highly efficient heterogeneous catalysts in green oxidation of terpenic alcohols with hydrogen peroxide

A green route to oxidize terpenic alcohols (nerol and geraniol) with H2O2over a solid catalyst was developed. The Dy-doped ZnWO4catalyst was synthesized by coprecipitation and microwave-assisted hydrothermal heating, containing different dysprosium loads. All the catalysts were characterized through infrared spectroscopy, powder X-ray diffraction, surface area and porosimetry, transmission electronic microscopy image, andn-butylamine potentiometric titration analyses. The influence of main reaction parameters such as temperature, the stoichiometry of reactants, loads, and catalyst nature was assessed. ZnWO42.0 mol% Dy was the most active catalyst achieving the highest conversion (98%) and epoxide selectivity (78%) in nerol oxidation. The reaction scope was extended to other terpenic alcohols (i.e., geraniol, borneol, and α-terpineol). The highest activity of ZnWO42.0 mol% Dy was assigned to the lower crystallite size, higher surface area and pore volume, higher acidity strength and the greatest dysprosium load.

Zwitterion-induced organic-metal hybrid catalysis in aerobic oxidation

In many metal catalyses, the traditional strategy of removing chloride ions is to add silver salts via anion exchange to obtain highly active catalysts. Herein, we reported an alternative strategy of removing chloride anions from ruthenium trichloride using an organic [P+-N-] zwitterionic compound via multiple hydrogen bond interactions. The resultant organic-metal hybrid catalytic system has successfully been applied to the aerobic oxidation of alcohols, tetrahydroquinolines, and indolines under mild conditions. The performance of zwitterion is far superior to that of many other common Lewis bases or Br?nsted bases. Mechanistic studies revealed that the zwitterion triggers the dissociation of chloride from ruthenium trichloride via nonclassical hydrogen bond interaction. Preliminary studies show that the zwitterion is applicable to catalytic transfer semi-hydrogenation.

carba Nicotinamide Adenine Dinucleotide Phosphate: Robust Cofactor for Redox Biocatalysis

Here we report a new robust nicotinamide dinucleotide phosphate cofactor analog (carba-NADP+) and its acceptance by many enzymes in the class of oxidoreductases. Replacing one ribose oxygen with a methylene group of the natural NADP+ was found to enhance stability dramatically. Decomposition experiments at moderate and high temperatures with the cofactors showed a drastic increase in half-life time at elevated temperatures since it significantly disfavors hydrolysis of the pyridinium-N?glycoside bond. Overall, more than 27 different oxidoreductases were successfully tested, and a thorough analytical characterization and comparison is given. The cofactor carba-NADP+ opens up the field of redox-biocatalysis under harsh conditions.

Unraveling the role of the lacunar Na7PW11O39 catalyst in the oxidation of terpene alcohols with hydrogen peroxide at room temperature

In this work, we have assessed the activity of various Keggin heteropolyacid (HPA) salts in a new one-pot synthesis route of valuable products, which were obtained from the oxidation of terpenic alcohols (i.e., aldehyde, epoxide, and diepoxide), using a green oxidant (i.e., hydrogen peroxide) at mild conditions (i.e., room temperature). Lacunar Keggin HPA sodium salts were the goal catalysts investigated in this reaction. Starting from the HPAs (H3PW12O40, H3PMo12O40, and H4SiW12O40), we synthesized lacunar sodium salts (Na7PW11O39, Na7PW11O39 and Na8SiW11O39) and a saturated salt (Na3PW12O40). All of them were investigated in oxidation reactions in a homogeneous phase with nerol as a model molecule. Na7PW11O39 was the most active and selective towards the oxidation products. All the catalysts were characterized by FT-IR, TG/DSC, BET, XRD, and SEM-EDS analyses and potentiometric titration. The main reaction parameters were assessed. Geraniol, α-terpineol, β-citronellol and borneol were also successfully oxidized. Special attention was dedicated to correlating the composition and properties of the catalysts with their activity.

Molecular cloning and functional characterization of a two highly stereoselective borneol dehydrogenases from Salvia officinalis L

Enzymes for selective terpene functionalization are of particular importance for industrial applications. Pure enantiomers of borneol and isoborneol are fragrant constituents of several essential oils and find frequent application in cosmetics and therapy. Racemic borneol can be easily obtained from racemic camphor, which in turn is readily available from industrial side-streams. Enantioselective biocatalysts for the selective conversion of borneol and isoborneol stereoisomers would be therefore highly desirable for their catalytic separation under mild reaction conditions. Although several borneol dehydrogenases from plants and bacteria have been reported, none show sufficient stereoselectivity. Despite Croteau et al. describing sage leaves to specifically oxidize one borneol enantiomer in the late 70s, no specific enzymes have been characterized. We expected that one or several alcohol dehydrogenases encoded in the recently elucidated genome of Salvia officinalis L. would, therefore, be stereoselective. This study thus reports the recombinant expression in E. coli and characterization of two enantiospecific enzymes from the Salvia officinalis L. genome, SoBDH1 and SoBDH2, and their comparison to other known ADHs. Both enzymes produce preferentially (+)-camphor from racemic borneol, but (?)-camphor from racemic isoborneol.

Electrochemistry Broadens the Scope of Flavin Photocatalysis: Photoelectrocatalytic Oxidation of Unactivated Alcohols

Riboflavin-derived photocatalysts have been extensively studied in the context of alcohol oxidation. However, to date, the scope of this catalytic methodology has been limited to benzyl alcohols. In this work, mechanistic understanding of flavin-catalyzed oxidation reactions, in either the absence or presence of thiourea as a cocatalyst, was obtained. The mechanistic insights enabled development of an electrochemically driven photochemical oxidation of primary and secondary aliphatic alcohols using a pair of flavin and dialkylthiourea catalysts. Electrochemistry makes it possible to avoid using O2 and an oxidant and generating H2O2 as a byproduct, both of which oxidatively degrade thiourea under the reaction conditions. This modification unlocks a new mechanistic pathway in which the oxidation of unactivated alcohols is achieved by thiyl radical mediated hydrogen-atom abstraction.