Decalin, also known as decahydronaphthalene, is a saturated bicyclic hydrocarbon with the molecular formula C₁₀H₁₈, consisting of two fused cyclohexane rings in a bicyclo[4.4.0]decane arrangement. Commercial decalin is usually a mixture of cis- and trans-isomers.[1][2] It is produced industrially by hydrogenation of naphthalene and exists as a colorless, oily liquid with a mild, menthol-like odor.[1] The two primary isomeric forms are cis-decalin and trans-decalin, with the trans isomer being more thermodynamically stable.[1][2]Decalin is a non-polar solvent miscible with organic solvents but insoluble in water, with a boiling point of 189–191 °C and density of 0.89 g/cm³ at 20 °C.[1] It is flammable (flash point 57 °C) and can form explosive peroxides on air exposure.[1] Industrially, it is used in lubricants, as a fuel additive, and in hydrogen storage via dehydrogenation to naphthalene (7.3 wt% H₂). The decalin motif is found in natural products like lovastatin.[1][2]Decalin is toxic by inhalation or skin absorption (LC₅₀ 710 ppm, rat, 4 h) and irritating to eyes and skin. It shows carcinogenic potential in male rats (renal tubule neoplasms) and high bioconcentration (BCF 839–3,050), posing aquatic risks.[1]
Structure and stereochemistry
Molecular structure
Decalin, also known as decahydronaphthalene, is a saturated bicyclic alkane with the molecular formula \ce{C10H18} and a molar mass of 138.25 g/mol.[1][3] Its preferred IUPAC name is decahydronaphthalene, while the systematic name is bicyclo[4.4.0]decane.[1][4]Decalin features two six-membered cyclohexane rings fused together, sharing two adjacent carbon atoms to form an ortho-fused bicyclic hydrocarbon.[1] This ring fusion creates a framework where the rings are connected at their 1,2-positions, resulting in a total of 10 carbon atoms in a compact, saturated structure.[1]The chair conformation is the dominant geometry for both rings in decalin, as it allows for staggered bonds that minimize torsional strain.[5] In this arrangement, the C-C-C bond angles approximate the ideal tetrahedral value of 109.5°, thereby avoiding significant angle strain in the fused system.[6] The overall chair-chair form ensures low energy due to the absence of eclipsed interactions at the fusion points.[5]The non-stereospecific SMILES notation for decalin is \ce{C1CCC2CCCCC2C1}.[1] Decalin exists in cis and trans isomeric forms based on the stereochemistry at the ring junction.[1]
Isomers
Decalin, or decahydronaphthalene, exists as two primary stereoisomers: cis-decalin and trans-decalin. These isomers differ in the relative orientation of the hydrogens at the ring fusion sites. In cis-decalin, the fusion between the two cyclohexane rings is axial-equatorial, meaning one ring junction bond is axial to one ring and equatorial to the other. In contrast, trans-decalin features an equatorial-equatorial fusion, with both junction bonds oriented equatorially relative to their respective rings.[7][8]The conformational properties of these isomers are markedly different. Trans-decalin adopts a rigid chair-chair conformation that is locked due to the trans fusion geometry, which prohibits ring flipping because it would require an axial-axial arrangement at the fusion, resulting in excessive ring strain. This rigidity minimizes steric interactions between hydrogens across the rings, contributing to the overall stability of trans-decalin. Cis-decalin, however, is more flexible and can undergo chair-chair flipping between two equivalent conformations, interconverting the axial and equatorial positions at the fusion. Although cis-decalin possesses inherent chirality arising from its C2-symmetric structure without a plane of symmetry, this flexibility allows rapid racemization at room temperature through the low-energy barrier of ring inversion, approximately 10-12 kcal/mol.[8]The stability difference between the isomers is significant, with trans-decalin being approximately 2.7 kcal/mol more stable than cis-decalin, primarily due to the absence of 1,3-diaxial interactions present in the cis form. This energy gap is reflected in their conformational preferences and is a key factor in the predominance of the trans isomer in equilibrium mixtures. Stereospecific representations of these structures can be denoted using SMILES notation: for cis-decalin, C1CC[C@H]2CCCC[C@H]2C1; for trans-decalin, C1CC[C@H]2CCCC[C@@H]2C1. These notations specify the absolute configurations at the bridgehead carbons, highlighting the stereochemical distinctions.[9][10][11]
Properties
Physical properties
Decalin is a colorless liquid with a mild aromatic odor.[1]The density of decalin is approximately 0.896 g/cm³ at 20–25°C for the typical commercial mixture, with minor variations between isomers: 0.8965 g/cm³ for cis-decalin and 0.8699 g/cm³ for trans-decalin at 20°C.[12][13]Physical properties of decalin differ notably between its cis and trans isomers due to conformational differences, as summarized in the following table:
These values are experimental data reported for pure isomers and commercial mixtures.[12]Decalin exhibits low solubility in water, with a value of 0.889 mg/L at 25°C, rendering it insoluble for practical purposes; however, it is miscible with common organic solvents such as ethanol, diethyl ether, chloroform, acetone, and benzene.[12]The flash point of decalin is 57°C (open cup) for the mixture, with a closed-cup value of 54–58°C depending on the isomer composition. Its autoignition temperature is 250°C for the mixture.[12]Additional transport properties include a surface tension of 30 dynes/cm (0.030 N/m) at 20°C and a vapor pressure of 2.3 mmHg at 25°C for the mixture.[12]
Chemical properties
Decalin, a fully saturated bicyclic hydrocarbon, demonstrates high thermal and chemical stability attributable to its robust C-C and C-H bonds, rendering it resistant to degradation by most acids and bases under standard conditions.[1] However, this stability is tempered by its flammability, with a flash point of 57 °C (135 °F), classifying it as a Class 3 flammable liquid under UN number 1147.[14][1]Due to its non-polar structure, decalin possesses a low dielectric constant of approximately 2.1 at 20 °C, which results in negligible solubility in water (0.889 mg/L at 25 °C).[15][1] This non-polarity underscores its utility as a solvent for non-aqueous systems but limits interactions with polar media.Prolonged exposure to air, especially in the presence of light or elevated temperatures, can lead to the slow formation of hydroperoxides in decalin, potentially accumulating to hazardous levels over time.[1][16]Basic spectroscopic characterization confirms its saturated hydrocarbon nature: the infrared (IR) spectrum features prominent C-H stretching absorptions near 2900 cm⁻¹, while the ¹H nuclear magnetic resonance (NMR) spectrum exhibits aliphatic proton multiplets between 1.2 and 1.8 ppm.[17][18]
Synthesis
Industrial production
Decalin is primarily produced on an industrial scale through the catalytic hydrogenation of naphthalene in the liquid phase. The reaction involves the addition of five equivalents of hydrogen to naphthalene (C₁₀H₈ + 5 H₂ → C₁₀H₁₈), typically employing nickel-based catalysts such as Ni/Al₂O₃, with copper catalysts also used in some processes.[1][19] These processes operate under elevated temperatures of 150–290°C and pressures of 10–70 atm to achieve high conversion rates, favoring the liquid-phase conditions for efficient heat transfer and catalyst contact.[20][1]The isomer distribution in the product mixture depends on the catalyst selection and reaction parameters, with thermodynamic control generally favoring the more stable trans-decalin. Industrial hydrogenations yield approximately 70–80% trans-decalin and 20–30% cis-decalin, as nickel catalysts promote a trans/cis ratio around 4:1 under optimized conditions such as higher temperatures and hydrogen-to-oil ratios exceeding 250.[20][21] Conversion efficiencies exceed 95%, often reaching near-complete naphthalene consumption with decalin selectivity approaching 100%, though minor byproducts like tetralin may form at suboptimal conditions.[20] Post-reaction purification typically involves distillation to isolate the isomers if required for specific applications, achieving purities greater than 99%.[22]This industrial process traces its origins to the early 20th century, when hydrogenation techniques were developed for producing solvents from aromatic feedstocks like naphthalene derived from coal tar.[1] Today, decalin production occurs both in dedicated plants and as a byproduct during petroleum refining, with global output estimated in the thousands of tons annually— for instance, China's production reached 11,900 tons as of 2010, while U.S. volumes were around 211 tons as of 2019.[19][23] The process's economic viability stems from its high yields and the availability of naphthalene as a low-cost precursor.[1]
Laboratory synthesis
In laboratory settings, decalin is commonly synthesized on a small scale by catalytic hydrogenation of naphthalene using palladium on carbon (Pd/C) or platinum (Pt) catalysts in ethanol solvent under ambient pressure conditions, typically yielding a mixture of cis- and trans-isomers in ratios depending on the reaction parameters. This method allows for flexible control over reaction scale and is preferred for research purposes where pure starting materials are available, contrasting with industrial bulk processes.[24]Alternative synthetic routes employ cycloaddition strategies to construct the decalin core. The Diels-Alder reaction between butadiene derivatives, such as 1,3-butadiene with suitable dienophiles like cyclohexenone, followed by hydrogenation to saturate any remaining double bonds, provides access to cis- or trans-decalin frameworks with high stereocontrol.[25] For substituted decalins, variants of the Robinson annulation—combining Michael addition and aldol condensation between a ketone and an α,β-unsaturated carbonyl—enable the formation of functionalized bicyclic systems, often on solid support for combinatorial synthesis.[26]Stereoselective methods are essential for accessing specific isomers, particularly in natural product synthesis. Organocatalytic approaches using chiral catalysts, such as Jørgensen's imidazolidinone derivatives, facilitate enantioselective Nazarov cyclization/Diels-Alder cascades with sulfonyl reagents, yielding enantiopure cis-decalins with enantiomeric excesses (ee) of 70-99%.[27] These methods prioritize cis-fused rings, which are thermodynamically less stable but prevalent in bioactive molecules.Purification of the resulting isomer mixtures relies on fractional distillation, exploiting the ~5-6°C boiling point difference between cis-decalin (194-195°C) and trans-decalin (189-190°C), or chromatographic techniques like column chromatography on silica gel for higher resolution when analytical purity is required.[22]Recent advances include enantioselective syntheses of polysubstituted cis-decalins, with methods reported as recently as 2024 employing asymmetric Diels-Alder strategies and epimerization for trans-decalin intermediates in natural product total syntheses, achieving high ee (>90%) and yields of 50-80% for complex scaffolds in medicinal chemistry.[28][29][30]
Reactions
Oxidation and functionalization
Decalin undergoes autoxidation upon exposure to molecular oxygen, typically initiated by light or heat, via a free radical chain mechanism involving hydrogen abstraction from the tertiary carbon to form a tertiary alkyl radical, which then reacts with O₂ to yield the corresponding peroxy radical and ultimately decalin hydroperoxide (C₁₀H₁₈O₂).[31] This process preferentially targets the tertiary hydrogens at the ringfusion positions due to their relative weakness, leading to the hydroperoxide at the 4a(8a)-position.[32]The decalin hydroperoxide is thermally and catalytically unstable; under acid catalysis, it decomposes through a radical or ionic pathway involving a 1,2-alkyl shift, rearranging to 2-cyclodecen-1-one (C₁₀H₁₆O).[33] This transformation exemplifies the general behavior of tertiary hydroperoxides in cyclic systems, where the peroxide bond breaks to facilitate ring expansion or contraction while forming the carbonyl group.[33]Industrially, 2-cyclodecen-1-one serves as a key intermediate for sebacic acid production (HO₂C(CH₂)₈CO₂H), achieved through oxidative cleavage of the enone using hydrogen peroxide under elevated temperatures (110–150°C), yielding the 1,10-dicarboxylic acid as the primary product alongside shorter-chain acids.[34] This route provides an alternative to castor oil-derived processes and highlights decalin's role in dicarboxylic acid synthesis for applications like nylon-6,10.[34]Other functionalization methods include electrophilic halogenation, where chlorination of trans-decalin occurs selectively at the tertiary 4a(8a)-position under free radical conditions, reflecting the stability of the resulting tertiaryradicalintermediate. Deuteration of decalin, often achieving perdeuteration at specific sites, has been utilized in mechanistic investigations of its oxidative and rearrangement reactions to probe kinetic isotope effects and reaction pathways.[35]The overall autoxidation and rearrangement can be summarized as:\mathrm{C_{10}H_{18} + O_2 \rightarrow C_{10}H_{18}OOH \rightarrow C_{10}H_{16}O}
Ring-opening and rearrangements
Decalin undergoes selective ring-opening reactions primarily through hydrogenolysis, where C-C bonds at the ring fusion site are cleaved under hydrogen pressure using metal catalysts such as iridium or platinum supported on silica, yielding monosubstituted cyclohexanes as primary products. These reactions typically occur at temperatures of 250–400 °C and pressures around 5 MPa, with iridium catalysts showing higher activity and selectivity for direct ring opening without prior skeletal isomerization compared to platinum, which favors dehydrogenation and bond-shift mechanisms. For trans-decalin, the process preferentially produces ethylcyclohexane via cleavage of the central C-C bond, as illustrated by the reaction:\text{trans-C}_{10}\text{H}_{18} + \text{H}_2 \rightarrow \text{C}_6\text{H}_{11}\text{-CH}_2\text{CH}_3 \quad (\text{ethylcyclohexane})This selectivity arises from the rigid, locked chair conformation of trans-decalin, which limits access to alternative bond-breaking pathways. In contrast, cis-decalin, with its more flexible structure allowing ring flipping, yields a mixture including butylcyclohexane and 1-methyl-2-propylcyclohexane due to initial isomerization steps before hydrogenolysis.Decalin serves as a valuable probe molecule in studies of bifunctional catalysis for hydrocracking, where metal sites handle hydrogenation/dehydrogenation and acid sites facilitate carbocation-mediated ring contraction and opening.[36] On bifunctional catalysts like Pt/HY zeolite at 533 K and 2 MPa H₂, cis-decalin exhibits higher reactivity and selectivity toward ring-opening products (up to 11 wt% alkylcyclonaphthenes) compared to trans-decalin, which predominantly undergoes cracking to lighter hydrocarbons.[37] The mechanism involves acid-catalyzed protolytic cracking or β-scission of protonated intermediates, followed by metal-catalyzed hydrogenation, highlighting decalin's utility in evaluating catalyst balance for naphthenic hydrocarbon conversion.[37] Key ring-opening products in these systems include ethylcyclohexane, n-propylcyclohexane, and methylpropylcyclohexane, with cis-decalin favoring the latter due to easier access to tertiary carbocations.[37]Rearrangements of decalin under acidic conditions involve skeletal isomerization to alkyl-substituted cyclohexanes, often at elevated temperatures above 500 K, proceeding via carbocation rearrangements on solid acid catalysts like HY zeolites.[37] These transformations include ring contraction to intermediates like ethylmethylcyclopentanes before opening, contrasting with direct hydrogenolytic paths on metals, and are influenced by acid site strength and pore topology.[36] In petroleum chemistry, such reactions model the cracking of fused naphthenic structures in refining processes, where decalin mimics bicyclic components of heavy oils, aiding optimization of hydrocracking catalysts for diesel and jet fuel production.
Uses and occurrence
Industrial applications
Decalin is widely employed as a non-polar solvent in various industrial processes due to its chemical stability and ability to dissolve resins, oils, waxes, and greases without reacting under normal conditions. In the paints and varnishes sector, it enhances formulation performance by improving flow and leveling properties while maintaining low volatility.[38][39] Its non-polar nature makes it particularly suitable for dissolving non-polar substances like natural and synthetic resins used in coatings and adhesives.[40]In the fuel industry, decalin functions as an additive to improve the cetane number of diesel fuels, enhancing ignition quality and combustion efficiency when blended with commercial diesel formulations.[41] It is also incorporated into aviation fuels for its high energy density and thermal stability, serving as a key component in high-performance jet fuel blends like JP-900.[42][43]Decalin plays a role as a model compound in petroleum refining research, particularly in investigating ring-opening mechanisms during hydrocracking processes. Studies using bifunctional catalysts, such as Ir- or Pt-loaded zeolites, demonstrate its utility in simulating the conversion of bicyclic naphthenes to linear hydrocarbons, aiding the development of more efficient cracking technologies.[44][45][46]As a chemical intermediate, decalin is oxidized to form sebacic acid, which is utilized in the synthesis of nylon-6,10 polymers and plasticizers for enhanced flexibility in materials.[47] Additionally, it finds applications in rubber processing as a solvent for dissolving and reclaiming styrene-butadiene rubber from scrap materials, facilitating recycling efforts.[1][48] In analytical chemistry, decalin serves as a reference standard in chromatography techniques, particularly for calibrating column packings in gel permeation chromatography of polymers.[49] Global annual production of decalin was estimated at approximately 10,000 to 12,000 tons as of 2017, primarily supporting these solvent and additive roles. The global market was valued at approximately USD 500 million in 2023.[23][50]
Natural occurrence
Unsubstituted decalin is rare in natural systems and primarily occurs in trace amounts within petroleum fractions, originating from the diagenetic transformation of ancient biomass.[51] These occurrences reflect geological processes rather than direct biological synthesis, with decalin representing a minor component of the naphthenic hydrocarbons in crude oil.[52]Decalin derivatives are more prevalent in biosynthetic pathways, particularly within terpenoids and polyketides. In terpenoids, the decalin core features prominently in abietane diterpenoids such as abietic acid, a major resin acid isolated from pine resin in conifer species like Pinus spp.[53] Polyketide derivatives, including compounds like peaurantiogriseols A–F, have been identified in fungal metabolites from endophytic fungi associated with mangroves.[54] These structures arise through enzymatic cyclization of linear polyketide precursors, often involving Diels-Alderase enzymes that form the trans-fused decalin ring system.[55]Biosynthetically, decalin motifs form via cyclization reactions in steroid pathways, where squalene epoxide undergoes oxidative cyclization to yield fused ring systems analogous to decalin in cholesterol and its derivatives.[56] In microbial contexts, decalin-like structures can emerge from the degradation of aromatic compounds under anaerobic conditions, contributing to the formation of naphthenes in sedimentary environments.[52] Environmentally, decalin and its alkylated isomers are detected in crude oil and marine sediments, serving as geochemical markers for thermal maturity during oil formation.[52]Biologically, the decalin scaffold provides a structural model for the A/B ring fusion in steroids, aiding in understanding steroid hormone biosynthesis and function.[56] Derivatives with this core have been isolated from marine sponges, such as tandyukisins E and F from sponge-derived fungi, highlighting their role in marine natural product diversity.[57]
Safety and toxicology
Health hazards
Decalin poses several health hazards through acute and chronic exposure, primarily affecting the respiratory, dermal, and renal systems in humans. Acute exposure via inhalation can cause irritation to the respiratory tract, leading to symptoms such as dizziness, headache, and coughing, with an LC50 of 4.08 mg/L over 4 hours in rats.[58] Oral ingestion results in moderate toxicity, with an LD50 of 4170 mg/kg in rats, potentially causing gastrointestinal distress and aspiration pneumonia if swallowed.[1] Dermal contact leads to severe skin burns and eye damage, classified under GHS as skin corrosion category 1C (H314) and serious eye damage category 1 (H318).[58]Chronic exposure to decalin vapors has been associated with liver and kidney damage in animal studies. Inhalation studies in rats over 90 days revealed hepatotoxicity as the critical effect, with increased liver enzyme levels and histopathological changes observed at concentrations above 7.9 mg/m³.[51]Kidney effects, particularly nephropathy characterized by hyaline droplets, tubular necrosis, and intratubular casts, occur predominantly in male rats due to alpha-2u-globulin accumulation, a mechanism not relevant to humans.[59] Regarding carcinogenicity, the National Toxicology Program (NTP) reported clear evidence of renal tubule neoplasms in male F344/N rats exposed to 100 or 400 ppm decalin for two years, but equivocal evidence in female B6C3F1 mice based on increased hepatocellular and uterine carcinoma incidences; no evidence was found in female rats.[60] Data on reproductive toxicity indicate potential effects, with no classification under GHS; studies, including a 2025 OECD TG 421 screen in Sprague Dawley rats, have shown impaired ovarian function at mid and high doses, along with signs of stress in dams.[58][61]Decalin also presents environmental health hazards due to its persistence and bioaccumulation potential. With a log Kow of 4.6, it exhibits moderate lipophilicity, leading to bioaccumulation in aquatic organisms, evidenced by bioconcentration factors (BCF) ranging from 800 to 3000 in fish such as carp.[1] It is highly toxic to aquatic life, with a 48-hour LC50 of 1.84 mg/L in medaka fish (Oryzias latipes), classifying it under GHS as acutely toxic to aquatic life category 1 (H400) and chronically toxic category 1 (H410).[1] Overall, decalin's GHS classifications include acute inhalation toxicity category 3 (H331), aspiration hazard category 1 (H304), and flammable liquid category 3 (H226), underscoring risks from vapor exposure and accidental ingestion.[58] No specific OSHA permissible exposure limits exist for decalin, though the German MAK value is 5 ppm (29 mg/m³) as an 8-hour time-weighted average.[1]
Handling and storage
Decalin should be handled in well-ventilated areas or under a fume hood to minimize inhalation risks, with personal protective equipment (PPE) including nitrile or butyl rubber gloves, safety goggles, and flame-retardant antistatic clothing to prevent skin contact and static discharge.[58] Containers must be grounded during transfer to avoid static sparks that could ignite vapors.[62]For storage, decalin requires cool, dry, well-ventilated locations away from heat, ignition sources, oxidizers, and direct sunlight, with containers kept tightly closed and under an inert atmosphere such as nitrogen to inhibit autoxidation and peroxide formation.[58][62] Periodic testing for peroxides is recommended during prolonged storage.[62] Addition of antioxidants, such as butylated hydroxytoluene (BHT), can further stabilize decalin against oxidative degradation.[63]In the event of a spill, evacuate the area, ensure adequate ventilation, and eliminate ignition sources before absorbing the liquid with an inert material like vermiculite or sand, then place in suitable containers for disposal; spills should not be flushed to sewers or waterways due to fire and environmental hazards.[58][62]Decalin is classified as a hazardous material for transport under UN 1147 (decahydronaphthalene, Class 3 flammable liquid, Packing Group III) and is registered under the European REACH regulation (EC 202-046-9, registration number 01-2119565127-37).[58]