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1-Octene

1-Octene is an unsaturated and a linear alpha-olefin with the C₈H₁₆, featuring a terminal carbon-carbon at the 1-position, which distinguishes it from other octene isomers. It appears as a clear, colorless with a gasoline-like odor, has a molecular weight of 112.21 g/mol, a melting point of -101 °C, a boiling point of 122–123 °C, and a density of 0.715 g/mL at 25 °C. Insoluble in water but miscible with organic solvents such as ether, alcohol, and acetone, it is highly flammable with a flash point of 10 °C (closed cup) and exhibits reactivity typical of alkenes, including potential exothermic polymerization or reactions with strong oxidizers. Industrially, 1-octene is primarily produced through the selective oligomerization of , specifically tetramerization, using chromium-based catalysts to yield linear alpha-olefins with high selectivity. This process, commercialized by companies like and , generates 1-octene as a key product alongside other olefins like , enabling large-scale production for downstream applications. The compound's most significant uses revolve around its role as a comonomer in the production of , particularly (LLDPE) and (HDPE), where it improves properties such as flexibility and impact strength. Additionally, 1-octene serves as a feedstock for polyalphaolefins (PAOs) in synthetic lubricants, offering high indices and thermal stability, and is employed in the synthesis of , plasticizers, and oxo-alcohols via . Its low toxicity and mild irritant effects make it suitable for these industrial applications, though handling requires precautions due to flammability.

Structure and Properties

Molecular Structure

1-Octene has the molecular formula C₈H₁₆ and the systematic IUPAC name oct-1-ene. Its structural formula is CH₂=CH(CH₂)₅CH₃, representing a linear chain of eight carbon atoms with a carbon-carbon at the terminal position. This configuration classifies 1-octene as an alpha-olefin, where the is located between the first and second carbon atoms, distinguishing it from internal olefins. The IUPAC nomenclature for 1-octene follows the standard rules for alkenes, which involve identifying the longest continuous carbon chain containing the and numbering it from the end that gives the lowest number to the double bond position, resulting in the suffix "-ene" with the "1". In the molecular structure of 1-octene, the carbons involved in the (C1 and C2) exhibit sp² hybridization, leading to a trigonal planar around these atoms with bond angles of approximately 120°. The C=C consists of a σ and a π , with a typical of about 1.33 , while the adjacent C-C single bonds have lengths of approximately 1.54 . 1-Octene exists among positional isomers of octene, such as 2-octene where the is between carbons 2 and 3, but its terminal position imparts unique reactivity, particularly in addition reactions and processes due to the accessibility of the unsubstituted .

Physical Properties

1-Octene is a colorless, clear at , exhibiting a mild . Its density is 0.715 g/cm³ at 20 °C, which is relatively low due to its linear molecular structure compared to branched octene isomers. The melting point is −101.7 °C, and the boiling point is 121–123 °C at 1 atm. The flash point is 10 °C (closed cup), indicating high flammability under standard conditions. 1-Octene is insoluble in , with a solubility of 0.004 g/L at 25 °C, but it is miscible with organic solvents such as and . The is 1.408–1.409 at 20 °C. Its is 15 mmHg (2 kPa) at 20 °C, and the is 220 °C. Key thermodynamic data include a standard of Δ_cH° = −5312.9 kJ/mol for the liquid phase and a of μ = 0.30 D.
PropertyValueConditions
Density0.715 g/cm³ °C
Melting point−101.7 °C-
Boiling point121–123 °C1
Flash point10 °CClosed cup
Refractive index1.408–1.409 °C
Vapor pressure15 mmHg °C
Autoignition temperature220 °C-
Heat of combustion−5312.9 kJ/molLiquid, standard
Dipole moment0.30 D-

Chemical Properties

1-Octene exhibits typical reactivity of an α-olefin, primarily undergoing electrophilic additions at its terminal carbon-carbon in accordance with . For instance, catalytic using (Pd/C) converts 1-octene to n-octane under mild conditions, as shown in the equation: \text{CH}_2=\text{CH}(\text{CH}_2)_5\text{CH}_3 + \text{H}_2 \xrightarrow{\text{Pd/C}} \text{CH}_3(\text{CH}_2)_6\text{CH}_3 This reaction proceeds via syn addition and is widely used to saturate the . Due to its terminal unsaturation, 1-octene readily undergoes catalyzed by complexes, such as those of or supported by PN or NPN ligands, yielding poly(1-octene) with controlled molecular weights and microstructures, as explored in a February 2025 Polymer Journal study. In terms of oxidation, 1-octene is prone to auto-oxidation in the presence of oxygen and metals, forming hydroperoxides as primary products through a free-radical chain mechanism. Additionally, treatment with (KMnO₄) under cold, dilute, alkaline conditions effects syn , producing the vicinal : \text{CH}_2=\text{CH}(\text{CH}_2)_5\text{CH}_3 + \text{KMnO}_4 \rightarrow \text{HO-CH}_2\text{-CH(OH)}(\text{CH}_2)_5\text{CH}_3 This reaction highlights the susceptibility of the double bond to oxidative cleavage or addition. 1-Octene demonstrates good stability under neutral conditions but can isomerize to internal olefins, such as 2-octene, when exposed to acidic catalysts like sulfuric acid or solid acids, via a carbocation mechanism that migrates the double bond. Spectroscopically, the (IR) spectrum of 1-octene features a characteristic C=C stretching absorption at approximately 1640 cm⁻¹, indicative of the terminal functionality. In the ¹H (NMR) spectrum, the protons appear as multiplets between 4.9 and 5.9 , while the allylic methylene protons resonate around 2.0 , providing key signatures for structural confirmation. Regarding acid-base properties, 1-octene behaves as a weak base owing to the availability of its π electrons for protonation, with the pKₐ of its conjugate acid (the protonated form) estimated at approximately −7, underscoring its low basicity compared to amines or ethers.

Production

Industrial Synthesis

The industrial synthesis of 1-octene has evolved significantly since its early production via thermal cracking of paraffinic waxes in the pre-1970s era, a method that yielded a broad distribution of linear alpha-olefins including 1-octene but suffered from low selectivity and energy inefficiency. Following the global surplus of ethylene from steam cracking in the 1970s, production shifted to catalytic oligomerization processes, which offer higher specificity and economic viability by directly assembling ethylene units into targeted C8 olefins. The primary commercial method today is the selective tetramerization of using chromium-based catalysts, typically Cr(III) precursors activated with aluminoxanes and coordinated by diphosphine ligands such as (R₂PCH₂CH₂)₂NHR' in a solvent, achieving selectivities exceeding 70% for 1-octene. This process operates under moderate conditions of 100–130°C and 30–50 bar , with the proceeding via metallacycle intermediates that favor linear alpha-olefin formation. The overall is represented by: $4 \ce{C2H4} \rightarrow \ce{CH2=CH(CH2)5CH3} Key industrial implementations include Sasol's proprietary ethylene tetramerization technology, commissioned in 2013 at their Lake Charles facility in the United States with an initial combined capacity of 100,000 tons per year for 1-octene and 1-hexene, and proprietary processes employed by Chevron Phillips Chemical, which involve ethylene oligomerization to produce linear alpha-olefins including 1-octene. INEOS also utilizes similar chromium-catalyzed oligomerization routes at their facilities. These processes co-produce lighter alpha-olefins such as and , alongside minor branched isomers and , which are managed through multi-stage leveraging differences (e.g., at -6.3°C, at 63.5°C, and 1-octene at 121.3°C) to achieve >97% purity for commercial grades. Global production capacity for 1-octene reached approximately 1 million tons per year as of 2023, dominated by , Chevron Phillips, and , with costs heavily influenced by feedstock prices, typically ranging from $0.80–1.00 per kg in that year. Recent advancements focus on tandem catalysis systems incorporating optimized PNP ligand architectures, as patented in the 2010s, which have boosted 1-octene yields to over 80% by enhancing metallacycle stability and reducing side reactions.

Laboratory Synthesis

One common laboratory method for synthesizing 1-octene involves the of 1-bromooctane using alcoholic (KOH). In this , 1-bromooctane is heated with KOH in , leading to the removal of HBr and formation of the terminal . The reaction proceeds via an E2 , favored under these conditions for primary alkyl halides, yielding predominantly 1-octene along with minor isomers. Another approach is the of , typically catalyzed by (H₂SO₄) at elevated temperatures around 180°C. This acid-catalyzed elimination follows Zaitsev's rule, which can result in to more stable internal alkenes like 2-octene; however, selectivity for 1-octene improves when using alumina (Al₂O₃) as a , achieving high (up to 99%) and selectivity (over 90%) under optimized conditions such as at 500°C. The reaction equation is: \mathrm{CH_3(CH_2)_6CH_2OH \xrightarrow{Al_2O_3, 250^\circ C} CH_2=CH(CH_2)_5CH_3 + H_2O} Organometallic routes, such as Grignard coupling, provide a versatile alternative. For instance, n-pentylmagnesium bromide reacts with allyl chloride to form 1-octene through nucleophilic substitution at the allylic position. This method requires anhydrous conditions and yields the terminal alkene selectively, though catalysts like copper may enhance efficiency in some variants. The reaction is: \mathrm{CH_2=CHCH_2Cl + CH_3(CH_2)_4MgBr \rightarrow CH_2=CH(CH_2)_5CH_3 + MgBrCl} Modern laboratory syntheses often employ olefin metathesis, particularly ethenolysis of internal alkenes from vegetable oils or rhamnolipids using Grubbs catalysts (e.g., ruthenium-based carbene complexes). In this cross-metathesis with ethylene, a fatty acid ester like methyl oleate reacts to cleave and form 1-decene and ethylene, but adaptations target 1-octene with selectivities up to 80% in aqueous or biphasic systems; yields for pure 1-octene remain moderate (around 50%) due to side products. An example equation is: \mathrm{R-CH=CH-R' + CH_2=CH_2 \xrightarrow{Grubbs\ catalyst} 2\ CH_2=CH-R} where R corresponds to a hexyl chain (e.g., from 7-tetradecene). Following synthesis, 1-octene is purified by fractional distillation under an inert nitrogen atmosphere to separate it from isomers, unreacted starting materials, and byproducts, exploiting its boiling point of 121°C. This prevents peroxidation of the alkene during heating. Typical laboratory yields across these methods range from 50% to 80%, depending on the route and optimization. Laboratory procedures emphasize safety, including the use of inert atmospheres (e.g., or ) to minimize oxidation risks, as 1-octene is highly flammable and can form vapor-air mixtures. Handling requires fume hoods, protective , and avoidance of ignition sources due to its to aquatic life and potential for .

Applications

Polymer Production

1-Octene serves primarily as a comonomer in the production of (LLDPE) through copolymerization with , utilizing either Ziegler-Natta or metallocene catalysts. The typical incorporation level of 1-octene ranges from 2 to 10 mol%, which introduces short-chain branches into the backbone. This process can be represented by the general copolymerization : n \ce{C2H4} + m \ce{CH2=CHC6H13} \to [\ce{CH2-CH2}]_n-[\ce{CH2-CH(C6H13)}]_m where the subscripts n and m denote the repeating units of ethylene and 1-octene, respectively. The addition of 1-octene branches disrupts the regularity of the polyethylene chain, lowering the polymer's density to 0.915–0.925 g/cm³ and reducing crystallinity. These modifications enhance key mechanical properties, including flexibility, tensile strength, and impact resistance, making LLDPE particularly suitable for applications such as stretch films, packaging bags, and agricultural films. Industrial-scale LLDPE production incorporating 1-octene typically occurs in gas-phase reactors operating at temperatures of 80–100°C and pressures of 20–30 , enabling efficient heat management and high throughput. Approximately 80% of global 1-octene output is consumed in production, with LLDPE demand driving an estimated use of approximately 1.8 million metric tons annually as of 2023. Beyond LLDPE, 1-octene is copolymerized with to produce polyoctene and ethylene-octene elastomers, such as Dow's Engage™ series, which exhibit rubber-like elasticity and improved toughness. These materials are used in blow-molding resins to enhance durability and processability in automotive and consumer goods applications. The of 1-octene as a comonomer in LLDPE began in the late 1970s, enabling the replacement of traditional (LDPE) in applications due to cost efficiencies and superior performance.

Chemical Intermediates

1-Octene is a versatile feedstock for producing chemical intermediates, primarily through reactions that functionalize its group to create value-added compounds for downstream industries. A major application is , known as the oxo process, which involves the addition of and to 1-octene using or catalysts to yield (linear ) and 2-methyloctanal (branched ). The reaction proceeds as follows: \ce{CH2=CHC6H13 + CO + H2 ->[cat.] O=CH(CH2)6CH3 + O=CHCH(CH3)C6H13} These aldehydes are subsequently hydrogenated to C9 alcohols, such as 1-nonanol, which serve as building blocks for plasticizers. Industrial hydroformylation conditions vary by catalyst: cobalt-based processes operate at 140–200 °C and 200–300 bar, while rhodium-based systems use milder conditions of 85–130 °C and 15–50 bar, achieving a linear-to-branched ratio of approximately 80:20 or higher with optimized ligands. Recent advances in reductive hydroformylation include the development of immobilized Rh-based solid molecular catalysts for the direct conversion of 1-octene to alcohols, enhancing process efficiency. Recent research published in October 2025 has demonstrated encapsulated heterogeneous rhodium single-atom catalysts for the linear selective hydroformylation of 1-octene, enhancing efficiency in oxo-alcohol production. In reactions, 1-octene reacts with under acidic conditions, often catalyzed by zeolites, to form linear alkylbenzenes. These are then sulfonated to produce alkylbenzenesulfonates, key components in branched formulations. Epoxidation of 1-octene with peracids, such as , generates 1,2-epoxyoctane, a reactive used as an intermediate in synthesis via ring-opening reactions. 1-Octene plays a significant role in providing C8–C9 building blocks for plasticizers, detergents, and in downstream chemical sectors.

Other Uses

1-Octene serves as a key raw material in the production of through sulfonation with (SO₃), yielding alpha-olefin sulfonates (AOS) that are widely used in detergents and . These AOS, derived from C8 alpha-olefins like 1-octene, consist of a of sulfonates and hydroxyalkane sulfonates, offering effective cleaning performance comparable to linear sulfonates while exhibiting superior stability in . AOS are noted for their ready biodegradability, achieving nearly complete primary degradation within days under aerobic conditions, and they produce moderate foam suitable for low-foam formulations in liquid soaps and shampoos. In the lubricants sector, 1-octene undergoes oligomerization to form polyalphaolefins (PAOs), which are essential base stocks for high-performance synthetic oils. These PAOs provide excellent thermal and oxidative stability, with viscosity indices typically exceeding 140 and pour points below -50°C, enabling reliable operation in extreme temperatures without gum formation or deposits. The resulting fluids are commonly applied in automotive and industrial lubricants, contributing to reduced volatility and extended service life. In agrochemicals, 1-octene finds minor application as a building block for synthesizing alkyl chains in certain herbicides and pesticides, though it represents a small fraction of overall consumption. With growing interest in bio-based alternatives emerging after to meet demands. In niche areas, 1-octene acts as an intermediate in and fragrance formulations, imparting a mild camphoraceous at low concentrations.

Safety and Handling

Hazards

1-Octene is classified as an extremely (NFPA Class IB) with a low of approximately 21°C, contributing to its high risk. It forms vapor-air mixtures, with lower and upper limits of 0.9% and 6.8% by volume in air, respectively, and an of 221°C. Exposure to 1-octene can cause effects primarily through and systemic . It acts as a and eye irritant, leading to redness, , and serious eye damage upon contact. Inhalation of vapors may result in and at high concentrations. data indicate low oral and dermal absorption risks, with LD50 values exceeding 5000 mg/kg (oral, ) and 2000 mg/kg (dermal, ). In terms of reactivity, 1-octene can form peroxides upon prolonged exposure to air, particularly if concentrated or distilled. It is incompatible with strong oxidizers, such as , which may cause violent reactions due to oxidation of the , and with strong acids, leading to exothermic . No specific OSHA permissible exposure limit (PEL) is established for 1-octene; however, the American Industrial Hygiene Association (AIHA) recommends a environmental exposure level (WEEL) of 75 as an 8-hour time-weighted average. It may be handled under limits for similar hydrocarbons like n-octane (300 ppm TWA). High-level exposures can produce symptoms such as and . Safe handling requires use in well-ventilated areas to minimize vapor accumulation, with equipment grounded to prevent static sparks that could ignite vapors. , including chemical-resistant gloves and safety goggles, is essential to protect against skin and eye contact. Incidents involving 1-octene are rare but typically involve fires resulting from vapor ignition during storage or transfer, emphasizing the need for proper and ignition source control.

Environmental Considerations

1-Octene is considered readily biodegradable under aerobic conditions, with safety data indicating it meets criteria for ready biodegradability in standard tests. Its potential for in organisms is moderate, supported by an estimated factor (BCF) of 660 and log Kow of 4.57 via QSAR modeling. toxicity of 1-octene is high, with an LC50 for of 0.87 mg/L (96-hour exposure), classifying it as very toxic to life; however, its contributes to reduced persistence in bodies by promoting over prolonged exposure. Regulatory classifications reflect chronic hazards, with no specific EC50 values for reported but overall ecological risk tied to its acute effects on sensitive . In industrial production, 1-octene contributes to (VOC) emissions, regulated under the U.S. EPA Clean Air Act to control air quality impacts from processes. 1-Octene is registered under the EU REACH regulation and listed on the U.S. TSCA inventory; it is classified as an aspiration hazard (H304) and very toxic to aquatic life with long-lasting effects (H410). Efforts toward include research into bio-based routes, such as a 2020 chemoenzymatic process converting carbohydrates to 1-octene via ethenolysis of rhamnolipids produced by , aiming to decrease reliance on fossil feedstocks. Waste for 1-octene involves with emission controls like to minimize atmospheric releases, alongside options in olefin process streams where purity allows recovery and reuse.

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