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2-Ethylhexanol

2-Ethylhexanol, also known as 2-ethyl-1-hexanol, is a branched-chain with the molecular formula C₈H₁₈O and a molecular weight of 130.23 g/mol. It appears as a clear, colorless to pale yellow with a characteristic mild , possessing a of approximately 184°C and a low that indicates limited volatility. This eight-carbon chiral compound is poorly soluble in (about 1 g/L at 20°C) but highly miscible with most organic solvents, making it versatile for industrial applications. Industrially, 2-ethylhexanol is produced via a multi-step starting with the of using and to form n-, followed by of the butyraldehyde to produce 2-ethylhex-2-enal, , and finally to yield the , with subsequent for purification. This , often conducted under controlled conditions (e.g., at 140–170°C and 10–30 bar), is a cornerstone of large-scale chemical , with global exceeding millions of tons annually to meet in downstream sectors. The compound's primary use is as a key in synthesizing plasticizers, particularly di(2-ethylhexyl) phthalate (DEHP), which is essential for flexible (PVC) products like cables, flooring, and medical tubing. Additional applications include its role as a solvent in coatings and inks, a component in synthetic lubricants and defoamers, and a building block for adhesives, , and even as a flavor volatile in certain foods. From a safety perspective, 2-ethylhexanol is classified as a flammable liquid (flash point around 78°C) and a skin and eye irritant, potentially causing respiratory irritation upon inhalation or dermatitis upon prolonged skin contact, though it poses low to moderate overall health risks under proper industrial hygiene practices. It is not considered persistent, bioaccumulative, or toxic to aquatic life at typical exposure levels, but handling requires ventilation, protective equipment, and adherence to regulations like those from the EPA for inert ingredient use in pesticides. Ongoing research focuses on optimizing production efficiency and exploring bio-based alternatives to reduce reliance on petrochemical feedstocks.

Structure and Nomenclature

Chemical Structure

2-Ethylhexanol has the molecular formula C₈H₁₈O. Its condensed is CH₃(CH₂)₃CH(C₂H₅)CH₂OH, representing a linear chain with an ethyl branch at the second carbon and a hydroxyl group at the first carbon. As a , 2-ethylhexanol features the -OH group attached to a terminal (primary) carbon atom within a branched eight-carbon aliphatic chain. The branching occurs via an ethyl substituent (-CH₂CH₃) at the 2-position of the hexyl backbone, which distinguishes it from straight-chain octanol isomers. The carbon at the 2-position serves as a chiral center, bonded to four distinct groups: a , the ethyl , a (-CH₂CH₂CH₂CH₃), and the (-CH₂OH). This asymmetry results in two enantiomers, (R)-2-ethylhexan-1-ol and (S)-2-ethylhexan-1-ol. Commercial 2-ethylhexanol is produced and supplied predominantly as a of these enantiomers. In representations, the molecule is depicted as a chain for the main hexyl backbone, with the ethyl branch extending from the second carbon and the -CH₂OH terminating the chain, emphasizing the branched without explicit hydrogen atoms. The IUPAC name, 2-ethylhexan-1-ol, systematically denotes the hexanol chain, the position of the ethyl , and the functionality.

Naming Conventions

The International Union of Pure and Applied Chemistry (IUPAC) recommended name for this compound is 2-ethylhexan-1-ol. It is commonly referred to as 2-ethylhexanol, often abbreviated as 2-EH in industrial and technical contexts, along with variants such as 2-ethyl-1-hexanol and 2-ethylhexyl alcohol. A historical synonym is isooctanol, reflecting its status as a branched isomer of octanol. The etymology of the name stems from its derivation as a based on hexan-1-ol, with an attached at the 2-position, which together form a branched C8 . This systematic designation is favored in modern chemical literature over older, less precise terms like octyl alcohol—originally used for both the linear and this branched form—to ensure clarity and avoid confusion in identification and classification. For regulatory and database purposes, 2-ethylhexanol is uniquely identified by the (CAS) 104-76-7 and the European Community (EC) Number 203-234-3. The nomenclature underscores the molecule's chiral center at the substituted carbon, though racemic mixtures are typical in commercial production.

Physical and Chemical Properties

Physical Properties

2-Ethylhexanol is a colorless, oily with a mild, characteristic at . The compound exhibits the following key physical properties under standard conditions:
PropertyValueConditions
184.7 °C760 mmHg
Melting point−76 °C-
0.833 g/cm³25 °C
1.43020 °C (D line)
These values reflect the branched alkyl chain structure, which contributes to its relatively high and low volatility compared to linear alcohols of similar molecular weight. 2-Ethylhexanol is practically insoluble in , with a solubility of approximately 1 g/L at 20 °C, but it is miscible with common organic solvents such as and . Its vapor pressure is low at 0.3 mmHg at 20 °C, indicating limited evaporation under ambient conditions, while the flash point is 75 °C (closed cup), classifying it as a combustible liquid.

Chemical Properties

2-Ethylhexanol functions as a primary alcohol due to its terminal -CH₂OH group, enabling characteristic reactions such as esterification with carboxylic acids to produce esters like 2-ethylhexyl acetate or 2-ethylhexyl acrylate. Etherification is also possible, as demonstrated by its reaction with epichlorohydrin to form 2-ethylhexyl glycidyl ether, a compound used in epoxy formulations. Additionally, oxidation of the alcohol group yields 2-ethylhexanal as an intermediate, which can further oxidize to 2-ethylhexanoic acid under appropriate conditions. In terms of stability, 2-ethylhexanol remains relatively inert under neutral conditions but slowly oxidizes in air to 2-ethylhexanal, particularly when exposed to light or catalysts; it is combustible and incompatible with strong oxidizing agents or acids, which can lead to hazardous reactions. The hydroxyl proton exhibits weak acidity with a of 15.05 ± 0.10, supporting hydrogen bonding interactions while limiting its role as a beyond such associations. Owing to its mild nature, 2-ethylhexanol demonstrates low corrosivity and good compatibility with construction materials, including metals like and , as well as polymers such as , Teflon, and , facilitating its handling in industrial settings.

Synthesis and Production

Laboratory Synthesis

In laboratory settings, 2-ethylhexanol is commonly prepared via the classic of n-butyraldehyde followed by . This multi-step process begins with the base-catalyzed self-condensation of two equivalents of n-butyraldehyde to yield 2-ethyl-3-hydroxyhexanal, which spontaneously dehydrates under the reaction conditions to form 2-ethylhex-2-enal; subsequent reduces the α,β-unsaturated first to 2-ethylhexanal and then to 2-ethylhexanol. The simplified reaction scheme is as follows: $2 \ce{CH3CH2CH2CHO} \xrightarrow{\ce{OH^-}} \ce{CH3CH2CH2CH=C(CHO)CH2CH3} \xrightarrow{\ce{H2, Pd}} \ce{CH3CH2CH2CH2CH(CHO)CH2CH3} \xrightarrow{\ce{H2, Pd}} \ce{CH3CH2CH2CH2CH(CH2CH3)CH2OH} Typical conditions for the involve dilute aqueous (5-10% NaOH) at 20-40°C for 1-2 hours, achieving conversions of 80-90% with selectivity to the dehydrated product around 80-85%. The is conducted stepwise using gas at 50-100 atm and (Pd/C) catalyst in or solvent at 50-100°C, yielding 95-99% for each reduction step. Overall yields for the sequence in small-scale preparations range from 70-90%, with the final product purified by under reduced pressure (boiling point 184-185°C at ). An alternative laboratory route involves the reduction of commercially available to the corresponding . This is typically accomplished using lithium aluminum hydride (LiAlH4) in anhydrous or at 0-25°C, followed by careful with and dilute to liberate the . Catalytic over or at 150-200°C and 100-200 atm can also be employed, though LiAlH4 is preferred for its simplicity in bench-scale work. Yields for this reduction exceed 90%, and purification proceeds via as in the aldol route.

Industrial Production

The industrial production of 2-ethylhexanol was commercialized in the as an extension of the Oxo process, originally developed in the late 1930s for reactions and scaled post-World War II for higher alcohols like n-butanol. The primary manufacturing route involves a three-step sequence starting with the of to produce n-butyraldehyde, followed by to form 2-ethylhex-2-enal (via self-condensation and dehydration of n-butyraldehyde), and concluding with to yield 2-ethylhexanol. In the step, (C₃H₆) reacts with (CO and H₂) over a or catalyst at 100–150°C and 10–30 bar to form n-butyraldehyde (C₄H₈O). The occurs under basic conditions (e.g., with dilute NaOH) at 80–120°C, producing 2-ethyl-2-hexenal as an intermediate, which is then hydrogenated over catalysts (H₂/Ni) at 120–150°C and 20–30 bar. Key raw materials include , derived from refining or , and , produced via reforming or . Major producers encompass SE in , and in the United States, and Ltd. in Asia, operating integrated facilities that leverage in and olefin production. Global production was approximately 4 million metric tons annually as of 2024, with capacity exceeding 5.7 million metric tons as of 2023; capacity is concentrated in (over 50% share, led by ), , and , with major plants in (), , and (). The process is energy-intensive, primarily for generation and , while byproducts such as higher alcohols ("heavies"), unreacted aldehydes, and n-butanol are recycled or sold as components. Recent research explores bio-based routes from biomass-derived syngas or butanal and integrated one-step processes using catalysts like TiO2 to simplify production and reduce energy consumption.

Applications

Primary Industrial Uses

The primary industrial use of 2-ethylhexanol is in the production of plasticizers, particularly di(2-ethylhexyl) phthalate (DEHP), which is synthesized by esterifying 2-ethylhexanol with phthalic anhydride (2-EH + phthalic anhydride → DEHP). Plasticizers, particularly DEHP, account for over 50% of global 2-ethylhexanol demand as of 2024, primarily serving as a softening agent in polyvinyl chloride (PVC) to enhance flexibility in products such as flooring, cables, and films. However, due to health concerns, DEHP use is being restricted in certain applications, such as medical devices, with phase-out timelines including 2030 for intravenous solution containers and 2035 for intravenous tubing in California. DEHP's widespread adoption stems from its cost-effectiveness and performance in making rigid PVC pliable without significantly compromising strength. In addition to plasticizers, 2-ethylhexanol functions as a reactive diluent in the formulation of alkyd resins and polyurethanes for coatings and adhesives, where it reduces viscosity during processing while incorporating into the final network to improve and . This role leverages its solvent-like properties, enabling better dispersion of resins and pigments in high-solids systems used for protective finishes. The sector dominates 2-ethylhexanol consumption, driving overall market demand through its integration into materials like and roofing, as well as automotive components such as dashboards and wiring. Annual usage fluctuates with these industries' , with and automotive sectors collectively accounting for over 40% of end-use demand due to rising and needs.

Secondary and Specialized Uses

2-Ethylhexanol serves as a defoaming agent in various formulations, leveraging its surface-active properties to reduce formation and improve processing efficiency. In the paints and inks industry, it acts as an antifoam additive, preventing unwanted bubbles during mixing and application, which enhances product quality and application performance. Similarly, in detergents and cleaning products, its low contributes to foam control in aqueous systems, aiding in the of emulsions and suspensions during . As a , 2-ethylhexanol finds application in lubricants and hydraulic fluids, where it provides for additives and improves characteristics without significantly affecting fluid stability. Its compatibility with compounds makes it suitable for formulating high-performance lubricants used in machinery. In processes, particularly in and separation, 2-ethylhexanol enhances the of triglycerides and other , achieving extraction yields up to 80% in solvent-assisted methods for residual oils from materials. At low concentrations, 2-ethylhexanol is incorporated into fragrances and flavors, imparting a mild, sweet, floral-rosy that blends well in cosmetic and products. Global annual usage in fragrance compounds is estimated at 0.1–1.0 metric tons, typically at trace levels in fine fragrances, shampoos, soaps, and flavorings for items like fruits and meats, where it occurs naturally or as an added component. Emerging applications include bio-based production routes for 2-ethylhexanol, derived from via processes like Guerbet coupling of bio-butanol or of , yielding 45–90% efficiency and serving as a sustainable to sources. It also plays a role in through derivatives like 2-ethylhexyl , a cetane improver additive that enhances ignition quality in diesel- blends, improving engine performance and reducing emissions. As a minor intermediate in pharmaceuticals, 2-ethylhexanol is used in synthesizing compounds for formulations and medical-grade materials, supporting the production of active pharmaceutical ingredients and biomedical polymers.

Safety, Health, and Environmental Impact

Human Health Effects

2-Ethylhexanol primarily enters the through , dermal , and , with being the most common occupational route due to its and use in settings. can occur in environments where the compound is aerosolized or vaporized, contributing to respiratory uptake. Acute to 2-ethylhexanol causes to the eyes, , and . It is classified as a irritant (Category 2), leading to redness and moderate upon dermal , and a severe eye irritant (Category 2A), resulting in serious eye damage including redness and pain. of vapors or aerosols at concentrations around 1 /m³ for short durations (e.g., 2 hours) induces in the eyes and , along with symptoms such as , , and respiratory discomfort in volunteers. Animal studies confirm low acute systemic toxicity, with an inhalation LC50 greater than 5,000 /m³ (4-hour ) in rats, indicating minimal lethality at high concentrations. Chronic exposure demonstrates low systemic toxicity, with no observed levels (NOAELs) established at 252 mg/kg/day via dermal route in rats for developmental effects and 36 mg/kg/day via oral route in rats for chronic effects, primarily involving reduced body weight and increased organ weights (e.g., liver, ) at higher doses. Direct endocrine-disrupting effects of 2-ethylhexanol are mild and not strongly evidenced, though it serves as a of the known di(2-ethylhexyl) phthalate (DEHP), potentially contributing indirectly to hormonal imbalances in contexts of phthalate exposure. No significant neurotoxic, mutagenic, or reproductive effects beyond those associated with general have been observed at relevant doses. Under the Globally Harmonized System (GHS), 2-ethylhexanol is classified with hazard statements H315 (causes skin irritation), H319 (causes serious eye irritation), and H335 (may cause respiratory irritation). It is not regulated by an OSHA (PEL), though the ACGIH (TLV) is 5 ppm (time-weighted average). Regarding carcinogenicity, 2-ethylhexanol is not classifiable as to its carcinogenicity to humans (IARC Group 3), with no evidence in rats and only equivocal evidence of liver tumors in mice at high chronic doses.

Environmental Fate and Regulations

2-Ethylhexanol is readily biodegradable in aerobic conditions, achieving greater than 70% degradation within 28 days according to 301 screening tests, such as the MITI-I (Modified MITI) method equivalent to TG 301C. It demonstrates rapid breakdown in and natural waters, with degradation rates of 79-99% observed in standard biotic processes. Due to its low bioaccumulation potential, with an (log Kow) of approximately 2.7-2.9 and a bioconcentration factor (BCF) estimated at 20-30 in , it does not significantly accumulate in organisms or chains. In the environment, 2-ethylhexanol exhibits moderate volatility, with a Henry's Law constant indicating potential for evaporation from surface waters and moist soils, estimated half-life in a model river around 3 hours. It shows low adsorption to and due to its moderate solubility (about 1 g/L), facilitating into , particularly from industrial spills or waste sites. Aquatic toxicity is relatively low compared to more persistent organics, with acute LC50 values for ranging from 17-100 mg/L (e.g., 17.1 mg/L for golden orfe in 96-hour 203 tests), indicating harm to sensitive species at elevated concentrations but limited broader impact under typical exposure. Under the European Union's REACH regulation, 2-ethylhexanol is registered (EC 203-234-3) with no specific substance restrictions, but its use in producing restricted like DEHP (Annex XVII entry 51) limits applications in consumer plastics to prevent indirect environmental release. , the EPA classifies 2-ethylhexanol as a List 4 inert ingredient exempt from tolerance requirements for formulations under 40 CFR 180.920, allowing its use as a or with assessments confirming low environmental risk from approved applications. Globally, emission controls under the Stockholm Convention indirectly affect 2-ethylhexanol through regulation of persistent organic pollutants like certain flame retardants and derived from it, though the compound itself is not listed as a POP.

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