98-85-1

Usage

Uses

Used in Flavor and Fragrance Industry:
DL-1-Phenethylalcohol is used as a fragrance ingredient for its pleasant, rose-like odor and is used in small quantities in perfumery. Its esters are more important as fragrance materials.
Used in Food Industry:
DL-1-Phenethylalcohol is used as a flavoring agent in the food industry due to its presence as a volatile component in various food items, such as tea aroma and mushrooms.
Used in Chemical Synthesis:
DL-1-Phenethylalcohol is used as a chemical intermediate for the production of other chemicals.
Used in Enzyme Applications:
Lipases show good activity and, in some cases, improved enantioselectivity when employed in pure ionic liquids for dynamic kinetic resolution of 1-phenylethanol by transesterification.
Occurrence:
DL-1-Phenethylalcohol is found in various natural sources, such as cranberry, grapes, chive, Scotch spearmint oil, cheeses, cognac, rum, white wine, cocoa, black tea, filbert, cloudberry, beans, mushroom, and endive. The commercial product is the racemic form, and two optically active isomers exist.

Preparation

By oxidation of ethylbenzene or by reduction of acetophenone.

Production Methods

1-Phenylethanol is coproduced with propylene oxide by reaction of a-peroxyethylbenzene (formed by the oxidation of ethylbenzene) with propylene. It is used as a fragrance additive in cosmetics such as perfumes, creams, and soaps and is an intermediate in styrene production. 1-Phenylethanol is also added to foods as a flavoring agent. Industrial exposure may occur from dermal contact and ingestion.

Synthesis Reference(s)

Tetrahedron Letters, 36, p. 3861, 1995 DOI: 10.1016/0040-4039(95)00679-7

Air & Water Reactions

Insoluble in water.

Reactivity Profile

Attacks plastics. [Handling Chemicals Safely, 1980. p. 236]. Acetyl bromide reacts violently with alcohols or water [Merck 11th ed. 1989]. Mixtures of alcohols with concentrated sulfuric acid and strong hydrogen peroxide can cause explosions. Example: An explosion will occur if dimethylbenzylcarbinol is added to 90% hydrogen peroxide then acidified with concentrated sulfuric acid. Mixtures of ethyl alcohol with concentrated hydrogen peroxide form powerful explosives. Mixtures of hydrogen peroxide and 1-phenyl-2-methyl propyl alcohol tend to explode if acidified with 70% sulfuric acid [Chem. Eng. News 45(43):73. 1967; J, Org. Chem. 28:1893. 1963]. Alkyl hypochlorites are violently explosive. They are readily obtained by reacting hypochlorous acid and alcohols either in aqueous solution or mixed aqueous-carbon tetrachloride solutions. Chlorine plus alcohols would similarly yield alkyl hypochlorites. They decompose in the cold and explode on exposure to sunlight or heat. Tertiary hypochlorites are less unstable than secondary or primary hypochlorites [NFPA 491 M. 1991]. Base-catalysed reactions of isocyanates with alcohols should be carried out in inert solvents. Such reactions in the absence of solvents often occur with explosive violence [Wischmeyer 1969].

Health Hazard

Irritating to the skin, eyes, nose, throat, and upper respiratory tract.

Fire Hazard

Combustible material: may burn but does not ignite readily. When heated, vapors may form explosive mixtures with air: indoors, outdoors and sewers explosion hazards. Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated. Runoff may pollute waterways. Substance may be transported in a molten form.

Flammability and Explosibility

Notclassified

Safety Profile

Poison by ingestion and subcutaneous routes. Moderately toxic by skin contact. A skin and severe eye irritant. Questionable carcinogen. Combustible when exposed to heat or flame; can react with oxidming materials. To fight fire, use alcohol foam, foam, CO2, dry chemical

Carcinogenicity

In an NTP study, both sexes of F344 rats were dosed by gavage with 0, 375, and 750 mg/kg 1-phenylethanol 5 days/week for 2 years. There was an increased incidence of neoplastic kidney tumors in the high-dose male rats but no evidence of carcinogenicity in the female rats . In the same NTP study, both sexes of B6C3F1 mice were dosed by oral gavage with 0, 375, and 750 mg/kg 1-phenylethanol 5 days/week for 2 years. There was no evidence that 1-phenylethanol was carcinogenic to mice in this study.

InChI:InChI=1/C8H10O/c1-7(9)8-5-3-2-4-6-8/h2-7,9H,1H3

Upstream product

• 100-42-5 styrene 
• 96-09-3 styrene oxide 
• 16133-83-8 tetrahydro-2-phenylfuran 
• 110-54-3 hexane 
• 15790-54-2 propyl sodium 
• 64-17-5 ethanol 
• 585-71-7 (1-bromoethyl)benzne 
• 123-51-3 i-Amyl alcohol 
• 526-95-4 gluconic acid 
• 1636-34-6 2,3-diphenyl-2,3-butanediol 
• 16002-63-4 phenylmagnesium iodide 
• 917-64-6 methyl magnesium iodide 
• 60-29-7 diethyl ether 
• 100-52-7 benzaldehyde 

Downstream Products

• 4799-66-0 2-(1-phenylethoxy)ethanol 
• 101952-66-3 1-phenylethyl pyridine-3-carboxylate 
• 100-42-5 styrene 
• 93-96-9 bis(1-phenylethyl)ether 
• 15600-32-5 chloroformiate de 1-phenylethyle 
• 33533-53-8 (+/-)-α-methylbenzyl hydrogen phthalate 
• 772-00-9 4-phenyl-1,3-dioxane 
• 14856-75-8 1-phenyl-1-trimethylsilyloxyethane 
• 19657-37-5 nonanedioic acid bis-(1-phenyl-ethyl ester) 
• 98-86-2 acetophenone 
• 3299-05-6 1-ethoxy-1-phenylethane 
• 18758-54-8 1-(triphenylsiloxy)-1-phenylethane 
• 55697-99-9 2,6-diisopropyl-4-(1-phenyl-ethyl)-phenol 
• 32511-53-8 (2,4-dinitro-phenyl)-(1-phenyl-ethyl)-ether 

Relevant academic research and scientific papers

A Convenient and Stable Heterogeneous Nickel Catalyst for Hydrodehalogenation of Aryl Halides Using Molecular Hydrogen

Hydrodehalogenation is an effective strategy for transforming persistent and potentially toxic organohalides into their more benign congeners. Common methods utilize Pd/C or Raney-nickel as catalysts, which are either expensive or have safety concerns. In this study, a nickel-based catalyst supported on titania (Ni-phen@TiO2-800) is used as a safe alternative to pyrophoric Raney-nickel. The catalyst is prepared in a straightforward fashion by deposition of nickel(II)/1,10-phenanthroline on titania, followed by pyrolysis. The catalytic material, which was characterized by SEM, TEM, XRD, and XPS, consists of nickel nanoparticles covered with N-doped carbon layers. By using design of experiments (DoE), this nanostructured catalyst is found to be proficient for the facile and selective hydrodehalogenation of a diverse range of substrates bearing C?I, C?Br, or C?Cl bonds (>30 examples). The practicality of this catalyst system is demonstrated by the dehalogenation of environmentally hazardous and polyhalogenated substrates atrazine, tetrabromobisphenol A, tetrachlorobenzene, and a polybrominated diphenyl ether (PBDE).

Amino Acid-Functionalized Metal-Organic Frameworks for Asymmetric Base–Metal Catalysis

We report a strategy to develop heterogeneous single-site enantioselective catalysts based on naturally occurring amino acids and earth-abundant metals for eco-friendly asymmetric catalysis. The grafting of amino acids within the pores of a metal-organic framework (MOF), followed by post-synthetic metalation with iron precursor, affords highly active and enantioselective (>99 % ee for 10 examples) catalysts for hydrosilylation and hydroboration of carbonyl compounds. Impressively, the MOF-Fe catalyst displayed high turnover numbers of up to 10 000 and was recycled and reused more than 15 times without diminishing the enantioselectivity. MOF-Fe displayed much higher activity and enantioselectivity than its homogeneous control catalyst, likely due to the formation of robust single-site catalyst in the MOF through site-isolation.

New Understanding of Selective Aerobic Oxidation of Ethylbenzene Catalyzed by Nitrogen-doped Carbon Nanotubes

Selective aerobic oxidation of hydrocarbons undergoes a free-radical chain reaction to yield corresponding value-added products is the significant process in the chemical industry. Nanocarbons with heteroatoms doping as free-metal catalysts have been prov

Mixed hetero-/homogeneous TiO2/N-hydroxyimide photocatalysis in visible-light-induced controllable benzylic oxidation by molecular oxygen

Homogeneous and heterogeneous types of catalysis are frequently considered as separate disciplines or even opposed to each other. In the present work, a new type of mixed hetero-/homogeneous catalysis was demonstrated for the case of selective alkylarene

Room Temperature Aerobic Peroxidation of Organic Substrates Catalyzed by Cobalt(III) Alkylperoxo Complexes

Room temperature aerobic oxidation of hydrocarbons is highly desirable and remains a great challenge. Here we report a series of highly electrophilic cobalt(III) alkylperoxo complexes, CoIII(qpy)OOR supported by a planar tetradentate quaterpyridine ligand that can directly abstract H atoms from hydrocarbons (R′H) at ambient conditions (CoIII(qpy)OOR + R′H → CoII(qpy) + R′?+ ROOH). The resulting alkyl radical (R′?) reacts rapidly with O2to form alkylperoxy radical (R′OO?), which is efficiently scavenged by CoII(qpy) to give CoIII(qpy)OOR′ (CoII(qpy) + R′OO?→ CoIII(qpy)OOR′). This unique reactivity enables CoIII(qpy)OOR to function as efficient catalysts for aerobic peroxidation of hydrocarbons (R′H + O2→ R′OOH) under 1 atm air and at room temperature.

Borane evolution and its application to organic synthesis using the phase-vanishing method

Although borane is a useful reagent, it is difficult to handle. In this study, borane was generated in situ from NaBH4 or nBu4NBH4 with several oxidants using a phase-vanishing (PV) method. The borane generated was directly reacted with alkenes, affording the desired alcohols in good yields after oxidation with H2O2 under basic conditions. The selective reduction of carboxylic acids with the evolved borane was examined. The organoboranes generated by the PV method successfully underwent Suzuki–Miyaura coupling. Using this PV system, reactions with borane can be carried out easily and safely in a common test tube.

Fe-Catalyzed Anaerobic Mukaiyama-Type Hydration of Alkenes using Nitroarenes

Hydration of alkenes using first row transition metals (Fe, Co, Mn) under oxygen atmosphere (Mukaiyama-type hydration) is highly practical for alkene functionalization in complex synthesis. Different hydration protocols have been developed, however, control of the stereoselectivity remains a challenge. Herein, highly diastereoselective Fe-catalyzed anaerobic Markovnikov-selective hydration of alkenes using nitroarenes as oxygenation reagents is reported. The nitro moiety is not well explored in radical chemistry and nitroarenes are known to suppress free radical processes. Our findings show the potential of cheap nitroarenes as oxygen donors in radical transformations. Secondary and tertiary alcohols were prepared with excellent Markovnikov-selectivity. The method features large functional group tolerance and is also applicable for late-stage chemical functionalization. The anaerobic protocol outperforms existing hydration methodology in terms of reaction efficiency and selectivity.

Direct use of the solid waste from oxytetracycline fermentation broth to construct Hf-containing catalysts for Meerwein-Ponndorf-Verley reactions

The oxytetracycline fermentation broth residue (OFR) is an abundant solid waste in the fermentation industry, which is hazardous but tricky to treat. The resource utilization of the waste OFR is still challenging. In this study, a novel route of using OFR was proposed that OFR was used as the organic ligands to construct a new hafnium based catalyst (Hf-OFR) for Meerwein-Ponndorf-Verley (MPV) reactions of biomass-derived platforms. The acidic groups in OFR were used to coordinate with Hf4+, and the carbon skeleton structures in OFR were used to form the spatial network structures of the Hf-OFR catalyst. The results showed that the synthesized Hf-OFR catalyst could catalyze the MPV reduction of various carbonyl compounds under relatively mild reaction conditions, with high conversions and yields. Besides, the Hf-OFR catalyst could be recycled at least 5 times with excellent stability in activity and structures. The prepared Hf-OFR catalyst possesses the advantages of high efficiency, a simple preparation process, and low cost in ligands. The proposed strategy of constructing catalysts using OFR may provide new routes for both valuable utilization of the OFR solid waste in the fermentation industry and the construction of efficient catalysts for biomass conversion.

Cascade Reductive Friedel-Crafts Alkylation Catalyzed by Robust Iridium(III) Hydride Complexes Containing a Protic Triazolylidene Ligand

The synthesis of complex molecules like active pharmaceutical ingredients typically requires multiple single-step reactions, in series or in a modular fashion, with laborious purification and potentially unstable intermediates. Cascade processes offer attractive synthetic remediation as they reduce time, energy, and waste associated with multistep syntheses. For example, triarylmethanes are traditionally prepared via several synthetic steps, and only a handful of cascade routes are known with limitations due to high catalyst loadings. Here, we present an expedient catalytic cascade process to produce triarylmethanes. For this purpose, we have developed a bifunctional iridium system as the efficient catalyst to build heterotriaryl synthons via reductive Friedel-Crafts alkylation from ketones, arenes, and hydrogen. The catalytically active species were generated in situ from a robust triazolyl iridium(III) hydride complex and acid and is composed of a metal-bound hydride and a proximal ligand-bound proton for reversible dihydrogen release. These complexes catalyze the direct hydrogenation of ketones at slow rates followed by dehydration. Appropriate adjustment of the conditions successfully intercepts this dehydration and leads instead to efficient C-C coupling and Friedel-Crafts alkylation. The scope of this cascade process includes a variety of carbonyl substrates such as aldehydes, (alkyl)(aryl)ketones, and diaryl ketones as precursor electrophiles with arenes and heteroarenes for Friedel-Crafts coupling. The reported method has been validated in a swift one-step synthesis of the core structure of a potent antibacterial agent. Excellent yields and exquisite selectivities were achieved for this cascade process with unprecedentedly low iridium loadings (0.02 mol %). Moreover, the catalytic activity of the protic system is significantly higher than that of an N-methylated analogue, confirming the benefit of the Ir-H/N-H hydride-proton system for high catalytic performance.

Effect of solvent in the hydrogenation of acetophenone catalyzed by Pd/S-DVB

A solvent effect was found in the hydrogenation of acetophenone catalyzed by a new Pd/S-DVB catalyst, immobilized on a styrene (S)/divinylbenzene (DVB) copolymer containing phosphinic groups. The porous structure of the catalyst was characterized by a specific surface area of 94.7 m2g?1. The presence of Pd(ii) and Pd(0) in Pd/S-DVB was evidenced by XPS and TEM. Pd/S-DVB catalyzes the hydrogenation of acetophenone (APh) to 1-phenylethanol (PhE) and ethylbenzene (EtB). The highest conversion of APh was obtained in methanol (MeOH) and in 2-propanol (2-PrOH), while in water it was lower. The conversion of APh correlates well with the hydrogen-bond-acceptance (HBA) capacity of the solvent. However, in all binary mixtures of alcohol and water the APh conversion and the yield of products significantly decreased. The observed inhibiting effect can be explained by the microheterogeneity of these mixtures and the blocking of the catalyst surface restricting access of the substrates to the Pd centers.