106-35-4

Usage

Uses

Used in the Perfume/Fragrance Industry:
3-Heptanone is used as a fragrance ingredient in the perfume and fragrance industry due to its fruity, green, and fatty scent, which adds a pleasant aroma to various products.
Used in the Solvent Industry:
3-Heptanone serves as a solvent for nitrocellulose and polyvinyl resins, as well as an intermediate in organic synthesis. It is also used in solvent mixes for air-dried and baked finishes, providing a versatile option for various applications in the chemical and industrial sectors.
Used in the Food Industry:
3-Heptanone's natural occurrence in various fruits, cheeses, and other food items contributes to its use in the food industry, where it can be employed to enhance or mimic the flavors and aromas of these products.
Used in the Flavor Industry:
Due to its melon and banana flavor, 3-Heptanone can be used in the flavor industry to create or enhance the taste of certain food products, particularly those with fruity or creamy notes.

Production Methods

EnBK is produced either by catalytic dehydrogenation of 3-heptanol or by hydrogenation of the mixed alcohol condensation product of propionaldehyde and methyl ethyl ketone. Commercial samples can be 95% pure.

Preparation

From n-hept-2-one by hydration.

Synthesis Reference(s)

Journal of the American Chemical Society, 94, p. 1788, 1972 DOI: 10.1021/ja00760a084Tetrahedron Letters, 23, p. 2379, 1982 DOI: 10.1016/S0040-4039(00)87347-5Synthetic Communications, 22, p. 1589, 1992 DOI: 10.1080/00397919208021632

Air & Water Reactions

Flammable.

Reactivity Profile

3-Heptanone is reactive with many acids and bases liberating heat and flammable gases (e.g., H2). The amount of heat may be sufficient to start a fire in the unreacted portion. Reacts with reducing agents such as hydrides, alkali metals, and nitrides to produce flammable gas (H2) and heat. Incompatible with isocyanates, aldehydes, cyanides, peroxides, and anhydrides. May react violently with aldehydes, HNO3, HNO3 + H2O2, and HClO4. Irritating vapors and toxic gases may be formed when involved in fire [USCG, 1999].

Hazard

Moderate fire risk.

Health Hazard

Short term exposure can cause irritation of eyes, nose, throat and lungs. High concentrations may cause headache, dizziness or unconsciousness.

Health Hazard

Inhalation of the vapor of ethyl butyl ketonecan cause irritation to the eyes, skin, andmucous membranes. Its irritation effect wasmild on rabbit skin and eyes. Prolonged skincontact can cause dermatitis. Exposure to4000 ppm for 4 hours proved fatal to rats.Ingestion can cause headache and narcosis,and in large doses coma can occur.LD50 value, oral (rats): 2760 mg/kg.

Fire Hazard

Special Hazards of Combustion Products: Irritating vapors and toxic gases, such as carbon dioxide and carbon monoxide, may be formed when involved in fire.

Safety Profile

Moderately toxic by ingestion and inhalation. A skin and eye irritant. A flammable liquid. Can react with oxidizing materials. To fight fire, use foam, Co2, dry chemical. See also KETONES.

Potential Exposure

Ethyl butyl ketone is used as a solvent and as an intermediate in organic synthesis. It is a solvent for vinyl and nitrocellulose resins. It is used in food flavoring

Environmental fate

Chemical/Physical. 3-Heptanone will not hydrolyze because it has no hydrolyzable functional group.

Shipping

UN1224 Ketones, liquid, n.o.s., Hazard Class: 3; Labels: 3-Flammable liquid, Technical Name Required.

Incompatibilities

May form explosive mixture with air. Violent reaction with strong oxidizers, acetaldehyde, perchloric acid. Attacks some plastics, rubber and coatings

Waste Disposal

Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed

InChI:InChI=1/C7H14O/c1-3-5-6-7(8)4-2/h3-6H2,1-2H3

Upstream product

• 2108-81-8 3-heptanone oxime 
• 4938-52-7 1-hepten-3-ol 
• 13820-09-2 trimethyl orthovalerate 
• 925-90-6 ethylmagnesium bromide 
• 122-62-3 bis(2-ethylhexyl)sebacate 
• 802294-64-0 propionic acid 
• 109-52-4 valeric acid 
• 557-20-0 diethylzinc 
• 638-29-9 n-valeryl chloride 
• 693-03-8 n-butyl magnesium bromide 
• 107-12-0 propiononitrile 
• 6443-92-1 (Z)-hept-2-ene 
• 1632-16-2 2-ethyl-1-hexene 
• 34910-43-5 2-azidohex-1-ene 

Downstream Products

• 28292-42-4 3-aminoheptane 
• 91635-39-1 5-Aethyl-5-hydroxy-decan 
• 5694-74-6 (2-ethyl-2-butyl-[1,3]dioxolan-4-yl)-methanol 
• 75024-35-0 5-butyl-5-ethyl-imidazolidine-2,4-dione 
• 589-82-2 heptan-3-ol 
• 5396-61-2 3-ethyl-1-heptyn-3-ol 
• 3622-67-1 heptan-3-one semicarbazone 
• 5310-05-4 4-(Hexanethioyl)morpholine 
• 345939-74-4 C₂₂H₃₈N₂O₂S 
• 57044-78-7 (2-ethyl-hex-1(E)-enyl)-benzene 
• 76184-05-9 (1-Ethyl-pentyl)-((1R,2R,5S)-5-isopropyl-2-methyl-cyclohexyl)-amine 
• 76184-05-9 (1-Ethyl-pentyl)-((1R,2S,5S)-5-isopropyl-2-methyl-cyclohexyl)-amine 
• 76184-05-9 (1-Ethyl-pentyl)-((1S,2R,5S)-5-isopropyl-2-methyl-cyclohexyl)-amine 
• 76184-05-9 (1-Ethyl-pentyl)-((1S,2S,5S)-5-isopropyl-2-methyl-cyclohexyl)-amine 

Relevant academic research and scientific papers

Oxidations by the reagent O2-H2O2-vanadium complex - Pyrazine-2-carboxylic acid. Part 7. Hydroperoxidation of higher alkanes

Alkanes (n-heptane, 2- and 3-methylhexane, cis- and trans-decalin) are readily oxidized under air in acetonitrile by the O2-H2O2-PCA-VO3- reagent at room temperature to produce alkyl hydroperoxides as main products as well as minor amounts of the corresponding alcohols and carbonyl compounds. The site selectivities of the reactions are very similar to those observed with hydroxylation of the alkanes with hydrogen peroxide under UV irradiation. The proposed mechanism involves the catalytic formation of hydroxyl radicals from hydrogen peroxide which abstract hydrogen atoms from the alkanes. The alkyl radicals react rapidly with molecular oxygen to produce peroxyl radicals which are transformed mainly into the hydroperoxides.

Activation of dioxygen by cobaloxime and nitric oxide for efficient TEMPO-catalyzed oxidation of alcohols

The aerobic oxidation of alcohols to their corresponding carbonyl compounds could be efficiently accomplished by using the combination of cobalt nitrate, dimethylglyoxime and 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) as a novel catalytic system, and various alcohols including primary and secondary benzylic, allylic and aliphatic alcohols could be quantitatively converted to the corresponding aldehydes or ketones at 70 °C under 0.4MPa dioxygen pressure in dichloromethane. During the oxidation, the in situ generated cobaloxime and nitric oxide (NO) were responsible for the activation of dioxygen, respectively, thereby, two concerted catalytic routes exist: cobaloxime-activating-dioxygen TEMPO-catalyzed and NO-activating-dioxygen TEMPO-catalyzed aerobic oxidation of alcohols. Copyright

Synergistic hydrogen atom transfer with the active role of solvent: Preferred one-step aerobic oxidation of cyclohexane to adipic acid by N-hydroxyphthalimide

In this work, we developed an one-step aerobic oxidation of cyclohexane to prepare adipic acid, catalyzed by N-hydroxyphthalimide (NHPI) under promoter- and metal-free conditions. A significant beneficial solvent effect for synergistic reaction is observed with varying polarity and hydrogen-bonding strength: detailed study reveals that the solvent environments manipulate catalytic activity and adipic acid selectivity. Cyclic voltammetry measurements and UV–visible spectra of the NHPI catalyst are examined in various solvent environments to understand the active role of solvent in influencing the catalytic-site structure (>NOH) of the molecule. Analysis of the UV–visible spectra reveals that these differences can be rationalized by considering hydrogen-bonding with solvent molecules, which modifies the catalytic-site structure. This observation is in agreement with cyclic voltammetry results: the different reversibility of the catalytic-site (>NOH/>NO[rad]) wave shows that the catalytic activity of NHPI is related to the formation of hydrogen bonds with the active participation of solvents. Computational studies presented herein have furnished mechanistic insights into the effect of solvent environments. Specifically, we present the structures, dissociation energies, and reaction barriers from DFT studies of the reactants and reaction intermediates involved in the two types of H-abstraction on >NO[rad] catalytic-sites for the rate-determining step. The results of modeling the solvent effects using the PCM continuum solvent method predict that the resulting reaction barrier of the rate-controlling H-abstraction for cyclohexane and cyclohexanone is modified significantly: the transition state barrier of H-abstraction for cyclohexane decreases from 22.36 (in benzene) to 20.78 kcal?mol?1 (in acetonitrile); the α-H-abstraction barrier for cyclohexanone decreases from 21.45 to 20.53 kcal?mol?1. The active participation of solvent molecule results in a strong interaction between pre-reaction complex (PINO???H???C NO[rad] catalytic-sites at the transition state. The lower calculated barriers of H-abstraction for cyclohexanone oxidation approximate more closely the experimental results of the higher adipic acid selectivity. Our work provides a dimension of sustainable chemistry for the metal-free preparation of adipic acid: a conversion of 27% with 79% adipic acid selectivity is achieved over use of NHPI catalysts in CH3CN solvent.

Manganese(II) based Oxidation of Alkanes: Generation of a High Valent Binuclear Catalyst in situ

The efficiently Mn2+ -catalysed oxidation of saturated hydrocarbons by alkylhydroperoxides or iodosylbenzene in the presence of 2,2'-bipyridine in acetonitrile follows the following pathway: Mn2+ + bipy -> 2+ -> 3+, the latter being identified as the catalytic species; it affords cyclohexanol and cyclohexanone in equal amounts and the remarkable robustness of the active complex, under oxidative conditions, is noted.

Effect of cis/trans isomerism on selective oxidation of olefins with nitrous oxide

Liquid phase oxidation of olefins with nitrous oxide is a promising synthetic route to ketones. The effect of cis/trans isomerism on the reactivity of olefins towards N2O and on the reaction mechanism was studied for the first time using 3-heptene oxidation as an example. Our experimental study revealed that cis- and trans-isomers of 3-heptene have similar reactivity and yield the same set of products. However, the cis/trans isomerism of the olefin has a pronounced effect on the reaction route involving the cleavage of the initial C=C bond and, accordingly, on the products ratio. The yield of ketones is lower for the trans-isomer due to higher contribution of the cleavage route.

Redox isomerization of allylic alcohols into carbonyl compounds catalyzed by the ruthenium(IV) complex [Ru(η3:η3-C 10H16)Cl(κ2 O,O -CH3CO 2)] in water and ionic liquids: Highly efficient transformations and catalyst recycling

Isomerization reactions of allylic alcohols into carbonyl compounds can be efficiently performed in both water and in ionic liquids using [Ru(η3:η3-C10H16) Cl(κ2O,O-CH3CO2)] as catalyst. In both cases, the catalytic system could be recycled up to five times.

Photocatalytic oxidation of heptane in the gas-phase over TiO2

VOC are important class of air pollutants, which are considered together with NOx, SOx, and particulates as the most important anthropogenic pollutants generated in urban and industrial areas. Gas-phase photocatalytic oxidation (PCO) of heptane over UV-illuminated TiO2 was performed at ambient temperature in a batch reactor. Complete oxidation of heptane with nearly stoichiometric production of CO2 and H2O was obtained. The intermediates were propanal, butanal, 3-heptanone, 4-heptanone, and CO. The photocatalytic activity of TiO2 could be sustained indefinitely due to the production of water in the system, which can replenish the consumed hydroxyl radicals. Reactive oxygen species, e.g., O2/-, O-, O, and ?OH, played important roles in the PCO of heptane. When hydroxyl radicals were consumed in the heterogeneous oxidation reactions, the surface must be continuously rehydrated if long-term catalytic activity is to be maintained.

In vitro double oxidation of n-heptane with direct cofactor regeneration

A novel concept for the direct oxidation of cycloalkanes to the corresponding cyclic ketones in a one-pot synthesis in water with molecular oxygen as sole oxidizing agent was reported recently. Based on this concept we have developed a new strategy for the double oxidation of n-heptane to enable a biocatalytic resolution for the direct synthesis of heptanone and (R)-heptanols in a one-pot reaction. The bicatalytic cascade employs an NADH driven P450 BM3 monooxygenase variant (WTNADH, 19A12NADH or CM1 NADH) and an (S)-enantioselective alcohol dehydrogenase (RE-ADH). In the initial step n-heptane is hydroxylated under consumption of NADH to produce (R/S)-heptanol. In the second oxidation step the (S)-heptanol enantiomers are transformed to the corresponding ketones, reducing and thereby regenerating the cofactor. Characterization of initial hydroxylation step revealed high turnover frequencies (TOF) of up to 600 min-1, as well as high coupling efficiencies using NADH as cofactor (up to 44%). In the cascade reaction a nearly 2-fold improved product formation was achieved, compared to the single hydroxylation reaction. The total product concentration reached 1.1 mM, corresponding to a total turnover number (TTN) of 2500. Implementation of an additional cofactor regeneration system (D-glucose/glucose dehydrogenase) enabled a further enhancement in product formation with a total product concentration of 1.8 mM and a TTN of 3500. Copyright

Mild homogeneous oxidation of alkanes and alcohols including glycerol with tert-butyl hydroperoxide catalyzed by a tetracopper(II) complex

The homogeneous catalytic system composed of the aqua-soluble tetracopper(II) triethanolaminate complex [O?Cu4{N(CH2CH2O)3}4(BOH)4][BF4]2 (1), t-BuOOH (TBHP), water and acetonitrile solvent (optional) has been applied for the mild oxidation of (i) linear and cyclic alkanes to the corresponding alkyl peroxides, alcohols and ketones, (ii) secondary or primary alcohols to ketones or aldehydes, respectively and (iii) glycerol (GLY) to dihydroxyacetone (DHA). Unusual regio-, bond and stereoselectivity parameters have been determined for the alkane oxygenations and discussed in terms of possible steric, hydrophobic and electronic effects. In alcohol oxidations, secondary alcohols are the most reactive substrates. Yields and TONs up to 82% and 1200, respectively, have been obtained in the oxidation of isopropanol to acetone. The selective oxidation of GLY to DHA by the 1/TBHP system has been also achieved, although providing lower conversions. The 1/H2O2 system for the GLY oxidation is particularly advantageous in terms of selectivity and oxidant efficiency. These systems constitute one of the first examples of a metal-catalyzed oxidation of glycerol under homogeneous conditions.

A NEW SYNTHESIS OF KETONES FROM 1,2-DIMETHOXYETHENYLLITHIUM, ORGANOBORANES, AND ALKYL FLUOROSULFONATES

The reaction of alkyl fluorosulfonates with lithium 1,2-dimethoxyethenyltrialkylborates readily prepared from organoboranes gives corresponding ketones in good yields.