4170-30-3

Usage

Uses

Used in Chemical Industry:
CROTONALDEHYDE is used as an important industrial chemical for the synthesis of tocopherol (vitamin E), the food preservative sorbic acid, and the solvent 3-methylbutanol.
Used in Organic Synthesis:
CROTONALDEHYDE is used as an intermediate in the production of butyl alcohol, butyraldehyde, methoxybutyraldehyde, sorbic acid, maleic acid, crotonic acid, and crotyl alcohol.
Used in Polymer Chemistry:
CROTONALDEHYDE is used as a manufacturing agent for resins and polyvinyl acetals, a solvent for polyvinyl chloride, and a rubber antioxidant that increases rubber strength with ketones.
Used in Agriculture:
CROTONALDEHYDE is used in the preparation of insecticides and fertilizers.
Used in Flavor Production:
CROTONALDEHYDE is used in the production of flavors.
Used as a Warning Agent:
CROTONALDEHYDE is used as a warning agent in fuel gases due to its strong suffocating odor.
Used in the Production of Scorbic Acid:
CROTONALDEHYDE is used as an intermediate for the production of scorbic acid.
Used in the Manufacture of n-Butyl Alcohol:
CROTONALDEHYDE was formerly used in the manufacture of n-butyl alcohol.
Used in the Formation of Emissions:
CROTONALDEHYDE is formed during the combustion of fossil fuels.

Air & Water Reactions

Highly flammable. Slightly soluble in water.

Reactivity Profile

CROTONALDEHYDE can react violently with strong oxidizing reagents, e.g., reaction with conc. nitric acid leads to instantaneous ignition [Andrussow, L., Chim. Ind. (Paris), 1961, 86, p. 542]. In contact with strong acids or bases CROTONALDEHYDE will undergo an exothermic condensation reaction. Reaction with 1,3-butadiene is particularly violent [Greenlee, K. W., Chem. Eng. News, 1948, 26, p. 1985]. Crotonaldehyde may rapidly polymerize with ethyl acetoacetate (Soriano, D.S. et al. 1988. Journal of Chemical Education 65:637.).

Hazard

An animal carcinogen. Irritating to eyes, skin, and upper respiratory tract irritant. Flammable, dangerous fire risk. Explosive limits in air 2.9–15.5% by volume. Questionable carcinogen.

Health Hazard

CROTONALDEHYDE is an extreme eye, respiratory, and skin irritant and can cause corneal damage. A 15 minute exposure at 4.1 ppm is highly irritating to the nose and upper respiratory tract and causes tearing. Brief exposure at 45 ppm proved very disagreeable with prominent eye irritation.

Fire Hazard

Flammable/combustible material; may be ignited by heat, sparks or flames. Vapor may travel to a source of ignition and flash back. Container may explode in heat of fire. Vapor explosion and poison hazard indoors, outdoors or in sewers. Runoff to sewer may create fire or explosion hazard. Readily converted by oxygen to hazardous peroxides and acids and is incompatible with caustics, ammonia, organic amines, mineral acids, and strong oxidizers. Readily resinifies to dimer when pure and slowly oxidizes to crotonic acid. Altered by light and air. Hazardous polymerization may occur. Polymerization may take place at high temperatures.

Safety Profile

Suspected carcinogen with experimental carcinogenic data. Poison by ingestion and inhalation. Mutation data reported. An eye, skin, and mucous membrane irritant. A lachrymating material that can cause corneal burns and is very dangerous to the eyes. Caution: Keep away from heat and open flame. Keep container closed. Use with adequate ventilation. Extremely irritating to eyes, slim, mucous membranes. When necessary, the lachrymatory effect of the vapors may be counteracted by ammonia fumes. Dangerous fire hazard when exposed to heat or flame; can react with oxidizing materials. To fight fire, use alcohol foam, CO2, dry chemical. Reacts violently with 1,3 butadlene. Violent hypergolic reaction with concentrated nitric acid. When heated to decomposition it emits acrid smoke and fumes. See also ALDEHYDES.

Carcinogenicity

Similar to acrolein, crotonaldehyde is suspected of having tumorigenic activity and of involvement in the metabolism of N-nitrosopyrrolidine . Nevertheless, it has been proven that crotonaldehyde does have a carcinogenic effect on rats. Indeed, crotonaldehyde and nitrosopyrrolidine (a metabolite of crotonaldehyde) induced neoplastic lesions in the liver, hepatocellular carcinomas, neoplastic nodules, and liver damage when administered orally to rats over long periods of time.

Source

Reported in gasoline-powered automobile exhaust at concentrations ranging from 100 to 900 ppb (quoted, Verschueren, 1983). Gas-phase tailpipe emission rates from California Phase II reformulated gasoline-powered automobiles with and without catalytic converters were 1.17 and 114 mg/km, respectively (Schauer et al., 2002). Schauer et al. (2001) measured organic compound emission rates for volatile organic compounds, gas-phase semi-volatile organic compounds, and particle phase organic compounds from the residential (fireplace) combustion of pine, oak, and eucalyptus. The gas-phase emission rates of crotonaldehyde were 276 mg/kg of pine burned, 177 mg/kg of oak burned, and 198 mg/kg of eucalyptus burned.

Environmental fate

Biological. Heukelekian and Rand (1955) reported a 10-d BOD value of 1.30 g/g which is 56.8% of the ThOD value of 2.29 g/g. Chemical/Physical. Slowly oxidizes in air forming crotonic acid (Windholz et al., 1983). At elevated temperatures, crotonaldehyde may polymerize (NIOSH, 1997). Crotonaldehyde undergoes addition of water across the CH=CH bond yielding 3- hydroxybutanal (Kollig, 1995). At an influent concentration of 1,000 mg/L, treatment with GAC resulted in effluent concentration of 544 mg/L. The adsorbability of the carbon used was 92 mg/g carbon (Guisti et al., 1974).

Toxicity evaluation

Crotonaldehyde (steric form not reported) has been identified as a volatile emission product from the arboreous plant Chinese arborvitae. It has also been detected in gases emitted from volcanoes. (E)-Crotonaldehyde is emitted to the atmosphere from the combustion of wood and in exhaust from gasoline and diesel engines. It is also released to the environment from tobacco smoke, polymer combustion, and turbine exhaust. (E)-Crotonaldehyde has been detected in drinking water and wastewater, and in human milk and expired air. If released to soil, (E)-crotonaldehyde will have very high mobility. Volatilization of (E)-crotonaldehyde may be important from moist and dry soil surfaces. Biodegradation studies suggest that (E)-crotonaldehyde may be biodegradable in soil and water, especially in anaerobic conditions. (E)-Crotonaldehyde readily polymerizes; therefore, if it is released to soil or water in a spill situation, a significant fraction may polymerize. If released to water, (E)-crotonaldehyde may not adsorb to suspended solids and sediment.

InChI:InChI=1/C4H6O/c1-2-3-4-5/h2-4H,1H3/b3-2-

Upstream product

• 3724-65-0 2-butenoic acid 
• 64-18-6 formic acid 
• 500-05-0 2H-pyran-2-one-5-carboxylic acid 
• 593-60-2 Vinyl bromide 
• 627-27-0 homoalylic alcohol 
• 497-06-3 3,4-butenediol 
• 6117-80-2 1,4-butenediol 
• 506-96-7 Acetyl bromide 
• 821-42-1 pentenedial 
• 64-17-5 ethanol 
• 107-01-7 butene-2 
• 18826-95-4 1.3-butanediol 
• 626-93-7 n-hexan-2-ol 
• 821-11-4 trans-butene-1,4-diol 

Downstream Products

• 80466-34-8 2,4-hexadienal 
• 17609-31-3 2,4,6-octatrienal 
• 40650-87-1 2,4,6,8-decatetraenal 
• 4433-34-5 11t-[2]furyl-undeca-2t,4t,6t,8t,10-pentaenal 
• 324-32-3 2-methyl-7-trifluoromethylquinoline 
• 52199-37-8 2,4-dimethyl-1,4-dihydro-pyridine-3-carboxylic acid ethyl ester 
• 106334-26-3 2-(2-bromopropyl)-1,3-dioxolane 
• 4528-26-1 2-propenyl-[1,3]dioxolane 
• 13893-40-8 3-hydroxyhex-4-enoic acid 
• 24581-03-1 hepta-1,5-dien-4-ol 
• 3033-82-7 8-chloroquinaldine 
• 20409-84-1 5-methyl-1-phenyl-4,5-dihydro-1H-pyrazole 
• 54059-73-3 crotonal phenylhydrazone 
• 5775-96-2 1,5-dimethyl-4,5-dihydro-1H-pyrazole 

Relevant academic research and scientific papers

Dual Role of the Rhodium(III) Catalyst in C-H Activation: [4 + 3] Annulation of Amide with Allylic Alcohols to 7-Membered Lactams

[4 + 3] annulation of primary and secondary benzamide and cinnamamide derivatives using allyl alcohol as a coupling partner catalyzed by Rh(III) is reported, where Rh(III) is playing a dual role of an oxidant and a catalyst for C-H activation. The Rh-catalyst oxidizes allyl alcohol to its carbonyl derivative, and the in situ-generated carbonyl compound reacts with benzamide in the presence of the Rh-catalyst, forming the corresponding alkylated products. Mechanistic studies show that AgSbF6 is also playing a dual role. Apart from being a halide scavenger, AgSbF6 catalyzes the cyclization of the alkylated product, forming the desired lactam. The current method has good synthetic application and is useful for synthesizing a few biologically active compounds that can act as the dopamine D3 receptor ligand, including berberine-like analogues. The deuteration study and control experiments helped us to propose the mechanism.

Method for preparing crotonaldehyde from ethanol

The invention relates to a method for preparing crotonaldehyde from ethanol. The method comprises the following steps of firstly, dehydrogenating ethanol into acetaldehyde by using a metal-loaded semiconductor photocatalyst under illumination, then carrying out aldol condensation under base catalysis, and finally dehydrating under a heating condition to form crotonaldehyde. The method starts from ethanol and has the advantages of wide raw material sources, mild reaction conditions and the like.

Rapid, chemoselective and mild oxidation protocol for alcohols and ethers with recyclable N-chloro-N-(phenylsulfonyl)benzenesulfonamide

Chlorine is the 20th most abundant element on the earth compared to bromine, iodine, and fluorine, a sulfonimide reagent, N-chloro-N-(phenylsulfonyl)benzenesulfonamide (NCBSI) was identified as a mild and selective oxidant. Without activation, the reagent was proved to oxidize primary and secondary alcohols as well as their symmetrical and mixed ethers to corresponding aldehydes and ketones. With recoverable PS-TEMPO catalyst, selective oxidation over chlorination of primary and secondary alcohols and their ethers with electron-donating substituents was achieved. The reagent precursor of NCBSI was recovered quantitatively and can be reused for synthesizing NCBSI.

Copper-Containing Catalysts Based on Cerium–Zirconium Oxide Supports in Ethanol Conversion Reaction According to In Situ IR Spectroscopic Data

Abstract: Copper-containing catalysts based on CeO2–ZrO2 solid solutions were prepared by the Pecini method and studied using a set of physicochemical methods. It was found that the bond strength of oxygen on the catalyst surface, which depends on the properties of supported copper oxide clusters and a ratio between CeO2 and ZrO2 in the support, plays a main role in ethanol conversion. Ethoxy groups, acetate and formate complexes, and condensation products were detected as main surface intermediates formed in the course of ethanol conversion on the catalysts. The decomposition of the formate complexes was the key stage in the formation of hydrogen. Its appearance on the surface of the catalysts was due to the competition between the reactions of formate and acetate complex formation for oxygen with suitable properties.

A study on the cataluminescence of propylene oxide on FeNi layered double hydroxides/graphene oxide

In this work, FeNi layered double hydroxides/graphene oxide (FeNi LDH/GO) was prepared, which exhibits excellent selective cataluminescent performance towards propylene oxide. The selectivity and sensitivity of the cataluminescence (CTL) reaction were investigated in detail. Moreover, the catalytic reaction mechanism, including the intermediate products and the conversion of reactants to products, was discussed based on both the experimental and computational results. Furthermore, the proposed FeNi LDH/GO based CTL sensor was successfully applied for the determination of propylene oxide residue in fumigated raisins, which indicates extensive application potential for rapid food safety evaluation.

Lewis Acidic Boranes, Lewis Bases, and Equilibrium Constants: A Reliable Scaffold for a Quantitative Lewis Acidity/Basicity Scale

A quantitative Lewis acidity/basicity scale toward boron-centered Lewis acids has been developed based on a set of 90 experimental equilibrium constants for the reactions of triarylboranes with various O-, N-, S-, and P-centered Lewis bases in dichloromethane at 20 °C. Analysis with the linear free energy relationship log KB=LAB+LBB allows equilibrium constants, KB, to be calculated for any type of borane/Lewis base combination through the sum of two descriptors, one for Lewis acidity (LAB) and one for Lewis basicity (LBB). The resulting Lewis acidity/basicity scale is independent of fixed reference acids/bases and valid for various types of trivalent boron-centered Lewis acids. It is demonstrated that the newly developed Lewis acidity/basicity scale is easily extendable through linear relationships with quantum-chemically calculated or common physical–organic descriptors and known thermodynamic data (ΔH (Formula presented.)). Furthermore, this experimental platform can be utilized for the rational development of borane-catalyzed reactions.

IBX-TfOH mediated oxidation of alcohols to aldehydes and ketones under mild reaction conditions

An efficient, practical and facile procedure has been developed for the oxidation of primary and secondary alcohols using IBX-TfOH catalytic system in 1,4-dioxane at ambient temperature. The reaction affords quantitative yields of the corresponding carbonyl compounds without the formation of over oxidized products. The present synthetic protocol is compatible with a variety of substrates having arene, heteroarene and alkene functionalities. The developed synthetic protocol can be used for higher scale reactions as evident by the oxidation of alcohol at 1 g scale in higher yields by a simple filtration process.

A kinetic and mechanistic study of the osmium(VIII)-catalysed oxidation of crotyl alcohol by hexacyanoferrate(III) in aqueous Alkaline medium

The kinetics and mechanism of the osmium(VIII)-catalysed oxidation of crotyl alcohol by hexacyanoferrate(III) in aqueous alkaline medium is studied. The role of the osmium(VIII) catalyst is delineated to account for the experimental observations. A plausible reaction mechanism is suggested. Activation parameters such as the energy and entropy of activation are evaluated by employing the Eyring equation and are found to be 36.833 kJ mol?1 and ?141.518 J K?1 mol?1, respectively.

Magnetic core-shell Fe3O4?Cu2O and Fe3O4?Cu2O-Cu materials as catalysts for aerobic oxidation of benzylic alcohols assisted by TEMPO and: N -methylimidazole

In this work, core-shell Fe3O4?Cu2O and Fe3O4?Cu2O-Cu nanomaterials for aerobic oxidation of benzylic alcohols are reported with 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and N-methylimidazole (NMI) as the co-catalysts. To anchor Cu2O nanoparticles around the magnetic particles under solvothermal conditions, the magnetic material Fe3O4 was modified by grafting a layer of l-lysine (l-Lys) to introduce -NH2 groups at the surface of the magnetic particles. With amine groups as the anchor, Cu(NO3)2 was used to co-precipitate the desired Cu2O by using ethylene glycol as the reducing agent. Prolonging the reaction time would lead to over-reduced forms of the magnetic materials in the presence of copper, Fe3O4?Cu2O-Cu. The nanomaterials and its precursors were fully characterized by a variety of spectroscopic techniques. In combination with both TEMPO and NMI, these materials showed excellent catalytic activities in aerobic oxidation of benzylic alcohols under ambient conditions. For most of the benzylic alcohols, the conversion into aldehydes was nearly quantitative with aldehydes as the sole product. The materials were recyclable and robust. Up to 7 repeat runs, its activity dropped less than 10%. The over-reduced materials, Fe3O4?Cu2O-Cu, exhibited slightly better performance in durability. The magnetic properties allowed easy separation after reaction by simply applying an external magnet.

Oxidation of crotyl alcohol by N-chloro-4-methylbenzene sulphonamide in acidic medium and in alkaline media in the presence of os(VIII) catalyst-a kinetic pathway

The kinetic pathway of oxidation of crotyl alcohol by sodium salt of N -chloro-4-methylbenzene sulphonamide (chloramine-T) in acidic and alkaline medium has been studied. The speciation of chloramine-T has been made to suggest a proper and reasonable reaction mechanism. The thermodynamic quantities such as activation energy and activation entropy are evaluated in acidic as well as in catalysed alkaline medium. An anticipated reaction mechanism has been suggested.