5371-49-3

Usage

Synthesis Reference(s)

Synthetic Communications, 18, p. 359, 1988 DOI: 10.1080/00397918808063999

InChI:InChI=1/C4H6O3/c1-4(6)7-3-2-5/h2H,3H2,1H3

Upstream product

• 2497-18-9 (E)-2-hexen-1-yl acetate 
• 591-87-7 Allyl acetate 
• 105-37-3 Ethyl propionate 
• 141-78-6 ethyl acetate 

Downstream Products

• 19191-10-7 (E)-1,2-diacetoxyethene 
• 19191-11-8 (Z)-1,2-diacetoxyethene 
• 73756-09-9 (E)-4-Acetoxy-2-phenylsulfanylmethyl-but-2-enoic acid methyl ester 
• 191721-67-2 (R)-2-Benzyloxycarbonylamino-3-(1,2-diacetoxy-ethylsulfanyl)-propionic acid methyl ester 
• 26586-02-7 (E)-4-acetoxy-2-methylcrotonaldehyde 
• 1114553-61-5 C₂₁H₁₉NO₅ 

Relevant academic research and scientific papers

Gas-Phase Oxidation of Allyl Acetate by O3, OH, Cl, and NO3: Reaction Kinetics and Mechanism

Allyl acetate (AA) is widely used as monomer and intermediate in industrial chemicals synthesis. To evaluate the atmospheric outcome of AA, kinetics and mechanism of its gas-phase reaction with main atmospheric oxidants (O3, OH, Cl, and NO3) have been investigated in a Teflon reactor at 298 ± 3 K. Both absolute and relative rate methods were used to determine the rate constants for AA reactions with the four atmospheric oxidants. The obtained rate constants (in units of cm3 molecule-1 s-1) are (1.8 ± 0.3) × 10-18, (3.1 ± 0.7) × 10-11, (2.5 ± 0.5) × 10-10, and (1.1 ± 0.4) × 10-14, for reactions with O3, OH, Cl, and NO3, respectively. While results for reactions with O3, OH and Cl are in good agreement with previous studies, the kinetics for the reaction with NO3 is reported for the first time in this study. On the basis of determined rate constants, the tropospheric lifetimes of AA are ρO3 = 9 days, ρOH = 5 h, ρCl = 5 days, ρNO3 = 2 days. On the basis of the products study, reaction mechanisms for these oxidations have been proposed and the reaction products were detected using thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) and Fourier transform infrared spectroscopy (FTIR). Results show that the main products formed in these reactions are carbonyl compounds. In particular, 2-oxoethyl acetate was detected in all four AA oxidation reactions. Compared to previous studies, several new products were determined for reactions with OH and Cl. These results form a set of comprehensive kinetic data for AA reactions with main atmospheric oxidants and provide a better understanding of the degradation and atmospheric outcome of unsaturated acetate esters in the troposphere, during both daytime and nighttime.

Tropospheric chemical degradation of vinyl and allyl acetate initiated by Cl atoms under high and low NOx conditions

The products of the reactions of Cl atoms with vinyl acetate (VA) and allyl acetate (AA) have been investigated in a 1080 L chamber using in situ FTIR. The experiments were performed at 296 K and atmospheric pressure of synthetic air in the presence and in the absence of NOx. For the reaction of Cl with VA in the presence of NOx formic acetic anhydride, acetic acid and formyl chloride are the major reaction products. In the absence of NOx, the yields of these products are significantly reduced and formation of the carbon-chain-retaining compound CH3C(O)OC(O)CH2Cl is observed. For the reaction of Cl with AA in the presence of NOx acetoxyacetaldehyde and formaldehyde were observed as the main products. In contrast, without NOx, the observations support that the major reaction pathway is the formation of the carbon-chain-retaining compound CH3C(O)OCH2C(O)CH2Cl. The reaction mechanisms leading to the products are discussed. The formation of the high yields of formyl chloride and formaldehyde in the reactions of Cl with VA and AA, respectively, are at odds with currently accepted mechanistic pathways.

Kinetic and mechanistic study of the atmospheric oxidation by OH radicals of allyl acetate

A potential source of acetates, including allyl acetate, is combustion of esterified rape oil used as substitution fuel. This new formulation of diesel fuel significantly reduces the emission of particulate matter. To better evaluate the environmental impact of acetates, OH-induced oxidation kinetic and mechanism of allyl acetate were studied at room temperature and 1 atm using three environmental chambers (an indoor Teflon-film bag, an indoor Pyrex photoreactor, and the outdoor smog chamber EUPHORE. The main oxidation products were acetoxyacetaldehyde and formaldehyde. A mechanism was developed to describe the OH-induced oxidation of the acetate in the presence of NOx. Reaction with OH radicals was the main tropospheric fate of allyl acetate. When it reacted with OH radicals, it could contribute to the formation of photooxidants close to the emission sources. Acetoxyacetaldehyde yield was slightly smaller in the experiment at low NOx since some peroxides could be produced from peroxy radical + HO2 reaction and compete with the acetoxyacetaldehyde production.

FTIR spectroscopic study of the OH-induced oxidation of two linear acetates: Ethyl and n-propyl acetates

OH-induced oxidation mechanisms of ethyl and n-propyl acetates have been investigated at room temperature (298 ± 5 K) and atmospheric pressure by photolysing CH3ONO/acetate/NO mixtures with FTIR spectroscopy as analytical device. The main oxidation products and their yields were as follows: from ethyl acetate, acetic acid (0.75 ± 0.13), acetoxyacetaldehyde (0.15 ± 0.05), acetic anhydride (0.02 ± 0.01), formic acetic anhydride (0.02 ± 0.01) and peroxyacetyl nitrate (PAN); from n-propyl acetate, acetoxyacetaldehyde (0.22 ± 0.06), formic acetic anhydride (0.28 ± 0.03), acetic acid (0.15 ± 0.02), acetaldehyde (0.35 ± 0.10), peroxypropionyl nitrate (PPN) and probably acetoxypropionaldehyde (0.30 ± 0.10). From these data, oxidation schemes of these two acetates were elucidated. This study reveals in particular the specifc reactivity of acetates by confirming the novel α-ester rearrangement proposed recently by Tuazon et al. (J. Phys. Chem. A, 1998, 102, 2316) and then by showing that oxygenated alkoxyl radicals may not follow the same rules of reactivity as other alkoxyl radicals. This last observation shows the necessity for further experiments to understand the influence of the oxygenated function on alkoxyl reactivity.

The synthesis of highly reactive, multi-functional α,β-epoxy- and α-acetoxy-nitrosamines

The synthesis of the reactive acetates, trans-3-acetoxy-2-hydroxy-N-nitrosomorpholine 3 and N-(1-acetoxy-2-hydroxyethyl)-N-nitrosoethanolamine 12, of two α-hydroxynitrosamines has been accomplished through the ring opening of the corresponding epoxides, NEMOR and 10 which were prepared by dimethyldioxirane oxidation of the vinyl nitrosamines.

Gas-phase reaction of ozone with trans-2-hexenal, trans-2-hexenyl acetate, ethylvinyl ketone, and 6-methyl-5-hepten-2-one

The gas-phase reaction of ozone with the unsaturated oxygenates trans-2-hexenal, trans-2-hexenyl acetate, ethylvinyl ketone, and 6-methyl-5-hepten-2-one, which are components of biogenic emissions and/or close structural homologues thereof, has been investigated at atmospheric pressure and ambient temperature (286-291 K) and humidity (RH = 55 ± 10%). Reaction rate constants, in units of 10-18 cm3 molecule-1 s-1, are 1.28 ± 0.28 for trans2-hexenal, 21.8 ± 2.8 for trans-2-hexenyl acetate, and 394 ± 40 for 6-methyl-5-hepten-2-one. Carbonyl product formation yields, measured with sufficient cyclohexane added to scavenge the hydroxyl radical, are 0.53 ± 0.06 for n-butanal and 0.56 ± 0.04 for glyoxal from trans-2-hexenal, 0.47 ± 0.02 for n-butanal and 0.58 ± 0.14 for 1-oxoethyl acetate from trans-2-hexenyl acetate, 0.55 ± 0.07 for formaldehyde and 0.44 ± 0.03 for 2-oxobutanal from ethylvinyl ketone, and 0.28 ± 0.02 for acetone from 6-methyl-5-hepten-2-one. Reaction mechanisms are outlined and the atmospheric persistence of the compounds studied is briefly discussed.