140-88-5 Usage
Chemical Description
Ethyl acrylate, ethyl crotonate, and diethyl fumarate are all esters that can be used in similar reactions.
Uses
1. Used in Polymer and Copolymer Production:
Ethyl acrylate is used as a monomer for the production of polymers and copolymers, which are utilized in manufacturing textiles, latex paints, paper coatings, dirt release agents, and specialty plastics.
2. Used in Acrylic Resins:
Ethyl acrylate is employed as a monomer for acrylic resins, which are essential components in various industries.
3. Used in Textile and Paper Coatings:
Ethyl acrylate is used as a component in the manufacture of acrylic resins, acrylic fibers, textile, and paper coatings, providing enhanced properties and performance.
4. Used in Adhesives and Leather Finish Resins:
Ethyl acrylate is also utilized in the production of adhesives and leather finish resins, contributing to their bonding and finishing properties.
5. Used as a Flavoring Agent:
Ethyl acrylate is used as a flavoring agent, characterized by its clear, colorless appearance, and a fruity, harsh, penetrating, and lachrymatous odor. It is sparingly soluble in water and miscible in alcohol and ether.
6. Used in Pharmaceutical Synthesis:
Ethyl acrylate serves as a reagent in the synthesis of various pharmaceutical intermediates, playing a crucial role in the development of new medications.
7. Used in the Production of Paints and Plastics:
Ethyl acrylate is used to make paints and plastics, thanks to its ability to polymerize and form useful materials with desirable properties.
8. Used in the Synthesis of Fragrances:
Ethyl acrylate's characteristic penetrating and persistent odor makes it a valuable component in the synthesis of fragrances, contributing to their unique scents.
Preparation
By esterification of acrylic acid; by heating acetylene with HCl in alcoholic solution in the presence of Ni(CO)4; also from
ethyl-3-chloropropionate passed over activated carbon at high temperature.
Production Methods
Ethyl acrylate is manufactured via oxidation of propylene to
acrolein and then to acrylic acid. The acid is treated with
ethanol to yield the ethyl ester .
Vinyl chloride reacts at 270 °C at >6895 kPa (68 atm)
with ethanol in the presence of a cobalt and palladium
catalyst to give ethyl acrylate in a yield of 17% .
Air & Water Reactions
Highly flammable. Insoluble in water.
Reactivity Profile
A flammable liquid, confirmed carcinogen. Ethyl acrylate can react vigorously with oxidizing reagents, peroxides,strong alkalis and polymerization initiators. [NTP] Ethyl acrylate reacts violently with chlorosulfonic acid [Sax, 9th ed., 1996, p. 1515]. When an inhibited monomer was placed in a clear glass bottle exposed to sunlight, exothermic polymerization set in and caused the bottle to burst. The use of brown glass or metal containers and increase in inhibitor concentration (to 200 ppm; tenfold) was recommended [MCA Case History No. 1759]. Ethyl acrylate may polymerize when exposed to light and Ethyl acrylate is subject to slow hydrolysis. Inhibitors do not function in the absence of air. Solutions in DMSO are stable for 24 hours under normal lab conditions. [NTP].
Hazard
Toxic by ingestion, inhalation, skin absorption; irritant to skin and eyes. Flammable, dangerous fire and explosion hazard. Possible carcinogen.
Health Hazard
Ethyl acrylate is a strong irritant to the eyes,skin, and mucous membranes. The liquid orits concentrated solutions can produce skinsensitization upon contact. It is toxic by allroutes of exposure. The toxicity is low inrats and mice and moderate in rabbits. Thetoxic effects from inhalation noted in animalswere congestion of lungs and degenerativechanges in the heart, liver, and kidney. Mon key exposed to 272 ppm for 28 days showedlethargy and weight loss; while exposure to1024 ppm caused death to the animals after2.2 days (Treon et al. 1949). By compari son, guinea pigs died of exposure to about1200 ppm for 7 hours. Ingestion of the liq uid may result in irritation of gastrointestinaltracts, nausea, lethargy, and convulsionsThe LD50 values varied significantly indifferent species of animals. The oral LD50values in rabbits, rats, and mice are in therange 400, 800, and 1800 mg/kg, respectively. Animals administered ethyl acrylateshowed increased incidence of tumors inforestomach. However, there is no evidenceof carcinogenicity caused by this compoundin humans.
Flammability and Explosibility
Flammable
Chemical Reactivity
Reactivity with Water No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: May occur; exclude moisture, light; avoid exposure to high temperatures; store in presence of air; Inhibitor of Polymerization: 13-17 ppm monomethyl ether of hydroquinone.
Safety Profile
Confirmed carcinogen
with experimental carcinogenic data. Poison
by ingestion and inhalation. Moderately
toxic by skin contact and intraperitoneal
routes. Human systemic effects by
inhalation: eye, olfactory, and pulmonary
changes. A skin and eye irritant.
Characterized in its terminal stages by dyspnea, cyanosis, and convulsive
movements. It caused severe local irritation
of the gastroenteric tract; and toxic
degenerative changes of cardiac, hepatic,
renal, and splenic tissues were observed. It
gave no evidence of cumulative effects.
When applied to the intact skin of rabbits,
the ethyl ester caused marked local irritation,
erythema, edema, thickening, and vascular
damage. Animals subjected to a fairly high
concentration of these esters suffered
irritation of the mucous membranes of the
eyes, nose, and mouth as well as lethargy,
dpspnea, and convulsive movements. A
substance that migrates to food from
packagmg materials.
Flammable liquid. A very dangerous fire
hazard when exposed to heat or flame; can
react vigorously with oxidizing materials.
Violent reaction with chlorosulfonic acid.
To fight fire, use CO2, dry chemical, or
alcohol foam. When heated to
decomposition it emits acrid smoke and
irritating fumes. See also ESTERS.
Safety
It is an acute toxin with an LD50 (rats, oral) of 1020 mg / kg and a TLV of 5 ppm. The International Agency for Research on Cancer stated, "Overall evaluation, Ethyl acrylate is possibly carcinogenic to humans (Group 2B)." The United States Environmental Protection Agency (EPA) states, "Human studies on occupational exposure to ethyl acrylate... have suggested a relationship between exposure to the chemical(s) and colorectal cancer, but the evidence is conflicting and inconclusive. In a study by the National Toxicology Program (NTP), increased incidences of squamous cell papillomas and carcinomas of the fore stomach were observed in rats and mice exposed via gavage (experimentally placing the chemical in the stomach). However, the NTP recently determined that these data were not relevant to human carcinogenicity since humans do not have a fore stomach, and removed ethyl acrylate from its list of carcinogens." (Occupational exposure generally involves exposure that occurs regularly, over an extended period of time.) One favorable safety aspect is that ethyl acrylate has good warning properties; the odor threshold is much lower than any level of health concern. In other words, the bad odor warns people of ethyl acrylate's presence long before the concentration reaches a level capable of creating a serious health risk.
Potential Exposure
This material is used in emulsion polymers for paints, textiles, adhesives, coatings and binders; as
a monomer in the manufacture of homopolymer and copolymer resins for the production of paints and plastic films
Carcinogenicity
A retrospective study found
an excess of colorectal cancers in one exposed population of
workers; however, the data were confounded by other exposures
and lack of association of causality and risk in similarly
exposed populations from other locations. Therefore, there
was inadequate evidence based on the study that ethyl acrylate
is a human carcinogen . Ethyl acrylate is listed as
USEPA group B2, “Probable human carcinogen”; IARC
group B2, “Possibly carcinogenic in humans”; NIOSH,
“Carcinogen with no further categorization”; NTP group 2,
“Reasonably anticipated to be a carcinogen” and listed as a
carcinogen by California Proposition 65 .
Dermal studies of acrylic acid, ethyl acrylate, and n-butyl
acrylate using mice did not result in local carcinogenesis,
but several mice in the ethyl acrylate-treated group did
exhibit dermatitis, dermal fibrosis, epidermal necrosis, and
hyperkeratosis .
Environmental fate
Chemical/Physical. Polymerizes on standing and is catalyzed by heat, light, and peroxides
(Windholz et al., 1983). Slowly hydrolyzes in water forming ethanol and acrylic acid. The
reported rate constant for the reaction of ethyl acrylate with ozone in the gas phase was determined
to be 5.70 x 10-18 cm3 mol/sec (Munshi et al., 1989).
At an influent concentration of 1,015 mg/L, treatment with GAC resulted in an effluent
concentration of 226 mg/L. The adsorbability of the carbon used was 157 mg/g carbon (Guisti et
al., 1974).
Shipping
UN1917 Ethyl acrylate, Hazard Class: 3; Labels:
3-Flammable liquid
Purification Methods
Wash the ester repeatedly with aqueous NaOH until free from inhibitors such as hydroquinone, then wash it with saturated aqueous CaCl2 and distil it under reduced pressure. Hydroquinone should be added if the ethyl acrylate is to be stored for extended periods. [Beilstein 2 IV 1460.] LACHRYMATORY.
Toxicity evaluation
The toxic mode of action for ethyl acrylate is unknown.
However, the parent compound may play a significant role
since pretreatment of rats with a carboxylesterase inhibitor
enhances the respiratory irritation and lethality produced by
the inhalation of ethyl acrylate. The enhanced toxicity could be
a direct effect of methyl acrylate on surrounding tissues and/or
a secondary effect due to the increased conjugation of methyl
acrylate with glutathione that occurs under these conditions
which in turn can result in toxicity due to the depletion of local
glutathione stores.
Incompatibilities
May form explosive mixture with air.
Atmospheric moisture and strong alkalies may cause fire
and explosions unless properly inhibited (Note: Inert gas
blanket not recommended). Heat, light or peroxides can
cause polymerization. Incompatible with oxidizers (may be
violent), peroxides, polymerizers, strong alkalis; moisture,
chlorosulfonic acid, strong acids; amines. May accumulate
static electrical charges, and may cause ignition of its vapors. Polymerizes readily unless an inhibitor, such as
hydroquinone is added. Uninhibited vapors may plug vents
by the formation of polymers.
Waste Disposal
Incineration or by absorption and landfill disposal
Check Digit Verification of cas no
The CAS Registry Mumber 140-88-5 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 1,4 and 0 respectively; the second part has 2 digits, 8 and 8 respectively.
Calculate Digit Verification of CAS Registry Number 140-88:
(5*1)+(4*4)+(3*0)+(2*8)+(1*8)=45
45 % 10 = 5
So 140-88-5 is a valid CAS Registry Number.
InChI:InChI=1/C5H8O2/c1-3-4(2)5(6)7/h2-3H2,1H3,(H,6,7)/p-1
140-88-5Relevant articles and documents
Asymmetric Counter-Anion-Directed Aminomethylation: Synthesis of Chiral β-Amino Acids via Trapping of an Enol Intermediate
Kang, Zhenghui,Wang, Yongheng,Zhang, Dan,Wu, Ruibo,Xu, Xinfang,Hu, Wenhao
, p. 1473 - 1478 (2019)
A novel enantioselective aminomethylation reaction of diazo compound, alcohol and α-aminomethyl ether enabled by asymmetric counteranion-directed catalysis is disclosed that offers an efficient and convenient access to furnish optically active α-hydroxyl-β-amino acids in high yield with high to excellent enantioselectivities. Control experiments and DFT calculations indicate that the transformation proceeds through trapping the in situ generated enol intermediate with methylene iminium ion, and the asymmetric induction was enabled by chiral pentacarboxycyclopentadiene anion via H-bonding and electrostatic interaction.
Liberation of acrylates from nickelalactones via Ni─O ring opening with alkyl iodides
Zhang, Zhizhi,Guo, Fangjie,Kühn, Fritz E.,Sun, Jing,Zhou, Mingdong,Fang, Xiangchen
, (2017)
The utilization of carbon dioxide as a feedstock for the production of raw chemicals is of high current industrial interest. One attractive reaction is the transformation of carbon dioxide into acrylic acid or acrylates. The cleavage of the Ni─O bond of nickelalactones may result in the formation of acrylates. In this work, C2H5I, CF3CH2I and CF3I are studied as alkylation reagents for the Ni─O ring opening of nickelalactones. The results indicate that both C2H5I and CF3CH2I are able to release acrylates from nickelalactones. Based on the experimental evidence and literature precedents, a mechanism – proceeding via Ni─O ring opening of nickelalactone, β-H elimination to release the acrylate and reductive elimination for recovery of the Ni(0) species – is proposed.
Homogeneous and Heterogeneous Catalyzed Esterification of Acrylic Acid with Ethanol: Reaction Kinetics and Modeling
Jyoti, Ghoshna,Keshav, Amit,Anandkumar,Bhoi, Stutee
, p. 370 - 380 (2018)
Kinetics of esterification of acrylic acid with ethanol in the presence of homogeneous (H2SO4, HCl, p-TSA, HI) catalysts as well as heterogeneous catalysts (Dowex 50WX, Amberlyst 15) was studied. The effects and performance of these catalysts on the conversion of acrylic acid were evaluated. In the kinetics of homogeneous catalyzed reaction, both concentration and activity-based model were employed. Activity coefficients were predicted by the Universal Functional group Contribution (UNIFAC) method to consider nonideal behavior of the liquid phase. The heterogeneous catalyzed reaction mechanisms were developed using Eley–Rideal theory. The model results were compared with the experimental results and were in good agreement. The temperature dependency of the constants, reaction enthalpy, and entropy, and activation energy were determined. The conversion of acrylic acid was obtained as 63.2%, 61.02%, 53.3%, 21.4%, 34.96%, and 14.84% for H2SO4, p-TSA, HCl, HI, Dowex 50WX, and Amberlyst 15, respectively, under process temperature of 70°C, reactant molar ratio of 1:1, and catalyst concentration of 2% (v/v) for homogeneous and 2.17 g for heterogeneous catalyst. These outcomes provide an approach to understand the significant effect of each catalyst on the esterification kinetics of acrylic acid and ethanol.
Efficient and selective conversion of methyl lactate to acrylic acid using Ca3(PO4)2-Ca2(P2O 7) composite catalysts
Hong, Ju Hyeong,Lee, Jong-Min,Kim, Hyungrok,Hwang, Young Kyu,Chang, Jong-San,Halligudi, Shiva B.,Han, Yo-Han
, p. 194 - 200 (2011)
Calcium phosphate Ca3(PO4)2 and calcium pyrophosphate Ca2(P2O7) composite catalysts of different weight ratios were prepared by a slurry-mixing method. These composite catalysts were calcined at 500 °C in air and characterized by N2 sorption for specific surface area by XRD for crystal phases and by TPD-NH 3 (acidity), TPD-CO2 (basicity) and SEM for morphological features. All the Ca3(PO4)2-Ca 2(P2O7) composite catalysts were found to be active in the vapor phase conversion of methyl lactate (ML) to give mainly acrylic acid (AA) and methyl acrylate (MA) as products. The catalyst Ca 3(PO4)2-Ca2(P2O 7) of 50:50 wt% ratio was the most efficient and selective catalyst in the conversion of ML, which gave 91% conversion of ML with selectivity for AA (75%) and MA (5%) together (80%) under optimized reaction conditions. The higher conversion of ML and formation of AA by Ca3(PO 4)2-Ca2(P2O7) [50:50 wt%] composite catalyst has been attributed to moderate acid-base strength regulated with surface properties.
WITTIG-HORNER REACTION CATALYZED BY ACTIVATED BARIUM HYDROXIDE IN THE PRESENCE OF ULTRASOUND
Fuentes, A.,Marinas, J.M.,Sinisterra, J.V.
, p. 2951 - 2954 (1987)
The sonochemical Wittig-Horner reaction, catalyzed by an activated barium hydroxide catalyst in interfacial solid-liquid conditions leads to E-acrylates with very good yields.The sonochemical process takes place at room temperature and with lower catalyst weight and reaction time than the thermal process.
Controlling the Lewis Acidity and Polymerizing Effectively Prevent Frustrated Lewis Pairs from Deactivation in the Hydrogenation of Terminal Alkynes
Geng, Jiao,Hu, Xingbang,Liu, Qiang,Wu, Youting,Yang, Liu,Yao, Chenfei
, p. 3685 - 3690 (2021/05/31)
Two strategies were reported to prevent the deactivation of Frustrated Lewis pairs (FLPs) in the hydrogenation of terminal alkynes: reducing the Lewis acidity and polymerizing the Lewis acid. A polymeric Lewis acid (P-BPh3) with high stability was designed and synthesized. Excellent conversion (up to 99%) and selectivity can be achieved in the hydrogenation of terminal alkynes catalyzed by P-BPh3. This catalytic system works quite well for different substrates. In addition, the P-BPh3 can be easily recycled.
Acid- And base-switched palladium-catalyzed γ-C(sp3)-H alkylation and alkenylation of neopentylamine
Zhang, Jinquan,Zhang, Shuaizhong,Zou, Hongbin
supporting information, p. 3466 - 3471 (2021/05/31)
The functionalization of remote unactivated C(sp3)-H and the reaction selectivity are among the core pursuits for transition-metal catalytic system development. Herein, we report Pd-catalyzed γ-C(sp3)-H-selective alkylation and alkenylation with removable 7-azaindole as a directing group. Acid and base were found to be the decisive regulators for the selective alkylation and alkenylation, respectively, on the same single substrate under otherwise the same reaction conditions. Various acrylates were compatible for the formation of C(sp3)-C(sp3) and C(sp3)-C(sp2) bonds. The alkenylation protocol could be further extended to acrylates with natural product units and α,β-unsaturated ketones. The preliminary synthetic manipulation of the alkylation and alkenylation products demonstrates the potential of this strategy for structurally diverse aliphatic chain extension and functionalization. Mechanistic experimental studies showed that the acidic and basic catalytic transformations shared the same six-membered dimer palladacycle.
Phosphine-Catalyzed Cascade Annulation of MBH Carbonates and Diazenes: Synthesis of Hexahydrocyclopenta[c]pyrazole Derivatives
Guo, Hongchao,Li, Hongxiang,Liu, Hao,Shi, Wangyu,Wang, Chang,Wang, Wei,Wu, Yongjun
supporting information, p. 5571 - 5575 (2021/07/31)
A phosphine-catalyzed cascade annulation of Morita-Baylis-Hillman (MBH) carbonates and diazenes was achieved, giving tetrahydropyrazole-fused heterocycles bearing two five-membered rings in moderate to excellent yields. The reaction underwent an unprecedented reaction mode of MBH carbonates, in which two molecules of MBH carbonates were fully merged into the ring system.
METHOD FOR PRODUCING α,β-UNSATURATED CARBOXYLIC ACID DERIVATIVE
-
Paragraph 0102; 0108; 0113; 0115, (2021/04/02)
To provide a method for producing α,β-unsaturated carboxylic acid derivative that is advantageous in a cost and efficient.SOLUTION: A method for producing α,β-unsaturated carboxylic acid derivative including: a process of allowing metal lactone compound and alkyl halide having the carbon number of 1 to 6 to react to obtain α,β-unsaturated carboxylic acid derivative and either or both of hydrogen iodide and hydrogen bromide; and a process of allowing either or both of the hydrogen iodide and hydrogen bromide and alcohol having the carbon number of 1 to 6 to react to regenerate the alkyl halide.SELECTED DRAWING: None
Palladium-catalyzed remote C-H functionalization of 2-aminopyrimidines
Das, Animesh,Jana, Akash,Maji, Biplab
supporting information, p. 4284 - 4287 (2020/04/27)
A straightforward strategy was developed for the arylation and olefination at the C5-position of the N-(alkyl)pyrimidin-2-amine core with readily available aryl halides and alkenes, respectively. This approach was highly regioselective, and the transformation was achieved based on two different (Pd(ii)/Pd(iv)) and (Pd(0)/Pd(ii)) catalytic cycles.
