| HS Code | 846881 |
| Name | Ethyl Cyanoacetate |
| Iupac Name | Ethyl 2-cyanoacetate |
| Cas Number | 105-56-6 |
| Einecs Number | 203-309-0 |
| Molecular Formula | C5H7NO2 |
| Molecular Weight | 113.11 g/mol |
| Appearance | Colorless to pale yellow liquid |
| Odor | Mild ester-like odor |
| Boiling Point | 206-208 °C |
| Melting Point | -22.5 °C |
| Density | 1.056 g/mL at 25 °C |
| Refractive Index | n20/D 1.417 |
| Flash Point | 110 °C (closed cup) |
| Solubility | Slightly soluble in water; soluble in ethanol, ether, acetone |
| Vapor Pressure | 0.1 mmHg at 20 °C |
| Assay | ≥98% |
| Storage Conditions | Store in a cool, dry, well-ventilated area away from heat and ignition sources |
| Hazard Statements | Harmful if swallowed; causes skin and eye irritation |
| Smiles | CCOC(=O)CC#N |
| Inchi | InChI=1S/C5H7NO2/c1-2-8-5(7)3-4-6/h2-3H2,1H3 |
As an accredited Ethyl Cyanoacetate factory, we enforce strict quality protocols—every batch undergoes rigorous testing to ensure consistent efficacy and safety standards.
| Packing | Ethyl Cyanoacetate is packaged in 200 kg net steel drums, properly labeled, sealed, and UN-approved for chemical transport. |
| Container Loading (20′ FCL) | Container Loading (20′ FCL) for Ethyl Cyanoacetate: palletized drums, securely stowed and lashed, sealed, with IMDG-compliant labels and documentation. |
| Shipping | Ethyl cyanoacetate is generally shipped as a non-hazardous liquid in 200L steel drums, plastic drums, or IBCs. It is not regulated for transport by DOT, IMDG, or IATA. Store in a cool, dry, well-ventilated area away from oxidizers. Label with chemical name and CAS, and follow SDS/local rules. |
| Storage | Store ethyl cyanoacetate in a cool, dry, well-ventilated place away from heat, sparks, flames, and direct sunlight. Keep containers tightly closed, clearly labeled, and upright. Segregate from strong oxidizers, acids, bases, and reducing agents. Use compatible, grounded containers with secondary containment. Protect from moisture, and maintain spill-control and firefighting equipment. Follow all local chemical storage regulations. |
| Shelf Life | Ethyl cyanoacetate typically has a 24-month shelf life when stored sealed, cool, dry, and away from moisture, heat, and light. |
The largest-volume downstream use of ethyl cyanoacetate (CAS 105-56-6) is the production of ethyl 2-cyanoacrylate, the active monomer in instant adhesives. The condensation of ethyl cyanoacetate with paraformaldehyde is carried out in a refluxing solvent with a secondary amine catalyst, typically piperidine or piperidine acetate. Water is removed azeotropically to drive the Knoevenagel condensation. The formaldehyde-to-ethyl cyanoacetate molar ratio is maintained between 1.0:1 and 1.5:1 depending on the desired prepolymer molecular weight. The resulting poly(ethyl cyanoacrylate) is washed with dilute acid and deionized water to remove catalyst residues. Washed prepolymer is dried to a water content below 0.1% before thermal depolymerization. Depolymerization takes place in a wiped-film evaporator or short-path distillation unit at jacket temperatures from 160 °C to 210 °C and absolute pressures below 10 mbar. Phosphorus pentoxide, p-toluenesulfonic acid, and hydroquinone are metered into the prepolymer melt to suppress repolymerization and radical side reactions. The monomer vapor is condensed on surfaces held between -10 °C and -25 °C and collected under dry nitrogen. Residual moisture in the finished monomer is controlled below 200 ppm. The distilled monomer is stabilized with methanesulfonic acid and sulfur dioxide, with residual stabilizer concentrations maintained below 50 ppm to avoid excessive acidic residues. Production-scale failure modes include gel buildup in the prepolymer transfer line and fouling of the short-path condenser by low-volatile oligomers. Final monomer purity is measured by gas chromatography with a target above 99.5 area%. Adhesive formulations are compounded by dissolving poly(methyl methacrylate) thickener into the monomer, adding dioctyl phthalate or acetyl tributyl citrate as plasticizer, and incorporating silane adhesion promoters. Cure is triggered by surface moisture through an anionic polymerization mechanism. Acidic substrates with pH below 4 extend fixture time, while alkaline substrates accelerate cure. The cured adhesive is tested for lap-shear strength according to ISO 4587:2003 or ASTM D1002-10. Where formulations are evaluated for medical device use, cytotoxicity testing under ISO 10993-5 and irritation testing under ISO 10993-10 are added to the standard adhesive test suite. The primary processing boundary is moisture exclusion; mixing vessels and transfer lines must be dried to a dew point below -40 °C, and amine-based additives must be excluded because they initiate premature polymerization.
Ethyl cyanoacetate is condensed with benzophenone to produce ethyl 2-cyano-3,3-diphenylacrylate, the direct precursor of octocrylene. The Knoevenagel condensation is run in refluxing cyclohexane or toluene with continuous azeotropic water removal. Catalysts include ammonium acetate, acetic acid, or piperidine acetate; selection depends on the required residual benzophenone level and the sensitivity of the ester to hydrolysis. Benzophenone-to-ethyl cyanoacetate molar ratios are kept between 0.95:1 and 1.10:1, with a slight ester excess preferred to suppress unreacted benzophenone carryover. Reaction completion is monitored by gas chromatography or HPLC until residual benzophenone falls below the specification limit for the downstream cosmetic intermediate. The intermediate diphenylacrylate ester is transesterified with 2-ethylhexanol in the presence of a titanate or organotin catalyst at 120–160 °C under reduced pressure, while ethanol is continuously removed. The finished octocrylene is purified by high-vacuum distillation or crystallization from alcohol. Octocrylene is listed in EU 1223/2009 Annex VI with a maximum ready-for-use concentration of 10% w/w; the US FDA sunscreen monograph also permits octocrylene up to 10%. The transesterification vessel is typically glass-lined or stainless steel, equipped with structured packing and a reflux ratio of 2:1 to 4:1 to separate ethanol from the higher boiling alcohol without excessive reboiler temperatures. The critical process limit is water ingress above 0.2%, which accelerates catalyst hydrolysis and reduces conversion. Published data for this specific configuration is limited when crude benzophenone streams contain high levels of ortho-substituted impurities; distillation of the incoming benzophenone is therefore required.
As a methylene-active C3 synthon, ethyl cyanoacetate is used in pharmaceutical intermediate synthesis. The nitrile and ester groups enable cyclocondensation with hydrazine, guanidine, urea, thiourea, and amidines. With hydrazine hydrate in ethanol at 20–50 °C, ethyl cyanoacetate gives 3-amino-5-pyrazolone or substituted pyrazole intermediates after pH adjustment. With guanidine carbonate in sodium methoxide, the condensation yields aminohydroxypyrimidine intermediates used in pharmaceutical heterocycle synthesis. These heterocyclic intermediates are isolated as drug substance building blocks under ICH Q7 guidance. The reaction mass is held in glass-lined or stainless steel vessels with jacket temperature control of ±2 °C. Residual water is measured by Karl Fischer titration because moisture hydrolyzes the ester group to cyanoacetic acid. Solvent selection includes methanol, ethanol, and dimethylformamide, with residual solvent limits assessed under ICH Q3C. The methylene position can be monoalkylated with alkyl halides in the presence of sodium ethoxide or potassium carbonate. Excess alkylating agent leads to dialkylation, which creates an off-spec byproduct removed by fractional distillation or crystallization. The process is monitored by in-line FTIR for the nitrile stretch near 2240 cm-1 and by gas chromatography for unreacted ethyl cyanoacetate. Incompatibilities include strong aqueous alkali, which rapidly hydrolyzes the ester and generates cyanoacetate salts, and strong reducing agents, which reduce the nitrile to the corresponding amine. Production-scale failure modes include uncontrolled exotherms during hydrazine addition if the feed rate exceeds cooling capacity; the addition is therefore conducted over 1–2 h with reaction mass temperature kept below 40 °C until the initial exotherm subsides.
In crop protection intermediate synthesis, ethyl cyanoacetate is converted to cyanoacetamide by ammonolysis with ammonia in methanol at 0–30 °C. The ammonia addition is exothermic and requires jacket cooling to prevent ester saponification and loss of ammonia overhead. Cyanoacetamide is the standard intermediate for several pyrimidine-derived crop protection agents. In a typical route, cyanoacetamide is condensed with an amidine or guanidine under basic conditions to produce the aminohydroxypyrimidine core common to several crop protection actives. The pyrimidinylamine obtained from this sequence is converted into a sulfonylurea herbicide through sulfonylation of the amine and subsequent coupling with a carbamoylating agent. Condensation pH is maintained between 7 and 9. Alkylation temperature is controlled below 60 °C to reduce N-alkylation byproducts and preserve active ingredient yield. Production-scale reactors are stainless steel with reflux condensers and scrubbers for ammonia and methanol vapors. Nitrile-containing process wastewater and residual organic nitriles are destructed by alkaline chlorination or wet-air oxidation before biological treatment; residual ethyl cyanoacetate in the aqueous phase is monitored by HPLC. The downstream sulfonylurea actives are formulated as water-dispersible granules or suspension concentrates. Crop protection intermediates derived from ethyl cyanoacetate fall under REACH registration obligations and may require ready biodegradability assessment under OECD 301F. The principal operational limitation is acidic pH shift, which can destabilize nitrile intermediates and accelerate pitting corrosion; reactors and transfer lines are therefore specified in 316L stainless steel or glass-lined steel.
Ethyl cyanoacetate is transesterified with n-butanol or 2-octanol to produce butyl cyanoacetate and octyl cyanoacetate. These higher alkyl esters are isolated and purified before undergoing the same paraformaldehyde condensation and depolymerization sequence used for ethyl 2-cyanoacrylate. The transesterification is equilibrium-limited; industrial batches use an excess of the higher alcohol, typically 1.5–3.0 molar equivalents, and remove ethanol continuously through a packed column operating at 300–500 mbar. Titanium(IV) butoxide or dibutyltin oxide is used as catalyst at 110–140 °C. Water must be held below 0.2% to prevent hydrolysis of the nitrile and ester functions. Above 140 °C, the cyanoacetate ester undergoes partial thermal discoloration and nitrile hydrolysis if trace water is present, generating cyanoacetic acid byproducts that inhibit the subsequent Knoevenagel condensation. After neutralization and filtration, the crude higher alkyl cyanoacetate is fractionated in a wiped-film evaporator; the target ester fraction is collected with gas chromatographic purity above 99.0 area%. The purified higher alkyl cyanoacetates are then converted to butyl or octyl cyanoacrylate monomers for medical adhesives and wound closure products. These monomers are evaluated for cytotoxicity under ISO 10993-5 and for tensile wound adhesion under ASTM F2255-05. Equipment for this transesterification includes agitated glass-lined reactors, structured packing columns, and vacuum receivers cooled to -10 °C to retain low-boiling alcohols. The primary process conflict is maintaining sufficient vacuum for ethanol removal without allowing alcohol loss from the reflux condenser; this requires reflux ratio control between 1:1 and 3:1 and in-line density measurement of the distillate.
Commercial derivatives of ethyl cyanoacetate include cyanoacetamide, malononitrile, and cyanoacetic acid. Ammonolysis with anhydrous ammonia in methanol or ethanol at 0–30 °C produces cyanoacetamide in high yield; the exothermic reaction requires cooling to prevent thermal loss of ammonia and ester saponification. Cyanoacetamide is dehydrated to malononitrile with phosphorus oxychloride or phosphorus pentoxide in a chlorinated solvent at 50–90 °C. Malononitrile is a C3 dinitrile used in the synthesis of heterocyclic intermediates, including chlorinated pyrimidines and other substituted pyrimidines. The dehydration reactor must resist hydrogen chloride and phosphorus acid corrosion; glass-lined or PTFE-lined equipment is standard. Off-gas from the dehydration unit is scrubbed with caustic before venting. Product malononitrile is purified by vacuum distillation and stored below 25 °C to prevent discoloration. Cyanoacetic acid is obtained by acid hydrolysis of ethyl cyanoacetate in aqueous hydrochloric acid at reflux, followed by crystallization. Cyanoacetic acid is a precursor to malonic acid and malonate esters. The operational boundary for these derivatives is strict control of nitrile-containing wastewater and solid residues; alkaline chlorination at pH above 9 oxidizes free cyanide before biotreatment. Analytical control includes gas chromatography for residual ethyl cyanoacetate and acetonitrile, Karl Fischer titration for water, and argentometric titration for chloride in hydrolyzed batches. Published data for specific heat-transfer coefficients in large-scale malononitrile dehydration is limited, so pilot-scale calorimetry is required before scaling to multi-tonne reactors.
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Ethyl cyanoacetate is the ethyl ester of cyanoacetic acid, identified under CAS 105-56-6 and EC 203-309-0. The linear formula NCCH₂COOCH₂CH₃ corresponds to a molecular weight of 113.11 g/mol. Industrial supply is commonly separated into two designations: a technical grade with a minimum purity of 99.0% and a distillation or intermediate grade with a minimum purity of 99.5%. At 20 °C, the liquid has a density of 1.060–1.064 g/cm³ and a refractive index of 1.4170–1.4190. The atmospheric boiling range is 205–210 °C at 101.3 kPa. The compound is miscible with ethanol, acetone, toluene, and chlorinated solvents; its water solubility is approximately 2.6 g/100 mL at 20 °C. This solubility profile allows phase separation after aqueous quench but requires drying before moisture-sensitive condensations. Production is carried out by reaction of sodium chloroacetate with sodium cyanide, followed by acidification and esterification with ethanol, or by direct acid-catalyzed esterification of cyanoacetic acid. The crude ester is washed with aqueous sodium bicarbonate to reduce residual acid and then vacuum-distilled through structured packing to meet low-acid, low-color specifications.
Methyl cyanoacetate, CAS 105-34-0, molecular weight 99.09 g/mol, and ethyl cyanoacetate both undergo base-catalyzed Knoevenagel condensation with formaldehyde to form 2-cyanoacrylate monomers. The selection between them is driven primarily by monomer physical properties rather than by large differences in condensation rate. Ethyl 2-cyanoacrylate, produced from ethyl cyanoacetate, polymerizes to a poly(ethyl 2-cyanoacrylate) film with a glass transition temperature commonly reported in the range 120–135 °C. Poly(methyl 2-cyanoacrylate), by comparison, is cited at 160–170 °C. The ethyl polymer therefore provides lower internal stress on flexible or low-surface-energy adherends, while the methyl polymer produces a harder, more brittle bond line. Ethyl cyanoacrylate monomer also has a lower vapor pressure than methyl cyanoacrylate, which reduces operator exposure and lowers the odor threshold during manual bonding. In condensation processing, ethyl cyanoacetate may require a slightly higher catalyst charge because the ethyl ester is marginally less electrophilic than the methyl ester; production records from glass-lined batch reactors often show piperidinium acetate additions rising from 0.5 mol% to 1.0 mol% relative to cyanoacetate when switching homologs. Published kinetic data for direct rate comparisons in mixed solvent systems is limited; industrial decisions therefore rely on boiling-point separation, monomer viscosity, and final polymer glass transition rather than absolute condensation rate constants. The higher boiling point of ethyl cyanoacetate allows a larger temperature difference between condensation and depolymerization stages, which simplifies recovery of unreacted ester in continuous units.
In ethyl 2-cyanoacrylate adhesive production, ethyl cyanoacetate is condensed with paraformaldehyde in a glass-lined or 316L stainless-steel reactor at 60–85 °C and 30–50 kPa absolute pressure. A typical formaldehyde-to-ester molar ratio is 1.05:1–1.20:1, with paraformaldehyde depolymerized in situ. Piperidinium acetate is used as the condensation catalyst. Water is removed by azeotropic distillation with toluene or cyclohexane, and residual solvent content in the oligomer is reduced before cracking. The oligomer is then transferred to a short-path or wiped-film evaporator operating at 180–220 °C and 1–5 kPa absolute pressure. Depolymerization releases ethyl 2-cyanoacrylate, which is condensed on a chilled surface and stabilized with acidic inhibitors such as phosphoric acid or boron trifluoride etherate at 10–100 ppm. Condenser fouling in short-path units is a documented bottleneck; an increase in absolute pressure from 1.5 kPa to above 4 kPa during a cracking campaign generally indicates oligomer carryover and is associated with monomer purity falling below 99.5%. Neat ethyl cyanoacetate itself does not require the monomer-type inhibitor package because the nitrile and ester substituents are not sufficiently activating for radical or anionic chain polymerization.
A comparison of ethyl cyanoacetate with methyl cyanoacetate, malononitrile, and ethyl acetoacetate illustrates differences in reactivity and application fit. Relative to malononitrile, ethyl cyanoacetate is less acidic and often more selective in aqueous alkaline condensations. Relative to ethyl acetoacetate, the nitrile group provides a stronger electron-withdrawing effect and routes to cyanoacetate-derived heterocycles. The values in the following table are compiled from standard reference data and safety data sheets.
| Property | Ethyl cyanoacetate | Methyl cyanoacetate | Malononitrile | Ethyl acetoacetate |
|---|---|---|---|---|
| CAS number | 105-56-6 | 105-34-0 | 109-77-3 | 141-97-9 |
| Molecular weight (g/mol) | 113.11 | 99.09 | 66.06 | 130.14 |
| Normal boiling point (°C) | 205–210 | 204–205 | 220 | 180.8 |
| Refractive index n20/D | 1.4170–1.4190 | 1.4160–1.4180 | 1.4140–1.4160 | 1.4180–1.4200 |
| Active-methylene behavior | Nitrile and ester; moderate acidity; forms cyanoacrylate and pyrimidine derivatives | Similar but lower boiling; methyl cyanoacrylate polymer has higher glass transition temperature | Two nitriles; stronger acidity; direct source of malononitrile adducts but no ester for cyanoacrylate cracking | Carbonyl and ester; lower acidity; forms pyrazolones and acetoacetate derivatives |
As an active-methylene building block, ethyl cyanoacetate is also consumed in pyrimidine, pyrazole, and thiophene chemistry. The Gewald reaction with elemental sulfur and an aliphatic ketone produces 2-aminothiophene intermediates; condensation with guanidine carbonate under basic conditions gives 2-amino-4,6-dihydroxypyrimidine, a standard intermediate for sulfonylurea herbicide synthesis. The methylene carbon reacts with aryl diazonium salts to form cyanoacetate hydrazone dyes. In these applications, the 99.5% distillation grade is selected when trace volatile nitrogen compounds or residual cyanoacetic acid consume base catalysts and complicate stoichiometric control. Residual acidity is specified as cyanoacetic acid at ≤0.20% by acid–base titration because higher acidity reduces the effective alkalinity of carbonate and acetate bases used in heterocyclic condensations. Published data for exact impurity profiles in specific drug intermediate syntheses is limited; however, supplier certificates of analysis commonly report the sum of unknown low-boiling impurities below 0.1% by GC.
Specifications for the 99.5% distillation grade are aligned to intermediate-level analytical methods. Gas chromatography with an internal standard is used instead of area normalization because it resolves ethyl cyanoacetate from ethanol, ethyl acetate, methyl cyanoacetate, cyanoacetic acid, and low-boiling homologs. Typical GC conditions use a 30 m × 0.32 mm × 0.25 µm polyethylene glycol capillary column with split injection at 250 °C and flame ionization detection. The following table lists typical certificate-of-analysis values and reference methods.
| Parameter | Specification | Reference method |
|---|---|---|
| Appearance | Clear liquid free of visible particles | Visual |
| Purity (GC, internal standard), wt% | ≥99.5 | GC-FID |
| Water, wt% | ≤0.10 | ASTM E203 |
| Acidity as cyanoacetic acid, wt% | ≤0.20 | Acid–base titration |
| Color, APHA | ≤20 | ASTM D1209 |
| Density at 20 °C, g/cm³ | 1.060–1.064 | ASTM D4052 |
| Refractive index n20/D | 1.4170–1.4190 | ASTM D1218 |
| Boiling range at 101.3 kPa, °C | 205–210 | ASTM D1078 |
| Residue after evaporation, wt% | ≤0.010 | ASTM D1353 |
Residual cyanoacetic acid above 0.20% neutralizes the piperidinium acetate catalyst during Knoevenagel condensation. Operators compensate by increasing base addition, but this narrows the processing window and can promote branched oligomer formation through competitive aldol-type self-condensation. Branched oligomer cracks less cleanly in the depolymerization step; pot residue increases, and the recovered monomer may show additional GC peaks for ethanol and acrylate byproducts. Water above 0.10% slowly hydrolyzes the ester during storage, releasing ethanol and cyanoacetic acid. At 35 °C and 65% relative humidity, unsealed product can exceed the water specification within 48 h. Storage therefore uses nitrogen blanketing at 5–10 kPa positive pressure and polished 316L stainless steel or glass-lined tanks. Carbon steel is not recommended because trace iron can reduce color stability and may accelerate nitrile hydrolysis. Contact with strong bases such as sodium hydroxide or primary amines such as monoethanolamine should be prevented in closed systems; rapid salt or cyanoacetamide formation can generate solids that obstruct vapor lines. Transfer lines should use mechanical seals or magnetic-drive pumps to minimize moisture ingress and fugitive emissions. The material is combustible but not classified as a flammable liquid; bulk storage is typically maintained at 15–30 °C away from oxidizers.
For occupational handling, ethyl cyanoacetate is classified under the harmonised system as Acute Tox. 4 for oral, dermal, and inhalation exposure; Skin Irrit. 2; Eye Irrit. 2; and STOT SE 3. Personnel exposure should be controlled with local exhaust ventilation and closed sampling loops. Spill control should use dry inert absorbent rather than water because the partial water solubility of the product can increase contamination area. Empty containers retain vapor and should be handled with the same precautions as full ones until cleaned or triple-rinsed. When the original nitrogen headspace remains intact, the product is stable for at least 12 months; after opening, the material should be used within 30 days or retested for water and acidity.
