Ethyl (2E)-cyano(phenylhydrazono)ethanoate , CAS No.27097-85-4

CAS: 27097-85-4 Cat. No.: E967069 Formula: C₁₁H₁₁N₃O₂ Peso molecolare: 217.220

Storage

Room temperature

Specifications

Condizioni di conservazione di stoccaggio

Room temperature

Nomi e identificatori

• Sorrisi canonici: CCOC(=O)/C(=N/NC1=CC=CC=C1)/C#N
• IUPAC Name: ethyl (2E)-2-cyano-2-(phenylhydrazinylidene)acetate
• InChIKey: NVOMLTILICGMJT-GXDHUFHOSA-N
• INCHI: 1S/C11H11N3O2/c1-2-16-11(15)10(8-12)14-13-9-6-4-3-5-7-9/h3-7,13H,2H2,1H3/b14-10+
• Peso molecolare: 217.220

Taxonomic Classification

Taxonomy Tree

• Kingdom Organic compounds
  • Superclass Benzenoids
    • Classe Benzene and substituted derivatives
      • Subclass Phenylhydrazines

• Kingdom: Organic compounds
• Superclass: Benzenoids
• Classe: Benzene and substituted derivatives
• Subclass: Phenylhydrazines
• Intermediate Tree Nodes: Not available
• Direct Parent: Phenylhydrazines
• Alternative Parents: Carboxylic acid esters Nitriles Monocarboxylic acids and derivatives Hydrazones Organopnictogen compounds Organic oxides Hydrocarbon derivatives Carbonyl compounds
• Molecular Framework: Aromatic homomonocyclic compounds
• Substituents: Phenylhydrazine - Carboxylic acid ester - Carboxylic acid derivative - Hydrazone - Monocarboxylic acid or derivatives - Carbonitrile - Nitrile - Carbonyl group - Organonitrogen compound - Organooxygen compound - Hydrocarbon derivative - Organic oxide - Organopnictogen compound - Organic oxygen compound - Organic nitrogen compound - Aromatic homomonocyclic compound
• Descrizione: This compound belongs to the class of organic compounds known as phenylhydrazines. These are compounds containing a phenylhydrazide moiety, which consists of a hydrazide substituent attached to a phenyl group.
• External Descriptors: Not available

Data sources

1. Djoumbou Feunang Y, Eisner R, Knox C, Chepelev L, Hastings J, Owen G, Fahy E, Steinbeck C, Subramanian S, Bolton E, Greiner R, and Wishart DS. ClassyFire: Automated Chemical Classification With A Comprehensive, Computable Taxonomy. Journal of Cheminformatics, 2016, 8:61.

DOI: 10.1186/s13321-016-0174-y

Proprietà chimiche e fisiche

• Peso molecolare: 217.220 g/mol
• XLogP3: 3.300
• Hydrogen Bond Donor Count: 1
• Hydrogen Bond Acceptor Count: 5
• Rotatable Bond Count: 5
• Exact Mass: 217.085 Da
• Monoisotopic Mass: 217.085 Da
• Topological Polar Surface Area: 74.500 Ų
• Heavy Atom Count: 16
• Formal Charge: 0
• Complexity: 310.000
• Isotope Atom Count: 0
• Defined Atom Stereocenter Count: 0
• Undefined Atom Stereocenter Count: 0
• Defined Bond Stereocenter Count: 1
• Undefined Bond Stereocenter Count: 0
• The total count of all stereochemical bonds: 1
• Covalently-Bonded Unit Count: 1

Application Protocols

No application protocols are specified for this catalog item. As a synthetic building block, its use conditions are highly context-dependent on the target transformation. Refer to the Reaction & Applications and Reaction Conditions sections for general guidance, and develop substrate-specific procedures through small-scale optimization.

• For analytical tracking, consider HPLC with diode-array detection (monitor 220–360 nm) and LC–MS for mass confirmation.
• For purification, start with small recrystallization screens (EtOAc/hexane, EtOAc/toluene, MeOH/EtOAc) before moving to flash chromatography.

Research Use Note: For research use only.

Biological Roles

This product is intended strictly for research and laboratory use. No biological function or role is assigned for this specific small molecule.

General context for similar chemotypes (literature-based, not product-specific claims):

• Hydrazone-containing small molecules are frequently used as intermediates in the preparation of bioactive scaffolds (e.g., pyrazoles, oxadiazoles), but the hydrazone itself is typically a transient synthetic handle rather than a biological ligand.
• The molecule is neutral and contains an H-bond-donating NH plus multiple acceptors (nitrile, carbonyl, imine N), features that are sometimes exploited in medicinal chemistry to tune properties in lead optimization. However, any such use requires bespoke evaluation of ADME/toxicity, which is outside the scope of this product listing.

No clinical, diagnostic, or therapeutic claims are made for this item.

Buffer Applications

Not typically applicable. Ethyl (2E)-cyano(phenylhydrazono)ethanoate is a neutral, hydrophobic organic building block rather than an acid/base buffering agent. For aqueous experimental systems, consider dedicated buffer salts (e.g., phosphate, HEPES, TRIS) and refer instead to the Solvent Selection and Reaction & Applications sections for guidance on using this compound in organic media.

Green Alternatives

When planning workups, purifications, and reactions with arylhydrazono cyanoacetates, solvent choice dominates the environmental footprint. Consider the following greener swaps where compatible with your process and analytical needs.

Comparison (general guidance):

• Chlorinated solvents (DCM, CHCl3): High performance for dissolution and chromatography, but poor EHS profile.
• Greener alternatives: Ethyl acetate, 2-MeTHF, Me-THF/EtOAc mixtures, propylene carbonate, acetonitrile (widely accepted, lower toxicity than DMF/DMAc), and aqueous ethanol for certain recrystallizations.

Small decision table (literature-based trends):

• Dissolution and reaction medium:
  • Prefer EtOAc, 2-MeTHF, MeCN where solubility allows.
  • Reserve DMSO/DMF for high-temperature needs; consider sulfolane or propylene carbonate as higher-boiling, greener polar aprotics if workup is manageable.
• Chromatography:
  • Replace DCM with EtOAc/hexanes or heptane where separation allows.
  • For difficult separations, consider supercritical CO2 (SFC) with polar modifiers.
• Workup:
  • Use brine-sparing extractions and minimal chlorinated waste; consider solid-phase extraction (SPE) for small-scale cleanup.

Trade-offs:

• Some greener solvents increase reaction times or alter selectivity; run small scouting experiments.
• Hydrazones can hydrolyze in protic media under acid; balance greenness with stability.

Pharmaceutical Uses

No pharmacopeial grade or excipient status is provided for this item. Not specified for this item; refer to CoA/Spec Sheet.

General R&D/manufacturing context (non-clinical; literature-based):

• Potential role as a synthetic intermediate toward heterocyclic scaffolds used in drug discovery campaigns (e.g., pyrazoles, oxadiazoles). Any progression into GMP or clinical supply would require respecification, impurity fate mapping, and validation of synthetic routes.
• Solvent and impurity control: Given the N–N functionality, assess residual hydrazine/hydrazide-type impurities and nitrosamine risk as part of ICH M7 considerations during route development (if applicable to your project).
• Solid form: Characterization of polymorph/hydrate forms can be prudent if scaling crystallizations, as hydrazone E/Z isomerism and hydrogen bonding may influence lattice packing.

This product is supplied for research use only and is not approved for use as a drug substance, excipient, or in diagnostic procedures.

Physical Properties

Item-specific physicochemical specifications are not provided in the Product Data.

• Appearance: Not specified for this item; refer to CoA/Spec Sheet.
• Melting point / Boiling point: Not specified for this item; refer to CoA/Spec Sheet.
• Density / Refractive index: Not specified for this item; refer to CoA/Spec Sheet.
• Solubility: Not specified for this item; refer to CoA/Spec Sheet.
• pKa / logP: Not specified for this item; refer to CoA/Spec Sheet.

General/literature-based expectations (for context only; verify experimentally):

• Hydrazone-bearing cyanoacetate derivatives are typically crystalline solids with moderate thermal stability and may exhibit E/Z isomerism around C=N; the E isomer often predominates.
• Likely sparingly soluble in water; soluble in polar aprotic organic solvents (e.g., acetonitrile, DMF, DMSO) and in moderately polar chlorinated/aromatic solvents (DCM, chloroform, toluene). Alcohols may also dissolve it depending on temperature.
• The molecule is neutral overall but has multiple H-bond donors/acceptors (hydrazone NH, nitrile N, carbonyl O), which can influence solvation and recrystallization behavior.

Important: Do not use the above generalizations as specifications. For exact acceptance criteria (mp range, GC/HPLC purity, water/peroxide/metal limits, UV cut-off), consult the item’s CoA/Specification Sheet.

Quality and Grades

• Grade/Purity: Not specified for this item; refer to CoA/Spec Sheet.

Interpretation and guidance:

• When provided, grade descriptors (e.g., AR, HPLC, >98%) define acceptance limits for assay, key impurities, and often moisture or residue on ignition. In absence of a declared grade, rely on the batch-specific CoA for assay (HPLC/GC/NMR) and impurity profiles.
• UV-sensitive or base/acid-sensitive hydrazones can show minor E/Z isomerization; reputable specifications typically define assay on a normalized basis with acceptance criteria for geometric isomers, if applicable.
• Stabilizers: None listed for this item. If a stabilizer is used in similar products, it will be disclosed on the label/CoA since stabilizers can impact downstream reactions (e.g., amines or acids catalyzing side reactions). For this item, stabilizer presence/absence is Not specified for this item; refer to CoA/Spec Sheet.
• Analytical considerations (general):
  • Identity: 1H/13C NMR (diagnostic hydrazone =CH shift, NH signal), IR (C≡N ~2220–2260 cm−1; C=O ~1720–1740 cm−1; C=N ~1600–1640 cm−1), HRMS.
  • Purity: HPLC with DAD at multiple wavelengths (254–360 nm) due to conjugation; GC may be less suitable for non-volatile solids.
  • Residual solvents/water: Karl Fischer and GC–headspace as applicable.

Always consult the batch CoA for definitive specifications and release criteria.

Reaction and Applications

Research-use contexts for ethyl (2E)-cyano(phenylhydrazono)ethanoate leverage its conjugated hydrazone flanked by two strong electron-withdrawing groups (nitrile and ester), creating a tunable electrophile and a precursor to N–N-containing heterocycles.

General/literature-based applications (expand/optimize per project):

• Heterocycle synthesis precursor: Base- or acid-promoted cyclizations transform arylhydrazono cyanoacetates into diverse azoles (e.g., pyrazoles, 1,3,4-oxadiazoles) via intramolecular nucleophilic attack and N–N participation. Reaction partners such as hydroxylamine, hydrazines, and amidines can direct ring outcomes.
• Michael-type additions: The activated C=N–C(CN)(CO2Et) system can undergo conjugate addition of soft nucleophiles (e.g., thiols, enolates), followed by tautomerization or subsequent cyclization.
• Electrophilic diazo surrogacy: Under nitrosative or oxidative conditions, hydrazones can be converted to diazo intermediates that further participate in cyclopropanation or insertion chemistry (requires careful control and safety review).
• Protective/latency function: The hydrazone masks a reactive carbonyl equivalent; selective cleavage under acidic conditions can regenerate corresponding carbonyl components (strategy-dependent).
• Azo/hydrazone switching: E/Z isomerism around C=N provides a handle for photochemical or base-catalyzed isomer control in materials-oriented studies (where applicable).

Practical tips:

• Dry, oxygen-limited conditions help suppress oxidative side reactions and isomerization during base-mediated steps.
• Use mild bases (e.g., triethylamine, pyridine, piperidine) to initiate condensations while minimizing hydrolysis of the ester.
• Monitor by HPLC/LC–MS; hydrazone E/Z ratios may shift with solvent and temperature.

Reaction Conditions

The following are general, literature-based condition ranges for typical transformations of arylhydrazono cyanoacetates. They are provided for planning purposes and should be optimized experimentally for your substrate and scale.

• Cyclizations to azoles (e.g., with hydroxylamine or hydrazides):

  • Solvent: Ethanol, acetonitrile, or DMF.
  • Base/catalyst: Pyridine, triethylamine, or catalytic acetate salts.
  • Temperature: 25–80 °C (reflux in EtOH for sluggish systems).
  • Time: 1–16 h depending on nucleophile and solvent.

• Michael-type additions of soft nucleophiles:

  • Solvent: MeCN, EtOH, or DCM.
  • Base: Piperidine or DBU (catalytic to substoichiometric), or preformed enolates (NaOEt) at 0–25 °C.
  • Temperature: 0–40 °C (higher temps risk isomerization/hydrolysis).
  • Time: 0.5–6 h, monitor by TLC/HPLC.

• Hydrazone-to-diazo conversions (advanced; safety critical):

  • Reagents: tert‑butyl nitrite or nitrosyl derivatives under controlled basic conditions; copper salts as promoters where applicable.
  • Solvent: MeCN or DCM at 0–25 °C.
  • Strict controls for gas evolution and quench; assess energetics before scale-up.

Workup and purification:

• Quench bases with buffered acid (pH ~6–7) to avoid hydrazone cleavage; extract into EtOAc; dry gently (avoid prolonged basic drying agents).
• Purify by recrystallization (EtOAc/hexane) or silica chromatography with minimal protic modifiers to limit isomerization.

Safety and Handling

GHS/SDS details are not provided in the Product Data. Always consult the official SDS for authoritative hazard classifications and response measures.

• GHS classification / pictograms / H-statements: Not specified for this item; refer to SDS.
• Signal word: Not specified for this item; refer to SDS.

General safety considerations for arylhydrazones and nitrile/ester-containing organics (literature-based guidance):

• Potential hazards: Irritation to skin/eyes/respiratory tract; harmful if swallowed. Hydrazone N–H can engage in acid/base reactions; avoid strong oxidizers and strong acids/bases that may induce decomposition or hydrolysis.
• Incompatibilities: Strong oxidizers; strong acids (may hydrolyze hydrazone and ester); strong bases (may induce E/Z isomerization or condensations); nitrosating agents (may form N-nitroso species).
• PPE: Lab coat, nitrile gloves, splash goggles. Use in a fume hood to control dust/vapor exposure.
• Handling: Avoid dust formation; weigh under local exhaust. Keep containers tightly closed. Prevent exposure to moisture if it affects stability.
• First aid (overview):
  • Inhalation: Move to fresh air; seek medical attention if symptoms persist.
  • Skin: Wash with soap and water; remove contaminated clothing.
  • Eyes: Rinse cautiously with water for several minutes; remove contact lenses if present and easy to do; continue rinsing.
  • Ingestion: Rinse mouth; do not induce vomiting; seek medical advice.
• Fire: Treat as combustible organic solid; use CO2, dry chemical, or foam. Thermal decomposition may release nitrogen oxides.
• Waste: Collect as organic hazardous waste per institutional and local regulations.

Solvent Selection

This compound is a neutral, moderately polar, conjugated hydrazone bearing nitrile and ester groups. It generally prefers polar aprotic media and certain chlorinated/aromatic solvents.

• Polarity class (general): Moderately polar, H-bond donor/acceptor; favors aprotic polar solvents.
• Likely good solvents (general guidance): DMSO, DMF, DMAc, NMP, acetonitrile, dichloromethane, chloroform, ethyl acetate, THF; toluene at elevated temperature.
• Limited solubility expected in: Aliphatic hydrocarbons (hexanes, heptane); water.

Choosing solvents by task (general best practices):

• Recrystallization: Ethyl acetate/hexanes or EtOAc/toluene mixtures are often effective for arylhydrazones; adjust polarity by adding a small amount of ethanol or acetonitrile if needed.
• Reaction medium for condensations/Michael-type additions: Acetonitrile or ethanol under catalytic base (e.g., piperidine) often provide good rates while minimizing side reactions; DMSO/DMF enable higher temperatures but complicate workups.
• Chromatography: Normal-phase silica using EtOAc/hexane or DCM/MeOH gradients; monitor at multiple UV wavelengths due to extended conjugation.

Green chemistry note:

• Prefer MeCN, 2-MeTHF, EtOAc, or aqueous ethanol where feasible over chlorinated solvents. Validate solubility and stability (hydrolysis risk in protic media) before scaling.

Storage and Reconstitution

• Storage Conditions (Product Data): Room temperature.
• Shipped In: Not specified for this item; refer to CoA/Spec Sheet.

General storage guidance:

• Keep tightly closed in the original container, protected from moisture and prolonged light exposure to minimize hydrazone E/Z isomerization or hydrolysis.
• Store in a dry place; include a small desiccant pack if opening frequently.
• Avoid storing with strong acids, bases, or oxidizers.

Reconstitution and preparation for use:

• For solution-phase work, prepare stock solutions in dry organic solvents such as DMSO, DMF, MeCN, or DCM. Filter through a PTFE syringe filter (0.2–0.45 µm) if particulate is present.
• If weighing small quantities, minimize exposure to ambient humidity and heat; close the vial promptly after dispensing.
• For long-term solution storage, prefer amber vials under inert gas at 2–8 °C; assess stability via periodic HPLC if solutions are kept >1 week.

Disposal: Treat as organic hazardous waste in accordance with institutional and local regulations.

Structure and Identity

Ethyl (2E)-cyano(phenylhydrazono)ethanoate is an azomethine (hydrazone) derived from ethyl cyanoacetate and an aniline/aryl diazonium precursor, featuring a conjugated C=N–NAr motif flanked by a nitrile and an ethyl ester.

• CAS: 27097-85-4 (Product Data)
• PubChem CID: 5354190 (Product Data)
• InChIKey: 249098 (as provided; note: atypical format, verify on CoA/SDS)
• SMILES: Not specified for this item; refer to CoA/Spec Sheet.
• Molecular formula: Not specified for this item; refer to CoA/Spec Sheet.
• Molecular weight: Not specified for this item; refer to CoA/Spec Sheet.

Structural features (from the chemical name; general/literature-based description):

• Contains an ethyl ester (–CO2Et), a nitrile (–C≡N), and a phenylhydrazone fragment (–C(=N–NH–Ph)).
• The descriptor “(2E)” indicates the C=N double bond adopts the E configuration across the hydrazone linkage in the named isomer.
• The central sp2 carbon is conjugated with the ester carbonyl and nitrile, creating a strongly electron-deficient center conjugated to the azomethine, enabling resonance stabilization.
• Aromatic ring: one unsubstituted phenyl attached via the hydrazone N.
• No stereocenters; one defined C=N geometric isomer as named.

2D description in words (general): an ethyl cyanoacetate core in which the methylene at C-2 is converted to a C=N–NH–phenyl hydrazone, leaving the nitrile and ester as vicinal electron-withdrawing groups aligned with the azomethine.

Synthetic Utility

Key functional elements and reactivity (general, literature-based):

• Conjugated hydrazone (–C=N–NH–Ph): acts as an electrophile at the imine carbon and can be transformed under nitrosative/oxidative conditions to diazo species; can also be cleaved to regenerate carbonyl precursors.
• Vicinal activating groups (–CN and –CO2Et): render the adjacent carbon highly electron poor, enabling conjugate additions and facilitating cyclizations to N-rich heterocycles.
• N–N unit: embedded nucleophile/Leaving group behavior in ring-forming reactions (e.g., forming pyrazoles/oxadiazoles depending on conditions and partners).

Representative synthetic maneuvers:

• Cyclocondensations with nucleophiles (hydroxylamine, hydrazides, amidines, ureas) to access 1,2,4- and 1,3,4-azoles.
• Michael addition of soft carbon nucleophiles (malonates, β-ketoesters) followed by intramolecular trapping to elaborate densely functionalized frameworks.
• Electrophilic capture: Halogenation or acylation at activated centers under mild conditions to install handles for cross-coupling.
• Deprotection/transform: Controlled hydrolysis or exchange at the ester (transesterification, amidation) without disrupting the hydrazone, with careful selection of catalysts and pH.

Practical guidance:

• Employ mild bases (pyridine, piperidine, Et3N) to avoid undesired hydrolysis/isomerization.
• Monitor E/Z isomer ratio by NMR; some transformations are stereospecific or show isomer-dependent rates.
• Protect from strong acids and nitrosating conditions unless those conversions are intended.

Target Specificity

Not applicable. This product is a small-molecule building block and is not an antibody, enzyme, ligand-directed probe, or biological affinity reagent. No target, epitope, isotype, or species reactivity information applies.