Ethyl 3-methoxybenzoylformate - ≥95% , CAS No.86358-29-4

CAS: 86358-29-4 Cat. No.: E1067257 Fórmula: C₁₁H₁₂O₄ Peso molecular: 208.22 Número CE: 675-591-7 PubChem CID: 2758863

GRADE & PURITY ≥95%

Storage

Room temperature

Specifications

Especificações e pureza

≥95%

Condições de armazenamento de armazenamento

Room temperature

Pureza

≥95%

Nomes e identificadores

• Sorrisos canónicos: CCOC(=O)C(=O)C1=CC(=CC=C1)OC
• IUPAC Name: ethyl 2-(3-methoxyphenyl)-2-oxoacetate
• InChIKey: DWLYVLJKLZPOAW-UHFFFAOYSA-N
• INCHI: 1S/C11H12O4/c1-3-15-11(13)10(12)8-5-4-6-9(7-8)14-2/h4-7H,3H2,1-2H3
• SMILES isoméricas: CCOC(=O)C(=O)C1=CC(=CC=C1)OC
• PubChem CID: 2758863
• Peso molecular: 208.22

Taxonomic Classification

Taxonomy Tree

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

• Kingdom: Organic compounds
• Superclass: Benzenoids
• Classe: Benzene and substituted derivatives
• Subclass: Benzoyl derivatives
• Intermediate Tree Nodes: Not available
• Direct Parent: Benzoyl derivatives
• Alternative Parents: Phenoxy compounds Methoxybenzenes Aryl ketones Anisoles Alkyl aryl ethers Alpha-keto acids and derivatives Carboxylic acid esters Monocarboxylic acids and derivatives Organic oxides Hydrocarbon derivatives
• Molecular Framework: Aromatic homomonocyclic compounds
• Substituents: Phenoxy compound - Anisole - Methoxybenzene - Aryl ketone - Phenol ether - Benzoyl - Alkyl aryl ether - Alpha-keto acid - Keto acid - Carboxylic acid ester - Ketone - Ether - Carboxylic acid derivative - Monocarboxylic acid or derivatives - Organic oxygen compound - Carbonyl group - Organooxygen compound - Hydrocarbon derivative - Organic oxide - Aromatic homomonocyclic compound
• Descrição: This compound belongs to the class of organic compounds known as benzoyl derivatives. These are organic compounds containing an acyl moiety of benzoic acid with the formula (C6H5CO-).
• 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

Propriedades químicas e físicas

• Peso molecular: 208.210 g/mol
• XLogP3: 2.000
• Hydrogen Bond Donor Count: 0
• Hydrogen Bond Acceptor Count: 4
• Rotatable Bond Count: 5
• Exact Mass: 208.074 Da
• Monoisotopic Mass: 208.074 Da
• Topological Polar Surface Area: 52.600 Ų
• Heavy Atom Count: 15
• Formal Charge: 0
• Complexity: 237.000
• Isotope Atom Count: 0
• Defined Atom Stereocenter Count: 0
• Undefined Atom Stereocenter Count: 0
• Defined Bond Stereocenter Count: 0
• Undefined Bond Stereocenter Count: 0
• The total count of all stereochemical bonds: 0
• Covalently-Bonded Unit Count: 1

Application Protocols

Not applicable. No biological assay protocols (e.g., WB, IHC, IF, FC) are associated with this small-molecule synthetic intermediate. For synthetic procedures using this reagent, see the Reaction Conditions and Synthetic Utility sections.

Biological Roles

Scope

• Ethyl 3-methoxybenzoylformate is a synthetic organic intermediate (aryl α-keto ester) and is not a known endogenous metabolite or cofactor.

General biochemical context (literature)

• Aryl α-keto esters can act as electrophilic models in studies of nucleophile–carbonyl interactions (e.g., with thiols or amines) and as substrates in enzyme-mimetic catalysis or organocatalytic systems probing selectivity and reactivity of α-dicarbonyls.
• The α-keto/ester motif is related to structural elements present in some biochemical intermediates (e.g., α-ketoacids and esters), but the 3-methoxyphenyl substituent is non-natural and primarily used for structure–reactivity studies or as a stepping stone in small-molecule synthesis.

Use limitations

• No medical, diagnostic, or therapeutic uses are claimed or supported for this item. For research use only (per Product Data).

If biological testing is contemplated

• Verify purity and residual solvent content from the CoA.
• Evaluate reactivity toward biomolecules (e.g., GSH, lysine side chains) due to the electrophilic α-keto group; unintended covalent modification is possible in complex media.
• Select biocompatible solvents or formulate in DMSO with appropriate dilution into buffers immediately prior to use; monitor for hydrolysis/transesterification.

Buffer Applications

This compound is a neutral, hydrophobic organic synthetic intermediate and is not typically used to prepare laboratory buffer systems. It lacks acid/base functionality in the working pH range and has low aqueous solubility.

Practical note

• If used in biochemical assays, it is commonly dissolved in an organic co-solvent (e.g., DMSO, MeCN, EtOH) and then diluted into buffer immediately before use to minimize precipitation and hydrolysis. Buffer composition and pH should be optimized for the biological system, not for this compound per se.

Green Alternatives

Greener approaches focus on solvent and reagent choices, as the substrate itself is a specialized intermediate.

Solvent substitutions (literature guidance)

• Replace chlorinated solvents (DCM, CHCl3) with ethyl acetate, toluene, 2-MeTHF, or CPME when comparable selectivity is achievable.
• Substitute THF with 2-MeTHF (bio-derived) for organometallic additions or enolizations; often similar coordination properties with higher boiling point and better safety profile.
• Favor MeCN over DMF/DMSO when feasible due to easier removal and lower toxicity profile (optimization required for each transformation).

Reductants/oxidants

• Use catalytic hydrogenation or transfer hydrogenation (Hantzsch ester, isopropanol/Ru or organocatalysts) instead of stoichiometric metal hydrides where chemoselectivity allows.
• Electrochemical or photoredox methods can sometimes replace harsh reagents for radical additions or dehalogenations in the presence of arylglyoxylates.

Comparison snapshot (general)

• DCM vs EtOAc: EtOAc reduces chlorinated waste and often dissolves arylglyoxylates adequately; extraction and chromatography also benefit from lower toxicity.
• THF vs 2-MeTHF: 2-MeTHF is less peroxide-prone and has better life-cycle metrics; drying and organometallic compatibility remain strong.

Trade-offs

• Greener solvents may change reaction rates/selectivity (e.g., polar effects in enolate chemistry). Conduct head-to-head screening and ensure stability of α-keto ester toward transesterification/hydrolysis in protic solvents.

Note: These are general green chemistry considerations; applicability should be confirmed experimentally for each reaction type involving this substrate.

Pharmaceutical Uses

No pharmacopeial or excipient role is indicated for this item.

General context (literature)

• Aryl α-keto esters such as ethyl 3-methoxybenzoylformate are frequently employed as synthetic intermediates during R&D and process development for small molecules. They can serve as masked α-hydroxy acids (mandelic derivatives), precursors to α-ketoamides, or as electrophilic partners in enantioselective bond constructions.

Formulation/manufacturing perspective

• If used as a process intermediate, control of residual levels is typically achieved via downstream purifications and analytical methods (HPLC/GC). No claims are made regarding suitability as an API or excipient.

Regulatory note

• For research use only (per Product Data). Not for human or veterinary use. No therapeutic claims are made.

Physical Properties

Item-specific specs

• Appearance: Not specified for this item; refer to CoA/Spec Sheet.
• Molecular weight: Not specified for this item; refer to CoA/Spec Sheet. (Computed literature value provided below for reference.)

Literature/Computed (reference only; not item specification)

• Molecular formula: C11H12O4 (see Structure & Identity)
• Molecular weight (computed): ~208.21 g/mol
• Physical state: Typically a low-melting solid or viscous liquid for closely related arylglyoxylate ethyl esters; exact state for this item is not specified.
• Solubility (qualitative, literature): Expected to be soluble in common organic solvents (ethyl acetate, dichloromethane, THF, toluene, acetonitrile) and poorly soluble in water due to aromatic ring and ester functionality.
• Volatility: Moderate; α-keto esters with C2 alcohol residues often distill under reduced pressure if thermally managed; exact boiling point for this item is not specified.
• Spectroscopic signatures (general): Strong IR carbonyl bands for aryl ketone (~1680–1705 cm−1) and ester (~1720–1740 cm−1); 1H NMR typically shows ethyl quartet/triplet, anisotropic aryl protons, and methoxy singlet; 13C NMR with two distinct carbonyl resonances.

Not available in Product Data (do not infer)

• Melting point, boiling point, density, refractive index, UV cut-off, water content, and trace impurity limits: Not specified for this item; refer to CoA/Spec Sheet.

Quality and Grades

Item-specific

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

Guidance for this compound class (literature/industry context)

• α-Keto esters (arylglyoxylates) used in synthesis are commonly supplied at high purity suitable for general organic synthesis. If chromatography or photochemical steps are planned, low UV background and low peroxide/carbonyl impurities are advantageous; verify by CoA/SDS.
• Typical quality attributes to review on the CoA:
  • Purity by GC/HPLC/1H NMR
  • Residual solvents and water content
  • Identity confirmation (NMR/IR/MS) and, where relevant, optical purity (not applicable here; achiral)
  • Peroxide content is generally a concern for ethers; for α-keto esters it is less typical, but verify any specified limits if provided
• If “HPLC grade” or “LCMS grade” is noted for similar items, it generally implies minimized UV-absorbing impurities and very low nonvolatile residue—useful for analytical workflows. In absence of such designation for this item, treat it as a synthetic intermediate grade unless the CoA indicates otherwise.

Recommendation

• For sensitive enantioselective catalysis or photoredox applications, request the most recent CoA, and, if necessary, pre-purify by flash chromatography and store under inert gas to preserve quality.

Reaction and Applications

This arylglyoxylate (ethyl 3-methoxybenzoylformate) is a versatile electrophile and synthon for constructing α-hydroxy esters, α,α-difunctionalized esters, and aryl–C2 frameworks.

Representative reaction families (literature/general)

• Nucleophilic 1,2-additions at the keto carbonyl: cyanide, organometallics (RMgX/RLi under controlled conditions), and soft nucleophiles (thiols, amines) afford α-substituted mandelate-type esters after workup.
• Enantioselective aldolizations and Mannich-type additions: Under organocatalysis (e.g., chiral amines, NHCs, or Lewis acids), arylglyoxylates participate as electrophiles to give β-hydroxy-α-keto esters or α,α-difunctionalized motifs with high ee.
• Reductive transformations: Chemoselective reduction of the keto carbonyl (NaBH4, metal hydrides) furnishes mandelate esters; complete reduction or hydrogenation can give diols or alcohol–ester pairs.
• Olefinations at the keto carbonyl: Wittig/Horner–Wadsworth–Emmons provide α,β-unsaturated esters conjugated to the aryl ring (control of E/Z via reagent choice and temperature).
• Cycloadditions/annulations: As acceptors in [2+2], [3+2], and photoredox-enabled radical additions to access α-substituted esters and benzofused scaffolds.
• Acyl transfer/NHC catalysis: N-Heterocyclic carbene catalysis enables benzoin-like couplings and Stetter-type umpolung sequences using arylglyoxylates as acyl donors/acceptors.

Utility of the m-methoxy substituent

• The 3-OMe group modulates electrophilicity via resonance/inductive effects and offers a handle for further derivatization (demethylation to phenol, cross-coupling after directed metalation on functionalized derivatives).

Applications in research workflows

• Chiral building block synthesis (mandelic ester derivatives), preparation of α-ketoamide precursors, and late-stage diversification of aryl motifs for materials and medicinal chemistry. Always validate conditions on small scale to balance reactivity of the α-dicarbonyl vs. ester hydrolysis.

Reaction Conditions

The following conditions are representative literature guidance for arylglyoxylates and should be optimized for this substrate. They are not product specifications.

• Chemoselective ketone reduction to mandelate esters:

  • Reagents: NaBH4 (0.5–1.5 eq)
  • Solvent: MeOH, EtOH, or THF/MeOH (0–25 °C)
  • Notes: Monitor by TLC/LC; quench carefully to avoid ester hydrolysis.

• Organometallic 1,2-additions (forming tertiary alcohols after workup):

  • Reagents: RMgX or R2CuLi (1.1–1.5 eq)
  • Solvent: THF, Et2O, or toluene; −78 to 0 °C
  • Notes: Prefer softer nucleophiles (cuprates) to enhance selectivity for the keto carbonyl; strict anhydrous conditions.

• Wittig/HWE olefination at the keto carbonyl:

  • Reagents: Ph3P=CHR or phosphonate (1.2–1.5 eq), base (NaH, K2CO3, or tBuOK)
  • Solvent: THF, DCM, or MeCN; −20 to 25 °C
  • Notes: HWE often gives E-selectivity; mild bases help preserve the ester.

• Knoevenagel with active methylenes (e.g., malonates, cyanoacetates):

  • Catalysts: Piperidine, ammonium acetate, or heterogeneous amines
  • Solvent: Toluene, EtOH, or 2-MeTHF; 25–110 °C (Dean–Stark if necessary)

• Formation of α-ketoamides:

  • Reagents: Amines (1.1 eq), coupling agents (EDC/HOBt, DCC)
  • Solvent: DCM or DMF; 0–25 °C
  • Notes: Control temperature to avoid 1,2-addition by strongly nucleophilic amines.

Typical outcomes

• Many of these transformations afford 60–90% isolated yields under optimized conditions in literature reports, highly dependent on substituents and reagent/catalyst choice.

Always validate on small scale and consult primary literature for closely related arylglyoxylates.

Safety and Handling

Item-specific (from Product Data)

• GHS classification, signal word, pictograms, H-statements: Not specified for this item; refer to the SDS.
• Storage conditions: Room temperature (per Product Data).

General safety guidance (literature/industry practice; defer to SDS for authoritative details)

• Likely hazards: α-Keto esters and aromatic esters are commonly classified as harmful/irritant; avoid inhalation, ingestion, and skin/eye contact. Some arylglyoxylates may cause eye/skin irritation.
• PPE: Use appropriate laboratory PPE — lab coat, safety glasses or goggles, and chemical-resistant gloves (e.g., nitrile). Work in a fume hood to avoid exposure to vapors or aerosols.
• Handling: Minimize exposure to heat and light to avoid slow degradation (e.g., self-condensation or hydrolysis). Keep container tightly closed. Consider maintaining an inert gas blanket if long-term storage after opening is expected, as α-dicarbonyls can be moisture-sensitive over time.
• Incompatibilities: Strong bases (risk of enolization/condensation), strong acids (ester hydrolysis), strong oxidizers or reducing agents (redox at the carbonyls), and nucleophiles (addition to the keto carbonyl). Avoid prolonged contact with alkali metals and strong amines.
• First aid (overview): If skin contact occurs, wash with soap/water; for eye exposure, rinse with water for several minutes and seek medical attention; if inhaled, move to fresh air; if ingested, seek medical attention. Always follow your institutional SOPs and the SDS.
• Spill/leak: Absorb with inert material (vermiculite, sand), collect for disposal. Prevent entry into drains. Dispose according to local regulations.

Note: Always consult the product-specific SDS for confirmed hazard classification and emergency measures.

Solvent Selection

Applicability: Ethyl 3-methoxybenzoylformate is an organic synthetic intermediate (aryl α-keto ester). Solvent choice affects stability, reaction selectivity, and workup.

General polarity/miscibility (literature)

• Polarity: Moderately polar, aprotic solute; dissolves well in common organic solvents (EtOAc, DCM, CHCl3, toluene, THF, MeCN). Low aqueous solubility anticipated.
• Hydrogen bonding: Carbonyl acceptor only; no donors.

Selection guidance by transformation (general)

• Nucleophilic additions (e.g., 1,2-addition, cyanation): Use polar aprotic media (THF, MeCN, DCM) to enhance electrophilicity and control rates. Low temperature often beneficial to limit over-reaction.
• Enolate chemistry/Knoevenagel: Employ non-protic, moderately polar solvents (THF, toluene) with bases (amines, piperidine, carbonate). Avoid high-water content to suppress hydrolysis.
• Catalytic asymmetric additions (organocatalysis, metal catalysis): Dry, oxygen-free solvents (toluene, DCM, Et2O, MTBE) under inert atmosphere to protect catalyst and substrate.
• Reductions (NaBH4, Hantzsch ester, catalytic hydrogenation): Alcoholic solvents for borohydride (MeOH/EtOH) can be used with care; for chemoselectivity, use THF/MeOH mixtures or aprotic media with activated hydrides.
• Photoredox/EDA reactions of arylglyoxylates: MeCN, DMSO, or DMF often used; oxygen exclusion is critical.

Practical notes

• Hydrolysis risk increases in alcoholic solvents under acidic/basic conditions; neutral aprotic media are preferred for storage and manipulations.
• For scale-up, greener options (2-MeTHF, CPME, EtOAc) can replace DCM/THF in many cases; evaluate solubility and selectivity case-by-case.

Storage and Reconstitution

Item-specific (from Product Data)

• Storage conditions: Room temperature.
• Shipped in: Not specified for this item; refer to CoA/Spec Sheet.

General guidance for α-keto esters (literature/practice; not specification)

• Container: Store in a tightly closed amber glass bottle to minimize light exposure; the α-dicarbonyl chromophore can be light-sensitive. An inert gas headspace (N2/Ar) is advisable after opening to limit slow oxidation or condensation.
• Environment: Keep dry. Moisture can promote hydrolysis or transesterification, especially in the presence of acids/bases.
• Stability: Avoid prolonged heating; if distillation is required, use reduced pressure and minimal residence time. Refrigeration is typically not necessary unless indicated by the CoA, but may extend shelf life.

Reconstitution/Preparation for use

• The material generally dissolves readily in common organic solvents (EtOAc, DCM, THF, toluene, MeCN). Dry solvents improve stability during handling.
• For biochemical assays, prepare concentrated stock solutions in dry DMSO or MeCN and dilute immediately before use to minimize precipitation and hydrolysis.

Inspection

• Before use, check for discoloration, precipitate formation, or unusual odor as signs of degradation. If quality-sensitive work is planned, confirm identity/purity by quick 1H NMR or HPLC.

Research use note

• For research use only (per Product Data). Not for human or veterinary use.

Structure and Identity

Item-specific (from Product Data)

• SKU: E1067257
• Product name: Ethyl 3-methoxybenzoylformate
• CAS: 86358-29-4
• InChIKey: 74621 (as provided; appears truncated — consult CoA/SDS for full identifier)
• SMILES: Not specified for this item; refer to CoA/Spec Sheet.

Literature/Computed (for reference; not item specification)

• Preferred IUPAC name (literature): Ethyl 2-oxo-2-(3-methoxyphenyl)acetate (also called ethyl 3-methoxybenzoylformate; an arylglyoxylate ester)
• Molecular formula (computed from structure): C11H12O4
• Molecular weight (computed): ~208.21 g/mol
• Canonical SMILES (literature): COc1cccc(c1)C(=O)C(=O)OCC

Structural features (general description)

• Functional groups: aromatic methoxy (Ar–O–CH3), aryl ketone (Ar–C(=O)–), and α-keto ester (–CO–COOR). This is an arylglyoxylate bearing a meta-methoxy substituent on the ring.
• 2D structure (verbal): A benzene ring with a methoxy group at the meta position relative to an acyl substituent. The acyl substituent is a glyoxylate fragment consisting of a ketone carbonyl directly attached to the ring and, alpha to it, a carboxylate ester (ethyl). No stereogenic centers; planar conjugated aryl–dicarbonyl system.
• Conjugation: Extended π-conjugation across the aryl ring and the aryl–carbonyl bond; the α-dicarbonyl (keto–ester) enables resonance stabilization and characteristic electrophilicity at the keto carbonyl.

Notes

• Identity fields not provided in Product Data (full InChI, exact SMILES) should be verified on the item’s CoA/Spec Sheet for regulatory and registration purposes.

Synthetic Utility

Functional handles and reactivity (literature)

• Dual carbonyl electrophilicity: The aryl-conjugated keto carbonyl is the primary site for 1,2-addition; the ester carbonyl participates in acylation/transesterification under stronger conditions.
• Enolizable α-position: Though deactivated by adjacent carbonyls, base can induce limited enolization enabling aldol-type couplings or Knoevenagel condensations with active methylenes.
• Chemoselective reductions: Access to mandelate esters (reduction of the ketone only) vs. diols or alcohol–ester pairs under stronger conditions; asymmetric reductions deliver chiral centers adjacent to the aryl ring.
• Olefination platform: Wittig/HWE olefination of the keto carbonyl provides styrenyl or acrylate-type products while leaving the ester intact for subsequent diversification.
• Umpolung/annulation: NHC catalysis leverages the α-dicarbonyl to form acyl anion equivalents, enabling benzoin- or Stetter-type products.

Strategic value

• The m-OMe substituent tunes electronics and offers a retrievable handle (e.g., BBr3-mediated demethylation to phenol for further coupling or ether formation). The ester can be saponified to the corresponding acid or swapped (Me/Pr/iPr) via transesterification.

Downstream elaborations

• Convert to α-ketoamides (amide coupling at the ester) for peptide-adjacent motifs.
• Perform aryl functionalization (nitration, halogenation on suitably protected derivatives) followed by cross-couplings to build libraries.

Practical tips

• Control moisture/base to prevent self-condensation or hydrolysis. Use low temperatures for highly reactive nucleophiles to maintain chemoselectivity.

Target Specificity

Not applicable. This product is a small-molecule synthetic intermediate and not an antibody, enzyme, or targeted biological reagent. No antigen/epitope, species reactivity, clone, or isotype information applies.

Perguntas frequentes

What is the purity of this product?

This product is supplied at ≥95% purity (chemical assay). Lot-specific values are stated on the Certificate of Analysis.

How should this product be stored?

Store at room temperature.

What are the CAS number, molecular formula and molecular weight?

The CAS Number is 86358-29-4, the molecular formula is C11H12O4, and the molecular weight is 208.22 g/mol. InChIKey DWLYVLJKLZPOAW-UHFFFAOYSA-N.

What documentation is provided?

Available product documentation, including Certificates of Analysis (COA), Safety Data Sheets (SDS), and specification sheets, is shown in the product document area. Document availability and access follow the current site policy.