ethyl 4-dimethylaminobenzoylformate - Reagent grade , CAS No.41116-24-9

CAS: 41116-24-9 Cat. No.: E479053 Formula: C₁₂H₁₅NO₃ Peso molecolare: 221.256 Numero EC: 675-583-3

GRADE & PURITY Reagent Grade

Synonyms

ETHYL 4-(N,N-DIMETHYLAMINO)BENZOYLFORMATE | NSC525211 | NSC-525211 | benzeneacetic acid, 4-(dimethylamino)-.alpha.-oxo-, ethyl ester | Ethyl 4-dimethylaminobenzoylformate | ethyl [4-(dimethylamino)phenyl](oxo)acetate | Ethyl 2-(4-(dimethylamino)phenyl)-2-

Storage

Room temperature

Specifications

Sinonimi

ETHYL 4-(N,N-DIMETHYLAMINO)BENZOYLFORMATE | NSC525211 | NSC-525211 | benzeneacetic acid, 4-(dimethylamino)-.alpha.-oxo-, ethyl ester | Ethyl 4-dimethylaminobenzoylformate | ethyl [4-(dimethylamino)phenyl](oxo)acetate | Ethyl 2-(4-(dimethylamino)phenyl)-2-

Specifiche e purezza

Reagent grade

Condizioni di conservazione di stoccaggio

Room temperature

Grado

Reagent Grade

Nomi e identificatori

• Sorrisi canonici: CCOC(=O)C(=O)C1=CC=C(C=C1)N(C)C
• IUPAC Name: ethyl 2-[4-(dimethylamino)phenyl]-2-oxoacetate
• InChIKey: IEQWYUJSPBZCTP-UHFFFAOYSA-N
• INCHI: 1S/C12H15NO3/c1-4-16-12(15)11(14)9-5-7-10(8-6-9)13(2)3/h5-8H,4H2,1-3H3
• Isomeri SMILES: CCOC(=O)C(=O)C1=CC=C(C=C1)N(C)C
• Peso molecolare: 221.256
• Reaxy-Rn: 2644634
• Reaxys-RN_link_address: https://www.reaxys.com/reaxys/secured/hopinto.do?context=S&query=IDE.XRN=2644634&ln=

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: Dialkylarylamines Aryl ketones Aniline and substituted anilines Alpha-keto acids and derivatives Carboxylic acid esters Amino acids and derivatives Monocarboxylic acids and derivatives Organopnictogen compounds Organic oxides Hydrocarbon derivatives
• Molecular Framework: Aromatic homomonocyclic compounds
• Substituents: Benzoyl - Aniline or substituted anilines - Dialkylarylamine - Aryl ketone - Tertiary aliphatic/aromatic amine - Alpha-keto acid - Keto acid - Amino acid or derivatives - Carboxylic acid ester - Tertiary amine - Ketone - Carboxylic acid derivative - Monocarboxylic acid or derivatives - Organic nitrogen compound - Organonitrogen compound - Organooxygen compound - Hydrocarbon derivative - Organic oxide - Carbonyl group - Organopnictogen compound - Organic oxygen compound - Amine - Aromatic homomonocyclic compound
• Descrizione: 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

Proprietà chimiche e fisiche

• Peso molecolare: 221.250 g/mol
• XLogP3: 2.100
• Hydrogen Bond Donor Count: 0
• Hydrogen Bond Acceptor Count: 4
• Rotatable Bond Count: 5
• Exact Mass: 221.105 Da
• Monoisotopic Mass: 221.105 Da
• Topological Polar Surface Area: 46.600 Ų
• Heavy Atom Count: 16
• Formal Charge: 0
• Complexity: 255.000
• 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

No assay or bioanalytical protocols are provided for this small-molecule reagent. For synthetic uses, see Reaction Conditions and Synthetic Utility for general, literature-informed procedures. Always optimize conditions for your specific substrate set and scale.

Biological Roles

This material is a synthetic organic intermediate and photoreactive electrophile. It is not known as a natural metabolite or biochemical cofactor.

• No endogenous biological role is established for aryl glyoxylate esters with para-dimethylamino substitution (general knowledge).
• The tertiary amine is not expected to be protonated at neutral pH to a biologically active ammonium under typical lab conditions; however, protonation can occur in acidic environments.
• Any interactions with biomolecules should be considered nonspecific electrophilic or photochemical in nature rather than target-directed.

Research Use Note: For research use only (from Product Data). Not for human or veterinary use.

Buffer Applications

Not typically applicable. Ethyl 4-dimethylaminobenzoylformate is a hydrophobic, reactive aryl ester and is not used as a buffering agent. For work in aqueous media, it is usually dissolved in an organic co-solvent (e.g., MeCN, DMSO) before dilution or biphasic operations. See Solvent Selection and Reaction & Applications for more relevant guidance.

Green Alternatives

Selection of greener options centers on solvent choice and activation mode rather than on changing the substrate, which is a specialized electrophile.

Greener solvent choices (general guidance):

• Replace chlorinated solvents (DCM, CHCl3) with ethyl acetate, 2-MeTHF, MeCN, or cyclopentyl methyl ether (CPME) where feasible.
• THF can be substituted by 2-MeTHF (bio-derived, higher boiling, forms fewer peroxides) for many organocatalytic and photoredox applications.

Comparison (general, literature-informed):

• DCM vs EtOAc/2-MeTHF:
  • Greenness: EtOAc/2-MeTHF superior in EHS metrics.
  • Reactivity: Similar for many nucleophilic additions; monitor for rate changes due to polarity differences.
• MeCN vs EtOH/MeOH (photoredox):
  • Greenness: Alcohols greener but can participate in hydrogen-atom transfer or transesterification; use mixed solvents to balance.

Process-intensification options:

• Photochemistry under LEDs (blue/green) to minimize energy input relative to UV lamps.
• Flow photochemistry for improved light utilization and thermal control.

Note: Substrate substitution is generally not possible without altering target outcomes; if a less hazardous electrophile is acceptable, simple aryl esters or activated acid derivatives may substitute, but with altered chemoselectivity.

Pharmaceutical Uses

No pharmacopeial monograph or excipient status is provided. This compound is not used as a formulated drug or common excipient; rather, it may serve as a synthetic intermediate or photoreactive building block in R&D settings.

• Potential roles in process R&D (general): • Precursor to α-hydroxy esters and 1,2-dicarbonyl frameworks found in intermediates.
  • Photochemical acylation partner enabling late-stage functionalization in discovery workflows.

Regulatory and quality notes:

• Grade/Purity: Reagent Grade (from Product Data). For GMP or clinical manufacturing, suitability must be independently established; this listing is for research use only.
• Residual solvents, elemental impurities, and low-UV background: Not specified for this item; refer to CoA/Spec Sheet.

No therapeutic or clinical claims are made or implied.

Physical Properties

Only limited item-specific physical data are provided for this catalog entry. Do not treat the following as specifications; consult CoA/SDS for authoritative values.

• Appearance: Not specified for this item; refer to CoA/Spec Sheet.
• Boiling point: Not specified for this item; refer to CoA/Spec Sheet.
  • Literature: aryl glyoxylate esters are typically high-boiling liquids or low-melting solids; thermal sensitivity and propensity for light-induced reactions should be considered.
• Melting point: Not specified for this item; refer to CoA/Spec Sheet.
• Density (20–25 °C): Not specified for this item; refer to CoA/Spec Sheet.
• Refractive index: Not specified for this item; refer to CoA/Spec Sheet.
• Solubility:
  • Expected (general chemistry): miscible with common organic solvents (e.g., dichloromethane, THF, acetonitrile, ethyl acetate); low water solubility typical of aryl esters.
• LogP, pKa: Not specified for this item; refer to CoA/Spec Sheet.
  • General note: the para-dimethylamino group increases polarity and may slightly increase basicity of the ring nitrogen (non-protonated tertiary amine under neutral conditions).

Important note: Light and heat can induce side reactions (photochemistry, decomposition) in aryl glyoxylates bearing donor substituents; handle under subdued light when precise composition is critical.

Quality and Grades

• Grade: Reagent Grade (from Product Data)

What Reagent Grade implies:

• Intended for general laboratory and synthesis use. Typical expectations include good chemical purity suitable for most synthetic and analytical workflows. It is not necessarily optimized for chromatographic background (unlike HPLC/LC–MS grades) nor for biocompatibility (unlike cell culture grades).
• UV cutoffs, trace-metal limits, water/peroxide content, stabilizer content: Not specified for this item; refer to CoA/Spec Sheet.

Stabilizers and additives:

• No stabilizer information is provided for this catalog entry. For light-sensitive aryl glyoxylates, suppliers may package in amber glass and under inert headspace; verify on the CoA if this is critical to your workflow.

Batch-specific documentation:

• For exact assay/purity, residual solvents, and impurity profile, consult the Certificate of Analysis provided with your lot. If low-UV background or specific metals limits are required (e.g., photoredox catalysis, pharmaceutical intermediates), contact Technical Support to confirm suitability.

Reaction and Applications

Ethyl 4-dimethylaminobenzoylformate is a versatile aryl glyoxylate electrophile. The para-dimethylamino donor enhances visible-light absorption and modulates the LUMO of the di-carbonyl system, enabling a wide range of transformations.

• Photochemistry and photoredox: • Acyl radical generation under visible-light photoredox catalysis (e.g., Ir/Ru photocatalysts, organic dyes), enabling acylation of alkenes, heteroarenes, and radical cascades (literature).
  • Paternò–Büchi [2+2] photocycloadditions with alkenes to furnish oxetanes from excited aryl glyoxylates (literature).
  • Photoenolization pathways can be exploited in intramolecular cyclizations (substrate-dependent; literature).
• Organocatalysis: • Enamine-catalyzed α-additions of aldehydes/ketones to aryl glyoxylates to form α-substituted α-keto esters; chiral secondary amines (proline-derived) enable enantioinduction (literature).
  • NHC catalysis (benzoin/Stetter manifolds) using aryl glyoxylates as electrophilic partners to provide acyloin-type products or 1,4-dicarbonyls (literature).
• Nucleophilic additions and reductions: • 1,2-addition of organometallic reagents (RMgX, R2CuLi) to the glyoxylate carbonyl generating α-hydroxy esters after quench (literature).
  • Chemoselective reductions (e.g., NaBH4, DIBAL-H) can access α-hydroxy esters or diols depending on conditions (literature).
• Synthesis enabling features: • Strongly activated carbonyl (adjacent to another carbonyl) offers high reactivity at the acyl center while the ester persists under moderately basic conditions.
  • The para-NMe2 group can be leveraged as a spectroscopic handle (UV–Vis) and modulates regio-/chemoselectivity in electrophotocatalytic settings.

Practical tips:

• Work under inert atmosphere for base- or metal-mediated couplings.
• Control light exposure; wrap vessels in foil unless photochemistry is intended.
• Use dry, oxygen-free solvents for radical or organometallic protocols.

Reaction Conditions

The following are general, literature-informed guidelines for aryl glyoxylate reactions. They are not item-specific specifications.

• Organometallic 1,2-additions:
  • Solvent: dry THF, Et2O, or toluene.
  • Temp: −78 to 0 °C (for RLi/RMgX); 0 to rt (for cuprates).
  • Quench: saturated NH4Cl or aqueous acid to furnish α-hydroxy esters.
  • Notes: control equivalents to limit over-reduction or ester cleavage.
• Enamine-catalyzed α-functionalization:
  • Catalyst: 10–20 mol% chiral secondary amine (e.g., proline-derived), with acid co-catalyst.
  • Solvent: toluene, DCM, or MeCN; dry conditions.
  • Temp: 0 °C to rt.
  • Time: 2–24 h depending on nucleophile; monitor by TLC/LC–MS.
• NHC-catalyzed benzoin/Stetter-type:
  • Catalyst: 5–20 mol% NHC precursor (triazolium/imiazolium) + base (DBU, KOtBu).
  • Solvent: THF, toluene, DCM.
  • Temp: 0 °C to rt.
  • Atmosphere: inert, moisture-free.
• Photoredox acylations:
  • Photocatalysts: Ir(ppy)3, Ru(bpy)3Cl2, or organic dyes (eosin Y, 4CzIPN).
  • Light: blue to green LEDs; shield from ambient light during setup.
  • Solvent: MeCN, MeOH/MeCN, acetone; O2 exclusion often beneficial.
  • Temp: rt; typical times 2–16 h.
  • Additives: Hantzsch esters or amines as reductants where needed.

Workup/purification:

• Standard aqueous quench, extraction with EtOAc or DCM, drying over MgSO4/Na2SO4, and silica gel chromatography. Protect from strong light during purification to minimize on-column photoreactions.

Safety and Handling

GHS hazards and pictograms are not specified in the Product Data for this item. Always review the SDS for authoritative classification and first-aid instructions.

• GHS classification, signal word, H-statements, pictograms: Not specified for this item; refer to SDS.
• Likely hazards (general for aryl glyoxylate esters; informational only): may cause skin/eye irritation; harmful if swallowed; combustible liquid. Avoid inhalation of vapors and contact with skin and eyes.
• Personal protective equipment (PPE): lab coat, safety glasses or splash goggles, and appropriate chemical-resistant gloves (e.g., nitrile). Use in a fume hood.
• Handling guidance: • Minimize exposure to strong light sources; para-dimethylamino aryl glyoxylates can undergo photochemical reactions.
  • Exclude moisture and strong nucleophiles when purity is critical (susceptible to nucleophilic addition/transesterification).
  • Avoid strong acids/bases and strong oxidizers; tertiary amine function can be protonated or oxidized.
• Incompatibilities (general): strong acids/bases, reducing/oxidizing agents, and reactive metals.
• First aid (overview; consult SDS):
  • Inhalation: move to fresh air; seek medical attention if symptoms persist.
  • Skin contact: wash with soap and water; remove contaminated clothing.
  • Eye contact: rinse cautiously with water for several minutes; seek medical attention.
  • Ingestion: rinse mouth; do not induce vomiting; seek medical attention.
• Spill/Fire response: absorb small spills with inert material; dispose per regulations. For fire, use CO2, dry chemical, or foam; cool containers with water spray.

Solvent Selection

This compound is a moderately polar, aprotic aryl ester with a tertiary amine donor and a di-carbonyl acceptor (glyoxylate). It dissolves readily in most common organic solvents.

• Miscibility/solubility (general): • Readily soluble: dichloromethane, chloroform, THF, acetonitrile, toluene, ethyl acetate, acetone, DMF, DMSO.
  • Poorly soluble: water (typical for aryl esters).
• Polarity profile: push–pull chromophore; dielectric compatibility from medium (EtOAc, toluene) to high-polarity solvents (MeCN, DMF). Choice often guided by the reaction mechanism (polar transition states benefit from higher dielectric media).
• When to choose which solvent: • Nucleophilic additions (enamine/organocatalysis): toluene, DCM, or THF for reactivity/selectivity balance.
  • Photoredox acylations: MeCN or MeOH/MeCN mixtures are common for catalyst solubility and oxygen control.
  • NHC-catalyzed benzoin/Stetter-type couplings: dry THF, toluene, or DCM under inert atmosphere.

Comparison notes (general):

• Versus simpler aryl benzoates, the glyoxylate is more electrophilic and tolerant of slightly more nucleophilic media, but is also more prone to side reactions in strongly basic alcohols (transesterification).
• Avoid protic strong bases that may trigger decomposition; use non-nucleophilic bases (e.g., DIPEA, DBU) where appropriate.

Storage and Reconstitution

• Storage Conditions: Room temperature (from Product Data). For optimal longevity, store in a tightly closed container, protected from light (amber bottle) and moisture. If prolonged storage is expected, consider an inert headspace (N2/Ar).
• Shipped In: Not specified for this item; refer to CoA/Spec Sheet.
• Stability notes (general for aryl glyoxylates): • Sensitive to strong light; may undergo photochemical reactions—minimize exposure.
  • Avoid strong acids/bases and nucleophiles to prevent decomposition/transesterification.
  • If solidification/crystallization occurs upon cooling, warm gently to re-liquefy and homogenize before use.
• Reconstitution: Not applicable—delivered neat. If preparing stock solutions, use dry, oxygen-free solvent (e.g., MeCN, THF, DCM), and store aliquots in amber vials at 2–8 °C or at room temperature as compatible with your workflow. Bring to ambient temperature before opening to minimize condensation.

Research Use Note: For research use only (from Product Data).

Structure and Identity

Ethyl 4-dimethylaminobenzoylformate is an aryl glyoxylate (ethyl phenylglyoxylate derivative) bearing a para-dimethylamino donor on the ring, giving a push–pull aromatic ester useful in photochemical and nucleophilic addition chemistry.

• SKU: E479053
• Product Name: ethyl 4-dimethylaminobenzoylformate
• CAS: 41116-24-9
• PubChem CID: 352160 (literature)
• InChIKey: 138955 (from Product Data)
• SMILES: Not specified for this item; refer to CoA/Spec Sheet.
  • Literature SMILES (for reference only): CCOC(=O)C(=O)C1=CC=C(N(C)C)C=C1
• Molecular Formula: Not specified for this item; refer to CoA/Spec Sheet.
  • Literature (computed) formula: C12H15NO3
• Molecular Weight: Not specified for this item; refer to CoA/Spec Sheet.
  • Literature (computed) MW: ~221.26 g/mol

Structural features (descriptive):

• Aromatic ring para-substituted with a strong electron-donating dimethylamino group [–N(CH3)2].
• Glyoxylate motif: an acyl–carbonyl (benzoyl) adjacent to an ester carbonyl (–CO–CO2Et), rendering the carbonyl α-carbon highly electrophilic.
• Conjugated push–pull system (donor NMe2 to acceptor di-carbonyl) often associated with enhanced visible-light absorption relative to unsubstituted aryl glyoxylates.
• No stereocenters; planar aromatic core with two carbonyls in conjugation with the ring.

Synthetic Utility

Key functional groups and reactivity:

• Activated 1,2-dicarbonyl system (aryl glyoxylate) renders the acyl carbonyl highly electrophilic—amenable to 1,2-additions by soft/hard nucleophiles to produce α-hydroxy esters after workup.
• The ester carbonyl typically survives under conditions that selectively engage the acyl carbonyl, enabling stepwise diversification.
• The para-dimethylamino donor tunes electronics for visible-light excitation and can stabilize intermediates via resonance.

Representative transformations (literature):

• Organometallic additions (RMgX, RLi, R2CuLi) → α-hydroxy ester derivatives after aqueous quench.
• Enamine/organocatalytic additions of aldehydes/ketones → α-substituted α-keto esters, with potential enantioselectivity using chiral amines.
• NHC-catalyzed benzoin/Stetter-type couplings using aryl glyoxylates as electrophiles → acyloin adducts/1,4-dicarbonyls.
• Photoredox-mediated acyl radical formation → radical acylations of alkenes/heteroarenes.

Retrosynthetic value:

• Serves as a masked acyl cation equivalent; after addition and reduction, can unmask diverse carbonyl patterns.
• Ester handle allows orthogonal downstream manipulations (hydrolysis, reduction, amidation) without disturbing earlier-formed C–C bonds.

Target Specificity

Not applicable. This product is a small-molecule reagent, not a biological affinity reagent. No antigen/epitope, species reactivity, clone, or isotype information applies.