Ethyl 2-Methyl-4-nitrobenzoate - ≥97% , CAS No.62621-10-7

CAS: 62621-10-7 Cat. No.: E1008490 Formula: C₁₀H₁₁NO₄ Peso molecolare: 209.201 PubChem CID: 21345698

GRADE & PURITY ≥97%

Storage

Room temperature

Specifications

Specifiche e purezza

≥97%

Condizioni di conservazione di stoccaggio

Room temperature

Purezza

≥97%

Nomi e identificatori

• Sorrisi canonici: CCOC(=O)C1=C(C=C(C=C1)[N+](=O)[O-])C
• IUPAC Name: ethyl 2-methyl-4-nitrobenzoate
• InChIKey: RMCICYWZZMDLLO-UHFFFAOYSA-N
• INCHI: 1S/C10H11NO4/c1-3-15-10(12)9-5-4-8(11(13)14)6-7(9)2/h4-6H,3H2,1-2H3
• Isomeri SMILES: CCOC(=O)C1=C(C=C(C=C1)[N+](=O)[O-])C
• PubChem CID: 21345698
• Peso molecolare: 209.201

Taxonomic Classification

Taxonomy Tree

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

• Kingdom: Organic compounds
• Superclass: Benzenoids
• Classe: Benzene and substituted derivatives
• Subclass: Benzoic acids and derivatives
• Intermediate Tree Nodes: Not available
• Direct Parent: Nitrobenzoic acids and derivatives
• Alternative Parents: Benzoic acid esters Nitrotoluenes Nitrobenzenes Nitroaromatic compounds Benzoyl derivatives Carboxylic acid esters Propargyl-type 1,3-dipolar organic compounds Organic oxoazanium compounds Organooxygen compounds Organonitrogen compounds Organic salts Organic oxides Hydrocarbon derivatives Organic cations
• Molecular Framework: Aromatic homomonocyclic compounds
• Substituents: Nitrobenzoate - Benzoate ester - Nitrobenzene - Nitrotoluene - Nitroaromatic compound - Benzoyl - Toluene - Carboxylic acid ester - C-nitro compound - Organic nitro compound - Allyl-type 1,3-dipolar organic compound - Organic oxoazanium - Carboxylic acid derivative - Propargyl-type 1,3-dipolar organic compound - Organic 1,3-dipolar compound - Organic oxygen compound - Organooxygen compound - Organonitrogen compound - Hydrocarbon derivative - Organic oxide - Organic nitrogen compound - Organic salt - Organic cation - Aromatic homomonocyclic compound
• Descrizione: This compound belongs to the class of organic compounds known as nitrobenzoic acids and derivatives. These are compounds containing a nitrobenzoic acid moiety, which consists of a benzene ring bearing both a carboxylic acid group and a nitro group on two different ring carbon atoms.
• 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: 209.200 g/mol
• XLogP3: 2.300
• Hydrogen Bond Donor Count: 0
• Hydrogen Bond Acceptor Count: 4
• Rotatable Bond Count: 3
• Exact Mass: 209.069 Da
• Monoisotopic Mass: 209.069 Da
• Topological Polar Surface Area: 72.100 Ų
• Heavy Atom Count: 15
• Formal Charge: 0
• Complexity: 248.000
• 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 antibody/assay protocols are associated with this small-molecule building block. For practical use, see Reaction Conditions and Application notes in Reaction & Applications and Synthetic Utility.

Biological Roles

This compound is a synthetic aromatic nitro ester and is not known as a natural metabolite or cofactor.

• General context (literature; not item-specific)
  • Nitroaromatic esters are typically xenobiotic to biological systems. If converted to the corresponding aniline via reduction, the aniline derivatives may engage in further biotransformations (e.g., N-acetylation, glucuronidation), but such behavior is highly structure-dependent.
  • The benzoate ester motif is broadly encountered in profragrances and proesters; however, Ethyl 2-Methyl-4-nitrobenzoate itself has no established physiological role.
• Practical implication for researchers
  • Use strictly for in vitro chemical synthesis or materials research as indicated; any biological testing should be preceded by appropriate hazard, stability, and solubility assessments and institutional approvals.

No clinical or therapeutic claims are made or implied for this product.

Buffer Applications

Not typically applicable. Ethyl 2-Methyl-4-nitrobenzoate is a neutral, hydrophobic organic building block and is not used to make aqueous biological buffers. For practical laboratory use with this compound, see the sections on Solvent Selection, Reaction & Applications, and Synthetic Utility.

Green Alternatives

The substrate itself is a specialty building block; green considerations focus on solvent/catalyst choices for its preparation and subsequent transformations.

• Greener solvent choices (general)

  • Prefer ethyl acetate, 2-MeTHF, CPME, IPA, or ethanol instead of chlorinated solvents for workup and reactions when feasible.
  • Use heptane in place of hexane for chromatography/crystallization to reduce n-hexane exposure concerns.

• Nitro reduction strategies (comparison)

  Greener approach | Typical conditions | Notes --- | --- | --- H2 with Pd/C in EtOH or EtOAc | rt–50 C, 1–5 bar H2 | Atom-efficient; avoid over-reduction of ester by controlling conditions. Iron powder/acid (Bechamp-like) | Fe, NH4Cl/H2O–EtOH, 60–90 C | Inexpensive, aqueous medium; generates iron oxide waste. Transfer hydrogenation (ammonium formate/Pd-C) | EtOH or water/EtOH, 25–60 C | Avoids compressed H2; benign byproducts (CO2, NH3).

• Ester transformations

  • Saponification in water/EtOH with NaOH minimizes organic solvent use; neutralize and extract product acid.
  • Enzymatic transesterification (lipases) under solvent-free or green solvents can provide selectivity and mild conditions.

• Energy and waste minimization

  • Favor catalytic over stoichiometric reagents; use continuous-flow hydrogenation to enhance safety and reduce solvent volume.
  • Apply solvent recycling (EtOAc, toluene) and crystallization-driven purifications to limit silica waste from chromatography.

Pharmaceutical Uses

• Item-specific pharmacopeial status: Not specified for this item; refer to CoA/Spec Sheet.
• General context (no therapeutic claims)
  • Role: This compound is best viewed as a synthetic intermediate for discovery chemistry and route scouting. The para-nitro group can be reduced to an aniline to access 4-amino-2-methyl benzoate derivatives relevant to medicinal chemistry SAR campaigns.
  • Excipient status: Aromatic nitro esters are not typical pharmaceutical excipients. No compendial excipient role is expected.
  • Process chemistry considerations: If used in preclinical route development, attention to nitro-reduction safety, control of residual catalysts (e.g., Pd), and purification strategies (crystallization vs. chromatography) is advised to meet research-quality expectations.

Physical Properties

• Item-specific specifications (this lot)
  • Appearance: Not specified for this item; refer to CoA/Spec Sheet.
  • Grade/Purity: Not specified for this item; refer to CoA/Spec Sheet.
  • Density, refractive index, UV cutoff, water/peroxide/metal limits: Not specified for this item; refer to CoA/Spec Sheet.
• Literature/General properties (for reference; not item specifications)
  • Molecular formula: C10H11NO4 (literature)
  • Molecular weight: ~209.20 g/mol (literature)
  • Physical state: Typically a low-melting solid or high-boiling liquid for analogous nitrobenzoate esters; exact MP/BP for this specific isomer should be confirmed from CoA or primary literature.
  • Polarity: Moderately polar, aprotic; strong π-system with an electron-withdrawing nitro and an ester carbonyl.
  • Solubility (qualitative): Expected to be sparingly soluble in water and freely soluble in common organic solvents (EtOAc, DCM, THF, toluene, acetone, acetonitrile, alcohols) based on functional group profile; confirm experimentally.
  • Acid/base behavior: No titratable basic nitrogen (nitro is nonbasic). Ester carbonyl is non-ionizable under neutral conditions; undergoes hydrolysis under strong acid/base.
  • Partitioning: Aromatic nitro esters generally exhibit moderate logP; exact value should be obtained from QSAR/database if needed for method development.

Quality and Grades

• Item-specific details
  • Grade/Purity: Not specified for this item; refer to CoA/Spec Sheet.
  • Stabilizers/Inhibitors: Not specified for this item; refer to CoA/Spec Sheet.
• Guidance on interpreting grades for this compound class (general)
  • Research grade vs. analytical/HPLC grade: For building-block esters like this nitrobenzoate, research grade often suffices for synthesis. If using in trace-sensitive catalysis or analytical method development, an analytical or HPLC grade material (lower UV background, tighter limits on residual solvents and metals) can be advantageous.
  • Water and acid/base impurities can accelerate ester hydrolysis or affect catalytic reductions; verify Karl Fischer and acid value on CoA when process robustness is critical.
  • Metals: If downstream steps involve Pd- or Ni-catalyzed coupling after nitro reduction and further derivatization, low metal background is beneficial. Check CoA or request a low-metals specification when needed.
  • Identity confirmation: Typical QC includes 1H/13C NMR (distinct ethyl quartet/triplet, methyl singlet, aromatic pattern), IR (strong C=O ~1730 cm−1; NO2 asymmetric/symmetric stretches), MS (M+), and HPLC purity.
  • Batch traceability: Use the SKU (E1008490) and CAS to align CoA with your lot; retain samples for reference chromatography where GMP-like documentation is required (for research only).

Reaction and Applications

Ethyl 2-Methyl-4-nitrobenzoate is a versatile aromatic building block combining an orthogonal nitro handle and an ester function.

• Transformations leveraging the nitro group
  • Reduction to an aniline (literature): H2/Pd-C, H2/Raney Ni, or transfer hydrogenation (e.g., Fe/AcOH, SnCl2/HCl) to give 2-methyl-4-aminobenzoate ethyl ester. This enables subsequent acylation, sulfonylation, diazotization, or Sandmeyer transformations after converting to the anilinium diazonium salt.
  • Nucleophilic aromatic substitution (SNAr): The single para-nitro on a relatively unsubstituted ring is generally insufficient for SNAr without additional activation; consider reduction first or install further electron-withdrawing groups.
• Transformations at the ester
  • Hydrolysis to the corresponding acid (saponification or acidic hydrolysis); subsequent coupling via amide bond formation (EDC/HOBt, HATU) or conversion to acid chlorides.
  • Transesterification to other alkyl esters under acid catalysis (Fischer–Speier) or with alkoxides under equilibrating conditions.
  • Reduction to benzyl alcohol derivatives (e.g., DIBAL-H to the aldehyde at low temperature; LiAlH4/Red-Al to the primary alcohol) while preserving the aromatic nitro only under carefully chosen conditions; note that strong hydrides may also reduce –NO2.
• Aromatic reactivity and directing effects
  • The nitro group is strongly deactivating and meta-directing; the ester is also deactivating/meta-directing. The ortho methyl is weakly activating/ortho–para directing but sterically hinders adjacent positions. Electrophilic substitution is therefore disfavored; most functionalization proceeds via reduction of –NO2 or cross-coupling after further derivatization.
• Use cases
  • Intermediate for dyes/pigments, agrochemical scaffolds, and medicinal chemistry libraries where para-aniline or para-heteroaryl motifs relative to a benzoate are desired.
  • Fragment for convergent synthesis: ester enables late-stage coupling; nitro serves as a masked amine handle.

Reaction Conditions

General literature guidance (for planning; verify with small-scale trials):

• Nitro reduction to aniline
  • H2/Pd-C (5–10 wt% Pd, 5–10 mol% Pd): EtOH, EtOAc, or MeOH; 1–5 bar H2; 20–50 C; 1–6 h. Monitor to avoid ester hydrogenolysis. Add base (e.g., Et3N) if ammonium salt formation impedes solubility.
  • Fe/NH4Cl (aqueous EtOH): Fe powder (3–6 equiv), NH4Cl (2–3 equiv), 60–80 C, 2–6 h; work up by basification and extraction.
  • SnCl2·2H2O/HCl: MeOH or EtOH, reflux, 1–4 h; quench with base, extract; generates tin waste.
• Ester hydrolysis (saponification)
  • NaOH (1–2 M) in MeOH/H2O (1:1–3:1), 20–50 C; 1–6 h; acidify to pH ~2 and isolate the acid by filtration or extraction.
  • Acidic hydrolysis: Aqueous HCl (3–6 M), dioxane/H2O or AcOH/H2O, reflux; slower but avoids base-sensitive substituents elsewhere.
• Transesterification
  • Fischer ester exchange: ROH (neat or solvent), catalytic H2SO4/p-TsOH, Dean–Stark if needed, 60–120 C depending on alcohol; remove EtOH to drive equilibrium.
• Ester reductions
  • DIBAL-H (1.0–1.5 equiv) in toluene or CH2Cl2, −78 to −20 C; quench carefully to give the aldehyde; minimize over-reduction and avoid concurrent nitro reduction.
  • LiAlH4 or Red-Al: THF, 0–25 C, 1–3 h; typically reduces both ester and nitro; use only when an aniline–benzyl alcohol outcome is desired.
• Workup/monitoring tips
  • TLC on silica with hexanes/EtOAc 3:1 to 1:1 often resolves starting material and products; UV-active with strong response; nitro group enhances UV.
  • Avoid prolonged exposure to strong base at elevated temperature to limit transesterification/saponification if undesired.

Note: Conditions are general literature ranges for nitrobenzoate esters and should be optimized for this specific isomer.

Safety and Handling

• Item-specific hazard data
  • GHS classification, signal word, pictograms, H-statements: Not specified for this item; refer to SDS.
• General safety guidance for aromatic nitro esters (literature; not a substitute for SDS)
  • Hazards: May cause skin/eye irritation and respiratory tract irritation. Nitroaromatics can have higher toxicity than unsubstituted aromatics; avoid inhalation and skin contact. Combustible organic compound.
  • PPE: Lab coat, safety glasses or goggles, appropriate chemical-resistant gloves (e.g., nitrile). Work in a fume hood to avoid inhalation exposure.
  • Handling: Avoid heat, sparks, and open flame. Prevent contact with strong bases and strong acids except when controlled for synthesis (hydrolysis risk). Avoid prolonged exposure to strong reducing agents unless intended (nitro reduction risk).
  • Incompatibilities: Strong oxidizers (risk of exotherm), strong bases/acids (ester cleavage), potent reducing agents or catalytic hydrogenation conditions (reduce –NO2 to –NH2).
  • First aid (overview): If inhaled—move to fresh air, seek medical advice. Skin/eye contact—rinse with water for several minutes; remove contaminated clothing; seek medical advice if irritation persists. If ingested—rinse mouth; do not induce vomiting; seek medical attention. Always follow SDS-specific instructions.
  • Spill/Disposal: Absorb small spills with inert material (vermiculite, sand). Dispose according to local regulations. Prevent entry into drains.
  • Fire-fighting: Use CO2, dry chemical, or foam. Combustion can produce CO/CO2 and nitrogen oxides; firefighters should wear SCBA.

Solvent Selection

• Polarity profile (general)
  • Moderately polar, aprotic aromatic ester; good solubility expected in EtOAc, DCM, THF, toluene, acetone, acetonitrile; limited solubility in water.
• Choosing solvents by task
  • Workup/crystallization: EtOAc/hexanes or toluene/heptane mixes are commonly used for nitroaromatic esters. Alcohols (EtOH/IPA) may dissolve well hot and crystallize upon cooling if the compound is solid.
  • Chromatography: Normal-phase silica with hexanes/EtOAc or heptane/EtOAc gradients separates nitrobenzoate esters cleanly. For greener methods, consider cyclopentyl methyl ether (CPME) or 2-MeTHF with ethyl acetate modifiers.
  • Reactions: Reduction of the nitro group proceeds in EtOH, EtOAc, MeOH, or acetic acid with hydrogenation catalysts; base- or acid-catalyzed hydrolysis typically uses MeOH/H2O or dioxane/H2O; transesterification in toluene or xylene with azeotropic water removal.
• Comparison snapshot (general)
  • EtOAc vs DCM: EtOAc is greener and supports ester solubility; DCM offers faster chromatography but higher environmental burden.
  • THF/2-MeTHF: Good solvency for catalytic reductions and nucleophilic steps; 2-MeTHF offers improved sustainability and water immiscibility.
  • Toluene/heptane: Useful for crystallizations and high-temperature steps; limited polarity can suppress side hydrolysis.

Storage and Reconstitution

• Item-specific storage and shipping
  • Storage: Room temperature (per Product Data). Protect from moisture and strong light to preserve ester integrity and minimize any photochemical nitro degradation.
  • Shipped in: Not specified for this item; refer to CoA/Spec Sheet.
• Handling and aliquoting (general guidance)
  • Keep container tightly closed. If long-term storage is anticipated, consider storing in an amber bottle with desiccant and headspace of inert gas (N2/Ar), especially if frequent opening is expected.
  • If solid: Gently warm to ambient temperature before opening to avoid condensation. If caking occurs, break up under dry conditions.
  • If liquid: Inspect for crystallization or phase separation; warm gently and swirl to homogenize before dispensing.
• Solution preparation (general)
  • Prepare stock solutions in dry organic solvents (e.g., EtOAc, DCM, THF, MeOH, ACN) as needed. Use anhydrous solvents for moisture-sensitive steps. Label solutions with solvent, concentration, and date; many solutions are stable for days to weeks at 2–8 C in sealed vials, but verify stability experimentally.
• Stability notes
  • Avoid prolonged exposure to strong acids/bases which can hydrolyze the ester. Strong reducing conditions will convert the nitro to an amine. Always consult the latest CoA/SDS for any additional storage notes specific to your lot.

Structure and Identity

Brief overview: Ethyl 2-Methyl-4-nitrobenzoate is an aromatic nitro ester bearing an ortho-methyl substituent relative to the benzoate carbonyl and a para-nitro group.

• Item-specific (from Product Data)
  • Product name: Ethyl 2-Methyl-4-nitrobenzoate
  • CAS: 62621-10-7
  • CID: 21345698
  • InChIKey: 319984 (as provided)
  • Storage: Room temperature
  • Research use: For research use only
• Literature/Computed identifiers and features (for reference; not item specifications)
  • Molecular formula (literature): C10H11NO4
  • Molecular weight (literature): ~209.20 g/mol
  • Representative SMILES (literature): CCOC(=O)c1cc(N+[O-])cc(C)c1
  • Functional groups: aromatic ring, ethyl benzoate ester (–CO2Et), nitro (–NO2) para to the ester, methyl ortho to the ester.
  • 2D structure description: A benzene core with a carboxylate ethyl ester at C1; a methyl at C2 (ortho) introducing modest steric bulk; and a nitro at C4 (para) strongly deactivating and meta-directing for further EAS.
  • Stereochemistry: None (achiral, no stereocenters).

Synthetic Utility

• Orthogonal handles
  • Nitro group (masked amine): Gateway to anilines via reduction; subsequent diversification through acylation, sulfonylation, urea formation, Buchwald–Hartwig coupling (after diazotization → halo), or azo chemistry (diazonium coupling).
  • Ethyl ester: Convertible to carboxylic acid (hydrolysis), amides (via coupling), aldehydes/alcohols (selective reduction), or other esters (transesterification).
• Strategic applications
  • Late-stage amine unveiling: Keep the nitro intact through multi-step sequences, then reduce to the aniline at the end to minimize protection/deprotection steps.
  • Divergent synthesis: From a single intermediate, generate acid (hydrolysis), amide (coupling), alcohol (reduction), and aniline (reduction) branches to build libraries.
  • Steric/electronic tuning: Ortho-methyl subtly perturbs torsion of the aryl–CO bond, affecting reactivity and physical properties (e.g., crystallinity), and can influence regioselectivity in downstream functionalizations.
• Named reaction linkages (literature)
  • Bechamp/ catalytic hydrogenation for –NO2 → –NH2.
  • DIBAL-H partial reduction for –CO2Et → –CHO.
  • HATU/EDC-mediated amidation after hydrolysis to the acid.
  • Diazotization/Sandmeyer sequences after aniline formation to introduce Cl/Br/CN at the para position relative to the ester.
• Protecting-group compatibility
  • Nitro group is robust to many electrophilic conditions; avoid strong nucleophilic or highly reducing environments if preservation is required.
  • Ester tolerates many neutral conditions but is labile to strong acids/bases and nucleophiles.

Target Specificity

Not applicable. This product is a small-molecule chemical building block and does not possess biological target specificity parameters (e.g., antigen, epitope, clone, isotype).