Methyl 4-(4-nitrophenoxy)benzoate - ≥95% , CAS No.21120-78-5

CAS: 21120-78-5 Cat. No.: M1026952 Fórmula: C₁₄H₁₁NO₅ Peso molecular: 273.240 Número CE: 140-971-9

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: COC(=O)C1=CC=C(C=C1)OC2=CC=C(C=C2)[N+](=O)[O-]
• IUPAC Name: methyl 4-(4-nitrophenoxy)benzoate
• InChIKey: PPRYORMDEJTYDQ-UHFFFAOYSA-N
• INCHI: 1S/C14H11NO5/c1-19-14(16)10-2-6-12(7-3-10)20-13-8-4-11(5-9-13)15(17)18/h2-9H,1H3
• Peso molecular: 273.240

Taxonomic Classification

Taxonomy Tree

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

• Kingdom: Organic compounds
• Superclass: Benzenoids
• Classe: Benzene and substituted derivatives
• Subclass: Diphenylethers
• Intermediate Tree Nodes: Not available
• Direct Parent: Diphenylethers
• Alternative Parents: Diarylethers Benzoic acid esters Nitrobenzenes Phenoxy compounds Phenol ethers Nitroaromatic compounds Benzoyl derivatives Methyl esters Propargyl-type 1,3-dipolar organic compounds Organic oxoazanium compounds Monocarboxylic acids and derivatives Organopnictogen compounds Organonitrogen compounds Organic oxides Hydrocarbon derivatives
• Molecular Framework: Aromatic homomonocyclic compounds
• Substituents: Diphenylether - Diaryl ether - Benzoate ester - Benzoic acid or derivatives - Nitrobenzene - Phenoxy compound - Benzoyl - Nitroaromatic compound - Phenol ether - Methyl ester - Organic nitro compound - Carboxylic acid ester - C-nitro compound - Organic 1,3-dipolar compound - Carboxylic acid derivative - Propargyl-type 1,3-dipolar organic compound - Ether - Monocarboxylic acid or derivatives - Allyl-type 1,3-dipolar organic compound - Organic oxoazanium - Organic oxide - Organopnictogen compound - Hydrocarbon derivative - Organic oxygen compound - Organonitrogen compound - Organooxygen compound - Organic nitrogen compound - Aromatic homomonocyclic compound
• Descrição: This compound belongs to the class of organic compounds known as diphenylethers. These are aromatic compounds containing two benzene rings linked to each other through an ether 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

Propriedades químicas e físicas

• Peso molecular: 273.240 g/mol
• XLogP3: 3.500
• Hydrogen Bond Donor Count: 0
• Hydrogen Bond Acceptor Count: 5
• Rotatable Bond Count: 4
• Exact Mass: 273.064 Da
• Monoisotopic Mass: 273.064 Da
• Topological Polar Surface Area: 81.400 Ų
• Heavy Atom Count: 20
• Formal Charge: 0
• Complexity: 338.000
• 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 vendor-tested biological application protocols are provided for this small-molecule reagent.

• General handling
  • Prepare stock solutions in DMSO, DMF, or EtOAc as required; filter through 0.2 µm PTFE for analytical use.
  • For synthetic steps, see Reaction Conditions for representative literature procedures.
• Recommended controls
  • Include solvent-only controls in biochemical assays if DMSO/DMF stocks are used.
  • Use UV at 254–280 nm for TLC/HPLC monitoring due to strong absorbance.

Biological Roles

• Item-specific biological data: Not specified for this item; refer to CoA/Spec Sheet. For research use only.
• General considerations (non-clinical)
  • This compound is a synthetic aromatic diaryl ether with a nitro group and an ester; it does not have a known endogenous biological role.
  • The nitro group can influence photophysical properties and electron distribution; derivatives after nitro reduction (anilines) are common motifs in ligands and probe scaffolds used in biochemical screening.
  • Strong UV absorption enables use as a tracer or internal standard in analytical method development (e.g., LC-UV optimization) when chemically compatible.
  • Potential utility as a haptenic building block after conversion to amine/acid for conjugation to biomolecules in immunochemistry workflows; any such uses require separate optimization and validation.
• No medical, diagnostic, or therapeutic claims are made for this material.

Buffer Applications

This is a neutral, water-insoluble aromatic compound and is not typically used as a buffer component.

• If dissolution into aqueous systems is required for assays, prepare concentrated stocks in DMSO or DMF and dilute into buffered media with attention to final cosolvent percentages (<1–2% v/v commonly targeted in biochemical assays).
• For pH control, use standard biological buffers (PBS, HEPES, Tris); this compound does not contribute buffering capacity.

Green Alternatives

• Solvent choices with greener profiles (general)

  • Replace DCM/CHCl3 with EtOAc, 2-MeTHF, CPME, or toluene where feasible (similar solubility for this aromatic ester/diaryl ether).
  • For polar reactions, consider MeCN or MeOH/EtOH as cosolvents instead of DMF/NMP; use water-tolerant catalysts when possible.

• Nitro reduction (greener options)

  • Catalytic hydrogenation (H2/Pd, H2/Pt) in EtOH or 2-MeTHF is often cleaner and generates water as the only byproduct, versus stoichiometric Fe or Sn salts that produce waste.
  • Employ transfer hydrogenation (e.g., ammonium formate/Pd-C) to avoid pressurized hydrogen when appropriate.

• Hydrolysis/activation of the ester

  • Use aqueous base in water/EtOH mixtures to minimize organic solvent; conduct solvent switch to greener media (EtOAc) for workup and crystallization.

• Comparison snapshot (general guidance)

  | Operation | Conventional | Greener swap | Trade-offs | |---|---|---|---| | Extraction | DCM | EtOAc/MTBE | Slightly lower capacity; improved safety | | Reaction solvent (polar) | DMF/NMP | MeCN/MeOH/H2O (when compatible) | Solubility, rate may drop | | Hydrogenation | CH3OH/DCM | EtOH/2-MeTHF | Catalyst wetting/pressure control needed |

• Item-specific environmental metrics: Not specified for this item; refer to CoA/SDS for any available EHS data.

Pharmaceutical Uses

• Item-specific pharmacopeial status: Not specified for this item; refer to CoA/Spec Sheet.
• General formulation context (non-clinical)
  • Not known as a pharmacopeial excipient. Primarily a synthetic intermediate for discovery chemistry and materials research.
  • The strong UV chromophores make it useful as an analytical probe or impurity standard during process development when structurally relevant.
  • Derivatives after functional group interconversion (acid, amide, aniline) may be explored as building blocks in medicinal chemistry libraries.
• Regulatory note: For research use only. Not for human or veterinary use, drug, or household applications.

Physical Properties

• Item-specific specifications
  • Appearance: 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.
• Literature/estimated reference data (non-spec)
  • Molecular formula (literature): C14H11NO5
  • Molecular weight (calculated from literature formula): ~273.24 g/mol
  • Expected physical state (literature): aromatic ester/diaryl ether; typically a crystalline solid.
  • Solubility profile (general):
    • Poorly soluble in water (aromatic neutral compound).
    • Soluble in common organic solvents: dichloromethane, chloroform, ethyl acetate, acetone, THF; high solubility in polar aprotic solvents (DMF, DMSO, NMP).
  • Partitioning (qualitative, general): lipophilic aromatic core with polar functionalities; expected moderate to high logP compared to simple benzoates due to diaryl ether.
  • UV activity (general): strong UV absorbance in 200–350 nm region due to conjugated aromatic/nitro chromophores; useful for UV detection in HPLC.
• Not provided for this specific item; consult CoA/Spec Sheet for: melting point, boiling point, density, refractive index, water content, residual solvents, metal content, and UV cutoff.

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.
• Interpreting grades (general guidance)
  • Research grade: Typically supports synthetic, analytical, and screening applications; specific impurity limits (water, metals, residual solvents) are batch-dependent and given on the CoA.
  • Chromatography/HPLC suitability: Diaryl ether/ester with strong UV response; if HPLC-grade expectations are needed (low UV background, particulates), request a chromatography-suitable grade or prefilter solutions.
• Purity considerations for this class of compound (general)
  • Likely impurities: unreacted starting phenols, anisole-type byproducts, regioisomers, residual inorganic salts, traces of nitro reduction products (anilines).
  • QC strategies: 1H/13C NMR (aromatic pattern and methoxy singlet ~3.8–3.9 ppm), IR (ester C=O ~1715–1735 cm−1; nitro asym/sym ~1510/1340 cm−1), HPLC/UPLC purity at 254–280 nm, HRMS for molecular ion confirmation.
  • Water/peroxide/metals/UV cutoff: Not specified for this item; refer to CoA/Spec Sheet.

Reaction and Applications

This diaryl ether bearing a para-nitro group and a para-methyl benzoate is a versatile synthetic intermediate for materials and medicinal chemistry.

• Transformations centered on the nitro group (literature)
  • Reduction to an aniline (e.g., H2/Pd-C, Fe/AcOH, SnCl2/HCl) yields 4-(4-aminophenoxy)benzoate methyl ester, enabling further coupling (amide, urea, sulfonamide formation) or diazotization to azo dyes/pigments.
  • Nucleophilic substitutions on derived anilines (Buchwald–Hartwig coupling after converting to aryl halides or via diazonium intermediates) expand scaffold diversity.
• Ester functionality (literature)
  • Hydrolysis (acidic or basic) gives the corresponding acid for amidation (EDC/HOBt, HATU), anhydride formation, or Suzuki-type cross-coupling after further derivatization (e.g., convert to acid chloride).
  • Transesterification to alter alcohol moiety; ortho/para directing effects irrelevant as ring is para-disubstituted.
• Ether linkage considerations (general)
  • The Ar–O–Ar bond is robust under many conditions; resists many bases and nucleophiles. Demethylation is not applicable here; cleavage requires harsh conditions (e.g., BBr3 not effective; reductive cleavage or strong Lewis acids may be needed but typically avoided).
• Applications (general)
  • Precursor to poly(arylene ether)-like materials, liquid crystal intermediates, UV-absorbing monomers, and colorants via azo coupling following nitro reduction.
• Practical tips
  • For reductions, protect the methyl ester if needed (e.g., avoid saponification in strongly basic metal reductions).
  • Ensure thorough removal of catalytic metals post-hydrogenation (filtration through Celite; ICP if metals-sensitive application).

Reaction Conditions

General literature guidance for transformations on this scaffold (non-item-specific; optimize per application):

• Nitro-to-aniline reduction
  • H2 (1–4 bar) with 5–10 wt% Pd/C in EtOH or EtOAc/EtOH at 20–40 °C; monitor by TLC/HPLC (0.5–6 h). Alternatively, Fe powder (4–6 equiv) in AcOH/H2O (60–80 °C) or SnCl2·2H2O (3–5 equiv) in EtOH/HCl.
• Ester hydrolysis
  • Basic: KOH or NaOMe in MeOH/H2O (rt–50 °C) to give the acid; acidic: H2SO4 or HCl in MeOH/H2O under reflux. Work up by neutralization and extraction into EtOAc.
• Amidation (from acid)
  • HATU or EDC·HCl/HOAt (or HOBt) in DMF/MeCN with DIPEA at 0–25 °C; 1–12 h. Typical yields for well-matched pairs: 70–95% (literature ranges).
• Diazotization/azo coupling (from aniline derivative)
  • NaNO2 (1.1 equiv) in 2–4 M HCl at 0–5 °C to form diazonium, then couple into activated aromatics/phenols in alkaline media; maintain low temperature to minimize side reactions.
• Crystallization/purification
  • Solvent systems: EtOAc/hexanes or toluene/EtOAc for crystallization; silica gel with hexanes/EtOAc 4:1→1:1 gradients for chromatography.

Note: The diaryl ether bond is typically stable under these conditions; avoid strong nucleophiles at high temperatures if ether cleavage would be problematic. Always confirm compatibility of conditions with the ester and nitro functionalities.

Safety and Handling

• Item-specific hazard data from Product Data
  • GHS Classification: Not specified for this item; refer to SDS.
  • Signal Word: Not specified for this item; refer to SDS.
  • H-Statements: Not specified for this item; refer to SDS.
  • Pictograms: Not specified for this item; refer to SDS.
• General safety guidance for nitroaromatic diaryl ethers and aromatic esters (informational; defer to SDS)
  • Hazards: May cause skin/eye irritation; nitroaromatics can be harmful if swallowed or inhaled. Dust may be irritating to respiratory tract. Not expected to be shock-sensitive; avoid dust generation.
  • Handling: Use in a fume hood. Avoid inhalation of dust and contact with skin/eyes. Keep away from strong bases and strong acids if hydrolysis is not desired; avoid strong reducing agents unless intentional (nitro reduction).
  • PPE: Lab coat, safety glasses or goggles, suitable chemical-resistant gloves (e.g., nitrile), and appropriate respiratory protection if dust/aerosol cannot be controlled.
  • Incompatibilities: Strong reducing agents (may reduce the nitro group); strong nucleophiles/bases or acids can cause ester cleavage; strong oxidizers may react with aromatic substrates.
  • 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; continue rinsing.
    • Ingestion: Rinse mouth; do not induce vomiting; seek medical advice.
  • Storage: As provided, store at room temperature in a tightly closed container, protected from moisture and light. Refer to SDS for authoritative guidance.
• Waste: Dispose of according to local regulations for organic laboratory chemicals; avoid release to the environment.

Solvent Selection

• Polarity and miscibility (general for this compound class)
  • Nonpolar-to-moderately polar aromatic compound with multiple heteroatoms; water-insoluble.
  • Readily soluble in chlorinated solvents (CH2Cl2, CHCl3), ethyl acetate, acetone, THF; high solubility in polar aprotics (DMF, DMSO, NMP). Limited solubility in hexanes/heptane; mixtures with EtOAc or toluene can aid crystallization.
• Use-case-driven choices
  • Reaction medium: DMF, DMSO, NMP, or MeCN for SNAr/diazotization follow-ups after nitro reduction; alcohols for esterifications/transesterifications; THF/EtOAc/DCM for general transformations and extractions.
  • Purification: Normal-phase silica using hexanes/EtOAc or toluene/EtOAc gradients. Reverse-phase HPLC feasible due to UV chromophores.
  • Analytics: MeCN/H2O or MeOH/H2O with formic acid or ammonium buffers for LC-UV/MS methods.
• Comparison (general)
  • DCM vs EtOAc: DCM dissolves more and elutes faster; EtOAc is greener and better for crystallizations.
  • THF vs 2-MeTHF: 2-MeTHF offers greener profile and improved phase separation; solubility similar for this scaffold.
• Item-specific solvent specs (if any): Not specified for this item; refer to CoA/Spec Sheet.

Storage and Reconstitution

• Item-specific storage
  • Storage Conditions: Room temperature (as provided in Product Data).
  • Shipped In: Not specified for this item; refer to CoA/Spec Sheet.
• General guidance for this compound class
  • Store tightly closed, in a dry place, protected from moisture and prolonged light to preserve integrity of the ester and nitro functionalities.
  • If long-term storage is anticipated, consider desiccation (P2O5 or silica gel) and use of an amber container.
• Reconstitution/solution preparation
  • Prepare concentrated stocks in DMSO, DMF, or dichloromethane/ethyl acetate depending on end use. Typical lab stocks: 10–100 mM in DMSO for screening or 10–100 mg/mL in organic solvents for synthesis.
  • Filter solutions for analytical applications (0.2 µm PTFE). Avoid aqueous media unless hydrolysis is intended; the compound is not water-soluble.
• Stability notes
  • The diaryl ether and nitro group are generally robust; the methyl ester can hydrolyze under strong acidic/basic conditions or in wet media over time. Minimize exposure to strong bases/acids and moisture during storage.
• Always consult the SDS and CoA for batch-specific handling and stability information.
• Research Use Only: For research use only; not for human or veterinary use.

Structure and Identity

A para–para linked, nitro-substituted diaryl ether bearing a methyl benzoate. The molecule features two benzene rings connected by an ether oxygen, a nitro group para to the ether on the outer ring, and a methyl ester para to the ether on the benzoate ring.

• Item-specific (from Product Data)
  • CAS: 21120-78-5
  • CID: 2246086
  • InChIKey: 283815 (as provided)
  • Storage: Room temperature
• Literature/computed structure identifiers (for reference; not item-specific specs)
  • Preferred IUPAC name (literature): methyl 4-(4-nitrophenoxy)benzoate
  • Molecular formula (literature): C14H11NO5
  • Molecular weight (literature, calculated): ~273.24 g/mol
  • Representative SMILES (literature): COC(=O)c1ccc(Oc2ccc(cc2)N+[O-])cc1
• Structural features (general description)
  • Functional groups: aromatic ether (Ar–O–Ar), nitro (–NO2), methyl ester (–CO2Me)
  • Ring systems: two para-disubstituted phenyl rings linked via oxygen
  • Conjugation: extended π-system across both rings; nitro group conjugated to the outer aryl ring
  • Stereochemistry: none (achiral, no stereocenters)
  • 2D description: one ring contains the methyl benzoate (ester para to the ether oxygen); the second ring bears a para-nitro substituent relative to the ether linkage.

Synthetic Utility

• Functional group handles
  • Nitro group: reducible to an aniline, enabling diazotization/azo coupling, acylation, sulfonylation, urea/carbamate formation, or cross-coupling after appropriate activation.
  • Methyl ester: convertible to acid (hydrolysis), acid chloride (SOCl2, oxalyl chloride), amide (coupling reagents), or different esters (transesterification).
  • Diaryl ether: confers rigidity and planarity; typically stable under many conditions, serving as an inert spacer in multi-step syntheses.
• Retrosynthetic value
  • Serves as a convergent junction: one branch derived from methyl 4-hydroxybenzoate, the other from p-nitrophenyl electrophiles. This modularity facilitates analog generation by varying either aryl partner or ester functionality.
• Named/related transformations (literature)
  • Nitro reduction (Bechamp-type with Fe/AcOH, catalytic hydrogenation).
  • Amidation via EDC/HOBt, HATU, or acid chloride routes after ester hydrolysis.
  • Azo dye formation via diazotization of the aniline derivative and coupling to activated aromatics or phenols.
• Practical notes
  • Maintain anhydrous conditions when coupling acids/esters; control base strength to avoid undesired ester saponification.
  • Purify intermediates by crystallization from EtOAc/hexanes or by silica chromatography; strong UV absorption simplifies tracking.

Target Specificity

Not applicable. This product is a small-molecule chemical reagent and does not possess biological target specificity data (no antigen/epitope, clone, or isotype). For biochemical assays, any target interactions must be established empirically.