Methyl 3-azidobenzoate solution - ~0.5M in tert-butyl methyl ether , CAS No.93066-93-4

CAS: 93066-93-4 Cat. No.: M462926 Summenformel: C₈H₇N₃O₂ Molekulargewicht: 177.16 EG-Nummer: 685-714-6

GRADE & PURITY ~0.5M in tert-butyl methyl ether

Synonyms

Methyl 3-azidobenzoate | Benzoic acid, 3-azido-, methyl ester | DTXSID80459754 | AKOS040814969 | F2157-0525 | EN300-207141 | SCHEMBL15714872 | BSQWYELDCUXPSJ-UHFFFAOYSA-N

Storage

Store at -20°C

Shipped In

Ice chest + Ice pads

Übersicht

Description

Review

Specifications

Synonyme

Methyl 3-azidobenzoate | Benzoic acid, 3-azido-, methyl ester | DTXSID80459754 | AKOS040814969 | F2157-0525 | EN300-207141 | SCHEMBL15714872 | BSQWYELDCUXPSJ-UHFFFAOYSA-N

Spezifikationen & Reinheit

~0.5M in tert-butyl methyl ether

Storage

Store at -20°C

Verschickt in

Ice chest + Ice pads

Dieses Produkt erfordert Kühlkettenversand. Grundversand und andere Economy-Optionen sind nicht verfügbar.

Namen und Kennungen

• Kanonisches Lächeln: COC(=O)C1=CC(=CC=C1)N=[N+]=[N-]
• IUPAC Name: methyl 3-azidobenzoate
• InChIKey: BSQWYELDCUXPSJ-UHFFFAOYSA-N
• INCHI: 1S/C8H7N3O2/c1-13-8(12)6-3-2-4-7(5-6)10-11-9/h2-5H,1H3
• Isomere SMILES: COC(=O)C1=CC(=CC=C1)N=[N+]=[N-]
• WGK Deutschland: 3
• Molekulargewicht: 177.16
• Reaxy-Rn: 3271617
• Reaxys-RN_link_address: https://www.reaxys.com/reaxys/secured/hopinto.do?context=S&query=IDE.XRN=3271617&ln=

Taxonomic Classification

Taxonomy Tree

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

• Kingdom: Organic compounds
• Superclass: Benzenoids
• Klasse: Benzene and substituted derivatives
• Subclass: Benzoic acids and derivatives
• Intermediate Tree Nodes: Not available
• Direct Parent: Benzoic acid esters
• Alternative Parents: Phenylazides Benzoyl derivatives Methyl esters Azo imides Azo compounds Organooxygen compounds Organic salts Organic oxides Hydrocarbon derivatives Organic cations
• Molecular Framework: Aromatic homomonocyclic compounds
• Substituents: Benzoate ester - Benzoyl - Phenylazide - Methyl ester - Azo compound - Azo imide - Carboxylic acid ester - Carboxylic acid derivative - Organic nitrogen compound - Organic oxygen compound - Organooxygen compound - Organonitrogen compound - Organic salt - Hydrocarbon derivative - Organic oxide - Organic cation - Aromatic homomonocyclic compound
• Beschreibung: This compound belongs to the class of organic compounds known as benzoic acid esters. These are ester derivatives of benzoic acid.
• 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

Chemische und physikalische Eigenschaften

• Flammpunkt (°F): -27.4 °F
• Flammpunkt (°C): -33 °C
• Molekulargewicht: 177.160 g/mol
• XLogP3: 3.400
• Hydrogen Bond Donor Count: 0
• Hydrogen Bond Acceptor Count: 4
• Rotatable Bond Count: 3
• Exact Mass: 177.054 Da
• Monoisotopic Mass: 177.054 Da
• Topological Polar Surface Area: 40.700 Ų
• Heavy Atom Count: 13
• Formal Charge: 0
• Complexity: 236.000
• 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 for biological assay protocols. This product is a small-molecule solution intended for chemical synthesis. No validated WB/IHC/IF/FC protocols or dilutions apply.

For chemical use, see the Reaction Conditions and Synthetic Utility tabs for representative procedures (e.g., CuAAC, Staudinger reduction). Always adjust stoichiometry based on the lot-specific concentration indicated on the CoA.

Biological Roles

This product is a synthetic aryl-azide ester intended for laboratory research and synthesis. It does not have a natural biological role.

• Research context (general)
  • The aryl azide group is widely used as a bioorthogonal handle for conjugation via azide–alkyne cycloaddition (CuAAC) to attach probes, affinity tags, or polymers to small molecules or surfaces. Methyl 3-azidobenzoate provides an azide on an aromatic ring with an ester that can later be hydrolyzed to reveal a carboxylate or transformed into amides/esters.
  • Aryl azides can serve as photoaffinity labels: upon UV activation, they form nitrenes capable of inserting into nearby bonds; however, application to biological systems requires stringent safety and is outside the scope of this product’s intended use.

No clinical or therapeutic claims are made. For research use only, as stated in the Product Data.

Buffer Applications

Not typically applicable. Methyl 3-azidobenzoate is an organic aryl-azide ester supplied as a non-aqueous solution; it is not a buffering agent and is generally incompatible with standard aqueous buffer preparation at significant concentrations. For aqueous-compatible reactions (e.g., CuAAC), it may be used in water-miscible solvent mixtures alongside buffers that control pH for catalysts, but the compound itself does not impart buffering capacity.

Green Alternatives

Greener practice focuses on solvent/catalyst choice and minimizing azide-related risk, since aryl azides themselves possess inherent energetic and toxicity concerns.

• Solvent choices (relative greenness)

  • Consider 2-MeTHF or CPME over THF/DCM for extractions or coupling steps; they offer improved safety/renewable content and facilitate phase separations.
  • Use aqueous/biobased ethanol or tBuOH/H2O mixtures for CuAAC when feasible; they reduce reliance on dipolar aprotic solvents.

• Copper catalysis management in CuAAC

  • Employ ligands like THPTA/BTBTA to enable low copper loadings (≤0.5 mol%) and aqueous media, reducing metal waste.
  • Implement copper scavengers or solid-supported copper to simplify removal and minimize effluent contamination.

• Energy and safety

  • Run reactions at ambient temperature/pressure when possible; photochemical processes should use LED sources with precise wavelengths to improve energy efficiency.
  • Avoid concentrating aryl azides to dryness; use in-solution handling and telescoped sequences to lower energetic risk.

• Comparative snapshot (general)

  • Traditional: DMSO/DMF, neat copper sulfate/sodium ascorbate, high catalyst loadings, chlorinated solvents for workup.
  • Greener alternative: aqueous ethanol or MeCN/H2O, low-copper ligand-accelerated CuAAC, non-chlorinated extraction solvents (EtOAc, 2-MeTHF), and solid-supported purification.

Note: While process choices can be greener, aryl azides remain hazardous; perform risk assessments and waste segregation for azide-containing streams.

Pharmaceutical Uses

This material is supplied for research use only and is not intended for human or veterinary use.

General formulation/manufacturing context (non-clinical)

• As a synthetic intermediate, methyl 3-azidobenzoate can be transformed into meta-aminobenzoate derivatives (after azide reduction) and subsequently into amides, carbamates, or triazole-containing motifs useful in medicinal chemistry campaigns.
• Aryl azides may be used in tracer or surface-attachment workflows via click chemistry during analytical or materials development; however, no pharmacopeial status or excipient role is implied.

Item-specific regulatory/compendial status: Not specified for this item; refer to CoA/Spec Sheet. No therapeutic or diagnostic use is claimed or supported.

Physical Properties

Item-specific physico-chemical specifications (for the supplied solution) are not provided in the Product Data.

• Item-specific values

  • Concentration: Not specified for this item; refer to CoA/Spec Sheet.
  • Solvent for solution: Not specified for this item; refer to CoA/Spec Sheet.
  • Density/viscosity of the supplied solution: Not specified for this item; refer to CoA/Spec Sheet.

• Neat compound (methyl 3-azidobenzoate) — literature/general values

  • Molecular formula: C8H7N3O2 (literature)
  • Molecular weight: ~177.15 g/mol (literature, calculated)
  • Physical state: typically a low– to mid-boiling aromatic ester; aryl azides can be light-sensitive (general note). Exact mp/bp for this isomer should be confirmed from primary literature or measured.
  • Solubility: expected good solubility in common organic solvents (e.g., DCM, EtOAc, THF, MeCN, DMF); very low in water (general for aryl esters/azides). Quantitative values not provided here.
  • UV–vis: aryl azides show strong UV absorption in the 250–280 nm region (literature, qualitative).

• Practical implications

  • Handle under subdued light to limit azide photolysis.
  • Avoid heating above necessity; aryl azides can form nitrenes on photolysis/thermolysis.

Always rely on the CoA/Spec Sheet for product-specific data of the supplied solution. Do not treat literature values as product specifications.

Quality and Grades

• Item-specific grade/purity: Not specified for this item; refer to CoA/Spec Sheet.
• Stabilizers/inhibitors: Not specified for this item; refer to CoA/Spec Sheet.

General guidance

• Azide-bearing building blocks are often provided as solutions to enhance handling safety, reduce crystallization/precipitation issues, and facilitate dosing by volume. Concentration accuracy and solvent selection directly impact performance in downstream reactions (e.g., click chemistry). Verify the exact concentration on the CoA and adjust stoichiometry accordingly.
• If described as “research grade” (Research Use Only note applies), materials are manufactured and tested for laboratory research purposes, not for clinical or diagnostic use.
• Chromatography-grade solvents (if used as the matrix) typically ensure low UV background and minimal metal/ion content; however, this listing does not specify the solvent grade.
• For azide content and identity, typical QA controls may include: 1H/13C NMR, IR (distinct azide stretch near ~2100 cm−1, literature), and HPLC/GC purity. Metal analysis and peroxides are generally not relevant unless solvent-specific.

What to check on receipt

• Confirm the solvent, concentration, and lot-specific assay on the CoA.
• Review stability notes (light sensitivity, freeze–thaw tolerance) and any inhibitor content if present.
• Ensure packaging is light-protective (amber vials) and compatible with azide solutions.

Reaction and Applications

Methyl 3-azidobenzoate is a versatile aryl-azide ester used in synthesis and labeling chemistry. As a solution, it is ready for direct dosing into reaction media.

Key application families (literature/general)

• Azide–alkyne cycloaddition (CuAAC and SPAAC): serves as the azide partner to generate 1,4- or 1,5-disubstituted 1,2,3-triazoles appended meta to a methyl benzoate. Useful for library synthesis and linker installation.
• Staudinger reduction: conversion of the aryl azide to the corresponding aniline (methyl 3-aminobenzoate) using PPh3 or other phosphines; the intermediate iminophosphorane can be trapped or hydrolyzed.
• Catalytic hydrogenation or transfer hydrogenation: azide to amine under Pd/C–H2 or Raney Ni (mindful of ester stability). Enables downstream amidation, urea, or sulfonamide formation at the meta-aminobenzoate stage.
• Photolysis to aryl nitrenes: under UV, generates nitrenes that can insert or rearrange (C–H/N–H insertion, addition to alkenes). Requires careful control due to potential side reactions and hazards.
• Diazo transfer and derivatization workflows: the aryl azide can function as a masked amine; subsequent transformations leverage the ester for hydrolysis or coupling.

Practical considerations

• Protect from light; wrap vessels with foil.
• Maintain moderate temperatures; avoid concentrating to dryness unless evaluated for energetic risk.
• For CuAAC, degas aqueous mixtures if aerobic inhibition is problematic; use Cu(I)-stabilizing ligands to accelerate and suppress side reactions.

Reaction Conditions

Representative conditions (literature/general guidance; not product-specific specifications)

• CuAAC (azide–alkyne cycloaddition)

  • Typical: terminal alkyne (1.0 eq), methyl 3-azidobenzoate (1.0–1.2 eq), CuSO4·5H2O (1–5 mol%), sodium ascorbate (5–20 mol%), ligand (e.g., TBTA/THPTA, 2–10 mol%). Solvent: tBuOH/H2O (1:1), MeOH/H2O, or MeCN/H2O. Temp: rt to 50 °C. Time: 1–12 h. Often quantitative to excellent yields with clean triazoles.
  • Heterogeneous/green variants: Cu wire or Cu powder as source; flow or supported catalysts to simplify workup.

• Staudinger reduction to aniline

  • Reagents: PPh3 (1.1–1.5 eq) in THF/Et2O/MeCN; quench with water or buffer to hydrolyze iminophosphorane. Temp: 0 °C to rt. Time: 1–6 h. Gives methyl 3-aminobenzoate; subsequent acylations possible.

• Catalytic hydrogenation

  • Pd/C (5–10 wt%) in MeOH/EtOH/EtOAc at 1–3 bar H2, rt to 40 °C, 2–8 h. Monitor for ester stability; alternative catalysts (Raney Ni) as needed.

• Hydrolysis/transesterification of the methyl ester

  • Basic saponification: NaOH/KOH (1–2 eq) in MeOH/H2O, 0 °C to rt, 1–4 h → 3-azidobenzoic acid; avoid prolonged heating.
  • Acidic methanolysis/ester exchange under mild acid catalysis if azide stability allows.

General notes

• Shield from light; purge with N2/Ar for air-sensitive steps.
• Avoid copper/lead contact in wetted parts; use PTFE or stainless steel.
• Always confirm compatibility of conditions with the azide functionality before scale-up.

Safety and Handling

Safety information specific to this catalog item (GHS signal word, pictograms, H-statements) is not provided in the Product Data. Always consult the product SDS before use.

General safety guidance for aryl-azide ester solutions (professional laboratory context)

• Primary hazards (general):
  • Aryl azides are photosensitive; UV exposure can generate reactive nitrenes capable of insertion and sensitization reactions.
  • Azides may be acutely toxic and can cause irritation to skin, eyes, and respiratory tract. Solutions containing azide can corrode lead and copper plumbing to form explosive metal azides; avoid contact with such metals.
  • Thermal decomposition risk increases with heat; avoid unnecessary heating or concentration to dryness unless risk-assessed.
• PPE: lab coat, safety glasses or face shield for splash risk, and appropriate chemically resistant gloves (e.g., nitrile). Work in a fume hood.
• Handling:
  • Minimize light exposure (wrap glassware with foil; use amber vials).
  • Keep away from strong reducing agents and strong acids that can form hydrazoic acid (HN3). Avoid contact with heavy metal salts.
  • Do not allow the solution to evaporate to dryness without assessing energetic hazard of the neat azide.
• First aid (overview):
  • Inhalation: move to fresh air; seek medical attention.
  • Skin/eye contact: rinse with water for at least 15 minutes; remove contaminated clothing; seek medical attention.
  • Ingestion: rinse mouth; do not induce vomiting; seek medical attention.
• Fire/explosion: use CO2, dry chemical, or foam. Cool containers with water spray. Combustion may produce hazardous nitrogen oxides.

Defer to the SDS for authoritative hazard classifications and emergency measures for this specific solution.

Solvent Selection

This product is supplied as a solution; the specific solvent is not disclosed in the Product Data. Selection of reaction solvent should therefore be guided by the transformation you plan to perform with methyl 3-azidobenzoate.

• Polarity/miscibility considerations (general for aryl azides/esters)
  • Readily soluble in moderately polar aprotic solvents (MeCN, DMF, DMSO, THF, DCM, EtOAc). Very low solubility in water.
  • For CuAAC (click) reactions, mixed tBuOH/H2O, MeOH/H2O, or MeCN/H2O are commonly used; ensure compatibility with the ester group and catalyst.
• Choosing among common options
  • MeCN: good balance of polarity and low viscosity; compatible with CuAAC and many nucleophilic substitutions.
  • DMF/DMSO: high polarity for difficult substrates; consider workup challenges and potential for azide decomposition at elevated temperatures.
  • THF/2-MeTHF: useful for organometallic or base-mediated steps; light-protect containers to limit azide photolysis.
  • DCM/EtOAc: effective for extractions and acylations; avoid prolonged sunlight exposure.
• Practical tips
  • Avoid copper/lead metal contact in plumbing or fittings to prevent formation of metal azides; use PTFE or compatible polymers.
  • For photolysis/nitrene chemistry, choose solvents that do not readily undergo insertion (e.g., acetonitrile) and irradiate with controlled wavelengths.
  • If the supplied solvent differs from your reaction medium, transfer under inert atmosphere and reduced light, then adjust volume precisely by mass or volumetric addition after verifying concentration.

Storage and Reconstitution

• Storage (from Product Data)

  • Store at −20 °C.
  • Shipped in ice chest with ice pads to maintain cold chain.

• Light and stability

  • Protect from light (use amber vials, wrap with foil) to minimize azide photolysis.
  • Avoid repeated freeze–thaw cycles when feasible; aliquot upon receipt if concentration permits.

• Container and compatibility

  • Use containers and caps compatible with organic solvents and azides (glass with PTFE-lined caps). Avoid contact with copper/lead surfaces; azides can form sensitive metal azides.

• Reconstitution/Preparation

  • The product is supplied as a solution; no reconstitution is required. If concentration adjustment is necessary, verify the exact concentration from the CoA, then dilute with a compatible, dry, oxygen-free solvent under reduced light.
  • Do not concentrate to dryness without an appropriate hazard assessment for the neat aryl azide.

• Handling tips

  • Allow the vial to warm toward room temperature before opening to prevent condensation ingress.
  • If precipitate or phase separation is observed at low temperature, gently warm and mix to redissolve before use.

Always refer to the CoA and SDS for lot-specific guidance and stability information. Research use only.

Structure and Identity

Methyl 3-azidobenzoate solution is an aryl azide-bearing methyl benzoate derivative supplied as a solution (solvent not specified for this item).

• Product-specific identifiers (from Product Data)

  • SKU: M462926
  • CAS: 93066-93-4
  • InChIKey: Not specified for this item; refer to CoA/Spec Sheet. (Provided value “33279” is not a standard InChIKey format.)
  • SMILES: Not specified for this item; refer to CoA/Spec Sheet.

• Structural features (general/literature description of the neat compound)

  • Core: benzene ring bearing a methyl ester (–CO2Me) and an azido (–N3) substituent in the meta (3-) position.
  • Functional groups: aryl azide (electron-withdrawing, photosensitive), aromatic ester (electrophilic carbonyl).
  • 2D description in words: a benzene ring with a methyl ester substituent at C1 and an azide substituent at C3 (meta) relative to the ester carbonyl. No stereogenic centers.

• Composition (literature, neat compound)

  • Molecular formula (literature): C8H7N3O2
  • Molecular weight (literature): ~177.15 g/mol

Notes

• The product is provided as a “solution”; exact concentration and solvent are not specified for this item. Consult the CoA/Spec Sheet for definitive structural strings (SMILES/InChI) and concentration details.

Synthetic Utility

Functional groups and reactivity (general)

• Aryl azide (–N3):
  • Nucleophilicity: low; serves mainly as a 1,3-dipole in cycloadditions and as a masked amine.
  • Transformations: CuAAC/SPAAC to triazoles; Staudinger reduction to anilines; catalytic hydrogenation; photolytic nitrene formation for insertion/cyclization.
• Methyl ester (–CO2Me):
  • Electrophilic at the carbonyl; suitable for hydrolysis (saponification to 3-azidobenzoic acid), transesterification, or amidation after activation.

Strategic value

• Orthogonal handles: the azide enables rapid conjugation, while the ester allows later diversification (acid, amide libraries) without disturbing the triazole or aniline motif.
• Retrosynthesis: access from 3-aminobenzoate via diazotization/azidation, or from 3-nitro-/3-bromo-benzoate via displacement/functional group interconversions, offering multiple entry points for SAR exploration.

Protecting group logic

• The methyl ester is a convenient temporary protection for the acid; choose base- or enzyme-catalyzed hydrolysis conditions that do not reduce or decompose the azide.
• Sequence planning: perform click or azide-specific transformations under neutral/mild conditions prior to strong nucleophiles or high heat.

Safety-conscious operations

• Keep reactions dilute for photolysis or nitrene chemistry; avoid concentration to dryness of azide-containing mixtures.

Target Specificity

Not applicable. This product is a small-molecule aryl-azide ester, not an antibody, enzyme, or affinity reagent. No antigen, epitope, clone, isotype, or species reactivity is relevant.