Ethyl 2-fluoro-3-mercaptobenzoate - ≥95% , CAS No.1359983-13-3

CAS: 1359983-13-3 Cat. No.: E993557 PubChem CID: 66765235

GRADE & PURITY ≥95%

Storage

Room temperature

Specifications

Specifiche e purezza

≥95%

Condizioni di conservazione di stoccaggio

Room temperature

Purezza

≥95%

Nomi e identificatori

• Sorrisi canonici: CCOC(=O)C1=C(C(=CC=C1)S)F
• IUPAC Name: ethyl 2-fluoro-3-sulfanylbenzoate
• InChIKey: KZMQZNAMQSWTRW-UHFFFAOYSA-N
• INCHI: 1S/C9H9FO2S/c1-2-12-9(11)6-4-3-5-7(13)8(6)10/h3-5,13H,2H2,1H3
• Isomeri SMILES: CCOC(=O)C1=C(C(=CC=C1)S)F
• PubChem CID: 66765235

Taxonomic Classification

Taxonomy Tree

• Kingdom Organic compounds
  • Superclass Benzenoids
    • Classe Benzene and substituted derivatives
      • Subclass Benzoic acids and derivatives
        • Level5 Sulfanylbenzoic acids and derivatives
          • Level6 M-sulfanylbenzoic acids and derivatives

• Kingdom: Organic compounds
• Superclass: Benzenoids
• Classe: Benzene and substituted derivatives
• Subclass: Benzoic acids and derivatives
• Intermediate Tree Nodes: Sulfanylbenzoic acids and derivatives
• Direct Parent: M-sulfanylbenzoic acids and derivatives
• Alternative Parents: Benzoic acid esters 2-halobenzoic acids and derivatives Thiophenols Benzoyl derivatives Fluorobenzenes Aryl fluorides Vinylogous halides Carboxylic acid esters Thiols Organooxygen compounds Organofluorides Organic oxides Hydrocarbon derivatives
• Molecular Framework: Aromatic homomonocyclic compounds
• Substituents: Benzoate ester - Halobenzoic acid or derivatives - 2-halobenzoic acid or derivatives - M-sulfanylbenzoic acid or derivatives - Thiophenol - Benzoyl - Fluorobenzene - Halobenzene - Aryl fluoride - Aryl halide - Vinylogous halide - Carboxylic acid ester - Arylthiol - Carboxylic acid derivative - Organooxygen compound - Organosulfur compound - Organic oxygen compound - Hydrocarbon derivative - Organic oxide - Organofluoride - Organohalogen compound - Aromatic homomonocyclic compound
• Descrizione: This compound belongs to the class of organic compounds known as m-sulfanylbenzoic acids and derivatives. These are benzoic acids (or derivatives) which bear a sulfanyl group (R-SH) attached to the benzene ring at positions 1 and 3, respectively.
• 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: 200.230 g/mol
• XLogP3: 2.400
• Hydrogen Bond Donor Count: 1
• Hydrogen Bond Acceptor Count: 4
• Rotatable Bond Count: 3
• Exact Mass: 200.031 Da
• Monoisotopic Mass: 200.031 Da
• Topological Polar Surface Area: 27.300 Ų
• Heavy Atom Count: 13
• Formal Charge: 0
• Complexity: 186.000
• 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 application protocols are specified for this item. As a chemical building block, protocol details depend on the chosen synthetic transformation.

• For practical use, see:
  • Reaction & Applications: overview of feasible transformations.
  • Reaction Conditions: representative setups for SNAr, S‑alkylation, oxidation, and ester chemistry.

Always adapt conditions to your substrate and scale, and validate procedures with small-scale trials.

Biological Roles

No item-specific biological data are provided for this research chemical.

• Item-specific note

  • Research Use Only (Product Data): not for human or veterinary use.

• General/background (not product claims)

  • Aryl thiols and aryl fluorides are common motifs in chemical biology probes and medicinal chemistry, but Ethyl 2‑fluoro‑3‑mercaptobenzoate is best viewed as a synthetic intermediate rather than a biological reagent per se.
  • The –SH functionality can participate in bioconjugation chemistry (e.g., formation of thioethers/disulfides) after incorporation into larger scaffolds, and the aryl–F can serve as a leaving group in SNAr for late-stage diversification under mild conditions.
  • Any biological activity, binding, or pathway relevance would derive from derivatives synthesized from this building block; none is specified for the parent compound here.

Buffer Applications

This compound is a hydrophobic aromatic ester with a free aryl thiol and is not a buffering agent.

• Applicability
  • Not typically used to prepare pH buffers or electrophoresis running buffers.
  • For relevant information, see the sections on Reaction & Applications and Synthetic Utility, which address its role as an organic building block.

Green Alternatives

Greener choices focus on solvent selection and oxidation control; the substrate itself is a specialized building block.

• Solvent substitution (general guidance)

  • Prefer 2‑MeTHF over THF for S‑alkylations and SNAr when feasible (higher boiling point, bio-based origin, improved safety profile).
  • Replace DCM with EtOAc or cyclopentyl methyl ether (CPME) for dissolutions/extractions and chromatography when polarity allows.
  • Use MeCN judiciously; IPA or EtOH can serve as greener media for certain base-promoted substitutions or transesterifications.

• Workup and protection strategies

  • Minimize air-induced thiol oxidation by using nitrogen sweeps rather than chemical antioxidants where possible; choose catalytic aerobic oxidations intentionally rather than experiencing adventitious losses.

• Comparison snapshot (literature guidance)

  | Use case | Conventional | Greener alternative | Trade-offs | |---|---|---|---| | SNAr at aryl–F | DMF/DMSO | 2-MeTHF with phase-transfer base or MeCN | May require higher temps/longer times | | S-alkylation | Acetone/DMF | 2-MeTHF, EtOAc | Solubility of bases can limit rates | | Extraction | DCM | EtOAc/MTBE | Partitioning may change; check recovery |

• Waste minimization

  • Employ catalytic quantities of base and avoid halogenated solvents when possible; recover and reuse EtOAc/2‑MeTHF by distillation.

Pharmaceutical Uses

No pharmacopeial grade or excipient role is specified for this item; it is offered for research and development use only.

• Item-specific information

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

• General context (not therapeutic claims)

  • Substituted benzoates like Ethyl 2‑fluoro‑3‑mercaptobenzoate are frequently employed as intermediates in API discovery and process route scouting. The orthogonal handles (aryl–F and –SH) enable rapid analog generation, while the ester provides a masked acid for late-stage functionalization.
  • If used in pharmaceutical R&D, downstream materials must be qualified; residual solvents, metals, and genotoxic impurities require control strategies per ICH guidelines. None of these controls are specified for this catalog item and should be established by the end-user as needed.

Physical Properties

• Item-specific specifications (Product Data)

  • 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/computed values (for general guidance; not product specifications)

  • Empirical formula (computed from structure): C9H9FO2S
  • Formula weight (computed): ~200.23 g/mol
  • Expected physical state: aromatic ester with a thiol; typically a pale solid or low-melting oil (literature expectation for analogous compounds)
  • Solubility: expected to be sparingly soluble in water; freely soluble in common organic solvents (EtOAc, DCM, THF, toluene) (literature)
  • LogP: likely moderate (aromatic ester with one heteroatom F and a thiol) (literature expectation)
  • Boiling/melting points, density, refractive index: Not broadly reported for this exact structure; consult literature or measure under your conditions.

• Practical notes (general)

  • The free aryl thiol can engage in H‑bonding and can oligomerize/oxidize in air; volatility may be reduced relative to the corresponding thioether. Handle and record exact physical constants experimentally for method development.

Quality and Grades

• Item-specific grade/purity information (Product Data)

  • Grade/Purity: Not specified for this item; refer to CoA/Spec Sheet.
  • Stabilizers/inhibitors: Not specified for this item; refer to CoA/Spec Sheet.

• How to interpret grades (general guidance)

  • Research grade building blocks are typically provided at assay purity suitable for synthesis; residual solvents, inorganic ash, and trace metals are not controlled to pharmacopeial limits unless explicitly stated.
  • If HPLC or GC assay is reported on the CoA, this reflects organic purity; UV cutoffs, residual peroxides, and metal limits are only relevant if declared.

• Practical QC considerations for this structure (general)

  • Identity confirmation: 1H/13C NMR expected features include ethyl ester quartet/triplet, aromatic multiplets, and a characteristic –SH resonance (often broad, ca. 3–6 ppm, solvent-dependent) with D2O exchange; 19F NMR: single aryl-F resonance with ortho/para couplings to aromatic protons.
  • Stability checks: monitor for disulfide formation (m/z doubling in MS) and ester hydrolysis (appearance of corresponding acid/ethanol) during stability studies.
  • Water content, residual solvents, and metals: Not specified for this item; refer to CoA/Spec Sheet.

Reaction and Applications

As a multifunctional aryl building block, Ethyl 2-fluoro-3-mercaptobenzoate supports orthogonal transformations on the aryl–F, the –SH, and the ester.

• Aryl–F handle (literature)

  • Nucleophilic aromatic substitution (SNAr): the ortho carbonyl activates the ring; fluoride is an excellent leaving group. Oxygen, nitrogen, sulfur, and carbon nucleophiles can be introduced under basic conditions (e.g., alkoxides, amines, thiolates) to construct 2‑substituted 3‑mercaptobenzoates.
  • Metal-catalyzed transformations: directed ortho metalation or catalytic defluorinative couplings are possible under specialized conditions, though less common than SNAr.

• Thiol handle (literature)

  • S‑Alkylation or S‑arylation to form thioethers using alkyl halides (K2CO3, DMF/MeCN) or cross-coupling (e.g., Buchwald–Hartwig-type or Migita C–S couplings with aryl halides, Pd/Cu catalysts, base).
  • Oxidation to disulfide dimers (I2, air/O2 with base, or mild peroxides) for protecting-group strategies.

• Ester handle (literature)

  • Hydrolysis to the acid (aq. base or acid); conversion to acid chlorides; subsequent amide couplings (e.g., EDCI/HOBt, HATU) to deliver benzamides bearing ortho‑heteroatom patterns.
  • Transesterification to tailor leaving groups or solubility.

• Applications (general)

  • Useful intermediate for assembling benzothiazoles/benzoxazoles via condensation/cyclization when the thiol or an introduced ortho‑amine/nitrogen is leveraged.
  • Scaffold for medicinal chemistry SAR where ortho‑F can be displaced and –SH diversified to explore C–S, C–N, or C–O vectors.

• Practical tips

  • Keep –SH reduced (inert atmosphere, minimal air exposure); dry solvents promote clean SNAr and S‑alkylation. Monitor reactions by 19F NMR where loss/shift of the aryl‑F signal rapidly indicates conversion.

Reaction Conditions

Representative literature-style conditions for each functional handle (guidance only; optimize per substrate and scale).

• SNAr at C2–F (literature)

  • Nucleophiles: alkoxides, amines, thiolates, stabilized carbanions.
  • Solvents: DMSO or DMF; MeCN or 2‑MeTHF with stronger bases.
  • Bases: K2CO3, Cs2CO3, t‑BuOK (for less nucleophilic partners).
  • Temperature/time: 50–120 °C, 1–24 h depending on nucleophile strength and solvent.
  • Notes: Water content suppresses rates; use dry conditions. Monitor by 19F NMR or LC–MS.

• S‑Alkylation (literature)

  • Electrophiles: primary alkyl halides, sulfonates.
  • Base/solvent: K2CO3 or Cs2CO3 in DMF/MeCN/acetone; triethylamine in DCM for more activated electrophiles.
  • Temperature: 0–40 °C typically; higher for hindered substrates.
  • Notes: Avoid strong bases that promote competing SNAr at C2 unless desired; protect –SH if necessary.

• Oxidation to disulfide (literature)

  • Reagents: I2, air/O2 with base, or mild H2O2; solvents: MeOH, EtOH, or MeCN.
  • Control: use stoichiometric oxidant for clean dimer; catalytic aerobic conditions can be slower but greener.

• Ester transformations (literature)

  • Hydrolysis: aq. NaOH or K2CO3 in MeOH/THF–H2O, rt–60 °C.
  • Coupling (after acid formation): HATU/EDC protocols in DMF/MeCN with DIPEA, 0–25 °C.

All parameters above are general literature guidance and not specifications for this item.

Safety and Handling

• Item-specific hazard data (Product Data)

  • Signal Word: Not specified for this item; refer to SDS.
  • H-Statements: Not specified for this item; refer to SDS.
  • GHS Classification: Not specified for this item; refer to SDS.
  • Pictograms: Not specified for this item; refer to SDS.

• General safety considerations for aryl thiols and aromatic esters (literature/good practice; defer to SDS for authoritative guidance)

  • Potential hazards: irritant to skin, eyes, and respiratory tract; thiols often have strong odor and low odor thresholds. Aryl thiols may oxidize to disulfides, potentially generating heat in the presence of oxidants.
  • PPE: lab coat, safety glasses, and appropriate chemical-resistant gloves (e.g., nitrile). Use in a fume hood to control vapors/odor.
  • Incompatibilities: strong oxidizers (risk of rapid oxidation of –SH); strong bases/acids can promote transesterification or hydrolysis; avoid contact with reactive metals if basic conditions are used.
  • First aid (overview):
    • Inhalation: move to fresh air; seek medical attention if symptoms persist.
    • Skin/eye contact: rinse with water for at least 15 minutes; remove contaminated clothing; obtain medical advice.
    • Ingestion: rinse mouth; do not induce vomiting; seek medical attention.
  • Fire safety: treat as combustible organic; use CO2, dry chemical, or foam extinguishers. Combustion may produce SOx and HF-containing species.
  • Storage practice: tightly closed container, at room temperature per Product Data; minimize air exposure to reduce thiol oxidation; consider storing under inert gas for long-term stability.

Solvent Selection

This compound is a moderately nonpolar aromatic ester bearing a polarizable –SH and an aryl–F. It behaves as an organic-soluble building block.

• Solubility/miscibility profile (literature expectations)

  • High solubility: dichloromethane, chloroform, ethyl acetate, THF, MTBE, toluene, DMF/DMAc/DMSO.
  • Low solubility: water and very polar protic solvents without cosolvent.

• Polarity guidance

  • Operates well in mid-polar aprotic media for SNAr or S-alkylation (DMF/DMSO/MeCN) and in less polar solvents (toluene/EtOAc) for workups and extractions.

• Choosing among common solvents (general)

  • SNAr at aryl–F: DMSO or DMF with inorganic bases enables deprotonation of external nucleophiles; MeCN can be used with phase-transfer or soluble bases when volatility is desired.
  • S‑Alkylation of the aryl thiol: acetone, MeCN, THF, or DMF with mild base (K2CO3, Cs2CO3) balance solubility and control rates; avoid strongly protic media to limit competing hydrolysis.
  • Hydrolysis/ester manipulation: alcoholic solvents under acid/base catalysis tune transesterification; aqueous-organic biphasic systems help isolate the acid.

• Small comparison (general)

  • DCM vs EtOAc: DCM offers faster dissolution and easy removal; EtOAc is greener and compatible with silica chromatography. THF vs 2-MeTHF: similar polarity; 2-MeTHF offers improved safety/greenness.

Storage and Reconstitution

• Item-specific storage (Product Data)

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

• General storage guidance for aryl thiols and esters (good practice)

  • Keep container tightly closed in a dry place; limit air exposure to minimize thiol oxidation to disulfides. If long-term storage is planned, consider blanketing the headspace with nitrogen or argon and storing in amber glass to reduce light exposure.
  • Avoid prolonged contact with strong acids/bases which may drive hydrolysis or transesterification.

• Reconstitution and handling

  • Dissolution: readily dissolves in common organic solvents (e.g., DCM, EtOAc, THF, MeCN, DMF). Prepare stock solutions immediately before use when possible; degas/dry solvents for base-promoted reactions.
  • Freeze–thaw: not typically necessary for solids/oils at ambient storage; if solutions are prepared, store aliquots to avoid repeated air exposure and concentration changes on solvent loss.

For definitive handling and stability parameters, consult the product’s CoA and SDS.

Structure and Identity

An ortho-fluoro, meta-mercapto substituted ethyl benzoate that combines an activated aryl fluoride with a free thiol on the ring.

• Item-specific identifiers (Product Data)

  • SKU: E993557
  • Product Name: Ethyl 2-fluoro-3-mercaptobenzoate
  • CAS: 1359983-13-3
  • PubChem CID: 66765235
  • InChIKey (as provided): 193724 (note: this is not a standard-length InChIKey; verify against databases before regulatory use)
  • SMILES: Not specified for this item; refer to CoA/Spec Sheet.

• Literature/computed identifiers and features (informational)

  • Proposed SMILES (literature/structure-derived; verify): CCOC(=O)c1c(S)cccc1F
  • Typical molecular formula (computed from name): C9H9FO2S
  • Typical molecular weight (computed): ~200.23 g/mol
  • Core scaffold: substituted benzoate (ethyl ester of 2-fluoro-3-mercaptobenzoic acid)
  • Functional groups: aryl fluoride (C–F), aryl thiol (–SH), aromatic ester (–CO2Et)
  • Positional pattern: relative to the carboxyl carbon as position 1, F at 2- (ortho) and SH at 3- (meta) positions.

• 2D structural description (general)

  • A benzene ring bearing an ethyl ester at C1 (–CO2CH2CH3), a fluorine at C2 (ortho to the ester), and a thiol group (–SH) at C3. The –SH is capable of oxidation to disulfides or S‑alkylation; the ortho‑F is a competent leaving group in SNAr on the ring activated by the adjacent carbonyl.

Synthetic Utility

Orthogonal functional handles make this substrate valuable in multi-step synthesis and library buildouts.

• Functional group leverage (literature)

  • Aryl–F: undergoes SNAr with O/N/S/C nucleophiles, aided by the ortho carbonyl’s –I/–M effects. Enables installation of phenoxy, anilino, thiolate, or carbon nucleophiles at C2.
  • Aryl –SH: readily forms thioethers (S‑alkylation/arylation), serves as a handle for intramolecular cyclizations (e.g., benzothiazole formation after introducing an ortho amino/imine partner), and can be temporarily masked as disulfide or thioacetate.
  • Ester: convertible to carboxylic acid, acid chloride, amide, or different esters; can serve as a directing/activating group in some transformations.

• Retrosynthetic value

  • Serves as a convergent node: diversify C2 via SNAr first, then elaborate S to tailor electronics/lipophilicity, or invert the sequence to exploit chemoselectivity. The ester can be unveiled late to access acylation chemistry or coupling.

• Selectivity and protection

  • Order of operations matters: protecting –SH (e.g., thioacetate, trityl) may be advisable prior to strong-base SNAr to prevent undesired S‑alkylation. Conversely, conducting S‑functionalization first can simplify mixtures if the incoming nucleophile could also attack at C2.

• Analytics

  • 19F NMR is a sensitive handle for following C2 transformations; disappearance or significant shift of the aryl‑F resonance tracks conversion. HRMS readily distinguishes the parent from disulfide dimer (M→2M–2H).

Target Specificity

Not applicable. This product is a small-molecule synthetic building block and is not an antibody, enzyme, or biological targeting reagent. No target, epitope, species reactivity, clone, or isotype information applies.