Ethyl 2-(Benzylsulfanyl)acetate - ≥95% , CAS No.2899-67-4

CAS: 2899-67-4 Cat. No.: E991265 Summenformel: C₁₁H₁₄O₂S Molekulargewicht: 210.290

GRADE & PURITY ≥95%

Storage

Room temperature

Specifications

Spezifikationen & Reinheit

≥95%

Storage

Room temperature

Reinheit

≥95%

Namen und Kennungen

Kanonisches Lächeln

CCOC(=O)CSCC1=CC=CC=C1

IUPAC Name

ethyl 2-benzylsulfanylacetate

InChIKey

GRUYTQCKCHPMJF-UHFFFAOYSA-N

INCHI

1S/C11H14O2S/c1-2-13-11(12)9-14-8-10-6-4-3-5-7-10/h3-7H,2,8-9H2,1H3

Molekulargewicht

210.290

Taxonomic Classification

Taxonomy Tree

• Kingdom Organic compounds
  • Superclass Benzenoids
    • Klasse Benzene and substituted derivatives

• Kingdom: Organic compounds
• Superclass: Benzenoids
• Klasse: Benzene and substituted derivatives
• Subclass: Not available
• Intermediate Tree Nodes: Not available
• Direct Parent: Benzene and substituted derivatives
• Alternative Parents: Carboxylic acid esters Sulfenyl compounds Monocarboxylic acids and derivatives Dialkylthioethers Organic oxides Hydrocarbon derivatives Carbonyl compounds
• Molecular Framework: Aromatic homomonocyclic compounds
• Substituents: Monocyclic benzene moiety - Carboxylic acid ester - Dialkylthioether - Sulfenyl compound - Thioether - Monocarboxylic acid or derivatives - Carboxylic acid derivative - Organic oxygen compound - Organic oxide - Hydrocarbon derivative - Organosulfur compound - Organooxygen compound - Carbonyl group - Aromatic homomonocyclic compound
• Beschreibung: This compound belongs to the class of organic compounds known as benzene and substituted derivatives. These are aromatic compounds containing one monocyclic ring system consisting of benzene.
• 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

• Molekulargewicht: 210.290 g/mol
• XLogP3: 2.800
• Hydrogen Bond Donor Count: 0
• Hydrogen Bond Acceptor Count: 3
• Rotatable Bond Count: 6
• Exact Mass: 210.071 Da
• Monoisotopic Mass: 210.071 Da
• Topological Polar Surface Area: 51.600 Ų
• Heavy Atom Count: 14
• Formal Charge: 0
• Complexity: 165.000
• 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 standardized bioassay or immunoassay protocols apply to this small-molecule reagent. For synthetic use, see the Reaction Conditions tab for representative procedures (enolate alkylation, hydrogenolysis, and sulfur oxidation). Reaction parameters must be optimized for the specific substrate set and scale.

Biological Roles

This product is an organic synthesis building block and does not have a defined biological role.

• General context (literature):
  • Thioethers and esters are common in biochemistry, but Ethyl 2-(benzylsulfanyl)acetate itself is not known as a metabolite, cofactor, or signaling molecule.
  • After synthetic transformation (e.g., deprotection to mercaptoacetate), derivatives can serve as linkers or handles in bioconjugation chemistry; however, such roles pertain to downstream products, not to this starting material.

No medical or clinical uses are claimed. For laboratory research use only.

Buffer Applications

Not typically applicable. Ethyl 2-(benzylsulfanyl)acetate is a neutral organic reagent, not used as a buffering agent or pH stabilizer.

• Practical note: When used in aqueous or biphasic systems, choose buffer components compatible with thioethers and esters (avoid strong bases/acids that promote hydrolysis or oxidation). If phase-transfer catalysis is employed, carbonate/bicarbonate buffers are common, but these buffer choices concern the reaction medium rather than this compound acting as a buffer.

Green Alternatives

Although this material is a reagent/substrate (not a process solvent), greener strategy considerations center on solvent choice, protecting-group strategy, and deprotection conditions.

• Greener solvent choices (when compatible):

  • Prefer 2-MeTHF over THF for enolate chemistry (biorenewable source, higher bp, easier phase separation).
  • Consider EtOAc or Me-THF as alternatives to DCM for extractions and mCPBA oxidations when reactivity/selectivity permit.
  • Use ethanol or isopropanol as media for hydrogenolysis in lieu of chlorinated solvents.

• Protecting-group and deprotection considerations:

  • Benzylthio deprotection uses Pd/C and H2. If palladium/H2 usage is undesirable, alternative S-protecting groups removable under basic (e.g., Acm with Hg-free protocols) or oxidative conditions could be evaluated; however, these can increase waste or hazard. Benzyl’s advantage is mild, selective cleavage and benign byproduct (toluene/benzyl species) but does use precious metal/hydrogen.

• Oxidants and waste minimization:

  • For sulfone formation, Oxone (KHSO5) in aqueous alcohols can replace chlorinated media/peracids. Balance against increased aqueous waste.

• Energy and safety:

  • Room-temperature hydrogenolysis at 1 atm H2 reduces energy input; employ balloon techniques and low Pd loadings to minimize metal usage, with downstream metal scavenging.

Comparison snapshot (general):

• THF vs 2-MeTHF: similar performance; 2-MeTHF greener, higher bp; may alter enolate selectivity.
• DCM vs EtOAc: EtOAc greener, but less inert toward strong acids/bases and has higher bp.
• mCPBA vs Oxone: Oxone safer/greener, but sometimes slower and more aqueous workups.

Pharmaceutical Uses

No direct excipient or dosage-form role is indicated for this material.

• Context (general, non-clinical):
  • As a protected thioglycolate, it can serve as an intermediate in the synthesis of sulfur-containing small molecules, pro-moieties, or linkers used during API development.
  • The benzylthio protecting group allows chemoselective unveiling of thiols under hydrogenolysis, which is valuable in multistep routes.

This product is supplied for research and laboratory synthesis only. No therapeutic, diagnostic, or clinical claims are made.

Physical Properties

• Item-specific specifications (this product):

  • Appearance: Not specified for this item; refer to CoA/Spec Sheet.
  • Any numeric specs (bp, mp, density, RI, water, metals, UV cutoff): Not specified for this item; refer to CoA/Spec Sheet.

• Literature/general properties (for context; not product specifications):

  • Physical state: typically a colorless to pale yellow liquid for many benzyl thioether esters.
  • Odor: thioethers often exhibit a characteristic sulfide odor.
  • Solubility: expected to be miscible with common organic solvents (DCM, CHCl3, THF, Et2O, EtOAc, toluene) and to have low solubility in water.
  • Polarity/partitioning: moderate hydrophobicity from the benzyl and ethyl groups tempered by the polar ester; thioether is weakly polarizable.
  • Acidity/basicity: enolizable methylene alpha to the ester (pKa for simple alkyl acetates ~25 in DMSO; thioether substitution can slightly enhance acidity; literature context only).

• Practical handling traits (general):

  • Miscibility with organic media enables use as a substrate/partner across polar aprotic and moderately nonpolar solvents.
  • The alpha-methylene is activated toward base-mediated deprotonation and alkylation.
  • Thioether sulfur is susceptible to oxidation to sulfoxide/sulfone under oxidizing conditions.

Note: For exact numeric physical constants and acceptance criteria of this catalog item, please consult the item’s CoA/Spec Sheet.

Quality and Grades

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

• Interpreting grades (general guidance):

  • “Research grade” or equivalent indicates suitability for synthetic and analytical research workflows; contaminants are controlled to levels compatible with standard organic synthesis and routine characterization.
  • If offered as “Analytical”/“AR” or “HPLC” grades in related products, these typically restrict UV-active or polar impurities and set tighter limits on metals/halides/water—relevant when using UV detection or metal-catalyzed couplings.

• Stabilizers/inhibitors: Not specified for this item; refer to CoA/Spec Sheet. Thioether esters ordinarily do not require inhibitors; however, trace antioxidants may occasionally be used to suppress oxidation—verify on CoA if critical to your application.

• What to check on receipt (practical):

  • Inspect appearance and odor; record lot number. Confirm identity by LC–MS/GC–MS and 1H/13C NMR if used in key steps. Check for sulfoxide/sulfone by 13C shifts or LC–MS if long shelf time is expected.
  • For moisture- or base-sensitive steps (e.g., strong-base enolations), consider a short-path distillation or silica plug under inert atmosphere to remove adventitious acids/oxidation products if purity is paramount.

• Documentation: For acceptance criteria (assay %, residual solvents, metals, water, etc.), rely on the product’s CoA/Spec Sheet.

Reaction and Applications

Ethyl 2-(benzylsulfanyl)acetate is valued as a masked thioglycolate and an enolizable alpha-ester synthon. Typical research applications include:

• Masked thiol chemistry:

  • The benzylthio group can be cleaved by catalytic hydrogenolysis (H2, Pd/C) to furnish ethyl 2-mercaptoacetate (or its salts), enabling late-stage introduction of thiol functionality under mild, chemoselective conditions.

• Alpha-functionalization via enolate chemistry:

  • The methylene alpha to the ester is activated; deprotonation with NaH, LDA, or KHMDS in ethers (THF, 2-MeTHF) gives the enolate for SN2 alkylations (allyl, benzyl, primary alkyl halides), acylations, or aldol-type additions. Subsequent S-deprotection affords alpha-substituted mercaptoacetates.

• Oxidation-level adjustments at sulfur:

  • Selective oxidation to sulfoxide (1 equiv mCPBA) or sulfone (2–3 equiv mCPBA or Oxone) modulates electronics, enabling alternative reactivity (e.g., enhanced acidity, potential for Julia-type or Ramberg–Bäcklund-related strategies with appropriately designed partners).

• Conjugate additions and thioacetal tactics:

  • Generation of thiolate (post-debenzylation) participates in Michael additions to activated alkenes, opening routes to beta-thioesters—useful in ligation chemistry and as handles for further cross-coupling after oxidation to sulfones.

• Protecting-group logic:

  • Benzyl on sulfur is orthogonal to many acid/base steps and is removable under hydrogenolysis, often compatible with base-sensitive motifs and avoiding exposure of free thiols until late stage.

Practical tips: rigorously dry conditions for enolate formation; control addition temperature (0 to −78 °C) to suppress O-alkylation; quench carefully to avoid hydrolysis of the ester; monitor for partial oxidation of sulfide during workup.

Reaction Conditions

General literature guidance for common transformations (not product specifications; optimize per substrate):

• Enolate alkylation (alpha-functionalization):

  • Base: NaH (60% dispersion, 1.2–1.5 equiv) or LDA (1.1–1.5 equiv).
  • Solvent: dry THF or 2-MeTHF.
  • Temperature: 0 °C to −78 °C for enolate formation; warm to 0–25 °C after electrophile addition.
  • Electrophiles: primary alkyl bromides/iodides, benzyl halides, allyl halides; add 1.2–2.0 equiv.
  • Typical times/yields: 1–6 h; isolated yields often 60–90% depending on electrophile and sterics (literature ranges).

• Debenzylation (hydrogenolysis of S–CH2Ph):

  • Catalyst: 5–10 wt% Pd/C (5–10 mol% Pd relative to substrate as a starting point).
  • H2 pressure: 1 atm (balloon) to 3 atm.
  • Solvent: EtOH, MeOH, or EtOAc; add Et3N (0–0.5 equiv) if acid-sensitive functionalities are present.
  • Temperature/time: rt to 40 °C; 2–12 h.
  • Outcome: ethyl 2-mercaptoacetate (or thiolate under basic conditions); filter over Celite and scavenge Pd as needed.

• Oxidation at sulfur:

  • To sulfoxide: mCPBA (1.0–1.2 equiv), DCM, 0 °C→rt, 1–3 h; monitor to avoid over-oxidation.
  • To sulfone: mCPBA (2.0–3.0 equiv) or Oxone (3–4 equiv active oxidant), DCM or MeOH/H2O, 0–25 °C, 2–8 h.

• Michael additions (after thiol unveiling):

  • Base: NaOMe/NaOEt (0.1–0.5 equiv) or organic base (DBU, 0.1–0.3 equiv).
  • Solvent: MeOH, EtOH, or MeCN.
  • Temperature: 0–25 °C; 1–6 h.

Notes: Exclude moisture and oxygen for base steps. Quench alkoxide/enolate reactions cautiously with protic solvents at low temperature. Verify compatibility of catalysts/electrophiles with thioethers (sulfur can poison some metals).

Safety and Handling

• GHS/SDS information (item-specific):

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

• General chemical safety (thioether esters; literature guidance):

  • Likely hazards: organic liquids may be combustible; thioethers can be irritants; avoid inhalation, ingestion, and skin/eye contact.
  • Incompatibilities: strong oxidizers (risk of rapid oxidation of sulfide to sulfoxide/sulfone), strong bases or nucleophiles (can induce ester saponification or alpha-deprotonation/side reactions), strong acids (hydrolysis).
  • Peroxide formation: not typically prone (contrast to ethers); nevertheless, follow good solvent hygiene.

• PPE and engineering controls:

  • Wear lab coat, safety glasses, and appropriate chemically resistant gloves (e.g., nitrile). Handle in a fume hood to minimize exposure to vapors and odors.

• First-aid overview (defer to SDS for specifics):

  • Skin/eye contact: rinse with copious water for 15 minutes; remove contaminated clothing; seek medical attention if irritation persists.
  • Inhalation: move to fresh air; obtain medical attention if symptoms occur.
  • Ingestion: rinse mouth; do not induce vomiting; seek medical advice.

• Handling tips:

  • Keep container tightly closed. Limit exposure to air/oxidants and excessive heat. Use amber or opaque containers if prolonged storage is anticipated to reduce adventitious oxidation.
  • Dispose in accordance with institutional and regional regulations; sulfide-containing wastes can be malodorous—cap and segregate accordingly.

Solvent Selection

This compound is a substrate/reagent, not a solvent. Selection pertains to dissolving and reacting it efficiently.

• Solubility/miscibility profile (general):

  • Good solubility in chlorinated solvents (DCM, CHCl3), ethers (THF, MTBE), esters (EtOAc), aromatics (toluene), and polar aprotics (MeCN, DMF, DMSO). Poorly soluble in water.

• Choosing the medium by transformation:

  • Base-mediated enolate alkylation: dry THF, 2-MeTHF, or DME with NaH/LDA; polar aprotics (DMF/DMSO) can increase rates for SN2 electrophiles but may complicate workup.
  • Hydrogenolysis of the benzylthio group: alcohols (EtOH/MeOH) or EtOAc under H2/Pd–C; co-solvent with DCM to improve solubility if needed.
  • Oxidation at sulfur (to sulfoxide/sulfone): DCM or EtOAc with peracids (mCPBA); acetone/H2O or MeOH/H2O with Oxone for sulfones.
  • Conjugate additions (thiolate formation): polar aprotics (MeCN, DMF) or biphasic conditions with phase-transfer catalysts.

• Comparison notes (general):

  • THF vs 2-MeTHF: similar solubility/enolate behavior; 2-MeTHF offers higher boiling point and greener profile.
  • DCM vs EtOAc: DCM provides fast dissolution and low polarity proticity; EtOAc is a safer, greener alternative when compatible with the reaction/catalyst system.

Dry, oxygen-lean conditions are preferred for strong-base steps and to minimize sulfide oxidation.

Storage and Reconstitution

• Storage (item-specific):

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

• General storage guidance (thioether esters):

  • Keep tightly closed in a dry, well-ventilated place. Minimize exposure to air and light to reduce slow oxidation at sulfur. For multi-month storage, consider amber glass and, if feasible, an inert-gas headspace (N2/Ar).
  • Avoid prolonged contact with strong bases/acids. Segregate from oxidizing agents.

• Reconstitution/Preparation:

  • Not applicable; supplied as a neat reagent. If solidification occurs at low temperature, warm gently to ambient and mix thoroughly before use.
  • For moisture-sensitive steps, pre-dry by passing through a short silica plug or by azeotropic drying with toluene under reduced pressure.

• Stability notes (general):

  • Thioethers can slowly oxidize to sulfoxides/sulfones over long storage or upon air exposure; assess by NMR/LC–MS if the material has been stored for extended periods.

• Research Use Note: For research use only.

Structure and Identity

Brief description: Ethyl 2-(benzylsulfanyl)acetate is a benzyl thioether of ethyl thioglycolate, combining an ethyl ester with a benzylic sulfide. It serves as a masked thiol and an enolizable alpha-ester building block.

• Product Data (item-specific):

  • CAS: 2899-67-4
  • SKU: E991265
  • Storage Conditions: Room temperature
  • InChIKey: Not specified for this item; refer to CoA/Spec Sheet.
  • SMILES: Not specified for this item; refer to CoA/Spec Sheet.

• Literature/computed identifiers and features (for reference; not item specifications):

  • Preferred name: Ethyl 2-(benzylthio)acetate (synonym: Ethyl S-benzyl thioglycolate)
  • Molecular formula (computed): C11H14O2S
  • Molecular weight (computed): ~210.30 g/mol
  • Representative SMILES (literature): CCOC(=O)CSCc1ccccc1
  • Structural features: one ethyl ester (–CO2Et); one thioether (–S–) linking a benzylic methylene (–CH2–Ph) to the methylene alpha to the ester (–CH2–C(=O)OEt); one aromatic phenyl ring; no stereocenters.
  • 2D description: A phenyl ring attached to –CH2–S–CH2–C(=O)–O–CH2–CH3.

• Category/Type (general): Thioether-containing aliphatic ester; protected thiol; enolizable alpha-ester building block.

Synthetic Utility

Key functional elements and reactivity profile:

• Enolizable alpha-ester (–CH2–C(=O)OEt):

  • Readily forms enolates with NaH, LDA, or KHMDS; supports SN2 alkylations (primary halides, sulfonates), acylations, and aldolizations. After C–C bond formation, the S-benzyl group can be removed to reveal a thiol.

• Benzyl thioether (–S–CH2–Ph):

  • Protective group strategy: hydrogenolysis (H2, Pd/C) cleaves to give 2-mercaptoacetate. Orthogonal to many acid/base steps.
  • Oxidation to sulfoxide/sulfone tunes acidity/electronics; sulfones enable further transformations (e.g., elimination chemistry or serving as leaving-group surrogates).

• Convergent building block:

  • Serves as a masked thiol glycine equivalent: enolate alkylation introduces side chains at the alpha position, followed by S-debenzylation to produce alpha-substituted mercaptoacetates—useful handles for thioether formation, disulfide coupling (after further manipulation), or ligation strategies.

• Representative downstream tactics (general literature):

  • Debenzylation → thiolate capture with electrophiles (alkyl halides, epoxides) to build thioethers/sulfides.
  • Oxidation to sulfone → base-induced elimination to alkenes or participation in Julia-type couplings when properly designed.
  • Michael additions of the corresponding mercaptoacetate to activated alkenes for beta-thioester synthesis.

Practical insights:

• Control chemoselectivity between C- vs O-alkylation via temperature and counterion choice; softer bases and lower temperatures favor C-alkylation.
• Use inert atmosphere to limit adventitious oxidation at sulfur during prolonged operations.

Target Specificity

Not applicable. This product is a small-molecule synthetic intermediate and does not possess biological target specificity (no antigen/epitope, clone, or isotype).