Ethyl 2-[2-(ethylthio)propyl]-4,6-dioxocyclohexanecarboxylate - ≥98% , CAS No.90498-50-3

CAS: 90498-50-3 Cat. No.: E984770 Summenformel: C₁₄H₂₂O₄S Molekulargewicht: 286.390

GRADE & PURITY ≥98%

Storage

Room temperature

Specifications

Spezifikationen & Reinheit

≥98%

Storage

Room temperature

Reinheit

≥98%

Namen und Kennungen

• Kanonisches Lächeln: CCOC(=O)C1C(CC(=O)CC1=O)CC(C)SCC
• IUPAC Name: ethyl 2-(2-ethylsulfanylpropyl)-4,6-dioxocyclohexane-1-carboxylate
• InChIKey: WYLFSJUSABJKTE-UHFFFAOYSA-N
• INCHI: 1S/C14H22O4S/c1-4-18-14(17)13-10(6-9(3)19-5-2)7-11(15)8-12(13)16/h9-10,13H,4-8H2,1-3H3
• Molekulargewicht: 286.390

Taxonomic Classification

Taxonomy Tree

• Kingdom Organic compounds
  • Superclass Organic oxygen compounds
    • Klasse Organooxygen compounds
      • Subclass Carbonyl compounds
        • Ebene5 1,3-dicarbonyl compounds
          • Ebene6 Beta-diketones

• Kingdom: Organic compounds
• Superclass: Organic oxygen compounds
• Klasse: Organooxygen compounds
• Subclass: Carbonyl compounds
• Intermediate Tree Nodes: 1,3-dicarbonyl compounds
• Direct Parent: Beta-diketones
• Alternative Parents: Cyclic ketones Carboxylic acid esters Sulfenyl compounds Monocarboxylic acids and derivatives Dialkylthioethers Organic oxides Hydrocarbon derivatives
• Molecular Framework: Aliphatic homomonocyclic compounds
• Substituents: 1,3-diketone - Cyclic ketone - Ketone - Carboxylic acid ester - Dialkylthioether - Sulfenyl compound - Thioether - Monocarboxylic acid or derivatives - Carboxylic acid derivative - Organic oxide - Hydrocarbon derivative - Organosulfur compound - Aliphatic homomonocyclic compound
• Beschreibung: This compound belongs to the class of organic compounds known as beta-diketones. These are organic compounds containing two keto groups separated by a single carbon atom.
• 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: 286.390 g/mol
• XLogP3: 2.200
• Hydrogen Bond Donor Count: 0
• Hydrogen Bond Acceptor Count: 5
• Rotatable Bond Count: 7
• Exact Mass: 286.124 Da
• Monoisotopic Mass: 286.124 Da
• Topological Polar Surface Area: 85.700 Ų
• Heavy Atom Count: 19
• Formal Charge: 0
• Complexity: 353.000
• Isotope Atom Count: 0
• Defined Atom Stereocenter Count: 0
• Undefined Atom Stereocenter Count: 3
• 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 protocols are specified for this item. As a synthetic building block, typical procedures involve standard organic synthesis operations:

• Prepare anhydrous solutions (e.g., in THF, MeCN, or EtOAc) under inert gas.
• For enolate chemistry, pre-cool and add base (e.g., LDA) at low temperature, then introduce electrophile.
• For condensations, combine with carbonyl partner and catalyst/base; remove water where advantageous.
• Purify by silica gel chromatography (eluent systems such as hexanes/EtOAc or DCM/MeOH, adjusted as needed) and confirm identity by NMR and MS. Refer to internal SOPs and the literature for detailed, reaction-specific protocols.

Biological Roles

This product is a synthetic organic building block rather than a biomolecule.

General biochemical context (informational)

• β-Keto esters do not have intrinsic biological roles but can serve as precursors/intermediates in the synthesis of small molecules for chemical biology, probe development, or structure–activity relationship (SAR) campaigns.
• Thioether-containing motifs occur in numerous bioactive scaffolds; selective oxidation to sulfoxides/sulfones can profoundly change physicochemical properties (polarity, H-bond acceptor count), aiding ADME exploration at the discovery stage.

No endogenous pathway or receptor specificity is implied for this catalog item. Any biological testing should be performed under appropriate research approvals and biosafety practices. No medical or clinical claims are made for this product.

Buffer Applications

Not typically applicable. This compound is a hydrophobic organic building block and is not used as a buffer component. For aqueous work, select standard buffer systems (phosphate, HEPES, acetate) appropriate to your biology, and handle this compound in a co-solvent or as a stock solution in organic solvent if needed for dosing in assays.

Green Alternatives

Greener solvent choices for typical transformations involving this β-keto ester (literature guidance)

Comparison (general benefits/tradeoffs)

• THF vs 2-MeTHF: 2-MeTHF is bio-derived, has higher boiling point and improved phase separation with water, and often supports similar enolate chemistry. Tradeoff: odor and peroxidation risks still exist; ensure inhibitor/peroxide control.
• DCM/CHCl3 vs EtOAc/Me-THF/CPME: Ethyl acetate and CPME can often replace chlorinated solvents for extractions and many reactions, reducing environmental and safety burdens. Tradeoff: different polarity may alter rates/selectivity.
• Toluene/hexanes vs cyclopentyl methyl ether (CPME): CPME offers broad solvency, low peroxide formation tendency compared to ethers like THF, and good water immiscibility.
• Oxidants: Use H2O2 (aqueous or urea–H2O2) with suitable catalysts as greener alternatives to peracids for sulfoxide/sulfone formation; tradeoff: careful control to avoid over-oxidation.

Process-intensification ideas

• Solvent recycling and in-process solvent swaps (e.g., to EtOAc for workup) can reduce waste.
• Employ solid-supported bases/acids to simplify workup and minimize aqueous effluent.
• Consider catalytic, organocatalytic, or electrochemical variants of condensations to reduce stoichiometric reagents.

Note: These are general recommendations; optimization is reaction- and substrate-specific.

Pharmaceutical Uses

Formulation relevance (general)

• This product is offered for research use only. It is not an excipient or API and has no pharmacopeial monograph.
• In discovery chemistry, β-keto esters like this can be intermediates toward candidate molecules. When transitioning to formulation studies, typical considerations include removal of residual solvents, control of ester stability (hydrolysis), and mitigation of sulfur oxidation products.

Manufacturing/analytical notes (informational)

• If used in route scouting, apply ICH-aligned impurity profiling (residual solvents by GC, identity by NMR/HRMS, assay by qNMR or HPLC) before any scale-up. Photostability and oxidative stability studies can be useful given the thioether functionality.

No therapeutic or clinical use is claimed or supported for this product.

Physical Properties

Item-specific (from Product Data)

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

Literature/typical expectations for related β-keto esters (informational only; not item specifications)

• Physical state: many substituted β-keto esters of comparable size are low-melting solids or colorless to pale oils.
• Solubility: typically miscible with common organic solvents (EtOAc, DCM, THF, alcohols) and poorly soluble in water due to hydrophobic ester and thioether moieties.
• Acid–base behavior: 1,3-dicarbonyl systems display enhanced acidity (pKa of the activated methylene frequently ~9–13 in DMSO, literature), enabling facile enolate formation under mild base.
• UV characteristics: conjugation in 1,3-dicarbonyls often yields UV absorbance in the near-UV; exact cutoff/ε Not specified for this item; refer to CoA/Spec Sheet.

Not provided for this item (consult CoA/Spec Sheet if needed)

• Boiling point, melting point, density, refractive index, logP, pKa (quantitative), vapor pressure: Not specified for this item; refer to CoA/Spec Sheet.

Quality and Grades

Item-specific (from Product Data)

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

Guidance on interpreting grade/purity (general)

• Research chemical/building-block grade typically indicates suitability for synthesis and method development. For chromatographic or photochemical applications, additional controls (UV cutoff, low-metal content, water/peroxide content) may be important; these are Not specified for this item; refer to CoA/Spec Sheet.
• Stabilizers/inhibitors: None are stated for this item. If present in a batch, stabilizers would be disclosed on the CoA/Spec Sheet.
• Verification: For moisture- or base-sensitive chemistry, consider confirming water content (e.g., Karl Fischer), residual solvents, and identity/purity (NMR, LC–MS, GC–MS) as required by your SOPs.
• Consistency: Reference the batch-specific CoA for exact assay, impurity profile, and any residual inorganic content when developing GMP-adjacent workflows (though this product is designated for research use only).

Reaction and Applications

Role in synthesis (general; expand based on functional group chemistry)

• Enolate-driven transformations: The 1,3-dicarbonyl motif facilitates formation of stabilized enolates/enols enabling C–C bond formation via alkylation, acylation (Claisen-type), and conjugate (Michael) addition to activated alkenes.
• Knoevenagel/condensation chemistry: The activated methylene adjacent to carbonyls engages aldehydes/ketones under basic or amine-catalyzed conditions to give enones or extended conjugated systems.
• Heterocycle construction: β-Keto esters are key inputs to pyridone, pyrazole, isoxazole, pyran, and quinolone syntheses (via condensation with hydrazines, hydroxylamine, amidines, or 1,3-bis-nucleophiles).
• Chemoselective oxidation at sulfur: The ethylthio substituent can be oxidized to sulfoxide or sulfone (m-CPBA, Oxone, H2O2/Ti catalysts), modulating polarity and serving as a handle for elimination or further functionalization.
• Julia-type tactics: Upon conversion to sulfones, β-elimination or olefination manifolds become accessible (context-dependent; choose bases like KHMDS/NaHMDS under low temperatures).
• Cross-coupling precursors: α-Halogenation (NBS/NCS, sulfuryl chloride, etc.) of the enolized core can deliver electrophiles suitable for subsequent substitution or coupling.

Practical tips

• Maintain anhydrous, oxygen-limited environments to avoid hydrolysis of the ester and unwanted sulfur oxidation.
• Temperature control during strong-base enolate chemistry (−78 to 0 °C) improves selectivity (mono- vs di-alkylation).
• Monitor reactions by LC–MS or TLC with UV detection; β-dicarbonyls typically show strong UV response at 254 nm.

Reaction Conditions

General literature guidance for β-keto ester chemistry (informational; optimize per project)

• Enolate formation/alkylation: LDA or LiHMDS in dry THF, −78 to 0 °C; quench with electrophiles (alkyl halides, sulfonates). Weaker bases (K2CO3, Na2CO3, Cs2CO3) in polar aprotics (DMF/MeCN) can suffice for particularly activated positions.
• Michael additions: Secondary amines or DBU in MeCN/THF at 0–25 °C; catalytic phase-transfer (toluene–water, K2CO3, TBAB) is often effective for soft Michael donors.
• Knoevenagel condensations: Piperidine, ammonium acetate, or secondary amines in toluene, MeCN, or ethanol; azeotropic water removal (Dean–Stark) improves conversions.
• Oxidation of thioether: m-CPBA (1.0 eq for sulfoxide; 2.0–2.5 eq for sulfone) at 0–25 °C in DCM; or H2O2 (30%) with acetic acid/catalyst at 0–40 °C. Monitor to prevent over-oxidation.
• α-Halogenation: NBS/NCS in MeCN, DCM, or acetone at 0–25 °C; radical inhibitors as needed to control pathways.

Analytical/operational tips

• Strictly anhydrous solvents and inert atmosphere reduce ester hydrolysis and undesired sulfur oxidation.
• Reaction monitoring by TLC (UV 254 nm), LC–MS, or in situ IR helps control di- vs mono-substitution.
• Typical isolated yields for well-optimized β-keto ester alkylations/condensations range widely (50–90%, literature) depending on sterics/electrophile; confirm on small scale before scale-up.

Safety and Handling

Item-specific (from Product Data)

• GHS classification, pictograms, signal word, H-statements: Not specified for this item; refer to SDS.
• Storage conditions: Room temperature (per Product Data).
• Research Use: For research use only.

General safety guidance for β-keto esters containing thioethers (informational; always defer to the SDS)

• Likely hazards: Organic esters and thioethers commonly cause skin/eye irritation and may be harmful if swallowed or inhaled. Avoid aerosol formation.
• PPE: Use lab coat, safety glasses or face shield, and suitable gloves (e.g., nitrile). Handle in a fume hood to minimize inhalation exposure.
• Incompatibilities: Strong oxidizers (thioether can oxidize to sulfoxide/sulfone), strong bases/acids (may induce hydrolysis, retro-Claisen, or decomposition), and strong reducing agents.
• First aid (overview):
  • Inhalation: Move to fresh air; seek medical attention if symptoms persist.
  • Skin/eye contact: Rinse with water for several minutes; remove contaminated clothing; seek medical attention if irritation persists.
  • Ingestion: Rinse mouth; do not induce vomiting; seek medical attention.
• Spill/Fire response: Absorb spills with inert material; for fires, use CO2, dry chemical, or foam. Combustion may produce COx and SOx. Prevent entry to drains.
• Waste: Collect as organic hazardous waste according to institutional and local regulations.

Solvent Selection

Applicability and polarity

• Compound class: β-keto ester with a thioether side chain; moderately polarizable but overall hydrophobic. Typically well soluble in medium-polarity organic solvents.

Literature-based solubility and handling considerations (informational)

• Highly suitable solvents: ethyl acetate, dichloromethane, chloroform, THF, toluene, acetone, acetonitrile, and alcohols (MeOH/EtOH/IPA). Water solubility is generally low for analogous structures.
• Enolate chemistry: for deprotonation/alkylation, dry ethereal solvents (THF/MTBE) or hydrocarbons (toluene/hexanes, with polar cosolvent) are common; maintain anhydrous conditions.
• Workup/partitioning: EtOAc/hexanes or DCM/water biphasic systems usually provide good phase separation; avoid strong aqueous base or acid during extractions to minimize hydrolysis.

When to choose alternatives

• If odor/oxidation of thioethers is a concern, use oxygen-poor solvents and include antioxidants or perform operations under inert gas.
• For greener profiles, consider 2-MeTHF or CPME in place of THF, and EtOAc in place of chlorinated solvents; see Green Alternatives tab for tradeoffs.

Storage and Reconstitution

Item-specific (from Product Data)

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

Best-practice handling (general recommendations)

• Store tightly closed in a dry, inert atmosphere (e.g., nitrogen or argon) to minimize moisture ingress (which can promote ester hydrolysis) and aerial oxidation of the thioether.
• Protect from prolonged light and heat. Keep separate from strong oxidizers and strong acids/bases.
• If preparing stock solutions, use dry, oxygen-poor solvents (e.g., anhydrous THF, MeCN, or EtOAc), and store aliquots at ambient or refrigerated temperature according to stability studies; minimize freeze–thaw cycles.

Reconstitution

• Solid/oil status is not specified. If needed, dissolve in a suitable dry organic solvent to the desired concentration with gentle warming and inert gas sparging. Filter through PTFE if particulate is observed.

Always refer to the SDS and batch-specific CoA/Spec Sheet for authoritative storage and stability guidance.

Structure and Identity

Item-specific (from Product Data)

• Product name: Ethyl 2-[2-(ethylthio)propyl]-4,6-dioxocyclohexanecarboxylate (SKU: E984770)
• CAS: 90498-50-3
• PubChem CID: 2834786
• InChIKey: 411324 (as provided)
• SMILES: 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.

General structural description (literature/structure-based reasoning)

• Core scaffold: a cyclohexane-1,3-dione (4,6-dioxo) ring bearing a carboxylate ester (–CO2Et) and an alkyl substituent at the 2-position.
• Functional groups: 1,3-dicarbonyl (activated methylene/enolizable), ethyl ester, thioether side chain [–CH2–CH(S–Et)–CH3]. The 1,3-diketone and ester together provide multiple acidic α-positions and strong enolization propensity.
• Stereochemistry: none explicitly defined in the name; the side chain contains a secondary carbon (–CH(S–Et)–) that could be prochiral; unless specified, treat as racemic when stereocenters are formed during synthesis.
• 2D description in words: a six-membered ring containing two opposing carbonyls (at positions 1 and 3 relative) and a carboxylate ethyl ester appended to the ring, with an alkyl chain at C-2 that contains an internal secondary carbon bearing an ethylthio substituent.

Synthetic Utility

Key functional elements and their reactivity (general)

• 1,3-Dicarbonyl/β-keto ester: Readily forms soft, resonance-stabilized enolates enabling C–C bond formation (alkylation, Michael additions, acylations), cyclizations, and condensations (e.g., Knoevenagel, Dieckmann intramolecular Claisen types when appropriately tethered).
• Thioether side chain: Convertible handle; oxidation to sulfoxide/sulfone (tunable), Pummerer-type chemistry from sulfoxides, and potential for β-elimination or α-functionalization adjacent to sulfur.
• α-Halogenation: NBS/NCS/NIS or halogen under acid can introduce halogens at activated positions to generate versatile electrophiles.

Retrosynthetic value

• Serves as a masked 1,3-dicarbonyl synthon that can be diversified at the α-position, followed by decarboxylation or transesterification to adjust polarity and protecting-group strategy.
• The side-chain sulfur is a strategic lever to modulate leaving-group ability after oxidation (sulfone), enabling Julia-like olefinations or fragmentation tactics.

Downstream elaborations (examples)

• Condensation with hydrazines → pyrazolones; with hydroxylamine → isoxazolones; with ureas/guanidines → pyrimidinones.
• Enolate capture with electrophiles (alkyl halides, aldehydes via aldol-type additions), followed by lactamization or ring closures to access polycyclic frameworks.

Target Specificity

Not applicable. This product is a small-molecule synthetic building block and is not an antibody, enzyme, or affinity reagent. No target binding or species selectivity information is provided or implied.