Benzyl 2-(diethoxyphosphoryl)acetate - ≥95% , CAS No.7396-44-3

CAS: 7396-44-3 Cat. No.: B590048 Fórmula: C₁₃H₁₉O₅P Peso molecular: 286.27

GRADE & PURITY ≥95%

Synonyms

SCHEMBL5849992 | (Diethoxy-phosphoryl)acetic acid benzyl ester | (Diethoxy-phosphoryl)-acetic acid benzyl ester | Benzyl 2-(diethoxyphosphoryl)acetate | OTRQFHJPBPUOES-UHFFFAOYSA-N | Acetic acid, (diethoxyphosphinyl)-, phenylmethyl ester | diethyl (benzyl

Storage

Room temperature,Argon charged

Shipped In

Normal

Specifications

Sinónimos

SCHEMBL5849992 | (Diethoxy-phosphoryl)acetic acid benzyl ester | (Diethoxy-phosphoryl)-acetic acid benzyl ester | Benzyl 2-(diethoxyphosphoryl)acetate | OTRQFHJPBPUOES-UHFFFAOYSA-N | Acetic acid, (diethoxyphosphinyl)-, phenylmethyl ester | diethyl (benzyl

Especificações e pureza

≥95%

Condições de armazenamento de armazenamento

Room temperature,Argon charged

Enviado em

Normal

Pureza

≥95%

Nomes e identificadores

Sorrisos canónicos

CCOP(=O)(CC(=O)OCC1=CC=CC=C1)OCC

IUPAC Name

benzyl 2-diethoxyphosphorylacetate

InChIKey

OTRQFHJPBPUOES-UHFFFAOYSA-N

INCHI

1S/C13H19O5P/c1-3-17-19(15,18-4-2)11-13(14)16-10-12-8-6-5-7-9-12/h5-9H,3-4,10-11H2,1-2H3

SMILES isoméricas

CCOP(=O)(CC(=O)OCC1=CC=CC=C1)OCC

Peso molecular

286.27

Reaxy-Rn

2564283

Reaxys-RN_link_address

https://www.reaxys.com/reaxys/secured/hopinto.do?context=S&query=IDE.XRN=2564283&ln=

Taxonomic Classification

Taxonomy Tree

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

• Kingdom: Organic compounds
• Superclass: Benzenoids
• Classe: Benzene and substituted derivatives
• Subclass: Benzyloxycarbonyls
• Intermediate Tree Nodes: Not available
• Direct Parent: Benzyloxycarbonyls
• Alternative Parents: Dialkyl alkylphosphonates Phosphonic acid esters Carboxylic acid esters Monocarboxylic acids and derivatives Organopnictogen compounds Organophosphorus compounds Organic oxides Hydrocarbon derivatives Carbonyl compounds
• Molecular Framework: Aromatic homomonocyclic compounds
• Substituents: Benzyloxycarbonyl - Dialkyl alkylphosphonate - Phosphonic acid diester - Phosphonic acid ester - Organophosphonic acid derivative - Carboxylic acid ester - Carboxylic acid derivative - Monocarboxylic acid or derivatives - Organic oxygen compound - Organooxygen compound - Organophosphorus compound - Hydrocarbon derivative - Organic oxide - Organopnictogen compound - Carbonyl group - Aromatic homomonocyclic compound
• Descrição: This compound belongs to the class of organic compounds known as benzyloxycarbonyls. These are organic compounds containing a carbonyl group substituted with a benzyloxyl 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

• Sensibilidade: Air sensitive
• Peso molecular: 286.260 g/mol
• XLogP3: 1.600
• Hydrogen Bond Donor Count: 0
• Hydrogen Bond Acceptor Count: 5
• Rotatable Bond Count: 9
• Exact Mass: 286.097 Da
• Monoisotopic Mass: 286.097 Da
• Topological Polar Surface Area: 61.800 Ų
• Heavy Atom Count: 19
• Formal Charge: 0
• Complexity: 302.000
• 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. This product has no antibody/assay application protocols (e.g., WB, IHC, IF, FC). For practical use, see Reaction Conditions and Application notes in Reaction & Applications and Synthetic Utility.

Biological Roles

This product is a synthetic organophosphorus building block intended for chemical synthesis. It does not have a defined physiological role.

• General context (biochemistry, literature)

  • Dialkyl phosphonates can mimic phosphate esters in some contexts, but benzyl 2-(diethoxyphosphoryl)acetate is primarily used as a carbon–carbon bond-forming reagent in organic synthesis rather than in biochemical systems.
  • No endogenous metabolic pathways are associated with this specific compound.

• Research use note

  • For research use only. Not intended for food, drug, cosmetic, or household use.

For biological or cellular studies, users typically employ products with defined biocompatibility and formulation data; such applications are not typical for this reagent.

Buffer Applications

Not typically applicable. Benzyl 2-(diethoxyphosphoryl)acetate is a synthetic reagent used in organic reactions and is not used to formulate laboratory buffer systems. For practical information, see the sections on Reaction & Applications, Synthetic Utility, and Reaction Conditions.

Green Alternatives

While this reagent is itself a substrate rather than a solvent, greener choices can be made around its use and, in some cases, by selecting alternative reagents that achieve similar outcomes.

• Greener solvent choices (general)

  • Replace THF with 2‑MeTHF or CPME: both offer improved lifecycle metrics and lower peroxide management than ethers like THF (2‑MeTHF still forms peroxides but is bio-based and has favorable boiling point).
  • Use MeCN or EtOAc instead of DCM where feasible to reduce chlorinated waste. Toluene can substitute DCM for higher-boiling requirements.

• Alternative reagents and protecting groups

  • Swap benzyl for tert‑butyl 2-(diethoxyphosphoryl)acetate when acidolytic deprotection (TFA) is preferred over hydrogenolysis, avoiding use of H2/Pd.
  • Employ triethyl phosphonoacetate (TEPA) if a permanent ethyl ester is acceptable, eliminating a hydrogenolysis step (tradeoff: less orthogonal deprotection).

• Base and process intensification

  • Use milder inorganic bases (K2CO3/Cs2CO3) in high-dielectric solvents (MeCN/EtOH co-solvent) to reduce hazards of pyrophoric bases (NaH) when substrate scope allows.
  • Explore continuous-flow deprotonation/olefination to improve thermal control and reduce solvent volumes.

• Comparison snapshot (general guidance)

  • THF vs 2‑MeTHF: similar reactivity; 2‑MeTHF often allows easier phase separations and can be derived from renewables.
  • DCM vs EtOAc: EtOAc is less hazardous and biodegradable, but solubility/selectivity may differ.

Adopt green metrics tracking (E-factor, PMI) and solvent selection guides (e.g., GSK/ACS) to optimize the sustainability of processes employing this reagent.

Pharmaceutical Uses

This product is a research chemical/reagent and is not an approved excipient or active ingredient.

• Formulation/excipient status

  • No pharmacopeial monograph or excipient status is indicated. Not specified for this item; refer to CoA/Spec Sheet.

• Relevance to medicinal chemistry (general)

  • Useful intermediate for constructing α,β-unsaturated carboxylic acid frameworks via HWE olefination. The benzyl ester enables late-stage deprotection by hydrogenolysis in route scouting.

• Manufacturing considerations

  • If employed in a GMP setting, impurity profiling (residual solvents, phosphorus-containing byproducts) and metal residues from hydrogenolysis catalysts require control. Such controls are process- and lot-specific and are not provided here.

No medical or clinical claims are made. For regulatory use, develop process-specific specifications and validate analytical methods.

Physical Properties

Item-specific physicochemical specifications (bp, mp, density, refractive index, elemental/impurity limits) are not provided in the Product Data.

• Item-specific specs

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

• Literature/computed properties (non-binding, for general reference only)

  • Molecular formula: C13H19O5P (literature)
  • Molecular weight: ~286.26 g/mol (literature)
  • Functional profile: neutral, polar organophosphorus ester; moderate lipophilicity due to benzyl and ethoxy groups; contains an acidic α-CH2 next to P(=O) and C=O (pKa of α-CH typically ~22–24 in DMSO for dialkyl phosphonoacetates; literature range)
  • Solubility: expected good solubility in common aprotic organic solvents (THF, DCM, EtOAc, DMF, acetonitrile) and poor solubility in water (general chemical knowledge for dialkyl phosphonoacetate benzyl esters).

• Notes on data use

  • The above values are typical for the structure class and are provided as literature/general guidance. Do not treat as acceptance criteria for this catalog item. For exact specifications, consult the Aladdin CoA/Spec Sheet for SKU B590048.

Quality and Grades

• Item-specific quality 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.
  • Appearance and acceptance criteria: Not specified for this item; refer to CoA/Spec Sheet.

• Guidance on interpreting common grades (general)

  • Research grade: Suitable for most synthetic and preparative work. Impurity profile may not be optimized for trace analysis.
  • High-purity or HPLC grade (when applicable): Lower UV-absorbing impurities and particulates; advantageous for photochemical applications or when used as a reagent in sensitive catalytic reactions.
  • Water/acid/base content: For phosphonate reagents, trace water and residual alcohols can influence base-mediated reactions (e.g., HWE). Verify Karl Fischer and residual solvent by CoA where critical.

• Practical considerations for this reagent class

  • Acidic impurities will quench the phosphonate carbanion; peroxides are generally not a concern (unlike ethers), but hydrolytic degradation to alcohols/acids can occur over long storage or with moisture exposure.
  • For stereosensitive HWE or base-sensitive substrates, consider pre-testing a small aliquot and, if needed, purifying by column chromatography under dry conditions to remove polar degradants.

For exact specifications and release criteria of SKU B590048, consult the Aladdin CoA/Spec Sheet accompanying your lot.

Reaction and Applications

Benzyl 2-(diethoxyphosphoryl)acetate is a stabilized phosphonoacetate reagent optimized for carbon–carbon bond formation via Horner–Wadsworth–Emmons (HWE) and related olefination chemistry.

• Key transformations (general/literature)

  • HWE olefination with aldehydes/ketones to furnish E-selective α,β-unsaturated benzyl esters. Subsequent hydrogenolysis (Pd/C, H2) unveils the corresponding acids, enabling convergent access to acrylic and cinnamic acid derivatives.
  • Knoevenagel-type condensations under basic conditions with suitable electrophiles.
  • Michael donor precursor: the phosphonate-stabilized carbanion can add to strong Michael acceptors, followed by elaboration.

• Practical tips

  • Base choice tunes reactivity/selectivity: NaH, KHMDS, or LiHMDS at 0 to −78 °C for reactive aldehydes; K2CO3/Cs2CO3 or DBU at 0–25 °C for milder conditions and base-sensitive substrates.
  • Order of addition: pre-generate the phosphonate anion in dry THF, then add carbonyl electrophile at controlled temperature to minimize self-condensation.
  • Quench and workup: quench with saturated NH4Cl or weak acid; remove inorganic salts by filtration; purify by silica gel chromatography using non-protic eluents.

• Strategic advantages of the benzyl ester handle

  • Orthogonal deprotection: benzyl group can be removed selectively by hydrogenolysis without affecting base-labile groups, enabling late-stage acid unveiling.
  • Improved lipophilicity can enhance solubility of intermediates during synthesis and facilitate extractions.

• Representative outcomes (literature)

  • E:Z ratios typically high (often >10:1) for aldehyde couplings; isolated yields commonly 60–90% depending on substrate and base.

Reaction Conditions

General literature guidance for HWE olefination and related reactions using benzyl 2-(diethoxyphosphoryl)acetate:

• Deprotonation and coupling (typical)

  • Base: NaH (60% oil), KHMDS, or LiHMDS (0.9–1.2 equiv) in dry THF or DME.
  • Temperature: 0 to −78 °C for enolization; then add the carbonyl electrophile (1.0–1.5 equiv) and warm to 0–25 °C.
  • Time: 0.5–4 h after electrophile addition, depending on substrate.
  • Workup: quench with saturated NH4Cl; extract with EtOAc or DCM; dry, filter, and concentrate.
  • Outcome: E‑alkenes favored; isolated yields commonly 60–90% for aldehydes (literature ranges).

• Milder conditions (base-sensitive substrates)

  • Base: K2CO3 or Cs2CO3 (1.5–3 equiv) in MeCN, DMF, or mixed MeCN/EtOH at 20–60 °C; longer times (4–24 h). Useful for electron-deficient aldehydes.

• Hydrogenolysis of benzyl ester (to unveil acid)

  • Catalyst: 5–10 wt% Pd/C (5–10 mol% Pd relative to substrate) in EtOAc, MeOH, or THF.
  • Conditions: H2 balloon to 3 bar at 20–40 °C, 1–12 h; monitor by TLC/HPLC. Filtration through Celite removes Pd/C.

• Notes and tips

  • Dry, oxygen-free conditions improve reproducibility. Moisture competes via hydrolysis, forming phosphonic acids/alcohols.
  • Strong bases can induce O– to C‑alkylation side reactions if electrophiles are present during deprotonation; pre-form the anion, then add carbonyl at low temperature.
  • For ketones, stronger bases/lower temperatures and longer times are typically required; E:Z ratios may be lower than with aldehydes.

All parameters are general literature guidance and should be optimized per substrate.

Safety and Handling

Safety information in the Product Data is not specified; consult the SDS for authoritative guidance.

• GHS classification (item-specific)

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

• General hazards and precautions (general chemical knowledge for dialkyl phosphonate esters)

  • May be harmful if swallowed or in contact with skin; may cause eye and skin irritation. Avoid inhalation of mists/vapors/aerosols.
  • Not expected to be a strong oxidizer or reducer; combustible organic liquid/solid depending on actual physical state.
  • Incompatibilities: strong bases (can deprotonate the α-CH2 and cause exotherm), strong acids (hydrolysis of ester/phosphonate), strong oxidants.

• Recommended PPE and handling

  • Use in a fume hood with lab coat, safety glasses, and appropriate chemical-resistant gloves (e.g., nitrile). Avoid moisture ingress when weighing/dispensing for air/moisture-sensitive reactions.
  • Keep containers tightly closed; minimize exposure to air if prolonged storage could lead to hydrolysis.

• First-aid overview (refer to SDS for full measures)

  • Skin/eyes: Rinse with water for several minutes; remove contaminated clothing; seek medical attention if irritation persists.
  • Inhalation: Move to fresh air; monitor for symptoms; seek medical advice if unwell.
  • Ingestion: Rinse mouth; do not induce vomiting; seek medical attention.

• Fire safety

  • Use CO2, dry chemical, or foam. Cool containers with water spray. Combustion may produce phosphorus oxides.

Always defer to the product-specific SDS from Aladdin for definitive safety classifications and response procedures.

Solvent Selection

This product is a reactive organophosphonate reagent (not a solvent). Solvent choice pertains to its use in synthesis.

• Polarity and solubility (general)

  • Moderately polar, neutral ester; typically soluble in THF, DCM, toluene, acetonitrile, DMF, and EtOAc; limited water solubility.

• Typical solvent choices by operation

  • Base-mediated deprotonation/HWE olefination: Dry THF, DME, or 2-MeTHF are common; DMF/MeCN for milder, higher-dielectric conditions (e.g., K2CO3, Cs2CO3).
  • Low-temperature control: THF or DME at 0 to −78 °C when using strong bases (NaH, LiHMDS) to suppress side reactions.
  • Workup/extraction: DCM or EtOAc for phase separation; hexanes/EtOAc gradients for chromatography.

• Comparison notes (general)

  • THF vs DMF: THF benefits include easier removal and compatibility with strong bases; DMF can increase rates with weak bases but complicates workup and may promote N-acylation of amine substrates.
  • DCM vs toluene: DCM enhances solubility for polar aldehydes at ambient temperature; toluene favored for higher-boiling conditions or when avoiding chlorinated waste.

• Moisture/air considerations

  • Use anhydrous solvents and inert atmosphere to limit hydrolysis and maintain reproducibility in base-mediated reactions.

Select solvents based on substrate solubility, base strength, and temperature window of the intended transformation.

Storage and Reconstitution

• Storage conditions (from Product Data)

  • Store at room temperature.
  • Argon charged: maintain under inert atmosphere. Keep container tightly closed when not in use.
  • Shipped in: Normal.

• Stability and handling (general for phosphonate esters)

  • Protect from moisture and strong acids/bases to avoid hydrolysis or transesterification. For long-term storage, an inert gas blanket (Ar or N2) and desiccation are recommended.
  • Minimize repeated exposure to air; if dispensing frequently, consider aliquoting under inert gas.

• Reconstitution/Preparation

  • Supplied neat; no reconstitution is required. If solidification occurs at low temperature, gently warm to ambient and mix thoroughly before use.
  • For moisture-sensitive reactions, pre-dry by azeotropic co-evaporation with toluene or by standing over activated molecular sieves in anhydrous solvent (general practice).

• Packaging/compatibility

  • Store in glass with compatible PTFE-lined cap. Avoid prolonged contact with reactive metals or strong base residues in caps.

Always consult the product label and Aladdin CoA/SDS for lot-specific guidance. For research use only.

Structure and Identity

Benzyl 2-(diethoxyphosphoryl)acetate is a benzyl ester of a diethyl phosphonoacetic acid derivative, combining a benzylic carbonate and a diethyl phosphonate for HWE-type olefination chemistry.

• Product identifiers (from Product Data)

  • SKU: B590048
  • CAS: 7396-44-3
  • CID (PubChem): 281239
  • InChIKey: 267139 (as provided)
  • SMILES: Not specified for this item; refer to CoA/Spec Sheet.

• Structural features (general/literature description)

  • Core scaffold: benzyl ester of 2-(diethoxyphosphoryl)acetic acid; connectivity is Ph–CH2–O–C(=O)–CH2–P(=O)(OEt)2.
  • Functional groups: aromatic ring (phenyl), benzylic methylene (–CH2–Ph), ester (–CO2–), and a diethyl phosphonate [P(=O)(OEt)2].
  • 2D description: a phenyl ring bearing a benzylic –CH2–O– linker to a carbonyl carbon; the carbonyl α-carbon is a methylene attached directly to a phosphoryl center that carries two ethoxy substituents and a P=O bond.
  • Stereochemistry: none (achiral as drawn); the α-methylene is the acidic site for anion formation.

• Computed/literature identifiers (for reference; not item-specific specs)

  • Typical SMILES (literature): O=C(OCH2c1ccccc1)CP(=O)(OCC)OCC
  • Typical molecular formula (literature): C13H19O5P
  • Typical molecular weight (literature): ~286.26 g/mol

Note: Exact identifiers for this catalog item should be confirmed against the Aladdin CoA/Spec Sheet.

Synthetic Utility

Functionally, benzyl 2-(diethoxyphosphoryl)acetate is a stabilized phosphonoacetate equivalent that enables convergent C=C bond formation and traceless unveiling of the acid functionality.

• Functional handles and reactivity (general)

  • The α-methylene next to P(=O) and C=O is acidic; deprotonation generates a carbanion that reacts with aldehydes/ketones (HWE) to give predominantly E‑alkenes.
  • Benzyl ester serves as a removable protecting group: hydrogenolysis (H2, Pd/C) liberates the free acid under mild conditions.

• Strategic value

  • Access to cinnamic/acrylic acid derivatives bearing sensitive protecting groups (Bn removal orthogonal to acid- or base-labile moieties).
  • Modular assembly: pair with diverse aldehydes to rapidly elaborate structure–activity series in medicinal chemistry campaigns.

• Complementary transformations

  • Alkylation at the α-position under strong base to install substituents prior to olefination.
  • Conversion to mixed anhydrides or further ester exchange after hydrogenolysis to tailor downstream functionality.

• Comparison to analogs

  • Versus triethyl phosphonoacetate: identical HWE reactivity profile but offers a deprotection handle (Bn) vs a persistent ethyl ester.
  • Versus tert‑butyl 2-(diethoxyphosphoryl)acetate: tBu offers acidolysis (TFA) deprotection; benzyl favors catalytic hydrogenolysis selectivity.

These attributes make it a versatile linchpin in route design where controllable olefination and selective acid unmasking are required.

Target Specificity

Not applicable. This product is a small-molecule synthetic reagent and does not possess antigen/epitope specificity, clone information, or species reactivity. No isotype or biological target data apply.