N-Caffeoylputrescine - ≥99% , CAS No.29554-26-5

CAS: 29554-26-5 Cat. No.: N977641 Formula: C₁₃H₁₈N₂O₃ Peso molecolare: 250.290

GRADE & PURITY ≥99%

Storage

Room temperature

Specifications

Specifiche e purezza

≥99%

Condizioni di conservazione di stoccaggio

Room temperature

Purezza

≥99%

Nomi e identificatori

• Sorrisi canonici: C1=CC(=C(C=C1/C=C/C(=O)NCCCCN)O)O
• IUPAC Name: (E)-N-(4-aminobutyl)-3-(3,4-dihydroxyphenyl)prop-2-enamide
• InChIKey: KTZNZCYTXQYEHT-GQCTYLIASA-N
• INCHI: 1S/C13H18N2O3/c14-7-1-2-8-15-13(18)6-4-10-3-5-11(16)12(17)9-10/h3-6,9,16-17H,1-2,7-8,14H2,(H,15,18)/b6-4+
• Peso molecolare: 250.290

Taxonomic Classification

Taxonomy Tree

• Kingdom Organic compounds
  • Superclass Phenylpropanoids and polyketides
    • Classe Cinnamic acids and derivatives
      • Subclass Hydroxycinnamic acids and derivatives

• Kingdom: Organic compounds
• Superclass: Phenylpropanoids and polyketides
• Classe: Cinnamic acids and derivatives
• Subclass: Hydroxycinnamic acids and derivatives
• Intermediate Tree Nodes: Not available
• Direct Parent: Hydroxycinnamic acids and derivatives
• Alternative Parents: Cinnamic acid amides Styrenes Catechols 1-hydroxy-4-unsubstituted benzenoids 1-hydroxy-2-unsubstituted benzenoids Secondary carboxylic acid amides Amino acids and derivatives Organopnictogen compounds Organic oxides Monoalkylamines Hydrocarbon derivatives Carbonyl compounds
• Molecular Framework: Aromatic homomonocyclic compounds
• Substituents: Cinnamic acid amide - Hydroxycinnamic acid or derivatives - Catechol - Styrene - 1-hydroxy-4-unsubstituted benzenoid - 1-hydroxy-2-unsubstituted benzenoid - Phenol - Monocyclic benzene moiety - Benzenoid - Amino acid or derivatives - Carboxamide group - Secondary carboxylic acid amide - Carboxylic acid derivative - Amine - Organonitrogen compound - Primary aliphatic amine - Organooxygen compound - Primary amine - Hydrocarbon derivative - Organic oxide - Organopnictogen compound - Carbonyl group - Organic oxygen compound - Organic nitrogen compound - Aromatic homomonocyclic compound
• Descrizione: This compound belongs to the class of organic compounds known as hydroxycinnamic acids and derivatives. These are compounds containing an cinnamic acid (or a derivative thereof) where the benzene ring is hydroxylated.
• External Descriptors: N-substituted putrescine

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: 250.290 g/mol
• XLogP3: 0.800
• Hydrogen Bond Donor Count: 4
• Hydrogen Bond Acceptor Count: 4
• Rotatable Bond Count: 6
• Exact Mass: 250.132 Da
• Monoisotopic Mass: 250.132 Da
• Topological Polar Surface Area: 95.600 Ų
• Heavy Atom Count: 18
• Formal Charge: 0
• Complexity: 281.000
• Isotope Atom Count: 0
• Defined Atom Stereocenter Count: 0
• Undefined Atom Stereocenter Count: 0
• Defined Bond Stereocenter Count: 1
• Undefined Bond Stereocenter Count: 0
• The total count of all stereochemical bonds: 1
• Covalently-Bonded Unit Count: 1

Application Protocols

No vendor-validated protocols are provided for this item. Typical research uses are summarized for convenience (general guidance; optimize in your laboratory):

• Preparation of LC–MS calibration standards

  1. Accurately weigh material under low light. 2) Prepare a primary stock in DMSO or methanol (e.g., 1–10 mM). 3) Serially dilute into 0.1% formic acid in water:organic (e.g., 50:50 MeOH/H2O) to desired calibration range. 4) Store aliquots at −20 °C, protected from light; minimize freeze–thaw.

• Enzyme assay substrate

  1. Prepare fresh working solutions in buffer pH 6–7 with 1–5% DMSO cosolvent. 2) Include 0.1–1 mM EDTA to limit metal-catalyzed oxidation if compatible. 3) Monitor reactions by LC–MS/UV at 320–330 nm.

• Derivatization for detection

  • React free primary amine with NHS–fluorophore in DMF with DIPEA (pH 8–9 equivalent) at RT for 1–2 h; purify by RP-HPLC.

Item-specific recommended dilutions/concentrations, validated applications (WB, IHC, IF, FC), and positive controls: Not applicable and not specified for this item.

Biological Roles

General literature context (no medical/clinical claims)

• Natural occurrence

  • N-Caffeoylputrescine is a plant phenolamide (hydroxycinnamoyl–polyamine conjugate) detected in several species, notably in Solanaceae (e.g., tomato, pepper, tobacco). It arises via acyltransferases that couple caffeoyl-CoA to putrescine.

• Biosynthesis and metabolism

  • Enzymatic formation by BAHD acyltransferases using caffeoyl-CoA as the acyl donor and putrescine as acceptor; subsequent metabolism can include oxidation, glycosylation of phenolic OHs, or further acylation to diacylated polyamines (literature).
  • Part of the phenylpropanoid network linking primary polyamine metabolism (ornithine/arginine decarboxylation → putrescine) with secondary metabolites.

• Physiological roles in plants (literature)

  • Accumulates during biotic/abiotic stress, contributing to defense responses; phenolamides may modulate cell wall reinforcement, radical scavenging, and signaling.
  • Potential roles in pollen development and reproductive tissues where polyamine conjugates are enriched.

• Analytical significance

  • Serves as a marker metabolite for pathway activity and environmental response profiling; robust UV chromophore facilitates LC–UV/LC–MS detection.

• Chemical properties relevant to biology

  • Catechol confers antioxidant and metal-chelating behavior; protonatable amine influences cellular partitioning and ion-trap behavior in MS.

Note: The above reflects general literature knowledge about phenolamides and N-caffeoylputrescine as a natural product standard for research use only.

Buffer Applications

This compound is a small-molecule metabolite, not a buffering agent. It lacks a defined, narrow pH buffering range suitable for preparing laboratory buffers. Practical notes for handling in buffers:

• Dissolve first in a miscible polar solvent (e.g., DMSO or ethanol), then dilute into mildly acidic aqueous buffers (pH 5–6.5; acetate, citrate, or formate) to improve solubility and limit catechol oxidation.
• Avoid strong alkaline buffers (pH > 8) unless necessary; if used, minimize oxygen exposure and include a chelator (e.g., EDTA) to suppress metal-catalyzed oxidation.

Green Alternatives

Although N-caffeoylputrescine is a solid metabolite rather than a process solvent, greener choices can be made for its handling, extraction, and analysis.

• Greener solvent choices (literature guidance)

  • Prefer ethanol:water or methanol:water mixtures over chlorinated solvents for extraction from plant matrices.
  • For LC mobile phases, use water with ethanol or methanol rather than acetonitrile where method performance allows; buffer with volatile, low-toxicity acids (formic/acetic).
  • For stock solutions, ethanol can substitute for DMSO in certain bioassays, reducing persistent solvent burden.

• Stabilization without hazardous additives

  • Limit use of strong amine bases and transition-metal salts; rely on pH control (pH 5–6) and oxygen exclusion instead of chemical antioxidants when feasible.

• Comparison (general; not item specifications)

  • Option: Ethanol–water (70:30) vs. ACN–water (70:30) • Safety: ethanol less toxic and from renewable sources; ACN is petrochemical and toxic. • Performance: ACN offers lower viscosity and stronger elution; ethanol may require higher temperature/pressure and adjusted gradients.
  • Option: Supercritical CO2 with polar modifiers for extraction • Pros: low solvent residue, recyclable CO2. • Cons: equipment-intensive; catechol polarity often necessitates significant polar co-solvent.

• Waste minimization

  • Adopt microscale assays and UHPLC to cut solvent consumption; consolidate standards and use multi-analyte methods when possible.

Pharmaceutical Uses

No pharmacopeial monograph or excipient designation is known for N-caffeoylputrescine. It is primarily used as a research chemical and analytical standard.

• Potential roles in pharmaceutical research workflows (general)

  • Analytical reference standard in natural product characterization and quality control of botanical materials.
  • Tool compound in enzyme assays investigating acyltransferases or polyamine metabolism.
  • Structural motif for SAR exploration of phenolamide scaffolds (as research only).

• Formulation considerations (if used in research formulations)

  • Solubility enhanced in mildly acidic aqueous vehicles or polar organics; prepare concentrated DMSO/ethanol stocks for addition to assay media.
  • Light and air sensitivity of catechols necessitate amber containers and oxygen-minimized handling.

Note: Not intended for human or veterinary use. For research use only, as stated in the Product Data.

Physical Properties

Item-specific specifications

• Melting point, solubility, density, refractive index, UV cutoff, water content, and related specifications: Not specified for this item; refer to CoA/Spec Sheet.

General/literature characteristics for N-caffeoylputrescine and related phenolamides (for context; not item specifications)

• Physical state: typically an off-white to tan solid for isolated phenolamides; may darken on exposure to air/light due to catechol oxidation.
• Solubility profile: good solubility in polar organic solvents (DMSO, DMF, methanol, ethanol); limited to moderate solubility in water at neutral pH; increased aqueous solubility upon mild acidification (e.g., acetate/citrate buffers) due to protonation of the primary amine.
• Acid–base properties: contains one primary amine (basic; pKa of similar putrescine primary amines ~10–11, literature) and two phenolic OH groups (acidic; pKa often ~9–10 for catechols, literature). The amide N is non-basic.
• Partitioning: expected low to moderate logP due to multiple heteroatoms and hydrogen bonding; commonly behaves as a polar, H-bonding analyte in chromatography (literature).
• UV/Vis: strong absorbance near 320–330 nm and 280 nm bands typical of caffeoyl chromophores; phenolic/cinnamamide conjugation supports sensitive UV detection (literature).
• Stability: catechol moiety is air- and light-sensitive; gradual oxidation/polymerization may occur, especially at basic pH or in presence of metal ions. Store protected from light with antioxidants/chelators if applicable (general guidance).

Quality and Grades

• Item-specific quality

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

• How to interpret typical grades for small-molecule reference materials (general guidance)

  • Research/biochemical grade: suitable for discovery research, metabolomics standards, and enzymology; impurity profiles prioritized for structural fidelity rather than chromatographic baselines.
  • HPLC/LC–MS grade standard: emphasizes low non-volatile residues and well-defined purity by HPLC/MS, enabling quantitative metabolite assays. UV impurities near 280–330 nm are especially relevant for caffeoyl chromophores.
  • Stabilization: phenolics sometimes include trace antioxidants or are packaged under inert gas; any stabilizer will be declared on the CoA/label if used. Absence of a declared stabilizer implies none is intentionally added.

• Recommended verification upon receipt (best practices)

  • Identity: confirm by LC–MS (m/z of [M+H]+ / [M–H]−), UV spectrum (caffeoyl maxima), and 1H NMR (catechol protons ~6.7–7.2 ppm; trans –CH=CH– coupling J ~15–16 Hz, literature).
  • Purity: assess by HPLC with diode-array at 325 and 280 nm; monitor for oxidized/dimeric byproducts.
  • Water/solvent content: determine by Karl Fischer/TGA if critical to your application (e.g., quantitative standards). Any item-specific numeric limits not listed here: Not specified for this item; refer to CoA/Spec Sheet.

Reaction and Applications

• Research applications (expanding on typical manufacturer use of life-science metabolite standards)

  • Analytical standard for plant phenolamides in metabolomics, food/plant biochemistry, and stress-response studies (LC–MS/UV quantitation).
  • Substrate or product standard for BAHD-type N-hydroxycinnamoyltransferases that acylate polyamines (biochemical pathway interrogation).
  • Chemical probe precursor: the primary amine allows further derivatization (e.g., fluorophore tags via NHS esters) for imaging/affinity studies.

• Representative reactions and transformations (literature-general)

  • Oxidation: catechol can be oxidized to o-quinone (with periodate, laccases, or air/O2 under basic conditions), enabling conjugate addition to nucleophiles (thiols/amines).
  • Metal complexation: catechol moiety chelates Fe3+/Al3+, affecting spectral properties; useful for binding/antioxidant assays.
  • Amine acylation/alkylation: the free primary amine can be protected (Boc, Fmoc), acylated, or converted to salts; selective diacylation with another hydroxycinnamoyl donor gives di-caffeoylputrescines.
  • Conjugate additions: the α,β-unsaturated amide can participate in Michael-type additions under strong conditions, though the amide conjugation reduces electrophilicity (less reactive than acrylates).

• Practical tips

  • Minimize oxidation by working under subdued light, with degassed solvents and added chelators/antioxidants as compatible.
  • For quantitative work, standardize by weight and confirm concentration spectrophotometrically using the caffeoyl chromophore (ε near 320–330 nm; determine experimentally for your system).
  • Use glassware free of metal contamination when studying redox properties; trace metals accelerate catechol oxidation.

Reaction Conditions

General literature conditions for preparing and manipulating N-caffeoylputrescine (not item specifications):

• Amide coupling (solution-phase)

  • Reagents: caffeic acid (protected or unprotected), putrescine (mono-protected, e.g., Boc), EDC·HCl (1.1–1.5 eq), HOBt or Oxyma (1.1–1.5 eq), DIPEA (2–3 eq).
  • Solvent: DMF, DCM/DMF, or MeCN; 0–25 °C; 2–16 h.
  • Workup: aqueous quench, extract, deprotect (TFA for Boc), and purify by silica or reversed-phase chromatography. Typical isolated yields reported for similar phenolamides: 50–80% depending on protection and purification (literature).

• Acid chloride route

  • Generate caffeoyl chloride with oxalyl chloride (1.2 eq) and a catalytic DMF in DCM at 0–25 °C; couple to mono-protected putrescine with DIPEA at 0–5 °C to control exotherm; 1–3 h.

• Enzymatic synthesis

  • BAHD acyltransferase with caffeoyl-CoA and putrescine in Tris/HEPES buffer (pH ~7–8) at 25–37 °C; Mg2+ often not required; monitor by LC–MS. Offers regioselectivity and mild conditions (literature).

• Derivatizations and stability

  • O-Methylation: MeI/K2CO3 or Me2SO4 to form mono/di-methyl ethers; strictly anhydrous, 0–25 °C.
  • Oxidation: NaIO4 (stoichiometric) or laccase-mediated for catechol → o-quinone; perform under controlled pH (6–7) and low temperature to avoid overoxidation.
  • Light/oxygen sensitivity: conduct under inert atmosphere (N2/Ar) and subdued light, particularly for basic media.

• Analytical methods

  • LC–MS: negative ESI often gives intense [M–H]− for caffeoyl amides; UV monitor at 320–330 nm. Employ 0.1% formic acid or acetic acid for reproducible peak shape.

Safety and Handling

Authoritative safety information is provided in the product SDS; consult it before use.

• Item-specific hazard data

  • Signal word, H-statements, GHS classification, pictograms: Not specified for this item; refer to SDS.

• General safety considerations for phenolic amides/polyamines (informational; not item-specific)

  • Likely hazards: may cause skin/eye irritation; dust may irritate respiratory tract. Phenolic compounds can stain and may oxidize to quinones that are more irritating.
  • PPE: lab coat, nitrile gloves, safety glasses; use a dust mask or handle in fume hood if powders become airborne.
  • Handling: avoid inhalation of dust; avoid contact with oxidizing agents. Keep away from strong bases (accelerates catechol oxidation) and strong oxidants (risk of exotherm/rapid darkening).
  • Incompatibilities: strong oxidizers; basic solutions in presence of air and transition metals (can catalyze oxidation of catechols). Add metal chelators (e.g., EDTA) to aqueous solutions if oxidation is a concern (general practice).
  • First aid (overview): rinse eyes/skin with water for at least 15 minutes upon contact; move to fresh air if inhaled; seek medical attention if symptoms persist. If ingested, rinse mouth and seek advice; do not induce vomiting unless directed by medical personnel.
  • Spill/cleanup: avoid dust generation; sweep up with minimal agitation; place in appropriate waste container. For solutions, absorb with inert material.
  • Fire safety: organic solid; use CO2, dry chemical, or foam. Combustion may produce CO/CO2 and nitrogen oxides.

• Waste: dispose of according to institutional and local regulations. Avoid drain disposal without proper neutralization and approval.

Solvent Selection

Given its polar functionality (catechol, amide, primary amine), N-caffeoylputrescine behaves as a hydrogen bond donor/acceptor–rich analyte.

• Polarity and miscibility (literature-based behavior)

  • Preferred solvents for stock solutions: DMSO, DMF, methanol, ethanol.
  • Aqueous solubility: enhanced in mildly acidic media (e.g., 0.1% formic or acetic acid) via amine protonation; reduced at basic pH due to deprotonation of phenols and potential aggregation/oxidation.
  • Partitioning: low to moderate hydrophobicity; often requires polar organic content for chromatographic elution.

• Chromatography considerations

  • Reversed-phase LC: start with water (0.1% FA) / acetonitrile (0.1% FA) gradients; retention influenced by ionization state. Negative ESI gives strong signal for phenolates; positive ESI captures protonated amine.
  • HILIC: viable for very polar retention; ensure adequate organic (acetonitrile-rich) content and buffer at pH 3–6.

• Practical selection

  • For bioassays/enzyme studies: prepare concentrated DMSO stocks (e.g., 10–50 mM) and dilute into buffered aqueous systems at pH 5–7 to minimize oxidation.
  • For extraction from plant matrices: methanol:water or ethanol:water (50–80%) with 0.1–1% acid often used; add EDTA to suppress metal-catalyzed oxidation (literature practice).

• Alternatives and caveats

  • Avoid strong base and prolonged exposure to air/light in solution (catechol oxidation). If basic conditions are necessary, deoxygenate solutions and include antioxidants (ascorbate/sulfite) where compatible.

Storage and Reconstitution

• Item-specific storage/shipping

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

• General best practices for this compound class (phenolic amides/catechols)

  • Storage: keep tightly closed, dry, and protected from light (amber vial). Although room temperature storage is indicated, cool, desiccated storage can further slow oxidation; avoid prolonged exposure to air.
  • Inert atmosphere: consider purging vials with nitrogen/argon after opening.
  • Packaging: use PTFE-lined caps; avoid reactive metals.

• Reconstitution guidance (research use)

  • Prepare a concentrated stock solution in DMSO, methanol, ethanol, or DMF (e.g., 10–50 mM). Filter if necessary through 0.22 μm PTFE.
  • For aqueous use, dilute stocks into mildly acidic buffers (e.g., 0.1% formic/acetic acid in water or pH 5–6 acetate/citrate) to enhance solubility and stability. Include EDTA (0.1–1 mM) to chelate trace metals if compatible with your assay.
  • Working solution stability: prepare fresh daily when possible; store short-term aliquots at 2–8 °C protected from light. For longer-term storage, freeze aliquots at −20 to −80 °C and avoid repeated freeze–thaw cycles.

• Specifications such as acceptable water content, peroxide levels, and stabilizers: Not specified for this item; refer to CoA/Spec Sheet.

• Research Use Note: For research use only.

Structure and Identity

Brief description: N-Caffeoylputrescine is a phenolic amide formed by acylation of the diamine putrescine (1,4-diaminobutane) with caffeic acid (3,4-dihydroxycinnamic acid). It belongs to the plant phenolamide (hydroxycinnamoyl–polyamine) family.

• Item-specific (from Product Data)

  • SKU: N977641
  • CAS: 29554-26-5
  • PubChem CID: 5280559
  • InChIKey: 189590 (as provided)
  • Storage: Room temperature
  • Grade/Purity: Not specified for this item; refer to CoA/Spec Sheet.
  • Appearance: Not specified for this item; refer to CoA/Spec Sheet.

• Structural features (general description)

  • Core motifs: a trans-cinnamamide linkage connecting a catechol-substituted phenyl ring (3,4-dihydroxyphenyl) to a 4-carbon aliphatic chain terminating in a primary amine (residual –NH2 of putrescine).
  • Functional groups: one amide (–CONH–), one primary amine (–CH2–CH2–CH2–CH2–NH2), two phenolic hydroxyls (catechol), and an alkene (–CH=CH–) conjugated to the amide carbonyl (caffeoyl).
  • Conjugation: extended π-system from the aromatic ring through the α,β-unsaturated amide, enabling UV absorbance in near-UV/visible.
  • Stereochemistry: typically the E (trans) geometry at the cinnamamide double bond (literature). No stereocenters present.

• Formula and SMILES

  • Molecular formula: Not specified for this item; refer to CoA/Spec Sheet.
  • Molecular weight: Not specified for this item; refer to CoA/Spec Sheet.
  • SMILES: Not specified for this item; refer to CoA/Spec Sheet.

• 2D structure in words: A 3,4-dihydroxyphenyl ring bearing a propenamide sidechain (–CH=CH–C(=O)–NH–), which is further bound to a butyl chain ending in –NH2.

Synthetic Utility

From a synthetic perspective, N-caffeoylputrescine integrates multiple functional handles that facilitate derivatization and method development.

• Functional group leverage

  • Catechol (3,4-dihydroxy): amenable to selective protection (benzyl, silyl, carbonate) and oxidative transformations to o-quinones for conjugation chemistry.
  • α,β-Unsaturated amide: participates in photochemical E/Z isomerization; limited Michael acceptor reactivity; UV-active handle for monitoring reactions.
  • Primary amine: site for salt formation, acylation (e.g., to form diacylated polyamines), urea/carbamate formation (e.g., with isocyanates/chloroformates), or labeling with NHS esters/activated carbonates.

• Retrosynthetic access (general routes)

  1. Protect one amine of putrescine (e.g., Boc), couple caffeic acid (or protected caffeic acid) via EDC/HOBt or HATU to give the monoamide, then deprotect.
  2. Use caffeoyl chloride (generated in situ with SOCl2/oxalyl chloride under mild conditions) and a base (DIPEA) for acylation; control mono- vs diacylation by stoichiometry and protection.
  3. Enzymatic synthesis using plant BAHD acyltransferases with caffeoyl-CoA as donor for regioselective N-acylation (literature).

• Applications enabled

  • Preparation of standards and isotopically labeled analogs (e.g., 13C/15N) for quantitative LC–MS.
  • Synthesis of conjugates (e.g., biotin, fluorophores) via the free amine for affinity assays.
  • Generation of O-derivatives (methyl/acetyl) to modulate polarity and improve chromatographic resolution during method development.

Target Specificity

This product is a small organic molecule, not a biological targeting reagent (e.g., antibody, inhibitor with defined protein selectivity panel, or oligonucleotide).

• Item-specific targeting data (antigen/epitope, species reactivity, clone, isotype): Not applicable and not specified for this item.

• Context note: In biochemical studies, N-caffeoylputrescine may be used as a substrate/standard for enzymes in the phenylpropanoid/polyamine conjugation pathway, but no specific molecular target selectivity claims are made for this catalog item.