4-bromo-N-hexylaniline - ≥95% , CAS No.125017-21-2

CAS: 125017-21-2 Cat. No.: B1008533 Formula: C₁₂H₁₈BrN Peso molecolare: 256.180

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: CCCCCCNC1=CC=C(C=C1)Br
• IUPAC Name: 4-bromo-N-hexylaniline
• InChIKey: CJMPJDXEPCOGTA-UHFFFAOYSA-N
• INCHI: 1S/C12H18BrN/c1-2-3-4-5-10-14-12-8-6-11(13)7-9-12/h6-9,14H,2-5,10H2,1H3
• Peso molecolare: 256.180

Taxonomic Classification

Taxonomy Tree

• Kingdom Organic compounds
  • Superclass Organic nitrogen compounds
    • Classe Organonitrogen compounds
      • Subclass Amines
        • Level5 Aralkylamines
          • Level6 Phenylalkylamines

• Kingdom: Organic compounds
• Superclass: Organic nitrogen compounds
• Classe: Organonitrogen compounds
• Subclass: Amines
• Intermediate Tree Nodes: Aralkylamines
• Direct Parent: Phenylalkylamines
• Alternative Parents: Aniline and substituted anilines Secondary alkylarylamines Bromobenzenes Aryl bromides Organobromides Hydrocarbon derivatives
• Molecular Framework: Aromatic homomonocyclic compounds
• Substituents: Phenylalkylamine - Aniline or substituted anilines - Secondary aliphatic/aromatic amine - Halobenzene - Bromobenzene - Benzenoid - Monocyclic benzene moiety - Aryl halide - Aryl bromide - Secondary amine - Hydrocarbon derivative - Organobromide - Organohalogen compound - Aromatic homomonocyclic compound
• Descrizione: This compound belongs to the class of organic compounds known as phenylalkylamines. These are organic amines where the amine group is secondary and linked on one end to a phenyl group and on the other end, to an alkyl 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

Proprietà chimiche e fisiche

• Peso molecolare: 256.180 g/mol
• XLogP3: 4.900
• Hydrogen Bond Donor Count: 1
• Hydrogen Bond Acceptor Count: 1
• Rotatable Bond Count: 6
• Exact Mass: 255.062 Da
• Monoisotopic Mass: 255.062 Da
• Topological Polar Surface Area: 12.000 Ų
• Heavy Atom Count: 14
• Formal Charge: 0
• Complexity: 130.000
• 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 predefined biological or analytical application protocols are provided for this small-molecule building block.

• For synthetic applications, follow standard procedures for aryl bromide cross-couplings, lithiation/electrophile trapping, or aniline derivatizations as outlined under Reaction Conditions. Always confirm stoichiometry and conditions on small scale before scale-up.

• If using for materials fabrication (e.g., film casting or device prototyping), determine solvent system and thermal profile empirically to suit your substrate and processing equipment.

Biological Roles

This item is supplied as a synthetic organic building block for research and development. It is not intended for biological system interrogation as-is, and no biological function or metabolic role is assigned for this specific compound.

• General note (informational): Aromatic amines can interact with biological systems, but any discussion of metabolism, toxicity mechanisms, or pharmacology would be project-specific and is outside the scope of this reagent listing.

• Recommendation: If used as a probe precursor or material component in biochemical contexts, evaluate cytotoxicity and stability independently and adhere strictly to institutional safety protocols.

For research use only. Not for human or veterinary applications.

Buffer Applications

Not typically applicable. 4-bromo-N-hexylaniline is a hydrophobic organic building block, not a buffering agent.

• Practical guidance: If a protonated form is required for solubility control or crystallization, mineral or organic acids (e.g., HCl, p-TsOH) can form anilinium salts, but these are not buffering systems. For any aqueous work, employ co-solvents or surfactants, and adjust pH with standard laboratory buffers appropriate to your biological or analytical system.

Green Alternatives

While 4-bromo-N-hexylaniline itself is the required substrate, greener choices can be made around solvents, bases, and catalysts, or by selecting alternative activation patterns.

• Greener solvent choices (for typical transformations):

  • Replace DCM/CHCl3 with toluene, EtOAc, or cyclopentyl methyl ether (CPME) when feasible.
  • Use 2-MeTHF over THF/Et2O for ether-mediated chemistry (renewable feedstock, higher bp, better phase separation).
  • Favor water or aqueous-organic biphasic systems in Suzuki couplings using micellar conditions (e.g., TPGS-750-M) where compatible.

• Catalyst and base considerations:

  • Employ ligand-optimized Pd systems that operate at low loadings (≤0.5 mol%) or nickel catalysis for reduced Pd footprint.
  • Use inorganic bases with better EHS profiles (K2CO3, K3PO4) over strong alkoxides when compatible.

• Alternative activation strategies (project-dependent):

  • If downstream sequence tolerates, prepare the corresponding aryl boronate/boronic acid and perform late-stage couplings from that manifold to reduce reliance on aryl bromides.
  • Consider C–H activation routes from non-halogenated precursors in research settings to minimize halogenated waste.

• Trade-offs:

  • Aryl bromides provide superior reactivity vs chlorides, enabling milder conditions; greener options (chlorides or C–H routes) may demand harsher conditions or specialized catalysts.

Comparison snapshot (general):

• THF vs 2-MeTHF: similar reactivity; 2-MeTHF is bio-derived, less peroxide-prone, easier separations; THF often offers broader solubility.
• DCM vs EtOAc: DCM excellent for dissolution but volatile and toxic; EtOAc safer, biodegradable, but may solubilize amines less effectively.

Pharmaceutical Uses

No pharmacopeial status or excipient role is specified for this item; refer to your regulatory team for any process-related considerations.

• Context (general, non-clinical): Aromatic amine building blocks like 4-bromo-N-hexylaniline may be used in discovery chemistry to assemble API candidates or material intermediates via cross-coupling and amide/sulfonamide formation. Any application remains strictly at the research stage.

• Compliance note: This product is for research use only and is not manufactured for use in human or veterinary drug products. No clinical or therapeutic claims are made or implied.

Physical Properties

• Item-specific specifications (this lot):

  • 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.
  • Other specs (bp, mp, density, refractive index, water/peroxide/metals/UV): Not specified for this item; refer to CoA/Spec Sheet.

• Literature/general properties for 4-bromo-N-hexylaniline (informational only; not product specifications):

  • Phase at RT: typically a viscous liquid or low-melting solid for N-alkylated anilines with C6 chain; exact mp depends on isomeric purity.
  • Solubility: Low in water; good solubility in nonpolar and moderately polar organic solvents (e.g., hexanes, toluene, DCM, THF, EtOAc). Miscibility improved in aromatic/chlorinated media.
  • Acid–base behavior: Weakly basic secondary aniline (conjugate acid pKa typically ~4.5–5.5 for anilinium; free-base basicity considerably attenuated vs aliphatic amines due to resonance).
  • Lipophilicity: Expected high logP due to para-bromo aryl plus hexyl chain (qualitatively >3).

• Practical notes:

  • The aryl bromide enhances density vs non-halogenated analogs; solutions may stratify slowly in biphasic systems.
  • The N–H permits H-bonding; expect modest polarity relative to tertiary anilines, aiding coordination to metals during catalysis.
  • Verify exact physical constants on the item’s CoA prior to process design.

Quality and Grades

• Item-specific grade/purity: Not specified for this item; refer to CoA/Spec Sheet.

• Interpreting typical grades (general guidance):

  • Research/technical grade: Suitable for general synthesis and method development; impurity thresholds defined by internal QC.
  • ≥95–98% (assay) organic building blocks: Fit for routine synthesis; verify residual solvents, isomers, and halide content when needed for catalysis.
  • High-purity or HPLC grade (when applicable): Lower UV-absorbing impurities; beneficial for photoredox or analytical uses. Absence/presence of stabilizers should be declared on the CoA.

• Characterization best practices for aryl bromide anilines:

  • Confirm identity by 1H/13C NMR (para pattern on Ar–H, N–H resonance, hexyl chain multiplets), HRMS (M, M+2 due to Br isotopes), and IR (N–H stretch ~3300 cm⁻¹, C–Br aryl stretch ~500–650 cm⁻¹).
  • Check halide content and residual palladium if material will be used downstream in metal-sensitive steps; metals limits are application-specific.
  • Water content, peroxide value, UV cutoff: Not specified for this item; refer to CoA/Spec Sheet.

• Stabilizers/inhibitors: None indicated for this item. If present in any lot, they will be declared on the Spec Sheet.

Reaction and Applications

As a para-brominated, N-alkylated aniline, 4-bromo-N-hexylaniline offers two complementary reactive sites: an aryl bromide for C(sp2)–X activation and an aniline N–H for derivatization.

• Aryl bromide transformations:

  • Cross-couplings: Robust substrate for Suzuki–Miyaura (to biaryls), Sonogashira (to aryl alkynes), Heck (to vinyl arenes), Negishi/Stille (to sp2–sp2 and sp2–sp3 couplings). The para position minimizes steric encumbrance and typically gives high conversions.
  • Halogen–metal exchange: Fast Br/Li exchange at low temperature (e.g., n-BuLi, s-BuLi) to generate aryllithium for electrophile trapping (aldehydes, CO2, borates). The anilide N–H may need protection or in situ quench control to avoid deprotonation/complexation.
  • Direct borylation: Pd-catalyzed Miyaura borylation to the corresponding pinacol boronate; serves as a gateway to diverse cross-couplings.

• Aniline N–H chemistry:

  • Acylation/Carbamoylation/Sulfonylation: Access to amide, urea, and sulfonamide libraries; the para-bromo handle then enables orthogonal diversification (two-directional synthesis).
  • N-alkylation: Formation of tertiary anilines; use mild bases to avoid competitive dehalogenation under strongly reducing conditions.
  • Reductive amination (after prior carbonyl introduction) and protecting group strategies (Boc, Cbz) for handling in strong-base chemistry.

• Materials/functional uses (research context):

  • Lipophilic anilines are common in organic electronics, dyes, and surfactant-like architectures; the para handle allows tuning of donor strength while the hexyl chain imparts solubility/film-forming properties.

• Practical tips:

  • Dry and degas coupling media; N–H can bind catalysts—ligand-rich systems (e.g., SPhos, XPhos) mitigate inhibition.
  • Consider preforming an anilinium salt for recrystallization/purification, then regenerate the free base.

Reaction Conditions

General literature guidance for transformations of para-bromo anilines (informational; adjust to your system):

• Suzuki–Miyaura coupling (to biaryls):

  • Catalyst: Pd(PPh3)4 (1–2 mol%) or Pd2(dba)3 (1 mol%) + SPhos/XPhos (2–4 mol%).
  • Base: K2CO3, K3PO4, or Cs2CO3 (2–3 equiv).
  • Solvent: 1,4-dioxane/H2O, toluene/H2O, or 2-MeTHF/H2O; 60–100 °C.
  • Typical times: 2–16 h; many substrates reach >80% conversion under these conditions.

• Sonogashira coupling (to aryl alkynes):

  • Catalyst: Pd(PPh3)2Cl2 (1–3 mol%) + CuI (2–5 mol%).
  • Base: Et3N, iPr2NEt, or K2CO3.
  • Solvent: THF, toluene, or 2-MeTHF; 25–80 °C; 2–12 h under inert gas.

• Miyaura borylation (to Ar–Bpin):

  • Catalyst: Pd(dppf)Cl2 (1–3 mol%).
  • Reagents: B2pin2 (1.2–1.5 equiv), KOAc (2–3 equiv).
  • Solvent: DMSO, dioxane, or 2-MeTHF; 60–90 °C; 4–12 h.

• Halogen–lithium exchange/electrophile trapping:

  • Base: n-BuLi or s-BuLi (1.1–1.3 equiv) at −78 to −40 °C in dry THF or Et2O.
  • Electrophiles: CO2 (carboxylation), DMF (formylation), trialkyl borates (borylation), Me3SiCl (silylation). Protect or manage the N–H as needed.

• N-functionalization:

  • Acylation: Ac2O or acyl chlorides with base (pyridine, Et3N) in DCM or EtOAc, 0–25 °C.
  • Sulfonylation: RSO2Cl, base (NaHCO3, Et3N); mild temperatures.

Note: The above are literature-style conditions for para-bromo anilines generally. Optimize catalysts, ligands, temperature, and stoichiometry for your specific substrate and scale.

Safety and Handling

• Item-specific hazard information: Signal word, H-statements, GHS classes, and pictograms are not specified for this item; refer to the product SDS for authoritative data.

• General hazards for aryl bromides and N-alkyl anilines (informational, not product-specific):

  • May cause skin/eye irritation and respiratory irritation; some anilines/metabolites can induce methemoglobinemia—avoid inhalation, ingestion, and prolonged skin contact.
  • Combustible organic liquid/low-melting solid; vapors and mists from heated operations may be irritating.

• PPE and engineering controls:

  • Use in a fume hood. Wear lab coat, safety glasses or face shield, and appropriate chemical-resistant gloves (e.g., nitrile). Consider double-gloving for extended handling.
  • Employ spill trays and closed transfers for scale-up.

• Incompatibilities and reactivity:

  • Strong oxidizers and strong acids can react; acylating agents and electrophiles will react at the amine. Bases/organometallics can deprotonate the N–H.
  • Aryl bromides are generally stable; avoid prolonged exposure to high heat and strong light to minimize decomposition.

• First-aid overview (consult SDS):

  • Skin/eye contact: Rinse with water for at least 15 minutes; remove contaminated clothing. Seek medical attention if irritation persists.
  • Inhalation: Move to fresh air; provide oxygen if breathing is difficult.
  • Ingestion: Rinse mouth; do not induce vomiting; get medical attention.

• Waste: Collect halogenated organic waste separately according to institutional and local regulations.

• Research use: For research use only. Not for human or veterinary use.

Solvent Selection

This product is a hydrophobic aromatic amine building block, not a solvent. The following guidance addresses media for its handling and reaction use.

• Polarity and miscibility (general behavior):

  • Practically insoluble in water; readily soluble in nonpolar and moderately polar organic solvents (hexanes, toluene, chlorobenzenes, DCM, chloroform, MTBE, EtOAc). Soluble in coordinating ethers (THF, 2-MeTHF, DME) and polar aprotics (DMF, DMAc, NMP, DMSO).
  • The secondary amine enables modest H-bonding; solubility improves in polar aromatics and chlorinated media.

• Choosing a solvent by task:

  • Cross-coupling (Suzuki/Negishi/Stille): Toluene, dioxane, THF, or mixed aqueous-organic (toluene/H2O, dioxane/H2O) with a base; for greener choices, 2-MeTHF or CPME.
  • Buchwald–Hartwig N-arylation (if used as amine partner): Toluene, dioxane, MTBE, or 2-MeTHF; avoid overly coordinating amide solvents if catalyst ligation is problematic.
  • Lithiation/halogen–metal exchange: Anhydrous Et2O or THF at low temperature; CPME or 2-MeTHF as greener ether alternatives.
  • Workup/purification: Hexanes/EtOAc or heptane/MTBE gradients for flash chromatography; aromatic amines often tail—0.1–1% Et3N in eluent can sharpen bands.

• Compatibility notes:

  • Avoid strong acids in solution unless forming a deliberate anilinium salt; protonation will drastically change solubility and reactivity.
  • Suppress amine adsorption on silica by adding a volatile base (Et3N) or pre-neutralizing silica.

Storage and Reconstitution

• Storage (item-specific from Product Data):

  • Store at room temperature.

• Packaging/shipping: Not specified for this item; refer to CoA/Spec Sheet. Typically shipped in airtight amber vials to limit light and moisture ingress.

• General handling recommendations:

  • Keep container tightly closed under inert headspace if possible, especially for long-term storage.
  • Protect from strong light and heat. Avoid prolonged exposure to air if subsequent moisture-sensitive reactions (e.g., lithiation) are planned; brief vacuum/N2 purge cycles before use can help.
  • If anilinium salt formation occurs inadvertently (acid exposure), basify and extract to regenerate the free base as needed; confirm by NMR before critical steps.

• Shelf life: Not specified for this item; refer to CoA/Spec Sheet. Monitor by NMR/LC for any signs of degradation before key experiments.

• Reconstitution/dissolution:

  • Dissolves readily in common organic solvents (e.g., toluene, THF, DCM, EtOAc). For analytical stock solutions, prepare under dry conditions and store at 2–8 °C if needed to minimize evaporation; equilibrate to room temperature before opening to reduce condensation.

• Freeze–thaw: Not generally applicable; avoid repeated heating/cooling cycles that can promote condensation or impurity uptake.

Structure and Identity

Brief overview: 4-bromo-N-hexylaniline is a para-brominated aniline bearing a single N-hexyl substituent (secondary aniline). It combines an aryl bromide handle for cross-coupling with a moderately lipophilic N-alkyl aniline motif.

• Item-specific identifiers from Product Data:

  • CAS: 125017-21-2
  • CID: 21940645
  • InChIKey: Not specified for this item; refer to CoA/Spec Sheet. (Product Data entry is non-standard)
  • SMILES: Not specified for this item; refer to CoA/Spec Sheet.

• Literature/typical identifiers (informational; not product specifications):

  • Preferred name: 4-bromo-N-hexylaniline (p-bromo-N-hexylaniline)
  • Structural formula description: A benzene ring with para-bromine and para-relationship to an anilide nitrogen; the aniline nitrogen is monosubstituted by a linear n-hexyl chain (–NH–(CH2)5CH3). No stereocenters.
  • Functional groups: Aryl bromide (C(sp2)–Br), secondary aniline (Ar–NH–R), lipophilic n-alkyl chain.
  • Molecular formula (literature): C12H18BrN
  • Molecular weight (literature): ~256.19 g/mol
  • Example SMILES (literature): CCCCCCNC1=CC=C(Br)C=C1

• 2D structure in words: A para-brominated phenyl ring; at the para position relative to Br is an anilide nitrogen bound to a straight-chain hexyl group and a single N–H hydrogen.

Synthetic Utility

Key functional elements and their synthetic implications:

• Aryl bromide (para to anilide nitrogen):

  • Excellent handle for Pd/Ni-catalyzed cross-couplings. Para-substitution favors predictable regioselectivity and minimized steric hindrance.
  • Ready access to aryl boronates (Miyaura borylation), aryl stannanes/silanes, or direct C–C/C–N/C–O bond construction.
  • Amenable to Br/Li exchange and subsequent electrophile trapping for rapid library diversification.

• Secondary aniline (Ar–NH–hexyl):

  • Tunable basicity; forms salts for purification/crystallization.
  • N-acylation/carbamoylation/sulfonylation to modulate electronics and attenuate catalyst binding during metal-catalyzed steps.
  • As a nucleophile partner in Buchwald–Hartwig couplings to form diarylamines when coupled with a second aryl (from another aryl halide/pseudohalide).

• Strategic applications:

  • Two-vector diversification: functionalize either the aryl bromide (to introduce complexity) or the aniline N–H (to introduce protecting/functional groups), enabling convergent routes.
  • Materials synthesis: The hexyl chain enhances solubility and processability of resultant dyes, conjugated materials, or polymeric amines.

• Selectivity and protection:

  • The aniline N–H can coordinate Pd/Ni and retard couplings; Boc or acetyl protection often improves rate/selectivity, with facile deprotection afterward.
  • Electrophilic aromatic substitution is deactivated at the para site after substitution; ortho positions are modestly activated by the –NH–R donor but sterics may limit further EAS.

Target Specificity

Not applicable. This product is a small-molecule building block and is not an antibody, enzyme, or targeted biological reagent. No antigen/epitope or species reactivity applies.