4-bromo-N-ethylaniline - ≥97% , CAS No.68254-64-8

CAS: 68254-64-8 Cat. No.: B1367057 Formula: C₈H₁₀BrN Molecular Weight: 200.08 EC Number: 827-786-5

GRADE & PURITY ≥97%

Storage

Room temperature

Shipped In

Normal

Specifications

Specifications & Purity

≥97%

Storage

Room temperature

Shipped In

Normal

Purity

≥97%

Names and Identifiers

Canonical Smiles

CCNC1=CC=C(C=C1)Br

IUPAC Name

4-bromo-N-ethylaniline

InChIKey

VYSQUDVPQJEULO-UHFFFAOYSA-N

INCHI

1S/C8H10BrN/c1-2-10-8-5-3-7(9)4-6-8/h3-6,10H,2H2,1H3

Molecular Weight

200.08

Taxonomic Classification

Taxonomy Tree

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

• Kingdom: Organic compounds
• Superclass: Organic nitrogen compounds
• Class: 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
• Description: 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

Chemical and Physical Properties

• Molecular Weight: 200.080 g/mol
• XLogP3: 3.000
• Hydrogen Bond Donor Count: 1
• Hydrogen Bond Acceptor Count: 1
• Rotatable Bond Count: 2
• Exact Mass: 199 Da
• Monoisotopic Mass: 199 Da
• Topological Polar Surface Area: 12.000 Ų
• Heavy Atom Count: 10
• Formal Charge: 0
• Complexity: 87.300
• 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. No antibody/assay protocols are associated with this small-molecule reagent. For synthetic use, see Reaction Conditions and Synthetic Utility for general guidance.

Biological Roles

This product is a synthetic aromatic amine building block and does not have established endogenous biological roles.

• General considerations (informational, non-clinical):

  • Aromatic amines can engage in hydrogen bonding (via N–H as donor and N as acceptor) and cation–π interactions upon protonation; they are common motifs in medicinal chemistry SAR exploration.
  • Protonation state: In physiological-like media, the aniline nitrogen is weakly basic (anilinium pKaH typically ~4.5–5.5, literature). As a result, at neutral pH the free base predominates; in acidic media it forms water-soluble salts.
  • Metabolism context: Anilines may undergo N-oxidation, N-dealkylation, and conjugation (glucuronidation/sulfation) in biological systems (literature). These notes are general and not specific to this item.

• Research-only note: Per Product Data, this reagent is for research use only and is not intended for diagnostic, therapeutic, or other clinical applications.

Buffer Applications

Not typically applicable. 4-bromo-N-ethylaniline is an organic building block rather than a buffering agent. If aqueous handling is required, temporary solubilization can be achieved by forming an anilinium salt in acidic media; otherwise, see Solvent Selection for suitable organic systems.

Green Alternatives

• Greener strategy considerations (general):

  • Cross-coupling solvent selection: Replace high-boiling amide solvents (DMF, NMP) with 2-MeTHF, CPME, green alcohol/water systems when compatible with catalyst/boronate.
  • Base choice: Favor inorganic bases in water/biobased solvents (K2CO3, K3PO4) over strong organic bases when feasible.
  • Catalyst loading: Employ modern ligand systems (e.g., biaryl phosphines) to reduce Pd loadings to ppm–low 0.1 mol% ranges (literature), minimizing precious metal footprint.
  • Direct C–H activation: In some routes, replace pre-halogenated substrates with direct C–H arylation/amination to avoid halide waste—evaluate case-by-case.

• Illustrative comparison (general; not product specifications):

  • Conventional: DMF or dioxane, 1–3 mol% Pd, 80–100 °C, stoichiometric organic base → effective but higher E-factor.
  • Greener alternative: 2-MeTHF/H2O (or EtOH/H2O), K2CO3, 0.1–0.5 mol% Pd, 60–85 °C → reduced solvent toxicity and easier solvent recovery.

• Workup/waste:

  • Utilize aqueous acid–base extractions to switch between free base and salt forms for efficient phase separations and to minimize silica usage.
  • Consider catalyst scavengers (silica–thiol, metal scavenging resins) to reduce metal residuals without repeated distillations.

Pharmaceutical Uses

• No excipient or pharmacopeial status is specified for this item; it is supplied for research and laboratory synthesis only.

• General formulation/manufacturing context (informational):

  • Intermediate: The para-bromide enables rapid diversification via cross-coupling to generate API intermediates or analog libraries during lead optimization.
  • Salt formation: Transient HCl or other acid salts of aromatic amines can aid in crystallization, purification, and handling during process development.
  • Impurity control: Residual palladium/nickel from cross-couplings should be monitored and controlled (e.g., ICP-MS) in pharmaceutical process settings.

No therapeutic claims are made or implied.

Physical Properties

• Item-specific values (from Product Data):

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

• General/literature expectations for 4-bromo-N-ethylaniline (informational, not product specifications):

  • Aggregate state: Typically a low-melting solid or high-boiling liquid depending on purity and polymorphism; many para-bromo anilines are crystalline at ambient conditions, while N-alkylation can depress melting point.
  • Polarity: Moderate; combines a polarizable aryl bromide with a basic secondary amine (pKaH of anilinium typically in the 4.5–5.5 range, literature), enabling salt formation with mineral acids.
  • Solubility: Readily soluble in most organic solvents (EtOAc, DCM, THF, toluene, alcohols). Poorly soluble in water as the free base; water-soluble as its protonated salt in acidic media.
  • Density/refractive index/logP: Not specified here; consult literature databases for indicative values if needed in process design.
  • For precise numeric data (bp, mp, density, RI), use the item’s CoA/Spec Sheet or measure under your lab conditions.

Quality and Grades

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

• Interpreting typical grades (general guidance):

  • Analytical/AR grade: Tight control on inorganic impurities; suitable for most synthetic applications.
  • Synthesis grade/technical: Suitable for early-stage route scouting; may require additional purification before sensitive steps.
  • HPLC grade (for solvents) / LC-MS grade: Not generally applicable to this solid/liquid reagent; for chromatography solvents only.
  • Assay/purity reporting: For building blocks like 4-bromo-N-ethylaniline, assay is commonly by GC, HPLC, or qNMR; residual solvents, water (KF), and halide content may be reported.

• Stabilizers/inhibitors: Not specified for this item; refer to CoA/Spec Sheet. Secondary anilines typically do not require stabilizers; headspace inerting can minimize oxidative discoloration.

• What to check on receipt:

  • Verify identity by GC/MS or 1H/13C NMR (diagnostic para-disubstituted AA′BB′ aromatic pattern; N-ethyl signals at ~3.3–3.5 ppm and ~1.1–1.2 ppm in 1H NMR, literature).
  • Inspect color; aromatic amines may darken upon air exposure—this rarely impacts assay but can indicate trace oxidation.

Reaction and Applications

• Synthetic roles (general/literature):

  • Aryl bromide handle: Amenable to Pd-catalyzed cross-couplings:
    • Suzuki–Miyaura (to install aryl/alkenyl groups)
    • Sonogashira (to install alkynes)
    • Heck (to install alkenes)
    • Stille/Negishi (when organostannanes/organometals are available)
  • Amination chemistry: Although already N-ethylated, the aryl bromide can undergo Buchwald–Hartwig amination to introduce an additional nitrogen functionality on the ring (at the bromide site), expanding SAR libraries.
  • Halogen–lithium exchange (n-BuLi, −78 to −40 °C) to generate the corresponding aryllithium for formylation (DMF), carboxylation (CO2), or electrophile trapping.
  • Electrophilic acylation/urea/carbamate formation at the aniline nitrogen to access amides, ureas, and carbamates (use base and acylating agent).

• Application areas (non-clinical):

  • Useful intermediate for dyes, agrochemical leads, polymer modifiers, and medicinal chemistry scaffolds where para-substitution patterns are explored.

• Practical tips:

  • The secondary aniline can coordinate to Pd/Ni catalysts; consider base and ligand choice to avoid catalyst inhibition (bulky phosphines or BrettPhos-type ligands are often effective).
  • Salt formation (e.g., HCl salt) can simplify handling/purification if the free base is oily.
  • Protect the amine (Boc, Cbz) if undesired side reactions occur during cross-coupling; deprotect post-coupling.

Reaction Conditions

General literature guidance (representative; optimize for your substrate and scale):

• Suzuki–Miyaura coupling (para-bromo anilines):

  • Catalyst/ligand: Pd(PPh3)4 (1–2 mol%) or Pd2(dba)3 (1 mol%) with SPhos/XPhos (2–4 mol%).
  • Base: K2CO3 or K3PO4 (2–3 equiv).
  • Solvent: 1,4-dioxane/H2O (3:1) or 2-MeTHF/H2O.
  • Temp/time: 70–95 °C, 2–12 h.
  • Notes: Additives (TBAB) can improve phase transfer; amine protection may improve yields if coordination inhibits catalysis.

• Buchwald–Hartwig amination (at Ar–Br):

  • Catalyst/ligand: Pd2(dba)3 (1–1.5 mol%) with BrettPhos or RuPhos (2–3 mol%).
  • Base: NaOtBu or KOtBu (2–3 equiv).
  • Solvent: Toluene or tBuOH; DMF/DME also used.
  • Temp: 80–110 °C; monitor by GC/HPLC.

• Sonogashira coupling:

  • Catalyst: Pd(PPh3)2Cl2 (1–2 mol%), co-catalyst: CuI (1–5 mol%).
  • Base/solvent: Et3N or DIPEA in THF/Et3N or DMF.
  • Temp: RT–60 °C.

• Halogen–lithium exchange:

  • Reagent: n-BuLi (1.1–1.5 equiv) at −78 to −40 °C in THF/Et2O.
  • Quench: DMF (for CHO), CO2 (for CO2H), electrophiles as desired.
  • Note: Protect or manage the aniline functionality (form the lithium anilide first, or protect as carbamate) to avoid side reactions.

All conditions are literature-style examples; validate and optimize for your specific use case.

Safety and Handling

• Item-specific hazard data (from Product Data):

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

• General safety considerations for aromatic amines and aryl bromides (informational; defer to SDS for authoritative guidance):

  • Hazards: Aromatic amines may cause skin/eye irritation and can be harmful if inhaled or ingested. Some anilines show methemoglobinemia potential; treat all with caution. Aryl bromides are generally of low acute reactivity but may be irritating.
  • PPE: Lab coat, nitrile gloves (change regularly), splash goggles. Use in a fume hood to avoid inhalation of vapors/aerosols.
  • First aid (overview):
    • Skin: Wash with soap and water. Remove contaminated clothing.
    • Eyes: Rinse cautiously with water for several minutes; seek medical attention if irritation persists.
    • Inhalation: Move to fresh air; seek medical attention if symptoms occur.
    • Ingestion: Rinse mouth; do not induce vomiting; seek medical attention.
  • Handling/storage incompatibilities: Avoid strong oxidizers and acylating/nitrosating agents. Protonated salts are incompatible with strong bases. Free base can react with acid chlorides/anhydrides; keep away unless intended.
  • Peroxide formation: Not applicable (non-ether), but always check solvent peroxides when using with peroxide-forming solvents.
  • Thermal stability: Aryl bromides are generally thermally stable; avoid overheating to decomposition.
  • Always consult the product-specific SDS before use.

Solvent Selection

• Polarity and miscibility (general):

  • Solvent class: Moderately polar, basic organic compound; miscible with many organic solvents (THF, DCM, EtOAc, toluene, alcohols, acetonitrile). Poor solubility in water as free base; soluble in dilute acids as the anilinium salt.
  • Acid–base behavior: Protonation (e.g., with HCl, TsOH) increases water solubility; useful for liquid–liquid separations and salt-mediated crystallizations.

• Choosing solvents for key operations:

  • Cross-coupling at Ar–Br: Polar aprotic media (DMF, DMAc, NMP, DMSO) or mixed dioxane/H2O; toluene with bulky ligands for high-temperature Buchwald–Hartwig.
  • N-acylation/alkylation of the amine: Use non-protic, non-nucleophilic solvents (DCM, CHCl3, THF, MeCN) with a suitable base (Et3N, DIPEA) to suppress side reactions.
  • Purification: Normal-phase silica works; add 0.1–1% Et3N in eluent to minimize amine streaking.

• Comparison snapshot (general):

  • THF vs dioxane: THF offers lower bp and faster evaporation; dioxane/water mixtures often superior for Suzuki couplings.
  • Toluene vs DMF: Toluene benefits air-sensitive catalyst systems and easier workup; DMF improves solubility of polar boronates/bases but complicates removal.

Storage and Reconstitution

• Item-specific storage/shipping (from Product Data):

  • Storage conditions: Room temperature.
  • Shipped in: Normal.

• General handling guidance for aromatic amines/aryl bromides:

  • Store tightly closed under dry, inert atmosphere if possible to minimize oxidative discoloration and moisture uptake (especially if supplied as free base/oily material).
  • Protect from prolonged light/heat. Use amber glass for long-term storage.
  • If solidification occurs or the material is viscous, gently warm (e.g., 30–40 °C) to facilitate dissolution; avoid overheating.
  • For solution preparation, use dry, oxygen-free solvents when performing air/moisture-sensitive transformations (e.g., metalations, cross-couplings).
  • If forming salts (e.g., HCl salt) for handling, document stoichiometry and counterion for reproducibility.

• Reconstitution: Not typically applicable. Dissolve directly in a suitable organic solvent (e.g., DCM, THF, MeOH, toluene) to the desired concentration. Filter through a PTFE membrane if particulate is present.

Always refer to the item’s CoA/Spec Sheet and SDS for product-specific details.

Structure and Identity

A para-brominated, N-ethylated aniline serving as an aryl bromide building block and secondary aromatic amine.

• Item-specific identifiers (from Product Data):

  • SKU: B1367057
  • Product name: 4-bromo-N-ethylaniline
  • CAS: 68254-64-8
  • PubChem CID: 11745656
  • InChIKey: 391904 (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.

• Representative structural description (literature/general):

  • Core motif: A benzene ring bearing a para-bromo (p-Br) substituent and a secondary anilide nitrogen (–NH–CH2CH3) at the para position relative to Br.
  • Functional groups: Aryl bromide (C–Br on sp2 carbon); secondary aniline (aromatic amine N–H with one ethyl substituent).
  • Substitution pattern: 1,4-disubstituted benzene (para relationship between Br and anilino nitrogen).
  • Stereochemistry: None (achiral molecule; no stereocenters).
  • Representative SMILES (literature): Brc1ccc(NCC)cc1 (one of several equivalent depictions).

• 2D structure in words: A benzene ring with bromine at the 1-position and an –NH–CH2–CH3 group at the 4-position (para).

Synthetic Utility

• Functional group handles:

  • Aryl bromide (para): Excellent leaving group for Pd/Ni-catalyzed couplings; compatible with a wide range of nucleophiles and organometallic partners.
  • Secondary aniline: N-acylation, sulfonylation, carbamate/urea formation; potential for directed ortho-metalation under strong base after formation of the lithium anilide (literature).

• Retrosynthetic perspective:

  • Enables modular access to 1,4-disubstituted aniline frameworks by coupling at C–Br followed by N-functional group interconversions, or vice versa.
  • Bromine–lithium exchange permits rapid introduction of electrophiles (CHO, CO2, CN equivalents) at the para position.

• Named reaction relevance (literature examples):

  • Suzuki–Miyaura coupling: With aryl/alkenyl boron reagents; bases such as K2CO3/K3PO4 in dioxane/H2O or 2-MeTHF/H2O.
  • Buchwald–Hartwig amination: Installation of amines on the aryl bromide site using Pd catalysts and biaryl phosphine ligands.
  • Sonogashira/Heck: Introduction of alkynes/alkenes at the bromide position to elaborate conjugated scaffolds.

• Practical notes:

  • If the aniline nitrogen interferes with catalysis, consider temporary protection (Boc, Cbz) or in situ base/ligand strategies to suppress catalyst deactivation.

Target Specificity

Not applicable. This product is a small-molecule chemical building block, not a biological targeting reagent (no antigen/epitope/isotype information).

Frequently Asked Questions

What is the purity of this product?

This product is supplied at ≥97% purity (chemical assay). Lot-specific values are stated on the Certificate of Analysis.

How should this product be stored?

Store at room temperature.

How is this product shipped?

This product ships under standard ambient conditions. No temperature-controlled packaging is required.

What are the CAS number, molecular formula and molecular weight?

The CAS Number is 68254-64-8, the molecular formula is C8H10BrN, and the molecular weight is 200.08 g/mol. InChIKey VYSQUDVPQJEULO-UHFFFAOYSA-N.

What documentation is provided?

Available product documentation, including Certificates of Analysis (COA), Safety Data Sheets (SDS), and specification sheets, is shown in the product document area. Document availability and access follow the current site policy.