3′-Amino-4′-bromoacetophenone - ≥97% , CAS No.37148-51-9

CAS: 37148-51-9 Cat. No.: A469136 Summenformel: C₈H₈NOBr Molekulargewicht: 214.05 EG-Nummer: 686-950-2

GRADE & PURITY ≥97%

Synonyms

3'-amino-4'-bromoacetophenone | SR-01000388877 | MFCD00466451 | SR-01000388877-1 | STL370781 | Z1269218710 | 1-(3-amino-4-bromophenyl)ethanone | 1-(3-Amino-4-bromo-phenyl)-ethanone | 3 inverted exclamation marka-Amino-4 inverted exclamation marka-bromoace

Storage

Room temperature

Specifications

Synonyme

3'-amino-4'-bromoacetophenone | SR-01000388877 | MFCD00466451 | SR-01000388877-1 | STL370781 | Z1269218710 | 1-(3-amino-4-bromophenyl)ethanone | 1-(3-Amino-4-bromo-phenyl)-ethanone | 3 inverted exclamation marka-Amino-4 inverted exclamation marka-bromoace

Spezifikationen & Reinheit

≥97%

Storage

Room temperature

Reinheit

≥97%

Namen und Kennungen

Pubchem Sid

488190697

Kanonisches Lächeln

CC(=O)C1=CC(=C(C=C1)Br)N

IUPAC Name

1-(3-amino-4-bromophenyl)ethanone

InChIKey

HYRBHUHCBGRDHI-UHFFFAOYSA-N

INCHI

1S/C8H8BrNO/c1-5(11)6-2-3-7(9)8(10)4-6/h2-4H,10H2,1H3

Isomere SMILES

CC(=O)C1=CC(=C(C=C1)Br)N

Molekulargewicht

214.05

Reaxy-Rn

2082485

Reaxys-RN_link_address

https://www.reaxys.com/reaxys/secured/hopinto.do?context=S&query=IDE.XRN=2082485&ln=

Taxonomic Classification

Taxonomy Tree

• Kingdom Organic compounds
  • Superclass Organic oxygen compounds
    • Klasse Organooxygen compounds
      • Subclass Carbonyl compounds
        • Ebene5 Ketones
          • Ebene6 Aryl ketones
            • Ebene7 Phenylketones
              • Ebene8 Alkyl-phenylketones

• Kingdom: Organic compounds
• Superclass: Organic oxygen compounds
• Klasse: Organooxygen compounds
• Subclass: Carbonyl compounds
• Intermediate Tree Nodes: Ketones - Aryl ketones - Phenylketones
• Direct Parent: Alkyl-phenylketones
• Alternative Parents: Acetophenones Benzoyl derivatives Aryl alkyl ketones 2-bromoanilines Bromobenzenes Aryl bromides Primary amines Organopnictogen compounds Organobromides Organic oxides Hydrocarbon derivatives
• Molecular Framework: Aromatic homomonocyclic compounds
• Substituents: Alkyl-phenylketone - Acetophenone - Benzoyl - Aniline or substituted anilines - Aryl alkyl ketone - 2-bromoaniline - Bromobenzene - Halobenzene - Aryl bromide - Aryl halide - Monocyclic benzene moiety - Benzenoid - Organohalogen compound - Hydrocarbon derivative - Organic oxide - Organopnictogen compound - Amine - Organobromide - Organonitrogen compound - Primary amine - Organic nitrogen compound - Aromatic homomonocyclic compound
• Beschreibung: This compound belongs to the class of organic compounds known as alkyl-phenylketones. These are aromatic compounds containing a ketone substituted by one alkyl group, and a phenyl 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

Chemische und physikalische Eigenschaften

• Schmelzpunkt (°C): 114-118°C
• Molekulargewicht: 214.060 g/mol
• XLogP3: 1.600
• Hydrogen Bond Donor Count: 1
• Hydrogen Bond Acceptor Count: 2
• Rotatable Bond Count: 1
• Exact Mass: 212.979 Da
• Monoisotopic Mass: 212.979 Da
• Topological Polar Surface Area: 43.100 Ų
• Heavy Atom Count: 11
• Formal Charge: 0
• Complexity: 160.000
• 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 vendor-validated bioassay or analytical protocols are specified for this item.

• General laboratory use (informational)
  • Stock preparation: Dissolve in dry DMSO or DMF to 10–100 mM; vortex and, if needed, warm gently (<40 °C). Filter (0.22 µm PTFE) for particulate removal.
  • Synthetic set-up: For Pd-catalyzed couplings, degas solvents (sparging or freeze–pump–thaw). Maintain inert atmosphere (N2/Ar). Titrate base to minimize aniline side reactions.

Refer to your internal SOPs. For research use only (per Product Data).

Biological Roles

This compound is a synthetic aromatic building block and is not known to occur in biological systems.

• General context (informational)
  • Aniline- and bromo-substituted acetophenones do not have established metabolic or signaling roles; they are primarily used as intermediates in medicinal chemistry and materials research.
  • The aniline function can engage in non-specific protein interactions in vitro; handle accordingly during biochemical assays (research use only).

No biological role or pathway specificity is claimed or implied for this product.

Buffer Applications

Not typically used as a buffering agent.

• Practical note: If used in biochemical assays as a test article, prepare stocks in DMSO or DMF and dilute into a pre-selected biological buffer (e.g., PBS, HEPES) ensuring final cosolvent levels compatible with the assay system. This compound itself does not define a buffer system or pH range.

Green Alternatives

• Greener solvent choices (literature/general)

  • Replace chlorinated solvents (DCM) with ethyl acetate or methyl tert-butyl ether (MTBE) for extractions; use 2‑MeTHF or CPME instead of THF/toluene where compatible.
  • Aqueous micellar catalysis (e.g., TPGS-750-M) can enable Suzuki/Buchwald couplings in water at lower catalyst loadings.

• Catalysis and process intensification

  • Employ ligand-enabled Pd catalysis at ppm levels or Ni-catalyzed couplings to reduce precious metal usage.
  • Flow chemistry for exotherm control and reduced solvent volumes during cross-couplings and nitrile oxide/oxime formations.

• Comparison snapshot (informational)

  | Dimension | Conventional | Greener alternative | Trade-offs | |---|---|---|---| | Solvent for Suzuki | Toluene/dioxane | 2‑MeTHF, CPME, water–EtOH micelles | Solubility/cycle times may change | | Workup solvent | DCM | EtOAc, MTBE | Partitioning may be slower | | Base | Inorganic carbonate | Aqueous carbonate in micelles | Emulsion handling | | Catalyst | Pd(PPh3)4 (0.5–2 mol%) | Pd/Ni (ppm–0.1 mol%), ligand-engineered | Optimization effort |

Note: Selection should be guided by LCA metrics (E‑factor, PMI) and product quality targets; pilot small-scale screens first.

Pharmaceutical Uses

• Formulation/excipient status: None. This product is not intended as an excipient.

• Research/manufacturing context (informational)

  • Serves as a synthetic intermediate in discovery and process chemistry. The 4′‑bromo handle enables late-stage diversification via Pd/Ni-catalyzed cross-couplings; the 3′‑aniline and acetyl moieties allow orthogonal protection and derivatization.
  • Can be incorporated into SAR campaigns targeting aryl‑ketone scaffolds; downstream purification typically by silica gel chromatography or crystallization.

No therapeutic or clinical claims are made. For research use only (per Product Data).

Physical Properties

• Item-specific specifications

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

• Literature/general properties (informational; not product specifications)

  • Molecular formula: C8H8BrNO (literature)
  • Molecular weight: ~214.06 g/mol (literature)
  • Physical state: typically a crystalline solid for analogous halo-amino acetophenones (literature trend)
  • Solubility: expected to be sparingly soluble in water; soluble in common organic solvents such as ethanol, methanol, acetone, dichloromethane, ethyl acetate; highly soluble in DMF and DMSO (literature/experience for aryl ketones with anilines)
  • Acid–base behavior: aniline pKaH typically ~4.5–5.5 (conjugate acid), free base is neutral at basic/neutral pH; the ketone is non-ionizable under neutral conditions (literature)
  • Partitioning: aryl bromides with a single aniline and ketone typically have moderate hydrophobicity (logP in the 1.5–2.5 range), exact value not determined for this compound (literature expectation)
  • Melting point, boiling point, density, refractive index: Not specified for this item; consult literature or CoA.

Note: Use the item’s CoA for any method-validation-relevant constants (e.g., melting range for ID testing).

Quality and Grades

• Item-specific quality

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

• Interpreting common grades (general guidance)

  • Research/technical grade: Suitable for synthetic R&D, assay development, and library synthesis. Impurity profiles are acceptable for most synthetic workflows but may require purification for sensitive transformations.
  • HPLC/LC–MS grade (if applicable): Emphasizes low non-volatile residue and low UV background; useful when using the compound as a reference standard or for analytical calibrations.
  • Pharma/USP/EP grade: Not applicable unless explicitly specified; would imply compendial tests and trace-level impurities control.

• Practical quality considerations for this scaffold

  • Aryl bromide reactivity: Trace metal impurities or adventitious water generally have minor effects, but cross-coupling workflows are sensitive to halide content and residual acids; consider pre-drying and, if necessary, re-crystallization.
  • Aniline functionality: Can undergo slow air oxidation to colored byproducts; store tightly closed and limit prolonged exposure to air/light for analytical uses.

Refer to the item’s CoA for exact purity assay, residual solvent levels, and any specific stabilizers used.

Reaction and Applications

This bifunctional aryl bromide/aniline ketone is a versatile building block enabling orthogonal chemistry at the aryl bromide, aniline, and ketone sites.

• Aryl bromide transformations (literature)

  • Suzuki–Miyaura cross-coupling to introduce aryl/heteroaryl moieties; Pd(0) catalysts with bases such as K2CO3/K3PO4 in toluene/dioxane/water.
  • Buchwald–Hartwig amination to install secondary/tertiary anilines on the 4′-position using Pd catalysts and tailored ligands (e.g., BINAP, XPhos) with NaOtBu or Cs2CO3.
  • Sonogashira and Heck couplings to access alkynylated or vinylated derivatives.

• Aniline site elaboration (literature)

  • Protection: Boc, Cbz, or acyl protection to tune electronic effects and direct cross-coupling regioselectivity.
  • Diazotization/Sandmeyer variants (when unprotected) for further diversification (e.g., convert –NH2 to –X/–CN), accounting for the para-bromo already present.

• Carbonyl chemistry (literature)

  • Formation of oximes (NH2OH), hydrazones (2,4‑DNPH, semicarbazide), and imines/enamines (with amines under acid catalysis).
  • Alpha-functionalization via enolate chemistry (Claisen condensation, alkylation, halogenation) at the methyl ketone.

• Practical tips

  • Sequence planning: Protect the aniline before Pd-catalyzed couplings to avoid catalyst poisoning; alternatively, use ligand/catalyst systems tolerant to free anilines.
  • Drying: For base-sensitive steps, dry solvents and use molecular sieves; degas for Pd-catalyzed protocols.
  • Analysis: Monitor by TLC (UV-active) and LC–MS; characteristic isotopic pattern (M/M+2) from bromine aids identification.

Reaction Conditions

General, literature-based guidance for aryl bromide/aniline acetophenones; optimize per substrate.

• Suzuki–Miyaura coupling

  • Catalyst: Pd(PPh3)4 (0.5–2 mol%) or Pd2(dba)3/XPhos (1–3 mol% Pd)
  • Base: K2CO3 or K3PO4 (2–3 equiv)
  • Solvent: 1,4-dioxane/H2O (3:1), toluene/H2O, or 2‑MeTHF/H2O
  • Temperature/time: 70–100 °C, 2–16 h

• Buchwald–Hartwig amination (Ar–Br to Ar–NR2)

  • Catalyst/ligand: Pd2(dba)3 (1–2 mol% Pd) with BINAP, BrettPhos, or XPhos
  • Base: NaOtBu, Cs2CO3, or K3PO4
  • Solvent: Toluene, dioxane, or t‑BuOH
  • Temperature: 80–110 °C

• Sonogashira coupling

  • Catalyst: Pd(PPh3)2Cl2 (1–2 mol%) + CuI (5–10 mol%)
  • Base: Et3N or i‑Pr2NH
  • Solvent: THF, DMF, or 2‑MeTHF; 25–60 °C

• Oxime formation (ketone → oxime)

  • Reagents: Hydroxylamine hydrochloride (1.2–1.5 equiv), pyridine or acetate buffer
  • Solvent: EtOH or MeOH; 25–60 °C, 1–4 h

• Enolate alkylation

  • Base: LDA or NaHMDS (1.1–1.5 equiv) in THF at −78 to 0 °C; then add alkyl halide (1.2–2 equiv)

Note: Free aniline may coordinate/poison Pd; consider N‑protection or catalyst/ligand systems tolerant to –NH2. These are literature norms and not product specifications.

Safety and Handling

• Item-specific hazard information

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

• General hazards for aryl bromide anilide ketones (informational)

  • May cause skin/eye irritation and respiratory irritation upon dust generation; harmful if swallowed (typical for aromatic amines/ketones). Avoid inhalation of dust and contact with skin/eyes.
  • Combustible organic solid; avoid ignition sources and static discharge. Use in well-ventilated area or fume hood.

• PPE and engineering controls

  • Wear lab coat, safety goggles, and suitable gloves (e.g., nitrile). Handle in a chemical fume hood, especially for weighing and transfers to minimize dust exposure.

• Incompatibilities and reactivity

  • Strong oxidizers (risk of exotherm/oxidation). Strong reducing agents or bases may promote side reactions at the carbonyl (e.g., condensation) or aniline (e.g., deprotonation/air oxidation). Avoid nitrosating agents (anilines can form N‑nitroso derivatives).

• First-aid overview (non-exhaustive)

  • Skin/eye contact: Rinse with water for 15 minutes; remove contaminated clothing; seek medical attention if irritation persists.
  • Inhalation: Move to fresh air; seek medical attention if symptoms develop.
  • Ingestion: Rinse mouth; do not induce vomiting; obtain medical attention.

Always consult the product-specific SDS for authoritative hazard classifications and response guidance.

Solvent Selection

• Polarity and miscibility (literature/general)

  • Moderately polar aromatic ketone with an aniline; expected to be soluble in DMSO, DMF, acetone, acetonitrile, ethyl acetate, toluene, THF, methanol, ethanol; sparingly soluble in water.
  • Suitable stock solutions for screening: 10–100 mM in DMSO or DMF; filter-sterilize if needed for biochemical assays (research only).

• Choosing solvents by operation

  • Cross-coupling (Suzuki/Heck/Sonogashira): Toluene, 1,4-dioxane, THF, CPME, or mixtures with alcohol/water under basic conditions.
  • Carbonyl derivatization (oxime/hydrazone/imines): EtOH, MeOH, i-PrOH, or MeCN with catalytic acid/base as needed.
  • N‑acylation/protection of aniline: DCM, THF, or acetonitrile with base (e.g., TEA, pyridine).

• Comparison (general)

  • DMSO vs DMF: DMSO offers broader solubility and higher boiling point; DMF can be advantageous for coupling but introduces formyl reactivity under strong base.
  • Ethyl acetate vs DCM for workup: EtOAc is greener and safer; DCM offers faster phase separations and higher capacity for aromatic solutes.

Note: Select solvent/cosolvent based on downstream purification (e.g., normal-phase vs reverse-phase) and base/catalyst compatibility.

Storage and Reconstitution

• Item-specific storage

  • Storage Conditions: Room temperature (per Product Data). Keep tightly closed in a dry, well-ventilated place.
  • Shipped In: Not specified for this item; refer to CoA/Spec Sheet.

• Practical guidance (general)

  • Protect from prolonged exposure to light and air to minimize potential discoloration from aniline oxidation. Include desiccant if humidity is high.
  • For long-term archiving, consider storage at 2–8 °C in amber glass, especially after first opening.

• Reconstitution/stock solutions

  • Prepare concentrated stocks in anhydrous DMSO or DMF (e.g., 100 mM). For synthetic operations, dissolve in compatible dry solvents (THF, toluene, dioxane) under inert gas when required.
  • Avoid repeated freeze–thaw of solutions; aliquot stocks for single use. Solid can be subdivided under dry conditions.

Always consult the CoA/SDS for lot-specific guidance and stability data.

Structure and Identity

Brief description: 3′-Amino-4′-bromoacetophenone is an anilide-type aryl ketone featuring a meta‑amino and para‑bromo substitution on the acetophenone ring, combining a cross‑coupling‑ready aryl bromide with a nucleophilic aniline and an electrophilic methyl ketone.

• Item-specific (from Product Data)

  • SKU: A469136
  • Product Name: 3′-Amino-4′-bromoacetophenone
  • CAS: 37148-51-9
  • CID: 608294
  • Storage Conditions: Room temperature
  • SMILES: Not specified for this item; refer to CoA/Spec Sheet.
  • InChIKey: Not specified for this item; refer to CoA/Spec Sheet.

• Computed/literature identity (not a specification)

  • Expected molecular formula (literature): C8H8BrNO
  • Approx. molecular weight (literature): ~214.06 g/mol
  • Functional groups: aryl bromide (para to acyl), aniline (meta to acyl), aryl methyl ketone (acetyl)
  • Structural description (2D): A benzene ring bearing an acetyl group (–COCH3) at position 1, a bromo substituent at the para (4′) position, and an amino group (–NH2) at the meta (3′) position relative to the acetyl. No stereocenters; planar aromatic core.

• General identifiers

  • Synonyms (literature): 1-(3-amino-4-bromophenyl)ethan-1-one; m‑amino‑p‑bromoacetophenone; 3‑amino‑4‑bromoacetophenone.

Note: Structural strings and exact identifiers should be verified on the CoA/SDS for this specific lot.

Synthetic Utility

• Functional group handles

  • Aryl bromide: platform for C(sp2)–C(sp2/sp) couplings (Suzuki, Stille, Negishi, Heck, Sonogashira) and C–N/C–S couplings (Buchwald–Hartwig).
  • Aniline: site for protection (Boc/Cbz/Ac), urea/carbamate/sulfonamide formation, diazotization, or electrophilic aromatic substitution directing effects.
  • Methyl ketone: enolate generation for alpha‑alkylation/acylation; condensation to oximes/hydrazones; reduction to secondary alcohols (NaBH4) or to ethyl chain (Clemmensen/Wolff–Kishner conditions).

• Retrosynthetic value

  • Enables convergent assembly: introduce complex aryl/heteroaryl fragments via 4′‑Br while using the aniline to tune electronics/reactivity and the ketone for further branching.

• Orthogonality strategy

  • Typical sequence: Protect –NH2, perform Pd-catalyzed coupling at Ar–Br, elaborate carbonyl (e.g., oxime/hydrazone or enolate chemistry), then deprotect and functionalize the aniline.

• Analytical cues

  • 1H NMR: methyl singlet (≈2.5–2.7 ppm for aryl methyl ketones), aniline NH2 broad resonance (exchangeable), aromatic pattern consistent with 1,3,4-trisubstitution.
  • MS: Bromine isotopic signature (M and M+2 ~1:1).

These points reflect general literature behavior for this scaffold and support diverse route design.

Target Specificity

Not applicable. This product is a small-molecule chemical building block and is not an antibody, enzyme, or targeted biological reagent. No target, isotype, clone, or species reactivity is defined.