3-Bromo-3',4'-dichlorobenzophenone , CAS No.844879-39-6

CAS: 844879-39-6 Cat. No.: B1010179 Summenformel: C₁₃H₇BrCl₂O Molekulargewicht: 330 PubChem CID: 2756902

Storage

Room temperature

Specifications

Storage

Room temperature

Namen und Kennungen

• Kanonisches Lächeln: C1=CC(=CC(=C1)Br)C(=O)C2=CC(=C(C=C2)Cl)Cl
• IUPAC Name: (3-bromophenyl)-(3,4-dichlorophenyl)methanone
• InChIKey: XFQXEVYYULCMIR-UHFFFAOYSA-N
• INCHI: 1S/C13H7BrCl2O/c14-10-3-1-2-8(6-10)13(17)9-4-5-11(15)12(16)7-9/h1-7H
• Isomere SMILES: C1=CC(=CC(=C1)Br)C(=O)C2=CC(=C(C=C2)Cl)Cl
• PubChem CID: 2756902
• Molekulargewicht: 330

Taxonomic Classification

Taxonomy Tree

• Kingdom Organic compounds
  • Superclass Benzenoids
    • Klasse Benzene and substituted derivatives
      • Subclass Benzophenones

• Kingdom: Organic compounds
• Superclass: Benzenoids
• Klasse: Benzene and substituted derivatives
• Subclass: Benzophenones
• Intermediate Tree Nodes: Not available
• Direct Parent: Benzophenones
• Alternative Parents: Diphenylmethanes Aryl-phenylketones Dichlorobenzenes Benzoyl derivatives Bromobenzenes Aryl chlorides Aryl bromides Organochlorides Organobromides Organic oxides Hydrocarbon derivatives
• Molecular Framework: Aromatic homomonocyclic compounds
• Substituents: Benzophenone - Aryl-phenylketone - Diphenylmethane - Benzoyl - 1,2-dichlorobenzene - Aryl ketone - Bromobenzene - Chlorobenzene - Halobenzene - Aryl chloride - Aryl bromide - Aryl halide - Ketone - Organooxygen compound - Hydrocarbon derivative - Organic oxide - Organic oxygen compound - Organohalogen compound - Organobromide - Organochloride - Aromatic homomonocyclic compound
• Beschreibung: This compound belongs to the class of organic compounds known as benzophenones. These are organic compounds containing a ketone attached to two phenyl groups.
• 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

• Molekulargewicht: 330.000 g/mol
• XLogP3: 5.200
• Hydrogen Bond Donor Count: 0
• Hydrogen Bond Acceptor Count: 1
• Rotatable Bond Count: 2
• Exact Mass: 327.906 Da
• Monoisotopic Mass: 327.906 Da
• Topological Polar Surface Area: 17.100 Ų
• Heavy Atom Count: 17
• Formal Charge: 0
• Complexity: 285.000
• 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 biological assay or immunoassay protocols apply to this small-molecule building block. For synthetic use, see Reaction Conditions and Synthetic Utility for representative setups and parameters. Adapt stoichiometry, catalyst loading, and workup to your specific transformation and scale.

Biological Roles

This product is a synthetic organic building block (halogenated benzophenone) rather than a biomolecule. It does not possess established biological roles or participate in native biochemical pathways.

• General notes (contextual, not product-specific):
  • Benzophenone cores are sometimes used as photoreactive probes or crosslinkers in chemical biology due to their triplet-state reactivity, but such use requires appropriate conjugation/derivatization and rigorous safety evaluation.
  • Tri-halogenation increases lipophilicity and may affect nonspecific binding in biological matrices; however, this material is provided strictly for research and synthetic applications, not for biological administration.

Research Use Note: For research use only.

Buffer Applications

Not typically applicable. 3-Bromo-3',4'-dichlorobenzophenone is a hydrophobic organic reagent and is not used to prepare aqueous buffer systems. For lab work involving this compound, focus on organic solvent systems described under Solvent Selection.

Green Alternatives

• Solvent substitution (greener choices):

  • Replace chlorinated solvents (CH2Cl2, CHCl3) with 2-MeTHF, CPME, toluene, or ethyl acetate where solubility/performance allows.
  • For Suzuki couplings, aqueous 2-MeTHF or ethanol/water mixtures can work with the right base/ligand set, simplifying workup.
  • For carbonyl reductions or Grignard additions, 2-MeTHF is a greener ether alternative to THF/Et2O with higher boiling point and improved safety.

• Catalysis and conditions:

  • Favor Pd- or Ni-catalyzed cross-couplings at room temperature to moderate heat, using low catalyst loadings and recyclable ligand systems where feasible.
  • Microwave or continuous-flow processing can reduce energy consumption and improve selectivity, reducing waste.

• Comparison snapshot (general guidance):

  • THF vs 2-MeTHF: similar coupling performance; 2-MeTHF has bio-based sourcing potential and better phase separation, but may dissolve inorganic bases less well.
  • DMF/DMAc vs Cyrene or propylene carbonate: greener dipolar aprotics; confirm catalyst compatibility and substrate solubility.

Note: “Greenest” conditions remain system-specific. Pilot a small matrix (solvent, base, ligand) to benchmark performance against conventional conditions while minimizing hazardous solvent use.

Pharmaceutical Uses

No excipient or pharmacopeial roles are indicated for this item. As a tri-halogenated benzophenone, it may serve as a synthetic intermediate in discovery or process chemistry campaigns (e.g., scaffold elaboration via cross-coupling at Ar–Br and subsequent modifications), but it is not intended for therapeutic or clinical use.

• Formulation context (general): typically handled as a solid reagent dissolved in suitable organic solvents for reaction steps; not formulated for dosing.

Always conduct appropriate impurity and residual solvent controls when employing this building block in GMP-adjacent research, and segregate from clinical manufacturing streams unless fully qualified according to your QA requirements.

Physical Properties

• Item-specific (from Product Data):

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

• Computed/literature values (informational; typical for this structure, not specifications):

  • Estimated molecular weight (from formula C13H7BrCl2O): ~330.00 g/mol
  • Physical state: halogenated benzophenones are typically crystalline solids at ambient conditions.
  • Solubility (literature/general): sparingly soluble in water; good solubility in halogenated solvents (e.g., CH2Cl2, CHCl3), aromatics (toluene), ethers (THF), and polar aprotics (DMF, DMSO).
  • LogP (expected, qualitative): high, consistent with tri-halogenated diaryl ketones; favors partitioning into nonpolar organic phases.
  • UV characteristics (general for benzophenones): strong π–π* absorption in near-UV; often λmax around 240–260 nm and a band near 325–350 nm (literature, parent benzophenone). Substituents shift intensities/positions.
  • Melting/boiling: specific values for this exact compound were not located; halogenated benzophenones commonly melt between ~80–160 °C and have very high boiling points/decompose before boiling at 1 atm (literature trend only).

Note: For exact physical constants (MP, purity, residual solvents, water/peroxide content, metal limits, refractive index), consult the item’s CoA/Spec Sheet. Values above are provided as general guidance and should not be used as specifications.

Quality and Grades

• Item-specific (from Product Data):

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

• Guidance on interpreting grade (general):

  • If provided as “research grade,” material is suitable for synthetic and analytical research but not for human/animal administration. HPLC/GC grades typically imply low non-volatile residue and low UV background (for chromatographic work). AR/ACS grades conform to general reagent purity standards.
  • Stabilizers/inhibitors: Not typically required for benzophenones; if present (rare), they may affect downstream photochemical studies. Any stabilizer would be declared on the CoA/Spec Sheet.
  • Trace analyses: For sensitive catalysis (e.g., Pd-catalyzed coupling), residual metal and halide content in substrates is less critical than in ligands/catalysts, but overall impurity profile can affect yields. If you require specific impurity limits (water, metals, UV cutoff), request the lot-specific CoA.

• Recommended verification:

  • Confirm identity by 1H/13C NMR and HRMS; assess halogen content by XRF or HRMS isotope pattern. Confirm purity by HPLC/GC or qNMR as appropriate for your application.

Reaction and Applications

With three distinct functional elements—an aryl bromide, two aryl chlorides, and a benzophenone carbonyl—this substrate is highly versatile in synthesis.

• Cross-coupling at Ar–Br (primary handle):

  • Suzuki–Miyaura, Negishi, Stille, and Kumada couplings enable rapid diversification. The bromide typically couples under milder conditions than chlorides; selectivity is achievable with Pd(0)/phosphine ligands or Ni catalysts.
  • Practical notes: Use well-dried bases (e.g., K3PO4, Cs2CO3) and degassed solvent. Monitor for competitive dehalogenation; bulky, electron-rich ligands (e.g., SPhos/XPhos) often improve selectivity.

• Aryl chlorides (secondary handles):

  • With modern catalysts/ligands (e.g., BrettPhos, RuPhos, or Ni/bipyridine), the 3′/4′-Cl sites can be engaged for C–N, C–C, or C–O couplings after installing functionality at Ar–Br. Electronic effects from the adjacent carbonyl may assist oxidative addition at the para-Cl.

• Carbonyl transformations:

  • Nucleophilic addition: Grignard/organolithium reagents add to give tertiary carbinols. Control halogen–metal exchange by temperature and reagent choice (e.g., iPrMgCl·LiCl for milder addition).
  • Reduction: NaBH4 affords benzhydrol analogs (often requires polar protic cosolvent); stronger methods (BH3·THF, LiAlH4) reduce more readily; Wolff–Kishner or Clemmensen reduce to the diarylmethane.
  • Acyl activation: Formation of oximes/hydrazones enables subsequent rearrangements or reductions.

• Photochemistry (general for benzophenones): n→π* triplet states enable H-abstraction and Paternò–Büchi chemistry; heavy atoms may modulate intersystem crossing.

Reaction Conditions

General, literature-based guidance for typical transformations of halogenated benzophenones like 3-bromo-3',4'-dichlorobenzophenone (optimize per substrate and scale):

• Suzuki–Miyaura at Ar–Br:

  • Catalyst: Pd2(dba)3 (1–2 mol%) + SPhos/XPhos (2–4 mol%) or Pd(PPh3)4 (3–5 mol%).
  • Base: K3PO4 (2–3 equiv) or Cs2CO3 (2 equiv).
  • Solvent: toluene/H2O, 1,4-dioxane/H2O, or 2-MeTHF/H2O; 0.1–0.3 M.
  • Temperature/time: 50–90 °C, 2–12 h. Typical isolated yields for aryl boronic acids: 70–95% (literature ranges).

• Buchwald–Hartwig amination (at Ar–Br; for Ar–Cl use more activated systems):

  • Catalyst/ligand: Pd2(dba)3 (1–2 mol%) + BrettPhos or RuPhos (2–4 mol%).
  • Base: NaOtBu or K3PO4 (2–3 equiv).
  • Solvent: toluene, tBuOH, or dioxane; 60–110 °C, 4–16 h.

• Nucleophilic addition to the ketone:

  • Grignard: RMgX (1.2–2.0 equiv) in anhydrous THF or 2-MeTHF, 0 to −20 °C addition, then warm to RT; quench with NH4Cl. Protect halides by choosing less aggressive R groups/temperatures.
  • NaBH4 reduction: MeOH/THF or EtOH, 0 °C to RT, 1–4 h to form benzhydrol analog; monitor for over-reduction under forcing conditions.

• Reductive deoxygenation:

  • Wolff–Kishner (hydrazone, then base/high-boiling solvent, 120–200 °C) or Clemmensen (Zn/Hg, HCl; substrate/corrosion compatibility required).

Notes: Degas solvents for cross-couplings. Use inert atmosphere. Verify that conditions do not activate the aryl chlorides unless intended.

Safety and Handling

• Item-specific (from Product Data):

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

• General safety considerations for halogenated aromatic ketones (informational; defer to SDS):

  • Likely hazards: May cause skin/eye irritation and respiratory tract irritation. Avoid dust generation and inhalation. Some benzophenones can be harmful if swallowed.
  • PPE: Use chemical-resistant gloves (e.g., nitrile), lab coat, and splash goggles. Employ a fume hood to control vapors/dust.
  • Handling: Avoid strong bases and strong reducing agents when unintended, as the ketone can be reduced and halogens may undergo metal–halogen exchange. Keep away from strong oxidizers. Prevent prolonged light exposure if photoreactivity is a concern (benzophenone chromophore).
  • Spill/first aid (overview): For small spills, avoid dust; sweep and collect for disposal. On skin/eyes: rinse with water for at least 15 minutes; remove contaminated clothing. If inhaled: move to fresh air. If ingested: rinse mouth; seek medical advice. Always follow institutional protocols.
  • Fire: Combustible organic solid; use CO2, dry chemical, or foam. Thermal decomposition may release HCl/HBr and other irritant fumes.

Always consult the Aladdin Scientific SDS for the definitive hazard classification, response measures, and regulatory information before use.

Solvent Selection

This compound is a hydrophobic, tri-halogenated diaryl ketone. Solvent choice depends on whether you target aryl–X cross-coupling at the bromide/chlorides or carbonyl transformations.

• Polarity/miscibility (literature/general):

  • Water: negligible solubility expected.
  • Good organic solvents: CH2Cl2, CHCl3, toluene, xylene, THF, dioxane, DMF, DMAc, NMP, DMSO, acetonitrile (moderate).
  • For crystallization: aromatics (toluene/xylene) or alcohol/nonpolar solvent pairs often give good crystals for benzophenones.

• Use-case-driven choices:

  • Pd-catalyzed cross-coupling (at Ar–Br): toluene, dioxane, THF, or polar aprotics like DMF/DMAc; base and ligand dictate final choice.
  • Nucleophilic additions to the carbonyl (Grignard/organolithium): strictly anhydrous ethers (Et2O, THF) under inert atmosphere.
  • Reductions (NaBH4 vs stronger): MeOH/EtOH for NaBH4 (if solubility permits); for selective reductions, consider THF/IPA mixtures or transfer hydrogenation solvents.

• Comparison (general):

  • Toluene vs DMF: Toluene offers greener profile and easier workup; DMF improves solubility and can accelerate couplings but complicates quench/purification.
  • THF vs 2-MeTHF: 2-MeTHF provides similar solvation with improved sustainability and phase-splitting advantages.

Always verify solvent compatibility with your catalyst/base system and thermal profile.

Storage and Reconstitution

• Item-specific (from Product Data):

  • Storage Conditions: Room temperature.
  • Shipped In: Not specified for this item; refer to CoA/Spec Sheet.

• General guidance for this class of compounds:

  • Keep container tightly closed in a dry, well-ventilated place. Store in the original amber or light-protective container if provided to minimize potential photochemical reactions of the benzophenone chromophore.
  • Desiccation: Recommended to minimize moisture uptake that can affect certain reactions (e.g., organometallic additions). Include a desiccant pack if long-term storage.
  • Inert atmosphere: Optional but beneficial for long-term storage, especially if repeated opening may introduce humid air.
  • Reconstitution/dissolution: Prepare stock solutions in dry organic solvents (e.g., CH2Cl2, THF, toluene, DMF, DMSO) immediately before use. Filter if necessary through PTFE. Avoid prolonged storage of solutions, particularly in reactive solvents or in light.
  • Freeze–thaw: Not applicable; store as solid. If preparing solutions for short-term use, aliquot to minimize repeated warming cycles.

Always refer to the lot-specific CoA and SDS for any additional storage or handling instructions unique to your material.

Structure and Identity

Brief description: 3-Bromo-3',4'-dichlorobenzophenone is a halogenated benzophenone bearing a bromine on one phenyl ring and two chlorines on the other, with a central ketone (benzophenone) linkage.

• Item-specific (from Product Data):

  • CAS: 844879-39-6
  • InChIKey: 416746 (catalog entry; full-length InChIKey not specified)
  • SMILES: Not specified for this item; refer to CoA/Spec Sheet.

• Computed/literature (for identification; not item specifications):

  • Molecular formula (calculated from name): C13H7BrCl2O
  • Molecular weight (calculated): ~330.00 g/mol
  • Structural features: two aromatic rings linked by a carbonyl (diaryl ketone); one ring bears a meta-bromine (3-bromo), the other ring bears meta- and para-chloro substituents (3',4'-dichloro). No stereocenters; planar ketone flanked by substituted phenyls.
  • 2D description: O=C(Ph–Cl at 3', Cl at 4')–Ph–Br at 3. The carbonyl carbon is sp2; both aryls are conjugated with the C=O, enabling typical benzophenone photophysical behavior.

• General notes: The presence of a bromine (more reactive) and two chlorines (less reactive) provides orthogonal handles for selective cross-coupling and other halogen–metal transformations while retaining the benzophenone carbonyl functionality.

Synthetic Utility

Key functional elements and reactivity:

• Aryl bromide (3-position): primary cross-coupling locus. Compatible with Suzuki, Buchwald–Hartwig (C–N), and etherification (C–O) after oxidative addition. Regioselective activation enables stepwise diversification.
• Aryl chlorides (3′, 4′): secondary, more robust handles. Employ tailored ligands (e.g., BrettPhos/RuPhos) or Ni catalysis to address these sites in later-stage modifications.
• Ketone (benzophenone): platform for nucleophilic additions (tertiary alcohols), reductive transformations (benzhydrol/diarylmethane), and imine/oxime/hydrazone formation for further manipulations (e.g., Wolff–Kishner, Beckmann-type pathways with suitable derivatives).

Retrosynthetic value:

• Enables convergent assembly: couple diverse boronic acids/alkenes at Ar–Br while preserving Ar–Cl sites for modular, orthogonal diversification. The carbonyl provides a strategic branch point for polarity inversion or protection as ketal if needed.

Orthogonality and chemoselectivity tips:

• Exploit relative reactivity: Ar–Br > Ar–Cl. Install sensitive groups after carbonyl chemistry to avoid over-reduction/dehalogenation.
• Use halogen–metal exchange at low temperature (e.g., iPrMgCl·LiCl or nBuLi at ≤ −78 °C) for directed lithiation on the bromo-aryl ring when cross-coupling is undesirable; quench with electrophiles then address carbonyl.

Purification:

• Aromatic ketones typically chromatograph well on silica; halogens aid UV detection. Avoid strongly basic eluents if chlorides are to be preserved.

Target Specificity

Not applicable. This product is a small-molecule chemical building block and is not an antibody, enzyme, or biologic with defined binding targets. No antigen/epitope or species reactivity data apply.