N-((3-bromophenyl)methylidene)hydroxylamine - ≥95% , CAS No.51873-95-1

CAS: 51873-95-1 Cat. No.: N1050397 Formula: C₇H₆BrNO Peso molecolare: 200.035 Numero EC: 610-748-5 PubChem CID: 5375574

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

C1=CC(=CC(=C1)Br)C=NO

IUPAC Name

(NE)-N-[(3-bromophenyl)methylidene]hydroxylamine

InChIKey

DBGBMIPNNIZQNN-WEVVVXLNSA-N

INCHI

1S/C7H6BrNO/c8-7-3-1-2-6(4-7)5-9-10/h1-5,10H/b9-5+

Isomeri SMILES

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

PubChem CID

5375574

Peso molecolare

200.035

Taxonomic Classification

Taxonomy Tree

• Kingdom Organic compounds
  • Superclass Benzenoids
    • Classe Benzene and substituted derivatives
      • Subclass Halobenzenes

• Kingdom: Organic compounds
• Superclass: Benzenoids
• Classe: Benzene and substituted derivatives
• Subclass: Halobenzenes
• Intermediate Tree Nodes: Not available
• Direct Parent: Bromobenzenes
• Alternative Parents: Aryl bromides Aldoximes Organopnictogen compounds Organobromides Organic oxygen compounds Hydrocarbon derivatives
• Molecular Framework: Aromatic homomonocyclic compounds
• Substituents: Bromobenzene - Aryl halide - Aryl bromide - Aldoxime - Organic nitrogen compound - Organic oxygen compound - Organopnictogen compound - Hydrocarbon derivative - Organonitrogen compound - Organobromide - Organohalogen compound - Aromatic homomonocyclic compound
• Descrizione: This compound belongs to the class of organic compounds known as bromobenzenes. These are organic compounds containing a bromine atom attached to a benzene ring.
• 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: 200.030 g/mol
• XLogP3: 2.300
• Hydrogen Bond Donor Count: 1
• Hydrogen Bond Acceptor Count: 2
• Rotatable Bond Count: 1
• Exact Mass: 198.963 Da
• Monoisotopic Mass: 198.963 Da
• Topological Polar Surface Area: 32.600 Ų
• Heavy Atom Count: 10
• Formal Charge: 0
• Complexity: 127.000
• 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

Not applicable. No immunoassay or cell-based “application” protocols are defined for this small-molecule reagent. For synthetic use, see the Reaction Conditions and Synthetic Utility sections for literature-style procedural guidance.

Biological Roles

This compound is a synthetic organic intermediate and is not a native metabolite. No item-specific biological data are provided.

General context (literature):

• Oximes are encountered in biochemistry as reversible condensation products of carbonyls and hydroxylamine, but aryl aldoximes like this are not typical biological intermediates. They can hydrogen bond and may chelate metals weakly via the N–O motif.
• The aryl bromide substituent facilitates further derivatization for chemical biology probes; however, any bioactivity would depend on the final scaffold and is not inherent to this oxime.

Use strictly for research and laboratory synthesis. Do not use for diagnostic or therapeutic applications.

Buffer Applications

Not typically applicable. This small-molecule aryl aldoxime is not used as a buffering agent. For aqueous workups or hydrolysis studies, conventional buffers (e.g., acetate, phosphate, citrate) should be used instead according to your reaction needs.

Green Alternatives

Greener choices relate to both solvent/reagent selection and step economy around oxime interconversions.

• Dehydration to nitrile (literature):
  • Greener approach: use acetic anhydride (reagent/solvent) or catalytic P2O5 on silica, vs SOCl2 or POCl3 which are corrosive and generate halogenated waste.
  • Solvent choices: replace CH2Cl2 with EtOAc or 2-MeTHF when feasible.
• Reduction to amine:
  • Prefer catalytic hydrogenation (H2/Pd-C, EtOH/EtOAc) over stoichiometric metal reductions (Zn/HCl) to minimize metal salt waste; capture Pd for recycling.
• Cross-coupling at Ar–Br:
  • Employ aqueous micellar catalysis (e.g., surfactant media) or bio-derived solvents (Cyrene, 2-MeTHF) instead of DMF/NMP when compatible with the catalyst system.
• Hydrolysis/reversion to aldehyde:
  • Use aqueous ethanol under catalytic acid at ambient temperature to reduce energy input.

Comparison (literature-based, not product specs):

• SOCl2/DMF vs Ac2O
  • Waste/impact: high vs moderate
  • Operational simplicity: moderate vs high (solvent doubles as reagent)
  • Selectivity: both effective; Ac2O less aggressive toward sensitive motifs
• CH2Cl2 vs 2-MeTHF/EtOAc
  • Regulatory pressure: higher vs lower
  • Worker exposure: halogenated vs non-halogenated

Always validate greener swaps on small scale; oxime E/Z composition and rate can change with solvent polarity and acidity.

Pharmaceutical Uses

No pharmacopeial status or excipient role is specified for this item. As a synthetic intermediate, N-((3-bromophenyl)methylidene)hydroxylamine may be used in process routes where oxime formation protects or channels aldehydes to nitriles or amines (literature). Any application would be upstream in R&D or process development, not as a finished formulation component. For GMP or regulatory uses, obtain grade-appropriate documentation and impurity/isomer profiles from the CoA. No medical or therapeutic claims are made or implied.

Physical Properties

Item-specific physical property specifications are not provided in the Product Data for this SKU. Do not treat any values below as product specifications; verify on the CoA/Spec Sheet for your lot.

• Appearance (item-specific): Not specified for this item; refer to CoA/Spec Sheet.
• Grade/Purity (item-specific): Not specified for this item; refer to CoA/Spec Sheet.
• Molecular weight (literature/computed for C7H6BrNO): ~200.03 g/mol.
• Physical state (general): aromatic aldoximes are typically crystalline solids; E/Z isomerism can influence melting behavior (literature).
• Solubility (general guidance):
  • Good solubility in polar organic solvents (EtOAc, acetone, MeOH/EtOH, acetonitrile, DMSO, DMF) (literature).
  • Limited solubility expected in nonpolar alkanes; low solubility in water (literature).
• Volatility: low; not expected to be volatile at room temperature (literature for aryl oximes).
• Acid/base behavior: weakly basic/acidic due to oxime tautomeric forms; can hydrogen-bond; forms salts only under forcing conditions (literature).
• UV behavior (qualitative): conjugation imparts aromatic/imine absorbance in UV; specific cutoff/ε not established here (literature; not a product spec).

If precise values such as melting point, density, or refractive index are critical for your method development or QC, please request the current CoA.

Quality and Grades

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

Guidance for interpreting grades (general):

• Research-grade aryl oximes are typically provided with assay by NMR/GC/LC and may include E/Z ratio reporting when relevant. Low residual solvents and controlled inorganic content are desirable for catalysis or medicinal chemistry programs.
• HPLC grade (if applicable) emphasizes low UV background and impurity levels to support analytical workflows. For synthetic use, “≥98%” or similar assay is commonly acceptable; for fragment screening or photochemical applications, higher purity and isomer definition may be warranted.
• Stabilizers: Oximes generally do not require stabilizers; absence/presence would be stated on the CoA. None is specified for this item.
• Trace specifications: Water content, residual metals, peroxides, and UV cutoff are not specified for this item; refer to CoA/Spec Sheet if such controls are critical to your use-case.

Recommendation: When selectivity depends on oxime geometry, request or verify E/Z composition. For cross-coupling at the aryl bromide, trace metal impurities in the substrate are usually less critical than in ligands, but high assay facilitates predictable kinetics.

Reaction and Applications

This meta-brominated aryl aldoxime is a versatile bifunctional building block that leverages both the aryl bromide and the aldoxime.

• Transformations of the aldoxime (literature):
  • Dehydration to the corresponding nitrile (3-bromobenzonitrile) using acetic anhydride, POCl3/pyridine, SOCl2/DMF, or Burgess-type reagents. Typically high-yielding under anhydrous, mildly heated conditions.
  • Reduction to the primary amine (3-bromobenzylamine) via catalytic hydrogenation (H2/Pd-C) or metal-mediated reductions (Zn/HCl, TiCl3), and by hydride donors under activating conditions (e.g., LAH in THF, chemoselectivity must be managed against Ar–Br).
  • Hydrolysis back to 3-bromobenzaldehyde under aqueous acidic conditions (reversible condensation).
  • O-Functionalization (O-acyl/O-aryl oxime esters) enabling N–O bond activation to generate iminyl radicals or undergo rearrangements/eliminations.
• Transformations of the aryl bromide (literature):
  • Cross-couplings: Suzuki–Miyaura (to arylate/alkenylate), Buchwald–Hartwig (N-arylation), Sonogashira (alkynylation), Stille/Negishi (C–C formation), with the oxime often tolerated under Pd catalysis.
  • Nucleophilic substitutions under lithium–halogen exchange (forming aryllithium) followed by electrophile trapping; protect the oxime as an O-derivative if needed.
• Strategic roles:
  • Orthogonal diversification: modify the aryl bromide first, then convert the oxime to nitrile/amine as needed.
  • Directing group chemistry: oxime derivatives can direct ortho-C–H functionalization (via oxime ethers/esters) in late-stage diversification.

Applications include synthesis of 3-bromobenzonitrile/adducts, generation of 3-bromobenzylamine intermediates, and two-point diversification in medicinal chemistry.

Reaction Conditions

The following are literature-derived, non-item-specific guidelines. Optimize per substrate/catalyst and verify compatibility with the oxime functionality.

• Dehydration to 3-bromobenzonitrile:
  • Ac2O (3–10 equiv), 80–120 °C, 1–4 h; often neat or in EtOAc; base (pyridine) can accelerate. Typical isolated yields: good to excellent.
  • POCl3 (2–4 equiv) in pyridine or MeCN, 0 °C to reflux, 1–3 h; aqueous workup neutralization required.
  • SOCl2 (3–6 equiv) with catalytic DMF in CH2Cl2 or MeCN, 0–25 °C then reflux 0.5–2 h.
• Reduction to 3-bromobenzylamine:
  • H2 (1–5 bar) over Pd/C (5–10 wt%), EtOH or EtOAc, 20–50 °C, 2–16 h; avoid over-reduction of Ar–Br by controlling pressure and catalyst loading.
  • Zn/HCl (aq) or TiCl3 in THF/MeOH, 0–25 °C to reflux; workup neutralization and extraction.
  • LAH in THF, 0 °C to reflux; caution with exotherm and possible Ar–Br reduction.
• Hydrolysis back to 3-bromobenzaldehyde:
  • 1–10% HCl in MeOH/H2O (1:1), rt–50 °C, 0.5–4 h.
• Cross-coupling at Ar–Br (oxime tolerated in many cases):
  • Suzuki–Miyaura: aryl/alkenyl boron (1.2–1.5 equiv), Pd(PPh3)4 (1–3 mol%), K2CO3 (2–3 equiv), dioxane/H2O (3:1), 70–90 °C, 2–12 h.
  • Buchwald–Hartwig: amine (1.2–1.5 equiv), Pd2(dba)3 (1–2 mol%) with BINAP/XPhos, NaOtBu, toluene or dioxane, 80–110 °C.
  • Sonogashira: terminal alkyne, Pd(PPh3)2Cl2/CuI, Et3N or DIPEA, THF or MeCN, 25–60 °C.

Notes: Control moisture for dehydrations; monitor E/Z interconversion if crystallinity/purity depend on isomer. Always perform small-scale trials to establish selectivity.

Safety and Handling

Authoritative safety information resides in the SDS for this product/lot. The following are general precautions for aryl aldoximes and aryl bromides.

• GHS classification, signal word, H-statements, pictograms (item-specific): Not specified for this item; refer to SDS.
• General hazards (literature/analogous materials): May cause skin/eye irritation and respiratory tract irritation; avoid dust formation and inhalation. Oximes can be sensitizers in some cases.
• Incompatibilities: Strong oxidizers; strong acids or bases (can promote hydrolysis/dehydration); agents that activate N–O bonds; reducing metals in the presence of moisture (risk of side reactions). Avoid prolonged exposure to light/heat that could induce E/Z isomerization or decomposition.
• Peroxide formation: Not a peroxide-forming solvent; no special peroxide risk typical of ethers.
• PPE: Lab coat, chemical-resistant gloves (e.g., nitrile), safety glasses or goggles; use fume hood to control vapors/dust.
• First aid (overview; consult SDS for details):
  • Inhalation: move to fresh air; seek medical attention if symptoms persist.
  • Skin/eye contact: rinse with water for several minutes; remove contaminated clothing; seek medical advice for irritation.
  • Ingestion: rinse mouth; do not induce vomiting; obtain medical attention.
• Spills: Avoid dust; collect solids by gentle sweeping; for solutions, absorb with inert material. Dispose per local regulations.
• Fire: Use CO2, dry chemical, or alcohol-resistant foam; decomposition can release corrosive/irritant fumes (e.g., HBr, NOx) per literature.

Solvent Selection

As an aryl aldoxime with a polar –CH=NOH and an aryl bromide, this compound balances moderate polarity with aromatic character.

• Polarity/miscibility (literature/general):
  • Soluble: DMSO, DMF, NMP, MeCN, EtOAc, acetone, MeOH/EtOH, CH2Cl2, THF.
  • Limited: toluene, ethylbenzene; may require heating.
  • Poor: aliphatic hydrocarbons; water.
• Selection guidance by task:
  • Cross-coupling at Ar–Br: dioxane/H2O, toluene, or MeCN with a suitable base (e.g., K2CO3, Cs2CO3). If substrate solubility is low in toluene, switch to dioxane or DMF.
  • Oxime dehydration to nitrile: acetic anhydride (also reagent/solvent), POCl3 in pyridine, or SOCl2 with an inert co-solvent (CH2Cl2, MeCN).
  • Reduction to primary amine: MeOH/EtOH for catalytic hydrogenation; EtOAc or THF for metal-mediated reductions (Zn/AcOH; TiCl3).
  • Hydrolysis back to aldehyde: aqueous EtOH or MeOH with catalytic acid.
• Practical tips:
  • If crystallization is desired, use EtOAc/hexanes or toluene/hexanes systems (screen due to E/Z behavior).
  • For N–O activation steps (e.g., O-acylation), employ dry, aprotic media (CH2Cl2, MeCN) and exclude water.

Note: No item-specific solvent restrictions are provided; choose based on reaction and safety profile.

Storage and Reconstitution

• Storage (item-specific): Room temperature (per Product Data). Store tightly closed in a dry, well-ventilated place. Protect from moisture and prolonged light/heat, which can promote oxime E/Z isomerization or hydrolysis.
• Container: Use amber glass with PTFE-lined cap when possible to limit moisture ingress and light exposure.
• Stability: Oximes are generally stable solids under dry conditions. Avoid strong acids/bases and reactive chlorinating/dehydrating agents unless in deliberate use.
• Reconstitution/preparation:
  • For stock solutions, dissolve in a dry, appropriate solvent such as DMSO, DMF, MeCN, EtOAc, acetone, MeOH, EtOH, or CH2Cl2 depending on the intended application.
  • Typical lab stock concentrations: 10–200 mM for DMSO/DMF; adjust to solubility and handling preferences. Filter if particulates are present.
  • For water-incompatible operations, ensure glassware and solvents are dry; include molecular sieves if storing solutions >24 h.
• Shelf life: Not specified for this item; refer to CoA/Spec Sheet. For best results, prepare fresh solutions before use and minimize freeze–thaw or repeated heating.
• Shipping: Not specified for this item. Given room-temperature storage, ambient shipment is generally suitable unless otherwise noted on the CoA/SDS.

Research use only.

Structure and Identity

N-((3-bromophenyl)methylidene)hydroxylamine is the aldoxime of 3-bromobenzaldehyde, i.e., a meta-brominated aryl aldoxime bearing an –CH=NOH functionality conjugated to the aromatic ring.

• Item-specific identifiers (from Product Data)
  • CAS: 51873-95-1
  • CID: 5375574
  • InChIKey: Not specified for this item; refer to CoA/Spec Sheet.
  • SMILES: Not specified for this item; refer to CoA/Spec Sheet.
• Structural features (general/literature description)
  • Functional groups: aryl bromide (m-Br), aldoxime (–CH=NOH) capable of E/Z (syn/anti) geometric isomerism about C=N.
  • Typical 2D description: a benzene ring bearing Br at the 3-position relative to the oxime-bearing benzylic carbon; the benzylic carbon is double-bonded to nitrogen and singly bonded to hydrogen; nitrogen bears a hydroxyl substituent.
  • Stereochemistry: exists as E/Z oxime isomers (literature); commercial materials may contain an isomeric mixture unless otherwise specified (not specified for this item).
• Empirical formula and formula mass (literature/computed for 3-bromobenzaldoxime)
  • Molecular formula (literature): C7H6BrNO
  • Molecular weight (literature): ~200.03 g/mol

Note: Exact structural identifiers and isomer composition for this catalog item are not specified; consult the CoA/SDS for definitive identity metadata.

Synthetic Utility

Key functional handles and their retrosynthetic value (literature/general):

• Aldoxime (–CH=NOH):
  • Protecting/linchpin function for 3-bromobenzaldehyde, enabling reversible protection (hydrolysis) or divergence to nitrile (dehydration) and primary amine (reduction). Useful for convergent routes where late-stage choice among –CHO/–CN/–CH2NH2 is desirable.
  • Activation via O-acylation affords oxime esters, enabling N–O bond chemistry (radical generation, rearrangements), or serving as a directing group precursor (oxime ethers/esters) for ortho-C–H functionalization.
• Aryl bromide:
  • Robust locus for cross-coupling diversification (Suzuki, Buchwald–Hartwig, Sonogashira, Negishi), allowing rapid SAR generation while retaining the oxime for subsequent functional group interconversions.
  • Lithium–halogen exchange permits introduction of electrophiles (e.g., formylation, borylation) with care to protect the oxime if necessary.

Orthogonal strategy examples:

• First, perform Suzuki coupling to install heteroaryl/alkenyl motifs under Pd catalysis; second, dehydrate oxime to nitrile to tune electronics/lipophilicity.
• Alternatively, reduce oxime to primary amine, then carry out Buchwald–Hartwig N-arylation on an appended amine (after bromide diversification), constructing benzylamine derivatives.

This orthogonality makes the compound a valuable two-point diversification node in medicinal and materials chemistry.

Target Specificity

Not applicable. This product is a small-molecule synthetic intermediate, not a biological targeting reagent. No antigen/epitope or species reactivity data are associated with this item.