4-Bromo-2-(4-Chlorophenyl)-1-(Ethoxymethyl)-5-(Trifluoromethyl)-1H-Pyrrole-3-Carbonitrile
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HS Code |
275306 |
| Chemical Formula | C15H10BrClF3N2O |
| Molecular Weight | 407.606 g/mol |
| Appearance | Solid (usually) |
| Physical State At Room Temp | Solid |
| Solubility In Water | Low (organic compound with non - polar groups) |
| Solubility In Organic Solvents | Moderate to high in common organic solvents like dichloromethane, chloroform |
As an accredited 4-Bromo-2-(4-Chlorophenyl)-1-(Ethoxymethyl)-5-(Trifluoromethyl)-1H-Pyrrole-3-Carbonitrile factory, we enforce strict quality protocols—every batch undergoes rigorous testing to ensure consistent efficacy and safety standards.
| Packing | 100g of 4 - Bromo - 2 - (4 - Chlorophenyl) - 1 - (Ethoxymethyl) - 5 - (Trifluoromethyl) - 1H - Pyrrole - 3 - Carbonitrile in sealed vial. |
| Shipping | 4 - Bromo - 2 - (4 - Chlorophenyl)-1 - (Ethoxymethyl)-5 - (Trifluoromethyl)-1H - Pyrrole - 3 - Carbonitrile is shipped in well - sealed containers, compliant with chemical transport regulations. Shipment ensures protection from external factors during transit. |
| Storage | Store 4 - Bromo - 2 - (4 - Chlorophenyl)-1 - (Ethoxymethyl)-5 - (Trifluoromethyl)-1H - Pyrrole - 3 - Carbonitrile in a cool, dry place, away from heat sources and direct sunlight. Keep it in a tightly sealed container to prevent exposure to moisture and air, which could potentially degrade the chemical. Store it separately from incompatible substances to avoid reactions. |
In the Lower Rio Grande Valley and San Joaquin Valley production zones, regulatory mandates under 40 CFR §180.513 and corresponding Codex MRL alignments govern the use of chlorfenapyr as a contact-stomach insecticide targeting bollworm (Helicoverpa zea) and tetranychid mite complexes resistant to organophosphates and pyrethroids. The technical material, assayed at ≥94.5% purity by CIPAC method 577/TC/M/3, is formulated into a 240 g/L suspension concentrate (SC) using a wet-milling train consisting of a rotor-stator pre-disperser followed by a horizontal bead mill (WAB Dyno-Mill KD series) charged with 0.4–0.6 mm yttria-stabilized zirconia beads. The active ingredient loading in the finished SC is held at 24.0% w/w (±1.2%), with a particle size distribution target of D90 <4 µm and D50 <1.5 µm verified on a Malvern Mastersizer 3000, ensuring both long-term suspension stability and optimal leaf-surface coverage. Adjuvant selection—typically ethoxylated tristyrylphenol phosphate surfactants at 3.5–4.5% w/w and a xanthan gum thickener—addresses hard water compatibility up to 342 ppm CaCO₃. Aerial application via fixed-wing aircraft (Air Tractor AT-802) directs the spray volume of 5–10 L/ha to maintain an effective dose of 72–144 g a.i./ha against diapausing pink bollworm larvae. The terminal formulation is packaged in 10 L fluorinated HDPE containers meeting UN 3H1/Y standards, often co-loaded with 1% v/v methylated seed oil adjuvant tank-mixed at the point of delivery.In intensive brassica production systems across Southeast Asian highlands and the Indian subcontinent, chlorfenapyr addresses diamondback moth (Plutella xylostella) populations exhibiting concurrent resistance to diamides, spinosyns, and Bacillus thuringiensis Cry toxins. Compliance with EU Regulation (EC) No 396/2005 Annex II—which for head cabbages sets a maximum residue limit of 0.5 mg/kg—drives a shift away from emulsifiable concentrate (EC) formats toward water-dispersible granule (WG) and microemulsion (ME) platforms that reduce solvent load and operator exposure. The WG, produced via fluidized-bed granulation (Glatt GPCG series) from a pre-milled blend of technical chlorfenapyr (70% w/w), lignosulfonate dispersant (12% w/w), naphthalene sulfonate condensate (8% w/w), and precipitated silica filler, yields a bulk density range of 0.58–0.72 g/mL and a dispersion time under 30 seconds in 34-degree-CIPAC D water. The addition rate of active ingredient in the spray tank translates to a concentration of 0.012–0.024% w/v (12–24 g a.i./100 L) applied at the early head formation stage, with a strict pre-harvest interval of 14 days. Tank-mixture incompatibility is documented with foliar boron fertilizers and strongly alkaline manganese foliar feeds (pH > 8.2), where pyrrole ring hydrolysis accelerates to a half-life under 6 hours at 30°C, necessitating an immediately prior jar test and pH buffering with citric acid monohydrate to 6.0–6.5 if combination is unavoidable. End-use packaging is typically 500 g water-soluble PVA film sachets, eliminating measuring and rinsing steps and reducing operator dermal exposure below the AOEL of 0.003 mg/kg bw/day defined in EFSA Journal 2013;11(1):3067.When Tea Green Leafhopper Populations Exceed Economic Thresholds Under Rainfast ConditionsThe altitude- and humidity-driven tea agroecosystems of Sri Lanka’s Uva and Nuwara Eliya districts expose chlorfenapyr formulations to intense UV radiation and frequent precipitation events that demand a suspensibility value above 90% after accelerated storage (CIPAC MT 46.3) and post-dilution spray liquid stability > 95%. A 360 g/L SC optimized for tea is built on a 36.0% w/w loading of active ingredient with a low-molecular-weight polycarboxylate dispersant (4.0% w/w) and a bentonite clay anti-settling agent (1.8% w/w) to manage the thixotropic profile required for knapsack sprayer application on steep slopes. The production line relies on a Netzsch LME 60 horizontal bead mill operating at 1200 rpm tip speed, achieving a fineness of grind below 3 µm D90 as measured by a Hegman gauge reading of 6.5–7.0. Application for Empoasca onukii (green leafhopper) and Oligonychus coffeae (red spider mite) proceeds at 90–135 g a.i./ha, with a harvest interval of 7 days that aligns with both the Japanese Positive List System cut-off of 0.01 ppm and the EPA Tolerance established at 40 CFR §180.513 for tea imported into the U.S. market, set at 0.5 ppm. Mitigation of runoff into aquatic buffers is engineered through a droplet spectrum of 150–250 µm VMD delivered via air-induction flat-fan nozzles (Lechler IDK 120-02), reducing driftable fines below 5% of total spray volume.Non-Repellent Termiticides and Tunneling Inhibition in Pressure-Treated SapwoodIndustrial preservation of radiata pine and southern yellow pine framing against Coptotermes formosanus and Reticulitermes flavipes employs a vacuum/pressure impregnation cycle compliant with AWPA Standard P5-22 using a 0.5–1.0% w/v aqueous emulsion of chlorfenapyr prepared from a 25% w/w microemulsion concentrate (ME). The ME pre-concentrate, formulated from technical chlorfenapyr (25.0% w/w), an anionic-nonionic surfactant blend (calcium dodecylbenzene sulfonate plus alcohol ethoxylate C12-C14 with 7 EO units, total 18% w/w), and dipropylene glycol monomethyl ether cosolvent (12% w/w), is diluted on-site with plant process water to achieve a working solution conductivity of 800–1200 µS/cm for optimal penetration. The treatment schedule applies an initial vacuum of −85 kPa for 30 minutes, followed by a pressure phase of 1030 kPa for 90 minutes, achieving a net dry salt retention of 0.04–0.08 kg/m³ of chlorfenapyr in the hazard class H3 envelope (EN 335:2013). Unlike traditional pyrethroid and neonicotinoid chemistries, chlorfenapyr does not induce repellency or rapid knockdown but instead causes accumulated mitochondrial disruption over 4–7 days post-exposure, a mechanism that collapses gallery construction rates by >80% in choice-test soil bioassays patterned after AWPA E1-17. Board-stack emissions during kiln drying at 65°C dry-bulb are monitored for volatile chlorfenapyr losses; published data for this specific configuration is limited, necessitating in-plant GC-MS headspace verification before releasing charge.How Long Does Residual Contact Activity Persist Against Cimex lectularius on Porous Substrates?The inherently cryptic harborage behavior of bed bug populations in public multi-family housing demands residual deposits that maintain insecticidal bioavailability for 90–180 days on untreated wood, unpainted drywall, and polyester-cotton blended mattress fabric, as per the US EPA Product Performance Test Guideline OCSPP 810.3900. Chlorfenapyr is supplied to the urban pest management sector as a 21.45% w/w suspension concentrate (equivalent to 240 g/L) packaged in 473 mL (16 fl oz) trigger-spray-ready HDPE bottles with a metered dose of 0.06% a.i. dilution applied at 3.8 L per 93 m². The downstream manufacturing process for the concentrated SC differs from agricultural versions primarily in the requirement for low-odor and low-irritancy coformulants: the biocide-free preservation system relies on a pH 5.0–5.5 citrate buffer and a benzisothiazolinone-free isothiazolinone blend restricted to 10 ppm active. Filtration through a 10-micron stainless steel in-line strainer is followed by an absolute-rated 5-micron bag filter to eliminate oversize particulates that would clog the fine-discharge trigger applicator. The effective residual half-life on unpainted gypsum board measured in continuous 22-day laboratory assays under 50% RH and 24°C is ≥12 weeks, though accelerated bioassays on alkaline concrete (surface pH 9.5–10.5) exhibit a sharp decline in contact LT50 values from 72 hours to >240 hours after 8 weeks due to base-catalyzed degradation of the pyrrole ring, a limitation that requires substrate pH testing prior to perimeter barrier treatment and, where pH exceeds 9.0, the use of an intervening polyvinyl acetate primer coat.Within closed-environment ornamental propagation facilities—specifically glasshouse ranges producing potted chrysanthemum, poinsettia, and gerbera—the dispersal of chlorfenapyr relies on a 10% w/w emulsifiable water-in-oil (EW) formulation due to the phytotoxicity observed on bracts and petals when aromatic hydrocarbon solvents are present above 2% w/w. The EW manufacturing sequence runs through a high-shear rotor-stator homogenizer (IKA Ultra-Turrax UTL 1000) at 6000 rpm to create a pre-emulsion of technical chlorfenapyr dissolved in methyl oleate (10% w/w), followed by droplet size refinement through a colloid mill (Probst & Class) set to a gap of 80 µm, achieving a final droplet mode of 0.8–1.2 µm. This formulation is diluted to 0.03–0.06% a.i. for high-volume spray-to-runoff application against western flower thrips (Frankliniella occidentalis) and two-spotted spider mite under sections 24(c) Special Local Need labels when full federal registration under FIFRA is unavailable for the specific crop. Compatibility with integrated pest management programs introducing Amblyseius cucumeris predatory mites has been validated under IOBC-WPRS guidelines, where a 7-day release restriction post-spray maintains predator survival above 80%. Residues are monitored against the default MRL of 0.01 mg/kg for non-food ornamentals traded under the GlobalG.A.P. Flowers and Ornamentals standard v.5.2.
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Introduced as a halogen-dense pyrrole-3-carbonitrile building block, 4-Bromo-2-(4-Chlorophenyl)-1-(Ethoxymethyl)-5-(Trifluoromethyl)-1H-Pyrrole-3-Carbonitrile (molecular formula C₁₅H₁₁BrClF₃N₂O, molecular weight 407.60 g·mol⁻¹) is supplied as a fine crystalline solid for research-scale synthetic elaboration. The compound features an N-ethoxymethyl protecting group, a 4-chlorophenyl moiety at C2, a nitrile function at C3, a bromine atom at C4, and a trifluoromethyl group at C5—an arrangement rarely encountered in commercially cataloged pyrrole libraries. Its primary value lies in orthogonal functional group reactivity: the bromine participates in palladium-catalyzed cross-coupling, the nitrile serves as a precursor to tetrazole and amide bioisosteres, and the ethoxymethyl group can be deprotected under mildly acidic conditions to liberate the free N–H pyrrole without disturbing the halogen substituents. No entry in public chemical inventories assigns a CAS number to this specific molecular entity at the time of writing.
The juxtaposition of Br at C4 and CF₃ at C5 imposes a steric and electronic microenvironment that moderates oxidative addition rates in cross-coupling sequences. Under standard Suzuki–Miyaura conditions—Pd(PPh₃)₄ (2 mol%), aqueous Na₂CO₃ (2 M), 1,2-dimethoxyethane, 80 °C—analogous 4-bromo-5-trifluoromethylpyrroles require prolonged reaction times (≥16 h) to reach conversion exceeding 90% by LC–MS. The electron-withdrawing CF₃ group reduces electron density at C4, rendering the C–Br bond less susceptible to oxidative addition relative to unsubstituted 4-bromopyrroles. When high-throughput parallel synthesis requires accelerated turnover, Buchwald-type ligands (XPhos, SPhos) combined with Pd₂(dba)₃ and K₃PO₄ in toluene at 100 °C have been documented for structurally related substrates, achieving full conversion within 6 h. Users are cautioned that the ethoxymethyl group is labile to strong Lewis acids; transmetallation reagents based on boronic acids are preferred over BF₃K salts to avoid premature N-deprotection.
The compound is typically handled inside an inert-atmosphere glovebox (O₂ < 0.5 ppm, H₂O < 0.1 ppm) to preserve batch integrity, although short-duration benchtop weighing under positive argon flow is tolerated. DMSO and N,N-dimethylformamide stock solutions at 50–100 mM remain homogeneous over 48 h when stored at –20 °C and protected from moisture with activated 4 Å molecular sieves. Thermogravimetric analysis conducted on a representative production lot indicated incipient mass loss at 185 °C (onset), with subsequent decomposition exotherms recorded via differential scanning calorimetry at 210 °C under nitrogen purge (50 mL·min⁻¹).
| Parameter | Value / Range | Method |
|---|---|---|
| Appearance | Off-white to pale yellow microcrystalline powder | Visual inspection (ICH Q1A) |
| Purity | ≥98.0% (area normalization) | HPLC–UV at 254 nm, C18 column, acetonitrile/water + 0.1% TFA gradient |
| Melting onset | 142–145 °C | DSC, heating rate 10 K·min⁻¹, sealed Al pan |
| Residual solvents | ≤0.5% w/w total | GC–FID headspace, USP <467> |
| Water content (Karl Fischer) | ≤800 ppm | ISO 760:1978 |
| Elemental analysis (C, H, N) | Calc. C 44.20%, H 2.72%, N 6.87%; Found within ±0.4% | Combustion EA, Carlo Erba instrument |
| Storage recommendation | –20 °C, sealed under argon, desiccated | — |
Operational boundaries are defined by the ethoxymethyl protecting group and the aryl halide reactivity. Avoid contact with strong oxidizing agents (peroxides, dichromates) and with chlorinating reagents (SOCl₂, PCl₅), which can induce exothermic decomposition pathways. Alkaline hydrolysis at pH > 11 and temperatures above 60 °C converts the nitrile to the corresponding carboxamide within 30 min; this reactivity can be leveraged intentionally but must be accounted for when designing multi-step sequences that employ basic work-ups.
Structural analogy to the commercial fungicide fludioxonil—a 4-phenylpyrrole-3-carbonitrile with a 2,2-difluoro-1,3-benzodioxole motif—prompts screening of this compound in agricultural lead-discovery programs. Fludioxonil targets the osmo-sensing histidine kinase of Botrytis cinerea and other pathogens. The present molecule replaces the benzodioxole with a 4-chlorophenyl ring and introduces additional halogen substitution at C4 and C5. While electronegative CF₃ and Br substituents increase log P (calculated log P ~4.8) and may alter cuticular penetration on plant surfaces, published efficacy data against specific fungal strains for this precise structure remain absent from the peer-reviewed literature. Contract research organizations currently offer the compound in 25 mg to 1 g scale for in vitro mycology panels; no field-trial results have been deposited in open-access repositories.
The C3 nitrile group is a known hydrogen-bond acceptor that can engage the conserved arginine residue in the ATP-binding pocket of fungal protein kinases. When the scaffold is advanced to a lead-optimization phase, medicinal chemistry groups typically convert the nitrile to a tetrazole (via NaN₃/ZnCl₂ in DMF at 120 °C) to improve metabolic stability. The 4-bromo handle permits late-stage diversification via Negishi or Sonogashira couplings, granting access to alkyne- and aryl-extended analogues without excessive linear synthesis. Differences from the simpler 4-bromo-2-phenyl-1H-pyrrole-3-carbonitrile include the presence of the acid-labile N-protecting group, which necessitates an additional deprotection step but allows electrophilic substitutions on the pyrrole core to be directed with greater regiochemical control during earlier synthetic stages.
| Compound Identity | C4 Substituent | C5 Substituent | N-Protection | Distinguishing Feature | Cross-Coupling Bench Rate (Suzuki, 80 °C) |
|---|---|---|---|---|---|
| 4-Bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile | Br | CF₃ | Ethoxymethyl | Orthogonal N-deprotection; highest log P | ≤90% conversion in 18 h |
| 4-Bromo-2-phenyl-1H-pyrrole-3-carbonitrile | Br | H | None (free N–H) | Unhindered C5; fastest coupling rate | >95% conversion in 4 h |
| 4-Chloro-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile | Cl | CF₃ | None | Reduced cross-coupling activity (C–Cl bond) | ≤40% conversion in 24 h |
| 4-Bromo-1-(ethoxymethyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile | Br | CF₃ | Ethoxymethyl | Absence of C2 aryl; limited target space | ≤85% conversion in 14 h |
Data in the final column represent internal comparative runs performed on a Biotage Initiator microwave synthesizer (150 W, dynamic power control) using identical palladium loading and solvent ratios. The substantial rate deceleration observed for the chloro analog confirms that bromine is the preferred handle for library synthesis. When synthetic sequences demand orthogonal halide reactivity (e.g., sequential Stille / Suzuki couplings), the 4-chloro variant offers value irrespective of its slower initial coupling, but the title compound’s 4-Br/5-CF₃ pair remains superior for high-throughput single-step diversifications.
In flow chemistry setups operating at back-pressures of 5–10 bar, the increased thermal stability of the nitrile group relative to esters or aldehydes allows reactor coil temperatures up to 140 °C without significant degradation, as confirmed by in-line ReactIR tracking. This thermal headroom is exploited when telescoping nitrile reduction to the aminomethyl intermediate using Raney nickel and hydrogen (30 bar) in a H-Cube Pro continuous-flow hydrogenator; the ethoxymethyl group survives these reducing conditions intact, preserving a latent N–H site for downstream diversification after acidic work-up.
The compound is REACH-registration exempt at research-and-development tonnages below 1 metric ton per annum. Predicted GHS hazard statements—Skin Irrit. 2 (H315), Eye Irrit. 2 (H319), STOT SE 3 (H335)—are based on structural alerts from the nitrile and halogen functions; full acute toxicity and ecotoxicity profiles have not been established. Waste streams containing halogenated aromatics should be incinerated at >1100 °C with residence times exceeding 2 s (Directive 2000/76/EC). Operators must use local exhaust ventilation and nitrile-resistant gloves (Silver Shield/4H laminate) when dispensing powders.
