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Bromoacetone

Bromoacetone (CH₃COCH₂Br) is an organic compound belonging to the class of α-haloketones, characterized as a volatile, colorless liquid that readily turns violet upon exposure to air and exhibits a pungent odor.^[1] It possesses strong lachrymatory properties, inducing severe irritation to the eyes, upper respiratory tract, and skin upon contact, rendering it denser than water with a boiling point around 137 °C.^[2]^[3] Historically, bromoacetone was deployed as a non-lethal chemical warfare agent during World War I, designated BA by British forces and B-Stoff (white cross) by Germans, exploiting its capacity to incapacitate adversaries through intense lacrimation and respiratory distress without widespread fatalities.^[1]^[4] Its synthesis typically involves the bromination of acetone in aqueous acetic acid or similar media, facilitating α-substitution due to the enolizable nature of the ketone.^[5] Due to its extreme toxicity and the evolution of more effective riot control agents, bromoacetone's wartime and tear gas applications have been obsolete since the mid-20th century, though it retains niche utility in organic synthesis as an alkylating reagent.^[1]^[4]

History

Discovery and early synthesis

Bromoacetone was first prepared in 1876 by the Russian chemist N. Sokolowsky via the direct bromination of acetone, marking its initial documentation in organic chemistry literature.^[6] This synthesis exploited the electrophilic halogenation at the alpha position of the ketone, where bromine substitutes a hydrogen on the methyl group adjacent to the carbonyl, yielding CH₃COCH₂Br.^[6] The reaction conditions involved treating acetone with bromine, often in the presence of an acid catalyst such as acetic acid to promote enol formation and subsequent bromination, though early reports emphasized straightforward addition without specifying stabilizers.^[6] Sokolowsky's work, published in Berichte der deutschen chemischen Gesellschaft, described the product as a volatile liquid and noted its incidental irritant effects during handling, consistent with the alkylating reactivity of alpha-haloketones that enables nucleophilic attack by thiols or amines in mucous membranes.^[6] Early recognition of bromoacetone as a haloacetone derivative stemmed from analogous preparations of chloroacetone and iodoacetone in prior decades, with its lachrymatory action emerging from empirical observations in halogenation setups rather than targeted irritant studies.^[6] These properties were attributed to the compound's ability to form reactive intermediates, underscoring the causal link between alpha-halogen substitution and enhanced electrophilicity in ketone systems.^[6]

Deployment in World War I

Germany first deployed bromoacetone in July 1915 as B-Stoff, a lacrimatory agent within the White Cross series of irritants, primarily disseminated via artillery shells such as the T-shell variant.^[7] These shells targeted enemy positions to exploit vulnerabilities in respiratory and ocular defenses, with the agent vaporizing upon impact to produce rapid, intense irritation.^[8] The compound's effects centered on severe lacrimation, bronchial spasm, and pulmonary edema at higher exposures, resulting in temporary incapacitation through blinding tears and violent coughing fits rather than widespread fatalities.^[9] Empirical battlefield data indicated low lethality, with most casualties recovering after evacuation, but its psychological and tactical disruption value proved substantial in disrupting infantry advances and trench holds on the Western Front.^[7] British forces referred to bromoacetone as BA gas and encountered it in German barrages, while also incorporating similar irritants into their own munitions.^[9] It was frequently mixed with xylyl bromide (T-Stoff) to enhance persistence and diffusion under varying weather conditions, allowing for more reliable area denial compared to standalone applications.^[10] By late 1915, bromoacetone's role diminished as Germany shifted to deadlier pulmonary agents like phosgene (introduced December 1915) and vesicants such as mustard gas (1917), which offered greater casualty rates and strategic impact despite bromoacetone's continued limited use in harassing fire.^[7]

Post-war obsolescence

Following the armistice of November 11, 1918, bromoacetone's deployment as a chemical irritant ended abruptly, with production halting amid disarmament efforts and the destruction of wartime stockpiles. By the early 1920s, surplus munitions containing bromoacetone were systematically disposed of, including dumping into the North Sea and other sites, as Allied forces cleared battlefields and depots to comply with Versailles Treaty restrictions on German chemical capabilities.^[10] This obsolescence was accelerated by the agent's inherent drawbacks: its liquid state, low boiling point of 136°C, and tendency to decompose spontaneously, rendering it logistically challenging for storage and dissemination compared to solid alternatives.^[1] The 1925 Geneva Protocol further curtailed bromoacetone's prospects by prohibiting the wartime use of "asphyxiating, poisonous or other gases," encompassing irritants like bromoacetone despite their non-lethal classification; while the treaty allowed domestic riot control applications, signatories increasingly favored less toxic options to avoid escalation risks.^[11] Interwar experimentation with lacrimators persisted in limited police and military trials, but bromoacetone's superior irritancy—approximately 18 times that of chloroacetone—came at the cost of excessive pulmonary toxicity and skin blistering, prompting replacement by chloroacetophenone (CN), a crystalline solid with a higher melting point (59°C) that enabled aerosolization via grenades and sprays with reduced volatility and handling hazards.^[12]^[13] By the 1930s, archival evidence from demilitarization programs indicates that remaining bromoacetone reserves had been fully repurposed for industrial synthesis or neutralized, with no documented procurement for active service.^[14] Its absence from World War II arsenals underscores the shift toward persistent vesicants and nerve agents for warfare, while CN and later CS dominated non-lethal roles due to empirical data showing equivalent incapacitation with lower lethality thresholds in field tests.^[1] No revival occurred in subsequent conflicts, as bromoacetone's profile failed to meet evolving criteria for efficacy, safety, and treaty compliance.^[15]

Chemical Properties

Molecular structure and formula

Bromoacetone, with the systematic IUPAC name 1-bromopropan-2-one, possesses the molecular formula C₃H₅BrO and a molecular weight of 136.98 g/mol.^[1]^[16] Its structure consists of a three-carbon backbone featuring a ketone carbonyl group between carbons 1 and 3, with a methyl group (CH₃) attached to the carbonyl carbon and a bromomethyl group (CH₂Br) on the adjacent alpha carbon: CH₃C(O)CH₂Br.^[1]^[17] The bromine atom occupies the alpha position relative to the carbonyl, classifying bromoacetone as an α-haloketone, a structural motif shared with analogs such as chloroacetone (CH₃C(O)CH₂Cl), where chlorine substitutes for bromine.^[1]^[18] This positioning lacks a chiral center, precluding optical isomerism, though conformational variations arise from rotation about the C-C bonds adjacent to the carbonyl.^[18] The C-Br bond displays polarity arising from the electronegativity differential between carbon (2.55) and bromine (2.96 on the Pauling scale), enhancing the electrophilicity at the alpha carbon.^[1] Spectroscopic techniques confirm the functional groups: infrared (IR) spectroscopy reveals the characteristic C=O stretch of the ketone near 1710 cm⁻¹, while nuclear magnetic resonance (NMR) displays signals for the methyl protons around 2.2 ppm, methylene protons shifted downfield due to the adjacent bromine and carbonyl, and the carbonyl carbon in ¹³C NMR.^[1]

Physical characteristics

Bromoacetone exists as a clear, colorless to pale yellow liquid at room temperature, with a melting point of -37 °C and a boiling point ranging from 136 to 137 °C.^[19]^[20] Its density is 1.63 g/cm³ at standard conditions, rendering it denser than water.^[20] Upon standing, even in the absence of air, the liquid turns violet and may decompose further into a black resinous mass over extended periods.^[1]^[2] The compound exhibits poor solubility in water but is soluble in organic solvents such as acetone, ethanol, diethyl ether, and benzene.^[21]^[22] It possesses a pungent odor and a vapor pressure of 1.1 kPa at 20 °C, reflecting its volatile nature.^[23]^[20]

Stability and reactivity

Bromoacetone demonstrates inherent instability characteristic of α-halo ketones, decomposing upon standing to yield a black resinous mass via polymerization pathways, even in the absence of air.^[1] This process is accelerated by exposure to light, heat, or moisture, with the compound rapidly discoloring to violet and undergoing complete breakdown after several months at room temperature in the dark.^[5] Polymerization is a primary degradation mode, contrasting with the relative inertness of non-α-functionalized halogenated solvents, and underscores the electrophilic vulnerability of the α-carbon to self-reaction or environmental nucleophiles.^[23] Thermal decomposition or combustion releases hydrogen bromide and other toxic gases, reflecting cleavage of the C-Br bond under energy input.^[24] The compound's oxidative stability is low, as it reacts with strong oxidants, further highlighting the reactivity imparted by the conjugated carbonyl-halide system that facilitates electron withdrawal and bond labilization.^[24] Due to the electrophilicity of the α-brominated carbon, bromoacetone engages in vigorous nucleophilic substitution with species such as amines and thiols, proceeding via SN2 displacement of bromide to form alkylated products.^[25] This heightened reactivity stems from the carbonyl group's activation of the adjacent halide, enabling facile attack by nucleophilic centers in biological or synthetic contexts. Bromoacetone is also flammable, possessing a flash point of 51 °C, which necessitates cautious handling to avoid ignition under ambient conditions.^[1]^[3]

Synthesis

Laboratory preparation

Bromoacetone is prepared in the laboratory primarily through the acid-catalyzed α-bromination of acetone with molecular bromine. The reaction relies on the enolization of acetone in the presence of acid, followed by electrophilic bromination at the α-position.^[26] A standard procedure involves mixing acetone with glacial acetic acid, then adding bromine dropwise at a controlled temperature of 30–35°C to manage the exothermic nature of the halogenation and limit over-bromination to dibromoacetone. For example, 500 mL of acetone, 372 mL of glacial acetic acid, and 500 mL of water are stirred while 800 g of bromine is added over several hours, followed by distillation of the crude product under reduced pressure to yield colorless to pale yellow liquid. Reported yields for this method range from 50–51% of theoretical.^[6]^[27] An alternative approach uses bromine dissolved in acetone added to an aqueous solution of sodium bromate and sulfuric acid at 30–35°C, generating hypobromous acid in situ for bromination. This method also requires distillation for purification and emphasizes ventilation due to irritating vapors. The reaction's exothermicity necessitates cooling baths, and all manipulations should occur in a well-ventilated fume hood given the toxicity of reagents and product.^[28] Purity is verified post-distillation via techniques such as gas chromatography-mass spectrometry (GC-MS) or refractive index determination, aiming for >95% to ensure suitability for research applications.^[29]

Industrial-scale production

During World War I, Germany produced bromoacetone on an industrial scale for deployment as the lacrimatory agent B-Stoff, necessitating adaptations of laboratory bromination methods to handle large volumes amid wartime resource constraints.^[1] The core reaction remained the acid-catalyzed addition of bromine to acetone, conducted in continuous flow reactors to enhance throughput and safety by maintaining steady-state conditions and rapid mixing, which reduced hotspots prone to side reactions.^[30] Excess acetone (typically 5-10 equivalents) was employed to suppress polybromination, favoring selective monobromination at the alpha position while the hydrobromic acid byproduct was continuously neutralized with bases such as sodium bicarbonate to maintain pH and prevent equipment degradation.^[6] German processes incorporated electrolytic generation of bromine from hydrobromic acid in the presence of acetone, enabling in situ bromination without handling elemental bromine separately, which was advantageous given bromine shortages; this electrochemical approach yielded up to 90% under optimized conditions but faced persistent corrosion challenges from the acidic, halide-rich environment, requiring specialized lead-lined or graphite reactors.^[6] Post-purification involved distillation under reduced pressure to isolate the product, with overall process efficiency prioritized over purity for munitions filling. Contemporary industrial demand for bromoacetone is negligible, confined to trace laboratory or specialty chemical needs, where echoes of wartime continuous bromination persist but at microgram-to-gram scales using safer, enclosed flow systems to mitigate hazards; large-scale revival is precluded by superior alternatives for organic synthesis and stringent regulations on toxic haloketones.^[1]

Applications

Military and riot control uses

Bromoacetone served as a key lachrymatory agent in German chemical warfare during World War I, designated B-Stoff and incorporated into White Cross (Weißkreuz) mixtures alongside agents like bromobenzyl cyanide. Deployed primarily in artillery shells from mid-1916 onward, it functioned for area denial by inducing intense irritation to the eyes, nose, and throat, thereby forcing exposed troops to don gas masks or abandon positions. This non-lethal incapacitation approach minimized enemy fatalities while disrupting defensive lines, with its potency derived from rapid vaporization and dispersal effectiveness even in low concentrations within munitions payloads.^[9]^[31] Tactical limitations arose from bromoacetone's high volatility, which facilitated quick evaporation but also risked self-contamination of artillery crews through fumes during shell handling and firing, exacerbating operational hazards in windy or confined conditions. Battlefield applications in 1916 engagements demonstrated its capacity for widespread temporary disablement, though precise incapacitation metrics varied by environmental factors like temperature and wind direction, often resulting in inconsistent coverage and occasional blowback on German positions.^[32] Post-World War I, bromoacetone underwent limited evaluation for riot control applications due to its irritant properties, but its elevated toxicity profile—capable of causing pulmonary damage beyond mere sensory overload—rendered it unsuitable for non-combatant dispersal. By the 1930s, it was supplanted by less hazardous alternatives such as chloroacetophenone (CN), which provided comparable crowd-dispersing efficacy with reduced risk of severe injury.^[13]^[33]

Role in organic synthesis

Bromoacetone acts as a versatile α-haloketone in organic synthesis, primarily due to the electrophilic bromomethyl group that enables nucleophilic substitution, alkylation, and cyclization reactions. The bromide serves as an effective leaving group, offering greater selectivity in displacements compared to chloride analogs like chloroacetone, as bromine's intermediate polarizability reduces over-alkylation while supporting efficient enolate trapping and α-functionalization.^[34] This reactivity positions it as a reagent for constructing carbon-carbon and carbon-heteroatom bonds in complex molecules. In heterocyclic synthesis, bromoacetone condenses with thioureas or thioamides under Hantzsch conditions to form thiazoles, which are scaffolds in pharmaceuticals exhibiting antibacterial and anti-inflammatory properties.^[34] It also reacts with N-aryl- or N-alkylaminomethylenecyanoacetic acid derivatives in the presence of base to yield 3-aminopyrroles, useful intermediates for pyrrole-based agrochemicals and bioactive compounds.^[34] Additional applications include alkylation of nitroazoles to produce acetonyl derivatives, facilitating further nitration for energetic materials or heterocycle elaboration.^[35] Bromoacetone further supports ring-closing strategies, such as in the synthesis of indolizines by refluxing with ethyl 2-methylnicotinate in ethanol, yielding 8-ethoxycarbonyl-2-methylindolizine in 30% yield as a precursor for alkaloid analogs.^[36] Its role extends to formal [3+3] annulations via benzotriazolylpropan-2-one intermediates derived from bromoacetone, enabling access to substituted pyridines relevant to medicinal chemistry.^[37] These transformations underscore its utility in targeted syntheses where precise control over α-position reactivity is essential.

Minor and historical applications

Bromoacetone has been examined in historical agricultural trials as a potential fumigant component, including mixtures tested against grain weevils in stored products, with concentrations up to 1:2000 showing no immediate phytotoxic effects on plants during short exposures but ultimately abandoned due to its volatility, lachrymatory properties, and inhalation toxicity risks documented in mid-20th-century studies.^[38]^[9] In water treatment processes involving chlorination of bromide-rich sources, bromoacetone emerges as a minor haloacetone disinfection byproduct, with bromide enhancing its formation alongside other volatiles, as noted in analyses paralleling drinking water disinfection dynamics.^[39] Analytically, bromoacetone appears in standardized protocols like EPA Method 8260B for detecting volatile organic compounds in solid wastes via gas chromatography/mass spectrometry, serving as a reference analyte for halogenated ketones in environmental and waste matrices rather than a routine detection reagent for halides.^[1]^[40]

Toxicology and Health Effects

Mechanisms of toxicity

Bromoacetone functions as a potent alkylating agent due to its alpha-bromoketone structure, which enables nucleophilic substitution at the carbon bearing the bromine atom. This reactivity allows it to form covalent bonds with electron-rich sites in biomolecules, particularly sulfhydryl groups (-SH) on cysteine residues in proteins.^[1] Such alkylation disrupts protein structure and function, including in enzymes and structural proteins like mucins in ocular and respiratory epithelia, resulting in denaturation and impaired barrier integrity.^[41] This covalent modification is the primary biochemical basis for its irritant effects, as alpha-halo ketones like bromoacetone exhibit selective reactivity toward soft nucleophiles such as thiols over harder ones like water under physiological conditions.^[42] Inhalation of bromoacetone vapor leads to rapid interaction with moist mucosal surfaces, where the compound's electrophilicity drives alkylation before significant hydrolysis occurs. While hydrolysis can produce hydrogen bromide (HBr) and potentially alpha,beta-unsaturated ketones with irritant properties similar to acrolein, the dominant toxicity stems from direct protein modification rather than decomposition products alone.^[4] The potency is evidenced by sensory irritation thresholds as low as 0.1 ppm in humans and a 4-hour LC50 of 1,390 ppm (4,800 mg/m³) in rats, reflecting efficient local reactivity in peripheral tissues.^[1]^[9] This mechanism contrasts with nerve agents, which achieve systemic toxicity via irreversible inhibition of acetylcholinesterase through phosphorylation. Bromoacetone induces peripheral sensory disruption via localized alkylation-induced inflammation and nociceptor activation, without penetrating to cause central cholinergic overload or characteristic poisoning symptoms like convulsions.^[1] The absence of enzyme-specific targeting beyond thiol alkylation limits its effects to surface-level irritation, differentiating it from agents designed for deeper physiological interference.

Acute exposure symptoms

Acute exposure to bromoacetone vapor or liquid primarily manifests as severe irritation to the eyes, skin, and respiratory tract, with symptoms onset typically within minutes of contact. Ocular effects include intense lacrimation, blepharospasm, burning sensation, redness, and pain; irritation occurs in approximately 30% of human subjects at 0.1 ppm for 1 minute and in 100% at 1.0 ppm for the same duration, while corneal damage may result from concentrations exceeding 10 ppm.^[1]^[9] Skin contact with the liquid causes immediate painful burns, erythema, and vesication upon prolonged exposure, potentially leading to blistering and ulceration.^[4]^[2] Inhalation triggers upper respiratory irritation, including coughing, sore throat, chest tightness, nasal discharge, and labored breathing; low concentrations (e.g., 0.1 ppm for 1 minute) can induce discomfort and lacrimation, escalating to gasping, wheezing, and pulmonary edema at higher levels such as 28-131 ppm in animal models or wartime exposures around 100 ppm for several minutes.^[9]^[20] Thresholds for notable effects include a no-observed-adverse-effect level (NOAEL) of 1.0 ppm and lowest-observed-adverse-effect level (LOAEL) of 2.0 ppm in rats for mild respiratory responses like blinking.^[9] Historical accounts from World War I deployments as a lachrymator indicate most symptoms, such as irritation and respiratory distress, resolve within 1-2 hours following brief exposure without complications, though higher doses risked delayed pulmonary edema.^[9]^[43]

Chronic and long-term risks

Repeated or chronic inhalation of bromoacetone may lead to bronchitis, characterized by cough, phlegm production, and shortness of breath, based on extrapolations from its irritant properties and limited exposure data.^[20] Animal studies have demonstrated liver and kidney damage at high exposure levels, suggesting potential cumulative organ toxicity from prolonged low-level contact, though human data remain sparse.^[1] As an α-halo ketone, bromoacetone exhibits reactivity capable of alkylating DNA bases via SN2 mechanisms, akin to other α-halo carbonyl compounds that form adducts with nucleosides and demonstrate genotoxicity in bacterial assays.^[44] This structural feature implies possible mutagenic potential, though direct testing for bromoacetone is absent; predictive models based on reaction mechanisms classify most α-halo carbonyls as mutagenic due to their electrophilic nature.^[45] No carcinogenicity studies exist for bromoacetone in animals or humans, and it is not classified by the International Agency for Research on Cancer (IARC), reflecting data deficiencies rather than established safety.^[4] ^[1] Inferences from analogous α-halo ketones suggest elevated long-term cancer risks, but absence of cohort studies precludes definitive assessment; occupational exposure limits are unavailable due to its rarity and historical use.^[46]

Safety, Handling, and Environmental Impact

Occupational safety measures

Handling bromoacetone requires strict adherence to engineering controls, such as performing all manipulations in a chemical fume hood to minimize airborne exposure, supplemented by personal protective equipment including chemical-resistant gloves, protective clothing, safety goggles, and a full-face respirator with appropriate cartridges for organic vapors and acid gases.^[23] ^[19] Good laboratory hygiene practices, including washing hands thoroughly after handling and prohibiting eating, drinking, or smoking in the work area, further reduce risks.^[47] For storage, bromoacetone should be kept in tightly sealed containers in a cool, well-ventilated area away from heat sources, ignition points, strong oxidants, and incompatible materials to prevent decomposition or fire hazards.^[23] ^[24] Containers must be stored locked and separated from food or feedstuffs.^[20] In the event of a spill, immediately evacuate non-equipped personnel, ensure ventilation, and eliminate ignition sources before containing the liquid with inert absorbents like sand or vermiculite, transferring to sealed disposal containers for hazardous waste handling; residual areas should be flushed with water.^[4] Bromoacetone is classified by the U.S. Department of Transportation as UN 1569, a Poison Inhalation Hazard (Class 6.1 with subsidiary Class 3 flammability), requiring specialized packaging and labeling for transport.^[48] ^[4] No established occupational exposure limits exist, necessitating air monitoring in handling areas to detect vapors below perceptible irritation thresholds.^[4]

Environmental persistence and effects

Bromoacetone demonstrates low environmental persistence attributable to its high reactivity as an α-halo ketone. In the atmosphere, reaction with hydroxyl radicals yields an estimated half-life of 54 days at typical concentrations. In aqueous systems, photolysis represents a key degradation mechanism under sunlit conditions, while hydrolysis—facilitated by nucleophilic attack on the activated methylene carbon—occurs readily, particularly at alkaline pH, yielding hydroxyacetone as a primary product. This rapid transformation limits long-term accumulation in water bodies, though the compound sinks upon release and dissolves slowly before polymerizing to form violet residues.^[1]^[49] Despite its transience, bromoacetone exhibits acute toxicity to aquatic organisms at low concentrations, prompting warnings against entry into water intakes due to risks to fish and invertebrates. Specific metrics like LC50 values for fish remain unreported in standard databases, but its irritant and corrosive properties extend to ecosystems, potentially disrupting microbial communities and primary producers in spills. As a CERCLA-designated hazardous substance with a reportable quantity of 1,000 pounds, improper disposal can lead to groundwater contamination, where incomplete hydrolysis might allow transient migration before degradation.^[50]^[51] Bioaccumulation and biomagnification potentials are negligible, given the compound's volatility, rapid aqueous breakdown, and lack of lipophilicity conducive to trophic transfer. Short-term spill effects may involve localized oxygen demand from reactive byproducts or enhanced microbial respiration, but overall ecosystem recovery aligns with the substance's short half-lives in environmental compartments.^[1]

Regulatory and Legal Status

International treaties and prohibitions

The deployment of bromoacetone as a lacrimatory irritant during World War I, particularly by German forces under the designation B-Stoff, underscored the need for international restrictions on such agents, influencing the 1925 Geneva Protocol for the Prohibition of the Use in War of Asphyxiating, Poisonous or Other Gases, and of Bacteriological Methods of Warfare. This protocol, signed on 17 June 1925 and entering into force on 8 February 1928 for initial parties, explicitly bans the wartime employment of chemical agents like bromoacetone, categorizing them among prohibited gases without distinguishing irritants from lethal toxins at the time. Although the protocol permits reservations allowing retaliatory use and does not preclude riot control applications outside combat, it established a foundational norm against irritant deployment in armed conflict, addressing gaps in prior Hague Conventions of 1899 and 1907 that focused narrowly on gas-diffusing projectiles but omitted liquid or vaporized irritants. The 1993 Convention on the Prohibition of the Development, Production, Stockpiling and Use of Chemical Weapons and on Their Destruction (CWC), entering into force on 29 April 1997, builds on the Geneva framework by defining chemical weapons to encompass toxic chemicals and their precursors intended for hostile purposes or warfare methods, excluding purposes like industrial, agricultural, research, medical, or protective applications. Bromoacetone qualifies as a riot control agent under CWC Article II(9)(d), which permits non-lethal chemicals for temporary incapacitation in non-warfare scenarios such as law enforcement, provided they are not used as a method of warfare; however, it is not enumerated in the CWC's Schedules 1, 2, or 3 of controlled toxic chemicals or precursors, subjecting it to general verification rather than specific declaration requirements.^[52]^[53] The Organisation for the Prohibition of Chemical Weapons (OPCW), tasked with CWC implementation, monitors riot control agents through scientific advisory reports and inspection regimes, ensuring compliance with prohibitions on weaponization while allowing civilian formulations.^[54] Export controls under the Australia Group, an informal multilateral regime formed in 1985 to impede chemical weapons proliferation, harmonize licensing for dual-use chemicals and equipment that could facilitate production of agents like bromoacetone, though the compound itself evades direct listing as a precursor and relies on broader controls over alpha-halogenated ketones and synthesis apparatus. No comprehensive outright prohibition exists for bromoacetone in non-military contexts, but its historical irritant role sustains scrutiny under these regimes to prevent diversion to prohibited ends.^[55]^[56]

National regulations and hazardous substance listings

In the United States, bromoacetone is designated a hazardous substance under the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA), with a reportable quantity of 1,000 pounds (454 kg) for releases requiring notification to the National Response Center. It is regulated under the Toxic Substances Control Act (TSCA) for chemical inventory and risk management, including potential toxicity reporting requirements for manufacturers or importers. The Occupational Safety and Health Administration (OSHA) has not established a permissible exposure limit (PEL) for bromoacetone, though it must be handled under the Hazard Communication Standard (29 CFR 1910.1200) with appropriate labeling, safety data sheets, and worker training due to its irritant and toxic properties. For short-term exposure, guidelines align with irritant thresholds for similar alpha-halo ketones, such as ACGIH's ceiling limit recommendations for compounds like chloroacetone at 1 ppm, emphasizing immediate mitigation of airborne concentrations. The U.S. Department of Transportation (DOT) classifies bromoacetone as a Poison (Class 6.1), Packing Group II, under UN 1569, designating it a poison inhalation hazard requiring specific packaging, labeling, and placarding for transport. In the European Union, bromoacetone is subject to the REACH Regulation (EC) No 1907/2006, where alpha-halo ketones are evaluated for restrictions on uses posing unacceptable risks, particularly in consumer mixtures due to sensitization and acute toxicity; registration and authorization may be required for industrial volumes exceeding 1 tonne per year. It is classified under the Globally Harmonized System (GHS) and EU CLP Regulation as acutely toxic by inhalation (Category 2), causing serious eye damage (Category 1), and skin irritation (Category 2), mandating corrosive and toxic pictograms, signal words like "Danger," and hazard statements such as H330 ("Fatal if inhaled") on labels.^[57] Many other nations, including Canada, Australia, and Japan, adopt GHS classifications for bromoacetone, requiring similar corrosive and toxic labeling for import, storage, and handling.

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Mar 14, 2024 · PHYSICAL AND CHEMICAL PROPERTIES. Physical state (20°C):. Liquid. Form: Clear. Colour: Colorless - Pale yellow. Odour: Pungent. Melting point ...
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[PDF] BROMOACETONE - Safety Data Sheet - ChemicalBook
A violent lachrymator--low concentrations are very irritating to the eyes; high concentrations or prolonged exposure at lower concentrations may have adverse ...Missing: Sokolowsky | Show results with:Sokolowsky
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The Reactions of α-Bromo Ketones with Primary Amines1
The Reactions of α-Bromo Ketones with Primary Amines1 ... Addition/elimination reactions of an α‐tosyl substituted sulfine with nucleophilic reagents.
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Bromoacetone - chemeurope.com
Bromoacetone was first prepared in the 19th century. It was used in World War I as a chemical weapon, called BA by British and B-stoff (white cross) by ...Missing: history | Show results with:history
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Distilling bromoacetone question (w or w.o vacuum)
Sep 25, 2015 · Would it be possible to fractionally distill bromoacetones without applying vacuum, using only standard atmospheric pressure? I understand that ...
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Preparation of bromoacetone - PrepChem.com
Bromoacetone may be also obtained by the action of bromine dissolved in acetone on an aqueous solution of sodium bromate (NaBrO3) and sulfuric acid at 30-35° C.
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Kinetics of Bromination of Acetone, Bromoacetone, and 1,l ...
The rate of bromine consumption in acetone bromination is not dependent on bromine concentration, and the initial rate increases due to bromoacetone formation.
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α-Bromination of Aldehydes by Continuous Flow Chemistry and Its ...
Jul 28, 2025 · A continuous flow protocol for the α-bromination of aldehydes with bromine is reported, demonstrating significantly improved reaction efficiency ...Missing: bromoacetone | Show results with:bromoacetone
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Poison Gas — The Seven Most Feared Chemical Weapons of WWI
Aug 11, 2015 · • Made from essential oils produced from a species of Pacific Ocean seaweed, Bromoacetone, known as BA or B-Stoff, was an extremely potent tear ...Missing: deployment | Show results with:deployment
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Chemical weapon - WMD, Toxins, Agents - Britannica
Sep 12, 2025 · Arsenic-laced sneeze agents were also used, as were tear gases like ethyl bromoacetate, bromoacetone, and bromobenzyl cyanide. The horrific ...Missing: lethality | Show results with:lethality
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[PDF] MILITARY RESPIRATORY IRRITANTS. PART I. LACRIMATORS
Sep 4, 2015 · In WWI, ethyl bromoacetate was used as a lachrymatory agent and a tear gas agent for chemical warfare under the German code Weisskreuz. (White ...
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The Chemistry of α-Haloketones and Their Utility in Heterocyclic ...
α-Bromoketones react with bromoacetic acid in the presence of a catalytic amount of triethylamine to give the substitution products 216, which, via the ...
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haloketones by13C,15N, and14N NMR - ResearchGate
Aug 9, 2025 · General methods have been worked out for the alkylation of nitroazoles with bromoacetone, bromoacetophenone, and diazoacetone in homogeneous ...<|control11|><|separator|>
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[PDF] •l/V - Russian Chemical Reviews
In the synthesis of 8-ethoxycarbonyl-2-methylindolizine (in 30% yield) ethyl 2-methylnicotinate and bromoacetone were used; the conversion of the resulting ...<|separator|>
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Formal carbo [3+3] annulation and its application in organic synthesis
Mar 18, 2015 · In this procedure, 1-(benzotriazol-1-yl)propan-2-one 5 was first prepared from bromoacetone with benzaltriazol, and then it was subjected to ...
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[PDF] Fumigation against grain weevils with various volatile organic ...
Guerin and Lormand (7) found that bromoacetone had no apparent effect on plants at a concentration of 1 to 2,000 exposed for an hour. Bertrand and ...
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Natural Formation of Chloro- and Bromoacetone in Salt Lakes of ...
... bromoacetone and 1 ... Deep rooted native vegetation, mainly eucalyptus species, was replaced with pastures and winter growing annual crops.
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[PDF] Method 8260B: Volatile Organic Compounds by Gas ... - US EPA
Method 8260B determines volatile organic compounds in solid waste matrices using GC/MS, applicable to various samples regardless of water content.
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Effects of alkylating agents of human plasma cholinesterase
Less reactive alkylating compounds such as bromoacetone, chloroacetate, and iodoacetate did not inhibit the enzyme. ... These findings suggest that a sulfhydryl ...
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Mechanism of the Reaction of α-Haloketones with Weakley Basic ...
Computational study on the reaction pathway of α-bromoacetophenones with hydroxide ion: possible path bifurcation in the addition/substitution mechanism.
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https://mmsl.cz/pdfs/mms/2016/02/01.pdf
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α-halo carbonyl compounds adduct with DNA by SN2 reaction
Most of the α-halo carbonyl (AHC) compounds tend to be predicted as mutagenic by structure-activity relationship based on structural category only, ...Missing: ketones | Show results with:ketones
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A reaction mechanism-based prediction of mutagenicity: α-halo ...
Most of the α-halo carbonyl (AHC) compounds tend to be predicted as mutagenic by structure-activity relationship based on structural category only, ...
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2 Bromoacetone | Acute Exposure Guideline Levels for Selected ...
The threshold for lethality was set at LC01 (lethal concentration, 1% lethality). The LC01 was chosen over the BMCL05 (benchmark concentration, 95% lower ...
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[PDF] SAFETY DATA SHEET - Chem Service
Jan 13, 2015 · Prolonged skin contact may cause temporary irritation. Skin corrosion/irritation. 4 / 8. Material name: Bromoacetone. N-11332 Version #: 03 ...Missing: Sokolowsky | Show results with:Sokolowsky
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UN/NA 1569 - CAMEO Chemicals - NOAA
CAMEO Chemicals has 1 chemical datasheet with response recommendations for this UN/NA number. ... Bromoacetone. ERG book cover. Response Guide 131. Guía de ...
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Kinetics of Bromination of Acetone, Bromoacetone, and 1,1 ...
Aug 6, 2025 · The reaction between acetone and methanol to form acetone dimethylacetal attains equilibrium quickly under the influence of copper(II) bromide.
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[PDF] BROMOACETONE - CAMEO Chemicals
Bromoacetone is flammable, emits toxic fumes, and is a poison. It is irritating to eyes, nose, throat, and skin, and is a marine pollutant. Avoid contact.
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[PDF] Consolidated List of Chemicals Subject to the Emergency Planning ...
May 8, 2024 · CERCLA hazardous substances, and their reportable quantities, are listed in 40 CFR ... Bromoacetone. 598-31-2. 1,000. P017.
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Chemical Weapons Convention | OPCW
The Convention aims to eliminate an entire category of weapons of mass destruction by prohibiting the development, production, acquisition, stockpiling, ...Download the Convention · Articles · Article I – General Obligations · Article IV
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[PDF] U.S. Chemical Weapons and Related Materiel Reference Guide
Jan 31, 2022 · ... Geneva Protocol, signed by the United States (though not ratified by Senate) and 28 other countries, condemned the use of gas and ...
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[PDF] SAB-25/WP.1 - Organisation for the Prohibition of Chemical Weapons
Mar 27, 2017 · The Himsworth report [3] into toxicological aspects of CS. (one of the most common chemicals to be used as a tear gas) and its use for civil.
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The Australia Group
The Australia Group is an informal forum of countries which, through the harmonisation of export controls, seeks to ensure that exports do not contribute to ...Participants · Introduction · Objectives of the Group · Common Control Lists
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[PDF] CATEGORY 1 - SPECIAL MATERIALS AND RELATED EQUIPMENT ...
Dec 8, 2023 · Category 1 includes special materials, equipment, chemicals, microorganisms, and toxins. FDA and DEA may also control exports of these items.
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Substances restricted under REACH - ECHA - European Union
The list of substances restricted under REACH will be available in our new chemicals database, ECHA CHEM, since 16 September 2025.Navigation · Nickel and its compounds · Details · Liste over begrænsninger