4-Bromoaniline

log Kow = 2.26

2.26

2.0

1.497 at 212 °F (NTP, 1992) - Denser than water; will sink

1.4970 at 99.6 °C/4 °C

Relative density (water = 1): 1.5 (100 °C)

Bipyramidal rhombic crystals, needles from 60% alcohol

Colorless crystals

less than 1 mg/mL at 73 °F (NTP, 1992)

Very soluble in alcohol and ether; insoluble in cold water

Solubility in water: poor

Decomposes (NTP, 1992)

219.7 °C

BP: decomposes

223 °C

151.5 °F (NTP, 1992)

66-66.5 °C

66 °C

5.9 (Air = 1)

Relative vapor density (air = 1): 5.9

0.04 [mmHg]

Vapor pressure, Pa at 25 °C: 22.6

P-bromoaniline is a brown solid with a sweet odor. (NTP, 1992)

Colorless solid; [Hawley] Brown solid; [CAMEO] White or brown powder; [MSDSonline]

COLOURLESS CRYSTALS.

Danger

H302 (100%): Harmful if swallowed [Warning Acute toxicity, oral]

P260, P261, P262, P264, P264+P265, P270, P271, P280, P301+P317, P302+P352, P304+P340, P305+P351+P338, P316, P317, P319, P321, P330, P332+P317, P337+P317, P361+P364, P362+P364, P403+P233, P405, and P501 (click each P-code to see the statement)

Aggregated GHS information provided per 53 reports by companies from 12 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.

Chemical: Benzenamine, 4-bromo-

4-Bromoaniline: Does not have an individual approval but may be used under an appropriate group standard

Flash point data are not available for this chemical, but it is probably combustible. (NTP, 1992)

Combustible. Gives off irritating or toxic fumes (or gases) in a fire.

SYMPTOMS: Symptoms of exposure to this compound may include cyanosis (blue-black lips and tongue; gray skin) due to methemoglobinemia, headache, nausea and vomiting, dry throat, confusion, dizziness, tinnitus, weakness, irritability, drowsiness, coma, seizures, hypotension, fainting, joint pains, hemolytic anemia, jaundice, hepatic and renal damage, and bloody urine.

Causes flaccid paralysis, cyanosis, and weight loss in high-dose feeding studies of rats; [RTECS] Emergency treatment: Methemoglobinemia; [HSDB] Can induce methemoglobinemia; [ICSC] An irritant; May induce methemoglobinemia; [MSDSonline] See 4-Chloroaniline.

Pursuant to section 8(d) of TSCA, EPA promulgated a model Health and Safety Data Reporting Rule. The section 8(d) model rule requires manufacturers, importers, and processors of listed chemical substances and mixtures to submit to EPA copies and lists of unpublished health and safety studies. 4-Bromoaniline is included on this list. Effective date: 10/4/82; Sunset date: 10/4/92.

Fires involving this compound should be controlled using a dry chemical, carbon dioxide or Halon extinguisher. (NTP, 1992)

Use water spray, powder, foam, carbon dioxide.

Fresh air, rest. Refer for medical attention.

Rinse and then wash skin with water and soap.

First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention.

Rinse mouth. Refer for medical attention .

EYES: First check the victim for contact lenses and remove if present. Flush victim's eyes with water or normal saline solution for 20 to 30 minutes while simultaneously calling a hospital or poison control center. Do not put any ointments, oils, or medication in the victim's eyes without specific instructions from a physician. IMMEDIATELY transport the victim after flushing eyes to a hospital even if no symptoms (such as redness or irritation) develop.

Special protective equipment for firefighters Wear self contained breathing apparatus for fire fighting if necessary.

Use water spray, powder, foam, carbon dioxide.

Precautions for safe handling: Avoid contact with skin and eyes. Avoid formation of dust and aerosols. Provide appropriate exhaust ventilation at places where dust is formed. Normal measures for preventive fire protection. Conditions for safe storage Keep container tightly closed in a dry and well-ventilated place. Light sensitive. Store under inert gas. Air sensitive.

Separated from strong oxidants and acids. Well closed.

Sweep spilled substance into covered containers. If appropriate, moisten first to prevent dusting. Carefully collect remainder. Then store and dispose of according to local regulations. Personal protection: particulate filter respirator adapted to the airborne concentration of the substance. Do NOT let this chemical enter the environment.

Removal of chloroaniline from wastewater by electrochemical treatment is discussed. /4-Chloroaniline/

Cover with the 9:1 mixture of sand and soda ash. After mixing, transfer into a paper carton, stuffed with ruffled paper. Burn in an open furnace with the utmost care or in the furnace with after burner and scrubber. /4-Chloroaniline/

SMALL SPILLS AND LEAKAGE: Should a spill occur while you are handling this chemical, FIRST REMOVE ALL SOURCES OF IGNITION, then you should dampen the solid spill material with 60-70% ethanol and transfer the dampened material to a suitable container. Use absorbent paper dampened with 60-70% ethanol to pick up any remaining material. Seal the absorbent paper, and any of your clothes, which may be contaminated, in a vapor-tight plastic bag for eventual disposal. Solvent wash all contaminated surfaces with 60-70% ethanol followed by washing with a soap and water solution. Do not reenter the contaminated area until the Safety Officer (or other responsible person) has verified that the area has been properly cleaned.

SRP: The most favorable course of action is to use an alternative chemical product with less inherent propensity for occupational harm/injury/toxicity or environmental contamination. Recycle any unused portion of the material for its approved use or return it to the manufacturer or supplier. Ultimate disposal of the chemical must consider: the material's impact on air quality; potential migration in soil or water; effects on animal and plant life; and conformance with environmental and public health regulations.

A good candidate for rotary kiln incineration at a temperature range of 820 to 1,600 °C and residence times of seconds for liquids and gases, and hours for solids. /4-Chloroaniline/

Sweep spilled substance into covered containers. If appropriate, moisten first to prevent dusting. Carefully collect remainder. Then store and dispose of according to local regulations. Personal protection: particulate filter respirator adapted to the airborne concentration of the substance. Do NOT let this chemical enter the environment.

SRP: Local exhaust ventilation should be applied wherever there is an incidence of point source emissions or dispersion of regulated contaminants in the work area. Ventilation control of the contaminant as close to its point of generation is both the most economical and safest method to minimize personnel exposure to airborne contaminants. Ensure that the local ventilation moves the contaminant away from the worker.

Avoid contact with skin, eyes and clothing. Wash hands before breaks and immediately after handling the product.

Do not eat, drink, or smoke during work.

TERRESTRIAL FATE: Based on a classification scheme(1), measured Koc values of 91(2) and 218(3) indicate that 4-bromoaniline is expected to have high to moderate mobility in soil(SRC). The pKa of 4-bromoaniline is 3.86(4), indicating that this compound is a weak base and will exist predominantly in the non-ionized form in the environment. However, anilines are expected to bind strongly to humus or organic matter in soils due to the high reactivity of the aromatic amino group(5,6), suggesting that mobility may be much lower in some soils(SRC). 4-Bromoaniline absorbs at wavelengths >290 nm(7) and, therefore, may be susceptible to direct photolysis on soil surfaces exposed to sunlight(SRC). 4-Bromoaniline has been shown to be biodegradable in acclimated soil and water(8,9), but biodegradation may be very slow in unacclimated soil(8). Volatilization of 4-bromoaniline from moist soil surfaces may have some importance(SRC) given an estimated Henry's Law constant of 9.1X10-7 atm-cu m/mole(SRC), using a fragment constant estimation method(10).

AQUATIC FATE: Based on a classification scheme(1), measured Koc values of 91(2) and 218(3) indicate that 4-bromoaniline is not expected to adsorb to suspended solids and sediment(SRC). The pKa of 4-bromoaniline is 3.86(4), indicating that this compound is a weak base and will exist predominantly in the non-ionized form in the environment. Anilines may bind strongly to humus or organic matter due to the high reactivity of the aromatic amino group(5,6), suggesting some adsorption to suspended solids and sediment may occur(SRC). Volatilization from water surfaces is expected(7) based upon an estimated Henry's Law constant of 9.1X10-7 atm-cu m/mole(SRC), developed using a fragment constant estimation method(8). Using this Henry's Law constant and an estimation method(7), volatilization half-lives for a model river and model lake are 53 and 389 days, respectively(SRC). According to a classification scheme(9), an estimated BCF of 14(SRC), from its log Kow of 2.26(10) and a regression-derived equation(8), suggests the potential for bioconcentration in aquatic organisms is low(SRC). 4-Bromoaniline absorbs at wavelengths >290 nm(11) and, therefore, may be susceptible to direct photolysis(SRC). Aromatic amines are susceptible to photosensitized degradation in natural waters exposed to sunlight due to reaction with OH and RO2 radicals(12); therefore, indirect photolysis may have some environmental importance in natural water(SRC). 4-Bromoaniline is not expected to undergo hydrolysis in the environment due to the lack of functional groups that hydrolyze under environmental conditions(7). In biodegradation studies using Elbe River water and a testfilter methodology, 4-bromoaniline had a mean degradation rate of 0.67/hr (half-life of about 1 hour; half-life in control samples was 99 hrs)(13). In anaerobic biodegradation tests using an estuarine sediment from the Tsurumi River in Japan, 4-bromoaniline had an observed degradation rate of 0.00557/day which corresponded to a half-life of 124.4 days(14).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), 4-bromoaniline, which has an estimated vapor pressure of 0.05 mm Hg at 25 °C(SRC), determined from a fragment constant method(2), is expected to exist primarily as a vapor in the ambient atmosphere. However, monitoring data have detected 4-bromoaniline in ambient atmospheric particulate material at relatively high concentrations of 109 ng/cu m(3). Vapor-phase 4-bromoaniline is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals(SRC); the half-life for this reaction in air is estimated to be 12 hours(SRC), calculated from its rate constant of 3.1X10-11 cu cm/molecule-sec at 25 °C(SRC) that was derived using a structure estimation method(2). Particulate-phase 4-bromoaniline may be removed from the air by wet and dry deposition(SRC). 4-Bromoaniline absorbs at wavelengths >290 nm(4) and, therefore, may be susceptible to direct photolysis by sunlight(SRC).

Blue lips, fingernails and skin. Headache. Nausea.

Blue lips, fingernails and skin. Dizziness. Headache. Laboured breathing. Nausea. Confusion. Convulsions. Unconsciousness.

The following link will take the user to the National Toxicology Program (NTP) Test Agent Search Results page, which tabulates all of the "Standard Toxicology & Carcinogenesis Studies", "Developmental Studies", and "Genetic Toxicity Studies" performed with this chemical. Clicking on the "Testing Status" link will take the user to the status (i.e., in review, in progress, in preparation, on test, completed, etc.) and results of all the studies that the NTP has done on this chemical.[Available from, as of July 17, 2013: http://ntp-apps.niehs.nih.gov/ntp_tox/index.cfm?fuseaction=ntpsearch.searchresults&searchterm=106-40-1]

Soil adsorption studies using four silt loam soils and a 2-hour adsorption period determined a mean log Kom (K organic matter) of 1.72 (which corresponds to a log Koc of 1.96 and Koc of 91 for 4-bromoaniline(1). A Koc of 217.9 was determined in sorption studies using a calcareous Spanish soil(2); manual addition of dissolved organic carbon (from peat or tannic acid) was found to increase 4-bromoanline adsorption on soil(2). According to a classification scheme(3), these Koc values suggests that 4-bromoaniline is expected to have moderate to high mobility in soil. The pKa of 4-bromoaniline is 3.86(4), indicating that this compound is a weak base and will exist predominantly in the non-ionized form in the environment. However, anilines are expected to bind strongly to humus or organic matter in soils due to the high reactivity of the aromatic amino group(5,6), suggesting that mobility may be much lower in some soils(SRC).

4-Bromoaniline's production and use as an intermediate in the production of azo dyes, dihydroquinazolines, metobromuron and resorantel(1,2) may result in its release to the environment through various waste streams(SRC). 4-Bromoaniline was qualitatively detected in stack effluents generated by hazardous waste incineration(3). It may also be released to the environment as a product of the microbial breakdown of the herbicide metobromuron in soil(4). 4-Bromoaniline has been detected in tobacco grown in soil treated with metobromuron(5).

AEROBIC: Soil enrichment cultures extracted from soils that had been treated with herbicides (such as linuron and metobromuron) over multiple years were able to readily degrade the herbicides and their degradation products (4-bromoaniline was the degradation product from metobromuron)(1); untreated control soil samples from the same location did not show any degradation activity(1). In biodegradation studies using Elbe River water and a testfilter methodology, 4-bromoaniline had a mean degradation rate of 0.67/hr (half-life of about 1 hour)(2); degradation rate in control samples was only 0.007/hr (half-life of 99 hours)(2).

ANAEROBIC: In anaerobic biodegradation tests using an estuarine sediment from the Tsurumi River in Japan, 4-bromoaniline had an observed degradation rate of 0.00557/day which corresponded to a half-life of 124.4 days(1).

PURE CULTURE: Purified enzymes of the soil fungus Geotrichum candidum biotransformed p-bromoaniline to 4,4'- dibromoazobenzene(1). A strain of Moraxella sp used p-bromoaniline as a sole source of carbon and nitrogen(2).

Pursuant to section 8(d) of TSCA, EPA promulgated a model Health and Safety Data Reporting Rule. The section 8(d) model rule requires manufacturers, importers, and processors of listed chemical substances and mixtures to submit to EPA copies and lists of unpublished health and safety studies. 4-Bromoaniline is included on this list. Effective date: 10/4/82; Sunset date: 10/4/92.

p-Bromoaniline metabolized to p-aminophenol in rabbits. From table/

p-Bromoaniline metabolized to p-bromoacetanilide in micro-organisms. From table/

p-Bromoaniline metabolized to p-bromoaniline-n-glucoside in beans. From table/

The metabolic fate of 4-bromoaniline (4-BrA) was investigated following intraperitoneal administration to the rat at 50 mg kg(-1), using high-performance liquid chromatography/time-of-flight tandem mass spectrometry (HPLC/TOF-MS/MS). Up to five metabolites were detected in urine that correspond to isomeric pentose conjugates (possibly ribosides) of a hydroxysulfate of 4-BrA. This identification is supported by further studies where the water used in the reversed-phase solvent system was replaced with deuterated water in order to confirm that the number of exchangeable protons present in the metabolites was consistent with the proposed structures.

The urinary excretion of 4-bromoaniline and its (carbonyl-(13)C)-labelled N-acetanilide, together with their corresponding metabolites, have been investigated in the rat following i.p. administration at 50 mg kg(-1). Metabolite profiling was performed by reversed-phase HPLC with UV detection, whilst identification was performed using a combination of enzymic hydrolysis and directly coupled HPLC-NMR-MS analysis. The urinary metabolite profile was quantitatively and qualitatively similar for both compounds with little of either excreted unchanged. The major metabolite present in urine was 2-amino-5-bromophenylsulphate, but, in addition, a number of metabolites with modification of the N-acetyl moiety were identified (from both the ((13)C)-acetanilide or produced following acetylation of the free bromoaniline). For 4-bromoacetanilide, N-deacetylation was a major route of metabolism, but despite the detection of the acetanilide following the administration of the free aniline, there was no evidence of reacetylation (futile deacetylation). Metabolites resulting from the oxidation of the acetyl group included a novel glucuronide of an N-glycolanilide, an unusual N-oxanilic acid and a novel N-acetyl cysteine conjugate.

Used in the preparation of azo dyes and dihydroquinazolines (condensed with formaldehyde); [Merck Index]

In preparation of azo dyes; condensed with formaldehyde in preparation of dihydroquinazolines

Intermediate in the production of metobromuron (a pesticide) and resorantel (a medicinal anthelmintic)