1-Bromopropane
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| Names | |
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| Preferred IUPAC name
1-Bromopropane[1] | |
Other names
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| Identifiers | |
3D model (JSmol)
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| Abbreviations | n-PB[citation needed] |
| 505936 | |
| ChEBI | |
| ChEMBL | |
| ChemSpider | |
| ECHA InfoCard | 100.003.133 |
| EC Number |
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| MeSH | 1-bromopropane |
PubChem CID
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| RTECS number |
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| UNII | |
| UN number | 2344 |
CompTox Dashboard (EPA)
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| Properties | |
| C3H7Br | |
| Molar mass | 122.993 g·mol−1 |
| Appearance | Colorless liquid |
| Density | 1.354 g mL−1 |
| Melting point | −110.5 °C; −166.8 °F; 162.7 K |
| Boiling point | 70.3 to 71.3 °C; 158.4 to 160.2 °F; 343.4 to 344.4 K |
| 2.5 g L−1 (at 20 °C) | |
| Solubility in ethanol | Miscible |
| Solubility in diethyl ether | Miscible |
| log P | 2.319 |
| Vapor pressure | 19.5 kPa (at 20 °C) |
Henry's law
constant (kH) |
1.4 μmol Pa−1 kg−1 |
Refractive index (nD)
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1.43414 |
| Viscosity | 5.241 mPa s (at 20 °C) |
| Thermochemistry | |
Heat capacity (C)
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134.6 J K−1 mol−1 |
Std enthalpy of
formation (ΔfH⦵298) |
−125.8 to −123.0 kJ mol−1 |
Std enthalpy of
combustion (ΔcH⦵298) |
−2.0580 to −2.0552 MJ mol−1 |
| Hazards | |
| GHS labelling: | |
  
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| Danger | |
| H225, H315, H319, H335, H336, H360, H373 | |
| P201, P210, P261, P305+P351+P338, P308+P313 | |
| NFPA 704 (fire diamond) | |
| Flash point | 22 °C (72 °F; 295 K) |
| 490 °C (914 °F; 763 K) | |
| Explosive limits | 4.6–?% |
| Lethal dose or concentration (LD, LC): | |
LD50 (median dose)
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2.950 mg kg−1 (intraperitoneal, rat) |
| Related compounds | |
Related alkanes
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Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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1-Bromopropane (n-propylbromide or nPB) is a bromoalkane with the chemical formula CH3CH2CH2Br. It is a colorless liquid that is used as a solvent. It has a characteristic hydrocarbon odor. Its industrial applications increased dramatically in the 21st century due to the phasing out of chlorofluorocarbons and chloroalkanes such as 1,1,1-trichloroethane under the Montreal Protocol.
Preparation
[edit]Industrial routes to 1-bromopropane involve free-radical additions to the corresponding alkenes. In this way, the anti-Markovnikov product is obtained.[2] Alternatively, n‑propanol may be substitutively brominated.[3] The latter reaction is also viable laboratory synthesis.
One laboratory technique for substitutive bromination treats propanol with a mixture of hydrobromic and sulfuric acids:
- CH3CH2CH2OH + HBr → CH3CH2CH2Br + H2O
Alternate synthetic routes include treating propanol with phosphorus tribromide[4] or via a Hunsdiecker reaction with butyric acid.[5]
Applications
[edit]Like many other liquid halocarbons, 1-bromopropane finds use as a liquid or gaseous solvent. It is a solvent for adhesives in aerosol glues that glue foam cushions together.[6] It is a solvent in asphalt production, in the aviation industry for maintenance, and in synthetic fiber production.[7] It is a solvent for degreasing plastics, optics and on metal surfaces, to remove soldering residues from electronic circuit boards.[8] It is an aggressive solvent with a Kauri-butanol value of 129 which is similar to 1,1,1-trichloroethane.[9]
Its increasing use in the 21st century resulted from the need for a substitute for chlorofluorocarbons and perchloroethylene as a dry cleaning solvent,[10] however its use in dry cleaning has been steadily declining and by 2020, its use for dry cleaning is nearly obsolete[11] while perchloroethylene remained the most common solvent in dry cleaning as of 2024.
Regulation
[edit]In the European Union, 1-bromopropane has been classified as reproductive toxicant per Registration, Evaluation, Authorisation and Restriction of Chemicals, which makes it a "substance of very high concern".[12]
As of January 5, 2022, 1-bromopropane has been added to the United States Clean Air Act list of Hazardous Air Pollutants (HAP).[13]
Since 2007, it has been approved for use under the U.S. EPA's Significant New Alternatives Policy (SNAP) as a suitable replacement for ozone depleting chemicals.[14] In 2013, the U.S. EPA announced that, based on a work plan developed under the Toxic Substances Control Act of 1976, it would begin a full risk assessment of 1-Bromopropane.[15] In December 2022, the U.S. EPA released a revised risk determination from the August 2020 risk evaluation, used to form a proposed risk management rule in July 2024.[16][17]
The North Carolina Department of Labor's Occupational Safety and Health Division issued a Hazard Alert in 6/2014, as it "is not regulated to protect workers, consumers or the environment".[18]
Safety
[edit]In 2003, the American Conference of Governmental Industrial Hygienists (ACGIH) set the time-weighted average threshold limit value for an 8-hour exposure at 10 parts per million (ppm). In 2014, the ACGIH adopted a lower threshold limit value of 0.1 ppm as an 8-hour time-weighted average. The California Occupational Safety and Health Administration set the permissible exposure limit at 5 ppm in 2010. Though symptoms of overexposure can begin within 2 days of exposure, typically long-term exposure is more harmful.[8]
In 2008, the U.S. CDC recommended that use of 1-bromopropane as a replacement for perchloroethylene may require adjustment and modification of equipment, improved ventilation, and use of personal protective equipment.[10]
In 2013, a peer-review panel convened by the U.S. National Toxicology Program unanimously recommended that 1-bromopropane, be classified as reasonably anticipated human carcinogens.[19]
Extended occupational exposure to 1-bromopropane in higher concentrations than recommended has resulted in significant injury to workers in the United States.[20] Its use as a solvent in aerosol glues used to glue foam cushions has been especially controversial.[6] Reported symptoms of overexposure affect the nervous system and include confusion, slurred speech, dizziness, paresthesias, and difficulty walking, unusual fatigue and headaches, development of arthralgias, visual disturbances (difficulty focusing), and muscle twitching. Symptoms may persist over one year.[10] Other symptoms include irritation of mucous membranes, eyes, upper respiratory tract, and skin, as well as transient loss of consciousness.[8] Loss of feeling in the feet, an example of paresthesia, is colloquially called "dead foot" by workers who suffer from it.[6] Of nationwide "more than 140 cushion workers nationwide, mostly from plants in Utah, Mississippi and North Carolina,[...] that had been exposed to dangerous levels of the chemical, many of them sickened and [are] unable to walk".[6] One worker's long-term exposure resulting in neurological damage was covered in the NY Times.[6] Air sampling for the level of 1-bromopropane and monitoring workers' urine for metabolites are both effective at measuring workers' exposure.[8]
Occupational exposure to 1-bromopropane typically occurs through breathing or skin contact; it is easily absorbed into the blood via the skin. Replacing 1-bromopropane with water or acetone-based adhesives is the preferred NIOSH option for controlling occupational exposure, but other options include engineering controls like isolation and ventilation, administrative controls, and PPE that includes respiratory and skin protection.[8] 1-Bromopropane can penetrate most gloves, but not those made of polyvinyl alcohol or laminates.[7]
Animal studies
[edit]Animal studies of 1-bromopropane have showed that it is a carcinogen in those models.[8] Rodents exposed to 1-bromopropane developed lung, colon, and skin cancer at higher rates.[7]
Environmental impact
[edit]Stratospheric ozone layer damage
[edit]Although 1-bromopropane is naturally produced,[citation needed] it is one of the very short-lived substances that depletes ozone. Because 1-bromopropane is so short-lived, its ozone depletion potential (ODP) is dependent on the latitude where it is released.[21][22] According to the United States Environmental Protection Agency, the ODP is 0.013-0.018 in U.S. latitudes and 0.071-0.100 in tropical latitudes.[21]
References
[edit]- ^ "1-bromopropane - Compound Summary". PubChem Compound. USA: National Center for Biotechnology Information. 27 March 2005. Identification. Retrieved 15 June 2012.
- ^ David Ioffe, Arieh Kampf "Bromine, Organic Compounds" in Kirk-Othmer Encyclopedia of Chemical Technology 2002 by John Wiley & Sons. doi:10.1002/0471238961.0218151325150606.a01.
- ^ Hensel, A. (2018). "Propanal". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. p. 5. doi:10.1002/14356007.a22_157.pub3. ISBN 978-3527306732.
- ^ Oliver Kamm and C. S. Marvel (1941). "Alkyl and alkylene bromides" (PDF). Organic Syntheses; Collected Volumes, vol. 1, p. 25.
- ^ Adams, Rodger (1957). Organic Reactions Volume IX. New York: John Wiley and Sons, Inc. p. 356. ISBN 9780471007265. Retrieved 3 September 2014.
- ^ a b c d e Ian Urbina (March 30, 2013). "As OSHA Emphasizes Safety, Long-Term Health Risks Fester". The New York Times. Retrieved March 31, 2013.
- ^ a b c "Hazard Alert: 1-Bromopropane" (PDF). DHHS (NIOSH) Publication Number 2013-150. National Institute for Occupational Safety and Health. July 2013. Retrieved 17 January 2015.
- ^ a b c d e f Trout, Doug; Hudson, Naomi; Dotson, Scott; Hanley, Kevin (1 August 2013). "1-Bromopropane". National Institute for Occupational Safety and Health. Retrieved 16 January 2015.
- ^ Kanegsberg, Barbara; Kanegsberg, Edward (2000-12-26). Handbook for Critical Cleaning. CRC Press. ISBN 978-1-4200-3982-5.
- ^ a b c "Neurologic Illness Associated with Occupational Exposure to the Solvent 1-Bromopropane --- New Jersey and Pennsylvania, 2007--2008". Centers for Disease Control. December 5, 2008. Retrieved March 31, 2013.
- ^ Smith, Carr J; Perfetti, Thomas A; Morford, Richard G (2020-01-01). "Use of 1-bromopropane (N-propyl bromide) in dry cleaning is rare and rapidly declining toward obsolescence". Toxicology Research and Application. 4: 2397847320966961. doi:10.1177/2397847320966961. ISSN 2397-8473. S2CID 228978817.
- ^ "AGREEMENT OF THE MEMBER STATE COMMITTEE ON THE IDENTIFICATION OF 1-BROMOPROPANE [n-PROPYL BROMIDE] AS A SUBSTANCE OF VERY HIGH CONCERN According to Articles 57 and 59 of Regulation (EC) 1907/20061" (PDF). European Union. 29 November 2012. Retrieved 6 August 2014.
- ^ 87 FR 396, https://www.govinfo.gov/content/pkg/FR-2022-01-05/pdf/2021-28315.pdf
- ^ "Protection of Stratospheric Ozone: Listing of Substitutes for Ozone- Depleting Substances-n-Propyl Bromide in Solvent Cleaning" (PDF). Federal Register. U.S. Environmental Protection Agency. May 30, 2007. Retrieved March 31, 2013.
This final rule lists n-propyl bromide (nPB) as an acceptable substitute when used as a solvent in industrial equipment for metals cleaning, electronics cleaning, or precision cleaning. General metals, precision, and electronics cleaning includes cleaning with industrial cleaning equipment such as vapor degreasers, in-line cleaning systems, or automated equipment used for cleaning below the boiling point.
- ^ United States Environmental Protection Agency. "List of Chemicals for Assessment". Archived from the original on 2013-10-18. Retrieved 23 April 2013.
- ^ United States Environmental Protection Agency. "Risk Evaluation for 1-Bromopropane (1-BP)". Archived from the original on 2024-07-09. Retrieved 28 August 2024.
- ^ United States Environmental Protection Agency. "Risk Management for 1-Bromopropane (1-BP)". Archived from the original on 2024-08-15. Retrieved 28 August 2024.
- ^ North Carolina Department of Labor (June 2014). "Hazard Alert" (PDF). State of North Carolina. Retrieved 6 August 2014.
- ^ "Report on Carcinogens Monograph on 1-Bromopropane" (PDF). National Toxicology Program. 21 March 2013. Retrieved 6 August 2014.
- ^ "1-BROMOPROPANE: Human Health Effects". Hazardous Substances Data Bank. Retrieved March 31, 2013.
- ^ a b "Q and A 2007 Final and Proposed Regulations for n Propyl Bromide (nPB)" (PDF). US EPA. 2007.
- ^ Wuebbles, Donald J.; Patten, Kenneth O.; Johnson, Matthew T.; Kotamarthi, Rao (2001-07-01). "New methodology for Ozone Depletion Potentials of short-lived compounds: n-Propyl bromide as an example". Journal of Geophysical Research. 106 (D13): 14. Bibcode:2001JGR...10614551W. doi:10.1029/2001JD900008. ISSN 0148-0227.