Butylated hydroxytoluene
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Butylated hydroxytoluene (BHT), also known as dibutylhydroxytoluene, is a lipophilic organic compound, chemically a derivative of phenol, that is useful for its antioxidant properties.<ref>Template:Cite journal</ref> BHT is widely used to prevent free radical-mediated oxidation in fluids (e.g. fuels, oils) and other materials, and the regulations overseen by the U.S. F.D.A.—which considers BHT to be "generally recognized as safe"—allow small amounts to be added to foods. Despite this, and the earlier determination by the National Cancer Institute that BHT was noncarcinogenic in an animal model, societal concerns over its broad use have been expressed.
Natural occurrenceEdit
Phytoplankton, including the green algae Botryococcus braunii, as well as three different cyanobacteria (Cylindrospermopsis raciborskii, Microcystis aeruginosa and Oscillatoria sp.) are capable of producing BHT as a natural product.<ref name="BHTalgae">Template:Cite journal</ref> The fruit lychee also produces BHT in its pericarp.<ref>Template:Cite journal</ref>
Several fungi (for example Aspergillus conicus) living in olives produce BHT. Volatile organic compounds such as BHT and odor chemicals are produced by resident fungi when olives are being stored awaiting pressing.<ref>Template:Cite journal</ref>
It has been detected in higher plants and herbivorous insects, but it is not clear whether the BHT is produced by the plant, the insect, or some other organism living in association.<ref>Template:Cite journal</ref>
ProductionEdit
Industrial productionEdit
The chemical synthesis of BHT in industry has involved the reaction of p-cresol (4-methylphenol) with isobutylene (2-methylpropene), catalyzed by sulfuric acid: <ref name=Ullmann>Helmut Fiege, Heinz-Werner Voges, Toshikazu Hamamoto, Sumio Umemura, Tadao Iwata, Hisaya Miki, Yasuhiro Fujita, Hans-Josef Buysch, Dorothea Garbe, Wilfried Paulus "Phenol Derivatives" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2002. {{#invoke:doi|main}} Article Online Posting Date: June 15, 2000.</ref>
- CH3(C6H4)OH + 2 CH2=C(CH3)2 → ((CH3)3C)2CH3C6H2OH
Alternatively, BHT has been prepared from 2,6-di-tert-butylphenol by hydroxymethylation or aminomethylation followed by hydrogenolysis.Template:Citation needed
ReactionsEdit
The species behaves as a synthetic analog of vitamin E, primarily acting as a terminating agent that suppresses autoxidation, a process whereby unsaturated (usually) organic compounds are attacked by atmospheric oxygen. BHT stops this autocatalytic reaction by converting peroxy radicals to hydroperoxides. It effects this function by donating a hydrogen atom:
- RO2• + ArOH → ROOH + ArO•
- RO2• + ArO• → nonradical products
where R is alkyl or aryl, and where ArOH is BHT or related phenolic antioxidants. Each BHT consumes two peroxy radicals.<ref>Template:Cite journal</ref><ref>Template:Cite journal</ref> The electron-donating alkyl groups on the ortho and para positions of BHT increase the electron density of the phenolic hydroxyl moiety through the inductive effect and the hyperconjugation effect,<ref name=":1">Template:Cite book</ref> reduce the bond dissociation energy of the phenolic hydroxyl group, and enhance its reactivity to lipid free radicals. Meanwhile, the phenoxy radical generated by BHT is stabilized due to the delocalization of unpaired electrons around the aromatic ring<ref name=":1" /><ref>Template:Cite journal</ref> and the steric hindrance effect of ortho tert-butyl groups.<ref>Template:Cite journal</ref><ref>Template:Cite journal</ref> Isobutene is one of the possible degradation products formed by BHT oxidation with computational studies suggesting that there are two possible mechanism that can lead to isobutene formation with the OH addition pathways at the C2 site of BHT more likely to result in isobutene formation than pathways of H abstracts from the t-butyl group.<ref>Template:Cite journal</ref>
ApplicationsEdit
BHT is listed by the NIH Hazardous Substances Data Bank under several categories in catalogues and databases, such as food additive, household product ingredient, industrial additive, personal care product/cosmetic ingredient, pesticide ingredient, plastic/rubber ingredient and medical/veterinary/research.<ref>US Dept of Health & Human Services. Household Products Database. [1] Template:Webarchive.US EPA. InertFinder. [2]. US National Library of Medicine. Haz-Map. [3] Template:Webarchive. US National Library of Medicine. Hazardous Substances Data Bank. [4].</ref>
Food additiveEdit
BHT is primarily used as an antioxidant food additive.<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref> In the United States, it is classified as generally recognized as safe (GRAS) based on a National Cancer Institute study from 1979 in rats and mice.<ref name=NTP>Bioassay of Butylated Hydroxytoluene (BHT) for Possible Carcinogenicity, National Cancer Institute, CARCINOGENESIS Technical Report Series No. 150, 1979, 128 pp National Institutes of HealthTemplate:Page needed</ref><ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref> It is approved for use in the U.S. by the Food and Drug Administration: For example, 21 CFR § 137.350(a)(4) allows BHT up to 0.0033% by weight in "enriched rice",<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref> while 9 CFR § 381.147](f)(1) allows up to 0.01% in poultry "by fat content".<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref> It is permitted in the European Union under E321.<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref>
BHT is used as a preservative ingredient in some foods. With this usage BHT maintains freshness or prevents spoilage; it may be used to decrease the rate at which the texture, color, or flavor of food changes.<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref>
Some food companies have voluntarily eliminated BHT from their products or have announced that they were going to phase it out.<ref name=atl>Template:Cite journal</ref>
AntioxidantEdit
BHT is also used as an antioxidant in products such as metalworking fluids, cosmetics, pharmaceuticals, rubber, transformer oils, and embalming fluid.<ref name=":0">Template:Cite journal</ref><ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref> In the petroleum industry, where BHT is known as the fuel additive AO-29 (Innospec), it is used in hydraulic fluids, turbine and gear oils, and jet fuels.<ref name=":0" /><ref>Template:Cite book</ref> BHT is also used to prevent peroxide formation in organic ethers and other solvents and laboratory chemicals.<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref> It is added to certain monomers as a polymerisation inhibitor to facilitate their safe storage.<ref>Template:Cite journal</ref> Some additive products contain BHT as their primary ingredient, while others contain the chemical merely as a component of their formulation, sometimes alongside butylated hydroxyanisole (BHA).<ref name="sciam13">Template:Cite news</ref>
CosmeticsEdit
The European Union restricts the use of BHT in mouthwash to 0.001% concentration, in toothpaste to 0.01% concentration, and to 0.8% in other cosmetics.<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref>
Health effectsEdit
Like many closely related phenol antioxidants, BHT has low acute toxicity<ref name=GESTIS/> (e.g., the desmethyl analog of BHT, 2,6-di-tert-butylphenol, has an Template:LD50 of >9 g/kg<ref name=Ullmann />). The US Food and Drug Administration classifies BHT as generally recognized as safe (GRAS) food preservative when used in an approved manner.<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref><ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref> In 1979, the National Cancer Institute determined that BHT was noncarcinogenic in a mouse model.<ref name=NTP />
The World Health Organization discussed a possible link between BHT and cancer risk in a 1986 report concluding there is limited evidence for carcinogenicity from animal studies.<ref name="WHOReport1986">Template:Cite reportTemplate:Page needed</ref> Primary research studies in the 1970s–1990s reported both potential for increased risk and potential for decreased risk in the area of oncology.<ref name=":2">Template:Cite journal</ref> A review report published in 2002 noted that BHT has shown anticarcinogenic effects, no effect, or tumor promoting effects depending on animal species and target organ considered.<ref name=":2" /> Because of this uncertainty, the Center for Science in the Public Interest puts BHT in its "caution" column and recommends avoiding it.<ref name="ucb">{{#invoke:citation/CS1|citation |CitationClass=web }}</ref>