Diacetyl

Diacetyl[1]
IUPAC name 2,3-Butanedione
Other names Diacetyl Biacetyl Dimethyl diketone 2,3-Diketobutane
Identifiers
CAS number	431-03-8 Y
PubChem	650
ChemSpider	630 Y
UNII	K324J5K4HM Y
KEGG	C00741 Y
ChEBI	CHEBI:16583 Y
ChEMBL	CHEMBL365809 Y
Jmol-3D images	Image 1
SMILES O=C(C(=O)C)C
InChI InChI=1S/C4H6O2/c1-3(5)4(2)6/h1-2H3 Y Key: QSJXEFYPDANLFS-UHFFFAOYSA-N Y InChI=1/C4H6O2/c1-3(5)4(2)6/h1-2H3 Key: QSJXEFYPDANLFS-UHFFFAOYAX
Properties
Molecular formula	C4H6O2
Molar mass	86.0892 g/mol
Appearance	Yellowish green liquid
Density	0.990 g/mL at 15 °C
Melting point	-2 to -4 °C
Boiling point	88 °C
Solubility in water	Soluble in 4 parts
Hazards
MSDS	External MSDS
R-phrases	R10 R22 R36 R37 R38
S-phrases	S9 S16 S33
Main hazards	Harmful, flammable
Y (verify) (what is: Y/N?) Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Diacetyl (IUPAC systematic name: butanedione or 2,3-butanedione) is a natural byproduct of fermentation. It is a vicinal diketone (two C=O groups, side-by-side) with the molecular formula C₄H₆O₂. Diacetyl occurs naturally in alcoholic beverages and is added to some foods to impart a buttery flavor.

In food products

Diacetyl and acetoin are two compounds that give butter its characteristic taste. Because of this, manufacturers of margarines or similar oil-based products typically add diacetyl and acetoin (along with beta carotene for the yellow color) to make the final product butter-flavored, because it would otherwise be relatively tasteless.^[2]

In alcoholic beverages

At low levels, diacetyl contributes a slipperiness to the feel of the alcoholic beverage in the mouth. As levels increase, it imparts a buttery or butterscotch flavor (butterscotch itself may have no diacetyl in it at all).

In some styles of beer (e.g. in most beers produced in the British Isles, such as English Pale ales) the presence of diacetyl can be acceptable or desirable at low or, in some cases, moderate levels. In other styles the presence of diacetyl is considered a flaw or undesirable.^[3]

Diacetyl is produced during fermentation as a by-product of valine synthesis, when yeast produces α-acetolactate, which escapes the cell and is spontaneously decarboxylated into diacetyl. The yeast then absorbs the diacetyl, and reduces the ketone groups to form acetoin and 2,3-butanediol, relatively flavorless compounds.

Beer sometimes undergoes a diacetyl rest, in which its temperature is raised slightly for two or three days after fermentation is complete, to allow the yeast to absorb the diacetyl it produced earlier in the fermentation cycle. The makers of some wines, such as Chardonnay, deliberately promote the production of diacetyl because of the feel and flavor it imparts. It is present in many California chardonnays known as "Butter Bombs," although there is a growing trend back toward the more traditional French styles.^{[citation needed]}

Concentrations from 0.005 mg/L to 1.7 mg/L were measured in chardonnay wines, and the amount needed for the flavor to be noticed is at least 0.2 mg/L.^[4][5]

In milk products

In milk, sour cream, cultured buttermilk or fermented butter are produced by inoculating pasteurized cream or milk with a lactic starter culture, churning (agitating) and holding the milk until a desired pH drop (or increase in acidity) is attained. This cultured sour cream, butter and buttermilk which are made by fermenting pasteurized and homogenised light cream or milk owes its tart flavour to lactic acid bacteria and its buttery aroma and taste to diacetyl.^[6]

Mosquito repellant

Hexanol^{[disambiguation needed ]} and 2,3-butanedione are strong inhibitors of the CO₂-sensitive neurons in the fruit fly. CO₂ emitted in human breath is the main attractant for the Culex mosquito to find people.^[7]

Safety

Worker safety

The United States National Institute for Occupational Safety and Health has suggested that diacetyl, when used in artificial butter flavoring (as used in many consumer foods), may be hazardous when heated and inhaled over a long period.

Workers in several factories that manufacture artificial butter flavoring have been diagnosed with bronchiolitis obliterans, a rare and serious disease of the lungs. The cases found have been mainly in young, healthy, non-smoking males. There are no known cures for bronchiolitis obliterans except for lung transplantation.

While several authorities have called the disease "Popcorn Worker's Lung," a more accurate term suggested by other doctors may be more appropriate, since the disease can occur in any industry working with diacetyl: diacetyl-induced bronchiolitis obliterans.

After the workers filed a lawsuit against the manufacturers, the United States Environmental Protection Agency began an investigation into the chemical properties of microwave popcorn butter flavoring. In March 2004, former microwave popcorn plant employee Eric Peoples, of Joplin, Missouri, was awarded $20 million for permanent lung-injuries sustained while on the job.^[8] On July 19, 2005, jurors awarded $2.7 million to another popcorn plant worker in Missouri for his claim of diacetyl-induced respiratory problems.^[9]

On July 26, 2006, the International Brotherhood of Teamsters and the United Food and Commercial Workers petitioned the U.S. Occupational Safety and Health Administration to promulgate an emergency temporary standard to protect workers from the deleterious health effects of inhaling diacetyl vapors.^[10] The petition was followed by a letter of support signed by more than thirty prominent scientists.^[11] The matter is under consideration. On 21 January 2009, OSHA issued an advance notice of proposed rulemaking for regulating exposure to diacetyl.^[12] The notice requests respondents to provide input regarding adverse health effects, methods to evaluate and monitor exposure, the training of workers. That notice also solicited input regarding exposure and health effects of acetoin, acetaldehyde, acetic acid and furfural.^[13]

There are currently two bills in the California Legislature to ban the use of diacetyl.^[14][15][16]

A 2010 OSHA Safety and Health Information Bulletin and companion Worker Alert recommend that employers use safety measures to avoid exposing employees to the potentially deadly effects of butter flavorings and other flavoring substances containing diacetyl or its substitutes.^[17]

Consumer safety

Dr. Cecile Rose, pulmonary specialist at Denver's National Jewish Medical and Research Center, in a letter, warned federal agencies or regulators that consumers, not just factory workers, are in danger of contracting bronchiolitis obliterans from fumes produced by microwaving popcorn containing diacetyl. David Michaels of the George Washington University School of Public Health first published Rose's letter on his blog.^[18] However, the only sample data known-to-date is the case where a consumer, who ate at least two bags of buttery microwave popcorn daily for 10 years, became diagnosed with the same disease affecting workers exposed to the substance, bronchiolitis obliterans.^[19] His lung problems were linked to breathing the vapors; although rare, the reported man's kitchen also had diacetyl levels comparable to those in popcorn plants.^[19]

The Flavor and Extract Manufacturers Association recommended reducing diacetyl in butter flavorings (24 September 2007). The Pop Weaver brand popcorn from the Weaver Popcorn Company of Indianapolis was the first to replace its butter flavoring with a new ingredient.^[20] Weaver makes also the Trail's End brand of popcorn, currently sold by the Boy Scouts of America and Scouts Canada. In a press release dated December 17, 2007, ConAgra Foods, maker of Orville Redenbacher's and Act II microwave popcorn brands, announced it had removed added diacetyl from all of its butter-flavored microwave popcorn varieties. The new products began hitting store shelves as early as October 2007.^[21]

European Union regulation

The European Commission has declared that diacetyl is legal for use as a flavouring substance in all EU states.^[22] As a diketone, diacetyl is included in the EU's flavouring classification Flavouring Group Evaluation 11 (FGE.11). A Scientific Panel of the EU Commission evaluated six flavouring substances (not including diacetyl) from FGE.11 in 2004.^[23] As part of this study, the Panel reviewed available studies on several other flavourings in FEG.11, including diacetyl. Based on the available data, the Panel reiterated the finding that there were no safety concerns for diacetyl's use as a flavouring. As a result of the Panel's 2004 study, acetylacetone (FL 07.191) was found to be genotoxic in vitro and in vivo, and was therefore deleted from the register of permitted flavouring substances.^[24] Recently, the European Food Safety Authority (EFSA), the EU's food safety regulatory body, stated that its scientific panel on food additives and flavourings (AFC) was evaluating diacetyl along with other flavourings as part of a larger study. "The experts of the EFSA AFC panel and its working group on food additives will look at this issue to see if new scientific evidence is available that may require further actions. If the experts conclude that consumer exposure to diacetyl can reach levels well above those considered as safe and, that a possible health risk for consumers cannot be excluded when inhaling diacetyl, EFSA will give priority to the re-evaluation of this substance and provide detailed scientific advice."^[25]

See also

• Bronchiolitis obliterans

References

1. ^ Merck Index, 11th Edition, 2946.
2. ^ Pavia et al., Introduction to Organic Laboratory Techniques, 4th ed., ISBN 978-0-495-28069-9
3. ^ Beer Judge Certification Program style guidelines http://www.bjcp.org/stylecenter.php
4. ^ Nielsen JC, Richelieu M (February 1999). "Control of flavor development in wine during and after malolactic fermentation by Oenococcus oeni". Appl. Environ. Microbiol. 65 (2): 740–5. PMC 91089. PMID 9925610. http://aem.asm.org/cgi/pmidlookup?view=long&pmid=9925610. 
5. ^ Martineau B, Henick-Kling T, Acree T (1995). "Reassessment of the Influence of Malolactic Fermentation on the Concentration of Diacetyl in Wines". Am Soc Enol Vitic 46 (3): 385–8. http://ajevonline.org/cgi/content/abstract/46/3/385. 
6. ^ Modern food microbiology, sixth edition, James M.Jay, page 120, starter cultures, products
7. ^ Discovery Of Natural Odors Could Help Develop Mosquito Repellents
8. ^ CBS News: Jury Gives Popcorn Worker $20M: Missouri Man Says Butter Flavor Vapor Ruined His Lungs
9. ^ International Flavors and Fragrances SEC Annual Report Form 10K: Item 1: Legal Proceedings. Filed August 5, 2005.
10. ^ UFCW and Teamsters Petition to OSHA
11. ^ Scientists Letter to Secretary Chao
12. ^ Federal Register, 21 January 2009 issue
13. ^ "OSHA begins rule on diacetyl". Chemical & Engineering News 87 (4): 24. January 26, 2009. http://pubs.acs.org/isubscribe/journals/cen/87/i04/html/8704govc4.html. 
14. ^ Flavoring-Factory Illnesses Raise Inquiries, New York Times, May 6, 2007
15. ^ SB 456 Senate Bill - Bill Analysis
16. ^ AB 514 Assembly Bill - Bill Analysis
17. ^ OSHA Recommends Safety Measures to Protect Workers from Diacetyl Exposure, EHS Today, December 10, 2010
18. ^ David Michaels. Popcorn Lung Coming to Your Kitchen? The FDA Doesn’t Want to Know
19. ^ ^{a b} Reuters New Report: FDA to probe popcorn link in man's lung disease.
20. ^ Weaver Popcorn Company. Press Release: Pop Weaver introduces first microwave popcorn with flavoring containing no diacetyl.
21. ^ ConAgra Foods Press Release ConAgra Foods press release announcing removal of added diacetyl
22. ^ http://www.fsai.ie/legislation/food/eu_docs/Flavourings/Dir99.217.pdf
23. ^ http://www.efsa.europa.eu/EFSA/Scientific_Opinion/afc_opinionflav_ej166_en1.pdf
24. ^ http://eur-lex.europa.eu/LexUriServ/site/en/oj/2005/l_128/l_12820050521en00730076.pdf
25. ^ Europe takes 'wait-and-see' stance on diacetyl flavouring

External links

• Research project on diacetyl reduction during beer fermentation
• Toxicology data
• NIOSH Alert: Preventing Lung Disease and Workers who Use or Make Flavorings
• Harber P, Saechao K, Boomus C (2006). "Diacetyl-induced lung disease". Toxicol Rev 25 (4): 261–72. doi:10.2165/00139709-200625040-00006. PMID 17288497. 
• A Case of Regulatory Failure - Popcorn Workers Lung, from www.defendingscience.org.
• Scientists Urge Secretary of Labor to Protect Workers from Diacetyl, a press release from defendingscience.org. Links to studies on the health effects of diacetyl, and to a variety of related documents including the recent OSHA petition and the scientists' letter of support may be found here.
• Flavoring suspected in illness, Washington Post, May 7, 2007.
• NIOSH International Safety Card for 2,3-butanedione
• National Institute for Occupational Safety and Health - Flavorings-Related Lung Disease
• IFIC - Diacetyl