Patent Application
20090162495
The present invention relates to derivatives of certain aromachemicals
There are a large number of aromachemicals that are used to modify the flavor and/or fragrance of food and drink products and/or to modify the fragrance of products such as consumer products. Some aromachemicals are highly reactive and may potentially be dangerous to the health of people working in environments in which these products are used. It is an object of the present invention to provide derivatives of a harmful compound which is far less likely to be a danger to health but which can also be used to provide flavors and fragrances.
One flavor that is very popular with consumers is butter flavor. Butter-flavored foods are highly desirable and widely consumed. For example, in recent years butter-flavored microwavable popcorn has become extremely popular.
A number of additives have been developed over the years that impart a butter flavor to food products. For example, Commercial Creamery Co. has developed a new butter flavor comprising an enzyme modified butter powder. Also on the market as a butter substitute is Acetyl Methyl Carbinol (Acetoin).
The most popular butter flavor additive employed today, however, is diacetyl [2,3-butanedione] which has the formula:
Diacetyl [sometimes marketed as “Starter Distillates”] has a FTV of flavor threshold of 0.10 mg/L. Carbonyl compounds make a particularly significant contribution to the flavor of fermented dairy products. Diacetyl is one of the most important carbonyls to the flavors of these products. It has a buttery, nut-like flavor. Diacetyl may be produced via the fermentation of citrate-containing material bacterial culture containing alpha-acetolactic acid, acidifying the bacterial culture which is then water vapor distilled in the presence of oxygen for oxidation of alpha-acetolactic acid to diacetyl. [Source book of Flavors, Reineccius, G, Ed. 1994 Chapman and Hall, New York].
Butter-flavored foods are highly desirable and widely consumed. For example, in recent years butter-flavored microwavable popcorn has become extremely popular. It is widely recognized within the art of producing and using butter flavors that diacetyl and butyric acid are key flavor components easily lost via evaporation (Merker, U.S. Pat. No. 2,773,772; Buhler, U.S. Pat. No. 3,653,921; Millisor, U.S. Pat. No. 4,384,008; Bakal, U.S. Pat. No. 4,414,229; and Darragh, U.S. Pat. No. 3,867,556). Buhler, U.S. Pat. No. 3,653,921, for example, notes the prior art has suggested the incorporation of selected lactones, diacetyl, constituents of cultured butter, short-chain fatty acids and alcohols and other chemical compounds into oleaginous foodstuffs to impart a butter flavor. Millisor, U.S. Pat. No. 4,384,008, discloses a specific formulation made from diacetyl, several short-chain fatty acids and lactones for preparing a butter flavored oil.
Diacetyl (2,3 butanedione) is an extremely powerful and highly volatile (b.p. 88C) odorant. The National Institute for Occupational Safety and Health (NIOSH), a federal workplace safety agency, believes that diacetyl may be the component of butter flavoring responsible for more than a dozen cases of a respiratory illness called “popcorn workers' lung” it has discovered in the past four years [Niosh Health Hazard Evaluation Report, HETA-2002-0408-2915 (October, 2003).
Diacetyl is a reactive molecule, attacks arginine residues in proteins and is known to inhibit enzymes. NIOSH describes the adverse effects of diacetyl: Potential symptoms: Eye, mucous membrane, respiratory system, skin irritation; persistent cough, phlegm production, wheezing, dyspnea (shortness of breath); unusual fatigue; episodes of mild fever or generalized aches; severe skin rashes. Health Effects: Irritation-Eyes, Nose, Throat, Skin (HE15); Suspected cumulative lung damage—bronchiolitis obliterans (HE10) Affected organs: Eyes, respiratory system, skin.
Other authors have also pointed out the dangers of exposure to diacetyl: DiFolco, Forum Casualty & Environment, Issue no. 14-Dec., 2004; Fix, BrewingTechniques' July/August 1993 [“—the involvement of diacetyl in sarcina sickness was discovered early, but it was not until 1939 that Shimwell linked this compound with the taste and smell of butter—”]; Kreiss, K., Gomaa, A., Kullman, G., Fedan, K., Simoes, E. J. and Enright, P. L.: Clinical bronchiolitis obliterans in workers at a microwave-popcorn plant. New Eng. J. Med. 347(5): 330-338, 2002; Lockey, J., McKay, R, Barth, E., Dahlsten, J. and Baughman, R.: Bronchiolitis obliterans in the food flavoring industry [abstract]. Am. J. Respir. Crit. Care Med. 165: A461, 2002; Parmet, A. J. and Von Essen, S.: Rapidly progressive, fixed airway obstructive disease in popcorn workers: a new occupational pulmonary illness? [Letter] J. Occup. Environ. Med. 44(3): 216-218, 2002; Hubbs, A. F., Battelli, L., Goldsmith, W. T., Porter, D. W., Frazer, D., Friend, S., Schwegler-Berry, D., Mercer, R. R., Reynolds, J. S., Grote, A., Castranova, V., Kullman, G., Fedan, J. S., Dowdy, J. and Jones, W. G.: Necrosis of nasal and airway epithelium in rats inhaling vapors of artificial butter flavoring. Toxicol. Appl. Pharmacol. 185: 128-135, 2002. Boggaram, V. and Mannervik, B.: Essential arginine residues in the pyridine nucleotide binding sites of glutathione reductase. Biochim. Biophys. Acta 701(1): 119-126, 1982; Borders, C. L. Jr., Saunders, J. E., Blech, D. M. and Frovich, I.: Essentiality of the active-site arginine residue for the normal catalytic activity of Cu. Zn superoxide dismutase. Biochem. J. 230(3): 771-776, 1985. Riordan, J. F.: Arginyl residues and anion binding sites in proteins. Mol. Cell. Biochem. 26(2): 71-92, 1979.
Other di-carbonyl compounds are also used as aromachemicals, e.g., 1,2-cyclohexanedione, 3,4-dimethyl-1,2-cyclopentaneadione, 3,5-dimethyl-1,2-cyclopentanedione, 2,3-heptanedione, 2,3-hexanedione, 3,4-hexanedione, 1-methyl-2,3-cyclohexanedione, 3-methylcyclopentane-1,2-dione, 5-methyl-2,3-hexanedione.
It is an object of the present invention to provide substitutes for these di-carbonyl compounds that imparts the same flavors and odors to food products as the compounds per se without any attendant disadvantages.
The above and other objects are realized by the present invention, one embodiment of which relates to an improved method for imparting a flavor to a product, the method comprising adding to said product an organoleptically effective amount of a di-carbonyl compound, wherein the improvement comprises substituting for the di-carbonyl compound, an organoleptically acceptable derivative thereof having the formula:
wherein m=0, 1 or 2, n=1 or 2, R1 and R2 are, independently, linear or branched saturated C1-4 alkyl, with the proviso that both of R1 and R2 may not be methyl, and X is a counterion of the sulfiting agent employed to synthesize the derivative. Typically, R1 and R2 are methyl (with the above proviso), ethyl, propyl (e.g. n- or i-propyl) or butyl (e.g. n-, i- or t-butyl). Preferably, X is H, an alkali metal or an ammonium salt. Most preferably, X is Na or K.
A still further embodiment of the invention concerns a product comprising an effective amount of the above additive to impart aromachemical properties thereto.
Another embodiment of the invention relates to an article of manufacture comprising the above-described product.
A still further object of the invention relates to an article of manufacture in kit form comprising separate packaging materials and a product contained within one of the packaging materials, and an additive described above contained within the other of the packaging materials.
An additional embodiment of the invention relates to a composition in unit dosage form comprising a derivative described above and an acceptable carrier therefore, wherein the derivative is present in said composition in an amount sufficient to impart aromachemical properties to a product to which the composition is added.
Diacetyl is known to form an adduct with sodium hydrogen sulfite [2-butanesulfonic acid, 2-hydroxy-3-oxo-, monosodium salt—CAS 13489-36-6]. See also French patent 2,845,903. This adduct is in equilibrium with the starting materials and, in practice, releases small amounts of diacetyl and sulfite continuously. The above-mentioned French patent discloses that the adduct is useful in hair care products as a straightening agent. The vapor pressure of the diacetyl adduct is negligible, thereby resulting in little or no odor. It is usually obtained and used in the form of a water-soluble salt, such as, e.g., an alkali metal (sodium) salt. Since it is water soluble, it can therefore be sprayed directly onto foodstuffs safely. The flavor imparted by the adduct is dominated by diacetyl, since at low concentrations, the sulfite taste and flavor is imperceptible.
Methods for the preparation of the adduct are well known. Briefly, diacetyl is. dissolved in water and an equimolar amount of sodium hydrogen sulfite (i.e., bisulfite) is added gradually over a period of 20 minutes. The color of the reaction mixture turns from yellow to white. At completion of the reaction, the water is evaporated and the adduct is obtained as a crystalline white powder with virtually no odor.
Suitable sulfite or sulfite generating species for use in this reaction include water-soluble sulfites, bisulfites, hydrosulfites, metabisulfites and sulfur dioxide. For example, ammonium or alkali metal, particularly sodium or potassium sulfites, bisulfites, hydrosulfites and metabisulfites. Particularly preferred are sodium metabisulfite, sodium sulfite, sodium bisulfite and sodium hydrosulfite, potassium sulfite, potassium bisulfite, potassium hydrosulfite and potassium metabisulfite, ammonium sulfite and ammonium bisulfite and sulfur dioxide. Sulfites and metabisulfites of alkaline earth metals such as calcium and barium may also be used. Sulfites and sulfite generating species which produce sodium salts are preferred.
The reaction can be summarized as follows:
This adduct is in equilibrium with the starting materials and, in practice, releases small amounts of diacetyl and sulfite continuously. These same methods are also applicable for the formation of sulfite adducts of other diones such as, e.g., 1,2-cyclohexanedione, 3,4-dimethyl-1,2-cyclopentaneadione, 3,5-dimethyl-1,2-cyclopentanedione, 2,3-heptanedione, 2,3-hexanedione, 3,4-hexanedione, 1-methyl-2,3-cyclohexanedione, 3-methylcyclopentane-1,2-dione, 5-methyl-2,3-hexanedione. These aromachemicals are illustrated below.
The preferred compounds of the invention are the sulfite adduct salts of these compounds (referred hereinafter as the “sulfite adducts”). The vapor pressures of the adducts are negligible, thereby resulting in little or no odor. They are usually obtained and used in the form of a water-soluble salt, such as, e.g., an alkali metal (sodium) salt. Since they are water soluble, they can therefore be sprayed directly onto foodstuffs safely. Thus, the adducts act as proflavorants or profragrances.
The term “aromachemcial” refers to a compound which has fragrance and/or flavor characteristics. For example, 3,4-dimethyl-1,2-cyclopentanedione has a sweet maple caramel sugar, fenugreek, licorice smell and flavor; 3,5-dimethyl-1,2-cyclopentadione has a brown, sweet, sugary, maple caramellic smell and flavor; 2,3-heptanedione has a buttery, cheesy, sweet, nutty, fruity, creamy, caramel smell and flavor; 3-methylcyclopentane-1,2-dione has a caramellic-maple smell and flavor; 5-methyl-2,3-hexanedione has a buttery, cheesy, sweet, nutty, fruity smell and flavor.
It will be understood by those skilled in the art that the adduct (or its salts) may be incorporated into any product or article manufactured therefrom much in the same manner and in the amounts employed in the industry for incorporating the di-carbonyl compound therein. Moreover, any product or article which may be enhanced by incorporating di-carbonyls therein may be also be treated with the adducts of the invention.
For the purposes of the description of the invention herein, the following definitions apply:
The term, “aromachemical”, as used herein refers to a chemical compound that has fragrance and/or flavor characteristics.
The term “organoleptic”, as used herein, refers to compounds of the invention which stimulate the sense of smell or taste, and are thus perceived as having a characteristic odor and/or flavor.
An “organoleptically effective amount” of a compound of the invention is an amount of a compound which when broken down to provide the aromachemical on which it is based exhibit(s) a sensory effect acceptable to a consumer, e.g. by stimulating the sense of smell or taste.
The term, “organoleptically acceptable” (for example when used in relation to the counterion (X) and the sulfiting agent described herein) refers to materials compatible with the derivatives of the invention and which do not affect the organoleptic properties of the latter.
“Unit dosage form” refers to a composition containing a predetermined amount of a compound of the invention in a form for application to a product.
“Organoleptically acceptable carrier” refers to the material employed for delivery of a compound of the invention to the desired substrate, e.g., water or other solvent in which the derivative is soluble or may be suitably suspended.
The terms “pro-odorant” and “pro-flavorant” refer to compounds which themselves have substantially no odor or flavor but degrade over time and/or under certain conditions to provide the odorant or flavorant molecule on which they are based and thus provide the odor or flavor of that parent molecule.
The term “food product” includes any product suitable for ingestion, be it food and/or drink or one or more components of food and/or drink.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/US06/26828 | 7/12/2006 | WO | 00 | 7/17/2008 |
| Number | Date | Country | |
|---|---|---|---|
| 60698013 | Jul 2005 | US |
