The present invention relates to 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone having the structure: ##STR4## which is useful for the augmenting or enhancing the aroma or taste of consumable material such as a foodstuff, chewing gum, toothpaste, medicinal product, chewing tobacco, perfume composition, cologne, perfumed article, smoking tobacco composition or smoking tobacco article, and processes for preparing 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone particularly processes which will give rise to compositions of matter having more than 85% by weight 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone and particularly pure crystalline 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone.
There has been considerable work performed relating to substances which can be used to impart (augment or enhance) flavors and fragrances to (or in) various consumable materials. These substances are used to diminish the use of natural materials some of which may be in short supply to provide more uniform properties in the finished product.
Coumarin-like, coconut, lactonic, hay-like, macaroon-like and sweet aroma nuances and coumarin-like, coconut, lactonic, hay-like, macaroon-like, sweet, almond and bitter taste characteristics are highly desirable for many uses in foodstuff, chewing gum, toothpaste, medicinal product and chewing tobacco flavors.
Coumarin-like, tonka-like, fruity, tobacco-like and sweet rum aroma nuances with spicy, hay, and tobacco-like topnotes are highly desirable in several types of perfume compositions, colognes and perfumed articles, e.g. perfumed polymers and anionic, cationic, nonionic and switterionic solid or liquid detergents.
Sweet, lactonic, coconut-like, creamy, coumarin-like, waxy, heliotropin-like, fruity, juicy, rum, sugary and woody nuances are highly desirable in smoking tobacco prior to smoking and sweet, smoothing rich, coumarin-like, creamy, coconut-like, rum-like and caramellic aroma and taste nuances are highly desirable in smoking tobacco on smoking in the main stream and in the side stream.
Coumarinic organoleptic characteristics have heretofore been provided in consumable material by coumarin or homologues or analogues thereof having the structures: ##STR5##
Coumarin, 1,2-benzopyrone having the structure: ##STR6## is described in "Perfume and Flavor Chemicals (Aroma Chemicals)" by Stephen Arctander, 1969 (Monograph 704) as being extensively used in perfumery to support herbaceous odors, lavender, lavendin, rosemary, citrus oils, oakmoss, etc. and as a fixative in numerous types of fragrances. Arctander states that coumarin is almost a standard ingredient in Fougere types with amyl salicylate and lavender notes with or without oakmoss. Arctander states that coumarin is not permitted for food use in the United States of America and is also banned from food flavorings in a number of other countries. Arctander further states that the hazardous level of coumarin is estimated at three grams per day for adult human beings. Accordingly, it has been found necessary in the flavor and fragrance industry to find one or a mixture of suitable replacements for coumarin. In U.S. Pat. No. 4,294,266 and in U.S. Pat. No. 4,241,097 bicyclic compounds defined according to the generic structure: ##STR7## wherein Z is benzo or cyclohexano which generic structure includes the structures: ##STR8## were designed as substitutes for 6-methyl coumarin, 7-methyl coumarin and coumarin itself. However, the compounds having the generic structure: ##STR9## although inexpensive replacements for coumarin, do not have all of the desired coumarin nuances necessary to be a total replacer therefor. Accordingly, a need has arisen for a compound or mixture of compounds which can totally replace coumarin yet which is inexpensive and organoleptically compatible with other flavorants or aromatizing agents in consumable materials.
Tetrahydro naphthalene derivatives are known in the prior art for augmenting or enhancing the aroma or taste of tobaccos. Thus, the compound defined according to the structure: ##STR10## is disclosed in U.K. Patent Sepecification No. 1,226,730 and in U.S. Pat. No. 3,217,717 as useful for augmenting or enhancing the aroma or taste of smoking tobacco. It is indicated in U.K. Patent Specification No. 1,226,730 (published on Mar. 31, 1971) that the compound defined according to the structure: ##STR11## may be produced by reacting the compound having the structure: ##STR12## with isopropenyl acetate in order to make a mixture of compounds defined according to the structure: ##STR13## wherein two of the non-adjacent dashed lines in the resulting mixture represent conjugated carbon-carbon double bonds and the other of the dashed lines represent carbon-carbon single bonds; and reacting the resulting mixture defined according to the structure: ##STR14## with methyl vinyl ketone according to the reaction: ##STR15## wherein in the resulting mixture defined according to the structure: ##STR16## one of R.sub.3 or R.sub.4 is acetyl and the other of R.sub.3 or R.sub.4 is hydrogen and one of R.sub.1 or R.sub.2 is acetoxy and the other of R.sub.1 or R.sub.2 is methyl; and then rearranging the resulting compounds defined according to the structure: ##STR17## (with the exception of the compound having the structure: ##STR18## which will not so rearrange), according to the reaction: ##STR19## However, the compound defined according to the structure: ##STR20## does not have the interesting and important coumarinic-type properties which provide the need that is provided by the material of the instant invention defined according to the structure: ##STR21## Indeed, the composition of matter of the instant invention, the 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone, has properties which are unexpected and unobvious and advantageous from an organoleptic standpoint.
The prior art has indicated that the compound defined according to the structure: ##STR22## may be prepared by means of a decarboxylation of "Hagemann's Ester" which has the structure: ##STR23## according to the reaction: ##STR24## Hagemann's Ester is shown in the prior art to be prepared by reacting two moles of acetoacetic ester with one mole of formaldehyde. Indeed, the compound defined according to the structure: ##STR25## prepared in this manner is shown to be useful in augmenting or enhancing the aroma or taste of foodstuffs, e.g. non-alcoholic beverages, ice creams, candy, baked goods, gelatines, pudding, milk and dairy products in Fenaroli's Handbook of Flavor Ingredients, second edition, volume 2 published by the CRC Press at page 360. Furthermore, Stoll, et al, Helv. Chim. Acta. 30, 2019, 1947 indicates that the compound having the structure: ##STR26## is a natural constituent of Menth. pulegium In addition, Fenaroli's Handbook of Flavor Ingredients at page 400 indicates that the compound having the structure: ##STR27## is useful in augmenting or enhancing the aroma or taste of foodstuffs.
In preparing the compound defined according to the structure: ##STR28## in order to further prepare the compound having the structure: ##STR29## it has been the practice to discard the higher boiling fractions. It is in these higher boiling fractions that the compound having the structure: ##STR30## exists. Heretofore, the prior art has failed to disclose and the flavor and fragrance industry has failed to ascertain that the compound defined according to the structure: ##STR31## has any utility whatsoever in augmenting or enhancing the aroma or taste of consumable materials.
Indeed, heretofore the prior art has disclosed complicated and uneconomical processes for preparing the compound having the structure: ##STR32## thusly: Prochazka at Chem. Abstracts volume 42:8162h discloses the complicated process: ##STR33##
Wilds and Werth, J. Org. Chem. 17, 1149(1952) applied a Robinson annelation reaction utilizing a quaterny ammonium derivative to make a tricyclic material from a bicyclic material. Applying this type of reaction, it is possible to form 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone according to the following reaction sequence: ##STR34##
Marshall, et al, Tetrahedron Lett. 1971, (41) 3795-8 disclosed a difficult to perform synthesis of 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone by means of a Birch reduction using liquid ammonia.
Hexahydro naphthalenones are known in nature and are known flavorants in nature as is stated in the publication Tob. Sci. 1972 16, 107-112 (abstracted at Chem. Abstracts Volume 78, 2099y) wherein the compound having the structure: ##STR35## is shown to be present in tobacco flavor. The compound having the structure: ##STR36## has organoleptic properties different in kind and unexpectedly and unobviously different from the organoleptic properties of the compound having the structure: ##STR37## Also, the compound of U.K. Patent Specification No. 1,226,730 having the structure: ##STR38## has sweet, woody, herbaceous, fruity notes in the main stream and the side stream on smoking in a smoking tobacco composition. It enhances tobacco character and imparts Virginia-like notes. From a flavor standpoint, the compound having the structure: ##STR39## has a dogwood, oak-like, Virginia tobacco-like aroma and taste characteristic at 0.2 ppm. From a perfumery standpoint, the compound having the structure: ##STR40## has a powerful tobacco, hay, dried fruit odor and is useful in clover fragrances. However, the compound having the structure: ##STR41## does not have the organoleptic utilities of the compound having the structure: ##STR42## as will be seen from the instant specification.
USPTO Backgrounds
USPTO Backgrounds