GB2058757A - Butanone Derivatives, Process for Preparation Thereof and the Organoleptic Use Thereof - Google Patents

Abstract

The invention relates to the compound <IMAGE> to the equilibrium mixture containing compounds having the structures <IMAGE> and <IMAGE> and to the organoleptic uses of the compound or equilibrium mixture. A process for the preparation of the equilibrium mixture is also described along with preparation of the organometallic compound having the structure <IMAGE> wherein X represents chlorine, bromine or iodine.

Description

1

GB 2 058 757 A 1

15

20

25

SPECIFICATION

Butanone Derivatives, Process for Preparation thereof and the Organoleptic Use Thereof

The present invention relates to 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione having the structure:

o O

and to an equilibrium mixture containing compounds having the structures:

O O

and

10

The present invention also relates to a novel process for preparing such an equilibrium mixture, the process comprising a solid or liquid detergent base is intimately admixed with from 0.005% up to 3% of the equilibrium mixture, and to uses of the mixture so prepared to alter, modify, augment or enhance the flavor and/or aroma of consumable materials or impart flavor and/or aroma to consumable materials.

A further aspect of the invention relates to an organometaliic compound having the structure:

10

wherein X represents halogen selected from chloro, bromo and iodo.

There has been considerable work performed relating to substances which can be used to impart (modify, 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, and to provide more uniform properties in the finished product. Sweet, honey-like, fruity, grape-like, roselike, ionone-like, tobacco, hay-like and floral aromas with sea-amber or ambergris-like or menthane-like undertones and sweet-floral top-notes are desirable in several types of perfume compositions, perfumed articles and colognes.

Sweet, fruity, berry-like, fresh squeezed fruit (apple and grape) juice-like, hay-like and tea-like aromas prior to smoking and sweet, dried fruit-like, floral, woody and hay/tea aroma characteristics in the main stream on smoking and sweet, tobacco-like and "fresh cigarette pack" aromas in the side stream on smoking are particularly desirable in tobaccos and in tobacco flavoring compositions. Raspberry juice-like, fruit juice-like, "Damascenone"-like (/5-Damascenone, for example, has the structure:

o

15

20

25

30

35

tea-like, tobacco-like, apple juice-like, and dried fruit-like aromas and tastes are particularly desirable for many uses in foodstuff flavors, chewing gum flavors, medicinal product flavors, toothpaste flavors and chewing tobacco flavors, particularly in the red berry juice area, tea area, apple juice area, and wine area.

The foregoing aroma and/or taste combinations are only useful if they are compatible with the notes already present in the particular consumable material to be consumed.

3-Hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-butanone, having the structure:

30

35

2

GB 2 058 757 A 2

has heretofore been indicated by Ayyar, Cookson and Kagi, J. Chem. Soc., Perkin 1,1727 (1975) (Title: "Synthesis of A-Damascone [trans-1-(2,6,6-trimethy!cyclohex-3-enyl)but-2-en-lonej and /3-Damascenone[trans-1 -(2,6,6-trimethylcyclohexa-1,3-dienyl)but-2-en-1 -one]") to be useful as an 5 intermediate in preparing "Damascenone" the "/}" isomer of which has the structure: 5

o

Ayyar, Cookson and Kagi do not, however, teach the usefulness of 3-hydroxy-1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1 -butanone for its organoleptic properties.

Schulte-Elte, U.K Patent Specification 1,391,736 discloses and claims a genus of compounds 10 which include 3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1 -butanone and uses of their 10 organoleptic properties but does not specifically teach any specific cydohexadien compounds per se or their uses for their organoleptic properties. Thus, U.K. Patent Specification 1,391,736 states: "The compounds to which the invention relates have the formula:

15 wherein:

X represents the group:

0

1

OH

- c - c = c - chjr"1

15

O O

II I

c - ch - c - ch-r1

oh

- c = c - c - ch2ra oh

20

c - ch - ch - ch->r

20

oh oh c = c - ch - ch2r or oh oh

I I 1

ch - ch - ch - ch2r

3

GB 2 058 757 A 3

R1, R2, R3, R4 and R5 may be the same or different, and each represents a hydrogen atom or a lower alkyl group having from 1 to 6 carbon atoms; and'the ring is saturated or contains one endocyclic double bond in position 1, 2,3, or 4, or an exocyclic double bond in position 2, or two conjugated double bonds in positions 1 and 3....

5 The new compounds of formula (I) include the following specific examples: 5

2,6,6-trimethyl-1-(1,3-dioxo-but-1-yl)-cyclohex-1-ene; 2-methylene-6,6-dimethyl-1-(1,3-dioxo-but-1-yl)-cyclohexane; 2,6,6-trimethyl-1-(3-hydroxy-butan-1-oyl)-cyclohex-1-ene;

2,6,6-trimethyl-1 -(3-hydroxy-butan-1 -oyl)-cyclohex-2-ene;

10 2,6,6-trimethyM -(2-methyl-1,3-dioxo-but-1 -yl)-cyclohex-1 -ene; 10

2,6,6-trimethyl-1 -(2-methyl-1,3-dioxo-but-1 -yl)-cyclohex-2-ene;

2-methylene-6,6-dimethyl-1 -(2-methyl-1,3-dioxo-but-1 -yl)-cyclohexane; 2,6,6-trimethyl-1-(2-methyl-3-hydroxy-butan-1-oyl)-cyclohex-2-ene; 2-methylene-6,6-dimethyl-1-(2-methyl-3-hydroxy-butan-1-oyl)-cyclohexane; 15 2,6,6-trimethyM -(2-methyl-1,3-dihydroxy-but-1 -yl)-cyclohex-2-ene; 15

2,6,6-trimethyl-1 -(2-methyl-1,3-dihydroxy-but-1 -yl)-cyclohex-1 -ene; 2,6,6-trimethyl-1-(1,3-dioxo-but-1-yl)-cyclohexane; 2,6,6-trimethyl-1-{1,3-dihydroxy-but-1-yl)-cyclohexane; 2,6,6-trimethyl-1-(1,3-dihydroxy-but-1-yl)-cyclohex-2-ene; and 20 2,6,6-trimethyl-1 -(1,3-dihydroxy-but-1 -yl)-cyclohex-1 -ene". 20

None of the exemplified compounds of United Kingdom Patent Specification 1,391,736 has a chemical structure which can be considered by one having ordinary skill in the art to be even remotely similar to 1 -(2,6,6-trimethyM ,3-cyclohexadien-1 -yl)-1,3-butanedione or to 3-hydroxy-1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1 -butanone.

25 Compounds similar to 1-(2,6,6-trimethyl-1,3-cyclohexadien-lyl)-1,3-butanedione having the 25 structure:

o have been reported in the literature, but their uses for their organoleptic properties have not been reported nor are such uses implied. Thus, the diketones having the structures:

O P

30

30

or their corresponding enolates having the generic structure:

where a double bond could be situated at the A1 or A2 positions in the ring, or at the methylene group 35 exocyclic to the ring, are reported by Schulte-Elte, Muller and Ohioff at Helv. Chim. Acta, Vol. 56, FASC 1 (1973) page 310 [Title: "Synthetische Ubergange von der Jononin die Damasconreihe"]. These

35

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GB 2 058 757 A 4

compounds are, however, indicated to be useful as intermediates in synthesizing compounds of the "Damascone" series having the generic structure:

wherein one of the dashed lines is a pi double bond and each of the other dashed lines represents 5 single bonds, and, individually, the structures:

and

which are, in turn, useful for their organoleptic properties. However, the organoleptic properties of the-members of the "Damascone" series are different in kind from the organoleptic properties of 1-(2,6,6-10 trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione.

A sulfur analogue of 3-hydroxy-1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1 -butanone, which sulfur analogue has the structure:

10

is disclosed as having useful organoleptic properties in U. S. Patent 3,979,422. 15 The organoleptic properties of the compound having the structure:

15

are different in kind from the organoleptic properties of 3-hydroxy-1 -(2,6,6-trimethyM ,3-cyclohexadien-1-yl)-1-butanone having the structure:

20 the properties of 3-hydroxy-1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1 -butanone being unexpectedly and unobviously advantageous insofar as the taste and aroma nuances are concerned and further insofar as the intensity and lasting power is concerned.

In addition, the diketone having the structure:

20

5

GB 2 058 757 A 5

is indicated to be useful as a chemical intermediate at Helv. Chim. Acta 31, 2135—42 (1948) [V.

Prelog and Frick, "Ubereinige Oxo-tetrahydro-jonone"].

The diketone 1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione of the instant 5 invention has properties different in kind from the diketones of the prior art. 5

It has now been discovered that novel solid and liquid foodstuff, chewing gum, medicinal product and toothpaste compositions and flavoring compositions therefor having tea-like, tobacco-like, apple juice-like and dried fruit-like aromas and tastes; novel perfume compositions and colognes having floral, fruity and tobacco aromas with rose and grape notes and hay-like and menthane-like 10 undertones; as well as novel smoking tobacco and smoking tobacco flavoring compositions having 10 sweet, dried fruit-like, floral and woody aromas prior to smoking and sweet and dried fruit aroma characteristics in the main stream and in the side stream on smoking, may be provided by the utilization of 3-hydroxy-1 -(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1 -butanone having the formula:

0 oh

15 in foodstuffs, chewing gums, toothpastes, medicinal products, perfume compositions, perfumed 15

articles, colognes and smoking tobaccos as well as smoking tobacco substitutes.

It has also been discovered that novel solid and liquid perfume compositions, colognes and perfumed articles having sweet, honey-like, fruity, grape-like, rose-like, ionone-like, hay-like and floral aromas with sea-amber and ambergris-like undertones and sweet-floral topnotes as well as novel 20 tobacco and flavoring compositions having sweet, fruity, berry-like, fresh squeezed fruit (apple and 20 grape) juice-like, hay-like and tea-like aromas prior to smoking with sweet, hay/tea aromas in the main stream on smoking and sweet, tobacco-like and "fresh cigarette pack" aromas in the side stream on smoking may be provided by 1 -(2,6,6-trimethyM ,3-cyclohexadien-1 -yl)-1,3-butanedione which may or by the equilibrium relationship:

30 in perfume compositions, perfumed articles, colognes and tobaccos as well as tobacco substitutes.

The cyclohexadienyl butanone of the present invention, and 3-hydroxy-1 -(2,6,6-trimethyM ,3-

6

GB 2 058 757 A 6

10

cyclohexadien-1 -yl)-1 -butanone in addition to augmenting or enhancing the taste or aroma or organoleptic properties of a consumable material, may also improve the de-odorising properties of such a consumable material when present in appropriate quantitites. Processes utilizing the organoliptic properties of 3-hydroxy-1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1 -butanedione and 1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione are claimed in our copending Application No. 7902754 (Serial No. ).

3-Hydroxy-1 -(2,6,6-trimethyl-1 -1,3-cyclohexadien-1 -yl)-1 -butanone may be produced according to the procedure set forth by Ayyar Cookson and Kagi at pages 1727—1736 of J. Chem. Soc. Perkin I (1975) (Title: "synthesis of A-Damascone [trans-1-(2,6,6-trimethyl-cyclohex-3-enyl) but-2-en-1-one] and /5-Damascone [trans-1-(2,6,6-trimethylcyclohexa-1,3-dienyl) but-2-en-1-one]") (see particularly column 1 at page 1735, first paragraph).

1 -(2,6,6-Trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione, useful as indicated supra, may be produced by first reacting 1 -acetyl-2,6,6-trimethyl-1,3-cyclohexadiene having the structure:

10

15 with a methyl magnesium halide having the structure:

CH3MgX

(X=halogen)

wherein X is halogen which may either be chloro, brome or iodo, thereby forming an organometallic . compound having the structure:

20

15

20

with the evolution of methane. The said organometallic compound having the structure may then be reacted with an acetyl halide having the structure:

?

25 wherein X' is chloro or bromo, thereby forming a second organometallic compound having the structure:

25

This second organometallic compound is a novel compound. The said second organometallic compound may then be hydrolyzed using dilute acid such as dilute organic acid, e.g., dilute acetic acid

7

GB 2 058 757 A 7

or dilute formic acid, or dilute aqueous mineral acid such as dilute hydrochloric acid, dilute sulfuric acid, dilute phosphoric acid or dilute paratoluenesulforiic acid.

The reaction of the methyl magnesium halide with the 1 -acetyl-2,6,6-trimethyl-1,3-cyclohexadiene takes place at a temperature in the range of from —10°C up to +10°C, preferably from 0—5°C at atmospheric pressure in the presence of an inert anhydrous solvent such as tetrahydrofuran or diethyl ether. The reaction of the first organometallic compound having the structure:

OtfaX

with the acetyl halide having the structure:

?

10 takes place at a temperature in the range of from 0—30°C, preferably at about 20°C. It is preferred that the acetyl halide be in slight molar excess with respect to the first organometallic compound having the structure:

10

The hydrolysis of the second organometallic compound having the structure:

15

Or"

15

preferably takes place using aqueous acetic acid (in excess) at a temperature of between 5°C and 20°C, preferably at about 10°C at atmospheric pressure. Following the hydrolysis of the second organometallic compound having the structure:

20 to 1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione having the structure:

20

O O

which is actually in equilibrium with the enolate having the structure:

8

GB 2 058 757 A 8

The reaction mass is worked up using standard extraction and distillation procedures. 5 The aforementioned reaction sequence is illustrated as follows:

+ CH4+

-4- ^ r |

OI»JgX

o

on* O

0^

+ hx'

Olty O

LA

wherein X is halogen selected from the group consisting of chloro, bromo, and iodo and X' is halogen 10 selected from the group consisting of chloro and bromo.

When it was attempted to oxidize the hydroxyketone having the structure:

10

using a standard oxidizing agent, no 1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione was formed but /5-damascenone having the structure:

o

15

was formed according to the reaction:

15

OH

i I ClfcCb c*frC0°Mo

^ O

n'

9

GB 2 058 757 A 9

Accordingly, the reaction sequence which was found to be workable is not easily replaceable with an alternative reaction sequence.

The diketone and diketone/enolate equilibrium mixture of the present invention may be used to provide an organoleptically improved smoking tobacco product and additives therefor in which specific 5 dried fruit-like flavor characteristics of natural tobacco (prior to smoking and'on smoking, in the main 5 stream and in the side stream) are created or enhanced or modified or augmented, and may be readily controlled and maintained at the desired uniform level regardless of variations in the tobacco components of the blend.

A preferred use for the diketone and diketone/enolate equilibrium mixture made by the method 10 according to the invention is for producing organoleptically improved smoking tobacco product and 10 additives therefor, in which specific desired sweet, fruity, berry, fresh squeezed fruit (apple and grape) juice-like, hay-like and tea-like aromas prior to smoking and improved body, enhanced tobacco character and sweet, pronounced hay/tea characteristics in the main stream on smoking and sweet, tobacco-like and "fresh cigarette pack" aromas in the side stream on smoking, are created or enhanced 15 or modified or augmented and may be readily controlled and maintained at the desired uniform level 15 regardless of variations in the tobacco components of the blend. In particular, low-grade Virginia type tobaccos may be upgraded using the 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione of our invention.

Improved tobacco additives may also be produced using the diketone and diketone/enolate 20 equilibrium mixture made according to the invention, whereby various desirable natural aromatic 20

tobacco flavoring characteristics with sweet, floral and fruity notes may be imparted to smoking tobacco products and may be readily varied and controlled to produce the desired uniform flavoring characteristics.

These latter additives may be made by adding to smoking tobacco materials or a suitable 25 substitute therefor (e.g., dried lettuce leaves) an aroma and flavor additive containing as an active 25

ingredient 1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione. 3-hydroxy-1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1 -butanone may also be incorporated with the 1 -(2,6,6-trimethyM, 3-cyclohexadien-1 -yl)-1,3-butanedione.

In addition, other flavoring and aroma additives may be added to the smoking tobacco material or 30 substitute therefor either separately or in mixture with the 3-hydroxy-1 -(2,6,6-trimethyl-1,3- 30

cyclohexadien-1-yl)-1 -butanone as follows: I. Synthetic Materials: Beta-ethyl-cinnamaldehyde;

eugenol, dipentene, -/5-damascenone; maltol; ethyl maltol; delta undecalactone; delta decalactone; benzaldehyde; amyl acetate; ethyl butyrate; ethyl valerate; ethyl acetate; 2-hexenal-1; 2-methyl-5-isopropyl-1,3-nonadiene-8-one; 2,6-dimethyl-2,6-undecadiene-10-one; 2-methyl-5-isopropyl 35 acetophenone; 2-hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene; 35

dodecahydro-3a,6,6,9a-tetramethyl naphtho-(2,6-b)-furan; 4-hydroxy hexanoic acid, gamma lactone; and polyisoprenoid hydrocarbons defined in Example V of U.S. Patent 3,589,273 issued on June 29th, 1971 and II. Natural Oils: celery seed oil; coffee extract; bergamot oil; cocoa extract; nutmeg oil; and origanum oil.

40 An aroma and flavoring concentrate containing one or both cyclohexadien-1 -yl-1 -butanone 40

derivatives and if desired, one or more of the above-indicated additional flavoring additives may be added to the smoking tobacco material, to the filter or to the leaf or paper wrapper. The smoking tobacco material may be shredded, cured, cased and blended tobacco material or reconstituted tobacco material or tobacco substitutes (e.g. lettuce leaves) or mixtures thereof. The proportions of 45 flavoring additives may be varied in accordance with taste, but insofor as enhancement or the 45

imparting of natural and/or sweet notes, we have found that satisfactory results are obtained if the proportion by weight of the sum total of cyclohexadien-1 -yl-1 -butanone derivatives to smoking tobacco material is between 50 ppm and 1,500 ppm (0.005%—0.15%) of the active ingredients to the smoking tobacco material. We have further found that satisfactory results are obtained if the 50 proportion by weight of the sum total of cyclohexadien-1-yl-1-butanone derivatives used to flavoring 50 material is between 500 and 15,000 ppm (0.05%—1.5%).

Any convenient method for incorporating the cyclohexadien-1 -yl-1 -butanone derivatives into the tobacco product may be employed. Thus, the cyclohexadien-1 -yl-1 -butanone derivatives taken alone or along with other flavoring additives may be dissolved in a suitable solvent such as ethanol, diethyl 55 ether and/or volatile organic solvents and the resulting solutions may either be spread on the cured, 55 cased and blended tobacco material or the tobacco material may be dipped into such solution. Under certain circumstances, a solution of the cyclohexadien-1-yl-1-butanone derivatives taken alone or taken together with other flavoring additives as set forth above, may be applied by means of a suitable applicator such as a brush or roller on the paper or leaf wrapper for the smoking product, or it may be 60 applied to the filter by either spraying, or dipping or coating. 60

Furthermore, it will be apparent that only a portion of the tobacco or substitute therefore need be treated and the thus-treated tobacco may be blended with other tobaccos before the ultimate tobacco product is formed. In such cases, the tobacco treated may have the cyclohexadien-1 -yl-1 -butanone derivatives in excess of the amounts of concentrations above indicated so that when blended with 65 other tobaccos, the final product will have the percentage within the indicated range. 65

10

GB 2 058 757 A 10

In accordance with one specific example of our invention, an aged, cured and shredded domestic Virginia tobacco is spread with a 20% ethyl alcohol solution of 1-(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1 -butanedione in an amount to provide a tobacco composition containing 100 ppm by weight of 1-(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione on a dry jpasis. Thereafter, the alcohol is 5 removed by evaporation'and the tobacco is manufactured into cigarettes by the usual techniques. The 5 cigarette when treated as indicated has a desired and pleasing aroma which is detectable in the main and side streams when the cigarette is smoked. This aroma is described as being sweeter with more pronounced hay/tea character with improved body and enhanced tobacco character in the main stream and sweeter, more tobacco-like with a "fresh cigarette pack" aroma in the side stream. Prior to 10 smoking the cigarette has a sweet, fruity, berry-like, fresh squeezed fruit (apple and grape) juice-like, 10 hay-like and tea-like aroma characteristic.

While our invention is particularly useful in the manufacture of smoking tobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco, other tobacco products formed from sheeted tobacco dust or fines may also be used. Likewise, the active ingredient or ingredients may be incorporated with 15 materials such as filter tip materials, seam paste, packaging materials and the like which are used 15

along with tobacco to form a product adapted for smoking. Furthermore, these active ingredients may also be added to certain tobacco substitutes of natural or synthetic origin (e.g., dried lettuce leaves) and, accordingly, by the term "tobacco" as used throughout this specification is meant any composition intended for human consumption by smoking or otherwise, whether composed of tobacco 20 plant parts or substitute materials or both. 20

1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione, either alone or with 3-hydroxy-1 -(2,6,6-trimethyM ,3-cyclohexadien-1 -yl)-1 -butanone, and one or more auxiliary perfume ingredients, including, for example, alcohols, aldehydes, ketones other than the cyclohexadien-1 -yl-1 -butanone derivatives of our invention, nitriles, esters, cyclic esters (lactones), dialkyl ethers, alkyl alkenyl ethers, 25 thioesters, thiols, carboxylic acids and natural essential oils may be admixed so that the combined 25

odors of the individual components produced a pleasant and desired fragrance, particularly and preferably in rose fragrances. Such perfume compositions usually contain (a) the main note or the "bouquet" or foundation stone of the composition; (b) modifiers which round off and accompany the main note; (c) fixatives which include odorous substances which lend a particular note to the perfume 30 throughout all stages of evaporation and substances which retard evaporation; and (d) topnotes which 30 are usually low boiling, fresh smelling materials.

In perfume compositions, it is the individual components which contribute to their particular olfactory characteristics, however, the over-all sensory effect of the perfume composition will be at least the sum total of the effects of each of the ingredients. Thus, the compound made according to the 35 invention, alone or in combination with the 3-hydroxy derivative, may be used to alter, modify or 35

enhance the aroma characteristics of a perfume composition, for example, by utilizing or moderating the olfactory reaction contributed by other ingredients in the composition.

The amount of cyclohexadien-1-yl-1-butanone derivatives additive which will be effective in perfume compositions as well as in perfumed articles and colognes depends on many factors, including 40 the other ingredients, their amounts and the effects which are desired. It has been found that perfume 40 compositions containing as little as 0.01% of cyclohexadien-1-yl-1-butanone derivatives or even less (e.g., 0.005%) can be used to impart a floral, fruity, tobacco, aroma with rose notes and hay, menthane undertones can be used to impart a sweet, honey-like, fruity, grape-like, rose-like, ionone-like, hay-like and floral aroma with sea-amber, and ambergris-like undertones and sweet-floral topnotes to soaps, 45 cosmetics and other products. The amount employed can range up to 70% of fragrance components 45 and will depend on considerations of cost, nature of the end product, the effect desired on the finished product and the particular fragrance sought.

The cyclohexadien-1-yl-1-butanone derivatives are useful as olfactory components in detergents and soaps, fabric softener compositions (especially for cloths drier uses), space odorants and 50 deodorants, perfumes, colognes, toilet water, bath preparations, such as lacquers, brilliantines, 50

pomades and shampoos; cosmetic preparations, such as creams, deodorants, hand lotions and sun screens; powders, such as talcs, dusting powders, face powders and the like. When used as an olfactory component as little as 0.25% of cyclohexadien-1 -yl-1 -butanone derivative(s) will suffice to impart an intense floral note to rose formulations. Generally, no more than 5% of cyclohexadien-1 -yl-1 -55 butanone derivative(s) based on the ultimate end product, is required in the perfume composition. 55

In addition, the perfume composition or fragrance composition of our invention can contain a vehicle or carrier for the cyclohexadien-1 -yl-1 -butanone derivative. The vehicle can be a liquid such as a non-toxic alcohol (e.g., ethyl alcohol), a non-toxic glycol (e.g., propylene glycol), or the like. The carrier can also be an absorbent solid, such as a gum, e.g., gum arabic, or components for encapsulating the 60 composition (such as gelatin) as by means of coacervation. 60

It will thus be apparent that the cyclohexadien-1 -yl-1 -butanone derivatives can be utilized to alter, modify or enhance sensory properties, particularly organoleptic properties, such as flavor(s)

and/or fragrance(s) of a wide variety of consumable materials.

Example I (A) serves to illustrate a process for preparing 3-hydroxy-1 -(2,6,6-trimethyl-1,3-65 cyclohexadien-1-yl)-1-butanone. 65

11

GB 2 058 757 A 11

10

Example I also serves to illustrate the unworkability of a process which was at first thought to have the ability to yield 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione. Example II, following, serves to illustrate the process for specifically producing 1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione useful in our invention. Examples III to XII serve to illustrate the utilities of the 1 -(2,6,6-trimethyM ,3-cyclohexadien-1 -yl)-1,3-butanedione of our invention. Examples XIII to XXX are included for reference and relate to the use of 3-hydroxy-1 -(2,6,6-trimethyM ,3-cyclohexadien-1 -yl)-1 -butanone. Example XXXI demonstrates the use of the combination of 1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione and 3-hydroxy-1 -(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-butanone.

It will be understood that these examples are illustrative, and the invention is to be considered restricted thereto only as indicated in the appended claims.

All parts and percentages given herein are by weight unless otherwise specified.

In the following Examples the words 'Primol' and 'Cab-O-Sil' are trade marks.

10

15

Example I (A)

Preparation of 3-hydroxy-1 -(2,6,6-trimethyl 1,3-cyclohexadien-1 -yl)-1 -butanone

15

4~ HP

[h*3

20 Into a 2-liter reaction flask equipped with a mechanical stirrer, cooling bath, 250 ml addition 20

funnel, nitrogen purge, water-cooled condenser, gas bubbler and thermometer, is placed 427 ml (1.3 moles) of a 3-molar solution of methyl magnesium chloride in tetrahydrofuran. 200 Grams (1.22 moles) of 2,6,6-trimethyl-1-acetylcyclohexa-1,3-diene are added dropwise from the addition funnel at a rate sufficient to produce methane. Cooling is applied as necessary to maintain the reaction •25 temperature between 30 and 35°C. Following completion of the addition of the 2,6,6-trimethyM- 25 acetylcyclohexa-1,3-diene, the reaction mass is stirred until no further methane is evolved. The reaction mass is then cooled to a temperature in the range of from 0°C to 5°C, and 59 grams of acetaldehyde is added dropwise with stirring while maintaining the reaction mass temperature at about 10°C. The reaction is slightly exothermic. 15 minutes after the completion of the addition of 30 acetaldehyde, acetic acid is added dropwise while maintaining the temperature of the reaction mass at 30 about 10°C. Following the addition of acetic acid, the reaction mass is permitted to reach room temperature. The reaction mass is then washed into a separatory funnel with water to dissolve the salt therein. The resulting organic layer is washed with saturated sodium chloride, saturated sodium bicarbonate, and then saturated sodium chloride. The washed organic layer is then dried over 35 anhydrous magnesium sulfate and concentrated on a rotovap yielding 256 grams of residue. 35

The resulting hydroxyketone having the structure:

12

GB 2 058 757 A 12

is distilled under vacuum in order to separate it from other impurities. 70 Grams of the distilled material is combined with 80 grams of Primol® and distilled under 0.25—0.60 mm Hg pressure into nine fractions. The distillation data is as follows:

Weight of

5 Vapor Temp. Liquid Temp. Fraction Fraction #

22°—40.5°

24°—85°

3.96

1

40.0

94

6.50

2

44

105

2.90

3

88

114

4.24

4

89.5

116.5

4.50

5

90.75

120.0

8.01

6

93.0

128.0

8.34

7

88.5

147.0

7.93

8

87.0

147.0

3.51

9

15 Fraction #6 is found to be substantially pure and is submitted for mass spectral, NMR, IR and UV

analyses. The NMR spectrum is set forth in Figure 1. The infra-red spectrum is set forth in Figure 2. The mass spectrum is set forth in Figure 3. The ultraviolet absorption spectrum (using a methanol solvent) is set forth in Figure 4. Jlmax=277 nm. E^m=176.65 in methyl alcohol. The NMR analysis is as follows:

Chem. Shift Signal Type Assignment Quantity

The infra-red analysis is as follows: 3400—3500cm 1 (strong); 3000cm 1 (moderate); 2950cm 1 (strong); 2800cm_1 (moderate); 1680cm_1 (strong); 1580om_l (weak); 1460om_1 (strong); 1360— 30 1400cm_1 (strong); 1280—1330cm~1 (strong); 1185cm~1 (moderate); 1160cm-1 (strong); 1125cm~1 30

(moderate); 1040cm_1 (moderate); 1005cm_1 (moderate); 935—980cm~1 (moderate); 850 cm-1 (weak); 820cm_1 (weak); 783cm~1 (moderate); 723—737om_1 (moderate); and 690cm_1 (moderate).

13

GB 2 058 757 A 13

The mass spectral analysis is (M/E Ratio followed by relative intensity): 43,100; 69,18; 77,13; 79,11; 91,18; 105,30; 121,81; 122,10; 149,9; 164,12; 190,2 and208p,1.

Example I (B)

Aborted Run

5 Attempted synthesis of 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione (actual production of "B-Damascenone").

Reaction:

effect

CtjjCOOtJ*.

o-cyu

It was attempted to oxidize the keto alcohol, the product of the process of Example I (A) to 1 o diketone according to the procedure of Cory and Suggs, Tetrahedron Letters No. 31, pages 2647— 2650 (1975). The Cory and Suggs reagent is pyridinium chlorochromate. However, /5-damascenone, having the structure:

0

10

was produced rather than 1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione, having the 15 structure:

O

15

Into a 250 ml three-necked, round-bottom flask equipped with water cooled condenser and magnetic stirrer is placed 12.30 grams of pyridinium chlorochromate slurried in 100 ml methylene dichloride (CH2CI2). The product of the process of Example l(A) having the structure:

oh

20

20

(7.93 grams [0.038 moles] is dissolved in 20 ml methylene dichloride and is added to the reaction mass with stirring. The resulting mixture is permitted to stir at room temperature for a period of two hours during which time the color of the solution changes from orange to black.

The reaction mass is removed from the reaction flask using 100 ml diethyl ether. The reaction 25 flask is then washed three times with diethyl ether leaving a black "tar-like" substance behind. The organic layer is then washed twice with sodium bicarbonate and saturated sodium chloride solution, and is then concentrated on a rotovap yielding 7.06 grams of crude material. A 5 microliter injection is made on a 20' SE-30 GLC column and run from 100—225°C at 4°C/min. The major peak is analyzed using infrared analysis and found to be /5-Damascenone having the structure:

25

30

30

14

GB 2 058 757 A 14

Example II

Preparation of 1-(2,6,6-trimethyl-1,3-cyclohexadien-1,3-butanedione

Reaction:

+ C^Cl-

O

II

Qc eryt o

+- H,0 ^

t- HCl

Into a 250 ml three-necked, round-bottom flask equipped with a mechanical stirrer, an immersion thermometer, a nitrogen purge, a dry ice/isopropanol cooling bath, a 125 ml addition funnel and a 10 water-cooled condenser with gas bubbler, is placed 42.7 ml of a tetrahydrofuran solution of methyl 10 magnesium chloride (3 molar). The methyl magnesium chloride/THF solution is chilled to 0—5°C with stirring, and 20 grams (0.122 moles) of acetyl-2,6,6-trimethyl-1,3-cyclohexadiene is added dropwise over a minute period. Following completion of the addition, the reaction mass is stirred at about 20°C until no further methane is observed to evolve (approximately a 30 minute period). The reaction mass 15 is then chilled to 0°C and 10.14 grams (0.13 moles) of freshly distilled acetyl chloride is added 15

dropwise over a 20 minute period. Following the addition of the acetyl chloride, the reaction mass is stirred at a temperature of 20°C for 15 minutes and then once more chilled to 10°C, and a solution of 8,1 grams of acetic acid in 10 ml water is added dropwise during a 5-minute period. Following the addition of the acid, water is added to dissolve salts, and the reaction mass is transferred to a 20 separatory funnel. Diethyl ether is added and the ether layer is separated and washed twice with 20

saturated sodium bicarbonate solution and then twice with saturated sodium chloride solution; dried and concentrated in vacuo. The concentrate is then analyzed using GLC (Conditions: 20'x 1/4" 5% SE-30 colunjn). NMR, IR and mass spectral data confirm that the last eluting major peak is 1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione. The residue is then submitted to fractional 25 distillation after adding thereto 50 grams primol R. The fractional distillation is carried out on a 25

14"x3/4" Vigreaux column yielding the following fractions.

30

35

40

Fraction No.

1

2

3

4

Vapor Temp. 23—39 67 61 94

Liquid Temp. 24—114.5 143 194 225

Vacuum (mm Hg) 0.175 0.20 0.28 0.25

Weight (grams) 7.81 5.92 3.90 5.56

Fraction 3 contains 95.4% 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione.

NMR spectrum for 1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione of fraction 3 is set forth in Figure 5. The IR spectrum for 1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione of fraction 3 is set forth in Figure 6. The UV absorption curve for 1 -(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione of fraction 3 is set forth in Figure 7 {E^m=473.04; Amax=284 nm).

The infra-red analysis (in carbontetrachioride solution) is as follows: 1000cm-1; 1160crrT1; 1175cm-1; 1225cm-1; 1250cm-1; 1295cm-1; 1360cm-1; 1440cm-1; 1600cm-1 (broad); 2920cm-1; and 2970cm-1.

The NMR analysis (in C Cl3 solution) is as follows:

30

35

40

15

GB 2 058 757 A 15

ppm Interpretation

1.10 (s) gem dimethyl protons 6H

1.75 (s) CH3—C=C—C— 3H

II

0

2.30 (s) CH— C=C— 3H

0

5.45 (s) olefinic proton 1H

5.80 (s) olefinic protons 2H

15.67 (broad) bonded H

The mass spectral analysis for 1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione is as follows (M/E) Ratio followed by relative intensity): 39,30; 41,24; 43,100; 77,10; 85,77; 91,11; 10 105,11; 121,21; 191,11 and206p,12. 10

Example III Rose Formulation

To demonstrate the use of 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione in a rose formulation, the following formula is provided:

15 Ingredient Parts by Weight 15

Phenylethyl alcohol 200

Geraniol 400

Trichloromethylphenyl carbinyl acetate 20

Phenylethyl acetate 60

20 Undecylenic aldehyde (10% in diethyl phthalate) 5 20

n-Nonyl aldehyde (10% in diethyl phthalate) 2

Musk ketone 10

Musk ambrette 10

Eugenol phenyl acetate 20

25 Citroneilol 100 25

Vanillin (10% in diethyl phthalate) 6

Eugenol 30

Citronellyl formate 30

Geranyl acetate 10

30 Linalool 40 30

Geranyl phenyl acetate 50

Cis beta, A-hexenyl acetate 2 1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione prepared according to Example II 5

35 The addition of 0.5% of 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione lends a 35 great deal of strength and character to the rose fragrance. It contributes great floralcy and the heady natural sweetness of the red rose flower together with honey-like, fruity, grape-like, and hay-like nuances and sea-amber undertones with sweet-floral topnotes.

At lower concentrations (0.01%) its contribution is more subtle; however, it still gives an 40 interesting natural effect with the ambergris-like undertone. 40

This product may normally be used from approximately 0.01% to 10% in perfume compositions. For special effects, however, higher concentrations (50% plus) can be used.

Example IV

Preparation of a Soap Composition

45 One hundred grams of soap chips are produced according to Example V of U.S. Patent 4,058,487 45

issued on November 1 5,1977, as follows:

The sodium salt of an equal mixture of C10/C14 alkane sulfonate (95% active), 40 pounds, is dissolved in a mixture of 80 pounds of anhydrous isopropanol and 125 pounds of deionized water at 150°F. In this mixture is dissolved 10 pounds of partially hydrogenated cocoanut oil 50 fatty acids and 15 pounds of sodium mono-C14 alkyl maleate, and the pH of this solution is 50

adjusted to 6.0 by the addition of a small amount of 50% aqueous solution of sodium

16

GB 2 058 757 A 16

hydroxide. The isopropanol is distilled off, and the remaining aqueous solution is drum dried. The resulting solid actives are then blended in a chip mixture with 10 pounds water, 0.2 pounds titanium hydroxide and 0.7 pounds of the material, 1-(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione. The chips are then plotted into logs, cut to size and 5 finally stamped into bars having a pH of approximately 6.9. 5

The perfumed soap manifests an excellent rose character with excellent sweet, honey-like, fruity, hay-like and floral nuances with a sea-amber and ambergris-like undertone and sweet-floral topnotes.

Example V

Preparation of a Detergent Composition

10 A total of 100 grams of a detergent powder prepared according to United States Patent 10

4,058,472 and containing 5% by weight of the sodium salts of a mixture of sulfonated C14—Cia alkyl catechol as a surface active component, the mixture being 60 parts by weight of mono-C14—C18 alkyl catechol and 40 parts by weight of di-C14—Cia alkyl catechol, 35% of sodium tetrapyrophosphate, 30% of sodium silicate, 20% of sodium carbonate, 3% of sodium carboxymethyl cellulose and 7% of 15 starch is mixed with 0.15 grams of 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione of 15

Example II until a substantially homogeneous composition is obtained. This composition has an excellent rose aroma with sweet, honey-like, fruity, grape-like, hay-like and floral nuances and a sea-amber/ambergris-like undertone with sweet-floral topnotes.

Example VI

20 Tobacco Formulation 20

A tobacco mixture is produced by admixing the following ingredients:

Ingredient Parts by Weight

Bright 40.1

Burley 24.9

25 Maryland 1.1 25

Turkish 11.6

Stem (flue-cured) 14.2

Glycerine 2.8

Water 5.3

30 Cigarettes are prepared from this tobacco. 30

The following flavor formulation is prepared:

Ingredient Parts by Weight

Ethyl butyrate .05

Ethyl valerate .05

Maltol 2.00 35

Cocoa extract 26.00

Coffee extract 10.00

Ethyl alcohol 20.00

Water 41.90

40 The above-stated tobacco flavor formulation is applied at a rate of 0.1% to all the cigarettes 40

produced using the above tobacco formulation. Half of the cigarettes are then treated with 50 or 150 ppm of 1 -(2,6,6-trimethyM ,3-cyclohexadien-1 -yl)-1,3-butanedione produced according to the process of Example II. The control cigarettes not containing the 1 -(2,6,6-trimethyM ,3-cyclohexadien-1 -yl)-1,3-butanedione and the experimental cigarettes which contain the 1 -(2,6,6-trimethyM ,3-45 cyclohexadien-1 -yl)-1,3-butanedione produced according to the process of Example II are evaluated by 45 paired comparison, and the results are as follows:

The experimental cigarettes are found, on smoking, to have improved "body", enhanced tobacco character, to be sweeter, and to have more pronounced hay/tea character in the main stream. The experimental cigarettes are also found, on smoking, to be sweeter, more tobacco-like, having a fresh 50 cigarette pack" aroma in the side steam. 50

The tobacco of the experimental cigarettes, prior to smoking, has sweet, fruity, berry-like, fresh squeezed fruit (apple and grape) juice-like, hay-like, and tea-like aroma characteristics.

All cigarettes are evaluated for smoke flavor with a 20 mm cellulose acetate filter. The 1-(2,6,6-trimethyM ,3-cyclohexadien-1 -yl)-1,3-butanedione produced according to Example 55 II enhances the tobacco-like taste and aroma of the blended cigarettes imparting to it sweet, natural 55 tobacco "fresh cigarette pack" notes as well as hay/tea notes.

Example VII

Preparation of a Cosmetic-powder Composition

A cosmetic powder is prepared by mixing in a ball mill, 100 grams of talcum powder with 0.25

17

GB 2 058 757 A 17

grams of 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-ylM ,3-butanedione prepared according to Example II. It has an excellent sweet, honey-like, fruity, grape-like, rose-like, ionone-like, hay-like and floral-like aroma with a sea-amber/ambergris-like undertone and sweet-floral topnotes.

Example VIII 5 Perfumed Liquid Detergent

Concentrated liquid detergents with sweet, honey-like, fruity, grape-like, rose-like, ionone-like, hay-like and floral aromas with sea-amber/ambergris-like undertones and sweet-floral topnotes are prepared by adding 0.10%, 0.15% and 0.20% of 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione prepared according to Example II. They are prepared by adding and homogeneously 10 mixing the appropriate quantity of 1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione in the liquid detergent. The detergents all possess sweet, honey-like, fruity, grape-like, rose-like, ionone-like, hay-like and floral aromas with sea-amber/ambergris-like undertones, the intensity increasing with greater concentrations of 1 -(2,6,6-trimethyl-1,3-cyclohexanedien-1 -yl)-1,3-butanedione.

Example IX

15 Preparation of a Cologne and Handkerchief Perfume

1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione prepared according to Example II is incorporated into colognes of several strengths at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0% and 5.0% in 85% aqueous ethanol; and into several concentrations of handkerchief perfumes at the rate of 15%, 20% and 25% (in 95% aqueous ethanol). Distinct and definite sweet, honey-like, fruity, grape-20 like, rose-like, ionone-like, hay-like and floral aromas with sea-amber/ambergris-like undertones and sweet-floral topnotes are imparted to the colognes and to the handkerchief perfumes of the several concentrations set forth above.

Example X

Preparation of a Cologne and Handkerchief Perfume

25 The composition of Example III is incorporated into colognes of several concentrations, 2.0%, 2.5%, 3.0%, 3.5%, 4.0% and 5.0%, in 85% aqueous ethanol; and into handkerchief perfumes at concentrations of 15%, 20% and 25% (in 95% aqueous ethanol). The use of the 1 -(2,6,6-trimethyM ,3-cyclohexadien-1-yl)-1,3-butanedione in the composition of Example III affords a distinct and definite strong rose aroma with sweet, fruity, hay-like, and floral aromas and sea-amber/ambergris-like 30 undertones with sweet-floral topnotes to the handkerchief perfumes and the colognes at all of the concentrations set forth above.

Example XI

Preparation of a Soap Composition

One hundred grams of soap chips and intimately admixed with one gram of 1-(2,6,6-trimethyl-35 1,3-cyclohexadien-1 -yl)-1,3-butanedione until a substantially homogeneous composition is obtained. The perfumed soap composition manifests an excellent sweet, honey-like, fruity, grape-like, rose-like, ionone-like, hay-like and floral aroma with sea-amber/ambergris-like undertones and sweet-floral topnotes.

Example XII 40 Preparation of a Detergent Composition

A total of 100 grams of a detergent powder is intimately admixed with 0.15 grams of 1-(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione prepared according to Example II until a substantially homogeneous composition is obtained. This composition has an excellent sweet, honeylike, fruity, grape-like, rose-like, ionone-like, hay-like and floral aroma with sea-amber/ambergris-like 45 undertones and sweet-floral topnotes.

Example XIII Raspberry Flavor

The following basic raspberry flavor formulation is prepared:

Ingredient Parts by Weight

50 Vanillin 2.0

Maltol 5.0

Parahydroxybenzylacetone 5.0

Alpha-ionone (10% in propylene glycol) 2.0

Ethyl butyrate 6.0

55 Ethyl acetate 16.0

Dimethyl sulfide 1.0

Isobutyl acetate 13.0

Acetic acid 10.0

Acetaldehyde 10.0

60 Propylene glycol 930.0

5

10

15

20

25

30

35

40

45

50

55

60

18

GB 2 058 757 A 18

To half of the above formulation, at the rate of 0.2%, 3-hydroxy-1 -(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1 -butanone prepared according to Example I (A) is added. Nothing is added to the other half of the above formulation. The raspberry flavor formulation with and without the addition of 3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1 -butanone are compared at the rate of 0.01% 5 (100 ppm) in water and evaluated by a bench panel of five members. 5

The flavor containing 3-hydroxy-1 -(2,6,6-trimethyM ,3-cyclohexadien-1 -yi)-1 -butanone has a very pleasing characteristic raspberry juice aroma. It is natu>al juice-like whereas the flavor without 3-hydroxy-1-(2,6,6-trimethyM ,3-cyclohexadien-1-yl)-1 -butanone has ionone-like notes dominating. The taste of the flavor formulation containing the 3-hydroxy-1 -(2,6,6-trimethyM ,3-cyclohexadien-1 -yl)-1 -10 butanone is also raspberry juice-like, round and pleasant as distinct fr;om the flavor without the 3- 10

hydroxy-1-(2,6,6-trimethyM ,3-cyclohexadien-1-yl)-1 -butanone which is unbalanced, ionone-like.

Therefore, the panel prefers, unanimously, the flavor formulation containing the 3-hydroxy-1 -(2,6,5-trimethyl-1,3-cyclohexadien-1 -yl)-1 -butanone.

Example XIV

15 A. Powder Flavor Composition 15

20 Grams of the flavor composition of Example XIII is also emulsified in a solution containing 300 gm gum acacia and 700 gm water. The emulsion is spray-dried with a Bowen Lab Model Drier utilizing 260 c.f.m. of air with an inlet temperature) of 500°F, an outlet temperature of 200°F, and a wheel speed of 50,000 rpm.

20 B. Sustained Release Flavor 20

The following mixture is prepared:

Ingredient Parts by Weight

Liquid Raspberry Flavor Composition of Example II 20

Propylene glycol 9

25 Cab-O-Sil M-5 5.00 25

(Brand of Silica produced by the Cabot Corporation of 125 High Street,

Boston, Mass. 02110

Physical Properties:

Surface area: 200 m2/gm

30 Nominal particle size: 0.012 microns 30

Density: 2.3 Ibs/cu.ft.)

The Cab-O-Sil is dispersed in the liquid raspberry flavor composition of Example XIII with vigorous stirring, thereby resulting in a viscous liquid. 71 parts by weight of the powder flavor composition of Part A, supra, is then blended into said viscous liquid, with stirring, at 25°C for a period of 30 minutes 35 resulting in a dry, free flowing sustained release flavor powder. 35

Example XV

10 Parts by weight of 50 Bloom pigskin gelatin is added to 90 parts by weight of water at a temperature of 150°F. The mixture is agitated until the gelatin is completely dissolved and the solution is cooled to 120°F. 20 Parts by weight of the liquid flavor composition of Example XIII is added to the

40 solution which is then homogenized to form an emulsion having particle size typically in the range of 40 2—5 microns. This material is kept at 120°F under which conditions the gelatin will not gel.

Coacervation is induced by adding, slowly and uniformly, 40 parts by weight of a 20% aqueous solution of sodium sulphate. During coacervation, the gelatin molecules are deposited uniformly about each oil droplet as a nucleus.

45 Gelation is effected by pouring the heat coacervate mixture into 1,000 parts by weight of 7% 45 *

aqueous solution of sodium sulphate at 65°F. The resulting jelled coacervate may be filtered and washed with water at temperatures below the melting point of gelatin, to remove the salt.

Hardening of the filtered cake, in this example, is effected by washing with 200 parts by weight of 37% solution of formaldehyde in water. The cake is then washed to remove residual formaldehyde.

50 Example XVI 50

Chewing Gum

100 Parts by weight of chicle are mixed with 4 parts by weight of the flavor prepared in accordance with Example XIV. 300 Parts of sucrose and 100 parts of corn syrup are added. Mixing is effected in a ribbon blender with jacketed side walls of the type manufactured by the Baker Perkins Co.

55 The resultant chewing gum blend is then manufactured into strips 1 inch in width and 0.1 inches 55 in thickness. The strips are cut into lengths of 3 inches each. On chewing, the chewing gum has a pleasant, long-lasting raspberry flavor.

19

GB 2 058 757 A 19

Example XVII Chewing Gum

100 Parts by weight of chicle are mixed with 18 parts by weight of the flavor prepared in accordance with Example XV. 300 Parts of sucrose and 100 parts of corn syrup are then added. Mixing 5 is effected in a ribbon blender with jacketed side walls of the type manufactured by the Baker Perkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inch in width and 0.1 inches in thickness. The strips are cut into lengths of 3 inches each. On chewing, the chewing gum has a pleasant, long-lasting raspberry flavor.

10 Example XVIII

Toothpaste Formulation

The following separate groups of ingredients are prepared:

Parts by Weight

Ingredient

Group

"A"

30.200

Glycerin

15.325

Distilled water

.100

Sodium benzoate

.125

Saccharin Sodium

.400

Stannous Fluoride

Group

"B"

12.500

Calcium carbonate

37.200

Dicalcium phosphate (dihydrate)

Group

"C"

2.000

Sodium N-lauroyl sarcosinate (foaming agent)

Group

"D"

1.200

Flavor Material of Example XV

100.000 (Total)

Procedure:

1. The ingredients in Group "A" are stirred and heated in a steam jacketed kettle to 160°F. 30 2. Stirring is continued for an additional three to five minutes to form a homogeneous gel.

3. The powders of Group "B" are added to the gel, while mixing until a homogeneous paste is formed.

4. With stirring, the flavor of "D" is added and lastly the sodium n-lauroyl sarcosinate.

5. The resultant slurry is then blended for one hour. The completed paste is then transferred to a 35 three roller mill and then homogenized, and finally tubed.

The resulting toothpaste when used in a normal toothbrushing procedure yields a pleasant raspberry flavor, of constant strong intensity throughout said procedure (1—1.5 minutes).

Example XIX

Chewable Vitamin Tablets 40 The flavor material produced according to the process of Example XIII is added to a chewable vitamin tablet formulation at a rate of 10 gm/Kg which chewable vitamin tablet formulation is prepared as follows:

In a Hobart Mixer, the following materials are blended to homogeneity:

Ingredients

Tablets Gms/1000

45

Vitamin C (ascorbic acid) as ascorbic acid-sodium ascorbate mixture 1:1 Vitamin B, (thiamine mononitrate) as Rocoat thiamine mononitrate

70.0

33-1/3% (Hoffman La Roche)

4.0

Vitamin B2 (riboflavin) as Rocoat riboflavin 33-1/3%

5.0

Vitamin B6 (pyridoxine hydrochloride) as Rocoat pyridoxine hydrochloride

50

33-1/3%

4.0

Niacinamide as Rocoat niacinamide 33-1/3%

33.0

Calcium pantothenate

11.5

Vitamin B12 (cyanocobalamin) as Merck 0.1 % in gelatin

3.5

Vitamin E (dl-alpha tocopheryl acetate) as dry Vitamin E acetate 33-1/3%

55

Roche

6.6

d-Biotin

0.044

Certified lake color

5.0

Flavor of Example XIII

(as indicated above)

Sweetener—sodium saccharin

1.0

60

Magnesium stearate lubricant

10.0

Mannitol q.s. to make

500.0

5

10

15

20

25

30

35

40

45

50

55

60

20

GB 2 058 757 A 20

Preliminary tablets are prepared by slugging with flat-faced punches and grinding the slugs to 14 mesh. 13.5 g dry Vitamin A acetate and 0.6 Vitamin D are then added as beadlets. The entire blend is then compressed using concave punches at 0.5 g each.

Chewing of the resultant tablets yields a pleasant, long-lasting, consistently strong raspberry

5 flavor for a period of 12 minutes. 5

Example XX Chewing Tobacco

Onto 100 pounds of tobacco for chewing (85% Wisconsin leaf and 15% Pennsylvania leaf) the following casing is sprayed at a rate of 30%:

10 Ingredients Parts by Weight 10

Corn Syrup 60

Licorice 10

Glycerine 20

Fig Juice 4.6

15 Prune Juice 5 15

Flavor Material of Example XIV 0.4

The resultant product is redried to a moisture content of 20%. On chewing, this tobacco has an excellent, substantially consistent, long-lasting raspberry (20 minutes) nuance in conjunction with the main fruity tobacco note.

20 Example XXI 20 Rose Formulation

To demonstrate the use of 3-hydroxy-1 -(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1 -butanone in a rose formulation, the following formula is provided:

Ingredient Parts by Weight

25 Phenyl ethyl alcohol 200 25

Geraniol 400

Trichloromethylphenyl carbinyl acetate 20

Phenyl ethyl acetate 60

Undecylenic aldehyde (10% in diethyl phthalate) 5

30 n-Nonyl aldehyde (10% in diethyl phthalate) 2 30

Musk ketone 10

Musk ambrette 10

Eugenol phenyl acetate 20

Citronellol 100

35 Vanillin (10% in diethyl phthalate) 6 35

Eugenol 30

Citronellyl formate 30

Geranyl acetate 10

Linalool 40

40 Geranyl phenyl acetate 50 40

Cis beta, y-hexenyl acetate 2 3-hydroxy-1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1 -butanone prepared according to Example I (A) 5

1000

45 The addition of 0.5% of 3-hydroxy-1 -(2,6,6-trimethyM ,3-cyclohexadien-1 -yl)-1 -butanone lends 45 a great deal of strength and character to the rose fragrance. It contributes floralcy and fruitiness with hay-like and menthane-like undertones.

At lower concentrations (0.01 %) its contribution is more subtle, however, it gives an interesting natural effect.

50 This product may normally be used from approximately 0.01% to 10% in perfume compositions. 50 For special effects, however, higher concentrations (50%) can be used.

Example XXII

Preparation of a Soap Composition

100 Grams of soap chips are produced according to Example V of United States Patent 4,058,487 55 issued on November 15,1977, as follows: 55

The sodium salt of an equal mixture of C10/C14 alkane sulfonates (95% active), 40 lbs., is dissolved in a mixture of 80 lbs. of anhydrous isopropanol and 125 lbs. of deionized water at 150°F. In

21

GB 2 058 757 A 21

this mixture is dissolved 10 lbs. of partially hydrogenated coconut oil fatty acids and 15 lbs. of sodium mono-C14-alkyl maleate, and'the pH of this solution is adjusted to 6.0 by the addition of a small amount of a 50% aqueous solution of NaOH. The isopropanol is distilled off and the remaining aqueous solution is drum dried. The resulting solid actives are then 5 blended in a chip mixer with 10 lbs. water 0.2 lb. titanium hydroxide and 0.75 lb. of the perfume composition of Example XXI. The chips are then plodded into logs, cut to size and finally stamped into bars, having a pH of approximately 6.9.

The perfumed soap manifests an excellent rose character with excellent sweet, floral and fruity notes.

10 Example XXIII

Preparation of a Detergent Composition

A total of 100 grams of a detergent powder prepared according to U.S. Patent 4,058,472 and containing 5% by weight of the sodium salts of a mixture of sulfonated C14—C18 alkyl catechol as a surface active component, the mixture being 60 parts by weight of mono-C14—C18 alkyl catechol and 15 40 parts by weight of di-C14—C18 alkyl catechol, 35% of sodium tetrapyrophosphate, 30% of sodium silicate, 20% of sodium carbonate, 3% of sodium carboxy-methylcellulose and 7% of starch, is mixed with 0.15 grams of the perfume composition of Example XXI until a substantially homogeneous composition is obtained. This composition has an excellent rose aroma with sweet, floral and fruity notes.

20 Example XXIV

Preparation of a Cosmetic Powder Composition

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcum powder with 0.25 g of 3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)~1 -butanone prepared according to Example I (A). It has an excellent floral, fruity, tobacco-like fragrance having rose, hay and menthane undertones.

25 Example XXV

Perfumed Liquid Detergent

Concentrated liquid detergents with floral, fruity, tobacco-like fragrances having rose, hay and methane undertones are prepared containing 0.10%, 0.15% and 0.20% of 3-hydroxy-1-(2,6,6-trimethyi-1,3-cyclohexadien-1 -yl)-1 -butanone prepared according to Example I (A). They are prepared 30 by adding and homogeneously mixing the appropriate quantity of 3-hydroxy-1 -(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-butanone in the liquid detergents. The detergents all possess a floral, fruity, tobacco-like fragrance having rose, hay and menthane undertones, the intensity increasing with greater concentrations of 3-hydroxy-1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1 -butanone.

Example XXVI

35 Preparation of a Cologne and Handkerchief Perfume

3-Hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-butanone prepared according to the process of Example I (A) is incorporated in a cologne at a concentration of 2.5% in 85% aqueous ethanol; and into a handkerchief perfume at a concentration of 20% (in 95% aqueous ethanol). A distinct and definite floral, fruity, tobacco-like fragrance having rose, hay and menthane undertones is 40 imparted to the cologne and to the handkerchief perfume.

Example XXVII

Preparation of a Cologne and Handkerchief Perfume

The composition of Example XXI is incorporated in a cologne at a concentration of 2.5% in 85% aqueous ethanol; and into a handkerchief perfume at a concentration of 20% (in 95% aqueous 45 ethanol). The use of 3-hydroxy-1-(2,6,6-trimethyM ,3-cyclohexadien-1-yl)-1-butanone in the composition of Example XXI affords a distinct and definite strong, floral, fruity, tobacco-like fragrance having rose, hay and menthane undertones to the handkerchief perfume and cologne.

Example XXVIII

Preparation of Soap Composition

50 One hundred grams of soap chips produced according to Example V of U.S. Patent 4,058,487 are mixed with one gram of 3-hydroxy-1 -(2,6,6-trimethyM ,3-cyclohexadien-1 -yl)-1 -butanone until a substantially homogeneous composition is obtained. The perfumed soap composition manifests an excellent floral, fruity, tobacco-like fragrance having rose, hay and menthane undertones.

Example XXIX 55 Preparation of a Detergent Composition

A total of 100 g of a detergent powder prepared as in Example XII, supra, is mixed with 0.15 g of the 3-hydroxy-1 -(2,6,6-trimethyM ,3-cyclohexadien-1 -yl)-1 -butanone of Example I (A) until a substantially homogeneous composition is obtained. This composition has an excellent floral, fruity, tobacco-like fragrance having rose, hay and menthane undertones.

5

10

15

20

25

30

35

40

45

50

55

22 GB 2 058 757 A 22

Example XXX Tobacco Formulation

A tobacco mixture is produced by admixing the following ingredients:

Ingredient Parts by Weight

5 Bright 40.1 5

Burley 24.9

Maryland 1.1

Turkish 11.6

Stem (flue-cured) 14.2

10 Glycerine 2.8 10

Water 5.3 Cigarettes are prepared from this tobacco.

The following flavor formulation is prepared:

Ingredient

Parts by Weight

Ethyl butyrate

.05

15

Ethyl valerate

.05

Maltol

2.00

Cocoa extract

26.00

Coffee extract

10.00

Ethyl alcohol

20.00

20

Water

41.90

The above-stated tobacco flavor formulation is applied at the rate of 0.1% to all of the cigarettes produced using the above tobacco formulation. Half of the cigarettes are then treated with 150 or 300 ppm of 3-hydroxy-1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1 -butanone produced according to the 25 process of Example I (A). The control cigarettes not containing the 3-hydroxy-1 -(2,6,6-trimethyM,3- 25 cyclohexadien-1-yl)-1-butanone produced according to the process of Example I (A) and the experimental cigarettes which contain the 3-hydroxy-1-(2,6,6-trimethyM ,3-cyclohexadien-1-yl)-1-butanone produced according to the process of Example I (A) are evaluated by paired comparison and the results are as follows:

30 The experimental cigarettes are found to have more body and to be sweeter, more aromatic, 30

more tobacco-like and less harsh with sweet, distinctive dried fruit-like, floral and woody notes. The tobacco of the experimental cigarettes, prior to smoking, has sweet, distinctive dried fruit-like, floral and woody notes. All cigarettes are evaluated for smoke flavor with a 20 mm cellulose acetate filter.

The 3-hydroxy-1 -(2,6,6-trimethyM ,3-cyclohexadien-1 -yl)-1 -butanone produced according to 35 the process of Example I (A) enhances the tobacco-like taste and aroma of the blended cigarettes, 35

imparting to it, sweet, dried fruit-like, floral and woody notes. In addition, the smoke flavor is cleaner.

Example XXXI

Utilizing the procedure of Example I of column 15 of United States Patent 3,632,396, a nonwoven cloth substrate useful as a dryer-added fabric-softening article of manufacture is prepared 40 wherein the substrate, the substrate coating and the outer coating and the perfuming material are as 40 follows:

1. A water "dissolvable" paper ("Dissolvo Paper"):

2. Adogen 448 (m.p. about 140°F) as the substrate coating; and

3. An outer coating having the following formulation (m.p. about 150°F):

45 57 percent C20_22 HAPS 45

22 percent isopropyl aicohol 20 percent antistatic agent 1 percent of the cyclohexadien-1 -yl-1 -butanone derivative or mixtures thereof of our invention as set forth in the Table I below and giving rise to the aroma nuances 50 set forth in the Table I below: 50

Table I

Name of Compound (or Mixture) Fragrance Characteristic

3-hydroxy-1 -{2,6,6-trimethyl- A floral, fruity, tobacco

1,3-cyclohexadien-1 -yl)-1 - aroma with rose notes and

55 butanone hay, menthane undertones. 55

1 -(2,6,6-trimethyM ,3-cyclohexadien-1 -yl)-1,3-

Imparts a sweet, honeylike, fruity, grape-like,

23

GB 2 058 757 A 23

Name of Compound (or Mixture) butanedione

10

15

50:50 mixture of 3-hydroxy-1 -(2,6,6-trimethyM ,3-cyclohexadien-1 -yl)-1 -butanone and 1-(2,6,6-trimethyl-1,3-cyclohexa-dien-1 -yl)-1,3-butanedione (mole ratio: 1:1)

Table I (Cont.)

Fragrance Characteristic rose-like, ionone-like,

hay-like and floral aroma with sea-amber and amber-gris-like undertones and sweet-floral topnotes.

Imparts a floral, fruity, tobacco, sweet, honey-like, fruity, grape-like, rose like, ionone-like, haylike and floral aroma with strong sea-amber and ambergris undertones and rose, hay, floral and menthane topnotes.

10

15

20

Fabric-softening compositions prepared as set forth above having the above aroma characteristics essentially consist of a substrate having a weight of about 3 grams per 100 square inches, a substrate coating of about 1.85 grams per 100 square inches of substrate and an outer coating of about 1.4 grams per 100 square inches of substrate, thereby providing a total aromatized substrate and outer coating weight ratio of about 1:1 by weight of the substrate. The aromas as set forth in Table I above are imparted in a pleasant manner to the head space in the dryer on operation thereof using the said dryer added fabric softening no'nwoven fabric.

Brief Description of the Drawings

Figure 1 is the nuclear magnetic resonance (NMR) spectrum for 3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-butanone produced according to Example I (A).

Figure 2 is the infra-red (IR) spectrum for 3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-butanone produced according to Example I (A).

Figure 3 is the mass spectrum (MS) for3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-butanone produced according to Example I (A).

Figure 4 is the ultraviolet (UV) absorption spectrum for 3-hydroxy-1 -(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-butanone produced according to Example I (A) using a methanol solvent.

Figure 5 is the NMR spectrum for 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione produced according to Example II.

Figure 6 is the infra-red spectrum for 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione produced according to Example II.

Figure 7 is the UV absorption curve [E|*m=473.04; Lambdamax=284nm] for 1-(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione produced according to Example II.

Claims (1)

1. Claims

   40 1.1 -(2,6,6-trimethyl-1,3-cyclohexadien-1 -yl)-1,3-butanedione having the structure:

   20

   25

   30

   35

   25

   30

   35

   40

   Q 0

   2. An equilibrium mixture containing compounds having the structures:

   o and

   3. A process for preparing a mixture according to Claim 2, which comprises the steps of (i) 45 intimately admixing methyl magnesium halide having the structure:

   45

   CH3MgX

   24

   GB 2 058 757 A 24

   with 1-acetyl-2,6,6-trimethyl-1,3-cyclohexadiene having the structure:

   whereby a first organometallic compound having the structure:

   5 is formed; (ii) intimately admixing the first organo-metallic compound with an acetyl halide having the 5 structure:

   ?

   3

   whereby a second organometallic compound is formed having the structure:

   10 (iii) hydrolyzing, in the presence of acid, the second organometallic compound whereby the desired 10

   equilibrium mixture is formed, wherein X represents halogen selected from chloro, bromo and iodo, and x' is halogen selected from chloro and bromo.

   4. A process according to Claim 3, wherein X and X' each represent chloro.

   5. A process according to Claim 3 or 4, wherein the hydrolysis of the second organometallic

   15 compound is carried out using acetic acid in aqueous media. 15

   6. An equilibrium mixture whenever produced according to any one of Claims 3 to 5.

   7. A process for utilising the equilibrium mixture according to Claim 2 or Claim 6 to augment or enhance the organoleptic properties of a consumable material, the process comprising adding to the consumable material an organoleptically effective quantity of the equilibrium mixture.

   20 8. A process according to Claim 7 in which the consumable material is a perfume composition. 20

   9. A process according to Claim 7 in which the consumable material is a cologne.

   10. A perfume composition comprising the equilibrium mixture according to Claim 2 or Claim 6 and an adjuvant comprising at least one alcohol, aldehyde, ketone other than 1 -(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione, nitrile, ester, lactone, dialkyl ether, alkyl alkenyl ether, thio ether,

   25 thiol, carboxylic acid or natural essential oil. 25

   11. A cologne comprising the equilibrium mixture according to Claim 2 or Claim 6 and ethanol and water.

   12. A process according to Claim 7 in which the consumable material is a detergent.

   13. A process according to Claim 12 in which a solid or liquid detergent base is intimately

   30 admixed with from 0.005% up to 3% of the equilibrium mixture. 30

   14. A process according to Claim 13 in which the detergent base is admixed with from 0.005%

   up to 0.2% of the equilibrium mixture.

   15. A process according to Claim 13, in which the detergent base is admixed with from 0.01 % up to 0.2% of the equilibrium mixture.

   35 16. A process according to any one of Claims 12 to 15 in which the detergent is a soap. 35

   17. A process according to Claim 7 in which the consumable material is tobacco.

   18. A process according to Claim 7 in which the consumable material is a smoking tobacco article.

   19. An organometallic compound having the structure:

   25

   GB 2 058 757 A 25

   wherein X represents halogen selected from chloro, bromo and iodo.

   20. An organometallic compound according to Claim 19, wherein X represents chloro.

   21. A process for preparing the compound according to Claim 19, which comprises the steps of 5 (i) intimantel, admixing methyl magnesium halide having the structure:

   CH3MgX

   with 1 -acetyl-2,6,6-trimethyl-1,3-cyclohexadiene having the structure:

   whereby a first organometallic compound having the structure:

   0/*laX

   10

   10

   is formed; (ii) intimately admixing the first organometallic compound with an acetyl halide having the structure:

   ?

   whereby a second organometallic compound is formed having the structure:

   i DfflgX

   15

   15

   22. A process in accordance with Claim 3, substantially as described in foregoing Example II.

   23. A process in accordance with Claim 7 substantially as described in foregoing Example XXXI.

   24. Any novel feature or combination of features described herein.

   Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1981. Published by the Patent Office, 25 Southampton Buildings, London, WC2A 1 AY, from which copies may be obtained.